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HEJ1, Group # 9, Mr. Jason Vedad Date Submitted: March 1, 2012
I. Abstract Qualitative analyses of test samples of alcohols and phenols, aldehydes and ketones, amines, and carboxylic acid and its derivatives were done. Sodium metal test, Lucas test, and potassium test were used for the identification and differentiation of alcohols. Ferric chloride test, bromine water test, and Millon’s Test were used for the analyses of phenols. Eight tests, namely 2,4-DNPH test, Bisulfite test, Schiff’s test, Tollen’s test, Iodoform test, Fehling’s test, Molisch Test, and Benedict’s Test were used to identify and differentiate aldehydes and ketones. Aldehydes are more reactive to tests than ketones. The presence and differentiation of amines were tested using Hinsberg test where 1°, 2°, and 3° amines reacted differently, allowing for its differentiation. The formation of esters, hydrolysis of the acid derivatives: benzamide, ester, and anhydride were observed and hydroxamic acid test was used for the presence of carboxylic acid and its derivatives. II. Keywords: Qualitative Analysis, Alcohol, Phenol, Ketone, Aldehyde, Amine, Acid Derivatives III. Introduction Chemists must regularly identify compounds that are formed in reactions or found in natural resources. In order to do this, chemists must classify the functional groups present in an unknown compound for successful identification of its identity and its properties. The most commonly used methods for qualitative analyses of organic substances are chemical and spectroscopic methods. In this experiment, the focus is on the use of chemical methods in identifying and differentiating various organic compounds. Different tests with different specific reactions to different functional groups are used to successfully identify the compound being analyzed. The typical indicators for positive test results are a change in the color of solution and the formation of precipitates. Tests are also used to differentiate types of compounds containing the same functional group based on the rate of the reaction and formation and dissolution of precipitates. IV. Experimental E. Tests for Alcohols and Phenols 1. Reaction of Alcohols 1.1 Reaction with Sodium Metal Twenty drops of n-butyl alcohol were placed in a 5mL test tube. A piece of sodium metal was carefully added. The evolution of bubbles was observed. The test was repeated with sec-butyl alcohol and tertbutyl alcohol. The relative rates of bubble formation were compared. 1.2 Lucas Test Twenty drops of Lucas reagent and 10 drops were placed in a 5-mL test tube. The test tube was Chemistry 31.1, Qualitative Analysis 2.2 Bromine Water Test Twenty drops of 95% ethanol and 5 drops of liquid phenol were placed in a 5-mL test tube. Bromine water was added dropwise while being shaken until the color of bromine persisted. Observations were recorded. The procedure was repeated for αnaphthol, catechol, and resorcinol. 2.3 Millon’s Test Five drops each of Millon’s reagent and phenol were placed in a 5-mL test tube. The test tube was shaken and heated in a water bath for 2 minutes. Observations were recorded. The procedure was repeated for α-naphthol, catechol, and resorcinol. F. Tests of Aldehydes and Ketones Page 1 of 13 shaken vigorously and covered with a stopper. The formation of an insoluble layer was observed and timed. The procedure was repeated using sec-butyl alcohol and tert-butyl alcohol. The relative rates of layer formation were compared. 1.3 Reactions with Potassium Dichromate Twenty drops of n-butyl alcohol were placed in a 5mL test tube. The solution was acidified with 2M H2SO4. Five drops of 3% K2Cr2O7 solution was added. Observations were recorded. The procedure was repeated for sec-butyl alcohol and tert-butyl alcohol. 2. Reactions of Phenol 2.1 Ferric Chloride Test Twenty drops of 95% ethanol and 5 drops of liquid phenol were placed in a 5-mL test tube. Five drops of 3% FeCl3 solution was added and mixed. Observations were recorded. The procedure was repeated for α-naphthol, catechol, and resorcinol.
