1 | Short Formula (Chemistry) WNGesece! SHORT FORMULA (GYAN SUTRA) ATOMIC STRUCTURE Estimation of closest distance of approach (derivation) of a-particle The radius of a nucleus R=R(A)"om he Planck's Quantum Theory : Energy of one photon = hy = 5, Photoelectric Effect : hveny,+ SMe Bohr’s Model for Hydrogen like atoms : h 4. mve=n 3 (Quantization of angular momentum) Ey z z 2 ae 222178 «10% 2 atom = 196 Zev gE, ae xn? 20? ane De Gig ve? Vs Zant erm Zz nh 7 wavelength : oD ing = p for photon) Wavelength of emitted photon : 1 Za (of ne No. of photons emitted by a sample of H atom : An(an+4) 22 Short Formula (Chemistry) MNResenence Heisenberg’s uncertainty principle : axap> fe axave fe aeave To ape ge maxave gh or ve ‘Quantum Numbers: * Principal quantum number (1)= 1,2, 3,4. 10. ah + Orbital angular momentum ofelectronin any obit = . Azimuthal quantum number (1) = 0, 1, ..... to (n= 1). * Number of ortitalsin a subshell= 2¢-+ 1 * Maximum number of electrons in patoularsubshell= 2 « (2/+ 4) LC hb + ofbital angular momentum L= 3 YEH =A Jee ar STOICHIOMETRY Mass of one atom of an element Relative atomic mass (R.A.M) = Total Number of nucleons 1 $5 xmass of one carbonatom Yemap Number] 1, 7 Netame at SP] VK a" <= mol. wt | mol. wt At wt || At wt Density density of the substance Specific gravity = “density of water at 4°C For gases : Molar massof the gas PM Absolute densiy (massivolume)= yoiar-yoiume ofthe gas «=O ow PMyasrer Mone _ iM, Vapourdensity V.D= G. = Pier = My ==3 Short Formula (Chemistry) MNResenence Mole-mole analysis : + At wt Mol Wt Mole-mole (| =A 56] —| eran] — [HB] =| — 8 xzde Concentration terms : Molarity (M) : : w>1000 Molarity (M)= (yi wt of solute) Vans Motality (m) : number of moles of solute 7 1000 w,/ Mw Molality= “mass of solvent in gram 1000 w,/ Mw, Mole fraction (x) : Mote fraction of solution) = "> Mole fraction of solvent (x) = mass of solute in gm 199 © %WiW= Tass of solution ingm mass of solute in gm @ wiv = Mass OF sollte ing 409 @ —%ewIv= Tass of solution in mi fo seviva Youme of solution in M499 Volume of solution Derive the following conversion : x,p 1000 Mole fraction of solute into molarity of solution M= tempon absolute scale Ideal gas Equation : PV=nRT =DRT pm RT p, aRT Total pressure = P, +P. + B, and so on.Short Formula (Chemistry) MNResenence Partial pressure = mole fraction X Total pressure ‘Amagat’s law of partial volume : VEV AVE Average molecular mass of gaseous mixture : Total mass of mixture MM +My +My Mac™ Fetal no. of moles in moture yn, + Graham's Law 1 Rate of diffusion r= 5 ie | [dy My 7 VV.D; Kinetic Theory of Gases : 4 aR PV= 3 mN UP Kinetic equation of gases 3 2 KNT 1) Average KE. for one mole = N, | >™U' ( ) Root mean sugare speed [3RT Up = PET mmol mass must bo in kpote Average speed UL =U, + UF UL [Rr . fet K is Bota tant t= fo is Bortemman consta Most probable speed art eo Vm Vander wall's equation : peat - “i |(v=nt) =0RT Critical constants: V,=3b,7 | Short Formula (Chemistry) WNGesece! Vander wall equation in virial form : Reduced Equation of state : 7 P+ : ir g]ey-9=87, THERMODYNAMICS ‘Thermodynamic processes : 1. Isothermal process: T= constant dT=0 ATs 2, Isochoric process: V= constant 3. Isobaric process : constant 4. Adiabatic process: or heat exchange with the surrounding = O(zero) IUPAC Sign convention about Heat and Work : ‘Work done on the system = Positive ‘Work done by the system = Negative 1 Law of Thermodynamics AUF (U,-U)=q+w Law of equipartion of energy : U=SoRT (only forideal gas) 1 AE = 5 nk (AT) where f= degrees of freedom for that gas. (Translational + Rotational) 2 formonoatomic 5 fordiatomic or linear polyatmic =6 fornon-linear polyatmic Calculation of heat (q) : Total heat capacity 4q _ 94 = po Gieuec8 | Short Formula (Chemistry) MNBesenence Molar heat capacity dq ape mole ‘Specific heat capacity (s) : 4q__ da maT md s = Jom K-! WORK DONE (w) Isothermal Reversible expansion/compression of an ideal gas W=-nRT In (V/V) Reversible and irreversible isochoric processes. since dv=0 So dW=-P,,.dV=0, Reversible isobaric process Reversible Work PaVp —PiVy _ AR (Te —Th) yt 1 Irreversible Work PrVp-PVy _ aR (TT) yt y-1 Free expansion - Always going to be so dW=-P.,.dV=0 Ino, heat is supplied q = 0 then AE oA Application of Ist Law : AU= AQ + AW = aw AU= aa -Pav nC, (T,-T,)=—P., (V,-V) and use irterversible and since P,,,= 0 PAV Constant volume process Heat given at constant volume du= (dq), hhange in internal eneray‘9 | Short Formula (Chemistry) MNBesenence Constant pressure process : H = Enthalpy (state function and extensive property) H=U+PV => 6,=C, = R (only for ideal gas) ‘Second Law Of Thermodynamics AS sen = AS gaan * AS syany >9 fora spontaneous process Entropy (S) 78. 8S pan ® J Entropy calculation for an ideal aas undergoin a process : state “5 State e Pa My Ty PVy Ts h Ve BS jaye FG, IN + ORIN (only for an ideal gas) ‘Third Law Of Thermodynamics : ‘The entropy of perfect crystals of al pure elements & compounds is zero at the absolute zero off Gibb’s free energy (G) : (State function and an extensive property) = Hae TS Criteria of spontaneity : (IAG... 8(-ve) <0 process is spontaneous iy tfac, .,is> 0 = processiis non spontaneous Gipttac ° > systems at equixium, Physical interpretation of AG : > The maximum amount of non-expansional (compression) work which can be performed. AG= aw, I= Tas, Standard Free Energy Change (AG®) 1. AG? = -2,303 RT log, K 2.Atequilibium AG=0, 3. The decrease in free energy (-AG) is given as. -AG = W,¢= Va 308 nRT log, Vy 4.46) forelemental state=0 5. AG} = Gasset Gieactants smperature,10 Short Formula (Chemisty) MNBesenence ‘Thermochemistry : Change in standard enthalpy AH’ = Hf, > — Hi. = heat added at constant pressure, = CAT. ee » Reaction should be endothermic as we have to give extra heat to reactants to gel these converted into products Nd Hyoaye SH, + Reaction wll be exothermic as extra heat content of reactants will be released during the reaction, Enthalpy change ofa reaction AH can * Hyoaea™ Hrs AH sets HY peaucts ~ Hpac =postive "=" endothermic negative — exothermic ‘Temperature Dependence Of AH : (Kirchoff's equation) : Foraconstant volume reaction AH," = MH,” + AG, (T,-T,) where AC, = C, (products) -C, (reactants) For aconstant volume reaction AE} = aE} + [acy aT Enthalpy of Reaction from Enthalpies of Formation : The enthalpy of reaction can be calculated by AHS SEV, AH ac 2Vp4Hyerane Vuisthe stoichiometric Estimation of Enthalpy of a reaction from bond Enthalpies : Enthalpy required to) (Enthalpy released to aH [break reactants into |-| form products from the gasesous atoms gasesous atoms Resonance Energy: aH", =H", CHEMICAL EQUILIBRIUM At equilibrium () Rate of forward reaction = rate of backward reaction (i Concentration (moleftre) of reactant and product becomes constant. (ii) AG = 0.41 | Short Formula (Chemistry) MNBesenence mark, Equilibrium constant (k) rate.constant of forward reaction Ky. fate constant of backward reacton = Ky Equilibrium constantin terrms of concentration (K,): Ki (cr 101" ky, (rer Equilibrium constant in terms of partial pressure (K, ): Pel’ Pol? Pal PsP Equilibrium constant in terms of mole fraction (K,): Relation between K, & K,: = KART Relation between K, & K, : = Ke i Ha + too = a30nR [TT | AH Enthalpy of action Relation between equilibrium constant & standard free energy change : AG? = ~2.303 RT log K Reaction Quotient (Q) : [cr oy rer ‘The values of expression Q Degree of Dissociation (a) @ = no, of moles dissociated / initial no. of moles taken raction of moles dissociated out of 1 mole, Note: % dissociation = a x 100 ‘Observed molecular weight and Observed Vapour Density of the mixture : lar weight of equilibriummixture Totalno.of moles Observed molecular weight of A,(g) M,-M, =m,12 Short Formula (Chemisty) MNBesenence External factor affecting equilibrium Le Chatelier’s Principle: I system at equilibrium is subjected to a disturbance or stress that changes any ofthe factors that determine the state of equilibrium, the system will react in such a way as to minimize the effect of the disturbance. Effect of concentration I the concentration of reactants increased at equilibrium then reaction shift in the forward direction Ifthe concentration of product is increased then equilibrium shifts in the backward direction Effect of volume: If volume is increased pressure decreases hence reaction will shift in the direction in which pressure increases that is in the direction in which number of moles of gases increases and vice versa, If volume isincreased then, for ‘An > 0 reaction will shift in the forward direction An <0 reaction will shit in the backward direction An = 0 reaction wll not shift Effectoof pressure * If pressure is increased at equilibrium then reaction will try to decrease the pressure, hence it will shift in the direction in which less no. of moles of gases are formed. Effect of inert gas addition : @ Constant pressure inert gas is added then to maintain the pressure constant, volume is increased, Hence equilibrium ‘il shift in the direction in which larger no. of moles of gas is formed ‘4n > 0 reaction will shift in the forward direction ‘An <0 reaction wil shift in the backward direction n= 0 reaction will not sift @® Constant volume Inert gas addition has no effect at constant volume, Effect of Temperature : Eaquilibrium constant is only dependent upon the temperature, As and intercept = 1 It plot of ink vs = is plotted then itis a straight line with slope For endothermic (AH > 0) reaction value of the equilibrium constant increases with the rise in temperature For exothermic (AH < 0) reaction, value of the equilibrium constant decreases with increase in temperature For AH > 0, reaction shiffts in the forward direction with increase in temperatutre * For aH <0, reaction shifts in the backward direction with increases in temperature, * Ifthe concentration of reactants increased at equilibrium then reaction shift in the forward direction * Ifthe concentration of product is increased then equilibrium shifts in the backward direction Vapour Pressure of Liquid : Partialpressure of H,0 vapours Relative Humidity = Y= Vapour pressure of Oat that temp.13 | Short Formula (Chemistry) WNGesece! ‘Thermodynamics of Equilibrium AG = AG"+ 2.303 RT 10g, kK) oa Vant Hoff equation- tog] i a 2308R (TT IONIC EQUILIBRIUM 4. OSTWALD DILUTIONLAW: HWA") _[CallCa] _ Ca? © Dissociation constant of weak acid (K) Kx MRT = IERIE Weset then 1-05 tork,= enor a= f= Ro i Ve -Higher the value of K,/K,, strong isthe acid / base. 2 Similarly for a weak base ity and pH scale : pH log a. (where @, is the activity of H* ions = molar concentration for dilute solution) Note: pH can also be negative or > 14] pH =~ log (H'); IH] = 10% POH=—log[OH]; [OH ]= 10" pka=~log Ka ; Ka= 10% kb log Kb kt PROPERTIES OF WATER : 1. Inpure water [H']=[OH] _soitis Neutral. 2. Moler concentration / Molarity of water = 55.56 M. 3. Ionic product of water (K,,) [HOH] = 10-* at 25° (experimentally) pOH = neutral pH PH<7 orpOH>7 => acidic pH>TorpoH<7 = Basic 4. Degree of dissociation of water: ‘no. of molesdissociated 107 = 107 s9c10- oF 1.8410" Total No.of molesinitiallytaken ~ 55.55 1ex10 18x10 % 5. Absolute dissociation constant of water: [H'JOH) _ 1077x107 at8x10%% {H,0] 55.55, val K=44 | Short Formula (Chemistry) WNGesece! BK, = pK, =—Iog (1.8% 10" 16 —log 1.8= 15.74 Kk, = [HT [OHT=K,, = Note: fora conjugate acid-base pairs pk, + pK,=PK, = 14 at 25°C. pK, of H,0" jons=—1.74 pK, of OH ions =-1.74. Q PH Calculations of Different Types of Solutions : {a) Strong acid solution : © Ifconcentration is greater than 10M In this case H* ions coming from water can be neglected, ()fconcentration is less than 10% M. Inthis case H” ions coming from water cannot be neglected {b) Strong base solution : Using similar method as in par (a) calculate first [OH] and then use [H'] [OH (6) pHof mixture of two strong acid ‘Number of Hons from I-solutio Number of H' ions from Il-solution = N,V, NaMh + NeVo WieN= oe (4) pH of mixture of two strong bases : eye NtMetNeVe TOWI= NET Vv, (e) pH of mixture of a strong acid and a strong bast IFN,V, > N,V, then solution will be acidic in nature and (H'] = N ICN,V, > N,V, then solution willbe basic in nature and. [OH () _ pHof aweak acid(monoprotic) solution HOH] _ cw HA” Ha fact >(1-a) = Ke ©. (is valid if a <0.1 or 10%) Onincreasing the dilution > Cl sat — andjHyl pot (9) pH ofa solution of a polyprotic weak acid : pH =2(PKe, “o00{d)_ Strong acid & strong base : 15 | Short Formula (Chemistry) WNGesece! RELATIVE STRENGTH OF TWOACIDS. [H'] furnished by 1 acid _ cys _ [Ks.61 TH] furnished by Hl acid ~ e202 ~ | ky,c2 (h) pH of amixture of two weak acid(both monoprotic) solutions : Kar (a, << 1and(a,<<1) 9 KS Fg, H1= C0, +0,0,= \OK a+ CK ** If water is again considered third weak acid in solution of two weak acid then T= KG Kate *K, CK = 10-4 = K, TH1= (OKy +O. Ka, 10 ()__pHof amixture of weak acid(monoprotic) and a strong acid solution : r [SA]=C, and [WAJ=C,, then (H'] from SA=C, and [H'] from WA=C, Let HA is a weak acd = Ort OF ak Gp t= : ** Ifa strong acid of low conc is added in water then [H’] of solution can be calculated as OF + Kw 2 ° SALT HYDROLYSIS : Salt of ‘Type of hydrolysis ik, h pH k, 1 1 (a) weak acid & strong base anionic ~ we 7+ > pk,+ > loge ke ae 2 P&T [b) sti id & ik bi ti Kw Kw z : k, : K (b) strong acid & weak base cationic i we 3 Pk, 5 loge kw Kur (c) weak acid & weak base both Kak ky Hydrolysis of ployvalent anions or cations For Na,PO, Ky Ky = Ky46 | Short Formula (Chemisty) MNGezcnecce Kx KEK, Ka* Ky = Ky Generally pH is calculated only using the first step Hydrolysis. cr oa. (lees 1 $0 pH= S1PKy + PK,o *log¢] Hydrolysis of Amphiprotic Anion. (Cation is not Hydrolysed e.g. NaHCO,, NaHS, etc.) ( PKay+PKag pH (Ho03) = |“ (©) Similartyfork,PO~ and HPO,” amphirotic anions. _ {Kay *PKap Pap +PKay Meypoy [S| at Prot z ° HPO, 5 HPO, Ke 5 PO ionisation Lok-bs) KK Ky 1 pHofNaH,PO,= > (0K, +PK) pHoINaHPO,= 2 (0K,,+ pK.) ottorNapo,» Hokies pa +1090) + Sec hytatls can net BUFFER SOLUTION : (a) Acidic Buffer: e.g. CH,COOH and CH,COONa, (weak acid and salt of its conjugate base) I= {salt ' DHE pK, + 109 facay {Henderson's equation] (b) Basic Buffer: e.g. NH,OH + NH,Cl. (weak base and salt of its conjugate acid) [sary [Base] POH = pK, + log Buffer capacity (index) : Total no. of molesof acid alkali added perlitre Change in pH 3 @010-¥) S03 a+b‘Short Formula (Chemistry) INDICATOR : Hin He +n 0 o Ky Koo : SIGNIFICANCE OF INDICATORS : WAGssenencs {lonised form) PH= PKe, +109 Unionised form] Extent of reaction of different bases with acid (HCl) using two indicators Phenolphthalein NacH 100% reaction is indicated NaOH + HC! — Nacl+ H,0 Na.co, ‘50% reaction upto NaHCO, stage is indicated Na,CO, + HC! — NaHCO, + NaCl NaHico, No reaction is indicated Methyl Orange 100% reaction is indicated NaOH + HCI — NaCl+H,0 100% reaction is indicated Na,CO, + 2HCI— 2NaCl+H,0+CO, 10035 reaction is indicated NaHCO, + HCI NaCl+H,0+ CO, Q ISOELECTRIC POINT: SOLUBILITY PRODUCT : K,, = (es) (ysy= ays CONDITION FOR PRECIPITATION : Ifionic product K,» > Kep precipitation occurs, IK, p= Kp Saturated solution (precipitation just begins or is just prevented), _ ELECTROCHEMISTRY ELECTRODE POTENTIAL For any electrode —» oxidiation potential E.,, = RP of cathode -R-P of anode E_, = RP. of cathode + O.P of anode E_,, is always a +ve quantity & Anode will be electrode of low R.P E®,,,.= SRP of cathode - SRP of anode, Reduction potential Greater the SRP value greater will be oxidising power.48 | Short Formula (Chemisty) MNGezcnecce GIBBS FREE ENERGY CHANGE : AG = — FE. yy AG? == nFE* 4, NERNST EQUATION : (Effect of concentration and temp of an emt of cel = AG=AGP+RT MQ (where Qis raection quotient) 2.303RT, 2A ag Egy Esa SP tog (at 288K) Atchemical equirium AG : Ea 2 '09 Kaa 9.0581 0.0881 2g oO Dog Ky Foran electrode M(s\/M* .2a0aRT Bae Eh a to Gap CONCENTRATION CELL : A cell in which both the electrods are made up of same material. For all concentrs ncell —E°, (a) Electrolyte Concentration Cell : 0.0581, Sa 69,23) 2n* (6) Zn(6) (Zn) = 20594 hog (©) Electrode Concentration Cel: eg. PLHP, alm)/H (IM) /H, P, atm) / PL oe tog [pr DIFFERENT TYPES OF ELECTRODES: ee ee) ee 2 Gas-ion Electrode Pt/H,(Patm)/H* (XM) ‘aS areduction electrode Haq se —> 4H, (Patm) E=49 | Short Formula (Chemisty) MNGezcnecce 3. Oxidation-eduction Electrode Pt/ Fe, Fe duct lectrode Fe Fe E=E?-0,0591 | Fe") a reduction electode Fe + © : =€*—00801 og Fes} 4, MetakMetalinsolublesatElecrode eg, AglAgCI, Cr as areduction electrode AgCl(s) + e- ——> Ag(s) + Cr © Eerygarty * ESriigate ~ 0.0891 log CH. ‘CALCULATION OF DIFFERENT THERMODYNAMICS FUNCTION OF CELL REACTION OQ aG=-nFE, as ° a (Alt costant pressure) ° ° Esa+bT+cr+ 0 anene{t(%]-<| Q —Acp of cell reaction _ dH C= d Aop= (aH) O ELECTROLYSIS : @ Ki, Ca®, Nat, Mg, AIS, Zn", Fe", HY, Cu, Ag’, Au ee Increasing order of deposition. (©) Similarly the anion which is strogner reducing agent(low value of SRP) is liberated first at the anode. 0% Nog..0FF, oF, BF. 1 Incteasingerer a petion20 | Short Formula (Chemistry) MNBesenence FARADAY'S LAW OF ELECTROLYSIS : First Law wszq weZit Z= Electrochemical equivalent of substance ‘Second Law: w Wie Woe Ez eonstant Be W _ixtxcurrent efficiency factor E (96500 actual mass deposited/produced (CURRENT EFFICIENCY = E 100 Theoritical mass deposited/produced » CONDITION FOR SIMULTANEOUS DEPOSITION OF Cu & Fe AT CATHODE 0.0591 1 ge o0se1 4 219 Gyr = Erte 5 109 aa Condition forthe simultaneous deposition of Cu & Fe on cathode, Faw seu CONDUCTANCE: 1 Conductance = tance © Specific conductance or conductivity : (Reciprocal of specific resistance) K = specific conductance ° * Equivalent conductance : K1000 Normality =e > Molar conductance : 9, -Kxt000 2m = Motay Unit ohm cm? mole" spect comauctanoe = conductance x £ KOHLRAUSCH’S LA\ Variation of 4, /2,, of a solution with concentration : () — Strongelectrolyte Aye= Bia ~ Dv (i) Weak electrolyte: a, 1 Atm, where Ais the molar conductivity 'No of cations obtained after dissociation per formula unit n= No of anions obtained after dissociation per formula unit,21 | Short Formula (Chemisty) WNSesenen: APPLICATION OF KOHLRAUSCH LAW: 4. Calculation of , of weak electrolytes : My exycocin = Maencoenn * ape Biacr 2. Tocalculate degree of diossociation of a week electrolyte ay ca? on Ka oa 3. Solubility (S) of sparingly soluble salt & their K,, 1000 aye ** Solubility k= IONIC MOBILITY :Itis