[_ Exercise-1 |] OBJECTIVE PROBLEMS (JEE MAIN) 41,0ut of boiling point (1), entropy (11), pH (III) and density (IV), Intensive properties are : wit (e)1, 1, 0 (Lm, (0) All ofthese 2.Consider the reaction at 300 K H,(9) + C1,(9) — 2HCI(9) aH° = -18540 If 3 mole of H, completely react with 3 mole of Cl, to form HCI. What is AU® for this reaction ? ao (8) -18510 (0) 55510 (D) None of these ‘3.Ethyl chloride (C,H,Cl), is prepared by reaction of ‘ethylene with hydrogen chloride GH.(g) + HCI (9) + C,H,d(9) aH = - 72.340 What is the value of sE (in i), if 70.9 of ethylene and 73 of HCI are allowed to react at 300K. (A) 69.8 (8) -180.75 (C)-174.5, (0) -139.6 ‘4.What Is AU for the process described by figure. Heat supplied during the process q = 100 ki. Tm am V (A) +5040 (8)-S0t0 (C)-150 kd (0) + 15010 '5.One mole of ideal gas is allowed to expand reversibly ‘and adiabatically from a temperature of 27°C. If the work done by the gas in the process is 3 ki, the final temperature will be equal to (C, = 20./K mol) (A) 100K (8)450K (c) 150k (0) 400k 6.What is the change In internal energy when a gas contracts from 377 ml to 177 ml under 8 constant Dressure of 1520 torr, while at the same time being cooled by removing 124 J heat ? (Take: (1Latm) = 1003) (A)-243 (B)-84) (C)-1643 (0-248) 7.The heat capacity of liquid water is 75.6 J/mol K, while the enthalpy of fusion of ice is 6.0 k/mol. What Is the smallest number of ice cubes at 0°C, each containing 9.0 g of water, needed to cool 500 g of liquid water from 20°C to 0°C? aya (8)? (cia (D) None of these 8.An ideal gas is taken around the cycle ABCDA as shown in figure. The net work done during the cycle is equal to: “ov (A) zero (8) positive: (C) negative {D) we cannot predict ‘9. Molar heat capacity of water in equilibrium with ice ‘at costant pressure is (ayzero (©) 40.45 kd K* mot! (8) (D) 75.48 JK" mol 10. cyclic process ABCD is shown in PV diagram for anideal gas. Which of the following diagram represents the same process ? 7 5 cp wm We (a) (8) |p ‘> Aen v y (©) Jal (0)11.A diatomic ideal gas initially at 273 K is given 100 cal heat due to which system did 209 } work. Molar heat capcity (C,.) of gas for the process is : cw 3a (@) 5R © gr (os 12. One mole of an ideal monoatomic gas expanded irreversibly in two stage expansion. State-1 (8.0 bar, 4.0 litre, 300 K) State-2 (2.0 bar, 16 litre, 300 K) State-3 (1.0 bar, 32 litre, 300 K) Total heat absorbed by the gas in the process Is : (a) 1163 (8) 403 (©) 40003 (D) None of these 13.For an ideal monoatomic gas during any process T = ky, find out the molar heat capacity of the ‘92s during the process. (Assume vibrational degree of freedom to be active) 5 z (ay 3R > (e)3R (oar 14.A.925 (C,,.= $R) behaving ideally was allowed to expand reversibly and Sélabaticaly from 1 litre to 32 titre. Its intial temperature was 327°C. The molar enthalpy change (in 3/mole) for the process is (A)-1125R (8)-575R. ()-1575R (0) None of these 15. What is the net work done (In calories) on 1 mole f monoatomic ideal gas in 3 process described by 1,2,3,4 in given V-T graph. Use: R = 2cal/mole K 300K 600K n2=0.7 (A) ~600 cal (8) -660 cal (©) +660 ca! (0) +600 cal A6.Two moles of an Ideal gas (C, = £8) was compressed adiabatically against constant pressure of 2 atm. Which was initially at 350 K and 1 atm pressure. The work involve in the process is equal to (A)250R (8) 300R —(C)400R_ (0) SOOR 17. An insulated container of gas has two chambers Separated by an insulating partition. One of the ‘chambers has volume V, and contains ideal gas at pressure P, and temperature T,. The other chambers hhas volume v, and contains ideal gas at pressure P, and temperature T,. If the partion is removed without doing any work on the gas, the final equilibrium temperature of the gas in the container will be TTyPM +P.) PMT, + Pa, BMT: PNET, PY, +PA¥, PMT, +PAV,T, oy ER OM PV) PY, +PVs PMT +PVATs 18. The maximum efficiency of a heat engine operating between 100°C and 25°C is (A) 20.11% (8)22.2% (25.17% (0) None 19, A heat engine operating between 227°C and 27°C absorbs 2 Kcal of heat from the 227°C reservoir reversibly per cycle. The amount of work done in one cycle is : (A) 0.4 Keal_ (B) 0.8 Kal (C)4 Keal_ (D) 8 Kcal 20. A reversible heat engine A (based on carnot cycle) absorbs heat from a reservoir at 1000 K and rejects heat to 2 reservoir at T,. A second reversible engine B absorbs, the same amount of heat as rejected by the engine A, from the reservoir at T, and rejects energy toa reservoir at 360 K. If the efficiencies of engines A and B are the same then the temperautre T, is (A)680K — (B)640K —(C) 600K (D) None 21,For the reaction at 300 K ‘A(g) + B(9) -+C{g) XE = - 3.0 kcal; value of 4G is (A) -600 cal (8) -6600 cal(C) -6000 cal (D) None = 10.0 cal/K22.The entropy change when two moles of ideal ‘monoatomic gas is heated from 200 to 300°C reversibly ‘and isochorically 9 3en(3m) (8) °F $73) co RH 23) 573) 3 (2) 2PM a73) 23. What is the free energy change (4G) when 1.0 mole of water at 100° C and 1 pressure is converted Into steam at 100°C and 1 atm pressure ? (A) 80 cal (B) 540cal_ (C) 620.cal (D) zero 24, What if the free energy change (AG) when 1.0 ‘mole of water at 100°C and 1 atm pressure is converted into steam at 100°C and 2 atm pressure 7 (A) zero cal (8) 540 cal (C) 517.13 cal (D)510cal 28. What can be concluded about the values of AH ‘and AS from this graph ? 140200300400500 Temperature, K (8) aH > 0,45 <0 (A) AH > 0, aS > 0 (0) aH < 0,05 <0 (C)aH < 0,05 >0 26.1f 3H, of substance X (/) (molar mass : 30 ‘g/mol) is'$60'79 at it’s boiling point 300 K, then molar ‘entropy change for revesible condensation process (s (A) 30 /mol.k (8) ~300 3/mol K (©) =303/mol K (0) None of these 27. Pressure of 10 moles of an ideal gas is changed from 2 atm to 1 at against constant extemal pressure without change in temperature. If surrounding temperature (300K) and pressure (1 atm) always ‘remains constant then calculate total entropy change Syran * SSyenanang) fOF given process. [Given : iz = 0.70 and R = 8.0 3/mol/K] (A) 567K (8) 147K (O16 7K (0) None of these 28. The enthalpy of tetramerization of X in gas phase (4X(g) -+ X,(9)) is~100 k/mol at 300 K. The enthalpy ‘of vaporisation for liquid X and X, are respectively 30 kJ/mol and 72 k3/mol respectively. AS for tetramerization of Xin liquid phase is -125 3/K mote at ‘300 K. What is the AG at 300 K for tetramerization of xin iquid phase. (A) -5240/mot (C)=14.5 ko/mol (8)-89.5 t/t (D) None of these 29. The change in entropy of 2 moles of an ideal gas upon iosthermal expansion at 243.6 K from 20 litre until the pressure becomes 1 atm, is : (A) 1.385 cal/K (B)-1.2 cal/k (C) 1.2K (0) 2.77 cal/k 30, Standard entropy of X,, ¥, and XY, are 60, 40 and 50 JK-! mol, respectively. For the reaction, $41 3¥2+ 9%, abt = -30 to be at equilibrium, the temperature will be (A)1250K (8)SOOK — (C) 750K (D) 1000k 31. When two equal sized pieces of the same metal at Gifferent temperatures T, (hot piece) and T, (cold piece) are brought into contact into thermal contact and isolate from it’s surrounding. The total change in entropy of system is given by Th 1, (A) Cea (6) hy +h? (T+ Ty? (om Saar + (0) cn aT,1,An ideal gas is taken from state A (Pressure P, Volume V) to the state 8 (Pressure P/2, Volume 2V) along 2 straight line path In PV diagram as shown in the adjacent figure. tel bis pb os Volume Select the correct statement (s) among the following (A) The work done by gas in the process A to B exceeds the work that would be done by it if the system were. taken from A to B along the isotherm. (B)Inthe T-V diagram, the path AB become part of parabola. (C) In the P-v diagram, the path AB becomes a part of hyperbola. (D) In going from A to B, the temperature T of the gas first increases to a maximum value then decreases. 2.The normal boiling point ofa liquid'A’is 350K. at normal boiling point is 35 ki/mole. Pick out the ‘correct statement (5), (Assume AH, to’be independent of pressure), (A) AS ann > 100 J/K mote at 350 K and 0.5 atm (B) 3S. saan © 100 1/K mole at 350 K and 0.5 atm (©) AS scan $ 100 3/K mole at 350K and 2 atm (D) 35.2.4. = 1003/K mole at 350K and 2 atm '3.Which of the following statement(s) is/are false : (8) 45 for 2Ns(0) + N(g) i postive (B) 3G,,... 