CLASSIFICATION TESTS FOR ORGANIC HALIDES

Lorraine M. Ramos, Sharmaine Michelle M. Reyes, Rhone Arevyn E. Roque

Joseph T. Sabido and Jan Armelynn S. Santos
Group 7 2A Medical Technology Organic Chemistry Laboratory

ABSTRACT
The experiment is to understand and classify organic halides as organic compounds containing a halogen atom bonded
to a carbon atom. Most organic halides are synthetic and not flammable. To attain the objectives of this experiment,
different samples of organic halides; primary, secondary and tertiary were classified according to S N reactivity and also
to differentiate the SN1 and SN2 mechanisms. Sample compounds of chlorobenzene, n-butyl chloride, sec-butyl chloride,
tert-butyl chloride were analyzed with Beilstein test, alcoholic AgNO3 and NaI in acetone. All the sample compounds
had produced a positive result with Beilstein test, affirming the presence of Chloride ion. When the compounds were
reacted with 2% ethanoic AgNO 3 to observe SN1 reactivity, all have attained a white precipitate in different time
required except for chlorobenzene which had observed to exhibit no reaction. While in the S N2 phase reactivity using
NaI in Acetone, it was observed that all have exhibit the presence of white precipitate except for chlorobenzene; noted
that the time required for each compound was different from that of S N1. Therefore, it was observed that there are
differences of the results attained from each S N reactivity or mechanisms and that these differences can be used to
classify organic halides.

INTRODUCTION
Chlorine, fluorine, bromine and iodine are
halogen atoms. A halogen atom that have been
substituted in one or more hydrogen atoms are
organic compounds commonly known as organic
halides. These compounds are considered to be
flame retardant and synthetic. [1] The reactivity
of organic halides depends on the halogen atom
that is bonded to the carbon atom in the
particular compound and can be classified
depending on the halogen atom position on the
chain of carbon atoms. The carbon which is
attached with the halogen atom is linked up with
only one other alkyl group in primary
halogenoalkanes, whereas directly linked up with
two and three other alkyl groups in secondary
halogenoalkanes and tertiary halogenoalkanes
respectively. [2] An organic halide can be named
as primary, secondary and tertiary depending on
the degree of substitution of the alpha hydrogen
atom by an R group on an sp3 hybridized alpha
carbon atom. [3]
By the use of substitution reaction with a
nucleophile, the reaction of an electron pair
donor (the nucleophile, Nu) with an electron pair
(the electrophile). A sp3-hybridized electrophile
must have a leaving group (X) in order for the
reaction to take place. [4] The reaction is SN1 or
unimolecular is a multi-step process and happens
if the rate of reaction is dependent on the organic
halide and it is SN2 or bimolecular is a single step
process and happens if the rate of reaction is
dependent on both the organic halide and the
nucleophile. [3]
For the compounds to be classified, it must be
subjected to some tests. Beilstein test is a simple
chemical test used in chemistry as a qualitative
test which uses color of the flame to indicate the

presence halides and was developed by Friedrich

Konrad Beilstein. [5] To test for SN1 reactivity the
samples were reacted with alcoholic AgNO 3 and to
test for SN2 reactivity it is reacted with NaI in
acetone. [3]
The experiment must be able to attain the
following objectives: (1) to differentiate primary,
secondary, and tertiary organic halides based on
their SN reactivity and (2) to differentiate S N1 and
SN2 mechanisms with organic halides.

EXPERIMENTAL
A. Samples used
n-butyl chloride
sec-butyl chloride
tert-butyl chloride
chlorobenzene
2% ethanoic AgNO3
15% NaI in anhydrous acetone
B. Procedure
1. Beiltein Test: Copper Halide Test

Figure 1. Organic Halide Samples

A small loop was made in one end of the

copper wire and was heated in the oxidizing zone
of a non-luminous flame until the green color
imparted to the flame disappeared. The loop was
cooled and dipped into the solid or liquid sample.
And the loop was heated together with the
sample in the inner zone to the outer zone of a
non luminous flame. A blue-green (or green)
colored flame was observed to indicate the
presence of chlorine, bromine or iodine.
2. SN1 Reactivity: Reaction with Alcoholic
AgNO3
Five drops of the sample was added to 20
drops of 2% ethanoic AgNO3. The sample was
shaked and the time in seconds or minutes for a
silver halide precipitate to form was observed and
recorded. The color of the precipitate was then
observed and described.

