PERGERAKAN

MOLEKUL
/DIFFUSION
By : Berlian Sitorus, Ph.D
Universitas Tanjungpura
 DIFFUSION

qWhy do you need to know q What is the key q What do you need to know already?
this? idea? This Topic draws on arguments relating to
Molecules and ions the calculation
The diffusion of chemical
tend to spread into of flux (Topic 16A) and the notion of drift
species through space speed introduced
determines the rates of many a uniform
distribution. in Topic 16B. It also uses the concept of
chemical reactions in chemical chemical
reactors, living cells, and the potential to discuss the direction of
atmosphere. spontaneous change.

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DIFFUSION
q Several derivations in this Topic use Fick’s first law of diffusion, which is discussed in Topic
16A and repeated here for convenience:

q Where 𝒩 is the number density and D is the diffusion coefficient.

q In a number of cases it is more convenient to discuss the flux in terms of the amount of
molecules and the molar concentration, c.
q Division by Avogadro’s constant turns eqn 16C.1a into

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THE POINT OF VIEW
That solutes in gases, liquids, and
solids have a tendency to spread can
be discussed from three points of
view as follows.
1. The thermodynamic viewpoint makes use of the Second Law of thermodynamics and
the tendency for entropy to increase and, if the temperature and pressure are constant,
for the Gibbs energy to decrease.
2. The second approach is to set up a differential equation for the change in
concentration in a region by considering the flux of material through its boundaries.
3. The third approach is based on a model in which diffusion is imagined as taking place
in a series of random small steps.
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 At constant temperature and pressure, the maximum non
Expansion work that can be done by a spontaneous process
is equal to the change in the Gibbs energy.

In this case the spontaneous process is the spreading of a solute,

and the work it could achieve per mole of solute molecules can be
identified with the change in the chemical potential of the solute.
THE d𝑤! = 𝑑"
THERMODYNAMIC
VIEW The difference in chemical potential between the locations 𝑥 +
𝑑𝑥 dan 𝑥 is :

so the molar work associated with migration through dx is

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 The Thermodynamic View - 2
q The work done in moving a distance d𝑥 against an opposing force, ℱ in this context, a molar quantity) is
d𝑤! = ℱ𝑑𝑥.

q By comparing the two expressions for d𝑤! it is seen that the slope of the chemical potential with respect to
position can be interpreted as an effective force per mole of molecules.
q This thermodynamic force is written as

q There is not a real force pushing the molecules down the slope of the chemical potential: the apparent force
represents the spontaneous tendency of the molecules to disperse as a consequence of the Second Law and
the tendency towards greater entropy.

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 The Thermodynamic View - 3
q In a solution in which the activity of the solute is a, the
chemical potential is 𝜇 = 𝜇! + 𝑅𝑇𝑙𝑛𝑎
q The thermodynamic force can therefore be written in terms
of the gradient of the logarithm of the activity:
q If the solution is ideal, a may be replaced by c/c𝜃., where c is
the molar concentration and c𝜃 is its standard value (1 mol
dm-3):
q The thermodynamic force acts in many
respects like a real physical force. In
particular it is responsible for accelerating
solute molecules until the viscous drag
they experience balances the apparent
driving force and they settle down to a
steady ‘drift speed’ through the medium.
q By considering the balance of apparent
driving force and the retarding viscous
force it is possible to derive Fick’s first law
of diffusion and relate the diffusion
coefficient to the properties of the
medium.
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Example :
Calculating the thermodynamic force

C=C0 + 𝛼𝑥
!" !"! !$#
= +
!# !# !#
!"
=0+𝛼
!#
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 Self Test :
Suppose that the concentration of a solute decreases
"#
exponentially to the right as 𝑐 𝑥 = 𝑐! 𝑒 ⁄$ .
Derive an expression for the thermodynamic force at
any position.
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Deriving Fick’s first law of diffusion

𝑅𝑇 𝑑𝑐
𝑁$ 𝑓𝑠 = −
𝑐 𝑑𝑥
%& *) %
𝑠=− ; =𝑘
'!() *+ '!

!×∆$×%×&
𝐽= %×∆$
= 𝑠𝑐
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Deriving Fick’s first law of diffusion - 2

𝐽 = 𝑠𝑐 𝑘𝑇 𝑑𝑐
𝑠=−
𝑓𝑐 𝑑𝑥

𝑘𝑇 𝑑𝑐
𝐽=−
𝑓 𝑑𝑥

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Deriving Fick’s first law of Brief Illustration-1
diffusion - 3

