Liquid NH3 Research Articles

Density and Viscosity of Liquid ND3

The density and viscosity of liquid ND3 have been measured over the temperature range from +30° to −25° and compared with the density and viscosity of liquid NH3. At any given temperature, the ratio of densities ρND3/ρNH3 is 1.187± 0.001 and the ratio of viscosities ηND3/ηNH3 is 1.20± 0.01. The fact that both ratios are independent of temperature suggests that the strengths of intermolecular interactions are essentially the same in the two liquids and that the density and viscosity differences are to be attributed to differences in molecular size and mass. The density ratio indicates that the molecular volume of NH3 in the liquid is ∼ 1% larger than that of ND3 while the viscosity ratio indicates that the viscosity varies directly as M/Vm (Vm=molar volume) for these two liquids.

Melting curve and high-pressure polymorphism of NH 4HF 2

The melting curve of NH 4HF 2 I rises from 125.2°C at atmospheric pressure to a triple point II/I/liquid at 9.3 kbar, 220°C. The I/II phase boundary is terminated at a triple point III/I/II at ∼45 kbar, 295°C. The melting curve of the new phase NH 4HF 2 II passes through a broad maximum at ∼39 kbar, 306°C, and is terminated at a triple point III/II/liquid at 46.3 kbar, 301°C. The melting curve of NH 4HF 2 III rises with pressure. The NH 4HF 2 III may be a dense hydrogen-bonded phase. Liquid NH 4HF 2 appears to be anomalous in several respects, and has a high compressibility relative to the solid phases.

Zur kenntnis der chemie der metallcarbonyle und der cyanokomplexe in flüssigem ammoniak : XXVI Über neue carbamoyl-carbonyl-komplexe des mangans

The carbamoylcarbonyl manganese complexes cis-Mn(CO) 4(NH 3)(CONH 2), cis-Mn(CO) 3(PPh 3)(NH 3)(CONH 2) and cis-Mn(CO) 3(PPh 3) 2(CONH 2), which split off water from the -CONH 2 group at different temperatures, are obtained after very short reaction times by the reactions of Mn(CO) 5Cl, Mn(CO) 4(PPh 3)Cl and [Mn(CO) 4(PPh 3) 2]Cl with liquid NH 3. Because of this cleavage the cyanotricarbonyl complexes Mn(CO) 3(NH 3) 2CN or Mn(CO) 3(PPh 3)(NH 3)CN are formed in liquid NH 3 or ether. The properties of these compounds are described and their structures are discussed on the basis of their IR spectra.

Studies on the syntheses of heterocyclic compounds—CDLXXXIV : One-step synthesis of dibenzoindolizinium salt and phenolic aporphine by benzyne reaction

An indisputable benzyne reaction of 1-(5-bromo-2,4-dimethoxybenzyl)-1,2,3,4-tetrahydro-7-hydroxy-6-methoxy-2-methylisoquinoline ( 1) with NaNH 2 in liquid NH 3 afforded 1-hydroxy-2,8,10-trimethoxy-6-methylaporphine ( 4) and 5,6,12,12a-tetrahydro-2-hydroxy-3,9,11-trimethoxy-7-methyldibenzo[ b,g]indolizinium salt ( 6).

Preparation, characterisation, and europium-151 Mössbauer spectra of some carbides, nitrides, nitride-carbides, cyanides, and thiocyanates of europium

The reaction of europium metal with HCN and (CN)2 at elevated temperatures has been shown to yield Eu2C3, EuC2, and compounds of the type EuNxCy. X-Ray parameters for these phases are reported and they are shown by 151Eu Mossbauer spectroscopy to be band systems. EuN is shown to be ionic and to contain Eu3+ ions. The reactions in liquid NH3 of europium with HCN, C2H2, and NH4SCN have been shown to produce europium(II) and europium(III) cyanide, europium(III) acetylide, and europium(III) thiocyanate respectively. The width of the 151Eu Mossbauer resonance is discussed in relation to possible bonding situations and the relationship between chemical isomer shift and bond ionicity is considered.

