04 - أثر الحرارة على سرعة التفاعلات الكيميائية

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬
‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ‬
‫ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ‬
‫ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬
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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ‬
‫ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬
‫ﻣﻘﺪﻣﺔ‬
‫ﻋﺎﻟﺠﻨﺎ ﻓﯿﻤﺎ ﺳﺒﻖ اﻟﺤﺮﻛﯿ ﺔ اﻟﻜﯿﻤﯿﺎﺋﯿ ﺔ ﻣ ﻦ ﻣﻨﻈ ﻮر اﻟﺘﻐﯿ ﺮ ﻓ ﻲ اﻟﺘﺮﻛﯿ ﺰ‬

‫ﻣﻊ اﻟﺰﻣﻦ ﺣﯿﺚ ﻧﻈﺮﻧﺎ إﻟﻰ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﻋﻠ ﻰ أﻧ ﮫ ﻣﺠﻤﻮﻋ ﺔ ﻣ ﻦ‬
‫اﻟﻤﺘﻔ ﺎﻋﻼت ﺗﻌﻄ ﻲ ﻧ ﻮاﺗﺞ‪ ،‬ﻟﻜ ﻦ اﻟﺠ ﺰء اﻷﻛﺜ ﺮ دﻗ ﺔ أن ﻧﻨﻈ ﺮ اﻟ ﻰ‬
‫اﻟﺘﻔﺎﻋﻞ ﻋﻠﻰ اﻟﻤﺴ ﺘﻮى اﻟﺠﺰﯾﺌ ﻲ وﺗ ﺄﺛﯿﺮ ھ ﺬه اﻟﺠﺰﯾﺌ ﺎت ﻋﻠ ﻰ ﺣﺮﻛﯿ ﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ ﻣﻤ ﺎ ﯾﻤﻜﻨﻨ ﺎ ﻣ ﻦ ﻣﻌﺮﻓ ﺔ اﻟﻨﻈﺮﯾ ﺎت اﻟﺘ ﻲ ﺗﻘ ﻮم ﻋﻠﯿﮭ ﺎ ﺣﺮﻛﯿ ﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﺑﺸ ﻜﻞ ﻋ ﺎم وأﺻ ﻞ ھ ﺬه اﻟﻨﻈﺮﯾ ﺎت ﻣﻌﺮﻓ ﺔ ﺗ ﺄﺛﯿﺮ‬
‫درﺟﺔ اﻟﺤﺮارة ﻋﻠﻰ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ‪.‬‬
‫ﺗﺄﺛﲑ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬
‫• ﻟﻘﺪ ﻻﺣﻈﻨﺎ أﻧﻨﺎ ﺗﻌﺎﻣﻠﻨﺎ ﻓﻲ اﻟﻔﺼﻮل اﻟﺴﺎﺑﻘﺔ ﻣﻊ اﻟﺠﺰﯾﺌﺎت اﻟﻤﺘﻔﺎﻋﻠﺔ‬

‫ﻋﻠﻰ أﻧﮭﺎ ﻣﺘﻤﺎﺛﻠﺔ اﻷﻣﺮ اﻟ ﺬي ﯾﻘﻮدﻧ ﺎ إﻟ ﻰ اﻟﻘ ﻮل أﻧﮭ ﺎ ﺗﺘﻔﺎﻋ ﻞ ﺑ ﻨﻔﺲ‬
‫اﻟﻄﺮﯾﻘﺔ وﻧﻔﺲ اﻟﺴﺮﻋﺔ ﻋﻨﺪ اﻟﻈﺮوف اﻟﻤﺤ ﺪدة اﻷﻣ ﺮ اﻟ ﺬي ﯾﻘﻮدﻧ ﺎ‬
‫اﻟﻰ اﻟﺘﺴﺎؤل ‪ :‬ﻟﻤﺎذا ﺗﻨﺘﻈﺮ ﺑﻌ ﺾ اﻟﺠﺰﯾﺌ ﺎت زﻣﻨ ﺎ ً ﺣﺘ ﻰ ﺗﺼ ﻞ اﻟ ﻰ‬
‫ﻧﻮاﺗﺞ؟ وﯾﻘﻮدﻧﺎ ھﺬا اﻟﺘﺴ ﺎؤل إﻟ ﻰ اﻻﺳ ﺘﻨﺘﺎج ﺑ ﺄن اﻟﺠﺰﯾﺌ ﺎت ﻟﯿﺴ ﺖ‬

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‫ﻣﺘﻤﺎﺛﻠﺔ ﺑﺸﻜﻞ ﻛﻠﻲ وإﻻ ﻟﺤﺪث اﻟﺘﻔﺎﻋﻞ ﻟﮭﺬه اﻟﺠﺰﯾﺌﺎت ﺑﻨﻔﺲ اﻟﻮﻗﺖ‬
‫أي ﺑﺸﻜﻞ ﻟﺤﻈﻲ وھﺬا ﻣﺎ ﺗﻨﻔﯿﮫ اﻟﺘﺠﺮﺑﺔ‪.‬‬
‫• وﻧﻌﻠﻢ أﻧﮫ ﻟﻜﻲ ﺗﺘﻔﺎﻋﻞ اﻟﺠﺰﯾﺌﺎت ﻓﺈﻧﮫ ﯾﺠ ﺐ ﻋﻠﯿﮭ ﺎ أن ﺗﺘﺼ ﺎدم‪ .‬ﻓﻠ ﻮ‬
‫ﻧﻈﺮﻧ ﺎ إﻟ ﻰ اﻟﺠﺰﯾﺌ ﺎت اﻟﻐﺎزﯾ ﺔ ﺳ ﻨﻼﺣﻆ أﻧ ﮫ ﻣ ﻊ ﺳ ﺮﻋﺘﮭﺎ اﻟﻌﺎﻟﯿ ﺔ‬
‫وﺳﯿﺮھﺎ ﺑﺸ ﻜﻞ ﻋﺸ ﻮاﺋﻲ‪ ،‬ﻣﻤ ﺎ ﯾ ﻮﺣﻲ ﺑ ﺄن ھﻨ ﺎك ﺗﺼ ﺎدﻣﺎت ﻛﺜﯿ ﺮة‬
‫ﺑﯿﻦ اﻟﺠﺰﯾﺌﺎت‪ ،‬إﻻ أن ﺳﺮﻋﺔ ﺑﻌﺾ اﻟﺘﻔﺎﻋﻼت اﻟﻐﺎزﯾﺔ ﺑﻄﯿﺌﺔ ﺟ ﺪاً‪.‬‬
‫ھﺬا ﯾﻌﻨﻲ أن ﻛﻞ اﻟﺘﺼﺎدﻣﺎت ﻻ ﯾﻨﺘﺞ ﻋﻨﮭﺎ ﺑﺎﻟﻀﺮورة ﻧ ﻮاﺗﺞ أو أن‬
‫ﻋﻠ ﻰ ﺑﻌ ﺾ اﻟﺠﺰﯾﺌ ﺎت أن ﺗﻨﺘﻈ ﺮ وﻗﺘ ﺎ ً أط ﻮل ﻣ ﻦ اﻟ ﺒﻌﺾ اﻵﺧ ﺮ‬
‫ﺣﺘﻰ ﺗﺘﺴﺒﺐ ﺑﺤﺪوث ﻧﻮاﺗﺞ ﻓﻜﯿﻒ ﯾﺤﺪث ذﻟﻚ؟‬
‫• ﻓ ﻲ ﻋ ﺎم )‪ 1897‬م( ﺣ ﻞ اﻟﻌ ﺎﻟﻢ أرھﯿﻨﯿ ﻮس ھ ﺬا اﻟﻠﻐ ﺰ ﺑﻔ ﺮض أن‬
‫طﺎﻗﺔ اﻟﺠﺰﯾﺌﺎت اﻟﻤﺘﻔﺎﻋﻠﺔ ﻟﯿﺴﺖ ﻣﺘﺴ ﺎوﯾﺔ ﺣﯿ ﺚ ﯾﺤﺘ ﺎج اﻟﺠ ﺰيء‬
‫ﻟﻜﻲ ﯾﺘﻔﺎﻋ ﻞ إﻟ ﻰ ﻛﻤﯿ ﺔ ﻣ ﻦ اﻟﻄﺎﻗ ﺔ أﺳ ﻤﺎھﺎ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ‪ ،‬اﻟ ﺬي‬
‫ﯾﺆﻛﺪ أن اﻟﺠﺰﯾﺌﺎت ﻟﯿﺴﺖ ﻣﺘﻤﺎﺛﻠ ﺔ وأن ﻋ ﺪد اﻟﺠﺰﯾﺌ ﺎت اﻟﺘ ﻲ ﺗﻤﺘﻠ ﻚ‬
‫طﺎﻗ ﺔ ﺗﻨﺸ ﯿﻂ ﻗﻠﯿﻠ ﺔ ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﻌ ﺪد اﻟﻜﻠ ﻲ ﻟﻠﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻣﻤ ﺎ‬
‫ﯾﻔﺴﺮ اﻟﺰﻣﻦ اﻟﺬي ﯾﺤﺘﺎﺟﮫ ﺗﻔﺎﻋﻞ ﻣﺎ ﻟﻜﻲ ﯾﺼﻞ اﻟﻰ ﻧﻮاﺗﺞ‪.‬‬
‫ﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ ‪Activation Energy‬‬
‫ﯾﻤﻜﻦ ﺗﺨﯿﻞ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﺑﺤﺎﺟﺰ ﯾﺠﺐ ﻋﻠ ﻰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﺗﺨﻄﯿ ﮫ‬
‫ﺣﺘﻰ ﺗﺘﺤﻮل اﻟﻰ ﻧﻮاﺗﺞ‪ ،‬وﻟﻜﻲ ﺗﺘﺨﻄﺎه ﺟﺰﯾﺌﺎت اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ﯾﺠ ﺐ‬

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‫أن ﺗﻤﺘﻠﻚ طﺎﻗﺔ ﻛﺎﻣﻨﺔ أﻛﺒﺮ ﻣﻦ اﻟﻄﺎﻗﺔ اﻟﻜﺎﻣﻨﺔ ﻟﮭ ﺬا اﻟﺤ ﺎﺟﺰ‪ .‬ﻓ ﺈذا ﻛ ﺎن‬
‫ﻟﺪﯾﻨﺎ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪‬‬
‫‪→C + D‬‬
‫‪A + B ←‬‬
‫‪‬‬
‫ﺣﯿ ﺚ ﯾﺘﺼ ﺎدم ﺟ ﺰيء )‪ (A‬ﻣ ﻊ ﺟ ﺰيء )‪ (B‬اﻟﻠ ﺬﯾﻦ ﯾﻤﺘﻠﻜ ﺎن طﺎﻗ ﺔ‬
‫ﻛﺎﻣﻨﺔ أﻛﺒﺮ ﻣﻦ اﻟﺤﺎﺟﺰ اﻟﻄﺎﻗﻲ ﺳ ﯿﻜﻮﻧﺎن ﻣﺮﻛﺒ ﺎ ً اﻧﺘﻘﺎﻟﯿ ﺎ ً ]‪ [AB‬ﻧﺸ ﻄﺎ ً‬
‫اﻟ ﺬي ﺳ ﯿﻔﻘﺪ ﺟ ﺰءاً ﻣ ﻦ طﺎﻗﺘ ﮫ اﻟﻜﺎﻣﻨ ﺔ ﻟﻜ ﻲ ﯾﺘﺤ ﻮل اﻟ ﻰ ﻧ ﻮاﺗﺞ ﺣﺴ ﺐ‬
‫اﻟﺸﻜﻞ )‪.(١-٤‬‬
‫ﺷﻜﻞ )‪ : (١-٤‬ﺗﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﻜﺎﻣﻨ ﺔ ﻟﻠﻤﺘﻔ ﺎﻋﻼت واﻟﻨ ﻮاﺗﺞ ﻓ ﻲ ﺗﻔﺎﻋ ﻞ أ( ط ﺎرد‬
‫ﻟﻠﺤﺮارة‪ .‬ب( ﻣﺎص ﻟﻠﺤﺮارة‪.‬‬
‫وﻣﻦ اﻟﺸﻜﻞ )‪ (١-٤‬ﻧﻼﺣﻆ أن ‪:‬‬

‫‪∆E = E1 - E -1‬‬
‫‪ΔH = ΔE = E1 - E -1‬‬

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‫ﻣﻌﺎﺩﻟﺔ ﺃﺭﻫﻴﻨﻴﻮﺱ‬
‫‪Arrhenius Equation‬‬
‫ﺗﺄﺛﲑ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﻣﻌﺪﻝ ﺍﻟﺘﻔﺎﻋﻞ ﻭﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ‬
‫‪Effect of temperature on reaction rate and activation energy‬‬
‫ﺗ ﺆﺛﺮ درﺟ ﺔ اﻟﺤ ﺮارة ﻋﻠ ﻰ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗ ﺄﺛﯿﺮاً ﻛﺒﯿ ﺮاً ﺣﯿ ﺚ وﺟ ﺪ‬

‫ﻋﻤﻠﯿﺎ ً أن رﻓﻊ درﺟﺔ اﻟﺤﺮارة ﯾ ﺆدي اﻟ ﻰ زﯾ ﺎدة ﻣﻠﺤﻮظ ﺔ ﻓ ﻲ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ‪ ،‬وﻣ ﻦ ﺛ ﻢ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‪ ،‬وﯾﻤﻜ ﻦ أن‬
‫ﯾﻜ ﻮن ﺗﻐﯿ ﺮ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ أو ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻛﺘ ﺎﺑﻊ ﻟﺪرﺟ ﺔ‬
‫اﻟﺤﺮارة ﯾﺘﺒﻊ أﺣﺪ اﻷﻧﻮاع اﻟﻮاردة ﻓﻲ اﻟﺸﻜﻞ )‪.(٢-٤‬‬
‫ﺷﻜﻞ )‪ : (٢-٤‬أﻧﻮاع اﻟﻤﻨﺤﻨﯿﺎت اﻟﺘﻲ ﺗﺒﯿﻦ ﺗﻐﯿﺮ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻊ درﺟﺔ‬

‫اﻟﺤﺮارة‪.‬‬

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‫ﺍﻟﻨــﻮﻉ ﺍﻷﻭﻝ )ﺷ ﻜﻞ ‪ (٣-٤‬ھ ﻮ اﻟﺸ ﺎﺋﻊ‪ ،‬وﻗ ﺪ ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿ ﮫ ﻣ ﻦ‬

‫ﻣﻌﻈﻢ اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ‪ ،‬وﺳﻮف ﻧﻨﺎﻗﺸﮫ ﻻﺣﻘﺎ ً‪.‬‬
‫ﺷﻜﻞ )‪ : (٣-٤‬ﻣﻨﺤﻨﻰ أرھﯿﻨﯿﻮس ﻟﺘﺄﺛﯿﺮ درﺟﺔ اﻟﺤﺮارة‬
‫ﺍﻟﻨــــﻮﻉ ﺍﻟﺜــــﺎﻧﻲ )ﺷــــﻜﻞ ‪ : (٤-٤‬ﯾﺤ ﺪث ﻋﻨ ﺪ ﺣ ﺪوث اﻧﻔﺠ ﺎر‬
‫)‪ (explosion‬ﺧ ﻼل اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة اﻻﺷ ﺘﻌﺎل‬

‫)‪ ،(ignition temperature‬وﯾﻼﺣﻆ وﺟ ﻮد زﯾ ﺎدة ﻣﻔﺎﺟﺌ ﺔ ﻓ ﻲ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺷﻜﻞ )‪(٤-٤‬‬

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‫ﺍﻟﻨــﻮﻉ ﺍﻟﺜﺎﻟــﺚ )ﺷــﻜﻞ ‪ : (٥-٤‬ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿ ﮫ ﻣ ﻦ ﺗﻔ ﺎﻋﻼت‬
‫اﻟﮭﺪرﺟﺔ اﻟﻤﺤﻔﺰة‪ ،‬وﺗﻔﺎﻋﻼت اﻹﻧﺰﯾﻤﺎت )‪،(enzyme reactions‬‬
‫ﺷﻜﻞ )‪(٥-٤‬‬
‫ﺍﻟﻨﻮﻉ ﺍﻟﺮﺍﺑﻊ )ﺷﻜﻞ ‪ (٦-٤‬ﻟﻮﺣﻆ ﺧﻼل أﻛﺴﺪة اﻟﻜﺮﺑﻮن‬
‫ﺷﻜﻞ )‪(٦-٤‬‬

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‫ﺃﻣﺎ ﺍﻟﻨﻮﻉ ﺍﳋﺎﻣﺲ )ﺷﻜﻞ ‪ (٧-٤‬ﻓﺈﻧ ﮫ ﻟ ﻮﺣﻆ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﻔﺎﻋ ﻞ أﻛﺴ ﯿﺪ‬
‫اﻟﻨﯿﺘﺮﯾﻚ )‪ (NO‬ﻣﻊ اﻷﻛﺴﺠﯿﻦ ﻓﻘﻂ‪.‬‬
‫ﺷﻜﻞ )‪(٧-٤‬‬
‫• ﻟﻘﺪ ﺗﻢ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ اﻟﻨ ﻮع اﻷول )ﺷ ﻜﻞ ‪ (٣-٤‬ﻧﺘﯿﺠ ﺔ ﻟﻠﺪراﺳ ﺎت‬

‫اﻟﺘ ﻲ أﺟﺮاھ ﺎ اﻟﻌ ﺎﻟﻢ أرھﯿﻨﯿ ﻮس )‪ (Arrhenius‬ﻋﻠ ﻰ ﺗﻐﯿ ﺮ ﺛﺎﺑ ﺖ‬
‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻊ درﺟ ﺔ اﻟﺤ ﺮارة‪ ،‬ﻟ ﺬا ﻓ ﺈن ھ ﺬا اﻟﻨ ﻮع ﯾﻌ ﺮف‬
‫ﺑﻤﻨﺤﻨﻰ أرھﯿﻨﯿﻮس ﻟﺘﺄﺛﯿﺮ درﺟﺔ اﻟﺤﺮارة‪ ،‬وﯾﻄﻠﻖ ﻋﻠ ﻰ اﻟﻤﻨﺤﻨﯿ ﺎت‬
‫اﻷﺧﺮى اﻟﻤﻨﺤﻨﯿﺎت اﻟﻤﻨﺎﻗﻀﺔ ﻟﻤﻨﺤﻨﻰ أرھﯿﻨﯿﻮس‪.‬‬
‫• وﯾﺘﻮاﻓ ﻖ اﻟﻨ ﻮع اﻷول ﻣ ﻊ ﺗﻌﻤ ﯿﻢ ﻣﮭ ﻢ ﻓ ﻲ ﺣﺎﻟ ﺔ اﻟﺘﻔ ﺎﻋﻼت‬
‫اﻟﻤﺘﺠﺎﻧﺴﺔ ﯾﻨﺺ ﻋﻠﻰ أن ‪:‬‬

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‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ ﯾﻤﻜﻦ أن ﺗﺘﻀﺎﻋﻒ ﻣﺮﺗﯿﻦ أو ﺛﻼﺛ ﺎ ً ﻟﻜ ﻞ‬

‫زﯾﺎدة ﻣﻘﺪارھﺎ ﻋﺸﺮ درﺟﺎت ﻣﺌﻮﯾﺔ ﻓﻲ درﺟﺔ اﻟﺤﺮارة‪.‬‬
‫• وﻟﻘ ﺪ اﻗﺘ ﺮح اﻟﻌ ﺎﻟﻢ ھ ﻮد )‪ (Hood‬ﻋ ﺎم )‪١٨٧٨‬م( أول ﻗ ﺎﻧﻮن‬
‫ﺗﺠﺮﯾﺒﻲ ﯾﻮﺿﺢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (k‬ﻟﺘﻔﺎﻋ ﻞ ﻣ ﺎ‬
‫ﻣﻊ درﺟﺔ ﺣﺮارة )‪ (T‬ﻣﺎ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪B‬‬
‫‪log k = A' -‬‬
‫‪T‬‬
‫ﺣﯿﺚ ‪:‬‬
‫)'‪ (B , A‬ﺛﻮاﺑﺖ ﻗﯿﻤﮭﺎ ﻣﻮﺟﺒﺔ‬
‫)‪ (T‬درﺟﺔ اﻟﺤﺮارة اﻟﻤﻄﻠﻘﺔ‪.‬‬
‫• وﯾﻤﻜ ﻦ اﻟﺘﺤﻘ ﻖ ﻣ ﻦ ھ ﺬه اﻟﻤﻌﺎدﻟ ﺔ ﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ )‪(log k‬‬
‫وﻣﻘﻠﻮب درﺟﺔ اﻟﺤﺮارة )‪: (1/T‬‬
‫‪1‬‬
‫‪log k = A' - B  ‬‬
‫‪T‬‬
‫وھﻲ ﻋﻼﻗﺔ ﺧﻄﯿﺔ ﻣﯿﻠﮭﺎ )‪ (-B‬ﺳﺎﻟﺐ ﻟﻤﻌﻈﻢ اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ‪.‬‬

‫• وﻓ ﻲ ﻋ ﺎم )‪ (1884‬ﺑ ﯿﻦ اﻟﻌ ﺎﻟﻢ ﻓﺎﻧ ﺖ ھ ﻮف )‪(Van't Hoff‬‬
‫أھﻤﯿﺔ ﻧﻈﺮﯾﺔ ﻟﮭﺬا اﻟﻘﺎﻧﻮن ﺣﯿﺚ ﻧ ﺎﻗﺶ ﻓﻜ ﺮة ﺗ ﺄﺛﯿﺮ درﺟ ﺔ اﻟﺤ ﺮارة‬
‫ﻋﻠﻰ ﺛﻮاﺑﺖ اﻟﺘﻮازن‬

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‫• وﻟﻘ ﺪ ﺗﻮﺳ ﻊ اﻟﻌ ﺎﻟﻢ أرھﯿﻨﯿ ﻮس )‪ (1889‬ﻓ ﻲ ﺗﻄﺒﯿ ﻖ ھ ﺬه اﻟﻔﻜ ﺮة‬

