LAB #1 Reactions of Hydrocarbons Return

Hydrocarbons, compounds which contain only carbon and hydrogen, can be

classified into several types, depending on their structure. Aliphatic
hydrocarbons are divided into three classes: alkanes have only single bonds,
and are said to be saturated; alkenes and alkynes have carbon-carbon double
or triple bonds, and are said to be unsaturated.Aromatic hydrocarbons are
cyclic compounds whose structure is related to that of benzene, with six
-electrons in a six-membered ring.

The following experiments illustrate some of the fundamental reactions of

saturated, unsaturated, and aromatic hydrocarbons. The three classes
sometimes react differently toward the same reagent, in which case it may be
used to distinguish between them.

Aliphatic Hydrocarbons
All tests should be carried out in dry test tubes, and observations should be
recorded on the report sheet as each experiment is performed.

1. Bromine or chlorine water

Alkanes react slowly or not at all with bromine at room temperature in the
dark, but in the presence of sunlight, substitution is fairly rapid:

R-H + Br2 --light--> R-Br + HBr (a substitution rxn)

The reaction is easily detected by loss of the bromine colour and by evolution
of hydrogen bromide.

On the other hand, bromine adds rapidly at room temperature to alkenes in a

reaction which does not require light. Since the product is colourless, the
bromine is rapidly decolorized when added to an alkene.

Procedure
Put 1 mL portions of cyclohexane into two separate test tubes. Add 10-15
drops of bromine or chlorine water. After shaking the tubes, place one in the
dark, (under the counter) and expose the other to sunlight or a bright light for
a few minutes. Then compare the colour of the two tubes. Test for the presence
of hydrogen bromide or hydrogen chloride by holding a piece of moist blue
litmus at the mouth of each tube.

Add 1 mL of cyclohexene to a clean test tube. Add 10-15 drops of bromine or

chlorie water, shake the tube and observe the result. Test for the presence of
hydrogen bromide or hydrogen chloried evolution.

2. Aqueous Potassium Permanganate (Baeyer's Test)

Alkanes are relatively inert to chemical oxidizing agents such as neutral or
alkaline permanganate, where alkenes are readily oxidized at room
temperature. The change in colour can be used as a test for a double bond,
provided the molecule contains no easily oxidizable group.

Procedure
Place 5mL of potassium permanganate solution in two separate test tubes.
Add about five drops of alkane to one tube and the same of alkene to the other
test tube. Shake the tubes well for 1 -2 minutes, and note the results.

3. Sulphuric Acid
Although alkanes are inert to cold, concentrated sulphuric acid, alkenes react
by addition. The product, alkyl hydrogen sulphate, is soluble in concentrated
sulphuric acid.

Procedure
To each of two 2 mL portions of concentrated sulphuric acid in separate test
tubes add about 10 drops of alkane and alkene, respectively. Shake the tubes
well and note the results. Discard the contents by pouring them into a beaker
containing at least 50 mL of water.

Rxns of Aromatic Hydrocarbons

Toluene will be used in each of the following experiments. Although formally
unsaturated, C6H6CH3 in the sense that it has multiple carbon-carbon double
bonds, toluene does not give the usual reactions expected of an alkene. It is not
easily oxidized, and preferably undergoes substitution rather than addition
reactions.

1. Bromine
Add 1 mL of toluene to a small test tube. To another, add a few iron filings,
followed by 1 mL of toluene, using the latter to rinse down any filings stuck on
the test tube walls. To each test tube add three drops of bromine. Place the
tubes in a beaker of warm water for 15 minutes. Observe the colour of each
tube, and whether or not hydrogen bromide was evolved and record the
results.

2. Aqueous Potassium permanganate

To a test tube containing 1 mL of toluene add 2 mL of dilute (2.0% w/w)
potassium permanganate solution, shake and record the results.

Rxns of Alcohols and Phenols

The following tests and experiments are designed to illustrate some properties
and reactions of alcohols and phenols.
R-OH Ar-OH
 alcohol phenol

1. Solubility
The presence of a hydroxyl group in alcohols and phenols permits hydrogen
bonding between then and the similar substance water, H-OH. This leads to
appreciable water solubility for these classes of compounds, particularly the
lower members of the series.

