Experimental Research of OH and N<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> Spatially Resolved Spectra in a Needle-Plate Pulsed Streamer Discharge

In this study, the spatial distributions of the emission intensity of OH (\(\hbox{A}^{2}\Upsigma {\rightarrow}\hbox{X}^{2}\Uppi,\) 0-0) and \(\hbox{N}_{2}^{+} (\hbox{B}^{2}\Upsigma_{\rm u}^{+}\rightarrow \hbox{X}^{2}\Upsigma_{\rm g}^{+},\) 0-0, 391.4 nm) are investigated in the atmospheric pressure pulsed streamer discharge of H₂O and N₂ mixture in a needle-plate reactor configuration. The effects of pulsed peak voltage, pulsed repetition rate, input power, and O₂ flow rate on the spatial distributions of the emission intensity of OH (\(\hbox{A}^{2}\Upsigma {\rightarrow}\hbox{X}^{2}\Uppi,\) 0-0), \(\hbox{N}_{2}^{+} (\hbox{B}^{2}\Upsigma _{\rm u}^{+} \rightarrow \hbox{X}^{2}\Upsigma _{\rm g}^{+},\) 0-0, 391.4 nm), and the vibrational temperature of N₂ (C) in the lengthwise direction from needle to plate are attained. It is found that the emission intensities of OH (\(\hbox{A}^{2}\Upsigma {\rightarrow}\hbox{X}^{2}\Uppi,\) 0-0) and \(\hbox{N}_{2}^{+} (\hbox{B}^{2}\Upsigma_{\rm u}^{+} \rightarrow \hbox{X}^{2}\Upsigma_{\rm g}^{+},\) 0-0, 391.4 nm) rise with increasing the pulsed peak voltage, the pulsed repetition rate and the input power, and decrease with increasing O₂ flow rate. In the direction from needle to plate, the emission intensity of OH (\(\hbox{A}^{2}\Upsigma {\rightarrow}\hbox{X}^{2}\Uppi,\) 0-0) decreases firstly, and rises near the plate electrode, while the emission intensity of \(\hbox{N}_{2}^{+}(\hbox{B}^{2}\Upsigma_{\rm u}^{+} \rightarrow \hbox{X}^{2}\Upsigma_{\rm g}^{+},\) 0-0, 391.4 nm) is nearly constant along the needle to plate direction firstly, and rises sharply near the plate electrode. The vibrational temperature of N₂ (C) is almost independent of the pulsed peak voltage and the pulsed repetition rate, but rises with increasing the O₂ flow rate and keeps nearly constant in the lengthwise direction. The main physicochemical processes involved are discussed.     

Oxide eines neuen Formeltyps: Zur Kenntnis von K3Ni2O4 und K3Pt2O4

Oxides of a New Type of Formula: On the Knowledge of K₃Ni₂O₄ and K₃Pt₂O₄ K₃Ni₃O₄, greyblack single crystals, obtained by heating K₂O and NaNiO₂ [K:Ni = 2:1, 500°C, 7d, Ag-cylinders], crystallizes orthorhombic with a = 6.04₄, b = 9.04₉, c = 10.56₇ Å, Z = 4, space group Cmcm (d_rö = 3.43, d_pyk = 3.32 g · cm^?3). Due to four cycle diffractometer data (374 hkl, MoKα, R = 8.6percnt;) a new type of structure is found with wavebands of [NiO_4/2] \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm 1} $\end{document} exhibits the C.N. 6, \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm 2} $\end{document} the C.N. 4. Effective Coordination Numbers, ECoN, calculated by means of Mean Fictive Ionic Radii, MEFIR, the Madelung Part of Lattice Energy, MAPLE and the magnetic properties are discussed. K₃Pt₂O₄, black single crystals with metallic lustre, obtained by heating KO_x (x = 1.55 or 1.88) and Pt (powder) [K:Pt = 4:1,1000°C, lh, 600°C, 2d, Pt-capsules] is isotypic to K₃Ni₂O₄ (four cycle diffractometer data: 458 hkl, MoKα, R = 12percnt;). Cellparameters are a = 6.15, b = 9.27, c = 11.51 Å (single crystal data), d_rö = 5.79 and d_pyk = 5.77 g · cm^?3.     

