CIVIL SERVICES (MAIN)EXAM- 2023, SKYC-U-CHM ered -fega (9A-Wa-1) raifta aaa : fa a2 aftrea a : 250 WeA-aa aeapelt fase arqeet (S&P Praia Aer A ge Tauris: GU) waa ore we Fst at awel A fanfar & wen feet sik stteh Ae A wt ee ater at ga ute weil % ser 23 F wa der 1 it 5 stand & ven ah wet 4a wee es 8 an-8-am Uw we GHAR A eT Te ifr was wea % fer faa sis sae ar fee ae wet & on afl waits are # fora ort afte, farerar see sas wan-sa 4H fen en 2, sh ga Te a TE FPG WH-we-sM (Ae Hho Uo) yfera % gaye w fee waa ow fen sr aafee era AeA & setae aT fire ream fora ame see He HE sim eT AH wel craw A, Penis site a we ar oe 2% fee qm ea FA aT eI wa we sigfen 3, daa cen erat wafers ae sal Fo wge eI a sree @, a sage atest a ear Aq ae seat fee Fifa wet & seret A ern sagen A areh stirs eo 8 faq me wet ay A A aM A sre ale za aI Srey 1 we-ae- a yea A are Ee aE gE steer yey aT A Pla: ae AAU CHEMISTRY (PAPER-I) Time Allowed : Three Hours Maximum Marks : 250 QUESTION PAPER SPECIFIC INSTRUCTIONS (Please read each of the following instructions carefully before attempting questions) There are EIGHT questions divided in two Sections and printed both in HINDI and in ENGLISH. Candidate has to attempt FIVE questions in all. Question Nos. 1 and 5 are compulsory and out of the remaining, THREE are to be attempted choosing at least ONE question from each Section. The number of marks carried by a question/part is indicated against it. Answers must be written in the medium authorized in the Admission Certificate which must be stated clearly on the cover of this Question-cum-Answer (QCA) Booklet in the space provided. No marks will be given for answers written in a medium other than the authorized one. Coordinate diagrams, wherever required, shall be drawn in the space provided for answering the question itself. Unless otherwise mentioned, symbols and notations have their usual standard meanings. Assume suitable data, if considered necessary, and indicate the same clearly. Attempts of questions shall be counted in sequential order. Unless struck off, attempt of a question shall be counted even if attempted partly. Any page or portion of the page left blank in the Question-cum-Answer Booklet must be clearly struck off. SKYC-U-CHM/5 1 [P-7.0.we sah wifes Ferries atte wate TT ‘Some useful fundamental constants and conversion factors SKYC-U-CHM/8 N, =6-022x107? mol"! Rydberg constant =2-178x10'8 J c=2-998x108 ms? kp =1-38x10°9 JK! e=1-602x10" C Me =9-109x107*! kg F =96485 C mol! R=8-314 JK mol”! =0-082 L atm K"! mol! h=6-626x10 Js m=3-142 1 amu = 66x10?" kg 1 cal =4-184J5 1 J =1kgm?s? 1A =10° cm =107'° m =0-1 nm =100 pm 1 atm = 760 torr =1-01325x10° Pa 1 bar =1x10° Pa = -9869 atm 1 eV =1-602x10719 J 1 L atm =101-34 J 1 eV/atom = 23060 cal mol”! 2 1 Pa =1 kgm lvelsgct Acceleration of free fall, g=9-81 ms? 1 torr = 133-322 Nm 1N=1kgms?vE—A / SECTION—A 1. (@) (i) ¥41-0x107" gm am 3A wa H-sraMh ataW An, =2 Bn, =1 arm &, dh sae ara seafita sare ar vented ara AL (i) erent aera fata A caren APE () Find the wavelength of the emitted light when 1-0x10-?7 g particle in a one-dimensional box of length 3A goes from n, =2 to n, =1 level. (i) Explain the Heisenberg uncertainty principle. 