432

chapter 10 Gases

Key Equations
• PV = nRT [10.5] Ideal-gas equation

P1V1 P2V2
• = [10.8] The combined gas law, showing how P, V, and T are related
T1 T2
for a constant n

Pℳ
• d = [10.10] Calculating the density or molar mass of a gas
RT

• Pt = P1 + P2 + P3 + c [10.12] Relating the total pressure of a gas mixture to the partial pressures of its
­components (Dalton’s law of partial pressures)

n
• P1 = a 1 b Pt = X1Pt [10.16] Relating partial pressure to mole fraction
nt

3RT
• urms = [10.20] Definition of the root-mean-square (rms) speed of gas molecules
A ℳ

r1 ℳ2
• = [10.22] Relating the relative rates of effusion of two gases to their molar masses
r2 A ℳ1

n2a
• aP + b1V - nb2 = nRT [10.25] The van der Waals equation
V2

Exercises
Visualizing Concepts
10.1 Mars has an average atmospheric pressure of 0.007 atm.
Would it be easier or harder to drink from a straw on Mars
than on Earth? Explain. [Section 10.2]
10.2 You have a sample of gas in a container with a movable piston,
such as the one in the drawing. (a) Redraw the container to
show what it might look like if the temperature of the gas is in- 10.4 Imagine that the reaction 2 CO1g2 + O21g2 ¡ 2 CO21g2
creased from 300 to 500 K while the pressure is kept constant. ­occurs in a container that has a piston that moves to main-
(b) Redraw the container to show what it might look like if the tain a constant pressure when the reaction occurs at constant
external pressure on the piston is increased from 1.0 atm to temperature. Which of the following statements d ­ escribes
2.0 atm while the temperature is kept constant. (c) Redraw the how the volume of the container changes due to the
container to show what it might look like if the temperature of ­reaction: (a) the volume increases by 50%, (b) the volume
the gas decreases from 300 to 200 K while the pressure is kept increases by 33%, (c) the volume remains constant, (d) the
constant (assume the gas does not liquefy). [Section 10.3] ­volume ­decreases by 33%, (e) the volume decreases by 50%.
­[Sections 10.3 and 10.4]
10.5 Suppose you have a fixed amount of an ideal gas at a con-
stant volume. If the pressure of the gas is doubled while the
volume is held constant, what happens to its temperature?
[Section 10.4]
10.6 The apparatus shown here has two gas-filled containers and
one empty container, all attached to a hollow horizontal
tube. When the valves are opened and the gases are allowed
to mix at constant temperature, what is the distribution of
atoms in each container? Assume that the containers are of
10.3 Consider the sample of gas depicted here. What would the
equal volume and ignore the volume of the connecting tube.
drawing look like if the volume and temperature remained
Which gas has the greater partial pressure after the valves are
constant while you removed enough of the gas to decrease the
opened? [Section 10.6]
pressure by a factor of 2? [Section 10.3]
 Exercises 433

HCl gas is introduced at one end of the tube, and simultaneously

NH3 gas is introduced at the other end. When the two gases diffuse
through the cotton plugs down the tube and meet, a white ring
appears due to the formation of NH4Cl1s2. At which location—
a, b, or c—do you expect the ring to form? [Section 10.8]
10.12 The graph below shows the change in pressure as the tem-
perature increases for a 1-mol sample of a gas confined to a
10.7 The accompanying drawing represents a mixture of three
1-L container. The four plots correspond to an ideal gas and
different gases. (a) Rank the three components in order of
three real gases: CO2, N2, and Cl2. (a) At room temperature,
increasing partial pressure. (b) If the total pressure of the
all three real gases have a pressure less than the ideal gas.
mixture is 1.40 atm, calculate the partial pressure of each gas.
Which van der Waals constant, a or b, accounts for the influ-
[Section 10.6]
ence intermolecular forces have in lowering the pressure of a
real gas? (b) Use the van der Waals constants in Table 10.3 to
match the labels in the plot (A, B, and C) with the respective
gases (CO2, N2, and Cl2). [Section 10.9]

45
Ideal gas
Gas A
10.8 On a single plot, qualitatively sketch the distribution of 40 Gas B
­molecular speeds for (a) Kr(g) at -50 °C, (b) Kr(g) at 0 °C, Gas C
(c) Ar(g) at 0 °C. [Section 10.7]
35

Pressure (atm)
10.9 Consider the following graph. (a) If curves A and B refer
to two different gases, He and O2, at the same temperature,
which curve corresponds to He? (b) If A and B refer to the 30
same gas at two different temperatures, which represents the
higher temperature? (c) For each curve which speed is high- 25
est: the most probable speed, the root-mean-square speed, or
the average speed? [Section 10.7]
20

15
Fraction of molecules

250 300 350 400 450 500 550

Temperature (K)
A

B Gas Characteristics; Pressure (Sections 10.1 and 10.2)

10.13 How does a gas compare with a liquid for each of the following
properties: (a) density, (b) compressibility, (c) ability to mix
with other substances of the same phase to form homogeneous
Molecular speed mixtures, (d) ability to conform to the shape of its container?
10.14 (a) A liquid and a gas are moved to larger containers. How
10.10 Consider the following samples of gases: does their behavior differ once they are in the larger contain-
ers? Explain the difference in molecular terms. (b) Although
= He liquid water and carbon tetrachloride, CCl41l2, do not mix,
their vapors form a homogeneous mixture. Explain. (c) Gas
= N2 densities are generally reported in grams per liter, whereas
liquid densities are reported in grams per milliliter. Explain
the molecular basis for this difference.
(i) (ii) (iii)
10.15 Suppose that a woman weighing 130 lb and wearing high-
If the three samples are all at the same temperature, rank heeled shoes momentarily places all her weight on the heel
them with respect to (a) total pressure, (b) partial pressure of one foot. If the area of the heel is 0.50 in.2, calculate the
of helium, (c) density, (d) average kinetic energy of particles. pressure exerted on the underlying surface in (a) kilopascals,
[Section 10.6 and 10.7] (b) atmospheres, and (c) pounds per square inch.
10.11 A thin glass tube 1 m long is filled with Ar gas at 1 atm, and
the ends are stoppered with cotton plugs:
a b c

