The reaction of nitric oxide with vibrationally excited ozone

The reaction between nitric oxide and vibrationally excited ozone was studied in a fast flow reactor by monitoring the visible emission from electronically excited NO₂¹. The antisymmetric mode (ν₃) of O₃ was excited with a Q-switched 9.6 μm CO₂ laser, and a laser-induced signal was detected, with a rise rate constant of (4.0 ± 0.5) × 10¹¹ cm³/mole sec and a decay rate constant of (1.1 ± 0.1) × 10¹¹ cm³/mole sec for an NO-rich mixture. The latter was unaffected by addition of large amounts of He or Ar, indicating that the signal was not a thermal effect. Most of the measurements were made at 350°K; however, the He and Ar dilution results suggest that the enhanced reaction rate is not very sensitive to temperature. In order to explain the observed rise times, it was necessary to postulate an intermediate step prior to the chemical reaction. A model which is consistent with our data has energy transferred from ν₃ to ν₂ (the bending mode) at a rate of (2.9 ± 0.5) × 10¹¹ cm³/mole sec for NO and a rate of (1.1 ± 0.2) × 10¹¹ cm³/mole sec for He. According to this model, the rate constant for the reaction of NO with O₃ (ν₂= 1) producing vibrationally excited ground state NO₂²,

$\text{NO + O}{}_3{}^2\text{(010)}\text{3}\text{NO}{}_2{}^2\text{+ O}{}_2$

is (1.5 ± 0.2) × 10¹¹ cm³/mole sec, and the relative rate for the reaction of O₃ (ν₂ = 1) and O₃(ν₂ = 0) with NO was estimated to be $\text{k}{}_3\text{(1)}\text{k}{}_3\text{(0)}\text{≈ 22}$.     

Nachbargruppeneffekte bei der aminolyse von estern—I: Kinetik der aminolyse von nitrophenylacetaten mit n-butylamin in dioxan

The kinetics of the aminolysis of different nitrophenylacetates were investigated with n-butylamine in dioxane at 20°C. The reaction rate can be described up to high concentrations of amine (~1 mole dm^?3) by the equation v=k₂[ester][amine]+k₃[ester][amine]². The ratio $\text{k}{}_3\text{k}{}_2$ is larger for p-nitrophenylacetates than for o-nitrophenylacetates, while for 2,4-dinitrophenylacetates a third order term is not observed.     

Determination of the vapour pressures of o-, m-, and p-dinitrobenzene by the torsion-effusion method

The vaporization of o-, m-, and p-dinitrobenzenes was investigated by means of the torsion-effusion method and the selected equations for vapour pressure p as a function of temperature T are:

$\text{o-dinitrobenzene: log}{}_{10}\text{(}\text{p}\text{atm}\text{)=(7.03±0.34)?(4270±120)}\text{K}\text{T}\text{,m-dinitrobenzene: log}{}_{10}\text{(}\text{p}\text{atm}\text{)=(7.66±0.28)?(4400±100)}\text{K}\text{T}\text{,p-dinitrobenzene: log}{}_{10}\text{(}\text{p}\text{atm}\text{)=(8.34±0.34)?(4860±120)}\text{K}\text{T}$

The sublimation enthalpies ΔH^o(o-, 298.15 K) = (21.0 ± 0.5) kcal_th mol^?1, ΔH^o(m-, 298.15 K) = (20.8 ± 0.2) kcal_th mol^?1, and ΔH^o(p-, 298.15 K) = (23.0 ± 0.6) kcal_th mol^?1, are also derived by means of the second- and third-law treatments of the results.     

Mutual solubility of n-butanol + water under high pressures

The mutual solubilities of {xCH₃CH₂CH₂CH₂OH+(1-x)H₂O} have been determined over the temperature range 302.95 to 397.75 K at pressures up to 2450 atm. An increase in temperature and pressure results in a contraction of the immiscibility region. The results obtained for the critical solution properties are: T_o(U.C.S.T.) = 397.85 K and x_o = 0.110 at 1 atm; $\text{(}\text{dT}{}_{\mathrm{o}}\text{d}\text{p}\text{) = ?(12.0±0.5)×10}{}^{\mathrm{?3}}\text{K atm}{}^{\mathrm{?1}}$ at p < 400 atm and $\text{(}\text{dT}{}_{\mathrm{o}}\text{d}\text{p}\text{) = ?(7.0±0.7)×10}{}^{\mathrm{?3}}\text{K atm}{}^{\mathrm{?1}}$ at 800 atm < p < 2500 atm; $\text{(}\text{dx}{}_{\mathrm{o}}\text{d}\text{T}\text{) = ?(4.0±0.5)×10}{}^{\mathrm{?4}}\text{K}{}^{\mathrm{?1}}$.     

