Chapter 5

Gases
 Air Pressure & Shallow Wells
• water for many homes is
supplied by a well less than
30 ft. deep with a pump at
the surface
• the pump removes air from
the pipe, decreasing the air
pressure in the pipe
• the outside air pressure then
pushes the water up the pipe
• the maximum height the
water will rise is related to
the amount of pressure the
air exerts
Tro, Chemistry: A Molecular Approach 2
 Atmospheric Pressure
• pressure is the force
exerted over an area
• on average, the air
exerts the same
pressure that a column
of water 10.3 m high
would exert
 14.7 lbs./in2
 so if our pump could
get a perfect vacuum,
the maximum height
the column could rise is Force
Pressure 
10.3 m Area
Tro, Chemistry: A Molecular Approach 3
 Gases Pushing
• gas molecules are constantly in motion
• as they move and strike a surface, they
push on that surface
 push = force
• if we could measure the total amount of
force exerted by gas molecules hitting
the entire surface at any one instant, we
would know the pressure the gas is
exerting
 pressure = force per unit area
Tro, Chemistry: A Molecular Approach 4
 The Effect of Gas Pressure
• the pressure exerted by a gas can cause some
amazing and startling effects
• whenever there is a pressure difference, a gas
will flow from area of high pressure to low
pressure
the bigger the difference in pressure, the stronger
the flow of the gas
• if there is something in the gas’s path, the gas
will try to push it along as the gas flows
Tro, Chemistry: A Molecular Approach 5
 Atmospheric Pressure Effects
• differences in air pressure result in weather
and wind patterns
• the higher up in the atmosphere you climb, the
lower the atmospheric pressure is around you
at the surface the atmospheric pressure is 14.7 psi,
but at 10,000 ft it is only 10.0 psi
• rapid changes in atmospheric pressure may
cause your ears to “pop” due to an imbalance
in pressure on either side of your ear drum
Tro, Chemistry: A Molecular Approach 6
 Pressure Imbalance in Ear

If there is a difference
in pressure across
the eardrum membrane,
the membrane will be
pushed out – what we
commonly call a
“popped eardrum.”

Tro, Chemistry: A Molecular Approach 7

 The Pressure of a Gas
• result of the constant
movement of the gas
molecules and their collisions
with the surfaces around them
• the pressure of a gas depends
on several factors
number of gas particles in a
given volume
volume of the container
average speed of the gas
particles
Tro, Chemistry: A Molecular Approach 8
 Measuring Air Pressure
• use a barometer
• column of mercury
supported by air
gravity
pressure
• force of the air on the
surface of the mercury
balanced by the pull of
gravity on the column
of mercury

Tro, Chemistry: A Molecular Approach 9

 Common Units of Pressure
Unit Average Air Pressure at
Sea Level
N
pascal (Pa), 1 Pa  1 2 101,325
m
kilopascal (kPa) 101.325
atmosphere (atm) 1 (exactly)
millimeters of mercury (mmHg) 760 (exactly)
inches of mercury (inHg) 29.92
torr (torr) 760 (exactly)
pounds per square inch (psi, lbs./in2) 14.7
Tro, Chemistry: A Molecular Approach 10
Example 5.1 – A high-performance bicycle tire has a pressure
of 132 psi. What is the pressure in mmHg?
Given: 132 psi
Find: mmHg
Concept Plan:
psi atm mmHg
1 atm 760 mmHg
14.7 psi 1 atm
Relationships: 1 atm = 14.7 psi, 1 atm = 760 mmHg
Solution:
1 atm 760 mmHg
132 psi    6.82  103 mmHg
14.7 psi 1 atm

Check: since mmHg are smaller than psi, the answer

makes sense
 Manometers
• the pressure of a gas trapped in a container can be
measured with an instrument called a manometer
• manometers are U-shaped tubes, partially filled with a
liquid, connected to the gas sample on one side and
open to the air on the other
• a competition is established between the pressure of the
atmosphere and the gas
• the difference in the liquid levels is a measure of the
difference in pressure between the gas and the
atmosphere
Tro, Chemistry: A Molecular Approach 12
 Manometer

for this sample, the gas has

a larger pressure than the
atmosphere, so

Pressure gas  Pressure atmosp here  Pressure h

Pressure gas (mmHg)  Pressure atmosp here (mmHg)  difference in Hg levels (mm)

Tro, Chemistry: A Molecular Approach 13

 Boyle’s Law
• pressure of a gas is inversely proportional
to its volume
constant T and amount of gas
graph P vs V is curve
graph P vs 1/V is straight line
• as P increases, V decreases by the same
factor
• P x V = constant
• P1 x V1 = P2 x V2
Tro, Chemistry: A Molecular Approach 14
 Boyle’s Experiment
• added Hg to a J-tube with Length of Air Difference in
air trapped inside in Column Hg Levels
• used length of air column (in) (in)
as a measure of volume 48 0.0
44 2.8
40 6.2
36 10.1
32 15.1
28 21.2
24 29.7
22 35.0

Tro, Chemistry: A Molecular Approach 15

 Boyle's Expt.

140

120

100
Pressure, inHg

80

60

40

20

0
0 10 20 30 40 50 60

Volume of Air, in3

Tro, Chemistry: A Molecular Approach 16
 Inverse Volume vs Pressure of Air, Boyle's Expt.

