Experiment 8A

Qualitative Analysis

QUALITATIVE ANALYSIS used to A set of procedures and techniques

identify and quantify the chemical composition of a given sample of a substance; Seeks to identify the substances in a sample, i.e. functional groups; Relies on certain chemical reactions to detect particular functional groups, such as alcohol, amine, aldehydes. A visible reaction indicates the presence of a functional group. The presence of Functional Groups is identified by reacting the compound to a reagent which gives a specific visible result.

QUALITATIVE ANALYSIS
Four basic areas of inquiry are useful for identifying the nature of an unknown compound namely, physical properties of compounds, classification by solubility, elemental analysis, and classification test for functional groups. This experiment focuses on the fourth area of inquiry.

1. Reaction with Bromines in Methylene Chloride 2. Baeyer Test 3. Ignition Test

TEST FOR UNSATURATIO N

METHODOLOG Y

PREPARATION OF ACETYLENE
Place a piece of CaC2 lump in a 250-ml distilling flask. Fill a 125-ml separatory funnel with 50-ml water.

CaC2 + 2H2O

C2H2 + Ca(OH)2

TEST FOR UNSATURATION

Reaction with Bromines in Methylene Chloride

METHODOLOG Y

3 drops of 2% SOLUTION OF BROMINE IN METHYLENE CHLORIDE

3 DROPS

ACETYLENE BENZENE

STYRENE HEXANE

RESULTS

Acetylene
Two layers Clear Orange Evolution of gas

Benzene
Dark orange-red

Styrene
Cloudy white

Hexane
Orange red

Reaction with Bromines in Methylene

DISCUSSION

ELECTROPHILIC ADDITION (HALOGENATION)

ALKENE

ALKYNE

Reaction with Bromines in Methylene

DISCUSSION

ELECTROPHILIC ADDITION (HALOGENATION)

The decoloration of Bromine solution test and Baeyer test differentiate saturated from unsaturated hydrocarbons. In decoloration of bromine solution test, if the test compound is unsaturated, the orangebrown color of the aqueous bromine solution rapidly disappears. Bromine adds to each of carbon of the bond then the pi bond converts into a sigma bond and thus become saturated. As a result of this reaction, an OH group is added to each carbon at each end of a multiple bond. When this happens, the multiple bond becomes saturated.

Reaction with Bromines in Methylene

TEST FOR UNSATURATION

Baeyer Test

METHODOLOG Y

3 drops of 1% AQUEOUS SOLUTION OF KMnO4

3 DROPS

ACETYLENE BENZENE

STYRENE HEXANE

RESULTS

Acetylene
Dark brown precipitate

Benzene
Two layers Clear Violet

Styrene
Cloudy white Brown precipitate

Hexane
Two layers Clear Violet

DISCUSSION

REDOX REACTION

 

Potassium Permanganate (KMNO4) is an oxidizing agent. It is purple. Following the oxidation of an unsaturated compound, the Permanganate ion is reduced to Manganese Dioxide (MnO4), a brown precipitate.

TEST FOR UNSATURATION

Ignition Test

METHODOLOG Y
ACETYLENE TOLUENE

STYRENE HEXANE

RESULTS

Acetylene
Orange & blue flame
Al

Xylene
Orange & blue flame Formation of soot
Ar

Styrene
Dark orange flame Formation of soot
Ar

Hexane
Orange flame
Al

DISCUSSION

HIGH DEGREES OF UNSATURATION

Differentiate aliphatic substances from aromatic unsaturated hydrocarbons 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

1.Nitration 2.Le Rosen Test

TEST FOR AROMATICITY

TEST FOR AROMATICITY

Nitration

METHODOLOG Y

RESULTS

SMEL L COLO R

Naphthalene-like odor Light yellow Slightly immisicible

DISCUSSION

ELECTROPHILIC AROMATIC SUBSTITUTION (NITRATION)

