Name: Gonzaga, Jane H.

Date Performed: April 6, 2017

Gumafelix, Ira Candice C. Date Submitted: April 17, 2017
Nieves, Syndy C.
Pormilda, Gracechel Ann C.
Group #: 1
EXPERIMENT 9
ORGANIC DERIVATIVES OF WATER

I. INTRODUCTION

Alcohols, phenols, and ethers can be thought of as organic derivatives of water in which one or
both of the hydrogens have been replaced by organic parts. They are different functional groups whose
common denominator is the presence of a singly bonded Oxygen atom in their chains. Thus, all three
classes of compounds have nearly the same geometry as water. The C-O-H or C-O-C bond angles are
approximately tetrahedral—109° in methanol and 112° in dimethyl ether, for instance—and the oxygen
atoms are sp3-hybridized. The leaving groups of alcohols and ethers 1HO-, RO- 2 are much stronger
bases than the leaving group of an alkyl halide. Because they are stronger bases, they are poorer leaving
groups, and therefore are harder to displace. Consequently, alcohols and ethers are less reactive than alkyl
halides in substitution and elimination reactions. (McMurry, 2011)
Alcohol is an organic compound in which a hydroxyl functional group (-OH) is bound and
connected to a carbon atom or hydrogen atom. It has two reactive covalent bonds, C-O bond and the O-H
bond. Alcohol also contains both polar (OH group) and nonpolar alkyl group, which is a factor why
alcohol tends to be water-soluble. Similar to water, an alcohol can be pictured as having an sp3
hybridized tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of the four sp3
hybrid orbitals. Alkyl groups are generally bulkier than hydrogen atoms however, so the R−O−H bond
angle in alcohols is generally larger than the 104.5° H−O−H bond angle in water. Water and alcohols
have similar properties because water molecules contain hydroxyl groups that can form hydrogen bonds
with other water molecules and with alcohol molecules, and likewise alcohol molecules can form
hydrogen bonds with other alcohol molecules as well as with water. Because alcohols form hydrogen
bonds with water, they tend to be relatively soluble in water. The hydroxyl group is referred to as a
hydrophilic (“water-loving”) group, because it forms hydrogen bonds with water and enhances the
solubility of an alcohol in water. Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and t-butyl
alcohol are all miscible with water. Alcohols with higher molecular weights tend to be less water-soluble,
because the hydrocarbon part of the molecule, which is hydrophobic (“water-hating”), is larger with
increased molecular weight (Wade, 2011).
The chemical behavior of phenols is different in some respects from that of the alcohols, so it is
sensible to treat them as a similar but characteristically distinct group. A compound which contains a six-
membered aromatic ring, bonded directly to a hydroxyl group (-OH) is called phenol. Its structure is that
of a hydroxyl group (-OH) bonded to a phenyl ring and it is an aromatic compound. It is much acidic
compared to alcohol and has limits in solubility in water. Because phenol contains an alcohol group, it is
not only able to form a very strong hydrogen bond with other molecules, but this bond contributes to
phenol's affinity towards polar substances. As a polar molecule, phenol is soluble in water. In other
words, phenol and water are friends (Essays, 2013).
Ethers are similar in structure to alcohols, and both ethers and alcohols are similar in structure to
water. Ethers are a class of organic compounds that contain an ether group. An ether group is an oxygen
atom connected to two alkyl or aryl groups. Ethers are stable in bond and are relatively inert molecules
that results to being generally unreactive. It has an oxygen atom directly bound to two hydrocarbon (alkyl
or aryl) groups and its common example is diethyl ether. The ether linkage C–O–C, is quite stable and can
be cleaved only under drastic conditions. The oxygen of the ether is more electronegative than the
carbons. Thus, the alpha hydrogens are more acidic than in regular hydrocarbon chains. The unshared
pairs of electrons on the oxygen atom, however, make the ethers susceptible to electrophilic attack. Ethers
are rather nonpolar due to the presence of an alkyl group on either side of the central oxygen. The
presence of the bulky alkyl groups that are adjacent to it means that the oxygen atom is largely unable to
participate in hydrogen bonding. Ethers, therefore, have lower boiling points compared to alcohols of
similar molecular weight. However, as the alkyl chain of the ethers becomes longer, the difference in
boiling points becomes smaller. This is due to the effect of increased Van der Waals interactions as the
number of carbons increases, and therefore the number of electrons increases as well. The two lone pairs
of electrons present on the oxygen atoms make it possible for ethers to form hydrogen bonds with water
(Boundless, 2016).
In this experiment, 1-butanol, 2-butanol, t-butyl alcohol, diethyl ether and phenol will be tested
for their solubility behavior and chemical reactivity to different solvents.

