‫ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ‪Bond Energies‬‬

‫ﺩﺭ ﻣﻮﺭﺩ ﻣﻮﻟﻜﻮﻝ ﺩﻭ ﺍﺗﻤﻲ ﺍﻧﺮﮊﻱ ﺗﺠﺰﻳﻪ ﻳﺎ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ‪ D‬ﻋﺒﺎﺭﺗﺴﺖ ﺍﺯ ﺗﻐﻴﻴﺮﺍﺕ ﺁﻧﺘﺎﻟﭙﻲ ﻭﺍﻛﻨﺶ‬

‫ﻛﻪ ﺩﺭ ﻃﻲ ﺁﻥ ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﺩﻭ ﻳﺎ ﭼﻨﺪ ﺍﺗﻤﻲ ﺩﺭ ﺣﺎﻟﺖ ﮔﺎﺯﻱ ﺗﺒﺪﻳﻞ ﺑﻪ ﺍﺗﻤﻬﺎﻱ ﻣﺮﺑﻮﻃﻪ ﻣﻲﺷﻮﻧﺪ‪ .‬ﺑﺮﺍﻱ ﻣﺜﺎﻝ‪:‬‬

‫‪H 2 ( g ) → 2H ( g ) , D ( H − H ) = ∆H = 109Kcal / mole‬‬

‫ﻳﺎ ﺑﻪ ﻋﺒﺎﺭﺕ ﺩﻳﮕﺮ‪ ،‬ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ )‪ (D‬ﻋﺒﺎﺭﺗﺴﺖ ﺍﺯ ﻣﻘﺪﺍﺭ ﺍﻧﺮﮊﻱ ﻻﺯﻡ ﺑﺮﺍﻱ ﺷﻜﺴﺘﻦ ﭘﻴﻮﻧﺪ‪.‬‬

‫ﺟﻬﺖ ﻋﻨﺎﺻﺮ ﻭﺍﻗﻊ ﺩﺭ ﺳﺘﻮﻧﻬﺎﻱ ﺟﺪﻭﻝ ﺗﻨﺎﻭﺑﻲ )ﻣﺜﻼﹰ ﻓﻠﺰﺍﺕ ﻗﻠﻴﺎﻳﻲ( ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺑﺎ ﺍﻓﺰﺍﻳﺶ ﻋﺪﺩ ﺍﺗﻤﻲ ﻓﻠـﺰ‬

‫ﻛﺎﻫﺶ ﻣﻲﻳﺎﺑﺪ ﻭ ﺩﺭ ﻣﻮﺭﺩ ﻫﺎﻟﻮﮊﻧﻬﺎ ﻧﻴﺰ ﻫﻤﻴﻨﻄﻮﺭ ﺍﺳﺖ ﻭﻟﻲ ﺩﺭ ﻣﻘﺎﻡ ﻣﻘﺎﻳﺴﻪ ﺑﺎ ﻓﻠﺰﺍﺕ ﻗﻠﻴﺎﻳﻲ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧـﺪﻱ‬

‫ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﺩﻭ ﺍﺗﻤﻲ ﻫﺎﻟﻮﮊﻧﻬﺎ ﺑﻴﺸﺘﺮ ﺍﺳﺖ‪ .‬ﺟـﺪﻭﻝ ﺯﻳـﺮ ﺍﻧـﺮﮊﻱ ﺩﻳـﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﻣﻮﻟﻜﻮﻟﻬـﺎﻱ ﺩﻭ ﺍﺗﻤـﻲ ﺭﺍ‬

‫ﺑﺮﺣﺴﺐ ‪ Kcal/mole‬ﻣﻌﻠﻮﻡ ﻣﻲﺩﺍﺭﺩ‪.‬‬

‫ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﺩﻭ ﺍﺗﻤﻲ‪ D ( X − X ) = Kcal / mol  :‬‬

‫ﻣﻼﺣﻈﻪ ﻣﻲﺷﻮﺩ ﻛﻪ ﺩﺭ ﻣﻮﺭﺩ ﻫﺎﻟﻮﮊﻧﻬﺎﻱ ﻫﻴﺪﺭﻭﮊﻥ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻧﺴﺒﺘﺎﹰ ﺧﻴﻠﻲ ﺯﻳﺎﺩ ﺍﺳﺖ‪ .‬ﺩﺭ ﺍﻳﻦ ﻣﻮﺭﺩ‬

‫ﻧﻴﺰ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺑﺎ ﺍﻓﺰﺍﻳﺶ ﻋﺪﺩ ﺍﺗﻤﻲ ﻛﺎﻫﺶ ﻣﻲﻳﺎﺑﺪ‪.‬‬

