Experiment 1: Solubility Behavior of Organic Compounds

Test compound

Legend:
+ : Soluble
- : Insoluble

+ distilled H2O

Solubility by IMFA

Solubility by reaction
-

+
+ Ether

+ 5% NaOH
-

+
S1

S2

Water-soluble compounds

+ 5% HCl

+ 5% NaHCO3
-

A2

Basic compounds

+
A1

Acidic compounds
+ H2SO4

Inert compounds

Miscellaneous compounds

+
I

Neutral compounds

Experimental results:

I.

S1: Ethanol, Acetone

A2: Phenol

N: -

S2: Sucrose

B: Aniline

I: Hexane, Toluene, Tert-butyl chloride

A1: Benzoic acid

M: Benzamide

Water-soluble compounds have, at least, 1 hydrogen-bonding group per 5 carbon atoms along its path.
As such, all possible paths towards the hydrogen-bonding group must be taken to ascertain water
solubility.

II. Ether-soluble compounds have 2 or more carbon atoms per hydrogen-bonding group.
III. Solubility in water and ether is governed by intermolecular forces of attraction, specifically by hydrogen
bonding and Van der Waals forces. Entire dissolution of sample is required for a positive result.

IV. Solubility in acidic and basic reagents is governed by chemical reactions, specifically by neutralization
and forced protonation (via sulfuric acid) reactions. Partial dissolution of sample is sufficient for a
positive result.
V. A1 compounds are strong acids since they were dissolved both by sodium hydroxide, a strong base, and
sodium bicarbonate, a weak base. Carboxylic acids and phenols with strong electron-withdrawing
groups, such as A2,4-dinitrophenol and B2,4,6-trinitrophenol, belong to this group.

2,4-dinitrophenol
B

2,4,6-trinitrophenol

The acidic proton of activated phenols is more easily cleaved since strong electron-withdrawing
groups weaken the hydrogen-oxygen bond.
VI. A2 compounds are weak acids since they were not dissolved by sodium bicarbonate, a weak base.
All other phenols belong to this category.
VII. B compounds are bases since they were dissolved by hydrochloric acid, a strong acid. Amines, primary,
secondary, and tertiary, belong to this category. However, electron-withdrawing groups make the basic
lone pair less stable and, as a result, such amines belong to the M class. These amines are usually Adiand tri- arylamines, Barylamines with electron-withdrawing groups, and Csimple monosubstituted
amides.

Diphenylamine
B

Acetamide

2,4,6-trinitroaniline

VIII. M compounds are miscellaneous. These compounds have nitrogen and/or sulfur atoms and dont
belong to any of the previous classes as well. AAmides belong to this group.

Benzamide

Amides are ammonia derivatives wherein the one of the hydrogen atoms has been replaced by an acyl
(R-C=O) group.

IX. N compounds are neutral. Aldehydes, ketones, alcohols, ethers, esters, alkynes, and alkenes belong to
this category.
X. I compounds are inert. Alkanes, alkyl halides, and aromatic compounds, especially molecules with
benzene rings, belong to this category.

Experiment 2: Recrystallization and Melting Point Determination of Benzoic Acid

I.

The properties of an ideal solvent are as follows:

A.
B.
C.
D.

Should readily dissolve solute at elevated temperatures and only sparingly at room temperature
Should readily dissolve impurities at any temperature or not at all
Should not react with the solute
Should be sufficiently volatile to permit easy removal or separation of crystals

II. To prevent recrystallization, the following may be employed during hot filtration:
A. Fluted filter paper: Faster filtration occurs due to the larger surface area available.
B. Insertion of wire: Faster filtration occurs since escaping vapors need not pass through the funnel,
counter-current to the downward flow of the filtrated solution.
C. Lifting of funnel during filtration: Faster filtration occurs due to the same reason as above.
D. Addition of recystallization solvent to the receiving flask: The volatilizing solvent will heat up the
entire system without introducing impurities. The solution is also forced through the filter paper by
atmospheric pressure.
III. The cooling rate has to be controlled as well. If the filtrate is rapidly cooled, equilibrium conditions will
not be met and small crystals will be formed. If the filtrate is slowly cooled, large crystals with
extensive mother liquor inclusion will be formed. Therefore, the hot filtrate should be allowed to cool
at a rate between these two extremes.

IV. Failure to recrystallize the solute may happen due to supersaturation, unsaturation, or colloidal
formation due to an impurity.
V. To facilitate recrystallization, one may add a small crystal of the pure substance to the solution, or
scratch the containers inner walls to introduce small sites for recrystallization or seeds into the
solution.
VI. Animal charcoal or boneblack absorbs colored impurities in most organic substances.
VII. For the hot filtration procedure, a wide bore short-stemmed funnel is used.
VIII. If the solvent is evaporated after one recrystallization step, the hot step is skipped for the subsequent
recrystallization. If the solvent is decreased to half its volume, solubilities are halved as well.
IX. Percent purity and percent recovery are to be determined from the final insoluble phase in the final
recrystallization step.
masscompound
100 %
massfinal insoluble phase
masscompound in final insoluble phase
Percent recovery =
100 %
masstotal compound used
Percent purity =

Percent purity is the main basis for determining the best recrystallization solvent. If the used solvents
yield the same percent purity, percent recovery then serves as the tiebreaker.
X. Percent recovery is somewhat synonymous to percent yield, though the later is only used for solutions
involving chemical reactions.

