PYROTECHNICS: SAMPLING, INSPECTION AND …everyspec.com/MIL-STD/MIL-STD-1100-1299/download.php?spec=MI… · mil-std-1234 notice 1 18 december 1965 military standard pyrotechnics:

MIL-STD-1234NOTICE 118 December 1965

MILITARY STANDARD

PYROTECHNICS: SAMPLING,

INSPECTION AND TESTING

TO ALL HOLDERS OF MIL-STD-1234:

1. The followinglisted:

New Pageiiivv

2. The following

Revised Method101.1.1101.2.1101.8.1101.4.1102.1.1102.2.1

3. The following

Method No.101.5

pages of MIL-STD-1234 have been revised

Date Superseded Page18 December 1965 ii18 December 1965 iv18 December 1965 v

and supersede the pages

Date22 June 196222 June 196222 June 1962

methods have been revised and supersede the methods listed:

Date Superseded Method Date18 December 1965 101.1 22 June 196518 December 1965 101.2 22 June 196518 December 1965 101.3 22 June 196218 December 1965 101.4 22 June 196218 December 1965 102.1 22 June 196218 December 1965 102.2 22 June 1962

method has been added:

Title DateMoisture (Kari Fischer Distilation Method) 18 December 1965

4. Retain this notice and insert before the Table of Contents.

FSC 1370

Project No. 1370-0205

Downloaded from http://www.everyspec.com

DEPARTMENT OF DEFENSE

Washington 25, D.C.

Pyrotechnics: Sampling, Inspection and Testing

MIL-STD-1234

1. This Military Standard has been approved by the Department of Defense and ismandatory for use by all Department and Agencies of the Department of Defense.

2. Recommended corrections, additions, or deletions should be addressed to Command-ing Officer, Picatinny Arsenal, Dover, New Jersey 07801, ATTN: SMUPA-DC7.

ii

Supersedes Page ii of 22 June 1962


MIL-STD-123418 December 1965

ALPHABETICAL INDEX OF TEST METHODS–Continued

Title Method No.

Hygroscopicity (Equilibrium Method) . . . . . . . . . . . . . . . . . . . . . . .Impact Sensitivity (U.S. Bureau of Mines Apparatus) . . . . . . . . . . .76°C. International Test . . . . . . . . . . . . . . . . . . . . .Iron (Jones Reductor Method) . . . . . . . . . . . . . . . . . . . . . . . .Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Lead Sulfocyanate (Silver Nitrate Method) . . . . . . . . . . . . . . . . . . . . . . . .Magnesium (Audiometer Method) . . . . . . . . . . . . . . . . . . . . . . . . .Magnesium (Pyropophosphate Method) . . . . . . . . . . . . . . . . . .Methyl Orange Indicator Solution . . . . . . . . . . . . . . . . . . . .Methyl Red Indicator Solution . . . . . . . . . . . . . . . . . . .Moisture (Desiccation Method) . . . . . . . . . . . . . . . . . . . . . . . . .Moisture (Karl Fischer Extraction Method) . . . . . . . . . . . . . . . . . . . . . . . . .Moisture (Karl Fischer Distillation Method) . . . . . . . . . . . . . . . . . . . . . . . . .Moisture (Karl Fischer Method) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Moisture (Modified Karl Fischer Method) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Multiple Solvent Extinction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Nickel (Dimethylglyoxine Method) . . . . . . . . . . . . . . . . . . . . . . . . . . .Nitro-Compounds (Titanous Chloride Method) . . . . . . . . . . . . . . . . . . . . . . . . . .Organic Destruction and Sample Dissolution . . . . . . . . . . . . . . . . . .Perchlorate (Ammonium Chloride Method) . . . . . . . . . . . . . . . . . . . . . . . . . .Phenolphthalein Indicator Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . .Potassium and Barium Salts (Flame Spectrophotometric Method) . . . . . . . . .Potassium Dichromate (0.1N Standard Solution) . . . . . . . . . . . . . . . . . . . . .Potassium Permanganate (0.1N Standard Solution) . . . . . . . . . . . . . . . . . . . . .Potassium (Tetraphenyl Boron Method) . . . . . . . . . . . . . . . . . . . . . . . .Potassium Thiocyanate (0.1N Standard Solution) . . . . . . . . . . . . . . . . . . . . . . .Reactivity Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Selective Solvent Extraction (Extraction Method) . . . . . . . . . . . . . . . . . . . . .Selective Solvent Extraction (Insoluble Residue Method) . . . . . . . . . . . . . . . . . .Selective Solvent Extraction (Leaching) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Selective Solvent Extraction (Soxhlet Method) . . . . . . . . . . . . . . . . . . . . . . . . . .Silver Nitrate (0.1N Standard Solution) . . . . . . . . . . . . . . . . . .Sodium Diphenylbenzidine Sulfonate Indicator Solution . . . . . . . . . . . . . .Sodium Hydroxide (0.1N Standard Solution) . . . . . . . . . . . . . . . . . .Sodium Oxalate (Potassium Permanganate Method) . . . . . . . . . . . . . . . .Soxhlet Extraction . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . .Starch Indicator Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . .Strontium Nitrate (Sulfate Method) . . . . . . . . . . . . . . . . . . . . . . . .Sulfur (Carbon Disulfide Insoluble) . . . . . . . . . . . . . . . . . . . .Sulfur (Carbon Disulfide Soluble) . . . . . . . . . . . . . . . . . . . .Titanous Chloride (0.2N Standard Solution) . . . . . . . . . . . . . . . . . . .Titanium and Titanium Dioxide (Jones Reductor Method) . . . . . . . . . . . . . . .Tota l Lead (Chromate Method) . . . . . . . . . . . . . . . . . . . . . . . .Total Lead (Sulfate Method) . . . . . . . . . . . . . . . . . . . . . . . . . .100°C. Vacuum Stability Test . . . . . . . . . . . . . . . . . . . . . . . . .V o l a t i l e s ( O v e n M e t h o d ) . . . . . . . . . . . . . . . . . . . . . . . .Volatiles (Vacuum Method) . . . . . . . . . . . . . . . . . . .Z i n c O x i d e . . . . . . . . . . . . . . . . . . . . . . . .Zirconium or Zirconium Hydride (Cupferron Method) . . . . . . . . . . . . . . .

