Level Chapter 6 Thermodynamics Solutions (Set-1) SECTION -A 4.) AG) —> BG): AH = 10 kJ mort (i) B(g) — C(g); 4H = 25 kd mol" ‘Adding (i) and (ii) A(g) > C(g), AH = —10 + 25 = +15 kJ molt 2. Molar mass of benzene = 78g. 78g benzene > 3000 kJ heat 39 Sag benzene + 3000x32 = 1500 kJheat 3. Hy(g) + CL{g) > 2HC\g), aH = 185 kJ/mol Ai ig+teitg) Heng), aH =—18 92.5 ksmot" ghz 2 4. BauH = AugH + AvagH AugH = «+ y) kd mort 5. Heat of atomisation of Cl, = Bond dissociation of Cl, = x ki mol 6. Answer (2) ag = 9 DRT, TOT Py Vv). (BY In| Ye) = nen 2.) MJ 7. Answer (3) Ang =n,—n, = +ve 8. Answer (2) Se _5 4.67 for monoatomic gases. cy 3 Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345654) Thermodynamics Solutions of Assignment (Set-1) (Level!) 9. Answer (4) 410. Answer (2) 449 49 mat, }00,0821% 300 a Woe = -PAV = ~1(246.3 - 5) = = 246.3 L 11. Answer (B) 12. Answer (B) 13. Answer (D) 14. Answer (B) 45. Answer (C) 16. (i) Open system (i) Closed system (ii) Isolated system 17. Approcess during which no heat flows between the system and the surroundings is called an adiabatic process. 18. Because most of the processes are carried out in open vessels as constant pressure (atmospheric pressure) whereas internal energy is measured at constant volume. 19. Free energy change signifies the useful work done by a system. 20, AU =4q+w, where w = negative as work is done by the system, 21. The enthalpy change is equal to the heat of reaction at constant pressure. AH=q, 22, The reference state of the substance is the state in which the substance is stable at 1 bar pressure and 298 K. It is represented by the sign in superscript, 23. Hess's law states that the total enthalpy change of reaction is the same, regardless of whether the reaction completes in one step or in several steps. Example : aH, a——_+8 D+F It means the change in enthalpy from A to D i.e., AH, is equal to AH, + AH, + AH, for A> B > C > D, Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-1) (Level) ‘Thermodynamics | 55 24, Its the quantity of heat required to raise the temperature of the system by one degree, 25. The change in enthalpy when a substance is dissolved in an infinite amount of solvent. At this point the interactions between the ions are negligible, 26. The internal energy of a system changes when (Heat is given or absorbed by the system (ii) Work is done on or by the system (ii) Matter enters or leave the system 27. When reversible expansion of an ideal gas is taken into consideration, the change is brought about in number of infinite steps. The change is infinitesimally smaller such that the difference between the driving force and opposing forces are almost in equilibrium. The work done is -EpAV. So, when the graph is plotted, they gives a smooth curve. 28. First law of thermodynamics states that whenever a certain quantity of some form of energy is consumed, an equivalent amount of energy is produced. For example when 4.184 joules of mechanical work is done 1 calorie of heat is produced and vice-versa 29. The change in internal energy is given by the expression AU=qtw Here, q= 20 kJ w=-50 kJ (negative sign implies the work is done by the system on the surrounding) AU = 20 kd + (50) kd = 20 -50kd =-30 kd The internal energy of the system decreases by 30 ki. 30. W = 2.303 nRT log Y Ms =-2.303 «1 * 8314 « 200 * log Se = -2.308 x 8.314 x 300 « 0.699 = 4015.16 J 31. () When the reaction is carried out in a closed vessel so that the volume remains constant, ie., AV = 0. (i) When the reaction involves only solids or liquids or solutions but no gaseous reactants or products. This is because the volume changes of the solids and liquids during a chemical reaction are negligible (ii) When the reaction involves gaseous reactants and products but their number of moles are equal (ie., n, =n), eg., in the reaction » H,{g) + Cl(g) —> 2HCi(g) 32. Mass of water = (10° x 10° mL) x (1. gmL-1) (v= &, considering density of water = 4 gml-") =10%9 qQ.=mC.AT (Where AT = 35-30 = 5) 10° g x 4.184 JK-gt x 5 = 20.92 « 10° J Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345656 33, 36, 36. 37. 38. 