EXPERIMENT 10

Reporters: Groups 3, 4

1. Based on your observations, what kind of substances react with:

a. Test Group 1
i. Alcoholic AgNO​3​ - alkyl halides
ii. Lucas Test - alcohols (1°, 2°, 3°)
b. Test Group 2
i. 2,4-DNPH Test - aldehydes & ketones
ii. Bisulfite Test - aldehydes
iii. Schiff’s Test - aldehydes
c. Test Group 3
i. Iodoform Test - methyl ketone, secondary alcohol
ii. Hinsberg Test - amines (1°, 2°, 3°)
iii. Fischer Reaction - carboxylic acid and alcohol
iv. Hydrolysis - single primary amides
v. Hydroxamic Acid Test -carboxylic acid derivatives

2. What mechanism does each test group employ?

a. Test Group 1 - Nucleophilic substitution
b. Test Group 2 - Nucleophilic acyl addition
c. Test Group 3 - Nucleophilic acyl substitution

3. What are the substances responsible for each result? Tabulate your answers and indicate if they are
positive or negative results.a

Test Substance Responsible for Result Remarks: (+) or (-)

TEST GROUP 1

1. Alcoholic AgNO​3 silver halide precipitate +

● (Cl-bright white, Br-light yellow,
I-light tan)

2. Lucas Test alkyl chloride precipitate +

(primary-unreactive, secondary-cloudy
within 5-15 minutes, tertiary-cloudy
instantly)

TEST GROUP 2

1. 2,4-DNPH Test 2,4-DNP hydrazone +

2. Bisulfite Test Hydroxysulfonates +

3. Schiff’s Test Quinoid dye +

TEST GROUP 3
1. Iodoform Test triiodomethane (iodoform) +

2. Hinsberg Test Benzene sulfonyl chloride (forms +

sulfonamides)

3. Fischer Reaction Methyl-2-hydroxybenzoate +

4. Hydrolysis Ammonia +

5. Hydroxamic Acid Test Hydroxamate complexes +

4. Using reaction mechanisms, show the difference between acyl addition and acyl substitution.

Acyl addition:

​ ttp://www.chem.ucalgary.ca/courses/350/Carey5th/Ch17/ch17-3-0.html
Source: h

Acyl substitution:
5. The Lucas Test cannot be used for larger reactants (i.e. compounds with more than 6 carbons).
Explain why.
The Lucas test cannot be used for larger reactants (i.e. compounds with more than 6 carbons). Explain why.
The Lucas test can only be used if the alcohol is soluble to the the Lucas reagent (concentrated HCl is polar).
When the alcohol has more than 6 carbons, the compound becomes more nonpolar, lowering its solubility with
the reagent, hence Lucas test can’t be used.

6. What is the trend found in the substrates used in Test A for test group 1? Rationalize this trend.
Substrate (Alcoholic AgNO3 test): Alkyl Halide

Ethyl chloride
Tert-butyl chloride
Sec-butyl chloride
chlorobenzene

Ethyl bromide

7. What role does solvent play in AgNO3 test?

The alcoholic AgNO3 test proceeds through the SN1 mechanism, wherein there is an initial loss of a leaving
group. The alcoholic solvent, usually ethanol, acts as a nucleophile and attack the carbocation, forming an
R-ethyl ether. The halide leaving group then forms an ionic bond with the silver ions in solution and precipitates
based on their insolubility in the particular solvent, since ethanol is a polar protic solvent that promotes
ionization of organo-halides.

8. What reagents could interfere with the 2,4-DNPH test ? (Hint: What properties does 2,4-DNPH have?)
A positive test will yield a precipitate. However, some ketones may give oils which will not solidify. Some allylic
alcohols are oxidized by the reagent to aldehydes and give a positive test. Also, some alcohols, if not purified,
may contain aldehyde or ketone impurities.

9. Can Schiff’s test differentiate ketones and aldehyde? Why?

Aldehydes can be differentiated from ketones based on the unknown substance’s reaction to Schiff’s reagent.
Aldehydes react faster than ketones because of steric constraints. The solution turns into a magenta/purple
color which indicates a positive test specifically for aldehydes, while no reaction indicates the presence of a
ketone. This is because the Schiff reagent acts as a nucleophile that joins with the carbonyl group of an
aldehyde, and due to the bulky nature of this nucleophile, a ketone will not produce a positive reaction because
it is more sterically crowded than an aldehyde at a carbonyl carbon.

