CHEMISTRY CLASS-XI a PART 1 & Il TRCTLY ACCORDING To THE NEW SYLLABUS @ Nitra INDIA'S FIRST SMART BOOK ONytra Dr. S.P. JauharPERIODIC TA 9 Moder gop 4 2 3 4 5 6 7 8 gow [1A WA mB) WB vB vB vis. vil Period i | S-BLOGK (ns**) 7 tom ‘oH rarogen Relative omeMass |_| Alkali metas [Oo Atcatine cart 2 Name || Transition me Electronic Lanthanides He Configuration o 3 BLOCK [(n-1) dns”) fis TRANSITION ELEMENTS 4 Ar s s Rb Rubiann Kr 6 xe 7 Rn +N EMENTS C Solid LANTHANIDES, (at"5a"'6s") Br Liquid H_ Gas * Most stable isotope (discovery claimed) ACTINIDES To Synthetic (8 "*ed""7s")BLE OF THE ELEMENTS 10 11 12 43 14 15 16 47 18 1B 1B 1B WA WA VA VIA VILA VIIA Actnides _—, ‘ermal tals [Oy] non-motais e [El note gases co “ - a —_— _Al i r 38%3pt i, se ag oo - Ni Cu Zn |Ga Ge (As |Se |Br Kr | 2 | ee b yas?| ad?4s2| ac'94s'| ga'%4s?| ac!4s2apt| ad!O4s2ap? joaar 8) a7 egg Teelgg lg EN 5) BIE 46 Pd Ag Cd In Sn Sb {Te e ae a ee ee waa] 7q waa 7 IT] 9g TOP gy TL BD Aa gg A Bg Pt WAu Wig Wl Beeb SBI BPo t n sada ssciadllie' ssc Soils xe ail ileas on Aol 10 a2 ns es eS ic =a; te = Ds_|Rg |Cn_ | Nh |FI Mc |Lv_ | Ts | Og m | Darmsiatiom |ponigastm | CoPemcion | num | Flerov Moscovium | Lvermorum | Tennessina | _OganeSion 17752 5t'*6d°7s? | St'4ed'°7s" | S{'46d'°7s? 5t'*6d'°7s"7p\st"*ea'°7s27¢? 5t'*6d"°7s"7p|=t"*6a'°7527p* | Sf'46d"°7s"7p"| St'*6d"°7s*7p° BLOCK [(n-2 "(nt ns} | <—_— REPRESENTATIVE ELEMENTS» - INNER TRANSITION ELEMENTS 15035] @g 15195/ gq 19725/g5 19803 gq 16240 67 69 1 |Eu |Gd |Tb |Dy |Ho |Er |Im /¥b jLu » | Eoepam | Gaeta Dypdaiun | Homiom | Emm “Then vyooman | Laeoom fes?| af’es®| af’sd'es?| ates? atlas?) at"es?| —ar'2es?| —atl96s%) ates?) atl4sd'es® 80695 2806/9 2707/97 A707! gg 108 | gq 5208 499 2718 | 494 HF10| 49D PIO 49g BENT Am |Cm |Bk |Cf |Es |Fm jMd_ |No /|Lr 1 | Amerim | Caran Beraiom | Calera | stoma | Fermium | Mendolevum | Nobo | Lawrencam S78? sf'7s?| sf’6d'7s* Shs? 57s? St" 75? sf'?7s? Sts? st'47s?) st'4ed'7s? 209.98 tess] gg 19726) 6095/79 tract) 74 17497Actinium ‘Aluminium Americium_ ‘Antimony Argon Arsenic Astatine Ravinim Berkelium Beryllium, Bismuth Boron Bromine Cadmium Calcium, Californium Carbon Cerium Cesium Chlorine Chromium. Cobalt Copernicium Copper Curium Dysprosium Einsteinium: Exbium Europium Fermium Flerovium, Fluorine Francium, Gadolinium Gallium Lanthanum Livermorium Lutetium ‘Magnesium BREESE SPER STOP EEE REP OSE PUSS E ERS OSS PASE CAPR EUR PR PEER OR EE 2.00) and Electronic Configurations of Elements Atomic Number Atomic Electronic Configuration Mass: 227 [Rn] 6a! 792 26.9 [Ne}? 352 gp! 243, [Rn] 57757 121.75 [Kr] 4a 552 5p® 39.94 [Ne}® 3s? 3p® 7492 [Ar}#8 3° 452 4p? 210 [xe]5* 4/4 5c” Gs? 6p? taza [xe] ae? 247 [Bn] 5/76? 9.01 [He]? 25? 208.98 [Xe] 4714 5al° 6s? 6p? 10.81 [He] 2s2 2p! 79.90 [Ar]}® 3d! 42 4p> 112.40 [r]8® 4a? 52 40.02 [Ar}'§ 4s? 251 [Rin] 5972 2 [He]? 2s? 2p? 140.12 [Xe] 47 5d 632 132.90 Pxe}** 6st 35.45 [Ne}}9 3s? p> 51.99 [Ar}#8 38 det 58.93 Ar}! 3d? 4s? 285 [Rn]* 54 6d" 75% 63.54 [Ar}#8 342? dot 245 [Rn]®°5/? 6a! 792 162.50 xe] 4/19 6s? 254 [Ra] 5p 752 167.26 Xe) 2 662 151.96 [Xe] 4/7 6s? 257 [Rn] 52762 289 [Rl*546d2°7=°Tp2 18.99 [He]? 252 2p 228 [Rn] 73! 157.25 [Xo] 471 Be 6s? 69.72 [Ar}#8Sd°® 492 4p! 72.59 [Ar]#83ed2® 452 4p? 196.99 [Xe]** 4/4 5d"? 6s" 178.48 Pxe}** 47% 5a? 652 260 [Rn]** 5f'* 6d? 75? 4 dst 164.93 xe} 47" 6s? 1 iat 114.82 Uir]?* 4a 5s? 5p! 126.90, [Kr] 4a 532 5p 192.2 [Xe}®* 47% 5a 6s? 55.84 [Ar]'$ 3d° 45% 83.80 [Ar}# 32° 452 4p 138.91 [Xe]** 5" 6s? 251 [Rn}® 5/4 6a" 752 207.19 Xe] 4/4 5d! 63? 6p? 6.93 [Bte)? 1s? 293 Ral*5/46d°7527p¢ 17497 [Xe] 47°4 5a” 6s? 2431 [Ne}!° 352 54.93 [Arp * 344sSilver Sodium Strontium Sulphur ‘Tantalum ‘Technetium ‘Tellurium, ‘Tennessine ‘Terbium ‘Thallium ‘Thorium ‘Thulium, Tin ‘Titanium ‘Tungsten Uranium Vanadium Xenon Ytterbium Yttrium, Zine Zireonium a SBOP ZEA CORP AREER SP PAS PRU LOPL Zz NeMse 1, itis called positive deviation. It means that the gas is less compreesiblo than expeeted from ideal behaviour. pea 2TRb ae =/3b ‘+ decreases with rise in temperature Units : Pa.s or Nov? s Viscosity QL Qe Textbook Exercises f/f] What will be the minimum pressure required to compress 500 dm® of air at 1 bar to.200 dm’ at 30°C. PNa PM Ve (bar) x (500 dm*) (200dm*) = 25 bar Avessel of 120 mL capacity contains a certain amountof gasat35°C and 1.2 bar pressure. The gas is transferred to another vessel of volume 180 mL. at 85°C. What would be its pressure? Refer Solved Example 2 (Page 12) Using the equation of state pV =nRT;show that, at a given temperature density of a gas is proportional to gas pressure p. DW, (at constant T) Pao pV = nRT RT or pe y Now, number of moles (n) = Mass of substance (m) ‘Molar mass(XD mRT Pe Qs. But J = density, d so that aR Po ow or pM RT cor d= p (for a given gas at constant T) Thus, at a given temperature donsity of a gas is proportional to gas pressure, ALO°G, the density of a certain oxide of a gas at 2harissameas that of dinitrogen at Shar. What is the molecular mass of the oxide? Mp Density, ar At the same temperature and for the same density. Mp, = Mp, (Gaseous oxide) (Ny) 1M, x(2bar) = 28 «(5 bar) RK M 2 Pressure of | gofan ideal gas A at27°Cis found to be 2 bar. When 2 g of another ideal gas Bis introduced in the same flask at same temperature the pressure becomes 3 bar. Find arelationshipbetween their molecular masses. Let the molceular masses ofA and B are M, and My, respectively. vu WWW.JEI DKS.INrs a6. Moles