ESR studies on solvation by using <Emphasis Type="Italic">s</Emphasis>-butyl trifluoroacetyl nitroxide probe

Stable s-butyl trifluoroacetyl nitroxide (3) has been generated in electron-transfer reaction of O-benzoyl-N-s-butylhydroxylamine (1) and trifluoroacetyl peroxide (2) in F113 (CFCl₂CF₂Cl) solution at room temperature. ESR measurement of a _N and a _H values for 3 in 21 solvents has been carried out at 24~ 25°C. The a _N values for 3 in 12 aprotic solvents show a linear correlation with the cybotactic solvent parameters E _T and Z, i.e. a _N = 1.35×10-² E _T+6.84, a _N = 0.78×10-² Z+6.88. The physical significance for the slopes, slope × E _T or slope × Z, the extrapolated intercepts on the a _N axis are linked to the sensitivity of the nitroxide toward the solvation, the magnitude of the overall solvaton effect on the a _N values, and the intrinsic a _N value of 3 in the ideal gaseous state, respectively. The plots of a _N versus noncybotactic solvent constants, such as dipolar moment () and dielectric constant (), all show random cases.     

A study of chromic oxide decomposition in an RF argon plasma

Vapor-phase thermal decomposition of chromic oxide in an rf argon plasma was studied using a new experimental system. Homogeneous and heterogeneous modes of reaction were compared, the overall process efficiency being substantially higher for the process carried out entirely in the vapor phase. Reaction products were collected along the reactor wall and studied by chemical methods as well as SEM, X-ray, and IR absorption. The collected powder was highly reactive, fine-grained, and of semiamorphous nature, the average particle size being well below 100 nm. Temperature profiles recorded below the coupling coil by spectroscopic methods were typical of an rf plasma, showing maxima slightly exceeding 5000 K, with the presence of off-axis peaks. Local Cr contents and concentration ratio (Cr)/(Cr₂O₃) in the plasma were determined from the deposition data obtained. A diffusion process was assumed for the wall-deposit buildup. The results obtained confirmed the advantages of using plasma vapor-phase systems, these being higher-efficiency processes and more reliable models than those obtained in the case of gas-solid plasma reactors, where solid particles are injected into the plasma. The thermal decomposition conversion of Cr₂O₃ into Cr was about 8 times higher in the homogeneous gas phase than in the plasma solid phase, all other conditions being equal.Nomenclature c velocity of light, cm × s^–1 - C _Cr ^m metallic Cr content, % by wt. - C _Cr ^t total Cr content, % by wt. - D species diffusivity, cm² · s^–1 - E energy of excited level, eV - f oscillator strength - F rate of species deposition, mol · cm^–2 · s^–1 - g statistical weight - h Planck's constant, J · s^–1 - I radial emission intensity for a given spectral line at a given radius in the plasma, W · sr^–1 · cm^–3 - k Boltzmann's constant, J · K^–1 - l length of collected deposit, cm - m mass of collected deposit, g - M molar weight of Cr - M _Ar ^a molar flow of axial argon, mmol · s^–1 - M _Ar ^p molar flow of peripheral argon, mmol · s^–1 - M _{Cr 2}O₃ molar flow of evaporated Cr₂O₃, mmol · s^–1 - Cr(I) concentration, cm^–3 - Q _T partition function at temperatureT - r reaction radius, cm - R radius of quartz tube, cm - t duration of deposition, s - T temperature, K - total extent of Cr₂O₃ decomposition into Cr, % - Z position of a plane normal to the plasma axis downward the lower turn of rf coil, cm Greek Letters molar ratio of Cr and Cr₂O₃ in deposit - wavelength, nm - species concentration, mol · cm^–3     

Zur Entmischung von kubischen Mehrstoffcarbiden

Zusammenfassung Die Mischungslücke in den Systemen: TiC–{ZrC, HfC} und VC-{NbC, TaC} wird im Bereich von 1200° C bis zur Temperatur des kritischen Punktes experimentell ermittelt und mit Hilfe der freien Exzeß-Enthalpie von der Form: G ^E =x(1–x) {(a ₀+a ₁ T)+(2x–1)(b ₀+b ₁ T)} berechnet.

---

The miscibility gap within the systems: TiC–{ZrC, HfC} and VC—{NbC, TaC} has been experimentally determined in the region from 1200°C up to the temperature of the critical point. A calculation of the binodal curve has been carried out by means of an excess free enthalpy of the form: G ^E =x(1–x){(a ₀+a ₁ T)+(2x–1)(b ₀+b ₁ T)}.

