396 lines
21 KiB
Plaintext
396 lines
21 KiB
Plaintext
ÉÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ»
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º Improvised PETN º
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º º
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º Agent Orange (c) 1993 cTs º
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ÈÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍͼ
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Warning.
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There may be certain federal, state or local laws which prohibit the possesion
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or manufacture of certain substances mentioned herein. Severe penalities may
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be prescribed for violation of such laws. Be warned!
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The procedures to be followed in this manual and the resulting end-product
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are extremly dangerous. Whenever dealing with high explosives, special
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precautions should be followed in accordance with industry standards for
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experimentation and production of high explosives. Failure to strictly such
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industry standards may result in harm to life or limb.
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Therefore, the author disclaim any liability from any damages or injuries of
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any type that a reader or user of information contained within this manual may
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encounter from the use of said information. Use this manual and any end-
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product or by-product at your own risk.
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Preface.
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The information in this manual serves as an introduction to the organic
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explosive PETN, pentaerythritol tetranitrate. Included are important physical
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and chemical properties with which the reader should be familiar before
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proceeding to the section that describes in detail one of several proven
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methods for the manufacture of high-grade PETN. Finally it should be
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mentioned that the chemicals listed in this text are hazardous if used im-
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properly or handled carelessly. The reader is urged to adopt a "think before
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you do" attitude, pay attention to details, and use safe laboratory equipment
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and procedures.
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1. PETN: Its Discovery and Properties.
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The high explosive pentaerythritol tetranitrate was first synthesized in
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1894 at the Rheinish-Westfalische Sprengstoff Company in Germany by a chemist
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researching the nitration process of pentaerythritol in a high concentration
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of nitric acid. The resulting explosive was collected, tested, and found to
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have a very fast rate of detonation, high density, and good chemical stability,
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making it an ideal substance for military use. Unfortunately, at that time
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there was no means available to mass-produce the raw ingredient pentaery-
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thritol. PETN thus remained a laboratory interest until World War II, when it
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was used in ammunition, bombs, and other fragmention devices. During this time,
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Germany produced as much as 1,440 tons of PETN per month, with the USA and the
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USSR following suit.
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Still manufactured on a large scale, PETN remains one of the most powerful
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conventional explosives ever developed, rivaled only by HMX and RDX. The
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military, as might be expected, is the largest user of PETN, with annual
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purchasing well over 2,000 tons. Nonmilitary use is primarily limited to
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demolition work and as a booster material for secondary explosives such as
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ANFO, dynamite, etc.
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Physical and Chemical Properties.
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PETN is a white crystalline substance that feels powdery to the touch. In
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its pure form, PETN melts at 141.3 degrees centigrade. The boiling point is:
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160øC at 2mm Hg
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180øC at 50mm Hg
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200øC at 760mm Hg (standard atmosphere)
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The molecular structure is:
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O NOCH H CONO
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2 2 2
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\ /
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\ /
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C C H O N
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/ \ 5 8 12 4
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/ \
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O NOCH H CONO
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2 2 2 2
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The calculated nitrogen content is as follows:
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Element # Atoms
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x Atomic Wt.
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Carbon 5 x 12.011 = 60.055
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Hydrogen 8 x 1.00794 = 8.064
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Oxygen 12 x 15.9994 = 191.993
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Nitrogen 4 x 14.0067 = 56.027
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ÄÄÄÄÄÄÄ
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Total 316.139
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56.027
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ÄÄÄÄÄÄÄ
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316.139 (100) = 17.722% Nitrogen
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Correspond with the military specification MIL-P-387 for PETN:
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Melting Point 140.0øC
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Nitrogen Content 17.5% Minimum
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Substances Insoluble
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in Acetone .10% Maximum
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Acid or Alkali Content .003% Maximum
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Vacuum Stability at 120øC 5ml of gas / 20 hours
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Overall Purity 98.7%
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If we examine the ultraviolet absorption spectrum of a single PETN crystal,
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we find a narrow band in the 280æm area. Because ordinary sunlight emits UV in
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the same range, PETN should not be exposed to the sun for a long period of
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time as damage in the form of cracks in the crystals will appear and render
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the PETN useless.