1-butanol 2-butanol tert-butyl diethyl ether phenol

(primary alcohol) (secondary alcohol) (tertiary alcohol)

II. METHODOLOGY

A. Solubility behavior
The solubility behavior of the compounds in water, NaOH and conc. H2SO4 were tested. In order
to do so, 2 ml distilled water was placed in 5 different test tubes. The test tubes were then labeled as 1-
butanol, 2-butanol, t-butyl alcohol, diethyl ether and phenol. In each of the test tubes, 10 drops of the
sample was added and was then mixed and examined. After so, the same process was done but instead of
using water, NaOH was used. For compounds that were slightly soluble and insoluble in NaOH, their
solubility was then again tested with H2SO4. The observations were then recorded.

B. Chemical Reactivity
1. Reaction with potassium permanganate
To test for the sample’s reactivity with slightly acidic potassium permanganate, 3 ml of the said
solvent was placed on 5 clean test tubes. The test tubes were labeled 1-butanol, 2-butanol, t-butyl alcohol,
diethyl ether and phenol. In each of the test tubes, 5 drops of the sample was added and were then gently
warmed in a water bath for 5 minute and was examined.

2. Reaction with Tollen’s reagent (ammoniacal silver nitrate)

To test for the sample’s reactivity with Tollen’s reagent, 3 ml of the said solvent was placed on 5
clean test tubes. The test tubes were labeled 1-butanol, 2-butanol, t-butyl alcohol, diethyl ether and
phenol. In each of the test tubes, 5 drops of the sample was added and the tube was shaken. They were
then gently warmed in a water bath and was examined.

3. Lucas Test: reaction with HCl – ZnCl2 mixture

Five test tubes each containing 2 ml of the HCl – ZnCl2 mixture were prepared. Five drops of
each of the samples were then added. The test tubes were immediately covered with a stopper and were
shaken. The mixtures were allowed to stand and were observed noting the time of the appearance of an
insoluble layer or emulsion.

4. Reaction with ferric chloride (FeCl3)

Two drops of the samples in 2 ml water were placed in 5 test tubes. Several drops of 2.5%
aqueous ferric chloride were then added to each of the samples. The resulting mixture were then
examined and the results were compared to that of the blank (water only).
5. Iodoform test: reaction with I2, NaOH
About 1 ml of the samples with 2 ml water was placed in separate test tube. One ml of I2/KI
solution was then added to the mixture. A solution of 10% NaOH was also added dropwise while shaking
until the iodine color disappeared and the solution was faintly yellow. The contents were examined and
the odor of the mixture was noted. The tests that seemed negative were shaken and when no reaction was
observed, they were heated gently in a water bath for 1-2 minutes and was examined again.

III. RESULTS AND DISCUSSION

A. Solubility Behavior
Water is a polar solvent which dissolves polar compounds. Several structural features of the
unknown can be deduced if it is water-soluble. It must be of low molar mass and will usually contain no
more than four to five carbon atoms, unless it is polyfunctional. It must contain a polar group that will
form a hydrogen bond with water, such as the hydroxyl group of an alcohol. Aqueous sodium hydroxide
is a strong base that dissolves compounds to form sodium salts that are soluble in aqueous medium.
Concentrated sulfuric acid protonates all organic compounds that contain oxygen and/or nitrogen, as well
as alkenes and a few aromatic hydrocarbons. These protonated organic compounds exist as ionic salts in
sulfuric acid. Because sulfuric acid is a highly polar liquid, it dissolves the protonated compounds. The
dissolution of compounds in H2SO4 may also produce large amounts of heat and/or a change in the color
of the solution (Festin, A. J. M. & Raquepo, V. V., 2014).

