‘Miscellaneous Solved Examples 1. Sixmoles ofan ideal gas expand isothermally and reversibly {fom a volume of Iitretoa volume of 10 litres at 27°C. What is the maximum work done? Express the results in various units. Sol, Work done Wenkt nV =2308nRTIog V2 a h aexon0062 301g !2 240919 If we put the value of Re83145Kt mol! W=34464.83 W=3.44x10'! ergs W = 8236.91 cal R=8.314x107 ergsK “mol” R=1.987cal K+ molt 2. Acsystem performs 101.31 of work on its surroundings and absorbs 15 kJ of heat from surroundings. What isthe change in internal energy of the system. Sol. Work done by the system is taken as negative w=-101.35 Heat absorbed by the system is taken a5 positive q=15K)= 150005 AE = qtw ( First law of thermodynamics) 50005-101.3)= 14898.7 3, One mole of liquid water at its boiling point vapourises against a constant external pressure of | atm. at the same temperature. Assuming ideal behaviour and initial volume of water vapours as zero, calculate the work done by the system. ‘Sol, For ideal behaviour of water vapour PV = nRT can be applied to find the volume. 1xV= 10,0821 *373 V=30.62it AV = V> ~Vj =30.62 it -Olit. = 30.62 lit ‘work done =~ PAV =~ «30.62 =~30.62 lit atm. =~ 30.62 « 101.33=-310185 4. A gas expands from 3 dm? to 5 dm? against a constant pressure of 3 atm. The work done during expansion is used toheat 10 mole of water of temperature 290 K. Calculate the final temperature of water. Specific heat of water is 4.184 )g 1K ‘Sol, Work done is irreversible as at constant pressure, AV=5-3=2dm"=21it, W = -Pay =-3*2= ~6 atm lit. =~ 6 « 101.3) = 607.8) ‘This work is used for heating water W=m*s* AT 607.8" 10% 18% 4.184% AT. ‘Therefore 4 =0.807 Hence final temperature = 290 + 0.807 = 290.807 K 5, 10gof argon gasiis compressed isothermally and reversibly at a temperature of 27° C from 10 litres to Slitres. Calculate q, w, AE and AH for this process. R=2.0 cal K"! mot"! log 2=0.3010 ‘Atomic weight of Argon = 40 2.303% 122x300 log = 0 io W= 103.635 cal For isothermal proceess AE =0, 4 AH=0 6. Show that in an isothermal expansion ofan ideal gas (@)AE=Oand (b) aH =0 Sol (a) For one mole ofa gas C,= (8E/ STI, W =~ 103.635 cal For finite change AE =C, AT For isothermal process AT = 0 therefore AE = 0 (&) We know that AH= AE + A(PV) = AE + A(RT) @v=Rn) ‘Therefore AH = AE + RAT. Since AT = 0, AE = AH=0. 7. Calculate the change in free energy at 25° C for the reaction ), therefore 57.37 keal 1 CO(g) + 502 @) > 0218) and the change in entropy accompanying the process is — 20.7 cal deg" mot! Sol. SG= AH-TAS =-67.37-298(-20.7 « 10) = ~61.2014 keal mol”! 8, Calculate AH, AS, AG and AE when 1 mole of water is ‘vapourised at 100° C and I atm pressure, The latent heat of ‘vapourisation of water is 540.cal gBass ‘Sol (@) 1 mole of water is 18 g therefore enthalpy change (AH: * $40 cal= 9720 cal @ Entropy change AS = AH/T=9720/373 26.06 cal K-! (ii) Free energy change AG = AH-TAS AG= 9720-373 x 26.06=0 (iy) AH=AE+PAV therefore AE = AH~PAV=AH-P(V,-V,) ‘V, = Volume of 1 mole of liquid water: 'V,= Volume of | mole of steam at 373K Applying ideal gas equation, vy = BMT _1x22400%373, Pot 1273, ‘V2, =30600cm? AV= V,~V, = (30600 18) om?=30600 em? (18 negligible) PAV=1atmx30600cm? =1%30.6lit. = 30.6 atm, 30.6 «24.2 cal=740.5 cal (Iatmlit=242 cal) Hence AE= AH ~ PAV =9720-740,5=8979.5 cal 9. Acertain volume of dry air at NTP is expanded reversibly to three times its volume (a) isothermally (b) adiabatically, Calculate the final pressure and temperature in each case, assuming ideal behaviour. (C/C, for airs 1.4) ‘Sol, Let V, be the initial volume of dry: (@) Isothermal expansion. Since AT =0 hence PV, =P;V; Py = BML PM 9355 sam V2 3V, () Adiabatic expansion we have ayy” m Ly T)=176K =-97°C Final pressure under adiabatic conditions 1" 4 Bf va 1 [=] A sts Seni geeieets LY P Vi P: 17 atm 10. The latent heat of fusion of ice is $.99ki/mol a its melting. point. Calculate. (9 AS for fusion of 900g ice i) AS for freezing of liquid water Sol. 120%) ES 1,00) Sok gre (Latent heat of fusion for 900 g 9005.99 15 = 299 51 Atty, = 2207S? by = 299.51 AH ys _ 2995x1000 _ 997K -1 Se 273 Avs (il) AS for freezing of liquid water = — ‘when liquid water freezes heat is evolved 25971000; 273 : , U1. Calculate the entropy change in isothermal reversible expansion of 5 moles of an ideal gas from a volume of {0 litres toa volume of 100 litres at 300 K. : ‘Sol, For isothermal process T, = hence the equation 21.94 JmolK-! as= AS=Cy In 22 +nRIn¥2 is reduced to Ti vi y, Vp AS =nRIn—2 = 2.303nRlog—2 vi “yy, Givenn=5, V, =l0litres, V, = 100litres, R =8.314IK~!mor! AS =2303x5%8.314 log ~ = 95.75IK"! 12. Caleulate the temperature at which the reaction 1 482018) 92Ag(6)+>0 () at 1 atmospheric pressure Will be in equilibrium. The value of AB and AS for the Taetion ate 30.58 ky and 66.11JK™ respectively and these ‘value do not change much with temperature, ‘Sol AG=AH-TAS for equilibrium AG=0 AH _ 30580 if the value of AH°=28.40kImol"! and ‘equilibrium constant is 18x 107 at 298K. '=-2.303RT logk, ~2.303x8.31IK" mol!x298, log. 8x1077 =38466)moI" ‘ass AH°-4G" _ 28400~ 38466 T 298 14. Caloulate the equilib at 400K librium constant forthe following reetion 2NOCKE) > 2NO(R) + Cl, (g) AH*=77.2ksmol™ ase =~33.78 JK"! mol =122JK"'mot™ at 400K Sol AG*=AH?—Tase = 712 x10 ~400 x 122 > $284 10° Imor!AG? = -2.303RT logK bok, =- age -28dxi0’_ = "F309 x RT 2.303x8.314%400 taking antilog, we get K, =1.995x10 15. Show thatthe reaction COV) + 40218) ©09(g) at 300 Kisspontaneous and exothermic, when the standard entropy change is ~ 0.094 kl mol-! K", The standard Gibbs free energies of formation of CO, and CO are~394.4and—137.2 KS mot respectively. Sol. The given reaction is 1 CO(g)+ 7028) C02 (8) AG? (for reaction) = G? products ~ AG? reactants, = Go, ~(G'co +8%o,) 394.4~(-137.2+0)=-2572 AG?=AH?-TAS* -251.2=AH* +298 (0.094) or AH? = -285.2KI ‘Since AG? is negative the process is spontaneous and AH” is also negative the process is exothermic. 16. ‘Theheat ofcombustion of gaseous methane CH, at constant ‘Volume measured in bomb calorimeter at 298.2 Kis found to te 885389 Jmol. Find the value of enthalpy change. Sol, CHy (g)+202 (g) ¥CO2 (8)+2H200) Given AE =-885389) mol”! 2 T=298.2K; R=8.314JK'mol” (142) sAH=AE+ AnRT = -885389+(-2) 8.314%298.2 =-890.341) For solving the heat of reaction follow the following rules @ When standard enthalpy of formation of compounds are given, apply the equation ‘AH = EAH? (products) — EAH" ¢ (reaction). (ji) When heat of combustion of compounds are given apply the equation AH=E AHpompof reactants ~ EAH comp of products. 17, ‘The molar heats of combustion of C)H (8) » C(eraphite) and H, (g) re ~310.62,~9405 and ~68.32keal respectively. Calculate the heat of formation of C,H, So. The desired equation is 2C (graphite)+H(g) > C2Ha(e) ‘AH= Heats of combustion of reactants -ZHestsof combustion of products =2(-94.05) + (68.32) ~(-310.62) =54.2keal ec = 18 The heats of combustion of CgHy (g). aH (8) and (g) ae -1400.S,-18583 and-285.6 1 espotively Calculate the heat of hydrogenation of ethylene, ‘Sok The desired equation is CoH (g)+ Hy (6) CH (8) {AH = Heat of combustion of reactants ~— Heat of combustion of products == 1409.5 + (-285.6)}4-1558.3)=-136.8KI 19. At300 K the standard enthalpies of formation of CeH,COOH (9),CO, (g)andHj0(Dare respectively =408,-393 and 286kJ mol". Calculate the heat of combustion of benzoic acid at (i) Constant pressure (i Constant volume (R =8314J mol'K) ‘Sol, AH=E Enthalpies of formation of products =. Enthalpies of formation of reactants, Desired equation is cy COOH) +4505 > 7C02(6)+34200) AH=7(-393)+ 3(-286)-(—408 -0) == 3201k) ‘Alo AH =AE4 AnRT or-3201 KI = AB+(-0,5)x8.314x10 x300 => AE =-3199.75kI 20, Given thatthe bond enthalpies for C~H, Cl-Cl, C~Cland H_Clare respectively 9, 8, 78and 103 keal /mol, determine {BH for the reaction CHg(g)+Cla(g) > CHsCl(s)+HCWB) ‘Soh. AH (reaction) = Bond energy of (bond broken in reactants = bond formed in products. =Bondenergyof [(C-H+C1-C)~(C-Cl+H-C)] ={(99+58)-(78+103)]=-24keal 21, Estimate the S -F bond energy in SF. The standard heat of formaton values of SF (g), S{g) and F(g) are~1100, 275 and 80k) mol respectively. Sol. SE, (g) -»5(g)+6F (8) AH=(AH, +64H p)-AH gp, 175 + 6x80 ~(-1100) = 1855 -. Average bond energy= 82° = 309.174)Bass 2. ‘The heat of reaction, (AH) for the formation of water at 25°C #8 68.4 kcal Find the value at90°C. The moler heat capacities (Of), HO (0) are 6.62, 6.76 and 18 cal respectively Sol AH, —AH, = AC, (1-1) Sok wo MT=T) ~ 1997.86. 