Heats of Solution,Transition, and Formation of Three Crystalline Forms of Metaboric Acid

The three crystalline forms of metaboric acid HBO₂ were prepared, purified, and analyzed. Heats of solution in water or of reaction with sodium hydroxide solution were compared with those of orthoboric acid H₃BO₃(c). The best values for the heats of transition at 25 °C are: (c,I) to (c,II), 2.33±0.23 kcal/mole; (c,II) to (c,III), 1.30±0.05 kcal/mole; (c,I) to (c,III), 3.63±0.24 kcal/mole. The following heats of formation at 25 °C were derived: −192.77 ± 0.35 kcal/mole for the cubic HBO₂(c,I), −190.43 ±0.34 kcal/mole for the monoclinic HBO₂ (c,II), and −189.13 ± 0.34 kcal/mole for the orthorhombic HBO₂(c,III).     

Heat of Formation of Titanium Tetraiodide

The heat of formation of titanium tetraiodide was determined relative to that of titanium tetrabromide by comparison of their heats of hydrolysis in dilute sulfuric acid. The difference in the heats of formation may be expressed by the equation: TiI4(c)+2Br2(liq)=TiBr(c)+2I2(c),ΔH(25°C)=−230.91±0.75kj/mole(−55.19±0.18kcal/mole).By taking the heat of formation of TiBr₄(c) as −616.72 ±4.60 kj/mole, the heat of formation of TiI₄(c) is calculated to be −385.81 ±4.64 kj/mole (−91.21 ±1.11 kcal/mole). The heats of hydrolysis of TiBr₄ and TiCl₄ were similarly measured; the value obtained for the difference (186.77 ±1.34 kj/mole) is in good agreement with the difference between the directly determined heats of formation (187.11 ±5.35 kj/mole).     

Mass Spectrometric Study of NF2, NF3, N2F2, and N2F4

Appearance potentia’s have been measured for selected ions from NF₂, NF₃, N₂F₂, and N₂F₄. Ionization-dissociation processes are identified and bond dissociation energies are calculated. In addition, the bond dissociation energy, D(F₂N–NF₂), has been directly measured to be 5.14±0.38 kj/mole (21.5± 1.6 kcal/mole). A summary is made of available thermochemical and mass spectrometric data for N–F compounds and some evidence is presented to support the designation of cis and trans structures for the N₂F₂ isomers.     

Heats of Hydrolysis and Formation of Dimethoxychloroborane

The heat of hydrolysis of dimethoxychloroborane has been measured; for the reaction, (CH3O)2BCl(liq)+3H2O(liq)=H3BO3(c)+2CH3OH(liq)+HCl(g)ΔH(25°C)=−26.6±0.8kj/mole=−6.4±0.2kcal/mole.From this, we have calculated the heat of formation of dimethoxychloroborane: for the liquid, ΔHf° (25 °C) = −782.1 ± 1.8 kj/mole (−186.9±0.4 kcal/mole), and for the gas, ΔHf° (25 °C) = −747.9 ±2.2 kj/mole (−178.8±0.5 kcal/mole).     

Heat of Combustion of Borazine,B3N3H6

The heat of combustion of liquid borazine has been determined according to the following equation: B3N3H6(liq)+15/4O2(g)+3/2H2O(liq)=3H3BO3(c)+3/2N2(g),ΔH°(25°C)=−2313.3±12.6kj/mole(−552.90±3.0kcal/mole).From this value the heat of formation of liquid borazine may be calculated as ΔHf°(25 °C) = −548.5 ± 13.4 kj/mole (−131.1 ± 3.2 kcal/mole), and for the gas, ΔHf°(25 °C) = −519.2 ± 13.4 kj/mole (−124.1 ± 3.2 kcal/mole).     

Thermodynamic Properties of Polyethylene Predicted from Paraffin Data

Thermodynamic data on the n-paraffins from n-C₆H₁₄ through n-C₁₈H₃₈ have been used to obtain values for the specific heat, entropy, enthalpy, and Gibbs free energy of a large, ideal CH₂-chain crystal from 0 to 420 °K and of the liquid above 200 °K. Analytical expressions are given for the properties of the crystal and liquid above 200 °K. For the crystal, a modified Einstein function was used to adjust the melting temperature to 414.3 °K. Values between 975 and 1025 cal/mole for the heat of fusion were found to be the ones most consistent with the data. Comparison of the results with polyethylene data shows reasonable agreement.     

