7.56 @ Chemical Kinetics 28, 1-32 ‘Test by substituting the given values ofa and b 2,b=3, we get Whena 32! 2.303 log,, 100 = 127.7 see 825 «10490 pe 208 ‘1600 * 365 * 24 «86400 156.023 10 226 =3.7~ 10" Fora first order reaction, 3 k= 2303 jog hy 2.303 jy 100 _ 2.303 ; GO lB 40 ~~ GO O05 As k-Act Ink=Ina—fe Ea log,.k = log, A 3303 RT Ea logeA~ log, k + 398 ep Jog,,A™log,, (1.8 104) + 15,7082 log,,A = 0.2553 ~$ + 15.7082 = 10.9635 A= Antilog (10.9635) A=91.94 10" collision/see. Suppose k and k’ are the rate constants of the unca- talysed and catalysed reactions and Ea and E’a are their corresponding activation energies. k=Aem 15 kJ mot! ero Ask’= (1+ 1718) k=2718k=e =k Soe= e™-Fnt Ea-E’a=RT Ea=B’a + RT=4.15 +83 » 500 10° =83kI mot! 21. 28, 29. 30, slope --B2 N,0, > 2NO, Initial moles 1 Molesafter 1-02 04 disso. =08 ‘Total moles after dissociation -08+04=12 Initial temperature = 300 K ASP,V ev a) ‘Temperature after dissociation = 600 K. n, RT, 12 R« 600 @ ing equation (2) by (1), we get 1.2 « 600 = 00 — 9.4 atm 7 (Arthenius equation) when T+ 2 k=Ae%ork=A Thus k= 6 = 10's 64443 Order = 14+ 13 +4 = Sb =13/12, According to hit and trial method, if reaction is of ze10 order, ATA], [AD * 241A], -[A} adi2x Baio 30°? * i001 Ask is constant So the give reactions of zero order.CHAPTER 8 Chapter Contents Classification of solids, crystalline state, seven crystal systems (cell parameters a, b, c, alpha, beta, gamma), close packed structure of solids (cubic), packing in fec, bec and hep lattices; Nearest neighbours, ionic radii, simple ionic compounds, point defects and Various level of multiple-choice questions. SOLID STATE Solid is the state of any matter in which constituents are firmly attached due to strong forces. = Solids have a definite shape, mass and volume. = Solids are almost incompressible, rigid and have mechanical strength, 1m Solids have close packed arrangement of atoms. = Solids have high density but very slow diffusion rate = Solids can have only vibrational motion as the constituents have fixed positions. = In solids constituents have strong foree of attrac- tion as intrermolecular distances are short. Type of Solids Solids are mainly of the following two types Crystalline Solids In such solids, the constituents are arranged in a defi- nite or orderly manner which repeats itself over long distances. = They have a definite geometry with flat faces and sharp edges. = Such solids have sharp melting points and undergo clean cleavage. = They are considered as true solids.8.2 ™ Solid State = These show anisotropy that is, different physical | m Such solids do not have sharp melting points properties in different directions, and clean cleavage that is, have an irregular = They show clean cleavage. cut = They are normally incompressible. Example, | m These are considered as pseudo solids. Diamond, Quartz, @ These show isotropy that is, same physical prop- = Allelements and compounds are of this kind, Py Physical prop- erties in all directions Amorphous Solids = They do not show clean cleavage. In such solids, the constituents are not arranged in a regular or orderly manner over the long range REMEMBER Due to short range order, amprphous solids may even have small parts in crystalline and the rest in non-crystalline form. Crystalline parts of an otherwise amorphous substance are called crystallites. line Solids On the basis of nature of constituent particles and binding forces such solids are of following four types Type Constituents Nature Physical M.P. BE.in Condue- Examples of Solids Particles of Force State in Kelvin kJ/mole Ionic Cations and Strong. Hard but Very high> — 400-4000 Condue- NaCl, KCI, anions: electrostatic brittle 1300K tors KNO,, forces a0, LiF Covalent Atoms Covalent Very hard Very-very 150-500 Insulators Diamond, ‘or network bonds high >3900 K SiC, SiO,, Quartz Molecular Molecules Van der Waal’s Soft Low<273K Low<40 Insulators Dry ice, forces likes 1, solid London forces argon, P,, dipole dipole S,etc., interaction and hydrogen bonding Metallic — Atoms Metallic Hard but High 800 ~ 80~ 1000 Conduc- All metals bonds malleable 1000 tors and most and ductile of the alloysSolid State M_8.3 Terms Related to Crystals Crystal Itis a homogeneous part of a solid substance made by regular pattem of structural units bonded by plane surface making definite angles with each other, Crystal Lattice or Space Lattice It is the regular arrangement of constituent parti- cles (atom, ions etc.,) of a crystal in three dimen- sional space. Face It is the plane surface of the crystal. Space lattice and unit cell Edge It is formed due to inter section of two adjacent faces. ¢—__ INTERFACIAL. ” ANGLE Normal to face B Nomnal to face A Interfacial Angles It is the angle between the perpendiculars of two intersecting faces, When three or more edges inter- sect, a solid angle is formed. Unit Cell It is the smallest unit or three dimensional portion of the space lattice which when repeated over and again in different directions give rise to the com- plete space lattice. m= Itis the smallest geometrical figure having all the properties of a crystal in a erystal lattice. = Any crystal may have 2 number of unit cells. m= Itis characterized by a,b, ¢ (edge distance) and a, By, (angles). Type of Unit Cell Unit cells are of following types: 1. Simple or Primitive or Basic Unit Cell: Here lat- tice points or particles are present only at the cor- ners and no where else. In this arrangement each ‘atom is in contact with six immediate neighbour- ing species hence co-ordination number is six. 2. Face Centered Unit Cell: Here lattice points or particles are present not only at comers but also at the centre of each faces, 3. Body Centered Unit Cell: Here particles are present at all comers and centre of the body of the unit cell. 4. End Face Centered: Here particles are present at all comers as well as in the centre of two opposite faces. 4 | i Ee 1 + Simple cubic Body-centred cubic Face-centred cubie Types of Symmetry in Crystals m= A crystal may have center of symmetry plane of symmetry and axis of symmetry which can be explained as follows. = Plane of symmetry is that imaginary plane which passes through the centre of the crystal and divide it into Wo equal portions (just mirror images of each other). m= Center of symmetry is an imaginary point which divides the surface of the erystal at equal distances in both directions by drawing any line through it A crystal ean have only one centre of symmetry.8.4 ™ Solid State = Axis of symmetry is that imaginary straight line on which rotation of crystal gives similar appear- ance more than one time. It is two fold, three fold, four fold and six fold type respectively. Rectangular plane Diagonal plane of symmetry (a) of symmetry (6) Axis of four-fold Axis of three-fold symmetry (c) symmetry (d) Centre of symmetry () Axis of two-fold symmetry (e) Various elements of symmetry in a cubic crystal. CRYSTAL SYSTEMS There are seven type of erystal systems and 14 bra- vais lattices as given below Crystal system Parameters of Unit Cell Bravais lattices Intercepts Interfacial angle Examples Cubic Orthorhombie Tetragonal Monoclinic ‘Triclinie Hexagonal Rhombohedral Total = 14 Primitive, face centered, a=b=e body centered = 3 Primitive, face centered, a#b#e body centered, end cen- Ag. Au, Hg, Pb, dia- mond, NaCl, ZnS K,S0,, KNO, BaSO, Rhombic Sulphur tered=4 Primitive, body centered a=b#e TiO,, SnO, , CaSO, =2 White Tin Primitive,endcentered a¢b#e a= B=90 CaSO,2H,0 =2 yee Primitive = 1 a¢b¢e a #P #y #90" CuSO, 5H,O, K,Cr,0,, HBO, Primitive = 1 a=bde Zn, Mg, Cd, SiO, Graphite, Zno Primitive = 1 a=b=c Bi, As, Sb, CaCO, HgsSolid State M85 and Le / ee Simple or Primitive (P) Body-centred (I) Face-centred (F) Cubie Space Lattices Simple or Primitive (P) Body-centred (I) End-centred (C)_Face-centred (F) Orthorhombic Space Lattices Simple (P) __ Body-centred (1) Simple (P) _End-centred (C) Tetragonal and Monoclinic Space Lattices ie 4 Triclinie Hexagonal Rhombohedral or Trigonal (R) Triclinic, Hexagonal and Rhombohedral Space Lattices8.6 M Solid State Tetragonal B= 90°| a Orthorhombic a A Rhombohedral /o Triclinic Seven primitive unit cell in erystals Packing of Constituents in Crystals One can better understand the general geometrical requirements for crystal formation by considering various modes of packing in a number of identical spheres, It is of the following two types: Close Packing In Two Dimensions Here close packing arrangement in two dimensions are as follows: @ Square Close Packing: Here cach sphere is in contact with four other spheres. Here voids are square. Here 52.4% space is oocupied by spheres. Horizontal alignment Central sphere in contact Vertical with 4 other sphere alignment (ii) Hexagonal Close Packing: It ismore dense than the square Close packing. Here, voids are triangu- lar. and 60.4 % space is occupied by spheres Hexagon Vertical contact with 6 other alignment sphere Central sphere in Packing In Three Dimensions Atoms/lons are space filling entities and structures can be described as resulting from the packing of spheres. The most efficient arrangement of spheres is called closest packing.In this kind of arrangement cach sphere is in contact with the maximum possible number of adjacent neighbours. Here each sphere is surrounded by six nearest neighbours, lying in one plane, three spheres are just above it and some num- ber are just below it also, This means the total num- ber of nearest neighbours is twelve (Co. no=12). This kind of arrangement is further devided into H.CP and C.CP. arrangements. In order to obtain hex- agonal close packing, first, spheres are placed on a flat surface to form layer (A) as shown in the figure (g). Now in order to form another another layer ‘B” equally bunched spheres so as to nestle into the voids. From the given figure, it is clear that two types of voids (p.q) are formed. If a sphere is placed on the p- type of voids it resembles the A-layer of spheres. This kind of AB-AB type of arrangement is called H.CP. If spheres are placed on q type of voids, itis another kind of unique layer let us call it ‘C’- layer. It means. ABC, ABC type of arrangement is formed which is called C.CP.() Hexagonal Close Packing: = Atoms are located at the comers and the center of two hexagons placed parallel to each other, three more atoms are placed in a parallel plane midway between these two planes. Here packing gives the arrangement of layers as AB, AB , ----- It has a six fold symmetry = Here 74 % space is occupied = Here same appearance is obtained by rotating the crystal at 60°. = Co-ordination is 12. Example, Mg, Zn, Mo, V, Ca’ ‘& . & : : . Arrangements in HCP (ii) Cubic Close Packing: ‘The sphere in the fourth layer will correspond to those in first layer and give rise to ABC, ABC, -- type of packing It has 3 fold axis of symmetry which are passing through the diagonal of the cube. Here co-ordination number is 12 Examples, Cu, Ag, Au, Ni, Pt © BS, Arrangments in CCP Body Centered Cubic Packing: Here each sphere is in contact with 8 spheres four in the lower layer and four in the upper layer It is possible when the spheres in first layer are slightly opened that is, none of the sphere is touching each other. It is shown by Li, Na, K, Rb, Cs, Ba etc., Solid State ™ Packing Efficiency in HCP and CCP Structures G B Cubic close packing-other sides are not provided with spheres for sake of clarity. Both types of close packing (hep and cep) are equally efficient. Let us calculate the efficiency of packing in cep structure. In the figure, let the unit cell edge length be ‘a’ and face diagonal AC = b. In A ABC Act C+ AB sata? =2a? or b=v2a If ris the radius of the sphere, we find b= 4r V2a At 9y) ora= i= 220 v2 (We can also write, w2 As we know, that each unit cell in cep structure, has effectively 4 spheres. Total volume of four spheres is equal to 4 « (4.3) x1? and volume of the cube is a3 or (2V2r)? Therefore,8.8 M Solid State Packing efficiency Volume occupied by four spheres in the unit cell x 100% Total volume of the unit cell _4*@B) xP 100 , (2N2)° _ (06/3) n° 100 _ "162 4% Efficiency of Packing in Body Centered Cubic Structure Body centred cubic unit cell (sphere alone the body diagonal are shown with solid boundaries). From figure, it is clear that the atom at the centre is in touch with the other two atoms diagonally arranged. In AEFD, = attat= 2a? b=v2a Now in AAFD 2 = a2 4b?= c= Ba 2a? = 3a ‘The length of the body diagonal c is equal to 4r, here is the radius of the sphere (atom), as all the three spheres along the diagonal touch each other. So V3a=3r In this type of structure, total number of atoms is 2 4 and their volume is 2x Qn a Volume of the cube, a? will be equal to © . ora? v 4p? 3 There fore, Packing efficiency _ Volume occupied by two spheres in the unit x 100% ~ Total volume of the unit cell a4 4B) RPx 100 y, [43 ep = 45 3) rx 100,, 6433) ° = 68% Interstitial Voids Itis the space left after different type of packings like hep, cep due to the spherical nature of atoms that is, the three dimensional interstitial gaps are called voids. These are of the following types: @ TrigonalVoids: Itisthe vacantspace touch- ing three spheres that is, it is a two dimen- sional void formed when three spheres are in same plane whose centers are at corners of triangle Tetrahedral Voids: It is the vacant space touching four spheres that is the void whose surrounding spheres are located at the comers of regular tetrahedron. In gen- eral the number of these voids in a unit cell is double the number of effective atoms in that unit cell. (ii) Octahedral Voids: It is the vacant space touching six spheres that is void resulting from overlapping of two trigonal voids of adjacent layer whose surrounding spheres are located at the comers of octahedron. In general, the effec- tive number of these voids in a unit cell is equal is to the number of effective atoms present in the unit cell (iv) Cubie voids: It is the vacant space touching eight spheres located at the comers of a cube.Solid State ™ _aistlayer % . ‘Tetrahedral e Detahedrall void Undlayer void Co.No, £72... P Co, No.=8. Co.No.=4 Location of Voids in Unit Cell (@ Tetrahedral Voids: These voids are located at the body diagonals, two in each body diagonal at one fourth of the distance from each end. Total ‘number of these voids per unit cell = 8 (ii) Octahedral Voids: These voids are located at the middle of the cell edges and at the cen- tre of cubic unit cell Total number of octahedral voids = «12 +1 So in cep, the total number of voids per unit cell +4= (letrahedral) (Octahedral) Vg 0414Xr = 0.214Xr V,, = OS Xr Ven> Ves” Vx Here ris the radius of the biggest sphere Illustrations 1. A compound is formed by two elements M and N. The element N forms cep and atoms of M oceupy 1/3 rd of tetrahedral voids. What is the formula of the compound? Solution Nincop= dxs+4xo=4 (comer) Min tetrahedral voids = 8 « 4=3 =3:2 Thus formula of the compound is M,N, 2. Inacubicclosepacked structure (cep)ofmixed oxide, it is found that lattice has O> ions and one half of the octahedral voids are occupied by trivalent cations (X) and one eighth of the tetrahedral voids are occupied by diva- lent cations (Y"). What is the formula of the mixed oxide? Solution a =px4=2 ‘Number of divalent cation (Y") Number of trivalent cation (X™) al =gx8el pal tiga Number of OF = 4 x8+5x6 =4 (cep) (comer) (face) ‘Therefore formula is X,YO,, 3. Acubic solid is made up of two elements A and B. Atoms B are at the comers of the cube and A at the body centre: (i) What is the formula of the compound? Gi) What are the co-ordination numbers of Aand B?8.10 ™ Solid State Solution () Number of atoms of A (present at comers) contributed per unit cell =}x 8 =1atom Number of atoms of B (present in the cube) con- tributed per unit cell = I atom Ratio of atoms A and B in the unit cell = 1: 1 So the formula of the compound = AB (ii) The co-ordination number of each element (Aand B) is 8. 4. Calculate the number of atoms in a cubic based ‘unit cell having one atom on each comer and two atoms on each body diagonal. Solution Number of atoms contributed by 8 comer atoms per unit cell =y%8= atom ‘As number of atoms contributed by one diagonal =2 atoms So number of atoms contributed by 4 diagonals = 4x 2 atoms =8 atoms Therefore, total number of atoms contributed per unit cell = 1 +8=9 atoms. Mathematical Analysis Of Cubic System 1, Atomic Radius and Edge Length It is half of the distance between two nearest neighbour atoms in a crystal. It is expressed in terms of length of the edge (a) of the unit cell of a crystal (a) In Simple Cubic: Here atoms located at comers are in contact, Kea [ty @ a=2r (ii) Distance between two nearer neighbour =all=r that is, d= 5 =2 (b) In face centered cubie (FCC): a 4 c Here atoms on face diagonal are in contact In triangle ABC AC= \(AB? +BC*) \@r +a?) \2 xa That is, 4r = V2 x a Gi) d=2r Here d = distance between two nearest atoms (©) In Body Centered Cubie (BC): A B D Here atoms on body diagonal are in contact that is, +2rtr Ir AD=BD = 4r= (AC? +CD*) Body trigonal =V (a? + a) + a] 4r=\3%a @ a= forBec 3 (i) d=2r Here d = distance between centers of two closest atomsSolid State ™ 8.11 Property Primitive Fcc BCC — Facial Facial Body diagonal . ar 4r 4r Edge length fre ua eTength ame ear 2 Volume occupied by spheres. 1x $ar° 4xder ‘Volume of unit cell a= (2\2 np} Packing fraction . 4x4B a0 2x4 ar _ Vol. occupied by atoms “gr 7052 “ohn Tansy 08 *~~Yol. of unit cell Percentage of free space per 47 6 9, pea aoe unit cell 2. Number of Atoms Per Unit Cell or Unit Cell Content (Z) = Itis the total number of atoms contained in a unit cell for a simple cubic crystal n Here n,=3,n,=6,n,=1 These are number of atoms at comer, face and inside body. In case of simple cubic erystal: 1 Z=8xh=1 As each comer atom is shared by eight surround- ing cubes so it contributes for 1/8 of an atom. m= In face Centred Cubic Structure: Z=341=4 As the eight comers atom contribute for 1/8 of an atom that is, one atom per unit cell As each of 6 face centered atom is shared by two adjacent unit cells so one face centered atom con- tributes only half of its share that is, 6x }- 3 (atoms per unit cell) = In Body Centered Cubic Structure: Here Z=1+1=2 As eight comers atoms will contribute only one atom per unit cell and centre atom contributes only one atom per unit cell Address of Faceof Comer of Body Comerof Side of Edge of an atom, Cube Cube centre __Hexagenal _Hexaganol Cube Contribution % 18 V6 ‘ v4 3. Co-ordination Number (C. No.) It is equal to the number of nearest neighbours (atoms onr ions) that is, touching Particles present around a species in a crystal, Its value gives us a measure of now tightly and closely the spheres are packed together the larger value of its means more closer packing Its values depends upon the structure of crystal. Example, S.C Co-ordination number is 6 F.C.C: Co-ordination number is 12 BCC: Co-ordination number is 88.12 ™@ Solid State 4. Density of Lattice Matter (d) 1 It is the ratio of mass per unit cell to the total volume of a unit cell and it is find out as follows. Zx omic weight = Nx Volume of unit cell @) Here d= Density Z= Number of atoms N, = a= Edge length Here in order to find density of unit cell in g fem’, m must be taken in g/mole and should be in cm. Packing Fraction = Itis the ratio of the volume occupied by spheres or effective atoms in a unit cell to the total volume of that unit cell. The fraction volume of the unit cell, that is empty is known as void fraction. zx 4132 — PF. = In Simple Cubic: =052=52% m= In Face Centered Cubic: 4B ae p = ABER 74 = 74% (ray As a=4r/V2 % void = 26% © Radius Ratio: (R,=r/r-) Itis the ratio of radius of octahedral void to the radius of sphere forming the close packed arrangement Normally ionic sol- ids are more compact as voids are also occupied by cation (smaller in size) pattem of arrangements and type of voids both depend upon relative size ionic size) of two ions in solid. Example, when r® = r° the most probable and favourable arrangement is BCC type. With the help of a relative ionic radii, it is easier to predict the most probable arrangement. This property is expressed as radio ratio. 