NYTIDNOVN woodvA TM wOnIPA wanogy Adoosonoadg ze[noojopy pue Anstweyo umiuend, «sun Is) fp aUINJOA, Asrumayy [essdyd Jo NoomAL Vg ‘sonueupomaqy, 2 A sung anumey ‘do aeumog OME JO SAIS : J unjo4 Aaisuoy porsdyg J0 1009.0,-A ©KL Kapoor, 1985, 204, 2006, 2011 ke Fourth edtion 2011 Reprinted 2013 MACMILLAN PUBLISHERS INDIA LTD ie by Amitabh Nagpal for Macs Publishes India Ltd, Floss, DLF Corporate Park, Gurgaon 122002 (Hatysna), india ighthas been inadvnely ings, pease nly ie bliin writng fr corte aston, To ‘My Mother and to the ‘Memory of My FatherAooiey 9 ‘woueBeanoaus wnsuos pu uoreoaidd aay 03 nung PE IyqEINS Pte kdoasonseds senaejoyy 40 sao among snaosy "srando anu kdeoso vore0 3 sos ou waBou fe ms pur y yo Poe aoa uonsginued Jo Sep apNoU SSH, ‘PIPE UDG ANE nvouue Se seneju rudd euonpe a pIsoqrsuoNoy dey pus UU 28 R09}0W4, Papua sIdeND MAU SAPNA yAIUNIOA JO VORP MOUSIUL + 5 Jo uoreausp am pu sjoquks win senoojcu pue 2/uOR 30 2F9P J0L9¥ oso sopjsoq ‘stun ayo pur svoelado wnivowour seine ory puz wopezrueng Ate “oIueOVY ane JAE tp pap Stem SEunxaune JO uy ap u spoyeu swoWwa|ddas ‘voMpa puodes 2p Uy ‘ovffnamp posn azesyun 1s. + joureu onusansés stow vu xo tp pusistopu of J2pead 24h EF 01 SSupeouans sedoxd oxy yyy pawasaid usaq sey Jae 19afgas AUS ay, « “ssi Suouepuatswosas yan ay seresods00u1 409 tL + auyeay Buoy}oj ay 0}90) 7 SHIDLOA 30 vowpe pasynay ayy ‘stdoyp jo yung] WEW 21p SUEGIMSIP MOURA, W2¥8Kid JO rag a roojowosoew pur sojueucpoutoyn ms spc} noun " Noosoaoads sn29}ous pure ‘saquadeud ajouSew pur [e91s199|9 “Suspuog [earwayp “gmnssare ue sds ppm pen 0 WORD YIN 9p 0} ovJorgPreface to the First Edition three types of problems with different objectives in view are listed at the cach chapter: (1) Revisionary Problems, (2) Try Yourself Problems, and (3) Numerical ‘smeeaisarun areataz0¢ Bade0>, ysUEIL 2onDay XI amy (67 ummUaWOYy Buy or paddy poyray soresado-s0ppe1 941 MA emeouuy 987 SUN IRwWOIY TA oY 59) wory vafexpsy Jo uonsiby JeFUpONDS Jo HumNds [A Bou £9] sarPuIpioeD repod jeouDHAS OF SeUIpIeE.) uvyseneg wosy 10}850d0 ueI93} 110-0185 Bupa ory sabe SH U5 Avinsomny ALemmouy I eraouay out PPE ay) PUE PONaWY seUAS JBNO 10 awoUEH ® 20} von ZPupans jo ZIT wou0yy anoufeyy am pue wmUSUIOHY IINEUY Gy (66. soteeds 247-0961] 20} suonNaLASICS Avsuoey Kugigeqarg pur stonoung aanys jo SuoneUasaiday jeH0IIg $1 og wory waBosphy ayy :ioug 69° satnsajoyy nworec J.soug YeuoRBOR Jo VORA G1 [86 _S@zou3 feuoneyy Jo wonezTUER) ST Ze $Sroug feuonesueAy jo uonerAUEN YL Of Asoayy, 24n}4 298upanos ET 2g wonoora ayn yo sum 2A =P SPIUNOL TI 1 Gaoony, umn? spree, 1 ‘AMLINLLS UNOLY 1 (GNV NOLLYZUINVNO OWING 'SOINVEDAIN AVAL "T 2 somnpa t8ng 24 0 201g m0 oma Panu 248 01 200P% $}U9}U0> nares onasatsnneRn Ron 004 to0de 19 S861 *B20H1 mpd #29 100 pr swwauo> “yo que 20 404% kue 04 20) eumesg 2pm Au oF 08 syueey roads oy vag i i | i spreito} suons98ns aqqenyea pue “ye 3 Ausssaru 98 ¥ soneojoo pus syuapms Su 01 uo 2 suo fm pio ‘Csmbur oasies yo ds 2 20 wt pomtsur ow "ERI id" Fold oHpea Kuo souporgspur sqea Aus aBpmoMrye 1 yst | 2009 amp wou uous 4p o ats en yy ‘ane se yor i 0p youoneunay uses) sun 1 ip [op sureas dns 30 mote a sons sapstongun if 0 sp F830 Aston amy Jo sosmoo aenpesipu 1 9 9 0 UEMBIN FYOOANa) MosaNd aN WhoRL, “suspis an o someday 205 G00 pas aro oD Sat goad yong “Papcid are oquosoad raeiks a :2yso, pad am eousuma porn 2% jo a8popNouy 9 poo pms a nse pwn nga 29 paar sua Gaara ‘uonenyesa-sfos Ur sywapRIs exp o2 AaTUMUOddO ue pIOYR a evn Popo am oor Seve saa amfuugAnnexure X ‘Annexure XI 2. THEORIES OF COVALENT BOND 220 20 22 Expression of Schrddinger Equation 220 23 Bam-Oppenteimer Approximation 221 24 Two Approaches fr Approximate Solution of Schdinger Equation 222 25 LCAOG-MO Treatment of Hy 228 Molecule 249 29 MO Treatment of Homonuclea Diatomic Molecules 252 Molecular Term Symbols ° 267 Heteronuclear Datorie Molecules” 363 United-Atom Concept and the Carelation Diagrams 268 Hybrid Orbits 272 214 Triatomic Melecules 282 21S Comel 216 Conjugsted Organic Molecles 309 Anesure I Localized Molecular Obitals of CO and Ny Molecules 329 Annexure ML” Evaluat HY 335 ‘Anmesure I Conventional Representation af sp? Hybrid Orbitals 338 3: ELECTRICAL AND MAGNETICPROPERTIES OF MOLECULES 341 33 Effect ofa Dielectric on the Electrostatic Field of Parallel Plate Capacitor 345 i Equation 346 35 Debye Equation 348 36 Experimental Method to Determine crand p 351 37 Variation of Molar Polarization withthe Frequency of Electric Field 353 38 Lorenu-Lorenz Equation _ 354 39 Union of the Debye dnd the Loreniz-Lorenz Equations 357 50 Tonic Character of Diatomic Molecules, 360 311 Bond Moments. 