chapter5 e-learning

Chapter 5
Gases
氣體
黃俊嬴
高雄醫學大學
醫藥暨應用化學系;
Lab: 第一教學大樓 N1128
Tel: (07)312-1101*2810
Mail: genin@kmu.edu.tw
Chapter 5
Table of Contents
5.1 Pressure
5.2 The Gas Laws of Boyle, Charles, and Avogadro
5.3 The Ideal Gas Law
5.4 Gas Stoichiometry
5.5 Dalton’s Law of Partial Pressures
5.6 The Kinetic Molecular Theory of Gases
5.7 Effusion and Diffusion
5.8 Real Gases
5.9 Characteristics of Several Real Gases
5.10 Chemistry in the Atmosphere
Copyright © Cengage Learning. All rights reserved 2

Chapter 5
Why Study Gases?
Although relatively few substances exist in

the gaseous state under typical conditions,
gases are very important.
• An understanding of real world phenomena.

• An understanding of how science “works.”

Section 5.1
Pressure
學習目標
1. 了解氣體的特性以及描述氣壓的方式
2. 認識三個基本的氣體定律，合體後的理想氣體
方程式，以及熟悉相關的計算問題
3. 熟悉吞哥的分壓定律以及相關計算
Return to TOC

Section 5.1
Pressure
A Gas
• Uniformly fills any container.
• Mixes completely with any other gas.
• Exerts pressure on its surroundings.
The pressure exerted by the gases in the atmosphere can be demonstrated by boiling water in a
large metal can (a) and then turning off the heat and sealing the can. As the can cools, the water
vapor condenses, lowering the gas pressure inside the can. This causes the can to crumple (b). Return to TOC
Section 5.1
Pressure Torricellian Barometer
Barometer (氣壓計)
• Device used to measure
atmospheric pressure.
• Mercury flows out of the
tube until the pressure of
the column of mercury
standing on the surface of
the mercury in the dish is
equal to the pressure of the
air on the rest of the
surface of the mercury in
the dish.
Return to TOC

Section 5.1
Pressure
Units of Pressure
Because instruments used for measuring pressure, such as

the manometer.
The unit mm Hg (millimeter of mercury) is often called the
torr in honor of Torricelli.
A related unit for pressure is the standard atmosphere
(abbreviated atm):
1 standard atmosphere = 1 atm = 760 mm Hg = 760 torr
Return to TOC
Copyright © Cengage Learning. All rights reserved

Section 5.1
Pressure A simple manometer
A device for measuring the pressure of a gas in a container. The pressure of the gas is
given by h (the difference in mercury levels) in units of torr (equivalent to mm Hg).
Return to TOC

Section 5.1
Pressure
Pressure force
Pr essure =
area
• SI units = Newton/meter2 = 1 Pascal (Pa)
1 atm ＝ 760 mm Hg
＝ 760 torr
＝ 101,325 Pa
＝ 29.92 in Hg
＝ 14.7 lb/in2 (psi)
Return to TOC

Section 5.1
Pressure
Pressure Conversions: An Example
The pressure of a gas is measured as 2.5 atm.

Represent this pressure in both torr and pascals.
 760 torr 
 2.5 atm     = 1.9  10 3
torr
 1 atm 
 101,325 Pa 
 2.5 atm     = 2.5  10 5
Pa
 1 atm 
Return to TOC

Section 5.2
The Gas Laws of Boyle, Charles, and Avogadro
Liquid Nitrogen and a Balloon
• What happened to the gas in the balloon?

• A decrease in temperature was followed by a decrease in
the volume of the balloon. Return to TOC

Section 5.2
Liquid Nitrogen and a Balloon
• This is an observation (a fact).
• It does NOT explain “why,” but it does tell us
“what happened.”
Volume and Temperature

• What law results from observations like these? 查理…
• The volume of a gas depends on the temperature of the

gas (constant P, pressure, and n, # of moles of gas).
Return to TOC

Section 5.2
Boyle’s Law
• Pressure and volume are inversely related
(constant T, temperature, and n, # of moles of
gas).
• PV = k (k is a constant for a given sample of air
at a specific temperature)
P1  V1 = P2  V2
Return to TOC

