Concept explainers
(a)
Interpretation:
The standard enthalpy of reaction has to be calculated using the values of bond dissociation enthalpies.
Concept Introduction:
The value of standard enthalpy change
Where,
(a)
Explanation of Solution
Given reaction (1):
The reaction is given below:
Therefore, standard enthalpy of given reaction is
Given reaction (2):
The reaction is given below:
Therefore, standard enthalpy of given reaction is
(b)
Interpretation:
A pair of chain propagation steps for each reaction has to be proposed; the value of
Concept Introduction:
Radical Bromination: A type of halogenation reaction in which the bromine atom gets bonded with the
Radical reaction of
Stability of Radicals: Radicals are highly unstable due to its unpaired valence electron of an atom.
The increasing order of radical stability is given below,
Benzylic > allylic > tertiary > secondary > primary > methyl
Radical chain reaction:
Initiation reaction:
Chain propagation:
Chain termination:
(b)
Explanation of Solution
Given reaction (1):
The propagation step involves extremely reactive fluorine radicals react towards the propane by abstracting the terminal hydrogen forming primary radical and
Hence, the pair of propagation steps is shown above.
Given reaction (2):
Initiation step involves the homolytic bond cleavage of fluorine molecule by irradiation of light or heat leads to the formation of two Fluorine radicals.
The propagation step involves extremely reactive fluorine radicals react towards the propane by abstracting the secondary hydrogen forming secondary radical and
Hence, the pair of propagation steps is shown above.
Therefore, for each reaction step the value of
(c)
Interpretation:
The regioselectivity of radical fluorination relative to that of radical chlorination and Bromination has to be predicted using Hammond’s postulate.
Concept Introduction:
Radical Bromination: A type of halogenation reaction in which the fluorine atom gets bonded with the alkane or alkyl substituents resulting to the product with added fluorine atom via radical mechanism.
Radical reaction of
Stability of Radicals: Radicals are highly unstable due to its unpaired valence electron of an atom.
The increasing order of radical stability is given below,
Benzylic > allylic > tertiary > secondary > primary > methyl
Radical chain reaction:
Initiation reaction:
Chain propagation:
Chain termination:
(c)
Explanation of Solution
In each radical fluorination sequence, the hydrogen abstraction step is highly exothermic, thus the transition state is reached too early and the transition state more closely resembles the reactant; so the intermediate has very little radical character of product. Therefore, the relative stabilities of primary versus secondary radical is of little of importance in determination of product.
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Chapter 8 Solutions
Organic Chemistry
- Chlorination of 2-butanone yields two isomeric products, each having the molecular formula C4H7ClO. (a) What are these two compounds? (b) Write structural formulas for the enol intermediates that lead to each of these compounds. (c) Using curved arrows, show the flow of electrons in the reaction of each of the enols with Cl2.arrow_forwardUse bond-dissociation enthalpies (Table 4-2, p. 167) to calculate values of ∆H° for the following reactions. (a) CH3¬CH3 + I2 ¡ CH3CH2I + HI(b) CH3CH2Cl + HI ¡ CH3CH2I + HCl(c) (CH3)3C¬OH + HCl ¡ (CH3)3C¬Cl + H2O (d) CH3CH2CH3 + H2 ¡ CH3CH3 + CH4 (e) CH3CH2OH + HBr ¡ CH3CH2¬Br + H2Oarrow_forward(a) What is the standard enthalpy of reaction for the reaction of 1.00 mol of propene with 1.00 mol of hydrogen to yield 1.00 mol of propane. (All gas phase) (b) What is the standard entropy change for the reaction? (c) What is the standard free energy change for the reaction carried out at 400 K? (You cannot use ∆Gfo data from the appendix). (d) Is the reaction spontaneous? (a) (b) (c) (d)arrow_forward
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- Organic ChemistryChemistryISBN:9781305580350Author:William H. Brown, Brent L. Iverson, Eric Anslyn, Christopher S. FootePublisher:Cengage Learning