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Names: Balo, Marielle Date Performed: 17 April 2017

Deseo, Ma. Rogemae Date Submitted: 27 April 2017


Gerolaga, Winston Jake

Group: 4

EXPERIMENT 10

CARBONYL COMPOUNDS AND CARBOHYDRATES

I. Introduction

II. Methodology

III. Results and Discussion

Table 1. Solubility behavior of representative substances.

Sample Solubility in
Observation Homogeneity
H2O

1. benzaldehyde Presence of emulsions

(-) (-)
Top layer: clear liquid

Bottom layer: pale yellow liquid

2. acetone (++) Clear, colorless (+)

3. glucose (solid) (++) Clear, colorless (+)

4. starch (solid) (+) Cloudy (-)

5. cellulose (solid) (+) Viscous, clear, colorless (+)

Legend:
Solubility in H2O

(++) - highly soluble

(+) - slightly soluble

(-) - insoluble

Homogeneity

(+) - homogeneous

(-) - non-homogeneous

Table 2. Hydrolysis of Di- and Polysaccharides.

Sample Drops of NaOH to Neutralize Appearance After


the Hydrolysates Heating

1. Sucrose 45 Pale yellow bottom layer

2. Starch 47 Pale yellow bottom layer

3. Cellulose 44 Cloudy bottom layer

Table 3. Chemical reactivity of carbonyl compounds with Tollens reagent.

Sample Precipitate Formed

1. acetaldehyde silver

2. acetone none

Table 4. Chemical reactivity of carbonyl compounds on Iodoform Test.

Sample Miscibility Observations

1. cyclohexanone (-) Brownish insoluble layer

Turbid aqueous layer

2. acetaldehyde (+) Faint yellow, clear


3. acetone (+) Colorless, clear

Legend:

Miscibility

(+) - miscible

(-) - immiscible

Table 5. Chemical reactivity of carbonyl compounds with 2, 4- DNP.

Sample Color of Precipitate

1. benzaldehyde orange

2. cyclohexanone orange

3. fructose yellow

4. glucose yellow

5. acetaldehyde orange

Table 6. Color reactions of carbohydrates using Molisch Test.

Sample Formation of Purple Product

1. Sucrose +

2. Cyclohexanone -

3. Glucose +

4. Starch +

Table 7. Color reactions of carbohydrates using Benedicts Test.

Sample Final Appearance of the Mixture


1. Glucose Dark brown

2. Fructose Dark brown

3. Sucrose Dark brown

4. Lactose Dark brown

5. sucrose hydrolysate Dark brown

6. starch hydrolysate Red

7. cellulose hydrolysate Dark brown

Table 8. Osazone Formation.

Sample Time of Precipitation Observations After Cooling

1. Glucose 4 minutes and 8 seconds Yellow precipitate, opaque

2. Fructose 1 minute and 13 seconds Fine, cotton-like yellow


precipitate

3. Lactose After 30 minutes Dark orange precipitate with


(unreactive) clear upper liquid layer (when
cooled)

4. Sucrose After 30 minutes Fine, yellow precipitate with


(unreactive) slight visibility within the
spaces of its vicinity (when
cooled)

Carbonyl group is an important source of variety of reactions in organic chemistry.


The carbon-oxygen pi bond results to polarization and reactivity of the compound due
to the relatively high electronegativity of oxygen and the dipolar resonance structures
of this functional group.
Thus, this allows the carbonyl group to undergo reactions in which the electrophilic
carbon is attacked by nucleophiles (Lewis bases) and the oxygen reacts with
electrophiles (Lewis acids). This type of reaction is the nucleophilic addition.
Aldehydes and ketones share much of their chemistry as they both have carbonyl
group attached to them. Even so, the two compounds still differ enough in a several
aspects as proven in the series of tests performed.

