Silver Fulminate Research Articles

Taming the Dragon: Complexation of Silver Fulminate with Nitrogen-Rich Azole Ligands.

The almost ancient and very sensitive silver fulminate (SF), which was involved in the establishment of fundamental chemical concepts, was desensitized for the first time with different nitrogen-rich triazoles and tetrazoles, yielding SF complexes [Agx(CNO)x(N-Ligand)y] (x = 1-4; y = 1-3). These were accurately characterized (X-ray diffraction, scanning electron microscopy, IR, elemental analysis, differential thermal analysis, and thermogravimetric analysis) and investigated concerning their energetic character. The highly energetic coordination compounds suddenly show, in contrast to SF, sensitivities in a manageable range and are therefore safer to handle. In particular, compounds [Ag4(CNO)4(BTRI)] [3; BTRI = 4,4'-bis(1,2,4-triazole)] and [Ag4(CNO)4(2,2-dtp)] [8; 2,2-dtp = 1,3-di(tetrazol-1-yl)propane] show values in the range of desired lead styphnate alternatives with similar energetic performances. The crystal structure experiments reveal silver cluster formation in all complexes with distinct argentophilic interactions close to 2.77 Å. Furthermore, it was possible to synthesize 8 in a one-pot reaction, avoiding the isolation of highly sensitive SF.

Structural, electronic and optical properties of well-known primary explosive: Mercury fulminate.

Mercury Fulminate (MF) is one of the well-known primary explosives since 17th century and it has rendered invaluable service over many years. However, the correct molecular and crystal structures are determined recently after 300 years of its discovery. In the present study, we report pressure dependent structural, elastic, electronic and optical properties of MF. Non-local correction methods have been employed to capture the weak van der Waals interactions in layered and molecular energetic MF. Among the non-local correction methods tested, optB88-vdW method works well for the investigated compound. The obtained equilibrium bulk modulus reveals that MF is softer than the well known primary explosives Silver Fulminate (SF), silver azide and lead azide. MF exhibits anisotropic compressibility (b > a > c) under pressure, consequently the corresponding elastic moduli decrease in the following order: C22 > C11 > C33. The structural and mechanical properties suggest that MF is more sensitive to detonate along c-axis (similar to RDX) due to high compressibility of Hg⋯O non-bonded interactions along that axis. Electronic structure and optical properties were calculated including spin-orbit (SO) interactions using full potential linearized augmented plane wave method within recently developed Tran-Blaha modified Becke-Johnson (TB-mBJ) potential. The calculated TB-mBJ electronic structures of SF and MF show that these compounds are indirect bandgap insulators. Also, SO coupling is found to be more pronounced for 4d and 5d-states of Ag and Hg atoms of SF and MF, respectively. Partial density of states and electron charge density maps were used to describe the nature of chemical bonding. Ag-C bond is more directional than Hg-C bond which makes SF to be more unstable than MF. The effect of SO coupling on optical properties has also been studied and found to be significant for both (SF and MF) of the compounds.

Polymorphism and thermodynamic ground state of silver fulminate studied from van der Waals density functional calculations.

Silver fulminate (AgCNO) is a primary explosive, which exists in two polymorphic phases, namely, orthorhombic (Cmcm) and trigonal (R3) forms at ambient conditions. In the present study, we have investigated the effect of pressure and temperature on relative phase stability of the polymorphs using planewave pseudopotential approaches based on Density Functional Theory (DFT). van der Waals interactions play a significant role in predicting the phase stability and they can be effectively captured by semi-empirical dispersion correction methods in contrast to standard DFT functionals. Based on our total energy calculations using DFT-D2 method, the Cmcm structure is found to be the preferred thermodynamic equilibrium phase under studied pressure and temperature range. Hitherto Cmcm and R3 phases denoted as α- and β-forms of AgCNO, respectively. Also a pressure induced polymorphic phase transition is seen using DFT functionals and the same was not observed with DFT-D2 method. The equation of state and compressibility of both polymorphic phases were investigated. Electronic structure and optical properties were calculated using full potential linearized augmented plane wave method within the Tran-Blaha modified Becke-Johnson potential. The calculated electronic structure shows that α, β phases are indirect bandgap insulators with a bandgap values of 3.51 and 4.43 eV, respectively. The nature of chemical bonding is analyzed through the charge density plots and partial density of states. Optical anisotropy, electric-dipole transitions, and photo sensitivity to light of the polymorphs are analyzed from the calculated optical spectra. Overall, the present study provides an early indication to experimentalists to avoid the formation of unstable β-form of AgCNO.