---

---

Mit 4 Abbildungen     

Heat transfer to a particle under plasma conditions with vapor contamination from the particle

Heat transfer to a copper particle immersed into an argon plasma is considered in this paper, including the effects of contamination of the plasma (transport coefficients) by copper vapor from the particle. Except for cases of high plasma temperatures, the vapor content in the plasma is shown to have a considerable influence on heat transfer to a nonevaporating particle, and, to a lesser extent, on heat transfer to an evaporating particle. Evaporation itself reduces heat transfer to a particle substantially as shown in a previous paper [Xi Chen and E. Pfender, Plasma Chem. Plasma Process.,2, 185 (1982)]. Comparisons of the calculated results with those based on a method suggested in the above reference show that the simplified assumptions employed, i.e., that the surface temperature is equal to the boiling point and that plasma properties based on a fixed composition are applicable, can be employed to simplify calculations for many cases. This study reveals that a considerable portion of a particle must be vaporized before a steady concentration distribution is established around the particle.Nomenclature C _p specific heat at constant pressure - D diffusion coefficient of copper in the mixture - D _a diffusion coefficient of copper atoms in the mixture - D _i ambipolar diffusion coefficient of copper ions in the mixture - f mass fraction of copper in the mixture - f _a mass fraction of copper atoms in the mixture - f _i mass fraction of copper ions in the mixture - f mass fraction of copper in the plasma far away from the particle - f _s mass fraction of copper at the particle surface - G total mass flow rate due to evaporation - G _a mass flow rate of copper atoms - G _i mass flow rate of copper ions - H function defined in Eq. (19) - h specific enthalpy - h _s specify enthalpy at the particle surface - h specific enthalpy corresponding toT andf - k thermal conductivity - L latent heat of evaporation - M ₁ molecular weight of argon (M ₁=39.99) - M ₂ molecular weight of copper (M ₂=63.55) - p ₀ pressure of the gas mixture - p _s partial pressure of copper vapor at the particle surface - Q ₀ heat flux to a particle without evaporation - Q ₁ heat flux to a particle with evaporation - R gas constant - r radical coordinate - r _s particle radius - S heat conduction potential defined in Eq. (4) - S _s surface value ofS, corresponding toT _s andf _s - S free-stream value ofS, corresponding toT andf - T temperature - T _b boiling temperature of particle material - T _s particle surface temperature - T plasma temperature - density - T temperature step for numerical integration     

Mass transfer from copper melts by top-blowing of an argon-hydrogen plasma jet

The volatilization of lead, copper, tin, and zinc from copper melts using the technique of top-blowing with an argon-hydrogen plasma jet was experimentally investigated and theoretically evaluated. A plasma burner with 16 kW power was used in the experiments. The mole flow of the plasma gases was 0.017 mol/s (25 liters/min when T = 25°C and P_G = 1 bar). The temperature was 1830°C on the surface of the melt and between 1200 and 1500°C in the molten solution. When the zinc concentration is above 2 mole%, supersaturation of zinc occurs on the surface. In this range of concentrations the ratio of dilution of the concentration in relation to time is linear (zeroth-order reaction). When the concentration of zinc is below 2 mole%, the time dependence of volatilization can be described by an exponential law corresponding to a first-order reaction, because in this case the rate-determining step is the mass transport of zinc in the molten copper phase. From the change from zeroth-order to first-order reaction during the volatilization of zinc, the temperature on the surface of the melt can be estimated with a high degree of accuracy. On the other hand, the volatilization of tin and lead is determined by mass transfer in the gas phase, which leads to an exponential law for the whole range of concentrations. Reaction models were set up on the basis of the experimental data. The relationships thereby obtained permit one to evaluate in advance the yield of future industrial volatilization processes with top-blown plasma jets.Nomenclature A activity - A _e , m² effective mass-transport or mass-transfer area - k, mol/m² s^–1 mass-transfer coefficient - k _g , mol/m² s^–1 mass-transfer coefficient in the gas phase - k _s , mol/m² s^–1 mass-transfer coefficient in the melt phase - k, mol/m² s^–1 overall mass-transfer coefficient - K =P _i /x _i equilibrium coefficient (distribution coefficient) - K _T =P _i /a _i equilibrium coefficient - n _s , mol number of moles of the melt phase - n _G , mol number of moles of the gas phase - n _g , mol/s mole flow of the top-blown gas - n _i , mol/s mole flow of the extract i into the gas phase - P _i , N/ M² partial pressure of extract substance i in the gas phase - t, s time - T, °C or K temperature: T_s, in the melt; T , at the phase interface - x _i , mol/mol concentration in the melt - X _f ¹ , mol/mol concentration in the melt at the phase interface - w, s^–1 rate constant - y _i , mol/mol concentration in the gas phase - y _f ⁱ , mol/mol concentration in the gas phase at interface - z, m coordinate in the direction of mass transfer - activity coefficient - ^O Henry coefficient     

