Enthalpies of solution and of crystallization of lithium nitrate and of lithium nitrate trihydrate in water at 25°C

The enthalpies of crystallization of LiNO₃ and LiNO₃–3H₂O from aqueous solutions at 25°C, measured by a calorimetric method and determined from the previously published data on the concentration dependence of the enthalpy of solution, are reported. The results are compared with the values obtained from the concentration dependences of the activity coefficients and from the temperature dependences of the solubilities. The enthalpy of solution at infinite dilution and the enthalpy of hydration are given.     

Conversions between ordered and disordered cellulose. Effects of mechanical treatment followed by cyclic wetting and drying

An investigation into the effects of mechanical treatment and hydration on the order of cellulose substrates (microcrystalline cellulose and Cladophora cellulose) was performed by the use of ball milling followed by cyclic wetting and drying. The results, monitored by¹³C-CP/MAS NMR-spectroscopy, were evaluated by calculation of the crystallinity indices and principal component analysis of the NMR data acquired. The results showed that a large part of the disorder induced by the mechanical treatment of cellulose by ball milling is reversible and reordering upon hydration leads to the cellulose I form initially present. The C4 signals corresponding to the reversibly disordered cellulose chains are observed in the amorphous region between 79 and 86 ppm in the¹³C-CP/MAS NMR-spectra together with signals from cellulose chains on the surface of ordered regions. The peak cluster which contains the C2, C3 and C5 ring carbons can be divided into two specific spectral regions; one between 74 and 77 ppm largely originates from ring carbons within disordered cellulose structures, and one between 70 and 74 ppm contains larger contributions from ordered cellulose. The behaviour of the celluloses upon milling is in accordance with a concept of ordered cellulose fibrils containing amorphous cellulose mainly as surface layers and induced reversible lattice distortions.     

Bound water measurements for aqueous protein solutions and food gels

The role of aqueous media in the stabilization of globular proteins and formation of gels was studied by absorption millimeter spectroscopy. This method allowed to measure bound water, the fraction of water which had decreased rotational mobility owing to the presence of solute. Hydration data for globular proteins were compared with data obtained previously for low-weight molecules and groups. It was found that rotational mobility of water molecules in the hydration shells of various kinds of solutes (groups) decreased in the following order: water structure breaking compounds>polar groups>unfolded proteins>globular proteins>non-polar groups. Time courses of the storage modulus were determined for the chemical acidification by glucono-δ-lactone (GDL) of milk samples prepared from skimmed milk powder (SMP). Gelation of unheated milk was a monotonous process that started at pH 4.9. Heat-treated milk from SMP (16 and 14 g per 100 ml) acidified by GDL (3 g per 100 ml) at 43 °C gave non-monotonous kinetics of gelation with two phases corresponding to the mechanisms induced by denatured whey proteins at pH>5 and by casein–casein interactions at pH 4.8–4.9. For heat-treated milk, measurement of bound water gave two stages of decrease in water mobility. Additional hydration of SMP during acidification gave 0.15–0.2 g and 0.8 g bound H₂O per gram of SMP for unheated and heat-treated milk, respectively.     

A statistical thermodynamic supermolecule-continuum study of ion hydration: Cell and shell methods

A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li⁺, Na⁺, K⁺, F^– and Cl^– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties.     

Hydraulic activity of C4A3Cr in presence of C4A3S

This paper deals with synthesis and assessment of the hydraulicity of C₄A₃Cr, analog phase C₄A₃S to , relevant to the phase chemistry and properties of sulfoaluminate cements. C₄A₃Cr, synthesized at 1250 °C is well crystallized phase, latently hydraulic, with hydration accelerated in the presence of C₄A₃S, or CS. Calorimetric curves show reciprocal influence of sulfate and chromate phase in hydration of C₄A₃S-C₄A₃Cr system. The total heat expressed at hydration is nearly the same for all specimens, but the rate of heat evolution depends on the ratio of C₄A₃S/C₄A₃Cr phases. X-ray diffraction pattern and DTA curves showed that, increasing content of C₄A₃Cr in hydrating mixture results in a coexistence of two types of ettringite (chromate and sulfate ettringite) hydrogarnet, gibbsite and monosulfate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Specific surface of two hydrated cements differing in strength