HCl NH3
434 chapter 10 Gases

10.16 A set of bookshelves rests on a hard floor surface on four legs, the gas pressure? (a) Lifting up on the piston to double the
each having a cross-sectional dimension of 3.0 * 4.1 cm in volume while keeping the temperature constant; (b) Heat-
contact with the floor. The total mass of the shelves plus the ing the gas so that its temperature rises from 25 °C to 50 °C,
books stacked on them is 262 kg. Calculate the pressure in while keeping the volume constant; (c) Pushing down on the
pascals exerted by the shelf footings on the surface. piston to halve the volume while keeping the temperature
10.17 (a) How high in meters must a column of water be to exert constant.
a pressure equal to that of a 760-mm column of mercury? 10.26 A fixed quantity of gas at 21 °C exhibits a pressure of 752 torr
The density of water is 1.0 g>mL, whereas that of mercury and occupies a volume of 5.12 L. (a) Calculate the volume
is 13.6 g>mL. (b) What is the pressure, in atmospheres, on the gas will occupy if the pressure is increased to 1.88 atm
the body of a diver if he or she is 39 ft below the surface while the temperature is held constant. (b) Calculate the vol-
of the water when atmospheric pressure at the surface is ume the gas will occupy if the temperature is increased to
0.97 atm? 175 °C while the pressure is held constant.
10.18 The compound 1-iodododecane is a nonvolatile liquid with a 10.27 (a) Amonton’s law expresses the relationship between pres-
density of 1.20 g>mL. The density of mercury is 13.6 g>mL. sure and temperature. Use Charles’s law and Boyle’s law to
What do you predict for the height of a barometer column derive the proportionality relationship between P and T.
based on 1-iodododecane, when the atmospheric pressure is (b) If a car tire is filled to a pressure of 32.0 lbs>in.2 1psi2
749 torr? measured at 75 °F, what will be the tire pressure if the tires
10.19 The typical atmospheric pressure on top of Mt. Everest heat up to 120 °F during driving?
(29,028 ft) is about 265 torr. Convert this pressure to (a) atm, 10.28 Nitrogen and hydrogen gases react to form ammonia gas as
(b) mm Hg, (c) pascals, (d) bars, (e) psi. follows:
10.20 Perform the following conversions: (a) 0.912 atm to torr, N21g2 + 3 H21g2 ¡ 2 NH31g2
(b) 0.685 bar to kilopascals, (c) 655 mm Hg to atmospheres,
(d) 1.323 * 105 Pa to atmospheres, (e) 2.50 atm to psi. At a certain temperature and pressure, 1.2 L of N2 reacts with
10.21 In the United States, barometric pressures are generally reported 3.6 L of H2. If all the N2 and H2 are consumed, what volume of
in inches of mercury (in. Hg). On a beautiful summer day in NH3, at the same temperature and pressure, will be produced?
Chicago, the barometric pressure is 30.45 in. Hg. (a) Convert
this pressure to torr. (b) Convert this pressure to atm.
The Ideal-Gas Equation (Section 10.4)
10.22 Hurricane Wilma of 2005 is the most intense hurricane on re-
cord in the Atlantic basin, with a low-pressure reading of 882 10.29 (a) What conditions are represented by the abbreviation
mbar (millibars). Convert this reading into (a) atmospheres, STP? (b) What is the molar volume of an ideal gas at STP?
(b) torr, and (c) inches of Hg. (c) Room temperature is often assumed to be 25 °C. Calculate
the molar volume of an ideal gas at 25 °C and 1 atm pressure.
10.23 If the atmospheric pressure is 0.995 atm, what is the pressure
(d) If you measure pressure in bars instead of atmospheres,
of the enclosed gas in each of the three cases depicted in the
calculate the corresponding value of R in L-bar/mol-K.
drawing? Assume that the gray liquid is mercury.
10.30 To derive the ideal-gas equation, we assume that the vol-
Open end Open end Closed end ume of the gas atoms/molecules can be neglected. Given the
atomic radius of neon, 0.69 Å, and knowing that a sphere has
a volume of 4pr3 >3, calculate the fraction of space that Ne
atoms occupy in a sample of neon at STP.
h
h 10.31 Suppose you are given two 1-L flasks and told that one con-
h tains a gas of molar mass 30, the other a gas of molar mass
Gas Gas Gas
60, both at the same temperature. The pressure in flask A is
X atm, and the mass of gas in the flask is 1.2 g. The pressure
h = 52 cm h = 67 cm h = 10.3 cm in flask B is 0.5X atm, and the mass of gas in that flask is 1.2 g.
Which flask contains the gas of molar mass 30, and which
(i) (ii) (iii) contains the gas of molar mass 60?
10.32 Suppose you are given two flasks at the same temperature,
10.24 An open-end manometer containing mercury is con- one of volume 2 L and the other of volume 3 L. The 2-L flask
nected to a container of gas, as depicted in Sample Exer- contains 4.8 g of gas, and the gas pressure is X atm. The 3-L
cise 10.2. What is the pressure of the enclosed gas in torr flask contains 0.36 g of gas, and the gas pressure is 0.1X. Do
in each of the ­following situations? (a) The mercury in the the two gases have the same molar mass? If not, which con-
arm ­attached to the gas is 15.4 mm higher than in the one tains the gas of higher molar mass?
open to the atmosphere; atmospheric pressure is 0.985 atm.
10.33 Complete the following table for an ideal gas:
(b) The mercury in the arm attached to the gas is 12.3 mm
lower than in the one open to the atmosphere; atmospheric P V n T
pressure is 0.99 atm.
2.00 atm 1.00 L 0.500 mol ?K
0.300 atm 0.250 L ? mol 27 °C
The Gas Laws (Section 10.3)
650 torr ?L 0.333 mol 350 K
10.25 You have a gas at 25 °C confined to a cylinder with a mov-
? atm 585 mL 0.250 mol 295 K
able piston. Which of the following actions would double
 Exercises 435

