Gases and The Kinetic-Molecular Theory

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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
Table 5.1
Some Important Industrial Gases
Name (Formula) Methane (CH4) Ammonia (NH3) Chlorine (Cl2)
Origin and Use

natural deposits; domestic fuel from N2+H2; fertilizers, explosives electrolysis of seawater; bleaching and disinfecting
Oxygen (O2)
Ethylene (C2H4)
liquefied air; steelmaking

high-temperature decomposition of natural gas; plastics
Atmosphere-Biosphere Redox Interconnections
5-3
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.
5-4
Figure 5.1
The three states of matter.
5-5
Figure 5.2
Effect of atmospheric pressure on objects at Earths surface.
5-6
Figure 5.3
A mercury barometer.
5-7
Figure 5.4 closed-end
Two types of manometer
open-end
5-8
Table 5.2 Common Units of Pressure

Unit pascal (Pa); kilopascal (kPa) atmosphere (atm) millimeters of mercury (Hg) torr pounds per square inch (psi or lb/in2) bar Atmospheric Pressure 1.01325 x 105 Pa; 101.325 kPa 1 atm* 760 mm Hg* Scientific Field SI unit; physics, chemistry chemistry chemistry, medicine, biology
760 torr* 14.7 lb/in2 1.01325 bar
chemistry engineering meteorology, chemistry, physics
*This is an exact quantity; in calculations, we use as many significant figures as necessary.
5-9
Sample Problem 5.1 PROBLEM:
Converting Units of Pressure
A geochemist heats a limestone (CaCO3) sample and collects the CO2 released in an evacuated flask attached to a closedend manometer. After the system comes to room temperature, Dh = 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
1 mmHg
= 291.4 torr
291.4 torr
1 atm 760 torr
= 0.3834 atm
0.3834 atm 101.325 kPa 1 atm
= 38.85 kPa
5-10
Figure 5.5
The relationship between the volume and pressure of a gas.
Boyles Law
5-11
Figure 5.6
The relationship between the volume and temperature of a gas.
Charless Law
5-12
Boyles Law VxP
V a = constant
1
P n and T are fixed V = constant / P
Charless Law
V T Amontonss Law P T combined gas law
V a T
P and n are fixed
= constant P a T
V = constant x T
V and n are fixed P = constant x T T P PV T
= constant T P
V a
V = constant x
= constant
5-13
Figure 5.7
An experiment to study the relationship between the volume and amount of a gas.
Van
[fixed P and T), V/n = constant
5-14
STP : 0 C (273 K) and 1 atm (760 torr); Under this condition the volume of 1 mol of ideal gas called Standard molar volume.
5-15
Figure 5.9
The volume of 1 mol of an ideal gas compared with some familiar objects. A basketball 7.5 L, 5 gal of fish tank 18.9 L, 13-in TV 21.6L , 22.4L He gas in a ballon
5-16
Figure 5.10
THE IDEAL GAS LAW
PV = nRT
3 significant figures
R=
PV nT
1 atm x 22.414 L 1 mol x 273.15 K

IDEAL GAS LAW
0.0821 atm*L mol*K
R is the universal gas constant
nRT
PV = nRT or V =
fixed n and T Boyles Law V= constant P fixed n and P Charless Law V=
P fixed P and T Avogadros Law V= constant X n
constant X T
5-17
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)? SOLUTION: P1 = 1.12 atm n and T are constant P2 = 2.64 atm
PLAN: V1 in cm3
unit V1 in mL conversion 103 mL = 1 L

