Chapt05 Lecture Chemistry

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Lecture PowerPoint
Chemistry
The Molecular Nature of
Matter and Change
Fifth Edition
Martin S. Silberberg
5-1
Chapter 5
Gases and the Kinetic-Molecular Theory
5-2
Gases and the Kinetic Molecular Theory

5.1 An Overview of the Physical States of Matter
5.2 Gas Pressure and Its Measurement
5.3 The Gas Laws and Their Experimental Foundations
5.4 Further Applications of the Ideal Gas Law
5.5 The Ideal Gas Law and Reaction Stoichiometry
5.6 The Kinetic-Molecular Theory: A Model for Gas Behavior
5.7 Real Gases: Deviations from Ideal Behavior
5-3
Table 5.1
Some Important Industrial Gases
Name (Formula)
Origin and Use
Methane (CH4)
natural deposits; domestic fuel
Ammonia (NH3)
from N2+H2; fertilizers, explosives
Chlorine (Cl2)
electrolysis of seawater; bleaching and

disinfecting
Oxygen (O2)
liquefied air; steelmaking
Ethylene (C2H4)
high-temperature decomposition of natural gas;

plastics
Atmosphere-Biosphere Redox Interconnections
5-4
An Overview of the Physical States of Matter

The Distinction of Gases from Liquids and Solids
1. Gas volume changes greatly with pressure.

2. Gas volume changes greatly with temperature.
3. Gases have relatively low viscosity.
4. Most gases have relatively low densities under normal conditions.
5. Gases are miscible.
5-5
Figure 5.1
5-6
The three states of matter.
Figure 5.2
5-7
Effect of atmospheric pressure on objects

at Earths surface.
Figure 5.3
5-8
A mercury barometer.
Figure 5.4
closed-end
Two types of
manometer
open-end
5-9
Table 5.2 Common Units of Pressure

Unit
Atmospheric Pressure
Scientific Field
pascal (Pa);
kilopascal (kPa)
1.01325 x 105 Pa;

101.325 kPa
SI unit; physics, chemistry
atmosphere (atm)
1 atm*
chemistry
millimeters of
mercury (Hg)
760 mm Hg*
chemistry, medicine, biology
torr
760 torr*
chemistry
14.7 lb/in2
engineering
1.01325 bar
meteorology, chemistry,
physics
pounds per square

inch (psi or lb/in2)
bar
*This is an exact quantity; in calculations, we use as many significant figures as necessary.
5-10
Sample Problem 5.1
Converting Units of Pressure
PROBLEM:
A geochemist heats a limestone (CaCO3) sample and collects

the CO2 released in an evacuated flask attached to a closed-end
manometer. After the system comes to room temperature, h =
291.4 mm Hg. Calculate the CO2 pressure in torrs,
atmospheres, and kilopascals.
PLAN: Construct conversion factors to find the other units of pressure.
SOLUTION:
291.4 mmHg
1torr
= 291.4 torr
1 mmHg
291.4 torr
1 atm
= 0.3834 atm
760 torr
0.3834 atm 101.325 kPa
1 atm
5-11
= 38.85 kPa
Figure 5.5
The relationship between the volume

and pressure of a gas.
Boyles Law
5-12
Figure 5.6
The relationship between the

volume and temperature of a
gas.
Charless Law
5-13
Boyles Law
VxP
V T
= constant
T
Amontonss Law
T
combined gas law
5-14
= constant
Charless Law
P T
= constant
T
P
n and T are fixed

V = constant / P
P and n are fixed
V = constant x T
V and n are fixed

P = constant x T
V = constant x
PV
= constant
Figure 5.7
5-15
An experiment to study the relationship between the

volume and amount of a gas.
Figure 5.8
5-16
Standard molar volume.
Figure 5.9
5-17
The volume of 1 mol of an ideal gas compared with some

familiar objects.
THE IDEAL GAS LAW
Figure 5.10
PV = nRT
PV
R=
nT
1 atm x 22.414 L
1 mol x 273.15 K
3 significant figures
0.0821 atm*L
mol*K
R is the universal gas constant
IDEAL GAS LAW

PV = nRT or V =
fixed n and T
Boyles Law
V=
5-18
constant
P
nRT
P
fixed n and P
fixed P and T
Charless Law
Avogadros Law
V=
constant X T
V=
constant X n
Sample Problem 5.2

PROBLEM:
Applying the Volume-Pressure Relationship
Boyles apprentice finds that the air trapped in a J tube occupies

