Solid State INTRODUCTION Matter may exist in solid, liquid or gaseous state Liquids and gases are called fluids. Itis due to their ability to flow. Their fluidity is due to the fact that molecules are free to move about. Solids are rigid and possess definite shape and volume. In solids, molecules, atoms or ions are held together by strong intermolecular, interatomic or interionic forces. This confers rigidity, definite shape, volume and long range order in solids The properties of the solids depend upon the nature of constituent particles and the binding forces operating between them, The correlation between structure and properties helps in discovering new solid materials with desired properties like high temperature superconductors, magnetic materials, biodegradable polymers for packing, biocompliant solids for surgical implants ete. Whether a substance will exist as a solid, liquid or gas depends upon the net effect of following two opposing forces 1, Intermolecular forces : These exist among the constituent particles which keep them together. 2. Thermal energy : This is the energy possessed by the constituent particles due to temperature. Thermal energy tries to keep the constituent particles apart as it ends to make them move faster. ‘At low temperature, thermal energy is quite low but intermolecular forces are strong, The net result is that the particles are brought very close together. Therefore, constituent particles occupy fixed positions and are unable to move except that they can oscillate about their mean positions. Definition : A true solid may be defined as a matter which possesses rigidity, definite shape, definite volume and long range of order. GENERAL CHARACTERISTICS OF SOLID STATE Solids have the following characteristic properties (1) They have definite volume and shape. (2)intermolecular distances are short. () Their constituent particles (atoms, molecules or fons) have fixed positions and can only oscillate about their mean positions. Therefore, solids diffuse very slowly as compared to liquids and gases. (4) They are incompressible and rigid. {5)Soliés have high densicy. AMORPHOUS AND CRYSTALLINE SOLIDS Depending on the nature of order present in the arrangement of constituent particles, solids are classified as crystalline or amorphous. Il] Crystalline Solids Crystalline solids have a regular arrangement of atoms, ions or molecules. Their particles are arranged in a definite ‘geometrical fashion. Crystalline solids have definite melting point, definite heat of fusion and a definite crystal lattice. Crystals are made up of regular and periodic three dimensional pattern of particles in space. They possess a long range order of crystals. In some crystalline solids,constituent particles are arranged in two dimensional covalent network. Graphite has two dimensional structure. Examples of crystalline solids are diamond, graphite, NaCl, CsCl, CaF, ZnS ete Definition : Those solids which have definite geometrical shape, sharp edges, flat faces and long range order of the constituent particles are called crystalline solids. [ll] Amorphous Solids In amorphous solids, atoms or molecules are not arranged in any regular fashion. The atoms and molecules have a random and disordered arrangement. Amorphous solids do not have sharp melting points and definite heat of fusion. Amorphous solids do not have a definite crystal lattice and geometrical form. Glass, rubber, glue, plastics, polymers of high molecular mass ete. are the examples of amorphous solids. Glass and plastics are important amorphous solids. Amorphous silica is likely to be the best material for converting sunlight into electricity (photo voltaic) Microscopic studies show that amorphous solids have small regions of orderly arrangement. These small regions of orderly arrangement are called erystallites. Such portions are scattered and the arrangement between such portions are disordered. Amorphous solids do not possess long range order of crystals. Definition : Those solids which do not have regular arrangement of its constituent particles or have short range order of their constituent particles are called amorphous solids. Difference between Crystalline and Amorphous Solids Crystalline and amorphous solids differ in their physical properties : [1] Arrangement of Constituent Particles Crystalline solids Jong range order ‘This arrangement repeats itself periodically over the entire crystal Amorphous solids have a regular arrangement of particles in a small region only. It is called short range order. It is important to know that structures of crystalline ‘quartz, and that of amorphous quartz, glass appear to be identical. But in the amorphous quartz glass, there is no long range order. have ISC Chemistry-XIT @ CO) Fig. 1.1 Two dimensional structure of: (a) quartz ‘and (b) quartz glass [1] Melting Points and Enthalpy of Fusion Crystalline solids have sharp melting points. The amorphous solids melt gradually over a temperature range. They do not have sharp melting point. Crystalline solids have definite enthalpy of fusion whereas amorphous solids do not have definite enthalpy of fusion. ‘After melting, amorphous solids can be moulded and blown into various shapes. On heating, they become ‘crystalline at some temperature. Some glass objects from ancient civilisations are found to become milky in appearance because of some crystallisation. [111] Isotropy and Anisotropy In case of amorphous solids, properties such as electrical conductance, refractive index, thermal expansion ete. are identical in all directions like gases ot liquids. This property is called isotropy. Thus amorphous substances are isotropic. On the other hand, the crystalline solids have different values of above mentioned properties in different directions. This type of behaviour is called anisotropy and crystalline solids are anisotropic in nature. This property in crystalline solids is due to different arrangements of particles along different directions, Crystalline solids are the true solids. Unlike liquids, amorphous solids have very slow tendeney to flow and are called pseudo solids or supercooled liquids. Itis supported by the fact that glass panes of windows or doors of old buildings are found to be thicker at the bottom showing some fluidity possessed by glass.Solid State Fig. 1.2 Anisotropy in crystals is due to different arrangement of parlcles along diferent directions [IV] Cleavage with a Knife When cut with a knife, crystalline solids undergo clean cleavage whereas amorphous solids undergo irregular cut. ‘Table 1.1; Distinetion between Crystalline and Amorphous Solids Property Crystalline Solids Amorphous Solids 1. Shape Definite characteristic Iregular shape ‘geometrical shape 2.Melting Melt at a sharp and Gradually soften overa point characteristic tempe- range of temperature ature 3, Cleavage When cut with a sharp When cut with a sharp property edged tool, they split edged tool, they cut inco two pieces and the into two pieces with newly generated irregular surfaces surfaces are plain and smooth 4.Enthalpy of ‘They have a definite They do not have fusion and characteristic definite enthalpy of ‘enthalpy of fusion fusion, 5. Anisotropy Anisotropic in nature Isotropic in nature 6. Nature ‘True solids Pseudo solids or super- ‘cooled liquids 7. Order in Long range order. Only shore range order. arrangement of constituent particles Size and Shape of Crystals ‘Size of the crystals depend on the rate at which they are formed. Slower the rate, bigger is the crystal, I is because atoms or molecules have enough time to find their position in the crystal structure, It is for this reason that crystals of 1.3 ‘most of the minerals formed by geological processes are often very large. Inferfacial angles : Crystals are bound by plane faces. The angle between any two faces is called an interfacial angle. The shape and size of crystals of one and the same substance may be different, but the interfacial angles always remain the same. EE] CLASSIFICATION OF CRYSTALLINE SOLIDS Crystals may be classified according to the nature of binding forces which hold the constituent particles together as shown below [l] Molecular Solids Sulphur (Sg), phosphorus (P,), solid methane (CH,), solid carbon dioxide, iodine, solid argon etc. are molecular solids. These contain discrete molecules. The different ‘molecules are not linked by any bond in solid state. They are classified into following three categories : 1. Non-polar molecular solids : In these solids, the constituent particles are either atoms (e.., helium, neon, argon ete.) or non-polar molecules like H.,, Clz,Tz, CH,P etc. The atoms or molecules are held together by weak dispersion forces or London forces (a type of van der Waals forces). Such solids are soft with low boiling and melting points and are non-conductor of electricity. Due to the presence of weak intermolecular forces, they are usually gases or liquids under ordinary conditions. Important Characteristics : (1) They are soft and have low melting points. (2) They have low heats of vaporisation so that they exist asin gaseous state or liquid state at room temperature. (3) They are bad conductors of electricity 2, Polar molecular solids : In these solids, the constituent particles are polar molecules like HCl, SO, NH ete, They contain polar covalent bonds (H—C). Atoms have partial +ve or -ve charge. The molecules are held together by relatively stronger dipole-dipole interactions. These solids are soft and non-conduetor of electricity. Theit melting points are higher than those of non-polar molecular solids. They are usually gases or liguids under room temperature and pressure, Important Characteristics : (1) They are soft and have higher melting points than those of non-polar molecular solids. But they exist in ‘gaseous or liquid forms at room temperature and pressure.