Polymerization of σ-bonded organo-transition metal derivatives of styrene

Five new monomers of transition metal complexes containing a styryl group, trans-\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Pd}({\rm PBu}_{\rm 3})_2 \rlap{--} ({\rm C}_6 {\rm H}_4 {\rm CH} \hbox{=\hskip-2pt=} {\rm CH}_2 ){\rm X\ X \hbox{=\hskip-2pt=} Cl(Ia),\ X \hbox{=\hskip-2pt=} Br(Ib)},\ {\rm X \hbox{=\hskip-2pt=} CN(Ic),\ X \hbox{=\hskip-2pt=} Ph(Id)} $\end{document} and trans-\documentclass{article}\pagestyle{empty}\begin{document}${\rm Pt(PBu}_{\rm 3} {\rm )}_{\rm 2} \rlap{--} ({\rm C}_{\rm 6} {\rm H}_{\rm 4} {\rm CH} \hbox{=\hskip-2pt=} {\rm CH}_2 ){\rm Cl}({\rm II})$\end{document}, were synthesized. The monomers were readily homopolymerized in benzene with the use of AIBN or BBu₃–oxygen as the initiator. Copolymerization of Ia with styrene was carried out by using AIBN. From the Cl content of the copolymers by analysis, monomer reactivity ratios and Q–e values were obtained as follows: r₁ = 1.49, r₂ = 0.45; Q₂ = 0.41, e₂ = ?1.4 (M₁ = styrene, M₂ = Ia). Based on the above data, the σ-bonded palladium moiety at para position of styrene acts as a strongly electron-donating group to the phenyl ring. This is also supported by the olefinic β-carbon chemical shift of ¹³C NMR for Ia.     

Zur Kenntnis der Organophosphorverbindungen. XV. Darstellung und Reaktionen von Trimethylsilylestern der Phosphinsäuren

On Organophosphorus Compounds. XV. Preparation and Reactions of Trimethylsilyl Esters of Phosphinic Acids Trimethylsilylesters of Phosphinic acids R₂P(X)YSi(CH₃)₃ (R ? CH₃, C₂H₅, C₃H₇, t?C₄H₉, C₆H₅; X, Y ? O, S) were prepared by 7 different methods as in some cases easily hydrolysable but thermally remarkably stable compounds. The properties and some reactions of these substances are reported, their structures confirmed by IR? as well as ¹H- and ³¹P-NMR-spectroscopy. Dimethylsilylen-bis(phosphinic acid esters) were obtained according to \documentclass{article}\pagestyle{empty}\begin{document}$ 2{\rm R}_{2} {\rm P(\rm X)\rm ONH}_{4} + {\rm R}_{\rm 2} {\rm SiCl}_{2} \to 2{\rm E NH}_{4} {\rm Cl + R}_{2} {\rm P(X) - O - SiR}_{2} - {\rm O - P(X)R}_{2} ({\rm R = CH}_{3};{\rm X = O,S}) $\end{document}.     

Mass spectra of esters of α-hydroxy and α-methoxy acids

The most abundant fragment produced by electron bombardment of esters of the type R¹R²C(OR³)CO₂R⁴ is the R¹R²C = \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm O}\limits^{{\rm + } \cdot } $\end{document}R³ ion. Methyl glycollate (R¹ = R² = R³ = H, R⁴ = Me) eliminates the HCO˙ radical by a complex rearrangement involving the methylenic hydrogen atoms. The methyl and ethyl esters of methoxyacetic acid (R¹ = R² = H, R³ = Me, R⁴ = Me or Et) eliminate formaldehyde by the McLafferty rearrangement.     

Ion cyclotron resonance studies of alkylsilyl ions: V—The reactions of alcohols and ethers with the allyldimethylsilyl cation

Diallyldimethylsilane provides a source of the allyldimethylsilyl cation in the ion cyclotron resonance spectrometer; reaction of this cation with alcohols (ROH) produces adducts which decompose by loss of C₃H₆ to yield the ion \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm Me}_2 \mathop {\rm S}\limits^{\rm + } {\rm i} - {\rm OR}} \right] $\end{document}. This elimination is thought to occur by a 1,5-hydrogen shift, together with either stepwise or concerted silicon-carbon bond cleavage. The corresponding aducts from ethers R? O? R¹ (R¹?R, R¹?Et) first lose (R¹? H˙) and then undergo the elimination described above.     

