Chapter 5

Gases and the Kinetic-Molecular Theory

5-1
 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

5-2
 An Overview of the Physical States of
Matter
Distinction Between Gases and Liquids/Solids (condensed phases)

1. Gas volume changes greatly with pressure.

2. Gas volume changes greatly with temperature.

3. Gas have relatively low viscosity.

4. Most gases have relatively low densities under

normal conditions.

5. Gases are miscible.

5-3
 States of Matter

Figure 5.1

5-4
 A Mercury Barometer

Pressure = force/area

A device used to
measure
atmospheric
pressure

Figure 5.3
5-5
 Two Types of
Manometer

Figure 5.4

5-6
 Table 5.2 Common Units of Pressure

Unit Atmospheric Pressure Scientific Field

pascal (Pa) 1.01325 x 105 Pa; SI unit; physics, chemistry;

kilopascal (kPa) 101.325 kPa (1 Pa = 1 N/m2)
atmosphere (atm) 1 atm chemistry

millimeters of 760 mm Hg chemistry, medicine, biology

mercury (Hg)

torr 760 torr chemistry

pounds per square 2 engineering

inch 14.7 lb/in
(psi or lb/in2)
bar 0.01325 bar meteorology, chemistry,
physics

5-7
 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:
1 torr
291.4 mm Hg x = 291.4 torr
1 mm Hg

1 atm
291.4 torr x = 0.3834 atm
760 torr

101.325 kPa
0.3834 atm x = 38.85 kPa
1 atm

5-8
 Three laws (Boyle’s, Charles’s and Avogadro’s) are
combined to
describe a universal relationship among the key gas
variables (volume, pressure, temperature, amount).
This universal relationship is known as the Ideal Gas
Law.
Let’s examine the three individual laws first, and then see how
they are combined to generate the Ideal Gas Law.

5-9
 Relationship between volume and pressure of a
gasLaw
Boyle’s

Figure 5.5

5-10
 1
Boyle’s Law V  n and T are fixed
P
(volume is inversely proportional to pressure)

PV = constant or V = constant / P

P = pressure
V = volume
n = number of moles of gas
T = temperature

5-11
 Relationship between volume and temperature
of a gas
Charles’s Law

Figure 5.6

5-12
 1
Boyle’s Law: V  n and T are fixed
P

Charles’s Law: V T P and n are fixed

V
= constant V = constant x T
T

Amonton’s Law: P T V and n are fixed

P
= constant P = constant x T
T

Combined Gas Law: T T PV

V  V = constant x = constant
(Boyle’s + Charles’s) P P T

5-13
 An experiment to study the
relationship between volume and
amount of a gas

Figure 5.7
Avogadro’s Law

V n
(P and T fixed)

At fixed T and P, equal volumes of any ideal gas contain

equal numbers of particles (or moles).

5-14
 Standard Molar
Volume

STP
0 oC (273.15 K)
1 atm (760 torr)

Standard
Molar
Volume:
22.4141 L or
22.4 L

Figure 5.8
5-15
 THE IDEAL GAS
LAW
PV = nRT

PV 1 atm x 22.414 L 0.0821atm L

R= = =
nT 1 mol x 273.15 K mol K

nRT
PV = nRT or V =
P

At fixed n and T: At fixed n and P: At fixed P and T:

Boyle’s Law Charles’s Law Avogadro’s Law
constant V = constant x n
V= V = constant x T
P

5-16
 Sample Problem 5.2 Applying the Volume-Pressure Relationship

PROBLEM: Boyle’s 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: n and T are constant

V1 in cm3
P1 = 1.12 atm P2 = 2.64 atm
1 cm3 = 1 mL
V1 = 24.8 cm3 V2 = unknown
V1 in mL
1 mL L
3
10 mL = 1 L 24.8 cm x 3
3
x 3
= 0.0248 L
1 cm 10 mL
V1 in L
P1 V1 P2 V2
x P1/P2 = or P1 V1 = P 2 V2
n1T1 n2T2
V2 in L P1 V1 1.12 atm
V2 = = 0.0248 L x = 0.0105 L
P2 2.64 atm
5-17
 Sample Problem 5.3 Applying the Temperature-Pressure Relationship

