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    )\ Resonsence Educating for better tomorrow TRL A Formula Book for Engineering Entrance Examinations (S25 UP ae ele {The Gateway to ITs, NT, IT, ISERs & Prominent Engineering/Science Ins! Best Wishes for Your Success in Competitive Examinations ahead !!! This Booklet has been prepared by Resonance for the benefit & academic support to sincere students. You can send your feedback/suggestion on this booklet at feedback@resonance.ac.in PCW Resonance J iw.nimission Announcement eT a eas nan Toca at a Nurturing Talent... Creating Champions. From 'Within' You To A 'Winning' You -—————> Grand Success in IIT-JEE 2011 "The Best Ranks fom Yourlong Classroom Programmes nlIT-JEE 2011 by any estat in Kot nd entre Wes, East, North & Central ni ‘SHUBHAM MEHTA Toran Desseen ea Total Selections in IIT-JEE 2011 prriiet Gods Erp rere 1816 rere pane Pec (Vearlong Classroom: 1197 | Distance: 619) 17 All india Ranks in TOP: 100 (Wearlong Classroom: 13 | Distance: 4) F/ 9/9/9/ 2/F (2 ADMISSION ANNOUNCEMENT 2012-13 |¥e Programmes (YCCPs) oo fomsorrry foment a eo Taper Gh en) aT Tet Tins Tage de a ons Cement 2013 [Avo MI Moving Stdemis| 25.00.2012 | 15.04.2002 = Ll M13 | vex Moving Stoderes | is.ne2012 | 14.05.2002 [oenoami2 [| — 2013_| Hl Apparing Soden | ascaa012 | owasama | once | Ey Wl Appeaing Sheders | 16.0¢2012 | 2a05.2072 | reo6.2012 | a7 2012 ce [eee en ee cee ie 2 sen wet Ge Dal litt Tie Seed sara [io noag Suns |_aeaz02 | 005202 | paren | ReStDefrs Adis eSt Det Aiss Dasn of eS Sara [tettvag Ser] Sma |_— en sem | mem | masa | sin PM (2) Onine\iee wacsonnc in rover deta an by ONL paying ro CubeCart Net aki. 1 Intent Conrad state Oe neta nie Msn rennin Rona atesaaan snes apons tea ‘COST OF ADMISSION PACKET: For ISEET [NTJE/AIEEE) Courses: 1000 |For NEET (AIPMIT)/SAT Courses: 500: [For PCCP Course: ® 200%. NotI yu make D or Ads ace tan pas anon yor nar, ths an, dss nlc ting pres, sta ads and contactable runbas an the baksde th ant OD. Ase tp te phaacopy af D wih you ue lens Resonance Eduventures Pvt. Ltd. CORPORATE OFFICE: CG Tower, A-48 & 52, Near ity Mal haw Hood, Kta Rj) 324005 | Tl: 07463192222, 3012222, 3022222, 2437144 To Know more: sms RESO at 56677 | Toll Free : 1800 200 2248 | contact@resonance.ac.in | wwveresonance.acin | WAPsite: m.resonance.acin @ tecebook.convResonancetas @ twittercon/ResonancetGy @ly wwonyoutbecamiesawatch E) Resorancesutogspet.com Ef lnkosn comwvRosonanceE dy Short Formula (Chemisty) WNReserecce SHORT FORMULA (GYAN SUTRA) - a CHEMISTRY aE ATOMIC STRUCTURE Estimation of closest distance of approach (derivation) of a-parice nae ‘The radius of a nucleus : R=R, Aon Planck's Quantum Theory : Energy of one photon = hy = 3° ioscan oe Bohr's Model for Hydrogen like atoms : 4. mur=n 2 (Quantization of angular mornentur) & : : E. aeziextot = yom = 13620; a 0:529 xn? yu E20", 248x108 xz Zz mi oh 0 ‘ De-Broglie wavelength : h h ‘p(for photon) Wavelength of emitted photon : ta genet, 7 of ne) No.of photos emited by a sample of M atom : an(an+t) 2 Short Formula (Chemistry) Heisenberg’s uncertainty principle : WN Sesenecce ee A a axap> Geof maxave ow axava Ze Quantum Numbers: + Principal quantum number (7) =1,2,3,4 tO. nh * Orbital angular momentum of electron in any orbit = 5 . Azimuthal quantum number (£) = 0, 1, ..... to (n= 1). id Number of orbitals in a subshell = 2¢ + 1 ot Maximum number of electrons in particular subshell = 2 « (2¢ + 1) h + onital angular momentum L= 2 Jah =n fTED STOICHIOMETRY Mass of one_atom of an element o Relative atomic mass (R.A.M) = = Total Number of nucleons. macs of one earbonatom Yemen Tanber Se Volime a STP e Mole) mal. wt} | mol. we Att | [At wt (sss ] Density: density of the substance ‘Specific gravit density of water at 4°C Forgases: Molar massof the gas Pu Absolute density (massivolume)= ior volume ofthe gas. «= SS= PORT Gm PMs Mose _ Mine Vapour density VO= gq, M,,= 2D. Pier = My, 2 Short Formula (Chemistry) WNSeserence Mole-mole analysis : = At. wtf Mal. WA. Mole-mote: (egy =A ge) +] | —o] fal we e204 oo [Wass] ee Molarity (M) ___wet000 Molarity (M)= gL wi of solute) Vase Molality (m) number of moles of solute . 1900 ww, Mw, Molality= “mass of solvent in gram 1000 w,/ Mw, Mole fraction (x) Me acinotstonge)= 0 reaction wil shift in the forward direction ‘An <0. reaction will shift in the backward direction An = 0 reaction will not shift Effectof 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 IFinert gas is added then to maintain the pressure constant, volume is increased, Hence equilibium will shift in the direction in which larger no. of moles of gas's formed ‘An > 0. reaction will shift in the forward direction ‘An <0 reaction will shift in the backward direction ‘An-= 0 reaction will not shift @ Constant volume: Inert gas addition has no effect at constant volume. Effect of Temperature Equilibrium constant is only dependent upon the temperature, aH a as AE and intercept = 2S R mt R Upto nkys potent asain wh spe * 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 shiffs in the forward direction with increase in temperatutre * For aH < 0, reaction shifts in the backward direction with increases in temperature, * Ifthe concentration of reactantis 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 = —Pattialpressure of #;O vapours _ Vapour pressure of H,Oat that temp, 48 | Short Formula (Chemistry) WNResenence 1 ° Thermodynamics of Equilibrium : AG = AG*+ 2,303 RT log, Ky) an? (44 Vant Hoff equation- 10g | Lh 2303R IONIC EQUILIBRIUM OSTWALD DILUTION LAW: _ HAT] _[Coleo) HA] (=o) Dissociation constant of weak acid (K,) , Ky Mace 1, then t— Similaty for a weak base , “Yq. Higher the value of K, /K, , strong isthe acid / base. Acidity and pH scale : pH==log (where @,> is the activity of Ht ions = molar concentration for dilute solution) [Note: pH can also be negative or > 14] PH = — log [H'); POH = — log [OH] pka=~log Ka : pk log Kb ; PROPERTIES OF WATER : 5 In pure water [H']=[OH] _soitis Neutral. Moler concentration / Molarity of water = 55.56 M. lonic product of water (K,) = H'][OH'] = 10- at 26° (experimentally) pH=7=pOH = neutral pH<7 orpOH>7 => acidic pH >TorpOH<7 = Basic Degree of dissociation of water: no. of moles dissociated 107 Total No.ofmolesinitiallytaken ~ 55.55 Seater eee Absolute dissociation constant of water: IHUTIOH] _ 107? x10 10x10" 21.810 1H.0] 35.55 14 | Short Formula (Chemistry) WNSeserence log (1.8 x 10° = 16-109 1.8= 15.74 KK, = 011 [0H]=K, => Note: for a conjugate acid- base pairs pK,+ pK, = pk, = 14 at 25°C. pK, of H,0 jons=—1.78 PK, of OH ions =—1.74. © pH Calculations of Different Types of Solutions : (a) Strong acid solution : __feoncentration is greater than 107M. In this case H* ions coming from water can be neglected, (Mf concentration is less than 10M Inthis case H* ions coming from water cannot be neglected (b) Strong base solution : Using similar method as in part (a) calculate first [OH] and then use [Ht] x [OH © PH of mixture of two strong acids Number of H" ion trom Fsolutio Number of H’ ions from ll-solution = N,V, NM ENV WIEN (@ —_ pHof mixture of two strong bases : NV +NeVe VytVe (e) pH of mixture of a strong acid and a strong base : [oH]=N NiV4—NoVe VaVe IFN,V,> NLV,. then solution wil be acidic innature and tH'}= N= IFN,Y, > N,V,, then solution will be basic in nature and [OH (9 pHofaweak acia{monoprotic} solution: HIIOH] _ ca? WA” a ifaxta(t-a)=1 3 K=Ce = (is vali if « <0.1 oF 10%) Onincreasing thedition = > = CL at and [HY L + pHT (9) pHofa solution of a polyprotic weak acid : paz oro). 