360 Contents 314 Magnetic Feld in a Substance 37 BS Molecular Interpretation of Diamagnetism and Paramagnetism 371 316 Total Molar Magnetic Susce 317 Calculation ofthe 318 Gouy Balance Metfod to Measure Magnetic Suscept 5 Annexure 1 Magnetic Fields 383 Annexure I Expres entation Polarizability 391 . MOLECULAR SPECTROSCOPY 393 Al Introduetion 393 42 (Nuclear Magnetic Resonance Spectroscopy 401 43 Electron Spin Resonance Spectroscopy 430 ve Study of Quantum Mechanical Treatment of Spin ns in AX, A and AX; Systems $27 MOLECULAR SYMMETRY AND ITS APPLICATION 336 51, Symmouy Blements and Symmetry Operations 536 try Elements 542 ions of Geometric Operations $48 Group $51 of Symmetry Operations of a Molecule 552 ‘of Symmetry Operations 559 ry Operations of Point Group 560 538 Reducible and Ireducible Representations 587 59 Characters of aM: 510 The Great Orthogonalty Theorem 584 teristics of Ireducible Representations 586 ‘Worked out Examples of reducible Represer ‘aCharacter Table 592 515 Desciption of Mulliken Symbols 592 Readucible Representation basepoway uous £909 xo ou poo oa, Tsp pu woul w Yate roawoun end UIE age SEH VORP] foamy feos sta, ‘donetpes ojo Karas 2430 apuedapu 290 alpIsue> fen pe ‘one 30 apd ayy 30 abs ayo} twuonzodond se (3sau9 “rv anew apouleonsye 9 0 pabapsuns Ses 961 PHBL HH OHI Nowviavd Adoe-xOV7E ay aon pa Frouea er pandde uoyy ious yo snowayoq wiramenb a3 uo pase A1oom 4 toes on any ay) sem young ey GS0oKp JON stHOs 30} YOHaS af O Par STL ‘soofgo Tews Jo ano1Aeyoq a} 20; now a aN se ADAH TOAST 3H 1g panna eneds amsip 2p pu ef 2m JO ‘sloweslosqo jusuruods jo qn v Yomuse yuosi2uu ox Jo sane] amp SENG fpog 19018 e Aq pons, suoneipey wwore}peH Jo ‘Aaoou eo}9Se19 vononponut AMO3HLWIALNYND SAEVMOL Hb aaNjan.g sWI0yY pue wonezyuRnd Assoug ‘soTUBYIITA| AAC AA I oe xepuy Toe seaeysy yea15 pur suossandyg oneMAKMAYaUiOg. = xpurddy 469 swoIeg woIsIoNUeD puE SII) =| mpuoddy 689. sega soEEID PosN fYUOUWOD diio§ —axmauy (049 swaurvosirg Tepeweae, Pu" apoqog UE Yop 30} UEP UOREHIE 45 199 tensed © Jo Smyqegoug Zunotpana ¢zs 959° suonoyy uae, Jo suonewesaxd>q otaronpauy Zr¢ 659. (eden we yo ony 0x27 Burampary ize 829. SENRIO PAK Jo VoNEALOY Ore 129 wreks oehoonsy 30 SIEIO TINOEIOWLL GTS some ape2 A Textbook of Physical Chemisiry Fig. Variation of intensity of| ‘Two Fundamental Laws of Black- Body Radiations Various Attempts to Construct the Spectra nent Inseniy fzaiaton al theory, attempts were made to explain qualitatively ature of the curves depicted in Fig, LL. Two fundare {ows regarding the nature ofthe curves were established These ae docoubaa Stefan-Bolteman law This law was es conting to whic, te itesity of lr Proportional tothe fou power of he kel Ez oTte (24) bs wer ois 3 consan, know 5.672% 10° Jn? SK. Subse thermodynamic principles by Stefan, (Ghe area under the curve) is ature T, i. ie is found to be was derived by Boltzmann using Wen's displacement law Accowtng to this law, the wavelength 2 at ther Pinus. 