es ko States of Matter : Gases and Liquids In this Chapter... + Factors Governing States of Matter * The Gaseous State ++ Ideal Gas and Ideal Gas Equation ‘+ Dalton’s Law of Partial Pressure + Deviation from Ideal Gas Behaviour There are three states of matter whi physical forms. These three forms of and gas. + Solid state A matter in solid state possesses a de (volume), a definite shape and a defi examples of solid are iro + Liquid state A matter in liquid state possesses a definite volume, a definite mass but nota definite shape. It acquires the shape of the container in which itis placed. It has a tendency to flow. Some common examples are water, oil, milk ete + Gaseous state A matter in gaseous state definite volume nor definite shape but it has a de Itacquires the shape and volume of the container. Some common examples are air, oxygen, carbon dioxide ete Factors Governing States of Matter State of'a matter is the result of combined effect of intermolecular forces and thermal energy, thus to u their role in deciding the state of matter understand the following terms. Intermolecular Forces Intermolecular forces are the forces of attraction and repulsion between interacting particles (atoms and molecules). These are erent I liquid te mass. Some common mion salt ete and generally affect the physical properties ical properties of matter the weak fo and some cher Attractive intermolecular forces are known as van der Waals’ forces. van der Waals’ forces vary considerably in magnitude, They include dispersion forces or London. forces, dipole-dipole forces and dipole-induced dipole forces. 1. Dispersion or London Forces + These forces exist in between neutral atoms and non-polar molecules, as in them electronic cloud is distributed symmetrically and hence have no dipole + The interaction energy of these forces is proportional to Lie", (where, ris the distance between two particles) 2. Dipole-Dipole Forces + These forces exists between dipole ends of polar molecules and are the strongest ofall van der Waals’ forces. + Dipole-dipole interaction energy between stationary polar molecules is proportional to 1/r? and that between, rotating polar molecules is proportional to1/r® where, r is distance between polar molecules.a tion «hicieron ake than cia Herbie ~ Dipole pipole Induced ee net iol perma os of the pole mek its electron os hut than Landon forces Hi st interactions ceules having rv hep: maces hosing eG whe moles Tack perm \duices dipole on clond Types of Bonding onding and types of bonding. ic. hydrogen bonding. There are two metalic bonding | Hydrogen Bon’ e-tipole int ly ene soaps hydrogen is bonded bondi formed (or su Jectronegative atom (like, N, O and F)) toa more electronega ie, HF 7 ion. A hydrogen HF ted Ener of hydrogen bond varies between 10 0100 kj mol-!, i. these are strong forces and play a key role in determining the structure and properties of many compounds like proteins, nucleic acid ete 2. Metallic Bonding son peculiar typeof bonding which holds the metal atoms [ether a metal crystals called metallic bonding Different models have been proposed to explain the nature of ‘metallic bonding, the two important of them are as follows Electron Sea Mode| Band Model metal lattice ha cording to this theory, a metal 25 a x valor ofatoms. The atomic orbitals OF these atone together due to vetry and similar nen to the formation of energy bands me arrangement af electrons inthe diferent ey, The arrange t : "9 determines the characteristic of a meta me | e band | “ Partially Overlapping | oT ae ot tne Distinction among metals, insulators aps Semiconcucge ‘The highest occupied energy band is called "he valence While the lowest unoccupied energy band 1 called the conduction band. site Properties of various elemental solids Can be exling SP present between the top of valence band and the Thermal Energy * The energy of a body which arises because ofthe motion [The intermolecular forces tenet to keep the molecules tog: but thermal energy tend eo keep them apart. Thus, these two compete and the competition between thee ‘wo (i.e. intermolecular forces and thermal energy) results three States of matter, The Gaseous State Cases have neither definite shape nor definite volume. The characterised by their high Ges laws are the Telationships between measurable prope Of gases. Let's discuss the various gas laws,Vo egse Term it | Chemistry xt Ye 4, Boyle's Law (Pressure Volume Rettionship ates thal at MLN HMM epee aye mn 1 te ; AM constant 7 p¥ constant WN, = PN 5 Seonstant 2. Charles’ Law (Temperature Volume Relationship) Acconing to this law. “the vo diveth proportional tothe abode of a civen mass ofa ers is in Ver [at constant pressure) V on = constant T vo or TT, 3, Gay-Lussac’s Law (Pressure-Temperature Relationship) According to this law, “at constant volume, the pressure ofa seven mass of a gas is directly proportional to ite absolote temperature he pel or 2 = constant (at constant V) T Ps Ps or aE 4. Avogadro's Law (Volume-Amount Relationship) + Itstates that, “equal volumes of all gases under same conditions of temperature and pressure contain equal number of molecules.” ie Ven (n=number of moles of gas) + The volume of one mole of a gas at STP is known as molar gas volume + The number of molecules in one mole of a gas has been determined as 6.022 x 10®, is known as Avogadro constant. deal Gas and Ideal Gas Equation aw and Avogadro's A gas that follows Boyle's law, Cha law strictly is culled an ideal gas, The combination of various yas laws such as Boyl Charles’ law and Avogadro's law leads to the ideal gas equation, At constant T and n; V 1/p (Boyle's law) eT (Charles’ law) law, At constant p and n; V At constant pand TV = n(Avosgado's law) On combining the shove three elations, we set vent on vea"t 4) Here, R= proportionality ennstant On rearranging the eqpiation (4), we get pV = nT where, n= w/M] The valies of R, are R= 8314 Pam'K ‘mol SOK ‘mol Latm K ‘mol = 820574 10 + Ideal sas eqquation is a relation hetween four variables and it describes the state of any gas, therefore it is also Called equation of st ‘The combine gas law is ziven by PM _ vy TT, and molar mass of a gaseous substance are related as, M=dRT/p Dalton’s Law of Partial Pressure It states that “the total pressure exerted by the mixture of non-reactive gases is equal to the sum of the partial pressure of each gas present in the mixture under the same conditions of T and V. Pana =P + Pa +P oo (At constant T and V) In terms of mole fraction, (p)=mole fraction % X Puy partial press Deviation from Ideal Gas Behaviour Real Gases 2ases that do not obey gas laws under all conditions of | pressures are called real gases. Most of the gases are real in nature, i. they follow gas laws only at very low pressures and high temperatures, Under such conditions the gas molecules are far apart, ie. hot in the influence of each other and hence, intermolecula forces of attraction are negligible. (i) pV vs p Plot * Plots are not straight, + Gases show deviation from ideal behaviour,mono 2. Volume Correction Volume available for compression total volume of the gas — volume of the = nb ley the volume occupied by one mole of the mo, of moles of the molecules on Vem where. bis and nis the number. 3. van der Waals’ Equation Putting the values of corrected pressure and volume in gas equation. we get where, a and b = van der Waals’ constants. value of whicg depend upon the nature of the gas. This equation is knows |p tonaigas qT] van der Waals’ equation. 