Nitrification Inhibition in Soil: II. Evaluation of Anhydrous Ammonia‐Potassium Azide Solutions in Eastern Washington

AbstractThe effectiveness of potassium azide (KN3) as a nitrification inhibitor for field‐applied anhydrous NH3 was evaluated on a Naff silt loam in the winter wheat (Triticum aestivum L.) area of eastern Washington. Formulations of KN3 in liquid NH3 of 0, 2, and 6% (w/w) were applied to fallow soil in August 1969 at a rate of 112 kg N/ha (81‐cm spacing) with a special field applicator. The 2% formulation was also applied at a rate of 224 kg N/ha. The NH3 retention zone was sampled periodically through February 1970 and analyzed for NH4+‐N, NO2‐‐N, and NO3‐‐N. Both levels of KN3 were effective in reducing the nitrification rate during the early post injection period, but the higher level was more effective at later dates. Two months after application, the amounts of NO3‐‐N recovered from the retention zone as percent of total extractable N were 67, 48, and 36 for NH3 alone, NH3 + KN3 (2%), and NH3 + KN3 (6%), respectively. Percentage amounts of NO3‐‐N decreased with increase in N application rate. Nitrification inhibition due to KN3 was still evident 6 months after application, particularly at the high N rate. The inhibitory effect of low soil temperature during the winter months was also apparent. These results indicate that KN3 formulated with anhydrous NH3 was an effective nitrification inhibitor for this N source.

Differential capacitance and frequency dispersion on solid and liquid mercury in liquid ammonia

The behaviour of solid and liquid mercury electrodes in 0·1 M ammonium nitrate solutions of liquid ammonia is investigated. The differential-capacitance/potential curves for the solid (at −40°C) and the liquid (at −38°C) are U-shaped and have a minimum of 11·2 μF/cm 2 at 0·45 V ( vs Cd/satd. Cd(NO 3) 2 in liquid NH 3) for the solid of and 10·25 μF/cm 2 at 0·4 V for the liquid. The curves have no anodic hump. The values for the solid are about 10% higher than that for the liquid but this is still within the error of the surface area measurement. The frequency dispersion of the interfacial impedance was measured between 400 and 20,000 Hz at 0·60, 0·40, 0·10, and −0·25 V. Assuming de Levie's model of parallel grooves of depth l and aperture 2 β to be applicable, the parameter l/sin β was calculated from the data. Values obtained for the liquid mercury electrodes are 5·5–6·8 × 10 −2 cm and are attributed to shielding and solution creepage. For the solid electrodes l/sin β is 12–23 × 10 −2cm. Although these numbers are too large, the increase in l/sin β by a factor of 3 when going from a liquid to a solid surface is parallel to an increase in roughness factor to about 3 expected for this case. This suggests that l/sin β may be a useful way to measure surface roughness and/or surface roughness changes.

ESR, 1H, and 2D Studies of the Radical Anion of 1,3,5-Triphenylbenzene

MO calculations predict that the monoanion of 1,3,5-triphenylbenzene (Tpb) is in an orbitally degenerate ground state. Nevertheless, the ESR spectrum in liquid NH3 is well resolved; the derivative linewidth is equal to 0.06 Oe only. The g value and the electronic relaxation times T1 and T2 were comparable in magnitude to those of orbitally nondegenerate radicals. It is suggested that twisting of the phenyl rings out of the plane of the molecule, which may lift the orbital degeneracy, is the principal reason of this behavior. 1H and 2D NMR experiments were performed on a reduced sample of Tpb, containing both normal and perdeutero-Tpb. From the Fermi contact shifts signs and magnitudes of all hyperfine splitting constants have been determined, and they agreed very well with the ESR splitting constants. From the proton linewidths the electronic and dipolar correlation times were inferred. Quadrupole coupling constants for all deuterium nuclei were calculated from the 2D linewidths.

Electrochemical anionic polymerization of 4‐vinylpyridine in pyridine

AbstractThe preparation of poly‐4‐vinylpyridine (poly‐4VP) by electrochemical polymerization of 4‐vinylpyridine (4VP) in pyridine containing sodium tetraphenylboron (NaBPh4) is described. Information on the influence of monomer concentration, current density, polymerization rate, molecular weight, and electrochemical efficiency is presented. The polymerizations were performed under conditions of constant electrolysis current. Polymer formed in the cathodic compartment only, where a red‐orange solution developed after about 15 min of electrolysis time. The optical absorption spectra of these colored solutions were studied. Cyclic voltammograms of 4VP in pyridine and NaBPh4 are also reported, and the influence of the scan rate upon peak current is described. The results indicate that the polymerization was anionic and nonterminating. The characteristics of the electrochemical polymerization of 4VP in pyridine are compared with those of the same monomer in liquid NH3. In the former case, the catholyte was homogeneous, and polymer growth occurred in the liquid phase, while in the latter growth took place in a heterogeneous environment. Kinetic consequences of these physical differences are pointed out. Suggestions for the mechanism of this electrochemical initiation are advanced.