Polymerization in liquid crystals—IV: The polymerization of cholesteryl-vinyl-succinate

The solid-, cholesteric- and liquid-state polymerizations of cholesteryl-vinyl-succinate (CVS) are studied. Only one of the three polymorphic modifications of CVS oligomerizes in the solid state into oligomers of degree $\text{P}\text{= 2}\text{to}\text{6}$ in a homogeneous topochemical reaction. The rate of polymerization in the cholesteric state is lower than that in the liquid state at the same temperature. Kinetic constants were measured at 85° using benzoyl peroxide as initiator and the Banfield radical, giving E_overall = 15.4, 36.4 kcal/mole^?1; $\text{f = 0.52, 0.19; k}{}_{\mathrm{p}}\text{/k}{}_{\mathrm{t}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 0.0167, 0.0192}$, (1/mole sec)^{$\text{1}\text{2}$}, ($\text{E}{}_{\mathrm{p}}\text{?}\text{1}\text{2}\text{E}{}_{\mathrm{t}}\text{) = 0.40, 21.4}$ kcal mole^?1. The values refer to the liquid- and the cholesteric-state reactions, respectively. The average degree of polymerization is low in both cases ($\text{P}\text{= 20}\text{and}\text{22}$). It was concluded that the molecular weights are controlled by chain transfer and that the initiation reaction is mostly dependent on the phase where the reaction takes place.     

Tracer diffusion coefficient of oxide ions in LaCoO3 single crystal

The tracer diffusion coefficient, $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$, of oxide ions in LaCoO₃ single crystal was determined over the temperature range of 700–1000°C by a gas-solid isotopic exchange technique using ¹⁸O tracer. For the determination, two methods, the gas phase analysis and the depth profile measurement, were employed. Under an oxygen pressure of 34 Torr, the temperature dependence of $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$ in LaCoO₃ was expressed by

$\text{D1}{}_{\mathrm{<mtext>O</mtext>}}\text{(}\text{cm}{}^2\text{·}\text{sec}{}^{\mathrm{?1}}\text{) = 3.63 × 10}{}^4\text{exp}\text{?}\text{(74 ± 5)}\text{kcal}\text{·}\text{mole}{}^{\mathrm{?1}}\text{RT}$

$\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$ at 950°C was found to be proportional to P^?0.35_O2. The diffusion of oxide ions occurs through a vacancy mechanism. The activation energy for the migration of oxide ion vacancies was estimated as 18 kcal · mole^?1.     

The thermal polymerization of styrene at temperatures up to 250°

The kinetics of the thermal polymerization of styrene have been studied over the range 60–250°. The overall energy of activation was 86 ± 2 kJ/mole, a value identical to that obtained for the thermal polymerization of styrene in diethyl adipate. As expected, the molecular weight of the polymer decreases with increase in the temperature of the polymerization, and the ratio $\text{M}{}_{\mathrm{<mtext>w</mtext>}}\text{M}{}_{\mathrm{<mtext>n</mtext>}}$ becomes greater than 2 for polymer formed at above 140°. The plot of log ($\text{1}\text{M}{}_{\mathrm{<mtext>n</mtext>}}$) against (absolute temperature)^?1 can be represented by two straight lines yielding 24.5 and 32,0 kJ/mole for the activation energies at temperatures below 120° and above 140°, respectively. The former value is in keeping with the molecular weight being controlled by chain transfer with monomer; the latter value would be that expected if the termination process controls the molecular weight of the polymer. Mark Houwink relationships between intrinsic viscosity and $\text{M}$_n and $\text{M}$_w have been found to apply to polymer samples when the molecular weight averages were determined by osmometry and by light scattering. However, deviations were found for low molecular weight material when measured using gel permeation chromatography. The K values were considerably lower, and the α values higher than reported in the literature.     

