Hydration heat capacity

Brunauer and co-workers [129, 130] found values of of 1310, 1180, and 386 ergs/cm for CaO, Ca(OH)2 and tobermorite (a calcium silicate hydrate). Jura and Garland [131] reported a value of 1040 ergs/cm for magnesium oxide. Patterson and coworkers [132] used fractionated sodium chloride particles prepared by a volatilization method to find that the surface contribution to the low-temperature heat capacity varied approximately in proportion to the area determined by gas adsorption. Questions of equilibrium arise in these and adsorption studies on finely divided surfaces as discussed in Section X-3. 

The properties of calcium chloride and its hydrates are summarized in Table 1. Accurate data are now available for the heats of fusion of the hexahydrate, the incongment fusion of the tetrahydrate, and the molar heat capacities of the hexahydrate, tetrahydrate, and dihydrate (1). These data are important when considering the calcium chloride hydrates as thermal storage media. A reevaluation and extension of the phase relationships of the calcium chloride hydrates, has led to new values for the heats of infinite dilution for the dihydrate, monohydrate, 0.33-hydrate, and pure calcium chloride (1). 

K. S. Pitzer and L. V. Coulter. "The Heat Capacities. Entropies and Heats of Solution of Anhydrous Sodium Sulfate and of Sodium Sulfate Decahydrate. The Application of the Third Law of Thermodynamics to Hydrated Crystals". J. Am. Chem. Soc.. 60. 1310-1313 (1938). 

G. Brodale and W. F. Giauque, "The Heat of Hydration of Sodium Sulfate. Low Temperature Heat Capacity and Entropy of Sodium Sulfate Decahydrate", J. Am. Chem. Soc., 80, 2042-2044 (1958). 

Hammett correlation, 225-228 Hammond s postulate, 242 Heat capacity of activation, 160-161 Hydrated electrons, 266-267 Hydroxyl radicals, 266-268... 

The fact that the water molecules forming the hydration sheath have limited mobility, i.e. that the solution is to certain degree ordered, results in lower values of the ionic entropies. In special cases, the ionic entropy can be measured (e.g. from the dependence of the standard potential on the temperature for electrodes of the second kind). Otherwise, the heat of solution is the measurable quantity. Knowledge of the lattice energy then permits calculation of the heat of hydration. For a saturated solution, the heat of solution is equal to the product of the temperature and the entropy of solution, from which the entropy of the salt in the solution can be found. However, the absolute value of the entropy of the crystal must be obtained from the dependence of its thermal capacity on the temperature down to very low temperatures. The value of the entropy of the salt can then yield the overall hydration number. It is, however, difficult to separate the contributions of the cation and of the anion. 

What is the evaporation rate and yield of the sodium acetate hydrate CH3C00Na.3H20 from a continuous evaporative crystalliser operating at 1 kN/m2 when it is fed with 1 kg/s of a 50 per cent by mass aqueous solution of sodium acetate hydrate at 350 K The boiling point elevation of the solution is 10 degK and the heat of crystallisation is 150 kJ/kg. The mean heat capacity of the solution is 3.5 kJ/kg K and, at 1 kN/m2, water boils at 280 K at which temperature the latent heat of vaporisation is 2.482 MJ/kg. Over the range 270-305 K, the solubility of sodium acetate hydrate in water s at T(K) is given approximately by ... 

Study of hydrated kaolinites shows that water molecules adsorbed on a phyllosilicate surface occupy two different structural sites. One type of water, "hole" water, is keyed into the ditrigonal holes of the silicate layer, while the other type of water, "associated" water, is situated between and is hydrogen bonded to the hole water molecules. In contrast, hole water is hydrogen bonded to the silicate layer and is less mobile than associated water. At low temperatures, all water molecules form an ordered structure reminiscent of ice as the temperature increases, the associated water disorders progressively, culminating in a rapid change in heat capacity near 270 K. To the extent that the kao-linite surfaces resemble other silicate surfaces, hydrated kaolinites are useful models for water adsorbed on silicate minerals. 

Figure 3. The heat capacity (Cp) for the water intercalated between the layers of kaolinite in the 10A hydrate. Standard values for ice and liquid water are also shown. The heat capacity of the intercalated water was measured using the procedure described in Reference 2.

Matveev, Y. I., Elankin, N. Y., Kalistrova, E. N., Danilenko, A. N., Niemann, C., and Yuryev, V. P. (1998). Estimation of contributions of hydration and glass transition to heat capacity changes during melting of native starches in excess water. Starch/Starke 50, 141-147. 

Handa, Y.P. (1985). Heat capacities in the range 95 to 260 K and enthalpies of fusion for structure-II clathrate hydrates of some cyclic ethers. J. Chem. Thermodynamics, 17... 

Urea, as a cosolvent, is at the other extreme. All the concentration dependences of the binary and ternary systems are quite regular. The excess volume (Figure 6) is positive, which is rarely observed for nonelectrolytes in water. With the exception of the heat capacities of Bu4NBr, all the parameters Beu are positive for volumes and heat capacities, and the sign of the transfer functions is always opposite what we would expect for the structural hydration contribution to V° and Cp°. 

Rueff, R.M., The Heat Capacity and Heat of Dissociation of Methane Hydrates A New Approach, Disssertation, Colorado School of Mines, Golden, CO (1985). 

For si and sll, Davidson et al. (1977a, 1981) performed NMR spectroscopy and dielectric relaxation measurements where applicable, in order to estimate the barriers to molecular reorientation for simple hydrates of natural gas components, except carbon dioxide. Substantial barriers to rotation should also affect such properties as hydrate heat capacity. 

Evaluating Equations 5.28 through 5.30, and assuming that the heat capacity of the hydrate is not affected in the process, Ballard proposed that the activity coefficient of water in the hydrate be expressed as... 

---