10 (®) (Bry) 3% HNCSNH, (#4 c yy, a4 N very sx s TTY a aria eam 8) AL gen fry sew wae ecg Hyer aur A A? a at, aaa aaa stew wir an 8? Draw Lewis dot structure of [Brg]” and HyNCSNHp (central C atom is bonded to both the N atoms and to the S atom). Does thiourea contain polar bonds? If yes, which is the most polar bond? 10 Co) ee ime apa Are at X-faret & aented & are ow Brea A GoM A ae te Aga daa (i) x-fi, fare cited 220 pm %, 23° ator Us orate freee & fafa eet 1 Taal, at ga Peat & fare faedan &, & ata A et a 8? () Derive an expression that relates the wavelength of the X-rays with the distance between the layers of atoms in a crystal. (i) The X-rays of wavelength 220 pm are diffracted from an ionic crystal at an angle of 23°, What is the distance between the layers that are responsible for this diffraction? 10 (2) ae are are Ae Fra we oF & arse A alm aT 719 ms} BH (i) 473 KA agai a aiea-ae A a eT? () Find the temperature at which the water molecules can have the 1 root-mean-square speed of 719 ms7!. (i) What is the root-mean-square velocity of water molecules at 473 KP? 5. fe) Fra ad-afifen & fore 2° a A ern fare Cr3* (aq) +3e~” + Cr 25°C % fea 7H 8 fH crt @q)+e” > Cr?*faq) EB” Cr?* (aq)+2e” > Cr SKYC-U-CHM/5 3 [P.-T.0.Calculate the E* value for the half-reaction Cr+ (aq) +3e” > Cr Given that at 25°C Cr" (aq)+e" + Cr?*(aq) E* =-0-424,V Cr?* (aq) +2e" > Cr E -0:90V 5 @ Ba AR Be wR aM ATI t) (Q) fea za 4 ata & ara se eal air wa A sae 87 (2) WHA wes za% 10 mL A 100 mL & srem-srerm ha & aR F ea sre 8 erat Ba az OF wa xa He afte act 8? The surface tension of liquid A is seven times higher than that of liquid B. (1) Which liquid is expected to have higher contact angle with glass? (2) 10 mL of each of these liquids are placed in separate 100 mL glass beakers. How do these liquids respond if the gravitational field is switched off ? 5 2. (a) fen date etre ari A argaheala A we ae Papa & fee tea wafer ar sear a ‘frafafas % am aire : @ Gar Tan PX ae fram & fq semniteha day aa AA (i) Sree Sete % Patel en 8? (i) GAM Ta ore wR otk ree aA TTA A Tea Ae, ate FE A (iv) (1) ref she (2) sitet softs aeiafeearstt A sofeaft te A ter fea ae sat Fee ares am & ade S8 waiad ach %, aren Fife Using the Gibbs equation for a closed system in the absence of non-expansion work at constant composition, answer the following : () Deduce the thermodynamic relations for the variation of G with T, and with P, (i) What are the implications of the above relations? (ii) Draw G versus T graph and identify the phase transition temperatures, if any. (iv) Explain how the presence of (1) attractive and (2) repulsive molecular interactions affects the molar Gibbs free energy of a gas relative to its normal value. 20 () aren Afr fi ait os ym a A Sai ora fia eh & afta UH ata A us am A Sal wifes ae 81 Explain why the energy of a free particle can vary continuously but the energy of a particle in a box is quantized. 10 SKYC-U-CHM/5 4() Sm Aw ae wee tT & fran Ff) (Www ae A feat ares fry safe 87 (i) AT A BR very A see don enh? (ii) FH eT A fara fom Sar eT RP fv) WR a Te HF sera Gey A ART 178-1 pm %, a saa A fren aa Fife ta wit was 8a Sa Fo TH (vo) Taha A seReRtts Hen eT AT Consider a primitive cubic lattice structure of an element. () How many lattice points are present in this unit cell? (i) What is the coordination number of the atom present in this structure? (ii) What is the percentage void volume of this structure? (iv) If the radius of the atom present in this lattice is 178-1 pm, then find the radius of the sphere that can fit in the centre of this cubic unit cell. (v) What is the coordination number of this sphere? 