Acid Dissociation Constant and Related Thermodynamic Quantities for Triethanolammonium Ion in Water From 0 to 50°C

Earlier studies of the dissociation constants of monoethanolammonium and diethanolammonium ions and the thermodynamic constants for the dissociation processes have been supplemented by a similar study of triethanolammonium ion from 0° to 50° C. The dissociation constant (K_bh) is given by the formula ?log K_bh = 1341.16/T + 4.6252 ? 0.0045666Twhere T is in degrees Kelvin. The order of acidic strengths of the ions is as follows: Triethanolammonium >diethanolammonium>monethanolammonium. Conversely, monoethanolamine is the strongest of the three bases. The thermodynamic constants for the dissociation of one mole of triethanolammonium ion in the standard state at 25° C are as follows: Heat content change (ΔH°) 33.450 joule mole⁻¹; entropy change (ΔS°), −36.4 joule deg⁻¹ mole⁻¹; heat-capacity change (ΔCp°), 52 joule deg⁻¹ mole⁻¹.     

Preparation and Calibration of Carrier-Free 209Po Solution Standards

Carrier-free ²⁰⁹Po solution standards have been prepared and calibrated. The standards, which will be disseminated by the National Institute of Standards and Technology as Standard Reference Material SRM 4326, consist of (5.1597 ±0.0024) g of a solution of polonium in nominal 2 mol · L⁻¹ hydrochloric acid (having a solution density of (1.031±0.004) g · mL⁻¹ at 22 °C) that is contained in 5 mL flame-sealed borosilicate glass ampoules, and are certified to contain a ²⁰⁹Po alpha-particle emission rate concentration of (85.42±0.29) s⁻¹ · g⁻¹ (corresponding to a ²⁰⁹Po activity concentration of (85.83 ±0.30) Bq · g⁻¹) as of the reference time of 1200 EST 15 March 1994. The calibration was based on 4πα liquid scintillation (LS) measurements with two different LS counting systems and under wide variations in measurement and sample conditions. Confirmatory measurements by 2πα gas-flow proportional counting were also performed. The only known radionuclidic impurity, based on α- and photon-emission spectrometry, is a trace quantity of ²⁰⁸Po. The ²⁰⁸Po to ²⁰⁹Po impurity ratio as of the reference time was 0.00124 ±0.00020. All of the above cited uncertainty intervals correspond to a combined standard uncertainty multiplied by a coverage factor of k = 2. Although ²⁰⁹Po is nearly a pure α emitter with only a weak electron capture branch to ²⁰⁹Bi, LS measurements of the ²⁰⁹Po a decay are confounded by an a transition to a 2.3 keV (J^π= 1/2⁻) level in ²⁰⁵Pb which was previously unknown to be a delayed isomeric state.     

Measurement of the Parity-Violating Neutron Spin Rotation in 4He

In the meson exchange model of weak nucleon-nucleon (NN) interactions, the exchange of virtual mesons between the nucleons is parameterized by a set of weak meson exchange amplitudes. The strengths of these amplitudes from theoretical calculations are not well known, and experimental measurements of parity-violating (PV) observables in different nuclear systems have not constrained their values. Transversely polarized cold neutrons traveling through liquid helium experience a PV spin rotation due to the weak interaction with an angle proportional to a linear combination of these weak meson exchange amplitudes. A measurement of the PV neutron spin rotation in helium (φ_PV (n,α)) would provide information about the relative strengths of the weak meson exchange amplitudes, and with the longitudinal analyzing power measurement in the p + α system, allow the first comparison between isospin mirror systems in weak NN interaction. An earlier experiment performed at NIST obtained a result consistent with zero: φ_PV (n,α) = (8.0 ±14(stat) ±2.2(syst)) ×10⁻⁷ rad / m[1]. We describe a modified apparatus using a superfluid helium target to increase statistics and reduce systematic effects in an effort to reach a sensitivity goal of 10⁻⁷ rad/m.     

