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By E Jak, M Shevchenko, E Nekhoroshev, D Shishin

In the field of pyrometallurgy, the presence of multiple molten phases with distinct chemical compositions, such as slags, mattes, speiss liquids, metals and molten salts, is a well-known phenomenon. These phases exhibit strongly non-ideal solution behaviour and are mutually miscible to varying degrees. To describe these complex molten liquids, the Modified Quasichemical Model (MQM) has proven effective and has been applied to numerous binary, ternary and several higher-order multicomponent systems related to pyrometallurgy. In recent decades, the complexity of high-temperature processes has escalated due to increased impurity concentrations in primary ores, the incorporation of recycled consumer products and the integration of metallurgical plants through by-product and waste exchanges. To address these issues, PYROSEARCH laboratory has been developing large 20-component thermodynamic database using a generalised CALPHAD (CALculation of PHAse Diagrams) methodology integrated with experimental investigations. Over the past decade, strategic decisions were made balancing the ability to generate experimental data, prediction power, accuracy, stability of calculations, as well as computational time, which are discussed in the paper. Examples provided for issues of >3 liquid immiscibility, non-ionic behaviour and exaggerated ‘sharp’ enthalpies of mixing in silicate slags, dealing with multiple oxidation states, as well as comparative analysis of pair and quadruplet approximation in MQM.

Aug 21, 2024

By Minji Jun

Leaching of the surface-coated metals from waste acrylonitrile butadiene styrene plastics (WABSP) has been investigated in the ammoniacal solution. The ammoniacal leaching of WABSP (typically containing 4.1 wt% Cu, 1.3 wt% Ni, 0.03 wt% Cr) efficiently dissolved copper and nickel, leaving unleached chromium as fine particles. The results indicate that the anions of different buffer media for metals leaching follow the order: CO3 2− > Cl− > SO4 2−. A declined leaching with high NH4OH–(NH4)2CO3 ratio (8:1) and a steep rise in extraction with high pulp in solution revealed the influence of anion (CO3 2−) and cation (Cu2+) present in the system. The leaching performed in carbonate solution by maintaining 5.0 M total NH3 concentration as NH4OH–(NH4)2CO3 ratio, 4:1; pulp density, 200 g/L; agitation speed, 400 rpm; temperature, 20 °C and time, 120 min yielded the maximum extraction (>99%) of copper and nickel. The study reveals a plausible recovery of the surface-coated metals from the WABSP without altering the properties of polymer material that can be recycled separatel

By W. Jilowa, C. Nguni, M. Simukoko, C. Nampungwe

The upsurge in cobalt price and demand is propelled by high demand from the electronics and electric vehicle industry. Konkola Copper Mines has cobalt occurring with copper in the ratio 1:10 in ore. The ore is treated in the concentrator and recovered at the smelter as an alloy (Cu 70%, Co 4%–7%, 15% Fe). Subsequent processing of the cobalt alloy is challenging, with very few plants able to treat it, leading to marketing challenges. Konkola Copper Mines sought to improve the cobalt alloy by producing a slag that is easier to handle and process in subsequent processes. Cobalt alloy (3.60% Co, 85.4% Cu) was re-melted in a copper bath four times the mass of the alloy. Silica and lime were added for phase separation and fire refining commenced. Following completion of fire refining and after holding the temperature at 1200°C, cobalt-rich slag was skimmed and blister copper was cast into anodes for electrorefining

Jan 1, 2023

Paper presented at the Mining Institute of Scotland's annual general meeting held in Glasgow, 8th April 1916. Although there is nothing novel or difficult about the sinking described, circular shafts are not numerous in Scotland so the details connected with such a sinking may be of interest. The shaft was sunk at Dykehead Colliery, Larkhall, which has been worked for over 50 years from the upper seams. It became necessary to sink another shaft to serve as a replacement downcast, by which the output might be maintained and some of the lower seams won. As the sandy clays regularly caused bulging into the rectangular shaft and sinking of the surrounding ground it was decided to make the new shaft circular and to enclose its mouth in a foundation-block of concrete resting on the solid clay. Details are given of the sinking, brick seating and lining, kettle strike, water-rings and doorhead lintels as well as the permanent fittings, winding gear and the cages themselves

