Experiment # 8: Qualitative Analysis

GO, Jeremy Owen G.

KALAW, Maria Nerissa F.
Group # 8, Chem 31.1, HEJ, Mr. Harold Henrison C. Chiu
March 24, 2011

I. Abstract
Organic compounds may be classified from each other by identifying their nature and
composition. Qualitative Analysis is used to determine the substance present in a sample or a
compound. Several tests can be performed to identify a compound’s properties. This experiment
includes the test for unsaturation, aromaticity, acidity and basicity, and alkylhalides. The tests conducted
were also divided into four, namely for alcohols and phenols, aldehydes and ketones, amines, and
carboxylic acid and its derivatives. Reacting compounds with certain reagents would result in reactions
that can be used to determine its properties. For each analysis, it is important to know the results which
indicate the presence of the functional groups being sought.

Keywords: saturation, aromaticity, qualitative analysis, functional groups, acidity and basicity

II. Introduction III. Experimental

The analysis and identification of unknown A. Test for Unsaturation

organic compounds constitutes a very important A piece of calcium carbide lump was
aspect of experimental organic chemistry. placed in a 250 mL distilling flask and a 125 mL
Qualitative analysis is a set of procedures used in separatory funnel was filled with 50 mL water.
the identification of substances in a mixture, i.e, The acetylene gas generator was then setup as
functional groups. It relies on certain chemical shown below:
reactions to detect particular functional groups such
as hydroxyl and carbonyl groups, and certain
elements such as nitrogen and oxygen. The
presence of functional groups is identified by
reacting the compound to a reagent which gives a
specific visible result. Meaning, a visible reaction
indicates the presence of a functional group.

Four basic areas of inquiry are useful for

identifying the nature of an unknown compound
Figure 1. Acetylene gas generator setup.
namely, physical properties of compounds,
classification by solubility, elemental analysis, and
Water was allowed to trickle on the
classification test for functional groups. This
calcium carbide. Three test tubes of the gas
experiment focuses on the fourth area of inquiry.
were collected for each group by water
displacement and the test tubes were kept
There are seven tests performed in the
tightly stopped.
experiment: test for unsaturation; test for
aromaticity; test for acidity and basicity; test for
When enough acetylene gas was
alkylhalides; test for alcohols and phenols; test for
collected, water was added to decompose the
aldehydes and ketones; test for amines; and, test
remaining calcium carbide. The acetylene gas
for carboxylic acid and its derivatives.
generator was then placed near the window with
the end of the delivery tube outside the window
Through this experiment, we were able to
to allow acetylene to escape in the atmosphere
conduct chemical tests to organic compounds
outside the room. After the calcium carbide was
containing different functional groups.
completely reacted, the aqueous layer was
decanted and the residue was thrown in the
trash can.

Chem 31.1: Qualitative Analysis Page 1 of 20

1. Reaction with Bromine in Methylene
Chloride
In a test tube containing acetylene, 3
drops of 2% solution of bromine in methylene
chloride was placed. The same test was done
for other organic hydrocarbons: benzene,
styrene, and hexane – using 5 drops of each
sample. The decolorization of bromine indicates
a positive result.
2. Baeyer Test for Unsaturation
In the second test tube containing
acetylene, 3 drops of 1% aqueous solution of
potassium permanganate (KMnO4) was placed.
The same chemical test was done for benzene,
styrene, and hexane – using 5 drops of each
sample. The decolorization of KMnO4 from
purple into light color and the formation of a
brown to dark precipitate indicate a positive
result.
B. Test for Aromaticity
Nitration
Ten drops concentrated nitric acid
(HNO3) and ten drops concentrated sulfuric acid
(H2SO4) were cautiously mixed in a test tube
placed in a beaker containing cold water. Ten
drops of toluene was added dropwise to the acid
mixture. The mixture was then heated in a water
bath at 50°C for 5 minutes. The mixture was
shaken occasionally. The mixture was then
poured drop by drop into a beaker containing 5
mL of ice-cold water. The color and odor of the
product formed were observed. The formation of
yellow solution and aromatic odor indicate a
positive result.
C. Test for Acidity and Basicity
1. AgNO3 Test
In a 5 mL test tube, 2 drops of acetic
acid and 20 drops of 95% ethanol were placed.
Then, 20 drops of 2% ethanolic AgNO3 solution
was added. If a precipitate formed, 5% HNO3
was added dropwise until precipitate dissolved.
The procedures were then repeated using
phenol, aniline, and benzoic acid. Formation of
precipitate indicates acidity.
2. Silver Acetylide Test
Tollen’s reagent was prepared by
adding 1M NH3 solution dropwise to 20 drops of
2% AgNO3 solution until the precipitate which
forms just dissolves. The prepared reagent was
then poured into a test tube containing acetylene
Chem 31.1: Qualitative Analysis
gas. The tube was shaken and stoppered, and
the color of the precipitate formed was noted.
Formation of a pale-yellow to gray-silver
precipitate indicates a positive result.
D. Test for Alkyl halides
Alcoholic AgNO3 Test
In a 5 mL test tube, 20 drops of 2%
alcoholic AgNO3 and 2 drops of ethylchloride
was placed. The test tube was shaken and then
heated in a water bath for 1 minute. The
procedures were repeated using ethylbromide,
ethyiodide, benzylchloride, tert-butylchloride,
sec-butylchloride, and cholorobenzene.
E. Tests for Alcohols and Phenols
1. Reaction of Alcohols
1.1 Reaction with sodium metal
20 drops of n-butylalcohol/sec-butyl
alcohol/tert-butyl alcohol was placed in a 5 mL
test tube. A tiny piece of Na metal was carefully
added and the appearance of bubbles was
observed. The rates of evolution of gas of the 3
test samples were compared.
1.2 Lucas Test
20 drops of Lucas reagent and 10 drops
of n-butylalcohol/sec-butyl alcohol/tert-butyl
alcohol were placed in a 5 mL test tube. The
tube was shaken vigorously and was stopped
using a stopper. The formation of a layer was
observed. The time which the insoluble layer
appeared was recorded. The rates of formation
of a layer in the 3 test samples were compared.
1.3 Reactions with Potassium
20 drops of n-butylalcohol/sec-butyl
alcohol/tert-butyl alcohol was placed in a 5 mL
test tube. 2M H2SO4 and 5 drops of 3% K2Cr2O7
solution was used to acidify the mixture. The
visible result was observed afterwards.
2. Reaction of Phenol
2.1 Ferric Chloride Test
20 drops of 95% ethanol and 2 drops of
liquid phenol/α-napthol/catechol/resorcinol were
placed in a 5 mL test tube. 5 drops of 3% FeCl3
solution was added and the mixture was mixed.
The visible result was observed afterwards.
Page 2 of 20
2.2 Bromine Water Test
20 drops of 95% ethanol and 5 drops of
phenol/α-napthol/catechol/resorcinol were
placed in a 5 mL test tube. Bromine water was
added dropwise with shaking until the bromine
color persisted. The observed data was
recorded.
2.3 Millon’s Test
5 drops of Millon’s reagent and 5 drops
of phenol/α-napthol/catechol/resorcinol were
placed in a 5 mL test tube, and then was shook.
The mixture was heated in a water bath for 2
minutes. The observed data was recorded.
F. Tests for Aldehydes and Ketones
1. 2,4-DNPH Test
Five drops of 2,4-DNPH soluiton and 3
drops of formaldehyde/acetaldehyde/ acetone/
benzaldehyde were placed in a 5-mL test tube.
The test tube was heated in a water bath for 5
minutes. Observations were recorded.
2. Bisulfite Test
Twenty drops of sodium bisulfite and 5
drops of formaldehyde/acetaldehyde/acetone/
benzaldehyde were placed in a 5-mL test tube.
The contents were mixed thoroughly. The test
tube was placed in an ice bath. Observations
were recorded.
3. Schiff’s Test
Twenty drops of Schiff’s reagent and 5
drops of formaldehyde/acetaldehyde/acetone/
benzaldehyde were placed in a 5-mL test tube.
Observations were recorded.
4. Tollen’s Test
Twenty drops of Tollen’s reagent and 5
drops of formaldehyde/acetaldehyde/acetone/
benzaldehyde were placed in a 5-mL test tube.
The test tube was heated in a water bath.
Observations were recorded.
5. Iodoform Test
Four drops of formaldehyde/
acetaldehyde/acetone/benzaldehyde and 10
drops of distilled water were placed in a test
tube. Five drops of 6M NaOH was then added,
then 5 drops of water. Five drops of KI/I2 was
now added, then observations were noted after
10 minutes.
Chem 31.1: Qualitative Analysis
6. Fehling’s Test
Twenty drops of Fehling’s reagent and 5
drops of formaldehyde/acetaldehyde/acetone/
benzaldehyde were placed in a 5-mL test tube.
The test tube was heated in a water bath.
Observations were recorded.
7. Molisch Test
Twenty drops of Molisch reagent and 5
drops of 1% glucose/1% maltose/1% sucrose/
1% boiled starch were placed in a 5-mL test
tube. The test tube was inclined. Two mL of
concentrated H2SO4 was run down through the
sides of the test tube. The test tube was
carefully brought to an upright position. The
formation of a blue-violet ring was observed.
8. Benedict’s Test
Twenty drops of Benedict’s reagent and
5 drops of 1% glucose/1% maltose/1% sucrose/
1% boiled starch were placed in a 5-mL test
tube. The test tube was heated in a water bath.
Changes were observed for.
G. Test for Amines
Hinsberg Test
Twenty drops of 10% NaOH, 5 drops of
methylamine/dimethylamine/trimethylamine/
aniline/n-methylaniline, and 5 drops of
benzenesulfonyl chloride were placed in a 5-mL
test tube. The test tube was covered with a
stopper and shaken for 5 minutes. The solution
was tested using litmus to see if it was basic.
Ten percent NaOH was added dropwise until the
solution was basic to litmus. If a precipitate was
observed to form, 40 drops of water was added.
The solution was shaken. Observations were
recorded. To the result in the previous step, 3M
HCl was added dropwise while the solution was
being mixed. The result was observed and
recorded.
H. Test for Carboxylic Acid and its Derivatives
1. Formation of Esters
1.1 Reaction of Carboxylic Acid and Alcohol
A pinch of salicylic acid and 20 drops of
methanol were mixed in a 10-mL test tube. Five
drops of concentrated H2SO4 was added. The
mixture was shaken and heated in a water bath
for 5 minutes. Observations were recorded.
Page 3 of 20
2. Hydrolysis of Acid Derivatives Test Samples Visible Structure/Formula
Result of Compound
Responsible for the
2.1 Hydrolysis of Benzamide Visible Result
A pinch of benzamide and 20 drops of Acetylene Dark brown MnO2 – brown
10% NaOH were placed in a 5-mL test tube. A precipitate precipitate
piece of moist red litmus paper was held, using Benzene No change
Styrene Burnt MnO2 – brown
a stirring rod, above the mouth of the test tube brown precipitate
while the latter was being heated to boiling in a precipitate
water bath. Changes in the color of the litmus Hexane No change
paper and in the odor of the mixture were noted. Table 2. Baeyer Test.