48 | Short Formula (Chemistry) WNSecerecce RELATIVE STRENGTH OF TWOACIDS : IH’ furnished by 1 acid _ 10 _ [aio IH] furnished by acd 202 Yka,¢2 (b) pH ofa mixture of two weak acid(both monoprotic) solutions : Ka a (cams) = Raat AOR CK weak acid in solution of two weak acid then ** it water is again considered thi TH] = JKC, +K 2S + Ky Koy = 10% THI (CK +CaKg +10 ( —_ pHof amixture of weak acid{monoprotic) and a strong acid solution : ¥[SA]=C, and [WA] =C., then [H'] from SA=C, and [H'] from WA= C, Let Ha is a weak acid crn OP eK Ge 2 “* If a strong acid of low conc is added in water then [H’] of solution can be calculated as Hy Oy + yOF Hak, f= 7 Q SALT HYDROLYSIS : Sait of type of nydroysis ® pH (a) weak acid & strong base anionic Ke ee 7+ 4 p+ + tage Ke kee 2PKta : k fe 1 (0) strong acid &weak base cationic, «ee. few ok toge ko pe 2 2 ka Ky 1 (6) weak acid & weak base both ey ovens 30k, {d) Strong acid & strong base do not hydrolysed- Hydrolysis of ployvalent anions orcations For [Na,PO,]=C. Kx K eK, TE] short Formula (Chemistry) WARezcrecce Kye Kea Ky KAxKyeK, Gonorally pH is calculated only using the frst stop Hydrolysis Ch? one ach SIOH]= 0h = (Raxe 1H 1 So pH FIpKy+PK yy +ogC] Hydrolysis of Amphiprotic Anion. (Cation is not Hydrolysed.e.g. NaHCO,, NaHS, etc.) orbs) (©) Similarly for HPO,” and HPO amphiprotic anions. a, = [ PRantPKas " PHenpow | >| and Papo ° Hypo, Kes HPO” Kn HPO, —K»_5 PO, ionisation 12> Ky? Ky, pHotNaHPO, pHofNa,PO,= 3 (okw+ pKa, + log 6) + Sec hydrolysis can negioct BUFFER SOLUTION : (a) Acidic Buffer : e.g. CH, COOH and CH,COONa. (weak acid and salt of its conjugate base). (san) PH PK, * 109 fest [Henderson's equation} (&) Basic Buffer: ¢ 9. NH,OH + NH(CI. (weak base and sal ofits conjugate acid). : (sat POH = pk, + 109 iBase] Buffer capacity (index) : Total no. of molesof acid /alkal added petive ‘Change in pH Buffer capacity (asxb—x) 03 a+b 47 | Short Formula (Chemistry) WNResenence INDICATOR : Hin =H! + 1n7 HT Ko to") llonisedform) PH= PK. #109 iin) = PH= PK, +109 Uionised form) SIGNIFICANCE OF INDICATORS ‘© Extent of reaction of different bases with acid (HCI using two indicators Phenolphthalein Methyl Orange NaOH 100% reaction is indicated 100% reaction is indicated NaOH + HCI —> Nacl+ H,0 NaOH + HCI — NeCl+ HO Na.co, ‘50% reaction upto NaHCO, 100% reaction is indicated stage is indicated Na,CO,+HCI—>NaHCO,+NaCl ——Na,CO, + 2HC! > 2NaCl+H,0+60, NaH No reaction isindicated 100% reaction is indicated NaHCO, + HCI—> NaCl+ H,0 + CO,. © ISOELECTRICPOINT: ITs (Ke Kar PK ay + PK ap p= Peas SOLUBILITY PRODUCT : K, = Gs) sy=xsyuisy CONDITION FOR PRECIPITATION : Ionic product Kp > Kap precipitation occurs, iI Kj» = Kgp Saturated solution (precipitation just begins or is just prevented). ELECTRODE POTENTIAL For any electrode > oxidiation potential RP of cathode—R.P of anode RP. of cathode + OP of anade always a+ve quantity & Anode will be electrode of low RP. SRP of cathode ~ SRP of anode. Reduction potential O Greater the SRP value greater will be oxidising power. WN Sesenecce NERNST EQUATION : (Effect of concentration and temp of an emt of cel) = AG=AG*+RT ¢nQ (where Qis raection quotient) ‘At chemical equilibrium ase0 ae i "00 Kon 9.0597" 0.0591 Fs MO Kg Foran electrode M(s)/M"" a 2.303RT 1 Eve Ei ne 8 CONCENTRATION CELL : Acell which both the electrods are made up of same mat For all concentration cell E°,, fa) Electrolyte Concentration Cell : ‘eg, Zn(6) /Zn* (c,) || Zn™(0,)IZn15) = 2058t og {b) Electrode Concentration Cell : 9. PILH,(P, atm)/H' (1M) /H, (P, alm) /Pt DIFFERENT TYPES OF ELECTRODES : 0.0591 4. Metal-Metal ion Electrode M(s)/Mr". Mr" + ner —> M(S) exer OO ogi 2 Gas-ionElectrode —_PLIH,(Patm) HH" (XM) 4 Pas? 4a reduction electrode Haq) +e —> 5H, (Pam) = EP 0.0501 log sr ‘Short Formula (Chemistry) WNSecerecce Oxidation-eduction Electrode Pt/ Fe, Fo 2 1 ete tete ttt eet ie etectuiey i Ee 4. MetakMetalinsoluble salt Electrode eg. Ag/AgCl, Cr as areduction electrode AgCl(s) + © — Ag(s) + Cr — Ecrrngeting = Fer gctsag ~ 0.0581 log (CH. (CALCULATION OF DIFFERENT THERMODYNAMICS FUNCTION OF CELL REACTION O AG=-nFEy ° dc ar (At costant pressure) f (ae-0| = Temperature cofficient of .m fof the cel Esatpr+cr+ 0 atenr[1(]-¢| 2 —Aep of cell reaction cp= at sop= (aH) OQ ELECTROLYSIS : (@ —K,Ca%, Nar, Mg’, AI®, Zn’, Fe", H', Cure, Ag’, Au, Ts Increasing order of deposition, (©) Similarly the anion which is strogner reducing agent(low value of SRP) is liberated first at the anode. SO. NO; OFF, CF 81 Tneeeaingerderof postion 20 | Short Formula (Chemistry) WNSecerecce FARADAY'S LAW OF ELECTROLYSIS : weZit 2.= Electrochemical equivalent of substance: wee Weozsart W steer tiny ee oul nas dyostoddeed CURRENT EFFICIENCY = pes rod 100 ‘Theortical mass deposited/produced © CONDITION FOR SIMULTANEOUS DEPOSITION OF Cu& Fe AT CATHODE Ee Meo eee eect O0eDt ai cer rew S109 Guz = Ere ire (00 ae Condition for the simultaneous deposition of Cu & Fe on cathode. ‘CONDUCTANC! Conductance = a © Resistance = Specific conductance or conductivity : (Reciprocal of specific resistance) K= specific conductance © Equivalent conductance: a, = Keto00 : Nomaliy wit sob eno = Molarconductance: _ 1000 paras - Nalay -ohm' om? mole t specific conductance = conductance * = KOHLRAUSCH'S LAW Variation of}, /2, ofa solution with concentration : @ Strongelectroyie Ag hy DYE (ii) Weak electrolytes where iis the molar conductivity No of cations obtained after dissociation per formula unit 1, = Noof anions obtained afler dissociation per formula unit 21 | Short Formula (Chemistry) WNResenence APPLICATION OF KOHLRAUSCH LAW: 1, Calculation of 45, of weak electrolytes : My oucocin = Macacooey * Magen” Paen 2. Tocaiculate degree o dlossociation ofa week electroyte i cat? ae ce : Ka Goa 3. Solubility (6) of sparingly soluble sat & their, 1000 AOS = Bi K,=S © IONIC MOBILITY :Itis the distance travelled by the ion per second under the potential gradient of 1 volts per Absolute ionic mobility : eu, 5 Ae, WeFuo ; eR «ue tonic Mobilty y= Seed (Wij —potentialgradient ‘Transport Number: wlete) slat] Bema) * Ma +He ransport Number of cation & t, = Transport Number of anion SOLUTION & COLLIGATIVE PROPERTIES 1. OSMOTICPRESSURE 0 = pgh where, p= density of soln., h = equilibrium height (i) Vont- Hoff Formuta (For calculation of O.P.) n= CST = cRT= "RY Gut ike idalges eatin fotal conc. of all types of particles. Lt 4Cy# (424 4g bod v Note : IfV, ml of, cone. + V,mL of, cone. are mixed CN, +0.V5 mV. mVp (Ca) = (a) Type of solutions : (2) Isotonic solution - Two solutions having same ©.P. 1, = m, (at same temp.) 22 | Short Formula (Chemistry) WNResenence (b) Hyper tonic if x,>x,. = |* solution is hypertonic solution wrt. 2% solution, (c) Hypotonic ~ I!" solution is hypotonic w.rt. solution. Abnormal Colligative Properties : (In case of association or dissociation) VANT HOFF CORRECTION FACTOR (): exp/observed/actual/ abnormal value of colligative property : Theortical value of colligative property exp./observed no. of particles / conc. _ observed molality ‘Theoriical no. of particles Theositical molality 2 theoretical moler mess (formula mass) = ‘ppp etimental /observed molar mass apparent molar mass) OQ i>t = dissociation, ist = association Fea ° in =ICRT HE (yO, + Cy + 1gCy....) RT Relation between i & a (degree of dissociation) : Sina where, ne xey, Relation biw degree of association B& i (1 o (ta tel, bs 2 RELATIVE LOWERING OF VAPOUR PRESSURE (RLVP) > Vapour pressure Pan ? =x, ap O — Ostwald-Walker Method : Experimental or lab determination of Sor a P-P,__lossinwtof solvent wL.of solution loss in wt.of solvent P ~ gainin w.of dehydrating agent 3. ELEVATIONINBOILING POINT: ateiekm RT RTM sity KE Goong (AHsan ) bor [Pa | 4. DEPRESSIONINFREEZING PONT: at, sink, m RT? RTM. i, = molal depression constant = aq — * 7960 aFcas RAOULT’S LAW FOR BINARY (IDEAL) MIXTURE OF VOLATILE LIQUIDS : PX, Pye Ky feo 2 Alsmore'votatietnan 8 BPOfA x20 Me Ideal solutions (mixtures): Mixtures which follow RaouTts law at all temperature, AoA Anne B, BB AH. = 0 Vy, AS,,,= + ve as for process to proceed :AG,. eg. (1) Benzene + Toluene. (2) Hexane + heptane, CHB CHL Non - Ideal solutions : wnich do not obey Raoult’ fav. (a) Positive deviation : ~ 0) Pray? GP%t XpPaP) cohrnfon a Weatertrectatrecon (aH, =*ve energy absorbed (wy aV,,=4ve (1L# 1L> 2) 8,2 4¥0 (wac.