‫ﺍﺧﺘﻼﻑ ﺯﻳﺎﺩﻱ ﺩﺭ ﻣﻮﺭﺩ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﻣﺠﺎﻭﺭ ﺑﻬﻢ ﺩﺭ ﺟﺪﻭﻝ ﺗﻨﺎﻭﺑﻲ ﺩﻳﺪﻩ ﻣﻲﺷﻮﺩ‪ ،‬ﻣﺜﻼﹰ ﺩﺭ‬

‫ﻣﻮﺭﺩ ﺍﻛﺴﻴﮋﻥ ﻛﻪ ﻋﺪﺩ ﺍﺗﻤﻲ ﺁﻥ ﻳﻜﻲ ﺑﻴﺸﺘﺮ ﺍﺯ ﺍﺯﺕ ﺍﺳﺖ ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﻣﻮﻟﻜﻮﻝ ‪ O 2‬ﻧﺼﻒ ﺍﻧﺮﮊﻱ‬

‫ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ‪ N 2‬ﻣﻲﺑﺎﺷﺪ ﻭﻟﻲ ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﺁﻥ ﭼﻬﺎﺭ ﺑﺮﺍﺑﺮ ‪ F2‬ﺍﺳﺖ ﻛﻪ ﺩﻟﻴـﻞ ﺍﺻـﻠﻲ ﺁﻥ ﺭﺍ‬

‫ﻣﻲﺗﻮﺍﻥ ﺑﻪ ﻣﺮﺗﺒﻪ ﭘﻴﻮﻧﺪﻱ ﻣﺮﺑﻮﻁ ﺩﺍﻧﺴﺖ‪ .‬ﺑﻪ ﻣﺜﺎﻝ ﺯﻳﺮ ﺗﻮﺟﻪ ﻛﻨﻴﺪ‪.‬‬

‫ﻣﺜﺎﻝ‪ .‬ﺑﺎ ﺭﺳﻢ ﺳﺎﺧﺘﺎﺭ ﻟﻮﺋﻴﺲ ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ‪ N 2 , O 2 , F2‬ﻭ ‪ CO‬ﻋﻠﺖ ﺍﺧﺘﻼﻑ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺁﻧﻬﺎ‬

‫ﺭﺍ ﻣﺸﺨﺺ ﻛﻨﻴﺪ‪.‬‬

‫ﺣﻞ ﺑﺎ ﺍﺳﺘﻔﺎﺩﻩ ﺍﺯ ﻗﻮﺍﻋﺪ ﺭﺳﻢ ﺳﺎﺧﺘﺎﺭ ﻟﻮﺋﻴﺲ‪ ،‬ﺁﺭﺍﻳﺸﻬﺎﻱ ﺯﻳﺮ ﺑﺪﺳﺖ ﻣﻲﺁﻳﺪ‪.‬‬

‫ﻫﻤﭽﻨﺎﻥ ﻛﻪ ﺳﺎﺧﺘﺎﺭﻫﺎﻱ ﻟﻮﺋﻴﺲ ﻧﺸﺎﻥ ﻣﻲ ﺩﻫﺪ ﭼﻮﻥ ﻣﺮﺗﺒﻪ ﭘﻴﻮﻧﺪﻱ ﺩﺭ ‪ CO‬ﻭ ‪ N 2‬ﺑﻴـﺸﺘﺮ ﺍﺳـﺖ ﺍﻧـﺮﮊﻱ‬

‫ﭘﻴﻮﻧﺪﻱ ﺁﻧﻬﺎ ﺑﻴﺸﺘﺮ ﺍﺯ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ‪ F2 ,O 2‬ﻣﻲﺑﺎﺷﺪ‪ .‬ﭘﻴﻮﻧﺪ ﺩﻭﮔﺎﻧﻪ ﺩﺭ ‪ O 2‬ﻣﻮﺟﺐ ﻣﻲﺷﻮﺩ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ‬

‫ﺁﻥ ﺍﺯ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺳﺎﺩﻩ ﻣﻮﻟﻜﻮﻝ ‪ F2‬ﺑﻴﺸﺘﺮ ﺑﺎﺷﺪ‪.‬‬

‫ﺗﻤﺮﻳﻦ‪ .‬ﺑﺮﺍﺳﺎﺱ ﺳﺎﺧﺘﺎﺭ ﻟﻮﺋﻴﺲ‪ ،‬ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺭﺍ ﺩﺭ ﮔﻮﻧﻪﻫﺎﻱ ﺷﻴﻤﻴﺎﻳﻲ‪،‬‬