(2) They are non-conductors of electricity. (3) They have relatively higher heat of vaporisation. For example : Solid SO, solid NH, ete 3. Hydrogen bonded molecular solids : In these solids, the constituent particles are covalently bonded ‘molecules which contain hydrogen atom linked to I, O or N, eg., HE H,0, NH, etc. HE H,0 and NH, molecules are themselves associated through hydrogen bonding. There are strong intermolecular forces of attraction due to the presence of H-bonds. ‘These solids are soft and non-conductor of electricity. Their melting and boiling points are higher than the molecular solids of first two types, ‘They exist as volatile liquids or soft solids (like ice) under ordinary conditions. Important Characteristics : (2) They are soft and are non-conductors of electricity. (2) They are volatile liquids or soft solids at room temperature and pressure. [ll] tonic Solids NaCI, KBr, NaOH, CaF, MgO, CaCl, ete. are ionic solids These contain only ions. The cations and anions are held together by strong electrostatic force of attraction. ‘Therefore, these have high melting and boiling points. They do not conduct electricity in solid state, It is because the ions are not free to move in solid state, These conduct electricity in molten (fused) state and in solution. Itis because the ions ‘become free to move in molten state as well as in solution, The solids are hard, brittle in nature and electrical insulators. The ions are arranged in a definite geometrical fashion in crystal latice. Sodium chloride erystal is cubical and the coordination number of both Na* and Cl” is 6. The caesium chloride (CsCI) crystal is described as a body-centred cubic type of arrangement and not a perfectly body-centred cubic crystal and coordination number of both Cs* and CI” is 8. Coordination number depends upon the size and charge of the ions. Important Characteristics : @) Ionic solids have high melting and boiling points. @) They have high density, low volatility and high stability, ) They are highly soluble in water and other polar solvents having high dielectric constant but insoluble in organic solvents. There are few exceptions also, ¢.g.,PbSO 4, BaSO,., AgCl, AgBr, PbS, CuS ete. are jonic compounds but they are insoluble in water, ISC Chemistry-XIT Solubility of ionic compounds in water is due to the high dielectric constant value (80) of water. The high dielectric constant reduces the electrostatic force of attraction to 1/80 of its original value and ions get separated, Separated ions get solvated by water molecules. Solvation (hydration) is always an exothermic reaction and energy is released. ‘The energy liberated makes the ions present in ionic solids separated. An ionic solid dissolves in water if its (i) Hydration energy is large (i) Lattice energy is small, Compounds like NaCl, NaBr, KCl, KBr, Kl etc. are soluble in water. This is because their hydration energy is much ‘more than their lattice energy. Ionic compounds like BaSO,, PbSO,, AgCl, CaF, ete. are almost insoluble in water. This is because their hydration energy is much smaller than their lattice energy. (4) They are hard and brittle (5) Ionic compounds do not conduct electricity in solid state, This is because ions are held together by strong electrostatic force of attraction. Ionic compounds conduct electricity in molten state and in aqueous solution. This is because ions become free to move in molten state and in solution, (6) Aqueous solutions of ionic compounds give the reactions of ions present in solution, Ionic reactions are very fast. Crystals arrangement of atoms and geometry. Such crystals are known as isomorphous and the phenomenon is called isomorphism. For example : ZnSO, -7H,0 and FeSO, -7H,0 are isomorphous. of some ionic solids have similar (8) Ionic solids have high densities. (9) Tonic bonds are non-directional and compounds do not exhibit isomerism. (10) Crystal structure : Ionic solids are made up of large aggregates of cations and anions and these ions arrange themselves in such a way that the compound attains ‘minimum potential energy and maximum stability. ionic Structure of Sodium Chloride (Rock Salt) Sodium chloride crystal is composed of Na* and CI” ions and the radius ratio r,,,/ 1 is equal to 0.524. This suggests that it has octahedral structure and co-ordination number of Na* or Cl” ion 6.Solid State octahedral surrounded by six Na" ions Nations coctanecraly surrounded by sic Cr-ions: Fig. 1.3 Structure of NaCl Salient features of sodium chloride crystal are: (2) The CI” ions have face centred cubic arrangement. (2) Na* ions occupy all the octahedral sites. There will be one Na* ion for every Cl- ion. Thus the ratio of Na* and Lions in NaCl crystal is 1:1. (3) Each Na" jon is surrounded by 6CI~ ions and vice versa. Thus coordination numbers of Na* and Cl” ions in NaCl structure are 6 and 6. (4) The number of Cl- ions required to form cubic close packed lattice is 14, (.e.,8 at the corners and 6 at the face centres) while number of Na* ions required to fill the vacant octahedral sites formed byl ions is 13 (12 edge centres + ‘one body centre position). (5) The total number of ions present per unit cell is 8 (4Na” ions and 4CI” ion). In this way, there are 4NaCl formula units in each unit cell. (©) Neither Na* nor Cl- ions touch each other due to the presence of similar charges. Some other examples of this type of structure are Agi Ag¢l, NH, Cl ete, Increase in pressure increases the coordination number of Na’ and Cl” ions and NaCl acquires CsCl structure. [ll] Metallic Solids In metallic solids, metal atoms are bonded by metallic bonds. The metallic erystals contain metal ions (M"*) and free mobile electrons. The cations are formed by the loss of valence shell electrons of the metal. MM" +ne Thus each metal atom is supposed to consist of two constituents : (i) mobile valence electrons and (ii) positively charged residues called kernels (M"* }. The electrons given ‘out are not localised, ie, their positions are not fixed. The emitted electrons are mobile and spread over the entire lattice. In metallic crystal, the electrons surround an array of positive ions, It is called electron pool or electron sea or electron gas. Electron sea is formed by the electrons lost from the outermost shell of metals. Metallic bond may be defined as : The force that binds a metal ion to a number of electrons is called metallic bond. Fig. 1.4 Postive ions in a sea of mobile electrons (Metalic solid) Due to the presence of mobile electrons, metallic solids have following important characteristics : ) They are malleable and ductile. (2) They are good conductors of heat and electricity due to free movement of electrons throughout the crystal. (3) They have metallic lusture. (4) The hardness of metals depends upon the number of valence electrons as well as the strength of bonds present in them. Stronger the bond, harder is the metal and vice-versa (5) They have moderate heats of fusion. It is important to know that metallic bond explains the properties of metals. 