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By G. W. Jones, R. E. Kennedy

Most gasolines and naphthas are mixtures of paraffin- series hydrocarbons and comprise such substances as pentane , hexane , heptane , octane , and others up to perhaps dodecane . Many of these hydrocarbons , when mixed with the proper proportions of air and ignited , are highly explosive . It is due to this characteristic that gasoline has become so important as a fuel in internal -combustion engines . Gasoline and naphtha also are used in the industry as solvents and cleaning agents . Because of their explosive properties they are dangerous to use unless the composition is so chosen that the vapor pressure of the mixture is not high enough to produce explosive mixtures with air at the temperature at which they are used . Hydrocarbon mixtures may be made less hazardous by adding some incombustible liquid , such as carbon tetrachloride . Barrier reports the amount of carbon tetrachloride that must be added to different naphthas to render such mixtures free from fire and explosion hazards . He found that the amount of carbon tetrachloride that must be present in the final mixture of naphtha and carbon tetrachloride varied with the density of the naphtha . Of the naphthas tested the amount of carbon tetrachloride necessary to render such mixtures free from fire and explosion hazards ranged from 30 to 70 percent . .. Determination of the fire and explosion hazards of carbon tetrachloridehydrocarbon mixtures would be easy if the boiling points and vapor pressures of the two were the same at any given temperature . The fact that carbon tetrachloride boils at 76° C. while the boiling points of the hydrocarbons found in gasoline and naphtha may range from 37° , the boiling point of pentane ,

Nov 1, 1934

By D. Harrington, C. W. Owings

The mining industry is gradually realizing that safety education and safety inspection are economic factors that may not be overlooked as a means of reducing operating costs . Many mine operators , however , have failed to realize the benefits of safety , and the efforts of the more progressive mining companies are offset by the carelessness of neighboring companies when the accident records of a community or a State or the nation as a whole are considered . This tendency is indicated by the data collected by the safety division of the United States Bureau of Mines . During the fiscal year ended June 30, 1930 , relatively definite information: was secureä concerning 34 mine explosions , 24 mine fires , and 29 miscellaneous accidents ; these accidents are by no means all of the explosions , fires , and miscellaneous accidents which occurred in the mines of the United States during the period; but the data on the fires and explosions constitute a record of all of those types of accidents that were called specifically to the attention of the safety division , and the miscellaneous accidents include those on which definite , detailed data were obtained by the safety division .

Jan 1, 1931

By Fred Turin, Kim Cornelius, Lisa Steiner

NIOSH researchers have been examining underground coal mining activities in order to evaluate work crew hazards. In 1994 a continuous mining machine operator was killed by falling roof during extended cut mining. Many aspects of the incident were used by NIOSH researchers to develop a scenario interview. The goal was to provide a realistic framework for acquiring frank and detailed insights. The interview consists of two sections. The first describes the underground mining conditions. The second recounts the fatal incident. Each section is supplemented by a diagram and a set of questions addressing relevant safety issues. The interview was administered at three mines that actively take extended cuts. Researchers found the scenario approach to be an effective interview tool as well as an effective hazard awareness and safe work practices training platform.

By Joseph A. DeCarlo

This information circular presents data for 1960 on individual coke plants in the United States. All oven-coke plants in existence, whether active or idle at the close of the year, are listed in this report. With two exceptions, only beehive plants on which reports were submitted to the Bureau of Mines are included. Although the Bureau was unable to obtain reports from these two active plants in 1960, the number of ovens and annual coke capacity are estimates, based on previous reports filed with the Bureau of Mines. Accordingly, there were 73 oven-coke plants in existence at the end of 1960 of which 70 were active. Reports were received on 44 beehive plants of which only 13 were in operation at year end. Oven-coke plants are listed alphabetically by States in table 1 which shows the name and address of the company, location of plant, classification or type of ownership, number and type of ovens, annual coke capacity, and coal-chemical materials produced. The terms "furnace" and "merchant" plants used in this and all other reports of the Bureau of Mines designate the type of ownership. Furnace plants are those owned by iron and steel companies whose main business is production of coke for use in their own blast furnaces. Merchant plants are those associated with chemical companies, gas utilities, as well as those that produce for sale on the open market metallurgical, industrial, and residential-heating grades of coke and coal-chemical materials. The annual coke capacity shown for each plant in this table is based on the minimum coking time necessary to produce coke with qualities suitable for its intended use. Therefore, the annual capacity of a plant may change from year to year, depending on age and condition of ovens, the character and quality of coal carbonized, the grade of coke required, and other factors. For example, annual coke capacity of a coke plant primarily making foundry coke with longer coking cycles would be lower than one making blast-furnace coke. Also some ovens must be operated at slightly lower than normal flue temperature because of the condition of the refractories and maximum capacity would be somewhat lower than designed capacity. For this reason, the capacity reported to the Bureau of Mines may differ from the designed or rated capacity estimated by the coke-oven builders at the time of construction. For example, if the generally accepted standard coking rate of one inch per hour were used on all ovens to calculate total annual capacity, it would have been 80.4 million tons or 2 percent higher than the capacity reported to the Bureau. Because of the factors mentioned above, the annual coke capacity shown in this table is believed to be a reliable measure of the practical operating capacity of the industry.