2457.92KI t 373 28, Calculate AH at358 K forthe reaction Fe,03(8)+3 Hz (g) —? 2Fe(6) + 3H20() Given that AH9g =-33.29 kJ mol"! and C, for Fe0, (9), Fe(s), HO () and H (g) are 103.8, 25.1, 75.3 and 28.85 1K AC, = molar heat capacities of products . ~molar heat capacities of reactants ‘The formation of water ins +.09-+1130 mal, Sol, ACy=(2*25,1+3%75.3)~(103.8+3%28.8) 818 (6526 667) ae dst0°ka 599K ‘AH, =~68.4+8x10" (363-298) =-67.88k cal AHa=AHL _ ac, (Kirchoff's equation) 23. The heat of solution of MgSO, and MgSO,.7H,0 are R-l ~20.3 and 3.8 keal respectively. Find heat of Hydration of Meson Aig -(-23290) _ 954 358-298 ‘Sol. Heatof hydration =Heatof solution of anhydrous salt ae aaaritel Issa =~ Heat of solution of hydrated salt. ==28.136 ~20.3-(3.8) = -24.1kcal. 29. K, for CHyCOOH at 25°C is 1.754% 10-5 at $0°C. Kis 24, Integral heat of solution (AH) for 1 mole of KCI dissolved ‘i in 20 moles of water is + 15.90 kJ. When 1 moleis dissolved 1,633 x 105. What are AH? and AS® for the ionisation of in 200 moles of water, AH is 18.58 KJ. Calculate heat of cH,CooH ? dilution. Sol (AG*) 29g =—2.303 RT log Sol. KC\(s)+20H,0 + KCI(20H,0) AH, =15.90k) 0" 200 eK, = x «298 x. x 1075 KCI(s)+200H,0 > KCI(200H,0) AH, =18.58kI 5 meet 298 * log 1.754 x 10 Heat of dilution = AH, ~ AH, =18.58-15.90=2.68kI 2 . At what temperature will water boil when the atmospheric (AG*)a25 =~2.303 8.314 x 323%Log 1.623 x 10° pressure is 528 mm Hg. Latent heat of vaporisation of water =-296053 is 545.5 cal g! AG? = AH? —T ase Sol. The integrated form of Clapeyron equation is 27194= AH? ~298 ase Py AHy ft 29605= AH? ~323 ase lost = Sel Ee PR 2303R[T, Ty AH? =—1.55Ky/mol be AS° =_ 96.44 Jmol =latm=760mmHg; T; =?: Here Pj = 528 mm Hg;P ~latm=760mmHg; 1; =?; $0. Calculate the heat of neutralisation from the following data T, = 100°C =373K 200 mil of | MHC is mixed with 400 ml of.5 MINaOHL The 8 (AmPerature rise in the calorimeter was found to be 44°C. le! x 18=9819 cal. 2 ‘was found to’ AH, = 545.5cal g”!=545.5 x 18=9819 cal mot Water equivalent ofelorimeteris 12 gand specific heat is 1 9 fi cal/ml/degree for solution 760___9819_[1 1 ‘Sol, When HCI and NaOH are mi i 108-558” 2303x1987 3 +] OT, = 363K ate mixed (neutralised) the heat Produced is taken up by calorimeter and solution int AH = msiAT + mosgAT 12% 14.44 600% 134.4 (Total sol. = (200+ 400) mt 26, Calculate the maximum efficiency of steam engine working. between 110°C and 25°C. Sol, Efficiency of a heat engine is given by 383-298 2692.8 cal -h « = 0.222 oF 22.2% neBeh oe nl n° so is is neutralisation of 200 Meq 7. Calculate the useful work done by the heat engine ‘which - 2 ects between 10°C and 100°C. Heat supplied to engine is "Neutralsation of 1000 Meg. or one equivalent =~2692.8 « 5=— 13464 cal 19978610 eal3. 2 10. oil Exercise-1 | NCERT Based Questions | Be Crane en U. Predict AH> AU or AH < AU or AH (@) C(graphite) +0, @) > C0,(8) ©) PCI, @) PCG) +Ch, @) Inthe equation N,(g)+ 3H1(¢) — 2NH,(), what whould ‘be the sign of work done? Givean example of following energy conversions: @ Radiation energy into chemical energy. (@_ Radiation energy into electrical energy. A system is changed from an initial state toa final state by a manner such that AH = q. Ifthe change from the initial state to a final state were made by a different path, would ‘AH be the same as that for the first path? would q too be the same? What property of enthalpy provides the basis of Hess's while studying the properties of gaseous C,CI,F,, @ chlorofluorocarbon refrigerant, cooled 1.25 g sample at constant atmospheric pressure of 1.0 atm from 320 K to 293 K. During cooling, the sample volume ‘decreased from 274 to 248 ml. Calculate AH and AU for the chlorofluorocarbon for this process. ‘The value of molar heat capacity is 80.7 J mol"! K-! Gobar gas obtained by bacterial fermentation of animal refuse contains mainly methane. The heat of combustion ‘of methane to CO, and water as gas is given by CH,(@)+20,(g)— CO,(g)+2H,0(@) + 80910 How much gober gas would have to be produced per day for a small vllagg community of 100 families if we assume that each family has to be supplied 20000 Ki of energy per day to meet al its needs and thet the methane content in the gobar gas is 80 percent by weight. Why is it more convenient to predict the direction of reaction in terms of AG instead of AS qj? Under what conditions can AG,,, be used to predict the spontaneity of reaction? Which of the following processes are accompanied by increase of entropy ? (@) Stretching of rubber band, (©) Boiling ofan egg (©) A doodrant is sprayed. ‘Comment on the following statements (a) Anexothermic reaction is always thermodynamically ‘spontaneous. nL 2. ‘The entropy of substance increases in going from the liquid othe vapour state at any temperature Reaction with AG? < 0 always have an equilibrium constant greater than 1 Give reasons forthe following : (@) Why the heat produced be different if same mass of diamond and graphite are burnt in oxygen? (©) Thedissolution ofammonium chloride in water is en- dothermie stil it dissolves in water (© Areal erytal has more entropy than an ideal crystal. Calculate the value oflog K, for the reaction N3(g)+ 3H(@) —= 2NH,(g) at 25°C. The standard enthalpy of formation of NH, (¢) is~46 kJ mol" and standard entropies of Ny(g), H,(g) and NH,(g) are 191, 130,192.JK"' mol! respectively ) © EPC 1B. 4 15. Define the following terms (@) System (©) Isothermal processes (©) Adiabatic processes (@ State variables/state functions © Work (Calculate the standard molar entropy ctiange for the following reactions at 298 K. (@) 4Fe(s)+30; (g)—> 2Fe,0,6). (b) Ca (s)+2H,0 () —> Ca(OH), (aq) + H, (8) Given: S° Fels) =27.28, $°O;(g) = 205.14, $°Fe,0, (9)=87.4 S{Ca(s)=41.42, SH,O{) = 69.9, S*Ca(OH) (ag) =74.5, SH,@)= 13068, Calculate the standard molar Gibbs energy of formation ‘of CS,, given that its standard enthalpy of formation is 89.7 KJ mot! and the standard molar entropies of ‘graphite, S and CS, are 5.7, 31.8 and 151.3)K"!mot-! respectively. For the reaction 2H,0(!) == 2H (g) +02(g) 125°C, the equilibrium constant is 7.0 10". @ Calculate the standard Gibbs energy formations of water at 28°C. G4, H’yyo = ~ 280 kd mot, Calculate the entropy changeTor the reaction. i)Bs: 16, A 18, 19. Multiple Choice Qui ‘Thermodynamics is not concerned about__. (@) energy changes involved in a chemical reaction. (©) the extent to which a chemical reaction proceeds. (© the rate at which a reaction proceeds (@ the feasibility ofa chemical reaction. Which of the following statements is correct? (@) The presence of reacting species in a covered beaker is an example of open system. (©) There is an exchange of energy as well as matter between the system and the surroundings in a closed system, (©) The presence of reactants in a closed vessel made up ‘of copper is an example of a closed system. (@ The presence of reactants in a thermos flask or any other closed insulated vessel isan example ofa closed system, ‘Which one of the following statements is false? (@) Work isa state function (©) Temperature is a state function (©) Change in the’state is completely defined when the initial and final states are specified @ None of the above Anheat engine absorbs heat Q, at temperature T, and heat , at temperature T,. Work done by the engine is J(Q, + ,). This data @ Violates 1* law of thermodynamics (©) Violates 1* law of thermodynamics ifQ, is ve (©) violates 1* law of thermodynamics of Q, is—ve (@) does not violate 1* law of thermodynamics. ‘The pressure-volume work for an ideal gas can becalculated y, by using the expression w = { PexdV v 21. 