=-ve eg. H,0+CHOH. H,0+C,H,0H C.H.OH + hexane C,H,OH + cyctohexane. CHCI, + CCl, + dipole dipole interaction becomes weak. | ‘Short Formula (Chemistry) WNSeserence Negative deviation 0 P, xD < x," + XP", @ strong force of atraction a 4H,.=-¥e AV,Fave | (1L#4L<2Ly © as,.=+ve )AG,.==¥ eg. H,0+HCOOH H,0+CH,COOH H,0+HNO, CHCL+CHOCH, = => PA PB YALO xe=0 Immiscible Liquids : Pew Pat Pe (P,=PEX,=PE (Since, X,= 1) (PL=PgX=Pe Since, x,= 1 peeps Pa te FE _ Wa Ms OP agtPEtPS BE = ne ©) po Me ee ART gg MoRT Pe v Pe v Te. BP. of solution is less than the individual B.P.’s of both the liquids, 28 | Short Formula (Chemistry) WNResenence Henry Law : This law deals with dissolution of gas in liquid i.e. mass of any gas dissolved in any solvent per unit volume is Proportional to pressure of gas in equilibrium with liquid, map m=kp weight of gas ™~ Volume of liquid SOLID STATE © Classification of Crystal into Seven System Crystal System Unit Cell Dimensions Example ‘and Angles Cubic azbeo;aspzy= 90" sc, BCC, Fee Naci onhorhombie arbecja=p=7=90° SC, BCC, end centred & FCC 8 Tetragonal azbeoia= sc, ace SnZn0, Monoclinic arbecsa SC, end centred 5, Rhombohedral so Quariz Teilinic azbscjaspey290 sc HB0, Hexagonal asbecia= 10°77 = 120° sc Graphite © ANALYSIS OF CUBICAL SYSTEM Property sc Bec Foo atomic radius . ae Ze At edgelengtn 0 oc a 22 = edge leng! i) No. of atoms per unit cell (Z) 1 2 4 Gi) CN. 8 8 2 (i) Packingefficiency 52% 68% 78% No. voids @octanedral(Z) a 4 (0) Tetrahderal (22) ae pee 8 © NEIGHBOUR HOOD OF APARTICLE: wo ‘Simple Cubic (SC) Structure : Type of neighbour Distance no.of neighbours nearest a 6 (shared by 4 cubes) (vex a2 12 (shared by 2 cubes) (nexty? ays 8 (unshared) 27 | Short Formula (Chemistry) WNResenence ay Body Centered Cubic (BCC) Structure : ‘Type of neighbour Distance No.of neighbours (00x)! 6 (next 2 12 (ext) a ey (next)¢ = ay 8 Face Centered Cubic (FCC) Structure : Type of neighbour no. of neighbours 3x8 nearest 2-( ) 3x8 (ne! a 3 (next? ays Pa exp ad 2 (oa! af nm z(M DENSITY OF LATTICE MATTER (4) = fg, (3 where N, = Avogadro’s No. M= atomic mass or molecular mass, IONIC. CRYSTALS No. Limiting raaius ratio ( 3 0.185 ~0,226 (Triangular) 4 0.226 ~ 0.414 (Tetrahedral) 6 0.414 ~0.732 (Octahedral) 8 0.732 -0.999 (Cubic) EXAMPLES OF AIONIC CRYSTAL (a) Rock Salt (NaCl) Coordination number (6 : 6) (b) CsCl C.No. (8: 8) 2 Edge length of unit cell:- an ery (c) Zinc Blende (2n8) C.No. (4: 4) WN Sesenecce (a) Fluorite structure (CaF,) C.No. (8:4) Fler +e) O Crystal Defects (Imperfections) ‘Crystal Defects (Point Defects) metic Non-Stoichiomettic Schottky Frenkel Metal excess Non-Metal excess (on pairs missing) (dislocation ot ions) electron in place edna cation iN Vacant site ‘extra anion in ‘of anion the interstitial in place of cation intersttal (not found CHEMICAL KINETICS & REDIOACTIVITY RATE/VELOCITY OF CHEMICAL REACTION: Ac _ molt at" sec ‘Types of Rates of chemical reaction : Fora reaction R —> P Rat = mol it time-* = mol din time" Total change in concentration ‘Average rate Total time taken []-#--. ad eaaaaaaaeeee 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 = (cone)'-*% time Order of reaction : mA+m,8—> products. Re [AI [BF Where p may or may not be equal to m, & similarly q may or may not be equal to m,. pis order of reaction with respect to reactant A and q is order of reaction with respect to reactant B and (p + q) is overall order of the reaction. 29 | Short Formula (Chemisty) WN Sesenecce INTEGRATED RATE LAWS : , or ‘ais initial concentration and , or axis concentration at time (a) zero order reaction: So Unit of K = mol lit’ sec, Time for completion ie att, C, So so Kt, So = So t C, a2 Bohs > tet oP a Co (b) First Order Reactions ; () Let a 1" order reaction is, A. ——+ Products. 2.900 |, So a 220 oa Ge 3 7 = Independent of intial concentration a log ¢, RC, : “an 2.308 2909 6 ‘ [ log CYC, og alo ee, {c) Second order reaction 2 order Reactions Two types A+ A > products A +B > products fee ai. ° (a-%) (a) a-x b-x & : x & ck ewe ok (a-s) 0-0 1 2300 Man eit k bla-x) ? aw Ya=b) '9 ax) {d) Psuedo first order reaction : ForA+8—>Products [Rat KEP Ir ‘Shat Formula (Chemisty) WARezcrecce 13 b(a-x) = ye) °F a—») is taken in large excess b> > a 'b’is very large can be taken as constant 2.303 2.303 = Ko=™ tog = ve ig - K’Is psuedo first order rate constant METHODS TO DETERMINE ORDER OF AREACTION {a) Initial rate method : T= KIAPIBPICK =F [B]= constant [C]= constant then for two different inal concentrations of Awe have fos fo, = KIA! . to, = KADY Seice@edil (Aalsi {b) Using integrated rate law = itis method of tial and error. {c) Method of halt lives = forn® orderreaction ty, = aR yRT we Rol! (d) Ostwald Isolation Method = rate = k [AP BP? [CI METHODS TO MONITOR THE PROGRESS OF THE REACTION: @ © Progress of gaseous reaction can be monitored by measuring total pressure ata fixed volume & temperature 2308 9g or by measuring total volume of mixture under constant pressure and temperature. «. k= Pont) {Formula is not applicable when n = 1, the value of n can be fractional also.} P,P, By titration method: 2303 Yo an nxn, = xe BB gt Study of acid hydrolysis of an easter. 2.303 V.=Vp k= tog Vay, ‘By measuring optical rotation produced by the reaction mixture : 34 | Short Formula (Chemistry) WNSecerecce EFFECT OF TEMPERATURE ON RATE OF REACTION. Ky Ki Arhenius theroy of reaction rate. I Entapy ont 0 = 2 to 3 (for most ofthe reactions) Tes 1 SH, = Summation of enthalpies of reactan Tigstelsonhaby 54° = summation of enthalpies of reactants Energy of activation of the forward reaction ae Eneray of activation of the backward reaction aren ction cont) E,>E, —> endothermic E, exothermic AH =(E,—E,) = enthalpy change AH=E,-E,, Erame = Eu + E, Arhenius equation +E, ote feone,j" dink | E, aT * RT? |2 slog tog k= ["2303 8 JT" If, and k, be the rate constant ofa reaction at two different temperature T, and T, respectively, henwe have a} Ee (4 2303 (7, na sina Ea, slope = - Es %ink=ina~ Ee R Tae kKoa Ink it REVERSIBLE REACTIONS RT WN Sesenecce endothermic t/t exothermic 1 BI _ Ex ki +E ke te Ke = ky tke (ii) REVERSIBLE 1°" ORDER REACATION ( both forward and backward ) Ka Ky +Kp | "bia S| (iii) SEQUENTIAL 1°" ORDER REACTION W=tale geet a fewae* (Ke) MK, CASEI K>>K, CASEM: — K,>>K, 38 | Short Formula (Chemistry) WNResenence PERIODIC TABLE & PERIODICITY Development of Modern Periodic