BY M.R.VIJAYA KUMAR,ASST PROFESSOR DEPT OF CIVIL ENGINEERING, RYMEC.BELLARY.

KARNATAKA

Water A gentle introduction to water and its structure

Water has long been known to exhibit many physical properties that distinguish it from other small molecules of comparable mass. Chemists refer to these as the anomalous properties of water, but they are by no means mysterious; all are entirely predictable consequences of the way the sire and nuclear charge of the oxygen atom conspire to distort the electronic charge clouds of the atoms of other elements when these are chemically bonded to the oxygen. A covalent chemical bond consists of two atoms that share a pair of electrons between them. In the water molecule H20, the single electron of each H is shared with one of the six outer-shell electrons of the oxygen, leaving four electrons which are organized into two nonbonding pairs. Thus the oxygen atom is surrounded by four electron pairs that would ordinarily tend to arrange themselves as far from each iiI5lIn order to minimize repulsions between these clouds of negative charge This would ordinary result In a tetrahedral geometry in which the angle

angle between electron pairs (and therefore the H-O-H bond angle) is 109. However, because the two non-bonding pairs remain closer to the oxygen atom, these exert a stronger repulsion against the two covalent bonding pairs, effectively pushing the two hydrogen atoms closer together. The result is a distorted tetrahedral arrangement in which the HO--H angle is 104.5. These two computer- generated images of the H2 O molecule come from calculations that model the electron distribution in molecules. The outer envelopes show the effective surface of the molecule.

The average electron density around the oxygen atom in a water molecule is about 10 times that around the hydrogen atoms. This non-uniform distribution of positive and negative charges leads to the substances unusual behavior.

In liquid and solid water, hydrogen (blue) and oxygen (red) molecules form so-called hydrogen bonds between the positive hydrogen atoms (d+) and negative oxygen atoms (d -). This bonding results in a relatively strong tetrahedral structure.

The liquid air interface of water has an abundance of molecules whose hydrogen atoms are oriented into the air. The phenomenon, known as surface relaxation, may increase the reactivity of molecules in this region of water.

The H2 O molecule is electrically neutral, but the positive and negative charges are not distributed uniformly. This is shown clearly in the two images above, and in the schematic diagram at the left. The electronic (negative) charge is concentrated at the oxygen end of the molecule, owing partly to the nonbonding electrons (solid blue circles), and to oxygens high nuclear charge. This charge displacement constitutes an electric dipole, represented by the arrow at the bottom you can think of this dipole as the electrical image of a water molecule.

As we all learned in school, opposite charges attract, so the partially-positive hydrogen atom on one water molecule is electro statically attracted to the partially- negative oxygen on a neighboring mo1ecule This process is called (somewhat misleadingly) hydrogen bonding. Notice that the hydrogen bond (shown by the dashed blue line) is somewhat longer (117 pm) than the covalent OH bond (99 pm). This means that it is considerably weaker; it is so weak, in fact, that a given hydrogen bond cannot survive for more than a tiny fraction of a second.
Pico meter: a metric unit of length equal to one ten billionth of a meter 10-12 (or 0.0001 micron); used to specify wavelengths of electromagnetic radiation 1 pm = 1 x 10-12 metre 1 pm = 1000 femtometre 100 pm = 1 ngstrm 1000 pm = 1 nanometre

ATOMS AND ATOMIC BONDS

Atoms Molecules of minerals are composed of atoms of chemical elements and these are the basic building blocks of all matter. The atoms of an element are formed of basic particles, viz., protons, neutrons and electrons. An atom consists of a nucleus with one or more protons, each carrying a positive electromagnetic charge, and may or may not contain one or more neutrons carrying no charge. The number of satellite electrons revolving about the nucleus is the same as the protons but carry the opposite charge, that is, the negative charge. The individual elements are determined by the atomic number which is equal to the number of protons in the nucleus or the number of electrons attached to the nucleus of their atom. Each atom of every element is electrically balanced since the number of protons and electrons are equal in number and carry opposite charges.