140

120

100
P re s s u re , in H g

80

60

40

20

0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09

Inv. Volume, in-3

Tro, Chemistry: A Molecular Approach 17
 Boyle’s Experiment, P x V
Pressure Volume P x V
29.13 48 1400
33.50 42 1400
41.63 34 1400
50.31 28 1400
61.31 23 1400
74.13 19 1400
87.88 16 1400
115.56 12 1400
Tro, Chemistry: A Molecular Approach 18
 When you double the pressure on a gas,
the volume is cut in half (as long as the
temperature and amount of gas do not change)

Tro, Chemistry: A Molecular Approach 19

 Boyle’s Law and Diving
• since water is denser if your tank
than air, for each 10 m contained air at 1
you dive below the atm pressure you
surface, the pressure would not be able to
on your lungs inhale it into your
increases 1 atm lungs
at 20 m the total
pressure is 3 atm

Tro, Chemistry: A Molecular Approach 20

Example 5.2 – A cylinder with a movable piston has a volume
of 7.25 L at 4.52 atm. What is the volume at 1.21 atm?
Given: V1 =7.25 L, P1 = 4.52 atm, P2 = 1.21 atm

Find: V2, L
Concept Plan: V1, P1, P2 V2
P1  V1
V2 
P2
Relationships: P1 ∙ V1 = P2 ∙ V2
Solution: P1  V1
V2 
P2


 4.52 atm    7.25 L 
 27.1 L
1.21 atm 
Check: since P and V are inversely proportional, when the pressure
decreases ~4x, the volume should increase ~4x, and it does
Practice – A balloon is put in a bell jar and the pressure is
reduced from 782 torr to 0.500 atm. If the volume of the
balloon is now 2780 mL, what was it originally?

Tro, Chemistry: A Molecular Approach 22

 A balloon is put in a bell jar and the pressure is reduced
from 782 torr to 0.500 atm. If the volume of the balloon is
now 2780 mL, what was it originally?
Given: V2 =2780 mL, P1 = 762 torr, P2 = 0.500 atm

Find: V1, mL
Concept Plan: V1, P1, P2 V2
P2  V2
V1 
P1
Relationships: P1 ∙ V1 = P2 ∙ V2 , 1 atm = 760 torr (exactly)
Solution: P2  V2
V1 
1 atm P1
782 torr   1.03 atm  0.500 atm    2780 L 
760 torr   1350 mL
1.03 atm 
Check: since P and V are inversely proportional, when the pressure
decreases ~2x, the volume should increase ~2x, and it does
 Charles’ Law
• volume is directly proportional to
temperature
constant P and amount of gas V1 V2
graph of V vs T is straight line 
• as T increases, V also increases T1 T2
• Kelvin T = Celsius T + 273
• V = constant x T
if T measured in Kelvin

Tro, Chemistry: A Molecular Approach 24

 Charles’ Law – A Molecular View
• the pressure of gas
gas inside
inside
and outside the balloon
balloon are
the
are same
the same
• at low
hightemperatures,
temperatures,the the
gas molecules are are not
moving
moving
faster, soasthey
fast,hit
sothe
theysides
don’t
of thehit the sides
balloon of the
harder –
balloon
causing asthehard – therefore
volume to
the volume
become is small
larger
Tro, Chemistry: A Molecular Approach 25
 Charles' Law & Absolute Zero
0.6
Volume (L) of 1 g O2 @ 1500 torr

Volume (L) of 1 g O2 @ 2500 torr

0.5 Volume (L) of 0.5 g O2 @ 1500 torr

Volume (L) of 0.5 g SO2 @ 1500

torr

0.4

The data fall on a

V o lu m e , L

0.3
straight line.
If the lines are
extrapolated back to a
0.2
volume of “0,” they all
show the same
0.1 temperature, -273.15°C,
called absolute zero
0
-300 -250 -200 -150 -100 -50 0 50 100 150
Temperature, °C 26
Example 5.3 – A gas has a volume of 2.57 L at 0.00°C. What
was the temperature at 2.80 L?
Given: V1 =2.57 L, V2 = 2.80 L, t2 = 0.00°C

Find: t1, K and °C

Concept Plan: V1, V2, T2 T1
V1
T1  T2 
V2 V1 V2

Relationships: T(K) = t(°C) + 273.15, T1 T2
Solution: T2  V1 t1  T1  273.15
T1 
T2  0.00  273.15 V2 t1  297.6  273.15
T2  273.15 K

 273.15 K    2.57 L 
 297.6 K
t1  24 C
 2.80 L 
Check: since T and V are directly proportional, when the volume
decreases, the temperature should decrease, and it does
Practice – The temperature inside a balloon is raised from
25.0°C to 250.0°C. If the volume of cold air was 10.0 L,
what is the volume of hot air?

Tro, Chemistry: A Molecular Approach 28

The temperature inside a balloon is raised from 25.0°C to 250.0°C.
If the volume of cold air was 10.0 L, what is the volume of hot air?
Given: V1 =10.0 L, t1 = 25.0°C L, t2 = 250.0°C

Find: V2, L
Concept Plan: V1, T1, T2 V2
T2
V2  V1 
T1 V1 V2

Relationships: T(K) = t(°C) + 273.15, T1 T2
Solution: T2  V1
T1  25.0  273.15 V2 
T1
T1  298.2 K
T2  250.0  273.15 
 523.2 K   10.0 L   17.5 L
T2  523.2 K  298.2 K 
Check: since T and V are directly proportional, when the temperature
increases, the volume should increase, and it does
 Avogadro’s Law
• volume directly proportional to V1 V2
the number of gas molecules 
V = constant x n n1 n2
constant P and T
more gas molecules = larger
volume
• count number of gas molecules
by moles
• equal volumes of gases contain
equal numbers of molecules
the gas doesn’t matter
Tro, Chemistry: A Molecular Approach 30
Example 5.4 – A 0.225 mol sample of He has a volume of 4.65 L.
How many moles must be added to give 6.48 L?
Given: V1 =4.65 L, V2 = 6.48 L, n1 = 0.225 mol

Find: n2, and added moles

Concept Plan: V1, V2, n1 n2
V2
n1   n2
V1 V1 V2

Relationships: mol added = n2 – n1, n1 n2
Solution: n  V moles added  0.314  0.225
n  1 2
2
V1 moles added  0.089 mol