10.34 Calculate each of the following quantities for an ideal gas: 10.45 In an experiment reported in the scientific literature, male
(a) the volume of the gas, in liters, if 1.50 mol has a pressure of cockroaches were made to run at different speeds on a minia-
1.25 atm at a temperature of - 6 °C; (b) the absolute tempera- ture treadmill while their oxygen consumption was measured.
ture of the gas at which 3.33 * 10-3 mol occupies 478 mL at In 1 hr the average cockroach running at 0.08 km>hr con-
750 torr; (c) the pressure, in atmospheres, if 0.00245 mol oc- sumed 0.8 mL of O2 at 1 atm pressure and 24 °C per gram of
cupies 413 mL at 138 °C; (d) the quantity of gas, in moles, if insect mass. (a) How many moles of O2 would be consumed in
126.5 L at 54 °C has a pressure of 11.25 kPa. 1 hr by a 5.2-g cockroach moving at this speed? (b) This same
10.35 The Goodyear blimps, which frequently fly over sporting cockroach is caught by a child and placed in a 1-qt fruit jar with
events, hold approximately 175,000 ft3 of helium. If the gas is a tight lid. Assuming the same level of continuous activity as in
at 23 °C and 1.0 atm, what mass of helium is in a blimp? the research, will the cockroach consume more than 20% of the
available O2 in a 48-hr period? (Air is 21 mol % O2.)
10.36 A neon sign is made of glass tubing whose inside diameter is
2.5 cm and whose length is 5.5 m. If the sign contains neon at 10.46 The physical fitness of athletes is measured by “VO2 max,” which
a pressure of 1.78 torr at 35 °C, how many grams of neon are is the maximum volume of oxygen consumed by an individual
in the sign? (The volume of a cylinder is pr2h.) during incremental exercise (for example, on a treadmill). An
average male has a VO2 max of 45 mL O2 >kg body mass/min,
10.37 (a) Calculate the number of molecules in a deep breath of air but a world-class male athlete can have a VO2 max reading
whose volume is 2.25 L at body temperature, 37 °C, and a pres- of 88.0 mL O2 >kg body mass/min. (a) Calculate the volume
sure of 735 torr. (b) The adult blue whale has a lung capacity of of oxygen, in mL, consumed in 1 hr by an average man who
5.0 * 103 L. Calculate the mass of air (assume an average molar weighs 185 lbs and has a VO2 max reading of 47.5 mL O2 >kg
mass of 28.98 g>mol) contained in an adult blue whale’s lungs body mass/min. (b) If this man lost 20 lb, exercised, and in-
at 0.0 °C and 1.00 atm, assuming the air behaves ideally. creased his VO2 max to 65.0 mL O2 >kg body mass/min, how
10.38 (a) If the pressure exerted by ozone, O3, in the stratosphere is many mL of oxygen would he consume in 1 hr?
3.0 * 10-3 atm and the temperature is 250 K, how many ozone
molecules are in a liter? (b) Carbon dioxide makes up approxi- Further Applications of the Ideal-Gas Equation
mately 0.04% of Earth’s atmosphere. If you collect a 2.0-L sam- (Section 10.5)
ple from the atmosphere at sea level (1.00 atm) on a warm day
127 °C2, how many CO2 molecules are in your sample? 10.47 Which gas is most dense at 1.00 atm and 298 K: CO2, N2O, or Cl2?
Explain.
10.39 A scuba diver’s tank contains 0.29 kg of O2 compressed into a
volume of 2.3 L. (a) Calculate the gas pressure inside the tank 10.48 Rank the following gases from least dense to most dense at
at 9 °C. (b) What volume would this oxygen occupy at 26 °C 1.00 atm and 298 K: SO2, HBr, CO2. Explain.
and 0.95 atm? 10.49 Which of the following statements best explains why a closed
10.40 An aerosol spray can with a volume of 250 mL contains balloon filled with helium gas rises in air?
2.30 g of propane gas 1C3H82 as a propellant. (a) If the can (a) Helium is a monatomic gas, whereas nearly all the mol-
is at 23 °C, what is the pressure in the can? (b) What volume ecules that make up air, such as nitrogen and oxygen, are
would the propane occupy at STP? (c) The can’s label says diatomic.
that exposure to temperatures above 130 °F may cause the can (b) The average speed of helium atoms is greater than the
to burst. What is the pressure in the can at this temperature? ­average speed of air molecules, and the greater speed of
10.41 A 35.1 g sample of solid CO2 (dry ice) is added to a container ­collisions with the balloon walls propels the balloon upward.
at a temperature of 100 K with a volume of 4.0 L. If the con- (c) Because the helium atoms are of lower mass than the av-
tainer is evacuated (all of the gas removed), sealed and then erage air molecule, the helium gas is less dense than air.
allowed to warm to room temperature 1T = 298 K2 so that The mass of the balloon is thus less than the mass of the
all of the solid CO2 is converted to a gas, what is the pressure air displaced by its volume.
inside the container?
(d) Because helium has a lower molar mass than the average
10.42 A 334-mL cylinder for use in chemistry lectures contains air molecule, the helium atoms are in faster motion. This
5.225 g of helium at 23 °C. How many grams of helium must means that the temperature of the helium is greater than
be released to reduce the pressure to 75 atm assuming ideal the air temperature. Hot gases tend to rise.
gas behavior?
10.50 Which of the following statements best explains why nitrogen
10.43 Chlorine is widely used to purify municipal water supplies and to gas at STP is less dense than Xe gas at STP?
treat swimming pool waters. Suppose that the volume of a par-
(a) Because Xe is a noble gas, there is less tendency for
ticular sample of Cl2 gas is 8.70 L at 895 torr and 24 °C. (a) How
the Xe atoms to repel one another, so they pack more
many grams of Cl2 are in the sample? (b) What volume will the
densely in the gaseous state.
Cl2 occupy at STP? (c) At what temperature will the volume be
15.00 L if the pressure is 8.76 * 102 torr? (d) At what pressure (b) Xe atoms have a higher mass than N2 molecules. Because
will the volume equal 5.00 L if the temperature is 58 °C? both gases at STP have the same number of molecules
per unit volume, the Xe gas must be denser.
10.44 Many gases are shipped in high-pressure containers. Consider a
steel tank whose volume is 55.0 gallons that contains O2 gas at a (c) The Xe atoms are larger than N2 molecules and thus take
pressure of 16,500 kPa at 23 °C. (a) What mass of O2 does the up a larger fraction of the space occupied by the gas.
tank contain? (b) What volume would the gas occupy at STP? (d) Because the Xe atoms are much more massive than the
(c) At what temperature would the pressure in the tank equal N2 molecules, they move more slowly and thus exert
150.0 atm? (d) What would be the pressure of the gas, in kPa, if it less upward force on the gas container and make the gas
were transferred to a container at 24 °C whose volume is 55.0 L? ­appear denser.
436 chapter 10 Gases