Dec 1, 1916

By Shaojun Bai

Siderite ore with high phosphorus content was reduced isothermally at 1,050° C with pulverized coal and different dosages of sodium carbonate. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energydispersive analysis of X-rays (EDAX) were used to characterize the samples. The influence of sodium carbonate on the carbothermic reduction process was investigated. Sodium carbonate and its dosage played a considerable role in the carbothermic reduction. The iron particle size in the reduced ore was below 20 µm, and fayalite was abundant without sodium carbonate additive. With a mass ratio of Na2CO3-to-ore of 5% additive, the iron particle size in the reduced ore was generally above 50 µm, and the diffraction intensity associated with metallic iron in the XRD pattern increased. The effect of sodium carbonate on the phase transformation of fluorapatite during carbothermic reduction was also addressed via thermodynamic calculations and aqueous leaching experiments. The results showed that the fluorapatite was not reduced to P2 at 1,050° C, and a portion of the fluorapatite was converted to soluble phosphate. The reduction of siderite can be catalyzed by adding an appropriate amount of sodium carbonate. This catalytic activity was caused by an increase in the reducing reaction activity of FeO and the acceleration of the carbon gasification reactions. The decrease in phosphorous content in the iron concentrate was attributed to an improvement in the separation of the iron phase from the slag phase when sodium carbonate was added and with the formation of soluble phosphate.

By A. R. Sorta, D. C. Sego

ABSTRACT Temperature, solute, texture, and thixotropic effects on time domain reflectometry (TDR) measurements of water content in oil sands tailings are investigated. Results indicate that TDR water content measurements are influenced by temperature, residual bitumen, and percent clay in the tailings. A correction of 0.03–0.10/ °C must be applied to the apparent dielectric constant (Ka) to account for the effect of temperature. The Ka-volumetric water content relationships of slurries differ significantly from the commonly used Topp calibration equation. The age of the tailings and the addition of phosphogypsum did not influence TDR water content measurements.

Jan 1, 2013

By F. Ernest Brackett

Much new data on the flow of gases have been discovered by recent experiments by the United States Bureau of Mines and others. Although additional investigation is still desirable, the information now collected seems sufficient to attempt a tentative coördination of the friction factors. This study is confined entirely to fluid friction when the density throughout the duct is so nearly constant that it may be so considered. In the subsequent discussion the following notation is used: v = mean velocity of fluid in duct, feet per second. v' = mean velocity of fluid in duct, meters per second. R = hydraulic radius of duct, feet. R' = hydraulic radius of duct, meters. S = the hydraulic slope. P = pressure absorbed by friction, pounds per square foot. p = pressure absorbed by friction, pounds per square inch. p' = pressure absorbed by friction, kilograms per square centimeter. A = sectional area of duct, square feet. O = perimeter of duct, feet. L = total length of duct, feet. L' = total length of duct, meters. d = diameter of a cylindrical duct, inches. w = density of the fluid, pounda per cubic foot. g = specific gravity of the fluid compared with water = w % 62.4. C, k and B, coefficients for formulas using English measures. C' = metric coefficient, v' = C'R'S. n = coefficient of roughness for English or metric units. The basic formula for the flow of all fluids at constant density appears in the three following forms, which may be denominated: (a) The slope formula, v = CRS (b) The ventilation formula, " n = (c) The pipe formula, C is Kutter's coefficient, which is extensively applied to the flow of water in ducts and channels of all kinds; E is Atkinson's coefficient, used principally with air in ventilation problems; B is a coefficient conveniently adapted to studying the flow of water, gases and vapors in pipes. 312

Jan 1, 1927

By J. Christophe Niyonzima, Ekata Emmanuel Edo, Sayaf Mustafa, Liqun Luo

Iron and manganese both are important ferrous metals, and they usually need to be extracted separately for better usage. Ferromanganese ore from the Yunnan Province of China was investigated by subjecting it to reduction roasting, leaching, magnetic separation, hydrometallurgical separation process, X-ray diffraction (XRD), electron probe micro-analysis (EPMA) and scanning electron microscopy/energy-dispersive spectroscopy (SEM-EDS). It is noted that the ferromanganese ore contains valuable components or elements of 21.41 wt%Fe2O3 and 19.88 wt%MnO, which are 14.99% and 15.40% of the total of Fe and Mn, respectively, with a large amount of impurities comprising 33.00 wt% SiO2, 9.81%wt%Al2O3, etc. After roasting, microscopic examination showed the presence of haematite, magnetite, pyrolusite, psilomelane, hollandite, marcasite, pyrite, limonite, braunite and manganite, while XRD analysis showed that the magnetite content increases with the increase in roasting temperature, reflecting the increase in conversion of haematite to magnetite. Based on EPMAand SEM-EDS analysis, it was shown that the haematite and magnetite interface were the main Fe-bearing minerals; however, the dissemination of the two minerals, that is, haematite andmagnetite with the coexistence of Fe- and Mn-bearing minerals, will result in difficulty in effective separation of Fe and Mn. The effective roasting temperature and roasting time were 800 °C and 60 min, respectively, to avoid the formation of a composite oxide of MnxFe3-xO4 beyond 800 °C. The Fe recovery via roasting and magnetic separation only was 66.56%, whereas a combination of magnetic separation which ensued after the leaching process showed a recovery of 80.08% and 59.95% of Fe and Mn, respectively.

