Summary of Last lecture

Basic concepts of Thermochemistry

• Enthalpy
• H = E + PVIs a state function,
• heat change at constant pressure

• Hess Law and its use

• Standard enthalpies of formation and their

use

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 Chapter 9. Gases

Outline
1. Property of gases and gas laws
2. The Kinetic Molecular Theory of Gases
3. Real Gases

Reference and suggested reading

“Chemistry, an atoms first approach”, S. S. Zumdahl, S. A.
Zumdahl, 2rnd Ed.; 2016, Chapter 8.
 1. Property of Gases and gas laws
Gas is one of the three classical states of matter
 Importance of Gases
Gases are widely used in chemical industries.

e.g. ammonia (NH3) synthesis.

 General Properties of Gases
Property Description

Volume (V): Space occupied by the gas

Amount (n): quantity of gas

Temperature (T): Kinetic energy of gas particles

Force exerted by gases against

Pressure (P): the walls of the container.

• These properties are all related to one another.

 The Ideal Gas Law

The values for R:

The Ideal Gas Law:
PV = nRT
The constant of proportionality
is known as R, the gas
constant.

Note: The unit of T is K (Kelvin temperature), not oC.

Ideal gas:
•Gas particle has no volume
•No force between the particles
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 Other Gas Laws
Do you still remember the following Gas Laws?

1. Boyle P1V1 = P2V2

2. Charles or PV= k,
or V/T = k, V = kT
3. Gay-
Lussac
4. Avogadro
or P/T = k, P = kT 5. Dalton or V/n = k, V = kn

Ideal gas law: PV = nRT

 Other Gas Laws
Dalton’s Law of Partial Pressures
•The total pressure of a mixture of gases equals the sum of the
pressures that each gas would exert if it were present alone.

• In other words,
Ptotal = P1 + P2 + P3 + …

Thus,
RT
Ptotal 
V
n
 Exercise
1. You are holding two balloons of the same volume.
One contains helium, and one contains hydrogen.
Complete each of the following statements with
“different” or “the same”

a) The pressures of the gas in the two He

the same
balloons are _______________.

b) The numbers of moles of the gas in the

H2
the same
two balloons are _____________.

n = (PV)/(RT)

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 Exercise
2. VNe = 2VAr
PV= nRT
Molar Mass: Ne = 20.18; Ar = 39.95 n = PV/RT

Which of the following best represents the mass

ratio of Ne:Ar in the balloons?  

a) 1:1 b)1:2 c) 2:1 Ne

d) 1:3 e) 3:1
A
Since VNe = 2VAr, nNe = 2nAr, r

 Mass ratio of Ne:Ar

= 2x20.18:1x39.95 = 1:1
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 4. Kinetic-Molecular Theory of Gases
(KMT)
For ideal gases

PV = nRT

How can we explain the gas law?

A simple model is the Kinetic-Molecular Theory

4. Kinetic-Molecular Theory of Gases
1) The particles are so small
compared with the distances
between them that the volume
of the individual particles can
be assumed to be negligible
(zero).

2) The particles are in constant

motion. The collisions of the
particles with the walls of the
container are the cause of the
pressure exerted by the gas.

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 Constant Motion

The particles are in constant motion.

P  speed, and
frequency

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 Assumptions of the
Kinetic Molecular Theory
3) The particles are assumed to exert no
forces on each other; they are
assumed neither to attract nor to
repel each other.
4) Energy can be transferred between
molecules during collisions, but the
average kinetic energy of the
molecules does not change with time.

The average kinetic energy of a

For 1 molecule,
collection of gas particles is assumed Ek = (1/2)mv2
to be directly proportional to the For 1 mole gas
Kelvin temperature. Ek = (3/2)RT

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 Velocity of Gas Molecules
• Molecules of a given gas have a range of speeds at a
given temperature.

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Root Mean Square Velocity of Gases

3RT
urms =
M
• u = the speed in m/s
• R = 8.3145 J/K·mol
• T = temperature of gas (in K)
• M = mass of a mole of gas in kg

• Speed INCREASES with T

• Speed DECREASES with M

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 Velocity of Gas Molecules
• Average velocity increases with increasing
temperature.

3RT
urms =
M

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 Velocity of Gas Molecules
• Average velocity decreases with increasing mass.

3RT
urms =
M

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 Using KMT to Understand Gas Laws

• Origin of Pressure – Gas

molecules hitting
container walls

– KE  , P?
force , P 

– # n , P?
# collisions  , P 
 KMT and Boyle’s Law

V 1.
Decrease V

Volume  , Collision rate  ,

thus P 
 KMT and Charles’ Law

V = kT increase T

T , kinetic energy , gas molecules

hit walls with greater force, this
increases the Pressure if volume is
not change.

To keep the pressure constant, only

volume has to be increased

Volume Increase to reduce

Pressure
 5. Real (Non-Ideal) Gases

For Ideal Gases:

PV = nRT
1
PV
=1
nRT P

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 5. Real (Non-Ideal) Gases
For Ideal Gases: However, in real world….
PV = nRT Plots of PV/nRT Versus P for
Several Gases (200 K)

PV
=1
nRT

Deviate from
1 especially
at high
pressure

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 5. Real (Non-Ideal) Gases
For Ideal Gases: However, in real world….
PV = nRT Plots of PV/nRT Versus P for N2 at
three temperature

PV
=1
nRT

Deviate from 1
is also
significant at
lower
temperature Why?
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Main Reasons for Deviations from Ideal Gas
Law
• Real molecules have volume.

• There are intermolecular

forces.
– Otherwise a gas could not
become a liquid.

The assumptions made in

the kinetic-molecular model
break down especially at
high pressure and/or low
temperature.

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Corrections for Non-Ideal Behavior
Ideal Gases: PV = nRT
less
A real gas has volume. V (Videal) is _____
than Vactual
Videal < Vactural or Vmeasured

V = Vactural - nb
For a real gas, there are
intermolecular attractions. The
lower
observed pressure is ____ than the
pressure expected for an ideal gas

Pideal > Pactual

P = Pactural + n2a/V2

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Deviations from Ideal Gas Law: The van der
Waals Equation
• Equation accounting for volume of
molecules and intermolecular forces

Measured P Measured V

J. van der
Waals, 1837-
1923, Professor
of Physics,
intermol. forces vol. correction Amsterdam.
Nobel Prize
1910.
n: number of mole
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 Exercises
1. Why is non-ideal gas behavior important in the
following cases?
• Pressure of the gas is high.
• Temperature is low.

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 Exercises
1. Why is non-ideal gas behavior important in the
following cases?
• Pressure of the gas is high.
• Temperature is low.

• When Pressure of the gas is high:

• Concentration of gas particles is high.
• Volume of gases can not be ignored.

• When Temperature is low.

• Kinetic energy is less
• Attractive forces become important.

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 Chapter Summary
• Gas laws:
– Ideal gas law: PV=nRT
– Related gas laws:
Boyle, Charles, Gay-Lussac, Avogadro, Dalton

• The Kinetic Molecular Theory of Gases

– Pressure is caused by collisions of particles with wall.
– Average speed: u 3RT
rms =
M

– Average kinetic energy of 1 mole gas: Ek = (3/2)RT

• Real gases
– Real gases behave less ideally at high pressures or low
temperatures (volume, intermolecular forces)