‫ﺏ‪ CN − ,CN .‬ﻭ ﺝ‪ NO + , NO .‬ﺑﺎ ﻳﻜﺪﻳﮕﺮ ﻣﻘﺎﻳﺴﻪ ﻛﻨﻴﺪ‪.‬‬ ‫ﺍﻟﻒ‪، O 2− ,O 2 .‬‬

‫ﻋﻼﻭﻩ ﺑﺮ ﻣﺮﺗﺒﻪ ﭘﻴﻮﻧﺪ ﻋﺎﻣﻠﻲ ﺩﻳﮕـﺮﻱ ﻛـﻪ ﺩﺭ ﺍﻧـﺮﮊﻱ ﭘﻴﻮﻧـﺪﻱ ﻣـﺆﺛﺮ ﺍﺳـﺖ ﺟـﺮﻡ ﺍﺗﻤـﻲ ﺍﺗﻤﻬـﺎﻱ‬

‫ﺗﺸﻜﻴﻞﺩﻫﻨﺪﻩ ﭘﻴﻮﻧﺪ ﻣﻲﺑﺎﺷﺪ‪ .‬ﺑﺎ ﻛﺎﻫﺶ ﺟﺮﻡ ﺍﺗﻤﻲ‪ 1‬ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺍﻓﺰﺍﻳﺶ ﻣﻲﻳﺎﺑﺪ‪ .‬ﻳﻜـﻲ ﺍﺯ ﺩﻻﻳﻠـﻲ ﻛـﻪ‬

‫ﻣﻮﺟﺐ ﻣﻲ ﺷﻮﺩ ‪ H 2‬ﻗﻮﻳﺘﺮﻳﻦ ﭘﻴﻮﻧﺪ ﺳﺎﺩﻩ ﺩﺭ ﺑﻴﻦ ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﺩﻭ ﺍﺗﻤﻲ ﺟﻮﺭ ﻫﺴﺘﻪ ﺭﺍ ﺩﺍﺷﺘﻪ ﺑﺎﺷـﺪ‪ .‬ﺟـﺮﻡ‬

‫ﺍﺗﻤﻲ ﺑﺴﻴﺎﺭ ﻛﻮﭼﻚ ﺍﺗﻤﻬﺎﻱ ﻫﻴﺪﺭﻭﮊﻥ ﺍﺳﺖ‪ .‬ﻭﺍﺑﺴﺘﮕﻲ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺑـﻪ ﺟـﺮﻡ ﺭﺍ ﺩﺭ ﻗـﺪﺭﺕ ﭘﻴﻮﻧـﺪﻱ ﺩﺭ‬

‫ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﺩﻭ ﺍﺗﻤﻲ ﻫﺎﻟﻮﮊﻧﻬﺎ )ﺑﻪ ﺍﺳﺘﺜﻨﺎﻱ ‪ ( F2‬ﺑﻪ ﺧﻮﺑﻲ ﻣﻲﺗﻮﺍﻥ ﺩﻳﺪ‪ .‬ﻋﺎﻣﻠﻲ ﻛـﻪ ﻣﻮﺟـﺐ ﻛـﺎﻫﺶ ﺍﻧـﺮﮊﻱ‬

‫ﭘﻴﻮﻧﺪﻱ ﺩﺭ ﻣﻮﻟﻜﻮﻝ ‪ F2‬ﻣﻲﮔﺮﺩﺩ‪ .‬ﺩﺍﻓﻌﻪ ﺷﺪﻳﺪ ﺟﻔﺘﻬﺎﻱ ﻏﻴﺮﭘﻴﻮﻧﺪﻱ ﺩﺭ ﻓﺎﺻﻠﻪ ﻃﻮﻝ ﭘﻴﻮﻧﺪﻱ ﻧﺴﺒﺘﺎﹰ ﻛﻮﭼـﻚ‬

‫‪ F-F‬ﻣﻲﺑﺎﺷﺪ‪.‬‬

‫ﻫﻤﭽﻨﻴﻦ ﺩﺍﺩﻩﻫﺎﻱ ﺟﺪﻭﻝ ﻧﺸﺎﻥ ﻣﻲﺩﻫﺪ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ‪ HF‬ﺑـﺴﻴﺎﺭ ﺑﻴـﺸﺘﺮ ﺍﺯ ﻣﻴـﺎﻧﮕﻴﻦ ﺍﻧﺮﮊﻳﻬـﺎﻱ‬