Infrarotspektroskopische und röntgenographische Untersuchungen von Bleihydroxylapatit,Bleioxyapatit und Bleialkaliapatiten

The infrared spectra of lead hydroxyapatite Pb₁₀(PO₄)₆(OH)₂, oxyapatite Pb₁₀(PO₄)₆O, and the lead alkaliapatites Pb₈M₂(PO₄)₆ (M = Na, K, Rb, T1) were investigated down to 200 cm^?1. There are significant differences between all these spectra. In the hydroxy- and oxyapatite spectrum one band is ascribed to the translational motion of the OH^? and O^2? ions, respectively. The thermal dependance of the dehydration of hydroxy to oxyapatite was studied by X-ray methods, both compounds forming a solid solution. The heat of decomposition of hydroxyapatite was found to be ΔH = 5 kcal/mole. Moreover, complete miscibilities could be shown to exist in the systems $\text{Pb}{}_8\text{Na}{}_2\text{(PO}{}_4\text{)}{}_6\text{Pb}{}_{10}\text{(PO}{}_4\text{)}{}_6\text{O}$ and $\text{Pb}{}_8\text{Na}{}_2\text{(PO}{}_4\text{)}{}_6\text{Pb}{}_{10}\text{(PO}{}_4\text{)}{}_6\text{(OH)}{}_2$, respectively.     

Molecular structure of 1,1-dichloroethylene as studied by gas electron diffraction and microwave data. Estimation of equilibrium structure by an extended anharmonic model analysis

The r_z structure of 1,1-dichloroethylene has been determined by a joint analysis of the electron diffraction intensity and the rotational constants as follows: $\text{r}{}_{\mathrm{<mtext>z</mtext>}}\text{(}\text{CH}\text{) = 1.088 ± 0.011, r}{}_{\mathrm{<mtext>z</mtext>}}\text{(}\text{CC}\text{) = 1.329 ± 0.003, r}{}_{\mathrm{<mtext>z</mtext>}}\text{(}\text{CCl}\text{) = 1.725 ± 0.002}\text{A}\text{?}\text{, ∠}{}_{\mathrm{<mtext>z</mtext>}}\text{HCH}\text{= 121.4 ± 0.7}\text{and}\text{∠}{}_{\mathrm{<mtext>z</mtext>}}\text{ClCCl}\text{= 114.1 ± 0.2°}$. The uncertainties represent estimated limits of error. The observed structural parameters are compared with those for related compounds and the systematic trends in the bond lengths and bond angles are discussed. The effective constants representing anharmonicity have been obtained from an analysis of the isotopic differences in the r_z structure. By using the r_z parameters and the effective constants, the equilibrium structure has been estimated as follows: $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{(}\text{CH}\text{) = 1.079 ± 0.012, r}{}_{\mathrm{<mtext>e</mtext>}}\text{(}\text{CC}\text{) = 1.324 ± 0.005, r}{}_{\mathrm{<mtext>e</mtext>}}\text{(}\text{CCl}\text{) = 1.721 ± 0.003}\text{A}\text{?}\text{, ∠}{}_{\mathrm{<mtext>e</mtext>}}\text{HCH}\text{= 120.5 ± 0.8}\text{and}\text{∠}{}_{\mathrm{<mtext>e</mtext>}}\text{ClCCl}\text{= 114.0 ± 0.3°}$.     

Primary radical termination in polymerization: Evaluation of the characteristic constant

Polymerization experiments with styrene in benzene at 60°, initiated by benzoyl peroxide, covering a wide range of concentration of both monomer and initiator are reported; the results cannot be explained in terms of the classical rate relationship with $\text{R}{}_{\mathrm{p}}\text{∝ [}\text{I}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{[}\text{M}\text{]}$. Deviations were reflected in unexpected orders of monomer up to [M]^1·4 and of initiator down to [I]^0·42 when the initiator concentration is increased and monomer concentration is decreased. Based on the concept of primary radical termination, an equation, viz.

$\text{ln}\text{R}\text{p}\text{2}\text{[I][M]}{}^2\text{=}\text{ln}\text{2f}{}_{\mathrm{k}}\text{k}{}_{\mathrm{d}}\text{k}\text{p}\text{2}\text{k}{}_{\mathrm{t}}\text{?2}\text{k}{}_{\mathrm{prt}}\text{k}{}_{\mathrm{i}}\text{k}{}_{\mathrm{p}}\text{×}\text{R}{}_{\mathrm{p}}\text{[M]}{}^2$

is proposed. Semi-log plots of R_p²/[I] [M]² vs R_p/[M]² show a wide range of linearity; the characteristic constant k_prt/k_ik_p and also f_k can be obtained from the slope and intercept, respectively, k_prt, k_i and k_p are, respectively, the rate constants of primary radical termination, initiation and propagation and f_k is the efficiency of initiation, defined as the fraction of radicals which come out of the solvent cage and take part in initiation, primary radical termination and primary radical recombination. The definition of f_k is thus differentiated from the conventional efficiency of initiation. Finally, we have derived an equation which allows determination of the classical efficiency of initiation as a function of [I]/[M]² and also allows a correction of R_p in handling the above equation by taking into account the small amount of monomer consumed in initiation.     

