Rogeni Misaelle M.

Petinglay Date performed: April 6, 2017

B.S. in Chemistry II Date submitted: April 7, 2017

Experiment No. 9
ORGANIC DERIVATIVES OF WATER

I. Summary of Results

Table 1. Solubility Behavior

Solubility Test Observations
Sample 10%
H20 H2SO4 H20 10% NaOH H2SO4
NaOH
Colorless,
Colorless with
2 layers, soluble,
1-butanol S+ - + emulsions, oily
emulsions exothermi
layer
c
Neon
Colorless -> turbid
2 layers, bubble yellow,
white (upon
2-butanol + - + suspennsions soluble,
shaking) ->
upon shaking exothermi
colorless
c
Yellow,
t-butyl Colorless w/ small soluble,
+ - + 2 layers,
alcohol white particles exothermi
c
Pale
2 layers, yellow 2 layers, yellow
brown,
Diethyl bubbly upper layer, upper layer,
S+ - + soluble,
ether coloress bottom colorless
exothermi
layer bottom layer
c
Gelatinous
Turbid white on cloudy white
Phenol - - n/a top, dirty white on solution w/ n/a
bottom small white
precipitates

Legend: + = soluble S+ = slightly soluble - = insoluble

Table 2. Reaction with Potassium Permanganate

KMnO4
Sample
Before heating After heating Result
Brown violet solution with dark Light brown solution with
1-butanol +
violet precipitate dark violet precipitate
2-butanol Brown dark violet solution with Dark brown solution with +
 violet precipitate dark brown precipitate
t-butyl Dark violet solution, no
Dark violet solution -
alcohol changes
Diethyl Dark violet solution with violet Dark brown solution with
+
ether precipitate dark brown precipitate
Pale yellow -> brown
Light brown solution with dark solution with dark red
Phenol +
brown precipitate precipitate, light red
precipitate on the surface

Table 3. Reaction with Ammoniacal Silver Nitrate

Ammoniacal AgNO3
Sample Result
Before heating After heating
Colorless liquid,
1-butanol Colorless liquid -
emulsions
2-butanol Colorless liquid Colorless liquid -
t-butyl alcohol Colorless liquid Colorless liquid -
Diethyl ether Colorless liquid Colorless liquid -
Colorless bottom Pale yellow solution
Phenol layer with pale yellow with emulsions, dark -
upper layer brown precipitate

Table 4. Lucas Test: Reaction with HCl ZnCl2 Mixture

HCl ZnCl2 Mixture
Sample
Observations Results
1-butanol Colorless solution -
2-butanol Colorless solution -> Cloudy white solution +
t-butyl alcohol Colorless solution -> Cloudy white solution +
Diethyl ether Colorless liquid -
Phenol Colorless solution -

Table 5. Reaction with Ferric Chloride

Ferric Chloride
Sample
Observations Result
1-butanol Colorless solution -> Pale yellow solution -
2-butanol Colorless solution -> Pale yellow solution -
t-butyl alcohol Colorless solution -> Pale yellow solution -
Diethyl ether Colorless solution -> Pale yellow solution -
Colorless solution -> light violet with
Phenol +
emulsion
Table 6. Iodoform Test: Reaction with I2, NaOH
Sample Before addition of NaOH
1-butanol Orange solution, 2 layers
Orange solution, 2 layers,
2-butanol
oily upper layer
2 layers, yellow orange upper
t-butyl alcohol
layer, orange bottom layer
2 layers, orange upper layer,
Diethyl ether
yellow orange bottom layer
2 layers, orange upper layer,
Phenol
gelatinous pink bottom layer
After addition of NaOH Result
2 layers, pale yellow upper layer,
-
colorless lower layer
2 layers, pale yellow upper layer,
-
colorless lower layer
Soluble, pale yellow solution -
2 layers, yellow upper layer with
-
some yellow immiscible liquid
2 layers, colorless upper layer, oily
-
white turbid lower layer

II. Discussion

Solubility Behavior

This part of the experiment examined the solubility of the each sample in water, 10%
NaOH and H2SO4 if insoluble in the basic solvent. The samples used were 1-butanol, 2-butanol,
t-butyl alcohol, diethyl ether, and phenol.

Solubility in Water. The presence of a polar functional group in a sample will be soluble
in water following the rule like dissolves like. Alcohols are insoluble in water except if they
are in Carbon-6. The more branching is present in a compound, the more it will be soluble
because branching lowers intermolecular forces and deceases intermolecular attraction. The
higher the number of carbon atoms, the more nonpolar the compound making it insoluble in
water. Diethyl ether is a diprotic solvent which means that it has limited solubility in water. In
the experiment, results showed that phenol was insoluble in water while 1-butanol and diethyl
ether are slightly soluble. Samples soluble in water are 2-butanol and t-butyl alcohol.

