Thermodynamics Numericals

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THERMODYNAMICS NUMERICALS
1. Calculate the internal energy change in each of the system: (i) A system absorbs 15KJ of heat and does 5KJ of work. (ii) 5KJ work is done on the system and 15KJ of heat is given out by the system. Ans: (i) q =15KJ w= -5 KJ U=q+w = 15 + (-5) = 10KJ (ii) W =5KJ q=-15KJ U= q+w = -15 + 5 = -10KJ
2. Calculate the amount of work done in each of the following: (i) one mole of an ideal gas contain in a bulb of 10 litre capacity at 1 atm pressure is allowed to enter in evacuated bulb of 100 litre capacity. (ii) One mole of gas is allowed to expand from a volume of 1 litre to volume of 5 litres against constant external pressure of 1 atm. (1 litre atm=101.3J) Ans: (i) W= -PV heat absorbed=+ve , heat evolved =-ve Q=0 , w=0 (ii)P=1 atm , V=V2-V1=5-1=4litres W=-PextV=-1 x 4litres=-4 litres atm = -4 x 101.3J =-405.2J -ve sign work is done by the system.
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3. Calculate q,w & U when 0.75 mol of an ideal gas expands isothermally and reversibly at 27.C from a volume of 15L to 25L. Ans- Work done on isothermal reversible expansion W=-2.303 nRT log V2/V1 =-2.303 x 0.75 mol x 8.314 JK-1mol-1 x 27 + 273 log 25/15 =-955.5J ( -ve expansion work) For isothermal expansion of gas U=0,Q=-w=+955.5J
4. If water vapour is assumed to beperfect gas 1 molar enthalpy change at 1 bar and 100C is 41 KJmol-1. Calculate internal energy change when (i) 1 mol of water is vapourised at 1bar P 100 C (ii) When 1 mol of water is converted into ice. Ans: (i) H2O(l) H2O(g) ng = 1-0 =1 , H=U + ngRT U=H - ngRT 41 KJmol-1 x 8.314 x 10-3 KJK-1 mol-1 x 373K =37.90 KJ mol-1 (ii) For conversion of water into ice The change is H20 (l)H20 (s) Change of volume is negligible hence H=U=41 -1 KJ mol
5. Find internal energy change for the reaction A( l) A (g) AT 373 K . Heat of vapourisation is 40.66 KJ mol-1 and R= 8.3 Jmol-1 K-1 Ans- A (l) A (g) ng =p nr = 1-0=1 T = 373 K , vap H =40.66 KJ/mol-1
U=H - ngRT =40.66 x 1 x 8.314 x373=37.56 KJ mol-1
6. 1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298k and 1 atm pressure acc.to eqation C(graphite) + O2(g) = CO2(g). During this reaction the temp rises from 298k to 299k ,if heat capacity of the bomb calorimeter 20.7 KJ/K ,what is the enthalpy change for above reaction at 298k at 1atm. Ans: Rise in temp=299-298=1k Heat capacity C=20.7KJ/K Heat absorbed Q= Cvt at constant volume 20.7 KJ/k x 1K =20.7KJ This is heat evolved in combustion of 1g graphite Heat evolved in combustion of 1 mole of graphite=12g of graphite=-20.7 x 12KJ =-248.4KJ Heat evolved and vessel is closed . enthalpy change isU=248.4KJ
7. Calculate the entropy change involved in the conversion of 1 mole of liquid water at 373k to vapour at same temp. latent heat of vapourisation of water vap H=2.251 KJ/g Ans: Water vapour vap S = vap H / Tb = 2.257 KJ/g = 2.257 x 18 KJ/ mol Tb = 373k vap S= (2.257 x 18 KJ/mol ) / ( 373k) = .1089 KJ mol-1 k-1 = 108.9 JK-1 mol-1 8. A heated copper block at 130 C loses 340 J of heat to surrounding which are at room temp of 32C. Calculate