203.1506.1501.1414.1301.4406.1412.1412.2704.1702.1101.1.1101.4.1101.5101.2.1101.2.1301.7411.1420.1301.5403.1703.1421.1605.1606.1416.1608.1604.1204.2204.4204.1204.9607.1707.1602.1416.1301.6701.1418.1409.1409.2601.1413.1408.1408.2503.1102.1102.2.1419.1416.1

iv

Supersedes Page iv of 22 June 1962



Method No.101.1.1101.2.1101.3.1101.4.1101.5102.1.1102.2.1

201.1202.1203.1204.1204.2204.3204.4

301.1301.2301.3301.4301.5301.6301.7

401.1402.1403.1404.1405.1406.1406.2407.1407.2408.1408.2409.1409.2410.1411.1412.1412.2419.1414.1415.1416.1417.1418.1419.1420.1421.1


NUMERICAL INDEX OF TEST METHODS

GROUP 100 — GENERAL TEST METHODS

MoistureMoistureMoistureMoistureMoistureVolatilesVolatiles

(Desiccation Method)(Karl Fischer Method)(Modified Karl Fischer Method)(Karl Fischer Extraction Method)(Karl Fischer Distillation Method)(Oven Method)(Vacuum Oven Method)

GROUP 200 — PHYSICAL TEST METHODSGranulationAverage Particle Size (Fischer Subsieve Sizer)Hygroscopicity (Equilibrium Method)Selective Solvent Extraction (Leaching Method)Selective Solvent Extraction (Extraction Method)Selective Solvent Extraction (Soxhlet Method)Selective Solvent Extraction (Insoluble Residue Method)

GROUP 300 — SAMPLE PREPARATIONSDissolutionDissolution — ExtractionExtractionLeachingOrganic Destruction and Sample DissolutionSoxhlet ExtractionMultiple Solvent Extraction

GROUP 400 — CHEMICAL TEST METHODS -

Chloride (Silver Nitrate Method)Chlorate (Ferrus Sulfate Method)Perchlorate (Ammonium Chloride Method)Hexachlorobenzene (Parr Bomb Method)Lead Sulfocyanate (Silver Nitrate Method)Barium Salts (Sulfate Method)Barium Salts (Chromate Method)Aluminum (Ammonium Hydroxide Method)Aluminum (8-Hydroxy-quinoline Method)Total Lead (Chromate Method)Total Lead (Sulfate Method)Sulfur (Carbon Disulfate Insoluble)Sulfur (Carbon Disulfide Soluble)Antimony Sulfide (Permanganate Method)Nickel (Dimethylglyoxime Method)Magnesium (Audiometer Method)Magnesium (Pyrophosphate Method)Titanium and Titanium Dioxide (Jones Reductor Method)Iron (Jones Reductor Method)Potassium Salts (Tetraphenyl Boron Method)Zirconium or Zirconium Hydride (Cupferron Method)Sodium oxalate (Potassium Permanganate Method)Strontium Nitrate (Sulfate Method)Zinc Oxide (Formic Acid Method) Nitro-Compounds (Titanous Chloride Method)Potassium and Barium Salts (Flame Spectrophotometric Method)

v

Supersedes Page v of 22 June 1962




MOISTURE

1. SCOPE

Method 101.1.1

(DESICCATION METHOD)

4.1 Place the specimen in the weighingdish and weigh the dish, contents and cover.

1.1 This method is used for determiningthe moisture content of pyrotechnic compo- 4.2 Place the dish with cover removed insitions on a basis of loss of weight in a the desiccator maintained at 25 degrees plusdesiccated atmosphere. This method is used or minus 5 degrees C.on compositions when it is undesirable to Note. Vacuum may be applied to the desiccatoruse heat due to the sensitivity and volatility to shorten the period of drying. The desiccator isof the material being tested.

