FANS Lid, FIITIEE House, 29-A, Kalu Sara, Sarvapriva Gur. The energy of the electron in 542 x 10°" erg and -2.4] x 197! when the electron drops from third to TB respect A 100 ml flask containing ©. 0.6 atm and 300 K, by means of a narrow tube to form NO), Fi lly NO» (g) dimerized, ‘ ; , partial . tobe 0.41 atm at the same temperature, Frad oy ena 2NO, (3) ==N,0, (g) 2 at 1.2 atm and 30 of negligible volume, when they combine quantitatively y ‘and pressure inside the flask was f id % dimerization of NO, as pe A sample of lithium was burnt i of HCI and resultin; end point. An exc burnt to the oxide. Find the work done when 1 mole of the gas is expanded reversibly and isothermally from 5 atm to 1 atm at 25°C. A vessel at 100 K contains CO) with a pressure of 0.5 atm. Some of the COs is converted into CO on addition of graphite. Calculate the value of Ky if the total pressure at equilibrium is 0.8 atm, For the reaction: SnO, (s)+2H, (g)=—*2H,0(g)+Sn(s) Calculate Kp at 900 K, where the equilibrium steam-hydrogen mixture was 45% Hy by volume. Find the concentration of Ag* at A Galvanic cell is constructed with Ag'|Ag and Fe" | Fe* electrode snag and Fe which the emf of the cell is zero at equimolar concentrations of Ft (Ebay yuo =0-80 V and E2.,... =0.77 V) Use the following data to answer the question below: rt O ah, oS AH =~ 28.6 kCal mol Ni CO oe AH (wi) 89 kCal mot! naphthalene i I. Calculate the resonance energy of naphthalene in kCal/mol Fin constant) for the solvent, p-chlorobenzene, from the ind the value of Ky (freezing point depression constant) vent, val e following data. © (Ky /mol)=17.88 Molar mass = 147,01, Melting point (K) = 326.28, A jae ( ) Answer must be in the units of 10” K kg/mol- Tew Delhi = 16, Ph 46106000, 26569493, Vihar , New Delhi‘GMP-1516-CH-ASSIGN-432 13, 14, 15. 16. ay. 18. 19. 20. 21. ae. pay 24. Calculate the value of molal elevation constant for water if ASyapoursasin 18 26.33 cal Kt mob! Consider the reaction, 2Ag’ +Cd—>2Ag +Cd” The standard electrode potentials for ad “i lard Wetts Alston An’ os Ap and Cdl —+ Cd couples are 0.80 volt a 0.40 volt respectively. : S baie (i) What is the standard potential E° for this reaction? (it) For the electrochemical cell, in which this reaction takes place which electrode is negative electrode? At 353 K, the vapor pressure of pure ethylene bromide and propylene bromide are 22.93 and 16.93 K 'N m “ respectively and these compounds form nearly ideal solution. 3 mole of ethylene bromide and 2 mole of propylene bromide are equilibrated at 353 K and at a total pressure of 20.4 K N m-*. (a) Whatis the composition of the liquid phase? (0) How many moles of each compound are present in the vapour phase? The unit cell length of NaCl is observed to be 0.5627 nm by X-ray diffraction studies; the measured density of NaCl is 2.164gem™, Calculate the difference of observed and calculated density and calculate % of missing Na” and CI ions. [Fe(CN),]* and [Fe(H:0).]” are of different colours in dilute solutions. Why? Explain from the VB method the possibility of the formation of the CNz molecule. Water can react with hydrogen ions to make the oxonium ion, H;O". What is present in a water molecule that allows it react with a hydrogen ion? Describe the bonding in the oxonium ion. Why the bond angle of H — C — Hin methane (CH,) is 109° 28° while H ~ N ~H bond angle in NH; is 107° though both carbon and nitrogen are sp’ hybridized. The melting point of KCI is higher than that of AgCl though the crystal radii of Ag” and K” ions are almost same. ‘An element of group V on reaction with concentrated HsSO, gives an acid (B) and an oxide (C). (C) on reaction with acidified dichromate produces the acid (D). (D) is having very strong affinity towards water. (A) with metal (E) produces as