+ + + + + + + +

+ + + + + + + +

+ + + + L

+ + + +

+ + + +

+ +

+ +

+ +

+ +

+ +

I
backflo w

2h
m

JV
+ + + + + + + + + + + + + +

Lm
, ; the

Positively charged surfaces in the nano-block and micro-channel; velocity of pressure-driven back-flow, v, is >0. The current density, I, is considered constant (galvanostatic mode).

It is absolutely essential to derive the salt equations proceeding from the ionic ones in both nano-block and micro-channel. This derivation can be found nowhere in the micro-/nano-fluidic literature. Nano-block

(1)

(2) specific chemical capacity.

(3) p is hydrostatic pressure, electro-viscosity). is defined at zero current (i.e., subject to

(4) The hydraulic resistance of nano-block is assumed to be much larger than that of micro-channel. Therefore, the condition of zero hydrostatic pressure difference can be imposed at the edges of nano-block.

(5)

(6) Eq(6) has to be substituted to Eqs(1,2) to obtain a closed equation in terms of Micro-channel In the micro-channel, the volume flux is assumed to be controlled by the nanoblock. (7) .

(8)

(9) v is the average velocity of the backflow. Further, the space variable, x, is scaled on the length of micro-channel, (10) and the salt is assumed to be (1:1) ( , )

(11) (12)

(13) (14) (15) hydrodynamic radius of salt molecule (16)

(17) dimensionless solute flux in the microchannel (18) (19)

(20) Here we have neglected the capillary osmosis (put the reflection coefficient equal to zero) in the term proportional to the longitudinal Pclet number. This is justified in not too narrow microchannels. Dimensionless solute flux in the nano-block

(21) (22)

(23) is the nano-block porosity (including the possible pore tortuosity); are the distribution coefficients of cations and anions averaged over the cross-section of nanopores (nanochannels).

(24)

(25) are the entrainment coefficients of cations and anions. By definition, they are the distribution coefficients weight-averaged with the parabolic fluid velocity profile. By neglecting the electro-viscosity (and, thus, the dependence of the hydraulic permeability of nano-block on the salt concentration), from Eq(6), we obtain this

(27) (28) (28)

(28) Characteristic time

(29) (30) In the microchannel

(31) (32)

(33)

(34) (35) In the nano-block

(36) (37)

(38)

(39)

(40)

(41) Boundary conditions: (41) (42) (43) Initial condition: (44) The simplest case: (45) Homogeneous model:

(46)

(47)

(48)

(49)

(50)

(51)

(52) (53)

(54) B is the dimensionless surface charge density defined with the half-height of nanochannels this way

(55) In the expression for the zeta-potential of surface of micro-channel, the half-height of nano-channel cancels out. In fact, in micro-channel the dimensionless surface charge density is defined with the Debye length as the characteristic length.