HYDROGEN PEROXIDE AND ITS ANALOGUES: V. PHASE EQUILIBRIA IN THE SYSTEM D2O–D2O2

1954 ◽  
Vol 32 (5) ◽  
pp. 550-556 ◽  
Author(s):  
Paul A. Giguère ◽  
E. A. Secco
Keyword(s):  
Hydrogen Peroxide ◽  
Melting Point ◽  
Freezing Point ◽  
Eutectic Point ◽  
Cooling Curves ◽  
Addition Compound ◽  
Concentrated Solutions ◽  
Number Of Solutions ◽  
Point Curve ◽  
Solid Liquid

The cooling curves of a number of solutions of deuterium peroxide in heavy water in the concentration range 11% to 95% were measured in order to determine the solid-liquid phase diagram for that binary system. The apparatus of Herington and Handley, which uses a pulsing pressure for stirring the solutions, and a thermistor, was found to be particularly suitable for that purpose. As could be expected the freezing-point curve of the deuterated compounds is closely similar to that of the hydrogen compounds, being shifted up only by about 4° for water-rich solutions and by 2° for peroxide-rich solutions. The melting point of the addition compound, D2O.2D2O very nearly coincides with one of the eutectic points at 46.2% D2O2 and −51.5 °C.; the other eutectic point is at 60.5% D2O2 and −55.1 °C. By extrapolation the melting point of pure deuterium peroxide is found to be 1.5 °C. as compared with −0.43 °C. for hydrogen peroxide. Concentrated solutions of deuterium peroxide exhibit an extreme tendency to supercool, resulting sometimes in formation of glasses even at liquid-air temperature. The previous results of Foley and Giguère for the system H2O–H2O2 were confirmed, specially as regards the melting point of the addition compound H2O2•2H2O.

Phase Relationships in the Calcium Chloride – Calcium Carbide System

1972 ◽  
Vol 50 (6) ◽  
pp. 839-843 ◽  
Author(s):  
J. F. Maillot ◽  
D. R. Morris
Keyword(s):  
Thermal Analysis ◽  
Melting Point ◽  
Calcium Chloride ◽  
Freezing Point ◽  
Eutectic Point ◽  
Calcium Carbide ◽  
Carbide System ◽  
Phase Relationships

The system calcium chloride – calcium carbide has been examined by thermal analysis. The depression of the freezing point of CaCl2 by CaC2 is ideal. The system is a eutectic one, with a eutectic point at 90 mol% CaCl2 at 740 °C. Carbon is believed to be present in the electrolyte as the so called acetylide ion [Formula: see text] The melting point of pure CaCl2 was found to be 775.2 ± 0.6 °C.

scholarly journals On the results of chilling copper-tin alloys

1901 ◽  
Vol 68 (442-450) ◽  
pp. 171-178 ◽  
Keyword(s):  
Singular Point ◽  
Freezing Point ◽  
Cooling Curves ◽  
Satisfactory Explanation ◽  
Research Committee ◽  
Tin Alloys ◽  
The Third ◽  
Point Curve

In the Third Report of the Alloys Research Committee, published in 1895, Sir W. Roberts-Austen gives an appendix, by Dr. Stansfield, containing an extremely interesting series of cooling curves of the copper-tin alloys. These curves made it evident that for many percentage compositions there were three or even four halts in the cooling due-to separate evolutions of heat, and that some of these changes must have occurred when the metal was solid. A freezing-point curve was also deduced from the cooling curves. The report contained interesting remarks on the meaning of the curves, but a satisfactory explanation was not at that time possible. In June, 1895, Professor H. Le Chatelier also published a freezing-point curve, giving the upper points only. These two curves agree in locating a singular point near the composition Cu 4 Sn, but do not give any singular point nearer to the copper end of the curve.

scholarly journals On the spontaneous crystallisation and the melting and freezing point curves of mixtures of two substances which from mixed crystals and posses a minimum or eutectic freezing point. —Mixtures of azobenzene and benzylaniline

1910 ◽  
Vol 84 (571) ◽  
pp. 344-369 ◽  
Keyword(s):  
Freezing Point ◽  
Eutectic Point ◽  
Mixed Crystals ◽  
Continuous Series ◽  
Melting Points ◽  
Point Curve ◽  
Series Of Experiments ◽  
Pure Substances ◽  
New Feature