2.2 Hydrolysis of an Ester Tests for Aromaticity

Twenty drops of ethylacetate were Test Samples Visible Structure/Formula
placed in a 5-mL test tube. Five drops of 25% Result of Compound
NaOH solution were aadded. The test tube was Responsible for the
loosely covered with a stopper and heated in a Visible Result
Toluene Yellow color
water bath for 15 minutes. A 1M solution of HCl on top of
was added dropwise until the solution was sol’n; rugby
neutral to litmus. Changes in the odor of the smell
mixture were noted.

2.3 Hydrolysis of an Anhydride Table 3. Nitration.

Twenty drops of water and a piece each
Tests for Acidity and Basicity
of red and blue litmus papers were added to a 5-
mL test tube. Twenty drops of acetic anhydride Test Samples Observation
were carefully added. The tube was gently Acetic Acid White ppt
shaken and felt. Observations were recorded. Phenol No ppt
Aniline No ppt
Benzoic Acid White ppt
3. Hydroxamic Acid Test for Acid Derivatives Table 4. AgNO3 Test.
Five drops of ethylacetate/benzamide/
acetic anhydride/benzoylchloride and 20 drops Test Samples Visible Structure/Formula
of 7% methanolic hydroxylamine hydrochloride Result of Compound
Responsible for the
solution were added to a 5-mL test tube. The Visible Result
acidity/basicity of the solution was tested using Acetylene Pale yellow
red litmus paper. Ten percent methanolic KOH ppt
was added until red litmus paper turned blue, Table 5. Silver Acetylide Test.
then ten more drops was added. The solution
was heated to boiling in a water bath and was Tests for Alkylhalides
allowed to slightly cool. Ten drops of 3% FeCl3 Test Samples Visible Result Structure Formula of
was addd. Observations were recorded. Compound
Responsible for the
IV. Results Visible Result
Ethylchloride White ppt AgCl
Ethylbromide Gray to black AgBr
Tests for Unsaturation Ethyliodide Pale yellow ppt AgI
Tert-butylchloride White ppt AgCl
Test Visible Result Structure/Formula Sec-butylchloride White ppt AgCl
Samples of Compound Responsible Chlorobenzene No ppt; clear
for the Visible Result sol’n
Acetylene Cobra yellow Benzylchloride White ppt AgCl
Table 6. Alcoholic AgNO3 Test.

Benzene No change
Styrene Translucent
white

Hexane No change
Table 1. Reaction with Bromine.