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entropy change of system( copper block) Entropy change of the surrounding Total entropy change due to this process Assume that total entropy change of the system and the surrounding remains constant. Ans: Tsys = 130C =130+273= 403 k Tsurr = 32C = 32 =273 =305 K qsys = -340 J , qsurr= +340J i) entropy change of the system Ssys = +qsys / Tsys = -340J / 403 K = -0.84JK-1 (non spontaneous) ii) entropy change of surrounding Ssurr = qsurr / T surr = +340 / 305 = + 1.11JK-1 ( spontaneous) iii) total entropy change Stotal = S sys + Ssurr = -0.84JK-1 + 1.11 JK-1 = 0.27JK-1 9. Enthalpy and entropy of a reaction are 40.63 KJmol-1 & 108.8 KJmol-1 resp. Predict the feasibility of a reaction at 27C. Ans: G = H - TS =( 0.40630 Jmol-1 - 300) x 108.8 JK-1 mol-1 = 7990 J mol-1 Since G is positive (G 0) the reaction is not feasible in forward direction. 10. At 0C ice and water are in equilibrium and H = 6.00 KJmol-1 for the process H2O (s) H2O (l) . What will be the S & G for conversion of ice to liquid water. Ans: Since reaction is in equilibrium G = 0 G = H - TS
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0 = H - TS or S = H /T = 6000 Jmol /273 = 21.98 JK-1 mol 11. Calculate the standard free energy change of the reaction 4NH3 + 5O2 (g) 4NO (g) + 6H2O (l) Given that the standard free energies of formation rG of NH3 (g) , NO, 2H2O are -16.8 ,+86.7 and 237.2KJmol-1 resp. predict feasibility of above reaction. Ans: rG =fG products - fG reactants [ 4( 86.7) + 6(-237.2) ] [ 4 x -16.8 + 5 x0 ] = -1009.2KJ rG is negative so reaction is feasible. 12. For equilibrium constant K for following reaction 2NOCl 2NO + Cl2 , given rH= 80.0KJmol-1 , rS =120JK1 mol-1 at 400 k. Ans: rG = rH - TS = 80000Jmol-1 400 x 120 J = 32000J rG = -2.303 Rt log K 32000= -2.303 x 8.31 x 400 logK log k = -4.1782= 5.8218 K = Antilog 5.8218 = 6.634 x 10-5 For equilibrium PCl5 PCl3 (g) + Cl2 (g) At 298 k Kc =1.8 x 10-7. What is G for the reaction R= 8.314 JK-1 mol-1 Ans: Kp = Kc (RT) n n = np nr = 2-1 =1 Kp = (1.8 x 10 -7 ) ( 8.314 x 298 ) = 4.46 x 10-4 rG = -2.303 RTlogKp 12.
-1
= -2.303 x 8.314 x298 x log(4.46 x 10-4) = 19118.6 mol-1 =19.12 KJ mol-1 13. At 60C dinitrogen tetraoxide is 50% dissociated .Calculate the standards free energy at this temp and one atmosphere Ans: N2O4 2NO2 (g) Initial amount 1mol is 0 At eq , 1- 0.5 = 0.5 ml , 0.5 -0.2 = 1 mol , total = 1.5 mol PN204= ( 0.5/1.5) x 1atm = 1/3 atm PNO2 = (1/1.5) x 1 atm = 2/3 atm Kp = ( PNO2 /PN2O4 = [(2/3)2 / (1/3)] = 1.33 atm rG = -2.303RTlogKp = -2.303(8.314J) K-1 mol-1 =33K log 1.33 = -790Jmol-1

Thermodynamics Numericals

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Thermodynamics Numericals

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Prepared by Mrs. Jhala

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Prepared by Mrs. Jhala

U=H - ngRT =40.66 x 1 x 8.314 x373=37.56 KJ mol-1

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Prepared by Mrs. Jhala

Prepared by Mrs. Jhala

Prepared by Mrs. Jhala

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