Chapter 10

Gases

10.1 Characteristics of Gases

10.2 Pressure
10.3 The Gas Laws
10.4 The Ideal-Gas Equation
10.5 Further Applications of the Ideal-Gas Equation
10.6 Gas Mixtures and Partial Pressures
10.7 The Kinetic-Molecular Theory of Gases
10.8 Molecular Effusion and Diffusion
10.9 Real Gases: Deviations from Ideal Behavior
Lecture Goal
• The implication of gas pressure (P)

• Understanding how the gas properties are interrelated

each others:

• The ideal behavior of gas molecules

• Energy of gas molecules

▪ The kinetic-molecular theory

• Non-ideal behavior of gas molecules

2
10.1 Characteristics of Gases

• At ordinary temperatures and pressures, the gaseous

elements are
▪ Either monatomic (He, Ne, Ar, …) or diatomic (H2, N2, O2, …)

3
10.1 Characteristics of Gases

• Many molecule compounds are gaseous

▪ All of these gases are composed entirely of nonmetallic elements

▪ Simple molecular formulas with low molar masses

• Vapor
▪ Gaseous state of substances that are liquid or solids under
ordinary conditions

4
10.1 Characteristics of Gases

• Characteristics of gases
▪ Different gaseous substances may have very different chemical
properties

▪ They behave quite similarly as far as their physical properties are

concerned

▪ For example, N2 and O2 have very different chemical properties

but these two components of air behave physically as one
gaseous material

5
10.1 Characteristics of Gases

• Physical characteristics of gases

▪ Differ significantly from those of solids and liquids

▪ Gas expands spontaneously and are highly compressible

▪ Two or more gases form a homogeneous mixture regardless of the

identities or relative proportions of the gases (e.g., atmosphere)

▪ The physical characteristics of gases arise because the molecules

are relative far apart

6
10.2 Pressure

• Pressure
▪ The gaseous molecules move chaotically (무질서하게) and collide
with each other and walls of their container

▪ The force with which the gas pushes the wall outward

▪ Gas exert a pressure on any surface with which they are in contact

▪ Pressure (P) is defined as the force (F) divided by the surface area
(A)

𝐹 𝑁
𝑃= 1 𝑁 = 1 𝑘𝑔 ∙ 𝑚Τ𝑠 2
𝐴 𝑚2

7
Atmospheric Pressure and the Barometer

• Atmospheric pressure (대기압)

▪ Gravitational force causes the gaseous atoms and molecules in the
atmosphere to press down on the Earth’s surface

▪ Atmospheric pressure is defined as the force exerted by the

atmosphere on a given surface area

➢ 𝐹 = 10,000 𝑘𝑔 9.8 𝑚Τ𝑠 2 = 1 × 105 𝑁

𝐹 1×105 𝑁
➢𝑃 = 𝐴
= 1 𝑚2
= 1 × 105 𝑁Τ𝑚2

= 1 × 105 𝑃𝑎 = 1 × 102 𝑘𝑃𝑎

Figure 10.1 Calculating

atmospheric pressure.8
Atmospheric Pressure and the Barometer

• Unit of pressure
▪ SI unit of pressure is the pascal (Pa), 1 Pa = 1 N/m2

▪ Related pressures units

➢ Bar : 1 bar = 102 kPa = 105 Pa = 105 N/m2

➢ Pounds per square inch (psi, lbs/in.2)

At sea level, atmospheric pressure is 14.7 psi

9
Atmospheric Pressure and the Barometer

• Barometer
▪ Evangelista Torricelli (1608 – 1647) invented the mercury barometer

▪ The height, h, of the mercury column is a measure of atmospheric

pressure and changes as atmospheric pressure changes

Figure 10.2 A mercury barometer. 10

Atmospheric Pressure and the Barometer

• Standard atmospheric pressure (표준 대기압)

▪ The pressure sufficient to support a column of mercury 760 mm high
at sea level

▪ In SI units, this pressure is 1.01325 × 105 Pa

▪ Non-SI units (e.g., atm, mmHg, torr, …)

1 atm = 760. mmHg = 760. torr = 1.01325 × 105 Pa = 101.325 kPa

= 1.01325 bar

11
Atmospheric Pressure and the Barometer

Sample Exercise 10.1

▪ What is the pressure, in kilopascals, on the body of a diver if she is
31.0 m below the surface of the water when the atmospheric
pressure on the surface is 98 kPa? Assume that the density of the
water is 1.00 g/cm3 = 1.00 × 103 kg/m3. The gravitational constant is
9.81 m/s2, and 1 Pa = 1 kg/m-s2.