8° #22 isebutin is inversely proportional othe tmpernare Thus Agu T = constant (1.12) Theoretical attanpts were also made to the shape of the energy spectra tis emg of Wavelength. We describe below te te important torent this dieetion, Wien's co assuring th size, Wien ation Based on the classical electromagnetic theory and oscillators from which the radiations are emited ate of molec, le to obtain the expression B= Sexpe wai Free biar) 3) cera the enemy emited between wavelengths Aand 2+ and a and bare constants, It was found thatthe above equation curves in the low wavelength region, by wavelength region (Fig, 1.2), 8 very good fitting reproduce the res ‘and Atomic Structure 3 Wave Mechanics, Energy Quant range Land 44d per ax dn = SF aa wate avelegth eon is equal to (mE) ad is The energy deny in his waelegth ei Baia eqgal to £42 wh. she comesponding energy ened. Ths, we E,dA= (dn) E a of dn and E, we get Substintng the exresi (in az (a) an One nk # Accoring 10 Eq, (11.6, 6, the wavelength, Hence, E, conics to 6) is found to tthe experimental data a the high wavelength s completely athe ow wavelength eon and ths leads to wht is violet catastrophe (ig. 112). a6, Hence B= proportional tothe fourth power of ease with decreasing 2. Keeping in view thatthe Wi egion and that of Rayleig 3 intermediate expres range of values of 2. He derived the expression: aan is very much Behaviour of Eq. (1.1.7) at low values of A The factor exp(b( A) is very(! aye ata om (: a nee (#5) =09 3 Ws, sal on (611) ba uy up 30 uowsanno on poe (HTT) “a BonMDSANS erry oxen song aH OBE x on) Na se panoud aq wo ve aetret N N ru + (aylw + (g)®u] X= [oot xe e nen] = [-+G0%+ ous oO T=2 pm sa Boyoxiua 18 om N wwe nye a woa8 61. &@row9 aBesoAe am MON, 5 aimonuig snacry po wopiysiondsKBinu ‘sonUmyDapy 20 oneieu _sueop-ybjiorey, ‘1 uonanpou ‘YanBuojonem we porwr A61003 ) 30 worsuedya amp ours x1 “GTN 198 da @TI) ba bg wou Wy Sumunsqng, {W'S <1 Sowyos0 yo squint peo, ‘smo. Se panna 29 ues 0 ai Jo AfsouaaBtzane a woIsaudx9 SMH Ml 1HI5U09 w su atin Cys 6x0 % = J asmneday 1 9 KBsoua 01 Bupaoo9y sores am yo 1 8 pacogdina2y ‘snp Jay {efon we 61 w poe soveoso mm a 30 ABtauD am st onan gu='3 £9 vont Bawey sore>s0 Jo qu ai nef uO | A@soua aferane tm anda oy worssaxdxo woe c ‘Siow wunurupu 2uos fo pdm yousory 2y Bow fo nou kun 9304, 9H “ynser 241 ureydxa of 29p30 ur y>pour "woutiper Spo9-y2HI9 "8 = (9) Popwond pra 3% Lh WOH Youre gy gw? Te 'bg ur woneya) ahoge oq Sun SF +1 Gripes 8 wont 9 089 (y/q)de9 uo aq) sm pu anqea ems © asey Deeg wasn an WB 8 Y BLY Jo somon YY 0 (CT) “by fo mojoyeg UT Pa) von sys 9 (arnrtio £ ary 01 soenpar (11) ‘ba ‘womeps axoge ap HAN (arigebe = 1 Urraytxo ‘um Kea am snp pu ‘900 wey oH wept uorssaxa ue 2018111950 2tn jo ‘6103 @Be10ny your} 30 epow reojes0oys Kaspucyy poostyg fo yoouren ¥6 A Textbook of Physical Chemistry ously—aa assumption ofthe classical theory. In the shove approximation, expenr) © te & i and thus B= 5. » our # ik if a In ocder that Bq ould be reduced to the Wien Wien's Relation wavelength regi, Plank sso tok bal ten te ¢ state tat Airecy propor othe fequency of te adatom a chy Where is the Planck's constant and has a value of 6.6252 x 10% 1. Since v= 1A, we have coe 2 Substituting Eq. (1.1.17) in Bg 1 we have With the above bak from a black body as a fui of wavelength, both in the a high a we have " Hoe aS) a (#e)] exp(-he2ir) =0 ‘summary of Planck's Contribution Problem 1.1.1 Solution Wave Mechanics, Energy Quantization and Atomic Structure 7 Thus 94 FE =O oe are He constant 5k ‘This expression is, in fact, Wien's displacement law (Ea. 1.1.2) Planck's contribution may be summarized as follows: £7) may be reduced to Rayleigh and nck assumed an do 50 In order that the Planck's equation called quanta n may be reduced to the Wien's equation bution, radiation law, obtain the Stefan Boltzmann law E = o°T“ where is the total cation energy from A= 010 Aso, Le es fearon" Gree f ‘The Planck's equation i she Fa Biexpihc ART) =) Let x =helAKT. Therefore AvsholekD and da =~ he desk ‘Substituting the above relation in the Planck's equation, we get Iiegrating the above expression from 0 t=, we have e-faw- fas | Skeyo suo sepia sms 5 3908 JO omen ap aEEp o1 spOUTA tp J0 200 20 "pamesion souejg am oa ado Hi 90m BENS w SPM rte tp Jo 6@x0ue anu] ‘soja suonoe}> yg wo2 ar or jou a jo Fuanbayy sns2\ sUOH} fo wordy -uoneypes waprot 2tp yo Kovanbayy ap a 4 panna oi so KBzau9 onouny a WN papmSn0D a9 AL tay ay =a 3 Oey ea anv 2m (HET Pe (OTT) sb BuHEGHICD carp ax Jo uy oswoxouy ep sepv0u9ur popu stro JO FogKN 2H ‘SAL biaip uo 204 pire panwa suon22[e Jo JoquTs 24 1 foo 19 vam mn od you a SUPRA wyuenb Jo Aqui omy woot 28 "WE caaay ain A484 Jo A4ysuzpe ap uo 708 poe LORE ‘vo spuadap svonsap Jo ABsou> oneuly =n vet SO “uot sr 0} SBraU WL ne wonooye a % ue yes erp any an “0809 pengns 2q ue wonoof amy Souenbayypyogsus 30 st UoREPE? 