Jan 1, 1961

By L. C. IlsLey

The Burrell methane indicator developed by Col. G. A. Burrell in 1915 was modified during 1918 to the " insulated type " Burrell indicator . Though this instrument has been used in mines since its first introduction , it was not formally approved as safe and efficient for use in gaseous mines until March , 1922. The indicator is built by the Mine Safety Appliances Co. , Pittsburgh , Pa . Approval No. 800 has been assigned to this company covering the device in the form approved . The principle of the Burrell indicator is fairly well known . It works on the same principle as the Haldane apparatus - measuring by means of a graduated scale , the contraction resulting from burning the methane content of an air and gas sample . A given aniount of the mine atmosphere to be tested for methane is taken into the indicator . This sample is then thoroughly shaken with the water in the indicator for one minute . The methane in the sample is now burned for two minutes by a heated platinum coil , which is energized by a small storage battery containing two Edison cells connected in series . After the glower or coil has burned for two minutes , it is disconnected from the battery , and the indicator is again shaken for The amount of contraction observed by reading the height the water rises in the U- tube of the indicator , which is calibrated to register the percentage of gas in the sample . The indicator as approved by the Bureau of Mines is equipped with an Edison M- 8 mine- lamp battery , and with a glass and scale graduated from zerɔ tɔ four per cent methane . The approval of a corbination service that is , an attachment for giving illumination from the same battery from which the platinum glower is operated has been withheld pending the development of a battery with larger capacity . - Under laboratory operating conditions , a single glower was capable of making at least 20 determinations if proper precautions were observed with respect to the use of freshly charged batteries . A battery should be allowed to stand off charge several hours before using in an indicator , as the peak voltage of a freshly charged Edison cell is abnormally high and is likely to send enough current through the glower to melt the platinum wire . Fifty-seven satisfactory operations were obtained from a completely charged battery . The point where the voltage of the cell fell below 2.3 volts with the glower attached was taken as the lower limit of successful operation . A voltage less than 2.3 does not permit the lower to burn at a temperature that will completely burn the gas in the air , thus giving a false indication .

Jun 1, 1922

By McHenry Mosier

This paper describes the practice in diamond drilling blast holes and discusses the relative merits of this method as compared with drilling by percussion rock-drills at eastern magnetite mine A. The rooke that were drilled included: (1) Gneiss; (2) sohist; (3) crystalline limestone; and (4) granular masses of magnetite. The principal stoping methods were: (1) Sublevel open stoping and (2) inclined room-and-pillar. Diamond drilling was used in the sublevel stopes and in some of the large pillars in an old section of the mine. Experimental work on diamond drilling blast holes began in 1943. Drill- ing proved difficult owing to the occurrence of fingers of extremely hard barren rock in the magnetite ore. All diamond drilling was contracted to a firm that furnished everything necessary for drilling except compressed air and water. In most instances the diamond-drill machine is clamped directly to a 3.5-inch column to reduce vibration. For drilling in floor pillars in open stopes, the drill was set on a demountable, sectionalized steel, frame with four legs carrying a 20-foot, 3.5-inch, extra-heavy pipe. "Both coring and noncoring bits were tried. In holes drilled with a cor- ing bit, the core was ground into sludge as the bit advanced so that it was unnecessary to delay drilling for pulling core. Data on tests with several types of bits are given as well as some oper- ating results. A direct comparison of costs between diamond drilling and percussion drilling was not available. The advantages of diamond drilling blast holes at mine A included: (1) Safer working conditions in open stopes. (2) The recovery of additional ore. (3) A reduction in the amount of stops development.

