Chapter 14

The Ideal Gas Law & Kinetic

Theory

14.1 Molecular Mass, Avogadro Number

14.2 Equation of state of an Ideal Gas
14.3 Kinetic Theory of Gases
14.4 Diffusion
Molecular Mass & Avogadro’s
Number
 The atomic mass unit (1u) is defined
as:

1u = mass of the neutral 12C atom.

1u=1.6605
  10 −27 Kg
Molecular mass of a molecule is the
sum of its atomic masses.

Example:
The molecular mass of H2O is:

2mH + mO = 21.00794 u + 15.9994 u = 18.0153 u

Molecular Mass & Avogadro’s
Number
Macroscopic amount of materials contain large
numbers of atoms or molecules. It is more
convenient to express such large numbers in mole
(mol).
One mole of a substance contains Avogadro’s number (NA)
of molecules NA = 6.022x1023 mol-1

The number of moles n contained in any sample is given

by:
  𝑁
𝑛=
𝑁𝐴
Where N is the number of particles (atoms or molecules) in the sample.
Equation of State of an Ideal gas
Since solids and liquids have a fixed volume at a
given temperature, it is possible to describe the
volume expansion by:
∆ 𝑉 =𝛽 𝑉 𝑖 ∆ 𝑇
 

In case of gases however, the interatomic forces are usually

weak such that there is no equilibrium separation for the
atoms. The volume of a gas is always variable and can be
defined only by the container holding the gas.
Thus, for a gas it is important to find the relation between the pressure
P, temperature T and volume V:

𝑃= 𝑃(𝑇 , 𝑉 )
  Equation of State
Equation of State of an Ideal gas
Keeping the temperature of the gas
constant while increasing the pressure,
we see a decrease in the volume, this is
linear as function of 1/P. Boyle’s law.

  𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃=
𝑉

The volume V varies proportional to T

at constant pressure. Charles’s Law
 𝑃=𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × T
Equation of State:
𝑃𝑉 =𝑛𝑅𝑇
 
Animation Credits goes to:
https://en.wikipedia.org/wiki/Boyle%27s_law
https://en.wikipedia.org/wiki/Charles%27s_law
Equation of State of an Ideal gas
Equation of State of an ideal gas:
 
𝑃𝑉 =𝑛𝑅𝑇
 Where is the gas constant  𝑅=0.08314 Liters . atm
mol . K
It follows: the volume of 1 mol of a gas at atmospheric pressure and at 0°C (273
K) is 22.4 Liters.

The equation of state can be expressed in terms of the total

number molecules N:
  𝑁 𝑁
 
𝑃𝑉 =𝑛𝑅𝑇 → 𝑃𝑉 = 𝑅𝑇 =𝑘 𝐵
𝑁𝐴 𝑁𝐴
 
𝑃𝑉 =𝑁 𝑘 𝐵 𝑇
 
Example
A spray can at pressure 202 kPa and a volume of 125 cm3 at
22 C. The can is tossed into open fire and heated up to 195
C.
What is the pressure inside the can?
The can has a fixed volume and a fixed content, So, n and V are constant.
 𝑃 𝑃𝑖 𝑃 𝑓 𝑇 4 68
𝑇
=𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → =
𝑇𝑖 𝑇𝑓 𝑇𝑖 ( ) ( )
→ 𝑃𝑓 = 𝑓 𝑃𝑖 =
295
202=320 kPa

What is the number of mole in the can?

5 −6
  𝑃𝑉 ( 2.02×10 )(125 ×10 )
𝑛= = =0.0103mol
𝑅𝑇 8.314 × 295
Molecular Model of an Ideal Gas
 Macroscopic properties of a gas were
pressure, volume and temperature
 Can be related to microscopic description
 Matter is treated as a collection of molecules
 Newton’s Laws of Motion can be applied
statistically
 The microscopic description is consistent
with the macroscopic description developed
earlier
Ideal Gas Assumptions
 The number of molecules in the gas is large,
and the average separation between the
molecules is large compared with their
dimensions
 The molecules occupy a negligible volume within
the container
 This is consistent with the macroscopic model
where we assumed the molecules were point-like
Ideal Gas Assumptions, 2
 The molecules obey Newton’s laws of
motion, but as a whole they move randomly
 Any molecule can move in any direction with any
speed
 The molecules interact only by short-range
forces during elastic collisions
Ideal Gas Assumptions, 3-4
 The molecules make elastic collisions with
the walls leading to the macroscopic
pressure on the walls of the container
 The gas under consideration is a pure
substance i.e. All molecules are identical