Terpenoids—XIV : Formal chemical conversion of enmein into ent-kaurene, atisine, garryine and veatchine

Lactone ester 5 derived from enmein ( 2) was subjected to acyloin condensation to give 18 as a main product. Compound 18 was converted into 27, which on ozonolysis gave ketone 31. The latter was treated with Ca in liquid NH 3 to afford 3. The work constitutes a formal chemical conversion of enmein into ent-kaurene, atisine, garryiae and veatchine.

The conductivity of AgNO3 in liquid and dense gaseous NH3 as a function of temperature

Abstract The main work on dense gaseous electrolytes had been done with water as the solvent. The practical application of such electrolytes is limited due to the high critical temperature and pressure of water (374 °C, 217.7 atm). Ammonia, on the other hand, while not as strongly ionizing a solvent as water, has more convenient critical constants (133 °C, 112 atm) and is, in addition, less reactive toward metals than is water. Consequently, it is of interest as a dense gaseous solvent and the properties of dense gaseous ammonia electrolytes are in need of investigation. Silver nitrate was chosen for the present experiment because of its good solubility in NH3 and because of the high reversibility of silver electrodes in silver nitrate. The following reports a measurement of the conductivity of a solution of silver nitrate in ammonia over a range of temperatures including the liquid and dense gaseous region.

Diffusion von gelöstem Wasserstoff und Deuterium in flüssigem Ammoniak

Diffusion coefficients of H2 and D2 in liquid NH3 were determined from rates of solution at constant partial pressure of the gases (9 atm) in the range -60 to + 1 0 °C. D0(H2) = 9.4±0.4 ; D0(D2) = 7.4+0.4 cm2/sec; ΔE(H2) =2090 ± 30 ; ΔE(D2) =2030 ± 30 cal/mole. The mechanism of diffusion and the isotope effects are discussed on the basis of the structure of liquid NH3 .

Density and viscosity of sodium + ammonia and ammonium iodide + ammonia solutions

The densities and viscosities of the Na + NH3 and NH4I + NH3 solutions were measured as a function of temperature and composition. In the NH4I + NH3 system, the density and viscosity increase with NH4I concentration, while those of the Na + NH3 system decrease with increasing sodium composition. The concentration dependence of viscosity is discussed in terms of the theory of transport processes based upon a small step-diffusion process. Liquid NH3 near the boiling point can be described as a rigid-sphere liquid. The calculated viscosities are in qualitative agreement with the experimental data.

A Portable Injector for Dispensing Liquid Anhydrous NH3 in the Field

AbstractA portable injector for metering and dispensing small aliquots of anhydrous NH3 rapidly and with good precision in the field has been constructed and tested. The device is versatile and should be equally suitable for dispensing other high‐pressure solutions in the field. The portable injector is simple in design, easily operated, and readily transportable. Injecting liquid NH3 with the portable injector produces little soil disturbance compared with usual application methods.The absolute mass of a single injection of anhydrous NH3 in the field may be determined by direct calibration in the field or by a laboratory calibration and a calculated correction for temperature. The latter method appears to be more practical and involves no more error than that involved in a direct field calibration.A procedure for sampling soil by taking successive hemispheres around the injection point was found to be satisfactory for characterizing NH3 concentrations and pH in the retention zone.

The electrochemical polymerization of 4‐vinylpyridine in liquid ammonia

AbstractThe polymerization of 4‐vinylpyridine (4VP) in an electrochemical cell in liquid NH3 solutions was studied. With monomer concentrations of 5 to 25 vol.‐% in the temperature range −33 to −78°C. rapid polymerization takes place when current is passed through the cell. Polymer yields of 80 to 90% are easily obtained in a few hours with NaN3 or NaCl as electrolyte and smooth Pt electrodes in a stirred three‐compartment cell. Current densities of 1 × 10−2 to 10 ma./cm.2 and applied voltages of 2.5 to 50 v. were employed. Different anodic materials were used, including Pt and pyrolitic graphite. The electrochemical yield is about 1 mole of polymer per faraday for current densities of ⩽ 1 × 10−2 ma./cm.2, and it becomes 0.5 and lower at higher current densities. The rate of polymerization was found to increase, and the molecular weight of the polymer to decrease, with increasing current density. It is concluded that the initiation step consists of electron transfer between the cathode and the monomer. Depending on the amount of polymer deposited on the cathode and on the current density, initiation may occur on the cathode surface or within the polymer deposit on the cathode or in the free liquid solvent. The consequence of the electron transfer to monomer is the formation of radical anions. Electrochemical yields of about 1.0 mole of polymer per faraday suggest that radical anion dimerization does not take place extensively, while dimerization may predominate when electrochemical yields are about 0.5. Subsequent chain growth occurs through an anionic mechanism, as evidenced by the nonterminating nature of the polymerization, the presistent red color of the polymer formed, and the sensitivity of the polymerization to the addition of protic substances. Polymer molecular weights were in the range of 10,000 to 360,000. Molecular weight distributions with Mw/Mn ratios of 1.21 or larger were found. Softening points, solubility characteristics, and infrared spectra of the electrochemical polymer are presented and discussed in comparison with those of poly(4‐vinylpyridine) prepared with chemical initiators.

