• Ch.

21 Molecules in motion
Molecular motion in gases
Molecular motion in liquids
Diffusion: migration of matter down a concentration gradient

• The molecular motion in gases

1. The kinetic model of gases
b) The collision frequency
c) The mean free path
2. Collisions with walls and surfaces
3. The rate of effusion
4. Transport properties of a perfect gas
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-1
 • The kinetic model enables us to calculate the frequency with
which molecular collisions occur (called collision frequency) and
the average distance a molecule travels between collisions
(called mean free path).

d • We count a hit whenever the centers of

two molecules come within a distance d
d of each other.

• The distance d is the collision diameter*.

* The collision diameter is of the order of the molecular diameters.

Assuming the molecules are hard spheres, the d is the diameter of the
molecules.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-2
 • The collision frequency (z) is the # of
collisions made by one molecules
divided by a time interval t.

• When there are N molecules in a
volume V, (number density N)
*
z   crel N

where the  is called the collision

cross-section of the molecules.  = d2
p N
• In terms of pressure, using pV  nRT  nkN AT  NkT  
kT V
N p
z   crel z   crel
* See Justification 21.3. V kT
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-3
 N
z   crel
V
• At constant V, the collision frequency increases with
increasing T due to the faster relative mean speed.

p
z   crel
kT
• At constant T, the collision frequency is proportional to
pressure due to the greater the number density.

Ex) For an N2 molecule at 1 atm and 25 oC, z ~ 5109/s

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-4
 • The mean free path (), which is the average distance
traveled by a molecule between collisions, can be calculated
from the collision frequency.

• If a molecule collides with a frequency z, it spends a time 1/z

in free flight between collisions.
c rel
• Therefore, the mean free path is:  
z
p
Substituting z   crel ,
kT

crel crel kT kT kT
   
z  crel p p p
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-5
 kT V 1
pV  nRT  nN AkT  NkT  
p N N
kT V
 
p N

• Doubling the p reduces the  by half (if V is variable).

• However, at constant V, the distance between collisions is

determined by the number of molecules (N) present in the
given V, not by the speed at which they travel.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-6
 • A typical gas N2 at 1 atm and 25 oC travels with a mean
speed of ~ 500 m/s.

• Each molecule makes a collision within ~ 1 ns.

• Each molecule travels ~ 1000 molecular diameters between

collisions.

At these conditions, N2 gas behaves nearly perfectly.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-7
 • For accounting for transport in the gas phase, the rate at
which molecules strike an area (called collision flux) should
be obtained.

• The collision flux (Zw) is the number of collisions with an area

in a given time interval.
*
# of collision 1 p
ZW  ZW  c N 
area  time 4 2mkT

• Ex) At 1 atm and T = 300 K, a container receives

~31023/cm2·s.

* See Justification 21.4.  Correct the printing typos.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-8
 • Effusion is the process where individual molecules flow
through a hole without collisions between molecules.
• Effusion occurs if the diameter of the hole is considerably
smaller than the mean free path of the molecules.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-9
 • When a gas (p and T) is separated from a vacuum by a small
hole, the rate of escape of its molecules is equal to the rate at
which they strike the area of the hole.
• For a hole of area Ao, pAo
reffusion, A  ZW Ao 
2mkT

• Using R = kNA and M = mNA, pAo N A

reffusion, A 
2MRT

• The rate of effusion is inversely proportional to M .

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-10
 •The Graham’s law: For two gases, their effusion rates are
related to their masses (mA and mB) as:

reffusion, A MB

reffusion, B MA

• The Graham’s law of effusion reveals that the rate of effusion

is inversely proportional to M because the rate at which they
strike the area of the hole is also inversely proportional to M .

pAo N A
reffusion, A 
2MRT

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-11
 pAo
reffusion, A  ZW Ao 
2mkT
• The equation is utilized to determine the vapor pressures of
liquids and solids, particularly of substances with very low vapor
pressures.  called Knudsen method

• When particles (mass m) are escaped

through a hole by the effusion, the mass loss
m is monitored to determine p.
Knudsen cell:
a cavity with a
m  ZW Ao mt
small hole
*
2RT m
, p
p
• Substituting the equation for ZW 
2mkT M Ao t
* See Example 21.2.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-12
 • Transport properties of a substance are its ability to transfer
matter, energy, or some other property from one place to
another.
• Diffusion: the migration of matter down a
 concentration gradient.
 • Thermal conduction: the migration of energy down a
Gas
 temperature gradient.
 • Viscosity: the migration of linear momentum down a
velocity gradient.
• Electrical conduction: the migration of electric charge
along an electrical potential gradient.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-13
 • Transport properties are commonly expressed by
phenomenological or empirical equations.
• The rate of migration of a property is measured by its flux (J).
• The flux is the quantity of a property passing through a given
area in a given time interval (quantity per area per time).
ex) matter flux for diffusion, energy flux for thermal conduction
• Experimental observations on transport properties show that
the flux of a property (J) is usually proportional to the 1st
derivative of some other related property.
Ex) Diffusion: concentration gradient.
Thermal conduction: temperature gradient.
Viscosity: velocity gradient.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-14
 • For the diffusion, the matter flux diffusing
parallel to the z-axis of a container is
proportional to the 1st derivative of the
concentration.
dN
J (matter) 
dz

where N is the number density of particles.

• The SI units of the matter flux is [number/m2·s]

• If the concentration varies steeply with position, the diffusion
will be fast.
• If the concentration is uniform (dN/dz = 0), there is no net flux.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-15
 • Because matter flows down a concentration
gradient from high to low concentration, J is
positive if dN/dZ is negative.
• Therefore, the proportionality coefficient
must be negative. We write it –D.
dN
J (matter)   D
dz

Fick’s 1st law of diffusion

• The constant D is called the diffusion coefficient .

• The SI units of D are [m2/s]

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-16
 • For the thermal conduction, the energy flux associated with
thermal motion is proportional to the temperature gradient.
dT
J (energy) 
dz
• The SI units of the energy flux are [J/m2·s]
• The proportionality coefficient is –.
dT
J (energy)  
dz

where the  is called the coefficient of thermal conductivity.

• The SI units of is  are [J/K·m·s]

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-17
 • To see the connection between the momentum flux and the
viscosity, consider a fluid in a state of Newtonian flow.

• The Newtonian flow can be imagined as

occurring by a series of layers moving past
one another.
• The velocity of successive layers varies
linearly with distance z from the wall.
• The particles bring their initial momentum
when they enter a new layer which is
accelerated or retarded.
• The net retarding effect is interpreted as the fluid’s viscosity.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-18
 • Because the retarding effect depends on the transfer of the x-
component of momentum, the viscosity depends on this
momentum flux in the z-direction.
• The flux of x-component of momentum is
proportional to dvx/dz.
• As a proportionality coefficient, we use –.
dv x
J (x - component of momentum)  
dz

• The  is called the coefficient of viscosity

or simply the viscosity.
• The SI units of  are [kg/m·s].
• Viscosities are sometimes reported in poise (P).
1P = 0.1kg/m·s
Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-19
 • Next Reading:

8th Ed: p.758 ~ 766

9th Ed: p.757 ~ 762

Prof. Yo-Sep Min Physical Chemistry II, Fall 2013 Lecture 2-20