‫ﭘﻴﻮﻧﺪﻱ ‪ F2 , H 2‬ﺍﺳﺖ‪ .‬ﺍﻳﻦ ﺗﻔﺎﻭﺕ ﺍﺯ ﻗﻄﺒﻴﺖ ﭘﻴﻮﻧﺪ ‪ HF‬ﻧﺎﺷﻲ ﻣﻲﺷﻮﺩ‪ .‬ﺍﺧﺘﻼﻑ ﺍﻟﻜﺘﺮﻭﻧﮕـﺎﺗﻴﻮﻱ ﺩﻭ ﺍﺗـﻢ‬

‫ﻣﻮﺟﺐ ﺍﻳﺠﺎﺩ ﺑﺎﺭﻫﺎﻱ ﻳﻜﺴﺎﻥ ﻏﻴﺮﻫﻤﻨﺎﻡ ﺑﺮ ﺭﻭﻱ ﺩﻭ ﺍﺗﻢ ﻣﻲﺷﻮﺩ‪ .‬ﺟﺎﺫﺑﻪ ﺣﺎﺻﻞ ﺍﺯ ﺍﻳﻦ ﺑﺎﺭﻫـﺎ ﻣﻮﺟـﺐ ﻛﻮﺗـﺎﻩ‬

‫ﺷﺪﻥ ﻃﻮﻝ ﭘﻴﻮﻧﺪ ﻭ ﺩﺭ ﻧﺘﻴﺠﻪ ﺍﻓﺰﺍﻳﺶ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﻣﻲﮔﺮﺩﺩ‪.‬‬

‫ﺑﻨﺎﺑﺮﺍﻳﻦ ﻧﻈﺮﻳﻪ ﭘﻴﻮﻧﺪﻫﺎ ﺑﻪ ﺭﻭﺷﻲ ﺳﺎﺩﻩ ﺭﺍﺑﻄﻪ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺑﻌﻀﻲ ﺍﺯ ﻣﻮﻟﻜﻮﻟﻬﺎ ﺭﺍ ﺑﺎ ﻳﻜﺪﻳﮕﺮ ﺑﺮﺍﻱ ﻣـﺎ‬

‫ﺗﻔﺴﻴﺮ ﺧﻮﺍﻫﺪ ﻛﺮﺩ‪ .‬ﮔﺎﻫﻲ ﺍﻭﻗﺎﺕ ﻣﻤﻜﻦ ﺍﺳﺖ ﺷﻜﺴﺘﻦ ﭘﻴﻮﻧﺪ ﺳﺒﺐ ﺑﻮﺟﻮﺩ ﺁﻣـﺪﻥ ﺭﺍﺩﻳﻜـﺎﻝ ﻳـﺎ ﺑﺨـﺸﻲ ﺍﺯ‬

‫ﻣﻮﻟﻜﻮﻝ ﮔﺮﺩﺩ‪ ،‬ﻣﺜﻼﹰ‪ :‬ﺩﺭ ﺍﺛﺮ ﺷﻜﺴﺘﻦ ﻣﻮﻟﻜﻮﻝ ﺁﺏ ﺭﺍﺩﻳﻜﺎﻟﻬﺎﻱ ‪ OH‬ﻭ ‪ H‬ﺗﻮﻟﻴﺪ ﻣﻲﺷﻮﺩ‪.‬‬

‫ﺑﻪ ﻃﻮﺭ ﺩﻗﻴﻖﺗﺮ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺑﻪ ﻣﻌﻜﻮﺱ ﺟﺮﻡ ﻛﺎﻫﺶ ﻳﺎﻓﺘﻪ ﺭﺑﻂ ﺩﺍﺭﺩ‪ .‬ﺟﺮﻡ ﻛﺎﻫﺶ ﻳﺎﻓﺘﻪ ﻣﻮﻟﻜﻮﻝ ﺩﻭ ﺍﺗﻢ ‪ AB‬ﺑﻪ‬ ‫‪1‬‬

‫‪mA × mB‬‬
‫=‪µ‬‬ ‫ﺻﻮﺭﺕ ﺭﻭﺑﺮﻭ ﺗﻌﺮﻳﻒ ﻣﻲ ﺷﻮﺩ‪.‬‬
‫‪mA + mB‬‬
‫) ‪H 2O ( g ) → H ( g ) + OH ( g‬‬

