Chapter 11: Properties of Gases

• Gases have a number of properties that are

very different from liquids and solids:
1) Gases are compressible
2) Gases exert a pressure
3) Gas pressure depends on the amount of confined
gas
4) Gases fill their container
5) Gases mix freely with each other
6) Gas pressure increases with temperature
 The qualitative observations
of the properties of gases
leads to the conclusion that a
gas is comprised of widely
spaced molecules in rapid
motion. Collisions of
molecules with the walls are
responsible for the gas
pressure.

• This simple model of gases is the basis of

the kinetic-molecular theory (discussed in
Section 7.2)
• Recall the pressure is a force per unit area
force
pressure 
area
• The earth exerts a gravitational force on
everything with mass near it
• What we call weight is the gravitational
force acting on an object
• The pressure due to air molecules colliding
with an object is called the atmospheric
pressure
Atmospheric pressure is
measured with a
barometer. A Torricelli
barometer consists of a
glass tube sealed at one
end, about 80 cm in
length. The tube is filled
with mercury, capped,
inverted, and the capped
end immersed in a pool of
mercury. When the cap is
removed the atmosphere
supports a the column of
mercury about 760 mm
high.
• The height of the mercury column varies
with altitude
• The average pressure at sea level or the
standard atmosphere (atm) was defined as
the pressure needed to support a column of
mercury 760 mm high measures at 0oC
• The SI unit of pressure is the pascal (Pa)
1N 2
1 Pa   1 N m
1 m2
1 atm  101,325 Pa (exactly)
• You may encounter a number of pressure
units
• The standard atmosphere is
o
760 mm Hg (measured at 0 C)
760 torr
101,325 Pa  101.325 kPa
1.013 bar  1013 mb
2
14.7 lb in
• Chemical reactions often involve gases
• A manometer is used to measure the
pressure inside closed containers

Open-end manometer. (a) The pressure of the trapped gas,

Pgas equals the atmospheric pressure, Patm. Trapped gas
pressure (b) higher and (c) lower than atmospheric pressure.
A closed-end manometer for
measuring gas pressures less than
1 atm. When constructed (a) the
tube is fully evacuated and
mercury is allowed to enter and fill
the closed arm completely. (a)
Mercury flows out of the closed
arm when the bulb contains gas at
low pressure. The difference in
mercury levels, PHg, is the pressure
of the confined gas, Pgas.
• Mercury is so dense (13.6 g mL-1) that small
pressure changes are difficult to measure
• Other liquids can be used to make
manometers
Columns of mercury and
water that exert the same
pressure. Mercury is 13.6
times more dense than
water. Both columns have
the same weight and
diameter, so they exert the
same pressure.
• Thus for a given difference in pressure, the
difference in heights between the two levels
is inversely proportional to the density of
the liquid used in the manometer
• There are four variables that affect the
properties of a gas: pressure, volume,
temperature, and the amount of the gas
• Simple experiments can be conducted that
relate how these variables change
• The gas laws summarize these experiments
Compressing a gas
increases its pressure.
A molecular view of
what happens when a
gas is squeezed into a
smaller volume. The
number of collisions
with a given area of the
walls increases which
causes the pressure to
rise.
Robert Boyle studied how the volume of a fixed amount of
gas varies with pressure at constant temperature. (a) Air
trapped in a J-tube by mercury. (b) As more mercury is
added, the pressure of the trapped gas increases and the
volume decreases.
(a) A typical graph of volume versus pressure showing volume
decreasing as pressure increases. (b) A straight line is obtained
when volume is plotted against (1/P), which shows that
1
V
P
• The relationship between volume and
pressure is called Boyle’s law or the
pressure-volume law
– The volume of a given amount of gas held at
constant temperature varies inversely with the
applied pressure
• The proportionality can be removed by
introducing a proportionally constant, C
1
V   C or PV  C (constant amount and temperatu re)
P
• Boyle’s law is remarkably successful,
especially for common laboratory
conditions
• However, no real gas obeys Boyle’s law
exactly over a wide range of temperatures
and pressures
• The hypothetical gas that does exactly
obey Boyle’s law is called an ideal gas
• Real gases act more like ideal gases as their
pressures decrease and temperatures
increase
• Jacques Alexander Charles studied how the
volume of a gas sample varied with
temperature Charles’ law plots.
Each line shows
how the gas
volume changes
with temperature
for different sized
samples of the
same gas.
• When extrapolated to zero volume all the
samples have the same temperature:
 273.15 C o

• This temperature is called absolute zero

and is the basis of the Kelvin temperature
scale:
TK  T C  273.15
o

• Charles’ law or the temperature-volume law

can be expressed mathematically
 V T or V  C ' T (constant amount and pressure)

