02- قانون سرعة التفاعل - رتب التفاعل

(360)
‫ ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬: ‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ‬
‫ ﺍﳍﺰﺍﺯﻱ‬‫ ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‬.‫ ﺩ‬/‫ﺇﻋﺪﺍﺩ‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ‬
‫ﻗﺎﻧﻮﻥ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

(Reaction Rate Law)
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‫)‪(361‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬
‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ‬
‫ﻗﺎﻧﻮﻥ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬
‫)‪(Reaction Rate Law‬‬
‫ﺗﻐﲑ ﺗﺮﻛﻴﺰ ﺍﳌﺎﺩﺓ ﺍﳌﺘﻔﺎﻋﻠﺔ ﻣﻊ ﺍﻟﺰﻣﻦ‬
‫ﺗﻮﺿ ﺢ ﻣﻌﺎدﻟ ﺔ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻛﯿ ﻒ ﺗﺘﻐﯿ ﺮ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺘﻐﯿ ﺮ‬

‫ﺗﺮﻛﯿﺰ اﻟﻤﺎدة أو اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ .‬وإن اﺷ ﺘﻘﺎق ﻣﻌﺎدﻟ ﺔ رﯾﺎﺿ ﯿﺔ ﺗﺒ ﯿﻦ‬
‫ﺗﻐﯿﺮات ﺗﺮﻛﯿﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻣ ﻊ اﻟ ﺰﻣﻦ أﺟ ﺪى وأﻧﻔ ﻊ ﻣ ﻦ اﻟﻨﺎﺣﯿ ﺔ‬
‫اﻟﻌﻤﻠﯿﺔ ﺣﯿﺚ أن ﻣﻌﺎدﻟﺔ ﻛﮭﺬه ﯾﻜﻮن ﺗﻄﺒﯿﻘﮭﺎ ﻣﺒﺎﺷ ﺮة ﻋﻠ ﻰ اﻟﻤﻌﻠﻮﻣ ﺎت‬
‫اﻟﺘﺠﺮﯾﺒﯿﺔ واﻟﺘﻲ ﻋﺎدةً ﻣﺎ ﺗﻜﻮن ﻋﺒﺎرة ﻋﻦ ﺗﺮاﻛﯿﺰ ﻋﻨﺪ أزﻣﻨ ﺔ ﻣﺨﺘﻠﻔ ﺔ‪.‬‬
‫إﺿ ﺎﻓﺔ اﻟ ﻰ ذﻟ ﻚ ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ اﻟﺘﻨﺒ ﺆ ﺑ ﺎﻟﺘﺮﻛﯿﺰ ﻋﻨ ﺪ أي زﻣ ﻦ ﻣﻌ ﯿﻦ‬
‫وﺑﺎﺳ ﺘﺨﺪاﻣﮭﺎ ﯾﻤﻜ ﻦ اﻹﺟﺎﺑ ﺔ ﻋﻠ ﻰ ﺗﺴ ﺎؤﻻت ﻣﺨﺘﻠﻔ ﺔ ﻣﺜ ﻞ ‪ :‬ﻣ ﺎ اﻟ ﺰﻣﻦ‬
‫اﻟ ﻼزم ﻟﺘﻔﺎﻋ ﻞ )‪ (50 %‬أو )‪ (90 %‬ﻣ ﻦ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ؟ وﯾﻤﻜ ﻦ‬
‫اﺷﺘﻘﺎق ھﺬه اﻟﻤﻌﺎدﻟﺔ ﺑﺎﺳﺘﺨﺪام ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ وﺷ ﻜﻞ اﻟﻤﻌﺎدﻟ ﺔ‬
‫ﯾﻤﻜ ﻦ أن ﯾﻜ ﻮن ﺑﺴ ﯿﻄﺎ ً أو ﻣﻌﻘ ﺪاً ﺣﺴ ﺐ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ وﻋ ﺪد اﻟﻤ ﻮاد‬
‫اﻟﻤﺸﺘﺮﻛﺔ ﻓﻲ اﻟﺘﻔﺎﻋﻞ‪.‬‬
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‫)‪(362‬‬
‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺴﺮﻋﺔ‬
‫ﻧﻌﺘﺒﺮ ﺗﻔ ﺎﻋﻼً ﻛﯿﻤﯿﺎﺋﯿ ﺎ ً ﯾﻨﺤ ﻞ ﻓﯿ ﮫ اﻟﻤﺘﻔﺎﻋ ﻞ )‪ (A‬ﻣﻌﻄﯿ ﺎ ً ﻧ ﺎﺗﺠﯿﻦ ھﻤ ﺎ ‪:‬‬

