Indian Institute of Technology Roorkee =| & DEPARTMENT OF CHEMISTRY CY-101 Chemistry, B. Tech. 1" Year 2006-2007 Autumn Semester * Tutorial No. 1 Maximum Marks: 30 Answer all questions 1. [TiGH20).]Ch is violet in color, however TICI is white. Explain Gmar Ans: Ti? is 3d! ion. In ITH2O)6ICh there are six water molecules in a octahedral Configuration is: tg' 4°. A single absorption peak is possible for this complex corresponding {0 the tag? ey! & tap! transition (and 4 = 20,300 cm"). (2 marks). However, in TiCl; the d- orbitals are degenerate (no splitting) due to the lack of coordination sphere, and no d-d transition is possible (1 mark). | Briefly, in (Ti(E2O)ICl, presence of octahedral hhexaquo ligand field splits the d-orbitas Gegeneracy is lost). So a d-d transition is Possible. However in TiCl; there is no octahedral ~~ ligand field present, 2. Pt prefers octahedral coordination while P2* mostly adopts square planar geometry. Why? (3 mark: Ans: Pt** is a dion, d-orbital diagram is tzp®, The CFSEye is: -2.4 ‘Ao While the CFSE,» is -2.24 o The preference energy for octahedron coordination (OSPE) (compared to square planar Coordination) is -0.16 Ay. Because of this Pt!* Prefers octahedral environment, PO's ad® ion, CFSE =-1.2 A, CFSEy = -2.44 Ay, Notice that in this case, the crystal field Stabilization (in terms of A.) is much greater for square planar coordination than for octahedral coordination! In fact, the preference energy (compared to octahedral coordination) for square Planar coordination of a d* metal ion is -1.24 A,. So PE prefers ‘Square planar geometry, Te both (Pt & P2*) the answers are Correct award three marks. If one answer is correct give only one mark. 3. Explain why the complex [Co(CN).}* is diamagnetic whereas [Co(F).]* is paramagnetic? (2 marks) Ans: Co” is a 3d ion, Electronic configuration of the free ion is: wlll | | { { { I ICO(CN)e]*, CN’ isa strong field ligand and so o> P. This results in the configuration, el CO} No unpaired electrons. So {Co(CN),}*, is= diamagnetic, (1 mark) However, in [CoF,]*, F” isa week field ligand, so 4, COOH > CHy> H; absolute configuration is “R”. (1 mark) B: Priority: NH? > COOH > CH;> H; absolute configuration “S* (1 mark) 8. Which of the following statements are trué? (Write "trine” or "false", as applicable.) Gmaa. Fischer projection always displays the same molecule after its rotation in the plane of - projection by 90°. (false, 90° rotation leads to its enantiomer) (1 mark) b. All compounds which have carbon atom with four different ligands are chiral. (false, because meso compounds which are achiral have chiral carbon atoms) (1 mark) ¢. Molecules which are nonsuperimposable mirror images of each other are always enantiomers, (true, by definition of enantiomer) (1 mark) 9. Assign R/S configurations for the following Fischer projections? (1 mark) ee CHICHa), sa Hyco CH;CHs # cHO NG _ , Priority: OCHs > CHO > CH(CHs)2> CH2CHs; absolute configuration is “R”. (0.5 mark) 10. Indicate the relationship (enantiomer/diastereomer/identical) between the structures in each (3 marks) Priority: Br> COOH > Phenyl> cyclohexyl; absolute configuration is “S", (0.5 mark) pair given below. H CH 4 Ke me ean por a COOH COOH Br cl Identical (1 mark) Identical (1 marke) CN iN 3) oe & a 'H Hi HOH,C’ ‘CHZOH ‘CHO OHG Enantiomers (1 mark)o- vx Department of Chemistry Indian Institute of Technology Roorkee BTech 1 Year, CY-101 Chemistry 2010 Autumn Semester Tutorial No. | Maximum Marks: 30 Physical Chemistry, L @ >) @ @) Tf Wx) = ¢ sin (m/a) + d sin (27x/a) for a particular system, find out whether (2 marks) (x) is an eigen function of Hamiltonian operator and write down the eigen value. Assume that the potential energy is zero. Answer: To find out whether y(x) is an eigen function of the Hamiltonian operator, the ‘operator has to be applied to the function, i. [-h? / 2m)d"/dx"] (x) = - (h? / 2m)d?/dx? [¢ sin (ax/a) + d sin (220/a)) e = t'x2/ 2ma? [e sin (rea) + 4d sin (2m/a)] (1 Mark) ‘The result of the operation is not y(x) multiplied by a constant. Hence (x) is not ‘an eigen function of the Hamiltonian operator. Since y(x) is not an eigen function, we cannot mention its eigen value. (1 Marke) Evaluate the commutator,[2, f,]. (1 mark) Answer: Py= (hA)[dsdy) [2.6y]=[28, -2,2] (12 mark) Let us assume a function f Rbyf — By®f = 0 ‘The commutator = 0 (2 Mark) If yx) = N a (a —x) over the interval 0 =fy'A wdt = (1/2 Mark)‘An operator A is Hermitian if the following condition is satisfied: yA y ac= fy(ayear (or) Sud ye dt= dys" widt)* (V2 Marky 3. When an electron confined ina one dimensional box of length 2A and in certain excited (4 marks) energy level makes a radiative transition to the ground state, a photon of 2= 8.79 nm is emitted. Find out the quantum number of the excited state. Also, what will be the zero point energy of the electron? Answer: AE= (02-01) b?