Polymerisation radiochimique de l'acetaldehyde en phase solide

The radiation induced solid-state polymerization and post-polymerization of crystalline acetaldehyde were studied in a diathermic calorimeter by measuring the heat evolution during polymerization. The heat of melting of crystalline acetaldehyde was found to be 1,4 ± 0,07 kcal mol^?1 and the heat of polymerization 2,5 ± 0,5 kcal mol^?1 at 80–150°K. Under isothermal conditions the rate of the solid state polymerization of acetaldehyde increased with irradiation time up to a maximum and thereafter it decreased. This phenomenon is connected with an increase of the concentration of active centres during irradiation. The propagation rate constant is $\text{k}{}_{\mathrm{p}}\text{? 5 × 10}{}^{\mathrm{?4}}\text{exp(?11,000/RT) cm}{}^3\text{sec}{}^{\mathrm{?1}}$ at 130–140°K and the average time of addition of one monomer unit is 10^?1–10^?2 sec.     

Termination and transfer of the polymer chain to a maleimide derivative containing the azo group

The copolymerizations of N-(3-dimethylaminophenyl) maleimide (I) and 4-(2-chlorophenyl)azo-3-maleimido-N,N-dimethylaniline (II) with styrene were investigated; the copolymerization parameters of the pairs ($\text{I}\text{+}\text{styrene}$) and ($\text{II}\text{+}\text{styrene}$) and $\text{k}{}_{\mathrm{p}}\text{/k}{}_{\mathrm{t}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ hr I at 50° were determined; chain transfer to the maleimide ring of I was proved. The homopolymerization of styrene in the presence of 4-(2-chlorophenyl)azo-succinimide-N,N-dimethylaniline (III) was used to determine the ratio of the rate constant for addition of the polystyrene radical to the azo group in III to k_p for styrene.     

Diffusion of oxide ions in LaFeO3 single crystal

The tracer diffusion coefficient, $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$, of oxide ions in LaFeO₃ single crystal was determined over the temperature range of 900–1100°C by the gas-solid isotopic exchange technique using ¹⁸O as a tracer. For the determination of $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$, the depth profile of ¹⁸O was measured by means of a secondary ion mass spectrometer (SIMS). The surface exchange reaction was found to be slow and the surface exchange rate constant, k, was determined together with $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$. It was found that $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$ at 950°C is proportional to P^?0.58_O2, where P_O2 is an oxygen pressure. The vacancy mechanism was determined for the diffusion of oxide ions from the P_O2 dependence. The vacancy diffusion coefficient, D_V, for LaFeO₃ was nearly the same as that for LaCoO₃ at the same temperature. The activation energy for migration of oxide ion vacancies was 74 kJ · mole^?1 for both oxides.     

Thermal degradation and oxidation of polystyrene studied by factor-jump thermogravimetry

Factor-jump thermogravimetry has been used to study the activation energy of polystyrene degrading in a vacuum, in N₂ flowing at 4 mm/s and in $\text{N}{}_2\text{O}{}_2$ mixtures. The results show the activation energy to be 44·9 ± 0·2 kcal/mole (188 ± 0·8 kJ/mole) for degradation above 350°C in vacuum or in flowing N₂. This agrees well with work reported in 1949 by Jellinek⁷ but with few results reported subsequently.The apparent activation energy for polystyrene losing weight above 280°C in an atmosphere of abundant O₂ is 21·5 ± 0·2 kcal/mole (90·2 ± 0·8 kJ/mole). In all cases where O₂ was deliberately introduced (partial pressures >4 mm Hg), the sample degraded to a black tar and the activation energy was ≤30 kcal/mole, depending on the amount of oxygen present and on the thermal history of the sample.     

