Experiment 8A

Qualitative Analysis (A to D)

Objectives
The objectives of the experiment include
testing the samples for the determination of
different functional groups, as well as the
positions of these functional groups in the
compound. Thus, the exact structure of the
compound could be determined.
The saturation and aromaticity of compounds
are also tested in this experiment, as well as the
acidity, basicity and presence of alkyl halides in
the compounds.

Introduction
Qualitative Analysis (A to D)

Qualitative analysis

-is a set of procedures and techniques used to

identify and quantify the chemical composition of
a given sample of a substance. It relies on certain
chemical reactions to detect particular functional
groups in a compound.

Qualitative analysis
There are four general schemes of analysis
useful for identifying the nature of an unknown
compound.
preliminary test,
physical constants
solubility tests
functional group classification test
**This experiment however only focuses on the
on the tests for identifying the functional groups a
compound is classified.

Functional groups

-are classified chemical groups attached to a

parent chain, which could react and determine
the chemical and physical properties of a
compound, and the reactions that are
characteristic of certain compounds

Functional groups
A visible reaction indicates the presence
of a functional group. The presence of
functional groups is identified by reacting
the compound to a reagent which gives a
specific visible result. Some of these tests
include:
Unsaturation
Aromaticity
Acidity and basicity
Alkyl halides.

Saturated compound

-is a compound that has single bonds only,

with no delocalizing electrons, and contains
as many hydrogen atoms as possible.
Compounds of this kind are called alkanes.

Unsaturated compound

-contains double or triple bonds, and thus

has less hydrogen atoms than a saturated
compound of the same number of carbon
atoms. Compounds of this type are called
alkenes, for those with double bonds, and
alkynes, for those with triple bonds

Aromaticity

-is a chemical property in which a

conjugated ring of unsaturated bonds, lone
pairs, or empty orbitals exhibit a
stabilization of conjugate alone.
-refers to the property of compounds to
release aroma or odor.

Aromaticity
There are certain requirements for a
compound to be aromatic:
(1)Cyclical
(2)planar
(3)has delocalized, conjugated double or pi
bonds
(4)follows Huckels rule where the number
of pi electrons = 4n + 2

Acid

-is defined as a compound whose pH is less than

7, and can turn blue litmus paper to red, such as
acetic acid or vinegar.
-has three types :
Arrhenius (increases the concentration of H+
ions in an aqueous solution)
Lewis (accepts electron pairs)
Bronsted-Lowry acids (donates protons)

Base

-is defined as a compound whose pH is greater

than 7, and can turn red litmus paper to blue,
such as sodium hydroxide or lye.
has three types :
Arrhenius (increases the concentration of
OH- ions in an aqueous solution)
Lewis (release electron pairs)
Bronsted-Lowry acids (accepts protons)

Alkyl halides

-have a general form of R-X where R is

typically an alkyl group and X is a halogen
replacing one of the hydrogens.

Qualitative Analysis
A. Test for Unsaturation

Test for
Unsaturation

Preparation
of Acetylene

CaC2(s) + 2H2O(l)

C2H2(g) Ca(OH)2(aq)

Test for
Unsaturation

3 drops of 2% SOLUTION OF BROMINE

IN METHYLENE CHLORIDE

Reaction
with Bromine
in Methylene
Chloride

Acetylene

Benzene
(5 )

Styrene
(5 )

Hexane
(5 )

Test for
Unsaturation

Reaction
with Bromine
in Methylene
Chloride

Test
Sample

Visible Results

Acetylene

Evolution of gas;
Formation of dark
orange layer
(bottom) and light
orange layer (top)

Benzene

No change (Blood
red solution)

Styrene

Evolution of gas;
No change in the
color of solution

Hexane

Red orange
solution

Structure/Formu
la of Compound
responsible for
the visible
result

Test for
Unsaturation

Acetylene
(+)

Reaction
with Bromine
in Methylene
Chloride
(Unsaturatio
n)

Benzene
(-)

Styrene
(+)

Hexane
(-)

Test for
Unsaturation

Reaction
Mechanism

Reaction
with Bromine
in Methylene
Chloride

Test for
Unsaturation

Reaction
with Bromine
in Methylene
Chloride

The
reaction
involved
is
electrophilic addition (halogenation)
with Br2 acting as the electrophile,
because the
bromine adds to each carbon of the
bond,
pi bond converts into a sigma bond
compound become saturated.
an OH group is then added to each
carbon at each end of a multiple
bond
the
multiple
bonds
become
saturated.

