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The Basics of Water Chemistry (Part 3)

to the crosslinking level of the cation resin. Crosslinking does not change By: C.F. “Chubb” Michaud the order of selectivity but it does accentuate the differences. Higher Summary: In Part 1 of this series, we discussed chemistry fundamentals and the formation of ions by various crosslinking spreads the differences compounds and salts that dissolve in water. We also pointed out that the ion exchange process is simply and therefore becomes the resin of an example of the applied chemistry we learn from observation. Part 2 examined the water analysis and choice for separating ions of similar (chromatography). As its conversion to usable information for setting up ion exchange design. Part characteristics 3 of this series deals with the the crosslinking is reduced, the differselectivity of ion exchange resins and how to best design ion exchange treatment systems for optimizing ences diminish. results. It also provides some useful information on using the Periodic Table of the Elements for predicting

l w d a

i w w c

selectivity in ion exchange.

Table 1 Cation Selectivity vs. Ever wonder why softeners work? How does the ion ex-change resin know Crosslink Level (DVB)*

it’s only supposed to remove hardness? Why does it release sodium during the service run and yet we can use a sodium salt to recharge that same resin during regeneration? We can use sea water to regenerate a softener and then use that same resin to soften sea water. How? The answer is ion exchange selectivity. Selectivity is the most important single aspect of ion exchange. Designing your system around selectivity can really make ion exchange work for you.

Element Monovalent Li (lithium) H (hydrogen) Na (sodium) NH4 (ammonium) K (potassium) Rb (rubidium) Cs (cesium) Ag (silver) Divalent Mg (magnesium) Zn (zinc) Co (cobalt) Cu (copper) Cd (cadmium) Be (beryllium) Ni (nickel) Mn (manganese) Ca (calcium) Sr (strontium) Pb (lead) Ba (barium)

4% 0.63 0.84 1.00 1.20 1.44 1.56 1.69 2.99 1.87 1.98 2.04 2.08 2.13 2.17 2.18 2.16 2.63 2.97 4.15 4.72

8% 0.51 0.64 1.00 1.29 1.46 1.60 1.64 4.30 1.66 1.75 1.90 1.94 1.96 2.02 1.98 2.07 2.61 3.29 5.00 5.80 3.84

16% 0.42 0.62 1.00 1.41 1.90 1.95 1.97 9.66 1.48 1.60 1.61 1.88 2.09 2.63 1.71 2.07 3.07 4.26 7.60 8.78 4.43

b e w f s 1

O

2

O

If we take two soluble salts such as calcium chloride and sodium carbonate, as described in the first part of this series (see “Part I,” WC&P, April 1998), and mix them together in solution, eventually the calcium will react with the carbonate ion and precipitate out as CaCO3. Since the calcium prefers to be with the carbonate ion, we can say it has a higher “selectivity.” Mother Nature likes to have things quietly at rest. If we look around at the myriad of rocks and natural compounds, we might ask, “Why does that compound exist?” We may also ask, “Why is the sea salty?” or “If water is the universal solvent, why doesn’t the silica in beach sand dissolve away?” Again, the answer is selectivity. If we solubilize the entire planet in a giant tank of water, then allow the water to slowly evaporate, we would have our rocks and compounds back and in approximately the same purity and quantity.

t f t a

3 P

4 C

t

The tendency of one ion to react preferentially with another is the same 5.35 7.17 5.40 7.17 principle by which ion exchangers work. Each resin type has its own exchange selectivity preference. Generally speaking, for dilute solutions, trivalent ions NOTE: In this table, sodium (Na) is arbitrarily given are preferred over divalent ones, which, in turn, are preferred over monovalent a value of 1.00 in each column. The relative strength of sodium attraction goes up with cross linking. If ones. One would expect calcium with an atomic number (AN) of 20 to be more we assign a value of 1.0 to the 4% cross link only, selective than family member magnesium (AN=12), but less than strontium then the selectivity value of sodium becomes 1.25 for the 8% and 1.50 for the 16%. (AN=38) or barium (AN=56). Experience (and lab testing) confirms this. We * DVB, or divinyl benzene, is the crosslinker in most would therefore expect potassium to be more selective than sodium (which ion exchange resins. it is) and, (refer to Periodic Table, “Part 1,” WC&P, April 1998), the halogen The next table shows the relative family (F, Cl, Br, I) to have a pecking order (which they do). In general, the higher the atomic number (for a selectivity of selected anions for typigiven family) the higher the selectivity of its ion in an ion exchange system. In concentrated solutions, such cal, strong base Type I resins. as regenerant brines, acids and bases, selectivity can change. In addition, we can alter selectivity by pH for