Mar 26, 2021

By P. O. Akinseye, F. T. Cawood

Mineral royalties are one of the oldest forms of mining taxation, and were initially introduced to extract economic rents from mining. Over time, the royalty regime has become more complex as it was identified as an important policy instrument that can achieve more multi-faceted outcomes. Such a multi-tiered approach in the use of the royalty instrument is also the case with South Africa. With South Africa’s new mineral royalty regime now in place for ten years, it is perhaps time to assess its impact and effectiveness. To carry out this assessment, an econometric evaluative study was undertaken using four major commodities in South Africa, namely gold, platinum, iron ore, and coal. The study explored five different policy options for government to consider and tested them to determine the most favourable one that will realize the regime’s policy objectives. After the assessment, two major options stood out. Hence, this paper seeks to highlight which of the two options is the most favourable for consideration by policymakers. Based on that study, we find that the current structure is effective, but also recommend that the factors in the formula for refined minerals be ‘modified’ to reduce the capped profitability ratio from the current 60% to 30% and the maximum royalty rate for refined minerals from 5% to 3%. The minimum rate of 0.5% during times of depressed mineral prices and no or low profitability will not be affected.

Dec 1, 2021

By Leonard Obert

THE CRACKING AND POPPING of rock, often heard by men working underground, for years has been interpreted as a warning of danger and unstable ground. However, not until 1939 was it discovered that rock under stress generates subaudible and sometimes audible seismic disturbances (referred to as "micro-seismims" 4), which can be detected with the use of a suitable seismic apparatus. Since that date laboratory and field investigations have been in progress to ascertain to what extent this phenomenon can be utilized to detect, localize, and determine the magnitude of areas of instability in and around mine openings and to predict if and when failure will occur. These investigations have included a determination of the types of problems to which the method is applicable and the effect of rock type, geological defects, such as joints, fractures, faults, and other uncontrollable factors, on the reliability of results. Six reports have been prepared covering the investigations conducted between 1940 and 1952 (4-9). 5 These reports describe some of the characteristics of micro-seismims, as determined from both laboratory and field tests; the equipment used to pick up and record micro-seismims; the general test procedure and method of analyzing results; and applications of the method to specific mining problems.

Jan 1, 1957

By Ted H. Eyde

Both private industry and the Interior Department have become alarmed about the enormous amount of Federal land that has been withdrawn from appropriation either under the Mineral Leasing Laws or the Mining Law of 1872. According to a recent article by Gary Benethum and L. Courtland Lee, governmental actions have withdrawn nearly 400 million acres from the operation of the Mining Law of 1872 and over 500 million acres from the Leasing Laws. An addition al 100 million acres for the Mining Law of 1872 and 70 million acres for the Leasing Laws are either encumbered or being managed in such a way as to constitute a defacto withdrawal from mineral development. This means simply that mineral exploration end development under the Mining Law of 1872 is either prevented or discouraged in an area the size of the states of California, Arizona, Washington, Oregon, Nevada, Utah, Idaho, and one half of Colorado combined. Under the Mineral Leasing Laws, exploration and development is either prevented or discouraged in an area equal in size to all the states east the Mississippi River, except Maine.