𝐹 𝑚𝑔 𝑑𝑉𝑔 𝑑 𝐴ℎ 𝑔
𝑃= = = = = 𝑑ℎ𝑔
𝐴 𝐴 𝐴 𝐴

𝑑 = density of the water;

𝑉 = Volume of the water column; 38 m
𝐴 = Cross-sectional area;
ℎ = Height
12
Atmospheric Pressure and the Barometer

Sample Exercise 10.1

𝑃𝑤𝑎𝑡𝑒𝑟 = 𝑑ℎ𝑔 = 1.00 × 103 𝑘𝑔/𝑚3 31.0 𝑚 9.81 𝑚/𝑠 2

= 304,110 𝑘𝑔Τ𝑚 ∙ 𝑠 2 = 3.04110 × 105 𝑃𝑎 = 304.110 𝑘𝑃𝑎

𝑃𝑡𝑜𝑡𝑎𝑙 = 98 𝑘𝑃𝑎 + 304.110 𝑘𝑃𝑎 = 402 𝑘𝑃𝑎

13
Atmospheric Pressure and the Barometer

Sample Exercise 10.2

▪ On a certain day, a laboratory barometer indicates that the
atmospheric pressure is 764.7 torr. A sample of gas is placed in a
flask attached to an open-end mercury manometer, and a meter stick
is used to measure the height of the mercury in the two arms of the U
tube. The height of the mercury in the open-ended arm is 136.4 mm,
and the height in the arm in contact with the gas in the flask is 103.8
mm. What is the pressure of the gas in the flask (a) in atmospheres,
(b) in kilopascals?

14
Atmospheric Pressure and the Barometer

Sample Exercise 10.2

• Pgas = Patm, the Hg levels are equal

• Pgas > Patm, the Hg level in the arm on

the flask side is lower than the level
in the arm open to the atmosphere

• Pgas < Patm, the Hg level in the arm on

the flask side is higher than the level
in the arm open to the atmosphere

• The height difference (h) measures

the pressure difference the gas and
the atmosphere

Figure 10.3 A mercury manometer. 15

Atmospheric Pressure and the Barometer

Sample Exercise 10.2

Pgas = Patm + h

= 764.7 torr + (136.4 torr – 103.8 torr)

= 797.3 torr

(a) In atmosphere, 1 atm = 760. mmHg = 760. torr

1 𝑎𝑡𝑚
797.3 𝑡𝑜𝑟𝑟 × 760.𝑡𝑜𝑟𝑟 = 1.049 𝑎𝑡𝑚 = 1.05 atm

(b) In kilopascals, 1 atm = 101.3 kPa

101.3 𝑘𝑃𝑎
1.049 𝑎𝑡𝑚 × = 106.3 𝑘𝑃𝑎 = 106 kPa
1 𝑎𝑡𝑚

16
10.3 The Gas Laws

• Gaseous physical condition, or state, can be defined by the

four variables
▪ Temperature

▪ Pressure

▪ Volume

▪ Amount of gas (number of moles)

• Gas laws are the equations that express the relationships

among these four variables

17
The Pressure – Volume Relationship: Boyle’s law

• Boyle’s law
▪ Gas volume increases as the pressure exerted on the gas decreases

▪ Robert Boyle (1627 – 1691), British chemist,

investigated the quantitative relationship
between the pressure of a gas and its volume

▪ The volume of a fixed quantity of gas

maintained at constant temperature is
inversely proportional to the pressure

1
𝑉 = constant ×
𝑃
or 𝑃𝑉 = constant Figure 10.4 As a balloon rises in the
18
atmosphere, its volume increases.
The Pressure – Volume Relationship: Boyle’s law

• Boyle’s law

Figure 10.5 Boyle’s Law. For a fixed quantity of gas at constant temperature,
the volume of the gas is inversely proportional to its pressure

19
The Temperature – Volume Relationship: Charles’s Law

• Charles’s law
▪ The volume of a balloon increases with increasing the gas
temperature

▪ Jacques Charles (1746 – 1823), French scientist

discovered the relationship between gas volume
and temperature

▪ The volume of a fixed amount of gas

maintained at constant pressure is
directly proportional to its absolute temperature
𝑉 Figure 10.6 The effect of
𝑉 = constant × 𝑇 or = constant
𝑇 temperature on volume.
20
The Temperature – Volume Relationship: Charles’s Law

• Charles’s law
▪ Data between volume and temperature are extrapolated through
-273 oC

▪ The volume at -273 oC is predicted to zero,

however, this condition is never realized,
because all gases liquefy or solidify before
reaching this temperature

▪ Absolute zero (0 K) equals -273.15 oC

Figure 10.7 Charles’s Law.