‫)‪ (C ،B‬ﻋﻠﻰ اﻟﻨﺤﻮ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪A ‬‬
‫‪→B + C‬‬
‫وﻓ ﻲ أﺛﻨ ﺎء ﺳ ﯿﺮ اﻟﺘﻔﺎﻋ ﻞ ﯾﻘ ﻞ ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔﺎﻋ ﻞ )‪ (A‬ﻓ ﻲ ﺣ ﯿﻦ ﯾ ﺰداد‬

‫ﺗﺮﻛﯿﺰ ﻛﻞ ﻣﻦ )‪ .(C) ،(B‬وﯾﻤﻜﻦ ﺗﻤﺜﯿﻞ ذﻟﻚ ﺑﯿﺎﻧﯿ ﺎ ً ﺑﺎﺳ ﺘﺨﺪام اﻟﻌﻼﻗ ﺔ‬
‫ﺑﯿﻦ اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ ﻟﻠﻤﺘﻔﺎﻋﻞ )‪ (A‬ﻋﻠﻰ اﻟﺼﻮرة ﺑﺎﻟﺸﻜﻞ )‪.(١-٢‬‬
‫ﺷﻜﻞ )‪ : (١-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ‬

‫)‪(363‬‬
‫وﺗﻌﯿﻦ اﻟﺴﺮﻋﺔ ﺑﺎﻟﺘﻐﯿﺮ ﻓﻲ ﻛﻤﯿﺔ ﻣﻘﺎﺳﺔ ﻣﻊ اﻟﺘﻐﯿﺮ ﻓ ﻲ اﻟ ﺰﻣﻦ‪ .‬وﺗﻘ ﺎس‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ ﺑﺎﻟﺘﻐﯿﺮ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔﺎﻋ ﻞ ﻣ ﻊ اﻟﺘﻐﯿ ﺮ ﻓ ﻲ‬
‫اﻟﺰﻣﻦ‪ .‬وﺗﻌﻄﻰ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ أي زﻣﻦ "‪ "t‬ﺑﻤﯿﻞ اﻟﻤﻨﺤﻨﻰ ﻋﻨ ﺪ‬
‫ھ ﺬه اﻟﻠﺤﻈ ﺔ‪ ،‬ﺑﻤﻌﻨ ﻰ أﻧ ﮫ ﯾﺴ ﺎوي اﻟ ﻨﻘﺺ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ )‪ (A‬ﻋﻨ ﺪ ھ ﺬه‬
‫اﻟﻠﺤﻈ ﺔ‪ .‬وﯾﻤﻜ ﻦ أن ﯾﻌﺒ ﺮ ﻋ ﻦ اﻟﺴ ﺮﻋﺔ ﺑﺎﻟﺰﯾ ﺎدة ﻓ ﻲ ﺗﺮﻛﯿ ﺰ )‪ (B‬أو‬
‫)‪ (C‬ﻣﻊ اﻟﺰﻣﻦ ‪:‬‬
‫] ‪d [ A ] d [ B] d [ C‬‬
‫‪rate = -‬‬ ‫=‬ ‫=‬
‫‪dt‬‬ ‫‪dt‬‬ ‫‪dt‬‬
‫ﻓﯿﻌﺒ ﺮ ﻋ ﻦ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﺑﻤﻌ ﺪل اﺧﺘﻔ ﺎء اﻟﻤﺘﻔﺎﻋ ﻞ أو‬