/ mF? 79 nm = 1137656.4 em = 141.1 eV = 2.2597 x 10° 3 (1 mark) Since the electron falls from an excited state to the ground state, n) = find out the value of m. (02 =n)? / 8m? and we have to (ng? — 1) [ (6.62 x 1077/8 x9.1 x 10°'x (2x 10" ] (1 Mark) . 2.2597 x 10" J = (nz*— 1) 1.5049 x 10" (ny ~1)= 15 ny =15+1=16 m=4 (1 Mark) ‘The zero point energy corresponds to that of n BP / 8maP = 1.5049 x 10° J = 1.5049 x 10" J/ 1.602 x 10" J =9.39 ev of 75735 em" or 132.nm (1 mark) (cut % mark for arithmetic error, iffany) I emis 4. (@) Show the erystal field splitting for hexaaquairon(II1) and calculate its CFSE. (1 mark) Angwer: Hexaaque iron(II) is an octahedral complex with HO as a weak ligand. Fe" = dP eystom [Fe(tOyel tet i, CFSE =0 Siontmatase (1/2 mark for diagram and 1/2 mark for (CFSE; full mark only ifthe diagram is correct) (b) Inthe case of (Cr(#0).]** ion, the magnitude of A, and the mean pairing energy (3 marks) @) is found 13,900 cm” and 23,500 cm", respectively. Calculate the CFSE fey this ion corresponding to high spin and low spin state. Which state is more stable? Answer:‘Complex ion Cr is present as Cr’? ion which is a d* ion. For a d* ion in a high spin state, CFSE =-0.6 Ay =-0.6 x 13,900 cm" =-8,340 cm" (1 mark) Fora d* ion in a low spin state, CFSE= -1.6 B+ P=-1.6 x 13,900 em! + 23,500 em = +1,260 om’ (1 mark) Since A. (=13900 cm)

P) and H,0 is weak field ligand (4, > P)(1 Mark). The soli grams are shown below. (1 Mark) Pe imnttsor (miner the Aaa 2. (TNE complex i violet in colar. IF is replace by every strung fie liguml will there he an change in evlor Explain your answer @ Wis a d! system where the transition is.t3" ,° to 1," e'(1 Mark). This corresponds to 10Dq and Ue color of the complex corresponds to transmitted light. Thus by replacing the ligand X by a sirong field ligand, Y, the value of 10Dq willbe increased, The complex will absorb radiation of shorter wave length (1 Mark). In other words. the complex will absorb in the ultraviolet region anal hence will appear colorless (1 Mark. 3 Dran te crystal field dagrant and explain the spinstate of the allowing compere. Go) {CoF.}” > Co(M}) a*-> High spin >t! e," (1 Mark) (b) [CoUNH:).]"—> Co(Itt) d*-> Low spin +t," e! (1 Mark) (c) [Fe(H:0).]" > Fe(lt) d°— High spin rts," e,! (1 Mark) ( [Fe(CNI]" > Fe( til) d'> Low spin 13, -e," (1 Mark) (For each splitting diagram, please give one mark each)(CoFa* (high spin) [Co(NH)a* (low spin) ts as 4t¢ +5 4 ft tL te [FetH0).)* IFe(cn)eP att + _ . 4+tte aon, Q4 Cri, Matty and Fett) are allowed 10 react with Cl under some specified conditions where [MCIap" thd = Cr, ht, Fe) wil be the sole product. Predict the possitity of formation of MCIf? in cach cuse. eo The answer is based on crystal field stabilization energy (CFSE). Cr(lII), Mn(Ill), and Fe(ttl) are 6°, a, and * systems, respectively. Being a weak-field ligand, the CFSE for [MCI] will be —12Dg ( oF 1.204) for d, — 6Dq (or ~0.6a,) for d* and Dg for din high spin octahedral splitting. So for Cr(II1), the possibility is the most and for Fe(II}, the possibility is the least. (11 Marks) ae aes Reg es ee ¢ ¢ ¢ (1% Marks) S. Hus the configuration changed in the esterification of (lactic avid with methanol to give ermelil lactate? Show the reaction using Fischer projection aml justife briefly (ste)There is no change in Mark) iguration a CH3OH ie —— coon = —— 5 HCl OH (Hectic acid 06. State Trae’ or ‘False cand justi briefly: a) A hos files with pairs of shies or left shen ‘one enantiomer only The :50 in number-racemic. Only (b) Meso eat be alternatively referred to us raceme False, (1 Mark) Racemic is a 50:50 mixture of the two inactive because the special arrangement is such that it provides 4 separate configuration. (1 Mark) image and thus represents 07 Arrange the following sets of groups in decreasing order of party (a) -CHO.