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Chapter 10: Gases

Part 3: Real Gases


Prepare for Recitation October 20th
ALEKS Objective 8 due October 18th
ANGEL Quiz 8, October 20th
Lecture 22: October 12th
Lecture 23: October 14th
Lecture 24: October 17th
Read: Ch. 10.1-10.9
Additional Preparation:
BLB 10: 5,23,30,45,71,75,82-84; Packet 10: 1-15
BLB 25: 11,12,25

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Chapter 10: Gases


Part 3: Real Gases
KEY QUESTIONS: THE BIG PICTURE
What does partial pressure mean?
What type of mixtures do gasses form?
What state equation can we use to
describe mixtures of gasses?
Remember: macroscopic properties
come from microscopic origins
How does the energy of a molecule in a
gas compare with intermolecular forces?
How can we describe mixtures of
gasses?
How do real gasses differ from ideal
gasses?

By the end of Todays Lecture you should know:


Kinetic-molecular theory
Real gases (van der Waals)

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Effusion and Diffusion


Effusion:
Diffusion:

Heavy molecules diffuse (or effuse)


more ______ than lighter ones.
r proportional to

1
M

Grahams Law of Effusion:

r1
r2

M2
=

M1

Note: Diffusion is more complicated due to


collisions between gas molecules, but it also
obeys Grahams Law.
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Practice Problem
An unknown gas effuses at a rate 1.49 times
faster than Cl2. What is the molecular weight
of the gas?
A.
B.
C.
D.
E.

16.0 g/mol
31.9 g/mol
47.6 g/mol
106 g/mol
157 g/mol

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Collisions and Diffusion


The rate of diffusion
follows Grahams Law
At STP molecules
collide ~ 1010 times
per second
N2 speed = 500 m/s
but
in 1 s it collides 1010 times
Mean Free Path (MFP):

What happens to the MFP as density and


pressure decrease?
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Review of Density and Molar Mass


The Ideal Gas Law

The Connection between moles and mass


m (mass)
n moles =
M (molar mass)
The Ideal Gas Law becomes:

The definition of density:

m
d=
V

Density and the Ideal Gas Law:

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Practice Problem
Silicon tetrachloride is a starting material for
the production of electronics-grade silicon.
Calculate the density of pure silicon
tetrachloride vapor at 85oC and 758 torr.
A.
B.
C.
D.
E.

0.238 g/L
5.77 g/L
1.00 g/L
24.3 g/L
0.056 g/L

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Real Gases Deviate from Ideal Behavior


For an ideal gas:
PV
=1
nRT

PV = nRT

For a non-ideal gas (a real gas) this is not


true for ____ pressure or ___ temperature.
Reasons:
1. Molecules have finite size.
PV
>1
nRT
2. Molecules exert attractive forces (IMF)
PV
<1
nRT

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KMT and Non-Ideal Gas Behavior


Why does PV = nRT ?
Kinetic Molecular Theory has 5 key
postulates:
1) straight-line motion in random directions
2) Molecules are small & have no volume
3) No intermolecular interactions
4) Elastic collisions
5) Mean kinetic energy temperature
E = mv2
Deviations from ideal gas behavior are
caused because gas molecules/atoms have
___________ and have _______________
when they are close together.
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Real Gases: At High Pressure,


Postulate 2 in KMT is Not True
For 1 mole of ideal gas: PV/RT = 1

At low pressures, deviation from ideal


behavior is small.
At high pressures, use of the ideal gas law
leads to an appearance of larger n.
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Real Gases: At Low Temperature,


Postulate 3 in KMT is Not True
For 1 mole of ideal gas: PV/RT = 1

At low T or high P, attractive forces lead to


the appearance of a smaller n.
(IMF cause molecules to stick together)
As temperature increases the behavior of
real gases becomes more ideal.
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How Do We Account for This Behavior?


Attractive forces lead
to the appearance of a
smaller volume or
smaller n (depending
on which was given)

High
Pressure

Very High
Pressure

Finite molecular
volume leads to
repulsion and the
appearance of a larger
volume or larger n

Low Pressure

Attractive forces and


finite molecular
volume have minimal
impact

As Temperature
increases the
behavior of
real gases
becomes more ideal
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@ high temps the


kinetic energy
overcomes the
attractive forces

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Non-Ideal Behavior and


Measured Pressure
For any gas we can
measure P, V, T
But at higher P, the
measured P is too
small because of
attractive forces

The amount of missing P is proportional


to:
1) the size of the attractive forces (a)
2) the frequency of collisions (n/V)2
To compensate, use:
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Non-Ideal Behavior and


Measured Volume
For any gas we can measure P, V, T
But at higher P, the measured V is too
large because of the finite molecular
volume per mole (b)

(BLB Figure 10.25)

Actual volume:
Vactual = Vmeasured Vexcluded
To compensate, use:
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van der Waals Equation


The Equation of state for IDEAL gases:

PV = nRT
The Equation of state for REAL gases:
2

n
( P + 2 a )(V nb) = nRT
V

Table 10.3 lists van der Waals constants (a,b)


for various gas molecules.
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Practice Problem
What is the pressure P of 1.0 mol Cl2 in a
2.0 L vessel at 273 K?
Ideal Gas:

van der Waals:


a = 6.49

L2 atm
mol2

b = 0.0562 L/mol

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KMT and Non-Ideal Gas Behavior:


Does This Make Sense?
2

n
( P + 2 a )(V nb) = nRT
V

Kinetic Molecular Theory has 5 key


postulates and two have caused
problems:
2) Molecules are small & have no volume
3) No intermolecular interactions
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KMT and Non-Ideal Gas Behavior:


Does This Make Sense?
n2
( P + 2 a )(V nb) = nRT
V
Molecules are small & have no volume.
At LOW Pressure:
The volume of the container is ________
compared with the volume of the particles
At HIGH pressures:
The volume of the particles becomes
________ and the volume available to the
gas is _________ the container volume
Gas
Ne
Ar
Kr
Xe

b (L/mol)
0.0171
0.0322
0.0398
0.0510

Size

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KMT and Non-Ideal Gas Behavior:


Does This Make Sense?
n2
( P + 2 a )(V nb) = nRT
V
Molecules in a gas have no interactions.
At LOW Temperature:
Intermolecular forces tend to be _________
and the KE is insufficient to overcome them
At HIGH Temperature:
The KE of the particles becomes ________
the intermolecular forces and the behavior
of the gas becomes __________
Gas a (atm L2/mol2) IMF
CH4
2.25
NH3
4.17
H2O
5.46

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Strength

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What You Should Know


Kinetic Molecular Theory
How does KMT explain the pressure and
temperature of a gas, the gas laws, and
the rates of effusion and diffusion?
Real Gases
What effect does the V of a gas particle
have when we assume an ideal gas?
What effects do intermolecular forces
have on the observed properties of gases
when we assume an ideal gas?
How does the van der Waals Equation
explain the properties of real gases?
In what way do you expect a real gas to
deviate from ideal behavior as pressure
is increased from low to high?
In what way do you expect a real gas to
deviate from ideal behavior as
temperature increases?
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