the distance travelled by the ion per second under the potential gradient of 1 volts per Com, i's unit is mes "v" Absolute ionic mobility : Dep, Po Age i =F ud 29 SF x ue lonie Mobility x = —* rere (Wi —potentiaigradient -|, Me * [ns + He | ransport Number of cation & t, = Transport Number of anion ‘Transport Number SOLUTION & COLLIGATIVE PROPERTIES 1... OSMOTIC PRESSURE: o gh Where, density of soln., h= equilibrium height, ()—_ Vont-Hoff Formula (For calculation of O.P.) n= CST scnt= © Rr Gustite alga euston ‘tal conc. of all types of particles, +0, + Cy + (44g 4Mg Freed v Note: If V, mL of ©, cone. + V, mL of C, cone. are mixed. (create (mV) +m2V2 (a) Isotonic solution ~ Two solutions having same O.P.22 | Short Formula (Chemisty) MNBesenence (b) Hyper tonic if x,> x,, = IM solution is hypertonic solution w.rt, 2%! solution. {c) Hypotonic — II" solution is hypotonic w-rt. I solution Abnormal Colligative Properties : (In case of association or dissociation) VANT HOFF CORRECTION FACTOR (i): ;._ 2xblobserved/ actual/ abnormal value of colligative property Theoritical value ofcoligative properly exp./observed no. of particles / conc. _ observed molality Theortical no. of particles ~Theortical molality theoretical molar mass (formula mass) ‘experimental /observed molar mass apparent molar mass) OQ 1>1 > dissociation. iP,°) Ideal solutions ( mixtures): Mixtures which follow Raoutts law at all temperature, A> Anon B, 8 8 AH,,.= 0 ay, AS,,,= + ve as for processto proceed :AG,,,=-ve eg. (1) Benzene + Toluene. (2) Hexane + heptane, ()CHBr+ CH. Non - Ideal solutions : Which do not obey Raoult’ lav, (@) Positive deviation :— OP yap? (KPAAXPL) AsA—B L Weaker force of attraction (i aH, = +ve energy absorbed (w)aV,,=4ve (1L#1L> aL) WAS, =4Ve (ac. =-ve eg. H,0+CHOH. H,0+C,HOH C.H,OH + hexane H,OH + cyclohexane, CHCl, + CCI, + dipole dipole interaction becomes weak we PoA> P'B25 | Short Formula (Chemisty) WNSesenen: (&) Negative deviation © Pexp PB XA=0 immiscible Liquids : Pram = Pat Pa, GP,=PEX, Gi) y= POX, PE PR _ Wa My Gv) Py Poe PS 9 50 wg RT po ta LT. Ir. BP. of solution is less than the individual B.P.'s of both the liquids,‘Short Formula (Chemistry) Henry Law : ‘This law deals with dissolution of gas in liquid .e. mass of any gas dissolved in any solvent per unit volume is 0 proportional to pressure of gas in equilibrium with liquid map m Pp weight of gas. ™ > Volume of liquid SOLID STATE Classification of Crystal into Seven System Crystal System ——_UnitCell Dimensions and Angles ‘Cubic a=b=cia ‘orthorhombic arbecra Tetragonal azbecja=B=y= 90" Monoclinic asbec; 90" 2p Rhombohedcal asb=e Trilinic arbec;azpey200 Hexagonal a=beo;a=B= 90%y= 120° ANALYSIS OF CUBICAL SYSTEM Property sc Bcc () atomic radius (°) (No. of atoms per unit cell (2) 1 2 Gi) C.No. 6 8 (Ww) Packingefficiency 52% 68% ™ No. voids (@) octahedral (Z) (©) Tetrahderal (22) NEIGHBOUR HOOD OF A PARTICLE: ‘Simple Cubic (SC) Structure : ‘Type of neighbour Distance nearest a (next) (next MNBesenence Bravais Example Lattices Sc, BCC, FC Nac SC, BCC, end centred & FCC 8, sc, Bcc Sn,2n0, SC, end centred Sy sc Quartz sc H,0, sc Graphite Fee a= edge length no.of neighbours 6 (shared by 4 cubes) 12 (shared by 2 cubes) 8 (unshared)2 aw ay ° Short Formula (Chemisty) Wsesece: Body Centered Cubic (BCC) Structure ‘Type of neighbour Distance no.of neighbours nearest 8 (vex) 6 (oxy? 2 (vex) ” (ext) 8 Face Centered Cubic (FCC) Structure : ‘Type of neighbour no. of neighbours ee) nearest (>) , 3x8) tox : x) B (vent ae 2 (roxy a 2 [5 ox ale 2 (oo V2 z(m) DENSITY OF LATTICE MATTER (d)= jag |“ where N= Avogadro's No. M= atomic mass or molecular mass, tonic ervstats Ne. Limiting radius ratio a 01155~0.225 Criangula 4 0.225 — 0.414 (Tetrahedral) 8 414-0722 (Octanedral 8 0.732 - 0.999 (Cubic). EXAMPLES OF AIONIC CRYSTAL (a) Rock Salt (Nach) Coordination number (6:6) (by cect CiNo. (8:8) 2 Edge length of unit el:- ae FoI {c) Zinc Blende (ZnS) C.No. (4: 4)28 | Short Formula (Chemisty) WNRexcne! 4 a= Moe He) (@) Fluorite structure (CaF,) C.No. (8: 4) © Crystal Defects (Imperfections) oom Defects (Point Detects Stoichiometric Non-Stoichiometric Schottky Frenkel Metal excess Non-Metal excess {(on pairs missing) (dislocation of ions) electron in place extracation In Vacant sie extra anionin ‘of anion the interstitial in place of cation intersiial (not found) CHEMICAL KINETICS & REDIOACTIVITY RATE/VELOCITY OF CHEMICAL REACTION: Ac _ mollit at "sec ‘Types of Rates of chemical reaction = Fora reaction R —> P Rate = = mol it’ time-* = mot dm timer Total change in concentration Average rate Total time taken concentration —+ de __ AR), dP = lim = Reamae = 158 [at | = at =~ dt = at — — RATE LAW (DEPENDENCE OF RATE ON CONCENTRATION OF REACTANTS): Rate=K(conc,) differential rate equation or rate expression ‘Where K= Rate constant = specific reaction rate = rate of reaction when concentration is unity Unit of K = (eono)"=* time Order of reaction : m,A+ m,8 > products RIAD [BP Where p may or may not be equal to m, & similarly q may or may not be equal tom, p is order of reaction with respect to reactant A and q is order of reaction with respect to reactant B and (0+ q) is overall order of the reaction.28 | Short Formula (Chemisty) MNBesenence INTEGRATED RATE LAWS : ©, or ‘ais initial concentration and C, or a ~xis concentration at time (a) zero order reactions Rate = k [cono.}°= constant c or C=0,-kt So Unit of K = mot lit® sec-', Time for completion = <2. k o So So atts C= 250 My= Site SP t=, (b) First Order Reactions : (@ Leta 1 order reaction is, A —> Products 2903 45 2 y k Max = 2.688 independent of intial concentration Graphical Representation : 2.303 2.303 t= -2205 tog c,+ “2 log C, 2.308 5 ‘ane 2.303 tano=— 2308 6 . 6 Tog O, orl alas Toa, (6) Second order reaction : 2 order Reactions Two types A + A — products A +B —> products 6 4 ao ° @-» a») a-x bo Cees a at 7K e¥) Ge 7K 0-0 od 2.309 ax ait ke wen) P@n ma ta=b) '°9 apo—x) (d) Psuedo first order reaction : ForA+B—>Products [Ral KAN Br30 | Short Formula (Chemistry) WNGesece! 2308 a») = ib "9 ab») Now if "is taken in large excess b> > a = 2308 4. a > pt 9 ax ‘b's very large can be taken as constant 2303, a 2.303, : = k= tog 5o > K=S* bog is psuedo first order rate constant METHODS TO DETERMINE ORDER OF AREACTION {a) Initial rate method : r= KAP BP [ # — [B]= constant [C]= constant then fortwo different intial concentrations of Awe have fo _( (Aol Y fo, =KIAL* » fo) = KIAL* =e lien) (b) Using integrated rate law : Itis method of trial and error, (c) Method of half lives : Tor n? order “Ey fornmorderresction ty. = Ry (d) Ostwald Isolation Method rate = k [A} [BI (C} METHODS TO MONITOR THE PROGRESS OF THE REACTION: (@) Progress of gaseous reaction can be monitored by measuring total pressure ata fixed volume & temperature 2.303 ‘orby measuring total volume of mixture under constant pressure and temperature, «. K=""|~ log Po(n-1) Py =F, {Formulais not applicable when n = 1, the value of n can be fractional also.} ©) Bytitration method: 2303 Vo 1. axV, a-x=V, = ke oo yy 2. Study of acid hydrolysis of an easter. 2303 Va=Vp we SP to (© By measuring optical rotation produced by the reaction mixture : 2.903 { M k= SF og |g31 | Short Formula (Chemisty) MNBesenence EFFECT OF TEMPERATURE ON RATE OF REACTION. K.+10 i ~ 209 (for most ofthe reactions) Te. Arhenius theroy of reaction rate. 1 Entaley summation of enthalpies of reactants 1ummation of enthalpies of reactants Enthalpy change during the reaction nergy of activation ofthe forward reaction nergy of activation ofthe backward reaction E> => endothermic E. exothermic AH= (E,—E,) = enthalpy change Enns = Ey E,=E, +E, Arhenius equation kaAeERT = k [oone.)> dink _ E5 oT RT? . ae If k, and k, be the rate constant of a reaction at two different temperature T, and T, respectively, then we have jog hfe (41 8K, 2BOTR |T Te Ina * =ina- Es slope = %ink=InA- To 6 Koa Ink wT REVERSIBLE REACTIONS A ota een RT (EyEu RT32 | Short Formula (Chemistry) MNBesenence mK, re nk. ‘endothermic 1/T exothermic VT BK Ey +Ea,he Iq“ kK, S keke (i) REVERSIBLE 1®" ORDER REACATION ( both forward and backward) (ii) SEQUENTIAL 1*" ORDER REACTION wl=tale“* 1 Ke oma = (Ka) Ky cone a {c] = cASEA kK 7 BL tA, cone (a CASE: — K,>>K, a33 | Short Formula (Chemistry) MNBesenence PERIODIC TABLE & PERIODICITY Development of Modern Periodic Tabl (a) Dobereiner’s Triads : He arranged similar elements in the groups of three elements called as triads (b) Newland's Law of Octave : He was the first to corelate the chemical properties ofthe elements with their atomic masses (c) Lother Meyer's Classification : He plotted a graph between atomic masses against their respective atomic volumes for a number of elements, He found the observations ; (i) elements with similar properties, ‘occupied similar positions on the curve, (i) alkali metals having larger atomic volumes occupied the crests, (ii) transitions elements occupied the troughs, (iv the halogens occupied the ascending portions of the curve before the inert gases and (v) alkaline earth metals occupied the positions at about the mid points of the descending portions of the curve, On the basis of these observations he concluded that the atomic volumes (a physical property) of