1 Molecular Diffusion

Notion of concentration Molecular diffusion, Ficks Law Mass balance Transport analogies; salt-gradient solar ponds Simple solutions Random walk analogy to diffusion Examples of sources and sinks

Motivation
Molecular diffusion is often negligible in environmental problems Exceptions: near interfaces, boundaries Responsible for removing gradients at smallest scales Analytical framework for turbulent and dispersive transport

Concentration
Contaminant => mixture

Carrier fluid (B) and contaminant/tracer (A) If dissolved, then solvent and solute If suspended, then continuous and dispersed phase

Concentration (c or A) commonly based on mass/volume (e.g. mg/l); also

Note: 1 mg/l ~ 1 mg/kg (water) = 1ppm

mol/vol (chemical reactions) Mass fraction (salinity): A/

Molecular Diffusion
z
(2)

One-way flux (M/L2-T)

= A wA
lm

Net flux
wA

= wA ( A1 A 2 ) = wAl m A / z

(1)

c or

DAB r J A = DAB A

Ficks Law and Diffusivities

r J A = DAB A
r r r ( ) = ( ) i + () j+ ()k x y z
DAB is isotropic and essentially uniform (temperature dependent), but depends on A, B Table 1.1 summarizes some values of DAB Roughly: Dair ~ 10-1 cm2/s; Dwater ~ 10-5 cm2/s

Diffusivities, contd
Diffusivities often expressed through Schmidt no. Sc = /D Roughly: air ~ 10-1 cm2/s; water ~ 10-2 cm2/s Scair ~ 1 Scwater ~ 103 Also: Prandlt no. Pr = / ( = thermal cond.) Add advection; total flux of A is:

r r N A = A q DAB A

macroscopic velocity vector

Conservation of Mass
z Like a bank account except expressed as rates: z (NA)x y x y (rate of) change in account = (rate of) (inflow out) +/(NA)x+x (rate of) prod/consumption x Example for x-direction
in = ( N A ) x yz N out = ( N A ) x + x yz = ( N A ) x + A x yz x N net in = A x yz x

Conservation of Mass, contd

z Account balance

= A xyz
Rate of change of account balance x

= ( A )xyz t
Rate of production

= rA xyz

Conservation of Mass, contd

z Sum all terms (incl. advection in 3D)
A + (N A )x + (N A ) y + (N A )z t x y z r A + N A = rA t
Flux divergence (dot product of two vectors is scalar)

For carrier fluid B r B

t

+ N B = rB

Conservation of Mass, mixture

rA = rB r r r N A + N B = q
r + ( q ) = 0 t 0 t r q = 0
Conservation of total mass A +B =

Liquids are nearly incompressible Divergence = 0; Continuity

Conservation of Mass, contaminant

A = c
drop subscript A

r c + (cq ) = ( Dc) + r Conservative form of mass cons. t r r c + c q + q c = D 2 c + (D)(c) + r t 0 0 c r N.C. form + q c = D 2 c + r t r c 2 = D c If q = r = 0 => Ficks Law of Diffusion t

Heuristic interpretation of Advection and diffusion

c t-1 U t ut c x c Diffusion t t-1 J J x
Difference in fluxes (divergence) ~ curvature

Advection
Flux ~ negative gradient

Analogs
c Ficks Law (mass transfer) = D 2 c t T Fouriers Law (heat transfer) = 2T t r r r rm q r 2r + ( q ) q = q + Newtons Law (mom. Transfer) t
/D / Sc Pr Air ~1 ~0.7 D~ Water ~103 ~8 D<<<

Example: Salt Gradient Solar Ponds (WE 1-1)

like El Paso Solar Pond

~3m
S T

UCZ GZ BCZ

dense brine

Solar Pond, diffusive salt flux to UCZ

S = 50 o oo

Area = 10,000 m2
UCZ GZ

Z1=0.3m Z2=1.8m
S T

BCZ

c = S

S = 250 o

oo

cUCZ = (1033 Kg/m3)(50x10-3 Kg/Kg) = 52 Kg/m3 cBCZ = (1165 Kg/m3)(250x10-3 Kg/Kg) = 291 Kg/m3

J s = Ddc / dz =(2x10-9)(239 Kg/m3)/1.2m = 4.0x10-7 Kg/m2-s = 344 Kg/day

Solar Pond: diffusive thermal flux to UCZ

T1 = z1 z2
T

30oC

sn = 250 W/m2

s(z) = sn(1-)e-z T2 = 80oC

= fraction of sn absorbed at surface = extinction coefficient Cp = heat capacity (4180 J/KgoC); = thermal diffusivity (1.5x10-7 m2/s)

d 2T 0 = C p 2 + (1 ) sn e z dz * T = 2 e z + c1 z + c 2

* = (1 ) sn / C p
c1, c2 from T=T1 at z1, T=T2 at z2

Solar Pond: thermal flux

T1 = z1 z2
T

30oC

sn = 250 W/m2

s(z) = sn(1-)e-z T2 = 80oC

J t = C p (dT / dz ) z = z2

z2 (e z2 e z1 ) T2 T1 = C p + (1 )sn e + z 2 z1 ( z z ) 2 1

z1 = 0.3m; z2 = 1.5m, =0.5, = 0.6 => Jt = 7 W/m2 Compare with (1-0.5)(250)exp(-0.6*1.5) = 51 W/m2 reaching BCZ (~13% lost)