Ionic Bond or Electrovalent Bond. When two atoms , one of which can lose one or more electrons to attain a noble gas configuration and the other can receive these electrons and thereby acquire a noble gas configuration, they are said to be bonded by an ionic band. Since the loss and gain of electrons by atoms results in the formation of ions , ionic bond is formed when two ions interact with each other and are thus held together by electrostatic attraction. Let us consider the formation of potassium chloride (KCI), and aluminium fluoride (AlF3 to illustrate ionic bonds.

Covalent Bond.The covalent bond Is formed when two atoms achieve stability by the sharing of an electron pair, each contributing one electron to the electron pair. in many cases the atoms can be regarded as having acquired a noble gas configuration. The arrangement of electrons in a covalent molecule is often shown by a Lewis structure In which only valence shells (outer shells) are depicted. For clarity sake the electrons are denoted by dots and crosses. For example,

Polarity of Bonds.A covalent bond is set up by sharing u electrons between two atoms. It is further classified as polar or non-polar depending upon the fact whether the electron pair is shared unequally between the atoms or shared equally. For example, the covalent bond in H2 and Cl2 are called non-polar as the electron pair is equally shared between the two atoms.

In the case of hydrogen fluoride the bond is polar as the electron pair is unequally shared. Fluorine has a greater attraction for electrons (or has higher electro negativity) than does hydrogen and the shared pair of electrons is nearer the fluorine atom than hydrogen. The hydrogen end of the molecule, therefore, appears positive with respect to fluorine. Arrangement of some atoms In the decreasing order of eletronegativity is

Bond polarities affect both physical and chemical properties of compounds containing polar bond. The polarity of a bond determines the kind of reaction that can take place at that bond and even affects the reactivity at nearby bonds. The polarity of bonds can lead to polarity of molecules and affect melting point, boiling point and solubility. A

A polar molecule like that of HF having two centres of charge is called affect a dipole. The degree of polarity in a polar compound is specified by its dipole moment (a vector quantity) which is equal to the charge times the distance between the positive and negative centres. Mathematically,

In general a polar bond is established between two atoms of different radii and different electro negativities while positive centres (nuclei) of different magnitudes combine to share an electron pair. Greater the value of the dipole moment, greater is the polarity of the bond. The following points may be borne in mind regarding dipole inn (I) In case a molecule contains two or more polar bonds, its dipole moment is obtained by the vectorial addition of the dipole moments of the constituent bonds. (II) A symmetrical molecule is non-polar even though It confa1us polar bonds. For example, carbon dioxide, methane and carbon tetrachloride. being symmetrical molecules, have zero dipole moments. Dipole moment of methyl chloride is a vectorial addition of dipole moments of three CH bonds and one CCl bond.

The Hydrogen Bond.Compounds containing OH or NH groups often exhibit unexpected properties, e.g., relatively high boiling points. To account for these abnormalities and on the basis of available evidence of many kinds, it is proposed that when a hydrogen atom lies between two atoms having strong electro negativities, it shows a unique property of forming a bond or bridge between them, holding one by covalent bond and the other by purely electrostatic forces. The electrostatic bond (hydrogen bond) has a strength of about 208 kJ mol-1 (compared with 200-400 kJ mol-1 for most covalent bonds). Liquids whose molecules are held together by hydrogen bonds are said to he associated and their high boiling points are doe to greater energy required to break the hydrogen bonds. Hydrogen bonding between two atoms is generally indicated by dotted lines. For example, in the following compounds hydrogen bonding is represented below:

Covalent BOND ELEROSTATIC ORCES

Hydrogen bonding is only a kind of specially strong dipole-dipole attraction. When hydrogen is attached to a strongly electronegative atom (e.g., F, o or N), the electron cloud is strongly distorted towards the electronegative atom, exposing the hydrogen nucleus. The strong positive charge of the thinly shielded hydrogen nucleus is strongly attracted by be negative charge of the electronegative atom of the second molecule. This force of attraction is much weaker than that of the covalent bond holding it to the first electronegative atom. The electrostatic attraction is, however, much stronger than other dipole-dipole attractions.