39, ‘Thermodynamics Solutions of Assignment (Set-1) (Level!) Enthalpy of a reaction is the amount of heat evolved or absorbed at constant temperature and at constant pressure, when number of moles of reactants represented by the chemical equation have completely reacted. Example : CaO(s) + CO,(g) —> CaCO,(s); AH® = -178.3 kJ/mol Here we can see that CaCO,(s) has not been obtained from the constituent elements C, O, and Ca, Whereas, enthalpy of formation is the amount of heat absorbed or evolved when 1 mole of compound is formed from its constituent elements under given conditions of temperature and pressure. Example C{s) + O,(g) —> CO,{g); 4H® -393.5 kJ mol Extensive properties : Those properties which depends on the quantity of matter present in the system. Example : mass, volume, internal energy, heat capacity etc Intensive properties : Those properties which is independent of the quantity of matter present in the system. Example : density, melting point, boiling point, specific heat, refractive index etc. AG? = AH’ — TAS? AG? = [-87.20 « 10% - (298(-175.83)] = 87200 + 2397.34 = ~4802.66 J Since AG° is negative ie., the process is spontaneous. 4C{graphite) + SH,(g) —> C,Hyo(9) AH® = EAH Products ~ EAH Resctante = [C4Hyo] = [4(C) + 5(H2)} = [2878.5] — [4(-393.5) + 5(-285.8)] = -2878.5] - [-1574— 1429] 124.5 kJ molt () AG = 4H - TAS = 40.63 - 373.4 x 108.8 x 10° = 40.63 x 40.63 = 0 Since AG = 0, system remains at equilibrium. (i) Bond enthalpy is the amount of energy necessary to break bonds in one mole of gaseous covalent substance to form products in the gaseous state. N,{g) + 3H(g) —> 2NH,(9) ‘AH = -92.38 kJ and An, = 2-4 R= 8.314 x 10° kJ moh K+ We know that AH = AU + An,RT = AU = AH —An,RT AU = [92.38 kd] — [(-2) 8.314 10° x 298 kd] = -87.42 kd () Heat is a form of energy that is transferred between the system and its surroundings as a result of temperature difference. Its symbol is q (ii) By work we mean the energy is spent during the act of moving an object against an opposing forces such as gas inside the cylinder acting against the piston. Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-1) (Level) ‘Thermodynamics | 57 40. Entropy increases when (Number of molecules of products are more than the number of molecules of reactants. (i) When solid state changes to liquid state. (i) When liquid state changes to gaseous state. (wv) When the substance undergo sublimation. 41. The fundamental properties which determine the state of the system are termed state variables. The change in state property depends only upon the initial and final states of the system ie., independent of the path followed. Example pressure, volume, temperature, entropy, force etc. 42. Number of moles of ideal gas (n) = 1 Initial pressure (P,) = 10 atm Final pressure (P,) = 1 atm Temperature, T = 300 K Gas constant R = 8.314 x 10-? kJ mol" K~* Work done for isothermal reversible expansion of an ideal gas. Py, We -2.303 nRT log P = 2.303 » 1 x 8.314 x 10-9 kJ mol K+ x 300 K = -5744,14 « 10-8 kJ molt 43. Enthalpy of formation is defined as the enthalpy accompanying the formation of one mole of a compound from its constituent elements. It is denoted by A.H®. ‘The knowledge of standard enthalpies of variotls substances can help us to calculate standard enthalpy change of any reaction. Where standard enthalpy change of a reaction is equal to the difference of the standard enthalpies of all the products and standard enthalpies of reactants, AH? = [EAH ductal — LEAH Seactans 44, PH,(g)— P(g) + 3H(g); AH, = 228 kcal mot" PH, - PH, —> 2P(g) + 4H(g); AH, = 355 kcal molt On the basis of the given data AH, = AHy_p + 40H, _ r aH, 228 o 385 = aH, _p +a x 2S AHp y= At | AH _ » = 51 kcal mol-* 45. In an ideal gas, there are no intermolecular forces of attraction. Hence, no energy is required to overcome these forces, Moreover, when a gas expands against vacuum, work done is zero (because Px = 0). Hence, internal energy of the system does not change ie., there is no absorption or evolution of heat. 46. Average bond energy is used in the case of polyatomic molecules because even though the molecule may be containing identical bonds with the identical bond length and energy, the energy required to break the individual bonds differ in each successive step. So in such cases average bond energy is used. For example in CH, molecule, all the four C-H bonds are equal in bond length and energy but differs in terms of energy required to break the bonds. Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345658) Thermodynamics Solutions of Assignment (Set-1) (Level!) CH,(g) —> C(g) + 4H(g); A,H® = 1665 kJ mot CH,(g) —> CH,(9) + H(Q); AyongH® = #427 kd mot-t CH,(g) —> CH, (9) + H(Q); AygngH® = +439 kd mot-t CH,(g) —> CH(g) + H(g); ApongHt® = +452 kJ molt CH(g) —> C(g) + H(g); Agong® = +347 kJ mot 427 +439 + 452+ 347 ‘Therefore, A,H® 7 = 416.25 kJ mol Itis different from bond energy of a diatomic molecule because the energy required in diatomic molecules is to completely dissociate the molecules into atoms by breaking the covalent bonds of a gaseous covalent compound to form the products in the gaseous phase. 47. Initial volume V, = BRT. - 9-150%0.081% 294 _ 9 369 am? p 10 Final volume V, = MRT — 9.150%0.0821%294 _ 5 6 ime 1 1(3.62 — 0.362) = -3.26 atm dm? >| w = -pAV = -1 « (V,-Vy) 3.26 Latm = -3.26 « 101.3 J (1 Latm = 101.3.) = -330.2 J 48, Al,C,(s) + 12H,O(l) —> 4AKOH), + 3CH,(9) 1 mol 3 mol When vessel is closed, volume = constant ie., AV = 0. Hence W = -PAV When the vessel is open, initial volume, V, = 0 (as no gas is present) Final volume, V, = Volume of 3 mole of CH, _ RT V,=nRT = v, PV, n= BE ART =a 0.914 » 200 The work is done by the system on the surroundings. 49. The difference between AH and AU is not usually significant for the system consisting of only solids and/or liquids, IT Vq = total volume of the gaseous reactants Vp = total volume of the gaseous products ig = number of moles of gaseous reactants np = number of moles of gaseous products Then at constant temperature and pressure, assuming ideal gas behaviour, we can write RT Vp =" R= Mae Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-1) (Level-l) Thermodynamics | 59 and Va =np et P and AV =Vp We know that AH = AU + paV = aU + an ST and AH = AU + An,RT 50. Energy is released in the formation of a chemical bond between two atoms and energy is required to break the bond. Chemical reactions involve the making and breaking of chemical bonds. Energy changes in a chemical reaction is the net difference between the energy needed to break the old chemical bonds in the reactant molecules and the energy released when new bonds are formed in the products. For example H,(g) + Cl,(g) —> 2HCI(g) H-H(0) —peceeapes 2H(Q); AH = +436 kd Bieagbors Cl- Ci(g) 2CK(g); AH = 242 kJ Energy absorbed in broaking bonds 2H(g) + 2C\(g) 2H — Cl(g); AH = -866 kd (For two moles of HCI formed) Energy eased when new Bonds ae formed Thus, for the reaction H,(g) + C1,{g) —> 2HCK(g) Enthalpy change, AH = (436 + 242) — 866 = 678 — 866 = -188 kJ 51. The spontaneity of a reaction can be decided by considering Sia = Sie) * ASsuroundings For calculating AS,,,, we have to consider the heat absorbed by the surroundings which is equal to A|H°. At temperature T, entropy change of the surroundings is = SHS (at constant pressure) 1648 x10° J mot 7298 K = 5530 JK“! mol" Thus, total entropy change for this reaction ASyggi = 8530 JK“ mol + (849.4 J KI molt) = 4980.6 JK“! molt This shows that the reaction is spontaneous. Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345660) Thermodynamics Solutions of Assignment (Set-1) (Level!) 52. Suppose an ideal gas is enclosed in a cylinder fitted with weightless and frictionless piston of area of cross- section A. If the pressure of the gas inside the cylinder is greater than the pressure outside the cylinder (extemal pressure) /€., Pn, > Pay: Piston will move outside. This will bring a change in the volume of the gas, The process is considered to be happening at constant temperature i.e., isothermal process, The change in volume of the gas, AV= V, — V, Fina) diay During this expansion procedure the piston moves by a certain length ‘AI’ in a single step. The volume change = Al x A aV=(V,-V4) We know, p= £ Vs A F=PA av] 1 If w = force x displacement ‘,| = py XA Al Pox v | [areaArY, = PexlAV) = py AV ‘And w = ~py,(V>— V,) ‘The negative sign implies that work is done by the system on the surroundings. 