University of the Philippines Manila College of Arts and Sciences Department of Physical Sciences and Mathematics

CHEM 31.1 Organic Chemistry

-Experiment

8A

Angela Ray T. Abala Kurt Roland A. Asperas

1. 2. 3. 4.

Physical Properties of compounds Classification by solubility Elemental analysis Classification test for functional groups

This experiment focuses on the fourth area of inquiry.

1. 2. 3. 4.

Test Test Test Test

for for for for

Unsaturation Aromaticity Acidity and Basicity Alkylhalides

Identification of Functional groups

Test for Alkylhalides

Test for Acidity and Basicity

Test for Aromaticity

Test for Unsaturation

The carbon atom has the capability to bond with four other atoms. However, this ability to bond to several atoms (especially to H atoms) becomes reduced because of the presence of multiple bonds. The presence of double or triple bonds is an indication of the unsaturation of the compound. Alkenes and Alkynes

How to prepare Acetylene? Test for Unsaturation Bromine in Methylene Chloride Test

Preparation of Acetylene

Test for Unsaturation Bromine in Methylene Chloride Test

- electrophilic addition or halogenation

Test for Unsaturation Bromine in Methylene Chloride Test

 Addition reaction of Bromine (Br2), a red liquid, to a compound containing a double or triple bond produces a colorless Dibromide. (A positive Test!) The double (or triple bond) must be sufficiently electron-rich to initiate the reaction. Therefore, minimal electron withdrawing groups (Deactivators), such as Carboxyl Groups attached to molecule, would hinder the reaction. Unsubstituted Aromatic compounds (Benzene) do not react with the Bromine reagent. Even if the ring has substituted activating groups (donate electrons to the ring) the reaction would be a substitution and not an addition.

Test for Unsaturation Bromine in Methylene Chloride Test

Test Samples Acetylene

Visible Result Unpleasant odor, produced smoke, pale yellow-clear solution Red solution Presence of smoke, cloudy-clear solution Negative test

Structure/Formula of Compound Responsible for the visible result

Benzene Styrene

No visible result

Hexane

No visible result

POSITIVE TEST: clear solution

Test for Unsaturation Bromine in Methylene Chloride Test

Test for Unsaturation Baeyer Test

- Redox reaction

Test for Unsaturation Baeyer Test

  

Potassium Permanganate (KMNO4) is an oxidizing agent. It has a Purple color Following the oxidation of an unsaturated compound, the Permanganate ion is reduced to Manganese Dioxide (MnO4), a brown precipitate. The reaction is important because it doesnt work on alkanes (compounds with carbon-carbon single bonds) or aromatic compounds.

Test for Unsaturation Baeyer Test

Drawbacks:  Easily oxidized compounds give a positive test: a) Most aldehydes give a positive test. b) Formic acid and its esters give a positive test. Often, the brown precipitate fails to form and the solution turns reddish-brown. Alcohols with trace impurities give a positive test. Phenols and aryl amines give a positive test.

  

Test for Unsaturation Baeyer Test

Test Samples Acetylene

Visible Result

Benzene Styrene

Hexane

Brown solution, chocolate brown precipitate Dark purple No visible result solution Dark brown MnO2 for the brown precipitate in clear precipitate solution Violet precipitate No visible result

Structure/Formula of Compound Responsible for the visible result MnO2 for the brown precipitate

POSITIVE TEST: The disappearance of the KMnO4's purple color and the appearance of a brown suspension of MnO2 is a positive test.

Test for Unsaturation Ignition Test

Test for Unsaturation Ignition Test

 Ignition test is used for High Degrees of Unsaturation. The ignition test is used to differentiate aliphatic substances from aromatic unsaturated hydrocarbons. Multiple bonds of carbon cause the deposition of carbon in the ignition medium soot positive test!

Test for Unsaturation Ignition Test

Highly unsaturated compounds such as aromatic compounds, give off a yellow sooty flame. The yellow color is due to the presence of carbon and the soot is credited to the deposition of carbon. Positive test is indicative of a high degree of Unsaturation and is probably Aromatic

Test for Unsaturation Ignition Test

Test Samples **Acetylene Toluene Styrene Hexane

Visible Result Orange-blue flame Yellow flame, soot Yellow flame, soot Yellow flame

Structure/Formula of Compound Responsible for the visible result C C C No visible result for carbon deposition

POSITIVE TEST: Positive test is a sooty yellow flame.

Test for Unsaturation Ignition Test

Identification of Functional groups

Test for Alkylhalides

Test for Acidity and Basicity

Test for Aromaticity

Test for Unsaturation

Test for Aromaticity Nitration

- electrophilic aromatic substitution

Test for Aromaticity Nitration

 Benzene derivatives in a general sense react in the same way that benzene does, although there are some interesting differences. Nitration of toluene generates a mixture of products. The major products are those with substitution at the ortho and para positions. In the case of toluene, ortho (and para) attack result in the positive charge being spread over two secondary carbons and one tertiary carbon atom (the one bearing the CH3 group). When reaction of toluene occurs at the meta position, then the resonance forms of the sigma complex put positive charge over 3 secondary carbons - the same as for benzene.

Test for Aromaticity Nitration

 Appearance of the product (Nitration of toluene) : light yellow to darker yellow-green liquid

Test for Aromaticity Nitration

Test Samples Toluene

Visible Result

Structure/formula of compound responsible for the visible result

Yellow color on top of solution; similar to oil-water mixture; smoky; smells like rugby

POSITIVE TEST: Yellow solution

Test for Aromaticity Nitration

Test for Aromaticity Le Rosen Test

Test for Aromaticity Le Rosen Test

In the Le Rosen test, same processes in nitration take place. However, instead of HNO3, formaldehyde is used.