the elements are the periodic functions of their atomic masses. (d) Mendeleev's Periodic Tabi Mendeleev's Periodic’s Law the physical and chemical properties of the elements are the periodic functions oftheir atomic masses. Per ‘Number of Elements Called as (rast 2 Very short period en 3 ‘Short period Gn=3 3 ‘Short peiog (@Fn=4 8 Long period OF n=5 8 Long period (Orn=6 2 Very long petiod rns? 8 Tnoomplete period ‘© thas simplified and systematised the study of elements and their compounds. © thas helped in predicting the discovery of new elements on the basis of the blank spaces given inits periodic table Demerits in Mendeleev’s Periodic Table © Position of hydrogen is uncertain I has been placed in A and VIIA groups. © —_Noseparate positions were given to isotopes. © Anomalous positions of lanthanides and actinides in periodic table. © Order of increasing atomic weights isnot strictly followed in the arrangement of elements in he periodic. table. © Similar elements were placed indifferent groups. © didn't explained the cause of periodicity (@) Long form of the Periodic Table or Moseley's Periodic Table = Modern Periodic Law (Moseley's Periodic Law) : Ifthe elements are arranged in order of their increasing atomic number, after @ regular interval, elements with, similar properties are repeated Periodicity The repetition of the properties of elements after regular intervals when the elements are arranged in the order of increasing atomic number is called periodicity, Cause of Periodicity.‘34 | Short Formula (Chemistry) NSesenence ‘The periodic repetition ofthe properties of the elements is due tothe recurrence of similar valence shell electronic configurations after certain regular interval. ‘The modem periodic table consists of horizontal rows (periods) and vertical column (groups). Periods : ‘There are seven periods numbered as 1,2, 3,4, , 8 and 7. © Each period consists of a series of elements having same valence shell © Each period corresponds to a particular principal quantum number ofthe valence shell presenti it © Each period starts with an alkali metal having outermost electronic configuration as ns! . Each period ends with a noble gas with outermost electronic configuration ns:np® except helium hnaving outermost electronic configuration as ts Each period starts with the filing of new energy level. © The number of elements in each period is twice the number of atomic orbitals available in energy level ‘thats being filed, Groups: ‘There are eighteen groups numbered as 1, 2,3, 4, 5, ..... 13, 14, 15, 16, 17, 18, Group consists of a series of elements having similar valence shell electronic configuration, Block Elements Block Elements noe nf « of letals(-Block elements) = — = Lantharides | ss | wdsor| atx | Ste | ote sto sores | wsacs| seo | wto| worse | wasoe| sine | vase wactintes | im | | oo fm [atime |& le] & | ele |i] S| Classification of the Elements : (a) s-block elements Group 1 & 2 elements constitute the s:block. General electronic configuration is [inert gas] ns** ‘s-block elements lie on the extreme left ofthe periodic table, (b) p-block elements Group 13 to 18 elements constitute the p-block. General electronic configuration is [inert gas] nsap'* (©) @Block elements Group 3 to 12 elements constitute the d-block. General electronic configuration is [inert gas]35 | Short Formula (Chemisty) WNsese ESSPOROSS (n—1) a" ns!? (d)f-Block elements General electronic configuration is (n 2) f** (n—1) d&* ns® All -block elements belong to 3° group. Elements of f-blocks have been classified into two series. (1) I" inner transition or 4 fseries, contains 14 elements ,,Ce to ,Lu. (2). Ind inner transition or f-series, contains 14 elements ,,Th to ,,Lr Prediction of period, group and block : 2 Period of an element corresponds to the principal quantum number of the valence shell The block of an element corresponds to the type of subshell which receives the last electron, The group is predicted from the number of electrons in the valence shell or/and penultimate shell as, follows, (@) For s-block elements Group no. = the no, of valence electrons. (©) Forp-block elements Group no. = 10+ no. of valence electrons, (©) Fordsblock elements; Group no. Metals and nonmetals : ‘+ The metals are characterised by their nature of readily giving up the electron(s) and from shinning lustre. Metals comprises more than 78% of all known elements and appear on the left hand side of the periodic table, Metals are usually solids at room temperature (except mercury, gallium). They have high melting and boiling points and are good conductors of heat and electricity, Oxides of metals are generally basic in nature (Gore metals in their higher oxidation state form acid oxides e.g. CrO), ‘+ Nonmetais do not lose electrons but take up electrons to form corresponding anions. Nonmetals are located at the top right hand side ofthe periodic table, Nonmetals are usually solids, liquids orgases at room. ‘temperature with low metting and boiling points. They are poor conductors of heat and electricity. Oxides of nonmetals are generally acidic in nature, 10. of electrons in (n= 1) d sub shell + no. of electrons in valence shell Metalloids (Semi metals) : The metalloids comprise of the elements B, Si, Ge, As, Sb and Te. \gonal relations! 2peod = Be BC 3* period Mg Al Si Diagonal relationship arises because of ; © ondescending a group, the ators and ions increase in size. On moving from left to sight in the periodic. table, the size decreases. Thus on moving diagonally, the size remains nearly the same. (i= 1.23.4 & Mg = 1.36 A; Li= 0.76 A & Mg = 0.72) @ itis sometimes suggested that the diagonal relationship arises because of diagonal similarity in electronegativity values, (i= 1.0 Mg S&Al=15;B=208Si= 1.8) The periodicity of ator () Effective nuclear charg ‘The effective nuclear charge (Z,,) = Zo, (where Zis the actual nuclear charge (atomic number of the element) and a is the shielding (screening) constant). The value of « i.e. shielding effect can be determined using the Slater's rules. (i) Atomic radius (A) Covalent radius : It is one-half of the distance between the centres of two nuclei (of like atoms) bonded by a single covalent bond, Covalent radius is generally used for nonmetals,36 | Short Formula (Chemisty) WNsese ESSPOROSS (8) Vander Waa's radius (Collision radius) : It is one-half of the internuclear distance between two adjacent atoms in two nearest neighbouring molecules of the substance in solid state. (C) Metallic radius (Crystal radius) Iti one-half ofthe distance between the nucte of two adjacent metal atoms in the metalic crystal latice. + Thus, the covalent, vander Wall's and metalic radius magnitude wise follows the order, ‘Variation in a Period Variation in_a Group Ina patiod ltt ight Ina group top to botom ‘Nuclear charge (Z) ereases by one unit ‘Nuclear charge (2) increases by more than ene unt Effective nuclear charge (Ze) almost remains constant Effective nuclear charge (Zu) also inctases | because of increased screening effect of nner shells elecrona, But number ofertas () remains constant But numberof eras (n) increases, ‘Asa esul, the electrons are puled coser to the | The effect of increased numberof atomic shells Geeatyraiecasioe overweighs the effect of increased nuclear charge, As a resultof this the sizeof atom increases fom top to feo bottom ina given group. Hence atomic radi decrease with increase in ‘toric number in @ period fom loft right. (iii) tonic radius : The effective distance from the centre of nucleus ofthe ion up to which it has an influence in the ionic bond is. called ionic radius. Cation ‘Anion [fi Tormed by the lose of one or mare clecirone Wom|f is Tormed by The Gain of one or more cleans 1h Te Ihe valence shell ofan atom of an element valence shell of an stom of an element Ications are smaller than the parent atoms because, | Anions are larger than the parent atoms because li) the whole of the outer shell of electrons is usualy) anion is formed by gain of one or more electrons in the removes neural atom and thus. number of electrons incceases bu |i) in 2 cation, the number of positive charges on thelmagnitude of nuciear charge remains the same. Jnucieus is greater than number of ortital electrons) nuciear charge per electrons is thus reduced and the leading to inctesed inward pull of remaining electronslelecrons clouds held less tghty by the nucleus leading to Jcausing contraction in size ofthe ion tre expansion of the outer shell, Thus size of anion is increased (v)_onisation Energy : lonisation energy (IE) s defined as the amount of energy required to remove the most loosely bound electron from an isolated gaseous atom to form a cation Mg) ©) M@+e ; M@)+IE,—> Me@+re MP @) +1E, —> P@ +e IE, IE, & IE, are the I, IF" & Ionization energies to remove electron from a neutral atom, monovalent and divalent cations respectively. In general, (IE), < (IE), < (IE), < + Factors Influencing lonisation eneray (A) Size of the Atom : lonisation energy decreases with increase in atomic size. (8) Nuclear Charge : The ionisation energy increases with increase in the nuclear charge. (©) Shielding or screening effect: The larger the number of electronsin the inner shells, greateristne