National Chungbuk University

March 28, 2019 (Thu)

Chapter 2. Membrane Transport Theory

Chang-Han Yun / Ph.D.

Contents of Chapter 2

2.1 Introduction

2.2 Solution-Diffusion Model

Contents
Contents 2.3 Structure–Permeability Relationships

2.4 Pore Flow Membrane

2.5 Conclusions and Future Directions

Chapter 2. Membrane Transport Theory 2

 2.1 Introduction
❖ Most important property of membranes = control the rate of permeation of different species.
❖ Model for transport mechanism
✓ Solution-diffusion model
• Dissolve permeants in membrane
• Diffuse through membrane to permeate-side or strip-side by concentration gradient
• Separate permeants by differences in solubility and diffusivity against to membrane
✓ Pore-flow model
• Transport permeants by pressure-driven convective flow through tiny pores
• Separate permeants by filtering through pores in membrane
✓ Solution-diffusion
Pore-flow model
✓ Dense membrane
✓ Microporous membrane
✓ Difference in solubility and
✓ Molecular filtration mobility of permeants in
membrane material

<Figure 2.1> Molecular transport model through membranes

Chapter 2. Membrane Transport Theory 3
2.1 Introduction
❖ Diffusional flow
✓ Inherently slow process
✓ To get useful flux in practical diffusion-controlled separation
• Membrane = very thin • Concentration gradients(dci/dx) in membrane = large

✓ Fick’s 1st law of diffusion : (2.1)

where Ji = flux of i (g/cm2 · s)

dci/dx = concentration gradient of component i
Di = diffusion coefficient(cm2/s) of component i ⇨ mobility of component i
※ Minus sign ⇨ direction of diffusion to concentration gradient
❖ Pressure-driven convective flow though porous or capillary medium

✓ Darcy’s law : (2.2)

where dp / dx = pressure gradient, ci = concentration of component i

K´ = coefficient reflecting the nature of the medium

Chapter 2. Membrane Transport Theory 4

2.1 Introduction
❖ On the point of free-volume elements(pores) in the membrane
✓ Free volume = tiny spaces between polymer chains caused by thermal motion molecules
✓ Appear and disappear on about the same timescale as the motions of the permeants
✓ Pore-flow model(Darcy’s law) free-volume
• Relatively large and fixed
• Not fluctuate in position or volume on the timescale of permeant motion
• Connected to one another
✓ Transition between solution-diffusion and permanent (pore-flow) pores = 5∼10 Å
❖ Prediction of transport performance from model
✓ Dense membrane by solution diffusion model
• Good agreement with experimental data(well describe properties of membranes)
✓ Microporous membrane(UF, MF) by sieving mechanism
• Ability of theory to rationalize transport in these membranes = poor
• Simple quantitative description of the process = not possible

Chapter 2. Membrane Transport Theory 5

2.1 Introduction

<Figure 2.2> Schematic representation of the nominal pore size and best theoretical model
Chapter 2. Membrane Transport Theory 6
 2.2.1 Molecular
2.2 Solution-diffusion Model Dynamics Simulations

Process Driving Force Applied Pressure

RO Δp Very high
Pervaporation vapor Δpi between feed liquid↔permeate vapor small
Gas separation Δpi or dci/dx

❖ Use similar membranes in very different processes

✓ <Example 1> cellulose acetate membrane
• Used for desalination by RO
• Used for dehydration of alcohol by pervaporation
• Used for separation of CO2 from natural gas by gas separation
✓ <Example 2> silicone rubber membrane(very hydrophobic)
• Not useful in reverse osmosis
• Used to separate volatile organics from water by pervaporation
• Used to separate organic vapors from air in gas permeation.

Chapter 2. Membrane Transport Theory 7

 2.2.1 Molecular
2.2 Solution-diffusion Model Dynamics Simulations
❖ Example of molecular dynamics simulations
✓ System : CO2 in a 6FDA-4PDA polymer matrix
✓ During 1st 100 ps, CO2 molecule bounces around in
the cavity within about 5 Å(diameter of microcavity)
✓ After 100 ps, thermal motion ⇨ moves a segment of
the polymer chains sufficiently ⇨ CO2 molecule to
jump approximately 10 Å to an adjacent cavity
✓ Repeating these steps
✓ Average distance moved
✓ Calculate Di

<Figure 2.3> Motion of a CO2

in a 6FDA-4PDA polymer matrix
Chapter 2. Membrane Transport Theory 8
 2.2.1 Molecular
2.2 Solution-diffusion Model Dynamics Simulations
❖ Another example of molecular dynamics simulations (<Figure 2.4>)
✓ System : three different permeate molecules over a period of 200 ps in silicone rubber polymer
✓ Move more frequently and make larger jumps : He(2.55 Å) > O2(3.47 Å) > CH4 (3.76 Å)
❖ Effect of polymer structure on diffusion
✓ Figure 2.3 (diffusion in a glassy rigid-backbone polyimide) ⇨ only one large jump in 200 ps
✓ Figure 2.4 (diffusion in silicone rubber, very flexible) ⇨ a number of large jumps in 200 ps

<Figure 2.4> Simulated trajectories of He, O2 and CH4 molecules

during a 200-ps time period in a poly(dimethylsiloxane) matrix.

Chapter 2. Membrane Transport Theory 9

 2.2.2 dCi/dx and dpi/dx
2.2 Solution-diffusion Model in Membranes

❖ Gradient in chemical potential ⇨ Overall driving force ⇨ Movement of a permeant

❖ Flux of component i (Ji, g/cm2 · s) : (2.3)
where dμi/dx = chemical potential gradient of component i
where ni = mole fraction of i
Li = coefficient of proportionality (not constant)
γi = activity coefficient of i
❖ Chemical potential of concentration and pressure gradients
p = pressure
✓ dμi = RT d ln(γi ni) + υi dp (2.4) υi = molar volume of i
❖ For incompressible phases(liquid or solid membrane) ⇨ Molar volume = constant ≠ f(p)
✓ Integrating Eq(2.4) with respect to ci and pi ⇨ μi = μio + RT ln(γi ni) + υi(p − pio) (2.5)
where μio = chemical potential of pure i at a reference pressure(pio )
pio = reference pressure = saturation vapor pressure of i (pi, sat)
✓ Eq(2.5) ⇨ μi = μio + RT ln(γi ni) + υi(p − pi, sat) (2.7)
❖ For compressible gases ⇨ Molar volume = f(p)
✓ Eq(2.4) by using ideal gas law ⇨ μi = μio + RT ln(γi ni) + RT ln(p) − RT ln(pio) (2.6)
✓ Eq(2.6) with pio = pi, sat ⇨ μi = μio + RT ln(γi ni) + RT ln(p) − RT ln(pi, sat) (2.8)

Chapter 2. Membrane Transport Theory 10

 2.2.2 dCi/dx and dpi/dx
2.2 Solution-diffusion Model in Membranes
❖ <Assumption> governing transport through membranes
1. Equilibrium between fluids and membrane material
• Continuous gradient in chemical potential from one side of the membrane to the other
• Absorption and desorption rate at membrane 》diffusion rate through membrane
※True for most of membrane processes
Not true ① for transport processes involving chemical reactions(facilitated transport)
② in diffusion of gases through metals (interfacial absorption = slow)
2. p within membrane = uniform in solution-diffusion model ⇨ dμi/dx = expressed only as dCi/dx

<Figure 2.5> Pressure driven permeation of

one-component solution through a membrane
according to the solution-diffusion transport
model.
Chapter 2. Membrane Transport Theory 11
 2.2.2 dCi/dx and dpi/dx
2.2 Solution-diffusion Model in Membranes

❖ In solution-diffusion model
✓ Pressure within the membrane = constant at the high-pressure value (po) ⇨ no gradient
✓ Gradient in chemical potential across membrane = smooth gradient in solvent activity (γi ni)
✓ Combining Equations (2.3) and (2.4) and assuming γi = constant
⇨ (2.3)
(2.9)
dμi = RT d ln(γini) + υidp (2.4)
※ Eq(2.9) : Expression of gradient of i across membrane as a gradient in mole fraction of i
✓ More practical term, concentration ci (g/cm3) defined as ci = mi ρ ni (2.10)
where mi = MW of i (g/mol)
ρ = molar density (mol/cm3)

✓ Eq(2.9) ⇨ (2.11) ⇨ : Fick’s 1st law (2.12)

