CLASSIFICATION TESTS FOR N-BUTYL CHLORIDE, SEC-BUTYL CHLORIDE,

TERT-BUTYL CHLORIDE AND CHLOROBENZENE

Sadhwani, Alysha Joy V., San Andres, Twizle DP., Santos, Luisa Marie A., Suzuki, Mikorin A., Sy,
Marieneth Angela U.

Group 8, 2F - Pharmacy, Faculty of Pharmacy, University of Santo Tomas

Abstract

Organic halides are not flammable. If the ά -carbon atom is tetragonal or sp3 hybridized in the compound, the organic
halide may be classified as primary, secondary or tertiary, depending on the degree of substitution of the ά-hydrogen
atom by an R group. Reactivity of these types of organic halides can be differentiated via a substitution reaction with a
nucleophile, depending on which reactant molecule (nucleophile or organic halide) is involved in the rate-determining
step. If the rate of the reaction is dependent on the organic halide, the reaction is unimolecular, thus saying that it is a
SN1 mechanism. If the rate is dependent on both the organic halide and the nucleophile, the reaction is bimolecular or
a SN2 mechanism. The sample compounds, n-butyl chloride, sec-butyl chloride, tert-butyl chloride and chlorobenzene
were subjected to different classification tests. First the Beilstein test, where the blue-green (green) flame is observed
through the looped copper wire. Second is the reactivity with Alcoholic silver nitrate, where the silver halide precipitate
is observed and noted. The same with the third, the reactivity test with sodium iodide in anhydrous acetone, where
precipitate was observed. All the sample compounds showed enough reactions with the different classification for us
to say that all of them are organic halides.

halogen bond of alkyl halides is polarized; the

Introduction
Organic halides are organic compounds
containing a halogen atom bonded to a
carbon (C) atom. Fluorine (F), chlorine (Cl),
bromine (Br), and iodine (I) are all types of
halogen atoms. A compound that contains a
carbon atom bonded to a fluorine atom (C-F)
is called an organofluoride. If the carbon atom
is part of a chain of carbon atoms, the
organofluoride compound is referred to as an
alkyl fluoride. If the carbon atom is contained
in a benzene or phenyl ring, the
organofluoride is called an aryl fluoride. Other
halide compounds are named in a similar
fashion.
The reactivity of organic halides depends
on the halogen atom that is bonded to the
carbon atom in the particular compound.
Organoiodides are the most reactive and can
be converted into many other compounds.
Organobromides are less reactive than
organoiodides but more reactive than
organochlorides. Organofluorides are the
least reactive of the organic halides.
The halogen atom of an alkyl halide is
attached to an sp3 – hybridized carbon. The
arrangement of groups around the carbon
atom, therefore, is generally tetrahedral.
Because halogen atoms are more
electronegative than the carbon, the carbon –
carbon atom bears a partial positive charge,
the halogen atom a partial negative charge.
The size of the halogen atom increases as
we go down the periodic table: fluorine atoms
are the smallest and the iodine atoms are the
largest. Consequently, the carbon – halogen
bond length also increases as we go down
the periodic table.
In the laboratory and in the industry, alkyl
halides are used as solvents for relatively
non-polar compounds. The halogen of an
alkyl halide can be easily replaced by other
groups, and the presence of a halogen atom
on a carbon chain also affords us the
possibility of introducing a multiple bond.
(Solomons-2011)
Table 1.1 Carbon – Halogen Bond Lengths
(Solomons-2011)
Bond Bond Length
CH3 – F 1.39
CH3 – Cl 1.78
CH3 – Br 1.93
CH3 – I 2.14
The experiment was done for the group to
(1) differentiate primary, secondary, and
tertiary organic halides based on their SN
reactivity and for the group to (2) differentiate
SN1 and SN2 mechanisms with organic
halides.
 Materials and Methods Compound used Beilstein test
n-butyl chloride Green flame
The materials in this experiment were the
Sec-butyl chloride Green flame
sample compounds, n-butyl chloride, sec-
butyl chloride, tert-butyl chloride and Tert-butyl chloride Green flame

chlorobenzene. This experiment also used Chlorobenzene Green flame

copper wire for the Beilstein test, 2%

ethanolic silver nitrate for SN1 Reactivity:
Reaction with Alcoholic silver nitrate, 15%
sodium iodide for SN2 Reactivity: Reaction
with sodium iodide in acetone.
A. Beilstein Test: Copper Halide Test
A copper wire looped on one end was
heated directly in the oxidizing zone of a non-
luminous flame until the green color impaired
to the flame disappeared. The copper wire,
after being cooled, was dipped into the solid
or liquid sample. The loop wad heated with
the sample in a non-luminous flame: first in
the inner zone, then in the outer zone near
the edge of the flame. And a blue-green (or
green) – colored flame indicates the presence
of chlorine, bromine, or iodine.
The Beilstein test is a quick preliminary
check for halogens. It is the simplest method
for establishing presence of a halogen, but
does not positively differentiate between Cl,
Br, I
The blue – green color is due to the emission
of light from excited states of copper halide
that has vaporized in the burner flame.
Heating the copper wire before the test is
carried out removes traces of sodium chloride
that may be present on the wire from
handling it with the fingers.
Cu+O CuO
Loop black solid

