02 141 aryana octet rors ight vatnthenet ester orloss of 200 eno pushers vs conneston ae! Contents _PART-A Jt. The Solid’State ~~ 2s 8. 4. Solutions g* 6 Electrochemistry Chemical Kinetics & (@)Surface Chemistry vb. General Principles and Processes of Isolation of Elements . The p-Block Elements . The d- and f- Block Elements & . Coordination Compounds . Haloalkanes and Haloarenes g & . Alcohols, Phenols and Ethers . Aldehydes, Ketones and @ Carboxylic Acids . Amines J . Biomolecules . Polymers . Chemistry in Everyday Life 49 101 151 201 233 259 319 349 401 445 495 559 601 631 653Se Syllabus 671 CENTRAL BOARD OF SECONDARY EDUCATION, 681 NEW DELHI 691 | CHEMISTRY (Theory) | CLASS-XII , Total Periods (Theory 160+ Practical 60) 392 mes 3 One paper Time: 3 hours 70 marks 19. I | Solid State a Solutions: - / - oe - _| 0 MI Electrochemistry - al eB IV | Chemical Kinetics |e V [Surface Chemistry de VI__ General Principles and Processes of Isolation of Elements os a ba . } | VIL | p-Block Elements vit | d-and f-Block Elements IX | Coordination Compounds x Haloalkanes and Haloarenes x1 | Alcohols, Phenolsand Ethers QS, | XII | Aldehydes, Ketones and Carboxylic Acids | to | XIII Organic Compounds containing Nitrogen wo 28 | XIV__ | Biomolecules (| XV | Polymers | | XVI | Chemistry in Everyday Life | 06 | : “vn = et a E oo 70i. E> Lesunsme Bas! , PTS' pe acked and held together by strong intermolecular forces. The _bi ig warticles in solid are closely p: 2 y in studs ave fiX€d positions and can only oscillate about their mean positions. They have definite shape and o 1,only Oscillate about their mean positic winite volume. The density of solids is high and they have low compressil “1, Stsses of Solids: Two types of solids are known: _@-Amorphous solids, (i)/Crystalline solids. (i) Amorphous solids: In amorphous solids, the arrangement of 9 building constituents is ard. They may have a short range order. Theif melting points z harp—They are, ei melting points are-not-sl 5 ey are isotropic in nature Le., their properties such as mechanical strength, se dn etc, are same in all directions. Examples: o r, quartz glass, ete. (i) Crystalline solids: In Sas 5 e eeeean ieee Ged building constituents is throughout the entire \three- dimensional network) A crystalline solid has sharp melting point Fig. 1 and is anisotropic in nature i.e., some of their physical properti such as electrical resistance or refractive index show different values when measured a¥ong different directions in the same crystal. Ti_has a definite-geometrical shape with flat faces and sharp edges. Examples: sodium chloride, quartz, etc. | Table 1.1; Distinction between Crystalline and Amorphous Solids nisotropic behaviour of crystal = SA Property Crystalline Solids Amorphous Solids i : Shape Definite characteristics and geometrical | Irregular shape. — shape. —— Melting point Melt at_a_sharp_and_characterjstic | Gradually soften over_a range of — temperature. temperature. ¢ Cleavage propery, When cut _with_a_sharp edged tool, | When cut_with a sharp edged tool, they split_into two pieces and_the | they cut into two pieces with iregulay newly’ generated surfaces are plain and | surfaces. “ smogth. — Heat of fusi i i of fusion They have a definite and characteristic They do not have a definite heat of heat of fusion 7 fusion, a ee Isotropy Anisotropic it i i isotropic in nature, Isotropic in nature. Nature True solids. ids. ; “ — - True solids. Pseudo solids or super cooled liquids Order in arrangement of Long range order: ane ; constituent particles ——“V Only short range order. aifferent Types of Sol ase - ee Physical Nature Molecular solids Very k Insulator ‘ery low L@Non-polar | Molecules | Dispersion Ar, CCly Hal, Soft a —_S or Lon CO, forces Lo GpPolar Dipole- HCI, SO, Soft Insulator yw dipole interactions_ | —-_| ydrog: Low Gif ydrogen, Hydrogen HO (ice) Hard Insulator bonded bonding | - i but —Insulatorsin High TTonie sous — i , MgO, ZnS, | Hard De = | stem cant ae brittle, solid state but dk 7 ——~ | conductors in electrostatic molten state and in aqueous solutions Hard but | Conductors Fairly high nfalleable | in Solid'state '3,) | Metallic solids Positive | Metallic | Fe, Cu, Ag, Mg ions bonding asea of LU and ductile | ag well asin | silocalised —— | molten state (electron: 4})/ Covalentor | Atoms Covalent | SiO, (quartz), SiC, | Hard Insulators Very high network solids bonding. Cidiamond), AIN,| —_ * Cegrphit) Sot Conductor (exception) 2. Space Lattice and Unit Cell Space Lattice: It_is_the_three- dimensional arrangement of identical * poipisin the sp ich represent fow the constituent particles (atoms, i iolecules) are arranged ‘in a crystal. Each particle is depicted as a Point. j Fig. 1.3: llustration of Unit Cell: A unit cell is the smallest paramet f portion of a ‘space lattice which, ae val wHtel when repeated in different directions, lato’ and fs unt ell — | genefates the entire lattice. A unit cell is characteri ix parameters, i.e., axial angles a, B and y and axial, lengths a, b and c. Thus, unit cell of a crystal possesses all the structural properties of a given crystal. ee Properties of a given crysts 3. Crystal Systems: On the basis ofthe axial distances and the axial angles between the edges, the various .Lrystals can be divided into seven systems. These are listed inTable [3 Table 1.3: Seven Primitive Unit Cells and their Possible Variations as Centred Unit Cells - ee Nartation ured prime, Body centre, NaCl, Zine blende, Cu, =n KCl, Diamond Primitive, Body-cent a=bee White tin, SnO,, TiO, = caso,b 90° ie sulphur, KNOs, | thor ic | Primitive, Body-centred, aebec a= Bp=y=90° | Rhombic sulphur s ‘Rhombic ate - ‘Graphite, ZnO, CdS, Mg, } Hexagonal | Primiiive oe ombohedral | Primi Calcite (CaCO) HeS et [mene (cinnabar), ICI, As, Sb, Bi * i | (Ginnabar), IC, As, Sb, Bi | by End-gented Monoclinic sulphur, Nowe came Foie PbCrO,, Na,SO,.10H,0 tive K,Cr,07, CuSO, 5H;0, { | H3BO3 ’ Primitive Body-contred (Fosecentred (CLSIMPIC) Te three cuble all sideg of same ‘ane Sa esate - Primitive Body-centred The two tetragonal: one side different in length from the other, Ao angles between faces al 0" ] 2 Prive Eng-csatred Body-centred The four ortherhamblc lattices: unequal sides, 18S between faces all 90" Primitive The two monoclinic lattices: un i "Wo Tacos ade engl Sher aass than 0° see Seer aeront Sener ienginte tester vo, eel eeles on twoTaces are 0° and Bhombohedralt alfsides, of equal 4 0 length, angles on two ices are less than 90° ‘tig remaining angle 7 - ista 7 ‘Tiiglinic lattice: 5. i . Ce Fas with none equal to 90 2 Init Cells of 14 Types of Bravais Lattices 4, Number of Atoms in a Unit Cell érKn stom lying atthe comer ofa unit cel is shared equally by eight unit cells and therefore, only one- ighth (1/8) of an atom belongs to the given unit cell. #27An atom present on an edge is distributed among the four unit cells, therefore only one-fourth (1/4) of an afom belongs to the given unitcelL (WA face-contred atom is shared between two adjacent unit cells. Therefore, one-half (1/2) of an atom ligsin each unit cell. || <> iri X body-centzed atom belongs entirely to one unit cell since it is not shared by any other unit cell. ‘Therefore, its contribution to the unit cell is one. Applying above stated points, let us calculate the number of atoms in the different cubic unit cells. jimple cubie: 8 (comer atoms) x > atom per unit cell = 1 atom (Deroay-contrea cubic: 8 (comer atoms) x + atom per unit 3 cell + 1 (body centre atom) x 1 atom per unit cell | ——___38__ RE atom per ur =14+152 Q /Face-centred cubie: 8 (comer atoms) x + atom per unit cell ~~ Comer atoms) x atom per unit ¢ 1 +6 (face atoms) x 2 atom per unit cell = 1+3=4 Xam idea Chemis}pable 1.4: Number of Atoms per Unit Cell | im ‘Number of atoms PO noe in faces 0 | jinn etic jody-centred cubic (bee) 0 2 sace-centred cubic (fee) - ae a = ° 4 a a, dis the density of the substance Density of Unit Cell: Suppose edge of a unit cell of a cubic crystal is and M is the molar mass, feubic crystal, — Mass of unit cell = Number of atoms in unit cell x Mass of each atom, / =zxm (olar mass Mass of each atom (m) = 7 ooedro number = m=, 2zxM M - Volume