✓ Integrating over the thickness of the membrane ⇨ (2.13)

Chapter 2. Membrane Transport Theory 12

 2.2.2 dCi/dx and dpi/dx
2.2 Solution-diffusion Model in Membranes
❖ Semipermeable membrane for desalination(a) Dense solution-diffusion membrane

※ Gradient of salt (j) = not shown in this figure

✓ <Assume> Membrane = very selective
⇨ cj within membrane = low
✓ dμi / dx = continuous, smooth from μiℓ to μio
✓ po = pm = pℓ
✓ γi(m) ni(m) falls continuously from pure water
(solvent) side to saline (solution) side.
❖ Osmotic equilibrium(b)
❖ Supply pressure on saline side ⇨ J = 0
❖ pm = assumed to be constant at po
❖ Discontinuity in pressure at the permeate side,
Δp = po − pℓ = Δπ

<Figure 2.6> μ, p, and solvent activity(γini) profiles

through an osmotic membrane following the
solution-diffusion model.
Chapter 2. Membrane Transport Theory 13
 2.2.2 dCi/dx and dpi/dx
2.2 Solution-diffusion Model in Membranes

✓ Equilibrium at permeate side of membrane between membrane and permeate

⇨ Eq(2.7) ⇨ μiℓ(m) = μiℓ (2.14)
and so, RT ln(γiℓ(m) niℓ(m)) + υi po = RT ln(γiℓ niℓ) + υi pℓ (2.15)
✓ Rearranging ⇨ RT ln(γiℓ(m) niℓ(m)) − RT ln(γiℓ niℓ) = −υi (po − pℓ) (2.16)
✓ Osmotic equilibrium ⇨ Δ(γi ni) = γiℓ niℓ − γi(m) ni(m) (2.17)
✓ and, since γiℓ niℓ ≈ 1
✓ Substituting Eq(2.17) into (2.16) ⇨ RT ln[1 − Δ(γi ni)] = −υi (po − pℓ) (2.18)
✓ Since Δ(γi ni) = small ⇨ ln[1 − Δ(γi ni)] ≈ Δ(γi ni)

✓ Eq(2.18) ⇨ (2-19)

❖ Δp > Δπ ⇨ Reverse Osmosis(<Figure 2-6(c)>) ⇨ Flow from left to right

❖ Important conclusion
Even though different p and ci on either side within a perfect solution-diffusion membrane
no pressure gradient ⇨ only a concentration gradient ⇨ expressed by Fick’s law[Eq(2.13)]

Chapter 2. Membrane Transport Theory 14

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
❖ Transport equation by solution-diffusion model
✓ Transport equations ⇨ linking J ↔ driving forces ⇨ comparison with experimental data
❖ Procedure to drive transport equation
1. Use the 1st assumption of the solution-diffusion model
• μ of feed and permeate fluids are in equilibrium with membrane. ⇨ μio = μio(m)
※ Eq(2.7) : μi = μio + RT ln(γi ni) + υi(p − pi, sat) for liquid and solid(incompressible)
※ Eq(2.8) : μi = μio + RT ln(γi ni) + RT ln(p) − RT ln(pi, sat) for gas(compressible)
2. By rearranging ⇨ obtain cio(m) and ciℓ(m) = f(p, cif, cip)

3. Substitution cio(m) and ciℓ(m) into the Fick’s law, ⇨ transport equation

Chapter 2. Membrane Transport Theory 15

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
2.2.3.1 Dialysis
❖ Dialysis = only concentration gradients involved ⇨ simplest application of the model
✓ Membrane separates two solutions of different compositions, feed and dialysate.
✓ The concentration gradient across the membrane ⇨ flow of solute and solvent
❖ Transport equation for feed-side
1. Equating chemical potentials at feed-side interface ⇨ μio = μio(m) (2.20)
2. Eq(2.7) : μi = μio + RT ln(γi ni) + υi (p − pi, sat)
⇨ μio + RT ln(γioL nio) + υi (p − pi, sat) = μio + RT ln(γio(m) nio(m)) + υio(m) (p − pi, sat) (2.21)

⇨ ln(γioL ni) = ln(γio(m) nio(m)) (2.22) ⇨ (2.23)

3. Eq(2.10) : ci = mi ρ ni ⇨ (2.24)
cio(m) = KiL · cio (2.26)
4. Define sorption coefficient as (2.25)

❖ Transport equation for permeate-side : ciℓ(m) = KiL · ciℓ (2.27) by same procedure
Chapter 2. Membrane Transport Theory 16
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes

❖ Substitution cio(m) and ciℓ(m) into Fick’s 1st law, Eq(2.13) :

⇨ Transport equation for dialysis : (2.28)

✓ DiKiL = normally referred to as the permeability coefficient, PiL
✓ For many systems, Di, KiL and PiL = f(concentration) ⇨ use averaged over membrane thickness
❖ Permeability coefficient (PiL)
✓ Often treated as a pure materials constant ✓ PiL = f(membrane and permeant ) only
✓ Eq(2.28) and (2.25) ⇨ (2.29)
• γ iL = f(solvent) ⇨ PiL = f(solvent) ※ Refer <Figure 2.7>
❖ <Figure 2.7> : Plot of Ji·ℓ verse Δci or (cio − ci ) according to Eq(2.28) ⇨ Slope = Permeability(PiL)
✓ PiL for water : 9.5 × 10−7 cm2/s
※ 1,000 times difference according to solvent
✓ P iL for PEG 600 : 6.5 × 10−10 cm2/s
✓ Driving force = Δci × Δci, sat ⇨ all the data fall on a single line(<Figure 2.7(d)>)
✓ For dilute solution, ⇨ ⇨ Slope = PiL ·csat or Di mi ρm / γi(m)

Chapter 2. Membrane Transport Theory 17

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes

<Figure 2.7> Permeation of progesterone through polyethylene vinyl acetate films.

Solvents for the progesterone : (a) water, (b) silicone oil and (c) poly(ethylene glycol) (PEG 600)
✓ By different solubilities, PiL calculated from these data through Eq(2.28) vary 1000-fold.
✓ Slope : [PiL ·csat or Di mi ρm / γi(m)] = f(membrane, permeant) only ≠ f(solvent)
Chapter 2. Membrane Transport Theory 18
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
2.2.3.2 RO i = water and j = salt
❖ Feed side for water(i)
✓ No pressure difference exists at the permeate interface (<Figure 2.6c>)
✓ Equating the chemical potentials across this interface ⇨ μio = μio(m) (2.20)
✓ Eq(2-16) ⇨ cio(m) = KiL · cio (2.32) : same equation as in dialysis

<Figure 2.8> A schematics of the relationship between osmosis (dialysis), osmotic equilibrium and RO
Chapter 2. Membrane Transport Theory 19
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
❖ Permeate side for water(i)
✓ Pressure difference at the permeate interface(Δp = po − pℓ within membrane(<Figure 2.6c>))
✓ Equating the chemical potentials across this interface ⇨ μiℓ = μiℓ (m) (2.33)
✓ Eq(2.7) ⇨ μio + RT ln(γiℓL niℓ) + υi(pℓ − pi, sat) = μio + RT ln(γiℓ(m) niℓ(m)) + υi (p − pi, sat) (2.34)

⇨ (2.35)

✓ By definition of KiL, ⇨ (2.36)

❖ Transport equation for water(i)

✓ Substituting Eq(2.32) and (2.36) ⇨ (2.37)

❖ Similarly, transport equation for salt(j) : (2-44)

❖ For more common application

✓ <Assume> Membrane selectivity = very high ⇨ DiKiL / ℓ≫ DjKjL / ℓ
✓ At osmotic equilibrium ⇨ pi − pℓ = Δπ
Eq(2.37) ⇨ (2.39)
⇨ Ji = 0
Chapter 2. Membrane Transport Theory 20
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
✓ At high hydrostatic pressure ⇨ pi − pℓ ≫ Δπ
• Combining Eq(2.37) and (2.39) ⇨ (2.41)
where Δp = difference in hydrostatic pressure across the membrane (pi − pℓ )
• By trial calculation ⇨ −υi (Δp − Δπ) / RT = small under the normal conditions of RO
<Example> Water desalination
Δp = 100 atm, Δπ = 10 atm, and υi = 18 cm3/mol, ⇨ υi (Δp − Δπ) / RT = 0.06
• <Simplification> 𝒍𝒊𝒎[𝟏 − 𝒆𝒙𝒑 𝒙 ] = 𝒙 as x → 0