Test for
Unsaturation

General Mechanism:
ELECTROPHILIC ADDITION (HALOGENATION)
Equation 1

Reaction of
unsaturated
compounds
with Bromine
in Methylene
Chloride

Equation 2

Test for
Unsaturation

Br2 + C = C dibromoalkane
Br2 + C C tetrabromoalkane

Reaction
with Bromine
in Methylene
Chloride

When this reaction occurs:

molecular bromine is consumed
its characteristic dark red-brown
color disappears (if bromine is not
added in excess)
positive test for unsaturation.

Test for
Unsaturation

Reaction
with Bromine
in Methylene
Chloride

Bromine solution does not react with

the ring structure of aromatic
compounds like benzene because of
its stability. The shared electrons in
the unsaturated bonds of the
aromatic compound ring prevent
aqueous solution from reacting with
them.
Benzene gave a negative result
because
unsubstituted
aromatic
rings undergo substitution reactions
and not addition reactions.

Test for
Unsaturation

Reaction
with Bromine
in Methylene
Chloride
(drawbacks)

Negative
results
if
electronwithdrawing groups are present in
the vinylic position. Position slows
down bromine addition to the point
that a negative test is erroneously
produced.
tertiary amines (like pyridine) form
perbromides upon treatment with
bromine which can lead to false
positive tests
aliphatic
and
aromatic
amines
discharge the bromine color without
the evolution of HBr gas even with
the absence of multiple bonds.

Test for
Unsaturation

3 drops of 1% AQUEOUS SOLUTION OF

KMnO4

Baeyer
Test for
Unsaturati
on

Acetylene

Benzene
(5 )

Styrene
(5 )

Hexane
(5 )

Test for
Unsaturation
Test
Sample

Visible Results

Acetylen
e

Dark brown
precipitate in
brown solution
Formation of red
violet layer
(bottom) and red
layer (top)
Red brown
precipitate in
clear solution
Formation of
violet layer
(bottom) and

Benzene

Baeyer Test
for
Unsaturation

Styrene
Hexane

Structure/For
mula of
Compound
responsible
for the visible
result

MnO2

MnO4
MnO2

MnO4-

Test for
Unsaturation

Acetylene
(+)

Baeyer Test
for
Unsaturation

Benzene
(-)

Styrene
(+)

Hexane
(-)

Test for
Unsaturation

Reaction Mechanism

Baeyer Test
for
Unsaturation

Test for
Unsaturation

General Mechanism:
REDOX REACTION)
Equation 3

Equation 4

Baeyer Test
for
Unsaturation

Test for
Unsaturation

Baeyer Test
for
Unsaturation

The potassium permanganate test

(Baeyer test) depends on the ability of
potassium permanganate to oxidize
the carbon-carbon double bond to give
alkane diols (equation 3) or the carboncarbon triple bond to give carboxylic
acid (equation 4).

Test for
Unsaturation

Baeyer Test
for
Unsaturation

Redox reaction
Oxid. Agent: KMnO4 (e- acceptor)
Oxidation: MnO4- (purple soln) MnO2
(brown ppt)
The disappearance of the characteristic
color of the permanganate ion is then
considered a positive test for unsaturation.

Test for
Unsaturation

Baeyer Test
for
Unsaturation

Does not work on: alkanes and aromatic

compounds
Benzene and hexane did not show the
brown precipitate because of benzenes
aromatic stability and hexanes lack of pi
bonds.

Test for
Unsaturation

Baeyer Test
for
Unsaturation
(drawbacks)

Other easily oxidized compounds containing

other functional groups also give a positive
test. Most aldehydes, phenols, aryl amines,
impure alcohol, formic acid and its esters,
would give a positive test.
Brown precipitate often fails to form, instead
turning the solution reddish-brown, because
water insoluble compounds formed are
dissolved in ethanol, methanol, or acetone

Test for
Unsaturation

Ignitio
n Test

Acetylene

Benzene
(2 )

Styrene
(2 )

Hexane
(2 )

Test for
Unsaturation
Test
Sample

Ignition Test

Visible
Results

Structure/For
mula of
Compound
responsible
for the visible
result
Acetylene Blue-yellow
C(s) + CO2(g)
flame w/
soot
Benzene
Yellow
C(s) + CO2(g)
orange
flame w/
soot
Styrene
Orange
C(s) + CO2(g)
flame w/
soot
Hexane
Yellow
CO2(g)

Test for
Unsaturation

Acetylene
(+)

Ignition Test
(Unsaturatio
n and
Aromaticity)

Benzene
(+)

Styrene
(+)

Hexane
(-)

