Chapter 5

Gases and the Kinetic-Molecular Theory

Macroscopic vs. Microscopic
Representation
Kinetic Molecular Theory of Gases
1. Gas molecules are in constant motion in
random directions. Collisions among
molecules are perfectly elastic.
 Kinetic Molecular Theory of Gases
2. The average kinetic energy of the molecules is proportional
to the temperature of the gas in kelvins. Any two gases at
the same temperature will have the same average kinetic
energy
3. A gas is composed of molecules that are separated from
each other by distances far greater than their own
dimensions. The molecules can be considered to be points;
that is, they possess mass but have negligible volume.
4. Gas molecules exert neither attractive nor repulsive forces
on one another.
5. Each gas molecule “behaves” as if it were alone in
container (due to #3 and #4)
 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(Kk) of the particles is constant.
Distribution of molecular speeds at three temperatures.
Relationship between molar mass and
molecular speed.
 Physical Characteristics of Gases
• Gases assume the volume and shape of their containers.
• Gases are the most compressible state of matter.
• Gases will mix evenly and completely when confined to
the same container.
• Gases have much lower densities than liquids and solids.
Pressure – KMT Viewpoint
• Origin of Pressure –
Gas molecules hitting
container walls

–  Temp, KE,  #
collisions,  P

–  Volume,  #
collisions,  P
 Pressure – Macroscopic
Viewpoint

Pressure = Force •  Temp, KE, 

Area
Force,  P

Units of Pressure • Volume,  Area,

1 pascal (Pa) = 1 N/m2 P
1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa
Common Units of Pressure

Unit Atmospheric Pressure Scientific Field

pascal(Pa); 1.01325x105Pa; SI unit; physics, chemistry

kilopascal(kPa) 101.325 kPa
atmosphere(atm) 1 atm chemistry

millimeters of 760 mmHg chemistry, medicine, biology

mercury(Hg)

torr 760 torr chemistry

pounds per square 14.7lb/in2 engineering

inch (psi or lb/in2)

bar 0.01325 bar meteorology, chemistry,

physics
Atmospheric Pressure

Barometer
Two types of manometer
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,
Dh = 291.4mmHg. Calculate the CO2 pressure in torrs,
atmospheres, and kilopascals.
PLAN: Construct conversion factors to find the other units of pressure.

291.4mmHg 1torr = 291.4torr

1mmHg

291.4torr 1atm = 0.3834atm

760torr

0.3834atm 101.325kPa = 38.85kPa

1atm
 Effect of Pressure on Volume
Boyle’s Law

1 atm 2 atm 5 atm

5 5 5

3 3 3

1 1 1
The relationship between volume and the pressure of a gas.
 Boyle’s Law

P a 1/V
P x V = constant Constant temperature
Constant amount of gas
P1 x V1 = P2 x V2
 1
Boyle’s Law V a n and T are fixed
P

PV = constant V = constant/P
 Kinetic
Molecular theory of gases and …

• Boyle’s Law
P a collision rate with wall
Collision rate Increases with decreased volume
P a 1/V
Increase P, decrease volume
 A sample of chlorine gas occupies a volume of 946 mL
at a pressure of 726 mmHg. What is the pressure of
the gas (in mmHg) if the volume is reduced at constant
temperature to 154 mL?

P1 x V1 = P2 x V2
P1 = 726 mmHg P2 = ?
V1 = 946 mL V2 = 154 mL

P1 x V1 726 mmHg x 946 mL

P2 = = = 4460 mmHg
V2 154 mL
Applying the Volume-Pressure Relationship

PROBLEM: Boyle’s apprentice finds that the air trapped in a J tube occupies
24.8cm3 at 1.12atm. By adding mercury to the tube, he increases
the pressure on the trapped air to 2.64atm. Assuming constant
temperature, what is the new volume of air (inL)?