Dec 1, 1946

Treat contaminated coal mine drainage to meet EPA and State water quality requirements. Approach A model (fig. 1) is presented for selecting, designing, and sizing one or several passive mine drainage treatment systems that can be used in remediation of abandoned mine lands (AML). The three principal types of passive mine drainage technologies for the treatment of coal mine drainage are an aerobic system, a compost wetland, and an anoxic limestone drain. The multistep approach presented here provides a simplified method to characterize the type and magnitude of the water quality problem and then to select either a single treatment system or a combination of treatment systems to address the specific site situation. How It Works Step 1. Discharge Characterization. Characterization of the discharge consists of measuring the discharge flow rate and collecting water samples at the point of discharge for chemical analysis. Both the flow rate and chemistry of a discharge can vary seasonally and in response to storm events. It is important to account for this variability by determining flow rates and water chemistry under various conditions.

Jan 1, 1992

By Stephen L. Tillim

Tubular Handles can negatively affect the contents of the carpal tunnel. Years of injuries from grasping handles for tools and machines can cause carpal tunnel syndrome, tendonitis and wrist joint injuries. The can cause inability to use a hand and resulted in the longer absences from work than injuries from falls, accidents or fires.1 Cylindrical, tubular and rectangular handles are rolled flat structures. They place the hand on a rolled flat surface where the ends of the middle and ring fingers overlap the index and small fingers. They are pulled along a series of lines that contact the end joint of the index finger, the middle bones of the middle and ring fingers and the end bone of the small finger. Cylinders are pulled diagonally in the hand toward the carpal tunnel (CT) area. Gripping in this manner tenses asymmetric muscle groups in the forearm. Handles could work better if they do not place pressure on the CT and conform to the natural function or neutral hand position where the hand rests or dangles at the side of the body, the finger tips form a diagonal, the palm and fingers form a cup, the thumb rests between the index and middle fingers and the wrist is mildly extended. However, handles designed for the neutral position are pulled by diagonally oriented fingers into the valley between the thenar and hypothenar muscles where they can compress the median nerve and tendons exiting the CT. Seven principles for handles that do not place pressure on the carpal tunnel and employ optimal hand position are presented. First, handles should align the ends of the fingers parallel to the horizontal crease and not diagonally. Second, handles should extend from the cupped fingers to meet the muscles at the base of the thumb on the radial side of the hand and extend further on the other or ulnar side to meet a portion of the small muscles. Third, handles should have a recess on the proximal side to prevent contacting or placing pressure on the carpal tunnel. Fourth, handle design should be based on hand measurements in a position of function. Fifth, handles should come in sizes. Sixth, handles should be placed on tools to maintain the wrist and elbow in neutral position. The seventh is handles should support the maximum area of the hand and absorb, but not direct, vibration to the carpal tunnel. These principles led to prototypes and patents for handles for gripping, pinching and squeezing2,3,4 . The poster will illustrate and explain the principles Bonsil handles. Research, with existing tools, is needed to substantiate claims made for the Bonsil handle.

Jan 6, 2006

By Launa Mallett, Michael J. Brnich

The first step to emergency preparedness is defining and analyzing hazards. Although all hazards should be addressed, resource limitations usually do not allow this to happen all at once. Risk assessments are used to establish priorities so that the most dangerous situations are addressed first and those least likely to occur and least likely to cause major problems can be considered later. While the examples provided in this training package are specific to mine fires, the concepts and tools can be applied to any mine hazard. Purpose: This training package was developed to assist instructors, as they: 1) determine how to use risk assessment to improve preparedness for mine fire emergencies and 2) present risk assessment concepts and tools to trainees. Audience: This package is appropriate for workers/trainees from all types of mines. A risk analysis can be conducted by anyone familiar with the location(s) being studied. Why Conduct a Fire Risk Assessment? During a risk assessment, hazards are evaluated in terms of the likelihood that a problem may occur and the damage it might cause. Mine fire preparedness requires consideration of all possible fires that could occur. However, at a given mine some fires are more likely than others and some would result in greater damage than would others. Conducting a risk analysis identifies these differences. The results can be used to target resources at the types of fires that are most likely and/or are most destructive. Hazards that are very likely to result in fires that would do considerable damage to people and property should be targeted first for remediation and/or effective response if remediation isn't possible. Potential fires that are less likely or that would have less severe consequences are identified for attention later, after the more serious situations have been addressed.

