Name: Jobel D.

De Pedro Date Performed:

Group #: 6 Date Submitted:

Experiment 9
ACYL COMPOUNDS: SOAPS AND DETERGENTS

I. OBJECTIVES

1. To observe the general properties of carboxylic acids.

2. To compare the acidity of carboxylic acids and phenols.
3. To verify experimentally the interconversion among acyl compounds.
4. To become familiar with the physical and chemical properties of fats and oils and
to understand the chemical basis of these properties.
5. To learn how to prepare soap.
6. To compare the properties of soap and synthetic detergents.

II. THEORETICAL FRAMEWORK

Soap is an anionic surfactant used in conjunction with water for washing and
cleaning that historically comes in solid bars but also in the form of a thick liquid. Soap,
consisting of sodium (soda ash) or potassium (potash) salts of fatty acids is obtained by
reacting fat with lye in a process known as saponification. The fats are hydrolyzed by
the base, yielding alkali salts of fatty acids (crude soap) and glycerol.
Many cleaning agents today are technically not soaps, but detergents, which are
less expensive and easier to manufacture.
Soaps are useful for cleaning because soap molecules attach readily to both
nonpolar molecules (such as grease or oil) and polar molecules (such as water).
Although grease will normally adhere to skin or clothing, the soap molecules can attach
to it as a "handle" and make it easier to rinse away. Applied to a siled surface, soapy
water effectively holds particles in suspension so the whole of it can be rinsed off with
clean water.
(Fatty end):CH3-(CH2)n - COONa: (water soluble end)
The hydrocarbon ("fatty") portion dissolves dirt and oils, while the ionic end
makes it soluble in water. Therefore, it allows water to remove normally-insoluble matter
by emulsification.
The most popular soapmaking process today is the cold process method, where
fats such as olive oil react with lye, while some soapers use the historical hot process.
Handmade soap differs from industrial soap in that, usually, an excess of fat is
sometimes used to consume the alkali (superfatting), and in that the glycerin is not
removed leaving a naturally moisturising soap and not pure detergent. Superfatted
soap, soap which contains excess fat, is more skin-friendly than industrial soap, though
if too much fat is added it can leave users with a "greasy" feel to their skin. Often,
emollients such as jojoba oil or shea butter are added 'at trace' (the point at which the
saponification process is sufficiently advanced that the soap has begun to thicken), after
most of the oils have saponified, so that they remain unreacted in the finished soap.
Superfatting can also be accomplished through a process called superfat discount,
where, instead of putting in extra fats, the soap maker puts in less lye.

III. DATA AND RESULTS

Table 1. Solubility and acidity of Carboxylic acids

SAMPLE WATER SOLUBILITY RXN TO LITMUS PAPER TEST

Acetic acid Soluble Acidic: turns blue LP to red
Benzoic acid Insoluble Acidic: turns blue LP to red
Sodium benzoate Soluble Basic: no change in blue LP

Table 2. Relative acidities of Carboxylic acids and Phenols

SAMPLE Solubility in 10% NaOH Solubility in 10% NaHCO3

Phenol Soluble Soluble
Benzoic acid Soluble Insoluble

Table 3. Observations upon addition of water and heating the samples, as well as
their reactions to litmus paper test.

SAMPLE RXN SIGNS WATER BATH

Acetyl Chloride Heat; semi-cloudy; bubble formation No change
Acetic anhydride Clear, homogeneous solution No change
Benzamide Insoluble Dissolved, clear solution

Table 4. Comparison of Soaps and Detergents

SOAP DETERGENT
Hydrolysis Cloudy, basic Clear, basic
Rxn with Acid Turbid Clear
Rxn with Soft Water Turbid Clear
Rxn with Hard Water Formation of scums Turbid, no scums
Emulsifying Action Formation of smaller bubbles More bubbles were formed

IV. DISCUSSION

Solubility and Acidity of Carboxylic Acids

For table 1, Acetic acid and sodium benzoate were both soluble in water while benzoic
acid was not. Unlike aldehydes and ketones, instead of protonation to be undergone to yield an
alcohol, the initially formed alkoxide intermediate expels one of the substituents originally
bonded to the carbonyl carbon, leading to the formation of a new carbonyl compound by a
nucleophilic acyl substitution reaction.
The different behavior towards nucleophiles of carboxylic acids derivatives is a
consequence of structure. In the case of benzoic acid, the C=O carbon is electron-rich making
the compound less ready to react with water, a nucleophile. The more electron-poor the C=O
carbon, the more readily the compound reacts with nucleophiles. This is why acetic acid and
sodium benzoate were able to dissolve in water.
In table 2, both phenol and benzoic acid were soluble in 10% NaOH and were both
insoluble in 10% NaHCO3. Because acid dissociation is an equilibrium process, anything that
stabilizes the carboxylate ion favors increased dissociation and increased acidity. Phenols and
carboxylic acids are much more acidic than alcohols. In fact, some nitro-substituted phenols
even approach or surpass the acidity of carboxylic acids. One practical consequence of their
acidity is that phenols and carboxylic acids are soluble in dilute aqueous NaOH but remain
undissolved in NaHCO3.