1, Metallic Iusture : When light falls on the surface of a metal, the mobile electrons absorb photons of visible light. The electrons start vibrating at a frequency equal to that of incident light. The vibrating electrons emit electromagnetic radiations in the form of light. The metal surface begins to shine,2. Thermal conductivity : It is also due to mobile electrons, When a metal is heated, the kinetic energy of the ‘electrons in that region increases. The energised electrons move towards the cooler part of the metal and give their ‘excess kinetic energy to the electrons present in the cooler part. Now the electrons in the cooler part get energised, ‘These energised electrons now move and give their excess kinetic energy to other electrons. The process continues and heat is conducted throughout the metal. 3. Electrical conductivity : It is also due to the ‘mobile electrons. In a metal crystal, electrons move equally in all directions. But when a potential difference is applied across a metal, the electrons move towards the +ve electrode. The moving electrons carry the electric current from one point to another. Thus electrical conductivity is due to the directed flow of electrons towards the positive electrode. Effect of temperature on electrical conductivity : It decreases with the increase in temperature. It is because ‘when temperature is increased, the +vely charged kernels (M1** also start vibrating and interfere with the movement of electrons. 4, Metallic bond has no directional character : Therefore, wires of metals can be drawn, these can be beaten into sheets and twisted. Crystal Structure of Copper Metal Crystal lattice of copper is made up of identical positive ions forming a close packed structure, Copper crystal has fee structure in which metal ions occupy the corners of the cube and the centres of its faces. Each metal ion is surrounded by ‘twelve other identical metal ions. Six of the metal ions are in ‘one plane and three are above and three below this plane. (Fig. 1. Fig. 1.5. Unit cal of face centred cubic lattice of copper. The shaded (red)citcles indicate the metal ions at the face centres while the unshaded (yellow) circles indicate the metal ions situated at the comers. Face centred cubic lattices are also found in crystals of sve, gold, aluminium and lead ISC Chemistry-XIT [IV] Atomic or Network or Covalent Solids ‘The crystal lattice is made up of neutral atoms which are linked together by covalent bonds. They form a big structure. A covalent bond has directional character. The net-work solids form two dimensional or three dimensional structure, Due to the presence of large number of covalent bonds, atomic solids have high melting point. Such solids are very hard and brittle. They are called giant molecules. Diamond, graphite, silicon carbide (SiC), borazon (BN) ete. are covalent solids Important Characteristics : (2) They are generally hard. (2) They are bad conductors of electricity due to the absence of mobile electrons in them. But graphite is good conductor of electricity. (3) They have high heats of fusion and have high ‘melting points. Structure of Diamond Diamond has face centred cubic structure with extra carbon atoms inside the cube. Each carbon atom in diamond is sp®-hybridised and is bonded tetrahedrally to four other carbon atoms by covalent bonds. The coordination number of each carbon atom is four. Fig. 1.6 Structure of diamond Important Characteristics : (@) Diamond is very hard due to the presence of strong. carbon-carbon covalent bonds. (2) The melting point of diamond is about 3600°C because it requires large amount of heat to break strong CC bonds 2) Since all the valence electrons are involved in bonding and no free electrons are left to conduet the cleetrcity, hence diamond is a bad conductor of electricity,Solid State Structure of Graphite Unlike diamond, graphite has two dimensional sheet like structure. Each carbon atom in graphite is sp”. hybridised, Fach carbon atom is bonded to three other ‘earbon atoms through covalent bonds forming hexagonal planar rings. The C—C covalent bond distance in rings is 141.5 pm. Graphite has two dimensional sheet like Fig. 1.7 Structure of graphite ne polymeric rings. Two successive sheets are far apart from each other by 340 pm. Therefore the two successive layers are not able to form covalent bonds. These layers are held together by weak van der Waals’ forces. Important Characteristics : (2) Different layers in graphite are held together by weak van der Waals’ forces. Therefore one layer can slide over another giving rise to its slippery nature. This also permits the cleavage of the structure along the lines of planes. In this way, graphite is soft and slippery and can be used as lubricant. (2) Bach carbon atom in graphite is sp?-hybridized. Thus, one valence electron of each carbon atom is free to ‘move from one point to another. The unhybridized orbitals containing one electron each overlap laterally to form s-bonds in the same layer. These electrons are delocalized and are free to move under the influence of heat and electric field, Therefore graphite is good conductor of heat and electricity. (8) The carbon atoms are strongly held together by strong covalent bonds. Therefore melting point of graphite is very high (about 350°C). (4) Graphite has lower density than diamond due to the large distance between the successive layers ‘Table 1.2 : Different Types of Solids S. Type ofSolid Consttutent Bonding! Examples Physical Electrical Melting No. Particles Attractive nature conductivity point forces 1. oniesoliés Tons Coulombic or NaCl, MgO, ZnS, Hard but Insulators in solid state but conductors High lectostatic CaF brite inmolten sate and in a, solitons. 2 Covalentor Atoms Covalent SiO, (quar), Hard Insulators Very high network solids bonding SiC; (diamond) AN Cpe Soft Conductor exception) 3. Moleculasolids (Non-polar Molecules Dispersion or Ar, CCl Sof Insulator Very low ondon forees Has, €0, (ip Polar Molecules ipole-dipole HC1,S0,—Soft_——_nsulator Low interactions (ii) Hydrogen Molecules Hydrogen -H,0 ice) Hard——_Insulator Low bended bonding 4, Metallic solids Postve ons Metallic ‘Fe, Cu,Ag, Mg_ Herd but Conductors in solid state as wells in Fairly high inaseaot bonding ralleable molten sae. deloealised & ductile tleetronsQ.1 Classify the following solids into ionic, molecular, covalent and metallic. Diamond, Brass, Graphite, NaCl, Nitre, Sulphur, Methane. Ans. Metallic Brass Covalent: Diamond, Graphite Ionic NaCl, Nitre Molecular : Sulphur, Methane ERE] SPACE LATTICE OR CRYSTAL LATTICE AND UNIT CELLS Space Lattice or Crystal Lattice In crystalline solids, there is a regular repeating pattern of constituent particles. Space or crystal lattice may be defined in different ways. Fig. 1.8 A portion of a three dimensional cubic lattice and its unit cell First definition : A regular arrangement of atoms, ions or molecules in space to show the geometry of a crystal is called space lattice or crystal lattice. Second definition : A three dimensional collection of points is called space lattice provided each lattice point has the same environment as that of any other point in the lattice. Third definition : A crystal lattice is an arrangement of points in space which if repeated in all directions gives the shape of the crystal. There are 14 possible three dimensional lattices. These are called Bravais lattices. Some characteristics of a crystal lattice are (2) Each point in the lattice is called lattice point or lattice site. ISC Chemistry-XIT (2) Bach point in a crystal lattice represents one consti tuent particle which may be an atom, an ion or a molecule. (3) Lattice points are joined by straight lines to represent the geometry of the lattice, Unit Cells ‘The smallest repeating pattern is called unit cell. Such. units are repeated over and over again in three dimensions and generate the entire crystal Definition : A unit cell may be defined as the smallest block or geometrical figure which when repeated in different directions produces the entire crystal A unit cell of a crystal possesses all the structural properties of the given crystal. Thus, if a crystal is cube, the unit cell must also have its constituents arranged so as to sive a cube. Parameters of Unit Cells A unit cell is characterised by the distance a, b, ¢ along the three edges of the unit cell and the angle a, and y. For simple cubic system, a = f = y = 90° anda = b=. Thus, a unit cell is characterised by 6 parameters a, b,c, a, and 7, ‘The number of unit cells depends upon the size of crystal. (2) a, band emay and may not be perpendicular to each other, (2) Edge length a,b and ¢ may and may not be equal. (3) Angle between the edges : a, and y angles may and may not be of 90°. Fig. 1.9 Illustration of parameters of a unit cell Types of Unit Cells Based upon the lengths