of gas A 2 Moles of gas B= eae B= 3 bar Pat pg= 3 bar 0 that py bar Applying gas equation, pV = nRP DaV = met Dividing eqn (2 by ogni “ ltt) My | My 27M, ~ 2M, or Ben ax2 i = My. ‘Thedraincleaner,Drainexcontains small bitsof aluminium which react with caustic soda to produce dihydrogen. What volume of dihydrogen at 20°C andonebar willbereleased ‘when 0.15g of aluminium reacts? Refer Solved Example 23 Page 21), ‘What will be the pressure exerted by a mixture of 3.2 g of methane and 4.4 g of carbon dioxide contained in a9 dm flask at 27°C? Motes f CH= 22-02 6 nner Peay? 0.2 mol x (8.314 Pa m°K “lino "}x 300K 9x10%m? 5.54 x 104 Pa 44 Moles of CO, = 4 =0.1 O.Amol> (8.814 Pa m®K Tmo!) «300K Peco 910 ml 2.77 « 108 Pa ‘Total pressure = 5,54 «108 Pay2.77 x 104 Pa 831% 10¢Pa ‘What willbethe pressure ofthe gaseous mixture when 0.5 LofH, at0.8 bar and 2.0L of dioxygen. at 0.7 bar are introduced ina IL vessel at 27°C? Ans. Refer Solved Example 29 (Page 25) Q.9. Density ofa gasiisfound to be 5.49 gidm* at 27°C at 2 bar pressure, What will be its density at sre? Ans. Refer Solved Example 26 (Poge 22). @.10. $4.05 mL of phosphorus vapour weighs (0.0625 gat 546°C and I bar pressure. Whatiis the ‘molar mass of phosphorus? ‘Ans. Molecular mass of phosphorus, M= “RT. pv 0.0625 g, Qu. Ans. Qa. Qu MODERN'S abe + OF CHEMISTRY-X! V=34.05 mL p=1.0 bar ‘T=273 + 546 = 819K, R=0,08314 L bar K-! molt 4.05 x 10° L, = 220625 gx (0.08914 bar I, Kmol™)<819 K 134.0510" = 124.98 g mol"! M |. Astudent forgot to add the reaction mixture to the round bottomed flask at 27°C but instead he/she placed the flask on the flame. After a apse of time, he realized his mistake and using ‘a pyrometer he found the temperature of the flask was 477°C. What fraction of air would have been expelied out? weve Ty 27427 213 477 200, 7508 Calculate the temperature of 4.0 mol of a gas occupying 5 dm? af 3.82 bar. (R = 0.083 bar dm” K+ mot) Refer Solved Example 20 (Page 20). Calculate the total number of electrons present in 14 g of dinitrogen gas. La 24 0.05 28 No. of molecules of dinitrogen = 0.05 x 6,02 x 10% O11 x 102 No. of electrons in one molecule of Ny = 14 «No. of electrons in 1.4 g of N = 3.011 x 10% x 14 4.2154 x 108 How much time would it take to distribute one Avogadro number of wheat grains, if 10" grains are distributed each second? Avogadro number = 6,022 x 10% 10" grains are distributed in = 1 see. 6.022 x 10 grains would be distribtued in 6,022 x 10 70 6.022 10" 10" x 8600 x 24 <865 1,9096 x 10° years. Calculate the total pressureinamixtureof8gof dioxygen and 4 g of dihydrogen confined in a weasel of 1 das at 27°C, R= 0.062 bar din” Ko mol, Moles of dinitrogen Refer Solved Bxample 30 (Page 25). ;. Pay load is defined as the difference between the mass of displaced air and the mass of the balloon. Caleulatethe payload whenaballoonof radius 10m, mass 100 kg is filled with helium at 2 kgm and 1.66 bar at 27°C. (Density of air = R= 0.083 bar dm? K+! mol"), v WWW.JEEEessing, © Understanding Text ‘¢ Conceptual Questions 92,55 4 Adunneed Tevel Probleme £1,40,4R, + HOTS & Advanced Level 1 © Quick Memory Test with An- 00% Topiewise MCQs 0 UC ne aii Virmeintion Oe SOLUTION FILE i: > AIFMDS& Other State Boards! ‘¢ Hints & Solutions for Practice Questions with Answers 71” Medical Entrance 81 Problems 57 REVISION EXERCISES 72 7 (CHAPTER SUMMARY & QUICK ye zin Cb Sia aaa) CHAPTER ROUND UP a1. Hints & Answers for Engineering Entrance 82 NCERT FILE Revision Exercises 78 > JHE (Advance) for IT Entrance 84 4 Intext Qo & Exercises with ‘+ NCERT Exemplar Problems Solution 64 UNITPRACTICETEST 102 (Objective Questions) 90 ‘¢ NCERT Exemplar Problems with, + Hints & Rxplanations for Difficult, Answers & Solutions (Subjective) 68 Questions 0% SOLID STATE OF MATTER CLASSIFICATION OF SOLIDS ‘The properties of the sotids not only depend upon the nature ofthe constituents but also on their arrangements and the types of forees which hold the constituent particles together in a tightly packed arrangement, (GENERAL CHARACTERISTICS OF SOLID STATE Some ofthe important characteristic properties of solids are : (@ Solids have definite mass, volume and shape. (i) The intermolecular distances in solids are short and intermolecular forces are strong. Gii) The constituent particles (atoms, ions or molecules) of solids have fixed positions and ean only oscillate about: their mean positions. iv) Solids are almost incompressible and rigid. (@) The density of solids is greater than that of liquids and gases. (i) Solids diffuse very slowly as compared to liquids and gases, (vii) Most solids become liquids when heated. ‘This process is known as melting and the temperature at which a solid changes into a liquid is called the melting point. The ‘melting point of a solid depends upon the nature of the solid and melting points of solids vary widely. Solids can be classified on the basis of nature of order present in the arrangement of constituent particles (atoms, ions or molecules) into two types as: 1. Crystalline solids 2, Amorphous solids 1, Crystalline solids The substances whose constituent particles (atoms, ions or molecules) are arranged in a definite geometric pattern in three dimensional space are called crystalline solids. X-ray diffraction studies of crystalline solids reveal that in these solids, the constituents (atoms, ions or molecules) are arranged in a definite orderly arrangement. The regular arrangement