Experiment 3: Purification of Crude Benzoic Acid by Sublimation

I.

For this method of purification to work, the solid must possess a relatively high vapour pressure at a
temperature below its melting point. Weak intermolecular forces give way to a large tendency for
evaporation or sublimation, which in turn leads to high vapor pressures.

II. Two phase changes occurred in this experiment: sublimation and deposition.
III. Purification by sublimation has several limitations. For one, it is only useable for compounds that
sublimate at easily attainable temperatures. Also, it can only be used for volatile substances with nonvolatile impurities. Although, this need not be fulfilled; at the very least, there should be a significant
difference in the sublimation temperatures of the desired compound and the impurities in the solution.

IV. A comparison between purification by recrystallization and sublimation:

Procedure
Recystallization
Description
Tedious; many steps
Percent purity
Low
Percent recovery
High

Sublimation
Easy; one step
High
Low

Experiment 4: Liquid Phase Chromatography

I.

There are generally two types of chromatography. In the normal phase, a polar stationary phase with a
relatively less polar mobile phase is used. In the reverse phase, a non-polar stationary phase with a
relatively less non-polar mobile phase is used.

II. Paper chromatography is the separation of components based on polarity. Here, the stationary phase
is the water adsorbed on the cellulose in the Whatman #1 filter paper, while the mobile phase is the
solvent, which was n-butanol diluted with an aqueous acetic acid solution in the experiment. Evidently,
paper chromatography is carried out as normal phase.
III. Important concepts about paper chromatography:

11

C, D

10

A
Distancesolvent

Solvent front

DistanceA
1

Mobile phase

Starting line

The retention factor refers to the degree to which the solvent carried a component of the solution
through the filter paper. In paper chromatography, wherein the mobile solvent is dominantly non-polar,
the higher the retention factor, the less polar the constituent is.
Retention factorA =

DistanceA
Distancesolvent

Note that the topmost dot contains two components. In order to separate the two, 2-dimensional
paper chromatography should be used. This simply involves redoing the procedure with the same filter
paper sideways but with a different solvent. That is:

D
C

IV. The procedure is done in a container to minimize the volatilization of the solvent from the paper. This
reduces the possibility of contamination as well.
V. Tailing may occur in paper chromatography, wherein dots overlap or even streaks of varying hues are
formed. This may be caused by sample overload, the inability of the solvent to distinctly separate
constituents, or prolonged exposure to moving air, wherein the solvent is constantly volatilizing.
VI. The properties of an ideal solvent are as follows:
A. Cheap, for practicality
B. Relatively volatile, since solvent vapors aid capillary action in lifting the solvent and solute
C. Does not react with the sample
VII. Evidently, for colored ones, human eyes are sufficient to determine the presence of the spot. Colorles
spots, on the other hand, require certain techniques to allow elucidation. Visualization techniques for
these are as follows:
A. Ultraviolet light: For conjugated compounds, wherein double bonds alternate with single bonds
B. I2 chamber: For unsaturated compounds, such as alkenes and alkynes
Dark brown spots that become lighter towards the solvent front become visible.
C. KMnO4 washing: For oxidizable compounds, such as alcohols and aldehydes
Brown spots become visible.

Experiment 5: Isomerism and Stereochemistry

I.

Isomers are compounds that have the same molecular formula, but differ in the position of functional
groups, length of the parent carbon chain, geometric orientations of substituents, chirality, etc.

Isomers
3-dimensional

2-dimensional
Structural

Stereoisomer
Chain

Geometric

Positional

Optical

Functional

Conformational

Chain isomers refer to the length of the parent carbon chain and the presence of alkyl branches.

Butane
2-methylpropane
Somewhat similar to chain isomers are positional isomers, which tackle all other functional groups.
Functional isomers refer to the presence of a different functional group for each isomer; it is possible
that a ketone and an aldehyde may be formed from a single moleculer formula:

Propanal
Propanal
Propan-2-one
Geometric isomers refer to the position of substituents about a double bond. Conformational isomers
refer to the possible three-dimensional appearances of a cyclical compound, such as chair and boat
isomers for cyclohexane:

Chair conformation

Boat conformation

Another type of conformational isomers deals with the staggered and eclipsed orientation of
substituents, with respect to each other, as a result of rotation about a single bond.