.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 2 gm of the pyrotechnic weighed towithin 0.2 mg or as the applicable specifica-tion specifies.

3. APPARATUS

3.1 Weighing dish with tight fitting coverand of suitable diameter so that the speci-men can be spread out in a thin layer.

3.2 Desiccator containing a suitable desic-cant such as anhydrous calcium sulfate, oras specified in applicable specifications,

4. PROCEDURE

evacuated to a pressure of 380 mm plus or minus20 mm of mercury and maintained at a temperature of 25 degrees plus or minus 5 degrees C. Results obtained in this manner are usually reported as loSSon vacuum desiccation, percent.

4.3 Weigh the stoppered dish and contentsat intervals until the loss in weight betweenweighings does not exceed 0.5 mg.

4.4 Determine the loss in weight and cal-culate the loss as the percentage moisturein the sample.

4.5 Calculation

Percent moisture = A100W

where:A = loss in weight, gm.W = weight of sample, gm.

1 Method 101.1.1




Method

MOISTURE (KARL

1. SCOPE

1.1 This is a general method for determin-ing the moisture in pyrotechnics which donot react with the Karl Fischer reagent andfrom which the moisture is easily extract-able.

Note. Although the application of the Karl Fischerreagent for determining the moisture content ofpyrotechnics is general in scope, its chemical activi-ty with materials other than moisture imposes cer-tain limitations that must be taken into account bymodification of the method for the purpose of adap-tion to specific applications. Detailed specificationsshould be consulted for adaptations to materials thatrequire modifications of the procedure listed herein.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 8 to 10 gm of the pyrotechnic.

Note. The specimen shall contain not more than0.01 gm of water, The specimen weight should beadjusted after a preliminary determination, so thatthe water will not exceed 0.01 gm.

3. APPARATUS

The arrangement now used at PicatinnyArsenal will be described although numerousmodifications, which give equally satisfac-tory results, may be used. There are alsoavailable automatic titrimeters and aqua-meters especially designed for use with theKarl Fischer dead-spot end point method,which are compact and satisfactory.

3.1 Titration assembly consisting essen-tially of:

(a) Burets, automatic, Machlett auto-buret, 50 ml capacity, 2 required,one left and one right.

(b) Titrator stand.(c) Magnetic stirrer with Teflon coated

stirring bar.

101.2.1

FISCHER METHOD)

3.2 Titration flask (fig. 2) consistingessentially of:

(a) Beaker, Berzelius, 200 or 300 mlwithout spout, at least 4 re-quired.

(b) Rubber stopper to fit beaker, pre-pared as shown in (fig. 3).

(c) Glass stopper for sample portholeof rubber stopper (fig. 3).

(d) Iron ring support (fig. 2).

(e) Drying tube, calcium chloride, 3required.

(f) Weighing bottles with cap-styleground covers, 2 required.

3.3 Direct dead-stop circuit assembly (fig.1) consisting essentially of:

(a)

(b)

(c)

(d)

Dry cell battery, 1.5 volts.

Rheostat, 250,000 ohms.

Micro-ammeter, Weston Model 440,resistance 164 ohms, or equal.

Platinum electrodes, 2 required.

3.4 Over

3.5 Assemble the apparatus as follows:

(a) Attach each buret to the titratorstand.

(b) Clamp the iron ring support to thetitrator stand so that it holds therubber stopper firmly in place,allowingthrough(see fig.

(c) Pass theholes inconnectcircuit

the buret tips to passthe designated holes

3) in the stopper.

electrodes through thethe rubber stopper andthem to the dead stop

with electrical wire asshown in (fig. 1).

Method 101.2.11


MlL-STD-123418 December 1965

(d) Insert a drying tube in the hole inthe robber stopper and attachthe other two drying tubes to thevents of the burets.

(e) Place the glass stopper in the sam-ple port hole.

(f) Place the magnetic stirrer so thatwhen the rubber stopper is firm-ly fitted in the mouth of thetitration beaker, the beaker willrest on the magnetic stirrer.