Section 5.2
Boyle’s Law
Return to TOC

Section 5.2
EX. Sulfur dioxide (SO2), a gas that plays a central role in the formation of acid
rain, is found in the exhaust of automobiles and power plants. Consider a 1.53-
L sample of gaseous SO2 at a pressure of 5.6 × 10³ Pa. If the pressure is
changed to 1.5 × 104 Pa at a constant temperature, what will be the new volume
of the gas?
As pressure increases, the volume of SO2

decreases.
Boyle’s law also can be written as

P1V1 = P2V2
0.571 L Return to TOC

Section 5.2
Exercise
A sample of helium gas occupies 12.4 L at 23°C

and 0.956 atm. What volume will it occupy at
1.20 atm assuming that the temperature stays
constant?
9.88 L
Return to TOC

Section 5.2
Charles’s Law
• Volume and Temperature (in Kelvin) are
directly related (constant P and n).
• V=bT (b is a proportionality constant)
• K = °C + 273
• 0 K is called absolute zero.
V1 V2
=
T1 T2
Return to TOC

Section 5.2
Plots of V versus T (℃) for several

gases. The solid lines represent
experimental measurements on
gases. The dashed lines represent
extrapolation of the data into
regions where these gases would
become liquids or solids. Note that
the samples of the various gases
contain different numbers of
moles.
Return to TOC

Section 5.2
Charles’s Law
Return to TOC

Section 5.2
Exercise
Suppose a balloon containing 1.30 L of air at 24.7°C is
placed into a beaker containing liquid nitrogen at
–78.5°C. What will the volume of the sample of air
become (at constant pressure)?
V1 V2
=
T1 T2 0.849 L
Return to TOC

Section 5.2
Avogadro’s Law
• Volume and number of moles are directly
related (constant T and P).
• V = an (a is a proportionality constant)
n1 n2
=
V1 V2
Return to TOC

Section 5.2
Exercise
If 2.45 mol of argon gas occupies a volume of

89.0 L, what volume will 2.10 mol of argon
occupy under the same conditions of
temperature and pressure?
76.3 L
Return to TOC

Section 5.3
The Ideal Gas Law
• We can bring all of these laws together into

one comprehensive law:
V = bT (constant P and n) Émile Clapeyron

V = an (constant T and P) (1834)
V = k/P (constant T and n)
PV = nRT
(where R = 0.08206 L·atm/mol·K, the
universal gas constant)
Return to TOC

Section 5.3
The Ideal Gas Law
Example. A sample of hydrogen gas (H2) has a volume of 8.56 L

at a temperature of 0℃ and a pressure of 1.5 atm. Calculate the
moles of H2 molecules present in this gas sample.
Solution
Solving the ideal gas law for n gives
PV = nRT
In this case P ＝ 1.5 atm, V = 8.56 L, T = 0℃ ＋ 273 ＝ 273 K,

and R ＝ 0.08206 L ･ atm/K･ mol. Thus
Return to TOC

Section 5.3
The Ideal Gas Law
The reaction of zinc with

hydrochloric acid to produce
bubble of hydrogen gas.
Return to TOC

Section 5.3
The Ideal Gas Law
Example. Suppose we have a sample of ammonia gas with a

volume of 7.0 mL at a pressure of 1.68 atm. The gas is
compressed to a volume of 2.7 mL at a constant temperature.
Use the ideal gas law to calculate the final pressure.
Solution
We always place the variables that change on one side of the
equals sign and the constants on the other.
Return to TOC

Section 5.3
The Ideal Gas Law
Sample Exercise 5.7
In this
Since n and T remain the same in this case, we can write

P1V1 ＝ nRT and P2V2 ＝ nRT.
Reality Check: The volume decreased (at constant

temperature), so the pressure should increase, as the
result of the calculation indicates.
Return to TOC

Section 5.3
The Ideal Gas Law
As pressure increases, the

volume decreases.
Return to TOC

Section 5.3
The Ideal Gas Law
Exercise
An automobile tire at 23°C with an internal

volume of 25.0 L is filled with air to a total
pressure of 3.18 atm. Determine the number
of moles of air in the tire.
3.27 mol
Return to TOC

Section 5.3
The Ideal Gas Law
Exercise
What is the pressure in a 304.0 L tank that

contains 5.670 kg of helium at 25°C?
114 atm
Return to TOC

Section 5.3
The Ideal Gas Law
Exercise
At what temperature (in °C) does 121 mL of