5 Z Measurement of Deviation : Compressibility Factor a Tr + The extent of deviation shown by real gases from ideal Potot pressive vs volume for behaviour is measured in terms of compressibility facter ves ere coal pases (2 of ‘ons Ideal Behaviour * 2 defined asthe ratio of product of pV and nA ‘Two assumptions on which ideal gases are based are not valid ° ze at high pressure or low temperature, | oar ae mead - eizecton between ito «+ For ideal gas, Z = 1 at all temperatures and pressures. z ipa Sec tupcratureandressare are ters low pressure, all gases have Z~ 1 and behave as beh rata essuTe ideal gas. At high pressure, all gases have Z> 1 . eecissie a stags onaaghty a fs At intermediate pressure, most gases have Z< L comparison to the space occupied by the gas. + Gases show ideal behaviour when the volume occupied is The corect assumption at the conditions of high pressure large, because then the volume of the molecules can be sie oa neglected as comparison to volume of gas. + The forces of ettraction or repulsion between the molecules may not be negligible. te er + The volume occupied by the gas may be so small that the 14 3, volume occupied by the molecules may not be negligible. _ 12 nt, Corrections of Deviations s* ea 1. Pressure Correction oe “ So Peet = Pw + Ap ‘ aa 4p « (Number of particles per unit volume)* orp =(n/¥)? wi Q Visti ume chan he mumber of moe ofthe zs, ae eet Variation of compressibility factor for some gases 27 (where, a= constant) *+ The temperature at which the real gases behave ideall Pa “Prsny + ent) 2 over a wide range of pressure is called Boyle temperatur® ee or Boyle point, T,. It depends upon the nature of the #5 oe and is specific for a particular gas.he Chemical Thermodynamics In this Chapter... «Thermodynamic Terms « Heat and Work * Internal Energy « First Law of Thermodynamics * Enthalpy “Thermodynamics deals with the study of different energy transformations and the quantitative relationship between them Thermodynamic Terms «A system in thermodynamics refers to that part of universe in which observations are made and remaining universe constitutes the surroundings. « The wall that separate the system from the surroundings is called boundary « Depending upon the movement of matter or energy in or out of the system, the system can be classified as i) Open system In which energy and matter both can be -d with surroundings, e.g. reactants in an open (ii) Closed system In which only energy can be exchanged with surroundings, e.g hot water kept in closed container. (iii) Isolated system In which neither matter nor energy can be exchanged with surroundings, e.g. thermos flask. + Extensive properties are those properties which depend upon the quantity or size of matter, e.g, mass, volume, internal energy, enthalpy, heat capacity, ete. + Intensive properties are those which do not depend upon the quantity or size of matter, e.g. pressure, temperature, concentration, viscosity, etc « Thermochemical Equation « Spontaneity Entropy «Second Law Thermodynamics ‘e Third Law of Thermodynamics + The state of a system is described by its measurable .p ete., of the system. properties such as T, V + These properties of the system are called state varia state functions as their values depends upon these, system and not on the path followed. + The variables, values of which are affected by the path followed are called path functions, e.g. work( Wheat Thermodynamic Process The state of a system can be changed via thermodynamic process. These processes are of the following types + Adiabatic process The process in which system das exchange heat with its surrounding is called adiabatic process. For adiabatic process, dq = Oand AU=U,-l? + Isothermal process This process is carried out at const temperature, i. dT = Oand thus, dE = 0. + Isobaric process In this process, change of state is br! about at constant pressure, ie. dp = 0 ochoric process In this process, volume of thes ant, ie. dV + Cyclic process When a system has undergone different states and finally returns to its initial stte™ Process is called cyclie process dE or dU = O.and dH =0 a numbet!CBSE Term I! | Chemistry XI + Reversible process A system where change takes phhee Reston hw ane thevetn of whih a pov be reversed by infinitesimal change in the state of the eeeversiblep Weep ese tat pve cael ewes ysl 16 An irreversible process is one in changes in variables Heat and Work «+ Heat is defined as the quantity of energy which flows hetween system and sur temperature difference. Tis a path fiction, nmings on acconnt of « When work of the system involves gaseous substances and there is a difference of pressure hetween system and. surroundings. this type of work is referred as pressure-volume work «+ Ifmechanical work is done in a single step, W=-p, AV or W=-pa(V, -V,) Pou (Vy «+ The negative sign (-ve) represents the work is done by the system in case of expansion. In case of compression, the sign should be positive (+ve). «+ Ifthe pressure changes in number of steps, then work done on the gas will be given as, W=-2pav «+ Ifpressure is not constant at each stage of compression and, the process is reversible isothermal, then work done is given as Woe == Pw AV or w, isi ~ 2.308 nBT log or Ww, ~ 2.303 nT log P+ Py where, n = number of moles of gas Re=gasconstant, — T emperature (in K) V, =final volume V, =initial volume, initial pressure, p, = final pressure * Work done is maximum in case of reversible isothermal expansion of a gas. * Incase of free expansion, a gas expands under vacuum (a = 0). In this case, Wis also zero, ie. no work is done. Internal Energy In thermodynamics, energy of the system is called internal energy (E oF U. It isa state function. Its the sum of ical, electrical, mechanical or any other form of energy anyone may think of, First Law of Thermodynamics mics, the energy ean According, to first law of thermody rat ee paither be created nor be destroyed but can be into one form to another called Law of conser 1 expression of first law of thermodynamics srvation of energy. That's why, itisa id The is given as, nathernatical AU=q+W where, AU =change in internal energy = heat consumed W = work done on the system - Ifthere is no heat transfer or work done (ie. in an isolated system), AU will be zero. ; aa ried out at constant volume, then AU = Gy- at constant volume). Ifa process is (Here, q denotes heat that is supplied For isothermal irreversible q=-W and for isothermal reversible change. q= 7 W= 2303 nRT log ‘Sign Convention + q is +ve=heat is supplied to the system. «+ q is ve =heat is lost by the system. + Wis +ve= work is done on the system. + Wis —ve =work is done by the system «+ AU is—ve=energy transfer from system to surrounding, + AU is +ve = energy transfer from surrounding to system. Enthalpy The total heat content of a system at constant pressure is called enthalpy of the system. Tt isa state functic 1 and is given by the expression (AH = AU + pAV. Note AH = q,, heat absorbed by the system at constant pressure. + Atconstant volume; AU=q,, ie. heat supplied at constant volume. + AH =~ vefor an exothermic reaction and AH = + ve for an endothermic reaction, + For solidls and liquids, AH and AU is insignificant but for gases, if pressure and temperature remain constant, then pAV = An, RT 1 =N, ~My umber of moles of gaseous product and ny is total the number of moles of gaseous product; Here, where, n, is the total An, is the total number of moles of gaseous product minu that of reactantsQV Moreover “This equation is helpful for c An= AU + An, RT and slewlating AH from AU treme n= 0. then A= AU ‘ease An, <0. then A < AU case MI An, > 0. then AH > AU. Thermochemical Equation chemical equ cdi A thermochemical equation isa balance inwhic he ae 017 ao mentioned on: g) —+ 2CO, (e)+ HO EHD OO EN = = 1367 ku/0 Negative (ve sign indicates, it isan exothermic reaction pa pore related to thermochemical equations are as follows ; + Negative A, H” means the reaction is exothermic and positive A, ]* means the reaction is endothermic. + The coefficients of different substances in a balanced thermochemical equation show only their number of moles (never molecules) involved in that reaction. of AH is also reversed but + On reversing a reaction, the si its magnitude remain the same. + Enthalpy is an extensive property, thus ifa thermochemical equation is multiplied or divided by an integer, n, the value of 4H” is also multiplied or divided by the integer, n Enthalpy Change of a Reaction, A,H Itis the heat change that accommpanies a chemical reaction represented by a balanced chemical equation. 