a, b, c and angles af, y, there are 7 types of unit cells. These are also called crystal habits or crystal system. A crystal may belong to any one of these seven types of unit cells.Solid State [1] Simple, Primitive or Basic Unit Cell When the particles are present only at the corners of a unit cell, itis called simple unit cell. A crystal lattice having simple ‘unit cell is called simple crystal lattice. [11] Centred Unit Cells (Non-primitive unit cells) Those unit cells in which the constituent particles are present at the comers of the unit cells and also at some other positions are called centred unit cells (non-primitive unit cells). These are of following three types 1, Face centred unit cell : When particles are present at the corners and at the centre of each face of unit cel, itis called face centred unit cell. 2, Body centred unit cell : When particles are present at the corners and one particle is present at the body-centre within the unit cell, it is called body centred unit cell 3. End centred unit cell : In such a unit cell, particles are present at the corners and there are particles at the centres of any two opposite faces. Table 1.3 : Seven Primitive Unit Cells and Their Possible Variations as Centred Unit Cells crystal Possible ere oer a system variations Edge lengths 1. Cubic. Primitive, Body centred, a=Buy= 90° Copper, Zinc blende, KCl, NaCl brea 2.Tetragonal Primitive, Body centred a=be a=p-y=90° White tin, Sn0,,TI0,, CaS0y 3 Onthorhombic Primitive, Body centred, bec a=f=7-90° ——_Rhombie sulphur, Face centred, End centred CaCO, KNO,, B&O, A-Monodinie Primkive,End centred abe £0°;490° Monoclinic sulphur, Pbcr0,, Na,S0, 101.0 S. Hexagonal Primbve more 90°;7= 120° Graphite, 2n0, Cds 6. Rhombohedral Primitive a=B=7490% CaCO, (Cait), HgS (Cinnabar) oe 7. Triclinie Primitive arbre aeBry 290° K,Cr,0; , CuSO, 5H,O, HBO, ORemember, ‘© There are 7 crystal systems and there are four possible variations 1) Primitive, (2) Body centred, (3) Face centred, (4) End centred ‘There are 14 possible three dimensional lattices. These are called Bravais tices, Characteristics of 14 Bravais lattices have been given in the table.ISC Chemistry-XII ‘Simple cube (cubic Ge Simple tetragonal Body centred tetragonal Face centred eube (lec) ae Body centred cube (bee) ) ‘Simple monoctinic End centred monectinie ‘Simple orthorhombic Face centred orthorhombic —_—Bdy canted orthorhombic End centred orthorhombic arbee, oo Simple mombohedral Simple tcc carer a asbye, 290" epee 80" 120" Fig. 1.10 Fourteen Bravais latticesSolid State Calculation of the Contribution of Atoms Present at Different Lattice Sites (1A point at the corner is shared by 8 other unit cells, Therefore, contribution of each point towards unit cell = 1/8. (2)A point present on the edges is shared by 4 unit shells. Therefore, contribution of each point on the edge towards the unit cell = 1/4, (B)A point on the face is shared between two unit cells Therefore, contribution of each point towards unit cell = 1/2. (4)A point present within the body is not shared by any other unit cell. Therefore, contribution of each point within the body towards unit cell = 1. Calculation of Number of Particles in a Unit Cell [1] Primitive or Simple Cubic Cell (sce) Ina simple cubic cell, there is one atom at each of the 8 ‘comers of the cell, In a simple cubic cell, each corner atom is, ‘equally shared among eight unit cells and so the contribution of each comer atom towards unit cell = 1/8, Thus a simple ‘cubic unit cell has 8 x 1/8 = 1 atom. Figure represents only the centre of particle occupying that position and not its actual size. Such structures are called open structures. Fig. 1.11 (a) An atom at the lattice point shared by 8 unit cells (0) An atom at the edge centre shared by 4 unit calls (6) An atom at the face centre shared by two unit cells (a) An atom at the body centre not shared by any other unit cell [11] Body Centred Cubic Unit Cell (bee) This type of unit cell has one atom at each of the 8 comers and one atom at the body centre. Thus a body centred cubic unt cell has 8 +1 = 2 atoms, [IMI] Face Centred Cubic Unit Gell (fee) It contains 8 corner atoms and 6 face centre atoms. The face centre atoms are shared between two cells. Thus, a face 1 cenved cin el has 8x 26 4 ams It is important to know that the number of atoms in a unit cell are in the same ratio as the stoichiometry of the compound. Therefore, it may be used to determine the formula of the compound. ‘Table 1.4: Number of Particles in a Unit Gell Unit cell No.of atoms No.of No.of Total atcorners atoms at__atoms at faces centre Simple eubie ° ° 1 cell (See) Body centred ° 1 2 cubic (bce) Face centred eo o 4 ceubie (fee) Example coiculate the number of atoms per unit cell present in simple fee and bee unit el Solution : Number of such atoms have been calculated in the above table [ERG] CLOSE PACKED STRUCTURES (PACKING OF CONSTITUENT PARTICLES IN CRYSTALS) In the formation of exystals, the constituent particles get closely packed together. These particles pack in such a way that the volume is minimum. Thus a state of maximum possible density and stability is attained. This type of packing is called elose packing. The mode of packing depends upon the shape of the constituent particles. Here we will discuss the packing modes of spherical particles of equal size, An edge of the crystal is formed when the spheres are placed touching each other1.12 1. Close Packing in One Dimension There is only one way in which the spheres can be arranged in a one dimensional close packed structure, ic., spheres are arranged in a row touching each other. Each sphere is touching two neighbouring spheres. ‘Thus, in this arrangement coordination number is 2, O0COCOO Fig. 1.12 Close packing in one dimension 2. Close Packing in Two Dimensions ‘There are two possible arrangements : [1] Square Close Packing (sep) In this arrangement, the spheres of equal size in the adjacent rows lie just one over the other and show a horizontal as well as vertical alignment and form squares. Each sphere is in contact with four other spheres. Thus coordination number is 4. If we call the first row as ‘A’ type row, then the second row is also‘ A’ type because both are exactly same. We may place more rows to obtain AAA type arrangement as shown in the figure 1.14(a). If the centres of 4 immediate neighbouring spheres are joined, a square is formed. Hence, it is called square close packing in two dimensions. [It] Hexagonal Close Packing (hep) In this arrangement, the spheres in every second row are placed in the gaps between the spheres of the first row. ‘The particles in the second row are not in vertical alignment of the first row. The particles in the third row will be vertically aligned with those in the first row and so on. Ifthe arrangement of spheres in first row is called ‘A’ type, the arrangement in second row is different and may be called B’ type. The third row and fourth tow are of ‘A’ and ‘B’ type respectively. Hence, this arrangement is of ABAB type. Each sphere is touching 6 neighbouring spheres. Therefore, coordination number is 6. If the centres of 6 immediate neighbouring atoms ate joined, a regular hexagon is formed. It is called two dimensional hexagonal close packing. The second mode of packing (I) is more efficient because it leaves less space unoccupied by particles. It has been shown that in arrangement (I), 52.4% of the space is ‘occupied by particles while in arrangement (II) 60.4% of the space is occupied by particles. ISC Chemistry-XI Fig. 1.13 Close packing of spheres in two dimensions = {@) Square close packing (o) Hexagonal close packing, In hexagonal close packing, there are number of vacant spaces or voids. These voids lie between three touching spheres. These are roughly triangular in shape. The triangular voids are of two types. In one row, the apex of the triangles are pointing upwards and in the next layer downwards. 3. Close Packing in Three Dimensions All real structures are three dimensional structures. ‘They can be obtained by stacking two dimensional layers fone above the other. ‘There are many layers in three dimensional packing. Let us see how a three dimensional packing can be obtained from two dimensional packings [1] Three Dimensional Close Packing from ‘Two Dimensional Square Close Packed Structures In this arrangement, the second layer is placed over the first layer such that the spheres of the upper layer are Fig. 1.14 Three dimensional packing of square close packed layers forming simple cubic lattice with AAdcarrangementSolid State PPEy ‘exactly above those of first layer: In this arrangement spheres of both the layers are perfectly aligned horizontally as well as vertically. Similarly, we may place more layers one above the other. Ifthe arrangement of spheres in the first layer is called‘ A’ type, all the layers have the same arrangement. Thus this lattice has AAA type pattern. This will be a simple cubic lattice and its unit cell will be primitive cubic unit cell. [11] Three Dimensional Packing from Two Dimensional Hexagonal Close Packed Layers They can be generated by placing layers one over the other. 