'S always zero for a reversible process in a dlosed system (C) AG* for an ideal gas is 2 function of temperature and pressure (0) entropy of a closed system is always maximized at equilibrium ‘4.Which statement is/are correct : (A) Final temperature in reversible adiabatic expansion Is lesser than in irrevesible adiabatic expansion. (8) When heat is supplied to an ideal gas in an 'sothermal process, kinetic energy of gas will increase OBJECTIVE PROBLEMS (JEE ADVANCED) (C) When an ideal gas is subjected to adiabatic expansion it gets cooled (D) Entropy increases in atomisation of dihydrogen '5.Which is /are correct statement. (A) Wyasear > Wasoema if an ideal gas compression from same intial state to same final volume LG (B) The volume of 1|7= =) remains constant for diatomic gas at all temperature (C) Entropy increases when an ideal gas expanded isothermally. (D) AH & 4S both are +ve for the decomposition of Maco). 6.Two moles of an ideal gas (C. , = 3/2 R) is subjected ta following change of state. A (S00K, 5.0 bar) ae? B pee COS0K, 1.0 ber) = = Sigs se canaie [osaprenicn om The correct statement is/are : (A) The pressure at B is 2.0 bar (8) The temperature at D is 450 k (C) aH) = 1000 (0) AU, = 375R ‘7.In isothermal ideal gas compression (A) wis +ve (B) aH is zero (CAS, 15 +ve (D) aGis +ve B.A piston cyclinder device initially contains 0.2 m? ‘neon (assume ideal) at 200 kPa inside at T,°C. A valve Is now opened and neon is allowed to escape until the volume reduces to half the initial v=-""—~ ‘At the same time heat transfer with outside at T° C ensures a constant temperature inside. Select correct statement(s) for given process (A) aU must be zero (B) AU may not be zero (C)amay be +ve (0) qmay be -ve9.1f one mole monoatomic ideal gas was taken through proces AB as shown in figure, the select comet epion s). (A) Wy = “1496.52 (8) dug ~ 5237.82) (©) AH, = 3741.33 (0) aSgistve 10, Which ofthe following statements) is/are correct (A) Reversible isothermal compression of an ideal gas represents the limiting minimum value of the workdone (Iwl) by the surrounding on the system. (B) In an irreversible process, the cyclic integral of work Is not zero. (C) For thermodynamic changes in adiabatic process. [en 7! p= constant (D) Work done by 1 mole of a real (vander waals) gas Y=b_ [¥=%) V-b y-\! ASSERTION REASON : (A) Statement-I is true, statement-II is true and statemert-LIis correct explanation for statement-I (@) Statement is true, staternent-Iis true and statement: {SNOT the correct explanation for staternent-1 (C) Statement-Iis false, statement-II is true, (D) Statement-I is true, statement-II is false. 11, Statement-1 : There is nochange in enthalpy of an Ideal gas during compression at-constant temperautre. ‘Statement-I1 : Enthalpy of arvideal gas is a function of temperature and pressure. 12. Statement-1 : Due to adiabatic free expansion, temperature of a real gas always increases Statement-II : If a real gas is at inversion temperature then no change in temperature is observed in adiabatic free expansion. 13, Statement-1 : There is no change in enthalpy of {an ideal gas during compression at constant pressure. ‘Statement-IT : Enthalpy of an ideal gas is 2 function of temperature . 14, Statement-1 : Two reversible adiabats can never Intersect. Statement-II : Efficiency of camot engine cannot be one. W--RTIn 15.Statement-1 : Adiabatic process must be isentropic process. ‘Statement-II: 45 = “=. 16.Statement-1 : During irreversible adiabatic ‘expansion of ideal gas entropy must increase. ‘Statement-II : Increase in entropy of the system ‘due to expansion 1s only partially compensated by Gecrease in temperature. (COMPREHENSTON-I A cylindrical container of volume 44.8 litres is containing equal no. of moles (in integer no.) of an ‘ideal monoatomic gas in two sections A and B separated by an adiabatic frictionless piston as shown in figure. The initial temperature and pressure of gas in both Section is 27.3 K and 1 atm. Now gas is section’A’ is slowly heated till the volume of section B becomes (1/ 8)" of initial volume. sm ek gy 28 ar 17, wht wil be the final pressure in container B. (A)2atm_ (8) Batm — (C) 16 atm (D) 32 atm 18. Final temperature in container A will be (A) 1638k (8) 6988K | (C)3274K (D)S1K 19. Change in enthalpy for section A in Keal. (A) 48.3 (8)80.53(C)4.83 (0) 8.05 (COMPREHENSION - 2 ‘The vapour pressure of H,O(") at 353K ts 532 mmHg. The external pressure on H,0 (/) taken In a cylinder fitted with frictionless movable piston initially containing 0.9L (= 0.9 kg) of H,0 (7) at 353 K is increased to 1 atm. Temperature remained constant. Now, heat is supplled keeping pressure constant till 0.45 L of H,O (O)= (0.45 kg) is evaporated to form H,0 (g) at 373K. Carefully observe the diagrams provided and from given data, answer the following questions. “ES Ee ae ea ape 120. sH when system is taken fram state 1 to state 2 (Qoule) ? (A)zero (80.27 (C)27_— (0) 9021. Total change in aU going from state 1 to 3 (k3) ? (A) 75.6 (8)1075.6 (C) 1001 (0) 74.6 22. Total change in enthalpy going from state 1 to state 3 (43)? (A) 75.6 (8)1075.6 (C) 1001 (0) 74.6 123. What is the work done in going state 1 to state 3 toin Joules. (A)zero(8)45——(C) 90 COMPREHENSION-3 ‘Two_moles of helium gas are taken over the cycle ‘ABCDA, as shown in the P-T diagram. (0) None anol & Pai! amt oh 300K 00x” * 24. Assuming the gas to be ideal the work done by the gas in taking it from A to Bis - (A)200R —(B)300R (C)400R_ (0) SOOR 25. The work done involved in taking It from D to Ais. (A)-414R_ (8) +414R (C)~690R (0) +690R 26. The net work done involved in the cycle ABCDA is! (A) zero (B)276R_— (C)1076R"(D) 1904R Match the column : 27. Match Columin-I with Colume-t1 Column - 1 (Column (ideal Gas) (Related equation) (A) Reversible Isothermal (P)W = 2.303 nRT og (P/P,) process (B) Reversible adiabatic process (C) Irreversible adiabatic _(R) PV = nRT process (0) Ireversible isothermal (5) W=~ [Puc Process (Q) W= nc, (7-7) 28.Match the column - I with column-IT ‘Note that column - Imay have more than one matching ‘options in column-II Colume-t Cohumn-1r (A) Reversible adiabatic (P) 5, > 0 compression (B) Reversible voporisation(Q) AS jum < 0 (C) Free expansion of = (R) 45," < 0 ‘deal gasin vacuum (0) Dissociation of (5) 35. aney = 0 CaCO,(s) -+ Ca0(s) + C0,(9) (29.Column I (Cohan (A) For the process ACN) — A(s), AH & AV may be (P) -ve, +ve (B) ACS) + B,(9) > Cs) + y's) (Q) +e, -ve aH & AG may be (©) For the given reaction (R) 4ve, +ve (9) > BG) + C9). Esrenarg = 50 K3/mol at very high temperature AH & AG are (0) For the givenreaction (S) -ve, -ve A(g) === 8(g), at very low temperature 3H & SG may be 30,Column - I may have more than one matching ‘options in cohumn-IT Colume-t (Cohan (A) Reversible condensation of vapour (P) AS yn > 0 (8) Irreversible adiabatic ‘compression of an ideal gas (Q Syren 0 (C) isothermal free expansion of an ideal 92s in vaccum (D) Reversible adiabatic expansion of an ideal gas (Ry as, <0 (S) BS rserany 0 31. Column-1 (Related to process) (Related to system) (A) Fusion at melting point ()aG=0 (8) Vapourisation at boiling point (Q) AG < 0 (C) Condensation at triple point (R) AS > 0 (0) Metting at normal boiling point (S) 4H = AU Column-IT[ EXERCISE — I SUBJECTIVE PROBLEMS (JEE ADVANCED) ] First law : Heat (q), work (w) and aU, aH 1.[n which of the following changes at constant pressure is work done by system on surrounding? By ‘the surrounding on system ? Intal state Final state 4,09) +H,0 (1 (i) H,0 (s) > H,0(9) W)H_O1) + H,O(s) (iv) 3HA(9) + N60) >» 2HH(9) (v)Cac0,(s) + Ca0{s) + CO,(9) 2.The gas is cooled and loses 65 } of heat. The gas contracts as it cools and work done on the system equal to 20 J is exchanged with the surroundings. What are a, w and sE ? 3.The enthalpy change for the reaction of 50 ml of ethylene with 50.0 mi of H, at 1.5 atm pressure is AH = ~0.31 KJ. What is the AE. ‘4.The enthalpy of combustion of glucose is -2808 K) mol"! at 25°C. How many grams of glucose do you need to consume [Assume wt = 62.5 Kg] (2) to climb a flight of stairs rising through 3M (b) to climb a mountain of altitude 3000 M? Assume that 25% of enthalpy can converted to useful work, '5.What is AE when 2.0 mole of liquid water vaporises ‘at 100*? The heat of vaporisation, aH vap. of water ‘at 100° Cis 40.66 KJ mol". G.If 1.0 kcal of heat is added to 1.2 L of 0, in a cylinder of constant pressure of 1 atm, the volume increases to 1.5 L. Calculate AE and AH of the process. 