Ion Exchange

Soil colloids carry electrical charges on them and attract ions of opposite charges coming in contact with soil colloids. The ions are held reversibly in equilibrium proportions and are termed exchangeable ions and the process is ion exchange. Ion exchange is reversible process by which two ions are interchanged between solid and liquid phases in equivalent proportions. Exchange of two cations is called cation exchange and that of two anions is called anion exchange. Reactions: Capacity of holding cations is called cation holding capacity (CHC) and that of holding anions is called anion holding capacity. Capacity of exchange cations is known as cation Exchange capacity (CEC) and that of anions is known as AEC. If CHC is high, CEC will be high. Similarly, if AHC is high, AEC will be high. CEC is expressed as m eq/100 g soil or c mol (p+)/ kg soil. (p+ = proton ) AEC is expressed as m eq/100 g soil or c mol (e-)/kg soil.(e- = electron ) Soil colloids: Soil colloids can hold both cations and anions. Soil clay is called inorganic colloid and humus is called organic colloid. Under ideal situations, soil colloids hold more cations than anions as because soil colloids are internally negatively charged. For the same reason cation exchange is dominant than anion exchange in soils. Soils dominated by allophone and oxides of Fe and Al may have net positive charge at low pH and in that case anion may be dominant. Development of charges in soil colloids: Why are soil colloids negatively charge? There are two types of sources of negative charge on soil colloids i) Permanent negative charge pH ii) dependent negative charge i) Permanent negative charge: Permanent negative charge develops due to isomorphous substitution of one ion with another ion having similar size (radius).It may occur in both silicon tetrahedral and Aluminum octahedral sheets. Once this charge is developed, this becomes permanent. So, this is called permanent (or constant) negative charge. This charge is less common in 1:1 type clay minerals. e.g kaolinite and more common in 2:1 type (e.g. smectite) and 2:1:1 type minerals (e. g. chlorite). ii) pH dependent negative charge: pH dependent negative charge arises due to ionization of functional groups attached to the inorganic and organic structure. The functional groups includes the following- OH group (clay & oxides of Fe & A1 minerals) - COOH group - C6H4OH group Humus - NH4 group Generally, 5-10% negative charge of 2:1 type and more than 50% of 1:1 type of clay minerals are p H dependent.

Factors affecting Cation Exchange reactions:

Cation exchange takes place between solid and liquid phases. There are some factors, which govern this processa) Nature of cations: Higher is the valency, higher is the binding strength of cations. So, trivalent cations are more tightly held than divalent cations and similarly, divalent elations are strongly boned than monovalent cations. Likewise, the replacing power increases with increase of valency. That is, M3+> M2+>M+ Al3+>Ca2+>K+ For ions of same charge or valency replacing power increases with atomic number. b) Concentration of ions: Replacing power increases with concentration of ions. XCa2+ + 2Na+ X(Na)2 + Ca2+ Solid L Solid Liquid [ X = Solid surface ] C) Hydrated ions: Binding strength or replacing power decreases with hydration of ions. An ion of larger hydrated radius is less lightly held by soil colloid than that of smaller hydrated radius. Thus, the replaceability of different ions follows the orderLi+ > Na+ > K+ NH4+ > Mg2+ > Ca2+ >Al3+ Size (radius) Ions K+ NH4+ Na+ Li+ Mg2+ Ca2+ d) Complementary cation: Exchange of one cation for another would be easier as the retention strength of third cation (complementary) increases. Thus, replacement of Ca2+ by NH4+ would be easier from Ca2+- A13+ saturated soil than from Ca2+- Na+ soil. Ca2+ + Al3+ Solid Ca2+ NH4
>

Hydrated 0.53 0.54 0.76 1.00 0.64 0.56

Non-hydrated 0.27 0.29 0.20 0.15 0.16 0.21

+ NH4+ Na
+

liquid

Solid

liquid

Mechanism of ion Exchange:

Cations are electrostatically adsorbed onto the surface of a clay particle. The adsorption is subjected to both inter ionic forces and kinetic forces. The emetine forces tend to hold eaters more tightly to the surface of clay. On the after hand, kinetic forces tend to dissociate cations from the clay surface i.e. these two forces act in the opposite direction. As a result, an electrical potential gradient is set up near the clay surface. On equilibrium, an ionic distribution results between clay surface and free solution. Practically in the immediate vicinity of clay surface, there is an access of cations and anion concentration is approximately zero. This is sometimes called Stern layer (according to Stern theory). On the reciprocal way, the anion concentration increases as the distance from the clay surface to the outer solution increases where cation and anion conc. are virtually equal. The double layer as described above contains an excess of cations on the surface of clay and extends from the clay surface to the free solution is known as Gouy-Chapman layer. Gouy (1910) and Chapman (1913) have described this double layer in this way. The thickness of the clay surface to the free solution is 5-10 nm. Factors affecting CEC: The following factors affect the CEC1) Soil texture: Fine - textured soils have higher CEC than sandy soils. CEC for clay soils usually exceeds 30 meq/100 g soil while the value ranges from 0 5 for sandy soils. 2) Organic matter content: The higher the content of organic matter in soil, the higher will be the CEC. 3) Amount and kind of clay: Soils with higher quantity of 2:1 type clay will have higher CEC than soils having higher quantity of 1:1 type of clay mineral. Montmorillonite has higher CEC in comparison to illite or Kaolinite. 4) Soil pH: The CEC of most soils increases with pH. The CEC is generally law at a very low pH. As the pH is raised, the negative charges on some 1:1 type clays (Kaolinite), humus and Fe/Al oxides increases, thereby increasing the cation exchange capacity. Anion Exchange Anion Exchange: Exchange of two anions between solid and liquid phases is known as anion exchange. Anion adsorber (Soil colloids) includes: i. Fe and Al oxides (e.g. Goethite, Gibbsite ) ii. Fe and Al organic complexes iii. CaCO3 iv. 1:1 type clay minerals v. 2:1 type clay minerals Surface Fe-OH and Al-OH are particularly responsible for anion adsorption for both inorganic and organic colloids. There are two kinds of anion adsorptions: a) Legand exchange. b) Protonation. Ligand exchange take place with OH group and it is chemical interaction and this is anion specific. Protonation involves electrostatic interaction, thus it is non-specific. In soils, cation exchange is dominant. Anion Exchange may take place under low pH (acid) conditions with rich in Fe and Al.

Factors affecting Anion Exchange: i) Soil pH: Anion exchange capacity increases as the soil pH decreases. ii) Valency of ions: Anion exchange increases with the valency of the anions but decreases with increasing valency of the cation. iii) Type and amount of clay colloid: Anion exchange capacity is much greater in soils high in 1:1 type of clay minerals and those containing hydrous oxides of Fe and Al than that of soils containing high amount of 2:1 type of clay minerals. Clay minerals in the montmorillonite group of expanding larger silicates usually have anion exchange capacities of less than 5 cmol/Kg. On the other hand kaolinites can have an AEC as high as 43 cmol/Kg at an accidic equilibrium p H of 4.7. 4) Salt concentration: AEC generally decreases with increasing salt concentration. Addition of salts suppresses the unequal ion distribution. In general, the relative order of exchange is OH- > H2PO4- > SO4= > NO3-. Base saturation: The total cations exchange capacity (CEC) satisfied with basic cations is termed base saturation. It is defined as the extent to which the exchange complex of a soil is saturated with exchangeable cations other then H+ and Al3+. It is expressed as a percentage of the total cation exchange capacity. % BS =
S 100 T

Where, BS=Base saturation S=Total exchangeable bases (cmol kg-1 soil or meq 100g/soil). The difference between the total CEC and total exchangeable bases (T-S) gives the extent of unsaturation or the amount of exchangeable H+ present in a soil. All cations are included in the cation exchange capacity. But in ease of base saturation, all cations except H+ and Al3+ are considered. Because, these two groups of cations contribute H+ ions in the soil solution adsorbed H+ ions contributes directly to the H+ concentration in the soil solutation Al3+ ions also contribute H+ ions indirectly to the soil solution through hydrolysis as follows: Al3+ + H2O Al (OH)2+ + H+ Al(OH)2+ + H2O Al(OH)2+ + H+ + A1(OH)2 + H2O A1(OH)3 + H+ Therefore, an A13+ ion is not considered as basic cations and the other cations are called exchangeable bases. The degree of base saturation is an important properly of soil, which usually reflects the extent of leaching and weathering of the soil. It increases at the expense of the exchange acidity. Base saturation calculation: Suppose the following quantities of ions were found in the ammonium acetate extract from leaching 20g of soil. Ca2+ = 0.02g or
0.02 10 3 or 1 meq 20(40 / 2) 0.006 10 3 or 12( 24 / 2) 0.0115 10 3 23( 23 / 1)

Mg2+ = 0.006g or Na+ = 0.0115g or

+

0.5 meq or 0.5 meq or 0.5 meq

0.0195 10 3 K = 0.0195g or 39.1(39.1 / 1)

Total = 2.5 meq The meq of ions present in 20g of soils is being calculated and the total amount of these basic cations is 2.5 meq/20g soil or 12.5 meq per 100 gm soil (
12.5 100 = 12.5meq ) 20

Suppose, the total CEC of the soil was 15 meq/100 g soil. So, the percentage of base saturation will be calculated as follows
% BS = S 12.5 100 = 100 = 83.33 T 15