Carbohydrates, on the other hand, is a class of compounds that somehow


consists hydrated carbon. The class is an organic compound consisting carbon,
hydrogen, and oxygen with the general formula Cm(H2O)n. Carbohydrates make up
the bulk of organic substances on earth and perform numerous roles in living things.
The smallest carbohydrate molecules are called monosaccharides and which are the
basic building blocks for larger carbohydrate molecules, the disaccharides and
polysaccharides. Monosaccharides and disaccharides are collectively referred to as
sucrose or sugars. Polysaccharides include the starches and cellulose. Most
monosaccharides can exist as either an open-chain or a cyclic structure,
monosaccharides that contain an aldehyde group in their open-chain form are
classified as aldoses and ketoses group if they contain a ketone group. An important
reaction observed in this experiment is the formation of hemiacetals. The hemiacetal
functional group has a carbon attached to an -OH and an -OR groupwhich is basically
an alcohol and an ether. The formation is due to the reaction between alcohols and
aldehydes and unhindered ketones.

In aqueous solution, an equilibrium is established in which molecules of the alcohol


and carbonyl components react to form molecules of the hemiacetal at the same time
that other molecules of the hemiacetal are breaking apart to form molecules of alcohol
and carbonyl compound.

The experiment consisted several tests that aimed to distinguish one class of
compound to another by understanding the chemistry of each and the reactions it
undergoes. First part of the experiment focused on the solubility behavior of different
representative compounds. Results showed that all the samples except
benzaldehyde, which represents the aldehyde group, remained insoluble. The
solubility of glucose, starch, and cellulose was due to the presence of oxygen which
introduced partial charges with its high electronegativity. In the case of acetone, which
is a ketone, not only the presence of oxygen but the pi bond that introduced hydrogen
bonding between the compound and water molecule. Meanwhile, benzaldehyde
although it contains carbon doubly bonded to oxygen was not solvated because of the
nonpolar aromatic ring attached to the carbonyl group. As governed by the theory,
like dissolves like, the solubility behavior of different representative compounds for
carbohydrates and carbonyl group also depend on the strengths of the intermolecular
forces of attraction present among the solute, the solvent and between the solute and
the solvent. The domination of carbon and the absence of electronegative elements
promotes insolubilty in polar solvents such as water.

Hydrolysis of disaccharides and polysaccharides were also perfomed in the


experiment. Theoretically, the hydrolysis of any di- or poly- saccharide is the breaking
down of complex saccharides back to the original monosaccharides. Polysaccharides
are hydrolyzed by specific enzymes based on the type of linkage in the
polysaccharide. Enzymes that hydrolyze beta linkages such as in cellulose are
different from the enzymes that hydrolyze alpha linkages. In the hydrolysis of sucrose,
the acetal bond, which is a bond between carbon and two ether oxygens, is broken
and the H in water formed glucose and the OH formed fructose. Starch was
hydrolyzed by an acid become dextin, a polysaccharide, then yield glucose and with
the enzyme diastase yield maltose, a disaccharide. Lastly, hydrolysis of cellulose
yielded glucose and cellobiose which is a disaccharide.

Chemical reactivity of carbonyl compounds was identified with the use of different
tests namely, Tollens test, Iodoform test, and Reaction with
2,4-Dinitrophenylhydrazine. Each class of compound react differently making it
possible for the experimenters to distinguish one class from the other.

Tollens test is governed by oxidation. Silver ion, a weak oxidizing agent, oxidizes
aldehyde to the corresponding carboxylic acid and, in turn, is reduced to metallic
silver which is deposited on the walls of the test-tube such as a mirror. Ketones are
not usually oxidized by the reagent, which significantly indicated that the silver ion in
the tollens reagent is not strong enough to oxidize acetone. As a result, the test tube
with acetaldehyde became a silver mirror and the one with acetone remained to be a
clear liquid with small bubbles. The chemical equation below shows the reaction
between the aldehyde and the Tollens reagent.

Based on the structure of aldehyde, the hydrogen atom directly bonded to the
carbonyl carbon makes it more reactive to oxidation than ketones, which have
R-groups attached to it instead of hydrogen requiring severe conditions in order to
oxidize.

Iodoform test is another test done in this experiment which is commonly used to
test the presence of methyl ketones. Results showed that only in cyclohaxanone and
barely in acetaldehyde did the reaction occur. Other ketones are not capable of
reacting with iodine as proven by the results for acetone. The reaction was very
selective and only occurred for compounds with structures similar to that of methyl
ketones.

