The reaction is exothermic with $$\Delta$$H$$^\circ$$ = $$-$$25 kcal mol$$-$$1
CH4(g) + Cl2(g) $$\buildrel {hv} \over \longrightarrow $$ CH3Cl(g) + HCl(g)
(a) Initiation step is breaking of Cl$$-$$Cl bond which requires energy and hence, this step is endothermic.
(b) Propagation step involving formation of CH3 is also endothermic as bond between C$$-$$H is breaking.
(c) Propagation step involving formation of CH3Cl is exothermic as bond is formed between C$$-$$Cl
(d) $$\mathop H\limits^ \bullet $$ + $$\mathop {Cl}\limits^ \bullet $$ $$\to$$ HCl, $$\Delta$$H4$$^\circ$$ = $$-$$103 kcal/mol
Enthalpy of reaction, $$\Delta$$H$$^\circ$$ = $$\Delta$$H$$_1^o$$ + $$\Delta$$H$$_2^o$$ + $$\Delta$$H$$_3^o$$ + $$\Delta$$H$$_4^o$$
= 58 + 105 $$-$$ 85 $$-$$ 103
= $$-$$25 kcal mol$$-$$1
Hence, the reaction is exothermic with $$\Delta$$H$$^o$$ = $$-$$25 kcal/mol
Column J Molecule |
Column K BDE (kcal $$mo{l^{ - 1}}$$) |
---|---|
(P) H-CH($$C{H_3}$$)$$_2$$ | (i) 132 |
(Q) H-CH$$_2$$Ph | (ii) 110 |
(R) H-CH=CH$$_2$$ | (iii) 95 |
(S) H-C $$ \equiv $$ CH | (iv) 88 |
A more stable radical means lesser the bond dissociation energy.
Radicals formed are
Radical formed from Q (PhCH2$$-$$H) is most stable due to resonance.
Stability of free radical decreases with increase in % s-character.
P radical $$\to$$ sp3 $$\to$$ % s-character 25%
R radical $$\to$$ sp2 $$\to$$ % s-character 33%
S radical $$\to$$ sp $$\to$$ % s-character 50%
Thus, order of stability of free radical is
Q > P > R > S
Order of bond dissociation energy is
S > R > P > Q
P | Q | R | S |
---|---|---|---|
2 | 3 | 2 | 2 |
P | Q | R | S |
---|---|---|---|
3 | 1 | 1 | 2 |
P | Q | R | S |
---|---|---|---|
2 | 1 | 1 | 3 |
P | Q | R | S |
---|---|---|---|
2 | 3 | 3 | 1 |