Chem 31.1: Qualitative Analysis Page 4 of 20

 Tests for Alcohols and Phenols Test Samples Visible Result Structure Formula
of Compound
Responsible for
Test Samples Visible Result Structure Formula
the Visible Result
of Compound
Phenol Layered: bottom
Responsible for
(brown), top
the Visible Result
(darkened)
n-butylalcohol Very rapid H2
formation of gas
sec-butylalcohol Fast formation H2
of gas
tert-butylalcohol Very slow H2
Catechol If Br2CH2Cl2
formation of gas
used – darker
Table 7. Data from reaction with Na metal. red
If added with 3%
Test Samples Visible Result Structure Formula FeCl3 – muddy
of Compound (not viscous)
Responsible for black
the Visible Result Resorcinol Lighter red color
n-butylalcohol No layer –
formation
sec-butylalcohol Layer appeared
slowest

tert-butylalcohol Layer appeared

fastest α-napthol If Br2CH2Cl2
used – layered:
bottom (brown),
top (red)
If BrH2O (wrong
mix) –layered:
bottom (brown),
Table 8. Data from Lucas Test.
top (transparent)
Table 11. Data from Bromine Water Test.
Test Samples Visible Result Structure Formula
of Compound
Test Samples Visible Result Structure Formula
Responsible for
of Compound
the Visible Result
Responsible for
n-butylalcohol Formation of 2 Cr3+
the Visible Result
liquid layers:
Phenol Layered: bottom Complex of Hg
bottom (blue),
(cream color),
top (clear)
top (dark brown)
sec-butylalcohol Clear to blue Cr3+
Catechol Dark orange, Complex of Hg
green liquid
didn’t dissolve
tert-butylalcohol Orange liquid no reaction
Resorcinol Dark orange Complex of Hg
(color of
potassium α-napthol Light brown color Complex of Hg
dichromate) Table 12. Data from Millon’s Test.
Table 9. Data from reaction with Potassium Dichromate.
Tests for Aldehydes and Ketones
Test Samples Visible Result Structure Formula
of Compound Test Samples Visible Result
Responsible for Formaldehyde Dark ppt
the Visible Result Acetaldehyde Change from yellow to orange with dark
Phenol Dark brown, orange ppt
with ppt Acetone Yellow to darker color
Catechol Dark blue to Benzaldehyde Change from yellow to orange with ppt
black, with ppt Table 13. Data from 2,4-DNPH Test.
Resorcinol Olive green to
black, no ppt Test Samples Structure Formula of Compound
α-napthol Brown, cloudy Responsible for the Visible Result
with ppt Formaldehyde
Table 10. Data from Ferric Chloride Test.

Chem 31.1: Qualitative Analysis Page 5 of 20

 Acetaldehyde Test Samples Visible Result
Formaldehyde Formation of purple solution
Acetaldehyde Formation of purple solution
Acetone –
Benzaldehyde Didn’t mix but purple coloration was
observed in one of the layers
Acetone Table 16. Data from Schiff’s Test.
Test Samples Structure Formula of Compound
Responsible for the Visible Result
Formaldehyde

Benzaldehyde

Acetaldehyde

Table 14. Structure formula of 2,4-DNPH Test.

Test Samples Visible Structure Formula Acetone –

Result of Compound Benzaldehyde
Responsible for the
Visible Result
Formaldehyde Evolution of
gas, very
miscible and
observed Table 17. Structure formula of Schiff’s Test.
release of
Test Samples Visible Result Structure Formula
heat
of Compound
Acetaldehyde Evolution of Responsible for
gas, turned the Visible Result
olive green, Formaldehyde Silver mirror Ag(s)
release of Acetaldehyde Silver mirror Ag(s)
heat Acetone – –
Benzaldehyde No reaction Ag(s)
Table 18. Data from Tollen’s Test.

Acetone No change Test Samples Visible Result Structure Formula

of Compound
Responsible for
the Visible Result
Formaldehyde Turned NaOH-
colorless,
formation of 2
layers
Benzaldehyde Yellowish Acetaldehyde Turned orange CHI3
white, cloudy Acetone Still cloudy, CHI3
solution with formation of 2
ppt layers
Benzaldehyde Formation of 2 NaOH-
layers
Table 19. Data from Iodoform Test.
Benzenesulfonyl Cloudy white Test Samples Visible Result Structure Formula
of Compound
Responsible for
the Visible Result
Formaldehyde Bronze brown Cu2O
with black ppt
Acetaldehyde Turned orange Cu2O
with red ppt
Table 15. Data from Bisulfite Test. Acetone 2 layered –
formation, red
ppt
Benzaldehyde Orange brown Cu2O
with orange ppt
Table 20. Data from Fehling’s Test.

Chem 31.1: Qualitative Analysis Page 6 of 20

 Test Samples Visible Result Structure Formula Aniline
of Compound
Responsible for
the Visible Result
Glucose White ppt, red
solution, blue to
violet ring N-methylaniline negative result
Table 24. Structure formula of Hinsberg Test.
1% Sucrose White ppt, red
solution, blue to Tests for Carboxylic Acid and its Derivatives
violet ring
Test Samples Visible Result Structure Formula
Maltose White ppt, blue of Compound
violet ring Responsible for
the Visible Result
Salicylic acid Sweet aroma,
Table 21. Data from Molisch Test. clear solution,
fiber-like ppt
Test Samples Visible Result Structure Formula (salicylic acid
of Compound dissolved)
Responsible for Table 25. Data from reaction of carboxylic acid and alcohol.
the Visible Result Test Samples Visible Result Structure Formula
Glucose Blue that turned Cu2O of Compound
blue green after Responsible for
heating the Visible Result
1% Sucrose Blue that Cu2O Benzamide Dissolved, CH3COOH
contained red ppt yellow solution,
after heating litmus from red
Maltose No color turning no reaction to blue, foul odor
deep violet after Table 26. Test results for hydrolysis of benzamide.
heating
Table 22. Data from Benedict’s Test. Test Samples Visible Result Structure Formula
of Compound
Tests for Amines Responsible for
the Visible Result
Test Samples Visible Result Ethylacetate Acetic acid odor CH3COOH
Methylamine Basic, ppt (solid dissolved), cloudy Table 26. Test results for hydrolysis of an ester.
Dimethylamine Basic, ppt (clear, substances settled)
Trimethylamine – Test Samples Visible Result Structure Formula
Aniline Basic, slight ppt (cloudy), became of Compound
cloudier Responsible for
N-methylaniline Basic, ppt (solid substances settled), the Visible Result
became cloudier Acetic Anhydride Litmus turns red CH3COOH
Table 23. Data from Hinsberg Test. Table 27. Test results for hydrolysis of an anhydride.

Test Samples Structure Formula of Compound Test Samples Visible Result Structure Formula
Responsible for the Visible Result of Compound
Methylamine Responsible for
the Visible Result
Ethylacetate Sweet and sour Ferric Hydroxamate
sauce odor, Complex (HX)
white ppt at the
Dimethylamine bottom, did not
turn blue
Benzamide Yellow ppt, did Ferric Hydroxamate
not turn blue Complex (NH4)
Acetic Anhydride White ppt, did Ferric Hydroxamate
not turn blue Complex (RCO2H)
Trimethylamine Benzoylchloride White ppt, did Ferric Hydroxamate
not turn blue; Complex (ROH)
upon addition
of FeCl2: dark
purple color,
white ppt
Table 28. Test results for Hydroxamic Acid Test for Acid
Derivatives.