Test for Aromaticity Le Rosen Test

Test Samples Toluene

Visible Result Exhibited two layers Rose pink solution

Structure/formula of compound responsible for the visible result

p - aquinone

Test for Aromaticity Le Rosen Test

Identification of Functional groups

Test for Alkylhalides

Test for Acidity and Basicity

Test for Aromaticity

Test for Unsaturation

Test for Acidity and Basicity pH of an Aqueous Solution

Test for Acidity and Basicity pH of an Aqueous Solution

pH is a measure of the acidity or alkalinity of a solution. Aqueous solutions with a pH less than seven are considered acidic, while those with a pH greater than seven are considered basic. When a pH level is 7.0, it is defined as 'neutral' because at this pH the concentration of H3O equals the concentration of OH in pure water. pH is formally dependent upon the activity of hydronium ions (H3O+).

Test for Acidity and Basicity pH of an Aqueous Solution

Solution Acetic Acid Phenol Aniline Benzoic Acid *water

pH 2 4 7 2 5

Test for Acidity and Basicity pH of an Aqueous Solution

Test for Acidity and Basicity NaHCO3 Test

Test for Acidity and Basicity NaHCO3 Test

Solubility will be indicated by the formation of a homogeneous solution, a color change, or the evolution of gas or heat. If soluble, then it is a strong organic acid. If not, then it is a weak organic acid. The most common weak organic acid are phenols. Typically, only a carboxylic acid will react with NaHCO3. Negatively substituted phenols such as nitrophenols, aldehydrophenols, and polyhalophenols are sufficiently acidic to dissolve in 5% sodium bicarbonate.

Test for Acidity and Basicity NaHCO3 Test

Sample Acetic Acid Phenol Aniline Benzoic Acid

Observation Evolution of gas Brown solution Distinct 2 layers Dissolved

POSITIVE TEST: Evolution of a carbon dioxide gas is a positive test for the presence of the carboxylic acid

Test for Acidity and Basicity NaHCO3 Test

Test for Acidity and Basicity AgNO3 Test

Test for Acidity and Basicity AgNO3 Test

The silver nitrate test is designed to detect strong acids especially carboxylic acids. The presence of an acid is detected by the presence of replaceable H+ atoms and the formation of precipitates. The essence of this test is the reaction between carboxylic acids and silver nitrate. Silver nitrate reacts with carboxylic acids to form salts of the carboxylic acid. To verify the presence of the silver salt, dilute nitric acid should be added. Silver salts are soluble in the aforesaid acid.

Test for Acidity and Basicity AgNO3 Test

Sample Acetic Acid Phenol Aniline Benzoic Acid

Observation Cloudy solution Precipitate appeared Brown-yellow precipitate White precipitate

POSITIVE TEST: Appearance of precipitate and dissolution of the precipitate in Nitric acid

Test for Acidity and Basicity AgNO3 Test

Test for Acidity and Basicity Silver Acetylide Test

- Silver acetylide is formed when acetylene is passed into an ammoniacal solution of silver nitrate.

Test for Acidity and Basicity Silver Acetylide Test

 These substitution reactions which ethynes undergo to form compounds with metals are not occur with the alkenes. These reactions can be used as tests to distinguish between acetylene and ethylene. When acetylene is passed through an ammonical solution of silver nitrate or cuprous chloride, at room temperature, precipitates of silver acetylide (white) or cuprous acetylide (red) are formed.

Test for Acidity and Basicity Silver Acetylide Test

Sample Acetylene

Observation Pale yellow precipitate gray-silver precipitate

Test for Acidity and Basicity Silver Acetylide Test

Identification of Functional groups

Test for Alkylhalides

Test for Acidity and Basicity

Test for Aromaticity

Test for Unsaturation

Test for Alkylhalides Beilstein Test

 The Beilstein test is a simple chemical test used in chemistry as a qualitative test for halides. In Beilstein test, a green flash is indicative of chlorine, bromine, and iodine. Fluorine is not detected because copper fluoride is not volatile. This test is very sensitive, thus halogencontaining impurities may give misleading results.

Test for Alkylhalides Beilstein Test

Test Samples

Visible Result

Structure / Formula of Compound Responsible for the visible result CuCl2 CuCl2 CuCl2 CuCl2 CuCl2 CuBr2 CuI2

Tert-butylchloride Sec-butylchloride Benzylchloride cholorobenzene ethylchloride ethylbromide Ethyliodie

Blue-green flame Green flame Red flame; soot Red-orange flame; soot Green flame Green flame Green flame

Test for Alkylhalides Beilstein Test

Test for Alkylhalides Alcoholic AgNO3 Test

Test for Alkylhalides Alcoholic AgNO3 Test

 this test can be used to differentiate aromatic halides from aliphatic halides. The reaction of an alkyl halide with silver nitrate in ethanol will result in the formation of a white or yellow silver halide precipitate that is insoluble in nitric acid. This reaction quite often proceeds slowly, and occasionally slight warming is necessary. Different rate if silver halide precipitation would be expected from halogen in each of these environments, namely, primary<secondary<tertiary. Alkyl bromides and iodides react more rapidly than chlorides Aryl Halides are unreactive toward the test reagent.

Test for Alkylhalides Alcoholic AgNO3 Test

Test Samples

Visible Result

Tert-butylchloride Sec-butylchloride Benzylchloride cholorobenzene Ethylchloride Ethylbromide Ethyliodide

White precipitate White-silver precipitate Distinct 2 layers White precipitate White precipitate White precipitate White precipitate

Structure / Formula of Compound Responsible for the visible result AgCl AgCl AgCl AgCl AgCl AgBr AgI

Test for Alkylhalides Alcoholic AgNO3 Test