There are six known major energy levels in which an electron or a group of electrons revolve around the nucleus of an atom. Each energy level is termed as a shell, only a limited number of electrons can exist in any one energy level or shell. Table 2.5 gives the number of electrons that can exist at each shell. The closest and the farthest shells to the nucleus are termed as K and P respectively.

Valence
Valence of an element is the number of electrons that is in excess or deficient at a shell level. If the electrons are in excess it is termed as positive valence, and negative if deficient. For example, Magnesium atom contains 12 electrons and protons with 10 of the electrons below shell level M, and 2 at shell level M. It is an excess of two above the shell level L or lacks 6 to complete the shell level M. The least of the two is 2 which is taken as the valence of Mg and is positive. Table 2.6 gives the valence of some of the common elements that compose the rocks of the earth crust.

Atomic Bonds
Atoms unite together to form molecules and molecules to aggregates. There are certain forces that bind them together. The nature of these bonding forces is not completely understood. However, some of the important bonding forces that are recognized as useful in the field of soil mechanics are: 1. Primary valence bond 2. Secondary valence bond

Primary Valence Bond[Ionic Bond]

Primary valence bond is a chemical combination of two or more elements because of the lack of a complete complement of electrons in their outermost shells. One atom joins with another atom by adding electrons to its outer shell or by losing them to arrive at a stable compound. The number of electrons an atom gains or loses depends upon the valence of the element given in Table 2.6. Atoms which lose or gain electrons in this manner are called ions and the forces binding them together are called Ionic Bonds. For example in the formation of a molecule, two ions of Al join with three ions of 0 to form A1203. This is possible because each Al ion has an excess of 3 electrons in its outer ring and 0 lacks 2 electrons in its outer ring. A stable compound can be formed since the two Al ions are in excess of 6 electrons and the three 0 ions lack 6 electrons. The ionic bonds are the strongest of the bonds that hold atoms together.

Secondary valence forces. Secondary valence forces are also

sometimes called residual valence forces, Van der Waals forces, Van der Waals-London forces, intermolecular forces of attraction, and intermolecular cohesive forces. Lambe (1953) recognized two types of secondary valence forces : the Van der Walls forces and the hydrogen bonds. Secondary valence forces acting between molecules are attributed, to the presence of electric moments in the individual molecules. If, in an electrical s stem the centre of action of positive charge coincides wit the centre of action of negative charges, the system has no dipole moment, and is termed non-polar Fig. 5.2 (a)]. Although a molecule is electrically neutral, the centre of gravity of the positive and negative...charges may not coincide. An electric moment is thus developed, and the system is referred to as being polar. System of Fig. 5.2 (b) has a dipole moment of e X L. The atoms in the water molecule are held together by a heteropolar bond and the resulting molecule is not electrically symmetrical; the hydrogen oxygen bonds are at an angle of 105 [Fig. 5.2 (c )] . The water molecule is therefore a dipole. Similarly, the unsymmetrical distribution

of electrons in the silicate crystals (the most widespread and abundant constituent of clay particles) makes them polar.

The hydrogen bond. The hydrogen bond occurs when an atom of hydrogen is rather strongly attracted by two other atoms. The hydrogen cannot decide to which atom to bond, and oscillates between them. The best example of the hydrogen bond is the bond between water molecules (Fig. 5.5). The hydrogen bond is normally considered a secondary valence bond. It is, however, stronger than the usual secondary valence bond, and

is somewhat similar in character to the coordinate bond, a primary valence bond. It can be considered a strong secondary or a weak primary valence bond, or a unique bond between the secondary and primary bonds. An indication of the relative strength of the various bonds and the distance between bonded atoms can be obtained from the typical values given below (Lambe 1953)

CLAY PARTICLE-WATER RELATIONS

Introduction
The property of a soil mass depends upon the behaviour of the discrete particles composing the mass and the pattern of particle arrangement. In all these cases water plays an important part. The behaviour of the soil mass is profoundly influenced by the inter-particle-water relationships, the ability of the soil particles to adsorb exchangeable cations and the amount of water present.

