Chapter 5

The Gaseous
State
Pressure, P
The force exerted per unit area.

It can be given by two equations:

F
P P  dgh
A

The SI unit for pressure is the pascal, Pa.

kg  m kg m kg
s 2  kg  2 m 
m 3
s m  s2
m2 m  s2  Pa (pascal)
 Pa (pascal)
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Other Units
atmosphere, atm
mmHg
torr
bar

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A barometer is a device for measuring the
pressure of the atmosphere.

A manometer is a device for measuring the

pressure of a gas or liquid in a vessel.

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Empirical Gas Laws
All gases behave quite simply with respect to
temperature, pressure, volume, and molar amount.
By holding two of these physical properties
constant, it becomes possible to show a simple
relationship between the other two properties.

The studies leading to the empirical gas laws

occurred from the mid-17th century to the mid-19th
century.

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Boyle’s Law
The volume of a sample of gas at constant
temperature varies inversely with the applied
pressure.
1
The mathematical relationship: V 
P

In equation form: PV  constant

PiVi  PfVf

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 Figure A shows the Figure B shows the
plot of V versus P for plot of (1/V) versus P
1.000 g O2 at 0°C. for 1.000 g O2 at
This plot is nonlinear. 0°C. This plot is
linear, illustrating the
inverse relationship.
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At one atmosphere
the volume of the
gas is 100 mL.
When pressure is
doubled, the
volume is halved to
50 mL. When
pressure is tripled,
the volume
decreases to one-
third, 33 mL.

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 When a 1.00-g sample of O2
gas at 0°C is placed in a
container at a pressure of 0.50
atm, it occupies a volume of
1.40 L.

When the pressure on the O2 is

doubled to 1.0 atm, the volume
is reduced to 0.70 L, half the
original volume.

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 A volume of oxygen gas occupies 38.7

? mL at 751 mmHg and 21°C. What is

the volume if the pressure changes to
359 mmHg while the temperature
remains constant?

Vi = 38.7 mL Vf = ?
Pi = 751 mmHg Pf = 359 mmHg
Ti = 21°C Tf = 21°C

PiVi
Vf 
Pf
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 Vi = 38.7 mL Vf = ?
Pi = 751 mmHg Pf = 359 mmHg
Ti = 21°C Tf = 21°C

PiVi
Vf 
Pf

(38.7 mL)(751 mmHg)

Vf 
(359 mmHg)

= 81.0 mL
(3 significant figures)

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The temperature -273.15°C is called absolute
zero. It is the temperature at which the volume of a
gas is hypothetically zero.

This is the basis of the absolute temperature scale,

the Kelvin scale (K).

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Charles’s Law
The volume of a sample of gas at constant
pressure is directly proportional to the absolute
temperature (K).

The mathematical relationship: V T

V
In equation form:  constant
T
Vi Vf

Ti T f
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A balloon was immersed As the air inside warms,
in liquid nitrogen (black the balloon expands to
container) and is shown its orginial size.
immediately after being
removed. It shrank
because air inside
contracts in volume.
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When the absolute A 1.0-g sample of O2 at
temperature of the sample a temperature of 100 K
is raised to 200 K, the and a pressure of 1.0
volume of the O2 is atm occupies a volume
doubled to 0.52 L. of 0.26 L.

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 You prepared carbon dioxide by adding

? HCl(aq) to marble chips, CaCO3.

According to your calculations, you
should obtain 79.4 mL of CO2 at 0°C
and 760 mmHg. How many milliliters of
gas would you obtain at 27°C?
Vi = 79.4 mL Vf = ?
Pi = 760 mmHg Pf = 760 mmHg
Ti = 0°C = 273 K Tf = 27°C = 300. K

T fVi
Vf 
Ti
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 Vi = 79.4 mL Vf = ?
Pi = 760 mmHg Pf = 760 mmHg
Ti = 0°C = 273 K Tf = 27°C = 300. K

T fVi
Vf 
Ti
(300. K)(79.4 mL)
Vf 
(273 K)

= 87.3 mL
(3 significant figures)

