Topic

Qualitative Analysis of Organic Compounds (Chart)

Compiled by

Dr. Parixit Bhandurge

Department

Pharmaceutical Chemistry

KLE College of Pharmacy, Belagavi.

Constituent Unit of KLE Academy of Higher Education and Research.
e-mail: principal@klepharm.edu Website: http://www.klepharm.edu/
Phone: 0831-2471399 Fax: 0831-2472777
JNMC Campus, Beside KLE’s Dr. Prabhakar Kore Charitable Hospital and Research Centre,
Nehru nagar, Belagavi – 590010.
 KLE College of Pharmacy, Belagavi.

Identification of Unknown Organic Compound

The analysis and identification of unknown organic compounds constitutes a very important
aspect of experimental organic chemistry. Often, a common first step in the identification of an
unknown substance is to determine what elements are present in the sample. Although it is often
possible to establish the structure of a compound on the basis of spectra alone (IR, NMR, etc.), the
spectra typically must be supplemented with other information about the compound: physical state and
properties (melting point, boiling point, solubility, odour, colour, etc.), elemental analysis, and
confirmatory tests for functional groups.

In this experiment you will carry out several qualitative tests that will allow you to identify
functional groups in organic molecules. You will then apply what you have learned by characterizing
unknown organic compounds in terms of their functional group and solubility behavior.

There is no definite set procedure that can be generally applied to organic qualitative analysis.
Various books have different approaches, but a systematic approach based on the scheme given below
will give good results. Each functional group has a particular set of chemical properties that allow it to
be identified. Some of these properties can be demonstrated by observing solubility behavior, while
others can be seen in chemical reactions that are accompanied by color changes, precipitate formation,
or other visible effects.

In carrying out identification of an organic compound following tests and observations are
carried out:

I. Preliminary Tests and Physical Examination

II. Determination of Physical Constants (M.P/B.P)
III. Detection of Elements
IV. Determination of Solubility Group
V. Detection of Functional Group
VI. Special Tests, if any.
 Test Observation Inference
I. Preliminary Test and Physical Examination

