NMR investigation of certain hydrated fluorosilicates

Proton and fluorine NMR were investigated in the temperature range 90–425 °K in the hexahydrated fluorosilicates of Zn, Cu, Mn, Co, and Ni and in the tetrahydrated CuSiF6 to obtain information about the internal motions in these solids. Second moment transitions were observed at widely different temperatures for the different substances, and these are ascribed to the onset of reorientation of the M(H2O)₆²⁺ and SiF₆^2- octahedra. The correlation frequency and the potential barrier hindering the motion were calculated in all the cases. Apart from the narrowing taking place at higher temperatures, the Co salt showed a change in the line structure at 248 °K, where a phase transition was reported from magnetic susceptibility measurements. Studies on the single crystals of ZnSiF6 · 6H2O and NiSiF6 · 6H2O showed that there are three nonequivalent p-p vectors, and after the transition they all become equivalent, with the M(H2O)₆²⁺ octahedron reorienting about the fourfold axes.

Stereochemical Analysis of Higher α,α-Dialkylglycine Containing Peptides. Characterization of Local Helical Conformations at Dipropylglycine Residues and Observation of a Novel Hydrated Multiple β-Turn Structure in Crystals of a Glycine Rich Peptide

The peptide Boc-Gly-Dpg-Gly-Gly-Dpg-Gly-NHMe (1) has been synthesized to examine the conformational preferences of Dpg residues in the context of a poor helix promoting sequence. Single crystals of 1 were obtained in the space group P21/c with a = 13.716(2) Å, b = 12.960(2) Å, c = 22.266(4) Å, and β = 98.05(1)°; R = 6.3% for 3660 data with |Fo| > 4σ. The molecular conformation in crystals revealed that the Gly(1)-Dpg(2) segment adopts φ, ψ values distorted from those expected for an ideal type II‘ β-turn (φGly(1) = +72.0°, ψGly(1) = −166.0°; φDpg(2) = −54.0°, ψDpg(2) = −46.0°) with an inserted water molecule between Boc-CO and Gly(3)NH. The Gly(3)-Gly(4) segment adopts φ, ψ values which lie broadly in the right handed helical region (φGly(3) = −78.0°, ψGly(3) = −9.0°; φGly(4) = −80.0°, ψGly(4) = −18.0°). There is a chiral reversal at Dpg(5) which takes up φ, ψ values in the left handed helical region. The Dpg(5)-Gly(6) segment closely resembles an ideal type I‘ β-turn (φDpg(5) = +56.0°, ψDpg(5) = +32.0°; φGly(6) = +85.0°, ψGly(6) = −3.0°). Molecules of both chiral senses are found in the centrosymmetric crystal. The C-terminus forms a hydrated Schellman motif, with water insertion into the potential 6 → 1 hydrogen bond between Gly(1)CO and Gly(6)NH. NMR studies in CDCl3 suggest substantial retention of the multiple turn conformation observed in crystals. In solution the observed NOEs support local helical conformation at the two Dpg residues.

Using Water as a Design Element in Crystal Engineering. Host-Guest Compounds of Hydrated 3,5-Dihydroxybenzoic Acid

Thirteen host guest compounds of 3,5-dihydroxybenzoic acid (DHBA) have been structurally characterized. Water molecules occupy the peripheries of a hexagonal void, created with DHBA molecules, and act as ``hooks'' to connect the guest molecules with the host-framework via hydrogen bonding. The ``water hook'' is an OH group acting as a donor. Consequently, the guest molecules were chosen so that they contain good hydrogen bond acceptor functionalities. A number of multicomponent hydrates were isolated with stoichiometries (DHBA)(x)(H2O). (guest),. Of these, compounds with the following as guests were obtained as crystals that were good enough for single crystal work: ethyl acetate (EtOAc), diethyl oxalate, dimethyl oxalate, di(n-propyl) oxalate, diethyl malonate, diethyl succinate, chloroacetonitrile, N,N-dimethyl formamide (DMF), acetone, dimethyl sulfoxide (DMSO), 1-propanol, and 2-butanol. From 2-butanol, a hemihydrate, (DHBA)(2)(H2O), was also obtained concomitantly. Further to guest stabilization, water acts as a good mediator of effective crystal packing and also determines the topology of the host framework. En the present series of compounds, the role of water is wide ranging, and it is not easy to classify it specifically as a host or as a guest.