10 (@) we aftr Ay) 2A) % fran fm, frat A, ta 25°C 3k lL bar W 18:5% Pein & art #1 ) 25°C RK, Her Fhe) (i) 100°C RK, #1 tee FARR! fea ma & ff AH® =57-2 kJ mol”! (sage aa-att ) | (ii) Fe Aen aes ae Ta vem RP Consider the equilibrium reaction Aj()->2A(), in which Ap gas is 185% dissociated at 25°C and 1 bar. f) Calculate Kgq at 25 (i) Calculate Kgq at 100°C. Given that AH® =57-2 kJ mol”! (at the above temperature range). (ii) What is the effect of compression on this reaction? 10 3. (a) [BrFs] 3 [Cl,)” sinteier tira A yeas sik onftas Sarita Aafia Afr Determine the electronic and molecular geometry of [BrFs] and [ICl]” interhalogen compounds. 10 SKYC-U-CHM/5 5 [P.7.0.(6) Prafefion weit % sm Gre, st fe a8 fee me ween arta we sree & : (Fe man site feat weal st enti 8? (i) Sra ara aR Hare Aa D ae % fegsll A wear Ae) (i) WES BO HME SP G5 Ha aie att A aren Afr! Answer the following questions based on the phase diagram given below : ‘Temperature, T () How many components does this phase diagram represent? (i) Identify the points A to D with corresponding degrees of freedom. (ii) Explain the changes expected in the paths E+B—+H and E+F3G5H. 20 () ‘fA He) +20 (@) + HO() % Pram fe, 3 WE Hy -Oy fe Ber Ae BL () Fast aA seahe fad atacten stk srraea ate t1 fi) 25°C Tae afte fea ge Sal (A,.G*) a ofr Af) (ii) FAAS ser a -shBreane fafere (iv) Bag 7 Tice Afra) fem en 8 A,H"(H,0, ) = -285- 83 kJ mol! Sn (H20, 1) =69-91 JK“! mol? Sm (Ha, g) = 130-68 J K™ mol? Sin (Oa, 8) = 205-14 JK"! mol! SKYC-U-CHM/5 6Consider the reaction Ha @)+2026) > #,0(0, which occurs in a H-O, fuel cell. (j Identify the elements that undergo oxidation and reduction. (i) Calculate the standard reaction Gibbs free energy (4,G°) at 25°C. (iii) Write down the two reduction half-reactions for the cell. (iv) Calculate the Been. Given that ApH" (HO, I) =-285- 83 kJ mol! Si, (20, 1) = 69-91 JK"! mol! ‘Sin (Ha, g) =130-68 JK mol? (Og, g) = 205-14 JK"! mol? 20 4. (a) 273 K 3 3-0x10° Pa % wm Pfeaa fa aI sa 5-0x10~ m3 mol”! ya am RI ae fa arerarea whee a Wer Bh 8, Ta a=0-50 m® Pa mol? %1 @ a areca frie, ba site Ar (i) HO AIA sk zara H eH He} fore ates IS eT A? (ii) eA snes stapes % aes eH oh fe ‘The volume of a certain gas is found to be 5-0x10™* m* mol”! at 273 K and 3-0x10° Pa. This gas obeys the van der Waals’ equation with @=0-50 m® Pa mol”. () Calculate the other van der Waals’ constant, b. (i) What is the compression factor for this gas at the same temperature and pressure? (iii) Comment on the nature of the molecular interactions of this gas. 20 (b) HWA fra Fw] 15 cm A A A eh (Rl) 45° FH seh aT BUH A a fore 4A A ach (Rl) A crane 4 Pen cara stem (torr 4) sera Be eae? eA aT AA 10 gem™ & A 15 cm drinking straw is inserted in a glass of water at an angle 45°. What pressure difference (in torr) must be generated across the length of the straw to drink water? The density of water is 1-0 gcm™. 10 SKYC-U-CHM/5 7 [P-7.0.() (a) 5. (a) () ( wan fea r % gage Isr (blow) & fare fea r A wa Shee ae a za A Hae Pe arm 81 a gage a sor & fore sraeas aftr aa 2-16 torr &, ah aftr eh at om cm 4 am 8? 