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A graph of V versus T is linear. Note that all lines cross
zero volume at the same temperature, −273.15°C.
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Combined Gas Law
The volume of a sample of gas at constant
pressure is inversely proportional to the pressure
and directly proportional to the absolute
temperature.
T
The mathematical relationship: V 
P
PV
In equation form:  constant
T
PiVi PfVf

Ti Tf
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 Divers working from a North Sea

? drilling platform experience pressure of

5.0 × 101 atm at a depth of 5.0 × 102
m. If a balloon is inflated to a volume of
5.0 L (the volume of the lung) at that
depth at a water temperature of 4°C,
what would the volume of the balloon
be on the surface (1.0 atm pressure) at
a temperature of 11°C?
Vi = 5.0 L Vf = ?
Pi = 5.0 × 101 atm Pf = 1.0 atm
Ti = 4°C = 277 K Tf = 11°C = 284 K
Copyright © Cengage Learning. All rights reserved. 5 | 20
 Vi = 5.0 L Vf = ?
Pi = 5.0 × 101 atm Pf = 1.0 atm
Ti = 4°C = 277 K Tf = 11°C = 284 K

T f PiVi
Vf 
Ti Pf
(284 K)(5.0  10 atm)(5.0 L) 1
Vf 
(277 K)(1.0 atm)
= 2.6  102 L
(2 significant figures)

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Avogadro’s Law
Equal volumes of any two gases at the same
temperature and pressure contain the same
number of molecules.

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 Avogadro’s Law

Relationship between Volume and Amount of Gas

• Avogadro’s law states:
-Equal volume of gases at the same temperature
and pressure contain the same number of
molecules.
𝑉
Thus, 𝑉 ∝ 𝑛 or 𝑉 = 𝐶𝑎 𝑛 or = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑛
-One mole of any gas contains 6.02×1023
molecules(Avogadro’s number)
-According to Avogadro’s Law, one mole of gas
must occupy the same volume at a given
temperature and pressure.
-The volume that is occupied by one mole of a gas
at a given temperature and pressure is called
Molar Gas Volume, Vm.
-Volumes of gases are often compared at standard
temperature and pressure(STP), the conditions for
gases chosen by convention to be 0°C (273K)
and 1atm.
-At STP, the gas volume is found to be 22.4L/mol
-Avogadro’s Law can be re-expressed as follows:
• The molar Gas Volume at a given temperature
and pressure is a specific constant independent
of the gas.
Thus, 𝑉𝑚 = 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡(22.4 L/mol at STP)
 Exercise

• Ammonium can be made directly from elements

according to the following equation:
N2(g) + 3H2(g) → 2NH3(g)
• Question
If one begins with 12.6L of H2(g) at a given
temperature and pressure, what volume of N2(g) is
required for complete reaction (at the same
temperature and pressure)? What is the theoretical
yield of N2(g) in Litres??
 Solution
• Since gas volume is proportional to the number
of moles of gas, we can use volumes instead of
moles.
• Recall 𝑉 ∝ 𝑛
First Calculate Litres of N2 required
1L of N2(g) requires 3L of H2(g)
? Requires 12.6 L H2(g)
1𝐿 (𝑁2 )×12.6 𝐿 (𝐻2 )
Cross multiply = 4.2L of N2(g)
3𝐿 (H2(g))
• Or you can use number of moles
• Recall
Vm = 22.4L at STP
So, if
1mole → 22.4L
? → 12.6L
1𝑚𝑜𝑙𝑒 ×12.6 𝐿
= 0.5625𝑚𝑜𝑙𝑒𝑠 N2(g)
22.4 𝐿
Now, from stoichiometric equation
1 mole N2(g) → 3 moles H2(g)
? → 0.5625 moles H2(g)
1 𝑚𝑜𝑙𝑒×0.5625 𝑚𝑜𝑙𝑒𝑠
3 𝑚𝑜𝑙𝑒𝑠
= 0.1875 moles of N2(g)
To get moles of N2(g)
1 mole → 22.4 L
0.1875 moles → ?
0.1875 𝑚𝑜𝑙𝑒𝑠×22.4 𝐿
=4.2L
1 𝑚𝑜𝑙𝑒
Standard Temperature and Pressure (STP)
The reference condition for gases, chosen by
convention to be exactly 0°C and 1 atm pressure.