Jan 10, 1992

Background: The National Institute for Occupational Safety and Health (NIOSH) recently investigated ignition incidents resulting from drilling holes into sealed and filled plow frame sections. A farmer and farm worker were seriously burned in two separate incidents that occurred in the same county in New York under similar conditions. They had just penetrated sealed sections of their plow frames with electric drills when a roar of escaping gas at high pressure was heard, and the victims were thrown back by the gas jet and engulfed in flames. The flames were quickly extinguished ,but the victims suffered burns. NIOSH experts were asked to help find the cause of these hazardous incidents.

Jun 1, 1998

By Barbara Fotta

According to the Bureau of Labor Statistics (BLS), workforce estimates of median age suggest that the median age of the mining workforce, which has been experiencing overall declines in numbers of employees, is rising more rapidly than for the overall U.S. civilian labor force. In the absence of detailed demographic data for the mining industry, the current study uses injury and illness data reported to the Mine Safety and Health Administration (MSHA) to examine differences, over time and by commodity, in the proportions of injured or ill workers aged 45 years and older. These data indicate that from 1988 to 1998, the percentage of injured or ill older workers (aged 45 years and older) have been steadily increasing. The most notable increase occurred at coal mining operations where the proportion of injured/ill older workers increased from 24 to 44 percent. A more detailed breakdown of the industry by commodity for 1998 showed the highest proportions of older injured/ill workers (over 40%) occurring in coal, iron ore, alumina mills, cement, and trona operations. In coal operations, as the employment size of the mine operation increased, so did its proportion of older injured/ill workers. Also, higher proportions of older injured/ill workers were observed at surface coal work locations than at underground locations. The distribution of older injured/ill miners by occupation for several select commodities shows the highest proportions for supervisors, electricians, mechanics, and surface equipment operators, and the lowest proportions for surface laborers and for underground coal roof bolters and scoop operators. With few exceptions, older injured workers have the highest median number of days lost per injury when examined by type of mining operation and by occupation. Given the high proportions of older injured or ill workers in many sectors of the mining industry, health and safety programs must consider the physiological changes associated with aging when evaluating job tasks and the working environment.

Jan 1, 2004

By R. V. Ramani, C. B. Manula, A. Owili-Eger

The mine ventilation system consists of the fan, the roadways, and the regulatory devices. Sufficient fresh air must reach each working face in the mines to render harmless noxious, toxic, and respirable pollutants and to provide for the breathing of men. This is achieved by the proper selection of fan and regulatory devices. Because a mining system is dynamic, the mine ventilation system must also be dynamic. In short, mine ventilation engineers are frequently called upon to provide answers to the following questions: 1. Given a mine or the projected plan of a mine, what fan must be selected for the quantities specified in the section? At what point in its characteristic must it be operated? Are any speed changes or changes in blade settings warranted? 2. What should be the regulation in a section to insure cer¬tain desired quantity in that section? How does it affect the overall ventilation system? 3. What are the effects of driving a new shaft? Where should it be located? What size fan should be installed in the shaft? How does this affect the overall ventilation sys¬tem? 4. How much quantity increases can be obtained by cleaning up falls and streamlining roadways and by driving addi¬tional parallel airways? These questions are in no way exhaustive, nor are answers easy. Most of the operational and planning problems discussed above are to a cer¬tain extent solved by ventilation engineers using rules of thumb from experience. Both natural conditions and regulatory requirements have changed so drastically recently that use of scientific methods in ventilation planning and of faster methods in evaluating the plans is a must. Fortunately, computers offer the greatest hope for good

Jan 1, 1975

By Arthur L. Murray

"Oil-shale camps are peculiarly favored, in that before they are established it can be ascertained with a,of certainty, that the life of the project is not limited. Unlike camps at metal mines, where the metal content of a given area is frequently an unknown quantity until after years of development, oil-shale camps should, from the outset, be planned and built as permanent types of camps. Where this procedure is followed camps will be established which better serve the needs of the industry and the cost of their general care and upkeep will be less.Selection of camp or townsite.The site of the camp or town, whether on company property or not, should be selected with care. It should be separate if possible from the location of the plants of the company so as to be free from noise and fumes and so as to provide a change of environment for employees in going from their work to their homes.The principal features governing the site to be selected are as follows:Drainage. The general contour of the surrounding country should be such that drainage is away from the site. The camp or town should, if practical, be situated on higher ground than that in its immediate vicinity.Soil. The nature of the soil on which the camp or town is located may bear a decided relation to health. A porous, well under drained top soil of at least four feet in depth insures dryness and facilities the placing of foundations and the laying of water mains and sewer pipes. Such a soil also is an advantage in growing trees, shrubs and grass plots, which are a decided adjunct to making the community attractive."

