6/7/2011 1 What is ∆U? • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. 2400 Paul Franklyn – School of Chemistry – Wits - 1 J 1 What is ∆U? • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. • ANSWER: For a perfect gas Cv = dU dT ∴ dU = CvdT. For an appreciable change f Tf ∆U = ∫ dU = ∫ CV dT i Ti Since Cv is given as independent of temperature, ∆U = Cv.∆T = nCv.m∆T = (0.500 mol)(1.5R)(384 K) = 2.40 kJ Paul Franklyn – School of Chemistry – Wits - 2 1 6/7/2011 2 What is ∆H? • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. 4000 Paul Franklyn – School of Chemistry – Wits - 3 J 2 What is ∆H? • • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. ANSWER: Similarly, for a perfect gas ∴ Cp = dH dT dH = Cp dT , which, on integration, gives ∆H = Cp.∆T = nCp.m∆T = (0.500 mol)(2.5R)(384 K) = 4.00 kJ Paul Franklyn – School of Chemistry – Wits - 4 2 6/7/2011 3 Calculate w: • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. -1600 Paul Franklyn – School of Chemistry – Wits - 5 J 3 Calculate w: • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. • ANSWER: Vf w = − ∫ p.dV = -P(V - V ) = -(0.789 atm)(2000cm3) 2 1 Vi = 1578 atm cm3 Hence, w = 1578 [(8.315 J)/82.06] = -1.60 kJ. Paul Franklyn – School of Chemistry – Wits - 6 3 6/7/2011 4 Calculate q: • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. 4000 Paul Franklyn – School of Chemistry – Wits - 7 J 4 Calculate q: • 2.00 g of He(g) with CV.m = 1.5R essentially independent of temperature undergoes a reversible constant-pressure expansion from 20.0 to 40.0 dm3 at 0.800 bar. • ANSWER: – q = qp = ∆H = 4.00 kJ. Paul Franklyn – School of Chemistry – Wits - 8 4 6/7/2011 5 Calculate ∆Ssys? • When Argon at 25 oC and 1 bar in 0.5 dm3 contained is allowed to compress to 0.0500 dm3 and is simultaneously cooled to -25 oC. -0.43 Paul Franklyn – School of Chemistry – Wits - 9 J/K 6 Calculate ∆H°370 : • Given ∆H°298 = -956.5 kJ mol-1 2HN3(g) + 2NO(g) → H2O2(l) + 4N2(g) Use data in the Appendix and the approximation of neglecting the temperature dependence of C°P,m to estimate ∆H°370 for the reaction above. (to 4 sig figs) 952400 Paul Franklyn – School of Chemistry – Wits - 10 J/mol 5 6/7/2011 6 Calculate ∆H°370 : • Given ∆H°298 = 956.5 kJ mol-1 2HN3(g) + 2NO(g) → H2O2(l) + 4N2(g) • ANSWER: Using Kirchhoff's Law: ∆H°(Tf) = ∆H°(Ti) + Tf ∫ ∆C dT o p ------------------------(1) Ti ∆C°P = C°P(H2O2) + 4C°P(N2) - 2C°P(HN3) - 2C°P (NO) = 89.1 + 4(29.125) - 2(43.68) - 2(29.844) = 58.55 J K−1 mol−1 Tf = 370 K Ti = 298 K Substituting numerical values into Kirchhoff's Law := −956 500 J mol−1 + 58.88 J K−1 mol−1 x (70 K) −1 = −952.4 kJ Paul mol Franklyn – School of Chemistry – Wits - 11 7 How old (in years)? • A Mayan mummy was radiocarbon dated by three different laboratories. The three 14C/12C ratios were found to be 63.10%, 62.91% and 64.15% of that found in living organisms. Use the half-life for 14C as 5715 years to determine the average age of the Mayan mummy. Do not enter any units!!! 3759 Paul Franklyn – School of Chemistry – Wits - 12 6 6/7/2011 7 Answers Correct answer is: 3759 Paul Franklyn – School of Chemistry – Wits - 13 8 Calculate EA • For a reaction whose rate constant at room temperature is doubled by an increase in temperature (T) by 10oC. 53000 Paul Franklyn – School of Chemistry – Wits - 14 J/mol 7 6/7/2011 8 Answers Correct answer is: 53000J/mol Paul Franklyn – School of Chemistry – Wits - 15 8
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