1. 2,4-DNPH Test Five drops of 2,4-DNPH soluiton and 3 drops of formaldehyde were placed in a 5-mL test tube. The test tube was heated in a water bath for 5 minutes. Observations were recorded. The test was repeated for acetaldehyde, acetone, and benzaldehyde. 2. Bisulfite Test Twenty drops of sodium bisulfite and 5 drops of formaldehyde were placed in a 5-mL test tube. The contents were mixed thoroughly. The test tube was placed in an ice bath. Observations were recorded. The test was repeated for acetaldehyde, acetone, and benzaldehyde. 3. Schiff’s Test Twenty drops of Schiff’s reagent and 5 drops of formaldehyde were placed in a 5-mL test tube. Observations were recorded. The test was repeated for acetaldehyde, acetone, and benzaldehyde. 4. Tollen’s Test Twenty drops of Tollen’s reagent and 5 drops of formaldehyde were placed in a 5-mL test tube. The test tube was heated in a water bath. Observations were recorded. The test was repeated for acetaldehyde, acetone, and benzaldehyde. 5. Iodoform Test Twenty drops of 10% NaOH and 5 drops of formaldehyde were placed in a 5-mL test tube. KI/I2 solution was added dropwise, while being mixed until the brown color of I2 persisted. The test tube was heated in a water bath at 60°C for 2 minutes. Ten percent NaOH solution was added dropwise with mixing until the brown color of I2 disappeared and a yellow color persisted. Five drops of distilled water were added. The test tube was shaken vigorously. The test tube was allowed to stand for 15 minutes. Observations were recorded. The test was repeated for acetaldehyde, acetone, and benzaldehyde. 6. Fehling’s Test Twenty drops of Fehling’s reagent and 5 drops of formaldehyde were placed in a 5-mL test tube. The test tube was heated in a water bath. Observations were recorded. The test was repeated for acetaldehyde, acetone, and benzaldehyde. 7. Molisch Test Twenty drops of Molisch reagent and 5 drops of a% glucose were placed in a 5-mL test tube. The test tube was inclined. Two mL of concentrated H2SO4 was run down through the sides of the test tube. The test tube was carefully brought to an upright position. The formation of a blue-violet ring was Chemistry 31.1, Qualitative Analysis
observed. The test was repeated using 1% maltose, 1% sucrose, and 1% boiled starch. 8. Benedict’s Test Twenty drops of Benedict’s reagent and 5 drops of 1% glucose were placed in a 5-mL test tube. The test tube was heated in a water bath. Changes were observed for. The test was repeated using 1% maltose, 1% sucrose, and 1% boiled starch. G. Test for Amines Hinsberg Test Twenty drops of 10% NaOH, 5 drops of methylamine, and 5 drops of benzenesulfonyl chloride were placed in a 5-mL test tube. The test tube was covered with a stopper and shaken for 5 minutes. The solution was tested using litmus to see if it was basic. Ten percent NaOH was added dropwise until the solution was basic to litmus. If a precipitate was observed to form, 40 drops of water was added. The solution was shaken. Observations were recorded. To the result in the previous step, 3M HCl was added dropwise while the solution was being mixed. The procedure was repeated using dimethylamine, trimethylamine, aniline, and nmethylaniline. H. Test for Carboxylic Acid and its Derivatives 1. Formation of Esters Reaction of Carboxylic Acid and Alcohol A pinch of salicylic acid and 20 drops of methanol were mixed in a 10-mL test tube. Five drops of concentrated H2SO4 was added. The mixture was shaken and heated in a water bath for 5 minutes. Observations were recorded. 2. Hydrolysis of Acid Derivatives 2.1 Hydrolysis of Benzamide A pinch of benzamide and 20 drops of 10% NaOH were placed in a 5-mL test tube. A piece of moist red litmus paper was held, using a stirring rod, above the mouth of the test tube while the latter was being heated to boiling in a water bath. Changes in the color of the litmus paper and in the odor of the mixture were noted. 2.2 Hydrolysis of an Ester Twenty drops of ethylacetate were placed in a 5-mL test tube. Five drops of 25% NaOH solution were aadded. The test tube was loosely covered with a stopper and heated in a water bath for 15 minutes. A 1M solution of HCl was added dropwise until the solution was neutral to litmus. Changes in the odor of the mixture were noted.
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2.3 Hydrolysis of an Anhydride Twenty drops of water and a piece each of red and blue litmus papers were added to a 5-mL test tube. Twenty drops of acetic anhydride were carefully added. The tube was gently shaken and felt. Observations were recorded. 3. Hydroxamic Acid Test for Acid Derivatives Five drops of ethylacetate and 20 drops of 7% methanolic hydroxylamine hydrochloride solution were added to a 5-mL test tube. The acidity/basicity of the solution was tested using red litmus paper. Ten percent methanolic KOH was added until red litmus paper turned blue, then ten more drops was added. The solution was heated to boiling in a water bath and was allowed to slightly cool. Ten drops of 3% FeCl3 was added. Observations were recorded. The procedure was repeated for benzamide, acetic anhydride, and benzoylchloride. V. Results
Single layer: asparagus green→darkBG Single layer: golden brown
2. Reaction of Phenols
Table 4: Ferric Chloride Test
Catechol Resorcinol α-napthol
