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Physical Sciences 2: Lecture 10c December 01, 2015

Lecture 10c: Diffusion Ficks Laws


Learning objectives: After this lecture, you will be able to:

1. Explain how random microscopic motion leads to a macroscopic flux (Ficks law)
2. Explain how a concentrated region of solute in a fluid spreads out over time (diffusion equation)
3. Understand where and how small living cells rely on diffusion for transport.
4. Explain that the macroscopic diffusion equations tell us the amount of stuff that diffuses in a given
time, for given concentration conditions.
!"(!)
5. Explain how Ficks first law relates flux to a concentration gradient: = !" .
6. Explain how Ficks second law (diffusion equation) relates changes in concentration in both position
!"(!,!) ! ! !(!,!)
and time: !" = !! ! .
7. Explain why and how concentration gradients relax over time.

Pre-reading: We have two main ideas for this lecture, Ficks 1st and 2nd law.

Fick's first law relates the diffusive molecular flux to the concentration. It says that the flux goes from regions of
high concentration to regions of low concentration, with a magnitude thats proportional to the concentration
!
gradient (spatial derivative, ), or in simplistic terms the concept that a solute will move from a region of high
!"
concentration to a region of low concentration across a concentration gradient. In one (spatial) dimension, Ficks
!
first law is: = , where:
!"
- is the "diffusion flux" [# molecules per unit area per unit time], for example / ! . The flux
measures the amount of substance that will flow through a small area during a small time interval.
- D is the diffusion coefficient with dimensions of [m2/s].
- C is the concentration with dimensions of amount of substance/ ! , for example / ! .
As we saw in the previous lecture, D is proportional to the squared velocity of the diffusing particles, which
depends on the temperature, viscosity of the fluid and the size of the particles according to the Stokes-Einstein
relation. In dilute water solutions the diffusion coefficients of most ions are similar and have values at room
temperature in the range of 0.6x109 to 2x109 m2/s. For larger biological molecules the diffusion coefficients is
smaller and normally ranges from 1011 to 1010 m2/s.

Fick's second law predicts how diffusion causes the concentration to change with time:
(, ) ! (, )
=
!
! ! !(!,!)
If there is a concavity in the concentration of molecules as a function of (i.e. 0), the concentration at
!!!
position x will change with time.

1
Physical Sciences 2: Lecture 10a November 20, 2014
ion of small particles in fluids is
dom: RobertActivity
Browns 5:Lecture
Towards
Motion
Sciences 2:experiment
a small
of quantitative
(1828) particles in theory
fluids is ofwalk): 01, 2015
Lecture 22: Therm
Physical 10c December
2-D random walk (also known as drunkards
Brownian motion
random:Although
Robert Browns
motion experiment
is random, (1828)
average values can
Robert
be predicted

Summary: Diffusion and Random Walks


Boltzmann D
Brown
own suspended
n 1828 micron sized
Brown suspended pollen
micron grains
sized in water
pollen grainsand
in water and looked through a microscope Robert
oked through a microscope
n saw Brownian motion and saw Brownian motion
Brown suspended micron sized pollen grains in water and
Brown
1773-1858
1. We developed a fundamentallooked
relation between
through the diffusionand
a microscope coefficient and friction
saw Brownian motionusing:

Kinetic theory Einsteins model of Brownian motion is


based on the concept of the random walk
Random walk diffusion coefficient
Movement you see is the result of We dont see the
Random walk frictionstatistical
coefficientfluctuations.
individual kicks, but we
can seeofthe
2. We saw that viscous friction and diffusion both come from random fluctuations summolecules
solvent of them
(Fluctuation-Dissipation Pollen grain (a few microns)
theorem). (which itself is a random
variable)
Pollen grain (a few microns)
as this life?3.He denied
The them light and air and
Einstein-Smoluchowski they continued
equation = ! is the most general relation between diffusion and
dance. He friction
suspended soot and ground sphinx and found the Analogy: If you repeatedly
Was this life? He denied them light and air and they continued
me behaviour.
to dance.from
He suspended
flip a coin 100 times, once
soot and ground sphinx and found the
. Lets first4.look at the speed of water molecules Kinetic theory:
The Stokes-Einstein equationsame behaviour.for spheres, but works veryin
is specifically a long
well while it will
to approximate the come
diffusion coefficient of even non-spherical molecules: = ! /6 up heads 90 times out of
Each water molecule kicks the
pollen grain randomly in the x the 100
direction, to the left and to
ards a quantitative theory ofFicks Brownian
the
Law derivation
right. Sometimes there are
ion
. Two questions arise:
many small kicks to Readings:
the right which
add up to a large kick with a longer
such tiny molecules make anWhat
a) How canToday: is the net flux to the right J ?
enormous Simulation:
time scale. particle (pollen grain)x move so much? particle being bounced around by
peed of water
b) If the molecules
water molecules
Randomness
are movingTwo # crossing
questions
so fast, to
why do we theis
that part
right is
seearise:
of Todays lecture: B&W, sections 19.
physics
N(x)/2 (and life) molecules
the particle moving so slowly? Adolf Fick
- theory:
Understand how random microscopic
# crossingmotion leads to a +macroscopic flux (Ficks law)
x)/2 http://www.aip.org/history/einstein/brownian.htm
om kinetic 1. How can to the left
such tinyis N(x Next lecture: Handout on Brownia
Net Flux
molecules = J
make
- Understand how a concentrated region of solute x=- [ N(x
an + x) N(x) ] / (2A t)
in a fluid spreads out over time (diffusion equation)
Fluids (liquids
enormous particle and(pollen
gases)
- Ficks first law tells us howgrain)
the flux relates
consistmove
of lots to
so andthe
much?concentration:
lots of This
N(x) allows us to calculate, forN(x + x)
example, the amount of solute passing through a membrane, like skin or a contact lens
2. Ifmolecules
Lecture 24: Ficks Law and the Diffusion
- The diffusion equation tells us
the water molecules are
Each
howmolecule
moving the fast, why obeys
soconcentration do the) changes with position and time.
(,
x x+ x
laws
we seeofthe
physics
particle (mechanics)
equation
Note about Brownian motion:
moving so slowly?but
They collide with each
We cant see atoms with visible light, because
other,atoms
and endare ~1/10nm
up moving while the wavelength of light is ~1um.
In some ways however, Brownian motion in random directions withof
allows us to see the effects a individual atoms. Its pretty
Simulation of gas particles
amazing. variety of speeds colliding
Last lecture: Introduction to
As you saw in the lab, you can use Brownian motion to count how many atoms are in a 1 mole. Your
http://comp.uark.edu/~jgeabana/mol_dy
results have ranged from 3x1023 to 9x1023, compared with 6.022x1023. Quite stunning.
n/KinThI.html

Motion and Statistical Mecha


Ficks law: on average, moleculesin
Everything move
a3 fluid exhibits flu
toward regions of lower concentration

2Hence
Ficks First Equation: J
things inside living cells
= -D(dc/dx) or J =D( c/ x)
x x
motions
9
Physical Sciences 2: Lecture 10c December 01, 2015
Example: Diffusion of 1-micron spheres in water
Activity 1: Putting it all together
Larger viscosity smaller D
Einstein-Smoluchowski and Stokes-Einstein
Larger diameter smaller D
(Smaller
For spherical particles we know the drag coefficient from the Stokes x
RMS
law !"#$ = for the
(6) same
= !"#$ : t)

Example 1: Diffusion of 1-micron and 3-micron spheres in water. Which distribution corresponds to the 1 vs
3 spheres?

= 10!! kg/m2
= 0.5 10!!
= 300
! = 1.38 10!!" /

Motivation: Diffusion
Motivation: is central
Diffusion to lifeto life
is central
O2 and CO2 are transferred to and from lungs to red blood cells.
Example 2: What is the ratio of the average distances that Breathe in, blood flows past, oxygen diffuses in. How many alveoli do
oxygen will diffuse in a given time in air and water? (Why is D you need to get enough oxygen to survive?
less in water)?
oxygen

Quantifying the amount of stuff that diffuses:


Example 3: Oxygen reaches the vein-less cornea of the eye by

Concentration and
it take the average oxygen molecule to do flux
diffusing through its 0.500-mm thick tear layer. How long does
this? A bacterium gets its oxygen
from the fluid around it. Is
there a limit to the size of a
bacterium set by the diffusion
rate of oxygen?