Anti

Gauche

II. Optical isomers possess chiral carbon atoms. These carbon atoms have four different substituents and
as a result, these molecules are asymmetric with respect to the chiral carbon centers.
III. Enantiomers are non-superimposable mirror images of a molecule. They have the same properties,
except for the rotation of plane-polarized light. Being mirror images, their absolute configurations are
switched, with one being R and the other being S. For each compound, there are 2n enantiomers, where
n is the number of chiral centers.
IV. To determine the absolute configuration of a chiral center, the least prioritized group should be
positioned the farthest. This can be achieved by performing an even number of ligand switches. The
three other substituents are then assigned their priorities based on atomic weight. The absolute
configuration is determined by the circular position of the three substituents according to their
priorities.
V. An R configuration is assigned for centers that have clockwise-positioned priority while an S
configuration is assigned for centers that have counterclockwise-positioned priority.
VI. Diastereomers are non-superimposable non-mirror images of a molecule. This is formed by performing
only one ligand switch. As a result, only one absolute configuration, given multiple chiral centers is
different.
VII. Mesomers, or meso compounds, are superimposable onto its mirror image. These are symmetrical
molecules, which reduce the number of enantiomers by one.

Experiment 6: Synthesis of an Alkyl Halide

I.

SN1 reactions form carbocation intermediates, while SN2 reactions form pentavalent carbon transition
states.

II. The SN1 mechanism for the synthesis reaction, which is the formation of tert-butyl chloride from tertbutanol and hydrochloric acid, is as follows:

III. The E1 mechanism for the side reaction, which is the formation of 2-methylpropene from tert-butanol
and hydrochloric acid, is as follows:

IV. Good leaving groups are weak bases, such as halides, which are conjugate bases of hydrohalogenic
acids, water, which is the conjugate base of hydronium, ammonia, ethanol, etc.
V. Rationalization of steps in the experiment:
A.
B.
C.
D.

E.
F.
G.
H.

Cold hydrochloric acid: Prevents the E1 reaction.

Concentrated hydrochloric acid: Practicality, since less volume of acid is needed.
Excess hydrochloric acid: Pushes the synthesis reaction forward
Saturated sodium chloride: Squeezes out organic molecules from the aqueous layer and pulls
water molecules into the aqueous layer; slightly increases the purity of the organic layer by
removing some water molecules.
Sodium bicarbonate: Neutralizes unreacted acid while showing equivalence indication via
effervescence.
Solid sodium bicarbonate: Aqueous sodium bicarbonate has water, which is counterproductive for
the experiment.
Boiling chips: Promotes even boiling and facilitates bubble formation; prevents superheating,
bumping, and loss of solution.
Anhydrous calcium chloride: Complexes with oxygen-containing compounds, such as water and
unreacted alcohols.
Clumped drying agent: wet solution
Free-floating drying agent (grains): dry solution

Experiment 7: Alcohols, Phenols, and Ethers

I.

Lucas reagent (Zinc chloride in concentrated hydrochloric acid) differentiates primary, secondary, and
tertiary alcohols through a modified SN1 reaction. The positive result of this test is layer formation, due
to the presence of the aqueous zinc, chloride, and hydronium layer, and the organic alkyl halide layer.
Benzyl alcohol is a false positive since it readily forms an organic layer on its own. However, it should be
noted that a reaction still took place. Benzylic and allylic alcohols still undergo the SN1 reaction as they
more reactive than tertiary alcohols given the said mechanism.

II. Oxidation by neutral potassium permanganate, also known as Baeyers test, is only possible for
alcohols with -hydrogen atoms. As such, tertiary alcohols give a negative result, which is a purple
solution. The positive result for this test is the decolorization of the purple solution accompanied by
the formation a brown precipitate. This occurs to the reduction of manganese in the reaction:

4H(aq
) + MnO4 (aq ) + 3e MnO2 (s) + 2H2 O(l)

Primary alcohols are oxidized to carboxylic acids by strong oxidants such as potassium permanganate,
chromic anhydride, and potassium dichromate. Weak oxidants, such as pyridium chlorochromate,
reduce the alcohols to aldehydes instead.

Pyridium chlorochromate
On the other hand, secondary alcohols are always oxidized to ketones. Finally, phenols are oxidized to
quinones.

Quinone
III. Ferric chloride confirms the presence of phenols via complex formation, the colors of which differ
depending on the structure of the phenol. Most complexes are greenish or yellowish, but some may
exhibit totally different colors, such as red in nitrophenols case.

IV. Bromine in water indicates the presence of phenols. The positive result is the formation of
tribrominated phenol, a white precipitate.

2,4,6-tribromophenol

Experiment 8: Aliphatic and Aromatic Hydrocarbons

I.

Alkanes, alkenes, and alkynes are aliphatic hydrocarbons. Hydrocarbons with benzene rings are
aromatic.