Visible Result Dark brown; no ppt; separates into lighter above, darker below Dark blue w/ no ppt Olive green w/ dark layer at bottom Purplish black w/ powders (darker)
E. Tests for Alcohols and Phenols 1. Reaction of Alcohols
Table 1: Reaction with Na metal
Bromine water test was not conducted due to lack of reagents. But this is the theoretical result:
Table 5: Bromine Water Test
Sample n-butylalcohol sec-butylalcohol tert-butylalcohol
Visible Result Evolution of gas Evolution of gas Evolution of gas
Formula H2 H2 H2
Sample Phenol Catechol Resorcinol
Visible Result Light Brown Dark solution
Formula 2,4,6tribromophenol Bromination of benzene Ring Tribromoresorcinol 2,4-dibromo-1naphthol
Rate of evolution of gas: n-butyalcohol>sec-butyalcohol >tert-butyalcohol
Table 2: Lucas Test
Sample n-butylalcohol sec-butylalcohol
Visible Result No change Formation of layers Clear to light blue
CH3CHClCH2CH3 + H2O (CH3)3CCl + H2O
Yellow with ppt Dak cloudy solution
Table 6: Millon’s Test
Sample Phenol Catechol
Rate of formation of insoluble layer: tert-butyalcohol>sec-butyalcohol >n-butyalcohol
Table 3: Reaction with Potassium Dichromate
Visible Result More viscous than α-napthol; dark brown Black Prior to melting: brownish yellow w/ small suspended particles; after heating: brownish orange w/ more
Formula Hg complex with Phenols Hg complex with Phenols Hg complex with Phenols
Visible Result Ring: brown→ green→darkBG; nd 2 layer: dark yellow→green →clear; Bottom: orange→dark green→darkBG
Chemistry 31.1, Qualitative Analysis
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suspended particles Viscous brown; smells like burned plastic
Hg complex with Phenols
Acetaldehyde Acetone Benzaldehyde Sample
Yellow ppt Yellow ppt No change Visible Result Turned orange w/ dark brown ppt at bottom Brick-red ppt No change Translucent yellow green →cloudy orange layer Fehling’s: royal blue→brown
CHI3 CHI3 n/a Formula Cu2O Cu2O n/a Cu2O
Table 12: Fehling’s Test
F. Tests of Aldehydes and Ketones Formaldehyde
Table 7: 2,4-DNPH Test
Sample Formaldehyd e Acetaldehyde
Visible Result Yellow ppt
Formula 2,4dinitrophenylhydra zone 2,4dinitrophenylhydra zone (theoretical) 2,4dinitrophenylhydra zone 2,4dinitrophenylhydra zone
Orange, brown (when heated) Yellow color; ppt did not dissolved Orange color; 2 layers; ppt dissolved Visible Result Ppt formation Ppt formation No ppt Ppt formation Visible Result Turned dark violet Red-purple purple
Table 13: Molisch Test
Visible Result (+) violet ring (++) violet ring (+++) violet ring
Table 8: Bisulfite Test
Sample Formaldehyde Acetaldehyde Acetone Benzaldehyde
Table 9: Schiff’s Test
Formula H2CH(OH)SO3 + Na + H3C(OH) SO3 Na H3CC(OH)SO3 + Na (C6H6)CH(OH)SO3 + Na Formula
Sample Formaldehyd e Acetaldehyde Benzaldehyde Acetone Sample Formaldehyde Acetaldehyde Acetone Benzaldehyde Sample Formaldehyde
Table 14: Benedict’s Test
Sample Formaldehyde Acetaldehyde Acetone
n/a Formula Ag Ag n/a Ag Formula n/a
Visible Result (++) brick red layer (+++) brick red layer (+) brick red layer (-) no change
Formula Cu2O Cu2O Cu2O n/a
Table 10: Tollen’s Test
G. Tests for Amines
Table 15: Hinsberg Test
Visible Result Silver mirror Silver mirror clear Silver mirror Visible Result No change
Sample Methylamine Dimethylamine Trimethylamine Aniline
Visible Result ppt in acid ppt in base/acid ppt in base ppt in base/acid
Formula C6H5SO2NRH C6H5SO2NR2 R3NHCl C6H5SO2NRH
Table 11: Iodoform Test
Chemistry 31.1, Qualitative Analysis
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ppt in acid
H. Test for Carboxylic Acid and its Derivatives 1. Formation of Esters
Table 16: Reaction of Carboxylic Acid and Alcohol
determination factor. It has been observed that based on the rate of bubble formation, it would be possible to differentiate between primary, secondary and tertiary alcohols. Based on the experiment, it can be inferred that the more acidic an alcohol is, the faster the rate of bubble formation. Thus, n-butyalcohol>sec-butyalcohol >tert-butyalcohol. Lucas test: This test is also used to distinguish among primary, secondary, and tertiary alcohols. The reagent used is a mixture of concentrated Hydrochloric Acid (HCl) and Zinc Chloride (ZnCl2), which on reaction with OHs converts them to the corresponding alkyl chlorides. Rather than focusing on the rate of bubble formation, this test focuses mainly on the speed in which an insoluble layer is formed. A positive test depends on the fact that the alcohol is soluble in the reagent, whereas the alkyl chloride is not; thus the formation of a second layer or an emulsion constitutes a positive test. But the solubility of the alcohol in the reagent limits the test in a general to monofunctional alcohols lower than hexyl and certain polyfunctional molecules. Alcohols, depending on their structure, forms varied carbocations or species containing a positively charged carbon. It is expected for an alcohol with a 30 carbocation to form an alkyl halide the fastest because it is the most stable. Halogenation is the process which takes place when alcohols react with the Lucas solution or ZnCl2 solution in concentrated HCl. When the alcohols react, the H+ from HCl will protonate the – OH group of the alcohol. Water will then leave since it is a weaker nucleophile than OH. When water leaves, the nucleophile Cl- will be substituted for it.