Table 1. Solubility behavior of the samples in water, NaOH, and conc. H2SO4
Solvent 1-butanol 2-butanol t-butyl diethyl ether Phenol
Water - ++ ++ - -
NaOH - - - - ++
conc. H2SO4 - - + + untested
Note: (++)-soluble, (+)-slightly soluble, and (-)-insoluble

Table 1 shows the results of the solubility behavior test performed for each of the sample and
only 2-butanol and t-butyl alcohol were soluble in water. This is because, as the alkyl group increases in
size, becoming a more significant fraction of the entire alcohol molecule, the compound becomes less and
less soluble in water. In other words, the molecule becomes more and more like an alkane. Groups with
four carbons such as 1-butanol, 2-butanol and tert-butanol tend to straddle the dividing line at room
temperature. So alcohols with fewer than four carbons are soluble in water, but alcohols with more than
four carbons are insoluble in water. Thus, an OH group can drag about three or four carbons into solution
in water. Alcohols with branched alkyl groups are more soluble in water than alcohols with unbranched
alkyl groups with the same number of carbons. Branching minimizes the contact surface of the nonpolar
portion of the molecule. Thus, tert -butyl alcohol is more soluble than 2-butanol. N-butanol however, did
not show any sign of solubility in water because of its unbranched alkyl group. Diethyl ether is insoluble
in water because it is a nonpolar molecule. The oxygen of an ether, like the oxygen of an alcohol, can
drag only about three carbons into solution in water, thus rendering the diethyl ether insoluble in water.
Phenol is also insoluble in water and was observed to form a layers when it was added to the water. This
might be due to the large amount of phenol that was made to react with water. In theory, phenol should be
slightly soluble in water due to its ability to form hydrogen bond. (Bruice, 2014)
For the test in NaOH, only Phenol had an observable reaction to the solvent. Phenol dissolves in
aqueous sodium hydroxide because it behaves as an acid and gives up its proton to the hydroxide ion,
which is a base. A soluble ionic product is formed. In this reaction, the hydrogen ion has been removed by
the strongly basic hydroxide ion in the sodium hydroxide solution. The alcohols and the diethyl ether did
not have any observable reaction to the solvent. Alcohols are about as acidic as water thus, they do not
react with weak bases such as amines or bicarbonate ion and they react to only a limited extent with metal
hydroxides, such as NaOH (McMurry, 2011).
 The insoluble samples in NaOH were tested again for their solubility in conc. sulfuric acid. The
only sample that had a visible reaction to the solvent was tert-butyl and diethyl ether. The two samples
were observed to be slightly soluble in the solvent. This is because the dehydration reaction of alcohols to
generate alkene proceeds by heating the alcohols in the presence of a strong acid, such as sulfuric or
phosphoric acid, at high temperatures. The required range of reaction temperature decreases with
increasing substitution of the hydroxyl-containing carbon. For 1° alcohols: 170° - 180°C, 2° alcohols:
100°– 140 °C, and 3° alcohols: 25°– 80°C (Huang, 2016). This proves that at room temperature, among
the alcohols only tert-butyl would have a visible reaction to the solvent. Ethers serve as Lewis bases and
Bronsted bases in a reaction. Therefore, when strong acids are made to react with it the oxygen is
protonated to give "onium ions".

