Part (G) Molecular Spectrosco} A-Choose the most correct answer 1-The relation between frequency o. wavelength \ and wave himber v' is given by ar =cv'=clA Alo’ © =he A /o Ey 2sThe excited state configuration of element is (9=6, I=3,m=2) so its ground state is a-n=4, 3-The selection rules of photoelectron spectroscopy are. _AtThe valence electrons have the energies because they are. @-highest, more shielded and farther from the nucleus b-high, of more energy lowest, more shielded and farther from the fucleus d- none of them binding aa PES spect., the intensity of the peak tells is a- relative number of electrons in subshell b- concentration of electrons _A=1P. of valence electrons — d- population state 6-The term symbol of ground and excited states of *X element, are... and respectivel a *Pin, be "Paz 2820 Paz, Diz d *Pye ,2Ds2 7-The IP of the 2p? electron of element 18x is given by a 9R/1B b- 4°R/18 c- 18?R/9 ABR 8- The 1° AT spectral line of the outer electron of 20X is splitting in MF into a 5 2 c3 a6 ¥ (60 marks. @ The two elements »X and 22¥ have AT spectra due to < biferent AT mass, n and I quant. No be Different AT No, n and I quant. No ¢- Reduced mass and radius dé lonization potential 10- Three differences between Harmonic and anharmonic IR are a Selection Rules, No. of Spectral lines, and effect of electric field b- Selection Rules, No. of Spectral lines, and effect of temperature Selection Rules, zero paint energy, and effect of electric field _S” No. of Spectral lines, change in bond length Ar and effect of magnetic field Aa How many peaks would you expect in the PES spectrum of Ca2; a3 we 8 6 12-Beer Lambert's law gives the relation between ...... (@) Reflected radiation and concentration (b) scattered radiation and concentration (c) Energy absorption and reflected radiation _{9) Eneray absorption and concentration \ 13- Beer's law states that the intensity of light °° eseenee th FESPECt 10... (a) decreases, Concentration ABS decreases, composition (0) increases, length (d) increases, Concentration 14- The elastic scattering of photons is called (a) Atmospheric scattering (b) Rayleigh scattering _(c) Conserved scattering _Ad§ Raman scattering 15- The inelastically scattered photons are called as _AS Raman scattering (b) Rayleigh scattering (c) Atmospheric scattering (@) Conserved scatteringig inthe spectrum of sodium the number of fines obtained are Bio b) three four d) five 17) SFe and H20 are ..,,..and...... rotors respectively a) spherical, asymmetric b) lingar, symmetric ©) symmetric) asymmetric A pherical, symmetric Expected and experimental number of wibrations in ally! bromide, CH.=CHCHuBr are gh) 21815 (c) 144810 —A9) The A of the emission fluorescence spectra is shifted due to a- blue, intersystem crossing _b- red ntersystem crossing _c- red, thermal degradation d) none of them 20) The order of increasing vib. freq. Yor C—Cl, C-Br, C-C, C-O and C-H bonds is .......due to (a) CH, C-C, C-O, C—Cl, C-Br increasing p (b) C-Cl, C-Br, C-C, C-H, C-0 increasing k (c) C-O.C-H, C-Br, C-Cl, C—C increasing ky SB CBr CCl, C-C,C—0, C-H decreasing pz 21) In poly atomic molecules, silent vibrations which involve no change of dipole moment or polarizability are (a) !R active but Raman inactive 46) IR inactive but Raman active (©) Neither IR active nor Raman active (@) Both IR and Raman active 22) The PES of an element X shows 5 peaks at 1.76, 2.29, 4.89, 6.84 and 104 ‘Md/mol with intensity ratio 3: 2: 6: 2: 2 . the element is ap b)N py Al dP 23) For quest. 22, the peak at ....... represents 2s subshell a)l76 b)229 «489 O84 24) The first ener ) gy leve ee Oia if rotation of a 0, 6.4, 19.1, 38.2 cme. theres 5 MW spectral lines appear at = a"6.4,12.8, 19.9 a Sages 4, 12.7, 19 © 128,192,256 — q.¢ af 25- The polar mate N f S are MW active due &- Their dipole moment vector b- possessing of magnetic field © Having difference in electro negati 9 both of a ani b 26- Use the FEM, what is the ‘wavele absorbing photon e molecule butadi HaC=CHCH=CH, If its length is about 0.48 nr a 290nm b-217 nm c 527m d- 172 nm 27- In Raman spectroscopy, the ph a- Loses its energy on excitatio be scatters and lose its energy 4o~ changes its energy and frequency due'to Collision d- changes its intens: 28- In Raman spectroscopy the wavenumber (©) of the spectral lines is given by a0’ ex + wy be 29) The vibration freq. and rotation constant of HF are 4150 and 20 cm". The wavenumber (0) of the 1 spectral lines of R and P branches are a 40, 60 cm! 4100, 4200 c ¢- 4130, 4170 cm 4170, 4130 c 30) Morse curve describing the .......of diatomic molecule a) relation between vib. quant)No. and bon length ) variation of bond length and attraction ner a 4 men between attraction an repuisior the bond Z ae rate we lengthan line associated with the normal stetching mode of (CO) bond is found the Ram: acetone: a=500NM). Bt hen excited by Hight 0 yn asa raise ent explanation of Raman spectroscopy, what are the selection rules? & Now many cindamental peaks associated with acetone, and what are their types? G’pauate Rofthe center of Orr sponding IR band. pa Dawa schematic representation of Rotn.