The molar volume, Vm, of a gas at STP is 22.4

L/mol.

The volume of the

yellow box is 22.4 L. To
its left is a basketball.

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Ideal Gas Law
The ideal gas law is
given by the equation
PV=nRT

The molar gas

constant, R, is the
constant of
proportionality that
relates the molar
volume of a gas to T/P.

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 IDEAL GAS LAW
• Three laws that we have dealt with:
Boyles Law Charles Law Avogadros Law
1
V∝ 𝑝 𝑉 ∝𝑇 𝑉 ∝𝑛
At constant T, n At constant P, n At constant T,P

• They tell how one gas property is affected as

another is changed assuming the other two
properties remain fixed.
• If all three laws are combined and the result is:

𝑛𝑇 thus 𝑛𝑇
𝑉 ∝ 𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 x
𝑃
𝑃
• This constant, is a number that connects P,V,T
and n and is called the gas constant labelled R,
so:
𝑛𝑇 or
𝑉 ∝ 𝑃𝑉 = 𝑛𝑅𝑇
𝑃

• Thus the ideal gas equation (law)

• Note: ideal gas - a gas in which there re no
intermolecular forces (sometimes is called perfect
gas).
• To use the ideal gas equation, PV = nRT, we
need the value of R.
• Experiments have shown that under the condition
of standard temperature and pressure (STP). i.e.
at gas temperature of 0 oC or 273.15 K and
pressure of 1 atm, 1 mole of gas occupies 22.4 L
• Thus, 22.4 L is known as molar volume Vm.
• Substituting this value into the ideal gas law, we can
solve for R,
𝑃𝑉
• Where: 𝑅 =
𝑛𝑇
1.000 𝑎𝑡𝑚 𝑥 22.4 𝐿
• 𝑅= = 0.082057 L.atm.k-1.mol-1
1.000 𝑚𝑜𝑙𝑒𝑠 𝑥 273.15 𝐾

• Note: units of R, the gas constants depends on the

units of pressure;
• R = 0.0821 L.atm.K-1.mol-1 or 8.31 L.kPa.K-1.mol-1
• Note: R also appears in thermodynamic calculations
but with different units and numerical value 8.315 J.K-
1.mol-1, therefore use the one appropriate to the

relevant calculations.
Exercise 1: Ideal Gas Law
The He gas in 1.5 L flask at 25 oC exerts a
pressure of 425 mmHg. How many moles of
He are there in the flask?

Solution:
Information provided:
V = 1.5 L, P = 425 mmHg, T = 25 oC, n = ?
Recall:
𝑃𝑉 = 𝑛𝑅𝑇 and to use R, P has to be in atm, T in
kelvin and V in liters.
• Now arrange the ideal gas equation to solve for n,
𝑃𝑉
• Thus 𝑛= and substitute to get the
𝑅𝑇
ANSWER as 0.034 moles
Exercise 2: ideal gas law
The balloon used by Charles in his historic
flight in 1783, was filled with about 1300
moles of H2. if the temperature of the gas was
20 oC and its pressure was 750 mmHg, what
was the volume of the balloon?
Solution:
Information provided;
T = 20 oC + 273.15 K = 273.15 K
n = 1300 moles
P = 750 mmHg = 0.9868 atm
V=?
R = 0.08205 L.atm.K-1.mol-1
𝑛𝑅𝑇
• 𝑃𝑉 = 𝑛𝑅𝑇 thus 𝑉 =
𝑃
• ANS: 316874.11 L
Exercise 3 ideal gas law.
How many grams of oxygen (O2) are there in
a 50.0 L gas cylinder at 21 oC? When the
oxygen pressure is 15.7 atm.
Solution:
Information provided:
V = 50.0 L.
T = 294.15 K.
P = 15.7 atm.
n=?
𝑃𝑉 = 𝑛𝑅𝑇 solve for n, number of moles.
Then use moles and Mr to calculate grams.
ANS: moles = 32.5 moles , grams =1040 g O2 or
1.04 x103 g O2.
 A 50.0-L cylinder of nitrogen, N2, has a

? pressure of 17.1 atm at 23°C. What is the

mass of nitrogen in the cylinder?

