Dumas Method for Organic Nitrogen FRED SHEA
D
AND
C. E. WATTS, Commercial Solvents Corporation, Terre Haute, Ind.
Pure copper in wire form is used instead of rolled copper gauze in the end of the combustion tube nearest the azotometer, to ensure tight packing of the tube and to obtain close contact of the gases with the surface of the hot copper. Copper in the form of short lengths of wire is more convenient to use than the spiral form and can be more effectively packed in. The co per is easily made by reducing the regular 0.94-em. (0.375-in&) length of copper oxide wire with hydrogen gas in a combustion tube. An electric furnace is used to heat the copper oxide and the pure copper wire in the azotometer end of the tube to a temperature of 650” C., a dull red heat. Gas burners are used to ignite and burn off the sample, starting cold and gradually heating to a maximum of 550” C. The burner under the copper oxide spiral is lighted first. This prevents the gas from receding towards the rear end of the tube. After the spiral is red hot, the second burner is li hted with a low flame to allow the sample to burn off slowly. In &is way the rate of gas flow from the burning sample can be regulated very satisfactorily. Towards the end the third burner is lighted to ensure carrying the last traces of gases from the sample into the furnace section. Temperatures may be determined in advance of actual introduction of the sample by placing a thermocouple in the combustion tube and noting approximate setting of the rheostats and gas flames. A little experience will quickly familiarize the operator with the control of temperature in different sections of the tube. A convenient method of checking the complete removal of nitrogen from the combustion tube is to take readings a t 3- or 4-minute intervals after the combustion is apparently complete, recording the time and volume on a scratch pad. In this way a waste of time is avoided, as the increase in the volume of gas in the azotometer rapidly ceases and a constant final volume varying within only 0.1 ml. is obtained. Determinations may be made in from 35 to 50 minutes, using samples with a total nitrogen content of 0.03 to 0.05 gram of nitrogen. A two-way sto cock is attached at each end of the train. These are very helpful for the following reasons: The combustion tube may be swept out with carbon dioxide while the whole apparatus is completely assembled without having to pass the carbon dioxide through the azotometer and reduce the absorptive power of the alkaline solution. Also the carbon dioxide itself may easily be tested for impurities when desired, simply by diverting the flox through the two-way stopcock into the azotometer. The carbon dioxide supply can be connected to the opposite end of the train during the insertion of the sample. This allows one to reverse the flow of carbon dioxide and prevents air from entering- the apparatus while the sample is being pushed into _place.
IFFICULTY is frequently experienced in obtaining ac-
curate results in the determination of nitrogen by the Dumas method, errors sometimes being introduced by too rapid combustion of the sample and by impurities in the carbon dioxide. The error due to too rapid combustion is especially encountered in the analysis of liquid compounds of nitrogen of a semi-explosive nature which tend to dissociate suddenly on heating, and which cannot be analyzed accurately by the Kjeldahl method because of losses during digestion. After considerable experimenting, several modifications of the standard Dumas assembly have been made, with the result that the apparatus described below can be depended upon to give consistently good results even with relatively unstable liquid compounds. Compounds giving “nitrogenous charcoal” and requiring additional oxygen as described by Spies and Harris (1) are not included in the scope of the present apparatus, since these compounds are a t the opposite end of the scale so far as ease of combustion is concerned. The present method is concerned with the analysis of compounds which burn too readily rather than too slowly. The modified apparatus makes use of both gas and electric heating, the former to secure the very low, easily controlled heat essential for the proper burning off of the sample. Near the exit end of the combustion tube, the electric furnace is preferable for heating the copper reduction section of the assembly. The complete setup is shown in Figure 1.
Recommended Modifications The combustion boat is filled with a mixture of 50 per cent by weight of powdered copper oxide and 50 per cent by weight of calcium carbonate instead of with pure copper oxide. The use of this mixture allows the sample to burn off more slowly, because of the inhibiting effect of the calcium carbonate, and prevents a sudden spurt of gas from forcing its way through the tube immediately after ignition of the sample. Volatile liquids should be weighed in glass ampoules. The ampoule is then laid in the combustion boat and covered with the calcium carbonate-copper oxide mixture, taking care to have the open end of the stem beneath the surface. High-boiling liquids may be weighed directly onto a layer of the mixture in the boat; then, after re-weighing, the boat should be filled to cover the sample.