CO2 at 27°C and 1.05 atm occupy a volume of
293 mL at a pressure of 1.40 atm?
696°C
Return to TOC

Section 5.4
Gas Stoichiometry
Molar Volume of an Ideal Gas

• For 1 mole of an ideal gas at 0°C and 1 atm, the
volume of the gas is 22.42 L.
V=
nRT
=
1.000 mol 0.08206 L  atm/K  mol 273.2 K  = 22.42 L
P 1.000 atm
• STP = standard temperature and pressure

 0°C and 1 atm
 Therefore, the molar volume is 22.42 L at STP.
 Regardless the identity
Return to TOC

Section 5.4
Gas Stoichiometry
Molar Volumes for Various Gases at STP condition
Return to TOC

Section 5.4
Gas Stoichiometry
Example. Quicklime (CaO) is produced by the thermal

decomposition of calcium carbonate (CaCO3). Calculate the
volume of CO2 at STP produced from the decomposition of
152 g CaCO3 by the reaction
Solution
Thus the decomposition of 152 g CaCO3 produces 34.1 L
CO2 at STP.
Return to TOC

Section 5.4
Gas Stoichiometry
Exercise
A sample of oxygen gas has a volume of

2.50 L at STP. How many grams of O2
are present?
3.57 g
Return to TOC

Section 5.4
Gas Stoichiometry
Molar Mass of Gas

One very important use of the ideal gas law is in the
calculation of the molar mass (molecular weight) of a
gas from its measured density.
Grams of gas mass m
n＝＝＝
molar mass molar mass molar mass
Substitution into the udeal gas equation gives.
P ＝ nRT ＝ (m/molar mass)RT ＝ m(RT)

V V V(molar mass)
Return to TOC

Section 5.4
Gas Stoichiometry
Molar Mass of a Gas

 g   L  atm 
  
dRT  L   mol  K   K
g
Molar mass = = =
P  atm  mol
 d = density of gas
 T = temperature in Kelvin
 P = pressure of gas
 R = universal gas constant
Return to TOC

Section 5.4
Gas Stoichiometry
Exercise
What is the density of F2 at STP (in g/L)?
1.70 g/L
Return to TOC

Section 5.5
Dalton’s Law of Partial Pressures
吞哥的分壓定律
• For a mixture of gases in a container,
PTotal = P1 + P2 + P3 + . . .
• The total pressure exerted is the sum of the
pressures that each gas would exert if it were
alone.
Return to TOC

Section 5.5
The partial pressure of each gas in a mixture of gases in a container

depends on the number of moles of that gas. The total pressure is the
sum of the partial pressures and depends on the total moles of gas
particles present, no matter what they are.
Return to TOC

Section 5.5
The symbols P1, P2, P3, and so on represent each partial

pressure.
n1RT n RT n RT
PTOTAL＝ P1 ＋ P2 ＋ P3 ＋･･･＝＋ 2 ＋ 3 ＋･･･
V V V
RT
＝(n1＋ n2＋n3＋･･･) ( V
)
Where n TOTAL is the sum of the numbers of moles of the
various gases.
Return to TOC

Section 5.5
mole fraction: the ratio of the number of moles of a

given component in a mixture to the total number of moles
in the mixture.
The mole fraction X1 is
n1 n1
X1 ＝ n TOTAL ＝ n1＋ n2＋n3＋･･･
Return to TOC

Section 5.5
Mole Fraction can be Displayed by Pressure

V
n＝ P ( )
RT
V V
n1 ＝ P1 ( RT
), n2 ＝ P2 ( RT
)
n1
n1 P1(V/RT)
X1 ＝ n TOTAL ＝
P1(V/RT)＋ P2(V/RT) ＋ P3(V/RT) ＋･･･
n1 n2 n3
P1
＝ P
TOTAL
Return to TOC

Section 5.5
Collecting a Gas over Water
The production of oxygen by thermal decomposition of KClO3.

