Lecture 14: Cation Exchange and Surface Charging

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1 Lecture 14: Cation Exchange and Surface Charging

2 Cation Exchange

3 Cation Exchange Reactions Swapping of cations between hydrated clay interlayers and the soil solution Also occurs on organic matter functional groups These reactions have the following properties: Reversible Na + + X-K K + + X-Na Charge equivalent (no change in mineral charge) Na + + X-K K + + X-Na Ca X-K 2K + + X 2 -Ca

4 Cation Selectivity Higher charge (Z) ions favored Ions with small hydrated radii (r) favored Ion Al 3+ Sr 2+ Ca 2+ Mg 2+ Cs + NH 4 + K + Na + Li + Hydrated Radius (nm) Charge:Radius (Z 2 /r) Common Cation Exchange Preferences Al 3+ > Sr 2+ > Ca 2+ > Mg 2+ > Cs + > K + = NH 4+ > Na + > Li + Vermiculite and weathered Illite strongly favor K +, NH 4+, and Cs + because these cause interlayer collapse

5 Special Case: Potassium (K + ) Ammonium (NH 4+ ) and Cesium (Cs + ) with Vermiculite and Weathered Illite K +, Cs +, and NH 4+ are all just the right size and charge to fit in the ditrigonal cavity in clay tetrahedral sheets

6 Clay Mineral Complementary Cations Cations from solution are more likely to replace weakly-held cations first Example: Exchange after NH 4+ added to soil 20 Ca 2+ 5 K + 10 Mg 2+ 3 Na + 10 Al 3+ Soil Solution + 20 NH 4 + Clay Mineral 19 Ca charges replaced: All Na + replaced, most K + replaced, a little Ca 2+ and Mg 2+ replaced, no Al 3+ replaced 1 K + 8 Mg NH Al 3+ Soil Solution + 4 K Na Mg 2+ + Ca NH 4 +

7 Cation Exchange Capacity (CEC) Amount of exchangeable cations (in terms of charge) per mass of soil (or soil colloid) Units of centimoles of charge per kilogram (cmol c /kg) The amounts of specific cations that a soil can hold depend on the charge of the cations If CEC = 30 cmol c /kg, then a soil can hold 30 cmol Na + /kg, 15 cmol Ca 2+ /kg, 10 cmol Al 3+ /kg Effective CEC: CEC at a specific ph value Soils also may have an Anion Exchange Capacity (AEC)

8 CEC of Different Soil Materials Soil Colloid Type CEC (cmol c /kg) AEC* (cmol c /kg) Kaolinite 1:1 Clay 0 to 15 0 to 15 Smectite 2:1 Clay 80 to 150 ~0 Vermiculite 2:1 Clay 100 to 200 ~0 Illite 2:1 Clay 0 to 40 0 to 10 Allophane SRO Clay 0 to to 20 Gibbsite Al oxide 0 to 5 0 to 10 Goethite Fe oxide 0 to 5 0 to 20 Humus OM 100 to 500 ~0 *AEC = Anion Exchange Capacity

9 Clay CEC and Soil Classification The CEC of soil clay minerals influences how soils are classified High activity clays (e.g., smectite, vermiculite) have a high CEC Swelling clays are always high activity clays Soils with high activity clays retain cation nutrients Low activity clays (e.g., kaolinite) have a low CEC Soils with low activity clays do not retain cation nutrients well, susceptible to leaching

10 CEC of Different Soils Soil Order Average CEC (cmol c /kg) Alfisols 15 ± 11 Andisols 31 ± 18 Aridisols 18 ± 11 Entisols 20 ± 14 Histosols 140 ± 30 Inceptisols 21 ± 16 Mollisols 24 ± 12 Oxisols 8 ± 6 Spodosols 27 ± 30 Ultisols 9 ± 6 Vertisols 50 ± 17 From: Sposito (2003) The Chemistry of Soils

11 Acid and Base (Nonacid) Saturation Base Saturation = Nonacid Saturation Old Name New Name Acid Saturation % of CEC occupied by acid cations (Al 3+, H +, Fe 3+ ) Nonacid (Base) Saturation % of CEC occupied by nonacid cations (Na +, K +, Mg 2+, Ca 2+, NH 4+ ) Cation Saturation % of CEC occupied by a single cation

