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8/29/2010

1.5
A constant Volume perfect gas thermometer indicates a pressure of 6.69 kPa at the triple point temperature of water (273.16 K). (a) what change of pressure indicates a change of 1.00 K at this temperature? (b) What pressure indicates a temperature of 100.00C? (C) what change of pressure indicates a change of 1.00 K at the latter temperature Solutions a) This is a perfect gas, thus can use P1V 1/T1 = P 2V 2/T2 Since this is at constant volume; equation simplifies to: P 1/T1 = P 2/T2 T2 = the change + original temperature = 1.00 k + 273.16 = 274.16 k P 2 = (6.69 kPa / 273.16 k) x 274.16 k = 6.71449 kPa Change in Pressure = 6.71449 - 6.69 = 0.0244911 kPa, Answer = A change in 0.0245 kPa, would indicate a change of 1.0 K.
b)

Chem 251 TUT + SOLUTIONS

Perfect gas, therefore can use same equation from part (a); P 2 = (6.69 kPa / 273.16 k) x 373.16 k = 9.139114072 kPa Answer = 9.14 kPa Same steps as in part (a) P 2 = (9.14 kPa / 373.16 k) x 374.16 k = 9.1644935 kPa Change in pressure = 9.164493 - 9.14 = 0.024493 kPa Answer = 0.0245 kPa

AUGUST 27TH 2010

c)

2.4(A)
A sample consisting of 1.00 mol of perfect gas atoms, for which CV,m = 3/2R, initially at p1 = 1.00 atm and T1 = 300 K, is heated reversibly to 400 K at constant volume. Calculate the final pressure, U, q, and w. Solution: This is a perfect gas, thus can use P1V1/T1 = P2V2/T2 to: Since this is at constant volume; equation simplifies to: P1/T1 = P2/T2 P2 = (1.00 / 300) x 400 = 1.333333 atm Answer = Final pressure = 1.33 atm W = 0 because there is no change in volume U = q + w; but w = 0, thus U = q CV,m = 3/2R = (3/2) * 8.31447 = 12.471705 J K-1 mol-1 Cv = 12.471705 J K-1 mol-1 x 1 mol (from the question; 1 mol of perfect) qv = CvT = 12.471705 J K-1 x (400 300) = 1247.1705 J Answer = U = q = 1.25 kJ

2.15
Silylene (SiH2) is a key intermediate in the thermal decomposition of silicon hydrides such as silane (SiH4) and disilane (Si2H6). Moffat et al. (H.K. Moffat, K.F. Jensen, and R.W. Carr, J. Phys. Chem. 95, 145 (1991)) report fHO(SiH2) = +274 kJ mol1. If fHO(SiH4) = +34.3 kJ mol1 and fHO(Si2H6) = +80.3 kJ mol1 (CRC Handbook (2004)), compute the standard enthalpies of the following reactions: (a) SiH4(g) SiH2(g) + H2(g) (b) Si2H6(g) SiH2(g) + SiH4(g) Solutions: Use equation below, from the slides (see equation 2.34 on p55 in your text book); (0 (a) [(+274 x 1) + (0 x1 )] [34.3 x 1] = 239.7 kJ mol1 (b) [(+274 x 1) + (34.3 x 1)] [+80.3 x 1] = 228 kJ mol1

8/29/2010

2.18(B)
From the following data, determine fHo for diborane, diborane, B2H6(g), at 298 K:
(1) (2) (3)

B2H6(g) + 3O2(g) B2O3(s) + 3H2O(g) rHO = 1941 kJ mol1 2B(s) + 3/2O2(g) B2O3(s) rHO = 2368 kJ mol1 H2(g) + 1/2O2(g) H2O(g) rHO = 241.8 kJ mol1

Solution: B2O3(s) + 3H2O(g) B2H6(g) + 3O2(g) rHO = +1941 kJ mol1 2B(s) + 3/2O2(g) B2O3(s) rHO = 2368 kJ mol1 3H2(g) + 3/2O2(g) 3H2O(g) rHO = (3 x241.8 kJ mol1) _____________________________________________+ 3H2(g) + 2B(s) B2H6(g) = 1152.4 kJ mol1

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