‫‪D (H − OH ) = 119 / 7 Kcal / mole‬‬

‫ﻭ ﮔﺎﻫﻲ ﺍﻭﻗﺎﺕ ﻧﻴﺰ ﺷﻜﺴﺘﻦ ﻳﻚ ﭘﻴﻮﻧﺪ ﻣﻤﻜﻦ ﺍﺳﺖ ﺩﻭ ﺭﺍﺩﻳﻜﺎﻝ ﻣﺸﺎﺑﻪ ﺗﻮﻟﻴﺪ ﻧﻤﺎﻳﺪ‪:‬‬

‫) ‪HO − OH ( g ) → 2OH ( g‬‬

‫‪D (HO − OH ) = 48 Kcal / mole‬‬

‫ﺍﮔﺮ ﭘﻴﻮﻧﺪ ﺑﻴﻦ ﺩﻭ ﺍﺗﻢ ﻣﺸﺨﺺ ﻧﻈﻴﺮ ‪ H‬ﻭ ‪ C‬ﻛﻪ ﺩﺭ ﻣﻮﻟﻜﻮﻟﻬﺎﻱ ﻣﺨﺘﻠﻒ ﻭﺟﻮﺩ ﺩﺍﺭﻧﺪ‪ ،‬ﺩﺭ ﻧﻈﺮ ﮔﺮﻓﺘﻪ ﺷﻮﺩ‪ ،‬ﺑﺎﻳﺪ‬

‫ﺗﺄﺛﻴﺮ ﻣﻮﻟﻜﻮﻝ ﺩﻳﮕﺮ ﭘﻴﻮﻧﺪ ﺷﺪﻩ ﺑﺎ ‪ C‬ﺭﺍ ﺑﺮ ﺭﻭﻱ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﻄﺎﻟﻌﻪ ﻧﻤﻮﺩ‪ .‬ﻣﺜﻼﹰ‪ :‬ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ) ‪ (C − H‬ﺟﻔﺖ‬

‫ﻫﻴﺪﺭﻭﻛﺮﺑﻮﺭﻫﺎﻱ ﻣﺨﺘﻠﻒ ﻋﺒﺎﺭﺗﺴﺖ ﺍﺯ‪:‬‬

‫) ‪CH 4 ( g ) → CH 3 ( g ) + H ( g‬‬

‫‪D (H − CH 3 ) = 103 Kcal / mole‬‬

‫) ‪CH 3CH 3 ( g ) → CH 3CH 2 ( g ) + H ( g‬‬

‫‪D (H − CH 2CH 3 ) = 96 Kcal / mole‬‬

‫) ‪(CH 3 )3CH → (CH 3 )3C ( g ) + H ( g‬‬

‫‪D H − C (CH 3 )3  = 90 Kcal / mole‬‬

‫ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﺍﺗﺼﺎﻟﻬﺎﻱ ‪ C-H‬ﺩﺭ ﺗﺮﻛﻴﺒﺎﺕ ﺩﻳﮕﺮ‪ ،‬ﺑﻴﻦ ‪ 90‬ﺗﺎ ‪ 103‬ﻛﻴﻠﻮﻛﺎﻟﺮﻱ ﺍﺳﺖ‪ .‬ﻛـﻪ ﺩﺭ‬

‫ﺟﺪﻭﻝ ﻣﻴﺎﻧﮕﻴﻦ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪﻱ ﺩﺭﺝ ﻣﻲﺷﻮﺩ‪.‬‬

‫ﺛﺒﺎﺕ ﺗﻘﺮﻳﺒﻲ ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﻳﺎ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﻔﻬﻮﻡ ﺟﺎﻟﺒﻲ ﺩﺍﺭﺩ‪ ،‬ﺯﻳﺮﺍ ﺩﺭ ﻭﺍﻗﻊ ﻧـﺸﺎﻥﺩﻫﻨـﺪﻩ‬

‫ﺍﻳﻦ ﺍﺳﺖ ﻛﻪ ﺧﺼﻮﺻﻴﺎﺕ ﺍﺻﻠﻲ ﺩﻭ ﺍﺗﻢ ﺑﻮﺟﻮﺩ ﺁﻭﺭﻧﺪﻩ ﭘﻴﻮﻧﺪ ﻋﺎﻣﻞ ﺍﺻﻠﻲ ﺗﻌﻴﻴﻦﻛﻨﻨﺪﻩ ﻣﻘﺪﺍﺭ ﺍﻧـﺮﮊﻱ ﭘﻴﻮﻧـﺪ‬

