Chemical Tests

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Chemical tests test for fucntional groups and are vital in the organic lab

In CHEM 2274, the first test performed is the sodium fusion test, this test tests for
halides and nitrogen.

The following material is quoted from:

Supplement to Laboratory Manual

(Fall 2009) Hagen J. and Wood J.

 Amines
o Hinsburg Test
o Diazo Coupling Test
 Nitrile
o Hydrolysis
 Carboxylic Acid
o Nutralization equivalent
 Acid Chloride
o Silver Nitrate
 Ester
o Hydroxamate
 β-Dicarbonyl
o Ferric Chloride Complex

CHEM 2274 mandatory chemical test

  Halides and Nitrogen
o Sodium Fusion Test

Chemical Tests by functional group

 Alkenes and Alkynes
o Bromine Addition
o Bayer Test
 Aromatic Hydrocarbons
o Aluminum Chloride/Chloroform
 Halohydrocarbons
o Alcholoic Siver Nitrate Test
o Beilstein Flame Test
 Alcohols
o Ceric Ammonium Nitrate Test
o Lucas Test
o Chromic Acid Oxidation
 Phenols
o Ceric Ammonium Nitrate
o Ferric Chloride
 Aldehyde and Ketones
o 2,4-Dinitrophenylhydrazine
o Chromic Acid Oxidation
o Iodoform Formation
o Tollen's Test
o Schiff's Test

Alkenes and Alkynes

Bromine Addition
Add bromine and look for loss of bromine color
Bayer Test
Add potassium permanganate for loss of purple color

Aromatic Hydrocarbons
Aluminum Chloride/Chloroform
Add anhydrous aluminum chloride and look for bright colors indicating
electrophilic Qualitative Analysis of Organic Compounds.

The analysis and identification of unknown organic compounds constitutes a very important aspect
of experimental organic chemistry.

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.
Students should, however, consult the laboratory manual and Textbook of Practical Organic
Chemistry, A.I. Vogel (4th Edition).
Practical Notes
Before outlining the general scheme, one or two points of practical importance should be noted.

(a) Quantities of substance for tests. For most tests about 0.1 g solid or 0.1 - 0.2 mL (2 - 3
drops) of liquid material (NOT MORE) should be used.

(b) Reagents likely to be met within organic analysis are on the reagent shelves. Students are
advised to develop a general knowledge of the physical characteristics of common organic
compounds. If in doubt about the expected result of a test between a certain compound and a
reagent, carry out a trial test with a known compound and compare with the unknown.

(c) Quantities of substance derivatives. Students have wasted much time and material in the
past by taking too large a quantity of substance for preparation of a derivative. In general, 0.5
- 1 g (or 0.5 - 1 mL) of substance gives the most satisfactory results.

If a practical book instructs one to use larger quantities (3 - 4 g or more), the quantities
should be scaled down to 1 g or 1 mL of the unknown substance and corresponding quantities
of reagents should be used.
General Scheme of Analysis
A. Preliminary Tests

(a) Note physical characteristics - solid, liquid, colour and odour.

(b) Perform an ignition test (heat small amount on metal spatula) to determine whether the
compound is aliphatic or aromatic (i.e. luminous flame - aliphatic; sooty flame - aromatic).

B. Physical Constants

Determine the boiling point or melting point. Distillation is recommended in the case of
liquids (see Appendix 3). It serves the dual purpose of determining the b.p., as well as
purification of the liquid for subsequent tests.

C. Analysis for elements present

At C10 level, the elements present will be told to you, but read up the method.

D. Solubility tests

The solubility of the unknown in the following reagents provides very useful information. In
general, about 3 mL of the solvent is used with 0.1 g or 0.2 mL (2 - 3 drops) of the substance.
The class of compound may be indicated from the following table:

SOLUBILITY TABLE
REAGENT AND TEST CLASS GROUP OF COMPOUNDS

Soluble in cold or hot water. Neutral, acidic or

Lower members of series. Neutral, e.g.
(If the unknown is soluble do basic. (Test with litmus
alcohols; Acidic, e.g. acids, phenols; Basic,
NOT perform solubility tests or universal indicator
e.g. amines
below) paper)

Most amines (except III amines with only

Soluble in dil. HCl Basic
aromatic groups

Soluble in dil. NaOH Acidic Most acids, most phenols.

Soluble in NaHCO3 Strongly acidic Most carboxylic acids.

Hydrocarbons, nitrohydro-carbons, alkyl

Insoluble in water, acid and or aryl halides, esters and ethers. Higher
Neutral
alkali molecular weight alcohols, aldehydes and
ketones

E. Group Classification Tests

From the previous tests it is often possible to deduce the functional groups present in the
unknown compound. Consult i.r. spectra when available.

Individual tests are then performed to identify and confirm the functional groups present.

NOTE:
1. Students are strongly advised against carrying out unnecessary tests, since not only are they a
waste of time but also increase the possibility of error. Thus it is pointless to first test for alcohol or
ketone in a basic compound containing nitrogen! Instead tests for amines, etc. should be done on
such a compound.

2. A systematic approach cannot be overemphasised in group classification tests to avoid

confusion and error.

F. Consultation of Literature

Once the functional group has been identified, reference is made to tables in a book on
organic analysis, for assessing possibilities and for the preparation of suitable solid
derivatives.

It should be noted that whilst two substances with the same functional group may sometimes
have very similar b.p. or m.p., solid derivatives canusually be chosen from the literature, with
m.p. differences of about 10 (or more), which distinguish between the two possibilities.

Example:
COMPOUND B.P. DERIVATIVES (M.P.)
2,4-DNPH SEMICARBAZONE
Diethyl ketone 102 156 139
Methyl n-propyl ketone 102 144 112
G. Preparation of derivatives

The final characterisation of the unknown is made by the preparation of suitable solid
derivatives. The derivative should be carefully selected and its m.p. should preferably be
between 90 - 150 for ease of crystallisation and m.p. determination.

Preparation of one derivative should be attempted. The derivative should be purified by

recrystallisation, dried and the m.p. determined. Derivatives should be submitted correctly
labelled for assessment together with the record.

Recording of Results

The results should be recorded in a systematic manner. Results should be recorded in the
practical book at the time (not written up afterwards).

A record should be made of every test carried out, no matter whether a NEGATIVE
RESULT HAS BEEN OBTAINED.

Test, observation and inference should be given.

At the conclusion of the analysis a brief summary of results should be included, giving the
name, b.p. or m.p., and formula of the analysed compound.

Qualitative Analysis for Elements (for reference only)

In organic compounds the elements commonly occurring along with carbon and hydrogen,
are oxygen, nitrogen, sulphur, chlorine, bromine and iodine. The detection of these elements
depends upon converting them to water-soluble ionic compounds and the application of
specific tests.

Lassaigne's Sodium Fusion Test

C, H, O, N, S, X NaX
NaCN
-> Na2S
NaCNS
PROCEDURE

Place a piece of clean sodium metal, about the size of a pea into a fusion tube. Add a little of
the compound (50 mg or 2 - 3 drops).* Heat the tube gently at first, allowing any distillate
formed to drop back onto the molten sodium. When charring begins, heat the bottom of the
tube to dull redness for about three minutes and finally plunge the tube, while still hot, into a
clean dish containing cold distilled water (6 mL) and cover immediately with a clean wire
gauze.**

*For liquids it is better to first melt the sodium add the liquid drop by drop.

**CAUTION: The tube shatters, and any residual sodium metal reacts with water. Stir the
mixture, boil for 1 - 2 minutes, on a tripod and filter hot through a fluted paper.
The 'fusion' filtrate which should be clear and colourless, is used for the SPECIFIC TESTS
DESCRIBED BELOW:

1. To a portion (2 mL) of the 'fusion' filtrate add 0.2 g of powdered ferrous sulphate crystals.
Boil the mixture for a half a minute, cool and acidify by adding dilute sulphuric acid
dropwise. Formation of a bluish-green precipitate (Prussian blue) or a blue solution indicates
that the original substance contains nitrogen. If no precipitate appears, allow to stand for 15
minutes, filter and inspect filter paper.

2. SULPHUR (SULPHIDE)
To the cold 'fusion' filtrate (1 mL) add a few drops of cold, freshly prepared, dilute solution
of sodium nitroprusside. The latter may be prepared by adding a small crystal of the solid to 2
mL of water. Production of a rich purple colour indicates that the original substance contains
sulphur. This test is very sensitive. Only strong positive results are significant.

3. HALOGENS (HALIDES)
Acidify a portion (1 mL) of the 'fusion' filtrate with 2N nitric acid, and if nitrogen and/or
sulphur are present, boil for 1 - 2 minutes.* Cool and add aqueous silver nitrate (1 mL),
compare with a blank. Formation of a heavy, white or yellow precipitate of silver halide
indicates halogen. If a positive result is obtained: acidify the remaining portion of the 'fusion'
filtrate with dilute sulphuric acid, boil and cool. Add carbon tetrachloride (1 mL) and a few
drops of freshly prepared chlorine water. Shake the mixture.

(a) If the carbon tetrachloride layer remains colourless - indicates chlorine.

(b) If the carbon tetrachloride layer is brown - indicates bromine.

(c) If the carbon tetrachloride layer is violet - indicates iodine.

*If nitrogen and/or sulphur are also present, the addition of silver nitrate to the acidified
'fusion' solution will precipitate silver cyanide and/or silver sulphide in addition to the silver
halides. The removal of hydrogen cyanide and/or hydrogen sulphide is effected by boiling the
'fusion' solution. GROUP CLASSIFICATION TESTS

Some functional group tests are listed below. Students should refer to a practical text book for
details, and further information, e.g. Vogel.

Tests for unsaturation

1. Cold dilute potassium permanganate solution.
2. Solution of bromine in carbon tetrachloride.

Tests for compounds containing nitrogen

1. Amines
(a) Nitrous acid.
(b) Confirmatory tests.

2. Compounds which give amines or ammonia on acid or alkaline hydrolysis:

Amides, substituted amides, anilides, nitriles.
3. Compounds which give amines on reduction:
Nitro, nitroso, azo, hydrazo, nitriles.

Tests for compounds containing C, H and possibly oxygen

1. Carboxylic acids
Na2CO3 or NaHCO3 solution liberate carbon dioxide.

2. Phenols
(a) Sodium hydroxide solution (soluble). Insoluble in and no CO2 from NaHCO3 (except
when electron attracting groups present, e.g. 2,4-dinitrophenol).
(b) Ferric chloride solution.
(c) Bromine water.

3. Aldehydes and Ketones

(a) 2,4-dinitrophenylhydrazine (as Brady's reagent) for C=O.
(b) Iodoform test for CH3CO-.

4. Aldehydes only (reducing properties)

(a) Fehling's solution.
(b) Tollen's reagent (ammoniacal AgNO3 solution).
(c) Jones reagent.

5. Alcohols
(a) Lucas' reagent to distinguish I, II and III alcohols.
(b) Jones reagent.
(c) Metallic sodium (use dry liquid and dry tube).

6. Sugars
(a) Molisch's test.

7. Esters
(a) Hydroxamic acid test.
(b) Hydrolysis.

Write up of the identification of an unknown organic compound

Date......................................

Compound containing C, H (N, Hal, S)

Physical characteristics ...................... (solid, liquid, gas,

colour, odour, etc.)

Ignition test .............................. (aromatic or aliphatic)

Physical constant ........................ (boiling point or melting

point)
Solubility tests (in tabular form)

Group classification tests (in tabular form)

Test Observation Inference

From the above tests and observations the given compound is probably a
.........................(acid, phenol, aldehyde, etc.)

Consultation of literature (Possibilities) M.P. of derivative

(a)

(b)

(c)

Preparation of derivative (method of preparation)

Observed m.p. of derivative

Lit. m.p. of derivative

Result

Compound No. ........................ is ............................

(give formula)

TESTS FOR FUNCTIONAL GROUPS

I. UNSATURATED COMPOUNDS

Two common types of unsaturated compounds are alkenes and alkynes characterised by the
carbon-carbon double and triple bond, respectively, as the functional group. The two
common qualitative tests for unsaturation are the reactions of the compounds with (a)
bromine in carbon tetrachloride and (b) potassium permanganate.

(a) 2% Bromine in carbon tetrachloride

Dissolve 0.2 g (or 0.2 mL) of the compound in 2 mL of carbon tetrachloride or another
suitable solvent and add the solution dropwise to 2 ml of 2% bromine solution in carbon
tetrachloride and shake.

e.g.
Rapid disappearance of the bromine colour to give a colourless solution is a positive test for
unsaturation.

