The Categorizing of Primary, Secondary, and Tertiary Organic Halides Based on their

Nucleophilic Substitution Reactivity

Chua, K.M.D., Cocjin, C.M.PH.R, Dizon, J.A.H., Donato, L.P.G., Dumaplin, R.A.L, Elepao,
M.A.S.P., 2B-PH, Group 3, Department of Pharmacy, Faculty of Pharmacy, University of Santo
Tomas, Espaa Boulevard, 1015 Manila, Philippines
ABSTRACT
Organic halides are organic compounds that contain one or more halogens in addition to carbon
and hydrogen [1]. This experiment was conducted to differentiate primary, secondary, and
tertiary organic halides based on their S N reactivity and to differentiate between S N1 and SN2 as
reactive mechanisms with organic halides [2]. The samples used for this experiment are n-butyl
chloride, sec-butyl chloride, tert-butyl chloride, and chlorobenzene. The Beilstein Test, also
called the Copper Halide Test, was utilized to detect the presence of chlorine in the samples [2].
Upon dipping a copper wire to each of the samples, each sample showed a positive reaction
which resulted in an appearance of a green flame. The samples were analyzed with alcoholic
silver nitrate and sodium iodide. For SN1 reactivity, the samples were reacted with 2% ethanolic
silver nitrate. The fastest to form a precipitate was tert-butyl chloride, then sec-butyl chloride,
followed by n-butyl chloride while chlorobenzene did not form a precipitate. For S N2 reactivity,
the samples were reacted with 15% sodium iodide in acetone. The fastest to form a precipitate
was sec-butyl chloride, followed by tert-butyl chloride while chlorobenzene and n-butyl chloride
did not form a precipitate. From the results, it can be observed that for S N1 reactions, tertiary
alkyl halides like tert-butyl chloride are favored. Theoretically, SN2 reactions favor primary alkyl
halides but in this experiment n-butyl chloride did not form a precipitate upon addition of 15%
sodium iodide. Based on the results, the fastest to form a precipitate was sec-butyl chloride while
the slowest was tert-butyl.

INTRODUCTION
Organic halides are organic compounds
consisting of a halogen atom bonded to
carbon (C) atom. A halogen can be fluorine
(F), chlorine (Cl), bromine (Br), and iodine
(I) [3]. Organic halides are mostly synthetic
and are not flammable [2]. An -carbon is a
carbon atom that is bonded to a functional
group in an organic compound [4].
They can be classified into primary,
secondary, or tertiary organic halides
depending on how the halogen atom is
positioned on the chain of carbon atoms [5].
They can only be classified as such if the carbon is tetragonal or sp3 hybridized [2].
An -carbon can be classified as primary
when the carbon atom which has the

halogen is only attached to one other alkyl

halide, as secondary when the carbon atom
with the halogen is joined together directly
to two other alkyl groups which may be the
same or different, as tertiary when the
carbon atom with the halogen is directly
attached to three other alkyl groups [6]. The
reactivity of these types of organic halides
can be differentiated through the substitution
reaction with a nucleophile, which is
dependent on which reactant molecule is
involved in the rate-determining step [2].
Nucleophilic substitution reaction is a
reaction in which a nucleophile displaces
another nucleophile and takes its place. It is
represented by the symbol SN [7]. The SN1
reaction is a multi-step reaction that

indicates a substitution, nucleophilic,

unimolecular reaction. It is implied here that
the rate-determining step of the reaction is
dependent on the decomposition of a single
molecular species [8]. The SN2 reaction is a
bimolecular with a simultaneous bondmaking and bond breaking-steps. It does not
need an intermediate to proceed [9].
The objectives of this experiment are: (1) to
differentiate primary, secondary and tertiary
organic halides based on their nucleophilic
substitution reactivity, and (2) to
differentiate between SN1 and SN2 as
reactive mechanisms with organic halides.
METHODOLOGY
The apparatus that were used for this
experiment are: test tubes, test tube holder
and rack, matches, copper wire, and Bunsen
burner. The reagents used are 2% ethanoic
silver nitrate and 15% sodium iodide in
anhydrous acetone. The samples that were
used are n-butyl chloride, sec-butyl chloride,
tert-butyl chloride, and chlorobenzene.
After the apparatus were prepared, the
Beilstein test was performed. A small loop
was made on one end of the copper wire.
The Bunsen burner was ignited and the
copper wire was heated directly in the
oxidizing zone of the non-luminous flame.
This was continued until the green flame
that was imparted has totally disappeared.
The loop of the copper wire was allowed to
cool and was dipped into the sample. It was
then heated to the non-luminous flame: first
in the inner zone, then to the outer zone that
is near the edge of the flame. This process
was done for all the samples that were
given. All the samples imparted a green
flame indicating that all of them have
contain chlorine.
For the SN1 reactivity, 5 drops of each
sample were put into separate test tubes and
were labeled accordingly. Twenty drops of
2% ethanoic silver nitrate was put in a test

tube and was labeled. The reagent was made

four times to test each sample. It must be
noted that the solution of the reagent is not
turbid when used. The samples were added
into the reagent. They were then agitated
and formed precipitates in varied times. The
time of each change was recorded.
For the SN2 reactivity, 5 drops of each
sample were put into separate test tubes and
were labeled accordingly. Two drops of 15%
sodium iodide in anhydrous acetone was put
in a test tube and was labeled. It was made 4
times to test each sample. It must be noted
the solution of the reagent is not turbid when
used. The samples were added into the
reagent. They were then agitated and formed
precipitates in varied times. The time of
each change was recorded.
RESULTS AND DISCUSSION
The Beilstein test can be used to detect the
presence of a halogen in a compound [10].
For this experiment, the samples n-butyl
chloride, sec-butyl chloride, tert-butyl
chloride, and chlorobenzene were tested for
the presence of chloride. The presence of
chloride will impart a green flame [2]. The
data from the test is tabulated as shown in
Table 1.
TABLE 1. DATA
BEILSTEIN TEST