7.When the following reaction was carried out in 3 bomb calorimeter, aE Is found to be -742.7k3/mol of NH,CN(s) at 298 K. NH,CN(s) + 20,0) + N,(9) + CO,(9) + H,0(0 Calculate AH, for the reaction. B.When 1 mole of ice melt at 0°C and at constant pressure of 1 atm. 1440 calories of heat are absorbed by the system. The molar volumes of ice and water ‘are 0.0196 and 0.0180 litre respectively. Calculate aH {and AE for the reaction. '9,Water expands when it freezes. Determine amount ‘of work in joules, done when a system consisting of 1.0 Lof liquid water freezes under a constant pressure of 1.0 atm and forms 1.1 L of ice. 10. Lime is made commercially by decomposition of limestone CaCO, Whats the change in Internal energy when 1.00 mole of solid CaCO, (V'= 34.2 ml) absorbs 177.9 kd of heat and decomposes at 25°C against 3 Pressure of 1.0 atm to give solid CaO. (Volume = 16.9 ‘ml) and CO, (9) (V = 24.4 L) 14, One mole of solid Zn is placed in excess of dilute H,S0, at 27°C in a cylinder fitted with a piston. Find the value of AE, q and w for the process if the area of piston is 500 cm? and it moves out by 50 cm against 3 pressure of 1 atm during the reaction. The heat given tosurrounding Is 36.5 KJ. Zn(s) + 2H" (aq) = Zn (aq) + H,(9) 12. Two mole of ideal diatomic gas (C,,, = 5/2 R) at 300 K and 5 atm expanded irreversly & adiabatically toa final pressure of 2 atm against a constant pressure of 1 atm. Calculate a, w, aH & AU. 13. 4 moles of an ideal gas (Cy, = 15 JK"! mol") is Subjected to the following process represented on P- T graph from the data given. Find out (a), The process is isochoric or not (127°C, 4am) Peat | ram) Te {(b) Calculate q, w, aU & 4H for the process. 14, Calculate the max. work done by system in an Irreversible (single step) adiabatic expansion of 1 mole of a polyatmic gas (7 = 1.33) from 300 K and pressure 10 atm to 1 atm. 15.1 mole of CO, gas at 300 K is expanded under reversible adiabatic condition such that its volume becomes 27 time. (a) What is the final temperature (b) What is work done Given y = 1,33 and C, = 25.08.} mol"! K-! for CO, 16. Three moles of a ideal gas at 200K and 2.0 atm pressure undergo reversible adiabatic compression unt the temperature becomes 250 K for the gas C, is 27.5 is temperature range. Calculate a, w, |AU, aH and final V and final P.17. A sample of a fluorocarbon was allowed to expand to expand reversibly and adiabatically to twice its jume. In the expansion the temperature dropped from 298.15 K to 248.44 K, Assume the gas behaves erfectly Estimate the value of C, 18.Find the work done when one mole of the gas is. ‘expanded reversibly and isothermally from 5 atm to 1 atm at 25°C 19. One mole of ideal monoatomic gas is carried through the reversible cyclic process as shown in figure. Calculate . (a) work done by the gas. (b) The heat changed by the gas in path CA and AB. (c) Net heat absorbed by the gas in the path BC. ae va (d) The max. temperature attained by the gas during the cycle. 20. One mole of an ideal monoactomic gas Is carried through the reversible cyde ofthe given figure consisting ‘of step A, B and C and involving state 1, 2 and 3. Fillin the blank space inthe table given below assuming 21. One mole of an ideal monoatomic gas is put through ‘reversible path as shown in figure. Fill inthe blank in. the table given below f tan f—f S52 Ab 05 aim} 22.0ne mole of » pertect monostomic gas is put through a cycle consisting of the following three Feversible steps. (CA) Isothermal compression from 2 atm and 1 to 20.atm and 1 litre tt (AB) Isobaric expansion 2014 2 to return the gas to the original volume of 10 tres with T going from T, to T,.. 7 —y (BC) Cooling at constant volume to bring the gas to original pressure and temperature. The steps are shown schematically in the figure shown. (a) Calculate T, and 7, (b) Calculate. ak, q and w in calories, for each step and for the cycle. ‘23. The given figure shows a change of state A to ‘state C by two paths ABC and AC for a an ideal gas. Calculate the : (2) Path along which work done is least. (b) Internal energy at C ifthe internal energy of gas. Ais 10 J and amount of heat supplied to change its, state to C through the path AC is 200 J. (©) Amount of heat supplied to the gas to go from A to B, if internal energy change of gas is 103. 24.4 monoatomic ideal gas of two moles Is taken ‘through a reversible cyclic process starting from Aas show in foue. Te vue rt are Yt? and Yo 4. the temperature T, at Ais 270, ealeulate (8) The temperature of the gas at point B.(b) Heat absorbed or released by the gas in each process. Ty (€) The total work done by the gas during complete cyde. Kirchoft’s Rule : Variation of Enthalpy with ‘Temperature 25. The standard enthalpy of formation of water liquid is -285.76 kd at 298 K. Calculate the value of He at 373 K. The molar heat capacities at constant pressure (G) im the given temperature range of H,(9), 0,(9) and H,0 (/) are respectively 38.83, 29.16 8nd 75.312 aK" mot, 26, Methane (considered to be an idela gas) initially ‘at 25°C and 1 bar pressure is heated at constant pressure until the volume has doubled. The variation of the molar heat capacity with absolute temperature isgiven by C, = 22.34 + 48.1 x 10°T where C, in JK"! mot. Calculate molar (a) sH(b) aU. Second & third law & Entropy’¢h thermodynamic processes 27. One mole of NaCl (s) on melting absorbed 30.5 KI of heat and its entropy is increased by 28.8 JK~' What Is the melting point of sodium chloride ? 28, Oxygen is heated from 300 to 600 at a constant Dressure of 1 bar. What is the increase in molar entropy 2 The molar heat capacity in JK"! mol" for the O, is C, = 25.5 + 13.6 x 10° T- 42.5 x 10° 7 29. A heat engine absorbs 760 k) heat from a source at 380 K. It rejects (i) 650k, (il) 560 ki, (ii) 504 kd of heat to sink at 280 K. State which of these represent a reversible, an irreversible and an impossible cycle. 30. Calculate the entropy of a substance at 600 K Using the following data. (() Heat capacity of solid from 0 K tonormal meting point 200K G,,, (3) = 0.035 T a mot" (i) Enthalpy of Rision = 7.5 kd mot", (i) Enthalpy of vaportsation = 3040 mat (Ql) Heat capadtty of liquid from 200 Kk to normal baling point 300KC,,()=60+0.016T —— 'mot! (iv) Heat capacity of gas from 300 K to 600 K at 1 atm C. (9) = 50.0 aK mol, Gibb’s Function 31. Calculate the free energy change at 298 K for the reaction ; Br3(1)+ Chalg)—+ 2BrCiKg). For the reaction aH® = 29.3 1B the entropies of 8r,(/).Ci(9) & BrCI(g) at the 298 K are 152.3, 223.0, 239.7 J mol Kt respectively. 32.Using the data given below, establish that the vaporization of CCI,(/) 298 K to produce CCI(g) at atm pressure does not occur spontaneously. Given : CCI,(i, tatm)-+ CO4(g 1 atm) ; 35°= 9498 JK" mot" AHP, (CCy.g) = 108:7k mal"* 8 AMP, (COL, 0) = -138.3kI mol” 33. Animals operate under conditions of constant Pressure and most of the processes that maintain life are electrical (in a broad sense). How much energy is available for sustaining this type of muscular and nervous activity from the combustion of 1 mol of glucose molecules under standard conditions at 37°C (blood temperature)? The entropy change is +182.4 JK" for the reaction as stated. Heormacriuenl = -2808K) SAA 298K, Scene (80088) =-5737KI/ mal, AG" comeuason (SUCTOSE) = ~6333 KJ/ mol Estimate additional non-PV work that is obtained by raising temperature to 310K. Assume 4,Cp =0 for this temperature change '35. From the given table answer the following questions. _ wow [cue [nee |e femcocumn | ee | wo | ve | 0 Reaction : H,0(g) + CO(g) => H2(9) + CO2(9) (1) Calculate A,Hing (ll) Calculate 4, Ging (il) Calculate 3,Sigq —(Wv) Calculate 4, Eng (v) Calculate Sou FH,O(@) 36, Calculate workdone in adiabatic compression of ‘one mole of an ideal gas (monoatomic) from an init (2) If process is carried out reversibly (b) If process is carried out irreversible against 2 atm external pressure. ‘Compute the final volume reached by gas in two cases and describe the work graphically.3 37.0.5 mole each of two deal gases A(C. = 38) and 5 oc, =) retaken na coeaner ond expanded reversbty ad aiebtcaly fom V= 1 Lie V = 4 Serteg Nominal tomperareT © 300 Fn Saforthe aces eae, ‘38. 