 0.225 mol    6.48 L 
 0.314 mol
 4.65 L 
Check: since n and V are directly proportional, when the volume
increases, the moles should increase, and it does
 Ideal Gas Law
• By combing the gas laws we can write a general equation
• R is called the gas constant
• the value of R depends onatmthe
L
units of P and V
• we will use 0.08206 mol  Kand convert P to atm and V to L
• the other gas laws are found in the ideal gas law if
two variables are kept constant
• allows us to find one of the variables if we know the other 3

 P   V  R or PV  nRT
 n  T
Tro, Chemistry: A Molecular Approach 32
 Example 5.6 – How many moles of gas are in a basketball
with total pressure 24.3 psi, volume of 3.24 L at 25°C?
Given: V = 3.24 L, P = 24.3 psi, t = 25 °C,
Find: n, mol
Concept Plan:
P, V, T, R n
PV
n
RT
Relationships: 1 atm = 14.7 psi atmL
PV  nRT, R  0.08206 mol
T(K) = t(°C) + 273.15 K

Solution: PV
1 atm n
24.3 psi   1.6531 atm R T
14.7 psi

 1.6531 atm    3.24 L 
 0.219 mol
T(K)  25C  273.15
T  298 K
 
0.08206 molK   298 K 
atm L

Check: 1 mole at STP occupies 22.4 L, since there is a much smaller

volume than 22.4 L, we expect less than 1 mole of gas
 Standard Conditions
• since the volume of a gas varies with pressure
and temperature, chemists have agreed on a set
of conditions to report our measurements so that
comparison is easy – we call these standard
conditions
STP
• standard pressure = 1 atm
• standard temperature = 273 K
0°C
Tro, Chemistry: A Molecular Approach 34
 Practice – A gas occupies 10.0 L at 44.1 psi and 27°C.
What volume will it occupy at standard conditions?

Tro, Chemistry: A Molecular Approach 35

 A gas occupies 10.0 L at 44.1 psi and 27°C. What
volume will it occupy at standard conditions?
Given: V1 = 10.0 L, P1 = 44.1 psi, t1 = 27 °C, P2 = 1.00 atm, t2 = 0°C

Find: V2, L
Concept Plan:
P1, V1, T1, R n P2, n, T2, R V2
PV nRT
n V
RT P
Relationships: 1 atm = 14.7 psi atmL
PV  nRT, R  0.08206 mol
T(K) = t(°C) + 273.15 K

Solution: PV
n  R  T1 atm n
V  psi 
44.1  3.00 atm R T
P 14.7 psi
 1.219 mol   0.08206 mol
atm  L
   273 K  
 3.00 atm  10.0 L   1.219 mol

 0.08206 mol    300. K 
K

T(K)  27C 273.15

1.00 atm 
atm  L
K

127
T  .300
L .K
Check: 1 mole at STP occupies 22.4 L, since there is more than 1 mole, we
expect more than 22.4 L of gas
 Molar Volume
• solving the ideal gas equation for the volume of
1 mol of gas at STP gives 22.4 L
6.022 x 1023 molecules of gas
notice: the gas is immaterial
• we call the volume of 1 mole of gas at STP the
molar volume
it is important to recognize that one mole of
different gases have different masses, even though
they have the same volume
Tro, Chemistry: A Molecular Approach 37
 Molar Volume

Tro, Chemistry: A Molecular Approach 38

 Density at Standard Conditions
• density is the ratio of mass-to-volume
• density of a gas is generally given in g/L
• the mass of 1 mole = molar mass
• the volume of 1 mole at STP = 22.4 L
Molar Mass, g
Density 
22.4 L
Tro, Chemistry: A Molecular Approach 39
 Gas Density
1 mol mass
mass   moles  moles 
molar mass molar mass
mass in grams
density 
volume in liters

PV  nR T
mass
PV  RT
molar mass
mass P  (molar mass)
 density 
V RT
• density is directly proportional to molar mass
Tro, Chemistry: A Molecular Approach 40
 Example 5.7 – Calculate the density of N2
at 125°C and 755 mmHg
Given: P = 755 mmHg, t = 125 °C,
Find: dN2, g/L

Concept Plan: P, MM, T, R d

P   MM 
d
R T P  MM
1 atm = 760 mmHg, MM = 28.01 g
d
R T
Relationships: T(K) = t(°C) + 273.15 atm  L
R  0.08206 mol K

Solution: P  MM
1 atm d
755 mmHg   0.99342 atm R T
760 mmHg
T(K)  125C  273.15 

 0.99342 atm   28.01 molg   0.852 g/L
T  398 K
 0.08206 atm  L
mol K
   398 K 
Check: since the density of N2 is 1.25 g/L at STP, we expect the density
to be lower when the temperature is raised, and it is
 Molar Mass of a Gas
• one of the methods chemists use to determine
the molar mass of an unknown substance is to
heat a weighed sample until it becomes a gas,
measure the temperature, pressure, and volume,
and use the ideal gas law
mass in grams
Molar Mass 
moles
Tro, Chemistry: A Molecular Approach 42
 Example 5.8 – Calculate the molar mass of a gas with mass
0.311 g that has a volume of 0.225 L at 55°C and 886 mmHg
Given: m=0.311g, V=0.225 L, P=1.1658
P=886 mmHg,
atm, T=328
t=55°C,K,
Find: molar mass, g/mol

Concept Plan: P, V, T, R n n, m MM
PV m
n MM 
R T n
atm L
1 atm = 760 mmHg, PV  nRT, R  0.08206 molK
m
Relationships: T(K) = t(°C) + 273.15 MM 
n
Solution: m 0.311 g
PV 1 atm MM  
 mmHg 
n886  1.1658 atm n 9.7454  10-3 mol
R T 760 mmHg
 31.9 g/mol