II. Criteria for determining aromaticity:

A. + = , where n should be a whole number
B. Conjugated molecule with a cyclic structure
C. Planar structure via sp2 bond hybridization
III. Bromination in light is a free radical substitution reaction. As such, only alkanes can undergo this
reaction. The positive result is decolorization of the yellow solution to a colorless one. In the
experiment, hexane and limonene gave positive results. The latter was able to undergo free radical
bromination due to the presence of alkane substituents in its structure:

Limonene
IV. Bromination in dark is a halogenations substitution reaction. Here, pi bonds are broken and bromide
ions attach themselves to the (previously) vinylic carbon atoms. As with the previous bromination
reaction, the positive result is decolorization of the yellow solution to a colorless one. In the
experiment, limonene was the only one that gave a positive result. Benzene didnt react because it
lacked true double bonds.

Benzene resonance
V. Baeyers test indicates the presence of double bonds. The pi bonds are broken and diol formation
ensues. The positive result for this test is the decolorization of the purple solution accompanied by the
formation a brown precipitate. In the experiment, only limonene gave a positive result since it was the
only compound of the three that possessed double bonds.

4-(1,2-dihydroxypropan-2-yl)-1-methylcyclohexane-1,2-diol
VI. Combustion distinguishes between aliphatic and aromatic compounds based on the sootiness of the
produced flame. Carbon double bonds make the flame somewhat sooty and aromatic rings increase
the sootiness all the more. As such, in the experiment, hexane showed a clear, yellow flame, limonene
gave a sooty, orange flame, while benzene exhibited a sootier, dark orange flame.
VII. Friedel Crafts Alkylation, with tert-butyl chloride and aluminium chloride, is an electrophilic aromatic
substitution reaction. The said reactants are needed, since a Lewis acid must catalyze the reaction.
Aluminum choride forms a complex by abstracting the halide of the tert-butyl chloride:
AlCl3 (s) + CH3 3 CCl(aq ) AlCl4

(aq )

+
+ CH3 3 C(aq
)

The negative charge of the complex allows to it act as a strong nucleophile for abstracting a hydrogen
atom from benzene rings. As a result, alkylation involving the hydrogen-deficient ring and the tertiary
carbocation proceeds faster.
The positive result of this test is the colorization of white anhydrous aluminium chloride crystals to
orange or red.
VIII. Powdery aluminium chloride is no longer anhydrous.

IX. Steam distillation is used when the boiling points of the solute and solvent are very near each other.
Otherwise, fractional distillation is used. In the experiment, this was used since limonene had to boil at
a lower temperature since it degrades at a temperature that is a few degrees past its normal boiling
point. Steam distillation accomplishes the lowering of the boiling point since the vapor pressure of the
solvent contributes to the total pressure within the set-up. As a result, atmospheric pressure is more
easily reached.

Experiment 9: Electrophilic Aromatic Substitution Reaction

I.

Electron-donating groups increase electron density on the aromatic ring. They stabilize the
carbocation intermediate through resonance and inductive effects. As such, the aromatic molecule
becomes more reactive towards electrophilic attack. Examples are, arranged from most activating to
least activating:
O

NH2

NHR

NR 2

NHC = OR

OH

OR

O C = OR

CH = CR 2

Electron-donating groups are ortho- and para-directing.

II. Electron-withdrawing groups decrease the electron density on the ring. As a result, they destabilize
the carbocation intermediate. The aromatic molecule becomes less reactive towards electrophilic
attack. Examples are, arranged from most deactivating to least deactivating:
NO2

NR 3

NH3

SO3 H

CN

CF3

ClC = O

HC = O

RC = O C = OOH

C = OOR X

Electron-withdrawing groups are meta-directing. Exceptions to this are the halogens, which are orthoand para-directing.
III. In the experiment, the reaction was bromination in dark. A possible error in the experiment involves
acetanilide. Since it has a methyl substituent, it can undergo bromination in light and, as a result, it may
seem to react faster than normal.

Acetanilide
IV. A polarizing solvent increases the rate of reaction since it imparts partial charges, or dipoles, to the
halogen reactant. The carbocation intermediate is more readily formed. In the experiment, diluted
glacial acetic acid was used. Besides the presence of the strongly polarizing carbonyl and hydroxyl

groups, the water present in the solution allowed the carboxylic acid to partially dissociate to form an
ionic solution.

Resonance and final product

Experiment 10: Aldehydes and Ketones
I.

2,4-dinitrophenylhydrazine tests for the presence of carbonyl compounds, namely ketones and
aldehydes. The positive result for this test is the formation of a yellow or orange precipitate. The acidcatalyzed reaction is:

Imine formation
The negative result is the formation of a yellow solution. Note that the 2,4-DNPH solution is already
yellow. Such a result would signify that no reaction took place.
This test is affected by acid concentration. In a very acidic environment, the 2,4-DNPH molecules
become protonated, which greatly hinders the continuation of the reaction. In a very basic
environment, not all of carbonyl oxygen atoms are protonated and, as a result, activated. The pH of the
solution must be kept between these two extremes.
II. Schiffs test makes use of Schiffs reagent, which contains acidified leucofuchsin dye, which is colorless
or light purple. This test indicates the presence of aldehydes. The positive result is the formation of a
(dark) purple solution. The negative result is the formation of a light purple or pink solution.
III. Tollens test makes use of Tollens reagent, which is ammoniacal silver nitrate. In an aqueous solution,
this dissociates to form diamminesilver(I) ions. This test indicates the presence of aldehydes only via a
reduction-oxidation reaction. The positive result of this test is the formation of an elemental silver

mirror. Due to the basicity of the solution, as a result of the presence of ammonia, a carboxylate ion
was formed instead of a carboxylic acid. The reaction is:
2 Ag NH3