3a & Yea GH 0-072 Nm! #1) A capillary tube of radius r is inserted into a liquid to blow a bubble of the same radius r, If the excess pressure required to blow the bubble is 2:16 torr, then what is the diameter of the capillary tube in cm? The surface tension of the liquid is 0-072 N m™!. aeteds, Year stk orecifefert, faterte % quite aye &, a rial A are sna Bsa fafaea & aera as faery she TA WE terres wart a Yaihea APR! Pyroxenes, amphiboles and phyllosilicates are well-known groups of silicates that occur in crust of the earth. Write the empirical formulae and draw the basic structural units of the above-mentioned silicates. ‘avs—B / SEcTION—B AB, ® ABW BA sree we wena A afiiem %, Pat k=2-8x107 8) & T= 1000 K Ri A 7H B® Wry YR HAW: 12 3k 32 F1 @ 1000 °C) 8 aftiren A stig wa Ff) (i) PRA RA 1 g AB, saMha Bar 06 g AB, HATE? (i) 1g AB, 35 fea % are fern we sre? The decomposition of AB, to AB and B is a first-order reaction with k=2-8x10~7 s" at T= 1000 K. The atomic weights of A and B are 12 and 32, respectively. (Find the half-life of this reaction at 1000 °C. (i In how many days will 1 g of ABz decompose to the extent that 0°6 g of AB remains? (ii) How much of 1 g of ABy would remain after 35 days? sy A urs ok fe eagle aaensit % a aon sit afaPeoh wien A are Af) we Face ata a i aren Ff) Explain radiative and non-radiative processes by singlet and triplet electronic states of molecule. Also explain it through Jablonski diagram. wredeta aat uret aafaersitens an A sha we aka wer al ee AAA ate aT rales Assign a geometry and hybridization to each carbon atom present in cytosine and thymine nucleotide bases. SKYC-U-CHM/5 8 10 10 10 10 10(@) Ras seri & UV-gem serie Sag # ta me de Ger wen & agi dari AL aren fare Explain three main types of electronic transitions observed in UV-visible absorption spectra of actinide ions. 10 (o) P88 aE area sien A oie BA EAR : PPtcl4]?- +Noz —> [4] S43_, jp} wn feaia aro ates Zie-we A caren ard ge cifras fre Ff) Identify A and B in the substitution reaction given below : [PtCl4]?- +NO3 — [4] —NE_, Justify by explaining the kinetic trans-effect using polarization theory. 10 6. (a) fafafaa aftienst a ym Ae ok at ara wa@ sere (serel) A een sareT f) 2XeF,+Si0, 80°C, (iy) NH,No, —220K_, + fii) NO + NaNH, —270K_, (iv) 2ByHg + 6NH, —182°C_, + (v) 6SCl, +16NHy —> + + Complete the following reactions and draw the structure of the major product(s) formed : ) 2XeF, +Sio, —22°C _, (i) NH,NO, —920K_, + (ii) NgO + NaNH, —270K_, (iv) 2ByH, +6NH, —180°C_, + (x) 6SCl, +16NH, —> + + 10 (b) (Co(CN2(H20)(NH3))* Hea SrA % fer wh ava fen amraael an tenes aera) Draw all possible stereoisomers for [Co(CN)9(H20)2(NHg)2]" complex ion. 10 SKYC-U-CHM/5 9 [P-T.0.(c) Frafeftad eget A TUPAC amHTala fefax : (9 [Cr(H20)qCl2]C1 (i) [Colen)3] Fe(CN)g] (iti) Na[Cr(H20)2 (x)2) (iv) (Pa(CO}2(H,0\CI)* (vy) Nag{(H20)4V(H-OH)2VH20)4) Write the IUPAC nomenclature of the following complexes : () [Cr(H0)4Clg]Cl (i) [Colen)g] Fe(CN,) (iti) Na[Cr(20)2 (ox)2] (iv) [Pd(CO}2(H20)Cl]* (v) Nag[(H20)4V(H-OH)2V(H20)4) 10 (@) Sasi A dean on oa cent A caren Fifi) ae Bteifeea a Aa fra 87 Explain the structural and other features of rubredoxin. How does it differ from ferredoxins? 10 fe) Prafeftra ai % sree (framework) arid wagh A dea she dean % ah A wry AR: @ ByHF (i) BH (ii) BQH Predict the number of framework bonding electrons and the structure of the following boranes : ByHF (i) Buy (i) BaHy 10 7. (a) Ara ate a tg a age se gH ideas othe aac A aa dee frdensi & aren Fife) stetheirehiaa stk A-siteeheinche A ama ata Ig very seach weer A aren Afiel wae Fata ag see A EM se, Sa8e orp oh sitet don a1 a fel Explain the common structural features of two major iron-containing proteins—haemoglobin and cytochrome c present in the human body. Explain the coordination chemistry involved at the central metal atom in case of oxyhaemoglobin and deoxyhaemoglobin. Give the details of the spin states, magnetic moment and oxidation number of central metal ion in both the cases. 