12 7 4 rr wt au 5 ad Da ‘ yo ap oe wonooye pongo xp Jo Kua xn ‘snore amp 30 Ezan0 ep O1 To oonbse wonDafe atp ‘eu 241 Jo WD! a Ms Sepmico WIONA SD UAL A (01 nbs £81000 feo sated sjnoip Jo dn pene 2q 01 pats Boykoydts q 18x amy yo Aowenbayy ag wo von29f2 paNTID oR 50 asoua apaury 0 epudap amp pe Zovonbay progr 0 2uateH9 “uO ]0 6 asmonug nuory pun uomomuond Bin ‘MOyreH 0A ‘suonoera powiwa yo AB1003 NUD paya auporooiedd oa ‘WSU ‘ossrue soars a 24 ‘a4oge pats nay 2u922qeoqo4d Jo SONS ARIES “sm qsuo. st wo spuadap ueoq wy 2p Jo ABsou9 amp “Sz0a e ‘Brana o2uny pe KBiou9 paras ‘24901 penbo st uonsoyo amp 03 30 Bsou2 9n0URy 24, Aysu>}0 SH wo YOU uP ‘1p jo Sovonkayy 2x9 uo spuodap suonsoto pons aq Jo A@isU9 aNA0P| a], « “Kouonbaaf poysany am paqe> Souanbay, tunaurar aus wey 2,08 20 07 fondo Kouenbayy Jo uoReIpE iv pompEA a1 way are perow anS e uno KjsnoauzreRsu ponruD ax SUON29}9 UL, & ‘panrsgo are sonsuaoeqp Suojo} 2, wo ST 8 Jo uo € Uoye MMe IIS PAE ‘eo ¥ wy AjsnoouRNEU paymHD axe SoONFA|9 =p YaayD owIAA}DCIOK 3p YL s ot coats spam a Bnaabont uy Tayssooons sea 24 8H Jo aTEU yNOsNAO> am NYA Ay 01 Tonba ABsa09 Uo ayGaeo uopoyd yoed wpm aumgeu wr ejposndicn 29 o} axe WBN a pasgpIsu0D ‘rou ‘mi, ‘suonoyd poqe> ewenb 184 Sunssuoo “peznuEND SHER PD Yooys 2eF—CI0N idx 09 Kou. yeojsser9 jo aunyes su0s993 Jo uorssw3 ain Jo) uowosnbow, ‘61003 oH 2u29}00}0Ud Jo ‘sopsuajoeieyy, Aasqucyy powtys fo youeL V §10 A Testbook of Physical Chemistry Experimental Determination of Kinetic Energy of Emitted Electrons Decrease of photoeectriecurrent withthe retarding otentiat Example 1.1.1 Solution ‘The kinetic in Fig, 1.14, increased ‘of emited electrons can be determined with a device sho this method, retarding voltage is applied and its value is electrons from the metal plate each the col | ‘The electrical work done inthe above process is Ve, where V, isthe retarding Yollage and is the electronic charge, The electrical work willbe equal to te netic energy ofthe electrons. Thus, we have 1 Vex d mits hy hy, hes g mite ky dy (ia) (a) Calculate the kinetic energy of a phorolecronemited by a sodium surface when ‘wavelength 400 nm is incident on it. The work function of sodium is 2.28 eV. sue ofthe longest wavelength Which ean result in tcf he gest wave tin the emission of oF ms") =4969 «10s Based on ‘of Equiparttion of Energy Disagreement with Experimental Fact Wave Mechanics, Energy Quantization and Atomic Structure M1 ‘The wok funtion of sodium is Bye 208eV = .28e¥) (L602 «10 23.653 105 [Bnergy cared by the electron is y= By B= 4.606 (@) Wavelength of te incident phot je 6b 0 ‘work fonction G63 x10 25441 107m = S441 om HEAT CAPACITY also showed thatthe problem of variation of heat capacity of mor ith temperature can be resolved by employing Planck's idea of quan The monatomic solid may be considered a cof oscillators with thre: ‘vibrational degrees of freedom. On the basis ofthe classical law of equipatition ‘tenergy, each oscillator of such a solid possesses an average energy equal 3ET. ‘Thus, for one mole of oscillators, the molar energy is E = N,GET) = 3RT Since Cy = @EIOT)y, we have Cy =3R ‘According o E (I.1.28), monatomic solids have a constant heat capaci {03R(a vale which was obtained empirically by Dulong and Petit) Experi itis found that this value of heat capacity is observed only at high tempe 24) ical theory, the heat capacity of a monatomic solid should ever, does not agree with the decreases with the ations for Pb, Cu, Si experimental fini secrease in temperature, Figure 1.1.6 depicts such and C. By employing Planck's idea of quantization, Bin vatation of heat capacity with temperature. He have vibrational energy which is an integr in was able to explain the Bane oven 126) frequency ofthe oscillator and vis the smallest allowed frequency scillators are not vibrating withthe same frequency but have value ‘an integral multiple of the smallest frequency vp. The numbe sessing