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2. PETN Manufacture.
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PETN can be made in a number of different ways, but the overall process is
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always the same and consists of the following steps:
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1. Nitration. Adding pentaerythritol to a given amount of nitric acid for
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a specific time at a specific temperature to form crude PETN.
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2. Washing. The crude PETN is rinsed with distilled water until free of acid,
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filtered, and throughly dried.
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3. Recrystallization. The dry PETN is dissolved in heated acetone, purified
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with a neutralizing agent, and then poured into cold water where the purified
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PETN is precipitated.
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4. Washing. The pure PETN is again rinsed with distilled water to remove
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remaining traces of acid and acetone, filtered, and dried to a 10 percent
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water content. The PETN is now ready for use.
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We will now proceed to the actual method for making high-grade PETN on a
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laboratory scale (larger amounts can be made by increasing the size of the
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equipment) that will yield about 500ml per batch. The amount of chemicals used
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can vary if one wishes to produce more or less PETN per batch. However, the
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proportions and the temperatures are exact and must not be changed under any
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circumstances. We will begin with a list of equipment and chemicals needed.
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Then each of the steps mentioned above will be detailed and fully discussed.
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Hardware Required
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1. Stirring hotplate, with at least a 10" x 10" surface area. This type of
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hotplate will heat solutions and stir them by spinning a glass-coated bar
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magnet that is dropped into the solution being treated. The temperature
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and mixing rate are both adjustable by turning two dials on the face of
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the machine. The magnetic stir bar should be about 2.75 inches long and
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glass coated. If a regular hotplate of the nonstirring type is used, then
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all stirring must be done by hand with a glass rod.
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2. Glass coated magnetic stir bar 2.75" long
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3. One 4,000ml Pyrex beaker of standard configuration, with graduation
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4. One 1,000ml Pyrex beaker, tall form with graduation
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5. One thermometer graduated in degrees centigrade
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6. One thermometer clip to hold thermometer to the beaker
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7. A few glass stirring rods
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8. Pack of fine-grade filter paper (grade: 230, 33cm diameter)
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9. Glass funnel
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10. Plastic bucket: one or two
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11. Wood or plastic cookspoon (used to scoop PETN crystals)
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12. Several pans for drying (disposable pizza pans work well)
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13. One graduated cylinder used for measurement. A 100 or 200ml cylinder will
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do.
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14. Several paper cups
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15. Full face shield to protect eyes and face while working with acid.
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16. Plastic or rubber gloves
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Chemicals Required
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The amount of chemicals listed is just enough to make one 500ml lot of PETN.
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The reader will have to decide how much to purchase if he decides to vary the
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amount of PETN produced.
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1. 600ml nitric acid with a purity of 98 percent. (Don't use 70 percent or
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90 percentÄuse only 98 percent.)
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2. 250ml pentaerythritol, reagent grade
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3. 1,500ml acetone, reagent grade
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4. One teaspoon sodium carbonate powder, reagent grade
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5. 800ml distilled water
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6. 30 to 40 gallons of tap water for rinsing. Should tap water be hard or
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contain chlorine, distilled water must be used.
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7. One vial of red litmus paper, used to test pH level alkaline range 7 to 14
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8. One vial of blue litmus paper, used to test pH level in acid range 0 to 7
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9. Small bag of crushed ice
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10. Optional: Full range 0 to 14 pH indicator strips. These are helpful in
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determining the pH of a solution, but litmus will suffice.
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All of the hardware and chemicals listed are readily available from major
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scientific supply companies. Consult the yellow pages and don't be afraid to
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shop around for the best prices.