‫ﺍﺳﺖ‪ .‬ﺩﺭ ﺣﻘﻴﻘﺖ ﺍﺗﻤﻬﺎ ﻭ ﻳﺎ ﺭﺍﺩﻳﻜﺎﻟﻬﺎﻱ ﻣﺘﺼﻞ ﺑﻪ ﺑﻘﻴﻪ ﻣﻮﻟﻜﻮﻝ ﺗﺄﺛﻴﺮ ﻛﻤﻲ ﺩﺭ ﻣﻘﺪﺍﺭ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺍﻳﻦ ﺩﻭ ﺍﺗﻢ‬
‫ﺑﺨﺼﻮﺹ ﺩﺍﺭﻧﺪ‪ .‬ﺑﻨﺎﺑﺮﺍﻳﻦ‪ ،‬ﻟﺰﻭﻡ ﺍﻳﺠﺎﺩ ﻳﻚ ﻧﻈﺮﻳﻪ ﻛﻪ ﻗﺎﺩﺭ ﺑﻪ ﺗﻮﺟﻴﻪ ﻣﺸﺨﺼﺎﺕ ﭘﻴﻮﻧـﺪ ﺷـﻴﻤﻴﺎﻳﻲ ﺑﺮﺣـﺴﺐ‬

‫ﺧﻮﺍﺹ ﺍﺻﻠﻲ ﺍﺗﻤﻬﺎﻱ ﻣﺘﺼﻠﻪ ﺑﺎﺷﺪ‪ ،‬ﺍﺣﺴﺎﺱ ﻣﻲﮔﺮﺩﺩ‪.‬‬

‫ﻛﺎﺭﺑﺮﺩ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ‪Use of Bond Energies‬‬

‫ﺍﺯ ﻧﻈﺮ ﻋﻤﻠﻲ ﺛﺒﺎﺕ ﺗﻘﺮﻳﺒﻲ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺩﺭ ﺗﺮﻛﻴﺒﺎﺕ ﻣﺨﺘﻠﻒ ﻧﺘﻴﺠﻪ ﻣﻬﻤﻲ ﺩﺍﺭﺩ‪ ،‬ﺯﻳﺮﺍ ﻣﻲﺗـﻮﺍﻥ ﻳـﻚ‬

‫ﭘﻴﻮﻧﺪ ﺑﺨﺼﻮﺹ )ﻣﺜﻼﹰ ‪ (C-H‬ﻳﺎ ﻫﺮ ﭘﻴﻮﻧﺪ ﺩﻳﮕﺮ ﺍﺯ ﺍﻳﻦ ﻧﻮﻉ ﺭﺍ ﺑﻪ ﻭﺳﻴﻠﻪ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﺘﻮﺳﻂ ﻣﺸﺨﺺ ﻛـﺮﺩ‪،‬‬

‫ﻛﻪ ﻋﺒﺎﺭﺗﺴﺖ ﺍﺯ ﺍﻧﺮﮊﻱ ﺗﻘﺮﻳﺒﻲ ﻻﺯﻡ ﺑﺮﺍﻱ ﺷﻜﺴﺘﻦ ﺍﺗﺼﺎﻝ ﺩﺭ ﻫﺮ ﺗﺮﻛﻴﺒﻲ ﻛﻪ ﺍﻳﻦ ﺍﺗﺼﺎﻝ ﺩﺭ ﺁﻥ ﻭﺟـﻮﺩ ﺩﺍﺭﺩ‪.‬‬

‫ﺍﺧﺘﻼﻑ ﺍﻧﺮﮊﻱ ﻣﺘﻮﺳﻂ )‪ (E‬ﺑﺎ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺩﺭ ﺍﻳﻦ ﺍﺳﺖ ﻛﻪ ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﻋﺒﺎﺭﺗﺴﺖ ﺍﺯ ﻣﻘﺪﺍﺭ ﺍﻧﺮﮊﻱ‬

‫ﻛﻪ ﺑﺎﻳﺪ ﺑﻪ ﻳﻚ ﺗﺮﻛﻴﺐ ﻣﺸﺨﺺ ﺩﺍﺩ ﺗﺎ ﺍﺗﺼﺎﻝ ﺑﺨﺼﻮﺹ ﺁﻥ ﺷﻜﺴﺘﻪ ﺷﻮﺩ ﻭ ﺣﺎﻝ ﺁﻧﻜﻪ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﺘﻮﺳـﻂ‬

‫ﻣﺮﺑﻮﻁ ﺑﻪ ﻛﻠﻴﻪ ﺗﺮﻛﻴﺒﺎﺗﻲ ﻣﻲﺷﻮﺩ ﻛﻪ ﺍﻳﻦ ﭘﻴﻮﻧﺪ ﺑﺨﺼﻮﺹ ﺩﺭ ﺁﻥ ﻭﺟﻮﺩ ﺩﺍﺭﺩ‪ .‬ﺟﺪﻭﻝ ﺯﻳﺮ ﻓﻬﺮﺳﺘﻲ ﺍﺯ ﺍﻧـﺮﮊﻱ‬