• Joseph Louis Gay-Lussac studied how the

pressure and temperature of a fixed amount
of gas at constant volume are related
• Gay-Lussacs’ law or the pressure-
temperature law states:
– The pressure of a fixed amount of gas held at
constant volume is directly proportional to the
Kelvin temperature
• Mathematically this is
 P  T or P  C"T (constant amount and volume)

• The three gas laws are often used in a single

equation called the combined gas law
PV P1V1 P2V2
 constant or  (fixed amount)
T T1 T2
• When using this equation the temperature
must always be in kelvins
• Alternate forms of the previous gas laws
result when certain variables cancel
 Boyle' s Law :
P1V1  P2V2 (when T1  T2 )
Charles' Law :
V1 / T1  V2 / T2 (when P1  P2 )
Gay - Lussac' s Law :
P1 / T1  P2 / T2 (when V1  V2 )

• Problems involving the gas laws are

important
Example: What will be the the final pressure of a
sample of oxygen with a volume of 850 m3 at
655 torr and 25.0oC if it is heated to 80.0oC and
given a final volume of 1066 m3?
ANALYSIS: Use the combined gas law with
temperature in kelvins.
SOLUTION:
V1 T2
P2  P1  
V2 T1
850 m 3 (80.0  273.2)K
 655 torr  
1066 m (25.0  273.2)K
3

 619 torr
• The law of combining volume states:
– When gases react at the same temperature and
pressure, their combining volumes are in ratios
of simple, whole numbers
• Example:
hydrogen  chlorine  hydrogen chloride
1 volume 1 volume 2 volumes
• Amedeo Avogadro studied this and devised
Avogadro’s principle:
– When measured at the same temperature and
pressure, equals volumes of gases contain equal
number of moles
• A corollary to Avogadro’s principle is:
– The volume of a gas is directly proportional to
its number of moles, n
V n (at constant T and P)
• Thus, the volume of one mole of any gas at
standard temperature and pressure (STP) or
0oC and 1 atm is 22.4 L (a constant for all
ideal gases)
• This is called the standard molar volume of
a gas
• The combined gas law can be generalized to
include changes in the number of moles of
sample
• The ideal gas law is
PV  nRT
R  universal gas constant
atm L
 0.0821
mol K
• The molecular mass is obtained by taking
the ratio of mass to moles, which could be
determined using the ideal gas law
• Gas densities (d), a ratio of gas mass to
volume, can be calculated by taking the
ratio of the molar mass to molar volume
– Example: The molar mass of oxygen is 32.0
g/mol. What is the density of oxygen at STP?
32.0 g/mol
dO 2   1.42 g L1
22.4 L/mol
 One mole of each gas
occupies 22.4 at STP.
Carbon dioxide is
more dense that
oxygen due to molar
mass differences.
• We now need to consider mixtures of gases
• One useful way to describe a composition
of a mixture is in terms of its mole fractions
• The mole fraction is the ratio of the number
of moles of a given component to the total
moles of all components
• For a mixture of A, B, … substances, the
mole fraction of substance i (Xi) is
nA
XA  , ni  moles of i
n A  nB  ...  nZ
• This provides a convenient way to
`partition’ the total pressure of a mixture of
gases
• Dalton’s law of partial pressures states:
the total pressure of a mixture of gases is
the sum of their individual partial pressures
• For a system of only gases, mole fractions
and partial pressure partition the total
pressure in the same fashion
PTotal  PA  PB  ....
 PTotal X A  PTotal X B  ....
1  X A  X B  ...
• Gases are often collected over water in the
laboratory
• These (collected) gases are saturated with
water
• The space above any liquid contains some
of the liquid’s vapor
• The pressure this vapor exerts is called the
vapor pressure

As the gas bubbles through the water, water vapor gets into
the gas so the total pressure inside the bottle includes the
partial pressure of the water vapor.
 Temperatur e ( o C) Vapor Pressure (torr)
0 4.579
Vapor pressure
20 17.54
of water at
30 31.82 various
40 55.32 temperatures.
100 760.0

• The total pressure is the pressure of the gas

plus the vapor pressure of water
Ptotal  Pgas  Pwater vapor or
Pgas  Ptotal  Pwater vapor
 Example: A sample of oxygen is collected over
water at 20oC and a pressure of 738 torr. What
is the partial pressure of oxygen?
ANALYSIS: The partial pressure of oxygen is
less than the total pressure. Get the vapor
pressure of water from table 11.2 (page 478).
SOLUTION:
Pwater vapor  17.54 torr (from Table 11.2)
Pgas  (738  17.54) torr  720. torr
• Partial pressures can be used to calculate
mole fractions
• This is possible because the number of
moles of each gas is directly proportional to
its partial pressure
• Using the ideal gas equation for each gas
PAV
nA 
RT
• For a given mixture of gases, the volume
and temperature is the same for all gases
• Using C=V/RT gives
 PAC
XA 
PAC  PB C    PZ C
PA PA
 