TEST FOR AROMATICITY Le Rosen Test

METHODOLOG Y

5 drops Le Rosen reagent 5 drops xylene

INCLINE

RESULTS

COLOR 2 LAYERS

Pink Immisicible P-quinone

DISCUSSION

ELECTROPHILIC AROMATIC SUBSTITUTION (NITRATION)

Same as nitration; formaldehyde in place of HNO3

1. pH of Aqueous Solution 2. NaHCO3 Test 3. AgNO3 Test 4. Silver Acetylide Test

TEST FOR ACIDITY AND BASICITY

TEST FOR ACIDITY AND BASICITY

pH of Aqueous Soln

METHODOLOG Y

pH PAPER

2 DROPS OF TEST SAMPLE DISSOLVED IN 20 DROPS WATER

20 mg TEST SAMPLE DISSOLVE D IN 20 DROPS 95% ETHANOL

ACETIC ACID PHENOL

ANILINE BENZOIC ACID

RESULTS

Acetic Acid
2-3 (4.76 at 25oC)

Phenol
4-5 (9.95)

Aniline
6-7 (27; Pkb 9.42)

Benzoic Acid
3 (4.21)

DISCUSSION

ACIDS AND BASES

TEST FOR ACIDITY AND BASICITY

NaHCO3 Test

METHODOLOG Y

20 drops 5% NAHCO3

2 DROPS OF TEST SAMPLE DISSOLVED IN 20 DROPS WATER

20 mg TEST SAMPLE DISSOLVE D IN 20 DROPS 95% ETHANOL

ACETIC ACID PHENOL

ANILINE BENZOIC ACID

SHAKE GENTLY

RESULTS

Acetic Acid
Gas bubble Clear

Phenol
Brownish red Dark precipitate

Aniline
Two layers Aniline NaHCO3

Benzoic Acid
Gas bubbles Benzoic acid crystals deposit on walls (Clear solution)

DISCUSSION

If the compound is soluble, then it is acidic. Solubility indicated by evolution of gas, bubbles and change in color. Carboxlyic acid is a strong acid. Phenol is a common weak acid. Negatively substituted phenols such as nitrophenols, aldehydrophenols, and polyhalophenols are sufficiently acidic to dissolve in 5% sodium bicarbonate.

TEST FOR ACIDITY AND BASICITY

AgNO3 Test

METHODOLOG Y

ACETIC ACID

PHENOL

BENZOIC ACID

ANILINE

Place 2 drops test sample and 20 drops 95% ethanol.

Add 20 drops 2% ethanolic AgNO3

Precipitate forms, add 5% HNO3 dropwise.

Precipitate does not form.

RESULTS

Acetic Acid
No precipitate (White precipitate)

Phenol
No precipitate

Aniline
No precipitate

Benzoic Acid
No precipitate (White precipitate)

DISCUSSION

Only acids will react to form the precipitate due to the departure of H from the molecule and replacing it with a silver ion. The ammoniacal silver ion reacts with acetylene to form C2Ag2 (Silver acetylide), which is the solid precipitate.

DISCUSSION

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 should dissolve in nitric acid.

TEST FOR ACIDITY AND BASICITY Silver Acetylide Test

METHODOLOG Y

20 drops 2% AgNO3 solution

1M NH3 dropwise until precipitate dissolves

Pour into test tube with acetylene gas. Stopper and shake

RESULTS

Precipitate

White to yellow

DISCUSSION

Silver acetylide is formed when acetylene is passed into an ammoniacal solution of silver nitrate. These substitution reactions which ethynes undergo to form compounds with metals are not occur with the alknes. 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.

