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11/5/2019

Chapter 10
GASES

Properties of Gases
• Characteristics of Gases
• Sample of gas assumes both the shape and volume of its container
• Gases are compressible
• Densities of gases are much smaller than those of liquids and solids
and are highly variable depending on temperature and pressure.
• Gases form homogeneous mixtures (solutions) with one another in
any proportion

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Properties of Gases
• Gas Pressure: Definition and Units
• Pressure
• Defined as the force applied per unit area: pressure =
• SI unit of force is the newton (N) (1N = 1kg m⁄s )
• SI unit of pressure is the pascal (Pa)
• Defined as 1 newton per square meter
• 1Pa = 1N⁄m
• 1Pa = 1kg⁄m s

Unit Origin Definition


standard atmosphere Pressure at sea Level 1atm=101,325Pa
(atm)
mmHg Barometer measurement 1 mmHg= 133.322Pa
torr Name given to mmHg in honor of 1torr=133.322pa
Torricelli, the inventor of the barometer
bar Same order of magnitude as atm, 1bar=1× 10 Pa
but a decimal multiple of Pa

Properties of Gases
• Measurement of Pressure
• Barometer
• Instrument used to measure atmospheric pressure
• Standard Atmospheric Pressure (1 atm)
• Defined as the pressure that would support a column of mercury exactly 760 mm high at
0°C at sea level
• Manometer
• Device used to measure pressures other than atmospheric pressure

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The Gas Laws


• Boyle’s Law: The Pressure-Volume Relationship
• 𝑉∝
• 𝑃𝑉 =𝑃 𝑉 at constant temperature

SAMPLE PROBLEM 10.2


If a skin diver takes a breath at the surface, filling his lungs
with 5.82 L of air, what volume will the air in his lungs occupy
when he dives to a depth where the pressure is 1.92 atm?
(Assume constant temperature and that the pressure at the
surface is exactly 1 atm.)

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The Gas Laws


• Charles’s and Gay-Lussac’s Law: The Temperature-Volume
Relationship
• Temperatures in kelvins
• 𝑉∝𝑇
• =
• at constant pressure

SAMPLE PROBLEM 10.3


A sample of argon gas that originally occupied 14.6 L at 25.0°C
was heated to 50.0°C at constant pressure. What is its new
volume?

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The Gas Law


• Avogadro’s Law: The Amount-Volume Relationship
• 𝑉∝𝑛
• =

SAMPLE PROBLEM 10.4


If we combine 3.0 L of NO and 1.5 L of O2, and they react
according to the balanced equation 2NO 𝑔 + O 𝑔 →
2NO 𝑔 , what volume of NO2 will be produced? (Assume
that the reactants and product are all at the same
temperature and pressure.)

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The Gas Laws


• The Combined Gas Law: The Pressure-Temperature-
Amount-Volume Relationship
• =
• For a fixed amount of gas (n1 = n2):
• =

SAMPLE PROBLEM 10.5


If a child releases a 6.25-L helium balloon in the parking lot of
an amusement park where the temperature is 28.50°C and
the air pressure is 757.2 mmHg, what will the volume of the
balloon be when it has risen to an altitude where the
temperature is –34.35°C and the air pressure is 366.4 mmHg?

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The Ideal Gas Equation


• Deriving the Ideal Gas Equation from the Empirical Gas
Laws
• Boyle’s Law: 𝑉∝ Numerical Value Unit
0.08206 L atm⁄K mol
• Charles’s Law: 𝑉 ∝ 𝑇 62.36 L torr⁄K mol

• Avogadro’s law:𝑉 ∝ 𝑛 0.08314 L bar⁄K mol


8.314 m Pa⁄K mol
• 𝑉∝
8.314 J⁄K mol

• 𝑉=𝑅 1.987 cal⁄K mol

• 𝑃𝑉 = 𝑛𝑅𝑇

The Ideal Gas Equation


• Molar Volume of a Gas at STP
• Volume of 1 mole of an ideal gas at 0°C and 1 atm
• Conditions known as standard temperature and pressure (STP)

• 𝑉=
. ⁄ .
• 𝑉= = 22.41 L

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SAMPLE PROBLEM 10.6


Calculate the volume of a mole of ideal gas at room
temperature (25°C) and 1 atm.

The Ideal Gas Equation


• Applications of the Ideal Gas Equation
• Calculating the density of a gas
• d=

• Calculating the molar mass of a gas


• M=

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SAMPLE PROBLEM 10.7


Carbon dioxide is effective in fire extinguishers partly because
its density is greater than that of air, so CO2 can smother the
flames by depriving them of oxygen. (Air has a density of
approximately 1.2 g/L at room temperature and 1 atm.)
Calculate the density of CO2 at room temperature (25°C) and
1.0 atm.