-Vibn. energy level anc the corresponding Rotn.- ‘pon spectrum diagram nb 626x10 Js N=6.023 x10" molecule/mole =10° 2138x107 JK" c=3x10* m/sec ompear boy sical chem(414C) Mol 2 dents Ist trem _Jan 2023 /Choose the most correct answer 23 Mark: excited state configuration of an element . then that of its ground state Is Be 2 mat d-neg [e2m=1 ve number ois given by dv'=co fF A The selection rule of atomic electron sp Coro anything A= #1 At CAN= = Als 21 Ame 1 Am=0, +1 As=1 iything Al= 44 Am=0, #4 Bs 4- The expected and . Mall bromice, CH.HCH.Br are respectively --- (a) 188 21 ( yee (d) 16& 22 Ae C-# stretching frequency for an alkane Is 2 The value for C-D frequency is (a) 2900 cm? (b) 2060 em? 0 cm-! (2) 2130.m= \e order of decreasing viorational frequency fer@=Cl, C-Pr, C-C, C-O and C-His faV/C-H, C-C, 6-0, C—cl, CBr ‘ sCI, C-Br, C-C.C-H, C-0 J C-OCH. CBr, CCl, c—c (@) Br, c-ci,c-c 0-0, CH wre IP of the 2p* electron of element "X is ‘giver a PRB b- RMB @ 207R [1/16 1125) & 4R [116 1125] 4R [1116 -1/20] the presence of MF, the 1" Atomic spectral ling of the outer clectron of °X is ....... into ‘spitting, 3 tines: b-shiftey higher wavelength. & shifted, lower wavelength, ditferences of AT spectral ines of the clomerts [ wae ‘mass, nandiquantumNo “2 (em Reduced mass and radius a The polar materials are IR active due to eir dipole moment vector ~~ ing difference in electro negativity. 5 1% MWY spectral ine (0') of CO is 12.6 om", the ( 272 ©-126 ‘of the answer of above question is... ‘ brCO CCl)» ACB s atid to i Karna Perec nce ncB) 4 ey (SDC CREMCepe Mea) end olety wy ‘cl speeencopy and photochemistry dr in ae types and oer ih cosy and xvton sors Photon energy ands mechanism and aaa sy Pre at aretine between "C"Q and Ca-H0 mee Mi, biter meses and quant No a ire tn) gum NO— NW. . &? le s¥ © UY, Different 16-18 itre a Their different structure © Different function groups Question TWO 1. Calculate the bond strength ( Knowing that the first IR line appears a3. Draw a diagram to explain the Zeeman explanation 1 When 58.4 m i photoelectron have kinetic energy’ molecular level? Question Three ‘a- Write the electronic conti sas, ten dete uFe Al b. Which of the following 2s—5p(.B) Molecul: A» Choose the most correct answer 15 degrees 36. The Ionization eneray of 'H is 21.79x1041J. 3x lonization energy Of ALI" 18 exrmnnd ae 279x104 = be AB.91K1047 —e- 19.64t 18 a 15,20x10" The 1 of any element can experimentally be detected using .. spactrum a NMR b PES & Raman IR Atomic (0) of a line of Balmer series is 487.0nm, to what value of n does it correspond a b 3 eT a2 ‘The selection rules of Atomic spectroscopy Is a Anzany, B11, AJ=0,As=1 > An=any, Ol=s4, OJ=0,£4, Bs=0 be Aneany, 4121, Om=0,As=0 — d- An=any, Al=-4 Ams0,1; Bs=4 (J), o(Hz) and (em) of @ photon of (A=200 nm) are, respectivelly ae 9.9410, 3.210, 4x08 G-4.94n10, 1.810%, 2.510% be 9.94610", 2.5x10%, OxtO+ d- 9.9421 0%, 4.510%, Sx 0# The relation between frequency 0 wavelength 4 and wave number 0’ Is given by bweeitscA cushcltshcA d-v'scomelh ‘The expected and real no of total IR bands of chloromathane are a3 b 95 27,10 10,12 ‘The Intensity of light depends on a: energy of lightiarea be No. of phaton/ares e- type of light d+ No. of photon x aran ‘The classification of light spectrum Into certain light regions is according to a- energy of photons of light region b- enorgy level of a materiat effect of photons of light regionon material _—_d+ Intensity of light photons 45- The separation between successive MW spectral lines is 12.6 cm", the three energy levels exist at a 18.9, 25.2, 34.8. cm* b- 25.2, 37.8, 50.4em* cc 6.3,18.9, 37.8 cm d- 12.6, 25.2, 37.8 cm" 4G- The polar materials are MW active due to a: difference in electro negativity _¢ Their dipole moment vector b- both of ¢ and d d-possessing of magnetic field 7.0A7- IR is used to differentiate between “C-"'0 and “Ca-"0 due to a Differ in reduced mass, and k b - Differ in reduced mass, F ¢- Differ in reduced mass, and v quan No d- Differin k, andr 48 ‘The dependence of potential energy on bond length of diatomic molecule is described by a. The vib, Quant, energy ¢- Jablonski