PLAN: SOLUTION: P and T are constant

V1 in cm3 P1 = 1.12atm P2 = 2.64atm
1cm3=1mL
unit V1 = 24.8cm3 V2 = unknown
V1 in mL
conversion
103mL=1L 24.8cm3 1mL L = 0.0248L
V1 in L 1cm3 103mL
gas law
xP1/P2 P1V1 P2V2 P1V1 = P2V2
calculation =
V2 in L n1T1 n2T2
P1V1 1.12atm
V2 = = 0.0248L = 0.0105L
P2 2.46atm
Effect of Temperature on Volume
(Charles’ Law)

Low Temperature High Temperature

 Va T
V = kT
V/T = k
V1/T1 = V2/T2

As T increases, V Increases
Charles Law Animation
Applying the Temperature-Pressure Relationship

A 1-L steel tank is fitted with a safety valve that opens if the
internal pressure exceeds 1.00x103 torr. It is filled with helium at
230C and 0.991atm and placed in boiling water at exactly 1000C.
Will the safety valve open?

P1(atm) T1 and T2(0C) P1 = 0.991atm P2 = unknown

1atm=760torr K=0C+273.15 T1 = 230C T2 = 100 oC
P1(torr) T1 and T2(K)
P1V1 P2V2 P1 P2
x T2/T1 = =
n1T1 n2T2 T1 T2
P2(torr)
0.991atm 760torr = 753torr
1atm
T2
P2 = P1 373K
= 753torr = 949torr
T1 296K
 Kinetic theory of gases and …
• Charles’ Law
-Average kinetic energy a T
-Increase T, Gas Molecules hit walls with greater Force,
this Increases the Pressure
BUT since pressure must remain constant, and only
volume can change
-Volume Increase to reduce Pressure
-Increase Temperature, Increase Volume
Determination of Absolute Zero
 A sample of carbon monoxide gas occupies 3.20 L at
125 0C. At what temperature will the gas occupy a
volume of 1.54 L if the pressure remains constant?

V1/T1 = V2/T2

V1 = 3.20 L V2 = 1.54 L
T1 = 398.15 K T2 = ?

V2 x T1 1.54 L x 398.15 K
T2 = = = 192 K
V1 3.20 L
 Avogadro’s Law
V a number of moles (n)
V = constant x n
V1/n1 = V2/n2

5.3
Applying the Volume-Amount Relationship

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

volume of 55dm3. When 1.10mol of He is added to the blimp, the
volume is 26.2dm3. How many more grams of He must be added
to make it rise? Assume constant T and P.

We are given initial n1 and V1 as well as the final V2. We have to find
n2 and convert it from moles to grams.

n1(mol) of He P and T are constant

x V2/V1 n1 = 1.10mol n2 = unknown P1V1 P2V2
n2(mol) of He =
V1 = 26.2dm3 V2 = 55.0dm3 n1T1 n2T2
subtract n1 V1 V2 V2
mol to be added = n2 = n1
n1 n2 V1
xM
55.0dm3 4.003g He
g to be added n2 = 1.10mol = 2.31mol = 4.84g He
26.2dm3 mol He
 Kinetic theory of gases and …
• Avogadro’s Law
More moles of gas, more collisions with walls of
container
More collisions, higher pressure
BUT since pressure must remain constant and
only volume can change
Volume increases to decrease pressure to original
value
 1
Boyle’s Law V a n and T are fixed
P

Charles’s Law V a T P and n are fixed

V
= constant V = constant x T
T

Amonton’s Law P a T V and n are fixed

P
= constant P = constant x T
T

T T PV
combined gas law V a V = constant x = constant
P P T
Gas Law Animation
 Ideal Gas Equation
Boyle’s law: V a 1 (at constant n and T)
P
Charles’ law: V a T (at constant n and P)
Avogadro’s law: V a n (at constant P and T)

nT
Va
P
nT nT
V = constant x =R R is the gas constant
P P
R = 0.082057 L • atm / (mol • K)