10.51 (a) Calculate the density of NO2 gas at 0.970 atm and 35 °C. 10.58 Both Jacques Charles and Joseph Louis Guy-Lussac were avid
(b) Calculate the molar mass of a gas if 2.50 g occupies 0.875 L ­b alloonists. In his original flight in 1783, Jacques Charles
at 685 torr and 35 °C. used a balloon that contained approximately 31,150 L of H2.
10.52 (a) Calculate the density of sulfur hexafluoride gas at 707 torr He generated the H2 using the reaction between iron and
and 21 °C. (b) Calculate the molar mass of a vapor that has a ­hydrochloric acid:
density of 7.135 g>L at 12 °C and 743 torr. Fe1s2 + 2 HCl1aq2 ¡ FeCl21aq2 + H21g2
10.53 In the Dumas-bulb technique for determining the molar mass
How many kilograms of iron were needed to produce this
of an unknown liquid, you vaporize the sample of a liquid that
volume of H2 if the temperature was 22 °C?
boils below 100 °C in a boiling-water bath and determine the
mass of vapor required to fill the bulb. From the following 10.59 Hydrogen gas is produced when zinc reacts with sulfuric acid:
data, calculate the molar mass of the unknown liquid: mass Zn1s2 + H2SO41aq2 ¡ ZnSO41aq2 + H21g2
of unknown ­vapor, 1.012 g; volume of bulb, 354 cm3; pressure,
742 torr; ­temperature, 99 °C. If 159 mL of wet H2 is collected over water at 24 °C and a
barometric pressure of 738 torr, how many grams of Zn have
been consumed? (The vapor pressure of water is tabulated in
Appendix B.)
10.60 Acetylene gas, C2H21g2, can be prepared by the reaction of
calcium carbide with water:
Dumas bulb Boiling water
filled with CaC21s2 + 2 H2O1l2 ¡ Ca1OH221aq2 + C2H21g2
vaporized Calculate the volume of C2H2 that is collected over water at
unknown 23 °C by reaction of 1.524 g of CaC2 if the total pressure of
substance the gas is 753 torr. (The vapor pressure of water is tabulated
in Appendix B.)

Partial Pressures (Section 10.6)

10.61 Consider the apparatus shown in the following drawing.
(a) When the valve between the two containers is opened and
the gases allowed to mix, how does the volume occupied by
10.54 The molar mass of a volatile substance was determined by the N2 gas change? What is the partial pressure of N2 after
the Dumas-bulb method described in Exercise 10.53. The mixing? (b) How does the volume of the O2 gas change when
unknown vapor had a mass of 0.846 g; the volume of the the gases mix? What is the partial pressure of O2 in the mix-
bulb was 354 cm3, pressure 752 torr, and temperature 100 °C. ture? (c) What is the total pressure in the container after the
Calculate the molar mass of the unknown vapor. gases mix?
10.55 Magnesium can be used as a “getter” in evacuated enclo-
sures to react with the last traces of oxygen. (The mag-
nesium is usually heated by passing an electric current N2 O2
through a wire or ribbon of the metal.) If an enclosure of
0.452 L has a partial pressure of O2 of 3.5 * 10-6 torr at
27 °C, what mass of magnesium will react according to the
following equation? 2.0 L 3.0 L
1.0 atm 2.0 atm
2 Mg1s2 + O21g2 ¡ 2 MgO1s2
25 °C 25 °C
10.56 C alcium hydride, CaH2, reac ts with water to form
hydrogen gas: 10.62 Consider a mixture of two gases, A and B, confined in a closed
vessel. A quantity of a third gas, C, is added to the same ves-
CaH21s2 + 2 H2O1l2 ¡ Ca1OH221aq2 + 2 H21g2 sel at the same temperature. How does the addition of gas C
affect the following: (a) the partial pressure of gas A, (b) the
This reaction is sometimes used to inflate life rafts, weather
total pressure in the vessel, (c) the mole fraction of gas B?
balloons, and the like, when a simple, compact means of
generating H2 is desired. How many grams of CaH2 are 10.63 A mixture containing 0.765 mol He(g), 0.330 mol Ne(g),
needed to generate 145 L of H2 gas if the pressure of H2 is and 0.110 mol Ar(g) is confined in a 10.00-L vessel at 25 °C.
825 torr at 21 °C? (a) Calculate the partial pressure of each of the gases in the
mixture. (b) Calculate the total pressure of the mixture.
10.57 The metabolic oxidation of glucose, C6H12O6, in our bodies
produces CO2, which is expelled from our lungs as a gas: 10.64 A deep-sea diver uses a gas cylinder with a volume of 10.0 L
and a content of 51.2 g of O2 and 32.6 g of He. Calculate the
C6H12O61aq2 + 6 O21g2 ¡ 6 CO21g2 + 6 H2O1l2 partial pressure of each gas and the total pressure if the tem-
(a) Calculate the volume of dry CO2 produced at body tem- perature of the gas is 19 °C.
perature 137 °C2 and 0.970 atm when 24.5 g of glucose is con- 10.65 The atmospheric concentration of CO2 gas is presently 390
sumed in this reaction. (b) Calculate the volume of oxygen ppm (parts per million, by volume; that is, 390 L of every
you would need, at 1.00 atm and 298 K, to completely oxidize 106 L of the atmosphere are CO2). What is the mole fraction
50.0 g of glucose. of CO2 in the atmosphere?
 Exercises 437