V = 50.0 L PV
P = 17.1 atm n
RT
T = 23°C = 296 K
(17.1 atm)(50.0 L)
n
 L  atm 
 0.08206 (296 K)
 mol  K 
28.02 g mass = 986 g
mass  35.20 mol (3 significant figures)
mol
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 Gas Density and Molar Mass
Using the ideal gas law, it is possible to calculate
the moles in 1 L at a given temperature and
pressure. The number of moles can then be
converted to grams (per liter).

To find molar mass, find the moles of gas, and

then find the ratio of mass to moles.

PM m dRT
In equation form: d or Mm 
RT P

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 What is the density of methane gas

? (natural gas), CH4, at 125°C and 3.50

atm?

Mm = 16.04 g/mol MmP

d
P = 3.50 atm RT
T = 125°C = 398 K
g
(16.04 )(3.50 atm) g
mol d  1.72
d L
 L  atm 
 0.08206 (398 K) (3 significant figures)
 mol  K 

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 A 500.0-mL flask containing a sample

? of octane (a component of gasoline) is

placed in a boiling water bath in
Denver, where the atmospheric
pressure is 634 mmHg and water boils
at 95.0°C. The mass of the vapor
required to fill the flask is 1.57 g. What
is the molar mass of octane? (Note:
The empirical formula of octane is
C4H9.) What is the molecular formula of
octane?

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 d = 1.57 g/0.5000 L dRT
= 3.140 g/L Mm 
P
P = 634 mmHg
= 0.8342 atm
T = 95.0°C = 368 K

 g  L  atm 
 3.140  0.08206 368 K 
 L  mol  K 
Mm 
(0.8342 atm)

g
M m  114
mol
(3 significant figures)

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 Molar mass = 114 g/mol
Empirical formula: C4H9
Empirical formula molar mass = 57 g/mol

g
114
n mol  2
g
57
mol

Molecular formula: C8H18

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Stoichiometry and Gas Volumes
Use the ideal gas law to find moles from a given
volume, pressure, and temperature, and vice
versa.

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 When a 2.0-L bottle of concentrated

? HCl was spilled, 1.2 kg of CaCO3 was

required to neutralize the spill. What
volume of CO2 was released by the
neutralization at 735 mmHg and
20.°C?

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First, write the balanced chemical equation:

CaCO3(s) + 2HCl(aq) 
CaCl2(aq) + H2O(l) + CO2(g)

Second, calculate the moles of CO2 produced:

Molar mass of CaCO3 = 100.09 g/mol

1mol CaCO3 1mol CO2

1.2  10 g CaCO3 3

100.09 g CaCO3 1mol CaCO3

Moles of CO2 produced = 11.99 mol

Copyright © Cengage Learning. All rights reserved. 5 | 46

 nRT
n = 11.99 mol V 
P = 735 mmHg P
= 0.967 atm
T = 20°C = 293 K

 L  atm 
11.99 mol 0.08206 (293 K)
 mol  K 
V
(0.967 atm)

= 2.98 × 102 L
(3 significant figures)

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Gas Mixtures
Dalton found that in a mixture of unreactive gases,
each gas acts as if it were the only gas in the
mixture as far as pressure is concerned.

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Originally (left), flask A contains He at 152 mmHg
and flask B contains O2 at 608 mmHg. Flask A is
then filled with oil forcing the He into flask B (right).
The new pressure in flask B is 760 mmHg.
Copyright © Cengage Learning. All rights reserved. 5 | 49
Partial Pressure
The pressure exerted by a particular gas in a
mixture.

Dalton’s Law of Partial Pressures

The sum of the partial pressures of all the different
gases in a mixture is equal to the total pressure of
the mixture:
P = PA + PB + PC + . . .