Jan 1, 1976

By V. F. Petrov, O. D. Khmelnitskaya, V. M. Lodeischikov

"The processing of copper gold ores is one of the major issues of gold-mining industry in the beginning of 21st century. In this case, application of ammoniacal cyanidation process for this type of mineral raw materials deserves special attention. Irgiredmet Institute has carried out a wide range of studies on ammoniacal cyanidation process and evaluated the possible commercial use of this process for Russian operating plants. Copper gold-bearing ore from a current Russian deposit was studied. The content of gold and copper in the ore is 9.4 g/t and 0.4%, respectively. Based on the results of preliminary test work, a flow sheet was developed. It included gravity concentration followed by cyanidation of the gravity tailings using CIP. The flow sheet provides sufficient total gold recovery (91.5%). However, this technology has disadvantages, such as high specific consumption of reagents: 4.5 kg/t NaCN and 13.5 kg/t Ca(OCl)2 the ore and the increased gold grade in the liquid phase of the tails slurry (0.2 g/t). In order to improve cyanidation process parameters, test work on gravity tails processing using ammoniacal cyanidation was carried out. After the test work was completed, ammoniacal cyanidation flow sheet for copper gold-bearing ores was developed. Leaching conditions were optimized using recycled process solutions. Recommendations on gold recovery from the solutions and tails detoxification are given. The proposed flow sheet provides 91.5% gold recovery. In this case, compared to the conventional option, the consumption of cyanide decreases by 3-4 times.INTRODUCTION The technology of precious metals recovery from gold-bearing ores is based on cyanidation. This accounts for up to 90% gold recovery and the significant portion of silver (Lodeischikov, 1999). However, there exists the category of so called refractory ores. They are not amenable to direct cyanidation (without using additional expensive processes), or they are characterized by low indices of metals recovery and high consumption of reagents. The latter also include copper gold ores. Their deposits can be found extensively both worldwide and in Russian Federation. A feature of these ores is that they contain not only gold but also copper. It is considered not only as a valuable component but also as a harmful mineral impurity that hinders gold cyanidation, gold precipitation from the solutions by cementation onto zinc dust and adsorption onto activated carbon (CIL, CIP-processes), detoxification of cyanide bearing effluents."

Jan 1, 2018

By Richard A. Dick

Eight blasts were fired in a 2-1/2-ft bench in the Stewartville member of the Galena Limestone formation in an aggregate quarry near Stewartville, Minn. The shots were dimensionally proportional to production-size bench blasts and were about 5 to 10 percent of full scale. The effects of site, timing of initiation, and burden-to-spacing ratio were studied in a 2 x 2 x 2 factorial experiment, using three boreholes, caw;, containing a 1/2-in charge diameter of high-density ammonia dynamite, in each blast. Detonation velocity measurements indicated that the dynamite detonated satisfactorily in the 1/2-in charge diameter. The effects of the three experimental variables were analyzed by weight for the percentage of oversized material produced and for size distributions determined by screening the entire muckpiles. The bench faces were painted before each shot in an effort to determine the origin of the oversized material. The square pattern (burden and spacing = 15 in) produced finer overall fragmentation and less oversized material than the rectangular pattern (burden = 15 in; spacing = 22-1/2 in). Sites 1 and 2 were about ft apart. Although site 2 produced slightly better overall fragmentation than site 1, the amounts of oversized material produced showed no significant difference. The timing of initiation (instantaneous or delayed) did not significantly influence the overall fragmentation or the amount of oversized material produced.

Jan 1, 1973

By E. D. Stephenson

As part of the British Steel Corporation?s development plan during the 1970?s, it was decided to concentrate its bulk steelmaking processes based on the BOS at 4 major Works with access to deepwater ore terminals, for the supply of high-grade imported ores. These 4 sites were at: - 1. Rarenscraig Works in Scotland where the ore terminal would be hilt at Hunterston on the west coast some 50 miles away. Bavenscraig was already an integrated Works but suffered from having to discharge ore 27 Glasgow tenxinus on the River Clyde, which could only accommodate vessels up to 25,000 tonnes. In the future, ore was to be unloaded at Runterston and shipped by a rail-link into Ravenscraig, The new ore terminal would have the potential to unload vessels up to 300,000 tonnes. - 2. Port Talbot Works in south Vales where the existing harbour was developed to discharge large ore carriers. This again was an existing Integrated Works and the benefits of the new harbour also applied to Llanwern Works which was another integrated Works some 50 dies to the east, which would now receive ore from Port Talbot.