of the constituents extends throughout the three dimensional network of erystals. In other words, the erystalline substances are said to have long range order. This means that in crystalline solids, there is a regular pattern or arrangement of particles which repeats itself periodically over the entire erystal. In fact, a crystalline solid consists of a large number of small ceryotads, each uf then Laviang a definite chau acteristic geometrical shape. ‘Most of the substances (elements and compounds) form erystalline solids, For example, the elements like copper, silver, iron, sulphur, phosphorus and iodine and common compounds stich as sodium chloride, potassium nitrate, zinc sulphide, quartz, ete, all form crystalline solids, VWW.JEE S.IN Ea2. Amorphous solids The substances whose constituent particles arenot arranged in anyregulararrangement are called amorphous solids (Greek amorphos meaning no form). ‘The amorphous solids have a random, disordered arrangement of constituents. Therefore, they do not have definite shape or form like erystalline solids. It is observed that some amorphous solids have some orderly arrangement but it is not extended to more ‘than a few Angstrom units, Thus, the amorphous solids are said to have short range order. This means that in amorphous solids, a regular and periodically repeating pattern is observed over short distances only. These regular patterns are scattered and in between, the arrangement is disordered. ‘The common examples of amorphous solids are glass, rubber, plastic, coal, ete, Differences between Crvstalline and Amorphous solids The important, differences between crystalline and amorphous solids are: 1. Characteristic geometry. The crystalline solids have definite regular geometry because of orderly arrangement of constituents (atoms, molectles or ions) in three dimensionat space. On the other hand, amorphous solids do not possess any regular arrangement of constitnent particles and therefore, do not have any definite geometric shape. Structure of quartz (erystalline) and quartz glass (amorphous) Quartz is a form of Si0, (silica). Tt has tetrahedral] SiO, units which are orderly arranged in crystalline quattz as shown in Fig. 1 (a), In this arrangement, SiO, tetrahedra are connected to one another such thal oxygen atom of each SiO, tetrahedrallis shared with another atom, When SiO, is melted and themett| is cooled, it forms quartz glass which is amorphous. Tntthis state, the SiO, unite are ranclomly joined [Fig| 1)). Thus, in quartz (crystalline), SiO, units are orderly arranged while in quartz glass (amorphous), the SiO, units are randomly arranged, While the! two structures are almost identical, yet in case of amorphous quartz glass, there is no long range! order. The structure of amorphous solids is similar| to that of liquids. (a) Crystalline quartz () Amorphous quartz glass Fig.l. Two dimensional structure of (a) crystalline quartz and (6) quartz glass MODERN'S abe + OF CHEMISTRY-Xt 2. Melting points. The orystalline solids have sharp melting points, On the other hand, amorphous solids do not have sharp melting points. Therefore, crystalline solids have definite enthalpies of fusion whereas amorphous solids do not have definite enthatpies of fusion, ‘The amorphous solids, in fact, on heating first soften and then melt over a range of temperature, Therefore, amorphous solids ean be ‘moulded and blown into various shapes. For example, ‘when glass is heated gradually, it softens and starts to flow without undergoing a definite and abrupt change into liquid state, Therefore, glass can be moulded and given any desired shape. It has been observed that on heating and then cooling slowly (ie. annealing) some amorphous solids become érystalline at some temperature. It is for this reason that some glass objects from ancient civilizations are found to become millsy in appearance, Milkiness of glass is due to the fact that it undergoes heating during the day and cooling at night (.e., annealing) over a number of years. AS a result, it acquires some crystalline character. 5 Glass window panes of very old buildings are found to be slightly thicker at the bottom than at the top. » Glage is an amorphous solid which is euper cooled liquid of very high viscosity and behaves more or less like a liquid. The glass flows down very slowly and hhence makes the bottom portion slightly thicker. 8. Isotropy and anisotropy. In crystalline substances, some of the physical properties such, as electrical conductivity or refractive index have different values when measured along different, directions in the same crystals. Such substances which have physical properties different in different directions are called anisotropic. Thus, crystalline substances are anisotropic. Fig. 2. Anistropy in crystalline substances, IWW.JEE‘SOLID STATES On the other hand, amorphous substances have physical properties same in all directions and are called isotropic. For example, the velocity of light passing through a crystal varies with the direction in which it is measured. Thus, anisotropy is a strong evidence for the existence of orderly arrangement in crystalline solids. This is shown in Fig 2. In this figure, a simple two dimensional arrangement of two different kinds of atoms is shown. Tt is clear from the figure that if the properties are measured along two different directions AA’ and BB’, different types of particles come on the way. Along AA’ direction only one type of particles come on the way while along BB’ direction, alternate types of particles come on the way. Hence, the crystalline solids have different physical properties in different directions. In amorphous solids, the constituent particles are arranged at random and in disorderly manner and therefore, all directions sre identical and all properties are same in all directions. 