1 (radius of cation) Radius ratio = = (Radius of anion) From the value of radius ratio it is clear that larger the radius ratio larger is the size of cation and more will be the number of anions needed to surround it, that is, more co-ordination number. % void = 48 % = Shape Radius-ratio Co-ordination number = In Body Centered Cubic: x 4B an For cubic 0.732-1.000 8 p= TAB RE 9 6g = 68% (403P° For octahedral 0.414-0.732 6 As a=4ni3 For tetrahedral 0.225-0.414 4 % void = 32% For triangular 0.155-0.225 3 Ee eI z g ~ ( =~ BZ ae E E ae Se 7 <0.414 |i > 0.732 38 2k ~~ nd a5 2a 28 ge( — — | —_ 2 8 ge ce S& 5 Octahderal (Co-ord, No. 6) oad <0.732@ Radius ratio for tetrahedron (co-ordination number 4) Angle ABC is the tetrahedral angle of 109.5° 109.5 2 In triangle ABD, ZABD 475° Sin ABD = 0.8164 = AD/AB (ii) Radius ratio for octahedron ABar +r BD=r ZABC = 45° In triangle ABD Cos ABD = 0.7071 = BD/AB = Fer 1 oro7 = 44 Solid State m 4.13 Illustrations 5. Find the close-packed structure of an ionic ‘compound X*Y> in which the radius of the cat- ion = 148 pm and the radius of anion = 195 pm. What is the co-ordination number of cation? Solution — Radius ratio = r'/r 148 _ 975 488 = 0.759 As the value of radius ratio (0.759) is more than 0.732, the crystalline solid X"Y-has body cen- tered cubic lattice. The co-ordination number of X*: Y-:: 8:8 6. A solid X' Y- has NaCl type close packed structure, If the anion has a radius of 241.5 pm, what should be the minimum radius of the cation? Can a cation, Z* having radius of 30 pm be fitted into the tetrahedral hole of the crystal X* Y? Solution Radius ratio for an octahedral hole 1 _ Size of the cation X" Y *'Size of the anion Y Ala 0.4141 = 0.414 x 241.5 = 99.98 pm. Fora tetrahedral hole = = 0.225 The minimum radius of the cation X" to fit exactly into the octahedral hole should be 99.98. = 0.225 r = 0.225 x 241.5 = 54.34 pm As the size of the cation 2 (50 pm) is less than the ideal radius (54.34 pm), it can be fitted into tetrahedral hole of the crystal X* Y- In crystalline solid, anion Z are arranged in cubic close packing, cations X occupy 50 per cent of the tetrahedral voids and cations Y occupy 50 percent of octahedral voids. What is the formula of the solid? Solution Suppose the number of anions, Z, Number of cations, X 3G « Number of octahedral void8.14 @ Solid State = FR « @ «Number of anions Z) = 100 Number of Cations, Y = 50 100 = 0, « Number of anions Z x Number of octahedral void 50. Foo * 100=50 Ratio of ions : A: B: C (00 : 50: 100 1:2 So, formula of the compound is A,BC, 8 Copper which crystallizes asa face-centered cubic lattice has a density of 8.930 giom? at 20°C. (Calculate the length of the unit cell Gii) Calculate the radius of a copper atom. Solution The number of atoms per unit cell is 4/as copper crystallizes as face centered cubic lattice. Z=4 atoms/unit cell, Atomic mass of copper = 63.5 g/mol. Atomic mass * Z Density = “Gait cell volume (em) N, omic mass x Density x N, Unit cell volume = = OBS X44. 720 « 10 eamPhmnitc = FoR eG ODE TOS = 4722 « 10” cm’hanit ell Length of side of the unit cell = (V em’)! = [4.722 « 10° = 3.616 « 10%om 1 pm =3.616 x 10# x 7 = 361.6 pm For a face centered cubic lattice, a= V8 x r 361.6 pm a = = 128 se ia 9. An element crystallizes in BCC structure, The ‘edge of its unit cell is 288 pm. If the density of the crystals is 7.2 g em, What is the atomic ‘mass of the element? Solution As the element has BCC structure so number of atoms per unit cell is 2. Length of edge of the unit cell = 288 pm Lom = 288% Tp 288 x 10 em Volume of the unit cell = (288 x 10" cm)’ = 2.4 10% em? Atomic mass = Z. Density = Tit cell volume * N, Density x Unit cell volume x N, Atomic mass = 5? = 1.2424 x10 x 6,023 x 108 2 =52.gmot" 10. An clement crystallizes in FCC structure. Its density is 7.2 g cm. 208 g of this element has 4.283 x 10* atoms. Calculate the edge length of the unit cell Solution —Molarmass= Mass of 6 023 « 10° atoms: Mass of 4.283 * 10 atoms = 208 g Atomic mass = Mass of 6.023 « 10° atoms 208 x 6.023 = 10% RSet = 29.25 gimol Atomic mass x Z, V (em) « N, Density Atomic mass x Z Density x N, Unit cell volume = 29.25 x4 Tx 6.003 x 108 ~ 7698 * 10% om a=(V)'9 = 9(26.98 x 107 =3 x 10% om, 11. Tungsten has a density of 19.35 g cm and the length of the side of the unit cell is 316 pm. The unit cell in the most important erystalline form of tungsten is the body-centered cubic unit cell. How many atoms of the element does 50 g of the element contain? Solution Length of edge of the unit cell = 316 pm 316 x ThE = 316 x 10% em To" pmSolid State ™ 8.15 Volume of the unit cell = (316 * 10°” em) = 3.2 10 cm'funit cell Density x Unit cell volume x N, Z Atomic mass 9.35 x 3.2 x 10° x 6023 x 10" 2 86.5 gimol As 186.5 g of the element contains N, atoms = 6.023 « 10” atoms So 50 g of the element contain N, atoms 50 186.5 = 1.614 10? atoms = 6.023 x 10" « 12. Given for Fe: a pm = 286, p g em” = 7.86. Find the type of cubic lattice to which the erys- tal belongs. Also calculate the radius of Fe. (Atomic weight of Fe = 55.85). Solution — Length of edge of the unit cell = 286 pm = 286 « Lom x10" = 286% Typ = 286 « 10" pm Volume of the unit cell = (286 « 10" em)" = 234 10 cm? IL volume x Density x N, ‘Molar mass of Fe x 7.86 x 6,023 x 104 55.85 2 ‘As the number of atoms per unit cell is 2, iron has body centered cubie crystal structure. (Q2r) 3 AP «286 = 123.8 pm 13. Potassium fluoride has the NaCl type struc- ture. The density of KF is 2.48 gem? at 20°C. (@ Caleulate the unit cell length, (ii) Caleulate the nearest neighbour distance in KF. Solution NaCl has face centered cubic lattice. The number of formula units (ion-pairs) per unit cell of ‘NaCl or KF is 4 as it has a face centered cubic lattice. Formula mass of KF = 39+ 19= $8 amu Z = 4 formula unit/unit cell Formula mass x Z Density =Tnit cell volume = N, = Formula mass * Z Unit cell votume = Seri N, 58 x4 248 x 6.023 x 105 = 1,553 « 10% cm*funit cell Unit cell volums Unit cell length = (V)!" = (1.553 x 10% em’)! =5.377 « 108 = 537.7 pm The nearest neighbour distance is shortest distance between any two ions in the lattice. In a FCC unit cell of the compound of the type AB, the side of the cube contains ¥4 ion of A, | ion of B and % ion of A. Thus length of the side of the unit cell is twice the nearest neighbour distance. The nearest neighbour distance in KF Length of the side of unit cell 14, An element “X” (atomic mass 100) having BCC structure has unit cell edge 400 pm Calculate the density of X and the number of unit cells for 10 g of X. (N, = 6.023 x 10”) Solution Length of the unit cell edge = 400 pm = 490x<122_ = 40x10" = 400% Tym = 400% 10° em Volume of the unit cell = (400 x 10" em) =6.4% 10 em? As element ‘X’ forms a body centered cubic lattice so number of atoms per unit cell is 2. 2 atoms/unit cell Atomic mass of the element = 100 g/mol Atomic mass x Z Density of element = Grit cell volume » N,8.16 ™ Solid State 100 x2 64x 10 x 6.023 x 10" = 5.188 g/em? ‘Number of unit cells in 1.9275 em? volume — Volume of the substance Unit cell volume = 1.9275 = GPP iis = 3.0 « 10 unit cells 15. From the following data calculate the Avoga- dro number, sodium chloride crystal exists as a face-centered cube. The density of sodium chloride is 2.164 g ml and the distance between Na* and CI ions from X-ray analysis ‘was found to be 2.818 A. Solution The distance between Na* and Cions (4) =2.818A = 2.818 10%cm ‘The length of the unit cell for the face-centered cubic crystal = = 2x 2.818 x 10% em ‘Volume (V) of the unit cell = P= (2 x 2.818 x 10%) = 1.792 x 107? ml = Mx4 Volume of the unit cell = W*% Here M = molecular weight of the substance D=Density N= Avogadro number 22m) = 58-44 x4 1.792 x 10 ml = 352 58.44 x4 2.165 * 1.792 x 10 N 6.026 x 10" Structure of Some lonic Solids 1. Rock Salt (NaCl type): = Init Clions has C.CP. structure that is, F.C.C. and ‘Na’ ions occupies octahedral holes (voids) here. = Both Na’ and Cl-have co-ordination number sis. Number of formula units per unit cell are four. Example, Halodes of Alkali metals (except sx) like LiX, NaX, KX, other halides like AgCl, AgBr, NH,Cl and oxides like Ti0, FeO, NiO, mrt al2 tlt. must be 0.414 however, it is 0.525 CHONS SURROUNDED OCTAHEDRALLY BY SIX ‘Nat IONS, \Na* IONS SURROUNDED OCTAHEDRALLY BY SIX ‘CHIONS NaCl crystal (AB) 2. CsCl—Type: = Here Cl ions are at the comers of a cube and Cs" ions are in the cubic void (centered position) i.e.B.C.C like structure, = Here co-ordination number of both Cs* and Clris 8 and here number of formula units per unit cell is Lr, +1,=V3/2 @ Here r,,,/1,, should be 0.732 but it is 0.93. e.g. CsX, TiC1, TiBr, NH,Cl, NH,Br. Structure of CsCl @c ocs 3. Zine Blende (ZnS Type): m= Here S* occupies C C Por fC C arrangement while ‘Zn** ions occupy altemate tetrahedral voids.Solid State ™ 8.17 = Only half of the total voids is occupied = Here co-ordination number of both Zn** and S* is four and here number of formula units per unit cell is four. Example, ZnS, Beo CuCl, CuBr, Cul, Agl ete., ntnav3e @ sO a 4. Fluorite Structure (CaF, Type) = Here Ca® occupies C.C.P and F* ions occupy all the tetrahedral voids. = Here coordination number of Ca** is 8 while for F itis four and the effective number of Ca"? and F ions in a unit cell are 4 and & respectives here number of formula units per unit cell is four 1 +1,= 13/4 Example, CaF,,,BaCl,, BaF, SF, ,CO,, ThO,, PbO, ete. 5. Anti-fluorite Structure (Na,O Type): = Here negative ions (O*) occupy C.C.P. while cat- ions (Na*) occupy all the tetrahedral voids. = Here co-ordination number of Na’ is four while for O* itis eight here number of formula units per unit cell is four and the effective number of Li’ and O7 ions in a uniteell are 8, and 4 respectively r+1,= V3 ald Example, Na,O K,O, Li,O etc., t ie “d Rot @ 0 O Na 1Na,O Structure is an example of antifluorite structure. Normal Spinal Structure (XY,O,) = Spinal is MgA1,O, and spinals in general have the formula AB,O, Here A is divalent cation (Mg, Ca’) and B is trivalent cation (Al)”. = Here Mg’ occupy tetrahedral voids while oxide ions 1/8 of AP* occupy % octahedral voids, Im rn it a Ferites [ZnFe,0,] FeFe,O,, MnMn,0,,FeCr,0, also have this type of structure. m= As magnetic materials these are used in tele- phones, memory loops of computers. Inverse Spinal Structure (Fe,O,, Magnetite) m= InFe,O,, Fe™ and Fe® are present in 2 : | ratio. = Here oxides ions are in C C P while Fe™, ions occupy octahedral voids while Fe” occupy octa- hedral and tetrahedral voids. = Here O* ions forms FCC unit cell Here the formula ratio of Fe Fe": O%=1:2:48.18 M Solid State = MgFe,0,, Pb,O,, Mn,0, have also this type of structure, Effect of Temperature and Pressure on Crystal Structure (@_ On increasing the temperature of CsCI struc- ture co-ordination number decreases from 8:8106:6 csc] 4+ NaCI Structure 8:8 6:6 (ii) On subjecting the NaCI structure to high pressure it will increase co-ordination num- ber from 6 : 6 t0 8:8. vac Dishly pressurized 6:6 CsCl Structure 8:8 Imperfections in Solid Any deviation from the perfectly ordered arrange- ment constitutes a defect or imperfection. These defects are sometimes called thermodynamic defects because the number of these defects depend on the temperature, = Crystals may also possess additional defects due to the presence of impurities. Imperfection not only modify the properties of solids but also gives rise to new properties. Electronic Imperfection: Generally clectrons are present in fully occupied lowest energy states but at high temperatures, some of the electrons may occupy higher energy states depending upon the temperature. = For example, in the crystals of pure Si or Ge some electrons are released thermally from the covalent bonds at temperature above 0 K. These electrons are free to move in the crystal and are responsible for electrical conductivity. This type of conduction is known as intrinsic conduction = The electron deficient bond formed by the released of an electron is called a hole. In the presence of electric field, the positive holes move in a direction opposite to that of the electrons and conduct electrically Atomic Imperfection: The compounds in which the number of irregularity present in the arrangement of atoms or ions are called atomic imperfections. It is of two types: (@ Stoichiometric Defects: Those compounds in which the number of positive and negative ions are exactly in the ratio indicated by their chemical formula are called stoichiometric compounds example, NaCl. These solids show following types of defects (a) Schottky Defect SCHOTTKY DEFECT This type of defect is created when same number of positive ions and and negative ion are missing from their respective positions leaving behind a pair of holes. Schottky defect is more common in ionic com- pounds with high co-ordination number and where the size of positive and negative ions are almost equal. = This defect decreases density of crystals, however, it maintains electrical neutrality example, NaCl, CsCl, KCI, KBr ete. (b) Frenkel Defect This type of defect is created when an ion leaves its correct lattice site and occupies an interstitial site. = Frenkel defects are common in ionic compounds which have low co-ordination number and in which there is large difference in size between positiveSolid State ™ 8.19 and negative ions or when the crystal structure is of ‘an open type with large interstitial spaces. Example, ZnS, AgCl, AgBr, Agl ete Non Stoichiometric Defect: ‘There are many compounds in which the ratio of positive and negative ions present in the compound dif- fers from the required by ideal formula of the compound. Such compounds are called Non stoichiometric compounds. Example, VOx = In these compounds, a balance of positive and negative charges is maintained by having extra electrons or extra positive charge. These defects are of following types (@) Metal Excess Defects due to Anion Vacancies ‘A compound may have excess metal ion if a nega- tive ion is absent from its lattice site, leaving a hole which is occupied by an electron to maintain electri- cal neutrality. = The holes occupied by electrons are called F-centres and are responsible for the colour of the compound. Example, = The excess of sodium in NaCl makes the crystal to appear yellow: = Excess of potassium in KCI makes it violet. = Excess of lithium in LiCl makes it pink = Greater the number of F-centres greater is the intensity of colour. This type of defects are found in crystal which are likely to possess schottky defects. () Metal Excess Defects due to Interstitial Cations m= It may occur if an extra positive ion is present in an interstitial site m= Electrical neutrality is maintained by the pres- ence of an extra electron in the interstitial site m= This types of defects are exhibited by the crystals which are likely to exhibit Frenkel defects Example, Yellow colour of ZnS. (© Metal Deficiency due to Cation Vacanci The non stoichiometric compounds may have metal deficiency due to the absence of a metal ion from its lattice site. The charge is balanced by an adjacent ion having higher positive charge, These type of defects are generally shown by compounds of transition metals. Example, FeS NiO Enhance Your Knowledge Electrical Properties of Solid m Diamagnetic Substance: These substances are weakly repelled by the magnetic field and do not have any unpaired electron. They act as insulators Ththts Example, NaCl, Zn, Cd, Cu’, TiO,ete. m= Paramagnetic Substances: These substances are attracted by the magnetic field and have unpaired electrons. They lose magnetism in the absence of magnetic field. th tt8.20 ™ Solid State Example, Transition metals like Cr, Mn, Ni, Co, Fe etc, Metal oxides like CuO, VO, ete. = Ferromagnetic Substances: These substances are attracted by the magnetic field and show permanent magnetism even in the absence of magnetic field. Example, Fe, Co, Ni, CrO, (used in audio and video tapes) ete = This arises due to spontaneous alignment of magnetic momenta in the same direction tttttt = Above urie temperature, there is no ferromag- netism = Antiferromagnetic Substances: These are the substances which are expected to possess paramagnetism or ferromagnetism on the basis of unpaired electrons but actually have zero net magnetic moment. Example, MnO, MnO, Mn,0,, FeO, Fe,0, ete = Anti-ferromagnetism is due to equal number of parallel and antiparallel magnetic momenta which leads to zero resulting magnetic moment. titty m= Ferrimagnetic Substances: In_ ferrimagnetic substances, there are unequal number of parallel and antiparallel magnetic momenta which leads to some resulting magnetie moment. thdeth Example, Fe,O, , Ferrites Effect of Temperature = The ferromagnetic, anti-ferromagnetic and ferrimagnetic solids change into paramagnetic at a particular temperature. Example, Ferrimagnetic Fe,O, on heating to 850 K becomes paramagnetic this is due to alignment of spins in one direction on heating, Curie Temperature Each ferromagnetic substance has a characteris- tic temperature above which no ferromagnetism is observed this is called curie temperature. Piezoelectricity Itis the electricity produced when mechanical stress is applied on polar crystals Pyroelectricity It is the electricity produced when some polar erys- tals are heated. Ferroelectricity In some piezoelectric crystals, the dipoles are perma- nently polarized even in the absence of electric field. However, on applying electric field, the direction of polarization changes. This phenomenon is called ferroclectricity due to analogy with ferromagnetism. trtttt Example, Barium titanate (BaTiO), sodium potassium tartarate (Rochelle salt) and potas- sium dihydrogen phosphate (KH,PO,). Anti-ferroelectricity In some erystals, the dipoles align in such a way that they altemately point up and down so that the erys- tal does not possess