Structure and formation of gaseous [C4H5O]+ ions. I—isomeric ions of the type C3H5\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O

Characterization of [C₄H₅O]⁺ ions in the gas phase using their collisional activation spectra shows that the four C₃H₅\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O isomers CH₂?C(CH₃)\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O, CH₂?CHCH₂\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O, CH₃CH?CH\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O and ?? \documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O are stable for ≥ 10^?5 s. It is concluded further from the characteristic shapes for the unimolecular loss of CO from C₃H₅\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O ions generated from a series of precursor molecules that the CH₂?CH(CH₃)\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O- and CH₂?CHCH₂\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O-type ions dissociate over different potential surfaces to yield [allyl]⁺ and [2-propenyl]⁺ [C₃H₅]⁺ product ions respectively. Cyclopropyl carbonyl-type ions lose CO with a large kinetic energy release, which points to ring opening in the transition state, whereas this loss from CH₃CH?CH\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O-type ions is proposed to occur via a rate determining 1,2-H shift to yield 2-propenyl cations.     

Über Chalkogenolate. 171. Reaktion von N,N′-Diphenylformamidin mit Kohlenstoffdisulfid 4. Ester der N,N′-Diphenyl-N-formimidoyldithiocarbamidsäure

On Chalcogenolates. 171. Reaction of N,N′-Diphenyl Formamidine with Carbon Disulfide. 4. Esters of N,N′-Diphenyl-N-Formimidoyl Dithiocarbamic Acid Potassium N,N′-diphenyl N-formimidoyl dithiocarbamate reacts with alkyl halides to yield the corresponding esters \documentclass{article}\pagestyle{empty}\begin{document}${\rm C}_6 {\rm H}_5 {\rm N} = CH - {\rm N}({\rm C}_6 {\rm H}_5) - {\rm CR} - {\rm SR, where R = CH}_3,{\rm C}_2 {\rm H}_5,{\rm CH}_2 - {\rm C}_6 {\rm H}_5,$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}${\rm and (C}_6 {\rm H}_5 {\rm N} = CH - {\rm N}({\rm C}_6 {\rm H}_5) - {\rm CS)}_{\rm 2} = {\rm CH}_2 .$\end{document} The phenyl ester (R = C₆H₅) has been synthesized by reaction of N,N′-diphenyl formamidine with the phenyl ester of chlorodithioformic acid. The prepared compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Magnetische Struktur von Columbit,FeNb2O6

The atom parameters of columbite. FeNb₂O₆ and MnNb₂O₆, are refined by neutron diffraction. Low temperature measurements of FeNb₃O₆ provided magnetic reflections hkl with k half integer. From the intensities of the reflections a collinear magnetic structure \documentclass{article}\pagestyle{empty}\begin{document}$ \overrightarrow {\rm S} _1 = - \overrightarrow {\rm S} _2 = \overrightarrow {\rm S} _3 = \overrightarrow {\rm S} _4 $\end{document} results for the 4 atoms of the half of the magnetic unit cell. The moments lie parallel to the x-axis, φ_a = 0°. The moment is μ = 3.84 μ_B. For MaNb₂O₆ at 2.0°K reflections 010, 101 and 210 are observed additionally. From the observed intensities it is possible to distinguish a collinear model G: \documentclass{article}\pagestyle{empty}\begin{document}$ \overrightarrow {\rm S} _1 = - \overrightarrow {\rm S} _2 = \overrightarrow {\rm S} _3 = - \overrightarrow {\rm S} _4 $\end{document} with components G_x, G_z (φ_a = 10°, φ_c = 80°), and a non-collinear model C_x (\documentclass{article}\pagestyle{empty}\begin{document}$ \overrightarrow {\rm S} _1 = \overrightarrow {\rm S} _2 = - \overrightarrow {\rm S} _3 = - \overrightarrow {\rm S} _4 $\end{document}) with G_y in favour of the first one.     

Massenspektrometrische Untersuchungen an Azoverbindungen: I

A number of symmetrical and unsymmetrical azo compounds have been studied by electron impact mass spectrometry. In all cases (except azoisobutyronitrile) the compounds follow a two-step fragmentation mechanism \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm R}^{\rm 1} - {\rm N = N - R}^{\rm 2} } \right]_{}^{_.^ + } $\end{document} → [R¹? N₂]⁺ (+R²˙)→[R¹]⁺(+N₂).     