24.8 cm3 at 1.12 atm. By adding mercury to the tube, he increases
the pressure on the trapped air to 2.64 atm. Assuming constant
temperature, what is the new volume of air (in L)?
PLAN:
SOLUTION:
V1 in cm3
1 cm3 = 1 mL
unit
V1 in mL
conversion
103 mL = 1 L
V1 in L
xP1/P2
P2 = 2.64 atm
V1 = 24.8 cm3
V2 = unknown
P1 V1
V2 in L
n1T1
V1 P1
P2
5-19
P1 = 1.12 atm
L
24.8 cm3 1 mL
1 cm3 103 mL
gas law
calculation
V2 =
n and T are constant
P2 V2
= 0.0248 L
P1V1 = P2V2
n2T2
= 0.0248 L
1.12 atm
2.46 atm
= 0.0105 L
Sample Problem 5.3

PROBLEM:
Applying the Temperature-Pressure Relationship
A steel tank used for fuel delivery is fitted with a safety valve that
opens when the internal pressure exceeds 1.00x103 torr. It is
filled with methane at 23C and 0.991 atm and placed in boiling
water at exactly 1000C. Will the safety valve open?
PLAN:
P1(atm)
SOLUTION:
T1 and T2(0C)
1atm=760torr
P1(torr)
K=0C+273.15
T1 and T2(K)
x T2/T1
P2(torr)
P1 = 0.991atm
P2 = unknown
T1 = 23oC
T2 = 100oC
0.991 atm 760 torr = 753 torr

1 atm
P1 V1
n1T1
P2 = P1
5-20
T2
T1
= 753 torr
373 K
296 K
P2 V2
P1
n2T2
T1
= 949 torr
P2
T2
Sample Problem 5.4

PROBLEM:
Applying the Volume-Amount Relationship
A scale model of a blimp rises when it is filled with helium to a

volume of 55.0 dm3. When 1.10 mol of He is added to the blimp,
the volume is 26.2 dm3. How many more grams of He must be
added to make it rise? Assume constant T and P.
PLAN: Initial n1 and V1 as well as the final V2 are given. Find n2 and convert
moles to grams.
n1 (mol) of He
x V2/V1
n2 (mol) of He
subtract n1
mol to be added
xM
g to be added
SOLUTION:
n1 = 1.10 mol
n2 = unknown
n1T1
V1 = 26.2 dm3
V2 = 55.0 dm3
V1
n1
n2 = n1
V2
V1
= 1.10 mol
55.0 dm3
26.2 dm3
P2 V2
n2T2
V2
n2
= 2.31 mol
naddll = n2 n1 = 2.31 mol 1.10 mol = 1.21 mol He

1.21 mol He
5-21
P1 V1
P and T are constant
4.003 g He
mol He
= 4.84 g He
Sample Problem 5.5

PROBLEM:
PLAN:
Solving for an Unknown Gas Variable at Fixed

Conditions
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.
V, T and mass, which can be converted to moles (n), are given.

Utilize the ideal gas law to find P.
SOLUTION:
0.885 kg
V = 438 L
T = 21oC (convert to K)
n = 0.885 kg (convert to mol)
P = unknown
103 g
mol O2
kg
32.00 g O2
= 27.7 mol O2
27.7 mol x 0.0821

P=
5-22
nRT
V
438 L
atm*L
mol*K
21oC + 273.15 = 294.15 K

x 294.15 K
= 1.53 atm
Sample Problem 5.6

PROBLEM:
Using Gas Laws to Determine a Balanced Equation
The piston-cylinders below depict a gaseous reaction carried out

at constant pressure. Before the reaction, the temperature is
150K; when it is complete, the temperature is 300K.
Which of the following balanced equations describes the reaction?

(1) A2 + B2
(3) A + B2
2AB
AB2
(2) 2AB + B2
(4) 2AB2
2AB2
A2 + 2B2
PLAN: P and T are given. The depiction indicates the volume doesnt change
even though the temperature is doubled. Relate n to T at constant P and
V. Examine equations to determine which allows for that change in n.
SOLUTION:
n1T1 = n2T2
T2 = 2T1
n2 = n1
Looking at the relationships, the equation that shows a decrease in

the number of moles of gas from 2 to 1 is equation (3).
5-23
The Density of a Gas