4,H=Ex,H, ~ZyHy where, x, and y, = stoichiometric coefficients of products and reactants respectively in a balanced equation. H, = enthalpy of formation of products H, = enthalpy of formation of reactants * Molar enthalpy change (11, )is the enthalpy change when quantities (in moles) of reactants have reacted completely as indicated by the balanced chemical equation, eg. CH, (8) +20,(g) —9 CO, (g) + 2H, Q{) 4,H=[H, (CO, (g)) + 2H,(H,0()))] ~ 1, (CH, (g)) + 2H, (CO, (g))] * The enthalpy change occurving during a reaction when all the involved substances are in thet their standard states, j called the standard enthalpy of the reaction, * The purest and most stable fa € form of a substance: specified temperature is called itg standard state ‘dat standard state of solid iron at 500 K is pure iron at 1 bee ne far. ea BSE Term 1 s Neeser ‘ \ “Hess's 4 . changes for Diff standard Bnthatpy Chan erent, ition EathalPy Examples spy offasion — TOW) — 1,9, H,00— thoy ip Necordi Ol) aceompa «+ Enthalpy of 1,06) — Hoi) com sublimation _ - Ne «= Enthalpy of 28 — 1 0%, forration rnthalpy of Hg) — 2H(2) atomisation (In this case enthalpy of 4y, "eam be atomisation is same asthe bond dissociation exttay) Jorn Na(s) —> Na(g) Ttis a (Here, enthalpy of proce ation is same ast summ of sublimation enthalyy tat ~ Born. HX(g) — Hg) + x(q) > of Na + Lattice enthalpy KCI(s) —> "(H+ cr) >> a _ « ‘ «© Enthalpy of A(s)+ H,O(excess) 54, - solution is spor “A spor ee ee only b — ror + Enthalpy of 13 4 i Ria. Eathalpy of CHE) + FT Ole)— 4 Aten _ 4C0,(g)+5H,00) poets . Standard enthalpy CuSO ,(s)+5H,0(!) sy aes on ration CuSO, 5H0() produ * Standard enthalpy H*(aq)+OH(aq)—> Aft Te of neutralisation HO) ‘ * Standard enthalpy KI (200 11,0) —> To of dilution KCI GoOly, ° * Standard enthalpy CH,COOH(aq)—= Se _ of ionisation CH,COO (ag) +H (# a a Note Enthalpy change of reaction can ako be lt enthalpy as Decre follow A HP=y, occ orcas ~ DB! _ 3s, thoi” TESA TH scutesCBSE Term I! | Chemistry x1 Hess's Law of Constant Heat Summation According to this ie. “the total heat chance! AH accompanying. chemical reaction i the seme ehether the Feat takes place fn ont r mone spe > Forareaction, A ‘ 6 . al 7 am aw : | Itcan be represented as. . AH= AH, + AH, + An, + Born-Haber Cycle + Itisan approach to calculate energy involved duringa process and is hased on the Hess's Law of constant heat summation + Lattice enthalpy can he indirectly calculated by Born-Haber evele. It can be explained by using an example of NaCl as shown below air Nats) + 1/2 Clz(@) —“" Na+ cr (s) | 12 ogg [ss [12200 Siaie AP Neglt Clg) = cr ie) , sir Nate) Na’ (g) Spontaneity + A spontaneous process is an irreversible process and may only be reversed by some external agency, e.g, burning of carbon giving CO, heat flow, rolling ball, gas flow ete, + A tendency to attain the minimum energy, i.e. decrease in ‘energy is responsible for the spontaneity or feasibility of a reaction + The enthalpy diagram for an exothermic reaction, showing the decrease in enthalpy when reactants are converted into products is shown below Total enthalpy Hp of reactants sn A Net heat evolved Tat entapy| ___] inne reaction of products [7% Producis Reaction coordinates Enthalpy diagram for exothermic reactions * Decrease in energy, the crite following limitation, Reacianis ia for spontaneity has the In case of endothermic reactions, AH is. increases but there are wre spontaneous, ‘ mle reactions tha for sch reaetions # showen below several oni + The enthalpy diagram Reactants Products: Enthalpy dhagram for endothermic reactions Entropy Another thermodynamic function. entropy is introduced for determining spontaneous reaction. It is the measure of degree of randomness or disorderness in an isolated system and is represented by the symbol (S). ess, higher is the entropy. The greater the degree of rand) Its also a state fimnetion Entropy Change in Reversible Process Consider an isothermal reversible process. let the system absorbs q amount of heat from surroundings at temperature, T. The increase in the entropy of the system will be Surroundings lose the same amount of heat at the same temperature. The decrease in the entropy of the surroundings will be AS, — ann - Total change in entropy of the process = entropy change in system + entropy change in surroundings antag = Suan + AS, ~420 T When the reversible process is aliabatic, there will be no heat exchange between system and surroundings, ive. q=0 eam =O a) Entropy Change in Irreversible Processes Consider a system at higher temperature f, and its rowdings at lower temperature Tq amount of heat goes sibly from system to surroundings. invesag Sa ASan = 25am + MS 29 jt 77 re oF But n-nets Phase Transition ence, entropy nerease During a Entropy Crane from one state to another is called +The chan oF entropy changes at the time of I hase transition ge can be SSceng of substance, where, Ty, = melting poi entropy ofthe liquid, 5, MSaperoe where, T; = boiling point of substance Similarly, AS. sense = where, T,, = sublimation temperature. - + The totalentropy change for the spontaneous process is given as, MSpuat = BS yg + AS ure > O + The change in entropy at equilibrium, ie. AS= 0. Second Law of Thermodynamics The second law of thermodynamics can be stated as + whenever @ spontaneous process takes place, it is always accompanied by an increase in total entropy of the universe. In the above statement, the term universe means the system and the surroundings. Thus, AS... + itis impossible to take heat from a hotter reservoir and completely convert into work by a cyclic process without transferring a part of heat to a cooler reservoir. This statement of second law is called Kelvin’s statement. The above statements (i.e. the second law) in simplified form can be stated as “for a spontaneous process in an isolated system, the change in entropy is positive.” ibbs Energy and Spontaneity ibbs function or Gibbs energy is introduced because crease in enthalpy and increase in entropy cannot termine the spontaneity of the reaction, s given as, AG=AH-TAS [Cibbs Helmholtz equation} ere, AG =change in Gibbs energy AH = change in enthalpy and AS change in entropy ‘an extensive property and a state function, standard Free Energy Change et encanta 8 rey pines the standard ae Ph converted gy char werssy ofthe standard free energy of formation of products ‘Sum of the standard frog, - ney [fnmaven of reactants Wy = Ey Gipeaavry EAs es E aneity through Gibbs free ep, a ‘The criteria of spontaneity throug] eter, follows ven temperature and pressure. w (i) IPAGis negative, (< 0) the Process is spontanes, Wi If AGis postive > Os the process sno SPoMtaney, (ii) Gis zero, the process is in equilibrium yye © ‘The various conditions in which a reaction occur spontaneously are tabulated below Effect of Temperature on Spontaneity of React A,H® 48° 4,G° Description - = + -(atall T) Reaction is spontaneousatay temperature. - = (atlowT) Reaction is spontancousathy temperature, = +(athighT) Reaction is non-spontaneony high temperature +(atlowT) Reaction is non-spontaneassh + + temperature, + + ~(athighT) Reaction is spontaneousathid EX temperature. ext a Lt + = + (atall7) Reaction is non-spontaeasil 4 temperature Third Law of Thermodynamics According to third law of thermodynamics, “the entrop perfectly crystalline substance approaches zero as the Ex absolute zero of temperature is approached”. syst It forms the basis from which entropies at other cha temperatures can be measured, sl Lim S=0 rao Note In case of CO and NO molecules in solid sate thee # ‘andomness even at 0 K due to their dipole moet Entropy in such cases is not zero even at 0 K-CHAPTER 03 Equilibrium \ In this Chapter... + Equilibrium in Physical Processes + Equilibrium in Chemical Processes + Le-Chatelier’s Principle ‘slonic Equilibrium ‘* Buffer Solutions ‘Solubility and Solubility Product Solid-Vapour Equilibrium wersible reaction, the point at which there is no further Inare so areyty concentration of reactants and products is alled Certain solids on heating directly change fom solid to vapour equilibrium state state (sublimation) {tinay be represented by eer ant H,O() =H, Ovap.) & Behe ‘the misture of reactants and proxlucts in the equilibrium General Characteristics of Equilibria state is called an equilibrium mixture. The concept of equilibrium is applicable for both physical and chemical Involving Physical Processes Some important characteristics of physical equilibrium are as follows Equilibrium in Physical Processes rquiitsium is posible only naclosed aston agen A physical equilibrium is a state at which two phases of temperature compound ean co-exist and an equilibrium is established «All the measurable properties remain constant. Irencen these two states. Physical equbrivm may be «+ Both the opposing processes oceur at the same rate and biained by the following phase transformation processes. Poa cRinamnic but stable condition, «+ ‘The physical equilibrium is characterised by constant value of one of its parameter (Such as melting point) ata given. Teo(s) = Water(l) Rate of melting of ice = rate of freezing of water temperature. Liquid-Vapour Equilibrium Equilibria in Chemical Processes H,O() =H, O(wap) The equilibrium that involves only chemical change is il equilibrium, Its also called dynamic called chem equilibrium, fate of condensation of water Tate of evaporation of water ‘vapoursThe variation of concentration of reactants and P! reversible reaction can be seen as sroducts in # Time —> Variation of concentration of reactants and products Note Use of isotope (deuterium) in the equilibrium in whic ‘equal and there is no net change in composition. Characteristics of Chemical Equilibrium n are as The important characteristics of chemical equilib follows + Ata given temperature, the measurable properties like pressure, concentration, density or colour remain constant. + Chemical equilibrium can be attained from either side. + Chemical equilibrium remains unaffected