Specific surface, S, of CSH-gel particles of disordered layered structure, was studied by water sorption/retention in two cement pastes differing in strength, i.e. C-33 (weaker) and C-43 (stronger), w/c=0.4. Hydration time in liquid phase was t _h=1 and 6 months, followed by hydration in water vapour either on increasing stepwise the relative humidity, RH=0.5→0.95→1.0 (WS) or on its lowering in an inverse order (WR). Specific surface was estimated from evaporable (sorbed) water content, EV (110°C), assuming a bi- and three-molecular sorbed water layer at RH=0.5 or 0.95, respectively (WS). On WR it was three- and three- to four-molecular (50 to 75%), respectively, causing a hysteresis of sorption isotherm. At RH=0.5 the S increased with cement strength from 146 m² g^-1 (C-33, 1 m) to 166 m² g^-1 (C-43, 1 m) and with hydration time to 163 (C-33, 6 m) and to 204 m² g^-1 (C-43, 6 m). At RH=1.0 (and 0.95), higher S-value were measured but these differences were smaller: S amounted to 190-200 m² g^-1 in C-33 (1 and 6 m) and 198-210 m² g-1 in C-43 (1 and 6 m). Thus no collapse occurred on air drying of paste C-43 (6 m). This revised version was published online in July 2006 with corrections to the Cover Date.     

An analysis of the total ion-solvent encounter configuration of ClO 4 − and BF 4 − with Na+ and Li+ in water,studied by various nuclear magnetic relaxation times. Part 21

Proton relaxation rates of the solvent water in NaClO₄, NaBF₄, LiClO₄, and NiBF₄ solutions together with some self-diffusion coefficients are reported and interpreted in terms of structure-breaking effects.¹⁹F relaxation rates in⁷LiBF₄ and⁶LiBF₄ solutions in D₂O have been measured, and the relaxation contribution caused by⁷Li⁺ has been evaluated to give a cation-anion model pair distribution function.⁷Li relaxation rates in H₂O and D₂O are also reported, and conclusions concerning the hydration structure of Li⁺ have been drawn. The strong relaxation effects caused by the ions BF ₄ ^– and ClO ₄ ^– on²³Na⁺ and⁷Li⁺ have been subjected to a detailed analysis, and combined ion-solvent encounter configurations are presented which yield an electric field gradient strong enough to cause the observed effect.Part 1 was presented at the Faraday Discussion Ion-Ion and Ion-Solvent Interaction, Oxford, September 1977 (see ref. 1).     

Thermody namic functions of 1,2-alkanediols in dilute aqueous solutions

The heat capacities of binary aqueous solutions of 1,2-ethanediol, 1,2-propanediol and 1,2-butanediol were measured at temperatures ranging from 283.15 to 338.15 K by differential scanning calorimetry. The partial molar heat capacities at the infinite dilution were then calculated for the respective alkanediols. For 1,2-ethanediol or 1,2-propanediol, the partial molar heat capacities at the infinite dilution of increased with increasing temperature. In contrast, the partial molar heat capacities of 1,2-butanediol at the infinite dilution decreased with increasing temperature. Heat capacity changes by dissolution of the alkanediols were also determined. Heat capacity changes caused by the dissolution of 1,2-ethanediol or 1,2-propanediol were increase with increasing temperature. On the other hand, heat capacity changes caused by the dissolution of 1,2-butanediol are decrease with increasing temperature. Thus our results indicated that the structural changes of water caused by the dissolution of 1,2-butanediol differed from that of the two other alkanediols. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparison of the Temperature Effect on the π∗←n and π∗←π Electronic Transition Bands of NO<Subscript>3</Subscript><Superscript>−</Superscript>(aq)

The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO₃⁻(aq) centered at ≈200 nm was studied in the temperature range 10–70 ^∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion.     

Heat capacity of alcohols in aqueous solutions in the temperature range from 5 to 125°C

Using a precise technique of scanning microcalorimetry the heat capacity differences between water and dilute aqueous solutions of ethanol, n-propanol, n-butanol and n-pentanol were measured from 5 to 125°C and the partial molar heat capacities of these substances in water were determined. It was found that the heat capacity increment for alcohol disolved in water is proportional to the number of the-CH ₂ ^– groups and decrease with a temperature increase. The heat capacity increment of hydration of non-polar groups is shown to be positive and large at room temperature and decreases in magnitude as the temperature increases. In contrast, the heat capacity increment of hydration of polar groups is negative at room tempreature and increases as the temperature increases. From the temperature dependence of the heat capacity increment one can assume that the water molecules solvated by the non-polar groups of the alcohols behave in a non-cooperative manner.