1. Placing second layer over the first layer: Letus take a ‘two dimensional hexagonal close packed layer‘ A’ and place a similar layer above it such that the spheres of the second layer are placed in the depressions of the first layer. Since the spheres of the two layers are aligned differently, let us call the second layer as B. It can be 7 NT WY ‘observed from the figure that all the triangular voids of the first layer \ 8 on \ on are not covered by the spheres of the second layer. This gives rise to AANA different arrangements. Wherever a sphere of the second layer is above the void of the first layer (or vice-versa), a tetrahedral void is formed. These voids are called tetrahedral voids because a tetrahedron is formed when the centres of these four spheres are Joined. They have been marked as ‘T’ in figure. Fig. 1.15 Types of triangular voids in hexagonal close ‘Acother places, the triangular voids in the second layer are above packed layer. Apex of triangular voids a & point the triangular voids in che first layer, and the triangular shapes of towards downwards and upwards respectively these do not overlap. One of them has the apex of the triangle pointing upwards and the other downwards. Such voids are surrounded by six spheres and are called octahedral voids. ‘These voids have been marked as ‘O’ in figure. The number of these two types of voids depend upon the number of close packed spheres. Let the number of close packed spheres be N, then The number of octahedral voids generated = N The number of tetrahedral voids generated = 2N Fig. 1.16 A stack of two layers of close packed spheres and voids generated in them. T = Tetrahedral void, O = Octahedral void 2, Placing third layer over the second layer possibilities (a) Covering tetrahedral voids : The third layer may be placed above the second layer in a manner such that tetrahedral voids of the second layer are covered by the spheres of the third layer. In this case, the spheres of the third layer are exactly aligned with those of the first layer. Thus, the pattern of spheres is repeated in alternate layers. This pattern is When third layer is placed over the second, there are twobar) often written as ABAB .... pattern. This structure is called hexagonal close packed (hep) structure. This sort of arrangement of atoms is found in many metals like magnesium and zine () Covering octahedral voids : The third layer ‘may be placed above the second layer in a manner such that its spheres cover the octahedral voids. When placed in this ‘manner, the spheres of the third layer are not aligned with those of either the first or the second layer. This arrangement is called ‘C’ type. Only when fourth layer is placed, its spheres are aligned with those of the first layer as shown in figure. This pattem of layers is often written as ABCABC .... This structure is called eubie close packed (cep) or face centred cubic (fee) structure. Metals such as copper and silver crystallise in this structure. Tetranedral hale. ctahedtal Fig. 1.17 Hexagonal close packing (hep) Both these types of close packing are highly efficient and 74% space in the crystal is filled. In either of them, each sphere is in contact with twelve spheres. Thus, the coordination number is 12 in either of these two structures : hep : Mg, Be, Zn, Cd, Ti, Zr cep: Fe, Cu, Ag, Au, Al, Pt, Co ISC Chemistry-XI Fig. 1.18 Cubic close packing (ccp) or face centred cubic (foc) Voids (Depressions) ‘The empty space left between the close packed spheres is called void. The void has definite geometry. Since the voids are present between the spheres, therefore, they are called interstitial voids. They are of 3 types (1) Trigonal voids (2) Tetragonal voids (3) Octahedral voids. But tetragonal and octahedral voids are important. Important characteristics of these voids are (2) The ratio of the radii of void and the sphere is constant. (2) The size of octahedral void is greater than that of tetrahedral void (3) Coordination number of tetrahedral void and octahedral void is 4 and 6 respectively. (4) Number of tetrahedral voids = 2xnumber of octahedral voids NUMBER OF VOIDS FILLED AND FORMULA OF THE COMPOUND ‘There are tetrahedral voids and octahedral voids in three dimensional close packed structures (hep or ccp). It has been found that : (1) Number of octahedral voids = Number of particles present in the clase packing. (2)Number of tetrahedral voids = 2 x Number of ‘octahedral voids. (3)It has been found that in case of ionic compounds, the bigger ions (usually anions) are present in the packing whereas smaller ions (usually cations) ‘occupy the voids. The cations may occupy tetrahedral voids or octahedral voids or both. It is rot necessary that all the voids must be occupied. Only the fraction of total voids may be occupied. Knowing the fraction of the voids occupied, the formula of the compound may be calculated orSolid State Such questions can easily be solved if we remember that in hep or ccp arrangement number of octahedral voids is equal to the number of atoms. The number of tetrahedral voids is double the number of atoms. Example 1) 4 compound containing atoms A and B crystallises in cubic structure. The atoms A are present at the corners ofthe cube while atoms B are present atthe face centre. What is the formula of the compound ? Solution : The corners of the cube contain 8 atoms. Contribution of atoms A towards unit cell ‘The face centres contain 6 atoms. Contribution of atoms B towards unit cell = 6x $= 3 ‘Therefore, formula of the compound is AB. Example 2p an ionic solid, he anions B are arranged in a cubic close packing (ccp). The cations A are equally distributed between octahedral voids and tetrahedral voids. ‘Ifall the octahedral voids are occupied, what is the formula of ionic slid? Solution : Suppose , Number of anions B = N Number of octahedral voids = N, Number of tetrahedral voids = 2N Since all the octahedral voids are occupied, and octahedral and tetrahedral voids are equally occupied, therefore, N cations (A) are present in octahedral voids and N-cations (A) are present in tetrahedral voids. Thus if Number of anions (B. v5 ‘Number of cations (A) =N-+ N=2N Ratio of A : B will be 2N : Nor 2: 1 Therefore, formula of ionic compound is A,B. Example 3.) an oxide of aluminium, the oxide ions (0*) dare arranged in hexagonal close packing (hep). The alurniniurn ions occupy 2/3 of the octahedral voids. What is the formula of oxide? Solution : Suppose, Oxide ions = a, Octahedral voids =a 2a Octahedral voids occupied = 2%, Aluminium ions ‘The ratio of AI" + O* is 22: a or 2:3, ‘Thus oxide of aluminium is Al,0 5 Solved Numerical Examples for Calculating the Formula of the Compound from Occupancy of Voids BRample 4 4 solid contains elements Aand 8. Atoms A are arranged in exp way, atoms B occupy all the octahedral voids and hal ofthe tetrahedral voids, What isthe formula of the slid? Solution : Suppose, Number of atoms of A=a Number of octahedral voids =a [Number of tetrahedral voids = 2a [Number of atoms B in octahedral voids =a Number of atoms B in tetrahedral voids ==* =a Total number of atoms B=a+a=2a Ratio of atoms of A : B will be a : 2a or 1: 2. Therefore, formula of solid = AB, Example 5_ 4 solid contains atoms A and atoms B and has cubie structure. Atoms A are present at the corners of the cube and atoms B at the body centre of cube. What is the {formula of the solid ? ‘Solution : Total number of atomsA atthe corners = 8 Consribution of atoms A towards unit ell = 8 «2 Number of atom B in the body = 1 Contribution of atoms B towards unit cell = 1x1= 1 ‘Thus unit cell contains one atom of A and one atom B. Formula of solid is AB. Example 64 compound formed by elements X and ¥ cystallises in the cubic structure. ¥ atoms are present atthe comer ofa cube and X atoms are at alternate faces, What i the formuta of the compound? Solution : The comers of the cube contain 8 atoms, Contribution of atoms ¥ towards cubic unit cell = 87 =1. There are six faces in a cubic unit cell, out of