‫ﻣﻌ ﺪل ﺗﻜ ﻮﯾﻦ أو ظﮭ ﻮر اﻟﻨ ﻮاﺗﺞ‪ .‬ﻓﺎﻟﺸ ﻜﻞ )‪ (١-٢‬ﯾﻮﺿ ﺢ أن ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋﻞ ﺗﺘﻐﯿﺮ أﺛﻨﺎء ﺳﯿﺮ اﻟﺘﻔﺎﻋﻞ‪ .‬ﻓﺎﻟﺴﺮﻋﺔ اﻟﺘﻲ ﺗﻜﻮن ﻓﻲ أﻋﻠ ﻰ ﻗﯿﻤ ﺔ‬
‫ﻟﮭﺎ ﻓﻲ اﻟﺒﺪاﯾﺔ ﺗﻘﻞ أﺛﻨﺎء ﺳﯿﺮ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻭﺍﻋﺘﻤﺎﺩﻫﺎ ﻋﻠﻰ ﺗﺮﻛﻴﺰ ﺍﳌﺘﻔﺎﻋﻼﺕ‬
‫وﺟﺪ أن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﺗﺮﻛﯿﺰ اﻟﻤﺘﻔﺎﻋﻼت طﺒﻘﺎ ً ﻟﻠﻌﻼﻗﺔ ‪:‬‬
‫‪A ‬‬
‫‪→B + C‬‬
‫] ‪rate α [ A‬‬
‫‪n‬‬
‫ﺣﯿﺚ )‪ (n‬ﺛﺎﺑﺖ ﯾﺴﻤﻰ رﺗﺒﺔ اﻟﻤﺘﻔﺎﻋﻞ‪ .‬واﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬

‫واﻟﺘﺮﻛﯿﺰ ﺗﺴﻤﻰ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ وﺗﺄﺧﺬ اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫)‪(364‬‬
‫]‪d [A‬‬
‫]‪= k [A‬‬
‫‪n‬‬
‫‪-‬‬
‫‪dt‬‬
‫ﺣﯿﺚ )‪ (k‬ﺛﺎﺑﺖ ﻟﻠﺘﻔﺎﻋﻞ اﻟﻮاﺣﺪ ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﺔ وﯾﺴﻤﻰ ﺛﺎﺑ ﺖ‬
‫اﻟﺴﺮﻋﺔ اﻟﻨﻮﻋﻲ ﻟﻠﺘﻔﺎﻋﻞ‪ .‬وﺗﻮﺿﺢ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ أو ﻗ ﺎﻧﻮن اﻟﺴ ﺮﻋﺔ‬
‫أن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﺘﻐﯿ ﺮ ﺑﺘﻐﯿ ﺮ ﺗﺮﻛﯿ ﺰات اﻟﻤﺘﻔ ﺎﻋﻼت‪ ،‬وﻻ ﯾﺘﻀ ﻤﻦ‬
‫ﺗﺮﻛﯿﺰ اﻟﻨﻮاﺗﺞ‪.‬‬
‫ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ‬
‫ﯾﻜ ﻮن ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﺑﻤﺜﺎﺑ ﺔ ﻣﻘﯿ ﺎس ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﻋﻨ ﺪ‬
‫درﺟﺔ ﺣﺮارة ﻣﻌﯿﻨﺔ‪.‬‬
‫ﻭﺣﺪﺍﺕ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ )‪(k‬‬
‫وﺗﻌﺘﻤﺪ وﺣﺪات اﻟﺜﺎﺑﺖ ﻟﺴﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻠﻰ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‬

‫• ﻓﻌﻠﻰ ﺳﺒﯿﻞ اﻟﻤﺜﺎل ﯾﻜﻮن ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻷﺣﺎدي اﻟﺮﺗﺒﺔ ‪:‬‬
‫]‪d [A‬‬
‫‪-‬‬ ‫]‪= k [A‬‬
‫‪dt‬‬
‫وﺑﺬا ﺗﻜﻮن ‪:‬‬

‫‪concentration‬‬
‫) ‪= k ( concentration‬‬
‫‪time‬‬
‫ﻟﺬا ﻓﺈﻧ ﮫ ﻟﺠﻤﯿ ﻊ اﻟﻌﻤﻠﯿ ﺎت أﺣﺎدﯾ ﺔ اﻟﺮﺗﺒ ﺔ ﺗﻜ ﻮن وﺣ ﺪات اﻟﺜﺎﺑ ﺖ "‪'k‬‬

‫ھﻲ )‪.(time-1‬‬

‫)‪(365‬‬
‫• أﻣﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻼت ﺛﻨﺎﺋﯿﺔ اﻟﺮﺗﺒﺔ‪ ،‬ﺗﺄﺧﺬ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ‬

