Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry.

Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.

Qualitative Analysis for Organic

Compounds
Qualitative analysis is used to determine the presence or absence of a particular compound, but
not the mass or concentration of a particular compound in a sample. It is loosely termed as wet
chemical analysis and is the classical way of identifying compounds. However, it has fallen into
disuse in favor of modern analytical techniques that uses instruments to identify compounds.

Qualitative analysis for organic compounds is used to determine the presence of functional
groups in a particular compound. This is based on its physical and chemical properties
arising from the presence of functional groups.

Solubility Tests
Solubility tests are used to determine whether a particular compound has polar or ionizable
functional groups. It is performed in the following order:

Solubility in Water
Compounds containing up to four carbon atoms, and a nitrogen or an oxygen atom are
soluble in water. A solution of the unknown compound in water is tested with a litmus
paper. If blue litmus paper turns red, the compound is most likely a carboxylic acid
(RCOOH); if red litmus paper turns blue, the compound is probably an amine (RNH 2, R2NH
or R3N); however, if the resulting solution is neutral to both, the compound must have
neutral oxygen- or nitrogen-containing functional group such as an alcohol, ether,
aldehyde, ketone, ester or amide. If the compound is insoluble in water, it is necessary to
move on to other solubility tests.

Solubility in 5% NaOH
Compounds containing more than five carbon atoms and acidic protons, such as carboxylic
acids (RCOOH) or phenols (ArOH), are insoluble in water but soluble in a base. These
compounds react with a base to form water-soluble products:

O OH- O
R R + H2 O
-
OH O
carboxylic acid carboxylate ion

OH-
-
OH O + H2O
R R

phenolate ion
phenol
(phenoxide ion)

Phenols and carboxylic acids can be distinguished from each other using a weaker base,
sodium bicarbonate.

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Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.
Solubility in 5% NaHCO3
Sodium bicarbonate (pKa = 10.3) is a weaker base than sodium hydroxide (pKa = 13.8). It
reacts with carboxylic acids (pKa = ~4-5) but not with phenols (pKa = 10.0) to form water-
soluble products:

O HCO3- O
R R + H2O + CO2
-
OH O
carboxylic acid carboxylate ion

HCO3-
OH no reaction
R

phenol

The reaction also liberates carbon dioxide which effervesces out of solution. A positive test
result indicates the presence of a carboxylic acid.

Solubility in 5% HCl
Compounds containing more than five carbon atoms and basic nitrogen atoms, such as
amines (RNH2, R2NH or R3N), are insoluble in water but soluble in an acid. These
compounds react with an acid to form water-soluble products:

H3O+
+
R NH2 R NH3 + H2O

amine ammonium ion

Solubility in Concentrated H2SO4

Compounds with a lone pair of electrons such as unsaturated hydrocarbons or compounds
with a nitrogen or an oxygen atom are protonated by a strong acid such as sulfuric acid to
form products that are soluble in the acid. Compounds that only contain alkyl groups (RH),
halogens (RX) and benzene rings (ArH, ArX) cannot be protonated and will fail to dissolve in
sulfuric acid.

Test for Functional Groups

Compounds with certain functional groups are reactive towards a particular reagent but
compounds without these functional groups are unreactive. These reagents form
characteristic products (i.e. formation of precipitates or products with certain colors) only in
the presence of a particular functional group. The formation of these characteristic
products indicates the presence of a particular functional group.

Ignition Test
This test distinguishes unsaturated compounds from saturated compounds. Highly
unsaturated compounds burn with a yellow flame with a sooty smoke due to their

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Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.
incomplete combustion while saturated compounds burn with a yellow flame with a non-
sooty smoke.

Alcoholic Silver Nitrate Test

Haloalkanes react with silver nitrate in ethanol through an S N1 mechanism to form
insoluble silver halides:
-
AgNO3 O
+
R X R O N + AgX
O
haloalkane silver halide

Since the reaction occurs through an SN1 mechanism, primary alkyl halides react the fastest
and reactivity decreases through tertiary alkyl halides. Alkyl iodides react much faster alkyl
bromides and alkyl chlorides; they easily form a silver iodide precipitate upon mixing at
room temperature. Alkyl bromides and chlorides, however, may require heating. Acyl
halides and organic ammonium halides also react but aryl halides do not.