12 Key Concepts in Cation Exchange Clay minerals and other solids, including organic matter, can exchange cations with the soil solution 3 + ions are preferred over 2 + ions, which are preferred over 1 + ions CEC is a measure of a solid capacity to exchange cations, measured in units of total moles of ion charge that can be stored Saturation is the % CEC occupied by a cation or class of cations

13 Adsorption and Mineral Surface Charging

14 Concept of Adsorption Adsorption: Process of a solute molecule binding to the surface of a solid Adsorption occurs because: A mineral (e.g., clay) has excess charge that needs to be compensated The solute molecule forms a complex with (bonds to) a functional group on a mineral surface Adsorption is a major control on the availability and transport of nutrients and contaminants in soils and groundwater

15 Phosphate (PO 4 3- ) Adsorption to Soil Phosphate is an anion: Cannot be taking up by cation exchange!

16 Chromatographic Separation Caused by Adsorption Calcium Sodium Technetium Uranium Chromium Arsenic Ca 2+ Na + TcO - 4 UO 2 (CO 3 ) 4-3 CrO 2-4 AsO 3-4 Front of Waste Plume

17 Mineral Surface Charge

18 kaolinite Evidence of Surface Charge Effective CEC mixed illite-smectite smectite Charge on clay surfaces shows ph-dependence Clays without permanent charge show charge development as ph increases There are other sources of charge on clays surfaces!

19 ph-dependent Surface Charge of Soil Minerals Stumm, W. and Morgan, J. J. (1996) Aquatic chemistry: chemical equilibria and rates in natural waters.

20 Surface Sites Charging occurs at specific sites on a mineral surface This charging has two origins Fixed Charge Sites: Isomorphous substitution results in excess charge (as in clays) Ions are attracted to balance that charge Occur on smectite, vermiculite, zeolites, manganese oxides Variable Charge Sites: Surface functional groups protonate (add a H + ) and deprotonate (lose a H + ) The charge (protonation state) varies with ph Occur on iron oxides, aluminum oxides, edges of 1:1 and 2:1 clays, manganese oxides

21 Origin of Fixed Charge Sites T-sheet Substitutions: Al +3 (light blue) for Si +4 (dark blue) O-sheet Substitutions: Mg +2 (orange) for Al +3 (light blue) Interlayer: Cations (purple) balance the negative charge on the 2:1 layers Isomorphous substitution creates charged sites permanently fixed in mineral structure

22 Origin of Variable Charge Sites -OH Surface Sites Goethite [FeOOH] crystal structure The surfaces of oxide minerals and the edges of clays are terminated in OH groups These can gain or lose an H + ion from water, creating charged surface sites

23 Surface Charge Varies with ph Variable charge surface sites form when surface OH groups protonate or deprotonate =SOH o + H + =SOH + 2 =SOH o =SO - + H + This is dependent on ph = - log [H + ] Net surface charge can be positive or negative Positive: [=SOH 2+ ] > [=SO - ] Negative: [=SOH 2+ ] < [=SO - ] Zero: [=SOH 2+ ] = [=SO - ] =S means a surface site, not sulfur!

24 Point of Zero Charge (PZC) PZC of an Oxisol PZC = ph at which net surface charge is zero

25 ph-dependent Charge on Humus Carboxylic acid (R-COOH) and phenolic (R-OH) groups deprotonate as ph increases: negative charge Amine groups (R-NH 2 ) protonate as ph decreases: positive charge

26 Surface Sites and Types of Adsorption Cation exchange occurs at fixed charged sites Fully reversible, controlled by ion size and charge Ions are held in place by electrostatics (opposites attract) Surface complexation occurs at variable charged sites Ions and molecules forms chemical bonds with the surface of soil minerals Properties do not follow simple trends, are determined by the ways in which ions or molecules interact with solid surfaces

27 Key Concepts in Surface Charging Soil solids often develop charge at their surfaces Substitution in clays is one form of surface charge Functional groups on the edges of clays, the surfaces of iron and aluminum oxides, and organic matter may gain or lose an H + and develop charge Surface charge is ph-dependent PZC: ph where net surface charge is zero Observed CEC is often ph-dependent because of surface complexation reactions on mineral surfaces

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