Concentration: C(x,t) = number of molecules per unit volume at a


position x and time t.
Quantifying the amount of stuff that
Flux: Jx = number N of molecules passing an area A in time t (and moving
diffuses: Concentration and flux

in the x direction). 3 Concentration: C(x,t) = number of molecules per unit volume at a


position x and time t.
Flux: Jx = number N of molecules passing an area A in time t (and
Now consider what happens when we have a ingradient
moving the x-direction). in concentration of
Now consider what happens when we have a gradient in concentration
Physical Sciences 2: Lecture 10c December 01, 2015
Quantifying the amount of stuff that
Quantifying
diffuses: the
2: amount
Concentration
Activity ofand
stuff
Quantifying that
flux
how much stuff diffuses
diffuses: Concentration and flux
Defining concentration and flux:
Concentration: C(x,t) = number of molecules per unit volume at a
Concentration:
position x and timeC(x,t)
t. = number of molecules per unit volume at a
Concentration (, ) = number of molecules per unit volume at a position and time .
position x and time t.
Flux:
Flux:JJxx= = number
number NNofofmolecules
molecules passing
passing an area
an area A int time
A in time (and t (and
Flux:moving
moving in
= numberinthe x-direction).
of molecules
the passing an area in time (and moving in the -direction).
x-direction).
Now Nowconsider whathappens
consider what happens when
when we we
havehave a gradient
a gradient in concentration
in concentration
Now of ofsolute.
consider what How
solute. How do
happens do we
we
if we determine
determine
have in the
a gradientthe flux? of solute. How do we determine the flux?
flux?
concentration

Model:
Model: eachdoes
each molecule molecule does
a random walkaand
random walk
is equally and
likely is equally
to move likely to move
left or right:
Model: each molecule does a random walk and is equally likely to move
left or right
left or right Area%A"
N(x) N(x + x)
N(x) N(x + x)

x x+ x

x x+ x

What is the net flux to the right, through the area A?

Ficks first law

4
x
1%m" 2%m" x
Physical Sciences 2: Lecture 10c
C(x) water
C(x) %
Ficks law: on aver
Ficks Law
December 01, 2015derivation
A%=%1%m2"
"
x"
Activity 3A: Ficks first law
toward
Ficks regions
law:
What is the
1%m" 2%m"
neton to theof
right l
fluxaverage,
Am I getting it: toward
# crossingregions
to the rightofis lower
N(x)/2
# crossingxto the left is N(x + x
Ficks First Equatio
Oxygen molecules are diffusing in a small water-filled cylindrical tube with !! = 110
x
!
! /. Below are three
Ficks First Equation: J x=
Net
different concentrations of O2 molecules in water (, = 0) as a function of , along Flux
the small [
= Jx=- N(x + x)
tube.

1. What can you say about the flux of diffusing O2 molecules at 2m versus the flux at 1m for the following
concentration? C(x)

(a) ! 2 > ! 1 , both to the right C(x) C(x)


(b)
(c)
(d)
!
!
!
2
2
2
< !
= !
> !
1 , both to the right
1 , both to the right
1 , both to the left
Ficks law: on aver
2x1012%molecules/cm3% x
1x1012%molecules/cm3%
(e)
(f)
!
!
2
2
< !
= !
1 , both to the left
1 , both to the left toward C(x)
regions
Ficks law: of l
on average,
(g) ! 2 = ! 1 = 0
toward regionsx ofxlower
1%m" x
2%m"
Ficks First Equatio
Ficks First Equation: Jx =
C(x)
2. What can you say about the flux of diffusing O2 molecules at 2m versus the fluxC(x)
at 1m for the following
concentration?