In Resume:
VERY LARGE NUMBER OF MOLECULES
NEWTON LAW CONTROLS THE MOTION OF MOLECULES
ELASTIC COLLISIONS
PURE SUBSTANCE
Pressure and Kinetic Energy
 Assume a container is
a cube of edge d
containing N molecules

Assuming perfect elastic

collision.
Initial and Final Linear
momentum (pi before &
pf After collision) are:
Pi = mVx
Pf = -mVx “the particle bounces off”
Pressure and Kinetic Energy, 2
The Change in momentum
“along the x-axis” is:
DPx = Pf –Pi = 2mVx
But DPx = Fx.Dt
The time between two collisions is:

2d
t 
Vx
 2mVx  2mVx  mVx2
Fx   
t 2d
Vx d
Pressure and Kinetic Energy, 2
 mVx2 The force exerted by the
Fx 
d molecule on the wall is of
the same magnitude but
mVx2
opposite direction F 
d
The Total Force of N molecules:
Fx 
m 2
d

Vx1  Vx2
2
 ....  VxN
2

V 2
 V 2
 ....  V 2
Nm 2
But Vx2  x1 x2 xN
Fx  Vx
N d
Pressure and Kinetic Energy, 2
Nm 2
Fx  Vx But in three dimensions we have:
d
V2
x
2
,V & V
y
2
z  V 2  3Vx2
Thus, the total force exerted on the wall is:


N m V 2 
F N  m V 
2

F  P  
2  N  1
  m V 2

3 d  A 3 d  3
3  V  2 
 
 
Pressure and Kinetic Energy, 2
2  N  1 2
P    m V 
3  V  2 

In Conclusion, the pressure is proportional

to the Number of Molecules per unit Volume
and to their average Translational Kinetic
Energy
Pressure and Kinetic Energy,
final
 One way to increase the pressure is to
increase the number of molecules per unit
volume
 The pressure can also be increased by
increasing the speed (kinetic energy) of the
molecules
Molecular Interpretation of
Temperature
 We can take the pressure as it relates to the kinetic
energy and compare it to the pressure from the
equation of state for an ideal gas

2 1 2
PV  N m V   Nk BT
3 2 
1 2 3
K E   m V   k BT
2  2
The temperature is a direct measure of the Average
Kinetic energy
Molecular Interpretation of
Temperature, cont
 Simplifying the equation relating temperature
and kinetic energy gives
___
1 3
mo v  kBT
2

2 2
 This can be applied to each direction,
1 ___2 1
m v x  kBT
2 2
 with similar expressions for vy and vz
A Microscopic Description of
Temperature, final
 Each translational degree of freedom
contributes an equal amount to the energy of
the gas
 In general, a degree of freedom refers to an
independent means by which a molecule can
possess energy
 A generalization of this result is called the
theorem of equipartition of energy
Total Kinetic Energy
 The total kinetic energy is just N times the kinetic
energy of each molecule
 1 ___2  3 3
K tot trans  N  m v   NkBT  nRT
2  2 2
 If we have a gas with only translational energy, this
is the internal energy of the gas
 This tells us that the internal energy (U) of an ideal
gas depends only on the temperature
  3
U = 𝑛𝑅𝑇
2
Root Mean Square Speed
 The root mean square (rms) speed is the
square root of the average of the squares of
the speeds
 Square, average, take the square root
 Solving for vrms we find
3kBT 3RT
v rms  
m M
 M is the molar mass and M = mNA
Some Example vrms Values

At a given temperature, lighter molecules move

faster, on the average, than heavier molecules
Ludwig Boltzmann
 1844 – 1906
 Austrian physicist
 Contributed to
 Kinetic Theory of Gases
 Electromagnetism
 Thermodynamics
 Pioneer in statistical
mechanics
Distribution of Molecular
Speeds
 The observed speed
distribution of gas
molecules in thermal
equilibrium is shown at
right
 NV is called the Maxwell-
Boltzmann speed
distribution function
 Use the active figure to
measure the number of
molecules in the blue bar
Distribution Function
 The fundamental expression that describes the
distribution of speeds in N gas molecules is
3/2
 mo   mv 2 / 2 kBT
NV  4 N  
2
v e
 2 kBT 
 mo is the mass of a gas molecule, kB is Boltzmann’s
constant and T is the absolute temperature
Speed Summary
 Root mean square speed