any net dipole moment. titity Example, Lead zirconate (PbZr0,), Superconductivity Kammerlingh Onnes observed this phenomenon at 4K in mercury. ‘A substance is said to be superconducting when it offers no resistance to the flow of electricity There is no substance which is superconducting at room temperature. Example, YBa,Cu,O,, Nb,Ge alloy, La, ,,Ba, , CuO, (TMTSF), PF, (TMTSF stands for Tetra methyl tetra selena fulvalene) ete. = Superconductors are widely used in electronic power transmission, building super magnets etc. Semi-conductors: These are __ electronic conductors having electrical conductivity in the range of 10*~ 107 Q* em“ Example, Si, Ge, Sn (grey only), SiC, Cu,0 ete. m= Pure substances which are semi conductors are called intrinsic semi conductors Example, Si, Ge = Ifthe semi-conductors conductivity is due to impu- rities they are called extrinsic semi-conductors. = The addition of impurities to a semi conductor is called doping. Example, When phosphorous and arsenic (Vth group element) are doped in silica (IVth group element) n-type of conductance is observedSolid State ™ 8.21 When IlIrd group element (Ga) is doped p-type of conductance is observed. Conesive Energy: It is the energy needed to achieve in finitely separated gaseous ions from one mole of anionic crystal lattice that is negative of the Lattice energy. MX M* +X ee Bragg’s Equation M Von Laue told that there is a possibility of diffraction of X-rays by the crystals as the wavelength of X-rays is of nearly same order as the inter-atomie distances in a crystal. Considering this fact Bragg diffracted X-rays by using sodium chloride crystal. He also introduced his equation This equation gives a simple relationship between the wavelength of X-rays and the distance between the planes in the crystal and the angle of reflection. This equation can be written as: m= 2d sin Here n= Order of reflection; in general itis taken as 1 Vavelength of X-rays stance between two layers of the crystals :ngle of incident light m= As for a given set of lattice planes the value of “dis fixed so the possibility of getting maximum reflection depends only on 8. If we increase @ gradually a number of positions will be observed at which there will be maximum reflection. first layer of 8 atom w d second layer . third layer oe ee 0 ol” Path difference = WY+YZ_ = XY sin0+ XY sind =2XY sind = 2d sind The diffraction of two waves of X-rays by the regularly spaced atoms in a crystal Applications m= Bragg’s observation has been proved highly ben- ficial in determining the structures and dimen- sions of ionic crystalline solids. m= It also helped in describing many properties of X-rays also. = It helped in the construction of X-ray spectrom- eter by which the crystalline structure of crystals can be easily described. Example, face centered cubic structure of NaCl Solved Problems from the IITs 1, Sodium metal crystallizes in a body centred cubic lattice with the cell edge a = 4.29 A. What is the radius of sodium atom? UIT 1994) Solution Forb.c.. lattice, = 18576 A 2. A metallic element crystallizes into a lattice containing a sequence of layers of AB AB AB... any packing of spheres leaves out voids in the lattice. What percentage by volume of this lattice is empty space? LIT 1996) Solution cell =6 As number of atoms in hep per unit 6x4 ar So packing fraction = 3->areq x C As base area= 6 * or C=4 r\(2/3)8.22 ™ Solid State Now Packing fraction _ i EES aa 6* oa x 49x dr V(23) So. Void (space) = | - 0.74 = 0.26 =29% 3. Chromium metal crystallizes with a body cen- tered cubic lattice. The length of the unit cell edge is found to be 287 pm. Calculate the atomic radius. What would be the density of chromium in g/nm? UT 1997) Solution For b.cc. lattice, = 7.30 g/m, 4. A.unit cell of sodium chloride has four formula units. The edge length of the unit cell is 0.564 ‘nm, What is the density of sodium chloride? (IT 1997) Solution Z = 4, M for NaCl = 58.5 a= 0,564 nm = 0.564 x 107 cm 58.5% 4 6.02 x 10 « (0.564 10" =2.16 g/ml 5. Ametal crystallizes into two cubic phases, face- centred cubic (fc.c.) and body centred cubic (bcc. whose unit cell lengths are 3.5 and 3.0 A, respectively. Calculate the ratio of densities office, and bcc UIT 1999) Solution Unit cell length (fe.c.) =3.5 A =3.5« 10%em Unit cell length (b.c)=3.0A =3.0« 10%em M, din tee. = a M, Nyx a) dinfee.= (@Y _ 4.0 10%) “@) 7 2xGSx 10) [Z,=4fc.c)Z,= 2bc.0)] = 1.259 6. (i) AB crystallizes in a rock salt structure with A. B= 1: |. The shortest distance between A and Bis Y” nm, The formula mass of AB is 6.023 Y amu where Y is any arbitrary constant. Find the density in kg m- (ii) If measured density is 20 kg mr, identify the type of point defect UIT 2004, Solution (i) Asrock salt has fee structure, Z = 4 Now edge length of fec unit cell x shortest distance between A’ & B = 2x Ynm=2* Y! x 10%m ZxM Nea As Density of the erystal = - 4 «6023 Y 6.023 = 108 x (2 x ¥"9 x 10% m)* =Skgim* ii) Since there is large difference in theoreti- cally calculated density and actual density, the given solid will have metal excess defect or interstitial defect. 7. In face centred cubic (fee) crystal lattice, edge length of the unit cell is 400 pm. Find the diame- ter of the greatest sphere which can be fitted into the interstitial void without distortion of lattice. WIT 2005} Solution In fec unit cell o\2=4r av2 _ 400x V2 + 4 = 141.4 pm. For octahedral void, 2(@e+R)=aSolid State ™ 8.23 2R= 400-2 % 1414 Solution = 117.16 pm o-& So the diameter of greatest sphere = 117.16 pm. pNV _ 2x6 x 103 (Sx 105) 8. The edge length of unit cell of a metal hav- ‘ ° ing molecular weight 75 g/mol is 5 A which crystallizes in cubic lattice. If the density is 2 g/cc then find the radius of metal atom. (NA =6 x 10%), Give the answer in pm. LIT 2006 Bg = 43x 5=2,165A = 216.5 pm The answer may be 216 pm or 217 pm.8.24 @ Solid State MULTIPLE-CHOICE QUESTIONS Straight Objective Type Questions (Single Choice only) 1 4 6. The number of octahedral sites per sphere in fee structure is bz a4 ‘The erystal system in which abe and the angles a Be yis a. cubic b. hexagonal . triclinic 4. monoclinic Number of atoms present in the unit cell of a mono atomie substance of body centered lattice are a8 b6 e4 a2 In a fee lattice of anions, the cations oceupy the octahedral voids. The coordination number of cat- ions is a2 ba «6 a8 Frenkel defect appears in a. ZnS b. Agl © AgBr 4. all of these ‘The number of atoms per unit cell in a simple cubie, face-centered cubic and body centered cubie are respectively a 1,24 b. 14,2 © 4,21 4.143 In a simple cubie cell, an atom at the corner contributes to the unit cell b. 1 part . 1/8 part a. 1/2 part ¢. 16 part Sodium metal crystallizes in body eubic lattice with cell edge 2.49 A, the radius of the sodium atom is. 8. 068A ©. 286A b. 186A 4. 386A Presence of small impurities usually makes a metal uite hard because the impurities a. reduce the erystal symmetry b. reduce the number of slide planes uL. 2 13, 4. 15. 16. 17. «. change the lattice structure of metal 4. reduce the number of mobile electrons If we mix a pentavalent impurity in a crystal lattice of germanium, what type of semiconductor formation will occur? a. p-type semiconductor b. n-type semiconductor «. both of these . none of these If the anions (B) form hexagonal closest packing and cations (A) occupy only 2/3 octahedral holes imit, then the general formula of the compound is a AB, DAB, © AB, aap, ‘The erystal structure of NaCl is a. bee b. fee ©. see 4. cither (a) or (6) ‘The intermetallic compound LiAg crystallizes in cubic lattice in which both lithium and silver have coordination number of eight. The erystal class is a. simple cube b. body-centered cube «. face-centered cube 4. none of these ‘The number of atoms in one unit cell of a face centered cubic lattice is a2 63 ba as Close packing is maximum in the erystal lattice of a. body centered «face centered b. simple cubic 4. none of these In erystals of which of the following ionic com- pounds would you expect maximum distance between centers of cations and anions? b. CoE 4. Lil a LiF Cs If three elements A, B and C erystallized in cubic solid lattice with A atoms at comers, B atoms at cube centres and C atoms at the edges, the formula of the compound is a ABC b ABC, © ABC . ABC,Solid State ™ 8.25 18. 1. 20, 21. 2, 28, TThe presence of F-centres in a erystal makes it a. conducting b. non-conducting €. colourless 4. coloured Which of the following statement is correct? a, Silicon doped with Boron is an n-type semicon- ductor. . Metals are good conductors of electricity €. Electrical conductivity of semiconductors increases with increasing temperature. 4. Both (b) and (c) ‘The range of radius ratio (cationic to anionic) for an octahedral arrangement of ions in an ionic solid is a 0.155 ~0.225 ©. 0414-0.732 b. 0-0.155 4. 0225-0414 In diamond erystal each carbon atom is linked with carbon atoms. The number of carbon atoms linked is a2 «3 ba ad In spinel structure, oxides ions are cubical closest packed, whereas 1/8th of tetrahedral holes are oceu- pied by cations A* and ' of octahedral holes are cecupied by cations B* ions. The general formula of the compound having spinel structure is a. ABO, b. ABO, © ABO 4. ABO Zn converts its melted state to its solid state, it has HP structure, then find out nearest neighbours of Znatom a6 en b.8 a4 ‘Superconductors are derived from the compounds of a, Lanthanides b. p-block elements ¢. Transition elements d. Actinides A semiconductor of Ge can be made p-type by adding a. Divalent impurity b. Trivalent impurity ¢. Tetravalent impurity 4. Pentavalent impurity The interionie distance for Cesium chloride erystal willl be a Ba b. 2a/3 d. a2 27. 28, 29. 30. 31. 32, Which of the following metal oxides is anti-ferro- magnetic in nature? b. Mno, 4. Vo, 'Na,O has anti-fluorite structure. In Na,O, the coor- dination number of Na° and O* are respectively add b. 66 684 4.48 AnAB, type of structure is present in a NaCl b.NO © ALO, . CaF, ‘The melting point of RbBr is much fower than that ‘of NaF, the reason is a. The molar mass of NaF is smaller than that of RbBr. b. The two erystals are not isomorphous . The internuctear distance r, + r, is greater for RbBr than for NaF 4. The bond in RbBr has more covalent character than the bond in NaF. Schottky defect defines imperfection in the lattice structure of a a Gas ©. Liquid b. Plasma 4. Solid Number of atoms in the unit cell of Na (BCC type crystal) and Mg (FCC type erystal) are respec- tively a4 b. 4,2 24 att What is the coordination number of Cl- in NaCl crystal? a3 be 66 a8 A particular solid is very hard and has a very high melting point, In solid state it is a non conductor and its melt is a conductor of electricity. Classity the solid a Tonic ©. Network b. Molecular d. Metallic ‘What is the co-ordination number of body centred cube? ak ed b.6 a. 12 ‘What isthe coordination number of sodium in Na,O? a6 b4 68 a28.26 ™ Solid State 37. 38. 39, aL 2. Which has no rotation of symmetry? b. Cubie 4. Orthorhombic a. Triclinie . Hexagonal A p-type material is electrically a. Neutral b. Positive ©. Negative 4. Depends upon the concentration of p impurities, €. Depends on the difference of doping impurities and intrinsic impurities In a cubic unit cell, seven of eight corners are oceu- pied by atom A and having of faces are occupied of B. The general formula of the substance having this type structure would be a AB, b. A,B, © AB, a4 AB, Which of the following shows ferrimagnetism? ‘a. MnO b. Fe,0, ©. Tio, d. Cr0, In an anti-fluorite structure, cations occupy ‘a. Comers of the cube b. Tetrahedral voids ¢. Centre of the eube 4. Octahedral voids ‘The efficiency of packing is 68 per cent in ‘a, BCC structure b. FCC structure ¢. HCP structure 4. COP structure In AgBr, there can occur a. Only Frenkel defect 'b. Only Schottky defect ¢. Both of these 4. None of these In which of the following pairs, the cations occupy, same type of site? a. CsBr, ZnS b. NaCl, CsCl ©. Na,0, CaF, 4. Zine blende, Na,O Empty space in cep lattice is a. 46 ©. 64% 47. 48, 49. If'we know the ionic radius ratio in erystal of ionic solid, what ean be known of the following? a. Magnetic property b, Nature of chemical bond ¢. Type of defect ‘@. Geometrical shape of erystal ‘An example of a face centered cubic lattice is a. Caesium chloride b. Copper ©. Zine 4. Sodium ‘A. metallic crystal has the BCC type stacking pattern, What percentage of volume of this lattice is empty space? a 26% ©. 32% b, 84% 4. 68% Amorphous substances show @ short and long range order (i) short range order Gi) long range order Gv) have no sharp mp. a. @and Gi are correct b. Gi) and (iv) are correct © Gi), Gil) and Giv) are eorreet 4. @ and (iv) are correct The fraction of total volume occupied by the atoms present in a simple cube is a 6 b, W332 ©. wAN2 a. wis ‘A compound contains X and Q elements. Atoms Y are in cop arrangement while X occupy all tetrahedral sites. Formula of compound is: a XY b. XY, © XY axy With which one of the following elements sil- icon should be doped so as to give p-type of semi-conductor? b, Boron 4. Arsenic ‘&. Phosphorous . Germanium An ionic compound is expected to have tetrahedral structure ifr/t lines in the range of a. 0.987 to 12, b, 0.133 to 0.675 €. 1.234 t0 0.456 4. 0.225 100.414Solid State ™ 8.27 Body centred cubie and face centred unit cells have 1n, and n, effective numbers of atoms. Which one of the following (n, and n,) combination is correct? a 42 b. 24 21 412 58, Percentage of free space in a body centered cubie unit cell is a 34% b, 28% ©. 30% . 32% Brainteasers Objective Type Questions (Single choice only) $6. A compound formed by element ‘A’ and ‘B” crystallizes in the cubic structure where “A’ atoms occupy the corners of @ cube and “B’ atoms are at the face centres the compound must have the formula: a. AB, b. AB AB aA AB, 57. At 100°C and 1 atm, if the density of liquid water is 1.0 gm em? and that of water vapour is 0.0006 gm em, Then the volume occupied by water molecules in one litre of steam at that temperature is a. 0.6m" b. 600m! ©. 60.em* 4. 0.06 em* 58. In the unit cell of an fee system, the number of cetahedral and tetrahedral holes are a4 bs 48 4,4 59. The density of sotid argon is 1.65 giml at -233°C. If the argon atom is assumed to be sphere of radius 1.54 = 10 om, what percentage of solid argon is apprarently empty space? (atomic wt. of Ar = 40) a. 32% b. 52% «72 60. The second order Bragg diffraction of X-rays with 2.= 1A from a set of parallel planes in a metal ‘cours at an angle of 60°, The distance between the seattering planes in the erystal is a. 200A b. 100A ©. 0575 a. LISA 61. The number of unit cells is 585 g of NaCl is nearly a. 05 «10% b. 15 «10% 3 «10 . 60 = 10" 2, 65, 61. 0. A solid has a cubie cell with atoms A at the comers, atom B at each face centre and atom C at the body centre, The formula of the solid is a ABC b. ABC © ABC @. ABC Sodium metal erystallizes in body centred cubic lattice with the cell edge, 4.29 A. The radius of sodium atom is a 085A b. 0.185A 185A, . 285A ‘An element forms a body centered eubie erystal- line substance. The edge length of the unit cell is 287 pm and the density of the erystal is 7.92 g/em? Calculate the atomic weight of the substance a. 56.4 amu b. 46.4 amu © 36.5 amu . 65.4 amu The coordination number of the largest sphere which can be inserted in interstitial voids of an ideal BCC crystal without distorting the lattice would be as b.6 e4 a2 Ina simple cubic lattice of anions, the side length of the unit cell is 2.88 A. The diameter of the void in the bond centre is a 0461 b. 2.108A © 4.9084, 4. 1.984 A ‘A crystal is made of particle A, B & C. A forms FCC packing, B occupies all octahedral voids of Aand C occupies all tetrahedral voids of A, if all the particles along one body diagonal are removed then the formula of the erystal would be a ABK, b. ABC, © ABC, a ABC, Analloy of copper, silver and gold is found to have copper constituting the cep lattice. If silver atoms ‘occupy the edge centres and gold is present at body centre, the alloy will have the formula a Cu,Ag,Au b. CuAgAu ©. CuAg,Au 4d. Cu,Ag,Au The pyknometric density of sodium chloride erys- tal is 2.165 * 10° kg m* while its X-ray density is 2.178 « 10° kg n°, The fraction of unoceupied sites in sodium chloride erystal is a 5.96 « 10" b, 5.96 « 107 © 5.96 5.96 « 1078.28 ™ Solid State 70. 2. 73. 74, 16. 7. In the CsCI structure r “t* = 1.37. The side length of the unit cell in terms of r is Pa boar Lala a= ar a © ‘The erystal system of a compound with unit cell dimensions a = 0.387, b = 0.387 and ¢ = 0.504 nm and a= B= 90° and y= 120°is a. Hexagonal b. Cubic ¢. Rhombohedral 4. Orthorhombie Rhodium has a face centered cubic structure and has a density of 124 giem’. What is its atomic radius? ‘a. 194 pm ¢. 314 pm. b. 234 pm 4.134 pm If the distance between Na* and Cl-ions in sodium chloride erystal is X pm, the length of the edge of the unit cell is a. X/2 pm ©. X/d pm b. 2X pm 4. 4X pm ‘The intercepts made by a plane along the X, Y and Z axes are respectively 2a, 2b and <0 © where a, b and ¢ are the respective unit distances along these axes, The Miller indices of the plane are a. 0,2,2 b 110 22,0 a iio ‘The number of tetrahedral voids in the unit cell of a face-centred cubic lattice of similar atoms is a6 bs «10 a4 ‘A crystalline solid of unknown origin forms an aqueous solution that conducts an electrical current ‘The solid has a high melting point and shatters when struck with a hammer. The solid is likely to be a. Ametallic solid b. A molecular solid ©. Anionic solid 4. A covalent network solid At very low temperature, SO, crystallizes in a hex- agonal lattice. If the cross sectional area of unit cell is 17.77 » 10 emi, the lattice constant °b’is 7.41 A and density is 0.805 g/ce then the number of SO, molecules per unit cell is, al b2 “3 a4 78. 7. 80, 81. 82, ‘The most unsymmetrical and the most symmetrical crystal systems based on lattice parameters (that is, Unit cell lengths and angles), are respectively rep- resented by the examples a. Rhombic sulphur, NaCl b. Diamond, NaCl ‘¢. Monoclinic sulphur, diamond 4. CuSO, SHO, NaCl ‘What type of erystal defect is indicated in the dia- ‘gram below? Na’, Cr, Na’, Cl Na’, Cr Cho Ch Nat o Nat Ne Clo C-Ne* (Cl Nat Clr Na’ 5 Nat a. Frenkel defect b. Interstitial defect . Schottky defect 4. Frenkel and schotthy defeets If Z is the number of atoms in the unit cell that represents the closest packing sequence ...AB CA BC ..., the number of tetrahedral voids in the unit, cell is equal to az b. 22 622 4. Zia In a compound PQ,O,, oxide ions are arranged in CCP and cations P are present in octahedral voids Cations Q are equally distributed among octahedral and tetrahedral voids. The fraction of the octahe- dral voids oecupied is a v4 © 13 Assuming the atoms of an element to be hard spheres of radius 1.00 A in ep. or hep. the atomic vol- ume, (being defined as the ratio of atomic weight of the element to its density) calculated per atom is b. 12 4.23 a 5.6645 b. 6.1GAP ©. 