diagram b- Morse curve d-rotation vibration diagram 49- Near Absolute OK, gaseous molecules possess «..8NTSY a- Rotation, vibration ¢- electronic, Rotation, vibration b- electronic, vibration d- rotation and transiation 50- The selection rules are Rules controlling a- transition between different energy levels b- Energy of selected photons c- difference between energy levels d- selection of type spectroscopy 8. Answer the following (20 degrees) b Which of the following molecules may give pure rotn., vibn. And electronic spectra , explain HCI, Ny, DG, SFe, CHCl; 40 degrees ‘The vib. Freq. of H'"F is 4141.3 em’ and of H™CI Is 2988.9 em”. Explain Find the force constant of them. What happen as the temp. increases? the position of the 1" and final AT spectral lines (c') of the outer electron of element ,X. S degrees h=6.626x10™ c=3x10" €,=8.85x10" = N=6.023x10 4nm=10%mB- Choose the most correct answer (C) J+ Morse curve describing the ........ of diatomic molecule The dependence of potential energy on bond length The relation between vib, Quant. No and bond length ig the variation of bond length and attraction enerzy fe the relation between attraction and repalsion forces of the bond 2 The selection rules of photoelectron spectrascony are. ing Al= a1 Am=0, +1 be Anmanything Al= #1 Ari0, £1 At g Aleal Am=O, 21 Asad d- An= a0 A= ch Am=0, #1 4. The expected and experimental No of total IR bands of chloromethane are b10,¢ 8-27.12 e310 007 “4- Mechanical facior. state of material and Doppler Effect are factors controlling » a- width of band bb Intensity of band)—&+ band position 4-10 of bands eee ace tes ters controlling ‘The transition between different energy levels _—_b- Energy of selected photons ‘¢- The difference between energy levels 4: selection of type spectroscopy {6 The relation berween frequency o wavelength A and wave number is given by o ocd! beorelc, eonhelt to=eo ‘JeThe terin symbol of ground and excited states of "Xelement, are anid ... respgetively be Pia. ‘Dia 1b Pia, “So Py, “Dia Pia, Sia 5 Differ in isotope mass, and 1 27-In. Raman the wavenumber (0) of the spectral fines is given by i, ‘asi Os 4 B(6)4) bea in + B(A)-6) 01g = 0+ BAI) = 0, + IBIS) aa j tion the material be scatters and lose its,energy / due 19 collision changes its intensity eeceriten! Using light of o'100 cm", the wavenumber (0) of the1" Raman fines are 30nd 70 em" b 130.and 70 om" = 130and 170 cm" d- Band 7 en 30: The differences of AT spectral lines ofthe elements 9oX and _n¥ is due to b+ Reduced mazs and radius be Differ in AT mass, n and I quantum NO Differin AT No, wand | quantum No Ionization potential Morse curve describing the ..... of diatomic molecule +The dependence of potential energy on bond fengah js The relation becween vib, Quant, No and bond length A the variation of bond length and atraction energy 1+ the relation between attraction and repulsion forces ofthe bond 316 IR differentiates between HCN and HOC! through a» No of peaks and bar position bb reduced mats difference © Bond strength No.of peaks and intensity 32: For "C-"O at 300K, if 4440) =1000 cm and xe-0.42. The hot band appears at a 1041 cm! b- 958 cm" 2872 ee d= 1000 em! 3 The population ratioNN\/Ny of vibration energy levels oF ™C-!O a 300K if Ary. =1000cm" is 09 bot €- 0.008 4.0.99 4-IR differentiates between CH, CsHyand C3HCh because of a They have different sircture Difference in No of peaks and band position & Different function groups 4. Difference in Reduced mass and Bond strengths 435: Thrice differences between Harmonic and anharmonic IR are: fe-_ Selection Rules, No of Spectral lines, and effect of eletrie fed Selection Rules No. of Spectral ne, and effect of temperature |g Selection Rules. zero paint energy. and effect of electric ele ‘he No. of Spectral lines change in bond length Ar and effect of magnetic eld 36- Jablonski Diagram explains © Therelation between vib. Quant. No and bord length { ‘The diffecent types of transitions within MO levets {The various electron excitations within MO levels 1 “The dependence of bond length and potential energy 7 The intensity of light (A*256nm) pases through cel (I=fnim) containing 0.05M solution is reduced to 16% ofits intial value. Calculate its absorbance and extinction coefficient when t=2inm. “ae 003. 