Sample Salicylic Acid
Visible Result Mixed upon heating; cloudy
2. Hydrolysis of Benzamide
Table 17: Hydrolysis of Benzamide
Visible Result Smells like ammonia Visible Result Strong sour odor
Table 18: Hydrolysis of Ester
Table 19: Hydrolysis of Anhydride
Sample Acetic Anhydride
Visible Result Blue litmus to red; sour odor
3. Hydroxamic Acid Test
Table 20: Hydroxamic Acid Test
Sample Ethylacetate Benzamide Acetic Anhydride Benzoylchloride
Visible Result Wine-red Betadinecolored red Blood-red Blood-red
Formula Hydroxamate complexes Hydroxamate complexes Hydroxamate complexes Hydroxamate complexes
VI. Discussion E. Tests for Alcohols and Phenols 1. Reaction of Alcohols Reaction with Na metal: The reaction of an alcohol with sodium metal is similar as to sodium metal’s reaction with water given by the equation: which produces hydrogen gas and sodium hydroxide. In this reaction, the acidity of the alcohol is a primary Chemistry 31.1, Qualitative Analysis
This type of unimolecular nucleophilic substitution is called SN1. The reaction rate is much faster when the carbocation intermediate is more stabilized by a greater number of electron-donating alkyl group bonded to the positive carbon atom. This means that the greater the alkyl groups present in a compound, the faster its reaction would be with the Lucas solution. Thus primary alcohols do not react appreciably with HCl even in the presence of ZnCl2 at ordinary temperatures; the primary carbonium ion is too unstable to serve as an intermediate in the
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carbonium ion mechanism. However, the high reactivity of tertiary alcohols (wherein the alkyl halide is visible within a few minutes at room temperature) is a consequence of the relatively great stability of the intermediate carbonium ion. Theoretically, sec-butyl alcohol would react in about 5 minutes while primary alcohols do not appreciably react with the Lucas reagent at room temperature. Reaction with Potassium Dichromate:
excess of the oxidizing agent. Again by using ethanol to form ethanoic acid: Secondary alcohols, on the other hand, only get oxidized as far as being a ketone. No matter what the reaction conditions are, ketones are the endpoint for the oxidation of secondary alcohols. To illustrate:
Another test to differentiate primary, secondary and tertiary alcohols would be to use their reactive selectivity as a basis. This test is the reaction with potassium dichromate. Scientists consider this as the most reliable since it could allow accurate differentiation of the alcohols. Potassium dichromate requires an alcohol to have a H+ attached to the hydroxide group to be able to oxidize it. Since tertiary alcohols do not have this H+ atom, they do not react with the dichromate ion. The primary and secondary alcohols would be the only one to react with the potassium dichromate and that they can also be differentiated as they would produce different products during oxidation. Primary alcohols are generally the most reactive with potassium dichromate. When they first become oxidized, they become aldehydes. On the second oxidation, the aldehydes become carboxylic acids. Basically, primary alcohols are oxidized into both aldehydes and carboxylic acids depending on the reaction conditions. Primary alcohols become oxidized into aldehydes when there is an excess amount of the alcohol. What happens is that there is a lack of oxidizing agent to fully convert the alcohol. To understand the phenomenon, the electron half equation is:
The O between the carbon and hydrogen in the aldehyde group to form a carboxylic acid was present. Now, the hydrogen is nowhere signifying that the reaction ends there. Tertiary alcohols are generally unreactive with potassium dichromate. This is because the oxidizing agent has nothing to remove. In primary alcohols, the agent can remove the hydrogen from the –OH group. In secondary alcohols, the agent removes a hydrogen from the carbon atom attached to the –OH. Tertiary alcohols don’t have such. Illustrating this:
2. Reactions of Phenols Ferric Chloride Test: Most phenols create a reaction with iron (III) chloride to form a colored complex. The colors vary, depending not only on the nature of the phenol but also on the solvent, concentration, and time of observation. Some phenols that do not give coloration in aqueous or alcoholic solution do so in chloroform solution, especially after addition of a drop of pyridine.