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The Diffusion
Equation qDiffusion results in the
modification of the distribution
of concentration of the solute (or
of a physical property) as
inhomogeneities disappear.
qThe discussion is expressed in
terms of the diffusion of
molecules, but similar arguments
apply to the diffusion of other
entities, such as ions, and of
various physical properties, such
as temperature.
A) Simple Diffusion
qThe diffusion equation, one of
the most important equations for
discussing the properties of
fluids, is an equation that
expresses the rate of change of
concentration of a species in
terms of the inhomogeneity of its
concentration.
qIt is also called ‘Fick’s second law
of diffusion’, but that name is
now rarely used. The diffusion
equation can be derived on the
basis of Fick’s first law.
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How is that done?
-Deriving the diffusion equation-

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-Deriving the
diffusion
equation-
Step 2 : Relate the
fluxes to the
concentration
gradients

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Step 3 : Combine the expression for the net
flux with that for the time dependence of
concentration

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Brief
Illustration
16C.2

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 Convection is the bulk motion of
regions of a fluid.

B) Diffusion with This process contrasts with

diffusion in which molecules move
convection individually through the fluid.

The flux due to convection can be

analysed in a similar way to
diffusion

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How is that done?
- Evaluating the change in
concentration due to
convection -

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 Step 2
Evaluate the
net flux

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Step 3
Evaluate the
net rate of
change of
concentration

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Brief
illustration

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C) Solutions of the diffusion
equation

q The diffusion equation (eqn 16C.6) is a

second-order differential equation with
respect to space and a first-order differential
equation with respect to time.
q To find solutions it is necessary to know two
boundary conditions for the spatial
dependence and a single initial condition for
the time dependence.

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C) Solutions of the diffusion equation -2
qAs may be verified by direct substitution. Figure
16C.5 shows the shape of the concentration
distribution at various times and illustrates how
the concentration spreads.
q Another useful result is for the diffusion in three
dimensions arising from an initially localized
concentration of solute (a sugar lump suspended in
an infinitely large flask of water).
q The concentration of diffused solute is spherically
symmetrical, and at a radius r is
q Other chemically (and physically) interesting
arrangements, such as transport of substances across
biological membranes can be treated, but the
mathematical forms of the solutions are more
cumbersome.
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 q The diffusion equation is useful for
the experimental determination of
diffusion coefficients. In the capillary
technique, a capillary tube, open at
C) Solutions of one end and containing a solution, is
immersed in a well-stirred larger
the diffusion quantity of solvent, and the change of
concentration in the tube is
equation - 3 monitored.
q The solute diffuses from the open
end of the capillary at a rate that can
be calculated by solving the diffusion
equation with the appropriate
boundary and initial conditions, so D
may be determined.
q In the diaphragm technique, the
diffusion occurs through the capillary
pores of a sintered glass diaphragm
separating the well-stirred solution
and solvent.
q The concentrations are monitored and
then related to the diffusion equation
that has been solved for this
arrangement.
q Diffusion coefficients may also be
measured by a number of other
techniques, including NMR
spectroscopy.
q The diffusion equation can be used to
predict the concentration of particles
(or the value of some other physical
quantity, such as the temperature in a
non-uniform system) at any location.
q It can also be used to calculate the
average displacement of the particles
in a given time.
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 How is that done?
- Evaluating the average displacement in a one-dimensional system -

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Step 2 Evaluate the integral

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 q An intuitive picture of
diffusion is of the particles
moving in a series of small
steps and gradually migrating
from their original positions.
This picture suggests a model
The in which each particle jumps
through a distance 𝒅 after a
Statistical time, 𝝉.
q This model is called the
View
q The total distance travelled by
a particle in time t is therefore
q The probability that the
𝑡𝑑 ⁄𝝉.
q However, it is most unlikely
that a particle will end up at
this distance from the origin
because each jump might be
in a different direction.
q The discussion is
simplified by allowing the
particles to travel only
along a straight line (the
x-axis) with each step a
jump through distance d
to the left or to the right.
one-dimensional random
walk.
walk will end up at a
specific distance from the
origin can be calculated
by considering the
statistics of the process.
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How is that done?
Evaluating the probability
distribution for a one-dimensional
random walk

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Step 2 Simplify this expression by using Stirling’s
approximation

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 Step 3
Expand the
logarithms

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Step 4 : Recast the expression for
the probability in terms of the
time for each step

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Brief illustration

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 1) A thermodynamic force is 3) The diffusion equation
an apparent force that (Fick’s second law) can be
mirrors the spontaneous regarded as a mathematical
tendency of the molecules formulation of the notion
to disperse as a that there is a natural
consequence of the tendency for concentration
Second Law and the to become uniform.
Checklist tendency towards greater
4) Convection is the bulk
entropy.
concept motion of regions of a fluid
2) The drift speed is
5) A model of diffusion is of
achieved when the
the particles moving in a
viscous retarding force
series of small steps, a
matches the
random walk, and gradually
thermodynamic force.
migrating from their
original positions.

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Checklist of equations

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END of Molecules in
Motion (Pergerakan
Molekul)