ARTICLE pubs.acs.org/IECR
Ion-Exchange Membrane Electrodialysis for Saline Water Desalination and Its Application to Seawater Concentration Yoshinobu Tanaka IEM Research, 1-46-3 Kamiya, Ushiku-shi, Ibaraki 300-1216, Japan ABSTRACT: Membrane pair characteristics of commercially available ion-exchange membranes are measured by changing current density and seawater temperature supplied to the electrodialyzer. The hydraulic permeabilities (leading parameter) for three types of commercially available membranes are almost the same, and their averages are expressed by the empirical function of temperature. Hydraulic osmosis is predominant at lower current density and electro-osmosis is predominant at larger current density. The influence of temperature and salt concentration on the physical properties of saline water, such as solution density, specific conductance, and NaCl activity coefficient, is expressed by empirical equations. Ionic constituents in a concentrated solution are expressed by empirical equations. Electric current screening ratio of a spacer is defined and calculated. Direct current electric resistance of a membrane pair is calculated, and it is predominant over that of a desalting cell and a concentrating cell. It is necessary to decrease electric resistance of an ion-exchange membrane for reducing energy consumption in a salt manufacturing process.
1. INTRODUCTION Industrial application of ion-exchange membranes started from saline water desalination1 and the membranes are now applied in many fields, such as drinking water treatment, wastewater treatment, demineralization of amino acid, demineralization of whey, demineralization of sugar liquor, treatment of organic substances, etc. Among these applications, saline water desalination is the most important fundamental technology, and it is applied widely.211 Ion-exchange membranes have the functions of desalting and of concentrating saline water. The targets (products) of both functions are different from each other. However, the principles of both functions are fundamentally the same. In the previous investigation, a computer simulation program for evaluating the performance of saline water desalination was developed.1214 The overall mass-transport equation15 is the fundamental principle in this program, and it was established from seawater concentration. The equation makes it possible to evaluate the membrane pair characteristics, which are discussed initially in this article. Furthermore, in order to improve the precision of the computer simulation program, the following phenomena are also discussed: (1) Relationship between temperature and the overall hydraulic permeability F (leading parameter), (2) Influence of temperature and salt concentration on the physical properties of saline water, (3) Ionic constituent in a concentrated solution, (4) Electric current screening ratio of a spacer, and (5) Direct current electric resistance of an ion-exchange membrane. In Japan, there are no rock salt deposits and, because of its climate, is not suitable to manufacture salt; thus, salt requirements have been largely met by imported salt. Only table salt has been produced by a method in which seawater is introduced into a salt field and then thickened by solar energy. However, this method requires a wide area of land and is labor-intensive. In r 2011 American Chemical Society
addition, such conditions as wind, rain, and length of the dry season raise the cost to rather higher levels, compared to the price of imported salt.16 With the circumstances described above, research on seawater concentration by means of ion-exchange membranes has been progressed.1720 In 1971, all salt field methods were converted to ion-exchange membrane methods, which presently enable the production of ∼1 000 000 tons of edible salt per year. The largest problem in ion-exchange membrane methods is that the cost is still higher, compared to the price of imported salt. This problem has become more acute recently, because of rising energy prices. Therefore, cost reduction is the most important target in ion-exchange membrane technology. In this manuscript, we discuss also the fundamental performance of an electrodialyzer for seawater concentration, taking energy consumption reduction into consideration.
2. EXPERIMENTAL SECTION Three types of commercially available ion-exchange membranes were integrated in the electrodialyzers: Aciplex K172/ A172 (Asahi Chemical Co.), Selemion CMR/ASR (Asahi Glass Co.), and Neocepta CIMS/ACS3 (Tokuyama Corp.). Tables 1 and 221 respectively show electrodialyzer/ion-exchange membrane specifications and electrodialysis conditions. Seawater was supplied to the electrodialyzer, keeping a flow velocity of 5 cm/s at the inlets of desalting cells. By passing an electric current, a concentrated solution was extracted from concentrating cells. After the electrolyte concentration of the concentrated solution became constant, the solution was sampled, its volume velocity was measured, and the concentrations of Naþ, Kþ, Mg2þ, Ca2þ, Cl, and SO42þ ions were analyzed. In seawater electrodialysis, Received: November 26, 2010 Accepted: April 29, 2011 Revised: April 20, 2011 Published: April 29, 2011 7494
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Table 1. Specifications of the Electrodialyzer and Membranes manufacturer
Asahi Chemical Co.
