QUALITATIVE ORGANIC ANALYSIS SIM-ORG PROGRAM HELP SECTION
Dr. Scott Frees Ramapo College of New Jersey Mahwah, NJ 07430
CONTENTS: Introduction Strategy for Identifying and Unknown Solubility Classification Functional Group Classification Tests Derivative Formation and Use Final Identification of an Unknown Substance
This simulation program includes: 12 organic chemistry functional groups 24 classification tests 21 derivative tests 500 unknowns GENERAL INTRODUCTION TO QUALITATIVE ORGANIC ANALYSIS There are two methods for identifying the structure of an unknown organic compound. The first and older method is to run classification tests to identify the functional group of the compound following by the production of one or more derivative compounds to confirm the exact nature of the unknown. The second method is to determine the spectral properties of the unknown using mainly infrared and proton magnetic resonance spectroscopy. The first method will be covered in this simulation program. This program has 12 different functional group classes and 500 different unknowns. It is planned that the second method will be covered in a later revision of this program. The general method to determine the identity of an unknown substance by classical methods is to gather some introductory information about the compound. Note the odor, color, and melting or boiling point of the material. Then find its solubility characteristics by doing a solubility classification as described below. From the information obtained from the solubility classification run appropriate functional group tests to identify the group to which the unknown belongs. Then the unknown is converted into one or more different solids called derivatives. Consulting tables of derivative melting points one can then identify the exact identity of the unknown compound. In order to intelligently conduct the functional group classification tests a solubility classification is usually done first to narrow down the possible functional group possibilities.
STRATEGY FOR IDENTIFYING AN UNKNOWN The following steps should be taken to identify an unknown compound: 1. aldehyde. N2 These are medium size molecules (generally containing from 5 to 9 carbons) containing an oxygen atom. This classification method is not exact and may need further thought and imagination in certain cases. the amine will probably not be basic enough to form the salt and will. amine. Such unknowns are more difficult to identify. B1 Primary. Perform a solubility classification test to determine the possible functional group classes to which the unknown may belong. Beilstein test (for halogenated compounds) 6. if there are two or more phenyl groups on the nitrogen. or ketone. This may lead to confusion when interpreting the functional group and could lead one to the wrong table of derivatives. 3. Shown below is a list of possible functional groups for each solubility class. The tests are listed in numerical/alphabetical order. secondary and tertiary amines fall into this class. These solubility classes and their consequences can be summarized below: S1 These are very polar compounds which consist of salts of carboxylic acids or amines. Basic hydrolysis (for amides.A problem may arise when an unknown substance has two or more functional groups in the molecule. S2 These compounds are low molecular weight (generally less than 5 carbons) with a polar functional group such as carboxylic acid. The above approach should lead to a successful identification of an unknown about 80 % of the time. Acetyl chloride (for acidic hydrogen compounds such as alcohols) 4. Bromine in carbon tetrachloride (for alkenes and alkynes)
. be insoluble. SOLUBILITY TEST ANALYSIS: Obtain the solubility class for the assigned unknown. However. the unknown may pose difficulties that would require imagination and careful analysis of the data to be successful in its identification. Alkyl halides and alkanes fall into this class. alcohol. 2. Make one or more derivatives to finally determine the exact identity of the unknown. 2. IN These are neutral compounds. In other cases. FUNCTIONAL GROUP ANALYSIS: Below are listed 24 chemical tests that could be used to help identify an unknown. esters and nitriles) 5. N1 These are higher molecular weight compounds (generally more than 9 carbons) containing an oxygen atom. There are a few such compounds in this simulation program. A1 Higher molecular weight carboxylic acids fall into this class. Benedict test (for aldehydes and reducing sugars) 7.4-dinitrophenylhydrazine (for aldehydes and ketones) 3. then. A2 Phenols show this kind of solubility. Introduction to qualitative tests 2. Narrow the choices of possible functional groups to one group by performing appropriate functional group tests. 1. It is also possible the compound is of low molecular weight and has many polar functional groups such as a carbohydrate.
