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Week 1
J D
membrane
dc
dx
fluid 1
fluid 2
C1
C
1
C
2
x
C4
x1
x2
x3
x4
What is life?
Life is natures way of keeping meat fresh.
(Dr. Who?, 23/7/05)
Life is a set of ongoing controlled chemical reactions
occurring in prescribed locations.
Reactions need reactants
Delivery of reactants to the reaction site is mass
transfer (in part)
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Blood processing
Haemodialysis
Oxygenator
Peritoneal dialysis
Haemofiltration
Plasmapheresis
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Drug delivery
Implants
Skin patches
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Background we need
We are dealing with solutes in different phases
Liquids (water, blood, lipid bilayer membrane)
Gases (air)
Membranes
We have to know
how species move within phases
what governs the distribution of species between
phases
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We have to know
The properties of the barrier
The effect of flow rates on the overall rate of transfer
The effect of flow channel dimensions
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Todays topics
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Ideal gas
T0 =
P0 =
V0 =
R =
=
=
=
PV
273.16K (0C)
1 atm = 760 mmHg
= 101.3 kPa
= 1.013 106 dyne/cm2
22.4 L for 1 gram-mole of gas
Universal Gas Constant
0.0821 atm L/K mol
8.31 44 Pa m3/K mol
1.99 cal/K mol
P0V0/T0 *** (I use this often)
nRT
Advice: Implement this
in Excel (say). Store
conversion factors for
P and values of R.
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P
i
RT
RT
ni
nT
V
V
n
Pi i P xi P
nT
ni
xi
nT
Mole fraction
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dni
P,T ,all n j
dn
i
V
S
i
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volume
entropy
chemical potential of species i
Gibbs free energy per mole
the driving force for mass transfer by diffusion
(among other processes)
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Phase equilibrium
Phase: 4. Chem. A physically distinct and homogeneous form of matter characterized by
its state (as gas, liquid, or solid) and composition and separated by a bounding
surface from other forms. (OED)
T T
P P
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i i
11
Ideal solutions
A binary solution of A and B and its equilibrium vapour phase:
Asoln Avapour
PA
Bsoln Bvapour
But
XA
PB
Vapour
XB
Solution
Avapour Ao RT ln PA
Therefore
Asoln Ao RT ln PA
Or better:
o
soln
A
A RT ln
PA
PAo
A
A RT ln x A
PA x A PAo
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Osmotic pressure
When you dissolve a solute in a solvent,
you lower the chemical potential of the
solvent.
If the solution is separated from pure
solvent by a semi-permeable membrane
(permeable to the solvent but not the
solute), solvent will flow from the pure
side to the solution side.
If sufficient pressure is applied to the
solution, the osmotic flow can be
overcome.
This pressure is the osmotic pressure. It
is the hydrostatic pressure required to
overcome the osmotic flow.
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A+B
A A
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Osmotic pressure
At equilibrium we have
A A
but
A Ao RT ln
whereas
P = P+
PA
A+B
PAo
A oA
P P
A A
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Osmotic pressure
Vant Hoffs Law (ideal solutions)
Van't Hoff
cRT
ci RT
i
osmolarity
At 37C
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RT
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Concentrations
A concentration is a ratio:
amount of X
amount of Y
moles of i
ci
(mol/L)
litre of solution
Blood gases:
ml O 2 ( STP)
cO2
ml blood
Mole fraction:
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moles A
xA
total moles
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ci kPi
gas
Oxygen
Carbon dioxide
Carbon monoxide
Nitrogen
Helium
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k
0.024
0.57
0.018
0.012
0.008
High solubility of
CO2 in water
has implications
17
Liquid/liquid equilibrium:
Partition coefficients
II
iII iI
Define a partition coefficient i
such that
ciII i ciI
solute
glycerol
ethanol
N-propanol
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phase I
water
"
"
Phase II
olive oil
"
"
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0.000068
0.022
0.1
Does this
series make
sense?
Write the
formulas of
these three
alcohols.
18
lung
right
heart
left
heart
5%
The
circulation
(for reference)
heart
15
%
35%
brain
liver
gut
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15%
muscle
20%
kidneys
10%
skin,bone
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accumulation
output
accumulation
input
output
synthesis
destruction
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Example
210 ml/min
? ml/min
Under what
Assumptions?
220 ml/min
175 ml/min
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Example
Solutions flowing into and out of a device, steady state
210 ml/min
c = 0.4M
Assumptions?
185 ml/min
c= ? M
220 ml/min
c = 0.9M
175 ml/min
c = 0.5M
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Example
210 ml/min
c = 0.4 M
N ?
220 ml/min
c = 0.9 M
185 ml/min
c = 1.09 M
175 ml/min
c = 0.5 M
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Example
300 ml/min
c= 0 M
200 ml/min
200 ml/min
c= 2 M
Minimum possible c = ? M
Maximum possible c = ? M
300 ml/min
Minimum possible c = ? M
Maximum possible c = ? M
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Example
Minimum possible c = ?
c= 2 M
200 ml/min
200 ml/min
300 ml/min
c= 0
300 ml/min
Maximum possible c = ?