The MnO2 is mixed with the KClO3 to make the reaction faster.
Return to TOC

Section 5.5
Example. A sample of solid potassium chlorate (KClO3) was

heated in a test tube and decomposed by the following reaction:
2KClO3(s) 2KCl(s) ＋ 3O2(g)
The oxygen produced was collected by displacement of water
at 22℃ at a total pressure of 754 torr. The volume of the gas
collected was 0.650 L, and the vapor pressure of water at 22℃
is 21 torr. Calculate the partial pressure of O2 in the gas
collected and the mass of KClO3 in the sample that was
decomposed.
Return to TOC

Section 5.5
Solution
First we find the partial pressure of O2 from Dalton’s law of
partial pressure:
Thus
=0.964 atm
A mole ratio of 2 mol KClO3/3 mol O2. the moles of KClO3

can be calculated as follows:
Return to TOC

Section 5.5
Sample Exercise 5.18
Thus
A mole ratio of 2 mol KClO3/3 mol O2. The moles of

KClO3 can be calculated as follows:
Return to TOC

Section 5.5
Exercise
Consider the following apparatus containing helium in

both sides at 45°C. Initially the valve is closed.
•After the valve is opened, what is the pressure of the
helium gas?
2.00 atm
3.00 atm
9.00 L
3.00 L
Return to TOC

Section 5.5
Exercise
27.4 L of oxygen gas at 25.0°C and 1.30 atm, and

8.50 L of helium gas at 25.0°C and 2.00 atm were
pumped into a tank with a volume of 5.81 L at 25°C.
• Calculate the new partial pressure of oxygen.
6.13 atm
• Calculate the new partial pressure of helium.
2.93 atm
• Calculate the new total pressure of both gases.
9.06 atm
Return to TOC

Section 5.5
重點整理
Return to TOC

Section 5.6
The Kinetic Molecular Theory of Gases
學習目標
1. 了解氣體動力學的內涵以及如何用氣體動力學
推導出PV=nRT
2. 了解氣體的一些行為(擴散、逸散)以及衍生出來
的一些計算
3. 了解理想氣體與真實氣體行為的差異
Return to TOC

Section 5.6
氣體動力學
• So far we have considered “what happens,” but not

“why.”
• In science, “what” always comes before “why.”
Return to TOC

Section 5.6
假設
Postulates of the Kinetic Molecular Theory (KMT)
1) The particles are so small compared with the
distances between them that the volume of
the individual particles can be assumed to be
negligible (zero).
2) The particles are in constant motion. The

collisions of the particles with the walls of
the container are the cause of the pressure
exerted by the gas.
August Krönig (1856)  Rudolf Clausius (1857) Return to TOC

Section 5.6
Postulates of the Kinetic Molecular Theory

3) The particles are assumed to exert no forces
on each other; they are assumed neither to
attract nor to repel each other.
4) The average kinetic energy of a collection

of gas particles is assumed to be directly
proportional to the Kelvin temperature
of the gas.
Return to TOC

Section 5.6
V = bT (constant P and n; Charles)
Kinetic Molecular Theory V = an (constant T and P; Avogadro)
V = P-1k (constant T and n; Boyle)
Return to TOC

Section 5.6
V = bT (constant P and n; Charles)
Kinetic Molecular Theory V = an (constant T and P; Avogadro)
V = P-1k (constant T and n; Boyle)
Return to TOC

Section 5.6
Deriving the Ideal Gas Law
By applying the principles of physics to the assumptions
of the KMT, we can in effect derive the ideal gas law.
*課本附錄2有
推導這個式子
(A14-A17)
In brief: P=F/A
where P is the pressure of the gas, n is the number of

moles of gas, NA is Avogadro’s number, m is the mass of
each particle, u2 is the average of the square of the
velocities of the particles, and V is the volume of the
container. Return to TOC

Section 5.6
(KE)avg ＝ NA(½mu2)
The fourth postulate of the kinetic molecular theory is

that the average kinetic energy of the particles in the gas
sample is directly proportional to the temperature in
Kelvins.
Return to TOC

Section 5.6
Sine (KE)avg ∝ T
Note that this expression has been derived from the

assumptions of the kinetic molecular theory.
PV
＝ RT From experiment
n
PV
∝T From theory
n
Return to TOC

Section 5.6
Kinetic Molecular Theory
Return to TOC

Section 5.6
Concept Check
You are holding two balloons

of the same volume. One He
contains helium, and one
contains hydrogen. Complete H2
each of the following
statements with “different” or
“the same” and be prepared to
justify your answer.
Return to TOC

