GENERAL CHEMISTRY

Principles and Modern Applications 8 th EDITION

Petrucci • Harwood • Herring

Chapter 6: Gases

6
1
Gases
CONTENTS

6-1 Properties of Gases: Gas Pressure

6-2 The Simple Gas Laws
6-3 Combining the Gas Laws: The Ideal Gas Equation and
The General Gas Equation

6-4 Applications of the Ideal Gas Equation

6-5 Gases in Chemical Reactions

6-6 Mixtures of Gases
6-7 Kinetic—Molecular Theory of Gases

6-8 Gas Properties Relating to the Kinetic—Molecular

Theory
6-9 Nonideal (Real) Gases

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 6-1 Properties of Gases: Gas Pressure
• Gases expand to fill their containers and assume the sahpes of their containers. They
diffuse into one another and mix in all proportions.

• We can not see individual particles of a gas, but we can see the bulk gas if it is colored.

• Some gases, such as H2 and CH4, are combustible; whereas others, such as He and Ar,
are inert.

• Four properties determine the physical behavior of a gas: the amount of gas (in mole),
the gas volume, temperature and pressure.

• If we know any three of these, we can usually calculate the vale of the remaining one.

• Most common gases, such as CO2, O2, N2 and H2 are colorless.

Cl2(g) Br2(l) l2(s)

The gaseous state of three halogens (group 17)
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 The Concept of Pressure

• Pressure is the force per unit area.

• In SI, force is expressed in newtons (N) and area in square meters (m2).

• The unit of pressure in SI is the pascal (Pa) with the units N/m2.

• Kilopascals (kPa) are often used instead since the pascal is such a small unit.

• The atmosphere and mmHg (Torr) are the most common scientific units for
pressure.

• Converting from one unit to another simply requires the appropriate

conversion factor(s).

• e.g., 760 mmHg = 1.01325 bar

760 mmHg 1.01325 bar

or
1.01325 bar 760 mmHg
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 The Concept of Pressure

Force
Force (N) = g (m/s2) x m (kg)

Pressure
Force (N)
P (Pa) =
Area (m2)

• The two cylinders have the same mass and exert the same force on the
supporting surface (F = g x m).

• The tall, thin one has a smaller area of contact, however exerts a greater
pressure.

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 Liquid Pressure

• The pressure of a gas is usually measured indirectly, by comparing it with a

liquid pressure.

• The pressure of a liquid depends only on the height of the liquid column and
the density of the liquid.

F = W = gxm = gxVxd = gxhxAxd = gxhxd

P (Pa) =
A A A A A

• Liquid pressure is directly proportional to the liquid density and

the height of the liquid column.

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 Barometric Pressure
• In 1643, Evangelista Torricelli constructed a device to measure the pressure
exerted by atmosphere. This divece called a barometer.
A barometer is an instrument used to measure atmospheric pressure.
The pressure exerted by a column of mercury exactly 760 mm high is defined as
1 atmosphere (atm).

a) The liquid mercury levels are equal inside and outside the open-end tube.
b) A column of mercury 760 mm high is maintained in the closed-end tube, regardless of
the overall height of the tube.
c) as long as it exceeds 760 mm.
The pressure exerted by
the column of mercury
…

… must be the same

as that exerted by the
atmosphere. 7
Barometric Pressure

• The height of mercury in a barometer provides a measure of barometric

pressure.

• Barometric pressures may be expressed in a unit called millimeter of mercury

(mmHg),

• The pressure exerted by the atmosphere can support a column of mercury that is
about 760 mm high and thus, atmospheric pressure is typically about 760 mmHg.

• One standard atmosphere (atm) is defined to be exactly equal to 760 mmHg

when the density of mercury is equal to 13.5951 g/cm3 (0 ºC) and g is equal to
9.80665 m/s2.

1 atm = 760 mmHg

8
 Pressure units
• Calculate the pressure exerted by a column of mercury that is exactly 760 mHg
high when the density of mercury is d= 13.5951 g/cm3 = 1.35951x104 kg/m3 and
g = 9.80665 ms-2.