‫ﻟﺘﺸﻤﻞ ﺗﺄﺛﯿﺮ درﺟﺔ اﻟﺤﺮارة ﻋﻠﻰ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪ ،‬وﻟﻘﺪ طﺒﻘﮭﺎ‬
‫ﺑﻨﻔﺴ ﮫ ﺑﻨﺠ ﺎح ﻋﻠ ﻰ ﻋ ﺪد ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﺣﺘ ﻰ أﺻ ﺒﺢ اﻟﻘ ﺎﻧﻮن‬
‫اﻟﻤﺴﺘﺨﺪم ﯾ ﺪﻋﻰ ﺑﻘ ﺎﻧﻮن أرھﯿﻨﯿ ﻮس‪ ،‬وﻗ ﺪ ﺗﻤ ﺖ ﻣﻨﺎﻗﺸ ﺔ ﻣﻨﺎﻗﺸ ﺎت‬
‫اﻟﻌﺎﻟﻤﯿﻦ ﻓﺎﻧﺖ ھﻮف وأرھﯿﻨﯿﻮس ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫• اﻗﺘ ﺮح اﻟﻌ ﺎﻟﻢ ﻓﺎﻧ ﺖ ھ ﻮف أن ﺗ ﺄﺛﯿﺮ درﺟ ﺔ اﻟﺤ ﺮارة ﻋﻠ ﻰ ﺛﺎﺑ ﺖ‬
‫اﻟﺘ ﻮازن ﻷي ﺗﻔﺎﻋ ﻞ ﻋﻜﺴ ﻲ )‪ (reversible reaction‬ﯾ ﺘﻢ وﻓﻘ ﺎ ً‬
‫ﻟﻠﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪dlnK‬‬ ‫‪ΔU‬‬
‫=‬
‫‪dT‬‬ ‫‪RT 2‬‬
‫ﺣﯿﺚ ‪:‬‬
‫)‪ : (K‬ﺛﺎﺑﺖ اﻟﺘﻮازن ﺑﺪﻻﻟﺔ اﻟﺘﺮاﻛﯿﺰ‪،‬‬
‫) ‪ : ( ΔU‬اﻟﺘﻐﯿ ﺮ ﻓ ﻲ اﻟﻄﺎﻗ ﺔ‪ ،‬وھ ﻲ ﺗﻤﺜ ﻞ أﯾﻀ ﺎ ﺣ ﺮارة اﻟﺘﻔﺎﻋ ﻞ‬
‫)‪ (Heat of reaction‬ﻋﻨﺪ ﺣﺠﻢ ﺛﺎﺑﺖ‪،‬‬
‫)‪ : (R‬ﺛﺎﺑ ﺖ اﻟﻐ ﺎزات اﻟﻌ ﺎم‪ ،‬وﺣﯿ ﺚ أن اﻟﺘﻮازﻧ ﺎت ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت‬
‫ﺮ‬ ‫ﻞ اﻟﻤﺒﺸ‬ ‫ﺮﻋﺘﻲ اﻟﺘﻔﺎﻋ‬ ‫ﺈن ﺳ‬ ‫ﺔﻓ‬ ‫ﯿﺔ دﯾﻨﺎﻣﯿﻜﯿ‬ ‫اﻟﻌﻜﺴ‬
‫)‪ ،(forward reaction‬واﻟﺘﻔﺎﻋﻞ اﻟﻤﻌ ﺎﻛﺲ )‪،(reverse reaction‬‬
‫ﺗﺼﺒﺤﺎن ﻣﺘﺴﺎوﯾﺘﯿﻦ ﻋﻨﺪ ﺣﺎﻟﺔ اﻟﺘﻮازن‪ .‬ﻓﺈذا ﻛﺎن ﻟﺪﯾﻨﺎ ﺗﻔﺎﻋﻞ ﻣﺜﻞ ‪:‬‬

‫‪832‬‬
‫‪‬‬
‫‪A + B ‬‬
‫‪kf‬‬
‫‪‬‬
‫‪C + D‬‬
‫‪kr‬‬
‫ﻓﺈن ‪:‬‬
‫]‪k f [A][B] = k r [C][D‬‬
‫ﺣﯿ ﺚ )‪ (kf‬و )‪ (kr‬ھﻤ ﺎ ﺛﺎﺑﺘ ﺎ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ اﻻﺗﺠ ﺎھﯿﻦ اﻟﻤﺒﺎﺷ ﺮ‬

‫واﻟﻤﻌﺎﻛﺲ ﻋﻠﻰ اﻟﺘﻮاﻟﻲ‪ ،‬وﺣﯿﺚ أن ‪:‬‬
‫]‪k f [A][B] = k r [C][D‬‬
‫‪kf‬‬ ‫]‪[C][D‬‬
‫=‪=K‬‬
‫‪kr‬‬ ‫]‪[A][B‬‬
‫‪ dlnK‬‬ ‫‪ΔU ‬‬
‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪‬‬ ‫=‬ ‫‪‬‬ ‫ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ dT‬‬ ‫‪RT 2 ‬‬
‫‪dlnk f‬‬ ‫‪dlnk r‬‬ ‫‪ΔU‬‬

‫‪=-‬‬ ‫=‬
‫‪dT‬‬ ‫‪dT‬‬ ‫‪RT 2‬‬
‫وﺑﻤﺎ أن ‪:‬‬
‫‪ΔU = Eaf - E ar‬‬
‫ﺣﯿ ﺚ )‪ (Eaf‬و )‪ (Ear‬ھﻤ ﺎ طﺎﻗﺘ ﺎ اﻟﺘﻨﺸ ﯿﻂ ﻓ ﻲ اﻻﺗﺠ ﺎھﯿﻦ اﻟﻤﺒﺎﺷ ﺮ‬

‫واﻟﻤﻌﺎﻛﺲ ﻋﻠﻰ اﻟﺘﻮاﻟﻲ‪.‬‬
‫‪ dlnk f‬‬ ‫‪dlnk r‬‬ ‫‪ΔU ‬‬
‫‪( ΔH = E af‬‬ ‫) ‪- E ar‬‬ ‫و‬ ‫‪‬‬ ‫‪=-‬‬ ‫=‬ ‫‪‬‬ ‫وﺑ ﺪﻣﺞ اﻟﻤﻌ ﺎدﻟﺘﯿﻦ‬
‫‪ dT‬‬ ‫‪dT‬‬ ‫‪RT 2 ‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪833‬‬
‫‪dlnk f dlnk r‬‬ ‫‪E‬‬ ‫‪E‬‬

‫‪-‬‬ ‫‪= af2 − ar2‬‬
‫‪dT‬‬ ‫‪dT‬‬ ‫‪RT RT‬‬
‫وﻟﻘﺪ اﻗﺘﺮح اﻟﻌﺎﻟﻢ أرھﯿﻨﯿﻮس ﻓﺼﻞ اﻟﻤﻌﺎدﻟﺔ اﻟﻰ ﻣﻌﺎدﻟﺘﯿﻦ ھﻤﺎ ‪:‬‬
‫‪dln k f‬‬ ‫‪E‬‬
‫‪= af2 + I‬‬
‫‪dT‬‬ ‫‪RT‬‬
‫‪dln k r‬‬ ‫‪E‬‬
‫‪= ar2 + I‬‬
‫‪dT‬‬ ‫‪RT‬‬
‫ﺣﯿﺚ )‪ (I‬ﺛﺎﺑﺖ‪ ،‬وﻗ ﺪ وﺟ ﺪ ﻋﻤﻠﯿ ﺎ ً أن ﻗﯿﻤﺘ ﮫ ﯾﻤﻜ ﻦ أن ﺗﺴ ﺎوي اﻟﺼ ﻔﺮ‪،‬‬

‫اﻷﻣ ﺮ اﻟ ﺬي ﻣﻜ ﻦ ﻣ ﻦ اﻗﺘ ﺮاح ﻣﻌﺎدﻟ ﺔ ﻋﺎﻣ ﺔ ﺗﺒ ﯿﻦ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﺛﺎﺑ ﺖ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ودرﺟﺔ اﻟﺤﺮارة ھﻲ ‪:‬‬
‫‪dln k‬‬ ‫‪Ea‬‬
‫=‬
‫‪dT‬‬ ‫‪RT 2‬‬
‫ﺣﯿ ﺚ )‪ (Ea‬ﺗﺴ ﻤﻰ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ )‪ ،(activation energy‬وﺗﺴ ﻤﻰ‬
‫‪ dln k‬‬ ‫‪Ea ‬‬
‫ﺑﻤﻌﺎدﻟ ﺔ أرھﯿﻨﯿ ﻮس‪ ،‬وھ ﻲ ﺗﺸ ﺒﮫ اﻟ ﻰ ﺣ ﺪ‬ ‫‪ dT = RT 2 ‬‬ ‫اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪‬‬
‫‪ dlnK‬‬ ‫‪ΔU ‬‬

‫‪. ‬‬ ‫‪dT‬‬
‫=‬ ‫‪‬‬
‫‪RT 2 ‬‬
‫ﻛﺒﯿﺮ ﻣﻌﺎدﻟﺔ ﺛﺎﺑﺖ اﻟﺘﻮازن‬
‫ﻣﻠﺤﻮﻇﺔ ‪:‬‬
‫‪ dln k f‬‬ ‫‪E‬‬ ‫‪‬‬
‫أو‬ ‫‪‬‬ ‫‪= af2 + I ‬‬ ‫‪ (١‬ﻓﻜ ﺮة وﺿ ﻊ اﻟﺜﺎﺑ ﺖ )‪ (I‬ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ dT‬‬ ‫‪RT‬‬ ‫‪‬‬
‫‪ dln k r‬‬ ‫‪‬‬

‫ﻣﺴﺎوﯾﺎ ً ﻟﻠﺼ ﻔﺮ ذات ﻣﻐ ﺰى ﺧ ﺎص ﯾﻜﻤ ﻦ ﻓ ﻲ أن‬
‫‪E ar‬‬
‫‪ dT = RT 2 + I ‬‬
‫‪‬‬ ‫‪‬‬

‫‪834‬‬
‫ﻋﺪم ﻣﺴﺎواﺗﮫ ﻟﻠﺼ ﻔﺮ ﯾﺤ ﺘﻢ اﺳ ﺘﻨﺘﺎج أن اﻋﺘﻤ ﺎد ﺳ ﺮﻋﺘﻲ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ‬

‫اﻻﺗﺠﺎھﯿﻦ ﻋﻠﻰ درﺟﺔ اﻟﺤﺮارة ﯾﺘﺄﺛﺮ ﺑﻤﻌﺎﻣﻞ آﺧﺮ ﻣﺸﺘﺮك ﺑﯿﻨﮭﻤﺎ‪ ،‬أﻣ ﺎ‬
‫ﻛ ﻮن أن اﻟﺜﺎﺑ ﺖ )‪ (I‬ﯾﺴ ﺎوي اﻟﺼ ﻔﺮ ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ ﻣ ﻦ ﺗﻘﺴ ﯿﻢ اﻟﺘﻔﺎﻋ ﻞ‬
‫اﻟﺴ ﺎﺑﻖ ﻣ ﻦ )‪ (A + B‬اﻟ ﻰ )‪ (C + D‬اﻟ ﻰ ﺟ ﺰأﯾﻦ أﺣ ﺪھﻤﺎ ﯾﻌﻨ ﻲ‬
‫ﺑﺴﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣ ﻦ اﻟﯿﺴ ﺎر اﻟ ﻰ اﻟﯿﻤ ﯿﻦ أي ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻤﺒﺎﺷ ﺮ‪،‬‬
‫واﻵﺧ ﺮ ﯾﻌﻨ ﻰ ﺑﺴ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﯿﻤ ﯿﻦ اﻟ ﻰ اﻟﯿﺴ ﺎر أي ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋﻞ اﻟﻤﻌﺎﻛﺲ‪.‬‬
‫‪ (٢‬ظﮭﻮر طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ )‪ (Ea‬ﻓﻲ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ﯾﻘ ﻮد اﻟ ﻰ ﺣﻘﯿﻘ ﺔ‬
‫ﻣﮭﻤ ﺔ ﺟ ﺪاً ﺗﺘﻀ ﻤﻦ وﺟ ﻮب ﺗﻨﺸ ﯿﻂ اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻟﻜ ﻲ ﯾﺤ ﺪث‬
‫اﻟﺘﻔﺎﻋﻞ‪ ،‬أي ﻻ ﺑﺪ ﻣﻦ إﻋﻄﺎﺋﮭ ﺎ ﻛﻤﯿ ﺔ ﻣﻌﯿﻨ ﺔ ﻣ ﻦ اﻟﻄﺎﻗ ﺔ ﻟﻜ ﻲ ﺗﺘﺼ ﺎدم‬
‫ھ ﺬه اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﻨﺸ ﻄﺔ )‪ (activated molecules‬ﺑﺪرﺟ ﺔ ﻛﺎﻓﯿ ﺔ‬
‫ﻟﻜ ﻲ ﯾﺤ ﺪث اﻟﺘﻔﺎﻋ ﻞ‪ ،‬أﻣ ﺎ اﻟﺘﺼ ﺎدﻣﺎت اﻟﺤﺎﺻ ﻠﺔ ﺑ ﯿﻦ اﻟﺠﺰﯾﺌ ﺎت ﻏﯿ ﺮ‬
‫اﻟﻤﻨﺸﻄﺔ ﻓﺈﻧﮭﺎ ﻋﺪﯾﻤﺔ اﻟﺠﺪوى‪ ،‬وﻟﻦ ﺗﺆدي اﻟﻰ ﺣﺪوث أي ﺗﻔﺎﻋﻞ‪.‬‬
‫ﻋﻠﻰ ھﺬا اﻷﺳﺎس ﻓﺈن طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﺗﻌﺮف ﺑﺄﻧﮭﺎ أﻗ ﻞ ﻣﻘ ﺪار ﻣ ﻦ اﻟﻄﺎﻗ ﺔ‬
‫ﺗﺤﺘﺎﺟﮫ اﻟﺠﺰﯾﺌﺎت اﻟﻤﺘﻔﺎﻋﻠﺔ ﻟﻜﻲ ﯾﺤﺪث اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫• وﯾﺴﺘﻨﺘﺞ ﻣﻦ ﻓﻜﺮة اﻟﺘﻨﺸﯿﻂ أن ﺟﺰﯾﺌﺎت اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ﻻ ﺗﺘﺤ ﻮل‬

‫ﻣﺒﺎﺷ ﺮة اﻟ ﻰ ﻧ ﻮاﺗﺞ ﺑ ﻞ إن اﻟﺠﺰﯾﺌ ﺎت ﺗﺤﺘ ﺎج اﻟ ﻰ ﻣﻘ ﺪار ﻣﻌ ﯿﻦ ﻣ ﻦ‬
‫اﻟﻄﺎﻗﺔ ﻟﻜﻲ ﺗﻤﺮ ﺑﻤﺎ ﯾﺴ ﻤﻰ ﺑﺎﻟﺤﺎﻟ ﺔ اﻟﻤﻨﺸ ﻄﺔ )‪(activated state‬‬

‫‪835‬‬
‫وھ ﻲ اﻟﺘ ﻲ ﯾﺘﻜ ﻮن ﻋﻨ ﺪھﺎ ﻣ ﺎ ﯾﺴ ﻤﻰ اﻟﻤﻌﻘ ﺪ اﻟﻤﻨﺸ ﻂ‬

‫)‪ (activated complex‬وھ ﻮ ﻣﺮﻛ ﺐ ﻧﺸ ﻂ ﻏﯿ ﺮ ﺛﺎﺑ ﺖ‪ ،‬اﻗﺘ ﺮح‬
‫أن ﯾﻜﻮن ﺗﺮﻛﯿﺒ ﮫ وﺳ ﻄﺎ ً ﺑ ﯿﻦ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ واﻟﻤ ﻮاد اﻟﻨﺎﺗﺠ ﺔ‪،‬‬
‫وﻓ ﻲ ﺣﺎﻟ ﺔ ﺗ ﻮازن ﻣ ﻊ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﺛ ﻢ ﯾﺘﻔﻜ ﻚ ھ ﺬا اﻟﻤﺮﻛ ﺐ‬
‫ﺑﺴﺮﻋﺔ ﻣﻌﯿﻨﺔ اﻟﻰ ﻣﻮاد ﻧﺎﺗﺠﺔ ﻛﻤﺎ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪ Activated State ‬‬
‫‪Reactants ‬‬ ‫‪→ products‬‬
‫ﺑﻨﺎء ﻋﻠﻰ ذﻟﻚ ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﺗﻌﺮﯾﻒ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﺑﺸﻜﻞ آﺧﺮ ﺑﺄﻧﮭﺎ ‪:‬‬
‫أﻗ ﻞ ﻣﻘ ﺪار ﻣ ﻦ اﻟﻄﺎﻗ ﺔ ﺗﺤﺘﺎﺟ ﮫ اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻟﺘﺼ ﻞ اﻟ ﻰ اﻟﺤﺎﻟ ﺔ‬
‫اﻟﻤﻨﺸﻄﺔ‪ ،‬وﺗﻜﻮن ﻗﺎدرة ﻋﻠﻰ ﺗﻜﻮﯾﻦ اﻟﻨﻮاﺗﺞ‪.‬‬
‫• وھ ﺬا ﯾﻌﻨ ﻲ وﺟ ﻮد ﺣ ﺎﺟﺰ ﻟﻠﻄﺎﻗ ﺔ )‪ (energy barrier‬ﺑ ﯿﻦ‬

‫اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ واﻟﻨﺎﺗﺠﺔ‪ ،‬ﻓ ﺈذ ﻛﺎﻧ ﺖ اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻗ ﺎدرة‬
‫ﻋﻠﻰ ﺗﺨﻄﻲ ھﺬا اﻟﺤﺎﺟﺰ ﻓﺈﻧﮭ ﺎ ﺳ ﻮف ﺗﺘﺤ ﻮل اﻟ ﻰ ﻧ ﻮاﺗﺞ‪ .‬وﯾﻤﻜ ﻦ‬
‫ﻓﮭﻢ ذﻟﻚ ﺑﻤﺴﺎﻋﺪة ﻣﻨﺤﻨﻰ اﻟﻄﺎﻗﺔ ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪(٨-٤‬‬

‫‪836‬‬
‫ﺷﻜﻞ )‪ : (٨-٤‬ﻣﻨﺤﻨﻰ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪.‬‬
‫• ﺣﯿ ﺚ ﺗ ﻢ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ طﺎﻗ ﺔ اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ وﻣﺴ ﺎر‬

‫اﻟﺘﻔﺎﻋ ﻞ )‪ (reaction coordinate‬اﻟ ﺬي ﯾﻤﻜ ﻦ أن ﺗﻤﺜﻠ ﮫ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ‪ .‬ﯾﺘﻀ ﺢ ﻣ ﻦ اﻟﺸ ﻜﻞ )‪ (٨-٤‬أﻧ ﮫ ﻟﻜ ﻲ ﯾﺤ ﺪث اﻟﺘﻔﺎﻋ ﻞ ﺑ ﯿﻦ‬
‫ﺟﺰﯾﺌ ﺎت اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ )‪ (A‬و )‪ (B‬ﻻ ﺑ ﺪ أن ﺗﻤ ﺘﺺ ھ ﺬه‬
‫اﻟﺠﺰﯾﺌﺎت ﻛﻤﯿﺔ ﻣﻦ اﻟﻄﺎﻗ ﺔ ﻣﻘ ﺪارھﺎ )‪ (Eaf‬ﻟﻜ ﻲ ﺗﺼ ﻞ اﻟ ﻰ اﻟﺤﺎﻟ ﺔ‬
‫اﻟﻤﻨﺸ ﻄﺔ )‪ (AB‬أي أن )‪ (Eaf‬ھ ﻲ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫‪ ، ( A + B‬وھ ﻲ ﺗﺴ ﺎوي اﻟﻔ ﺮق ﻓ ﻲ اﻟﻄﺎﻗ ﺔ ﺑ ﯿﻦ طﺎﻗ ﺔ‬ ‫‪ AB‬‬
‫‪‬‬ ‫)‬
‫اﻟﺠﺰﯾﺌﺎت ﻓﻲ اﻟﺤﺎﻟ ﺔ اﻟﻤﻨﺸ ﻄﺔ )‪ ،(Uy‬وطﺎﻗ ﺔ اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ‬
‫)‪ (Ux‬أي أن ‪:‬‬
‫‪E af = U y - U x‬‬

‫‪837‬‬
‫‪( C + D ‬‬
‫وﺑﺎﻟﻤﺜﻞ ﻓﺈن )‪ (Ear‬ﺗﻤﺜﻞ طﺎﻗﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻤﻌﺎﻛﺲ ) ‪ AB‬‬ ‫•‬
‫أو أﻧﮭ ﺎ ﺗﻤﺜ ﻞ اﻟﻄﺎﻗ ﺔ اﻟﻤﻨﺒﻌﺜ ﺔ اﻟﻤﺼ ﺎﺣﺒﺔ ﻟﺘﻔﻜ ﻚ اﻟﻤﻌﻘ ﺪ اﻟﻤﻨﺸ ﻂ‬
‫)‪ (AB‬اﻟﻰ ﻣﻮاد ﻧﺎﺗﺠﺔ وھﻲ ﺗﺴﺎوي ‪:‬‬
‫‪E ar = U y - U z‬‬
‫• ﺑﺎﻹﻋﺘﻤﺎد ﻋﻠﻰ ﻣﺎ ﺳﺒﻖ ﻓ ﺈن اﻟﻔ ﺮق ﺑﺎﻟﻄﺎﻗ ﺔ ) ‪ ( ∆U‬ﻟﻠﺘﻔﺎﻋ ﻞ ﯾﻌﻄ ﻰ‬

‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪∆U = E af - E ar‬‬
‫) ‪∆U = ( U y - U x ) - ( U y - U z‬‬
‫‪∆U = U y - U x - U y + U z‬‬
‫‪∆U = - U x + U z‬‬
‫‪⇒ ∆U = U z - U x‬‬
‫• ﯾﺘﻀﺢ ﻣﻦ اﻟﻤﻌﺎدﻟﺔ ) ‪ ( ∆U = U z - U x‬أن ) ‪ ( ∆U‬ھﻲ اﻟﻔﺮق ﻓﻲ اﻟﻄﺎﻗﺔ‬

‫ﺑﯿﻦ طﺎﻗﺔ اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ وطﺎﻗﺔ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‪ ،‬وھ ﻲ ﻋﺒ ﺎرة ﻋ ﻦ‬
‫اﻟﺘﻐﯿﺮ ﻓﻲ ﺣﺮارة اﻟﺘﻔﺎﻋﻞ ) ‪ ( ∆H‬ﻋﻨﺪ ﺣﺠﻢ ﺛﺎﺑﺖ‬
‫• وﯾﻼﺣ ﻆ أن ﻗﯿﻤ ﺔ ) ‪ ( ∆H‬ﻛﻤﯿ ﺔ ﺳ ﺎﻟﺒﺔ ﻷن ) ‪ ، ( U x > U z‬وﻓ ﻲ ھ ﺬه‬
‫اﻟﺤﺎﻟ ﺔ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﻧﺎﺷ ﺮ ﻟﻠﺤ ﺮارة )‪،(exothermic reaction‬‬
‫ﺮارة‬ ‫ﺎ ً ﻟﻠﺤ‬ ‫ﻞ ﻣﺎﺻ‬ ‫ﻮن اﻟﺘﻔﺎﻋ‬ ‫ﻦ أن ﯾﻜ‬ ‫وﯾﻤﻜ‬
‫)‪ (endothermic reaction‬إذا ﻛﺎن ) ‪. ( U z > U x‬‬

‫‪838‬‬
‫• وﻧﻈﺮاً ﻟﻤﺎ ﺗﺘﻤﯿﺰ ﺑﮫ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿ ﻮس ﻣ ﻦ اﻟﻨﺎﺣﯿ ﺔ اﻟﻌﻤﻠﯿ ﺔ ﻓﺈﻧ ﮫ ﻻ‬

‫ﺑﺪ ﻣﻦ إﺟﺮاء اﻟﺘﻜﺎﻣﻞ ﻟﮭ ﺎ ﻋﻠ ﻰ اﻓﺘ ﺮاض أن )‪ (Ea‬ﺛﺎﺑﺘ ﺔ ﻓ ﻲ ﻣ ﺪى‬
‫ﻧﻄﺎق ﻣﻌﯿﻦ ﻣﻦ درﺟﺎت اﻟﺤﺮارة وذﻟﻚ ﻹﯾﺠﺎد ﺷ ﻜﻞ آﺧ ﺮ ﻟﻠﻤﻌﺎدﻟ ﺔ‬
‫ﯾﻤﻜﻦ ﺗﻄﺒﯿﻘﮫ ﻋﻠﻰ اﻟﻨﺘﺎﺋﺞ اﻟﻌﻤﻠﯿﺔ‪ ،‬وﺗﻜﻮن ﻧﺘﯿﺠﺔ اﻟﺘﻜﺎﻣﻞ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Ea‬‬
‫‪lnk = -‬‬ ‫‪+ constant‬‬
‫‪RT‬‬
‫• وﻟﻘ ﺪ وﺟ ﺪ أن اﻟﺜﺎﺑ ﺖ ھ ﻮ ﻋﺒ ﺎرة ﻋ ﻦ )‪ (ln A‬ﺣﯿ ﺚ )‪ (A‬ﯾﺴ ﻤﻰ‬