hydrolysis a gas (F) of odour of decaying fish, Find (A) to (F). From the following metallurgical flow chart, identify steps A, B and C. ‘Sulphide —“-> Oxide —*/ Impure metal—* >Puremetal Silver nitrate gives a white precipitate with aqueous sodium thiosulphate; the precipitate dissolves in excess of thiosulphate. If the precipitate is heated with water it tums black, and the supernatant liquid then gives a white precipitate with acidified barium nitrate solution. Give the reactions for the above observations. {A yellow solid (A) is unaffected by acids and bases. tis not soluble in water. It dissolves slowly in hot cone, HINO) and brown gas (B) is released. The solid (A) dissolves only in a boiling solution of sodium sulphite giving a clear solution (C). Acidification of solution (C) causes a colourless gas (D) t0 be liberated, accompanied by the appearance of a milky precipiate (E) in the solution. Identify (A) to ). Dehydrohalogenation of 1, 2-dihalides (with the elimination of two molar equivalents of HX) normally Jeads to an alkyne rather than to a conjugated diene. However, when 1-2-dibromoc, loxehane IS dehydrohalogenated, 1,3-cyclohexadiene is produced in good yield. Kalu Sarai, Sarvapriva Vihar, New Delhi - 16, FUTIEE Lid, FITIEE House, 29-4.28. GMP-1516-CH-ASSIGN-433 Show how an aldohexose can be a ied to synthesize 2. fructose by this method, w aba ae keto et Since luc ls ‘method, what can you say about the oi figurations oF Cees 8 core to pe ; Gun + C° and C* in the sugars, (GHOH). + SQHuNHI = f INH. Sra P= NNACH, HOH Ne (HOH), Avene me | CHOH One H-C=0 f FH:OH =O =O HOH) Zn/GHsCOOH (GH CH:OH CH.OH Osone 2ketohexose (a) Supply structures for H through K. Given: An aldohexose —N'sOH/base_,}4 __AcrO/NaOAC | ___HoAG: J—NaOMe/ MeOH (b) Explain the last step (c). What is net structural change (d) Name this overall method. (e) Discuss the possibility of epimer formation. A polyhydroxy alcohol having molecular weight = 168, On acetylation the molecular weight increases to 294, Determine the number of -OH groups present in the alcohol, CH; eee ee oe HO (A) CoH 3 — ea (Cae eee : CH Write the structure of (A) Arrange the following compounds in their increasing order of acidity: OH OH OH NOp oH ae A, No, b (a) (0) ei (F) NO2 OH (B) (OG ium is taken? In sodium fusion tests why excess of sodium is tak es es Chlorobenzene when treated with ethanolic AgNOs it does not give white precipitate. Explain lorobenzene ylation reaction why? Nitrobenzene does not undergo Friedel Crafts Alk: it ic acid, Starting from benzene how will you prepare m-nitrobenzoic Ga Vihar New Delhi - 16, Pk: 46106000, 26 Sanaprive Vikar. FUTSE€ Lid, FITTIEE House, 29-A, Kalu Sarai.WPANGIG-CHASSIGM-494 ety of substituent group are sehisbeddie Coatn hog up are listed. Indicate the effect of these group on electre Milena ify them as activating or deactivating and also rea itr drtoing iia fee yo, ~OH, ~CN, -NHCOCH;, -NHCHs, -OC3Hs, -C Hs, -SO, rie ° SH, -F, -1, ~ , Hs, Cos, ~N(CH. COOH, -COOR, -CHO, —C—, -Br. ine exists as © exists as (HsN°CH;COO ) while anthranilic acid (p-NHp~CsHs ~ COOH) does not exist as dipolar ion, 6 Compound A (C)H,C Cn WH/Cl) is hydrolysed by dilute Compass A y y dilute acids to give compound B (CsHsO) compound be enidised under mild conditions to compound C (CyH0). Compound (C) upon eine ot Zall nitrated HCI gives Ethyl benzene. Identify structures from (A) to (C). : 37, Predict the product ofthe following reactions oH CH.CH.CHs o. Cc w oO ‘0, 2 [Ems Rawson 38, Make tautomer of OH I! Il Why CH; ~ C ~ CH; ~ C ~ CH is known as active methylene compound? 