screening effect and smaller the force of attraction and thus ionization energy (IE) decreases. (0) Penetration effect of the electron : Penetration effect of the electrons follows the order s> p> d> # for, the same energy level. Higher the penetration of electron higher wil be the ionisation energy.37 Short Formula (Chemisty) NSesenence ©) Electronic Configuration: fan atom has exacly half-flled or completely filed orbitals, then such an “ eo o00000 arrangement has extra stabil, Electron Gain Enthalphy : (CHANGED TOPIC NAME) The electron gain enthalpy A.,H’, is the change in standard molar enthalpy when a neutral gaseous ‘atom gains an electron to form an anion, X@+e@—*X@) The second electron gain enthalpy, the enthalpy change for the addition of a second electron to an. initially neutral atom, invariably positive because the electron repulsion out weighs the nuclear attraction, Group 17 elements (halogens) have very high negative electron gain enthalpies (i. high electron affinity) because they can attain stable noble gas electronic configuration by picking up an electron. ‘Across a period, with increase in atomic number, electron gain enthalpy becomes more negative ‘As we move ina group from top to bottom, electron gain enthalpy becomes less negative Noble gases have large postive electron gain enthalpies Negative electron gain enthalpy of © or Fis less than $ or Cl Electron gain enthalpies of alkaline earth metals are very less or positive Nitrogen has very low electron affinity 1 (Electron atfnty =<" (ip Electron affinity « Effective nuclear charge (,.) 1 (id Electron atinty “Senay afect () Stability of hal filed and completely filed orbitals of a subshell is comparatively more and the addition of an extra electron to such an system is difficult and hence the electron affinity value decre (V) Electronegativity : (@) @ vi Electronegativity is a measure ofthe tendency ofan element to atract shared electrons towards itself ina covalently bonded molecules Pauling’s scale A=X,-X,= 0.208 Exo - Ean Ene E,_= Bond enthalpy! Bond energy of A~B bond £7" = Bond energy of A~A bond , = Bond energy of 8 -B bond {All bond energies are in kcal / mol) N=X,-X,#0.1017 Ex e-sExaxEaw All bond energies are in kd/ mol ‘Mulliken's scale : _IE+EA a= Paulings’s electronegativity z, isrelated to Mulliken's electronegativity x, as given below. %o* 1.35 (4)!?=1.37 ‘Muliken’s values were about 2.8 times larger than the Pauling’s values, Periodicity of Valence or Oxidation States : ‘Thore are many elements which extibt variable valence. This is particularly characteristic of transition ‘elements and actinoids,38 | Short Formula (Chemistry) MNBesenence (Vill) Periodic Trends and Chemical Reactivity O —Imagroup, basic nature of oxides increases or acidic nature decreases. Oxides of the metals are generally basic and oxides of the nonmetels are acidic, The oxides of the motalloids are generally amphoteric in nature. The oxides of Be, Al, Zn, Sn, As, Pb and Sb are amphoteric. O __ Inaperiod the nature of the oxides varies from basic to acidic. Nao MgO ALO, SiO, PO, S80, Strongly basic Basic amphoteric Weaklyacidic Acidic Acidic.~=—=— Strongly acidic CHEMICAL BONDING Chemical Bond : In the process each atom attains a stable outer electronic configuration of inert gases, Ionic or Electrovalent Bont ‘The formation of anionic compound would primarily depends upon ‘The ease of formation ofthe positive and negative ions from the respective neutral atoms. ‘The arrangement of the positive and negative ions inthe solid, thats the lattice ofthe crystalline compound. Conditions for the formation of ionic compounds : @ —_Electronegativity difference between two combining elements must be larger. _lonization enthalpy (M(g) ~» M'(g) + eof electropositive element must be low. Gi) Negative value of electron gain enthalpy (X (g) + eX (q) of electronegative element should be high. &) Lattice enthalpy (M'(@) + X-(@) -+ MX (5) of an ionic solid must be high Lattice Enthalpy : ‘The lattice enthalpy of an ionic solid is defined as the energy required to completely separate one mole of a solid ionic compound into gaseous constituent ions, Factors affecting lattice energy of an ionic compound : 1 © Lattice energy = = inter-ionic Distance. +e (Lattice energy «2,2 Z, = charge on cation in terms electronic charge. Z'= charge on anion in terms electroniccharge. Determination of lattice energ Bor-Haber Cycle : Itinter relates the various energy terms involved during formation of an ionic compound, Ita thermochemical cycle based on the Hess's law of constant heat summation where (7, +r39 | Short Formula (Chemistry) MNBesenence Hydration Allthe simple salts dissolve in water, producing ions, and consequently the solution conduct electricity. Since Li is very small, tis heavily hydrated. This makes radius of hydrated Li' ion large and hence it moves only ‘slowly. In contrast, Cs’ isthe least hydrated because of its bigger size and thus the radius of the Gs" jon is smaller than the radius of hydrated Li, and hence hydrated Cs moves faster, and conducts electricity more readily Hydrolysis Hydrolysis means reaction with water molecules ultimately leading to breaking of O-H bond into H and OH ions, Hydrolysis in covalent compounds takes place generally by two mechanisms (@) By Coordinate bond formation : Generally in halides of atoms having vacant d-orbitals or of halides of atoms having vacant orbitals, (©) By H-bond formation : For example in Nitrogen trihalides General properties of ionic compounds {a) Physical state : At room temperature ionic compounds exist either in solid state or in solution phase but not in gaseous state. {b) Simple ionic compounds do not shaw isomerism but isomorphism is their important characteristic, e9.. FeSO,.7H0 | MgSO, .7H,0 {c) Electrical conductivity : All ionic solids are good conductors in molten state as well as in their aqueous solutions because their ions are free tomove. (D) SOLUBILITY OF IONIC COMPOUNDS : Soluble in polar solvents like water which have high dielectric constant Covalent character in ionic compounds (Fajan’s rule) Fajan’s pointed out that greateris the polarization of anion in amolecule, Cation anion more is covalent character in : More distortion of anion, more will be polarisation then covalent character increases. Fajan’s gives some rules which govem the covalent character inthe ionic compounds, which are as follows: ® Size of cation :Size of cation « 1 / polarisation. (Size of anion : Size of anion polarisation (i) Charge on cation : Charge on cation « polarisation. Charge on anion : Charge on anion a polarisation. () Pseudo inert gas configuration of cation : Covalent Bond : It forms by sharing of valence electrons between atoms to form molecules e.g, formation of Cl, molecule be bee orci-c Covalent bond between to Cl atoms The important conditions being that @ Each bond Is formed as a result of sharing of an electron pairbetween the atoms, @ Each combining atom contributes at least one electron to the shared pair. Gi) The combining atoms attain the outer- shell noble gas configurations as a result of the sharing of electrons.40 | Short Formula (Chemistry) WNsese ESSPOROSS Coordinate Bond (Dative Bond) The bond formed between two atom in which contribution of an electron pair is made by one of them while the sharing is done by both, 4 i © Ne; (ammonium ion) Co when 4 if Donor ‘Acceptor 0a, 9, i) 0, (oz v Gi) ©, (ozone) BN oo YN Other examples: H,SO,, HNO, , HO", N,O, [Cu(NH,) Formal Charge Formatcharge%:) |] _ [Fro numer of valence] _[- Total nurte of ron bona on | Teal oun of ~©4)| bonding (shared) Formal charges help in the selection of the lowest energy structure from a number of possible Lewis structures fora given species. Limitations of the Octet Rule : The incomplete octet of the central atom LiCl, BeH, and BCI, AICI, and BF, Odd-electron molecules nitric oxide, NO and nitrogen dioxide. NO, O=N-6 The expanded octet # i ‘O: LF FAIA: t zt ; 1-8-8-8-n ti a i F F 7 PF, sr, 1480. A. Other dawbacks ofthe octet theory Sessa yee ee oe compounds like XeF, , KF, , XeOF, ete. (@ _—_Thistheory does not account for the shape of molecules, Gi) Itdoes not explain the relative stability of the molecules being totally silent about the energy of a molecule.a“ “ (ii) Short Formula (Chemisty) MNGesenence Valence bond theory (VBT) : H,(Q) + 435.8 kJ mol-—» H(g) + H(@) > Enereyitaimat) 4358 Bond Longin 74pm wremudear distancs—> Orbital Overlap Concept according to orbital overlap concept, the formation of a covalent bond between two atoms results by pairing of electrons present, in the valence shell having opposite spins. ‘Types of Overlapping and Nature of Covalent Bonds ‘The covalent bond may be classified into two types depending upon the types of overlapping (i) sigma(o) bond, and (i) pi (x) bond ‘Sigma (o) bond : This type of covalent bond is formed by th along the internuclear axis, 3d to end (head-on) overlap of bonding orbitals ‘¢s-soveriapping + — s-orbital s-orbital $-s overlapping ‘¢s-povertapping ) +@@ — @@ ©-orbital p-otbital s-p orbital «p-povetapring isp of overtakes lace between a filed ral theo epeoaching aos. @@ + @2S — &@?e@ prota portal pb ovetping pix) bond : Inthe formation of x bond the atomic orbitals overlap in such a way that their axes remain parallel to each other and perpendicular to the intemuclear axis. ; ‘ } _ $ ‘—— p-orbital p-orbital a ‘Strength of Sigma and pi Bonds : In case of sigma bond, the overlapping of orbitals takes place to a larger extent. Hence, itis stronger as compared to the pi bond where the extent of overlapping occurs to a smaller extent.42 ‘Short Formula (Chemistry) WNResenense Valence shell electron pair repulsion (VSEPR) theory : The main postulates of VSEPR theory areas follows: 0 ‘The shape of a molecule depends upon the number of valence shell electron pairs [bonded or nonbonded) aroundthe central atom @ Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged. Gi) __ These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise distance between them. ™ The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at maximum distance from one another. 