CHM 112 Lab Procedure 3

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ALCOHOLS, ALDEHYDES, AND KETONES

Objectives: (a) to use different chemical tests to differentiate the alcohol, aldehyde, and ketone functional groups. (b) to determine the functional group present in an unknown solution based upon those chemical tests

Introduction:
There are several tests that may be performed to distinguish among the different classes of alcohols, aldehydes, and ketones. All these tests exploit differences in the type and degree of reactivity of each of the functional groups. You will check the reaction characteristics of five different functional groups (primary alcohols, secondary alcohols, tertiary alcohols, aldehydes, and ketones), and an unknown, and, based upon reaction characteristics, determine the functional group of the unknown. The first step is to identify the structure of each of the functional groups. • Primary alcohols (1° alcohol) have the group –CH2OH, where the carbon atom with the alcoholic hydroxyl group has at least two additional hydrogens attached to that carbon. The alcoholic hydroxyl group is attached to a primary carbon. Think of a primary alcohol (1°) as one where the carbon with the hydroxyl group is attached to one R group (R stands for any other organic chain or group).

H
R C OH

H
• Secondary alcohols (2° alcohol) have the group –CHOH, where the carbon atom with the alcoholic hydroxyl group has only one additional H atom attached to it. There are two R groups (R stands for any other organic chain or group), and the alcoholic hydroxyl group is attached to a secondary carbon. So, a secondary alcohol (2°) is one where the carbon atom with the hydroxyl group is also attached to two R groups.

H
R C R OH

REV 02/05

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In the case of an aldehyde. there are several chemical tests that are used to distinguish these functional groups.) Now that the structures have been identified. In the case of ketones. O C Carbonyl group The difference between aldehydes and ketones is in the groups attached to the carbonyl carbon atom. you might want to think of the word “aldeHyde. there is always at least one H atom attached to the carbonyl carbon atom. An aldehyde has one R group attached. Potassium permanganate (KMnO4) or potassium dichromate (K2Cr2O7) or even atmospheric oxygen (O2) are oxidizing REV 02/05 2 . there are no H atoms attached to the carbonyl carbon.” It has an “H” in the name and an H atom attached to the carbonyl carbon atom. The ketone has two R groups attached. R R C R OH • Aldehydes and Ketones are characterized by a functional group called a carbonyl group – a carbon atom double-bonded to an oxygen atom. So. where the carbon atom with the alcoholic hydroxyl group has no additional H atoms attached to it. A. There are three R groups (R stands for any other organic chain or group). and the alcoholic hydroxyl group is attached to a tertiary carbon. Differences in oxidation: Several different oxidizing agents may be used to cause the oxidation of molecules. O C O C H R R Ketone R Aldehyde (To keep this straight. a tertiary alcohol (3°) is one where the carbon atom with the hydroxyl group is also attached to three R groups. Ketone is the one without an “H” in the name and without an H atom in the carbonyl structure.• Tertiary alcohols (3° alcohol) have the group –COH.

The symbol [O] is commonly used to mean any oxidizing agent. R R C R Tertiary alcohol OH [O] NR (no reaction) d. These two oxidation steps make sense because the primary alcohol functional group has two C-H bonds that can be broken. reduction is the opposite and is a reaction that decreases the number of C-O bonds and/or increases the number of C-H bonds. REV 02/05 3 . first to an aldehyde. One way to look at oxidation is that oxidation is the reaction that increases the number of C-O bonds and/or decreases the number of C-H bonds.agents. it is clear that aldehydes will oxidize to carboxylic acids. a. Therefore. any aldehyde can be oxidized to a carboxylic acid. R R C OH [O] R O C R Ketone H Secondary alcohol c. A primary alcohol oxidizes readily. The aldehyde produced by the oxidation of a primary alcohol can be again oxidized to the carboxylic acid. not its identity that is important here. then to a carboxylic acid. to a ketone. A tertiary alcohol has no C-H bonds that can be broken. no matter how strong the oxidizing agent may be. A secondary alcohol only has only one C-H bond that can be broken. An aldehyde has one C-H bond that can be broken. Think back to what happens to 1° alcohols. and therefore. It’s the action of the oxidizing agent. From this information on alcohols. so it can only oxidize once. so it is NOT oxidized. O H O [O] [O] C R C OH C H R R OH H Primary alcohol Aldehyde Carboxylic acid b.