Ein neues Verfahren zur Messung feldstärkeabhängiger Suszeptibilitäten mit der Faraday-Methode,angewandt auf Palladium-Mordenit

A New Method for Measuring Field-dependent Susceptibilities with the Faraday Method, Applied on Palladium Mordenite A simple method to calculate the mean value of an inhomogeneous magnetic field is described, which is needed for susceptibility measurements with a Faraday balance. By combination of the magnetic behaviour of paramagnetic and saturated ferromagnetic calibrating samples we get the magnetic field H = \documentclass{article}\pagestyle{empty}\begin{document}${\rm H} = \frac{{{\rm \sigma}_\infty .{\rm m}_{\rm f}}}{{\chi _{{\rm ges}} \cdot {\rm m}_{{\rm ges}} - \chi _{\rm p}\cdot m_{\rm p}}} $\end{document} $\end{document} (s?_∞ specific saturation magnetization, m mass, χ susceptibility). A Pd-mordenite sample is discussed as an example of a diamagnetic substance with a superparamagnetic impurity. Because the impurity is not magnetically saturated we must take into account the Langevin function. We calculated the diamagnetic susceptibility χ_dia = ?0.411 · 10^?6 cm³/g.     

Über Oxidsysteme mit Übergangsmetallionen in verschiedenen Oxydationsstufen. X. Elektronische und infrarotspektroskopische Untersuchungen am System Zn(ZnxV2−x)O4

The controlled valency semiconduction in the spinel system \documentclass{article}\pagestyle{empty}\begin{document}${\rm Zn}({\rm Zn}_{\rm x} \mathop {\rm V}\limits^{ + 3} _{2 - 2{\rm x}} \mathop {\rm V}\limits^{ + 4} _{\rm x}){\rm O}_4 (0 \le {\rm x} \le 0.50)$\end{document} is due to the controlled variation of the ratio V³⁺/V⁴⁺ at octahedral sites. The low temperature phase which is present according to X-ray patterns above x = 0.18 with an ordered cation distribution at the octahedral sites shows a higher specific electrical resistivity than the high temperature phase which is characterized by a random cation distribution. The activation energies, too, differ in the range x > 0.15. The whole region of solid solutions shows p-type conductivity. The thermo-EMF has a weak temperature dependence for x > 0.03. The IR spectra of both phases are identical in the range between 1000 and 200 cm^?1.     

The kinetics of the interaction of peroxy radicals. II. Primary and secondary alkyl peroxy

A chain mechanism is proposed to account for the very rapid termination reactions observed between alkyl peroxy radicals containing α-C—H bonds which are from 10⁴ to 10⁶ faster than the termination of tertiary alkyl peroxy radicals. The new mechanism is with termination by . \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}\overline {{\rm CHOO}} $\end{document} is the zwitterion originally postulated by Criegee to account for the chemistry of O₃-olefin addition. Heats of formation are estimated for \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {{\rm CH}_2 {\rm OO,}} {\rm }\overline {{\rm RCHOO}} $\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$ ({\rm C}\overline {{\rm H}_3 )_2 {\rm COO}} $\end{document} and it is shown that all steps in the mechanism are exothermic. The second step can account for (¹Δ)O₂ which has been observed. k₁ is estimated to be 10^9–2/θ liter/M sec where θ = 2.303RT in kcal/mole. The second and third steps constitute a chain termination process where chain length is estimated at from 2 to 10. This mechanism for the first time accounts for minor products such as acid and ROOH found in termination reactions. Trioxide (step 3) is shown to be important below 30°C or in very short time observations (<10 s at 30°C). Solvent effects are also shown to be compatible with the new mechanism.     