P= gxhxd
P =(9.80665 ms-2)(0.760000 m)(1.35951x104 kg/m3)
P = 1.01325x105 kgm-1s-2 (0 ºC)
P = 101.325 kPa

• One atmosphere (atm): pressure exerted by a column of mercury

exactly 760 mm high.

• One millimeter of mercury is called a Torr.

1 atm = 760 mmHg
= 760 Torr
= 101.325 kPa
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10
Manometers
• A manometer is used to measure the pressure of a sample of gas.
• Pressure is measured using the difference in the heights of mercury (or other
liquid) in the two arms of the manometer.

Ø A Closed-End Manometer

• If the liquid is mercury, Dh can be expressed

directly in mmHg.
P is zero here …
• For other liquids, the pressure exerted by a
liquid column is:
P=g.d.h

Pgas = Dh
… so Pgas = Dh
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Ø An Open-End Manometer

Pgas = Pbar Pgas = Pbar + DP Pgas = Pbar + DP

(DP = g x d x h > 0) (DP = - g x d x h < 0)
a) Gas pressure equal to b) Gas pressure greater than c) Gas pressure less than
barometric pressure barometric pressure barometric pressure

If Pgas and Pbar are expressed in mmHg, then ΔP is numerically equal to the
height h expressed in millimeters.

Measurement of gas pressure with an open-end manometer

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13
14
6-2 Simple Gas Laws
Ø Boyle’s Law: Pressure-Volume Relationship
• In 1662, Robert Boyle discovered the first of the simple gas law.
• For a fixed amount of gas at a constant temperature, the gas volume is
inversely proportional to the gas pressure.
• For a fixed amount of gas at a constant temperature, the product of pressure
and volume is a constant.
1
Pa PV = a (a constant)
V

• The equation PV = a can be used to derive another equation for a gas when
undegoes a change at constant temperature.
• We write equation for the initial state(i) and the final state (f), we get PiVi = a
and PfVf = a.

PV = constant or PinitialVinitial = PfinalVfinal (n constant, T constant)

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Graphical Representation of Boyle’s Law

Estimate the pressure at 3V and

at 5V. Which plot is easier to use
for making this estimation?

When volume is increased there is more area

for the molecules to “hit”; less force per area.
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 6-2 CONCEPT ASSESSMENT
A 50.0 L cylinder contains nitrogen gas at a pressure of 21.5 atm. The
contents of the cylinder are emptied into an evacuated tank of unknown
volume. If the final pressure in the tank is 1.55 atm, then what is the
volume of the tank?
(a) (21.5/1.55) x 50.0 L (b) (1.55/21.5) x 50.0 L
(c) 21.5/(1.55 x 50.0) L (d) 1.55/(21.5 x 50.0) L

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 6-2 CONCEPT ASSESSMENT (CONTINUED)

Use Boyle’s Law

P 1V 1
P 1V 1 = P 2V 2 V2 = therefore (a) is the answer
P2
'( #%.+
V# = V% x = 50 x = 694 L
') %.++

Calculation shows that Vtank = 694 – 50 644 L

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Ø Charles’s Law: Temperature-Volume Relationship

• The relationship between the volume of a gas and temperature was

discovered by the French physicist Jacques Charles in 1787 and by
Joseph Louis Gay-Lussac.

• The volume of a fixed amount of gas at constant pressure is directly

proportional to the Kelvin (absolute) temperature.

• Absolute zero is the temperature obtained by extrapolation to zero

volume.

• Absolute zero on the Kelvin scale = –273.15 °C

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Gas volume as a function of temperature

VaT

V=bT (b constant)

The equation V/T = b can be used to derive another equation for a gas
when undegoes a change at constant pressure.

We write equation for the initial state(i) and the final state (f), we get
Vi/Ti = b and Vf/Tf = b.

𝐕𝐢 𝐕𝐟
= (n constant, p constant)
𝐓𝐢 𝐓𝐟
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Standard Temperature and Pressure

• Gas properties depend on conditions.

• IUPAC defines Standard conditions of Temperature and Pressure (STP).