2. rom the pV-plot by usi Tower cn epee ik toe ar ty compressed (2) reversibly oF ()sTevery wi coe @ ww reversible) = w (irreversible) (b)_ w(reversible) < -w (irreversible) (©) w(reversible)> -w (irreversible) (@)_ w(reversible) = Ww! terre + Pas ae ae bustion of one mole of butane, Deg a eae change is @ 2CJHyo(g)+ 130,(g)—> 8CO,(g) + 10H,0() AJH=-2658.0k3 mot! 0) CyHila) +42 05) 400,(0)+ 5800 A.H=-1329.0 I mot © CyHhalg) +42 0408)» 4046) +5100) AH=-2658.01K) mot © Cala) +2 0,6) +400,6)+51,00 AH=+ 2658.0kI mot! ‘On the basis of thermochemical equations (1), (2) and (3), find out which of the algebric relationships given in options (@)t0(@) is correct. ©) C(graphite)+0;@)—> CO,@); AH=xid mol! @ Clgrapite)+F 0,60) C0); aaeyuee ® COW)+ 30,500,605 4t=2KImor! @ ty © x=ytz ®) xey-z @ y=2z-xaol Exercise-2 | Conceptual MCQs > ‘Which of the following is closed system ? (@) Jetengine (b) Tea placed ina stee kettle (©. Pressure cooker (@)_ Rocket engine during propulsion ‘An isolated system is that system in which: (@ Thereisno exchange of energy with the sirroundings (©) There is exchange of mass and energy with the surroundings (© There is no exchange of mass or energy with the surroundings (@ There is exchange of mass with the surroundings ‘The intensive property among these quantities is © mass (©) volume (© enthalpy (@_massvolume ‘Which is an extensive property of the system ? (@) Volume (®) Viscosity (©) Temperature (@ Refractive index Internal energy and pressure of a gas of unit volume are related as : 2 7 als @ Pate © PAZ © P= @ PH2E ‘The latent heat of vapourization of a liquid at $00 K and 1 atm pressure is 10,0 kcal/mol. What will be the change in internal energy (AU) of 3 moles of liquid at the same temperature (@) 13.0kealmot (&) -13.0keal/mol (© 27.0kcal mol @ -70kcalimot ‘Mechanical work is specially important in systems that © liquid -tiquid @ gases (©) solid -solid Ina closed insulated container a liquid is stirred with a paddle to increase the temperature. Which of the following is true? @ Ab=weo @) AE=W,q=0 (©) AE-0, W=qe0 (@ W-0,4W-qr0 ‘An adiabatic expansion of an ideal gas always has (@) decreaxin temperature (0) q=0 © w=0 (@ aH=0 For the reaction C+, -»CO () an > ae ©) aH 4E (@ AH=AE+RTAn (diamond )—> C (graphite), AH = —ve This shows that (a) Graphite is more stable (©). Graphite has more énergy than diamond (© Both are equaly stable (@ ‘Stability cannot be predicted One mole of a non-ideal gas undergoes a change of state (2.0 atm,3.01, 95K) (40atm, 5.0L,245K) with achange {n internal energy, AU=30.0 Latm. The change in enthalpy ‘AH ofthe process in L atm is. @ 40 @ 423 © 40 (@ Not defined because pressure is not constant ‘The enthalpy of vapourisation of water from the following, two equations is. Hy(@ +40, — 100, al=-2461d Hy (8) +40; (8) H,0 (@), AH=-245583 (b) 405 @ 125 @ 6a © 03Kfo 20. 21. 2 2. 4. 21. In the process C1(g)+e7 Mt 4c1"(g), AH is (a) positive (b) negative © zero @ unpredictable The variation of heat of reaction with temperature is given tye (a) Van't Hoff equation (©) Clausius- Clapeyron equation (©) Nemst equation (@ Kirchof’s equation Kirchof?'s equation is 28. 29, @ k=Aeh/RT k, E, T,-T, togk2 -—Ee_ (B= © eT 2305R ( ) 303RT | C tog 2 FC 30. © Beau = 31. AH, ~AH, @ Spaptsac, Hess's law deals with : (@) changes in heats of reaction (b) rates of reactions (©) equilibrium constants (@_ influence of pressure on the volume of a gas Ifa chemical change is brought about by one or more methods in one or more steps, then the amount of heat absorbed or evolved during the complete change isthe same: method was followed. This rule is known as : (@) LeChatelier principle (6) Hess's law (©) Joule Thomson effect (4) None of these ‘One mole of an ideal gas at 300 K is expanded isothermally from an initial volume of | litre to 10 litres. The AE for this process is (R=2 cal mol"! K"!) (@) 163.7cal (b) zero (©) 1381.1cal @ Slitatm (One mole of an ideal gas is allowed to expand reversibly and, adiabatically from a temperature of 27°C. Ifthe work done during the process is 3 kJ te final temperature wll be equal t0(C,=20JK) (@) 150K (b) 100K ©) 2685K (4) 295K 2 moles of an ideal gas at 27°C temperature is expanded reversibly from 2 lit to 20 lit, Find entropy change (R=2cal/mol K) (@) 21) 0 32. 33. © 4 (92 ‘Theheat required to raise the temperature ofa body by 1, iscalled (@) specific heat (¢) water equivalent For a reaction to occur (@ AS must be negative (e) (AH-TAS)must be negative (9) (AH +TAS) must be negative (@) asf must be negative ‘Theenthalpy and entropy change for a chemical reaction are — 2.5x 10° cal and 7.4 caldeg™! respectively. The reaction at 298K will be (@) spontaneous (b) reversible (©) inreversible (@_ non — spontaneous. Heat exchanged in a chemical reaction at constant temperature and constant pressure is called (&) thermal capacity (@_ none of these spontaneously (@) intemal energy (®) enthalpy © entropy @ free energy For the process Dryice~» CO2 (8) (@) AH is positive and AS is negative (b) Both AH and AS are negative (©) Both AH and As are positive (@ AHis negative whereas AS is positive ‘The favourable conditions for a spontaneous reaction are (@ TAS> AH, AH =4ve, (b) TAS>AH, AH =+4ve, (©) TAS=AH, AH =-ve, (@) TAS=AH, AH=4ve, AS=+ve AS=-ve AS=-ve AS=4ve Identify the correct statement. tegarding entropy. (@) At absolute zero temperature, entropy of a perfectly ear ‘substance is taken to be zero t absolute zero temy perature, the ott vet crytalline substance is postive solute determined "PY OF @ substance cannot b¢ LOC, the ents istaken tobe ery PeTeely crystalline substanoe For which ofthe following proces ® Hye) 2H@ ©) © @® ® © @ S, AS is negative? N2G@)(latm) — 9 (g)(Gatm) 280318) +2508) +0, Clans) Crain35, According to second law of thermodynamics a process (reaction )is spontaneous if during the process (@) MS riverse >0 © Syniverse =0 (©) MHyystem > 0 @ 346, ‘Thelaw formulated by Nerastis (a) first law of thermodynamics (©) second law of thermodynamics (©) third law of thermodynamics (8) Both (a)and(b) 37. 1900J/gofheatis exchanged atboiling point of water, then ‘what is increase in entropy? (© 434 Yimole (©) 872 Ymole © 900simole @ Zero 38. Given the following entropy values (in JK"! mot") at 298 Kand 1 atm: HG): 130.6, Cly(g): 223.0 and HCI (g): 186.7. Theentropy ‘change (in JK" mol“) for the reaction HA(g)+Cla(g) > 2HCl apis @ +5403 @) 7270 (© 169 (@ 198 39. Entropy change involved in the conversion of 1 mole of liquid water 373 K to vapour atthe same temperature will bbe (AH yap, =2.257KI 2) @ O119%s © 0.129% Which relation is correct ? (@) AG = aH-TAs ©) AG=AH+TAS (© AG=TAS-AH @ AG =aH-ser 41, The value of free energy change at equilibrium is (8) positive (©) negative (© 220 (@ not definite 42, The standard Gibb's free energy change, AG? is related to ao o [gy (&) 0.109% @ one cquilibrium constant, Ky as (® Kp=-RTinaG? AG © Ke=-pr @) Kp= 43, What isthe free energy change.'AC' when 1.0 mole of water at 100°C and | atm pressures converted into steam at 100°C and 1 atm. pressure (@) 540cal (©) -9800 cal (©) 9800-cal @) Ocal 45, 46. 47. 49. si. 161 According to third law of thermodynamics, which one of the following quantities fora perfectly crystalline solid is zero at absolute zero, (@ Entropy (© Internal energy ‘The calorific value of fat is (@) less than that of carbohydrate and protein () less than that of protein but more than carbohydrate (©) less than that of carbohydrate but more than that of protein (4) more than that of carbohycrate and protein. Heat of neutralisation of strong acid against strong base is constant and is equal to (@ 13.7kcal © s7 © S7x105 @ Allofthe above ‘The heat of formation of the compound in the following, reaction is H; (g)+Cl; (g) > 2HCI(g) + 44kcal (b) Freeenergy (@ Enthalpy. (@) -44kcal mot (©) -22kealmol™! © 1keatmot @ -88kcalmot™! Given that C+ CO, AH? =~ xkI 2CO +039 2CO, AH? =— yk the enthalpy of formation of carbon monoxide will be 2x-y : ya2x © o @ 2x-y @ y=2x. ‘The enthalpy of neutralization of acetic acid and sodium, hydroxide is ~$5.4 kJ. What is the enthalpy of ionization of acetic acid? @ -19k @) +19K ‘The neutralis (© +5540 (@)-SS4h) jon of a strong acid by a strong base liberates an amount of energy per mole of H* (depends upon which acid and base are involved (®)_ depends upon the temperature