A State i) Solid Generally high molecular weight,

usually having more than 6 carbon
atom chain.
Eg: Acids, Sugars, Amides, etc.
ii) Liquid Generally low molecular weight,.
Eg: Alcohols, Ethers, Esters, Aliphatic
amines, Aldehydes, Ketones,
Hydrocarbons, etc.
B Colour Pale Yellow Nitro Compounds s.a. nitrobenzene,
dinitrobenzene, nitrophenol, Quinones,
Iodoform
Yellow Orange Nitro-aniline
Pink -Naphthol, -Naphthol, resorcinol,
Red Azo compounds, methyl orange
Green Nitroso compounds
Greenish Yellow o/m-nitrobenzaldehyde
Brown-dark Phenols, Amines, (darken due to
oxidation)
Colourless Compounds not containing strong
Chromophore.
Eg: Acids, Hydrocarbons, ketones,
esters, urea, thiourea, acetamide,
acetanilide, benzamide, naphalene, etc
C Odour Pleasant Alcohols (low mol. Wt.), Aromatic
hydrocarbons, ethers, alkyl halides s.a.
chloroform, chlorobenzene.
Deep Sweet Chloroform
Fruity Esters
Phenolic / Carbolic Phenols and cresols
Fishy Aromatic amines
Kerosene Hydrocarbons
Moth Ball Naphthalene
Bitter Almond Benzaldehyde, nitrobenzene
Pungent/Irritating Aliphatic acids, Acid chlorides,
formaldehyde, and side chain halo
hydrocarbons
CAUTION:
 Do not taste an unknown compound.
 To note the odour, cautiously smell the cap of the container and do it only once. Never smell the contents
of the container directly.
2. Ignition Test
Flame Test: Non-sooty Flame Aliphatic compounds
Take a small quantity of compound Sooty Flame Aromatic compounds
and put it on a metallic spatula or in a Ammonical odour Urea, thiourea, amides may be present
porcelain dish and ignite it directly on
the Chars and swells without Sulphur containing compounds
melting
Melts and chars with a smell of Carbohydrates may be present
burnt sugar
Produces coughing upon Benzoic acid, salicylic acid etc may be
charring present
Chars without melting Sulphanilic acid, starch, uric acid may
be present
Beilstein’s Test: Burns with green flame Urea, Chlorides, Bromides may be
Make one end of a copper wire in the present
form of a loop and heat it on a burner
till flame is no longer coloured. Cool Burns without green flame Flourides may be present
the wire and dip the loop in little of
the sample and ignite the loop again
in flame.
3. Test for Unsaturation
a. Action of KMnO4(Baeyers test): Decolourization of KMnO4 Unsaturated compounds may be
Sub (solid/Liquid) + Sodium present
carbonate solution + few drops of No Decolourization of KMnO4 Saturated compounds may be present
2% KMnO4 solution – Shake
vigorously
b. Action of Bromine Water (for Decolourization Unsaturated compounds may be
freely or sparingly water soluble present
compounds): No Decolourization Saturated compounds may be present
Sub (solid/Liquid) + Bromine water
dropwise – Shake vigorously
c. Action of Bromine Water (for Decolourization Unsaturated compounds may be
water insoluble compounds): present
Sub (solid/Liquid) + 2ml CCl4 or
CHCL3 solution dropwise with shaking No Decolourization Saturated compounds may be present
+ Bromine in CCl4 dropwise – Shake
vigorously.
4. Lassaigne’s Test (Elemental Analysis)
Place about a pea size of freshly cut sodium metal into a sodium fusion tube and heat the tube gently to melt the
sodium to a shining globule. Add a small quantity of the sample (solid/liquid) into the fusion tube. Heat the tube
carefully at first and then as strongly as possible until the bottom of the tube is glowing red, holding the tube at
this heat for about 2 min. Quickly plunge the hot tube in a china dish containing about 8 ml of distilled water
and cover the china dish immediately with a wire gauge. The tube crumbles into pieces and the mass comes out
and dissolves in water. Boil the contents of the china dish thoroughly, filter the contents and collect the filtrate
(which is also called Stock solution) in a test tube. Divide the filtrate into 3-4 portions and test each portion for
the elements separately.
Test Observation Inference
1. Test for Nitrogen:
a. Prussian Blue test Green or Blue colour Nitrogen present
Stock solution + FeSO4 solution – boil No Green or Blue colour Nitrogen absent
and cool. Add conc. H2SO4
2. Test for Sulphur:
a. Sodium nitroprusside test Pink colour Sulphur present
Stock solution + Sodium nitroprusside No Pink colour Sulphur absent
b. Lead acetate Test Black Ppt Sulphur present
Stock solution + Acetic Acid + 2 ml
No Black Ppt Sulphur absent
Lead acetate (5%)
3. Test for Halogens:
a. Silver Nitrate test White ppt, which freely Chlorine present
Stock solution + dil. HNO3 – heat, boil dissolves in 2 ml of ammonia
and reduce to half the volume + a few solution
drops of silver nitrate solution. Pale yellow ppt, which is Bromine present
difficult to dissolve in 2 ml of
ammonia solution
Yellow ppt, which is insoluble Iodine present
in 2 ml of ammonia solution
No Ppt Halogens absent
Test for Nitrogen:
6 NaCN + FeSO4  Na4[Fe(CN)6] + Na2SO4
Sodium cyanide Sod. Ferrocyanide

FeSO4  2Fe2(SO4)3

Na4[Fe(CN)6] + 2Fe2(SO4)3  Fe4[Fe(CN)6] + Na2SO4dil. H

Ferricferrocyanide
(Persian Blue)
 Test for Sulphur:
Na2S + Na2[Fe(CN)5NO]  Na4[Fe(CN)5NOS] + 2NaOH
Sod. nitroprusside Sod. Ferric sulphocyanide
(purple-violet colour)