-CN. ~C=CH, -COOH ~CUOH ~CHO=CN > -C=CH (b) ~COCHs. ~CH=NH. ~C,H,, -OCHs “OCH: > -COCH; > =CH=NH > -CyHy Q8. Point out which of the following are chiral. fa) Screw diver’ (by Screw (c) Helix eh Sho es Hand glove) Tree Screw (b), helix (©), shoe (dl). hand glove (@), wee QQ (Uf the answer is ‘chiral’ or ‘achiral? (-methy! lactate nes onl is comparable with racemic. a5 there is no breaking of bond atthe stereogenic centre. (1 H Hc + cOocH; OH (2 Marks) milytire and @ « Pair of shoes represent non-superimposable mirror imayes and being in left shoe is therefore like one enantiomer only, @ opposite configurations. Meso is a superimposable mirror 4s per sequence rules: a o a are chiral. for all questions do uot award partial marks) OP Structure of CHCIBTE is represented in diferem Fischer projection formulas. Relane rns a) ta ll the stewctares hoon tb) to (@) and fill up the H wk Cl by Br Following table as per 0 cumple ea °) ft cl 4 wf BrBr H a dat, *otne scsi i : F _ Sequence of groups ‘Number of Relationship S.No. interchanges Intercha j——werchanges | @) 4H, Br I(odd) Enantiomer © HF 1 (odd) Enantiomer * @ H,F; Br, Cl 2 (even) Same © HBr Cl, F 2 (even) Same 3) F,BGF,CI 2 (even) Same ® F,Br; Br, Cl; H, Cl 3 (edd) Enantiomer (For each correct answer, give one mark) O10. (a) Indicate whether the following functions are acceptable or not as state function in the intervals indicated. Indicate the reason, @ DEO, oii) sin" (1, 5), il) tan, 29), 4) cosec x (0, 2n) A. wrave function is also called state function since it desribes the state of a system. Por a function to be acceptable state Luuetion (wave function) it should be single valued, continuous and finite in the given intervals, 5) £2) Yes. Single valued continuous and finite (L Marl) » 1, 1D. No. The function is muti-valued. eg. sin" = w2, 92+ 2m, etc, (1 sine Mark) iii) tanx (0, 2m). No. tunx tends to infinity at x = 9/2 (1 Mark) iv) ‘eosec x (0, 2m). No. The function tends to infinity at x= 0(1 Mark) 0) 8 dite and O= oats «the commuator fo a function, fix) (2) Let d and € act upon the frneti- {). The commutator is 4C- C4, (1 Mark) AC Ale) = (dids) is} fia) = 2 5) + Pate C4) =O) us) y= Ce Zr Ah fo fat HC Re 1CA KIRA EE CH) HERES. 1 Mare) eo The commutator 2 tatee JI we C5 [dlak santo? : Renca Commurrioler le 2 7-11. Show that fs) ts an eigen function A the given operators. What are the eigen values? a IF A ftx) = (constant) x), then 104) is called an eigen function, ‘ tex) i (hia?) (cosca) =~ * c0s( ars) Thien wt is the eigen value. (1 Mark) & [aw oe u (did (2) = ja em Ade ies the eigen value. (1 Mark) i) idx +2 das ayes ven yaar Ate = ate tO didn em Cert se = 243) eH salem @ + 2.0+3)is the eigen value, (1 Marty ‘False’ fog the following st and explain oO fae 2 i. Sue Operator re nts kinetic. ‘energy plus Potential I to Engen ai Q il). No. Schrodinger equation, Hy = Ey, is an eigen value cauation. The Fiamiltohian operator corcns 2m the wave function and the end meses is, i. ‘same wave function oe a a fonstant E, the en Bao beBlean 2 wat Conrunud ). Yes. The | commutgtor a ae in Beak eyekia a eC oe Is qual to. reas a No. If A fe) +8) =A ve) Age, ov . mae wa pe oon Ree ane 0 at AO eee <— e in Com bog v). No. Probability density is always posite QI EYE) = A sintawade ft out tie vse FA assiing ¥6s) is mormaliced inthe lint, 019 4 @ We have to use the norrtization oandichion Oe Svc" veaie= 1. cr xtanny NT E— : shone. ell, lone TE) fe een G Merk ‘i RA oa A=(a)";DEPARTMENT OF CHEMISTRY Indian Institute of Technology Roorkee C¥-101 Chemistry, B.Tech 1" Year 2007-2008 Spring Semester Maximum Marks: 30 ‘Tutorial No.1 Ql. Give the number of unpaired electron(s) and spin only magnetic moments for the following complex ions: @) [Fe(CNF” 0) [VFeP” (e) (Rufenys*(@) TRACI 0) (02. What will be the color of MaCl?* ion? Explain your answer. a) 11), Mn(IU) and Fe(Iit) with _® 4. Show the erystal field splitting for hexaaqua iron(II} and calculate its CFSE, (1) Q3. Compare the stabilities of [MCI] where M = C; Proper explanation. QS. Find out the total number of ehiral centers in each of the fol state whether they are optically active or optically inactive @) (@) Lactic acid () — meso-Tartarie acid (©) 3-Methylpentan-3-o1 @ — CHD(MeoH) Q6. State “True” or “False” and justify your answer, @ Compounds having only one asymmetric carbon are always chiral. (©) Diastereomers are supetimposable mirror images, (©) D-Glyceraldehyde and d-plyceraldehyde are identical, lowing compounds and @ Q7. Assign R/S configuration and indicate the relationship (enantiomers ‘siastereomers identical /no relation) between the srmarnen given below. (2)Q8. Find out the commutator, [Ex.y).