Units of Pressure
Pressure is the amount force applied to an area and it
is measured by Barometer.
Pressure = Force/ area.
Pascals
1 Pascal( pa) = 1 Nm-2 = 1 kg m-1s-2
A related unit used to report pressure is the Bar
1 bar = 101325 pa =standard pressure
mmHg (Torr)
760 Torr = standard pressure
Atmosphere
1 atmosphere = standard pressure
1 atm = 760 mmHg = 760 Torr = 101 325 Pa
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Boyle’s Law
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Charles’s Law
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Avogadro’s Law
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Ideal-Gas Equation
Example
Calculate the pressure exerted by 1.0 g of carbon dioxide in
a 1.0 L flask at 300 oC.
Solution
First find the number of moles and then use the ideal gas
equation, .
(recall 1 J = 1 kg m2s-2 and 1 Pa = J m-3 =1 kg m-1s-2)
OR
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Molecular Mass
We can manipulate the density equation to enable us
to find the molecular mass of a gas:
Example
The density of a gas was measured at 1.50 atm and
27oC and found to be 1.95 g/L. Calculate the molar
mass of the gas.
Solution
= 32.0 g mol-1
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Molecular Mass
Exercise
The oil produced from eucalyptus leaves contains
the volatile organic compound eucalyptol. At 190
O
C and 60.0 Torr, a sample of eucalyptol vapour
had a density of 0.320 g L-1. Calculate the molar
mass of eucalyptol.
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THE MOLAR VOLUME
The ideal gas law can also be used to predict the volume
of an ideal gas under any conditions of temperature and
pressure.
and
is called molar volume of a gas, i.e. volume occupied by
one mole of gas. Therefore at 25.00 oC (298.15 K) and
1.000 atm, the molar volume is
= 24.47 L mol-1
The expression standard temperature and pressure
(STP)means 0 oC and 1 atm. At STP, the molar volume of
an ideal gas is 22.41 L mol-1.
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THE MOLAR VOLUME
The molar volume can be used as a conversion
factor between moles and volume.
Example
A sample of nitrogen gas has a volume of 1.75 L
at STP. How many moles of N2 are present?
The molar volume at STP is 22.41 Lmol-1. We write
1 mol = 22.41 L
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Dalton’s Law of Partial Pressures
Dalton's law of partial pressures states that the total
pressure of a mixture of gases in the container is the
sum of the partial pressures of its components.
Ptotal = P1 + P2 + P3 + . .
Assuming we have a mixture of ideal gases, we can
use the ideal gas law to solve problems involving
gases in a mixture.
The pressure exerted by an individual gas in a
mixture is known as its partial pressure.
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MOLE FRACTION
Mole fraction (Xi) is number of moles of one
particular gas divided by the total moles of gas in the
mixture.
Calculating partial pressure (pi)
pi = ptotal Xi
Example
A mixture of 2 mol H2 and 3 mol He
exerts a total pressure of 3 atm. What is
the partial pressure of He? 9/5
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Dalton’s Law of Partial Pressures
Example
The composition of gases in a “neon” advertising sign of volume
0.75 L is 0.10 g of neon and 0.20 g of xenon. Calculate their
partial pressures and the total pressure in atmospheres at 40 oC.
Solution
First find the number of moles of each gas, use the ideal gas
equation to find partial pressures and then Daltons law to find
the total pressure.
=0.17 atm
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Dalton’s Law of Partial Pressures
=0.052 atm
0.22 atm
Exercise
Mixtures of helium and oxygen can be used in scuba diving
tanks to help prevent “the bends.” For a particular dive, 46 L
He at 25oC and 1.0 atm and 12 L O2 at 25 oC and 1.0 atm
were pumped into a tank with a volume of 5.0 L. Calculate the
partial pressure of each gas and the total pressure in the tank
at 25oC.
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Vapour Pressure of water
The vapor pressure of water is the pressure exerted by
molecules of water vapor in gaseous form.
Example
A sample of oxygen gas of volume 1.00 L was collected
over water at 25 oC and a total pressure of 1.00 atm. The
vapour pressure of water at 25 oC is 23.8 Torr. What is the
mass of oxygen collected?
Solution
Given
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Vapour Pressure of water
Next find the moles of O2 collected:
Now find the mass of O2:
Gases
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Kinetic-Molecular Theory
Gas laws describe how gases behave when
conditions change.
Gas laws do not tell why gas behave as they do
Need a model (theory) to help us understand the
behaviour of gases
The kinetic-molecular theory is such a model
This is a model that aids in our understanding of what
happens to gas particles as environmental conditions
change.
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Main Tenets of Kinetic-Molecular Theory
1. Gases consist of large numbers of molecules that are in
continuous, random motion. The collisions of the
particles with the walls of the container are the cause of
the pressure exerted by the gas.
2. The combined volume of all the molecules of the gas is
negligible relative to the total volume in which the gas is
contained – gas particles are infinitesimally small.
3. Attractive and repulsive forces between gas molecules
are negligible.
4. The average kinetic energy of the molecules is
proportional to the absolute temperature.
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Kinetic-Molecular Theory
The average speed of molecules, root mean square
speed, urmsis
M is molar mass
The true test of a model is how well its predictions fit
the experimental observations.
Let’s consider how this model accounts for the
properties of gases as summarized by the ideal gas
law:
PV =nRT.
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Kinetic-Molecular Theory
Pressure and Volume (Boyle’s Law)
At constant n and T if the volume of a gas is decreased, the
pressure increases:
KMT: A decrease in volume means that the gas particles will hit
the wall more often, thus increasing pressure.