Procedure
In six separate test tubes place 0.5 mL or 0.2 -0.5 g of each of the following:
ethanol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, iso-amyl alcohol, and
phenol. (Caution:Avoid any skin contact with phenol. In case of a burn, wash
thoroughly with water for 15 minutes sand notify the teacher.) Add 2 mL of
water to each tube, mix, and observe. Record the results on the report sheet.

2. Reaction with Alkali

Phenols are more acidic than alcohols and may be converted to their sodium
salts by reaction with aqueous sodium hydroxide. The sodium salts are usually
soluble in water.

Procedure
In four separate test tubes place 0.5 mL or 0.2-0.5 g of each of the
following: n-butyl alcohol, cyclohexanol, phenol, and 1-naphthol. Add 5 mL
of 10% sodium hydroxide to each tube, observe, and record the result.

3. Reaction with Metallic Sodium

Just as with water, the hydrogen atom of the hydroxyl group in alcohols and
phenols can be displaced by sodium:

2 R-OH + 2 Na -------> 2 R-O-Na+ + H2

an alkoxide

The resulting alkoxides are strong bases, useful when a basic catalyst is needed
for an organic reaction.

Procedure
Place 2 mL of each of the following in separate dry test tubes: ethanol, 1-
propanol, 2 -propanol, and orcinol. Add a small piece of sodium metal to each
test tube and note the result. Add a few drops of universal indicator to the
solution and record the result. (Caution:DO NOT discard the contents of any
tube with unreacted sodium down the drain; sodium reacts violently with
water. Add sufficient ethanol to destroy any unreacted sodium, then rinse the
solution down the drain.)

Tests for the Three Classes of Alcohols

Alcohols are classified as primary, secondary, or tertiary, depending on
whether the hydroxyl group is attached to a carbon that is bound to one, two
or three other carbon atoms. Alcohols treated with a particular reagent may
differ in the rates that they react, or indeed even in the type of product
obtained, depending upon the class to which they belong. Tests which
distinguish among the three classes can be useful in determining the structure
of an unknown alcohol.

The Lucas Test

The reagent is a solution of zinc chloride in concentrated hydrochloric acid.
The test is based on the different rates at which primary, secondary and
tertiary alcohols are converted to their chlorides.

ZnCl2
R-OH + HCl ---------> R-Cl + H2O

Tertiary alcohols react instantly, giving an insoluble alkyl chloride which

appears as a cloudy dispersion or as a separate layer. Secondary alcohols
dissolve to give a clear solution (provided R does not have too many carbon
atoms in the chain.), then form chlorides (cloudy solution) within five minutes.
Primary alcohols are not converted to chloride for several hours at room
temperature with this reagent.

Procedure
Place 2 mL of Lucas reagent in each of four test tubes. Add about five drops of
the alcohol to be tested, shake , and note the length of time it takes for the
mixture to become cloudy or separate into two layers. Test 1-butanol, 2-
butanol, cyclohexanol, n-amyl alcohol, benzyl alcohol and t-butyl alcohol and
record the results.

Chromic Acid Oxidation (Bordwell-Wellman Test)

Primary and secondary alcohols are oxidized rapidly by chromic acid, where
tertiary alcohol are not. In this test, an acetone solution of the alcohol to be
tested is treated with a solution of chromic anhydride (Cr5+) in sulphuric acid.
Alcohols which are oxidized reduce the chromium to Cr3+, causing the solution
to become opaque and take on a greenish cast.

Procedure
Place 1 mL of acetone in each of five separate test tubes.
To each tube, add one drop of a liquid alcohol or a few crystals (10 mg.) of a
solid alcohol to be tested and shake until the solution is clear. The add, with
shaking, one drop of the reagent. Test the following alcohols: 1-butanol, 2-
butanol, t-butyl alcohol, n-amyl alcohol, benzyl alcohol, and cholesterol.

Reactions of Phenols
A. With Bromine Water
The hydroxyl group of phenols activates the ring to electrophilic substitution,
so that reaction occurs under very mild conditions. With bromine water and
phenol, the product is 2,4,6-tribromophenol, which has such a low solubility in
water that it is often used not only as a qualitative test for phenol but also as a
quantitative measure of the amount of phenol present.
Procedure
To about 0.1 g of phenol dissolved in 3 mL of water add bromine water with
shaking, until the yellow colour persists. Observe the results.