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DALTON’S LAW OF PARTIAL
PRESSURES.
• This law applies to gases which do not react
chemically. The law state that: the total
pressure of a gas mixture is equal to the sum
of the partial pressures of the individual gases
in the mixture.
• Note: partial pressure of a gas in a mixture is
defined as the pressure that the gas would
exert if it alone occupied the container.
• Or the pressure exerted by a particular gas in a
mixture is the partial pressure of that gas.
• Thus, if you let Ptot be the total pressure of a
mixture of gases, available, Pa, Pb, Pc,…..Pn. Be
the partial pressures of the components of gases
in a mixture, the law of partial pressures,
Dalton’s Law can be written as:
𝑃𝑡𝑜𝑡 = 𝑃𝑎 + 𝑃𝑏 + 𝑃𝑐 + …
+ 𝑃𝑛

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 A 100.0-mL sample of air exhaled from

? the lungs is analyzed and found to

contain 0.0830 g N2, 0.0194 g O2,
0.00640 g CO2, and 0.00441 g water
vapor at 35°C. What is the partial
pressure of each component and the
total pressure of the sample?

Copyright © Cengage Learning. All rights reserved. 5 | 53

  1 mol N 2 L  atm 
 0.0830 g N 2  0.08206 308 K 
 28.01 g N 2 mol  K 
PN2   0.749 atm
 1L 
100.0 mL  3 

 10 mL 
 1 mol O 2  L  atm 
 0.0194 g O 2  0.08206 308 K 
 32.00 g O 2  mol  K 
PO2   0.153 atm
 1L 
100.0 mL  3 

 10 mL 
 1 mol CO 2  L  atm 
 0.00640 g CO 2  0.08206 308 K 
 44.01 g CO 2  mol  K 
PCO2   0.0368 atm
 1L 
100.0 mL  3 

 10 mL 
 1 mol H 2 O  L  atm 
 0.00441 g H 2 O  0.08206 308 K 
 18.01 g H O  mol  K 
PH2O 
2
 0.0619 atm
 1L 
100.0 mL  3 

 10 mL 
Copyright © Cengage Learning. All rights reserved. 5 | 54
 PN2  0.749 atm
PO2  0.153 atm
PCO2  0.0368 atm
PH2O  0.0619 atm

P  PN2  PO2  PCO 2  PH2O

P = 1.00 atm

Copyright © Cengage Learning. All rights reserved. 5 | 55

 The partial pressure of air in the alveoli

? (the air sacs in the lungs) is as follows:

nitrogen, 570.0 mmHg; oxygen, 103.0
mmHg; carbon dioxide, 40.0 mmHg;
and water vapor, 47.0 mmHg. What is
the mole fraction of each component of
the alveolar air?
PN2  570.0 mmHg
PO2  103.0 mmHg
PCO2  40.0 mmHg
PH2O  47.0 mmHg

Copyright © Cengage Learning. All rights reserved. 5 | 56

 P  PN2  PO2  PCO 2  PH2O

570.0 mmHg
103.0 mmHg
40.0 mmHg
47.0 mmHg
P = 760.0 mmHg

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 Mole fraction of N2 Mole fraction of O2
570.0 mmHg 103.0 mmHg
 
760.0 mmHg 760.0 mmHg
Mole fraction of CO2 Mole fraction of H2O
40.0 mmHg 47.0 mmHg
 
760.0 mmHg 760.0 mmHg
Mole fraction N2 = 0.7500

Mole fraction O2 = 0.1355

Mole fraction CO2 = 0.0526

Mole fraction O2 = 0.0618

Copyright © Cengage Learning. All rights reserved. 5 | 58
Collecting Gas Over Water
Gases are often collected over water. The result is
a mixture of the gas and water vapor.
The total pressure is equal to the sum of the gas
pressure and the vapor pressure of water.
The partial pressure of water depends only on
temperature and is known (Table 5.6).
The pressure of the gas can then be found using
Dalton’s law of partial pressures.

Copyright © Cengage Learning. All rights reserved. 5 | 59

The reaction of Zn(s) with HCl(aq) produces
hydrogen gas according to the following reaction:

Zn(s) + 2HCl(aq)  ZnCl2(aq) + H2(g)

The next slide illustrates the apparatus used to

collect the hydrogen. The result is a mixture of
hydrogen and water vapor.