at which the reaction takes place (© depends upon which catalyst is used (@ isalwaysthe same [Equal volumes of methanoic acid and sodium hydroxide are mixed. Ifx is the heat of formation of water, then heat ‘evolved on neutralization is (@) morethan x (© lessthanx (©) equtal tox (@) twicex.1 om 82, ST. s+Zo, 9805 +2xkeal $0, +50; ->803+ ykeal Find out the heat of formation of SO, @) (y-2%) &) Qxty) © (ty) @ 2x The enthalpy of neutralisation of a weak acid by a strong base is @ -5732K0 &) 497320 (© equal t0-57.32kJ + enthalpy of oni (@)_ morethan -57.32 kI ‘Theenthalpy of formation for C,H, (g), CO, (g) and H,0(1) at 25° Cand 1 atm pressure are 52, ~394 and-286 kJ mol"! respectively. The enthalpy of combustion of CH, (g) will be @ +412K mot! ©) -1412k mol! (© 141.2kb mol! @ -141.2kI mol ‘When water is added to quicklime, the reaction is @ explosive ©) endothermic (© exothermic @ photochemical Mark the correct statement (8) Forachemical reaction tobe feasible, AG should be (©) Entropy is a measure of order ina system (©) For a chemical reaction to be feasible, AG should be positive (@_ The total energy of an isolated system is constant, One mole of an ideal gas is allowed to expand freely and adiabatically into vaccum until its volume has doubled. The ‘expression which is not true concerning statement is @ aH=0 © as=0 © AE=0 @ W=0. Which of the following statements is true ? (@) AG maybe lesser or greater or equal to AH (©) Gis always proportional to AH © Gis always greater than aH (@) Gis always less than AH ‘Compounds with high heat of formation are less stable because (@) itis difficult to synthesize them “b) energy rich state leads to instability (©) high temperature is required to synthesize them (@)_ molecules of such compunds are distorted, fon of week acid bustion of CH,(g). C (Braphite), Hy(g) yy 60. Tae a 10K respectively. The heat of formaig 61. 67, ofmethane is. (b) +40kcal kal a err (©) +80keal Hy + Clp-> 2HCI,AH = ~ 194K. In this reaction gy ion of HCI in kd is st ®) +9 et Enthalpy of neutralisation of HCI with NaOH is x. They ‘evolved when 500 ml of 2'N HCI are mixed with 250 ml of4y NaOH willbe. @ 50x ) 10 ox @ 10x When 1MHjSQ, is completely neutralised by sodiuy hydroxide, the heat liberated is 114,64 kJ. What is the enthalpy of neutralisation ? @ +460 @) ~1146415 ©) -$732k5 @ +5732) ‘The amount of energy released when 20 ml of 0.5 MNaOH are mixed with 100 ml of 0.1 M HCl is x kJ. The heat of neutralisation (in kJ mol") is @) =100x. (b) 50x. © +100x @ +50x The AH, for CO, (g), CO(g) and H,0 (9) are-393.5,-110.5 and ~241.8 kJ mol"! respectively. The standard enthalpy change (in k3) for the reaction C0, (8) +H2 (3) CO. (8)+H0 (g) is @) S241 ) 412 (© 2625 @ as Ha (B)+Cly(g) 2 HCK(g) AH=~44 kal 2 NAG) +2 HCKg)-> 2NACI (5) + Ha(g) AH =~152kea For the reaction 1 N1(8)+5 Cla) — nace) aH=2 clements is equal to the heat evolved when the compound its el te (ib Cavan cad oa “This is in accordance wit:| Exercise-3 eco © Past Comperirion uco: Weft ‘Consider the following reactions: [CBSE-PMT 2007] @ Hq) + OH (aq) —> 1,00, AH=-X,K mol! Hy@)* 40K) — 400, aH=-X,) mo Gi) CO{@)+ H,@) —> CO®)+H,0, AH=-X, kd mol @) CqHa(@) + 30218) — 200,(g)+H,00, AH= + 4X,kmot Enthalpy of formation of H,0() is (@) +X,Kimor! — () ~X,kImol"! (© +XKmor! — @ ~X, Kimo 2. Given that bond energies of H- H and Cl — Cl are 430KS mot! and 240 KJ mol" respectively and At for HC! js -90 kJ mot-1, bond enthalpy of HC is [CBSE-PMT 2007] (@) 380kKimot! =) 425K mot" (© 245kImot! —()_ 2901 mot! 13. Which ofthe following are nor state functions ? [CBSE-PMT 2008] © atw m9 ra aw. WH-1S @ Mada) & @),anacvy © @,)andQ (@) and) 4. Forthe gus phase reaction, [CBSE-PMT 2008] PCIg) —= PCH@)*+CL®) “which ofthe following conditions are correct? (@ aH=0andas<0 (&) aH>Oand as>0 (© aH<0andas<0 (@ AH>Oandas<0 ‘5, Bonddissociaton enthalpy of Clyand Clare 434,242 and 431 KJmot! respectively Entalpy of mation of HClis: [CBSE-PMT 2008] (@ kim! (@) ~245 dott (© -93Kimol? —(@) 245Kimott & The values of AH and AS for the reaction, (graphite) + CO, (g) —> 2CO(g) are 170 kd and 170K", respectively This reaction wll be spontaneous at ‘ [CBSE-PMT 2009] © 10K @ 70K (@ 910K © s10kK 1 9. 10. [CBSE-PMT 2009] From the fllowing bond energies: H_—Hond energy: 431.37 kJ mo C=C bond energy: 606.10 kJ mol" C—Cond energy: 336.49 kI mol! (C—Hbond energy: 410.50 kJ mol? Enthalpy forthe reaction, HOH HH il [eel = C+H-H—9H-C-C-H rd TI HH HH willbe: (@) -243.6ldmor! -(b) -1200kImot"! (©) 553.0kI mot" @ 1523.6) mot" ‘Standard entropies of Xz, Y2 and XY3 are 60, 40 and ‘50 JK-!mol-! respectively. For the reaction (CBSE-PMT 2010] pati = XV, AH =-30K) tobe at equilibrium, the temperature shouldbe: @ 750K (©) 100K (© 150K © 0K For vaporization of wate a 1 atmospheric pressure the values ‘of AH and AS are 40.63 kimot"' and 108.8 JK+ mot, fespectvely The temperature when Gibbs energy change (AG) for his transformation will be 2er, i: [CBSE-PMT 2010] @ 4K 24K © 34K (@ 3B4K. Match List 1 (Equations) with ListIl (Type of processes) ‘and select the correct option. [CBSE-PMT 2010] List List Equations ‘Type of processes @ K>Q @ Non spontaneous @. aG? 2FeO(s)+CO,(g)is; @ +62k ©) +1031 © -83% @ -103%) 12. Three moles of an ideal gas expanded spontaneously into vacuum, The workdone will be: |CBSE-PMT 2010] (@) Zero (0) Infinite () 3 Joules (4) 9Joules 13. Ifthe enthalpy change for the transition of liquid water to steam is 30 kJ mol"! at 27°C, the entropy change for the process would be: ICBSE-PMT 2011] (@) 10Jmol"K-!—(b) 1.0) mot"! K-! (©) O.1Jmol*K7 (4) 100JmotK 14, Enthalpy change for thereaction, 4H(g) — 2H (8) is 869.610. The dissociation energy of H-H bond is ICBSE-PMT 2011] (@) ~ 434810 (b) - 869.610 © +44810 @ +2174 15. Consider the following processes : ‘AH (ki/mol) 12A+B +150 3B2C+D 125 E+A>2D +850 ForB+D—E+2C,AHwillbe: — (CBSE-PMT 2011 M] (@) 525ky/mol ©) ~175ksimol (©) ~325ks/mol (4) 325ki/mol 16. In which of the following reactions, standard entropy ‘change (AS*)is positive and standard Gibb’s energy change (AG*) decreases sharply with increase in temperature? ICBSE-PMT 20125} (@) C(graphite)+ $0.) > CO(e) ©) C0@)+ 40,@)C0,@) 1 (©) Mats) + > 0,(¢)—> Mg0(s) @ 5 Clorephitey+ 040) 00,8) 17. The enthalpy of fusion of water is 1.435 kcal/mol. The molar entropy change for the melting ofice at 0°C is: ICBSE-PMT 2012} (@) 10.52cal/(molK) (b) 21.04 cal/(molK) (©) 5.260cal/(molK) (4) 0526.cal/(molK) 18. 19, a, 2 23. 00 Ajay H® fr vate, thalpy of vapourisation Avy “ ania 1 The internal energy of of water at 100°C (in kJ mol") is: ICBSE-PMT 20195, (a) +3756 ) gee (©) +43.76 @ +H (Assume water vapour to behave like an ideal gas), Equal volumes of two monoatomic gases, A.and B, at sang temperature and pressure are mixed. The ratio of specie heats (CC, ofthe mixture willbe: [CBSE-PMT 2013) (a) 083 (b) 1.50 @ 33 (@) 1.67 A reaction having equal energies of activation for forward and reverse reaction has : INEET 2913) (@ AG=0 (b) AH=0 (© AH=AG=AS=0 (d) AS=0 Ifan endothermic reaction is non-spontaneous at freezing point of water and becomes feasible at its boiling point, then [AIEEE 2003, @) AH is—ve, AS is+ve (®) AH and As both are +ve (© AH and As both are-ve @ AH istve, As is-ve A heat engine abosrbs heat Q, at temperature T, and heat , at temperature T,. Work done by the engine is J(Q, + ,). This data [AIRE 2002} (@) Violates 1* law of thermodynamics (©) violates 1* law of hemodynamics if, is—ve (©) violates 1* iaw of thermodynamics of Q, is—ve (@ does not violate 1 law of themodynamics. For the reactions, [AIEEE 2002] C+0, > €0,; AH =.3935 2Zn+0, 22200; AH =-412 (@) carbon can oxidise Zn (©) oxidation of carbon is not feasible (© oxidation of Zn isnot feasible (@ Zn can oxidise carbon, . If the system Boes from A to Bby# oe ath and. Tetums to state A by an irreversible pah ‘would be the net change in internat energy? H,C—C,c=Candl the value ofenthaby cnet By 615 and435 kJ mol, '€ reaction. C= CH, (g) +4 298K will be 2@ HCC) . ~ 25015 O+5y [AIEEE 2003} (© ~1254y @ +2501g26. nan irreversible process taking place at constant T and P and in which only pressure-volume work is being done, thechange in Gibbs free energy (4G) and change in entropy (dS), satisfy thecriteria [AIEEE 2003] © (A9yp70( BG, p<0 ©) (AS\,2= 0.4.90 © (ASp70(AD.p>0 @ (ASW p<0,(AGy,p1,-ve () -ve,<1,-ve © *e,>1,ve (@ -ve.