The behaviour of mixtures of naphthalene and β-naphthol has already been investigated, and the freezing and melting point curves and the curve of spontaneous crystallisation for these mixtures described.* These substances were found to form a continuous series of mixed crystals, on a curve of Roozeboom’s Type 1, the melting and freezing points of all the mixtures lying between the melting points of the pure substances. The behaviour of mixtures of monochloracetic acid and naphthalene was also investigated, for it was stated by Cady that these substances form mixed crystals of Roozeboom’s Type 5, whose melting and freezing point curves exhibit a minimum or eutectic freezing point. Experiments were therefore made with these substances with the object of determining the form of the curve of spontaneous crystallisation, or supersolubility curve, for mixtures of this type. No sign of the formation of any mixed crystals was observed, however, in a lengthy series of experiments, and it was shown that naphthalene and monochloracetic acid give the ordinary V-shaped freezing point curve for the solutions of two substances in each other, similar to that already obtained for mixtures of salol and betol,§ the only new feature being introduced by the existence of three modifications of monochloracetic acid. The monochloracetic acid and naphthalene mixtures having thus failed as an example of mixed crystals possessing a minimum or eutectic freezing point, another attempt was made to obtain a pair of substances with convenient melting points which form mixed crystals and possess the melting and freezing point curves with minimum eutectic point characteristic of Roozeboom’s Type 5.

How Well Does Water Activity Determine Homogeneous Ice Nucleation Temperature in Aqueous Sulfuric Acid and Ammonium Sulfate Droplets?

2009 ◽  
Vol 66 (3) ◽  
pp. 741-754 ◽  
Author(s):  
Brian D. Swanson
Keyword(s):  
Sulfuric Acid ◽  
Melting Point ◽  
Acid Solution ◽  
Ammonium Sulfate ◽  
Water Activity ◽  
Freezing Point ◽  
Ice Nucleation ◽  
Point Temperature ◽  
Aqueous Sulfuric Acid ◽  
Point Curve

Abstract Frozen fraction measurements made using a droplet free-fall freezing tube apparatus are presented and used, along with other recent laboratory measurements, to evaluate how well both the water activity idea and the translated melting-point curve idea of Koop et al. predict homogeneous freezing-point temperatures for aqueous ammonium sulfate and sulfuric acid solution droplets. The new freezing-point temperature datasets agree with the previous lowest-temperature results for both solutes. The lowest measured freezing-point temperatures for aqueous ammonium sulfate solutions agree with a curve shaped like the translated melting-point curve. However, those for aqueous sulfuric acid solutions are significantly lower than predicted by the translated melting-point curve idea, and a single water activity freezing-point temperature curve does not represent the lowest-temperature freezing-point temperature data for both solutes. A linear extrapolation of the new aqueous sulfuric acid solution freezing data to low temperatures predicts that high critical supersaturations in cloud-free regions of the upper troposphere will occur when homogeneous ice nucleation in an aqueous sulfuric acid aerosol is the primary ice formation mechanism.

scholarly journals I. Bakerian lecture .―On the constitution of the copper-tin series of alloys

1904 ◽  
Vol 202 (346-358) ◽  
pp. 1-70 ◽  
Keyword(s):  
Microscopic Examination ◽  
Theoretical Basis ◽  
Freezing Point ◽  
Maximum Amount ◽  
Exact Nature ◽  
Cooling Curves ◽  
Point Curve ◽  
Microscopic Studies ◽  
Rate Of Cooling ◽  
Primary Crystals