Copyright © Cengage Learning. All rights reserved. 5 | 60

Copyright © Cengage Learning. All rights reserved. 5 | 61
 P  769 mmHg
At 19C, PH2O  16.5 mmHg
(See Table 5.6)
P  PH2  PH2O
PH2  P  PH2O
PH2  769 mmHg  16.5 mmHg
PH2  752.5 mmHg
PH2  753 mmHg
(no decimal places)
Copyright © Cengage Learning. All rights reserved. 5 | 62
 You prepare nitrogen gas by heating

? ammonium nitrite:
NH4NO2(s)  N2(g) + 2H2O(l)
If you collected the nitrogen over water
at 23°C and 727 mmHg, how many
liters of gas would you obtain from 5.68
g NH4NO2?

P = 727 mmHg
Molar mass NH4NO2
Pvapor = 21.1 mmHg
= 64.06 g/mol
Pgas = 706 mmHg
T = 23°C = 296 K
Copyright © Cengage Learning. All rights reserved. 5 | 63
 P = 727 mmHg Molar mass NH4NO2
Pvapor = 21.1 mmHg = 64.06 g/mol
Pgas = 706 mmHg nRT
V 
T = 23°C = 296 K P

1mol NH4NO2 1mol N2

5.68 g NH4NO2
64.04 g NH4NO2 1mol NH4NO2
= 0.8887 mol N2 gas

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 P = 727 mmHg
Pvapor = 21.1 mmHg
Pgas = 706 mmHg nRT
V
T = 23°C = 296 K P
n = 0.0887 mol
 L  atm 
0.0887 mol  0.08206 (296 K)
 mol  K 
V 
 1 atm 
 706 mmHg 
 760 mmHg 

= 2.32 L of N2
(3 significant figures)
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• The individual partial pressure follow the ideal gas
law, for component A, 𝑃𝐴𝑉 = 𝑛𝐴𝑅𝑇 or 𝑃𝐴 = 𝑛𝐴𝑅𝑇/𝑉
• Where nA is the umber of moles of component A.
𝑃𝐴 𝑛𝐴𝑅𝑇/𝑉 𝑛𝐴
• Recall 𝑃𝑡𝑜𝑡 = 𝑛𝑡𝑜𝑡𝑅𝑇/𝑉 thus = =
𝑃𝑡𝑜𝑡 𝑛𝑡𝑜𝑡𝑅𝑇/𝑉 𝑛𝑡𝑜𝑡
• Notice that the ratio of partial pressure of gas A, to the
total pressure of the gas mixture is the same as the ratio
of moles of gas A to the total moles of gas. The ratio
nA/ntot is called mole fraction of A.

𝑛𝐴 𝑃𝐴
• Thus: 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴, 𝑋𝐴 = =
𝑛𝑡𝑜𝑡 𝑃𝑡𝑜𝑡
• In general, the mole fraction of any component
gas A of a mixture is given as:

𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑟𝑖𝑜𝑛 𝐴 (𝑋𝐴)

𝑚𝑜𝑙𝑒𝑠 𝐴
=
𝑚𝑜𝑙𝑒𝑠 𝐴 + 𝑚𝑜𝑙𝑒𝑠 𝐵 + 𝑚𝑜𝑙𝑒𝑠 𝐶 + ⋯

• The sum of the mole fraction of all component

must always add to one.
XA + XB + XC +….. = 1
• Example
• Assume a 5.0 mole sample of air is composed
of 3.9 moles N2 and 1.1 moles of O2. calculate
mole fraction for each gas in a sample.
• Solution:
3.9 𝑚𝑜𝑙𝑒 𝑁2
• 𝑋𝑁2 = 3.9 𝑚𝑜𝑙𝑒 𝑁2+1.1 𝑚𝑜𝑙𝑒 𝑂2
= 0.78 𝑎𝑛𝑑 .

1.1 𝑚𝑜𝑙𝑒 𝑂2
• 𝑋𝑂2 = = 0.22
3.9 𝑚𝑜𝑙𝑒 𝑁2+1.1 𝑚𝑜𝑙𝑒 𝑂2

• And 𝑋𝑁2 + 𝑋𝑂2= 1

• Note; applying the concept of mole fraction to
gas law, you can see that the partial pressure
of a gas in a mixture is equal to the product of
its mole fraction and the total pressure.
• Thus: 𝑃𝐴 = 𝑋𝐴𝑃𝑡𝑜𝑡
Kinetic-Molecular Theory (Kinetic Theory)
A theory, developed by physicists, that is based on
the assumption that a gas consists of molecules in
constant random motion.

