Gas

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

Table 5.1 Some Important Industrial Gases

Name (Formula) Origin and Use

Methane (CH4) natural deposits; domestic fuel

from N2+H2; fertilizers, explosives
Ammonia (NH3)
electrolysis of seawater; bleaching and
Chlorine (Cl2) disinfecting

Oxygen (O2) liquefied air; steelmaking

high-temperature decomposition of natural gas; plastics
Ethylene (C2H4)

Atmosphere-Biosphere Redox Interconnections

 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.

Figure 5.1 The three states of matter.
Pressure
 Force
Pressure =
Area

Units of Pressure

1 pascal (Pa) = 1 N/m2

1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa

Barometer
10 miles 0.2 atm

4 miles 0.5 atm

Sea level 1 atm

Figure 5.2 Effect of atmospheric pressure on objects
at the Earth’s surface.
Figure 5.3 A mercury barometer.
Figure 5.4
closed-end

Two types of
manometer

open-end
 Table 5.2 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 mm Hg* chemistry, medicine, biology

mercury(Hg)

torr 760 torr* chemistry

pounds per square inch 14.7lb/in2 engineering

(psi or lb/in2)

bar 1.01325 bar meteorology, chemistry,

physics

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

 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 = 38.85 kPa

1 atm
Temperature
K = 0C + 273.15
273 K = 0 0C
373 K = 100 0C

9 0
F=
0
x C + 32
5
32 0F = 0 0C
212 0F = 100 0C
Some interesting
temperatures.

1- 16
The freezing and boiling points of water.

1- 17
 Temperature Scales and Interconversions

Kelvin ( K ) - The “Absolute temperature scale” begins at absolute zero

and only has positive values.

Celsius ( oC ) - The temperature scale used by science, formally called

centigrade, most commonly used scale around the world; water freezes
at 0oC, and boils at 100oC.

Fahrenheit ( oF ) - Commonly used scale in the U.S. for our weather

reports; water freezes at 32oF and boils at 212oF.

T (in K) = T (in oC) + 273.15 T (in oF) = 9/5 T (in oC) + 32

T (in oC) = T (in K) - 273.15 T (in oC) = [ T (in oF) - 32 ] 5/9

1- 18
Convert 172.9 0F to degrees Celsius.
9 0
0
F=x C + 32
5
9 0
0
F – 32 = x C
5
5 x (0F – 32) = 0C
9
C = 5 x (0F – 32)
0
9
0
C = 5 x (172.9 – 32) = 78.3
9
Gas’ laws
Figure 5.5 The relationship between the volume and
pressure of a gas.

Boyle’s Law
 Figure 5.6

The relationship between the

volume and temperature of a gas.

Charles’s Law
 1
Boyle’s Law V  n and T are fixed
P
VxP = constant V = constant / P

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

V
= constant V = constant x T
T

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

P
= constant P = constant x T
T

T T PV
combined gas law V  V = constant x = constant
P P T
Figure 5.7 An experiment to study the relationship between the volume
and amount of a gas.
Figure 5.8 Standard molar volume.
Figure 5.9 The volume of 1 mol of an ideal gas compared with some
familiar objects.
 Figure 5.10 THE IDEAL GAS LAW

PV = nRT
3 significant figures
PV 1atm x 22.414L 0.0821atm*L
R= = =
nT 1mol x 273.15K mol*K
R is the universal gas constant
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
 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: P and T are constant

V1 in cm3 P1 = 1.12 atm P2 = 2.64 atm
1cm3=1mL
unit V1 = 24.8 cm3 V2 = unknown
V1 in mL conversion
103 mL=1L 24.8 cm3 1 mL L = 0.0248 L
V1 in L 1 cm3 103 mL
gas law
xP1/P2 calculation P1V1 P2V2 P1V1 = P2V2
=
V2 in L n1T1 n2T2
P1 V1 1.12 atm
V2 = = 0.0248 L = 0.0105 L
P2 2.46 atm
 Sample Problem 5.3 Applying the Temperature-Pressure Relationship

PROBLEM: 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 230C and 0.991 atm and placed in boiling water at exactly
1000C. Will the safety valve open?