(g) Place the required number of beak-ers in the oven maintained at 100degrees plus or minus 2 degreesC. to dry.

(h) Fill the reservoirs of the buretswith the required reagents.

4. MATERIALS

4.1 Karl Fischer reagent, stabilized singlesolution, placed in the reservoir of a buret.

4.2 Standard water-in-methanol, 1 mg ofwater per 1 ml of solution, placed in thereservoir of the buret.

Note. The Karl Fischer reagent and standardwater-in-methanol solution are commercially avail-able as standard stock items. If it is desirous toprepare the reagents, their preparation can be foundin Mitchell, John Jr. and Smith, Donald Milton,“Aquametry”, Interscience Publishers, inc., NewYork, 1948, Chapter IV and ASTM Method E203-62T.

4.3 Sodium tartrate dihydrate, primarystandard for Karl Fischer reagents contain-ing 15.66 plus or minus 0.05 wt percentwater.

4.4 Special solvent as indicated in the applicable pyrotechnic specification.

Note. The special solvent or advents employed foreach material will vary depending on the natureof the ingredients. Some of the solvents commonlyemployed are methanol ethanol, dioxane, acetic acid,dimethyl formamide and pyridine: methanol (1 vol:3 Vol.).

Method 101.2.1

5. PROCEDURE

5.1 Reach a preliminary end point asfollows :

(a) Dry thetainedminus

(b) Remove

beakers in an oven main-at 100 degrees plus or

5 degrees C.

one of the dried beakersand attach it, while still hot,firmly to the rubber stopper andallow it to cool to room tempera-ture.

(c) Transfer 100 ml of the special sol-vent through the sample port-hole of the rubber stopper intothe dry beaker. Add the magneticstirring bar and stopper immedi-ately. The platinum electrodesshould be immersed in solutionand should never be exposedthroughout the determination.

(d) Start the magnetic stirrer andtitrate the water in the solventby adding a slight excess of theKarl Fischer reagent to producea reddish-brown color which per-sists for at least half a minute.

(e) Adjust the variable resistance atthis point, so that with excessKarl Fischer reagent present, theneedle of the micro-ammeter willbe at the upper end of the scale.

(f) Titrate the solution slowly with thewater-in-methanol solution untilthe end point is reached. The endpoint is defined as the point atwhich one drop of the standardwater-in-methanol solutioncauses the micro-ammeter needleto waver and slowly drift fromthe upper end of the scale towardthe lower end in not less than 15seconds.

5.2 Determine the milliliters of standard

2



water-in-methanol solution per milliliter of weighed at the end of the titra-Karl Fisher reagent, designating the ratio as tion and the difference in weigh-“R” as follows: ings (5.3a) is taken as the weight

(a) Reach a preliminary end point asspecified in 5.1.

(b) Immediately fill the burets and addan accurately measured portionof approximately 10 ml of theKarl Fischer reagent.

of sodium tartrate dihydrateused.

(d) Add excess of Karl Fischer re-agent and titrate immediatelyafter reaching the preliminaryend point.

(c) Immediately titrate the solution(e) Upon reaching the second end

with standard water-in-methanolpoint, repeat the determination,take the buret readings and refill

solution. them. Add a slight excess of KarlNote. The second end point may be used as the Fischer reagent; and titrate with

preliminary end point for a check determination. standard water-in-methanol solu-

(d) Calculate the ratio “R” as follows:tion to an end point.

R = A (f) Calculate the factor “F” for each

determination as follows:B

F = 0.1566Wwhere:

VR-SA = standard water-in-methanol re- where :

agent, ml.W = sodium tartrate dihydrate, added,

B = Karl Fischer reagent, ml. gm.Note. Standardization shall be made at least once V = Karl Fischer reagent, ml.

a day.R = ratio as determined in para. 5.2

5.3 Determine the grams of water per mil-liliter of standard water-in-methanol solu-

S = standard water-in-methanol solu-

tion designating the Factor as “F” as fol-tion, ml.

lows: (g) Determine “F” from the average of

(a) Place approximately 1 gm of thesodium tartrate dihydrate in aweighing bottle, close tightly

the two determinations. Dupli-cate results should agree within0.01.

with a ground glass, cap-style5.4 Determine the percent moisture of the

cover and weigh.specimen as follows:

(b) Reach a preliminary end point as(a) Place the specimen in a weighingspecified in 5.1.

bottle, cover tightly with a cap(c) Quickly introduce, from the weigh- style ground glass cover and

ing bottle, about 0.5 gm of the weigh.sodium tartrate d ihydratethrough the sample porthole. (b) Reach a preliminary end point as

Quickly stopper the porthole and specified in paragraph 5.1.

recover the weighing bottle. The (c) Immediately upon reading the pre-bottle and contents are re- liminary end point, fill the burets.