1600 be 160, 1.6 0.03, 160 > 1.6and 160 [38 The vibration freq. and ration constant of HF are 4150 and 20 cm. The wavenumber (¢) of the I spectra lines of R and P branches are 440,60." ‘best 100, 4200 em't & 4150, 4170 em" 4170, 4130.om" |38efn presence of magnetic field, the 3"! MW spectral line of HCN, ‘® Shiflto lower frequency ——besplit ino Sines e-notafected split into 7 tines ‘40-Calcolae the eneray per photon and per mole of photons when its. -60nm me ZOSKIO 19K BSA MIONL IRM cASINIO" I 257K de 31x10), 2391 fe Esso, eLor10" m29t00 ke heer en1Oh m/secCiinseny Saas. UFBPAUA) J (Choose the most enrrect answer 23 marks 1 The polar materials are MW active ue 10, ‘Their dipole moment vector ‘be possessing of magnetic Feld Having difference in electro nopatvity 6 bot of wand 12:The fegqueney €4:5x10"* He is wave gumbo a ods al em DegelsaiOtem® ccalSxi0tcm! danSoxtom Me The intemsity of band depends. om 1 No.of ptomarea tb energy level of material ‘ype of lit 4. No, of phoion absorbed 34. The elasificatbon of light spectruin ints certain fight cegions fs according te effect a he photons of light region on material tb encrgy level of a materia! Energy of photons of fight region a- Intensity of light photons 35-The selection rules are Rules eontrotting . ‘a Energy of solected photons ib The transition between different energy bevels ¢ The difference berween energy levels d- selection of type spectroscopy '36- The selection les of photoelectron spectroscopy ar. a-An=anythiag Ale] Am=0. 21 ib Ane anything At £1 Am~, #1 see sin= on Ale | Ant=0, 41 Ane anything Al= 1 m0, at As~! 4 -thecexcied sate canfgurtion of an clement in(a-S 1-2. ev>t}then ts ground sa > scant el mie? eee Bue, cee he tel deed 3 Bol 3 The inergase OF Temps .ccaee 0 MW specteal a Increases the Nd of lines '}- changes the intensity of fines. e de changes the position of lines pli the lines. 39-The expected no of total TR bands of ehloroethane are a- 12 be 10 od a9 40-Tiwee dtferences been normal IR and MW specirosso99 FE Selection rules, No of peaks, position of peaks -Sclection rules, intensity. peak position &Inensity, No oF peaks. peak position 4.Selection ules, No of peaks, effect of temp. “gqe-The 1 MW spectral line (2) 16 12,6.em\ "the following lines sppeat = a 184, 252 38cm! e252 378. S04 cm) fe 189 37.8 So7cm" d 282, $04, 75.0cm" 44a. The intensity of ight (1=296nn) passes through eal (tenn) Comm 0,05M solution is reduced 10, Tees ett inital value, Calelte its absorbance and extinction eoeiciert ‘when |=8mnm a 003.1600, br 1601.6 60.03, 160 & 1.6 0nd 160 “43. The IR ofthe 32 elestrom of element 9X is giver PY d- RIT baR/IT = FRO d-17 RM “44: Thexnetimental and ealentaed No of IR peaks ofehlerosthane Ess different which is aributed 19 ‘+ Enistense of similar bonds ‘b: nonpolar structure uring symmetrical stretching i ‘ce chlorocthiane is nonpolar i the twisting bending is week 3/545- Morse curve describing the of diatomic molecile @ The relation between vib. Quant. No and bond length fF the variation of bond length and attraction energy the relation between attraction and repulsion forces of the bond The dependence of bond length on potential energy 46- The AT spectral lines af the outer electron of element 2oX is apt be Electric field be Increase of Temp. c= Magnetic. ing due to Hd Isotopes 47. The difference of AT spectral tines of the elements 5X’ and 2 is due to & Differ in AT mass, n andl quantum No, be Differ in AT No, nand | quantum No & Reduced mass and radius - lonization potent 48-The selection rules of IR spectroscony are a Reduced mass and radius 'b- change in polarity and Al=#1 © Differin electronegativity and Ayo d- change in polarity and Ay=s! 49-18 spect. is not suitable to differentiate between "ACC and 'C ~ "0 dite to. a Differ in AT mass, and same bond strength 1b- Differin AT masses, ¥ quantum No: & Negligible Differ in reduced mass, and ¥ quanti No 4: Differ in botope mass, and x io a sinereniaes rerween HON and HOCT through No of pealks and intensity be reduced mass difference © Bond sirength No of peaks and band position DP) Anewer ne tottowing, J+ What are ALL the possible types of spectra for each of the following compounds, H, Mz. HCI COs, (CH, CH)CI? Explain your results, ‘Omarks 2 Inthe MW spectum of 4C!"0, the separation betwee the lines has been measured tobe 115270 MHz Explain: what happen when the temp, increases and when a magnetic field applied. Calculate the position of the first wo lines of FCM, ‘6 marks eer BESMON Ci, enhGO™ mB 1GO" ke, NGO end enisec 2(B) Molecular spectroscopy Ov nL: Choose the most corr rer 3O.degrees: 26. Tha IP of tH is 24 TOX10 MJ. The third IP OF PLE sel ae 217eaow bteormier —o1O8tTO ode 1B SOET 27 The If of any element can experimentally be detected using... sPSelram a. NMR be PES ce» Raman IR de Atomic 26 Aline of Balmer series has A= 487.6nm, to what value offm does it correspond, a 4 ba eT a2 29-The selection rules ef Atomic spectrascopy i= i co Aneany, Alett, 90.41, A5e0 4, am=0,i5=0 