Tabl (@) 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 fist to conelate the cesnical properties of the elements with their atomic masses. (€) Lother Meyer's Classification : He plotled a graph between atomic masses agains! their respective atomic volumes for a number of elements. He found the observations ; (i) elements with similar properties ‘occupied similar positions onthe curve, (ji) alkali metals having larger atomic volumes occupied the crests {i transtions elements occupied the troughs, (iv) the halogens occupied the ascending portions ofthe curve before the inert gases and (V) alkaline earth metals occupied the positions at ebout the mid points ofthe descending portions of the Curve. On the basis of these observations he concluded that the atomic volurnes (a physical property) ofthe elements are the periodic functions of thelr atomic masses, {d) Mendeleev's Periodic Tabl Mendeleev's Periodic’s Law the physical and chemical properties ofthe elements are the periodic functions oftheir atomic masses, Periods ‘Number of Elements Called as Fast z ‘Very shart period ana? 8 ‘Short pesiod grn=3 8 ‘Short period (@hand 7% Long period GPnes @ Long period ORn=6 2 Vary tong period OR n=7 8 Incomplete period Merits of Mendeleev's Periodic table: ‘© 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 ints, periodic table. Domerits in Mendeleev’ Periodic Table : Position of hydrogen is uncertain .It has been placed in IA and VIIA groups. No separate 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 the periodic table. © Similarelements were placed indifferent groups, © Itdidn't explained the cause of periadicity. (e} 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 a regularinterval, elements with similar properties are repeated. Periodicity : ‘The repetition ofthe properties of elements after regular of increasing atomic number is called periodicity ntervals when the elements are arranged inthe order Cause of Periodicity : ‘Shat Formula (Chemisty) WARezcrecce ‘The periodic repetition of the properties of the elements is due to the recurrence of similar valence shell electronic configurations after certain regular intervals, ‘The moder periodic table consists of horizontal rows (periods) and vertical column (groups). Periods : ‘There are seven periods numbered as 1, 2, 3,4, 5, 6 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 present init © Each period starts with an alkali metal having outermost electronic configuration as ns’ . Each period ends with a noble gas with outermost electronic configuration nsénp® except helium having outermost electronic configuration as 1s. © Each period starts with the filing of new energy level. © The number of elements in each period is twice the numberof atomic orbitals available in energy level thatis being filed. Groups: There are eighteen groups numbered as 1, 2,3, 4,8, ....... 18, 14, 15, 16, 17, 18 Group consists of a series of elements having similar valence shell electronic contiguration. oe Block laments creme orn c : A = : 4-Block Elements NN eee eee ~ seamarien | Sie | lool ll | S| ail ls atl oe | ela | fe | | | ete come [SPRL E Teale clslelelelelele Classification of the Elements : {@)s-blockelements, Group 1 & 2 elements constitute the s-block. General electronic configuration is [inert gas] ns*? ‘s-block elements lie on the extreme left of the periodic table, (b) p-block elements Group 13 to 18 elements constitute the p-block. General electronic configuration is [inert gas] ns?np"* (©) Block elements Group 3 to 12 elements constitute the d-block, General electronic configuration is [inert gas) ‘Short Formula (Chemistry) WARezcrecce (n= 1) 4° nst® (d)f-Blockelements General electronic configuration is (n= 2) {* (n= 1) ns? All Fblock elements belong to 3" group. Elements of blocks have been classified Into two series. (1) I* inner transition or 4 f-serles, contains 14 elements ,,Ce to,,Lu. (2). IInd inner transition or §f-series, contains 14 elements .Thto ,.Lr Prediction of period, group and block : © Period of an element corresponds tothe principal quantum number of the valence shell Q __ Theblock of an element corresponds to the type of subshell which receives the last electron, © Thegroupis predicted from the number of electrons in the valence shell orfand penultimate shell as ol (@)Fors-blockelements; __Groupno.= the no. of valence electrons (b)Forp-biockelements; Group. = 10+ no. of valence electrons (©)Fordeblock elements | Group no. = no. of electrons in n= 1) d sub shell + no. of electrons in valence shell 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% ofall known elements and appear on the left hand side ofthe periodic table, Metals are usually solids at room temperature (except mercury, gallium). They have high melting anc boiling points and are good conductors of heat and electricity. Oxides of metals are generally basic in nature (Some metals in their higher oxidation state form acid oxides e.g, CrO)) ‘+ Nonmetals do not lose electrons but take up electrons to form corresponding anions. Nonmetals are located at the top right hand side of the periodic table, Nonmetals are usually solids, liquids orgases at oom ‘temperature with low metting and boiling points, They are poor conductors of heat and electricity. Oxides of nonmetals are generally acidic in nature. Metalloids (Semi metals) : ‘The melalloids comprise of the elements B, Si, Ge, As, Sb and Te, \gonal relations! 2 period ub B ¢ Be period = Na Mg ALS Diagonal relationship arises because of ; —_ondescending a group, the atoms and ions increase in size. On moving from left o right in the periodic: table, the size decreases. Thus on moving diagonally the size remains nearly the same, (i= 1.23.48 Mg = 1.36 A; Li =0.78 A& Mg™= 0.72) @ __ itis sometimes suggested that the diagonal relationship arises because of diagonal similarity in electronegativty values. (U= 1.08 Mg= 1.2; Be=1.5&Al=15;B=2.08Si= 1.8) The periodicity of atomic properties : (Effective nuclear charge: ‘The offective nuclear charge (2,.)=Z—o, (where Z isthe actual nuclear chargo (atomic number of the element) and c is the shielding (screening) constant). The value of o i. 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. ‘Shat Formula (Chemisty) WARezcrecce Vander Waal’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. (©) Metallic radius (Crystal radius) : Itis one-half ofthe distance between the nucle of two adjacent metal atoms inthe metalic crystal latice. ‘© Thus, the covalent, vander Wall's and metalic radius magnitude wise follows the order, ni a ‘ean cea irs imcaencied piewereme Eo sa Ta SA tea pre chp) arom ora coma a ee atl ges pemstertastatt cater tees oe = Sitar ac intemal ere oo I cc CS Aaron be dete puedo oe | Te act seers. Al eee eee a Seeereeee Hence alomic radi decrease with increase in atomic umber ina porod ror eto right (iil) tonic radius : ‘The effective distance from the centre of nucleus of the fon up to which it has an influence in he lonie bond is called ionic radius. ation ‘Anion, |iPie-Tormed by tre lose of one or more slocrons From|it fe formed by the gain of ono or more electrons in He] Iho valonce shot ofan atom at an elament |vatence shel of an atom of an eloment [Cations are smaller than the parent atoms because, | Anions are larger than the parent atoms because i) the whole of the outer shell of electrons is usually) arion Is formed by gain of one or more electrons in the} lemoved neural atom and thus number of electrons increases |) in a cation, the number of positive charges on the}magnitude of nuclear charge remains the eame. Jnucieus is greater than number of ortital electrons) nuciear charge per electrons ie thus reduced and the} leacing to inctesed inward pull of remaining electrons elections clouds held less tightly by the nucieus leading [causing contraction in size of te fon line expansion of the outer shell, Thus size of anion i increased, ()—lonisation Energy: lonisation energy (IE) defined as the amount of energy required to remove the mast loosely bound electron from an isolated gaseous atom to form a cation. MQ) 2, M@te ; M@+iE, + MP@te MW @) +E, —> MP@ +e- IE, IE, &IE, are the, IP Il!