‫ﺑﻤﻌﺎﻣ ﻞ اﻟﺘ ﺮدد )‪ ،(frequency factor‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬
‫ﯾﻤﻜﻦ أن ﺗﻜﺘﺐ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪ ln k = -‬‬ ‫‪+ constant ‬‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬
‫‪Ea‬‬
‫‪ln k = -‬‬ ‫‪+ ln A‬‬
‫‪RT‬‬
‫‪or‬‬
‫‪Ea‬‬
‫‪ln k = ln A -‬‬
‫‪RT‬‬
‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ ﺑﺸﻜﻞ أﺳﻲ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪Ea‬‬
‫‪lnk = lnA -‬‬
‫‪RT‬‬
‫(‪k = A exp‬‬
‫) ‪- Ea /RT‬‬
‫وﯾﻤﻜﻦ أﯾﻀﺎ ً ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪Ea‬‬
‫‪log k = -‬‬ ‫‪+ log A‬‬
‫‪2.303 RT‬‬

‫‪839‬‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬

‫ﻣﺘﺸ ﺎﺑﮭﺔ ﻣ ﻊ اﻟﻤﻌﺎدﻟ ﺔ‬ ‫‪ log k = -‬‬ ‫‪+ log A ‬‬ ‫• واﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪2.303 RT‬‬ ‫‪‬‬
‫‪‬‬ ‫‪B‬‬
‫‪ ،  log k = A' -‬وطﺒﻘ ﺎ ً ﻟﮭ ﺬه اﻟﻤﻌﺎدﻟ ﺔ واﻟﻤﻌﺎدﻟ ﺔ‬ ‫‪‬‬ ‫اﻟﺘﺠﺮﯾﺒﯿ ﺔ‬
‫‪‬‬ ‫‪T‬‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬

‫ﯾﺠ ﺐ أن ﺗﻜ ﻮن ﻧﺘﯿﺠ ﺔ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ‬ ‫‪ ln k = -‬‬ ‫‪+ ln A ‬‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬
‫)‪ (log k‬أو )‪ (ln k‬وﻣﻘﻠﻮب درﺟﺔ اﻟﺤﺮارة )‪ (1/T‬ﺧﻄﺎ ً ﻣﺴﺘﻘﯿﻤﺎ ً‬

‫ﻣﯿﻠﮫ )‪ (- Ea/2.303R‬أو )‪ (- Ea/R‬ﻋﻠﻰ اﻟﺘﻮاﻟﻲ‪ ،‬وﯾﻘﻄﻊ ﻣﺤﻮر‬
‫اﻟﺼ ﺎدات ﺑﺎﻟﻤﻘ ﺪار )‪ (log A‬أو )‪ .(ln A‬وﺑﻤﻌﺮﻓ ﺔ ﻣﯿ ﻞ اﻟﺨ ﻂ‬
‫اﻟﻤﺴﺘﻘﯿﻢ ﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ )‪.(Ea‬‬
‫ﻣﺜﺎﻝ ﺗﻮﺿﻴﺤﻲ‬
‫وﺟﺪ أن ﻣﯿ ﻞ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﻔﻜ ﻚ اﻟﻤﺮﻛ ﺐ )‪ (N2O5‬ﺣﺮارﯾ ﺎ ً ﺑ ﯿﻦ‬

‫)‪ (273 K‬و )‪ (338 K‬ﯾﺴ ﺎوي )‪ (- 5400‬ﻋﻨ ﺪ رﺳ ﻢ )‪ (log k‬ﻣﻘﺎﺑ ﻞ‬
‫)‪ (1/T‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪(٩-٤‬‬

‫‪840‬‬
‫ﺷﻜﻞ )‪ : (٩-٤‬رﺳﻢ )‪ (log k‬ﻣﻘﺎﺑﻞ )‪ (1/T‬ﻟﺘﻔﻜﻚ )‪ (N2O5‬ﺣﺮارﯾﺎ ً‪.‬‬

‫وﺑﺎﻻﻋﺘﻤﺎد ﻋﻠﻰ ﻗﯿﻤﺔ ﻣﯿﻞ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ﯾﻤﻜﻦ ﺣﺴ ﺎب طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ‬
‫ﻟﺘﻔﻜﻚ اﻟﻤﺮﻛﺐ )‪ (N2O5‬ﺣﺮارﯾﺎ ً ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Ea‬‬
‫‪slope = -‬‬
‫‪2.303R‬‬
‫)‪E a = - (slope × 2.303R‬‬
‫)‪E a = - ( - 5400 × 2.303 × 8.314‬‬
‫‪E a = 103394.57 J mol-1‬‬
‫‪E a = 103.39 kJ mol-1‬‬
‫• ﻻ ﺣﻆ أن وﺣﺪات طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﺗﺤﺪدھﺎ ﻗﯿﻤﺔ )‪ (R‬اﻟﻤﺴﺘﺨﺪﻣﺔ‬

‫• وﯾﻤﻜ ﻦ أﯾﻀ ﺎ ً ﺗﻘ ﺪﯾﺮ ﻗﯿﻤ ﺔ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ )‪ (Ea‬إذا ﻋﺮﻓ ﺖ ﻗﯿﻤﺘ ﯿﻦ‬
‫ﻟﺜﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟﺘ ﻲ ﺣ ﺮارة ﻣﺨﺘﻠﻔﺘ ﯿﻦ‪ ،‬ﻓ ﺈذا ﻛ ﺎن‬
‫)‪ (k1‬ھ ﻮ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺔ اﻟﺤ ﺮارة )‪ (T1‬و)‪(k2‬‬

‫‪841‬‬
‫ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة أﺧ ﺮى )‪ ،(T2‬ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻣ ﻦ اﻟﻤﻌﺎدﻟ ﺔ‬

‫‪‬‬ ‫‪‬‬
‫ﻋﻠﻰ أن ‪:‬‬ ‫‪ log k = -‬‬
‫‪Ea‬‬
‫‪+ log A ‬‬
‫‪‬‬ ‫‪2.303 RT‬‬ ‫‪‬‬
‫‪k2‬‬ ‫‪E a  T2 - T1 ‬‬

‫‪log‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪k1‬‬ ‫‪2.303 R  T2T1 ‬‬
‫‪‬‬ ‫‪k2‬‬ ‫‪E a  T2 - T1  ‬‬

‫‪‬‬
‫‪ ‬أﻧﮫ ﯾﻤﻜﻦ ﺗﻘ ﺪﯾﺮ ﻗﯿﻤ ﺔ‬ ‫‪log‬‬ ‫=‬ ‫‪‬‬ ‫ﯾﺘﻀﺢ ﻣﻦ اﻟﻤﻌﺎدﻟﺔ ‪ ‬‬
‫‪‬‬ ‫‪k‬‬ ‫‪1‬‬ ‫‪2.303‬‬ ‫‪R‬‬ ‫‪ 2 1 ‬‬
‫‪T‬‬ ‫‪T‬‬
‫طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ )‪ (Ea‬إذا ﻋﺮﻓ ﺖ ﻗﯿﻤﺘ ﯿﻦ ﻟﺜﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟﺘ ﻲ‬

‫ﺣﺮارة ﻣﺨﺘﻠﻔﺘﯿﻦ‬
‫• ﻛﻤﺎ أﻧﮫ ﯾﻤﻜﻦ ﺗﻘﺪﯾﺮ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ أي درﺟ ﺔ ﺣ ﺮارة‬
‫إذا ﻋﺮﻓﺖ ﻗﯿﻤﺔ )‪ (Ea‬وﻗﯿﻤ ﺔ أﺧ ﺮى ﻟﺜﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺔ‬
‫ﺣﺮارة أﺧﺮى‪.‬‬

‫‪842‬‬
‫ﻟﺪﯾﻚ اﻟﺸﻜﻞ )‪ (١٠-٤‬اﻟﺬي ﯾﺒﯿﻦ ﻋﻼﻗﺔ ﺗﺠﺮﯾﺒﯿﺔ ﺑﯿﻦ )‪ (log k‬و )‪(1/T‬‬
‫•‬
‫ﺷﻜﻞ )‪ : (١٠-٤‬اﻟﻌﻼﻗﺔ اﻟﺨﻄﯿﺔ ﺑﯿﻦ ‪ log k‬و )‪.(1/T‬‬
‫ﺣﯿﺚ اﻟﻤﯿﻞ ﯾﺴﺎوي ‪:‬‬

‫‪Ea‬‬
‫‪2.303R‬‬
‫‪= - 4200 k -1‬‬ ‫•‬
‫ﻟﺬا ﻓﺈن طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪ Ea‬ﺳﺘﺼﺒﺢ ‪:‬‬

‫‪Ea‬‬
‫‪= - 4200 k -1‬‬
‫‪2.303R‬‬
‫‪E a = (- 4200 k -1 ) × (2.303) × (8.314J.mol-1K -1 ) = 80418 J/mol‬‬
‫• أﻣﺎ ﻗﯿﻤﺔ )‪ (A‬ﻓﺘﺤﺴﺐ ﻣﻦ ﺗﻘﺎطﻊ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ﻣ ﻊ اﻟﻤﺤ ﻮر )‪(log k‬‬

‫واﻟ ﺬي ﯾﺴ ﺎوي )‪ (log k = 11‬ﻟ ﺬا ﻓ ﺈن )‪ (A = 1011‬ووﺣﺪاﺗ ﮫ ھ ﻲ‬
‫وﺣﺪات اﻟﺜﺎﺑﺖ )‪ (k‬وﺗﺴﺎوي )‪.(M-1 s-1‬‬

‫‪843‬‬
‫ﻣﺰﻳﺪ ﻣﻦ ﺍﻟﻘﺮﺍءﺓ‬
‫ﺗ ﺆﺛﺮ درﺟ ﺔ اﻟﺤ ﺮارة اﻟﺘ ﻲ ﯾ ﺘﻢ ﻋﻨ ﺪھﺎ اﻟﺘﻔﺎﻋ ﻞ ﺗ ﺄﺛﯿﺮاً إﯾﺠﺎﺑﯿ ﺎ ً ﻋﻠ ﻰ‬
‫)ﻣﻌﺪل( ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫أي أﻧﮫ ﻛﻠﻤﺎ زادت درﺟﺔ اﻟﺤﺮارة اﻟﺘﻲ ﯾﺘﻢ ﻋﻨﺪھﺎ اﻟﺘﻔﺎﻋﻞ زاد ﻣﻌﺪل‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
‫وذﻟﻚ طﺒﻘﺎ ً ﻟﻘﺎﻧﻮن "ﻓﺎﻧﺖ ھﻮف"‪.‬‬
‫• وﯾﻨﺺ ﻗﺎﻧﻮن "ﻓﺎﻧﺖ ھﻮف" ﻋﻠﻰ أﻧﮫ ‪:‬‬
‫ﻋﻨ ﺪ زﯾ ﺎدة درﺟ ﺔ اﻟﺤ ﺮارة ﺑﻤﻘ ﺪار ﻋﺸ ﺮ )‪ (10‬درﺟ ﺎت ﻣﺌﻮﯾ ﺔ ﻓ ﺈن‬
‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﺗ ﺰداد ﺑﻤﻘ ﺪار ﻣ ﺮﺗﯿﻦ )اﻟﻀ ﻌﻒ( أو أرﺑ ﻊ‬
‫ﻣﺮات‪ ،‬وﻓﻲ اﻟﻤﺘﻮﺳﻂ ﺗﺰداد ﺑﻤﻘﺪار ﺛﻼث ﻣﺮات"‪.‬‬
‫• ﻣﻊ أن اﻟﻄﺎﻗﺔ اﻟﺤﺮﻛﯿﺔ ﻟﻠﺠﺰﯾﺌﺎت )ﻓ ﻲ اﻟﺤﺎﻟ ﺔ اﻟﻐﺎزﯾ ﺔ( ﻻ ﺗﺰﯾ ﺪ إﻻ‬
‫ﺑﻤﻘﺪار )‪ ،(3 %‬ﻣﻤﺎ ﯾﺜﺒ ﺖ أن اﻟﻄﺎﻗ ﺔ اﻟﺤﺮﻛﯿ ﺔ )ﺳ ﺮﻋﺔ اﻟﺘﺼ ﺎدم‪،‬‬
‫ﻋﺪد اﻟﺘﺼﺎدﻣﺎت( ﻟﯿﺴﺖ ﺑﺎﻟﻌﺎﻣﻞ اﻟﻤﺆﺛﺮ اﻟﻮﺣﯿﺪ ﻓﻲ ﺗﺤﺪﯾ ﺪ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ‪ .‬ﻓ ﺈذا ﻧﻈﺮﻧ ﺎ اﻟ ﻰ اﻟﻌﻼﻗ ﺔ اﻟﻌﺎﻣ ﺔ ﻟﺴ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ واﻟﺘ ﻲ‬
‫ﺗﻌﺘﻤﺪ ﻓﯿﮭ ﺎ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻠ ﻰ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻣﺮﻓﻮﻋ ﺎ ً‬
‫اﻟ ﻰ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣﻀ ﺮوﺑﺎ ً ﺑﺜﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة‬
‫ﻣﻌﯿﻨﺔ‪.‬‬

‫‪844‬‬
‫ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻞ ‪:‬‬

‫‪A + B ‬‬
‫‪→C + D‬‬
‫ﻣﻌﺎدﻟﺔ ﺳﺮﻋﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ ھﻲ ‪:‬‬

‫]‪Rate = k [ A ] 1 .[ B‬‬
‫‪n‬‬ ‫‪n2‬‬
‫وﯾﺒ ﯿﻦ ﻗ ﺎﻧﻮن اﻟﺴ ﺮﻋﺔ ﻷن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ ﺗﺮﻛﯿ ﺰ‬

‫اﻟﻤﺘﻔﺎﻋﻼت‪،‬‬
‫• وﺗﺨﺘﻠﻒ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﺧﺘﻼﻓﺎ ً ﻛﺒﯿﺮاً ﺑﺪرﺟﺔ اﻟﺤﺮارة ﻟﻠﺘﻔﺎﻋﻞ‪،‬‬
‫• وﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻖ وﺟﺪ أن أﯾﺎ ً ﻣﻦ اﻟﺘﺮﻛﯿﺰ ورﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫ﻻ ﺗﺘﻐﯿ ﺮان ﺑﺘﻐﯿ ﺮ درﺟ ﺔ اﻟﺤ ﺮارة‪ ،‬وﻟﻜ ﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ "‪ "k‬ھ ﻮ‬
‫اﻟﺤ ﺪ اﻟﻮﺣﯿ ﺪ اﻟ ﺬي ﯾﻌﺘﻤ ﺪ ﻋﻠ ﻰ درﺟ ﺔ ﺣ ﺮارة اﻟﺘﻔﺎﻋ ﻞ ﻟﻸﺳ ﺒﺎب‬
‫اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪ -١‬ﻣ ﻦ اﻟﻤﻌ ﺮوف أن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﻮاد ﻻ ﯾﺘﻐﯿ ﺮ ﺑﺘﻐﯿ ﺮ درﺟ ﺔ اﻟﺤ ﺮارة‬
‫ﺧﺼﻮﺻﺎ ً إذا ﻛﺎن اﻟﺤﺠﻢ ﺛﺎﺑﺘﺎ ً‪.‬‬
‫‪ -٢‬ﺗﻐﯿﺮ درﺟﺔ اﻟﺤﺮارة ﻻ ﯾﺆﺛﺮ ﻋﻠﻰ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ إﻻ ﻓﻲ ﺣﺎﻟ ﺔ ﺗﻐﯿ ﺮ‬
‫ﻣﯿﻜﺎﻧﯿﻜﯿﺔ اﻟﺘﻔﺎﻋﻞ وھﻮ اﻷﻣﺮ اﻟﺬي ﻻ ﯾﻤﻜﻦ ﺣﺼﻮﻟﮫ ﻓﻘﻂ ﺑﺘﻐﯿﺮ درﺟﺔ‬
‫اﻟﺤﺮارة‪.‬‬
‫ھﺬان اﻟﺴﺒﺒﺎن ﯾﻘﻮدان اﻟﻰ اﻹﺳ ﺘﻨﺘﺎج ﺑ ﺄن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ھ ﻮ‬
‫اﻟﻌﺎﻣ ﻞ اﻟ ﺬي ﯾﻌﺘﻤ ﺪ ﻋﻠ ﻰ درﺟ ﺔ اﻟﺤ ﺮارة اﻷﻣ ﺮ اﻟ ﺬي ﻻﺣﻈ ﮫ اﻟﻌ ﺎﻟﻢ‬

‫‪845‬‬
‫أرھﯿﻨﯿ ﻮس ﺣﯿ ﺚ وﺟ ﺪ ﻣﻌﻤﻠﯿ ﺎ ً أن ھﻨ ﺎك ﻋﻼﻗ ﺔ ﻋﻜﺴ ﯿﺔ ﺑ ﯿﻦ ﺳ ﺮﻋﺔ‬

‫اﻟﺘﻔﺎﻋﻞ ودرﺟﺔ اﻟﺤﺮارة أو ﺑﻤﻌﻨﻰ آﺧﺮ ‪:‬‬
‫‪b‬‬
‫‪log k = a -‬‬
‫‪T‬‬
‫ﺣﯿﺚ ‪:‬‬
‫)‪ (a , b‬ﺛﺎﺑﺘﺎن ﯾﺘﻐﯿﺮان ﺑﺘﻐﯿﺮ اﻟﺘﻔﺎﻋﻞ‬
‫و )‪ : (T‬ھﻲ درﺟﺔ اﻟﺤﺮارة اﻟﻤﻄﻠﻘﺔ اﻟﺘﻲ ﯾﺤﺪث ﻋﻨﺪھﺎ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫أو ﺑﻤﻌﻨﻰ آﺧﺮ ‪:‬‬
‫‪dln k‬‬ ‫‪b‬‬
‫‪= 2‬‬
‫‪dT‬‬ ‫‪T‬‬
‫‪‬‬ ‫‪‬‬ ‫‪b‬‬
‫• وﯾﻌﺒﺮ ﻋﻦ اﻟﻌﻼﻗ ﺔ ‪  log k = a - T ‬ﺑﯿﺎﻧﯿ ﺎ ً ﺑﺮﺳ ﻢ )‪ (log k‬ﻋﻠ ﻰ‬
‫‪1‬‬
‫ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ‪.‬‬ ‫‪ ‬‬ ‫ﻣﺤﻮر اﻟﺼﺎدات ﻣﻊ‬
‫‪T‬‬
‫اﻟﺸﻜﻞ )‪ (١٠-٤‬ﯾﺒﯿﻦ ﺗﻔﺎﻋﻞ اﻟﺪرﺟﺔ اﻟﺜﺎﻧﯿﺔ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪‬‬
‫‪→ C 2 H 5 OCH 3 + NaI‬‬
‫‪C 2 H 5ONa + CH 3 I ←‬‬
‫‪‬‬
‫‪ ( A + B ←‬اﻟ ﻰ ﺣﺎﻟ ﺔ ﺗ ﻮازن ﺳ ﺘﻜﻮن‬

‫‪‬‬‫وﻋﻨﺪﻣﺎ ﯾﺼﻞ اﻟﺘﻔﺎﻋﻞ ) ‪→ C + D‬‬
‫‪k1‬‬
‫‪k‬‬ ‫‪-1‬‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻄﺮدي )اﻷﻣﺎﻣﻲ( ﻣﺴ ﺎوﯾﺔ ﻟﺴ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻌﻜﺴ ﻲ‬

‫)اﻟﺨﻠﻔﻲ(‪.‬‬

‫‪846‬‬
‫ﺷﻜﻞ )‪ : (١١-٤‬ﺗﻐﯿﺮ ﻗﯿﻤﺔ ‪ k‬ﻣﻊ درﺟﺔ ﺣﺮارة اﻟﺘﻔﺎﻋﻞ ‪T‬‬
‫وﯾﻌﺒﺮ ﻋﻦ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻷﻣﺎﻣﻲ ﺑﺎﻟﻌﻼﻗﺔ ‪:‬‬

‫]‪V1 = k1 [A] [B‬‬
‫ﻓﻲ ﺣﯿﻦ ﯾﻌﺒﺮ ﻋﻦ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﺨﻠﻔﻲ ﺑﺎﻟﻌﻼﻗﺔ ‪:‬‬

‫]‪V2 = k -1 [C] [D‬‬
‫ﺣﯿ ﺚ )‪ (k-1 ،k1‬ھﻤ ﺎ ﺛﺎﺑﺘ ﺎ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔ ﺎﻋﻠﯿﻦ اﻷﻣ ﺎﻣﻲ واﻟﻌﻜﺴ ﻲ‬
‫)اﻟﺨﻠﻔﻲ(‪ ،‬ﻋﻠﻰ اﻟﺘﺮﺗﯿﺐ‪.‬‬
‫وﻋﻨﺪ اﻟﻮﺻﻮل اﻟﻰ ﺣﺎﻟ ﺔ اﻹﺗ ﺰان‪ ،‬ﺗﺘﺴ ﺎوى ﺳ ﺮﻋﺘﺎ اﻟﺘﻔﺎﻋ ﻞ اﻷﻣﺎﻣﯿ ﺔ‬
‫واﻟﺨﻠﻔﯿﺔ‪ ،‬أي أن ‪:‬‬
‫] ‪k1 [ A ][ B] = k -1 [ C ][ D‬‬
‫ﻟﺬا ﻓﺈن ﺛﺎﺑﺖ اﻟﺘﻮازن ﺳﯿﻜﻮن ‪:‬‬

‫‪847‬‬
‫] ‪k1 [ A ][ B] = k -1 [ C][ D‬‬

‫‪k1‬‬ ‫‪k‬‬
‫]‪[ A ][ B] = -1 [ C][ D‬‬
‫‪k -1‬‬ ‫‪k -1‬‬
‫‪k1‬‬ ‫]‪ A  B  = [ C][ D‬‬
‫‪k -1‬‬ ‫]‪  B  [ A ][ B‬‬
‫‪ A ‬‬
‫]‪k1 [ C][ D‬‬
‫=‬
‫]‪k -1 [ A ][ B‬‬
‫‪ k1 ‬‬
‫ﺗﻌﺮف ﺑﺜﺎﺑﺖ اﻻﺗﺰان )‪.(Kc‬‬ ‫‪ ‬‬ ‫واﻟﻨﺴﺒﺔ‬
‫‪ k -1 ‬‬
‫] ‪k1 [ C][ D‬‬

‫=‪K‬‬ ‫=‬
‫]‪k -1 [ A ][ B‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﺛﺎﺑﺖ اﻻﺗ ﺰان )‪ (Kc‬ﯾﺤﺴ ﺐ ﺑﺪﻻﻟ ﺔ اﻟﺘﺮﻛﯿ ﺰات اﻟﺠﺰﯾﺌﯿ ﺔ‬
‫ﻟﻠﻤﺘﻔﺎﻋﻼت‪.‬‬
‫ﻟﺪﯾﻚ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪N 2 (g) + 3H 2 (g) ‬‬
‫)‪→ 2NH3 (g‬‬
‫وﻟﻠﺘﻌﺒﯿﺮ ﻋﻦ ﺛﺎﺑﺖ اﻻﺗﺰان )‪ (K‬ﻓﺈن ‪:‬‬