density = m/V
n = m/M
PV = nRT
PV = (m/M)RT
m/V = M x P/RT
The density of a gas is directly proportional to its molar mass.
The density of a gas is inversely proportional to the temperature.
5-24
Sample Problem 5.7
Calculating Gas Density
PROBLEM: Find the density (in g/L) of CO2 and the number of molecules (a) at
STP (0oC and 1 atm) and (b) at room conditions (20.oC and 1.00 atm).
PLAN: Density is mass/unit volume; substitute for volume in the ideal gas
equation. Since the identity of the gas is known, find the molar mass.
Convert mass/L to molecules/L with Avogadros number.
MxP
d =
d = mass/volume
PV = nRT
V = nRT/P
RT
SOLUTION: (a)
44.01 g/mol x 1atm
d=
= 1.96 g/L
atm*L
0.0821
x 273.15 K
mol*K
1.96 g
mol CO2
44.01 g CO2
(b)
d=
6.022x1023 molecules
mol
44.01 g/mol x 1 atm
0.0821
5-25
1.83 g
mol CO2
44.01 g CO2
= 2.68x1022 molecules CO2/L
atm*L
x 293 K
mol*K
6.022x1023 molecules
mol
= 1.83 g/L
= 2.50x1022 molecules CO2/L
The Molar Mass of a Gas
n=
mass
M
PV
RT
M=
mRT
VP
d=
m
V
dRT
M=
P
5-26
Figure 5.11
Determining the molar

mass of an unknown
volatile liquid.
based on the method of
J.B.A. Dumas (1800-1884)
5-27
Sample Problem 5.8

PROBLEM:
Finding the Molar Mass of a Volatile Liquid
An organic chemist isolates a colorless liquid from a petroleum

sample. She uses the Dumas method and obtains the following
data:
Volume of flask = 213 mL
T = 100.0oC
P = 754 torr
Mass of flask + gas = 78.416 g Mass of flask = 77.834 g

Calculate the molar mass of the liquid.
PLAN: Use unit conversions, mass of gas, and density-M relationship.
SOLUTION:
M=
m = (78.416 - 77.834) g = 0.582 g
mRT
VP
0.582 g x 0.0821
atm*L
mol*K
0.213 L x 0.992 atm
5-28
x 373 K
= 84.4 g/mol
Mixtures of Gases
Gases mix homogeneously in any proportions.
Each gas in a mixture behaves as if it were the only gas present.
Daltons Law of Partial Pressures

Ptotal = P1 + P2 + P3 + ...
P1= 1 x Ptotal
where 1 is the mole fraction

1 =
5-29
n1
n1 + n2 + n3 +...
n1
ntotal
Sample Problem 5.9
Applying Daltons Law of Partial Pressures
PROBLEM:
In a study of O2 uptake by muscle at high altitude, a physiologist

prepares an atmosphere consisting of 79 mole % N2, 17 mole %
16
O2, and 4.0 mole % 18O2. (The isotope 18O will be measured to
determine the O2 uptake.) The pressure of the mixture is 0.75
atm to simulate high altitude. Calculate the mole fraction and
partial pressure of 18O2 in the mixture.
PLAN: Find the 18 and P18 from Ptotal and mol % 18O2.
mole % 18O2
O2
O2
divide by 100
18O2
SOLUTION:
P18
5-30
O2
18
4.0 mol % 18O2

100
= 18 x Ptotal = 0.040 x 0.75 atm

O2
O2
= 0.040
multiply by Ptotal
partial pressure P
= 0.030 atm
18
O2
Table 5.3 Vapor Pressure of Water (P
H2O
T(0C)
0
5
10
12
14
16
18
20
22
24
26
28
30
35
5-31
) at Different T
P (torr)
T(0C)
P (torr)
4.6
6.5
9.2
10.5
12.0
13.6
15.5
17.5
19.8
22.4
25.2
28.3
31.8
42.2
40
45
50
55
60
65
70
75
80
85
90
95
100
55.3
71.9
92.5
118.0
149.4
187.5
233.7
289.1
355.1
433.6
525.8
633.9
760.0
Figure 5.12
5-32
Collecting a water-insoluble gaseous reaction

product and determining its pressure.
Sample Problem 5.10 Calculating the Amount of Gas Collected over Water
PROBLEM:
Acetylene (C2H2) is produced in the laboratory when calcium