4, Cleavage. Crystalline solids can be cleaved along definite planes.When cut with a sharp edged tool (eg. knife) they split into two pieces and the newly generated surfaces are plain and smooth. On the other hand, amorphous solids cannot be cleaved along definite planes. When cut with a sharp edged tool (e.g., knife) they undergo irregular breakage and split into two pieces with irregular surfaces. This is shown in Fig 3. 4 (@) Crystatine sod undergoes ‘clean cleavage (Amorphous solid undergoes regular oavago Fig. 8. Cleavage of (a) crystalline and () amorphous solid En Pen Psoudo solids or Super cooled liquids Like liquids, amorphous solids have a tendency to flow. Therefore, sometimes these are also called pseudo solids or super cooled liquids. Glass is a common exainple of peeudo solid. It softens on heating to a certain temperature. Te behaves more or leas like a fluid. Pitch ie another example of pacudo solid. ‘Thus, the pseudo solids possess the following characteristice: Gi) They can be easily distorted by applying force. ii) They can flow slowly under their own weight and lese shape. () They do not have sharp melting point but coften over a rango of tomporature, ‘The important differences between erystalline solids and amorphous gotids are summed up below : Table 1. Distinction between crystalline and amorphous solids. 4.Enthalpy of They have a definite and characteristic enthalpy of| fusion Fusion, '5.Cleavage | When cut with asharp ged too, thay spitintotwe piseos property [andthe newly genenited surfhos re plain and month 6. Anisotropy | They are anisotropic and have different physical proper- ties indifferent directions. 7. Nature | They are true eolide Common |Copper, silver, iron, common salt, zine suphide, potas- examples sium nitrate, eta. Property -yalalline solide Amorphous solids 1. Shape [The eryatalline colds have definite charasteristic shape, [The amorphous solids have iregular shapes 2. Order in | They have segninr arrangement of the constitnent | They danothave any regular arrangement of potticles, They are said to exhibit long range order. | the constituent partion, They may have shor constituent range order particles. |&. Melting point | Thay havé sharp and characteristic melting point, | They donot have sharp melting point, They gradually soften over a range of temperature, They donot have definite enthalpy of fusion. [When eut with a sharp edged tool they eut into two pisces with irregular surfaces. They are isotropic and have same physical properties in all directions, They are pscudo colds and eupereooled Kiquids. Gass, rubber, plastics, ete. WWW.JEEBOOKS.INa (© The substances which show same physical properties (electrical conductivity, thermal conductivity, refractive index, ote.) in all directions are called isotropic substances, © The substances which show different physical propertios (olectrical conductivity, thermal| conductivity, refractive index, ete.) in different directions are called anisotropic substances. S Crystalline substances exhibit anisotropy while amorphous substances exhibit isotropy. = Liquids and gases are also isotropic. MODERN'S abe + OF CHEMISTRY-Xt ‘These solids have the following characteristics: G) They are generally soft Gi) They have low melting points, (iti) They are usually in liquid or gaseous state at room temperature and pressure. (iv) They are non-conduetors of electricity be- cause they consist of neutral molecules in solid as well as in dissolved state. (®) Polar molecular solids. These comprise of molecules of substances formed by polar covalent bonds. For example, solid HCl, solid SO,, solid NH, etc. The molecules in such solids are held together by relatively stronger dipole - dipole forces Uses of Amorphous Solids Amorphons solids such as glass, rubber, plastic, ete, find many uses in our daily lives because of their unique characteristies. For example, @ The most widely used amorphous solids are inorganie glasses which are used in construction, houseware, laboratoryware, etc. (i) Amorphous silicon is the best photovoltaic material for converting the sunlight into electricity (in photovottaic cella). Gii) Rubber is also an amorphous solid whieh. is used in making tyres, shoe soles, ete. (iv) A large number of plastics which are amor- phous solids are used in making articles of daily use. CLASSIFICATION OF CRYSTALLINE SOLIDS. The crystalline solids can be classified into following four types depending upon the nature of intermolecular forces operating in them. 1. Molecular solids. 