Asahi Glass Co.
Tokuyama Soda Co.
ion-exchange membrane membrane area (dm2)
Aciplex K172/A172 1.72
Selemion CMR/ASR 1.72
Neocepta CIMS/ACS3 2.00
membrane pairs (pairs)
10
10
9
membrane thickness (mm)
K172: 0.130.15 A172: 0.110.13
CMR: 0.11 ASR: 0.11
CIMS: 0.140.17 ACS3: 0.090.12
area electric resistance of the membrane (Ω cm2)
K172: 1.92.2
CMR: 2.36
CIMS: 1.51.6
A172: 1.72.1
ASR: 1.80
ACS3: 1.52.0
K172: >0.99
CMR: 0.94
CIMS: >0.98
A172: >0.99
ASR: 0.96
ACS3: >0.98
transport number exchange capacity (mequiv/g dry memb)
K172: 1.51.6
CMR: 3.7
CIMS: 2.22.5
A172: 1.81.9
ASR: 3.5
ACS3: 2.02.4
water content
K172: 0.200.30 A172: 0.240.25
CMR: 0.34 ASR: 0.33
CIMS: 0.300.35 ACS3: 0.200.30
intensity (MPa)
K172: 0.260.33
CMR: 0.2
CIMS: 0.30.4
A172: 0.220.30
ASR: 0.2
ACS3: 0.40.6
Table 2. Electrodialysis Conditions temperature (°C)
25, 35, 50, 60
current density (A/dm2)
1.0, 3.0, 5.0, 7.0
solution velocity in a desalting cell (cm/s)
5
the electrolyte concentration (C) is given as C ¼ CNa þ CK þ CMg þ CCa ¼ CCl þ CSO4 The cell voltage (Vcell) was measured from the voltage difference observed with Pt electrodes included in the concentrating cells that were integrated into both ends of the stack. The experiments were repeated by the changing seawater temperature and current density incrementally, via electrodialysis.
3. RESULTS AND DISCUSSION 3.1. Overall Mass-Transport Equation and Membrane Pair Characteristics. Ion-exchange membrane electrodialysis is a
process for transporting ionic species across the membranes. Ions and a solution in a desalting cell are transferred to a concentrating cell across a cation- and anion-exchange membrane under an applied electric current. Fluxes of ions (JS) and a solution (JV) transported across a membrane pair are expressed by the following overall mass-transport equation:15 JS ¼ C00 JV ¼ λi μðC00 C0 Þ ¼ λi μΔC
ð1Þ
JV ¼ φi þ FðC00 C0 Þ ¼ φi þ FΔC
ð2Þ
where i is the current density; C0 and C00 are the electrolyte concentrations in a desalting and a concentrating cell, respectively; the accents/superscripts 0 and 00 denote a desalting cell and a concentrating cell, respectively; λ is the overall transport number; μ is the overall solute permeability; φ is the overall electro-osmotic permeability; and F is the overall hydraulic permeability. These are membrane pair characteristics. The term “overall” means that the coefficients express the contributions of a cation- and anion-exchange membrane. It means also that the coefficients express the contributions of many types of ions that are dissolving in an electrolyte solution.
Figure 1. Plots of JS/i versus ΔC/i plot and JV/i versus ΔC/i. (Aciplex K172/A172, 25 °C.)
