In the temperature range of 0 to 100C, the density of water is maximum (1.000) at 4C, while at OoC it is 0.9999.

This is due to the collapse of some of the l,drogen bonds and the release of water molecules trapped in the cavities. Beyond 4C the density decreases to 0.9971 at 25C and 0.9584 at 100C. The decrease in density results in a decrease in the surface tension and viscosity, as shown in The combined effect of such decreases in density, surface tension and viscosity

of water (25 to 100C) is to increase the mobility of the cations end anions present. In the case of high purity water, this would mean an increase in the mobility of H+ and OH" ions that are present due to water dissociation. At ordinary temperatures, the ionic product (Kw) of water is very small (pKw or -log IOKw = 14). The pH is defined as log IOH+ and Kw is the product of [H+) and [OIl") concentrations. Thus a simultaneous and equal increase in the values of [H+] and [OH"] due to the \ increased dissociation of wate.r with temperature, would mean that the pH scale, as wei: as pH as defined wIll be effected by an increase in the temperature of water. The known range of the pH scale of 0 14 at 25C begins to contract with increase in temperature. For example, the ionic product, whose value at 25C is 1 x 10-14, increases to 52 x 10-14 at 100C. Consequently, the pH of pure neutral water defined to be 7.0 at 25C decreases to 6.25 at 100C. It should be made clear at this juncture that pure water at 100C will continue to remain neutral and because of the compression of the pH scale at 100C, the neutral point shows only an apparent decrease. The very fact that the hydrogen ion concentration increases with temperature in pure water, makes it much more aggressive to metallic surfaces at higher temperatures than at room temp. As is well known, electrolytes such as sodium chloride dissociate into their component ions on dissolution in water, due to its dielectric constant. This important property of water also undergoes a change with temperature. At OOC,the value of the dielectric constant of water is 88.0, which decreases to 78.5 at 25C and to 55.3 at 100C (and 760 mm Hg.) This means that water loses its ability to effect the dissociation of electrolytes and a fraction of the dissolved substances remains as an undissociated or neutral chemical species. The effects of high temperature are nowhere more striking than on the pH value or the pH scale of water and alkali sing weak electrolytes such as ammonium and lithium hydroxides dissolved in water. Figure 3.1 shows the temperature

dependence of the exponential of the ion product of water (pKw) in the range of 170 to 340C. Although there is some difference in the pKw values as determined by different workers, the trend is the same, viz., the pKw of water decreases (or

Kw increases) upto a certain temperature and then increases (or Kw decreases) as the temperature is increased further. The minimum ofpKw (or maximum of Kw) lies in the temperature range of230 to 250C. As seen earlier, since the pH scale and the point of neutrality of pure water are defined in terms of pKw and the minimum of pKw value as seen in Figure 3.1 being a little over 11.1, the neutr~l pH value of high purity water at say 240C is 5.55. Thereafter the neutral point shifts to higher values. It is once again emphasised that pure water will continue to remain neutral under such conditions, though both H+ and OHconcentrations will be at their maximum in equal measure. Thus, water would be most aggressive in the range of 230 to 250C. An ammonical solution of water that exhibits a pH of 9.5 at 25C is reduced to 6.4 at 220C. Similarly water spiked with LiOH that shows a pH of 10.5 at 25C is lowered to 7.76 at 220C.