10. Sulfate cannot be used as a substitute for sulfite in the bisulfite test. Explain why sulfate cannot act
as sulfite can. (Use reaction mechanisms to show this)
This test is for aldehydes and methyl ketones, where presence of both is manifested by the formation of a
water insoluble precipitate. Sulfite oxidizes the oxygen atoms present in the sample into an –OH group and
bonds with a carbon to form a precipitate, which cannot be achieved by a sulfate ion due to its lack of lone
pair[s]. This test exhibits the characteristic reaction of aldehydes and ketones wherein a base-catalyzed
nucleophilic addition occurs across the carbon-oxygen double bond. Polarization of the C=O bond gives the
carbon atom of the carbonyl group a partial positive charge because of its electron deficiency, which makes it
susceptible to nucleophilic attack. The bisulfite ion, a strong nucleophile, then attacks the carbonyl carbon,
oxidizing the oxygen to –OH and in turn bonds with carbon. The general reaction is shown below:

11. The iodoform reaction cannot work with I2 alone. What is the purpose/s of NaOH in this reaction?
The iodine solution is added to a small amount of an alcohol followed by just enough amount of sodium
hydroxide solution to remove the yellow color of the iodine which could interfere in the analysis of the product.
If no amount of NaOH was added, the yellow color which is an indication of a positive result may not be
observable.

12. What does water do in hydrolysis? For which functional group does hydrolysis not work? Why
does this occur?
The role of water in Hydrolysis is that it is used to break down the bonds of a particular substance. In the
Hydrolysis of Salts, water spontaneously ionizes into hydroxide anions and hydronium cations. In the
hydrolysis of Acids, water can act as an acid or a base, according to the Bronsted-Lowry acid theory. In this
case, the water molecule would give away a proton. Perhaps the oldest commercially-practiced example of this
type of hydrolysis is saponification, the formation of soap.

13. What test will differentiate the following? Explain your answers and the expected outcomes.
a. Acetaldehyde and benzaldehyde
Bisulfite test. Benzaldehyde is an aromatic compound whereas acetaldehyde is an aliphatic compound.

Bisulfite test is also an indication whether the sample is an aliphatic aldehyde or an aromatic aldehyde.
Acetaldehyde will react faster than benzaldehyde because an aromatic ring makes the compound more
electron-rich, making the compound less susceptible to nucleophilic attack. Both will form a red precipitate due
to cuprous oxide.

b. Acetaldehyde and acetic acid

2,4-DNPH test. This test will give an orange/red/yellow precipitate with aldehydes; no reaction with acetic acid.

Iodoform test. Acetic acid also contains a -COMe group however it will not give a positive result (i.e. a yellow
precipitate) unlike with acetaldehyde.

c. Acetamide and ethyl acetate

Hydrolysis. These two differ in the reaction rates when they undergo hydrolysis. Esters proceed at faster pace
than amides since the latter are significantly unreactive. In fact it is the most unreactive group among all the
carboxylic acid derivatives. This is because of its slight double bond characteristic that reduces the leaving
group ability of the nitrogen. This resonance form is more prevalent among amides than the other carboxylic
acid derivatives.

EXPERIMENT 11
Reporter: Group 5

1. What side products may be obtained from the reaction above? How are they formed? Draw the
structures of these side products.
A. Methyl Salicylate + 0.1 M NaOH

Side product: ​water

B. Methyl Salicylate + 0.1 M HCl
C. Methyl Salicylate + 0.1 M NH​4​OH
D. Methyl Salicylate + 0.1 M CH​3​COOH
2. In the liquid-liquid extraction of the crude mixture, what is the rationale behind the use of 10%
NaHCO​3​? What exactly does it separate out?
The unreacted salicylic acid drawn into the organic solvent is removed through the addition of aqueous
sodium bicarbonate solution. The 10% NaHCO3 reacts with the unreacted salicylic acid to form sodium
salicylate, and byproducts, water and carbon dioxide gas (thus the bubbles observed). Since sodium salicylate
is ionic, it has more affinity with the aqueous solution. It can now be removed from the extraction mixture, thus
leaving methyl salicylate in the organic layer free from impurities.