Test for
Unsaturation

General Mechanism:

Equation 5
Aromatic/Unsatd + O2(g) C(s) + CO2(g)
+ H2O

Equation 6
Aliphatic + O2(g) CO2(g) + H2O

Ignition Test

Test for
Unsaturation

Ignition Test

Differentiate
aromatic
unsaturated
compounds from aliphatic hydrocarbons
Positive: yellow sooty flame the yellow
color of the flame is due to the presence of
carbon while the soot is a result of the
deposition of a carbon from multiple bonds.
Unsaturated (positive): acetylene, benzene
and styrene (eq. 5)
Saturated (negative): hexane (eq. 6)

Methodology
B. Test for Aromaticity

Test for
Aromaticity

Toluene
10
Conc.
Conc.
HHNO
10
2SO4
3 10
drops
drops
drops

Nitration

50oC
5mins.

5mL H2O
(ice cold)

Test for
Aromaticity

Nitration

Test
Sample

Visible
Results

Toluene

Oily Light
Yellow color on
top of solution
which is similar
to oil water
mixture and
smells like
rugby

Structure/Formul
a of Compound
responsible for
the visible result

Test for
Aromaticity

General Mechanism:
ELECTROPHILIC AROMATIC SUBSTITUTION

Nitration

Test for
Aromaticity

Reaction Mechanism

Nitration

Test for
Aromaticity

Nitration

electrophilic aromatic substitution

Positive: yellow oily solution with evolution
of odor nitrotoluene
Sulfuric acid was used to protonate the nitric
acid, which then dehydrates to form the
highly electrophilic nitronium ion to be used
in the electrophilic substitution reaction. The
nucleophilic double bond attacks the double
bond of the benzene ring attacks the
nitronium ion to produce mostly ortho- and
para-nitrotoluene

Test for
Unsaturation

Nitration

The rate-determining intermediates for

ortho- and para- nitration each has a
resonance
form
that
is
a
tertiary
carbocation, while those of meta nitration
are secondary carbocations
Stability: Tertiary carbocations > secondary
carbocations
Therefore, the intermediates for attack at
the ortho- and para- positions are formed
faster than the intermediate for attack at
the meta position. This explains why the
major products are o- and p-nitrotoluene.
p-nitrotoluene > o-toluene (steric effect)
Major product: p-nitrolouene

Test for
Aromaticity

5 drops Le Rosen
reagent
5 drops xylene

Le Rosen
Test

INCLINE

Test for
Aromaticity

Le Rosen Test
Test
Visible
Sample
Results
Toluene

Le Rosen
Test

Cherry red
solution
with
formation
of red
precipitate

Structure/Formula of
Compound
responsible for the
visible result

Test for
Aromaticity

General Mechanism:
ELECTROPHILIC AROMATIC SUBSTITUTION

Le Rosen
Test

Test for
Aromaticity

Le Rosen
Test

Like nitration, but formaldehyde instead of

nitric acid
Electrophilic
aromatic
substitution

Oxidation reaction p-quinone

Positive: cherry red or pink color aromatic

Methodology
C. Test for Acidity and Basicity

Test for Acidity

and Basicity

20 drops 95% ethanol

20 drops 2% ethanolic AgNO3

Acetic Acid
(2 )

AgNO3 Test

Phenol
(2 )

Aniline
(2 )

Benzoic Acid
(2 )

**If a precipitate forms, + 5% HNO3,

dropwise

Test for Acidity

and Basicity

Test
Sample

Observation
Cloudy white solution
Acetic acid
clear
Cloudy reddish-brown
Phenol
solution
Aniline
Light brown solution
Benzoic
acid
Clear solution

AgNO3 Test

Test for Acidity

and Basicity

AgNO3 Test

Test for Acidity

and Basicity

Presence of strong acids

The relative acidity and basicity of
organic chemistry can be
determined by a general rule:
Relative acidities:

RCOOH > HOH > ROH > HC CH > NH > RH

Relative basicities:

RCOO- < HO- < RO- < HC C- < NH2- < R-

AgNO3 Test

Acetic & benzoic: positive

Phenol & aniline: negative

Test for Acidity

and Basicity

Tollen
s
Reage
nt:
1M
NH3

Silver
Acetaldehyd
e Test

20
2%
AgNO3

Test for Acidity

and Basicity

Silver
Acetaldehyd
e Test

Structure/for
mula of
Test
compound
Visible Result
Sample
responsible
for visible
result
Cloudy white
Acetyle
Ag2C2
solution with
ne
yellow crystals

Test for Acidity

and Basicity

Silver
Acetaldehyd
e Test

Test for Acidity

and Basicity

Silver
Acetaldehyd
e Test

Presence of terminal alkyne

diamminesilver(I) cation
([Ag(NH3)2]+): Tollens reagent
Since this test only works for
alkynes with a hydrogen atom
attached to a triple-bonded carbon,
this test could be used for
differentiating terminal alkynes with
alkenes

Methodology
C. Test for Alkyl Halides

Test for Alkyl

Halides

95%
ethanol
20

Alcoholic
AgNO3 Test

1 min.