3 Method 101.2.1



(d) Introduce the specimen from theweighing bottle through the sam-ple porthole and recover theweighing bottle. Close the port-hole and add an excess of KarlFischer reagent. The bottle andcontents are reweighed at theend of the titration and the dif-ference in Weighings (5.4a) istaken as the sample weight.

Note. Lose of 0.05 gm. of the specimen duringthe transfer to the titration flask has no appreci-able effect on the accuracy of the determination.

(e) Allow the contents of the beaker toto stir for approximately 1.5 min.or until the sample is dissolved.

(f) Titrate the solution with standardwater-in-methanol solution. The

volume of the back-titration withthe standard water-in-methanolsolution shall be less than 1 ml.

(g) Calculate the percent water as fol-lows:

Percent water = F(VR-S)100W

where:

F = factor determined as specified inpara. 5.3

R = ratio determined as specified inpara. 5.2

V = Karl Fischer reagent, ml.

S = standard water-in-methanol, ml.

W = weight of specimen, gm.

Method 101.2.1 4



FIGURE 1.

FIGURE 3.

FIGURE 2.

5 Method 101.2.1




Method 101.3.1

MOISTURE (MODIFIED KARL FISCHER METHOD)

1. SCOPE

1.1 This is a general method for determin-ing the moisture in pyrotechnics which donot react with the Karl Fischer reagent andfrom which the moisture is slowly extract-able.

Note. Although the application of the Karl Fischerreagent for determining the moisture content ofpyrotechnics is general in scope, its chemical reactivi-ty with materials other than moisture imposes certainlimitations that must be taken into account by modifi-cation of the method for the purpose of adaptationto specific applications. Detailed specifications shouldbe consulted for adaptations to materials that requiremodifications of the procedure listed herein.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 8 to 10 gm of the pyrotechnic.

Note. The specimen should contain not more than0.01 gm of water. The specimen weight should beadjusted after a preliminary determination so asto exceed the 0.01 gm maximum.

3. APPARATUS

3.1 The apparatus used in this method isidentical with that used in Method 101.2.1.

4. MATERIALS

4.1 The materialsidentical with those

5. PROCEDURE

used inused in

this method areMethod 101.2.1.

5.1 Follow the procedure described inMethod 101.2.1 from paragraph 5.1 to 5.3.

5.2 Determine the percent moisture in thespecimen as follows:

(a) Place the specimen in a weighing

bottle, cover tightlystyle ground glassweigh.

with a capcover and

(b) Reach a preliminary end point asspecified in Method 101.2.1 para-graph 5.1.

(c) Immediatily after reaching the pre-liminary end point, fill the burets.

(d) Introduce the specimen from theweighing bottle through the sam-ple porthole. Quickly restopperthe porthole and recover theweighing bottle. The bottle andcontents are reweighed at thecompletion of the titration andthe difference in weighings(5.2.a) is taken as the sampleweight.

Note. Loss of 0.05 gm of the sample during thetransfer to the titration flask has no appreciableeffect on the accuracy of the determination.

(e) Allow the contents of the beaker tostir for approximately 15 min.

(f) After the stirring period, add aslight excess of Karl Fischer re-agent.

(g) Titrate the solution with standardwater-in-methanol solution. Thevolume of the back titrationshould be less than 1 ml.

(h) Conduct a blank determination us-ing 100 ml. of the special solvent;titrating to a preliminary endpoint, stirring for 15 min; andthen titrating to an end pointspecified for the specimen.

(i) Calculate the percent water as fol-lows :

1 Method 101.3.1



Percent water = F [(VR–S) — (V´R–S´)] 100

W

Method 101.3.1

where:

F = factor determined as specified in Method 101.2.1, para. 5.3

R = ratio determined as specified in Method 101.2.1, para. 5.2

V = Karl Fischer reagent used in specimen, ml.

V´ = Karl Fischer reagent used in blank, ml.

S = standard water-in-methanol solution used in sample, ml.

S´ = standard water-in-methanol solution used in blank, ml.

W = weight of sample, gm.

2



Method 101.4.1

MOISTURE (KARL FISCHER EXTRACTION METHOD)

1. SCOPE

1.1 This is a general method for determin-ing the moisture in pyrotechnics which reactwith the Karl Fischer reagent and fromwhich the moisture is difficult to extract.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 8 to 10 gm. of the pyrotechnicweighed to within 1 mg.

3. APPARATUS

3.1 The apparatus used in this method isidentical with that used in Method 101.2.1except that two 50 ml capacity Schusterdropping bottles, having a curved necktapered to a tip which is stoppered with arubber policeman and a side tabulation fittedwith a rubber stopper are also employed.Alternatively, 50 ml. volumetric flasks maybe used in place of the Schuster bottles.