Plots of JS/i and JV/i versus (C00 C0 )/i = ΔC/i yield straight lines, such that λ, μ, φ, and F can be determined from the intercepts and the gradients of the lines. Figure 1 gives representative straight lines that were yielded in the experiment described in section . All membrane pair characteristics measured by changing the solution temperature are listed in Table 3. In the previous investigation,15 we plotted λ (equiv C1), μ (cm s1), and φ (cm3 C1) against F (cm4 equiv1 s1), and we found the following equations to be valid: λ ¼ 9:208 106 þ 1:914 105 F
ð3Þ
μ ¼ 2:005 104 F
ð4Þ
φ ¼ 3:768 103 F0:2 1:019 102 F
ð5Þ
Equations 35 are empirical equations that express the approximated regularity between membrane pair characteristics of commercially available ion-exchange membranes; they are not influenced by current density i. These equations mean that F is the leading parameter and represents all of the overall membrane 7495
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Table 3. Membrane Pair Characteristics ion-exchange membrane Aciplex K172/A172
Selemion CMR/ASR
Neocepta CIMS/ACS3
temperature (°C)
λ ( 106 equiv C1)
25
9.724
35
9.736
50
μ ( 106 cm s1)
φ ( 103 cm3 C1)
F ( 102 cm4 equiv1 s1)
1.434
1.403
1.218
1.289
1.370
1.626
9.972
4.515
1.542
1.996
60
9.692
2.123
1.405
2.765
25
9.389
1.482
1.409
1.116
35
9.422
2.421
1.501
1.377
50
9.475
3.614
1.563
1.937
60 25
9.583 9.349
5.103 1.055
1.621 1.004
2.380 1.254
35
9.373
1.679
1.067
1.538
50
9.459
1.239
1.067
1.835
60
9.547
0.561
1.405
2.059
Figure 2. Relationship between temperature (T) and the overall hydraulic permeability (F).
characteristics. λ, μ, and φ are determined by setting the value of F. In order to discuss the relationship between temperature T and the membrane pair characteristics, F is plotted against T, based on the data given in Table 3, as shown in Figure 2. F is the independent parameter, and each membrane must have its own F value. However, Figure 2 shows that the F value of each commercially available membrane is almost the same and can be expressed by the following empirical function of T (°C): F ¼ 3:421 103 þ 3:333 104 T
R ¼ 0:9364 ð6Þ
where R is the correlation coefficient. 3.2. Electromigration, Diffusion, Electro-Osmosis and Hydraulic Osmosis. Parameters λi and μΔC in eq 1 stand for the electromigration and solute diffusion, respectively. Parameters φi and FΔC correspond to the electro-osmosis and hydraulic osmosis, respectively. These parameters are computed from Table 3 and are shown in Figures 3 and 4 (Aciplex K172/ A172), Figures 5 and 6 (Selemion CMR/ASR), and Figures 7 and 8 (Neocepta CIMS/ACS3). The plots indicate that (i) μΔC
Figure 3. Electromigration (λi) and solute diffusion (μΔC) for Aciplex K172/A172.
is negligible, compared to λi, and (ii) FΔC is predominant at lower i and φi is predominant at larger i. 3.3. Influence of Temperature and Salt Concentration on the Physical Properties of Saline Water. In order to evaluate the performance of an electrodialyzer that was operated by changing the solution temperature and current density as described in section , it is necessary to make clear the influence of temperature T (°C) and electrolyte concentration C3 (g salt/kg solution) on the density D, specific electric conductance (k), and electrolyte (NaCl) activity coefficient (γ) of a solution. These relationships are determined as follows. Density D is determined using22 D kg=dm3 ¼ 1:001 1:101 104 T 3:356 106 T 2 þ ð7:881 1:368 102 T þ 8:978 105 T 2 Þ
ð7Þ
104 C3 7496
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Figure 4. Electro-osmosis (φi) and hydraulic osmosis (FΔC) for Aciplex K172/A172.
Figure 6. Electro-osmosis (φi) and hydraulic osmosis (FΔC) for Selemion CMR/ASR.
Figure 7. Electromigration (λi) and solute diffusion (μΔC) for Neocepta CIMS/ACS3.
NaCl activity coefficient (γ) is determined from the expression24 Figure 5. Electromigration (λi) and solute diffusion (μΔC) for Selemion CMR/ASR.
Specific electric conductance k (S/cm) is determined using the expression23 k ðS=cmÞ ¼ ð0:9383 þ 3:463 102 TÞ 103 C3 ð1:655 þ 3:863 102 TÞ 106 C3 2 ð1:344 þ 3:160 102 TÞ
γ ¼ 0:5927 þ 0:4355C3 0:5 7:201 105 C3 þ 3:503 106 C3 2 in the range from normal temperature to 70°C
ð9Þ Electrolyte concentration C3 (g salt/kg solution) is calculated from the electrolyte concentration C (equiv salt/cm3 solution), according the following steps:
ð8Þ
C1 ðequiv salt=dm3 solutionÞ
109 C3 3
¼ C ðequiv salt=cm3 solutionÞ 103 7497
ð10Þ
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Figure 8. Electro-osmosis (φi) and hydraulic osmosis (FΔC) for Neocepta CIMS/ACS3.
