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Nitration of an Aromatic Ring - M-Nitrobenzoic Acid from Benzoic Acid

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Exercise No. 11
Nitration of an Aromatic Ring
m-Nitrobenzoic Acid from Benzoic Acid
Archangel Gabriel J. Nudalo
Group No. 4
CHEM 40.1 12L


I.        Introduction

                Electrophilic aromatic substitution is a reaction used in many organic syntheses because it prohibits many functional groups from reacting to the aromatic ring. The general form for this reaction is:

Ar-H        +        E+        →        Ar-E        +        H+

                where Ar-H is an aromatic compound and E+ is an electrophile that can replace H from Ar-H.

                In this exercise, nitric acid is protonated by sulfuric acid to form nitronium ion (NO2+). This ion functions as an electrophile and reacts with benzene to produce nitrobenzene and benzene-sulfuric acid (Laali & Gettwert, 2000). In chemical equation, it is shown as:

[pic 1]
(Image obtained from https://socratic.org)

                Since COOH and NO2 are meta directors, they would always react in the 1,3- position of a benzene ring.

                Other reactions that accompanies the formation of m-nitrobenzoic are:

  1. Dinitration to form 3,5-dinitrobenzoic acid

[pic 2]

                Through the formula, the unfavourability of dinitration is seen since benzoic acid is more reactive than m-nitrobenzoic acid. In the formula, nitration is favored because NO2 is a stronger nucleophile than SO3.

  1. Sulfonation to form m-carboxybenzensulfonic acid

[pic 3]

                In the formula, nitration is favored because NO2 is a stronger nucleophile than SO3.        

                Molecules like -OH and -NH2 donates electrons and are called activated substituents while -NO2 and -Cl withdraw electrons, therefore, they are called deactivating substituents (Carey, 2006).

                

II.        Objectives

  1. To prepare an aromatic nitro compound by means of an EAS reaction
  1. To prepare m-nitrobenzoic acid from benzoic acid;
  2. To recrystallize the crude product; and
  3. To write the mechanism for the nitration of benzoic acid and the accompanying side reactions.
  1. To compare the starting material and the product.
  1. To differentiate between m-nitrobenzoic acid and benzoic acid by using chemical tests.

III.        Materials and Methods

  1. Schematic Diagram of the Procedure

Part A. Synthesis and Isolation of m-Nitrobenzoic Acid
NOTE: CONDUCT SYNTHESIS IN THE FUMEHOOD!
[pic 4][pic 5][pic 6][pic 7][pic 8]

[pic 9]

[pic 10]

[pic 11][pic 12]

[pic 13][pic 14][pic 15]

[pic 16][pic 17]

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[pic 22][pic 23][pic 24]

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[pic 30][pic 31][pic 32][pic 33]

Part B. Chemical test for the Comparison of Starting Material and Product

(For reaction with Bromine)[pic 34][pic 35][pic 36][pic 37][pic 38][pic 39][pic 40][pic 41]


(Place in “Halogenated Organic Wastes” after)

(For reaction Baeyer’s Test)

[pic 42][pic 43]

[pic 44]


(Place in “Mn-Containing Wastes” after)

(For Ferrous sulfate test)[pic 45]

[pic 46][pic 47]

[pic 48]


(Place in “Iron-Containing Wastes after”)

        B.        Setups

[pic 49]
        
Figure 1. Set-up for Suction Filtration
        (*Image obtained from http://what-when-how.com/organic-chemistry
        laboratory-survival-manual/recrystallization-part-1-laboratory-manual/)

[pic 50]
Figure 2. Set-up for Hot Gravity Filtration
(*Image obtained from https://www.emaze.com/@AQZFIWZI/filtration)

[pic 51]
        
Figure 3. Set-up for Melting Point Determination.
        (*Image obtained from https://www.yaksic.com/ispp2.html)

        C.        List of Necessary Chemicals

Name and Structure of the compound

Function in the Exercise

Physical Properties

Hazards

Precautions

m-Nitrobenzoic Acid

Final product

Solid, bitter, off-white in color, yellowish
MP: 142 °C
Solubility:
Soluble in CH
3OH, (C2H5)2O, C3H6O, cold & hot water

Health Hazard

Fire Hazard

Keep away from heat and sources of ignition.

