A simple and colorful demonstration of light-catalyzed bromination of

A Spontaneous Exothermic Reaction between Two Solids. A Safe Demonstration. Submitted by. Earle S. Scott. Ripon College. Ripon, WI 54971 ... the water...
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tested Jemonstrcrtions A Spontaneous Exothermic Reaction between Two Solids A Safe Demonstration Submitted by Earle S. Scott Ripon College Ripon, WI 54971 Checked by Ronald Stmthkamp Hofstra Universitv Long Island, NY i1550 When equal masses (1-2 g) of hydroxylamine hydrochloride and sodium nitrite are ground, mixed and then ground together, a reaction occurs that generates enough heat to char the paper on which the chemicals were mixed and to vaporize the water produced in the reaction to form a visible cloud. The reaction occurring may be represented by eq 1.

AH for this reaction is -136.5 kJ per mole or -32.62 kcal per mole. This reaction does not start spontaneously if the solids have been thoroughly dried before grinding and mixing them. However, both reagents are mildly hygroscopic so the required amount of water is usually present in the solids as they are taken from the bottle. If a mixture of the dried solids is sprayed with a mist ofwater, reaction occurs immediately. If a solution of sodium nitrite is added to a solution of hydroxylamine hydrohloride, nitrous oxide is formed and bubbles from the~solution.Thus, this system may be used to demonstrate an exothermic reaction between two solids, the importance of providing a mechanistic pathway for even such an exothermic reaction, or the preparation of Ntrous oxide through the reverse disproportionation type reaction that often occurs when compounds of nitrogen in high and low oxidation states are mixed. The customary preparation of nitrous oxide by the thermal decomposition of ammonium nitrate is another example of this type of reaction but is inherently more dangerous than this preparation of nitrous oxide, because overheating frequently leads to an explosion. For average-sized classrooms, the reaction can be run in a n 8-in. test tube to good effect. The concentrations need not be rigidly controlled. Dissolve between 1 and 1.5 e of sodium nitrite in 10 mL water. Dissolve between 1and-1.5 g hydroxylamine hydrochloride in 10 mL water. (This r e p resents arange ofioncentration from approximately 1.5 2 M for each reagent before mixina.~Pourthe two solutions together in a n s i n . test tube andshake enough to assure mixing. Hold the test tube against a dark background so the bubbles that form can be observed. Shortly, a froth will form on the top of the solution, and it will increase in height to 2 or 3 in. Gas evolution continues for several minutes. By the end of the reaction, the solution is hot to the touch. 1028

Journal of Chemical Education

GEORGE L. GILBERT Denisan University Granville,OH 43023

It is interesting to note that the corresponding reaction between sodium nitrite and ammonium chloride to produce nitrogen does not occur under these conditions even though the change in enthalpy (-221.7 kJ1mol) is more favorable. Ammonium chloride and sodium nitrite do not produce nitrogen readily from an aqueous solution without the addition of a mineral acid. It seems likely that the reaction actually occurs between nitrous acid and the m i n e . Hydroxylarnmonium ion is a much stronger acid than ammonium ion (ionization constants 2.2 x 10.' and 5.6 x 10-'', respectively) so is more capable of providing the nitrous acid needed for the reaction to proceed.

A Simple and Colorful Demonstration of Light-Catalyzed Bromination of an Alkane Submined by

Malcolm P. Stevens University of Hartford West Harlford. CT 0611 7

Checked by Leonard C. Grotz University of Wiswnsin Center, Waukesha Co. Waukesha, WI 53188-1 628 Light-catalyzed halogenation of alkanes is traditionally among the first react~o"~ students encounter in thr heg;nlng organic course Such a reactlon can be demonstrated in an extremely simple but colorful manner as follows Procedure Caution: The bromine solution is kept in

bottle.

a small dropping

Caution: If a sunlamp is used, precautions should be taken to shade the lamp so that the students cannot view the bulb directly. Caution:The organic compounds should be disposed of with other halogen-containingwaste solvents.

Add about 25 mL of water to each of two 25 x 200-mm test tubes. One drop of dilute (3 M) ammonia and 10 drops of phenol red indicator are added to impart a distinct violet color. Avolume of a liquid alkane equal to that of the water is then added to each test tube. (2,2,4-Trimethylpeutaneis recommended because it reacts rapidly and is relatively inexpensive, but any liauid alkane should suffice.) of a 5%(vlv)bromine solution in a n ~ ~ ~ r o x & a2t m e li ~ inert solvent, such as methylene chloride, is then added to one of the tubes slowly so that the bromine mixes only with the upper layer. Both tubes are then corked. Upon irradiation of both test tubes with a 275-W sunlamp, the brown color of the bromine-containing solution fades r a ~ i d l vto colorless. and a narrow vellow band anpears i;thi aqueous layer at the liquid;nterface. u p i n agitation of both test tubes, the aqueous layer in the brominated sample turns yellow throughout, thus indicating the generation of the acidic (hydrogen bromide) by-product. ~

