CHEM 101A TOPIC C GAS LAWS AND THE KINETIC THEORY

WHAT YOU SHOULD BE ABLE TO DO WHEN YOU HAVE FINISHED THIS TOPIC: 1) Use classical gas laws to relate changes in pressure, volume, temperature, and number of moles to one another. 2) Use vapor pressure information and the classical gas laws to describe the behavior of a gas when it is collected over water. 3) Relate the density of a gas at a given temperature and pressure to its molar mass. 4) Solve stoichiometry problems involving gases, using the ideal gas law. 5) Have sufficient understanding of basic kinetic theory to be able to: a) Solve problems involving kinetic energy, temperature, molar mass, and particle velocity for an ideal gas. b) Use effusion rates to determine the molar mass of a gas. c) Answer qualitative questions about the Boltzmann distribution of kinetic energies and velocities, and their relationships to temperature and molar mass. 6) Describe the factors that differentiate real gas behavior from the ideal gas model, and use the van der Waals equation to model real gas behavior. READING ASSIGNMENT: Sections 5.1 through 5.7 and section 5.10. Omit the quantitative kinetic molecular model on pages 164-167 (7th edition) or 157-161 (6th edition). RELEVANT PROBLEMS: (7th edition): Chapter 5, problems 21, 29, 31, 35, 45, 47, 53, 54, 65, 69, 77, 79, 81, 85, 87, 91, 109, 117, 121 and 145. (6th edition): Chapter 5, problems 21, 27, 29, 33, 41, 43, 45, 49, 61, 65, 73, 75, 77, 81, 83, 87, 103, 107, 111 and 135.

THE REQUIRED HOMEWORK ASSIGNMENT STARTS ON THE NEXT PAGE OF THIS HANDOUT.

TOPIC C HOMEWORK PROBLEMS 1) A container holds 451 mL of air at a pressure of 1.33 atm. If you want to increase the pressure to 1.65 atm without changing the temperature, to what volume must you compress the air? 2) A balloon is filled with 3.85 L of oxygen at 31C and a pressure of 744 torr. The balloon is then taken to the top of a mountain, where the pressure is 591 torr. The volume of the oxygen is found to be 4.13 L. What is the temperature of the oxygen? Give your answer in C. 3) A container is filled with 25.3 g of gaseous hydrogen at 31C and a pressure of 3.88 atm. What is the volume of the container? 4) A chemist collects 250.0 mL of gaseous methane (CH4) over water at a temperature of 22C and a pressure of 731 torr. The vapor pressure of water at 22C is 2645 Pa. What is the mass of the methane? 5) Copper reacts with nitric acid as shown below: Cu(s) + 4 HNO3(aq) ! Cu(NO3)2 + 2 NO2(g) + 2 H2O(l) If 4.17 g of copper reacts with excess 3 M nitric acid, what volume of nitrogen dioxide will be formed at 31C and 1.022 atm? 6) Consider the apparatus pictured below, which consists of two containers separated by a valve.
He(g) 422 mL 817 torr Ar(g) 761 mL 685 torr

Assuming that the two gases are the same temperature and that the temperature does not change, what will be the total final pressure in the system after the valve is opened and the gases mix completely? 7) At 100C, ethane (C2H6) reacts with chlorine as follows: C2H6(g) + 7 Cl2(g) ! 2 CCl4(g) + 6 HCl(g) A mixture containing 35.5 torr of C2H6 and 318 torr of Cl2 is allowed to react at 100C. a) What will be the partial pressure of each gas in the final mixture, assuming that the reaction goes to completion and the temperature and volume remain constant? b) What will be the total pressure in the container? 8) Consider the following reaction: 4 Cr2+(aq) + O2(g) + 4 H+(aq) ! 4 Cr3+(aq) + 2 H2O(l) A container that holds 562 mL of gaseous oxygen at 21C is prepared. Then, 21.3 mL of a solution that contains 0.131 M Cr2+ ions is added to the container. After the reaction, the partial pressure of the oxygen in the container is found to be 119 torr and the temperature is still 21C.