7] Amuttiple bond is treated as if it is a single electron pair and the two or three electron pairs of a multiple bond are treated as a single super pair w) Where two or more resonance structures can represent a molecule, the VSEPR model is applicable to any such structure The repulsive interaction of electron pairs decreases in the order: lone pair (‘p) - lone pair (¢p) > lone pair (ep) - bond pair (bp) > bond pair (bp) -bond pair (bp) Hybridisation : Salient features of hybridisation : “The numberof hybrid orbitals is equalto the numberof te atomic orbitals that get hybridised “The hybridised orbits are always equivalent in energy and shape The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals “These nybrid orbitals are directed in space in some preferred direction to have minimum repulsion between electron pairs and thus a stable arrangement is obtained. Therefore, the type of hybridisation indicates the ‘geometry of the molecules Important conditions for hybridisation : The orbitals present in the valence shell ofthe atom are hybridised The orbitals undergoing hyoralstion should have almost equal energy Promotion of electron isnot essential condition prior to hybridisation itis the orbital that undergo hybridization and not the electrons. 1 a 3. 4. lation of hybridisation of an atom in a molecule or ion: Steric number rule (given by Gillespie) : ‘Steric No, of an atom = number of atom boncled with that atom + number of lone pair(s) left on that atom. Table-3 ‘Steric number ‘Types of Hybridisati Geometry 2 sp Linear 3 sp Trigonal planar 4 3p Tetrahedral 5 spd Trigonal bipyramidal 6 spa Octahedral 7 spd Pentagonal bipyramidal Hybridization Involving d-orbital : ‘Type of orbital involved spd az spd dx —y°& dz? spd? em ye, dz? & dxy dsp" day43 | Short Formula (Chemistry) MNBesenence Molecular Orbital Theory (MOT) : developed by F. Hund and R.S, Mulliken in 1932. @ —_ Molecularorbitals are formed by the combination of atomic orbitals of comparable energies and proper symmetry. @ —_Anolectron in an atomic orbitals influenced by one nucteus, while in a molecular orbital tis influenced by two ‘or more nuclei depending upon the numberof the atomsin the molecule, Thus an atomic orbital is monocentric while a molecular orbital is polycentric. @_—__Thenumber of molecular orbitals formed fs equal to the number of combining atomic orbitals. When two atomic. orbitals combine, two molecular orbitals called bonding molecular orbital and anti-bonding molecular orbital are formed )—Themolecular orbitals ike the atomic orbitals are filled in accordance with the Aufbau principle obeying the Pauli Exclusion principle and the Hund's Rule of Maximum Multiplicity. But the filing order of these ‘molecular orbitals is always experimentally decided, there is no rule like (n + 1) tule in case of atomic orbitals CONDITIONS FOR THE COMBINATION OF ATOMIC ORBITALS : The combining atomic orbitals must have the same or nearly the same energy. 2 The combining atomic orbitals must have the same symmetry about the molecular axis. 3. The combining atomic orbitals must overlap to the maximum extent ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS : The increasing order of energies of various molecular orbitals for O, and F, is given below 918< 0" 15 < 025 < 0°25 < (x2p,= £2p) < 2p, <(t°2p,= K'2) <0'2P, “The important characteristic feature of this orders that the energy of o2p, molecular orbitalis higher than that of x2p, nd x2p, molecular orbitals. BOND ORDER Bond order (b.0.)= %#(N,—N,) A positive bond order (i.¢., N, > N,) means a stable molecule while a negative (ie., N, < N,) or zero (Le., N, = NJ bond order means an unstable molecule. NATURE OF THE BOND: Integral bond order values of 1, 2or3 correspond to single, double or triple bonds respectively BONDENGTH: ‘The bond order between two atoms in a molecule may be taken as an approximate measure ofthe bond length, The bond length decreases as bond order increases. MAGNETIC NATURE: Ifall the molecular orbitals in a molecule are doubly occupied, the substance is diamagnetic (tepelled by magnetic field) eg.,N, molecule Dipole moment : Dipole moment (j) = Magnitude of charge (q) x distance of separation (d) Dipole moment is usually expressed in Debye units (D). The conversion factors are 1D = 8.33564 « 10 Cm, where C is coulomb and mis meter. OQ 1 Debye= 1 10" e.s.u, cm, For example the dipole moment of HF may be represented as ad HE The shiftin electron density is represented by crossed arrow (| >) above the Lewis structure to indicate ‘the direction of the shit.44 | Short Formula (Chemisty) WNsese ESSPOROSS ‘a molecule will have a dipole moment ifthe summation of all ofthe individual moment vector is non-zero, \P? 1G? 1 Pa cose « Where Ris resultant dipole moment. Resonance Definition : Resonance may be defined as the phenomenon in which two or more structures involving in identical position of atom, can be written fora particular compound, For example, the ozone, O, molecule can be equally represented by he structures land I shown below Pe, —, rv JX of ¢ ' 0 Resonance in the O, molecule Resonance Hybrid : Its the actual structure of al different possible structures that can be written for the ‘molecule without violating the rules of covalence maxima for the atoms, o-0-. a Resonance hybis Hydrogen Bond : nan HPA Fe aa HS Conditions required for H-bond () Molecule should have more electronegative atom (F, ©, N) inked to H-atom (i) Size of electronegative atom should be smaller, (i Alone pair shouldbe present on electronegative atom Order of H-bond strength | a Hee —0-¢H- ‘TYPES OF H-BONDS: (A) Intramolecular H-Bonding : itis formed when hydrogen atom is present in between the two highly electronegative (F, O, N) atoms within the ‘same molecule. -nyoxy bonzaishyeo Ithas lower boiling point (/e. more volatile) than its para-derivative Necessary conditions for the formation of intramolecular hydrogen-bonding : (@) the ring formed as a result of hydrogen bonding should be planar. (b)a5-or6- membered ring should be formed (©) interacting atoms should be placed in such a way that there is minimum strain during the ring closure.Short Formula (Chemisty) MNBesenence (8) Intermolecular H-Bonding : itis formed between two different molecules of the same or different compounds, (@ — Inwater molecules Be Be be be bt be bt 4-0. W—-o. H#-0. Ho 1 H I Hee He HOF He (©) The hydrogen bonds in HF link the F atom of one molecule with the H-atom of another molecule, thus, forming a zig-zag chain (HF), in both the solid and also in the liquid, Intermolecular forces (Vander Waal’s Forces) : Intermolecular attractions hold two or more molecules together. These are weakest chemical forces and can be of following types. (@) lon-cipole attraction (b)Dipole-cipole attraction (©) lon-induced dipole attraction (@ Dipole-induced dipole attraction (€) Instantaneous dipole- Instantaneous induced dipole attraction : (Dispersion force or London forces) Q Strength of vander waal force ~ molecular mass, 2 van der Waal's force = boiling point. Metallic bond : ‘Two models are considered to explain metalic bonding: (A) Electron-sea mode! (8) Band model ‘Some special bonding situations : (@) Electron deficient bonding: ‘There are many compounds in which some electron deficient bonds are present apart from normal covalent bonds or coordinate bonds. These electron deficient bonds have less number of electrons than the expected ‘such as three centre-two electron bonds (0-2e) present in diborane BH, Al,(CH)), BeH,(s) and bridging metal carbons. (b) Back Bonding : Back bonding generally takes place when out of two bonded atoms one of the atom has vacant orbitals (generally his atom is from second or third period) and the other bonded atom is having some non-bonded electron pair(generally this atom is from the second period). Back bonding increases the bond strength and decreases the bond length, For example, in BF, GV F vacant Filed 2potial 2parbial the extent of back bonding in boron trihalides. BF,> BCI, > BBr,48 | Short Formula (Chemistry) MNBesenence COORDINATION COMPOUNDS Addition Compounds : ‘They are formed by the combination of two or more stable compounds in stoichiometric ratio. These are (1) Double salts and (2) Coordination compounds Double salts : ‘Those addition compounds which ose their