>1,+ve 32. Consider the reaction : Nz + 3H —> 2NHg carried out at constant temperature and pressure. If AH and AU are the enthalpy and intemal energy changes forthe reaction, which of the following expressions is true? TAIEEE 2005] (@® AH>AU () AH Ca0(s)+CO2(g) the values of AH? and |AS® are+179.1 mot! and 160.2./K respectively at 298 K and 1 bar, Assuming that AH® and AS® do not change with temperature, temperature above which conversion of limestone to lime will be spontaneous is @ 118K @) 108K (© 120K @ MK Assuming thai water vapour is an ideal gas, the internal energy change (AU) when | mol of water is vapourised at 1 bar pressure and 100°C, (given : molar enthalpy of (&) 247757 mot! ‘vapourisation of water at | bar and 373 K=41 kJ mot" and R=83 Jmol K) will be [AIEEE 2007] (@) 41.00kdmo? (b) 4.100kmor! (©) 3.79041 mot @ 3790410 motos 40. Identify the correct statement regarding a spontaneous process: [AIEEE 2007] (@) Lowering of energy in the process is the only criterion for spontaneity. (b) For a spontaneous process in an isolated system, the change in entropy is positive. (©) Endothermic processes are never spontaneous. (@ Exothermic processes are always spontaneous. 41. Oxidising power of chlorine in aqueous solution can be determined by the parameters indicated below: [AIEEE 2008} 1 Jat? ‘Begh® 7oh@) 2g) ore) tint? cr (ay (using the data, Saw, =240K5 mol, A, HG, =-349 ki mol’, Ajgg HQ = 381 KI mol”), will be (@ +152kmot! —&) -610ks mot! (© -850KImot! — @)_+120%Imor 42, On the basis of the following thermochemical data : [aH = O01 [AIEEE 2009] H0(/) > H* (aq) + OH” (aq); AH = 57.3243 Hg(@)+50,(@) —$1,0(0; At¥=-286-203 ‘The value of enthalpy of formation of OH” ion at 25° Cis: (@) -228.88K0 &) *288810 © —4352K (@ 288K 43. The standard enthalpy of formation of NH, is ~46,0 ki mot ifthe enthalpy of formation ofH, from its ‘atoms is -436 kJ mol~! and that of N, is—712kI mol", the average bond enthalpy of N ~ H bond in NH, is IAIEEE 2010] (@) -964kImot! — (b)+352KImot! (©) +1056kImor! —(@) ~1102KI molt 44, Fora particular reversible reaction at temperature T, AH and AS were found to be both +ve. If 7, isthe temperature at equilibrium, the reaction would be spontaneous when (@) 1,>T () T>T, {AIEEE 2010) (© T,isStimesT @) T=T, 45. The value of enthalpy change (AH) for the reaction CHsOH(O +303(g)> 2C03(g)+3H20(6) 27° Cis — 1366.5 kJ mol". The value of internal energy ‘change for the above reaction at this temperature will be: [AIEEE 2011 RS] &) ~1364015 (@) -136.010 @ -137150 (© -1361.5% 47. 49. 50. si. 52. consider the reaction: [AIEEE 211Rg 4NOp(g) + 028) > 2N205(8), =— 111 KS. . Eason fomed intend oN; 0, inthe above ren, y value will be: : ee! ‘AH of sublimation for NOs is 54 kJ mot!) @ +54KI (®) +2190 (© 2195 @ 165K ‘A piston filled with 0.04 mol of an ideal gas expand ‘eversibly from 50.0 mL to375 mL ata constant temperate 5f37.0°C. Ast does 50, it absorbs 208 J of heat. The value of q and w for the process will be: (JEE M2013) (R=8314 Simol K) (in 7.5=2.01) @ q=+208J,w=-208) (&) q=-2085,w=-208) © q=—208J,w=+ 208) (@ q=+208J,w= +2085 The value of log,, K for a reaction A = Bis + Given: A,H}9gx = 54.07 kJ mol”, ‘A,Syosk = 10K"! mol"! and R = 8.314 JK"! mol”; 23083 x 8.314 x 298= 5705) (ITSEE 2007) @ 5 ® 10 © 9% @ 10 For the process H,O(/) (1 bar, 373 K) > H,O(g) (1 bar, 373 K), the correct set of thermodynamic parameters is [UTE 2007] @) AG=0,AS=+ve (b) AC |, AS =—ve (©) A ‘ve, AS=0 (d) AG=~ve, AS=+ve The species which by definition has ZERO standard molat enthalpy of formation at 298 K is (IT-JEE 2010) @ Bw ) Che) © 1,0@ @ CH@ coe ‘Provided, calculate the multiple bond enerB) Cas of C = C bond in C,H,. That energy is (take he energy ofa CH bond as 350 kJ mot!) 2069)+ H,@) — Hom cH); AH=225 kJ mol" FeO — 2048); 141013 mot"! a sas 2H); AH=330kImot-! pT JEE 20121 ©) %7 © %5 @ ais The standard enthalpies of formation , 10 ~,sPectivelyo,The standard enthalpy Per gram of glucose at 25°C ig, @ +29001K5 ae ass © seu — @ arewL La For determining the spontaneity of a process which of the 9. following is considered ? (@) ASsystem () AS surroundings (©) AS system + AS surroundings (@) AS system — AS surroundings ‘Which of the following is always true for a spontaneous change at all temperatures ? (@) AH>0;AS<0 ()AH<0;AS<0 (©) AH<0;A8>0 (@)aH>0;aS>0 ‘What isthe change in entropy when ice melts at °C, enthalpy ‘of fusion of one mole oficeis 6.02 KI ? (@) 602K K mot (©) 2.1K! mor! (©) 41.61K"' mor @ 201K" mor In which of the following processes, the entropy decreases 2 (@) CaCOs(s)- CaQ{s)+C02(8) (0) 2NH3(g)—> No(6)+3H2(8) (© 2H2(g)+02(g) > 24200) @)_03(g)—> On(8)+ Ol) For which one ofthe processes represented by the following ‘equations the enthalpy heat) change is likely tobe negative © CH@)+aq CI (aq) ©) Clg) CI") +e © 1/2C1z(@)> CK) @)_ Cla > Cal) The enthalpy change of formation of CO> (e) is 393 klmot and that of HO (I) is - 286 kImof””. The enthalpy of combustion of one mole of ethanol (CH,OH) is 1360, The enthalpy change forthe formation of one mole of ethanol form its constituent elements is @ ~681d (@) ~2441a © 965K) @ BeOKw ‘What s An), for the combustion of| mole of benzene, when both the resctants and the products are at 298 K’? @ 0 (b) 12 © 32 @ +392 Which ofthe following statements is false ? (@) For | mole ofan ideal gas, C,-C,=R om 13. 14, © (3), sosentestom ' ae (© dq=Aw+pav (@) Forreversibl isothermal expansion of | mole ofan ideal {gas from volume V, to V,, work done is equal to RT In WN) What is the free energy change for the conversion of I mole of water into steam at 373.2 K . The heat of vaporization (AH,) of water of 373.2 K is 9.1 keal. mol, ‘The entropy changeis 25.5 cal/mol deg, (#) 401.6calimol (6)-416.6 call (© 516.5calmol (@) -516.5calimol ‘The ‘thermite reaction’ involving the reaction between ferric oxide and metallic aluminium produces molten iron, Given that 2AL+3/20» > Alg0s; AH, = ~400 keal/ mol 2Fe+3/202 —> Fez03; BH = ~200 kcal/mol. ‘What is AH forthe formation of 1 mole of iron ? (@) -100kcal (©)-200 kcal (©) H100kcal (© *200kcal Given the reaction at 927°C and 1 CaCO, (8} == CaO5)+CO9(g) SH AE equals, @ 1000 (16.0315, : © 180% @ 186410 ‘What isthe enthalpy change forthe reaction Hy (g)+CpH4(8) > CoH (a) ‘The bond energies are given below: (H-H) 7 103;¢ (C-H)»99,¢ (C-C) +80 and atm. '76 ki/mol; then (C=C) 9145 kcal/mol respectively (@ 10kcal mot" (#10 keal mot"! (© 30 keal mor"! (@ +30keal mor! Forthe process H,O())—> H,0(g) AH= 45.0 kJ mol"! and AS= 1.20% 102JK"! mol", At what temperature the above process is at equilibrium? @ mK 33K © 30K @ 395K Third law of thermodynamics is used to determine the (@) spontaneity of a process () enthalpy of substance (©) absolute values of entropy of a substance © free energy of a substance In thermodynamics, a process is called reversible when (@) surroundings and system change into each other () there is no boundary between system and surroundings (©) the surroundings are always in equilibrium with the system (@ the system changes into the surroundings spontaneously1° 16, 7. 19. 20. 21. 2. Which one of the following statements is false? (a) Work is a state function (©) Temperature is a state function (©) Change in the state is completely defined when the initial and final states are specified (@ Work appears at the boundary of the system The standard enthalpies of formation of H* and ‘OFF ions in water are zero and -229.6 kJ mol" respectively. ‘The standard enthalpy of formation of liquid water is—285.6kI ‘mot, Then the enthalpy of neutralization of HCl(aq) by KOH(aq) is @ 296k) mot! (&) 173.4 mot! (© 56.0kImot? (@ -56.0k5 mot Which of the following salts should cause maximum cooling when 1 mole of tis dissolved in the same volume of water ? (@) NaCl; AEP=5.35k mol (b) KNO,; AHP=53.5k) mot” (© KOH; a (@ HBr; Alp: ‘The molar enthalpies of combustion ofisobutane and n-butane are-2870 kJ mot-! & -2875 kJ mot“! respectively at 298 K and 1 atm, Calculate AH? for the conversion of | mole ofn-butane to 1 mole of isobutane @) -8k) mol (®) +8kI mol" (© -$748id mot" @ +5748 mot For the reaction CO(g)+4.03(g) +002) AH = ~67650 cal at 25°C. Calculate AHP at 100°C, given thatthe required molar heat capacities are as follows. C(CO,g)=6.97 cal C* Cy(COp@)=8.97 cal°C* Cy(On.8)=7.00 cal (@) -54.6cal ©) -67650.4cal (©) 616844 cal (@) -67762.5cal “The heat of atomization of PH,(g) is 228 kcal mol“! and that of PH,(a) is 335 keal mot. Theenergy ofthe P-P bondis (@) 102kcal mot! () 51 keal mot" (©) 26kcal mol" (@ 204kcal mot+ ‘The enthalpy of solution of a substance is given by (@) AHsoin = Ucatice energy) + AHnydration (b) AH Soin, = Ucinice every) ~ AH nydration (©) BHsoin, = ~Ucunice energy) + AM hydration (@) AH coin, = ~U aie ener) ~ AH hydration 26. 