Jan 1, 1980

By D Pateman, F de Fredrick

The Bentley underground mine, which is located 60km north of Leonora, Western Australia, is owned and operated by Round Oak Minerals Pty Limited. A high-grade Zn-Cu Volcanogenic Massive Sulphide (VMS) orebody, Bentley was discovered in 2008 with production commencing in 2012. Long-hole open stoping is employed to mine the steeply dipping ore body, and in recent years the Avoca method has been adopted. This requires all development in a particular area of the mine to be completed prior to stoping commencing in a bottom up sequence. Voids are commonly backfilled with loose Run-of-Mine (ROM) waste loose rockfill (LRF); or alternatively cemented rockfill (CRF) can be used. Stopes in the 3860 AOS and 3900 AOS panels were located below previously extracted Avoca zones, with LRF situated immediately above them. These high-grade stopes were originally designed with rib and sill pillars to maintain control of the existing backfill during extraction. Due to changing factors over time, including mining economics, alternative options to achieve full extraction of the stopes were reviewed, including: • Mining small successive full height stopes which would involve drawing a blanket of LRF down with the extracted ore (stoping under waste); • Stabilisation of the existing LRF above the stopes and implementing a primary/secondary stoping sequence, with the primary stopes backfilled using a cement fill. An assessment of these options was undertaken which determined that the second full extraction method was the most beneficial to the operation, and could be achieved using a cement grout (Minova’s FB200 grout) to stabilise the LRF in conjunction with implementing a sequence where the primary stopes would be backfilled with cemented aggregate fill (CAF). Footwall drives were developed adjacent to the rockfilled stopes, allowing for the installation of horizontal grouting conduits, as well as providing access to the top of the planned 3860 and 3900 level stopes for the placement of CAF. An interval at the base of the previously rockfilled stopes was grouted at multiple horizons to achieve the required thickness, with a comprehensive quality assurance/quality control (QA/QC) process undertaken. Primary stopes were CAF backfilled via an arrangement of downhole winzes, linking the top of primary stopes to cross-cuts developed off the associated footwall drives. CAF was delivered underground through an open reticulation network that was extended to the specific levels. Overall the successful implementation of the revised mining method effectively increased ore recovery while maintaining control of overbreak and dilution, providing significant financial upside. This was achieved while maintaining effective controls in light of the changes to the risk profile. Stabilisation of the existing rockfill has allowed the extraction of stopes to full height, including the originally designed sill pillars, representing an average 23% increase in ore tonnes on the initial design, with dilution from the stope crowns averaging less than 1%. The use of CAF in association with primary/secondary stoping, eliminating the need for rib pillars, has yielded an average 47% increase in ore tonnes compared to the base case mine design.

Mar 15, 2021

By F. T. Havard

(Canal Zone meeting, November, 1910.) I. INTRODUCTION. THE present truce in litigation between Western smelting and ranching interests gives opportunity for a summary of the results achieved by metallurgists in condensing fume and de-acidifying furnace-gases. In the absence of complete records of past experiments, there has been a good deal of unnecessary duplication of attempts and' failures. Yet, especially under the recent policy of our large corporations, looking to the economic recovery of the values of by- and waste products, original and, in some cases, effective measures have been developed by American metallurgists. In the case of Bliss vs. the Anaconda Copper Mining Co., the Montana Supreme Court, recognizing the progressive efforts made to render the flue-gases innocuous, and the value to the community of the smelting company's operations, refused to hamper its work, and returned a verdict in favor of the defendant. In the trial, the experimental firms of the company in the so-called "affected region" were proved to be thriving perfectly, showing that immunity was guaranteed to vegetation and stock by the wide distribution of the sulphurous acid gas in the dry air of Montana. Indeed, L. S. Austin has proved that by the time the fume is 4,000 ft.. distant from the stack, the percentage of sulphurous acid has been diminished from 2.28 to 0.00045; and Angus Smith has shown that rain must contain 40 parts per million of free acid before vegetation is affected. The arsenic in the stack-gases is but a very small part of the original content of the ore, of which 80 per cent. and over is rejected in the concentrator and furnace waste-products or recovered in the flues. Nevertheless, neither the peace in Montana nor the armistice

Aug 1, 1910

By R. M. Honey

An attempt is made to summarise the mining law of England, Wales and Scotland. Attention is also drawn to the recent privatisation of the electric power and gas industries and the intention of the present Government to follow suit as regards coal mining. The subject of mining law is discussed under the headings: minerals or rights that have been nationalised or are vested in the Crown; ownership (of land and mineral rights); special customs; tracing of owners; right of support (arising from mining); ancillary rights and easements; obtaining prospecting and mining rights; planning permission; statutory aids to obtaining rights; notes on the history, law and practices of petroleum (onshore and offshore), gas, coal, prescribed substances, gold and silver; electricity; safety, health and welfare; and technical information and boreholes. A correction in the subsequent issue amends errors on p.A75 and A82 and regrets the publication of misinformation on the availability of grants