Adsorbed Water
We have seen earlier the net charge on the surface of every particle is negative. The intensity of the charge depends to a considerable extent on the mineralogical character of the particle. The physical and chemical manifestations of the surface charge constitute the surface activity of the mineral. Minerals are said to have high or low surface activity, depending on the intensity of the surface charge. As pointed out earlier, the surface activity depends not only on the specific surface but also on the chemical and mineralogical composition of the solid particle. The surface activity of sand, therefore, shall not acquire all the properties of a true clay, even if it is ground to a fine powder. The presence of water does not alter its properties of coarser fractions considerably excepting changing its unit weight.

In nature every soil particle is surrounded by water. Since the centres of positive and negative charges of water molecules do not coincide, the molecules behave like dipoles. The negative charge on the surface of the soil particle, therefore, attracts the positive (hydrogen) end of the water molecules. The water molecules are arranged in a definite pattern in the immediate vicinity of the boundary between solid and water. More than one layer of water molecules sticks on the surface with considerable force and this attractive force decreases with the increase in the distance of the water molecule from the surface. The electrically attracted water that surrounds the clay particle is known as diffused double-layer of water. The water located within the zone of influence is known as the Adsorbed Layer as shown in Fig. 2.8. Within the zone of influence the physical properties of the water are very different from those of free or normal water at the same temperature. Near the surface of the particle the water has the property of a solid. At the middle of the layer it resembles a very viscous liquid and beyond the zone of influence, the properties of the water become normal. The adsorbed water affects the behaviour of clay particles when subjected to external stresses, since it comes between the particle surfaces.

To drive off the adsorbed water, the clay particle must be heated to more than 200 C, which would indicate that the bond between the water molecules and the surface is considerably greater than that between normal water molecule.

The adsorbed film of water on coarse particles is thin in comparison with the diameter of the particles. In fine grained soils, however, this layer of adsorbed water is relatively much thicker and might even exceed the size of the grain. The forces associated with the adsorbed layers therefore play an important part in determining the physical properties of the very fine-grained soils, but have little effect on the coarser soils. Soils in which the adsorbed film is thick compared to the grain size have properties quite different from other soils having the same grain sizes but smaller adsorbed films. The most pronounced characteristic of the former is their ability to deform plastically without cracking when mixed with varying amounts of water. This is due to the grains moving across one another supported by the viscous inter layers of the films. Such soils are called cohesive soils, for they do not disintegrate with pressure but can be rolled into threads with ease. Here the cohesion is not due to direct molecular interaction between soil particles at the points of contact but to the shearing strength of the adsorbed layers that separate the grains at these points.

Diffuse double layer. Experiments have shown that a soil colloid

suspended in water carries nearly always a net negative charge. The acidic nature of soil minerals suggests that hydrogen atoms of the hydroxyl groups come off in the presence of water and thereby give the minerals a net negative charge. Since the net electrical charge of the entire Soil water suspension must ( be zero the charge on each colloid must be neutralized by ions from the water which swarm around each colloid. These ions are called counter ions or exchangeable ions, since they can be replaced. If there were no thermal activity Possessed by these ions, and if there were no attraction exerted on them by other ions and colloids, these counter ions would all swarm to the surface of the particles to neutralize the surface charge of the particle. Thus, their positions are compromises between the particle charge which pulls them, and their thermal activities plus the attraction by other bodies, which keeps them away. The counter ions thus constitute the diffuse double layer (Fig. 5.6) of the colloid ; the surface charge of the colloid is the other layer of the double layer. The force fields that develop between the charged soil particles, the surrounding water, and the associated ions have a controlling influence on the soil properties which can be varied within wide limits by changing such factors as the types of ions, and their concentration, temperature, and the and amount of pore fluid.