Jun 1, 1921

By Wilbur I. Duvall

This paper presents arguments which show that a velocity seismograph should be used to measure building and ground vibrations produced by blasting . However , portable velocity seismographs suitable for this type of measurement are not commercially available . The paper describes how a velocity seismograph can be assembled from commercially available velocity gages , amplifiers , and recorders . Also , specifications are given which could be used in the design and manufacture of a portable velocity seismograph suitable for measuring vibrations from blasting .

Jan 1, 1964

By James J. Bryja, Thomas M. Barczak, Dennis R. Dolinar, Joe Bower, Thomas P. Mucha

Maintaining ground stability in the gate roads, particularly the tailgate, has always been critical to the success of longwall mining, both in terms of safety and productivity. Several new support technologies have been developed in recent years to replace conventional wood and concrete cribbing for secondary roof support. Since their performance characteristics are unique, the best practices that have been developed with conventional wood cribbing may not be applicable for these alternative support technologies. Therefore, with so many options to consider and the importance of achieving adequate ground control at minimal cost, the trial and error approach to longwall gate road support is no longer prudent. This paper discusses a design methodology for standing secondary tailgate supports. This design technique requires in-mine measurements of tailgate support loading and convergence to establish a tailgate ground, reaction behavior based on the support and strata interaction. The methodology uses the performance characteristics generated in the National Institute of Occupational Safety and Health (MOSH) Mine Roof Simulator (MRS) to match the stiffness and load characteristics of various supports to the measured ground reaction behavior. It can be used to determine the appropriate -- application of alternative roof support systems or to design in- mine trials such that a fair and equitable comparison of different support systems can be made. A case study if the methodology at a western Pennsylvania mine site is presented in the paper, including a comparison of four alternative support technologies to conventional wood and concrete cribbing historically used at this particular mine.

By L. L. NAUS, R. D. Currie

Hazards in connection with the use of compressed-air jets for ventilating gassy mines are given little consideration by most mine officials largely because compressed air is considered the safest means of transmitting power for operating various types of mining machinery, and the inherent dangers in its use for this purpose are virtually negligible . The installation of compressed-air lines in coal mines leads to the utilization of compressed air for ventilating working places , with the result that , although the primary ventilation systems may be adequate to meet existing needs , proper conduction of normal ventilation has been neglected , so the working faces receive only a small amount ofthe total air circulated through the mine . Reliance in part on compressed air or other auxiliary means for ventilation is always attended by danger that gas will accumulate , due to intermittent operation , and the tendency is to operate auxiliary schemes only. during the working shift ( or possibly only part of the shift ) and to dispense with them during off- shifts or at times during the working shift when gas may accumulate because of lack of ventilation . When the men come on shift the auxiliary ventilating device often may be started without a preliminary examination of the working place , or .. the examination may be made sometime before the oncoming shift arrives , the gas being allowed to accumulate in the meantime. This may result in uncontrolled movement of a body of gas if proper precautions are not taken . Several mine explosions have been caused by the movement of a known body of gas by compressed air into the haulageway, where it was ignited by an arc from a passing locomotive . This danger is more pronounced where supervision is lax .

Aug 1, 1937

By L. D. Tracy

Many bituminous coal-mining companies have inaugurated extensive safety programs, but the failure to have approved or permissible equipment or safe practice in only one part of a mine has resulted in disaster. The necessity of using only equipment bearing the U. S. Bureau of Mines approval plate is emphasized by the fact that many accidents are the direct result of carelessness on the part of trusted employees using non-permissible equipment. A concrete example is found in the case of an explosion on October 26, 1926, in a mine in the Pittsburgh district, Pennsylvania. Story of the Explosion At about 10 o'clock on the night of the explosion an examination was made in No. 2 butt left and parallel off No. 14 north, and was found to be clear of dangerous accumulations of gas. (See figure). Several hours later a crew of two men brought a self-propelling rock-dusting machine within 50 feet of the face of No. 2 butt parallel before they examined for gas. The machine operator found an accumulation of explosive gas about 13 inches from the roof. He began to wave his arms thoroughly mixing the gas and air. Undoubtedly a highly explosive mixture was created, and as the men attempted to run the machine back to fresh air as explosion occurred.