d-Aneany, Ol=4 Gma0,1, S364 30-Far elements having a configuration nsé, the allowed transition = a Aneany, Alt, bh be Ansany, 1S) Ps be So oP: e78e Py 2181 PS {i1-The ALSpeet. of elements having a configuration mst consists of two adjacent lines whieh is attributed to @ Zeeman Effect -c-np! exists in two states be ns! exists in two states effect af temp, 32-E), oft) and dem) of a photon of (h=200 9m) are, reapsctively a 9.94xtors, 1 2c10"1, dx10® ——&-1,-94n10H, 4 BLO, 2B KTOS be 9:94x10%, 25108, 9210" 9.94490, 4.541015, BIO 34:Electronic configuration of ground and excited states of GD are a (au )Xan")enk(om It (omPlent) 4on)4On") Aree) DIT be (onbant font 06") {OF Corea)! eT e (omp4ont) tan)": a} (aye) (6an)*U2 Pan Ue 240) (eu) Xere (om ICs") (ts) orw) Ore) +34. Tho relation botweea frequency 0 wavelength A and wave number fs Given BY {or Mfora" (B29) "(ms )A)AE soreg eel b-pacir*ed cu she for hed d-o'seus el 35-The expacted and real no of total IR bands of chioromethane are a30 bos © 27,10 10,92 36. The intonsity of light depends on avenergy of lightarea b- No, of photon/area ctype of tight d+ No, of photon x area: 7-The classification of light spectrum into certain light regions ie secording 12 a-energyot photons of light region _‘b-energy (evel of a material ‘¢-effeet of ight region photons on material de Inlensity of ight photons 38 The separation between successive MW spectral linesis 12.6 om’, the threa energy levels exist at a: 18.9, 25.2, 31 b-25.2, 37.8, 50.4.0m" © 6.3,18.9, 37.8 cm" 12.6 ,25.2, 37.8 cm’ ieP. 1,_ spectros: a- Compléte the followings: » Factors affecting the band position of IR spectra are - « Factors affecting the MW band intensity are .... leading The expected No of fundamental bands of COz is experimental No is... due to ... © Incase of IR spectra the raising of temp. leads to . MW it leads ta ...... The frequency of 1* & final lines of Lyman and Bracket series are The band intensity is defined as ..... and it depends on ... Beer-Lambert law is used to calculate and is given by .. Spectr. can differentiate between HCN and HOCI because... b-A solution of purine derivative (MW=586m/mol) of cone. 58.6 mg/l gave an absorbance of 1.014 with a light bath of 1cm. = Skeich the Jablonski diagram illustrating the possible transitions . What would be the transmittance of a 10 pM. 410 degrees ¢- The MW spectrum of IN ‘8Q consists of some lines appeared at 3.8, 7.6, 11.4 cm”. What is the position of the next three lines? Calculate the bond length. If the bond strength is 764 N, calculate the IR band position. 45 degrees: _ while in case of Se 8: 96 C 3 2% ” "Helwan Univesity 2,5 ek year * Seience Faculty 3h F i Jan 2014 Chemistry Department (Physical Chemistry 1 Three hr: . Mol. spectroscopy BS degrees The Band intensity 0’ ‘spectra is affected by .... fe “S31, The expected No of Bintdamental bands of CHF: is O.adhile the gapeiments a Csi = the followings fics For{fR) spectra the tye Gidepends on ..-.While the No of bands depends on w+ ae wr -. due 10 is... duetn.,, = D4. The MW can be used to differentiate between teil and 'HYTC! while IR, ene can't duet... “D'S. Incase of IR spectra at high temp. leeds to .... while in case of(t}¥ it leads’. G. The frequency of the first line of Lyman and Bracket series are... and... 7. The electronic (nes a ‘of ground and excited states of "x are....and ..., wave, No of the ad is calculated as . + * “ erive a relation to calculate the band position of the MW speatra if. = State which of the following are allowed or forbidden, explain. ~ hes(rigid) + Jy -a(nionr wigid) "=U ~afharmonic) + oe - Uj—: (unhannonic) -(n=2 J=1) 4 (n=5,1=3) ue ee fee hear. Ss = F Fre tR spectrum of ' yg “SC consiste of three Tines appear at 1233.8 8 (fundamemtal}, 249 cm". Calculate the IR band position of the oi , Zero point energy and the b = wt eoolga tey Fan 2013 Farta y ‘Time: Stirs. ‘ : Mol. Sassteoseopy &eorrosion . olecular spectroscopy 1. Give reasons for the following [five only) ' « (33 degrees) a. The temperature hiss no effect on the IR spectra (harmonic) but has an effect o7 the unharmonic cass. b, The MIV and UV spectra of diatomic molecules consist of many lines while that of IR consists of only one line. hoa 50, and COs give different IR spectra, no of bands and their positions. «. d. MW and IR can differentiate between the CH4 and HF | t, i . The lines of the MW have different intensities i ‘The band position of the uv bands depend on the material, 2. Which of the following transitions are allewed; (explain) _ a Jssls Ip-els Idols 3d—-3p ~ (‘Hatomic spectra) b dd—ds Sd Bos Sd2p (IAL atomic spectra) ee Tyla Tala