Eq(2.41) ⇨ (2.42) ⇨ Ji = A (Δp − Δπ) (2.43)

where A = Di KiL cio υi / RT = constant = water permeability constant

❖ Simplified expression for the salt flux(Jj)
✓ −υi (Δp − Δπ) / RT = small ⇨ exponential term in Eq(2.44) = 1

✓ Eq(2.44) ⇨ (2.45) ⇨ Jj = B (cjo − cjℓ) (2.46)

where B = = constant = salt permeability constant (2.47)

Chapter 2. Membrane Transport Theory 21

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
<Discussion>
1. Eq(2.43), water flux(Ji) = A (Δp ─ Δπ) ⇨ Δp↑ → Ji ↑
2. Eq(2.46), salt flux(Jj) = B (cjo ─ cjℓ) ⇨ Jj ≠ f(Δp)
3. Rejection coefficient(R), (2.48) ⇨ Δp↑ → Ji ↑ → R↑(∵ Jj = not change)

<Figure 2.9> Flux and rejection for 3.5% NaCl solution in FilmTec FT 30 as a function of pressure.
Chapter 2. Membrane Transport Theory 22
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
2.2.3.3 Hyper-filtration
❖ Use dense membrane as like RO ❖ Separate organic molecule from mixture
✓ <Example> MEK from MEK-oil mixture, lubricant production plant of Mobil
❖ Mathematical description of this process = same with RO in Eq(2.37) and (2.44)

(2.49) (2.50)

<Assume> Permeability of MEK = 10 × permeability of n-decane

<Figure 2.10> J & R calculated using Eq(2.49) and (2.50) for a 20 wt% n-decane solution in MEK.
Chapter 2. Membrane Transport Theory 23
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes

2.2.3.4 Gas Separation ※ po = pressure of feed side(gas mixture), pℓ = pressure of permeate gas
❖ Transport equation
✓ Chemical potential for gas phase : μi = μio + RT ln(γi ni) + RT ln(p) − RT ln(pi, sat) (2.8)
✓ Chemical potential for membrane : μi = μio + RT ln(γi ni) + υi (p − pi, sat) (2.7)
✓ Equating the chemical potentials across this interface ⇨ μio = μio(m) (2.20)

⇨ (2.51)

✓ By rearrange ⇨ (2.52)

✓ At very high pressure(po), =1⇨ (2.53)

✓ nio·po = pio ⇨ (2.54) or (2.55)

✓ Definition of gas phase sorption coefficient KiG, (2.56)

Chapter 2. Membrane Transport Theory 24

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
✓ At feed interface of membrane : Eq(2.55) and (2.56) ⇨ cio(m) = KiG ·pio (2.57)
✓ At permeate interface of membrane : Eq(2.55) and (2.56) ⇨ ciℓ(m) = KiG ·piℓ (2.58)

✓ Combining Eq(2.57) and (2.58) with the Fick’s law(Eq(2.13) : )

⇨ (2.59)

✓ Di KiG = permeation coefficient = piG = (2.61) ⇨ (2.60)

❖ Assumptions behind transport equation

1. Concentration gradient within membrane, but no gradient in pressure
2. Absorption into membrane = f(activity (partial pressure)) ≠ f(total gas pressure)

3. Approximation used for high feed pressure : =1

❖ Mass flux(g/cm2·s) ↔ molar flux(cm3(STP) / cm2·s) : (2.62)

❖ Mass permeability(PiG) ↔ molar permeability (cm3(STP)·cm / cm2·s·cmHg) : (2.63)

where υiG = molar volume of gas i (cm3(STP) / mol)
Chapter 2. Membrane Transport Theory 25
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes

❖ Eq(2.60) ⇨ (2.64)

❖ Combining Eq(2.61) and (2.63) ⇨ (2.65)

❖ For high permeability coefficients from Eq(2.65)

✓ High diffusion coefficient (high Di) ✓ High affinity for membrane material (small γi(m))
✓ Limited affinity for gas phase (high γiG) ✓ Low saturation vapor pressure (pi, sat)
❖ Molar gas permeation permeability (PiG) = f(materials, permeant) ≠ f(ci, p of feed and permeate)
❖ For vapor
✓ By plasticization and other effect changing Di and γi(m) ⇨ pi ↑→ PiG ↑ at pi ≈ pi, sat
✓ Occur significant non-ideality of vapor’s activity coefficient, γiG at high partial pressures(pi)

Chapter 2. Membrane Transport Theory 26

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
❖ Effect of MW on permeability from Eq(2.65)
✓ MW ↑ → pi,sat ↓ and Di ↓ ⇨ two opposite effects on PiG
Items Glassy polymers Rubbery polymers
Dominant term Di pi, sat for MW < 100 Di for MW > 100
As MW↑ Di ↓ and PiG ↓ significantly pi, sat ↑ → PiG ↑ generally Di ↓→ PiG ↓ generally

<Figure 2.11> Permeability coefficient (PiG)

of n-alkanes in poly(dimethylsiloxane) as a
function of saturation pressure (pi, sat )
Chapter 2. Membrane Transport Theory 27
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
2.2.3.5 Pervaporation
❖ Feed = multi-component liquid ❖ Permeate = one or more preferential vapor by vacuum
❖ Gradients in chemical potential(dμ/dx) = pressure, and activity across the membrane
❖ At feed side(liquid solution ↔ membrane interface)
✓ μ of feed liquid = μ in membrane at same pressure
✓ Eq(2.7) ⇨ μio + RT ln(γioL nio) + υi (po − pi, sat) = μio + RT ln(γio(m) nio(m)) + υi (po − pi, sat) (2.66)
✓ Expression for the concentration at the feed side interface

Eq(2.66) ⇨ (2.67)

where KiL = Liquid phase sorption coefficient

defined in Eq(2.26) in dialysis

<Figure 2.12> μ, p and γ profiles through a pervaporation

membrane following the solution-diffusion model.
Chapter 2. Membrane Transport Theory 28
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
❖ At permeate side(vapor ↔ membrane interface)
✓ Pressure drop : po → pℓ
✓ μ of permeate vapor = μ in membrane at same pressure(pℓ)
✓ Eq(2.7) ⇨ μio + RT ln(γiℓL niℓ) + RT (pℓ − pi, sat) = μio + RT ln(γiℓ(m) ni) + υi (po − pi, sat) (2.68)
✓ Rearranging Eq(2.68) ⇨ Expression for the concentration at permeate side interface
1
✓ Eq(2.68) ⇨ (2.69)&(2.70)

✓ niℓ pℓ = piℓ ⇨ (2.71)

✓ Change to concentration by Eq(2.10) ⇨ (2.72)

where KiG = Gas phase sorption coefficient defined in Eq(2.56) in gas separation
✓ Substitute Eq(2.67) and (2.72) into Fick’s 1st law :

⇨ Transport equation for pervaporation : (2.73)

Chapter 2. Membrane Transport Theory 29

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
❖ Liquid phase sorption coefficient(KiL) Gas phase sorption coefficient(KiG)
need interconversion
✓ Hypothetical vapor in equilibrium with a feed solution
✓ VLE ⇨ μio + RT ln(γiL niL) + υi (p − pi, sat) = μio + RT ln(γiG niG) + RT (p − pi, sat) (2.74)
where superscripts L and G = liquid phase and vapor phases, respectively

✓ Same procedure with Eq(68) to (2.72), Eq(2.74) ⇨ (2.75)

✓ Converting to concentration by Eq(2.10) ⇨ (2.76) & (2.77)

✓ Eq(2.73) ⇨ ※ more useful (2.78) & (2.79)

where pio and piℓ = partial pressure of vapor i (pi) on either side of membrane
❖ Eq(2.79) ⇨ explicitly expression of driving force in pervaporation by partial pressure difference
❖ Eq(2.77) ⇨ link cioL with equilibrium pi ⇨ Henry’s law (Hi · ciL = pi) (2.80)