+
2 (aq )

+
+ RCOH(aq ) + H2 O(l) 2 () +
() + 4NH3 (aq ) + 3H(aq )

The negative result of this test is the formation of a turbid solution. Occasionally, a colorless solution
may be formed as well.
IV. Benedicts test makes use of Benedicts reagent, which is a basic cupric solution. This test indicates the
presence of aliphatic aldehydes, which have their carbonyl functional groups directly attached to a
non-aromatic carbon atom, via a reduction-oxidation reaction. The positive result of this test is the
formation of a brick red precipitate. The reaction is:
+

2Cu2+
(aq ) + RCOH(aq ) + 2H2 O(l) () + () + 5H(aq )

The negative result is the formation of a blue solution, which signifies that no reaction took place.
V. The iodoform test makes use of iodine in basic potassium iodide solution, which indicates the presence
of methyl-ketones and 2-alkanols.

Butan-2-one

Butan-2-ol

The positive result is the formation of a bright yellow iodoform precipitate, which is CH3I. The
precipitation is base-catalyzed. The hydrogen atoms of the methyl group are first replaced by iodine
atoms. Then, an additional reaction with a hydroxide ion releases the iodinated carbon and a hydrogen
atom attaches to it. In reality, only methyl-ketones facilitate the formation of iodoform but the
hypoiodite ions (IO-) oxidize the secondary alcohols to methyl-ketones. The overall reaction is:

RCOCH3 (aq ) + 3I2 (aq ) + 4OH(aq

) RCOO(aq ) + () + 3I(aq ) + 3H2 O(l)

An exception to this test is ethanol. Hypoiodite oxidizes ethanol to ethanal, which is an aldehyde with a
terminal methyl group. This methyl group undergoes the said reaction above.
The negative result for this test is the formation of a yellow solution.

Experiment 11: Carbohydrates

I.

Six-membered carbohydrate rings are termed as pyranoses, while five-membered ones are furanoses.

II. Hexoses are dehydrated by strong acids to form 5-hydroxymethyl furfural, while pentoses form
furfural. Evidently, this test is limited to these two types of carbohydrates; carbohydrates with four or
less carbon atoms will always yield a negative result.

Furfural

5-hydroxymethyl furfural

Carbohydrates with more than six carbon atoms, such as disaccharides, oligosaccharides, and
polysaccharides, are first hydrolyzed by the acid into their monosaccharide constituents before
forming the corresponding furfural products.
III. Molisch test makes use of -naphthol, which indicates the presence of carbohydrates. The positive
result of this test is the formation of a purple interface.

-naphthol
IV. Bials test makes use of orcinol, which indicates the presence of pentoses or hexoses. Pentoses form a
blue to green solution or compound while hexoses form a yellow brown solution condensation
product.

Orcinol
V. Seliwanoffs test makes use of resorcinol, which differentiates between ketoses and aldoses. Ketoses
are more easily dehydrated by a hot strong acid than aldoses and, as such, for a given interval of time
before the completion of the dehydration and resorcinol reaction, ketoses will form bright red
condensation products or solutions while hexoses will only yield a pink coloration.

Resorcinol
VI. Benedicts test confirms the presence of reducing carbohydrates.
VII. Barfoeds reagent confirms the presence of monosaccharides. Though it has cupric ions, which are
readily reduced by reducing sugars, the reaction rate decreases for each carbohydrate ring in the
molecules structure. As such, the reduction-oxidation reaction with disaccharides proceeds much,
much slower than one involving a monosaccharide; oxidation of oligosaccharides proceeds even slower.
The positive result of this test is the formation of a brick red precipitate, Cu2O.
VIII. Osazone formation occurs in sugars that are capable of mutarotating, reduces Benedicts solution, and
has and forms. In short, only reducing sugars, ones which have free anomeric carbons or
hemiacetal structures, are capable of forming osazones. Phenylhydrazine replaces the attached groups
to the first two carbon atoms of the reacting carbohydrate and a double bond is formed between the
carbon and the terminal nitrogen atoms. The positive result for this test is the formation of yellow
precipitate or crystals.

