KUMASI POLYTECHNIC

CHEMICAL ENGINEERING DEPARTMENT

CHEMICAL ENGINEERING LAB. II ORGANIC CHEMISTRY PRACTICALS (CME 208)

REPORT ON IDENTIFICATION OF ALCOHOLS AND PHENOLS

BY SALIFU MUSAH (CME05061081)

DATE OF EXPERIMENT: 12TH MARCH, 2010 DATE SUBMITTED: 19TH MARCH, 2010

SUPERVISOR: MR. ISAAC FRIMPONG

INTRODUCTION
Specific groups of atoms in an organic molecule can be used in determining its physical and chemical properties. These groups are referred to as functional groups. Organic compounds which contain the functional group ±OH (hydroxyl group) are called alcohols. Alcohols are important commercially and include use as solvents, drugs, and disinfectants. The most widely use alcohols are methanol or methyl alcohol (CH3 OH), ethanol or ethyl alcohol (CH3CH2 OH), and 2-propane or isopropyl alcohol ((CH3)2CHOH). The general formula of an alcohol is ROH in which the R is an aliphatic hydrocarbon group. Alcohols may be looked upon as derivatives of water, HOH. One hydrogen of water is substituted by an alkyl group, R. Like water, alcohols show hydrogen bonding. As the chain of the R group increases the hydrocarbon character of the compound overshadows the polar character of the OH group. Consequently, the solubility and boiling point of an alcohol are affected by the length of the carbon chain and the shape of the molecule. The short chain alcohols are soluble in water, whereas the longer chain alcohols are insoluble in water. In general a molecule which is more compact (i.e., more branched) will be more soluble in water and will have a lower boiling point than the straight chain isomer. The hydroxyl group present in all alcohols is a polar functional group. The polarity of this group allows alcohols to form hydrogen bonds. Small chain alcohols are able to mix with water because
of the hydrogen bonding interactions that will occur between the hydroxyl functional group and the water. If the R-group of the alcohol becomes too large however, the solubility of the alcohol will decrease.

Although alkyl alcohols have an -OH group, they do not ionize in water, whereas phenols ionize like acids (donating a proton to water). The -OH group of alkyl alcohols can be positioned on different carbon atoms of the carbon chain and are classified as primary (1º), secondary (2º), or tertiary (3º) alcohols depending on whether the -OH group is attached to a carbon with 1, 2 or 3 other carbon atoms attached to it.
CH3 CH3 CH3 CH3 CH2 OH CH3 CH OH CH3 C OH

ethanol (primary)

2-propanol (secondary)

2-methyl-2-propanol (tertiary)

1

These different alcohols react differently with Lucas reagent and with Bordwell-Wellman reagent; hence these reagents can be used for identifying the class of alcohol. The relative acidity of phenols can be used to characterize this class of alcohols relative to the alkyl alcohols. Phenols are aromatic alcohols, in which R is an aromatic ring. This experiment will demonstrate some of the properties of alcohols and phenols. Phenols are closely related to alcohols because of the presence of the hydroxyl ( OH) group. In phenols, however, the hydroxyl group is directly bonded to an aromatic group, such as benzene. Phenol compounds often have curious but useful properties. Some are found in preservatives or medications. The chemistry of phenols is different than that of alcohols. Concentrated solutions of the compound phenol are quite toxic and can cause severe burns.

OBJECTIVES 1. To observe the solubility of alcohols relative to their chemical structure. 2. To determine the characteristics chemical reactions of alcohols and phenols of an organic compound. 3. To use chemical characteristics to distinguish primary, secondary and tertiary alcohols and a colour test will be performed for phenol.