21
The Quantity – Volume Relationship: Avogadro’s Law

• Law of combining volumes

▪ Gay-Lussac observed the law of combining volumes

▪ At a given pressure and temperature, the volumes of gases that

react with one another are in the ratios of small whole numbers

▪ Two volumes of H2 gas react with one volume of O2 gas to form two
volumes of H2O vapor.

22
The Quantity – Volume Relationship: Avogadro’s Law

• Avogadro’s law
▪ Avogadro’s hypothesis : Equal volumes of gases at the same
temperature and pressure contain equal numbers of molecules

Figure 10.8 Avogadro’s hypothesis.

At the same volume, pressure, and
temperature, samples of different gases
have the same number of molecules but
different masses.
▪ Avogadro’s law : The volume of a gas maintained at constant
temperature and pressure is directly proportional to the number of
𝑉
moles of the gas (𝑉 = constant × 𝑛 or = constant) 23
𝑛
10.4 The Ideal-Gas Equation

• Relationships among the four variables (P, V, T, and n)

1
▪ Boyle’s law: 𝑉∝ (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑛, 𝑇)
𝑃

▪ Charles’s law: 𝑉 ∝ 𝑇 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑛, 𝑃)

▪ Avogadro’s law: 𝑉 ∝ 𝑛 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃, 𝑇)

▪ We can combine these relationships into a general gas law:

𝑛𝑇
𝑉∝
𝑃
𝑷𝑽 = 𝒏𝑹𝑻 (Ideal-gas equation)

24
10.4 The Ideal-Gas Equation

• Ideal-gas
▪ Hypothetical gas whose pressure, volume, and temperature
relationships are described completely by the ideal-gas equation

▪ Assumptions

➢ The molecules of an ideal gas do not interact with one another,

➢ The combined volume of the molecules is much smaller than the

volume the gas occupies

25
10.4 The Ideal-Gas Equation

• Gas constant
▪ The term R in the ideal-gas equation

▪ You must choose the form of R in which the units agree with the
units of P, V, n, and T given in the problem

• Standard temperature and pressure (STP)

▪ The conditions of 0 oC and 101.325 kPa

▪ Molar volume (volume occupied by 1.000 mol) of ideal gas at STP

𝑛𝑅𝑇 1.000 𝑚𝑜𝑙 8.314 𝑚3 ∙ 𝑃𝑎Τ𝑚𝑜𝑙 ∙ 𝐾

𝑉= = = 22.41 𝐿
𝑃 101.325 × 103 𝑃𝑎

26
10.4 The Ideal-Gas Equation

• Ideal gas vs. real gas

▪ Ideal-gas equation accounts adequately for the properties of most
gases under a variety of circumstances

▪ The equation is not exactly correct for any real gas

▪ However, the real gas behavior differs so little from ideal behavior
that we can ignore any deviations

Figure 10.9 Comparison of molar

volumes at STP.
27
10.4 The Ideal-Gas Equation

Sample Exercise 10.4 [Page 449]

▪ Calcium carbonate, CaCO3(s), the principal compound in limestone,
decomposes upon heating to CaO(s) and CO2(g). A sample of
CaCO3 is decomposed, and the carbon dioxide is collected in a
250.-mL flask. After decomposition is complete, the gas has a
pressure of 131.72 kPa at a temperature of 31 oC. How many moles
of CO2 gas were generated?