The chemical equation above shows the oxidation of methyl ketone with iodine, as the
oxidizing agent, in aqueous sodium chloride. This yields carboxylic acid and the solid
yellow iodoform. Cyclohexanone showed a very clear positive result as expected
since it is a methyl ketone. However, aldehyde only given off a faint yellow color
solution and when heat was applied the color intensified and some iodoform were
formed eventually indicated the occurrence of the reaction. Acetone did not react at all
as indicated by the disappearance of iodine color and the colorless and clear resulting
solution.

The samples in the experiment were also subjected to 2,4-dinitrophenylhydrazine


in order to test for the presence of the carbon-oxygen double bond. Yellow and
orange precipitates were obtained and both indicated the presence of carbon-oxygen
pi bond. For aldehydes and ketones, represented by benzaldehyde, acetaldehyde,
and cyclohexanone, orange precipitates were observed. For carbohydrates, glucose
and fructose, yellow-colored precipitates were obtained. The color of the precipitates
does not indicate the class of compound it belongs, consequently, further
experimentation which involve filtration, purification and melting point determination
would help identify the class of compound to which the unknown belongs.

Color reactions of carbohydrates included three test; Molisch test, Benedicts test
and Osazone formation. All the three tests used color to indicate the occurrence or the
absence of the reaction. Molisch test is used for carbohydrates larger than tetroses is
based on the dehydration of the carbohydrate by sulfuric acid to produce an aldehyde.
Pentoses are dehydrated to form furfural which is the top reaction while hexoses are
dehydrated to form 5-hydroxymethyl furfural, the bottom reaction. The furfurals further
react with -naphthol present in the test reagent to produce a purple product. The
figures below show the reaction for the dehydration of pentose and hexose. (Neither
of the two were used as samples.)

Among the four samples tested, cyclohexanone was the only sample that did not have
the purple color in the resulting solution. This is because of the nature of the sample
which is a ketone. Ketones can not form furfurals that would react to produce the
purple layer. Meanwhile, the sucrose, glucose, and starch, all had a purple layer in
their final solutions. The three samples are carbohydrates that are larger than tetroses
which indicated the capability of the samples to react with the Molisch reagent (10%
naphthol in ethanol).

Benedicts test is basically used to determine whether or not the carbohydrate


contains a free aldehyde or ketone group. The carbohydrates that react positively are
reducing sugars. Theoretically, reducing sugars are oxidized by the copper ion in
solution to form a carboxylic acid and a reddish precipitate of Cu2O. Reduced copper
(I) oxide gives off a red color and the oxidized one gives off a blue color.
All monosaccharides based on theories yield positive results for benedicts test.
Hence, glucose and fructose as monosaccharides and reducing sugars must have
had a red precipitate or a red- colored mixture. The presence of alkali causes
extensive enolization especially at high pH and temperature. This leads to a higher
susceptibility to oxidation reactions than at neutral or acidic pH. These sugars,
therefore, become potential agents capable of reducing Cu+2 to Cu+. However,
resulting solution appeared to be dark brown due to probable human error most likely
during the heating process. For disaccharides, which include sucrose and lactose,
blue precipitate is anticipated as both are non-reducing sugars. This simply imply that
the resulting mixture for the benedicts tests of disaccharides is different from red. The
results obtained were dark brown. Hydrolysates technically contain either two
monosaccharides or a monosaccharide and a disaccharide. For sucrose hydrolysate,
two monosaccharides which are known to be glucose and frustose compose the
solution. Since both of them are reducing sugars, a positive result (red-brick red
precipitate) must have formed. Actual result is dark brown. For polysaccharides,
starch and cellulose, a monosaccharide and a disaccharide compose the solution. In
this case, the result can be affected by the reactivity of the disaccharide. Starch
hydrolyze and become dextrin then form glucose and maltose. Maltose having
exposed carbonyl groups is also a reducing sugar but less reactive than glucose.
Cellulose hydrolyze and form glucose and cellobiose. Results showed the final
appearance for starch hydrolysate is red and for cellulose dark brown. Theoretically,
studies proved that a number of sugars especially disaccharides or polysaccharides
have glycosidic linkages which involve bonding a carbohydrate molecule to another
one, and hence there is no reducing group on the sugar; like in the case of sucrose,
glycogen, starch and dextrin. This applies to some of the samples although the
experimetal results were not parallel with the theoretical results..

