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Chemistry
The Molecular Nature of
Matter and Change
Seventh Edition
Martin S. Silberberg
and Patricia G. Amateis
5-1 Copyright McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior written consent of McGraw-Hill Education.
Chapter 5
5-2
Gases and the Kinetic Molecular Theory
5-3
Figure 5.1 The three states of matter.
5-4
An Overview of the Physical States of Matter
Distinguishing gases from liquids and solids.
5-5
Gas Pressure and its Measurement
force
Pressure =
area
5-6
Figure 5.2 Effect of atmospheric pressure on a familiar object.
5-7
Figure 5.3 A mercury barometer.
5-8
Figure 5.4 A Closed-end manometer.
5-9
Figure 5.4 B Open-end manometer.
5-10
Table 5.1 Common Units of Pressure
5-11
Sample Problem 5.1 Converting Units of Pressure
5-12
The Gas Laws
5-13
Figure 5.5 Boyle’s law, the relationship between the volume
and pressure of a gas.
5-14
Boyle’s Law
V 1 or PV = constant
P
At fixed T and n,
P decreases as V increases
P increases as V decreases
5-15
Figure 5.6 Charles’s law, the relationship between the
volume and temperature of a gas.
5-16
Charles’s Law
At fixed P and n,
V decreases as T decreases
V increases as T increases
5-17
Figure 5.7 The relationship between the volume and
amount of a gas.
5-18
Figure 5.8 The process of breathing applies the gas laws.
5-19
Gas Behavior at Standard Conditions
5-20
Figure 5.9 Standard molar volume.
5-21
Figure 5.10 The volume of 1 mol (22.4 L) of an ideal gas and of
some familiar objects: 1 gal of milk (3.79 L), a
basketball (7.50 L), and 2.00 L of a carbonated drink.
5-22
The Ideal Gas Law
pV = nRT
P1V1 P2V2
=
n1T1 n2T2
5-23
Figure 5.11 The individual gas laws as special cases of the
ideal gas law.
5-24
Sample Problem 5.2 Applying the Volume-Pressure Relationship
V1 (cm3)
1 cm3 = 1 mL
V1 (mL)
1000 mL = 1L
V1 (L)
multiply by P1/P2
V2 (L)
5-25
Sample Problem 5.2
SOLUTION:
24.8 cm3 x 1 mL x L
= 0.0248 L
1 cm3 103 mL
P1V1 P2V2
= P1V1 = P2V2
n1T1 n2T2
5-26
Sample Problem 5.3 Applying the Volume-Temperature and
Pressure-Temperature Relationships
PLAN: We know the initial volume (V1) and the initial (T1) and final
temperatures (T2) of the gas; we must find the final volume (V2).
The pressure of the gas is fixed since the balloon is subjected to
atmospheric pressure and n is fixed since air cannot escape or
enter the balloon. We convert both T values to degrees Kelvin,
rearrange the ideal gas law, and solve for V2.
5-27
Sample Problem 5.3
T1 and T2 (ºC)
ºC + 273.15 = K
V1 (L) T1 and T2 (K)
multiply by T2/T1
V2 (L)
V1 = 1.95 L V2 = 1.95 L
T1 = 25ºC (convert to K) T2 = 90ºC (convert to K)
P and n remain constant
Converting T from ºC to K:
T1 (K) = 25ºC + 273.15 = 298 K T2 (K) = 90ºC + 273.15 = 363 K
5-28
Sample Problem 5.3
SOLUTION (continued):
Rearranging the generalized ideal gas equation and solving for V2:
At fixed n and P, we have
P1V1 P2V2 V1 V2
= or =
n1T1 n2T2 T1 T2
T2 363 K
V2 = V 1 x = 1.95 L x = 2.38 L
T1 298 K
CHECK: Let’s predict the change to check the math: Because T2 > T1, we
expect V2 > V1. Thus, the temperature ratio should be > 1 (T2 in the
Numerator). The T ratio (363/298) is about 1.2, so the V ratio should also be
about 1.2 (2.4/2.0).
5-29
Sample Problem 5.4 Applying the Volume-Amount Relationship
PLAN: The initial amount of helium (n1) is given, as well as the initial
volume (V1) and the volume needed to make it rise (V2). We
need to calculate n2, and hence the mass of He to be added.
n1 (mol) of He
multiply by V2 /V1
n2 (mol) of He
subtract n1
mol to be added
multiply by M
g to be added
5-30
Sample Problem 5.4
SOLUTION:
n1 = 1.10 mol n2 = unknown
V1 = 26.2 dm3 V2 = 55.0 dm3 T and P are constant
P1V1 P2V2 V1 V2
= =
n1T1 n2T2 n1 n2
n2 = n1 x V2 3
= 1.10 mol x 55.0 dm = 2.31 mol He
V1 26.2 dm3
4.003 g He
1.21 mol He x = 4.84 g He
1 mol He
5-31
Sample Problem 5.5 Applying the Volume-Pressure-Temperature
Relationship
PROBLEM: A helium-filled balloon has a volume of 15.8 L at a pressure of
0.980 atm and 22ºC. What is its volume on the top of Mt. Hood,
Oregon’s highest mountain, where the atmospheric pressure is
532 mmHg and the temperature is 0ºC?