the frequency Vcan mined from Boltzmantse my a4oge 2yp Ka poonposdas 24 uafeaphy om Jo we ELOY ue we Orep “ud Lo-9gy “HU ‘atqeasesqo oy ome ‘s Sat san wos oe oro same so so siren oy fq arse 8 satep ogy ot in pose serenop 4p otoovey "oy en 95m yom sseanapandey —— se possadio oq enoedg uaBoupiy wnoge x Aq s6uppung rrp rewounedeg WoLV 40 7COW uHOA 3HL facet soimproduioy we= ite ="9 son a wen07 ney am ‘Soi ‘Pato}H0U 9q UPD om ueYp ray sromod 2m ‘soamesoduia moj 2° Jo onyen Bul ‘um sual oy pur ffs A294 St Z4/%ay “2 Jo sonfea YBIy SpustonTS iV ‘ononbo was se unouy (oz) f+ cen’ sn o} oO ent Tay + ar 5 Aomdso wy ajo yo snea Sxpuedban an poe ; [eave ey aayean+t] of We(go'Nea ‘2ABY am YoIoey JeUaUOdKa amy Supuedysy eT) FEC ay dx ay t= Cenandal pay) 7 capes (oy) P89 8282 Saran ~arrayivo yom 51 ay sore ap ve os yBoUD YBly ame 19 2 1 paonpas aq n> (67 3 ‘ME Jo ane feqsse ap 09 s8ea23U org warmers gy w 288 agp on 30% yoanqea ap uodn spa | 4Wave Mechanics, Energy Quant 14 A Textbook of Physical Chemistry model of atom in which the ee shovwn in the following ne us ou ne nce ed ea nr radiate cc tous energy. By losing Slav wulcome nae an ete he ake nd enc. Thw gives ie fo a able oma Anfnan = 486.07 = 364.56 (. ern ; sn which contradicts the experimental observations (as at at 2 ( Sain acm cnt i : e rimer ‘determined discrete spectra. Aan 2900 «36455 (5) 6496 (2) «aco ea ng Pack’ idea of qutzatn of sled te sore problem by aso tom 2 Tc ng vo a cou ee cal cea oe sent systems of atomic dimensions and, therefore, it has ‘tarot adequately epeset 5 Set eo (Le 36 and Ayfom = 41013 = 36456 (©) - (¢ . Fae] 356 (B) «ato in the frequency nit, we have Expressing Bg, (1 meio tt (G56 107 m ich appears inthe Such that Av is equal t the difference in the energies ofthe two sates. can be generated by imposing ‘Bobr showed tha the allowed stationary the quantum restriction on the cascalexpesion given by Ea. Rotherfrd’s model. The quantum retition proposed = GEES mf wae" (F-4) Since nm, =2, we have ay ie uit of rromentun ofthe eevoving electron rile of the bas ™ wa Ohm) ie B56 x 107 @ Z on a (3-4) mere "\an) SP SEGE a) a.) svete nthe mmiber of quanta of angular momentum andi knows asthe quantum, umber! The number w can have only integral values auaton (1.132) as sugested by Riz. The constant ys known asthe Rydberg Const for byogen and has a vale cF3289 83 10" Hz (1.09737 10% Prana ttt Model Ts the Rutherford model ofthe stom, econs revolve around the sueles in ch oftiekogen Atom — way thatthe Colonbic atracion ofthe elton bythe mews tle by oe which ends fo pl the elecion and nucleus apart ie ) force = centrifugal force Ts qn binging energy Tis quan ency of rotation ofthe eeron fn an in terms of frequency of rotation is 33) KyTEND oq, werd ee: am op 2 ehh ero one eens ow upey asp 3 ane 90 sit, (at) 2, iCemn ieee Set out) 198 a8 (EET) “baw worsandso ode ap SuNSGRS ‘anny om sO AaeuoneIS 1 sh toujours 4 pou 99 ED Jo snipey ta scaspuoyg porskyg fo yooqna, ¥ 91 LL aumnayg snwory po woyrinuonts &Bs2ug “OCHO 2htization and Atomic Siracture 19 18 A Textbook of Physical Chemistry Wave Mechanic, Energy Quantization and Atomic Su Energy Expression Now according tothe Bohr postulate, the stom can emit radiations only when the for the Spectral Lines: “hese spect ines can be generated fom Bq (1.1.40) by giving diferent values to my and ty Thus, we have Lyman series Balmer series Paschen series Bracket series fund series ‘These are also shown in Fig, = a 8 ee oe Wy 1 where Ry = 2n?metMi®(4ne)?. This \n is, in fact, the Ritz equation nts eae eaten of Rydberg a ea = 3.2902 x 10'5 5“ 1 o Ra = 6979 x 10 mat 7 HOT 2% 10 wt i remarks about ‘may be made, The Bokr'stheoe ‘The value of fy is vey close to the experimental value of 1.097 37 x 10° en Bohr's Theory ws Tore, Boht by itoducing quantization of angular moment a - ines of hydrogen atom. His theory can very We ‘Spectral Series Five spectral series of atomic hydrogen are known, These are: pecan aoe oan pect lines forthe hydrogen species—species containing on rman series Lies in the ultraviolet spect eon. However, completely file whe