EXPERIMENT 8B

Qualitative Analysis
Part E: Tests for Alcohols and
Phenols
Methodology:
Test for alcohols
Reaction with Sodium Metal Lucas Test
5mL test tube:
20 drops of n-butyl
alcohol/ sec-butyl
alcohol/ tert-butyl
Tiny piece of sodium
metal
5mL test tube:
20 drops of Lucas
reagent
10 drops of n-butyl
alcohol/ sec-butyl
alcohol/ tert-butyl
alcohol
Shake test tube vigorously &
stopper
Test for Alcohols
Reactions with Potassium Dichromate
5mL test tube
20 drops of n-butyl alcohol/ sec-butyl/ tert-butyl
2M H2SO4 classifies
5 drops 3% potassium dichromate solution
Experimental Results
Theoretical Results
Discussion
Test for Alcohols
Reaction with Sodium Metal

Rate of the reaction depends on the alcohols structure: differentiates primary,

secondary, and tertiary alcohols
Sodium metal reacts with the hydroxyl group (proton donor) to release hydrogen gas &
form the salt of alcohol (alkoxide ion).
Acidity: Primary alcohols > secondary alcohols > tertiary alcohols
Steric effects
Primary alcohols: not sterically hindered, easily solvated and stabilized by the
solvent.
Tertiary alcohols: sterically hindered, less easily solvated.
Test for Alcohols

Lucas Test
Lucas reagent: HCl and ZnCl2 dissolved in water
Certain alcohols react with ZnCl2 in acidic aqueous solution to form alkyl halides
Substitution reaction: OH is replaced with Cl
Involves carbocation intermediate
Only secondary and tertiary alcohols react to form alkyl halide
Tertiary alcohols react readily (stable)
Secondary alcohols react slowly
Primary alcohols react negligibly slowly or do not react at all.
Test for Alcohols
Reaction with potassium dichromate

Alcohols can be oxidized using potassium dichromate

Hydrogen atoms are removed
OH group
Carbon attached to the OH group
Carbon attached to the OH group must at least have 1 hydrogen
Primary alcohols- oxidized into an aldehyde
Secondary alcohols- oxidized into a ketone
Tertiary alcohols are not oxidized
Green: oxidation has occurred (Cr+3 ion).
Methodology:
Test for Phenol

Ferric Chloride Test Bromine Water Test

5-mL test tube:
20 drops of 95%
ethanol + 2 drops of
liquid phenol/ -
naphthol/ catechol/
resorcinol + 5 drops of
3% Ferric Chloride
(FeCl3) solution
Mixed
5-mL test tube:
20 drops of 95%
ethanol + 5 drops of
phenol/ -naphthol/
catechol/ resorcinol +
Bromine water
(dropwise while shaking
until persistence of
bromine color)
Test for Phenol
Millons Test
5mL test tube
5 drops Millons reagent + 5 drops phenol/ -naphthol/ catechol/
resorcinol
Shake test tube
Heat in water bath (2 minutes)
Results
Ferric Chloride Test Bromine Water Test

Sample Visible Sample Visible

Results Results

Phenol Dark brown Phenol Copper

Catechol Dark blue Catechol Brown

Resorcinol Upper Layer: Olive
green
Resorcinol Upper Layer: Olive
Bottom Layer: Dark
green
green
Bottom Layer: Dark
-naphthol Upper Layer: Dark green
purple
Bottom Layer: Light
purple -naphthol Clear
Millons Test

Sample Visible
Results

Phenol Amethyst

Catechol Brown

Resorcinol

Pink

-naphthol Turned to purple

Discussion
Test for Phenol

Bromine Water Test

Phenol undergoes bromination
Positive: Decoloration of
bromine, formation of white
precipitate
Tri brominated product - white
precipitation
HBr: not observed
Discussion
Test for Phenol

Ferric Chloride Test

Iron(III) ions form strongly coloured
complexes
Color of complexes vary from
compound to
compound
Positive: Intense color ranging
from purple to reddish brown to
green
Discussion
Test for Phenol

Millons Test
Millons: Mercuric and mercurous ions in nitric
and nitrous acids
Formation of mercury salts after heating
Positive: Pink to red-colored solution, formation of
precipitate
Part F: Test for Aldehydes and
Ketones
Methodology for 2,4-DNPH test

a. Place 5 drops of 2,4-DNPH solution + 3 drops

of formaldehyde in 5mL test tube
b. Heat in water bath for 5 minutes
c. Repeat procedure using other test samples
(acetaldehyde, acetone, and benzaldehyde)
Results
*Experimental