NOTE: The reagent is potentially dangerous. Keep it off your skin and clothes; protect
your eyes and nose. (b) 2% Aqueous potassium permanganate
Dissolve 0.2 g (or 0.2 mL) of the substance in 2 mL of water (acetone may also be used as
solvent). Add the potassium permanganate solution dropwise and observe the result.

e.g.

For a blank determination, count the number of drops added to 2 mL of acetone before the
colour persists. A significant difference in the number of drops required in the two cases is a
positive test for unsaturation.

II. COMPOUNDS CONTAINING NITROGEN

1. Amines
(a) Reaction with nitrous acid Dissolve the amine (0.5 mL) in concentrated acid (2.0 mL) and
water (3 mL) and cool the solution to 0 - 5 in an ice-bath for 5 minutes. Add a cold solution
(ice-bath) of sodium nitrite (0.5 g) in water (2.0 mL) from a dropper, with swirling of the test
tube, still keeping the mixture in the ice-bath.

AMINE REACTION

I aliphatic N2 evolved.
RNH2 + HNO2 -> ROH + N2 + H2O
__________________________________________________________________
I aromatic Diazonium salt is formed.
ArNH2 + HNO2 -> ArN=N+
Add the cold diazonium solution and with swirling
to a cold solution of 2-naphthol (0.2 g) in 5% NaOH
solution (2 mL). An orange-red azo dye is formed.
__________________________________________________________________
II aliphatic and Yellow oily nitrosamines are generally formed.
II aromatic R2NH + HNO2 -> R2N-NO
__________________________________________________________________
III aliphatic No visible reaction.
__________________________________________________________________
III aromatic Dialkylanilines yield green solid p-nitroso
compounds (if p-position unsubstituted).
__________________________________________________________________

(b) Reaction with benzenesulphonyl chloride

Benzenesulphonyl chloride reacts with primary and secondary but not with tertiary amines to yield
substituted sulphonamides.
e.g. (a) C6H5SO2Cl + H-NHR + NaOH -> C6H5SO2NHR + NaCl + H2O
(b) C6H5SO2Cl + H-NR2 + NaOH -> C6H5SO2NR2 + NaCl + H2O
The substituted sulphonamide formed from a primary amine dissolves in the alkali medium whilst
that produced from a secondary amine is insoluble in alkali.

Place 0.5 mL (or 0.5 g) of the compound, 15 - 10 mL of 5% NaOH and 1 mL of

benzenesulphonyl chloride in a test tube, stopper the tube and shake until the odour of the
sulphonyl chloride has disappeared. The solution must be kept alkaline (if no reaction has
occurred, the substance is probably a tertiary amine).

If a precipitate appears in the alkaline solution, dilute with about 10 mL of water and shake; if
the precipitate does not dissolve, a secondary amine is indicated.

If there is no precipitate, acidify it cautiously to congo red with concentrated hydrochloric

acid (added dropwise): a precipitate is indicative of a primary amine.

2. Amides R-CO-NH2
Simple primary amides can be decomposed by boiling with alkali and thereby evolving
ammonia.

e.g. CH3-CO-NH2 + NaOH -> CH3-CO2- Na+ + NH3

Boil 0.5 g of the compound with 5 mL of 10% sodium hydroxide solution and observe whether
ammonia is evolved.

III. COMPOUNDS CONTAINING C, H AND POSSIBLY OXYGEN

1. Carboxylic acids - test with 5% aq. NaHCO3

R-CO2H + NaHCO3 -> R-CO2- Na+ + CO2 + H2O

Sodium hydrogen carbonate reacts with carboxylic acids to give the sodium salt of the acid and
liberates carbon dioxide. If the acid is insoluble in water and the reaction is sluggish dissolve the acid
in methanol and add carefully to a saturated sodium hydrogen carbonate solution, when a vigorous
effervescence will be observed.

2. Phenols [Soluble in NaOH and produce no CO2 from NaHCO3]

(a) Bromine water
Phenols are generally highly reactive towards electrophilic reagents and are readily
brominated by bromine water. e.g.

Dissolve or suspend about 0.05 g of the compound in 2 mL of dilute hydrochloric acid and
add bromine water dropwise until the bromine colour remains. A white precipitate of the
bromophenol may form. Solid bromophenol derivatives can be used for the confirmation of
the structure of a phenol (cf the preparation of derivatives).

(b) Ferric chloride test

Most phenols react with iron (III) chloride to form coloured complexes. The colours vary -
red, purple, blue or green - depending on various factors, e.g. the phenolic compound used,
the solvent, concentration. Since some phenols do not give colours, a negative test must not
be taken as significant without supporting information.

Dissolve 0.05 g of the compound in 2 mL water (or a mixture of water and ethanol if the
compound is not water-soluble) and add an aqueous solution of ferric chloride dropwise.
Observe any colour changes which may occur.

3. Aldehydes and ketones

(a) 2,4-Dinitrophenylhydrazine (as Brady's reagent) A test for the carbonyl group (C=O) in
aldehydes and ketones. 2,4-Dinitrophenylhydrazine gives sparingly soluble yellow or red 2,4-
dinitrophenylhydrazones with aldehydes and ketones.

Add 3 mL of the reagent to 2 drops of the compound in a test tube and shake. If no precipitate
forms immediately, warm and allow to stand for 5 - 10 minutes. A crystalline precipitate
indicates the presence of a carbonyl compound.

The bench reagent is very dilute and is intended for qualitative tests only and should not be
used in the preparation of a derivative for identification purposes. (b) Iodoform test for
CH3CO-
Dissolve 0.1 g (or 5 drops) of the compound in 2 mL of water; if it is insoluble in water add
sufficient dioxan to produce a homogeneous solution. Add 2 mL of 5% NaOH solution and
then introduce the potassium iodide - iodine reagent dropwise with shaking until a definite
dark colour of iodine persists. Allow to stand for 2 - 3 minutes; if no iodoform separates at
room temperature, warm the test tube in a beaker of water at 60 . Add a few more drops of
the iodine reagent if the faint iodine colour disappears. Continue the addition of the reagent
until a dark colour is not discharged after 2 minutes heating at 60 . Remove the excess of
iodine by the addition of a few drops of dilute sodium hydroxide solution with shaking, dilute
with an equal volume of water, and allow to stand for 10 minutes. The test is positive if a
yellow precipitate of iodoform is deposited. Filter off the yellow precipitate, dry upon pads of
filter paper and determine the m.p. Iodoform melts at 120 (it can be recrystallised from
methanol- water).

The reaction is given by acetaldehyde and simple methyl ketones. Alcohols containing the
CH3CHROH group will be oxidised under the reaction conditions and also give a positive
test.
4. Aldehydes only (reducing properties).
(a) Fehling's solution
Aldehydes reduce Fehling's solution to yellow or red copper (I) oxide.

Preparation of the reagent: Mix equal volumes of Fehling's solution solution I (aqueous
alkaline potassium tartrate) and Fehling's solution II (copper sulphate solution).

Add 2 drops (or 0.05 g) of the compound and 2 - 3 drops of the reagent and heat on a boiling
water bath for 3 - 4 minutes.

The test is positive for aliphatic aldehydes, but is often indecisive for aromatic aldehydes
where Jones' Reagent is often useful (see 5).

(b) Tollen's reagent (Ammonical silver nitrate solution)

Aldehydes are readily oxidised to carboxylic acids and will reduce Tollen's reagent to
produce a silver mirror on the inside of a clean test tube.

FIRST clean up a test tube with a little hot nitric acid (fume cupboard) and rinse with distilled
water.

Preparation of the reagent: To 1 mL of silver nitrate solution add a few drops of sodium
hydroxide. Then add dilute ammonium hydroxide dropwise until the precipitate just
dissolves.

Add 2 - 3 drops of the compound in methanol to 2 - 3 mL of Tollen's solution contained in a

very clean test tube. If no reaction takes place in the cold, warm gently in a water bath.

CAUTION: After the test, pour the contents of the test tube into the sink and wash the test
tube with dilute nitric acid. Any silver fulminate present, which is highly explosive when dry,
will be destroyed.

(c) Jones Reagent (See section under alcohols).

5. Alcohols
The tests for the hydroxyl group not only detect the presence of the group, but may also
indicate whether it is primary, secondary or tertiary.

(a) Jones Reagent (CrO3-H2SO4 in H2O)

This reagent distinguishes primary and secondary alcohols from tertiary alcohols; the test is
based on the much greater resistance to oxidation of tertiary alcohols compared to the other
two types. Aldehydes also give a positive test.

Place 1 mL of acetone in a test tube and dissolve one drop of a liquid or ca 10 mg of a solid
alcohol or aldehyde in it. Add one drop of the reagent to the acetone solution and shake the
tube to mix the contents. Primary and secondary alcohols react within two seconds as
indicated by the disappearance of the orange colour of the reagent and the formation of a
green or blue-green precipitate or emulsion.
Tertiary alcohols do not react even after 3 minutes.

(I) RCH2OH -> RCHO -> RCO2H

 (II) R2CHOH -> R2C=O

(III) R3COH -> no visible reaction.

(b) Lucas' Reagent [ZnCl2 - conc. HCl]

This reagent converts alcohols into the corresponding alkyl chlorides. Zinc chloride (a Lewis
acid) increases the reactivity of alcohols towards acid. The test depends on the rate of
reaction of primary, secondary, and tertiary alcohols with the reagent at room temperature.

(I) RCH2OH -> no reaction at room temperature.

(II) R2CHOH -> R2CHCl + H2O (1 hour or maybe longer)

(III) R3COH -> R3CCl + H2O (immediately)

To 1 mL of the alcohol in a small test tube add 6 mL of Lucas' reagent at room temperature. Close
the tube with a cork, shake and allow to stand.

(i) Primary alcohols - the aqueous phase remains clear (except allyl alcohol - droplets after 7
minutes).

(ii) Secondary alcohols - very slow reaction (~ 1 hour or maybe longer) when droplets of
alkyl chloride may be seen.

(iii) Tertiary alcohols - very fast reaction and droplets of the alkyl chloride formed almost
immediately.

6. Sugars, Carbohydrates
Molisch's Test
This is a general test for carbohydrates. Dissolve 20 - 30 mg of the compound in 2 mL water
and add 0.5 mL of the reagent (a 20% solution of 2-naphthol in ethanol). Pour 2 mL of
concentrated sulphuric acid from a dropper carefully down the side of the tube so that the
acid forms a layer beneath the aqueous solution without mixing with it. A red colouration,
changing to dark purple forms at the interface. Carry out a second test on a blank solution.

7. Esters
Hydroxamic acid test

R-CO-OR' + H2N-OH -> R-CO-NH-OH + R'-OH

Esters react with hydroxylamine in the presence of sodium hydroxide to form the sodium salt
of the corresponding hydroxamic acid. On acidification and addition of ferric chloride the
magenta-coloured iron (III) complex of the hydroxamic acid is formed.

It is always advisable to ensure that an unknown compound does not give a colour with iron
(III) chloride before carrying out the hydroxamic acid test.

Procedure for hydroxamic acid test

(a) Ferric chloride test
Dissolve a drop or a few small crystals of the compound in 1 mL of 95% ethanol (rectified
spirit) and add 1 mL of M hydrochloric acid. Note the colour produced when 1 drop of 5%
iron (III) chloride is added to the solution. If a pronounced violet, blue, red or orange colour
is produced, the hydroxamic acid test described below is NOT APPLICABLE.

(b) Hydroxamic acid test

Mix 1 drop or several small crystals (ca 0.05 g) of the compound with 1 mL of 0.5 M
hydroxylamine hydrochloride in 95% ethanol and add 0.2 mL of 6 M aqueous sodium
hydroxide. Heat the mixture to boiling and after the solution has cooled slightly add 2 mL of
M hydrochloric acid. If the solution is cloudy, add 2 mL of 95% ethanol. Observe the colour
produced when 1 drop of 5% iron (III) chloride solution is added. If the resulting colour does
not persist, continue to add the reagent dropwise until the observed colour pervades the entire
solution. Usually only 1 drop of the iron (III) chloride solution is necessary. Compare the
colour with that produced in test (a). A positive test will be a distinct burgundy or magenta
colour as compared with the yellow colour observed when the original compound is tested
with iron (III) chloride solution in the presence of acid. It is often advisable to conduct in
parallel the test with, say, ethyl acetate, to ensure that the conditions for this test are correct.