}onizalion energiesto remove electron from a neutral atom, monovalent and divalent cations respectively. In general, (E), < (IE), <(E),<... Factors Influencing lonisation energy (A) Size of the Atom : onisation energy decreases with increase in atomic size. ©) Nuclear Charge : The ionisation energy increases with increase inthe nuclear charge. Shielding or screening effect ; The larger the number of electrons in the inner shells, greater is the ‘screening effect and smaller the force of attraction and thus ionization energy (IE) decreases. (O) Penetration effect of the electron : Penetration effect of the electrons follows the orders > p>d> £ for, the same energy level. Higher the penetration of elecron higher will be the ionisation energy. 3 37 | Short Formula (Chemistry) WNResenence (©) __ Electronic Configuration : If an atom has exactly hal-filled or completely filed orbitals, then such an arrangement has extra stability () Electron Gain Enthalphy : (CHANGED TOPIC NAME) ‘The electron gain enthalpy 4,,H°, is the change in standard motar enthsipy when a neutrel gaseous ‘ator gains an electron to form an anion. X@+e@—xX@ ‘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. 2 Group 17 elements (halogens) have very high negative electron gain enthalpies (i.e. high electron «affinity because they can attain stable noble gas electronic configuration by picking up an electron © Across a period, wth increase in atomic number, electron gain enthalpy becomes more negative 2 _Aswemove in.a group from topto bottom, electron gain enthalpy becomes less negative 2 Noble gaseshave large positive electron gain enthalpies © Negative electron gain enthalpy of O or F is less than S or Cl © Electron gain enthalpies of alkaline earth metals are very less or positive 2 Nitrogen has very low electron affinity 1 Electron affinity ~ (i) Electron affinity « Effective muclearcharge @, (Electron arity = ron affinity « Effective nuctearcharge (@,) 1 Ai) Electron affinity ~ sssenng afea- (¥) Stability of half filed and completely filed orbitals of 2 subshellis comparatively more and the adcition of an extra electron to such an system isdificult and hence the electron affinity value decreases (W) Electronegativity : Electronegativity is a measure ofthe tendency of an elermentto attract shared electrons towards self ina covalently bonded molecules. (2) Pauling’s scale A=X,-X,=0.208 En g— vEaaXEoe E,,,= Bond enthalpy/ Bond energy of A~B bond. jond energy of A—A bond Bond energy of B-B bond (All bond energies are in kcal / mol) A=X,-X,=0.1017 Ens \ExanEes All bond energles are in kd / mol. (©) Mulliken’s scale: _ E+EA 2 Paulings's electronegatvity x, isrelated to Mulliken’s electronegativity 2, as given below. Hp 71.35 044)""=1.87 ‘Muliken’s values were about 2.8 times larger than the Pauling's values (Vil) Periodicity of Valence or Oxidation States : ‘There are many elements which exhibit variable valence, This s particularly characteristic of transition ‘elements and actinoids 38 | Short Formula (Chemistry) WNResenence (Vill) Periodic Trends and Chemical Reactivity : © Inagroup, basic nature of oxides increases or acidic nature decreases. Oxides of the metals are ‘generally basic and oxides of the nonmetals are acidic. The oxides of the metalloids are generally ‘amphoteric in nature. The oxides of Be. Al, Zn, Sn, As, Pb and Sb are amphoteric. 2 Ima period the nature of the oxides varies from basic to acidic. Nao M0 ALO, So, PO, 80, Strongly basic Basic amphoteric © Weaklyacidic Acidic Acidic Strongly acidic | CHEMICAL BONDING Chemical Bond : @ wi) co) Inthe process each atom attains stable outer electronic configuration of inert gases, Ionic oF Electrovalent Bon: ‘The formation of an ionic compound would primarily depends upon “The ease of formation ofthe postive and negative ons from the respective neutral atoms. +The arrangement of the postive and negative ios inte solid, thats the latice ofthe cnystaline compound, Conditions forthe formation of ionic compounds : Electronegativty cfference between wo combiring elements must be larger. Ionization enthalpy (M(g) ~ M'(q) +e) of elecropositve element must be lw. Negative value of electron gain enthalpy (X (g) + e- — X-(g)) of electronegative element should be high. Lattice enthalpy (Mra) + X (9) + MX () of an nic 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 : o Determination of lattice energ) where ((, £_) = Inter-ionic Distance. Lattice energy = = Lattice energy «ZZ. Z, = charge on cation in terms electroniccharge. Z.= charge on anion in terms electroniccharge, Born-Haber Cycle : inter 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. 38 | Short Formula (Chemistry) WNResenence Hydration : Allthe simple salts dissolve in water, producing ions, and consequently the solution conduct electricity. Since Lit is very small, it is heavily hydrated. This makes radius of hydrated Li* ion large and hence it moves only ‘Slowy In cont2st, Cs" isthe least hydrated because of is bigger size and thus he radius of the Cs" fon is smaller than the radius ofhydrated Lit, 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 trinalides General properties of ionic compounds : (2) Physical state : At room temperature ionic compounds exist either in solid stale or in solution phase but not in gaseous state. (©) Simple ionic compounds do not show isomerism but isomorphism i their important charactetstic. eg., FeSO,.7HO | MgSO, . 7,0 (Electrical conductivity : Allionic solids are good conductors in molten state as well asin their aqueous solutions because their ions are {ree to move. (D) SOLUBILITY OF IONIC COMPOUNDS : ‘Soluble in polar solvents ike water which have high dielectric constant Covalent character in ionic compounds (Fajan’s rule) : Fojen’s pointed out that greater's the polarization of anion ina molecule, Cation anion more is covalent character init More distortion of anion, more will be polarisation then covalent character increases. Fajan's gives some rules which govem the covalent character in the ionic compounds, which are as follows: © Size of cation :Size of cation «1 / polarisation. @ Size of anion : Size of anion « polarisation Gi) Charge on cation : Charge on cation a polari Charge on anion : Charge on anion « polarisation. Pseudo inert gas configuration of cation : Covalent Bond : forms by sharing of valence electrons between atoms to form molecules e.g., formation of Cl, molecule GOS Beet orci} Govelent bond between two Gl atoms ‘The important conditions being thal Each bond Is formed as result of sharing of an electron pair between the atoms, Each combining atom contributes at least one electron to the shared pair, ‘The combining