Na2S + Pb(CH3COO)2  PbS + 2CH3COOH

Lead sulphide

Test for Halogens: Dil. HNO3

AgNO3 + NaCl  AgCl(s) + NaNO3
White ppt
2NH4OH
[Ag(NH3)2]+ Cl- + 2H2O
Freely water soluble
5. Solubility test:
a. Sub + Water Soluble Group I or II present
Sub + Ether Soluble Group I or II present
Low molecular weight compounds like
acids, esters or resorcinol etc. present
Insoluble Group II present
Sugars, amides (urea) present
b. Sub + Dil HCl Soluble Group III present
10, 20 or 30 Amine present
c. Sub + Dil NaOH Soluble Group IV present
Acids, Phenols or phenolic acids
present
If Nitrogen is Absent
d. Sub + Conc. H2SO4 (In a dry test Soluble Group V present
tube)
Insoluble Group VI present
If Nitrogen is Absent
If all the solubility tests failed and the compound contains Nitrogen, then it belongs to Group VII

V
 Solubility Test:

Substance (Solid/Liquid) + Solvent (Water (ether) : dil. HCl : dil. NaOH (NaHCO3) : Conc. H2SO4)

Don’t change the above order of solubility test. If the substance is soluble in earlier groups do not proceed further.

If N is absent If N is present
Soluble in water In Conc. H2SO4
(Use dry test tube)
Soluble in dil. HCl Soluble in dil. NaOH Soluble/Chemical Indifferent
Soluble in Ether changes like heat or
Insoluble in Ether Insoluble
(Use dry test tube) colour development,
ppt etc.
Group IV
Group I Group II Group III Group V Group VI Group VII
Sub + Sodium bicarbonate soln
Resorcinol Sugars 10 Amines Soluble Insoluble Aldehydes Hydrocarbons Amides
(solid) Acids Phenols
(special phenol) Glucose (solid) Aniline (liquid) Benzaldehyde Toluene (liquid) Benzamide (solid)
(liquid) Naphthalene (solid)
Salicylic acid o, m & p – Cresols
Alcohols Ortho and meta Benzoic acid (all liquids) Diphenyl(solid) Anilides
Ketones
Aldehydes toluidine (both solids)
Ketones and Acids (both liquids) Acetophenone Halogen Acetanilide (solid)
of Low molecular Urea (solid) (liquid) hydrocarbons Benzanilide (solid)
weight (special amide) Para toluidine
(solid) Benzophenone Chlorobenzene Nitro Compounds
Acetamide (solid) (solid) Bromobenzene
20 Amines Benzylchloride Nitrobenzene
Thiourea Methyl and Ethyl Alcohols (all liquid) (liquid)
Aniline Dinitrobenzene
(both liquids) Benzylalcohol (solid)
(liquid)
Nitrotoluene
30 Amines (liquid)
Esters
Dimethyl and Dinitrotoluene
diethyl Aniline Methyl and ethyl (liquid)
(both liquids) benzoate
Methylsalicylate
(all liquids)
 Test Observation Inference