carbide (CaC2) reacts with water:
CaC2(s) + 2H2O(l)
C2H2(g) + Ca(OH)2(aq)
A collected sample of acetylene has a total gas pressure of 738 torr and a
volume of 523 mL. At the temperature of the gas (23oC), the vapor pressure of
water is 21 torr. How many grams of acetylene are collected?
PLAN: The difference in pressures will give P for the C2H2. The
ideal gas law allows n to be found. Converting n to
grams requires the molar mass, M.
Ptotal
SOLUTION:
P
C2H2 = (738 - 21) torr = 717 torr
P
C2H2
C2H2
0.943 atm x
0.0821
atm*L
mol*K
0.0203 mol
5-33
atm
= 0.943 atm
760 torr
0.523 L
= 0.0203 mol
x 296 K
26.04 g C2H2
mol C2H2
P
H2O
n=
n
C2H2
xM
= 0.529 g C2H2
g
C2H2
PV
RT
Figure 15.13
Summary of the stoichiometric relationships among the

amount (mol, n) of gaseous reactant or product and the gas
variables pressure (P), volume (V), and temperature (T).
P,V,T
of gas A
ideal
gas
law
5-34
amount
(mol)
amount
(mol)
P,V,T
of gas A
of gas B
of gas B
molar ratio from

balanced equation
ideal
gas
law
Sample Problem 5.11

PROBLEM:
Using Gas Variables to Find Amount of

Reactants and Products
What volume of H2 at 765 torr and 225oC is needed to reduce

35.5 g of copper(II) oxide to form pure copper and water?
PLAN: Write a balanced equation. Utilize stoichiometry and gas laws.

mass (g) of CuO
SOLUTION:
CuO(s) + H2(g)
Cu(s) + H2O(g)
divide by M
mol of CuO
35.5 g CuO
mol CuO
79.55 g CuO 1 mol CuO
0.446 mol H2 x 0.0821

1.01 atm
5-35
1 mol H2
atm*L
mol*K
= 0.446 mol H2
molar ratio
mol of H2
use known P
and T to find V
x 498 K
= 18.1 L
L of H2
Sample Problem 5.12
Using the Ideal Gas Law in a Limiting-Reactant

Problem
PROBLEM: What mass of potassium chloride forms when 5.25 L of chlorine gas
at 0.950 atm and 293 K reacts with 17.0 g of potassium?
PLAN: After writing the balanced equation, we use the ideal gas law to find the
number of moles of reactants, the limiting reactant and moles of product.
SOLUTION:
n
Cl2
PV
RT
2K(s) + Cl2(g)
0.950 atm x 5.25 L
0.0821
0.207 mol Cl2
atm*L
mol*K
2 mol KCl
1 mol Cl2
mol K
17.0 g
39.10 g K
0.435 mol K
5-36
2KCl(s)
x 293 K
V = 5.25 L
T = 293 K
n = unknown
Cl2 is the limiting reactant.
= 0.414 mol KCl

0.414 mol KCl
74.55 g KCl
mol KCl
= 0.435 mol K
2 mol KCl
2 mol K
= 0.207 mol
P = 0.950 atm
= 30.9 g KCl
= 0.435 mol KCl
Postulates of the Kinetic-Molecular Theory

Postulate 1: Particle Volume
Because the volume of an individual gas particle is so
small compared to the volume of its container, the gas
particles are considered to have mass, but no volume.
Postulate 2: Particle Motion
Gas particles are in constant, random, straight-line
motion except when they collide with each other or with
the container walls.
Postulate 3: Particle Collisions
Collisions are elastic, therefore, the total kinetic energy
(Ek) of the particles is constant.
5-37
Figure 5.14
5-38
Distribution of molecular speeds at three temperatures.
Figure 5.15
5-39
A molecular description of Boyles Law.
Figure 5.16
5-40
A molecular description of Daltons law of partial pressures.
Figure 5.17
5-41
A molecular description of Charless Law.
V n
Avogadros Law
Ek = 1/2 mass x speed2
Ek = 1/2 mass x u2
u 2 is the root-mean-square speed
urms =
3RT
M
R = 8.314 Joule/mol*K
Grahams Law of Effusion