3. Why should you use 10% sodium bicarbonate instead of aqueous sodium hydroxide as the
extracting solvent?
When NaOH is used, besides removing the free acid, it can hydrolyze the desired methyl salicylate
(since -OH is a strong nucleophile) to produce salicylate ion, which will be washed away with the aqueous
layer that will be disposed of. The mechanism of this is as follows:
Left curly thing: methyl
Right curly thing: the rest of salicylic acid (benzene ring and OH ortho to carboxylic acid)
With sodium bicarbonate, you can determine whether there is no free acid left when no bubbling
occurs. This is safer than NaOH, which may cause violent bubbling and rapid increase in temperature.

4. What is the mechanism of the Fischer esterification reaction of salicylic acid with methanol? Draw
the mechanism for this reaction and explain why H​2​SO​4​ is only need in catalytic amounts.

R group: the rest of salicylic acid (benzene ring and OH ortho to carboxylic acid)

As you can see in the mechanism, you add acid to protonate methanol which then protonates the
carboxylic group to render it more electrophilic. By doing so, an alcohol can act as the nucleophile and attack
the carbonyl group. If you add too much acid however, methyl salicylate can be hydrolyzed and return to
salicylic acid:

R group: the rest of salicylic acid (benzene ring and OH ortho to carboxylic acid)

5. Methyl salicylate cannot be produced by using methyl chloride through an S​N​2 process. Explain.
What is formed instead?
To prepare esters from carboxylic acids via SN2 reaction, the required reagents are a strong base and
an alkyl halide (primary is best). The base deprotonates the carboxylic acid, rendering it a strong nucleophile to
attack the carbon of the methyl halide, the electrophile. This happens simultaneously with the halide ion
leaving the carbon.
R group: the rest of salicylic acid (benzene ring and OH ortho to carboxylic acid)

Methyl salicylate cannot be produced using the above reaction because there is a stronger nucleophile
than the carboxylic group, which is the alcohol.

A possible product could be 2-methoxybenzoic acid, aka o-anisic acid. This can be formed by a
nucleophilic substitution (SN2), wherein the lone pair on a hydroxyl group attacks the electrophile methyl
chloride to displace the chloride ion. The chloride ion will then abstract hydrogen attached to the positively
charged oxygen to form an ether.

6. What other methods could produce esters besides Fischer esterification?

Mitsunobu reaction ​uses an acid and an alcohol, but also DEAD (diethylazocarboxylate) and triphenyl
phosphine. This is commonly used to give a clean inversion of the stereochemistry of the carbon where the
hydroxyl group of the alcohol is attached.
Transesterifications use alcohol and an ester as reactants. This switches the group attached to the
ester oxygen. A commercially important example is the reaction of methanol and triglyerides to form methyl
esters, which can be used as biodiesel and glycerol.
Decarboxylative esterification forms an ester by reacting a carboxylic acid with an acid anhydride to
form a mixed anhydride, which can then decompose into carbon dioxide and an ester.
Tishchenko reaction uses two aldehydes and an aluminium trialkoxide as a catalyst that can react to
form an ester.
Baeyer-Villiger reaction starts with a ketone, cyclic or acyclic, and reacts with either a peracid or
hydrogen peroxide and a Lewis acid, which forms an ester.

EXPERIMENT 12
Reporter: Group 6

1. What is the reaction involved in the synthesis of soap?

The reaction involved in the synthesis of soap is the hydrolysis of esters (alkaline hydrolysis of
triglyceride) or saponification reaction. This reaction involves an ester (hydrogenated shortening or
animal fat) and a strong base, NaOH.
The NaOH dissociates into Na​+ and OH​-​. The hydroxide then cleaves off the -OR group through
a nucleophilic attack of hydroxide. This produces a carboxylic acid which will react with the basic
leaving group -OR​- to produce an alcohol and carboxylate ion. The carboxylate anion forms a salt with
the Na​+​ - the soap.