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Procedure
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Step One: Nitration
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(a) Take the 100ml tall form beaker and fill it with 600ml of nitric acid. Be
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sure to wear your face shield when working with acid.
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(b) Place the tall form beaker with the acid inside of the larger 4000ml
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beaker and center it.
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(c) Fill the larger beaker with crushed ice up to the same level as the acid
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in the tall form beaker. Now pour tap water over the ice until the level
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reaches the 700ml mark on the tall form beaker. Do not let any ice or
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water fall into the acid.
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(d) Carefully place the stir bar into the beaker of acid.
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(e) Using the thermometer clip, attach the thermometer to the rim of the tall
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form beaker and adjust it so that the bulb (the part with the mercury)
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falls just slightly below the surface of the acid. Be sure the numbers can
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be clearly read.
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(f) With two hands, carefully lift the whole assembly and place it on the
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stirring hotplate and move it around so that the stir bar is centered in-
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side the tall form beaker. All controls on the hotplate should be in the
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off position.
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(g) Using the graduated cylinder, measure out 250ml of pentaerythritol and
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pour this into the paper cups (you will most likely need two paper cups).
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During the manufacture process, acetone is used to purify crude PETN and to
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safely remove crystals that may have condensed on various pieces of laboratory
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equipment. Because acetone readily dissolves PETN, a table of solubility is
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given below as a reference.
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ÚÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ¿
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³Amount of PETN ³ Acetone Soluble in Water ³
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³dissolved in ÃÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄ´
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³100 grams of ³ 55% ³ 70% ³ 80% ³ 90% ³ 92% ³
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³solution (grams)ÃÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄ´
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³ ³ Temperature of Solution in øC ³
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ÃÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄ´
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³ 5 ³ 1 gr @41C ³ 41.5 ³ 22 ³ ³ ³
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³ 10 ³ 4 gr @62 ³ 54.5 ³ 38.5 ³ 15 ³ 10 ³
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³ 15 ³ ³ 62 ³ 48 ³ 24.5 ³ 20.5 ³
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³ 20 ³ ³ ³ 54 ³ 34.5 ³ 29 ³
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³ 25 ³ ³ ³ 59 ³ 41.5 ³ 34 ³
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³ 30 ³ ³ ³ 63 ³ 46.5 ³ 40.5 ³
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³ 35 ³ ³ ³ ³ 51.5 ³ 45 ³
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³ 40 ³ ³ ³ ³ 55 ³ 50 ³
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³ 45 ³ ³ ³ ³ 58.5 ³ 54 ³
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³ 50 ³ ³ ³ ³ 61.5 ³ 57.5 ³
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³ 55 ³ ³ ³ ³ ³ 60.5 ³
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³ 60 ³ ³ ³ ³ ³ 62.5 ³
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ÀÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÙ
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The above table indicates a low solubility of PETN in water and this helps
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to explain the low toxicity of PETN on the human body. Handling or inhaling
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the dust in small amounts causes almost no effect. From a toxic point of view,
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PETN, unlike nitroglycerine, TNT, or dynamite, is safe to work with.
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Explosive Properties
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Pure PETN, when heated above its melting point, explodes at 205-225øC.
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A Table of Gaseous Products Released
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During Decomposition of PETN
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Initiation NO NO N O N CO CO H O
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2 2 2 2
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Detonation Ä 5.3 Ä 22.8 37.0 26.7 6.8 1.4
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Impact Ä 24.3 5.3 9.4 19.1 35.4 6.5 Ä
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Thermal 210øC 12.0 47.6 9.5 1.6 6.3 21.0 2.0 Ä
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Heat of Explosion: 1,530 Kcal/Kg.
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Volume of Gases: 768 L/Kg.
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Temperature: 4,230øC
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The rate of detonation of a single crystal of PETN, the density of which is
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1.77g/cubic centimeter, is 8,500 meters/second. In order to get a cartridge
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filled with PETN powder to detonate at the same rate, two things must be done:
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1. Pure, dry PETN must be mixed by weight with 10 percent water. This will
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drive the air out and allow the detonation wave to travel rapidly from one
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crystal to the next. The water also makes the PETN safer to work with, as dry
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PETN explodes when subjected to a slight impact.