Figure 10. Relationship between rNa and rK.
and B ¼ 1:001 1:101 104 T 3:356 106 T 2
ð15Þ
Solving eq 13 yields
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi B2 þ 4AC2 B C3 ¼ 2A
ð16Þ
3.4. Ionic Constituent in a Concentrated Solution. In an electrodialysis process for concentrating seawater, the permeability of divalent ions across the membranes is strongly suppressed for preventing CaSO4 scale precipitation in concentrating cells.2528 The membranes being discussed in this investigation are given such low permeability of the divalent ions. In order to evaluate NaCl concentration in a concentrated solution (the output of an electrodialysis process) and energy consumption to produce one ton of NaCl in an electrodialysis process, it is necessary to discuss the ionic constituents in the concentrated solutions. Figure 9 gives the equivalent ratio of Naþ ions to total ions rNa in the concentrated solution for three types of membrane pairs integrated in the electrodialyzer. Averaging these data, rNa is expressed by the following empirical function of i (expressed in units of A/dm2) and T (given in Celsius). Figure 9. Relationship between i and rNa.
C2 ðg salt=dm3 solutionÞ ¼ 57:87C1
ð11Þ
C2 C3 ðg salt=kg solutionÞ ¼ D
ð12Þ
3
r Na ¼ 0:9584 4:269 103 T þ ð0:7983 þ 9:824 102 TÞ 102 i0:5 8 > > 0:4421 > < 0:5100 R ¼ 0:5906 > > > : 0:6017
From eqs 7 and 12, C3 ¼
C2 AC3 þ B
ð13Þ
where A ¼ ð7:881 1:368 102 T þ 8:978 105 T 2 Þ 104
ð17Þ
ð25°CÞ ð35°CÞ ð50°CÞ ð60°CÞ
Figures 1012 show rNa versus rK, rMg, and rCa. These plots are expressed by the following equations, which do not include i and T. rK ¼ 1:905 102 þ 8:838 103 r Na
ð14Þ 7498
R ¼ 0:2440 ð18Þ
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Figure 11. Relationship between rNa and rMg.
Figure 13. Relationship between i and rCl.
3.5. Electric Current Screening Ratio of a Spacer. Spacers are integrated in desalting and concentrating cells to maintain the distance between the membranes and increase the limiting current density due to solution disturbance.2934 However, the spacers partially screen an electric current and increase the local current density. In order to discuss energy consumption of an electrodialyzer, it is necessary to evaluate the electric current screening ratio of a spacer. The structure of the diagonal net spacer incorporated in the electrodialyzer is illustrated in Figure 14, which shows that the rods arranging in two directions are piled upon each other. The solution supplied to the cell flows along two watercourses (channels); therefore, solution stagnation is prevented, because the solution stream fans out and solution mixing is promoted between the two watercourses. The electric current screening ratio ε of the diagonal net spacer in Figure 14 is represented by the following equation:
ε
Figure 12. Relationship between rNa and rCa.
r Mg ¼ 0:7405 0:7668r Na
R ¼ 0:9959
ð19Þ
rCa ¼ 0:2460 0:2482r Na
R ¼ 0:9654
ð20Þ
The relationship between i and rCl is exhibited in Figure 13, and it is approximated by eq 21, r Cl ¼ 0:9929 þ 1:947 103 i
R ¼ 0:3703
ð21Þ
in which T is not included. The relationship between rCl and rSO4 is given by eq 22: ð22Þ r SO4 ¼ 1 rCl
electric current screening area of an unit net mesh total area of an unit net mesh ða=2Þ r 2 ¼ r 2 sin R a ¼ r sin R ð23Þ ¼
where a is the flow-pass thickness in the cell, d the diameter of the spacer rod (d = a/2), r the distance between the rods, and R the crossing angle of the rods. The numeral “2” means that two screening parts are taken into account in the four screening parts that surround the unit net mesh. Substituting the specifications of the diagonal net spacer incorporated with the electrodialyzer (a = 0.075 cm (d = 0.0375 cm), r = 0.3 cm, sin R = sin 60° = 0.8660) to eq 23, ε is calculated to be equal to 0.2887. 3.6. Electric Resistance of a Desalting Cell, a Concentrating Cell, and an Ion-Exchange Membrane Pair. When the 7499
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Figure 14. Structure of a diagonal net spacer.