✓ Henry’s law constant coefficient, (2.81

Chapter 2. Membrane Transport Theory 30

 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes

✓ Eq(2.73) ⇨ (2.82)&(2.83)
❖ Eq(2.83) ⇨ explicitly expression of driving force in pervaporation by concentration difference
❖ Temperature dependency of Pi : PiG ≪ PiL
❖ Pressure dependency of Pi
<Example 1> Pervaporation of water(<Figure 2.13>)
• Permeate pressure(piℓ) ↑ → water flux(Ji) ↓
• Ji = 0 at piℓ = feed liquid vapor pressure (pi, sat)
• Slope = permeability coefficient (PiG)
• Membrane = Rubbery polymer
※ Moderate swollen by water

<Figure 2.13> Effect of permeate pressure on the water

flux through a silicone rubber pervaporation membrane.
The arrows on the lower axis represent the saturation
vapor pressures of the feed solution as predicted by
Eq(2.79)
Chapter 2. Membrane Transport Theory 31
 2.2.3 Application of
2.2 Solution-diffusion Model Solution-diffusion Model
to Specific Processes
<Example 2> Pervaporation of Hexane(<Figure 2.14>) : high swollen
• Rubbery polymer = high swollen by hexane
• <Figure 2.14(a)> : typical behavior of significant swollen membranes by permeant
• piℓ ↑ → Ji ↓ and a minimum value when piℓ = pi, sat (saturation vapor pressure of the feed)
• Ji ≠ f(pio) up to 20 atm (<Figure 2.14(b)>) at low fixed permeate pressure

<Figure 2.14> The effect of feed and permeate pressure on the flux of hexane through a rubbery
pervaporation membrane. Ji ≠ f(pio) up to 20 atm = f(piℓ) severely
Chapter 2. Membrane Transport Theory 32
 2.2.4 Evidence for
2.2 Solution-diffusion Model Solution-diffusion Model
❖ Issue in 1970s : po ↑ → ciℓ ↓ ? (2.37)

2.2.4.1 Rosenbaum and Cotton’s experiments

❖ Experimental procedure
✓ Laminated 4 thin CA films together
✓ Placed in a high pressure RO cell
✓ Feed pressures = 68 or 136 atm
✓ Permeate = maintained at atmospheric pressure
✓ After reaching steady state, quickly remove membrane
✓ Measure water concentration in each laminate membrane
❖ Results (2.36)
✓ Applied pressure ↑ ⇨ water concentration on permeate side ↓
✓ Δci at 136 atm = 2 × Δci at 68 atm
✓ Measured Δciℓ < 20% of Δciℓ calculated from Eq(2.36)
<Figure 2.15> Water concentration gradients in a laminated RO(CA
membrane) under applied pressures of 68 and 136 atm.
Chapter 2. Membrane Transport Theory 33
 2.2.4 Evidence for
2.2 Solution-diffusion Model Solution-diffusion Model
2.2.4.2 Paul and co-workers’s experiments
❖ Experimental procedure
✓ Same phenomenon using rubbery membranes(operated in RO mode)
✓ Permeation of organic solvents(hexane, benzene and CCl4) ⇨ Highly swollen by organic solvent
❖ Results
✓ High concentration gradients develop through
membrane even at modest applied pressures
⇨ pio ↑ → ciℓ ↓ → 0
⇨ pio ↑ → J = reaches a limiting value

<Figure 2.16> Pressure permeation (RO) of iso-octane

and MEK through crosslinked 265-μm-thick natural
rubber membranes.
✓ Change in concentration gradient in membrane as
applied pressure is increased is illustrated by
inserts.
✓ At high applied pressures, concentration gradient
and the permeation fluxes approach their limiting
values.
Chapter 2. Membrane Transport Theory 34
 2.2.4 Evidence for
2.2 Solution-diffusion Model Solution-diffusion Model
2.2.4.3 Paul and Paciotti’s experiments
❖ Experimental procedure : Same experiments with Paul and co-workers
✓ Measuring the flux of hexane through a membrane
• Pervaporation with a 1 atm on the feed and a vacuum on the permeate
• RO with liquid at elevated pressures on feed and at a 1 atm on permeate
❖ Results
✓ cio(m) & ciℓ(m) from Eq(2.26), (2.36) and (2.76).
✓ Sorption data ⇨ obtain KiL
✓ RO and pervaporation obey one unique transport
equation : Fick’s law(solution-diffusion model)
✓ Swelling ↓ → Di ↓→ ciℓ(m) ↓ → Δci ↑
⇨ Slope of the curve ↓

<Figure 2.17> Flux of hexane through a rubbery

membrane as a function of Δci in membrane.
✓ RO (●) and pervaporation (○) from experiments.
✓ cio(m) and ciℓ(m) from Eq(2.26), (2.36) and (2.76).
✓ Maximum flux at maximum Δci , when ciℓ(m) → 0.
Chapter 2. Membrane Transport Theory 35
 2.3 Structure–Permeability Relationships
❖ Permeability = Diffusion coefficient × Sorption coefficient ⇨ P = D ·K (2.84)
✓ Sorption coefficient (K)
• Sorption = equilibrium term ⇨ Link ci with ci(m)
• Thermodynamics ⇨ calculate solubilities of gases in polymers to within a factor of 2 or 3
✓ Diffusion coefficients (D)
• Diffusion = kinetic terms ⇨ Effects of surrounding on molecular motion of permeant
• Calculation of Di in liquids and gases = not difficult much
• Calculation of Di in polymers = much more difficult
• Simple correlations based on polymer free volume must be used.
✓ Molecular dynamics to predict Di in polymers
• Most accurate method
• Still under development (possible only for small gas molecules in amorphous polymers)
※ In general, effect of membrane material on Di of a permeant ≫ sorption coefficient(Ki)

Chapter 2. Membrane Transport Theory 36

 2.3 Structure–Permeability Relationships
❖ Plot for Di and Ki of 4 gases in 18 related polyimides
✓ Both Di and Ki are fairly well grouped for each gas.
✓ Difference in Di = approximately 100 fold
✓ Difference in Ki = only 2 ∼ 4 fold
⇨ Effects of change in polymer on Di ≫ Ki
❖ Relative position of each polymer = similar for all gases
⇨ Polymer with high Di for CH4 = high Di for N2, CO2, H2
⇨ Trend for Ki = similar
❖ As a general rule
By changing the membrane material
✓ Permeability = easily varied by orders of magnitude
✓ Selectivity = difficult to changing > 2∼3 times
※ Selectivity = ratio of permeabilities
<Figure 2.18> Diffusion and sorption coefficients plotted for
gases in a family of 18 related polyimides.
Chapter 2. Membrane Transport Theory 37
 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients

❖ Magnitude of Di = governed by restraining forces of medium on diffusing species

✓ C in diamond : move infrequently and each movement = very small(1∼2 Å) ⇨ very small Di
✓ CO2 in gas : constant motion and each jump > 1000 Å ⇨ extremely large Di
❖ Diffusion in liquids and polymers : Di = about 10−5 ∼ about 10−10 cm2/s

[Table 2.1] Typical diffusion coefficients in various media (25℃)

Permeant/material Diffusion coefficient, Di (cm2/s)
✓ O2 in air (atmospheric pressure) 1.0 × 10−1
✓ Salt in water 1.5 × 10−5
✓ Albumin (MW 60 000) in water 6.0 × 10−7
✓ O2 in silicone rubber 1.0 × 10−5
✓ O2 in polysulfone 4.0 × 10−8
✓ Na atoms in NaCl crystals 1.0 × 10−20
✓ Al atoms in metallic Cu 1.0 × 10−30

Chapter 2. Membrane Transport Theory 38

 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients

❖ Liquids : simple, well defined systems and the starting point for modern theories of diffusion

Stokes–Einstein equation

❖ <Assume 1> Shape of diffusing solute = sphere ⇨ (2.85)

where k = Boltzmann’s constant a = radius of the solute η = solution viscosity

✓ Good approximation for large solutes(5 ∼ 10 Å)
※ For smaller solutes, slip of solvent at the solute molecule’s surface ⇨ less valid

❖ <Assume 2> Complete slip at the surface of the solute sphere ⇨ (2.86)

✓ Best expression of Stokes–Einstein equation ⇨ 4≤n≤6 (2.87)

❖ Important conclusion of Stokes–Einstein equation
✓ Di of solutes in a liquid only changes slowly with MW
✓ because Di ∝ a－1 ⇨ Di ∝ approximately MW －3