of a unit cell = a? Therefore, density of the unit cell, Mass of unit cell = Mass of unit cell Volume of unit cell — d= 22M where dis in glom? sod aisinem. @ XN, 6. Other Parameters of a Cubic System (@) Atomic radius: It is defined as half of the distance between nearest neighbouring atom in a crystal. It is expressed in terms of length of the edge (a) of unit cell of the crystal. + as atoms touch each other along the edges. @ Simple cubic structure (sc): Radius of atom ‘r’ = 3 ~——_— a ————————_. — (i) Body-centred cubic structure (bcc): Radius of atom ‘7’ = 738 the atoms touch each other along the cross diagonal of the cube. : Radius of atom “7? = Ff 38 the atoms touch each other (di) Kace-centred cubic structure (fcc LE along the face diagonal of the cube. TY ©) Coordination number: It is defined as the number of nearest neighbours that a Particle has in a unit cell. It depends upon the structure of unit cell of the crystal. Simple cubic structure (se): Coordination number (C.N.) = 6 Gi) Body-centred cubie struct N= 8 Gz Face-centred cubic structure (fcc): C.N. = 12 oS 7. Packing Efficiency Packing efficiency isthe percentage of(iotal space Filled by the particles) 7 5 —— Packing efficiency = V&tu™e occupied by atoms in unit cell (+) 7 Total volume of the unit cell (V) @) Packing efficiency in simple cubic structures: Let ‘a’ be the cube edge and “7” the atomic radius, ese a the atomic radi ~ * 100As the particles touch each other along the edge, therefore a = 2r ‘Volume of the unit cell = a° “of the unit eel = 4 ; Since one atom is present in a unit cell, its volume 4 y _ma 6 x 100 x100 7 =“ Fig. 1.6: Simple cubic unit cell. The spheres = 52.36% = 52.4% are in Sontact with each otter along The edge of the cube. ~~ Therefore, 52.4% of unit cell is occupied by atoms and the rest 47.6% is empty space. Ox ing efficiency in cep and hcp structures: The efficiencies of both types of packing-cep and hep, “are equally good since in both, atom spheres occupy equal fraction (749%) of the available volume. We shalinaw calculate the efficiency of packing in ccp structure. Let the unit cell length be ‘a’ and face diagonal be *b’ (represented as AC in Fig. 1.7). In this figure other sides are not shown for the sake of rae clarity. Inn s B ( In triangle ABC, ZABC is 90°, therefore, AC =B =BC + AB | F =a 4a = 2a 4 b=Y2a_- If the radius of the sphere, we find or or, = we 2v2 aes As cop structure has 4 atoms per unit cell, therefore the total volume Fig. 1.7: Cubic close packing of 4 spheres (v) is = @=Qv2n Packing efficiency = 7 x 100 Total volume of the unit cell (| _ 4x @/3)xar7 iy (16/3) x m7 ee 5 oe x100= x1 16x ir 3y2 ~100 {74% Therefore, 74% of unit cell is occupied by atoms and the rest 26% is empty space. a Of packine in hae aha, Ss: Inthe case hen aS (©) Efficiency of packing in bec structures: Jn this case the isin touch wi 0 Toms which are diagonally arranged (see Fig, 1.8). The spheres along the body diagonal are shown « with solid boundaries. In AEFD, — Bat taard In aarp, bea, t Cab + Pa 420 23a G YBa Bae | xem icca chomisty Effective number of voids at edges = 12 x Ee 3 Total number of octahedral voids = 1 = a Ss. These re located at the body diagonals, two on each body In cep structure, there arc 8 tetrahedral void diagonal at one-fourth of the distance from cach end. Ze 11. Radius Ratio: For ionic solids, the ratio ofthe radius of cation to that of anion is called radivs rati Radius ofthecation = FS Radius of the anion a Radius ratio = 12. Crystal Defects: The defects are basically irregularities n thoarranggment of constituent particles. Broadly, cetal defects are of two types, namely, point defects and line defects, Point defects are the irvegulariticg or deviations from Tdeal arrangement around a point or i deTectsare the irregulari i irregularities are called crystal defects. 