Calcium Fluoride Precipitation and Deposition From 12 mmol/L Fluoride Solutions With Different Calcium Addition Rates

The effects of different Ca-addition rates on calcium fluoride (CaF₂) precipitation and deposition were investigated in 12 mmol/L sodium fluoride solutions to which 0.1 mol/L calcium chloride solution was continuously added at average rates of (5, 7.5, 10, 12.5, 15 or 20) mmol L⁻¹ min⁻¹. The changes in ionic fluoride and calcium concentrations, as well as turbidity, were continuously recorded by F and Ca electrodes, and a fiber optic based spectrophotometer, respectively. The F⁻ concentration decreased and turbidity increased with time indicating precipitation of CaF₂. For the systems with Ca-addition rates of (5, 7.5, 10, 12.5, 15, and 20) mmol L⁻¹ min⁻¹, the 1 min CaF₂ depositions in the model substrate (cellulose filter paper, pores 0.2 µm) expressed as mean ± SD of deposited F per substrate surface area were (3.78 ± 0.31, 11.45 ± 0.89, 9.31 ± 0.68, 8.20 ± 0.56, 6.63 ± 0.43, and 2.09 ± 0.28) µg/cm², respectively (n = 10 for each group). The 1-min F depositions did not show positive correlation to Ca-addition rates. The lowest 1-min F deposition was obtained in the systems with the highest Ca-addition rate of 20 mmol L⁻¹ min⁻¹ for which CaF₂ precipitation rate reached the maximum value of 0.31 mmol L⁻¹ s⁻¹ almost immediately after beginning of reaction (6 s). The largest 1-min F depositions were obtained from the systems with Ca addition rates of (7.5 to 12.5) mmol L⁻¹ min⁻¹ in which CaF₂ precipitation rates continuously increased reaching the maximum values of (0.13 to 0.20) mmol L⁻¹ s⁻¹ after (18 to 29) s, respectively. The 1-min F depositions were greatly enhanced in comparison with the control F solutions that did not have continuous Ca-addition. This indicates that continuous Ca addition that controls the rate of CaF₂ formation could be a critical factor for larger F depositions from F solutions. The efficacy of conventional F mouthrinses could be improved with addition of a substance that continuously releases Ca.     

Phase Equilibria in Systems Involving the Rare Earth Oxides. Part III. The Eu2O3?In2O3 System

The equilibrium phase diagram was determined for the Eu₂O₃−In₂O₃ system. An induction furnace, having an iridium crucible as the heating element (susceptor), was used to establish the solidus and liquidus curves. The 1:1 composition melts congruently at 1745 ± 10 °C. Melting point relations suggest that the 1:1 composition is a compound with solid solution extending both to 31 mole percent In₂O₃ and 71 mole percent In₂O₃. The compound is pseudohexagonal with a_H = 3.69 A and c_H = 12.38 A. Isostructural phases also occur in the 1:1 mixtures of both Gd₂O₃ and Dy₂O₃ with In₂O₃. The melting points of Eu₂O₃ and In₂O₃ were determined to be 2,240 ± 10 °C and 1910 ± 10 °C respectively. A eutectic occurs in the Eu₂O₃−In₂O₃ system at 1,730 °C and about 73 mole percent In₂O₃. The indicated uncertainties in the melting points are conservative estimates of the overall inaccuracies of temperature measurement.     

Experimental and Theoretical Study of Kinetics of Bulk Crystallization in Poly(Chlorotrifluoroethylene)