Asymptotic Behavior of the t Expansion

The asymptotic behavior of a system's ground-state energy from the t expansion of Horn and Weinstein has been suggested to have the form E ₁(t)=E ₁+exp(–a _n t+b _n ). In the limit of very large t, this becomes E ₁(t)=E ₁+exp(–a ₁ t+b ₁). A simple analysis shows that the parameters are a ₁=E ₂–E ₁ and b ₁=ln[(E ₂–E ₁)|c ₂|²/|c ₁|²]. Functions are introduced which allow determination of a ₁, b ₁ and lower bounds to E ₁.     

Thermodynamics of Mercurous Acetate from E M. F. Measurements

Measurements of the e.m. f.'s of the cell, have been made over a temperature range from 15° to 40°C. The standard e.m.f. of the Hg/Hg₂Ac₂(s), Ac^? electrode was given by E⁰=?0.8640+1.832×10_×3T?21.84×10_?7T₂. The thermodynamic properties of the reaction, Hg₂Ac₂(s)+2Cl^?=Hg₂Cl₂(s)+2Ac_? and those for the formation of Hg₂Ac₂(s) at 25°C were Computed.     

Study of a hollow cathode arc discharge in the presence of chromium oxide

A hollow cathode arc discharge in hydrogen has been used for the purpose of chromium oxide reduction, the solid oxide being placed inside the anode. Mass transport from the oxide to the gas phase and excitation conditions in the plasma have been investigated. The results show that a substantial amount of oxide is transferred to the gas phase with subsequent reduction and deposition inside the cathode cavity, in the form of a pure metal. The residual part condenses on the discharge chamber wall as an amorphous substance, containing 50–60% of Cr metal, and on the anode surface under the form of a mixture of chromium oxide and metal crystals (10%). From spectroscopic investigations it follows that, inside the anode zone, total Cr concentration in the gas phase is of the order of 10¹⁴ cm^–3, the excitation temperature of the atoms and ions being 4500 and 5500 K, respectively, and the ionization temperature being about 6000 K.Notation I absolute spectral line intensity (W cm^–2 sr^–1) - emission coefficient (W cm^–3 sr^–1) - A relative absorption - absorption coefficient (cm^–1) - L plasma diameter (mm) - f _tk oscillator strength - _D full Doppler width (cm^–1) - S( ₀ L) Ladenburg-Levy function - wave number (cm^–1) - k _pl mass transport rate (mol cm^–2 s^–1) - k _th thermal reduction rate (mol cm^–2 s^–1) - u ion mobility (mm V^–1 s^–1 ) - E electric field strength (V mm^–1) - drift velocity (cm s^–1)     

Estimation of the Critical Temperature of Thermal Explosion for the Highly Nitrated Nitrocellulose Using Non-isothermal DSC

Two methods for estimating the critical temperature (T_b) of thermal explosion for the highly nitrated nitrocellulose (HNNC) are derived from the Semenov's thermal explosion theory and two non-isothermal kinetic equations, d/dt=Af()e^–E/RT and d/dt=Af()[1+E/(RT)(1–T_o/T)]e^–E/RT, using reasonable hypotheses. We can easily obtain the values of the thermal decomposition activation energy (E), the onset temperature (T_e) and the initial temperature (T_o) at which DSC curve deviates from the baseline of the non-isothermal DSC curve of HNNC, and then calculate the critical temperature (T_b) of thermal explosion by the two derived formulae. The results obtained with the two methods for HNNC are in agreement to each other.This revised version was published online in November 2005 with corrections to the Cover Date.     