PLAN: We know the initial volume (V1), pressure (P1), and temperature (T1)
of the gas; we also know the final pressure (P2) and temperature (T2)
and we must find the final volume (V2). Since the amount of helium in
the balloon does not change, n is fixed. We convert both T values to
degrees Kelvin, the final pressure to atm, rearrange the generalized
ideal gas equation, and solve for V2.
SOLUTION: Summarizing the gas variables:
V1 = 15.8 L V2 = unknown
T1 = 22ºC (convert to K) T2 = 0ºC (convert to K)
P1 = 0.980 atm P2 = 523 mmHg (convert to atm)
n remains constant
Converting T from ºC to K:
T1 (K) = 22ºC + 273.15 = 295 K T2 (K) = 0ºC + 273.15 = 273 K
5-32
Sample Problem 5.5
SOLUTION (continued):
Converting P2 to atm: 1 atm
P2 (atm) = 532 mmHg x = 0.700 atm
760 mmHg
Rearranging the generalized ideal gas equation and solving for V2:
At fixed n, we have
CHECK: Let’s predict the change to check the math: Because T2 < T1, we
expect V2 < V1; but because P2 < P1, we expect V2 > V1. The temperature ratio
(T2 in the numerator) is about 0.93 (273/295) and the pressure ratio (P1 in the
numerator) is about 1.4 (0.980/0.700), so the V ratio should be about 0.93 x 1.4 or
1.3 (20.5/15.8 ≈ 1.3). The pressure decreased by a larger factor than the
temperature increased, so there is an overall increase in volume.
5-33
Sample Problem 5.6 Solving for an Unknown Gas Variable at
Fixed Conditions
PROBLEM: A steel tank has a volume of 438 L and is filled with
0.885 kg of O2. Calculate the pressure of O2 at 21ºC.
PLAN: We are given V, T, and mass, which can be converted to
moles (n). Use the ideal gas law to find P.
atm·L
27.7 mol x 0.0821 x 294 K
nRT mol·K
P= = = 1.53 atm
V
438 L
5-34
Sample Problem 5.7 Using Gas Laws to Determine a Balanced
Equation
5-35
Sample Problem 5.7
PLAN: We are told that P is constant for this system, and the depiction
shows that V does not change either. Since T changes, the volume
could not remain the same unless the amount of gas in the system
also changes.
n2 T1 150 K
SOLUTION: n1T1 = n2T2 = = =½
n1 T2 300 K
5-36
The Ideal Gas Law and Gas Density
m m
density = and moles =
V M
m
PV = RT
M
m M xP
=d=
V RT
5-37
Sample Problem 5.8 Calculating Gas Density
PROBLEM: Find the density (in g/L) of CO2 (g) and the number of
molecules per liter
(a) at STP and (b) at room conditions (20. ºC and 1.00 atm).
PLAN: We can use the molar mass of CO2 to find its density from
the ideal gas equation.
5-39
Molar Mass from the Ideal Gas Law
m PV
n= =
M RT
mRT
M=
PV
5-40
Sample Problem 5.9 Finding the Molar Mass of a Volatile Liquid
PLAN: The variables V, T and P are given. We find the mass of the
gas by subtracting the mass of the flask from the mass of
the flask with the gas in it, and use this information to
calculate M.
5-41
Sample Problem 5.9
atm·L
0.582 g x 0.0821 x 373.2 K
mRT mol·K
M= = = 84.4 g/mol
PV 0.213 L x 0.992 atm
5-42
Mixtures of Gases
5-43
Sample Problem 5.10 Applying Dalton’s Law of Partial Pressures
5-44
Sample Problem 5.10
SOLUTION:
5-45
Table 5.2 Vapor Pressure of Water (P ) at Different T
H2O
5-46
Figure 5.12 Collecting a water-insoluble gaseous product
and determining its pressure.
5-47
Sample Problem 5.11 Calculating the Amount of Gas
Collected over Water
PLAN: The difference in pressures will give P for the C2H2. The
number of moles (n) is calculated from the ideal gas law
and converted to mass using the molar mass.