What was the pressure of oxygen in the container before the Cr2+ solution was added? (You can assume that H+ is present in excess.) 9) Consider the apparatus pictured below, which consists of two containers separated by a valve.
C3H6(g) 367 mL 663 torr O2(g) 602 mL 2216 torr

The valve is opened and the gases react as follows (note that the temperature is high enough that the water is produced as a gas): 2 C3H6(g) + 9 O2(g) ! 6 CO2(g) + 6 H2O(g) What will be the total pressure in the apparatus when the reaction has gone to completion? Assume that the temperature does not change. 10) Consider the apparatus pictured below, which consists of two containers separated by a valve.
C3H6(g) 617 mL 317 torr O2(g) 933 mL unknown pressure

The valve is opened and the gases react as follows (note that the temperature is high enough that the water is produced as a gas): 2 C3H6(g) + 9 O2(g) ! 6 CO2(g) + 6 H2O(g) After the reaction, the total pressure in the apparatus is found to be 1133 torr. What was the initial pressure of the oxygen? Assume that the temperature remains constant. 11) What is the density of gaseous carbon dioxide at 51C and a pressure of 855 torr? 12) A gaseous compound has the following composition: 88.8% carbon, 11.2% hydrogen. The density of this compound is 1.91 g/L at 33.2C and a pressure of 675 torr. What is the molecular formula of the compound? 13) A sample of oxygen and a sample of nitrogen have the same density and are at the same temperature. If the oxygen exerts a pressure of 1.00 atm, what pressure does the nitrogen exert? 14) A 2.50 L container is filled with gaseous H2S at 13.0C and a pressure of 169.1 torr. Then 200.0 mL of water is added to the container (without allowing any of the H2S to escape). A small amount of H2S dissolves in the water. When the system has reached equilibrium, the gas pressure in the container is 155.9 torr and the temperature is still 13.0C. The vapor pressure of water at this temperature is 11.2 torr. What is the molar concentration of H2S in the water?

15) This question is intended to give you a feel for the size of the SI energy unit. a) Janice weighs 131 pounds. If her kinetic energy is 1.00 J, how fast is she moving? (1 pound equals 454 grams.) b) If Janice is walking at a speed of 1.34 m/sec (about 3 miles per hour), what is her kinetic energy in joules? 16) The average kinetic energy of the atoms in a sample of gaseous neon at a certain temperature is 6215 J/mol. a) What is the average kinetic energy of a single neon atom, in joules? b) If a neon atom has this kinetic energy, how fast is it moving? c) If the neon sample weighs 1.250 g, what is the total kinetic energy of the atoms in the sample? d) What is the temperature of the neon? e) What is the most probable kinetic energy for the neon, in J/mol? f) What is the root-mean-square speed of the neon atoms? g) What is the average speed of the neon atoms? h) What is the most probable speed of the neon atoms? 17) A molecule of water vapor is moving at 426 m/sec at 25C. a) What is the kinetic energy of this molecule, in joules? b) What is the kinetic energy of this molecule, in J/mol? c) Is this molecule moving faster than the average speed of water vapor molecules at this temperature? 18) A sample of argon is at 25C. a) What temperature would a sample of krypton need to be in order for it to have the same average kinetic energy as the argon? b) What temperature would the krypton need to be in order for it to have the same average molecular speed as the argon? 19) Two identical containers are filled with gases as shown below: Container 1: CO2(g) at 25C, 1 atm Container 2: CO(g) at 25C, 1 atm a) Which gas has the higher average kinetic energy? Explain how you can tell. b) Which gas has the higher average speed? Explain how you can tell. c) Which gas has a higher fraction of molecules with kinetic energies greater than 5 kJ/mol? Explain how you can tell. d) Which gas has a higher fraction of molecules with speeds greater than 500 m/sec? Explain how you can tell. e) Which gas weighs more? Explain how you can tell. 20) Two identical containers are filled with gases as shown below: Container 1: O2 at 75C, 1 atm Container 2: NO at 25C, 1 atm a) Which gas has the higher average kinetic energy? Explain how you can tell. b) Which gas has the higher average speed? Explain how you can tell. Problem 20 continues on the next page

c) Which gas has a higher fraction of molecules with kinetic energies lower than 5 kJ/mol? Explain how you can tell. d) Which gas has a higher fraction of molecules with speeds less than 500 m/sec? Explain how you can tell. e) Which gas weighs more? Explain how you can tell. 21) The graph below shows the kinetic energy distribution for N2(g) at an unknown temperature.