2

SOLUBILITY TEST Some liquids, such as water and alcohol, can dissolve in each other in any proportion. The solubility of a compound in a given solvent at a given temperature and pressure thus is defined as the maximum amount of that compound that can be dissolved in the solution. Solubility increases with the increasing temperature of the solvent for most substances. For some substances, such as gases or the organic salts of calcium, solubility in a liquid increases with a lowering of temperature. In general, solutions with molecules that is structurally similar to the molecules of the solvent have the highest solubility. For example, ethyl alcohol (C2 H5 OH) and water (HOH) have structurally similar molecules and are highly soluble in one another. Alcohols are highly soluble in water because the polar OH groups in water and alcohols make the two associate through hydrogen bonding when they are put together. H R O H . . . O H
Hydrogen bonding

FERRIC CHLORIDE TEST The ferric chloride test is a traditional colourimetric test for phenols, which uses a 1% iron (III) chloride solution that has been neutralised with sodium hydroxide until a slight precipitate of FeO (OH) is formed. The mixture is filtered before use. The organic substance is dissolved in water, methanol or ethanol, then the neutralised iron (III) chloride solution is added²a transient or permanent colouration (usually purple, green or blue) indicates the presence of a phenol or enol.

OH + FeCl3

OFeCl2 + HCl

CHROMIC TEST OR BORDWELL-WELLMAN TEST The Bordwell-Wellman test solution contains potassium dichromate dissolved in sulphuric acid. It is an orange-yellow solution. The orange-yellow colour is due to the Cr2O7 ion. The oxidation number of chromium is +6. This reagent will oxidize primary and secondary alcohols and, in turn, becomes reduced. The chromium in dichromate is reduced to chromic ion, Cr3+. A greenish coloured solution results. This colour change from orange-yellow to green serves as an indicator for the presence of a primary or secondary alcohol. A primary alcohol is oxidized first to an aldehyde, which will be further oxidized to an acid.

3

IODOFORM TEST The io o o
 

test is a test fo co C C=O OR H C R

oun s that contain either of the follo in grou s:
 

C

OH

R

This inclu es ethanal an ethanol. If a methyl secon ary alcohol is used it will be oxidised to the methyl ketone before the main part of the process takes place. The compound being tested is reacted with iodine in sodium hydroxide solution or sodium chlorate (I) and potassium iodate solution. A bright yellow precipitate of iodoform indicates a positive test. The reaction starts with the substitution of the hydrogens in the methyl group for iodine atoms. This causes a great withdrawing of electrons from the C C bond joining the methyl group to the ketone group, allowing nucleophillic attack and fission of the bond:

KMnO4 TEST

4

PROCEDURE

APPARATUS AND REAGENTS Test tubes, Bordwell-Wellman reagent, n-butyl alcohol (1-butanol), secondary-butyl alcohol (2propanol), tertiary-butyl alcohol , resorcinol, ferric chloride solution, 6M NaOH, I2-KI reagent, acetone, KMnO4, 250ml beaker, dropper, water bath and test tube holders.

SOLUBILITY TEST 1. 10 drops of each, 1-butanol, 2-propanol, tertbutyl alcohol and resorcinol were placed in a clean dry separate test tube. 2. 3ml of distilled water were added to each solution and shaken. 3. The observations were recorded on a reported sheet.

FERRIC CHLORIDE TEST 1. 5 drops of each, 1-butanol, 2-propanol, tertbutyl alcohol and resorcinol were placed into separate clean dry test tubes. 2. 2 drops of ferric chloride solution was added to each solution. 3. Any colour changes were noted. 4. The observations were recorded.

CHROMIC ACID TEST 1. 3 drops of each, 1-butanol, 2-propanol, tertbutyl alcohol and resorcinol were placed into separate clean dry test tubes. 2. To each test tube 3 drops of acetone and 3 drops of chromic acid were added and warmed in a water bath at a temperature of 60ºC for 5 minutes. 3. After heating the colour changes were observed. 4. The results were recorded.

IODOFORM TEST 1. 5 drops of each, 1-butanol, 2-propanol, and tertbutyl alcohol were placed into separate clean dry test tubes. 2. To each test tube 15 drops of 6M NaOH and drops of I2-KI reagent were added and warmed in a water bath. 3. After heating the colour changes were observed. 4. The results were recorded.

5

KMnO4 TEST 1. 2ml of each, 1-butanol, 2-propanol, and tertbutyl alcohol were placed into separate clean dry test tubes. 2. To each test tube 2ml of KMnO4 were added and shaken. 3. The colour changes were observed. 4. The results were recorded.

6

DATA Table 2.0 SOLUBILITY TEST TEST OBSERVATION INFERENCE 1-butanol is soluble in water.