5-48
Sample Problem 5.11
PLAN:
SOLUTION:
Ptotal
subtract P for H2O P
C2H2 = (738 - 21) torr = 717 torr
P of C2H2 1 atm
P = 717 torr x = 0.943 atm
use ideal gas law 760 torr
n of C2H2 V = 523 mL x 1L
= 0.523 L
103 mL
multiply by M
5-49
Sample Problem 5.11
SOLUTION:
26.04 g C2H2
0.0203 mol x = 0.529 g C2H2
1 mol C2H2
5-50
The Ideal Gas Law and Stoichiometry
P, V, T P, V, T
of gas A of gas B
Figure 15.13
The relationships among the amount (mol, n) of gaseous
reactant (or product) and the gas pressure (P), volume (V),
and temperature (T).
5-51
Sample Problem 5.12 Using Gas Variables to Find Amounts of
Reactants and Products I
5-52
Sample Problem 5.12
1 atm
P = 765 torr x = 1.01 atm T = 225ºC + 273.15 K = 498 K
760 torr
atm·L
0.446 mol H2 x 0.0821 x 498 K
V= nRT mol·K
= = 18.1 L H2
P
1.01 atm
5-53
Sample Problem 5.13 Using Gas Variables to Find Amounts of
Reactants and Products II
For Cl2:
P = 0.950 atm V = 5.25 L
T = 293 K n = unknown
5-54
Sample Problem 5.13
5-55
The Kinetic-Molecular Theory:
A Model for Gas Behavior
Postulate 1:
Gas particles are tiny with large spaces between them. The volume
of each particle is so small compared to the total volume of the gas
that it is assumed to be zero.
Postulate 2:
Gas particles are in constant, random, straight-line motion except
when they collide with each other or with the container walls.
Postulate 3:
Collisions are elastic, meaning that colliding particles exchange
energy but do not lose any energy due to friction. Their total kinetic
energy is constant. Between collisions the particles do not influence
each other by attractive or repulsive forces.
5-56
Figure 5.14 Distribution of molecular speeds for N2 at three
temperatures.
5-57
Figure 5.15 Pressure arise from countless collisions between
gas particles and walls.
5-58
Figure 5.16 A molecular view of Boyle’s law.
Pext increases,
T and n fixed
5-59
Figure 5.17 A molecular view of Dalton’s law.
5-60
Figure 5.18 A molecular view of Charles’s law.
5-61
Figure 5.19 A molecular view of Avogadro’s law.
5-62
Kinetic Energy and Gas Behavior
1
Ek = mass x speed2
2
5-63
Figure 5.20 The relationship between molar mass and molecular
speed.
5-64
Graham’s Law of Effusion
Effusion is the process by which a gas escapes
through a small hole in its container into an evacuated
space.
1
Rate of effusion
√M
5-65
Figure 5.21 Effusion. Lighter (black) particles effuse faster than
heavier (red) particles.
5-66
Sample Problem 5.14 Applying Graham’s Law of Effusion
rate
rate
He
CH4
= √ 4.003
16.04
= 2.002
5-67
Figure 5.22 Diffusion of gases.
5-68
Chemical Connections
Figure B5.1 Variations in pressure and temperature with altitude
in Earth’s atmosphere.
5-70
Real Gases: Deviations from Ideal Behavior
5-71
Table 5.3 Molar Volume of Some Common Gases at STP
(0ºC and 1 atm)
He 22.435 -268.9
H2 22.432 -252.8
Ne 22.422 -246.1
Ideal gas 22.414 ‒
Ar 22.397 -185.9
N2 22.396 -195.8
O2 22.390 -183.0
CO 22.388 -191.5
Cl2 22.184 -34.0
NH3 22.079 -33.4
5-72
Figure 5.23 Deviations from ideal behavior with increasing
external pressure.
5-73
Figure 5.24 The effect of interparticle attractions on
measured gas pressure.
5-74
Figure 5.25 The effect of particle volume on measured gas
volume.
5-75
The van der Waals equation
• The van der Waals equation adjusts the ideal gas law to
take into account
– the real volume of the gas particles and
– the effect of interparticle attractions.
5-76
Table 5.4 Van der Waals Constants for Some Common Gases
atm∙L2 L
a b
Gas mol2 mol
He 0.034 0.0237
Ne 0.211 0.0171
Ar 1.35 0.0322
Kr 2.32 0.0398
Xe 4.19 0.0511
H2 0.244 0.0266
N2 1.39 0.0391
O2 1.36 0.0318
Cl2 6.49 0.0562
CH4 2.25 0.0428
CO 1.45 0.0395
CO2 3.59 0.0427
NH3 4.17 0.0371
H2O 5.46 0.0305
5-77