‫اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫) ‪rate = k ( concentration‬‬
‫‪2‬‬
‫وﻟ ﺬﻟﻚ ﻓ ﺈن ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔ ﺎﻋﻼت ﺛﻨﺎﺋﯿ ﺔ اﻟﺮﺗﺒ ﺔ ﯾﺄﺧ ﺬ اﻟﻮﺣ ﺪات‬
‫)‪ (concentration-1 time-1‬وﯾﻌﺒ ﺮ ﻋﻨﮭ ﺎ رﻣﺰﯾ ﺎ ً ‪(dm3 mol-1 :‬‬
‫)‪ s-1‬أو )‪ (L mol-1 s-1‬وذﻟ ﻚ ﺣﺴ ﺐ وﺣ ﺪات اﻟﺤﺠ ﻢ واﻟ ﺰﻣﻦ‬
‫اﻟﻤﺴﺘﺨﺪﻣﺔ اﻟﺘﻲ ﻗﺪ ﺗﺘﻐﯿﺮ‪.‬‬
‫ﻭﺣﺪﺓ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ ﺑﺸﻜﻞ ﻋﺎﻡ‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ ذي رﺗﺒﺔ )‪ (n‬ﯾﺄﺧﺬ اﻟﻮﺣﺪات ‪:‬‬

‫) ‪( concentration‬‬
‫‪1-n‬‬
‫‪time-1‬‬
‫وﯾﻤﻜﻦ ﺗﻄﺒﯿﻖ ھﺬه اﻟﻘﺎﻋﺪة ﻋﻠﻰ اﻟﺮﺗﺐ ﻛﻤﺎ ﻓﻲ اﻟﺠﺪول )‪ (١-٢‬أدﻧﺎه‪.‬‬

‫ﺟﺪول )‪ : (١-٢‬وﺣﺪات ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ وﻓﻘﺎ ً ﻟﺮﺗﺒﺘﮫ‪.‬‬
‫وﺣﺪة ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‬ ‫) ‪( concentration‬‬ ‫اﻟﻘﺎﻋﺪة‬ ‫اﻟﺮﺗﺒﺔ‬
‫‪1-n‬‬
‫‪time-1‬‬
‫‪mol dm -3 s -1‬‬ ‫) ‪( mol dm‬‬ ‫‪3 1-0‬‬
‫)‪(s‬‬
‫‪-1‬‬
‫‪0‬‬
‫‪s -1‬‬ ‫) ‪( mol dm‬‬ ‫‪3 1-1‬‬
‫)‪(s‬‬
‫‪-1‬‬
‫‪1‬‬
‫‪mol-1 dm3 s -1‬‬ ‫) ‪( mol dm‬‬ ‫‪3 1-2‬‬
‫)‪(s‬‬
‫‪-1‬‬
‫‪2‬‬
‫‪mol-2 dm 6 s -1‬‬ ‫) ‪( mol dm‬‬ ‫‪3 1-3‬‬
‫)‪(s‬‬
‫‪-1‬‬
‫‪3‬‬

‫)‪(366‬‬
‫ﺗﻌﻴﲔ ﺭﺗﺒﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻭﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ‬
‫ﻣﻦ ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻌﺎم ‪:‬‬

‫) ]‪( rate = k A [B‬‬
‫‪n‬‬ ‫‪m‬‬
‫ﻧﺮى أن اﻟﻘﺎﻧﻮن ﻣﻜﻮن ﻣﻦ ‪:‬‬

‫• ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪(rate‬‬
‫• ﺗﺮﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ]‪[A][B‬‬
‫• رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻜﻞ ﻣﺎدة ﻣﺘﻔﺎﻋﻠﺔ )‪(n, m‬‬
‫• ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪.(k‬‬
‫وﻟﻘﺪ ﺧﻠﺼﻨﺎ ﻓﻲ اﻟﺠﺰء اﻟﺴﺎﺑﻖ اﻟ ﻰ أن ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﯾﺴ ﺎوي‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻣﻀﺮوﺑﺎ ً ﺑﺪاﻟﺔ اﻟﻤﺘﻔﺎﻋﻼت وﻣﺮﻓﻮع ﻛﻞ ﻣﻨﮭﺎ اﻟ ﻰ رﺗﺒ ﺔ‬
‫اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪dx‬‬
‫)ﺗﺮﻛـــــــــﯿﺰ اﻟﻤﺘﻔـــــــــﺎﻋﻼت( ‪= k f‬‬
‫‪dt‬‬