13. Point Defeets interstitials: Atoms or ions which occupy normally void: I Vacancy: When one of the constituent particles is missing from the crystal lattice, this unoccupied position is called vacancy. vacancy. in a crystal are called interstitials,Point defects can be classified into three types: a Oe a f the solid are call s, ity defects, and ( ioral J so oe fet at oo ist he stschiomete oF SO alg i stric Defects: The point defect i or thermodynam eee defects. They are also called intrinsic re of Ty stoichiometric def 5. stoichiomenie defeats, intersti 2 said to have vacan, iypes, vacancy defects and interstitial eee s stesare vacant, the ental is Sid 10 MOVE acon, Care ic substance j Vacancy defect: When Som ne substance. This defect can aise-when a substan is in decrease in density of the substan defect. Itresults in 3) occupy an interstitia, inert ticles (atoms or molecule: (By Interstitial defect: When some constituent erystal is said to hav ct. Di the density of the substanc, rystal t sity of the st i ‘Site, the crystal is said to have a eteet D ue to this defect site, ionic soli se ionic solids must joe. ly shown by non-ionic solids becau use ionic solids must jgcancy and interstitial defe = ttky and Frenke} aor a rial aeutalty Toni solids show these defects as Schottky and Frenk always maintain electric a jons_are missing defects as explained below. er of cations and anions are ay yhen equal number of cations oe en ber when @Sth fect ari ee eee: ition num frot Hone en defect in jonic compounds eo a ee to this def Pat ons and anions eof hg same 2» BOL Na rani Fig. 1.16(a)]; ensity of crystal decreases and it begins to.conduct electricity to a smaller interstitial : frome oe Tis defect arises when some of the ions of the lattice occupy 1 P Frenkel defect: is ini stals where anion sites leaving lattice sites vacant. This defect is neralyfgund in oni cesta swhere anion Stes Teaving faltics ; ennai y is much larger in size than the cation, e.g., Ag] Se neal — change, electrical conductivity increases to a small extent and there chemical composition of the crystal (Fig. 1.16(b)]. Fig. 1.489} Schottky defect ) Impurity Defects: These defects arise when foreign atoms of ions are present in the Tattice site (substitutional Solid solutions) or in the Interstitial sites (interstitial solid solutions). For example, when molten NaCl containing alittle amount of SrCl, is crystallised, some of the sites of Na* ions are occupied by Sr. Each Sr replaces two NaF ions. It occupies the site oF one iow-and the other site remains vacant. The cationic vacancies thus produced are equal in number to that of St™* ions, TF, (© Non-stoichiometric Defects: Thess defects arise when Stoichiometry of a substance is disturbed, two types, —s ceturbed. ‘Tse are oe (g)Metal excess defevt: Fig. 1.17: Introducti i f cation vacancy in This may occur in gi i tion ofa eS following two ways: y in-either of the NaCl by substitution of Na : @ Metal excess defect due to an; i eso : fect anion vacancies: In this def ive i a0 fatice fay be missing from its lattes ce feta San ee the electron originally aSsociaieg wit oes Vins 4 hole or vacancy which is occupied by 55 : x ialides like NaC] and Khe the anion In this Way crystal remains neutral. Alkall “Taide ike Nact Sn y crystal remains neutral s type of defect, | Xam idea Chemistry-xi|leg wo ney eis nce => F-centres: These are the anionic sites occupied by Gnpaii ro}. F-centres impart colour ‘TWarystals They impart yellow colour to NaCl eryStais- violeteatoar to KCI crystals and pink colour to LiCl crystals. The colour resulis by the excjtation of electrons when they absorb (ii) Metal excess defect due to interstitial cation: In this defect an extra positive ion occupies interstitial position in the lattice and the free electron ir icinity of this interstitial cation. In this way crystal remains neutral. For example, zinc oxide on heating loses oxygen and turns yellow? zno —Heting_| nt 4 10, +26" | The excess of Zn** ions mowSto interstitial sites and the s to figighbouring interstitial S. Oyen deficiency defect: This type of defect generally occurs when metal shows variable valency. The defect arises due to the missing of cation from its lattice site and the presenci tion having higher charge in the adjacent lattice site. For example, Fe,O, where x = 0.93 to 0.96. Fig. 