53. N,O,(9) === 2NO,(g) IFN,O, is 50% dissociated, the given equilibrium is N,0,(9) —= 2NO,{g) Initial moles 1.0 0 Equilibrium moles 0.5 2x08 Total mole = 1+ 0.5 Pressure = 1 atm Mole fraction of NOs, Xy,0, = 3 Mole fraction of NO,, Xyo, - 28 x4 atm, Paros = 7.5 | Pao = 7g The equilibrium constant K, is given by Since, AG® = -RT Ink, = (8.314 JK! mol") « (333 K) x (2.303) x (0.1239) 763.8 kJ mot" Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-1) (Level-l) Thermodynamics | 61 54. CH,COOH(!) + C,H,OH(!) > CH,COOC,H,(!) + H,0(!) Initial mote 4 mol 1 mol 0 0 ‘At equilib 4 4 2 2 equilibrium 3 3 5 5 ‘The equilibrium constant, [CH,COOC,H,][H,O] ‘© [CH,COOH][C,H,OH] Since, A,G® = -2.303 RT logk = -2.303 x 8.314 x 300 = -3457.97 J mot = 3.458 kJ mot? 2,303 x 8.314 x 300 * 0.6020 58. Roversiblo process Irreversible process 1. Risa process which folowe reversible path 1. Its a process which follows reversible path 2. itis an ideal process and takes infinite time 2. tis a spontaneous process and takes finite ime 3. Inthis process, the opposing force and driving foree | 3. Thereislarge difference between driving and differ only by infinitesimally small magnitude, opposing foree 4. Work obtained is maximum 4. Work obtained isnot maximum. itis only an imaginary process and cannot be 5. tis a natural process and occurs in a particular realised in actual practice directions under given set of conditions 6. IRoccurs through infinite numberof steps under | 6. Equilibrium existonly inthe beginning and atthe cequilbrium conditions at each step. completion stage. 56. Gibb’s Helmholtz equation is AG = AH — TAS ‘The conditions for AG to be negative arc (Both the energy factor as well as entropy factor are favourable ie., AH is negative and AS is positive. Under these conditions AG would be certainly negative and the process will be spontaneous. (ii) Energy factor favours but entropy factor opposes i.e., AH is negative and AS is also negative. Under these conditions AG would be negative if AH is greater than TAS in magnitude and that would be possible at low temperature. (ii) Energy factor opposes but entropy factor favours ie., AH is positive and AS is also positive. Under these conditions AG would be negative if TAS is greater than AH in magnitude and that would be possible at high temperature. 57. (i) C.H,(g) + 30,(g) —> 2C0,(g) + 2H,0; A,H®° = ~1410.8 kJ mort 1559.8 kJ mol-* (i) CHe(g) + Fos) 2C0,(g) + 3H,0; 4H Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345662 Thermodynamics Solutions of Assignment (Set-1) (Levelt) ii) Hyg) + $04) H,O()); A,H® = -285.9 kJ mort Our aim is : () C,H,(g) + 3H,(g) —> C,H,(g); A,H° = 2 Adding equations () & (il), C,H,(g) + 30,(g) —> 2C0,(g) + 2H,0; A,H® = -1410.8 kJ mot H,(o) + 0x9) — H,O()); A.H® = -285.9 kJ mort th eg4@)+Hga)= £0, —> 20,6) + 34,0; aH? = 10067 1 Subtract equation (i) from equation (v) C,H,(9) + H,(9) + Zo, —+ 2C0,(g) + 3H,0; AH? = 1696.7 ki CH,(9) + Foye) —> 2C0,(g) + 3H,0; 4,H® = -1559.8 kd or —CH,(g) + H,(g) —> C,H,(g); A,H® = -136.9 kd AH = AU + An,RT 196.9 = AU—1 « 8.314 * 10 x 298 -136. AU ~ 2.48 AU = 136.9 + 2.4% 134.42 kd mot 58. Our aim {s+ 28(s) > CS,(h); AH = 2 ‘The data provided is (i) C{s) + 0,(g) —> CO,(g); AH = -393.3 kd molt (iii) S(s) + O,(g) —s SO,(g); AH = -293.72 kJ mol (w) CS,) + 30,(g) —» CO,(g) + 280,(g); AH = 1108.76 kJ molt Multiply equation (ii) by 2, we get () 28(s) + 20,(g) —> 2S0,(g); AH = -587.44 kJ ‘Add equation (ii) with equation (v), we get (vi) C(s) + 28(s) + 30,(g) —> 280,(g) + CO,(g); AH = -980.74 kJ Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-1) (Level-l) Thermodynamics | 63 59, 60. a en Subtract equation (iv) from equation (vi), we get C(s) + 28(s) —> CS,(I); AH = #128.02 kJ mol" AH@y, = #128.02 ki () Normally the changes takes place at constant pressure (atmospheric pressure) and thus it is preferable to measure enthalpy changes. (ii) Yes, it is necessary to define ‘standard state’ because it holds significance for being at constant pressure of 1 bar and a temperature of 298 K. This state represents the most stable state of the substances. (ii) Yes, it is necessary to specify the phases of the reactants and products in the thermochemical equation because heat changes during the course of reaction depends on the physical states of reactants and products. () The first law of thermodynamics states that energy can neither be created nor destroyed but it changes its forms. This holds true for the law of conservation of mass. Hess's law also predicts