106A . 418A In face-centered cubie unit cell, edge length is a2r b. (V32)r « N3)r @. a2) r ‘A.compound alloy of gold and copper crystallizes in a cubie lattice in which the gold atom occupy the lattice points at the corners of a cube and the copper atoms occupy the centers of each of the ‘cube faces. Hence, compound alloy has formula: a Au,Cu b. AuCu, © AuCu @. AuCuSolid State ™ 8.29 85, 87. a1. ‘A solid X° Y" has the Y- ions arranged as below. Ifthe X* ions occupy half of the tetrahedral sites in the structure, The formula of solid is a. XY ©. XY, b XY a. XY, ‘Then number of nearest neighbours and next near neighbours of a Na” ion in a erystal of NaCl are respectively a. 12Cr, 6Na® ©. 6CI, 6Na" b, 6CI, 12Na 4. 6Na", 12Cr Total volume of atoms present in a face centred cubic unit cell ofa metal is (ris atomie radius) ae ae 12 ys 16 ays eke a Be CBr erystallizes in a body centered cubic lattice. ‘The unit cell length is 436.6 pm. Given that the atomic mass of Cs = 133 and that of Br = 80 amu and Avogadro number being 6.02 » 10° mol", the density of CsBr is a, 8.25 glem! . 42.5 glo? b. 425 giom? 4. 0.425 glem? Diamond has face-centred cubic lattice. There are two atoms per lattice point, with the atoms at (000) and (1/4, 1/4, 1/4) coordinates. The ratio of the carbon-carbon bond distance to the edge of the unit cell is a4 «. VGN6) b. Nz @. vay A solid has 3 types of atoms namely X, Y and Z. X forms a fee lattice with Y atoms occupying all the tetrahedral voids and Z atoms occupying half the octahedral voids. The formula of the solid is a. XYZ, b XYZ XYZ @. XYZ, ‘The Ca’? and Fare located in CaF, erystal, espec~ tively at face centred cubic lattice points and in a. tetrahedral voids b, half of tetrahedral voids €. octahedral voids 4. half of octahedral voids 92, 4, 98, 96. 97. 98. ‘The radii of Na’ and Cl-ions are 95 pm and 181 pm respectively. The edge length of NaCl unit cell is a. 276 pm b. 138 pm ©. 552 pm d. 415 pm An element (with atomic mass = 250 g) erystal- lizes in a simple cube. If the density of unit cell is 7.2.g.cm*, what is the radius of the element? & 1.93 10%em b. 1.93 10%om 193 «108A, d. 1.93 «10m For hep packing which of the following will be correct statement? (@ Volume of unit cell unoccupied ii) Coordination number of HCP = 12 8% ii) This is more efficient packing than cep Gv) Tteontains both tetrahedral and octahedral voids & (O, Gili) © @,6v) A certain metal with density 10.57gm/ml erystallizes in the fee system, If the number of unit cells per b. Gi), Gv) 4. (i), Gi), Gv) gram 1.4 » 10", find the side length ofthe unit cel, a 4A b. 205A ©. 425A 4. 675A For a cubie erystal structure which one the follow ing relations indicating the cell charactersties is correct? a a=b=candas Be y4 90° b afb #eand a= B= y=90° «afb feanday Bandy #90" cand a= ‘The chromium metal exists as a bec lattice with cell edge 2.88 A. Iis density is 720 glee. How many atoms does 55 of chromium contain? a. 32.60/55, ©. 5551.77, b. SLTISSN, . 55/32.60N, NaCl is doped with 10+ mol % of SrCl,, the concentration of cation vacancies will be. (N, = 6.02 » 10 mol) & 6.02 » 10" mol b. 6.02 » 10" mol ©. 6.02 « 10” mol . 6,02 » 10! mol8.30 ™ Solid State 99. 100, 101, 102. 103, 104, 108, NaCl is doped with 2 » 10 mol % SiCl., the con- centration of cation vacancies is a. 12.04 « 10!" mol b. 10.01 « 10% mol! ©. 12.04 « 10” mol . 4.02 » 10" mol ‘Ag crystallizes as FCC. If radius of Ag is 144 pm then its density will be a. Sgom? ©. 6.5 gem? b. 10gem* 4.16 gem Iridium crystallizes in a face-centered cubic unit cell that has an edge length at 3.832 A. The atom in the center of the face is in contact with the corner atoms, as shown in figure. Find the atomic radius of an iridium atom, ER ES b. 0675 A @. 1355A a 271A L916 A, In the problem and figure given above find the density of iridium metal, b, 2.26 giem’ 4d. 21.63 giem’ ‘a, 11.33 glem! ©. 22.67 glem! TThe cubic unit cell ofAl (molar mass 27 g mol") has an edge length of 4.5 pm. Its density is 2.7 g em” TThe cubie unit cell is a. Bdge centred b. Body centred ©, Face centred 4. Simple Ina compound atoms of element Y from cep lattice and those of element X occupy 2/3 of tetrahedral voids. The formula of the compound will be a XY, b. XY, “XY a XY, In an FCC unit cell, atoms are numbered as shown below. The atoms not touching each other are (Atoms numbered 3 is face centre of front face) 106. 107. 108. 109. 110, m1. 112, Potassium has @ bee structure with nearest neigh- bour distance 4.52 A. It s atomic weight is 39. Its density will be a 454 kgm? © 1098 kgm? b. 809 kgm? 4, 908 kgm? Percentage of free space in a body centered cubic unit cell is: a 34% ©. 30% b. 28% 4.32% In AO, the metal ions form a face eentred cubic lattice, The oxide ions occupy the tetrahedral sites, The metal ions occupy the faces and comers of the Unit cell the total number of metal ions and oxide ions per unit cell is a2 bs © 12 a4 ‘Choose the correct statement from the following: (1) Frenkel and Schottky defects are thermody- namie defects (2) Compounds with Schottky defects do not obey law of constant composition (3) In compounds with Frenkel defect, among a majority of metal ions of one valency, a few ‘metal ions of another valency are also found. a (I)only b. Q)only © (and 2) 4. (1), @)and @) Br has bee structure with edge length 4.3 A. The shortest interionie distance in between Cs* and Bris a 43A 632A b. 189A 732A If ‘a’ stands for the edge length of the cubic sys- tems: simple cubic, body centered cubic and face centered cubic, then the ratio of radii of the spheres in these systems will be respectively, 1,.8,,2 agacyaya bia: Ba: x: 1,.8 eta: Pa Lae a dasa G Ina CCP lattice of A and B, A atoms are present at the corners while B atoms are at face centres, Then the formula of the compound would be if ‘one of the A atoms from a comer is replaced by C atoms(also monovalent)?Solid State ™ 8.31 113. 14, 15. a ABC, © A,BC b. AB,C d. ABC ‘A solid compound contains X,Y and Z. atoms in @ cubic lattice with X atoms occupying the comers, ‘atoms in the body centered positions and Z. atoms at the centers of faces of the unit cell. what is the empirical formula of the compound? a. XYZ © XYZ, b. XYZ, a. XYZ, KCI crystallizes in the same types of lattice as does NaCl. Given that 1, ,/tqy = 0.55 and Ty fer" 0.74. Calculate the ratio of the side of the unit cell for KCl to that NaCl a. 1.123 b. 0.432 ©. 1876 d. 1.564 ‘A compound is formed by elements A and B. This crystallizes in the cubic structure where the A atoms are at the comers of the cube and B atoms are at the body centers. The simplest formula of the compound is a AB . AB b. AB, d. AB, Multiple Correct Answer Type Questions 116. 47. Titanium monoxide has a rock salt structure, X-ray diffraction data show that the length of one edge of the eubie unit ell for THO, where in the ratio of Ti to Ois 1: Lis 4.18 « 10" em and the density deter- mined by volume and mass measurements is 4.91 g em. which of the following defects are found a Schottky defects with cation and anion pair vacancy, . Schottky defects with equal number of vacancies on the cation and anion sites. ¢. Frenkel defects with cation and anion pair inter- stitial defects 4. Frenkel defects with equal numbers of inter- stitials on the cation and anion sites. Packing fraction in an identical solid sphere is 74 % in case of bee structure b, hep structure ¢. fee structure 4. . simple cubie structure. 18, 19, 120, 11. 12. 123. Select the correct statements here a. The co-ordination no. of U : O in UO, is 8:4 b, Inclosest packing of x ~ atoms, there are 2x tet- rahedral holes, and x- octahedral holes «. In hexagonal packing of oxide ion in Sapphire (the aluminium oxide) Al‘ ions crystallize in 2/3 rd of the Octahedral hole, then the formula of Sapphire is Al,O, 4. Ifanion B constitutes cep and all the octahedral voids ar occupied by cation (a), the crystal has the same molecular formula AB, if the cation (a) ‘oceupies the alternate tetrahedral voids. In anti-fluorite structure va 4 b, oxide ions are face centred «. cations are present in all the tetrahedral voids 4. cations are face centred and anions are present inal the tetrahedral voids Which of the following statements are correct? a halides of all alkali metals and alkaline earth metals have rock salt structure b. cesium halides and beryllium oxides have rock salt structure . in FCC unit cell, void percentage = 26% in zine blende structure, sulphide ions are face centred and zine is present in alternate tetrahe- dral voids Which of the following statements is/are consis- tent with the properties of a molecular solid? a. Alow melting solid b. A compound that conducts electricity when ‘molten A solid that is a non-conductor of electricity 4. A solid formed by the combination of two non- ‘metallic elements Ifthe radius of Na’ is 95 pm and that of C- ion is 181 pm then a. Length of the unit cell is 552 pm b. Length of the unit cell is 380 pm . Co- ordination no, of Na’ is 6 4. Co- ordination no. of Na* is 8 Which of the following statements is/are incorrect, in the rock-salt structure of an jonie eompound? a. Coordination number of cation is six and anion is four.8.32 ™ Solid State 124, 128, 126, 127, 128, b. Coordination number of cation is four and anion is six ¢. Coordination number of each cation and anion is six. 4. Coordination number of each cation and anion is four. Select the correct statements here. a, Hexagonal close packing (hep) and Cubie close packing (cep) structure has different co- ordina- tion no b. At high pressure €. Schottky defect is not shown by CsCl 4. Frenkel defect is shown by ZnS, the coordination number Which of the following statements is/are ineorrect in the body centered type centered type cubic struc~ ture of an ionie compound? ‘8, Coordination number of each cation and anion is eight b. Coordination number of each cation and anion is four ¢. Coordination number of each cation and anion 4. Coordination number of each cation and anion is two. In which of the following compounds, cations are present in tetrahedral voids? a. ZnS . NaBr Select the correct statements in a CsCl erystal a. Cs* occupies body centre of Cl b. It is impossible for Cl to occupy body centre of Cs" because the body centre void of Cs" is smaller than CI-ion size . Cs forms a simple cubie lattice, Cl- forms a simple cubic lattice 4. Cl occupies body centre of Cs" Which of the following statements for erystals having Schottky defect is/are correct? a Schottky defect are more common in ionie com- pounds with high co-ordination numbers. b. Schottky defect arises due to the absence of cation or anion from the position which it is expected to occupy. ©. The density of the crystals having Schottly defect is larger than that of the perfect crystal. 4. ‘The erystal having Schottky defect is electrical neutral as a whole. 129. 11. 132. 134. Select the correct statements here a. For NaCI unit cell (edge length = 1), r, + v2 b. For CsCl unit =\B/20 cell (edge-length = a), . The void epace in a.b.c.c unit cell is 68% 4. The void space ina face-centered unit cell is 26 % Which of the following statement for erystals hav- ing Frenkal defect is not correct? a. Frenkal defects are observed where the differ- ‘ence in sizes of cations and anions is larger b. The density of erystals having Frenkal defect is lesser than that of a pure perfect crystal ‘¢ Usually alkali halides do not have Frenkel detect. 4. In an ionic crystal having Frenkal defect may also contain Schottky defect In face centred cubic unit cell a face diagonal of the cube which is V2a is equal toar b. rank of unit cell is 3 ¢. effective number of atoms is 4 in FC 4. 8 tetrahedral voids per unit cell of FCC Select the correct statements here a. Frenkel defect usually shown by ionic com- pounds having low coordination number. b. Stoichiometry of erystal remains unatfected due to Schottky defect «. Density of crystal always increases due to sub- stitutional impurity defect. 4. F- centres generation is responsible factor for imparting the colour to the erystal ‘Which of the following does not represent the closet packed arrangement of uniform solid spheres? a. simple cubic unit cel b. hep unit eell . face centered cubic unit cell 4. body centered cubie unit cell Select the incorrect statements a. NaCI changes to CsCl structure on applying pressure. b, CsCl changes to NaCl structure on heating. ¢. Co-ordination number increases on heating, 4. Co-ordination number decreases on applying pressure.Solid State ™ 8.33 135, 136. 137, 138, 139, 140, Amorphous solids ‘a. have sharp melting points . have same physical properties in all directions . are super cooled liquids d._ are pseudo solids If we assume ‘M’ crystallizes in a fee unit cell and tetrahedral voids are also occupied by “M’ atoms. If the edge of the unit cell is 0.55 nm and the density of "M? is 2.23 g /ec, which of the following statements are correct? a 40 % of the tetrahedral voids are occupied by “M’-atoms in this lattice b. 50 % of the tetrahedral voids are occupied by “MP-atoms in this lattice ©. MeM bond length is equal to the sum of radii of 2M’ atoms which is equal to 0.24 nm, 4. 20% of tetrahedral voids are occupied by *M’ atoms in this lattice Which of the following statement is/are correct? a. The co-ordination number of each type of ion in CsCl erystal is 8 b. A metal that crystallizes in bee structure has a co-ordination no. of 12 . The length of the unit cell in NaCl is 522 pm (60 95, rb © 181pm) 4. A.nit cell of an ionic exystal shares some of its ions with other unit cells Pick out the incorrect statement about CsCl structure a. CsCl has a bos structure . Cl adopts a simple cubic lattice €. Coordination no, of both Cs and Clis 6 4. Cl-ions present at cubie sites Which of the following statements is/are correct? a, The number of carbon atoms in an unit eell of diamond is 4 b. The number of Bravais latices in which a crystal ccan be categorized is 14 ¢. The fraction of the total volume occupied by the atoms in a primitive cell is 0.48, d. Molecular solids are generally volatile. The correct statements (s) regarding defects in solids is/are a, Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion, b. Frenkel defect is a dislocation defect Linked-Comprehen: «. Trapping of an electron in the lattice leads to the formation of F-center 4. Schottky defects have no effet on the physical properties of solids [IT 2009) n Type Questions Comprehension 1 Clo: se-packing of particles results in two highly efficient lattice, hexagonal close- packing (hep) and cubie close- packed (cep). In both of these packing 74 space is occupied. The remaining space is present in the and frac the PR and form two types of voids that is, octahedral voids tetrahedral voids. Packing fraction of a unit cell is defined as the tion of the total volume of the unit cell occupied by atom(s) and it can be given as Volume of the atoms) present in a unit cell ‘Volume of unit cell zie 4 3 a % of empty space ~ 100 ~P.F. « 100 here Z = effective number of atoms in a cube 141. 142. © radius ofan atom = edge length of the cube ‘The percentage void spaces per unit volume of unit cell in Zine floride structure, a 2507 © 32% . Consider a cube containing n unit cells of a cubie system. X plane PRS obtained by joining the mid points of the edge on one of its identical faces had atoms arranged as shown. Let p be the packing fraction, Find the correct choice. P Q IR s Q R Arrangement of atoms8.34 M Solid State dn= p= Prone 143. A compound forms hexagonal close-packed structure, What is the total number of voids in 0.6 mol of it? a, 10,8396 « 107 b. 10.8396 « 108 7.2264 » 10% d. 11.2264 » Comprehension 2 Density of a unit cell ean be found out by the relation given below Effective no. of atoms » Mass ofa unit cell Volume of unit eell _ 2M. Na Here, mass of unit cell = mass of ellective no. of atoms or ions. M =At. wt/formula weight N, “Avogadro's no. = 6.023 » 10 a = edge length of unit cell 144, An unknown metal crystallizes in a body- centered cubic lattice witha unit cell edge length of 5344 A. Its density of 0.862 g/ont at 20°C. Identify the metal br 4.Na a. Fe ak 145. Copper has a specific gravity of 8.93 and crys tallizes in a face- centered cubic lattice. Use this information to determine the edge length of the unit cell and the radius of a copper atom, a an 3.S2Asr~-1.23A b. a=3.62A;r= 128A c.a-3A2Azr= 122A d. a= 3.82A;r= 132A 146. Cesium chloride, CsCl, crystallizes in a lattice in which there are chloride ions at each corner of a cube and a cesium ion in a body- centered position, The edge length, a, is 4.121 A and the radius of 4 chloride ion is 1.81 A. Assuming anion- cation contact along the body diagonal, j, determine the ionic radius of Cs. a 166A © 186A b. LI6A a. 157A Comprehension 3 Atomic radius is half of the distance between nearest neighbouring atoms in a crystal for various types of crystals it can be expressed in terms of edge length of the unit cell, In case of ionic erystals the geometrical shape and coordination number are decided on the bases of radius ratio(r,,7,) 147. 148. 149. Tungsten erystallizes ina body centered cubie unit cell with an edge length of 317 pm. What is the length (in Pico meters) of a unit cell diagonal that passes through the center atom and the radius of a tungsten atom respectively? a. 317 pm, 137 pm b. 549 pm, 137 pm. ¢. 549m, 274 pm 4.317 pm, 274 pm. The edge length CsCI unit cell is 412.4 pm. If the ionic radius of Cl- ion is 181 pm, Find the ionic radius for C3" a 173.28 pm © 176.148 pm Which of the following g represent the correct decreasing order of radius ratio? b, 186.224 pm 4. 231.4 pm a. CsCl > NaCl > ZnS > BLO, b. Agl> BeS >KC1>B.0, ¢. Agl=BeS > KCI>B,0, a. CsC1> ZnS > NaCl > B,O, Comprehension 4 In hexagonal systems of crystals, a frequently encoun- tered arrangement of atoms is described as a hexag- onal prism. Here, the top and bottom of the eell are regular hexagonal and three atoms are sandwiched in between them. A space-filling model of this structure, called hexagonal close-packed (HCP), is constituted of 4 sphere on a flat surrounded in the same plane by six identical spheres as closely as possible. Three spheres are then placed over the first layer so that layer so that they touch each other and represent the second layer. Finally the second layer is covered with a third layer that is identical to the bottom layer in relative position ‘Assume radius of every sphere to be ‘r”Solid State @ 8.35 150. The number of atoms in this HCP unit cell is ad b. 6 © 12 4.17 151. The volume of this HCP unit cell is a 24v2e b 1620 © 1228 = ABP 152. The empty space in this HCP unit cell is, a 4% b. 47.6% ©. 