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Joe A. Vinson and William T. Grabowski

University of Scranton

Scranton, Pennsylvania

18510

I

organic Qualitative Analysis

I An improved sodium fusion procedure and a new test for Nand S

Qualitative organic analysis has traditionally been a structured course for upper division chemistry majors. In many schools, infrared and nmr analyses are now taught in the sophomore course and used by students, along with wet chemical tests. for the identification of unknown oreanic compounds. 1; the interest of greater safety in the siium fusion method and in im~tovineand simnlifvine the elemental tests, we have developei a newsodium ?usLon~rocedureand a new single reagent test for nitrogen and sulfur.

ExperimentalProcedures

Sodium Fusion In a small test tuhe place about 0.5 g of sodium-lead alloy (dri-Nam from J. T. Baker Chemical Company). Clamp the tube in a vertical position and heat with a flame until the alloy melts and fumes of so- dium are seen up the walls of the tuhe. Do not heat the alloy tored- ness. Add a few drops of liquid sample or 10 mg of solid. During ad- dition be carefulnot to get any sample on thesides of the tuhe. Heat gently, if necessary, until the reaction is initiated; remove the flame until it subsides, then heat to redness fora minute or twoand let cool. Add 3 ml of H20and heat gently for a few minutes to react the excess sodium with the water. Filter the solution, if necessary. Wash the filter paper or dilute the decanted reaction mixture with about 2 ml of water and proceed with the elemental analysis.

Nitrogen or Sulfur Test I'ut ahout 10 drops of the fusion solution in a small test tube and saturate it with sohd sodium birarhonaw. Shake toensure saturation and check towe if excess solid is urwnt. Then add 1 or 2 drops of the saturated solution (it is permissible to transfer some of thesolid so- dium bicarbonate) to a test tube containing about 20 droos of a 1% p-nitrohenzaldrhydesa>lurionmdimethylsulfmide IPNBreagentr. This reagent should he discarded if the initial yellow cdur darkens and should be stored in a brown hottle A purple color indicates ni- trogen is present. A green color indicates sulfur is present. If both sulfur and nitrogen are present, only a purple color will he visible. Therefore, if a positive test for nitrogen is observed with PNB, a test for sulfur hv another method should he emoloved. The lead acetate or sodium &ro-prusside test (1)are suitadle. if only a positive test for sulfur is observed by the present method, then nitrogen is defi- nitely absent.

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&logen

Tests

Transfer about 10 drops of the fusion solution into a test tuhe, ac- idify with dilute nitric acid, and boil to remove any hydrogen cyanide and hvdrozen sulfide. Add 1 droo of aqueous silver nitrate to the so-

lutio'.

of chloride, bromide, or iodide. Specific tests are then necessary to

A ihite to yellow cloud or precipitate indicates the presence

identify the halogen(s)present.

Presented ar the 169th National Meeting of the American Chemical Society, Chemical Education Dwision. Philadelphia, I'ennrylvania. April, 1975.

Results and Discusion

Fusion

Although the Lassaigne procedure (1-3). commonly known as the sodium fusion test, is easy to perform, there are hazards in the use of metallic sodium: handling difficulties, instability in air, ignition of hydrogen during reaction with water, exothermic reactions with some oreanim. and dismal ~rohlems.The newer calcium oxide-zinc fusion procedure (4) rs less hnmrdous than sodium fusion. Nitrogen corn. puundr are converted to ammonia whrrh ~u deterted hy indicator paper. A blank must be nm ~imultanroualyto distinguish hetween a true and false positive test. False negatives result from eompounda such as 3,5-dinitrobenzoie acid and false positives result from poor technique when the fusion mixture sulatters onto the indicator

Paper.

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The use of a lead allov with sodium in the ratio 9:l is described bv Lance (5) for the decompmltian of orgames contamlog heteroele- ments. The alloy is m a dry, gmnular fom and gives no d~ffirultym handling. It is fairly stable in air and is easily stored in a screw-capped jar. When the material is added to water, it falls to the bottom of the &ntainer eivina a non-vigorous reaction without any ignition of the hydrogen. lt iskommended that thr residues from sbdium fusion with the alloy be pooled in an open vessel and disposed of properly in order to minimize lead pollution.

Elemental Analysis Nitrogen is the most difficult element to detect. During sodium fusion. cvanide ion is formed from the nitroeen in the oreanic eom- pound. cyanide ion is usually detected by t<e Pmssian glue test in whieh cyanide is converted to ferroeyanidewhieh reacts with ferric ion to farm a precipitate of ferric ferraeyanide or Prussian Blue. The test requires careful control of pH for best results (6). Green or greenish blue solutions after the test indicate poor fusion. The pres- ence of sulfur can obscure the test for nitrogen. When ferrous ion is added, iron sulfide must be removed by centrifugation or filtration before proceeding with the Prussian Blue test. Many nitrogen compounds, such as polynitro compounds, azo compounds, pyrrole derivatives, and proteins, are difficult to detect because of slow or incomplete reaction with sodium when followed by detection with the relatively insensitive Prussian Blue test. Cheronis (I) indicates these compounds should he decomposed hy alternative methods such as magnesium or soda-lime. Greater sen- sitivity can be obtained with henzidine-cupric sulfate. However, sulfide and iodide interfere with this test and henzidine is carcino- genic. A new modification of the pyrazolone color reaction has been developed (5). The cyanide is oxidized by chloramine T and detected by two reagents which are stable for 2 mo in the refrigerator, However, these reagents are dissolved in pyridine which is both obnoxious and tmic. A selective and sensitive cyanide test which ufilizesp-nitroben- znldehydc (I'NRI and o-dinitrohenzme has been published (7) and used successfullv in the oreanir lahmatorv 16).hrineaninvestieation of this reaction: we founlthat. if the initial reaction of o-nitGhen- ddehydrand cynnidc werecankl out in dimethylaulfonide,a purple color was formed. This color is the harivuf a simple test fur ryanrde. This new color test, in combination with the sodium alloy fusion

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Volume 54. Number3. March 1977 1 107

Table 1.