£, and Ly are given below and the function, fis a state function. @) L,=-ihly a/az ~ z lay) (2 d/Ox ~ x alaz) Q9. State “True” or “False” and explain your answer, 8) (a) Probability density is always positive (b) An acceptable wave function needs to be multi-valued at any point. (6) Orthogonal and normalized wave functions are the same Q10. What is a Hermitian operator? State whether the Hamiltonian operator is Hermitian or not? : ® QII. State clearly the difference (and similarity if any) between a wave function and an eigen function. @ QI2. Find the eigenvalues if the operator and wave functions are as follows. @ Operator Wave function @ Pidx? + (2/x)d/dx + 2x exp(-x), Plax + Ploy? + Flac (cosax)(cosby)(cosc2); a,b,c are constants.ca & call & ee DEPARTMENT OF CHEMISTRY SG Indian Institute of Technology Roorkee CY-101 Chemistry, B.Tech I* Year 2007-2008 Spring Semester Maximum Marks: 30 Tutorial No.1 OI. Give the number of unpaired electron(s) and spin only magnetic moments for the following complex ions: (a) [Fe(CN)e* 0b) [VFaP (c) [Rulen) P™ (A [RhCIa]™ @ : v Complexion | No. of unpaired ‘Spin only magnetic moment (Bohr @ electrons Magneton) [Fe(CN),) i 13 [IVFs 2 2.83 . [fRu(en)* 0 0.00 % [ERKCI)™ 2G ane 4. 9D (For each correct number of unparied electrons award ' mark; For each correct spin only magnetic moment award % mark) 2. What will be the color of MnCl," ion? Explain your answer, Q MnCl.* will be colorless or very faint color. (1/2 Mark) Explanation: MnCl.” is a tetrahedral complex with Mn possessing ® configuration, Since CI” is weak ligand, the teirahedral crystal field splitting would lead to 12e* configuration. Mn* = d? system 4+. +4 ‘The d-d transitions in this complex are Laporte forbidden (A= 0 for a d-d transition) and spin- forbidden. The transitions will be very weak. Hence the complex will be either colorless or faintly colored. (I 4 Marks) Q3. Compare the stabilities of [MClq]"" where M = ‘Cr(HII), Mn(11l) and Fe(Iil) with ‘proper explanation. @ [CrCle]* : @ electronic configuration with CFSE =~ 12 Dq [MnCl.}*: d* electronic configuration with CFSE =- 6 Dq [FeCl,}”: a electronic configuration with CFSE = 0 Dq (2 Marks) Based on CFSE values, the stability order is [CrClg]”” > [MnCl] > [FeCl,}* (1 Mark)04. Show the crystal field splitting for hexaaqua iron(I) and calculate ts CFSE, (1) Hexaaqua iron(II isan octahedral complex with H,0 as a weak ligand. Fe" =o system [Fe(H20)a)"* 4 + = CFSE =0 tHte 5. Find out the total mumber of chiral centers in each of the following compéunds and’ * Slate whether they are optically active or optically inactive. a a Lactic acid b. meso-Tartaric acid ©. 3-Methylpentan-3-ol d. CHD(Me)(OH) a) @ 6 on weProoon A : waebou Lactic acid meso-Tartaric acid 3-Methylpentan-3-01_ HD(MeXOH) Ichiral center 2chiralcenters no chiral centers 1 chiral center optically active optically inactive optically inactive optically active + (Structure is not needed. Number ‘Of chiral centers: 4 mark ‘each; optically activeoptically inactive: % mark each). Q6. State “True” or “False” and justify your answer, (0) (@) Compounds having only one asymmetric carbon are always chiral (©) __Diastereomers are superimposable mirror images. (©) D-Gilyceraldehyde and d-glyceraldchyde are identical, (@ Exchange of any two groups in the Fischer projection doesn’t change its configuration. [96 [TF | Justification ZS © Molecule with one asymmetric earbon will have non-superimposable (@)_| True | mirror image: hence itis chiral, (b)_| False _{ Diastereomers are not mirror images. (c)_| True_|D-Glyceraldehyde exhibits (¥)-rotation; hence tis d-enantiomer (a) | Fatse | Exchange of any two groups in the Fischer projection provides its enantiomer, (j.e., configuration is changed).> (True/False statement: % mark each; Justification: % mark each; Any other relevant Justification may be awarded marks). QI. Assign R/S configuration and indicate the relationship (enantiomers/diastereomers/ identical /no relation) between the structures given below. Q A: (8), B: (S)\(4 mark each) i A and B are identical. (/ mark) % — trueture A is in 3-D representation and structure B is in Fischer projection) 98. Find ou the commutator, (by). Lana f, are given below and the function, fis a state function. @ Ly = thly Fee 2 2B) f= ihe 2a -x Fa) The commutator (I£5] is Paty -2yly. This can be found out by evaluating he following. LLf Bie Lf=Cih/2n)[z Otf0x x af/02) CLE nes ‘az. zo Gilv2n)[z Offéx ~ x affaz] + yz PHlexdz — xy P02 ~ 2 FHfayax + xz Ployor) a> (A) /2n)[z Gx — x Gz] (—itv/2n)Ly atfee—z otvey) Hlda) [yz PHOxo2 — 7? BOxdy - xy PHO? + + xz PHfO20y)......