EXPERIMENT 9 – CLASSIFICATION TESTS FOR
–OH AND C=O CONTAINING COMPOUNDS
A. SOLUBILITY OF R-OH IN H2O
• Alcohols can be classified as primary, secondary and
tertiary
• SAMPLES
o Benzyl alcohol (1°)
o n-butyl alcohol (1°)
o sec-butyl alcohol (2°)
o tert-butyl alcohol (3°)
o Ethanol (1°)
• FACTORS TO CONSIDER ABOUT SOLUBILITY
o POLARITY à Presence of polar functional
groups
§ All are polar because of the
hydroxyl
o HYDROPHOBICITY à R groups present in
the structure of the alcohol
o BRANCHING
• All have hydroxyl so it’s not a factor we consider
anymore
• We look at the number of R groups and the branching
• RESULTS (Decreasing solubility in H2O)
o Ethanol (few C atoms)
o tert-butyl alcohol (branching)
o sec-butyl alcohol (branching)
o n-butyl alcohol (branching)
§ Borderline is four C atoms for
solubility in water
o Benzyl alcohol (presence of benzene ring)
B. LUCAS TEST
• REAGENT: Conc. HCl, ZnCl2
• POSITIVE RESULT: Formation of a cloudy
suspension or of two layers
• REACTION: Nucleophilic Substitution (SN1)
o REACTIVITY: 3° > 2° > 1°
• OBJECTIVE: Differentiate the types of alcohols
• RESULTS:
o First = 3° R-OH
o Second = 2° R-OH
o Third = 1° R-OH (No cloudy suspension)
C. 2,4 – DINITROPHENYLHYDRAZONE TEST
• REAGENT: 2,4 – dinitrophenylhydrazine
• POSITIVE RESULT: Formation of yellow/orange
crystals (ozazone crystals)
o Check which ppt is darker
o The color depends on the structure
• REACTION: Nucleophilic Addition followed by
Elimination (ANE)
• OBJECTIVE: Test for the presence of carbonyl group
(aldehydes and ketones)
• RESULTS:
o Positive for all aldehydes and ketones and
negative for alcohol
o n-butyraldehyde
o Benzaldehyde
o Acetone
o Acetophenone
o Acetaldehyde
• OTHERS NOTES
o Hydrazine reagent will add to the carbonyl
o Both aldehydes and ketones will show a
positive result but they will differ in the
(1) order of reaction AND the (2) color of the
crystals
§ (1) For aldehydes, the carbonyl
functional group is found at carbon
#1. For ketones, the carbonyl is
found at carbon #2.
§ (2) If aldehyde/ketone is
conjugated, the color is more
distinct or darker. We obtain orange
crystals instead of yellow crystals.
D. JONES OXIDATION TEST
• REAGENT: K2Cr2O7, conc. H2SO4
o Can also use H2CrO4 or KMnO4
o These are strong oxidizing agents
• POSITIVE RESULT: Blue-green solution
o Presence of Cr2(SO4)3 (visible result)
o Reduction product because the compounds
that go under oxidation is alcohols (primary
and secondary)
• REACTION: Redox
• OBJECTIVE: Check for the oxidizable and reducing
properties of the samples
• RESULTS:
o 1° ROH is oxidized to Aldehyde then to a
Carboxylic Acid (final oxidation product)
o 2° ROH is oxidized to Ketone (final oxidation
product)
• OTHER NOTES
o Use PCC (pyridinium chlorochromate) to
form Aldehyde
o Formation of Cr2(SO4)3 confirms that the
sample is oxidizable or has reducing
properties
E. TOLLENS’ TEST
• REAGENTS: AgNO3, NaOH, NH4OH
o Mix AgNO3 and NaOH first and this will
produce a ppt
o NH4OH is added to dissolve the ppt. This
forms the Tollens’ Reagent.
o Tollens’ Reagent is the Silver Ammonia
Complex/Ag(NH3)
2+
0
• POSITIVE RESULT: Formation of Ag
• REACTION: Redox
• OBJECTIVE: Only for aldehydes
• POSITIVE RESULT:
o Positive for Aldehydes
• OTHER NOTES
o Makes use of a weaker oxidizing agent that’s
why it cannot oxidize alcohol and is used
only for aldehydes
o All aldehydes will form a silver mirror
F. FEHLING’S TEST
• REAGENTS: CuSO4 pentahydrate (Fehling’s A) &
Rochelle salt (sodium potassium tartrate) and NaOH
(Fehling’s B)
o Purpose of adding Fehling’s B (?) is to
prevent the precipitation of copper as cupric
oxide which is color black
o The positive result of brick red is cuprous
oxide
• POSITIVE RESULT: Brick-red ppt
o Cu2O (reduction product)
• REACTION: Redox
• OBJECTIVE: Determine of aldehyde or ketone
 • POSITIVE RESULT:
o Positive for Aldehydes
• OTHER NOTES
o Makes use of a weaker oxidizing agent than
Tollens’
o Since it is a weaker oxidizing agent, we can
use it to differentiate Conjugated Aldehydes
from Unconjugated Aldehydes
§ Conjugated will have a (-) result
§ It has a hard time oxidizing
conjugated samples
§ Unconjugated aldehydes will still
form a brick red ppt but it takes a
longer time
o Aldehydes will be oxidized to carboxylic
acids

G. IODOFORM TEST
• REAGENT: KI, NaOCl
o NaOCl à sodium hypochlorite
o Bleach
• POSITIVE RESULT: Formation of yellow crystalline
ppt
o CHI3 (iodoform/triiodomethane)
• REACTION: Oxidation
• OBJECTIVE: Test for presence of methyl carbonyl
group in the structure
• RESULTS:
o Positive for those with methyl carbonyl after
oxidation
• OTHERS NOTES
o Isopropyl alcohol formed a yellow crystalline
ppt because it can be oxidized to a ketone
o If it’s a ketone already, it has methyl carbonyl
na.
o But not all secondary alcohols can make a
positive result. Basta if the ketone has a
methyl carbonyl after the secondary alcohol
is oxidized, dun siya magiging positive.