CLASSIFICATION TESTS FOR

CARBOXYLIC ACID AND

DERIVATIVES

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OBJECTIVES
1st Objective
To differentiate the reactions of carboxylic acid and
derivatives.

2nd Objective
To distinguish carboxylic acid derivatives using
classification tests.

3rd Objective
To explain through chemical equations and
mechanisms the reactions involved in each test.
 Carboxylic Acids
Carboxylic Carboxylic acids are another class of organic
compounds containing the carbonyl group. Their
Acids and occurrence in nature is widespread, and they are
Derivatives important components of foodstuffs such as vinegar,
butter, and vegetable oils. The most important chemical
property of carboxylic acids is their acidity. Furthermore,
carboxylic acids form numerous important derivatives,
including esters, amides, anhydrides, and acid halides.
The functional group of carboxylic acid is a carboxyl
group, so named because it is made up of a carbonyl
group and a hydroxyl group.
Methods/Tests Used

Hydrolysis of Acid Alcoholysis: Schotten-

Derivatives Baumann Reaction

Aminolysis Hydroxamic Test

EXPERIMENTS
Hydrolysis of Acid D 2%
erivatives AgNO3 NaHCO3

Acetic
Anhydr
ide
+
Water

2% NaHCO3
AgNO
 I. Hydrolysis of Acid Derivatives

Acyl halides and Acid Anhydrides Esters

1. Place 1 ml of water in 1. Add 2 mL of 25% NaOH

a test tube. Cautiously solution to 1 mL of ethyl
add dropwise 10 drops of acetate. Cover mouth of
the sample. Note for a the test tube with a
warming effect. marble and heat the test
tube in a boiling water
2. Divide the resulting bath for 5 minutes.
mixture in #1 into 2
portions. To the 1st, add 2. Neutralize the mixture
1ml of 2% AgNO3. Observe with 10% HCl solution.
for precipitation. To the With wafting motion, take
2nd portion, add 1 mL of note of the odor.
saturated NaHCO3. Note for
 THEORETICAL
Water 2% AgNO3 NaHCO3
SAMPLES RESULTS RESULTS RESULTS

Turbid, warming eff no ppt but

Acetyl Chloride white ppt
ect with effervescence
Clear colorless
Acetic Anhydride solution, no ppt effervescence
2 layers
EXPIREMENTAL
Water 2% NaHCO3
SAMPLES RESULTS AgNO
RESULTS
3 RESULTS

------------------- ------------------- -------------------

Acetyl Chloride -----------------
----------------- -----------------
Clear colorless no ppt/effervescenc
no ppt, slightly
Acetic Anhydride solution,
turbid e Tables 1
2% NaHCO3
AgNO3
DISCUSSI hydrolysis
The Table shows the results of the
of the different carboxylic acid

ON derivatives. In hydrolysis, the water molecules

+ -
are split into H and OH . The easiest acid
derivatives to hydrolyze is acyl chloride, which
requires only the addition of water. Carboxylic
acid salts are converted to the corresponding
acids instantaneously at room temperature simply
on treatment with water and a strong acid such
as HCL. According to Brown (2013), acid
chlorides (also called acyl chlorides), acetyl
chloride sample, react very rapidly with water
to form carboxylic acids and HCl. The positive
visible result is the turbidity of the substance
and its warming effect due to the presence of
HCl. Silver nitrate also reacted to the acetyl
chloride producing silver chloride (AgCl) which
DISCUSSI
ON
On the other hand, acetic anhydride (the sample
used in the actual experiment) is not as reactive as
acetyl chloride. Even though acid anhydrides undergo
reactions with the same nucleophiles that the acid
chlorides react with, the rate of reaction is slower.
As seen also in Figure 1, acetic anhydride reacts
with water to yield two acetic acids. Acetic
anhydride is the most carboxylic acid anhydride. It
is produced and used in large quantities in industry,
primarily for the synthesis of plastics and fibers.
Comparing the results of the experiment and the
 Hydrolysis
TESTS RESULTS

Clear colorless solution with plasti

Acetic Acid c balloon-like odor

The hydrolysis of esters, ethyl

DISCUSSI acetate was used, occurs very slowly
and only becomes rapid with the
ON introduction of an aqueous acid or
base. Hydrolysis of esters in aqueous
base is often called saponification
(Brown, 2013). In the experiment,
ethyl acetate when reacted with
 Alcohol
ysis:
Schotten-
Baumann
Reaction
 II. Alcoholysis: Schotten-Baumann
Reaction

Acyl halides and Acid Anhydrides Acetic Acid

In another test, Warm a mixture of 10

place 0.5 mL ethanol, 1 mL drops of acetic acid, 1 mL
water, and 0.2 mL of ethanol, and 5 drops of
acetic anhydride sample. conc. Sulfuric acid over a
Add 2 mL 20% NaOH water bath for 2 minutes.
solution. Plug the test Note he odor of the ester
tube with a cork stopper formed.
and shake mixture for
several minutes. Note the
odor and the layers of the
ester formed.
Acetic Acetic
Acid Anhydride
 THEORETICAL
Odor Formation of
Layers
SAMPLES RESULTS RESULTS
Strong plastic balloon-like/
Acetic Acid fruity odor