V1 in L xP1/P2 V2 in L V2 = V1P1 P2 gas law calculation
1 cm3 = 1 mL
V1 = 24.8 cm3
V2 = unknown
= 0.0248 L
L 24.8 cm3 1 mL 1 cm3 103 mL P1V1 n1T1 = P2V2 n2T2 1.12 atm = 0.0248 L 2.46 atm
P1V1 = P2V2
= 0.0105 L
5-18
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 230C and 0.991 atm and placed in boiling water at exactly 1000C. Will the safety valve open? SOLUTION: T1 and T2(0C) K=0C+273.15 P1 = 0.991atm T1 = 23oC P2 = unknown T2 = 100oC
PLAN: P1(atm)
1atm=760torr P1(torr) x T2/T1 P2(torr)
T1 and T2(K)
0.991 atm 760 torr = 753 torr 1 atm P1V1 n1T1
P2V2 n2T2 = 949 torr
P1 T1
P2 T2
P2 = P1
T2 T1 = 753 torr
373 K 296 K
5-19
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: P and T are constant n2 = unknown V2 = 55.0 dm3 55.0 dm3 26.2 dm3 P1V1 n1T1 V1 n1 n2 = n1 V2 V1 = 1.10 mol = = P2V2 n2T2 V2 n2
n1 = 1.10 mol V1 = 26.2 dm3
= 2.31 mol
naddll = n2 n1 = 2.31 mol 1.10 mol = 1.21 mol He 1.21 mol He 4.003 g He mol He = 4.84 g He
5-20
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.
PLAN:
V, T and mass, which can be converted to moles (n), are given. Utilize the ideal gas law to find P. V = 438 L n = 0.885 kg (convert to mol) T = 21oC (convert to K) P = unknown 21oC + 273.15 = 294.15 K
SOLUTION:
0.885 kg
103 g kg
mol O2 32.00 g O2
= 27.7 mol O2 atm*L
27.7 mol x 0.0821 P= nRT V = 438 L
mol*K
x 294.15 K = 1.53 atm
5-21
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. T2 = 2T1 n2 = n1 SOLUTION: n1T1 = n2T2 Looking at the relationships, the equation that shows a decrease in the number of moles of gas from 2 to 1 is equation (3).
5-22
The Density of a Gas

density = m/V = mass/volume Number of moles, n = m/M = mass/molar mass 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.
5-23
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 = mass/volume PV = nRT V = nRT/P d = RT 44.01 g/mol x 1atm SOLUTION: (a) d= = 1.96 g/L atm*L 0.0821 x 273.15 K mol*K 1.96 g L mol CO2 44.01 g CO2 6.022x1023 molecules mol 44.01 g/mol x 1 atm 0.0821 1.83 g mol CO2 44.01 g CO2 atm*L x 293 K = 2.50x1022 molecules CO2/L mol*K 6.022x1023 molecules mol = 2.68x1022 molecules CO2/L
(b)
d=
= 1.83 g/L
5-24
The Molar Mass of a Gas
n=
mass M
PV RT mRT VP
M=
d=
m V
dRT M= P
5-25
Determining the molar mass of an unknown volatile liquid.

based on the method of J.B.A. Dumas (1800-1884) 1. Place small volume of volatile liquid in the preweighed flask (known volume). 2. Place the flask in water bath with known temperature to boil the liquid. 3. Wait until the pressure gas = atm pressure (no more gas flows. 4. Reweigh the flask when cooled.
5-26
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: T = 100.0oC P = 754 torr
Volume of flask = 213 mL
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
M=
mRT VP
0.582 g x 0.0821
atm*L mol*K
x 373 K
= 84.4 g/mol
0.213 L x 0.992 atm
5-27
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 : P (humd air) = P(dry air) + P (added water vapour) Each gas in the mixture exerts a partial pressure( a portion of the total of the mixture)
Ptotal = P1 + P2 + P3 + ...
P1= c1 x Ptotal c1 = n1 n1 + n2 + n3 +... where c1 is the mole fraction = n1 ntotal
5-28
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 % 16O and 4.0 mole % 18O . (The isotope 18O will be measured to 2, 2 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. mole % 18O2 divide by 100 c
18O 2 2 2
18 PLAN: Find the c 18Oand P18O from Ptotal and mol % O2.
SOLUTION:
18O
=
2
4.0 mol % 18O2 100
= 0.040
multiply by Ptotal partial pressure P