basic hydrolysis. 1. ferric hydroxamate. Ferric hydroxamate (for esters. sodium fusion. secondary and tertiary amines) 15. Nitrous acid (to distinguish primary. Lucas test (to distinguish primary. N1 or N2. combustion test 8. Ceric nitrate (for alcohols and phenols) 9. Iodoform test (for methyl carbonyl compounds) 17. combustion test 10. ferric hydroxamate. Ester – Solubility class N1 or N2. combustion test 3. Nitrile – Solubility class N1 or N2. combustion test 5. Combustion test (for flammable or combustible compounds) 11. hydroxylamine hydrochloride. 2. iodoform test. Ketone – Solubility class S2. potassium permanganate. sodium fusion. Hydroxylamine hydrochloride (for aldehydes and ketones) 16. Ferric chloride (for phenols) 12. nitrous acid.4-dinitrophenylhydrazine. basic hydrolysis. Hinsberg test. After each functional group name are hints about tests that could be used to help narrow the unknown possibilities. sodium fusion. Ferrous hydroxide (for nitro compounds) 14. Sodium fusion (for compounds containing halogen. nitrogen or sulfur) 23.8. combustion test 4. Alcohol – Solubility class S2. sodium fusion. N1 or N2. pH test. Amide – Solubility class N1 or N2. N1 or N2. ferric hydroxamate. secondary and tertiary amines) 19. Silver nitrate in ethanol (for Sn1 reactions of alkyl halides) 22. Chromic acid (for aldehydes. Tollens test (for aldehydes and reducing sugars) Below are listed the 12 functional group classes that appear in this program. Acid – Solubility class S2 or A1. Amine (primary and secondary) – Solubility class B1. chromic acid. Acid chloride – Solubility class S2 or A1. potassium permanganate. ceric nitrate. sodium fusion. Amine (tertiary) – Solubility class B1. acetyl chloride. pH in ethanol/water (to distinguish low molecular weight acidic or basic compounds) 20. combustion test 9. N1 or N2. pH test.4-dinitrophenylhydrazine. chromic acid. Benedict test. Potassium permanganate (for compounds that can be oxidized) 21. pH test. nitrous acid. The groups are listed in numerical/alphabetical order. Solubility classification (for general classification or organic compounds) 25. Acid anhydride – Solubility class S2 or A1. 2. N1 or N2. combustion test 6. combustion test 7. Hinsberg test. Hinsberg test (to distinguish primary. basic hydrolysis. Tollens test. primary and secondary alcohols) 10. combustion test 11. hydroxylamine hydrochloride. acid chlorides and acid anhydrides) 13. Beilstein test. solubility test
. secondary and tertiary alcohols of six carbons or less) 18. Aldehyde – Solubility class S2. Sodium iodide in acetone (for Sn2 reactions of alkyl chlorides or bromides) 24. Lucas test. combustion test 2.
2. esters. Methiodide (for tertiary amines) 13. Oxime (for aldehydes and ketones) 15. Semicarbazone (for aldehydes and ketones) SOLUBILITY CLASSIFICATION The solubility of an organic compound in various solvents can give valuable information about the unknown. For unknowns that do not fall into either class S1 or S2.4-dinitrophenylhydrazone (for aldehydes and ketones) 4. the unknown’s solubility in 5% sodium bicarbonate is determined. amides and nitriles) 7. Phenol – Solubility class A2. Phenylhydrazone (for aldehydes and ketones) 16. Acetamide (for primary and secondary amines) 6. combustion test DERIVATIVE USAGE: Below are listed 21 derivatives that could be prepared from various unknowns to help in a final determination of the unknown. Acid from hydrolysis (for acid chlorides. An unknown in class S1 is then tested as above using ether as the solvent. 1-naphthylurethane (for alcohols and phenols) 3. esters. The derivatives are listed in numerical/alphabetical order. acid chlorides and anhydrides) 9. amides and nitriles) 14. Benzamide ( for primary and secondary amines) 10. Benzenesulfonyl chloride (for primary and secondary amines) 11.5-dinitrobenzoate (for alcohols) 5. Phenylurethan (for alcohols) 17. ferric chloride. If the unknown dissolves. acetyl chloride. acid chlorides and anhydrides) 8. If it is soluble. p-Toluidide (for primary and secondary amines) 22. it is a polar compound and in placed in solubility group S1. anhydrides. ceric nitrate. If it is not soluble. Picrate (for tertiary amines) 18. Neutralization equivalent (for acids. p-Nitrobenzyl ester (for carboxylic acids) 19. With this background. Amide (for carboxylic acids.12. organic acids (such as carboxylic acids and phenols) react with bases to form water soluble salts and organic bases (such as amines) react with acids to form water soluble salts. If it dissolved in both water and ether it is then placed in class S2. the unknown is placed in class A1. p-Toluenesulfonamide (for primary and secondary amines) 21. p-Nitrophenylhydrazone (for aldehydes and ketones) 20. The general rule of “like dissolves like” or “polar compounds dissolve more readily in polar solvents” is useful. 1. Introduction to derivative use 2. Also. Anilide (for carboxylic acids. one begins the solubility classification by adding 3 drops or 3 mg of the unknown to 3 ml of water and shaking the mixture. 3. It should be noted that the polarity of an organic compound is increased by the kind and number of polar functional groups in the molecule and that the polarity decreases as the size of the non polar aliphatic group (define aliphatic group in a hyperlink) in the molecule increases. the solubility in 5% sodium
. Bromo derivative (for phenols) 12.