1.18: Metal deficioncy defect due to missing cations 14. (a) 13-15 Compounds: When the solid state materials are produced by combi of elements of groups 13 and 15, the compounds thus obtained are called 13-15 compounds. For example, InSb, AIP, GaAs, oe. - ———E— errr () 12-16 Compounds: Combination of elements of groups 12 and 16 yield some solid compounds which are referred to as 12-16 compounds. For example, ZnS, CdS, CdSe, HgTe, etc. In these compounds, the Bonds have ionic character, 15, Magnetic Moments: The magnetic properties Magnetic Magnetic of substances _result_ from _their_ magnetic moment 4 moments associated with individual electrons. Each electron has a magnetic moment, origin of Which Ties in two sources. Itis a known fact, that an electron shows two types of motions, i.e., it rotates (spins) around its own axis and Atomic” 7 Direction simultaneously _revolves—around_the_nucleus nucle of spin 2 (orbital motion). An electron in motion is just like er er oe : , a Sinall current loop. Two types of motions Fig. 1.19: Magnetic moment associated with (a) orbital ride To 1Wo types of magnetic sone) ‘motion and (b) spin motion of an electron and dtbital magnet moments. Spin moment 1s » directéeratong the spin aXis and is shown up or down direction [Fig. 1.19(b)). Orbital motion also generates a fhggnetic field and thus gives rise to orbital moment along its axis of rotation [Fig. 1.19(@)]. In this wa cach electron of the atom behaves Tike a small bar magnet having permanent orbital and spin magnetic moments. Magnetic moments are measured in Bohr magneto i 5 ah s| cy Electron a 1BM.= armel =9.27x 10™ Am? or 9.27% 10! erg/gauss Where ¢ is charge on electron; is Planck’s constant; m is the mass of electron and cs the velocity of light. Dependifig upon two spin motions (clockwise and anticlockwise), spin magnetic moment may acquirei ent is equal to M,, My, where M, is magnoy Ines + Mp. Contribution of the orbital magnetle moment is caual 10 My: Mo» where Mi is magn, ‘nwo values CE substances cay be classified jy, be classified iy ied Se fthei ic properties, : jgnetic Properties of Solids: On the basis of their magnetic ic Proprio = five categories. Fray repelled by the external magnetic ficld. The atom, @_Diamagnetic: agnetic substances are}weakly TEP rons caneel their magnetic momeiy. ——Tpaired up clect paring” pe ee ortnse substances aveall pairedup cleet80s. ASPET rare some examples of diamagnee they lose their magnetic character. NaT') Na 2 substances .e external magnetic field, -. Paramagnetic substances are weakly attracted py th external magnetic Felt. The Lby Paramagnetic: Paramagnetic subse at gai CMO a atoms of these substances have one of more, ee Ce NO, WO,, Cue" are some example, present as long as external magnetic field is present: x» en Crs mn esent as Tong as extern i of paramagnetic substances. ; temal magnetic fel “Spr Ferromagnaie: Ferromagnetic substances are strongly atractd by the enemne ET ae solid state, the metal ions of these substances aré grou 7 ios Seeiacal Bes rnanetic field all the 7 stance IS rach domain acts as a tiny magnet, When such _a_substat Feet is produced. This is get oriented in the ; tic e domains get oriented in the direction ‘of magnetic field and a strong me a cube ordering of domains persists even when the magnet field is removed and the ferron 0 i -s can be permanent! Becomes a permanent magnet. Thus, besides strong attractions, these substances cm iy miagnetised, a 7” WAntiferromagnetic: These substances _have_domain sauce sini ne substances but their domains-are oppositely oriented and cancel out each other's magnetic moms _-Mn0 is an antiferromagnetic substance. , an paral Ferrimagnetic: In ferrimagnetic substances due to unequal number of magnetic moment in PAT and antiparallel directions. the net magnetic moment is small. These substances Tose ferimagnetism on heating and become paramagnetic. Fe,O, and ferrites like MgFe,0, and ZnFre,0« are examples of PAAR TUREEE TAU _ a Ferromagnetic (o-mtieromagnelic _(¢) Ferrimagnetic . Fig, 1.20; Schematic alignment of magnetic moments brie ‘Temperature: The temperature at which a ferromagnetic substance loses its ferromagnetism and attains paramagnétism only is called curie temperaiure. For iron, the curie temperature is 1033 K, for Ni it is 629 K and for Fe,O, it is 850 K. Below this temperature paramagnetic substances-behave ‘as ferromagnetic substances. 