Chem 31.1: Qualitative Analysis Page 7 of 20

V. Discussion
A. Test for Unsaturation
A hydrocarbon that contains one or more
double or triple bonds is said to be unsaturated
hydrocarbon. Alkenes contain at least one
carbon-carbon double bond and react with
hydrogen under the right conditions thus, they
are unsaturated. Alkynes, also unsaturated,
contain a carbon-carbon triple bond.
Reaction with Bromine in Methylene
Chloride - Preparation of acetylene gas was the
first step done in this test. It was done by adding
water to calcium carbide. The reaction is given
by this formula:
CaC2(s) + 2H2O(l) C2H2(g) Ca(OH)2(aq)
In the decolorization of bromine solution
test, if the test compound is unsaturated, the
orange-brown color of the aqueous bromine
solution rapidly disappears. The reaction
involved is electrophilic addition (halogenation),
because the bromine adds to each carbon of the
bond. When this happens, the C=C bonds
become saturated. This is the general
mechanism:
Alkene
Alkyne
The double (or triple bond) must be
sufficiently electron-rich to initiate the reaction.
Therefore, minimal electron withdrawing groups,
such as carboxyl groups attached to molecule,
would hinder the reaction.
Bromine adds to each of the carbon of
the bond then the pi bond converts into a sigma
bond and thus become saturated. As a result of
this reaction, an OH group is added to each
carbon at each end of a multiple bond. When
Chem 31.1: Qualitative Analysis
this happens, the multiple bonds become
saturated.
Benzene gave a negative result
because unsubstituted aromatic rings undergo
substitution reactions and not addition reactions.
Bromine solution does not react with the ring
structure of aromatic compounds like benzene.
The shared electrons in the unsaturated bonds
of the aromatic compound ring prevent aqueous
solution from reacting with them.
Baeyer Test - For this test, the
decolorization of KMnO4 from purple into light
color and the formation of a brown to dark
precipitate indicate unsaturation. In the
permanganate test, an unsaturated compound
reduces the purple permanganate ion (MnO4-),
forming a precipitate of brown manganese (IV)
dioxide (MnO2). Because KMnO4 oxidizes the
unsaturated compound, we call the reaction
redox reaction. The general mechanism is:
Alkene
Alkyne
The reaction is important because it
doesn’t work on alkanes (C–C) or aromatic
compounds.
Other test that can be used is the Ignition
Test.
B. Test for Aromaticity
Aromaticity is the special stability of planar,
cyclic, fully conjugated molecules with 4n+2π
electrons. Such molecules have orbital systems
with all bonding molecular orbitals completely
filled with all antibonding and nonbonding
orbitals empty. It can also be considered a
manifestation of cyclic delocalization and of
resonance.
Nitration - For this test, the formation of
yellow solution and naphthalene-like odor
indicate a positive result. The mechanism
governing this test is electrophilic substitution
reaction:
Page 8 of 20