THE PREPARATION
ORGANIC OF DERIVATIVES OF
COMPOUNDS
The preliminary examination and group classification tests indicate the particular class (functional
group) to which an unknown organic compound may belong. Further characterisation and
identification depends on the selection and preparation of a suitable solid derivative and accurate
determination of its melting point (best, between 90 - 150 ).

The following table lists some of the classes of organic compounds and a selection of
derivatives that may be prepared to characterise them. Check with the tables of melting points
in Vogel which derivatives are most suitable for the characterisation of your particular
compound.

CLASS OF COMPOUND DERIVATIVES

1. ALCOHOLS 3,5-dinitrobenzoate

2. PHENOLS benzoate, acetate, bromo-derivative

3. ALDEHYDES AND KETONES semicarbazone, 2,4-dinitrophenyl-hydrazone, oxime

4. ACIDS anilide, amide, p-toluidide.

5. AMINES benzoyl, acetyl and sulphonamide derivatives

METHODS FOR THE PREPARATION OF DERIVATIVES

ALCOHOLS

(i) 3,5-Dinitrobenzoates
3,5-Dinitrobenzoyl chloride is usually partially hydrolysed and should be prepared in the pure
state by heating gently a mixture of 3,5-dinitrobenzoic acid (1 g) and phosphorus
pentachloride (1.5 g) in a dry test tube, until it liquifies (5 min).* The liquid is poured on a
dry watch glass and allowed to solidify. The phosphoryl chlorides are removed by pressing
the solid with a spatula on a wad of filter paper. The residual acid chloride is suitable for
immediate use in the preparation of the derivatives.

*Work under fume hood. Fumes are irritating to the eyes and nose.

The 3,5-dinitrobenzoyl chloride is mixed with the alcohol (0.5 - 1 mL) in a loosely corked
dry test tube and heated on a steam bath for about 10 min. Secondary and tertiary alcohols
require up to 30 min. On cooling add 10 mL sodium hydrogen carbonate solution, stir until
the ester crystallises out, and filter at the pump. Wash with a little carbonate solution, water
and suck dry. Recrystallise from the minimum hot ethanol or light petroleum. Cool slowly to
avoid the formation of oily droplets of your ester.

PHENOLS

(i) Benzoates (Schötten-Baumann method).

To the phenol (0.5 g) is added 5% sodium hydroxide (10 mL) in a well-corked boiling tube or
a small conical flask. Benzoyl chloride (2 mL) is added in small quantities at a time, and the
mixture shaken vigorously with occasional cooling under the tap or in ice-water. After 15
min the solid benzoate separates out: the solution should be alkaline at the end of the
reaction; if not alkaline, or if the product is oily, add a solid pellet of sodium hydroxide and
shake again. Collect the benzoate, wash thoroughly with cold water, and recrystallise from
alcohol or light petroleum.

(ii) Acetates
Acetates of many simple phenols are liquids; however, this is a suitable derivative for
polyhydric and substituted phenols. The phenol (0.5 g) is dissolved in 10% sodium hydroxide
solution and an equal quantity of crushed ice is added, followed by acetic anhydride (2 mL).
The mixture is vigorously shaken in a stoppered test tube until the acetate separates. The
product is filtered and recrystallised from alcohol.

(iii) Bromo derivatives

The phenol (0.3 g) is suspended in dilute hydrochloric (10 mL) and bromine water added
dropwise until no more decolourisation occurs. The bromo derivative which precipitates out
is filtered off and recrystallised from alcohol.

ALDEHYDES AND KETONES

(i) Semicarbazones
Dissolve semicarbazide hydrochloride (1 g) and sodium acetate (1.5 g) in water (8 - 10 mL),
add the aldehyde or ketone (0.3 mL) and shake. Shake the mixture for a few minutes and then
cool in ice-water. Filter off the crystals, wash with a little cold water and recrystallise from
methanol or ethanol.

(ii) 2,4-Dinitrophenylhydrazones
Suspend 0.25 g of 2,4-dinitrophenylhydrazine in 5 mL of methanol and add 0.5 mL of
concentrated sulphuric acid cautiously. Filter the warm solution and add a solution of 0.2 g of
the carbonyl compound in 1 mL of methanol. Recrystallise the derivative from methanol,
ethanol or ethyl acetate.
(iii) Oximes
Hydroxylamine hydrochloride (0.5 g) is dissolved in water (2 mL). 10% sodium hydroxide (2
mL) and the carbonyl compound (0.2 - 0.3 g) dissolved in alcohol (1 - 2 mL) are added, the
mixture warmed on a steam bath for 10 min and then cooled in ice. Crystallisation is induced
by scratching the sides of the test tube with a glass rod. The oximes may be crystallised from
alcohol.

ACIDS

(i) Amides, anilides and p-toluidides

The acid (0.5 g) is refluxed with thionyl chloride (2 - 3 mL) in a fume cupboard for about 30
mins.* It is advisable to place a plug of cotton wool in the top of the reflux condenser to
exclude moisture. The condenser is removed and the excess of thionyl chloride is distilled off
(b.p. 78 ). The acid chloride thus produced is treated with concentrated ammonia solution (5
mL) or aniline (0.5 - 1 mL) or p-toluidine (0.5 - 1 g), when the solid derivative separates out.
It is collected and recrystallised from alcohol adding decolourising charcoal if found
necessary.

*Alternately use PCl5 to form the acid chloride.

AMINES

(i) Acetyl derivatives (acetamides)

Reflux gently in a small dry flask under a dry condenser the amine (1 g) with acetic
anhydride (3 mL) for 15 min. Cool the reaction mixture and pour into 20 mL cold water. Boil
to decompose the excess acetic anhydride. Cool and filter by suction the insoluble derivative.
Recrystallise from ethanol.

(ii) Benzoyl derivatives (benzamides)

Suspend 1 g of the amine in 20 mL of 5% aqueous sodium hydroxide in a well-corked flask,
and add 2 mL benzoyl chloride (fume hood!), about 0.5 mL at a time, with constant shaking.
Shake vigorously for 5 - 10 min until the odour of the benzoyl chloride has disappeared.
Ensure that the mixture remains alkaline. Filter off the solid derivative, wash with a little cold
water and recrystallise from ethanol.

(iii) Benzenesulphonamides
To 1 g of the amine in 20 mL of 5% sodium hydroxide solution in a well-corked flask add 1
mL benzenesulphonyl chloride (fume hood!). Shake the mixture until the odour of the
sulphonyl chloride disappears. Check that the solution is alkaline. Acidify if necessary to
obtain the precipitated derivative. Concentrated hydrochloric acid added dropwise should be
used. Filter the product, wash with a little cold water and suck dry. Recrystallise from
ethanol.
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Created and maintained by Prof. Robert J. Lancashire,

The Department of Chemistry, University of the West Indies,
Mona Campus, Kingston 7, Jamaica.

Created March 1997. Links checked and/or last modified 11th December 2005.
URL http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt25.html
Qualitative Analysis of Organic Compounds.
The analysis and identification of unknown organic compounds constitutes a very important aspect
of experimental organic chemistry.

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.

Students should, however, consult the laboratory manual and Textbook of Practical Organic
Chemistry, A.I. Vogel (4th Edition).
Practical Notes
Before outlining the general scheme, one or two points of practical importance should be noted.

(a) Quantities of substance for tests. For most tests about 0.1 g solid or 0.1 - 0.2 mL (2 - 3
drops) of liquid material (NOT MORE) should be used.

(b) Reagents likely to be met within organic analysis are on the reagent shelves. Students are
advised to develop a general knowledge of the physical characteristics of common organic
compounds. If in doubt about the expected result of a test between a certain compound and a
reagent, carry out a trial test with a known compound and compare with the unknown.

(c) Quantities of substance derivatives. Students have wasted much time and material in the
past by taking too large a quantity of substance for preparation of a derivative. In general, 0.5
- 1 g (or 0.5 - 1 mL) of substance gives the most satisfactory results.

If a practical book instructs one to use larger quantities (3 - 4 g or more), the quantities
should be scaled down to 1 g or 1 mL of the unknown substance and corresponding quantities
of reagents should be used.
General Scheme of Analysis
A. Preliminary Tests

(a) Note physical characteristics - solid, liquid, colour and odour.

(b) Perform an ignition test (heat small amount on metal spatula) to determine whether the
compound is aliphatic or aromatic (i.e. luminous flame - aliphatic; sooty flame - aromatic).

B. Physical Constants

Determine the boiling point or melting point. Distillation is recommended in the case of
liquids (see Appendix 3). It serves the dual purpose of determining the b.p., as well as
purification of the liquid for subsequent tests.
C. Analysis for elements present

At C10 level, the elements present will be told to you, but read up the method.

D. Solubility tests

The solubility of the unknown in the following reagents provides very useful information. In
general, about 3 mL of the solvent is used with 0.1 g or 0.2 mL (2 - 3 drops) of the substance.
The class of compound may be indicated from the following table:

SOLUBILITY TABLE
REAGENT AND TEST CLASS GROUP OF COMPOUNDS

Soluble in cold or hot water. Neutral, acidic or

Lower members of series. Neutral, e.g.
(If the unknown is soluble do basic. (Test with litmus
alcohols; Acidic, e.g. acids, phenols; Basic,
NOT perform solubility tests or universal indicator
e.g. amines
below) paper)

Most amines (except III amines with only

Soluble in dil. HCl Basic
aromatic groups

Soluble in dil. NaOH Acidic Most acids, most phenols.

Soluble in NaHCO3 Strongly acidic Most carboxylic acids.

Hydrocarbons, nitrohydro-carbons, alkyl

Insoluble in water, acid and or aryl halides, esters and ethers. Higher
Neutral
alkali molecular weight alcohols, aldehydes and
ketones

E. Group Classification Tests

From the previous tests it is often possible to deduce the functional groups present in the
unknown compound. Consult i.r. spectra when available.

Individual tests are then performed to identify and confirm the functional groups present.

NOTE:
1. Students are strongly advised against carrying out unnecessary tests, since not only are they a
waste of time but also increase the possibility of error. Thus it is pointless to first test for alcohol or
ketone in a basic compound containing nitrogen! Instead tests for amines, etc. should be done on
such a compound.

2. A systematic approach cannot be overemphasised in group classification tests to avoid

confusion and error.
F. Consultation of Literature

Once the functional group has been identified, reference is made to tables in a book on
organic analysis, for assessing possibilities and for the preparation of suitable solid
derivatives.

It should be noted that whilst two substances with the same functional group may sometimes
have very similar b.p. or m.p., solid derivatives canusually be chosen from the literature, with
m.p. differences of about 10 (or more), which distinguish between the two possibilities.

Example:
COMPOUND B.P. DERIVATIVES (M.P.)
2,4-DNPH SEMICARBAZONE
Diethyl ketone 102 156 139
Methyl n-propyl ketone 102 144 112
G. Preparation of derivatives

The final characterisation of the unknown is made by the preparation of suitable solid
derivatives. The derivative should be carefully selected and its m.p. should preferably be
between 90 - 150 for ease of crystallisation and m.p. determination.

Preparation of one derivative should be attempted. The derivative should be purified by

recrystallisation, dried and the m.p. determined. Derivatives should be submitted correctly
labelled for assessment together with the record.

Recording of Results

The results should be recorded in a systematic manner. Results should be recorded in the
practical book at the time (not written up afterwards).

A record should be made of every test carried out, no matter whether a NEGATIVE
RESULT HAS BEEN OBTAINED.

Test, observation and inference should be given.

At the conclusion of the analysis a brief summary of results should be included, giving the
name, b.p. or m.p., and formula of the analysed compound.

Qualitative Analysis for Elements (for reference only)

In organic compounds the elements commonly occurring along with carbon and hydrogen,
are oxygen, nitrogen, sulphur, chlorine, bromine and iodine. The detection of these elements
depends upon converting them to water-soluble ionic compounds and the application of
specific tests.

Lassaigne's Sodium Fusion Test

C, H, O, N, S, X NaX
NaCN
-> Na2S
NaCNS
PROCEDURE

Place a piece of clean sodium metal, about the size of a pea into a fusion tube. Add a little of
the compound (50 mg or 2 - 3 drops).* Heat the tube gently at first, allowing any distillate
formed to drop back onto the molten sodium. When charring begins, heat the bottom of the
tube to dull redness for about three minutes and finally plunge the tube, while still hot, into a
clean dish containing cold distilled water (6 mL) and cover immediately with a clean wire
gauze.**

*For liquids it is better to first melt the sodium add the liquid drop by drop.

**CAUTION: The tube shatters, and any residual sodium metal reacts with water. Stir the
mixture, boil for 1 - 2 minutes, on a tripod and filter hot through a fluted paper.