Phenylhydrazine
IX. Iodine in potassium iodide solution test for the presence of starch. The linear amylose can form a
helical tube-like or coil structure, which is made up of six D-glucose sub-units, linked together with 1,4 glycosidic bonds, per turn, that can encase triiodide ions, which were formed via the reaction:

I2 (aq ) + I(aq
) I3 (aq )

As a result, a blue-black solution is formed. The other component of starch, which is branched
amylopectin, is incapable of yielding the same physical result since it cannot form a helical structure.
On a side note, it has with -1,6 glycosidic bonds between some of its glucose sub-units.
(Acid-catalyzed) hydrolysis breaks down the linear amylose chains into its glucose sub-units, and
maltose units if the hydrolysis is not extensive enough.

X. Cellulose is very similar to amylose in structure, except for the fact that -1,4 glycosidic bonds are the
ones that link sub-units. This results to a two-dimensional polymer structure that is much more rigid
than that of starch. Amylopectin branching and helical coiling does not occur in cellulose as well; rather,
a stiff chain is formed. Hydrogen bonding, brought about by the hydroxyl groups and hydrogen atoms
between two chains, also increases the stability of the material. As such, cellulose is harder to break
down than starch.

Experiment 12: Carboxylic Acid and Derivatives

I.

Carboxylic acids are soluble in sodium bicarbonate via a neutralization reaction. Effervescence is
observed as the formed carbonic acid degrades to water and carbon dioxide:
Acetic acid: CH3 COOH(aq ) + NaHCO3 (aq ) CH3 COONa(aq ) + CO2 (g) + H2 O(l)
Benzoic acid: C6 H5 COOH(aq ) + NaHCO3 (aq ) C6 H5 COONa(aq ) + CO2 (g) + H2 O(l)

II. The positive result for the acetic acid test is the formation of a red complex or solution. Sodium
hydroxide neutralizes acetic acid to form acetate, which then complexes with ferric ions to form the
said result.

Ferric acetate complex

III. The positive result for the benzoic acid test is the formation of a flesh precipitate. Ammonium
hydroxide neutralizes benzoic acid to form benzoate, which then complexes with ferric ions to form
the said result.

Ferric benzoate complex

IV. In the two previous tests, the addition of excess hydroxide ions leads to the formation of ferric
hydroxide, a brown precipitate, which could be mistaken for a positive result.

V. The formation of esters proceeds faster with acyl halides than carboxylic acids since the latter is more
reactive due to the presence of the electron-withdrawing halide. For acyl halides, addition of the alcohol
is enough for the reaction to take place. However, for carboxylic acids, heat and an acid catalyst are
both required.
VI. The hydroxamic test indicates the presence of esters. The uncommon reagents that were used were
alcoholic hydrochloric acid, alcoholic potassium hydroxide, and alcoholic acidic hydroxylamine. These
reagents were simply diluted with alcohol in order to dissolve the ester sample. The positive result of
this test is the formation of a purple complex or solution.

Ferric hydroxamate complex

Hydrochloric acid was added to the solution in order to neutralize unreacted hydroxide ions from the
dissociation of potassium hydroxide. This is to prevent the formation of ferric hydroxide.
VII. Carboxylic acid derivatives hydrolyze in water to reform the parent acid. However, their reactivities
determine the ease of accomplishing the said reaction.
Anhydrides easily hydrolyze in water.
Esters require the presence of a base-catalyst during the reflux procedure to form the corresponding
carboxylate anion upon the expulsion of an alcohol, followed by a base catalyst to reform the carboxylic
acid.
Amides require the presence of an acid catalyst for the hydrolysis reaction. Ammonium cations are also
formed in this reaction.
VIII. The hydrolysis of amides can also produce a carboxylate product, instead of the acid, if a base catalyst
is used. In this case, ammonia is formed and this serves as the indicator for the completeness of the
reaction instead of the presence of a sour smell. This can be kept track of with a red litmus paper.

Experiment 13: Nucleophilic Acyl Substitution: The Synthesis of Esters

I.

In the reaction mechanism, Athe nucleophile attaches to the carbonyl group, producing a tetrahedral
intermediate. BThe electron pair from oxygen then displaces the leaving group to form a new carbonyl
compound product.