T(K)  55
1.1658 C273.15
atm
 T  328 KatmL
 0.225 L 
 9.7 454  103 mol
 
0.08206 molK   328 K 
Check: the value 31.9 g/mol is reasonable
 Practice - Calculate the density of a gas at 775 torr
and 27°C if 0.250 moles weighs 9.988 g

Tro, Chemistry: A Molecular Approach 44

 Calculate the density of a gas at 775 torr and 27°C if
0.250 moles weighs 9.988 g
Given: m=9.988g, n=0.250 mol, P=1.0197
P=775 mmHg,
atm, T=300.
t=27°C,K
Find: density, g/L

Concept Plan: P, n, T, R V V, m d
nR T m
V d
P V
atm L
1 atm = 760 mmHg, PV  nRT, R  0.08206 molK
m
Relationships: T(K) = t(°C) + 273.15 d
V
Solution:
nR  T 1 atm  1.0197 atm m 9.988 g
V 775 torr d 
P 760 torr V 6.0355 L
  27 C 0.08206
T(K)mol
0.250  273.15 atm L    300. K   1.65 g/L
 T  300. K mol K
 6.0355 L
1.0197 atm 
Check: the value 1.65 g/L is reasonable
 Mixtures of Gases
• when gases are mixed together, their molecules
behave independent of each other
 all the gases in the mixture have the same volume
 all completely fill the container  each gas’s volume = the
volume of the container
 all gases in the mixture are at the same temperature
 therefore they have the same average kinetic energy
• therefore, in certain applications, the mixture can be
thought of as one gas
 even though air is a mixture, we can measure the pressure,
volume, and temperature of air as if it were a pure substance
 we can calculate the total moles of molecules in an air sample,
knowing P, V, and T, even though they are different molecules
Tro, Chemistry: A Molecular Approach 46
 Partial Pressure
• the pressure of a single gas in a mixture of gases is
called its partial pressure
• we can calculate the partial pressure of a gas if
 we know what fraction of the mixture it composes and the
total pressure
 or, we know the number of moles of the gas in a container of
known volume and temperature
• the sum of the partial pressures of all the gases in the
mixture equals the total pressure
 Dalton’s Law of Partial Pressures
 because the gases behave independently
Tro, Chemistry: A Molecular Approach 47
 Composition of Dry Air

Tro, Chemistry: A Molecular Approach 48

The partial pressure of each gas in a mixture can
be calculated using the ideal gas law
for two gases, A and B, mixed together
nA x R x T nB x R x T
PA  PB 
V V
the temperatu re and volume of everything
in the mixture are the same
n total  n A  n B
n total x R x T
Ptotal  PA  PB 
V

Tro, Chemistry: A Molecular Approach 49

 Example 5.9 – Determine the mass of Ar in the mixture
Given: P
PArHe==341
0.275mmHg,
atm, V = P
1.00 L, T=298 K
Ne=112 mmHg, Ptot = 662 mmHg,
V = 1.00 L, T=298 K
Find: mass ,g
massArAr, g

Concept Plan: Ptot, PHe, PNe PAr PAr, V, T nA r mAr

PV
PAr = Ptot – (PHe + PNe) n m  n  MM
R T
atm L
Ptot = Pa + Pb + etc., PV  nRT, R  0.08206 molK
m
Relationships: 1 atm = 760 mmHg, MMAr = 39.95 g/mol MM 
n
Solution: 2 39.95 g
PAr  662
PV  341  112  mmHg 1.125  10 mol 
n 1 mol
R T
 209 mmHg  0.449 g Ar

 0.275 atm   1.00 L 
1 atm  1.125  10 2 mol
 0.08206
209 mmHg     298
atm  L
760 mmHg
mol  K
K 
0.275 atm

Check: the units are correct, the value is reasonable

 Practice – Find the partial pressure of neon in a mixture
with total pressure 3.9 atm, volume 8.7 L, temperature
598 K, and 0.17 moles Xe.

Tro, Chemistry: A Molecular Approach 51

 Find the partial pressure of neon in a mixture with total pressure
3.9 atm, volume 8.7 L, temperature 598 K, and 0.17 moles Xe
Given: Ptot = 3.9 atm, V = 8.7 L, T = 598 K, Xe = 0.17 mol

Find: PNe, atm

Concept Plan: nXe, V, T, R PXe Ptot, PXe PNe
n Xe  R  T PNe  Ptotal  PXe
PXe 
V
atm  L
Relationships: PV  nRT, R  0.08206 mol K
, Ptotal  PNe  PXe

Solution: n Xe  R  T
PXe 
PNe  Ptotal  PXe V
 3.9 atm  0.9589 atm 
 0.17 mol   0.08206 molK    598 K 
atmL

8.7 L
 2.9 atm  0.9589 atm
Check: the unit is correct, the value is reasonable
 Mole Fraction
the fraction of the total pressure that a
PA nA
single gas contributes is equal to the 
fraction of the total number of moles Ptotal n total
that a single gas contributes
the ratio of the moles of a single
component to the total number of nA
A 
moles in the mixture is called the n total
mole fraction, 
for gases, = volume % / 100%
the partial pressure of a gas is equal to
the mole fraction of that gas times the PA   A  Ptotal
total pressure
Tro, Chemistry: A Molecular Approach 53
 Mountain Climbing & Partial Pressure
• our bodies are adapted to breathe O2 at
a partial pressure of 0.21 atm
 Sherpa, people native to the Himalaya
mountains, are adapted to the much lower
partial pressure of oxygen in their air
• partial pressures of O2 lower than 0.1
atm will lead to hypoxia
 unconsciousness or death
• climbers of Mt Everest carry O2 in
cylinders to prevent hypoxia
 on top of Mt Everest, Pair = 0.311 atm, so
PO2 = 0.065 atm

