Classification Tests for Organic Halides

Arnau, C. L., Capunitan, V. N., Cerezo, O. U., Claudio, E. C., Co, M. A., Cortes, M. V.
2D-PH, Group 2, Department of Pharmacy, Faculty of Pharmacy, University of Santo Tomas
Espaa Boulevard, 1015 Manila, Philippines
Abstract
Organic halides are organic compounds in which one or more hydrogen atoms have been
substituted by a halogen atom. Most of these compounds are synthetic and flame retardant. In
this experiment, different tests were made to differentiate primary, secondary, and tertiary
organic halides based on their SN activity and to make a distinction between their SN1 and SN2
mechanisms. Sample compounds of n-butyl chloride, sec-butyl chloride, tert-butyl chloride and
chlorobenzene were subjected through the Beilstein test, SN1 Reactivity Test (alcoholic AgNO3)
and SN2 Reactivity Test (NaI in acetone). All compound samples produced a positive result with
Beilstein test by imparting a gree flame, affirming the presence of chlorine. In SN1 Reactivity
test the compounds were made to react with 2% ethanolic AgNO3 to observe SN1 Reactivity, all
samples produced a white precipitate with varying times of formation where tert-butyl chloride
exhibited the fastest and n-butyl chloride as the slowest. Chlorobenzene was observed to exhibit
no reaction in the SN1 Reactivity test. While in the SN2 reactivity test using NaI in Acetone as
the reagent, it was observed that all have samples exhibited the formation of a white precipitate
except for chlorobenzene; whereas n-butyl chloride exhibited the fastest time of formation and
tert-butyl chloride as the slowest.
Introduction
In the laboratory and in industry,
alkyl halides are used as solvents
for relatively non-polar compounds,
and they are used as the starting
materials for the synthesis of many
compounds. Alkyl halides are
classified
as
primary
(1o),
secondary (2o), or tertiary (3o)
according to the number of carbon
atoms directly bonded to the
carbon
bearing
halogen.
Compounds in which a halogen
atom is bonded to a sp2-hybridized
carbon are called vinylic halides or
phenyl halides. Vinylic halide is a
general term that refers to a

compound in which a halogen is

attached to a carbon atom that is
also forming a double bond to
another carbon atom. Phenyl
halides are compounds in which a
halogen is attached to a benzene
ring. Phenyl halides belong to a
larger group of compounds called
aryl halides. Together with alkyl
halides,
these
compounds
comprise a larger group of
compounds
known
simply
as
organic halides or organohalogen
compounds. [1]
Organic
halides
are
organic
compounds containing a halogen
atom bonded to a carbon atom.

The said halogen atom can either

be chlorine, fluorine, bromine, or
iodine. These compounds are
considered to be flame retardant
and most of them are synthetic.
The halogen atom of an alkyl halide
is attached to a sp3-hybridized
carbon. The arrangement of groups
around the carbon atom, therefore,
is generally tetrahedral. Because
halogen
atoms
are
more
electronegative than carbon, the
carbon-halogen bond of alkyl
halides is polarized. Halogen atom
size increases as we go down the
periodic table whereas fluorine

atoms are the smallest and iodine

atoms the largest. Consequently,
the carbon-halogen bond length
increases and carbon-halogen bond
strength decreases as we go down
the periodic table. [2]

Methodology

until the oxide adhered to the loop. The loop

was then then cooled slightly and was
dipped into the liquid sample. The loop was
heated again with the sample in a nonluminous flame where first in the inner zone
of the flame and then into the outer zone and
then near the edge of the flame. The color of
the flame imparted by each sample was then
recorded.

Samples
The samples used in the experiment were nbutyl chloride, sec-butyl chloride, tert-butyl
chloride and chlorobenzene.
Reagents
The reagents used in the experiment were
2% ethanolic AgNO3 and 15% NaI in
anhydrous acetone.
Beilstein Test: Copper Halide Test
The test was conducted by preparing one
copper wire for each sample to be used. On
one end of each copper wire a small loop
was made. The loop was then heated directly
in the oxidizing zone of a non-luminous
flame generated by a Bunsen burner. It was
continuously heated until the green color
imparted to the flame disappeared. While
the loop was hot, it was then dipped into
some copper oxide powder and reheated

The objectives of this experiment

are: (1) to differentiate primary,
secondary, and tertiary organic
halides based on their SN reactivity,
(2) and to differentiate between
SN1
and
SN2
as
reactive
mechanisms with organic halides.