Jacl Iain (4 WofCHyF, nigid) & pelooe?) p=|oe=3 pStove2 oetoos | (snharipontc) i 3- The IR spectrum of CO consists of some lines, the first two of them appear at 2050 and 4960 cm’! at 300°, Cefeulate the wavelength of the new band appears st SO0°K. ' ‘ 4- Compare between the following (two any): 2. MW spectra of HF, rigid acd nonrigid. b+ IR spectra of HF, harmoni¢ and enharmonic. c- Naatomie spectra in sbsence in presence of magnetic fieldMolecular Spectroscopy (70 _noints Answer the follow! westions Question 1 (20 points) - | 3Viat are the possible Voe appearance of a’new TR line is “The splitting of ER. and UV. Sgt “fhe polar Gomposndsared& and MW aoe re | = ‘ liii- Derive the tetursymbol of Li and. “B, aad a thi ciectronie spectre & iE Smastion 2 (25 points) \> Explain the factors contribute tw the broadening of UV lines such element- . lig What is the relalive rotational population NulNy of HCE, p=L.67Sa" lai Wika is meant by selection rules? --The # values for HCN and DCN are 1- 4 and 1.24 cm", respectively. Cateulate the Cand C-N bond lengths Y \ tion 3125 i ae a ‘igs pois’ expression of Aeyy (nou-rigid) syrmmettic top, knowing sat | qhe energy level expression is tax =BIG+E) +A “By? D, FU +1)" - Dx JQ+0)K? - Dy KY ié- TI rational canstants for methyl Muoride molecule are B= 0.85, Dy=2xE0" ant SEES Te Liye = LSx10°, calculate (he rota athumatfrequectiesdn suse of J-1,2 andl 3 F al, 2am tare the warelonig? Fike a ; ‘of the “irst and final lines in Balmer sertes of H ator dy- Which of the fulla wing are forbidden and w correct the forbidden ones’ hare allowed transtions , ciarmanic) i> 7pFaculty of Science Department: Chemistry acu of a ‘i a year chem Mol. Speeteascupy aad earrasint nates First semester: Jan 201! , Lecturers: Prof GAMAL Ei-Mabdy and Dr Adel Anmed j- Choose the correc! answer : (45 degree) F : 1- The incident mw photon will increase . 7 molecular rotational velocity” c! electronic potainnal velocity: a; "h. molecular vibrational velocity © d+ electrons in higher levels 4 2- According to the Born-€ Oppenheimer approximation ai nS a 648 c f&eG,+ 6+ 4. b § ¢ 8 -8+&+8 3- The eneroy of X-ray photons are equivalent to the energy of : a . a- Waleoce electrons c- ionization energy . + ' b- excitation energy (AF imoer electrons | BS oad, r — a4 yk broadeui a IR spectca + more effective in case of _AC UN spectra of gaseous of liquid states? ' b- ‘NMR sone Ge ig aes d- UV of solid-state j Because tinhtning : ie Later meinen 2 ; e 5. SOzis an active in MW while COris hat because i a- SOz is tingar while CO,is oot c+ CO; is linear while 8Ouis, not” f MSO; zolates while © d- SO, absorbs energy y while CO; it Beemer bk be HGtdeh Seewms " y kt a o- ‘ee of (RB spectral lines is propertiaaal to. f ~ Number of molecules Number of degenerate sthtes os (a) and d- pboton coergy 4 The term RIGID molecules means that they eae rotate h- rlon't vibrate vibrate and rotate d-(a) and (>) ae% The mounent of inertia of a trigiomic molecule ABC Is given by 41- MW or IR tan differentiate between HCl and HF because the two ‘molecules’! eae di ¢ Have different electronic levels a be Are polar compounds ah Atomic UV and Raman c- Molecular UV and vibMtian be Molestlec Stead Raman, _.G- Molecular UV and 19¢¢tion 5 ; , r ier ids it: = 22- The relation between the frequency of the incident (u) and the |“: thoy scattered photans (ug) is — a- WROTE, bo vsvot Eh c usugiAEh d- Yoru AEA ts 3, = 23- The energy of cnt male of photons of 2=10nm (om=10'cm) equals -Es 3 kd/mel c a-_E= he/10 kJfmol c- Es Nhe/i0 “EE Es Nbe/10 kI/mol d- E= ne k/mal ~ Because. . 54. The relation oetween the transmittance 4 2§-The allowed Lvalues for pw, ¥ given by L- ‘0 electrons (O)=1,0 2=2) Ian atom is iB ration: 1s” 3s* 2p? is a- Is* 2s? 2p! Ss" e- 1s? 2s" ap" 3a? | es | b- 1s? 9s? 3p! 2d! x \ dts? 3s?7-29) aq? a % Because... 4 at \ i t 4 28- Into how many levels will a "Dy slate will split ina magnetic elu” a- 3 b- 7 a 5 , Because ... t > The excited states for an atom of the ground state ng are *?, Py bP 'S: ce "Py Py Fe ds * Gecause... Fs, Pe 30- How many normal modes af vibrations are there for (a) $0; {bj HG, (e) Nz and (d) CO,, respectively a 3,603 it Sa TT I a - #3 |; 1. Doppler Effect and colli Pepi tet and collins are facir ead 4o degrees ad intensity ¢. trancd hroadeniag ds had ceergy 2+ The width of UV band of | J brozene in th p Sharper than b-more bred shew neh EINE Es vsscasue dpa tate, lower inenergy tham d-asme intensity ws 3+ In order of increas ing en a+ different electron tray fee 4> Slit is the part of the spectruphatemeter that ued to a- change i, of Incident light (change intensity of