Tro, Chemistry: A Molecular Approach 54

 Deep Sea Divers & Partial Pressure
• its also possible to have too much O2, a condition called oxygen
toxicity
 PO2 > 1.4 atm
 oxygen toxicity can lead to muscle spasms, tunnel vision, and
convulsions
• its also possible to have too much N2, a condition called nitrogen
narcosis
 also known as Rapture of the Deep
• when diving deep, the pressure of the air divers breathe increases
– so the partial pressure of the oxygen increases
 at a depth of 55 m the partial pressure of O 2 is 1.4 atm
 divers that go below 50 m use a mixture of He and O 2 called heliox that
contains a lower percentage of O 2 than air

Tro, Chemistry: A Molecular Approach 55

 Partial Pressure & Diving

Tro, Chemistry: A Molecular Approach 56

 Ex 5.10 – Find the mole fractions and partial pressures in
a 12.5 L tank with 24.2 g He and 4.32 g O2 at 298 K
Given: nmHeHe==6.05
24.2mol,
g, mnO2O2==43.2
0.135
g Vmol
= 12.5
V = L,
12.5
T =L,298
T =K298 K
Find: He=0.97817,
, O2, PHe, atm,
O2=0.021827,
PO2, atm, Ptotal
PHe, ,atm
atm, PO2, atm, Ptotal, atm
Concept Plan: mgas ngas gas ntot, V, T, R Ptot
n gas A n total  R  T
 gas A  Ptotal 
n total V
gas, Ptotal Pgas
Relationships: PA   A  Ptotal
MMHe = 4.00 g/mol
atm  L
PV  nRT, R  0.08206 mol , PA   A  Ptotal MMO2 = 32.00 g/mol
K

Solution:  mol
6.05
PHe He He
Ptotal
n t otal  R  T  He   0.97817
P 
g He 
1 mol He 6.05 mol 97817
 0.He  12mol
0.135 .099Oatm
V g  6.05 mol He
total
24.2 2
4.00  11.8 atm
 6.185 mol   2 0.08206 mo lOK 2   298 K 
1 mol O
 g O 2  32.00 g  0.135 mol
4.32
atmL
  Omol
PO0.135 POtotal
12.5 L  O  2 2 2
 0.021827
6.05 mol 021827
 0.He 0.135
 12mol
.099Oatm
2
2
 12.099 atm  0.264 atm
 Collecting Gases
• gases are often collected by having them displace
water from a container
• the problem is that since water evaporates, there is
also water vapor in the collected gas
• the partial pressure of the water vapor, called the
vapor pressure, depends only on the temperature
 so you can use a table to find out the partial pressure of
the water vapor in the gas you collect
• if you collect a gas sample with a total pressure of
758.2 mmHg* at 25°C, the partial pressure of the
water vapor will be 23.78 mmHg – so the partial
pressure of the dry gas will be 734.4 mmHg
 Table 5.4*
Tro, Chemistry: A Molecular Approach 58
 Vapor Pressure of Water

Tro, Chemistry: A Molecular Approach 59

 Collecting Gas by Water Displacement

Tro, Chemistry: A Molecular Approach 60

 Ex 5.11 – 1.02 L of O2 collected over water at 293 K
with a total pressure of 755.2 mmHg. Find mass O2.
Given: V=1.02 L, PP=755.2
O2=737.65 mmHg,
mmHg, T=293
T=293 KK
Find: mass O22, g

Concept Plan: Ptot, PH2O PO2 PO2,V,T nO2 gO2

PV
n
PO 2  Ptotal  PH 2O @ 20C R T
atm L
1 atm = 760 mmHg, PV  nRT, R  0.08206 molK
Relationships: Ptotal = PA + PB, O2 = 32.00 g/mol
Solution:
PO 2  P755.2
 V  17.55 (Table 5.4)
n 32.00 g
PO 2 R T
737 .65 mmHg 4.1175  10  2 mol 
1 mol

 0.97059 atm  1 atm
1.02 L 
L
737.65 mmHg atm  0.97059 atm  1.32 g
 0.08206 molK760
  mmHg
293. K 
 4.1175  10  2 mol
 Practice – 0.12 moles of H2 is collected over water in a
10.0 L container at 323 K. Find the total pressure.

Tro, Chemistry: A Molecular Approach 62

 0.12 moles of H2 is collected over water in a 10.0 L
container at 323 K. Find the total pressure.
Given: V=10.0 L, nH2=0.12 mol, T=323 K
Find: Ptotal, atm

Concept Plan: nH2,V,T PH2 PH2, PH2O Ptotal

n R T Ptotal  PH 2  PH 2O @ 50C
P
V
1 atm = 760 mmHg
atm L
Relationships: Ptotal = PA + PB, PV  nRT, R  0.08206 molK

Solution: 760 mmHg

nR T 0.3181 atm   2 41.8 mmHg
PH 2  1 atm
V

 0.12 mol   0.08206 mol K    323 K 
atmL

10.0 L  Ptotal  2 41.8  92.6 (Table 5.4)

 0.3181 atm Ptotal  330 mmHg
 Reactions Involving Gases
• the principles of reaction stoichiometry from Chapter 4
can be combined with the gas laws for reactions
involving gases
• in reactions of gases, the amount of a gas is often given
as a volume
 instead of moles
 as we’ve seen, must state pressure and temperature
• the ideal gas law allows us to convert from the volume of
the gas to moles; then we can use the coefficients in the
equation as a mole ratio
• when gases are at STP, use 1 mol = 22.4 L

P, V, T of Gas A mole A mole B P, V, T of Gas B

Tro, Chemistry: A Molecular Approach 64
 Ex 5.12 – What volume of H2 is needed to make 35.7 g of CH3OH
at 738 mmHg and 355 K?
CO(g) + 2 H2(g) → CH3OH(g)
Given: nmH2CH3OH
= 2.2284
= 37.5g,
mol,
P=738
P=0.97105
mmHg,atm,
T=355
T=355
K K
Find: VH2, L