‫] ‪[ NH3‬‬
‫‪2‬‬
‫=‪K‬‬
‫] ‪[ N 2 ][ H 2‬‬
‫‪3‬‬

‫‪848‬‬
‫وﻟﻘﺪ أﺛﺒﺖ اﻟﻌﺎﻟﻢ ﻓﺎﻧﺖ ھﻮف )‪ (Van't Hoff‬ﺑﺄن ﺗﻐﯿﺮ ﺛﺎﺑﺖ اﻹﺗ ﺰان‬
‫)‪ (K‬ﻣﻊ درﺟﺔ اﻟﺤﺮارة اﻟﻤﻄﻠﻘﺔ )‪ (T‬ﻣﻘﺘ ﺮن ﺑﺎﻷﻧﺜ ﺎﻟﺒﻲ ) ‪ ( ∆H‬ﺣﺴ ﺐ‬
‫اﻟﻌﻼﻗﺔ اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪dlnK c ΔH‬‬
‫=‬
‫‪dT‬‬ ‫‪RT 2‬‬
‫‪‬‬ ‫‪k1 ‬‬
‫ﺳﻨﺤﺼ ﻞ‬ ‫= ‪K‬‬ ‫‪‬‬ ‫ﻓﻠﻮ ﻋﻮﺿﻨﺎ ﻋﻦ ﺛﺎﺑ ﺖ اﻻﺗ ﺰان )‪ (K‬ﻣ ﻦ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪k -1 ‬‬
‫ﻋﻠﻰ اﻟﻌﻼﻗﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪d  k1 ‬‬ ‫‪ΔH‬‬
‫= ‪ln  ‬‬
‫‪dT  k -1  R T 2‬‬
‫ﻣ ﻦ اﻟﻌﻼﻗ ﺔ ) ‪ ( ΔH = ΔE‬ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬ ‫) ‪( ∆H‬‬ ‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ‬
‫‪d‬‬ ‫‪k‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪ΔH ‬‬
‫‪  dT‬وﺑﻌﺪ ﺗﺮﺗﯿﺒﮭﺎ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪ln ‬‬ ‫‪1‬‬
‫=‪‬‬ ‫‪2 ‬‬
‫‪‬‬
‫‪k‬‬ ‫‪‬‬ ‫‪ -1  R T ‬‬
‫‪d  k1 ‬‬ ‫‪ΔH‬‬

‫= ‪ln  ‬‬
‫‪dT  k -1  R T 2‬‬
‫‪d  k1 ‬‬ ‫‪ΔE‬‬
‫= ‪ln  ‬‬
‫‪dT  k -1  R T 2‬‬
‫‪d lnk1 d lnk - 1‬‬ ‫‪ΔE‬‬
‫‪−‬‬ ‫=‬
‫‪dT‬‬ ‫‪dT‬‬ ‫‪R T2‬‬
‫ﺗ ﺆول‬ ‫‪ d lnk1 d lnk - 1‬‬

‫‪‬‬ ‫‪−‬‬ ‫=‬
‫‪ΔE ‬‬
‫‪‬‬ ‫‪ ( ΔE = E1‬ﻓﺈن اﻟﻤﻌﺎدﻟ ﺔ‬ ‫) ‪- E-1‬‬ ‫وﺣﯿﺚ أن‬
‫‪ dT‬‬ ‫‪dT‬‬ ‫‪R T2 ‬‬
‫اﻟﻰ ‪:‬‬
‫‪d lnk1 d lnk - 1‬‬ ‫‪E1‬‬ ‫‪E‬‬
‫‪−‬‬ ‫=‬ ‫‪2‬‬
‫‪− -1 2‬‬
‫‪dT‬‬ ‫‪dT‬‬ ‫‪RT RT‬‬

‫‪849‬‬
‫• ﻟﻘ ﺪ اﻗﺘ ﺮح اﻟﻌ ﺎﻟﻢ أرھﯿﻨﯿ ﻮس أن ھ ﺬه اﻟﻌﻼﻗ ﺔ ﺗﺒ ﯿﻦ أن اﻟﺘﻔﺎﻋ ﻞ‬

‫اﻟﻄ ﺮدي واﻟﺘﻔﺎﻋ ﻞ اﻟﻌﻜﺴ ﻲ ﻟﮭﻤ ﺎ ﺗ ﺄﺛﯿﺮان ﻣﺴ ﺘﻘﻼن ﻋﻠ ﻰ ﺣﺮﻛﯿ ﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ اﻟ ﺬي ﺑ ﺪوره ﯾﺴ ﻤﺢ ﻟﻨ ﺎ ﺑﻔﺼ ﻞ اﻟﻌﻼﻗ ﺔ‬
‫‪ d lnk1 d lnk - 1‬‬ ‫‪E1‬‬ ‫‪E ‬‬
‫اﻟﻰ ﻋﻼﻗﺘﯿﻦ ﻣﺴ ﺘﻘﻠﺘﯿﻦ إﺣ ﺪاھﻤﺎ‬ ‫‪‬‬ ‫‪−‬‬ ‫=‬ ‫‪2‬‬
‫‪− -1 2 ‬‬
‫‪ dT‬‬ ‫‪dT‬‬ ‫‪RT RT ‬‬
‫ﻟﻠﺘﻔﺎﻋﻞ اﻟﻄﺮدي ‪:‬‬

‫‪d lnk1‬‬ ‫‪E‬‬
‫‪= 12 + I‬‬
‫‪dT‬‬ ‫‪RT‬‬
‫واﻷﺧﺮى ﻟﻠﺘﻔﺎﻋﻞ اﻟﻌﻜﺴﻲ ‪:‬‬
‫‪d lnk - 1‬‬ ‫‪E -1‬‬
‫=‬ ‫‪+I‬‬
‫‪dT‬‬ ‫‪R T2‬‬
‫ﺣﯿ ﺚ اﻟﻤﻌﺎﻣ ﻞ )‪ (I‬ﺛﺎﺑ ﺖ‪ ،‬وﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﻌﺪﯾ ﺪ ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﻓﻘ ﺪ وﺟ ﺪ‬

‫أرھﯿﻨﯿ ﻮس ﺗﺠﺮﯾﺒﯿ ﺎ ً أن )‪ (I = 0‬اﻷﻣ ﺮ اﻟ ﺬي ﯾﻘﻮدﻧ ﺎ اﻟ ﻰ اﻟﻌﻼﻗ ﺔ‬
‫اﻟﻌﺎﻣﺔ ﻟﻤﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس واﻟﺘﻲ ﺗﺠﻤﻊ ﺑ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ واﻟﻄﺎﻗ ﺔ‬
‫ودرﺟﺔ اﻟﺤﺮارة اﻟﻤﻄﻠﻘﺔ‪.‬‬
‫‪dlnk‬‬ ‫‪E‬‬
‫‪= a2‬‬
‫‪dT‬‬ ‫‪RT‬‬
‫ﺣﯿﺚ ‪:‬‬
‫)‪ : (k‬ھﻮ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ اﻟﻨﻮﻋﻲ ﻟﻠﺘﻔﺎﻋﻞ‬
‫‪ : Ea‬ھﻲ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬

‫‪850‬‬
‫‪ dlnk‬‬ ‫‪E ‬‬

‫ﺑﺪﻻﻟ ﺔ )‪ (T‬وﻣﻜﺎﻣﻠﺘﮭ ﺎ ﺑ ﯿﻦ ‪ 0‬و ‪T‬‬ ‫‪‬‬ ‫‪= a2 ‬‬ ‫وﺑﺘﺮﺗﯿ ﺐ اﻟﻌﻼﻗ ﺔ‬
‫‪ dT‬‬ ‫‪RT ‬‬

‫‪ln k T‬‬ ‫‪T‬‬
‫‪Ea‬‬ ‫‪1‬‬
‫∫‬
‫‪ln k 0‬‬
‫‪dlnk‬‬ ‫=‬
‫‪R‬‬ ‫‪∫0 T 2 dt‬‬
‫‪Ea‬‬
‫‪⇒ ln k = -‬‬ ‫‪+ ln A‬‬
‫‪RT‬‬
‫ﺣﯿﺚ ‪:‬‬
‫)‪ : (A‬ھﻮ ﺛﺎﺑﺖ اﻟﺘﻜﺎﻣﻞ وﯾﻌﺮف ﺑﻤﻌﺎﻣﻞ اﻟﺘﺮدد‬
‫‪ : Ea‬طﺎﻗﺔ أرھﯿﻨﯿﻮس أو ﻣﺎ ﯾﻌﺮف اﻵن ﺑﻄﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ‬
‫‪ : T‬درﺟﺔ اﻟﺤﺮارة اﻟﻤﻄﻠﻘﺔ‬
‫‪ : R‬ھﻮ ﺛﺎﺑﺖ اﻟﻐﺎزات اﻟﻌﺎم )‪(R = 8.314 J/mol K‬‬
‫‪ : k‬ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬
‫ﺑﻤﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس‪ ،‬واﻟﺘﻲ‬ ‫‪‬‬ ‫‪ln‬‬ ‫‪k‬‬ ‫=‬ ‫‪-‬‬ ‫‪+ ln A ‬‬ ‫• وﺗﻌﺮف اﻟﻤﻌﺎدﻟﺔ‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬
‫ﯾﻤﻜﻦ أن ﺗﻜﺘﺐ ﺑﺘﻌﺒﯿﺮ أﻛﺜﺮ ﺷﮭﺮة ‪:‬‬
‫‪k = A e - Ea /RT‬‬
‫• وﺑﺘﺤﻮﯾ ﻞ ‪ ln‬اﻟ ﻰ اﻟﻠﻮﻏ ﺎرﯾﺘﻢ اﻟﻌﺸ ﺮي ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬
‫‪  ln k = -‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪+ ln A ‬‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬

‫‪851‬‬
‫‪ E 1‬‬
‫‪2.303 log k =  - a  + ln A‬‬
‫‪ R T‬‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪1‬‬
‫‪⇒ log k =  -‬‬ ‫‪ + ln A‬‬
‫‪ 2.303 R  T‬‬
‫‪‬‬ ‫‪‬‬ ‫‪Ea‬‬ ‫‪1‬‬ ‫‪‬‬

‫ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ‪،‬‬ ‫‪ log k =  - 2.303 R  T + ln A ‬‬ ‫• واﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫‪1‬‬
‫ﻋﻠ ﻰ ﻣﺤ ﻮر‬ ‫‪ ‬‬ ‫ﺣﯿ ﺚ ﯾﻤﺜ ﻞ )‪ (ln k‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات‪ ،‬و‬
‫‪T‬‬
‫‪‬‬ ‫‪Ea ‬‬

‫‪.-‬‬ ‫‪‬‬ ‫اﻟﺴﯿﻨﺎت‪ ،‬ﻓﻨﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ‬
‫‪ 2.303 R ‬‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬

‫وﻋﻼﻗ ﺔ أرھﯿﻨﯿ ﻮس‬ ‫‪ ln k = - RT + ln A ‬‬ ‫• وﺑﻤﻘﺎرﻧ ﺔ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬
‫‪‬‬ ‫‪b‬‬
‫ﺗﺘﺴﺎوى اﻟﻌﻼﻗﺘﺎن ‪:‬‬ ‫‪ ln k = a - ‬‬ ‫اﻟﺘﺠﺮﯾﺒﯿﺔ‬
‫‪‬‬ ‫‪T‬‬
‫‪Ea‬‬
‫‪ln k = -‬‬ ‫‪+ ln A‬‬
‫‪RT‬‬
‫‪b‬‬
‫‪ln k = a -‬‬
‫‪T‬‬
‫‪E‬‬ ‫‪b‬‬
‫‪- a + ln A = a -‬‬
‫‪RT‬‬ ‫‪T‬‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬
‫أو‬ ‫‪ ln k = - RT + ln A ‬‬ ‫ﺗﺘﻐﯿ ﺮ ﻣﻌﺎدﻟ ﺔ أرھﯿﻨﯿ ﻮس ﺑﺸ ﻜﻠﮭﺎ‬
‫‪‬‬ ‫‪‬‬
‫‪ ( k = A e‬ﻣ ﻦ ﻋﻼﻗ ﺔ أرھﯿﻨﯿ ﻮس اﻟﺘﺠﺮﯾﺒﯿ ﺔ‬ ‫)‬

‫‪‬‬ ‫‪a‬‬ ‫‪- E /RT‬‬
‫‪ ln k = b - ‬‬
‫‪a‬‬
‫‪‬‬ ‫‪T‬‬
‫ﺑ ﺎﻓﺘﺮاض أن درﺟ ﺔ اﻟﺤ ﺮارة اﻟﻤﻄﻠﻘ ﺔ ﻻ ﺗ ﺆﺛﺮ ﻋﻠ ﻰ )‪ (Ea‬أو )‪(A‬‬

‫‪852‬‬
‫وﻟﻜ ﻦ ﻓﻘ ﻂ ﻋﻠ ﻰ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ ،(k‬ﻟ ﺬا ﻓ ﺈن وﺣ ﺪات ﻣﻌﺎﻣ ﻞ‬

‫اﻟﺘ ﺮدد )‪ (A‬ﺗﻜ ﻮن ﻣﺴ ﺎوﯾﺔ ﻟﻮﺣ ﺪات اﻟﺜﺎﺑ ﺖ )‪ (k‬وﺗﺘﺴ ﺎوى ﻗﯿﻤﺘﮭ ﺎ‬
‫ﻋﺪدﯾﺎ ً ﻋﻨﺪﻣﺎ ﺗﻜﻮن )‪ (Ea‬ﻣﺴﺎوﯾﺔ ﻟﺼﻔﺮ‪.‬‬
‫ﺍﻟﻄﺎﻗﺔ ﺍﻟﻔﻌﺎﻟﺔ‬
‫ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻞ اﻟﻤﺘﺰن اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪‬‬
‫‪A + B ‬‬
‫‪k1‬‬
‫‪‬‬
‫‪C + D‬‬
‫‪k -1‬‬
‫وﺟ ﺪ أن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻷﻣ ﺎﻣﻲ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ )‪ ،(E1‬ﻓ ﻲ ﺣ ﯿﻦ ﺗﻌﺘﻤ ﺪ‬

‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﺨﻠﻔ ﻲ ﻋﻠ ﻰ )‪ .(E-1‬وھ ﺬا ﯾﻮﺿ ﺢ أن ﻣﺴ ﺎر اﻟﺘﻔﺎﻋ ﻞ‬
‫ﻣﻦ )‪ (A + B‬اﻟ ﻰ )‪ (C + D‬ﯾﺘﻀ ﻤﻦ ﺗﻐﯿ ﺮاً ﻓ ﻲ اﻟﻄﺎﻗ ﺔ ﻗ ﺪره )‪(E1‬‬
‫ﻓ ﻲ ﺣ ﯿﻦ ﯾﻜ ﻮن ﺗﻐﯿ ﺮ اﻟﻄﺎﻗ ﺔ ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﺘﻔﺎﻋ ﻞ اﻟﺨﻠﻔ ﻲ )ﻣ ﻦ ‪(C + D‬‬
‫اﻟﻰ )‪ (A + B‬ھﻮ )‪ (E-1‬وﯾﻜﻮن اﻟﻔﺮق ﺑ ﯿﻦ اﻟﻘﯿﻤﺘ ﯿﻦ ھ ﻮ ﻋﺒ ﺎرة ﻋ ﻦ‬
‫) ‪. ( ∆E‬‬
‫• وﻻ ﺗﺤ ﺪث ﻣﺜ ﻞ ھ ﺬه اﻟﺘﻐﯿ ﺮات ﻓ ﻲ اﻟﻄﺎﻗ ﺔ إﻻ إذا أﺟ ﺮي اﻟﺘﻔﺎﻋ ﻞ‬
‫وﻣ ﺮ ﺑﺤﺎﻟ ﺔ وﺳ ﻄﯿﺔ ﺗﻜ ﻮن ﻟﮭ ﺎ ﻗ ﺪر ﻣ ﻦ اﻟﻄﺎﻗ ﺔ )‪ (E1‬ﻗﺒ ﻞ ﺗﻜ ﻮﯾﻦ‬
‫اﻟﻤﺘﺮاﻛ ﺐ اﻟﻮﺳ ﻄﻲ ﺛ ﻢ اﻟﻨ ﻮاﺗﺞ )‪ ،(C + D‬وﺗﺴ ﻤﻰ ھ ﺬه اﻟﻄﺎﻗ ﺔ‬
‫ب"اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ"‪ ،‬وﯾﺮﻣ ﺰ ﻟﮭ ﺎ ﺑ ﺎﻟﺮﻣﺰ ‪ .E1‬وھ ﺬه ھ ﻲ أﻗ ﻞ طﺎﻗ ﺔ‬

‫‪853‬‬
‫ﯾﻤﻜ ﻦ ﻟﻠﻤﺘﻔ ﺎﻋﻼت )‪ (A‬و )‪ (B‬أن ﺗﺴ ﺘﺤﻮذ ﻋﻠﯿﮭ ﺎ ﻗﺒ ﻞ أن ﯾﺴ ﯿﺮ‬

‫اﻟﺘﻔﺎﻋﻞ اﻟﻰ ﻧﮭﺎﯾﺘﮫ ﺣﯿﺚ ﯾﻌﻄﻲ )‪.(C + D‬‬
‫• وﻣ ﻦ اﻟﻨﻈﺮﯾ ﺎت اﻟﺤﺪﯾﺜ ﺔ‪ ،‬وﺟ ﺪ أن اﻟﻄﺎﻗ ﺔ اﻟﻼزﻣ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫اﻟﺤ ﺮاري ﯾ ﺘﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿﮭ ﺎ ﻣ ﻦ اﻟﺘﺼ ﺎدﻣﺎت اﻟﻤﺴ ﺘﻤﺮة ﺑ ﯿﻦ‬
‫اﻟﺠﺰﯾﺌﺎت اﻟﻤﺘﻔﺎﻋﻠﺔ‪ .‬وﻟﯿﺴ ﺖ ﻛ ﻞ اﻟﺠﺰﯾﺌ ﺎت ﺗﻤﺘﻠ ﻚ ھ ﺬا اﻟﻘ ﺪر ﻣ ﻦ‬
‫اﻟﻄﺎﻗﺔ‪ ،‬وﻟﻜﻦ ﺟﺰءاً ﻣﻦ اﻟﻤﺘﻔﺎﻋﻼت ھﻮ اﻟﺬي ﯾﻜﻮن ﻟﮫ اﻟﻘﺪرة ﻋﻠﻰ‬
‫اﻣ ﺘﻼك ھ ﺬه اﻟﻄﺎﻗ ﺔ‪ ،‬وﺑﺎﻟﺘ ﺎﻟﻲ‪ ،‬ﻓﮭ ﻮ ﻓﻘ ﻂ اﻟ ﺬي ﯾﻜ ﻮن ﻟﺪﯾ ﮫ اﻟﻘ ﺪرة‬
‫ﻟﻠ ﺪﺧﻮل ﻓ ﻲ ﺗﻔﺎﻋ ﻞ ﻛﯿﻤﯿ ﺎﺋﻲ ﺣﯿ ﺚ ﺗﺘﻜ ﻮن ﻣ ﻮاد ﺟﺪﯾ ﺪة ﺗﻌ ﺮف‬
‫ﺑ ﺎﻟﻨﻮاﺗﺞ‪ .‬وﺗﺴ ﻤﻰ اﻟﺘﺼ ﺎدﻣﺎت اﻟﺘ ﻲ ﯾﻨ ﺘﺞ ﻋﻨﮭ ﺎ ﺗﻔﺎﻋ ﻞ‬
‫"اﻟﺘﺼﺎدﻣﺎت اﻟﻔﻌﺎﻟﺔ" أو " اﻟﺘﺼﺎدﻣﺎت اﻟﻤﺜﻤﺮة"‪.‬‬
‫ﺷﻜﻞ )‪ : (١٢-٤‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ طﺎﻗﺔ اﻟﻮﺿﻊ وﺧﻂ ﺳﯿﺮ اﻟﺘﻔﺎﻋﻞ ﻟﺘﻔﺎﻋﻞ ﻣﺎص ﻟﻠﺤﺮارة‬

‫‪854‬‬
‫• وﺗﻌﺘﻤﺪ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ ﻋﻠﻰ ﻋﺎﻣﻠﯿﻦ‪ ،‬ھﻤﺎ ‪:‬‬

‫أ( ﺗﺮدد اﻟﺘﺼﺎدﻣﺎت ﺑﯿﻦ اﻟﺠﺰﯾﺌ ﺎت اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ ،‬وﯾﺮﻣ ﺰ ﻟﻠﺘ ﺮدد ﺑ ﺎﻟﺮﻣﺰ‬
‫"‪"A‬‬
‫ب( ﻗﯿﻤﺔ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ )‪(E‬‬
‫وﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﺗﻜﺘﺐ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ﻋﻠﻰ اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫) ‪k = A exp( - E / RT‬‬
‫وﯾﺄﺧ ﺬ ﻣﻌﺎﻣ ﻞ اﻟﺘ ﺮدد "‪ "A‬ﻧﻔ ﺲ وﺣ ﺪات ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ‪ ،k‬وﯾﻤﻜ ﻦ‬
‫ﻛﺘﺎﺑﺔ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ﻓﻲ اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪E‬‬
‫‪ln k = ln A -‬‬
‫‪RT‬‬
‫‪E‬‬
‫‪2.303 log k = 2.303 logA -‬‬
‫‪RT‬‬
‫‪2.303‬‬ ‫‪2.303‬‬ ‫‪E‬‬
‫= ‪log k‬‬ ‫‪logA -‬‬
‫‪2.303‬‬ ‫‪2.303‬‬ ‫‪2.303 RT‬‬
‫‪E‬‬
‫‪⇒ log k = logA -‬‬
‫‪2.303 RT‬‬
‫واﻟﺠﺪول )‪ (١-٤‬ﯾﺒﯿﻦ ﻗﯿﻤ ﺔ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ وﻣﻌﺎﻣ ﻞ اﻟﺘ ﺮدد ﻟﺘﻔ ﺎﻋﻼت‬
‫أﺣﺎدﯾﺔ وﺛﻨﺎﺋﯿﺔ اﻟﺠﺰﯾﺌﯿﺔ‬

855
‫ ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬: ‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ‬
‫ ﺍﳍﺰﺍﺯﻱ‬‫ ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‬.‫ ﺩ‬/‫ﺇﻋﺪﺍﺩ‬
(١-٤) ‫ﺟﺪول‬
Unimolecular reaction E kJ/mol A s-1
1- C2 H 5Cl 
→ C 2 H 4 + HCl 254.4 4 × 1014
2- C2 H5 Br 
→ C2 H4 + HBr 218.8 7 × 1012
3- CH 3COOC 2 H 5 
→ C2 H 4 + CH 3COOH 200.0 3 × 1012
4- C 6 H 2 (NO 2 )3COOH 
→ C 6 H 3 (NO 2 )3 + CO 2 96.2 1 × 1014
Bimolecular reaction E kJ/mol A L mol-1 s-1
1- 2HI 
→ H2 + I2 186.2 1.6 × 1011
2- 2NO 2 
→ 2NO + O 2 112.5 9.4 × 109
3- CH 3COOC 2 H 5 
→ CH 3COO- + C 2 H 5OH 6.5 7.9 × 105
4- CH 3 I + ( C2 H5 )3 N 
→ CH3 N(C2 H5 )3 I 40.6 2.1 × 104
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‫‪856‬‬
‫ﻃﺮﻕ ﺗﻌﻴﲔ ﺍﻟﻄﺎﻗﺔ ﺍﻟﻔﻌﺎﻟﺔ )ﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ(‬

‫ﯾﻤﻜﻦ ﺗﻌﯿﯿﻦ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ ﻟﻠﺘﻔﺎﻋﻞ ﺑﺈﺣﺪى اﻟﻄﺮﯾﻘﺘﯿﻦ اﻟﺘﺎﻟﯿﺘﯿﻦ ‪:‬‬
‫ﺍﻟﻄﺮﻳﻘﺔ ﺍﻷﻭﱃ ﳊﺴﺎﺏ ﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ‬
‫وﺗﻌﺘﻤﺪ ھﺬه اﻟﻄﺮﯾﻘﺔ ﻋﻠﻰ ﻗﯿ ﺎس ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺎت‬
‫اﻟﺤﺮارة اﻟﻤﺨﺘﻠﻔﺔ‪ ،‬ﺛﻢ ﺗﺮﺳﻢ اﻟﻌﻼﻗﺔ اﻟﺒﯿﺎﻧﯿﺔ ﻟﻠﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪E‬‬
‫‪log k = logA -‬‬
‫‪2.303 RT‬‬
‫ﺑﺘﻤﺜﯿ ﻞ )‪ (log k‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات‪ ،‬و )‪ (1/T‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬

‫اﻟﺴ ﯿﻨﺎت‪ ،‬ﺣﯿ ﺚ ﺗﻜ ﻮن اﻟﻌﻼﻗ ﺔ ﺧﻄﯿ ﺔ وﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ‪،‬‬
‫‪ -E ‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ‬ ‫‪‬‬ ‫‪‬‬ ‫وﯾﻜﻮن ﻣﯿﻠﮫ ھﻮ‬
‫‪ 2.303 R ‬‬
‫‪‬‬ ‫‪Ea ‬‬

‫ﺣﯿ ﺚ اﻟﻤﯿ ﻞ‬ ‫‪‬‬
‫‪‬‬
‫‪lnk‬‬ ‫=‬ ‫‪lnA‬‬ ‫‪-‬‬
‫‪RT ‬‬
‫)‪ .(E‬ﻛﻤﺎ وﯾﻤﻜ ﻦ اﺳ ﺘﺨﺪام اﻟﻤﻌﺎدﻟ ﺔ‬
‫)‪.(- E/R‬‬
‫س( وﺿ ﺢ طﺮﯾﻘ ﺔ ﺣﺴ ﺎب طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﺑﺎﺳ ﺘﺨﺪام ﻣﻌﺎدﻟ ﺔ‬
‫أرھﯿﻨﯿﻮس‪.‬‬

‫‪857‬‬
‫ﺗﻄﺒﻴﻘﺎﺕ ﺣﺴﺎﺑﻴﺔ ﻋﻠﻰ ﻣﻌﺎﺩﻟﺔ ﺃﺭﻫﻴﻨﻴﻮﺱ‬
‫ﻣﺜﺎﻝ )‪(١-٤‬‬
‫إن ﻣﻌ ﺪل ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻟﺘﺤﻠ ﻞ اﻷﺳ ﯿﺘﻮن ﺛﻨ ﺎﺋﻲ‬
‫ﺣﺎﻣﺾ اﻟﻜﺮﺑﻮﻛﺴﯿﻞ ﻓﻲ ﻣﺤﻠﻮل ﻣﺎﺋﻲ ﻣﺒﯿﻦ ﻓ ﻲ اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﻛﺪاﻟ ﺔ‬
‫ﻟﺪرﺟﺔ اﻟﺤﺮارة ‪:‬‬
‫‪T, ºC‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬ ‫‪60‬‬
‫‪k × 105 s-1‬‬ ‫‪2.46‬‬ ‫‪10.8‬‬ ‫‪47.5‬‬ ‫‪163‬‬ ‫‪576‬‬ ‫‪1850 5480‬‬
‫اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ‪:‬‬

‫‪ ΔE  1‬‬
‫‪log k = log A - ‬‬ ‫‪‬‬
‫‪ 2.303 R  T‬‬
‫‪1‬‬
‫ﻋﻠﻰ‬ ‫‪ ‬‬ ‫وﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪ (log k‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات‪ ،‬ﻣﻘﺎﺑﻞ‬
‫‪T‬‬
‫ﻣﺤﻮر اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ‪ .  − 2.303 R ‬وﯾﻤﻜ ﻦ‬

‫‪ΔE‬‬
‫‪‬‬ ‫‪‬‬
‫ﻣﻦ اﻟﻘﯿﻢ اﻟﻤﻮﺟﻮدة ﻓﻲ اﻟﺠﺪول اﻟﺴﺎﺑﻖ ﻋﻤ ﻞ اﻟﺒﯿﺎﻧ ﺎت اﻟﻼزﻣ ﺔ ﻟﺘﻤﺜﯿ ﻞ‬

‫ھﺬه اﻟﻌﻼﻗﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪858‬‬
‫‪T, ºC‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬ ‫‪60‬‬

‫‪T, K‬‬ ‫‪273‬‬ ‫‪283‬‬ ‫‪293‬‬ ‫‪303‬‬ ‫‪313‬‬ ‫‪323‬‬ ‫‪333‬‬
‫‪1‬‬ ‫‪36.6‬‬ ‫‪35.3‬‬ ‫‪34.1‬‬ ‫‪33.0‬‬ ‫‪32.0‬‬ ‫‪31.0‬‬ ‫‪30.0‬‬
‫‪ ‬‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬
‫‪T‬‬
‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬
‫‪1‬‬ ‫‪4‬‬
‫‪  × 10‬‬ ‫‪36.6‬‬ ‫‪35.3‬‬ ‫‪34.1‬‬ ‫‪33.0‬‬ ‫‪32.0‬‬ ‫‪31.0‬‬ ‫‪30.0‬‬
‫‪T‬‬
‫‪2.46‬‬ ‫‪10.8‬‬ ‫‪47.5‬‬ ‫‪163‬‬ ‫‪576‬‬ ‫‪1850‬‬ ‫‪5480‬‬

‫‪k s-1‬‬
‫‪× 10-5‬‬ ‫‪× 10-5‬‬ ‫‪× 10-5‬‬ ‫‪× 10-5‬‬ ‫‪× 10-5‬‬ ‫‪× 10-5‬‬ ‫‪× 10-5‬‬
‫‪- 46.1‬‬ ‫‪- 39.7‬‬ ‫‪- 33.2‬‬ ‫‪- 27.9‬‬ ‫‪- 22.4‬‬ ‫‪- 17.3‬‬ ‫‪- 12.6‬‬
‫‪log k‬‬
‫‪× 10-1‬‬ ‫‪× 10-1‬‬ ‫‪× 10-1‬‬ ‫‪× 10-1‬‬ ‫‪× 10-1‬‬ ‫‪× 10-1‬‬ ‫‪× 10-1‬‬
‫‪log k × 10‬‬ ‫‪- 46.1‬‬ ‫‪- 39.7‬‬ ‫‪- 33.2‬‬ ‫‪- 27.9‬‬ ‫‪- 22.4‬‬ ‫‪- 17.3‬‬ ‫‪- 12.6‬‬
‫وﺑﺘﻤﺜﯿﻞ اﻟﻘﯿﻢ اﻟﺘﺎﻟﯿﺔ ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات ‪:‬‬

‫‪log k × 10‬‬ ‫‪- 46.1 - 39.7 - 33.2 - 27.9 - 22.4 - 17.3 - 12.6‬‬
‫واﻟﻘﯿﻢ اﻟﺘﺎﻟﯿﺔ ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ‪:‬‬

‫‪1‬‬
‫‪ ‬‬
‫‪× 104‬‬
‫‪T‬‬ ‫‪36.6‬‬ ‫‪35.3‬‬ ‫‪34.1‬‬ ‫‪33.0‬‬ ‫‪32.0‬‬ ‫‪31.0‬‬ ‫‪30.0‬‬
‫ﺷﻜﻞ )‪(١٣-٤‬‬

‫‪859‬‬
‫وﻣ ﻦ اﻟﺮﺳ ﻢ ﺑﺎﻟﺸ ﻜﻞ )‪ (١٣-٤‬ﻓ ﺈن ﻣﯿ ﻞ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ ھ ﻮ‬

‫)‪(slope = - 5.08 × 103‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪ΔE‬‬
‫‪slope = -‬‬
‫‪2.303 R‬‬
‫) ‪ΔE = slope × ( - 2.303 R‬‬
‫) ‪ΔE = - 5.08 × 103 × ( - 2.303 × 8.314‬‬
‫‪ΔE = 97267.48 J/mol‬‬
‫‪ΔE = 97.3 kJ/mol‬‬
‫ﻣﺜﺎﻝ )‪(٢-٤‬‬
‫إذا ﻋﻠﻤﺖ أن ﺛﺎﺑﺖ ﺳﺮﻋﺔ ﺗﻔﺎﻋﻞ إﻣﺎھﺔ ﯾﻮدﯾﺪ اﻹﯾﺜﯿﻞ ﻓ ﻲ وﺳ ﻂ ﻗﻠ ﻮي‬

‫ﯾﺘﻐﯿﺮ ﻣﻊ درﺟﺔ اﻟﺤﺮارة ﻓﻲ اﻟﻤﺠﺎل )‪ (20 – 80 ºC‬ھﻲ ﻛﺎﻵﺗﻲ ‪:‬‬
‫‪Temperature/ ºC‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬ ‫‪60‬‬ ‫‪70‬‬ ‫‪80‬‬
‫‪K × 103 dm3 mol-1 s-1‬‬ ‫‪0.100‬‬ ‫‪0.335‬‬ ‫‪1.06‬‬ ‫‪3.06‬‬ ‫‪8.13‬‬ ‫‪21.10‬‬ ‫‪50.10‬‬
‫ﻓﺎﺣﺴﺐ ‪:‬‬
‫أ( طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﻠﺘﻔﺎﻋﻞ )‪(Ea‬‬
‫ب( ﻣﻌﺎﻣﻞ اﻟﺘﺮدد )‪.(A‬‬

‫‪860‬‬
‫ﺍﳊﻞ‬
‫‪‬‬ ‫‪Ea  1 ‬‬ ‫‪‬‬

‫ﺣﯿ ﺚ‬ ‫‪ lnk = - R  T  + lnA ‬‬ ‫ﻟﺤﺴ ﺎب طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻧﺴ ﺘﺨﺪم اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪ ‬‬ ‫‪‬‬
‫ﯾﻤﻜ ﻦ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ اﻟﻠﻮﻏ ﺎرﯾﺘﻢ اﻟﻄﺒﯿﻌ ﻲ ﻟﺜﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬

‫)‪ (lnk‬وﻣﻘﻠ ﻮب درﺟ ﺔ اﻟﺤ ﺮارة )‪ (1/T‬ﺑﺤﯿ ﺚ ﺗﻘ ﺪر درﺟ ﺔ اﻟﺤ ﺮارة‬
‫ﺑﺎﻟﻤﻘﯿﺎس اﻟﻤﻄﻠﻖ )‪ .(Kelvin‬وﻣﻦ ﻣﯿ ﻞ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ اﻟﻨ ﺎﺗﺞ ﯾﻤﻜ ﻦ‬
‫ﺣﺴﺎب طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Temperature/ ºC‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬ ‫‪60‬‬ ‫‪70‬‬ ‫‪80‬‬
‫)‪T (K‬‬ ‫‪293‬‬ ‫‪303‬‬ ‫‪313‬‬ ‫‪323‬‬ ‫‪333‬‬ ‫‪343‬‬ ‫‪353‬‬
‫‪(1/T) × 103‬‬ ‫‪3.413‬‬ ‫‪3.300‬‬ ‫‪3.195‬‬ ‫‪3.096‬‬ ‫‪3.003‬‬ ‫‪2.915‬‬ ‫‪2.833‬‬
‫‪k × 103 dm3 mol-1 s-1‬‬ ‫‪0.100‬‬ ‫‪0.335‬‬ ‫‪1.06‬‬ ‫‪3.06‬‬ ‫‪8.13‬‬ ‫‪21.10‬‬ ‫‪50.10‬‬
‫‪ln k‬‬ ‫‪- 9.210‬‬ ‫‪- 8.001‬‬ ‫‪- 6.850‬‬ ‫‪- 5.789‬‬ ‫‪- 4.812‬‬ ‫‪- 3.858‬‬ ‫‪- 2.994‬‬
‫ﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪ (ln k‬و )‪ (1/T‬ﻧﺤﺼﻞ ﻋﻠﻰ اﻟﺸﻜﻞ )‪.(١٤-٤‬‬
‫ﺷﻜﻞ )‪(١٤-٤‬‬

‫‪861‬‬
‫‪‬‬ ‫‪- 8 × 103 - (- 3.5 × 103 ) ‬‬ ‫‪‬‬

‫= ‪ slope‬‬
‫‪‬‬ ‫)‪(3.3 - 2.9‬‬
‫‪= - 11.25 × 10 ‬‬
‫‪3‬‬
‫‪‬‬ ‫واﻟﺬي ﻣﯿﻠﮫ ‪:‬‬
‫‪‬‬ ‫‪‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪:‬‬

‫‪Ea‬‬
‫‪slope = -‬‬
‫‪R‬‬
‫‪E a = - (slope) × R‬‬
‫‪E a = - ( - 11250) × 8.314‬‬
‫‪E a = 93532.5 J mol -1‬‬
‫‪E a = 93.53 kJ mol -1‬‬
‫ب( ﺣﺴﺎب ﻣﻌﺎﻣﻞ اﻟﺘﺮدد ‪:‬‬

‫‪‬‬ ‫‪Ea ‬‬
‫ﻋﻨ ﺪ‬ ‫‪‬‬ ‫‪lnk‬‬ ‫=‬ ‫‪lnA‬‬ ‫‪-‬‬ ‫‪‬‬ ‫ﯾﻤﻜﻦ ﺣﺴﺎب ﻣﻌﺎﻣﻞ اﻟﺘﺮدد ﺑﺎﺳ ﺘﺨﺪام اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪RT ‬‬
‫أي درﺟ ﺔ ﺣ ﺮارة‪ .‬ﻓ ﺈذا اﺳ ﺘﺨﺪﻣﻨﺎ درﺟ ﺔ اﻟﺤ ﺮارة )‪ (323 K‬ﻓﺈﻧﻨ ﺎ‬
‫‪Ea‬‬
‫‪lnk = lnA -‬‬
‫‪RT‬‬
‫‪E‬‬
‫‪ln A = lnk + a‬‬
‫‪RT‬‬
‫‪ 93532.5 ‬‬
‫‪ln A = - 5.789 + ‬‬ ‫‪‬‬
‫‪ 8.314 × 323 ‬‬
‫‪ln A = 29.041‬‬
‫‪k = 4.095 × 1012 dm3 mol-1s-1‬‬

‫‪862‬‬
‫ﻣﺜﺎﻝ )‪(٣-٤‬‬
‫ﻓ ﻲ ﺗﺠﺮﺑ ﺔ اﻟﺘﻤﯿ ﺆ اﻟﻘﻠ ﻮي ﻟﯿﻮدﯾ ﺪ اﻹﯾﺜﯿ ﻞ ﻋﻨ ﺪ ﻣ ﺪى ﻣ ﻦ درﺟ ﺎت‬

‫اﻟﺤﺮارة ﻣﻦ ‪ 20 ºC‬اﻟﻰ ‪ ، 80 ºC‬ﺗﻢ اﻟﺤﺼﻮل ﻋﻠﻰ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫)‪103 k (dm3 mol-1 s-1‬‬ ‫‪0.100 0.335 1.41‬‬ ‫‪3.06‬‬ ‫‪8.13‬‬ ‫‪21.1‬‬ ‫‪50.1‬‬
‫)‪T (ºC‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬ ‫‪60‬‬ ‫‪70‬‬ ‫‪80‬‬
‫اﺣﺴﺐ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ ﻟﺬﻟﻚ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻟﺤﺴ ﺎب اﻟﻄﺎﻗ ﺔ اﻟﻔﻌﺎﻟ ﺔ )طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ( ﻓﺈﻧﻨ ﺎ ﻧﻄﺒ ﻖ اﻟﻌﻼﻗ ﺔ ‪:‬‬
‫‪‬‬ ‫‪‬‬
‫وذﻟﻚ ﺑﺮﺳ ﻢ ﻗ ﯿﻢ )‪ (1/T‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت‬ ‫‪ log k = logA -‬‬
‫‪E‬‬
‫‪‬‬
‫‪‬‬ ‫‪2.303 RT ‬‬
‫وﻗﯿﻢ )‪ (log k‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات‪ ،‬ﻓﻨﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ‬

‫)‪ (- E/2.303R‬وﻣﻨﮫ ﻧﻮﺟﺪ ﻗﯿﻤﺔ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ )‪(E‬‬
‫ﻧﻘﻮم أوﻻً ﺑﻌﻤﻞ اﻟﺠﺪول اﻟﻼزم ‪:‬‬
‫)‪103 × k (dm3 mol-1 s-1‬‬ ‫‪0.100‬‬ ‫‪0.335‬‬ ‫‪1.41‬‬ ‫‪3.06‬‬ ‫‪8.13‬‬ ‫‪21.1‬‬ ‫‪50.1‬‬
‫)‪log k (dm3 mol-1 s-1‬‬ ‫‪- 4.00‬‬ ‫‪- 3.475‬‬ ‫‪- 2.851‬‬ ‫‪- 2.514‬‬ ‫‪- 2.090‬‬ ‫‪- 1.676‬‬ ‫‪- 1.300‬‬
‫)‪T (ºC‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬ ‫‪60‬‬ ‫‪70‬‬ ‫‪80‬‬
‫)‪T (K‬‬ ‫‪293‬‬ ‫‪303‬‬ ‫‪313‬‬ ‫‪323‬‬ ‫‪333‬‬ ‫‪343‬‬ ‫‪353‬‬
‫)‪10 - 3 × (1/T‬‬ ‫‪3.413‬‬ ‫‪3.300‬‬ ‫‪3.195‬‬ ‫‪3.096‬‬ ‫‪3.003‬‬ ‫‪2.915‬‬ ‫‪2.833‬‬
‫وﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ اﻟﺒﯿﺎﻧﯿﺔ ﺑﯿﻦ )‪ (k), (T‬ﻧﺤﺼﻞ ﻋﻠﻰ )ﺷﻜﻞ ‪.(١٥-٤‬‬

‫‪863‬‬
‫ﺷﻜﻞ )‪ : (١٥-٤‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ ﻟﻮﻏﺎرﯾﺘﻢ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ وﻣﻘﻠﻮب اﻟﺰﻣﻦ ﻟﻠﺘﻤﯿﺆ‬

‫اﻟﻘﺎﻋﺪي ﻟﯿﻮدﯾﺪ اﻹﯾﺜﯿﻞ‬
‫وﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ )‪ (log k‬ﻣ ﻊ )‪ (1/T‬ﻛﻤ ﺎ ﻧﺤﺼ ﻞ ﻋﻠ ﻰ اﻟﺸ ﻜﻞ‬

‫)‪.(١٦-٤‬‬

‫‪864‬‬
‫ﺷﻜﻞ )‪(١٦-٤‬‬
‫ﻓﺈﻧﻨﺎ ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ )‪(- E/2.303R‬‬

‫وﻣﻦ اﻟﺸﻜﻞ ﻓﺈن ﻣﯿﻞ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ‪:‬‬
‫‪slope = - 4.7 × 103‬‬
‫‪ -E ‬‬
‫‪slope = ‬‬ ‫‪‬‬
‫‪ 2.303 R ‬‬
‫)‪E = - (slope × 2.303 R‬‬
‫)‪E = - ( - 4.7 × 103 × 2.303 × 8.314‬‬
‫‪E = 89991.567 J‬‬
‫‪E = 89.99  90 kJ‬‬

‫‪865‬‬
‫ﻣﺜﺎﻝ )‪(٤-٤‬‬
‫ﺛﻮاﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ درﺟﺎت ﺣﺮارة ﻣﺨﺘﻠﻔﺔ ﻟﻠﺘﺤﻠﻞ اﻟﺤﺮاري ﻟﻐﺎز اﻹﯾﺜﺎن‬
‫ﻛﺎﻧﺖ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪105 k s-1‬‬ ‫‪2.5 4.7 8.2 12.3 23.1 35.3 57.6 92.4 141.5‬‬
‫‪T/K‬‬ ‫‪823 833 843 853 863 873 883 893 903‬‬
‫ﻣ ﻦ ھ ﺬه اﻟﻘ ﯿﻢ اﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﻠﺘﻔﺎﻋ ﻞ واﺣﺴ ﺐ ﻗﯿﻤ ﺔ )‪(A‬‬

‫ﻟﻠﺘﺤﻠﻞ‪ .‬وﺿﺢ اﻟﻮﺣﺪات اﻟﻤﺴﺘﺨﺪﻣﺔ ﻓﻲ اﻟﺘﻌﺒﯿﺮ ﻋﻦ اﻟﻜﻤﯿﺎت اﻟﻤﻘﺎﺳﺔ‪.‬‬
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‫‪866‬‬
‫ﻣﺜﺎﻝ )‪(٥-٤‬‬
‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ )‪ (k‬ﻟﺘﻔﻜ ﻚ ﺧ ﺎﻣﺲ‬
‫أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ﯾﺰداد ﻣﻊ درﺟﺔ اﻟﺤﺮارة ﻛﻤﺎ ﻓﻲ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪K × 105 s-1‬‬ ‫‪3.4‬‬ ‫‪13.5‬‬ ‫‪76‬‬ ‫‪487‬‬
‫‪TK‬‬ ‫‪298‬‬ ‫‪308‬‬ ‫‪323‬‬ ‫‪338‬‬
‫ﻓﺎﺣﺴﺐ ﻣﺎ ﯾﻠﻲ ‪:‬‬

‫أ( طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ )‪ (Ea‬ﻟﻠﺘﻔﺎﻋﻞ ﺑﻮﺣﺪات اﻟﻜﯿﻠﻮﺟﻮل ﻟﻜﻞ ﻣﻮل‪.‬‬
‫ب( ﻣﻌﺎﻣﻞ اﻟﺘﺮدد ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ )‪.(A‬‬
‫ﺍﳊﻞ‬
‫أ( طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪Ea = 102.0 kJ mol-1‬‬
‫ب( ﻣﻌﺎﻣﻞ اﻟﺘﺮدد ‪A = 2.7 × 1013 s-1‬‬
‫‪........................................................... .........................................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪............. ............................................................................................................................. ..........................................................‬‬
‫‪............................................................................... .....................................................................................................................‬‬
‫‪.................... ................................................... .............................................................................................................................‬‬
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‫‪........................................ ............................... .............................................................................................................................‬‬

‫‪867‬‬
‫ﻣﺜﺎﻝ )‪(٦-٤‬‬
‫ﻟﺪﯾﻚ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪2HI ‬‬
‫‪→ H 2 + I2‬‬
‫ﻓﺈذا ﻋﻠﻤﺖ أن ﺛﻮاﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ ‪:‬‬

‫‪k dm3 mol-1 s-1‬‬ ‫)‪T (K‬‬
‫‪3.11 × 10-7‬‬ ‫‪556‬‬
‫‪1.18 × 10-6‬‬ ‫‪575‬‬
‫‪3.33 × 10-5‬‬ ‫‪629‬‬
‫‪8.96 × 10-5‬‬ ‫‪647‬‬
‫‪1.92 × 10-4‬‬ ‫‪666‬‬
‫‪5.53 × 10-4‬‬ ‫‪683‬‬
‫‪1.21 ×10-3‬‬ ‫‪700‬‬
‫اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ وﻣﻌﺎﻣﻞ اﻟﺘﺮدد ﻟﻠﺘﻔﺎﻋﻞ‬

‫‪....................................................................... .............................................................................................................................‬‬
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‫‪868‬‬
‫ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﺜﺎﻧﻴﺔ ﳊﺴﺎﺏ ﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ‬
‫ﺗﺸﺘﻤﻞ ھﺬه اﻟﻄﺮﯾﻘﺔ ﻋﻠﻰ ﻗﯿﺎس ﺛﺎﺑﺘﻲ اﻟﺴﺮﻋﺔ )‪ (k2 ،k1‬ﻟﻠﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬

‫درﺟﺘﻲ ﺣﺮارة ﻣﺨﺘﻠﻔﺘﯿﻦ ﺣﯿﺚ ﯾﻤﻜﻦ ﺗﻌﯿﯿﻦ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪d lnk‬‬
‫‪= E/RT 2‬‬
‫‪dT‬‬
‫وﺑﺈﺟﺮاء اﻟﺘﻜﺎﻣﻞ ﻟﻠﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ‪ ،‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪k2‬‬ ‫‪T2‬‬
‫‪E‬‬ ‫‪dT‬‬
‫‪∫k d lnk = R‬‬ ‫‪∫T‬‬
‫‪T1‬‬
‫‪2‬‬
‫‪1‬‬
‫‪T‬‬
‫‪E 1 2‬‬
‫‪[ln k ]k‬‬
‫‪k2‬‬
‫‪=-  ‬‬
‫‪1‬‬
‫‪R  T  T1‬‬
‫‪k ‬‬ ‫‪E1 1‬‬
‫‪∴ ln  2  = -  - ‬‬
‫‪ k1 ‬‬ ‫‪R  T2 T1 ‬‬
‫‪k ‬‬ ‫‪E1 1‬‬
‫‪2.303log  2  = -  - ‬‬
‫‪ k1 ‬‬ ‫‪R  T2 T1 ‬‬
‫‪k ‬‬ ‫‪E‬‬ ‫‪1 1‬‬
‫‪log  2  = −‬‬ ‫‪ - ‬‬
‫‪ k1 ‬‬ ‫‪2.303 R  T2 T1 ‬‬
‫‪k ‬‬ ‫‪E‬‬ ‫‪1 1‬‬
‫= ‪log  2 ‬‬ ‫‪ - ‬‬
‫‪ k1  2.303 R  T1 T2 ‬‬
‫‪k ‬‬ ‫‪E‬‬ ‫‪ T2 - T1 ‬‬

‫= ‪⇒ log  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k1  2.303 R  T1T2 ‬‬
‫وﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻤﻌﺎﻣ ﻞ اﻟﺘ ﺮدد "‪ "A‬ﻓﺈﻧ ﮫ ﯾﺤﺴ ﺐ ﻣ ﻦ اﻟﺠ ﺰء اﻟﻤﻘﻄ ﻮع ﻓ ﻲ‬

‫اﻟﻤﺤ ﻮر اﻟﺼ ﺎدي ﻓ ﻲ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ )‪ (log k‬ﻣ ﻊ )‪ .(1/T‬وﻟﻜ ﻦ ذﻟ ﻚ‬

‫‪869‬‬
‫ﯾﺘﻄﻠ ﺐ ﺗﺤﺪﯾ ﺪ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ ﻋﻠ ﻰ اﺳ ﺘﻘﺎﻣﺘﮫ ﻟﻤﺴ ﺎﻓﺔ ﻛﺒﯿ ﺮة ﺣﺘ ﻰ‬

‫)‪ ،(1/T = 0‬ﻟ ﺬﻟﻚ ﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ ﻗﯿﻤ ﺔ اﻟﺜﺎﺑ ﺖ "‪ ،"A‬وذﻟ ﻚ‬
‫ﺑﺘﻄﺒﯿﻖ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪E‬‬
‫‪log k = log A -‬‬
‫‪2.303 RT‬‬
‫وﺗﻔﯿﺪﻧﺎ ﻣﻌﺎدﻟ ﺔ أرھﯿﻨﯿ ﻮس ﺑﺤﺴ ﺎب ﺗ ﺄﺛﯿﺮ زﯾ ﺎدة درﺟ ﺔ اﻟﺤ ﺮارة ﻋﻠ ﻰ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪،‬‬
‫ﻓﻤ ﺜﻼً ﺗ ﺄﺛﯿﺮ زﯾ ﺎدة )‪ (10 ºC‬ﻣ ﻦ )‪ (27 ºC‬اﻟ ﻰ )‪ (37 ºC‬ﺳﯿﺤﺴ ﺐ‬
‫‪‬‬ ‫‪Ea‬‬ ‫‪‬‬
‫ﻟﻤﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ﺣﯿ ﺚ أﻧ ﮫ‬ ‫‪ ln k = -‬‬ ‫‪+ ln A ‬‬ ‫ﺑﺎﺳﺘﺨﺪام اﻟﺼﯿﻐﺔ‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬
‫ﻋﻨﺪ ‪:‬‬
‫‪(27 ºC) T1‬‬
‫‪E‬‬
‫‪ln k1 = ln A -‬‬
‫‪RT1‬‬
‫وﻋﻨﺪ ‪: (37 ºC) T2‬‬
‫‪E‬‬
‫‪ln k 2 = ln A -‬‬
‫‪RT2‬‬
‫‪‬‬ ‫‪Ea ‬‬ ‫‪‬‬ ‫‪Ea ‬‬
‫‪ ln k 2 = ln A -‬‬ ‫‪‬‬ ‫ﻣﻦ اﻟﻌﻼﻗﺔ‬ ‫‪ ln k1 = ln A -‬‬ ‫‪‬‬ ‫ﺑﻄﺮح اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪RT2 ‬‬ ‫‪‬‬ ‫‪RT1 ‬‬

870
 E   E 
ln k 2 − ln k1 =  ln A -  −  ln A - 
 RT2   RT1 
k  E E
ln  2  = ln A - - ln A +
 k1  RT2 RT1
k  E E
ln  2  = - + a
 k1  RT2 RT1
k  E E
ln  2  = −
 k1  RT1 RT2
k  E  1 1 
ln  2  =  - 
 k1  R  T1 T2 
k  E T -T 
2.303log  2  =  2 1 
 k1  R  T1T2 
k  E  T2 - T1 
⇒ log  2  =  
 k1  2.303 R  T1 T2 
: ‫( ﻓﺈن‬E = 80418 J/mol) ‫وﻋﻨﺪﻣﺎ‬

k  E  T2 - T1 
log  2  =  
 k1  2.303 R  T1 T2 
k  80418 J mol-1  310 - 300 
log  2  = -1  
 k1  2.303 × 8.314 J mol K  310 × 300 
-1
k 
log  2  = 0.452
 k1 
k 
⇒  2  = 2.83
 k1 
k1
k2 =
0.353
k 2 = 2.83 k1
.ً ‫ﻣﻤﺎ ﯾﻌﻨﻲ أن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ زادت ﺛﻼﺛﺔ أﺿﻌﺎف ﺗﻘﺮﯾﺒﺎ‬
‫ﺗﻌﺘﺒﺮ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ﻣﺜﺎﻟﯿﺔ ﻟﻠﺘﻔﺎﻋﻼت ذات اﻟﺨﻄﻮة اﻟﻮاﺣﺪة ﻣﻤﺎ ﯾﻌﻨﻲ‬
(1/T) ‫( ﻣ ﻊ‬log k) ‫أن أي ﺣﯿ ﻮد ﻋ ﻦ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ اﻟﻨ ﺎﺗﺞ ﻋ ﻦ رﺳ ﻢ‬

‫‪871‬‬
‫ﯾﻌﻨﻲ وﺟﻮد ﺗﻔﺎﻋﻞ ﻣﻌﻘﺪ ‪ ،‬ﻟﻜﻦ اﻟﻌﻜ ﺲ ﻏﯿ ﺮ ﺻ ﺤﯿﺢ ﺣﯿ ﺚ ﺗﺘﺒ ﻊ ﻛﺜﯿ ﺮ‬

‫ﻣﻦ اﻟﺘﻔﺎﻋﻼت اﻟﻤﻌﻘﺪة ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس‪.‬‬
‫ﻣﺜﺎﻝ )‪(٧-٤‬‬
‫ﻣﻦ اﻟﻤﻌﺮوف أن رﻓ ﻊ درﺟ ﺔ ﺣ ﺮارة اﻟﻨﻈ ﺎم ) ‪ (10 ºC‬ﯾﺴ ﺒﺐ زﯾ ﺎدة‬

‫ﻣﻌﺪل ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣ ﺮﺗﯿﻦ‪ .‬اﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ) *‪ ( ΔE‬إذا ﻛﺎﻧ ﺖ‬
‫درﺟﺔ اﻟﺤﺮارة اﻹﺑﺘﺪاﺋﯿﺔ )‪ (25 ºC‬واﻟﻨﮭﺎﺋﯿﺔ )‪.(35 ºC‬‬
‫ﺍﳊﻞ‬
‫‪k ‬‬ ‫‪ΔE act  1 1 ‬‬

‫= ‪log  2 ‬‬ ‫‪ - ‬‬
‫‪ 1‬‬
‫‪k‬‬ ‫‪2.303‬‬ ‫‪R‬‬ ‫‪ T1 T2 ‬‬
‫‪2‬‬ ‫‪ΔE act‬‬ ‫‪ 1‬‬ ‫‪1 ‬‬
‫= ‪log  ‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪ 1  2.303 × 8.314  298 308 ‬‬
‫‪10.895 × 10-5 ΔE act‬‬
‫= ‪0.30103‬‬
‫‪19.147‬‬
‫‪0.30103 × 19.147‬‬
‫= ‪ΔE act‬‬
‫‪10.895 × 10-5‬‬
‫‪ΔE act = 52903.36 J/mol‬‬
‫‪ΔE act = 52.903 kJ/mol‬‬
‫ﻣﺜﺎﻝ )‪(٨-٤‬‬
‫إذا ﻋﻠﻤ ﺖ أن ﺗﻔﺎﻋ ﻞ اﻷﻣﻮﻧﯿ ﺎ ﻣ ﻊ ﺛ ﺎﻧﻲ أﻛﺴ ﯿﺪ اﻟﻜﺮﺑ ﻮن ﻓ ﻲ ﻣﺮاﺣﻠ ﮫ‬

‫اﻷوﻟﯿ ﺔ ﻣ ﻦ اﻟﻤﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‪ ،‬وﻛﺎﻧ ﺖ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬

‫‪872‬‬
‫درﺟ ﺔ ﺣ ﺮارة )‪ (327 ºC‬ﺗﺴ ﺎوي )‪ (0.385 M-1 s-1‬وﻋﻨ ﺪ درﺟ ﺔ‬

‫اﻟﺤﺮارة )‪ (443 ºC‬أﺻﺒﺤﺖ )‪.(16.0 M-1 s-1‬‬
‫ب( ﻣﻌﺎﻣﻞ اﻟﺘﺮدد‪.‬‬ ‫أ( طﺎﻗﺔ ﺗﻨﺸﯿﻂ اﻟﺘﻔﺎﻋﻞ‬ ‫ﻓﺎﺣﺴﺐ ‪:‬‬
‫ﺍﳊﻞ‬
‫أ( ﻟﻜﻲ ﻧﻮﺟﺪ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻧﺴﺘﺨﺪم اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪k ‬‬ ‫‪E a  T2 - T1 ‬‬
‫= ‪log  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k1  2.303 R  T2 T1 ‬‬
‫وذﻟﻚ ﺑﺎﻟﺘﻌﻮﯾﺾ ﻣﺒﺎﺷﺮة ﻋﻦ ﻗﯿﻤﺘﻲ درﺟﺔ اﻟﺤﺮارة ﺑﺎﻟﻤﻘﯿﺎس اﻟﻤﻄﻠ ﻖ‬

‫وﻗﯿﻤﺘ ﻲ ﺛ ﺎﺑﺘﻲ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ وﻗﯿﻤ ﺔ )‪(R = 8.314 J mol-1 K-1‬‬
‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪k ‬‬ ‫‪E a  T2 - T1 ‬‬
‫= ‪log  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k1  2.303 R  T1 T2 ‬‬
‫‪ 16.0 ‬‬ ‫‪Ea‬‬ ‫‪ 716 - 600 ‬‬
‫‪log ‬‬ ‫=‪‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ 0.385  2.303 × 8.314  716 × 600 ‬‬
‫‪1.619 = 1.41×10-5 E a‬‬
‫‪E a = 114822.695 J mol -1‬‬
‫‪E a = 114.82 kJ mol -1‬‬
‫‪‬‬ ‫‪Ea ‬‬

‫‪ lnk = lnA -‬‬ ‫‪‬‬ ‫ب( ﻟﺤﺴ ﺎب ﻣﻌﺎﻣ ﻞ اﻟﺘ ﺮدد )‪ (A‬ﻧﺴ ﺘﺨﺪم اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪RT ‬‬
‫وذﻟ ﻚ ﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ ﻗﯿﻤ ﺔ )‪ (k‬ﻋﻨ ﺪ إﺣ ﺪى اﻟ ﺪرﺟﺘﯿﻦ وﻟ ﺘﻜﻦ درﺟ ﺔ‬

‫اﻟﺤﺮارة )‪ (716 K‬ﻛﺎﻵﺗﻲ ‪:‬‬

873
Ea
lnk = lnA -
RT
114822.695
ln16.0 = lnA -
8.314 × 716
114822.695
lnA = ln16.0 +
8.314 × 716
lnA = 22.06
A = 3.8 × 109 M-1s-1
(٩-٤) ‫ﻣﺜﺎﻝ‬
‫( ﻋﻨ ﺪ درﺟ ﺔ‬k = 3.4 × 10-5 s-1) ‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﺘﻔﺎﻋ ﻞ‬
‫( ﯾﺴ ﺎوي‬364 K) ‫( وﻋﻨ ﺪ درﺟ ﺔ اﻟﺤ ﺮارة‬302 K) ‫ﺣ ﺮارة‬
.‫ اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﺑﻮﺣﺪة اﻟﺠﻮل‬.(k = 1.1 × 10-4 s-1)
‫ﺍﳊﻞ‬
 k  E  T -T 
ln  2  = a  2 1 
 k1  R  T2 T1 
 1.1 × 10- 4  E a  364 - 302 
ln  -5 
=  
 3.4 × 10  8.314  302 × 364 
 1.1 × 10- 4  E a  62 
ln  -5 
=  
 3.4 × 10  8.314  109928 
 1.1 × 10- 4 
ln  
Ea  3.4 × 10-5 
=
8.314  62 
 
 109928 
Ea
= 2081.75
8.314
E a = 2081.75 × 8.314
E a = 17307.67 J/mol

‫‪874‬‬
‫ﻣﺜﺎﻝ )‪(١٠-٤‬‬
‫ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ ﯾﺴ ﺎوي )‪(3.4 × 10-2 s-1‬‬

‫ﻋﻨ ﺪ درﺟ ﺔ اﻟﺤ ﺮارة )‪ (25 ºC‬وﻋﻨ ﺪ رﻓ ﻊ درﺟ ﺔ اﻟﺤ ﺮارة إﻟ ﻰ‬
‫)‪ (77 ºC‬أﺻﺒﺢ )‪ .(0.702 s-1‬اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫‪T1 = 25 + 273 = 298 K, T2 = 77 + 273 = 350 K‬‬
‫‪ k  E  T -T ‬‬
‫‪ln  2  = a  2 1 ‬‬
‫‪ k1  R  T2 T1 ‬‬
‫‪ 0.702 ‬‬ ‫‪E a  350 - 298 ‬‬
‫‪ln ‬‬ ‫‪-2 ‬‬
‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 3.4 × 10  8.314  298 × 350 ‬‬
‫‪ 0.702 ‬‬ ‫‪E a  52 ‬‬
‫‪ln ‬‬ ‫‪-2 ‬‬
‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 3.4 × 10  8.314  104300 ‬‬
‫‪ 0.702 ‬‬
‫‪ln ‬‬ ‫‪‬‬
‫‪Ea‬‬ ‫‪‬‬ ‫‪3.4 × 10-2 ‬‬
‫=‬
‫‪8.314‬‬ ‫‪ 52 ‬‬
‫‪‬‬ ‫‪‬‬
‫‪ 104300 ‬‬
‫‪Ea‬‬
‫‪= 6072.61‬‬
‫‪8.314‬‬
‫‪E a = 6072.61 × 8.314‬‬
‫‪E a = 50487.68 J/mol‬‬
‫‪E a = 50.5 kJ/mol‬‬

875
(١١-٤) ‫ﻣﺜﺎﻝ‬
: ‫ﻓﻲ ﺗﺠﺮﺑﺔ ﻋﻨﺪ درﺟﺘﻲ ﺣﺮارة ﻣﺨﺘﻠﻔﺘﯿﻦ وﺟﺪ أن ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
k (s-1) 1.5 2.4
T (ºC) 21 30
.‫اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ‬
‫ﺍﳊﻞ‬
T1 = 21 + 273 = 294 K, T2 = 30 + 273 = 303 K
 k  E  T -T 
ln  2  = a  2 1 
 k1  R  T2 T1 
 2.4  E a  303 - 294 
ln  =  
 1.5  8.314  303 × 294 
 2.4  Ea  9 
ln  =  
 1.5  8.314  89082 
 2.4 
ln  
Ea
=  1.5 
8.314  9 
 
 89082 
Ea
= 4652.1
8.314
E a = 4652.1 × 8.314
E a = 38677.6 J/mol
E a = 38.7 kJ/mol

‫‪876‬‬
‫ﻣﺜﺎﻝ )‪(١٢-٤‬‬
‫إن ﻗﯿﻢ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﺘﺤﻠﻞ ﺧﺎﻣﺲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ‪:‬‬

‫‪N 2 O5 ‬‬
‫‪→ N 2O4 +‬‬ ‫‪1‬‬
‫‪2‬‬ ‫‪O2‬‬
‫ھ ﻲ )‪ (k = 3.46 × 10-5‬ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة )‪،(25 ºC‬‬

‫و )‪ (k = 4.87 × 10-3‬ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة )‪ ،(65 ºC‬اﺣﺴ ﺐ طﺎﻗ ﺔ‬
‫اﻟﺘﻨﺸﯿﻂ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿﻖ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ‪:‬‬

‫‪k ‬‬ ‫‪ΔE  T2 - T1 ‬‬
‫= ‪log  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k1  2.303R  T1 T2 ‬‬
‫‪ 4.87 × 10-3 ‬‬ ‫‪ΔE‬‬ ‫‪ 338 - 298 ‬‬
‫‪log ‬‬ ‫‪‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 3.46 × 10  2.303 × 8.314  298 × 338 ‬‬
‫‪-5‬‬
‫= ‪2.148‬‬
‫‪(397.124 × 10 ) ΔE‬‬ ‫‪-6‬‬
‫‪19.147‬‬
‫‪2.148 × 19.147‬‬
‫= ‪ΔE‬‬
‫‪397.124 × 10−6‬‬
‫‪ΔE = 103564.0153 J/mol‬‬
‫‪ΔE = 103.564 kJ/mol‬‬

‫‪877‬‬
‫ﻣﺜﺎﻝ )‪(١٣-٤‬‬
‫ﻟﻠﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪2N 2O5 (g) ‬‬
‫)‪→ 2N 2O 4 (g) + O 2 (g‬‬
‫ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﯾﺴ ﺎوي )‪ (k = 1.72 × 10-5 s-1‬ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة‬

‫)‪ (25 ºC‬و )‪ (k = 2.40 × 10-3 s-1‬ﻓﻲ درﺟﺔ )‪ .(65 ºC‬اﺣﺴﺐ ‪:‬‬
‫أ( طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ‬
‫ب( ﺛﺎﺑﺖ أرھﯿﻨﻮس‬
‫ج( اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ درﺟﺔ )‪.(45 ºC‬‬
‫ﺍﳊﻞ‬
‫أ( ﺣﺴﺎب طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪:‬‬

‫‪k2‬‬ ‫‪ΔE  T2 - T1 ‬‬
‫‪log‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪k1 2.303 R  T2T1 ‬‬
‫‪ 2.40 × 10-3 ‬‬ ‫‪ΔE‬‬ ‫‪ 338 - 298 ‬‬
‫‪log ‬‬ ‫‪-5 ‬‬
‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 1.72 × 10  2.303 × 8.314  338 × 298 ‬‬
‫‪ΔE‬‬
‫= ‪2.145‬‬ ‫) ‪( 0.000397‬‬
‫‪19.147‬‬
‫‪2.145 × 19.147‬‬
‫= ‪ΔE‬‬
‫‪0.000397‬‬
‫‪ΔE = 103.452 × 103 J/mol‬‬
‫‪ΔE = 103.452 kJ/mol‬‬

‫‪878‬‬
‫ب( ﺣﺴﺎب ﺛﺎﺑﺖ أرھﯿﻨﯿﻮس )‪) (A‬ﻣﻌﺎﻣﻞ اﻟﺘﺮدد( ‪:‬‬

‫‪ΔE‬‬
‫‪2.303 RT‬‬
‫‪ΔE‬‬
‫‪log A = log k +‬‬
‫‪2.303 RT‬‬
‫‪103.452 × 103‬‬
‫‪logA = log (1.72 × 10 ) +‬‬ ‫‪-5‬‬
‫‪2.303 × 8.314 × 298‬‬

‫‪log A = 13.366‬‬
‫‪A = 2.325 × 1013 s -1‬‬
‫ج( ﺣﺴﺎب ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ درﺟﺔ ﺣﺮارة )‪: (45 ºC‬‬
‫‪k2‬‬ ‫‪ΔE  T2 - T1 ‬‬
‫‪log‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪k1 2.303 R  T2 T1 ‬‬
‫‪‬‬ ‫‪ 103.452 × 10  318 - 298 ‬‬
‫‪3‬‬
‫‪k2‬‬
‫‪log ‬‬ ‫‪‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 1.72 × 10  2.303 × 8.314  318 × 298 ‬‬
‫‪-5‬‬
‫‪log k 2 − log (1.72 × 10-5 ) = 1.140‬‬

‫) ‪log k 2 = 1.140 + log (1.72 × 10-5‬‬
‫‪log k 2 = −3.624‬‬
‫‪k 2 = 2.37 × 10− 4‬‬
‫ﻣﺜﺎﻝ )‪(١٤-٤‬‬
‫إن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﺤﻠ ﻞ ﯾﻮدﯾ ﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ ﻓ ﻲ درﺟ ﺔ )‪ (556 K‬ھ ﻮ‬
‫)‪ (k = 3.517 × 10-7 L mol-1 s-1‬وﻓ ﻲ درﺟ ﺔ )‪ (781 K‬ھ ﻮ‬
‫)‪ .(k = 3.954 × 10-2 L mol-1 s-1‬اﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﺘﺤﻠ ﻞ‬
‫ﯾﻮدﯾﺪ اﻟﮭﯿﺪروﺟﯿﻦ‪.(R = 1.987 cal/mol K) .‬‬

‫‪879‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿﻖ ﻣﻌﺎدﻟﺔ أرھﯿﻨﯿﻮس ‪:‬‬

‫‪ k  ΔE  T2 - T1 ‬‬
‫= ‪ln  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k1  R  T2T1 ‬‬
‫‪ 3.954 × 10−2 ‬‬ ‫‪ΔE  781 - 556 ‬‬
‫‪ln ‬‬ ‫‪−7 ‬‬
‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 3.517 × 10  1.987  781 × 556 ‬‬
‫‪5.18 × 10-4 ΔE‬‬
‫= ‪11.630‬‬
‫‪1.987‬‬
‫‪ΔE = 44611.60 cal/mol‬‬
‫‪ΔE = 44.61 kcal/mol‬‬
‫ﻣﺜﺎﻝ )‪(١٥-٤‬‬
‫ﻞ‬ ‫ﻰ ﻟﺘﺤﻠ‬ ‫ﺔ اﻷوﻟ‬ ‫ﻞ اﻟﺮﺗﺒ‬ ‫ﺮﻋﺔ ﻟﺘﻔﺎﻋ‬ ‫ﺖ اﻟﺴ‬ ‫إن ﺛﺎﺑ‬

‫)‪ (2- chloropropane‬إﻟ ﻰ اﻟﺒ ﺮوﺑﻠﯿﻦ )‪ (propylene‬وﻛﻠﻮرﯾ ﺪ‬
‫اﻟﮭﯿﺪروﺟﯿﻦ )‪ (HCl‬ﻛﺪاﻟﺔ ﻟﺪرﺟﺔ اﻟﺤﺮارة ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪T, K‬‬ ‫‪640.6 646.7 651.2 657.5 665.1 669.0 674.9 679.7‬‬
‫‪K × 103 s-1‬‬ ‫‪0.162 0.238 0.311 0.475 0.706 0.901 1.225 1.593‬‬
‫اﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ )ﺣﺴ ﺎﺑﯿﺎ ً وﺑﯿﺎﻧﯿ ﺎ ً( وﻣﻌﺎﻣ ﻞ اﻟﺘ ﺮدد)‪(A‬‬

‫)‪.(frequency factor‬‬
‫ﺍﳉﻮﺍﺏ‬
‫‪( ∆E‬‬ ‫‪cat‬‬ ‫) ‪= 211 kJ/mol, A = 2.5 × 1013 s -1‬‬