Leachability of trace elements from two stabilized low lime Indian fly ashes

Fly ash is a waste by-product obtained from the burning of coal by thermal power plants for generating electricity. When bulk quantities are involved, in order to arrest the fugitive dust, it is stored wet rather than dry. Fly ash contains trace concentrations of heavy metals and other substances in sufficient quantities to be able to leach out over a period of time. In this study an attempt was made to study the leachabilities of a few selected trace metals: Cd, Cu, Cr, Mn, Pb and Zn from two different types of class F fly ashes. Emphasis is also laid on developing an alternative in order to arrest the relative leachabilities of heavy metals after amending them with suitable additives. A standard laboratory leaching test for combustion residues has been employed to study the leachabilities of these trace elements as a function of liquid to solid ratio and pH. The leachability tests were conducted on powdered fly ash samples before and after amending them suitably with the matrices lime and gypsum; they were compacted to their respective proctor densities and cured for periods of 28 and 180 days. A marked reduction in the relative leachabilities of the trace elements was observed to be present at the end of 28 days. These relative leachability values further reduced marginally when tests were performed at the end of 180 days.

Role of Gypsum in the Strength Development of Fly Ashes with Lime

The strength of fly ash mixture often needs to be enhanced for its better utilization in geotechnical and environmental applications. Many fly ashes often improve their strength with lime but may not meet the requirements. Gypsum, which reduces the lime leachability, further improves the strength. An attempt is made in this paper to study the effect of gypsum on the strength development of two Class F fly ashes with different lime contents after curing them for different periods. The sustainability of improved strength has been examined after soaking the cured specimens in water and with different leachates containing heavy-metal ions. The strength of both the fly ashes investigated improved markedly up to a particular amount of the lime content, which can be taken as optimum lime content, and thereafter the improvement is gradual. The improvement in strength at higher lime contents continues for a longer period (even up to 180 days). Gypsum accelerates the gain in strength for lime-stabilized fly ashes, particularly in the initial curing periods at about optimum lime content. At high lime contents gypsum attributes very high strength after curing for long periods mainly due to the alteration of fly ash lime reaction compounds. Gypsum not only improves the reduction in the loss of strength due to soaking even at low curing periods but also improves the durability of stabilized fly ashes due to repeated cycles of wetting and drying.

Reactivity Of Silica From Rice Husk With Lime

The paper correlates the reactivity of rice husk ash with its physicochemical properties such as crystallinity, surface area, microstructure, particle size distribution, porosity and solubility. These properties, in tum, are dependent on the time-temperature conditions under which the ash is prepared. It is found that the reactivity of the ash cannot be quantified by any one of these parameters alone, though they all indicate it qualitatively. Therefore, a method for quantifying this property was developed, by which the Reactivity Index is obtained. There is only a gradual change in the reactivity index of RHA with ashing temperature, as in many other properties, like surface area, porosity and total volume of gas absorbed by unit mass of the silica ash. This reactive index is found to be useful in determining the optimum ash/lime ratios required to give the best performance for RHA-lime composites.

The crystal structure of hydrated barium copper oxalate

BaCu(C2O4)(2) . 6H2O is triclinic, P (1) over bar, with a = 6.5405(9), b = 9.202(3), c = 10.939(1) Angstrom, alpha = 85.46(2), beta = 79.22(1), gamma = 80.45(2), V = 636.99(1) Angstrom(3), Z = 2, D-0 = 2.14, D-c = 2.465 g . cm(-3), R = 0.074, wR = 0.0746 for 2219 significant reflections \F-0\ greater than or equal to 6.0 sigma F-0. The barium has eleven coordinations and the coordination polyhedra is a capped antiprism. Six water oxygen atoms are coordinated whereas the other five are coming from the oxalate group. In the unit cell the molecule's form a polymeric network. One lattice water molecule belongs to the coordinating water. The barium oxygen distances vary from 2.75 Angstrom to 3.15 Angstrom.