PV = nRT
 Obtaining Other Gas Law
Relationship
• PV = nRT
PV
R
nT

P1V1 P2V2

n1T1 n2T2
 THE IDEAL GAS LAW

PV = nRT
PV 1atm x 22.414L 0.0821atm*L
R= = =
nT 1mol x 273.15K mol*K
IDEAL GAS LAW
nRT
PV = nRT or V =
P

fixed n and T fixed n and P fixed P and T

Boyle’s Law Charles’s Law Avogadro’s Law

constant V= constant X n
V= V= constant X T
P
 Argon is an inert gas used in lightbulbs to retard the
vaporization of the filament. A certain lightbulb
containing argon at 1.20 atm and 18 0C is heated to
85 0C at constant volume. What is the final pressure of
argon in the lightbulb (in atm)?

PV = nRT n, V and R are constant

nR P
= = constant P1 = 1.20 atm P2 = ?
V T
T1 = 291 K T2 = 358 K
P1 P2
=
T1 T2
T2
P2 = P1 x = 1.20 atm x 358 K = 1.48 atm
T1 291 K
 Types of Problems

• Make Substitution into

P1V1 P2V2
 PV = nRT

n1T1 n2T2 moles (n) 

mass, g
MolarMass, g / mole

Given initial conditions, mass

determine final conditions; Density 
Cancel out what is constant Volume
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 765torr and 2250C is needed to form 35.5g of Cu from
copper (II) oxide?

PLAN: Since this problem requires stoichiometry and the gas laws, we have
to write a balanced equation, use the moles of Cu to calculate mols
and then volume of H2 gas.
mass (g) of Cu SOLUTION: CuO(s) + H2(g) Cu(s) + H2O(g)
divide by M
mol Cu 1mol H2
mol of Cu 35.5g Cu = 0.559mol H2
63.55g Cu 1 mol Cu
molar ratio
atm*L
0.559mol H2 x 0.0821 x 498K = 22.6L
mol of H2 mol*K
use known P and T to find V
1.01atm
L of H2
Solving for an Unknown Gas Variable at Fixed Conditions

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

O2. Calculate the pressure of O2 at 210C.

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

use the ideal gas law to find P.

V = 438L T = 210C (convert to K)

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

103g mol O2
0.885kg = 27.7mol O2 210C + 273.15 = 294K
kg 32.00g O2
atm*L
24.7mol x 0.0821 x 294K
nRT mol*K
P= = = 1.53atm
V 438L
Using the Ideal Gas Law in a Limiting-Reactant Problem

PROBLEM: The alkali metals [Group 1A(1)] react with the halogens [Group 7A(17)]
to form ionic metal halides. What mass of potassium chloride forms
when 5.25L of chlorine gas at 0.950atm and 293K reacts with 17.0g 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: 2K(s) + Cl2(g) 2KCl(s) P = 0.950atm V = 5.25L

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

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
Standard Molar Volume
Density (d) Calculations

m PM m is the mass of the gas in g

d= =
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M= d is the density of the gas in g/L
P
Finding the Molar Mass of a Volatile Liquid

A chemist isolates from a petroleum sample a colorless liquid

with the properties of cyclohexane (C6H12). The Dumas method
is used to obtain the following data to determine its molar mass:

Volume of flask = 213mL T = 100.00C P = 754 torr

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

Is the calculated molar mass consistent with the liquid being cyclohexane?
Use unit conversions, mass of gas and density-M relationship.

m = (78.416 - 77.834)g = 0.582g

atm*L
m RT 0.582g x 0.0821 x 373K
M= = mol*K = 84.4g/mol
VP
0.213L x 0.992atm
M of C6H12 is 84.16g/mol and the calculated value is within experimental error.
Calculating Gas Density

Calculate the density (in g/L) of carbon dioxide and the number
of molecules per liter (a) at STP (00C and 1 atm) and (b) at
ordinary room conditions (20.0C and 1.00atm).