PROBLEM: A 1 L steel tank is fitted with a safety valve that opens if the
internal pressure exceeds 1.00 x 103 torr. It is filled with helium
at 23 oC and 0.991 atm and placed in boiling water at exactly
100 oC. Will the safety valve open?
PLAN: SOLUTION: n and V are constant
P1 (atm) T1 and T2 (oC)
P1 = 0.991 atm P2 = unknown
1 atm = 760 torr K = oC + 273.15
T1 = 23 oC T2 = 100 oC
P1 (torr) T1 and T2 (K) P1 V1 P2 V2 P1 P2
= or =
x T2/T1 n1T1 n2T2 T1 T2

P2 (torr)
0.991 atm x 760 torr = 753 torr
1 atm
T2 373 K
P 2 = P1 = 753 torr x = 949 torr
T1 296 K
(valve will not open)
5-18
 Sample Problem 5.4 Applying the Volume-Amount Relationship

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

volume of 55 dm3 (V2). When 1.10 mol of He (n1) are added to the
blimp, the volume is 26.2 dm3 (V1). How many more grams of He
must be added to make it rise? Assume constant T and P.
PLAN: We are given the initial n1 and V1 and the final V2. We need to find
n2 and convert it from moles to grams.
n1(mol) of He
SOLUTION: P and T are constant
x V2 / V1
n1 = 1.10 mol n2 = unknown P1 V1 P2 V2
n2(mol) of He =
3 3
V1 = 26.2 dm V2 = 55.0 dm n1T1 n2T2
subtract n1
V1 V2 V2
mol to be added = or n2 = n1
n1 n2 V1
xM
55.0 dm3
g He to add n2 = 1.10 mol x = 2.31 mol
3
26.2 dm
4.003 g He
2.31 mol - 1.10 mol = 1.21 mol x = 4.84 g He
mol He
5-19
Sample Problem 5.5 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 21 oC.

PLAN: V, T and mass, which can be converted to moles (n), are given. Use
the ideal gas law to find P.

SOLUTION: V = 438 L T = 21 oC (convert to K)

n = 0.885 kg (convert to mol) P = unknown

103 g mol O2
0.885 kg x x = 27.7 mol O2 21 oC + 273.15 = 294 K
kg 32.00 g O2
atm L
27.7 mol x 0.0821 x 294 K
nRT mol K
P= = = 1.53 atm
V 438 L

5-20
 The Density of a Gas

PV = nRT or PV = m/M x RT where m = mass and M = molar mass

m/V = d = (M x P)/RT where d = density

5-21
 Sample Problem 5.6 Calculating the Density of a Gas

PROBLEM: Calculate the density (in g/L) of carbon dioxide and the number
of molecules per liter (a) at STP (0 oC and 1 atm) and (b) at
ordinary 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, the molar mass can be
determined. Convert mass/L to molecules/L using Avogadro’s number.
MxP
d = mass/volume PV = nRT V = nRT/P d =
RT
SOLUTION:
44.01 g/mol x 1 atm
(a) d= = 1.96 g/L
atm L
0.0821 x 273 K
mol K
1.96 g mol CO2 6.022 x 1023 molecules
x x = 2.68 x 1022 molecules CO2/L
L 44.01 g CO2 mol

5-22
 Sample Problem 5.6 (continued)

44.01 g/mol x 1 atm

(b) d= = 1.83 g/L
atm L x 293 K
0.0821
mol K

1.83 g mol CO2 6.022 x 1023 molecules

x x = 2.50 x 1022 molecules CO2/L
L 44.01 g CO2 mol

5-23
 The Molar Mass of
a Gas

mass PV
n= =
M RT

mRT m
M= d=
PV V

d RT
M=
P

5-24
 Determining the
molar mass of an
unknown volatile
liquid
[based on the method of J.B.A.
Dumas (1800 -1884)]

M = mRT/PV
or
M = dRT/P

Figure 5.11

5-25
 Sample Problem 5.7 Finding the Molar Mass of a Volatile Liquid

PROBLEM: An organic chemist isolates from a petroleum sample a colorless

liquid with the properties of cyclohexane (C6H12). She uses the
Dumas method and obtains the following data to determine its
molar mass:
Volume of flask = 213 mL T = 100.0 oC P = 754 torr

Mass of flask + gas = 78.416 g Mass of flask = 77.834 g

Is the calculated molar mass consistent with the liquid being cyclohexane?

