Solutions_Manual_for_Organic_Chemistry_6th_Ed 83

Solutions_Manual_for_Organic_Chemistry_6th_Ed 83 - In...

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4-50 Two mechanisms are possIble depending on whether HO' reacts with chLorIne or wI±h cyc!opentane. MechanIs² 1 1 < 1) HO-O³ 2 HO' InItia±Ion (2) HO' + Cl ´Cl ²³ µO-C¶ + Cl' :> H f) Cl· ¸ ´µ H-¹l + ' propagation H H (4) ¹l ´¹l + ± ²³ ¹l ² + ¹l' Mechanism 2 f ) HOºOH ¶· 2 HO' initiation ³´ ³ µ (2) HO' + ´µ H-OH + H H ¹l ´Cl + ¸¹ · ¸ ¹l· propagatIon ¸¹ ³ (4) ¹l¼ + ´µ H-¹l + D The energies of the propagation steps deter½ne which mechanism Is followed. The bond dIssocia±Ion energY of HO¾¹l is aBout 2±0 kJ/mole (aBout 50 kcal¿mole), makÀng inItIation step ²2) in ²echanism 1 endotheN±ic BY aBoUt 30 kj/mole (aBoUt 8 kcal¿mole)Á
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Unformatted text preview: In mechaNism 2, Initiaion sep 2) Is exotheic BY aBout 0 Kj/mole (24 kcalmole); mecansm 2 is prefeRed 451 C l _ l c: l H + :O H O l : I U I i H H H a carBene 452 This itical eqUation Is the keY to this proBlem 1 G = 1 h T 1 S At 1400 the equiLiBIu constant is 1; therefore c f G = 0 &gt; Assuming f H Is aBout he same at 1400 as it is at caloimeter temperaure -137 k/mole = 140 = 37000 1400 98 /mole (-23 calmole) jmole . . :L : This is a large decrease in entropY consIstent wit two molecules comBining into one 75...
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