2. Do as many tests that may be necessary to absolutely confirm the functional group to which the unknown belongs. some idea of the type of organic compound should be evident. IN These are neutral compounds.The first test that should be done is a solubility test to determine the class or classes to which the unknown belongs. then. From the results of the solubility tests. the unknown belongs in class A2. or ketone. Use the results of this classification only as a focus into which classification tests should be done first. Such compounds that are soluble in 85% phosphoric acid are placed in class N2. secondary and tertiary amines fall into this class. Be careful to interpret correctly the test results for those unknowns that may contain two or more functional groups.4-DINITROPHENYLHYDRAZINE TEST (for aldehydes and ketones) . proceed to the preparation of derivatives to identity the exact identity of the unknown. However. Unknowns soluble in only this acid are placed in solubility class N1. S2 These compounds are low molecular weight (generally less than 5 carbons) with a polar functional group such as carboxylic acid. be insoluble.hydroxide is studied. esters. Select a test from the list of tests that would help confirm the presence or absence of the suspected functional group class. B1 Primary. orange or
. N1 These are higher molecular weight compounds (generally more than 9 carbons) containing an oxygen atom. alcohol. ketones. A further distinction can be made for compounds soluble in concentrated sulfuric acid by testing their solubility in 85% phosphoric acid. It is also possible the compound is of low molecular weight and has many polar functional groups such as a carbohydrate. the amine will probably not be basic enough to form the salt and will. amine. if there are two or more phenyl groups on the nitrogen. amides. ethers. A1 Higher molecular weight carboxylic acids fall into this class. The results of a solubility classification should not be strictly interpreted as there are many overlaps. For compounds insoluble to this point the next solvent to try is concentrated sulfuric acid.This test will be positive for an aldehyde or ketone as indicated by the formation of a yellow. A2 Phenols show this kind of solubility. These solubility classes and their consequences can be summarized below: S1 These are very polar compounds which consist of salts of carboxylic acids or amines. alcohols. aldehyde. Compounds soluble in 5% hydrochloric acid are placed in solubility class B1. it is recommended that the classification tests be done in this order: aldehydes. FUNCTIONAL GROUP CLASSIFICATION TESTS INTRODUCTION TO QUALITATIVE TESTS . N2 These are medium size molecules (generally containing from 5 to 9 carbons) containing an oxygen atom. for compounds insoluble to this point are placed in class IN. Alkyl halides and alkanes fall into this class. If it is soluble at this point. nitriles. Finally. alkenes and alkynes. If an unknown is insoluble to this point it is next tested for solubility in 5% hydrochloric acid. If the solubility test results put the unknown substance in the ‘Neutral’ section. At that point.
Acidifying this solution with concentrated hydrochloric acid would result in a precipitate if the carboxylic acid is water insoluble. phenols and alcohols. Easily oxidized compounds may destroy the ceric nitrate solution before the test may be observed. So. In some cases. If the unknown is not soluble in the reagent a negative test may be observed due to the lack of a reaction. The color of the precipitate can help further identify the extent of conjugation for the carbonyl group. the brownish color of elemental bromine disappears as the bromine adds to the unsaturated organic compound. ACETYL CHLORIDE (for acidic hydrogen compounds) . a solid (usually white) may form. the test will probably give a false positive test as acetyl chloride reacts vigorously with water. primary and secondary alcohols) – Easily oxidized compounds convert the red chromium (VI) ion to a green chromium (III) precipitate. This reaction pH gives the acid as a water soluble carboxylate salt. CERIC NITRATE (for alcohols and phenols) – Alcohol with 10 carbons or less will give a red color with ceric nitrate solution whereas phenols will give a green-brown to brown precipitate. this test may give false positive or negative tests depending on the expertise of the person doing the test. Highly conjugated aromatic aldehydes or ketones generally give red solids whereas non conjugated carbonyl compounds give yellow products. it may evaporate before it burns resulting in a negative test.Placing a small amount of an organic compound on the end of a copper wire and heating it in the open flame of a Bunsen burner results in a transient green color in the flame if the compound contains a halogen atom. CHROMIC ACID (for aldehydes. the solid.4-dinitrophenylhydrazone. BASIC HYDROLYSIS (for amides. BEILSTEIN TEST (for halogenated compounds) . BENEDICT TEST (for aldehydes and sugars) – When easily oxidized organic compound (such as aldehydes and reducing sugars) is heated in Benedict’s solution (which is a blue solution containing a complexed copper (II) ion) a brick red precipitate of cuprous oxide forms. If this precipitate is formed.Amides and esters can be hydrolyzed by heating in a sodium hydroxide solution.red precipitate which is called a 2. it should be filtered and used as a derivative for the unknown. BROMINE IN CARBON TETRACHLORIDE (for alkenes and alkynes) – When a solution bromine in carbon tetrachloride is added dropwise to an unknown compound. If the unknown is volatile. This precipitate can also be used as a derivative for the unknown if its melting point is determined (see below for derivative use). A positive test will be noted by the evolution of heat which may be hard to detect.This test will help identify carboxylic acids. If water is present in the unknown. could be used as a derivative for the unknown. If this happens.