The 'fusion' filtrate which should be clear and colourless, is used for the SPECIFIC TESTS
DESCRIBED BELOW:

1. To a portion (2 mL) of the 'fusion' filtrate add 0.2 g of powdered ferrous sulphate crystals.
Boil the mixture for a half a minute, cool and acidify by adding dilute sulphuric acid
dropwise. Formation of a bluish-green precipitate (Prussian blue) or a blue solution indicates
that the original substance contains nitrogen. If no precipitate appears, allow to stand for 15
minutes, filter and inspect filter paper.

2. SULPHUR (SULPHIDE)
To the cold 'fusion' filtrate (1 mL) add a few drops of cold, freshly prepared, dilute solution
of sodium nitroprusside. The latter may be prepared by adding a small crystal of the solid to 2
mL of water. Production of a rich purple colour indicates that the original substance contains
sulphur. This test is very sensitive. Only strong positive results are significant.

3. HALOGENS (HALIDES)
Acidify a portion (1 mL) of the 'fusion' filtrate with 2N nitric acid, and if nitrogen and/or
sulphur are present, boil for 1 - 2 minutes.* Cool and add aqueous silver nitrate (1 mL),
compare with a blank. Formation of a heavy, white or yellow precipitate of silver halide
indicates halogen. If a positive result is obtained: acidify the remaining portion of the 'fusion'
filtrate with dilute sulphuric acid, boil and cool. Add carbon tetrachloride (1 mL) and a few
drops of freshly prepared chlorine water. Shake the mixture.

(a) If the carbon tetrachloride layer remains colourless - indicates chlorine.

(b) If the carbon tetrachloride layer is brown - indicates bromine.

(c) If the carbon tetrachloride layer is violet - indicates iodine.

*If nitrogen and/or sulphur are also present, the addition of silver nitrate to the acidified
'fusion' solution will precipitate silver cyanide and/or silver sulphide in addition to the silver
halides. The removal of hydrogen cyanide and/or hydrogen sulphide is effected by boiling the
'fusion' solution. GROUP CLASSIFICATION TESTS

Some functional group tests are listed below. Students should refer to a practical text book for
details, and further information, e.g. Vogel.
Tests for unsaturation
1. Cold dilute potassium permanganate solution.
2. Solution of bromine in carbon tetrachloride.

Tests for compounds containing nitrogen

1. Amines
(a) Nitrous acid.
(b) Confirmatory tests.

2. Compounds which give amines or ammonia on acid or alkaline hydrolysis:

Amides, substituted amides, anilides, nitriles.

3. Compounds which give amines on reduction:

Nitro, nitroso, azo, hydrazo, nitriles.

Tests for compounds containing C, H and possibly oxygen

1. Carboxylic acids
Na2CO3 or NaHCO3 solution liberate carbon dioxide.

2. Phenols
(a) Sodium hydroxide solution (soluble). Insoluble in and no CO2 from NaHCO3 (except
when electron attracting groups present, e.g. 2,4-dinitrophenol).
(b) Ferric chloride solution.
(c) Bromine water.

3. Aldehydes and Ketones

(a) 2,4-dinitrophenylhydrazine (as Brady's reagent) for C=O.
(b) Iodoform test for CH3CO-.

4. Aldehydes only (reducing properties)

(a) Fehling's solution.
(b) Tollen's reagent (ammoniacal AgNO3 solution).
(c) Jones reagent.

5. Alcohols
(a) Lucas' reagent to distinguish I, II and III alcohols.
(b) Jones reagent.
(c) Metallic sodium (use dry liquid and dry tube).

6. Sugars
(a) Molisch's test.

7. Esters
(a) Hydroxamic acid test.
(b) Hydrolysis.

Write up of the identification of an unknown organic compound

Date......................................

Compound containing C, H (N, Hal, S)

Physical characteristics ...................... (solid, liquid, gas,

colour, odour, etc.)

Ignition test .............................. (aromatic or aliphatic)

Physical constant ........................ (boiling point or melting

point)

Solubility tests (in tabular form)

Group classification tests (in tabular form)

Test Observation Inference

From the above tests and observations the given compound is probably a
.........................(acid, phenol, aldehyde, etc.)

Consultation of literature (Possibilities) M.P. of derivative

(a)

(b)

(c)

Preparation of derivative (method of preparation)

Observed m.p. of derivative

Lit. m.p. of derivative

Result

Compound No. ........................ is ............................

(give formula)

TESTS FOR FUNCTIONAL GROUPS

I. UNSATURATED COMPOUNDS

Two common types of unsaturated compounds are alkenes and alkynes characterised by the
carbon-carbon double and triple bond, respectively, as the functional group. The two
common qualitative tests for unsaturation are the reactions of the compounds with (a)
bromine in carbon tetrachloride and (b) potassium permanganate.
(a) 2% Bromine in carbon tetrachloride
Dissolve 0.2 g (or 0.2 mL) of the compound in 2 mL of carbon tetrachloride or another
suitable solvent and add the solution dropwise to 2 ml of 2% bromine solution in carbon
tetrachloride and shake.

e.g.

Rapid disappearance of the bromine colour to give a colourless solution is a positive test for
unsaturation.

NOTE: The reagent is potentially dangerous. Keep it off your skin and clothes; protect
your eyes and nose. (b) 2% Aqueous potassium permanganate
Dissolve 0.2 g (or 0.2 mL) of the substance in 2 mL of water (acetone may also be used as
solvent). Add the potassium permanganate solution dropwise and observe the result.

e.g.

For a blank determination, count the number of drops added to 2 mL of acetone before the
colour persists. A significant difference in the number of drops required in the two cases is a
positive test for unsaturation.

II. COMPOUNDS CONTAINING NITROGEN

1. Amines
(a) Reaction with nitrous acid Dissolve the amine (0.5 mL) in concentrated acid (2.0 mL) and
water (3 mL) and cool the solution to 0 - 5 in an ice-bath for 5 minutes. Add a cold solution
(ice-bath) of sodium nitrite (0.5 g) in water (2.0 mL) from a dropper, with swirling of the test
tube, still keeping the mixture in the ice-bath.

AMINE REACTION

I aliphatic N2 evolved.
RNH2 + HNO2 -> ROH + N2 + H2O
__________________________________________________________________
I aromatic Diazonium salt is formed.
ArNH2 + HNO2 -> ArN=N+
Add the cold diazonium solution and with swirling
to a cold solution of 2-naphthol (0.2 g) in 5% NaOH
solution (2 mL). An orange-red azo dye is formed.
__________________________________________________________________
II aliphatic and Yellow oily nitrosamines are generally formed.
II aromatic R2NH + HNO2 -> R2N-NO
__________________________________________________________________
III aliphatic No visible reaction.
__________________________________________________________________
III aromatic Dialkylanilines yield green solid p-nitroso
compounds (if p-position unsubstituted).
__________________________________________________________________

(b) Reaction with benzenesulphonyl chloride

Benzenesulphonyl chloride reacts with primary and secondary but not with tertiary amines to yield
substituted sulphonamides.

e.g. (a) C6H5SO2Cl + H-NHR + NaOH -> C6H5SO2NHR + NaCl + H2O

(b) C6H5SO2Cl + H-NR2 + NaOH -> C6H5SO2NR2 + NaCl + H2O
The substituted sulphonamide formed from a primary amine dissolves in the alkali medium whilst
that produced from a secondary amine is insoluble in alkali.

Place 0.5 mL (or 0.5 g) of the compound, 15 - 10 mL of 5% NaOH and 1 mL of

benzenesulphonyl chloride in a test tube, stopper the tube and shake until the odour of the
sulphonyl chloride has disappeared. The solution must be kept alkaline (if no reaction has
occurred, the substance is probably a tertiary amine).

If a precipitate appears in the alkaline solution, dilute with about 10 mL of water and shake; if
the precipitate does not dissolve, a secondary amine is indicated.

If there is no precipitate, acidify it cautiously to congo red with concentrated hydrochloric

acid (added dropwise): a precipitate is indicative of a primary amine.

2. Amides R-CO-NH2
Simple primary amides can be decomposed by boiling with alkali and thereby evolving
ammonia.

e.g. CH3-CO-NH2 + NaOH -> CH3-CO2- Na+ + NH3

Boil 0.5 g of the compound with 5 mL of 10% sodium hydroxide solution and observe whether
ammonia is evolved.

III. COMPOUNDS CONTAINING C, H AND POSSIBLY OXYGEN

1. Carboxylic acids - test with 5% aq. NaHCO3

R-CO2H + NaHCO3 -> R-CO2- Na+ + CO2 + H2O

Sodium hydrogen carbonate reacts with carboxylic acids to give the sodium salt of the acid and
liberates carbon dioxide. If the acid is insoluble in water and the reaction is sluggish dissolve the acid
in methanol and add carefully to a saturated sodium hydrogen carbonate solution, when a vigorous
effervescence will be observed.

2. Phenols [Soluble in NaOH and produce no CO2 from NaHCO3]

(a) Bromine water
Phenols are generally highly reactive towards electrophilic reagents and are readily
brominated by bromine water. e.g.

Dissolve or suspend about 0.05 g of the compound in 2 mL of dilute hydrochloric acid and
add bromine water dropwise until the bromine colour remains. A white precipitate of the
bromophenol may form. Solid bromophenol derivatives can be used for the confirmation of
the structure of a phenol (cf the preparation of derivatives).

(b) Ferric chloride test

Most phenols react with iron (III) chloride to form coloured complexes. The colours vary -
red, purple, blue or green - depending on various factors, e.g. the phenolic compound used,
the solvent, concentration. Since some phenols do not give colours, a negative test must not
be taken as significant without supporting information.

Dissolve 0.05 g of the compound in 2 mL water (or a mixture of water and ethanol if the
compound is not water-soluble) and add an aqueous solution of ferric chloride dropwise.
Observe any colour changes which may occur.

3. Aldehydes and ketones

(a) 2,4-Dinitrophenylhydrazine (as Brady's reagent) A test for the carbonyl group (C=O) in
aldehydes and ketones. 2,4-Dinitrophenylhydrazine gives sparingly soluble yellow or red 2,4-
dinitrophenylhydrazones with aldehydes and ketones.

Add 3 mL of the reagent to 2 drops of the compound in a test tube and shake. If no precipitate
forms immediately, warm and allow to stand for 5 - 10 minutes. A crystalline precipitate
indicates the presence of a carbonyl compound.

The bench reagent is very dilute and is intended for qualitative tests only and should not be
used in the preparation of a derivative for identification purposes. (b) Iodoform test for
CH3CO-
Dissolve 0.1 g (or 5 drops) of the compound in 2 mL of water; if it is insoluble in water add
sufficient dioxan to produce a homogeneous solution. Add 2 mL of 5% NaOH solution and
then introduce the potassium iodide - iodine reagent dropwise with shaking until a definite
dark colour of iodine persists. Allow to stand for 2 - 3 minutes; if no iodoform separates at
room temperature, warm the test tube in a beaker of water at 60 . Add a few more drops of
the iodine reagent if the faint iodine colour disappears. Continue the addition of the reagent
until a dark colour is not discharged after 2 minutes heating at 60 . Remove the excess of
iodine by the addition of a few drops of dilute sodium hydroxide solution with shaking, dilute
with an equal volume of water, and allow to stand for 10 minutes. The test is positive if a
yellow precipitate of iodoform is deposited. Filter off the yellow precipitate, dry upon pads of
filter paper and determine the m.p. Iodoform melts at 120 (it can be recrystallised from
methanol- water).

The reaction is given by acetaldehyde and simple methyl ketones. Alcohols containing the
CH3CHROH group will be oxidised under the reaction conditions and also give a positive
test.

4. Aldehydes only (reducing properties).

(a) Fehling's solution
Aldehydes reduce Fehling's solution to yellow or red copper (I) oxide.

Preparation of the reagent: Mix equal volumes of Fehling's solution solution I (aqueous
alkaline potassium tartrate) and Fehling's solution II (copper sulphate solution).

Add 2 drops (or 0.05 g) of the compound and 2 - 3 drops of the reagent and heat on a boiling
water bath for 3 - 4 minutes.

The test is positive for aliphatic aldehydes, but is often indecisive for aromatic aldehydes
where Jones' Reagent is often useful (see 5).

(b) Tollen's reagent (Ammonical silver nitrate solution)

Aldehydes are readily oxidised to carboxylic acids and will reduce Tollen's reagent to
produce a silver mirror on the inside of a clean test tube.

FIRST clean up a test tube with a little hot nitric acid (fume cupboard) and rinse with distilled
water.