which only three are occupied. Since each face contributes 1/2 to the unit cell, hence contribution of atoms X towards cubic unit cell =3x 2-3 22 Therefore, formula of | the ~~ compound is Xga¥ or X5¥a. Example7_ i @ solid, anions A are arranged in ccp manner. What is the formula of the solid if 50% of the octahedral voids are occupied by B and 50% of the tetrahedral voids are occupied by C. Solution : Ratio of number of octahedral voids and tetrahedral voids is 1: 2.Pl Ratio of A and B : 50% of the octahedral voids are ‘occupied by B Ratio is 24: B ao Ratio of A and C : 50% of the tetrahedral voids are ‘occupied by C RatioisA:C or 24:20 @ Comparing expressions (1) and (2), Ratio of elements is 2A :B: 2C. Therefore, formula of the compound is ABC, Example 8) if chree elements P,Q and R crystallize in a cui solid lattice with P-atom at the corners, Q-atoms at the cube centre and R-atoms at the centre ofthe faces, what is the formula of the compound ? Solution : Atoms of P per unit cell = 8 x ‘Atoms of Q per unit cell =1 Aoms oR per ni el = 6x23 Formla of the compound i POR Beample 9) 4 solid is made up of elements P and Q. Atoms Qare in cep arrangement while atoms P occupy all the tetrahedral sites, What is the formula of the compound ? Solution : Suppose number of Q-atoms =n Therefore number of P-atoms =2n Formula of compound is P,Q. Example 10 jp on ionic compound MgAl,0 4, oxide ions are in ccp arrangement. Mg”* ions occupy tetrahedral voids Fe 1. A compound formed between A and B acquires ccp structure. Atoms A are present at the comer of the cube and atoms B are occupying alternate tetrahedral voids. What will be the formula of the compound ? [Ans : AB] 2. A solid between A and B has the following characteristics (a) Atoms A are present in cep packing (6) Atoms B occupy all the octahedral voids and half of the tetrahedral voids. Deduee the formula of the compound, [Ans : AB,] 3. In an ionie solid, oxide ions are arranged in cep. One sixth of the tetrahedral voids are occupied by cations (A) whereas one third of the octahedral voids are ‘occupied by the anions (B). Deduce the formula of the compound Questions for Practice ISC Chemistry-XIT whereas AI ions occupy octahedral voids. What % of tetrahedral voids are occupied by Mg?" ions and octahedral voids by Al? ions ? Solution : In the formula MgA\l,0,, there is one Mg” ion, 241% ions and 40 ions. Four 0? ions are in cep arrangement. Octahedral voids = 4 Tetrahedral voids = 8 Only one tetrahedral void is occupied by Mg? ion, ie, 1x10 = 12.5% occupied. 2al% ions occupy 4 octahedral voids, ie, 50% ‘octahedral voids are occupied. Example 14 4 unit cell consists of a cube in which there are Aatoms at the corners and B atoms at the face centres. Two A atoms are missing from the two corners of the unit cell. ‘What is the formula of the compound ? Solution : A cube has 8 comers but only 6 comers are ‘occupied. 13 Contribution of atoms A towards unit cell = 6x 2= 3 a4 Contribution of atoms B towards six face centres = oxde3 2 Ratio of A: Bis 2:9, Hence formula fs AsByy or AB,. = tans: AR0,) 4. Acompound is formed by two elements X and ¥. Atoms of the element ¥ (as anions) make cep and those of element X (as cations) occupy all the octahedral voids. What is the formula of the compound ? [Ans : XY] 5. Atoms of element B form hep lattice and those of the element A occupy 2/3rd of tetrahedral voids. What is the formula of the compound formed by the elements Aand B? [Ans : A,Bs] 6. Ina face centred cubic arrangement of A and B atoms, Aare present at the corners of the unit cell and B are present at the face centres. If one atom of A is missing from its position at the corner, what is the formula of the compound ? [Ans : A,Bo,]Solid State 8. Suppose number of 0” Octahedral voids = N Tetrahedral voids =2N ions = N N Number of cations (4. x “4 5 Number of anions (8) Ratio of A: 8:0? =“: Ni 33 [ER] LOCATING TETRAHEDRAL AND OCTAHEDRAL VOIDS There are 8 tetrahedral voids and 4 octahedral voids in the cubie close packing (cep or fcc). 1. Locating Tetrahedral Voids Let us consider a unit cell of cep or fee. The unit cell is divided into 8 small cubes. Each small cube has atoms at alternate comers. Thus, each small cube has 4 atoms. When joined to each other, they make a regular tetrahedron. Thus, there is one tetrahedral void in each small cube, and 8 tetrahedral voids in total. In this way each of the eight small ‘cubes have one void in one unit cell of cep structure. We know that cep structure has 4 atoms per unit cell, and the number of tetrahedral voids is twice the number of atoms, ie, 8. Fig. 1.19 2. Locating Octahedral Voids One octahedral void is present at the body centre of the cube and 12 octahedral voids are present on the centres of Hints for Difficult Questions Formula is ABO. 6. Contribution of A towards the unit ce Contribution of B towards the unit cell =6 3 Ratio of A: B is2 13 of 7:24, Formula is A,Boy. the 12 edges of the cube, 12 octahedral voids are shared by 4 ‘unit cells. Thus octahedral voids per unit eell = 22-3, ‘Total number of octahedral voids is equal to 1 +3 = 4 (ac the body centre + per unit cell) We know that in ecp structure each unit cell has 4 atoms. Thus, the number of octahedral voids is equal to the number of such atoms, ie, 4, Fig. 1.20 Coordination Number Definition : Coordination number is defined as the number of equidistant neighbour atoms that an atom has in its crystal structure. In case of ionic crystals, coordination number is equal to the number of oppositely charged ions surrounding a particular ion. Greater the coordination number, the more closely packed is the crystalline structure. ‘The common coordination numbers in different types of crystals are 4, 6, 8 and 12.Pc) Example ) 4 cubic solid is made up of two elements P and Q. ‘Atoms Q are present at the corners of the cube. Atoms P are present at the body centre, What is the formula of the compound. What are the co-ordination numbers of atoms P and Q Solution : cube Atoms Q are present at the 8 comers of the Number of Qatoms in unit cll 8x21 ‘Atoms P are present at the body centre Number of P-atoms in unit cell =1 Hence, formula of compound is PQ. Coordination number of each element P and Q is 8. EE) RELATION BETWEEN NEAREST NEIGHBOUR DISTANCE (d), RADIUS (r) OF THE ATOM AND EDGE (a) OF THE UNIT CELL I! Simple Cubic Structure thas coordination number of six. If*@’is the side of the unit cell, then distance (d) between two nearest atoms is ‘@ (d=a). Radius (r) of the atom -d/ a/2. Fig. 1.21 [ll] Face Centred Cubic Structure (fec) It has coordination number of 12, e.g., Fe, Cu, Ag, Zn ete, If ‘a is the side of the unit cell, then distance (d) between two nearest atom is -& (d= 2) 2 ‘Simple cubic unit cell Radius (r) of the atom <. 2 22 Derivation : From the right angle triangle ABC, ISC Chemistry-XIT Fig. 1.22 Face centred cubic unit cell [ill] Body Centred Cubic Structure (bec) Ichas coordination number of 8, eg. in CsCl, CsBr, TIC, TiBretc., coordination number of each fon is 8. The nearest B(,_ avd distance (cb between two atoms is ax “*{ d B Fig. 1.28 Body centred cubie unit cell Derivation : In the right angle triangle ACD, cp =VAC? + aD® ButSolid State SE Solved Numerical Examples Based on Edge Length and Radius of the Atom “i Example 1) csc has bee arrangement. Its unit cell edge length is 400 pm. Calculate the interionic distance in CsCl. Solution : For bee structure : av3 _ 400 5 ae xB =100 13 Fg NF = 1004 d But dius (7) = 5, nm radius (9) = 5 Interionic distance (d) =2r =2 x 100V3 = 346.4 pm Example 2 jf che radius of an atom is 75 pmand the lattice ‘ope is bec, what is the edge length? Solution : For bee structure : 1. An element E crystallises in body centred cubic structure. The edge length of the cell is 1.469 x 10! metre and density is 19.3 g em~. Calculate the atomic radius of this element. [ans : 6.36x10- m] Questions for Practice Example 3 Tie radius of an atom is 500 pm. If the element crystallizes as fec lattice, what is the length of the side of unit cell ? Solution : For fee structure a 2a or 500 = —4— 22 a= 1414 pm Example 4 Xenon cyrstallises in the face centred cubic lattice. The edge length of the unit cell is 620 pm. What is the nearest neighbour distance (a) and radius (1) of the atom a _ 620 Solution : pe 4385 pm, aR F = 4 = 885 21925 pm 272 Example 5 _ an jonic solid A*B~ has bec arrangement. If the edge length of the unit cell is 404 pm, caleulate the interionic distance between A* and B Solttion: ao 95 LAS = 349.9 pm 2. Silver crystallises with face centred cubic unit cells. Each side