32% a. 26% Assertion-Reason Type Questions In the following question two statements (Assertion) A and Reason (R) are given, Mark (a) ifA and R both are correct and R is the correct explanation of A (b) ifA and R both are correct but R is not the cor- reet explanation of A (©) Ais true but Ris false (@) Ais false but Ris true (©) both A and R are false 153. (A): For fluorite structure, the F- ions occupy tetrahedral void, but Ca"*ions occupy c.cp. (R): The radius ratio of fluorite structure is 0.225, 154. (A): Electrical conductivity of semiconductors inereases with increasing temperature. (R): With the increase in temperature, large num- ber of electrons from the valence band can jump to the conduction band. 188. (A): When iodine is heated under atmospheric pressure condition, it transforms to vapour ‘without passing through the liquid state, (R): IF the triple point pressure of a system is high and unless external pressure is applied to exceed the triple point pressure, sublimation will take place, 156. (A): Repulsion energy term for sodium chloride is bein" chloride ions, The term 6be? is because in case of sodium chloride each sodium ion is surrounded by six 157. 158. 159, 160. 161. 162. 163. 164. 168. 166. ay Ry a: ®: @: ®: a: ®: Ay ®: Ay: ®: A: ®: Ay ®: ay ®: ay ®: In any ionic solid (MX) with Schottky defects, the number of positive and negative ions is the same. Equal number of cation and anion vacancies are present, Graphite is an example of tetragonal crystal system. fora tetragonal system, a=b#¢, a= B=90 y= 120° NaCl crystal is sometimes yellow in colour. Na’ in the crystal absorbs electron from air and hence gives yellow colour. Anion vacancies in alkali halides are pro- duced by heating the alkali halide crystals with alkali metal vapour Electrons trapped in anion vacancies are referred to as F -centres, In AgCl crystal, Frenkel defect can be observed ‘Ag’ isa small size cations. In CsCl, the limiting radius ratio should lie in between 0.414 — 0.732. Coordination numbers of both Cs" and Cl ions are 8, Amorphous silica is a photovoltaic substance. Photovoltaic substance converts sunlight into electricity. Large number of Schottky defect lead to lowering in density of erystal lattice. ‘The defect is due to missing cation and anion Equal number of cations and anions are miss- ing to maintain electroneutrality ‘The substance whose resistance reduces nearly to zero are called superconductors Superconductors are diamagnetic substances. The effective number of octahedral voids in CCP structures is 4 per unit cell In the CCP structure, there is one octahedral void in the centre of the body and 12 octa- hedral voids on the 12 edges of the cube and each of these edge based void is shared by four unit cells,8.36 ™ Solid State 167. (A): In close packing of spheres, a tetrahedral void is surrounded by four spheres whereas as octa- hedral void is surrounded by six spheres (R): A tetrahedral void has a tetrahedral shape whereas as octahedral void has an octahe- dral shape. 168. (A): Group -15 doped erystals of silicon are called a n-type semiconductor. (R): Neutrons are responsible for the semi-con- ducting properties. 169. (A): Group-13 doped crystals of silicon are called 4 p-type semiconductors. Holes (Positive in charge) appear to be respon- sible forthe semi-condueting properties ®): 170. (A): Band gap in germanium is small because (R): The energy spade of each germanium atomic energy level is infinitesimally small [ur 2007] Matrix-Match Type Questions 171. Match the following: Column 1 Column I ‘A. Trigonal () a= B= B. Monoclinic @ a=b-e ©. Rhombie (@atbee D. Cubie (8) a= 172, Match list with list-II and select the correct, answer: List I (shape) List II (Radius ratio) A. Planar triangle (p) 0.732 B, Square planar (@) 0.225 C. Body centred cubic (7) 0.115 D. Tetrahedral () 0.414 173 Match the following: List I List IT A. Fertimagnetic (p) Fe,0, b, Ferrclectrcity (q) BaTiO, C. Antiferoctectrcity (1) PbZ0, © To, () KHPO, D. Diamagnetic 174, Match the following: Column Column tt A. Fluorite structure (p) Distance of nearest ncigh- isa wba ¢ B. Zine blende structure (q) Packing Fraction 73.0 % C. CsCl structure D. Rock salt structure (®) Packing Fraction 74.0 % (3) Packing Fraction 79.4 % ‘Match the following: Column 1 Column I ‘A. Péype semiconductor (p) Heston ae responsible for movement of current B. N-type semi conductor (q) Holes are responsible for movement of current C. Graphite (®) Doping D. NaCl (8) Crystalline 176, Match the following: Column I Column I A. Cubie B, Rhombohedral . Tetragonal D. Hexagonal () a= f=90y= 120° ) a=B=y#90 177. Match the following Column I ‘Column I A. Diamagnetic (P) Unpaired electrons B, Paramagnetic @ unin C. Ferromagnetic otttttt D. Antiferromagnetic (3) TT Ot >t 178. Match the following: Column I ‘Column I A. 1f0.732<* <1 B, 1f0.414< « <0.732 ©. 1f0.225<«<0414 (p) Co-ordination no. is 2 (@) Co-ordination no. is 6 (1) Co-ordination no. is 4 D. tradi rato x (-) > abd 18. 30, 42. 54. 61. b 109. a nd &b %bD Wb he Ib 19.d 2c Md Wa We wd 3d 32e Be Bho 38a 36 Bic 4d 4d 46d 42d Be Ob Be 6ha 6d 6K GLa Hb Kb He Ma Bd We 8b 87d Ha Hc Me Ha 9c a 100.b Ld We 136 NOc Mle 2b 3b ha Se 19. abc ed aed 12. ac 260d Dacd 12 abd 129. a,b. Bad Bhed 138 bed 136. be 140. be Assertion Reason Type Questions 153. ¢ 154, 155. a 156. 187. 158, 159. © 160. b 161. a 162. 163. b 164, a 168. b 166. a 167. 168. 169. a 170. bSolid State ™ 8.39 Matrix-Match Type Questions 171 A-(p,@),B-(©,C-(8),D-(@s) 172. 173. A-(p),B+G,1), C-), D4) 174, 195. A-(4,0),B-(,p),C-(,8),D-G) 176. 177. A-(@),B-(p,0,C-(p.),D-(p.9) 178, 179. A-(9,B-(p),C-@,D-() 180. The IIT-JEE Corner 182 182 183. 184.6 185. 2 Hints and Explanations Straight Objective Type Questions 2 ‘As number of octahedral sites = number of ions in the packing So number of octahedral sites per sphere = A body centered lattice has 8 atoms. Contribution of a particle at the corner = 1/8, ‘The number of atoms to be assigned to unit cell -818-1 Contribution of a particle at the body centre So total number of atoms present in the unit cell wit, Body diagonal = 4» (Na) = 8 =a 4 1(Na)= V3 «429 1(Na)- "p< 429 = 186A ‘NaCl crystal has fee (face centered cubic) structure because in NaCl the Na’ atom occupy all the eight corners of the cube, Cl-ions are present at all the corners and at the centre of each face of the cube. ‘The maximum proportion of volume filled or maxi- ‘mum packing by hard spheres in simple cubic body centered and face centered cubie system are 0.52, 0.68 and 0.74 respectively. 21. 28, 28, 29. A-(,B-(9),C-(),D-@ A-@,3),B-(,1).C-@),D-@) A-(P,1),B-(p,0,C-@0.D-(@s) A-6),B-(@,9),C-(0,D-() A~(p,8),B(p, 9), Cq), D-(@.r) 186. b 187.b 188 a 189. A:B:C=(8* 18): (1 = 1):(6* 12) 13 So the formula is ABC, In diamond crystal each carbon atom is linked to four other carbon atoms by strong covalent bonds in a tetrahedral manner. HCPis a closed packed arrangement in which the unit, cell is hexagonal and co-ordination number is 12, Ge is group 14 element. Positive holes can be created by adding group 13 element icc. trivalent impurity. Anti-fluorite structures like Li,O, Na,O, K,O, Rb,O. Rb,S,Na,$ possess 4 8 coordination AB, type of structure is present in CaF, as, AY + 28> CaF, = Ca + 2F- Schottky defect defines imperfection in the lattice structure of a solid in which cation and anion are missing in equal numbers from their lattices. In Na,O each O* ion is surrounded by 8 sodium ions and cach sodium ion is surrounded by 4 O* ions Hence the coordination number of sodium is 48.40 ™ Solid State 39. A:B=7/8:3 =7:24 So the formula is A,B,,. 41. In antifluorite structure, oxide ions are present in FCC packing and metal ions occupy all the tetrahe- dral voids. S ‘AgBr has both Schottky and Frenkel defects 44. In ZnS and Na,0, the coordination number (4 : 4) and (4 ; 8) respectively. Zn° and Na® possess same coordination number and occupy the same sites that is tetrahedral sites 46. _Inionic erystas, the coordination numbers as well as the geometrical shapes of the erystals depend mainly ‘onthe relative sizes ofthe ions. The rato ofthe posi- tive and negative ions is called radius ratio. 47. Znis HCP, Na and CsCl are BCC while Cu is CCP or FCC. 48, In BCC, 68 % space is occupied and remaining 32 % is empty. 50, In simple cubic arrangement it is w'6 or 0.52. 52, _If-silicon is doped with any of the element of group Ill (B, Al, Ga ete.) of the periodie table, p-type of semiconductor will be obtained. 53. =0.225 10 0.414 for ionic compound having tetrahedral structure $5, For body centered cubie structure Packing fraction = 0.68 that is, 68 % of the unit cell is occupied by atoms and 32 % is empty. Brainteasers Objective Type Questions 56, It atoms “A’ occupy comers then total number of atom ‘A’ in a erystal =V8*8=1 Now atoms *B" occupy face centres thus number of atom ‘B’= 1/2 «6=3 ‘Therefore, formula of compound is AB, 57. Mass of water molecules in | it of steam = 1000 em = 0.0006 gm em” =06 gm ‘Volume occupied by water molecules in steam _ Mass of water __ 0.6m Density of water 1.0 gm/em* =0.6 em’ 60. 6. 02, Inan fee system, number of atoms in the unit cell is, at the comers 8 » U8 = 1 at the face centers 6 1/2 Total = 4 For each atom there is one octahedral void and two tetrahedral voids ‘As volume of one atom of Ar=4 xe? 3 Number of atoms in 1.65 g or one mL 1.65, " 40” 6,023 * 10 So total volume of all atoms of Ar in solid state 4 Ms . of ar AS 6023 «10 2 5 LSS 2a sso 8 + 6.023 « 108 380 em* Volume of solid argon = 1 em* Hence % of empty space (10380) 1 =02% m= 2dssino 2x1-2xdsino x3 2= 2d (sin 60° = V3/2) d= 2N3 = LISA 585 g NaCl ~ I mole = 6.02 10 NaCl units ‘One unit cell contains 4 NaCl units Hence number of unit eells present in 58.5 ¢ NaCl 6.02 « 10" pn 1S 108 Number of atom A, 1/8 = 1 ‘Number of atom B, %4 » 6=3 Number of atom at the body center C, 1x1= Formula is ABCSolid State ™ 8.41 67. 69. Cell edge = 4.29 A, 85A Body diagonal of cubic lati Diameter of the void in the body center =av3-a = (1.732 2.88) 2.88 = 4.988 -2.88=2.108 A (On removing all particles along one body diagonal are removed then 2A particles from corners, IB particles and 2C particles are removed this means the no. of particles atoms are as follows ‘No .of A- particles = 6 «1/8 +6» % 15 4 No. of B ~ particles = 6 No. of C - particles = 3 So the formula is,,,B,C, ie ABC, According to question Au is at the body centre so Au=1 Agisat the edge centre = 12» %=3 Cuis having cep lattice Cu atoms =8 « 18 +6 « 12 =1+34 So the formula is Cu, Ag, Au 4 (pyknometric) ~ d (observed) = 2.165 «10° kg/m’ 4 (Kray) ~ d (calculated) = 2.178 « 10° kp/m? So density decrease = 2.178 «10° -2.165 = 10°) = 0.013 » 10° kg/m? 3 kgim* Henee fraction of un-oceupied sites _ density decrease ‘(calculated) 70. n. 4, 75. n. 78. 7. B 2.178 = 108 96 « 10" So the fraction of unoccupied site in sodium chloride erystal is 5.96 « 10 Body diagonal = 2(°" +1-) =V3.a 20/137 +4-)= 17328 200.7324 +1-)~ 1.7328 2r For the given crystal ‘These are the characteristic of @ hexagonal system, Reciprocal of intercepts Ys, Me So integral numbers : 1.1 0 AA face centered cubic lattice has 4 atoms per unt cell in the packing, Number of tetrahedral voids is double ‘the number of atoms in the packing that is 8. ‘Volume of unit cell = Area = b = 17.77 «10% « 7.41 « 104 = 131.68 » 10 ee ‘Mass of unit cell = V = d = 131.68 » 10% « 0,805 =106 « 10%g number of SO, molecule per unit cell 10" 4 6.023 « 108 Most symmetric erystal system Cubic: a= b~e and a~ By 90° Example, NaCl, diamond ‘Most unsymmetric system: triclinic: a b#eand az PE TF 90" example, CuSO, SHO monoclinic: ab #e and a= B90, #90" ‘example, monoclinie sulphur ‘When equal number of eations and anions (such that charges are equal) are missing (1 Na’, 1 CIVIL Fe", 2Ch), Itis a case of Schottky defect.8.42 ™ Solid State 81. 85, 87. Number of tetrahedral voids in a unit cell = 2.» number of sphere in unit cell =22 Number of oxide ions = 4 ‘Number of octahedral voids = 4 ‘Number of Tetrahedral voids ~ 8 Fraction tar ‘Size (volume) of the sphere 4/3 mr’ =a PA? ‘The void in c.c.p. and h.c.p. = 26 %. So the required atomic volume 5 100 A2=5.66.A xax In FCC structure ro > or a2 2N2 -2r~ 2-4, 22 ‘Number of Au atoms at the corners = 8/ ‘Number of Cu atoms at the faces = 6/2 = 3 So formula of the compound = AuCu, ‘Number of Y- ions in unit cell = 8» 1/8+1=2 ‘Number of X' ions in unit cell = 4 So the formula is XY. NaCl erystal has face-centered lattices in Na” and CF ions, interpenetrating. The co-ordination num- ber of Na” is 6, that is, each Na” ion is immediately surrounded by 6CI- ions (similarly each CI ion is immediately surrounded by 6 Na’ ions) and the next nearest neighbour of Na’ is 12 Na' ions. 4 ‘Volume of atoms in cell = 3 a = n (n=4 for foc) 4g ul6 -jemeand me ZsM Density = 2 For BCC, Z=2, May =213 a1. 98, 98, 99. 24213 (4366 = 10) « 6.023 « 10 = 8250 glem’ X (feo) = 8 « 18 = 1 thats 1 Y (tetrahedral voids) =2 that is 2 2 (octahedral voids) ~ 1 that is %& X:¥2 1:2 2ed:1 So formula = XYZ. In CaF, erystal, the Ca ions are present at all comers and at the centre of each face of the cube and the F-ions occupy all the tetrahedral sites density = 10.57 gm/ml 1 Volumeigram = 75137 mV/em As this contains 1.4 ~ 10 unit cells, so the volume of | unit cell 1a 1057 «14 = 10" 10" 10.57 « 1.4 10% ay that is, =675(A) Hence side length = (67.5)!"A=4.1A As each Sr ion introduces one cation vacaney, therefore, concentration of ation vacancies = mole % of SrCl, added So concentration of cation vacancies =10* mole % _10* = Top * 6.023 «10 = 6.023 » 108 » 10= 6.023 » 10" For each Sr" added, one cationic vacancy is created, because two Na ions are removed. ‘Number of cation vacancy = 2 « 10 mole % of NaCl 210 = 2a og mol! of NaCl =2 «10 « 6.02 » 10? mol” of NaClSolid State ™ 8.43 101. 102. 104, 105, 107. 108, im. 112, = 12.04 = 10 mot" of NaCl a fens _ xb 3.832 4 =1355A 2M a= aN, @n 192228 832 = 10%em) 6.022 = 108 = 22.67 g/m Number of atoms of Y= 4 Number of atoms of X= 2 « 8 3 Hence, the formula of compound is X,Y, As atoms along one edge or at corners don’t touch each other in fee cell For body centered cubic structure Packing fraction = 0.68 that is, 68 % of the unit cell is occupied by atoms and 32 % is empty. AW ions =6 «+8 %=4 OF ions = Tae aA For simple cubic: Here a = edge length & r'/r- = interatomic dis- tance For body centered a3 4 For face centered: ere 22 ‘Therefore rato of radi ofthe tvee willbe a 88 2° 4° a2 No, of A atoms =7 « 1/8 No. of Batoms =%4 « 6=3 No of C atoms = 1/8 113, 14. us, Mult 139. 1a. So the formula is A,, B,C, ie A,B,C Atoms of X per unit cell Atoms of Y per unit eell = 1 ‘Atoms of Z. per unit cell Hence the formula is XYZ, AB compound crystallizes in the eubie structure, A.atoms are at the comers of the cube. So, No. of A atoms per unit cell - 86 U8~1 No, of B atoms per unit cell = AB As, Simplest formula of the compound = AB. ple Correct Answer Type Questions Packing fraction for a cubic unit cell is zd Sarid? Here a = Edge length, r = radius of cation and anion Efficiency of packing in simple cubie or primitive coll = 2/6 =0.52 that is, 52% of unit cell is occupied by atoms and 48, % is empty. It means itis incorrect. As there are four anions and & tetrahedral holes per unit cell, so the fraction of volume occupied by spheres/unit cell volume of the unit cell ean be given as 4 (43 ra) +44 * 8 « (43 wre) 16 \2r'a8.44 @ Solid State 143, 146, 147, = "€ 32 ‘As for tetrahedral holes, <= 0.225- -¥ (1+(0.225)} a2 = 0.7493, So void volume = 1- 0.7493 =0.2507/unit cell volume of unit cell per cent void space = 25.07 ® ‘No, of atoms in the close packing ~ 0.6 mol = 0.5 « 6.022 « 10" 6132 « 108 No. of octahedral voids ~ No. of atoms in the packing = 3.6132 » 10° ‘No. of tetrahedral voids = 2 « No. of atoms in the packing = 2 «3.6132 « 10% = 7.2264 « 108 Total no. of voids = 3.6132 = 10% + 7.2264 “108 = 10.8396 « 108 Body diagonal ~ a3 ~ 4.121 A V3 = 4.121 A(1.732) = 7.138. 2° + fey = TBA $021 7.138 ~ 2h = 7.138. -2(1.81 A) 24-352 AechCoraios= 2524 =176A Wisty centred ebie J ~317 pm a~ edge ~ d; b~ face diagonal; ¢ ~ body diagonal bP= 2a? be 24+ 2a? = 3a? en Ba unit cell body diagonal = 3 d= {3 (317) = 549 pm ret 4 _ 549 4 =137pm 148. Body diagonal = v3 d = V3 (412.4) = 714.297 pm. Cs ~ Cl bond ~ body diagonal 1/2 ~ (714.297) /2 57.1 pm C3- Cl bond lengh, 357.148 = 357.148 ~ 397.148 - 181 76.148pm 150, Total no. of atoms in 1 unit cell = (12 «1/6) +3 + (2 «112)=6 SI, Height of unt cell = 4rV 213 Base area = 6 «V3 /4 (21)? volume ~ height base area = ae V20B 6 » V34@20)?= 24 Vee 4182, Packing fraction = volume of the atoms in one unit cell volume of one unit cell 6d 3 m'/24N205 Fer’ =0.74=74 Packing fraction = 74% Empty space ~ 26 The IIT-JEE Corner 181. Number of atoms in hep is 6 per unit cell 6x4 Packing fraction = 5G Bo, Base area 6 * “> (4r?) C= 4r V(23)Solid State ™ 8.45 w3V2 =0.74 Packing fractio oid % = (1 - 0.74) « 100 = 26% 185 As“A’ atoms are at eight comers of the cube. So number of A atoms in the unit = 8 » 1/8 = 1 As “B’ atoms are at the face center of six faces, So number of B atoms share the unit cell =6*%=3 ‘Thus the composition of the substance is AB,. Numericals For Practice 1. Aluminium forms face centered cubic erystals. The density of Al is 2.7 gm/em*. Calculate the length of the side unit cell of Al [At. weight Al = 27] a. 205A b. 405A 805A 4. 605A 2, Calculate the 2 of X-rays which give a difftaction angle 20 = 16,80" for a erystal. (Given interpla- nar distance = 0.200 nm; diffraction = first order; sin 8.40° = 0.1461.) a. 58.4 pm 584 pm b. 5.84 pm 4. 648 pm. 3. An element crystallizes in a body-centered cubic lattice, The edge of the unit cell is 2.86 A, and the density of the erystal is 7.92 gem’, Calculate the atomie weight of the element. a. 508 b. 558 ©. 556 4. 548 4. The experimental density of cesium chlo- ride is 3.907 g/cm’, and the calculated density 3.920 g/ em*. What isthe per cent of empty lattice spaces in a erystal of cesium chloride? a. 0.33% b. 036% «030% 4. 0.38% 5. Ina crystallizes solid MX, the first onder reflections from (100), (110) and (111) faces using monochro- matic X- rays are 84 and 5.2 respectively. How does the spacing ofthe three planes vary in the solid MX? 10705 1.14 1.14 0.705: 1 0.70521: 1.14 2: 1.14: 0.705 poe 256 «10 «(5 = 104) 5 BB gs igsa- Pa = Si xS=2.165A =2165 pm the answer may be 216 pm or 217 pm. RbI crystallizes in bcc structure in which each Rb* is surrounded by cight iodide ions each of radius 2.17 A. Find the length of one side of RDI unit cel 2 201A b. 501A b. 401A a. 105A The edge length of a face centered cubic lattice of NaCl is 564 pm. What is the density of NaCl in g/ em"? a 126 © 4.46 b. 0.26 a. 216 ‘A metallic clement exists asa cubic structure. The cedge length of the unt cll is 2.9 A. The density of the metal is 7.2 gee. The number of unit cells in 100 g of the metal would be a 5.7% 10% b. 114 «108 6. 2.85 » 108 a. 5.7108 ‘The edge of the unit cell of KCI is 6.29 « 10-"m, and the density of KCI is 1.99 « 10° kgm, Ifthe KCI unit cell is face centered cubie and contains 4 K" ions and 4Clions per unit cell , then calculate the number of Kions in one kg of KCL a 8.07 « 10" b. 8.07 « 107" ©. 8.07 = 10" 4. 807 «10 Gold crystallizes as a face-centered cubic structure. ‘The side of a unit cel is 4.07 A. What is the radius of ‘2 gold atom, assuming the atoms to be in contact in the crystal? a LSA 140A, b. 148A 14d8.46 M Solid State u. 12, 4 16. 