20.0 din’ of an ideal gas (diatomic C, . = SR/2) at 673 K and 0.7 MPa expands until pressure of the gas is 0.2 MPa. Calculate q, w, AU and AH for the process ifthe expansion i (i) Isothermal and reversible (ii) Adiabatic and reversible i) Isothermal and adiabatic (iv) Against 0.2 MPa and adiabati (v) Against 0.2 MPa and isothermal 39. One mole of a ideal monoatomic gas (C,,, = 1.5) is subjected to the following sequence of steps : (2) The gas is heated reversibly at constant pressure of 101.325 kPa from 298 k to 373K. (b) Next, the gas is expanded reversibly and isothermaily to double its volume. (€)Finally, the gas is cooled reversibly and adiabatically to 308K. Calculate q, w, SU and sH for the overall process, 40.2 mole of an ideal gas undergoes isothermal compression along three different paths (i) reversible compression from P, = 2 bar and, to P, = 20 bar (ii) @ single stage compression against 8 constant external pressure of 20ber, and (il) 8 two stage compression consisting initially of compression against a constant external pressure of 10 bar until P,, = Pj, followed by compression against 2 constant pfessuré of 20 bar until Py. = Pay Calculate the work (in bar. L) for"tach"of these processes and for which of the irreversible processes IS the magnitude of the work greater 7[Given | R= 0.08 barL/rmote.K} ‘41,Calculate the heat of vaporisation of water per 9m at 25°C and 1 atm. Given aH H,OU]- -28557Kd/mot SHIH, O(g)] = -2418kJ/mal Comment why SHy(25°C)> AH.ap(100"C) 42. Given: 4.4, H at 373 K = 40.639 kd mot G,(H,0, ) = 5.3123 K" mot, C.(H,0, 9) = 33.3053 K" mol, Pressure over 1600 mi of aliquid is gradually increases from 1 bar to 1001 bar under adiabatic conditions. If the final volume of the liquid is 990 mi, calculate aU L and AH of the process, assuming linear variation of volume with pressure. 43. (2) An ideal gas undergoes a single stage expansion against 8 constant opposing pressure from (P,, V,, T) to(P,, V,,T)- What is the largest mass m which mass m which can be lifted through a height h in this expansion? (b) The system in (a) restored to initial state by 2 single compression. Whats the smallest mass'rv' which ‘must fall through the height h to restore the system? (€) What is the net mass lowered through height hin the cycle transformation in (a) and (b) ? 44. Derive a mathematical expression for the work done (on the surrounding when a gas that has the equation of state PV = nT - °* expands reversibly from V, to \V, at constant temperature. 45. Calculate AS? at 298 K of ; (i) NaCI(s) , (i) NH,CI (5) & diamond The values of S® of Na, Cl, NaCl, NH,CI, Ny Hy, diamond & graphite are 51, 223, 72, 95, 192, 131, 2.43 8 5.69 3K"! mol" respectively. 46. One mole of an ideal gas 1s expanded isothermally at 298 K until its volume is tripled, Find the values of 4S, and a5,4, under the following conditions. (1) Expansion fs carried out reversibly. Ali) Expansion is carried out irreversibly where 836.8.) of heat is less absorbed than in (i) (i) Expansion is free. ‘47. The enthalpy change for vapourization of liquid 'A’ at 200 K and 1 atm is 22 kJ/mol. Find OUt 35,4 ane for liquid ‘A’ at 200 K ? The normal Boiling point of liquid"A’is 300 K. ‘A(D [200 K, 1 atm] -» A(g) [200 K, 1 atm} Given :C,_(A,9) = 30,/m0lK, (A, = 40:/mo-K Use sn (872)'= 0.405, 48, Pressure of 10 moles of an ideal gas is changed from 2 atm to 1 atm against constant external pressure without change in temperature. If surrounding temperature (300 K) and pressure (1 atm) always Femains constant then calculate total entropy change (Sym * 'Syonnnang) f0F given process. [Use?7n2 = 6:70aRd R = 8.0,/mol/K} 49. Compute, 4G for the reaction 01,1 atm, 323K)» H,0 (a, 1 atm, 323K) Given that, H at 373 K = 40.639 kJ mot, C, (H.0, 1) = 75.313 9K" mol ,(H,0, 9) = 33.305 3K"! mot, $0. Forthe reaction 2NH, Naas * Ha ‘A graph is plotted between /G (Ki mole) and otal Dressure in atm, the equation of the graph ie P = (AGP AG + 3. When Initial pressure of NH, ls 2 ‘tm using the above data calculate the equilbstum ‘constant of the reaction.(Exercise -1v | PREVIOUS YEARS PROBLEMS ] (tee-t [ veeman ————«&dS “ ‘The quantity required to increase the tem- perature of a body by 1 Kelvin is called - (A) specific heat [ATEEE-2002) (B) water equivalent (C) thermal capacity (0) molar specific heat Even Camot engine cannot give 100% effi clency because we cannot - [AIEEE-2002) (A) prevent radiation (8) find ideal sources (C) reach absolute zero temperature (O)eliminate friction ‘Which statement is incorrect? [AIEEE-2002] (A) All reversible cycles have same efficiency (B) Reversible cycle has more efficiency than anirreversible one (C) Carnot cycle is a reversible one (0) Carnot cycle has the maximum efficiency in all cydes “Heat cannot be itself flow fram a body at lower temperature to a body at higher tem= erature” is a statement or consequence of - [AIEEE-2003] (A) Conservation of momentum (8) Conservation of mass (C) First law of thermodynamics (0) Second law of thermodynamics Which of the following parameters does not characterize the thermodynamic state of matter ? (ATEEE-2003) (A) Pressure (8) Work (C) Volume (0) Temperature A Camot engine takes 3 x 106 cal. of heat from 2 reservoir at 627°C, and gives it to 2 sink at 27° C. The work done by the engine is ~ TAIEEE-2003] (A) 8.4 x 106) (8) 16.8 x 1963 (C) Zero (0)4.2 x 108 In an irreversible process taking place at con- stant T and P and in which only pressure-vol- ume work is being done the change in Gibbs free energy (dG) and change in entropy (4S) satisfy the criteria - [ATEEE-2003] (A) (€S)y, € = 0, (4G)y, p= 0 (8) (AS)y, € = 0, (dG)y p> 0 (C) (dS)y € <0, (4G) p< 0 (©) (Sn, € > 0, (6), p< 0 rh 12. 13, The Internal energy change when a system goes from state A to B is 40 ki/mole. If the ‘System goes from A to B by a reversible path and returns to state A by an irreversible path what would be the net change in internal energy [ATEEE-2003) (A) < 40K (8) Zero (40K (0)> 40K) The correct relationship between free energy change in @ reaction and the corresponding equilibrium constant Kc is ~ [ATEEE-2003] (A) 3G°= RT inc (8) -3G9= RTiNKe (C)aG = RTInKe (D) 3G = RINK Which of the following statements is correct for any thermodynamic system ?. [ATEEE-2004] (A) The internal energy changes in all pro- cesses (8) Internal energy and entropy are state functions (C) The change in entropy can never be zero (D) The work done in an adiabatic process is ‘always zero An ideal gas expan: volume from wey are era 9 vars on oe ace ae work done Is - [ATEEE-2004) (A) -900 ) (8) - 900 k) (€)2710kK) (0) 900 kJ Se enc get eet ee ae [ATEEE-2005] Upmann eae (B) It is a restatement of the principle of ar Co Tea te mr energy (0) It introduces the concept of the entropy ‘The temperature-entropy diagram of a reversible engine cyde is given in the figure. Its efficiency is - (ATEEE-2005} aS (Az (8) 1/4 (C) 1/3 (0) 3.15. 16. 17. Asystem goes from A to B via two processes I and Il as shown in figure. If AU, and aU, are the changes in internal energies in the pro- ‘cesses I and Il respectively, then [ATEEE-2005) (A) aUy = AU2 (8) relation between aU and AU2 can not be determined (C) ag > aU, (D) aU < ay Consider the reaction : No + 3 Hy —+2 NH3 ‘carried out at constant temperature and pres- sure. If SH and aU are the enthalpy and inter- nial energy changes for the reaction, which of the following expressions is true ? (A) aH = au [ATEEE-2005] (8)aH=0 (C) aH > au (O)AH < AU The work of 146 ki is performed in order to compress one kilo mole of a gas adiabatically ‘and in this process the temperature of the gas increases by 78 C. The gas is - (R=8.32moltk-t)- [AIEEE 2006) (A) a mixture of monoatomic and diatomic (8) monoatomic (€) diatomic (0) tretomic An ideal gas is allowed to expand both revers- ibly and irreversibly in an isolated system. IT) is the initial temperature and Ty is the final temperature, which of the following statements is correct - [AIEEE 2006] (A) Ty > Tj for reversible process but Ty = Tj for Irreversible process (8) Teev = irrev (C) Ty = T) for both reversible and irreversible processes ©) Tpirrev > Trev (3H ~ SU) for the formation of carbon monox- ide (CO) from its elements at 298 K is - (R=8.314)k"! moll) [ATEEE 2006} (A) 1238.78 mol! (8) -2477.57 J mol" (©) 2477.57) mot? (0) -1238.78 3 mot! 19. A Carnot engine, having an efficiency of n= 1/10 as heat engine, is used as a refrig- erator, If the work done on the system is 10 J, ‘the amount of energy absorbed from the res~ ervoir at lower temperature is [AIEEE 2007] (A) 993 (8) 90) (cy13 (0) 1003 When a system is taken from state i to state f along the path iaf, it is found that Q = 50 cal and W = 20 