ChE 323 Physical Chemistry Compilation 1: PROPERTIES OF GASES Instructions: This assignment should be done individually. Read pp.

3-23 of the textbook Atkins Physical Chemistry (8th ed.) and answer the questions below. Write your answers on a long-size bondpaper. The answers should be hand-written. I. Concepts: 1. 2. 3. Explain why specifying the temperature, volume, and number of moles of a perfect gas fixes the pressure of that gas. Explain how the perfect gas equation of state arises by combination of Boyles law, Charless law, and Avogadros principle. A third year chemical engineering student relates the following story: I noticed my tires were a bit low and went to the gas station. As I was filling the tires I thought about the kinetic molecular theory (KMT), and I realized that I was increasing both the pressure and volume of the tires as I filled the tires with air. Hmmm, I thought, that goes against what I learned in chemistry, where I was told pressure and volume are inversely proportional. What is the fault of the logic of the student in this situation? Explain why we think pressure and volume to be inversely related (draw pictures and use the KMT). Consider two different containers, each filled with 2 moles of Ne(g). One of the containers is rigid and has constant volume. The other container is flexible (like a balloon) and is capable of changing its volume to keep the external pressure and internal pressure equal to each other. If you raise the temperature in both containers, what happens to the pressure and density of the gas inside each container? Assume a constant external pressure. Draw a qualitative graph to show how the first property varies with the second in each of the following (assume 1 mole of an ideal gas and T in Kelvins): i. PV versus V with constant T ii. P versus T with constant V iii. T versus V with constant P iv. P versus V with constant T v. P versus V with constant T vi. P versus 1/V with constant T vii. PV/T versus P Explain why Daltons law is a limiting law for partial pressures. Explain how the compression factor varies with pressure and temperature and describe how it reveals information about intermolecular interactions in real gases. Explain the significance of critical constants. Explain how the van der Waals equation accounts for critical behavior.

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II. Problem-solving: 1. 2. Prove mathematically that the % mole is equal to % volume for ideal gases. State underlying laws and principles. If water is added to magnesium nitride, ammonia gas is produced when the mixture is heated. Mg3N2(s) + 3H2O(l) 3MgO(s) + 2NH3(g) If 10.3 g of magnesium nitride is treated with water, what volume of ammonia gas would be collected at 24 C and 752 mm Hg? Calculate the density of ammonia under these conditions. 3. Calculate the pressure and composition of air on top of Mt. Everest, assuming that the atmosphere has a temperature of 0oC independent of altitude (h = 29141 ft). Assume that air at sea level has a pressure of 1 bar and contains 20% O 2 and 80% N2. Hint: The difference in pressure drop dP between h and h + dh is equal to the mass of the gas between these two levels times g and divided by the area dP gdh . (Ans: 0.333 bar)
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A 5-ml container with a hole 10 m in diameter is filled with hydrogen. This container is placed in an evacuated chamber at 0oC. How long will it take for 90% of the hydrogen to effuse out? (Ans: 347 s) A compound contains only C, H, and N. A chemist analyzes it by doing the following experiments: Complete combustion of 35.0 mg of compound produced 33.5 mg CO 2 and 41.1 mg H2O. A 65.2-mg sample of the o compound was analyzed for nitrogen by the Dumas method, giving 35.6 mL N2 at 740.0 torr and 25 C. The effusion rate of the compound as a gas was measured and found to be 24.6 mL/min. The effusion rate of argon gas, under identical conditions, is 26.4 mL/min. a. b. What is the molecular mass of the compound? (Ans: 45.7 g/mol) What is the molecular formula of the compound? (Ans: CH6N2)

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An impure 60.2 g sample of KNO3 was heated until al of the KNO3 had decomposed. 2 KNO3 (s) 2 KNO2 (s) + O2 (g) The oxygen produced occupied 4.22 L at STP. What was the percent purity of the KNO3 sample? Assume that KNO3 is the only source for the O2. (Ans: 63.3%)

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Hot air balloons gain their lift from the lowering of density of air that occurs when the air in the envelope is heated. To what temperature should you heat a sample of air, initially at 340 K, to increase its volume by 14%? (Ans: 373 K) A certain sample of a gas has a volume of 20.00 dm 3 at 0oC and 1.000 atm. A plot of the experimental data of its volume against the Celsius temperature, , at constant p, gives a straight line of slope of 0.0741 dm 3 (oC)-1. From these data alone (without making use of the perfect gas law), determine the absolute zero temperature in oC. Express the van der Waals equation of state as a virial expansion in powers of 1/V m and obtain expressions for B and C in terms of the parameters a and b. The expansion you will need is 1 x 1 1 x x 2 ... . Measurements on argon gave B = 21.7 cm3mol-1 and C = 1200 cm6mol-2 for the virial coefficients at 273 K. What are the values of a and b in the corresponding van der Waals equation of state?

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10. A plastic bag is weighed and then filled successively with two gases, X and Y. The following data are gathered: Temperatu Pressure Mass of empty Mass of bag filled Mass of 1.12 L of Vol. of Molar vol. at re bag with gas X air @ conditions bag STP given 0.0oC 1.00 20.77 g 24.97 g 1.30 g 1.12 L 22.4L atm The mass of 1.12 L of gas Y is found to be 6.23 g. Calculate the density and molar mass of the gas. 11. The pressure in interplanetary space is estimated to be of the order of 10 -14 Pa. Assume that only hydrogen atoms are present and that the temperature is 1000K. Assume d = 0.2 nm. Calculate the following: a. b. c. The average number of molecules per cubic centimetre (Ans: 0.724 cm -3) The collision frequency (Ans: 5.92 x 10-10 s-1) The mean free path in miles (Ans: 4.83 x 109 mi)