6. Group Detection:
A Test for Group I: Low molecular weight compounds like Acids, Alcohols, Aldehydes, ketones, esters, phenols, etc
a. Test for Aldehydes: Red ppt Aldehydes or Ketones present
Sub + 2,4-dinitrophenol
b. Test for Alcohols: Effervescence Alcohol present
Sub + Sodium metal in a dry test tube
c. Test for Acids: Effervescence Acids present
Sub + NaHCO3 solution
d. Test for Esters: Pink colour disappears Esters present
Sub + NaOH solution + 1 drop of
phenolphthalein indicator
e. Test for Phenols: Violet colour, greenish purple Phenols present
Sub + Alcoholic FeCl3 solution colour, bluish purple colour
B Test for Group II: Sugars and Amides
Nitrogen absent-Sugars: Glucose- see aldehydes, under group V;
Nitrogen present-Urea/Thiourea,
a. Test for Sugars
i. Molisch Test: Violet ring at the junction of 2 Sugars present
Sub + Molisch’s reagent + 2 ml Conc. layers
H2SO4 along sides of the test tube.
ii. Fehling’s test: Brick Red colour Reducing Sugar present
Sub + Fehling’s reagent A and B –
warm on water bath
iii. Benedict’s Test: Orange colour Reducing Sugar present
Sub + Benedict’s reagent - warm on
water bath
iv. Barfoed’s Test: Red colour Monosaccharide present
Sub + Barfoed’s reagent - warm on
water bath
v. Rapid Furfural test: Violet Colour Glucose present
Sub + rapid Furfural reagent + Conc.
HCl – boil
b. Test for Amides:
i. Burn substance over an open flame Burns without soot and leaves Aliphatic compounds.
white residue Urea may be present.
ii. Sub + NaOH solutions (heat in a Smell of NH3 / Red litmus held Amides (urea) may be present.
dry test tube) on top of test tube turns blue.
 iii. Nitrous acid test Effervescence due to evolution Amides present
Dissolve substance in dil. HCl and add of Nitrogen
to solution of NaNO2 – Boil off Clear solution Aliphatic amides present
nitrogen and cool test tube.
White ppt Aromatic amides present
iv. Biuret test Pink, Violet or Blue colour Urea confirmed.
Place 0.2 g of Urea in a dry test tube
and heat until it melts and all NH3 has
evolved – and it resolidifies. Dissolve
the residue in few ml of water + 1 ml
of dil. NaOH solution and finally add
CuSO4 solution dropwise.
c. Test for Thiourea
Sub + Potassium ferricyanide + dil. Green colour changing to blue Thiourea present
Acetic acid – warm slightly
C Test for Group III: 10, 20 and 30 Amines
i. Sub + Acetyl chloride or Benzoyl Vigorous reaction (solid 10 and 20 Amines
chloride (in dry test tube) separates)
ii. Diazotization Test: a. Clear solution/Brown oil 10 Amines
Sub + dil. HCl till soluble – cool in ice obtained – further add ice
water. Add ice cold solution of NaNO2 cold -naphthol in NaOH
in water. solution - Orange Dye
b. Yellow oil separates 20 Amines
c. Red/Brown oil - further add 30 Amines
NaOH solution - green solid
separates
iii. Carbylamine or Isocyanide reaction: Carbylamine smell 10 amine (Aliphatic / Aromatic)
Sub + CHCl3 + NaOH solution – Boil No Carbylamine smell 20 Amines
continuously
D Test for Group IV: Acids and Phenols
Sub + NaHCO3 solution Compound dissolves with Carboxylic Acids may be present
Effervescence of CO2
No Effervescence Phenols present
a. Test for Acids: Salicylic acid, Cinnamic acid, Benzoic acid
Confirmatory test for Acids: (Esterification reaction)
Sub + 1 ml of Alcohol + Conc. H2SO4 Fruity odour due to ester Acid confirmed
(few drops) – heat for some time on formation
water bath, cool and pour in a china
dish containing water
i. Sub + Alcoholic FeCl3 Purple-Violet colour Phenolic acids – Salicylic acid present
No colour, but ppt Salicylic acid absent.
Benzoic acid/Cinnamic acid may be
present
 ii. Sub + Bromine water – dropwise Decolourisation Cinnamic acid
with shaking No Decolourisation Benzoic acid
iii. Fluorescein Test: Dark red colouration with Phthalic acid/succinic acid may be
0.2 g Sub + 0.2 g resorcinol – heat the green fluorescence present
mixture + drops of Conc. H2SO4 + 1 ml (fluorescence can be observed
of water – heat (to dissolve the by addition of reaction mixture
residue) and add excess of NaOH in to a beaker with 10ml water)
dropwise. Dark red colour with green Benzoic acid is present
fluorescence not obtained
b. Test for Phenols: Cresols, Resorcinol
i. Sub + Alcoholic FeCl3 Purple/Green/Violet colour Phenols or Cresols present
ii. Libermann’s Nitroso test: Green/Blue colour with water Phenolic compound confirmed
Add little of phenolic compound to
minute crystal of NaNO2 (sodium Red colour with dil. HCl
nitrite) in a dry test tube – Heat
gently for a minute, cool and add few
Green colour with dil. NaOH
drops of Conc. H2SO4 from the sides
iii. Phthalein Test: Different colours Phenolic compound confirmed
0.2 g Sub + 0.2 g Phthalic anhydride + Violet / pink colour Phenol
2-3 drops of Conc. H2SO4 (in a dry Intense violet/red o-cresol
test tube) – heat a min and cool –
Bluish purple m-cresol
add 1 ml of water then pour in dil.
Pink-red / light green p-cresol
NaOH solution
Red colour with green fluorescence Resorcinol
Greenish blue / dark green - naphthol
Permangnate colour -naphthol
No colour / no reaction Salicylic acid
E Test for Group V: Aldehydes, Ketones, Alcohols, Esters
a. Test for Aldehydes
i. Sub + 2,4-dinitrophenylhydrazine Precipitate Aldehyde/Ketone present
solution (2,4-DNP)(excess) – warm (red/Orange/Yellow)
if necessary
ii. Tollen’s Test: Silver mirror formed on the Aldehydes present (aromatic aldehyde
Sub + Tollen’s reagent (ammonical walls of the test tube/ grey- gives test)
AgNO3 soln) – warm on a water bath black ppt
No Silver mirror Ketones present
iii. Sub + Fehling’s solution (A+B) – Red ppt Aldehyde present
warm on a water bath (benzaldehyde does not give red ppt)
iv. Sub + Schiff’s reagent (shake well & Violet-purple/Magenta colour Aldehyde confirmed (glucose does not
observe the colour after 3-4 min) (Note: Light pink colour should be give pink colour)
considered as negative result)
b. Test for Ketones
i. Sub + 2,4-dinitrophenylhydrazine Precipitate Aldehyde/Ketone present
solution (excess) – warm if necessary (red/Orange)
 i. Tollen’s Test: No Silver mirror Ketones present
Sub + Tollen’s reagent (ammonical
AgNO3 soln) – warm on a water bath
ii. Sub + Fehling’s solution (A+B) – No Red ppt Ketone present
warm on a water bath
iii. Sub + Schiff’s reagent (shake well) No Violet-purple/Magenta Ketone present
colour
iv. Sub + freshly prepared Sodium Pink/Red colouration Ketone with methyl group(-CO-CH3)
nitroprusside solution – shake well (Acetophenone/Acetone)
+ dil. NaOH solution in excess
v. Sub + 0.2 g naphthalene (in a dry Surface of Sodium appears Benzophenone confirmed
test tube) – heat until molten + greenish-blue
small dry piece of Sodium – heat.
c. Test for Alcohols
ii. Sub + 2,4-dinitrophenylhydrazine No Red Precipitate Aldehyde/Ketone absent
solution (excess) – warm if necessary Alcohol may be present
iii. Sub + freshly cut shiny Sodium Vigorous reaction (brisk Alcohol present
metal (in a dry test tube) effervescence of hydrogen gas)