The alcohol used is ethanol and when this equation is further simplified which shows O as the oxidizing agent to form ethanal:
The second illustration is the more visual approach towards understanding the full reaction in the formation of an aldehyde. As was said, a primary alcohol can also be further oxidized into a carboxylic acid. This happens when there is an
The nature of the colored complexes is still uncertain; they may be ferric phenoxide salts that absorb visible light to give an excited state in which electrons are delocalized over both the iron atoms and the conjugated organic system. The production of a color is typical of phenols; however, many of Page 6 of 13
Chemistry 31.1, Qualitative Analysis
them do not give colors, so a negative feric chloride test must not be taken as significant without supporting information. Bromine Water Test: With the same aim as the ferric chloride test, the bromine water test detects the presence of phenol and phenolic groups. The attached OH groups on the benzene ring are more receptive to electrophilic reagents as they can accommodate them. Therefore, as a phenol is mixed with bromine, it would undergo bromination. To check if the test for the presence of phenol is positive, bromine would decolorize and that the mixture would yield precipitates. Both alkenes and phenols react with bromine water. In both cases, there will be a significant color change from orange to colorless. There will be a decolorozation of bromine and this would signify that the functional group –OH attached directly to the benzene ring. A susbstitution reaction is expected of the phenol reacting with bromine. The product, 2,4,6tribromophenol, is formed. Such product is called a tribrominated product. The benzene ring in phenol is much more reactive than a normal benzene ring because of the hydroxyl group attached to it:
mercurous ions in nitric and nitrous acids, the visible result would be a white precipitate along with a red solution since there is a formation of mercury salts after heating. F. Tests of Aldehydes and Ketones 2,4 – DNPH Test: The reagent, 2,4dinitrophylhydrazine or 2,4-DNPH, reacts with the carbonyl groups of aldehydes and ketones. The reaction is given:
Reaction of 2,4-DNPH
It is important to note that even if there is a subsequent decolorization of the bromine, the reaction observed would still be a substitution reaction rather than an ordinary addition of a normal alkene. The difference between a phenol’s reaction with that of an alkene is quite observable. Both compounds would yield a decolorization of the bromine water but for phenols, the tribrominated product is formed. This would be quite observable as a white precipitate which forms just after the decolorization itself. In addition, HBr will be generated but will not be observed since the reagent is aqueous. Millon’s Test: The last test for phenols is the Millon’s test. The structure of the reagent is (Hg(NO3))2 in H2O. It has been observed that a positive test has a pink to red colored solution or precipitate. However, this test may have varying experimental results since some phenols such as catechol and resorcinol do not effectively form a compound with a free OH group. To detect the presence of a hydroxyphenyl group (phenolic-OH), this test is then applied. Since Millon’s reagent is made up of mercuric and Chemistry 31.1, Qualitative Analysis
2,4-DNPH detects the presence of aldehydes and ketones by replacing the oxygen atom attached to a carbon atom by a double bond. The formation of yellow-orange-red precipitate indicates a positive result for an aldehyde or ketone. Small, unconjugated aldehydes and ketones form close to yellow precipitates while large, conjugated aldehydes and ketones form close to red precipitates. The formation of an oily layer should also be noted as some ketones (and also enols) form oils that do not solidify or precipitate after the reaction of 2,4-DNPH. The 2,4-DNPH test is considered the simplest test for aldehydes and ketones but it can also lead to misleading results and data. For instance, excess acid catalyst may result to the reaction of the acid with 2,4-DNPH than with the test sample. Using impure alcohols may lead to inaccurate results as this might contain aldehyde or ketone impurities. Thus, other qualitative tests are also employed together with this test. Bisulfite Test Aldehydes and unhindered ketones add bisulfite to form water insoluble addition compounds. An example of the reaction is given by:
Reaction of Bisulfite A more detailed discussion of the characteristic reaction of aldehydes and ketones explains that a base-catalyzed nucleophilic addition occurs across the carbon-oxygen double bond. The carbon atom of the carbonyl group then acquires a partial positive charge as the C=O bond is polarized. The bisulfite ion, HSO3 , is an electron Page 7 of 13
rich and consequently a strong nucleophile. Thus it readily attacks the partially positive carbon atom of the carbonyl group. The oxygen atom is oxidized into a hydroxide ion, OH , by the bisulfite ion which then bonds with carbon to form the water soluble precipitate. Moreover, this test also differentiates aldehydes and ketones through the rate of reaction. Aldehydes are more reactive to ketones in the bisulfite test due to steric and inductive effects present in ketones. As shown in the figure below, the presence of bulky alkyl groups sterically hinders the nucleophile from approaching the carbocation. Moreover, alkyl subsituents which are weak electron donating groups make the carbonyl atom less electrophilic. These factors lead to slow formation of precipitates or the absence of precipitate in ketones.