The immediate origin of the present paper lay in a suggestion of the late Sir G. G. Stokes, made early in 1900, that we should attempt the microscopic examination of a few bronzes as an aid to the interpretation of the singularities of the freezing-point curve. This curve was at the time fairly accurately known, largely through the researches of the late Sir W. Roberts-Austen and Dr. Stansfield, published in 1895 and in 1897, and partly by our own work. Microscopic studies of the alloys had been also published by Dr. Charpy and by Mr. Stead, but, so far as we are aware, no attempt had been made to correlate the two lines of research, and the exact nature of this group of alloys remained very obscure. The ingots of alloy which we studied at first had been allowed to cool somewhat slowly and spontaneously in the furnace, so that there had been no sudden chill or alteration in the rate of cooling. Polished and etched sections of these ingots were found to contain very varied and complicated patterns that sometimes appeared to have no connection with the singularities of the freezing-point curve. For example, a tin-rich crystallisation which appeared to be primary, was found to increase to a maximum amount as we descended a branch of the curve, and in more than one region undeniable primary crystals which stood out in relief on the outside of the ingots were found, when polished half-through, to be full of smaller and quite different crystals. In fact, it became evident that the final patterns we were examining were of the nature of a palimpsest in which several different records were superposed, some of these being due to recrystallisations that had taken place after solidification. Two other considerations pointed to the same conclusion, the first was derived from the very valuable cooling curves, published by Roberts-Austen and Stansfield in 1895, which revealed the fact that far below the temperature of solidification considerable evolutions of heat occurred in the alloys as they cooled. The second was derived from Professor Poozeboom’s paper on the “Solidification of Mixed Crystals of Two Substances,” published in the ‘Zeitschrift für Physikalische Chemie,’ of December, 1899. These two researches have been respectively the experimental and the theoretical basis from which the present work has grown, and the possibilities of interpretation which they promised have induced us to make a much more serious study of the bronzes than we originally intended.

CHANGES OF DENSITY OF HYDROGEN PEROXIDE SOLUTIONS ON COOLING AND FREEZING

1950 ◽  
Vol 28b (10) ◽  
pp. 599-607 ◽  
Author(s):  
Paul A. Giguère ◽  
Pierre Geoffrion
Keyword(s):  
Hydrogen Peroxide ◽  
Solid Solutions ◽  
Freezing Point ◽  
Volume Changes ◽  
Concentrated Solutions ◽  
Binary Solutions ◽  
Dilatometric Method

The densities of binary solutions of hydrogen peroxide and water from 0 °C. down to their respective freezing point were measured by the dilatometric method with an estimated precision of ± 0.0003 gm. per ml. Volume changes during solidification were also measured but with lower precision. Solutions containing less than about 50% by weight of hydrogen peroxide expand on freezing whereas more concentrated solutions contract appreciably. Various observations on the phenomenon of supercooling seem to indicate that no solid solutions are formed between the two components. Under certain conditions hydrogen peroxide solutions decompose on melting.

Melting and Crystallization of Poly(oxyethylene) Mixtures

1995 ◽  
Vol 60 (11) ◽  
pp. 1855-1868 ◽  
Author(s):  
Ivo Lapeš ◽  
Josef Baldrian ◽  
Ján Biroš ◽  
Julius Pouchlý ◽  
Hanes Mio
Keyword(s):  
Melting Point ◽  
Lamellar Structure ◽  
Composition Dependence ◽  
Eutectic Phase ◽  
Eutectic Melting ◽  
Pure Polymer ◽  
X Ray ◽  
Long Period ◽  
Solid Liquid ◽  
Melting And Crystallization

Solid-liquid eutectic phase diagrams of mixtures of poly(oxyethylene) (M.w. 2 000) with hydroxy and methoxy endgroups, crystallizing in extended-chain macroconformation only, with glutaric acid, benzoic acid or 1,2-diphenylethane are given. The composition dependence of the melting temperature can be fitted by the Flory-Huggins equation. Interaction parameters X and interaction energy densities B evaluated from the diluent branch of the phase diagram are consistent with those obtained from the polymer branch provided the calorimetric value of enthalpy of polymer fusion is used in the latter computation. Measurements of small- and wide-angle X-ray scatterings showed a stacked lamellar structure of POE. Below the eutectic melting point, the long period of the polymer is almost independent of the diluent concentration. On raising temperature gradually from this melting point to the melting point of pure polymer, the increasing long period indicates the penetration of the diluent between the lamellae. As follows from SAXS measurements, the crystallinity of poly(oxyethylene) in the mixtures remains unchanged compared to that of the pure polymer.