Hydrogen Atom uy Lies in the ultraviolet spetal ae Balmer series Lies in the visible region, och as He* and Li, Bol’s Paschen sees Lies neat infared region. Bracket series the infared region. fund series the far infrared region.fo2arg2 Poy pm paige 4 ate ee oy aon tang ones = am euxorao pasnnoo xp SO, 7 Sut popes om ft NORE re ape 999 foo 5, 349q 61 woRSANN!Y aw ON sayaeay) sojed am por 69 pooeydat ret Sessa pomp a 54 : 0 rn aoa os FATIH ta 2 uodsaiey urna wnt © Jo WHS iow) sre Ot cy dou) wo J Sea a ang a8 CTT DI PTT) Wa BNO] 45 5, 2 sono) peings09y ai” oor eget =a (vd ‘ or yruodsasso suossanixe 0 72) OS "o ejuou jo quouou a S17 4 anu eBnyuon pe £8109 aay 2 0 ue eens @ uf “yno=gou A (12 Mo (te = of 22 }o ol thee ‘on sotgipoms (24°11) “DAL “SL aries oe ang 1-1-8 8D 4 amueo yo woRro0| a WOH UOH=ST? se zomanus agony pun women u01 SM? 07H, wna sey AG) = pus aut) =a So! 1 [pUEDE/KS JO qn) wpe jo Sombra Suess 308 ue Sstnen pez Jo DUET ‘snes aad a ‘wogmova! 200 of “paoey supe mt ponds. "wRNULDD A ‘2 pu uond tp voameg 4 sump a J0 sur wy possan oq uo % pues ‘eaves a, wren! pov UoHs> 030} as mp stay Kysop eA a aH, crv oftuso}tu=7 omy om sm, Sse Jo vrosd ax 0) pu “see 30 uanooye 24 3 Buenos TEU FAHD 2 30 ans ano obo 5 wuns2WU eB ENG TOYA wove ary. a JO wr su = 400 = uonsojaay Jo wnuowou ree [eHO aN HON, 4o=a woyssaxdxo we £97 ! nue sy yo sun 1 possaxdxo 2q una tujod © punore Sunjonay pane © 5 JPO0T 9 somos se pasoud og eur sta, 58 pauyop ‘wor amp Jo sseus poonpan mp *w uoMDa.2 40 sseur amp aoe}dat on 51 9peus 29 01 8un4> Ao ayy, PasopIsuOD s Feu Jo aU ‘wou 24) punom® uonoaye pu snofpnu Hurafoxat Jo sage} aAoge a J YEA ‘atovfeun strewiar Asoo 8.4 Jo WSTPUEI] arMUD a4 YL WMOHS 29 HED If ‘uaoys se 'seoused on 19 Su punose ujjosar ase uo ay am Jo asmeo9G“H pn 2930 ‘sne}onn ‘up jo sseMN UL 14 >u1 UY Je} OS 94 40) UOND_NIOD usury porsiye Jo yooanay ¥ Oz22 A Textbook of Physical Cher Example 1.1.2 Solution Example 1.1.3 Solution Example 1.1.4 Solution ay Calculate the sped ofan electron inthe fist Bobr ott ofthe hydrogen atom. Given: ay = 52.9 pm, We have Sh For the first Boh onic = 1. Hence ie) (529x107 Calculate the ionization energy of the hydrogen atom. ‘The ionization of an atom isthe enersy sequired to knock ou the electron completely fiom the stom to give a postive ion. Thus, inthis case we have =218 103 (Calculate in eV the third ionization potential of the Lithium ator ‘The third ionization potential means to knock ot the lat single electron from the Li?* Jn, je. Li* > Li?" + 6° In this ease, Z= 3 and thus, we have “eee Cle) Using the reslt of Example AB #9 x28 x 107 3, we get = 1962 « 10-5 4, we have Since 1eV = 1602 «1 1.2. TOWARDS THE WAVE NATURE OF THE ELECTRON Wave-Particle also possess particle characteristics, The converse of the above aspect, vi ‘material particles, whether big or small, possess the wave chara : proposed by de Broglie. The relation connecting the characteristics of wave and particle nature of radiation nay be desived a flows Wavelength of an lectron—A Specific Example n and Atomic Souctare 23 Wave Mechanics, Energy Quant Both the wave and patcle nature ofthe radiation are associated with the energy according tothe following relations be gabe Plancl’s relation oe 23) of pane mature (ema =) each other. Now cin wath 2) are iaversely related 10 the photon, and thus me may be considered to be the joton. Thus, we have For ordinary material patil to be equivalent 10 v (ie. the 4e Broglie velocities) and thus Eq, (1.24) small, asin the case of subatomic particles, the ‘foe them wave nature is expected. For a particle of ificance, on eclertt tn canple, let clelat he wavelength fran ele Asa aml alloca ¥. Te net ene of te econ woud begs pte eon 2 mvt = eV i snd hs Bement = mvs m(220)” = cmev!? as Ue Cm) 5 (125) ina (1.28), we hve gets tye ~p mevy™ Substituting the values, of A, m and ¢, we have Aim 21.227 x 107% 26, For example, for the potent . = 1207 x 1072 x (300)! m = 7.083 x 10m = 70.83 pm ofthe chapter forthe derivation of Eq, (24) based on iy.wx res ve og ta won yo Ao on ons Buen 1 x PE (aor 01 x sore) % 9299) ety 2% wont