Section 5.6
Concept Check
1. The pressures of the gas in the two

balloons are __________. He
2. The temperatures of the gas in the
two balloons are __________. H2
3. The numbers of moles of the gas in
the two balloons are __________.
4. The densities of the gas in the two
balloons are __________.
Return to TOC

Section 5.6
Concept Check
VNe = 2VAr Ne
Which of the following best represents
the mass ratio of Ne(20.18):Ar(39.95)
in the balloons? Ar
1:1
1:2
2:1
1:3
3:1
Return to TOC

Section 5.6
Concept Check
• You have a sample of

nitrogen gas (N2) in a
container fitted with a
piston that maintains a
pressure of 6.00 atm.
Initially, the gas is at 45C
in a volume of 6.00 L.
• You then cool the gas
PV=nRT sample.
Return to TOC

Section 5.6
Concept Check
Which best explains the final result that occurs

once the gas sample has cooled?
a) The pressure of the gas increases.

b) The volume of the gas increases.
c) The pressure of the gas decreases.
d) The volume of the gas decreases.
e) Both volume and pressure change.
Return to TOC

Section 5.6
Concept Check
The gas sample is then cooled to a

temperature of 15C. Solve for the
new condition.
(Hint: A moveable piston keeps the
pressure constant overall, so what
condition will change?)
5.43 L
Return to TOC

Section 5.6
The Meaning of Temperature
The exact relationship between temperature and
average kinetic energy can be obtained by combining
the equations:
PV 2
n
＝ RT ＝ 3 (KE)avg
3
(KE)avg ＝ RT
2
The meaning of the Kelvin temperature of a gas:
The Kelvin temperature is an index of the random
motions of the particles of a gas, with higher
temperature meaning greater motion. Return to TOC

Section 5.6
Root Mean Square Velocity
The square root of u2 is called the root mean square
velocity and is symbolized by urms:
urms ＝ u2
3
(KE)avg ＝ NA and (KE)avg ＝ RT
(½mu2)
2
3 3RT
NA(½mu ) ＝ 2 RT or u ＝ N m
2 2
A
3RT m: mass per particle

u2 ＝ urms ＝ NA: Avogadro’s number
NAm
R ＝ 0.08206 L･atm/K･mol Return to TOC

Section 5.6
Root Mean Square Velocity

3RT
urms =
M
R = 8.3145 J/K·mol
(J = joule = kg·m2/s2)
T = temperature of gas (in K)
M = mass of a mole of gas in kg
*越熱跑越快、越胖跑越慢
• Final units are in m/s.
Return to TOC

Section 5.7
Effusion and Diffusion
Behaviors of Gases
• Diffusion – the mixing of gases. 擴散
• Effusion – describes the passage of a gas

through a tiny orifice into an evacuated
chamber. 逸散
• Rate of effusion measures the speed at which

the gas is transferred into the chamber.
Return to TOC

Section 5.7
Diffusion
Return to TOC

Section 5.7
Effusion
Return to TOC

Section 5.7
Graham’s Law of Effusion
Rate of effusion for gas 1 M2


Rate of effusion for gas 2 M1
• M1 and M2 represent the molar masses of the

gases.
*
Return to TOC

Section 5.7
Example. Calculate the root mean square velocity for the

atoms in a sample of helium gas at 25℃.
Solution
The formula for root mean square velocity is
T ＝ 25℃ ＋ 273 = 298 K, R ＝ 8.3145 J/K･ mol, and
Return to TOC

Section 5.8
Real Gases
理想是美麗的，現實是殘酷的
• We must correct for non-ideal gas behavior
when:
– Pressure of the gas is high.
– Temperature is low.
• Under these conditions:

– Concentration of gas particles is high.
– Attractive forces become important.
Return to TOC

Section 5.8
Real Gases
Plots of PV/nRT Versus P for Several Gases
(200 K)
Return to TOC

Section 5.8
Real Gases
Plots of PV/nRT Versus P for Nitrogen Gas at
Three Temperatures
Return to TOC

Section 5.8
Real Gases
Real Gases (van der Waals Equation)
[ Pobs  a (n / V ) ]  V  nb  nRT 2
 
corrected pressure corrected volume
Pideal Videal
非理想氣體會因為分子非理想氣體其實有體積
間作用力導致壓力較理
想氣體低
Return to TOC