- after complete dissolution of sodium - Formation of hazy solution /

add little ether solid salt after addition of ether
iv. Esterification reaction: Fruity Odour Alcohol confirmed
Sub + Benzoic acid + Conc. H2SO4 (in
a dry test tube) boil for some time
and pour in a china dish containing
water or Na2CO3 soln.
v. Sub + Conc. H2SO4 (in a dry test Tube becomes hot and a white Benzyl alcohol confirmed.
tube) gelatinous product is obtained
d. Test for Esters
i. Sub + 2,4-dinitrophenylhydrazine No Red Precipitate Aldehyde/Ketone absent
solution (excess) – warm if Alcohol/Esters may be present
necessary
ii. Sub + Sodium metal (in a dry test No Reaction Alcohol absent
tube) Esters may be present
iii. Sub + dil. NaOH Solution + drop of Pink colour disappears Ester present
phenolphthalein – pink colour –
shake continuously for a few
minutes/heat on flame
iv. Hydroxamic acid test: Pink colour Ester present
Sub + 1 ml of methanolic
hydroxylamine hydrochloride +
methanolic KOH/NaOH – boil on a
water bath – cool and acidify with dil.
HCl + FeCl3 solution
F Test for Group VI: Hydrocarbons, Halogen hydrocarbons
a. Test for hydrocarbons
 i. Sub (In a dry test tube) + Conc. Clear solution Hydrocarbons present
H2SO4 – heat till a clear solution is (no oil layer/solid separates) (sulphonation takes place)
obtained – cool and pour in a
beaker of water
ii. Formalin test (Le Rosen test for Different colours like Red, Toluene, Benzene, Naphthalene
Aromatic compounds) Green etc. present
In a porcelain dish take 0.6 g of Sub
in CHCl3 + 4-5 drops of formaldehyde-
sulphuric acid reagent.
[Reagent: 5-6 drops of 37% HCHO +
5 ml of Conc. H2SO4. It should be
prepared freshly]
iii. Chloroform-Aluminium Test: Appearance of red, orange, blue Aromatic hydrocarbons confirmed
Heat strongly 0.2 g of AlCl3 in a test or green colour due to the
tube so that it sublimes and sticks on formation of triphenylmethane
the walls of the test tube. dyes.
Run down 2 ml of Sub in CHCl3 on
the sides of the test tube – note the
colour produced by contact of solution
of AlCl3
b.
Test for halogen hydrocarbons