Chapter 2. Membrane Transport Theory 39

 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients

2.3.2.1 Diffusion in Liquids

❖ With large solutes, n → 6 ⇨ Theory = valid for normal macroscopic fluid dynamics
❖ For solute radius < about 4 Å : n < 6
⇨ Theory = less valid
⇨ water ≠ continuous fluid

<Figure 2.19> Value of the coefficient n in

the Stokes–Einstein equation required to Theory = less valid Theory = valid
achieve agreement between calculation
and experimental solute Di in water.
Chapter 2. Membrane Transport Theory 40
 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients

❖ Stokes–Einstein equation
✓ Works well for diffusion of solutes in simple liquids
✓ Fails in more complex fluids, such as a solution of a high MW polymer
✓ Polymer in a liquid ⇨ solvent’s viscosity(η) ↑ → Di = ↓ slightly
<Example> poly(vinyl pyrrolidone) dissolved in water(from 0 to 20 wt %)
• η of solution ↑ by several orders of magnitude
• Di of sucrose(solute to diffuse) in these solutions ↓ by a factor of four only
❖ Effects of polymer dissolved fluid on diffusivity
✓ Long polymer chains link distant parts of water ⇨ change η of fluid substantially
✓ Immediately surrounding the diffusing species ⇨ effect of polymer chain length = low
❖ η difference between microscopic viscosity ↔ macroscopic viscosity
✓ In simple liquids ⇨ macroscopic η = microscopic η
✓ In gels or polymer films ⇨ microscopic η ≠ macroscopic η significantly

Chapter 2. Membrane Transport Theory 41

 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients
2.3.2.2 Diffusion in Polymers
❖ Key : local environment around permeant ⇨ determines Di of permeant
❖ 2 broad categories of polymer : rubbery and glassy
✓ Rubbery polymer : free rotation of polymer backbone
• Polymer = soft and elastic
• Thermal motion of segments ⇨ permeant’s Di = high
✓ Glassy polymer : steric hindrance along polymer backbone
✓ Prohibits rotation of segments
• Polymer = rigid and tough
• Thermal motion = limited ⇨ Di of permeant = low
❖ Glass transition temperature (Tg)
✓ T > Tg ⇨ thermal energy ⇨ rotate backbone segment
✓ T > Tg ⇨ Polymer : glassy state → rubbery state
<Figure 2.20> Permeant Di as a function of permeant MW in water,
natural rubber, silicone rubber and polystyrene.
Di of solutes in polymers usually lie between Di in natural rubber
(extremely permeable) and Di in PS (extremely impermeable) Chapter 2. Membrane Transport Theory 42
 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients
❖ For very small molecules(He or H2) : difference in Di for all media < factor of two or three
✓ Interact with only one or two atoms in their immediate proximity
✓ Local environment = not radically different to that in a liquid such as water
❖ For larger solutes (MW > 200, diameters of 6 to 10Å)
✓ Quite different local environments in the different media
✓ In water
• Follow Stokes–Einstein equation
• Resistance to movement of solutes = not much larger than that of a very small solute
✓ In polymer membranes
• Involving several segments of polymer chain in each movement of diffusing species
• Di = much smaller than in liquid water
• Differences of motion of polymer segments between in rubbery and in glassy = large

Chapter 2. Membrane Transport Theory 43

 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients
ci(m)
< 5% > 5% 20 % 20∼70 % >70%
Items
Di (cm2/s) 1∼5 × 10−9 1 × 10−7 1 × 10−6
Metrix Glassy Rubbery Solvent-swollen gel Polymer solution
Segment motion Small Relatively large

<Example> change in Di as matrix material changes

❖ Experiments conditions
✓ Polymer = Ethyl cellulose (Tg = 45∼50 ℃)
✓ Permeant = Dichloroethane(C2H4Cl2)
✓ ci(m) of C2H4Cl2 : < 1% ∼ > 90%
❖ Plasticization ⇨ change polymer matrix
❖ ci(m) ↑ of C2H4Cl2 : glassy → rubbery → solvent swollen
gel → polymer solution

<Figure 2.21> Changes in Di of C2H4Cl2 in ethyl cellulose

as a function of volume fraction of C2H4Cl2 dissolved in
polymer matrix
Chapter 2. Membrane Transport Theory 44
 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients
❖ Quantitative link between structure of polymers and permeation properties
✓ Not developed yet
✓ Developed a set of semi-empirical rules
• Permeation properties of polymer groups ↔ small changes in their chemical structures
✓ Fractional free volume (vf , cm3/cm3) : (2.88)
where v = specific volume of the polymer (cm3/g) = ρ－1 of polymer
vo = volume occupied by permeant (cm3/g)
❖ Free volume of polymer
✓ Sum of the many small spaces between polymer chains in amorphous polymer
✓ Measure specific volume(v) ⇨ determine free volume(vf) ⇨ calculate occupied volume (vo)
✓ ∑[molar volume(υi)] ⇨ occupied volume (vo) of polymer = 1.3 × Van der Waals volume
※ Some unoccupied space is inevitably present even in crystals at 0 K ⇨ factor of 1.3

Chapter 2. Membrane Transport Theory 45

 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients
❖ Polymer specific volume, v (cm3/g) as a function of temperature
✓ At high temperatures : loose packing of chain ⇨ occur free volume polymer ⇨ rubbery state
※ Free volume in a rubbery polymer coming from amorphous structure of polymer
✓ Only a few % of vf ⇨ allow rotation of segments of polymer backbone at high temperatures
※ Rubbery polymer has some of the characteristics of a liquid.(solid at macroscopic level)
✓ Temperature of polymer ↓ → vf ↓
❖ T → Tg ✓ vf ↓ ⇨ stop segmental motion
✓ Free volume elements between chains ⇨ essentially frozen into polymer matrix
❖ T ↓ further
✓ Vibrational energy of the groups forming the polymer ↓ → occupied volume ↓
✓ vf = essentially constant
✓ Free volume of a glassy polymer = Normal free volume + Excess free volume
• Normal free volume = elements caused by the incomplete packing of polymer chains
• Excess free volume = elements frozen into polymer matrix

Chapter 2. Membrane Transport Theory 46

 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients

[Table 2.2] Calculated fractional free volume(vf)

for representative membrane materials at
ambient temperatures (Bondi method)
Polymer Tg vf
Polymer
type (℃) (cm /cm3)
3

Silicone rubber Rubber -129 0.16

Natural rubber Rubber -73 0.16
Polycarbonate Glass 150 0.16
Poly(phenylene oxide) Glass 167 0.20
Polysulfone Glass 186 0.16
6FDA-ODA polyimide Glass 300 0.16
Poly(4-methyl-2-pentyne) Glass > 250 0.28
(PMP)
Poly(1-trimethylsilyl-1-propyne) Glass > 250 0.34
(PTMSP)
<Figure 2.22> Change in specific volume(v) as
a function of temperature for a typical polymer.

❖ Fractional free volume(vf) calculated by the Bondi method

✓ For rubbers polymer = about 10 to 15%
✓ Excess free volume contribution ⇨ For glassy polymers = slightly higher(15 to 20%)
Chapter 2. Membrane Transport Theory 47
 2.3.1
2.3 Structure–Permeability Relationships Diffusion Coefficients
❖ Polyacetylene polymers(PTMSP and PMP) : having extraordinarily rigid polymer backbones
✓ Tg = very high(> 250℃) ✓ Possible within a single class of materials
❖ Correlation of permeation properties with free volume
✓ Not possible for a wide variety of polymers ✓ vf = unusually high as much as 25 to 35%

<Figure 2.23> Structure of two high-free-volume

substituted polyacetylenes, PTMSP and PMP.
✓ C〓C double bond = completely rigid
✓ Depending on size of substituents, rotation around the
C–C can be very restricted also.
✓ Result is very stiff-backboned, rigid polymer chains
which pack very poorly, leading to unusually high [Figure 2.24] Correlation of Pi of O2 for a
fractional free volumes family of related polysulfones with vf －1
Chapter 2. Membrane Transport Theory 48
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients
❖ Sorption coefficients(KiG) of gases in polymers
✓ Relatively constant for polymers(<Figure 2.25>)
✓ Behavior of sorption in polymer ⇨ polymer = ideal fluids
✓ Di of CH4 in different polymers = vary by > 105
✓ KiG = vary by only a factor of 10
(about mean value = 15 × 10−3 cm3(STP)/cm3 · cmHg)
❖ Gas sorption in a polymer
✓ Henry’s law, cio(m) = KiG ·pio (2.57) ⇨ ci(m) = KiG ·pi (2.89)