Density is mass/unit volume; substitute for volume in the ideal gas

equation. Since the identity of the gas is known, we can find the molar
mass. Convert mass/L to molecules/L with Avogardro’s number.
MxP
d = mass/volume PV = nRT V = nRT/P d =
RT

44.01g/mol x 1atm
d= = 1.96g/L
(a)
atm*L
0.0821 x 273K
mol*K
1.96g mol CO2 6.022x1023molecules
= 2.68x1022molecules CO2/L
L 44.01g CO2 mol
Calculating Gas Density
continued

44.01g/mol x 1atm
(b) d= = 1.83g/L
atm*L x 293K
0.0821
mol*K

1.83g mol CO2 6.022x1023molecules

= 2.50x1022molecules CO2/L
L 44.01g CO2 mol
 The Molar Mass of a Gas

mass PV
n= =
M RT

m RT m
M= d=
VP V

d RT
M=
P
 Dalton’s Law of Partial Pressures

V and T
are
constant

P1 P2 Ptotal = P1 + P2
 Dalton’s Law of Partial Pressures

Ptotal = P1 + P2 + P3 + ...

P1= c1 x Ptotal where c1 is the mole fraction

n1 n1
c1 = =
n1 + n2 + n3 +... ntotal
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%
16O and 4.0 mol% 18O . (The isotope 18O will be measured to
2, 2
determine the O2 uptake.) The pressure of the mixture is
0.75atm to simulate high altitude. Calculate the mole fraction
and partial pressure of 18O2 in the mixture.

PLAN: Find the c 18 and P18 from Ptotal and mol% 18O2.
O2 O2
18
4.0mol% 18O2
mol% O2 SOLUTION: c 18 = = 0.040
O2 100
divide by 100
c 18O
2 P18 = c18 x Ptotal = 0.040 x 0.75atm = 0.030atm
O2 O2
multiply by Ptotal

partial pressure P
18O
2
 Kinetic theory of gases and …
• Dalton’s Law of Partial Pressures
Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = SPi
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) reaction 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 738torr and
the volume is 523mL. At the temperature of the gas (230C), the
vapor pressure of water is 21torr. How many grams of
acetylene are collected?
PLAN: The difference in pressures will give us the P for the C2H2. The ideal
gas law will allow us to find n. Converting n to grams requires the
molar mass, M.
P
Ptotal P C2H2 = (738-21)torr = 717torr
C2H2
P atm = 0.943atm
H2O PV 717torr
n=
RT 760torr
n g
C2H2 C2H2
xM
Calculating the Amount of Gas Collected Over Water
continued

0.943atm x 0.523L
n = = 0.203mol
C2H2
atm*L
0.0821 x 296K
mol*K

26.04g C2H2
0.203mol = 0.529 g C2H2
mol C2H2
Gas diffusion is the gradual mixing of molecules of one gas
with molecules of another by virtue of their kinetic properties.

NH4Cl

NH3 HCl
17 g/mol 36 g/mol
 Avogadro’s Law V a n

Ek = 1/2 mass x speed2 Ek = 1/2 mass x u 2

u 2 is the root-mean-square speed

urms = √3RT R = 8.314Joule/mol*K

M

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 a
√M
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 for each gas. Find the molar mass of both gases and find
the inverse square root of their masses.

SOLUTION: M of CH4 = 16.04g/mol M of He = 4.003g/mol

rate

rate
He

CH4
=
√ 16.04
4.003
= 2.002
 Real Gases
• Nonideal Conditions -
when gas gets close to
conditions where it
will liquify

– Lower Temperature
– Higher Pressure

 an 2 
 P  2 V  nb   nRT
 V 
 Real Gases
Effect of Intermolecular
Forces

– Corrected Pressure, a
– Corrected Volume, b