Rankine Cycle Heat Engine

Evaporator Brine Turbine generator

Feed pump

Cooling water Condenser

Figure by MIT OCW.

Solar Pond: total energy extraction

T1 = z1 z2
T

30oC

sn = 250 W/m2

s(z) = sn(1-)e-z T2 = 80oC

% of sn 100 20 14 2 1
Carnot efficiency c = (T2-T1)/(T2+273) [24 KWe for 1 ha]

Energy Flux at surface Energy Flux reaching BCZ Energy Flux extracted Electricity extracted (theoretical) Electricity extracted (net actual)

250 W/m2 51 34 4.8 2.4

Simple Solutions
Inst. injection of mass M A
c c =D 2 t x bc : c = 0 at x = M ic : c = ( x) at t = 0 + alternative A M r = ( x) (t ) with c = 0 at t = 0 A
2

Simple Solutions, contd

Inst. injection of mass M A x Solution by similarity transform (Crank, 1975) or inspection
c=

B t
1/ 2

x2 4 Dt

A cdx = M

M = 2 AB D

2 A Dt Add a current ( x ut )2 M 4 Dt c ( x, t ) = e 2 A Dt

c ( x, t ) =

x2 4 Dt

Gaussian Solution
c

t x

x x

Spatial Moments
mo = c( x, t )dx

interpretation

M = mo A m1 xc = = ut mo

Mass; indep of t Center of mass

2

m1 = cxdx

m2 = cx dx
2

m2 m1 = 2 Dt = mo m2

Plume variance

Spatial Moments, contd

Relationship of moments to equation parameters

m2 =

2A

Dt

x2 4 Dt

x 2 dt

M = 2 Dt A m2 2 MDt / A 2 x = = = 2 Dt mo M/A
Without current, odd moments are 0

Spatial Moments, contd

Rewrite in terms of
c ( x, t ) = M 2 A Dt e
x2 4 Dt

or in 3-D (isotropic)

M c ( x, t ) = e 3/ 2 8(Dt )

( x2 + y2 + z 2 ) 4 Dt

2 M = e 2 A 2 x

x2

M = e 3/ 2 3 (2 )

( x2 + y 2 + z 2 ) 2 2

Plume dilutes by spreading: In 1-D, c ~ t-1/2 ~ x-1 In 3-D, c ~ t-3/2 ~ -3

Moment generating equation

c c =D 2 t x
2

mi =

x cdx
i

Approach 1: moments of c(x,t) => 2 = m2/mo = 2Dt Approach 2: moments of ge => moment generation eq.

x (each term) dx
i

Moment generating eq., contd

c c =D 2 t x
2

mi =

0th moment 2nd moment

dmo c dx c dx = = t t dt 2c c dx D D = =0 2 x x dm2 c 2 dx x c dx x = = dt t t
2

x cdx
i

c 2c 2 c 2 2 ( ) dx = xD c xD dx Dx Dx = + 2 Dcdx = 2 Dmo 2 x x x
2

Moment generating eq., contd

c c =D 2 t x
2

mi =

x cdx
i

0th moment 2nd moment

dmo =0 dt

=> mo = const = M/A

dm2 = 2 Dmo dt => d2/dt = 2D or 2 = 2Dt d 2 mo = 2 Dmo dt

How fast is molecular diffusion?

z Creating linear salinity distribution from initial step profile Assume 80 cm tank; 40 2cm steps

S Time to diffuse: 2 = 2Dt slow!

Table 1-1

t = 2/2D ~(2cm)2/(2)(1.3x10-5 cm2/s) = 1.5x105s ~ 2 days If thermal diffusion (100 x faster), t < 1 hr

Spatially distributed sources

c co t

2c c 0 =D 2 x t bc c = 0 at x = c = co at x = ic c = co c=0 for for

or c = co/2 at x = 0

x < 0 at t = 0 x > 0 at t = 0

Spatially distributed sources

co d 0 x x

dc( , t ) = c ( x, t ) =
x

dM 2 A Dt c o d 2 Dt e

2
4 Dt

c o d 2 Dt

2
4 Dt

2 4 Dt

co = 2

x co x 1 erf = 2 erfc 2 Dt 2 Dt

Error Function

erf() erfc()
erf ( ) = erfc( ) = 2

e
0

d d

erf (0) = 0 erf () = 1 erfc( x) = 1 erf ( x)