. esters and nitriles) . if isolated and its melting point is determined.
secondary and tertiary alcohols of six carbons or less) – A solution of zinc chloride in aqueous hydrochloric acid can be used to distinguish primary. Highly oxygenated compounds burn with a blue flame. FERRIC CHLORIDE (for phenols) – Some (but not all) phenols give a color when ferric chloride solution is added. When a tertiary alcohol is added dropwise to the
. FERROUS HYDROXIDE (for nitro compounds) – Most compounds that contain a nitro group will give a brown to red-brown precipitate of ferric hydroxide by oxidation of ferrous hydroxide. Primary amines give a solid benzenesulfonamide product that is soluble in 5% sodium hydroxide. For example. aliphatic compounds give a yellow flame and aromatic compounds give a sooty flame. acetaldehyde and alcohols that have a methyl group bonded to the C-OH group can also give a positive test since such an alcohol can be oxidized to a methyl ketone by the iodoform reagent. The unknown compound must be soluble in the reagent in order for the test to be valid. Very volatile compounds may evaporate before burning or burn very rapidly. Acid chloride and anhydrides give a magenta or burgundy color with the test reagent. FERRIC HYDROXAMATE (for esters. Note that highly halogenated organic compounds may not burn. The iodoform regent iodinates the methyl group which they cleaves in the basic solution One should confirm the presence of a carbonyl group in the unknown before this test is done as misleading results could occur with other compounds. HINSBERG TEST (to distinguish primary. HYDROXYLAMINE HYDROCHLORIDE (for aldehydes and ketones) – Aldehydes and most ketones give a red color when added to a solution of hydroxylamine hydrochloride in ethanol-water that has a universal indicator added. LUCAS TEST (to distinguish primary. The manner in which a compound burns can give some information about its nature. IODOFORM TEST (for methyl carbonyl compounds) – This test is mainly used to identify methyl ketones. The amine functional group must be confirmed before this test can be performed as the test will give very confusing results with any other functional group. This test is not a definitive one and the results should be carefully evaluated. Tertiary amines do not react with benzenesulfonyl chloride. secondary and tertiary alcohols.COMBUSTION (for flammable or combustible organic compounds) – When a few milligrams of an organic liquid or solid are placed directly into a Bunsen burner flame they often burn. acid chloride and anhydrides) – Esters of carboxylic acids give a magenta color with this reagent. secondary and tertiary amines. Secondary amines give a solid benzenesulfonamide product that is insoluble in 5% sodium hydroxide. secondary and tertiary amines) – Benzenesulfonyl chloride can be used to distinguish primary.