B. Chemical Reactivity

1. Reaction with Potassium Permanganate

Bayer's reagent (KMnO4) is an alkaline solution of potassium permanganate, which is a powerful
oxidant. This reagent is used for oxidation (Bayer’s Oxidation). Reaction with double or triple bonds (-
C=C- or -C≡C-) in an organic material causes the color to fade from purplish-pink to brown. The
disappearance of the purple color and the appearance of a brown precipitates conclude that it is a positive
test. Often, the brown precipitate fails to form and the solution turns reddish-brown. Also, easily oxidized
gives a positive test (Frias, A, P. F.& Roque, J. R., 2011).
Alcohols with a hydrogen attached to the same carbon as the hydroxyl group, in other words
primary or secondary alcohols, can be oxidized by many oxidizing agents. If oxidation-reduction takes
place, the solution changes color and sometimes forms precipitates. Primary alcohols can be oxidized to
either aldehydes or carboxylic acids depending on the reaction conditions. In the case of the formation of
carboxylic acids, the alcohol is first oxidized to an aldehyde, which is then oxidized further to the acid.
Secondary alcohols are oxidized to ketones and that is it (Clark, 2015).

Table 2. Reaction of samples to Potassium Permanganate

Sample 1-butanol 2-butanol t-butyl diethyl ether Phenol
Reaction Formed a black Formed a black Formed a black Formed a black Insoluble,
precipitate precipitate precipitate precipitate formed a layer

All the samples except for phenol formed a black precipitate when they were added to the solvent
and heated. Due to the slight acidity of the solvent, it was able to positively react with the four samples
faster than it would have without the acidity. This means that the alcohols and ether are easily oxidizable
using potassium permanganate. Base on theory though, tert-butyl is not supposed to be oxidized by
potassium permanganate because it does not have a hydrogen atom attached to the alcohol carbon.
Phenols should have also been theoretically oxidized even though they do not have an H atom attached to
the C atom carrying the OH group. Their reaction with oxidizing agents is quite different from that of
primary or secondary alcohols. Only very strong oxidizing reagents, such as permanganate would be able
to oxidize it (Herges & Wenkler, 2017).

2. Reaction with Tollen’s reagent (ammoniacal silver nitrate)

Tollens’ test, also known as silver-mirror test, is a qualitative laboratory test used to distinguish
between an aldehyde and a ketone. It exploits the fact that aldehydes are readily oxidized, whereas
ketones are not. Tollens’ test uses a reagent known as Tollens’ reagent, which is a colorless, basic,
aqueous solution containing silver ions coordinated to ammonia [Ag(NH3)2+]. Silver ions in the presence
of hydroxide ions come out of solution as a brown precipitate of silver(I) oxide, Ag2O(s) (Gunawardena,
2016).
Table 3. Reaction of samples to Tollen’s reagent
Sample 1-butanol 2-butanol t-butyl diethyl ether Phenol
Reaction soluble Slightly soluble soluble Insoluble with
soluble with black
black precipitate
precipitate

Tollen’s test is used to detect aldehydes, therefore the result of

Figure 1. Reaction of aldehyde with
Tollen’s reagent
the experiment is correct. All the sample did not form any
“mirror” when they were added to Tollen’s reagent. Therefore,
they were no aldehydes in the sample. A positive test would
result into a silver mirror just like in Figure 1 (left test tube).
Negative results would form a colorless solution such that in
Figure 1 (right test tube). The formation of black precipitate in 2-
butanol and phenol maybe due to the unclean test tubes that
were used in performing the experiment.

3. Lucas Test: reaction with HCl – ZnCl2 mixture

This test is used for alcohols to differentiate whether it is primary, secondary, or tertiary. It is
based on the difference in the reactivity of the three classes of alcohols with hydrogen halides. When an
alcohol is reacted with Lucas reagent (anhydrous ZnCl2, HCl), the resulting mixture which is alkyl halide
will not be soluble in water, thus presence of cloudiness and second layer will form if only the test is
positive. With this reagent, time is essential in order to determine if the compound reacts with it (Herges
& Wenkler, 2017). The Lucas test involves a substitution reaction, where the –OH group of the alcohol is
replaced by a Cl atom. The Lucas reagent consists of a mixture of HCl and ZnCl2 that are dissolved in
water. The mechanism of this reaction involves a carbocation intermediate: first an OH- ion is removed
from the alcohol, leaving the carbon atom in the molecule positively charged. Then a Cl- ion adds to the
positively charged carbon atom. The result is the alcohol is converted to a chlorinated alkane, with the Cl
occupying the spot that the –OH was in (Fossum C., 2012).