identity in solutions €9.K,80, ,Al(S0,), Coordination Compounds : ‘Those addition compounds which retain their identity (i.e. doesn't lose their identity) in solution are Fe(CN), + 4KCN ——> Fe(CN), . AKCN or K, [Fe(CN),] (aq) <= 4K’ (aq.) + IFe(CN)_}* (aq) Central Atom/ton Ina coordination entity-the atomyion to which are bound a fixed number of ligands in a definite geometrical arrangement around it Ligands : The neutral molecules, anions or cations which ae directly inked with central metal torn orion inthe coordination entity are called ligands. Chelate ligand : Chelate ligand is adi or polydentate ligand which uses its two or more donor atoms to bind a single metal ion producing a ring. Ambidentate Ligand : Ligands which can igate through two different atoms present int nitito-O ° re MeNKS nition Meo M M) and ax acceptor (OC -2x where 0 Cu,S +2Fe0 + 380, CUS + FeO + SIO, —> FeSiO, (Fusiiesieg) + Cu,S (matte) “(easted wate) (woe tae Cowes layer Matte also contains a very small amount of ironll) sulphide, ‘To remove unwanted acidic impurities like sand and P,,,, smelting is done in the presence of limestone. Caco,» Ca0+c0, CaO + SiO, —+ CaSIO, (Usb se) 60a0 + P,0,, > 26a(PO,), (tbl sag- Thomas so) Reduction of a metal oxide : ‘The free metal is obtained by reduction of a compound, using either a chemical reducing agent or electrolysis.58 Short Formula (Chemisty) NSesenence Chemical reduction method : Reduction with carbon: PbO + C— Pb + CO (extraction of lead) Reduction with CO : In some cases CO produced in the furnace itself is used as a reducing agent. Fe,0,+3CO—52Fe+3C0, Reduction by other metals Metallic oxides (Cr and Mn) can be reduced by a highly electropositive metal such as aluminium that liberates 2 large amount of energy (1675 ks/mol) on oxidation to Al,O,. The process is known as Goldschmiat or aluminothermic process and the reaction is known as thermite reaction Cr,0, + Al 2Cr (1) +Al,0, Magnesium reduction method : Magnesium is used in similar way to reduce oxides. In certain cases where the oxide is too stable to reduce, electropositive metals are used to reduce halides. Ticl, +2 My Melee, T+ 2MgCl, Ticl,+4Na —MIPD*28_, Ti+ 4NaCl Self-reduction method : This method is also called auto-reduction method or air reduction method. Ifthe sulphide ore of some of the less electropositive metals ike Hg, Cu, Pb, Sb, etc. are heated in air, a part of these is changed into oxide or sulphate then that reacts with the remaining part ofthe sulphide ore to give its metal and SO, Cu,S +30, —> 3Cu,0 +20, 20u,0 + Cus —> 6Cu+SO, Electrolytic reductior Itpresents the most powerful method of reduction and gives a very pure product. Asit is an expensive method ‘compared to chemical methods, itis used either for very reactive metals such as magnesium or aluminum or {or production of samples of high purity. 4. Imaqueous solution : Electrolysis can be carried out conveniently and cheaply in aqueous solution that the products do nat react with water. Copper and zinc are obtained by electrolysis of aqueous solution of their ‘sulphates. 2, Infused melts : Aluminum is obtained by electrolysis of a fused mixture of Al,O, and oryolite Na {AIF Extraction of Aluminium : It involves the following processes (@) Purification of bauxite ()Bayer’s Method ij Halrs Method (il) Serpeck’s Method {used for red bauxte containing Fe,0, and ‘ileatesasimpurties) ALO.7#0+ 2NaaH HE 2NaAIO, (soluble) +34,0 Fe. (insoluble) separated as red mud by| fiteration solution is dluted with water and seeded with feshly prepared A(OH), Trnduces the preciptation of AKOH),. AKOM), i fered leaving behind silicates insoluton NaNO, +2H,0-» NaOH + AOH),L 2N(OH), — "> NLO,+3H.0 (sed for rod bette containing Fe,O,ane ‘sllcates.asimourties) ARLO,.2H,0 + Na,co, "> 2NANIO, (soluble) +00,+2H.0 2NaAl0,+3H,0+C0, "> 2AKOH,L+Na.CO, 2A10K), #25 AL0,+3H,0 (used "white bauxltecontaining ‘sileaasimputites) ALO, .2H.0 + 90 + Nien? 2AIN + 300 + 2H,0 2AIN + 3H,0-+ A(OH,L + NH, S10, + 260 -» 260, + si ‘Sticone volailises at this temp, 2A(0H), #2" 4,0, +34060 ‘Short Formula (Chemisty) MNGesenence (b) Electrolytic reduction (Hall-Heroult process) : 2ALO,+ 36 ——> 4Al+ 300, Cathode: A> (melt) 3° — Al() Anode Cis) + O* (melt) » COG) + 2e (6) +20 (mel) —+ CO, (@) +4e Metallurgy of some important metals Extraction of iron from ore haematite Reactions involved : ‘At 500 - 800 K (lower temperature range in the blast furnace) 3Fe,0,+CO —> 2Fe,0,+CO, Fo,0,+ CO —> 3Fe+4CO, Fe,0,+CO > 2Fe0 +0, ‘At 900 ~ 1500 K (higher temperature range in the blast furnace) c+c0, —> 200 FeO +CO > Fe+Co, Limestone is also decomposed tom CaO which removes silicate impurity of the ore as slag, The slag is in ‘molten state and separates out from iron. CaCO, —»Ca0+C0,; Cad+Si0, > Casio, Extraction of copper: From copper glance / copper pyrite (self reduction) : 2CuFeS, + 40, Cu. + 2FeO + 380, Cu,S + Fed + SiO, + FeSiO, (tsi sing) + Cu,S (ate) 2FeS+30,—> 2FeO +280, ; FeO+SI0, —» Fesio, 2Cu,S+30, —» 2Cu,0+280,; 2Cu,0+ Cu,S —> 6Cu+ SO, (solf reduction) Extraction of lead : 6 2805(6) +30, (6) —*-» 2F00 6) “2+ 2°04) +60, 6) (@ —aPbsis) T=" > Pps (s)+ 2Pb0 (6) NE > aPD(H) + SO, (Q) Extraction of zinc from zinc blend The ore is roasted in presence of excess of air at temperature 1200 K. 2ZnS +30, + 22n0+2S0, ‘The reduction of zinc oxide is done using coke, Zn0 +6 887", 20460 Extraction of tin from cassiterite : The concentrated ore fs subjected tothe electromagnetic separation to remove magnetic impurity of Wolframite, ‘SnO, is reduced to metal using carbon at 1200 - 1300°C in an electric fumace. The product often contains traces of Fe, which is removed by blowing air through the molten mixture to oxidise FeO which then floats to the surface, Sn0, + 20 —» Sa + 260 2Fo+ 0, —+ 2d Extraction of Magnesium : From Sea water (Dow's process) : ‘Seawater contains 0.13% magnesium as chloride and sulphate. itinvolves following steps. (@ Precipitation of magnesium as magnesium hydroxide by slaked lime, (©) Preparation of hexahydrated magnesium chloride61 co) ‘Short Formuta (Chemistry) MNBesenence ‘The solution on concentration and crystalisalion gives the crystals of MgCl. H.O. (Preparation of anhycrous magnesium chloride. (@ Electrolysis offused anhydrous MgCl, in presence of NaCI MgCl, <= Mg + 2c Atcathode: Mg + 2e° —> Mg(@9% pure); Atanode 2cr —> Cl, +26 Extraction of gold and silver (MacArthur-Forrest cyanide process) (@) From native ores : Extraction of gold and slverinvolves leaching the metal with CN ‘4hy Ag (8) + BCN (aq) + 2H,O(aq) + 0,9) > 4{AU/Ag (CN) Faq) * 40H-(aq) 21Au/ Ag (CN). (aq) * Zn(s) —» 2Au/Ag (s) + [2n(CN),F- (aa) (b) From argentite ore ‘Ag.S (conc. ore) + 2NaCN —“\— 2AgCN + Na.S. 4Na.S + 50, + 2H,0 > 2Na,SO, + 4NaOH + 28 AgCN+ NaGN ——+ NafAg(CN), (Soluble complex) 2NalAG(CN),}+ Zn (dust) —» 2Ag | + Na,(Zn(CN) Purification or Refining of metals : Physical methods : These methods include the following processes () Liquation process : This process is used for the purification of the metal, which itselfis readily fusible, but the impurities present in tare not, used forthe purification of Sn and Zn, and for removing Pb from Zn-Ag alloy. (lt) Fractional distillation process : This process is used to purify those metals which themselves are volatile ‘and the impuritiesin them are nonvolatile and vice-versa, Zn, Cd and Hg are purified by his process, (lil Zone refining method (Fractional crystallisation method) : This process is used when metals are required in very high purty, for specific application. For example pure Si and Ge are used in semiconductors Chemical methods : These methods include the following methods () OXIDATIVE REFINING : This method is usually employed for refining metals ike Pb, Ag, Cu, Fe, etc. Inthis method the molten impure metal is subjected to oxidation by various ways. (W) POLING PROCESS: This process is used for the purification of copper and tin which contains the impurities oftheir own oxides, Green wood + Hydrocarbons > CH, 4CuO + CH, + 4Cu (pure metal) + CO, + 2H,0 (lll) ELECTROLYTIC REFINING : ‘Some metals such as Gu, Ni, and Al are refined electrolytically (V)__ VAPOR PHASE REFINING : (Extraction of Nickel (Mond’s process) :The sequence of reaction is H,0(@) + —+ COG) +H, Nig) +4 CO) 2°, [NICO] (6) INI(CO),@) 20°, Ni+4c0@) (i) Van Arkel-De Boer process : Impure Ti+ 21, 50°, Ti), 00% _, Ti 21,62 Short Formula (Chemisty) MNBesenence s-BLOCK ELEMENTS & THEIR COMPOUNDS Group 1 of the periodic table consists of the elements : lithium, sodium, potassium, rubidium, caesium and francium ‘The elements of Group 2 include beryllium, magnesium, calcium, strontium, barium and radium, Hydration Enthalpy ‘The hydration enthalpies of alkali metal ions decrease with increase in ioniosizes.L* has maximum degree of hydration and for this reasons lithium salts are mostly hydrated e.9., LiCl. 2H,O Physical properties : Allthe alkali metal are silvery white, soft and light metals. Because of the larger size, these element have low density, The melting and boiling point of the alkali metals are low indicating weak metallic bonding alkali ‘metals and their salts impart characteristic colour to an oxidizing flame. Metal [or Na K RED Pee. Violet” Icolour |crimson Yellow tilec |Red — |Btue red violet Chemical Properties: ‘The alkali metal ae highly reactive due to their larger size and low ionization enthalpy. © Reactivity towards air : They bum vigorously in oxygen forming oxides. Lithium forms monoxide, sodium forms peroxide, the other metals form superoxide. © Reducing nature: The alkali metals, are strong reducing agents, thium being the most and sodium the least powerful Solution in liquid ammonia: The alkali metals dissolve in liquid ammonia giving deep blue solution which are conducting in nature. M+ (c+ y) NH, — IM(NH, ),'# [e(NH) ‘The blue colour of the solution is due to the ammoniated electron and the solutions is paramagnetic. Me(am)+0-+NH, (0 MNH,(arn) +1/2H.