THERMOMETER
MERCURY SAFETY VALVE
‘ I
1
,
,
TO PRESSURE
MULTIPLE UNIT HEATE FLASK
FIGURE 1. DIAGRAM OF SETUP 333
PRESSURE REGULATOR
334
INDUSTRIAL AND ENGINEERING CHEMISTRY
By careful use of both two-ways, at least 25 determinations may be made without repacking the train, although it may be necessary t o burn off the copper spiral plug directly above the first gas burner every 4 or 5 determinations. The stock azotometer tube has been cut off below the graduations and a bulb sealed on between the graduations and the mercury tra . This bulb is approximately 5 cm. (2 inches) in diameter an8is filled with small glass beads. The extra space in the bulb allows the use of an excess of caustic solution and the beads serve to break up the gas bubbles and thus facilitate comlete absorption of the carbon dioxide by the alkaline reagent. k i t h this modified azotometer there is no danger of exhausting all the alkali during one determination; in fact, the same solution has been used for two or more determinations. A satisfactory source of carbon dioxide is dry ice, finely broken up and packed tightly in a 1-liter Pyrex Erlenmeyer flask. Care should be taken in filling the flask t o avoid visible air spaces. The mouth of the flask is connected t o the rear end of the combustion tube by a piece of bent glass tubing. The flow of carbon dioxide is regulated through a Tirrill burner connected by another piece of glass tubing as shown in Figure 1. A mercury safety valve obviates the risk of breaking the dry ice flask by inadvertent closing of the screw valve of the burner. The rubber sto per through which the outlet tubing passes is wired into the #ask to withstand moderate pressure. For safety against possible breakage and to prevent too rapid evolution of carbon dioxide,
VOL. 11. NO. 6
the flask is wrapped in a towel or placed in a container or shield of some sort. This carbon dioxide generator, when set up and adjusted properly, will furnish a dependable supply of pure carbon dioxide for a period of about 10 hours. The following typical results have been obtained using this assembly :
2-Nitro-3-hexanol 2-Methyl-2-nitro-1-butanol
Nitrogen Found
Nitrogen Theoretical
%
%
I ;::; {;E; { 3:
3-Nitro-4-heptanol
3-Methyl-3-nitro-2-pentanol
{E;
9.52 10.53
8.70 9.52
Literature Cited (I) Spies and Harris, I N D . ENQ.C H ~ MAnal. . , Ed., 9,304 (1937). PRESENTED before the Division of Physical and Inorganic Chemistry at t h e 96th Meeting of the American Chemical Society, Milwaukee, Wis.
Methods of Representing Distribution of Particle Size J. B. AUSTIN, United States Steel Corporation, Kearny, N. J.
D
ISTRIBUTION of size in a particulate material is commonly represented by plotting either a frequency distribution curve showing the relative number of particles within each range of diameter, or a cumulative curve giving the fraction of the total number of particles which have a diameter greater, or less, than that indicated. The curve from the first method, which is essentially a differential method, resembles a probability curve (see Figure l),but is usually skewed rather than symmetrical as is the normal probability curve. The second, essentially an integral method, gives an S-shaped curve resembling the ogive or integrated probability curve (Figure 2). Each method has a number of disadvantages: A relatively large number of experimental points are required to fix the position of the curve, interpolation is sometimes difficult, and extrapolation may be uncertain. Moreover, it is not easy to convert the data from one form to the other unless a great many measurements have been made. When the experimental data give the frequency distribution directly, a large number of observations must be made in order to determine the course of the curve, but when such measurements are available, it is a simple matter to convert them to the cumulative form. When, on the other hand, only data on the cumulative percentage oversize or undersize are available it is by no means easy to obtain the frequency curve, because the conversion involves measuring the slope of the cumulative curve along its length and this is usually uncertain unless the curve is determined by a great many observations. Because of these difficulties numerous efforts have been made to find an equation which fits the distribution curves so that i t can be used as a guide in interpolation, extrapolation, and in expressing the form of one curve in terms of the form of the other. The results of these efforts which have been re-
viewed by Work (IQ),leave much to be desired. The simpler relations are not satisfactory, whereas the more successful ones, such as that derived by Rosin and Rammler (18) for broken cod, are somewhat cumbersome to use. It is also clear that no single expression will fit the distribution in size for all types of material. An alternative approach to the problem is to use a graphical rather than an analytical method and to devise a means of plotting which reduces the distribution curves to a straight line. If this can be done, the course of the curve can be completely determined, in principle a t least, from two experimental observations, and in practice a small number of points commonly suffices if the range covered is relatively wide. I n addition, interpolation is easy, the data can be extrapolated with reasonable certainty, and the consistency of a given set of measurements can be judged from the deviation of individual points from the best straight line through the set. Here again, no single method has been found which FIGURE 1. SCHEMATICFREworks for all mateQUENCY CURVE, SHOWING rials, b u t several TYPICAL DISTRIBUTION OF methods of plotting, PARTICLE SIZE