if the reaction occurs in the presence ofa catalyst. However, equilibrium can be attained in a lesser time by the use of a catalyst cei ee tind nd even eacONs aE fyytion f Mass Action ig law, ‘the rate at which a subse its active mass and hence the ra itt is proportional to the product ct Law" ding to thi retinal € reaction i reactants f the ret ass means the Molar Concent c, It is expressed by Jes per litre ssed by ene For ae nase of, is represented as (H, Ths acne pure solids and Higuids ae tay Active masses Gneentation (oF density) remain gy cause thet reaction. This is because Gibbs’ yn to dig are defined ult en pre solid ae tine pressure of system changes rand as the P Gil 1.00 bar ain constant. oe ‘Acco! proporti chemical masses ofthe re The term active masses of Law of Chemical Equilibria and Equilibrium Constant Law of chemical equilibrium states that, the value g dividing the product of concentration of products respective stoichiometric coefficient in a balanced equation by the product of concentration of reactany their individual stoichiometric coefficients is consty Fora reaction, aA+bB =" oC +dD; K, = (Cl (0) [al [aj where, [A], [B], [C] and [D] are molar concentration, + Chemical equilibrium is dynamic in nature (ive. the reaction and Dat equilibrium and K,, is equilibrium constan. does not stop but continues in both the directions with same of K, is mol L* speed). + The chemical equilibrium will continue indefinitely if the conditions such as temperature and concentration are not changed + The magnitude of such quantities at any stage indicates the extent to which the reaction has proceeded before reaching, equilibrium. Types of Chemical Equilibrium Depending upon the number of phases, chemical equilibrium can be of following two types. (@ Homogeneous Equilibrium If all the reactants and products of an equilibrium reaction are inthe same phase, the equilibrium is called homogeneous equilibrium, eg H,(g) +1, (g) = 2H (g) (ii) Heterogeneous Equilibrium Ifall the reactants and Products ofan equilibrium reaction are not inthe sam phase; i.e. they are present in two or more phases. then the equilibrium is called heterogeneous equilibrium. eg. MgC, (s) —=MgO(a) +O, () 1,00 =H, 0(g) Note The above equilibrium equation is also known as lay action The characteristics of equilibrium constant areas fl + The value of equilibrium constant for a particulars is always constant and depends only upon the tem of a reaction. + If the reaction is reversed, the value of equilibriun constant is reversed, i.e. K/ c * Ifan equation is divided by a factor of ‘r’, the new equilibrium constant is the nth root of the previous! ie. K’, =(K,)!", * I the equation is multiplied by a factor of 1, thet equilibrium constant is nth root of the previous ¥# ie. K’, =(K,)". Applications of Equilibrium Constatl The value of equilibrium constant i helpful in 3" Predicting the Extent of Reaction vt TEK, > 10°, Products predominates over ¥ Teaction proceeds completion. TK. < 10°, then reactants predominates oerF* and reaction Proceeds rarely,a " cease Term i!| Chemistry X! _ stn the range 10°10 10°, appreciable concentrations (HER J estan and proves represent ng the Direction of a Reaction reaction in equilibrium. reaction proceeds in forward direction. tion proceeds in backward direction, * eke Toke Top Ker (Qi reaction quotient. Her. Equilibrium Constant in Gaseous Systems wenallte products and reactants ofa reaction aren Net state. their concentration is expressed in term of expresses: Hin the allowing ention @A+DB==cC +dD ‘the partial pressure of A, B, Cand Dare p,, Pq. Pe and Py respectively, then, the expression of equilibrium constant, f bghenes K, =2278 ve PicPh . Relation between K, and K, L Fora gaseous phase reaction, ‘ ( nA+n,B=mC +m,D According to law of mass action, Ro Paps” | Interms of molar concentration, i x, -les*ID1" tap By" K, =K.(RT)™ then K, = Ke ve then K, > Ke ve then K, 1>K>1 Therefore, forward reaction is spontaneous. + LAG? >0;0%""" <1>K<1 ‘Therefore, backward reaction is spontaneous. Factors Affecting Equilibria (Le-Chatelier's Principle) According to Le-Chatelier’s principle, if any of the factors the equilibrium condition of a system is hat that deter changed, the system will move in such a direction, so t effect of the change is reduced or nullified or opposed. Different factors affecting equilibrium are as follows (i) Effect of Concentration Change Change in the concentration of either reactant(s) or product(s), shift the reaction in such a direction in which the effect of change is minimised or nullified. (ii) Effect of Pressure Change Increase in pressure, shifts the equilibrium in that direction, where the number of moles of the gas or pressure decreases and vice-versa. (iii) Effect of Temperature Change High temperature favours endothermic reaction and low temperature favours exothermic reaction. (iv) Effect of Inert gas Addition At constant volume, there is no effect of addition of inert gas. While, at constant pressure, when inert gas is added, reaction goes in the direction in which there is an increase in the number of moles of the gases. (¥) Effect of Catalyst A catalyst increases the rate of forward reaction as well as the backward reaction, so it does not effect the equilibrium and equilibrium constant. lonic Equilibrium Equilibria that involve ions only are studied under different class called ionic equilibrium. Michael Faraday classified the substances into two categories based on the ability to conduct electricity, i. electrolytes and non-electrolytes. Degree of dissociation/lonisation An electrolyte AB ionises as, AB A’ +B" The equilibrium established between AB and A’ and B™ is, called ionic equilibrium. The fraction of total number ofee rolyte dissol led sociation is cal molec the degree of ion number total number of molecules of elect Thus, c= ised amount of electrolyte io initial amount Degree of ionisation (ct) increases with dilution and reaches egree of ionisation (o to maximum limit (unity) at infinite dilution for weak cBs natn a dey 0 he Te se vee a es stn at scivtes. Such substance cond water, are € rectriity i E ion, the elec lution. Depending upon the cous sol trolstes ae further clssifed ing yf classes by Fay in at A1C oni Strong cir weak electrolytes are only ml completely, whl dissociated, - sand Bases Concept Acids _Bs : cl + Ch: NaOH — + OH nit , ease H” Furnish/release OH” ions: ES ; ; ‘in i ™ Weak acids HF, CH,;COOH a Strong bases NaOH, KOH, Ba(OH), Weak bases NH,OH, Al(OH), = : a - ——~ ane cot apairo + OH —> H,0 i Donate a pair of electrons H Ras Lewis concept Accept a pair of a eae ig compaunis compounels d-orbitals) n HH, , OH™ : ‘Addproton Brot Aclaptondonr Baie atone Note The acid-base pair which dtr NH(ag)+H,0() = NH;+(aq)+OH-(ag) Base cd CConugste Conjugate ' ‘id tase Tosspion by a proton are said to form a Bronsted acid isa strong acid, lonisation Constant of Acids and Bases For acid and bases, follows H,SO , (ag) =H" (44) +80; (aq) = onisation constant can be determined as (aq) +805 (aq); k,, =H" 80%] [H,S0,] Similarly, forthe bas ike NaOH, the ionisation constant can be written as NaOH(aq) —*Na* + 08-(aq), K, = !Na’ OH] - [NaOH] lonic Product of Water The ionisation co nstant of water and its ionic Product is F 1 then its conjugate base is weak and vice-versa, lonisation Consta: Conjugate acid-base pair, The pH Scale PH =~log[H*] IfDH <7, acidic solutio solution, "PH = 7 neutral, if pH > 7, basic’ PK, = pOH+ pPH=14 ints of Weak Acids ‘or a reaction, “HS ag) + iv@ +. l= a)ase crew) fa y. 4 ot term Il | i xr Factors Affecting Acid Strength flected by two main (WI ]_ca In genera the strength of un at (HX) l-a factors. () Im a grou of the periodic table, the acidic stremath is A bond. On moving down z(t -02) = Tand degree of ionisation is given as face [ a 1 decided hy the stremuth of H down 2 ae u Tenuta ence the tendency to ive a proton increases. | ensionless quantity. T ive acidic strength inereases adimen: W Bronger the acid ie increases H) Reiger isthe acid te ae a ronisation Constant of Weak Base clBrecHl, Fora reaction . - nth increases MOH(aq)—* M* (aq) + OW (aq) Similarly, H,O-<¢H,S 0.1M 0.01 M < Solubility < 0.1M A solid salt ofthe g solut 'Sineg represented by the equ A,B, (8) = xA"" (aq) + yB" (a9). AP TTBET! =(29)' (ys =x'yt8"”? Kyity? =(Ky ity" where, K., is called the solubility product, Ke sen Applications of K,, The value of Q (ionic Peter re ic product) and K,, (solubility) product are predicting, whether a precipitate is formed or not. Lose term) o tion takes place. ” then no precipitation takes place * is at equilibrium, K,,» the reaction i Effect of pH on Solubility The solubility of salts of weak