Electrocatalytic Reduction of O2 by a Cu(II)-Substituted Electron-Rich Wheel-Type Oxomolybdate Nanocluster

Catalysis of electron transfer by a Cu-substituted wheel-type oxomolybdate cluster–anion, , (1), is demonstrated. Data provided include aqueous-solution chemistry (stability) studies of 1 and , (2), derivatives of the “plenary” {Mo₁₅₄} anion, , (3). Combined use of cyclic voltammetry and UV–vis spectroscopy shows that, while both 1 and 2 appear to be stable in solution at pH 0.33 (0.5 M H₂SO₄), 1 is more stable than 2 at pH 3 (in 0.2 M Na₂SO₄). Cyclic voltammetric analysis in the presence of O₂ shows that 1 is an electrocatalyst for electron transfer to O₂. Bulk electrolysis of 1 in the presence of O₂ (ca. 1 mM) is used to assess catalyst stability under turnover conditions, and to demonstrate that the final product of electrocatalytic reduction is water, rather than H₂O₂. Finally, control experiments using 1, 2, and CuSO₄ (no oxomolybdate-cluster present), show that catalytic activity is due to specific interaction(s) between Cu ions and the Mo₁₄₂ type oxomolybdate structure of 1.     

Nitrosyl-tetrachloro-dichlorphosphato-molybdat(+II); Darstellung,IR-Spektrum und Kristallstruktur von (AsPh4)2[Mo(NO)Cl4(O2PCl2)]

Nitrosyl-tetrachloro-dichlorophosphate-molybdate(+II); Preparation, I.R. Spectrum and Crystal Structure of (AsPh₄)₂[Mo(NO)Cl₄(O₂PCl₂)] The title compound is prepared by the reaction of AsPh₄[Mo(NO)Cl₄] with AsPh₄? [PO₂Cl₂] in dichloromethane solution. It forms orange crystals which are only little sensitive to moisture. The complex crystallizes triclinic in the space group P1 with two formula units in the unit cell. The structure was solved by X-ray diffraction methods (2498 observed, independent reflexions, R = 5.4%). The compound consists of AsPh₄^⊕ cations and [Mo(NO)Cl₄(PO₂Cl₂)]^2? anions. The NO ligand is coordinated in linear array \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm MO}}\limits^ \ominus = \mathop {\rm N}\limits^ \oplus = {\rm O}(177^{\circ}) $\end{document}. The dichlorophosphate group is coordinated in trans position to the NO ligand with one of its oxygen atoms. The Mo?N bonding of the NO ligand causes the bond angle NMoCl of 93.2° in average. The IR spectrum is recorded and assigned.     

Propanoyl ion formation from metastable [C3H6O]+˙ ions

Collisionally activated spectra demonstrate that CH₃CH₂C?O⁺ rather than \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 2} = {\rm CHCH = }\mathop {\rm O}\limits^{\rm + } {\rm H}$\end{document} is formed in the metastable losses of hydrogen from [C₃H₆O]^+˙ ions with the oxygen on the first carbon. This provides another example of formation of an acyl ion following ‘ketonization’ prior to metastable decomposition.     

Loss of methyl radical from some small immonium ions: Unusual violation of the even-electron rule

Several small immonium ions of general formula \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}^{\rm 1} {\rm R}^{\rm 2} {\rm C = }\mathop {\rm N}\limits^{\rm + } {\rm R}^{\rm 3} {\rm CH}_{\rm 3} $\end{document} (R¹, R², R³ = H or alkyl) eliminate ^.CH₃; this reaction occurs in the mass spectrometer in both fast (source) and slow (metastable) dissociations. Such behaviour violates the even-electron rule, which states that closed-shell cations usually decompose to give closed-shell daughter ions and neutral molecules. The heats of formation of the observed product ions (for example, [(CH₃)₂C?NH]^+.) can be bracketed using arguments based on energy data. Deuterium labelling results reveal that the methyl group originally bound to nitrogen is not necessarily lost in the course of dissociation. Thus, for instance, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm{(CH}}_{\rm{3}})_2 = \mathop {\rm{N}}\limits^{\rm{ + }} {\rm{HCD}}_{\rm{3}} $\end{document} eliminates both CH₃^. and CD₃^., via different mechanisms, but very little CH₂D^. or CHD₂^. loss occurs.     