39, 40, Explain the order of hydrolysis of following CH,COCI (CH;CO);0 CH\COOGH; —— CHsCONH, (a) (b) © @ 41. Explain basic strength of following NH) H (a) (b) ©), 42, Amunsaturated hydrocarbon A (Celis) readily gives B on treatment with NaNH in iquid NH. When B is allowed to react with I-chloropropane a compound C is obtained. On partial hydrogenation oe 2, 2-dimethy! compound C gives D (CsHis). On ozonolysis, D gives presence of Lindlar catalyst, give the structures of A, B, C and D. propanal and I-butanal. With proper reasoning Write the intermediate steps for each of the following reactions. @ SS ete OH Cl Fo-A, Kalu Sarai. Sarvapriva Vihar, New Delhi - 43. FATIEE Lid, PUTIEE Howse,44. 48 49. 50. 51 52, 53, GMP-1516-CH-ASSIGN435 (i) CcHsCHOH)C = CH —_H,0: ae ete = Chat > CH 2 cH, CHCHO, i) Hy = GH—Chon CHs Suggest a mechanism for the d ec intermediate. Assign a catal f O in 1,0. ‘Wie role to the acid and keey List the possible products, in : in ord pentane with alcoholic KOH.” ° “&eteasing yield, from the reaction of 3-bromo -2,3 ~ dimethyl Account for the formation of both 3-bromo-2,2— from the reaction of HBr with ,3-dimayl dimethyl butane and 2-bromo-2,3 dimethyl butane Optically active 2+ ee iodooctane when treated with radioactive Nal!™* ity is twice the rate of isotopic exchange. Explain in dry acetone rate of loss of optical A solution of 0.2 g of a compound containing Cu’? and Cs0,? ions on titration with 0.02 M KMaO. in presence of H2SO, consumes 22.6 mL of the oxidant. The resultant solution is neutralized with Na,CO:, acidified with dilute acetic acid and treated with excess KI. The liberated iodine requires 11.3 mL. of 0.05 N NazS,03 solution for complete reduction. Find out the molar ratio of Cu"? to C:0.? in the compound. Write down the balanced redox reactions involved in the above titration. An equal volume of a reducing agent is treated separately with 1 M KMnO; in acid, neutral and alkaline medium. The volumes of KMnO, required are 20 ml in acid, 33.4 ml in neutral and 100 ml in alkaline medium. Find out the oxidation state of manganese in each reaction product. Find out the volume of 1 M K,Cr;0; consumed, if the same volume of the reducing agent is treated in acid medium. HO; is reduced rapidly by Sn”, the products being Sn** and water. H:O> decomposes slowly at room temperature to yield O; and water. Calculate the volume of 2 produced at 20°C and | atm. when 200 ‘gm. of 10% by mass HO; in water is treated with 100 ml. of 2 M Sn” and then the mixture is allowed to stand until no further reaction occurs. Identify the product of following reactions R o CHO SPANO P _enycmt_y¢ Furfural Also write the mechanism involved. Identify A, B, C and D, in the following schemes and write their structures, L(A) —at-(@) PSH 9) yoo \ CH, NH.NHCONH, >———— (0) (leer NaQDID,O (excess) ae) jum in dry ether forms an organometallic Csclobutytbromide on treatment with magnesivin HO os anol (B) after mild The organometallic compound reacts with et ; (06000, 26560095, Fax FNEE Ti, FUITIBE House. 29-4, Kalu Sarai, Sarvapriva Vihar. New Delhi 16. Ph 461 Pee deGMP-1516-CH-ASSIGN-436 $4 56, 57. 58, w, 61. PARTIEE Lid. PIITIEE Howse, 29-A, Kalu Sara, Sarvapriva Var, New Delhi - 16. Prolonged treatment of tani cohol (B) with an equivalent amount of HBr gives |-bromo-1- lopentane (C). Write the structures of (A), (B) and explain how C is obtained by (B). An alkene (A) CycHis on ozonolysis gives only one product (B) CxHsO. Compound (B) on reaction with NaOH/, yields sodium benzoate. Compound (B) reacts with KOH/NH-NHa yielding a hydrocarbon (C) C,Hjo. Write the structure of (B) and (C). Based on this information give two isomeric structures of (A). An organic compound (A) CxH,O3 in dry benzene in the presence of anhydrous AICI; gives compound (B), the compound (B) on treatment with PCI. followed by reaction with Hy/Pd (BaSO,) gives compound (C) which on reaction with hdyrazine gives a cyclized compound (D) CisHioNa, Identity (A), (B), (©), and (D). Explain the formation of (D) from (C). How would you bring about the following conversions? (i) Ethanal to 2-hydroxy-3-butenoic acid (ii) 2-methyl propanal to Fy ak wrk ‘cHo on (iii) 2-butanone from ethyl alcohol iv) 3-hexanon from n-propyl alcohol Cyclopentyl bromide on treatment with magnesium in dry ether from an organometallic compound (A). The organometallic compound reacts with ethanol to give an alcohol (B) after mild oxidation Prolonged treatment of alcohol (B) with an equivalent amount of HBr gives 1-bromo ~ 1- methyl cyclopentane (C). Write the structure of (A), (B) and explain how (C) is obtained from (B) What would be the major products in following reactions? a Hy, aes enon D} ss oe NO, CH et 2) a cl a e Explain the order of hydration of following: CHO CHO 0 0 Br 1 Br (a) (b) o} (d) Hydrolysis of 2- bromo ~ 3 ~ methyl butane (2°) yield only 2-methyl -2- butanol (3°), Explain echanism (SN', SN’, Et» Complete the following equations showing major produet, which reaction 1 E)) is likely H IC a) —* + ee Hsebi 65, HG, b) Br + KOH SON, 9 wet CH, Oe Carry out the following conversion Hy es b) lis) 2 op one OS 4) Co ilar asa Tare 3 OH OH An optically active amine (A) is subjected to exhi an alkene (B). (B) on ozonolysis gives an equimol GMP-1516-CH-ASSIGN-437 austive methylation and Hofmann elimination to yield jlar mixture of formaldehyde and butanal. Deduce the structures of (A) & (B). Is there any structural isomer to (A), if yes draw its structure. Which one is more basic and why? ano fa) (b) Which one is more nucleophilic and why?GMP-1516-CH-ASSIGN-438 67. 68, 69. 70. 71. Tae 73 74, (a) w Calculate the energy required to excite one litre of hydrogen gas at 1 atm and 298 K to the first exciteg state of atomic hydrogen. The energy for the dissociation of H-H bond is 436 kd mol! HCH BO CH; (a) (b) (a) cannot be resolved into enantiomers while (b) can, why? Pyrrolidine can be readily extracted from an ether solution into an aqueous solution of acetic acid (pK, = 4.75) but pyrrole cannot. Explain. A pungent smelling liquid (A) was analysed and found to contain carbon, hydrogen, chlorine and Possibly oxygen and upon reaction with aqueous ammonia a neutral compound (B) was formed. When this was treated with bromine and potassium hydroxide a base (C) resulted. In acidic solution, substance (C) reacted with sodium nitrite, giving nitrogen and an alcohol (D). Upon mild oxidation, the alcohol (D) was converted into compound (E) of M.F. C2H,O which gave a positive test with ammoniacal silver nitrate solution. Describe the chemistry involved in these reactions and identify the compounds (A), (B), (C), (D) and (E). (a) Calculate the velocity (cm/sec) of an electron placed in the third orbit of the hydrogen atom. Also calculate the number of revolutions per second that this electron makes around the nucleus, (b) An electron in a - H atom in its ground state absorbs 1.50 times as much as energy as the minimum required for its escape (13.6eV) from the atom. Calculate the wavelength of emitted electrons. One mole of an ideal monoatomic gas ially at 1200 K and 64 atm is expanded to a final state at 300 K and 1.00 atm. To achieve the above change, a reversible path is constructed that involve an adiabatic expansion in the beginning followed by an isothermal expansion to the final state. Determine the magnitude of net work done by the gas, in cal. (R = 2 Cal/K-mol, In 2 = 0.7) In a cycle ABCA consisting of isothermal expansion AB, isobaric compression BC & adiabatic compression CA. Find the % (approximate) efficiency of eycle. 