1. 18, 19, Chorium metal erystallizes in a body centred cubic lattice, The length of the unit cell is found to be 287 pm, Calculate atomic radius, a. 62.27 pm. b. 124.27 pm. 12.427 pm 4. 120.27 pm ‘At room temperature, polonium erystallizes in primitive cubie unit cell. If a = 3.35 A, Find the theoretical density of polonium. Molar mass M of polonium = 209 gmo“ a. 9.23 lem? ©. 932g em? b. 3.66 giem? 4d. 9.25 gem ‘The density of CaF, (lluorite structure) is 3.18 glem* TThe length of the side of the unit cell is: a. 353 pm. b. 444 pm . 546 pm. 4. 273 pm, Ina simple cubic lattice of anions, the side length of the unit cell is 2.88 A. The diameter of the void in the bond centre is a, 0.661 A, 6. 4208.4, b, 2.108A @. 104A Calculate the efficieney of packing in the diamond structure. The unit cell dimension of diamond is 3.567 A. a. 03411 ©. 03407 b. 03409 4. 0.3401 Iron erystallizes in a body-centered cubic cell hav ing an edge length of 287 pm. what isthe density of iron in gem’ a. 585 © 178 b, 3.87 4. 7.85 A compound with formula XY,O, adopts a erys- tal structure in which O* ions forms cep arrange- ‘ment. X* ions occupy octahedral void which Y* ions are distributed equally between tetrahedral and octahedral voids. The fraction of octahedral and tetrahedral voids occupied are respectively a. 12.5%, 50% ——b, 50%, 12.5% €. 25%, 7 . 75%, 25% CAO has NaCl structures with density 8.27 g/ ec. Ifthe ionic radius of O is 1.24 A, determine ionic radius of Cd. alsa bLA 18h 13k What is the density of KF(s) ifit has a NaCl struc~ ture and a unit cell length of 5.35 = 10 m? a. 1.37 g/m! b. 237 gem ¢. 247 glom? @. 257 g/m 20, 21. 22, 24, 26. 27. Volume occupied by one molecule of water (density = 1 gem) is a. 3.0» 10 em’ b. 5.5 10% em’ . 9.0» 10 em? d. 6.023 « 10 em’ ‘The second order Bragg diffraction of ‘X-rays with 2= 1A from a set of parallel planes in a metal ‘occurs at an angle of 60°. The distance between the scattering planes in the erystal is a 200A b. LO0A ©. 0S75A a LISA ‘The atomic radius of lead is 1.750 A. Lead erystal- lizes in a face- centered cubie lattice. What is the density of lead? a. 22.35 g/em* ©. 1135 g/cm’ b. 11.33 g/em* 4. 11.53 g/ em? Silver crystallizes in a face-centered cubic struc- ture, What is the edge length of the unit cell if the atomic radius of silver is 144 pm? a 203.5 pm b. 407 pm ©. 307 pm 4. 147 pm Clausthalite isa mineral composed of lead selenide, PbSe, The mineral adopts a NaCI ~ type structure. The density of PbSe at 25°C is 8.27 g/cm’. Find the length of an edge of the PbSe unit cell (molecular weight = 2862 g) a 644A © TA b. 613A d. 3.065.A Calculate the theoretical density of rhombic sulphur if a = 10.4646 A, b = 12.8660 A and © = 24.4860 A, Z = 128 for this unit cell a. 2.067 » 10° kg mr b. 2.067 » 10° kg m* ©, 2.067 » 10* kg m* 4. 2.067 » 10? kgm’ Sodium metal adopts bee structure, the distance between neatest sodium atoms is 367 nm, The edge length of the unit cell is nearly a 367A b. 418A © 521A 424A At room temperature iron erystalizes in @ body- centered cubic close-packed structure. The length of an edge of the cubic cell is 287 pm. A body- centered cubie structure has 2 atoms per unit cell,Solid State ™ 8.47 Given that the density of Fe is 7.86 g/em’, calculate the mass of an iron atom, & 9.25 «10 g /atom 29. b. 9.25 »10* g /atom ¢. 9.25 10 g /atom 4d. 9.25 10g /atom 28. Iron (II) oxide, FeO, crystal and each edge of the unit cell is 5.0 A. Taking density of the oxide as a6 ba e8 4.12 How many unit cells are present in a cube shaped ideal erystal of NaCl of mass 1.00 g? [Atomic mass of Na= 23, C1= 35.5] a 2.57» 10" b. 6.14 = 10" © 3.28 « 10" a. 1.71 108 ‘An unknown metal crystallizes in a body- centered cubic lattice with a unit cell edge length of 3.301 A. Its density is 8.569 g fom’ at 20°C. Identify the metal 4.0 g cm, calculate the number of Fe®* and O> a Mo bY ions present in each unit cell. Fe a. Nb Q Ans. Q. Ans. Q Ans. Q = Ans. Q. Ans. o{[. > 2030 b 4 i g Glos 2. a 8 2 9 © m a Blu >» m © wm © Mm » Bw a Blew eo mb m » m «© m ao cs < 21. d 22. © 23. b 24. b 28. b ee ee ee ee Hints and Explanations axM, M,*V 1. Density = here n= no, of atoms in one unit cell M,, = molar mass of atom or molecule For FCC unit cell, n = 4 Atomic weight at Al = 27 4x27 6.03 « 10 = 2.7 Vea a= 4.050 « 10% em= 405A 2 nh=2dsino (1) @)=2 «02 « sin(@4) hen 2~ 0.2 « 0.1461 = 0.05844 nm = 0.05844 » 10% m = 58.44 pm (1 pm = 10" m) Per cent empty lattice spaces 3.920=3.907 3.907 100 = 0.33% According to Bragg’s law, we have 2d sin =m. Fora first order reflection, n= 1 — $00” 250539" 1 0.1088.48 M Solid State a duo” 2 5in 8a" 2sin 52° 4 0.0906 -L, 1 1 ho duo! dus ~ G03" 0.146 | 010906 150.705 1.14 6 yl tH Ba, where a = edge length of the cube From question, H2I7A §; 217A 4x217 B a=S.01A & Mass of a unit cell = V = d = 29% 10472 = 1756 «10g, 100 Number of unit eells= 7500 gan =5.7* 10" 9. Since the edge of unit cell = 6.29 « 10" m ‘The volume of the unit cell = (6.29 » 10") m* Further the density of KCI = 1.99 » 10°kg m? Weight of the one unit cell = 1.99 = 10° 6.29 10°) kg 1kg of KCI contains 1 (6.29 » 10°) =1,99 » 10° Since each unit cell contains 4K‘ions , therefore, the number of K" ions present per kg of KCL ax L (6.29 » 10°) »1.99 « 10° =8.07 « 10" 10. ML. 2 14. 18. Each face of a unit cell consists of five atoms of ‘gold in contact, The diagonal of the square formed by connecting the centers of the four comer atoms is dr, where ris the radius of a gold atom. also, the diagonal of the square formed would be (4.07 V2) A. Equating the two values we have: 4r= (4.07 «V2)A, = 1.44 A= radius of gold atom. For b.c.e structure arab a © dro \3 «287 pm 287 4 © 1= 124.27 pm Or Volume, V = a = (3.35 AY = (3.35 » 10*em)! nM. NV . (1)209g mor) (6.022 = 10* mol) (3.35 « 10% em)’ = 9.23 g lem! ZM. Na Z=4,M=4042~ 19 Body diagonal of cubic lattice = aV3 Diameter of the void in the body center =a3 1.732 2.88) -2.88 = 4988-288 =2.108 A Here number of O* ions pe unit cell 8,6 8°2 Tetrahedral voids = 4 Octahedral voids = 4; Octahedral voids occupied by X° Octahedral voids occupied by Y" Total octahedral voids occupied = 2 Total tetrahedral voids occupied = 1 4 «128 827~ Son3 10? @ 46.8 10% emSolid State ™8.49 20. 21 21. = 468A Dts + Fea] 1A Weight of 6.023 » 10 molecule of water = 18 g As volume occupied by 6.023 = 10 molecule of water (density = 1g em) will be 18g Tgem? So volume occupied by one molecule of water 18 6.023 « 10" = 18cm’ or ml 988 «10 =3.0 10 em! m= 2d sin 2*1=2xdsind 3 2-24} d= QN3= 115A (sin 60° = V3/2) _ 452862 a= (229.87)""A =6.13A For bee structure of atoms, the nearest atoms touch along body diagonal Distance between nearest atoms 2.Ba 4 2nd B 25367 v3 =426A ‘The length of an edge of the cubic unit cell of iron is 287 pm, of 287 « 10 m= 2.87 « 0% em. From this length, the volume of the cubic cell of iron is calculated 28, 29. Vel «1 1=P= (87 « 10%em) = 2.36 « 107 Now mass = d« V = 7.86 « 2.36 « 10% 1.85 «10 As no, of atoms per unit cell = 2 185% 10 2 So mass of | atom = =9.25 « 10 g /atom ‘Volume of the unit cell = (5 « 10 em)! 25 x1 Density of FeO = 4.0 g/em* ‘Mass of the unit cell ~ 125 « 10 em’ « 40g =50« 108 ‘Mass of one molecule of FeO = Molar mass in grams Avogadro's number Tg mol 6.022 » 10* mol" = 1195 «10g Number of FeO molecules per unit cell 50 10%g 1.195 10° =419=4 ‘Mass of one unit cell (m) = volume « density pad Mz _Mz Ne Ny _ 85H 4 6.02 = 108 Number of unit cells in 1 6.02 « 10% a5 04 7257 10"CHAPTER 9 Chapter Contents Raoult’s law; Molecular weight determination from lowering of vapour pressure, elevation of boiling point and depression of freezing point and Various levels of multiple-choice questions. SOLUTION Solution is a homogeneous mixture of two or more chemically non-reacting substances whose compo- sition can be varied within certain limits. A solution which contains only two components is called a binary solution. The component which is present in smaller amount is called the solute and the other present in larger amount is called the solvent. Vapour Pressure of a Liquid It is the pressure exerted by vapours when in equi- librium with the liquid at a given temperature. It depends upon nature of liquid and temperature. Pure liquid has always a vapour pressure greater than its solution Vapour pressure of a liquid helps us to have an ideal of forces of attraction amongst the molecules of liquid that is, more the force of attraction, lower is the ‘vapour pressure and vice versa m= Vapour pressure of a liquid increases with a increase in temperature due to increase in kinetic energy of solvent molecules that is, increase in evaporation however it is independent of the nature of the vessel. The variation of vapour pressure with tempera- ture can be given by Clausius-Clapeyron equation as follows P, REMEMBER Addition of Hgl, to KI,,shows an increase in vapour pressure due to complex forma- tion number of spears present in solution decreases, 2KI + Hel, >K [Hel]9.2 @ Solutions and Colligative Properties Vapour Pressure of a Solution When a miscible solute is added to a pure solvent, it results in the formation of solution. As some molecules of solute will replace the molecules of the solvent from the surface, therefore, escaping tendency of solvent molecules decreases. This causes a lowering of vapour pressure. = The vapour pressure of a solution is less than that of pure solvent. = If vapour pressure of solvent is P and that of solu- tion is Ps then lowering of VP. = P - Ps. = Vapour pressure of solution decreases as surface area occupied by solvent molecule decreases and density increases. RAOULT’S LAW Raoult’s Law for Volatile Solutes Raoult’s law states that in a solution, the vapour pressure of a component at a given temperature is equal to the mole fraction of that component in the solution multiplied by the vapour pressure of that component in the pure state The total vapour pressure P of a solution con- taining two components A and B is 0% 2 XX Suppose a solution is obtained by mixing two volatile components A and B. If their vapour pres- sure in pure states are P,, P, respectively and mole fraction are X, and X, respectively then their partial pressures P,, P,, can be given or P=P,+P, =P, X, +P", X, Ls ASX, = Tone My Xo" aah, P So Pe +n, Here n, and n, represents moles of A and B respectively. As we know that X,+X,=1 X,=C1-X) P=(1-X,) P+ PX, P= (P,—Pr)X, +P, Composition of the Vapour The composition of the liquid and vapour that are in mutual equilibrium are not necessarily the same. ‘The mole fraction in vapour phase is high for more volatile component ‘Suppose the mole fraction of A and B in vapour phase be Y, or N, and Y, or N,, According to Dalton’s law, P, PX, PX,+P Y,orN, - PX Y,orN, = po“ PX +P) X, REMEMBER @® From here, we can say that the total VP of the solution can be related to the mole fraction of any component Gi) Total vapour pressure over the solution varies linearly with the mole fraction of ‘component also. i) Raoult’s Law as a special case of Hen- ry’s Law As according toRaoul’s law, the vapour pressure of a volatile component in a given by Henry's law which is given as ‘On comparing both these equations for Raoult’s law and Henry’s law, it can be said thatthe partial pressure of the volatile ‘component or gas is directly proportional to its mole fraction in solution. Only the proportionality constant K,, differs from P,". Thus, Raoult’s law becomes a special case of Henry’s law in which K,, becomes equal to P,*Solutions and Colligative Properties @ 9.3 Illustrations 1. Two liquids A and B on mixing form an ideal solution. At 30°C, the vapour-pressure of the solution containing 3 mol of A and | mol of, B is 550 mm Hg. But when 4 mol of A and 1 mol of B are mixed, the vapour pressure of the solution thus formed is $60 mm Hg. What would be the vapour pressure of pure A and B at this temperature? (i For a solution having 3 mol of A and I mol of Y P_.=P,+P, 2200 = 3 P», +P, @ (ii) Fora solution having 4 mol of A and I mol B. Pua Pat Py =p. ,—4mol_, p, ,—_Lmol (VP), BP). < BP) gy P>PYX PL> PY. X, P,> PX, + PX, = Here Hydrogen bonds are broken or weakened. Here AS is more while AG has less —ve value and the values of other colligative properties also decrease. = Here minimum boiling point azeotrop mixture is formed. Example, 1. C\H,OH + cyclohexane. 2. Acetone + carbon disulphide, 3. Acetone + benzene 4, Acetone + Ethylaleohol 5. Carbon tetrachloride + chloroform or Toluene 6. Methylalcohol + water 7. Water + Ethylaleohol x Vapour pressure ———> Mole fraction x, ‘x graph for non-ideal solution showing ve deviation (b) Non-ideal solutions showing negative devia tions: Negative deviation is seen when total vapour pressure for any mole fraction is less than that expected from Raoult’s law. This hap- pens when the new interactions are stronger than the interactions in the pure components (A -B>A-AorB -B interactions) = AH =-ve, AV=-ve = It forms maximum boiling azeotrope, for exam- ple, CHCI, + CH,COCH,, For such solutions AV and AH are negative. Example, 1. Chloroform + benzene 2. Acetone + aniline 3. Nitric acid (HNO), + water 4. Acetic acid + pyridine It does not obeys Rault’s Law = His -ve, Heat is evolved here) m= V=is-ve ( volume decrease as force increases) m= It forms maximum boiling azeotrop. Here (VP), <(VP),,, BP), > BP),,Solutions and Colligative Properties @ 9.7 P, —Mole Fraction >9.8 @ Solutions and Colligative Properties = The figure shows maximum vapour pressure at point M and therefore solution has lowest boiling point, Azeotropic Mixtures with Maximum Boiling Point ‘The mixtures of two liquids whose boiling point is more than either of the two pure components. = This is formed by that composition of a non-ideal solution showing negative deviation for which the vapour pressure is minimum, Example, HNO, (68%) + water (32%) mixture boils at 393.5 K Example, an aqueous solution of hydrochloric acid when subjected to distillation gives initially pure water and later forms a constant boiling mixture at 100°C which contains 20.24 % acid. = Ina mixture of two volatile liquids A and B, if A ismore volatile and present in excess, then during distillation the vapours will be rich of component A.and the liquid part will be richer in component B. Finally, we reach the point N where vapour pressure is minimum and the boiling point is maximum as shown in the figure. Vapour Vapour —Vapour pressure > x Liquid Tiana X,=0 X= —Mole Fraction > tage, the mixture distills unchanged in composition that is, complete separation of com- ponents from this type of solution into pure state is impossible. Mixture Showing Ideal Behaviour or Zeotropic Mixture Those liquid mixtures which distill with a change in composition are called zeotropic mixture. For this type of mixtures containing liquids A and B, vapour pres- sure composition curve is a straight line. On distilla- tion, A being more volatile, will collect as distillate Vapour of X x=0 —Mole Fraction > = The remaining fraction will be poorer in A and richer in B. By repeating the process of distillation again and again, we can get both the components in pure state, example, methanol-water mixture. Colligative Properties Colligative properties are properties of a solution which depend only on the number of particles like ions or molecules of the solute in a definite amount of the solvent but not on the nature of the solute. Colligative properties are mainly for dilute solu- tions (Ideal Solutions), non-volatile solute, and pro- cess involving no dissociation or association. Colligative Properties & No. of species fj (Molar mass) These ai (a) Relative lowering of vapour pressure (b) Osmotic pressure (©) Elevation in boiling point (d) Depression in freezing point as follows: ** Osmosis, Diffusion, BP, FP., VP. are not Col- ligative Properties Relative Lowering of Vapour Pressure When a non-volatile solute is added in a volatile sol- vent, the vapour pressure of the solution decreasesSolutions and Colligative Properties @ 9.9 or becomes less then the vapour pressure of pure solvent. It is due to the increase in density and decrease in naked surface area which decreases rate of evaporation. Asrate of evaporation & + vd If P» is vapour pressure of pure solvent and P is vapour pressure of solvent in solution than the lowering of vapour pressure (p) is given as AP =(P*-P) The relative lowering of vapour pressure is defined the ratio between lowering of vapour pressure and the vapour pressure of pure solvent. = Relative lowering of VP = When a solution is prepared by mixing the non volatile solute B and solvent A. X,+X, Here X, and X, are the mole fraction of solute and solvent respectively Here n= number of moles of solute N= number of moles of solvent P», =VP of pure solvent P,=VP of solution In dilute solution N> > > n and hence n w wM. N° m/WM ~ Wm Here w = weight of solute W = weight of solvent m = molecular weight of solute M= molecular weight of solvent Ps AP _ WM. So Se = Wm In place of this relation we can also use this alternative relation It is better to use this relation as it gives more accurate value If molarity is asked used the relation given below = The molecular weight of solute can be deter- mined with the help of the relative lowering of vapour pressure method. Measurement of lowering of Vapour Pressure using Ostwald and Walker Method Here a current of pure air is bubbled through the series of bulbs according to the adjacent figure. The air first get’s saturated with the vapours and carries some amount of vapours (&V.P of solute) and later an carries more amount of vapours(«tP*,-P,). Now these sets of bulbs and guard tube having CaCl, are weighted. Here loss in mass of solution bulbs & P, or P, loss in mass of solvent bulbs ot P*-P,or P,-P, Total loss in mass of both sets of bulbs & Por P:, or Gain in mass of CaCl, guard tube9.10 ™ Solutions and Colligative Prp erties a Dry air Solution Solvent CaCl,-U-tube Loss in weight se P Loss in weight = PP Gainin weight « P* Ps _ __loss in mass of solvent bulb ain in mass of CaCl, guard tube Illustrations 6. ‘The vapour pressure of pure benzene at 25°C is 639.7 mm Hg and the vapour pressure of a solution of a solute in benzene at the same tem- perature is 631.9 mm Hg. Calculate the molal- ity of the solution Solution Let n moles of solute are dissolve in 1000 g of benzene Number of moles of solvent (N) = 4980 P-Ps_n 639.7-631.9__n 639.7 TOOTS 78 _ x78 39.7 ~~ 1000 n= 281000 639.7 x78 = 0.156 m 7. The vapour pressure of pure water at 30°C is 31.50 mm Hg. When 3.0 g of a non-vola- tile solute was dissolved in 54 g of water, the ‘vapour pressure of the solution was found to be 31.30 mm Hg, Calculate the molar mass of the solute. Solution Given: P*,=31.50mm,P,=31.30mm, 0g, W,=54g, M,=? x 1 +16=18 g/mol W,-M, W,+W, MM, 3M, 31.50 3443" is’, 0.20. GM,) x (18M,) 31.50 “SEM, 71853 54 0.20 (M, + 1) =31.50* 1 0.20 M, + 0.20 = 31.50 0.20 M, 1.50 — 0.20 = 31.30 31,30 = Bae = 156.5 gémol 8. The vapour pressure of an aqueous solution of glucose is 750 mm of Hg at 373 K. Calculate the molality and mole fraction of solute. Solution At 373 K vapour pressure of water = 760 mm P=ps 1000 Pp — ‘Temperature oe Elevation in boiling point = Itis also termed as Ebullioscopy. m= It is measured by Lands Berger’s method and Koltrell’s method. = Suppose T*, and T, are the BP. of pure solvent and solution respectively than elevation in BP (AT, jis givenas AT.