PLAN: Use unit conversions, mass of gas and density-M relationship. MxP
d=
RT
SOLUTION: m = (78.416 - 77.834)g = 0.582 g of gas mRT
atm L M=
m RT 0.582 g x 0.0821 x 373 K VP
M= = mol K
VP = 84.4 g/mol
0.213 L x 0.992 atm

M of C6H12 is 84.16 g/mol - the calculated value is within experimental error

5-26
 Dalton’s Law of Partial
Pressures
In a mixture of unreacting gases, the total pressure is equal to the
sum of the partial pressures of the individual gases.

Ptotal = P1 + P2 + P3 + ...
where

P1 = 1 x Ptotal and 1 is the mole fraction

n1 n1
1 = =
n1 + n2 + n3 +... ntotal

5-27
 Sample Problem 5.8 Applying Dalton’s Law of Partial Pressures

PROBLEM: In a study of O2 uptake by muscle at high altitude, a physiologist

prepares an atmosphere consisting of 79 mol% N2, 17 mol%
16
O2, and 4.0 mol% 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.
O2 O2
mol% 18O2 4.0 mol% 18O2
SOLUTION:  18 = = 0.040
O2 100
divide by 100

 18
O2 P18 =  x Ptotal = 0.040 x 0.75 atm = 0.030 atm
O2 18
O2
multiply by Ptotal

partial pressure P
18
O2

5-28
 Figure 5.12
Collecting a water-insoluble gaseous
reaction product and determining its
pressure

5-29
 Sample Problem 5.9 Calculating the Amount of Gas Collected Over Water

PROBLEM: Acetylene (C2H2), an important fuel in welding, is produced in

the laboratory when calcium carbide (CaC2) reacts with water:

CaC2(s) + 2H2O(l) C2H2(g) + Ca(OH)2(aq)

For a sample of acetylene that is collected over water, the total

gas pressure (adjusted to barometric pressure) is 738 torr and
the volume is 523 mL. At the temperature of the gas (23 oC),
the vapor pressure of water is 21 torr. How many grams of
acetylene are collected?
PLAN: The difference in pressures will give P for C2H2. The ideal gas law
allows a determination of n. Converting n to grams requires the
molar mass, M.
SOLUTION: P
Ptotal P C2H2 = (738 - 21) torr = 717 torr
C2H2
-P atm
H2O PV 717 torr x = 0.943 atm
n=
RT 760 torr
n g
C2H2 C2H2
xM
5-30
 Sample Problem 5.9 (continued)

0.943 atm x 0.523 L

n = = 0.0203 mol C2H2
C2H2
atm L
0.0821 x 296 K
mol K

26.04 g C2H2
0.0203 mol x = 0.529 g C2H2
mol C2H2

5-31
 Summary of the stoichiometric
relationships between the amount (mol, n)
of gaseous reactant or product and the
gas variables pressure (P), volume (V) and
temperature (T)

amount amount
P,V,T (mol) P,V,T
(mol)
of gas A of gas B of gas B
of gas A
ideal ideal
molar ratio from gas
gas
balanced equation law
law

Figure 15.13

5-32
 Sample Problem 5.10 Using Gas Variables to Find Amount of
Reactants and Products

PROBLEM: A laboratory-scale method for reducing a metal oxide is to heat it

with H2. The pure metal and H2O are products. What volume of
H2 at 765 torr and 225 oC is needed to form 35.5 g of Cu from
copper(II) oxide?
PLAN: This problem requires stoichiometry and the gas laws; write a
balanced equation and use the moles of Cu to calculate moles and
then volume of H2 gas.
mass (g) of Cu SOLUTION: CuO(s) + H2(g) Cu(s) + H2O(g)
divide by M
mol Cu 1 mol H2
mol of Cu 35.5 g Cu x x = 0.559 mol H2
63.55 g Cu 1 mol Cu
molar ratio atm L
0.559 mol H2 x 0.0821 x 498 K = 22.6 L
mol of H2 mol K
use known P and T to find V 1.01 atm
L of H2

5-33
 Sample Problem 5.11 Using the Ideal Gas Law in a Limiting Reactant
Problem

PROBLEM: The alkali metals (Group 1A) react with the halogens (Group 7A) to
form ionic metal halides. 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: Write a balanced equation, and use the ideal gas law to find the number
of moles of reactants, the limiting reactant and the moles of product.