✓ Eq(2.89) and definition of KiG, (2.56)

⇨ (2.90)

✓ Definition of mole fraction [ci = mi ρ ni (2.10)]

⇨ ci(m) = mi ρm ni (2.91)
<Figure 2.25> Di and KiG of CH4 in different families of polymer.
Di change over a wide range but KiG are relatively constant.
Chapter 2. Membrane Transport Theory 49
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients

✓ Eq(2.90) ⇨ (2.92)

✓ γiG and γi(m) = 1 for ideal gas dissolving in ideal liquid. So Eq(2.92) ⇨ (2.93)
Where ni(m) = mole fraction of gas sorbed in liquid, pi = partial pressure of gas
Pi, sat = saturation vapor pressure at the pressure and temperature of the liquid
❖ Gas saturation vapor pressure(Pi, sat )
✓ Clausius–Clapeyron eq. ⇨ extrapolate from available VLE data to ambient range ⇨ Pi, sat
✓ Gas = supercritical at ambient temperatures [Table 2.3] ni(m) of CH4 in various
solvents at 25℃ and 1 atm.
⇨ Pi, sat = not correspond to a stable VLE for some gas
ni(m) of CH4 in an ideal liquid under
<Example> Pi, sat of CH4 by extrapolatation = 289 atm at 25℃.
same conditions = 0.0035
⇨ Mole fraction(ni(m)) of CH4 dissolved in an ideal liquid Liquid ni(m) of CH4
= 1/289 = 0.0035 from Eq(2.93) Ethyl ether 0.0045
Cyclohexane 0.0028
❖ Comparison of ideal KiG with measured KiG for CH4 Carbon tetrachloride 0.0029
✓ Some deviation for small polar solvent (H2O, MtOH) Acetone 0.0022
Benzene 0.0021
✓ Overall agreement is remarkably good. Methanol 0.0007
Water 0.00002
Chapter 2. Membrane Transport Theory 50
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients

❖ Flory–Huggins theory of polymer solution

✓ Large difference in molecular size between the two components
⇨ generate entropy of mixing of solutes in polymers
✓ Flory–Huggins expression for the free energy of mixing of a gas in polymer solution

(2.94)

where υi and υj = molar volumes of gas(i) and polymer(j) respectively

Vi = volume fraction of polymer(j) occupied by sorbed gas(i)

✓ υi ≈ υj ⇨ ideal liquid case : Eq(2.94) → reduce to Eq(2.93)

✓ υi ≪ υj ⇨ υi/υj ≈ 0 ⇨ Eq(2.94) → (2.95) ⇨ (2.96)

𝒏𝒊(𝒎)
✓ Vi = very small ⇨ exp(1－Vi) ≈ exp(1) = 2.72 ⇨ = (2.97)
𝟐.𝟕𝟐
『Meaning of Eq(2.97)』
✓ Vi of absorbed gas in ideal polymer = ni of absorbed gas in ideal liquid / 2.72
<Assume> Molar density of sorbed gas = MW －1 (mol/cm3) to calculate sorbed gas in cm3 (STP)/cm3
Chapter 2. Membrane Transport Theory 51
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients
[Table 2.4] and <Figure 2.26>
✓ Thermodynamics ⇨ Qualitative prediction of sorption of simple gases in polymers (< factor of 2)
✓ Eq(2.97) ⇨ predict almost same solubility for same gas for all polymer and solubility ∝(pi, sat)－1

[Table 2.4] Solubility of gases in an ideal liquid

and an ideal polymer (35 ℃)

Predicted
Gas Pi, sat ni(m) in liquid at Vi in polymer
(atm) 1 atm by Eq(2.93) by Eq(2.97)
N2 1,4000 0.0007 2.6
O2 700.0 0.0014 4.8
CH4 366.0 0.0027 18.4
CO2 79.5 0.0126 29.5

<Figure 2.26> Average sorption coefficients of

simple gases in a family of 18 related polyimides
plotted against the expected sorption in an ideal
polymer calculated by using Eq(2.97)
Chapter 2. Membrane Transport Theory 52
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients
❖ Another way of showing solubility of gas in polymer
✓ Plot gas sorption against convenient measure of pi, sat (ex, bp or Tc of gas)
❖ <Figure 2.27>
✓ Difference in gas sorptions of polymers
= relatively small
✓ Experimental data
= grouped around the calculated value
❖ Fine-tuning by dual-sorption model

<Figure 2.27> Solubility as a function of Tc

for a typical glassy polymer (polysulfone)
and a typical rubbery polymer (silicone
rubber) compared with values for the ideal
solubility calculated from Equation (2.97)
Chapter 2. Membrane Transport Theory 53
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients
❖ Fine-tuning by dual-sorption model : “gas sorption in a polymer (cm) occurs in two types of sites.”
✓ The 1st type
• Filled by gas in equilibrium free volume portion of material (concentration cD )
• Population of dissolved gas molecules in rubbery polymers
✓ The 2nd type
• Filled by gas in excess free volume of glassy polymer (concentration cH)
• Population of dissolved gas molecules in glassy polymers
• Total sorption in a glassy polymer : cm = cD + cH (2.98)
✓ Concentration cD
• Dissolved in the equilibrium free volume portion of the polymer
• Behave as in normal sorption in a liquid
• Henry’s law sorption ⇨ cD = KD·p (2.99)
• Fraction of total sorption = equivalent to the value calculated in Equation (2.97)

Chapter 2. Membrane Transport Theory 54

 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients
✓ Concentration cH
• Dissolved into the excess free volume elements of the polymer ⇨ limited amount
• Filled by gas in all site ⇨ sorption = stopped
• Best approximation = Langmuir-type absorption isotherm : (2.100)
✓ Dual sorption model : cm = cD + cH and at high pressures cH → c′H,

• Eq(2.99) and (2.100) ⇨ (2.101)

where c′H = saturation sorption concentration

⇨ filled all excess free volume sites

<Figure 2.28 >An illustration of the two components that

contribute to gas sorption in a glassy polymer according
to the dual sorption model.
✓ Henry’s law sorption occurs in the equilibrium free
volume portion of the polymer.
✓ Langmuir sorption occurs in the excess free volume
between polymer chains that exists in glassy polymers
Chapter 2. Membrane Transport Theory 55
 2.3.2
2.3 Structure–Permeability Relationships Sorption Coefficients
❖ Permeation of gases in glassy polymer described in terms of dual sorption model
• Follow by henry’s law ⇨ Diffusion coefficient = DD
• Gas contained in the excess free volume ⇨ Diffusion coefficient = DH
• Fick’s law expression ⇨ (2.102)

Chapter 2. Membrane Transport Theory 56

 2.4 Pore Flow Membrane
❖ No unified theory to describe transport in microporous membranes
✓ Extremely heterogeneous nature of
microporous membranes
✓ Significantly different in structure and
mechanism according to membranes
❖ Imperfect parameters to characterize the
complexity of microporous membranes

<Figure 2.29> SEM at approximately the same

magnification of 4 microporous membranes
having approximately same particle retention.
(a)Nuclepore (PC) nucleation track membrane
(b) Celgard® (PE) expanded film membrane
(c) Millipore CA/CN phase separation
membrane made by water vapor imbibition
(d) Loeb–Sourirajan anisotropic PS membrane
made by the phase separation process
Chapter 2. Membrane Transport Theory 57
2.4 Pore Flow Membrane
❖ Separation mechanism
✓ Molecular sieving
• Nucleation track membrane (<Figure 2.29a>)
• Asymmetric Loeb–Sourirajan membrane (<Figure 2.29d>)
✓ Depth filter (captures particles within the interior of the membrane by adsorption)
• Cellulose acetate(CA)/cellulose nitrate(CN) membrane (Figure 2.29c)
✓ By molecular sieving and depth filter (<Figure 2.29b>)
• Expanded film membrane
❖ Membrane materials
✓ Hydrophobic (low surface energy) : polyethylene(PE), polysulfone(PS)
✓ Hydrophilic : cellulose acetate(CA) ※ often carries charged surface groups