Electronic structures and MCD spectra of trigonal Cr(III)S6 systems

MCD, electronic absorption, external heavy atom, and crystal field data are presented for the low energy region (² E _g, ² T _1g, ⁴ T _2g) and high energy region (² T _2g, ⁴ T _1g) of Cr(dtp)₃, Cr(dtc)₃, and Cr(exan)₃. At low energy, MCD intensities of ² E(² E _g) and ² E(² T _g) are as large or larger than ⁴ T _2g, and the MCD technique is advantageous over electronic absorption in this respect. The MCD positions of ² E _g and ² T _1g are nearly the same for these molecules ( 13 kK and 13.6 kK) · ⁴ T _2g of this region appears trigonally split ( 500 cm^–1) in the MCD of dtp but to a smaller extent than in the electronic crystal spectrum of Lebedda and Palmer ( 600 cm^–1). MCD did not resolve such components for exan and dtc. The higher energy region includes ² T _2g and ⁴ T _1g, and the combined MCD and electronic absorption data of the three compounds taken together lead us to conclude the ordering ² A ₁(² T _2g)<² E(² T _2g)<⁴ E(⁴ T _1g). The potentially useful external heavy atom affect on the solution-observed electronic ² E and ⁴ E bands of Cr(dtp)₃ did not shed additional light on this order of E states. Finally, it is concluded that the order of ⁴ T _1g and ² T _2g cannot be decided from O _h crystal field calculations because of experimental uncertainties about choosing centers of gravity. In addition, ⁴ T _1g and ² T _2g are close together so that ordering ² E<⁴ E does not guarantee ² T _2g<⁴ T _1g. However, it can be concluded that the ratio C/B4 is not correct, whereas the larger 7<(C/B)<8 is consistent with the data of all three molecules because of small B parameters ( 0.4). Locating OO transitions may somewhat decrease C/B and Dq.

---

Zusammenfassung In der vorliegenden Arbeit werden folgende Meßergebnisse mitgeteilt; MCD, elektronische Absorption, Einfluß eines äußeren schweren Atoms sowie Kristallfelddaten für den Bereich niedriger Energie (² E _g, ² T _1g, ⁴ T _2g) und den Bereich hoher Energie (² T _2g, ⁴ T _1g) von Cr(dtp)₃, Cr(dtc)₃ und Cr(exan). Bei niedriger Energie sind die MCD-Intensitäten von ² E(² E _g) und ² E(² T _1g) genau so groß, oder größer als ⁴ T _2g, und die MCD-Technik bietet Vorteile gegenüber der elektronischen Absorptionsmethode. Die MCD-Werte von ² E _g und ² T _1g sind für die genannten Moleküle etwa gleich ( 13 kK und 13,6 kK). ⁴ T _2g dieses Gebietes erscheint trigonal aufgespalten ( 500 cm^–1) bei MCD von dtp, aber in einem geringeren Maß als im elektronischen Kristallspektrum von Lebedda und Palmer ( 600 cm^–1) MCD löste solche Komponenten bei exan und dtc nicht auf. Der Bereich höherer Energie enthält ² T _2g und ⁴ T _1g, und aus der Kombination von Daten der MCD-Methode sowie der elektronischen Absorption schlossen wir auf die Anordnung ² A _1g(² T _2g)<² E(² T _2g)<⁴ E(⁴ T _1g). Der möglicherweise nützliche Effekt eines äußeren schweren Atoms auf die in Lösung beobachteten elektronischen ² E- und ⁴E-Banden von Cr(dtp)₃ brachte bezüglich dieser Anordnung der E-Zustände nichts Neues. Weiterhin wird gefolgert, daß die Ordnung von ⁴ T _1g und ² T _2g nicht aus O _h-Kristallfeldberechnungen entschieden werden kann, da experimentelle Unsicherheiten bezüglich der Wahl von Schwerpunkten bestehen. Außerdem liegen ⁴ T _1g und ² T _2g nahe zusammen, sodaß aus der Anordnung ² E<⁴ E nicht notwendig ² T _2g<⁴ T _1g folgt. Es kann jedoch gefolgert werden, daß das Verhältnis C/B4 nicht korrekt ist, während 7<(C/B)<8 konsistent mit den Daten aller drei Moleküle ist, da die B-parameter klein sind (0,4). Die Vokalisierung der OO-Übergänge könnten C/B und Dq etwas erniedrigen.

---

---

Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.

---

NDEA Pre-Doctoral Fellow.     