=T.-T, Here A T, is directly propotional to molality of solution AT, am, AT=K,m If molality of the solution is one, then AT,=K, The elevation in B.P. is also given as ,. 1000 Molecular weight of solute can be find out as follows _ Kw x 1000 M= aT,» W Here w = weight of solute W= weight of solvent K, = molal elevation constant or ebullioscopic constant, M=molarmass of solute RE K.* [000 Lv or Sv Here Lv or AHy = latent heat of vapouriza- tion w= If molar of molecular elevation in boiling point constant (K) is used take 100 in place of 1000 that is, K is 10 times to that of Ko w 100 aT,=K= gt = kT K= TooLv Illustrations 9. Calculate the boiling point of a solution con- taining 0.61 g of benzoic acid in 50 g of car- bon disulphide assuming 84 % dimerisation of the acid. The boiling point and K, of CS, are 46.2°C and 2.3 K kg mol" 1000 x K, x w Solution t= — 1000 x 2.3 x 0.61 NS 122 « 50 (molecular weight of C,H,COOH = 122) AT y= 0.23 AT, AT,,=AT, (a+ #) = 023 x (1-0.84+ 284) 0.8 2 Boiling point = 46.2 + 0.1334 = 46.3334°C = 0.23 x (I=9.12 ™@ Solutions and Colligative Prp erties 10. Calculate the boiling point of a 5 % solution of cane sugar (C,,H,,0,,). Molal elevation con- stant for water is 0.52 K kg mol Solution w=5g.W=65¢ m=342,K, = 0.52 K,» w_ * 1000 Al ae W - OS sae <0 B.P of solution, T, 373 +0.08 FAT, (As T, = BP. of water = 373 K) = 373.08 K 11. Calculate the elevation in boiling point when 12.5 g of urea is dissolved in 170 g of water. Molecular mass of urea is 60 and molal eleva- tion constant of water is 0.52 K kg mol Solution w=125¢ m=60 W=170g K,=052K kgmol* AT, K,* w_ * 1000 m < W = 125 x 0,52 « 1000 = «170 ee Depression in Freezing Point Freezing Point: It is the temperature at which the liquid and the solid form of the same substance are in equilibrium and have the same vapour pressure. A Solution freezes when it’s vapour pressure is equal the VP of pure solid solvent. Due to lower vapour pressure of the solution, solid form of a solution separates out at a lower temperature. On adding a non-volatile solute to the solvent it’s vapour pressure decreases and becomes equal to the VP. of solid solvent at lower temperature hence the freezing point of solvent also decreases. Suppose T+,T, are the freezing point of pure solvent and solution respectively than decrease in freezing point AT is given as At, Liquid solvent Solid solvent ‘Vapour pressure —— + Temperature = This is also termed as cryoscopy and depression of freezing point (AT,) = It can be measured by Beckmann’s thermometer method and Rast’s method, = For a dilute solution, AT, is directly propotional to the molality (m) of the solution. Hence AT, m AT,=K,m If molality of the solution is one, then AT, and M can be found out by using these rela- tions.W = Weight of solvent K, = Molal depression constant or cryoscopic constant M=Molar mass of Non-volatile solute Rr 1000 L, or AH, K, Here Lor AH, = latent heat of fusion = Ifmolar of molecular depression in freezing point constant (K) is used take 100 in place of 1000 that is, K =10K, A= Kx gt x 10 RT K= Toor, REMEMBER = The value of K, orK, depends on only nature of solvent and not on the nature of the sol- ute, Illustrations 12. How much ethyl alcohol must be added to 1.00 litre of water so that the solution will freeze at 14F? (K, for water = 1.86°C/mol) Solution F-32_¢ 5 14~32 _C 10 AT = K,« molality = w 10 = 1.86 Jext w= 24731 g Solutions and Colligative Pro _prties @ 9.13 13. 1.4 g of acetone dissolved in 100 g of ben- zene gave a solution which freezes at 277.12 K. Pure benzene freezes at 278.4 K. 2.8 g of asolid (A) dissolved in 100 g of benzene gave a solution which froze at 277.76 K. Calculate the molecular weight of (A). Solution For acetone + benzene mixture: K’,* 1000 x w aw aT= 1000 x K, x 1.4 (278.40 -277.12)= Tog 55 _ 1000 x K, 1.4 = 100% 58 o For solute (A) + benzene mixture ‘Suppose m is the molecular weight of (A) 1000 x mK, x 2.8 (278.40 = 271.16) = 9g _ 1000 x K,x 28 0.64= 100% mr Gai) From equation (i) and (ii), we get m = 232 14, The freezing point of a solution containing 50 cm? of ethylene glycol in SO g of water is found to be -34°C. Assuming ideal behaviour, calcu- late the density of ethylene glycol (K, for water = 1.86 K Kg mol") Solution Ethylene glycol = 50 cm* K,= 1.86 K kg mol" Mass of glycol (w) = Vx d=50xdg Mass of water (W) = 50 g K, * w x 1000 aw 1.86 x 50 x d x 1000 62x50 34= d= 1.133 g/em*9.14 @ Solutions and Colligative Prp erties 15. Calculate the amount of ice that will separate out on cooling a solution containing 50 g of ethylene glycol in 200 g water to -9.3°C. (K, for water = 1.86 K kg mol”), Solution w=50g,AT,=93 K,= 1.86 K kg mol K, « w x 1000 mew 9.3 = 1.86.62 x W 50 x 1000 - 61x W w 161.298 Hence amount of ice separated from 200 g water, = 200- 161.29 = 38.71 g 16. Find the freezing point of an aqueous solution of anon-electrolyte having an osmotic pressure of 2.0 atm at 300K. (K, = 1.86 K kg mol, R = 0.0821 L atm K+ mol Solution PV=nRT aet V "RT - 2am ‘ORI atm K~ mol = 300K =0.0812 mol L-! As AT, = K, x molality = 1.86 K kg mol" x 0.0812 mol L* =0.151K Freezing point of aqueous solution = 273-0151 = 272.849 K Van’t Hoff's Factor Certain solutes, which undergo dissociation or asso- ciation in solution, are found to show abnormal molecular mass. Due to it the colligative property becomes abnormal which can be explained by Van’t Hoff factor “i” ‘Normal molar ma Observed molar mass Observed colligative property “Normal colligative property i Actual number of particles or species Sxpected number of particles or species = For solutes showing neither dissociation nor association, the Van't Hoff’s factor ‘i’ is 1 Example, Urea, glucose, sucrose = For solutes showing dissociation, the Van't Hoff's factor (i) is > 1 Example, FeCl, Fe +3Cl- Here i= 4, i=2 for NaX, KX, AgNo,, BaSO, i=3 for Srf,, CaCl, Na,O i=4 for AICL,, K, Fe(CN), i=5 for AL(SO,), CaPO),, KFe(CN), = Degree of dissociation (a) = M,-Mo / 4 Mo (a4) Here n is number of species formed after disso- ciation, Mo, M, are observed and theoretical molar mass respectively.. = For solutes showing association, the Van’t Hoff’s factor i <1 Example, In dimerization of acids like benzoic acid in benzene. (Due to HG-bonding) m= Degree of Association’ nd -i) n=1 Myo (Ger) Here n = Number of species formed after asso- ciation, = When dissociation occurs colligative properties increase while on association colligative proper- ties decreases.Solutions and Colligative Pro _prties @ 9.15 1.62 K, Molal depression constant of CH, is 4.9 K mol" kg. What is the percentage asso- ciation of acid if it forms double molecule in solution? REMEMBER Solution Given: w=2g W=25¢, AT= 162 K=49 1000 x K’,x w Mlustrations at = aw 17, ‘The freezing point of a solution containing 0.2 1000 49 «2 g of acetic acid in 20.0 g benzene is lowered 1.62 ea by 0.45°C. Calculate the degree of association of acetic acid in benzene. Assume acetic acid m,,= 241.98 dimerises in benzene. K, for benzene = 5.12 K mol! Kg, nC,H,COOH = (C,H,COOH), Solution Given: Before association 1 0 w=02¢, W=20g, After association = (I-@) ain preaase Total number of mole at equilibrium l-a + p= 100K meW A a 0.45 = 1000 5.12 x 0.2 20*m For dimmer formation, n=2 So m (observed) = 113.78 122.0 ae 24198 “18% 9 2CH,COOH = (CH,COOH), (m,, = 122.0 for CH,COOH) Before association 1 0 1-3 = 0.504 After association (=a) a2 a = 0.992 or 99.2% Here a is the degree of association 19. A 1.2% solution (weight/volume) of NaCl is m (normal) =j-at isotonic with 7.2% solution (weight/volume) m (observed) 2 ‘of glucose. Calculate degree of ionization and Van’t Hoff factor of NaCl So = att, 113.78 2 ; . Wt of solute Solution % of wtvolume=Vehime of solution” a= 0.945 of 64.5% Weight of glucose = 7.2 g 18. 2 g of benzoic acid dissolved in 25 g of C,H, shows a depression in freezing point equal to Volume of solution = 100 ml9.16 ™@ Solutions and Colligative Prp erties For glucose: & Vx ST Magy OF Ry = 1.2 x 1000 x 0,0821 xT 180 = 100 For NaCl y= ax Vx ST 2 x 1000 x 0.0821 xT 58.5% 100 As both the solutions are isotonic so, Tuy (NaCI) =m, (Glucose) For NaCl X gon ita (7.2 * 1000 x 0.0821 x T¥(180 x 100) x (58.5 « LOO)/(1.2 * 1000 * 0.0821 x T) =1+a=@ a=0.95 i= 1.95 20. Assuming complete dissociation, calculate the expected freezing point of a solution pre- pared by dissolving 6.00 g of Glauber’s salt, ‘Na,SO,,10H,0 in 0.100 kg of H,0. (Given for water, K,= 1.86 K kg mol", Atomic masses: Na =23, 8 = 32, 0= 16, H=1). Solution Molecular mass of Na,SO, 10H,0 = (2 23) +32 + (16 x 4) + (10 * 18) = 322 g/mol Na,SO, .10H,0 + 2Na* +SO,> + 10H,0 Van't Hoff factor (i) =2+1 10 H,O molecules are not considered for calculat- ing Van’t Hoff factor because water is solvent. Moles of Glauber salt ‘Mass of solvent in kg Molality = 68 322 gimol * 0.1 kg T,-1,=4T, =i.K,.m = 3x 1.86 x 104K =a 322 x01 T= 1.04 = 273 -1.04=271.96K 21, X g of a non-electrolyte compound (molar ‘mass = 200) are dissolved in 1.0 litre of 0.05 M NaCl aqueous solution. The osmotic pres- sure of this solution is found to be 4.92 atm at 27°C. Calculate the value of X. Assume complete dissociation of NaCl and ideal behaviour of this solution. (R = 0.082 litre atm mol"! K-). Solution Given n= 4.92 atm; T= 27 +273 = 300K V=1 litre = oe n, = mole of non-electrolyte = 585 1, = mole of NaCl = 0.05 According to. xV = nST Ven, ST +n,(1+a)ST xV=[n, +n, (1 +a)] ST; Here a= 1 given for NaCl 4.92 «1 = [C sh5) +005 x 2] « 0.082 «300 X=20g 22, 0.85 % aqueous solution of NaNO, is appar- ently 90% dissociated at 27°C. Calculate its osmotic pressure. (R = 0.082 L atm K-' mol) Solution NaNO, = Nat + NOS Initial 1 mol 0 0 Equilibrium m(1 -0.9) 09M 09MSolutions and Colligative Pro prties @ 9.17 Total particles after dissociation =1-09+09+09=19 Initial moles of NaNO, _ Mass of NaNO, in 10 ml solution ~—~“Molecular mass of NaNO, = 0.85 => = 0.01 mol Total moles of particles after dissociation =0.01 «19=0.019m a V= nRT a= OE = 0.019 « 0.082 » 30 (ioo7i00 Ly +674 atm. 23. A0.15 molar solution of phenol in water gave an osmotic pressure of 2.82 atm at 27°C, Caleu- late the Vant Hoff's factor. If phenol forms dou- ble molecules in solution, calculate the degree of association. Solution As theoretical osmotic pressure (r,) =eRT = 0.15 « 0.0820 x 300 = 3.69 atm Observed osmotic pressure (#,) = 2.82 atm ®, _ 282 Vant Hoff factor (i) = a = $55 = 0.7633 ‘The low value observed for osmotic pressure suggests that phenol molecules in water have undergone association 2C,H,0 = (C,H,OK), 1-aa/2 Here a is the degree of association. Total number of moles after association =1- a+ $=C- 4 )motes Number of moles if no association occurs = 1 mole i= Total moles after association ‘No.of moles when there is no association. 0.7633 = ad) 0.7633 = (1- ) a = 0.4734 = 47.34%. Enhance Your Knowledge Osmosis = Osmosis was first observed by Abbe Nollet in 1748. In osmosis there is a net flow of solvent molecules from the solvent to the solution or from a less concentrated solution to a more concen- trated solution through a semi permeable mem- brane (animal membrane, cell wall, CaPO)),, Copper ferrocyanide [Cu,Fe(CN),] = Plant and trees absorb water from soil by osmo- sis. = In osmosis, semi-permeable membrane is required but not in diffusion. In diffusion, flow is from higher to lower concentration, Osmotic Pressure It is the equilibrium hydrostatic pressure of the column set up as a result of osmosis, Or, It is the minimum pressure that must be applied on the solution to prevent the entry of the solvent into the solution through the semi permeable mem- brane, Or It is the minimum pressure needed to apply on a solution to make its vapour pressure equal to be vapour pressure of solvent m= Itis denoted by P or. Itismeasured by Pfefier’s method, Berkely-Hartley’s method, Townsend’s method ete. Townend method is used to find osmotic pressure of non aqueous solution with- out using semi permeable membrane. = Van’t Hoff’s Equation of Osmotic Pressure: It is as follows:9.18 @ Solutions and Colligative Prp erties n=CST Here x = osmotic pressure C =concentration of solution in mol/lit SorR = solution constant (© 0.0821 lit-atm/deg-mol) T = absolute temperature in K So «QC (at constant temperature) n= y ST(C=nV) aV=nST Here n= moles of solute, V = volume of solution =p mV =T7RT Asn=wM M = molar mass of solute w= gram weight of solute = Determination of Molecular Weight from Osmotic Pressure M _ST woR M=WSE nV=nST (n= W/M) ‘= When solute is not dissolved in one litre or it is dissolved in V litre then av=st wWxst M-"axV = Accurate molecular weight is obtained in follow- ing conditions (@) Solution must be very dilute, (ii) Solute must be non-volatile (ii) Solute should not undergo dissociation or association in the solution. = Isotonic Solution Solutions having equal molar concentrations or equal osmotic pressures are called isotonic solutions. Example, 0.91 % solution of, pure aqueous NaCl is isotonic with human RBC, = 6% urea and 0.1 M glucose are isotonic. P,= Porn, = In isotonic solution net is not possible osmosis, Molecular Masses of Polymers: It is best deter~ mined by osmotic pressure method firstly as other colligative properties give so low values that they cannot be measured accurately and secondly, osmotic pressure measurements can be made at room temperature and do not require heating which may change the nature of the polymer. = In a mixture of two solutions, the solution with lower osmotic pressure is Hypotonic while solu- tion with higher osmotic pressure is Hypertonic. Here osmosis can take place. m= At freezing point solid and liquid are in equilib- rium so have vapour pressure = On cooling solution at freezing point the crystals of solvent are separated first. Solved Problems from the IITs 1. The vapour pressure of benzene at a certain temperature is 640 mm of Hg. A non volatile and non electrolyte solid weighing 2.175 g is added to 39.08 of benzene. The vapour pres- sure of the solution is 600 mm of Hg. What is the molecular weight of solid substance? [IT 1990, MLNR 1992] p for benzene = 640 mm ps for solution = 600 mm. Weight of non-volatile and non-electrolyte solute (w) = 2.175 g Weight of solvent (benzene) = 39.0 gSolutions and Colligative Pro prties @ 9.19 Mol. wt. of benzene (M) = 72 +6 =78 Mol. wt. of non-volatile and non-clectrolyte solute (m) =? POR = wxM m*W 640 ~ 600 _ 2.175 x78 640 m x39) m = 69.60 Calculate the molality of one litre solution of 93% H,SO, (weight/volume). The density of solution is 1'84 g/ml [UT 1990} 93 % H,SO, solution (weight/volume) means that 100 ml solution contains = 93 g of H,SO, Hence, in 1000 ml solution contains = 930 g of HSO, Weight = volume x density 1000 x 1.84 = 1840 g solution contains = 930 g of H,SO, In this solution, weight of solvent = 1840-930 = 910 g=0.910kg Molality of H,SO, solution Wt. of H,SO,/mol. wt. of H,SO, Wt. of solvent in kg 930/98 BOISE = 10-428 m The vapour pressure of pure benzene at a cer- tain temperature is 640 mm Hg. A non-vola- tile non-electrolyte solid weighting 2.175 g is added to 39.0 g of benzene. The vapour pres- sure of the solution is 600 mm Hg. What is the molecular mass of the solid substance? [IT 1990} According to Raoult’s law, P: wxM, Mo W w=2175g ,W=390g M 8m P»,=640 mm of Hg P, = 600 mm of Hg 2.175 x78 390) x 600 60 = 600 2175 x78, 600 39.00 40 5.25 The degree of dissociation of Ca(NO,), in a dilute aqueous solution, containing 7.0 g of the salt per 100 g of solution at 100°C is 70 per cent. If the vapour pressure of water at 100°C is 760 mm, calculate the vapour pressure of the solution. [IT 1991) Solution Ap,_, = Lowering in vapour pressure when there is no dissociation wxM Wem AP = Po * 160 x 14 x 18 200 164 ~ 584mm 70 _ Foo 07 Ca® +2NO, (n= 3) Degree of dissociation = Ca(NO,), Ap, =No. of particles after dissociation. p,., No. of particles when there is no dissociation _lt@-Da_ 1+G-)x07_ =m ene So Ap,.=24 Ap, =24%5.84= 1402 mm 24 PoP. = AP,,, = 14.02 PL=P,~ 14.02 760 - 14.02 45.98 mm 5. Addition of 0.643 g of a compound to 50 ml of benzene (density = 0.879 g/mL) lowers the freezing point from 5.51°C to 5.03°C. If K, for benzene is 5.12, calculate the molecular weight of the compound. [IT 1990]9.20 ™ Solutions and Colligative Prp erties Solution Molality of the solution AT, _ 0.48 = ei = Sip = 0.09375 0.643/M. Goxo.879/1000) ~ 9975 M= 0.643 * 1000 30 0.879 x 0.09375 = 156.06 g mol 6. Addition of 0.643 g of a compound to 50 ml of benzene (density = 0.879 g/ml) lowers the freezing point from 5.51°C to 5.03°C. If K, for benzene is 5.12, calculate the molecular weight of the compound. [HT 1992} K,=5.12K kgmol w= 0.643 g AT,=T,-T, = 5.51 5.03 = 0.48 W= 43.95 (m=v xd =50 ml x 0.879) m=? K, x w x 1000 aT, = W = 5120.43 > 1000 0.48 « 43.95 = 156. 7. What mass of non volatile solute (urea) needs to be dissolved in 100 g of water in order to decrease the vapour pressure of water by 25%. What will be the molality of solution? Solution According to Raoult’s law P. = WxM Wxm Ifp,= 100 mm and p,=75 mm 100-75 _ _wx18 75 ~ 100 « 60 Wd _ wx 1000 Molality = “Se = MILI «1000 60x 100 ~ 1852m 8. 