Test for Alkyl

Halides

Test Sample

Ethyl
chloride
Ethyl
bromide

Alcoholic
AgNO3 Test

Ethyl iodide
t-butyl
chloride
s-butyl
chloride
Chlorobenze
ne

Visible
Result
White
layer
Milky
white
(yellow)
ppt
Yellow ppt
Grayish
white ppt
Grayish
white ppt
Clear
solution

Structure/form
ula of
compound
responsible
for visible
result
AgCl
AgBr
AgI
AgCl, t-butyl
chloride
AgCl
N/A (no
reaction)

Test for Acidity

and Basicity

Alcoholic
AgNO3 Test

Test for Acidity

and Basicity

Alcoholic
AgNO3 Test

Presence of halogens
t-butyl chloride > s-butyl chloride
Chlorobenzene clear solution
(negative)

Guide Questions
Qualitative Analysis (A to D)

Guide Questions

Question #1
What test/s
could be used
to differentiate
saturated and
unsaturated
hydrocarbons?
Explain how the
test could
differentiate
them?

Answer:
The decoloration of bromine solution test and
Baeyer test differentiate saturated from unsaturated
hydrocarbons. In decoloration of bromine solution
test, if the test compound is unsaturated, the redbrown color of the aqueous bromine solution rapidly
disappears. Bromine adds to each of carbon of the
bond then the pi bond converts into a sigma bond
and thus become saturated.
In
the
permanganate
test,
unsaturated
compounds reduce the purple permanganate ion
(MnO4-), forming a precipitate of brown manganese
(IV) oxide (MnO2). This then indicates that if a
compound is positive for the presence of
unsaturation, potassium permanganate will oxidize
the multiple bond resulting to the removal of its
purple color. This test will not give a positive result if
the sample tested is an alkane or an aromatic
compound.

Guide Questions

Question #2
Do alkynes
give all tests
which alkenes
exhibit? What
tests could be
used to
differentiate
them?

Answer:
No. The silver acetylide test could be
used to differentiate between an
alkyne and an alkene. It only produces
a positive test (formation of a silver
precipitate) on alkynes.

Guide Questions

Question #3
Illustrate with
equation the
reaction of Br2
in methylene
chloride with
acetylene.

Answer:

C2H2 + 2Br2 --> C2H2Br4

Guide Questions

Question #4
Does toluene
behave in the
same way like
the other
unsaturated
hydrocarbons?
Why?

Answer:
No. Toluene does not behave in the same way
like other unsaturated hydrocarbons since it is
an aromatic compound and because of the
presence of its benzene ring. The stable
structure due to resonance is less reactive
than the other saturated hydrocarbons
because the electrons in its double bonds are
delocalized and hence move freely about the
ring. The shared electrons in the saturated
bonds of the aromatic compound ring prevent
aqueous bromine solution from reacting with
them. Even if it does react with bromine, for
example, it would not be an electrophilic
addition reaction (which happens with aliphatic
compounds) but a substitution reaction.

Guide Questions

Question #5
What is the
role of
concentrated
sulfuric acid in
the nitration of
toluene?

Answer:
Concentrated sulfuric acid functions acts as
an electrophilic generator which serves as both
an acid (a source of H3O+ ions) and a
dehydrating agent to convert nitric acid into
nitronium ion, NO2+.
NO2+ is the one which reacts with toluene
to form the product.

Guide Questions
(a) Nitration

Question #6
Show the
mechanism for
the following
reactions:
(a) Nitration
(b) Le Rosen
Test

(b)

Le Rosen Test

Guide Questions

Question #7
Give the
equation
involved in the
reaction of
acetylene with
ammoniacal
silver nitrate.

Answer:

C2H2 + Ag(NH3)NO3 C2Ag2 + HNO3

Guide Questions

Question #8
Tollens
reagent for the
silver acetylide
test should
always be
freshly
prepared.
Why?