SAMPLE PROBLEM 10.8


A company has just patented a new synthetic alcohol for alcoholic
beverages. The new product is said to have all the pleasant
properties associated with ethanol but none of the undesirable
effects such as hangover, impairment of motor skills, and risk of
addiction. The chemical formula is proprietary. You analyze a
sample of the new product by placing a small volume of it in a
round-bottomed flask with a volume of 511.0 mL and an
evacuated mass of 131.918 g. You submerge the flask in a water
bath at 100.0°C and allow the volatile liquid to vaporize. You then
cap the flask and remove it from the water bath. You weigh it and
determine the mass of the vapor in the flask to be 0.768 g. What is
the molar mass of the volatile liquid, and what does it mean with
regard to the new product? (Assume the pressure in the laboratory
is 1 atm.)

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Reactions with Gaseous Reactants and


Products
• Calculating the Required Volume of a Gaseous Reactant

• 2Na 𝑠 + Cl 𝑔 → 2NaCl(𝑠)

SAMPLE PROBLEM 10.9


Sodium peroxide (Na2O2) is used to remove carbon dioxide
from (and add oxygen to) the air supply in spacecrafts. It
works by reacting with CO2 in the air to produce sodium
carbonate (Na2CO3) and O2.
2Na O 𝑠 + 2CO 𝑔 → 2Na CO 𝑠 + O 𝑔
What volume (in liters) of CO2 (at STP) will react with a
kilogram of Na2O2?

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SAMPLE PROBLEM 10.10


• Another air-purification method for enclosed spaces
involves the use of “scrubbers” containing aqueous lithium
hydroxide, which reacts with carbon dioxide to produce
lithium carbonate and water:
• 2LiOH 𝑎𝑞 + CO 𝑔 → Li CO 𝑠 + H O 𝑙
• Consider the air supply in a submarine with a total volume
of 2.5 × 105 L. The pressure is 0.9970 atm, and the
temperature is 25°C. If the pressure in the submarine
drops to 0.9891 atm as the result of carbon dioxide being
consumed by an aqueous lithium hydroxide scrubber, how
many moles of CO2 are consumed?

SAMPLE PROBLEM 10.11


The air bags in cars are inflated when a collision triggers the
explosive, highly exothermic decomposition of sodium azide
(NaN3):
• 2NaN 𝑠 → 2Na 𝑠 + 3N 𝑔
A typical driver-side air bag contains about 50 g of NaN3.
Determine the volume of N2 gas that would be generated by
the decomposition of 50.0 g of sodium azide at 85.0°C and
1.00 atm.

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Gas Mixtures
• Dalton’s Law of Partial Pressures
• States that the total pressure exerted by a gas mixture is the sum of
the partial pressures exerted by each component of the mixture:

• 𝑃 = ∑   𝑃 𝑃 =

SAMPLE PROBLEM 10.12


A 1.00-L vessel contains 0.215 mole of N2 gas and 0.0118
mole of H2 gas at 25.5°C. Determine the partial pressure of
each component and the total pressure in the vessel.

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Gas Mixtures
• Dalton’s Law of Partial Pressures
• Total pressure exerted by a gas mixture is the sum of the partial
pressures exerted by each component of the mixture:
nRT
Ptotal   Pi Pi  i

V
• Mole Fractions
• 𝑋 =
• Always less than 1
• Sum of mole fractions for all components of a mixture is always 1
• Mole fraction is dimensionless
• 𝑋 = 𝑛 and 𝑃 are proportional
• 𝑋 ×𝑛 =𝑛
• 𝑋 × 𝑃 =𝑃

SAMPLE PROBLEM 10.12


A 1.00-L vessel contains 0.215 mole of N2 gas and 0.0118
mole of H2 gas at 25.5°C. Determine the partial pressure of
each component and the total pressure in the vessel.

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SAMPLE PROBLEM 10.13


Calculate the mole fraction of NO in a 10.00-L gas cylinder at
room temperature (25°C) that contains 6.022 mol N2 and in
which the total pressure is 14.75 atm.

Gas Mixtures

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Gas Mixtures
TABLE 10.5 Vapor Pressure of Water 𝑃 as a Function of Temperature
𝐓° 𝐂 𝐏 𝐭𝐨𝐫𝐫 𝐓° 𝐂 𝐏 𝐭𝐨𝐫𝐫 𝐓° 𝐂 𝐏 𝐭𝐨𝐫𝐫
0 4.6 35 42.2 70 233.7
5 6.5 40 55.3 75 289.1
10 9.2 45 71.9 80 355.1
15 12.8 50 92.5 85 433.6
20 17.5 55 118.0 90 525.8
25 23.8 60 149.4 95 633.9
30 31.8 65 187.5 100 760.0

SAMPLE PROBLEM 10.14


Calcium metal reacts with water to produce hydrogen gas:
• Ca 𝑠 + 2H O 𝑙 → Ca OH 𝑎𝑞 + H 𝑔
Determine the mass of H2 produced at 25°C and 0.967 atm
when 525 mL of the gas is collected over water

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SAMPLE PROBLEM 10.15


Large hyperbaric chambers are used mainly to treat victims of
diving accidents. In one treatment protocol at a typical facility,
the chamber is pressurized to 6.0 atm with compressed air
and the patient breathes a mixture of gases that is 47 percent
O2 by volume. In another protocol, the chamber is pressurized
with compressed air to 2.8 atm and the patient breathes pure
O2. Determine the partial pressure of O2 in each treatment
protocol and compare the results.