Ø Standard temperature for gases

T = 0º C = 273.15 K

Ø Standard pressure for gases

P = 1 bar

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Ø Avogadro’s Law: Mole-Volume Relationship
Avogadro 1811

At a fixed temperature and pressure, the volume of a gas is directly

proportional to the amount of gas in moles (n) or to the number of
molecules of gas.

• At fixed T and P
• Van Þ V = cn Þ V/n = c (c constant)

• Standard Temperature and Pessure (STP) is equal to 0 °C and 1 bar.

• The molar volume of a gas is the volume occupied by one mole of the gas.

• At STP, molar volume of an ideal gas is 22.711 liters.

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Molar volume of a gas
visualized

• Wooden cube is 28.2 cm on edge and has

approximately the same volume (22.4 liters)
as one mole of gas at 1 atm and 0º C.

• Basketball = 7.5 L, Soccer ball = 6.0 L and

Football = 4.4 L

1 mol gas = 22.414 L (at 0º C, 1 atm)

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 Avogadro's Hypothesis

• Avogadro’s equal volumes-equal numbers hypothesis can be stated in either of

two ways:
1. Equal volumes of different gases compared at the same temperature and
pressure contain equal numbers of molecules.

2. Equal numbers of molecules of different gases compared at the same

temperature and pressure occupy equal volumes.

Formation of Water – actual observation and Avogadro’s hypothesis

If equal volumes of gases contain equal numbers of molecules, this means the
volume of O2(g) is one half that of H2(g) .
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 Avogadro's Law

• At a fixed temperature and pressure, the volume of a gas is

directly proportional to the amount of gas.

1 mol gas = 6.022 x 1023 molecules gas = 22.4 L gas (at STP)
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 6-3 Combining the Gas Laws:
The Ideal Gas Equation
and the General Gas Equation

1. Boyle’s law describes the effect of pressure, V µ 1/P

nT
2. Charles’s law describes the effect of temperature, VµT Vµ
P
3. Avogadro’s law describes the effect of the amount of gas, V µ n

Boyle’s law V µ 1/P

nT
Charles’s law VµT Vµ
P
Avogadro’s law Vµn

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• The Ideal Gas Equation
These three laws can be combined into a single equation—the ideal gas
equation—that includes all four gas variables: volume, pressure, temperature,
and amount of gas.

nT RnT
V α —— and V α ——
P P

PV = nRT

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• Gas constant (R)
Any gas whose behavior conforms to the ideal gas
equation is called an ideal or perfect gas.
PV
R=
nT

• Value for R at STP

(P in atm, V in L, n in moles, T in kelvins).

'0 % 345 × ##.7%78 9

R= = = 0.082057 atm L molJ% K J%
12 % 5:; × #<=.%+ >

• Value for R when using SI units

(P in Pa, V in m3, n in moles, T in kelvins).

'0 %8%,=#+ '3× #.#7%78 ×%8M) 5N

R= = = 8.3145 Pa m= molJ% K J%
12 % 5:; × #<=.%+ >

R = 8.3145 Pa m3 mol-1 K-1 = 8.3145 J mol-1 K-1

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Applying the ideal gas equation

This image cannot currently be displayed.

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31
• The General Gas Equation
Sometimes a gas is described under two different sets of conditions. The ideal gas
equation must be applied twice—to an initial condition and a final condition.

Initial condition (i) Final condition (f)

PiVi = niRTi PfVf = nfRTf

PiVi Pf V f
R= R=
niTi nfTf

PiVi Pf V f
= General Gas Equation
niTi nfTf

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Ø Amontons’s law:

The pressure of a fixed amount of gas confined to a fixed

volume is directly proportional to the Kelvin temperature.

If we hold the amount and volume constant:

P1 P2
=
T1 T2

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34
Using the Gas Laws

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6-4 Applications of the Ideal Gas Equation
• Molar Mass Determination

If we know the volume of a gas at a fixed temperature and pressure,

we can find the amount of the gas in moles and also molar mass of the gas.

