a0 Gat boo o% Thevmad A system performs 101.3J of work on its surroundings and Sol. G@ Sol. absorbs 15 kJ ofheat from surroundings. What is the change in internal energy of the system. Work done by the system is taken as negative W=-101.3) Heat absorbed by the system is taken as positive q= 15k] = 15000J AE = qtw ( First law of thermodynamics) =15000J-101.3J= 14898.75 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. For ideal behaviour of water vapour PV = nRT can be applied to find the volume. 1x V=1 0.0821 * 373 V=30.62 lit. AV = V2 —V, =30.62 lit. —Olit. = 30.62 lit. work done=- PAV =—1 x 30.62 =— 30.62 lit atm. = —30.62 x 101.3J=-3101.8Fa 9 gas expands from 3 dm? to 5 dm} against a constant pressure of 3 atm. The work done during expansion is used to heat 10 mole of water of temperature 290 K. Calculate the final temperature of water. Specific heat of water is 4.184 Jg'K" Sol. Work done is irreversible as at constant pressure, AV =5-3=2dm*=2 lit. =-PAV =-3 * 2=~—6 atm. lit. =— 6 x 101.3) = 607.8) This work is used for heating water W=m xs AT 607.8 = 10x 18x 4.184% AT Therefore AT =0.807 Hence final temperature = 290 + 0.807 = 290.807 KBO, The heat of combustion of gaseous methane CH, at constant volume measured in bomb calorimeter at 298.2 K is found to be — 885389 J/mol. Find the value of enthalpy change. Sol. CH, (g)+20y (g) > CO, (g)+ 2H,0(1) Given AE =-885389J mol ! An=1-(1+2)=-2 T =298.2K; R=8.314JK “mol! AH =AE+ AnRT = -885389+(—2) 8.314% 298.2 =-890.34kIo@ Sol. At 300 K the standard enthalpies of formation of C,H,COOH (s),CO, (g),andH,O(Jare respectively -408,-393 and—286kJmol”!. Calculate the heat of combustion of benzoic acid at (i) Constant pressure (ii) Constant volume (R =8.314J mol 'K7!) AH = Enthalpies of formation of products — Enthalpies of formation of reactants. Desired equation is CoHs COOKIE) +0, (g) 3700, (g) +3H,0(1) AH=7(-393) + 3(—286)—(—408 —0) = — 3201kJ Also AH =AE+AnRT or-3201 KI = AE +(-0.5)x8.314x107> x 300 => AE =—3199.75kI8© Sol. The heat of reaction (AH) for the formation of water at 25°C is—68.4 kcal. Find the value at 90°C. The moler heat capacities of H,(g), H,O (/) are 6.62, 6.76 and 18 cal respectively. AH, ~ AH, = AC, (I -T)) AC, =molar heat capacities of products ~—molar heat capacities of reactants The formation of water is H + $02 —>H,0 AC, =18—(6.62 +16 67)=8 cal=8x10 kcal AH, =—68.4+8x10 3 (363 —298)= —67.88k caloY Calculate AH at 358 K for the reaction Fe 203 (s)+3 H (g) ——> 2Fe(s) + 3H,O(1) Given that AH y9 =—33.29 kImol! and C, for Fe.03(s), Fe(s), HzO (/) and Hy» (g)are 103.8, 25.1, 75.3 and 28.85 /K mol. Sol, AC,=(2 x 25.1+3 x 75.3)—(103.8+ 3 x 28.8) =85.9 J/Kmol AH —AH, TT; = AC, (Kirchoff’s equation) =—28.136 kJ/molag Sol. Six moles of an ideal gas expand isothermally and reversibly from a volume of litre toa volume of 10 litres at 27°C. What is the maximum work done? Express the results in various units. Work done W =nRT in2 = 2.303nRT log ¥2 vi vi 10 =2.303x6x0.0821300log 7 = 340.3 lit. atm. If we put the value of R=8.314JK! mol? W=34464.8) ON R=8.314x107 ergsK~'mol! — W =3.44x10!! ergs R=1.987calK7! mol! W = 8236.91 calo@ 10 g of argon gas is compressed isothermally and reversibly at a temperature of 27° C from 10 litres to 5 litres. Calculate q, w, AE and AH for this process. R=2.0 cal K"! mol" log 2= 0.3010 Atomic weight of Argon = 40 Sol, W =—2.303nRT log ¥2- =~ 2.303x12x2300 log v 40 10 W= 103.635 cal For isothermal proccess AE = 0, q=—W =~ 103.635 cal AH=0OW 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. (Cyc, for air is 1.4) Sol. Let V, be the initial volume of dry air at NTP (a) Isothermal expansion. Since AT =0 hence P} Vj =P,V> _ BY _IxV, Vv, 3V, oP =0.333 atm (b) Adiabatic expansion we have y-t 14-1 1% [vl] 273 [3 1 | 2 oe f|—t T [VY TD | YV Ty =176K =-97°C Final pressure under adiabatic conditions asyf 1 fy)" yon P| Vj P, fv, | P O2t7atmaW Calculate the maximum efficiency ofa steam engine working between 110°C and 25°C. Sol. Efficiency of a heat engine is given by - 383-298 eho gy y= n= = 0.222 or 22.2% T 383 On Calculate the useful work done by the heat engine which works between 10°C and 100°C. Heat supplied to engine is 1897.86 kJ T, -T, - Sol w 42-1) _ 197.8655 —S _457.92k) T,8 The latent heat of fusion of ice is 5.99kJ/mol at its melting point. Calculate. (i) AS for fusion of 900g ice (ii) AS for freezing of liquid water 273K, Sol. H0(s) 2S 4,00) @) Latent heat of fusion for 900 g ice AH fgg =e? ey = 299.5KI sg —AHfus _ 299.5x1000 T 273 AS = 1097JK AH fas T when liquid water freezes heat is evolved AS =—2:22%1000 _ 51 94 Jmol 1K7! 