The rate of isothermal bulk crystallization of poly(chlorotrifluoroethylene), T_m=221° C, was measured from 170° to 200° C. The intrinsic bulk crystallization, which accurately followed an n = 2 law, was shown to be a result of the injection of primary nuclei sporadically in time, with one-dimensional growth of centers derived from these nuclei. The crystallites are exceedingly small. The one-dimensional growth process was isolated by nucleating specimens with seed crystals, and its temperature-dependence determined between 191° and 205° C. The seed crystal isotherms followed an n = 1 law. The temperature coefficients of the rate of nucleation and the rate of growth were both strongly negative.A theory of homogeneous nucleation that takes into account the segmental character of the polymer chains is developed in some detail. A cylindrical nucleus is assumed. In the temperature range near the melting point, region A, where the radius and length of the nucleus are unrestricted, the rate of nucleation is shown to be proportional to exp(−α/T³ΔT²). The nucleation rate is proportional to exp (−β/T²ΔT) in region B, which extends from somewhat below the melting point to considerably lower temperatures; the length of the nucleus has a constant value l₀ in this region, but the radius is unrestricted. (In the above expressions, α and β are constants). Finally, at sufficiently low temperatures, region C is entered. Under certain circumstances, the rate of nucleation in region C will be extremely rapid, and correspond to a “nucleative collapse” of the supercooled liquid state. A calculation of the one-dimensional growth rate shows that it is proportional to exp(−γ/T²ΔT) where β=γ.A careful analysis of the experimental data obtained between 170° and 200° C clearly showed that both the rate of nucleation and the rate of growth were proportional to exp(−β/T²ΔT), and not exp(−α/T³ΔT²). The primary nucleation event was thus of type B in this interval. A detailed analysis of the data is given, and surface free energies and the dimensions of the nuclei quoted. Quenching experiments, where the polymer was crystallized well below 170° C, gave a firm indication of the existence of region C.An experimental study was made of the extremely slow crystallization process that prevailed when the degree of crystallinity became high. The onset of this stage of the crystallization was interpreted as being the result of a massive degree of impingement. This interpretation is justified by the calculations of Lauritzen, who has given a theory of impingements that predicts a pseudoequilibrium degree of crystallinity.As indicated above, the growth process originating at homogeneous nuclei is not of a three-dimensional or spherulitic character in the region of study. Such stray spherulites as do appear in this region are shown to originate at heterogeneities. The possibility that the intrinsic growth process may become three-dimensional at crystallization temperatures sufficiently near T_m is discussed.     

Heat of Formation of Titanium Trichloride

A calorimetric comparison of the heat of hydrolysis of TiCl₄(liq) with the heat of oxidation and hydrolysis of TiCl₃(c) has been made. The following value is reported for the combination of these data according to the process: TiCl3(c)+½I2(c)+HCl(g)→TiCl4(liq)+HI(g),ΔH°(25°C)=8.37±0.30kcal/mole.A combination of this value with −192.3 ±0.7 kcal/mole for the heat of formation of TiCl₄(liq) and with the standard heats of formation of HCl(g) and HI(g) gives for TiCl₃(c), ΔHf°(25 °C) = −172.4±0.8 kcal/mole.     

Group characterization of impact-induced,in vivo human brain kinematics

Brain movement during an impact can elicit a traumatic brain injury, but tissue kinematics vary from person to person and knowledge regarding this variability is limited. This study examines spatio-temporal brain–skull displacement and brain tissue deformation across groups of subjects during a mild impact in vivo. The heads of two groups of participants were imaged while subjected to a mild (less than 350 rad s⁻²) impact during neck extension (NE, n = 10) and neck rotation (NR, n = 9). A kinematic atlas of displacement and strain fields averaged across all participants was constructed and compared against individual participant data. The atlas-derived mean displacement magnitude was 0.26 ± 0.13 mm for NE and 0.40 ± 0.26 mm for NR, which is comparable to the displacement magnitudes from individual participants. The strain tensor from the atlas displacement field exhibited maximum shear strain (MSS) of 0.011 ± 0.006 for NE and 0.017 ± 0.009 for NR and was lower than the individual MSS averaged across participants. The atlas illustrates common patterns, containing some blurring but visible relationships between anatomy and kinematics. Conversely, the direction of the impact, brain size, and fluid motion appear to underlie kinematic variability. These findings demonstrate the biomechanical roles of key anatomical features and illustrate common features of brain response for model evaluation.     