Double layer The double layer model is used to visualize the ionic environment in the vicinity of a charged colloid and explains how electrical repulsive forces occur as shown in figure 2. Initially, attraction from the negative colloid causes some of the positive ions to form a firmly attached layer around the surface of the colloid; this layer of counter-ions is known as the Stern layer. Additional positive ions are still attracted by the negative colloid, but now they are repelled by the Stern layer as well as by other positive ions that are also trying to approach the colloid. This dynamic equilibrium results in the formation of a diffuse layer of counter ions. They have a high concentration near the surface which gradually decreases with distance, until it reaches equilibrium with the counter-ion concentration in the solution. In a similar, but opposite, fashion there is a lack of negative ions in the neighbourhood of the surface,because they are repelled by the negative colloid. Negative ions are called co-ions because they have the same charge as the colloid. Their concentration will gradually increase with distance, as the repulsive forces of the colloid are screened out by the positive ions, until equilibrium is again reached.

The diffuse layer can be visualized as a charged atmosphere surrounding the colloid. The charge density at any distance from the surface is equal to the difference in concentration of positive and negative ions at that point. Charge density is greatest near the colloid and gradually diminishes toward zero as the concentration of positive and negative ions merge together. The attached counter-ions in the Stern layer and the charged atmosphere in the diffuse layer are what is called the double layer. The thickness of this layer depends upon the type and concentration of ions in solution. The point where the Stern layer and the diffuse layer meet is called the slip plane. The Stern layer is considered to be rigidly attached to the colloid, while the diffuse layer is not. The electrical potential at the slip plane in a basic sense, is related to the mobility of the particles and is called the zeta potential. (ZetaMeter,1997)(top)

Isomorphous Substitution
Frequently in a clay mineral lattice, metallic ions of one kind may be substituted by other metallic ions of a lower valence, but of the same physical size. Such a substitution is called isomorphous substitution and may lead to different clay minerals with different physical properties. For example, one silicon ion in a tetrahedral may be substituted by an aluminium ion, which could happen when aluminium ions are more readily able in water. As an aluminium ion has 3 positive charges and a silicon 4 positive charges, there would be a net unit charge deficiency of positive charge per substitution. This would mean an increase in the net negative residual charge. Different clay minerals simply consist of the two basic sheets-the silica sheet and the octahedral sheet-stacked together in certain unique fashions with certain metallic ions present in these sheets. The structures of a few important clay minerals are described below.

Base Exchange (CATION EXCHANGE) IN SOILS :

Electrolytes dissociate when dissolved in water into positively charged cations and negatively charged anions. Acids break up into cations of hydrogen and anions like Cl or SO4. Salts and bases split into metallic cations such as Na, K or Mg, and nonmetallic anions. Even water itself is an electrolyte, because of very small fraction of its molecules always dissociate into hydrogen ions H+ and hydroxyl ions OH.- These positively charged H ions migrate to the surface of the negatively charged particles and form what is known as adsorbed layer. These H ions can be replaced by the other cations like Na, K or Mg. These cations enter the adsorbed layers and constitute what is termed as an Adsorption complex. The process of replacing cations of one kind by those of another in an adsorption complex is known as base exchange. By base exchange is meant the capacity of colloidal particles to change the the cations adsorbed on their surface.

Thus a hydrogen clay (colloid with adsorbed H cations) can be changed to sodium clay (colloid with adsorbed Na cations) by a constant percolation of water containing dissolved Na salts. Such changes can be used to decrease the permeability of a soil. Not all adsorbed cations are exchangeable. The base exchange capacity is generally defined in terms of the mass of a cation which may be held on the surface of 100 gm dry mass of mineral. It is generally more convenient to employ a definition of base exchange capacity in milli-equivalent(meq) per 100 gm dry soil. one meq is one milligram of hydrogen or the portion of any ion which will combine with or displace 1 milligram of Hydrogen. This can be explained with examples.