2. Tonic solids 8, Metailic solids 4. Covatent or network solids 1, Molecular solids These are crystalline substances in which the constituent particles are molecules. The molecules are held together by dispersion forces or London forces, dipole-dipole forces or hydrogen bonds. These are further subdivided into the following categories : @ Non-polar molecular solids. These are those erystalline substanees in which the constituent articles are either atoms like those of noble gases (helium, neon, argon, etc.) or non-polar molecules. For example, solid helium, solid argon, solid hydrogen, solid carbon dioxide, iodine, ete. In these solids, the atoms or molecules are held by weak dispersion forces or London forces. ‘Forse af attzacton Fig. 4. Woak dispersion or London forces in solid Ho OB WIP Bigs 5, Dipole — dipole forces in solid HCL ‘They have characteristics similar to non-polar covalent molecules as given below : G@ These sotids are alzo eoft. (i) They are non-conductors of electricity. (iti) They have low melting and boiling points. But their melting and boiling points are higher than those of non-polar molecular solids. Gv) Because their melting and boiling points are not very high, most of these are gases or liquids under’ room temperature and pressure conditions, (©) Hydrogen bonded molecular solids. The molecules of such solids contain hydrogen bonds between them. For example, in case of solid water (ice), the negative end of one molecule (O*) attracts the positive end of a neighbouring molecule (H®) forming hydrogen bond between O and H. These solids eontain hydrogen bonds between H and highly electronegative elements; F, 0 or N. These solids have the following characteristics G@ They are generally volatile liquids or soft solids under room temperature and normal pressure conditions, (i) They are non-conductors of electricity. (ii) Their melting and boiling points are gener- ally higher than those of non polar molecular solids and polar molecular solids. 2 Tonie Solids Ionie solids consist of positinely and negatinely changed. ions arranged in @ regular manner throughout the solid. The ions are held together by strong coulombic (or electrostatie) forees. Thus, in ionic solids, the constituent particles are ions. ‘The regular arrangement of ions extends continuously throughout: the crystal. For example, in sodium chloride, Na* and Cl-ions have a definite WWW.JEI IN‘SOLID STATES regular arrangement as shown in Fig. 6. In this arrangement, each Na* is surrounded by six Cl ions and each Clr is surrounded by six Na’ ions. © ne oc Fig. 6, Structure of sodium chloride, Similar regular arrangements are also observed in other ionic solids. The main characteristics of ionic crystals are @ Ionie sotids are very hard and brittle. (ii) They have very high melting and boiling points. (ii) They are poor conductors of elec- tricity and, therefore, are insulators in solid state. This is because in the solid state, the ions are not free to move about, However, in the molten state or when dissolved in water (aqueous solution), the ions become free to move about and they conduct electricity. (iv) They have high enthalpies of vaporisation. (0) Ioniccrystals are soluble in water and also in otherpolarsolvents. They areinaolubleorvery slightly soluble in non-polar solvents such as benzene, carbon tetrachloride, earbon disulphide. ‘The common examples of ionic erystals are : salts like NaCl, KNO,» LiF, Na,SOy ete, 3. Metallic solids or erystals In metaitic erystats, the constituertt particles are positive ions (called kernels) immersed in a sea of mobile electrons. This ig shown in Fig. 7. ‘Soa oF eran Fig. 7, Electron sea model for a metal. ‘The electrons in metallic crystals are mobile and are evenly spread throughout the crystal. Each metal atom contributes one or more electrons towards this, sea of mobile electrons. These free mobile electrons are responsible for high electrical and thermal conductivities of metals. When electric field is, applied, these electrons flow through the network of positive ions (called kernels). Similarly, when heat is, supplied to one portion of a metal, the thermal energy is uniformly spread throughout the crystal by free clectrons. The forees present between the metal ions are metallie bonds. The main characteristics of metallic crystals are G@ Metallic crystals may be hard as well as soft. (i) They aré good conductors of heat and elec- tricity. (ui) They nave Metallle Iustre and colour in. certain cases. (iv) They are malleable and ductile. Due to malleable nature, they can be beaten into sheets and drawn into wires. (0) They have moderate enthalpies of fusion. ‘The examples of metallic crystals are common, metals such as nickel, copper and alloys. 4, Covalent or network solids or erystals In covalent crystals, the constituent particles are non- ‘metal atoms which are linked to the adjacent atoms by covalent bonds throughout the erystal. In other ‘words, there is a continuous network of covalent bonds forming a giant three dimensional structure. They are also called giant molecules. Covalent bonds are strong and directional in nature and therefore, atoms in these solids are held very strongly at their positions. The important characteristics of covalent crystals are @ The covalent erystals are hard. Gi) They have extremely high melting points and may even decompose before melting. (ii) They are poor conduetors of electricity and. are insulators. ‘The common examples of covalent crystals are : diamond, carborundum (silicon carbide), quartz (Si0,), boron nitride (BN), etc. Diamondisa typical example of covalent crystal. It has a network structure consisting of a very large number of carbon atoms bonded to each other. Each carbon atom is bonded to four other earbon atoms by single covalent bonds. It is clear from Fig. 8 (a, that each earbon atom lies at the centre of a regular tetrahedron