‫)‪(367‬‬
‫ﻃﺮﻕ ﺇﳚﺎﺩ ﺛﺎﺑﺖ ﺍﻟﺘﻔﺎﻋﻞ ﻭﺭﺗﺒﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺍﻟﺒﺴﻴﻄﺔ‬
‫ﺣﯿﻨﻤﺎ ﯾﻜﻮن ھﻨﺎك ﺗﻔﺎﻋﻞ ﺑﺴﯿﻂ‪ ،‬ﺗﺘﻔﺎﻋﻞ ﻓﯿﮫ اﻟﻤﺘﻔﺎﻋﻼت ﻟﺘﻌﻄﻲ ﻧ ﻮاﺗﺞ‬
‫ﺑﺨﻄﻮة واﺣﺪة ﺑﺪون ﺗﻜﻮﯾﻦ ﻧ ﻮاﺗﺞ ﺟﺎﻧﺒﯿ ﺔ‪ ،‬ﯾﻤﻜ ﻦ إﯾﺠ ﺎد رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫وﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﺑﺎﻟﻄﺮق اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪ (١‬ﻃﺮﻳﻘﺔ ﺍﻟﺘﻔﺎﺿﻞ )‪(Differential Method‬‬
‫ﻗﻮاﻧﯿﻦ اﻟﺴﺮﻋﺔ اﻟﻤﺴ ﺘﺨﺪﻣﺔ ھ ﻲ ﻋﺒ ﺎرة ﻋ ﻦ ﻣﻌ ﺎدﻻت ﺗﻔﺎﺿ ﻠﯿﺔ‪ .‬وﻟﻘ ﺪ‬
‫اﻗﺘﺮح ھﺬه اﻟﻄﺮﯾﻘﺔ اﻟﻌﺎﻟﻢ ﻓﺎﻧﺖ ھﻮف )‪ (Van't Hoff‬ﻋ ﺎم )‪1884‬‬

‫م(‪ ،‬وذﻟﻚ ﺑﻤﻌﺎﻟﺠﺔ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ ‪:‬‬
‫‪dx‬‬
‫)ﺗﺮﻛـــــــــﯿﺰ اﻟﻤﺘﻔـــــــــﺎﻋﻼت( ‪= k f‬‬
‫‪dt‬‬
‫وﺑﺎﻋﺘﺒ ﺎر )‪ (c‬ﻣﺴ ﺎوﯾﺎ ً ﻟﺘﺮﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ و )‪ (n‬ﻣﺴ ﺎوﯾﺎ ً ﻟﺮﺗﺒ ﺔ‬
‫اﻟﺘﻔﺎﻋﻞ ﻟﺘﺼﺒﺢ ‪:‬‬
‫‪dx‬‬
‫‪= k cn‬‬
‫‪dt‬‬
‫وإذا رﺳﻤﻨﺎ اﻟﻌﻼﻗﺔ ﺑﯿﻦ )اﻟﺘﺮﻛﯿﺰ – اﻟﺰﻣﻦ( ﻓﺈن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﻌ ﯿﻦ‬
‫ﻣﺒﺎﺷﺮة ﻣﻦ ﻣﯿﻞ اﻟﻤﻨﺤﻨﻰ‪ .‬وﯾﻤﻜ ﻦ رﺳ ﻢ ﻣﻤ ﺎس ﻟﻠﻤﻨﺤﻨ ﻰ ﻋﻨ ﺪ ﻣﺨﺘﻠ ﻒ‬