Optimization of Lime Content for Fly Ash

Abundant quantities of fly ash have been produced by thermal power plants situated ail over the world. Many applications of fly ash depend upon its pozzolanic reactivity. This reactivity depends upon many factors, including lime content. Many fly ashes show marked improvement with the addition of lime. However, for every fly ash, there is an optimum lime content for its maximum reactivity. There is no well-established simple test to determine the optimum lime content. In this paper an attempt is made to use a simple physical and physico chemical test to determine the optimum lime content. The principle behind the use of a pH test, liquid limit test, and free swell index test to determine the optimum lime content has been explained. All the methods predict nearly the same optimum lime content and correlate well with that determined by the strength test.

Nonlinear optical activity of anhydrous and hydrated sodium p-nitrophenolate

Differently hydrated sodium p-nitrophenolate (NPNa) crystals were obtained while growing them from different solvents such as methanol and water. Thermal analysis and powder X-ray diffraction studies were carried out on these crystals. Kurtz powder SHG technique was used for qualitative assessment of their nonlinear optical (NLO) activity. From the detailed single-crystal X-ray diffraction studies it is established that NPNa has three different forms, of which only one is found to possess NLO activity. Additionally, a new NLO active crystal was also found to grow from aqueous solution. (C) 1999 Elsevier Science B.V. All rights reserved.

Properties of lime stabilised steam-cured blocks for masonry

The paper addresses certain issues pertaining to the technology of lime-stabilised steam-cured blocks used for masonry construction. Properties of lime-stabilised steam-cured blocks using expansive soils and tank bed soils have been examined. Influence of parameters like steam curing period, lime content and fly ash content on wet strength of blocks is studied. Steam curing of lime stabilised blocks at 80degreesC for about 20 hours at atmospheric pressure leads to considerably higher strengths when compared with curing under wet cloth at ambient temperatures. Clay-fly ash fractions of the mix control the optimum lime content yielding maximum strength. Long-term strength behaviour of steam-cured blocks has been monitored. The results indicate a favourable lime-clay ratio for stable long-term strength. A small-scale steam cured block production system has been designed and implemented to construct a load bearing masonry structure, thus demonstrating the potential of steam-cured block as a material for masonry construction.

Enhancement of Strength of Soft Soils with Fly ash and Lime

Disposal of large quantities of fly ash poses a major environmental problem. To enhance its utilization, fly ash is considered for stabilizing of expansive soft soils. Improving the strength of soil, which is of major importance, depends on the pozzolanic nature of fly ash. Fly ashes with high pozzolanic reactivity are widely used but those with less pozzolanic reactivity are greatly inhibited. As the strength development in natural expansive soil considered in this investigation is very less with different percentages of fly ash, an attempt is made to increase the same by addition of lime along with fly ash. Based on several tests conducted, the optimum lime contents for fly ash and soils are 5% and 8% respectively. The strength of compacted soil with different fly ash contents of 10 to 40% with lime contents of 5% and 8% are determined after curing for different periods. The strength improvement for any soil-fly ash mixture, which is substantial with 5% of lime, is further improved with 8% of lime. The strength of soil-fly ash mixtures with any lime content increases with curing period.

Strength of lime-fly ash compacts using different curing techniques and gypsum additive

Lime-fly ash mixtures are exploited for the manufacture of fly ash bricks finding applications in load bearing masonry. Lime-pozzolana reactions take place at a slow pace under ambient temperature conditions and hence very long curing durations are required to achieve meaningful strength values. The present investigation examines the improvements in strength development in lime-fly ash compacts through low temperature steam curing and use of additives like gypsum. Results of density-strength-moulding water content relationships, influence of lime-fly ash ratio, steam curing and role of gypsum on strength development, and characteristics of compacted lime-fly ash-gypsum bricks have been discussed. The test results reveal that (a) strength increases with increase in density irrespective of lime content, type of curing and moulding water content, (b) optimum lime-fly ash ratio yielding maximum strength is about 0.75 in the normal curing conditions, (c) 24 h of steam curing (at 80A degrees C) is sufficient to achieve nearly possible maximum strength, (d) optimum gypsum content yielding maximum compressive strength is at 2%, (e) with gypsum additive it is possible to obtain lime-fly ash bricks or blocks having sufficient strength (> 10 MPa) at 28 days of normal wet burlap curing.