Preparation of the reagent: To 1 mL of silver nitrate solution add a few drops of sodium
hydroxide. Then add dilute ammonium hydroxide dropwise until the precipitate just
dissolves.

Add 2 - 3 drops of the compound in methanol to 2 - 3 mL of Tollen's solution contained in a

very clean test tube. If no reaction takes place in the cold, warm gently in a water bath.

CAUTION: After the test, pour the contents of the test tube into the sink and wash the test
tube with dilute nitric acid. Any silver fulminate present, which is highly explosive when dry,
will be destroyed.

(c) Jones Reagent (See section under alcohols).

5. Alcohols
The tests for the hydroxyl group not only detect the presence of the group, but may also
indicate whether it is primary, secondary or tertiary.
(a) Jones Reagent (CrO3-H2SO4 in H2O)
This reagent distinguishes primary and secondary alcohols from tertiary alcohols; the test is
based on the much greater resistance to oxidation of tertiary alcohols compared to the other
two types. Aldehydes also give a positive test.

Place 1 mL of acetone in a test tube and dissolve one drop of a liquid or ca 10 mg of a solid
alcohol or aldehyde in it. Add one drop of the reagent to the acetone solution and shake the
tube to mix the contents. Primary and secondary alcohols react within two seconds as
indicated by the disappearance of the orange colour of the reagent and the formation of a
green or blue-green precipitate or emulsion.
Tertiary alcohols do not react even after 3 minutes.

(I) RCH2OH -> RCHO -> RCO2H

(II) R2CHOH -> R2C=O

(III) R3COH -> no visible reaction.

(b) Lucas' Reagent [ZnCl2 - conc. HCl]

This reagent converts alcohols into the corresponding alkyl chlorides. Zinc chloride (a Lewis
acid) increases the reactivity of alcohols towards acid. The test depends on the rate of
reaction of primary, secondary, and tertiary alcohols with the reagent at room temperature.

(I) RCH2OH -> no reaction at room temperature.

(II) R2CHOH -> R2CHCl + H2O (1 hour or maybe longer)

(III) R3COH -> R3CCl + H2O (immediately)

To 1 mL of the alcohol in a small test tube add 6 mL of Lucas' reagent at room temperature. Close
the tube with a cork, shake and allow to stand.

(i) Primary alcohols - the aqueous phase remains clear (except allyl alcohol - droplets after 7
minutes).

(ii) Secondary alcohols - very slow reaction (~ 1 hour or maybe longer) when droplets of
alkyl chloride may be seen.

(iii) Tertiary alcohols - very fast reaction and droplets of the alkyl chloride formed almost
immediately.

6. Sugars, Carbohydrates
Molisch's Test
This is a general test for carbohydrates. Dissolve 20 - 30 mg of the compound in 2 mL water
and add 0.5 mL of the reagent (a 20% solution of 2-naphthol in ethanol). Pour 2 mL of
concentrated sulphuric acid from a dropper carefully down the side of the tube so that the
acid forms a layer beneath the aqueous solution without mixing with it. A red colouration,
changing to dark purple forms at the interface. Carry out a second test on a blank solution.

7. Esters
Hydroxamic acid test
 R-CO-OR' + H2N-OH -> R-CO-NH-OH + R'-OH

Esters react with hydroxylamine in the presence of sodium hydroxide to form the sodium salt
of the corresponding hydroxamic acid. On acidification and addition of ferric chloride the
magenta-coloured iron (III) complex of the hydroxamic acid is formed.

It is always advisable to ensure that an unknown compound does not give a colour with iron
(III) chloride before carrying out the hydroxamic acid test.

Procedure for hydroxamic acid test

(a) Ferric chloride test
Dissolve a drop or a few small crystals of the compound in 1 mL of 95% ethanol (rectified
spirit) and add 1 mL of M hydrochloric acid. Note the colour produced when 1 drop of 5%
iron (III) chloride is added to the solution. If a pronounced violet, blue, red or orange colour
is produced, the hydroxamic acid test described below is NOT APPLICABLE.

(b) Hydroxamic acid test

Mix 1 drop or several small crystals (ca 0.05 g) of the compound with 1 mL of 0.5 M
hydroxylamine hydrochloride in 95% ethanol and add 0.2 mL of 6 M aqueous sodium
hydroxide. Heat the mixture to boiling and after the solution has cooled slightly add 2 mL of
M hydrochloric acid. If the solution is cloudy, add 2 mL of 95% ethanol. Observe the colour
produced when 1 drop of 5% iron (III) chloride solution is added. If the resulting colour does
not persist, continue to add the reagent dropwise until the observed colour pervades the entire
solution. Usually only 1 drop of the iron (III) chloride solution is necessary. Compare the
colour with that produced in test (a). A positive test will be a distinct burgundy or magenta
colour as compared with the yellow colour observed when the original compound is tested
with iron (III) chloride solution in the presence of acid. It is often advisable to conduct in
parallel the test with, say, ethyl acetate, to ensure that the conditions for this test are correct.

THE PREPARATION
ORGANIC OF DERIVATIVES OF
COMPOUNDS
The preliminary examination and group classification tests indicate the particular class (functional
group) to which an unknown organic compound may belong. Further characterisation and
identification depends on the selection and preparation of a suitable solid derivative and accurate
determination of its melting point (best, between 90 - 150 ).

The following table lists some of the classes of organic compounds and a selection of
derivatives that may be prepared to characterise them. Check with the tables of melting points
in Vogel which derivatives are most suitable for the characterisation of your particular
compound.

CLASS OF COMPOUND DERIVATIVES

1. ALCOHOLS 3,5-dinitrobenzoate

2. PHENOLS benzoate, acetate, bromo-derivative

3. ALDEHYDES AND KETONES semicarbazone, 2,4-dinitrophenyl-hydrazone, oxime

4. ACIDS anilide, amide, p-toluidide.

5. AMINES benzoyl, acetyl and sulphonamide derivatives

METHODS FOR THE PREPARATION OF DERIVATIVES

ALCOHOLS

(i) 3,5-Dinitrobenzoates
3,5-Dinitrobenzoyl chloride is usually partially hydrolysed and should be prepared in the pure
state by heating gently a mixture of 3,5-dinitrobenzoic acid (1 g) and phosphorus
pentachloride (1.5 g) in a dry test tube, until it liquifies (5 min).* The liquid is poured on a
dry watch glass and allowed to solidify. The phosphoryl chlorides are removed by pressing
the solid with a spatula on a wad of filter paper. The residual acid chloride is suitable for
immediate use in the preparation of the derivatives.

*Work under fume hood. Fumes are irritating to the eyes and nose.

The 3,5-dinitrobenzoyl chloride is mixed with the alcohol (0.5 - 1 mL) in a loosely corked
dry test tube and heated on a steam bath for about 10 min. Secondary and tertiary alcohols
require up to 30 min. On cooling add 10 mL sodium hydrogen carbonate solution, stir until
the ester crystallises out, and filter at the pump. Wash with a little carbonate solution, water
and suck dry. Recrystallise from the minimum hot ethanol or light petroleum. Cool slowly to
avoid the formation of oily droplets of your ester.

PHENOLS

(i) Benzoates (Schötten-Baumann method).

To the phenol (0.5 g) is added 5% sodium hydroxide (10 mL) in a well-corked boiling tube or
a small conical flask. Benzoyl chloride (2 mL) is added in small quantities at a time, and the
mixture shaken vigorously with occasional cooling under the tap or in ice-water. After 15
min the solid benzoate separates out: the solution should be alkaline at the end of the
reaction; if not alkaline, or if the product is oily, add a solid pellet of sodium hydroxide and
shake again. Collect the benzoate, wash thoroughly with cold water, and recrystallise from
alcohol or light petroleum.

(ii) Acetates
Acetates of many simple phenols are liquids; however, this is a suitable derivative for
polyhydric and substituted phenols. The phenol (0.5 g) is dissolved in 10% sodium hydroxide
solution and an equal quantity of crushed ice is added, followed by acetic anhydride (2 mL).
The mixture is vigorously shaken in a stoppered test tube until the acetate separates. The
product is filtered and recrystallised from alcohol.

(iii) Bromo derivatives

The phenol (0.3 g) is suspended in dilute hydrochloric (10 mL) and bromine water added
dropwise until no more decolourisation occurs. The bromo derivative which precipitates out
is filtered off and recrystallised from alcohol.

ALDEHYDES AND KETONES

(i) Semicarbazones
Dissolve semicarbazide hydrochloride (1 g) and sodium acetate (1.5 g) in water (8 - 10 mL),
add the aldehyde or ketone (0.3 mL) and shake. Shake the mixture for a few minutes and then
cool in ice-water. Filter off the crystals, wash with a little cold water and recrystallise from
methanol or ethanol.

(ii) 2,4-Dinitrophenylhydrazones
Suspend 0.25 g of 2,4-dinitrophenylhydrazine in 5 mL of methanol and add 0.5 mL of
concentrated sulphuric acid cautiously. Filter the warm solution and add a solution of 0.2 g of
the carbonyl compound in 1 mL of methanol. Recrystallise the derivative from methanol,
ethanol or ethyl acetate.

(iii) Oximes
Hydroxylamine hydrochloride (0.5 g) is dissolved in water (2 mL). 10% sodium hydroxide (2
mL) and the carbonyl compound (0.2 - 0.3 g) dissolved in alcohol (1 - 2 mL) are added, the
mixture warmed on a steam bath for 10 min and then cooled in ice. Crystallisation is induced
by scratching the sides of the test tube with a glass rod. The oximes may be crystallised from
alcohol.

ACIDS

(i) Amides, anilides and p-toluidides

The acid (0.5 g) is refluxed with thionyl chloride (2 - 3 mL) in a fume cupboard for about 30
mins.* It is advisable to place a plug of cotton wool in the top of the reflux condenser to
exclude moisture. The condenser is removed and the excess of thionyl chloride is distilled off
(b.p. 78 ). The acid chloride thus produced is treated with concentrated ammonia solution (5
mL) or aniline (0.5 - 1 mL) or p-toluidine (0.5 - 1 g), when the solid derivative separates out.
It is collected and recrystallised from alcohol adding decolourising charcoal if found
necessary.

*Alternately use PCl5 to form the acid chloride.

AMINES

(i) Acetyl derivatives (acetamides)

Reflux gently in a small dry flask under a dry condenser the amine (1 g) with acetic
anhydride (3 mL) for 15 min. Cool the reaction mixture and pour into 20 mL cold water. Boil
to decompose the excess acetic anhydride. Cool and filter by suction the insoluble derivative.
Recrystallise from ethanol.

(ii) Benzoyl derivatives (benzamides)

Suspend 1 g of the amine in 20 mL of 5% aqueous sodium hydroxide in a well-corked flask,
and add 2 mL benzoyl chloride (fume hood!), about 0.5 mL at a time, with constant shaking.
Shake vigorously for 5 - 10 min until the odour of the benzoyl chloride has disappeared.
Ensure that the mixture remains alkaline. Filter off the solid derivative, wash with a little cold
water and recrystallise from ethanol.

(iii) Benzenesulphonamides
To 1 g of the amine in 20 mL of 5% sodium hydroxide solution in a well-corked flask add 1
mL benzenesulphonyl chloride (fume hood!). Shake the mixture until the odour of the
sulphonyl chloride disappears. Check that the solution is alkaline. Acidify if necessary to
obtain the precipitated derivative. Concentrated hydrochloric acid added dropwise should be
used. Filter the product, wash with a little cold water and suck dry. Recrystallise from
ethanol.

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Qualitative Analysis of Organic Compounds.
The analysis and identification of unknown organic compounds constitutes a very important aspect
of experimental organic chemistry.

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.

Students should, however, consult the laboratory manual and Textbook of Practical Organic
Chemistry, A.I. Vogel (4th Edition).
Practical Notes
Before outlining the general scheme, one or two points of practical importance should be noted.

(a) Quantities of substance for tests. For most tests about 0.1 g solid or 0.1 - 0.2 mL (2 - 3
drops) of liquid material (NOT MORE) should be used.

(b) Reagents likely to be met within organic analysis are on the reagent shelves. Students are
advised to develop a general knowledge of the physical characteristics of common organic
compounds. If in doubt about the expected result of a test between a certain compound and a
reagent, carry out a trial test with a known compound and compare with the unknown.

(c) Quantities of substance derivatives. Students have wasted much time and material in the
past by taking too large a quantity of substance for preparation of a derivative. In general, 0.5
- 1 g (or 0.5 - 1 mL) of substance gives the most satisfactory results.