1. Beilstein Test 2. Alcoholic AgNO3 Test

TEST FOR ALKYLHALIDE S

TEST FOR ALKYLHALIDES

Beilstein Test

METHODOLOG Y

METHODOLOG Y

Benzylchloride

Dip the loop into 5 ml test tube containing 20 drops of test sample and bring to flame

ethylbromide

chlorobenzene

Ethylcholoride

Tert-butylchloride
Green

RESULTS

(Green)

Ethylbromide
Green

Sec-butylchloride
Green

Ethyliodide
(Green)

Benzylchloride Chlorobenzene
Green Green

DISCUSSION

A positive test is indicated by a green flame caused by the formation of a copper halide. This test is little used nowadays; one reason why it is not popular is that it is possible to generate the highly toxic chloro-dioxins if the test material is a polychloroarene.

CuO + 2 R-X --> CuX2 + 2 R-O-?

TEST FOR ALKYLHALIDES Alcoholic AgNO3 Test

METHODOLOG Y

Ethylcholoride

Tert-butylchloride
Grayish white precipitate

RESULTS

(White layer)

Ethylbromide
Green precipitate Clear layer

Sec-butylchloride
Grayish white precipitate

Ethyliodide
(White layer)

Chlorobenzene
Unsoluble immiscible

DISCUSSION

ALIPHATIC HALIDE vs AROMATIC HALIDE

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, 3o>2o>1o Alkyl bromides and iodides react more rapidly than chlorides Aryl Halides are unreactive toward the test reagent.

DISCUSSION

ALIPHATIC HALIDE vs AROMATIC HALIDE

GUIDE QUESTIONS

What test/s could be used to differentiate saturated and unsaturated hydrocarbons. Explain.
ANSWER The decoloration of Bromine solution test and Baeyer test differentiate saturated from unsaturated hydrocarbons. In decoloration of bromine solution test, if the test compound is unsaturated, the orange-brown color of the aqueous bromine solution rapidly disappears. Bromine adds to each of carbon of the bond then the pi bond converts into a sigma bond and thus become saturated. In the permanganate test, an unsaturated compound reduces the purple permanganate ion (MnO4-), forming a precipitate of brown manganese (IV) oxide (manganese oxide, MnO2). As a result of this reaction, an OH group is added to each carbon at each end of a multiple bond. When this happens, the multiple bond becomes saturated.

QUESTION #1

Do alkynes give all tests which alkenes exhibit? What tests could be used to differentiate them?
ANSWER No. The silver acetylide test could be used to differentiate between an alkyne and an alkene. It only produces a positive test (formation of a silver precipitate) on alkynes.

QUESTION #2

Illustrate with equation the reaction of Br2 in methylene chloride with acetylene.
ANSWER

ALKYNE

QUESTION #3

Does toluene behave in the same way like the other unsaturated hydrocarbons? Why?
ANSWER In our case, we used xylene as a substitute for toluene. Xylene does not behave in the same way like other unsaturated hydrocarbons because of the presence of a benzene ring. This stable structure due to resonance is less reactive than the other saturated hydrocarbons. The shared electrons in the saturated bonds of the aromatic compound ring prevent aqueous bromine solution from reacting with them.

QUESTION #4

What is the role of concentrated sulfuric acid in the nitration of toluene?

ANSWER Concentrated sulfuric acid acts as an electrophilic generator. It displaces weaker acids from their salts with nitric acid itself, sulfuric acid acts as both an acid and a dehydrating agent, forming nitronium ion, NO2+.

QUESTION #5

Show the mechanisms for nitration and Le Rosen reaction.

ANSWER

QUESTION #6

Give the equation involved in the reaction of acetylene with ammoniacal silver nitrate
ANSWER

C2H2 + Ag(NH3)NO3 C2Ag2 + HNO3

Only acids will react to form the precipitate due to the departure of H from the molecule and replacing it with a silver ion. The ammoniacal silver ion reacts with acetylene to form C2Ag2 (Silver acetylide), which is the solid precipitate.

QUESTION #7

Tollens reagent for the silver acetylide test should always be freshly prepared. Why?
ANSWER It is because Tollen's reagent when left standing decomposes and forms a highly explosive precipitate-silver fulminate, which is dangerous in laboratory experiment.