Toluene reacts faster than benzene. In
nitration, the reaction is about 25 times faster.
That means that you would use a lower
temperature to prevent more than one nitro
group being substituted.
Nitration of toluene generates a mixture
of products. The major products are those with
substitution at the ortho and para positions.
The rate-determining intermediates for
ortho and para nitration each has a resonance
form that is a tertiary carbocation. All of the
resonance forms for the rate-determining
intermediate in meta nitration are secondary
carbocations.
Tertiary carbocations, being more
stable, are formed faster than secondary ones.
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.
Other test that can be used is the Le
Rosen’s Test.
C. Test for Acidity and Basicity
Acidity is a measure of the tendency of a
compound to give up a proton. Basicity is a
measure of a compound’s affinity for a proton. In
the Bronsted-Lowry definition, an acid donates a
proton while a base accepts a proton. In the
Lewis definition, an acid accepts an electron
pair while a base donates it.
AgNO3 Test - For this test, formation of
precipitate indicates acidity. The silver nitrate
test is designed to detect strong acids especially
carboxylic acids. The formula for the reaction of
AgNO3 with a carboxylic acid is:
Chem 31.1: Qualitative Analysis
Only acids would react with silver nitrate
if there is hydrogen ion that dissociates and gets
replaced by a silver ion, forming a silver salt
which is a precipitate that shows the tested
sample is an acid. To verify the presence of the
silver salt, dilute nitric acid should be added
which should dissolve the precipitate. Benzoic
acid and acetic acid would form silver precipitate
because they are strong acids with easily
detachable H+ ions. Phenol and aniline do not
form precipitates because they are weaker acids
whose H+ ions are not easily removed.
Silver Acetylide Test - For this test,
formation of pale-yellow to gray-silver precipitate
indicates a positive result. When an alkyne, like
acetylene, is passed through an ammonical
solution of silver nitrate or cuprous chloride –
the Tollen’s reagent (at room temperature),
precipitate of silver acetylide is formed The
equation for the reaction is:
HC CH + [Ag(NH3)2]NO3 AgCCAg +
2HNO3
This test is useful for determining the
difference between alkenes and alkynes
because only alkynes would react with Tollen’s
reagent and form a silver precipitate.
Other test that can be used are the pH
of the solution and the NaHCO3 Test.
D. Test for Alkyl halides
An alkyl halide is another name for a
halogen-substituted alkane. Alkyl halides are
compounds composed of hydrocarbons and
halogens. There can be one or more halogens
attached to the aliphatic hydrocarbon.
Alcoholic AgNO3 Test - This test is used to
indicate the presence of alkyl halides. For this
test, formation of precipitate with different colors
indicates a positive result (AgI – yellow; AgBr –
pale yellow; AgCl – white). By adding an alkyl
halide to alcoholic AgNO3, a silver halide
precipitate would form. The general equation for
this reaction is:
RX + AgNO3 RONO2 + AgX(s)
This reaction can occur slowly which is
why one minute of heating is suggested to
speed it up. Different rate of silver halide
precipitation would be expected from halogen in
Page 9 of 20
each of these environments. Tertiary halides
would react the fastest, followed by secondary
halides, while primary halides would react the
slowest.
Other test that can be used is the
Beilsten Test.
E. Tests for Alcohols and Phenols
Alcohols and phenols both have the
hydroxyl functional group –OH. Alcohols have –
OH that is connected to a carbon chain while
phenols have –OH that attach itself to aromatic
rings. Phenols are considered more acidic than
alcohols. Also, addition of sufficient aqueous
sodium hydroxide to a phenol will cause the –
OH group of most of the molecules present to be
deprotonated; this will not happen to an alcohol.
Reaction with sodium metal – This test
is used to describe the acidity of primary,
secondary and tertiary alcohols. The reaction of
alcohol and the sodium metal would exhibit an
evolution of gas (through the formation of
bubbles) that would indicate a positive test. The
test also promotes the formation of an alkoxide
(–RO). The sodium replaces the hydrogen in the
–OH bond and reduces it to hydrogen gas, as in
the reaction below:
R–OH + Na  R–O- Na+ + H2
The rate of evolution of gas is
dependent on the acidity of the terminal
hydrogen and the removal of H in the OH bond
(due to sodium), reducing it to hydrogen gas. In
the experiment, the rate of evolution of gas is
fastest with primary alcohols, then with
secondary alcohols, then the tertiary alcohols
which are the least reactive. Primary alcohols
have the least amount of electron donating alkyl
groups (known to decrease acidity) and the
terminal hydrogen is open for reaction, making it
reactive. As the alkyl group increases, the
reactivity of alcohol to sodium metal decreases.
Tertiary alcohols, one which have the most
number of alkyl groups, have an increased
electron density and exhibit steric hindrance,
lessening the reactivity of the compound.
The Na metal is highly exothermic in
water, therefore as a safety measure; the test
tube should be dry, since sodium will react with
water, which may cause explosions and may
procure incorrect results. Also, in conducting the
Chem 31.1: Qualitative Analysis
Na+ metal test, the alcohol must only contain up
to 8 carbons because more carbons would
neutralize the acidity of the –OH group,
rendering this test useless.
Lucas Test – This test is also used to
identify the degree of the hydroxyl functional
group in the compound. The Lucas reagent –
consisting of a solution of ZnCl2 (a good Lewis
acid, enhances the formation of carbocations) in
concentrated HCl – would result in layering in
secondary and tertiary alcohols.
The experiment depends on the degree
of the hydroxyl group to react; the more
alkylated the alcohol, the more reactive the
compound. During the reaction, the formation of
a stable carbocation intermediate is favored, and
it is evident in tertiary alcohols. The presence of
alkyl groups (electron donating groups),
abundant in tertiary alcohols, stabilizes the
carbocation intermediate through the donation of
electron to the compound. Secondary and
tertiary alcohols initiated the formation of layers,
but the latter produced a faster and a more
distinct layering. Reaction of the Lucas reagent
with primary alcohol yielded a homogenous
mixture.
It must also be noted that Lucas test
applies only to alcohols soluble in Lucas reagent
(monofunctional alcohols with less than hexyl
and some polyfunctional alcohols). The long
chains of C-bond makes the compound nonpolar
and the –OH group less polar, which will result
in the insolubility of the alcohol in the reagent,
making the test ineffective.
Reaction with potassium dichromate –
This redox reaction with K2Cr2O7 and H2SO4 (an
acid that would make dichromate an oxidizing
agent, which would react with alcohols) is a test
for oxidizables or any compounds that possess
reducing property (has an alpha acidic
hydrogen), which is an alcohol.
Page 10 of 20
 The dichromate ion will oxidize the
carbonyl oxygen, which in turn will reduce
chromium. Primary alcohols will be oxidized to
aldehydes then further into carboxylic acids,
while secondary alcohols will be oxidized to
ketones. Oxidation happens when the
hydrogens attached to the hydroxyl group are
removed, allowing the oxygen to form a double
bond with carbon. Tertiary alcohols will not
undergo oxidation because there is no available
hydrogen atom in the carbon with –OH group
that will participate in the oxidation process.
Primary alcohol:
Aldehyde:
Secondary alcohol:
Tertiary alcohol:
A primary or secondary alcohol will
reduce the orange-red chromic acid/sulphuric
acid reagent to an opaque green or blue
suspension of Cr (III) salts. In tertiary alcohols, a
yellow-orange solution is observed because the
dichromate ion was not reduced.
This test could also be used to identify
phenols, aldehydes, and many amines.
Ferric Chloride Test – It is a traditional
colorimetric test used to detect the presence of
phenol or a phenolic group in a compound. Iron
(III) forms a colored complex with phenol whose
color may vary (blue, violet, green, red-brown)
depending on the structure of phenol. It is
deliquescent, fuming in moist air due to
evaporation of HCl, which hydrates giving a
mist. When dissolved in water, FeCl3 undergoes
hydrolysis and gives off a heat (exothermic
Chem 31.1: Qualitative Analysis
reaction). The resulting brown acidic solution is
corrosive.
It uses iron (III) chloride solution that
has been neutralized with sodium hydroxide until
a slight precipitate of FeO(OH) is formed. Iron
(III) ions form strongly colored complexes with
several organic compounds. Phenols give a
certain color (pink, green or violet) because of
certain coordination complexes with the iron.
The test can be used to differentiate