aos ap aid (8) wong ya o uapien apse cond as on pauogson 9 uno We Hp jo 9 0 Joe (012 als tw oy popooe wae uoBeeo WE pes aA HH soma EMEA ey 31 (@) yw Tp 9 pfuant 04g ap a8oyN YORE we JO paads a TENA) 01 S80 X O90 x GOT} gawe) Ey oN StH 01 x 90ET= 1 a al + an) * aw © oouy nay an 42 = yaw © aoug {an 00g 30 aauarayp renvarod Ka yessaone uaog st ip ome} UE Jo BuEFEAEN 1/4 9p pu RODdS 9 STIEGN ore Jo {aoa si BuyquoseP a syoR La poonpanN! Sem YOIY UOTE e se (B)eerea » (ve 1) ‘bg uy woneyas s.anoug 2p SuronponD Re aamanag anweay pro voworinamg) (Bio ‘sorum4sey 240A uonnjos zee oduexa wonnies bes odes 29 200 ROM 2A IN ‘foeyppypow euro 2 wen “31 “pusjanea -paruasgo 24 s9xou ueo sopradoxd anton amp 05 fgo wash Aue jo suorsuauTp a seyp JONoys Yom IpAUapPAEA v AADIPUL (1 se yan 05 wnquatton ayy ‘SUH snp # 10} Hon 430g ‘anv ap Jo PBvaFOAOM ep Jo HH 5019p waoys ancy Suouedxa pied-n pov wore uafaupAy, EU 24BM ep “UO 100] ‘uopenbe saffoug 2p 219 Woy ora uomoyo xp Jo psu2fanem a pae|oqe> 0 ‘ape posn Soy], 2ounoH J2}] puE UOSSIAEC, 5 Jo aanvew xem aap Jo uo} Sones8 wonzeaytp © 0} “9A2HOH “to s9 wea auo "ig Kreupuo 30g "kb yp Jo pBUDJaNEA 24 JO FIO soymns aan amp AYA HA aK sep JO suorsuAUNP =P kN J0I0e) UEZOM ‘25u0 uo spusdap souai2n%qu1 puP uoR2eApHp Jo wawouayd jo oueweadde =x, ‘s0sseW 396107 Jo soomse's IN One ‘ayy uo quawwog uonoota Jo o1meN orem, Jo uoneoyrion, rewauuod3, Aassrucyy poosky Jo yoownas V- ve26 A Textbook of Physical Chemistry Statement of the Uncertainty Principle Qualitative Explanation of Uncertainty Principle Fig. 122 Location of the lect help ofa microscope fe 6628 10 03 10m) TexiT "aaa ele 2824 x10? m ‘THE UNCERTAINTY PRINCIPLE In de Broglies relation, the particle nature of the matter is characterized by the {erm momentum p and the wave nature by the term wavelength 2. The two tems ae inversely related to each other In other word related to the stave natu the wavelength as calculated from the de Brogle’s determined experimentally. For such a case, the wave nature may be completel jgnoted and this the particle fas oaly the corpuscular nature. The motion of st the precise value ofits pos also be determined exper ion of the particle can be Aesctbed by a well-defined trajectory. However, the same isnot te for a subatomic particle such as electron, proton, et, which besides the particle nature also have the significant wave nature, The question that whether the position and the ‘momentum of subatomic particles can be determined simultaneously with grest the following example to be determined with the help of = Approximate Expression of, tered photon will undergo a Compton shift. The stectron on str ‘2 momentum and will move in a 22. The momentum ‘iretion making an angle f withthe axis as shown in Fig. 12 n Of the photon befere and after the collision can be calculated from the de Broglie's relation, Thus, we have ‘Momentum of the photon before te collision, he mate Momentum ofthe photon afer he clision, — ape Now, by the law of conservation of energy, we have ened ate Z «2s, toe ho mb b B aed the comesponing expression forthe conservation of momentum inthe fa pedetons ae Foe xeomponent: MY = cos 0+ pcos B 20 by _ hv’ For y-component pin B Eliminating fi from Eas Equation (1.2.12) relates the momeotam wi angle @ to which the incident radiation is def detected ifthe scattered photon passes thro ates may have any value bet ated cone. Thus, we have the momentum of the se ‘which we may call the uncertainty in the value the electron introduces some uncertainty in its momentum value and therefore precise value cannot be determined connecting the uncertainty in the value of x ‘An approximate expression ‘Corresponding uncertainty inthe vale of pcan be derived start Uncertainty Principleojan pu wousod Jo sone astoaud one sp paw 1e9 YASH 2, fondo Ut ages Snap st IUTH290N STL, HH ay Ta voy wd g yo 2pu0 am yo ute st uot yD whe 10) "AL sqrwxo unouy ase wonaop J newt! am pu wonsod ai HOH HOE So spy og sats 1 200) ane aaron © tat 29 youueo fr abasic) 120198 see nt moqe Burge Uy aod Aue Ape sata woop “OR 6 FMOR sersad on panadxa $1 UDMDD 3) tu AGODA