M = molar mass and m = mass in grams

m (grams) m
M = ————— so n= —
n (moles) M

The ideal gas equation rearranges to:

PV
PV = nRT n = ——
RT
m m RT
PV = RT M=
M PV 36
37
• Gas Density
Gases are much less dense than liquids and solids, so gas densities are usually reported in g/L.

𝒎 𝒏 ×𝑴 𝒏 𝒏 𝑷
𝒅= = = ×𝑴 m = 𝒏 ×𝑴 =
𝑽 𝑹𝑻
𝑽 𝑽 𝑽

𝒎 𝑴𝑷
𝒅= =
𝑽 𝑹𝑻

The density of gases differs from that of solids and liquids in two ways.
1. Gas densities depend strongly on pressure and temperature, increasing as the gas
pressure increases and decreasing as the temperature increases. Densities of liquids
and solids also depend somewhat on temperature, but they depend far less on
pressure.
2. The density of a gas is directly proportional to its molar mass. No simple
relationship exists between density and molar mass for liquids and solids.

Density of a gas is directly proportional to its molar mass and pressure,

and is inversely proportional to Kelvin temperature.
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39
6-5 Gases in Chemical Reactions
The law of combining volumes
• Consider an example to illustrate Gay Lussac’s law of combining volumes:
2 NO(g) + O2(g) → 2 NO2 (g)
2 mol NO(g) + 1 mol O2(g) → 2 mol NO2 (g)

At any other T and P, one mole of gas = V L

Then,
2V L NO(g) + V L O2(g) → 2V L NO2 (g) (divide both sides by V)

2L NO(g) + L O2(g) → 2 L NO2 (g)

• The volume ratio of the gases consumed and produced in a chemical is the same
as the mole ratio, if temperature and pressure are constant.

• When gases measured at the same temperature and pressure are allowed to react,
the volumes of gaseous reactants and products are in small whole-number ratios.
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42
6-6 Mixtures of Gases

Partial pressure
Each component of a gas mixture exerts a pressure that it would
exert if it were in the container alone.

• Gas laws apply to mixtures of gases.

• Simplest approach is to use ntotal, but....

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Mixtures of Gases: Dalton’s Law of Partial Pressures

• Dalton’s law of partial pressures is used in dealing with mixtures of

gases.

• The total pressure exerted by a mixture of gases is equal to the sum of the
partial pressures exerted by the separate gases:

• Ptotal = P1 + P2 + P3 + …

• Partial pressure: the pressure a gas would exert if it were alone in the
container.

n1RT n2RT n3RT

P1 = ——— P2 = ——— P3 = ——— …
V V V

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Dalton’s Law of Partial Pressures

• The total pressure of a mixture of gases is the sum of the partial

pressures of the components of the mixture.

Ptot = PA + PB

Vtot = VA = VB

Dalton’s law of partial pressures illustrated

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Partial Pressure

Ptot = Pa + Pb +…

Va = naRT/Ptot Vb = nbRT/Ptot and Vtot = Va + Vb+…

Pa naRT/Vtot na Va naRT/Ptot na
= = = =
Ptot ntotRT/Vtot ntot Vtot n tot RT/P tot ntot

na Pa V
= = a = ca mole fraction (x) of a
ntot Ptot Vtot

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Mole Fraction

• The mole fraction (x) of a gas is the fraction of all the molecules
in a mixture that are of a given type.

n1
x1 = ——
ntotal
• Since pressure (at constant T and V) is directly
proportional to number of moles:
We can find the partial
pressure of a gas from
its mole fraction and the
total pressure.
P1
x1 = —— or P1 = x1 Ptotal
Ptotal
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49
Collection of Gases over Water

• As (essentially insoluble) gas is bubbled into the container for collection, the
water is displaced.

• The gas collected is usually saturated with water vapor.

• Assuming the gas is saturated with water vapor, the partial pressure of the water
vapor is the vapor pressure of the water.
Values of water vapour pressure
Ptot = Pbar = Pgas + PH2O
can be obtained from tables:

Pgas = Ptotal – PH2O(g) = Pbar – PH2O(g)

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