Laser-induced chemical kinetics: Absolute rate constants for the reactions Ċ2F2 + Br2 → C2F5Br + Ḃr and n-Ċ3F7 + Br2 → n-C3F7Br + Ḃr

Absolute rate constants at room temperature for the metathesis reaction have been measured under VLPP conditions: k₁ = (2.0 ± 0.5) × 10⁸M^?1·s^?1, k₂ = (3.0 ± 0.7) × 10⁸M^?1·s^?1. The radicals were generated through collisionless infrared-multiphoton decomposition of the corresponding iodides by irradiation from a high-power CO₂-TEA laser. The reaction of ?₂F₅ and ?₃F₇ with \documentclass{article}\pagestyle{empty}\begin{document}$$\mathop {\rm N}\limits^{\rm .} {\rm O}_{\rm 2} $$\end{document} are briefly discussed in relation to the reaction of ?₃ with \documentclass{article}\pagestyle{empty}\begin{document}$$\mathop {\rm N}\limits^{\rm .} {\rm O}_{\rm 2} $$\end{document}, which had been measured previously.     

The gas-phase pyrolysis of alkyl nitrites. III. Isopropyl nitrite

The rate of decomposition of isopropyl nitrite (IPN) has been studied in a static system over the temperature range of 130–160°C. For low concentrations of IPN (1–5 × 10^?5M), but with a high total pressure of CF₄ (～0.9 atm) and small extents of reaction (～1%), the first-order rates of acetaldehyde (AcH) formation are a direct measure of reaction (1), since k₃ » k₂(NO): \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$ {\rm IPN}\begin{array}{rcl} 1 \\ {\rightleftarrows} \\ 2 \\ \end{array}i - \Pr \mathop {\rm O}\limits^. + {\rm NO},i - \Pr \mathop {\rm O}\limits^. \stackrel{3}{\longrightarrow} {\rm AcH} + {\rm Me}. $\end{document} Addition of large amounts of NO (～0.9 atm) in place of CF₄ almost completely suppressed AcH formation. Addition of large amounts of isobutane – t-BuH – (～0.9 atm) in place of CF₄ at 160°C resulted in decreasing the AcH by 25%. Thus 25% of \documentclass{article}\pagestyle{empty}\begin{document}$ i - \Pr \mathop {\rm O}\limits^{\rm .} $\end{document} were trapped by the t-BuH (4): \documentclass{article}\pagestyle{empty}\begin{document}$ i - \Pr \mathop {\rm O}\limits^. + t - {\rm BuH} \stackrel{4}{\longrightarrow} i - \Pr {\rm OH} + (t - {\rm Bu}). $\end{document} The result of adding either NO or t-BuH shows that reaction (1) is the only route for the production of AcH. The rate constant for reaction (1) is given by k₁ = 10^{16.2±0.4–41.0±0.8}/θ sec^?1. Since (E₁ + RT) and ΔH°₁ are identical, within experimental error, both may be equated with D(i-PrO-NO) = 41.6 ± 0.8 kcal/mol and E₂ = 0 ± 0.8 kcal/mol. The thermochemistry leads to the result that \documentclass{article}\pagestyle{empty}\begin{document}$ \Delta H_f^\circ (i - {\rm Pr}\mathop {\rm O}\limits^{\rm .} ) = - 11.9 \pm 0.8{\rm kcal}/{\rm mol}. $\end{document} From ΔS°₁ and A₁, k₂ is calculated to be 10^10.5±0.4M^?1·sec^?1. From an independent observation that k₆/k₂ = 0.19 ± 0.03 independent of temperature we find E₆ = 0 ± 1 kcal/mol and k₆ = 10^9.8+0.4M^?;1·sec^?1: \documentclass{article}\pagestyle{empty}\begin{document}$ i - \Pr \mathop {\rm O}\limits^. + {\rm NO} \stackrel{6}{\longrightarrow} {\rm M}_2 {\rm K} + {\rm HNO}. $\end{document} In addition to AcH, acetone (M₂K) and isopropyl alcohol (IPA) are produced in approximately equal amounts. The rate of M₂K formation is markedly affected by the ratio S/V of different reaction vessels. It is concluded that the M₂K arises as the result of a heterogeneous elimination of HNO from IPN. In a spherical reaction vessel the first-order rate of M₂K formation is given by k₅ = 10^9.4–27.0/θ sec^?1: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm IPN} \stackrel{5}{\longrightarrow} {\rm M}_2 {\rm K} + {\rm HNO}. $\end{document} IPA is thought to arise via the hydrolysis of IPN, the water being formed from HNO. This elimination process explains previous erroneous results for IPN.