and the other four carbon atoms are present at the corners of the tetrahedron. Therefore, there isa three dimensional network of strong covalent, bonds. This makes dtamonct an extremely hard erystat with very high melting point (8843 K). Since ail the valence electrons of carbon are strongly held in carbon-carbon bonds, diamond is a poor conductor of electricity. Graphite is also a covalent solid but it is soft and a good conductor of electricity. Its exceptional WWW.JEI DKS.INEw properties are due to its typical structure as shown in Fig. 8 (6), 1415 0m +54 pm (@) Diamond (©) Graphite Fig. 8, Structure of (a) diamond and (®) graphite In graphite, carbon atomsare arranged in different layers consisting of hexagonal rings. In these layers, each carbon atom is covalently bonded to three other. neighbouring carbon atoms by single covalent bonds ‘The main characteristics of various types of eryatals are summed up in ‘Table 2. Table 2. Summary of the characteristies of various types of solids MODERN'S abe + OF CHEMISTRY-Xt in the same layer. The fourth valence electron of each carbon atom is present between different layers and is free to move about. Because of the presence of free electrons, graphite is a good conductor of electricity. Further, the different layers are separated by a large distance (340 pm), which is greaterthan carbon-carbon bond length. ‘This suggests that only weak van der ‘Waals forces are present between these layers and therefore, these layers can slide one over the other. This makes graphite a soft solid and a good solid lubricant. + Indiamond, each carbon atomis sp" hybridised. + In graphite, cach carbon atom is sp? > Graphite is a good conductor of electricity, though it is. a non-metal. 2 Graphiteisa covalent solid but itis soft and a good conductor of electricity. Its exceptional behaviours because ofits typical structnre having r- Brace, Rubidium Ionic ‘Metallic Molecular : P,Q,9,1,,P,, solid CO, Network (covalent) : Graphite, SiC, Si Amorphous : Plastics, CRYSTAL LATTICE OR SPACE LATTICE AND UNIT CELL The crystalline solids have definite orderly arrangement of their constittient particles in three dimensions. The positions of these particles in a crystal, relative to one another, are usually shown, by points. The arrangement of an infinite set of these points is called space lattice, The positions ‘which are occupied by the atoms, ions or molecules in the crystal lattice are called lattice points or lattice sites. ‘To understand space lattice, let us first learn about, ‘two dimensional lattices and then three dimensional lattices. A. ‘Dwo Dimensional Lattices A two dimensional lattice is @ regular arrangement of constituent partictes (atoms, ions or molecules) in a plane. A two dimensional pattern is shown in Fig. 9 (a) and the lattice is shown by points in Fig. 9). () Lattice points Fig. 9. Two dimensional pattern ‘There are five types of two dimensional lattices. These are, square, rectangular, parallelogram, thomhie and hexagonal lattice ax shawn in Fig 10 ahead. These differ in symmetry ofthe arrangement-of points, The hexagonal lattice has the most symmetrical arrangement of points white parallelogram lattice has the least symmetrical arrangement of points. (WWW.JEEBOOKS.INBAIS MODERN'S abe + OF CHEMISTRY-Xt (a) Square lattice __(b) Rectangular lattice Fig. 10, Five different two dimensional lattices. (©) Parallelogram, lattice (a) Rhombie lattice, Rectangular with interior point (e) Hexagonal lattice Because of the regular repeating arrangement of the points in a two dimensional lattice, we need only to describe a small part of the lattice (called motif) in order to specify it completely. For example, we select four points in two dimensional lattice and connect them to give a parallelogram. ‘This smallest part is known as unit cell. We can generate the complete lattice by repeatedly moving the unit cell in the direction of its edges by a distance equal to the cell edge as shown in Fig. 11. Lattice generated =i #4 Unit col Fig. 11. a) A unit coll (6) The completo lattied goriratod by repeatedly moving the unit cell in the direction of its call edges by distance equal to cell edge. ‘Thus, the unit cell gives the shape of the entire lattice. However, it may be noted that for any given lattice, the unit cells may be chosen in mang different. ways. This is because a lattice contains a very large number of atoms and numerous identical points may he found. Naturally, a question arises. “What are the characteristics of this unit cell?” The most convenient cell is the smallest unit cell which has the full symmetry of the lattice. For the square, rectangular and parallelogrant lattices, the unit cells chosen are the square, the rectangle and the parallelogram respectively. However, for the hexagonal lattice the unit cell is a rhombus with an angle of 60°, For the rhombic lattices, a rectangular unit cell ‘with an interior point is generally selected, A cell with an interior point is called a centered unit cell. The unit cells which do not contain any interior point are called primitive unit cells. Thus, we see that for describing a two dimensional lattice, we must specify the unit eell by the lengthe of the edges and the angles between them, Thus, the five two dimensional lattices and their unit cells are ‘Two Unit cell (a) Square 1AU Square (B) Rectanigular lattice | Rectangle (©) Parallelogram lattice | Parallelogram \d) Rhombic lattice Rectangular with an interior point (©) Hexagonal lattice | Rhombus with an angle of 60° B. Three Dimensional Crystal Lattice ‘Dhe crystalline solids have definite three dimensional arrangement of constituent particles (atoms, ions or molecules). If the three dimensional arrangement of constituent particles in a crystal is represented diagrammatically by depicting each particle by a point, the arrangement is ealled crystal lattice or space lattice, Thus, a erystal lattice is a regular arrangement of the constituent particles (atoms, ions or molecules) of a ‘crystalline solid in three dimensional space. A three dimensional crystal lattice is shown in Fig. 12. Space Lattice Showing Unit Call Fig. 12, Three dimensional lattice IWW.JEE‘SOLID STATES Like two dimensional lattice, if we carefully look a crystal lattice, it is observed that we ean select a group of lattice points ( a smallest three dimensional portion) which is repeated over and over again in the whole erystal lattice. This smallest repeating pattern notif) is called the unit cell. Thus, a unit cell may be defined as : the smaltest three dimensional repeating portion of a space lattice which when repeated over and again in different directions produces the complete crystal lattice. This smallest repeating pattern (unit cell) represents the shape of the entire crystal. We can generate the complete lattice by repeatedly moving the unit cell in the direction of its edges by a distance equal to the cell edge. In fact, the crystal may be considered to consist of an infinite number of unit cells. The unit cell in the above crystal lattice is shown by solid lines. Parameters of a Unit cell A unit cell is characterized by @ its dimensions (lengths) along the three edges as a, & and ¢. These edges may or ‘may not be mutually perpendicular. (i) angles ©, P and y between the pair of edges. ‘The angle 0. is between the edges 6 and c, angle i is between the edges c and a and angle 7 is between the edges a and b. Thus, a unit cell is characterized by six param- eters, a, b,c, a, B and . The parameters of a unit cell are shown in Fig, 18. The complete crystal lattice can be obtained by extending the unit cell in all the three directions. Fig. 12: Piamoters of unit cell Characteristics of a Crystal Lattice Let us sum up the characteristics of a crystal lattice. The following are the characteristics of a crystal lattice. (@ Each point in a erystal lattice is called lat- tice point or lattice site, (i) Bach point in a erystal lattice represents one constituent particle which may be an atom, a ‘molecule (group of atoms) or an ion. (ii) The three dimensional arrangement of lat tice points represents a crystal lattice (iv) Lattice points are joined by straight lines to bring out the geometry of the lattice. ‘Types of Unit Cells There are basically two types of unit cells constituting different erystal systems, These are : @ Primitive or simple unit cells (i) Non primitive or centred unit cells. (i) Primitive unit cells. These are unit cells whieh have points (or particles) only at the corners. ‘These are also called simple unit cells. Non-primitive or centred unit cells. ‘These are unit cells which» have points (or particles) at the corners as well as at some other positions. ‘The centred unit cells are of three types : (@) Face centred unit cells in which the points are present at the corners as well as at the centre of each face. (®) Body contred unit cells in which the points are present at all the corners as well as at the body centre of the unit cell. (c) End centred unit cells in which the points are present at all the corners and at the centre of two opposite faces. Seven Crystal Systems When a unit cell in a erystal lattice has lattice points only at its corners it is called a simple or primitive unit coll. In all, there are seven types of'simple or primitive unit cells among erystals. These unit cells are characterised by the axial lengths a, » and c and the angles 0, B and 7. These are called seven crystal systems or crystal habits. These are shown in Fig. 14. All erystals can be placed in one of these seven crystal systems, These are : 1, Cubic, All the three axes are of equal length and are at right angles to each other (a = 6 =<, all, angles = 90"), 2. Tetragonal. The three axes are at right angles, to each other but only the two axes are equal (a = #6, all angles = 90°). 8. Orthorhombie. Tt has three unequal axes which are at right angles to each other (a # 0 # ¢ alll angles = 00°). 4, Monoclinic. The three axes are of unequal length and two angles are of 90° (az 6 #.¢, two angles = 00° and one angle + 90°) 5, Hexagonal. It hag two edges of equal length, (a = 6) and two angles of 90” and one angle of 130° (a = 6c, two angles of 00° and one angle of 120°). 6, Rhombohedral or trigonal. The three axes are of equal length which are inclined at the same angle but the angle is not equal to 90° (a = 6 =, all, three angles equal but not equal to 90°). 