Difficult Nitrogen Compounds

 

Description

of Fusion

Color and

Type

Compound

Reaction

Rate

p~iynitro

m-dinitrobenzene

moderate

purple-rapid

piclic acid

violent

purple-medium

ALO

arobenlene

moderate

our~le-ra~id

methyl orange.

slow, charred

purple-medium

sodium Salt

Diazo

~astBlue B

moderate

pink-slow

Fast Red Salt B

fast

purple-rapid

Amino Acid phenyiaianine

fast

purple-rapid

 

arpartic acid

fast

purple-rapid

Protein bovine albumin slow

purple-rapid

 

hemogiobin

11ow.charred

purple-rapid

Aminonap-

4-amino-l-naptnalen

fast

pink-slow

thalene

ruifonic acid

Sulfonic

Acid

 

8-amino-3-napthaiene

fast

purple-slow

s~lfonicacid

Nitrite

butyl nitrite

fast

purple-rapid

i~opentylnitrite

fast

purple-rapid

Table 2.

Sulfur Compounds

Comoound

Color with PNB

IUI~OI~I~CYI~Cwid

green

2-mercatoethanol

green

dimethyl ruifoxide

light green

carbon dirulfide

dark green

thiophenol

green

p-toluenerulfonic acid

green

thiophene

green

tetrahydrothiophene-1.l.dioxide

yellow green

method, was used for the analysis of difficult to detect nitrogen compounds. The results are shown in Table 1. Only in the case of picricaeid was thereaction violent with the sodium alloy. A lessvig- orous reaction occurred if small amounts of pierie acid were added intermittently. Heating is necessary for those compounds with slow reactions and should be used routinely with unknowns. Color devel- ooment with PNB reaeent occurred within 15 s for all compounds

ekceot the slaw reactin; ones. These took a minute or two fir color

i,r pinkish-purple rdur wrth PNR. This is

formation gwng n pmk

pnnbahly a conrenrmtion cfferi, ir, that rheam~untut cyanidrformrd from fusion in these eases is low. Table 2 lists the sulfur compounds which were tested. All of these compounds reacted rapidly with the sodium alloy. The green color was not stable and disappeared after 5 mi". It could be reformed by

the addition of anotherdrooof fusion mixture which had been satu- rated with sodium bicarbonate. The sensitivity of the method was determined using a standard

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Table 3.

Representative Compoundr Given As Unknowns

Compound

~diphenylthiourea ethyl carbamate p-bramoaniiine coumarin carbon tetrabromide benzophenone p-nitrochiorobenzene tribenzyiamine dibenlyl tetraethyl ammonium bromide ~.t~l~ene~~lfoni~acid b-nitrobenryl bromide 4-amlno-l-napthaiene rulfonic acid dimethyi ruifoxide glycyiglycine iodbform

Element(s) Present

N.

S

N

N. X

none

X

none

N.

N

none

N. X

s

X

aqueous solution of sodium cyanide saturated with sodium bicar- bonate. One drop was added to 20 drops of PNB reagent. A brown- purple color was barely evident with 0.25 pg of cyanide. This sensi-

better

than Prussian Blue. Hydroxide ion gives a purple color but this in- terference is eliminated by lowering the pH of the fusion mixture by saturating with sadium bicarbonate. No interference was noted with any other anion tested. No problems in either prmedure or identification were encountered with comoounds in Table 3 eiven as unknowns to a class of 150 stu- dents rf the pnxedureunr tc~~'llou.edcurrrrtlv. The two critical steps nerwiary for good r~sdtcare first, suffiricnr hraring uf the sodium alhy with the unkncnvn and second, complrtc saturation uf the aqueous filtrate with sodium hiearbonate.

Summary

tivity is slightly better than the benzidine test (0.5 pg) and much

The proposed sodium allay fusion procedure is suitable for use in organic qualitative analysis and is safer with regards to handling and disoosal than the commonlv used sodium fusion method. The o-ni- trobenzaldehyde color test rs asimple, rapid, and sensitive color test far nitrogen or sulfur.

Literature Cited

Ill

Cherunii. N. D and Entriken, J. B., "SemimicroQualitafiveOqanic Analysis." 2nd Ed., IntorsciencePublishen. Inc New York. 1957. DD.172-180.

121

Pasto, D. J., and john^^. C. R "Orzanic Structure ~eterminstiun: ~rentiee-~sli.

Inc Eneiewood

Cliffs. N.J

19R9.p. 916.

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"TheS*rtematiclndentiflcation

Compounda,"Sth

Ed John Wiiey andLmr. lnc. New York, 1969.p. 62.

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