10 drops of 1-butanol + 3ml The two were miscible. of H2 O. 10 drops of 2-propanol + 3ml The two were miscible. of H2 O. 10 drops of tertbutyl alcohol The two were miscible. + 3ml of H2 O. 10 drops of 1-butanol + 3ml The two were immiscible. of H2 O.

2-propanol water.

is

soluble

in

Tertbutyl alcohol is soluble in water. Resorcinol is insoluble in water.

Table 2.1 FERRIC CHLORIDE TEST TEST OBSERVATION INFERENCE

5 drops of 1-butanol + 2 A light yellow colour was Primary alcohol is present. drops of ferric chloride. formed. Secondary alcohol is present.

5 drops of 2-propanol + 2 A yellow colour was formed. drops of ferric chloride.

5 drops of tertbutyl alcohol + A pale yellow colour was Tertiary alcohol is present. 2 drops of ferric chloride. formed.

5 drops of resorcinol + 2 A dark purple colour was Phenol present. drops of ferric chloride. formed.

7

Table 2.3 CHROMIC ACID TEST TEST OBSERVATION INFERENCE

3 drops of 1-butanol + 3 Orange colour changes to 1-butanol is present. drops of acetone + 3 drops of blue green. chromic acid + warming. 3 drops of 2-propanol + 3 Orange colour changes to 2-propanol is present. drops of acetone + 3 drops of green colour. chromic acid + warming. 3 drops of tertbutyl alcohol + No colour change 3 drops of acetone + 3 drops of chromic acid + warming. 3 drops of resorcinol + 3 Formation of brown tarry Phenol present. drops of acetone + 3 drops of masses. chromic acid + warming. Tertiary alcohol present. Secondary alcohol present. Primary alcohol present.

Table 2.4 IODOFORM TEST TEST OBSERVATION INFERENCE Primary alcohol present.

5 drops of 1-butanol + 15 Cloudiness formed. drops of 6M NaOH + drops of I2-KI reagent + warming.

5 drops of 2-propanol + 15 Two colour formation. A Secondary alcohol present. drops of 6M NaOH + drops pale yellow colour below and of I2-KI reagent + warming. a colourless above. Tertiary alcohol present.

5 drops of tertbutyl alcohol + Colourless colour formed. 15 drops of 6M NaOH + drops of I2 -KI reagent + warming.

8

Table 2.5 KMnO4 TEST OBSERVATION INFERENCE

2ml of 1-butanol + 2 drops of Light brown colour with Primary alcohol is present. KMnO4 + shaking. brown ppt. Formed. Secondary alcohol is present.

2ml of 2-propanol + 2 drops Pale brown colour formed. of KMnO4 + shaking. 2ml of tertbutyl alcohol + 2 No drops of KMnO4 + shaking. reaction.

Colour Tertiary alcohol present.

remained the same.

Table 2.6 OBSERVATIONS TEST Solubility Ferric Chloride Chromic acid Iodoform KMnO4 1-Butanol + + _ + 2-Propanol + + + + Tertbutyl alcohol + + Resorcinol + +

9

RESULTS AND DISCUSSION

FOR 1-BUTANOL The solubility test gave a result of two miscible clear layers indicating that 1-butanol is insoluble. The ferric chloride test gave a light yellow colour indicating presence of a primary alcohol. With the chromic test, there was a colour change from orange to blue-green after warming indicating the presence of primary alcohol. Primary alcohol turns to an aldehyde and then to a carboxylic acid. 3CH3CH2 OH + 4H2CrO4 + 6H2SO4 1º alcohol Orange 3CH3CO2H + 2Cr2 (SO4)3 + 13H2O carboxylic acid blue -green

With the iodoform test, cloudiness was formed with a disinfected smell indicating the presence of a primary alcohol. The KMnO4 test gave a light brown colour formation with brown precipitate indicating the oxidation of primary alcohol to an aldehyde. Further oxidation forms an acid. CH3CH2 OH + KMnO4/H+ Ethanol CH3CHO + Mn2+ CH3COOH Ethanoic acid

FOR 2-PROPANOL The solubility test gave a clear soluble mixture confirming the solubility of the solution. This is due to the strong intermolecular force of attraction. The ferric chloride test gave a light yellow colour indicating presence of a primary alcohol. With the chromic test, there was a colour change from orange to blue-green after warming indicating secondary alcohols are oxidized to a ketone.
OH R CH R +

O

H 2CrO4

R

C

OH +

Cr2 (SO4)3 + H2O (Blue-green)

(Secondary)

(Red-orange)

(Ketone)

Two layers of colour formed, a pale yellow colour below and a colourless colour above indicating no reaction between the two solutions.