The Five Senses of Christmas Chemistry

This article describes the organic chemistry of five compounds that are directly associated with the Christmas season. These substances and related materials are presented within the framework of the five senses: silver fulminate (sound), α-pinene (sight), sodium acetate (touch), tryptophan (taste), and gingerol (smell). Connections with the introductory organic curriculum are emphasized throughout to illustrate how the following lecture topics can be reviewed or introduced each November and December: Lewis structures, resonance theory, constitutional isomers, stereoisomers, cycloalkane ring conformations, thermodynamics, acids and bases, nucleophiles and electrophiles, carbonyl condensation reaction mechanisms, and functional group transformations.

Energetic Silver Salts with 5‐Aminotetrazole Ligands

Methylation of 5-amino-1H-tetrazole (1) gives 1-methyl-5-amino-1H-tetrazole (2) and 2-methyl-5-amino-1H-tetrazole (3). A new family of energetic silver complexes based on ligands 1, 2 and 3 with perchlorate and nitrate anions (10-15) were synthesized and characterized by using IR, Raman, and NMR ((1)H, (13)C, (14)N, and (35)Cl NMR) spectroscopy, elemental analysis, and mass spectrometry. The crystal structures of the compounds were determined where possible and reveal interesting structural details that are discussed herein. Additionally, differential scanning calorimetry was used to assess the thermal stability of the new salts, which showed excellent thermal stabilities at temperatures up to and above 225 degrees C. Standard tests were also used to assess the sensitivity of the materials towards impact and friction. All the silver complexes showed increased sensitivity values in comparison with analogous protonated 5-amino-1H-tetrazolium perchlorate and nitrate salts. Some of these materials have sensitivity values that are comparable to commonly used primary explosives and all of them either deflagrate (12-14) or detonate loudly (10 and 11) on contact with an open flame. Lastly, nitrate salt 11 is easily initiated by thermal shock. It shows reasonably low sensitivity in comparison with other silver salts (e.g., silver azide or silver fulminate), which makes handling it much less hazardous. Compound 11 also has good thermal stability, decomposing at approximately 300 degrees C, and shows interesting properties as a more environmentally benign alternative to lead(II) diazide in initiation devices for civil and military applications.

The First Chemical Achievements and Publications by Justus von Liebig (1803—1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry

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The First Chemical Achievements and Publications by Justus von Liebig (1803−1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry

AbstractThe first chemical investigations and publications by Justus von Liebig dealt with the fulminates of silver and mercury. Even as a boy Liebig had learnt how to prepare silver fulminate, and as student of chemistry in Erlangen (1821) he studied the properties and reactions of silver fulminate. In Paris in 1823 (together with Gay‐Lussac) he succeeded in analyzing quantitatively the highly explosive silver compound. This great experimental success with the dangerous silver fulminate was most important in three respects: i. The development of the experimental method later culminated in Liebig’s perfected and well‐known C,H,N analysis of organic compounds (1830). ii. It led to the concept of isomerism when F. Wöhler found that silver cyanate had the same composition as silver fulminate. iii. It was decisive for furthering the scientific career of Liebig, since Alexander von Humboldt was highly impressed by the great skill and talent of Liebig and — by recommendation of Humboldt — Liebig became Professor in Gießen in 1824 (at the young age of 21). The first (fulminato)metal complex, K[Ag(CNO)2], was also isolated by Liebig. Later, explosive (fulminato)metal complexes were prepared by Nef, Wieland, and especially by Lothar Wöhler and co‐workers. In Munich the HCNO structure of fulminic acid was established by its IR spectrum and the spectroscopic properties of (fulminato)metal complexes were studied. A series of new nonexplosive complexes could be obtained by dilution of the energy‐rich species with large cations or ligands. Recent X‐ray structure determinations have revealed the almost perfect linear, tetrahedral, square‐planar, or octahedral structures of these complexes with linear metal−C≡NO bonds, e.g. [Au(CNO)2]−, [Zn(CNO)4]2−, [Ni(CNO)4]2−, [Co(CNO)6]3−. DFT calculations have given very good agreement between the calculated and experimental structural parameters and CNO stretching frequencies. The (fulminato)metal complexes closely resemble the analogous cyano compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

A redetermination of the trigonal silver fulminate structure

A redetermination of the trigonal silver fulminate structure

On hazardous silver compounds

This review is intended to provide informatin so as to decrease likelihood that explosive silver compositions are formed by inadvertence: silver azide, silver fulminate, silver nitride, and silver ...