(a) ! 2 > ! 1 , both to the right C(x)


(b) ! 2 < ! 1 , both to the right x
! 2 = ! 1 , both to the right
C(x)
Ficks law: on xave
(c)
(d) ! 2 > ! 1 , both to the left
(e) ! 2 < ! 1 , both to the left 2x1012%molecules/cm3% x
(f) ! 2 = ! 1 , both to the left
(g) ! 2 = ! 1 = 0
toward
C(x) regions
1x1012%molecules/cm3%C(x)
Ficks law: of
on average
3. What is the magnitude of the flux ?
x lowe
toward regionsx of
(a) 1 O! /( ! ) 1%m" 2%m"
(b) 10 O! /( ! ) Ficks First Equatio
Ficks First Equation: Jx
(c) 10! O! /( ! )
(d) 10! O! /( ! )
C(x)
C(x)
x
4. The concentration of O2 molecules in water (, = 0) is C(x)
x
shown on the right.
C(x) x
What can you say about the concentration of O2 molecules at
x
1.5m for > 0?

(a) The concentration (, ) will stay the same C(x)


1012%molecules/cm3%C(x)
(b) The concentration (, ) will increase
(c)
(d)
The concentration (, ) will decrease
Impossible to tell with the information given
x
1%m" 2%m" x
A
5 "
C(x) water%
C(x)
x
x x+ x
Ficks law: on average, molecules mo
Physical Sciences 2: Lecture 10c
C(x)
December 01, 2015
C(x)
toward
Ficks regions
law: on of
average, lower
moleculesconcentration
Activity 3B: Ficks first law
move x

toward regions of10lower concentration


%molecules/cm C(x)
20 3%

Ficks First Equation: Jx = -D(dc/dx)


Ficks First Equation: J
Ficks law: on average, molecules x or Jx
x)x = -D(dc/dx) or!" Jx=D( c/
move toward regions of lower concentration.
!"
= , or =
x
!!
!!

1%m" 2%m"
A%=%1%m2"

Ficks law: on average, molecules mov


"
C(x)
C(x) water
C(x) %
x"
1%m" 2%m"
toward
C(x)
regions
Ficks law:
2x1012%molecules/cm3% of lower
on average, moleculesconcentration
move
x
x

toward regions of lower concentration x


1x1012%molecules/cm3%
C(x)
Ficks First Equation: J =
Ficks First Equation: Jx = -D(dc/dx)
x C(x) x -D(dc/dx) or
or Jx=D( c/ x) J x
1%m" 2%m" x

C(x)
C(x) C(x)
C(x) x
x
x
1012%molecules/cm3%C(x) x
x
C(x)
C(x)equation
Ficks law, diffusion water %
C(x) motivation
1%m" 2%m" x

"
Lecture 24:
A%=%1%m2"

x"
Very useful in calculating practical things:
- How much oxygen gets into the blood1%m" 2%m"
stream from the lungs
- How the kidneys work in filtering the blood x
- How capillaries take gases in/out from the interstitial fluid.
- How things pass across membranes x
- How big prokaryotic cells can be* (No motor proteins?)
- How to get the caffeine out of coffee beans
- Interpreting MRI of the brain
C(x)
Bonus: You don't always consume oxygen at the same rate. If you exercise,
your oxygen consumption rate goes up (i.e. ! increases). Which part of
Ficks 1st law can account for this increase in O2 flux?

x
6
Physical Sciences 2: Lecture 10c December 01, 2015

ActivityPractical
4: Ficksmembranes:
first law -- applications
flux and permeability
membrane%
Diffusion through a thin membrane: steady-state
Ficks law can appear in
disguise, depending on the
1. Consider potassium ions crossing a biological membrane 10 nm thick. for potassium in the
dimensions used for k+%
membrane is 1.0x10-16 m2/s. concentration:
(a) What number of potassium ions per second will move across an area 100nm x 100nm
Number
if the concentration difference across the membrane is maintained at 0.50 mol/litre? c1%
Mole or decrease the membrane thickness.
(b) Discuss how the flux changes if weincrease c2=0%
Note: 1 litre = 10-3 m3 Mass
Volume
Real membranes are usually
solids with some pores. They
are characterized by their
permeability Perm=Dk/ x 10%nm%
where k is a factor that takes
into account the pore fraction
or solubility, and x is the
thickness