Section 5.9
Characteristics of Several Real Gases
• For a real gas, the actual observed pressure is

lower than the pressure expected for an ideal
gas due to the intermolecular attractions that
occur in real gases.
Return to TOC

Section 5.9
Characteristics of Several Real Gases
Values of the van der Waals Constants for
Some Gases
• The value of a reflects

how much of a correction
must be made to adjust the
observed pressure up to
the expected ideal pressure.
• A low value for a reflects

weak intermolecular forces
among the gas molecules.
Return to TOC

Section 5.10
Chemistry in the Atmosphere
Air Pollution
• Two main sources:
 Transportation
 Production of electricity
• Combustion of petroleum produces CO, CO2,

NO, and NO2, along with unburned molecules
from petroleum.
Return to TOC

Section 5.10
Nitrogen Oxides (Due to Cars and Trucks)

• At high temperatures, N2 and O2 react to
form NO, which oxidizes to NO2.
• The NO2 breaks up into nitric oxide and
free oxygen atoms.
• Oxygen atoms combine with O2 to form
ozone (O3).
Radiant
NO2 (g ) 
 NO(g )  O(g )
energy
O(g )  O2 (g ) 
 O3 ( g )
Return to TOC

Section 5.10
Concentration for Some Smog Components vs.

Time of Day
Return to TOC

Section 5.10
Sulfur Oxides (Due to Burning Coal for Electricity)

• Sulfur produces SO2 when burned.
• SO2 oxidizes into SO3, which combines with
water droplets in the air to form sulfuric acid.
S(in coal)  O2 ( g ) 
 SO2 ( g )
2SO2 ( g )  O2 ( g ) 
 2SO3 ( g )
SO3 (g )  H2O(l ) 
 H2SO 4 (aq )
Return to TOC

Section 5.10
Sulfur Oxides (Due to Burning Coal for Electricity)

• Sulfuric acid is very corrosive and produces
acid rain.
• Use of a scrubber (滌塵器) removes SO2 from
the exhaust gas when burning coal.
Return to TOC

Section 5.10
重點整理
Return to TOC

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Chapter 5

Copyright © Cengage Learning. All rights reserved 2

Why Study Gases?

Although relatively few substances exist in

• An understanding of real world phenomena.

Copyright © Cengage Learning. All rights reserved 3

Copyright © Cengage Learning. All rights reserved 4

Copyright © Cengage Learning. All rights reserved 6

Because instruments used for measuring pressure, such as

1 standard atmosphere = 1 atm = 760 mm Hg = 760 torr

Copyright © Cengage Learning. All rights reserved

Copyright © Cengage Learning. All rights reserved

Copyright © Cengage Learning. All rights reserved 9

Pressure Conversions: An Example

The pressure of a gas is measured as 2.5 atm.

Copyright © Cengage Learning. All rights reserved 10

• What happened to the gas in the balloon?

Copyright © Cengage Learning. All rights reserved 11

Volume and Temperature

• The volume of a gas depends on the temperature of the

Copyright © Cengage Learning. All rights reserved 12

Copyright © Cengage Learning. All rights reserved 13

Copyright © Cengage Learning. All rights reserved 14

As pressure increases, the volume of SO2

Boyle’s law also can be written as

0.571 L Return to TOC

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A sample of helium gas occupies 12.4 L at 23°C

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Plots of V versus T (℃) for several

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If 2.45 mol of argon gas occupies a volume of

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• We can bring all of these laws together into

V = bT (constant P and n) Émile Clapeyron

V = k/P (constant T and n)

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Example. A sample of hydrogen gas (H2) has a volume of 8.56 L

In this case P ＝ 1.5 atm, V = 8.56 L, T = 0℃ ＋ 273 ＝ 273 K,

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The reaction of zinc with

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Example. Suppose we have a sample of ammonia gas with a

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Since n and T remain the same in this case, we can write

Reality Check: The volume decreased (at constant

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As pressure increases, the

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An automobile tire at 23°C with an internal

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What is the pressure in a 304.0 L tank that

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At what temperature (in °C) does 121 mL of

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Molar Volume of an Ideal Gas

• STP = standard temperature and pressure

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Molar Volumes for Various Gases at STP condition

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