28
10.4 The Ideal-Gas Equation

Sample Exercise 10.4 [Page 449]

𝑃𝑉
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑛 =
𝑅𝑇

𝑉 = 250. 𝑚𝐿 = 0.250 𝐿 = 2.50 × 10−4 𝑚3

𝑃 = 131.72 𝑘𝑃𝑎 = 131.72 × 103 𝑃𝑎
𝑇 = 31 ℃ = 31 + 273 𝐾 = 304 𝐾

131.72 × 103 𝑃𝑎 2.50 × 10−4 𝑚3

𝑛= = 0.0130 𝑚𝑜𝑙 𝐶𝑂2
8.314 𝑚3 ∙ 𝑃𝑎Τ𝑚𝑜𝑙 ∙ 𝐾 304 𝐾

29
Relating the Ideal-Gas Equation and the Gas Laws

• If n and T are constant,

▪ 𝑃𝑉 = 𝑛𝑅𝑇 = constant

▪ The values of 𝑃 and 𝑉 can change, but the product 𝑃𝑉 must remain
constant
𝑃1 𝑉1 = 𝑃2 𝑉2

▪ If a cylinder fitted with a movable piston holds 50.0 L of O2 gas at

1.875 MPa and 21 oC, what volume will the gas occupy if the
temperature is maintained at 21 oC while the pressure is reduced to
101.3 kPa?

𝑃1 1.875 × 103 𝑘𝑃𝑎

𝑉2 = 𝑉1 × = 50.0 𝐿 = 925 𝐿
𝑃2 101.3 𝑘𝑃𝑎
30
Relating the Ideal-Gas Equation and the Gas Laws

• Combined gas law

▪ We can derive relationships between any other two variables,
𝑉 and 𝑇 (Charles’s law), 𝑛 and 𝑉 (Avogadro’s law), or 𝑃 and 𝑇.
𝑃𝑉
▪ = 𝑛𝑅 = constant
𝑇

𝑃1 𝑉1 𝑃2 𝑉2
▪ =
𝑇1 𝑇2

31
Relating the Ideal-Gas Equation and the Gas Laws

Sample Exercise 10.5 [Page 450]

▪ The gas pressure in an aerosol can is 152 kPa at 25 oC. Assuming
that the gas obeys the ideal-gas equation, what is the pressure when
the can is heated to 450. oC?

V and n are constant

P T
𝑃 𝑛𝑅
𝑃𝑉 = 𝑛𝑅𝑇 ⟶ = = constant
𝑇 𝑉 Initial 152 kPa 25 oC (298 K)
𝑃1 𝑃2 Final P2 450. oC (723 K)
=
𝑇1 𝑇2
𝑇2 723 𝐾
𝑃2 = × 𝑃1 = 152 𝑘𝑃𝑎 = 369 𝐿
𝑇1 298 𝐾
32
Relating the Ideal-Gas Equation and the Gas Laws

Sample Exercise 10.6 [Page 451]

▪ An inflated balloon has a volume of 6.0 L at sea level (101.3 kPa)
and is allowed to ascend until the pressure is 45.6 kPa. During
ascent, the temperature of the gas falls from 22 oC to -21 oC.
Calculate the volume of the balloon at its final altitude.

n is constant
P V T
𝑃𝑉 Initial 101.3 kPa 6.0 L 22 oC (295 K)
= 𝑛𝑅 = constant
𝑇 Final 45.6 kPa V2 -21 oC (252 K)
𝑃1 𝑉1 𝑃2 𝑉2
= 𝑃1 𝑇2 101.3 𝑘𝑃𝑎 252 𝐾
𝑇1 𝑇2 𝑉2 = 𝑉1 × × = 6.0 𝐿
𝑃2 𝑇1 45.6 𝑘𝑃𝑎 295 𝐾
= 11 𝐿
33
10.5 Further Applications of the Ideal-Gas Equation

• Defining the relationship between the density of a gas and

its molar mass using the ideal-gas equation

• Calculate the volume of gases formed or consumed in

chemical reaction

34
Gas Densities and Molar Mass

• Gas density
▪ Units of mass per unit volume (d = m/V)

𝑛 𝑃
=
𝑉 𝑅𝑇
𝑛 ∙ 𝑀𝑀 𝑃 ∙ 𝑀𝑀
=
𝑉 𝑅𝑇

𝑚𝑜𝑙𝑒𝑠 𝑔𝑟𝑎𝑚𝑠 𝑔𝑟𝑎𝑚𝑠

× = = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦(𝑑)
𝑙𝑖𝑡𝑒𝑟 𝑚𝑜𝑙𝑒 𝑙𝑖𝑡𝑒𝑟

𝑚 𝑛 ∙ 𝑀𝑀 𝑃 ∙ 𝑀𝑀 𝑑𝑅𝑇
𝑑= = = 𝑀𝑀 = =
𝑉 𝑉 𝑅𝑇 𝑃
35
Gas Densities and Molar Mass

• Density
▪ The density of a gas depends on its pressure, molar mass, and
temperature