Incident light Jf change the polychromatic fight to monochromatic d+ permit only pawage of certaia) of incident light S Moment of inertia of 3 molecule by given by a Tempel tage Xe be Done? eo deme 6 The expression of rotation energy feeb (lr euprened a aa ee serene be Be scl ritual oe Ped hs a! J+ The population state ratio Sia of Mean ar Mink, fe a 3.82 Ie 35 ett The 6 of the transition aor "eher wats Joon, Matiseam®, 10,00 tv eae! it Po be Th «a de de gg. In presence of electric ficld, the 8” SOW fice is oplet bate... ¢menpaansents at pois eo att biting, i tented to TN Teldt round vaies oo reniveal ol degemeracy a-electeic field generates new 6 bnew evcitel stales are gearrateal he Stark effect 11-Seleetion rules of Haman rutal eon spectra are be afend, pebarity de Meet, polarsty ‘ tras beat [2-K and Na atom lh Hue nanne what "Sys bat Ms «pe ran eoigersio8 diferent ge. state comtipuralyms TT uttenent atm weight ab they cothey've differ spin configuration [2-The expected pa of total IR bands ef chaburameetae eo a-77 be te 3 [4 While experimental ne cof ine OBR baal Fee due Bett eee coed liibar nes same MOS'S-Normal MW ond Raman MW speetrascopy differ in ‘ t Selection rules, Ni af peaks, position af peaks Solection rules, intensity, peak position & Intensity, No of peaks, peak position a- Scleetion rules, No of peaks, effet of temp. 16-Anti-Stock lines result when moteenle wavenutalier side. energy from photon and appear at... pi Loses, high be loses, low c-gains, high d- gains, low Te The Pr rene of Vil-Rot, Spectr, appears at.... wavenumber side and its eqn. fs... How, statins 1-39) be high, o'92ltm + (1-22) A low, ot on t-2y) «28m ibhigh, o'= oo{1-2x) 20m 18-In wave curve, the distance between any two polnts of the same phase is known as a- hand length te 2H © wave member JE Wavetengtts 19-The intensity af transmi AE No. of phrtomelar b- energy of light/ares = No. of active molecules in cell d- No. of phofon*area 20- Jablonski Diagram represents ne The relation between vib, Quant, No and boned length b- The various electron exeitat at The different types of transitions within MO levels i The dependeare of bond length and potential energy 21+ Morse curve deseribing the f diatomic mafecate at The dependence pf hond length and potential energy be The relation hetween ib, Quast, Ne and bond length ce the variation bored tempeh and attraction energy de the relation between attraction and repulsion forces of os excited stare cwnfiguration of Q2 malecate lx Isa!sa'*2ee 200/22 toatisa a an a The grown ae ae Lent hsa ?200?2en2per 2p 73 be Lents’? 2s0%256"23pe tyu paps 2p 2po" Pisa"! dea Jpn’ 2p 2p Iso" ae i ce bent hsa!2s0"2s pa? aml ent fsa?bso!2s0 Spada 2pe and lambs 1 Qpaipes apr 2pm ‘. aa eta net ay a ee Q]- The wavenumber (0°) of the AT spectral fine of element Nis given ae JR [NIG -125] ee nye ae be 22'R [16 1/25) de #RE a= The 1" AT spectral line af the outer electron of element aX fs splitting in Mie a is “i rr 26 Theto'poFAT spectral linecofsX aed a! wy torte ie i a AT congue i 7 Reduced mass and raddies \- F ¥ ‘The traneiaiel Intensity of light 25601 pat 05 stn ee mt a ‘of its initial value, Calculate its alworbanee and ext\ = O03, beng be 160, 6 0.03, 160 A 16 and 168) arramgement (CH)> (CHF o(CC> (CBr) ls attributed to & PCH a (FC a CIC} (Ce) be band polarity - N(CH RPO RCI} & (Cin) # a (Cll) pF < (CIC) a (CMe) US-The difference between Neoreseence and phosphorescence sj is Phosa pectra & the behavior of electron ‘ple dering eniisiog be change ia wavelength femergy of the emitted photon d-energy of the emitted photon 29 The i of the elite ul fheorescence photon fv longer than the initial abworbed because af « Different grou eof he Ie pirecesven e-alnglet- triplet spin change & WMeating emisnkon during Muarescenee d-vibration of bands Me Aecteoscopy by wed th itterentinte between "O-"O and Me. "o u o- Mal UV Me Rana MW MW d= Photon electron AD-The vibration freq. amd rotation FTN are 4120 ond fo") OF the 1" spectral lines of If ranches are 8-40, 60 cn” JF A100, A200 con 4190, 4070 cm" by eRe aie a “The wavenumber de 4070, 4130 emt 32-The I) of the 2p’ etect » PRR Ja-Electronic spect, ix mot suitable to differentiate behween “Ca-"O and “Ca-"'O doc te 9 Differ in AT mass, and J quantam Ne h. Differ is isotope man, amd r & Differ jn reduced mass, ancl J quantum No tame electrasie configuration “MW spect, is med tn lifferentiste betmeek OC! aad “Cg gy durte ® Differin AT mass, and J quuntam b+ Ditfer (a AT manes, bond length # Differ ia reduced mar, and J quantum No ol Differ in hotope man, and ¢ AS For "C0 at 300K, IF At) 1000 cen anid 1470.02, The hot band appears