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Thermodynamics PEC201 Mid Semester Test 2011 Instructions to candidates: Attempt all questions. Time allowed is 50 minutes. Total marks available on the paper is 50 (1 mark = 1 minute). The examination is closed-book. Graphic display and programmable calculators are allowed but must be reset before commencing the examination. Data and formulae are attached. Question 1 (5 marks) Give a brief explanation of the following: a. Path b. Adiabatic process c. Equilibrium d. Steady state e. Phase [1 mark each] Question 2 (12 marks). Calculate U, H, q and w when one mole of helium is heated from 25C and 1 atm to 100 C (a) at constant volume; (b) at constant pressure; and (c) by adiabatic compression. Assume helium is ideal with Cv,m and Cp,m constant over the temperature range. Question 3 (5 marks) Calculate the enthalpy for the conversion of graphite into diamond given the following heats of combustion for each substance. C(diamond) + O2(g) CO2 (g) C(graphite) + O2(g) CO2 (g) H = 395.3 kJ mol-1 H = 393.4 kJ mol-1
Question 4 (8 marks). A closed system is formed by mixing HCl(g) and NH4Cl(s). The system rapidly reaches an equilibrium position for the reaction below. NH4Cl (s) NH3 (g) + HCl (g) Is it possible to independently vary the temperature, total pressure and p NH3 in this system? Briefly explain the logic supporting your answer. Question 5 (5 marks). Sm for the equilibrium melting of all metals is approximately the same. If gold has a higher melting point than silver, is Hmelt,m for each of these metals also the same? (question 6 follows)
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Question 6 (5 marks). The U.S. Geological Survey Open-File Report 99-324 gives the following data for the solid phase transition of sulfur (S8) from the orthorhombic to monoclinic forms. Transition temperature at 1 atm. Enthalpy of transition orthorhombic monoclinic 368.3 K +401.3 J mol1 2.07 g cm3 1.96 g cm3
Assuming that the phase transition enthalpy is constant as the pressure is increased to 100 atm, predict whether the transition temperature will increase or decrease at the higher pressure. Show your logic. Question 7 (10 marks) The gas phase dimerisation of NO2 proceeds according to the reaction below. 2NO2(g) N2O4(g) A closed isochoric, isothermal system at 298 K, 1.00 atm and containing only 1.00 mmol of NO2 is established. When the system reaches equilibrium, only 20 % of the original amount of NO2 gas remains. a. At the equilibrium position, how much N2O4 is formed in the system? b. Since the system is not isobaric estimate the pressure in the system at equilibrium. c. Estimate a value for the thermodynamic equilibrium constant of this reaction.
End of Questions
Data and formulae sheet follows
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Data and formulae:
1 atm = 1.013 105 (kg m2 s-2, Pa) = 760 Torr = 760 mm Hg, R = 8.314 J K1 mol1, 0.0 C = 273.15 K pV = nRT for an ideal gas w = p V at const. p and T w = n R T ln(p2/p1) for a reversible process at const. V and T U = q + w First law U = qv for const. V H = qp = Cp T for const. p Cv,m = 3/2 R for an ideal monatomic gas Cp - Cv = n R for an ideal gas U = n Cv,m (T2 - T1) for const. Cv H = n Cp,m (T2 - T1) for const. Cp S > 0 for a spontaneous process in an isolated system dU = T dS - p dV Master equation - true for all paths dG = V dp - S dT true for all paths G = n R T ln(p2/p1) G = G(p2) - G(p1) ideal gas d = Vmdp -SmdT for any phase equilibrium dp / dT = Sm/Vm Clapeyron equation dp / dT = Hm/(Vm Tmelt) Clapeyron equation dln p/dT = H0m/(R T2 ) Clausius-Clapeyron equation ln(p2/p1) =(-H/R){(1/T2)-(1/T1)} Ho = molar enthalpy of sublimation or vaporisation ln(K2/K1) =(-H/R){(1/T2)-(1/T1)} vant Hoff equation (if Ho is constant) giving effect of temperature on K; note K f(p) Go = R T lnK G = R T ln (Q/K) F=CP+2 Phase rule combined with C = S - R H = qp = Cp T for const. p, definition of enthalpy S > 0 criterion for a spontaneous process in an isolated system; second law (entropy increases) dU = T dS p dV master equation - true for all paths; derived from U = q + w but has only state functions G = H TS the capacity of a system to perform work under isothermal and isobaric conditions; provides a criterion for spontaneous change at const. T&p (G<0); the balance of dSsur & dSsys dG = V dp S dT true for all paths; gives effect of T & p on Gibbs energy; derived from master equation o A = A + R T ln aA defines activity, a, in terms of chemical potential = dG/dn = (partial) molar Gibbs energy gives the effect on of concs. & of non-ideal effects since a = c (std. state is ideal with c = 1) c d a C .a D Q = activity quotient, Q, is defined for any generalised reaction b aa . a A B aA + bB = cC + dD equilibrium constant, K, is the activity quotient,Q, at equilibrium; Go = RT lnK this must be constant whatever the process or reaction may be (because Go, R and T are const.) S =
dq rev T A
for a reversible process (absorbs max. heat, does max. work)
End of MST Paper