Kinetics of the reactions Br2 + HCN,BrCN + I−, S(CN)2 + I− in aqueous acid solution

Spectrophotometric methods have been used to obtain rate laws and rate parameters for the following reactions: with k_a, k_b, E_a, E_b having the values 85±5 l./mole · s, 5.7±0.2 s^?1 (both at 298.2°K), and 56±4 and 66±2 kJ/mole, respectively. with k_c=0.106±0.004 l./mole ·s at 298.2°K and E_c=67±2 kJ/mole. with k_d=(3.06 ±; 0.15) × 10^?3 l./mole ·s at 298.2°K and E_d=66±2 kJ/mole. Mechanisms for these reactions are discussed and compared with previous work.     

Quadrupole polarizability and hyperpolarizability of carbon monoxide

Summary We report a study of the electric dipole-quadrupole (A _,,), quadrupole-quadrupole (C _,,), dipole-octopole (E _,) polarizability and the dipole-dipole-quadrupole (B _,,) hyperpolarizability of carbon monoxide. All values are obtained from finite-field self-consistent field (SCF) and fourth-order manybody perturbation theory (MP4) calculations. Our best values for the dipole-octopole polarizability areE _z,zzz=60.19 andE _x,xxx=–38.06e ² a ₀ ⁴ E _h ^–1 . For the dipole-dipole-quadrupole hyperpolarizability we reportB _zz,zz=–296,B _xz,xz=–170,B _xx,zz=88 andB _xx,xx=–178e ³ a ₀ ⁴ E _h ^–2 .     

Electroanalytical method for determination of the pesticide dichlorvos using gold-disk microelectrodes

This paper reports the use of laboratory-prepared gold microelectrodes and square-wave voltammetry for analytical determination of low concentrations of the pesticide dichlorvos in pure and natural water samples. After optimization of the experimental and voltammetric conditions, the best voltammetric responses—current intensity and voltammetric profile—were obtained in 0.1 mol L^–1 NaClO₄ with f=100 s^–1, a=50 mV, and E_s=2 mV. The observed detection and quantification limits in pure water were 7.8 and 26.0 g L^–1, respectively. The reproducibility and repeatability of the method were also determined; the results were 1.4% (n=5) and 1.2% (n=10), respectively. Possible interfering effects were evaluated in natural water samples collected at different points with different levels of contamination from agricultural, domestic, or industrial waste from an urban stream. Results showed that the detection and quantification limits increased as a function of the quantity of organic matter present in the samples. Nonetheless, the values observed for these method characteristics were below the maximum value allowed by the Brazilian code for organophosphorus pesticides in water samples. Recovery curves constructed using the standard addition method were shown to be satisfactory compared with those obtained from high-performance liquid chromatography, confirming the suitability of the method for analysis of natural water samples. Finally, when the method was used to determine dichlorvos in spiked cows milk samples, satisfactory recovery and relative standard deviations were obtained.     

Penetration of sodium cetylsulfate into monolayers of 1,2-dipalmitoyl- and 1,2-dimyristoyl-phosphatidylethanolamine

The penetration of sodium cetylsulfate into monolayers of dipalmitoyl- and dimyristoyl-phosphatidylethanolamine was studied by the measurement of surface and penetration pressures using the vertical plate method of Wilhelmy. The penetration isotherms in two systems were investigated at different initial molecular areasA _M :System I: Sodium cetylsulfate/1,2-dipalmitoyl-phosphatidylethanolamine atA _M = 0.85; 0.75; 0.65; 0.55; 0.50; 0.46 and 0.44 nm² · molecule^–1.System II: Sodium cetylsulfate/1,2-dimyristoyl-phosphatidylethanolamine atA _M = 0.85; 0.75; 0.60 and 0.55 nm² · molecule^–1.(T=295 K; substrate 0.1 M NaCl)The penetration isotherms (F _t vs. logc _s ) increase linearly atF _t > 10 mN · m^–1 in system I and atF _t >25 mN · m^–1 in system II. The isotherms of both systems are shifted to lower surfactant concentrations with decreasing molecular area of spread monolayer. A maximum of the slopes (dF_t/d logc _s )occurs at A_M=0.50 nm² · molecule^–1. This behavior is also reflected in the dependenceG _p ⁰ (free standard penetration enthalpy) and _s (relative surface excess concentration of surfactant) onA _M . These changes are related to a different packing of the compounds in the binary penetrated monolayers.In the high pressure region both system are nearly identical. Differences in the low pressure region arise from the penetration into different monolayer states.Nomenclature _M effective cross sectional area of monolayer molecule - a _M partial molecular area of monolayer molecule - a _s partial molecular area of surfactant molecule in the penetrated film - a _s ⁰ molecular area of surfactant molecule at definite film pressure (eq. (3)) - A _M molecular area of theF/A-isotherm - A _N constant in equation (2) - A _K collapse area - b penetration coefficient in equations (2); (2 a) - c _s bulk concentration of surfactant - logc _s relative shift of penetration isotherm with regard to the adsorption isotherm at constantF _t - F film pressure of monolayer component in absence of surfactant - F _t total film pressure - F _p film pressure change due to penetration - F _p,max constant in equation (1) - G _p ⁰ free standard penetration energy - k Boltzmann constant - K constant in equation (1) - R gas constant - T temperature - x _s ⁰ mole fraction of surfactant in the penetrated film - _M surface concentration of monolayer molecules - _s relative adsorption of surfactant - _w ⁰ surface concentration of surfactant in monolayer-free surface - factor in equation (6 a) - surface tension     