10 SKYC-U-CHM/5 10(b) ra sigs Sears ar ye-sraeen yagi fara fafaq ()soPr (aftrieifier) (i) g3Eu (gah) (iii) ggGa (eter) a faek A ered A +3 ated seen Fang sre & foe aga war data seeph (Hs¢1) A en Fife) Write the ground-state electronic configuration of lanthanides mentioned below : () s9Pr (Praseodymium) (i) gE (Europium) (ii) g4Gd (Gadolinium) Calculate the predicted effective magnetic moment (1s, ,) for the metal ions in +3 oxidation state in the units of Bohr magneton. () Reanfters yie ofiinn & fae a aire aa HPC! ga wa FA aie A serfs we fear Fife, va feta afters A ott Ban Prafeftar we @ saftrato ant: AtB> 3A @ Aah Bam afeehia Bae (i) A, BA Gera aearga aire wa Ta siete eT BL Derive a rate expression for a bimolecular surface reaction. Discuss the Kinetics of such a reaction, when the gaseous reactants, say A and B, are adsorbed in the following way : A+B -— Product () A and B are sparsely adsorbed. (ii) A is relatively more strongly adsorbed than B. (a) [Ni(OS(CH,))g)?* Wea APA } UV-eeR Ban A Raa A state & ae ‘sraeehfira on ten) aifers ws 8 fret A den a aga eT atk He Gra Tai dari A Puitte Af Nickel was found to be coordinated with oxygen in the UV-visible spectrum of [Ni(OS(CHg)2)6]?* complex ion. Predict theoretically the number of peaks and assign them to the corresponding electronic transitions. 10 10 10 SKYC-U-CHM/S coy (PTO.(fe) w aed 4a (V,=0-05L 4k PB =8 atm) 25°C % sarha aah waK (Vp =0-40 L att Py =1 atm) % wera 8 aref vg 81 ge wien % fore fe me ari, AU, AH at aS vitae aif en ga vise A Sen (q), AH % GAR 8? ale ae, at eal? An ideal gas (V; =0-05 L and P, = 8 atm) is subjected to reversible isothermal expansion (Vj =0-40 L and P, =1 atm) at 25°C. Calculate the work done, AU, AH and AS for this process. Is the heat (q) same as AH in this process? If not, why? 10 8. (a) [Fe(n’-CsHs)q] 8 YR FA | [Fe(n®-CsHs)(n°-CsH4COCH,)] 3k FFe(nS-CsHs)(n°-CsH4COOH)] get % dea FH Ketan TART Sketch the synthesis of —[Fe(n°-CsHs)(n°-CsH,COCH,)] and [Fe (n°-CHs)(n°-CsH,COOH)] complexes starting from [Fe(n°-CsHs)2]- 10 (bo) FPreaferftan eget 3 Asta org weary & Bact vee Garhta sampl (1.) I Vie I : @ (Fe(H,0}sNO}?* (i) [CrNCS)6)*~ (i) [V020)6]°* (iv) (Colbpy)3]?* Calculate the spin only magnetic moment (j1,.,) of the central metal atom in the following complexes (@ (Fe(H,0);No}** (9 [CrINCS)6)>~ (iii) [V(H20}6]°* (iv) (Colbpy)s}?* 10 (co) 34 300 nm airtel ar srafta var ue faa 4 8 arr ara 2, af 1 cm aa Ha, A ae srafar ware I Fae 10% aT et Tata FET Bi OS om Fa 4 WAM fae eA W var a1 fern wierd srazitfica erm? When an incident light of wavelength 300 nm is passed through a solution ina 1 cm cell, it transmits only 10% of the incident light. What percentage of light would be absorbed by the same solution if taken in a 0-5 cm cell? 10 (a) sitter a & fare dan-saen faaia A caren Ae! HS ga fein A snitasra atta A eset re A A afte i sare wer aaa # dug feraia 8 Feet APT are 8? Explain the transition-state theory for reaction rates. How is this theory considered superior to collision theory in providing a much more complete interpretation of the pre-exponential factor A in the Arrhenius equation? 20 ae SKYC-U-CHM/5 12 SB24—504