8.0575 107 kg of Glauber’s salt is dissolved in water to obtain 1 dm: of a solution of density 1077.2 kg m>, Calculate the molarity, molality and mole fraction of Na,SO, in the solution. [ur 1994) ‘Volume of solution = | dm? Density = 1077.2kg m> Mass of Na,SO, = 1077.2 - 1000 =77.2 gin | litre of solution 712 = 0.5436 Moles of Na,SO,= 35 Molarity = 0.5436 M Molality = 0.5436 m 0.5436 0.5436 + 55.55 oe Mole fraction = ‘The molar volume of liquid benzene (densit 0.877 g mL“! increases by a factor of 2750 as it vaporizes at 20°C and that of liquid toluene (density = 0.867 g mL) increases by a fac- tor of 7720 at 20:C. A solution of benzene and toluene at 20°C has a vapour pressure of 46.0 torr, Find the mole fraction of benzene in the vapour above the solution. [IT 1996] Solution In vapour phase 1 mole that is, 78 g benzene has volume at 293 K For benzene Similarly, 1 mole of 92 g toluene has volume at 293K = 92x = Gae7 * 7720 mL As PV=aRT Pe, 7 «2750 Fae" Tar ag = 1 * 0.0821 x 293 So 74.74 mmSolutions and Colligative Pro erties @ 9.21 Similarly, for toluene Py 92x 720 760 * 0.867 x 1000 ~ | * 0.0821 * 293 Pe, =22.37 mm As P. =P, X, +PLX, P,=P*,X,+P*, (1-X,) 46 = 74.74 X, + 22.37 (1-X,) Hence X= 045 (in liquid phase) As So X,=0.55 (in liquid phase) As Py X,=P,X’, thatis, 74.74 x 0.45 =46* X’, So X°, (In gas phase) = 0.73 10. A very small amount of a non volatile solute (that does not dissociate) is dissolved in 56.8 em? of benzene (density = 0.889 gem”). At room temperature vapour pressure of this solu- tion is 98.88 mm Hg while that of benzene is 100mm Hg. Calculate the molality of this solu- tion, Ifthe freezing temperature of this solution is 0.73 degree lower than that of benzene, what is the value of molal freezing point depression constant of benzene? [rr 1997] Solution According to Raoult’s law, 1000 778° Wn 1000 12 x 1000, 100 * 78, n= =0.144m x molality 0.73 =K,« 0.144 073 0.144 7 = 5.07 K kg mol" 1. A 6.90 M solution of KOH in water contains 30% by weight of KOH. What is the density of the solution? [IT 1997] Solution Molarity of KOH solution = 6.90 M Mol. wt. of KOH = 39 + 16 +1 =56 Weight of KOH in one litre solution = Molarity x mol. wt = 6.90 x 56 = 386.4 g Since the solution of KOH is 30% it means that 30 g of KOH are present in 200 386.4 g of solution = 1288 g of solution Density = Weighting _ 1288 g Volume in ml ~ 1000 mi = 1.288 gml* 12. A solution of a non-volatile solute in water freezes at -0.30°C. The vapour pressure of pure water at 298 K is 23.51 mm Hg and K, for water is 1.86 degree/molal. Calculate the vapour pressure of this solution at 298 K, [IT 1998] Solution AT,=K,xm According to Raoult’s law, = x 1000 x M m * Wx 1000 =m (molality) « a aT, om ‘K, * 10009.22 @ Solutions and Colligative Prp erties Ps, = 23.51 mm Hg K,= 1.86 K/molal M=18 eel 03, 18 Pe 186 * Tog 23-44 mi Hi 13. To 500 cm? of water, 3.0 x 10kg acetic acid is added. If 23 % of acetic acid is dissociated, what will be the depression in freezing point? K, and density of water are 1.86 K kg mol! and 0.997 g cm~ respectively. [IT 2000) Solution A1,=K, x molality x (I+ a for CH,COOH CH,COOH a CH,COO- + Ht 1 0 0 1 a a Asa=23%=0.23, mol of CH,COOH Molality = “ras of water in kg. 3.0 x 10° x 1000 {60 x $00 x 0,997 1000 0.10 AT, = 1.86 «0.1 «1.23 = 0.288K 14, The vapour pressure of two miscible liquids (A) and (B) are 300 and 500 mm of Hg respectively. Ina flask 10 mole of (A) is mixed with 12 mole of (B). However, as soon as (B) is added, (A) starts polymerizing into a completely insoluble solid. The polymerization follows first order Kinetics. After 100 minute, 0.525 mole of a solute is dissolved which arrests the polymer- ization completely. The final vapour pressure of the solution is 400 mm of Hg. Estimate the rate constant of the polymerization reaction. Assume negligible volume change on mixing and polymerization and ideal behaviour for the final solution [IT 2001] Solution A(@+BM—@, + BO Insoluble As P,=P+,X,+P,X, - a 5 12 So P,=300( 755 )+500( 434) Here a mole of A are left after polymerization after 100 minute As 08, “e 2.303, 10 So K= 705 tog, P.-C) After 100 minutes polymerisation is checked. After 100 minute solute is added and final vapour pressure is 400. P,- 400 = 0.525 (a+12) So Gi) 400 After solving equation (i) and (ii) 99 (iv) On Putting the value of ‘a’ in equation (ii) 2303 K=7q bog, Jo 9 K=1.0x 104 15. Match the boiling point with K, for X, ¥ and Z, if molecular weight of X, Y and Z are same, Boiling point K, x 100 0.68 Y 27 0.53 Zz 253 0.98 [IT 2003] RTM 1000 AH, RT, M 1000 AS, Also ASolutions and Colligative Properties @ 9.23 ‘As during vaporization, entropy increases because randomness increases. AS, may be taken as almost constant as for, liquid = vapour even if the extent of disorderness varies from liquid to liquid because the S, is abnormally higher than S, — S, = AS, is almost constant. If Mand R are constant K, oT, ie, KO) =0.68 K,(Y)=0.53 K,Z)=0.98. 16. 1.22 g of benzoic acid is dissolved in (i) 100 g acetone (Kb for acetone = 1.7) and (ii) 100 g benzene (Kb for benzene = 2.6). The eleva- tion in boiling points AT, is 0.17°C and 0.13°C respectively. (a) What are the molecular weights of benzoic acid in both the solutions? (b) What do you deduce out of it in terms of structure of benzoie acid? IIT Mains 2004] Solution (@) If M, = molecular mass of benzoic acid in acetone = 17«1.22 x 10000 T7x 100g > 122 #mol molecular mass of benzoic acid in 2.6 x 1.22 x 1000 O13 100g ~ 244 g/mol (b) i =—-Noumal molecular mass of benzoic acid ‘Abnormal molecular mass of benzoic acid 122 g/mol “244 gimol =05 This indicates than benzoic acid exists as dimmer in benzene 17, 75.2 g of C,H,OH (phenol) is dissolved in a solvent of K,= 14. if the depression in freez- ing point is 7 K then find the % of phenol that dimerizes. [IT 2006 2C,H,OH + (C,H,OH), c-Ca Cal 2 7 = 140.8 (2-a/2) a=0.75=75%.9.24 @ Solution and Colligative Properties MULTIPLE-CHOICE QUESTIONS Straight Objective Type Questions (Single Choice only) For which case would AH,,, be expected to be nega- tive? (a) If solute-solvent interactions are the same as solvent-solvent and solute-solute interactions (b) If'solute-solvent interactions are much greater than solvent-solvent and solute-solute interae- tions (©) If solute-solute interactions are much greater than solvent-solvent and solute-solvent inter- actions (@) Ifsolvent-solvent interactions are much ‘greater than solute-solvent and solute-solute interactions Aliquid isin equilibrium with its vapour at its boil- ing point. On the average, the motecules in the two phase have equal (a) intermolecular forces (b) potential energy (©) temperature (@) kinetic energy A molal solution is one that contains one mole of solute in (2) 1000 g of the solvent (b) one litre of solvent (©) one litre of solution (@) 22. litre ofthe solution Osmotic pressure of a solution is 0.0821 atm at a temperature of 300 K. The concentration in mole! lit will be (033 (©03 «107 (6) 0.066 @3 When mercuric iodide is added to the aqueous solution of potassium iodide, the (@) freezing point is raised (b) freezing point does not change (© freezing point is lowered (@) boiling point does not change A sugar syrup of weight 2142 g contains 34.2 g of water. The molal concentration is 10. ML. 2 13. (@ 055 © 35 55 @or ‘The depression in fp. of 0.01 m aqueous solution of urea, sodium chloride and sodium sulphate is in the ratio @lta (12:4 (b) 1:2:3 (a) 2:2:3 ‘The freezing point of equimolal aqueous solution will be highest for (@) CN’ HC (aniline hydrochloride) (b) CaeNO,), (©) La(NO,), we, ‘The molal elevation constant of water is 0.51. The boiling point of 0.1 molal aqueous NaCl solution is nearly (a) 100.05°C (©) 1002° (b) 100.1°¢ (a) 101.0¢ Which of the following solutions will have the low- est fteezing point? (@) 0.0100 mLi,$0, () 0.015 mCacl, (60.0100 mkcl (4) 0.035 m CH,CH,CH,OH ‘otal vapour pressure of mixture of 1 mol X (P*, = 145 tort) and 2 mol ¥ (P*, ~ 245 torr)is 200 torr In this case (a) There is a negative deviation from Raoult’s law (b) There isa positive deviation from Raoult’s law (©) There is no deviation from Raoult’s law (@) Cannot be decided On freezing an aqueous solution of sodium chlo- ride, the solid that starts separating out is (b) sodium chloride (A) none of these @) ice (©) solution How many moles of Fe ions are formed when exeess iron is treated with $00 mL. of 0.4 N HCI under inert atmosphere? Assume no change in volume.Solutions and Colligative Properties @ 9.25 4 15. 16. v7. 18. 19. @ 04 © 02 (b) 0.1 08 ‘The vapour pressure of a solution of Sg of non elec~ trolyte in 100 g of water at a particular temperature is 2985 Nm. The vapour pressure of pure water at that temperature is 3000 Nm. The molecular weight of the solute is, (@ 180 © 270 (b) 90 (@ 360 A solution obtained by dissolving 0.2 gm of solute in 100 em! of solution in benzene at 21°C develops a rise of 24 mm osmotic equilibrium. Find molar- ity and molality in the solution (If density of solu- tion is 0.88 gmvem’) (a) 83» 10° mol. (b) 4.15 « 10 mo/L. (© 83104 (@) none ‘An aqueous solution containing 1 gm of urea boils at 100.25°C. The aqueous solution con- taining 3 gm of glucose in the same volume will boil at (@) 100.75°C (© 100 (b) 100.5°C (@) 100.25%C Increasing the temperature of an aqueous solution will cause (a) decrease in molality (b) decrease in molarity (©) decrease in mole fraction (@) decrease in % (w/w) Lowering of vapour pressure, \p; elevation in boil- ing point AT,; and depression freezing point AT, of a solvent for the same molar concentration of each of the three solutes: (A) sugar, (B) NaCl and (C) BaCl, following the sequence (@ AT,:C>B>A (b) AT,:ASB 0, AS mix > 0 (@ AV mix = 0, AS mix > 0 For an aqueous solution, freezing point is 0.186°C. Elevation of the boiling point of the same solution is (K,= 186° mol" kg and K, = 0.512" mol kg) (a) 0.186 (b) 0.0512" (©) 1.86" (@ 5.12" A solute is soluble in two immiscible liquids which are present in a mixture. The concentration of the solute in the upper layer will be (@) More than in the lower layer (b) In fixed ratio with that in the lower layer (6) Same as in the lower layer (@) Less than in the lower layer Ina 0.2 molal aqueous solution of a weak acid HX, the degree of ionization is 0.3. Taking K, for water as 1,85, the freezing point of the solution will be nearest to (@) -0.480°C (©) -0.260%C (b) -0.360°C (@) 40.4800 Formation of a solution from two components can be considered as: (1) Pure solvent — separated solvent molecules, AH, (2) Pure solute + separated solute molecules, AH, 3) Separated solvent and solute molecules > solution, AH, Solution so formed will be ideal if:Solutions and Colligative Properties @ 9.27 41 2, 45, (@) AH iuag AH, — AH, ~ AH, (b) AH jag AH, ~ AH, ~ AH, (©) AFL conan = AH, + AH, ~ AH, @ AF ogg” AH, + AH, + AH, ‘Camphor is often used in molecular mass determi- nation because (a) Itis readily available (b) It has a very high eryoscopic constant (© Itis volatile (@) Itis solvent for organic substances ‘Vapour pressure of dilute aqueous solution of ghi- cose is 750 mm of mercury at 373 K. The mole fraction ofthe solute is @ 76 © v10 (b) 176 (@) 138 1M and 2.5 litre NaOH solution is mixed with another 0.5 M and 3 litre NaOH solution. Find out molarity of resultant solution. (@ 10M (b) 084M, (© 073M @ 056M ‘The azeotropic mixture of water and C,H,OH boils at 78.15°C. When this mixture is distilled, itis pos- sible to obtain (@) pure H,0 (b) pure C,H,0H (6) pure H,O as well as pure CH,OH (2) neither H,0 nor C,H,OH in their pure state ‘Two aqueous solutions, A and B, are separated by 4 semipermeable membrane. The osmotic pres- sure of solution A immediately begins to decrease. Which of the following statement is true? (a) The solvent molecules are moving from the solution of higher osmotic pressure to that of lower osmotic pressure (b) ‘The initial osmotic pressure of solution B is greater than that of solution A. (©) Solvent molecules are moving from solution Binto solution A. (@) Both (a) and (b) are true statements. Ethylene glycol is added to water as anti-freeze. It will (a) Only increase the boiling point of water (b) Be used for cleaning the radiator in a car (6) Prevent corrosion of automobile parts (a) Decrease the freezing point of water in water and increase the boiling point of water in summer 47. The volumes of 4 NHCI and 10.'N HCI required to make | litre of 6 NHC are (a) 0,67 litre of 4 N HCI and 0.33 litre of 10 N Hel (b) 0:80 lite of 4 N HCI and 0.20 litre of 10N HCI (©) 0.50 litre of 4 N HCI and 0.50 litre of 10 N Hel (@) 0.75 litre of 4'N HCL and 0.25 litre of 10N HCI 48. Which has minimum osmotic pressure? (a) 200 ml of 1M glucose solution (b) 200 ml of 2 M urea solution (©) 200 ml of 2 M NaCl solution (@) All have same 49. fais the degree of dissociation of Na,SO, the vant Hoff’s factor (i) used for calculating the molecular @ isa ) 1a (@1+2a @ 1-24 50. Osmotic pressure observed when benzoic acid is dissolved in benzene is less than that expected from theoretical considerations. This is because (a) benzoic acid is an organie solute (b) benzoic acid has higher molar mass than benzene (©) benzoic acid gets associated in benzene (A) benzoic acid gets dissociated in benzene 51. At same temperature, which pair of the following. solutions are isotonic solutions? (a) 02M BaCl, and 0.2M urea (b) 0.1 M urea and 0.1 M NaCl (©) 0.1 MNaCl and 0.1 MK,SO, (@) 0.1 MBa(NO,), and 0.1 MNa,SO, 52, If at certain temperature the vapour pressure of pure ‘water is 25 mm Hg and that of a very dilute aqueous9.28 ™ Solutions and Colligative Pre erties ‘urea solution is 24.5 mm Hg, the molality of the solu- tionis (a) 0.02 © Lu If the molecule of HCI were totally polar, the expected value of dipole moment is 6.12 D but the experimental value of dipole moment was 1.03 D. calculate the percentage ionic character? Oy (17 © 90 @ 9 (b) 12 (@) 0.08 50 ml of 10 N H,SO,, 25 ml of 12 N HCI and 40 ml of 5 N HNO, are mixed and the volume of the mixture is made 1000 ml by adding water. The nor- imality of resulting solution will be @ IN () AN © 3N @2N Equal volumes of ethylene glycol (molar mass = 62) and water (molar mass = 18) are mixed. The depression in freezing point of water is (given K, of water ~ 1.86 K mol-I kg and specific gravity of ethylene glycol is 1.11) (a) 0.0033 © 033 (b) 0.033 (@) 333 An azeotropie solution of two liquids has a boiling point lower than either of them when it (a) Shows no deviation from Raoult’s law (b) Shows positive deviation from Raoult’s law is saturated (©) Shows negative deviation from Raoult’s law (@) None of these In the process of osmosis (a) the osmotic pressure of dilute solutions is always very small (b) molecules of the solvent pass through the membrane while molecules of the solute may not (©) the value of the osmotic pressure is given by V=nRT (@ the osmotic pressure of blood (-25 tort) is due to the many dissolved microparticles such as Na‘, K*, Cl-and HCO, A solution containing 10 g per dm3 of urea (molec- ular mass = 60 g mol") is isotonie with a 5% solu- tion of a nonvolatile solute. The molecular mass of this non-volatile solute is (@) 350g mol (b) 200 g mot! (©) 250g mol (@ 300g mot 0. 61. a, cr 6, 1.00 g of a non-electrolyte solute (molar mass 250 g mol") was dissolved in 51.2 g of benzene. If the freezing point depression constant, Kf of benzene is 5.12 K kg mol", the freezing point of benzene will be lowered by (@) 05K (© 04K (b) 02K @) 03K 18 g of glucose (C,111,0,) is added to 178.2 g of water. The vapour pressure of water for this aque- cous solution at 100 (2) 759.00 torr (©) 76000 torr (b) 7.60 torr (@) 752.40 torr ‘Which has the highest freezing point? (@) 1 M rock salt solution (b) 1 mK ,{Fe(CN),] solution (©) 1mC,H,,0, solution (@ 1 mKCl solution Which will form maximum boiling azeotrope? (@) CH, + CJH,CH, solution (b) HINO, + 1,0 solution (©) C,H,OH + 1,0 solution (A) None of these Which of the following exhibits the greatest freez~ ing point lowering per mole of solute? (@) 0.01 m NaCl (b) 0.1 m Nac (©) 0.01 mC,H,0H (@) 0.1 mC,H,0H 5 litres of a solution contains 25 mg of CaCO, What is its concentration in ppm? (Molecular ‘weight of CaCO, is 100) @1 5 © 2 (@ 250 At 25, the total pressure of an ideal solution obtained by mixing 3 moles of A and 2 moles of B is 184 torr What is the vapour pressure (in tort) of pure B at the same temperature? (Vapour pressure of pure A, at 25°C, is 200 tor) (@ 100 () 16 © 160 @1 0.5 molal aqueous solution of a weak acid (HX) is 20 % ionized. If K, for water is 1.86 K kg mol, the lowering in freezing point of the solution isSolutions and Colligative Properties @ 9.29 67. 69. 70. 2. @ -Li2K (© 112K (b) 056K (@) 056K Phenol dimerizes in benzene having Van't Hoff factor 0.54. What is the degree of association? (@ 045 (b) 0.92 © 46 92 In the solubility of liquid solutions (@) & positive heat of solution means heat is absorbed as the solute dissolves to form the saturated solution (b) 4 positive enthalpy of solutions is when the system gains thermal energy on becoming saturated at the fixed temperature (©) there is no noticeable temperature changes (@ the solubility of a solute always increases with inereasing temperature What characteristics must a slightly soluble salt have if it is to be dissolved in water by increasing the temperature? (a) A smaller value for K,, atthe higher tempera- ture (b) A high negative slope for the solubility curve (©) Allow positive slope for the solubility curve (@) Ahigh positive slope for the solubility curve ‘A mixture of ethyl alcohol and propyl alcohol has vapour pressure of 290 mm at 300 K. The vapour pressure of propyl alcohol is 200 mm. If the mole fraction of ethyl alcohol is 0.6, its vapour pressure (in.mm) at the same temperature will be (a) 300 (b) 700 © 360 @ 350 ‘The relative lowering of vapour pressure produced by a solution of 18 g of urea in 100 g of water is approximately (a) 0.025, (© 005 (b) 05 (@ 025 4.5.25 % solution of a substance is isotonic with a 1.5 % solution of urea (molar mass = 60 g mol”) in the same solvent. If the densities of both the solu- tions are assumed to be equal to 1.0 g em, molar ‘mass of the substance will be (@) 115.0g mol" (b) 105.0 g molt () 210.0 mol (@) 90.0 g mot* 2B. 4. 78, At 80°C, the vapour pressure of pure liquid “A” is 520 mm Hg and that of pure liquid “B”is 1000 mm Hg. If a mixture solution of “A’ and ‘BY boils at 80°C and 1 atm pressure, the amount of ‘A’ in the mixture is (1 atm = 760 mm Hg) (a) 52 mol per cent (b) 34 mol per cent (6) 48 mol per cent (A) 50 mol per cent Vapour pressure of pure A = 100 torr, moles = ‘vapour pressure of pure B = 80 tort, mole Total vapour pressure of mixture is a 187 torr b. 450 torr © 44 torr 4. 88 torr ‘The vapour pressure of water at 20°C is 17.5 mm Hg. If 18 g of glucose (C,H,,0,)is added to 178.2 ¢ of water at 20°C, the vapour pressure of the result- ing solution will be (a) 17.675 mm Hg (b) 15.750 mm He (©) 16.500 mm Hg (a) 17325 mm He. Brainteasers Objective Type Questions (Single choice only) 16. 7. 78. Solution S, contains 6 g of urea per litre and solu- tion S, contains 18 g glucose per litre. At298 K, the ‘osmotic pressure of a S,8, «. both the solution is 1 atm 4. both the solution is same ‘4.0.2 molal aqueous solution of a weak acid (HX) is 20% ionized, The freezing point of this solution is Given K,= 1.860C kg mol-I for water) a -045C b, -0.90%C «021°C 043°C ‘An aqueous solution of suerose, C1,H,,O,,, con- taining 34.2 alt has an osmotic pressure of 2.38 atmospheres at 17°C for an aqueous solution of glucose, C,11,0, to be isotonie with this solution, it would have9.30 ™ Solutions and Colligative Pre erties 79. 81. - 18.0 git b. 162 gilt 36.6 plit of glucose 4. 14.0 gilt ‘The freezing point of water is depressed by 037°C ina 0.01 molar NaCI solution. The freezing point 00.02 molal solution. of urea is dependent by a. 037°C b. 0 ©. 056 4. 0.1870 The relative lowering of vapour pressure of an aqueous solution containing non-volatile solute is 0.0125. The molarity of the solution is a. 0.70 b. 045 «034 4. 0.50 FeCl, reacts with K,Fe(CN), in aqueous solution to give blue colour if these two are separated by a s.p.m. as shown in the figure then due to osmosis OM K FeO), Solution Side A SPM, Side B a, blue colour is formed towards side A b, blue colour is formed towards side B €. blue colour is formed on both the sides side 4. no blue colouration ‘The osmotic pressure of 0.1 M solution of NaNO, and CH,COOH are P, and P, respectively. thus, b.P,

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