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2. The PETN must be loaded into the cartridge under high pressure so that
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the density of the powder approaches the crystal density.
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The ideal loading density of a cartridge containing PETN should be in the
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range of 1.72 to 1.73g/cubic centimeter. At this density, the 8,500 meter/
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second detonation rate can be achieved and the maximum explosive power of PETN
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obtained. It should be mentioned, however, that even if a cartridge is only
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packed by hand, a very powerful explosive device will still result.
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The loading density of a cylindrical cartridge can be determined by using
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the following equations:
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Force
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Pressure = ÄÄÄÄÄÄÄ
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Area
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Volume = Area x Length
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Mass (amount of PETN)
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Loading Density = ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
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Volume of Cartridge
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We are now ready to continue. Be sure the work area has good ventilation,
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and wear your face shield to avoid acid burns in case any beakers are
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accidently knocked over.
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(h) Turn on the stirrer and adjust until a smooth rapid motion occurs in the
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acid. The heater will be in the "off" position during the whole nitration
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process. If you are not using a stir bar, the stirring must be
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continuously done by hand with a glass rod.
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(i) Look at the thermometer. When the temperature falls to 10øC, very slowly
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sprinkle in some of the pentaerythritol by squeezing the rim of the cup
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to form a spout and shake lightly. As soon as the temperature starts to
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rise, stop adding. Look to see where the temperature stops. If it is below
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20øC, then continue adding the pentaerythritol and stopping whenever the
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thermometer reads 20øC. Allow the whole mixture to cool back to 10øC and
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then start sprinkling in the pentaerythritol until 20øC is again obtained.
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Continue adding in this manner until all 250ml of pentaerythritol has been
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added. When the temperature again falls to 10øC, remove the thermometer
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and the stir bar. Take the small beaker out of the larger one and set it
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aside for forty-five minutes. The stir switch can be turned off and the
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ice-water mixture thrown out.
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Important: Never let the temperature of the mixture rise above 25øC during
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this operation.
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This concludes Step One.
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Step Two: First Washing
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(a) After forty-five minutes have elapsed, the crude PETN will have settled to
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the bottom of the beaker, as a thick yellow-white sludge, with a layer of
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acid on top. Pick up the beaker and slowly pour off the top layer of acid,
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being careful not to disturb the PETN sludge. When finished, set the
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beaker aside and dispose of the waste acid.
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(b) Fill a plastic bucket with two gallons of water. Use distilled water if
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your tap water is hard or chemically treated.
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(c) Pour the beaker of PETN into the bucket and scoop out any sludge with a
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wood cookspoon. Using a glass rod, stir the contents of the bucket
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vigorously for ten seconds and then wait for the PETN to settle. If a foam
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has developed on the surface of the water, be sure to agitate the surface
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with your stirring rod. The foam, which is just air trapped in PETN, will
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settle to the bottom of the bucket.
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(d) After the contents have settled, take a strip of blue litmus paper and dip
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it into the bucket. You will notice that the litmus paper turns red,
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indicating the presence of any acid. This acid must be removed, so take
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the bucket and slowly pour off the layer of water. Be careful not to pour
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off any PETN by accident.
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(e) Take two gallons of fresh water and pour it into the bucket. As before,
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stir to break up the foam and then allow the contents so settle again.
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Using a new blue litmus paper, test for the presence of any acid. Should
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acid be present, continue the cycle of pouring off the water adding fresh
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water, stirring, settling, and testing with litmus paper.
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(f) After several wash cycles, you will find that the litmus paper no longer
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turns red but instead remains blue, indicating that the rinse water is now
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neutral. Wash the PETN one more time, let settle, and pour off the water.