Chapter 2. Membrane Transport Theory 58

 2.4 Pore Flow Membrane
❖ Widely used parameters
✓ Membrane porosity (ε)
• Fraction of total membrane pore volume
• Typical porosity = 0.3 ∼ 0.7
• Measured easily by weighing membrane before and after filling pores with an inert liquid
※ Anisotropic membranes(Loeb–Sourirajan phase separation membrane, <Figure 2.29(d)>)
➢ Average porosity : 0.7 ∼ 0.8
➢ Porosity of the skin layer(actual separation) : 0.05
✓ Membrane tortuosity (τ )
• Reflects the length of the average pore compared to the membrane thickness
• Typical tortuosity = 1.5 ∼ 2.5

Chapter 2. Membrane Transport Theory 59

 2.4 Pore Flow Membrane
❖ Pore diameter (d)
✓ Most important property characterizing microporous membrane
✓ Pore diameter in UF = usually an average value
✓ Pore diameter in MF = usually in terms of the largest particle able to penetrate the membrane
※ Nominal pore diameter = 5 to 10 times smaller than the apparent pore diameter

<Figure 2.30> Characterization of

microporous membranes by their
✓ Tortuosity (τ )
✓ Porosity (ε)
✓ Average pore diameter (d)

Chapter 2. Membrane Transport Theory 60

 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
❖ Filtration category in MF and UF (<Figure 2.31>)
Items 1st category (surface or screen filter) 2nd category(depth filter)
Capture Surface pores smaller than particles to be Some by small constriction of interior of
mechanism removed membrane and others by adsorption
Usually anisotropic
Pore structure ✓ Top-layer = fine microporous Usually isotropic
✓ Sub-layer = more open porous support
Apply process UF MF
Accumulate particulates on the surface of Average pore diameter
Remarks
membrane = often 10 × smallest particle

<Figure 2.31> Separation of

particulates by porous membrane.
a. Remove particulates at the
membrane surface according to
a screen filtration mechanism
b. Remove particulates in interior
of the membrane by a capture
mechanism as in depth
filtration
Chapter 2. Membrane Transport Theory 61
 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
2.4.1.1 Screen Filters Relatively easily described by mathematics
❖ Ferry’s model
✓ Equal circular capillaries pores(radius = r)
⇨ transport solvent through area of pores

(2.103)

where A = area of pore available for solute

molecule transport
Ao = area of pore available for solvent
molecules transport
a = Radius of solute molecule
❖ Renkin’s model
✓ Modify Eq(2.103) to account for parabolic
velocity profile of fluid

<Figure 2.32> Illustration of the Ferry mechanical

exclusion model of solute transport in small pores
Chapter 2. Membrane Transport Theory 62
 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
✓ Effective fractional pore area available for solutes

and so (2.104) & (2.105)

where cℓ = solute concentration in the filtrate

co = solute concentration in the feed
✓ Definition of rejection[Eq(2.48)] & Eq(2.105) MW Predicted
Species
(×1000) diameter(Å)
⇨ Rejection of membrane
Sucrose 0.34 11
Raffinose 0.59 13
(2.106)
Vitamin B12 1.36 17
Bacitracin 1.41 17
Insulin 5.7 27
Cytochrome c 13.4 38
Myoglobin 17 40
α-Chymotrysinogene 25 46
Pepsin 35 50
Ovalbumin 43 56
Bovine albumin 67 64
[Table 2.5] Marker molecules used to characterize Aldolase 142 82
UF membranes γ –Globulin 150 84
Chapter 2. Membrane Transport Theory 63
 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
❖ Comparison of theoretical prediction with experimental data(<Figure 2.23>)
※ Molecular radius ≈ (protein MW)1/3

<Figure 2.33 (a)> Rejection of globular

proteins by UF of increasing pore size

<Figure 2.33 (b)> Calculated rejection

curves from Ferry–Renkin Eq(2.106)
plotted on the same scale
Chapter 2. Membrane Transport Theory 64
 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
2.4.1.2 Depth Filters Mathematically more complex
❖ 2 kinds of capturing phenomena in the interior of the membrane
✓ Simple capture of particles by sieving at pore constructions ⇨ minor contribution
✓ Adsorption of particles on the interior surface of the membrane
• Capture particles smaller than the diameter of the pore
• Mechanism : Inertial interception, Brownian diffusion, Electrostatic adsorption
❖ Inertial interception
✓ Relatively large particle are captured as they impact the pore wall.
<Example> In experiments with colloidal gold particles by Davis
• Depth filtration membranes having about 5 μm diameter tortuous pores
• Capture 60% of 0.05 μm diameter particles
※ 0.05 μm particle rejection by 5 μm pore nucleation track membranes = only 1%
『Meaning』Higher tortuosity ⇨ lead to inertial capture

Chapter 2. Membrane Transport Theory 65

 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
❖ Capture by Brownian diffusion
✓ Relatively small particles in random Brownian motion
✓ Particulates contacting with pore walls ⇨ capture them by surface adsorption
❖ Electrostatic adsorption
✓ Capture of charged particles by
opposite charged membranes
✓ Colloid : slight negative charge
✓ Membrane : excess positive group
✓ Problem
Filtration proceeds
⇨ lose the charged group

<Figure 2.34> Particle capture mechanism

in filtration of liquid solution by depth MF.
Chapter 2. Membrane Transport Theory 66
 2.4.1
2.4 Pore Flow Membrane Permeation in UF & MF
❖ In filtration of gas-borne aerosol particles by MF membranes (<Figure 2.35>) ※ Paradoxical result
✓ Major mechanism : Capture by adsorption, not sieving
✓ Larger particles
⇨ capture by inertial interception
✓ Smaller particles
⇨ capture by Brownian diffusion
✓ Most penetrating particle
⇨ intermediate diameter

<Figure 2.35> Gas-borne particle penetration

through an ultrathin PVDF membrane.
Chapter 2. Membrane Transport Theory 67
 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion

※ Most of all industrial gas separation membranes = use dense polymeric membranes
❖ History of microporous membrane to use gas separation
✓ Gas permeation through microporous membrane = Graham’s work in the 1850s
✓ Unique application at present = Separation of U235F6 and U238F6 in the Manhattan project
✓ More recently finely microporous membranes = carbonizing poly(vinylidene chloride)
✓ Other polymers = still in development at pilot plant scale
❖ Poiseuille’s flow : Pores of MF > 0.1 μm ⇨ gas permeation by normal convective flow
❖ Knudsen diffusion
✓ Pore radius (r) < mean free path (λ) of the gas
※ λ of common gas = 500 ∼ 2000 Å(0.05 ∼ 0.2 μm) at atmospheric pressure
✓ Collision of diffusing gas molecules with pore walls > collision with other gas molecules
✓ Collision with pore walls ⇨ adsorb gas molecules and then reflect in a random direction
✓ Gas mixtures move at different velocities ⇨ separation = possible

Chapter 2. Membrane Transport Theory 68

 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion
✓ Gas flow in straight capillaries for Knudsen diffusion : (2.107)

where m = MW of gas j = flux (gmol/cm2 · s)

r = pore radius ℓ = pore length ε = porosity of the membrane
po and pℓ = absolute pressures of gas species at x = 0 and at x = ℓ, respectively
※ Gas flow by Poiseuille flow

(2.108)
coming from
✓ η = viscosity of gas gas expansion
❖ Selectivity of membrane for Knudsen diffusion
✓ Permeability of gas i ∝(mi)1/2

✓ Selectivity, (2.109)

⇨ Graham’s law of diffusion

※ Selectivity for U235F6 and U238F6 = only 1.0043
⇨ Need hundreds of separation stage to separate
<Figure 2.36> Illustration of proportion of
Knudsen to Poiseuille flow as a function of r / λ
Chapter 2. Membrane Transport Theory 69
 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion

❖ Molecular sieving membrane

✓ Pore size : 5∼10 Å ⇨ Occur molecular sieving for non-condensable gases
✓ Very difficult to make membranes without defect for industrial purpose
✓ Possible to separate gases with only 0.1 Å difference in diameter in laboratory only
• Gas sieving by silica membrane(<Figure 2.37>)
• Not possible with polymeric membranes

<Figure 2.37> Permeability coefficients as a function of the

gas kinetic diameter in microporous silica hollow fine fibers
Chapter 2. Membrane Transport Theory 70
 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion

❖ Surface adsorption and diffusion

(<Figure 2.38>)
✓ Pore diameter < about 100 Å(0.01 μm)
⇨ area of pore walls ≈ 100 m2/cm3
✓ Adsorb large volume of gas onto pore
walls (particularly condensable gas)
⇨ Absorbed gas volume ≫
non-absorbed gas volume