atoms attain the outer- shell noble gas configurations as a result ofthe sharing of electrons. “0 | Short Formula (Chemisty) WNResenence 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. (NH; (ammonium ion) (i), (ozone) *, N,O, [Cu(NH,) ‘Other examples : H,SO,, HNO, , Hy Formal Charge : Fomalcirge 0) | | oui amber et vance") _[ tom number ofnon bona Srannomin stots) = [Satintnchee an | -[ eS naeece eo] en | Ttlnber | oetng Tay 4. ob Formal charges help in the selection of the lowest energy structure from a number of possible Lewis, structures for a given species. Limitations of the Octet Rul 1. The incomplete octet of the central atom LiCl, BeH, and BCI, AICI, and BF,, 2, Odd-electron molecules nitric oxide, NO and nitrogen dioxide. NO, Neo G 3, The expanded octet q H-0-8-5-n cr z —p ie FE PF, H,SO, 10 electrons around the P atom 12 elecirons around the S atom 12 electfons around the $ atom 4. Other drawbacks of the octet theory @ some noble gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of ‘compounds lke XeF, , KiF, , XeOF, etc, (This theory does not account for the shape of molecules. Gi) tdoes not expiain the relative stability of the molecules being totally silent about the energy of a molecule. “| short Formula (Chemisty) WNResenence Valence bond theory (VBT) : H,(@) + 435.8 kd mol--> H(g)+ Hig) rereyecdmet) 4358 Bord Longth 742 Iniomucese deanco—> 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 overiapping () sigma(o) bond, and (i) pi (x) bond (—_Sigma(o) bond : This type of covalent bond is formed by the end to end (head-on) overtap of bonding orbitals along the internuclear axis, @s-s overlapping ey + e--— 2 s-orbital s-ortital s-8 overlapping © s-p overlapping: +@oS — @e@ orbital potital sporti! ‘@ pp overlapping: Thistype of overlap takes place between half filed p-oritals ofthe two approaching atoms. of -+ea 24> p-ottital potbital p-poverlaping pifx) bond In the formation of x bond the atomic orbitals overtap in such a way that their axes remain paralle| to each other and perpendicular tothe intemuclear axis. 9.9 -_ fire p-orbital p-orbital a ianaens ‘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, 4 | Short Formula (Chemisty) WNResenence Valence shell electron pair repulsion (VSEPR) theory : 0 14 2. 3. (ii) (iy w ‘The main postulates of VSEPR theory are as follows: The shape of ¢ molecule depends upon the number of valence shell electron pairs [bonded or nonbonded) around the central atom, Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged. ‘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 asa sphere with the electron pairs localising on the spherical surface at maximum, distance from one another. ‘Amultiple bond is teated as if itis a single electron pair and the two or three electron pairs of @ multiple bond are treated as.a single super pair. 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 (ip) - lone pair (zp) > lone pair (ép)- bond pair (bp) > bond pair (bp) -bond pair (bp) Hybridisation : Salient features of hybridisation : “The numer of hybrid orbitals is equal tothe number ofthe atomic orbitals that get hybriised “The hybridised orbitals are aways equivalent energy and shape. “The hybrid orbitals are mare efectve in forming stable bonds than the pure atomic orbital. “These hybrid otal are arocted in space in some preferre direction to have minimum repulsion between electron pairs and thus a stable arrangement is obtained. Therefore, the type of hybridisation indicates the ‘geomet ofthe molecules Important conditions for hybridisation : “The oritals present inthe valence shell ofthe atom ae hybridised. “The orbitals undergoing hybridisation should have almost equal energy Promotion of electron isnot essertal contin priorto hybridisation. itis the orbital that undergo hybritization and not he electrons 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 bonded with that ator + number of lone pair(s) left on that atom. Table-3 ‘Steric number ‘Types of Hybridisation Geometry 2 8p Linear 3 sp TTrigonal planar 4 sp Tevvahedral 8 spd ‘Trigonal bipyramidal 6 spa Octanedral 7 spd? Pentagonal bipyramidal Hybridization Involving d-orbital = Type of 'f orbital involved spd de spd dxt—y? & dz? sped xe — 2, dz? & dxy esp! “| Short Formula (Chemisty) WNResenence Molecular Orbital Theory (MOT) o @ wo developed by F. Hund andi R.S, Mulliken in 1932. ‘Molecular orbitals are formed by the combination of ator orbitals ot comparable energies and proper symmetry. ‘An electron in an atomic orbitals influenced by one nucleus, while in a molecular orbital itis influenced by two ‘or more nuclei depencing upon the number ofthe atomsin the molecule. Thus an atomic orbital is monocentric while a molecular orbital is polycentric. The number of molecular orbitals formed is 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. ‘The molecular orbitals lke 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 (a + 1) rule 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. ‘The combining atomic orbitals must have the same symmetry about the molecular axis ‘The combining atomic orbitals must overtap to the maximum extent. ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS: ‘The increasing order of energies of various molecular orbitals for O, and F's given below: 6 18<0" 18 < 028 < "2s < (n2p_= 12p,) < 020, < (n"20,= R°2P,)< 0°20, ‘The important characteristic feature ofthis order's that the energy of «2p, molecular orbital is higher than that of x2p, and x2p, molecular orbitals. BONDORDER Bond order (b.0.) = % (N,—N) A positive bond order (i.¢., N, > N,) means a stable molecule while a negative (.e., N, < NJ or zero (ie.,N, = N,) bond order means an unstable molecule. NATURE OF THE BOND: Integral bond order values of 1, 20r 3 correspond to single, double ortrigle bonds respectively. BOND-LENGTH: “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 NATURI {all the molecular orbitals in a molecule are doubly occupied, the substance is diamagnetic (repelled by magnetic field) ¢.g.,N, molecule. Dipole moment : Dipole moment (1) = Magnitude of charge (a) « distance of separation (d) Dipole moment is usually expressed in Debye units (D). The conversion factors are 1D =3.33564 x 10 Gm, where C is coulomb and mis meter. O 1 Debye = 1 x 10°%e.su, om. For example the dipole moment of HF may be represented as ‘The shiftin electron density is represented by crossed arrow (| >) above the Lewis structure to indicate the direction ofthe shit 4 | Short Formula (Chemisty) WARezcrecce a molecule will have a dipole moment ifthe summation of all ofthe individual moment vector s non-zero. wep q FET VP? 1 BPQoas6 - where R is resultant dipole mament. Resonance Definition : Resonance may be defined as the phenomenon in which two or more structures invalving in identical position of atom, can be written for particular compound, For example, the ozone, O, molecule can be equally represented by the structures | and Il shown below PE, £P%y A KS of % ¢ 9 é 1 1 Resonance inthe ©, molecule Resonance Hybrid : It isthe actual structure of al different possible structures that can be written for the ‘molecule without violating the rules of covalence maxima forthe atoms. O-0-.0 Resonance hybrid Hydrogen Bond : =H FE—--H Conditions req () Molecule should have more electronegative atom (F,O, N) linked to H-atom, (i) Size of electronegative atom should be smaller. Gi lone pair should be present on electronegative atom — Orderot H-bond strength —O-eH- TYPES OF H-BONDS: (A) Intramotecular H-Bonding : itis fommed when hydrogen atoms present in between the two highly electronegative (F, 0, N) atoms within the same molecule. " i 6, oN, ot oonytrorybenzatienyde Ithas lower boiling point (ve. 