Lastly, the osazone formation involved the reaction of ketoses and aldoses with
phenylhydrazine in order to yield phentlhydrazone which further reacts with another
two molecules of phenylhydrazine to produce osazone. Resulting solutions were all
yellow colored liquid and precipitates. The shape of the precipitates vary depending
on the size of the carbohydrate. The test is also used to determine the reactivity of the
carbohydrate. Based on the results, fructose had the shortest time indicating that it
was the most reactive followed by glucose, lactose and least reactive was sucrose.
Results implied that smaller molecules are more reactive as compared to the larger
molecules.

IV. Conclusion

Since carbonyl group is mainly a result of polarization of the carbon-oxygen- -


bond due to the relatively high electronegativity of the oxygen atom, it undergoes a
variety of reactions in which the electrophilic carbon atom is attacked by nucleophiles
(Lewis bases) and the oxygen atom, in turn, reacts with electrophiles (Lewis acids).
The carbonyl functional group also acts to increase the acidity of any hydrogens on
carbons directly attached to the carbonyl group. Moreover, aldehydes and ketones
share the carbonyl functional group which features carbon doubly bonded to oxygen.
In the case of ketones there are two carbon atoms bonded to the carbonyl carbon and
no hydrogens. In the case of aldehydes there is at least one hydrogen bonded to the
carbonyl carbon, the other attachment may be to a carbon or a hydrogen. However, if
the compound has an aromatic ring and a presence of a substituent, the ring has a
greater pi electron density while the substituent takes away electron from the ring
making it less negative. With this mechanism, it made the ring less polar became
insoluble in water.

Carbohydrates, on the other hand, are class of natural compounds that contain
either an aldehyde or a ketone group and many hydroxyl groups, and are often called
polyhydroxy aldehydes or ketones. These can be classified as monosaccharides,
disaccharides or polysaccharides. OH molecules in carbohydrates are hydrophilic that
makes the carbohydrates polar and form bonds with water making them soluble with it.
Hydrolysis of non-reducing di-saccharides is catalyzed by strong acids and certain
enzymes. Furthermore, polysaccharides are hydrolyzed by specific enzymes based
on the type of linkage in the polysaccharide.

Ketones are not usually oxidized by the tollens reagent, which is significantly
indicated by silver ion. Iodoform test was done to test the presence of methyl
ketones. The reaction was very selective and only occurred for compounds with
structures similar to that of methyl ketones. The samples in the experiment were also
subjected to 2,4-dinitrophenylhydrazine in order to test for the presence of the
carbon-oxygen double bond. Yellow and orange precipitates were obtained and both
indicated the presence of carbon-oxygen pi bond.

Molisch test is used for carbohydrates larger than tetroses is based on the
dehydration of the carbohydrate by sulfuric acid to produce an aldehyde. Benedicts
test is basically used to determine whether or not the carbohydrate contains a free
aldehyde or ketone group. The carbohydrates that react positively are reducing
sugars. The test is also used to determine the rate of reactivity of the carbohydrate.

Minor variations, in some experimental results, with the theoretical results are
possibly due human error. However, in general, the objectives of this experiment were
met. The experimenters were acquianted with the chemical properties of carbonyl
compounds and carbohydrates. The experimenter also observed the differences in
the chemical reactivity of aldehydes and ketones, and applied the chemical tests that
can distinguish the different types of carbohydrates.

V. References:

vlab.amrita.edu,. (2011). Qualitative Analysis of Carbohydrates. Retrieved from


vlab.amrita.edu/?sub=3&brch=63&sim=631&cnt=1 Retrieved 26 April 2017

Fox and Whitesell, 3rd Ed. Chapter 13 section 13.1 (643-644). (2007). Reactions of
Aldehydes and Ketones. Retrieved 26 2017

Clark, J. (2015) Oxidation of Aldehydes and Ketones. Retrieved from:


oxidation%20of%20aldehydes%20and%20ketones.html Retrieved 26 2017

(n.d), 2015. The reactions of carbohydrates. Retrieved from:


The%20reactions%20of%20carbohydrates.html Retrieved 26 2017