QUESTION #8.

Explain why terminal hydrogen in acetylene is acidic when in fact the electronegativity values of hydrogen and carbon are almost the same.
ANSWER Terminal alkynes are unusual hydrocarbons for they can be deprotonized using an appropriate base to generate carbanion. This is an acidic situation since terminal alkynes have an sp-hybridized orbital with 50% s character, meaning it is a highly electronegative orbital, the electron pair shared with H(terminal and directly attached to the unsaturation) is tightly held by the nucleus of C making it electrostatically stabilized. So, The H+ now, to relieve the tension can leave off the chain. Since this is a positive H, then terminal alkynes are acidic.

QUESTION #9

What test/s could be used to carboxylic acids from phenol. Explain.

ANSWER The NaHCO3 test could be used. Carboxylic acids are soluble in sodium bicarbonate solution while phenols are not. A visible evolution of bubbles happens during the reaction of a carboxylic acid. Phenols do not. Ethanolic silver nitrate test could also be used. Carboxylic acids initiate the production of precipitate (silver carboxylate salt). Phenols do not.

QUESTION #10

Why is the order of reactivity of the alkylhalides toward alcoholic silver nitrate 3o>2o>1o?
ANSWER Tertiary carbocations formed by the heterolysis of alkyl halide is more stable due to C-H hyperconjugation. The positive charge is distributed to a greater number of surrounding hydrogen atoms compared to the secondary and primary alkylhalides. The primary carbonium ion is the least stable since its positive charge is concentrated only to the carbon atom.

QUESTION #11

In the Beilstein test, the appearance of green flame indicates the presence of what compound?
ANSWER The green flame is caused by the copper halide which is formed from the combustion reaction of copper (II) oxide (from heated copper wire) and the alkyl halide.

QUESTION #12

In the silver nitrate test for halides, explain why alcohol is used as the solvent for silver nitrate and not water.
ANSWER Water is not used as the solvent because it is highly polar, considering that the reaction proceeds with a hydrocarbon. Ethanol, having both hydrophobic and hydrophilic portion, can considerably dissolve the polar nitrate and the nonpolar alkyl chain. Alkylhalides AgBr and AgCl form precipitates insoluble in ethanol and provides indicator for the alkylhalide test.

QUESTION #13

UNSATURATION

(+)

(-) No reaction. Color does not become clear

TESTS FOR

BROMINE IN METHYLENE CHLORIDE

Disappearance of orange-red color

UNSATURATION (REACTIVITY TO HALOGEN)

BAEYER TEST

Clear color; brown precipitate

Immiscible

UNSATURATION (REACTIVITY TO KMnO4) AROMATICITY/ HIGH DEGREE OF UNSATURATION

IGNITION TEST

A sooty yellow flame

No soot

ACIDITY / BASICITY

(+) pH OF AQ. SOLN --Solubility (evolution of gas, bubbles, change in color)

(-) ---

TESTS FOR ACIDITY/ BASICITY

NaHCO3

No change

ACIDITY

AgNO3

White precipitate

No formation of precipitate

ACIDITY (REACTIVITY TO AMMONIACAL SILVER ION) ALKYNE

SILVER ACETYLIDE TEST

Silver precipitate

No formation of precipitate

ALKYLHALIDE S

(+) BEILSTEIN TEST ALCOHOLIC AgNO3 TEST Green flame White-Gray precipitate

(-) Other color flame Insoluble

TESTS FOR Cl, Br, I but not F ALIPHATIC HALIDE

CONCLUSION

Identification of the functional groups gives the grounds for establishing the nature and full-identity of an organic compound. Positive results from the tests confirm the presence of a specific functional group. The limitations of the experiments are the fact that the true identity of the compound cannot be determined through the tests conducted. Only the functional groups present in the organic compound can be determined. Further investigations can be conducted to find out the real nature and components of the organic compound.