Hydrolysis of Acyl Compounds

Acyl compounds differ in their reactivities toward nucleophilic acyl substitution and this is
evident from their hydrolysis reactions. Hydrolysis is a chemical reaction in which compound is
broken down by reaction with water. Acid halides are among the most reactive of the various
carboxylic acid derivatives and can be converted into many other kinds of substances. The
halogen can be replaced by the –OH to yield an acid, by –OR to yield an ester or by –NH 2 to
yield an amide. The table below shows the different observations upon addition of water and
heating the samples, as well as their reactions to litmus paper test.
Acetyl chloride, an acid chloride, was the first sample to react with water to yield
carboxylic acids by the substitution of –Cl by –OH.
The chemistry of acid anhydrides is similar to that of acid chlorides. Thus, results
showed that acetic anhydride reacted with water to form acids, after heating. The ease
of which the leaving group is lost depends upon its basicity: the weaker the base, the
better the leaving group. For acid and anhydrides, the leaving group is the very weak
base Cl- and CH3 respectively.
Benzamide, an amide, is less reactive than acid chlorides and acid anhydrides.
Amides undergo hydrolysis to yield carboxylic acids plus amine on heating in either
aqueous acid or base. Although the reaction is slow and requires prolonged heating, the
overall transformation is a typical nucleophilic acyl substitution of –OH for –NH2.

Saponification of Coconut Oil

Triglycedrides are tri-esters of glycerol. They are the most naturally occurring fats
and oils. Alkaline hydrolysis of the three-ester linkages can break down triglycerides into
their component parts and yield long-chain carboxylate salts and glycerol. The
hydrolysis of fats and oil (coconut oil, in this experiment) in a basic medium is commonly
called saponification and the sodium salts produced are called soaps. Coconut oil is a
source of lauric acid (12 carbons) which can be made into sodium laurate.

Comparison of Soaps and Detergents

Soaps and detergents are similar in their general structure and properties, but
different in their composition and some specific properties. This was apparent their
hydrolysis reactions, ability to react with mineral acids behavior in “soft” and “hard”
water, and emulsifying properties were studied. Table 4 shows the results of the
experiment.
Soap from triacylglycerols is a mixture of long chain carboxylate salts. Detergents, on the other
hand, are amphiphatic and are generally characterized by the presence of a sulfonate group. It
is a cleansing substance that acts similarly to soap but is made from chemical compounds
rather than fats and lye.
Soaps are the sodium salts of fatty acids. They are water soluble but the fatty acids
themselves are not. Soap can be converted into the fatty acid by means of a reaction with a
strong mineral (non-organic) acid. Acidification of detergents, on the other hand, produces acids
which are often water soluble. Because of this, soaps are ineffective in acidic water.
Although soap is a good cleaning agent, its effectiveness is reduced when used in hard
water. Hardness in water is caused by the presence of mineral salts such as calcium and
magnesium as well as iron and manganese. Soaps react with metal ions in the water to form
insoluble precipitates. The precipitates can be seen in the soapy water and are referred to as
“soap scum”. Unlike soaps, though, sulfonate in detergents does not form precipitates with the
metal ions of hard water, reducing the discoloration of clothes due to the precipitated soap.

V. CALCULATION

VI. ANSWERS TO QUESTIONS

1. Explain the difference in the solubility of benzoic acid and sodium benzoate in
water. Which of the two would you predict to be more soluble in CHCl 3?
Explain.

The different behavior towards nucleophiles of carboxylic acids derivatives is

a consequence of structure. In the case of benzoic acid, the C=O carbon is electron
rich making the compound less ready to react with water, a nucleophile. The more
electron-poor the C=O carbon, the more readily the compound reacts with
nucleophiles. When placed in water, sodium benzoate dissociates to form sodium
ions and benzoic acid ions. It is a weak organic acid that contains a carboxyl group.
This accounts for the higher solubility of sodium benzoate in water.