Table 4. Reaction with HCl – ZnCl2 mixture

Sample 1-butanol 2-butanol t-butyl diethyl ether Phenol
Time No reaction 4:29.6 Reacted No reaction No reaction:
immediately insoluble

Only the 2-butanol and t-butyl had changes when they were added to the solvent. When tert-butyl
was added to the solvent, it immediately formed a cloudy mixture pertaining to a positive test. The 2-
butanol however took a little while before a cloudy mixture was observed. The other samples did not react
at all with the solvent. Since tertiary carbocations are much more stable than primary or secondary
carbocations, tertiary alcohols will react readily with the Lucas reagent. Secondary alcohols will react
slowly (usually in 5-10 minutes). Primary alcohols will not react much at all, since a primary carbocation
is so unstable (Fossum C., 2012). Therefore, the experiment was correct and no errors were made.

4. Reaction with ferric chloride (FeCl3)

Ferric chloride is used to determine the presence or absence of phenols in a given sample. 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. A transient or
permanent coloration (usually purple, green or blue) indicates the presence of a phenol or enol, which
indicates a positive reaction also. Phenols react with FeCl3 to form a colored complex with the Fe3+ ion.
The color varies from purple to orange depending on the structure of the phenol tested. Alcohols do not
form colored complexes with iron ion. In this test, the appearance of a color is taken as a positive test and
it indicates that a phenol was present in the original solution (Herges & Wenkler, 2017).

Table 5. Reaction of the samples to Ferric Chloride

Sample 1-butanol 2-butanol t-butyl diethyl ether Phenol
Reaction No reaction No reaction No reaction No reaction From yellow-
orange to
indigo

Only the phenol had a positive reaction with the solvent. Therefore, the experiment’s result is
correct and no error was made. The alcohols and ethers had no reactions because comparing the mixture
of the sample and the solvent with their blanks, there were no color change.

5. Iodoform test: reaction with I2, NaOH

The iodoform test is used to identify secondary alcohols that have a methyl group on the alcohol
carbon. This type of alcohol will react with I2 in NaOH to give a yellow precipitate of iodoform, CHI3.
The formation of a yellow precipitate in the test solution is taken as a positive reaction, and it means that
the reactant alcohol was a secondary alcohol with a methyl group on the alcohol carbon (Fossum C.,
2012).

Sample 1-butanol 2-butanol t-butyl diethyl ether Phenol

Reaction Formed layer Formed layer Soluble, no Formed layer Formed layer
of orange and with the same precipitate of pale orange of yellow and
yellow color, little and yellow peach
precipitate

The tert-butyl did not form any layer or precipitate with the solvent but it appeared to be soluble
in it. The 2- butanol however, formed a layer of the same color with the solvent. Among the other samples
used, it was the only one that had the same colored layer and formed little precipitates. We can therefore
say that the experiment was correct. On why the diethyl ether appear to be soluble though might be due to
some errors as it was not supposed to react with the solvent.

IV. CONCLUSIONS AND RECOMMENDATION

Alcohols, phenols, and ethers can be thought of as organic derivatives of water in which one or
both of the hydrogens have been replaced by organic parts. Though phenol and alcohol are somewhat
similar to each other, they react differently to solvents. As the number of carbon atoms in an alcohol
increases, its solubility in water and its acidity decreases. However, as the number of branched group
increases, the solubility of the alcohol in water also increases. The different types of alcohols can also be
identified using different solvent or their reactivity to a certain solvent (Lucas Test). Iodoform Test can
tell whether a sample contains a methyl group and if it is a secondary alcohol. Reaction with Ferric
Chloride can tell when a sample contains phenol due to the color change. The rate of oxidation of the
samples could also help in telling what type of alcohols they are. It is recommended that the experimnets
be done on a clean and dry test tube to avoid any contamination and to ensure that the results are accurate
to the theoretical ones.

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