Example: DO in Fish aquarium (WE 1-4)

2(c2-c1)
C1 C2 2C2 C1 c

t=0: c=c1=8 mg/l (csat at 27oC) t>0: c(0)=c2=10 mg/l (csat at 16oC)

1 c( z ,t ) = c1 + 2(c 2 c1 ) erfc z / 2 Dt 2
c c1 = erfc z / 2 Dt c 2 c1
erfc[(z/(4Dt)0.5] 0 10-15 0.15

Evaluate at z =15 cm, D = 2x10-5 cm2/s (Table 1-1)

t 1hr 1d 1 mo z/(4Dt)0.5 28 5.7 1.0

Again, very slow!

Diffusion as correlated movements

x=0 at t=0

x (t ) =

u ( t ' ) dt '
0

p(x,t)

x Analogy between p(x) and c(x); ergotic assumption For many particles, both distributions become Normal (Gaussian) through Central Limit Theorem

Statistics of velocity
u =0 u 2 = const. u (t )u (t ) u (t )
2

mean velocity variance

u (t )u (t ) = u (0)u ( ) = u ( )u (0) auto co-variance = R( )

auto correlation

R() 1

Statistics of position
x(t ) = u (t ' )dt '
0 t t

x = u (t ' )dt ' = u (t )dt = 0

0 0

x 2 (t )

increases with time, as follows

t t dx 2 (t ) dx = 2 x(t ) = 2 u (t ' )dt 'u (t ) = 2 u (t )u (t ' )dt ' dt dt 0 0

d x 2 (t ) = 2u 2 (t ) R (t t ' )dt ' = 2u 2 (t ) R ( )d dt 0 0 d x 2 d 2 D= = = u 2 R( )d Taylors Theorem (1921); classic 2dt 2dt 0

t

[D] = [V2T] Earlier, D = wAl m [VL] or

D=

2
2t

[L2/T]

Random Walk (WE 1-3)

Special case: u (t ) = U or U direction changes randomly after t Walkers position at time t=Nt Probability distribution
0.5

x = ut
1

p ( , N ) =

N! 1 N + N 2N 2 2

3/8 0.375 2/8

0.25

Bernoulli Distribution Approaches Gaussian for large N

-3

1/8 0.125
0

-3

= x/Ut 1 -1 1
-1

Example for N=3

Statistics of position
x (t ) = u ( t ) = 0
i =1 N

N 2 = ut = t 2 [(u 1 + u 2 K u i + K u N )(u 1 + u 2 + K u N )] i =1 = Nt 2U 2 = tU 2 t = tx 2 / t

U 2 t x 2 D= = = 2t 2 2t

[L2/T ]

Alternatively, derive D from Taylors Theorem

Examples of Sources and Sinks (r terms)

1st order 0th order 2nd order Coupled reactions Mixed order

1st Order
Example: radioactive decay c/co
1

dc = kc dt kt c / co = e

0.5 0.37 0.1

0
Half life e-folding time

t1/2

k-1

t90

Linearity => 1st O decay multiplies simple soln by e-kt; e.g. Also very convenient in particle tracking models

0th Order
S/So Example: silica uptake by diatoms (high diatom 1 conc)

dS = B dt S = S o Bt

0
So/B

S=substrate (silica) concentration B=rate (depends on diatom population, but assume large)

2nd Order
Example: particleparticle collisions/reactions; flocculant settling) dc = Bc 2 dt 1 c = co 1 + Btco c/co
1

co

Behavior depends on co; slower than e-kt. Can be confused with multiple species undergoing 1st order removal

Coupled Reactions
Example: Nitrogen oxidation dN1 = K12 N1 dt dN 2 = K12 N1 K 23 N 2 dt dN 3 = K 23 N 2 dt

N1 = NH3-N N2 = NO2-N N3 = NO3-N

If Ns are measured as molar quantities, or atomic mass, then successive Ks are equal and opposite

Mixed OrderSaturation Kinetics (Menod kinetics)

Example: algal uptake of nutrientsfocus on algae

dc kS = dt S + S o

rmax Rmax/2

c = algal concentration S = substrate concentration So = half-saturation const S << So => S >> So =>
dc kS = k'S dt S o dc k dt

So (1st Order) (0th Order)

1 Wrap-up
Molecular diffusivities Molecular motion; Eulerian frame D = wl m

d 2 D= 2dt 2 D = u 2 R ( )d
0

Method of moments Molecular motion; Lagrangian frame

D is small ~ 1x10-5 cm2/s for water Inst. point source solutions are Gaussian; other solutions built from

Spatial and temporal integration, coordinate translation, linear source/sink terms