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REACTION OF ALCOHOLS
Rate of Reaction
Fast formation evolution of gas of bubbles,
Moderate formation of bubbles, evolution of gas Slow formation evolution of gas of bubbles,
LUCAS TEST
Results:
Sample
N-butyl alcohol Sec-butyl alcohol
Rate of Reaction
Slow formation of layers (37.5 sec) Moderate formation of layers (23.6 sec)
Tert-butyl alcohol
LUCAS TEST
Discussion:
ROH + HCl --ZnCl2-> RCl + H2O R2CHOH + HCl --ZnCl2-> R2CHCl + H2O R3COH + HCl --ZnCl2-> R3CCl + H2O
>Lucas reagent: zinc chloride in concentrated hydrochloric acid >Applicable only to alcohols soluble in Lucas reagent; to monofunctional alcohols lower than hexyl and certain polyfunctional molecules >Faster rate= higher reactivity of alcohol
LUCAS TEST
Discussion:
>Dominant force is the ability of the chloride in the Lucas reagent to replace the OH- group, resulting in water and a water-insoluble substance >Theoretically, tertiary alcohols would react fastest, then the secondary, and then the primary alcohols. >The difference in rates would be explained by the difference in strengths of the CO bond and the density of the electron cloud of the O atom.
REACTION OF PHENOLS
Visible Result
Formation of brown-black complex Formation of black-green complex Formation of violet complex Formation of dark violet complex
blue-violet complex
-naphthol gives a violet or blue coloration. Catechol gives a green color which rapidly darkens. Resorcinol gives a violet or blue coloration.
Sample
Phenol Catechol
Visible Result
Orange, 16 drops Dark brown, 4 drops Yellow with precipitate, 2 drops Dark brown, 7 drops
Resorcinol
-naphthol
The OH group in phenol activates the ring. The ring more receptive to electrophiles. Bromination occurs readily, in the ortho and para positions.
Positive test: Decolorization of bromine, presence of precipitates. TRIBROMINATED PRODUCT. Theoretically, the product should
MILLONS TEST
Results
Sample
Phenol Catechol Resorcinol -naphthol
Visible Result
dark upper layer, light bottom dark blackish (solution) dark purple greenish yellow
Millons Test
Discussion
Millons reagent is an analytical reagent with mercuric and mercurous ions in nitric and nitrous acids used to detect the presence of phenolic compounds.
Tyrosine: the only amino acid containing a phenol group The phenol group of tyrosine is first nitrated by nitric acid in the test solution. Then, the nitrated tyrosine complexes with mercury(I) and mercury(II) ions to form a red solution or precipitate. Positive test: brick red precipitqte
Millons Test
Discussion
Acetaldehyde, CH3CHO
Anhydrous monomer
Acetone, (CH3)2CO
Simplest ketone
Benzaldehyde, C6H5CHO
Simplest aromatic aldehyde
2, 4 DNPH TEST
Reagent: 2, 4 Dinitrophenylhydrazine (+) Result: insoluble yellow, orange ppt Detects: C=O of aldehydes and ketones Overall Rxn:
2, 4 DNPH TEST
Mechanism: Nucleophilic Addition-Elimination RXN
2, 4 DNPH TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results 2,4 dinitrophenylhydrazone 2,4 dinitrophenylhydrazone 2,4 dinitrophenylhydrazone 2,4 dinitrophenylhydrazone
Yellow ppt Yelllow ppt Orange ppt Thick, paint-like orange ppt
BISULFITE TEST
Reagent: bisulfite , NaHSO3 (+) Result: white ppt Detects: aliphatic and aromatic aldehydes S (nucleophile) is bulky, it will only add to:
aldehyde in w/c one of the R groups is H ketone having small R groups
RXN:
BISULFITE TEST
Mechanism:
BISULFITE TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results (C6H6)CH(OH)SO3Na+ (C6H6)CH(OH)SO3Na+ (C6H6)CH(OH)SO3Na+ (C6H6)CH(OH)SO3Na+
SCHIFFS TEST
Reagent: Schiff reagent (Fuschin and NaHSO3) (+) Result: purple or magenta soln Detects: aliphatic and aromatic aldehydes
Fuschin (roseaniline hydrochloride) is a red-pink triphenylmethane dye that is converted to a colorless compound upon reaction with sulfurous acid via an electrophilic addition Nucleophile very bulky, general test for aldehydes The colored product is due to conjugation of tri-aryl group present
SCHIFFS TEST
Mechanism:
SCHIFFS TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results
Light purple soln, fast-spread of color Red-violet soln, slow diffusion of color No color change Violet solution, slowest color diffusion
TOLLENS TEST
Reagent: diamminesilver(I) ion, [Ag(NH3)2]+. (+) Result: silver mirror, black ppt Detects: aliphatic and aromatic aldehydes
Aldehydes easily oxidized by silver ion, silver ion then reduced to silver metal test should not be used if a triple bond is present due to similar result RXN:
TOLLENS TEST