acids like phosphate, with decrease in pH as at lower pH. the anion getg protonated and, hence its concentration decreases Common lon Effect The decreasein the ionisation of a weak electrolytety, presence of acommon ion from a strong electrolyte isa ‘commonion effect. eg. lonisation of a weak acid (HA) decreases in the presence of a strong acid such as HCI becauseH’ ax common ion combines with A” toformHA It is usedin purification of common sat (b) in qualitative analysis WW salting out of soap. 2 inica lement, : ck E cn s-Blo ae incre @) ' t 4 i i ter. in this Chap ji Metals — \ «+ Group 1Elements:Alkal Group 2 Elements: AlKeInS 1 « Anamolous behaviour of Berylliu a (iii) F h isation Enthalpy The elements in which the last electron enters the lonisati nistion enthalpies and it decree ‘outermost s-orbital are called s-block elements. Sion + They te Tow i iy) F elements (alkali metals) and group 2 elements (alkaline down the group. ; a k cath metals) constitute sblock elements « This s because the effect of increasing size outweigh increasing nuclear charge. : Group 1 Elements : Alkali Metals " : Li, Na, K, Rb, Cs and Fr belong to alkali earth metals. Hydration Enthalpy 7 They are collectively known as alkali metals because Hydration enthalpy of these metal ions decreases with ing P i fey to — ‘on reaction with water which are tonic size, Hence, the order for increasing hydration enthdy ) The general electronic configuration is ne! Li" > Na* > K* > Rb* > Cs" 7 Occurrence Metallic Character ( * They are never ound in free state as they are highly Thevare the most electropositive elements in the period: reactive, and their metallic character i icte tt i * Sodium and potassium are the most ubundant tolose valence electron i tr al j aupesws alkali metals in the earth's crust. : iain h * Francia, the longest lived isotope wi half. of sical Properties i 21 minutes occurs only in traces, * They are si ‘hi p a“ ve silvery whit : Atomic and lonic Radii + The have tow density ot an light metals t They have the largest mae * The melting nf ‘nsity which increases down the group Tl | a 1 a ili ‘ - Foren estima ee PORE Pont ofthe ala mete) hoving down the group. T nate is ond i istic sltieetsioe Mateus” agg edie inca increases resulting in decreased yng ut “HABE also materi colour w stanton bound an re given as valence electrons te Offlame, 88 excited to high: energy levels by ba!r germ Il | Chemistry XI ve No Kk Rh Gs | ar ceimsonred Yellow Violet Red violet le J gm 6708 SMO 7885 7800 ASS | chemical Properties Mik metal are hichltrvactive due to thet lange ‘Theat nication enthalpy. The reactivity of these metals and imtes down the group. tivity Towards Air On combustion lithium forms 0 sodium forms peroxide (NaO; Dand the ather metals form superoxides (KO, RbOs, Cs) 4Li+O;— 2Li,0 (monoxide) Na+0;—+ NazO (peroxide) M+O—+ MOg (superoxides)(.M =K, Rb.Cs) ¢ stability of peroxides and superoxides increases with Fe atomic numberof alee Hivity Towards Water Alkali metals react with Bese rm metal hydroxide and dihydreoes, 2M + 2H;0—> 2M* + 20H” + HT Because oftheir high reactivity towards air and water, alla metals are kept in kerosene oil ii) Reactivity Towards Dihydrogen All the alkali metal hydrides are ionic solids with high melting points. 2M+H, —3 2M" H- liv) Reactivity Towards Halogens Alkali metals react vigorously with halogens to form ionic halides M*X~ Lithium halides are somewhat covalent due to small size and high polarisation of Li. \ Reducing Nature It depends upon the value of standard electrode potential or standard reduction electrode potential (E° or E°red). Higher the negative value of E®, more will be the reducing nature. Electrode potential mainly depends upon the following three factors, i. (i Li(s) —> Li(g); Sublimation enthalpy (i) Lig) —> Lit(g) +e"; fonisation enthalpy (i) Li*(g) + HO —> Li*(aq) senthalpy of hydration With the small size of its ion, lithium has the highest hydration enthalpy. However, ionisation enthalpy of Li is highest among alkali metals but hydration enthalpy Predominates over ionisation enthalpy. Therefore, lithium is the strongest reducing agent in #queous solution mainly because of its high enthalpy of hydration, Among other elements of the ‘group, Eis least negative sodium and hence, sodium has the least reducing tendency, Jmmonia The solution of alkali metals a viramvgnetie and has high (0) Solution in 1 fn Hquid ammonia is: blue reducing eapaetty This is hecanise of the presence of solvated electrons »[M (NH) 1° + fe(NH ay) param M+ (r+ yNHy «d solution, the blue colour changes to In concentra ranetic Uses of Alkali Metals seful alloys, in thermonuclear + Li metal is used to: make ake electrochemical cells reactions, to a coolant in fast breeder nuclear reactors. + Liquid Na is used + KOH is used as a fertilizer + Csis used in devising photoelectric cells, General Characteristics of the Compounds of the Alkali Metals Most of the compounds of alkali metals are ionic in nature. The general characteristics of some of these compounds are discussed below Oxides and Hydroxides + The stability of peroxides and superoxides of alkali metals inereases down the group. Order of solubility Normal oxides > peroxides > superoxides + Alkali metal oxides hydrolysed with water to give alkali metal hydroxides. M,0+H,O —>2M* +20H™ Halides + All metal chlorides of group-I elements are ionic except LiCl, which is covalent in nature. + The order of melting and boiling point of metal halides is ‘MF > MCI > MBr > MI. + All the halides are water soluble, The low solubility of LiF in water is due to high lattice enthalpy, whereas low solubility of CsI is due to smaller hydration enthalpy. Salts of Oxoacids + The alkali metals form salts with all the oxo-acids which are generally soluble in water and thermally stable, Their carbonates and in most cases the hydrogen carbonate are also highly stable to heat * As the electropositive character increases down the group, the stability of the alkali metal carbonates and hydrogen carbonates also increases down the group, + Lithium carbonate (Lig CO g) is thermally unstable and leads to the formation of more stable Lig and CO gon heating, Its hydrogen carbonate does not exist as solid.mg Jd ydroxides are mich les. fa . et on des decompose om heating Ny, heir hy —4+1i,0+ jour of Lithium f 2LiOH > Li,0+H,6 Anomalous Behaviour o1 ation A . Due to smallest size of lithium, it shows very high ions Mg (OH)2 —>Mg0 + H,9 Heo salle! io ih, shows ney ih “nano, enthalpy and highest clectronet TT garn ringnitrates of Land Me docompia, & Italso shows following properties which di + On heating Terogen dioxide and oxygen, other alkali metals ficbond.* Injgture oF Bs 504 4LINOg 21120 +4No, | + Itis harder than other alkali metals due to stron ‘> form ‘+ Unlike other alkali metals, it reacts with nitrogen” tisco sluble in water, * gC, LiF, L480 and LiPOg are lable while the corresponding salts of other alkali me Group 2 El 2 +9, A \ 2Mg(NO3)2 —> 2MgO+ 4 No ; lements : Alkaling i Soluble in wate soluble in water re + Its melting and boiling points are higher than that Earth Metals alkali metals, tamonggll sr, Baand Ra belong to group I, 7p, + Itis least reactive but strongest reducing agen Be, Mi, Ca ie alkaline earth metals bee ® oe metal collective Fyydroxides are alkaline in nature ang tae earth's crust whereas *+ LiCl is deliquescent and erystallises as LiCl-2H 0, wher ides configuration is ns? othe ala metal chlorides do not frm bya. oats are found in the * Lilie other alla metal doesnot form ethynide on ecto reaction with ethyne. " . + LiNO, on heating gives LigO, while other alkali metal ‘Atomic and lonic Radii + They have smaller atomic and ionic radi than hy, nitrates give nitrites. . * Bicarbonates and carbonates of Li are unstable towards covespandingalal metals becais of nent heat and decomposes to give LisO. charge Points of Similarities between + Within the group, the atomic and ionic radi increase in atomic number due to addition ofa Lithium and Magnesium Lithium resembles magnesium in many ofits properties. due {2 hei lost similar atomic and ionic adias shown below 1 tion Enthaly py electrons in succeeding element ive. shows diagonal relationship. ail a! + They have low ionisation enthalpies due to lange sx om a on) 18pm: Mg ie atoms but larger than that of alkali metals. | ened om) =76pm; Mg! = 72pm *+ Second ionisation enthalpy is more than alkal met alkali metals acquire noble gas configuration whi: These properties are as follows Configuration becomes ns! after losing one elect + Both Li and Mg are harder and lighter than the other metals in their respective grou, pe are higher than the other nenters fae a * Dov the