Preparation of Fluorocyclopropanes by Reductive Dechlorination of Chlorofluorocyclopropanes

Angewandte Chemie International Edition in EnglishVolume 6, Issue 7 p. 629-629 Communication Preparation of Fluorocyclopropanes by Reductive Dechlorination of Chlorofluorocyclopropanes† Priv.-Doz. Dr. M. Schlosser, Priv.-Doz. Dr. M. Schlosser Organisch-Chemisches Institut der Universität, Tiergartenstr., 69 Heidelberg (Germany)Search for more papers by this authorDipl.-Chem. G. Heinz, Corresponding Author Dipl.-Chem. G. Heinz Organisch-Chemisches Institut der Universität, Tiergartenstr., 69 Heidelberg (Germany)Organisch-Chemisches Institut der Universität, Tiergartenstr., 69 Heidelberg (Germany)Search for more papers by this author Priv.-Doz. Dr. M. Schlosser, Priv.-Doz. Dr. M. Schlosser Organisch-Chemisches Institut der Universität, Tiergartenstr., 69 Heidelberg (Germany)Search for more papers by this authorDipl.-Chem. G. Heinz, Corresponding Author Dipl.-Chem. G. Heinz Organisch-Chemisches Institut der Universität, Tiergartenstr., 69 Heidelberg (Germany)Organisch-Chemisches Institut der Universität, Tiergartenstr., 69 Heidelberg (Germany)Search for more papers by this author First published: July 1967 https://doi.org/10.1002/anie.196706291Citations: 6 † Dedicated to Professor G. Wittig on his 70th birthday AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article.Citing Literature Volume6, Issue7July 1967Pages 629-629 RelatedInformation

Umwandlung von cis‐ und trans‐1,4‐polybutadien in polymere mit konjugierten doppelbindungssystemen

Abstract1,4‐Polybutadienes (cis and trans) are transformed into conjugated polymers by bromination and dehydrobromination. trans‐1,4‐Polybutadiene of both a high and lower molecular weight as well as cis‐1,4‐polybutadiene are completely brominated by means of pyridinium perbromide in pyridine‐carbon disulfide solution. The bromination products obtained from the polymers with a trans structure are much less soluble than the corresponding addition products from the cis‐structured polymeride. The addition products are dehydrobrominated to a large extent with KOH/Py, and with KNH2 in liquid NH3 and NaH in DMF the elimination is even complete. The brownish black insoluble products obtained have long sequences of conjugated double bonds and exhibit a single narrow ESR signal; the conductivity obeys an exponential dependence on temperature.

Half-cell potentials of the Ca/Ca 2+ couple in thiocyanate-liquid-ammonia solutions

The emf of the cells Ca/Ca (C) 2+ | Pb (0·1N) 2+/Pb, with liquid NH 3 and liquid NH 3 containing 20 mol-% KSCN or NH 4SCN, as solvents, was measured at −34°C. In the thiocyanate solutions no metallic solution of calcium is formed and the calcium potential follows the Nerst dependence on concentration with n = 2. The emf measurements indicated that the standard oxidation potential of calcium in liquid NH 3 on the lead scale is E Ca,Ca 2+ ≥ +2·185 V (at −34°C).

The Ring-opening Polymerization of Ethylene-methylphosphite

Abstract Several Lewis acids have been found to be effective catalysts for the polymerization of ethylene-methylphosphite, giving a solid polymer with a poly(ethylene-methylphosphonate) structure. The use of Al(C2H5)3 gave a wax-like polymer with the structure of poly(ethylene-methoxy-phosphinate), while Na and Li in liquid NH3 at −78°C produced a jelly-like polymer partly composed of poly(ethylene-methylphosphite).

UV and Visible Spectra Reveal Ionization Constants of Weak Acids in Liquid NH

UV and Visible Spectra Reveal Ionization Constants of Weak Acids in Liquid NH