Figure 1.1 Beilstein Test

silver halide precipitate to form was then

recorded. The color of the precipitate was
also recorded.
SN2 Reactivity: Reaction with Sodium
Iodide in Acetone (15% NaI in anhydrous
acetone)
SN1 Reactivity: Reaction with Alcoholic
Silver Nitrate (2% ethanolic AgNO3)
The test was conducted by placing 20 drops
of 2% ethanolic silver nitrate in each of the
four test tubes (Taking into consideration
that the solution of the reagent should not be
turbid when used). 5 drops of n-butyl
chloride, sec-butyl chloride, tert-butyl
chloride and chlorobenzene were then added
to their respective test tubes. The test tubes
were then shaken and the time it took for a

Results and Discussions

Beilstein Test
Beilstein Test is a quick preliminary check
for halogens. A positive result would impart
a blue-green flame. It is the simplest method

The test was conducted by placing 2 drops

of 15% NaI in anhydrous acetone in each of
the four dry test tubes (Taking into
consideration that the solution of the reagent
should not be turbid when used). 5 drops of
of n-butyl chloride, sec-butyl chloride, tertbutyl chloride and chlorobenzene were then
added to their respective test tubes. The
contents of each test tube were then mixed
and the time it took to form a precipitate was
then recorded. The color of the precipitate
was also recorded.

for identifying the presence of a halogen, but

does not positively differentiate between Cl,
Br and I. Heating the copper wire before the
test is carried out removes the traces of
impurities which may affect the result of the
test.[3]

Table 2.1 Beilstein Test Results

Organic Sample
n-butyl chloride
sec-butyl chloride
tert-butyl chloride
chlorobenzene

Beilstein Test
green flame
green flame
green flame
green flame

Table 2.1 shows the result of the said test

where all of the samples imparted a green
flame. The presence of a green flame
indicates that there is chlorine present. The
concept behind this reaction is shown below:
2Cu + O2 2CuO
RX + CuO CuX2 + CO2 + H2O

CuX2 is volatile and imparts a blue-green

flame. The blue-green color is due to the
emission of light from excited states of
copper halide that has vaporized in the
burner flame. [4]

SN1 Reactivity: Reaction with Alcoholic

Silver Nitrate (2% ethanolic AgNO3)
Testing for halogenoalkanes

Silver nitrate solution can be used to find out

which halogen is present in a suspected
halogenoalkane. The most effective way is
to do a substitution reaction which turns the
halogen into a halide ion, and then to test for
that ion with silver nitrate solution. [5]

AgCl
AgBr

Doing the reaction

The halogenoalkane is warmed with some
sodium hydroxide solution in a mixture of
ethanol and water. Everything will dissolve
in this mixture and so you can get a good
reaction.
The halogen atom is displaced as a halide
ion:

Various precipitates may be formed from the

reaction between the silver and halide ions:

ion present
ClBrI-

observation
white precipitate
very pale cream precipitate
very pale yellow precipitate

Confirming the precipitates

It is actually quite difficult to
distinguish between these colours,
especially if there isn't much
precipitate. You can sort out which
precipitate you have by adding
ammonia solution.

original
precipitate

observation

AgI

precipitate dissolves to give

a colourless solution
precipitate
is
almost
unchanged using dilute
ammonia solution, but
dissolves in concentrated
ammonia solution to give a
colourless solution
precipitate is insoluble in
ammonia solution of any
concentration

In this case, various halogenoalkanes are

treated with a solution of silver nitrate in a
mixture of ethanol and water. Nothing else is
added. After varying lengths of time
precipitates appear as halide ions (produced
from reactions of the halogenoalkanes) react
with the silver ions present.
As long as you are doing everything under
controlled conditions (same amounts of
everything, same temperature and so on), the
time taken gives a good guide to the
reactivity of the halogenoalkanes - the
quicker the precipitate appears, the more
reactive the halogenoalkane.
The halide ion is formed in one of two ways,
depending on the type of halogenoalkane
you have present - primary, secondary or
tertiary. [6]
For a primary halogenoalkane, the main
reaction is one between the halogenoalkane
and water in the solvent.

A tertiary halogenoalkane ionises to a very

small extent of its own accord.

Secondary halogenoalkanes do a bit of both

of these.
Comparing the reaction rates as you
change the halogen
You would have to keep the type of
halogenoalkane (primary, secondary or
tertiary) constant, but vary the halogen. You
might, for example, compare the times taken
to produce a precipitate from this series of
primary halogenoalkanes:

Obviously, the time taken for a precipitate of

silver halide to appear will depend on how
much of everything you use and the
temperature at which the reaction is carried
out. But the pattern of results is always the
same.
For example:

A primary iodo compound produces

a precipitate quite quickly.

A primary bromo compound takes

longer to give a precipitate.

A primary chloro compound

probably won't give any precipitate
until well after you have lost interest
in the whole thing!