10.66 A plasma-screen TV contains thousands of tiny cells filled 10.76 Indicate which of the following statements regarding the
with a mixture of Xe, Ne, and He gases that emits light of kinetic-molecular theory of gases are correct. (a) The aver-
specific wavelengths when a voltage is applied. A particu- age kinetic energy of a collection of gas molecules at a given
lar plasma cell, 0.900 mm * 0.300 mm * 10.0 mm, con- temperature is proportional to m1>2. (b) The gas molecules
tains 4% Xe in a 1:1 Ne:He mixture at a total pressure of are assumed to exert no forces on each other. (c) All the mol-
500 torr. Calculate the number of Xe, Ne, and He atoms in ecules of a gas at a given temperature have the same kinetic
the cell and state the assumptions you need to make in your energy. (d) The volume of the gas molecules is negligible in
calculation. comparison to the total volume in which the gas is contained.
10.67 A piece of dry ice (solid carbon dioxide) with a mass of 5.50 g (e) All gas molecules move with the same speed if they are at
is placed in a 10.0-L vessel that already contains air at 705 torr the same temperature.
and 24 °C. After the carbon dioxide has totally sublimed, what 10.77 Which assumptions are common to both kinetic-molecular
is the partial pressure of the resultant CO2 gas, and the total theory and the ideal-gas equation?
pressure in the container at 24 °C? 10.78 Newton had an incorrect theory of gases in which he assumed
10.68 A sample of 5.00 mL of diethylether 1C2H5OC2H5, that all gas molecules repel one another and the walls of their
density = 0.7134 g>mL2 is introduced into a 6.00-L vessel container. Thus, the molecules of a gas are statically and uni-
that already contains a mixture of N2 and O2, whose partial formly distributed, trying to get as far apart as possible from
pressures are PN2 = 0.751 atm and PO2 = 0.208 atm. The one another and the vessel walls. This repulsion gives rise to
temperature is held at 35.0 °C, and the diethylether totally pressure. Explain why Charles’s law argues for the kinetic-
evaporates. (a) Calculate the partial pressure of the diethyl- molecular theory and against Newton’s model.
ether. (b) Calculate the total pressure in the container. 10.79 WF6 is one of the heaviest known gases. How much slower is
10.69 A rigid vessel containing a 3:1 mol ratio of carbon dioxide the root-mean-square speed of WF6 than He at 300 K?
and water vapor is held at 200 °C where it has a total pres- [10.80] You have an evacuated container of fixed volume and known
sure of 2.00 atm. If the vessel is cooled to 10 °C so that all mass and introduce a known mass of a gas sample. Measuring
of the w
­ ater vapor condenses, what is the pressure of carbon the pressure at constant temperature over time, you are sur-
dioxide? ­Neglect the volume of the liquid water that forms on prised to see it slowly dropping. You measure the mass of the
cooling. gas-filled container and find that the mass is what it should
10.70 If 5.15 g of Ag2O is sealed in a 75.0-mL tube filled with 760 torr be—gas plus container—and the mass does not change over
of N2 gas at 32 °C, and the tube is heated to 320 °C, the Ag2O time, so you do not have a leak. Suggest an explanation for
­decomposes to form oxygen and silver. What is the total pres- your observations.
sure inside the tube assuming the volume of the tube ­remains 10.81 The temperature of a 5.00-L container of N2 gas is increased
constant? from 20 °C to 250 °C. If the volume is held constant, predict
10.71 At an underwater depth of 250 ft, the pressure is 8.38 atm. qualitatively how this change affects the following: (a) the
What should the mole percent of oxygen be in the diving average kinetic energy of the molecules; (b) the root-mean-
gas for the partial pressure of oxygen in the mixture to be square speed of the molecules; (c) the strength of the impact
0.21 atm, the same as in air at 1 atm? of an average molecule with the container walls; (d) the total
10.72 (a) What are the mole fractions of each component in a mix- number of collisions of molecules with walls per second.
ture of 15.08 g of O2, 8.17 g of N2, and 2.64 g of H2? (b) What 10.82 Suppose you have two 1-L flasks, one containing N2 at STP,
is the partial pressure in atm of each component of this mix- the other containing CH4 at STP. How do these systems com-
ture if it is held in a 15.50-L vessel at 15 °C? pare with respect to (a) number of molecules, (b) density,
10.73 A quantity of N2 gas originally held at 5.25 atm pressure in a (c) average kinetic energy of the molecules, (d) rate of effu-
1.00-L container at 26 °C is transferred to a 12.5-L container sion through a pinhole leak?
at 20 °C. A quantity of O2 gas originally at 5.25 atm and 26 °C 10.83 (a) Place the following gases in order of increasing average
in a 5.00-L container is transferred to this same container. molecular speed at 25 °C: Ne, HBr, SO2, NF3, CO. (b) Calcu-
What is the total pressure in the new container? late the rms speed of NF3 molecules at 25 °C. (c) Calculate the
10.74 A sample of 3.00 g of SO21g2 originally in a 5.00-L vessel at most probable speed of an ozone molecule in the stratosphere,
21 °C is transferred to a 10.0-L vessel at 26 °C. A sample of where the temperature is 270 K.
2.35 g of N21g2 originally in a 2.50-L vessel at 20 °C is trans- 10.84 (a) Place the following gases in order of increasing average mo-
ferred to this same 10.0-L vessel. (a) What is the partial pres- lecular speed at 300 K: CO, SF6, H2S, Cl2, HBr. (b) Calculate
sure of SO21g2 in the larger container? (b) What is the partial the rms speeds of CO and Cl2 molecules at 300 K. (c) Calculate
pressure of N21g2 in this vessel? (c) What is the total pressure the most probable speeds of CO and Cl2 molecules at 300 K.
in the vessel?
10.85 Explain the difference between effusion and diffusion.
[10.86] At constant pressure, the mean free path 1l2 of a gas mol-
ecule is directly proportional to temperature. At constant
Kinetic-Molecular Theory of Gases; Effusion
temperature, l is inversely proportional to pressure. If you
and Diffusion (Sections 10.7 and 10.8) compare two different gas molecules at the same temperature
10.75 Determine whether each of the following changes will in- and pressure, l is inversely proportional to the square of the
crease, decrease, or not affect the rate with which gas mol- diameter of the gas molecules. Put these facts together to cre-
ecules collide with the walls of their container: (a) increasing ate a formula for the mean free path of a gas molecule with a
the volume of the container, (b) increasing the temperature, proportionality constant (call it Rmfp, like the ideal-gas con-
(c) increasing the molar mass of the gas. stant) and define units for Rmfp.
438 chapter 10 Gases