phenols from alcohols because alcohols do not
undergo this complexation reaction. Also, some
phenols do not give colors so a negative test
must not be taken as significant without
supporting information.
Bromine Water Test – This is an
electrophilic reaction that aims to perform
bromonation to a phenol (highly reactive against
electrophilic reaction). The hydroxyl group of
phenols activates the ring to electrophilic
substitution, so the reaction occurs under very
mild condition (eg. water, a solvent which
increase the stability of the intermediate which
will increase the overall rate of reaction, is
satisfactory polar). The –OH group is an ortho-
para director, so bromine would either react in 2-
bromophenol or 4-bromophenol. Phenol will
react with a solution of bromine in water in the
cold and in the absence of any catalyst. The
increased electron density, caused by the
donation of oxygen’s lone pair (in the –OH
group), attracts the attack of electrophiles to
initiate electrophilic substitution.
Both alkenes and phenols react with
bromine water. Both would indicate color
changes from brown to colorless. For alkenes,
the reaction that occurs is an addition reaction.
Page 11 of 20
In phenols, the reaction undergoes a substitution
reaction, forming a white precipitate which
smells of antiseptic. The precipitate is 2,4,6-
tribromophenol, a compound which has a low
solubility in water used not only as a qualitative
test for phenol but also as a quantitative
measure of the amount of phenol present.
Millon’s Test – The last test for phenols
is Millon’s test, said to be the most delicate yet
the most popular test, is used to detect phenols
and hydroxyl groups in compounds. Millon’s
reagent,(HgNO3)2 in HNO3, is made up of
mercuric and mercurous ions in nitric and nitrous
acids. The test is also used for protein detection,
specifically for tyrosine (contains a phenyl
group), which gives a red precipitate or a red
solution as a positive result. The process is that
the phenol group of tyrosine is nitrated and then,
the nitrated phenol complexes with mercury (I)
and mercury (II) ions. The process is the same
with other phenol compounds. Phenols
containing more than one hydroxyl group do not
give the typical red color. With a few drops of
Millon’s reagent, the aqueous solution of
monacid phenol, even in the cold, or when
warmed (if only traces of phenol are present),
takes on a light to dark red color. This reaction
takes place when one or more hydrogen atoms
of the benzene ring of monacid phenols are
replaced by hydrocarbon radicals. Substituents
such as chlorine, bromine, iodine or carbon free
radicals prevent the replacement. Resorcinol or
catechol may have varied results because they
do not effectively form a compound with a free
–OH group.
F. Tests for Aldehydes and Ketones
Aldehydes and ketones are both
carbonyl compounds. They are organic
compounds in which the carbonyl carbon is
connected to C or H atoms on either side. An
aldehyde has one or both vacancies of the
carbonyl carbon satisfied by a H atom, while a
ketone has both its vacancies satisfied by
carbon.
2,4-DNPH – This test is used to test
aldehydes and ketones. The 2,4-DNPH (2,4-
dinitrophenylhydrazine; also known as Brady’s
reagent) is used to detect the presence of a
C=O group of an aldehyde or a ketone. The
mechanism on which the test revolves is about
condensation or addition/elimination, and
Chem 31.1: Qualitative Analysis
involves nucleophilic addition of NH2 to C=O and
elimination of H2O.
The varying amounts of precipitates
formed between the reagent and the samples
shows the ease with which the reagent could
react with the sample. This shows the solubility
of DNP reagent in a chemical test, and the
indication of DNP-derivatives
(dinitrophenylhydrazone crystals) via the
precipitates. Because of the extensive
conjugation after the reaction, the DNP-
derivatives tend to be highly crystalline. The
yellow derivatives distinguish saturated / non-
conjugated carbonyl compounds while the red or
orange derivatives are the one used to identify
conjugated carbonyl compounds or unsaturated
aldehydes or ketones. The better electrophile
the sample is the greater the amount of
precipitate is formed which indicates a more
complete reaction. It should also be considered
that the presence of a C=O group may be
indicated by an oily layer. Some ketones give
oils which do not solidify (because of high
molecular weight), but the oxygen is still being
replaced, thus an oily layer is formed.
Aside from the oily compounds coming
from ketones, another source for caution is the
presence of an orange-red solution, because
you may be looking at 2,4-DNPH as it is. Also,
some allylic alcohols are oxidized by the reagent
to aldehydes and give a positive test.
Bisulfite Test - This test is for aldehydes
and methyl ketones, where presence of both is
manifested by the formation of a water insoluble
precipitate. Bisulfite oxidizes the oxygen atoms
present in the sample into an –OH group and
simultaneously, sulfur bonds with carbon to form
the precipitate. This test exhibits the
characteristic reaction of aldehydes and ketones
wherein a base-catalyzed nucleophilic addition
occurs across the carbon-oxygen double bond.
Polarization of the C=O bond gives the carbon
atom of the carbonyl group a partial positive
Page 12 of 20
charge because of its electron deficiency, which
makes it susceptible to nucleophilic attack. The
bisulfate ion, a strong nucleophile, then attacks
the carbonyl carbon, oxidizing the oxygen to –
OH and in turn bonds with carbon. The general
reaction is shown below:
Aldehydes react to the bisulfate ion
because of the steric (hinders the attack of the
nucleophile) and inductive (alkyl groups are
weakly electron donors, making the carbon atom
in the carbonyl less electrophilic) effects.
Ketones, on the other hand, react slower,
yielding a yellow precipitate in turn. Also, the
reaction is reversible.
Schiff’s Test – It is the general test for
aldehydes. The Schiff’s reagent which is
fuschine (p-rosaniline hydrochloride) in NaHSO3
is colorless when the carbon to which the three
arene rings are attached is tetrahedral, meaning
no conjugation coming from the rings. The
Schiff’s reagent acts as a nucleophile which
attacks the carbonyl group. The formation of a
purple solution is an indicator of a positive test
for aldehydes. The purple color is now due to
the conjugation of the tri-aryl group present.
Bisulfite produces an sp3 hybridization while the
aldehyde oxidizing to an alcohol will remove the
bisulfate ion. This will now then allow
conjugation as the sp3 hybridization will turn to
an sp2 hybridization, as seen below:
The test is an acid-catalyzed addition of
a weak nucleophile to a carbonyl compound. It
results to the elimination of the sulfuric group
which makes the carbon trigonal. Ketones do
not react with Schiff’s test because of steric
crowding, making the Schiff’s reagent not able to
react with the carbonyl carbon. Also, addition of
the Schiff’s reagent to aldehydes is reversible.
Tollen’s Test – The Tollen’s reagent, a
colorless, basic, aqueous solution containing
silver ions coordinatied to ammonia [Ag(NH3)2+],
based on the formation of a silver diamine
Chem 31.1: Qualitative Analysis
complex that is water soluble in basic solution, is
used to test the presence of aldehydes. This
redox reaction oxidizes the aldehyde into the
corresponding carboxylic acid. The silver ions in
Tollen’s reagents are reduced to metallic silver
(Ag1+ to Ag0), deposited and seen as “siver
mirror”.
No reaction will occur between a ketone
and Tollen’s reagent (except alpha-
hydroxyketone), because ketones are not
oxidized by Tollens’ reagent. A ketone has no
available hydrogen atom on the carbonyl carbon
that can be oxidized. Complications may include
the reaction of formic acid and hydroxylamine,
which can also produce a positive result.
Iodoform Test – The iodoform reagent is
a mixture of iodine (I2) and potassium iodide
(KI). It is used to determine the presence of the
methylketones (CH3-CO) in a molecule. The
reaction of a methylketone with a strong base
will lead to the creation of an enolate. Enolate
reacts with electrophilic I2, undergoing through a
series of enolate anions which are iodinated,
until the hydroxide ion reacts with the carbonyl
carbon of the ketone in a nucleophilic acyl
substitution, liberating iodoform (CHI3) from the
reaction mixture. The displacement of the anion
underwent an addition/elimination pathway. The
method in which iodoform was produces is also
called the haloform reaction. Formation of a
yellow precipitate with a crystal-like appearance,
which is iodoform, is an indication of a positive
result.
Only one aldehyde, acetaldehyde
(ethanal), gives a positive iodoform test. Ethanol
is the only primary alcohol that gives a positive
iodoform test. Naturally, many ketones and
secondary alcohols with the correct structural
components also give a positive test.
Page 13 of 20
 Benedict’s test will not work with
aromatic aldehydes. This is often used in place
of Fehling’s Test.