cal. Along the path ibf Q= 36 cal. Walongthe pathibfis- [AIEEE 2007) Cy (8) 16 cal (0) 14 cal (A) 6 cal (C) 66 cal In conversion of lime-stone to lime, CaCO3(s) “+ Ca0{s),+ CO3(9) the values of aH® and AS® ‘are + 179.1 kI mol! and 160.2 3/K respec- tively at 298K and 1 bar. Assuming that aH? and 35°4do not change with temperature, tem- erature above which conversion of limestone to lime will be spontaneous. -[ AIEEE 2007] (A) 1008 (8) 1200 (c) 845K (0) 118K ‘Assuming that water vapour is an ideal gas, the internal energy change(aU)) when 1 mol of water is vapourised at 1 bar pressure and 100°C, (Given : Molar enthalpy of vapourisation of water at 1 bar and 373K = 41 kd mol”! and R= 8.3) mal71k™! )will be- [AIEEE 2007] (A) 4.1004 mol" (8) 3.7904 13 mot! (C)37.90410 mot! (0) 41.003 mol"! Identify the correct statement regarding 3 spontaneous process ~ [AIEEE 2007} (A) For a spontaneous process in an isolated ‘system, the change in entropy is positive (B) Endothermic processes are never sponta- neous (C) Exothermic processes are always sponta neous (0) Lowering of energy in the reaction process is the only criteria for spontaneity‘Standard entropy of Xp, Y2 and XV3 are 60, 40 and 50.1 K™* mol” *, respectively. For the reaction, xg + Byp-19yg t= = 2000, tobe at equilibrium, the temperature will be [AIEBE 2008) (a) 500k (8) 750K (c)1000k (0) 1250k Ina fuel cell methanol is used as fuel and oxy- gen gas is used as an oxidizer. The reaction is. CHy0H(N + 20269) —rCOp{9) + 24010 ‘At 298 K standard Gibb’s energies of forma- thon for CH3OH(), H2O(/) and CO2(g) are ~ 166.2, -237.2 and ~394.4 k) mol”? respectively. If standard enthalpy of combustion of methanol 1s -726 k) mol”, efficiency of the fuel cell wall be- [AIEEE 2009) (A) 87% (8) 90% (€)97% (0) 80% ‘A diatomic ideal gas is used in a Carnot engine as the working substance. If during the adia- atic expansion part of the cycle the volume of the gas increases from V to 32'V, the effi- clency of the engine is- [AIEEE 2010) (A) 0.25 (8) 0.5 (©) 0.75 () 0.99 For a particular reversible reaction at tem- erature T, ai1and as were found to be both +Ve. If T, isthe temperature at equilibrium, the reaction would be spontaneous when [AIEEE 2010} T= 1 (8), >T (T>1 (0) 7, is Stimes T ‘The entropy change involved in the isathermal reversible expansion of 2 moles of an ideal gas from a volume of 10 dm? to a volume of 100 dm? at 27° Cis: (ATEcE 2011] (A) 38.3) mol K+ (8) 35.8) mol K> (C) 32.3.]mol K+ (0) 42.33 mot K" 29. _In view of the signs of 4,G* for the following reactions : PbO, + Pb->2 PbO, 4G <0 ‘Sn0, + Sn + 2 Sn0, AP > 0, which oxidation states are more characteristic for lead and tin ? (AIEEE 2011) (A) For lead + 2, fortin + 2 (B) For lead + 4, fortin +4 (C) For lead + 2, fortin + 4 (0) Forlead + 4, for tin + 2 30. The incorrect expression among the following is- [ATEEE-2012] (A) In isothermal process, Wenn = ~ART In Me v, AH?—Tas* RT (C)Ke ewer (8) Ink = 3G, Aan OSes t 31+ A piston filled with 0.04 mol of an ideal gas ex- pands reversibly from 50.0 mL to 375 mL at a ‘constant temperature of 37.0°C. As it does so, it ‘absorbs 208 } of heat. The values of q and w for the process will be: (R = 3.314 J/mol K) (Ln 7.5 = 2.01) [ATEEE-2013} (A) q = + 2083, w = + 208) (8) q= + 2083, w= - 208) (C)q= - 208), w= - 208) (0) q = - 2083, w = + 208) 32. The above p-v diagram represents the thermodynamic cycle of an engine, operating with an ideal monoatomic gas. The amount of heat, extracted from the ingle cycle is: [ATEEE~2013) ny (pore (0) 40,%, (Pv, (ol Bove[ LeveL - Il I JEE ADVANCED J A sample of argon gas at 1 atm pressure and 2: expands reversibly and adiabatically from 1.25 dm’ to 2.50 dm?. Calculate the enthalpy change in this process. C,,, for argon is 12.48 JK" mol". 2. Which of the following statement Is false ? (A) Work is a state function (B) Temperature is a state function (©) Change of state is completely defined when initial and final states are specified. (0) Work appears at the boundary of the system 43.Show that the reaction CO(a) + $0,(g) -+ C0,(9) at 300 K is spontaneous and exothermic, when the Standard entropy 's-0,094 K) mot. The standard Gibbs free energies of formation for CO, and CO are “394.4 and “137.2 mol, respectively. 4. Two moles of a perfect gas undergoes the following processes: (JE 2002] (2) a reversible isobenc expansion from (1,0 atm, 20.0 L) to (1.0 atm, 40.0 L) ; (b) 2 reversible isochoric change of state from (1.0 atm, 40.0 L) to (0.5 atm, 40.0 L) ;, (c) a reversible isothermal compression from (0.5 atm, 40.0L) to (1.0.atm, 20.01) ; (i) Sketch with’ labels each of the processes on the same P-V diagram, (i) Calculate the total work (w) and the total heat change (q) involved in the above processes. (iil) What will be the values of AU, SH and 3S for the overall process ? '5.One mol of non-ideal gas undergoes change of state (2.0 atm, 3.0L, 95K) to (4.0 atm, 5.01, 245K) with a change in internal energy (aU) = 30.0 L-atm. The change in enthalpy (4H) of the process in L-atm (A)40.0 (8)42.3 (C)44.0 (D) not defined, because pressure is not constant (EE 2002] 6.Two mole of an ideal gas is expanded isothermally and reversibly from 1 litre to 10 litre at 300 K. The enthalpy change (in ki) for the process is (A) 11.440 (B)-11.440 (C)0Kd (0) Bk) 7.The enthalpy of vapourization of a liquid is 30 ki mot" and entropy of vapourization is 75) mol" K, The boiling point of the liquid at 1 atm is (A)250K — (B)400K —(C)450K (0) 600K 'B.One mole of a liquid (1 bar, 100 mi) is taken in an ‘adiabatic container and the pressure increases steeply to 100 bar. Then at a constant pressure of 100 bar, volume decreases by 1 mi. Find aU and aH 9.One mole of monoatomc ideal gas expands adiabatically at Initial temp. T against a constant external pressure of 1 atm from one litre to two litre. Find out the final temp. (R = 0.0821 litre. atm K:! mol?) ayt (8) coer (6) Tae (0) Te ” ) ap © 3.0087 » 3 «0.0821 10.A process A.» Bis difficult to occur directly instead it takes place in the three successive steps. cD ssascy=soeu f | as(c+d)=30eu. A 8 AS (B+ D) = 20 e.u. where eau. i$ entropy unit. ‘Then the entropy change for the process AS (A -» 8) is: (A) +100e.u. (8) -60e.u. (C) 100 exw. ()+60eu. 111. The molar heat capacity of a monoatomic gas for which the ratio of pressure and volume is one. (A)4/2R — (B)3/2R — (C)5/2R_(D) zero 12.For the reaction. 2CO{9) + 0,(9) — » 200,(g) ; AH = -560k0 mot In one litre vessel at 500 K the initial pressure is 70 ‘atm and after the reaction it becomes 40 atm at constant volume of one litre. Calculate change in internal energy. All the above gases show significant deviation from ideal behaviour. (1 Latm = 0.1 kd) 13. For the process H,0(/) (1 bar, 373 K) + H,0 (9) (1 bar, 373 K), the correct set of thermodynamic parametes is (ANG =0,aS=4ve (8) AG = 0, a5 = -ve (C)aG= +e, aS (0) AG = ~‘ve, aS = +ve 14, Statement-1 : There is anatural asymmetry between Converting work to heat and converting heat to work. Statement-II : No process is possible in which the sole result Is the absorption of heat from a reservoir and its complete conversion into work. (A) Statement-I is True, Statement-II is Tue, ‘Statement-1 is 2 correct explanation for Statement-I (8) Statement-I is True, Statement-II is Tue, Statemant-II is NOT a correct explanation for Statement-1(C) Statement-I is True, Statement Tris False (0) Statement-Iis False, Statement-II is True115. Among the following, the state function(s) is (are) (A) Internal energy [EE 2009) (B) Irreversible expansion work (C) Reversible expansion (D) Molar enthalpy 16, One mole of an idea gas is taken from a tob along two paths denoted by the solid and the dashed lines as shown in the graph below. If the work done along the solid ine paths w, and that along the dotted line pathis wg, then integer closest to the ratio We/ ws 5 (ae 2020] 00 05 1015 2025 3035 vay 45 $055 60 17. Match the transformations in Column-Z with ap- Propriate options in Column-t1. [EE 2011] ‘Column (Column (A)COxs}+C02(9) _(P) Phase transition (8) CaCO,(s) »Ca0(s)+ C09) (Q) allotropic change (C) 2H -H2(9) (R) aH is positive (0) Pra syle, SOL 1 tte (1) ASis negative 418.For an ideal gas, consider only P-V work in going from a initial state X to the final state Z. The final state Z can be reached by either of the two paths ‘shown in the figure. Which of the following choice (s) is (are) correct ? [take aS as change