Primary alcohols are unreactive with the Lucas reagent. SODIUM FUSION (for compounds that contain halogen. acid chloride or anhydride.Once the classification tests have indicated an organic family of compounds (e. Aryl and vinyl halides do not react. The halide is identified by precipitation with silver ions. an immediate second layer or a liquid alkyl chloride is formed. reducing sugars. DERIVATIVE FORMATION AND USE INTRODUCTION TO DERIVATIVE USE . one
. If the pH is in the acid range the compound can be a carboxylic acid.g an aldehyde). Any halogen. Aryl or vinyl halides do not react. NITROUS ACID (to distinguish primary. Secondary alcohols form a second layer of the insoluble alkyl chloride in three to 5 minutes. nitrogen or sulfur) – When an organic compound is placed in molten elemental sodium the molecules are violently destroyed. primary or secondary alcohols and some alkenes and alkynes. secondary and tertiary amines) – Primary aromatic amines give nitrogen gas evolution with the nitrous acid reagent. pH IN ETHANOL (to distinguish low molecular weight acidic or basic compounds) – The pH of compounds that are soluble in water or aqueous alcohol can be measured. Such organic compounds include: aldehydes. TOLLENS TEST (for aldehydes and reducing sugars) – Water soluble aldehydes and reducing sugars give a silver mirror or black precipitate of elemental silver with the Tollens reagent. Alkyl iodides will not give the precipitate. Some secondary halides will react more slowly. Other aromatic amines can undergo coupling reactions to form colored products. the compound may be an amine. SODIUM IODIDE IN ACETONE (for alkyl halides that can undergo Sn2 reactions) – Primary and some secondary alkyl chlorides or bromides will give a precipitate of sodium iodide in the reagent. Organic salts may hydrolyze in water which can lead to acidic or basic solutions.Derivative Tests . POTASSIUM PERMANGANATE ( for compounds that can be oxidized) – Organic compounds that can be readily oxidized will convert the purple of the permanganate ion to a brown precipitate of manganese dioxide. SILVER NITRATE IN ETHANOL (for alkyl halides that can undergo Sn1 reactions) – Tertiary alkyl halides will give a white to yellow silver halide precipitate with this reagent. The cyanide ion formed the nitrogen in the molecule is converted into Prussian blue by ferrous sulfate. If the pH is in the basic range. nitrogen or sulfur in the original molecule are converted to ionic materials which are then identified. The sulfide ion is identified by precipitation with lead ions. SOLUBILITY (for general classification of organic compounds) See SOLUBILITY CLASSIFICATION section above.reagent.
which derivative tests to use can be determined. Order all the derivative tests relevant to the search (e.can see if derivatives of the unknown can be synthesized to help in its identification. Based on the results of the classification tests. 1-NAPHTHYLURETHANE DERIVATIVE – (for alcohols and phenols) 2. the results will be illustrated. it is evidence that the correct family of compound has been chosen.4-dinitrophenylhydrazine derivatives) and then proceed to the final identification of the unknown substance.4-DINITROPHENYLHYDRAZONE – (for aldehydes and ketones) 3. ester. obtain the melting points of both the semicarbazone and 2. and nitriles) AMIDE – (for carboxylic acids. acid chlorides. anhydride. On selecting the relevant test. amides.(for aldehydes and ketones) p-TOLUENESULFONAMIDE – (for primary and secondary amines)
. and anhydrides) BENZAMIDE – (for primary and secondary amines) BENZENESULFONAMIDE – (for primary and secondary amines) BROMO DERIVATIVE – (for phenols) METHIODIDE – (for tertiary amines) NEUTRALIZATION EQUIVALENT – (for acids.5-DINITROBENZOATE – (for alcohols) ACETAMIDE – (for primary and secondary amines) ACID FROM HYDROLYSIS – (for acid chloride. and the melting point of the derivative should be recorded on a data sheet. amides. esters and nitriles) OXIME – (for aldehydes and ketones) PHENYLHYDRAZONE – (for aldehydes and ketones) PHENYLURETHAN – (for alcohols and amines) PICRATE – (for tertiary amines) p-NITROBENZYL ESTER – (for carboxylic acids) p-NITROPHENYLHYDRAZONE . for an aldehyde. and anhydrides) ANILIDE – (for carboxylic acids.g. If the derivative test is positive. acid chlorides.
Select the family that the unknown belongs to. then you will need to go back into the program in order to correctly identify the unknown sample. Also listed are the melting points of any derivatives that can be synthesized from the class of the unknown compound. ANSWER TRIAL . one will now have an idea of what the unknown sample is. A list of all the compounds of that type.p-TOLUIDIDE – (for primary and secondary amines) SEMICARBAZONE – (for aldehydes and ketones) FINAL IDENTIFICATION OF AN UNKNOWN SUBSTANCE Tables of organic substances can be used to identify the unknown based on the results of the classification tests and the derivative melting point results. you can enter it into the program by selecting Answer Trial. exactly as it appears in the table of unknowns. TABLES OF UNKNOWNS – Once the derivative melting point data have been recorded enter the Tables of Unknowns by selecting the suspected functional group class. Make sure that you select the compound correctly. Here a list of organic compounds separated by type will appear. By matching the table data with the unknown compound data obtained above. To see if you are correct. a congratulation message will appear.Based on all the melting point data in the Tables of Unknowns. If you are wrong. presented in order of increasing boiling/melting point will appear. If you are correct. one can identify the unknown.
. first re-check your of the unknown. If it is still incorrect.