Electronic conduction in La-based perovskite-type oxides

A systematic study of La-based perovskite-type oxides from the viewpoint of their electronic conduction properties was performed. LaCo_0.5Ni_0.5O_3±δ was found to be a promising candidate as a replacement for standard metals used in oxide electrodes and wiring that are operated at temperatures up to 1173 K in air because of its high electrical conductivity and stability at high temperatures. LaCo_0.5Ni_0.5O_3±δ exhibits a high conductivity of 1.9 × 10³ S cm⁻¹ at room temperature (R.T.) because of a high carrier concentration n of 2.2 × 10²² cm⁻³ and a small effective mass m∗ of 0.10 m_e. Notably, LaCo_0.5Ni_0.5O_3±δ exhibits this high electrical conductivity from R.T. to 1173 K, and little change in the oxygen content occurs under these conditions. LaCo_0.5Ni_0.5O_3±δ is the most suitable for the fabrication of oxide electrodes and wiring, though La_1−xSr_xCoO_3±δ and La_1−xSr_xMnO_3±δ also exhibit high electronic conductivity at R.T., with maximum electrical conductivities of 4.4 × 10³ S cm⁻¹ for La_0.5Sr_0.5CoO_3±δ and 1.5 × 10³ S cm⁻¹ for La_0.6Sr_0.4MnO_3±δ because oxygen release occurs in La_1−xSr_xCoO_3±δ as elevating temperature and the electrical conductivity of La_0.6Sr_0.4MnO_3±δ slightly decreases at temperatures above 400 K.     

Heat of Formation of Calcium Aluminate Monosulfate at 25 °C

The heat of formation of calcium aluminate monosulfate, 3CaO·Al₂O₃·CaSO₄·12H₂O, at 25 °C, and of less completely hydrated samples of the same compound, was determined by the heat-of-solution method, with 2N HCl as the solvent, and 3CaO·Al₂O₃·6H₂O(c) and CaSO₄·2H₂O(c), as the reactants. The results were as follows:

Heats of Hydrolysis and Formation of Potassium Borohydride

The heat of reaction of potassium borohydride with 0.060 molal HCl has been measured by solution calorimetry. The heat of solution of the hydrolysis products has also been measured and combined with certain literature values to calculate the process: KBH4(c)+HCl(g)+3H2O(liq)→KCl(c)+H3BO3(c)+4H2(g),ΔH°(25°C)=−354.06±1.84kj/mole(−84.62±0.44kcal/mole).A combination of this value with literature values for the heats of formation of HCl(g), H₂O(liq), KCl(c), and H₃BO₃(c) gives for KBH₄(c): ΔHf°(25°C) = ?228.86 ± 2.30 kj/mole(?54.70 ± 0.55 kcal/mole).Other data on the heats of formation of the alkali-metal borohydrides are discussed briefly.     

The 0–2 Transition of CO in Condensed Oxygen,Nitrogen, and Argon

Infrared absorption spectra of CO in the region of the first overtone have been observed in dilute (approximately 1 to 10 parts in 1000) liquid solutions of oxygen, nitrogen, and argon, and clear crystalline nitrogen and argon matrices. The overtone band was found at 4249.0, 4252.4, and 4252.0 cm⁻¹ with half widths of 18.4, 17.8, and 13.7 cm⁻¹ in liquid oxygen, nitrogen, and argon solutions at 82, 78, and 82 °K, respectively. The half width in liquid oxygen varied from 18.4 to 10.0 cm⁻¹ in the temperature range 82 to 57 °K. The band position was the same but its width was smaller in the crystalline nitrogen matrix. Two bands were observed in the clear crystalline argon solid at 4245 and 4256 cm⁻¹. The solution results cannot be interpreted with the recent theory of Buckingham.Infrared absorption spectra of carbon monoxide in the region of the first overtone have been observed in the liquid solvents oxygen, nitrogen, and argon. In addition, the spectra have been obtained in clear crystalline solutions of argon and of nitrogen near the triple points of these solvents. The purpose of these experiments was to determine the influence of temperature, phase changes, and solvents on half width, position, and shape of the CO absorption band.A Perkin-Elmer model 99 monochromator with a 2000 lines/cm grating blazed at 10° (1.7μ in first order) was used in the first order with a spectral slit width of about 1 cm⁻¹. An antireflection coated germanium filter eliminated the higher orders from the 1000 w tungsten filament lamp used as the light source. The quartz absorption cell used, recently described by Bass and Broida [1], was modified slightly by recessing the windows further into the coolant tube. The resultant increased thermal contact between the refrigerant and the solution greatly simplified the growing of the clear crystalline matrices. The temperature of the refrigerant, liquid oxygen, was regulated by pumping on it with a small vacuum pump (capacity 14 liters/min). The vapor pressure of the liquid oxygen refrigerant, measured with an aneroid type gauge, provided an indication of the temperature. The direct measurement of the vapor pressure above the solution with a mercury manometer also provided an indication of the temperature. Solutions were prepared from the gases which had been mixed in the ratios of 1 to 10 parts carbon monoxide to 1000 parts of the various solvents. The position, the half width, and the shape of the spectral band did not depend on the concentration in this range. The clear solid solutions were grown slowly from the liquids at or near the triple points of the solvents.The measured frequencies and half widths of the 0–2 transition of CO in condensed oxygen, nitrogen, and argon are summarized in 2]). There were no changes in the position or the shape of the band in liquid oxygen at temperatures from 57 to 82 °K. However the half-band width varied from 10.0 to 18.4 cm⁻¹ in this temperature range. In liquid argon the band is slightly asymmetric with more absorption on the high-frequency side.