273 (ii) AS for freezing of liquid water = —a® Sol. Calculate the entropy change in isothermal reversible expansion of 5 moles of an ideal gas from a volume of 10 litres to a volume of 100 litres at 300 K. For isothermal process T, = T, hence the equation AS=C, ny aRIn v2 is reduced to T, vi AS =nRInd2. = 2.303nR log ¥2 Vi Vi Given n=5, V, =l0litres, V> = 100litres, R =8.314JK~!mol™! AS =2.303x5x 8.314 log ~ = 95.75IK 18-49 Calculate the chan; at 25°C for the reaction CO(g) + 5% (g) > CO,(g) AH =-67.37 kcal and the change in entropy accompanying the process is — 20.7 cal deg"! mol! Sol. AG= AH-TAS =~ 67.37 —298 (-20.7 x 10%) = ~61.2014 kcal mol! a Calculate AH, AS, AG and AE when 1 mole of water is vapourised at 100° C and 1 atm pressure. The latent heat of vapourisation of water is 540 cal g!Sol. (i) 1 mole of water is 18 g therefore enthalpy change AH= 18 x 540 cal = 9720 cal (ii) Entropy change AS = AH/T = 9720/373 = 26.06 cal K"! (iii) Free energy change AG = AH— TAS AG= 9720-373 x 26.06=0 (iv) AH=AE+ PAV therefore AE = AH ~ PAV = AH~ P(V,~ V,) V, = Volume of | mole of liquid water = 18 cm V,= Volume of | mole of steam at 373 K Applying ideal gas equation, Vy = PiViT2 _ 1x22400 x 373 P3T; 1x273 V> = 30600 em? AV=V,—V, = (3060018) cm? = 30600 em> (18 negligible) PAV =1atmx30600cm? = 1x30.6lit. = 30.6 lit atm. 30.6 x 24.2 cal= 740.5 cal (latm lit= 24.2 cal) Hence AE= AH — PAV =9720—740.5=8979.5 cala Calculate the temperature at which the reaction 1 Ag20(8) > 2Ag(8) +5 O2 (g) at 1 atmospheric pressure will be in equilibrium. The value of AH and AS for the reaction are 30.58 kJ and 66.11JK™! respectively and these value do not change much with temperature. Sol. AG=AH-TAS for equilibrium AG=0 _AH _ 30580 68) wag =AH 7p AH _ 30980 _ geo 6k T AS 66.1 Calculate the standard entropy change for the reaction A==B if the value of AH°=28.40kImol! and equilibrium constant is 1.8 x 10-7at 298K Sol. AG°=—2.303RT logK, =~ 2.303«8.31JK~! mol 'x298 log1.8x107 =38466J mol | @ Ages AHP=AG® _ 28400-38466 _ 33 9g | mol! 6 T 298 Calculate the equilibrium constant for the following reaction at 400K 2NOCK(g) > 2NO(g) + Cl,(g) AH®=77.2kJmol!;AS° = 122JK7'mol! at 400K Sol. — AG°=AH°-TAS? = 77.2 x 10° — 400 x 122 = 28.4 x 10° Jmol!AG° = —2.303RT logK, ° o 3 logk, = -—A@ = _=284x10"___3 19g 2.303 RT = 2.3038.314« 400 taking antilog, we get K, = 1.995x10~ 80 Show that the reaction CO(g)+ 502 (g) > CO3(g) at 300 K is spontaneous and exothermic, when the standard entropy change is — 0.094 kJ mol !K!, The standard Gibb’s free energies of formation of CO, and CO are —394.4 and —137.2 KJ mol" respectively. Sol. The given reaction is CO(e)+ 5 02(2)-> C02 (8) AG? (for reaction) = G° products— AG° reactants = Geo, —(Gco +G%, ) = —394.4—(-137.2+0)=—257.2 AG°=AH°?-TAS°® —257.2=AH° + 298 (0.094) or AH® = —285.2KJ Since AG’ is negative the process is spontaneous and AH® is also negative the process is exothermic.At what temperature will water boil when the atmospheric pressure is 528 mm Hg. Latent heat of vaporisation of water is $45.5 cal g ! Sol. The integrated form of Clapeyron equation is ooh AMY [1 ‘] Sp, 2.303R|T, Ty Here P, = 528 mmHg; P;=latm=760mm Hg; T, = ?; Ty = 100°C =373K AH, =545.Scalg !=545.5 x 18=9819 cal mol" jog 260-9819 ft 528 2303x1.987/T, 373, %M7363KA@ K, for CH3COOH at 25°C is 1.754 = 107> at 50°C. K,is 1.633 x 1075. What are AH® and AS° for the ionisation of CH,COOH ? Sol. (AG*)y9g =—2.303 RTlog K, =—2.303 x 8.314 x 298 x log 1.754 x 10-5 =-27194J (AG°)393 =—2.303 x 8.314 x 323xlog 1.623 x 1o-* =-29605 J AG° = AH° _T Ase 27194= AH® —298 As° 29605 = AH° —323 AS? AH® =~ 1.55KJ/mol AS° =— 96.44 J/mol