'· !Pobsolute Values of both internal b determined.
wever, change in internal energyen:(U)rgy (U) and ~nthalpy (H) .:Wot b: determined. and charge m enthalpy can (M.11
p,.ccording · to( principle
h . of conservat,on · • of energy of first law of therrnodynarnics. · , /), lJ : :;:; q +- w w ere V.w 1s work done On the system).
w::::: -2 •303nRTlog- 2 v. =-2 ·030nRTlog- P., ' R2
c1iange in internal energy and change in enthalpy are related as AH aU + p"V or AH
' tu+t/gRT. . standard enthalpy changes (Ml") are measured at 298 K and I atmosphere pressure. ' co1nbustion is an exothennic reaction and the enthalpy of combustion is always ' . negative. , According to Gibb's Helmholtz equation, AG= AH-TAS.
, free energy change and useful work are related as: AG =-W non-expansion·
. In case useful work is electrical work.
.
, iG0 === -nFE
0 cell
, iG0 === -2.303RT log K
, According to third Jaw of thermodynamics,
re dT Sr =11 s D T =J.J.- Use the following data to calculate ~lattice If for NaBr. 1 Lisub If for sodium metal==l08.4KJ mor 1 Ionization enthalpy of sodium==496KJ mor Electron gain enthalpy of bromine== -325 1
Bond dissociation enthalpy ofbromine==192 KJ mor
MI for NaBr (s) == -360.l KJ mor'
I , tifY the state functions and path fun . 1, 1defl lpY, entropy, heat, temper tu ct10ns out of the following: 1 . e11tba a re, work, free energy.
o: fb' e11th~PY 2;7orization ofCCl, is 30.5 KJ mor' Calculate the heat required 1 for the 3, vaporization° g of CCl4 at constant pressure. (M~lar mass CC1 4=154g mor )-
fhe enthalpy of reaction for the reaction:
4, zf!z (g) + 02 (g) -+ 2H2O (I) is ~rH = -572KJ W}lat will be standard enthalpy of formation ofH2o (I)? I (a) Although _the dis~olution of NaCl(s) in water is endothermic but it dissolves. Explain. 15, (b) Whe~ a piece of ice is placed on your hand, you get a cold sensation. Why? · (c) Why 1s standard heat of formation of diamond not zero although it is an element?
(i) For a reaction both M! and ~Sare negative. Under what conditions does the reaction 6, occur spontaneously? (ii} For a reaction both M! and ~Sare positive. Under what conditions does the reaction occur spontaneously? · st 7, (a) An exothermic reaction may not be always thermodynamically spontaneous. Ju Oifyf ·. (b) Explain why entropy of a perfectly crystalline substance is less than that · its imperfect crystals. (c) The entropy of steam is more than that of water at its boiling point. Explain.
8; The reaction N2 (g) + 0 2 (g) 2NO (g) is endothermic reaction but is spontaneous. Explain. 1 Neither q nor w are state functions but q + w is a state function. Why?
10. Out of diamond and graphite which has greater entropy?
1: How can a chemical reaction with positive enthalpy and entropy changes be made entropy driven? 2. From the available data predict at what temperature will the reaction. given below becomes spontaneous? · N2 (g) + 02 (g) 2NO (g) 1 1 1 Given: SN2(g)= 191.4 JK" 1 mo1" ; S02(g)= 204.9 JK" mor 1 1 and SNO(g)~ 210.5 JK"1 mor and Aff=180.8 KJ mor
3. At 300 K the_standard enthalpi~s of fonnation of C6H5COOH (s), CO2 (g) and H20 (l) are -408, -393 and -286 KJ mol 1. Calculate the heat of combustion ofbenzoic acid at (i) 1 constant pressure (ii) constant volume (R=8.314KJ K" mor1). · . th ·dation of glucose is -288.0 KJ mor 1• Tw . Q14. The enthalpy change in~olved_ ID ef~: muscular work. If 100 KJ of muscularenty ft1v ii percent of this energy is available . th imum ·distance that a person will b War~ needed to walk one kilometer, what is e max e abl~t1 walk after eating 120g of glucose. ½ (g) · ---+ CO2 (g) at 300 K1is spontane 0 Q15. Show that the reaction CO (g) + 20 2 is . KJ mor K" Th us c1~ 0 094 exothermic when the stand~d entropy chang~ ~~(g·) are -394.4 and _·13 7 ; ;.t~nctc\t Gibb's free energy of formation of CO2 (g) an · l'-J 11\())· respectively. . Q16. Using the data given below, calculate the· value Of the equilibrium constant fior th reaction at 298 K 3HC = CH (g)~C6H/g) 1 Given that /:J.1G0 (HC =CH)= 2.09 x10 5 mor /:J.1G0 (CJ16) = 1.24 x105 mor 1 R = 8.314 JK." 1 mor 1
Q17. Derive the .relationship
/:J.G = -T/:J.S 101a1
Q18. What is meant by total entropy change for a process, assuming the thermodynamj relationship?