group, the ionisation enthalpy decreas groups. Hydration Enthalpy + Both decompose water slowly to liberate hydrogen, Hydration enthalpy of these metal ions decreases wit ( 2Li+2H,O—> 2LiOH +H, increase in ionic size, Mg + 2H;0—+Mg (OH), +H, Be™* > Mg? 5 cy2+ > Sr? > Ba” * Both form only monoxide when heated in presence of jhe hydration enthalpies of alkaline earth metal an Grvgen, The monoxides are less soluble in waterandd not | I Combine with excess of onygen to form siperode°'°* lO than those of alkali metal tone 41i+0, — 21,0 Physical Properties 2Mg +0, —+2Mgo * Alkaling . + Cutts oft ine ‘eammportorheat ow relatveh a metals are silvery white Justrous ad oxide and carbon dioxide gas ees Thema ot eutharder than the aalmetis * melting and boiling Points are higher that “orresponding alkali metals, 4 LizCO; “41,04 Oe * Melting and haem ° iffere ss Polling point trend is not regula MgCO; 45 Mp0 4.c0, a 2 erent ory; * Ther bicarbonate do not exist in sid * The clectry St Ueture of metal we from Be a ‘positive character increases dow"cast Term It | Chemistry XI tals (except Be and Me) give coloured flame, «let in Metal Beare tightly boned die to their «getusen ae alaltine earth and sol ‘Ther have high electrical \l thermal conduct | chemical Properties ealaline earth metals are less reactive than alkali metals The feactvity ofthese elements inereases on going down the or ; | i) Reactivity Towards Air and Water Be and Mare kinetically inert towards oxygen ané water bes the formation of an oxide film, while Ca, Sr and B: readily attacked by air to form oxide and nitride. As compare to alkali metal, alkaline earth metal have less tendency to react with water eof Be shows no reaction with water (cold as well as hot in the form of steam): Mg does not react with cold water, ie. itreacts with hot water (steam) only to give its hydroxide while rest of the members react with cold water to give their hydroxide and hydrogen gas. Ca+2H,0 —>Ca(OH), +H? Like, alkali metal hydroxides, these hydroxides are basic innature. (i) Reactivity Towards Halogens All alkaline earth metals combine with halogen at elevated temperatures forming halides of type, MX. M+X,—>MX, (ii) Reactivity Towards Hydrogen Except beryllium, all, alkaline earth metals combine with hydrogen upon heating to form their hydrides. MH, SoM Bell can be prepared by the reaction of BeCl with LAH. 2BeCl, + LiAIH, —> 2BeH, + LiCl+ AICI; (iv) Reactivity Towards Acids Alkaline earth metals readily react with mineral acids liberating dihydrogen. M+2HCIl —> MCI, +H? () Reducing Nature Alkaline earth metals are strong reducing agents but their reducing power is less than those of their corresponding alkali metals. Reducing nature increases from Be to Ba, as the ionisation enthalpies decreases and electrode potential become ‘more and more negative with increasing atomic number. (Wi) Solutions in Liquid Ammonia The solution of alkaline earth metals is deep blue black. M-+(x+y)NH, —>[M(NH; ), '* + 2[¢ (NH ), J" M +(x + 2y) NH; —>[M(NHs),]** + 2[e(NHg)y] In concentrated form, the colour of become bronze heeanse ofthe formation of metal clusters: e(NHy 9 NH, +s 4D Ny Pin ra APN ly decomposed to give corresponding inetal are obtained amides [M (NH, )g]2" #2) —M(NH3)2 + 4NH3 +H, Uses of Alkaline Earth Metals sed in the manufacture of alloys, Mg. is used in flash \d bulbs, MgCO,, is an ingredient of toothpaste. + Bei powder + Calcium is used in the extraction of inetals from oxides. wetals have often been used to remove air from + Cand P vacuum tubes. + Rasaltsare used in radiotherapy, e.g.,in treatment of cancer, General Characteristics of Compounds of the Alkaline Earth Metals ‘The general characteristics of compounds of alkaline earth metals are discussed below Oxides and Hydroxides + All the alkaline earth metals, oxides and hydroxides are basic except BeO and Be(OH), which are amphoteric in nature. + The solubility, thermal stability and basic character of these hydroxides increases from Mg(OH), to Ba(OH) + The basic character of these hydroxides increases on moving from Mg to Ba. This is because as the size of metal atom increases, M—O bond length increases or the M—O bond become weaker thus, readily breaks to release ions which are responsible for the basicity of these solutions. + Solubility increases on moving down the group because both lattice and hydration enthalpy decreases down the group but the decrease in lattice enthalpy is more rapid than that in hydration enthalpy. Halides + Allhalides of alkaline earth metals are ionic except Be which are covalent and electron deficient. + Beryllium chloride has a chain structure in the solid state.] Hydrides * The stability of hydrides of alkaline earth decreases from Be to Ba due to decrease in lattice enthalpy. + Bell, and MgH, are covalent in nature and CaH, StH, and BaH, are ionic in nature. ypati eeoce alkaline earth + Solubility efearbonates and sulphates of a metals decreases on moving down the gD ofearbonates increases with " eatocsoe Theme tse of se carbonate is mnch larger dnd hence, small cha size do not make a difference. em + The nitrates of alkaline earth metals are wad dissolution of carbonates in at nit el + Nitrates decompose on heating to give ovide 2M(NO,); —+2MO+ 4NO; +02 Anomalous Behaviour of Beryllium ally small atomic and ionie size, + Beryllium has excepti ic high charge density and absence of vacant d-orbitals, * Heforms covalent compounds ts exie and hydroxide ae amphoteric. It does not exhibit coordination number mor than four. * Ieshows diagonal relationship with aluminium. ©-8 both Al and Be are not readily attacked by acids. * The chloride of both Be and Al have bridged chloride (CI”) structure in vapour state * Be and Al ions have strong tendency to form complexes. Diagonal Relationship between Beryllium and Aluminium The atomic and ionic radii and charge/tadius ratio of bersllium and aluminium are almost similar: That's why these ‘wo resemble in some of their properties, aT oy erties are given below. rion i 9 the surface of I pind ide, which makes it nko its oxide, ess s lium and al " path erin and slung, de otrwve soluble omplees ie of ah eand aluminate j,. bey!) ph, Ein ease of Be huminat ion phase of both ve chr f. shown below. cl Ck Ngo : Be—Cl -Q oY avs | « os are soluble in organie so Both the chloride on eles and Beha, beng like benzene, chloro! . 88g ‘id. . ly The oxides of both beryllium (BeO) and alumi * re hard, high melting insoluble solids n + The oxides and hydroxides of both Be and lan amphoteric and dissolve in sodium hydroxide sol, well as in hydrochloric acid. i BeO + 2HCl—> BeCl, +H,0 BeO+2NaOH —> Na, Beo, Sodium berylate Alz03 + BHC! —> 2 AlCl, +3H,0 4l05 +2N20H —> 2NaAlO, 44,0 Sodium ‘meta aluminate +o= ( " ul eel block Elements = - visti te ae Gone ast Member of E2°P . = P « omaous Benaviou 1B — + Group M4 Elements: The Ct = — “jgProperties and AllOtroPeS Carbo! : Anomalous General Characteristics of p-block Elements + In p-block elements, the last electron enters in the outermost prorbital + There are six groups of p-block elements in the periodic table numbering from 13 to 18, Their valence shell electronic configuration is ns*np'* (except for He). + Differences in the inner core oftheir electronic configuration ‘greatly influence their physical and chemical properties. + ‘The maximum oxidation state shown by a p-block element is ‘equal to the total number of valence electrons, + The number of possible oxidation states increases towards the right of the periodic table. + In addition to this, socalled group oxidation state, p-block elements may show other oxidation states as well of the two electrons in the itermost i nutermost atomic s-orbital to remain unshared in compounds of post-teanciy metals is called inert pair effect. estfransin + The combined effect of size and availabilty and availability of orbital considerably influences the abilit ; conser es the ability ofthese elements to form + Non-metals have higher ionisation entha lectronegativities than metals, mined + Non-metal oxides are acidic or are basie in nature neutral, whereas metal oxides ee Anomalous Behaviours of First Member of Each Family Eu ‘The first member of each group of p-block diferst, the members of its corresponding group due toi F size and unavailability of d-orbitats. Few of such anomalies are as follows x () Maximum Covalency Because of the absence orbitals, the elements of second period lie s— member of each group) cannot expand its cnikRe beyond four, ie. their maximum covaleneyisie (because of the availability of one 2s and thre 2p-orbitals). Other members of the groups because ofthe d-orbitals can expand their covalence above lt (ii) Formation