the similar fact that total energy change during the same course of reaction is independent of the path by which reaction is made. (ii) Formation of a bond involves decrease in the potential energy of atoms forming the bond and thus eneray is released when a bond is formed. This decrease in potential energy is evolved as heat in the reaction and brings about stability of the atoms. ‘The energy released (or change in enthalpy) when a bond is formed from isolated gaseous atoms is known ‘as bond enthalpy, SECTION -B For isothermal process, AU = 0 For isothermal process q = -w = ~ (-100) = 100 J For isothermal AH = nCpAT = nC, x 0 = 0 ‘Answer (4) AH? =0 for elements in their elemental state ‘Answer (1) AG = 0 (At equilibrium) = 42100 = 119.26 J/K-mol ‘Answer (A) Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345664 10. "1 12. 13, 14, 15. 16. 17. 18. 19, ‘Thermodynamics Solutions of Assignment (Set-1) (Level!) ‘Answer (C) ‘At absolute zero or at -273°C the entropy of a perfectly crystalline substance is zero. Enthalpy of hydration represents the change in enthalpy in the conversion of 1 mole of an anhydrous salt into its hydrate by combining with specific number of moles of water. Because the change of state is accompanied by the enthalpy changes. AG® = -2.303 RT log K Itis defined as the enthalpy change accompanying the formation of one mole of a compound from its constituent elements in the standard state This is the law obeyed in all those processes which occurs on their own without the help of any external agency. Second law of thermodynamics states that “in any spontaneous process, the entropy (randomness) of the universe (system and surroundings) always increases. Gibb’s energy (G) of a system is a measure of its capacity to do useful work. itis the part of the total energy of the system that is freely available for conversion into useful work. That is why itis called as Gibb's energy Itis given by the equation. AG® = AH - TAS® S(s) + O,(9) —> SO,(9) 22g 0.5 g of sulphur on burning produces = 4.6 kJ of heat 32.9 of sulphur on burning produces = $832 = 204.4 kd ‘The enthalpy of formation of sulphur dioxide will be = 294.4 kd Hydrogen gas will have the highest entropy because gaseous particle have the least intermolecular force of attraction hence, they behave more randomly. So greater is the randomness among the particles greater is the entropy 5 Heat capacity per gram = [>= 4.17 Jg 1 q=mc.aT 1000 1000) = 100 gx 4.17 JxAT = AT=7 2° =2.39K AU=q+w Since, AU is a state function. Hence q + w is a state function. wo =-nRT Inve a Me mor! 6 2.808 NRT logy = -2.303 * 2 x 8.314 JK" mot x 300 x logs -2.303 = 2 x 8.314 x 300 x 0.3010 = -3457.9 J Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-1) (Level-l) Thermodynamics | 65 20. AG = AH-TAS = (40.63 x 10° J molt) - (300 x 108.8 J mol 7.99 kdimot-+ ie. AG > 0, ». The reaction is non-spontaneous. 21. CH,(g)—> C(g) + 4H(g), An, = 5-1=4 AH = AU + AnJRT AU. = AH ~An,RT = 400 ~ 4 * 0.002 x 298 = 397.6 kcal 22. AG = AH TAS () AG =—10.5 « 10° J mo — 298 K x 31 JK mol = ~19.738 kJ K-1 molt Reaction is spontaneous. (iy) a 11700 J mol-* + 31290 = +19590 Reaction is non-spontaneous. 23. Intemal energy is the energy associated with the substance, depending upon the nature where it may be physical or chemical. It is the sum of many types of energies such as translational, vibrational, rotational, electronic bonding energy etc., of the molecule. U = sans + Ups + Uy + + secure + U. Means Usonaing * steer 24. 2P(s) + 3Br,!) —» 2PBr,(g); AH = ~243 kulmol 62g 62 g of phosphorus on reaction with Br, releases 243 kJ of heat, 2.63 g of phosphorus on reaction with Br, releases ex 2.63 kd = 10.14 kd 28. CH,(g) + H,(g) — C,H,(g) H, H Hr Momod = Bond energy (reactants) — 2Bond energy (products) = [BE(C=C) + 2 » BE(C-H) + BE(H-H)] - [4 * BE(C-H) + BE(C=C) = [(827.6) + 2(414.0) + (430.5)] — [4(414.0) + (606.0)] = 2086.1 - 2262 = -175.9 kJ molt 26. (i) The third law of thermodynamics states that a substance which is perfectly crystalline at absolute zero of temperature has an entropy of zero. However, there are certain substances which possesses certain entropy even at absolute zero. This ‘entropy is known as residual entropy. (i) Standard enthalpy of combustion is the amount of heat evolved when one mole of the substance under standard conditions (298 K, 1 bar pressure) is completely bumt to form products. It is represented by ASHE. Example CH,(g) + 20,(g) —> CO,(g) + 2H,0()); A,H® = -890.4 kJimol Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345666 Thermodynamics 27. Tyyg = 200°C = 273 + 200 = 473 K ae = 30°C = 303 K ayn = 480 J = yp _ -480 4 88cm = Fe Gry OK (i) as,,, = See - 489 4 58 JK-t 0 Tour 303 (ili) AS.) OF AS yiverse = ASgysiem * AS, 1.01 JK! + 1.58 JK: Solutions of Assignment (Set-1) (Level!) 