‫‪880‬‬
‫ﻃﺮﻳﻘﺔ ﺍﳊﻞ‬
‫‪...................................................................................................... ..............................................................................................‬‬
‫‪........................................... ............................ .............................................................................................................................‬‬
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‫‪....................................................................... .............................................................................................................................‬‬
‫‪.................. ............................................................................................................................. .....................................................‬‬

‫‪881‬‬
‫ﻣﺜﺎﻝ )‪(١٦-٤‬‬
‫اﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﺘﺤﻠ ﻞ )‪ (N2O5‬ﻣ ﻦ اﻟﻨﺘ ﺎﺋﺞ اﻟﻤﺨﺒﺮﯾ ﺔ اﻟﺘﺎﻟﯿ ﺔ‬
‫ﺣﺴﺎﺑﯿﺎ ً وﺑﯿﺎﻧﯿﺎ ً‪.‬‬
‫‪T, ºC‬‬ ‫‪0‬‬ ‫‪25‬‬ ‫‪45‬‬ ‫‪65‬‬
‫‪K, min-1‬‬ ‫‪4.7 × 10-5‬‬ ‫‪2 × 10-3‬‬ ‫‪3 × 10-2‬‬ ‫‪3 × 10-1‬‬
‫‪ΔE act = 103 × 103 J/mol‬‬
‫‪................................... .................................... .............................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪................................................ ............................................................................................................................. .......................‬‬
‫‪.................................................................................................................. ..................................................................................‬‬
‫‪....................................................... .............................................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪.................................................................... ............................................................................................................................. ...‬‬
‫‪......... ............................................................................................................................. ..............................................................‬‬
‫‪........................................................................... .........................................................................................................................‬‬
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‫‪............................................................................................... .....................................................................................................‬‬
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‫‪882‬‬
‫ﻣﺜﺎﻝ )‪(١٧-٤‬‬
‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻟﺘﻔﻜ ﻚ )‪ (HI‬ﯾﺴ ﺎوي )‪(0.079 L mol-1 s-1‬‬
‫‪ (540‬ﯾﺴ ﺎوي‬ ‫‪ (580‬وﻋﻨ ﺪ اﻟﺪرﺟ ﺔ )‪ºC‬‬ ‫ﻋﻨ ﺪ اﻟﺪرﺟ ﺔ )‪ºC‬‬
‫)‪ .(0.24 L mol-1 s-1‬اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫اﻟﺠﻮاب ‪Ea = 183311.78 J/mol :‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪.......................... ............................................................................................................................. .............................................‬‬
‫‪............................................................................................ ........................................................................................................‬‬
‫‪................................. ...................................... .............................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪.............................................. ............................................................................................................................. .........................‬‬
‫‪................................................................................................................ ....................................................................................‬‬
‫‪..................................................... .................. .............................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
‫‪.................................................................. ............................................................................................................................. .....‬‬
‫‪.................................................................................................................................... ................................................................‬‬
‫‪......................................................................... ...........................................................................................................................‬‬
‫‪.............. ......................................................... .............................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬

‫‪883‬‬
‫ﻣﺜﺎﻝ )‪(١٨-٤‬‬
‫وﺟ ﺪ أن ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﺘﻔﺎﻋ ﻞ ﻣﻌ ﯿﻦ ﻋﻨ ﺪ درﺟ ﺔ اﻟﺤ ﺮارة )‪(50 ºC‬‬
‫ﯾﺴﺎوي ﺛﻼﺛﺔ أﺿﻌﺎف ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻧﻔﺴﮫ ﻋﻨﺪ درﺟ ﺔ اﻟﺤ ﺮارة‬
‫)‪ .(25 ºC‬اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ‪.‬‬
‫ﺍﳊﻞ‬
‫‪T1 = 25 + 273 = 298 K, T2 = 50 + 273 = 323 K‬‬

‫‪ k  ∆E a  T2 -T1 ‬‬
‫= ‪ln  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ 1‬‬
‫‪k‬‬ ‫‪R‬‬ ‫‪ 2 1 ‬‬
‫‪T‬‬ ‫‪T‬‬
‫‪ 3 k  ∆E a  323 - 298 ‬‬
‫‪ln ‬‬ ‫=‪‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k  8.314  323 × 298 ‬‬
‫‪∆E a  25 ‬‬
‫= ‪ln 3‬‬ ‫‪‬‬ ‫‪‬‬
‫‪8.314  96254 ‬‬
‫‪ln 3 × 8.314‬‬
‫= ‪∆E a‬‬
‫‪ 25 ‬‬
‫‪‬‬ ‫‪‬‬
‫‪ 96254 ‬‬
‫‪∆E a = 35166.83 J/mol‬‬
‫‪∆E a = 35.167 kJ/mol‬‬

‫‪884‬‬
‫ﻣﺜﺎﻝ )‪(١٩-٤‬‬
‫إذا ﻛﺎن ﺛﺎﺑﺖ ﺳﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (40 ºC‬ﺗﺴ ﺎوي‬
‫ﺛﻼﺛﺔ أﻣﺜﺎل ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ درﺟﺔ ﺣﺮارة )‪ .(20 ºC‬اﺣﺴ ﺐ طﺎﻗ ﺔ‬
‫اﻟﺘﻨﺸﯿﻂ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫‪Ea = 41882.87 J/mol = 41.883 kJ/mol‬‬
‫‪................................................................................... .................................................................................................................‬‬
‫‪........................ ............................................... .............................................................................................................................‬‬
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‫‪885‬‬
‫ﻣﺜﺎﻝ )‪(٢٠-٤‬‬
‫إذا زادت ﺳﺮﻋﺔ ﺗﻔﺎﻋﻞ ﻣﺎ ﺛﻼﺛﺔ أﺿ ﻌﺎف ﻋﻨ ﺪ زﯾ ﺎدة درﺟ ﺔ اﻟﺤ ﺮارة‬
‫ﻣﻦ )‪ (30 ºC‬اﻟﻰ )‪ ،(50 ºC‬أوﺟﺪ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ‪.‬‬
‫‪Ea = 44696.1 J/mol = 44.696 kJ‬‬
‫‪................................................................... ............................................................................................................................. ....‬‬
‫‪........ ............................................................................................................................. ...............................................................‬‬
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‫‪886‬‬
‫ﻣﺜﺎﻝ )‪(٢١-٤‬‬
‫اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﺘﻔﺎﻋﻞ ﻣﺎ ﯾﻜﻮن ﻓﯿﮭ ﺎ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬

‫درﺟ ﺔ ﺣ ﺮارة )‪ (27 ºC‬ﺗﺴ ﺎوي ﺿ ﻌﻒ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬
‫)‪) .(10 ºC‬ﻋﻠﻨﺎ ً ﺑﺄن )‪(R = 8.314 J mol-1 K-1‬‬
‫‪Ea = 28780.23 J = 28.78 kJ‬‬
‫‪............................... ............................................................................................................................. ........................................‬‬
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‫‪887‬‬
‫ﻣﺜﺎﻝ )‪(٢٢-٤‬‬
‫اﺣﺴﺐ ﻗﯿﻤﺔ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ إذا زادت ﻗﯿﻤﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ أرﺑ ﻊ‬
‫ﻣ ﺮات ﻋﻨ ﺪﻣﺎ ﺗﺮﺗﻔ ﻊ درﺟ ﺔ اﻟﺤ ﺮارة ﻣ ﻦ )‪ (20 ºC‬اﻟ ﻰ )‪.(40 ºC‬‬
‫)‪(R = 8.314 J mol-1 K-1‬‬
‫‪52850.30 J = 52.850 kJ‬‬
‫‪...................................... ................................. .............................................................................................................................‬‬
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‫‪888‬‬
‫ﻣﺜﺎﻝ )‪(٢٣-٤‬‬
‫إذا ﻛﺎن ﻣﻌﺪل ﺳﺮﻋﺔ ﺗﻔﺎﻋﻞ ﻣ ﺎ ﻋﻨ ﺪ )‪ (100 ºC‬أﺳ ﺮع )‪ (4‬أﺿ ﻌﺎف‬

‫ﻣﻤ ﺎ ﻛ ﺎن ﻋﻨ ﺪ )‪ ،(30 ºC‬وإذا ﻛﺎﻧ ﺖ ﺗﺮاﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ ھ ﻲ‬
‫ﻧﻔﺴ ﮭﺎ ﻋﻨ ﺪ درﺟﺘ ﻲ اﻟﺤ ﺮارة‪ .‬اﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﻠﺘﻔﺎﻋ ﻞ ﻣﻌﺒ ﺮاً‬
‫ﻋﻨﮭﺎ ﺑﺎﻟﻜﯿﻠﻮﺟﻮل ﻟﻜﻞ ﻣﻮل‪.(R = 8.314 J mol-1 K-1).‬‬
‫‪18608.82 J = 18.088 kJ‬‬
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‫‪889‬‬
‫ﻣﺜﺎﻝ )‪(٢٤-٤‬‬
‫إذا ﻛﺎﻧ ﺖ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﺗﺴ ﺎوي )‪ (138 kJ/mol‬ﻟﺘﻔﺎﻋ ﻞ ﻣ ﺎ‪ ،‬وأن‬

‫ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﯾﺴﺎوي )‪ (k1 = 1.1 × 10-6 L mol-1 s-1‬ﻋﻨﺪ‬
‫)‪ ،(100 ºC‬ﻓﺎﺣﺴ ﺐ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (k2‬ﻋﻨ ﺪ )‪(300 ºC‬‬
‫)ﻋﻠﻤﺎ ً ﺑﺄن )‪.(R = 8.314 J mol-1 k-1‬‬
‫ﺍﳊﻞ‬
‫‪T1 = 100 + 273 = 373 K, T2 = 300 + 273 = 573 K‬‬

‫‪ k  E  T -T ‬‬
‫‪ln  2  = a  2 1 ‬‬
‫‪ k1  R  T2 T1 ‬‬
‫‪‬‬ ‫‪ 138 × 10  573 - 373 ‬‬
‫‪3‬‬
‫‪k2‬‬
‫‪ln ‬‬ ‫‪-6 ‬‬
‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪ 1.1 × 10 ‬‬ ‫‪8.314  573 × 373 ‬‬
‫‪‬‬ ‫‪k2‬‬ ‫‪‬‬
‫‪ln ‬‬ ‫‪-6 ‬‬
‫‪= 15.532‬‬
‫‪ 1.1 × 10 ‬‬
‫‪k2‬‬
‫‪= e15.532‬‬
‫‪1.1 × 10‬‬ ‫‪-6‬‬
‫‪k 2 = 1.1 × 10-6 × e15.532‬‬

‫‪k 2 = 1.1 × 10-6 × 5564958‬‬
‫‪k 2 = 6.12 L mol -1 s -1‬‬

890
(٢٥-٤) ‫ﻣﺜﺎﻝ‬
: ‫( ﻟﻠﺘﻔﺎﻋﻞ‬625 ºC) ‫اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ‬

CH 4 (g) + 2S2 (g) 
→ CS2 (g) + 2H 2S(g)
‫( ﺗﺴ ﺎوي‬550 ºC) ‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬

(140 kJ mol-1) ‫( وطﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﺗﺴ ﺎوي‬k1 = 1.1 L mol-1s-1)
.(R = 8.314 J mol-1 K-1 ‫)ﻋﻠﻤﺎ ً ﺑﺄن‬
‫ﺍﳊﻞ‬
T1 = 550 + 273 = 823 K, T2 = 625 + 273 = 898 K

 k  E  T -T 
ln  2  = a  2 1 
 k1  R  T2T1 
 k 2  140 × 10  898 - 823 
3
ln   =  
 1.1  8.314  898 × 823 
k 
ln  2  = 1.71
 1.1 
k2
= e1.71
1.1
k 2 = 1.1× e1.71
k 2 = 1.1× 5.53
k 2 = 6.08 L mol-1 s -1

‫‪891‬‬
‫ﻣﺜﺎﻝ )‪(٢٦-٤‬‬
‫إذا ﻛﺎن ﻟﺪﯾﻚ ﺗﻔﺎﻋﻼً ﻣﺎ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ وﻛﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫ﻟﮫ ﻋﻨﺪ )‪ (289 K‬ﯾﺴﺎوي )‪ ،(k1 = 3.46 × 10-2 s-1‬اﺣﺴ ﺐ ﺛﺎﺑ ﺖ‬
‫‪ (359‬إذا ﻛﺎﻧ ﺖ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ‬ ‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ )‪K‬‬
‫)‪) (50.2 kJ mol-1‬ﻋﻠﻤﺎ ً ﺑﺄن )‪.(R = 8.314 J mol-1 K-1‬‬
‫ﺍﳊﻞ‬
‫‪T1 = 289 K, T2 = 359 K‬‬

‫‪ k  E  T -T ‬‬
‫‪ln  2  = a  2 1 ‬‬
‫‪ k1  R  T2 T1 ‬‬
‫‪‬‬ ‫‪ 50.2 × 10  359 - 289 ‬‬
‫‪3‬‬
‫‪k2‬‬
‫‪ln ‬‬ ‫‪-2 ‬‬
‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪‬‬ ‫‪3.46‬‬ ‫×‬ ‫‪10‬‬ ‫‪‬‬ ‫‪8.314  359 × 289 ‬‬
‫‪‬‬ ‫‪k2‬‬ ‫‪‬‬
‫‪ln ‬‬ ‫‪-2 ‬‬
‫‪= 4.074‬‬
‫‪ 3.46 × 10 ‬‬
‫‪k2‬‬
‫‪= e 4.074‬‬
‫‪3.46 × 10‬‬ ‫‪-2‬‬
‫‪k 2 = 3.46 × 10-2 × e 4.074‬‬

‫‪k 2 = 3.46 × 10-2 × 58.792‬‬
‫‪k 2 = 2.03 s -1‬‬

‫‪892‬‬
‫ﻣﺜﺎﻝ )‪(٢٧-٤‬‬
‫إذا ﻛﺎﻧ ﺖ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﺘﻔﺎﻋ ﻞ ﻣ ﺎ ﺗﺴ ﺎوي )‪(38.68 kJ mol-1‬‬

‫وﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﺴ ﺎوي )‪ (k = 1.5 s-1‬ﻋﻨ ﺪ )‪(21 ºC‬‬
‫ﻓﺎﺣﺴﺐ ﻗﯿﻤﺔ اﻟﺜﺎﺑﺖ )‪.(A‬‬
‫ﺍﳊﻞ‬
‫‪Ea‬‬
‫‪ln k = ln A -‬‬
‫‪RT‬‬
‫‪E‬‬
‫‪ln A = lnk + a‬‬
‫‪RT‬‬
‫‪38.68 × 103 J mol-1‬‬
‫‪ln A = ln 1.5 +‬‬
‫‪8.314 J mol-1K -1 × 294 K‬‬
‫‪ln A = 16.23‬‬
‫‪A= e16.23‬‬
‫‪A = 11184058.79 s-1‬‬
‫‪A = 1.12 × 107 s -1‬‬

‫‪893‬‬
‫ﻣﺜﺎﻝ )‪(٢٨-٤‬‬
‫ﻓﻲ اﻟﻤﺮاﺣ ﻞ اﻷوﻟﯿ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ اﻟﻐ ﺎزي ﺑ ﯿﻦ اﻷﻣﻮﻧﯿ ﺎ )اﻟﻨﺸ ﺎدر( وﺛ ﺎﻧﻲ‬
‫أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ )‪ (NO2‬واﻟﺘﻲ ﺗﺘﺒﻊ ﺗﻔﺎﻋﻼً ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒ ﺔ ﻛ ﺎن ﺛﺎﺑ ﺖ‬
‫اﻟﺴ ﺮﻋﺔ ﻋﻨ ﺪ ‪ 600 K‬ھ ﻮ )‪ ،(k1 = 0.385 dm3 mol-1 s-1‬وﻋﻨ ﺪ‬
‫درﺟﺔ ﺣ ﺮارة )‪ (716 K‬ﻛ ﺎن اﻟﺜﺎﺑ ﺖ )‪(k2 = 16.0 dm3 mol-1 s-1‬‬
‫اﺣﺴﺐ اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟﺔ )‪ (Ea‬وﻣﻌﺎﻣﻞ اﻟﺘﺮدد )‪.(A‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪k ‬‬ ‫‪E‬‬ ‫‪ T2 - T1 ‬‬
‫= ‪log  2 ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ k1  2.303 R  T1T2 ‬‬
‫‪ 16.0 ‬‬ ‫‪E‬‬ ‫‪ 716 - 600 ‬‬
‫‪log ‬‬ ‫‪‬‬ ‫=‬
‫‪ 0.385  2.303 × 8.314  716 × 600 ‬‬
‫‪0.00027 E‬‬
‫= ‪1.619‬‬
‫‪2.303 × 8.314‬‬
‫‪2.303 × 8.314 × 1.619‬‬
‫=‪E‬‬
‫‪0.00027‬‬
‫‪E = 114811.94 J‬‬
‫‪E = 114.81 kJ‬‬
‫وﻹﯾﺠﺎد ﻗﯿﻤﺔ ﻣﻌﺎﻣﻞ اﻟﺘﺮدد ﻓﺈﻧﻨﺎ ﻧﻌﻮض ﺑﺄﺣﺪ اﻟﻘﯿﻤﺘﯿﻦ ﻟ ـ )‪(k1 or k2‬‬
‫ﻓﻲ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪894‬‬
‫‪E‬‬
‫‪2.303 RT‬‬
‫وﻟﺘﻜﻦ )‪ (k2 = 16.0‬ﻋﻨﺪ )‪: (T = 716 K‬‬

‫‪E‬‬
‫‪2.303 RT‬‬
‫‪E‬‬
‫‪log A = log k +‬‬
‫‪2.303 RT‬‬
‫‪114811.94 J‬‬
‫‪log A = log (16.0) +‬‬
‫‪2.303 × 8.314 × 716‬‬
‫‪log A = 9.5788‬‬
‫‪A = 3.792 × 109 dm3 mol-1s -1‬‬
‫ﻣﺜﺎﻝ )‪(٢٩-٤‬‬
‫إذا ﻋﻠﻤﺖ أن ﻣﺮﻛﺐ )‪ (benzene diazonium chloride‬ﯾﺘﻔﺎﻋ ﻞ‬

‫ﻓﻲ وﺟﻮد اﻟﻤﺎء ﺣﺴﺐ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬وﻛﺎن ﺛﺎﺑﺘﺎ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬
‫درﺟﺘ ﻲ اﻟﺤ ﺮارة )‪ (25 ºC‬و )‪ (35 ºC‬ھﻤ ﺎ )‪(2.8 × 10-3 min-1‬‬
‫و )‪ (5.37 × 10-3 min-1‬ﻋﻠﻰ اﻟﺘ ﻮاﻟﻲ ﻓﺎﺣﺴ ﺐ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻟﮭ ﺬا‬
‫طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪Ea = 49.70 kJ/mol‬‬

‫‪895‬‬
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‫‪896‬‬
‫ﻣﺜﺎﻝ )‪(٣٠-٤‬‬
‫ﻓﻲ ﺗﺤﻠﻞ ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ وﺟ ﺪ أن ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔﺎﻋ ﻞ ھ ﻮ‬

‫)‪ (k1 = 5.22 ×10-5 dm-3 mol-1 s-1‬ﻋﻨ ﺪ )‪ ،(T1 = 592 K‬أﻣ ﺎ‬
‫ﻋﻨ ﺪ )‪ (T2 = 627 K‬ﻓﻘ ﺪ وﺟ ﺪ أن ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔﺎﻋ ﻞ ھ ﻮ‬
‫)‪.(k2 = 17.00 × 10-5 dm-3 mol-1 s-1‬‬
‫اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫‪........................ ............................................................................................................................. ...............................................‬‬
‫‪.......................................................................................... ..........................................................................................................‬‬
‫‪............................... ........................................ .............................................................................................................................‬‬
‫‪....................................................................... .............................................................................................................................‬‬
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‫‪897‬‬
‫ﻣﺜﺎﻝ )‪(٣١-٤‬‬
‫وﺟ ﺪ ﻓ ﻲ ﺗﻔﺎﻋ ﻞ أﺣ ﺎدي اﻟﺮﺗﺒ ﺔ أن اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻻﺳ ﺘﮭﻼك ﻧﺼ ﻒ‬

‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻤﺘﻔﺎﻋﻞ ھﻮ )‪ (5000 S‬ﻋﻨ ﺪ )‪ ،(325 K‬أﻣ ﺎ ﻋﻨ ﺪ‬
‫)‪ (335 K‬ﻓﻘ ﺪ وﺟ ﺪ أن اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻻﺳ ﺘﮭﻼك ﻧﺼ ﻒ اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻹﺑﺘﺪاﺋﻲ ﻟﻤﺘﻔﺎﻋﻞ ھﻮ ‪1000 S‬‬
‫اﺣﺴ ﺐ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻋﻨ ﺪ درﺟﺘ ﻲ اﻟﺤ ﺮارة واﺣﺴ ﺐ ﻣﻨﮭ ﺎ طﺎﻗ ﺔ‬
‫اﻟﺘﻨﺸﯿﻂ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
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‫‪898‬‬
‫ﻣﺜﺎﻝ )‪(٣٢-٤‬‬
‫ﻓﻲ أﺣﺪ اﻟﺘﻔﺎﻋﻼت وﺟﺪ أن ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ )‪ (35 ºC‬ﺿﻌﻒ ﻗﯿﻤﺘﮫ‬
‫ﻋﻨﺪ )‪ ،(25 ºC‬اﺣﺴﺐ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
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‫‪899‬‬
‫ﻣﺜﺎﻝ )‪(٣٣-٤‬‬
‫إذا ﻋﻠﻤ ﺖ أن ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﺗﺘﻀ ﺎﻋﻒ ﺛ ﻼث ﻣ ﺮات‬

‫ﻋﻨ ﺪﻣﺎ ﺗ ﺰداد درﺟ ﺔ ﺣ ﺮارة اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ )‪ (300 K‬اﻟ ﻰ )‪(310 K‬‬
‫ﻓﺎﺣﺴﺐ طﺎﻗﺔ ﺗﻨﺸﯿﻂ ھﺬا اﻟﺘﻔﺎﻋﻞ‬
‫طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ‪Ea = 84.49 kJ/mol :‬‬
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‫‪900‬‬
‫ﻣﺜﺎﻝ )‪(٣٤-٤‬‬
‫أﻋﻄﯿ ﺖ ﻣﻌﺎدﻟ ﺔ أرھﯿﻨﯿ ﻮس ﻟﺴ ﺮﻋﺔ ﺗﺤﻠ ﻞ ﺛﻨ ﺎﺋﻲ ﺑﯿﻮﺗﯿ ﻞ اﻟﺰﺋﺒ ﻖ وﻗ ﺪ‬

‫وﺟﺪ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪ 193 × 103 J mol-1 ‬‬
‫‪ −‬‬ ‫‪‬‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬
‫‪k (s-1 ) = 1015.2 exp‬‬
‫‪ 180 × 103 J mol-1 ‬‬
‫‪ −‬‬ ‫‪‬‬
‫‪‬‬ ‫‪RT‬‬ ‫‪‬‬
‫‪k (s-1 ) = 1014.1exp‬‬
‫اﺣﺴﺐ درﺟﺔ اﻟﺤﺮارة اﻟﺘﻲ ﯾﺘﺴﺎوى ﻋﻨﺪھﺎ ﺛﺎﺑﺘﺎ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻠﯿﻦ‪.‬‬
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‫‪901‬‬
‫ﻣﺜﺎﻝ )‪(٣٥-٤‬‬
‫إذا ﻋﻠﻤ ﺖ أن طﺎﻗ ﺔ ﺗﻨﺸ ﯿﻂ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﺗﺴ ﺎوي )‪(146.3 kJ/mol‬‬