of pn-pn Bonds The first mene group have a unique tendency to form prst® =~ with itself or with the other elemen’— nod, In case of heavier members, since d-orbi# available, so they form pm-dat bond or dr-dth* TI instead of pn-pn bond. Ne pines, i energy of d-orbitals is higher ii o s, the pr-dn or da-dn bonding oor to me mel stability of the moleeu* mi . teaa | ase tril | Chemistry X! El Group 13 Elements : The Boron Family yp 13 contains six elements, ez,, B, Al, Ga, In, Tl, Nh and is collect y called boron family. jr oasbeen reper in small amounts and its half-life of most stable isotope is 20 seconds, Due to these reasons, its chemistry has + Mi jeen established yet. pot been est Auminium is the most abundant metal and third most abundant element in Earth's crust, after oxygen and silicon General Properties {i Electronic Configuration Their general electronic configuration is [inert gas] ns?np! {i Atomic Radi Tt increases on moving down the group from B to TI. However, the atomic radius of Ga is less than that of AL The presence of additional 10cl-electrons offer only poor screening effect for the outer electrons from the increased A dear charge in gallium (Ga), {ai lonisation Enthalpy Tt follows the trend given below nc Al 2 TOs) 11,0, + B,0, is acidic, Al and Ga oxide are amphoteric and those of In and 1 are basic. Reaction with nitrogen + All elements readily form nitrides at high temperature. 2E|s)+N,(g) —*> 2EN(s) et = Reaction with halogen *+ The covalent trihalides, e.g. BF, being electron deficient are strong Lewis 2E(6)+ 3X,(¢) — 2EX,(¢) (X=F, Cl, BrI) acids and the tendency to behave as Lewis acids decreases with increase in size ‘tenon Tt) ” = down the group. . + The trihalides of B exist as dierete molecules while the trihalides of nts exists as dimeric form, both in vapour state and in non-polar + These halides have an ability of complex formation. The boron trihalides have the tendency to form BX,L type complexes (where, Lis neutral or anionic ss donor) - Reaction with Water + M(OH), type hydroxide follow the same trend of basicity _| The form hydroxide ofthe type M(OH), as shown by oxides, | Mako gives hydroxide of TOH type. + Aluminium is very reactive even at lower temperature. Nc Pwaction occurs between boron and water. 2K(s)+3H,0(I) —> Al,0, +3H, (g)7Reaction with acids and alkalies a + 2Mis) + 6HCIiag) —+ 2M" (ag) + BCT (4 a HC 2M{s)# 2NOHag)+ 24,040) —9 2NaMO, (a0) +9 HT) even at Boron neither reacts with acide nor with alkalies ¢ anodlerate temperature + Aluminium, being amphoteric, reacts with both Anomalous Behaviour of Boron high + Due to its extremely small size, high electron d sy ailability of d-electron, bor electronegativity and non-a exhibits following anomalous properties, while other members of the + Boron isa typical non: group are metals, + Its melting and boiling points are higher than the other members of the group. * It forms only covalent compounds while other members ea form covalent as well as ionic compounds. The maximum covalency of B is four. + Only: boron exhibits allotropy and exists in crystalline as well as amorphous forms. *+ Except boron all other halides ofthe group elements are hydrolysed in water and exist as tetrahedral species [M (OH) J" and octahedral species(.M (H,O),]°”. in aqueous medium + The monomeric trihalides are electron deficient and act as strong Lewis acids, Boron trifluoride easily reacts with Lewis bases, such as NH, to complete its octet around boron F,B+:NH, —> F,BCNH, Similarity with Silicon Boron due to its small size and similar e/m ratio, shows resemblance with silicon, present diagonally opposite to it —, ilarities pwing, sirhilaritie: 1c follo Gil pits the FI non-metal with high Mein une vints and low at = «ductor com {oth Band ater. 1 si both are very hard und use gg ene in coy « trisa ba 1 si forms fi an chlorides * Fydralysed by jos of Band mt p14 Elements : The Carb, i he + arbi si, Ge, Sn, Pb, Fl. Fleroviu mall amount and its half-life ig 00 se nat been established. The genera ‘these elements is ns * np’ -aland Chemical Properties Gener alas It increases considerably fom 1) Covalent Radi It nereases consi c. 0 pereatter from Sito Pb a small increase in rad shxerved. This is because of the poor shielding fi jntervening d and f-orbitals. ii) Ionisation Enthalpy It decreases down the groy Fawever, there is small erease in, H rom Sn and slight increase in A, from Sn to Pbis oby. Thus, the trend is, C > Si > Ge > Sn < Pb, Electronegativity While moving down the group electronegativity decrease upto Si and from Si top, almost the same, Carbon and silicon are non-metds germanium is a metalloid, whereas Sn and Pb ae metals with low melting points. (iv) Oxidation State Carbon and silicon mostly show oxidation state while other elements show both +a +4 oxidation states, Stability of +2 oxidation state increases down theg due to inert pair effect, ele Important Chemical Reactions of Group 14 Reactions Reaction with oxygen 1 Mis) + 50,(g)—+ MO (Limited supply) Mis) + O,(g)—+ MO, (Excess) “Reaction with water Mls)+2H,O() —-4MO, + 244g) (Exception-Pb) Properties {Fors two types of oxides, ie. monoxide and dioxide, *+ Nature of monoxide is * Nature of dioxides js CO-neutral, GeO-acidic, SnO and PbO-ampbotet CO,, SiO,, ae = * C.Si, Ge are not afesrea erie allected by water. "Reaction with halogen i, a a Tg ge HO de tothe formation of ocide Alm. Ms x, ou, «6 covalent in nature M+ 2k, —oMK, (Excention-P,asitdoes nat exigy * Silty of, aks ineeaee ge re FORD. (where, X = F, Cl Br, 4) * Thecrder, bi gon “To themal stabil othaldes ie CCl, ther: saber totrachori, ee > Sik, > GeX, > Sux, > Pbx, “Sate easily hydrolysed by water: oA the same element decreases Wi dae orn “a CF, > CCl, > CBr, > Ch (sown the goup,nalous Properties and Allotropes of Hon cal non-metal form cr atypical 1 i ning covalent bonds isa nfs our valence electrons pits fou valence electrons. T shows the property sti [ani featemation power is > > Si > Geox sy seat antallotopes of carbon and their properties are feaedielow spiamond scnsaline lattice. Heid D network of sp °hybridised C-atoms. vi pe ardest substance known 17 sltoraf electricity, but a conductor of heat {EChond lenath is 154 pm : : esl ssed as gem stone, "eave diamonds are used in knives for cutting glass and rock eset 1Graphite “pisotmaterial having layered structure. *+ Bach layer has sp*-hybridised earbon atoms in hexagonal ring and adjacent layers are held together by van der Waals’ forces, thus graphite shows lubricating properties + Itisa good conductor of electricity, so used in making electrodes. Uses + Graphite fibres embedded in plastic material form high strenath. light weight composites *+ Being a good conductor, graphite is used for electrodes in batteries and industrial electrolysis. 3. Fullerenes + It contains 60 carbon atoms with sp*-hybridisation + Cy molecule has a shape, like soccer balls are called Buckminster fullerene. + It contains 25 six-membered and 12 five-membered rings. + Other forms of elemental carbon like carbon black, coke and charcoal are all impure forms of graphite or fullerenes Uses * Itact as wonderful lubricants. * The alkali compounds of C,, are used as supper conducting substance at the temperature rang of 10-40 K.Hydrocarbons In this Chapter... * Classification of Hydrocarbon * Alkanes * Alkenes * Alkynes ‘* Aromatic Hydrocarbons '* Carcinogenicity and Toxicity _gpeatbons are the compounds of carbon and hydrogen. They are obtained from coal and petroleum. classification of Hydrocarbon imcarbons are cl sified into three main categories, i.e. saturated (C—C and C—H single bonds), unsaturated multiple bonds-double and triple) and aromatic hydrocarbons. Hydrocarbons (Compounds of C and H only) {Aromatic hydrocarbons. (Alternate single, double bond and (41 + 2)r electrons are present) | (Carbon atoms are (Two or more bond{(s) are Saturated hydrocarbons | Unsaturated hydrocarbons | joined together through |_| presentbetween the carbon | single bonds only). |_| atom). | |—JAikanes| (C,Hoy.2) {alkenes | (CiHo») ae | [Open chain, e-g- (have atleast one double bond (Benzene) CHa— CH, (ethane)] between carbon atoms). €.g. CH)=CHy (ethene), |_{eyctoatkanes] = CH) propene) : “(Closed chain), (Naphthalene) eg /\ ttt L_{atiynes | (CuHar-2) We {have atleast one triple bond 2 between carbon atoms) (Cyetopropane) e.g. CH=CH (acetylene), Clip—C=CH (propyne), eteAlkanes Alkane are saturated pe ha ‘ single bonds . contain “hse I. joine Im alkanes Caton are tetahedals jon Om which C— Cand CH bond lengths are 1542 112 pm respectivels i vs are sp'-hybridised All the C-atoms in alka ” i ons n hydrocar ther in w phy foridised \ sos Structure of methane (CH,) molecule