TOLLENS TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results Ag(s) Ag(s)
Ag(s)
IODOFORM TEST
Reagent: I2 in KI (+) Result: formation of lemon yellow ppt(CHI3) Detects: CH3-C=O groups Differentiates acetaldehyde from benzaldehyde Mechanism:
IODOFORM TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results
Clear soln With lemon yellow ppt With lemon yellow ppt Clear soln CHI3 CHI3
FEHLINGS TEST
Reagent: CuSO4 in Tartrate and NaOH (+) Result: brick red ppt(Cu2O) Detects: aliphatic aldehydes and reducing sugars Fehlings solution= Fsoln No. 1 (copper (II) sulfate) + Fsoln No. 2 (sodium potassium tartrate and sodium hydroxide). Aldehydes reduce the complexed copper(II) ion to copper(I) oxide RXN:
FEHLINGS TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results Cu2O Cu2O
Brick red ppt Brick red ppt No visible change No visible change
MOLISCH TEST
Reagent: A- naphtol in H2SO4 (+) Result: purple-brown/red ring at junction Detects: Carbohydrates
Conc. H2SO4 converts carbohydrates to furfural or its derivatives which reacts to Molisch reagent RXN:
MOHLISCH TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results
Violet ring Violet ring Violet ring; most noticeable Violet ring; least noticeable
BENEDICTS TEST
Reagent: CuSO4 in Sodium citrate and NaHCO3 (+) Result: brick red ppt (Cu2O) Detects: aliphatic aldehydes and reducing sugars Benedict's reagent =blue copper(II) ions (Cu2+) reduced to copper(I) (Cu+). Then, precipitated as red copper(I) oxide which is insoluble in water. Reducing sugars: All monosaccharides and ome disaccharides that have exposed carbonyl groups RXN:
BENEDICTS TEST
Results
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results Cu2O Cu2O
G. TESTS OF AMINES
Amines= have basic nitrogen atom with a lone pair
HINSBERG TEST
Reagent: 10% NaOH and Benzenesulfonyl chloride (+) Result: 1deg Amines- insoluble in acid and soluble in base 2deg Amines- insoluble in both acid and base 3deg Amines- soluble in acid and insoluble in base Detects: 1 deg, 2 deg and 3deg amines differentiates primary, secondary and tertiary amines and anilines depending on the solubility of the precipitate or oily layer which would form from the reaction
HINSBERG TEST
RXN:
HINSBERG TEST
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results C6H5SO2NRH C6H5SO2NR2 R3NHCl C6H5SO2NRH C6H5SO2NRH
N-methylaniline
FORMATION OF ESTERS
Test sample
Visible results
Salicylic Acid
Benzamide
Minty Odor
red litmus to blue, pungent odor
HYDROLYSIS OF BENZAMIDE
Benzamide contains NH2. When NaOH was added to benzamide, the OH reacted and the product was formed by C-OH bond. The odor was caused by the release of ammonia The red litmus paper turned blue because the solution turned basic.
HYDROLYSIS OF AN ESTER
Esters
produced from the condensation of an alcohol with a carboxylic acid react with nucleophiles at the carbonyl carbon. The carbonyl is weakly electrophilic, but is attacked by strong nucleophilies. The C-H bonds adjacent to the carbonyl are weakly acidic, but undergo deprotonation with strong bases.
HYDROLYSIS OF AN ESTER
Reagent: 10% or 25% NaOH (+) Result: sour odor due to acetic acid Detects: ester
in alkaline conditions, the carboxylate ion is formed addition of a strong acid, to free the carboxylic acid molecule
HYDROLYSIS OF AN ESTER
Mechanism:
HYDROLYSIS OF AN ESTER
Results:
Test Samples Visible Results Structural Formula of Cmpd Resp for Vis Results CH3COOH
Ethylacetate
HYDROLYSIS OF AN ANHYDRIDE
Acetic anhydride dissolves in water to approximately 2.6% by weight. Aqueous solutions have limited stability because, like most acid anhydrides, acetic anhydride hydrolyses to give acetic acid.
Acyl Halide
Ester
GUIDE QUESTIONS
1. WHAT PROPERTY OF ALCOHOL IS DEMONSTRATED IN THE REACTION WITH NA METAL? WHAT IS THE FORMULA OF THE GAS LIBERATED?
The alcohol exhibited acidic property in the test of the reaction with Na metal. This is because the hydroxyl group contains the electronegative oxygen while hydrogen has a positive charge. 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?
A dry test tube should be used because Na metal is highly reactive. Its reaction with water is highly exothermic that it may ignite violently due to the H2 gas produced.
3. WHY IS THE LUCAS TEST NOT USED FOR ALCOHOLS 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). The greater the number of carbon atoms in a compound, the longer the hydrocarbon chain gets. Since long chains of carbon atoms make the compound nonpolar and the OH group less functional, the alcohol in the reagent becomes insoluble, thus rendering the test ineffective.