‫ﭘﻴﻮﻧﺪ ﻣﺘﻮﺳﻂ ﺭﺍ ﻧﺸﺎﻥ ﻣﻲﺩﻫﺪ‪.‬‬

‫ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﺘﻮﺳﻂ ﺟﻬﺖ ﭘﻴﻮﻧﺪﻫﺎﻱ ﺳﺎﺩﻩ ﻭ ﻣﺮﻛﺐ ﺑﺮﺣﺴﺐ ‪K cal/mole‬‬

‫ﺑﺎ ﺑﻜﺎﺭ ﺑﺮﺩﻥ ﺍﻧﺮﮊﻱ ﻣﺘﻮﺳﻂ ﭘﻴﻮﻧﺪ ﻣﻲﺗﻮﺍﻥ ﺍﻧﺮﮊﻱ ﺁﺯﺍﺩ ﺷﺪﻩ ﺭﺍ ﺩﺭ ﻣﻮﻗﻊ ﺗﺸﻜﻴﻞ ﻳﻚ ﻣﻮﻟﻜﻮﻝ ﮔـﺎﺯﻱ‬

‫ﺍﺯ ﺍﺗﻤﻬﺎﻱ ﮔﺎﺯﻱ ﺍﻭﻟﻴﻪﺍﺵ ﺗﺨﻤﻴﻦ ﺯﺩ‪ .‬ﻣﺜﻼﹰ ‪ ∆H‬ﻳﺎ ﺍﻧﺮﮊﻱ ﺁﺯﺍﺩ ﺷﺪﻩ ﺩﺭ ﻓﺸﺎﺭ ﺛﺎﺑﺖ ﺭﺍ ﺑﺮﺍﻱ ﻭﺍﻛﻨﺶ ﺯﻳﺮ ﺑﺪﻳﻦ‬

‫ﺗﺮﺗﻴﺐ ﺣﺴﺎﺏ ﻣﻲﻛﻨﻨﺪ‪.‬‬

‫‪H‬‬

‫) ‪3H ( g ) + C ( g ) + Cl ( g ) → H − C − Cl ( g‬‬

‫‪H‬‬

‫‪ ∆H‬ﺑﺮﺍﺑﺮ ﺍﺳﺖ ﺑﺎ ﻣﺠﻤﻮﻉ ﺍﻧﺮﮊﻳﻬﺎﻱ ﺳﻪ ﺍﺗﺼﺎﻝ ‪ C-H‬ﻭ ﻳﻚ ﺍﺗﺼﺎﻝ )‪ (C-Cl‬ﻭ ﭼﻮﻥ ﺳﻴﺴﺘﻢ ﻓـﻮﻕ‬

‫ﺍﻧﺮﮊﻱ ﺍﺯ ﺩﺳﺖ ﺩﺍﺩﻩ ﺍﺳﺖ ﻟﺬﺍ ‪ ∆Η‬ﺑﺎ ﻋﻼﻣﺖ ﻣﻨﻔﻲ ﻧﺸﺎﻥ ﺩﺍﺩﻩ ﻣﻲﺷﻮﺩ‪.‬‬

‫‪∆Η = −3E (C − H ) − E (C − Cl ) = −294 − 80 = −374 Kcal / mole‬‬

‫ﺑﺮﺍﻱ ﭘﻴﺪﺍ ﻛﺮﺩﻥ ‪ ∆Η‬ﻣﺮﺑﻮﻁ ﺑﻪ ﺗﺸﻜﻴﻞ ‪ CH 3Cl‬ﺍﺯ ﻋﻨﺎﺻﺮ ﻛﻠﺮ ﻭ ﻛﺮﺑﻦ ﻭ ﻫﻴﺪﺭﻭﮊﻥ ﺑﺎﻳﺴﺘﻲ ﺭﺍﺑﻄﻪ ﺯﻳـﺮ ﺭﺍ‬