2. For the reaction H(6) + 1502(8) —4002(8) + 6204) 1 at 298 K. Calculate AH? Ht ) -760.3 kJ mot (a) +760.3KJ mol ©) 6 +6703 mot @ 7903 ki mot' uivalent of H,SO, is treated with 112 8 0fKOH fy eee ee eutratization, Which of the following statemeny, 2CHsCO2! ‘AuP=-772.7 kb mol complete is correct? (@ 13:7 keal of heat is evolved with the formatio 87 gofK,S0, leaving no KOH. 274 keal of heat is evolved with the formation of 87 gofK,SO, leaving 4 gram equivalent of KOH, 15.7 kcal ofheat is evolved with the formation of | gram equivalent of K,SO,, leaving 56 g of KOH. (@ 13.7 kcal ofheat is evolved with the formation of 87gof K,SO, leaving I gram equivalent of KOH. From the following data AH of the following reactions ) © 49) £0218) —> CO(g), AH=-110kdand C(s)+ HyO(g) ——> CO(g) + Hp (g); AH= 132K) Calculate the mole composition of the mixture of steam and ‘oxygen on being passes over coke at 1273 K, keeping the temperature constant. (@ 1:06 © 2:3 () 06:1 @ 3:2 AHP of water is - 285.8 kJmol"'. If enthalpy of neutralisation of monoacidic strong base is ~57.3 kImol™'. AH? of OH™ ion will be (@ ~11425 kml"! (&) 114.25 kImol™ © 285 kImol™ (@) -2285 kJmol"! ‘Temperature of 5 moles ofa gas is decreased by 2K at const pressure. Indicate the correct statement (@) Work done by gas is= 5 R (©) Work done over the gas is=10R (©) Work done by the gas=10 R © Work done=0 ‘An ideal gas occuping & volume of 2dm? and a pressure ofS bar undergoes isothermal and irreversible expansion agai" external pressure of | bar. The final volume of the syste and the Work involved in the process is 3 (@) 10 dm? 1000) (b) 8 dm?,—800J 3 OG dn’ toa (@ 10 dm? ,~ 1000329. at. 32. 33. ‘At 25°C and 1 bar which of the following has a non-zero HE @ Ba) (©) C(graphite) © %@ @ L© Bond enthalpies of Hy, Xp andHX are in theratio2 : 1:2. Ifenthalpy of formation of HX is~50 kJmol" the bond enthalpy of X2 is @ 100 kimol (b) 300 kImol™ (© 200 kimol @ 400 kimol™ When I mole of oxalic acid is treated with excess of NaOH in dilute aqueous solution, 106 kI of heat is liberated. Predict the enthalpy of ionisation of the acid @ 43 kimol () -43 kimol™ © 86 kImol™ @ -86 kimol™ “Anatlete is given 100 g of glucose (CgH,0g) of energy equivalent o 1560 kJ. He utilises 50% ofthis gained energy in the event. In order to avoid storage of energy in the body. Calculate the weight of water he would need to perspire. “The enthalpy of evaporation of water is 44 kmol”*. @ 319.18 ©) 119-78 © 2158 @ 25028 ‘The enthalpy change for hydration Cu804(6)+ SH,0(g) —> CuS0« 5H0 6) is—71.50 kealmol™ enthalpy of vaporisation of water is, 10.5 kealmol™ at2S°C, what would be the enthalpy change for the hydration CuS0,4 (8) + 5H201] —> CuSO, 5H; (8) (@ -19.0 kcalmol™ (©) 19.0 kealmol” (© 610 kealmol" (@) ~ 61.0 kealmol” “The lattice energy of solid NaCl is 180 kealmof” and enthalpy of solutions | kealmot”’.Ifthehydration energies of Nat and CI” ions are in the ratio 3 : 2, what is the ceathalpy of hydration of sodium ion ? (@) -1074 kealmol ——_(b)_ 1074 kealmol"* (©) 716 kealmol” (@ -71.6 kealmol ee © 8 35. The AH at 358 K forthe reaction Fe03(5) +3 H2(@) —> 2Feis)+3 #20) given that AH 9g =-33.29 KJmol" and G, for Fez03(8), Fe(s), HO (and Hi (g) and 103.8, 25.1, 75.3 and 288K mal (@ 28136 Kimo! @&) ~38.3 k mol” (© 425 kJmol @ 362 kJ mol" 36. AH; of NF, is 113kJ mol”! and N-F bond energy is 273.0 kJ mol” . fN=N and F-F bond energies are in the rates 6 I, their magritudes will be (a) 780.0 kJ mot" 130.0 kJ mol” (b) 840 kJ mol" ,140 kJmol (©) 950.0 kJ mol , 158.3 kJ mol” (@ 941.3 kJ mol", 156.9 kJ mol" 437. The enthalpy of neutralisation of NH,OH and CH,COOH is - 10.5kcalmot and enthalpy of neutralisation of CHjCOOH with strong base is - 12.5 kcalmol", The enthalpy of ionisation of NH OH will be (b) 2.0 kealmot™ @ 40 kealmol (@ 32 kcalmol' (© 30 kealmot ‘Standard enthalpy ofcombustion of CH, is—890 kImol™* ‘and standard enthalpy of vaporisation of water is 40.5 kimol”, The enthalpy change of the reaction CH, (@ +203 (g) —> CO (@)+2,0(8) (@) -809.5 kimot (©) -890 KJmor (© 809 mor" @ -971 mor! 39. The enthalpy of combustion of 2 moles of benzene at 27°C differs from the value determined in bomb calorimeter by (@) 249440 ©) 249410 (©) -748310 (@ 748310 40. Theheats of neutralisation of CH3COOH , HCOOH, HCN and HyS are~132,~134,-2.9 and~3.8keal per equivalent respectively. Arrange the acids in increasing order of strength (@) HCOOH> CH,COOH > Hy >HCN () CHjCOOH > HCOOH> HS >HCN (© HS >HCOOH> CHjCOOH > HCN (@ HOOOH> H;8> CH,COOH >HCNim 41, When 1.8 g of steam at the normal boiling point of water is ‘converted into water at the same temperature, enthalpy and entropy changes respectively will be (AF yaprsaion fF HO =40.8 kImol”') @ 408k,1093 1K") -4.081,- 10.93 JK (© -4.08ks,-408 IK" (4) 4.081, 40.8 JK“ 42. The enthalpy of neutralisation ofa weak acid in 1 M solution with a strong base is - 56.1 KImol, If the enthalpy of ionisation of acid is 1.5 kJmol' and enthalpy of ‘neutralisation of the strong acid with a strong base is —57.3 kJeq”'. What is the % ionisation of the weak acid in molar solution (assume the acid is monobasic) @s ©» © 1s @ 10 The enthalpy of atomisation of CH, and CoH are 3g) and 620 keal mol™! respectively: ‘The C—C bond energyiy expected to be 1 (@ 210 kcalmol” () 80 kcal mol “1 (© 130 kealmol (@) 180 kcal mot ._Acertain reaction is non spontaneous at 298K. The entropy change during the reaction is 121 JK" Is the reaction ‘endothermicor exothermic ? The minimum value of AH for the reaction is (@ endothermic, AH =36.06k) ©) exothermic, AH =~ 36.0610 (©) endothermic, AH =60.12kI (@ exothermic, AH =- 60.1215_ Hints & Solutions _ eco e AU because An = 1 2. The sign of work done will be+ve 3. @ Photosynthesis (Photoelectric effect. 4, . AHisthe same but q will be different. S. (@_ Enthalpyisa state fiction and (b) law of conservation of energy are the two basis of Hess's law. 6 AU=-20487 aH=-23.113 +7. Amount of gobar gas produced per day = 49-44 kg 9. (pando). TL. (@) because they have different crystal structure. (b)_ AG will be -ve. Hence, the process is spontaneous, (© Areal crystal has some disorder due to presence of 83% 103 |AS?=-549,74 JK"! mol"! (0)AS°=23.96 JK"! mot" () 6527KImot, » 15. @ A(Gy,0%-237.22 Kb mor! (i 48°=3273 mor! KT 6 © 1.08 @ % @ 2. © 2. © 2 © 12. og. 4. 1. © Closed system can exchange energy and not mater with Surroundings. Pressure cooker provides closed system. 2. (© Isolated system cannot exchange mass or ener. A @ Mass/volume = density, hence itis intensive property. 4. {@ Volume depends upon mass. Hence itis extensive property 5. (@) Kinetic gas equation, =fmnu? =F KE, For unit volume, P = PV 6 © 3H,0() > 3H,0(8); 2 dan © 3, AE = AH~AnRT =30~3%5555%500 =27keal 7. @ Gases can undergo expansion hence perform mechanical work. (PAV work) 8 (@ In insulated system no heat or matter is exchanged, q=0 «.SE=W. The work done on the system increases internal ene"By. 9. @) For adiabatic process 4 = 0 10. (@ AH=AE+AnRT ; An=0=2AH=AE. In the given reaction Cis soli. Enthalpy ofreaction, AH= SAH gates” 9) 4H reco In accordance with Hess's law 1. @ 12.© 13. © 14 @ AH=AE+PAV 15. () AH=AE+PAV, for solid and liquid, AV=0 or AH= AE + AnRT, for solids and liquids An = 0 16, (a) As heat is evolved, heat content of diamond > heat ‘content of graphite. Hence graphite is more stable. +.AH =—245.5k5-(-28610) =40.510 17. © aH=Hy —Hy = G2 #P,¥2) - E+) = (E:-Ei)+ V2 - RW) =304+4x5-2x3244L atm 48.) Desired equation is H0() ->H0(8), AH =? (Equation Ik- Equation 1) ‘AH =-245.5 10 -(-286K))= 4051 19, @ Thisiselectronaffnityand exothermic process. 