➢ CO2 has a higher molar mass than N2 or O2 and is therefore denser

than air

➢ The hotter gas is less dense than the cooler one, so

the hotter gas rises

Figure 10.10 CO2 gas flows

downward because it is denser
36
than air.
Gas Densities and Molar Mass

Sample Exercise 10.8 [Page 452]

▪ A large evacuated flask initially has a mass of 134.567 g. When
the flask is filled with a gas of unknown molar mass to a pressure
of 97.99 kPa at 31 oC, its mass is 137.456 g. When the flask is
evacuated again and then filled with water at 31 oC, its mass is
1067.9 g. (The density of water at this temperature is 0.997 g/mL.)
Assuming the ideal-gas equation applies, calculate the molar mass
of the gas.
Unknown Water
gas
Evacuated
flask

Mass : 134.567 g Mass : 137.456 g Mass : 1067.9 g 37

P : 97.99 kPa T : 31 oC T : 31 oC
Gas Densities and Molar Mass

Sample Exercise 10.8 [Page 452]

Volume of flask (V) = Volume of water filled in the flask
𝑚𝑤𝑎𝑡𝑒𝑟 (1067.9 𝑔 − 134.567 𝑔) 933.33 𝑔
𝑉= = = = 936.1 𝑚𝐿
𝑑𝑤𝑎𝑡𝑒𝑟 0.997 𝑔Τ𝑚𝐿 0.997 𝑔/𝑚𝐿

= 0.9361 𝐿

𝑑𝑅𝑇 𝑚𝑔𝑎𝑠 𝑅𝑇
𝑀𝑀 = = ∙ 𝑚𝑔𝑎𝑠 = 137.456 − 134.567 𝑔 = 2.889 𝑔
𝑃 𝑉 𝑃

2.889 𝑔 8.314 𝑚3 ∙ 𝑃𝑎Τ𝑚𝑜𝑙 ∙ 𝐾 × 31 + 273 𝐾

𝑀𝑀 = ×
0.9361 × 10−3 𝑚3 97.99 × 103 𝑃𝑎

= 79.6 𝑔/𝑚𝑜𝑙
38
Volumes of Gases in Chemical Reactions

• Identify and/or quantity of a gas

▪ Calculate the volumes of gases consumed or produced in
reactions

▪ The coefficients in a balanced chemical equation tell us the

relative amounts (in moles) of reactants and products

▪ The ideal-gas equation relates the number of moles of a gas to 𝑃,

𝑉, and 𝑇

39
Volumes of Gases in Chemical Reactions

Sample Exercise 10.9 [Page 453]

▪ Automobile air bags are inflated by nitrogen gas generated by the
rapid decomposition of sodium azide, NaN3:
2 𝑁𝑎𝑁3 𝑠 ⟶ 2 𝑁𝑎 𝑠 + 3 𝑁2 (𝑔)
If an air bag has a volume of 36 L and is to be filled with nitrogen
gas at 116.5 kPa and 26 oC, how many grams of NaN3 must be
decomposed?

𝑃𝑉 116.5 × 103 𝑃𝑎 36 × 10−3 𝑚3

𝑛= = = 1.69 𝑚𝑜𝑙 𝑁2
𝑅𝑇 8.314 𝑚3 ∙ 𝑃𝑎Τ𝑚𝑜𝑙 ∙ 𝐾 26 + 273 𝐾

2 𝑚𝑜𝑙 𝑁𝑎𝑁3 65.0 𝑔 𝑁𝑎𝑁3

1.69 𝑚𝑜𝑙 𝑁2 × × = 73 𝑔 𝑁𝑎𝑁3
3 𝑚𝑜𝑙 𝑁2 𝑚𝑜𝑙 𝑁𝑎𝑁3
40
10.6 Gas Mixtures and Partial Pressures
• John Dalton observed that
▪ The total pressure of a mixture of gases equals the sum of the
partial pressures that each would exert if it were present alone

▪ Daltons’ law of partial pressures

: 𝑃𝑡 = 𝑃1 + 𝑃2 + 𝑃3 + ⋯

▪ If each gas obeys the ideal-gas equation

𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑃1 = 𝑛1 , 𝑃2 = 𝑛2 , 𝑃3 = 𝑛3
𝑉 𝑉 𝑉