2°. ZnCl2 C OH + HCl C Cl Clear solution Cloudy from the insoluble chloride Surprisingly enough. and 3°). so ketones cannot be oxidized. just like the product of the oxidation of a 2° alcohol. where a Cl from HCl (mixed with ZnCl2) replaces the hydroxyl group on the alcohol. the solution will turn blue-green. by the speed with which they react. they would both give a negative Lucas test. 3° alcohols react very fast with the Lucas reagent (HCl mixed with ZnCl2). It should be noted that. has no C-H bonds that can be broken.O O C R [O] H C R OH Aldehyde Carboxylic acid e. REV 02/05 4 . but more slowly and must be heated in a water bath in order to react and turn cloudy. and will turn cloudy almost immediately. but if any oxidation takes place. The starting solution of potassium dichromate is yellow-orange. B. O C R Ketone R [O] NR (no reaction) This lab experiment will use a solution of potassium dichromate (K2Cr2O7) as the oxidizing agent. because aldehydes and ketones do not have a hydroxyl group to replace with Cl. Secondary alcohols do react. The Lucas test for alcohols: This test distinguishes among the three types of alcohols (1°. A yellow or yellow-orange color without any precipitate is a negative result. The reaction is a replacement reaction. This color change is due to the Cr+6 ion (orange in K2Cr2O7) being reduced to the Cr+3 ion (blue green). Any ketone. Primary alcohols react so slowly (even in a warm water bath) that NO REACTION is observable.

only aldehydes will give a positive result. It is based upon the ability of the aldehyde group to reduce the Cu+2 ion of Cu(OH)2 (which is blue) to the Cu+1 ion of Cu2O (which is dark red) in the presence of a base. forming no precipitate. the solution will remain translucent yellow. ketones) + 2Cu(OH) 2 + NaOH NR -. Any alcohol or ketone will give a negative result. to distinguish the carbonyl compounds (aldehydes and ketones) from the non-carbonyl compounds (the alcohols).C.4-dinitrophenylhydrazine O2N H2N HN NO2 + C OH No Reaction -.4-Dinitrophenylhydrazine test: This test uses an organic reactant.4-dinitrophenylhydrazine Any alcohol D.NR clear solution 2. 2. O C R + 2Cu(OH)2 + NaOH O C R O+ Cu 2O + 3H 2O Na+ H Aldehyde Carboxylate ion Any other group (alcohols. The 2.4dinitrophenylhydrazine reagent is a translucent yellow solution.4dinitrophenylhydrazine. In the presence of an alcohol. Fehling’s test: This test is very specific for aldehydes. but in the presence of a carbonyl compound.No reaction REV 02/05 5 . a yellow-colored precipitate will form. O2N O2N O NO2 + C Carbonyl group Cloudy from the insoluble product H2N HN C N HN NO2 + H2O 2. 2.

slow Tertiary alcohol-fast Aldehydes. Except for testing the assigned unknown solution (which you must do individually). Wash tubes out with soap and water. Procedure: Use clean test tubes for all these tests – wash them out between tests so that cross-contamination does not occur. you deduce which functional group (not which compound) is in the unknown. a ketone. 3° alcohol Primary alcohol. DO NOT HEAT STOPPERED TUBES -. This paragraph should discuss the tests performed. REV 02/05 6 . and fill the results in on the tables provided on the Report Sheet. As part of the report. rinsing out tubes with acetone will contaminate the tubes and invalidate results. the results of each test.REMOVE STOPPERS BEFORE HEATING! DO NOT rinse out tubes with acetone! Since acetone is a known solution in this procedure. write a paragraph explaining the reasoning used to identify the functional group present in the unknown.4dinitrophenylhydrazine test (aldeydes. using deionized water as a final rinse.4dinitrophenylhydrazine No solid formed Cu(OH)2 and OH- Blue to something else (red. allowing identification the functional group in the unknown. There are also four questions at the end of the report to be answered. and how the results confirmed or ruled out certain functional groups. Ketones Groups that give negative result Ketones. blue or blue/green Clear to cloudy Form yellow/ orange solid Negative result (seen) Remains orange Remains clear Groups that give positive result 1° and 2° alcohols. a secondary alcohol. ketones All alcohols Potassium dichromate Oxidation Lucas test (to distinguish alcohols) 2. Tubes do not need to be dry for these procedures. Aldehydes. you may work in pairs for this experiment unless directed otherwise by your instructor. a tertiary alcohol and the assigned unknown). Based on the results of the tests with the known solutions and the unknown.Here is a summary table of all the reactions: Reaction Chemical Positive result (seen) Orange to green. green yellow) Remains blue Aldehydes Ketones All alcohols Experimental Procedure: You will perform each test indicated on 6 solutions (an aldehyde. ketones from alcohols) Fehling’s Test (aldehydes from ketones) K2Cr2O7 ZnCl2 and HCl 2. aldehydes Secondary alcohol. a primary alcohol.