On the Role of Surface Forces in Contact Interaction between Elastic Sphere and Hard Surface

The works preformed earlier were reviewed briefly, and the new problem of the contact interaction between the elastic sphere and hard surface was formulated. The solution of a problem to the generalized surface force and its contact and noncontact components was obtained. The specific case of the obtained solution, when the separation = 0, was considered. The existence of two states of contact interaction between the elastic sphere and hard plane was revealed at = 0: (i) the stable state, at contact with the neck of radius a ₁= , where Ris the sphere radius, = (1 – )/(E), Eis the modulus of elasticity of the sphere, is its Poisson's coefficient, and () is the specific energy of adhesion of the surfaces at the lowest possible separation between these surfaces; and (ii) the unstable (metastable) state, at contact with radius a ₂= 0, i.e., at the point contact between the sphere and the plane. In this case, however, the stable contact with the neck at 0 when the modulus of elasticity E , i.e., at the interaction between the hard sphere and hard plane, is also degenerated into the point contact. It was shown that at the point contact, the contact component F _s ^"of the generalized surface force F _svanishes, whereas the noncontact component F _s ^"acquires the value F _s ^"= F _s= 2R() equal to the force of adhesion.     

Discussion on the method for the measurement of the flexural modulus of coupled materials and reasons of the shifts of theQ −1 maxima caused by coupling

Summary When measuringQ ^–1 and the flexural resonance frequency of bars clamped at one end, constituted by a viscoelastic polymeric material glued to a rigid support of modulusE ₁, it is possible to calculate the componentsE ₂ andE ₂ of the complex elastic modulus of the polymeric material examined. In this work the minimum (critical) value of the ratioa=E ₂ /E ₁=a _c and the values of the ratioQ ₂ ^–1/Q ^–1=F ₁ are evaluated beyond which no exact calculation ofE ₂ and ofQ ₂ ^–1 is possible.Within the confidence limits of the linear viscoelasticity theory, these values depend on the accuracy of measurement of both frequency and resonance curve, as well as on the instrument employed, on the operating temperature and on the ratio between the thicknesses of the two coupled materials.In order to keep outside the critical conditions, the most convenient method involves the use of measurements of coupled test-pieces having different ratiosz between their thicknesses and of supports having different modulusE ₁, depending on the field of temperature of the analysis ofE ₂ and tg ₂ concerning and E.P.R. elastomer and a vulcanized cis-1,4 polyisoprene in very wide ranges of temperature comprising the glass transition. Moreover, it is demonstrated by analysis the shift on the temperature axis of the tg maximum of the composite test-piece with respect to the position of the tg maximum of the polymeric material alone.With 11 figures and 1 table     

Characterisation of the surface of a cellulosic multi-purpose office paper by inverse gas chromatography

The surface of multi-purpose cellulosic office paper has been analysed by inverse gas chromatography (IGC). The parameters determined were the dispersive component of the surface free energy, the enthalpy of adsorption and the entropy of adsorption of polar and apolar probes, the Lewis acidity constant, K _a, and the Lewis basicity constant, K _b. It can be concluded that the dispersive component of the surface free energy, _s ^d decreases with temperature, in the range 50–90°C. The temperature coefficient of _s ^d, d_s ^d/dT, is –0.35 mJm ^–2K^–1. The values of K _a and K _b were determined to be 0.11±0.011 and 0.94±0.211, respectively. The predominant surface basicity agrees with expectation, bearing in mind the presence of calcium carbonate, and of a styrene-acrylic copolymer, in the surface sizing formulation. It is thought that during the drying stages following the surface sizing treatment, the starch used as the binder migrates to the interior of the surface sizing layer and then to the paper bulk itself. This migration contributes to a decrease in the hydrophilicity of the surface, and also results in the surface showing only slight Lewis.     