Kinetic energy is related to the mass and velocity:

1
E K  mv 2
2
m = mass
v = velocity

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Postulates of the Kinetic Theory
1. Gases are composed of molecules whose
sizes are negligible.
2. Molecules move randomly in straight lines in all
directions and at various speeds.
3. The forces of attraction or repulsion between
two molecules (intermolecular forces) in a gas
are very weak or negligible, except when the
molecules collide.
4. When molecules collide with each other, the
collisions are elastic.
5. The average kinetic energy of a molecule is
proportional to the absolute temperature.

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An elastic collision is one in which no kinetic
energy is lost. The collision on the left causes the
ball on the right to swing the same height as the
ball on the left had initially, with essentially no loss
of kinetic energy.

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Each of the gas laws can be derived from the
postulates.

For the ideal gas law:

P  frequency of collision x average force

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The average force depends on the mass of the
molecules, m, and its average speed, u; it depends
on momentum, mu.

The frequency of collision is proportional to the

average speed, u, and the number of molecules,
N, and inversely proportional to the volume, V.
 1 
P   u   N   mu
 V 

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 Rearranging this relationship gives

PV  Nmu 2

The average kinetic energy of a molecule of

mass m and average speed u is 1/2mu2.

Thus PV is proportional to the average kinetic

energy of the molecule.

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However, the average kinetic energy is also
proportional to the absolute temperature and the
number of molecules, N, is proportional to moles of
molecules. We now have
PV  nT

Inserting the proportionality constant, R, gives

PV  nRT

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Molecular Speeds
According to kinetic theory, molecular speeds vary
over a wide range of values. The distribution
depends on temperature, so it increases as the
temperature increases.

Root-Mean Square (rms) Molecular Speed, u

A type of average molecular speed, equal to the
speed of a molecule that has the average
molecular kinetic energy
3RT
u
Mm
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When using the equation

R = 8.3145 J/(mol · K).

T must be in Kelvins
Mm must be in kg/mol

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 What is the rms speed of carbon

? dioxide molecules in a container at

23°C?

T = 23°C = 296 K 3RT

CO2 molar mass =
u rms 
Mm
0.04401 kg/mol

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Recall  kg  m 2 
 
kg  m 2
3 8.3145 s 296 K 
2
J
s2 mol  K 
 
 
u rms 
 kg 
 0.04401 
 mol 

2
m
urms  1.68  105 2
s
m
urms  4.10  10
2

s
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Diffusion
The process whereby
a gas spreads out
through another gas
to occupy the space
uniformly.
Below NH3 diffuses
through air. The
indicator paper tracks
its progress.

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Effusion
The process by which a gas flows through a small
hole in a container. A pinprick in a balloon is one
example of effusion.

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Graham’s Law of Effusion
At constant temperature and pressure, the rate of
effusion of gas molecules through a particular hole
is inversely proportional to the square root of the
molecular mass of the gas.
1
rate of effusion of molecules 
Mm

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 Both hydrogen and helium have been
used as the buoyant gas in blimps. If a
? small leak were to occur, which gas
would effuse more rapidly and by what
factor?
1
Rate H2 2.016 4.002
 
Rate He 1 2.016
4.002

Hydrogen will diffuse more quickly by a factor of 1.4.

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Real Gases
At high pressure the relationship between pressure
and volume does not follow Boyle’s law. This is
illustrated on the graph below.

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At high pressure, some of the assumptions of the
kinetic theory no longer hold true:

1. At high pressure, the volume of the gas

molecule (Postulate 1) is not negligible.
2. At high pressure, the intermolecular forces
(Postulate 3) are not negligible.

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Van der Waals Equation
An equation that is similar to the ideal gas law, but
which includes two constants, a and b, to account
for deviations from ideal behavior.

The term V becomes (V – nb).

The term P becomes (P + n2a/V2).
Values for a and b are found in Table 5.7
 n 2a 
P  V  nb   nRT
 2 
 V 
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