4. EXPLAIN WHY THE ORDER OF REACTIVITY OF THE ALCOHOLS TOWARD LUCASS REAGENT IS 3>2>1? Primary, secondary, and tertiary alcohols differ from one another in their abilities to produce stable carbocations, Since the reaction of alcohols with Lucas reagent is a nucleophilic substitution reaction or SN1 reaction, the rate determining step is the formation of carbocation. The carbocation is most stable in a tertiary alcohol due to the electrondonating methyl groups which stabilize the positive charge left behind by the removed hydroxyl group through inductive effect 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 solution: (o = 1.33 V) (o = -0.13 V) n-butylalcohol (oxidized to aldehyde/carboxylic acid)
5. ILLUSTRATE WITH EQUATIONS THE REACTIONS OF THE FOLLOWING ALCOHOLS WITH POTASSIUM DICHROMATE.
sec-butylalcohol (oxidized to ketone)
tert-butylalcohol (cannot be oxidized because tertiary alcohols do not have a hydrogen atom attached to a carbon)
6. WHAT FUNCTIONAL GROUP IS RESPONSIBLE FOR THE OBSERVED RESULT IN MILLONS TEST
Phenol interacts with nitric acid producing nitrated phenol. It then reacts with mercury and mercury salts are formed. This reaction accounts for the observed result. The phenolic group of the phenol derivatives is mainly responsible for the observed result in Millons test.
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 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.
9. SHOW THE MECHANISM FOR THE REACTION OF ACETALDEHYDE WITH THE FOLLOWING REAGENTS: 2,4-DNPH
NaHSO3
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?
For a positive iodoform test, there must be a methyl carbonyl in the compound. A positive result will be obtained from ethanol 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.
12. WHAT TEST WILL YOU USE TO DIFFERENTIATE EACH OF THE FOLLOWING PARTS? GIVE ALSO THE VISIBLE RESULT.
Acetaldehyde and acetone Schiffs and Tollens test would differentiate acetaldehyde from acetone. A purple solution formed from Schiffs test indicates presence of aldehydes. On the other hand, a silver mirror will be observed from a compound with aldehydes in Tollens test. However, both will not form any reaction with acetone. Acetaldehyde and benzaldehyde Benedicts test should be used. Upon its addition brick red precipitates would be produced, showing a positive result only to aliphatic aldehydes. This would thus differentiate acetaldehyde from benzeldehyde which is an aromatic aldehyde.
QUESTION 13
13. A colorless liquid has a bp of 199-201C and burns with smoky flame. The sodium fusion test proved negative for the presence of halogens, nitrogen, and sulfur. It was not soluble in water, 5% hydrochloric acid. However, it was dissolved in sulphuric 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 to 136. Identify the unknown liquid.
QUESTION 13
colorless liquid means there is an absence of color (clear-means no solid material present) BP 199-201 C [consulting a Handbook of Physical constants], unknown is close to:
Benzyl Chloride Phenol Aniline N-methylaniline Benzoyl Chloride Methyl Benzoate Salicylic Acid 179 C 181.7C 184.13 C 194-196 C 197.2 C 199.6 C 211 C
burns with a smoky flame presence of aromatic compound sodium fusion test proved negative for the presence of halogens, nitrogen and sulfur negative to Test for Alkylhalides (Beilstein Test and Alcoholic AgNO3 Test) and Schotten-Baumann Reaction note: absence of nitrogen note: absence of sulfur
QUESTION 13
not soluble in water, 5% aqueous sodium hydroxide, or 5% hydrochloric acid
high molecular weight, low polarity NOT an acid, not a base has a a and a (pi-electron) NO ketone or aldehyde functional groups presence of alkenes or alkynes possibly an Acid Anhydride possibly an Ester possibly a Ferric Hydroxamate Complex Formation CANNOT BE an Acyl Halide the unknown is an ester
dissolved in sulfuric acid with evolution of heat did not give a precipitate with 2,4-DNPH solution did not decolorize bromine-methylene chloride solution did give a positive hydroxamate test
saponification equivalent of 136 The quantity of fat in grams that can be saponified by 1 liter of normal alkali
METHYL BENZOATE
CONCLUSIONS
AND RECOMMENDATIONS
CONCLUSIONS
Identification of organic compounds is usually done using various qualitative tests. In qualitative analysis, a general scheme of tests is followed to detect the presence of certain functional groups and to further classify the organic compounds. Functional groups dictate the properties which a compound possesses. In this experiment, alcohols, phenols, aldehydes, ketones, amines, and carboxylic acids and its derivatives were classified and detected through the numerous qualitative tests. The specific reactivity of the functional groups to the different tests made the classification and identification of functional groups present in the organic compounds possible. By knowing the functional groups present, combined with its physical properties, the identity of an unknown organic compound may be recognized.
CONCLUSIONS
Discrepancies may be attributed from: contaminated reagents wrong procedure and misinterpretation of results equipment malfunctions environmental errors personal errors
RECOMMENDATIONS
Use proper protection equipment like gloves, masks and goggles Use fresh and well-prepared reagents Use a complete set of reagents Use different droppers for various reagents Close the lids Attentiveness & carefulness