20, (9 Kirchot’s equation, h 21. @ 32. (@) Hess's law deals with changes in heat of reaction. 23, (@) Hess's law 24. ) For a finite change AE=C,AT. For an isothermal process AT= 0. Hence AE = 0 25, (a) Work done during adiabatic expansion =Cy(T; ~T)) ‘or ~3000 = 20(T; ~300) = T, = 150K, 26. (@ Entropy change at constant temperature «= natanag 2 «2300102 gen! 27. (@) Concept of thermal capacity is, the heat required to raise the temperature of a body. 28.) AG=AH-TAS, AG must be negative hence AH-TAS must be negative 2.5x10? ~298%7.4= —ve , hence 29, (@) AG = AH-TAS= spontaneous 30. ©) 4p = 4H (Enthalpy)Em 3M. © Endothermic process, AH= +ve,AS=+ve 32, (@) AG=AH-TAS, AH +ve, AS is +ve; TAS>AH for ‘spontandous process. It will make AG, -ve 33, (a) Third law of Thermodynamics. 34. (&) High pressure reduces volume, decreases entropy, hence AS negative. 35. (a) For spontaneous process, AS jis +e 36, (€). Third law of thermodynamics is due to Nernst. ‘age All _ 900318 rT: AS?=28"yoy-(S? 4, +5 increase in entropy, = 43.4)" mot" 32. @) 38. @) cg) =2%186,7 -(130.6+ 223.0) =19.8)K"'mot! 2.257x18 39. () 33 40. (@) AG=AH-TAS 41, (2) Atequilibrium, AG=0 42, @ AG=-RTIn K,orK,= 40%" 43. (@ Condition of equilibrium, hence AG=' 4, (@) Statement of third law. 48. (@)Calorific value of fat> carbohydrate and protein; Butter 34, Sugar 16, Egg 14, 46, (@ Allvalues are same 47. (®) For one mole the value is -22 keal mol 48, (@) C+0,-+CO,; AH® 2C0+0, - 2C0;; (2) ‘multiply equation (1) by 2 and substract equation (2) and divide final equation by 2 49, (@) 57.3-55.4= 1,9 kJ (57.3 KJ isheat of neutralisation of strong acid and strong base) $0, (@) Its infact the formation of one molecule of H,O always as= = 0.109 KI K“'mol"! (a* +0” —3H,0) 451, (©) Neutralisation of weak acid with strong base hence < x. Extra heat is utilised to effect the ionisation of weak acid, '52, (@) Equation (1)—Equation (2) gives. S+02 -»S02,AH =(y-2x) 53, (@) Itis always=— 57.32 + ionisation of weak acid 54, (b) Desredeqn; C)Hy +303 —+2CO +2H,0 ‘AH = 2(-394) + 2(-286)—(52)=—1412kI Ca0+H,0 > Ca(OH), ; Exothermicprocess. Energy of isolated system is constant. Depending upon the value of TAS, AG can be lesser, equal or greater to AH = 59, (b) The more the energy, the lesser isthe stability. AH = 20keal.....(1) CO; +2H,03 (2) 60. (8) CH4+202 “al = 40 keal. +0, 70025 52H, ;AH=-20keal...-(8) (C+2H, >CH, =~ 40kcal 2H, +02 (2) +@)-(@wehave, or AH =-20+(-40) ~ (-20) 194kJ.Foronemole 61, (9) Atffortwomoles 62. ( Enthalpy of neualistion of HCI with NaOH i. question gev of HCI. 250%4 500x2 1gev Jhence ti ( se igor [ SS lg ‘ a vabex i Ipy change when | 63. (©) Enthalpy of neutralisation is enthalpy chang: © ‘ev of acid is neutralised by 1 gev of base. In question, 2 gev of HSO4 is being neutralised. Hence enthalpy of 114.64 neutralisation is 57.324 In question 0.01 gev of NaOH is being neutralised by 0.01 gev of HCl and value is x kJ, for 1 gev the valueis- 100x (exothermic process). AH = HY (products) ~ H?, (reactants) =-110.5 + (-241.8)~(-393.5+0)=41.2 64. @) 65. ) 66, (@) Add equation (I) and (II) divide by 2 the equation obtained - 44 + (—152) v6. —98kcal Lavoisier and Laplace law. @ This reaction shows the formation of H,0, and the -X, Tepresents the enthalpy of formation of H,O because as the definition suggests that the enthalpy of formation is the heat evolved or absorbed when one mole of ‘Substance is formed from its constituent elements. 1 1 2 ©) pth +7Ch —> Hl 4rHci =D BE. of reactants ~ZBE of products 1 430+5240-BE of HCL * BE ofHCl=215 +129 +99 @ We know that heat @ ada functions but and work (w) are not state anh WitaaateRneion HeToeO tions 4 ©) Forthe cela correct PCL) = Pag) 4 Chie)6 i a 9. ‘The reaction given is an example of decomposition reaction and we know that decomposition reactions are endothermic in nature, ie-, AH> 0. Further An=(I+1)-1=+1 Hence more number of gaseous molecules are present in products which shows more randomness ic., AS> 0 (AS is positive) (©) Thereaction for formation of HCI can be writen as H+ Cl, >2HCL H-H+Cl-Cl42(H-C) ‘Substituting the given values, we get enthalpy of formation of 2HCI = ( 676-862) = -186 KJ. «i Enthalpy of formation of HCI = 1885 =-9314. @ AG=AH-TAS Atequilibrium, AG= = 0= (170 * 10° )—T(1705K!) T= 100K For spontaneity, AG is — ve, which is possible only if T> 1000K. @) Enthalpy of reaction = BE peacast) B-E (produc) = [BE (coo +4BE c+ BEW-w ] -[Beyc-c)+6BEc1] = [606.1 + (4410.5) +431.37)] -[336.49+(6* 410.9) =-120,0K) mol (@) AS forthe reaction teins XY AS =50- (30+ 60)=-405 Forequilibrium AG =0= AH - TAS @ H,0() == 1,00) ‘av =40630 Jmal~! ‘a5 = 108.8 JK"! mol! AG = AH-TAs When AG ~0 AH-TAS =0 ‘AH. _406305moI! 79557 oneal mort OPE © Correct choice : (8) @ () K,>0 (iv) Spontaneous @) AG 2s) + 300,02); AH=-26.8KJ Ai) FeO{s) + CO) —> Fe(s)+C0368): AH=-165KJ (ii) 4. ()-2e9. (i), we get Fe,0,(9) + CO) —> 2FeOKs)+ CO,() AH=-268+33.0-+6210 Ideal gas during spontaneous expansion into ‘vacuum does not do any external work. Given AH = 30K3 mol! T=273+ 27=300K Hy _ 3x10! as, = Ht = 3210" J mot! Sp == Fog Jmol = 100) mot K* Given 4H(g) > 2H (2); 4H = -869.6 1) 2H (g)—4H(g); AH = 869.6 15 Ha(g) 92H) a= ®S5S ~asasia Given AH 1p 40 0 3B—2C+D 125 ~Q) Bai! Han ® ‘To calculate AH operate 2.x eq. (1) +9. (2)—e9.3) ‘AH =300-125-350=-175 Since, inthe first reaction value of An is positive. 1 oe An = 1-}= hence entropy will ierease i.e. 2 As=+ve, Clar)+ £ O42) > CO; AS"= +8 Since, AG° = AH? ~ TAS hence the value of AG decreases on increasing temperature, A35x10° 2B © 25,260 cal/molK H,0 (0) == H,0 (g) AH=40.66 KImol"! T=373K Y AE = AH-AnRT = 40,66*10° Jmot" 1% 8.314]K"tmot «373 K AE=37558/ mol AE=37.56 Kimoti> 21. ®) At low temperature the AS is ~ ve which makes AG positive (AG= AH TAS). Butat higher temperature AS is +ve which makes the AG negative (condition for spontaneity) @ It violate 2nd law of thermodynamics, not Ist. 23. @ aHinegative shows that the reaction is spontaneous. Higher value for Zn shows that the reaction is more feasible. 24, (©) Fora cyclic process the net change inthe internal energy is zero because the change in internal energy does not depend on the path. 28. (6) CH,=CH, (g) +H, (g) > CH,-CH, (@) AH: ‘C)+4(C-H)+1 (H-H)-1(C-C)-6(C-H) (C=0)+1(H-H)-1(C-C)-2(C-H) 15 +435-347-2%414 =1050-1175=— 1251. 26. (a) For spontaneous reaction, dS > 0 and AG and AG should benegativei.e. <0. 27. (2) AG?=—RT ink, or-AG?=RT Ink, 28. (&) Enthalpy change for a reaction does not depend upon @ C+0, = co,; AH =-393.5 Kimo!” 00; @ corto, —2c0,:aH1--2830 Kinet" After, @-@), We have C+40, CO aH =-1105 kimot" 31. @ For spontaneous reaction AG should be negative. Equilibrium constant should be more than one (AG=~2.308 RT logK, IfK,= I then AG=0; IfK, <1 then AG=+ve). Again AG = -nFEQ.y - Ey must be +ve tohave AG ~ve. 32. @) AH=AU+AnRT for Np +3Hy —> 2NHy An,=2-4=-2 2.AH=AU-2RT or AUSAH2RT -.AU>AH 33. (N) Xy-+¥;—> 2XY AH=2(-200) Let x be the bond dissociation energy of X,. Then sig etna era: Mer ant ee en Oe, 400 a x = 42 800 id mol or X= Fog = 800 Kd mol ‘option was not mentioned. So the ) (in the question paper. anewer has been marked cH, cH, cH, H. ce Ce HOH ce cl H ce ce ch, ch, cH, .e work done is greater than 34.0 arora Seow ree the heat absorbed in ‘sible process: Hen P erable process would be greater than in the latte, case. So Trev) < Tein) ; ‘The standard enduiry ‘of formation of CH, is given by the equation : (3) + 2H2(¢) 7H) Hence, dissociation energy of hydrogen and enthalpy of sublimation of carbon is: required. 1n(6)+Cl(@) — 21) AH= [AH )—@)* ‘AH, ;+ AHCHCI) “[anll— regio + 242.3 + 62.76-2*211.3=33.46 35. (©) 36. @) 33.46 =16.73 kJ/mol fen = 28 31. @ Cy #Z0xq) 7 OO® AH-AU=AnRT s 4x8.3144298 = 1238.78 1 mol 38, (@) AG?=AH?—TAS* For a spontaneous reaction AG® < 0 ‘AH? as? or AH?