PA  PB    PZ Ptotal
• The partial pressure of a gas can be
calculated using the total pressure and mole
fraction
PA  X A Ptotal
• Gas volumes can be used in stoichiometry
problems
2H 2 ( g )  O 2 ( g )  2H 2 O(g)
2 volumes 1 volume 2 volumes (same temperatu re and pressure)

2 volumes H 2 ( g )  1 volume O 2 ( g )
2 volumes H 2 ( g )  2 volumes H 2 O( g )
1 volumes O 2 ( g )  2 volumes H 2 O( g )
just as
2 moles H 2 ( g )  1 mole O 2 ( g )
2 moles H 2 ( g )  2 moles H 2 O( g )
1 mole O 2 ( g )  2 moles H 2 O( g )
• Diffusion is the spontaneous intermingling
of the molecules of one gas with another
• Effusion is the movement of gas molecules
through a tiny hole into a vacuum
• The rates of both diffusion and effusion
depend on the speed of the gas molecules
• The faster the molecules, the faster
diffusion and effusion occur
• Thomas Graham studied effusion
• He found that the effusion rate of a gas was
inversely proportional to the square root of
the density (d)
• This is known as Graham’s law
1
effusion rate  (constant P and T )
d
effusion rate ( A) dB MB
 
effusion rate ( B) dA MA
• Where Mi is the molar mass of species i
 (a) Diffusion (b) Effusion
• The behavior of ideals gases can be
explained
Postulates of the Kinetic Theory of Gases
1) A gas consists of a large number of tiny
particles that are in constant, random motion.
2) The gas particles themselves occupy a net
volume so small in relation to the volume of
their container that their contribution to the
total volume can be ignored.
3) The collisions between particle and with the
walls of the container are perfectly elastic.
• Calculations show that PV is proportional to
the average kinetic energy and the Kelvin
temperature, thus
PV  average molecular KE
PV  T
 T  average molecular KE
• The kinetic theory also explains the gas
laws
The kinetic theory and
the pressure volume
law (Boyle’s law).
When the gas volume
is made smaller going
from (a) to (b), the
frequency of collisions
per unit area of the
containers’ wall
increases. Thus the
pressure increases.
The kinetic theory and the pressure-temperature law (Gay-Lussac’s
law). The pressure increases from (a) to (b) as measured by the
amount of mercury that must be added to maintain a constant
volume.
The kinetic theory and the temperature-volume law (Charles’
law). The pressure is the same in both (a) and (b). At higher
temperatures the volume increases because the gas molecules
have higher velocities.
• Graham’s law requires that the rate of
effusion for the different gases be compared
at the same temperature and pressure
• When different gases have the same
temperature, they have the same average
kinetic energy
• The average kinetic energy can be
expressed in terms of the average of the
velocities squared or root mean square
• For the two gases labeled 1 and 2
 KE1  KE2
1 1
m1 v1  m2 v2 rearrangin g
2 2

2 2


2
v m2
1
 or with vi rms
 v
2
i
v2 m1
2

v  
m2

M2
v 
1 rms

2 rms
m1 M1
• Note that heavier gases move slower than
lighter gases
• The rate of effusion is proportional to the
average molecular speed, thus



effusion rate (gas 1) v1 rms

M2
 
effusion rate (gas 2) v2 rms M1
• The kinetic theory predicts that absolute
zero is the temperature at which the average
kinetic energy of an ideal gas is zero
• Real gases exhibit non-ideal behavior
 Deviation from the ideal
gas law. A plot of PV/T
versus P for an ideal gas
is a straight line. The
same plot for oxygen is
not a straight line

• Deviations from ideal behavior occur

because:
1) Gas molecules interact, and
2) Gas molecules occupy a finite volume.
(a) In an ideal gas, molecules would travel in straight lines.
(b) In a real gas, the paths would curve due to the attractions
between molecules.

• J. D. van der Waals corrected the ideal gas

equation in a simple, but useful, way
• He did this by modifying the measured
pressure and volume of a real gas so it fits
the ideal gas equation
 n2a 
 Pmeasured  2 Vmeasured  nb   nRT
 Vmeasured 
n2a
2
: brings measured P up to ideal gas value
Vmeasured
nb : reduces measured V to ideal gas value
• The constants a and b are called the van der
Waals constants
 a b
Substance
L2 atm mol  2 L mol 1
Helium, He 0.03421 0.02370
Neon, Ne 0.2107 0.01709
Hydrogen, H 2 0.02444 0.02661
Ammonia, NH 3 4.170 0.03707
Water, H 2 O 5.464 0.03049

• Table 11.3 (page 493) has a more complete

set of van der Waals constants