Fehling’s Test – Fehling’s solution is G. Tests for Amines

used to detect aldehydes. The reagent used is a
mix of CuSO4 and NaOH (Cu2+ in alkaline
solution). Aldehydes are oxidized in the
presence of Fehling’s solution (redox reaction),
turning into carboxylic acid. Copper is reduced
from Cu2+ to Cu1+. Formation of brick red
precipitate (Copper (I) Oxide) is an indication of
positive result.

Fehling’s will not work with aromatic

aldehydes and ketones (unless they are alpha-
hydroxy-ketones).

Molisch’s Test - This test is used to test

for carbohydrates, based on the dehydration of
the carbohydrate by sulphuric acid to produce
an aldehyde. The carbohydrates are eventually
hydrolyzed to monosaccharides by strong
mineral acids. The formation of a blue-violet ring
is an indication of the presence of
carbohydrates. The colored ring is a result of the
furfural (dehydrated carbohydrate, coming from
pentoses) condensing with α-naphtol.

C5H10O5 (pentose) + (conc.) H2SO4 → C5H4O2 +

3 H2O

C5H4 + 2 C10H8OH (α-naphthol) → colored

product
Benedict’s Test –Benedict’s reagent is a
solution of sodium citrate; CuSO4 and sodium
bicarbonate, used in the identification of the
presence of aldehydes and alpha-hydroxy-
ketones, from reducing sugars [sugars with a
free aldehyde or ketone group], mostly
monosaccharides. It is also used to identify
which are reducing sugars since it tests the
ability of the sugar to reduce cupric ion to
cuprous oxide. . The copper sulfate (CuSO4)
present in Benedict's solution reacts with
electrons from the aldehyde or ketone group of
the reducing sugar to form cuprous oxide
(Cu2O), a red-brown precipitate.
Hinsberg Test – Benzenesulfonyl
chloride can be used to distinguish primary,
secondary and tertiary amines based upon the
sulphonamide formation. The amine functional
group must be confirmed before this test can be
performed as the test will give very confusing
results with any other functional group. If a
product forms in the reaction of an amine with
benzene sulfonyl chloride, the amine is either a
primary or secondary amine since tertiary
amines do not form stable sulfonamides. If the
sulfonamide formed dissolves in aqueous
hydroxide solution, it is a primary amine. If it is
insoluble in aqueous sodium hydroxide, it is a
secondary amine. The sulfonamide of a primary
amine is soluble in an aqueous base because it
still possesses an acidic hydrogen on the

Chem 31.1: Qualitative Analysis Page 14 of 20

nitrogen, which can be lost to form a sodium
salt.
Complications include the positivity of
some sodium salts of benzenesulfonamides,
and some tertiary amine hydrochloride salts
(insoluble in dilute HCl) and amphoteric
compounds.
H. Tests for Carboxylic Acid and its Derivatives
Hydrolysis of Acid Derivatives
Hydrolysis of Benzamide – Benzamide,
an amide, contains NH2 and when NaOH was
added, the OH reacted and the product was
formed by C-OH bond. It is possible that
protonation of the O atom came from the
aquaeous (and diluted) NaOH (still has water).
The resulting vapor from the reaction upon
testing with moist litmus paper was basic due to
the basic nature of NH3, a Lewis base. Yet,
sometimes, amides of higher amines do not turn
the litmus paper blue but nevertheless give an
amine-like odor. Some amides also yield a
precipitate or a separated liquid phase (the
carboxylic acid).
Reaction of Carboxylic Acid and
Alcohol/ Hydrolysis of Esters – These reactions
are three-fold: splitting them into carboxylic
acids (or their salts) and alcohols by the action
of water (can be acid or base), dilute acid or
dilute alkali. In the experiment, we used a strong
acid, and in the presence of it, a carboxylic acid
will react with an alcohol to form an ester and
water. This process is called saponification. The
reaction is an equilibrium reaction (reversibility
of reaction). The reaction will be faster if more
dilute acid would be used.
Chem 31.1: Qualitative Analysis
Formation of layers will be seen since
the alcohol and carboxylic acids are water
soluble and the ester is not. There is also a
distinctive change in odor. Alcohols and acids
have usually sharp and extremely unpleasant
odors while esters have pleasant odors.
Note that because the reaction is
reversible, the option to have an ester or to
break them down to carboxylic acids and
alcohols will depend in the environment.
Hydrolysis of Anhydride – Hydrolysis of
an anhydride produces carboxylic acid and heat
(exothermal reaction). Acid anhydrides react
more slowly than acyl halides, but they both
exhibit nucleophilic acyl substitution process,
initiated by the attack of water on the anhydride
group (O), and would not need the assistance of
a catalyst. Unpleasant odor will be observed.
Hydroxamic Acid Test for Acid Derivatives
The Hydroxamic acid test is used to
verify the presence of carboxylic acid
derivatives. Preliminary test is done to eliminate
those phenols and enols that give color with
ferric chloride in acidic solution and would
therefore give a false positive result in the ferric
hydroxamate test. The derivative is allowed to
react with hydroxylamine hydrochloride to
produce hydroxamic acid. The produced
hydroxamic acid is allowed to react with ferric
chloride solution which produces the ferric
hydroxamate complex characterized by a
distinct magenta color. Yellow colors are
indications of negative results.
The mixture cannot be used if the color
produced by the ferric hydroxamate test is not
yellow. A positive test is indicated by the
formation of a blue-red (burgundy or magenta)
color. Esters react with hydroxylamine in basic
solution to form hydroxamic acids, which in turn
react with ferric chloride in acidic solution to form
bluish-red ferric hydroxamates.
Acid Anhydride
Acyl Halide
Page 15 of 20

Ester
Ferric Hydroxamate Complex Formation
VI. Conclusion and Recommendations
Qualitative analysis is one of the best ways
to test compounds and is a very helpful way in
identifying unknown compounds.
Identification of the functional groups gives
the grounds for establishing the nature and full-
identity of an organic compound. Positive results
from the tests will confirm the presence of a
specific functional group.
Mere identification of the functional group
or groups in the organic compound is not sufficient
to establish the full identity of the sample. Further
investigations regarding its chemical and physical
properties should be conducted.
It is recommended to increase
proportionally the increments of the reagents and
the test samples. It is also important to watch out
for false positive results and know the drawbacks of
each test.
Chem 31.1: Qualitative Analysis
VII. References
Bruice, P.Y. (2006). Essential Organic
Chemistry. Prentice Hall: Pearson Education,
Inc.
University of the Philippines Manila (2010).
Laboratory Manual in Organic Chemistry.
University of the Philippines Manila. Learning
Guide in Organic Chemistry.
http://www.cliffsnotes.com/study_guide/Reaction
s-of-Alcohols.topicArticleId-23297,articleId-
23272.html
http://www.jbc.org/content/71/2/445.full.pdf
http://www.scribd.com/doc/24691082/Post-Lab-
Notes
http://www.cerlabs.com/experiments/10875404723.
pdf
http://www.wellesley.edu/Chemistry/chem211lab/Or
go_Lab_Manual/Appendix/ClassificationTests/unsa
turation.html
http://www.scribd.com/doc/25377353/Classification
-Tests-for-Hydrocarbons
http://www.chemguide.co.uk/organicprops/arenes/n
itration.html
http://www.scribd.com/doc/13569421/Experiment-8
I hereby certify that I have given substantial
contribution to this report.
Jeremy Owen G. Go
Maria Nerissa F. Kalaw
Page 16 of 20
GUIDE QUESTIONS AND ANSWERS (Experiment 8A)
1. What test/s could be used to differentiate saturated and unsaturated hydrocarbons? Explain how the test
could differentiate them.
The decolorization of Bromine solution test and Baeyer Test differentiate saturated from
unsaturated hydrocarbons. In the decoloration of Bromine solution test, if the test compound is
unsaturated, the orange-brown color of the aqueous bromine solution rapidly disappears. Bromine adds
to each of the carbon bond then the pi bond converts into sigma bond, thus become saturated. In the
permanganate test, an unsaturated compound reduces the purple permanganate ion (MnO4-), forming a
precipitate of brown manganese(IV) oxide (MnO2). As a result of this reaction, an OH group is added to
each carbon at each end of a multiple bond. When this happens, the multiple bond becomes saturated.

2. Do alkynes give all tests which alkenes exhibit? What tests could be used to differentiate them?
No. The silver acetylide test can be used to differentiate an alkyne from an alkene. Formation of a
silver precipitate can only happen with an alkyne. Another test is the bromine with methylene
tetrachloride. Alkenes will form a red liquid.

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

4. Does toluene behave in the same way like the other unsaturated hydrocarbons? Why?
No. It is because of the presence of a benzene ring. This stable structure due to resonance is less
reactive than the other saturated hydrocarbons. The shared electrons in the saturated bonds of the
aromatic compound ring prevent aqueous bromine solution from reacting with them.