in entropy and [BEE 2012) was work done] 19.The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in the figure. Which of the following statement(s) is are correct? (pee 2012) (PMT) Isothermal (PaNyT) adiabat (PNT) Vv TN =T 27 (C) Wirsmemat > oaistec (0) SUseeremat > AUscubatic 20, Benzene and naphthalene form af ideal solution at room temeprature. For this process the true statement(s) is (are) [9EE 2013) (A) AG is positive (B) ASyuem iS positive (C) ASpirounding = 9 (0) AH'S Pragraph for Questions 21 and 22 A fixed 'm’ of a gas is subjected to transformation of states from K to LM to N and back to K as shown in the figure Pressure (DEE 2013) N Volume ser The succeeding operations that enable this transformation of states are (A) Heating, cooling, heating, cooling (B) Heating, cooling, cooling, heating (C) Cooling, heating, cooling, heating (0) Cooling, heating, heating, cooling The pair of isochoric processes among the transformatin of states is (A) Kto Land Lto M (8) Lto Mand Nto kK (C) Lto Mand M ton (0) MtoN and N to K23. The figure below shows the variation of specific heat capacity (C) of a solid as a function of temperature (T). The temperature is increased continuously from 0 to SOO K at a constant rate. Ignoring any volume change, the following statement(s) iS (are) correct to a reasonable approximation. 100 200 300 490 soo (A) the rate at which heat is absorbed in the range 0- 100 K varies linearly with temperature T. (B) heat absorbed in increasing the temperature from 0-100 K is less than the heat required for increasing the temperature from 400-500 K. (C) there is no change in the rate of heat absorption in the range 400-500 k. (0) the rate of heat absorption increases in the range 200-300 k 24. One mole of a monatomic ideal gas Is taken ‘along two cyclic processes E oF »G sE and E oF +H 16 as shown in the PV digram. The processes involved. are purely isochorc, sobanc, isothermal or adiabatic, Match the paths in List I with the magnitudes of the work done in List II and select the correct answer using the codes given below the lists. User Ust 11 (PGE 4, 160 P.V,In2 (Q)GoH 2.36 P,V, (R)FoH 3.24PV, (S) FG 4.31 PV; Codes: - r Mm 4 3 2 71 ® 4 3 1 2 © 3 1 2 4 © 1 3 2 4 ‘The standard enthalpies of formation of CO2(9), H,0(1) and glucose(s) at 25°C are ~400 ki/ mol, ~300 ki/mol and -1300 k}/mol, respectively. The (C)-16.11 bd (0) +16.1110Answers Answer Ex-i OBJECTIVE PROBLEMS (JEE MAIN) te zo ab «8 &c¢ @ 8 TFC BA ar wc 0 mC 868A COCO mA mA 98 mc mA mc BD MC mA mo | om mc mp mM COD Answer Ex-ll OBJECTIVE PROBLEMS (JEE ADVANCED) 4 ABD 82 AC] 863 BCD 64 ACD 8 ACD & ABC 7. ABD & BcDO 88 ABD 108 1. we wc 14.4 15. 16.4 7.0 aA 28 mc 21.c 2.8 a0 24.6 23.8 23.8 2. A)-+PRS,B)-+ORS.(C)+ORS,0)+RS 2B. (A)-+5, (8) +PR(C)+PS, (0) +P,R 2 (A) »PS,(B)-+PRS,(C) +0,(0) RS 30. (A) +0. (8) »PS,(C) »PS,(0) 9S 31. (A)-+PS.R(B)-+PR,(C) +P, (0) ORS SUBJECTIVE PROBLEMS (JEE ADVANCED) 4. OW, Ww, (il) =, (iv) w, (W) = 2. Q@=-85J,w= 20); AE =~455 2 03024 (a) 0.47 gen, (b) 0.47 kg. BOE = 75.11 ks © AE= 0900 kcal, a= thcal 7. -741.5k 8. AH 2 AE = 1440 caren % -105 40. = 177 9kJ,we-25Kd: aE = 175.4K ‘41. AE = ~39.03 Kole; q = ~36.5 ki; w = -2.53 kd 12. AU = w= —1247.1 ; AH = -1745.94.) 13. (yes (H) w= 0; q= AE = 6000 J: 4H = 9325.6) 14, -1.683 ks 18 1,= 100K:w=5016K) =O; w= AU= 4.42 KS: AH = 5.37 KL, = 11.8 de; P= 5.21 atm 17. C.,=31.6.4%mat* few=-aoe8K awe ryieues Seviggeevigs feetS72 R273) -32R (273) R273) ‘32 R (273) =32 R (273) 52 R (273) 52 R (273) (2), = 243.60 K; T, = 2436.0, (0) AE = 0; q=—w = +3262.88 cal (8)AC. (6) 170, (c) 105 (8) 600 K, (6) ay * 3000 col: ay, * 1663 cal: cg = ~1800 cat dy, (c)w= ~1200 cal ‘HT, (4,0 (7) =-284.11 kJ 26, (0) 13.064 KJ mot’, (0) 10.587 ks mot” T= 1059K 2B. 21.18.JK" mot (i reverse, (i) reversible, (i) possible 205.08 JK" mot" 1721.84 32. 4G" = 4.3K mot 39, -2864.5KJ 24 kato ()-8.83 Kcalimole.(#)-6.81 Kcalimole, (a)—10.13 CaliKmole, (v)~0.83 Kcallmole (v) $45.13 CalKmole 1663 cal; Total q = 1200 cal, BESERBNR RIP ‘ (a)T,=3058; Vj=18.24L;w, = 1194.72, FATQHL; Ty *420K, w= 1496.52) 37, - 900 calories 38. ()q=— w= 17.54 KJ, AU = 0 and AH = 0; (3) q = 0, w= AU =~10.536 kd and AH = ~14.75 kd (Hi) q= 0, w=0, aU =O and SH = 0 (wv) q=0; AU = w= ~7.14 KJ; SH = ~9.996 KS, ()q*-w= 10.0KJ, AU =AH=0 38, (a) q= AM = 1558.88, AU = 935.33; w (0) w=-2149.7: UB SH=0,q=-w (¢)q= 0, w=-810.62, AH = -1351.03 Jmot” {or overall process q = 3708.59 ; w= ~3583.88, AU = 124.71 ; 3H = 207.85 (AU) = ~ 623.55 J mot’ 40, () 18.424 bar. L; (1972 bar. L: (i) 40 bar. Magnitude of work is maimum in single stage compression 41, AH__(25°C)=43.97 huimol= 2.433 kalgm, AH. (100°C) = 40.62 Kim (gen) 42, AU= 501 J; AH = 90.540eRT/P,_,) BRT (=P) ) BE corms Bele tl (eom—m= S| ape] ( tever-1 JEE MAIN B tc De a a er a8 10500 LARA 138A) ABC 17.0 WA BA aA ac wc 8 cA BB 2D (teva. - J JEE ADVANCED _] 1. OH> 1150 Ra 3. GH’ = -285.4 ki/mal, AG* = -257.2 kj/mat 4. Wwe q=62077y, fd) =o au = 0/58 #0 sc ec 278 © sUs01Weamst=99neam == -& C8 Dt. A887 WA aA 18. AD 16.2 17, A-PRS, B-RS, C-T, D-PQT WAC -ABACD 20.8,C,0 2c ane 23.ABcD 24.4 25.¢THERMOCHEMISTRY Tans0 aannse BNO) + 31, fo) —+ ANCOVA above eq" can be get after 2 RxD +R Q]-3xK RE] 2. 4,H= 0 ; If all the reactants & products have 1 zero 4, H. = aH INCl,9)= > 4H 1 3. Ca0(S) + 3C(S)-+CaC, + CO = 5[-2aH,+aH,-3a4,) AM =~ 14-26 + 152 = 112 per mole for 1.28 Kg = 112 x 20 = 2240 Kcal aH, 3 =-AH,+ 2 -F aH, ar | 50x0.1 4. HCL= NaH = “So = Sx 10Mole 9. Hr = 1 Mole; OH = 0.75 Mole 3H = 0.75 x(-57) Hear enolved = 57 x 3/4 Q 24.25 3x jogp = 12610. in One 126 4 AuBrj+4 HO)» HAC), + 4B permole => oa aH = -28 4 36.8 = 8.8KCal/mol But aH = 0.44 K Cal 1 = 2.5 x10°KI/Mole 044 os 5. HABOH oe ge OM % dissociation = 5% bd Th He A +B OH —_ H,0 + BA ad EG vend ~ EQeead ~56.1= AH xa 57.3 tad Stone nL butene 3 iSa*12 30508 ‘AM,-AH,> 0 ® 6 C (graphite) —» (diamond) ; aH, - aH, FQ a6 ~ Equen7 19 t= 2- butene —+ 1- butene AM AK > (69 AH,- aH, >0 . H =~ 647 + 649.8 = 2, =055 = aH = - 647+ 649.8 =2.8 = AH,~ AH, = 2.8 and i 9AH,+5AH,=0 7. H+ 50,» #0) =H, = 1.0 and 4H, =1.8 12, 25 = (4x +y) ~ (3x + 84 + 103) 0 = 0+ H,0() —+ H,0 (1) 62 and ~ 3 x+y = 162 and ~ = Y y = y=57.85Ht ; ©, —+0H(g) ; 42 ....(1) 13. I H, (9) + 5 0,(9) —oH,0(9) ; -242 H,(9) —»2H(g) ; 436 oof) 0,(9)—» 20(9) ; 495 seul) (2) ' (2) Eqe---3 + 5Eq 4 Eq 2 495 Ay 242 + 436 + —— 7 7925.5; True 1 1 (b) ;Ea 3+ 5 qr 4-Eqrt aa 20 38 9523.5, te (c) H,—> 2H; AH = 24,4 (H.9) 436 A.H(H,9) = “> = 218 ; False (0) First reaction is a, = 4, H(OH,9) = 42; Tue “On0 ‘AH =H (cyclohexane) - H(Benzene) = 156-49 AH = 3x(-19) + RE = RE=- 156-494 (3119) = 152K/ Mole 15.4 ‘A(g) + B(g) -» C(g) + D(g) Ang = 0, aM = AU + AngRT sH= aU 16. B Ca(OH)(s) + Ca0(s) + CO,(9) aH = 176K) ang=1 AH = AU + angRT AU = sH-ang RT = 176 - RT = 176 ~ 8.31 x 107 x 1240 = 165.6 kj Energy unit Cal>3>erg 16.8 CAH, (0) + 18/2 0,(9) + 6C0,(9) + 34,0(7) (AH = AU = AngRT (~3/2 x 8.31 x 10° x 300 7A kj = 3.74 kj 19.8 CH,(9) + 20,(9) + CO,(9) + 24,0(1) AH = 10 kcal 4gm 2.5 kcal 16 gm... G716 = 10 kcal 20. ¢ NH,NO,(s) -+ N,0 + 2H,0(1) aH = -37.0 ki/mole 2.5 gm NH,NO, = 2,5/80 mole: Heat evolved during heating of 2.5/80 mole 2.8/80 x 37.= 1.161. me Ca0{s) + H,0(1) > Ca(OH), (s) AH = - 15.26 kCal ~15.26 = abt? Ca(OH),(s) - aH1®Ca0(s) ~ aH. 2H,0(+) = AH9Ca(OH), + 151.8 + 68.37 = aHeCa(OH), = - 235.43 KCal 22.8 H,0(s) -» H,0(1) aH>0 2a.D ‘heat of formation may be +e or -ve it depends, ‘on the process of the formation of compound. 8 ‘The heat of combustion is always negative except N, 8 F,. c HA+ OH: +H,0+ A+, Hr + OH +H,0+ a, HA + OH: +H,0+ A +4, HO | +H + OH -q, HA oH +A +a,-a, aH =~,26. BaCl,(s) + (2a) + BaC!, (aq) aH = BaCl,.2H,O+ ag. »BaCl, (aq) sH= +b B2Ci,(s) + 24,0 BaCl, .2+,0 sH=-a-b 27.8 T,=T, ‘As the no. of m,, changes heat evolved changes but temperature rise remains same, 28.8 29. 30.8 H,SO, + 2NaOH -» Na,SO, + 24,0 1 mole B= 2Gm. Eq. Heat Evolved .7 x 2 = 27.4 KCa 31.8 A, + §/20, (9) + 3C0,(g) + 3H,0(1) DH = ~40041/mole 4000 kj. 2 x 10° kj... wt. of cyclo propane = 2100 gm =24kg 32.0 SH eee (2) = 80 x 18 = 1440 Hyun (0) = 45 * 20 = 900 Hiren (€) = 90 x 30 = 2700 AH, (0) = 60 x 45 = 2700 Hye, (e) = 45 « 30 = 1350 ©. 