at Ae 188 cnt be HOT eistiem" d= 1090 emt J6-The right MW spectra] lines approe af 12 6, 25.2, 7.8 cm’ nerigid MW apectral Ines ral - 32, she em! Af IDS, 1A, 316m © 116, 253, 179 em! 4-125, 18.2, 38.8 em 37. TR differentiates between Mh, CM, and ¢; HO; beenuse of a Thelr different Mirwctare 28. Difference in No of peaks aed band potion & Different fanctlon groupe de Different Reduced marsuee and Pond eirengrhsy ' pe aa etey B- Molecular spectroscopy \~ An aqueous solution of toluene derivative (MTW=247pm/moal) of cone. 9.7 mg/L gave an absorbance of 1,-1.4 with alight bath of Vemand A=14- om. -What would be the transmittance of a }+ pM. ~The UV. band of benzene does not equal T4-nm, why? -Explain why both molecules have different IR spectra , 7. What are ALL the possible types of apectra for cach of the following compounds, Hr, Mg, HCI, CO:, CHi, CH-CI? Explain your results ' T. [n the MW spectrum of '"C''O, the separation Balen the lines has been measured to be 19% MHz, Caleulate the position of the first two lines of “"c' OQ. What is the relative population of the first two levels of "CO at room temp? Explain: what happen when the temp. increases and when a magnetic field is applied. ~ Estimate the electronic spectrum for each of the following elements: "X and "Y, in presence and in absence of magnetic Field (T° degrees)- Complete the followings: 30 degrees . Colki lai igggyand idered ax the main factor f sian explains the wrare considerta ay thi in case oS Ww 2. Stark effect'explains ...sgu fag off spleflee heey 3. IR spectrum of HCN differs than that of HOC! compound i.) and? becaw: 4 4 dgatheets P= oa 4 cps ate = g 2 4. The term symbol of the electronic provid and oxcited States of "NX metal are so the No of its atomic spectral peaks is 4», Un the presence of mignetic £7 NOG, because 9 74 fh re «ee taifet siete 5. For IR spectra the dou siden apie 6. The band intensity of MW spectra is affected 5 The expected No of fundamental bands of CH is. 2 due to2tsenete tl lis i i : MW ce Sand ‘HUG! while 1% a : ‘s . Sea 5. In cuse of IR spectra high temp. leads to J... while in cage of MW itleads to # a 10. The value of fréquency of the first line of Lyman and Bracket scrica.ase and IL The fundamental [R bard shows some vibrations which is artribated to The pure MW spectrum of 1H] consists of a series of lines separated by 0.34sx “What is the value of J in the mast populated state? Predict the bond length - What happen-‘when the spectrum is carried out in the presence of electric field? 2 i Ot Cot tee eat ae 2+ a- Derive an expression for the P and Q branches frequencies. 2idegree b- The first four vibrational 3917.44, 6398.94 and 877 enerpy and equilibrium vibration frequency swere found to be lie al 1231.84, jores-cunstant, the exact zero. Borat f i i oumvnel) of tone. 58,6 malt an absorbance of 1.014 with & light Bath of [ein nd §=280nm As-tgT S| - -What would be the trangmittance of a 10 phy » “The UV band of benzene does not equal 280nim, why? (yr ~ Explain why both mofecules have differait IR snecusy, 3+ a- An aqueous solution of toluene derivative (MMeme Department No a- Complete WINS! ht . i- The rigid case means 9 Y= SS" ,, while the non-rigid means Energetically, they differ in ....f-£" while the differences in their spectra are... ¢ TA aT e used to differentiate between two unknown compound 5 sutilferat Mati mhrahebsh,. boreal ithe oie rae, hibrenvic sh te while for Lo onudee ed if t ! a nd and excited states of Al metal are... I vt peaks is 9). In the prescience of magneti sy perpen s Re Egat ty - iS aapeae 1 : ‘ ‘ 3 vetu 5. Two differences between atomic and PES specira are .. ue of teed < * eush > enw a mat, 5 6- Factors affecting the band position a pectra are..." .... leading Lo .f% Sfok Po _. leading (0 ymes ye Yn 8-The tay photons are used in case of atomic spectra while in case of rotatic spectra the MLM, photons are used due eertatilcg warts Pmerng diy bs we anh 7- Factors affecting the MW band intensity of spectra ae i 9- The frequency of the first line of Lyman and Bracket series can be calculated usir the relations... where oT Ay are fy! peat dee PY Behe Wis 8lA ma of P CL ba 10- State which of the following are allowed or forbidden, explain. ~~ Jz j(rigid) < Tyay(nonrigid. er é (n=? l=l)— (m=5,1=3) ed if b- The MOWipectnaga of 'N "0 consists of some linies the first one appears at 3.Bcut Stete qualitatively and explain what happen when; . i- The spectrum is carried outat higher temp. varet Be pnd Self tis The spectrum is carried aut in the presence of electric field site@4 > Mi i+ The spectrum is carvied out for !'N !¢y Chew ~ bend P esi él