SOLUTION: 2K(s) + Cl2(g) 2KCl(s) P = 0.950 atm V = 5.25 L

T = 293 K n = unknown
PV 0.950 atm x 5.25 L
n = = = 0.207 mol Cl2
Cl2 RT atm L
0.0821 x 293 K
mol K
mol K 2 mol KCl
17.0 g x = 0.435 mol K 0.207 mol Cl2 x = 0.414 mol
39.10 g K 1 mol Cl2 KCl formed
2 mol KCl
0.435 mol K x = 0.435 mol
2 mol K KCl formed
74.55 g KCl
0.414 mol KCl x = 30.9 g KCl
mol KCl Cl2 is the limiting reactant
5-34
 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.

5-35
 Distribution of molecular speeds at three
temperatures

The most probable

speed increases as For N2 gas
the temperature
increases

The average kinetic

energy, Ek, is
proportional to the
absolute temperature

Figure 5.14

5-36
 A molecular description of
Boyle’s Law

Figure 5.15

5-37
 A molecular description of Dalton’s law of partial
pressures

Figure 5.16
5-38
 A molecular description of
Charles’s Law

Figure 5.17

5-39
 A molecular description of
Avogadro’s Law

Figure 5.18

5-40
 Why do equal numbers of molecules of two different gases, such
as O2 and H2, occupy the same volume (c.f. standard molar volume)?

At constant T, two gases possess the same kinetic energy; thus,

the heavier gas must be moving more slowly.

Ek = 1/2 massx u2

Ek = 1/2 mass x speed2 u2 is the average of the squares of

the molecular speeds; its square root
equals urms

urms = √ 3RT
M
=
root-mean-square speed; a molecule moving
at this speed has the average kinetic energy
R = 8.314 joule/mol K
1
urms √M
5-41
 Relationship between molar mass and
molecular speed
Figure 5.19

At a given temperature, gases with lower molar masses

have higher most probable speeds

5-42
EFFUSION: the process by which a gas escapes from its container
through a tiny hole into an evacuated space

Graham’s Law of
Effusion

The rate of effusion of a gas is inversely related to the square root of its molar mass.
1
rate of effusion (related to the rms speed)
 √M

rateA/rateB = MB1/2/MA1/2

The same relationships pertain to gaseous diffusion rates!

5-43
 Sample Problem 5.12 Applying Graham’s 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 of 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 M of He = 4.003 g/mol

rate

√
He 16.04
= = 2.002
rate 4.003
CH4

5-44
 Diffusion of a gas
particle through a
space filled with
other particles

Distribution of Molecular Speeds

Mean Free Path: the average distance

a molecule travels between collisions at
a given T and P

Collision Frequency: the average number Figure 5.20

of collisions per second (has implications
for chemical reaction rates)

5-45
 Real Gases
Molecules are not
points of mass.
QuickTime™ and a
There are attractive and Photo - JPEG decompressor
are needed to see this picture.

repulsive forces between

molecules.

Real gases approach ideal

behavior at high T and low P.

5-46
 Figure 5.21

The behavior of
several real gases
with increasing
external pressure

At moderately high P: intermolecular attractions dominate

At very high P: molecular volume effects dominate

5-47
he effect of intermolecular attractions on measured gas pressure

Figure 5.22

5-48
 The effect of molecular volume on measured gas volume

Figure 5.23

5-49
 The van der Waals equation for n moles of a real gas

(adjusts
V down)

(P + n2a/V2) (V - nb) = nRT

(adjusts QuickTime™ and a
Photo - JPEG decompressor
P up) are needed to see this picture.

a and b are the

van der Waals constants

5-50