The rate of effusion of a gas is inversely related to the square root of its molar mass.
rate of effusion
5-42
1
M
Figure 5.18
5-43
A molecular description of Avogadros Law.
Figure 5.19
Relationship between molar mass and molecular speed.
Ek = 3/2 (R/NA) T
5-44
Sample Problem 5.13
Applying Grahams Law of Effusion
PROBLEM: Calculate the ratio of the effusion rates of helium and methane (CH4).
PLAN: The effusion rate is inversely proportional to the square root of the
molar mass for each gas. Find the molar mass of both gases and find
the inverse square root of their masses.
SOLUTION:
M of CH4 = 16.04 g/mol

rate
rate
5-45
He
CH4
16.04
4.003
= 2.002
M of He = 4.003 g/mol
Figure 5.20
Diffusion of a gas particle through a

space filled with other particles.
distribution of molecular speeds
mean free path
collision frequency
5-46
Figure B5.1
Variations in pressure, temperature, and composition of

the Earths atmosphere
Variations in pressure, temperature, and

composition of the Earths atmosphere.
5-47
5-48
5-49
Table 5.4 Molar Volume of Some Common Gases at STP
(0oC and 1 atm)
Gas
He
H2
Ne
Ideal gas
Ar
N2
O2
CO
Cl2
NH3
5-50
Molar Volume
(L/mol)
22.435
22.432
22.422
22.414
22.397
22.396
22.390
22.388
22.184
22.079
Condensation Point
(oC)
-268.9
-252.8
-246.1
---185.9
-195.8
-183.0
-191.5
-34.0
-33.4
Figure 5.21
The behavior of several

real gases with
increasing external
pressure.
5-51
Figure 5.22
5-52
The effect of intermolecular attractions on

measured gas pressure.
Figure 5.23
5-53
The effect of molecular volume on measured gas volume.
Table 5.5 Van der Waals Constants for Some Common Gases
Van der Waals
equation for n
moles of a real gas
n2a
(P 2 )(V nb) nRT
V
adjusts P up adjusts V down
a
Gas
5-54
He
Ne
Ar
Kr
Xe
H2
N2
O2
Cl2
CH4
CO
CO2
NH3
atm*L2
mol2
mol
0.034
0.211
1.35
2.32
4.19
0.244
1.39
1.36
6.49
2.25
1.45
3.59
4.17
5.46
0.0237
0.0171
0.0322
0.0398
0.0511
0.0266
0.0391
0.0318
0.0562
0.0428
0.0395
0.0427
0.0371
0.0305

Chapt05 Lecture Chemistry

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Gases and the Kinetic-Molecular Theory

Gases and the Kinetic Molecular Theory

Some Important Industrial Gases

Origin and Use

natural deposits; domestic fuel

from N2+H2; fertilizers, explosives

electrolysis of seawater; bleaching and

liquefied air; steelmaking

high-temperature decomposition of natural gas;

Atmosphere-Biosphere Redox Interconnections

An Overview of the Physical States of Matter

1. Gas volume changes greatly with pressure.

The three states of matter.

Effect of atmospheric pressure on objects

Table 5.2 Common Units of Pressure

1.01325 x 105 Pa;

SI unit; physics, chemistry

chemistry, medicine, biology

pounds per square

*This is an exact quantity; in calculations, we use as many significant figures as necessary.

Sample Problem 5.1

Converting Units of Pressure

A geochemist heats a limestone (CaCO3) sample and collects

The relationship between the volume

The relationship between the

n and T are fixed

V and n are fixed

An experiment to study the relationship between the

Standard molar volume.

The volume of 1 mol of an ideal gas compared with some

THE IDEAL GAS LAW

R is the universal gas constant

IDEAL GAS LAW

Sample Problem 5.2

Applying the Volume-Pressure Relationship

Boyles apprentice finds that the air trapped in a J tube occupies

n and T are constant

Sample Problem 5.3

Applying the Temperature-Pressure Relationship

0.991 atm 760 torr = 753 torr

Sample Problem 5.4

Applying the Volume-Amount Relationship

A scale model of a blimp rises when it is filled with helium to a

naddll = n2 n1 = 2.31 mol 1.10 mol = 1.21 mol He

P and T are constant

Sample Problem 5.5

Solving for an Unknown Gas Variable at Fixed

A steel tank has a volume of 438 L and is filled with 0.885 kg of

V, T and mass, which can be converted to moles (n), are given.

n = 0.885 kg (convert to mol)

27.7 mol x 0.0821

21oC + 273.15 = 294.15 K

Sample Problem 5.6

Using Gas Laws to Determine a Balanced Equation

The piston-cylinders below depict a gaseous reaction carried out

Which of the following balanced equations describes the reaction?

Looking at the relationships, the equation that shows a decrease in

The Density of a Gas

Sample Problem 5.7

Calculating Gas Density

= 2.68x1022 molecules CO2/L

= 2.50x1022 molecules CO2/L