Tollen’s Test: This test is another test for aldehydes. Tollen’s reagent consists of a silver diamine complex which is responsible for the formation of a ―silver mirror‖ in the presence of an aldehyde. The reaction is given by:
Reaction of Tollen’s Reagent The silver diamine complex is reduced by aldehyde to metallic silver which is observed as the formation of a silver substance similar to a mirror. Tollen’s reagent also reacts with triple bonds and can produce the same results as aldehydes and thus can lead to inaccurate results. Iodoform Test: Iodoform test is a classical test for methyl ketones. However, it can also give positive results for acetaldehyde, ethanol, and other secondary alcohols. Secondary alcohols with an adjacent methyl group can be oxidized by iodine bleach into methyl ketones. The reactions are given by:
Steric Hindrance in Carbonyl Carbon
Electrophilic Character of Carbonyl Carbon Schiff’s Test: Schiff’s test is specifically used for the differentiation of aldehydes and ketones as the rate of reaction of the Schiff’s reagent differs greatly for aldehydes and ketones. Schiff’s reagent, a pink triphenylmethane dye which is converted into a colorless leucosulfonic acid by sulfurus acid, is known as fuschine or p-rosaniline hydrochloride. It reacts mostly with aldehydes by the same reasons stated above for ketones with bulky alkyl groups and substituents with weak electron donating groups. The reaction of Schiff’s reagent with an aldehyde is given by:
Reaction of Iodine
Oxidation of Secondary Alcohols into Methyl Ketones The reagent in an iodoform test contains I2 in KI solution. In basic solution, the hydrogen atoms of the carbon next to the carbonyl group are replaced by iodine to produce tri-iodo-methyl carbonyl compounds, as shown below. In the next firgure, the tri-iodo-methyl compound then reacts with OH to form iodoform and carboxylic acid or salt.
Reaction of Schiff’s Reagent The bisulfite ion present in the reagent produces an sp3 hybridization. The aldehyde reacts similarly in the bisulfite test and is oxidized into an alcohol, displacing the bisulfite and changing the hybridization to sp2. The appearance of a purple color indicates a positive result for the Schiff’s test.
Reaction of Methyl Ketone and Iodine
Reaction of Tri-iodo-methyl and OH Chemistry 31.1, Qualitative Analysis
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The formation of a yellow precipitate with crystal-like appearance indicates a positive result for the iodoform test. Fehling’s Test: Fehling’s test is another test for the presence of aldehydes and is also used for tests for the presence of sugars since sugars, when dehydrated are actually aldehydes (aldoses). A positive result shows the formation of a brick red precipitate which is actually caused by the formation of Cu2O. The reactions involved are given below:
the formation of the precipitate Cu2O. This test allows for the identification of sugars that have the ability to reduce cupric ion to cuprous oxide. The reaction is given below:
Reaction in Benedict’s Test G. Test for Amines Hinsberg Test: Hinsberg test is used to differentiate primary, secondary and tertiary amines and anilines depending on the solubility of the precipitate or oily layer which would form from the reaction. In this test, benzenesulfonyl chloride is used as reagent present as insoluble oil in an aqueous basic solution. Primary amines dissolve in base and precipitates from acidic solutions. Secondary amines precipitate from base and no change is observed in acid. Tertiary amines precipitate from base and dissolves in acid. The reactions are given below:
Reactions in Fehling’s Test This test is very sensitive that even minute amounts of aldehydes or carbohydrates can result to the brick red color of the compound. Molisch Test: The Molisch test is used to test for the presence of carbohydrates. The dehydration of carbohydrates through sulfuric acid produces an aldehyde. The formation of a purple ring indicates a positive result. It is a result of the dehydrated carbohydrate condensing with αnaphthol. The reactions are given by:
Reactions for 1°, 2°, and 3° Amines
Sample Reaction in Molisch Test Thus, it is specifically instructed not to shake the test tube containing the test sample so as not to disturb the purple ring that forms in the presence of an aldehyde or carbohydrate. Benedict’s Test: Benedict’s test is a test employed in the identification of the presence of glucose. Similar to Fehling’s test, a positive result is given by the appearance of brick red color due to Chemistry 31.1, Qualitative Analysis
H. Test for Carboxylic Acid and its Derivatives 1. Formation of Esters Reaction of Carboxylic Acid and Alcohol: An ester is a product of the reaction of an acid (usually organic) and an alcohol (the hydrogen of the acid R-COOH is replaced by an alkyl group R'). Esters mainly result from the condensation (a reaction that produces water) of a carboxylic acid and an alcohol. The process is called esterification. The esterification reaction is both slow and reversible. To have a positive test, the reaction must be subjected to heat (the reaction is said to be endothermic and that an increase in heat causes more collision) and an acid catalyst, H2SO4 in this case, to favor forward reaction. Ester, in big amount, gives off a fruity smell. When salicylic acid combines with methanol it becomes the ester known as methyl salicylate or oil of wintergreen. Methanol is also known as methyl alcohol and wood alcohol. The Page 9 of 13
reaction of salicylic acid C6H4 (OH) CO2H and methanol CH3OH forms this ester.
hydroxide group and elimination of amide ion. When heated with a base (NaOH), ammonia gas is given off.