4. MATERIALS

4.1 The materials used in this method areidentical with those used in Method 101.2.1except that an extraction solvent specified inthe applicable pyrotechnic specification isemployed.

5. PROCEDURE

5.1 Place the specimen in a Schuster drop-ping bottle and fit a rubber policeman overthe tip and a rubber stopper in the side tabu-lation and weigh the assembly. If a volumet-ric flask is used, transfer the weighed speci-men directly to the flask.

5.2 Add approximately 35 ml of the ex-traction solvent into the Schuster dropping

bottle through the side tabulation, replacethe rubber stopper and weigh the assembly.The difference between this weight and theweight of the Schuster assembly obtained inparagraph 5.1 is taken as the weight of ex-traction solvent added. If a volumetric flaskis used, simply dilute to volume with theextraction solvent.

Note. Care should be taken to exclude atmosphericmoisture.

5.3 Prepare a blank as follows:

(a) With Schuster bottle. Tare a sec-ond Schuster bottle that is fittedwith a rubber policeman and arubber stopper. Add approxi-mately 35 ml of the extractionsolvent through the side tabula-tion, replace the rubber stopperand weigh the assembly. The dif-ference between this weight andthat obtained in 5.2 is taken asthe weight of extraction solventadded.

(h) With volumetric flask. Fill a secondvolumetric flask to the mark withthe extraction solvent.

5.4 Allow the two bottles to stand for atleast 17 hours or for the time required in theapplicable specification.

5.5 After the required extraction period,determine the “R’ and “F’ as described inMethod 101.2.1 paragraph 5.1 to 5.3.

5.6 Determine the percent moisture in thespecimen as follows:

(a) Reach a preliminary end point asspecified in Method 101.2.1 para-graph 5.1.

(b) Immediately upon reaching the pre-liminary end point, fill the burets.

1 Method 101.4.1



(c) Add rapidly, through the sampleporthole, a 20 to 25 gm. portionof the supernatant solutionthrough the tapered tip of theSchuster dropping bottle contain-ing the specimen. Quickly stop-per the porthole and replace therubber policeman on the Schusterbottle. The Schuster bottle isweighed at the conclusion of thetitration and the difference be-tween this weight and that ob-tained from the Schuster assem-bly after the addition of the

umetric flask is used, take a 25ml aliquot.

(d) Allow the contents of the beaker tostir for 30 seconds.

(e) After the stirring period, add aslight excess of Karl Fischer re-agent.

(f) Titrate the solution with standardwater-in-methanol solution.

(g) Repeat the determnination of mois-ture of the prepared blank in thesame manner used to determine

extraction solvent as in para- moisture ingraph 5.2 is taken as the weightof extraction solvent added to (h) Calculate thethe titration beaker. If a vol- follows:

Schuster bottle:

Percent water =

the specimen.

percent moisture as

Volumetric flask:F[ (RV–S)—(RV´S´ ) ]

Percent water = W´

where:

F = factor determined as specified in Method 101.2.1, para. 5.3

R = ratio determined as specified in Method 101.2.1, para. 5.2

V = Karl Fischer reagent used for sample, ml.

V´ = Karl Fischer reagent used for blank ml.

S = standard water-in-methanol solution used for sample, ml.

S´ = standard water-in-methanol solution used for blank, ml.

G = weight of decanted portion of extraction solvent used toextract sample, gm.

G´ = weight of decanted portion of extraction solvent used forblank, gm.

T = total weight of extraction solvent used to extract thesample, gm.

W = weight of pyrotechnic, gm.

W´ = weight of pyrotechnic represented by aliquot, gm.

2Method 101.4.1


Method

MOISTURE (KARL FISCHER

1. SCOPE

1.1 This method is used for determiningthe moisture content of pyrotechnic compo-sitions which contain materials which reactwith the Karl Fischer reagent and whichcannot be separated by extraction.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 25 grams (gm) of the mixtureweighed to within 1 milligram (mg). In theevent that the sample has begun to hardenbefore weighing, it should be rubbed gentlythrough a 20-mesh screen with a rubberstopper.

3. APPARATUS

3.1 Allihn condensers, 300 millimeter(mm) jacket with standard taper 24/40inner-member joint, such as Kimax No.18260, protected by drying tubes containinga suitable desiccant

3.2 Automatic burets-two, 25 milliliter(ml), such as Kimax No. 17138F,

3.3 Boiling flasks, 250 ml, flat-bottomed,with standard taper 24/40 joint, such asKimax No. 25055.

3.4 Dead-stop indication circuit consistingof platinum electrodes in series with micro-ammeter and source of direct current (de)voltage variable from 0 to 1½ volts such asshown in figure 1 of MIL-STD-1234, Method101.2.1; the apparatus described in Method101.2.1 may be used.