May 1, 1991

"An innovative concept is proposed whereby the operating power for haul trucks in certain areas of an underground mine are reduced in order to lower ventilation costs. Airflow that must be provided for diesel-powered equipment in most jurisdictions are regulated based on engine peak power capability and engine emissions, both of which can be lowered by artificially reducing the capacity of the engine through the engine control unit. Advances in asset tracking and ventilation on demand enable this methodology and this study demonstrates that it could represent significant value for mine operators. An examination of haul truck duty cycle indicates that de-rating of engine operating power based on the truck’s location in the mine can enable a step change in ventilation rates, often with no material impact on working conditions. Methods for implementation and estimate of cost savings will be defined.INTRODUCTION Ventilation of underground workings remains a significant operating cost burden for modern mine operators. In particular, ventilation rates for underground diesel mining equipment are often defined by local regulatory bodies and are assumed to present minimal opportunity for optimization or savings, at least until battery propulsion systems can be adopted. Commonly, the quantity of air flow required is defined by the peak rated engine output power of diesel equipment. For example, Ontario Regulation 854 SS 183.1 (3) states that “The flow of air must be at least 0.06 cubic metres per second for each kilowatt of power of the diesel-powered equipment operating in the workplace”. Jurisdictions that define air flow using the prescribed CANMET or MSHA ratings use peak engine emissions to calculate air flow required for dilution ventilation. These approaches are similar in that the maximum power capability of a vehicle’s engine is used to define the ventilation rate in all areas where it travels, regardless of what power output is actually used in any of those areas. Examination of the duty cycle of a typical underground haul truck identifies a large variance in the power output of the vehicle depending on its location in the mine and the activities undertaken at these locations. For example, travel on a mining sub-level requires a fraction of the truck’s peak power due to the minimal grade and significantly reduced travel speed. So if we can reliably reduce the peak engine power capacity and engine emissions in areas where peak power is not required, we can logically cut the ventilation rates for those areas."

Jan 1, 2017

By Earl C. Redman

The Juneau Gold Belt, centered on Juneau and approximately 120 miles long by 10 miles wide, stretches from Berners Bay on the north to Windham Bay on the south (fig. D-l). Access within the Juneau Gold Belt is provided by the Glacier, Thane, and North Douglas Highways. The Glacier Highway extends northwest from Juneau for approximately 40 miles to Echo Cove, and the other two roads end 5.5 miles southeast and 12.6 miles west from Juneau, respectively. None of these roads connect with other highway systems and access to other areas is restricted to airplanes, the State ferry system, and commercial barge lines. BUREAU ACTIVITIES The majority of lode gold produced in Alaska came from the Juneau Gold Belt portion of the Juneau Mining District. To evaluate the economic potential of the Gold Belt, the Bureau located 173 mines and prospects within the area. A total of 263 ad its and shafts were found and 56,650 feet of underground workings were mapped. The Bureau collected and analyzed 1,557 samples during the study. In addition, considerable detailed geologic map-ping was done in the vicinity of the mines and prospects from which ore control models were developed.

Jan 1, 2012

By Glenn L. Cook

Correlations between mass spectra and molecular structures of 186 organic sulfur compounds are discussed. The olefinic ions, the alkyl ions, the CnE2n+1 ions, the m/e 61 ions, and the m/e 35 ions in the spectra of thiols are related to molecular structure. In the spectra of sulfides, the olefinic ions, the m/e 61 ions, the m/e 35 ions, the CnH2n+1S+ ions, and the CnH2n+1SH+ ions are correlated with molecular structure. For disu1fides, the correlations relate HSSF+& and RSSH+ ions to molecular structure. Base peaks of alkylthiophenes are correlated to their molecular structures. Some unimolecular reactions of sulfur compounds in the mass spectrometer are considered. A cyclic intermediate is suggested for the reaction which produces m/e 47, CH3S+, and m/e 48, CH4S+, ions in the spectra of sulfides. An expanded ring is suggested as a possible intermediate in the reactions of thiophenes. Heats of formation of sulfur-containing ions and their appearance potentials are presented in tabular form. Ionization potentials for sulfur-containing radicals and molecules are also given. Discussion of the spectra, tabulated in the appendixes, provides an insight into the relationship of the molecular structure of a compound to the mass-to-charge ratios and the intensities of the ions in its mass spectrum. Correlations of the mass spectra with molecular structures are empirically developed by observing regularities in the spectra of the reference compounds. Correlations extend the usefulness of mass spectra because they can be employed to determine the molecular structure of an unknown compound.

Jan 1, 1965