Macroscopic vs.
Microscopic
Chapter 5
Gases and the Kinetic-
Kinetic-Molecular Theory
Kinetic Molecular Theory of Gases
1. Gas molecules are in constant motion in
random directions. Collisions among
molecules are perfectly elastic.
Representation
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)
1
 Distribution of molecular speeds at three temperatures.

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.

Relationship between molar mass and Physical Characteristics of Gases

molecular speed.
• 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.

2
 Pressure – Macroscopic
Pressure – KMT Viewpoint
Viewpoint
• Origin of Pressure –
Gas molecules hitting
Pressure = Force • ↑ Temp, ↑KE, ↑
container walls Area
Force, ↑ P
– ↑ Temp,↑ KE, ↑ #
Units of Pressure • ↓Volume, ↓ Area,
collisions, ↑ P
1 pascal (Pa) = 1 N/m2 ↑P
– ↓ Volume, ↑ # 1 atm = 760 mmHg = 760 torr
collisions, ↑ P
1 atm = 101,325 Pa

Common Units of Pressure

Unit Atmospheric Pressure Scientific Field Atmospheric Pressure

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

Barometer

3
 Converting Units of Pressure
Two types of manometer

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,
Δh = 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

The relationship between volume and the pressure of a gas.

Effect of Pressure on Volume

Boyle’s Law

1 atm 2 atm 5 atm

5 5 5

3 3 3

1 1 1

4
 Boyle’s Law
1
Boyle’s Law V α n and T are fixed
P

PV = constant V = constant/P

P α 1/V
P x V = constant Constant temperature
Constant amount of gas
P1 x V1 = P2 x V2

Kinetic
A sample of chlorine gas occupies a volume of 946 mL
Molecular theory of gases and … at a pressure of 726 mmHg. What is the pressure of
the gas (in mmHg) if the volume is reduced at constant
• Boyle’s Law temperature to 154 mL?

P α collision rate with wall

P1 x V1 = P2 x V2
Collision rate Increases with decreased volume
P α 1/V P1 = 726 mmHg P2 = ?
Increase P, decrease volume
V1 = 946 mL V2 = 154 mL

P1 x V1 726 mmHg x 946 mL

P2 = = = 4460 mmHg
V2 154 mL

5
Applying the Volume-Pressure Relationship

Effect of Temperature on Volume

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
(Charles’ Law)
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 High Temperature
Low Temperature

Applying the Temperature-Pressure Relationship

A 1-L steel tank is fitted with a safety valve that opens if the
Vα T internal pressure exceeds 1.00x103 torr. It is filled with helium
at 230C and 0.991atm and placed in boiling water at exactly
V = kT 1000C. Will the safety valve open?
V/T = k
V1/T1 = V2/T2
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
As T increases, V Increases

6
 Kinetic theory of gases and …
• Charles’ Law Determination of Absolute Zero
-Average kinetic energy α 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

A sample of carbon monoxide gas occupies 3.20 L at Avogadro’s Law

125 0C. At what temperature will the gas occupy a
volume of 1.54 L if the pressure remains constant? V α number of moles (n)
V = constant x n
V1/T1 = V2/T2
V1/n1 = V2/n2
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

5.3

7
Applying the Volume-Amount Relationship Kinetic theory of gases and …

A scale model of a blimp rises when it is filled with helium to a • Avogadro’s Law
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 More moles of gas, more collisions with walls of
to make it rise? Assume constant T and P. container
We are given initial n1 and V1 as well as the final V2. We have to find More collisions, higher pressure
n2 and convert it from moles to grams.

n1(mol) of He P and T are constant

BUT since pressure must remain constant and
only volume can change
x V2/V1 n1 = 1.10mol n2 = unknown P1V1 P2V2
n2(mol) of He V1 = 26.2dm3 V2 = 55.0dm3
= Volume increases to decrease pressure to original
n1T1 n2T2
subtract n1 value
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

1
Boyle’s Law V α n and T are fixed
P

Charles’s Law V α T P and n are fixed

V
= constant V = constant x T
T

Amonton’s Law P α T V and n are fixed

P
= constant P = constant x T
T

T T PV
combined gas law V α V = constant x = constant
P P T

8
 Ideal Gas Equation Obtaining Other Gas Law
Boyle’s law: V α 1 (at constant n and T) Relationship
P
Charles’ law: V α T (at constant n and P)
• PV = nRT
Avogadro’s law: V α n (at constant P and T)
PV
nT =R
Vα nT
P
nT nT P1V1 P2V2
V = constant x =R R is the gas constant =
P P n1T1 n2T2
R = 0.082057 L • atm / (mol • K)

PV = nRT

THE IDEAL GAS LAW Argon is an inert gas used in lightbulbs to retard the
vaporization of the filament. A certain lightbulb
PV = nRT containing argon at 1.20 atm and 18 0C is heated to
85 0C at constant volume. What is the final pressure of
PV 1atm x 22.414L 0.0821atm*L argon in the lightbulb (in atm)?
R= = =
nT 1mol x 273.15K mol*K
PV = nRT n, V and R are constant
IDEAL GAS LAW
nR
= P = constant
nRT
PV = nRT or V = P1 = 1.20 atm P2 = ?
P V T
fixed n and T fixed n and P fixed P and T T1 = 291 K T2 = 358 K
P1 P2
Boyle’s Law Charles’s Law Avogadro’s Law =
T1 T2
constant
= 1.20 atm x 358 K = 1.48 atm
V= V= constant X T V= constant X n T2
P P2 = P1 x
T1 291 K