i. Elemental Analysis (Lassaigne’s test) Halogen present. Halogen hydrocarbon

Chlorine/Bromine
ii. Sub + alcoholic AgNO3 solution – White ppt Halogen present in side chain
Warm
No white ppt Halogen present in nucleus
iii. Test for Alkyl/Aryl halides Yellow ppt Indicates arylhalides
Sub + 2 ml Conc. HNO3 + 2 ml Conc.
H2SO4 – warm gently for 3 mins and
pour in a beaker of water
G
Test for Group VII: Amides, Anilides, Nitro compounds

a.
Test for Amides
i. Sub + NaOH solution – heat Evolution of NH3 detected by Amide present
smell or red litmus turned blue
No smell of NH3 Amides absent
ii. Nitrous acid test: Effervescence due to evolution Amides present
- Place and dissolve little of of nitrogen
compound in dil. HCl and add to Clear solution Aliphatic amide present
solution of NaNO2
- Boil off nitrogen and cool the test
White ppt Aromatic amine present
tube
b. Test for Anilides
i. Sub + NaOH + CHCl3 – boil for Smell of carbylamine Anilide Present
some time
No Smell of carbylamines Anilide absent
 ii. Sub + Conc. HCl – boil for some Red/Orange dye Anilide confirmed
time till clear solution is obtained.
Dilute with water – cool + ice cold
NaNO2 solution. Finally add ice cold
-naphthol in NaOH in solution
dropwise
c. Test for Nitro Compounds
i. Sub + NaOH solution – boil No smell of NH3 Amides absent
ii. Sub + NaOH solution + CHCl3 – No smell of carbylamines Anilide absent
boil continuously for some time
iii. Sub + Conc. HCl + Tin pieces – Clear solution Nitro compound present
wait till reaction ceases – then boil - Further add ice cold -
till layer disappears – cool, filter, naphthol in NaOH in
dilute and add ice cold NaNO2 solution dropwise.
solution - Red/Orange dye
obtained
iv. Neutral Reduction: Grey/Black ppt Nitro compound present
Dissolve 0.1 g of sample in 2 ml (NO2 group present)
ethanol + 5 drops of CaCl2 solution +
pinch of Zinc dust and boil the
contents for 5 mins. Filter the solution
in a test tube containing 1 ml of
Tollen’s reagent
v. Test for Aromatic nitro compounds: Pink colour Dinitro compound
Sub + acetone + NaOH solution No pink colour Mononitro compound
 Derivative Preparation

Derivatizations are the synthetic procedures regarding ‘conversions’ of one simple common
organic compound into another compound that can be thoroughly characterized. After performing the
preliminary and elemental analysis, solubility tests, functional groups test and determination of
melting/boiling point, the student can propose a list of possible compounds for the given unknown
sample. These possible compounds may contain a number of structural differences; therefore the final
confirmation for the identity of the given unknown sample can be accomplished by preparation of a
suitable derivative of the given sample and noting its melting/boiling point.