Sample Results

Formaldehyde Orange

Acetaldehyde Red orange

Acetone

Benzaldehyde red
Results
*Theoretical

Sample Results

Formaldehyde

Acetaldehyde
POSITIVE RESULTS

Acetone

Benzaldehyde
Discussion
- They yield dinitrophenylhydrazones that are insoluble solids
- precipitate may be oily first and become crystalline
- alcohols may give positive test because of the air oxidation
Methodology for Bisulfite Test

a. Place 20 drops of methylamine and 5 drops of

benzenesulfonyl chloride in 5mL test tube
b. Mix and cool in an ice bath
c. Repeat procedure using the other samples
(acetaldehyde, acetone, and benzaldehyde)
Results
*Experimental

Sample Results

Formaldehyde clear with white precipitate

Acetaldehyde clear

Acetone

Benzaldehyde Formation of layers

Results
*Theoretical

Sample Results

Formaldehyde With precipitate

Acetaldehyde With precipitate

Acetone No precipitate

Benzaldehyde With precipitate

Discussion
- To differentiate ketones and aldehyde

- Aldehyde has precipitate

- The carbon atom of the carbonyl group acquires a partial positive

charge

- Aldehydes is steric and inductive.

- Nucleophilic addition process, the substrate is the ketone or

aldehyde, while the nucleophile is the bisulfite ion
Methodology for Schiffs Test

a. Place 20 drops of Schiffs reagent + 5 drops of

formaldehyde
b. Repeat procedure using other test samples
(acetaldehyde, acetone, and benzaldehyde)
Results
*Experimental

Sample Results

Formaldehyde magenta

Acetaldehyde violet

Acetone

Formation of layers; top: pink,

Benzaldehyde
bottom: clear
Results
*Theoretical

Sample Results

Formaldehyde Positive test

Acetaldehyde Positive test

Acetone Negative test

Benzaldehyde Positive test

Discussion
Discussion

- Schiffs test reacts with an aldehyde and

not with ketone, since a ketone has a
hindered electrophile. The -NHSO2H of
the Schiffs reagent bonds with the
electrophilic carbon
Methodology for Tollens Test

a. Place 20 drops of the Tollens Reagent + 5

drops of formaldehyde
b. Heat in water bath
c. Repeat using other test samples
(acetaldehyde, acetone, and benzaldehyde)
Results
*Experimental

Sample Results

Formaldehyde Positive for silver glass

Acetaldehyde Positive for silver glass

Acetone

Benzaldehyde Positive for silver glass

Results
*Theoretical

Sample Results

Formaldehyde Positive for silver glass

Acetaldehyde Positive for silver glass

Acetone Positive for silver glass

Benzaldehyde Positive for silver glass

Discussion
- The silver mirror indicates the presence of aldehydes

- This test involves redox reaction

- Positive test: aromatic amine, phenols, -alkoxy and -

dialkylaminoketones, compounds with triple bonds

- False negative test: water insoluble aldehydes

Methodology for Iodoform Test

a. Place 4 drops of formaldehyde / acetaldehyde /

acetone / benzaldehyde in a test tube
b. Add 10 drops of water, 5 drops of 6M NaOH
solution
c. Add 5 drops of water, 5 drops I2/KI solution
Results
*Experimental

Sample Results

Formaldehyde Clear

Acetaldehyde Yellow Precipitate

Acetone

Benzaldehyde Clear
Results
*Theoretical

Sample Results

Formaldehyde -

Acetaldehyde +

Acetone +

Benzaldehyde -
Discussion
- The yellow precipitate
indicates the presence
of aldehyde or ketone
with this grouping:

http://www.chemguide.co.uk/organicprops/
carbonyls/iodoform.html
Methodology for Fehlings Test

a. Place 20 drops of Fehlings reagent and 5

drops of formaldehyde / acetaldehyde /
acetone / benzaldehyde in a test tube
b. Heat in a water bath
Results
*Experimental

Sample Results

Formaldehyde Aquamarine

Acetaldehyde Green

Acetone

Benzaldehyde Blue-Green
Results
*Theoretical

Sample Results

Formaldehyde +

Acetaldehyde +

Acetone -

Benzaldehyde +
Discussion
- The green suspension and red precipitate
indicates a positive test.
- Aldehydes: +

- Ketones: - (except for alpha-hydroxy-

ketones)

- Complexed copper(II) ions with tartrate ions

in a NaOH solution
http://www.chemguide.co.uk/organicprops/
carbonyls/oxidation.html
Methodology for Benedicts Test

a. Place 20 drops of Benedicts reagent and 5

drops of 1% glucose / 1% maltose / 1%
sucrose / 1% boiled starch in a test tube
b. Heat in a water bath
Results
*Experimental

Sample Results

Glucose Light Brown with white ppt.