10.87 Hydrogen has two naturally occurring isotopes, 1H and 2H. 10.93 Based on their respective van der Waals constants (Table
Chlorine also has two naturally occurring isotopes, 35Cl and 10.3), is Ar or CO2 expected to behave more nearly like an
37
Cl. Thus, hydrogen chloride gas consists of four distinct ideal gas at high pressures? Explain.
types of molecules: 1H35Cl, 1H37Cl, 2H35Cl, and 2H37Cl. Place 10.94 Briefly explain the significance of the constants a and b in the
these four molecules in order of increasing rate of effusion. van der Waals equation.
10.88 As discussed in the “Chemistry Put to Work” box in Section 10.95 In Sample Exercise 10.16, we found that one mole of Cl2 con-
10.8, enriched uranium can be produced by effusion of gas- fined to 22.41 L at 0 °C deviated slightly from ideal behavior.
eous UF6 across a porous membrane. Suppose a process were Calculate the pressure exerted by 1.00 mol Cl2 confined to a
developed to allow effusion of gaseous uranium atoms, U(g). smaller volume, 5.00 L, at 25 °C. (a) First use the ideal-gas
Calculate the ratio of effusion rates for 235U and 238U, and equation and (b) then use the van der Waals equation for
compare it to the ratio for UF6 given in the essay. your calculation. (Values for the van der Waals constants are
10.89 Arsenic(III) sulfide sublimes readily, even below its melting point given in Table 10.3.) (c) Why is the difference between the
of 320 °C. The molecules of the vapor phase are found to effuse result for an ideal gas and that calculated using the van der
through a tiny hole at 0.28 times the rate of effusion of Ar atoms Waals equation greater when the gas is confined to 5.00 L
under the same conditions of temperature and pressure. What is compared to 22.4 L?
the molecular formula of arsenic(III) sulfide in the gas phase? 10.96 Calculate the pressure that CCl4 will exert at 40 °C if 1.00 mol
10.90 A gas of unknown molecular mass was allowed to effuse occupies 33.3 L, assuming that (a) CCl4 obeys the ideal-
through a small opening under constant-pressure conditions. gas equation; (b) CCl4 obeys the van der Waals equa-
It required 105 s for 1.0 L of the gas to effuse. Under identi- tion. ­(Values for the van der Waals constants are given in
cal experimental conditions it required 31 s for 1.0 L of O2 Table 10.3.) (c) Which would you expect to deviate more
gas to effuse. Calculate the molar mass of the unknown gas. from ideal b­ ehavior under these conditions, Cl2 or CCl4?
(Remember that the faster the rate of effusion, the shorter the Explain.
time required for effusion of 1.0 L; in other words, rate is the [10.97] Table 10.3 shows that the van der Waals b parameter has units
amount that diffuses over the time it takes to diffuse.) of L/mol. This implies that we can calculate the size of atoms
or molecules from b. Using the value of b for Xe, calculate
the radius of a Xe atom and compare it to the value found in
Nonideal-Gas Behavior (Section 10.9) ­Figure 7.7, that is, 1.40 Å. Recall that the volume of a sphere is
10.91 (a) List two experimental conditions under which gases devi- 14>32pr3.
ate from ideal behavior. (b) List two reasons why the gases [10.98] Table 10.3 shows that the van der Waals b parameter has units
deviate from ideal behavior. of L/mol. This means that we can calculate the sizes of atoms
10.92 The planet Jupiter has a surface temperature of 140 K and a or molecules from the b parameter. Refer back to the discus-
mass 318 times that of Earth. Mercury (the planet) has a sur- sion in Section 7.3. Is the van der Waals radius we calculate
face temperature between 600 K and 700 K and a mass 0.05 from the b parameter of Table 10.3 more closely associated
times that of Earth. On which planet is the atmosphere more with the bonding or nonbonding atomic radius discussed
likely to obey the ideal-gas law? Explain. there? Explain.

Additional Exercises
10.99 A gas bubble with a volume of 1.0 mm3 originates at the fueled by coal, oil, or natural gas. One potential way to re-
­bottom of a lake where the pressure is 3.0 atm. Calculate its duce the amount of CO2 added to the atmosphere is to store
volume when the bubble reaches the surface of the lake where it as a compressed gas in underground formations. Consider
the pressure is 730 torr, assuming that the temperature doesn’t a 1000-megawatt coal-fired power plant that produces about
change. 6 * 106 tons of CO2 per year. (a) Assuming ideal-gas behavior,
10.100 A 15.0-L tank is filled with helium gas at a pressure of 1.00 atm, and 27 °C, calculate the volume of CO2 produced
1.00 * 102 atm. How many balloons (each 2.00 L) can by this power plant. (b) If the CO2 is stored underground as
be ­i nflated to a pressure of 1.00 atm, assuming that the a liquid at 10 °C and 120 atm and a density of 1.2 g>cm3, what
­temperature remains constant and that the tank cannot be volume does it possess? (c) If it is stored underground as a gas
emptied below 1.00 atm? at 36 °C and 90 atm, what volume does it occupy?

