Class 12th

7.1

The general characteristics of Group 15 elements are:

Electronic configuration: All Group 15 elements have 5 electrons in their valence The general electronic configuration of these elements is ns² np³

Oxidation state: Group 15 elements have 5 valence electrons and they require 3 more electrons to complete their However, the gaining of 3 electrons is difficult

Atomic size: Atomic size increases as we move down the group due to increase in the number of

Ionisation enthalpy: Ionisation enthalpy decreases as we move down the group because of increase in atomic

Electronegativity: Electronegativity decreases on moving down the group due to increase in atomic

Since ethanol is a alcohol, so in presence of alcoholic KOH, alkyl chloride undergo elimination reaction, which results in the removal of proton and being substituted by a bromide ion.

It is also a simple substitution reaction in which under the presence of aqueous NaOH, bromide ion is replaced by hydroxide ion as it is a better leaving group than hydroxide ion.

 

It is a simple substitution reaction in which a better leaving group leaves and is being substituted by an ion.

CH₃CH₂Br + KCN - CH₃CH₂CN + kBr

5-C₆H₅ONa + C₂H5Cl

It is a simple substitution reaction in which a better leaving group leaves and is being substituted by an ion.

C₆H₅ONa + C₂H₅Cl? C₆H₅ – O – C₂H₅ + NaCl

6-CH₃CH₂CH₂OH + SOCl₂

This reaction is called as wurtz reaction in which in which clubbing together of a alkyl halide group with a sodium or potassium salt of an ether group.

 

7-CH₃CH₂CH = CH₂+ HBr

It is an antimarkovnikoff reaction in which under presence of a peroxide an alkene undergoes substitution, wherein the halo group is attached to that carbon which has least no. Of alkyl groups attached to it.

 

8-CH₃CH = C (CH₃)₂ + HBr

It is a markovnikoff reaction in which an alkene undergoes substitution reaction with hydrohalide, wherein a halo group is attached to that carbon atom which has the largest no. Of alkyl groups attached to it.

(i) Freon 12:- the chlorofluorocarbon compounds of methane and ethane are collectively known as freons. They are extremely stable, unreactive, non-toxic and non-corrosive. Example of Freon 12 is CCl₂F₂. It is mainly used in refrigeration and eventually makes its way into the atmosphere where it diffuses unchanged into the stratosphere. In stratosphere, Freon is able to initiate the radical chain reactions that can upset the natural ozone balance.

• DDT: - it stands for p, p'-Dichlorodiphenyltrichloroethane (DDT). It is mainly used as an
• Iodoform: - it was earlier used as an antiseptic but the antiseptic properties are due the liberation of free iodine and not due to the iodoform itself. Due to its objectionable smell, it has been replaced by other formulations containing iodine.
• Carbon tetrachloride (CCl₄):- it is used as an industrial solvent for oils, fats, resins etc. and also in dry Used as a cleaning fluid both in industries, as a degreasing agent and in the home, as a spot remover and as a fire extinguisher.

Let us explain each question from Haloalkane and Haloarenes chapter one by one. Students who are currently in school and plan to take the CBSE board exam for class 12th soon, need to prepare all these questions. Let us get started.

(i) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.

Sp² hybrid carbon (s-character=33.33%) in chlorobenzene is more electronegative than a sp³-hybrid carbon (s-character=25%) in cyclohexylchloride, due to greater s-character. Thus, Carbon atom of chlorobenzene has less tendency to release electrons to Cl than carbon atom of cyclohexylchloride.

Chlorine atom in chlorobenzene is attached to the benzene ring. Here, the carbon-chlorine bond is polar. However, electron delocalization is possible in the benzene ring. Due to the electron delocalization, the overall dipole moment reduced since the polarity is distributed over the entire ring structure.

On the other hand, the chlorine atom in cyclohexyl chloride is attached to a saturated carbon atom in the cyclohexane ring. Because of this, there is no electron delocalization in the saturated structure. Hence, the dipole moment is more localized and stronger as compared to chlorobenzene.

 (ii) Alkyl halides, though polar, are immiscible with water.

Alkyl halides are polar because of the difference in electronegativity between carbon and halogen atoms. Here, there is not enough polarity to make them soluble in water.

The alkyl part of molecule is non-polar as well as hydrophobic in nature. This portion is large enough to dominate the solubility characteristics of the molecule. The entire molecule becomes insoluble in water due to this.

Water molecules create extensive hydrogen bonds with each other. However, Alkyl halides cannot form hydrogen bonds with water, which reduces their solubility in water. Haloalkane and Haloarene NCERT excercise discusses this question in further detail.

(iii) Grignard reagents should be prepared under anhydrous conditions.

Grignard reagents are very reactive organometallic compounds and they react readily with water to produce hydrocarbons. This destroys the Grignard reagent and makes it ineffective for its original purpose.

The reaction with water not only destroy Grignard reagent but also it produces by products that can complicate the synthetic pathway.

Preparing Grignard reagents under anhydrous conditions makes sure that they remain stable and effective for use in further reactions. Moisture-free conditions are important for the formation and utilization of reagents.