Acetyl Faint plasticballoon-

Chloride like/fruity odor

Acetic Faint plasticballoon-like/fr

Anhydride uity odor EXPIREMENTAL
Odor Formation of
Layers
SAMPLES RESULTS RESULTS

----------------------------
Acetic Acid fruity odor
-------------------------

Acetyl ------------------------------------------ -----------------------------------------

---------------------------------------- --------------------------------------- Tables 2
 In the table, it shows the results
DISCUSSI of alcoholysis using the Schotten-
Baumann reaction. Acetic acid and acetic
ON anhydride were the samples used. Acetic
acid when reacted with ethanol produced
ethyl acetate, an ester, which was
accounted for the fruity odor, and
water. Acetyl anhydride also has the
same odor but after some time, the odor
disappeared.

Acetyl chloride also produced ethyl

acetate, an ester with a plastic
Aminolysis: Anilide
Formation
III. Aminolysis: Anilide Formation

Aminolysis: Anilide Formation

1. Add a few drops of
acetyl chloride or
acetic anhydride sample
to 0.5 mL aniline.
Transfer the mixture
into new test tube
containing 5 mL water.
Describe precipitate
formed.
 Acetic
Anhydrid
e
 THEORETIC
AL
TESTS RESULTS

Acetyl Chloride White ppt with oily layer

Acetic Anhydride White ppt with oily layer

EXPIREMENT
AL
TESTS RESULTS
---------------------------------------------
Acetyl Chloride -----------------------------------------

Acetic Anhydride Brown ppt with oily layer

Tables 3
 The table shows the results
DISCUSSI obtained from the aminolysis of the
samples. Acetyl chloride showed a white
ON precipitate with an oily layer. Brown
(2013) stated that acid chlorides react
readily with ammonia and with 1º and 2º
amines to form amides. Acetyl chloride
readily formed an amide in the form of
N-phenylacetanamide or commonly known as
acetanilide, as the white precipitate,
and HCl, which accounts for the oily
layer.
Acetic anhydride reacted with
aniline produced acetanilide, which will
theoretically form white precipitate and
Hydroxamic Acid
Test
 Hydroxamic Acid Test

Preliminary test: mix 2 drops of the sample, 1 mL of 95% ethanol

and 1 M HCl. Note color produced when 1 drop 5% FeCl3 solution is added
to the mixture. If a color other than yellow is obtained, the test cannot be
used. Otherwise, the test is conducted as follows:

Add 2 drops of the samples to 2 mL of alcoholic NH2OH.HCl and 1

mL of 1M KOH. Heat in a boiling water bath for 2 minutes. Cool the
mixture. Add 1 mL of 5% FeCl3. Note the color of the solution.
 Preliminary Upon addition of 5% FeCl3
Test
SAMPLES RESULTS RESULTS

Ethyl Acetate Yellow solution Deep burgundy color

Table 4 shows the results to the

DISCUSSI Hydroxamic Acid Test. A preliminary test was
conducted before proceeding to the main test. It
ON was done to prevent the formation of phenols and
enols that might give colors to the solution,
thus giving the test an erroneous result. In
test proper, hydroxylamine is treated with
esters, in this experiment ethyl acetate was
used, which substitute a hydroxylamino (NH-OH)
group for the ester alkoxyl radical. The
Break
Guide
questions
1.Arrange the following in the
order of decreasing reactivity
towards a nucleophile. (number
them 1 – 5):
v
4 acid amide
1 acid halide
3 ester
5 carboxylic acid
2 acid anhydride
2. Rationalize the order of reactivity in #1.

There are five main types of acyl derivatives.

Acid halides are the most reactive towards
nucleophiles, followed by anhydrides, esters, and
amides. Carboxylate ions are essentially
v
unreactive towards nucleophilic substitution,
since they possess no leaving group. The
reactivity of these five classes of compounds
covers a broad range; the relative reaction rates
of acid chlorides and amides differ by a factor of
10.
A major factor in determining the reactivity
of acyl derivatives is leaving group ability,
which is related to acidity. Weak bases are better
3. Draw the condensed structural
formulas of the sample compounds.

a.Acetic Anhydride: (CH3CO)2O

b.Acetyl Chloride: CH3COCl
c.Ethyl Acetate:v CH3COOCH2CH3
d.Acetic Acid:CH3COOH
4. Write the equations involved in
the chemical tests.

v
Alcoholysis: Schotten-Baumman React
4. Write the equations involved in
the chemical tests.

Aminolysis: Anilide formation

v

Hydroxamic Test