10.101 To minimize the rate of evaporation of the tungsten 10.103 Propane, C3H8, liquefies under modest pressure, allowing
­f ilament, 1.4 * 10-5 mol of argon is placed in a 600@cm3 a large amount to be stored in a container. (a) Calculate the
lightbulb. What is the pressure of argon in the lightbulb at number of moles of propane gas in a 110-L container at 3.00
23 °C? atm and 27 °C. (b) Calculate the number of moles of liquid
propane that can be stored in the same volume if the density
10.102 Carbon dioxide, which is recognized as the major con-
of the liquid is 0.590 g>mL. (c) Calculate the ratio of the num-
tributor to global warming as a “greenhouse gas,” is formed
ber of moles of liquid to moles of gas. Discuss this ratio in
when fossil fuels are combusted, as in electrical power plants
light of the kinetic-molecular theory of gases.
 Additional Exercises 439

[10.104] Nickel carbonyl, Ni1CO24, is one of the most toxic substances

known. The present maximum allowable concentration in
laboratory air during an 8-hr workday is 1 ppb (parts per
billion) by volume, which means that there is one mole of
Ni1CO24 for every 109 moles of gas. Assume 24 °C and 1.00
atm pressure. What mass of Ni1CO24 is allowable in a labora-
tory room that is 12 ft * 20 ft * 9 ft?
10.111 The density of a gas of unknown molar mass was measured
10.105 When a large evacuated flask is filled with argon gas, its
as a function of pressure at 0 °C, as in the table that follows.
mass increases by 3.224 g. When the same flask is again
(a) Determine a precise molar mass for the gas. [Hint: Graph
evacuated and then filled with a gas of unknown molar
d>P versus P.] (b) Why is d>P not a constant as a function of
mass, the mass increase is 8.102 g. (a) Based on the molar
pressure?
mass of argon, estimate the molar mass of the unknown
gas. (b) What assumptions did you make in arriving at your
answer? Pressure (atm) 1.00 0.666 0.500 0.333 0.250
10.106 Consider the arrangement of bulbs shown in the drawing. Density (g/L) 2.3074 1.5263 1.1401 0.7571 0.5660
Each of the bulbs contains a gas at the pressure shown. What
is the pressure of the system when all the stopcocks are
opened, assuming that the temperature remains constant? 10.112 A glass vessel fitted with a stopcock valve has a mass of
(We can neglect the volume of the capillary tubing connect- 337.428 g when evacuated. When filled with Ar, it has a mass
ing the bulbs.) of 339.854 g. When evacuated and refilled with a mixture of
Ne and Ar, under the same conditions of temperature and
pressure, it has a mass of 339.076 g. What is the mole percent
N2 Ne
H2 of Ne in the gas mixture?
10.113 You have a sample of gas at -33 °C. You wish to increase the
rms speed by a factor of 2. To what temperature should the
gas be heated?
10.114 Consider the following gases, all at STP: Ne, SF6, N2, CH4.
(a) Which gas is most likely to depart from the assumption
1.0 L 1.0 L 0.5 L of the kinetic-molecular theory that says there are no attrac-
265 torr 800 torr 532 torr tive or repulsive forces between molecules? (b) Which one
is closest to an ideal gas in its behavior? (c) Which one has
10.107 Assume that a single cylinder of an automobile engine the highest root-mean-square molecular speed at a given
has a volume of 524 cm3. (a) If the cylinder is full of air at temperature? (d) Which one has the highest total molecular
74 °C and 0.980 atm, how many moles of O2 are present? volume ­relative to the space occupied by the gas? (e) Which
(The mole fraction of O2 in dry air is 0.2095.) (b) How has the highest average kinetic-molecular energy? (f) Which
many grams of C8H18 could be combusted by this quantity one would ­effuse more rapidly than N2? (g) Which one would
of O2, assuming complete combustion with formation of have the largest van der Waals b parameter?
CO2 and H2O?
10.115 Does the effect of intermolecular attraction on the properties
10.108 Assume that an exhaled breath of air consists of
of a gas become more significant or less significant if (a) the
74.8% N2, 15.3% O2, 3.7% CO2, and 6.2% water vapor. (a) If
gas is compressed to a smaller volume at constant temperature;
the total pressure of the gases is 0.985 atm, calculate the par-
(b) the temperature of the gas is increased at constant volume?
tial pressure of each component of the mixture. (b) If the vol-
ume of the exhaled gas is 455 mL and its temperature is 37 °C, 10.116 Which of the noble gases other than radon would you expect
calculate the number of moles of CO2 exhaled. (c) How many to depart most readily from ideal behavior? Use the density
grams of glucose 1C6H12O62 would need to be metabolized to data in Table 7.8 to show evidence in support of your answer.
produce this quantity of CO2? (The chemical reaction is the 10.117 It turns out that the van der Waals constant b equals four
same as that for combustion of C6H12O6. See Section 3.2 and times the total volume actually occupied by the molecules of
Problem 10.57.) a mole of gas. Using this figure, calculate the fraction of the
10.109 A 1.42-g sample of helium and an unknown mass of O2 are volume in a container actually occupied by Ar atoms (a) at
mixed in a flask at room temperature. The partial pressure STP, (b) at 200 atm pressure and 0 °C. (Assume for simplicity
of the helium is 42.5 torr, and that of the oxygen is 158 torr. that the ideal-gas equation still holds.)
What is the mass of the oxygen? [10.118] Large amounts of nitrogen gas are used in the manufac-
[10.110] An ideal gas at a pressure of 1.50 atm is contained in a bulb ture of ammonia, principally for use in fertilizers. Suppose
of unknown volume. A stopcock is used to connect this 120.00 kg of N21g2 is stored in a 1100.0-L metal cylinder at
bulb with a previously evacuated bulb that has a volume 280 °C. (a) Calculate the pressure of the gas, assuming ideal-
of 0.800 L as shown here. When the stopcock is opened gas ­behavior. (b) By using the data in Table 10.3, calculate the
the gas expands into the empty bulb. If the temperature is pressure of the gas according to the van der Waals equation.
held constant during this process and the final pressure is (c) Under the conditions of this problem, which correction
695 torr, what is the volume of the bulb that was originally dominates, the one for finite volume of gas molecules or the
filled with gas? one for attractive interactions?
440 chapter 10 Gases

