Appendix III - Appendix III to Part 150—Testing Procedures for Determining Exceptions to the Chart
General safety precautions—Chemical reactivity tests have, by their nature, serious potential for injuring the experimenter or destroying equipment. The experimenter should 1) have knowledge of the magnitude of the reactivity to be expected, 2) use adequate facilities and protective equipment to prevent injury from splatter of materials or release of fumes, and 3) start on a small scale so that unexpected reactions can be safely contained. All tests should be performed in a well-ventilated laboratory hood provided with shields.
Testing chemicals other than liquids—The procedure outlined below was developed for chemicals which are liquids at ambient temperatures. If one or both chemicals are normally shipped at elevated temperatures, the same procedure may be followed except the chemicals are tested at their respective shipping temperatures and the oil bath in Step 3 is maintained at a level 25 °C above the higher temperature. This information is then indicated on the data sheet. If one of the chemicals is a gas at ambient temperatures, consult the Coast Guard for additional instructions before proceeding with the compatibility test.
Step 1Objective—To determine if the test chemicals react violently and present a safety hazard in further tests.
Procedure—Place 0.5ml of one (A) of the test chemicals in a 25 × 150mm test tube. Clamp the test tube to a stand behind a safety shield (in a hood). Carefully add from a dropper 0.5ml of the other substance (B). Shake to induce mixing. If no immediate reaction occurs, retain the mixture for at least 10 minutes to check for a delayed reaction.
Results—If a violent reaction occurs, such as sputtering, boiling of reactants or release of fumes, record the results on the Data Sheet (appendix IV) and do not proceed to Step 2. If no reaction or a minor reaction occurs, proceed to Step 2.
Step 2Objective—To determine the heat of reaction of two chemicals on mixing under specified conditions.
Procedure—These separate mixes of the proposed binary combination will be tested. These are 2 ml : 18 ml, 10 ml : 10 ml, and 18 ml : 2 ml, respectively, to result in a final mixture of about 20 ml in each case.
A reference-junctioned thermocouple is prepared by inserting two lengths of 20 gauge or finer iron-constantan or chromelalumel duplex thermocouple wire into glass capilary sheaths. The common wire of each probe is joined, while the other wire of each is connected to a strip-chart recorder. The thermocouple probe which produces a negative pen deflection upon warming is the reference junction and is placed in a test tube of water at ambient laboratory temperature. The other probe is placed near the bottom of a Dewar flask of about 300ml capacity, such that the thermocouple will be below the surface of the test mixture. The Dewar flask is equipped with a magnetic stirrer having a stirring bar coated with an inert material such as a fluorinated hydrocarbon.
Start the temperature recorder and stirrer. Deliver the test chemicals to the Dewar Flask simultaneously from separate graduated syringes. If an exothermic reaction occurs, continue the test until the maximum temperature is reached and begins to subside. If no apparent reaction occurs, continue the test for at least 30 minutes to check for a delayed reaction. Stop agitation and observe the mixture at five-minute intervals to determine if the mixture is miscible, if gases are evolved, or if other visible changes occur. In the interest of safety, a mirror can be used for these observations. Repeat the above test for the other mixture combinations.
Results—Record the results in the appropriate places on the Data Sheet. If no reaction occurs or if the temperature rise is less than 25 °C, proceed to Step 3. If the observed temperature rise exceeds 25 °C or gases are evolved, do not proceed to Step 3.
Step 3Objective—To determine if exothermic reactions occur at temperatures up to 50 °C.
Procedure—If a non-hazardous reaction occurred in Step 2, the ratio of chemicals which resulted in the greatest temperature rise will be tested. Fresh chemicals will be used with a total volume for this test of about 10ml (a ratio of 1ml:9ml, 5ml:5ml, or 9ml:1ml). If no reaction was observed in Step 2, use a ratio of 5ml:5ml. Using the thermocouple prepared for Step 2, insert the reference probe into a 25 × 150mm test tube containing 10ml of water. Place the other probe into an empty test tube. Start the temperature recorder and add the two chemicals of the combination, one at a time, to the empty test tube. Lower the two test tubes into an oil bath maintained at 50 ±2 °C. Hold the samples in the oil bath until the maximum temperature differential is recorded, and in all cases at least 15 minutes. Observe the test mixture to determine if gases are evolved or if other visible changes occur. Follow prescribed safety precautions.
Results—Record the maximum differential temperature measured, the time required to reach this temperature, and any other observations in the proper space on the Data Sheet.
Send a copy of the Data Sheet for each binary chemical mixture tested to: Commandant (CG-ENG-5), Attn: Hazardous Materials Division, U.S. Coast Guard Stop 7509, 2703 Martin Luther King Jr. Avenue SE., Washington, DC 20593-7509.