4 [Given : T, =Tp = 400K; y= 1.5, n2=0.693, 2°= 1.26] P } B Lt Vaan In solid NH3, each NH3 molecule has six other NH molecules as nearest neighbours. The enthalpy of sublimation of NH3 (s) at its melting point is 30.4 kJ mot! and the estimated value of enthalpy of sublimation of NH; (5), when there were no hydrogen bonds, is 15.4 kJ mol! What is the average strength of hydrogen bonds in solid NH in kJ mol! 2 PUNIGE Lid, FIITIEE Howse, 29-4. Kalu Sarai, Sarvapriva Vihar, New Delhi -16. Ph:79. 80. 81 83, 84, 85, 86, GMP-1516-CH-ASSIGN-439 Draw a graph between degree of dissociation («1 ) Vs time for zero order reaction. A 50 litre vessel is equally divided into three membrane (SPM). The vessel contains 60 2 Hy g Np in the right one. The left SPM tt arts with the help of two stationary semi permeable Bas in the left chamber, 160 g O> in the middle & 140 = allows transfer of only Hy gas while the right one allows the transfer of both Hp ® Np, Calculate the tial tao of resstie tie ee eter feed 5.22 * 10° moles of a gas containing Hi, O> and N; exerted. pressure of 67.4 mm in a certain volume. The gas was Passed! over a hot Pt-filament which combined H, and Os into H,0 which was frozen out When the gas was returned to the same volume, the pressure was 14.3 mm, Extra O; wae added to increase the pressure to 44.3 mm. The combustion was repeated after which the pressure read 32,9 mm, What was the mole fraction of H, O» and N; in the gas sample. A flask containing same He gas at 1.5 atm & 300 K is connected to another flask, four times larger in volume containing Nz at same temperature and pressure by means of narrow negligible volume tube. The bigger flask was then kept in a thermostat both maintained at 500 K, while other still at 300 K. Find final pressure, Iron crystallizes in several modifications. At about 910°C, the body centred cubic o-form undergoes a transition to the face centred cubic y-form. Assuming that the distance between nearest neighbours is same in the two forms at the transition temperature, Calculate the ratio of density of y-iron to that of a- iron at the transition temperature Titanium crystallizes in a face centred cubic lattice. It reacts with C or H interstitially, by allowing atoms of these elements to occupy holes in the host lattice. Hydrogen occupies tetrahedral holes, but carbon occupies octahedral holes (a) Predict the formula of titanium hydride and titanium carbide formed by saturating the titanium lattice with “foreign” element. (b) What is the maximum ratio of “foreign” atom radius to host atom radius that can be tolerated in a tetrahedral hole without causing a strain in the host lattice? 5.35 g of a salt ACI (of weak base AOH) is dissolved in 250 ml of solution. The pH of the resultant solution was found to be 4.827. Find the ionic radius of A* and Cl’ if ACI forms CsCl type erystal 0.732 for this cell unit A g/em*. Given Kiyaoiy = 1.8 x 10° F having Ina face centred lattice with all the positions occupied by A atoms the body centred octahedral hole i it is occupied by an atom B of an appropriate size for such a crystal, calculate the yoid space per unit volume of unit cell. Also predict the formula of the compound. 0.10 mol sample of AgNOs is dissolved in 1.00 L of 1.00 M NH). If 0.010 mol of NaCl is added to this Solution will AgCI(s) precipitate? In hypophosphorus acid P is in +1 state (HsPO.) and in phosphoric acid (HsPO,) P is in +5 state but Still HyPO> is stronger than HsPO,. Explain. On the basis of H-bonding explain that the second ionization constant K2 for fumaric acid is greater than for maleic acid. The fixing of photographic plate film involves dissolution of unexposed silver bromide in hypo Solution according to the equation AgBr(s) + 28,0;7(eq) Ag(S:03)"(aq) + Br(aq) Calculate molar solubility of AgBr in 0.1 M hypo solution assuming its complete dissociation FEE Lid, FIITIEE House, 20-A, Kalu Sarai, Sarvapriva Vihar, New Delhi - 16, Ph; 46106000, 26569493. Fax 26513942