Reactions Involved Carbo Cation Chem

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

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.
5-3
Figure 5.1 The three states of matter.
5-4
Figure 5.2 Effect of atmospheric pressure on objects

at the Earth’s surface.
5-5
Figure 5.3 A mercury barometer.
5-6
Table 5.1 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 14.7lb/in2 engineering

inch (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.

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:
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
5-8
Figure 5.4 The relationship between the volume

and pressure of a gas.
Boyle’s Law
5-9
Figure 5.5
The relationship between the

volume and temperature of a
gas.
Charles’s Law
5-10
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
5-11
Figure 5.6 An experiment to study the relationship between the

volume and amount of a gas.
5-12
Figure 5.7 Standard molar volume.
5-13
Figure 5.8 The volume of 1 mol of an ideal gas compared with some
familiar objects.
5-14
Figure 5.9 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
5-15
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 P1 V1 P2 V2 P1V1 = P2V2
calculation =
V2 in L n1T1 n2T2
P1 V1 1.12 atm
V2 = = 0.0248 L = 0.0105 L
P2 2.46 atm
5-16
Sample Problem 5.3 Applying the Pressure-Temperature 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)
P1 V1 P2 V2 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
5-17
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 P2 V2
n2(mol) of He =
V1 = 26.2 dm3 V2 = 55.0 dm3 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 dm 3
mol He
5-18
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
P= = = 1.53 atm
V 438 L
5-19
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).
5-20
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.
5-21
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
5-22
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
5-23
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
5-24
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
5-25
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%
16
O2, and 4.0 mol% 18O2. (The isotope 18O will be measured to
determine the O2 uptake.) The pressure of the mixture is
0.75atm 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
4.0 mol% 18O2
mol% O2
18
SOLUTION:  18 = = 0.040
O2 100
divide by 100
 18O2 P18 =  18 x Ptotal = 0.040 x 0.75 atm = 0.030 atm
O2 O2
multiply by Ptotal
partial pressure P
18
O2
5-26
The Molar Mass of a Gas
mass PV
n= =
M RT
m RT m
M= d=
VP V
d RT
M=
P
5-27
Table 5.2 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
5-28
Figure 5.10 Collecting a water-insoluble gaseous reaction

product and determining its pressure.
5-29
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: PC H = (738-21)torr = 717torr
Ptotal P 2 2
C2H2
P atm = 0.943atm
H2O PV 717torr
n=
RT 760torr
n g
C2H2 C2H2
xM
5-30
Sample Problem 5.10 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
5-31
Figure 15.11
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
5-32
Sample Problem 5.11 Using Gas Variables to Find Amounts 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
5-33
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
39.10 g K KCl formed
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
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
Figure 5.12 Distribution of molecular speeds at three temperatures.
5-36
Figure 5.13 A molecular description of Boyle’s Law.
5-37
Figure 5.14 A molecular description of Dalton’s law of partial pressures.
5-38
Figure 5.15 A molecular description of Charles’s Law.
5-39
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
5-40
Figure 5.16 A molecular description of Avogadro’s Law.
5-41
Figure 5.17 Relationship between molar mass and molecular speed.
Ek = 3/2 (R/NA) T
5-42
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
√
He 16.04
= = 2.002
rate 4.003
CH4
5-43
Figure 5.18 Diffusion of a gas particle through a

space filled with other particles.
distribution of molecular speeds
mean free path
collision frequency
5-44
Table 5.3 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
5-45
Figure 5.19
The behavior of several

real gases with increasing
external pressure.
5-46
Figure 5.20 The effect of intermolecular attractions on

measured gas pressure.
5-47
Figure 5.21 The effect of molecular volume on measured gas volume.
5-48
Table 5.54 Van der Waals Constants for Some Common Gases
n2a
Van der Waals
(P  2 )(V  nb)  nRT
equation for n V
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
5-49 H2O

Reactions Involved Carbo Cation Chem

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Reactions Involved Carbo Cation Chem

Uploaded by

Copyright:

Available Formats

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

Gases and the Kinetic-Molecular Theory

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

An Overview of the Physical States of Matter

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.

Figure 5.2 Effect of atmospheric pressure on objects

Figure 5.3 A mercury barometer.

Table 5.1 Common Units of Pressure

Unit Atmospheric Pressure Scientific Field

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

millimeters of 760 mm Hg* chemistry, medicine, biology

torr 760 torr* chemistry

pounds per square 14.7lb/in2 engineering

bar 1.01325 bar meteorology, chemistry,

*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

291.4 torr 1 atm = 0.3834 atm

0.3834 atm 101.325 kPa = 38.85 kPa

Figure 5.4 The relationship between the volume

The relationship between the

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

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

Figure 5.6 An experiment to study the relationship between the

Figure 5.7 Standard molar volume.

Figure 5.9 THE IDEAL GAS LAW

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

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

Sample Problem 5.2 Applying the Volume-Pressure Relationship

PLAN: SOLUTION: P and T are constant

Sample Problem 5.3 Applying the Pressure-Temperature Relationship

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

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

Sample Problem 5.5 Solving for an Unknown Gas Variable at Fixed

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

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

Sample Problem 5.6 Using Gas Laws to Determine a Balanced Equation

PROBLEM: The piston-cylinders below depict a gaseous reaction carried out

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

The Density of a Gas

•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

Sample Problem 5.6 Calculating Gas Density

44.01 g/mol x 1 atm

1.83g mol CO2 6.022x1023 molecules

Sample Problem 5.8 Finding the Molar Mass of a Volatile Liquid

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