In the experiment, the carbonyl oxygen atom is protonated by the acid catalyst before the formation of
the tetrahedral intermediate through the attack of the alcohol on the carbonyl carbon and the
breaking of the carbonyl pi bond. The hydroxyl hydrogen atom of the attached alcohol transfers to the
hydroxyl group of the carboxylic acid, forming water. A free water molecule then abstracts the proton
catalyst from the carbonyl oxygen and the carbonyl double bond is reformed.
II. Rationalization of steps in the experiment:
A. Excess alcohol: Pushes the synthesis reaction forward.
B. Carboxylic acid as the limiting reagent: It is the substrate for the reaction, while the alcohol is the
reactant that bonds to the substrate. Furthermore, excess acid hinders the observation of esters
smell. Its sourness overpowers the products scent.
C. Boiling chips: Promotes even boiling and facilitates bubble formation; prevents superheating,
bumping, and loss of solution.
D. Concentrated sulfuric acid: Catalyst for the reaction by protonating the carbonyl oxygen atom. The
nucleophilic attack of the alcohol proceeds faster due to the full positive charge of the molecule.
Also acts as a dehydrating agent; removes water from the solution which prevents the reverse
reaction according to Le Chateliers principle.
E. Cooling to room temperature: Prevents the volatilization of the ester as it is being transferred to
the separatory funnel
F. Cold water: Prevents the volatilization of the ester
G. Rinsing the round bottom flask: Collects all of the formed products
H. Saturated sodium chloride: Squeezes out organic molecules from the aqueous layer and pulls
water molecules into the aqueous layer; slightly increases the purity of the organic layer by
removing some water molecules.
I. Sodium bicarbonate: Neutralizes unreacted acid (both from sulphuric acid and the used carboxylic
acid) while showing equivalence indication via effervescence.
J. Solid sodium bicarbonate: Aqueous sodium bicarbonate has water, which is counterproductive for
the experiment.
K. Anhydrous sodium sulfate: Dries the solution. Calcium chloride cannot be used since the product
contains oxygen atoms.

III. Distillation increases the percent yield of the procedure. There are two cases for this, regarding the
boiling points of the formed ester and used (unreacted) alcohol:
A. BPester > BPalcohol: The ester is in the distilling flask.
B. BPester < BPalcohol: The ester is in the receiving flask.
IV. The use of excess alcohol and cold water, the addition of saturated sodium chloride, concentrated
sulphuric acid, and anhydrous sodium sulfate, and refluxing the reaction solution all increased the
percent yield of the reaction.
V. The addition of saturated sodium chloride, solid sodium bicarbonate, and anhydrous sodium sulfate, and
distillation all increased the percent purity of the ester product.

Experiment 14: Saponification: Herbal Soap-Making

I.

Saponification is the exothermic base hydrolysis of triesters or triglycerides. Triglycerides are broken
down into glycerols and fatty acid salts, which is soap.

II. These fatty acid salts have very long carbon chains, termed usually as the hydrophobic tail, and an ionic
carboxylate end, also known as the hydrophilic head.

Sodium palmitate

III. Soaps solidify due to the ionic and Van der Waals forces.
IV. The reverse reaction of saponification process does not take place due to the lack of any good leaving
groups in the resulting intermediate from the bonding of the glycerol and the carboxylate anions.

Reverse reaction intermediate

As such, after tracing occurs, the reaction mixture will no longer revert back into oil and caustic soda.

V. Soap can function as an emulsifier, capable of mixing a liquid into another immiscible one. When
hydrophobic matter, such as oil and grease, is added into a solution containing soap molecules, layers
are not formed. Rather, a solution containing small globules, called micelles, is the result. The nonpolar
side of the soap molecules allows them to trap dirt and oily matter while their polar side allows them
to stay soluble in, and be easily washed away by, water. This property is also handy when it comes to
washing dirt, especially by hand. Since human skin has a natural thin coat of oil, dirt particles easily
adheres to it and consequently becomes harder to remove due to their newly-acquired oily coating. This
becomes more troublesome due to the fact that oil is not volatile and as a result, these particles will just
stay there. However, upon the introduction of soap molecules to the skin surface, they are evidently
washed away with ease as the nonpolar tails of the soap molecules adhere to dirt particles oil coating.
VI. Soaps dont work as efficiently when used with hard water. This is because metal cations in the water
bond to the ionic head of the soap molecules to form insoluble precipitates. Certain additives have to
be added to the water, such as sulfite compounds, to prevent the precipitation reaction by reacting
with the metal ions themselves.
VII. In transesterification, water is replaced by an alcohol; the reaction is still base-catalyzed. Regarding the
final product, the sodium cation is replaced by the alkyl group of the alcohol that was used for the
reaction. In performing this reaction, the environment has to be completely dry or else soap formation
will occur.

Experiment 15: Hinsbergs Method for Characterizing Primary, Secondary, and Tertiary Amines
Amine sample

+ Benzenesulfonyl chloride, + Excess sodium hydroxide

-

+
Primary amine

+ Hydrochloric acid
Legend:
+ : Soluble
- : Insoluble

+
Tertiary amine

I.

Discard.
-

Secondary amine

Primary amines form a sulfonamide precipitate with benzensulfonyl chloride. A hydrogen atom is
abstracted from the amine, while the halide is removed from the reagent. Upon the addition the of

excess sodium hydroxide, the final hydrogen atom is cleaved from the molecule by sodium cations,
giving it a full negative charge.
II. Secondary amines form a sulfonamide precipitate with benzenesulfonyl chloride as well. However, due
to the lack of hydrogen atoms bonded to the nitrogen atom, the precipitate stays insoluble after the
addition of sodium hydroxide.
III. Tertiary amines are incapable of forming sulphonamides and, as such, no reaction takes place between
one and benzensulfonyl chloride. However, hydrochloric acid, the second reagent, protonates the
amine, making it soluble.
IV. A summary of the solubilities in the first and second reagent:

First reagent
Second reagent

Primary amine
Soluble
Insoluble

Secondary amine
Insoluble
No reaction

Tertiary amine
No reaction
Soluble

V. The discarded layer contains sodium hydroxide and benzenesulfonate. The latter is a result of the
reaction between benzensulfonyl chloride and hydroxide ions to form benzenesulfonic acid, which was
neutralized by excess hydroxide ions to form the said compound.
VI. The residue, may it be solid or liquid, may contain either the amine sample, sulfonamide precipitate, or
both. Sulfonamides are usually denser than water but, occasionally, the opposite occurs.
VII. Hinsbergs test cannot be used to classify amphoteric amines, which possess (carboxylic) acid and
amine structures. They are soluble both in the first, due to the neutralization reaction of acid
substituent, and second, due to the neutralization reaction of the amine substituent, reagents.

Experiment 16: Synthesis of 1-phenylazo-2-naphthol

I.

Azo compounds are organic compounds that contain an azo group (N=N). The azo group is attached
to aryl groups on both sides. Azo dyes also exhibit resonance of electrons which stabilizes the
compound.

II. Dyes are colored for they contain at least one color-bearing group or chromophore. In azo dyes, the
extended conjugated pi electron system found in the azo group allows the dyes to absorb light in the
visible region. The conjugated structure also adds to the color of the dye. Furthermore, the
delocalization of electrons and conjugation are both extended due to the nitrogen-nitrogen double
bond linkage and this further deepens the color of the dye.

Aside from chromophores, azo dyes also contain auxochromes or color helpers in the form of NHR,
NR2, OH, and OR. The presence of auxochromes can deepen the color of the dye. Auxochromes are
also used to influence dye solubility.
III. The synthesis of azo dyes involves two reactions: diazotization reaction and coupling reaction. In
diazotization, a primary aryl amine is made to react with nitrous acid, which was generated from the
reaction between sodium nitrite and a concentrated acid, to form diazonium ions. This reaction is
carried out under freezing conditions. The diazonium ion is among the most versatile intermediates in
organic synthesis.

The produced diazonium ion then reacts with highly activated aromatic substrates in the coupling
reaction to give the azo dye. The coupling reaction is an electrophilic aromatic substitution wherein the
diazonium ion serves as the electrophile. Since the diazonium ion is a relatively weak electrophile, the
aromatic ring it attacks must be highly activated with groups such as OH and NH2.
IV. Dyes are made with the following properties in mind: fastness and levelness. Fastness refers to the
ability of the dye to strongly bond to the fibers of the material being dyed. The dye must not fade
after repeated washings (water fast) and exposure to light (light fast). On the other hand, levelness
refers to the uniformity of the dye on the fiber when applied. The dye must evenly color the fabric
upon application.
V. When dying fabric, it is important to know the structure of both the dye and the fabric to be used to
determine the appropriate dyeing method. Dyes can be classified according to the method by which
they were applied to a fabric. Dyes are commonly classified as follows: direct dyes, ingrain dyes, vat
dyes, and disperse dyes.
Direct dyes attach themselves to a fabric via a direct chemical interaction.
Ingrain dyes, such as simple dyes, are synthesized within the fabric itself. Smaller molecules that can be
used to synthesize the ingrain dye are allowed to penetrate the fabric. These two smaller molecules
then react to form the larger ingrain dye which gets trapped in the fabric. Ingrain dyeing is commonly
used for cotton fabric.
Mordant dyes make use of substances known as mordants that bond with the dye itself to form lakes,
which are dye-mordant complexes. The same principle when the dye bites onto the fabric. Coordinate
covalent bonds are formed between the lakes and the fabric molecules.
Water-insoluble disperse dyes are applied to fabric such as polyesters by allowing them to penetrate a
fabric by using an organic solvent to carry the dye. The fabric is first suspended in an aqueous solution
with a little amount of the organic solvent. The organic solvent then dissolves the dye and disperses it
into the fabric. The dye gets trapped in the fabric because of water-insolubility.

VI. The synthesis is a 2-pot reaction. In the first pot, phenyldiazonium chloride is formed, while in the
second pot, naphthalen-2-olate or -naphthoxide is produced. The two are then reacted later to form
the crude Sudan-1 solution, which consists of the synthesized dye, unreacted reactants, and water.
VII. Nitrous acid was generated in-situ in the first pot since it is unstable. A prepared solution cannot be
used.
VIII. -naphthol was reacted with sodium hydroxide to give it a negative charge, which activates it toward
electrophilic aromatic substitution. It also increases reaction rate since naphthalen-2-olate is soluble in
water.
IX. The dye was recrystallized to remove any occluded molecules or ions.
X. To determine the reactants needed to form an azo dye, the aromatic rings on both sides of the
nitrogen-nitrogen double bond have to be inspected. The breaking of the linkage to the nitrogennitrogen double bond takes place beside the ring that directed the bond correctly or beside the more
activated one.