Maltose -----

Sucrose Blue

Boiled Starch Blue

Results
*Theoretical

Sample Results

Glucose +

Maltose +

Sucrose -

Boiled Starch -
Discussion
- The brick-red precipitate
indicates a positive test.

- Reducing sugars (aldehydes,

alpha-hydroxy-ketone): +

- Non-reducing sugars: -

- Complexed copper(II) ions

with citrate ions in a Na2CO3
solution
http://www.chemguide.co.uk/organicprops/
carbonyls/oxidation.html
Discussion
- Reducing Sugars: has a
free aldehyde group or
free ketone group;
galactose, glucose,
fructose, maltose,
lactose, starch

- Non-reducing sugars:
sucrose, trehalose
Methodology for Molisch Test

a. Place 20 drops of Molisch reagent and 5 drops

of 1% glucose / 1% maltose / 1% sucrose / 1%
boiled starch in a test tube
b. Incline the test tube and run down through the
walls about 2mL of conc. H2SO4
Results
*Experimental

Sample Results

Glucose Violet Ring

Maltose -----

Sucrose Violet Ring

Boiled Starch Violet Ring

Results
*Theoretical

Sample Results

Glucose +

Maltose +

Sucrose +

Boiled Starch +
Discussion

- The purple ring

indicates a positive test.
- +: carbohydrates,
glycoproteins, nucleic
acids
- Alpha-naphthol in
ethanol
Part G: Test for Amines
Methodology
Test the
1. Hinsberg Test solution with
20 drops of 10% NaOH Cover with cork and litmus. Add 10%
5 dropys methylamine shake for about 5 NaOH if still not
5 drops of benzenesulfonyl minutes basic.
chloride *BASIC

Repeat using:
Dimethylamine Add 3 M HCL Add water if it
Trimethylamine (if it has has precipitates.
Aniline precipitates). Shake and
N-methylaniline Observe observe
Results
Experiment
Methylamine -- -- --

Dimethylamine BASIC Has cloudy solid +

nothing
happened

Trimethylamine BASIC Clear light brown -

Anline BASIC Reddish brown -

N-methylaniline BASIC Reddish brown +

brown
Discussion
Hinsberg Test - to differentiate primary, secondary, & tertiary amines

Benzenesulfonylchloride - reacts w/ amines in basic/alkali

Solutions SALTS

NaOH - makes the solution basic

Water - to test solubility

HCl - to test precipitation

reactions, solubility, & precipitation differentiates the amines

Discussion
1) Methylamine (PRIMARY)

+ H2O soluble salts = NO PRECIPITATION

+ HCl acidification = PRECIPITATION

2) Dimethylamine (SECONDARY)

+ H2O insoluble salts = PRECIPITATION

+ HCl acidification = NO CHANGE

Secondary amines undergo reaction with benzenesulfonyl chloride to

precipitate the sulfonamide, and acidification does not result in any change -
Shriner
3) Trimethylamine (TERTIARY)

+ H2O insoluble salts = PRECIPITATION; quaternary ammonium sulfonate

salts => sodium sulfonates

+ HCl acidification = NO PRECIPITATION; sulfonic acids

4) Aniline (PRIMARY)

+ H2O soluble salts = NO PRECIPITATION

+ HCl acidification = PRECIPITATION (milky)

5) N-methylaniline (SECONDARY)

+ H2O insoluble salts = PRECIPITATION

+ HCl acidification = NO CHANGE (reddish brown brown)

Part H: Test for Carboxylic
Acid and its Derivatives
Methodology - Formation of Esters
- Reaction of Carboxylic Acid and Alcohol

- In 10 mL test tube:

- Pinch of salicylic acid

- 20 drops of methanol

- 5 drops of conc. H2SO4

- Mix and shake well

- Heat in water bath for 5 mins.