Sr.
Procedure
No.
1. Urea Nitrate (For Urea)
To a saturated solution in water add Conc. Nitric acid – Shake well. Crystals of Urea nitrate separate.
2. Benzoate Derivative (For Alcohols/Phenols)
Place 0.5 g of sample in 2.5 ml of water in a test tube. To this add 2.5 ml of 10% NaOH, followed by by 0.3
ml of benzoyl chloride. Shake for several mins. (or boil on low heat). The odour of benzoyl chloride should
disappear. The mixture is poured into water and the product is recrystallized from alcohol.

(Caution: Benzoyl chloride is highly corrosive and irritating – Handle with care)

3. 2,4-Dinitrophenylhydrazone (For Aldehyde/Ketone)

Dissolve 0.1 g of aldehyde/ketone in 5 ml of alcohol. To this add 2 ml of 2,4-DNP reagent. Shake vigorously
and allow the resulting mixture to stand for some time at room temperature. Crystallization of 2,4-
dinitrophenylhydrazone usually occurs within 5-10 mins. The ppt is recrystallized from alcohol.
(2,4-DNP reagent: 0.4 g 2,4-DNP + 2 ml Conc.H2SO4 + 3 ml water – Shake well until 2,4-DNP is dissolved –
To this add 5 ml 95% alcohol)
4. Oxime Derivative (Aldehydes/Ketone)
Dissolve 0.8 g of hydroxylamine hydrochloride in 5 ml of water. Add 4 ml of 10% NaOH solution and 0.4 g of
unknown aldehyde/ketone (If sample is insoluble in water, add sufficient ethanol to give a clear solution).
Warm the mixture on a water bath for 10-15 mins and allow the product to stand in an ice bath so that
crystalline product is obtained from water or dilute ethanol.

5. Benzoate Derivative – Schotten-Baumann reaction (For 10/20/30 Amines, Phenols, Sulphonamide)

Dissolve 0.5 g of unknown compounds in 10 ml of 5% NaOH. Add 0.5 g of Benzoyl chloride with continuous
shaking for 20 mins – Allow to cool. The reaction mixture is again vigorously shaken for 15 mins – Ppt
obtained is filtered off and recrystallized in alcohol.

(Caution: Benzoyl chloride is highly corrosive and irritating – Handle with care)
6. Base Catalyzed Derivative (For Amides/Anilides/Imides/nitriles)
Reflux a mixture of 0.5 g unknown sample and 15 ml of NaOH for 15-20 mins. The aqueous solution is
allowed to cool in ice bath. Add conc. HCl drop-wise until the mixture becomes acidic to litmus. Filter the
solid carboxylic acid ppt. (If no ppt obtained extract the mixture thrice with 8 ml diethyl ether and pass the
combined extract over anhydrous magnesium sulphate and evaporate the ether at room temp to leave the acid
residue.)

7.

8.

9.

10.
11.

12.

13.

14.

15.

16.

17.

18.

19.

20.
 Physical Constants of Compounds and their derivatives
Name of the Name of the Name of the
Compound Derivative with Compound Derivative with Compound Derivative with
Structure Structure Structure
[M.P./B.P. (0C)] [M.P./B.P. (0C)] [M.P./B.P. (0C)]
[M.P./B.P. (0C)] [M.P./B.P. (0C)] [M.P./B.P. (0C)]
Acetic acid Phenylhydrazine Benzoic acid Phenylhydrazine Phthalic acid Amide [219]
B.P – 118 [129] M.P - 121 [167] M.P – 208 Anilide [251]
Amide [82] Amide [139]
Anilide [162]
Cinnamic acid Amide [153] Salicylic acid Amide [135] Acetylsalicylic acid Amide [135]
M.P - 133 Anilide [147] M.P – 158 Anilide [139] M.P – 135 Anilide [139]

Methyl acetate Amide [82] Ethyl acetate Amide [82] Methyl benzoate Amide [130]
B.P – 57 3,5- B.P – 77 3,5- B.P – 199 3,5-
Dinitrobenzoate Dinitrobenzoate Dinitrobenzoate
[108] [93] [108]