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Discussion This demonstration also works satidwtorily with an ordinam 150-W liaht bulb. but the reaction time is lonaer(30 to 45; compared with 10to 20 s with the sunlamp). That the test tube containing no bromine remains violet offers proof that the indicatorcolor change was not caused by the light alone. Under normal room lighting, the brown bmmine color persists in the upper layer for 10 to 30 min, dependina on the amount of bromine added and the room iightin& Phenol red is not the only indicator that can he used. Of thc several tested, however, the contrast of violet and ycllow s~emedthe most pleasing aesthetically. Universal indicator is not suitable because it is Dartitioied between the aqueous and organic phases. If there is sufficient class time left followillg the demonstration, bromine may be added to the untr;ated sample and left to react under room lighting during the continuation of the lecture. Students then see the brown color fadine slowlv and thus can better a ~ ~ r e c i ahow t e lieht intensity affects the reaction. One mi&t also wish to f h o w this demonstration with either a complementary demonstration (1)or a n experiment (2)illustrating the relative reactivities of primary, secondary, and tertiary hydrogens towards light-catalyzedbromination. An overhead projection demonstration of alkane bmmination has been published recentlyX3) Literature Cited

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1 Uohcny A .I lrmdcn.

C M I

C k n l Fdur 1880.57607 2.\I'rrkmtln.J J C h ~ r nEdur l S B B . U . 3 3 1 . J P.mn.3. I . >llanowr D .I l k r m E d w . 1 9 0 66. 2 7

collapses upon exposure to the water and forms a tight fit around the test tube and stopper. The fact that the volume was observed to decreased by over 100-fold dramatically demonstrates the relative volumes of NH3(g)and NHdaq). The demonstrator handling the balloon will notice that the reaction is exothermic. This Journal recently published an article entitled Ammonia Bottle (3). A 2-L plastic soft drink bottle filled with ammonia collapses as water is injected into the bottle and the gas dissolves. The ammonia bottle and the ammonia balloon demonstrations both share the same learning objectives and each is effectivedue to the fact that a volume decrease is observed. Interested readers should try both approaches. 'Caution: Compressed ammonia cylinders should be handled in a fume hood only by individuals familiar with the use of cornmessedeases. Filled balloons mav be rcmuved from the h o d in ordw to perform the demonsmation in a classroom Aside from the bnlloon-filhng proress, t h demonsrrotion ~ has no signilirant hazard.

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Literature Cited 1.summerlin,L R.;Ealy,J. L.,Jr. C h e m i m l D e m o n s t r o t i o n s . A S ~ ~ ~ ~ ~ b * ~ k k m ; Am&Chemical Society: 1985. 2. Shakhashul, B. 2. Chmrcol Demonstmtions; Uni~rsityafWkmsin:Madison, WI, 1980;VoL 2. 3. Sheets, M.; DiStefana, R J. C h .Edac 1691,68,247.

Cleavage Patterns in a Layer of Talc Spread over Water Surface Submitted by

Ammonia Balloon Submined by

Jamil Ahmad University of Bahrain P.O. Box 32038 Bahrain

Bruce Mattson Checked by

Checked by

Erwin Boschmann IU-PU at Indianapolis Indianapolis, IN 46202 A Drawback of the Ammonia Fountain The ammonia fountain has been the traditional demonstration of the solubility of ammonia gas in water. This Journal has Drinted numerous variations of the demonstration over 'the years. Interested readers also will fmd a practical description of the basic ammonia fountain in most chemical demonstration books including Summerlin and Ealy (1)and Shakhashiri (2). Despite its beauty, the ammonia fountain suffersa t least one shortfall in terms of offerina viewers a conce~tuallv meaningful chemical demonstration, The fact that the container volume does not change seems to detract from its main objective: to demonstrate ammonia's solubility in the water. A Demonstrationof Ammonia's Aqueous Solubility I offer here a simple, effective, and impressive demonstration of ammonia's aqueous solubility. First, a small test tube is fdled w i t h 2 3 mL water and tightly stoppered. The tube is then worked into a balloon. Next, the balloon is inflated with ammonia gas from a tank or lecture bottle and tied shut. At the time of the demonstration. the s t o ~ per is removed from the test tube by grasping it throuih the inflated balloon. This is not difficult orovidina the balloon has not been inflated to its limit. ~e balloon quickly

Ronald E. DiStefano Northampton Area Community College Bethlehem, PA 18017

Adrop of oil brought in contact with the surface of water s ~ r e a d sto form a monomolecular film. The Dresence of akphiphilic molecules of oleic acid results in t