Baeyer Test
Alkenes react with potassium permanganate at room temperature to give a vicinal diol and
potassium permanganate (purple solution) is reduced to manganese(IV) oxide (reddish-
brown precipitate):
-
MnO 4 MnO 2
OH

OH

alkene vicinal diol

Only alkenes react with potassium permanganate; aromatic rings are unreactive to
potassium permanganate.

Lucas Test
Tertiary and secondary alcohols with up to 5-6 carbon atoms react with Lucas reagent
through an SN1 mechanism to form their corresponding alkyl chlorides. Lucas reagent
consists of zinc chloride dissolved in concentrated hydrochloric acid. Tertiary alcohols react
the fastest; secondary and allylic alcohols may take some time while primary alcohols do
not react at room temperature. The alcohols are soluble in Lucas reagent but their
corresponding alkyl chlorides are not and would form a second phase.

Chromic Acid Test

Primary and secondary alcohols react with chromic acid. Primary alcohols are oxidized to
aldehydes while secondary alcohols are oxidized to ketones. Tertiary alcohols, however,
can no longer be oxidized further and are unreactive to chromic acid. Aldehydes also react
with chromic acid as they are readily oxidized to carboxylic acids. Chromic acid (yellow
solution) is reduced to Cr3+ (green precipitates) after the reaction.

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Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.
2- 3+
CrO 4 Cr
O
R OH
R OH

alcohol carboxylic acid

Iron(III) Chloride Test

Phenols and enols (vinylic alcohols) form colored complexes with iron(III). Solutions of free
iron(III) ions are yellow; however, phenols form purple, red, or green complexes while enols
form red, tan or violet complexes.
3-
Fe3+
-
OH Fe O
H2O
6
phenol iron(III)-phenolate complex

Hydroxamic Acid Test

Esters react with hydroxylamine in an alkaline medium to form a hydroxamic acid;
hydroxamic acids then form red-violet complexes with iron(III) in an acidic medium.
However, other carboxylic acid derivatives such as acid chlorides, anhydrides and imides
also react in the same manner.
O O
R' + NH2OH OH + R' OH
R O R NH
ester hydroxylamine hydroxamic acid
R
O Fe3+ O
OH Fe
R NH H2O HN
O 3
hydroxamic acid iron(III)-hydroxamate complex

Iodoform Test
Methyl ketones, ethanol and methyl carbinols (alkylmethanol) react with hypoiodite (HIO-),
produced in situ from iodine and sodium hydroxide, to produce a carboxylate ion and
iodoform (yellow precipitate):
O I2 O
+ HCI3 (s)
-
R CH3 NaOH R O
methyl ketone carboxylate ion iodoform

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Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.
2,4-Dinitrophenylhydrazine (2,4-DNPH) Test
Aldehydes and ketones react with 2,4-dinitrophenylhydrazine to form 2,4-
dinitrophenylhydrazones (yellow to red precipitates):

O H2N NH NO2
+
R R'
NO2
ketone/aldehyde 2,4-dinitrophenylhydrazine
R
N NH NO2
+ H2 O
R'
NO2
2,4-dinitrophenylhydrazone

The intensity of the red color of the precipitates indicates the degree of conjugation in the
sample. Allylic and benzylic alcohols also react but form only a small amount of precipitate.
Only a considerable amount of precipitate indicates a positive test result; very small yields
are ignored.

Tollens Test
Aldehydes react with Tollens reagent to form a carboxylate ion and a silver mirror. Tollens
reagent consists of silver ions in aqueous ammonia. The test tube containing the reagents
must be clean and grease free to produce the silver mirror; otherwise, a black precipitate of
silver oxide is formed. Ketones do not react with Tollens reagent.
+
Ag(NH 3) 2 Ag (s)
O O

-
R H OH- R O

aldehyde carboxylate ion

References:
Most CF. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.

Palleros DR. Experimental Organic Chemistry. USA: Wiley & Sons; 2000.

[Author unknown]. USA: Xavier University of Louisiana; [cited 2005 Jun]. Available from:
http://xula.edu/Academic/as_college/chem_dept/organic/Notes/23Qual.pdf (dead link)

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