BS is closely related to soil pH and also to the level of soil fertility. The availability of plant nutrients like Ca+, Mg2+ and Ca+ increases with the degree of base saturation. It is evident that soils with large amounts of 1:1 type of clay colloids can supply the nutrient cations to plants at a much slower degree base saturation than soils high in 2:1 type of clay colloids. ESP: The percentage of CEC of a soil occupied by Na is known as exchangeable sodium percentage (ESP). It is expressed as follows Exchangeable sodium (cmol/kg soil or meq/100 g soil) 100 ESP = CEC (cmol/ kg soil or meq/100 g soil) SAR (Sodium adsorption ratio): It is the ratio of the conc. of Sodium to conc. of Ca. plus Mg and is expressed as follows
SAR = Na + Ca + + Mg 2+ 2

Where the cations concentrations are in millimoles of charge/L (m mol/L).

Mechanism of nutrient uptake by plants:

Plants obtain nutrients from 4 devices:i. Through leaves. ii. From the soil solution. iii) From exchangeable ions on the surface of clay and humus particles. iv) From readily decomposable minerals. All crop plants feed mostly by root uptake of nutrients from the soil. The principle exception is the intake of conc. CO2, which enter the plant almost entirely through the stomata of the leaves. Water also is absorbed through the stomata, but the relative amount is small in comparison to the water that enters the roots. Many nutrients are capable of being absorbed by the leaves of plants. Two states of nutrients in soil were recognized, first the nutrients in the solid portion which were considered unavailable to plants, second nutrients dissolved in the liquid phase which could be readily taken in by plant-roots. These dissolved nutrients were known to diffuse freely in the soil moisture, and they were known also to move with the flow of water in the soil. Water containing the dissolved nutrients constituted the soil solution. Most of the nutrients enter to plants root as ions, either anion or cation. Ion absorption process is an important phenomenon in plant nutrition. It is through this process most of the nutrient elements are absorbed by the plants roots as ions from the soil. Many theories of the mechanism of ion absorption have been developed in recent years are given below:(i) H jenny Mr. over street 1938 contact effects between plant root and soil colloids. (ii) Lundigardh,s theory (iii)Robertsons theory (iv)Jacobsons carrier theory (iii) jennys contact exchange theory (iv) The solution theory Jennys Contact exchange theory: Jenny and associates (1951) have postulated a direct ionic exchange between the root cell add the colloidal matter of the soil. If the root and the soil colloid are in very intimate contact, the ion. Swarms of the root and of the colloid will intermingle. In other words oscillation volumes of some of the cations on the soils collard would. Overlap those of some of the H+ ions of the root cell. Under such a condition there could be a direct exchange of root H + for soil colliod cation. This process would not involve the soil water or this intermediate reaction of CO2. It is further assumed that may move from plant cell to plant cell by this same process through over lap pins oscillation volumes. It is also possible for the ions swarm of closely associated.

Colloids to overlap, and hence ions may move from one particle to another and ultimately into the plant root. Jenny supports his theory by citing the greater uptake of Na by barley root from a Na clay suspension than from a solution of NaCl or NaHlo3 having equal concentrate of cations .Fns: A diagrammatic ache me for souring how a root hair in nutrients from the soil solution and from exchangble ions on a clay. Crystal and on hummus. Londigarda theory: According to undergrad 1933 the root calls contain enzymes Cytochrome oxidize and dehydrogenase. The dehydrogenase enzyme. Contains hydrogen which can be given out during the respiration of plants roots while cytochrone oxidase contains ferrous ion. During respiration of plants roots oxygen is taken in from the soil air. This oxygen oxidizes the Fe 2+ of the cytochrome to Fe 3+ state which beins powerful pulls am ion e.g. Cl from soil solution. At the same time dehydrogenase given of H which becomes positively charged given off an electron. The H+ tends to exchange position with a cation like K + from soil solution. The H+ begins much more energetic than K+ repels it inside and the caton K+ comes insidely. The electron given off y the dehydrogenises enzyme combines, with Fe3 to reduce it to Fe2+ The Fe2+ beins less powerful than Fe3+ cannot held Cl- ion any longer and it repels the Cl- inside the roots. Thus the plants roots take up nutrient from the soil by respiration with the help of enzymes. Jacobsons carrier theory: Jacobson and his fellow workers (1950) developed the carrier hypnotherapy which is widely carpeted and is supported by many observations. According to the carrier hypo hens the cytoplasm contains certain carriers that absorb ions at the outer membrane and are responsible for transportations the ions to the cell valuable which is considered to be the storehouse of the cell. The cytoplasm appears to be able to withdrew substances from the valuable as needed these carriers are presumably pertinacious.