𝑅𝑇 𝑅𝑇
𝑃𝑡 = 𝑛1 + 𝑛2 + 𝑛3 + ⋯ = 𝑛𝑡
𝑉 𝑉
41
Partial Pressures and Mole Fractions

• Partial pressure of gas 1

𝑃1 𝑛1 𝑅𝑇 Τ𝑉 𝑛1
▪ = =
𝑃𝑡 𝑛𝑡 𝑅𝑇 Τ𝑉 𝑛𝑡

▪ Mole fraction 𝑋 is a dimensionless number that express the ratio

of the number of moles of one component in a mixture to the total
number of moles in the mixture
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 1 𝑛1
𝑋1 = =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑛𝑡

𝑛1
▪ 𝑃1 = 𝑃𝑡 = 𝑋1 𝑃𝑡
𝑛𝑡

42
Partial Pressures and Mole Fractions

• Nitrogen molecules in air

▪ Mole fraction of N2 in air is 0.78

▪ That is, 78 % of the molecules in air are N2

▪ If the barometric pressure is 101.3 kPa, the partial pressure of N2

is
𝑃𝑁2 = 0.78 101.3 𝑘𝑃𝑎 = 79 𝑘𝑃𝑎

43
10.7 The Kinetic-Molecular Theory of Gases

• Ideal-gas equation describes how gases behave but not

why they behave as they do

• Kinetic-molecular theory of gases

▪ Rudolf Clausius (1822 – 1888) published this theory

▪ This model helps us understand what happens to gas particles

when pressure or temperature change

44
10.7 The Kinetic-Molecular Theory of Gases

• Kinetic-molecular theory of gases

1. Random motion
: Gases consist of large numbers of molecules that are in
continuous, random motion

2. Negligible molecular volume

: The combined volume of all the molecules of the gas is
negligible relative to the total volume in which the gas is
contained

3. Negligible forces
: Attractive and repulsive forces between gas molecules are
negligible
45
10.7 The Kinetic-Molecular Theory of Gases

• Kinetic-molecular theory of gases

4. Constant average kinetic energy
: Energy can be transferred between molecules during collision
but, as long as temperature remains constant, the average
kinetic energy of the molecules does not change with time

5. Average kinetic energy proportional to temperature

: The average kinetic energy of the molecules is
proportional to the absolute temperature. At any given
temperature, the molecules of all gases have the same average
kinetic energy

46
10.7 The Kinetic-Molecular Theory of Gases

• The kinetic-molecular theory explains both pressure and

temperature at the molecular level
▪ The pressure of a gas is caused by collisions of the molecules with
the walls of the container
(how often and how forcefully)

▪ The absolute temperature of a gas is a measure

of the average kinetic energy of its molecules

Figure 10.11 The molecular

47
origin of gas pressure.
Distributions of Molecular Speed

• Gas molecular speed

▪ The gas molecules have an average speed, but the individual
molecules are moving at different speeds

▪ At any instant, the molecules in the sample have a wide range of

speeds

Figure 10.12 Distribution of

molecular speeds for nitrogen gas.
(a) The effect of temperature on
molecular speed. (b) Position of
most probable (ump), average (uav),
and root-mean-square (urms)
48
speeds of gas molecules.
Distributions of Molecular Speed

• Gas molecular speed

▪ Gas samples at 100 oC move at the higher speeds, therefore, they
have the higher average kinetic energy

▪ Most probable speed (ump)

: the peak of the curve
- 4 × 102 m/s for the 0 oC sample
- 5 × 102 m/s for the 100 oC sample

49
Distributions of Molecular Speed

• Gas molecular speed

▪ Root-mean-square (rms) speed (urms)
: the speed of a molecule possessing a kinetic energy identical to
the average kinetic energy of the sample

▪ Average (mean) speed (uav)

▪ urms is not quite the same

as the uav, but the difference
between the two is small

▪ Average kinetic energy

1 2
= 𝑚 𝑢𝑟𝑚𝑠
2
50
Distributions of Molecular Speed

• Gas molecular speed

▪ The distribution curve broadens as we go to a higher temperature,
which tells us that the range of molecular speeds increases with
temperature

▪ Because mass does not change with temperature, the increase in

the average kinetic energy as the temperature increases implies
that the speed of the molecules (urms, ump, and uav) increases as
temperature increases

51
Application of Kinetic-Molecular Theory to the Gas Laws

• An increase in volume at constant temperature causes

pressure to decrease (Boyle’s law)
▪ At constant temperature, the rms speed of the molecules remains
unchanged, but the distance between molecules is increased