Concept Plan: g CH3OH mol CH3OH mol H2 P, n, T, R V

1 mol CH 3OH 2 mol H 2 n R T
V
32.04 g 1 mol CH 3OH P

Relationships: 1 atm = 760 mmHg, CH3OH = 32.04 g/mol

atm L
1 mol CH3OH : 2 mol H2 PV  nRT, R  0.08206 molK
Solution:
1 mol CH 3OH n 2 mol
R HT2
37.5 g CH 3OH  V 
32.04 g 1 molPCH 3OH
 2.2 284 mol H 2

 2.2284 mol   0.08206    355 K 
atmL
molK

1 atm  0.97105 atm 

738 mmHg   0.97105 atm
760 mmHg  66.9 L
 Ex 5.13 – How many grams of H2O form when 1.24 L H2 reacts
completely with O2 at STP?
O2(g) + 2 H2(g) → 2 H2O(g)
Given: VH2 = 1.24 L, P=1.00 atm, T=273 K
Find: massH2O, g

Concept Plan: L H2 mol H2 mol H2O g H2 O

1 mol H 2 2 mol H 2 18.02 g
22.4 L 2 mol H 2O 1 mol H 2O

Relationships: H2O = 18.02 g/mol, 1 mol = 22.4 L @ STP

2 mol H2O : 2 mol H2
Solution:
1 mol H 2 2 mol H 2 O 18.02 g H 2 O
1.24 L H 2   
22.4 L H 2 2 mol H 2 1 mol H 2 O
 0.998 g H 2 O
 Practice – What volume of O2 at 0.750 atm and 313 K is
generated by the thermolysis of 10.0 g of HgO?
2 HgO(s)  2 Hg(l) + O2(g)
(MMHgO = 216.59 g/mol)

Tro, Chemistry: A Molecular Approach 67

 What volume of O2 at 0.750 atm and 313 K is generated by
the thermolysis of 10.0 g of HgO?
2 HgO(s)  2 Hg(l) + O2(g)
Given: nmO2HgO= =0.023085
10.0g, P=0.750
mol, P=0.750
atm, T=313
atm, T=313
K K
Find: VO2, L

Concept Plan: g HgO mol HgO mol O2 P, n, T, R V

1 mol HgO 1 mol O 2 n R T
V
216.59 g 2 mol HgO P

Relationships: 1 atm = 760 mmHg, HgO = 216.59 g/mol

atm L
2 mol HgO : 1 mol O2 PV  nRT, R  0.08206 molK

Solution:
nR T
10.0 g HgO  
V O2
1 mol HgO 1 mol
216.59 g 2 mol HgO P
 0.023085 mol O 2

 0.023085 mol    0.08206 atm  L
mol  K
   313K 
 0.750 atm
 0.791 L
 Properties of Gases
• expand to completely fill their container
• take the shape of their container
• low density
much less than solid or liquid state
• compressible
• mixtures of gases are always homogeneous
• fluid
Tro, Chemistry: A Molecular Approach 69
 Kinetic Molecular Theory
• the particles of the gas (either atoms
or molecules) are constantly moving
• the attraction between particles is
negligible
• when the moving particles hit another
particle or the container, they do not
stick; but they bounce off and
continue moving in another direction
like billiard balls

Tro, Chemistry: A Molecular Approach 70

 Kinetic Molecular Theory
• there is a lot of empty space
between the particles
compared to the size of the particles
• the average kinetic energy of the
particles is directly proportional to
the Kelvin temperature
as you raise the temperature of the
gas, the average speed of the particles
increases
but don’t be fooled into thinking all the
particles are moving at the same speed!!
Tro, Chemistry: A Molecular Approach 71
 Gas Properties Explained –
Indefinite Shape and Indefinite Volume

Because the gas

molecules have As a result, gases
enough kinetic take the shape and
energy to overcome the volume of the
attractions, they container they
keep moving around are in.
and spreading out
until they fill the
container.

Tro, Chemistry: A Molecular Approach 72

 Gas Properties Explained -
Compressibility

Because there is a lot of unoccupied space in the structure

of a gas, the gas molecules can be squeezed closer together
Tro, Chemistry: A Molecular Approach 73
 Gas Properties Explained –
Low Density

Because there is a lot of

unoccupied space in the
structure of a gas, gases do
not have a lot of mass in a
given volume, the result is
they have low density

Tro, Chemistry: A Molecular Approach 74

 Density & Pressure
• result of the constant movement
of the gas molecules and their
collisions with the surfaces
around them
• when more molecules are added,
more molecules hit the container
at any one instant, resulting in
higher pressure
also higher density

Tro, Chemistry: A Molecular Approach 75

 Gas Laws Explained -
Boyle’s Law
• Boyle’s Law says that the volume of a gas is inversely
proportional to the pressure
• decreasing the volume forces the molecules into a
smaller space
• more molecules will collide with the container at any
one instant, increasing the pressure

Tro, Chemistry: A Molecular Approach 76

 Gas Laws Explained -
Charles’s Law
• Charles’s Law says that the volume of
a gas is directly proportional to the
absolute temperature
• increasing the temperature increases
their average speed, causing them to
hit the wall harder and more
frequently
 on average
• in order to keep the pressure constant,
the volume must then increase
Tro, Chemistry: A Molecular Approach 77
 Gas Laws Explained
Avogadro’s Law
• Avogadro’s Law says that the volume of a gas
is directly proportional to the number of gas
molecules
• increasing the number of gas molecules causes
more of them to hit the wall at the same time
• in order to keep the pressure constant, the
volume must then increase