2. Based on the results in Part A.2, what can be said about the relative acidities
of phenols and carboxylic acids? Arrange the following compound types in
order of increasing acidity: carboxylic acid, alcohol, phenol and water.

Carboxylic acids are much more acidic than alcohols even though both
contain O—H group due to the relative stabilities of carboxylate anions versus
alkoxide anions. In an alkoxide ion, the negative charge is localized on one oxygen
atom. In carboxylate ion, however, the negative charge is delocalized, or spread out
over both oxygen atoms. In other words, a carboxylate ion is a stabilized resonance
hybrid of two equivalent structures.

Phenols, on the other hand, are more acidic than alcohols because the
phenoxide anion is resonance-stabilized by the aromatic ring. Sharing the negative
 charge over the ring increases the stability of the phenoxide anion and thus
increases the tendency of the corresponding phenol to dissociate. Therefore,
carboxylic acids > phenols > alcohols in terms of their acidities.

3. Based on the results in Part B, arrange the following compound types in the
order of decreasing hydrolysis rate: acid halides, acid anhydrides, esters, and
amides. Give the theoretical explanations for the observed differences in
reaction rates.

The more highly polar a compound is, the more reactive it is. As confirmed by
the results of the experiment, the polar acid halides are the most reactive of the
carboxylic acid derivatives because the electronegative halide atom strongly
polarizes the carbonyl group. Acid anhydrides react in almost the same manner as
acid halides, although at a slower rate. Only “half” of the anhydride molecule is used.
The other half acts as the leaving group during the nucleophilic acyl substitution step
and produces carboxylate anion as a by-product. Thus, anhydrides are inefficient to
use, and acid chlorides are normally preferred for introducing acyl substituents other
than acetyl groups. Esters show the same kinds of chemistry as the first two
compounds mentioned, but are less reactive toward nucleophiles than acid chlorides
or anhydrides. The slowest to hydrolyze are the amides since their linkage is very
stable and is enough to serve as the basic unit from which proteins are made.

4. The soap water mixture a true solution? Cite examples to support your
answer.

A soap solution is not a real solution but a colloidal mixture that aroused after
the addition of soap to water. It is considered a colloid, a cloudy mixture where one
substance is dispersed evenly throughout another. Because of this effective
dispersal, some colloids have are mistaken to be solutions since they have similar
appearances.

5. What is a colloidal mixture? How does a colloidal mixture arise when soap is
mixed with water?

A colloid or colloidal dispersion is a substance with components of one or two

phases. It is a heterogeneous mixture where very small particles of one substance
are distributed evenly throughout another substance. A colloidal mixture has an
outer layer of ions with the same charge so that these repel each other. This results
to lesser aggregation to form particles that are large enough to precipitate.
Oil is a pure hydrocarbon so it is non-polar. The non-polar hydrocarbon tail of
the soap dissolves into the oil. That leaves the polar carboxylate ion of the soap
molecules sticking out of the oil droplets. These spherical clusters, called micelles,
which surfaces are negatively charged is where droplets of grease or oil are
solubilized in water. Then, they become coated by the hydrophobic non-polar tails of
soap molecules. As a result, the oil droplets repel each other and remain suspended
in solution to be washed away by a stream of water.
6. On the basis of the litmus test, are the soap-water and detergent-water
mixtures acidic, basic or neutral? Explain the difference, if any in the
reactions of the soap-water and detergent-water mixtures to litmus paper.

Reaction with litmus paper shows the alkalinity of both soap-water and
detergent-water mixtures. Soaps undergo a hydrolysis reaction upon hydration and
as a result, they tend to be alkaline. Detergent-water mixtures are also alkaline but
in a lesser degree.

7. Which would you predict to have a greater emulsifying power in “hard water”,
soaps or synthetic detergent? Explain.

Synthetic detergents have greater emulsifying in “hard water” because of the

presence of the sulfonate group in detergents. The sulfonate group doesn’t react
with the calcium and magnesium ions in hard water to form films or scums, a
property typical of soaps.

8. Explain the cleaning property of soaps and detergents based on your

observations of their emulsifying action.

The cleaning action of both soaps and detergents results from their ability to
emulsify or disperse water-insoluble materials (dirt, oil, grease, etc.) and hold them
in suspension in water. This ability comes from the molecular structure of soaps and
detergents. When a soap or detergent is added to water that contains oil or other
water-insoluble materials, the soap or detergent molecules surround the oil droplets.
The oil or grease is “dissolved” in the alkyl groups of the soap molecules while the
ionic end allows the micelle to dissolve in water. As a result, the oil droplets are
dispersed throughout the water, as emulsification takes place, and can be rinsed
away.