Jan 1, 1927

By A. M. Dale, J. Standeven, B. Evanoff

Tool manufacturers continue to incorporate new designs to the internal mechanism of tools in order to decrease the vibration that is delivered to the hand during operation. Modification of some tools to minimize tool vibration is not easily resolved through internal tool design. For this reason, vibration damping materials applied between the tool and the hand are a simple alternative. The damping materials may be applied to the area of the tool directly contacted by the operator or in a glove containing a vibration absorbing pad. These interventions are developed specifically to damp vibration but are not necessarily produced and tested under the same work conditions that a company may expose their workers. Therefore, it is important to test the value of the proposed interventions for the specific applications. This study evaluates the effectiveness of anti-vibration interventions currently in use at a local manufacturing company. Methods The design of this study evaluates the vibration energy produced at the tool handle and from the back of the operator’s hand. Each operator performed a series of fastener installations in metal using several interventions and one series with no intervention as a control. Four of the interventions were gloves containing anti-vibration material and the fifth intervention was an anti-vibration material wrapped around the tool handle. The protocol for wrapping the tool handle was developed and is part of the equipment procedure at this manufacturing company. Test conditions mimicked production work conditions including similar materials, fasteners and technique for installation. Vibration values were collected using 3 tri-axial accelerometers with one firmly glued to the tool handle close the hand grip as recommended by ISO 5349. A second accelerometer was placed on the top of the pistol shaped tool. The third accelerometer was attached to the back of the hand close to the third knuckle using double sided tape. Results Preliminary results for 3 volunteers show a difference between the vibration values of the control condition (mean hand vibration on bare hand = 1.77 Gs) compared to all of the interventions (p=.0001 using Mixed Procedure, Tests of Fixed Effects). The graph below shows individual trials for each subject for each condition. Glove 3 with the air bladder insert shows large variability between subjects (Range = 0.84-3.33 Gs). The other interventions show much less variability both within subjects and between subjects indicating consistent response with use of the intervention.

Jan 6, 2006

By H. S. Chiang, Zhao. Y. F., G. C. Sun, S. S. Peng

"Chiang; H. S. West Virginia UniversityPeng, S. S. West Virginia UniversitySun, G. C. West Virginia UniversityZhao, Y. F.West Virginia UniversityDust sampling was performed in two longwall faces working in two separate seams. Instantaneous dust samples were measured by RAH's. for various locations In the longwall faces. Preliminary analysis of the data shows that in addition to the shearer's haulage speed, there are four major factors that influence the airborne dust distribution in longwall face areas: locations with respect to the position of the shearer's cutting, hardness of the materials, characteristics of water spray, and roof conditions. This paper presents the effects of those four parameters in detail.INTRODUCTIONA research project was initiated in September 1983 to measure and construct .a dust distribution map for the longwall face. During the first year, airborne dust samplings were performed in two longwall panels located in northern and southern West Virginia and working in the Pittsburgh and Eagle Seams, respectively. The physical parameters and equipment employed for both panels are 1 isled in Table 1. Figure 1 shows the detailed characteristics of the coal seams. Notice in both panels floor cutting was involved either to gain sufficient mining height or to reduce the adverse effects associated with a soft floor.The purpose of the research is to define the dust distribution at any instance in the longwall face area so that proper working positions can be determined and/or effective dust control techniques can be developed.This paper presents the partial results obtained during the first year."

Jan 1, 1988

By Bernard Lewis, Guenther von Elbe

"Explosive gas mixtures are characterized by their ability to undergo a self-accelerating reaction that may culminate in ignition. In the case of methane and air there are two interdependent causes of this acceleration. First, if a sufficiently fast reaction is induced, heat may be evolved faster than it is lost to the surroundings; consequently, the temperature rises and the reaction rate increases. Second, the reaction rate is determined not only by temperature but by the concentration of reactive intermediate products if the latter increases during the course of the reaction the rate will increase. To understand the role of these active intermediates, it should be realized that molecules of methane and oxygen, per se, show little tendency to react with each other even at high temperatures.(1) If, however, free radicals like OH and CH3, are present in the mixture, the methane and oxygen are attacked in the reactions(2):In these reactions the radicals are regenerated, and thus a chain of reactions is set up by an individual radical or chain carrier which is broken only if the latter is destroyed in some process. Not all collisions of a chain carrier with CH4 or 02 result in reaction, since one requirement for a successful collision is that the colliding particles have a certain minimum energy. The percentage of collisions in which this energy condition is fulfilled increases with temperature, so that for equal chain-breaking probabilities the length of the reaction chain increases with increasing temperature. Thus, there exists an interplay of temperature and concentration of chain carriers that determines the reaction rate. To carry the rate to the stage of self-acceleration, higher temperatures are required for lower than for higher chain-carrier concentrations, other conditions being equal."

Sep 1, 1939