SOLVED PROBLEM 1. The heat of combustion of ethylene at 17°C and at constant volume is — 332.19 keals. Calculate the heat of combustion at constant pressure considering water to be in liquid state. (2 =2 cal degree"! mol-!) SOLUTION The chemical equation for the combustion of ethylene is CH{g)+30,(g) —+ 2C0,(g)+2H,0() 1mole 3moles 2moles _ negligible volume. No. of moles of the products = 2 No. of moles of the reactants = 4 * An = (2-4)=-2 We know that AH = AE+ An RT Given that AE =~332.19kcal T = 273+17=290K R =2cals=2 «10-3 kcals AH = ~332.19+2 «103 x2 «290 =~ 333.3 kcalSOLVED PROBLEM 2. The heat of combustion of carbon monoxide at constant volume and at 17°C is — 283.3 kJ. Calculate its heat of combustion at constant pressure (R= 8.314 J degree“ mol"). SOLUTION CO) +} 0) —> Coxe) Imole mole mole No. of moles of products = No. of moles of reactants = An =No. of moles of products — No. of moles of reactants wal 2 2 Given that AE = ~283.313 T = Q73+17)=290K and R= 8314 J 068.314~ 107k Substituting these values in the equation AH = AE+ An* RT we get a =—2833+| 4314 x10) 290] = — 2833-120 = -284.5k7 + Heat of combustion of CO at constant pressure is — 284.5 kJ.SOLVED PROBLEM 3. The heat of formation of methane at 298 K at constant pressure is —17.890 kcal. Calculate its heat of formation at constant volume. (R= 1.987 cal degree“ mol!) SOLUTION The thermochemical equation for the heat of formation of methane at 298 K at constant pressure is: C(s)+2H,(¢) —4 CHg) AH = -17.890keal No. of moles of gaseous products =1 No. of moles of the gaseous reactants = 2 Change in No. of moles, An= 1-2 =-1 Given that AH=-17.890keal; T=25+273=298K and R=1.987 cal= 1.987 « 10*keal Substituting these values in the equation AH = AE + An® RT AE ==17.89+ [21 «(1.987 10%) x 298] =-18.482keal The heat of formation of methane at constant volume is — 18.482 keal.SOLVED PROBLEM 1. The heat ofreaction 4H,+ [Link], sHclat27Cis—22 1 kcal. Calculate the heat of reaction at 77°C. The molar heat capacities at constant pressure at 27°C for hydrogen, chlorine and HCI are 6.82, 7.70 and 6.80 cal mol" respectively. SOLUTION Here. 1 1 yh + oh — HCl AH =—22.1 kcal ACp= Heat capacities of products — Heat capacities of reactants = 6.80- [te 82) + x00 70)| = 6.80-7.26=—0.46 cal=—0.46 10*keal Tq, 73 +77 =350K; T, = 273 +27=300K Ty T, = (350-300) K=50K Substituting these values in Kirchoff's equation, we have AH, — AH, = AC, (T,-T)) 22.1+ (0.46 104) «50 = -22.1+ (0.023) = -22.123 keal <. Heat of reaction at 77°C is — 22.123 kealSOLVED PROBLEM 2. The heat of reaction N,, + 3H, — 2NH, at 27°C was found to be —21.976 kcal. ‘What will be the heat of reaction at 50°C ? The molar heat capacities at constant pressure and at 27°C for nitrogen. hydrogen and ammonia are 6.8, 6.77 and 8.86 cal mol degree. SOLUTION Here, AH = ~21.976keal Ty = 273+ 50=323K T, = 273+27=300K [1-1] = G23-300)K=23K AC, = Heat capacities of products — Heat capacities of reactants = 2*8.86)—[68+(3 «6.77)] = 17.72-(68+20.31)=—9.39 cal = 9.39 «107 keal ‘Substituting these values in Kirchoff's equation, we have AH, = AH, + (T,-1)) AC, = —21.976+ [23 x 9.39 « 105)] = —21.976+(-0.216)=-22.192 kcal Heat of reaction at 50°C is = 22.192 kealSOLVED PROBLEM 1. Calculate AFP for the reaction CO,@)* ys) —> COl)*H,0@) given that AH for CO,(g), CO(g) and H,0(g) are-393.5,-111.31 and-241.80 kT mol respectively. SOLUTION Here we have CO,g)+ Hyg) —> CO(g)+H,0G) AFP = AH; (products) — AH (reactants) = [AH [CO(g)] + AH} [H,0(g)]]-[AH [CO, (g)] + AH} [H,Q)]] = [1113+(241.8))-[393.5+0] = -353143935 = 404 kJSOLVED PROBLEM 