Pressure and Temperature
The ideal gas law predicts that,
KMT: When T increases, the speeds of gas particles increase,
the particles hit the wall with greater force and greater
frequency. Since V is the same, this results in increased gas
pressure.
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Kinetic-Molecular Theory
Volume and Temperature (Charles’s Law)
The ideal gas law indicates :
KTM: High T means high speeds and hence particleshit the
walls more often and with more force. For P to be constant, the
volume of the container must increase.
Volume and Number of Moles (Avogadro’s Law)
KMT: An increase in the number of gas particles at
constant T would cause the P to increase if V is
constant. The only way to return the pressure to its
original value is to increase the volume.
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Kinetic-Molecular Theory
Mixture of Gases (Dalton’s Law)
The observation that
where the PJ is the partial pressure of J
KMT assumes that all gas particles are independent
of each other and that the volumes of the individual
particles are unimportant. Thus the identities of the
gas particles do not matter.
Ideal gas law can be derived from KMT model by
applying the definitions of velocity, momentum, force,
and pressure to the collection of particles.
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EFFUSION
Effusion is the movement of gas molecules from one
container to another through a tiny hole.
Thomas Graham, a 19th century Scottish chemist, found
that the rate of effusion is inversely proportional to the
square root of its molar mass. This observation is now
called Graham’s law:
If we have two gases at same temperature and pressure
in identical vessels with identical pin-holes, Graham’s law
states
R1 and R2 are the rates of effusion of gases 1 and 2 with
molar masses M1 and M2, respectively.
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EFFUSION
Example
An unknown gas composed of diatomic molecules effuses at a
rate that is only 0.355 times that of O2 at the same
temperature. Calculate the molar mass of the unknown gas
and identify it.
Solution
which gives Mx = 254g mol-1
or
Since unknown is diatomic, its an element and its
atoms have molar mass 127 gmol-1, hence it is
iodine, I2 (use periodic table)
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Diffusion
Diffusion is the spread of one substance throughout
a space or throughout a second substance.
Diffusion like effusion is faster for lower mass
molecules than higher mass.
Molecular collisions make diffusion more complicated
Average distance a molecule travels per unit time is
called the mean free path.
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Real vs Ideal Gases
Real gases are non-hypothetical gases whose
molecules occupy space and have interactions.
An ideal gas is a theoretical gas composed of many
randomly moving point particles that do not interact.
Ideal gas obeys the gas laws or gas equation ( PV =
RT), at low pressure and relatively high temperature
Deviations from Ideal Behavior
At low pressure and fairly high temperature, real
gases show nearly ideal behavior and the ideal –gas
equation is obeyed.
At low temperature and sufficiently high pressure,
a real gas deviates significantly from ideality and the
ideal gas equation is no longer valid
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Explanation of deviations
Van Der waals attributed the deviation of real
gases from ideal behavior to two erroneous
postulates of the kinetic theory.
(i) The molecules in a gas are point masses
and posses no volume
(ii) There are no intermolecular attraction in a
gas
Therefore, the ideal gas equation derived
from kinetic theory could not hold for real
gasses. Volumes and pressure need to be
corrected to consider real gases.
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Corrections for Non-ideal Behavior
Volume correction
The volume of a gas is the free space in the
container in which molecules move about.
Volume of an ideal gas (v) is the same as the
volume of the container.
Therefore, the volume of the real gas is ideal Gas
volume (v) minus the volume occupied by gas
molecules (b)
(v-b)
For n moles of the gas, the corrected volume is
(v-nb)
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Corrections for Non-ideal Behavior
Pressure correction
A molecule in the interior of a gas is attracted by
other molecules on all sides. These attractive forces
cancel out.
Molecules about to strike the wall of the vessel is
attracted by the molecules on one side only.
Therefore, it strikes the wall with reduced velocity and
the actual pressure of the gas p will be less than the
ideal pressure
If the actual pressure p is less than pideal by a product
p, we have
p = pideal – p or pideal = P + P
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Corrections for Non-ideal Behavior
Pressure correction
A molecule about to strike the wall has a net inward
pull of attraction while a molecule in the interior of
gas has balanced attractions.
Therefore, pressure is determined by the force of
attraction between molecules (A) striking the wall of
container and the molecules (B) pulling them
inwards.
The net force of attraction is proportional to the
concentration of (A) type molecule and (B) type of
molecule
p = CA X CB or n/v X n/v (a is constant property)
p = an2/v2
Pressure in the ideal gas equation is corrected as
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(p + an2/v2 )
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Van Der waals Equation
Substituting the values of corrected volume and
pressure, in the ideal gas equation, PV = nRT, we
have
(p + an2/v2 ) (v-nb) = nRT (R=0.08205 L atm / mol·K)
This equation is called van der waals equation
For 1 mole of a gas (n=1), van der waals equation
becomes
(p + a/v2 ) (v-b) = nRT
constants a and b are called van der waals
constants. These constants are the characteristics of
each gas.
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Real Gases
Example
Consider a sample of 1.000 mol CO2(g) confined to a volume
of 3.000 L at 0.0 oC. Calculate the pressure of the gas using
(a) the ideal gas equation and (b) the van der Waals equation.
Solution
= 7.472 atm
= 7.5794 atm – 0.3989atm = 7.181 atm
Note:1st term is pressure corrected molecular volume. 2nd term
corrects for intermolecular forces.
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