Table 1

The 0–2 transition of CO in condensed oxygen, nitrogen and argon

Standardization of 63Ni by 4πβ Liquid Scintillation Spectrometry With 3H-Standard Efficiency Tracing

The low energy (E_βmax = 66.945 keV ± 0.004 keV) β-emitter ⁶³Ni has become increasingly important in the field of radionuclidic metrology. In addition to having a low β-endpoint energy, the relatively long half-life (101.1 a ± 1.4 a) makes it an appealing standard for such applications. This paper describes the recent preparation and calibration of a new solution Standard Reference Material of ⁶³Ni, SRM 4226C, released by the National Institute of Standards and Technology. The massic activity C_A for these standards was determined using 4πβ liquid scintillation (LS) spectrometry with ³H-standard efficiency tracing using the CIEMAT/NIST method, and is certified as 50.53 kBq ·g⁻¹ ± 0.46 Bq · g⁻¹ at the reference time of 1200 EST August 15, 1995. The uncertainty given is the expanded (coverage factor k = 2 and thus a 2 standard deviation estimate) uncertainty based on the evaluation of 28 different uncertainty components. These components were evaluated on the basis of an exhaustive number (976) of LS counting measurements investigating over 15 variables. Through the study of these variables it was found that LS cocktail water mass fraction and ion concentration play important roles in cocktail stability and consistency of counting results. The results of all of these experiments are discussed.     

Compressibility of Natural Rubber at Pressures Below 500 kg/cm2

The specific volumes of unvulcanized natural rubber and of a peroxide-cured vulcanizate of natural rubber were measured at pressures of 1–500 kg/cm² at temperatures from 0 to 25 °C. Observations on mercury-filled dilatometers were made through a window in the pressure system. No time effects or hysteresis phenomena were observed. The specific volume V in cm³/e over the range studied can be represented by V = V_0,25{1 + A(t ? 25)}{1 + [α₂₅ + k₁(t ? 25)]P + [β₂₅ + k₂(t ? 25)]P²}where P is the pressure in kg/cm², and t the temperature in °C. The constants for the unvulcanized and for the peroxide-cured samples are:

• V₀,₂₅= 1.0951 and 1.1032 cm³/g;
• 10⁴A = 6.54 and 6.36 per degree;
• 10⁶α₂₅= −50.5 and −50.4 (kg/cm²)⁻¹;
• 10⁶k₁ = −0.227 and −0.203 per degree;
• 10⁹β₂₅= 10 and 11.5 (kg/cm²)⁻²;
• and 10⁹k₂=0.048 and 0.073 per degree, respectively. The compressibility of unvulcanized natural rubber at 25° and 1 kg/cm² is thus 50.5×10⁻⁶ (kg/cm²)⁻¹ falling to 40.6×10⁻⁶ (kg/cm²) ⁻¹ at a pressure of 500 kg/cm². It is concluded that a low degree of vulcanization produces no significant changes in the constants listed. The values are not far different from those obtained by extrapolating to zero sulfur content the observations of Scott on the rubbersulfur system. Calculations of values of compressibility (and its reciprocal the bulk modulus), “internal pressure”, bulk wave velocity, difference between specific heats, and several other physical properties are in reasonable agreement with those obtained by direct observation by other workers. For the prediction of values at pressures above 500 kg/cm² the use of the Tait equation is recommended.