Q19. For a hypothetical process, A !:J.H is positive and T/:J.S is also positive. T/:J.S is greate than /:J.H. predict whether above process is spontaneous or not.
Q20. Calculate the amount of work done by 2 mole of an ideal gas at 298 K in a reversibl isothermal expansion from 10 liters to 20 liters. ·
Q21. Calculate the standard internal energy change for the reaction OFi(g)+ H2O(g) Oi(g) 2HF(g) at 398 K, given that enthalpies of formation of OFi(g), H2O(g), and HF(g) ar +20, -250 and -270 KJ mol" 1 respectively.
Q22. The heat change for the reaction:
Ni(g) + 3H2 2NHJ(g) is -92.2KJ. Calculate the heat of formation of ammonia.
Q23. The thermo chemical equations for solid and liquid rocket fuels are given below: 2Al(s) + 3/2O2(g) AhO3(s); trH = -1667.8 KJ. + H(g) 1/2O2(g) H2O(s); L'.1rH = -285.9 KJ. If equal masses of aluminium and hydrogen are used, which is a bettenocket fuel. A cylinder of cooking gas is ass . h thermo , (a) b rnical equation for th b . urned to contam 11.2kg of butane. T e ,i4 c e + 13/2 0 e com ustion of butane is: C4B1 1(g)_ . 2 (g) 4 CO2 (g) + SH2O (!)· 1::,. H = -2658 KJ · If a. family ?needs 15000 KJ 0 f energy per day ' c for cooking, how long wouId the cyhnder 1ast. (c) Assuming that 3 o per cent of the gas is wasted due to incomplete combu 5tion, how long would the cylinder last in that case?
5 calculate ~e enthalpy of transition when C (diamond) changes to C (graphite) given that
2 · the enthalp1e~ of combustion of C (diamond) and 1 c (graphite) are -393.5 and -395.4 KJ Jt10r 1 respectively.
, • Calculate the h:at of combustion of glucose from the following data:
(!ii) HCl (g) + aq HCl (aq); !::,.H = -73.2 KJ (iv) AhC16 (s) + aq AliC16(aq); MI= -643.0 KJ
28. Calculate the enthalpy of formation of acetic acid, given that the enthalpy of compounds of acetic acid is -867.0 KJ and the enthalpy of formation CO2 (g) and H20 (!) are -393.5 KJ and -285.9KJ respectively. 1 29. Calculate that bond energy of C -H bond energy is 416 KJ mor • (i) 2C (graphite)+ 3H20 (g) C2~(g); l::,.H = -84.67 KJ !::,.H = + 716.7 KJ (ii) C (graphite) C(g); !::,.H=+435.9KJ (iii) . H2 (g) 2H (g); 1 Assume that bond energy of C - H bond energy is 416 KJ mor • 1 30. Using the data provided, calculate the multiple bond energy (KJ mor ) of C 1 = C bond in . C2H2, (take the bond energy of a C - H bond as 350 KJ mor ) · · 1 2C(s) + H2(g) C2H2(g); !::,.H = 225 KJ mor 1 2C(s) 2C(g); !::,.H = 1410 KJ mor
~H = 330 KJ mor 1 the lattice energy of NaCl from the foUo , Q31. Construct Born - Haber cycle to calculate • \\r1~ 1 data: _1 = + 108.4 KJ mo1" i'.\H NaCl (s) = -411.2 KJ mol , !'.\(sub) H Naes) _1 1 H Cl (g) - + 242 0 KJ mol , i'.\HNa (g) = + 495.8 KJ mor, L\o 2 - · i'.\(egJ HCl (g) = -348 KJ mor' · , h · creased or decreased and conse Q32. In the following changes state whether order as m · quen.11 the direction of change of entropy of the system. (i) Stretched rubber band Loose rubber band • (ii) H20(l) H20(s) (iii) Dry ice (solid carbon-dioxide) C02(g) (iv) Water (v) Cr3++ 6H2O(aq) Cr(H20)i+ (vi'I1 CO2 +H2O Light Phorosythesis Denaturing >carbohudrate ._,, +0 2 (vii) Proteins (helical Proteins (random coil form) (viii) Natural egg Hard boiled egg.. (ix) Temperature of a crystalline solid from OK to 115 K. (x) 2NaHC03(s) Na2C03(s) + C02(g) + H20(g) (xi) Hi(g) 2H(g)
Q33. For the reaction,
NfiiCl(s) NH3(g) + HCl(g) At 25°C, enthalpy change, i'.\H = +177KJ and entropy change, i'.\S = +285 JK" 1• Calcul the free energy change, i'.\G at 25°C and predict whether the reaction is spontaneous not. / Q34. Determine whether or not it is possible for sodium to reduce aluminium oxide aluminium at 298 K. Given: L\fJ0 Ah03(s) = -1582 KJ mol" 1; L\fJ8 Na20(s) = -377 KJ mor 1•
Q35. What is the equilibrium constant (Kc) for the following reaction at 400 K 2NOCl(g) 2NO(g) + Ch(g) Given: L\H = 77.2 KJ mo1" 1 and i'.\S = 122.JK.· 1 at 400 K.