9
 Using Gas Variables to Find Amount of Reactants and
Products
Types of Problems 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?
• Make Substitution into
P1V1 P2V2 PLAN: Since this problem requires stoichiometry and the gas laws, we have

= PV = nRT to write a balanced equation, use the moles of Cu to calculate mols

and then volume of H2 gas.

n1T1 n2T2 moles(n) =

mass, g
MolarMass, g / mole
mass (g) of Cu
divide by M
SOLUTION: CuO(s) + H2(g) Cu(s) + H2O(g)

mol Cu 1mol H2
mol of Cu 35.5g Cu = 0.559mol H2
63.55g Cu 1 mol Cu
Given initial conditions, molar ratio
mass atm*L
determine final conditions; Density = mol of H2
0.559mol H2 x 0.0821
mol*K
x 498K = 22.6L
Cancel out what is constant Volume use known P and T to find V
1.01atm
L of H2

Solving for an Unknown Gas Variable at Fixed Conditions Using the Ideal Gas Law in a Limiting-Reactant Problem

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

O2. Calculate the pressure of O2 at 210C. 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
V, T and mass, which can be converted to moles (n), are given. We potassium?
use the ideal gas law to find P. 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.
V = 438L T = 210C (convert to K)
SOLUTION: 2K(s) + Cl2(g) 2KCl(s) P = 0.950atm V = 5.25L
n = 0.885kg (convert to mol) P = unknown
PV 0.950atm x 5.25L T = 293K n = unknown
n = = = 0.207mol
103g mol O2 Cl2 RT atm*L
0.885kg = 27.7mol O2 210C + 273.15 = 294K 0.0821 x 293K
kg 32.00g O2 mol*K
2mol KCl
atm*L 17.0g mol K 0.207mol Cl2 = 0.414mol
24.7mol x 0.0821 x 294K = 0.435mol K 1mol Cl2
mol*K 39.10g K KCl formed
nRT
P= = = 1.53atm 2mol KCl
V 438L 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

10
 Standard Molar Volume

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

Finding the Molar Mass of a Volatile Liquid

Density (d) Calculations
A chemist isolates from a petroleum sample a colorless liquid
with the properties of cyclohexane (C6H12). The Dumas method
PM m is the mass of the gas in g is used to obtain the following data to determine its molar mass:
d= m =
V RT M is the molar mass of the gas
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?
Molar Mass (M ) of a Gaseous Substance Use unit conversions, mass of gas and density-M relationship.

m = (78.416 - 77.834)g = 0.582g

dRT
M= d is the density of the gas in g/L m RT 0.582g x 0.0821
atm*L
x 373K
P 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.

11
Calculating Gas Density Calculating Gas Density
continued

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). 44.01g/mol x 1atm
(b) d= = 1.83g/L

Density is mass/unit volume; substitute for volume in the ideal gas atm*L x 293K
0.0821
equation. Since the identity of the gas is known, we can find the molar mol*K
mass. Convert mass/L to molecules/L with Avogardro’s number.
MxP 1.83g mol CO2 6.022x1023molecules
d = mass/volume PV = nRT V = nRT/P d = = 2.50x1022molecules CO2/L
RT
L 44.01g CO2 mol
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

Dalton’s Law of Partial Pressures

The Molar Mass of a Gas

mass PV
V and T
n=
M
=
RT
are
constant

m RT m
M= d=
VP V

d RT
M=
P

P1 P2 Ptotal = P1 + P2

12
 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
2, and 4.0 mol%
18O . (The isotope 18O will be measured to
2
Dalton’s Law of Partial Pressures determine the O2 uptake.) The pressure of the mixture is
0.75atm to simulate high altitude. Calculate the mole fraction
Ptotal = P1 + P2 + P3 + ... and partial pressure of 18O2 in the mixture.

PLAN: Find the χ 18 and P18 from Ptotal and mol% 18O2.
O2 O2
P1= χ1 x Ptotal where χ1 is the mole fraction 4.0mol% 18O2
mol% 18O2 SOLUTION: χ 18 = = 0.040
O2 100
n1 n1 divide by 100
χ1 = =
n1 + n2 + n3 +... ntotal χ 18O
2 P18 = χ18 x Ptotal = 0.040 x 0.75atm = 0.030atm
O2 O2
multiply by Ptotal

partial pressure P
18O
2

Kinetic theory of gases and …

THOUGHT FOR THE DAY
• Dalton’s Law of Partial Pressures When you are in deep trouble, say nothing, and try to look like you know what you're doing.
Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = ΣPi

13
 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

14
 Gas diffusion is the gradual mixing of molecules of one gas
with molecules of another by virtue of their kinetic properties.
Avogadro’s Law V α n

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

u 2 is the root-mean-square speed

NH4Cl 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 α
NH3 HCl √M
17 g/mol 36 g/mol

Applying Graham’s Law of Effusion

PROBLEM: Calculate the ratio of the effusion rates of helium and methane (CH4). Real Gases
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 • Nonideal Conditions -
the inverse square root of their masses. when gas gets close to
SOLUTION: M of CH4 = 16.04g/mol M of He = 4.003g/mol
conditions where it
will liquify
rate

rate
He

CH4
=
√ 16.04
4.003
= 2.002 – Lower Temperature
– Higher Pressure

⎛ an 2 ⎞
⎜⎜ P + 2 ⎟⎟(V − nb ) = nRT
⎝ V ⎠

15
 Real Gases
Effect of Intermolecular
Forces

– Corrected Pressure, a
– Corrected Volume, b

16