Slowly (a few drops at a time with mixing) add 2 mL of the solution to be tested. Observe the results. and temperature at which the reaction occurred. A yellow or yellow-orange color without any precipitate is a negative result. use the bottle marked “95% ethanol” as the solvent in the 2. fill a 600-mL beaker slightly less than halfway with tap water to begin heating for the water baths needed on two parts of the procedure Remember the definition of “precipitate”: it isn’t just particulate or “clumpy” particles. A. This procedure must be performed for each of the 5 known solutions and the unknown. if no color change takes place. Lucas test: Place 10 drops of the solution to be tested into a labeled test tube. cloudiness after 5 minutes at room temperature (slightly delayed positive reaction). warm the unstoppered test tube in a 60-75 °C water bath for 15 minutes. C. Chromium is very toxic. Allow mixture to stand at room temperature and observe how long it takes for any precipitate (cloudiness) to form. cloudiness after 3 minutes in 60° C water bath (delayed positive reaction). Observe the results. Stopper with a cork and shake vigorously for a few seconds. then oxidation has taken place (the Cr+6 ion has been reduced to the Cr+3 ion) and the reaction is positive. If no cloudiness is observed after 15 minutes. Sample results might include: immediate cloudiness (immediate positive reaction).Before starting the procedure.4-dinitrophenylhydrazine test: Place 5 drops of the solution to be tested into a labeled test tube. and the results recorded in your notebook for the Report Sheet. and the results recorded in your notebook for the Report Sheet. and should NEVER go down the sink! B. A positive result is the formation of a yellow/orange precipitate. Then rinse out beaker with water (tap water is acceptable) and add this to the waste bottle. then the reaction is negative. be sure to place the chromium waste into the proper waste bottle. including the amount of time taken for the reaction to occur. Add approximately 30 drops of Lucas reagent. carefully swirl until it dissolves). When you have completed these tests. and the persistence of the translucent REV 02/05 7 .4 dinitrophenylhydrazine reagent to the tube and mix. This procedure must be performed for each of the 5 known solutions and the unknown. Record the results. Carefully add 1 mL (about 20 drops) of concentrated sulfuric acid (if a precipitate appears at this point. 2. If the color of the solution changes to green or blue-green. a change in the cloudiness (becoming more cloudy) is also indicative of a precipitate – the cloudiness represents very fine particles that do not settle out! Use the bottle marked “ethanol” as a known primary alcohol solution. Add 10 drops of 95% ethanol (as a solvent) and then add 5 drops of the 2. no cloudiness after 15 minutes in 60°C water bath (negative reaction). A negative test result is the absence of a precipitate.4dinitrophenylhydrazine test (given in the directions for that test). Oxidation by K2Cr2O7: Place 3 mL (about 60 drops) of 5% aqueous K2Cr2O7 in a 50 mL beaker.