Nomenclature and Isomerism ptes to he followed while writing IUPAC names are as follows ') First of all. the longest chain of carbon atoms Comesponding to the parent alkane is identified. (i) The substituents attached to the carbon atoms are pumbered such that the branched C-atoms get the lowest possible numbers, (a) The substituents are written in alphabetical order before the name of parent alkane * The Dhenomenon in which hydrocarbons posses same fuolecula formula but different strucurests knowns isomerism. Allanes show structural position and chain isomerism, Dillerence in properties is due to difference their Structures and chain of carbon atoms, * Based upon the number of carbon atoms attached to a C-atoms, Preparation of Alkanes From unsaturated hydrocarbons CH=CH, +H, AiR Bene? He Hydrogenation ClCH, CH, —CH=cH, +H, PAPA /Ni SCH, oy cn Propene Z epee CH tpg Puayns 3 Popyre OE CHa Frepane “lay, ides y alk al PHS CH, + Hey = cl+ He Methane CHa tion Dry ether reac! : H. wo 4 + BrCH, hc cH,Br + any Fthane it shane F cometh ids we fic aci sarboxy! C20 + From + NaOH Zc, + ? -,c00” Na —— cH wan ries reeolar molecules frees the fist four members, , Physical Prope ¢ Alkanes are nom 2 to the wei 2 containing 15 Ca aoa aeeevre liquids and those containing "cathen oC ce slid at 298 K . aoe ossess weak van-Der Waals’ forces, Alkanes posses kanes are colourless and odourless. «+ Alkanes are nel odourtes / Boiling point of alkanes increases with increase in oy Chemical Reactions HalosenstOn. CH, + Cl, CH,CI ae chinv Chity cHi01 SE cre, BP coy, Conrad cws23K/100, SHEE 4 2CH, + 0, S200 am, 2CH,0H (CH3CO0), Mn * 2CH,CH;+30, HCO, 2cH,coomy KMn0, *(CHysCH + 0,4 Hy .con n+ 1 Complete “nsf OD) Set CHa Cs) + Ox(@) Traps’ CO) +2400) combustion ONC ca (cays CH; +CH; CH CHCH * CH Ho __ aw crs 20 — Sco + ath CoH + H, * Co, 773K 12+ Hy a CoHg + CoH, C3Hg + CyHy+ CHytions of Ethane n ofthe sigma MO in alk abe ane is symmetrical fon about its axis. The rotation, ments of ato wns in space which, vor rotamer number of cont ions of eth ases are : eclipsed (hydrogen atoms att ren atoms attached to asclose together as possible) and staggered art as possible), ediate conformation is called a skew jon. Felipsed and staggered conformations can be Hi by Sawhorse and Newman projections ae shown H H H a n/t HOH H H wn en one Se (@ Baipsed (i) Staggered ‘Sawhorse projection of ethane Angle of rotation or angle of torsion or dihedral angle iH a H H H (4) Staggered (Bcipsed Newmann projection of ethane ieatve Stability of Conformations sstirapart as possible and have minimum repulsive forces. «Tierepulsive interaction between the electron clouds, which shies stability of conformation is called torsional strain. “ Mogutude of torsional strain depends upon the angle of rotation shutC—Chond. This angle is called dihedral angle or torsional age, *Outfsaggered and eclipsed conformations of ethane, staggered ‘aufmation is more stable as H-atoms are farthest. Alkenes Ales: cre unsaturated hydrocarbons containing at least one ce — Alkenes are also known as olefins, since the first ethylene or ethene was found to form an oily liquid. ‘ect of Double Bond ‘qurbon double bond in alkenes consists of one trong (6)bond due to head on overlapping of sp*-hybridised ‘and one weak pi(m) bond obtained by lateral or sideways ‘of the two 2p-orbitals of the two carbon atoms. *+ The doble bond is shorter in bond length (134 pm) then the C—€ single bond (15 pm), 5 ong ston ng hn, H ’ / 6 + nt | spp) 4 7 pee Orbital diagram of ethene molecule Nomenclature + For nomenclature of alkenes in IUPAC system, the longest chain of carbon atoms containing the double bond is selected. + Numbering is done from the end which is nearer to double bbond. The suffix ‘ene’ replaces “ane Isomerism + Alkenes show both structural and geometrical isomerism. + Alkenes exhibit geometrical (cis-trans) isomerism due to restricted rotation around the C—C double bond. + cis-form of alkene is found to be more polar than trans-form because dipole moment of rans-form is almost zero. i HEC. CH CCS yl omc PSHE. # 4 H Gis 020) (us00) [cis-but-2-ene] [trans-but-2-ene] Preparation of Alkenes -Instigered form of ethane, the electron clouds of C—H bonds are} can be summarised as follows conc. H2S05 From alcohol ete \ From alkylhalide Ss From vicinal dihalide CH2Br 7 CH,Br Hp, Pa/C Cl Linalar’ catalyst From alkynes Cl Physical Properties «+ First three members are gases, the next fourteen are liquids and higher ones are solids. «+ Alkenes are colourless, odourless, insoluble in water but fairly soluble in non-polar solvents. «They show a regular increase in boiling point with inerease in sizepre PO, 1,C—CH, chr feat ies Me eee sublet BE — aa one —a Oe gaa se cae aoa Aaion oro | rocomymetie . Le aye be on H+ HCO one severe of Persie CH3CH,CHBr Aion othe bos _, HCC e _— re ro pee, CH, + HBr ' see seg HACC kof negative part ofthe addendne? Markoni aes the eB . seat poses ese be oie to hat carbon a ° A ‘CH; I WC C—CHs Addition ot water fro Be cH DIL KMeO4 , Cih—CH, H,C= Cl, + H,0+ 10] — p94 a 2 | OH OH Polymerisation reaction Alkynes Alkynes are unsaturated hydrocarbons that co Nomenclature and Isomerism + IBTUPAC system, they are named as deriva * They generally show position oo ris : " whi we com nding alkanes alistog ad by the suffix ‘yne’ y ly "omerism. In which, to compound di ;, Pounds differ in their Structures due to the position of triple be! Structure of Triple Bond : Ba exon st ei has Wo sp-hybridised orbital “Reet an gg 5 Koen eae eer ere Mereside netpning ao leeset chet XI soon Nits FONE C6 Fond tne : Wa toad and tant: —€ mem et (QV Ora gram of athynw a Properties ores a RAEN NOME cht ae Hg wal ighew Sans eoour Tess ites are solids Fa aks pola in nate fe jac tha HO anal énmniseibe with water bat = ih ater but solute in organic solven Fane boing point nereases with increase ng " jon and Chemical Reactions of Alkynes Chemical reac " Ser we Cy CHy — ie 7 rena [Ch CHB MS CH, CHB reparation cHACHO Br Br (Addition reactions) Bry Bry BCH CHBr HoH Br Be Ozonolysis CHO Vicinal dinalidle 7 [Na (Acidic nature) diy Sodium scetylide Aromatic Hydrocarbons ‘ena hydrocarbons, also known as arenes, were found to c sung benzene ring are known as benzenoids and those ‘anenclature and Isomerism "SILF\C nomenclature, the substituent is placed as prefix to the word benzene. “Vi ntain benzene ring (highly unsaturated). Aromatic compounds jot containing a benzene ring are known as non-benzenoids. "vo hydrogen atoms in benzene are replaced by two similar or different monovalent atoms or groups, three different Pion some n isomers are possible. ‘Tel.20°1, Gis known as the ortho (o-), the 1, 3 or 1, 5 as meta(m-) and the 1, 4 as para (p-) disubstituted compounds. ‘ncture of Benzene uazested the structure of benzene by the concept of oscillating nature of double bonds as shown below O-O7 met _ ermediate between ( shone + Renz ty det sa ee be Taree 40 horace CC double hand pes the followin 6" + For a compenind tr be: aromatic. it amust pose Planar (8) Compete deloalst “eon — co CC aS Uo) J fee Cc ibaa ntracene Rencene Cylopniaeyaion al toe on {On-electrons Teelectrons electrons velectons Preparation and Chemical Reactions i Chemical reactions HINOs/HSOs NO 323-383 K itration) Ch,/Anhyd. AICIs o (Halogenation) Fuming H,S0, ‘Gulphonation) Preparation Zavdust CotisoH estes — ie Gott; Bedot Fe /~ iedel-Crafis nin tube alkylation) CoHsCOONa 4 (Friedel-Crafts acylation) ote ON XG0H a Ben) N&COCI Anya =o econqn cert XI fe é ’ properties ie oa-polar molecules and are colourless liquids or al 1s amis with water but are sendy miscbte with ovens a e Influence of a Functi i substituted Benzene i! jon ops of behaviour are observed. Either ofp or m oo ed predominantly. This Dehaviour depends upor Sct he eoup already present in the benzene ne a ee Geetve influence of substituents lonal Group pe redirecting Groups ag eg. —OH, —NH3, —NHA, —NHCOCI 1 CH called ortho and as well as activating groups ein + ia Halogens are deactivating but they are ortho re erecting SPOUDS. a ting Groups eg. —NO,, —CN, — CHO, —cor, ; Te H,_—-COOR —SO,H ete., are called sieting as wel as deactivating groups, ‘benzene ring towards electrophilic substitution. oe ek, + They reduce th s strong ~1 effect, tron density in the benzene ring due to Carcinogenicity and Toxicity ‘The polynuclear hyde ons having two oF more fused and have carcinogenic (cancer ng) property. These are obtained by incomplete Hbustion of orginie materials like tobacco, petroleum. nto the hu reactions, nples of earei body and undergo se hey damaze DNA and cause cancer Some 1,2benzanthracene CH 3-methylcholanthrene cH, J CH. 10-dimethy!-12-benzanthracene