On the kinetics of polymer degradation in solution—VI Laser flash photolysis and pulse radiolysis studies of polymethylvinylketone in solution using the light scattering detection method

Polymethylvinylketone (PMVK) was irradiated in solution with 2 μs pulses of 15 MeV electrons or with 15 ns flashes of 265 nm light. The change of the intensity of the light scattered by the solution (LSI) after the irradiation was measured. For the radiolysis experiments, a main chain scission process ($\text{τ}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(}\text{decr}\text{) ≈ 20 μ}\text{s}$) and a subsequent crosslinking process [$\text{τ}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(}\text{incr}\text{) ≈ 0.4}\text{sec}$] could be discriminated. The LSI change pertaining to the main chain degradation was found to be due to disentanglement diffusion, whereas the LSI change pertaining to the crosslinking process could be correlated to a chemical reaction. The rate constant for combination of lateral macroradicals in acetone solution was estimated as 2 k₂ = (4.5 ± 1.5)10⁶M^?1 sec^?1. Stationary irradiations with ⁶⁰Co-γ-rays showed that PMVK is predominantly crosslinked to form a macrogel when irradiated in the solid state or in solution at concentrations greater than 100 g/l. At lower concentrations, microgel formation occurred.Photolysis of PMVK in solution yielded only main chain degradation. The LSI change was found to be due to disentanglement diffusion as during radiolysis. It was concluded that the same mechanism for main chain rupture is operative as in radiolysis. Stationary irradiations with u.v. light (λ > 260 nm) resulted in main chain degradation; no indication of crosslinking was obtained.     

Standard enthalpies of formation of uranium compounds I. β-UO3 and γ-UO3

The standard enthalpy of formation of γ-UO₃ has been critically assessed; the value ?(292.5 ± 0.2) kcal_th mol^?1 is suggested.The enthalpies of solution of β-UO₃ and γ-UO₃ in 3 M H₂SO₄ have been measured and used to derive:

$\text{ΔH}{}_{\mathrm{f}}{}^{\mathrm{°}}\text{(β?}\text{UO}{}_3\text{, 298.15}\text{K}\text{) = ?(291.6 ± 0.2)}\text{kcal}{}_{\mathrm{th}}\text{mol}{}^{\mathrm{?}}$

     

Chiral 1,4-benzodiazepines—-XI: Kinetics of degenerate nucleophilic exchange of C(3)-hydroxy group

The rate for degenerate nucleophilic exchange (k_e) of the C(3)-OH group in the racemic compound 1 was determined in DMSO/H₂¹⁸O using mass spectrometry. Epimerization rates for diastereomers 15 and 16 were determined by polarimetry (k_ep) and NMR spectroscopy (k_r-c—for $\text{r}$ing-$\text{c}$hain tautomery). The ratio $\text{k}{}_{\mathrm{e}}\text{k}{}_{\mathrm{ep}}$ ~ 3.5 35° is close to that obtained for degenerate nucleophilic exchange of the C(3)-OMe group in the compound 1a ($\text{k}{}_{\mathrm{e}}\text{k}{}_{\mathrm{\alpha }}$ ~4, Refs. [3,4]). These data confirm the C(3)-OH substituted 1,4-benzodiazepin-2-ones lose the configurational identity of the C(3) chiral centre by both direct nucleophilic substitution of the OH group, and ring-chain tautomery processes.The synthesis of the diastereomeric compounds 15 and 16, and their chromatographic separation is described.     

Diffusion of point defects participating in solid-phase chemical reactions (trap diffusion): Demonstration for the Ti3+ → Ti4+ transition in corundum

A problem of trap diffusion, that is diffusion of point defects in crystals participating in a solid-phase chemical reaction with motionless impurity ions, is solved. Time dependences of the reaction-front displacement, X_f, and its steepness, $\text{(}\text{?C}\text{?X}\text{)}{}_{\mathrm{f}}$ are determined analytically for N₀ ? C₀ and numerically for all relations of N₀ and C₀$\text{x}{}_{\mathrm{f}}{}^2\text{=2}\text{N}{}_0\text{C}{}_0\text{Dt; (}\text{ac}\text{ax}\text{)}{}_{\mathrm{f}}\text{=0.3C}{}_0{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{(}\text{g}\text{D}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2></mtext>}}$where C₀ and N₀ are the initial concentration of impurity and the eqilibrium defect concentration, respectively, D is a diffusion coefficient, and g is a chemical reaction constant. Dependence of X_f vs C₀ and t is confirmed for oxygen annealing of corundum crystals doped with titanium which, reacting with the point defects, changes its valency. The data are obtained for dependence of displacement X_f upon partial oxygen pressure and thermotreatment temperature as well as upon the sign of the constant electric field applied to the sample. From these data we conclude that the reaction of titanium impurity, changing from the three-valent to the tetravalent state at the activation energy of 80 ± 8.5 kcal/mole is due to anisotropic diffusion of charged aluminum vacancy and holes in the valence band. The diffusion coefficient for that process at 1500°C is estimated to be larger than 10^?5 cm²/sec. Using the trap-diffusion features, the concentration of optical centers of the 0.315-μm absorption band in ruby is also estimated.