of the unit cell has a length of 409 pm. What is the radius of one silver atom ? Assume that each face atom is touching the four corner atoms. [Ans : 144.6 pm] ERT) size OF TETRAHEDRAL AND OCTAHEDRAL VOIDS ‘There are two types of voids present in the erystals of close packing structures (hep or cep) = (2) Tetrahedral voids, (2) Octahedral voids. The radii (r) of the voids in the close packed structures and the size of the spheres (R) are related to each other as given below : Radius of tetrahedral void (r) = 0.225 R Radius of octahedral void (r) = 0.414 RHere R is the radius of the spheres in the close packed arrangement. In ionic compounds, anions are present in the packing and cations occupy the voids. Then, 1. For cations occupying tetrahedral voids, 225 ro (r* and r- is the radius of cation and anion respectively) 2. For cations occupying octahedral voids, rt 50.414 r~ Interstitial Compounds ‘The tetrahedral void is smaller than octahedral void. ‘The maximum radius (r) of octahedral void is equal to 0.414 R. Transition metals accommodate atoms of small size such as H, B, C and N in the voids of their erystal lattice. ‘Thus, in transition metal hydrides, borides, carbides and nitrides the non-metal atoms H, B, C and N are respectively accommodated in the interstices. These compounds are called interstitial compounds. Derivation of the Relationship between the Octahedral Radius (r) of the Void and Radius (®) of Spheres in Close Packing ‘The sphere accommodated into the octahedral void has been shown by a small shaded sphere. ABC is a right angle triangle. Fig. 1.28 BC? =aB? 4 Ac? or (2R)? =(R +? +(R4 9? =2 (R40? or Rer=RV2 or r=Rv2 -R = R(.414-1) =0.414R or r=Rx 0.414 ISC Chemistry-XIT Derivation of the Relationship between the Tetrahedral Radius (r) of the Void and Radius (R) of Spheres in Close Packing ‘Three spheres A, F and F form the triangular base, the fourth sphere (B) lies at the top. The red small sphere represents the tetrahedral void. Fig. 1.25 Face length of the cub Radii of the void =r Radii of the sphere From the right angle triangle ABC, AB =VAC? + BC? = Ya? +a? =av2_ ‘The sphere A and B touch each other in close packing, face diagonal AB =2R. 2R avd or R i) ez ‘Again, from the right angle triangle ABD, AD =VAB? + BD? =yav2)? +a? = av3 As the red small sphere touches other spheres, AD =2R +) AR +N =a a Ror o - «) Dividing equation (ii) by equation () Rer Vax? _ = “5 =1.225 R 2 v2 or 142 =1,225 R or r= Rx0.225Solid State Radius Ratio Effect and the Shape of Crystals ‘An ionic solid contains both cations and anions. Thes ions are held together by strong electrostatic force of attraction, lonic bond is non-directional. Therefore, arrangement of ions within the ionie crystal is determined by the size of the anion and cation. The ratio of the radius of cation to that of anion is known as radius ratio, Radius of cation(r*) Radius of anion(r~) Radius ratio = The coordination number may be determined from the radius ratio. Greater the radius ratio, greater is the coordination number, ed Bxample 1 rhe radii of A” and X~ are 95 pm and 181 pm. respectively. Predict the coordination number of A’ Solution FL Losoq ri ‘The value lies between 0.414 ~ 0.732. Hence coordination number of A* is 6. It will occupy octahedral voids Example 2) 4 solid Av B- has NaCl type structure. The radius of anion is 250 pm What is the ideal radius of cation ? Can a cation C* having radius of 180 pm be slipped into the tetrahedral site of the crystal A* B Solution : Solid A*B~ has NaCl structure. A* ions are present in the octahedral voids. Ideal radius of the cation will be equal to the octahedral void. Thus cation will touch the anions and the arrangement will be close packed Radius of octahedral void =r,, =0.414 «7, 0.414250 =103.5pm Toil = 9,225 t0 0.414 Trig =RX0.225 to Rx 0.414 For tetrahedral voids = 250pm) =250.x0.225 to 250 x 0.414 6.25 t0103.5 pm Radius of given cation C* =180 pm. Its larger than the range of ryoig- Hence it cannot slip into the void of solid ANB. Example 3.) jf the close packed cations in NaCl type solid have a radius of 75 pm, what would be the maximum and minimum sizes of the anions filling the voids ?@DSB 2001) Solution : For closed packed NaCl type solid , Solved Numerical Examples on Radius Ratio ‘Table 1.5: Radius Ratio in 1: 1 or AB Type Structure Structure Coord- type nation number Limiting Examples radius ratio ry 0.732 and 0.414-0.732 Octahe- ron Polyhe- dron Cube Cesium 8 chloride Cs, CsBr, THB, NILBe ‘MgO, NaBr, CaS, ‘MnO, KBr, CaO Sodium chloride (rock salt) 0.225-0.414 Tetrahe. Sphalerite, 4 dron Zn CuCl, CuBr, Cul, BaS, Hgs =0.414 - 0.732 Minimum value of - =" _=—75__ 02.5 pm a7 0.732 Maximum value of a 7S = 181.2 pm a4 0414 Example 4 4 solid AB has NaCl structure, If the radius of the cation is 170 pm, calculate the maximum possible value of radius of anion B>. Solution : For NaCl type structure : = 0.414 t0 0.732 %, e r,. =170 pm ‘The maximum possible value of radius, 170 = 410.62 pm oai4 Example 5_ the length of the unit cell edge of body centred cubic (bee) crystal is 352 pm. Calculate the radius of an atom of the metal. ava Solution : Forbee structure radius of sphere (r) Here a= 352 pm (edge length of unit cell) 3 radius of atom (1) = 4 = 152.42 pm Beample 6 sodium metal crystallises in body centred cubic lattice with cell edge = 4.29 A. What isthe radius of sodium atom ?Solution : For bee lattice, nearest distance between 5 two atoms = 293 : + 429.8 7 Radius of atom 1.86 A ERample 7 57 jons form a closed packed structure. Ifthe radius of Br ions is 195 pm, calewate the radius ofthe ation that just its into the tetrahedral hole. an a cation A* having a radius of 82 pm be slipped into the octahedral hole of the crystal A*Br- ? a 1. A solid AB has the NaCl structure. If the radius of the cation is 120 pm, calculate the maximum possible radius of anion B. [Ans : 289.85 pm] 2. A solid A*B™ has NaCl type close packed structure Radius of anion is 241.5 pm, what is the minimum radius of the cation? Can a cation C~ having radius of 50 pm be fitted into the tetrahedral hole of the crystal AaB? [Ans : 99.98 pm, yes] Wiese emtoent ont or ret 120 _ 989.85 pm 414 0.414 2, rh =r x 0414 =241.5 x 0.414 =99.98 pm Again, —s#_=0.225 10 0.414, For minimum size, eid = 0,225 ao EERE] PACKING FRACTION OR PACKING EFFICIENCY ‘The constituent particles are closely packed in the crystal lattice. But the total space is not occupied. Some ‘empty space (voids) is always present. Questions for Practice Hints for 1 fricult Questions ISO Chemistry-XIL Solution : (a) Radius of the cation just fitting into the tetrahedral hole= radius of tetrahedral hole = 0.225% r,,. =0.225% 195 = 43.875 pm (b) radius ofr, =195 pm radius of r,, =82 pm Radius ratio = P15 ‘The radius ratio lies between 0.414 ~ 0.732. Therefore, the cation A* can be slipped into the octahedral hole of AY Br crystal = 3. Predict the structure of MgO crystal and co-ordination number of its cation in which cation and anion radii are equal to 65 pm and 140 pm respectively, [Ans : Octahedral, 6) 4. Predict the close packed structure of an ionic compound A'B~ in which radius of the cation is 148 pm and that of anion is 195 pm. What is the co-ordination number of the cation ? [Ans : Body centred cubic, 8] oid =241.5x 0.225 = 54,34. Hence, the cation having radius of 50 pm can be fitted into the void. 3. Radius ratio =" = ©5 =, 0.464. r 140 Hence structure is octahedral. © = ¥8 ~ 076. Hence structure is bee. 195 Packing Fraction It is equal to the ratio of the volume occupied by the ‘atoms present in a unit cell to the total volume of the unit, cell. packing fraction = Volume of atoms present in unit cel Total volume of the unit cellSolid State Packing fraction depends upon the packing of spheres. Packing Efficiency It is defined as the percentage of total space which is ‘occupied by the particles in a certain packing. ‘Volume of atoms present in unit cell Total volume of the unit cell x 100 Packing efficiency Spheres (particles) present in simple cubic structure, body centred cubic (bec) structure and face centred cubic (icc) structure are 1, 2 and 4 respectively. [1] Efficiency of Packing in Simple Cubic Structure Suppose, Edge length of cube Radius of sphere =r For simple cubic structure : r 2 Volume of unit cell = a* = (2r)$=8r? a nr Volume of one sphere (atom) Atoms present in one unit cell Volume of atoms pi Total volu 40? 