Use proper lab attire in handling.

Benzoic Acid

Starting sample

Solid
BP: 249.2 °C
MP: 122.4 °C
Solubility:
Soluble in oil and water, slightly soluble in cold water

Health Hazard

Fire Hazard

Flammability

Keep away from heat and sources of ignition.

Use proper lab attire in handling.

Seek medical advice if ingested.

Avoid contact with skin and eyes.

Nitric Acid

Reagent used in the synthesis of m-Nitrobenzoic acid

Acidic liquid, clear to light yellow in color
BP: 121 °C
MP: -41.6 °C
Solubility:
Soluble in cold & hot water, and diethyl ether.

Health Hazard

Keep locked in a dry container.

Keep away from heat, sources of ignition, and combustible material.

Keep away from incompatibles such as reducing agents, combustible materials,

organic materials, metals, etc.

Sulfuric Acid

Reagent used in the synthesis of m-Nitrobenzoic acid

Thick oily odorless liquid with an acidic taste
BP: 270 °C
MP: -35 °C to 10.36 °C
Solubility:
Soluble in cold water, ethyl alcohol, and water with liberation of much heat

Health Hazard

Fire Hazard

Keep locked in a dry container.

If ingested, seek medical advice immediately and show the container or the label.

Keep away from incompatibles such as reducing agents, combustible materials,

organic materials, metals, etc.

Ethanol

To be mixed with KOH and to be used in the FeSO4 test

Colorless liquid that smells like wine or whiskey
BP: 78.5 °C
MP: -114.1 °C
Solubility:
Soluble in cold & hot water, methanol, diethyl ether, and acetone.

Health Hazard

Fire Hazard

Keep locked up and away from heat and sources of ignition. If ingested, seek medical advice immediately and show the container or the label.

Avoid contact with skin and eyes.

Potassium Hydroxide

To be mixed with C2H6O and to be used in the FeSO4 test

White odorless solid
BP: 1384 °C
MP: 380 °C
Solubility:
Soluble in diethyl ether, cold & hot water.

Health Hazard

Reactivity

Personal Protection

Keep container dry.

Do not ingest and breathe dust.

In case of insufficient ventilation, wear suitable respiratory equipment.

Avoid contact with skin and eyes.

Keep away from incompatibles such as organic materials, metals, acids, moisture.

Ferrous Sulfate

Reagent used in the comparison test

Grayish white to yellowish solid
Solubility:
Soluble in cold water

Health Hazard

Personal Protection

Do not breathe dust.

In case of insufficient ventilation, wear suitable respiratory equipment.

If you feel unwell, seek medical attention and show the label when possible.

Avoid contact with skin and eyes.

Bromine

Reagent used in the comparison test

Pungent red-brown liquid
BP: 58.78 °C
MP: -7.25 °C
Solubility:

Soluble in diethyl ether, cold water, alcohol, chloroform, carbon disulfide, carbon tetrachloride, concentrated hydrochloric acid, and aqueous solution of bromides.

Health Hazard

Keep in a locked dry container.

Do not ingest and breathe gas/fumes/ vapor/spray.

In case of insufficient ventilation, wear suitable respiratory equipment.

Keep away from incompatibles such as reducing agents, combustible materials, and organic materials.

Potassium Permanganate

Reagent used in the comparison

Purple odorless solid with a sweetish taste
MP: decomposes
Solubility:
Soluble in methanol, acetone, sulfuric acid cold water, and hot water

Health Hazard

Personal Protection

Keep away from heat, sources of ignition, and from combustible material.

Do not ingest and breathe dust.

Avoid contact with skin and eyes.

Keep away from incompatibles such as organic materials, metals, acids.

*Data obtained from www.sciencelab.com

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