>(B) (A) ~(B) = -H7/4r2 y offex + W/4z? x flay ; Fis a state function. Ee GhUaW (y O1Gx — x offey) ie Lr Cif= (if, Ligaen y atta x effay) TA, -B haa G0 lox —x 09) oF Gin’2n) Lg b= —itvon (Kay ~y alex)Q9. State “True” or “False” and explain your answer. @ (@) Probability density is always positive. True; the probability density is given by, le? = ¥ if is real. IF Y is complex, then the Probability density is equal to ¥*Y, (©) An acceptable wave function needs to be multi-valued at any point. False; According to the postulates of quantum mechanics, an acceptable wavefunction must be single valued, finite and continuous. (¢) Orthogonal and normalized wave functions are the same. False; If two wave functions, ‘Y, and 'f, are orthogonal if {YY (or fa" dz) = 0. They are normalized, if fewar=1. 210. What is a Hermitian operator? State whether the Hamiltonian operator is Hermitian or not? a. @ ‘An operator (A) is called Hermitian operator ifthe following condition is satisfied SesAmar = fy, Aye (12 Mary a ‘The Hamiltonian operator is Hermitian (1/2 Mark) QUI. State clearly the difference (and similarity if any) between a wave function and an eigen function @ Difference: ‘A wave function need not be an cigen function. A wave function is an eigen function if AY =E'; A is an operator and E is the eigen value. (1 Mark) Similarity: Any eigen function is @ wave function but not vice-versa. (1 Mark) 012. Find the eigenvalues if the operator and wave functions are as follows. @ Operator Wave fnction OQ bldbe + Q)dide + Ix exp(-x) Gi) Fab + Bap + Oa? (cosax)(cosby)(coscz); a,b,c are constants. (@ (Cx? + (2hxydldx + 2x J exp-x) = [dx] exp(-x) + [(2/x)d/dx] exp(—x) + 2x exp(-x) = dldx (-1) exp(-x) + 2/x (-1) expl—x) + 2h exp(x) exp(-x) Eigen value = 1 (1 Mark) (ii) (Plex? + Pray? + Faz] (cosax(cosby\(coscz) = F10x* [(cosax)(cosby)(coscz)] + Bay? [(cosax\(cosby)(coscz)] + #1é2 U(cosax)(cosby)(cascz)} = 2" [(cosax)(casby\(coscz)] + b* [(cosax\(cosby)(cascz)] + [(cosaxXcosby)(cosez)] @ +b +c!) {(cosax)(casbyXcoscz)] Eigen value=(a°+b'+c*) (1 Mark)Minor Corrections in CY-101-Tutorial-1 QL. Give the number of unpaired electrons) and spin only magnetic moments for the Jollowing complex ions: (@) [Be(CN)a}™ (b) (VFef (e) (Ruten)sy* ©) [RhCL @ Award full marks for the following answer also. Complexion [~ No. of unpaired Spin only magnetic moment (Bohr electrons Magneton) [hci 4 i 4.90 Q9. State “True” (a) Probat 1 “False” and explain your answer. @ density is always positive. If the answer is False, full marks may be awarded if the student has, written that the Probability density can also be equal to zero, : 12. Find the eigenvalues ifthe operator and wave fanctions are as follows, 7) Operator Wave DQ Bid? + Qtx)dide + Ie exp(-*). fii) 168 + 2B) + G1ae (cosax)(cosby) (coscz); a.b,c are constants, i) The correct answer is Eigen value =~ (a? +b? +c) Q mr Me@) DEPARTMENT OF CHEMISTRY Indian Institute of Technology Roorkee CY-101 Chemistry, B.Tech I* Year 2008-2009 Autumn Semester Maximum Mar! torial No.1 Ly Q4. Draw the spliting energy diagram of d-orbials and predic the ‘erystal field stabilization ‘energy (CFSE) in the following complexes: (24242) @ treemng Gy orem) manatee . At. 2 wy (ctahedral C.F.) (Crystal field splitting diag. of five d-orbitals in () weak and (il) strong field tigands (diag. drawn not to scale). (units: 10Dq = A, 0.4 A,= 2/5 A, 08 As= 315 A.) (2) Mion (Fe*) is a d*-system. Since, CN" is a strong ligand (Le., itforms LS-complex) Therefore, the electronic configuration is te’ @,°. CFSE = [-0.4x 6406 x 0] A, + mP =- 24 Ay + mP = - 2.4 A. + 3P. (where, m’- number of Paired electrons) (Diag. (ii) Is correct) (b) M™-ion (Cr) is a d*-system. Since, CN" is a strong ligand (Le,, it forms LS-compley). Therefore, the electronic configuration is tay! @,° CFSE =[-0.4x 4406 x 0] A, + mP =~ 18 Ae + mP = - 1.6 A, +P.” (where, m'- umber of paired electrons) (Diag. (ii) is correct (c) Mion (Mn) is a d®.system. Since, H,0 is a weak ligand (ve. it forms Hs- SOmplex), Therefore, the electronic configuration is t,? ey’ CFSE = [-0.4 x 3 + 0.6 x 2] Ao=0 A, (Diag. (i) is correct). (Marks distribution- 1 for diag. & 1 for correct explanation, {fpairing energy is not included award % for each) @2 Draw and explain why d-orbitals experience diferent ligand field effects and split into two degenerate "groups tx and! ¢, in octahedral caordination compounds? Whe will be the ligand effect on outermost s- and p-orbitals? +)‘A2. The ligands approaching to the metal ion have different electrostatic interactions with d-orbitals, For example, axial orbitals (d,2-,2 & d,2 shown below) experience the greater repulsion as compared to non axial orbitals (d,,, d,, and d,. shown below) due to their presence in the path of the approaching ligands. Therefore, d,2-,2 and d,2 orbitals acquire higher energy level (0.6 times) from the barycenter. Conversely, non axials orbitals are directed in space between the path of the approaching ligands and