10

FOR TERTBUTYL ALCOHOL The two were miscible with the solubility test showing the presence of tertiary alcohol. In the ferric chloride test, a yellow colour was obtained from the reaction. The chromic acid test gave no colour change, indicating no reaction between the two solutions
(CH3)3CHOH + H2CrO4 + H2SO4 3º alcohol Orange NO REACTION

Iodoform test gave a colourless colour showing presence of a tertiary alcohol. The KMnO4 test showed there is no reaction with tertiary alcohol. Colour remained purple.

FOR RESORCINOL The resorcinol is insoluble in water. In the ferric chloride test, a dark purple colour was formed showing the presence of phenol. The chromic acid test gave a green colour formation indicating the presence of a phenol.

SOURCES OF ERROR 1. Not measuring the required volume of solution. 2. Not warming the reagents at the required temperature. 3. Drops of water left beneath the test tubes during cleaning. 4. Used one dropper for two different solutions.

11

PRE-LAB 1. Compound Structure
CH3-CH2-CH2-CH2-OH

1,2 or 3 Alcohol

Molecular weight 74g/mol 60g/mol

Boiling point 117ºC 82.5 ºC

Hazards

1-butanol 2-propanol 2-methyl-2propanol

Primary alcohol Secondary alcohol Tertiary alcohol

Poisonous Poisonous

CH3-C(CH3)-OH

C(CH3)3-OH OH

74g/mol

82.5 ºC

Poisonous

Resorcinol

OH

94g/mol

276.5 ºC

Can cause severe skin burn

2. Alcohols and water have the polar OH groups and it makes them associate free hydrogen bonding when they are put together. The strange interaction that happens when they are put together evolves enough hydration energy which overcomes the intermolecular forces of hydrogen bonding of the alcohols. The hydration energy produced is greater than the hydrogen bonding in the alcohols thereby causing its dissolution in water.

3. CH3CH (OH) CH2CH3

conc. HCl/ZnCl 2

CH3CH (Cl) CH2CH3 + H20

12

POST LAB A. 1. Using the Lucas test, 5 drops 1-hexanol and 2-methyl-2-hexanol is placed in separate clean dry test tube. 2. 1ml of Lucas reagent is added to both solutions and swirled. 3. After 10 minutes the 2-methyl-2-hexanol reacts slowly and after heating slightly gives a white layer. The 1-hexanol does not react.

B.

Chromic acid (acidified dichromate, an oxidizing agent) can also be used to distinguish between types of alcohols by oxidizing the alcohol. Primary alcohols are oxidized to carboxylic acids; secondary alcohols are oxidized to ketones; and tertiary alcohols are not oxidized. During the oxidation, the orange-red color of the chromic acid changes to a blue-green solution. Oxidation involves the breaking of C-C or C-H bond.

O
R CH2 OH +

H 2CrO4 (Red-orange)

R

C

OH

+

Cr2 (SO4)3 + H 2O (Blue-green)

(Primary alcohol)

(Carboxylic acid)

OH R CH R +

O

H 2CrO4

R

C

R

+

Cr2 (SO4)3 + H2O (Blue-green)

(Secondary alcohol)

(Red-orange)

(ketone)

OH R C R R

+

H2CrO4

No Reaction

(Tertiary alcohol)

13

REFERENCE Ralph J. Fessenden and John S. Fessenden, Organic Chemistry, 4TH Edition, Page 257-300, Pacific Grove Inc., California, U.S.A B.S. Furniss, A.J. Hannaford, P.W.G. Smith and A.K. Tatchell, Practical Organic Chemistry, 5TH Edition, Page 517-550, 1989, Singapore

14