Answer:
When left standing and unused
for a period of time, Tollens
reagent decomposes and forms a
highly explosive precipitate
silver fulminate. To avoid this,
unused
reagent
should
be
neutralized with a little nitric acid
and then discarded.

Guide Questions

Question #9
Explain why the
terminal
hydrogen in
acetylene is
acidic when in
fact the
electronegative
values of
hydrogen and
carbon are
almost the same.

Answer:
Terminal
alkynes
are
unusual
hydrocarbons
for
they
can
be
deprotonated using an appropriate
base to generate carbanion. This is an
acidic situation since terminal alkynes
have an sp-hybridized orbital with 50%
s character, meaning it is a highly
electronegative orbital, the electron
pair shared with H(terminal and
directly attached to the unsaturation)
is tightly held by the nucleus of C
making it electrostatically stabilized.
So, The H+ now, to relieve the tension
can leave off the chain. Since this is a
positive H, then terminal alkynes are

Guide Questions

Question #10
What test could
be used to
differentiate
carboxylic acids
from phenol?
Explain how the
test could
differentiate
them?

Answer:
The NaHCO3 test can be used to
differentiate carboxylic acids from
phenols. Only strong acids like
carboxylic acids would react with
NaHCO3, resulting in an evolution of
gas. Phenols, which are weak acids,
would not react with NaHCO3, which is
a weak base.
The alcoholic silver nitrate test can be
used as well because only carboxylic
acids would form a white precipitate
(silver carboxylate salt) while phenols
would give a negative result.

Guide Questions

Question
#11
Why is the
order of
reactivity of
alkylhalides
toward
alcoholic silver
nitrate
3>2>1?

Answer:
Tertiary carbons formed by the
hetrolysis of alkyl halides are more
stable due to C-H hyperconjugation.
The positive charge is distributed to a
greater
number
of
surrounding
hydrogen atoms compared to the
secondary and primary alkylhalides.
The primary carbonium ion is the least
stable since its positive charge is
concentrated only to the carbon atom.
Also, with increasing branching the
electron
density
of
a
molecule
increases and the alcoholic silver
nitrate which is an electron pair
acceptor tends to be attracted more to

Guide Questions

Question #12
In the silver
nitrate test for
halides, explain
why alcohol is
used as the
solvent for
silver nitrate
and not water.

Answer:
Water is not used as the solvent
because it is highly polar considering
that the reaction proceeds with a
hydrocarbon. Ethanol, having both
hydrophobic and hydrophilic portion
can considerably dissolve the polar
nitrate and the nonpolar alkyl chain.
Water can only dissolve the polar
nitrate but it couldnt dissolve the alkyl
halide. To dissolve both the alkyl
halide, an organic solvent (alcohol) is
needed, not necessarily a polar solvent
(water).
AgBr
and
AgCl
from
precipitates are insoluble in ethanol
which then provides a good indicator

Conclusion and
Recommendation
Qualitative Analysis (A to D)

Conclusion

The functional groups of compounds could be

determined by causing the reaction of the
samples with certain known compounds that
follow a general mechanism. Some functional
groups have different reactions and observable
results with others, and these properties could be
used to determine the identity of the compound.

Recommendation

The amount of reagents used in each test could

be lessened, since a qualitative test does not rely
on the amount but on the properties of each
compound used.
The careful handling of chemicals should also be
exhibited since some reagents are highly toxic.
It is also very important that the chemicals to be
used are freshly prepared, and that there should
be separate droppers and pipettes to be used in
obtaining the samples, to prevent contamination
of the chemicals. Since the experiment is
qualitative, contaminated chemicals could
greatly affect the results.

References

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(n.d.).
Retrieved
from
http://mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey04oc/r
ef/ch11aromaticity.html
Eberlein, T. (1996). Degree of Unsaturation. Retrieved from
http://www.personal.psu.edu/the1/unsatura.htm
Organic
qualitative
analysis.
(n.d.).
Retrieved
from
http://www.analyticalchemistrygsu.com/2012/03/organic-qualitativeanalysis.html
Qualitative
analysis.
(n.d.).
Retrieved
from
http://bcs.whfreeman.com/mohrig2e/content/cat_010/techniques.pdf
Qualitative analysis of organic compounds. (n.d.). Retrieved from
http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt25.html
Qualitative analysis of organic compounds. (n.d.). Retrieved from
http://academics.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/A
ppendix/ClassificationTests/index.html
Unsaturation.
(n.d.).
Retrieved
from
http://www.britannica.com/EBchecked/topic/618441/unsaturation
Unsaturation.
(n.d.).
Retrieved
from
http://dictionary.reference.com/browse/Unsaturation