3x8r ‘This shows that 52.4% space of the unit cell is occupied and the rest 47.6% space is empty. Packing fraction = 0.524 or 52.4% Fig. 1.26 Top-bottom side view of simple cubic unit cell 1.23 [11] Efficiency of Packing in Body Centred Cubie (bec) Structure Suppose, Edge length of cube =a, Radius of sphere =r Since the sphere at the centre touches the spheres at the corners, diagonal AD =4r. From the right angle triangle ABC, AB? + BC? =Va? +a? =V2a? From the right angle triangle ACD , AD = Vac? cD? = 2a? +a ar= a3 ney Fig. 1.27 Body centred cubie unit cell Thus for body centred cubic structure : a = 4% B = a =Car ¥)3 = 42 Volume of unit cell= a* =(4r/ V3)’ 3 a) avi Number of spheres per unit ell = 8x2 41-2 Volume of 2 spheres (atoms) =2 x 48-88" (ay 3 8 Volume of atoms present in unit cell “Total volume of unit cell Bax 38 _ ni 3x 6479 8 ‘This shows that 68% space is occupied by atoms and the remaining 32% space is vacant. Packing fraction 0.68 [111] Efficiency of Packing in hep and cep (fee) Strueture Both type of close packing (hep and cep) are equally efficient. In both the cases, 74% of the available volume is ‘occupied by spheres (atoms)Fig. 1.28 (©) Top view of face centred cubic unit cell Suppose, Edge length of cube ~a, Radius of the sphere =r ‘Since the spheres on the face touch the spheres on the comers, AC =4r From the right angle triangle ABC, (@) Face centred cubic unit cell AC = VAB? +BC? =Va? + ISC Chemistry-XI ‘Thus for fee (cep) structure : @=2rJZ Volume of unit cell =a? = (2ri2)°=16 r3W2 ay ‘Atoms present in one unit cell = 8x2 +6x3=4 ae"2 Axdnr? 16 nr? Volume of 4 spheres (atoms 2) 4 spheres (at < = ..@) Packing fraction = Volume of atoms present in unit el Total volume of unit cell Sok 16x = 0.74 3 i r'y2 3y; 1. This shows that 74% space is occupied by atoms and the remaining 26% space is empty. Thus packing density decreases in the order: fee > bee > simple cubic. 3. Packing fraction shows how closely the atoms are packed together in a unit cell. It is possible to calculate the volume of unit cell from its dimensions. From the mass of one atom, Avogadro constant can also be determined. The derivation of the formula for the calculation of density is given below: ‘Suppose the length of the side of unit cell =apm=ax 10" em (ax 10)? em? a? x 10 cm? Mass of unit cell = Number of atoms in the unit cell Volume of one unit cell % Mass of one atom =2 xm Suppose, Atomic mass =M, “Avogadro's number = N Mass of one atom (m)=M / N N ‘Mass of unit cell Mass of unit cell = s xm = Density of the unit cell (p) = MASS OT UNSS zxM B Density of the unit cell () = ram /cm OTe x10 Atomic mass , N = Avogadro's number ‘a= Rage length of the cube in pm (picometers) , 2 Number of atoms present in one unit cell Calculation of the Density of a Crystal (Calculations Involving Unit Cell Dimensions) (2) Number of atoms (2) for simple cubic structure = 1 (2)Number of atoms (2) for body centred cubic (bec) structure=2 (3)Number of atoms (z) for face centred cubic (fee) structure = 4 (4)IE edge length is given in em, then zxM > gram / em? Density of the unit cell = Nxa (5)Density of the unit cell is equal to the density of ‘xystalline compound, Example 1 chromium has monoatomic body centred cubic structure, Its cell edge is 300 pm, What is its density. Given that Cr = 52 g mol = 4.13 A Interionic distance (r* +7) = 357A or rv =2.065 A rer =3.57k 1” $3.57 - 2.065 = 1.505 A rt 1505 _9 799 2.065 Beample 14 6561 has cubic srucrure. tts density is 3.99 gram/em °, What is the distance between Cs* and Cl- ions. Solution : xu Nxa@x10™ Density of unit cell = Lx 168.5 @ x 10 x 6.02 x 10” (2 =1, M for CsCl = 168.5) 7015x108 or a=4,124 x 10? pm ag, A124 x 10% 3,99 = But interionic distance = ¥' = 357.1 pm Example 15 calculate the density of silver which crystallises in fee form. The distance between nearest atoms is 287 pm, N =6.022 x 10% mol”, Ag = 107.87) axM Solution : — Nx a? x10 Density of unit cell = Distance between nearest atoms (d)=287 pm Edge length (a) for fcc erystal ~dJ2 =287 V2 = 405.87 For fe structure, 2 =4 4 x 107.87 6.022 « 10 « (405.87)° «10 10.72 g/em* Example 16 what is the distance between Na* and Cl” in NaCl erystal if its density is 2.165 gem? and it erystallises in fee lattice. Density of silver Solution : Density of unit cell = Nx @x10™ }, M for NaCl = 58.5 , N =6,022 x 107%, a® 2165=——___4*585 6.022 x10" x a? x10" or 562.2 pm Distance between Na* and Cl” ions = see = 281.1 pmSolid State Example 17, clement cpstallizes in a bc. latice with cell edge of 400 pm. Calculate the density if 250 g ofthis element contain 2.5 x 107* atoms. 1. 3. Solution : For bec, Z =2 Mass of 2.5 x 10 atoms =250 gram 250 x 6,023 x10 25x10" = 60.23 (Molecular weight) M=6023, Z=2, a=400x10" cm ZxM Mass of 6.023 x 10 atoms d= a xNy 26023 © (400% 10) «6.023 x10 260.23 546.028 d =3.125 g/em* Calculate the number of atoms in a cubic based unit cell having one atom on each corner and two atoms on each diagonal. [Ans : 9] Calculate the number of atoms in fee unit cell of a monoatomic elementry substance. [Ans : 4] ‘An element has bee structure having edge length of unit cell equal to 288 pm. Ifthe density of the element is 7.2 g/cc, calculate the number of atoms present in 208 gram of the element, [Ans : 24.17x 10% atoms] ‘An clement crystallizes in a structure having fee unit cell of edge length 200 pm. Calculate its density, if 200g of this element contain 24x 10% atoms. [ans : 41.67 g/em*] The density of KBr is 2.75 g/cm® and edge length of unit cell is 654 pm. Show that KBr has fee structure, KF has NaCl structure. Its density is 2.48 g/em® and distance between K* and F~ is 268 pm. Calculate Avogadro's number. [Ans : 6.07 x10] Density of iron is 7.86 g/em? and edge length of unit cell is 286 pm. Find the structure of lattice (fee or bee) [Ans : bec] The nearest neighbour Ag-atoms in the silver erystal are 2.5% 10°° em apart. Presuming fec structure of the crystal, what will be the density of the silver. (At. we. of Ag = 108 g mol!) [Ans : 16.3 gem“) 1.27 eample 18 py element ¥ (At. mass=40 g mol") having fee. c g Questions for Practice 9. 10. 12. 13. 14. structure, has unit cell edge length of 400 pm. ‘alculate the density of X" and the number of unit cells in 4 of X. Solution :d aM 4x40 @Na* +e). The released electrons occupy the anion vacancies produced by Cl” ions. Now the crystal has excess sodium ion. Hole occupied byan electron Fig. 1.34 Metal excess defect due to anion vacancy The holes occupied by electrons are called colour ‘centres (Fcentres). Excess Na in NaCl, excess K* in KCL and excess Lit in LiCl makes the erystals yellow, violet and pink respectively. The colour is due to the excitation of electrons by absorbing the visible light. Due to the presence of unpaired electrons, such solids are paramagnetic. Metal excess defect due to the presence of extra cations at interstitial sites : In this defect, one ‘or more extra cation may be present in interstitial space and its charge is balanced by a free electron with it. ZnO is white at room temperature. On heating it becomes yellow, When ZnO is heated, it loses oxygen reversibly. The excess Zn? ions are accommodated in interstitial sites, The electrons present in neighbourhood of Zn® keep the crystal electrically neutral. The electrical conductivity and yellow colour of hot ZnO is explained by the extra electrons trapped, 20 =Zn™ +20, +2e~ 2 Now there is excess of Zn in the crystal and its formula becomes Zn; ,,0. Electrons trapped in anion vacancies are referred to as F-centres (F : farbe, meaning colour in german), In the following diagram, the cation A* and electron (©) occupy the interstitial sites. Crystal is electrically neutral, Extra cation inners space Extra electron in intorstial space Fig. 1.35 (@) Metal excess defect caused by extra cation in the Interstitial site Fig. 1.35 (b) An F-centre in a crystal 2, Metal deficiency defect : This defect occurs when the metal shows variable valencies. ‘This defect is shown by FeO, FeS, NiO etc. Three Fe” ions are replaced by two Fe® ions. The electrical neutrality is maintained but the solid contains less amount of Fe atoms, Same is true for NiO. Three Ni ions are replaced by two Ni* ions. ‘There are many solids which are difficult to prepare in the stoichiometric composition and contain less amount of the metal as compared to the stoichiometric proportion. A typical example of this type is FeO, which is mostly found with a composition of Fe.9s0. It may actually range from Feq930 to Feg9¢0. In crystals of FeO, some Fe cations are missing and the loss of positive charge is made up by the presence of required number of Fe** ions. In NiO, some Ni2* ions are replaced by Ni* ions. To maintain the electrical neutrality 3M* =2M**