R-Mg-X + H-OH → R-H + Mg (OH)X

Do note that questions based on such equations from organic chemistry are also be asked in the CUET exam which makes it important for students to remember it.

Thus, Grignard reagents must be prepared under anhydrous conditions.

(i) Since the conversion of ethanol to but-1-yne involves the addition the two extra carbons that is why the conversion is carried out in 3 steps.

1. In the first step ethanol is treated with thionyl chloride (SOCl₂) in the presence of pyridine to give chloroethane

• In the second step the acetylene is treated with sodamide(NaNH₂) in the presence of liquid ammonia to give sodium acetylide

• The last step involves the reaction between chloroethane and sodium acetylide to give the final product as the But-1-yne and NaCl as the by-product.

• The bromination of ethane (Br₂ in the presence of light at 520-670K) gives bromoethane which on further treatment with alcoholic KOH results in the alkene called ethane which again on bromination with Br₂/CCl₄ gives dibromide(vicinal bromide) called 1,2-dibromoethane which on treatment with alcoholic KOH gives bromoethene as the final product.

• Propene on treatment with HBr in the presence of peroxide (anti-markovnikoff's rule which states the negative part e. Br^- goes to the carbon which has more number of hydrogens and positive part i.e. H⁺ goes to the carbon which has lesser number of hydrogens) gives 1-bromopropane which on treatment with silver nitrite in the presence of alcohol or water gives 1-nitropropane as the final product.

• Chlorination of toluene (Cl₂ at 773K) gives benzyl chloride with the removal of HCl. Benzyl Chloride on further treatment with dilute KOH in the presence of heat gives benzyl alcohol as the final (dilute KOH removes Cl from the benzyl chloride and replaces it by OH)

• Propene is treated with Br₂/CCl₄e. bromination of alkene takes place to give dibromides, in this case 1,2-dibromopropane which on further treatment with alcoholic KOH gives propyne.(two times removal of KBr)

• Ethanol in treatment with thionyl chloride(SOCl₂) in the presence of pyridine gives ethyl chloride with the evolution of SO₂ The ethyl chloride on treatment with mercury fluoride gives ethyl fluoride (the Cl of ethyl chloride is being replaced by F from Hg₂F₂).

• Bromoethane on treatment with alcoholic KCN forms Acetonitrile with the removal of KBr. CN is added in the case where there is a need to increase the number of Further the acetonitrile is treated with CH₃MgBr(Grignard reagent) in the presence of ether, the intermediate so formed is hydrolysed, and the product formation takes place i.e. Propanone and NH₃ is obtained as the by- product.

• But-1-ene reacts with HBr to form 2-bromobutane(acc. To markovnikoff's rule) and further 2- bromobutane is treated with alcoholic KOH in the presence of heat to form But-2-ene with the removal of HBr.(alcoholic KOH removes H from the carbon which has less number of hydrogens just next to the carbon to which halide is attached and gives the major product e. Saytzeff rule)

• The conversion of 1-chlorobutane to n-octane in the presence of Na metal and dry ether is called Wurtz Two equivalent Chlorobutane reacts to give n-octane as a final product and NaCl as the by-product.

 

The conversion of benzene to biphenyl using Na and dry ether is called FITTIG reaction.

Firstly, the benzene is treated with Br₂/FeBr₃ results in the formation of bromobenzene. It is an electrophilic substitution. Further the bromobenzene is treated with Na metal in presence of dry ether to form biphenyl as the final product and NaBr as the by-product.

 

If instead of Na metal, bromobenzene is treated with Cu metal then the reaction is called Ullmann's reaction. The final product obtained in this reaction will also be biphenyl.

Carbon due to its chemical property of catenation, tetravalency and the ability to form stable covalent bonds form hydrocarbon and halo-alkanes easily.

The process of removal of hydrogen and halogen from adjacent carbon atoms of haloalkens is called dehydrohalogenation. NaOEt ( Sodium ethoxide) used in Dehydrohalogenation.  It is a strong base and helps remove a β-hydrogen from the haloalkane.

The chemical reaction for

Reaction:

R–CH2 –CHX–R′+NaOEt   ethanol > R–CH=CHR'+NaX+EtOH

(i) 1-Bromo-1-methylcyclohexane: 

      Br
       |
 CH3–C1–cyclohexane  + NaOEt/EtOH → CH3–C=cyclohexane (double bond at C1-C2) + NaBr + EtOH

Major Product: 1-Methylcyclohexene

(ii) 2-Chloro-2-methylbutane

      CH3
           |
 CH3–C–CH2–CH3   + NaOEt/EtOH → CH3–C=CH–CH3 + NaCl + EtOH
           |                                
          Cl                             CH3

Major Product: 2-Methyl-2-butene (major), 2-Methyl-1-butene (minor)

(iii) 2,2,3-Trimethyl-3-bromopentane

       CH3         CH3
         |            |
 CH3–C–C–CH2–CH3  + NaOEt/EtOH → CH3–C=C–CH2–CH3 + NaBr + EtOH
         |   |                           
        CH3  Br                        CH3

Major Product: 2,2,3-Trimethyl-2-pentene