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)2$- or 6- membered ring should be formed. (0) interacting atoms should be placed in such a way that there is minimum strain during the ring closure. ‘Shat Formula (Chemisty) WARezcrecce Intermolecular forces (Vander Waal’s Forces) Metal Intermolecular H-Bonding : itis formed between two different molecules of the same or different compounds, @®) — Inwater molecules Be Be Gy be Ge bro oe HHA GWA 8.8 i Hoe He HOE 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 inthe liquid, Intermoieoular attractions hold two or more molecules together. These are weakest chemical forces and can be of following types. (@) lon-dipole attraction (©) Dipole-dipole attraction: (6) lon-induced dipole attraction (€) Dipole-induced dipole atraction (6) Instantaneous dipole- instantaneous induced dipole attraction: (Dispersion force or London forces) O Strength of vander waal force e« molecular mass. van der Waal’s force « boiling point. ic bond: ‘Two models are considered to explain metallic bonding (A) Electron-sea model (@)Band model Some special bonding situations : (2) 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 (80-2) present in diborane B,H,,AL(CH),, BeH,(s) and bridging metal carbonyls (b) Back Bonding : Back bonding generally takes place when out of two bonded atoms one of the atom has vacant orbitals (Generally this atom is from second or third period) and the other bonded atom is having some non-bonded electron pair(generally his atom is from the second period), Back bonding increases the bond strength and decreases the bond length. For example, in BF, aS ro vacant Files 2patil Zoe the extent of back bonding in boron trihalides, BF,>8Cl, > BBr, “6 | Short Formula (Chemisty) WNResenence COORDINATION COMPOUNDS Addition Compounds : ‘They are formed by the combi are (1) Double satts and (2) Coordination compounds ion of two or more stable compounds in stoichiometric ratio. These Double salts : “Thase aduliton compounds which lose thelr identity in solutions £9. K,S0, Al(SO,), Coordination Compounds : ‘Those addition compounds which retain ther identity (.c. doesn't lose their identity) in solution are Fe(CN), + 4KCN ——» Fe(CN),. AKCN or K, [Fe(CN),] (aq.) <> 4K* (aq.) + [Fe(CN),]* (aa) Central Atom/lon : {na coordination entty-ihe atorvion to which are bound a fixed number of ligands ina definite geometrical arrangement aroundit, Ligands : ‘The neutral molecules, anions or cations which are directly linked with central metal atom or ion in the coordination entity are called ligands. Chelate ligand : Chelate ligandis adi or polydentate ligand which usesits two or more donor atoms to bind a single metal on producing a ring Ambidentate Ligand : Ligands which can ligate through two different atoms present init - a MNS nites Mc O-N=O ritit-O M<-SCN thiocyanato orthioeyanalo-S_; M+NCS_ isothiocyanato or thiooyanato-N Coordination Number : ‘The number of ligand donor atoms to which the metal is directly attached. Oxidation number of Central Atom : ‘The oxidation number ofthe central atom is defined as the charge it would carry fall the ligands are removed along with the electron pairs that are shared with the central atom. [Fe(CN),I* is + and itis written as Fe‘). 47 | Short Formula (Chemistry) Denticity and Chelation : Table :1 ‘Common Monodentate Ligands PAG Na Formule rrathyeeoyenao CHINE ‘engl phosphine Tighen hosshinatiohen arcane | PPIs byrne Pyne CHa) moni sng a Tatianna ‘rather Teen vate aqua aa KO, cater exon 00, Tecan Tecan ce vitooyt ritooy nO ‘oe hee oF Fon F chin chor orc © ‘wom rome or bromo" ee "edo Todo an T ane jade wf eyaniaoS ondod) ow onan Teosyando or aria W" bondedy |e tesyane Thecyanat> Siborded) sen ‘ectaocyane ecyarato Bonded nos rena (evaaie) eronato-0 O-bedec) ca Teonyarato (soe/aate) | eyanaton weboneeo) noo" Traore Tysoxo or hyo oF te rio (Boneh nor ae tO (O-bonaeed ONO ate iat Roe aio ado ne me Trade ue ae rik oa eee ay Ne tate ye 5 oeae ote = pee peor oF super twee or soa seatto HCO" Fart ipa SO hope heeuphato SO fate sat 307 Ieropen euahte yerogenauphito HOF (spn spn othe = irerogen ure rcrogansupido or ever + Pena hen (oer (atosyto Titooyur or nseetare cy intron ion ry WN Sesenecce 48 | Short Formula (Chemistry) tetedensie —ethyleneterarine pontedensts lerathyonoportsemne Pinanediersne Sretayensttrine IN. Ntbs2ammoetytys Damanedarsne| vnainoomsaine —eosavariinanne can sachincnciN, Sait oo ea +H.GH.NHCH,CH.NHGH,CH.NHCH.CH.NH, ‘of tevvaethylenepertaanine lar she al le Table: 2 Common Chelating Amines ‘chelating Common Name TUPAC Nama ARbraviation —_ Fommuta Points bertac——_—liyloneclanine 2aberedianine NCHA, Shane hase ticentaie——prupanadlnrins {.2-ropanedierne mere cH, widerate ——_detylenrsamine N-2aminoetyt- den NH.CH.CHNHGHLCHNM, Wien NKICHCH.NHCH.CHLNHCH.OHNH, 00k encoo heats chyfnatonnoermacanls 12 hanes ttle) ota S : Groene” Droncan SRieriorberonile ogc ci.c00 Table : 3 Common Multidentate (Chelating) Ligands | b.sermnsone eetcetors E,sseramoone, sew lemcooicooss Lzemvidre basen ver fours pica }indiniegreniinene | senccten Loins reac [iow fee laniyairccatanas —— [aupeatancarnn oe sue ee ee com fonpcieen ltr) fieatraser) co fostuasction lsnctyiyinss Pugrnteratanin one roncetaccHine Jrvcnaumenamneito [niopamucnate com frocccrancncrncnicoan Eremrennarneerace fran peer [(prrazo-t-yhiborto 4 | Short Formula (Chemisty) WNResenence Homoleptic and heteroleptic complexes Complexes in which a metal is bound to only one type of donor groups, e... [Cx(NH.),", are known as hhomoleptic. Complexes in which a metal is bound to more than one type of donor groups. e.9.. [Co(NH), Br, are known asheterolepic. Nomenclature of Coordination Compounds Writing the formulas of Mononuclear Coordination Entities = 0 ® a) ™ ® o wi The central atom is placed first. ‘The ligands are then placed in alphabetical order. The placement ofa ligand inthe lst oes not depend on its charge. Polydentate ligands are also placed alphabetically In case of abbreviated ligand, the firtetter ofthe abbreviation is used to determine the position ofthe ligandin the alphabetical order. The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets. When ligands are polyatomic, their formulas are enclosed in parentheses. Ligands abbreviations are also enclosed in parentheses, There should be no space between the ligands and the metal within a coordination sphere ‘When the formula of a charged coordination entity isto be written without that of the counterion, the ‘charge is indicated outside the square brackets asa right superscript with the number before the sign. For example, [Co(H, 0}, [Fe(CN), ‘The charge of the cation(s) is balanced by the charge of the anion(s) ‘Writing the name of Mononuclear Coordination Compounds 0 @ oy » 0 wo wi Like simple salts the cation is named first in both positively and negatively charged coordination enlites. ‘The ligands are named in an alphabetical ower (according lo the name of igand, not the prefix) before the name of the central atonvion. "Names ofthe anionic ligands end in ~o and those of neutral ligands are the same except aqua for H.0, ‘amine for