The cations surrounding the clay micelle are called exchangeable cations because they can be replaced by other cations. For example when ammonium sulphate is added to the soil, the ammonium ions gradually replace other cations specially calcium as shown in the following equation:

The above reversible process of replacement of one cation from the clay micelle by another cation is called cation exchange. CATION EXCHANGE CAPACITY (C.EC.) OF SOILS The total number of cation adsorption sites per unit weight of soils is called the cation exchange capacity of soils. The cation exchange capacity of the soil may also be defined as the total number of negative charges per unit weight of the soil. It is expressed in Mill equivalent* per 100 gms of soil. FACTORS AFFECTING CATION EXCHANGE CAPACITY OR THE SOIL (i) Soil texture: Since the negatively charged clay micelle attracts positively charged cations, and holds them, the cation exchange capacity of soils increases when their percentage of clay increases i.e. their texture becomes finer. (ii) Soil humus content: Since a negatively charged humic micelle attracts cations and holds them, the cation exchange capacity of soils increases when their percentage of humus increases. The cation exchange capacity of humus varies from 200 to 400 mill equivalent per 100 gms. So C.E.C. of soils also depends on the nature of humus they contain.

(iii) Nature of clay: The cation exchange capacity of soils also depends on the nature of clay minerals which are present it. The cation exchange capacities of different clay minerals are as follows:

Hence the cation exchange capacity of a soil dominated by montmorillonite or vermiculite is much higher than the cation exchange capacity of another soil dominated by Illite or Kaolinite. (iv) Soil reaction: When the pH (See Sec. 7.14) of soils increases, more. hydrogen ions dissociate from the hydroxyl groups located on the broken edge of clay minerals especially kaolinite exposing more hydroxyl groups. Hence the cation exchange capacity of soils dominated by Kaolinite increased when the pH of the soil increased.

one meq is one milligram of hydrogen or the portion of any ion which will combine with or displace 1 milligram of Hydrogen. This can be explained with examples.

Base (Cation) Exchange Capacity The surface atoms are

predominantly negative oxygen hydroxyl ions, whereas the metallic (Al, Si) ions occupy positions within the gibbsite or silica sheets Thus, although the particle as a whole may be electrically neutral, its surface can be considered to strongly negatively charged. Also, with the exception of Kaolin, isomorphous substitution, mentioned earlier, is one of the sources of negative charge at the surface of the clay crystal. Positive ions or cation the water are, therefore, attracted to these surfaces of the particles to render the crystal electrical neutral. Different clays have different charge deficiencies and have varying ability to adsorb exchangeable cations. The ability of a clay particle to adsorb ions on its surface or edges is called its base or cation exchange capacity which is a function of the mineral structure of the clay and the size of the particles.

The cations are termed exchangeable because one cation can easily be exchanged with one of these valence or by two of the cations with one-half the valence of the original cation. The base exchange capacity is expressed in terms of the weight of a cation which may be held on the surface of 100 g of dry soil material. Conventionally, it is measured in milli equivalent (meq) per 100 gm of dry soil where 1 meq is 1 mg of hydrogen or the portion of any ion which will combine with or displace 1 mg of hydrogen. On the basis of earlier discussions, it can be seen that montmorillonite has a much greater base exchange capacity than kaolinite, with Illite being intermediate in position, as shown in Table 4.3 below:

Depositional environment, weathering action, leaching, etc., will govern the kind of ions present in a deposit. Ca and Mg are the major exchangeable cations in soils. Marine clays have predominantly Na and Mg cations. The valence of the cation is the basic factor in the process of replacement or exchange. Higher Valency cations can easily replace lower valence cations. When the ions have the same valence, larger the size ion, greater its replacement capacity. Potassium ion, even though monovalent, has more replacement capacity than sodium (which is also monovalent) because of its ability to fit into the hexagonal holes in the silica sheet. Cations can be placed in approximate order of their replacement ability as follows:

Li+ < Na+ < H+ < K+ < NH+ < Mg++ < Ca++ < Al+++ The principle of cation exchange can be used with advantage in many practical situations, as for example, the stabilization of sodium clay soil by using lime. Here, calcium ions replace the sodium ions by virtue of their superior replacing power and reduces the swelling of sodium montmorillonite, because the adsorbed layer of water would be thinner when the valence of the cation is larger. one meq is one milligram of hydrogen or the portion of any ion which will combine with or displace 1 milligram of Hydrogen. This can be explained with examples.