3.5 Distillation receiver, similar to figure1, of borosilicate glass. This item may beconveniently fabricated by attaching a


101.5

DISTILLATION METHOD)

standard taper No. 2 stop-cock such asKimax No. 41004, to a crankcase dilutionreceiver ASTM standard D-322 such asKimax No. 22009, and drawing-out and curv-ing the outward stem to serve as a draw-offspigot, as shown in the figure. Alternatively,a receiver such as Scientific Glass App. Co.No. JD 8100 may be used with the spigotattached to the bottom of the graduatedportion (figure 2).

3.6 Electric hot plate.

3.7 Oven, 70 degrees Centigrade (C), suit-ably heated.

3.8 Tall-form beakers, 300 ml., such asKimax No. 14030, or other suitable titrationflask.

3.9 Volumetric flasks, 50 ml, with standardtaper stopper, such as Kimax No. 28015.

Note. The boiling flasks, receivers, beakers ortitration flasks, and volumetric flasks must be dry.

4. MATERIALS

4.1 Karl Fischer reagent, stabilized, FisherScientific Company No. SO–K–3 or equiva-lent, stored in an automatic buret the air-inlet of which is protected by a drying tubecontaining a suitable desiccant.

4.2 Methanol, anhydrous, suitable for KarlFischer analyses.

4.3 Sodium tartrate dihydrate containing15.66 plus or minus 0.05 percent of water asdetermined by the loss of weight when driedat 160 degrees C. for 3 hours.

4.4 Trichlorethylene, Fisher certifiedgrade, Catalog No. T–341, or equivalent,prepared by shaking with water in a separa-

1 Method 101.5



tory funnel at least two minutes and left tostand in contact with water at least over-night.

4.5 Water-in-methanol standard solution,1 mg of water per ml of anhydrous methanol,stored in an automatic buret, the air-inletof which is protected by a drying tube con-taining a suitable desiccant.

5. PROCEDURE

5.1 The specimen is weighed and trans-ferred to the dried boiling-flask which isimmediately re-stoppered. Another suchflask without sample is subjected to the samesubsequent treatment and serves as a blank.Just previous to use the condenser and re-ceiver are rinsed with anhydrous methanolwhich is discarded. (A small residue ofmethanol in the condenser and receiver doesno harm.) The stopper is now removed fromthe flask, the receiver (its stopcock closed)is inserted in its place, and a 100 ml portionof water-saturated tichlorethylene pipettedinto the receiver so that Column A (Fig. 1)remains substantially filled. The assembly isnow connected to the condenser. (In theevent that these operations are interrupted,the receiver should be stoppered). The tem-perature of the heat source is adjusted sothat the reflux from the condenser is about 2drops per second. The distillation is con-tinued for 2 hours, at the end of which timethe flask and contents are allowed to cool.When condensate no longer drips from thecondenser into the receiver, the contents ofthe receiver are drawn off through the stop-cock into a drid 50-ml volumetric flask. Thedrying tube is removed and the condenserand receiver washed with a few portions ofanhydrous methanol which are drained intothe volumetric flask. The boiling-flask andreceiver are now detached from the con-denser and the receiver is further washedwith successive portions of methanol whichshould be sufficient in volume to substantial-ly fill the capillary E (fig. 1) without causing

it to overflow, until the volumetric flask isfilled to its mark. The flask is stoppered andmixed by shaking and may be set aside untiltitrated.

5.2 Transfer a 20 ml aliquot from the vol-umetric flask into a dried titration vesselcontaining a stirrer, and sufficient neutral-ized solution to cover the electrodes. Thevessel is quickly covered, stirring com-menced, and Karl Fischer reagent added, 1ml at a time, until the titrated solution re-mains a distinct red-brown color (not lighttan) for at least a minute. The solution isnow back-titrated with standard water-in-methanol solution, which is added in a steadystream until the brown color is replaced byyellow, then drop-wise until the microam-meter reading commences to fall as describedin Method 101.2.1, paragraph 5.1. The per-centage of water is calculated as follows:

Percent water =

where:

F = gm weight of water per ml ofstandard water-in-methanol so-lution determined as follows:

V a and Vb = ml Karl Fischer re-agent added to specimen andblank respectively.

R = ml of standard water-in-methanol solution per ml ofKarl Fischer reagent deter-mined as shown in paragraph5.3.

S a and Sb = ml of standard water-in-methanol solution for back-titration of specimen and blankrespectively.

W = weight of specimen in aliquot, gm= 10 gm (as directed).