0.57 Jk Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-2) (Level) ‘Thermodynamics | 67 Solutions (Set-2) SECTION - A 1. Answer (3) ‘A thermos flask does not allow exchange of energy and matter. Hence, itis an isolated system. 2 Answer (2) ‘A system which undergoes change such that temperature remains constant. Such a change is called isothermal process, 3. Answer (2) Since the system is thermally isolated, energy can only be transferred through a non-thermal mode i.e. work. 4, Answer (3) g (heat) and w (work done) are both path functions. q+w 5. Answer (2) ‘According to 1* law of thermodynamics, AU, which is change in internal energy, which is a state function. AUSq+w weer (+ work is done on the system) q=-5 (~ heat is evolved out of system) AUE ras 6. Answer (2) As per I* law, AU=qtw = +10 kd (heat is absorbed by the system) w= ~4 kJ (work is done by the system) AU= q+ w= 10-4 kJ = +6 kJ 7. Answer (2) The absolute value of internal energy cannot be determined since it is the sum total of all the energies at a molecular level. These energies cannot be determined and hence the absolute value of U cannot be determined 8. Answer (3) Entropy is an extensive property (mass dependent). Temperature is intensive since it is mass independent 9. Answer (3) For the 3" reaction, CaCO3(s) —> Cad(s) + COp(9) 1 solid reactant gives 1 solid and 1 gaseous product and as a result increases disorder liness, = AS = positive Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345668 10. " 12. 13, 14, 15. ‘Thermodynamics Solutions of Assignment (Set-2) (Level!) ‘Answer (3) For stretched rubber, entropy decreases. Upon releasing, it regains its original shape =3 Spontaneous process, AS = positive So, for the reverse process (stretching), ‘AS must have been negative. ‘Answer (1) Least random state of H,O would be its solid state, ie. ice ‘Answer (3) MgCO,(s) —> MgO(s) + CO,(9) AS = Sco, +Sugo - Sgcos MgO and MgCO, are solids, so their entropy is almost same. AS = Sco, i.e., AS is positive. Answer (1) AS® = S*yy. -StHy -S'ny = 192.6 JK" — 196.75 JK" — 95.75 JK" = 98.9 JK" for 1 mole of NH, Answer (2) AS,,,= ~ 9 R x 2.303 (X}, logy + Xo, log Op) Total moles = (0.5 + 0.5) moles = 1 mole 1 My, =%op = 11.2 moles of 0, = 57 = 0.5 11.2 moles of H, = 7 = 0.5 AS = — 1 mol * 8.314 JK" (0.5 log 0.5 + 0.5 log 0.5) = 8.314 JK (log 2) = + 5.76 JK" ‘Answer (2) For the reaction, CyHy + Hp — CH AS’ = S’ona -S"on, — = (225 ~ 220 130) JK" Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456 HeSolutions of Assignment (Set-2) (Level) ‘Thermodynamics | 69 16. 7. 18, 19. 20. Answer (1) Let melting temperature = T = SHtusion Syren = _ _7.26calmol _ 107875 K *e73.calmortKt 0! T= 1078.75 K or (1078.75 ~ 273)"C = 805.75°C ‘Answer (1) 2H,(g) + O,(g) —> 2H, O(¢) AS = 2xSp,0 ~ (2x8, +So,) % 68.0 JK mol" ~ (2 x 126.6 J mol" JK + 201.20 J K mot") 136 - (253.2 + 201.2)] J K+ mo = — 318.4 J K* mot" ‘Answer (2) If AH > O and AS <0 = TAS would always be positive (+ Tis positive always) AH + (- TAS) is always positive tf Always Always positive postive => AG is always positive. Answer (2) Molar entropy of vaporisation of water, (AHyap)m _ 9710 cal mott (AS, = KK (8S vap 2 Sealer” = 26.03 cal mot K Answer (2) A reaction is spontaneous when AG < 0, We know, aG= aH+(-TAS) So, AG < 0 only when AH < TAS So, the reaction would proceed only when temperature is high Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345670) Thermodynamics Solutions of Assignment (Set-2) (Level-!) 21. Answer (3) Itis impossible for a reaction to occur when AG > 0 which is possible only when AH > 0 and when AS < 0. 