If a practical book instructs one to use larger quantities (3 - 4 g or more), the quantities
should be scaled down to 1 g or 1 mL of the unknown substance and corresponding quantities
of reagents should be used.
General Scheme of Analysis
A. Preliminary Tests

(a) Note physical characteristics - solid, liquid, colour and odour.

(b) Perform an ignition test (heat small amount on metal spatula) to determine whether the
compound is aliphatic or aromatic (i.e. luminous flame - aliphatic; sooty flame - aromatic).

B. Physical Constants

Determine the boiling point or melting point. Distillation is recommended in the case of
liquids (see Appendix 3). It serves the dual purpose of determining the b.p., as well as
purification of the liquid for subsequent tests.

C. Analysis for elements present

At C10 level, the elements present will be told to you, but read up the method.
D. Solubility tests

The solubility of the unknown in the following reagents provides very useful information. In
general, about 3 mL of the solvent is used with 0.1 g or 0.2 mL (2 - 3 drops) of the substance.
The class of compound may be indicated from the following table:

SOLUBILITY TABLE
REAGENT AND TEST CLASS GROUP OF COMPOUNDS

Soluble in cold or hot water. Neutral, acidic or

Lower members of series. Neutral, e.g.
(If the unknown is soluble do basic. (Test with litmus
alcohols; Acidic, e.g. acids, phenols; Basic,
NOT perform solubility tests or universal indicator
e.g. amines
below) paper)

Most amines (except III amines with only

Soluble in dil. HCl Basic
aromatic groups

Soluble in dil. NaOH Acidic Most acids, most phenols.

Soluble in NaHCO3 Strongly acidic Most carboxylic acids.

Hydrocarbons, nitrohydro-carbons, alkyl

Insoluble in water, acid and or aryl halides, esters and ethers. Higher
Neutral
alkali molecular weight alcohols, aldehydes and
ketones

E. Group Classification Tests

From the previous tests it is often possible to deduce the functional groups present in the
unknown compound. Consult i.r. spectra when available.

Individual tests are then performed to identify and confirm the functional groups present.

NOTE:
1. Students are strongly advised against carrying out unnecessary tests, since not only are they a
waste of time but also increase the possibility of error. Thus it is pointless to first test for alcohol or
ketone in a basic compound containing nitrogen! Instead tests for amines, etc. should be done on
such a compound.

2. A systematic approach cannot be overemphasised in group classification tests to avoid

confusion and error.

F. Consultation of Literature
Once the functional group has been identified, reference is made to tables in a book on
organic analysis, for assessing possibilities and for the preparation of suitable solid
derivatives.

It should be noted that whilst two substances with the same functional group may sometimes
have very similar b.p. or m.p., solid derivatives canusually be chosen from the literature, with
m.p. differences of about 10 (or more), which distinguish between the two possibilities.

Example:
COMPOUND B.P. DERIVATIVES (M.P.)
2,4-DNPH SEMICARBAZONE
Diethyl ketone 102 156 139
Methyl n-propyl ketone 102 144 112
G. Preparation of derivatives

The final characterisation of the unknown is made by the preparation of suitable solid
derivatives. The derivative should be carefully selected and its m.p. should preferably be
between 90 - 150 for ease of crystallisation and m.p. determination.

Preparation of one derivative should be attempted. The derivative should be purified by

recrystallisation, dried and the m.p. determined. Derivatives should be submitted correctly
labelled for assessment together with the record.

Recording of Results

The results should be recorded in a systematic manner. Results should be recorded in the
practical book at the time (not written up afterwards).

A record should be made of every test carried out, no matter whether a NEGATIVE
RESULT HAS BEEN OBTAINED.

Test, observation and inference should be given.

At the conclusion of the analysis a brief summary of results should be included, giving the
name, b.p. or m.p., and formula of the analysed compound.

Qualitative Analysis for Elements (for reference only)

In organic compounds the elements commonly occurring along with carbon and hydrogen,
are oxygen, nitrogen, sulphur, chlorine, bromine and iodine. The detection of these elements
depends upon converting them to water-soluble ionic compounds and the application of
specific tests.

Lassaigne's Sodium Fusion Test

C, H, O, N, S, X NaX
NaCN
-> Na2S
NaCNS
PROCEDURE
Place a piece of clean sodium metal, about the size of a pea into a fusion tube. Add a little of
the compound (50 mg or 2 - 3 drops).* Heat the tube gently at first, allowing any distillate
formed to drop back onto the molten sodium. When charring begins, heat the bottom of the
tube to dull redness for about three minutes and finally plunge the tube, while still hot, into a
clean dish containing cold distilled water (6 mL) and cover immediately with a clean wire
gauze.**

*For liquids it is better to first melt the sodium add the liquid drop by drop.

**CAUTION: The tube shatters, and any residual sodium metal reacts with water. Stir the
mixture, boil for 1 - 2 minutes, on a tripod and filter hot through a fluted paper.

The 'fusion' filtrate which should be clear and colourless, is used for the SPECIFIC TESTS
DESCRIBED BELOW:

1. To a portion (2 mL) of the 'fusion' filtrate add 0.2 g of powdered ferrous sulphate crystals.
Boil the mixture for a half a minute, cool and acidify by adding dilute sulphuric acid
dropwise. Formation of a bluish-green precipitate (Prussian blue) or a blue solution indicates
that the original substance contains nitrogen. If no precipitate appears, allow to stand for 15
minutes, filter and inspect filter paper.

2. SULPHUR (SULPHIDE)
To the cold 'fusion' filtrate (1 mL) add a few drops of cold, freshly prepared, dilute solution
of sodium nitroprusside. The latter may be prepared by adding a small crystal of the solid to 2
mL of water. Production of a rich purple colour indicates that the original substance contains
sulphur. This test is very sensitive. Only strong positive results are significant.

3. HALOGENS (HALIDES)
Acidify a portion (1 mL) of the 'fusion' filtrate with 2N nitric acid, and if nitrogen and/or
sulphur are present, boil for 1 - 2 minutes.* Cool and add aqueous silver nitrate (1 mL),
compare with a blank. Formation of a heavy, white or yellow precipitate of silver halide
indicates halogen. If a positive result is obtained: acidify the remaining portion of the 'fusion'
filtrate with dilute sulphuric acid, boil and cool. Add carbon tetrachloride (1 mL) and a few
drops of freshly prepared chlorine water. Shake the mixture.

(a) If the carbon tetrachloride layer remains colourless - indicates chlorine.

(b) If the carbon tetrachloride layer is brown - indicates bromine.

(c) If the carbon tetrachloride layer is violet - indicates iodine.

*If nitrogen and/or sulphur are also present, the addition of silver nitrate to the acidified
'fusion' solution will precipitate silver cyanide and/or silver sulphide in addition to the silver
halides. The removal of hydrogen cyanide and/or hydrogen sulphide is effected by boiling the
'fusion' solution. GROUP CLASSIFICATION TESTS

Some functional group tests are listed below. Students should refer to a practical text book for
details, and further information, e.g. Vogel.
Tests for unsaturation
1. Cold dilute potassium permanganate solution.
2. Solution of bromine in carbon tetrachloride.

Tests for compounds containing nitrogen

1. Amines
(a) Nitrous acid.
(b) Confirmatory tests.

2. Compounds which give amines or ammonia on acid or alkaline hydrolysis:

Amides, substituted amides, anilides, nitriles.

3. Compounds which give amines on reduction:

Nitro, nitroso, azo, hydrazo, nitriles.

Tests for compounds containing C, H and possibly oxygen

1. Carboxylic acids
Na2CO3 or NaHCO3 solution liberate carbon dioxide.

2. Phenols
(a) Sodium hydroxide solution (soluble). Insoluble in and no CO2 from NaHCO3 (except
when electron attracting groups present, e.g. 2,4-dinitrophenol).
(b) Ferric chloride solution.
(c) Bromine water.

3. Aldehydes and Ketones

(a) 2,4-dinitrophenylhydrazine (as Brady's reagent) for C=O.
(b) Iodoform test for CH3CO-.

4. Aldehydes only (reducing properties)

(a) Fehling's solution.
(b) Tollen's reagent (ammoniacal AgNO3 solution).
(c) Jones reagent.

5. Alcohols
(a) Lucas' reagent to distinguish I, II and III alcohols.
(b) Jones reagent.
(c) Metallic sodium (use dry liquid and dry tube).

6. Sugars
(a) Molisch's test.

7. Esters
(a) Hydroxamic acid test.
(b) Hydrolysis.

Write up of the identification of an unknown organic compound

Date......................................

Compound containing C, H (N, Hal, S)

Physical characteristics ...................... (solid, liquid, gas,

colour, odour, etc.)

Ignition test .............................. (aromatic or aliphatic)

Physical constant ........................ (boiling point or melting

point)

Solubility tests (in tabular form)

Group classification tests (in tabular form)

Test Observation Inference

From the above tests and observations the given compound is probably a
.........................(acid, phenol, aldehyde, etc.)

Consultation of literature (Possibilities) M.P. of derivative

(a)

(b)

(c)

Preparation of derivative (method of preparation)

Observed m.p. of derivative

Lit. m.p. of derivative

Result

Compound No. ........................ is ............................

(give formula)

TESTS FOR FUNCTIONAL GROUPS

I. UNSATURATED COMPOUNDS

Two common types of unsaturated compounds are alkenes and alkynes characterised by the
carbon-carbon double and triple bond, respectively, as the functional group. The two
common qualitative tests for unsaturation are the reactions of the compounds with (a)
bromine in carbon tetrachloride and (b) potassium permanganate.
(a) 2% Bromine in carbon tetrachloride
Dissolve 0.2 g (or 0.2 mL) of the compound in 2 mL of carbon tetrachloride or another
suitable solvent and add the solution dropwise to 2 ml of 2% bromine solution in carbon
tetrachloride and shake.

e.g.

Rapid disappearance of the bromine colour to give a colourless solution is a positive test for
unsaturation.

NOTE: The reagent is potentially dangerous. Keep it off your skin and clothes; protect
your eyes and nose. (b) 2% Aqueous potassium permanganate
Dissolve 0.2 g (or 0.2 mL) of the substance in 2 mL of water (acetone may also be used as
solvent). Add the potassium permanganate solution dropwise and observe the result.

e.g.

For a blank determination, count the number of drops added to 2 mL of acetone before the
colour persists. A significant difference in the number of drops required in the two cases is a
positive test for unsaturation.

II. COMPOUNDS CONTAINING NITROGEN

1. Amines
(a) Reaction with nitrous acid Dissolve the amine (0.5 mL) in concentrated acid (2.0 mL) and
water (3 mL) and cool the solution to 0 - 5 in an ice-bath for 5 minutes. Add a cold solution
(ice-bath) of sodium nitrite (0.5 g) in water (2.0 mL) from a dropper, with swirling of the test
tube, still keeping the mixture in the ice-bath.

AMINE REACTION

I aliphatic N2 evolved.
RNH2 + HNO2 -> ROH + N2 + H2O
__________________________________________________________________
I aromatic Diazonium salt is formed.
ArNH2 + HNO2 -> ArN=N+
Add the cold diazonium solution and with swirling
to a cold solution of 2-naphthol (0.2 g) in 5% NaOH
solution (2 mL). An orange-red azo dye is formed.
__________________________________________________________________
II aliphatic and Yellow oily nitrosamines are generally formed.
II aromatic R2NH + HNO2 -> R2N-NO
__________________________________________________________________
III aliphatic No visible reaction.
__________________________________________________________________
III aromatic Dialkylanilines yield green solid p-nitroso
compounds (if p-position unsubstituted).
__________________________________________________________________

(b) Reaction with benzenesulphonyl chloride

Benzenesulphonyl chloride reacts with primary and secondary but not with tertiary amines to yield
substituted sulphonamides.

e.g. (a) C6H5SO2Cl + H-NHR + NaOH -> C6H5SO2NHR + NaCl + H2O

(b) C6H5SO2Cl + H-NR2 + NaOH -> C6H5SO2NR2 + NaCl + H2O
The substituted sulphonamide formed from a primary amine dissolves in the alkali medium whilst
that produced from a secondary amine is insoluble in alkali.

Place 0.5 mL (or 0.5 g) of the compound, 15 - 10 mL of 5% NaOH and 1 mL of

benzenesulphonyl chloride in a test tube, stopper the tube and shake until the odour of the
sulphonyl chloride has disappeared. The solution must be kept alkaline (if no reaction has
occurred, the substance is probably a tertiary amine).