Thermodynamische Interpretation der Schmelzdiagramme binärer Systeme aus Methylchlorsilanen und Pyridazin bzw. Pyrazin

1987 ◽  
Vol 42 (4) ◽  
pp. 341-351
Author(s):  
Karl Hensen ◽  
Jens Gaede
Keyword(s):  
Melting Point ◽  
Thermodynamic Functions ◽  
Liquidus Curve ◽  
Optical Measurements ◽  
Miscibility Gap ◽  
Excess Functions ◽  
Cooling Curves ◽  
Acid Base ◽  
Thermodynamic Excess Functions ◽  
Thermodynamic Excess

By analyzing the cooling curves and the resulting melting point diagrams of the chloromethylsilane- pyridazine and pyrazine systems the existence of the incongruently melting addition compounds CH3SiCl3 • Pyridazine, (CH3)2SiCl2 • (Pyridazine)2, (CH3)3SiCl • (Pyridazine)2, CH3SiCl3 • (Pyrazine)2, (CH3)2SiCl2 • (Pyrazine)2 , (CH3)3SiCl • (Pyrazine)2 was proved. By electro-optical measurements of the turbidity point it was proved that the system (CH3)3SiCl- Pyridazine exhibits a miscibility gap which intersects the liquidus curve of the amine. Based on certain approximations it was possible to fit thermodynamic functions to the experimental results to obtain the excess data of mixing of the corresponding systems. These data allow for a more profound understanding of the Lewis-acid base behaviour of the silanes and amines.Chloromethylsilanes, Pyridazine, Pyrazine, Phase Diagrams, Addition Compounds, Thermodynamic Excess Functions

HYDROGEN PEROXIDE AND ITS ANALOGUES: II. PHASE EQUILIBRIUM IN THE SYSTEM HYDROGEN PEROXIDE – WATER

1951 ◽  
Vol 29 (2) ◽  
pp. 123-132 ◽  
Author(s):  
William T. Foley ◽  
Paul A. Giguère
Keyword(s):  
Hydrogen Peroxide ◽  
Phase Equilibrium ◽  
Solid Solutions ◽  
Freezing Point ◽  
Platinum Resistance Thermometer ◽  
Platinum Resistance ◽  
Radioactive Tracers ◽  
Resistance Thermometer ◽  
Pure Solution

A precision freezing point apparatus with platinum resistance thermometer was used to investigate the system hydrogen peroxide – water over the whole concentration range. The freezing point of the purest sample of hydrogen peroxide obtained by repeated fractional crystallizations of a large quantity of 99.6% pure solution was found to be −0.461°C; that of the dihydrate was −52.10°C. The two eutectics occur at concentrations of 45.2% and 61.2% H2O2 and at temperatures of −52.4° and −56.5°C. respectively. Contrary to what has been reported previously, water and hydrogen peroxide do not form solid solutions together. This was proved conclusively by applying the technique of radioactive tracers to the 'wet residue' method of Schreinemakers.

Optimized Design of Various Ag Decorated Sn-xAg-Cu0.7 Solder Bump on Cycling Fatigue Reliability for Wafer-Level Chip Scale Packaging

2021 ◽  
Author(s):  
Hwa-Teng Lee ◽  
Ching-Yuan Ho ◽  
Chao Chin Lee
Keyword(s):  
Eutectic Point ◽  
Optimized Design ◽  
Fatigue Reliability ◽  
Wafer Level ◽  
Fatigue Lifetime ◽  
Coexistence Phase ◽  
Ag Additions ◽  
Plastic Displacement ◽  
Solid Liquid ◽  
Solder Interface

Abstract Effects of Ag content (0 ~ 3 wt.%) in Sn-xAgCu0.7 solders on microstructure characteristics and low cycling fatigue at different temperature conditions are overall investigated. To increase Ag content, the solidus point 228.8 ? of Sn-Cu0.7 gradually decreases to 218.5 ? and temperature range of solid-liquid coexistence phase is also decrease. The Sn-Cu0.7 matrix consisted of small particles of Cu6Sn5 within ß-Sn equiaxial grains and did not significantly influence solder hardness. Moreover, much intermetallic compound of plate-like Ag3Sn and rod-like Cu6Sn5 existed in Sn-xAgCu0.7 solders enables to enhance the hardness due to dense network of Ag3Sn precipitation and near eutectic point. As a result of plastic displacement decreases with higher Ag additions, better fatigue lifetime could be achieved at Ag content to 1.5 wt.%. Besides, crack stemmed from thicker IMC layer in Sn-3.0Ag-Cu0.7 solder interface will decrease fatigue performance especially for 80 ? and 120 ?.

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