Tro, Chemistry: A Molecular Approach 78

 Gas Laws Explained –
Dalton’s Law of Partial Pressures
• Dalton’s Law says that the total pressure of a mixture of
gases is the sum of the partial pressures
• kinetic-molecular theory says that the gas molecules are
negligibly small and don’t interact
• therefore the molecules behave independent of each
other, each gas contributing its own collisions to the
container with the same average kinetic energy
• since the average kinetic energy is the same, the total
pressure of the collisions is the same
Tro, Chemistry: A Molecular Approach 79
 Dalton’s Law & Pressure
• since the gas
molecules are not
sticking together,
each gas molecule
contributes its own
force to the total
force on the side

Tro, Chemistry: A Molecular Approach 80

 Deriving the Ideal Gas Law from
Kinetic-Molecular Theory
• pressure = Forcetotal/Area
• Ftotal = F1 collision x number of collisions
 in a particular time interval
 F1 collision = mass x 2(velocity)/time interval
 no. of collisions is proportional to the number of particles
within the distance (velocity x time interval) from the wall
 Ftotal α mass∙velocity2 x Area x no. molecules/Volume
• Pressure α mv2 x n/V
• Temperature α mv2
• P α T∙n/V,  PV=nRT
Tro, Chemistry: A Molecular Approach 81
 Calculating Gas Pressure

Tro, Chemistry: A Molecular Approach 82

 Molecular Velocities
• all the gas molecules in a sample can travel at different
speeds
• however, the distribution of speeds follows a pattern
called a Boltzman distribution
• we talk about the “average velocity” of the molecules,
but there are different ways to take this kind of average
• the method of choice for our average velocity is called
the root-mean-square method, where the rms average
velocity, urms, is the square root of the average of the
sum of the squares of all the molecule velocities
 v2
u rms   u2
n
Tro, Chemistry: A Molecular Approach 83
 Boltzman Distribution
Distribution Function

O2 @ 300 K
Fraction of Molecules

Molecular Speed

Tro, Chemistry: A Molecular Approach 84

 Kinetic Energy and
Molecular Velocities
• average kinetic energy of the gas molecules depends on
the average mass and velocity
 KE = ½mv2
• gases in the same container have the same temperature,
the same average kinetic energy
• if they have different masses, the only way for them to
have the same kinetic energy is to have different
average velocities
 lighter particles will have a faster average velocity than more
massive particles
Tro, Chemistry: A Molecular Approach 85
 Molecular Speed vs. Molar Mass
• in order to have the same average kinetic
energy, heavier molecules must have a slower
average speed

Tro, Chemistry: A Molecular Approach 86

 Temperature _and Molecular Velocities
• KEavg = ½NAmu2
NA is Avogadro’s number
• KEavg = 1.5RT
R is the gas constant in energy units, 8.314 J/mol∙K
1 J = 1 kg∙m2/s2
• equating and solving we get:
NA∙mass = molar mass in kg/mol
3RT 3RT
urms  
NA m MM
• as temperature increases, the average velocity increases
Tro, Chemistry: A Molecular Approach 87
 Temperature vs. Molecular Speed
• as the absolute
temperature increases,
the average velocity
increases
the distribution
function “spreads out,”
resulting in more
molecules with faster
speeds

Tro, Chemistry: A Molecular Approach 88

 Ex 5.14 – Calculate the rms velocity of O2 at 25°C
Given: O2, t = 25°C

Find: urms
Concept Plan: MM, T urms
3RT
u rms  3RT
MM u rms 
MM
Relationships: T(K) = t(°C) + 273.15, O2 = 32.00 g/mol
Solution: 3RT
urms 
MM
T(K)  t(C)  273.15
T  25  273.15  kgm 2 

3   8.314 s 2 
  298 K 
T  298 K molK 
 


32.00 10 -3 kg
mol
  482 m/s
 Mean Free Path
• molecules in a gas travel in
straight lines until they collide
with another molecule or the
container
• the average distance a
molecule travels between
collisions is called the mean
free path
• mean free path decreases as the
pressure increases
Tro, Chemistry: A Molecular Approach 90
 Diffusion and Effusion
• the process of a collection of molecules spreading out
from high concentration to low concentration is called
diffusion
• the process by which a collection of molecules escapes
through a small hole into a vacuum is called effusion
• both the rates of diffusion and effusion of a gas are
related to its rms average velocity
• for gases at the same temperature, this means that the
rate of gas movement is inversely proportional to the
square root of the molar mass
1
rate 
MM
Tro, Chemistry: A Molecular Approach 91
 Effusion

Tro, Chemistry: A Molecular Approach 92

 Graham’s Law of Effusion
• for two different gases at the same temperature,
the ratio of their rates of effusion is given by the
following equation:
rategas A Molar Mass gas B

rategas B Molar Mass gas A

Tro, Chemistry: A Molecular Approach 93

 Ex 5.15 – Calculate the molar mass of a gas that
effuses at a rate 0.462 times N2
Given: rateunknown gas
 0.462
rate N 2
Find: MM, g/mol
Concept Plan: rateA/rateB, MMN2 MMunknown
Molar Mass N 2
Molar Mass unknown  2
 rate unknown 
 
 rate N  rategas A Molar Mass gas B

Relationships: N2 = 28.01 g/mol  2 
rategas B Molar Mass gas A

Solution:

Molar Mass unknown 

Molar Mass N 2

 28.01 g mol
 131 g
 rate unknown 
2
 0.462 2 mol
 
 rate N 
 2 
 Ideal vs. Real Gases
• Real gases often do not behave like ideal gases
at high pressure or low temperature
• Ideal gas laws assume
1) no attractions between gas molecules
2) gas molecules do not take up space
 based on the kinetic-molecular theory
• at low temperatures and high pressures these
assumptions are not valid

