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Saturday, January 25, 2020

The relative reactivity of primary : Secondary : tertiary hydrogen to chlorination is 1: 3.8: 5. Calculate the percentage of all the monochlorinated products obtained from 2-methylbutane.

How to calculate ercentage yield of halogenated products of alkene at 25° temperature?

We know that halogenation of alkane take place via free radical substitution reaction mechanism and stability of carbocation follow as 3°> 2° > 1° and rate of reaction of Halogens with alkanes, follows the order: F2 > Cl2 > Br2 > I2
(1) Iodination is very slow and a reversible and carried out in the pressure of oxidizing agents such as HIO3 or HNO3 to oxidised HI to I2.
(2) Chlorination of most alkanes whose molecules contain more than two carbon atoms gives a mixture of isomeric monochloro products. The percentages given are based on the total amount of monochloro products formed in each reaction. The numbers of mono-halogenated products formed are equal to the number of different type of H-atoms.
The ratios of products that we obtain in chlorination reactions of higher alkanes are not identical with what we would except if all the hydrogen atoms of the alkane were equally reactive.
We find that there is a correlation between reactivity of different hydrogen atoms and the type of hydrogen atom (1 ° 2 ° or 3 ° ) being replaced. The tertiary hydrogen atoms of an alkane are most reactive, secondary hydrogen atoms are next most reactive and primary hydrogen atoms are the least reactive.
 (3) Bromine is less reactive toward alkanes in general than chlorine, but bromine is highly selective means the difference between relative rate of bromination is large. Bromine shows a much greater ability to discriminate among the different types of hydrogen atoms. The reaction of isobutane and bromine, for example, gives almost exclusive replacement of the tertiary hydrogen atom.
(5) Fluorination is too violent to be controlled, Fluorine being much more reactive than chlorine is even less selective than chlorine. Because the energy of activation for the abstraction of any type of hydrogen by a fluorine atom is low, there is very little difference in the rate at which a 1°, 2° or 3° hydrogen reacts with fluorine. Reactions of alkanes with fluorine give (almost) the distribution of products that we would expect if all of the hydrogens of the alkane were equally reactive.
(5) Relative rate of substitution of H-atoms of alkane in free radical halogenation is: 
Illustrative Example:
The relative reactivity of primary : Secondary : tertiary hydrogen to chlorination is 1: 3.8: 5. Calculate the percentage of all the monochlorinated products obtained from 2-methylbutane.

Related Questions:


How to calculate packing fraction or packing efficiency of two dimensional (2D) hexagonal packing solid atoms?

 Hexagonal close packing:
The particles in every next row are placed in the depressions between the particles of the first row. The particles in the third row will be vertically aligned with those in the first row. This type of packing gives a hexagonal pattern and is called hexagonal close packing
Packing efficiency calculation:
(1) One sphere will be in constant contact with 6 other spheres hence coordination number is 6
(2) Side of hexagon is a and a=2r where r is the radius of atom (sphere) .
(3) Area of hexagon unit cell is 6*area of six equilateral triangles 
       (4) Area of atoms in the hexagon unit 
      Packing fraction (PE) , fraction of area occupied by spheres 

Why Boric acid become strong acid in the presence of cis 1,2-diol or 1,3-diol ?

Boric acid is a weak monoprotic acid (Ka=6.4×10−10).Therefore, it cannot be directly titrated with standard strong alkali (NaOH). But by the addition of an organic poly hydroxy compound such as 1,2- or 1,3-diol, (Like Sugar, Mannitol, Catechol)  it is converted to a much stronger acid, which can be titrated using phenolphthalein. This is due to the complex formation between hydrated borate ion and either 1,2- or 1,3-diol  for example .

Ploy hydroxy (Cis-diol) increases acidity of boric acid due to formation of complex with metaborate and reaction goes to farward to produce more H+.

Friday, January 24, 2020