2. The standard heats of formation of C,H,OH(I), CO,(g) and H,0(/) are -— 277.0, -393.5 and -285.5 kJ mol respectively. Calculate the standard heat change for the Teaction CH,OH()+30,() —+ 2CO,(¢)+3H,0() SOLUTION We know that : AH® = AH; (products) — AH (reactants) In the present case A = [2x AH5[CO,@)]+3 «AH 7[H,0()] ~AHFICHOH(D] +3 « AH} (02) = [2 «(-393.5)+3 x-285.5]-[-277.0-0] =-16435-(277) =~ 1366.5 kJSOLVED PROBLEM. Calculate the standard heat of formation of propane (C;H,) if its heat of combustion is— 2220.21 mot. The heats of formation of CO,(¢) and H,O()) are 393.5 and —285 8 KI mot respectively. SOLUTION We are given. ( C,Hy()+50,(¢) —> 3C0,(@)+44,0() AH, = -222021I @) ~~ C+ Og) — COW) AH = -3935K] (i) H@+40,¢) —> #00 AH =-2858kI We should manipulate these equations in a way so as to get the required equation 30(s)+4H(¢) —> CH,@) AH =? Multiplying equation (fi) by 3 and equation (iii) by 4 and adding up we get 3C(s)+30(¢) —> 3CO,(e) AH =-118051I 4H,(g)+20,(¢) —> 4H,0() AH =-1143.2k) (o) 30) +4H(g)+50,@) — 3CO,(g)+4H,00) AH = -2323.7 Subtracting equation (7) from equation (iv). we have 3C(s) +4H,(g) +50,(2)-50,(¢) —+ C)Hy@) AH =-1085K0 . The heat of formation of propane is— 103.5 kJ mol".SULVED PRUBLEM 1. Calculate the heat of formation of potassrum hydroxide Irom the lollowmg data. @ K()+H,0(aq) “3 KOH+ 3H, 9 AH =~48.0keal (ii) H,@)+40,@) —3 1,00) AH =-685kcal a) KOH(s) —4 KOH(ag) AH =-140kcal SOLUTION We should aum at finding the value of AH for the equation, which is the heat of formation. K(s)+ 40,¢)+ 4HY@) — KOHG) AH =? Adding equations (i) and (i) and subtracting equation (iii) will give K(5)+H,0() +H) + 10,(g)-KOH(s) —+ KOH(aq)+ Lit (g) +H,0()-KOH(ag) AH = -48.0+(-685)-(-14.0) =-1025 cal or K()+$H,@)+ $0,¢) —> KOHG) AH = -102.5kcal Thus heat of formation of KOH 1s— 102.5 kealSOLVED PROBLEM 2. The heat of combustion of ethyl alcohol is — 330 kcal. If the heat of formation of CO,(g) and H,O(/) be — 94.3 kcal and — 68.5 kcal respectively, calculate the heat of formation of ethyl alcohol. SOLUTION We are given @ C)H,OH()* 30g) —» 2CO{¢)+3H,0() AH =—3300kcal @® C()+O,g) —> CO,g) AH = —94.3keal © Hg)+ 40,¢) —> H,0() AH = -68.5kcal We have to manipulate these equations so as to get the required equation : 2C(s) + 3H) + 30) —>s CHOH() AH =? where A His the heat of formation of ethyl alcohol. Multiplying equation (b) by 2 and equation (c) by 3 and adding up these, we get 2C(s) + 3H,(g)+ 40,2) —+ 2C0,(e)+3H,0() AH = —394.1 kcal Subtracting equation (c) from the above equation, we have 2C(6)+3H(g)+ 4.0¢) —+> CHLOH() AH = -394.1—(—330.0) Thus the heat of formation of ethyl alcohol is — 64.1 keal.SOLVED PROBLEM 3. Determine AH of the reaction Cs) + 2g) —> CH(e) from the following data : . @ C(s)+0,e) — CO) AH =-393.710 @) Hg)+ $0,¢) —+ 1,00) AH = ~285.7k0 (iit) CH,(@)+20,(e) —> CO,¢)+2H,0() AH =-8903kI SOLUTION Multiplying equation (71) by 2 and adding to equation (i), we get (a) CG)+0x¢)+2H,g)+ 0g) —> 0O,(g)+2H,0() AH = (2x -285.7)+(-393.7) = -965.1kI On subtracting equation (if) from equation (iv), we get C(6)+2H(@) = CHE) AH = -965.1-(-8903) AH =-148K0 Thus the heat of formation of methane 1s - 74.8 kJ.SOLVED PROBLEM 1. Given that energies for HH, O=O and O-H bonds are 104, 118 and 111 keal mol! respectively, calculate the heat of the reaction Hyg)*+ }0,@) — 2,02) SOLUTION In this reaction, two O-H bonds are formed and one H-H bond 1s broken. Therefore we can waite for A AH = -2 AH(O-H)+AH(H-H)+ 4AH(0=0) = (2111) +104+ (}x118) =-222+104459 = —59kcal mol! :. The heat of the given reaction is — $9.0 keal mol