If you have looked at the mechanisms for

these reactions, you will know that a lone
pair on a water molecule attacks the slightly
positive carbon atom attached to the
halogen. It is slightly positive because most
of the halogens are more electronegative
than carbon, and so pull electrons away from
the carbon.
It is tempting to think that the reaction will
be faster if the electronegativity difference is
greater. The slight positive charge on the
carbon will be larger if it is attached to a
chlorine atom than to an iodine atom.
That means that there will be more attraction
between a lone pair on the water and a
carbon atom attached to a chlorine atom
than if it was attached to an iodine atom.
The electronegativity difference between
carbon and iodine is negligible.
However, the fastest reaction is with an
iodoalkane. In these reactions, bond
strength is the main factor deciding the
relative rates of reaction. [7]

Table 2.2 SN1 Reactivity Test Results

The order of reactivity reflects the strengths

of the carbon-halogen bonds. The carboniodine bond is the weakest and the carbonchlorine the strongest of the three bonds. In
order for a halide ion to be produced, the
carbon-halogen bond has to be broken. The
weaker the bond, the easier that is.

Organic
Sample
n-butyl
chloride
sec-butyl
chloride
tert-butyl
chloride
chlorobenzene

SN1
Reactivity
White
precipitate
White
precipitate
White
precipitate
No reaction

Time
needed
5 minutes
1 minute
15 seconds
No
reaction

Table 2.2 shows the result of the said test

where n-butyl chloride, sec-butyl chloride
and tert-butyl chloride yielded a white

precipitate. Only chlorobenzene did not

show any signs of reaction. Tert-butyl
chloride was the fastest to form a precipitate,
sec-butyl chloride as the second and n-butyl
chloride as the last.

SN2 Reactivity: Reaction with Sodium Iodide

in Acetone (15% NaI in anhydrous acetone)
Table 2.3 SN2 Reactivity Test Results
Organic Sample
n-butyl chloride
sec-butyl chloride
tert-butyl chloride
chlorobenzene

SN2 Reactivity
White precipitate
White precipitate
White precipitate
No reaction

Table 2.3 shows the result of the said test

where n-butyl chloride, sec-butyl chloride
and tert-butyl chloride yielded a white
precipitate. Only chlorobenzene did not
show any signs of reaction. N-butyl chloride
was the fastest to form a precipitate, secbutyl chloride as the second and tert-butyl
chloride as the last.

in which iodide ion is the nucleophile; the

order of reactivity is primary > secondary
>
tertiary.
[8]
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
50C, but the tertiary chlorides fail to react
in a reasonable time. It should be noted
Time needed
that this test is necessarily limited to
6 seconds
bromides
and
chlorides.
7 seconds
30 seconds
SODIUM IODIDE IN ACETONE (for alkyl
halides that can undergo SN2 reactions)
No reaction
Primary and some secondary alkyl chlorides
or bromides will give a precipitate of
sodium iodide in the reagent. Alkyl iodides
will not give the precipitate. Aryl or vinyl
halides do not react.
Positive

Test

The formation of a white precipitate

indicates the presence of halides.
Complications

Another method for distinguishing between

primary secondary and tertiary halides
makes use of sodium iodide dissolved in
acetone. This test complements the alcoholic
silver nitrate test, and when these two tests
are used together, is possible to determine
fairly accurately the gross structure of the
attached alkyl group. The test depends on
the fact that both sodium chloride and
sodium bromide are not very soluble in
acetone, whereas sodium iodide is. The
reactions that occur are SN2 substitutions

1.When the sodium iodide solution is added

to the unknown, a precipitate of sodium
iodide might occur leading to a false
positive test. Upon mixing, the precipitate of
sodium
iodide
should
dissolve.
2.Excessive heating can cause the loss of
acetone and the production of solid salt
leading to a false positive test. [9]

References

Lehman, J.W.(2010). Multiscale Operational

Organic Chemistry: A Problem-Solving
Approach to the Laboratory Course (2nd
edition). pp. 253-254. Upper Saddle
River,NJ:Pearson Education, Inc.
Solomons, T.W., Fryhle, C.B. (2011).
Organic Chemistry (10th edition). pp. 231234. Hoboken,NJ: John Wiley & Sons,Inc.
Pavia, D.L., Lampman, G.M., Kriz,G.S.,
Engel, R.G.(1999). Introduction to Organic
Laboratory Techniques: A Microscale
Approach (3rd edition). pp. 438-439.
Troy;Mo:Saunders College Publishing.
Beilstein
Test:
http://www.chemguide.co.uk/inorganic/grou
p7/testing.html#top (accessed Nov. 23,
2015).

Test
for
Halides:
http://www.chemguide.co.uk/inorganic/grou
p7/testing.html#top (accessed Nov. 23,
2015).
Klein, D. (2012). Organic Chemistry as a
Second Language. pp. 523-530. USA: John
Wiley & Sons, Inc.
SN1
Reactivity
Test:
http://www.chemguide.co.uk/organicprops/h
aloalkanes/agno3.html
Williamson, K.L., Minard, R.D., Masters,
K.M.(2007). Macroscale and Microscale
Organic Experiments. pp. 450-455. USA:
Houghton Mifflin Company.
SN2
Reactivity
Test:
http://kimiagar2010.blogspot.com/2010/04/s
odium-iodide-in-acetone-test-for.html