SAY MM SEI 798} raneure hy sy. 49 wToHAAUR SUC GoHDATE OTPK MD HT + (ay) (ty) =49 20 ney “mya Arevzoun op Bus panoge 9 ve SRE weiepuodsano> 941 ud yg poe wd 40S Jo sanmea 4 9g PONE oe ay ain uF won oy saue sa 2 es wd ¢ 39 AYoH2ON paurauoep 9g ues sna. oMp wos} YONI 2 ysod om TEM) "oy oye ayo unoe We Jo 359 xy “pdex9 Jo ye, soe asAAE fay 39eors (trquenso 30) Axo. a Pu wosod ap pod see! aane ounnste paujap-% axe ONES "212 ‘Suoqox suoNDdT se yon s3]9N ‘xwowegns rad Speaun 29 30 S2ovanTb2su09 19s 3 JO 200 rags Jane ap stp pu ofgo am Ho paHaHP 0 ue Jo donysad agp Jo woreTUNEI 219 japan ajonsed op -umuawou sy 296 GOTH| su ng yo wag @“oaoge uaes 9 "wasnt Busnseous agp epi sIUseHU} UOHEATES ‘room agdiomad Kurexaodn af 0 ase TIUATEpUN a4, 7H ap JO 809 2D TE ‘pasa pastas 2 we wae 30200 suo snoone Hs PSUNP <8) dp x jog Jo Sone staid popeyouoo oq SeUr Ht sM, 328%] dw rmmpoom tpuodsasso ay feta BK 4H SrURHHEOUN a 25831099 1 UENO ‘ons Aouonbayy gS Jo oda ay 32988 150 211 80 juresaoun upuodseL09 Ge. among nuory pr uoennuond) aawy ‘son@yeeHy * HA aidourd Ayuyeye0un 0 seouanbasuog Senos so gC EE Boas 2) aes sete a ren wlt- G2) =29 pu “vonod put wnuauoe a snuevcun seb cay hee oe Hy ney at aren =. zy Regent awa aon Sanam jo sah bese a, (amuode 19pous Jo adaosouoqut {made rus albsobnas fom 921) pu) SURE 9 2 Pt wMBERIOW an oapen ayy uy AHERDOUN ap (pL 1) “ba © Supsoy “Soo se pond HPD “Smote} se popAdN 29 Kew (S171) pue (p21) ston, wren = AH] (oma)- > savdy ‘ary 9m sm, ae edu oxo Sapcoe ps pfoydua voip ajo winpnes mode spealey ‘sozsas e yap p2ie20} 09 ueD 1Afqo Ue YOR Yl. AaeBNOOe a MON, ) usp W a ‘weamioq anpea Kur any Kew uo aot Sateen ony aa eee 30 wooodues oxp sywasosdan (€{°Z'1) ‘bg JO 9pIS Yo] UL, (9800-22952 2-2 2 DZr0mT- Tadd 0 mod +9 002 = am ama Kasay porssyg fo yooqney ¥ 830_ A Textbook of Physical Chemistry hence a precise rsjectory. For macroscopic particles, classical mechanics may be employed without any derectable discrepancies, 1.3. SCHRODINGER WAVE THEORY Necessity of Wave theory is based on the corpuscular nature of elect, We have seen that ‘Theory ny, besides being inadequate, theory which takes into account the wai distribution of the electron instead of the wel Schydinger proposed the wave theory whic that the behaviour of an electron in an atom can be described by an equation analogous to that used to describe the standing wave systems sch asthe vibrating string fixed at both the ends. An alerative theory was developed by Heisenberg and is known as matrix mechanics. Schr8dinger later showed that the to ‘mechanics, ame, wave and matrix, re essentially the same. Of hese two mechanics, the wave mechanics have proved to be more useful in applications to chemistry. Equation ‘The equation used fr the wave motion in one direction is Representing Standing Wave » System where is the amplitude of vibration at any point whose coordinate is x a ime 1, and isthe speed of propagation ofthe wave, If w doesnot depend on the time, the displacement ¥can be writen asa product of two functions, one depending only on the space coordinates x and ths other depending periodically on the ime. Tus the form of where » Ba. (13, the frequency of the wave and i= JT. i we get “The frequency Vof the vibration and the speed w are related by the eg uz dy where 2 is the wavelength of the associated wave, Substituting Eq, Bg. (1.33), we get Wave Mechanics, Energy Quantlation and Atomic Structure 3i Eigenvalue Problem ‘known as the eigenvalue equation, the function is an mand the constant (~ 47/2, i this case) is an eigenvalue (sometimes 3 proper value of chi ie value). fn order that the (vis an acceptable solution of a. the basic constaits. In the case of a vibrating string ( ‘© The function yrust be zero at each end ofthe sting, at these Fig. 1 Vibrating stringed at bo ends 3.5) an be extended to describe motion in three dimensions by ) by w(x, yt) and the operator d¥/dx” by (36) Equation vive aan where V?is wri ay?) + @V80%) and is known as Laplacian fperator.Itis proaounced as del squared. Schrodinger cei al ao pies Equation sms of momentum by employing, (138)