Solubility in 10% NaOH. A compound is deemed soluble in NaOH if it is significantly

soluble in water. Insoluble compounds in this solvent are some sodium salts with highly
substituted phenols. In the experiment, all of the samples were insoluble in this solvent.
Alcohols are insoluble in NaOH solution because it is the hydroxide reacting with the alcohol,
not the sodium ions (Rxn: NaOH + R-OH -> R-ONa + H2O). The free energy difference between
the products and reactants side of the equation is not very large, however, so there will be some
equilibrium between hydroxide ions (OH-) and alkoxide ions (R-O-) in solution, which will
depend on the pKa of the alcohol (Net ionic equation: OH- + R-OH -> R-O- + H2O). The reaction
of phenol with NaOH gave a gelatinous cloudy white solution w/ small white precipitates.
Theoretically, it should give a colorless solution containing sodium phenoxide. Phenol behaves
as an acid and gives up its proton to the OH- which is a base that is why it dissolves in NaOH
solution.

Solubility in H2SO4. Sulfuric acid protonates all organic compounds that contains oxygen
and/or nitrogen, as well as few aromatic carbons and alkenes. The reaction of the compound with
this solvent may produce color changes and heat. In the experiment all the samples tested as
observed to have an exothermic reaction. Some color changes were observed in 2-butanol
(colorless to neon yellow solution), t-butyl alcohol (colorless to yellow solution), diethyl ether
(yellowish to pale brown solution). In 1-butanol, no color change was observed.

Reaction with Potassium Permanganate

Baeyer's reagent is an alkaline solution of cold potassium permanganate, which is a

powerful oxidant making this a redox reaction. Reaction with double or triple bonds in an
organic material gives a positive test which includes the disappearance of purple color and
appearance of brown precipitate.

In the experiment, all of the samples turned into a brown colored solution with the
appearance of precipitates except for t-butyl alcohol which had no changes. Tertiary alcohols
cannot be oxidized for the reason that all the hydrogen atoms are already filled or occupied by
the remaining 3 spaces needed and there are no hydrogen atoms attached to the alcohol carbon.
KMnO4 oxidizes phenol to para-benzoquinone while alcohols will be oxidized to carbonyls.

Reaction with Tollens reagent (Ammoniacal Silver Nitrate)

Tollens' reagent is a chemical reagent used to determine the presence of an aldehyde,

aromatic aldehyde and alpha-hydroxy ketone functional groups and not for alcohols. The reagent
consists of a solution of silver nitrate and ammonia.

It can oxidize aldehydes into corresponding carboxylate ion, while it reduces itself to
metallic silver. The aldehyde itself is oxidised to a salt of the corresponding carboxylic acid
because the solution is alkaline. Only phenol reacted to the reagent but it was not a positive
result. The solution turned pale yellow instead of a silver mirror solution. The rest of the
samples remained colorless.

Lucas Test: Reaction with HCl ZnCl2 Mixture

Lucas test distinguishes tertiary, secondary and primary alcohols from each other by
using zinc chloride as the reagent in concentrated hydrochloric acid. It is based on the rate of
formation of insoluble alkyl chloride. An emulsion is formed. This test is reliable only for
alcohols that are fairly soluble in water. The rate of reaction of the alcohols is determined by the
ease of formation of the carbocation intermediate. Tertiary alcohols react quickly because they
form a relatively stable tertiary carbocation while secondary alcohols react more slowly because
the secondary carbocation is less stabilized than the tertiary carbocation. Primary alcohols
generally take to react, about an hour.

The reaction of a tertiary alcohol, involves a Lewis acid- base reaction between zinc
chloride and a lone pair of electrons on the alcohol oxygen. In a slow, rate determining step, the
HO-ZnCl complex leaves and the carbocation is then attacked by a chloride anion from the HCl
solvent to form the insoluble alkyl chloride which forms the cloudy emulsion indicative of a
positive test. Again, the overall rate of the reaction is determined by the slow step, which is the
breaking of the C-OH-ZnCl bond. This rate is determined by the stability of the carbocation
being formed.

Experimental results show that only 2-butanol and t-butyl alcohol gave positive results
while t-butyl alcohol, diethyl ether and phenol gave negative results. Experimental results
slightly deviated from the expected result because of t-butyl alcohol. It should have given a
positive result. The experimenters might have thought that no more reaction will take place,
immediately after 30 minutes, the samples were discarded because the test tubes will be used for
the next part of the experiment.

Reaction with Ferric Chloride

The ferric chloride test is used to determine the presence of phenols in a given sample or
compound. This test is traditional calorimetric test for phenols which uses a 1% iron (III)
chloride solution that has been neutralized with sodium hydroxide until a slight precipitate of
FeO(OH) is formed. Enols, hydroxamic acids, oximes, and sulfinic acids give positive results as
well. A positive result forms a violet complex with iron (III), which is intensely colored. In the
experiment, only the phenol setup obviously turned into a violet solution while the rest turned
into pale yellow solution which indicates a negative result. Phenol is acidic, and can form the
phenoxide ion. This ion can complex with iron (III) and form a coloured substance. Alcohols are
much less likely to form ions than phenol is, meaning alcohols cannot complex the iron(III) ion
and therefore cannot form coloured compounds.

