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Theory of shock electrodialysis

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Theory of shock electrodialysis ( theory-shock-electrodialysis )

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fluxes together to get the electric current density: N i = 􏰎zkFJk, (2) k=1 where F is the Faraday constant. The conservation of species k leads to ∂ck +∇·Jk =Rk, (3) ∂t where Rk is the volumetric reaction rates of species k. In this work, we assume no reaction for salt ions, and only water dissociation reaction for water ions. So ∂ck +∇·Jk =0 {k=1,2,···,Ns}, (4) ∂t ∂cw +∇·Jw =0, (5) ∂t where cw = cNs+1 − cNs+2 and Jw = JNs+1 − JNs+2 are respectively the difference of concentration and flux of the two water ions (H+ and OH−). Assuming fast dissociation of water, cNs+1cNs+2 = Kw, (6) where Kw is the water dissociation constant. On the other hand, the flow is not only driven by a pressure gradient, but also by an electric force. A typical shock ED system involves an incompressible fluid and operates at low Reynolds number, hence the Stokes equations can be applied for momentum conservation: μ∇2u − ∇p − ρe∇ψ = 0, (7) where ρe is the local charge density. In addition, the continuity equation should be satisfied: ∇ · u = 0. (8) Finally, the electric potential should satisfy the Poisson equation: N ǫ∇2ψ=−ρe =−􏰎zkFck, (9) k=1 where ǫ is the permittivity of the solution and is assumed to be a constant. To summarize, Eq.(4)-(9) provide N +5 equations so the system should be solvable with proper boundary conditions. 2.2. Thin channel assumption In this part, we will simplify the full model in Sec.2.1 under the assumption of thin channels. The assumption includes two aspects. First, the z-dimension (less than 10 μm) is much smaller than the x- and y-dimensions (∼ mm), and thus we can assume | ∂ | ≫ | ∂ |, | ∂ | and parallel flow (w = 0), which means ∂z ∂x∂y that we can neglect the electroosmotic instability and electroosmotic vortices in xz or yz planes [11, 27]. Second, the P ́eclet number Pek = |u|h/Dk, which represents the convection in the x- and y-directions over the diffusion in z-direction, is so small (≪ 1) that we can neglect Taylor-Aris dispersion [28] and assume local equilibrium (Jz,k = 0) to a virtual reservoir (where ρe = 0) at each (x, y) position [29, 26]. We define cvk(x, y), ψv(x, y), pv(x, y) as the concentration, electric potential, and pressure in the virtual reservoirs. In the following, we will denote u = (u,v) and Jk = (Jx,k,Jy,k) since w = 0 and Jz,k = 0, and we will denote ψ ̃ = ψ/VT for simplicity. 4

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