Trivalent Cr (chromium) 4.17 Ce (cerium) 4.75 La (lanthanum) 4.81

Strong acid, weak acid, strong base (I and II) and weak base have

This makes the separation of metals possible. the differences diminish.80 1.60 1.97 4.78 for lead.40 7.15 4.84 Ce (cerium) 4.17 2. (less moisture level decreases.02 1.63 2.) Service: SO3= O + O2 SBA Oxygen SO4= O SBA Example 2: A weak acid resin in the calcium form will still exchange for lead. Dichlorophenate 53 a value of 1. If assign a valuemore of 1. in turn. different selectivities for the same The next table shows the relative selectivity base Type I resins. attract all cations more strongly. 1. weak acid. density and.) +++ Ca++ Cr Page 2 of 5 Cr2(SO4)3 + O + CaSO4 O trichrome WAC WAC chrome free WAC lead free Technical Article The following selectivity chart shows the relationship of relative selectivity of The next table shows the relative certain cations with respect to the crosslinking level of the cation resin.07 2. Strong acid. the higher crosslinked resins have a higher charge for the 8% and 1.71 2.43 trivalent Anion Selectivity for Type I Resin (chromium) 4.09 2. 3.08 2.13 2.61 3.30 2.00. Ion exchange resins can be put into any form and can be regenerated with almost any compound soluble in water.72 1.87 1. ion. Selecting the proper resin in the proper form can help you to remove and concentrate most ions from dilute solutions. . Crosslinking selectivity of selected anions for typidoes not change the order of selectivity but it cal.) Regeneration: ClO SBA SO3= + Na2SO3 O + NaCl Converted Resin 2.13 NOTE: In this table.07 3. We are not limited to sodium chloride.96 2.01 1.50 for the 16%.18 0.10 3. which makes it very attractive for cartridge and waste treatment application.00 0.61 1.26 7.94 1.30 6.17 ions. which makes it very attractive for cartridge and waste treatment application.17 or 3.75 1.certain resins. does accentuate the differences.48 1. its of sodium attraction goes up with cross linking.30 1.66 1. thus. strong base (I and II) and weak base have different selectivities for the same ion. choice for separating ions of similar characteristics (chromatography).30 1. This may help explain why any one manufacturer may offer dozens of ion exchange resins.00 in each column.75 5.88 2. * DVB.81 5. strong base Type I resins.07 4.25 moisture. hydrogen or hydroxide.60 8.63 1.29 5.35 7. which appear to do the same job. less swelling). is the crosslinker in most ion exchange resins. Higher crosslinking spreads the differences and therefore becomes thestrong resin of Strong acid. Selecting the proper resin in the form can help you to remove of proper selected anions for typical. Ionic complexes such as gold cyanide and other metallic solutions Table 2 Trivalent can have very high selectivity—more so thanCrother divalent even 4.22 0. NOTE: In this table. Example 1: Strong base anion can be placed in the sulfite form by regenerating with sodium sodium sulfite which. or divinyl benzene.30 1.53 0.7 7. will scavenge oxygen from feed streams by converting to sulfate.18 2. weak acid.0 to the 4% cross link only. strong and concentrate most ions from diWater Conditioning & Purification Salicylate Phenate I (iodide) HSO4 (bisulfate) NO3 (nitrate) Br (bromide) NO2 (nitrite) CN (cyanide) HSO3 (bisulfite) BrO4 (bromate) Cl (chloride) OH (hydroxide) HCO3 (bicarbonate) H2PO4 (acid phosphate) Formate Acetate F (fluoride) 28 8. With their polymerwe strands compacted then the selectivity value of sodium becomes 1.98 2. As the base (I and II) and weak base have crosslinking is reduced.65 0.00 5.04 2.98 2. The relative strength As the crosslinking level of the standard strong acid cation resin increases. Our ability to manipulate the Ion Selectivity 4.17 selectivity of ion exchange is what gives it suchLa a (lanthanum) high utility.30 1. sodium (Na) is arbitrarily given Mg Zn Co Cu Cd Be Ni Mn Ca Sr Pb Ba (magnesium) (zinc) (cobalt) (copper) (cadmium) (beryllium) (nickel) (manganese) (calcium) (strontium) (lead) (barium) 1.90 1. chloride is arbitrarily given a value of 1.16 2.) Ca++ Pb++ Pb(NO3)2 + O + Ca(NO3)2 O WAC 4.34 0.