Results
- Presence of white precipitate

- Salicylic Acid

- From white mixture Clear

- Formula of compound responsible for visible results : Phenyl

ester

*H2SO4 = acid catalyst

Discussion
ESTERIFICATION
Mainly the reaction between alcohols and carboxylic acids to make esters.
Also looks briefly at making esters from the reactions between acyl chlorides
(acid chlorides) and alcohols, and between acid anhydrides and alcohols.
Both reactions are slow and reversible.
To have a positive test, the reaction must be subjected to: heat and an acid
catalyst to favor the forward reaction.
Discussion
Positive test
Ester, in big amounts, gives off a fruity smell
Formation of an oily layer on top of the water is a positive test
Methodology - Hydrolysis of Acid Derivatives

- Hydrolysis of Benzamide

- In 5 mL test tube:

- Pinch of Benzamide

- 20 drops of 10% NaOH

- Hold pc of red litmus paper

over the mouth of the test tube

- Heat to boiling in water bath

Hydrolysis of Acid Derivatives

- Hydrolysis of an Ester

- In 5 mL test tube:

- 20 drops ethyl acetate

- 5 drops 25% NaOH soln

- Loosely cover with cork

- Heat in water bath (15 mins)

- Add 3M HCl dropwise until neutral to litmus

- ** note color change

Hydrolysis of Acid Derivatives

- Hydrolysis of an Anhydride

- In 5 mL test tube:

- 20 drops of water

- Pc of red & blue litmus paper

- 20 drops acetic anhydride

- Gently shake & feel test tube

Results
Acid Derivatives: Litmus paper Odor
Hydrolysis of Turned blue Vinegar smell
Benzamide

Hydrolysis of an Turned Red Vinegar smell

Ester

Hydrolysis of an Blue turned red Vinegar smell

Anhydride Red stayed red
Discussion

Hydrolysis of Acid Derivatives

Hydrolysis reactions are said to be acid-catalyzed or base-
catalyzed, heat is also used to speed up the reaction.
 In the overall process of hydrolysis, a bond in an organic
molecule is broken and an O-H bond in a water molecule also
breaks. Then, from the water molecule, an O-H group adds to
one part from the organic molecule, and an H atom to the other.
Discussion
Hydrolysis of Benzamide
Amide
Functional group:
Alkyl or aromatic group attached to an amino-carbonyl / nitrogen
atom
much-less reactive than acid chlorides, acid anhydrides, or
esters.
Undergo hydrolysis to yield carboxylic acids plus amine on heating
in either aqueous acid or aqueous base.
Discussion
Hydrolysis of Benzamide
Acidic hydrolysis: Nucleophilic addition of water to the protonated amide,
followed by the loss of ammonia.
Basic hydrolysis: Nucleophilic addition of hydroxide to the amide
carbonyl group, followed by the deprotonation of the hydroxide group
and elimination of amide ion. When heated with a base, ammonia gas
is given off.
Discussion
Hydrolysis of Anhydride

Functional group:
Anhydride
Anhydrides hydrolyze to form acid, in the experiment.
Hydrolysis of an anhydride produces carboxylic acid and heat.
Unpleasant odor will be observed.
Hydroxamic Acid test for Acid Derivatives

- In 5 mL test tube:

- 5 drops ethyl acetate

- 20 drops 7% methanolic hydroxylamine hydrochloride soln

- 10% methanolic KOH (until it turns blue)

- 10 drops more of methanolic KOH

- Heat to boiling in water bath

- Cool slightly

- 7% methanolic HCl (until litmus turns red)

- 10 drops 3% FeCl3 soln

** Repeated with Benzamide, Acetic Anhydride, Benzoyl choride

Results
Results

Acid Derivatives: # of drops until # of drops until

litmus turned BLUE litmus turned RED
Ethyl Acetate 7 (white ppt) 26
Benzamide 15 (white ppt) 56
Acetic Anhydride 25 (change in temp) 53
Benzoyl Chloride 28 (Presence of 43
smoke, change in
temp)
Discussion
Hydroxamic acid test for acid derivatives

A class of chemical compounds sharing the same functional group in

which an hydroxylamine is inserted into a carboxylic acid.
Usually conducted to test ester.
Discussion

Hydroxamic acid test for acid derivatives

Discussion

Hydroxamic acid test for acid derivatives

Too much hydrochloric acid prevents the development of colored
complexes.
The solution must be cooled before adding FeCl3 since an acid will be
produced, precipitation is also expected.

A distinct burgundy or magenta color of the ferric hydroxamate

complex is a positive test.
References
G - Shriner. (2004). The systematic identification of organic compounds
8th Ed. Hoboken NJ: John Wiley & Sons Inc.

Laboratory manual in organic chemistry (2010 ed.). (2010). Philippines:

UP Manila.