electrolyte concentration C (equiv salt/cm3 solution) and the electrolyte activity coefficient γ in a desalting cell and in a concentrating cell respectively become (C0 , γ0 ) and (C00 , γ00 ) at an applied current density i, the cell voltage Vcell is given by the following equation:35 Vcell ¼ ðrmemb þ r 0 þ r 00 Þi 00 00 RT γ C þ 2ðtK þ tA 1Þ ln 0 0 F γC 0 00 ¼ ðrmemb þ r þ r Þi þ Vmemb
ð24Þ
tK þ tA 1 ¼ λF
ð25Þ
Figure 15. Electric resistance of a desalting cell, a concentrating cell, and an ion-exchange membrane pair for Aciplex K172/A172.
in which γ is computed using eq 9, and λ is listed in Table 3. Vmemb is the membrane potential. Direct current electric resistance of an ion-exchange membrane pair (rmemb = rK þ rA) is introduced from eqs 24 and 25 as follows: 00 00
1 γ C Vcell 2λRT ln 0 0 rmemb ¼ ðr 0 þ r 00 Þ i γC ð26Þ 1 ðVcell Vmemb Þ ðr 0 þ r 00 Þ ¼ i r0 and r00 represent the electric resistance of a desalting cell and a concentrating cell: r0 ¼
a0 ð1 ε0 Þk0
ð27Þ
r 00 ¼
a00 ð1 ε00 Þk00
ð28Þ
in which k is computed using eq 8, ε = 0.2887 (eq 23), and a = 0.075 cm. The parameters rmemb, r0 , and r00 are computed by substituting experimental data and electrodialyzer specifications into eqs 2628. Figures 1517 represent i vs r0 , r00 , and rmemb for the three ionexchange membranes, showing that rmemb is predominant over r0 and r00 . rmemb is influenced by concentration polarization, so it must increase with current density. On the other hand, rmemb is influenced by ion concentration in the membrane, which is equivalent to ion concentration in the solution passing through the membrane and it is equal to the value in the concentrating cell (C00 ) at steady state. So, rmemb must decrease with increasing current density. Inspecting Figures 1517, the influence of concentration polarization is assumed to be minor and rmemb
Figure 16. Electric resistance of a desalting cell, a concentrating cell, and an ion-exchange membrane pair for Selemion CMR/ASR.
decreases with increasing current density, because of the increased concentration in the membrane. 3.7. Concentration of a Concentrated Solution and Energy Consumption in an Electrodialysis Process for Seawater Concentration. In order to enhance the performance of the electrodialyzer, one is expected to increase the NaCl concentration in a concentrated solution (C00NaCl (g NaCl/L)) and decrease the energy consumption necessary to produce one ton of NaCl (ENaCl (kWh/(t NaCl))). The current technical target for strengthening the competitive position of an electrodialysis system in the salt market is assumed to be C00NaCl > 200 g NaCl/L 7500
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Figure 17. Electric resistance of a desalting cell, a concentrating cell, and an ion-exchange membrane pair for Neocepta CIMS/ACS3.
Figure 18. Relationship between the NaCl concentration in a concentrated solution (C00NaCl) and the energy consumption necessary to produce one ton of NaCl (ENaCl) for Aciplex K172/A172.
and ENaCl < 120 kWh/(t NaCl).36 Figures 1820 give the relationship between CNaCl and ENaCl obtained in electrodialysis experiments in section . Comparing the experimental data with the target indicates that a reduction in energy consumption is desirable. Figures 1820 are combined and are shown in Figure 21. ENaCl can be expressed as a function of cell voltage (Vcell), electric current (I), and NaCl output (PNaCl) as follows: ENaCl ¼
Vcell I PNaCl
ð29Þ
Figure 19. Relationship between NaCl concentration in a concentrated solution (C00NaCl) and the energy consumption necessary to produce one ton of NaCl (ENaCl) for Selemion CMR/ASR.