17, Electrical Properties? Solas are classified into three groups on the basis of their electrical conductivities: (@ Conductors: These generally include metals. Their conductivity is of the order of 10-10" ohm“ m, © Semiconductors: Those solids which have intermediate conductivities ranging from 10° to 10* ohm"! m"" are classified as semiconductors. As the temperature rises there js a rise in conductivity because electrons from the valence band jump to conduction band. © asain ‘These are solids which have very low conductivity values ranging from 10° to 10° ohm m4, > if i orati pe ce in sot i in most of the solids conduction takes place-duc to migration of influence of electric field. However, in ionic compounds, it is the ions that are responsible for the conducting behaviour due to their movement, In metals, conductivity strongly depends upon the number of valencé electrons available in an atom ‘A band is formed due to closeness of molecular orbitals which are'formed from atomic orbifal > orbiqals. 1 this band is partially filled or it overlaps the higher energy unoccupied conduct the electrons can flow easily under applied ele: ae ean ‘tric field and the solid behaves'as conductor [Fig. 1.21(a)].Jfthe ga? ion band is large, electrons cannot ji? J between valence band and next higher unoccupied conducti into it and such a substance behaves as Insulator. Fig. 21) Xam idea Chemistry-Xl| I sto-xNetig Lint, toms Tits, neti Retic d is Ples, , In the ‘his, nce tly lel ™m eh ae Conduction band, Empty Empty ban band” 4 Forbidden zone «| ‘small energy 9P | (Large energy 68°) Filled ah es Bar Partially Overlapping tally ft te | Jey Semiconductor “get pytisulator Fig, 1.21: Distinction among metas, insulators and semiconductors If the gap between the valence band and conduction band is small, some electrons may jump from valenee band to the conduction band, Such a substance shows some conductivity and it behaves 26 a semiconductor [Fig. 1.21(¢)]. Electrical conductivity of ‘semiconductors increases with increase in temperature, since more electrons can jump from valence to conduction band. Silicon and show this type of behaviour and are called intrinsic semiconductors. . (¢) Doping: Itis a process by which impurity is introduced in semiconductors to enhance their conductivity 1 -type semiconductor: When silicon or germanium crystal is doped witha Group 15 element like P or ‘As, the dopant atom forms four covalent bonds like a Si or Ge atom but the fifth electron, not used in bonding, Becomes delocalised and contributes its share towards electrical conduction, Thus, silicon germanium doped with Por As is called n-type semiconductor, n indicates negative charge of electron since itis the electron that conducts electricity [Fig. 1.220]. =» p-type semiconductor: When silicon or germanium is doped witha group 13 element like B or Al, the dopant atom forms three covalent bonds, but at the place of fourth 1 electron a hole is created. This hole moves through the crystal like a positive charge giving rise to electrical conductivity. Thus, Si or Ge doped with B or Al is called p-type semiconductor (p stands for positive hole), since it is the positive hole that is responsible for conduction [Fig. 1.22(c)]. ” germanium Silicon atom Mobile electron Feaiive le ino electron) fy Pertect crystal Pi mtype Fig. 1.22: Creation of n-type and p-type semiconductors Diode: Diodes are made by the combination of n-type and p-type semiconductors, They are used as rectifiers, 28 Transistors: These are used to detect or amplify radio or audio si; sandwich semiconductors, ~*F Photodiode: These are diodes which are capable of converting light energy into electrical energy and, are used in solar cells. pide ignals. They consist of pnp or npn