22. Answer (1) We know, AG = AG* + RT In Q; Q = Reaction quotient At equilibrium, AG = 0; Q=K 0=AG* + RTInK or, AG? = — RT In K = ~ 2.303 RT log K 23, Answer (4) The sole criterion for the spontaneity of a process is the tendency to acquire maximum stability 24. Answer (3) Whatever the process be (endothermic or exothermic), AG has to be negative for the process to be spontaneous. 25. Answer (2) For the given reaction, AS = negative (~ Lesser number of gaseous products are formed) => -TAS = positive But AH = -ve Since, it is a combustion reaction and hence exothermic: AG = AH - TAS ; So for AG to be negative, |AH| > [TAS] 26. Answer (2) PCls(g) —= PCl3(g) + Cla(a) an,=2-1=4 AH = AU + An, RT = AU+RT or, AH > AU (+ RT is positive) where AU AE i.e., change in internal energy 27. Answer (2) For the reaction, An, = (¢- b) [> rest are solid substances} We know, AH = AU + An, RT or, AH = AU + (¢—b) RT or, AH — AU = (¢— b) RT 28. Answer (3) All reactants and products are liquid, hence, An,=0 Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-2) (Level) ‘Thermodynamics | 74 where, An, signifies change in moles of gaseous substances. AH = AU + An, RT or, AH = AU 29. Answer (2) Required equation Creaatie) —? Csamonty Corot) * Op —> CO,(9); AH = —%, cal CO, — Cogan + O,(9); AH = +x, cal Adding, We g&t Cian —? Crsanmny = AH 30. Answer (1) Given reactions are We know, AH = AH, + AH, + AH, or, AH, = AH— AH, ~ AH, = % +x) 31. Answer (4) 5 1 Pyalow) +502 (8) —>-FPL0s (5): AH) = +9.91K Pires) + $02(9) —> FP205 8); Hy ==8.78 kd Rearranging, we get Pryetiow) 9.91kd y+ F02(9) — P205(g); AH P05 —>P, 320) AH= 48:78 kd rod) * ‘Adding these two equations, we get (9.91 + 8.78) KJ= Prvoaony —? P, 1.13 kd ‘vem sa 32. Answer (3) Given 2x{ JNe(@) +02 (¢) —>NO- (9) AH => N,(g) + 20, —s 2NO,(g); AH, = 2x Also, Np + Oz ——» 2NO(g); AH=y 2NO +0, ——> 2NO, ; AH=z Adding, we get N, + 20, —s 2NO, ; AH, = y +z AH, = AH, (+ His state function) > may+z Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345672) Thermodynamics Solutions of Assignment (Set-2) (Level-!) 33. Answer (3) HCI + NaOH —> NaCl + H,0 + x cal where x cal is the heat released due to neutralisation of 1 g equivalent of acid by 1 g equivalent base. In the 2" reaction, HySQ4 + 2NaOH —> NazSO, +2H,0 + y cal Now, 2g equivalents of strong acid reacts with 2g equivalent of strong base, thus releasing double of energy released in the 1* reaction, y= 2x 34. Answer (1) Given 2 ssrasrne) + 2H,{9) —> C,H,(9); AH, AH, = Bond dissociation enthalpy of reactants — Bond dissociation enthalpy of products = 125 = (171 x 2) +2 104.3 - (4 « 99.3 + BE...) BE, = 140.9 kcal 35. Answer (1) Given reaction: 2CgHs (I) + 1503 (g) —> 12C05(g) +6 H,0(1) An, = 12-15 = -3 mol AH = AU + An, RT or, AH — AU =~ 3 * 8.314 Jk' mol" x 298 K x mol = 36. Answer (4) Sichombic) + Oz (9) —> $02 (9); AH= -297.5 kJ a) S{monoctinie) + 2 (9) —» S02 (g); AH = ~300 kd @) Subtracting (2) from (1), Stchombic) — S{monoct ic) § AH = (-297.5 + 300) kJ=+2.5kJ => This transition is endothermic. 37. Answer (1) H, (g) + S(s) + 20,(g) —> H,S0, ; AH, Given S+0,—> 80, 298.2 kd 1 $0 +502 —> 80g 98.7 kd S03 +H,0—>H,S0, i 130.2 kJ Hy + Fo, >H0 287.3 kJ Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-2) (Level) ‘Thermodynamics | 73 Adgiting all these, we get Hy +S +20, —>H,SO, AH =~ 814.4 kd AH, 814.4 kd 38. Answer (2) We know, work done, w =~ P,, + AV. Given, pressure is 10°N m= and, AV = 0.25 m? =~ 10°Nnv? « 0.25 m? =~ 250 J So, work done by the gas is 250 J 39. Answer (1) H,C20,4 (s) + (oxalic acid) Oz (g) —= 200, (9) + H,0(!) We know, AH.ccoutun = Amount of heat liberated when 1 mole of substance reacts with oxygen. Mol. wt. of oxalic acid = 90 g mol 1 g oxalic acid liberates 2.835 kJ 90 g (1 mole) oxalic acid liberates 2.835 = 90 kJ mor” 255.15 kJ 255.15 kJ Heat involved = 40. Answer (2) Let heat of ionization be a of LOH LIOH >Lit +OH” +HCI—“thest. 5 Licl + H,0 [| _t ‘AH = — 34.868 kJ x — 87.1 kJ mol" = ~ 34.868 kJ mol of, x = (67-1 = 34.868) kJ mol = 22.232 kJ 41. Answer (3) Maximum heat is absorbed by NH,NO, AH = + 16.08 (maximum positive value) 42. Answer (3) HA—> Ht + Ar; AH’ Given: HA + OH” —>H,0 + A™ +g; kJ; AH = —qy kd ay kJ + Hg ——y H” + OH | AH= + 49 kd Adding, we get HA —>H* + Aq ; AH’ =(qp - qi) kd Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345674 Thermodynamics Solutions of Assignment (Set-2) (Level) 43, Answer (2) 100g 1560 kd 1560 1880 480 180g 790 <180 kd wt of 1 gram molecule 1560x180 = 180 g which gives 55 — kd = 2808 kJ 44, Answer (1) An, = 6-9 AH = AU + An, RT of, AU = AH — An, RT = ~ 936.9 kcal — (— 3 R * 298 k) of, — 936.9 keal = AU + (- 3 X 2 cal k-! mob x 298 K) = AU ~ (8 «2 298 x 10) kcal AU = AE = change in internal energy. 