0.0005

Fraction per J/mol

0.0004 0.0003 0.0002 0.0001 0

2000 4000 6000 8000 Kinetic energy (J/mol)

10000

a) What is the most probable kinetic energy for the gas? b) What is the approximate temperature of the gas? c) What is the y value when x = 2000 J/mol? What does this y value tell you? d) The area of the shaded region is 0.259. What does this value tell you? 22) The following questions relate to the graph on the next page, in which curve B represents the kinetic energy distribution for Ne(g) at 300 K. a) Which curve (A, B, or C) could represent the kinetic energy distribution for Ar(g) at 300 K? Explain your answer briefly. b) Which curve could represent the kinetic energy distribution for Ne(g) at 600 K? Explain your answer briefly.

Graph for problem 22

Fraction

B C Kinetic energy

23) Consider the graph below, in which curve B represents the distribution of speeds for H2(g) at 25C.

Fraction

B C Molecular speed

a) Which curve (A, B, or C) could represent the distribution of speeds for H2(g) at 125C? Explain your answer briefly. b) Which curve could represent the distribution of speeds for N2(g) at 25C? Explain your answer briefly. c) Which curve could represent the distribution of speeds for He(g) at 319C? Explain your answer briefly.

24) The graph below shows the distribution of speeds for an unknown gas at 200C.

0.004

Fraction per m/sec

0.003

0.002

0.001

0 0 200 400 600 800 1000

Speed (m/sec)
a) What is the most probable speed for this gas? b) This gas is one of the inert gases. Which one is it? c) What is the y value when x = 200 m/sec? What does this y value tell you? d) The area of the shaded region (which extends out to infinite speed) is 0.111. What does this value tell you? e) What is the area of the region under the curve that is not shaded? What does this value tell you? 25) At 62C, 5.00 mL of argon effuses through a porous barrier in 5 minutes and 13 seconds. In an identical apparatus at 62C, 5.00 mL of an unknown gas effuses through the barrier in 6 minutes and 10 seconds. The empirical formula of the unknown gas is CH2. Determine the molecular formula of the gas. 26) If we compare the van der Waals constants for water and nitrogen, we see a curious discrepancy; water has a higher value of a while nitrogen has a higher value of b. The numbers are: H2O: a = 5.46 atmL2/mol2 b = 0.0305 L/mol N2: a = 1.39 atmL2/mol2 b = 0.0391 L/mol a) Explain why water has the higher a value. b) Explain why nitrogen has the higher b value.

27) An engineer is designing a reactor that will be filled with oxygen under high pressure. The volume of the reactor is 253 L, the maximum temperature inside the reactor will be 250C, and the pressure inside the reactor must not exceed 150 atm. The engineer uses the ideal gas law to calculate the maximum number of moles of oxygen that can be put into the reactor without exceeding 150 atm. a) What number of moles does the engineer calculate using the ideal gas law? b) Now use the van der Waals equation to calculate a more accurate value for the pressure inside the reactor at 250C, using the number of moles you obtained in part a. Will the reactor be at risk of failure, based on your answer? (Van der Waals constants for oxygen are given in the textbook.) 28) The graph below shows how the actual pressure of a sample of O2 deviates from the ideal gas prediction.

Ideal versus real gas behavior for 1 mol O2 at 273 K

1.5 1.4 1.3

real P/ideal P

1.2 1.1 1 0.9 0.8 0.7 0 0.5 1 1.5 2

Volume (L)

a) Based on this graph, under what conditions is the actual pressure lower than the ideal gas prediction? Why is this? b) Based on this graph, under what conditions is the actual pressure higher than the ideal gas prediction? Why is this? 29) Explain the following observations, using the kinetic theory of gases. a) When a gas is heated, the pressure that it exerts increases. b) Gases can easily be compressed into smaller volumes. c) Raising the temperature of 1 mole of helium by 1C requires the same amount of energy as raising the temperature of 1 mole of argon by 1C.