2. Hydrolysis of Acid Derivatives Hydrolysis reactions are said to be acidcatalyzed or base-catalyzed. In the overall process of hydrolysis, a bond in an organic molecule is broken (for acid derivatives, forming an acyl group), and an O-H bond in a water molecule also breaks. Then, from the water molecule, an O-H group adds to one part from the organic molecule, and an H atom to the other.
In the experiment, the base-catalyzed reaction was performed that yielded to the ammonia odor that was observed. Hydrolysis of an Ester: The hydrolysis of ester in acidic and alkaline conditions is represented below:
Base-catalyzed is a one way reaction while the acid-catalyzed is reversible. The products of the former are easier to separate (sodium salt is formed rather than carboxylic acid itself, to obtain the carboxylic acid, dilute acid must be added after distilling the other product), while that latter’s can’t be separated easily thus harder to test.
Notice that in alkaline conditions, the carboxylate ion is formed. The addition of a strong acid, such as dilute HCl, is required to free the carboxylic acid molecule. In the base-catalyzed hydrolysis above, you could think of the reaction as with water, and the carboxylic acid molecule formed losing a proton to a hydroxide ion. A strong sour odor will be observed due to the formation of acetic acid. Hydrolysis of an Anhydride: Anhydrides are derivatives of carboxylic acids. All derivatives of carboxylic acids can be converted to the corresponding acid through reaction with water. Some less reactive derivatives require a catalyst for the reaction to occur in a reasonable time, but anhydrides do not. In the hydrolysis of an anhydride, water attacks the anhydride in a nucleophilic substitution. The solution obtained from this reaction turns blue litmus to red due to conversion to acid.
Hydrolysis of Benzamide: Benzamide is less reactive than acid chlorides, acid anhydrides, or esters. It undergoes hydrolysis to yield carboxylic acids plus amine on heating in either aqueous acid or aqueous base. In acid-hydrolysis, there is a nucleophilic addition of water to the protonated amide, followed by the loss of ammonia.
On the other hand, in a basic solution, there is a nucleophilic addition of hydroxide to the amide carbonyl group, followed by the deprotonation of the Chemistry 31.1, Qualitative Analysis
3. Hydroxamic Acid test for Acid Derivatives
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Hydroxamic acid is a class of chemical compounds sharing the same functional group in which a hydroxylamine is inserted into a carboxylic acid. In the Hydroxamic Test for acid derivatives, hydroxylamine hydrochloride attacks the acid derivative in a nucleophilic substitution reaction. During the formation of hydroxylamine, KOH is added to consume HCl so the reaction will not proceed backward. During ferric hydroxamate complex formation, the solution is acidified by HCl to prevent the excess base from reacting with FeCl3 (a Lewis Acid). A distinct burgundy or magenta color of the ferric hydroxamate complex is a positive test, a dark brown solution is uncertain while a yellow solution means negative. RCOOH derivatives, esters, acid anhydrides and aryl/acyl halides would give positive results. Primary and secondary nitro compounds, imides, some amides, most nitriles, and aldehydes with no alphahydrogens give a positive test. When an ester, like ethyl acetate, is reacted with hydroxamic acid, it produces an alcohol.
A dry test tube should be used because Na metal is highly reactive with water and may ignite violently due to the H2 gas produced. 3. Why is the Lucas test not used for alchols containing more than eight carbon atoms? The Lucas test applies only to alcohols soluble in Lucas reagent (monofunctional alcohols with less than 6 carbons and some polyfunctional alcohols). Long chains of carbon make the compound nonpolar and the –OH group less functional. This results to the insolubility of the alcohol in the reagent, rendering the test ineffective. 4. Explain why the order of reactivity of the alcohols toward Lucas’s reagent is 3°>2°>1°? The reaction of alcohols with Lucas reagent is a nucleophilic substitution reaction. In an S-n1 reaction, the rate determining step is the carbocation. The carbocation is most stable in a tertiary alcohol and is therefore formed faster than a secondary and a primary carbocation. 5. Illustrate with equations the reactions of the following alcohols with Potassium Dichromate. Proof that dichromate is a strong oxidizing reagent in an acidic sol’n: (ε0 = 1.33 V) (ε0 = −0.13 V) • n-butylalcohol (oxidized to aldehyde/carboxylic acid)
When an acid anhydride, like acetic anhydride, is reacted with hydroxamic acid, it produces a carboxylic acid.