Diffusion of O2 through contact lenses: steady-state


membrane%
2. The cornea is alive and needs oxygen but it does not contain blood
vessels (needs to be transparent). It gets its oxygen by diffusion from the
tear fluid. k+%
Example: Contact lenses
Old contact lenses were made from glass and would often lead to
Neovascularization when worn for long periods of time. To avoid this 02%
condition, modern contact lenses are Theccornea
permeable to does
oxygen.
not contain cornea% Tear%%
1%
blood vessels (needs to
c =0%
2 be
Real membranes (e.g. contact lenses)transparent).
are usually solidsItwith some pores. uid% Air%
gets its oxygen
They are characterized by their permeability Perm= / where is a
by diffusion from the tear fluid
factor that takes into account the pore fraction or solubility, and is the
membrane thickness. Contact lenses need to be
Lens%
permeable
Be careful, the O2 permeability of contact to oxygen,
lenses decreases or blood
significantly
when contact lenses dry out! vessels will grow toward the
cornea 10%nm%
(a) Re-write Ficks first law in terms of the permeability ! Perm= /.

Neovascularization: extra
blood vessels grow to carry
7 oxygen to the cornea
Physical Sciences 2: Lecture 10c December 01, 2015

Activity 5: Ficks second law (diffusion equation)

!"
Ficks first law ( = !") gives us a relation for the flux. We can calculate the flux when we know the
concentration gradient

But what if the concentration and the gradient change over time (non-steady state diffusion)?
Describing these time-dependent diffusion problems with Ficks 1st law can be quite tedious!
As an example, see question 4 in the Am I Getting it on p.5

- Need to find (, ) for all time given an initial concentration (, 0).


- Start by finding the change in concentration at a point given the flux from the left and right

sion equation derived


sion Equation: describes c(x,t) for all time given c(x,0)
The diffusion equation describes (, ) for all time given (, 0):
Ficks second law

c c

x x

8
c Concept question answer

Physical Sciences 2: Lecture 10c December 01, 2015


x
Consider a gaussian concentration distri
Concept question: diffusion equation
Activity 6: Ficks second law examples
The concentration of a protein
1. The concentration in a long
of a protein cylindrical
in a long axon
cylindrical at at
axon time t = 0 is
time by
represented = the
0 issolid curve by
represented onthe
thesolid
graphs
curvebelow.
on theIfgraphs
the protein is A%=%1%m2"
allowedbelow. If the protein
to diffuse, is allowed
on which of the to diffuse, on
following whichdoes
graphs of thethe dashed " c
following graphs does the dashed line represent a possible
line represent a possible distribution of the protein at some later time x"
t > 0? distribution of the protein at some later time > 0? x
Concept
Neurotransmitter pulse question: diffusion equation

The concentration of a protein in a long cylindrical axon at time t


represented by the solid curve on the graphs below. If the protein
allowed to diffuse, on which of the following graphs does the dash
line represent a possible distribution of the protein at some later t
t > 0?
Neurotransmitter pulse

The diffusion equation: application to drug


delivery
2. Some drug delivery mechanisms utilize diffusion to carry active
ingredients from a reservoir to the target (e.g. blood). Which initial
concentration profile below will lead to the fastest initial increase in
the concentration of drug in the blood? The diffusion equation:
10
appl
c(x,t=0)%
How long does c(x,t=0)% delivery
(A)% (B)%it take for a given amount
of drug to be absorbed into the body?

x" x"
Blood% patch% Blood% patch% How long does it take for a given amount
of drug to be absorbed into the body?
c(x,t=0)%
(C)% (D)% c(x,t=0)%

x" How can we control the release of the


x"
Blood% patch%
Blood% patch% drug?

Ho
dru

9
Physical Sciences 2: Lecture 10c December 01, 2015

10
Physical Sciences 2: Lecture 10c December 01, 2015

One-Minute Paper

Your name: _________________________________ TF: _____________________________

Names of your group members: _________________________________

_________________________________

Please tell us any questions that came up for you today during lecture. Write nothing if no
questions(s) came up for you in class from 9:30am11am.

What single topic left you most confused after todays class?

Any other comments or reflections on todays class?

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