Figure 20. Relationship between NaCl concentration in a concentrated solution (C00NaCl) and the energy consumption necessary to produce one ton of NaCl (ENaCl) for Neocepta CIMS/ACS3.
Vcell is given by eq 24, including the ohmic term and membrane potential term. With regard to the electric resistances in the ohmic term, rmemb, r0 , and r00 are evaluated in Figures 1517, which reveal that rmemb is predominant over r0 and r00 . Considering that the membrane potential term in eq 24 is inevitable in the electrodialysis process, energy consumption is estimated to be reduced with reductions in rmemb. However, this situation is accompanied by a decrease in C00 (C00NaCl), because of the increase in F. The policy that can be applied to decrease the electric resistance of the membrane is assumed to be (1) decrease the 7501
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’ ACKNOWLEDGMENT We are grateful to Mr. M. Akiyama (Sea Water Science Research Laboratory, Japan Tobacco & Salt Public Corporation) for offering the experimental data obtained by electrodialysis. We thank Mr. G. Takahashi and Miss A. Shinohara (Department of Chemistry, School of Hygienic Science, Kitasato University) for assistance in the fundamental investigation.
Figure 21. Relationship between the NaCl concentration in a concentrated solution (C00NaCl) and the energy consumption necessary to produce one ton of NaCl (ENaCl) for all three ion-exchange membranes.
thickness of the membrane and (2) form a double-layered membrane consisting of a fine porous thinner functional layer and porous reinforced layer. Another approach to be discussed is (3) apply an electrodialysis process in which the optimal operating condition is applied.
4. CONCLUSION Electrodialysis was performed using an electrodialyzer integrated with commercially available ion-exchange membranes, and the overall membrane pair characteristics (λ, μ, φ, and F) of commercially available membranes are measured. In order to improve the computer simulation program developed in the previous investigation,1214 the following phenomena are discussed: (1) Relationship between temperature and the overall hydraulic permeability F (leading parameter), (2) Influence of temperature and salt concentration on the physical properties of saline water, (3) Ionic constituent in a concentrated solution, (4) Electric current screening ratio of a spacer, and (5) Direct electric current resistance of an ion exchange membrane. This manuscript is one of the series describing the computer simulation of the electrodialysis process. The computing technique developed here must contribute to developing the computer program in the next version. Energy consumption and salt concentration in concentrating cells for seawater concentration are measured, and they are compared to the technical target for strengthening the competitive position of an electrodialysis system in the salt market. In order to improve the performance of the seawater concentration process, it is necessary to decrease the electric resistance of ionexchange membranes.
’ NOMENCLATURE a = flow-pass thickness in a cell (cm) C = electrolyte concentration (equiv cm3) d = diameter of a spacer rod (cm) D = solution density (kg dm3) ENaCl = energy consumption to produce one ton of NaCl (kWh/t NaCl) F = Faraday constant (C equiv1) i = current density (A cm2) I = electric current (A) JS = flux of ions across a membrane pair (equiv cm2 s1) JV = flux of a solution across a membrane pair (cm3 cm2 s1) r = electric resistance (Ω cm2) R = correlation coefficient r = distance between spacer rods (cm) ri = concentration ratio of ion i to total ions in a concentrated solution (equiv equiv1) t = transport number of ions in a membrane T = temperature (°C) Vcell = cell voltage (V pair1) Greek Letters
R = crossing angle of spacer rods (degrees) γ = activity coefficient of electrolyte (NaCl) ε = electric current screening ratio of a spacer k = specific electric resistance (S cm1) λ = overall transport number of a membrane pair (equiv C1) μ = overall solute permeability of a membrane pair (cm s1) ΔC = C00 C0 (equiv cm3) F = overall hydraulic permeability of a membrane pair (cm4 equiv1 s1) φ = overall electro-osmotic permeability of a membrane pair (cm3 A1 s1) Subscripts
A = anion exchange membrane K = cation exchange membrane Superscripts/Accents 0
00
= desalting cell = concentrating cell
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