experience less electrostatic repulsion from approaching ligands, resulting in lowering of energy level (0.4 times) from the barycenter. By convention, the axial orbitals (02,7 & 4) are known as the ey orbitals and the non axial orbitals (dy, dye & dy.) known as the te, orbitals in an octahedral complex. (Diagram as in Q1.) Due to spherical shape of s-orbitals, the outermost s-orbital experience same electrostatic interaction from the approaching ligands. However, its energy is increased in the hypothetical state and remains degenerate in all ligand fields. Similarly, p, py and P; orbitals are axially oriented. The ligands approaching to the metal ion have same electrostatic interaction with all axial orbitals. Therefore, the orbitals are raised in energy and remain degenerate. My (Spatial arrangement of the five d-orbitals) (Marks distribution- 1 for diag. & 2 for correct explanation) 03. Explain why the crystal field stabilization energy (CFSE) of [Co(H;O)q)"' is larger than [Co(Hy)ef"'? @ 3. A metal ion in higher oxidation state attracts ligands closer than its low oxidation states due to increasing nuclear charge and poor shielding, resulting in larger splitting and hence high crystal field stabilization energy (CFSE). e.g., In [Co(H.O)é[", cobalt has +3 oxidation state while in [Co(H:0):]”, +2 oxidation state. Therefore, [Co(H,0).)** gives higher CFSE than [Co(H,0)<]”". Q4. Complexes with d-electronic configuration prefer to give high spin (HS) coordination compounds. Give reason with an example @Correct O4. Complexes with d-clectronic configuration in moderate to weak ligand fields prefer 10 give high spin (HS) coordination compounds. Give reason with an example. (Note: 1 mark for this question is adjusted in Q2). Q5. Which of the following molecules are chiraachiral: Q @ —— CHpCHp-CHyCH(OH)-CH, (i) HO-CH-CH(OH)-CH;-OH amy ancts 2 oH 1 (iv) HyC-CH;-C(CH)(CD;CHy)-C(CHy)s AS. (i), (il) and (iv) are chiral 26. Draw Fischer projections for the following; a (@) — CHYCI)-CHYCY ()) — HO-CHyCH(OH)-CHO (©) (H\C)CH-CH(Br)-CH-CHy AS. (i) No chiral carbon so no Fischer projections. (erc#—|—enyons ong HEC I l Q7.Which ofthe following are (i) identical (i) pairs of enantiomers or diastereomers? (2) 4 CH on—[-1 w AT.| -are identical @ & (¥)-enantiomeric pair Q8. Assign R/S configurations for the following Fischer projections: a o ee enol ener tote oro # Oty 0 AB. (i) Cl> CH=CH, > CHyCH,>H (s) (il) Br > CH(CHs), > CH,CHs > CHs (s) (ii) Br> Cl> COOH > H ®) 29. Explain the difference between Orthogonal and Orthonormal functions? (2) A8. Two functions are said to be orthogonal if their scalar product is zero i.e. fe. cov, (nee =0 (m#n) ‘And they are orthonormal if they are normalized wave functions jerow, (x)dr = 1 sng ¥.OF, (x)dx =1 gin ECs) = Ae” oa sx sacivnes ECR) i ncrmatiat te constants A and Xq are real and the limits of integration are from ~ 2, 00 (3) A40. The condition for normalization is given by J Ya) (x) de = 1 A fete a = Subsitute 2” = 2A(x —x,)*, then 2 = V2A(x ~ x,), dz = 2A de“16 QIL. Suppose the state of a system is described by Y(X,t) = We % + ye with WW being real. Derive the condition under which ‘U(X, t) behaves like a stationary state. @ Alt. Stationary state is defined as a state whose probability density is independent of time ie. L(x, t).\¥"(x,£) = Constant ea V(x, ).E (x) = wh + Y2 + 2y,y, cosf(E, - E,¥/n] Only when E, = E, , the probability density is a constant. Q12. Why should the wave-function describing a state in quantum mechanics be “square- integrable ? Q ‘12. Awave function ‘¥(X) is said to be square-integrable if the scalar product of the wave function with itseff is finite ie. jv “GOW (x)dx #0 This condition is in agreement with Born's interpretation of probability density and ensures that the probability of finding a particle some where in space is equal to 1 ON oF = af, 9 YCr, Ek (at) = fy, (621 8-AWND) +, (gap esting) X 1 vt (08 r4sing) + Y.Neo A etsin grb " i 5 f FR By yt + we teytet BO) ty ay, oh Oe = ye TWIN oy pee (6-6) = TAT Dyas r2y, vcesf (5B) i Q ny@ % | Department of Chemistry 6) Indian Institute of Technology Roorkee CY-101 Chemistry, B.Tech Ist Year 2009-10, Autumn Semester Maximum Marks = 30 Tutorial No.1 {1 Maric the chirality centers inthe following compound and assign RIS notations (42443) ° Seno 2 N Ho : Draw all the possible stereoisomers (WEDGE-DASH DIAGRAMS ONLY), mark R/S nétation for each chirality ecnter and identify the relationship between the isomer, falowiae tun behaved wave function, probability density and probability. Prove that whether the 3 saenng functions ae the eigen