PLAN: SOLUTION:

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

1atm=760torr K=0C+273.15 T1 = 230C T2 = 1000C
P1(torr) T1 and T2(K)
P1V1 P2V2 P1 P2
x T2/T1 = =
n1T1 n2T2 T1 T2
P2(torr)
0.991 atm 760 torr = 753 torr
1 atm
T2
P2 = P1 373K
= 753 torr = 949 torr
T1 296K
 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. 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: 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 SOLUTION: P and T are constant

x V2/V1 n1 = 1.10 mol n2 = unknown P1 V1 P2V2
n2(mol) of He =
V1 = 26.2 dm 3
V2 = 55.0 dm 3
n1T1 n2T2
subtract n1 V1 V2 V2
mol to be added = n2 = n1
n1 n2 V1
xM
55.0 dm3 4.003 g He
g to be added n2 = 1.10 mol = 2.31 mol = 9.24 g He
26.2 dm3 mol He
 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 210C.

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

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

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

103 g mol O2
0.885kg = 27.7 mol O2 210C + 273.15 = 294.15K
kg 32.00 g O2
atm*L
24.7 mol x 0.0821 x 294.15K
nRT mol*K
= 1.53 atm
P= =
V 438 L
 Sample Problem 5.6 Using Gas Laws to Determine a Balanced Equation

PROBLEM: 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.

New figures go here.

Which of the following balanced equations describes the reaction?

(1) A2 + B2 2AB (2) 2AB + B2 2AB2

(3) A + B2 AB2 (4) 2AB2 A2 + 2B2

PLAN: We know P, T, and V, initial and final, from the pictures. Note that the
volume doesn’t change even though the temperature is doubled. With a
doubling of T then, the number of moles of gas must have been halved in
order to maintain the volume.

SOLUTION: Looking at the relationships, the equation that shows a

decrease in the number of moles of gas from 2 to 1 is equation
(3).
 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.

 Sample Problem 5.7 Calculating Gas Density

PROBLEM: To apply a green chemistry approach, a chemical engineer uses waste

CO2 from a manufacturing process, instead of chlorofluorocarbons, as
a “blowing agent” in the production of polystyrene containers. Find the
density (in g/L) of CO2 and the number of molecules (a) at STP (00C
and 1 atm) and (b) at room conditions (20.0C 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, we can find the molar mass. Convert
mass/L to molecules/L with Avogadro’s number.
MxP
d = mass/volume PV = nRT V = nRT/P d =
RT
SOLUTION:
44.01 g/mol x 1atm
d= = 1.96 g/L
(a)
atm*L
0.0821 x 273.15K
mol*K
1.96 g mol CO2 6.022x1023 molecules
= 2.68x1022 molecules CO2/L
L 44.01 g CO2 mol
Sample Problem 5.6 Calculating Gas Density

continued

44.01 g/mol x 1 atm

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

1.83g mol CO2 6.022x1023 molecules

= 2.50x1022 molecules CO2/L
L 44.01g CO2 mol
 Figure 5.11

Determining the molar mass of

an unknown volatile liquid.

based on the method of

J.B.A. Dumas (1800-1884)
 Sample Problem 5.8 Finding the Molar Mass of a Volatile Liquid

PROBLEM: 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 = 100.00C 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 = (78.416 - 77.834) g = 0.582 g

atm*L
m RT 0.582 g x 0.0821 x 373K
M= = mol*K = 84.4 g/mol
VP
0.213 L x 0.992 atm
Mixtures of Gases

•Gases mix homogeneously in any proportions.

•Each gas in a mixture behaves as if it were the only gas present.

Dalton’s Law of Partial Pressures

Ptotal = P1 + P2 + P3 + ...