For acyl halide,
• sec-butylalcohol (oxidized to ketone) For amide, • tert-butylalcohol (cannot be oxidized because tertiary alcohols do not have a hydrogen atom attached to a carbon)
VII. Guide Questions & Answers 1. What property of alcohol is demonstrated in the reaction with Na metal? What is the formula of the gas liberated? The alcohol exhibits acidic property in the reaction with Na metal. The hydrogen atom is replaced by Na producing H2 shown in the reaction: 2 R–O–H + 2 Na → 2 R–O( )Na( ) + H2 2. Dry test tube should be used in the reaction between the alcohols and Na metal. Why? Chemistry 31.1, Qualitative Analysis
6. What functional group is responsible for the observed result in Millon’s test? Phenol interacts with nitric acid, nitrated phenol reacts with mercury and mercury salts are formed. This reaction accounts for the observed result in Millon’s test. 7. Why is the Schiff’s test considered a general test for aldehydes? Page 11 of 13
Differentiation of aldehydes from ketones becomes the main purpose of using Schiff’s test since it cannot distinguish one kind of aldehyde from another. 8. Why is it disadvantageous to use a strong acid catalyst in the reaction of aldehyde or ketone with 2,4-DNPH? The use of a strong acid reverses the sequence of the reaction. Instead of the nucleophile attacking the substrate followed by the electrophile, in the presence of a strong acid, the weaker nucleophile attacks the carbon to stabilize the forming hemiacetal. Water abstracts the H+ of the hemiacetal. Hemiacetals are less stable and will form acetals which do not show the visible changes expected of the test.
12. What test will you use to differentiate each of the following pairs? Give also the visible result. a. acetaldehyde and acetone Schiff’s test – reaction with acetaldehyde will result to a purple solution. Acetone on the other hand will not react. Tollen’s test – acetaldehyde will form a silver mirror. Acetone on the other hand will not have any reaction. b. acetaldehyde and benzaldehyde Bisulfite test – will differentiate an aliphatic aldehyde from an aromatic aldehyde. Aldehyde will react faster than benzaldehyde. Both will form a red precipitate due to cuprous oxide. 13. A colorless liquid has a bp of 199-201°C and burns with a smoky flame. The sodium fusion test proved negative for the presence of halogens, nitrogen, and sulfur. It was not soluble in water, 5% aqueous sodium hydroxide, or 5% hydrochloric acid. However, it was dissolved in sulfuric acid with evolution of heat. It did not give a precipitate with 2,4-DNPH solution and did not decolorize brominemethylene chloride solution. The unknown liquid did give a positive hydroxamate test and was found to have a saponification equivalent of 136. Identify the unknown liquid. Smoky flame indicates that the compound is aromatic. It tested negative for 2,4-DNPH, telling us that it is neither an aldehyde nor a ketone. A negative test for bromine in methylene chloride solution also indicates that it is neither an alcohol nor a phenol. A positive test for hydroxamate test tells us that it is an acid derivative, which can undergo saponification—therefore it is an ester. Finally, an aromatic ester with a boiling point range o of 199-201 C is methyl benzoate. VIII. Conclusions & Recommendations There are many tests which can be conducted in order to differentiate organic compounds from one another. Some tests are also able to differentiate primary, secondary and tertiary designated carbon atoms. The functional groups, the number of carbon atoms present, the degree of (un)saturation, the reactivity of the compounds to certain reagents at certain conditions, and the presence of electron-withdrawing or –donating
9. Show the mechanism for the reaction of acetaldehyde with the following reagents: a. 2,4-DNPH
10. What structural feature in a compound is required for a positive iodoform test? Will ethanol give a positive iodoform test? Why or why not? Ketones and alcohols with a methyl group directly adjacent to a carbonyl group or a carbon atom bearing a hydroxyl group react with an alkaline solution of iodine to produce a yellow solid, iodoform. Ethanol will give a positive result because it can be oxidized to an aldehyde with a methyl group attached to a carbonyl group. 11. Show the mechanisms for the iodoform reaction using acetaldehyde as the test sample.
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groups are some of the essential factors which make organic compounds vary from one another.
IX. References Shriner, R., et al. (1956). The systematic identification of organic compounds. New York: John Wiley & Sons, Inc. Fieser, L., & Williamson, K. (1992). Organic experiments. MassachusettsL D.C. Health and Company. Roberts, R., et al. (1985). Modern experimental organic chemistry. New York: CBS College Publishing. Hydrolysis of organic compounds. Retrieved from: http://www.avogadro.co.uk/organic/hydrolys is/hydrolysis.htm Tests for aldehydes and ketones. In Online lab manual home. Retrieved from http://www.wellesley.edu/Chemistry/chem2 11lab/Orgo_Lab_Manual/Appendix/Classifi cationTests/aldehyde_ketone.html#Iodofor m Chemical Tests Page. Retrieved from: http://www.chemistry.ccsu.edu/glagovich/te aching/316/qualanal/tests/tests.html Aldehydes and Ketones. In Chemistry comes alive. Retrieved from:http://www.jce.divched.org/ JCESoft/CCA/CCA5/MAIN/1ORGANIC/OR G12/MENU.HTM Organic chemistry microscale projection experiments. Retrieved from: ://www.demochem.de/proj-e.htm
I hereby certify that I have given substantial contribution to this report. ___________________________ Bacareza, Maxine Nicole ___________________________ Guiñez, Abigail Ann A.
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