33.8 More calorific value better will be the fuel. SH cen Calorifc value = “oem wae NH,OH + CH,COOH > CH,COONH, + H,0 AH = ~ 10.5 kCal NaQH + CH,COOH -+ CH,COONa + H,0 aH = ~ 12.5 kCal NaOH + HCI + NaCl + H,0 aH = = 13.7 kCal SH dissociation of CH,COOH = 13.7 ~ 12.5 = 1.2kCal 710.5 = -(13.7 -1.2-y] 10.5 = 13,.7-1.2-y Y= 12.5~ 10.5 y= 2kCal 35.8 O-—O SH =IC=C+EH-H-EC-C-2EC-H = 611 + 437 - 346-2 413 = 1048 ~ 1172 124 ki/mole Iyely one abso 22 1 x 1 yy x He) = 50= DRH-H + > EK OX DHX x i = Farms pea e i = yP- 2-5 P= 100K) Bond energy of H, = 2P = 200k) 37.¢€ CH, + 0,» 2C0,(9) + 24,0() AH = -1420k) 1 Taq “355 = 0.25 mole BSB KY essesessernee Volume at S.T, P = 0.25 x 22.4 = 5.6 lit. 38.¢ HINO, + KOH + — KNO,+H,0 meg.cx 100 3005 if KOH Is limiting than heat produced = 57.3 323.30 «1.7134 meq of HNO, = meq of KOH 100 x C= 30 c=3/8-03Mc 3C,H,(9) + CHC") AHO = AH,°C,H, - 3 5HC,H, = 85-3 230 85 - 690 = -60Skj/mole a) @ @ AH = ~ 295 litmole Cu(g) + (9) + Cut(o) (2) + @) +3) SH = - 446 + 745-295 = 44) o Cur(g) + 1(9) + Cul (9) AH = ~ 446 ki/mole Cu(g) + Cur(a) + € AH = 745 ki/mole 1g) +e 4b 41.0 For solubility magnitude of hydration energy should be greater then lattice energy. Therefore ans will be PBR. 42, (i) As atomicity mereases ; Cy increases (ii) for maximum temp = H, and O,react completely reaction is in closed container => volume = constant 2H, + 0,—42H,0 x x o 0 x Heat = 4,U= - 57.8 «2x In container after reaction 2x mole H,O and 4x mole N, will be present = {2XC,(H,0,9)+4xC,(N,,9)) AT # 57-8x2« x10° => (113 - 2) +2 (8.3 -2)) AT = 57800 => AT = 2639.27 = T, = 2639.27 + 298 = 2937.3K (iti) Close container => Constant Volume (= because : w = 0 (Rigid vessel) q= 0 (Adiabatic) => abo “8 H, + C1, + 2HCI AH = ~ 182 182 = TH - H+ ECI- Cl 22H - Cl = 430 + 242-23H-C1 SH- Cl = 427 kj/mole 4.8 Heat of neutralisation of HF is > 13.7 because the hydration energy of Fis very high. an When strong acid & strong base reacts heat of neutralisation remains constant. 47.8 meg. of N@OH = 100 « 0.1 = 10 1000 meq. = S7 kj 57 1omea. = 325 as.0 C{s) +2H,(9)-+CH(g)_ AH = -74.810 H74.810 = ANG, C(s) + 2EH-H ~ 450-4 2718 + 2 438.4 ~42C-H WuC-H~ 718 + 870.8 +748 ‘EC -H = 416 kj/mole x10 0.5710. 49.4 H,0,()»H,0(0) + 1/2. 0,(9) - aH = -23.5 kCal H(9) + 1/20,(9) +#4,0() AH = ~68.3KCal /mole Eq. (2)-(1) H, + 0,(9) + H,0,(1) ‘AHS = -68.3 + 23.5 = ~44.8kCal /mole (2) 50. A 2H+H, aH = -104 EH-H = 104 EH-H = 104 KCal[Exercise-u | MULTIPLE CHOICE PROBLEMS(JEE ADVANCED) 2 Arrhenius equation ; K = Ae-t**" Kirchaft’s Equation 4(a,M) = 4, Car AG < 0 for spontaneous (D) Assumed to zero not unity Internal Energy depend on only temperature = If temp. Is constant than dU or dE = 0 ‘Thermochemical reaction equation does not Give information about ,G or spontanity A.M does not depend on the manner cause it is the state function. Url) —> UL) + 5 F,(9) A.M = A HiU.9) = 4 AKUR) = 128-22 = 106 o AHR Ey, 1 > Ey, 9 106 + = x37 2 = 124.5 KCal /Mole o 521 KY/Mole Enthalpy of formation : follow the definition Follow the theory 10. uu. 12. 14. 15. 16. 7. Pose, < Pg (Stability) = Bxothermic 3U0, +0, —+ U0, ~ 76,01 = - 853.5 - (3x 4 H(UO,) 53.5 + 76.01 3 = AH= = ~ 259.16 Kcal /Mole € (diamond) ; AH + 0 Solid —» liquid Endthemic? 4H > 0 AHS, HOH = -670.48 KCal/mole chon + 30,69) = 26049) + 34,00) stead + ang RT SU = aH ~ ang RT = -670.48+ RT = ~670.48 + 2 x 10° x 298 = = 699.28 cal Ifan,>0:35>0 Kireat?’s equation 6(A,H) = A,C,dt = AH= AU + AngkT Sac a Asef Stable state had zero standard molar enthalpy N, +0, —$2N0; 4,H>O N, +20, —52N0, ; 4,H>0 Endothermic reactions are favourable High temperature.18, (diamond) +0, C0, ; - 94.3 (Amorphous) + 0,—+CO,; - 97.6 (diamond) —s (amorphous) ; 4, AH = -94.3 497.6 =3.3KCal /Mole 1 for 69 C=; Mole C 33 AH= > 65 KCal 19. H,0 (1) —» H,0(9) = 18 x 0.62778 = 4 H(H,0, 9) - 4,H(H,0.1) = A,H(H,O, 9) + 68.3 = AWM(H,O, 9) = - 68.34 11.3 = -$7.0KCal 620 905 6 +E 3 Ee = 80 26. To Keep the temp. constant HH overall = 0 Let x mole 0, and y mole steam 29110 x2 = 132y 20. 1s) —91,(9) aH,- aH, = aC, (TT) za) x no, AH, ~ 6.096 = (0.031 - 0.055) j599 «254 32-4 Y Meee ‘AH, = ~ 0.3048 + 6.092 n ' =5.78 na > gs hess 21, Acetic acid ; weak acid (Less than 13.7) ‘And HF is the exceptional case having langer >, He 7 value for Heat of neupralization than 13, 1,0 (5) —» H,0 (0 ; 1.44 Kal 22. (i) True las (ii) Due tocont. volume it measure AU For 279—» —g x27 = 2:16 Gi) an=0 > aH= AU (iv) False (due to involve ment of R.E) 23, Case; H* = 0.1 x 100 x 2 = 20m.eq. OH: = 0.1 x 100% 2 = 20m.eq. Case IT; H = 50 x 0.1 + 2 = 10 m.eq. OH = 100 x 0.1 = 10 meq. = 24H, = AH, aH, = 274 cal; AH, = 137 AT, = AT, (Because amount of substasace in case I ts double than case I) 24, 1 True 2 True 3 True 4 True 5 False 25.Exerc! (JEE ADVANCED) 1 1. Ng) + 2H) + C(s) + 50,() —> INH,CONH,(s) 7 ones auase 7.8344 “3 * 2% 1000 = 7324.8 2. By Eq (1) ~(2)+(3) a w(s) +e(9r) —» we(s) AH? = ~ 837 + 1196 - 393.5 45 3. gH 3(-393.5) - 3x (-110.5) - (-822.2) -26.8 KI/Mole 4, CH, +20,(9) —» €O,(9) + 24,001) AH 2x (-241.6) + (-391 = B05.8KI/Mole = (76.2) 1000 For sag Mole CHy Heat evolved 1000 = 805.8% Sy a 73597 x 1010 14000 = ay Mole 14000 Total energy produced = 2658 x10! 38 = 641,58) Total energy used = 20 x 26 = S20) 641.58-520 % waste = 100 641.58 8.05% a. 2658%11.2«1000 58 2658» 1.21000 '58* 20000 6 Energy formed = no. of days = = 25.66 days 10. AU= JH= AngRT = 30.64 - (=z) 1000 = 27.905 K)/ Mole For 7.8.9 ° 0.1 Mole benzene ‘aH = 3.08440 = vit 3.08410" wo tw SHO 514 Sec. 12x05 1 € + 5 0, + C0; - 24 kcal/mole 10s 1 1 C+ 5 0,—» C0,; ~ 95 + 24 = -71 Keal/mole Heat evolved in first reaction = 24 Keal Heat evolved in Second reaction = 71 »2y 24-471 x 2y = 75, Sl Ve 73 v= 0.359 Mole total O, Mole = 0.5 + 0.359 = 0.859 mass of 0, = 0.859 » 32 = 27.49 AM), .-22:123 KCal ‘CaCl, (ag.) + Na,(CO,(29.) + CaCO,(s) + 2NaCl(ag.) overall reaction Ca,+ (2q.) + CO,*(aq) —+ CaCO,(s) 288.5- (129.8 - 161.65) NaCl + H,0; 1) NaOH + HCl» NHCI + H,0; = 12270 ) From €q (1) ~ ¢ NH,Cl + NaH —> NH,OH + Nact => AH = ~ 13680 + 12270 == 1410 Cal12. CuSO, + 2g. —» CuSO,(29.) 5 CuSO, . SHO + 0g. —> CuSO,(ag.) ; 2.8 15.9 CuSO; + CuSO,.5H,0 v7 BN ™ OH penn =~ 15.9 - 2.8 = 18,7 Keal 23H + KOH |» | H+ OH —5H,0 = ~ 13.6810 + aH, = -2480 = AM, = 11200 Cal 18, = 11:2 Kea 14, HCI (9) —> H+ (aq.) + Cr (2a) AH (HCI, 9) = (0+ (~ 167.44) ) ~{- 923) = 74.1443 / Mole 15, At Constant volume 1 evolved = 17.7 5 = 8.854) For 0.01 Mole = eae — 19. AU=a= Do, 7 ~885K0/Mole ‘At Constant Pressune aH=q= a U+ anat CH, + 20, —-» COs 24,0 (1); v= wag 2283142300 ane 1000 = 2889.98) / Mole 16. CH, = xmole CH, +20,» CO, + 4.0 (1) q = 1260 Cal/k x 6.667 = 840 Cal ‘AHesnaseun (CH,) = ~ 215 » 1000 Cal /Mole 0 CH,(mole) = 355 jg9p 7 9.004 mole for total mole ont > n= oe Py= RT > n= ae 740 pt 2. ntotal = _\760/ _ = 0.0397 0.04 0.0821 298 0.004 % Mole ot CH, = “5 5g *100 = 10% 4.18 Be 596 KI by 1.92 g of CH,OH 43.596 4.2 « 202K) + +2000 «4.2 coma coxons ('32) saat = 728.6 ae HN po 1” NA Nae 10" = 48, +8, aH dE =~ 120.08 ki/mole (0) —» 2H (9); 104.2, (3) (ea) 5 171.8 et 9) —>(c9) + 4H(g) 5 ? 396 +03) (g) —»2Cicg) GH(g) ; 676 ..(4) Far hoot formation 2C(s) + 3H,(9) —» CH4(9) ~ 6g (5) = 2x (2)+8x(1)-(4) => ANG H,) = 171.8 « 2 + 104.153 - 676 1 KCal / Mole AM (GH) we Xe (6) + 36a) ot End an From (3) E.a= —4- = 99 => ~ 20.1 = (2171.8) + (3x 104.1) -E, =e. < =82 KCal / Mote CH, = CH, —» (CH,~ CH, )n AH mE. 2 E. zim Forn mole a,H = - 720 For 1 mole q,H = - 72K)/Mole= CH, —» 6C(g) + 6 H (9) ; $506 then 3 1 22, AC) + FH (9) + 5 Ny (9) —» CHC! 3 5506 = IR.E] + 66, + 3E... + 3E, GEM ie —ocp ame 2 MTB ©," — 4c) 7718.68 03) = Ren 23.68 Nilg) —+2N(9) ; 945. Hi(g) —52H(g) ; 435:: 27. RE 143 From Eq. 2x3 + 3x5 3 CH, —> 209) + 609); aH, CCH,OH (1)+ 5 0, (9) —s€0, (9) +24,001) (24719.65) +(34 435.14) +83.68= AH a. He (195.5) 436.+6,..46,.,) > 2828.4 = 6E,,,, + E,.c= 6 x414.22 +E, ~{3-fo.0}- 43+ 3e. ol = (Eec= 343.08 = { (40.6 x2) + 4E,,,} 1 3 ‘After puting the data Former 2x 245 244 5 x(5)-u(1) AH = ~66.97 CHIN —» 2(9) + 3H (9) + N(Q) 2476.94 = 2476.94 = BE +E c+ EL 1 2476.9~ (3 x 414.22) 343,08 78 Na(S) + > F, —» NaF(S) 5-571 5 fio [= = 80 2. ¢H,+ $0, —92c0,#H,0();-312KCal 5 Na(g) F(9), = 312 = [2 x(~ 94.38) + (- 68,381) - La AMCH,)] => A, H(CH,) = 54.86 Kcal / Mole |e |» > AC) +H, (9) —> GM, | $4.86 => 54.86 = [2 x AH,., (c) + E,_,]- Nav + F- ere) S Wis4ses 60+ gh 900-571 > Ere an fhe) - 2.98.68 = AH =—35210/ Male = foes 24, HC-G— CH, (mol formula C,H,0) 1 ll 29. Cs(s) + 5 Cl, (9) —» CsCl (9) ; - 388.6 243 , (B) —» CHO Joe fe ° 3e1s) + 3440) + 4 1 csia) ag) AM = [3 x718) + (3435.8) + 5 x 495) = UG x 413.4) + (2 « 347) + 728) [> 348.3 = 1935 oe 25. CM, ~ S - GH,+S(9) —9C,H,-S -S~ C,H, 201.9 ~ (~ 147.2 +222.8) = - 277.5 AM -E. = 2775 30. X= DE 2775 = 618.7 (05 + 159.5 - 96 - 20.5 - 28.75 75, 26. 