The Kinetic Molecular Theory of Gases


• Explains how the molecular nature of gases gives rise to their
macroscopic properties
• The basic assumptions of the kinetic molecular theory are as
follows:
1. A gas is composed of particles that are separated by relatively large
distances. The volume occupied by individual molecules is negligible.
2. Gas molecules are constantly in random motion, moving in straight paths,
colliding with the walls of their container and with one another in
perfectly elastic collisions. (Energy is transferred but not lost in the
collisions.)
3. Gas molecules do not exert attractive or repulsive forces on one another.
4. Average kinetic energy, 𝐸 of gas molecules in a sample is proportional to
the absolute temperature:
• 𝐸 ∝𝑇 𝐸 = 𝑚𝑢

• The mean square speed : 𝑢 =

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The Kinetic Molecular Theory of Gases


• Kinetic molecular theory enables us to understand some of
the properties and behavior of gases in the following ways.
• Compressibility
• Gases are compressible because molecules in the gas phase are
separated by large distances (assumption 1) and can be moved
closer together by decreasing the volume occupied by a sample

The Kinetic Molecular Theory of Gases


• Boyle’s Law (V  1/P) • Charles’s Law (V  T)
• The pressure exerted by a gas is the • Heating a sample of gas increases its
result of the collisions of gas molecules average kinetic energy (assumption 4).
with the walls of their container • An increase in average kinetic energy
(assumption 2). must be accompanied by an increase in
the mean square speed of the
• The magnitude of the pressure molecules. In other words, heating a
depends on both the frequency of sample of gas makes the gas molecules
collision and the speed of molecules move faster.
when they collide with the walls.
• Dalton’s Law of Partial Pressures
• Decreasing the volume occupied by a (Ptotal  Pi)
sample of gas increases the frequency • Gas molecules do not attract or repel
of these collisions, thus increasing the one another (assumption 3), so the
pressure. pressure exerted by one gas is
unaffected by the presence of another
• Avogadro’s Law (V  n) gas.
• Because the magnitude of the pressure • Consequently, the total pressure
exerted by a sample of gas depends on exerted by a mixture of gases is simply
the frequency of the collisions with the the sum of the partial pressures of the
container wall, the presence of more individual components in the mixture
molecules would cause an increase in
pressure.

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The Kinetic Molecular Theory of Gases


• Molecular Speed
• Root-mean-square (rms) speed (urms)
 
• 𝑢 =
M
• R=8.314 J/mol K

The Kinetic Molecular Theory of Gases


• Molecular Speed
• Diffusion
• Mixing of gases as the result of random
motion and frequent collisions
• Effusion
• Escape of gas molecules from a container
to a region of vacuum

• Graham’s law
• Rate of diffusion or effusion of a
gas is inversely proportional to the
square root of its molar mass:

• Rate ∝  
M
  M
• =
M

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SAMPLE PROBLEM 10.16


• Determine how much faster a helium atom moves, on
average, than a carbon dioxide molecule at the same
temperature.

Deviation from Ideal Behavior


• Factors That Cause Deviation from Ideal Behavior
• At high pressures, gas molecules are relatively close together
• Assume that gas molecules occupy no volume only when the distances between
molecules are large
• When the distances between molecules are reduced, the volume occupied by each
individual molecule becomes more significant
• At low temperatures, gas molecules are moving more slowly
• Assume that there are no intermolecular forces between gas molecules, either attractive
or repulsive, when the gas molecules are moving very fast and the magnitude of their
kinetic energies is much larger than the magnitude of any intermolecular forces
• When molecules move more slowly, they have lower kinetic energies and the magnitude
of the forces between them becomes more significant

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Deviation from Ideal Behavior


• The van der Waals Equation
L L
atm L 𝑏 atm L 𝑏
Gas 𝑎 mol Gas 𝑎 mol
mol mol

He 0.034 0.0237 O 1.36 0.0318


Ne 0.211 0.0171 Cl 6.49 0.0562
Ar 1.34 0.0322 CO 3.59 0.0427
Kr 2.32 0.0398 CH 2.25 0.0428
Xe 4.19 0.0510 CCl 20.4 0.138
H 0.244 0.0266 NH 4.17 0.0371
N 1.39 0.0391 H O 5.46 0.0305

Deviation from Ideal Behavior


• Van der Waals Equation
• One way to measure a gas’s deviation from ideal behavior is to
determine its compressibility factor, Z, where 𝑍 = 𝑃𝑉/𝑅𝑇
• For one mole of an ideal gas, Z is equal to 1 at all pressures and
temperatures

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Areas to Study for Weekly Quizzes


• Chapter 10 Summary
• Chapter 10 Key Words
• Checkpoint Questions
• 10.1.1, 10.1.2
• 10.2.1, 10.2.2. 10.2.3, 10.2.4, 10.2.5, 10.2.6
• 10.3.1, 10.3.2, 10.3.3, 10.3.4
• 10.4.1, 10.4.2
• 10.5.1, 10.5.2, 10.5.3, 10.5.4, 10.5.5, 10.5.6
• 10.6.1, 10.6.2
• 10.7.1

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