‫ﻓﺎﺣﺴﺐ ﺑﺄي ﻧﺴﺒﺔ ﺳﻮف ﺗﺰداد ﻗﯿﻤﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪﻣﺎ‬
‫ﺗﺰداد درﺟﺔ ﺣﺮارﺗﮫ ﻣﻦ )‪ (25 ºC‬اﻟﻰ )‪.(35 ºC‬‬
‫ﺗﺰداد ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻧﺴﺒﺔ ‪ 6.8 : 1‬أي أن )‪.(k2/k1 = 6.8‬‬
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‫‪902‬‬
‫ﺍﳌﱰﺍﻛﺐ ﺍﻟﻔﻌﺎﻝ‬
‫ﯾﻌﺘﺒﺮ اﻟﻤﺘﺮاﻛﺐ اﻟﻔﻌﺎل ﺣﺎﻟﺔ وﺳﻄﯿﺔ ﻓ ﻲ ﺟﻤﯿ ﻊ اﻟﺘﻔ ﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿ ﺔ‪.‬‬
‫وﻟﻜ ﻲ ﯾﻤﻜ ﻦ اﺳ ﺘﻨﺒﺎط ﻣﻌ ﺪل ﺳ ﯿﺮ اﻟﺘﻔﺎﻋ ﻞ ﻧﻈﺮﯾ ﺎ ً‪ ،‬ﻓ ﻼ ﺑ ﺪ ﻣ ﻦ وﺿ ﻊ‬
‫ﺗﺼﻮر ﻟﺘﺮﻛﯿﺐ ذﻟﻚ اﻟﻤﺘﺮاﻛﺐ اﻟﻔﻌﺎل‪.‬‬
‫وﺑﻔﺮض أن ھﻨﺎك ﺗﻔﺎﻋﻼً ﺑﯿﻦ ذرة "‪ "A‬وﺟﺰيء ﺛﻨ ﺎﺋﻲ اﻟ ﺬرة‪ ،‬ﻣﺜ ﻞ ‪:‬‬
‫)‪ ،(BC‬ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﺗﻤﺜﯿﻞ ذﻟﻚ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪A + BC ‬‬
‫‪→ AB + C‬‬
‫وﻟﻜ ﻲ ﯾﺤ ﺪث اﻟﺘﻔﺎﻋ ﻞ‪ ،‬ﻓ ﻼ ﺑ ﺪ أن ﺗﻘﺘ ﺮب اﻟ ﺬرة )‪ (A‬ﻣ ﻦ اﻟﺠ ﺰيء‬

‫)‪ (BC‬وﻛﻠﻤﺎ اﻗﺘﺮﺑ ﺖ )‪ (A‬ﻣ ﻦ )‪ (BC‬ﻓﺈﻧ ﮫ ﯾﺤ ﺪث ﺗ ﺪاﺧﻞ إﻟﻜﺘﺮوﻧ ﻲ‬
‫وﺗﺰداد طﺎﻗﺔ اﻟﻮﺿﻊ‪ ،‬وﺗﺴﺘﻤﺮ ﻓﻲ اﻟﺰﯾﺎدة ﺣﺘﻰ ﻧﺼﻞ اﻟﻰ اﻟﺘﺮﻛﯿﺐ ‪:‬‬
‫‪) A-B-C‬اﻟﻤﺘﺮاﻛﺐ اﻟﻔﻌﺎل(‬
‫ﺛﻢ ﺑﻌﺪ ذﻟﻚ ﯾﻮﺟﺪ اﺣﺘﻤﺎﻻن‪ ،‬وھﻤﺎ إﻣﺎ ‪:‬‬
‫‪ (١‬اﺳﺘﻤﺮار واﺳﺘﻜﻤﺎل اﻟﺘﻔﺎﻋﻞ اﻟﻰ اﻷﻣﺎم )ﻓ ﻲ اﻹﺗﺠ ﺎه اﻷﻣ ﺎﻣﻲ( ﻓ ﻲ‬
‫اﺗﺠﺎه ﺗﻜﻮﯾﻦ اﻟﻨﻮاﺗﺞ‪ ،‬أي ﻓﻲ اﺗﺠﺎه ﺗﻜﻮﯾﻦ )‪...(AB + C‬‬
‫أو‬
‫‪ (٢‬اﻟﻌﻮدة ﻟﻠﺨﻠﻒ )اﺗﺠﺎه اﻟﺘﻔﺎﻋﻞ اﻟﺨﻠﻔﻲ( ﻓﻲ اﺗﺠ ﺎه اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪،‬‬
‫أي ﻓﻲ اﺗﺠﺎه ﺗﻜﻮﯾﻦ )‪. (A + BC‬‬

‫‪903‬‬
‫واﻟﻤﺘﺮاﻛ ﺐ اﻟﻮﺳ ﻂ ﯾﻄﻠ ﻖ ﻋﻠﯿ ﮫ اﺳ ﻢ اﻟﻤﺘﺮاﻛ ﺐ اﻟﻔﻌ ﺎل ﻟﮭ ﺬا ﻟﺘﻔﺎﻋ ﻞ ‪،‬‬

‫وﯾﺘﻢ ذﻟﻚ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪→ [ A - B - C ] ‬‬
‫‪A + BC ‬‬ ‫‪→ AB + C‬‬
‫وﻋﻨﺪ اﻧﻔﺼﺎل اﻟﺬرة "‪ "C‬وﺗﻜﻮن اﻟﺠﺰيء "‪ ،"AB‬ﻓﺈن طﺎﻗﺔ اﻟﻮﺿﻊ‬
‫ﺗﻘﻞ أﯾﻀﺎ ً‪.‬‬
‫وﻋﻠ ﻰ ذﻟ ﻚ‪ ،‬ﻓﺎﻟﺤﺎﻟ ﺔ اﻟﻔﻌﺎﻟ ﺔ ﺗﻤﺜ ﻞ أﻋﻠ ﻰ طﺎﻗ ﺔ وﺿ ﻊ ﻋﻠ ﻰ ﻣﺴ ﺎر‬
‫• وﯾﻮﺿ ﺢ اﻟﺸ ﻜﻞ )‪ (١٧-٤‬اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ طﺎﻗ ﺔ اﻟﻮﺿ ﻊ وﺧ ﻂ ﺳ ﯿﺮ‬

‫اﻟﺘﻔﺎﻋﻞ )ﻣﺴﺎر اﻟﺘﻔﺎﻋﻞ( ﻟﻠﻌﻤﻠﯿﺔ ﻛﻠﮭﺎ‪.‬‬
‫ﺷﻜﻞ )‪ : (١٧-٤‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ طﺎﻗﺔ اﻟﻮﺿﻊ وﺧﻂ ﺳﯿﺮ اﻟﺘﻔﺎﻋﻞ‬

‫‪904‬‬
‫• وﻋﻨﺪ ﺗﻜﻮﯾﻦ اﻟﻤﺘﺮاﻛﺐ اﻟﻔﻌﺎل ﻣﻦ اﻟﻤﺘﻔﺎﻋﻼت‪ ،‬ﻓ ﺈن اﻟﻄﺎﻗ ﺔ اﻟﻔﻌﺎﻟ ﺔ‬

‫ﻟﻠﻌﻤﻠﯿﺔ اﻟﻄﺮدﯾﺔ ﺗﻜﻮن )‪ .(E1‬وﺑﺎﻟﻤﺜﻞ ﺗﻜﻮن اﻟﻄﺎﻗﺔ اﻟﻔﻌﺎﻟ ﺔ ﻟﻠﻌﻤﻠﯿ ﺔ‬
‫اﻟﻌﻜﺴﯿﺔ )اﻟﺨﻠﻔﯿﺔ( ھﻲ )‪ ،(E-1‬واﻟﻔﺮق ﺑﯿﻨﮭﻤﺎ ﯾﻌﻄﻰ ﺑﺎﻟﻌﻼﻗﺔ ‪:‬‬
‫‪∆E = E1 - E -1‬‬
‫وﺑﺎﻟﻨﺴﺒﺔ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪ ،‬ﻓﺈﻧﮫ ﻻ ﯾﻮﺟﺪ ﺗﻐﯿﺮ ﻓﻲ ﻋﺪد اﻟﺠﺰﯾﺌﺎت ﯾﺼ ﺎﺣﺐ‬
‫ﺣ ﺪوث اﻟﺘﻔﺎﻋ ﻞ‪ ،‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻻ ﯾﻮﺟ ﺪ ﺗﻐﯿ ﺮ ﻓ ﻲ اﻟﻀ ﻐﻂ )ﯾﺒﻘ ﻰ اﻟﻀ ﻐﻂ‬
‫ﺛﺎﺑﺘﺎ ً( وﻋﻠﻰ ذﻟﻚ ﺗﻜﻮن ) ‪ ( ΔH‬ھﻲ ﻧﻔﺴﮭﺎ ) ‪. ( ΔE‬‬
‫• وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ ﻋﻠﻰ اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪ΔH = ∆E = E1 - E -1‬‬
‫وﺑﻨﺎ ًء ﻋﻠﻰ ذﻟﻚ‪ ،‬ﺗﻮﺟﺪ ﺣﺎﻟﺘﺎن‪ ،‬وھﻤﺎ ‪:‬‬

‫< ‪ ( E1‬وﺗﻜﻮن ) ‪ ( ΔH‬ﺳ ﺎﻟﺒﺔ اﻟﻘﯿﻤ ﺔ‪ ،‬وﯾﻜ ﻮن اﻟﺘﻔﺎﻋ ﻞ‬ ‫) ‪E -1‬‬ ‫أ( إذا ﻛﺎﻧﺖ‬
‫ﻣﻦ اﻟﻨﻮع اﻟﻄﺎرد ﻟﻠﺤﺮارة‪.‬‬
‫‪ ، ( E1‬وﺗﻜ ﻮن ) ‪ ( ΔH‬ﻣﻮﺟﺒ ﺔ اﻟﻘﯿﻤ ﺔ‪ ،‬وﯾﻜ ﻮن‬ ‫) ‪> E -1‬‬ ‫ب( إذا ﻛﺎﻧ ﺖ‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﻨﻮع اﻟﻤﺎص ﻟﻠﺤﺮارة‪.‬‬
‫س( ﻋﺮف اﻟﻤﺘﺮاﻛﺐ اﻟﻨﺸﻂ اﻟﻔﻌﺎل‪.‬‬
‫س( أرﺳﻢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ طﺎﻗﺔ اﻟﻮﺿﻊ وﺧ ﻂ ﺳ ﯿﺮ اﻟﺘﻔﺎﻋ ﻞ )ﺷ ﻜﻞ ﻣﻨﺤﻨ ﻰ طﺎﻗ ﺔ‬
‫اﻟﻮﺿﻊ( وذﻟﻚ ﻟﺘﻔﺎﻋﻞ طﺎرد ﻟﻠﺤﺮارة ﻣﻮﺿﺤﺎ ً ﻛﯿﻔﯿﺔ ﺣﺴﺎب ) ‪ ( ΔH‬ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬

‫‪905‬‬
‫ﺗﺄﺛﲑ ﺍﻟﻌﺎﻣﻞ ﺍﳌﺴﺎﻋﺪ ﻋﻠﻰ ﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ‬
‫• ﻓ ﻲ أﻏﻠ ﺐ اﻟﺘﻔ ﺎﻋﻼت ﻻ ﺗﺨﺘﻠ ﻒ ﻗﯿﻤ ﺔ ﻣﻌﺎﻣ ﻞ اﻟﺘ ﺮدد )‪ (A‬ﻛﺜﯿ ﺮاً‬
‫)ﺗﺘﺮاوح ﻗﯿﻤﺔ )‪ (log A‬ﺑﯿﻦ )‪ (12-7‬ﻟ ﺬا ﺗﻌﺘﺒ ﺮ ﺗ ﺄﺛﯿﺮه ﻋﻠ ﻰ ﻗﯿﻤ ﺔ‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ (k‬ﻣﮭﻤﻼً وﺑﺎﻟﺘﺎﻟﻲ ﻋﻠﻰ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫• إذا ﺗﺨﯿﻠﻨﺎ ﺗﻔ ﺎﻋﻠﯿﻦ ﻟﮭﻤ ﺎ ﻧﻔ ﺲ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟﺘ ﻲ ﺣ ﺮارة‬
‫ﻣﺨﺘﻠﻔﺘﯿﻦ ﻓﺈن اﻟﺤﺪ )‪ (Ea/RT‬ﺳﯿﻜﻮن ﺛﺎﺑﺘ ﺎ ً اﻷﻣ ﺮ اﻟ ﺬي ﯾﺘﻐﯿ ﺮ ﻓﯿ ﮫ‬
‫اﻟﺤ ﺪﯾﻦ )‪ (T ،Ea‬ﻓ ﺈذا زادت درﺟ ﺔ اﻟﺤ ﺮارة اﻟﻤﻄﻠﻘ ﺔ ﯾﺠ ﺐ أن‬
‫ﺗﺰداد ﻗﯿﻤﺔ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ واﻟﻌﻜﺲ ﺻﺤﯿﺢ‪.‬‬
‫ﻣﻦ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪∆H = E1 - E -1‬‬
‫ﻣﻮﺟﺒﺔ ﻓﺈن طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ اﻟﻄﺮدﯾﺔ ‪ E1‬ﯾﺠﺐ أن‬ ‫‪∆H‬‬ ‫أي أﻧﮫ ﻟﻜﻲ ﺗﻜﻮن‬
‫ﺗﻜﻮن أﻛﺒﺮ ﻣﻦ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ اﻟﻌﻜﺴﯿﺔ ‪ E-1‬وﺳﺘﺴﺎوي ‪:‬‬
‫‪E1 = ∆H + E -1‬‬
‫أو ﺑﻤﻌﻨﻰ آﺧﺮ أن ‪:‬‬

‫‪E1 > ∆H‬‬
‫• ﻓ ﻲ ﺣﺎﻟ ﺔ اﻟﺘﻔ ﺎﻋﻼت اﻟﻄ ﺎردة ﻟﻠﺤ ﺮارة ﺗ ﻨﻌﻜﺲ اﻟﺼ ﻮرة وﺳ ﺘﻜﻮن‬
‫طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ اﻟﻌﻜﺴ ﯿﺔ )‪ (E-1‬أﻛﺒ ﺮ ﻣ ﻦ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ اﻟﻄﺮدﯾ ﺔ‬

‫‪906‬‬
‫)‪ (E1‬وﻋﻠﯿ ﮫ ﻓ ﺈن ) ‪ ( ∆H‬ﺳﺘﺼ ﺒﺢ ﺳ ﺎﻟﺒﺔ أي أن اﻟﻌﻼﻗ ﺔ‬

‫‪ ( E1‬ﺳﺘﻨﻌﻜﺲ وﺗﻜﻮن ‪:‬‬ ‫‪> ∆H‬‬ ‫)‬
‫‪E1 < ∆H‬‬
‫• ھﺬا ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻼت اﻟﻤﺎﺻﺔ ﻟﻠﺤﺮارة ﺗﺤﺘﺎج اﻟﻰ طﺎﻗ ﺔ ﺗﻨﺸ ﯿﻂ‬
‫أﻛﺒﺮ ﻣﻦ اﻟﺘﻔﺎﻋﻼت اﻟﻄ ﺎردة ﻟﻠﺤ ﺮارة وھ ﻲ ﺑ ﻨﻔﺲ اﻟﻮﻗ ﺖ ﺗﺤﺘ ﺎج‬
‫اﻟ ﻰ درﺟ ﺔ ﺣ ﺮارة أﻋﻠ ﻰ ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت اﻟﻄ ﺎردة ﻟﻠﺤ ﺮارة ﻟﻜ ﻲ‬
‫ﺗﺤﺪث‪.‬‬
‫• وﻛﻠﻤﺎ أردﻧﺎ زﯾ ﺎدة ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﯾﺠ ﺐ زﯾ ﺎدة درﺟ ﺔ اﻟﺤ ﺮارة أو‬
‫ﺧﻔﺾ طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﺣﯿ ﺚ ﯾﻤﻜ ﻦ زﯾ ﺎدة درﺟ ﺔ اﻟﺤ ﺮارة ﺑﺴ ﮭﻮﻟﺔ‪،‬‬
‫أﻣﺎ ﺧﻔﺾ طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻓ ﺄﻣﺮ ﻻ ﯾﻤﻜ ﻦ ﺣﺪوﺛ ﮫ إﻻ ﺑﺘﻐﯿ ﺮ اﻟﻄﺮﯾ ﻖ‬
‫اﻟﺬي ﺗﺴﻠﻜﮫ اﻟﻤﺘﻔﺎﻋﻼت ﻟﻠﻮﺻﻮل ﻟﻠﺤﺎﻟﺔ اﻹﻧﺘﻘﺎﻟﯿ ﺔ ﺑﻄﺎﻗ ﺔ ﺗﻨﺸ ﯿﻂ‬
‫أﻗ ﻞ وھ ﺬا ﻣ ﺎ ﯾﺤ ﺪث ﻋﻨ ﺪ إﺿ ﺎﻓﺔ ﻋﺎﻣ ﻞ ﺣ ﺎﻓﺰ ﺣﯿ ﺚ ﯾﻐﯿ ﺮ ﻣ ﻦ‬
‫ﻣﯿﻜﺎﻧﯿﻜﯿﺔ اﻟﺘﻔﺎﻋ ﻞ ﻟﻜ ﻲ ﯾﺤ ﺪث ﺑﻄﺎﻗ ﺔ ﺗﻨﺸ ﯿﻂ أﻗ ﻞ دون أن ﯾﺴ ﺘﮭﻠﻚ‬
‫ﻓﻲ اﻟﺘﻔﺎﻋﻞ‪.‬‬

04 - أثر الحرارة على سرعة التفاعلات الكيميائية

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04 - أثر الحرارة على سرعة التفاعلات الكيميائية

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﻋﺎﻟﺠﻨﺎ ﻓﯿﻤﺎ ﺳﺒﻖ اﻟﺤﺮﻛﯿ ﺔ اﻟﻜﯿﻤﯿﺎﺋﯿ ﺔ ﻣ ﻦ ﻣﻨﻈ ﻮر اﻟﺘﻐﯿ ﺮ ﻓ ﻲ اﻟﺘﺮﻛﯿ ﺰ‬

‫ﺗﺄﺛﲑ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫• ﻟﻘﺪ ﻻﺣﻈﻨﺎ أﻧﻨﺎ ﺗﻌﺎﻣﻠﻨﺎ ﻓﻲ اﻟﻔﺼﻮل اﻟﺴﺎﺑﻘﺔ ﻣﻊ اﻟﺠﺰﯾﺌﺎت اﻟﻤﺘﻔﺎﻋﻠﺔ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﻃﺎﻗﺔ ﺍﻟﺘﻨﺸﻴﻂ ‪Activation Energy‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫وﻣﻦ اﻟﺸﻜﻞ )‪ (١-٤‬ﻧﻼﺣﻆ أن ‪:‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺗ ﺆﺛﺮ درﺟ ﺔ اﻟﺤ ﺮارة ﻋﻠ ﻰ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗ ﺄﺛﯿﺮاً ﻛﺒﯿ ﺮاً ﺣﯿ ﺚ وﺟ ﺪ‬

‫ﺷﻜﻞ )‪ : (٢-٤‬أﻧﻮاع اﻟﻤﻨﺤﻨﯿﺎت اﻟﺘﻲ ﺗﺒﯿﻦ ﺗﻐﯿﺮ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻊ درﺟﺔ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺍﻟﻨــﻮﻉ ﺍﻷﻭﻝ )ﺷ ﻜﻞ ‪ (٣-٤‬ھ ﻮ اﻟﺸ ﺎﺋﻊ‪ ،‬وﻗ ﺪ ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿ ﮫ ﻣ ﻦ‬

‫ﺷﻜﻞ )‪ : (٣-٤‬ﻣﻨﺤﻨﻰ أرھﯿﻨﯿﻮس ﻟﺘﺄﺛﯿﺮ درﺟﺔ اﻟﺤﺮارة‬

‫ﺍﻟﻨــــﻮﻉ ﺍﻟﺜــــﺎﻧﻲ )ﺷــــﻜﻞ ‪ : (٤-٤‬ﯾﺤ ﺪث ﻋﻨ ﺪ ﺣ ﺪوث اﻧﻔﺠ ﺎر‬

‫)‪ (explosion‬ﺧ ﻼل اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة اﻻﺷ ﺘﻌﺎل‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺍﻟﻨــﻮﻉ ﺍﻟﺜﺎﻟــﺚ )ﺷــﻜﻞ ‪ : (٥-٤‬ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿ ﮫ ﻣ ﻦ ﺗﻔ ﺎﻋﻼت‬

‫اﻟﮭﺪرﺟﺔ اﻟﻤﺤﻔﺰة‪ ،‬وﺗﻔﺎﻋﻼت اﻹﻧﺰﯾﻤﺎت )‪،(enzyme reactions‬‬

‫ﺍﻟﻨﻮﻉ ﺍﻟﺮﺍﺑﻊ )ﺷﻜﻞ ‪ (٦-٤‬ﻟﻮﺣﻆ ﺧﻼل أﻛﺴﺪة اﻟﻜﺮﺑﻮن‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫اﻟﻨﯿﺘﺮﯾﻚ )‪ (NO‬ﻣﻊ اﻷﻛﺴﺠﯿﻦ ﻓﻘﻂ‪.‬‬

‫• ﻟﻘﺪ ﺗﻢ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ اﻟﻨ ﻮع اﻷول )ﺷ ﻜﻞ ‪ (٣-٤‬ﻧﺘﯿﺠ ﺔ ﻟﻠﺪراﺳ ﺎت‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ ﯾﻤﻜﻦ أن ﺗﺘﻀﺎﻋﻒ ﻣﺮﺗﯿﻦ أو ﺛﻼﺛ ﺎ ً ﻟﻜ ﻞ‬

‫وھﻲ ﻋﻼﻗﺔ ﺧﻄﯿﺔ ﻣﯿﻠﮭﺎ )‪ (-B‬ﺳﺎﻟﺐ ﻟﻤﻌﻈﻢ اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ‪.‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫• وﻟﻘ ﺪ ﺗﻮﺳ ﻊ اﻟﻌ ﺎﻟﻢ أرھﯿﻨﯿ ﻮس )‪ (1889‬ﻓ ﻲ ﺗﻄﺒﯿ ﻖ ھ ﺬه اﻟﻔﻜ ﺮة‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺣﯿ ﺚ )‪ (kf‬و )‪ (kr‬ھﻤ ﺎ ﺛﺎﺑﺘ ﺎ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ اﻻﺗﺠ ﺎھﯿﻦ اﻟﻤﺒﺎﺷ ﺮ‬

‫‪dlnk f‬‬ ‫‪dlnk r‬‬ ‫‪ΔU‬‬

‫ﺣﯿ ﺚ )‪ (Eaf‬و )‪ (Ear‬ھﻤ ﺎ طﺎﻗﺘ ﺎ اﻟﺘﻨﺸ ﯿﻂ ﻓ ﻲ اﻻﺗﺠ ﺎھﯿﻦ اﻟﻤﺒﺎﺷ ﺮ‬

‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ ‪ :‬ﺃﺛﺮ ﺍﳊﺮﺍﺭﺓ ﻋﻠﻰ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫‪dlnk f dlnk r‬‬ ‫‪E‬‬ ‫‪E‬‬

‫ﺣﯿﺚ )‪ (I‬ﺛﺎﺑﺖ‪ ،‬وﻗ ﺪ وﺟ ﺪ ﻋﻤﻠﯿ ﺎ ً أن ﻗﯿﻤﺘ ﮫ ﯾﻤﻜ ﻦ أن ﺗﺴ ﺎوي اﻟﺼ ﻔﺮ‪،‬‬

‫‪ dlnK‬‬ ‫‪ΔU ‬‬

‫‪ dln k r‬‬ ‫‪‬‬

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