2C(9) + 6H (9) —»CH. 2C{g) + 4H (5) —> CH, S€{a) + 6H (g) —s Ge - rom eq. 2839.2" GE, >E...E,.¢ = 373.98 (Hg0) = 90.38 K0/ Mole 2275.2 = 4B. + Ee. Epc = 631.72 1 32. Hgo + Hg + 50, (9) a= - aHcostP Heat Let n mole Hgo get decomposed A184 3 90.8 xn = 41.64 = SO 41.84 mole of Hg = “Gog => massof Hg 84 200.6 90.8 = 92.4359 const. volume eat b. At 1 R3dx298 1000 ) => 89.561 «n= 41.84 ALks * 39.561 a = mole of Hgo = mole of Hg x 200.6 = 93,719 232, Kirchot's Eq 4M, = AKT, = 4G -T) At ath, == 26K); a,Hr@ 35.110 AG, #(3475.3 + 2425.5)-(106.543428.9) = 65.77 AiG = 0.0857 13 *'26 ~ (-35.1) = 0.0857 (T, - 298) \ * ooas7 16 298 + 106 = 404K = T,-298 =T 34, To Keep the temperature constant 4H overall =0 Let x mole 0, & y mole steam = MO x2 x x= 132 xy i = ip 708 Fy Me 06 o % oF 0, (by mole ) = 7-5 *100 =e 237.5 % of steam (by mole) = 62.5% AU = oH= aU + anRT 35a) () q=af eT =aaT , b (ge f@srbTeT sagt + Sc-1) (ina = fo arbT+CT! +aT aT ® € anagts 3OP- T+ GT + 3 " aor) 5; b= 15x10 = 5 (500 ~ 300) = 1000 b Gaea(T,-T) + 7-17) 15x10 * = 1000+ (20000 - 90000) = 1000+ 12 = 1012 12 1012 % error = 100 = 1,1858% 36. Fe,0, + 2Al —5Al,0, + 2Fe 3H = aH (AL0,) 4H (Fe,0,) = = 399 - (-199) -200 KCal / Mole Fuel value per gm (for given nx 1 mole Fe,0,,2 mole Al) ‘Total mass of fuel = mass of Fe,0, + mass of a = 16042427 = 2149 fuel value per gm = 5 = 0.9346 KCal/g (102222) Total volume ot fuel = | ¢> +35 Jee = $0.77 ce Fuel val 7 = 3.94 kcal uel value per cc = 097 5 “al fee u 37. In single breath 0, contain = 448 x Fa5 ml ©, Contain inhaled per M minute =AAR IIIS 100 AABx 16x15 0, exhaled per mehute = 3m HOS ig) n HBnlSeS 0, remain = 5, — (21 -16) = 99 CM O#120, —p12C0, +11H,0 “8n18%5) xiby moleof 0, M inhaled = ( 100 x 1000 0.0821 = 300 Pv=nRT ‘= 0.013642 mole in one minute In one minute Sucrose burnt =mde per day sucrose burnt = 2460 = 1.637 mole energy evolved = 1.63 6000 Ki per day = 9822 K)/day = 9,822 MI / day . Let the of HA = xeq & HB = yea. reacted reacted =369x+29y=39 x+y = eq. of NBOH xtyel 10 25 + S0, —+ 80, + 94,0 (1) ...(1) HO) —> H,0(9) (2) 5 ~ 57.59 - (-68.32) = 10.53 1 co + 50, + coz (-26.4) = ~ 67.64 ....3 149%2-8. 3569.4 x = ~ 1302.7 + (9 10.53) - 8 x(- 67.64) =~ 665.81 = \rHKI/Mole (3) 5-94.05 = mass of octaine = 3.785 x 10x 0.7025 9 = 26599 2659 = [14 Mole = 23.325 mole Heat evolved = 666.81 » 23.325 = 15553.3Kcal = 15.55 Mcal 40. C,(9)+ 20, (9)-+2C0,(9) +34,000 a? = 1559.8 K) G)HA(g) + 30,(9) + 2C0,(9) + 21,001) SH? = -1410.9 Kj/mole CH #CH + 0, + 2C0,(g) + H,0(1) BHP = 1299.74 cx,cHo + 30, -+2¢0,(9)+ 24, 0(1) si 4 1192.3 Ky/mole -1559.8 =23H°,CO, +3aH", H,0-aH®, CH, = 2(-393.5) + 3(-28! eyeeen, = 787 - 857.4~ aH SHC, = -84.6K) 2C(5)+ 3H(G)+C)H(9) at? = -84.6 84.6 = 23H" (8) + 3EH-H-[6Le-+ TC-C] 6x + y = 2x716.68 + 3x435.94 + 84.6 1433.36 + 1307.82 6x +y = 2825.78-----(1) Ee -H= 454K) 6 x 454+ y = 2825.78 y= 2625.78 - 2724 c-C = 100K) ‘Similarty other part can be calculated. “CH, a. SG) + 4 (0) 9 EF -Cc=CH, H ar = ((5x171) +4 x6.) (8 rEg + 2E +26 = (S171 + 4° 104) - (8 » 98.8 +25 147+ 2 «147 + 2x 83) = 1271 - (1250.4) = 20.6 KCal 42, Desiredeg.C( grap) +2H,(9) + aH given CH,OH (1) —» CH,OH (9) ; 38K) Hy(g) —> 2H(g) ; 218 x2 clorap) —» (9) ; 735 0, —» 20(g) | 5249 x2 1 7 0,(9) —oCH,OH (1): aC soatC) +2» Bae Heo 0} -{(4H (CH,OH,I)#3E,., Ec. + Eon? 1 = (TAS + 2x (218 x 2)+ 5 x (249 «2)) = (38 + 3 « 415 + 356 +463) =~ 266 KI/ Mole 43, XeF, 9 Xe + P+ P+ F AH =4 x E,,- CIE, + EA +E, 234 x4 - {279 + (85) + 38) = 136 + 279 - 85-38 = 292 KCal / Mole XeF—> Xe'+ F + FF Y, fo» f= p> Xe(g) + F(g) +2F(9)+F. 44, NaCl (s) ——» Nar(g) + Cr(9), AH = 772 Na: (9) —¥'Na" (aq) AH= - 390 OG) + Cr (ag.) AH = x NaCl (s) —» Na* (aq) + Ch (aq.); AH =x + 772 390 NaCl (s) —» Na*(aq) + C(aq) ; + 772-390 X+ 772-390 ~ 384K) / Mole * aH=x 2ox=-2+390-772= ‘Simritarty For I (9) — T(aa) AH = +24 390- 699 = ~ 307 KI/Mole 45. Elerobve oxidation C,, H,,0,,+120,—p12C0,+11H,0:4H = - 5645, ~ 5645 = 12x aH(CO,)+11x 4,H(H,0) = AH (sucrose) = S645 = 12 x (- 395) + 11 » (-286) - AH (sucrose) = 4740 ~ 3146 - 4H (sucrose) = AH (sucrose) = - 2241 yy H,O,,+ H,0 —» 4C,H,0, (lache wod) atte 4x aH (CHO) =AH(Sucrose)~ 44 (HO) = 4 » (- 694) ~ (- 2241) - (- 286) = - 2776 + 2241 + 286 = ~ 249) Advantage of energy = 5645 - 249 = 5396 K) 46, NH,(g) +H +(9)—» NH."(9) 5 A.M = ?---(1) NH,CI (s) —» NH,*(Q) + O° (9); SH = 683.....(2) H—> H+ (9); AH = 1310 ...(3) C4 ah = - 248 HM, — 5218 i, 124 From above eqn From 2nd eq" 683 = a H(NH,",9) + aH (Cl 19) aH (NHC) From (4) & (6) G, —+ 20-(9) } aH = =-s72 2 348 +124 -5 SAH (Ct,9)= 7 = - 286 => 686 = AH (NH,*, 9) - 296 - (- 314) = AH (NH,* , 9) = 686 + 286 - 314 = 655 From (3) & (5) H, —+ 2H + (9): 4H = 1310x218 = 2838 2838 AM (HY, g)= > = 1419 = forieqn AH = a HCNH,' 9) ~ AM (NH, @) ~ AH (HY, 9) = 655 - ( - 46) ~ (1419) = - 718 K1/ Mole 47. CH, = CH- C= CH, + 70, —» 5CO, + 4H,0 cH, =; AH = - 3186 K)/mole AH =-3186=5 4H (CO,)+4.4,4 (H,0)AMMsoprene) = = A.H(soprene) = 3186=5,(-393.5)+4 (-285.84)- A H(lsoprene) 1967.5 - 1143.36 + 3186 = 75.14 ~ 3186={IR-E1 +86, ., +26, ,+26,..+2 E..) +76.) uu = 3186 = { IRE] 8x413 +2 615 +2 x 348) +7» Ey.)) ~ {10 x Ec. 9 + BE.) oQ) (C,) +0, —» 5 - 393.5 ~ 393.5 (718.4 +E, =0)- Ee.) (2) 1 Hy + 3 0, + H,0 (I); - 285.84 = 285.84 = (435.8 + fea (En) sf) + (Heat of atomisahm of C(s) Ego 1111.9 «5 and Eglo > AE gt ~ 1443.28 «2 STE 5 g~ 46. om 8446.06 ¥5:(4) Putting the values of Eq”. 4 into Eqr ~ 3186 = JRE] 5230 - 8446.06 = IRE] = - 3186 - 5260 + 8446.06 = 30.06 RE always in - ve 30.06 HOH —+ CH, -0-CH, a=? CH, - 0 CH, 5200, + 34,0; - 48 = 34B = 35 4, (H,0) +2 4H (CO,)~ 4H (cH) = 3x (-68)+2x (- 94 )- 4H (CH,-O - CH,) AM(CH,-O-CH,)=-68, 3- 942 +348 = - 44 for rst reaction A H= a,H (CH,OCH, )~ 4H (C,H,0H) 44-(- 66) = +22KCal/ Mole 1 49, 2H + 50,» H,0: A.M, l H, + 50, +H: 4,H, ;- 242K) H,—52H 436 A.M, =~ 436 - 242 = /- 678 4H, -678 = Tyan 7280 AM (FeO,) = 390%4 AH, + AH, + (2 x490) + AK, + Le x 2x 1092 = 390x + 7 = (760 + 1560) + = (460 + 1560 + 2960) + ( 2x490) 4 x (844 - 142) ~ 18930 2320x 3 10s60% 3 = 1092 = 290% + ~ 18142 14050x = 1092 = 1514 3 st42 14050x 3 = = 15142 - 1092 = 14050 =xKs3[Exercise -1V_[ PREVIOUS YEARS PROBLEMS] [ LeveL -1 I JEE MAIN ] 7 A 8 H,0(1) +H, + OFF", SH = 57,32k CH, = CH,(g) + H,(9) - CH, - CH,(9) 1 1 = CH(9) +H I~ CH «10, +40 aH = Sreactants— Y products Hie30, HOU = 42C-H + IC = C+ TH-H AH = -386.2Kj = 63C -H-EC-C 32 = 3H p, OF 3H, H,0 24x 414 + 615 + 435 Pou anon S sys 2062 76(414) -347 = -228.88 Kj. 1050 - 1175 ac 2 gt 2 A =F) The Enthalpy change of the reaction does 349 {Sos NG" CHy nat depend upon the nature of tne mermediate, 7 3044 + 2(7257.2)+ 1682 so" : Isc “ ence =i 0 Cy, #40 yy > CO 702.6 AH AH react ~ aH product = 2025 5100/8 37% = -363.5 + 283 726 =-110.5 wc oe rhe 2 AAAS a ay ye = inratio 1:1: 0.5 Far Here N,=22N om a7i2 1, 3 En, «3H, Ne, aa —46 = SIN ane 3/2THCH 46 = 471243 <436-30N-H = 356 + 654—30N-H IN-H= 382) = 200=-8 105 OHA) +30,(9) + 2C0,(9) + 34,00) (I) +: > ,(9) + 3H,¢ P= 200 on See Bord energy of X, is p SH = du + Sng RT P= 800 AU = AH-ang RT = ans RT = 71366.5 + 8.31 «10 «300 26g 5.0 aH CH= 74.8 Ky mole ac 7 4NO,(9)+ 0,(9) + 2N,05(9) AKT 43 o4 SH -111K) eA IEN,O, (5) is formed Energy involved in the conversion of ‘Then heat of reaction will be 1 -111 -54x2 20h toCh aqis =-219 12¢ 1 PbO2 + Pb-» 2PbO. 62 250 360 29 Spontaneous process Pot? is sable 8058 Non Spontancous rpocess Sa wil De more stable‘Combustion : Exothermic ‘graphite is more stable than diamond ‘S(9) + 6F(9) —» SF, (9) AH = ~ 1100 - (275 + 6 » 80) == 1855 Sho) —+ S(9) + 6 F(9) St,(0) aH 10855 tess= «—6€,, 185s > Eat Gg = 309.16 KY/Mole €O,(9) + H,(9) —+ CO(g) + H,0(9) A,H= .H(H,0) +44 (CO) ~ 4H (CO,) = (~ 241.8) + ( ~ 110.5) ~ (393.5) 412 by performing (2) +3 x(4) + 3 x (3)-(5) BH, (9) + 30,(9) —»8,0, (S) + 3H,0(9) 1273 + (3 x 44) = (3 x 286) - 36 = -2035K)/Mole AM= A: {diamond ) wrong B: Correct Cz _2Mole NH, (wrong) D: CO (g) not elemental stale 35 Mole of gas = > aT = 043K was © oa a=25 045K = 1.12510 J JEE ADVANCED Heat evolved by 1 Mole 1.125 = (35) = 91a /Mole 2 7. Remenber the fact E.. = 100KCal / Mole 8. AM (Bru!) = 0; AH (Br,9) = 0 9. C,H, (9) — 2C(s) + H,(9) ~ 225 = 2BEC-H + B.E. ECs C= 1410 - 330 = BE C=C =~ 225-700 +1740 = 815 10..¢ ,H,,0, +O, —» 6CO, + 6H,0 ~1300 400-300 AH, = (~400 ~ 300) x 6 ~ (-1300) 2900 ka/mote 2900 =~ Fag 7716-11 Vom