18O
P 18
= c 18 x Ptotal = 0.040 x 0.75 atm O2 O2
= 0.030 atm
5-29
Figure 5.12
Collecting a water-insoluble gaseous reaction product and determining its pressure.
5-30
Collecting a gas over water Partial pressure frequently used to determine yield of a water insoluble gas formed in a reaction. The gaseous product bubbles through water collected. The water vapour that mixes with the gas contributes a portion of total pressure called vapour pressure (depend on water temperature-refer to data given). Therefore, need to find vapour pressure and subtract with the total pressure- give partial pressure of gas product.
5-31
Table 5.3 Vapor Pressure of Water (P T(0C) P (torr)
H2O
) at Different T
P (torr)
T(0C)
0 5 10 12 14 16 18 20 22 24 26 28 30 35
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
5-32
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. SOLUTION: P C H = (738 - 21) torr = 717 torr
2 2
Ptotal P H2O P C2H2 n= PV RT
atm
= 0.943 atm
C2H2
0.943 atm x 0.0821 atm*L mol*K 0.0203 mol
760 torr 0.523 L = 0.0203 mol x 296 K 26.04 g C2H2 mol C2H2 = 0.529 g C2H2
C2H2 xM
g C2H2
5-33
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
amount (mol) of gas A ideal gas law
amount (mol) of gas B molar ratio from balanced equation ideal gas law
P,V,T of gas B
of gas A
5-34
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
1 mol H2
79.55 g CuO 1 mol CuO 0.446 mol H2 x 0.0821 1.01 atm 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
5-35
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 atm*L mol*K 0.207 mol Cl2 17.0 g 2 mol KCl 1 mol Cl2 = 0.435 mol K = 30.9 g KCl = 0.435 mol KCl = 0.414 mol KCl 0.414 mol KCl 2KCl(s) = 0.207 mol P = 0.950 atm T = 293 K V = 5.25 L n = unknown
0.0821
x 293 K
Cl2 is the limiting reactant. 74.55 g KCl mol KCl
mol K
39.10 g K
0.435 mol K
2 mol KCl 2 mol K
5-36
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
Distribution of molecular speeds at three temperatures.
5-38
Figure 5.15
A molecular description of Boyles Law.
5-39
Figure 5.16
A molecular description of Daltons law of partial pressures.
5-40
Figure 5.17
A molecular description of Charless Law.
5-41
Avogadros Law
V a
Ek = 1/2 mass x speed2
Ek = 1/2 mass x u 2
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 a 1 M
5-42
Figure 5.18
A molecular description of Avogadros Law.
5-43
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: rate He rate CH4 = M of CH4 = 16.04 g/mol M of He = 4.003 g/mol
16.04 4.003
= 2.002
5-45
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)

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
Gas
He H2 Ne Ideal gas Ar N2 O2 CO Cl2 NH3
5-50
Figure 5.21
The behavior of several real gases with increasing external pressure.
5-51
Figure 5.22
The effect of intermolecular attractions on measured gas pressure.
5-52
Figure 5.23
The effect of molecular volume on measured gas volume.
5-53
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
atm*L2
mol2
L
mol
Gas
5-54
He Ne Ar Kr Xe H2 N2 O2 Cl2 CH4 CO CO2 NH3 H2O
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

Gases and The Kinetic-Molecular Theory

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Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Gases and the Kinetic-Molecular Theory

Gases and the Kinetic Molecular Theory

Some Important Industrial Gases

Name (Formula) Methane (CH4) Ammonia (NH3) Chlorine (Cl2)

Origin and Use

liquefied air; steelmaking

Atmosphere-Biosphere Redox Interconnections

An Overview of the Physical States of Matter

1. Gas volume changes greatly with pressure.

3. Gases have relatively low viscosity.

The three states of matter.

Effect of atmospheric pressure on objects at Earths surface.

Figure 5.4 closed-end

Two types of manometer

Table 5.2 Common Units of Pressure

760 torr* 14.7 lb/in2 1.01325 bar

chemistry engineering meteorology, chemistry, physics

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

Sample Problem 5.1 PROBLEM:

Converting Units of Pressure

1 atm 760 torr

0.3834 atm 101.325 kPa 1 atm

The relationship between the volume and pressure of a gas.

The relationship between the volume and temperature of a gas.

Boyles Law VxP

P and n are fixed

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

[fixed P and T), V/n = constant

THE IDEAL GAS LAW

1 atm x 22.414 L 1 mol x 273.15 K

0.0821 atm*L mol*K

R is the universal gas constant

P fixed P and T Avogadros Law V= constant X n

Sample Problem 5.2 PROBLEM:

Applying the Volume-Pressure Relationship

unit V1 in mL conversion 103 mL = 1 L

Sample Problem 5.3 PROBLEM:

Applying the Temperature-Pressure Relationship

1atm=760torr P1(torr) x T2/T1 P2(torr)

0.991 atm 760 torr = 753 torr 1 atm P1V1 n1T1

P2V2 n2T2 = 949 torr

Sample Problem 5.4 PROBLEM:

Applying the Volume-Amount Relationship

n1 = 1.10 mol V1 = 26.2 dm3

Sample Problem 5.5 PROBLEM:

Solving for an Unknown Gas Variable at Fixed

= 27.7 mol O2 atm*L

27.7 mol x 0.0821 P= nRT V = 438 L

x 294.15 K = 1.53 atm

Sample Problem 5.6 PROBLEM:

Using Gas Laws to Determine a Balanced Equation

Which of the following balanced equations describes the reaction?

The Density of a Gas

Sample Problem 5.7

Calculating Gas Density

The Molar Mass of a Gas

Determining the molar mass of an unknown volatile liquid.

Sample Problem 5.8 PROBLEM:

Finding the Molar Mass of a Volatile Liquid

Volume of flask = 213 mL

0.213 L x 0.992 atm

0.0821 atmL molK

0.943 atm x 0.0821 atmL molK 0.0203 mol