If a precipitate appears in the alkaline solution, dilute with about 10 mL of water and shake; if
the precipitate does not dissolve, a secondary amine is indicated.

If there is no precipitate, acidify it cautiously to congo red with concentrated hydrochloric

acid (added dropwise): a precipitate is indicative of a primary amine.

2. Amides R-CO-NH2
Simple primary amides can be decomposed by boiling with alkali and thereby evolving
ammonia.

e.g. CH3-CO-NH2 + NaOH -> CH3-CO2- Na+ + NH3

Boil 0.5 g of the compound with 5 mL of 10% sodium hydroxide solution and observe whether
ammonia is evolved.

III. COMPOUNDS CONTAINING C, H AND POSSIBLY OXYGEN

1. Carboxylic acids - test with 5% aq. NaHCO3

R-CO2H + NaHCO3 -> R-CO2- Na+ + CO2 + H2O

Sodium hydrogen carbonate reacts with carboxylic acids to give the sodium salt of the acid and
liberates carbon dioxide. If the acid is insoluble in water and the reaction is sluggish dissolve the acid
in methanol and add carefully to a saturated sodium hydrogen carbonate solution, when a vigorous
effervescence will be observed.

2. Phenols [Soluble in NaOH and produce no CO2 from NaHCO3]

(a) Bromine water
Phenols are generally highly reactive towards electrophilic reagents and are readily
brominated by bromine water. e.g.

Dissolve or suspend about 0.05 g of the compound in 2 mL of dilute hydrochloric acid and
add bromine water dropwise until the bromine colour remains. A white precipitate of the
bromophenol may form. Solid bromophenol derivatives can be used for the confirmation of
the structure of a phenol (cf the preparation of derivatives).

(b) Ferric chloride test

Most phenols react with iron (III) chloride to form coloured complexes. The colours vary -
red, purple, blue or green - depending on various factors, e.g. the phenolic compound used,
the solvent, concentration. Since some phenols do not give colours, a negative test must not
be taken as significant without supporting information.

Dissolve 0.05 g of the compound in 2 mL water (or a mixture of water and ethanol if the
compound is not water-soluble) and add an aqueous solution of ferric chloride dropwise.
Observe any colour changes which may occur.

3. Aldehydes and ketones

(a) 2,4-Dinitrophenylhydrazine (as Brady's reagent) A test for the carbonyl group (C=O) in
aldehydes and ketones. 2,4-Dinitrophenylhydrazine gives sparingly soluble yellow or red 2,4-
dinitrophenylhydrazones with aldehydes and ketones.

Add 3 mL of the reagent to 2 drops of the compound in a test tube and shake. If no precipitate
forms immediately, warm and allow to stand for 5 - 10 minutes. A crystalline precipitate
indicates the presence of a carbonyl compound.

The bench reagent is very dilute and is intended for qualitative tests only and should not be
used in the preparation of a derivative for identification purposes. (b) Iodoform test for
CH3CO-
Dissolve 0.1 g (or 5 drops) of the compound in 2 mL of water; if it is insoluble in water add
sufficient dioxan to produce a homogeneous solution. Add 2 mL of 5% NaOH solution and
then introduce the potassium iodide - iodine reagent dropwise with shaking until a definite
dark colour of iodine persists. Allow to stand for 2 - 3 minutes; if no iodoform separates at
room temperature, warm the test tube in a beaker of water at 60 . Add a few more drops of
the iodine reagent if the faint iodine colour disappears. Continue the addition of the reagent
until a dark colour is not discharged after 2 minutes heating at 60 . Remove the excess of
iodine by the addition of a few drops of dilute sodium hydroxide solution with shaking, dilute
with an equal volume of water, and allow to stand for 10 minutes. The test is positive if a
yellow precipitate of iodoform is deposited. Filter off the yellow precipitate, dry upon pads of
filter paper and determine the m.p. Iodoform melts at 120 (it can be recrystallised from
methanol- water).

The reaction is given by acetaldehyde and simple methyl ketones. Alcohols containing the
CH3CHROH group will be oxidised under the reaction conditions and also give a positive
test.

4. Aldehydes only (reducing properties).

(a) Fehling's solution
Aldehydes reduce Fehling's solution to yellow or red copper (I) oxide.

Preparation of the reagent: Mix equal volumes of Fehling's solution solution I (aqueous
alkaline potassium tartrate) and Fehling's solution II (copper sulphate solution).

Add 2 drops (or 0.05 g) of the compound and 2 - 3 drops of the reagent and heat on a boiling
water bath for 3 - 4 minutes.

The test is positive for aliphatic aldehydes, but is often indecisive for aromatic aldehydes
where Jones' Reagent is often useful (see 5).

(b) Tollen's reagent (Ammonical silver nitrate solution)

Aldehydes are readily oxidised to carboxylic acids and will reduce Tollen's reagent to
produce a silver mirror on the inside of a clean test tube.

FIRST clean up a test tube with a little hot nitric acid (fume cupboard) and rinse with distilled
water.

Preparation of the reagent: To 1 mL of silver nitrate solution add a few drops of sodium
hydroxide. Then add dilute ammonium hydroxide dropwise until the precipitate just
dissolves.

Add 2 - 3 drops of the compound in methanol to 2 - 3 mL of Tollen's solution contained in a

very clean test tube. If no reaction takes place in the cold, warm gently in a water bath.

CAUTION: After the test, pour the contents of the test tube into the sink and wash the test
tube with dilute nitric acid. Any silver fulminate present, which is highly explosive when dry,
will be destroyed.

(c) Jones Reagent (See section under alcohols).

5. Alcohols
The tests for the hydroxyl group not only detect the presence of the group, but may also
indicate whether it is primary, secondary or tertiary.
(a) Jones Reagent (CrO3-H2SO4 in H2O)
This reagent distinguishes primary and secondary alcohols from tertiary alcohols; the test is
based on the much greater resistance to oxidation of tertiary alcohols compared to the other
two types. Aldehydes also give a positive test.

Place 1 mL of acetone in a test tube and dissolve one drop of a liquid or ca 10 mg of a solid
alcohol or aldehyde in it. Add one drop of the reagent to the acetone solution and shake the
tube to mix the contents. Primary and secondary alcohols react within two seconds as
indicated by the disappearance of the orange colour of the reagent and the formation of a
green or blue-green precipitate or emulsion.
Tertiary alcohols do not react even after 3 minutes.

(I) RCH2OH -> RCHO -> RCO2H

(II) R2CHOH -> R2C=O

(III) R3COH -> no visible reaction.

(b) Lucas' Reagent [ZnCl2 - conc. HCl]

This reagent converts alcohols into the corresponding alkyl chlorides. Zinc chloride (a Lewis
acid) increases the reactivity of alcohols towards acid. The test depends on the rate of
reaction of primary, secondary, and tertiary alcohols with the reagent at room temperature.

(I) RCH2OH -> no reaction at room temperature.

(II) R2CHOH -> R2CHCl + H2O (1 hour or maybe longer)

(III) R3COH -> R3CCl + H2O (immediately)

To 1 mL of the alcohol in a small test tube add 6 mL of Lucas' reagent at room temperature. Close
the tube with a cork, shake and allow to stand.

(i) Primary alcohols - the aqueous phase remains clear (except allyl alcohol - droplets after 7
minutes).

(ii) Secondary alcohols - very slow reaction (~ 1 hour or maybe longer) when droplets of
alkyl chloride may be seen.

(iii) Tertiary alcohols - very fast reaction and droplets of the alkyl chloride formed almost
immediately.

6. Sugars, Carbohydrates
Molisch's Test
This is a general test for carbohydrates. Dissolve 20 - 30 mg of the compound in 2 mL water
and add 0.5 mL of the reagent (a 20% solution of 2-naphthol in ethanol). Pour 2 mL of
concentrated sulphuric acid from a dropper carefully down the side of the tube so that the
acid forms a layer beneath the aqueous solution without mixing with it. A red colouration,
changing to dark purple forms at the interface. Carry out a second test on a blank solution.

7. Esters
Hydroxamic acid test
 R-CO-OR' + H2N-OH -> R-CO-NH-OH + R'-OH

Esters react with hydroxylamine in the presence of sodium hydroxide to form the sodium salt
of the corresponding hydroxamic acid. On acidification and addition of ferric chloride the
magenta-coloured iron (III) complex of the hydroxamic acid is formed.

It is always advisable to ensure that an unknown compound does not give a colour with iron
(III) chloride before carrying out the hydroxamic acid test.

Procedure for hydroxamic acid test

(a) Ferric chloride test
Dissolve a drop or a few small crystals of the compound in 1 mL of 95% ethanol (rectified
spirit) and add 1 mL of M hydrochloric acid. Note the colour produced when 1 drop of 5%
iron (III) chloride is added to the solution. If a pronounced violet, blue, red or orange colour
is produced, the hydroxamic acid test described below is NOT APPLICABLE.

(b) Hydroxamic acid test

Mix 1 drop or several small crystals (ca 0.05 g) of the compound with 1 mL of 0.5 M
hydroxylamine hydrochloride in 95% ethanol and add 0.2 mL of 6 M aqueous sodium
hydroxide. Heat the mixture to boiling and after the solution has cooled slightly add 2 mL of
M hydrochloric acid. If the solution is cloudy, add 2 mL of 95% ethanol. Observe the colour
produced when 1 drop of 5% iron (III) chloride solution is added. If the resulting colour does
not persist, continue to add the reagent dropwise until the observed colour pervades the entire
solution. Usually only 1 drop of the iron (III) chloride solution is necessary. Compare the
colour with that produced in test (a). A positive test will be a distinct burgundy or magenta
colour as compared with the yellow colour observed when the original compound is tested
with iron (III) chloride solution in the presence of acid. It is often advisable to conduct in
parallel the test with, say, ethyl acetate, to ensure that the conditions for this test are correct.

THE PREPARATION
ORGANIC OF DERIVATIVES OF
COMPOUNDS
The preliminary examination and group classification tests indicate the particular class (functional
group) to which an unknown organic compound may belong. Further characterisation and
identification depends on the selection and preparation of a suitable solid derivative and accurate
determination of its melting point (best, between 90 - 150 ).

The following table lists some of the classes of organic compounds and a selection of
derivatives that may be prepared to characterise them. Check with the tables of melting points
in Vogel which derivatives are most suitable for the characterisation of your particular
compound.

CLASS OF COMPOUND DERIVATIVES

1. ALCOHOLS 3,5-dinitrobenzoate

2. PHENOLS benzoate, acetate, bromo-derivative

3. ALDEHYDES AND KETONES semicarbazone, 2,4-dinitrophenyl-hydrazone, oxime

4. ACIDS anilide, amide, p-toluidide.

5. AMINES benzoyl, acetyl and sulphonamide derivatives

METHODS FOR THE PREPARATION OF DERIVATIVES

ALCOHOLS

(i) 3,5-Dinitrobenzoates
3,5-Dinitrobenzoyl chloride is usually partially hydrolysed and should be prepared in the pure
state by heating gently a mixture of 3,5-dinitrobenzoic acid (1 g) and phosphorus
pentachloride (1.5 g) in a dry test tube, until it liquifies (5 min).* The liquid is poured on a
dry watch glass and allowed to solidify. The phosphoryl chlorides are removed by pressing
the solid with a spatula on a wad of filter paper. The residual acid chloride is suitable for
immediate use in the preparation of the derivatives.

*Work under fume hood. Fumes are irritating to the eyes and nose.

The 3,5-dinitrobenzoyl chloride is mixed with the alcohol (0.5 - 1 mL) in a loosely corked
dry test tube and heated on a steam bath for about 10 min. Secondary and tertiary alcohols
require up to 30 min. On cooling add 10 mL sodium hydrogen carbonate solution, stir until
the ester crystallises out, and filter at the pump. Wash with a little carbonate solution, water
and suck dry. Recrystallise from the minimum hot ethanol or light petroleum. Cool slowly to
avoid the formation of oily droplets of your ester.

PHENOLS

(i) Benzoates (Schötten-Baumann method).

To the phenol (0.5 g) is added 5% sodium hydroxide (10 mL) in a well-corked boiling tube or
a small conical flask. Benzoyl chloride (2 mL) is added in small quantities at a time, and the
mixture shaken vigorously with occasional cooling under the tap or in ice-water. After 15
min the solid benzoate separates out: the solution should be alkaline at the end of the
reaction; if not alkaline, or if the product is oily, add a solid pellet of sodium hydroxide and
shake again. Collect the benzoate, wash thoroughly with cold water, and recrystallise from
alcohol or light petroleum.

