Kate Coleen D.

Galera BS in Chemistry II May 4, 2017

Experiment 11
ACYL COMPOUNDS: SOAPS AND DETERGENTS

I.Data and Results

A. Solubility and acidity of carboxylic acids
A.1.Water solubility
Compound Appearance Solubility Test with Blue Litmus Paper
Acetic acid Clear solution Soluble Blue to Red (pinkish-red)
Acidic
Benzoic acid Clear solution with Insoluble Blue to Red (pinkish-red)
white precipitate Acidic
Sodium benzoate Clear solution Soluble Blue to Blue (no color change)
Basic

A.2. Relative acidities of carboxylic acids and phenols

Compound Appearance (10% NaOH) Solubility Appearance (10% Solubility
NaHCO3)
Benzoic acid Clear solution Soluble Clear solution but some Slightly
particles were soluble
undissolved
Phenol Clear solution with white Insoluble Cloudy white solution Insoluble
gelatinous precipitate with settled white
making the solution look precipitates
cloudy white

B. Hydrolysis of acyl compounds

Compound Appearance Test with Blue Litmus Paper
Acetyl chloride Clear solution. Exothermic Blue to Red, Acidic
Acetic anhydride Colorless solution with bubbles formation Blue to Red, Acidic
Benzamide Colorless solution with white flaky Blue to Red, Acidic
precipitates

C. Saponification of coconut oil

Observations
Mixture of 10 ml ethanol in 400 ml beaker, 15 ml 6M NaOH and 15 ml commercial coconut oil produced a
whit to pale solution and yellow oily layer on top. When the mixture was heated and continuously swirled,
it slowly turned into viscous pinkish white substance with small bubble formation on the top. The substance
has a pleasant smell.

D. Comparison of soaps and detergents

D.1. Hydrolysis
Sample Test with Red Litmus Paper Test with Blue Litmus Paper
Soap Red to Red (no color change) Blue to Blue (no color change)
Detergent Red to Red (no color change) Blue to Blue (no color change)

D.2. Reaction with acid

 Sample Appearance
Soap Cloudy white solution with no precipitate
Detergent Colorless solution with no precipitate

D.3. Reaction with “soft” and “hard” water

Sample 0.02 M NaCl (soft water) 0.02 M CaCl2 (hard water
Soap Cloudy white solution Colorless solution
Detergent Less cloudy white solution Cloudy white solution with white
precipitate

D.4. Emulsifying action

Sample Appearance (with 8 drops of kerosene)
Soap Cloudy white solution with white emulsion and white precipitate
Detergent Pale yellow solution with emulsions

II.Discussion
Solubility and Acidity of Carboxylic Acids
A.1.Water solubility
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.

A.2. Relative acidities of carboxylic acids and phenols

Theoretically, both phenol and benzoic acid must soluble in 10% NaOH and 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.

B. 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 –NH2 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.

C. 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.

D. 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 triacylglycerol is a mixture of long chain carboxylate salts. Detergents, on the other
hand, are amphipathic 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.

III.Conclusion

The acyl compounds differ in their reactivity toward nucleophilic acyl substitution and this is
evident from their hydrolysis reactions. The more reactive compounds are hydrolyzed by water alone. The
less reactive ones either require a strong nucleophile as the hydroxide ion or an acid catalyst to enhance
the electron deficiency of the carbonyl carbon, making it more attractive to a nucleophile. Alcohols,
phenols, ammonia and amines react with acyl compounds in much the same way as water does.
Many cleaning agents today are technically not soaps, but detergents, which are less expensive
and easier to manufacture.
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 moisturizing
soap and not pure detergent.
IV.References

McMurry, John. Organic Chemistry. Thomson Publications. 2004

“Acyl Compounds” Retrieved from

https://www.coursehero.com/file/14330962/Exp-9-Acyl-Compounds-Soaps-and-Detergentspdf/

“ACYL COMPOUNDS: SOAPS AND DETERGENTS” Retrieved from:

https://www.scribd.com/doc/209337048/Exercise-9-Acyl-Compounds-Soaps-and-Detergents

V.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 CHCl3? 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.