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

It acts as an electrophilic generator by displacing weaker acids from their salts. It turns HNO3 to
NO2+ which would react with toluene.

6. Show the mechanism for the nitration reaction.

Chem 31.1: Qualitative Analysis Page 17 of 20

7. Give the equation involved in the reaction of acetylene with alcoholic silver nitrate.
C2H2 + Ag(NH3)NO3 C2Ag2 + HNO3

8. Tollen’s reagent for the silver acetylide test should always be freshly prepared. Why?
This is because when left standing it decomposes and forms a higly explosive precipitate, silver
fulminate, which is dangerous in lab experiments.

9. Explain why the terminal hydrogen in acetylene is acidic when in fact the electro negativity values of
hydrogen and carbon are almost the same.
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 is
tightly held by the nucleus of C making it electrostatically stabilized. The H+ now, to relieve tension, can
leave off the chain. Since this is a positive H, then terminal alkynes are acidic.

10. What test could be used to determine carboxylic acids from phenol. Explain how the test/s could
differentiate them.
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 while phenols would give a
negative result.

11. Why is the order of reactivity of the alkylhalides toward alcoholic silver nitrate 3°>2°>1°?
Tertiary carbocations formed by the heterolysis of alkyl halide is 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 alkyl halides. The primary carbonium ion is the least stable
since its positive charge is concentrated only to the carbon atom.

12. In the silver nitrate test for halides, explain why alcohol is used as the solvent for silver nitrate and not
water.
Alcohol is used because ethanol can dissolve the polar nitrate and non-polar alkyl chain while water
can only dissolve the polar nitrate. Also, AgBr and AgCl precipitates formed which would indicate halide
presence, would be insoluble in ethanol, making it easier to observe.

Guide Questions / Problems (Experiment 8B)

1. What property of alcohol is demonstrated in the reaction with Na metal? What is the formula of
the gas liberated?

The property of alcohol exhibited in its reaction with sodium metal is its acidity. It releases H+ in the form
of H2 gas.

2. Dry test tube should be used in the reaction between the alcohols and Na metal. Why?

A dry test tube should be used when handling alcohol and sodium metal because sodium metal is highly
reactive and may ignite in the presence of water. It has a low ionization energy, therefore allowing it to
lose electrons readily and release a great amount of energy.

Chem 31.1: Qualitative Analysis Page 18 of 20

 3. Why is the Lucas test not used for alcohols containing more than eight carbon atoms?

The reagent used for Lucas test is composed of zinc chloride in hydrochloric acid. Looking back at the
solubility table, highly nonpolar compounds can no longer be dissolved in hydrochloric acid, therefore
preventing exchange of protons needed to exhibit a positive result.

4. Explain why the order of reactivity of the alcohols toward Lucas reagent is 3°>2°>1°?

The rate of formation of products is based on the stability of the intermediates produced. In the presence
of the Lucas reagent, a tertiary alcohol forms the most stable intermediate: a tertiary alkyl halide, which
requires the least energy for the reaction to proceed. On the other hand, a primary alcohol produces the
least stable intermediate: a primary alkyl halide, which demands a higher energy for the reaction to
proceed. This difference in the energy needed for each reaction accounts for the observed order of
reactivity of the three kinds of alcohols.

5. Illustrate with equations the reactions of the following alcohols with Potassium Dichromate
solution:

a. n-butylalcohol

3CH3CH2OH + Cr2O7 2- + 8H+  3CH3CHO + 2Cr3+ + 7H2O

b. sec-butylalcohol

c. tert-butylalcohol

CH3CH2CCH3CH3OH + Cr2O7 2-  no reaction

6. What functional group is responsible for the observed result in Millon’s test?

Phenol interacts with nitric acid, nitrated phenol reacts with mercury and mercury salts are formed. This
reaction accounts for the observed positive result in Millon’s test.

7. Why is the Schiff’s test considered a general test for aldehydes?

Differentiation of aldehydes from ketones becomes the main purpose of using Schiff’s test since it cannot
distinguish one kind of aldehyde from another.

8. Why is it disadvantageous to use a strong acid catalyst in the reaction of aldehyde or ketone with
2,4-DNPH?

It is because a strong acid when used as a catalyst reverses the sequence of reactions. In the presence
of a relatively weaker acid, the strong nucleophile attacks the substrate then the electrophile follows suit.
Whereas in the presence of strong acid, the strong hydronium ion is more ready for protonation to the
oxygen of carbonyl group. The weaker nucleophile (which thrives in basic medium) then attacks the
carbon to stablilize the forming hemiacetal. Water abstracts the H+ and a hemiacetal is formed.
Hemiacetals are relatively less stable products that will form acetals and will not show the visible changes
that are expected of the test.

Chem 31.1: Qualitative Analysis Page 19 of 20

 9. Show the mechanism for the reaction of acetaldehyde with the following reagents:

a. 2,4-DNPH b. NaHSO3

10. What structural feature in a compound is required for a positive iodoform test? Will ethanol give a
positive iodoform test? Why or why not?

Compounds with methyl carbonyl groups give a positive result for the iodoform test. Such compounds
include acetaldehyde, ketones and secondary alcohols. Through ethanol does not appear in the list
mentioned, it also gives a positive result for the iodoform test, since it can be oxidized to form
acetaldehyde, (BLANK), which has a methyl carbonyl group.

11. Show the mechanisms for the iodoform using acetaldehyde as the test sample:

12. What test will you use to differentiate each of the following pairs? Give also the visible result.
a. Acetaldehyde and acetone

Aldehydes and ketones can be differentiated using the Schiff’s test, where a violet solution forms in the
presence of an aldehyde.

b. Acetaldehyde and benzaldehyde

Acetaldehyde and benzaldehyde can be distinguished from each other using the Bisulfite test since it is
also an indication whether the sample is an aliphatic aldehyde or an aromatic aldehyde. Aldehyde will
react faster than benzaldehyde. Both will form a red precipitate due to cuprous oxide.

13. A colorless liquid has a bp 199-201°C and burns with a smoky flame. The sodium fusion test
proved negative for the presence of halogens, nitrogen and sulfur. It was not soluble in water, 5%
aqueous sodium hydroxide, or 5% hydrochloric acid. However, it dissolved in sulfuric acid with
evolution of heat. It did not give a precipitate with 2,4-DNPH solution and did not decolorize
bromine-methylene chloride solution. The unknown liquid did give a positive hydroxamate test
and was found to have a saponification equivalent of 136. Identify the unknown liquid.

The solubility of the unknown in concentrated sulfuric acid only denotes that it belongs in Group IX
composed of the neutral compounds: alcohols, aldehydes, anhydride, esters, ethers, ketones and
unsaturated hydrocarbons. However, its negative results for the 2,4-DNPH test and bromine in methylene
chloride signify that it is saturated but is neither an aldehyde nor a ketone. Also, the positive result in the
hydroxamic test denotes that alcohols and acyl halides are absent. The high boiling point and high
saponification value eliminate anhydrides and ethers from the list of possibilities, leaving behind ester as
the unknown liquid. The compound is hexyl butyrate.

Chem 31.1: Qualitative Analysis Page 20 of 20