45. Answer (1) 1 mole of strong monoprotic acid reacts with 1 mole of strong base to give — 87.1 kJ 0.25 mol of strong acid will react with only 0.25 mol of strong base (and not 0.5 mol) Energy involved = ~ 87.1 kJ x 0.25 46. Answer (3) COOH +3 0,(@)—> 7602(a)+ 34,0 We know, AH = AU + An, RT AH AU= q. = 4, + An, RT =~ 321.3 + {-4x200%xR) == 321.3-150R 47. Answer (4) H2(@)~4.02@) “> H,0(@) “ H,0 (4) Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set2) (Level!) Thermodynamics {175 Now, for Hp (a) + 2.0, (g) —>H,0(2):aH AH = BDE) ena ~ (B08), 1 = x, +2xp - 2x, rests = 1 + X2 ~ 2X3 1 Xy + 2x9 ~ 2xg +x, y+ 5X2 — Oxy + Xq 48. Answer (2) 12 ml of gas requires 54 ml of O, 9 or, 1 mole of gas requires > mole of O, I the gas is CH, CyHy +302 ——> 260, + 2H,0 Ifthe gas is propylene Cos + Go, —+3C0, +3H,0 9 Its clear that propylene (1 mole) requires > moles of oxygen. As per the data, 12 mi of gas requires 9 54 ml of oxygen and hence 1 part of gas requires > parts of oxygen by moles. The gas is propylene 49. Answer (1) Specific heat = 0.075 calories Molar specific heat capacity, C, 075 x 40 = 3 cal mot k* C, = C,+ R= 3 cal mot" "+2 cal mol k= 5 cal mot k* 66 => Monoatomic gas. 50. Answer (2) H(g)+0(g) —> 0-H(g); 4H AH = (B.DE) san ~ (B-.D.E) = O - Bond energy of 0-H = AH =—Bond energy of 0-H 51. Answer (3) H, (g), ——>2H(g);AH ‘mole (29) AH = (BDE) cays ~ (B.D-E)pguns= Bond energy of H, Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-4762345676) Thermodynamics Solutions of Assignment (Set-2) (Level-!) Given that 4 g of H, requires 872 kJ to dissociate 2.9 of H, requires 436 kJ => 1 mole of H, require 436 kJ AH = +436 kJ = Bond energy of H, 52. Answer (4) H I GC, —» Cla) +4H(g) AH, HH H Hw L He -G- H—> 2C(g) + 6H (g); AH, H H Given: AH, = 360 kcal mol ; AH, = 620 kcal mol Also, AH, = 4 * Bond energy of C —H = 360 keal mot* = Bond energy of C —H = 90 kcal mol Now, AH, AH, x Bond energy of C - H + Bond energy of C - C. 6 * 90 kcal mot’ + Bond energy of C - C 620 kcal mol” = 620 kcal mol" = 640 kcal molt + Bond energy of C = © or, Bond energy of C — C = 80 kcal mol* 53. Answer (2) Given: 2H-C=C-H+50=0540= AH is enthalpy of reaction, HH = (B.D-E) sscurts — (B-D-E)prauts = (2x(Ecy + Ec) +2Ecac + 5Eo-0) ~ (4%(Ec-0 +Ec-0) + 2 (Eon + Eo.4)) = (460.11 +2Eosc +5E0.0) - (8Eo.0 + 4Eo-n) = 4p + 2q + Sr — (8s + 4t) 54, Answer (2) Given 50(8) +4 Hig) Sy 3 |s AN Wa Soy e4nig—] " AH = (B.D.E), stan ~ (B.D-E) cous 4 Ey -(ZEg ct BE. yt Eee) Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456Solutions of Assignment (Set-2) (Level) ‘Thermodynamics AH, |, = 5x + AH ( His a state function) 71 kcal AH, = 5 * 174 koal + [4 x 104 keal — (2 « 147) ~ 8 x 98.8 kcal] — 2 x 83 kcal = 855 kcal + (416 kcal ~ 294 kcal - 790.4 kcal ~ 166 kcal) = 20.6 kcal = 21 kcal 55. Answer (2) N,O, == 2NO, Upon heating, brown colour deepens, ie. NO, is formed. => The reaction is as follows NzOg + AH= NO, The reaction is, hence, endothermic, SECTION -B 4. Answer (2) AU = AH - An,RT Ang =(2-1)=1 AH=-xJ AU = {x + 8.314 T) J/mol 2. Answer (3) B.E = BE pesca) — B-E products) =x + dy + 32 - (4a + 4b) =x + 4y + 3z—4(a +b) 3. Answer (2) n=18=8 mol 2 ge 3488 8 4. Answer (3) 5. Answer (2) According to Hess's Law, U = W + V. Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456 778) Thermodynamics Solutions of Assignment (Set-2) (Level-!) 6. Answer (1) For non-spontaneous reaction AG>0 AH — TAS > 0 AH > TAS 7. Answer (2) 8. Answer (4) 9. Answer (1) AU = 0 ({sothermal process) AU Q+w Q=-w W=-P,(V-¥,) = -2 atm (100 - 50) L = -100 L atm So, Q = 100 L atm 10. Answer (3) AH = AU + APV AU = 0 (For isothermal process) AH = PV, - P,V, = 0 11. Answer (4) 12. Answer (4) Rhombic sulphur is most stable allotrope of sulphur. 13. Answer (2) Intensive properties are independent of the amount of substance present in the system, 14. Answer (2) AH ono = Calorific value * Molar mass 30x 15. Answer (3) Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456