Ethyl benzoate Amide [130] Benzyl benzoate Amide [130] Methyl salicylate Amide [142]
B.P – 212 3,5- B.P – 323 3,5- B.P – 224 3,5-
Dinitrobenzoate Dinitrobenzoate Dinitrobenzoate
[93] [113] [108]

o-cresol p-Nitrobenzoate m-cresol p-Nitrobenzoate p-cresol p-Nitrobenzoate

M.P – 30 [94] M.P – 12 [90] M.P – 36 [98]
B.P -191 B.P -202 B.P -202

Phenol Benzoate [69] Resorcinol Benzoate [117] -naphthol Benzoate [56]

M.P- 30 M.P – 110 M.P – 94
B,P – 182

-naphthol Benzoate [107] Formaldehyde - Benzaldehyde 2,4-dinitrophenyl

M.P – 123 B.P - B.P – 179 hydrazone [237]
HCHO

Acetone 2,4-dinitrophenyl Acetophenone 2,4-dinitrophenyl Benzophenone 2,4-dinitrophenyl

B.P – 56 hydrazone [128] B.P – 202 hydrazone [250] M.P – 49 hydrazone [238]
B.P – 306
Methyl alcohol - Ethyl alcohol - Benzyl alcohol p-3,5-
B.P - B.P - B.P – 205 Dinitrobenzoate
CH3-OH C2H5-OH [113]

Acetic Acetanilide [114] Phthalic Anilide [170] Diethyl ether -

Anhydride Anhydride B.P – 34
B.P – 140 M.P – 132

Urea Nitrate [163] Thiourea Hydrochloride Benzamide Benzoic acid [122]

M.P – 132 M.P – 182 [136] M.P – 130

Aniline Acetamide [114] Nitroaniline Acetamide [155] Acetanilide p-bromo [167]

B.P – 183 M.P – 114 M.P – 114

Benzanilide Benzoic acid [122] Benzene 1,3 – Dinitro [90] Toluene 2,4-dinitro [71]
M.P – 160 B.P – 80 B.P – 111

Naphthalene 1-nitro [61] Nitrobenzene Acetamide [114] m-dinitrobenzene 2,4-dinitrophenol

M.P – 80 B.P – 211 Dinitro [91] M.P – 91 [114]

Chlorobenzene 2,4-dinitro [52] Bromobenzene 2,4-dinitro [75] Dichlorobenzene 2,4-dinitro [110]

B.P – 132 B.P – 156 B.P – 179
 Physical Constants

Melting Boiling
Sr. Sr.
Solids Point Liquids Point
No. No.
(M.P) ( C)
0
(B.P) ( C)
0

1 Resorcinol 110 1 Aniline 184

2 p-toluidine 44 2 o toluidine 199
3 Glucose 144 3 m-toluidine 202
4 Glucose hydrated 90 4 Methylaniline 192
5 Urea 132 5 Ethylaniline 204
6 Salicylic acid 158 6 Dimethylaniline 292
7 Cinnamic acid 133 7 Diethylaniline 215
8 Benzoic acid 120 8 Phenol 182
9 Benzophenone 40 9 o-cresol 191
10 Naphthalene 80 10 m-cresol 203
11 Diphenyl 70 11 p-cresol 202
12 p-dichlorobenzene 53 12 Benzaldehyde 179
13 Benzamide 128 13 Acetophenone 202
14 Acetanilide 114 14 Benzyl alcohol 206
15 Benzanilide 160 15 Methylbenzoate 199
16 Dinitrobenzene 90 16 Ethylbenzoate 213
17 Dinitrotoluene 72 17 Toluene 110
18 Thiourea 172 18 Chlorobenzene 132
19 o-nitrophenol 45 19 Bromobenzene 155
20 Diphenyl amine 54 20 o-dichlorobenzene 179
21 p-nitrophenol 114 21 Benzyl chloride 179
22 Benzophenone 49 22 Nitrobenzene 210
23 m-dinitrobenzene 90 23 o-nitrotoluene 222
24 Phthalic acid 208 24 n-butanol 118
25 -naphthol 94 25 Bromobenzene 156
26 Lactose 223 26 Benzene 80
27 Anthracene 240 27 Xylene 144
28 p-nitroaniline 148 28 Ethyl acetate 77
29 Sulphanilamide 165 29 Chloroform 61
30 Acetlysalicylic acid 135 30 Acetic acid 118