3kBT kBT
v rms   1.73
mo mo
Speed Distribution
 The peak shifts to the
right as T increases
 This shows that the
average speed increases
with increasing temperature
 The asymmetric shape
occurs because the
lowest possible speed is
0 and the highest is
infinity
Speed Distribution, final
 The distribution of molecular speeds depends
both on the mass and on temperature
 The speed distribution for liquids is similar to
that of gases
Evaporation
 Some molecules in the liquid are more energetic
than others
 Some of the faster moving molecules penetrate the
surface and leave the liquid
 This occurs even before the boiling point is reached
 The molecules that escape are those that have
enough energy to overcome the attractive forces of
the molecules in the liquid phase
 The molecules left behind have lower kinetic
energies
 Therefore, evaporation is a cooling process
Diffusion
The process in which molecules move from a
region of higher concentration to one of lower
concentration is called diffusion.

For example: You can smell the perfume

(or cigarette smoke) at some distance from
an open bottle because perfume molecules A drop of ink placed in water
leave the space above the liquid in the eventually becomes completely
dispersed because of diffusion.
bottle and diffuse to lower concentration
area.

The host medium, such as the air or

water in the adjacent examples, is
referred to as the solvent, while the
diffusing substance, like the perfume
molecules or the ink, is known as the
Perfume
solute. bottle
Diffusion
Why Diffusion is Relatively Slow
A gas molecule has a translational speed Vrms of hundreds of
meters per second at room temperature as we saw in the
previous section.
At such speed, a molecule could travel
across an ordinary room in just a fraction of
a second. Yet, it often takes several
seconds, and sometimes minutes, for the
perfume smell to reach the other side of the
room. Why does it take so long?
Perfume
bottle
When a perfume molecule diffuses through air,
it makes millions of collisions each second with
air molecules.
Although it does move very fast between collisions, a perfume molecule
wanders only slowly away from the bottle because of the zigzag path.
Diffusion
“Transdermal” Drug delivery:
Nicotine patches, for example, are used to
deliver nicotine through your skin in programs
designed to help you stop smoking.

Quantifying Diffusion:
To quantify diffusion we shall use the same
logic for the flow of heat by conduction
between a hot and a cold reservoir.

  𝑄 ( 𝐽 ) 𝑘 A ( 𝑇 2 −𝑇 1 )
𝑃= = Conduction
∆ 𝑡 ( 𝑠) 𝐿

  (𝐷 . 𝐴 . ∆ 𝐶)∆ 𝑡 mass of Diffused solute

𝑚=
𝐿
D = diffusion coefficient
DC = concentration difference
between the two ends of the Channel
 Diffusion, FICK’s Law
  (𝐷 . 𝐴 . ∆ 𝐶)∆ 𝑡
𝑚= m is mass of diffused solute in Kg
𝐿
D = diffusion coefficient in m2/s.
DC = concentration difference
between the two ends of
the Channel in (Kg/m3).
  = Cross Sectional Area in (m2).

  = Length of the Channel in (m).

  = the time, duration of the process in (s).

Diffusion, FICK’s Law
In the lungs, oxygen in very small sacs called alveoli diffuses into the
blood. The diffusion occurs directly through the walls of the sacs, which
have a thickness L. The total effective area A across which diffusion
occurs is the sum of the individual areas (each quite small) of the
various sac walls. Considering the fact that the mass m of oxygen that
enters the blood per second needs to be large and referring to Fick's
law of diffusion, what can you deduce about L and about the total
number of sacs present in the lungs?

a) The thickness is large and the total number of sacs is small.

b) The thickness is small and the total number of sacs is large.
c) The thickness is small and the total number of sacs is small.
d) The thickness is large and the total number of sacs is large.

  (𝐷 . 𝐴 . ∆ 𝐶)∆ 𝑡
𝑚=
𝐿
Energy in Your Lungs
The volume of human adult lungs is approximately 6 liters
(6.0×10−3 m3), and the pressure in your lungs is approximately 1
atm (1.0×105 Pa). Assume the temperature of the air is close to
internal body temperature or 37°C (310 K). How much internal
energy is contained in the air within your lungs?

  𝑃𝑉 105 ×6 ×10 −3
𝑛= = =0.23 𝑚𝑜𝑙
𝑅𝑇 8.314 ×310
  3 3
U = 𝑛𝑅𝑇 = 0.23 ×8.314 × 310=890 𝐽
2 2

This value is large and is equivalent to the Kinetic energy of a

baseball moving at 400 Km/h.