Pentacarbonylfulminatowolframat, NEt 4[W(CNO)(CO) 5], und isomerisierung fulminat→isocyanat am metall

Zusammenfassung NEt 4 [W(CNO)(CO) 5 ] (I) has been prepared from NEt 4 [WBr(CO) 5 ] and silver fulminate. Rapid isomerisation of I to give NEt 4 [W(NCO)(CO) 5 ] occurs in dichloromethane.

A redetermination of the silver fulminate structure

A redetermination of the silver fulminate structure

A Reappraisal of Silver Fulminate as a detonant

AbstractThe preparation and properties of silver fulminate have been examined to assess its potential for use as a primary explosive. It is an extremely effective detonant but does not appear promising as a stab‐sensitive material. It is concluded that its extreme sensitiveness and the hazards and difficulties associated with its preparation render it unsuitable for military applications. It does find commercial use in the manufacture of toys and crackers when it is normally handled exclusively in small quantities and in the wet state.

The crystal structure of silver fulminate

The crystal structure of silver fulminate

259. Solid-phase reactions in silver fulminate

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Crystal structure of silver fulminate

Crystal structure of silver fulminate

Reaction of Fulminate with Methemoglobin

The addition of a few drops of saturated aqueous mercuric fulminate or of 2% sodium fulminate solution to about 5 cc of millimolar methemoglobin prepared by the action of ferricyanide on laked human erythrocytes, causes the formation of a scarlet pigment which shows a spectroscopic picture similar to that of cyanmethemoglobin. It differs from cyanmethemoglobin, however, in that the addition of alkali causes a change in the spectroscopic band to those of alkaline methemoglobin, in the case of the fulminate derivative, whereas when cyanmethemoglobin is treated with alkali its band persists. The color intensity of the fulminate derivative appears to be about half that of an equimolecular solution of cyanmethemoglobin.Saturated silver fulminate precipitates methemoglobin from solution, the precipitate being red in color. Where the methemoglobin solution has been prepared by the action of quinhydrone on hemoglobin, mercuric fulminate likewise causes a similar precipitate. This would indicate a difference betwe...

EXPLOSION OF SILVER FULMINATE IN HISTOPATHOLOGIC LABORATORY

An explosion occurred Tuesday, March 11, which has jeopardized the eyesight of a research worker in one of the laboratories at the University of California. Sections of bone and teeth with their contained soft tissues had been stained by the so-called silver nitrate method. 2 The stender dishes containing the ammoniacal silver oxide solution were inadvertently left standing in the sun from Saturday noon until Tuesday morning. There were traces of alcohol in the silver solutions carried there by the sections of tissue. The sunlight hastened a chemical reaction between the silver, the ammonia and the alcohol and there resulted from it a highly explosive, very sensitive and unstable compound, silver fulminate (C=N-O-Ag), to be distinguished from the so-called fulminating silver, which explodes on drying. When the dish was taken up to be emptied and cleaned, it was warm from the sun. The mere movement of the liquid was responsible

VII.—On the decomposition of silver fulminate by hydrochloric acid

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Recent Contributions to the History of Detonating Agents 1

II. THAT the power possessed by different very highly explosive substances, of inducing the detonation of such bodies as gun-cotton and nitro-glycerine, is not solely ascribable to the operation of mechanical force very suddenly developed, is indicated not only by the singular inertness of gun-cotton to the influence of nitro-glycerine as a detonating agent, but also by a comparison of the behaviour of other detonating substances wich that of the mercuric fulminate, when applied to the detonation of gun-cotton. Thus the detonation of silver fulminate is very decidedly sharper than that of the mercury compound, yet it is in no way superior to the latter in its power as an initiative detonating agent; indeed, a somewhat larger amount of it appeared to be required than of the mercury salt to induce detonation of gun-cotton with certainty. Again, the iodide and chloride of nitrogen are far more susceptible of sudden detonation than the silver fulminate; yet while 5 grains of the latter, confined in a stout metal envelope, suffice to detonate gun-cotton, 50 grains of chloride of nitrogen confined by water, appeared to be the minimum amount with which the detonation of gun-cotton could be accomplished with certainty, while no success attended the employment of confined iodide of nitrogen in quantities ranging up to 100 grains.