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(g) Place a filter paper into the glass funnel. Scoop the PETN from the bottom
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of the bucket and put it into the filter. The filter paper and funnel
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serve to allow the water to drip away, thus allowing the PETN to dry fas-
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ter. Allow the PETN to filter for at least thirty minutes.
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(h) After filtering, take the PETN and spread it out as a thin layer in the
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drying pans. The PETN must be allowed to dry completely. When dry, it will
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be a white crystalline powder. The drying might take several days.
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(i) Clean and dry the beakers, stir bar, and thermometer, as they will be used
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again during the next step.
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(j) After the PETN has dried, place it in any handy containerÄother than the
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beakersÄand set it aside.
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This concludes Step Two.
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Step Three: Recrystallization
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(a) Take one teaspoon of sodium carbonate and place it in the tall form beaker.
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Add 800ml of distilled water and stir until completely dissolved. This,
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your neutralizing solution, will be used shortly.
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(b) Fill the 4,000ml beaker with 1,500ml of acetone. Put in the stir bar and
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thermometer and place on top of the hotplate. Turn the stir dial to a
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medium speed and turn on the heat. The temperature of the acetone will
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rise and must be held between 50øC and 60øC. Do not let the temperature
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stray out of this range during the next steps. Aim for a temperature of
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55øC. Heated acetone is highly flammableÄuse caution!
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(c) Take two heaping tablespoons of dry PETN, add it to the acetone, and let
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it dissolve completely. The temperature will now drop slightly, but if it
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is still above 50øC, take two more tablespoons of PETN, add it to the
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acetone, and let it dissolve. Keep up this method of adding two tablespoons
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of PETN and letting it dissolve until the temperature reaches 50øC, stop
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adding PETN and let the temperature rise to just under 60øC. Then begin
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adding PETN again two spoons at a time and allowing it to dissolve until
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all the PETN has dissolved
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(d) With all the PETN now dissolved in acetone and the temperature held at
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55øC, we will begin neutralizing the solution.
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(e) Have both the blue and red litmus papers ready.
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(f) Fill the graduated cylinder with the sodium carbonate solution that was
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prepared in the tall form beaker.
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(g) Keeping the contents of the large beaker in the 50ø to 60øC range, add to
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it 10ml of the sodium carbonate solution (SCS). Insert a blue litmus paper.
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if the paper turns red, add 10ml more of the SCS, and test again with the
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litmus paper. Keep up this process of adding 10ml of SCS at a time, until
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the litmus paper remains blue. When this happens, add a final 10ml of SCS.
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Test with both the red and blue litmus paper. If neither paper changes
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color, the solution is neutral. Turn off the hotplate.
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(h) Immediately fill a bucket with two gallons of cold water. Pour the con-
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tents of the large beaker into the bucket and stir. The PETN will now pre-
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cipitate with its new fine crystalline structure.
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(i) Test the water in the bucket with blue and red litmus paper. If the inst-
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ructions in this text were followed carefully, there will be no reactions.
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If they do react, then an error was made and salvaging the PETN will be
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beyond the scope of this text. You will have to try again.
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This concludes Step Three.
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Step Four: Second Washing.
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(a) This washing process is similar to Step Two, only we will be removing
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acetone instead of acid from the PETN. When the contents in the bucket
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(including the foam) have settled, pour off the water.
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(b) Add two gallons of fresh water, stir, and allow to settle. If you smell
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the water, you will notice a strong acetone odor. Continue the wash cycle
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until the acetone odor is no longer apparent and then rinse the PETN two
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more times to complete the washing.
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(c) After the PETN has settled, pour off the water. Filter the PETN and allow
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to dry to a 5 to 10 percent moisture content. The finished PETN should not
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||
feel wet when a sample is squeezed between your fingers. When the PETN has
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||
been dried, it will be ready for use. Store in a cool, dark place.
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This concludes the manufacture of PETN.
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