2. Write the reaction mechanism for the synthesis of soap.

3. Why was the dilute soap solution poured in a solution of NaCl in water?
Adding NaCl in the soap solution, which is the process of salting out, will precipitate the soap.
The precipitation of soap is through common ion effect. Soap is the sodium salt of a fatty acid
and is partially soluble in water. When soap dissolves, it ionizes into sodium ions and fatty acid ions.
When we add Sodium chloride, it gets ionized in water and its sodium ions cause the sodium ions of
soap to combine with the fatty acid ions and separate as solid soap.

4. Explain the result obtained when the dilute soap solution is treated with CaCl​2​, MgCl​2​, and FeCl​3
solutions.
CaCl​2​, MgCl​2​, and FeCl​3 are
​ salts like NaCl; they dissociate in water. The dissociated ions (Ca​2+​,
Mg​2+​, and Fe​3+​) bonds with the carboxylate anions to form precipitates.
Sodium salts are generally soluble in water. When it is replaced by calcium, magnesium or iron
ions, the new salt will now be insoluble in water forming a soap scum which is a white solution usually
found in bathrooms. This is why soaps do not work well in hard water which contains Ca​2+​, Mg​2+​, and
Fe​3+​ ions. 1

5. How does soap function as an emulsifying agent for oil in water? Draw a picture of an oil droplet and
several molecules to illustrate your answer.
Written explanation: Soap has both polar and nonpolar structures. The long hydrocarbon chain is nonpolar and
hydrophobic while the "salt" end of the soap molecule is ionic and hydrophilic. When oil, which is non-polar, is
mixed with a soap-water solution, the soap molecules work as a bridge between polar water molecules and
nonpolar oil molecules. Since soap molecules have both properties of non-polar and polar molecules, it acts as
an emulsifying agent. This means that while oil doesn't naturally mix with water, soap can suspend oil/dirt in
such a way that it can be removed. When mixing soap and water, the soap molecules arrange themselves into
tiny clusters ('micelles'), wherein the water-loving part of the soap molecules points outwards, forming the outer
surface of the micelle, and the oil-loving parts group together on the inside, where they don't come into contact
with the water at all. Micelles can trap oil (which attracts dirt) in the center. Then, since the micelle is soluble in
water, it can easily be washed away.
EXPERIMENT 13
Reporter: Group 7

1. Which of the substances produced a positive result for each test? What are the substances or
process is responsible for the observable change?

2. For each test, which functions as the oxidizing reagent? Based from your data which is the
strongest oxidant? Which is the weakest?

The oxidizing reagents used in the tests performed were potassium permanganate (KMnO​4​), potassium
dichromate (K​2​Cr​2​O​7​), Tollen’s reagent (Ammoniacal AgNO​3​), Benedict’s reagent and Fehling’s reagent.
Among them, KMnO​4​ and K​2​Cr​2​O7 are the strongest while the other three are mild oxidants. In theory,
however, Tollen's reagent is a relatively stronger oxidant than the other two copper(II)-based reagents
(Benedict’s reagent and Fehling’s reagent) because Cu(II) ion has a lower standard reduction potential than
Ag(I) ion.

3. Based on the results, make a comparison of the capability to be oxidized of the functional groups
present? Explain your answer.
Aldehydes are very easy to oxidize, meaning they are strong reducing agents because of the H atom attached
to their –C=O group. Meanwhile, ketones are mostly resistant to oxidation because of the absence of that H
atom attached to their –C=O group. Only very strong oxidizing agents like KMnO4 can oxidize ketones,
although in a destructive manner. For alcohols, only primary and secondary alcohols can be oxidized while
tertiary alcohols cannot be oxidized because there is no H atom attached to the C in R3C-OH for the oxidizing
agent to remove.
4. Can the oxidation reactions above distinguish between substances of the same functional group?
Explain your answer.

Functional groups of a compound react the same way regardless of the compound that they are a part of.
Thus, substances of the same functional group cannot be distinguished from each other by simply performing
oxidation reactions. A positive result for a particular test may confirm the presence of a functional group, but
does not indicate how much of it is present, or what percentage it takes up in the substance.

5. Which of the following tests can be used to distinguish between the following unknowns?
a. Benzaldehyde and Benzophenone
b. Ethanol and Ethanal
c. Ethene and Ethanol