(0) In concentrated solution, the blue colour changes to bronze colour and becomes, diamagnetic. ANOMALOUS PROPERTIES OF LITHIUM (9 exceptionally small siz ofits atom and ion, and (i) high polarising power (.e., charger radius rato). ‘The similarity between lithium and magnesium is particularly striking and arises because of their similar size: atomic radi, Li = 152 pm, Mg = 160 pm; ionic radil: Lir= 76 pm, Mg = 72 pm. GROUP 2 ELEMENTS : ALKALINE EARTH METALS ‘The frst element berylium differs from the rest of the member and shows diagonal relationship to aluminium, Hydration Enthalpies Hydration enthalpies of alkaline earth metal ons. Be* > Mg > Ca > Si > Ba. The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions. Thus, compounds of alkaline earth metals are more extensively hydrated than those of alkali metals ,e.g., MgCl, and CaCl, exist as MgCl, 6H. and CaCl, 6H, while NaCl and KCI do not form such hydrates. on standing Physical Properties ‘The alkaline earth metals, in general, are silvery white, lustrous and relatively soft but harder than the alkali ‘metals. The melting and boiling point of these metals are higher due to smaller sizes. Because of the low ionisation enthalpies they are strongly electropositive in nature. The electrons in berylium and magnesium are too strongly bound to get excited by flame, Hence these elements do not impart any colourto the flame, Calcium, strontium and barium impart characteristic colour tothe flame,63 Short Formula (Chemisty) MNGezcnecce Metal Be Mg ca St Ba colour | No | No | Brick [Crimson] Apple colour | colour | rea green Chemical Properties (© Reactivity towards air and water: Beryllium and magnesium are inert to oxygen and water. Magnesium is more electropositive and bums with dazzling briliance in airto give MgO and Mg.N, Calcium, strontium and barium are readily attacked by airto form the oxide and nitride (© Reducing nature : The alkaline earth metals are strong reducing agent. This is indicated by large negative value of ther reduction potentials. © Solution in tiquid ammonia: The alkaline earth metals dissolve in liquid ammonia to give deep blue black solution forming ammoniated ions. M+ (x+y) NH, > [ M(NH),P"+2 [e(NH), > From these solutions, the ammoniates, [M(NH.),|* can be recovered. ANOMALOUS BEHAVIOUR OF BERYLLIUM Beryllium the first member of the Group 2 metals, shows anomalous behaviour as compared to ‘magnesium and rest ofthe members. Further, it shows diagonal relationship to aluminium. Diagonal Relationship between Beryllium and Aluminium ‘The ionic radius of Be* is estimated to be 31 pm; the charge/radius ratio isnearly the same as that of the AP*ion. Hence beryllium resembles aluminium in some ways. Compounds of s-block elements : ‘Sodium Oxide (Na,O) : oe] Jo, limited amount ) O.lexcess) ‘comnbustionShort Formula (Chemistry) MNGezcnecce 3. Potassium Super oxide (KO,): Combustion] 0, (From ar HG + 0, KOR] 4. x+x0 ‘Sodium Carbonate (Na,CO,): NH, = 00,7} > [NCO] + Na‘Short Formula (Chemistry) Aiescnecse 6. Potassium sulphate (K,SO,): TS Ko} 0, SANK) 5 Tram 7. Quick Lime, Slaked Lime and Lime Water wove no Linens OE ayerine MO Stes e aes ‘ates ‘exon ‘Suspension <—— eal anded in water este, re ir Coston tm wae ook fe H+ ct pene furnace at 200°C Cac Bee FES coy an Nin ARMA NHL(Ammonio) ay er Nik Flim (ito wasting wo | Lime waar or he detection of 60, cao #2 caon| oh Quickie Sioked Bleaching powder im” | aco, stk win | NE2. _aohicaustosota) eben aa LS. tinea or dprsvwater sotatine Sehos Sea (amos OH) a Nao = Soveicren tombe roses ae (eutdg ets 3Ca(OH), + 2Cl, —+ Ca(OC!),, Ca(OH),.CaCl,. 2H,0 (bleaching powder.‘Short Formula (Chemistry) WNSes ESSPOROSS p-BLOCK ELEMENTS & THEIR COMPOUNDS TRENDS IN PROPERTIES OF p-BLOCK ELEMENTS. connate, ee ee (A) GROUP 13 ELEMENTS : THE BORON FAMILY ‘Oxidation state and trends in chemical reactivity : General Oxidation State = + 3 Reactivity towards acids and alkalies 2Al(s) + 6 HCI(aq) —> 2Al* (aq) + 6 CH1aq)+3 H,(9) 2Al(S) + 2NaCH (aq) + 6H,0 (1) —> 2Na" [AIOH),| (aq) + 3H,(9) Sodium tetrahydroxoaluminate (I) Reactivity towards halogens 2E(6) + 3X, (@)->2EX,(8) X= F,CIBF,) BORON (B): ‘Some Important Reactions of Boron and its compounds :WAGssenencs some be ont eto strstr Hse laps (ac} 180°C, 750m 12. BOR, x 6H neo, 78H: » Aoetrer Tati sa0r © carting, OF Ce iWPBCI+Hel MBH, BM, NH EE HLENH LS IBM H,80,(EN), a RCH.CHOH BAR, (borazine} ‘Small amines such as NH,, CH,NH, and (CH), NH give unsymmetrical cleavage of diborane. BH, + 2NH, —> [H.B (NH).J"+ [BH Large amines such as (CH,).Nand pyridine give symmetrical cleavage of diborane. 2(CH),N+8.H, —> 2H,B <— N(CH), | +200 286204", 264.0 porane carbony) (B) GROUP 14 ELEMENTS : THE CARBON FAMILY Carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) are the members of group 14. Electronic Configuration = ns* np’. ‘Oxidation states and trends in chemical reactivity ‘Common oxidation states = +4 and +2. Carbon also exhibits negative oxidation states. In heavier members the tendency to show +2 oxidation state increases in the sequence Ge < Sn > Si> Ge ~ Sn, Lead does not show catenation. Due to the property of catenation and pr-pr bonds formation, carbon is able to show allotropic forms. Bond Bond enthalpy (kJ mot) Bond Bond enthalpy (kJ mo!) co 348 Si-Si 237 Ge—Ge 260 ‘sn—Sn 240 Allotropes of Carbon Diamond: Crystalline lattice sp" hybridisation and linked to four other carbon atoms by using hybridised orbitals in tetrahedral manner. The C-C bond lengths 154 pm. and produces a rigid three dimensional network of carbon atoms. Graphite : Graphite has layered structure. Layers are held by van der Waal's forces and distance between two layers is, 340 pm. Each layers composed of planar hexagonal rings of carbon atoms. CC bond length within the layer is 141.5 pm, Each carbon atom in hexagonal ring undergoes sp* hybridisation graphite conducts electricity along the sheet. Graphite cleaves easily between the layers and therefore, itis very soft and slippery. For this, reason graphite is used as a dry lubricant in machines running at high temperature, Fullerenes : C,, molecule has a shape like soccer ball and called Buckminsterfullerene. It contains twenty six membered rings and twelve five membered rings. This ball shaped molecule has 60 vertices and each one is occupied by ‘one carbon atom and it also contains both single and double bonds with C —C distance of 143.5 pm and 138.3, pm respectively. SOME IMPORTANT REACTIONS OF CO, CO, AND METAL CARBIDES : KIFo(CN}]+ H,S0. (cone) FeiCo, HcooH Fe CO, Cis) + H01@) A atone [Mts n.cont rey Nx. ho no CHO Fe41,0, mgior,+ Bcc HSo-—+ Hoo; —+ co}a) ) © 0) «) ) ‘Short Formula (Chemisty) MNGezcnecce CLASSIFICATION OF SILICATES V4 Onthositicates:| AS Pyrosilicate : i\ fos, cyclic silicates i N A LN Chain silicates : Two dimensional sheet silicates : In such silicates, three oxygen atoms ofeach tetrahedral are shared with adjacent SiO,“ tetrahedtals. Such sharing forms two dimension sheet structure wit general formula (Si,0,),°~ Three dimenstional sheet silicates : “These silicates involve al four oxygen atom in sharing wih adjacent SiO, * tetrahedral units. SILICONES Silicones can be prepared from the following types of compounds only ORS! — RSC, Gi) RSICI, = Silicones from the hydrolysis of (CH), SiCl cH, cH, cH cH 2(CH),SICI 29, 2(CH,), Si (OH) —> ok-iom +HO— 0H, 89, cn a i—cH, oH, on, éu eM, = Silicones from the hydrolysis of a mixture of (CH,), SiCI & (CH), SICl, ode Lot al : fs i u70 | Short Formula (Chemistry) MNBesenence “= When compound like CH, SiCl, undergoes hydrolysis, a complex cross-linked polymer is obtained. = The hydrocarbon layer along the silicon-oxygen chain makes silicones water-repelient COMPOUNDS OF LEAD: fy Pe co, prorn.raco. + Hot PRC | HC. pac10,4 (elon) 4 « ws. Spa tom {1schd |] 0, rem ay pe fo PS re oemnr Pao. | -2780.PH0, Poinio,,+ 120, + oN PLO, HE sprcs sows fA Ee Peo “No,+0, Poon COMPOUNDS OF TIN: S90, «OH 2H sna Fc <2 [Src Ft Sel] + Hg,c 2 ig : (wists pet ‘oe o£ lo Hot \i0 ove smoHier jsncur Sec sou, (©) GROUP 15 ELEMENTS : THE NITROGEN FAMILY Electronic Configuration : ns? np* Covalent and ionic (in a particular state) radii increase in size down the group, ‘Atomic and lonic Ra Physical Properties Allthe elements of this group are polyatomic. Metallic character increases down the group. The boiling points » In general , increase from top to bottom in the group but the melting point increases upto arsenic and then. decreases upto bismuth. Except nitrogen , al the elements show allotropy.