B. With Ferric Chloride

Phenols and compounds with a hydroxyl group attached to an unsaturated
carbon atom(enols) give a coloration (pink, green, or violet depending on the
structure of the phenol or enol) with ferric chloride. This is due to the
formation of certain coordination complexes with the iron. Ordinary alcohols
do not react. This test may be used to distinguish most phenols from alcohols.

Procedure
In three separate test tubes dissolve one or two crystals, or one or two drops of
the compounds to be tested in 5 mL of water. To each tube, add one or two
drops of 1% ferric chloride solution, shake, and observe the results. Test
phenol, resorcinol and 2-propanol, and record the results.

Reactions of Aldehydes and Ketones

Aldehydes and ketones both have, as their functional group, a carbon-oxygen
double bond (carbonyl group). Accordingly, they undergo similar reactions.
With the same reagent, aldehydes usually react faster than ketones, mainly
because there is less crowding at the carbonyl carbon. Aldehydes are also
more easily oxidized than ketones.

Oxidation
Aldehydes are easily oxidized to acids which have the same number of carbon
atoms.

An analogous reaction is not possible for ketones, whose oxidation to an acid

requires the rupture of a carbon-carbon bond and results in two acids, each
with fewer carbon atoms than the original ketone.

Several simple tests which are based on this difference in reactivity toward
oxidizing agents are used to distinguish between the two classes of carbonyl
compounds.

Aldehyde and Ketone Tests

1. Tollen's Silver Mirror Test
Tollens' reagent is an ammoniacial solution of silver ion prepared by dissolving
silver oxide in ammonia.

---->R-C-OH + HO-C-R'

Several simple tests which are based on this difference in reactivity toward
oxidizing agents are used to distinguish between the two classes of carbonyl
compounds.
The reagent is reduced to metallic silver by aldehydes which, in turn, are
oxidized to the corresponding acids. Ketones are not oxidized by the reagent.

O O
|| ||
R-C-H + 2 Ag(NH3)2+OH- -----> R-C-O-NH4+ + 2 Ag + 3 NH3 + H2O

If the test is carried out with dilute solutions of reagents, in scrupulously clean
glassware, the silver deposits finely in the form of a mirror on the walls of the
beaker or test tube. Otherwise, the silver is deposited as a black precipitate.

Procedure
Tollin's reagent is explosive on standing for long periods of time, therfore the
reagent is prepared fresh just before it is needed as follows: Clean a test tube
thoroughly with soap and water, and rinse with distilled water. To 2 mL of 5%
silver nitrate solution add two drops of 5% sodium hydroxide solution and mix
thoroughly. Then add drop by drop, and with stirring, only enough 2%
ammonium hydroxide (concentrated ammonium hydroxide is 28%) to dissolve
the precipitate. The test will fail if excess ammonia is added.

Prepare four test tubes with Tollen's reagent. Test each of the following by
adding two drops of the substance: benzaldehyde, acetone, ethyl methyl
ketone, and acetaldehyde. Shake the mixture, then allow it to stand for 10
minutes. If no reaction has occurred place the tube in a beaker of warm water
(35-50oC) for five minutes. Record your observations.

2. Fehling's or Benedict's Test

The reagent in each of these tests is cupric ion, Cu2+ in an alkaline solution. To
keep the copper from precipitating as the hydroxide, it is complexed with
either tartrate ion (Fehling's reagent) or citrate ion (Benedict's reagent). For
simplicity's sake we will write the equation with just the cupric ion. Aldehydes
reduce the copper; the solutions usually turn from blue to muddy green, and
gradually a reddish precipitate of cuprous oxide, Cu2O is formed. Most simple
ketones do not react, although certain hydroxyketones and carbohydrates do.

O O
|| ||
R-C-H + 2 Cu2+ + 5 OH- ----> R-C-O- + Cu2O + 3 H2O
brown

Procedure
To each of four test tubes add either 5 mL of Benedicts reagent or 5 mL of
freshly prepared Fehling's reagent (made by mixing 10 mL of Fehling's A and
10 mL of Fehling's B solutions). To each tube add a few drops of the substance
to be tested. Place the tubes in a beaker of boiling water and observe the
changes which occur during 10-15 minutes. Test acetaldehyde, acetone and
methyl isobutyl ketone and glucose.
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