function of the given operators (A) or not? Whe ett corresponding eigen value in each case? Yo operators, eee Fs Gi) costmy/L) Pi pif2m {B) Evaluate the commutator (1,1 ], where, and H are positon and Hamitonian operators, respectively. ’ (C) Consider a particle confined in a 1-d box of lensth a, 2 (2 Write the wave function for this system under condition O- (D) Explain briely how degenerate energy levels arse inthe case of paticle ina. ed box - () Cateulate the wave length forthe transition of an electron fom the ground stale to the fst excite state contined in a wo-dimensional box of length and width of 0.14 nm (A) Draw crystal field splitting diagram of he following complexes a) [Fe(H.0),)" ») IRC ©) [Coch &) Ni(CO), nes Calculate their erysal ld stabilization energies and magnetic moment (sin only) respectively, ij (8) What would be the characteristic colow for (Mn(H.O})” and [MaBra}* respectively? Give reasons eSOLUTION TO TUTORIAL ~ 1. Cy101 1 Mark the chirality centers in the following compound. (1424443) Draw all the possible stereoisomers (USE WEDGE-DASH DIAGRAMS ONLY), mark RS notation for each chirality center and identify the relationship between the isomers. Answer: s ° N. ( Sy 4 ‘CHO Z ni Ho 4 4 (7 mark) ° ° Re esi ne hon i Sei i ST Youo 2 2 Wor 4 WO “oH o o For each correct drawing (4 mark) (4.x #= 2) If both R/S notations of an isomer are correct then award 1 mark (4x / = 4). If one notation is correct award mark. (D) and (I) & (III) and (IV) are enantiomeric pairs (I mark) (1) and (1), (1) and (LV), (1D) and (IH) & (U1) and (LV) and diastereomeric pairs (2 marks) (A) Define well behaved wave function, probability density’ and probability. Prove that whether thefollowing functions are the eigen function of the given operators (A) or not? What is the corresponding 3 eigen value in each case? Ye operators ® ee Pp Gi) coset Pos pil2m Answer: Iie well behaved wave function shouldbe init, single valued and continuous. The probability density tells us the probability of finding a particle at a given point and itis the square of wave function, The wave funetion is a complex, then itis equal toy y’. Probability is the finding the particle in a given voluwe element dv or in a given range, x and x + dx, i. it is equal toy y'dv or y yide (mark) i) 1a function is an eigen function of an operator A, then the following eigen equation must be satisfied Wo A=E Ys igen equation (24 mark) z wor pt = Cina Pe Yor [iby dtdx? (e™)] = hi dldel(-iky (ey) SRC s) WEE = yey (4 mark) Therefore, yj an eigenfunction of > and eigenvalue ish k? i) Yea) cosaawL); pp, = ih) did P, Migs~ (ih) didx (costax/L) in(/L) sin(nx/L) Therefore, yy is not an eigen function of p, (4 mark) You costx/L): pi /2m = Citytam ads? B; 12m y= (Ciby'?2m) B/E? (cos(ax/L)] = (Nm) (RLY cos(an/L)= (N7/2m) (a/L)* Yay /8mL* Omar) Therefore. yi isan eigen function of p? / 2,1 and eigen value is = (82m) (W/L (8) Evaluate the commutator [x, Af], where, X.and H are position and Hamiltonian ‘operators,f. jf ‘spectively. 4 a3 5 Answer: [x1 }= x HH x é If “P is a function, then cH f-Hxf= Daf tas) (af Ide) — xd? f tate? 2m ‘m 2m x f-Hx f=" (ata (df File) apie) = cap tae) 2m 2m 2m m (x, |= x Hx =commutator=" (1d) (1 mark) mm (C) Consider a particle confined ina 1-d box of length a (© Write the wave function for this system under condition 0- Answer: AD ols) = A sin (n/a) for 0S x 2a, where A is the normalization constant and n is an integer which can take value 1 - (4 mark) , ad(4-0-0-0) AA (al2)=1 A= (2h)! (mark (id) Ifthe wave functions ys and ys. ate orthogonal, they must satisfy following equation: . Jey wax ie = fur Wega ales(asin = AA fon’ 2 sin ™ a a aa ssin{( py tea) (2-1) 2(2+1) i (4 mark) (i) Yep = @/L)'Gsin me/L), where L-10.0 nm Probability ide = [(2/1)sin* (ax! Lyd 2s nm 1 = eto = 2 r ial L 10 (4 mark) iv) Substitute Fi = ~(h"2m)(272,7) and y,(x) = A sin (anx/a) for 0 of a particle described by the following ‘wave function in the range of -o to « using momentum operator ( p= f/i.d/dx ). woe cB Solution: The average momentum = fy” Buy ydx/[y" ydx ai

= Alify’ dytdx)dx fy" ydx Given ¥ = e™, hence d¥/dx =ik¥

Ali.ikfy’ ydx/fy" ydx

