VCE Chemistry — Redox & Renewables

Nanofluidic Reverse Electrodialysis Explorer

REDOX & Renewables · VCE Chemistry Unit 3
Salinity Gradient Power · "Blue Energy"

When a river meets the sea, an enormous amount of free energy is released as entropy of mixing.

Nanofluidic reverse electrodialysis (RED) captures a portion of that energy as electrical work by allowing salt ions — but not water — to cross between fresh and salt water through ion-selective nanochannels.

Because each channel only lets one charge sign pass, the two reservoirs become electrically charged. Electrodes at the ends of a stack convert this ionic current into an electronic current that powers a load.

~0.8 kWh
Per m³ fresh water mixed
2.6 TW
Global theoretical potential
~0.1–0.2 V
Per cell pair
RED PLANT RIVER · ~0.01 M SEA · ~0.5 M NaCl → TO GRID
RED Cell — Operating Principle

What you are looking at

A RED stack consists of alternating cation- and anion-exchange membranes separating compartments of salt water and fresh water. Two electrodes terminate the stack.

Ion movement (drag to rotate)

  • Na⁺ cations diffuse from salt → fresh through the cation-exchange membrane (CEM)
  • Cl⁻ anions diffuse from salt → fresh through the anion-exchange membrane (AEM)
  • Both ions move down their concentration gradient — the entropy of mixing is the energy source.

Where the voltage comes from

Each membrane develops a Donnan (membrane) potential because only one ion sign crosses. The potentials of all CEM/AEM pairs add in series along the stack.

≈ 80–150 mV per cell pair under realistic river/sea conditions.

Closing the circuit — electrode reactions

Inside the stack, the current is ionic. To deliver power to a load, electrodes convert it to electronic current via a reversible redox couple. A common choice is the iron(II/III) hexacyanoferrate couple recirculating in both end-compartments:

Cathode (reduction, gains e⁻):
[Fe(CN)₆]³⁻(aq) + e⁻ → [Fe(CN)₆]⁴⁻(aq)
Anode (oxidation, loses e⁻):
[Fe(CN)₆]⁴⁻(aq) → [Fe(CN)₆]³⁻(aq) + e⁻

Because the couple is recycled, no net electrolysis or reagent consumption occurs — the only consumed input is the salinity gradient itself.

Half-equation language (VCE Unit 3)

  • Reduction (cathode): Fe oxidation state goes from +3 → +2
  • Oxidation (anode): Fe oxidation state goes from +2 → +3
  • Conventional current flows cathode → external circuit → anode; electrons flow the opposite way.

Why "nanofluidic"?

Traditional polymer membranes have fixed ionic groups (e.g. –SO₃⁻ for CEM, –NR₄⁺ for AEM) that exclude co-ions chemically.

In nanofluidic RED the membrane is a sheet of nanopores (graphene oxide, MoS₂, BN nanotubes, anodised alumina). Selectivity comes from the geometry of the pore and its surface charge — see the Nanochannel tab.

Reported lab power densities in nanofluidic devices reach 10²–10³ W·m⁻², compared with ~3 W·m⁻² for commercial polymer RED.

Practical reality check

  • Open-circuit voltage per pair (~120 mV) is lower than the thermodynamic limit because of imperfect selectivity and concentration-polarisation films either side of each membrane.
  • Power output is maximised when the load resistance equals the stack's internal resistance.
  • Commercial pilot plants exist in the Netherlands (Afsluitdijk) and Norway (Tofte).
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Cell pairs3
V per pair0.12 V
Stack voltage0.36 V
Load current3 mA
CircuitCLOSED
Na⁺ cation
Cl⁻ anion
CEM (lets Na⁺ through)
AEM (lets Cl⁻ through)
Electron in circuit
Speed 1.00×
Stack
Circuit
Nanochannel — Why it Selects

Wall charge sets the rules

The pore wall in this view carries a fixed negative surface charge (deprotonated –OH or –COO⁻ groups, for example).

Ions of opposite sign — the counterions (Na⁺) — are attracted toward the wall and form a thin layer called the electric double layer (EDL).

Ions of the same sign — the co-ions (Cl⁻) — are repelled and excluded.

Try it

  • Use the Channel Width slider to shrink the pore.
  • When the channel is narrower than ~2× the Debye length, the EDLs overlap and the channel becomes perfectly cation-selective.

The Debye length, λ_D

λ_D is the distance over which the surface charge is screened by the surrounding ions. For aqueous NaCl at 25 °C:

λ_D ≈ 0.304 / √c nm (c in mol·L⁻¹)
  • Sea water (c ≈ 0.5 M): λ_D ≈ 0.4 nm
  • River water (c ≈ 0.001 M): λ_D ≈ 10 nm

So a 5–20 nm pore behaves very differently against fresh vs salt solutions — and that's exactly the regime we want for a salinity-gradient generator.