-TAS° <0 =» T> 179.1x10° =T> >1117.9K = 118K 2 © ‘AU= AH—AnRT=41000~(1 x 8.314% 373) =37898.88 Jmol" ~ 37.9 kimot-! Spontaneity of reaction depends on tendency 10 acquire minimum energy state and maximum randomness. For a spontaneous process in an isolated system the change in entropy is positive. e energy involved in the conversion of 40. © 4. ® 1 C128) to CI (ag) is given by 1 AH = =A ging, ZAaiste, + MegHE + Ag HS Substituting various values from given data, we 8¢ an-(J, ($20) +2648! = (120— 349-381) kd mot! =— 610i mot! 2 @ (OH,0) —H1* (ag) + OH” (aq.); 4H, = 57.32 ky @M@)+ 306), #201; AH, = ~286.20 idFor reaction (i) ‘4H, = AH°s (H” aq)+AH®; (OH aq) AH?s(H0, 0) 57.32 = 0+ OH" (OH™,aq)~ AH*,(H,0,0) (iii) For reaction (ii) AH, = AH?¢(H,0, &)~ AHP (Ha, 8)~ Sat (0p,g) 286.20 = AH?;(H,0, 6) On replacing this value in eq, (ii) wehave 57.32 = AH*,(OH™ aq) ~ (-286.20) ‘AH?;(OH™ ,aq) = ~286.20+57.32 = 228.88 43. (@) N2+3H2—+2NH, AH =2x-460 kimor “ 45. Let x be the bond enthalpy of N—H bond then (Note : Enthalpy of formation or bond formation enthalpy is given which is negative but the given reaction involves bond breaking hence values should be taken as positive.) AH= 5 Bond energies of reactants ¥ Bond energies of products 2%-46= 712+ 3 x (436)-6x —92=2020-6x 6:=2020+92 6e=2112 x=+352ki/mol . ©) Atequilibrium AG=0 Hence, AG= AH-T,AS=0 AH aS For a spontaneous reaction ‘AG must be negative which spossible onlyifAH—TAS <0 ¢ AH< TAS “AH=TAS or T, AH o> SLT ©) C,HsOH(O +302(g) + 2C02(g)+3H20(4) An, =2-3=-1 AU = AH -An,RT 8314 =-1366.5-(-D xy «300 8314 8384 «300 = 71366.5+ (I) Tos == 1366.5 +0.8314 x3 =~ 1364 00610 41. 51. ® ® © 2. © LZtermodsnonico EU 4NO3(8)+02(g) + 2N20s(g), 4, H=- 111 KS [se 2N30s(8) AH? -111-S4= aH AH'=- 1651 Process is isothermal reversible expansion, hence AU= 0, therefore q=—W. Since q= +208 J, W=-208 5 2.303 RTlog,,K 52.303 RT log,, K= AH®— TAS? 2.303 RT log,, K= TAS°— ARP Iogig K = ZAS°=AH® _ 29810+54.07*1000 10K = Rr oe 2303RT ~~ 2303x8 314x298 = 9.99810 Since, liquid is passing into gaseous phase so entropy will increase and at 373 K during the phase transformation it remains at equilibrium, So, AG=0. The species in its elemental form has zero standard ‘molar enthalpy of formation at 298 K. At298K, Cl, is 28 while Bry is liquid. @ 20)+H,() —> H-C =C-H@) ‘AH=225 kd mot"! @ 203) 20) ‘AH= 14100 mot! 1410 t €(e) —+C¢g)aH =“? = 705khmot Gi) Hy) —> 2H) ‘AH=330k mot! From equation (i): 225=[2* Ay, cig) *BEW-H] ~[2xBEc_y +1XBEcac] 225=[1410-+1x330]-[2 «350+ 1x BEc c] = Haid alae. Beil oi palate ‘Ths Standard enthalpy of the combustion of glucose can be calculated by the eqn. a CeH,20(8) + 60,(g) > 6CO,(g) + 6H,0( eekagos)o~ aio) AiG ,0) AH? = 6 (-400) + 6(-300) - (-1300) AH? =-2900kJ/mol For one gram of glucose, enthalpy of combustion 2900 ane =- 2 16.1110/; 180 LyLo 1. (© The criteria for the spontaneity, AS system + AS surroundings, must be + ve 2 (© AG~=AH~TAS. For spontaneous process AG <0. To et AG <0, we must have AH <0; AS>0 22.03K™ mot 3 @ 4s An as = 602x100 4. (©) Examine the chemical equations. Ifthereis decrease in ‘number of moles of gaseous products, the entropy will decrease and vice versa. 5. (@ Gaseous ions, when dissolved in water, get hydrated ‘and heat is evolved (heat of hydration). CI (g)+a9 > CI" (ag) is such reaction 6. (@) Writethe proper chemical equations. (graphite) +0,(g) > CO,(g) AH =-393k ven) H,(@) +5020) 1,00) att 28619 sl) C,HOH()+30;(@)$2C0,(g)+3H,00) aH=-13603 “~“@ From (2x1+3xHl)~ (All) we get 2C+3H, +40, >C;H,OH #- 2-393Ks) + 5(-286K) — (136080) 1 @ CoH o+¥0, (8) 6COz (g)+3H20 (1) An=6-15/2=-3/2 8 (© Cisincorrect ; The correct is AE = Aq+ Aw 9. @) AG=AH-TAS AG = 9100 ~373.2x25.5=-4166 cal mol"! 10. (a) 1-Il, gives, 2Al+Fe,03 + 2Fe+ Al, we have ~400-(-200) = -200; For one mole of iron the value is 100 cal 1. BG alee bamy eet tr ining ot €) bonds~ Energy evolved by formation of bonds H mise HOH OH. Wa, H-H+ ease Hf #H Peis i -H (103), (80,, )o-c 1 BHO 2) (peso 13. @) AG =AH-TAS ; At equilibrium AG = 0; AH=TAS ; aH T=38 2 £5000 975K 12x10? 14, (@) The third law of thermodynamics is about entropy, . 16. (a) tied ir ° Itisneutralisation of strong acid with strong base jothermic, hence he Dissolution of KNO, is end at Tee orbed and cooling is observed. 19, (@) Isobutane + oxygen > CO? +H20 AH = =2870 KJ mot" ..4p n-butane + oxygen > CO; +H,0 AH = ~2878 kJ mot”.() -butane Isobutane, ‘AH =(-2878 +2870) 8 KI mol" “AH, @ Apply Kirchof’s equation Sone =AC, 21. (0) Bond dissociation energy of PH,(g) = 228 kcal mot! PH bond energy = 228 Gi 76 kcal mol oe fs n/Nu Bond energy of 4 (P—H) + (PP) = 355 keal mol or x716+(P-P)=355 kcal mol”! P-Pbond energy= 51 keal mol“! 22, (@) AHP solution =U (lattice energy) + AH? hydration ©) aHe=au'sanRT 5x8314x298 AH? = -772,7 + -——~ **" 760, rt - 760.3 id mel 24. @)HzS04+2KOH + K,804+2H,0 8 oS % o faae 13.7 keal is the heat evolved when 1 gev of strong acidis neutralised by 1 gev of strong base. The fist reaction is exothermic and the second reaction is endothermic. If on passing the mixture of Oy and 25. (@) Constant AH of both the reactions must be same. Moles of O2 needed to evolve 132 kJ _ 5x132 206 Hence steam: O ratio must be 1 :0,6 1 6 H2®* 5020) — H,007 AH =~ 285 813 a HY (04) + OFF ( Spel, ane te) — 1.0.0 A “ 22@ Hq — + (age e; antaa (y convention) oo27.0) 28. @ 29.) 30. @) 3.0 (-Ci-Gid gives, 1 = Lanta) + 30x18 + +a —+ OFF (AH =—285.8 + 57.3=—228.5 kd For 5 moles of gas at temperature T, PY; =SRT For Smoles ofgasat temperature T-2, PV; =SRF-2) P(Vq Vy) =SROT=2- PAV=-10R, - Pav =10R When AV is negative, W is + ve. RM = PaV2 * sbarx2dm? 165 4m? y- eee = 10 dn Work, W= Pye (Val ~ Visa) 1 bar (10-2) 1x 108Pax8% 107m? =-800) COzoneisallotropic form of oxygen and is of higher enerey (by 68 kcal mol™!) than O2 . Hence it cannot be taken 4s the reference a standard state. ‘eee pHa + 5X2 > Let the bond enthalpy of X—X bond be x. 1 AH, (HX) =-50= 5H yt Fally-x =e 1 e axe px ee 2: x=50%2=100 kImol” HY (aq) + OH (aq) = H20 0; AH=—5731 10643 Gi) For the second reaction the value should have been 2x(-573)=-11461 ‘The difference (114.6 - 106) = 8.6 ‘Jmol is used to effect of the ionisation of oxalic: ‘Afier the event the energy remained in the body of the athe = 58° = ro0ks “= Weight of water to be evaporated by 780 kd ofeneray H,C,0,420H <> C207 +2840; 18 a7 On 391E ee” 33, (@) CuSO, (3)+ $H20(@) —> CuSO4-5H20(8) A AH =-71.5keal 51,0) > 5H,0@); ‘AH =5 x 10.5 keal =52.5 keal @+m), CuS04(s)+5H,0() —? CuS04.5H20(8) ‘AH =-71.5+52.5=-190 kealmot"! 34. (0) OHiya, = AH sot, ~ AH aie 180 =-179 kealmol” ‘Then AHiyg (Na*) + BHyyg(CI") =—179 ce ABlyy(Na*) + Z hyd (Na*) =-179 OF AHlyg (Ne*) =—107.4kealmol™ AC, =2*25.143%753-[1038+3*288] 35. @) =85.9 1K*mol* AH) —AM) _ ac, Th n 358-298 ae AH =-281363mol™ =-28.136k mol” pr@+ 3r,() — NB: AH =U 13k 3 ot Alvan + 5 Aer ~3 Hy Let x kimol" be the bond energy of F — F bond then bond energy of N #N bond = 6x co Pxort Poca ‘On solving, x= 15691Imor” and NeNbondenergy=6 « 156.9=941.4 kImot! 37. @) Ally for strong base and strong acid 213.7 kealeq ‘AHTiqq (CH COOH) -12.5-(13.7)= 1.2 kealmol™ ‘AHgg (NH4OH) == 105—(-13.7)— AH jn (CH3COOH ) =13.7-105-12 =2 kealmol”ttom 38. (a) 39. ©) 40. @) 41. @ 42.) CH, (@)+20>(g) —> CO,(—)+2H,0() AH = 89010 =@ 2H20() 42,0), AH =2x405=8110 ~~ (ii) From (i)+ (i), weget CH, (8) +203 (8) —> CO,(g)+2H,0() AH =—890+81=—80910 By bomb calorimeter we get AE 2C6Hg (+1503 (@) —s 12C0,(g) +640 (0, AH - AE = AnRT =(12-15) «8.314 %300=-7.483 ky ‘The greater the (negative value) ofheat of neutralisation, ‘the more is the strength ofthe acid. Hence, HCOOH> CH;COOH > HS > HCN H,0@—> H,0@ AH=408 mol Hence for H20(g) —4 H,0() AH =—408 kmor! AH =—40.8 s =-4.0810 _ AH 408x107 4 aS = - S 771093 3K: The enthalpy of ionisation of weak acidis given by AMion(HA) AHN (weakaci/ strong base) 4H N strong oid /strong bse) =~56.1~(-$73)=1.2 kimol 4. @) 1.5 imo ion in 1 Msotution ‘AH (ionisation) Hence % ionisati _ 512) , 19920 ” LS ‘Atomisation of methane CH, @ —> C@)*+4H(@) AH =360 kcal 360 4 C—Hbond energy =~ = 90 kcal mol“! CH (@) —> 201g) + 6H(g); 4H =620 kcal of He_c + 6 He = 620 He-c = 620-6 He =620-6%90= 80 keal For non spontaneous reaction AG =+ve 4G = AH -TAS and AS =121 JK For AG =+ve ‘AH has to be positive. Hence the reaction is endothermic. AH = TAS=298 x 1215 = 36.06 15