Iodoform Test: Reaction with I2, NaOH

This test does not distinguish 1, 2, 3 alcohol but is specific for only one class of
alcohol. This is the secondary methyl alcohol. If the alcohol contains a methyl group attached to
a carbon that also has a hydrogen and an OH group then it will give a positive iodoform test. The
formation of a yellow precipitate indicates a positive test. Apart from its colour, this can be
recognised by its faintly "medical" smell. In the reaction, there is a formation of a mild oxidizing
agent sodium hypoiodite, NaOI, from sodium hydroxide and iodine. NaOI oxidizes the alcohol to
a carbonyl. The alcohol is oxidized to a ketone and iodine gains two electrons. In the third step,
which really consists of several individual steps, the methyl ketone is converted to the anion of a
carboxylic acid (with one carbon less than the alcohol) and iodoform (yellow precipitate).
Experimental data shows that all the samples were negative. There were color changes to a
yellow solution, however, no yellow precipitate formations were observed.
 III. Conclusion

The organic derivatives of water, such as alcohols, phenols and ethers have different
chemical properties. To be acquainted with these properties, certain tests can be made. The
solubility behavior follows the general rule like dissolves like. Reaction with potassium
permanganate involve redox reaction with double or triple bonds in an organic material. A
positive test which includes the disappearance of purple color and appearance of brown
precipitate. The Tollens test is used to determine the presence of an aldehyde, aromatic aldehyde
and alpha-hydroxy ketone functional groups. The formation of black precipitates indicates a
positive result. Lucas test distinguishes tertiary, secondary and primary alcohols from each other
by using zinc chloride as the reagent in concentrated hydrochloric acid. A positive test turns a
solution into cloudy white. The ferric chloride test is used to determine the presence of phenols
in a given sample or compound. A positive result forms a violet complex with Fe3+, which is
intensely colored. Iodoform test is used to determine the presence of secondary methyl alcohol.
If the alcohol contains a methyl group attached to a carbon that also has a hydrogen and an OH
group then it will give a positive iodoform test.

Some errors were observed based on the experimental results. This may be due to human
errors, contaminations, and inappropriate proportions.

IV. Answers to Questions

1. Explain the solubility behavior of the representative compounds in water as a function of:
a) branching in the molecule
The more branching is present in a compound, the more it will be soluble in water
because branching lowers intermolecular forces and decreases intermolecular attraction
b) relative proportions of hydrophilic bonds to hydrophobic bonds
Hydrophilic bonds are water soluble while hydrophobic bonds are water insoluble.
Hydrophobic bonds are those without any functional groups or C-C bonds and have
change in the cluster or position of water and solute. Hydrophilic bonds have O, N- very
electronegative atoms and involves H-bonding.
2. Explain the acidity differences observed for the compounds used in this exercise in terms of
the stability of the corresponding conjugate bases.
K-OH bond gives alkoxide anion. It is a strong base which can easily attract proton. R-
OH acts as lewis acids. All samples except phenol are insolubkke on the 10% NaOH.
Phenol is a strong base.
3. Based on the results of the oxidation test, classify the compounds tested according to the
following categories: easily oxidizable, oxidizable, and resistant to oxidation.
The appearance of black particles indicates that all compounds except phenol were easily
oxidizable according to the students experimentation. Phenol can be oxidizable to easily
oxidizable due to change with solutions color.
4. Discuss the reactivity differences of alcohols towards the Lucas reagent.
Possible error could have occurred despite the formation of a cloudy white solution in in
the experiment.
 Tertiary alcohols react immediately, secondary alcohols react for about 8-10 minutes and
primary alcohol react the longest for about an hour, and sometimes it gives no reaction.
1-butanol- primary alcohol (no reaction when time was stopped)
2-butanol- secondary alcohol
t-butyl alcohol tertiary alcohol

5. Suggest simple chemical test that will differentiate between the following pairs of compounds.
Write the equations for the reactions involved.
a. phenol and isopentyl alcohol -> dilute NaOH solution
C6H5OH(s) + OH-(aq) -> C6H5O-(aq) + H2O(g)
b. tert-butyl alcohol and isobutyl alcohol -> water oxidation
C4H9OH(s) + H2O(l) -> C4H10O(aq)
c. neopentyl alcohol and ether -> evaporation
C5H912O + H2O -> C4H10O
d. sec-butyl alcohol and neopentyl alcohol -> Lucas Test
C5H912O + HCl -> C5H12O
e. propene and butanol -> Acid hydrolysis
C3H6 + H2O -> C4H9OH

V. References

Experiment 6: Qualitative Tests for Alcohols, Alcohol Unknown, IR of Unknown. Retrieved

April 8, 2017 from http://myweb.brooklyn.liu.edu/swatson/Site/Laboratory_Manuals_
files/Exp6.pdf

Organic Derivatives of Water. Retrieved April 8, 2017 from https://www.scribd.com

/doc/48026330/Organic-Derivatives-of-Water

The Iodoform Test. Retrieved April 8, 2017 from http://www.harpercollege.edu/tmps/chm/

100/dgodambe/thedisk/qual/iodo.htm

Physics Forums. Retrieved April 9, 2017 from https://www.physicsforums.com/threads/why-

cant-alcohol-react-with-aqueous-naoh.410255/