COLLECTED

FROM

THE

SAMPLE USED

COLOR OF FLAME

n-butyl chloride

green flame

sec-butyl chloride

green flame

tert-butyl chloride

green flame

chlorobenzene

green flame

The above data confirmed that all four

samples contain chloride.
In the test for SN1 reactivity ethanoic silver
nitrate was reacted with the samples, tert-

butyl chloride formed a white precipitate

first, followed by sec-butyl chloride, then nbutyl chloride. Ethanoic silver nitrate was
used because it is an alcohol which is an
aprotic solvent. Aprotic solvents are favored
in SN1 reactions [11]. Chlorobenzene did not
form a precipitate because it is an aromatic
compound. Aromatic compounds are sp2
hybridized and for a nucleophilic
substitution to occur the compound must be
sp3 hybridized. Also, phenyl cations are
unstable which has made the reaction
impossible [12]. The data from the reaction
is tabulated as shown in Table 2.
TABLE 2. DATA COLLECTED FROM THE SN1
REACTION

SAMPLE USED

REACTION WITH
2%
ETHANOLIC
SILVER NITRATE

n-butyl chloride

white ppt. formed

after 15 sec.
white ppt. formed
after 10 sec.
white ppt. formed
after 1 sec.
no ppt. was formed

sec-butyl chloride
tert-butyl chloride
chlorobenzene

Based on the data, the SN1 reaction favored

tert-butyl chloride which is a tertiary organic
halide. Tertiary organic halides are favored
because carbocation stability is highest in
these types of compounds [11].
In the test for SN2 reactivity, of 2% sodium
iodide in anhydrous acetone was reacted
with the samples, tert-butyl chloride formed
a white precipitate first, followed by secbutyl chloride, then tert-butyl chloride. Nbutyl chloride and chlorobenzene did not
form a precipitate. Theoretically, n-butyl
chloride should have reacted first however,
due to an unknown circumstance it did not
form a precipitate. Chlorobenzene did not
form a precipitate because it is an aromatic
compound. Aromatic compounds are sp2

hybridized and for a nucleophilic

substitution to occur the compound must be
sp3 hybridized [12].
TABLE 3. DATA COLLECTED FROM THE SN2
REACTION

SAMPLE USED

REACTION
WITH
15% SODIUM IODIDE
IN
ANHYDROUS
ACETONE

n-butyl chloride

no ppt. formed

sec-butyl chloride

white ppt. formed

after 7 sec.
white ppt. formed
after 11 sec
no ppt. was formed

tert-butyl chloride
chlorobenzene

Based on the data, the SN2 reaction favored

sec-butyl chloride which is a secondary
organic halide. The favored reaction should
have been n-butyl chloride which is a
primary organic halide. Primary organic
halides are favored because steric hindrance
is highest in these types of compounds [11].
REFERENCES:
[1] Rasheed, M.K. (n.d).Organic Halides.
Retrieved November 17, 2015 from:
http://www.comed.uobaghdad.edu.iq/upload
s/Lectures/Biochemistry%20first
%20year/Organic%20Halides.pdf
[2] Bathan, G., Bayquen, A., Crisostomo, A.,
Cruz, C., De Guia, R., Farrow, F.,Torres, P.
(2014). Classification Tests for Organic
Halides. In Laboratory Manual in Organic
Chemistry Revised Edition (pp. 97-98).
Quezon City. C & E Publishing
[3] Organic Halide - Organofluorides,
Organochlorides,
Chlorofluorocarbons,
Organobromides, Organoiodides (n.d.).

Retrieved November 17, 2015 from

http://science.jrank.org/pages/3192/HalideOrganic.html
[4] Alpha Carbon. (2009). Retrieved
November
18,
2015
from
http://science.uvu.edu/ochem/index.php/alph
abetical/a-b/alpha-carbon/
[5] Clark, J. (n.d). Physical Properties of
Alkyl Halides. Retireved November 17,
2015
from
http://chemwiki.ucdavis.edu/Organic_Chemi
stry/Alkyl_Halides/Properties_of_Alkyl_Hal
ides/Physical_Properties_of_Alkyl_Halides
[6] Clark, J. (2000). Halogenoalkanes.
Retrieved November 18, 2015 from
http://www.chemguide.co.uk/mechanisms/n
ucsub/types.html
[7] Nucleophilic Substitution Reactions.
(n.d). Retrieved November 18, 2015 from
http://www.citycollegiate.com/alkyl_halide2
.htm
[8] Hunt, I. (n.d). Nucleophilic Substitution.
Retrieved November 18, 2015 from
http://www.chem.ucalgary.ca/courses/351/C
arey5th/Ch08/ch8-2.html

[9] Chem 4563 Organic Qualitative

Analysis. (n.d). Retrieved November 19,
2015 from
http://faculty.swosu.edu/william.kelly/pdf/q
o2a.pdf
[10] Interactive Organic Mechanisms.
(2004). Retrieved November 19, 2015 from
http://www.chem.ox.ac.uk/vrchemistry/iom/
sn2/
[11] Comparing SN1 and SN2 reaction. (n.d).
Retrieved November 19, 2015 from
http://www.masterorganicchemistry.com/20
12/08/08/comparing-the-sn1-and-sn2reactions/
[12] Harcourt, H.M. (2015). Reactions of
Aryl Halides. Retrieved November 19, 2015
from http://www.cliffsnotes.com/studyguides/chemistry/organic-chemistryii/phenols-and-aryl-halides/reactions-ofaryl-halides