‫ﻧﻮﺷﺖ‪:‬‬

‫‪1‬‬
‫) ‪3 / 2 H 2 ( g ) + Cl 2 ( g ) + C ( graphite ) → CH 3Cl ( g‬‬
‫‪2‬‬

‫ﺍﻳﻦ ﻭﺍﻛﻨﺶ ﺩﺭ ﺣﻘﻴﻘﺖ ﻣﺠﻤﻮﻉ ﺩﻭ ﻭﺍﻛﻨﺶ ﺯﻳﺮ ﻣﻲﺑﺎﺷﺪ‪.‬‬

‫‪1‬‬
‫→ ) ‪3 / 2 H 2 ( g ) + Cl 2 + C ( graphite‬‬
‫‪2‬‬

‫) ‪= 3H ( g ) + Cl ( g ) + C ( g‬‬

‫) ‪3H ( g ) + Cl ( g ) + C ( g ) → CH 3Cl ( g‬‬

‫‪∆Η = −374Kcal / mole‬‬

‫ﻣﻘﺪﺍﺭ ‪ ∆Η‬ﺭﺍ ﺑﺮﺍﻱ ﻭﺍﻛﻨﺶ ﮔﺎﺯﻱ ﻣﻌﻴﻦ ﻛﺮﺩﻳﻢ ﻭﻟﻲ ﺑﺮﺍﻱ ﻭﺍﻛﻨﺶ ﺑﻌﺪﻱ ‪ ∆Η‬ﺭﺍ ﻣﻲﺗـﻮﺍﻥ ﺑﺮﺣـﺴﺐ‬

‫ﺍﻧﺮﮊﻱ ﺩﻳﺴﻮﺳﻴﺎﺳﻴﻮﻥ ﭘﻴﻮﻧﺪ ‪ H 2 ,Cl 2‬ﻭ ﮔﺮﻣﺎﻱ ﺗﺒﺨﻴﺮ ﮔﺮﺍﻓﻴﺖ ﺑﻪ ﺍﺗﻢ ﻛـﺮﺑﻦ ﮔـﺎﺯﻱ ﻣﺤﺎﺳـﺒﻪ ﻧﻤـﻮﺩ ﻛـﻪ‬

‫ﻋﺒﺎﺭﺗﺴﺖ ﺍﺯ‪:‬‬

‫= ) ‪∆Η = 3 / 2 D ( H − H ) + 1 / 2 D (Cl − Cl ) + ∆Η v (C‬‬

‫‪3 / 2(104) + 1 / 2(57 / 9) + 170 / 9 = 351 Kcal‬‬

‫ﻭ ﺑﺎﻻﺧﺮﻩ ﺑﺮﺍﻱ ﻭﺍﻛﻨﺶ ﻣﺠﻤﻮﻉ‪:‬‬

‫) ‪3 / 2 H 2 ( g ) + 1 / 2Cl 2 ( g ) + C ( graphite ) → CH 3Cl ( g‬‬

‫‪∆Η = −374 + 356 = −18Kcal / mole‬‬

‫ﻣﻘﺪﺍﺭ ‪ ∆Η‬ﺑﺪﺳﺖ ﺁﻣﺪﻩ ﺑﻪ ﻭﺳﻴﻠﻪ ﻛﺎﻟﺮﻳﻤﺘﺮﻫﺎﻱ ﺧﻴﻠﻲ ﺩﻗﻴﻖ ﺑﺮﺍﺑﺮ ﺍﺳـﺖ ﺑـﺎ ‪ -19/6 Kcal/mole‬ﻭ‬

‫ﺑﻴﺎﻥ ﻣﻲﻛﻨﺪ ﻛﻪ )‪ (E‬ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﻣﺘﻮﺳﻂ ﺭﺍ ﻣﻲﺗﻮﺍﻥ ﺑﺎ ﺟﺰﺋﻲ ﺗﻘﺮﻳﺐ ﺑﻪ ﺟﺎﻱ ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺟﺎﻧﺸﻴﻦ ﻛﺮﺩ‪ .‬ﺍﺯ‬

‫ﺍﻧﺮﮊﻱ ﭘﻴﻮﻧﺪ ﺑﺮﺍﻱ ﻣﺤﺎﺳﺒﻪ ﮔﺮﻣﺎﻱ ﺍﻳﺠﺎﺩ ﺷﺪﻩ ﺩﺭ ﻭﺍﻛﻨﺸﻬﺎﻱ ﻣﺨﺘﻠﻒ ﻫﻨﮕﺎﻣﻲ ﻛﻪ ﺑﻪ ﻭﺳـﺎﺋﻞ ﺍﻧـﺪﺍﺯﻩﮔﻴـﺮﻱ‬

‫)ﻛﺎﻟﺮﻳﻤﺘﺮﻱ( ﺩﺳﺘﺮﺳﻲ ﻧﺒﺎﺷﺪ ﺍﺳﺘﻔﺎﺩﻩ ﻣﻲﮔﺮﺩﺩ‪.‬‬