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CHEM 31.1 ORGANIC CHEMISTRY

AMINES

2009-37564

2-BSB

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Amines are organic compounds which are relative with ammonia; they are polar
basic and are miscible with water if it contains a smaller chain (Morrison & Boyd,
1992). There are three classifications of ammonia: primary, secondary and tertiary.
In order to distinguish which class does aniline, N,n-Dimethylaniline and
Diethylamine belongs to, Hinsberg test was conducted. Primary amine dissolves in
 base and precipitates with reaction to acid. Secondary amine precipitates from base
and does not react with acid while tertiary amine precipitates in reaction with bases
and dissolves in acid (Glagovich, 2007). From the experiment, it was determined that
aniline is a primary amine, diethyamine is a secondary amine and N,n-dimethylaniline
is a tertiary amine. c


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Amines are basic organic compounds which has the general formula of RNH2, R2NH, or R3N,
where R symbolizes an alkyl or aryl group. Amines are nearly relatives with NH3, since like ammonia
amines are polar, except for tertiary amines. In addition to their polarity, amines have higher boiling
points than non-polar compounds but have lower boiling point compared to alcohols or carboxylic acid.
(Morrison & Boyd, 1992) Since amines are polar compounds, most of it can form hydrogen bond with
water and itself, especially for small amines and except for tertiary amines; however this solubility
decreases as the hydrocarbon chain increases (Clark, 2004).

There are three classifications of amines according to the number of groups attached to the
nitrogen atom: primary (RNH2), secondary (R2NH) and tertiary (R3N). Like ammonia, this functional group
is also considered as a base due to the presence of a lone pair on nitrogen; however its association with
an aromatic ring weakens its basicity due to the delocalized lone pair in the pi system of benzene (Hunt,
n.d.). This lone pair also gives amine its nucleophilic ability in able for it achieve stability (Chemistry of
Amines, n.d.). In order to classify the given compounds into what type of amines they belong to,
Hinsberg test was conducted. Primary amine dissolves in base and precipitates with reaction to acid.
Secondary amine precipitates from base and does not react with acid while tertiary amine precipitates
in reaction with bases and dissolves in acid (Glagovich, 2007). Figure 1 shows the mechanism of
Hinsberg test.
 Figure 1. The mechanism reaction of Hinsberg Test.

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The experiment on Amines aimed to achieve the following objectives:

1.c To determine the physical properties of amines

2.c To classify amines into their three classes: primary, secondary and tertiary
3.c To study how the structures of amines affect their chemical properties.

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The experiment was based on the Chemistry 31.1 Organic Chemistry laboratory manual of the
University of the Philippines in Mindanao with reference to Organic Experiments by Fieser and
Williamson and Experimental Organic Chemistry by Most. There were no modifications done during the
experiment proper.

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Table 1. Physical Property of Amines

COMPOUND SOLUBILITY IN WATER LITMUS TEST ADDITION OF CONC. HCl

Aniline Not soluble Acidic Presence of gas which made the
compound miscible with the reagent
N,N-Dimethylaniline Not soluble Acidic Smoke was emitted but the
compound remained immiscible
Diethylamine Soluble Basic The smoke emitted remained
contained in the tube on top of the
compound
Table 2. Chemical Property of Amines and their Classification

HINSBERG TEST Aniline N,N-Dimethylaniline Diethylamine

AFTER ADDITION OF Milky, heterogenous Presence of green Milky, homogenous
BENZENE SULFONYL appearance of liquid substance and the appearance of liquid
CHLORIDE liquid appears in 2
phases
AFTER ADDITON OF Presence of crystals Formation of gel-like Formation of milky gel-
CONC. HCl substance like substance
AFTER WARMING WITH Soluble Immiscible with blue immiscible
10% NaOH color of solution
AMINE CLASSIFICATION Primary Tertiary Secondary
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Given the idea that the given test compounds, which were Aniline, N,N-Dimethylaniline and
Diethylamine, are amines the experiment aimed to classify into what class of amines each of the
compounds belongs to. Before classifying the compounds their physical properties were first observed.
According to Morrison and Boyd, smaller amines are miscible in water due to their short hydrocarbon
chain and because of the hydrogen molecule present in their structure. However the experimental result
showed that aniline is not miscible with water. Amines are bases, as stated on the introduction, due to
the lone pair present on nitrogen however basicity decreases when it is associated with an aromatic
ring. Aniline and N,N-Dimethylaniline resulted to an acidic pH due to its association with a benzene ring
while Diethylamine turned red litmus paper to blue indicating its basicity.

Hinsberg test was conducted to classify amines into primary, secondary and tertiary amines. It
was observed that Aniline became turbid after adding benzene sulfonyl chloride, then precipitated with
the addition of HCl and lastly became soluble after the addition of NaOH. On the other hand, N,N-
Dimethyllaniline turned to a green heterogenous solution after the addition of benzene sulfonyl
chloride, then formed a green gel-like substance after the addition of HCl and with the addition of NaOH
the solution was still immiscible and turned to blue. Lastly, Diethylamine turned to a milky homogenous
solution that when added with HCl remained unaffected and when added with NaOH the liquid is still
immiscible.

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c In conclusion, amines are polar compounds which can form hydrogen bonds with water due to
the presence of hydrogen molecule in its structure. However, their solubility with HCl varies since aniline
and diethylamine became soluble with the formation of smoke while N,N-Dimethylamine remained
immiscible. They are considered as bases due to the presence of lone pair present in nitrogen, this was
exhibited by Diethylamine, and however this basicity decreases in the presence of an aromatic ring thus
making the compound more acidic, this is exhibited by Aniline and N,N-Dimethylamine.

Amines are classified into primary, secondary and tertiary amines and this can be determined by
doing the Hinsberg test. Primary amine dissolves in base and precipitates with reaction to acid.
Secondary amine precipitates from base and does not react with acid while tertiary amine precipitates
in reaction with bases and dissolves in acid (Glagovich, 2007).

Based from the given results, Aniline is a primary amine, while Diethylamine is a secondary
amine and lastly N,N-Dimethylaniline is a tertiary amine.

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Aniline was soluble in alkali due to the formation of salt during the reaction of aniline and
concentrated HCl. The production of salt led to the solubility of aniline to NaOH to produce
a clear liquid.
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 ›
. (n.d.). Retrieved September 25, 2010, from

http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/amine1.htm

Clark, J. (2004). ÷
÷ ›÷  Retrieved September 25, 2010, from Understanding Chemistry:
http://www.chemguide.co.uk/organicprops/amines/background.html

Fieser, L., & Williamson, K. (1992).  

 
  Lexington, Mass.: D.C. Heath.

Glagovich, N. (2007, July 19).

 
. Retrieved September 30, 2010, from
http://www.chemistry.ccsu.edu/glagovich/teaching/316/qualanal/tests/hinsberg.html

Hunt, D. I. (n.d.). 
 ›
. Retrieved September 25, 2010, from
http://www.chem.ucalgary.ca/courses/350/Carey/Ch22/ch22-1.html#Properties

Morrison, R. T., & Boyd, R. N. (1992). Organic Chemistry 6th. Ed. Pearson Education Inc.

Most, J. C. (1988).  
 
 


  John Wiley & Sons.