(ii) Acetates
Acetates of many simple phenols are liquids; however, this is a suitable derivative for
polyhydric and substituted phenols. The phenol (0.5 g) is dissolved in 10% sodium hydroxide
solution and an equal quantity of crushed ice is added, followed by acetic anhydride (2 mL).
The mixture is vigorously shaken in a stoppered test tube until the acetate separates. The
product is filtered and recrystallised from alcohol.

(iii) Bromo derivatives

The phenol (0.3 g) is suspended in dilute hydrochloric (10 mL) and bromine water added
dropwise until no more decolourisation occurs. The bromo derivative which precipitates out
is filtered off and recrystallised from alcohol.

ALDEHYDES AND KETONES

(i) Semicarbazones
Dissolve semicarbazide hydrochloride (1 g) and sodium acetate (1.5 g) in water (8 - 10 mL),
add the aldehyde or ketone (0.3 mL) and shake. Shake the mixture for a few minutes and then
cool in ice-water. Filter off the crystals, wash with a little cold water and recrystallise from
methanol or ethanol.

(ii) 2,4-Dinitrophenylhydrazones
Suspend 0.25 g of 2,4-dinitrophenylhydrazine in 5 mL of methanol and add 0.5 mL of
concentrated sulphuric acid cautiously. Filter the warm solution and add a solution of 0.2 g of
the carbonyl compound in 1 mL of methanol. Recrystallise the derivative from methanol,
ethanol or ethyl acetate.

(iii) Oximes
Hydroxylamine hydrochloride (0.5 g) is dissolved in water (2 mL). 10% sodium hydroxide (2
mL) and the carbonyl compound (0.2 - 0.3 g) dissolved in alcohol (1 - 2 mL) are added, the
mixture warmed on a steam bath for 10 min and then cooled in ice. Crystallisation is induced
by scratching the sides of the test tube with a glass rod. The oximes may be crystallised from
alcohol.

ACIDS

(i) Amides, anilides and p-toluidides

The acid (0.5 g) is refluxed with thionyl chloride (2 - 3 mL) in a fume cupboard for about 30
mins.* It is advisable to place a plug of cotton wool in the top of the reflux condenser to
exclude moisture. The condenser is removed and the excess of thionyl chloride is distilled off
(b.p. 78 ). The acid chloride thus produced is treated with concentrated ammonia solution (5
mL) or aniline (0.5 - 1 mL) or p-toluidine (0.5 - 1 g), when the solid derivative separates out.
It is collected and recrystallised from alcohol adding decolourising charcoal if found
necessary.

*Alternately use PCl5 to form the acid chloride.

AMINES

(i) Acetyl derivatives (acetamides)

Reflux gently in a small dry flask under a dry condenser the amine (1 g) with acetic
anhydride (3 mL) for 15 min. Cool the reaction mixture and pour into 20 mL cold water. Boil
to decompose the excess acetic anhydride. Cool and filter by suction the insoluble derivative.
Recrystallise from ethanol.

(ii) Benzoyl derivatives (benzamides)

Suspend 1 g of the amine in 20 mL of 5% aqueous sodium hydroxide in a well-corked flask,
and add 2 mL benzoyl chloride (fume hood!), about 0.5 mL at a time, with constant shaking.
Shake vigorously for 5 - 10 min until the odour of the benzoyl chloride has disappeared.
Ensure that the mixture remains alkaline. Filter off the solid derivative, wash with a little cold
water and recrystallise from ethanol.

(iii) Benzenesulphonamides
To 1 g of the amine in 20 mL of 5% sodium hydroxide solution in a well-corked flask add 1
mL benzenesulphonyl chloride (fume hood!). Shake the mixture until the odour of the
sulphonyl chloride disappears. Check that the solution is alkaline. Acidify if necessary to
obtain the precipitated derivative. Concentrated hydrochloric acid added dropwise should be
used. Filter the product, wash with a little cold water and suck dry. Recrystallise from
ethanol.

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The Department of Chemistry, University of the West Indies,
Mona Campus, Kingston 7, Jamaica.
Created March 1997. Links checked and/or last modified 11th December 2005.
URL http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt25.html
aromatic substitution

Halohydrocarbons
Alcoloic Siver Nitrate Test
Add, ppt means halide present, yellow = bromine, purple = iodine, milky = chlorine
Beilstein Flame Test
Flame substance on copper wire, color indicates halides

Alcohols
Ceric Ammonium Nitrate Test
test
Lucas Test
test
Chromic Acid Oxidation
test

Phenols
Ceric Ammonium Nitrate
test
Ferric Chloride
Add ferric chloride and look for a red ppt.

Aldehyde and Ketones

2,4-Dinitrophenylhydrazine
Aldehydes and Ketones (but not acids, esters, amides, anhydrides, and other
carbonyl containing groups) react with 2,4-dinitrophenylhydrazine to form Shift's
base derivatives (2,4- dinitrophenylhydrazones) as colored precipitates. A positive
test is indicated by formation of a copious quantity of precipitate. Some alcohols
contain small amounts of ketone or aldehyde impurities which will give a false
positive test. Also, contamination of the test tube by acetone will give a false positive
test.

Procedure -- In a large test tube add two drops (or half a microspatula) of the organic
compound to 1 mL of ethanol. Once the substrate has dissolved, add 2-3 drops of
the 2,4-DNP in H2SO4 reagent and shake the test tube vigorously. If no precipitate
forms immediately, heat the solution in hot tap water for 1 min and then add five
drops of water. The formation of a yellow to red precipitate is a positive test. Clean
up: Organic waste container.
Chromic Acid Oxidation
Aldehydes are readily oxidized to acids by this reagent. Ketones are relatively
unreactive at room temperature. The reagent is reduced in the process to a blue-
green precipitate of chromium (III) sulfate. Any other colored precipitate is not a
positive test. Aromatic aldehydes react more slowly than aliphatic aldehydes;
therefore, if no precipitate forms at once let the tube stand for several minutes.
Other oxidizable groups like phenols, alcohols, alkenes, and alkynes give false
positive tests.

Procedure --In a large test tube add one drop of the organic compound to 2 mL of
acetone and then add one drop of the chromic acid reagent. Note the time interval
required for formation of the blue-green precipitate. Clean up: Acids/Metals waste
container.
Iodoform Formation
look for carboxyl type ketones
Tollen's Test
use silver nitrate and make a silver mirror
Schiff's Test
test

Amines
Hinsburg Test
The Hinsberg test indicates whether a water insoluble amine is 1°, 2 °, or 3°. Primary
amines give a sulfonamide derivative soluble in NaOH. Secondary amines give a
base insoluble sulfonamide derivative. Water insoluble tertiary amines are inert (two
layers would be seen). If a precipitate forms in the Hinsberg test, it can serve as a
benzenesulfonamide derivative of your unknown amine. Alternatively, a larger
quantity of a benzenesulfonamide derivative can be made by following the procedure
in the "Preparation of Derivatives of an Unknown Amine" section below. If you know
that your unknown is an amine, it will save you time to go to #2 below and follow the
procedure on the larger scale.
Procedure -- In a large test tube, add 2 ml of methanol, five drops of the amine and
eight drops of benzenesulfonyl chloride. Warm the mixture over a steam bath for at
least 5 min with agitation. Add 2 mL of 6M aqueous sodium hydroxide. Cork the tube
and then vigorously shake the solution for 10 min. Keep the mixtyie warm during this
period in order to hydrolyze any excess benzenesulfonyl chloride that remains. Cool
in an ice bath.

If the unknown amine is a 1° amine boiling less than 100°C, the mixture should be a
homogeneous solution. Larger and higher boiling primary amines sometimes give
salts insoluble in the concentrated base. If you get a solid at this point, see if it
dissolves in water (cool then warm). If the unknown amine is a secondary amine, a
precipitate of the sulfonamide derivative is usually observed in the test tube and it
will NOT dissolve in water. If the amine is a water- insoluble tertiary amine, a layer of
the unreacted amine is observed on the top of the aqueous solution.

If an precipitate formed in the basic solution, it can be collected by filtration and then
washed twice with 5 mL of water. It is a sulfonamide derivative of a secondary
amine.

If no precipitate appeared, add 6M HC1 (concentrated HC1 is 12M) slowly to the

mixture until the solution is acidic. The sulfonamide of a 1° amine is insoluble in
acidic solution. It can be collected by filtration, washed with 10% HC1 and then
thoroughly with water to give the sulfonamide derivative.

If two layers were present, indicating an insoluble 3° amine, addition of 10% HC1
should give a homogeneous solution as the water soluble amine hydrochloride salt
forms.

Clean up: Aqueous solutions of acids and bases are neutralized and put down the
drain.
Diazo Coupling Test
test

Nitrile
Hydrolysis
test

Carboxylic Acid
Nutralization equivalent
test

Acid Chloride
Silver Nitrate
test

Ester
Hydroxamate
Esters can be converted into hydroxamic acids by reaction with hydroxylamine
hydrochloride. The hydroxamic acid derivatives form red or violet complexes with
aqueous ferric chloride. Phenols also give colored complexes with ferric chloride so
an unknown compound must be tested first with ferric chloride before reaction with
hydroxylamine to eliminate this possibility.

Procedure -- If 20 mg of the unknown compound shows no color change when

treated with 0.5 mL of 5% aqueous ferric chloride, perform the rest of this procedure.
To a clean test tube add 20 mg of the unknown compound tol mL of 1M
hydroxylamine hydrochloride in ethanol. Then add dropwise a 15% ethanolic solution
of potassium hydroxide until the test solution is just basic to pH test paper. Add five
additional drops of 15% ethanolic potassium hydroxide. Heat the mixture to boiling
for 30 seconds and then allow it to cool to room temperature. With thorough mixing,
add dropwise an aqueous solution of 10% aqueous HC1 until the pH of the mixture
is approximately 3. Add two drops of the 5% aqueous ferric chloride and note the
color. The immediate formation of a red-blue or violet color is an indication that the
original compound is an ester. Clean up: Place into the bottle marked "metals".

β-Dicarbonyl
Ferric Chloride Complex
test

Soduim Fusion Test

Some of the unknowns in this and subsequent experiments may contain nitrogen.
Henceforth it will be necessary to test the sodium fusion filtrate for this element as
well as for halides and to report the results on your cards and in your conclusions.
While sodium fusion converts halogens into the corresponding halide ions, it
converts nitrogen into the cyanide ion. The test for nitrogen is based upon the
intense color produced when the cyanide ion adds to p- nitrobenzaldehyde.

Procedure -- Test for Halogens -- Place a wax coated pellet of sodium in a small
pyrex test tube. Using tongs hold the tube over a flame to melt the wax and the
sodium. Use the Bunsen burner only in the designated area. While still hot add two
drops of the compound (10 mg of a solid) to the molten sodium. Heat the tube to red
hot for 2 mins and then at once plunge the bottom into 10 mL of distilled water
contained in a 50 mL beaker. Filter the solution by gravity into a large test tube. It
should be colorless. A brown tinge will interfere with the later test for bromine.
Remove 0.5 mL of the filtrate to test for the presence of C1-, Br-, or I- (F- is not
detected). Use concentrated nitric acid to make the solution very acidic. Since
nitrogen may be present in the filtrate, add a boiling stone and then boil the solution
gently for two minutes to expel this element as HCN. Do this in the hood. Then add
three drops of aqueous 5% AgNO3 (never use ethanolic AgNO3!). A white or light
yellow precipitate indicates halide. A dark brown precipitate indicates that the pH is
too high. Add more concentrated nitric acid. If this test is positive, continue.

To detect the specific halogen present, place 0.5 mL of the filtrate in a large test tube
and then add 0.5 mL of CH2C12 as well as 3 drops of concentrated nitric acid.
Shake carefully. A purple color indicates that iodide has oxidized to iodine. If no
purple appears, go to *. If purple appears, remove the CH2C12 layer with a pipet.
Add fresh CH2C12 and then shake to extract more iodine from the water layer.
Again remove the bottom layer. Repeat this extraction process until the purple color
is gone. The bottom CH2C12 layer should be colorless.

*Add 2 mL of concentrated nitric acid to the test tube and shake with care. A change
from colorless to a faint brown color indicates that bromide has been oxidized to
bromine. If no brown color appears, go to #. If brown color did appear, it must be
extracted with CH2C12 as described above for iodine until the bottom layer is
colorless.

#Finally, add three drops of 5% aqueous silver nitrate solution. A white precipitate is
AgCl.

Clean up: Your test tube may have two layers (organic and aqueous) at this point.
Put the aqueous supernatant layer down the drain. The methylene chloride layer
must be put into the organic waste

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