Comparison: macropore

If the pore is much larger than λ_D (right of slider), the EDLs are thin films on the wall, the channel interior is essentially neutral electrolyte, and both ions pass freely. There is no selectivity, and no useful voltage.

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Channel ø6.0 nm
Debye λ_D~ 1.36 nm
SelectivityPARTIAL
ModeEDL-CONFINED
Na⁺ counterion (passes)
Cl⁻ co-ion (excluded)
Negative wall charge
Electric double layer
Channel width 6.0 nm
Bulk salinity 0.05 M
Speed 1.00×
Reverse Osmosis — Comparison

The opposite of RED

RED extracts energy from mixing two solutions. Reverse osmosis (RO) consumes energy to do the opposite — separating pure water from a salt solution against the osmotic gradient.

Both processes use a membrane, but:

  • RED: ions move; water stays. Selectivity is charge-based.
  • RO: water moves; ions stay. Selectivity is size/affinity-based (a dense polyamide film).

Pressure is the driver

To force water through against osmotic pressure π, the applied pressure P must satisfy P > π. For sea water:

π_seawater ≈ 27 bar (at 25 °C)
P_operating ≈ 55–80 bar

The slider lets you raise the piston pressure and watch the membrane flux.

What happens at the membrane

The polyamide film is dense — there are no continuous pores at all. Water dissolves into the film and diffuses across (the solution-diffusion mechanism). Hydrated Na⁺ and Cl⁻ ions can't fit through the polymer matrix.

Energy ledger

  • Modern seawater RO uses ~3–4 kWh·m⁻³ of fresh water produced.
  • The thermodynamic minimum is ~1 kWh·m⁻³.
  • Energy recovery devices (Pelton wheels, isobaric exchangers) recover most of the residual brine pressure.

Symmetry with RED

Notice: RED's theoretical maximum (~0.8 kWh·m⁻³ mixed) and RO's theoretical minimum (~1 kWh·m⁻³ separated) sit on either side of the same Gibbs free energy of mixing. They are thermodynamic opposites.

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Applied P55 bar
Osmotic π~27 bar
Net ΔP28 bar
Permeateflowing
Salt rejection> 99 %
Water (H₂O)
Na⁺ (rejected)
Cl⁻ (rejected)
Polyamide membrane
Pressure 55 bar
Speed 1.00×
Energy ▸ Out

Reverse Electrodialysis

Salinity-gradient power generator
⚡ Spontaneous · ΔG_mix < 0 → Electrical work out
Driving force
Salinity gradient between two reservoirs (chemical potential of dissolved salt)
What moves
Ions (Na⁺ through CEM, Cl⁻ through AEM)
Water stays put
Membrane role
Charge-selective — only counterions permitted
Thermodynamics
Entropy of mixing increases (ΔS > 0)
Gibbs free energy released as electrical work
Voltage
~0.1–0.2 V per cell pair (Donnan potential, sea/river)
Electrode chemistry
Reversible redox couple, e.g.
[Fe(CN)₆]⁴⁻ ⇌ [Fe(CN)₆]³⁻ + e⁻
Power density
Conventional: ~1–3 W·m⁻²
Nanofluidic (lab): 10²–10³ W·m⁻²
Where used
River-mouth power plants (Netherlands, Norway pilots); waste-brine energy recovery
Limitations
Membrane fouling by organics; concentration polarisation; cost of high-area selective membranes
VCE links
Galvanic cells · half-equations · oxidation states · electrochemistry of electrolyte solutions
Energy ▸ In

Reverse Osmosis

Pressure-driven desalination
⚠ Non-spontaneous · ΔG_sep > 0 ← Mechanical work in
Driving force
Applied hydraulic pressure exceeding osmotic pressure π
What moves
Water molecules through the membrane
Ions stay behind in the concentrate
Membrane role
Solution-diffusion barrier — dense polyamide film, no continuous pores
Thermodynamics
Entropy of concentrate decreases — work must be supplied to fight mixing
Pressure
Sea water π ≈ 27 bar
Operating P: 55–80 bar
Electrode chemistry
None — RO is a purely mechanical process. No electron transfer, no redox.
Energy use
Modern SWRO: ~3–4 kWh·m⁻³
Theoretical minimum: ~1 kWh·m⁻³
Where used
Drinking-water plants (Adelaide, Perth, Sydney, Gold Coast, Melbourne), industrial water treatment
Limitations
High pumping energy; concentrate brine disposal; membrane scaling and fouling
VCE links
Colligative properties (osmotic pressure) · solubility · separation techniques