▪ There are fewer collisions per unit time with the container walls,
which means the pressure decrease

52
Application of Kinetic-Molecular Theory to the Gas Laws

• A temperature increase at constant volume causes

pressure to increase
▪ An increase in temperature means an increase in the average
kinetic energy of the molecules and in urms

▪ In the constant volume, the temperature increase causes more

collision with the walls per unit time

▪ A great number of more forceful collisions mean the pressure

increase

53
10.8 Molecular Effusion and Diffusion

• The average kinetic energy has a specific value at a given

temperature
▪ A gas composed of He has the same average kinetic energy as
one composed of Xe

▪ The mass of He is smaller than that of Xe

▪ Therefore, He particles must have a higher rms speed than the Xe

particles

3𝑅𝑇 2𝑅𝑇
𝑢𝑟𝑚𝑠 = 𝑢𝑚𝑝 =
𝑀𝑀 𝑀𝑀

54
10.8 Molecular Effusion and Diffusion

The slowest; 2𝑅𝑇

= the heaviest 𝑢𝑚𝑝 =
𝑀𝑀

The fastest
= the lightest

Figure 10.13 The effect of molar mass on molecular speed at 25 oC.

55
10.8 Molecular Effusion and Diffusion

• The dependence of molecular speed on mass causes

effusion and diffusion
▪ Effusion (유출) : Escape of gas molecules through a tiny hole

▪ Diffusion (확산) : Spread of gas molecules throughout a space or

throughout other substance

56
Graham’s Law of Effusion

• Graham’s Law
Figure 10.14 Effusion.
▪ Assume we have two gases at the same temperature and pressure
in two containers with identical pinholes

▪ The faster the molecules are moving, the more often they hit the
partition wall and the greater the likelihood that a molecule will
effuse

▪ It implies that the rate of effusion is directly proportional to the rms

speed of the molecules

𝑟1 , 𝑟2 ∶ effusion rate of gas 1 and gas 2

𝑟1 𝑢𝑟𝑚𝑠1 3𝑅𝑇Τ𝑀𝑀1 𝑀𝑀2
= = =
𝑟2 𝑢𝑟𝑚𝑠2 3𝑅𝑇Τ𝑀𝑀2 𝑀𝑀1 𝑀𝑀1 , 𝑀𝑀2 ∶ Molar mass of gas 1 and gas 2
57
Graham’s Law of Effusion

• Graham’s Law
▪ Helium escapes from containers through tiny pinhole leaks more
rapidly than other gases of higher molecular weight

Figure 10.15 An illustration of Graham’s law of effusion.

58
Diffusion and Mean Free Path

• Diffusion rate
▪ The rms speeds of molecules are quite high (N2 is 515 m/s at 25 oC)

▪ If someone opens a vial of perfume at one end of a room, some

time elapses before the scent is detected at the other end of the
room

▪ Diffusion rate of gases throughout a volume of space is much

slower than molecular speeds, due to molecular collisions, which
occur frequently for a gas at atmospheric pressure (about 1010
times per second for each molecule)

59
Diffusion and Mean Free Path

• Mean free path

▪ The direction of motion of a gas molecule is constantly changing

▪ The diffusion of a molecule consists of many short, straight-line

segments as collisions buffet it around in random directions

➢ Mean free path : average distance traveled by

a molecule between collisions

➢ At low pressure, a molecule has a long mean free

path

➢ At high pressure, a molecule has a short mean

free path
Figure 10.17 Diffusion of
a gas molecule. 60
10.9 Real Gases: Deviations from Ideal Behavior

• Real gas
▪ In the real world, the behavior of gases only conforms to the ideal-
gas equation at relatively high temperature and low pressure
𝑃𝑉
▪ Ideal-gas equation for 1 mol of gas : =1
𝑅𝑇

- At high pressure, the

deviation from ideal behavior
is large
- At low pressure, the deviation
from ideal behavior is small
1.013 MPa
Figure 10.18 The effect of pressure
on the behavior of several real gases.
61
10.9 Real Gases: Deviations from Ideal Behavior

• Real gas
▪ As temperature increases, the behavior of a real gas more nearly
approaches that of the ideal gas

▪ The deviation from ideal behavior is significant near the

temperature at which the gas liquefies

Figure 10.19 The effect of temperature and

pressure on the behavior of nitrogen gases.
62
10.9 Real Gases: Deviations from Ideal Behavior