B. SN1 Reactivity: Reaction with the RX + CuO CuX + CO + H O

Alcoholic Silver Nitrate
5 drops of each sample was added to 20 CuX2 is volatile and imparts a blue-green
drops of 2% ethanolic silver nitrate, shaked flame.
and noted the time for a silver halide
precipitate is formed. Also the color of the Table 2.2 Classification test results on
precipitate was noted. organic halides using SN1 & SN2 reactivity
Reaction with 2% Reaction with 15%
C. SN2 Reactivity: Reaction with the
Compound used ethanolic silver sodium iodide in
Sodium Iodide in Acetone
nitrate anhydrous acetone
5 drops of each sample was added to 2
1 min.
drops of 15% sodium iodide in anhydrous 3 secs.
acetone. The contents were mixed and the n-butyl chloride No ppt. – slightly
White ppt.
time required for a precipitate to from and the cloudy
color of the precipitate was recorded and 12 secs. 3.61 secs.
Sec-butyl chloride
noted. Cloudy ppt White ppt.
1 sec. 3.69 secs.
Results and Discussion Tert-butyl chloride
Light purple ppt. Light yellow ppt.
1 sec. 2.66 secs.
Qualitative tests for alkyl halides are useful Chlorobenzene
Purple ppt. White crystalline ppt.
in deciding whether the compound in
question is a primary, secondary, or tertiary
halide. In general it is quite difficult to prepare
solid derivatives of alkyl halides. On the SN1 Reactivity: Reaction with
Alcoholic Silver Nitrate, if a compound is
Performing different kinds of classification known to contain a halogen (bromine,
test for organic halides, certain results were chlorine, or iodine), information concerning its
obtained. environment may be obtained from
observation of its reaction with alcoholic silver
Table 2.1 Classification test results on nitrate. The overall reaction is shown in the
organic halides using Beilstein test following equation:
 Ethanol
RX + AgNO3 ---------------> AgX + RONO2
Such a reaction will be of the S N1 type.
Tertiary halides are more reactive in an SN1
reaction than secondary halides, which are in
turn more reactive than primary halides.
Differing rates of silver halide precipitation
would be expected from halogen in each of
these environments, namely, primary <
secondary < tertiary. These differences are
best determined by testing in separate test
tubes authentic samples of primary,
secondary, and tertiary halides with silver
nitrate and observing the results. Alkyl
bromides and iodides react more rapidly than
chlorides, and the latter may require warming
to produce a reaction in a reasonable period.
Aryl halides are unreactive toward the test
reagent, as are any vinyl or alkynyl halides
generally. Allylic and benzylic halides, even
when primary, show reactivities as great as or
After subjecting all 6 organic samples to
different physical and chemical tests, it was
observed that all 6 organic samples were
flammable and immiscible in concentrated
H2SO4. All except hexane and heptane
produced soot when ignited. Only
cyclohexene behaved as an actively
unsaturated hydrocarbon. All were aromatic
compounds except cyclohexane and
cyclohexene. The only compound oxidized
was cyclohexene.
A strong nuclephile favors the SN2 reaction
mechanism, and a weak nuclephile favors the
SN1 reaction mechanism.
References
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Chemistry (7th edition). Hoboken, NJ: Wiley

greater than tertiary halides because of 2. Bailey, P. S., Bailey, C. A. (2000). Organic chemistry: a
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Another method for distinguishing between organic chemistry. Oxford: Pergamon Press
primary secondary and tertiary halides makes 4. Sorrell, T. N. (2006). Organic chemistry. Sausalito,
use of sodium iodide dissolved in acetone. California: University Science Books
This test complements the alcoholic silver 5. http://chemistry.gravitywaves.com/CHE301/Alkyl
nitrate test, and when these two tests are
%20Halide%20Classification%20Tests.htm
used together, is possible to determine fairly
6. http://www.scribd.com/doc/24691082/Post-Lab-Notes
accurately the gross structure of the attached
7. Bayquen, A., Cruz, C., de Guia, R., Lampa, F., Peña, G.,
alkyl group. The test depends on the fact that
both sodium chloride and sodium bromide are Sarile, A., Torres, P. (2009). Laboratory Manual in Organic
not very soluble in acetone, whereas sodium Chemistry. Manila: C&E Publishing, Inc.
iodide is. The reactions that occur are SN2
substitutions in which iodide ion is the
nucleophile; the order of reactivity is primary
> secondary > tertiary.
acetone
RCl + NaI ------------> RI + NaCl
acetone
RBr + NaI ------------> RI + NaBr

With the reagent, primary bromides give a

precipitate of sodium bromide in about 3 min
at room temperature, whereas the primary
and secondary chlorides must be heated to
about 500C before reaction occurs.
Secondary and tertiary bromides react at
50EC, but the tertiary chlorides fail to react in
a reasonable time. It should be noted that
this test is necessarily limited to bromides
and chlorides.