) Regeneration: O SAC Na+ + K+ KCl Potassium Salt O Converted Resin + NaCl 8.Technical Article Page 3 of 5 3. Again.) Cr2(SO4)3 + Trichrome Ca++ O WAC Pb++ O WAC + Ca(NO3)2 Lead Free Ca++ O WAC Cr++ O WAC + CaSO4 Chrome Free Example 3: Weak base resins in salt form (acid form) will exchange their acid radicals for ones of higher selectivity.) Service: HCl Na2CrO4 + Hex Chrome O WBA H2CrO4 O + WBA NaCl 6.) Pb(NO3)2 + 4.) Service: K+ O SAC Na+ + NaHCO3 Sodium Salt O SAC + KHCO3 Sodium Free . 7. 5.) Regeneration: H2CrO4 O + WBA FB NaOH Caustic O + NaCrO4 + H 2O Free Base Form FB O WBA HCl + HCl Acid O Example 4: A strong acid resin can be converted with potassium chloride (KCl) to put resin in the K+ form and be used to scavenge sodium from a reverse osmosis (RO) supply for sodium free water. this makes for a very selective scavenger for certain metal contaminated groundwater.

0 to the 4%in cross link only.00.96 2.) Service: * DVB.72 1. it will undergo exchange with any other ion in solution.07 2.43 Ion Selectivity Example complex (FeCl )-3 when dissolved Dichlorophenate 6 53 in concentrated hydrochloric acid. It also allows the use of seawater to regenerate a softener (although there are limitations on the total dissolved solids or TDS of the feed stream). Should HCl become contaminated NOTE: In this table.10 then the selectivity value of sodium becomes 1.18 FeCl 6 Clion.04 2. the higher the atomic number within a family (of the same valence) the higher the selectivity.13 2.30 next table6shows the relative O +The H 3 (FeCl ) O + HCl BrO4 (bromate) 1.00 5. In addition to the water chemistry of the feed stream.) Regeneration: H2PO4 (acid phosphate) 0.78 tive for cartridge and waste treatment application. weak acid.71 2. -3 ClFeCl CN 6(cyanide) 1.) Service: O K+ SAC + NaHCO3  O sodium salt Na+ SAC + KHCO3 sodium free 4. is the crosslinker in most NO2 (nitrite) 1.Other common uses with NaCl or KCl regenerations include the reduction/ Table 3 Table 2 Trivalent removal of: Cr (chromium) 4. If the resin contains very little of that ion (because of a clean regeneration). September 1996) fairly effectively if the water chemistry is right. If I (iodide) 7. This allows the use of anion exchange to remove fluorides (“Fluoridation—Friend or Foe.98 2.22 different selectivities for the same -3 Acetate 0.80 1. However. 3.13 Ce (cerium) 4.84 4.) for regeneration.65 HCO3 (bicarbonate) 0.35 7.00). strong 10.17 2. HCl. then the exchange will occur.02 1.07 3. the interplay of equilibrium and ion selectivity is key.25 4 water converts iron back to a trivalent cation flushes it from3.30 9.30 we assign a value of 1.30 HSO3 (bisulfite) 1. We see this in our description of the anion dealkalizer. That condition has to do with the equilibrium process and we refer to it as mass action.00 in each column. There’s an additional consideration that comes into play that expands the use of ion exchange.) Ca++ Pb++ Pb(NO3)2 + O + Ca(NO3)2 O WAC WAC lead free 8. Br (bromide) 2.) Ca++ Cr+++ Cr2(SO4)3 + O + CaSO4 O trichrome WAC WAC chrome free Other common uses with NaCl or Technical Article KCl regenerations include the reducPage 4 of 5 tion/removal of: Example 5: Iron forms a very strong Reduction/Removal Applications Regenerant NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl NaCl or KCl O SBA proper + form Hcan 2 O help you to remove O and concentrate most ions from diSBA NOTE: In this table.63 1.01 selectivity of selected anions for typiSBA Iron Contamination SBA Clean Acid Cl (chloride) 1.60 1.09 2.17 Anion Selectivity for Type I Resin Resins and Their Common 3.75 5. regardless of selectivity. Water Conditioning & Purification . sodium (Na) is arbitrarily given Salicylate 28 with iron.10). The capacity is fairly low (about 5-to-7 kilograins per cubic foot or Kgr/ft3) but viable.94 1.61 1. or divinyl benzene.16 2.75 1.53 vs 1. Simply stated.30 ion exchange resins. Bicarbonate is actually further down the list than chloride (selectivity 0. Conclusion There are many variables of feed streams and regenerants that will define the performance of an ion exchange application. the higher the valence of the ion the higher the selectivity. the exchange between bicarbonate in the water and the chloride on the resin will take place.17 La (lanthanum) 4.08 2. That same resin might exhibit a 20 Kgr/ft3 capacity in removing sulfates because of selectivity (sulfate selectivity is 6.81 5.17 anion Problem Alkalinity Arsenic +5 Cyanide Copper Iron Nitrate Selenium Radium Sulfates Uranium Fluoride Resin SBA II SBA I SBA I SAC SAC SBA II SBA I SAC SBA II SBA II SBA II Zn Co Cu Cd Be Ni Mn Ca Sr Pb Ba (zinc) (cobalt) (copper) (cadmium) (beryllium) (nickel) (manganese) (calcium) (strontium) (lead) (barium) 1.15 4. OH (hydroxide) 0.97 4. + FeCl3 Where: SAC = strong acid cation exchanger SBA I = strong base anion Type I SBA II = strong base anion Type II JUNE 1998 Ferric Salt We’ve discussed selectivity as the backbone of the ion exchange process along with the subtle influence of crosslinking and feed concentration. of sodium attraction goes up with cross linking. and it only requires a small amount of salt (5 pounds or lbs.18 2.29 5. strong base Type I resins.7Since the one can use a strong base anion in the chloride form to remove it.88 2.26 7.34 base (I and II) and weak base have Formate 0. flow rate and regenerant level.53 Strong acid. The relative strength Phenate 8.30 the resin. Also.50 for the 16%.61 3.00 cal. if we have a clean resin in an ionic form.07 4.60 8. rinsing the spent resin with plain complexed specie only exists strong HSO (bisulfate) 6. Selecting the proper resin in the F (fluoride) 0. Mass action seeks to form an equilibrium between the ionic concentrations in solution (the feed stream) and the ionic concentration of that same species on the resin.90 1. In general. chloride is arbitrarily given a value of 1.” WC&P. NO3and (nitrate) for thethe 8% and 1.40 5: Iron forms a very strong7.98 2. a value of 1.63 2.