=hk | 3- If following are the eigen functions for a particle in two different states in a box of width L, then prove that they are orthonormal wave functions. y.=V2/Lsin xwWL and vy, =V2/L sin nx Solution: For orthonormal function: fy," w, dx =0 ¥L Hence, hve y) dx =2/Lfsinax/L.sin2ax/L.dx ee 9 7 = *L(Vsin.xx/L )-(1/6sin.3 xx AL) = 0, these functions are orthonormal. 4. Calculate probability (p) of the particle in one dimensional box for zero point energy between (L/2 +0.04 L )and (L/2 - 0.04 L). Solution: The wave function for zeto point energy at x = L/2i =V2/Lsin #(L2)/L and Probability density (p) at x= L/2 in one dimensional box is: p(L2) = y.w = 2/Lsin? 2(L2VL =2/L and probability fora limit (dx ) of 0.08 L is: (p(L).dx) = 2/L.0.08L = 0.16. 5. Prove that operators d/dx anad/ty do commute on follwoing function, 2, waxy dy dx dx dy hence the operators d/dx and d/dy do commute on function y=x?y.Inorganic Chem 6. Calculate wave length for absorption maxima (74ax) for [Co(NHs)6] ** and [Mn(H,0),] °* complexes; if their crystal field stabilization energies are 66 k cal/mol ‘and 60 k cal/mol respectively.Comments on their crystal ficld stabilization energy (CFSE). ne Solution: 350 kcal/mol = lem", hence, vax ({Co(NH3)6] *) = 1/ (66 x350 om Dax ([Mn(H20)6]?") = 1/ (60 x350 cm 329 A® 1% Higher the CFSE lower the ?.stex % 7. Draw crystal field splitting diagrams for the following complexes and comments on their magnetic properties. ‘a= [Mn(CN)o] °° and b- [Ir(NH3)6] ** A Solution: [Mn(CN)6]* UeNHD)SP™ a = 4 40 4 4h t+4 +h tt + og Both are low spin complexes and [Mn(CN)s] ** is paramagnetic 4 8, Draw low and high spin state erystal field splitting diagram for (Cr(H0)s P* complex und predict, which spin state of the Cr*” ion in the complex would be less stable, if A, and the mean pairing (P) energies are 12,000 emt 20,000 cmt respectively. 4[Cr(H,0)617 [Cr(H,0).7" i .. ——s4 lao 4 +++ qt ++. In [Cr(H:0)¢J"* complex, the Cr is in d* state. 0.6 Ao =-0.6 x 12,000 em" — = - 7,200 cm = 1.6 A +P ae = - 1.6 x12, 000 em™ + 20,000 em’ = + $00 cm al CFSE: High spin state Cr°* ion Low spin state Cr’* ion Cele CFSE is less than the pairing energy (20,000 cm"), hence low spin state of Cr°* ion complex would be less stable. | structures of C3H (2)5 6 n ais. gis. “ee ‘ a> * Fee ‘The general solution for Eqn.(1) is w(x) = A cos(kx) + B sin(kx) Aand B are constants Applying boundary condition I, when x = 0, y=0 yO) = A cos(0) + B sin(0) = A cos(0) ~ 0. This means, A= 0, Applying the second boundary condition, when x ‘y) * B sin(k/) = 0. This condition leads to k/ = 2) a ‘Substitution of k into equation (2) will lead to E,= n7h'/8n? ‘An electron in a one dimensional box of width 10 A undergoes a transition from the ‘ground state to the first excited state. Pind out the wavelength of the photon . absorbed. © E,=0°h'8m?” (1 Mark) For ground state, n= | and for the first excited state, n= 2 E,=h'/8ml? and EB; = 4h?/8mP? ‘The energy involved inthe transition will be AE ~ (4h?/8mi) ~ (hY8mE) = 3 18mi? Length of the box = 7= 10 A= 10 10° m= 10°m Substituting the values, AE = (3 x (6,626 x 10™)V(8 x 9.1094 x 10°" 10") = 1.3171 « 10 / 7.2875 x 10° £8073 x 10" Joules (3 Marks) i.e. he/ 4 = 1.8073 x 10" Joules 2 = (6.626 x 10™ x 3 x 10°) / 1.8073 x 10 0998 x 10% m (0998. A~ 1099.8 nm (1 Mark) Alternatively: hY8mi? = 6.0248 x 1074 x Ey = 2.4099 x 10" AE= 1.8073 x 10" J=he/ A, 2.= (6.626 x 10 x 3 x 10°) / 1.8073 x 10 .0998 x 10% m 10998 A = 1099.8 nm Culeutate the degeneracies of the first sic energy levels for a partiete in a cubical Bos (6% %=3 Marks) i) 111; degeneracy = 1 ii) 112, 121, 211; degeneracy iit) 221 212 122;; degeneracy = 3 iv) 311 131113; degeneracy = 3 ea nieeeeraGy =" k vi) 123 132.231 312 213 321; degeneracy = 6 yok oh ee at 3 4 ea at “ret ". Gat omar gh Coy = tL(b) It is a octahedral d° low spin complex (t,°,€,°) tL th Lt IRh(C)6]* I isa 4d* system (M” oxidation state), so large crystal field spliting, pairing is favourable CFSE = (6 x 0.44,) ~ 0x0.64,) = 2.44, (12 mark) Magnetic moment (1 (no unpaired electron, n SQRT{n(n+2} =O (1 mark) 0) 6 (€) It isa tetrahedral d? system (e*,:') fem ef a [Co(Cl).* % mark CFSE = 4 X 0.64, 3 X O.4xd,= 1.20, (122 mark) Magnetic moment (1) = SQRT {n(n+2} = 3.88 iy (n=3) (I mark) (deduct % mark for no unit) 4) Ni(CO)s is ad” tetrahedral system (ec 8) (% mark) fh th] th HELL Grose 10 (C2 mark) moment = zero jis (1/2 mark) (no unpaired electron) (8) What would be the characteristic colour for (Mn(H,0)]” and [Mur] respectively? Give reasons. UMn(H0),}* is pale pink as its « d° high spin octahedral complex and the d-d transition forbidden (spin as swell as laporte forbidden), therefore molar absorption co-efficient is very low. mack) While [Mn(B1),]° is a d° tetrahedral complex and it appears blue in colour. Because, Laporte selection rule is partly allowed due to asymmetric tetrahedral structure. mark) (fastudert does not specify blue colour, instead simply writes “[Mn(Br),)” is coloured” Bui, able to give proper reasoning, give full marks)