--%>

What are different mechanisms for nucleophilic substitution?

Nucleophilic substitution reactions in halides containing  - X bond may take place through either of the two different mechanisms,SN1 and SN2.

    
SN1 Mechanism (unimolecular Nucleophilic Substitution)

In this type, the rate of reaction dependent only on the concentration of alkyl halide, i.e.

Rate = k [RX]

The tertiary alkyl halides react by SN1 mechanism via formation of carbocations as intermediates as given below:

Step I: in the first step the alkyl halide slowly dissociates into halide and carbocation.

1475_nucleophillic.png 

This step is the slowest and reversible. It involves the cleavage of C-Br bond for which the energy is obtained through salvation of halide ion with the proton of protic solvent. Since the rate of reaction depends upon the slowest step, the rate of reaction depends only on the concentration of alkyl halide and not on the concentration of nucleophile.

Step IInd: in the second step, carbocation at once combines with the nucleophile to form the final substituted product.

2268_nucleophillic1.png 

The order of reactivity of a variety of alkyl halides from SN1 mechanism is as below:

The 3+ alkyl halides are most reactive because the intermediate carbocation formed in their case is the most stable. The more stable intermediate is formed at faster rate.
    
SN2 Mechanism (Bimolecular Nucleophilic Substitution)

In this type of reaction is dependent on the concentration of alkyl halide as well as nucleophile, i.e. 

Rate = k [RX] [Z-]

In this mechanism the incoming nucleophile interacts with alkyl halide causing the carbon-halide bond to break while forming a new carbon nucleophile bond. These two processes occurs at the same time in a single step and no intermediate is formed. As the reaction progresses and the bond between the nucleophile and the carbon atom starts forming and the bond between carbon atom and leaving group starts breaking. Finally, the product formed and the leaving group goes away.

In the transition state, the carbon atom is simultaneously bonded to incoming nucleophile and the leaving group. Such structures formed are unstable and cannot be isolated. This is due to the carbon atom in the transition state is at the same time bonded to five atoms and consequently is unstable.
    
The order of reactivity can be explained in terms of stability of transition state. Bulky alkyl groups attached to the carbon carrying halogen make the transition state unstable due to crowding (steric hindrance and decrease the reactivity of the alkyl halide through SN2mechanism. In 3° alkyl halide three alkyl groups are attached to the carbon carrying halogen. Therefore, transition state in this case has maximum energy and hence the reactivity is least. The 2° alkyl halides with two alkyl groups are most reactive whereas 1° alkyl halide with one alkyl group is most reactive.
    
Starting with an optically active alkyl halide, the reaction through SN2 mechanism results in complete inversion of configuration as it involves attack of nucleophile from backside. For example, when (-) -2-bromoethane is allowed to react with sodium hydroxide, (+)-2-octanol is formed. In (+)-2-octanol the position of -OH group is opposite to what bromide had occupied in (-)-2-bromooctane

   Related Questions in Chemistry

  • Q : Molar concentration Choose the right

    Choose the right answer from following. Molar concentration (M) of any solution : a) No. of moles of solute/Volume of solution in litre (b) No. of gram equivalent of solute / volume of solution in litre (c) No. of moles os solute/ Mass of solvent in kg  (

  • Q : Normality of acetic acid Give me answer

    Give me answer of this question. The normality of 10% (weight/volume) acetic acid is: (a)1 N (b)10 N (c)1.7 N (d) 0.83 N

  • Q : Negative deviation Which one of the

    Which one of the following non-ideal solutions shows the negative deviation: (a) CH3COCH3 + CS2   (b) C6H6 + CH3COCH3   (c) CCl4 + CHCl3  

  • Q : Define tripod and its use Illustrate a

    Illustrate a tripod? And how it’s used?

  • Q : Precipitation problem On passing H 2 S 

    On passing H2S  gas through a solution of Cu+ and Zn+2 ions, CuS is precipitated first because: (i) Solubility product of CuS is equal to the ionic product of ZnS (ii) Solubility product of CuS is equal to the solubility product o

  • Q : Molar solution of sulphuric acid Choose

    Choose the right answer from following. The molar solution of sulphuric acid is equal to: (a) N solution (b) 2Nsolution (c) N/2solution (d) 3Nsolution

  • Q : Amines arrange in decreasing order of

    arrange in decreasing order of basicity pi pyridine,pyridine,pyrrole, morphine

  • Q : Molarity of Sodium hydroxide Select the

    Select the right answer of the question. Molarity of 4% NaOH solution is : (a) 0.1M (b) 0.5M (c) 0.01M (d) 0.05M

  • Q : Freezing point of equimolal aqueous

    The freezing point of equi-molal aqueous solution will be maximum for:            (a) C6H5NH3+Cl-(aniline hydrochloride)  (b) Ca(NO3

  • Q : Colligative property related question

    Select the right answer of the question. Which of the following is not a colligative property : (a) Osmotic pressure (b) Elevation in B.P (c) Vapour pressure (d) Depression in freezing point