Integrative Exercises
10.119 Cyclopropane, a gas used with oxygen as a general anesthetic, (Note: Less than this amount of methane is actually com-
is composed of 85.7% C and 14.3% H by mass. (a) If 1.56 g of busted daily. Some of the delivered gas is passed through to
cyclopropane has a volume of 1.00 L at 0.984 atm and 50.0 °C, other regions.)
what is the molecular formula of cyclopropane? (b) Judging 10.125 Chlorine dioxide gas 1ClO22 is used as a commercial bleach-
from its molecular formula, would you expect cyclopropane ing agent. It bleaches materials by oxidizing them. In the
to deviate more or less than Ar from ideal-gas behavior at course of these reactions, the ClO2 is itself reduced. (a) What
moderately high pressures and room temperature? Explain. is the Lewis structure for ClO2? (b) Why do you think that
(c) Would cyclopropane effuse through a pinhole faster or ClO2 is reduced so readily? (c) When a ClO2 molecule gains
more slowly than methane, CH4? an electron, the chlorite ion, ClO2-, forms. Draw the Lewis
[10.120] Consider the combustion reaction between 25.0 mL of liquid structure for ClO2-. (d) Predict the O ¬ Cl ¬ O bond angle
methanol 1density = 0.850 g>mL2 and 12.5 L of oxygen gas in the ClO2- ion. (e) One method of preparing ClO2 is by the
measured at STP. The products of the reaction are CO21g2 reaction of chlorine and sodium chlorite:
and H2O1g2. Calculate the volume of liquid H2O formed if
Cl21g2 + 2 NaClO21s2 ¡ 2 ClO21g2 + 2 NaCl1s2
the ­reaction goes to completion and you condense the water
vapor. If you allow 15.0 g of NaClO2 to react with 2.00 L of chlo-
10.121 An herbicide is found to contain only C, H, N, and Cl. The rine gas at a pressure of 1.50 atm at 21 °C, how many grams of
complete combustion of a 100.0-mg sample of the herbicide ClO2 can be prepared?
in excess oxygen produces 83.16 mL of CO2 and 73.30 mL of 10.126 Natural gas is very abundant in many Middle Eastern oil
H2O vapor at STP. A separate analysis shows that the sample fields. However, the costs of shipping the gas to markets in
also contains 16.44 mg of Cl. (a) Determine the percentage other parts of the world are high because it is necessary to liq-
of the composition of the substance. (b) Calculate its empiri- uefy the gas, which is mainly methane and has a boiling point
cal formula. (c) What other information would you need to at atmospheric pressure of -164 °C. One possible strategy
know about this compound to calculate its true molecular is to oxidize the methane to methanol, CH3OH, which has
formula? a boiling point of 65 °C and can therefore be shipped more
10.122 A 4.00-g sample of a mixture of CaO and BaO is placed readily. Suppose that 10.7 * 109 ft3 of methane at atmo-
in a 1.00-L vessel containing CO2 gas at a pressure of 730 spheric pressure and 25 °C is oxidized to methanol. (a) What
torr and a temperature of 25 °C. The CO2 reacts with the volume of methanol is formed if the density of CH3OH is
CaO and BaO, forming CaCO3 and BaCO3. When the re- 0.791 g>mL? (b) Write balanced chemical equations for the
action is complete, the pressure of the remaining CO2 is oxidations of methane and methanol to CO21g2 and H2O1l2.
150 torr. (a) Calculate the number of moles of CO2 that Calculate the total enthalpy change for complete combus-
have reacted. (b) Calculate the mass percentage of CaO in tion of the 10.7 * 109 ft3 of methane just described and for
the mixture. complete combustion of the equivalent amount of methanol,
as calculated in part (a). (c) Methane, when liquefied, has a
[10.123] Ammonia and hydrogen chloride react to form solid ammo-
density of 0.466 g>mL; the density of methanol at 25 °C is
nium chloride:
0.791 g>mL. Compare the enthalpy change upon combus-
NH31g2 + HCl1g2 ¡ NH4Cl1s2 tion of a unit volume of liquid methane and liquid methanol.
From the standpoint of energy production, which substance
Two 2.00-L flasks at 25 °C are connected by a valve, as shown has the higher enthalpy of combustion per unit volume?
in the drawing on the next page. One flask contains 5.00 g of
[10.127] Gaseous iodine pentafluoride, IF5, can be prepared by the
NH31g2, and the other contains 5.00 g of HCl(g). When the
­reaction of solid iodine and gaseous fluorine:
valve is opened, the gases react until one is completely con-
sumed. (a) Which gas will remain in the system after the re- I21s2 + 5 F21g2 ¡ 2 IF51g2
action is complete? (b) What will be the final pressure of the
A 5.00-L flask containing 10.0 g of I2 is charged with
system after the reaction is complete? (Neglect the volume of
10.0 g of F2, and the reaction proceeds until one of the r­ eagents
the ammonium chloride formed.) (c) What mass of ammo-
is completely consumed. After the reaction is complete, the
nium chloride will be formed?
temperature in the flask is 125 °C. (a) What is the partial pres-
sure of IF5 in the flask? (b) What is the mole fraction of IF5 in
the flask (c) Draw the Lewis structure of IF5. (d) What is the
NH3(g) HCl(g) total mass of reactants and products in the flask?
[10.128] A 6.53-g sample of a mixture of magnesium carbonate and
calcium carbonate is treated with excess hydrochloric acid.
5.00 g 5.00 g
2.00 L 2.00 L The resulting reaction produces 1.72 L of carbon dioxide gas
25 °C 25 °C at 28 °C and 743 torr pressure. (a) Write balanced chemical
equations for the reactions that occur between hydrochloric
10.124 Gas pipelines are used to deliver natural gas (methane, acid and each component of the mixture. (b) Calculate the
CH4 ) to the various regions of the United States. The total total number of moles of carbon dioxide that forms from
volume of natural gas that is delivered is on the order of these reactions. (c) Assuming that the reactions are complete,
2.7 * 1012 L per day, measured at STP. Calculate the total calculate the percentage by mass of magnesium carbonate in
enthalpy change for combustion of this quantity of methane. the mixture.
 Design an Experiment 441

Design an Experiment
You are given a cylinder of an unknown, non-radioactive, noble gas and tasked to determine its
molar mass and use that value to identify the gas. The tools available to you are several empty
mylar balloons that are about the size of a grapefruit when inflated (gases diffuse through mylar
much more slowly than conventional latex b­ alloons), an analytical balance, and three graduated
glass beakers of different sizes (100 mL, 500 mL, and 2 L). (a) To how many significant figures
would you need to determine the molar mass to identify the gas? (b) Propose an experiment or
series of experiments that would allow you to determine the molar mass of the unknown gas.
Describe the tools, calculations, and assumptions you would need to use. (c) If you had access to
a broader range of analytical instruments, describe an alternative way you could identify the gas
using any experimental methods that you have learned about in the earlier chapters.