<Figure 2.38> Permeation of non-

condensable and condensable gas mixtures
through finely microporous membranes.
✓ 5∼10Å pore for non-condensable gases
⇨ occurs molecular sieving
✓ r↓ & T↓ for condensable gases ⇨
adsorption↑ ⇨ Surface diffusion↑
Chapter 2. Membrane Transport Theory 71
 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion
✓ Adsorbed gas molecules : move through membrane by surface diffusion
✓ Fick’s law : (2.110)
where Js = contribution to permeation by surface diffusion of the adsorbed gas, cs
Ds = surface diffusion coefficient(10−3 ∼ 10−4 cm2/s at room temperature)
✓ Normalized permeability
P·m0.5 for gas = constant
only for very low boiling
gases (He, H2 and Ne)
✓ Condensability of gas↑
(measured by bp or Tc)
⇨ surface sorption↑
<Example> Butane gas
80% of total permeation
by surface diffusion
<Figure 2.39> MW normalized
permeability of gases through Vycor
microporous glass membranes
Chapter 2. Membrane Transport Theory 72
 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion
❖ Pore(or Capillary) condensation (first noticed by Barrer and Pope by SO2 / H2 separation)
✓ Adsorbed condensable gas ⇨ restrict or block permeation of the non-condensable gas
✓ Adsorbed SO2 on pore walls of microporous carbon membrane ⇨ inhibits the flow of H2
✓ pSO2 ↑ or T ↓ ⇨ adsorption of SO2 ↑
⇨ cause capillary condensation of SO2
⇨ completely block permeation of H2
⇨ permeates SO2 only through membrane

<Figure 2.40> Blocking of H2 in H2 / SO2 mixture

permeation experiments with finely microporous
membranes as a function of the amount of SO2
adsorbed by membrane.
✓ SO2 sorption↑ ⇨ H2 permeability↓
until at about 140 cm3(SO2)(STP)/g ⇨ membrane
blocked completely and only SO2 permeates
✓ Data obtained at several temperatures fall on the
same master curve.
(● : 0℃, ▲ : −10℃, □ : −20.7℃, △ : −33.6℃)
Chapter 2. Membrane Transport Theory 73
 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion

❖ Capillary condensation by microporous carbonized hollow fiber membrane

✓ Developed by Carbon Membranes Ltd. over a period of 20 years
✓ Difficult to make defect-free membrane ⇨ available small module scale module only
✓ Relatively sensitive to fouling and breaking
❖ Capillary condensation by vacuum carbonized polymer onto microporous ceramic membrane
✓ Sponsored project by Air products
✓ Separate H2/light HC gas mixtures in refinery waste gas streams with pilot scale
• Permeate adsorbed hydrocarbons through membranes by surface diffusion
• Block the permeation of H2 by capillary condensation
• Permanently adsorbed higher HC in feed ⇨ blocked pore ⇨ eventually abandoned
✓ Selectivity = very good, even for simple gas mixtures (O2 / N2 or CO2 / CH4)
✓ Price of carbon membranes = 10 ∼ 100 × price of polymeric membranes

Chapter 2. Membrane Transport Theory 74

 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion

❖ Gas separation by microporous polymer membranes – Pore flow transport

✓ Membrane = substituted polyacetylenes (< Figure 2.23>)
• poly(1-trimethylsilyl-1-propyne) (PTMSP)
• poly(4-methyl-2-pentyne) (PMP)
✓ Free volume = about 25 vol% : extra-ordinarily high
⇨ Occur interconnecting among free volume elements
⇨ Pore size = 5 ∼ 15 Å diameter : finely microporous materials
✓ Gas permeability through extremely high free volume membrane
• Much higher than poly(dimethylsiloxane), the most permeable polymer known before
➢ Sorption capacity ≈ 10 × conventional glassy polymer
➢ Di = 103 ∼ 106 × conventional glassy polymers.
✓ <Example> Diffusivity ratio of O2 and N2(DO2 / DN2) = 1.4
• Not enough for separation by a glassy polymer membrane
• Enough for separation by a simple Knudsen diffusion membrane

Chapter 2. Membrane Transport Theory 75

 2.4.2
2.4 Pore Flow Membrane Knudsen & Surface Diffusion

<Example> Unusual permeability characteristics of high-free-volume polymers(PTMSP)

• Gas mixture : 1,200 ppm of FC-77 (perfluoro octane-perfluoro decane mixture) in N2
• N2 (1,200 ppm) permeability in FC-77 < pure N2 permeability ÷ 20 (<Figure 2.41>)
• Adsorption of FC-77 vapor ⇨ Cause capillary condensation ⇨ Partially or completely
blocked pores ⇨ Preventing the flow of non-condensed gases (N2) through the membrane

<Figure 2.41> Change in N2 flux through a

PTMSP membrane caused by the presence
of a condensable vapor in feed gas.
✓ Characteristic of extremely finely porous
microporous ceramic or ultrahigh free
volume polymeric membranes such as
PTMSP.
✓ Condensable vapor adsorbs in the
5∼15Å diameter pores and block flow of
the non-condensable N2 gas.
Chapter 2. Membrane Transport Theory 76
 2.4.3
2.4 Pore Flow Membrane Transition Region
❖ Transition between pore-flow and solution-diffusion transport
✓ UF membranes : reject sucrose and raffinose,
NF = might be
but pass all micro-ions ⇨ clearly pore flow transition range
✓ SWRO ⇨ clearly follow the solution-diffusion model
✓ NF membrane
• Rejections of divalent ions and most organic solutes = Good
• Rejection of monovalent ions = 20∼70%
Solute rejection(%)
[Table 2.6] Rejection of micro Solute
FT-30 XP-45 XP-20
solutes by NF(FilmTec data)
NaC1 99.5 50 20
MgCl2 > 99.5 83 -
MgSO4 > 99.5 97.5 85
NaNO3 90 < 20 0
Ethylene glycol 70 24 11
Glycerol 96 44 15
Glucose 99 95 60
Sucrose 100 100 89
Remarks good RO intermediate small pore flow UF
Chapter 2. Membrane Transport Theory 77
 2.4.3
2.4 Pore Flow Membrane Transition Region
❖ Transition region in water permeation Transition Area(NF region)
✓ Rapid change in water flux(<Figure 2.42>) RO 95% > Salt Rejection > 10% UF

✓ Water permeability : UF > 10 × RO 50 < MWCO < 1,000

※ MWCO : Molecular Weight Cut-Off
❖ Transition region in gas permeation
transition area
✓ Solution diffusion Pore flow
High free volume membrane(PTMSP)

<Figure 2.42> Diagram of the region of NF

performance relative to RO and UF
Chapter 2. Membrane Transport Theory 78
 2.5 Conclusions and Future Directions
❖ Permeation model based on solution-diffusion ⇨ become much clearer during the last 30 years
✓ Now almost universally accepted for RO, GS and PV particularly
✓ Well matched with experimental evidence
✓ Provides simple equations that accurately link driving forces with flux and selectivity
❖ Less successful to link nature of membrane material with membrane permeation properties
✓ Requires an ability to calculate membrane diffusion and sorption coefficients
✓ To do, require knowledge of
• molecular level of interactions of permeant
• motion of permeant molecules in the polymer matrix
✓ These = not yet available.
✓ Only semi-empirical correlations = available(dual sorption model or free volume correlations)
❖ Future progress towards a priori methods of calculating permeant sorption and diffusivity
✓ Computer-aided molecular dynamic simulations
✓ Accurate predictions using this technique are years—perhaps decades—away.

Chapter 2. Membrane Transport Theory 79

2.5 Conclusions and Future Directions

❖ Theory of permeation through microporous membranes(UF and MF )

✓ Much less developed
✓ Difficult to see a clear path forward
✓ Permeation through these membranes
• Affected by a variety of hard-to-compute effects
• Strong function of membrane structure and composition
❖ Membrane made by nucleation track method
✓ Ideal uniform-pore-diameter membranes
✓ Measurements of permeation = good agreement with theory
❖ Industrially useful microporous membrane
✓ Non-uniform tortuous pores (often anisotropic)
✓ Prediction of permeation properties = not yet available by current theories

Chapter 2. Membrane Transport Theory 80