NH,, carbonyl for CO, thiocarbonyl for CS. and nitrosyl for NO. But names of catio ligands end in-tum, Prefixes mono, di, tri etc, are used to indicate the number of the one kind of ligands in the coordination entity. When the names ofthe ligands include a numerical prefix or are complicated or whenever the use of normal prefixes creates some confusion, its set off in parentheses and the second set of prefixes is used. 2 di bis 3 th ‘tis 4 tetra tetrakis 5 penta entakis 6 hexa hexakis T hepta heptakis ‘Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman ‘numeral in the parentheses after the name of metal. It the complexion is cation, the metal isnamed same as the element. For example, Co in a complex cation is called cobalt and Pt is called platinum. I the complex ion is an anion, the name of the metal ‘ends with the suffix- ate. For example, Co in a complex anion, [Co(SCN),|*is called cobaltate. For some metals, the Latin names are used in the complex anions. iron (Fe) ferrate lead (Pb) plumbate silver Ag) argentate tin Sn) stannate gold (Au) aurate The neutral complex molecule is named similar to that of the complex cation, BO | Short Formula (Chemisty) WNResenence Werner's Theory ‘According to Wemer most elements exhibit two types of valencies : (a) Primary valency and (b) Secondary valency. (@) Primary valency ‘This corresponds to oxidation state of the metal lon. This is also called principal, ionisable orlonic valency. It Is satisfied by negative ions and its attachment with the central metal ion is shown by dotted lines, () Secondary or auxiliary valency : Itis also termed as coordination number (usually abbreviated as CN) of the central metal ion. Itis non-ionic or ‘non-ionisable (.e. coordinate covalent bond type). In the modem terminology, such spatial arrangements are called coordination polyhedra and various possibilties are ON=2 linear ON ON=4 tetrahedral or square planar ON Effective Atomic Number Rule given by Sidgwick : Etfective Atomic Number (EAN) = Atomic no, of central metal ~ Oxidation state of central metal + No. of electrons donated by igands. Valence bond theory : “The model ullizes hybridisation of (a-1) dns, np ons. np, nd orbitals of metal atom or ion to yield a set of equivalent orbitals of dente geometry to account for tho observed structures such as octahedral, square planar and tetrahedral, and magnetic properties of complexes. The number of unpaired electrons, measured by the magnetic moment of the compounds determines which d-orbtals ae used, 3 Triangular 6 octahedral Table 5 Coordiantion number of metal | Type of hybridisation [ Shape of complex 4 so Tetrahedral 4 dsp" ‘Square planer 5 spd “Trigonal bipyramial é spo" ‘Octahedral 8 dsp" ‘Octahedral [Co(NH,,J*, the cobalt ion is in +3 oxidation state and has the electronic configuration represented as shown below. roonty — YATE sp" hybrid orbital “The complex [FeF,* Is paramagnetic and uses outer orbital (4) in hybridisation (sp*dF) ; Ls thus called as outer orbital or high spin or spin free complex. So, Forge mt TA p°6? hybrid orbitals ‘Coordination Number Four: Inthe paramagnetic and tetrahedral complex {NIC1,. the nickel is in +2 oxidation state and the ion has the electronic configuration 34%, The hybridisation scheme is as shown in figure, sp hybrid orbitals, 1 | Short Formula (Chemisty) WNResenence aeons ‘Similarly complex (Ni(CO),Jhas tetrahedral geometry and is diamagnetic as it contains no unpaired electrons, ‘The hybridisation scheme is as shown in figure. IN«CO).) Ab /AL Ab Ab [Ab sp’ hybrid orbitals ‘The hybridisation scheme for INI(CN),|* is as shown in Figure. INKCN) Ab ANA AL Se] LE @) ; CP* (@) ; two vacant ‘orbitals are easily available for octahedral hybridisation. The magnetic behaviour ofthese free ions and their coordination entities similar. When more than three 3d electrons are present ike in Gr and Mr (4): Mn and Fe" ('); Fe and Co™ (4) ;the required two vacant orbitals for hybridisation isnot directly available (as a consequence of Hund's rules). Thus, ford, d° and o® cases, two vacant d-rbitals are only available for hybridisation as aresult of pairing of 3d clectrons which leaves two, one and zero unparod electrons respectively. Crystal Field Theory : ‘The crystal field theory (CFT) is an electrostatic model which considers the metaligand bond to be ionic arising purely from electrostatic interaction between the metal ion and the ligand, (a) Crystal field splitting in octahedral coordination entities : Energy correspond @ bpp 10 nbsorplin. 305 A, or average = err (Bone) ; 5 fie orate tol eeu s ra ‘ oa crystal eld 15-4, “Energy comesponds to evolution of energy. Crysta fal spiiting for octahedral complex Free met! ion Figure showing crystal field splitting in octahedral complex. “The crystal field spitting, depends upon the fields produced by the ligand and charge on the metal fon. 2 | Short Formula (Chemisty) WNResenence Ligands can be arranged in a series in he orders of increasing field strength as given below 1-< Br-< SON-< Ch @ oe bc a ate ‘arp ‘aa Coordination Number Si ‘Geometrical isomerism is also possible in octahedral complexes. t i NH, cl NH, NH, Im IL NA Co: Co: NH TNH, NH { NH, NH, cl ols trans Geometrical isomers (cis and trans) of [Co(NH,),CLT Number of possible isomers and the spatial arrangements of the ligands around the central metal ion for the specific complexes are given below. ‘Complexes containing only unidentate ligands Map, - 2 Mabe = 2 iy mayb, Compounds containing bidentate igand and unidentate ligands. @ — M(AA)a,b—Two geometrical isomers are possible. » a A e A a M, M, Al a ‘al lb e a bia ata (i) M(AA)a,b,—Three geometrical isomers are possible, ‘85 | Short Formula (Chemistry) WASeserecce a a b A b A a A a M. M, M, A b Al b Al a a b b ata amb bib Note: With IM(AA)b,, only one form is possible, M(AA)abod have six geometrical isomers. Gi) M(AA),0,~Two geometrical isomers are possible. aN abo cee rh Buena Geometrical isomers (cis and trans) of [CoCl (en), Optical Isomerism : coordination compound which can rotate the plane of polarised light is said to be optically active, Octahedral complex : Optical isomerism is common in octahedral complexes involving didentate ligands. For example, [Co(en) J" hasd and ¢ forms as given below. a O eno > rnitror ‘eve dand ¢ of [Co(en),)* Square planar complex = ‘Square planar complexes are rarely found to show the optical isomerism. The plane formed by the four ligating atoms and the metal ion is considered to be a mirror plane and thus prevents the possibility of chirality Organometallic compounds Metal Carbonyls : Compounds of metals with CO as a ligand are called metal carbonyls ‘They are of two types. (2) Monomeric: Those metal carbonyls which contain only one metal atom per molecule are called monomeric, carbonyls. For examples :[Ni(CO)4 (sp°, tetrahedral) ; [Fe(CO),] (dsp, trigonal bipyramidal). (0) Polymeric : Those metal carbonyls which contain two of more than two metal atoms per molecule and they have metal-metal bonds are called polymeric carbonyl. For example : Mn, (CO),» , Co,(CO},, ete 56 | Short Formula (Chemisty) WNResenence (@) {b) © @ ‘The M—C x bond is formed by the donation of a pair of electrons from a filled d orbital of metal into the vacant antibonding r* orbital of carbon monoxide. Thus carbon monoxide acts as.a donor (OC -> M) and a x acceptor (OC

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