5.3 To determine R, a 100 ml portion ofanhydrous methanol in a dried titration ves-sel is “neutralized” by titration with Karl

Method 101.5 2


Fischer reagent and back-titration withwater-in-methanol solution in the manneralready described (These volumes need notbe recorded). An accurately measured vol-ume (approximately 5 ml.) of Karl Fischerreagent is added to the neutralized methanoland titrated back to thestandard water-in-methanolthen calculated as follows:

SrR =

Vrwhere:

endpoint withsolution. R is

Vr = ml. of Karl Fischer reagent added(5, as directed).

Sr = ml. of standard water-in-methanolsolution required to neutralizeV r.

Note. R. should be the average of at least twodeterminations which do not differ by more than 0.03.

5.4 To determine F, and accuratelyweighed 0.3 plus or minus 0.1 gram portionof sodium tartrate dihydrate is added to a100 ml volume of anhydrous methanol whichhas previously been neutralized as describedin the foregoing paragraph. When dissolved,the solution is titrated with Karl Fischerreagent and back-titrated with standardwater-in-methanol solution in the same man-


ner as the methanol solution resulting fromdistillation of the sample. F is calculated inthe following manner:

15.66 Wf

F =V fR — Sf

where:

W f = grams of sodium tartrate dihy-drate.

V f = ml. of Karl Fischer reagent addedto sodium tartrate dihydratesolution.

Sf = ml. of standard water-in-methanosolution for back titration ofsodium tartrate dihydrate solu-tion.

Note. F should be the average of at least twodeterminations which do not differ by more than0.003.

5.5 For production control, where it is im-practical to perform a blank determinationfor each sample, the blank value should be

determined daily by a minimum of twotitrations and should be rechecked more fre-quently whenever new reagents are used.

Note. The range of values obtained for the blankshould not change the value of the moisture contentby more than 0.02 percent.

3 Method 101.5



Method 101.5

FIGURE 1. Distillation receiver

4



FIGURE 2. Distillation receiver.

5 Method 101.5




Method 102.1.1

VOLATILES (OVEN METHOD)

1. SCOPE

1.1 This method is used for determiningthe volatiles content of pyrotechnics on thebasis of loss in weight on heating at atmos-pheric pressure, at a specified temperatureand for a specified time.

Note. This method is applicable to a variety ofheating conditions and is not intended to restrict orlimit such factors as temperature or time of drying.For specific instructions refer to the applicablepyrotechnic specification.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 2 gm of the pyrotechnic weighed towithin 0.2 mg.

3. APPARATUS

3.1 Weighing dish of suitable diameter sothat the specimen can be spread out in athin layer.

Note. Samples that exhibit hygroscopicity requirea glass receptacle with a ground glass, cap styletype of cover.

3.2 Oven.

3.3 Desiccator containing a suitable desic-cant such as anhydrous calcium sulfate.

4. PROCEDURE

4.1 Place the specimen in a tared stop-pered weighing dish.

4.2 Heat the dish and contents with thecover removed at 100 degrees plus or minus5 degrees C., and at atmospheric pressurefor 4 hours or as specified in the applicablespecification.

4.3 Cover the dish and cool to room tem-perature in a desiccator.

4.4 Determine the loss in weight, and cal-culate the percentage of volatiles in thesample.

4.5 Calculations.

Percent volatiles = A100W

where:

A = loss in weight, gm.


1Method 101.2.1




Method 102.2.1

VOLATILES (VACUUM OVEN METHOD)

1. SCOPE

1.1 This method is used for determiningthe moisture and volatile solvent content ofpyrotechnics on the basis of loss of weighton heating at 55 degrees C. under vacuum.

2. SPECIMEN

2.1 The specimen shall consist of approxi-mately 2 gm of the pyrotechnic weighed towithin 0.2 mg.

3. APPARATUS

3.1 Weighing dish: diameter, 60 mm;depth, 30 mm, or of suitable size to allowthe specimen to be spread out in a thin layer.

3.2 Vacuum oven.

3.3 Desicator containing a suitable desic-cant such as anhydrous calcium sulfate.

4. PROCEDURE

4.1 Place the specimen in the tared weigh-ing dish, and heat it for 4 hours, or untilconstant weight is obtained, in the vacuumoven at a temperature of 55 degrees plus orminus 2 degrees C. and a pressure (absolute)of 80 plus or minus 10 mm of mercury.

4.2 Cool the specimen to room temperaturein the desiccator.

4.3 Determine the loss in weight, and cal-culate (by weight) the percentage of vola-tiles in the sample as follows:

Percent volatiles = A100W

where:

A = loss in weight, gm.


1 Method 102.2.1

* U.S. GOVERNMENT PRINTING OFFICE: 201073—1966—(V-496)



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