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Example
Minimum
possible c = ?
c= 2 M
200 ml/min
200 ml/min
300 ml/min
Maximum
possible c = ?
300 ml/min
c= 0
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k.e.
1m
2
vx2
1 kT
2
vx2
kT / m
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12
vx2
kT
RT
8.3110 erg K
7
-1
mol-1 310K
14000 g mol-1
1356cm s 1
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xi (n) xi (n 1)
Averaging over all particles
1
x ( n)
N
1
N
1
x ( n)
i 1
x (n 1)
i
i 1
N
x (n 1)
i 1
x(n) x(n 1)
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No net movement
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xi (n) xi (n 1)
Squaring,
x 2 (n) x 2 (n 1) 2
or
x 2 (n) n 2
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If we define
we get
or
2
D
2
x 2 (t ) 2 Dt
2
x (t )
2 Dt
tdiff
L2 D
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Flux
The flux of X is the flow of X, per unit
area, with respect to a coordinate system.
If the mean relative velocity of X is v and
its concentration is ci, the flux is
J cv
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-2 -1
ML T
kg m-2 s-1
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Convection
The flow of matter (or heat) due to the
bulk motion of a fluid.
vci
J i ci v
If a fluid is flowing in a conduit with crosssection area A, the total flow of species i is
Ni Ji A ci v A Qci
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Qci
36
Diffusion
before
after
diffdemo2a.m
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dci
J xi Di
dx
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Diffusion coefficient D
Depends on
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Nernst-Einstein equation
kTvA kT
DAB
FA
fA
k
FA
fA
So
D = thermal energy / friction factor
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Stokes law
The friction factor for a spherical molecule of radius rA in a
medium with viscosity B is
What is viscosity?
(resistance to flow)
fA 6 BrA
Stokes-Einstein
DAB
kT
6 BrA
3M A
rA
4 A N Avog
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3
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Example
For aqueous solutions at 37C, assume solute molecular density ~1
7
-1
-1
A = 1 g cm-3
B = 0.0069 dyne s cm-2
-1
8.314 J mol K
-1
1000 kg m-3
0.00069 Pa s
1 Da = 1 g mol-1
For M = 1000 Da, we find
r = 7.35x10-10 m
D = 4.48x10-10 m2 s-1
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Advice:
Implement this in Excel (say).
Make a table of MW vs. D
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Medium
Water
"
"
"
air
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D (cm2/sec)
3.1 10-5
2.6 10-5
1.9 10-5
1 10-6
0.15
43
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diffusion
out at x+dx
x
x+dx
c( x, t )
dxdydz J x ( x, t )dydz J x ( x dx, t )dydz
t
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J ( x, t )
c( x, t ) J x ( x, t ) J x ( x dx, t )
x
t
dx
x
or simply
J
c
x
t
x
Jx D
to give
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c
x
c
2c
D 2
t
x
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J D
C
1
C
2
x
c
J
0 (steady state)
t
x
Flux is independent of position if SS. Therefore the
concentration profile is linear.
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dc
dx
47
c c
c c
1 2 1 2
R D
D
R
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Dm
C1
C1m
C2
C2m
c1m c2m
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c1m mc1
We now write
Dm m
c1 c2 Pm c1 c2
Pm
Dm m
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Resistances in series
Usually we must consider 2 or more
resistances in series, as in this 2chamber diffusion apparatus. We want to
relate the flux to the difference between
the measured concentrations in samples
taken from the chambers.
membrane
fluid 1
fluid 2
C1
x 3< x < x 4
C4
x1
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x2
x3
51
x4
Assume
<v> = 0
1 = 2 = 3 = 1
SS
dc
J constant Dn
dx
n 1, 2,3
c3 c2
c4 c3
c2 c1
J D1
D2
D3
x2 x1
x3 x2
x4 x3
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J ( x2 x1 ) J
JR1
D1
P1
J ( x3 x2 ) J
c2 c3
JR2
D2
P2
c3 c4
J ( x4 x3 ) J
JR3
D3
P3
The sum
c1 c4
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J J
J
J R1 R2 R3
P1 P2 P3
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1
1 1
1
Po P1 P2 P3
or in terms of resistances
Ro R1 R2 R3
Easier to work with resistances when we have multiple layers!
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References
Berg HC: Random walks in Biology. Princeton, Princeton
University Press (1993).
Cussler EL: Diffusion: Mass transfer in fluid systems.
Cambridge, Cambridge University Press (1984).
Fournier RL: Basic transport phenomena in biomedical
engineering. Taylor and Francis (2012)
Trusky GA, Yuan Fan, Katz DF: Transport Phenomena in
Biological Systems, Pearson Prentice Hall (2004). GSBME
library.
Keller KH: Fluid mechanics and mass transfer in artificial
organs. (1973).
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