He holds several US Patents on ion exchange processes. He has been associated in direct sales for the past 23 years with The Purolite Company. New York. Environmental Ion Exchange. a world-wide manufacturer of Ion exchange resins.Michaud. 1972. September 1996. 3. ©June 1998 Reprinted with permission of Water Conditioning & Purification Magazine. must be with written consent of the Publisher. He has authored or presented over 100 technical publications and papers. He has served on the Board of Directors of the Pacific WQA since 2001 and chairs its Technical Committee. “Fluoridation—Friend or Foe. fruit acids or metals by applied ion exchange choice and proper design. base or acid can be used as the regenerant resulting in the conversion of one or more elements of the feed to a totally different chemistry. 1994. New York. Michaud chaired the Ion Exchange Task Force (1999-2001) and currently chairs the Commercial/Industrial Section (since 2001). CA.Kunin. He was a founding member of (and continues to serve on) the Technical Review Committee for Water Conditioning and Purification Magazine. he holds both a Bachelors and Masters degree in Chemical Engineering and has over thirty years of field experience in water and fluid treatment applications and systems design.M. Any soluble salt. A. Any reuse or republication.Technical Article Page 5 of 5 Ion exchange resins can be made to do more than soften or deionize water by selecting the proper resin and proper regenerant for the job.E.Dictionary of Chemistry. Lewis Publishers. It’s even possible to achieve selective removal of a single ionic species such as nitrates. Krieger Publishing.. A University of Maine graduate. An active member of the Water Quality Association. 4. Chubb Michaud is the CEO and Technical Director of Systematix Company. sulfates. . in part or whole..” WC&P. New York. McGraw-Hill Inc.Wachinski. which he founded in 1982.F. Michaud began his technical career with Rohm and Haas Company in 1964 and founded Systematix in 1982. 1997. He was elected to the WQA Board of Directors and Board of Governors in 2005 and is a Certified Water Specialist Level VI. References 1. and J. He also serves on the Board of several diverse manufacturing companies.. Etzel. of Buena Park. 2. Ion Exchange Resins. C. Robert.