95
 The Effect of Molecular Volume
• at high pressure, the amount of space occupied
by the molecules is a significant amount of the
total volume
• the molecular volume makes the real volume
larger than the ideal gas law would predict
• van der Waals modified the ideal gas equation
to account for the molecular volume
b is called a van der Waals constant and is
different for every gas because their molecules are
different sizes nRT
V  nb
Tro, Chemistry: A Molecular Approach P 96
 Real Gas Behavior
• because real
molecules take up
space, the molar
volume of a real gas
is larger than
predicted by the ideal
gas law at high
pressures

Tro, Chemistry: A Molecular Approach 97

The Effect of Intermolecular Attractions
• at low temperature, the attractions between the
molecules is significant
• the intermolecular attractions makes the real pressure
less than the ideal gas law would predict
• van der Waals modified the ideal gas equation to
account for the intermolecular attractions
 a is called a van der Waals constant and is different for
every gas because their molecules are different sizes
2
nRT n
P  a 
V V
Tro, Chemistry: A Molecular Approach 98
 Real Gas Behavior
• because real
molecules attract each
other, the molar
volume of a real gas
is smaller than
predicted by the ideal
gas law at low
temperatures

Tro, Chemistry: A Molecular Approach 99

 Van der Waals’
Equation
• combining the equations to
account for molecular volume
and intermolecular attractions
we get the following equation
 used for real gases
 a and b are called van der Waal
constants and are different for each
gas
 2
 P  a n     V - nb   nRT
  V  
 
Tro, Chemistry: A Molecular Approach 100
 Real Gases
• a plot of PV/RT vs. P for 1 mole of a gas shows
the difference between real and ideal gases
• it reveals a curve that shows the PV/RT ratio for
a real gas is generally lower than ideality for
“low” pressures – meaning the most important
factor is the intermolecular attractions
• it reveals a curve that shows the PV/RT ratio for
a real gas is generally higher than ideality for
“high” pressures – meaning the most important
factor is the molecular volume
Tro, Chemistry: A Molecular Approach 101
 PV/RT Plots

Tro, Chemistry: A Molecular Approach 102

 Structure of the Atmosphere
• the atmosphere shows several
layers, each with its own
characteristics
• the troposphere is the layer closest
to the earth’s surface
 circular mixing due to thermal currents
– weather
• the stratosphere is the next layer up
 less air mixing
• the boundary between the
troposphere and stratosphere is
called the tropopause
• the ozone layer is located in the
stratosphere

Tro, Chemistry: A Molecular Approach 103

 Air Pollution
• air pollution is materials added to the atmosphere that
would not be present in the air without, or are increased
by, man’s activities
 though many of the “pollutant” gases have natural sources as
well
• pollution added to the troposphere has a direct effect on
human health and the materials we use because we
come in contact with it
 and the air mixing in the troposphere means that we all get a
smell of it!
• pollution added to the stratosphere may have indirect
effects on human health caused by depletion of ozone
 and the lack of mixing and weather in the stratosphere means
that pollutants last longer before “washing” out
Tro, Chemistry: A Molecular Approach 104
 Pollutant Gases, SOx
• SO2 and SO3, oxides of sulfur, come from coal
combustion in power plants and metal refining
as well as volcanoes
• lung and eye irritants
• major contributor to acid rain
2 SO2 + O2 + 2 H2O  2 H2SO4
SO3 + H2O  H2SO4

Tro, Chemistry: A Molecular Approach 105

 Pollutant Gases, NOx
• NO and NO2, oxides of nitrogen, come from burning of
fossil fuels in cars, trucks, and power plants
 as well as lightning storms
• NO2 causes the brown haze seen in some cities
• lung and eye irritants
• strong oxidizers
• major contributor to acid rain
4 NO + 3 O2 + 2 H2O  4 HNO3
4 NO2 + O2 + 2 H2O  4 HNO3
Tro, Chemistry: A Molecular Approach 106
 Pollutant Gases, CO
• CO comes from incomplete burning of fossil
fuels in cars, trucks, and power plants
• adheres to hemoglobin in your red blood cells,
depleting your ability to acquire O2
• at high levels can cause sensory impairment,
stupor, unconsciousness, or death

Tro, Chemistry: A Molecular Approach 107

 Pollutant Gases, O3
• ozone pollution comes from other pollutant
gases reacting in the presence of sunlight
as well as lightning storms
known as photochemical smog and ground-level
ozone
• O3 is present in the brown haze seen in some
cities
• lung and eye irritants
• strong oxidizer
Tro, Chemistry: A Molecular Approach 108
 Major Pollutant Levels
• government
regulation has
resulted in a
decrease in the
emission levels for
most major
pollutants

Tro, Chemistry: A Molecular Approach 109

 Stratospheric Ozone
• ozone occurs naturally in the stratosphere
• stratospheric ozone protects the surface of the
earth from over-exposure to UV light from the sun
O3(g) + UV light  O2(g) + O(g)
• normally the reverse reaction occurs quickly, but
the energy is not UV light
O2(g) + O(g)  O3(g)

Tro, Chemistry: A Molecular Approach 110

 Ozone Depletion
• chlorofluorocarbons became popular as aerosol
propellants and refrigerants in the 1960s
• CFCs pass through the tropopause into the stratosphere
• there CFCs can be decomposed by UV light, releasing Cl
atoms
CF2Cl2 + UV light  CF2Cl + Cl
• Cl atoms catalyze O3 decomposition and removes O atoms
so that O3 cannot be regenerated
 NO2 also catalyzes O3 destruction
Cl + O3  ClO + O2
O3 + UV light  O2 + O
ClO + O  O2 + Cl
Tro, Chemistry: A Molecular Approach 111
 Ozone Holes

• satellite data over

the past 3 decades
reveals a marked
drop in ozone
concentration over
certain regions

Tro, Chemistry: A Molecular Approach 112