The Beiltein test was performed as a quick

preliminary check for the presence of halogens,
wherein all samples was observed with a blue
green colored flame, exhibiting the presence of
halide. It was also the simplest method for
establishing the presence of such, but does not
positively differentiate between Chloride, Bromide
and Iodide ion.
The blue-green color was observed due to the
emission of light from excited states of copper
halide that has vaporized in the burner flame. To
remove the traces of sodium chloride that may be
present on the wire from handling it with fingers
was carried out by heating the copper wire before
the test.
Cu + O2

CuO (black solid)

RX + CuO

CuX2+ CO2+H2O

CuX2 is volatile and imparts a blue-green flame.

Table 2. Data obtained using SN1 reactivity to
organic halides

Figure 2. SN reactions or mechanisms

3. SN2 Reactivity: Reaction with NAI in
Acetone
5 drops of each sample was added to 2 drops
of 15% sodium iodide in anhydrous acetone. The
contents were mixed and the time required for a
precipitate to form and the color of the
precipitate was recorded and noted.

RESULTS AND DISCUSSION

On the experiment performed using different
kinds of classification tests for organic halides,
certain results were obtained.
Table 1. Data obtained from Beilstein Test
Compound used

Beilstein test

n-butyl chloride

Green flame

Sec-butyl chloride

Green flame

Tert-butyl chloride

Green flame

Chlorobenzene

Green flame

Compound used

Reaction with 2%
ethanolic silver
nitrate

n-butyl chloride

5 mins
White ppt.

Sec-butyl chloride

2 mins.
White ppt.

Tert-butyl chloride

18 secs
White ppt.

Chlorobenzene

No reaction
No ppt.

In the test for SN1 Reactivity by reaction with

alcoholic AgNO3 tert- butyl chloride was the first
to produce a white precipitate followed by secbutyl chloride, n-butyl chloride and no reaction
with chlorobenzene. The kinetics of the reaction
is dependent on the alkyl halide. The more stable
the carbocation intermediate the faster the rate
of SN1 reaction. A good leaving group was
important for the reaction to occur. The solvent
used should be a protic, polar solvent that
stabilizes the carbocation intermediate by
solvation that increases the reaction rate. In
terms of stereochemistry, this involves inversion
and retention. The SN1 reaction happens when
substrate dissociate to a carbocation in a slow
rate-limiting step, followed by a rapid attack of a
nucleophile. This reaction shows first order

kinetics and take place with racemization of

configuration at the carbon atom.
Table 3. Reactions obtained using SN2 reactivity
to organic halides
Compound used

Reaction with 15%

sodium iodide in
anhydrous acetone

n-butyl chloride

immediately
White ppt.

Sec-butyl chloride

immediately
White ppt.

Tert-butyl chloride

immediately
White ppt.

Chlorobenzene

No reaction
No ppt.

In the test for SN2 reactivity by reaction of NaI

in acetone, n-butyl chloride is the first to show a
white precipitate followed by sec-butyl chloride,
tert- butyl chloride and no reaction in
chlorobenzene. The kinetics of this reaction was
dependent on the alkyl halide and nucleophile.
Due to steric effect, the substrate effect in SN1
reaction was the opposite in S N2 reactions. It
favors primary and secondary substrates. A
strong nucleophile was needed for reaction to
occur because it parallels basicity. The solvent
should be a polar, aprotic solvent. In terms of
stereochemistry, it involves Walden inversion of
configuration. The reaction occurs as the entering
nucleophile attacks the halide 180
away from
the leaving group. The reaction exhibits secondorder kinetics and it was affected by steric effect
caused by the bulky group of the reagents. The
SN2 reaction favors primary and secondary
substrates compared to SN2 reaction that favors
tertiary substrates.

REFERENCES
[1] Bayquen, A.V., Cruz, C.T., de Guia,
R.M.,Lampa, F.F., Pena, G.T., Sarile, A.S., Torres,
P.C. (2009).Laboratory Manual in Organic
Chemistry. Quezon City: C & E Publishing, Inc.
[2] Organic Chemistry Portal. Nucleophilic
Substitution.
http://www.organicchemistry.org/namedreactions
/nucleophilic-substitution-sn1-sn2.shtm 9/12/11
[3] Chemical Land. Butyl Chlorides
http://chemicalland21.com/industrialchem/organi
c/TERT-BUTYL%20CHLORIDE.htm 9/12/11
[4] Chemistry education. Beilstein Test
http://ull.chemistry.uakron.edu/organic_lab/beil/
9/12/11

[5] Paar, L. et al. (2008). Organic Chemistry

Laboratory Experiments for Organic Chemistry
Laboratory.
http://webcache.googleusercontent.com/search?
q=cache:2LqimCkaFBYJ:cns.uni.edu/~manfredi/8
60-121/ORG%2520LAB%2520MAN%2520S08.
pdf+sublimation+formal+report&hl=tl&gl=ph
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