Collision-induced emission of O2(b1Σ → a1Δg) in the gas phase

In flow tube studies of the quenching of O₂(b¹Σ), broad band emission of O₂(b):M collision complexes was found to appear under the discrete rotational lines of the 0–0 band of the b¹Σ → a¹Δ_g electric quadrupole transition at higher oxygen pressures and on addition of foreign gases. Bimolecular rate constants for the collision-induced emission processes have been derived from the ratio of the intensities of the discrete lines and the continuum as well as from low-resolution measurements of the relative intensities of the b → a and b → X bands as a function of O₂ and added gas pressure. They range from ≈10^?21 cm³ s^?1 for He to ≈4 × 10^?19 cm³ s^?1 for PCl₃ vapor.     

Optical and Electrical Properties of Polymerizing Plasmas and Their Correlation with DLC Film Properties

Diamond-like carbon (DLC) films were grown from radiofrequency plasmas of acetylene-argon mixtures, at different excitation powers, P. The effects of this parameter on the plasma potential, electron density, electron temperature, and plasma activity were investigated using a Langmuir probe. The mean electron temperature increased from about 0.5 to about 7.0 eV while the mean electron density decreased from about 1.2 × 10⁹ to about 0.2 × 10⁹ cm^–3 as P was increased from 25 to 150 W. Both the plasma potential and the plasma activity were found to increase with increasing P. Through actinometric optical emission spectrometry, the relative concentrations of CH, [CH], and H, [H], in the discharge were mapped as a function of the applied power. A rise in [H] and a fall in [CH] with increasing P were observed and are discussed in relation to the plasma characteristics and the subimplantation model. The optical properties of the films were calculated from ultraviolet-visible spectroscopic data; the surface resistivity was measured by the two-point probe method. The optical gap, E _G, and the surface resistivity, _s, fall with increasing P. E _G and _s are in the ranges of about 2.0–1.3 eV and 10¹⁴–10¹⁶ /, respectively. The plasma power also influences the film self-bias, V _b, via a linear dependence, and the effect of V _b on ion bombardment during growth is addressed together with variation in the relative densities of sp² and sp³ bonds in the films as determined by Raman spectroscopy.     

Some perspectives on the modeling of plasma jets

A mathematical representation is developed describing the temperature and the velocity profiles and mixing in a plasma jet discharging into ambient air. In the model, realistic allowance is made for turbulent behavior, the temperature-dependent property values, and also for the boundary conditions, including entrainment. The more precise definition of the boundary conditions, mixing, and entrainment are thought to be important novel features of this work. The theoretical predictions were found to be in good agreement with measurements reported by Vardelle regarding the behavior of a nitrogen plasma, but the agreement was less satisfactory for an argon plasma jet. Possible reasons for the discrepancy are discussed.Notation C ₁,C ₂,C _D constants inK- turbulence model - h enthalpy - H ₁ length of integration region - H ₂ width of integration region - K turbulent kinetic energy per unit mass - m mass concentration of plasma - Q _f mass flow rate of plasma gas for flat inlet profiles - Q _P mass flow rate of plasma gas for parabolic inlet profiles - P _w torch power - r radial coordinate - R ₀ internal radius of torch exit - S source term for dependent variable - S _R radiation loss per unit volume of plasma - T _a ambient temperature - T _m maximum temperature - T _t torch tip temperature - u velocity inz-direction - u _{C 1} velocity at and in the direction of the symmetry axis of the flow - u _m velocity of plasma atr=0 andz=0 (maximum velocity) - u axial direction velocity difference across the width of the mixing region - v velocity in r direction - Y radial width of the mixing region - z axial coordinate - density - , _e, _t molecular, effective, and turbulent viscosities, respectively - dissipation rate of turbulence energy - thermal efficiency of plasma torch - Prandtl/Schmidt number forh, K, , andm Visiting Fulbright Scholar and Associate Professor of Chemical Engineering, on leave from the Institute of Chemical Engineering and Technology, Punjab University, Lahore-20, Pakistan.