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

n1 n1
1 = =
n1 + n2 + n3 +... ntotal
 Sample Problem 5.9 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% 16O2, and
4.0 mol% 18O2. (The isotope 18O will be measured to 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  and P from P total and mol% 18

O2.
18
O2 18
O2
4.0 mol% 18O2
mol% 18O2 SOLUTION:  = = 0.040
O2
18
100
divide by 100
 18
O2 P18 = x P = 0.040 x 0.75 atm = 0.030 atm
O2 O2 total
18

multiply by Ptotal

partial pressure P
18
O2
 The Molar Mass of a Gas

mass PV
n= =
M RT

m RT m
M= d=
VP V

d RT
M=
P
Table 5.3 Vapor Pressure of Water (P ) at Different T
H2O

T(0C) P (torr) T(0C) P (torr)

0 4.6 30 31.8
5 6.5 35 42.2
10 9.2 40 55.3
11 9.8 45 71.9
12 10.5 50 92.5
13 11.2 55 118.0
14 12.0 60 149.4
15 12.8 65 187.5
16 13.6 70 233.7
18 15.5 75 289.1
20 17.5 80 355.1
22 19.8 85 433.6
24 22.4 90 525.8
26 25.2 95 633.9
28 28.3 100 760.0
Figure 5.12 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), 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.
SOLUTION: P = (738-21)torr = 717torr
Ptotal P C 2H 2
C2H2
P atm = 0.943atm
H2O PV 717torr
n=
RT 760torr
n g
C2H2 C2H2
xM
Sample Problem 5.9 Calculating the Amount of Gas Collected Over Water

continued

0.943atm x 0.523L
n = = 0.0203mol
C2H2
atm*L
0.0821 x 296K
mol*K

26.04g C2H2
0.0203mol = 0.529 g C2H2
mol C2H2
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).

amount (mol) amount (mol)

P,V,T P,V,T
of gas A of gas B
of gas A of gas B

ideal ideal
molar ratio from
gas gas
balanced equation
law law
 Sample Problem 5.11 Using Gas Variables to Find Amount of Reactants
and Products

PROBLEM: Dispersed copper in absorbent beds is used to react with oxygen

impurities in the ethylene used for producing polyethylene. The beds
are regenerated when hot H2 reduces the metal oxide, forming the pure
metal and H2O. On a laboratory scale, what volume of H2 at 765 torr
and 2250C is needed to reduce 35.5 g of 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 1 mol H2
mol of Cu 35.5 g Cu = 0.559 mol H2
63.55 g Cu 1 mol Cu
molar ratio
atm*L
0.559 mol H2 x 0.0821 x 498K = 22.6 L
mol of H2 mol*K
use known P and T to find V
1.01 atm
L of H2
 Sample Problem 5.12 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 5.25 L of
chlorine gas at 0.950 atm and 293K 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: 2K(s) + Cl2(g) 2KCl(s) P = 0.950 atm V = 5.25 L

PV 0.950 atm x 5.25L T = 293K n = unknown

n = = = 0.207 mol
Cl2 RT atm*L
0.0821 x 293K
mol*K
2 mol KCl
17.0g mol K 0.207 mol Cl2 = 0.414 mol
= 0.435 mol K 1 mol Cl2 KCl formed
39.10 g K
2 mol KCl
Cl2 is the limiting reactant. 0.435 mol K = 0.435 mol
2 mol K KCl formed
74.55 g KCl
0.414 mol KCl = 30.9 g KCl
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.
Figure 5.14 Distribution of molecular speeds at three temperatures.
Figure 5.15 A molecular description of Boyle’s Law.
Figure 5.16 A molecular description of Dalton’s law of partial pressures.
Figure 5.17 A molecular description of Charles’s Law.
 Avogadro’s Law V  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 
√M
Figure 5.18 A molecular description of Avogadro’s Law.
Figure 5.19 Relationship between molar mass and molecular speed.

Ek = 3/2 (R/NA) T
 Sample Problem 5.13 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
Figure 5.20 Diffusion of a gas particle through a space
filled with other particles.

distribution of molecular speeds

mean free path

collision frequency
Figure B5.1

Variations in pressure, temperature, and

composition of the Earth’s atmosphere.
Table 5.4 Molar Volume of Some Common Gases at STP
(00C and 1 atm)

Molar Volume Condensation Point

Gas (L/mol) (0C)

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
22.388 -191.5
CO
22.184 -34.0
Cl2
22.079 -33.4
NH3
Figure 5.21

The behavior of several real

gases with increasing
external pressure.
Figure 5.22 The effect of intermolecular attractions on
measured gas pressure.
Figure 5.23 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 (P       
moles of a real gas 
adjusts P up adjusts V down

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
3.59 0.0427
CO2
2.25 0.0428
CH4 4.17 0.0371
NH3 5.46 0.0305
H2O