• Two assumptions in the kinetic-molecular model

▪ Negligible volume of gas molecules themselves and

▪ No attractive forces between gas molecules

→ The assumptions break down at high P and/or low T

63
10.9 Real Gases: Deviations from Ideal Behavior

• Non-ideal kinetic-molecular behavior

▪ At high P, the unoccupied volume available to the molecules is
less than the container volume
→ gas volumes tend to be slightly greater than those predicted by
the ideal-gas equation

▪ At high P, the attractive forces between molecules come into play

at the short intermolecular distances
→ The attractions lessen the force with which the molecule hits the
wall, so the gas pressure is less than that of an ideal gas

▪ When the P is sufficiently high, the volume effects dominate, and

PV/RT increases to above the ideal value
64
10.9 Real Gases: Deviations from Ideal Behavior

• Non-ideal kinetic-molecular behavior

Figure 10.21 In any real gas, attractive

Figure 10.20 Gases behave more ideally
intermolecular forces reduce pressure to
at low pressure than at high pressure.
values lower than in an ideal gas. 65
10.9 Real Gases: Deviations from Ideal Behavior

• Non-ideal kinetic-molecular behavior

▪ T determines how effective attractive forces between gas
molecules are in causing deviations from ideal behavior at lower P

▪ As the gas cools,

the average kinetic energy of
the molecules decreases

▪ The molecules will be more likely

to stick to each other than bounce
off each other

66
The van der Waals Equation

• Van der Waals equation

▪ Johannes van der Walls (1837 – 1923), the Dutch scientist
proposed useful equation to predict the behavior of real gases

▪ He introduced two constants for correction of the ideal-gas equation

𝑛2 𝑎
𝑃+ 2 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇
𝑉

➢ a : measure of how strongly the gas molecules attract one another

➢ b : measure of the finite volume occupied by the molecules

67
The van der Waals Equation

• Van der Waals equation

- The constants, a and b,

generally increase
with increasing
molecular mass

- Lager, more massive

molecules have larger
volumes and tend to
have greater
intermolecular
attractive forces

68
The van der Waals Equation

Sample Exercise 10.15 [Page 466]

▪ If 10.00 mol of an ideal gas were confined to 22.41 L at 0.0 oC, it
would exert a pressure of 1.013 MPa. Use the van der Waals
equation and Table 10.3 to estimate the pressure exerted by 1.000
mol of Cl2(g) in 22.41 L at 0.0 oC.

𝑛 = 10.00 𝑚𝑜𝑙 𝑎 = 658 𝐿2 ∙ 𝑘𝑃𝑎Τ𝑚𝑜𝑙 2

𝑅 = 8.314 𝑚3 ∙ 𝑃𝑎Τ𝑚𝑜𝑙 ∙ 𝐾 𝑏 = 0.0562 𝐿Τ𝑚𝑜𝑙

= 0.0562 × 10−3 𝑚3 /𝑚𝑜𝑙
𝑇 = 0.0 + 273.15 𝐾 = 273.15 𝐾
𝑛2 𝑎
𝑉 = 22.41 𝐿 = 22.41 × 10−3 𝑚3 𝑃+ 2 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇
𝑉

69
The van der Waals Equation

Sample Exercise 10.15 [Page 466]

𝑛𝑅𝑇 𝑛2 𝑎
𝑃= −
𝑉 − 𝑛𝑏 𝑉 2

10.00 𝑚𝑜𝑙 8.314 𝑚3 ∙ 𝑃𝑎Τ𝑚𝑜𝑙 ∙ 𝐾 273.15 𝐾

𝑃=
22.41 × 10−3 𝑚3 − 10.00 𝑚𝑜𝑙 × 0.0562 × 10−3 𝑚3 Τ𝑚𝑜𝑙
2
10.00 𝑚𝑜𝑙 658 𝐿2 ∙ 𝑘𝑃𝑎Τ𝑚𝑜𝑙 2
−
22.41 𝐿 2

= 1039.4 𝑘𝑃𝑎 − 131.0 𝑘𝑃𝑎 = 908.4 𝑘𝑃𝑎 = 908 𝑘𝑃𝑎

70
 Homework : Chap 10

• Exercise [Page 468 ~ ]

▪ 10, 17, 23, 26, 34, 52, 65, 79, 83, 90

▪ Due : ~ 5/29 (Mon) 09:00

▪ Blackboard system – 과제 및 시험

71