7, Triclinic. The three axes are of unequal length, and all angles are different but none is perpendicular to any of the others (a #6 #6, all angles different and none equal to 90°) IWW.JEE S.INEi MODERN'S abe + OF CHEMISTRY-Xt ‘These seven crystal systems are shown in Fig. 14 and are summed up in Table 8. Te may be noted that among the seven erystal systems : = Cubio is the most symmetrical while + Triclinic is the most ‘unsymmetrical system, aroee ae Beye 90° Fig. 14, The seven erystal eystems. ‘The characteristics of the seven erystal systems are summed up in Table 8. ‘Table 8. The seven crystal systems. Syston Fossinie Variations Axial distances Axial Migles()/ ___Remuples Cubie Primitive = 90% NaCl, KCl, Zine blende, Cu, Ag eects a iro iecrao = 90" White tin, 80, TH0,, Ca80, Bodgceneed Onthorkombic Primitive @abae/, Waa Ra7=00" Rhombic ulphor, KNO,, POCO, peice! Base, ae Eadccated Monod Pintimn «fag 90,490" Monodini elghnr, PHCKO, ed one Na.80, 1080 | Hexagonal Primitive ze = 00°, y= 120" Graphite, Zn0, BoO, CaS, Rhombohedral or Trigonsl Primitive a=Beo = 7290 Caleite (CaCO,), NaNO,, cinnabar (gS), cunts Sb ee Primitive/Q e2b4e _azP#Y #90 CuS04SHL,0, K,Cr,0,, H,BO, tmay be noted that all crystals do nothave simple lattices fe, having lattice points only at the comers. In addition, there are some lattices which are different from the simple lattice. For example, if we consider a cubic aystem, which is simplest, of all these seven systems, itis observed that-a cube has three types of lattices. ‘Types of Cubic Lattices ‘There are three types of cubic unit cells or lattices. ‘These are: 1. Simple or Primitive. It has points at all the corners of the unit cell. A primitive cubic unit cell is shown in Fig. 15 (a). Ttconsists of one atom at each of the eight corners. 2. Body centred cubic unit cell (bee). It has points at ail the corners as well as at the body centre of the cube (Fig. 15 @®)). Itis labelled as dee. As shown in the figure, in a body centred cubic unit cell, there are eight atoms at the comers and one at the centre. 8. Face centred cubic unit cell (fee). In this, case, there are points at all the corners as.’ well as at the centre of each face. It is shown in Fig 15 (©). It is labelled as fee. As shown in the figure, it has eight atoms at the corners and six atoms’ at the centre of faces. Simple (Body centred 3 (© Face centred cubic: Atoms at of primitive euple: Atems at ‘hetocners ann centre ofeach fac, feubie: Atoms the comers and at ‘Atom 1,2,5,4,5, and Gare present ateight corners the body centre ot | QE 1% .@ | at the centres of ix faces (atom 5 only theeube.Atmtis | # 24, correspondsto atom atthe centre ot at the body centre ‘ack face and atom 6 corresponds ofthe eube, ° tthe contre of front thee.) Fig. 15, Three types of cubic lattices. VWW.JEE‘SOLID STATES Similarly, if we consider the other lattices, in addition to simple lattices for other systems, it is observed that there are 14 different types of space lattices. These are known as 14 Bravais lattices after the name of French mathematician who first described them. These are given in Fig. 10. Orthorhombie arbre =p y= 00" ‘Trielinie arbre a+ B+7200" Bot Primitive ‘The full hexagonal prism is shown, although the unit cell isjust the part shown in eolid lines. Gere Fig, 16. Unit cells of 14 Bravais lattices N WWW.JEIEn tmay be noted that there is another type of non-primitive ‘unit cell known as end centred unit cell. In this ense, there are points (or atoms) at all the corners and at the ‘centres af any two opposite faces, 2 There is no end eontzed cubie unit cell. 2 Only orthorhombic and monoclinic erystal systems Ihave end centred unit cells, TYPES OF CUBIC CRYSTALS AND NUMBER, OF ATOMS PER UNIT CELL We know that a crystal lattice is made up of a very large number of unit cells and every lattice point is occupied by one constituent particle (atom, molecule or ion). In different types of unit celle, the particles may be at the corners, at the body centre or, at the centre of faces. Since every unit cell in a crystalline solid is adjacent to other unit cells, most of the atoms (or constituent particles) are shared by neighbouring unit cells. As a result, only some portion of each atom belongs to a particular unit cell. For example, in all types of enbie cells, each corner atom belongs to eight adjacent unit cells as shown’ in Fig 17(@), four unit cells in the same layer and four unit cells of the upper layer. Therefore, only ‘USth of an atom (or molecule or ion) actually belongs toa particular unit cell Fig. 17a). A.comer atom in eubie unit cell is chared by 8 unit celle MODERN'S abe + OF CHEMISTRY-Xt Similarly, each face centred atom is shared by ‘two unit cells (shown in Fig. 176) and only 1/2 of an atom (or molecule or ion) belongs to a particular unit cell Fig. 17(6). A face @ntred atom in al cubic unit coll i¢ shared by two unit coll, An atom at the body centre of a unit cell is not shared by other unit cells and it completely belongs to the unit cell (Fig. 17¢). OQ Fig. 17(0). A body centred atom in ‘any cubie unit cell is not shared by any other unit cell ‘Thna, the contribution of each atom to the unit. cell is : 1 ni gi within the Forsimplicity assume thatthe constituent particle isan atom. The unit cell may be represented in three different ways. (a) Each small sphere in figure represents only the centre of the particle occupying that position and not its actual size. Such type of structures are called open structures, Tt is easier to follow the arrangement of particles in open structures [Fig. 18 (@)]- (®) Space filling representation of the unit cell with actual particle size (Fig. 18 (6)]. ‘This gives a more realistie picture showing how the partieles actually pack within the solid. (© Actual portion of different atoms present in a unit cell (Fig. 18 (©). IWW.JEE