Fehling’s test: Place 15 drops of Fehling’s reagent (Part A) and 15 drops of Fehling’s reagent (Part B) into a labeled test tube and mix. REV 02/05 8 . Observe the results. and the persistence of the blue solution. put it in your notebook and fill in results there. Add 10 drops of the solution to be tested. Remove the stopper and place the tubes in a boiling water bath for five minutes. be sure to place the 2. This procedure must be performed for each of the 5 known solutions and the unknown. If no patterns match. and should NEVER go down the sink! D. To figure out your unknown you may construct a table (like this one) in your notebook to help keep track of results filling by “positive” or “negative” depending upon your results in lab. stopper the tube and shake for a few seconds. and the results recorded in your notebook for the Report Sheet. either with one of the known solutions or the unknown solution in one of the tests. When you have completed these tests. Your instructor can help you determine which tests to repeat. You can determine the error and repeat the erroneous tests. A positive result is the formation of a brick red precipitate. 2. 2. an error in testing/reporting was made. and the results recorded in your notebook for the Report Sheet. Then rinse out tubes with water (tap water is acceptable) and add this to the waste bottle.solution.4dinitrophenylhydrazine waste into the proper waste bottle. If you use a table like this.4-dinitrophenylhydrazine is very toxic. A negative result is the absence of a precipitate. This procedure must be performed for each of the 5 known solutions and the unknown.4Test: Chromate Lucas test: Fehling’s test oxidation dinitrophenylhydrazine 1° alcohol (ethanol) 2° alcohol (2propanol) 3° alcohol (2-methyl2-propanol) Aldehyde (formaldehyde) Ketone (acetone) Your unknown: The pattern of positive and negative results for your unknown should match the pattern for one of the known solutions to identify the functional group of your unknown. Don’t fill out this sheet and NOT put this information in your notebook.

Draw structures of these molecules which illustrate the FIVE known functional groups tested here (draw the structure above the name). The unknown assigned to you is number________________ (A) ethanol (1º alcohol) (B) 2-propanol (2º alcohol) (C) 2-methyl-2-propanol (3º alcohol) (D) formaldehyde (aldehyde) (E) acetone (ketone) Test #1: Oxidation by K2Cr2O7 Observation of test results Conclusion (is test positive or negative?) (Did the color or odor change? Did the solution become cloudy or clear? How fast did any changes occur?) Solution tested: ethanol 2-propanol 2-methyl-2-propanol formaldehyde acetone assigned unknown Rev 02/05 9 . this report sheet is for your final report only. AND KETONES You will be testing six solutions (five with known functional groups and one will be an unknown functional group) with each of the four tests. Record all experimental data in your notebook.Lab partner(s) ________________________ Date ______________________ Notebook points/initials __________ Name ___________________________ REPORT FOR LAB PROCEDURE 3: ALCOHOLS. ALDEHYDES.

Test #2: Lucas test Observation of test results (Did the color or odor change? Did the solution become cloudy or clear? How fast did any changes occur?) Conclusion (is test positive or negative?) Solution tested: ethanol 2-propanol 2-methyl-2-propanol formaldehyde acetone assigned unknown Test #3: 2.4-Dinitrophenylhydrazaine test Observation of test results (Did the color or odor change? Did the solution become cloudy or clear? How fast did any changes occur?) Conclusion (is test positive or negative?) Solution tested: ethanol 2-propanol 2-methyl-2-propanol formaldehyde acetone assigned unknown REV 02/05 10 .

the results.Test #4: Fehling’s test Observation of test results (Did the color or odor change? Did the solution become cloudy or clear? How fast did any changes occur?) Conclusion (is test positive or negative?) Solution tested: ethanol 2-propanol 2-methyl-2-propanol formaldehyde acetone assigned unknown The functional group of your unknown is:__________________ Write a paragraph explaining how you arrived at the conclusion concerning the functional group of the unknown. REV 02/05 11 . and how the results confirmed or ruled out certain functional groups. so that you could conclude the type of functional group in the unknown. This should include what tests you performed.

or tertiary alcohol? Write out the structures of 2-methyl-2-propanol and also any oxidation products of 2-methyl-2propanol. give the structure of each of the products. 2. Is ethanol a primary. secondary. or tertiary alcohol? Write out the structures of 2-propanol and also any oxidation products of 2-propanol. If there is more than one oxidation product. If there is more than one oxidation product. Is 2-propanol a primary. 3. give the structure of each of the products. secondary.Answer the following questions: 1. 2-Propanol is the IUPAC systematic name of this alcohol. give the structure of each of the products. If there is more than one oxidation product. 4. Give that common name. It has a common name by which it is much better known (You’ll see it in the grocery store or pharmacy). REV 02/05 12 . or tertiary alcohol? Write out the structures of ethanol and also any oxidation products of ethanol. secondary. Is 2-methyl-2-propanol a primary.

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