‫)‪(368‬‬
‫اﻟﻨﻘ ﺎط وﻧﺤﺼ ﻞ ﻋﻠ ﻰ اﻟﻘﯿﻤ ﺔ )‪ .(- dc/dt‬وﯾﻌﻄ ﻲ اﻟﻤﯿ ﻞ اﻹﺑﺘ ﺪاﺋﻲ‬

‫ﻟﻤﻨﺤﻨﻰ اﻟﺴﺮﻋﺔ اﻹﺑﺘﺪاﺋﯿﺔ‪.‬‬
‫‪ dx‬‬ ‫‪n ‬‬
‫‪ =kc ‬‬ ‫وﺑﺄﺧ ﺬ اﻟﻠﻮﻏ ﺎرﯾﺘﻢ اﻟﻌﺸ ﺮي )‪ (log‬ﻟﻠﻄ ﺮﻓﯿﻦ ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬
‫‪ dt‬‬ ‫‪‬‬
‫ﺳﯿﻨﺘﺞ ‪:‬‬
‫‪ dx ‬‬
‫) ‪log   = log ( k cn‬‬
‫‪ dt ‬‬
‫‪log rate = log k + n log c‬‬
‫‪log rate = n log c + log k‬‬
‫واﻟﻌﻼﻗ ﺔ اﻟﻨﺎﺗﺠ ﺔ ) ‪ ( log rate = n log c + log k‬ﺗﻤﺜ ﻞ ﻣﻌﺎدﻟ ﺔ ﺧ ﻂ‬

‫ﻣﺴ ﺘﻘﯿﻢ‪ ،‬ﻣﯿﻠ ﮫ )‪) (n‬رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ( واﻟﺠ ﺰء اﻟﻤﻘﻄ ﻮع ﻣ ﻦ ﻣﺤ ﻮر‬
‫)‪.(log k‬‬ ‫اﻟﺼﺎدات ھﻮ‬
‫وﯾﻤﻜﻦ رﺳﻢ ھﺬه اﻟﻌﻼﻗﺔ واﻟﺤﺼﻮل ﻋﻠﻰ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ﺑﺘﻤﺜﯿﻞ ‪(log‬‬
‫)‪ rate‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات و )‪ (log c‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت‪.‬‬
‫ﺇﳚﺎﺩ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ )‪(rate‬‬
‫ﻟﻜﻲ ﻧﻮﺟﺪ )‪ (rate‬ﻟﻠﺘﻔﺎﻋ ﻞ ﯾﻘ ﺎس ﺗﻐﯿ ﺮ اﻟﺘﺮاﻛﯿ ﺰ )اﻟﻨ ﻮاﺗﺞ ﻋ ﺎدة( ﻣ ﻊ‬

‫اﻟﺰﻣﻦ‪ ،‬وﺑﺮﺳﻢ ﻋﻼﻗﺔ اﻟﺘﺮﻛﯿﺰ)‪ (c‬ﻣﻊ اﻟﺰﻣﻦ )‪ (t‬ﻧﺤﺼﻞ ﻋﻠﻰ ﻣﻨﺤﻨﻰ‬
‫ﻣﯿﻞ ﻣﻤﺎﺳﮫ ھﻮ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪.(rate‬‬

‫)‪(369‬‬
‫ﻃﺮﻕ ﺣﺴﺎﺏ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬
‫ﻫﻨﺎﻙ ﻃﺮﻳﻘﺘﺎﻥ ﳊﺴﺎﺏ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫ﺃ( ﻃﺮﻳﻘﺔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺍﻻﺑﺘﺪﺍﺋﻴﺔ‬
‫)‪(Initial Rate Method‬‬

‫ﻛﻤ ﺎ ﻓ ﻲ اﻟﺸ ﻜﻞ )‪ (٢-٢‬ﺣﯿ ﺚ ﺗﻘ ﺎس ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻟﻤﻨﺤﻨﯿ ﺎت ﻋﻨ ﺪ‬
‫ﺗﺮاﻛﯿ ﺰ اﺑﺘﺪاﺋﯿ ﺔ ﻣﺨﺘﻠﻔ ﺔ ﻟﻠﻤﺘﻔ ﺎﻋﻼت وذﻟ ﻚ ﺑﺄﺧ ﺬ اﻟﻤﻤ ﺎس ﻋﻨ ﺪ ﺑﺪاﯾ ﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ )‪ .(t = 0‬وﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ اﻟﺒﯿﺎﻧﯿ ﺔ ﻣ ﻊ ﻟﻮﻏﺎرﯾﺘﻤ ﺎت‬
‫اﻟﺘﺮﻛﯿ ﺰ)‪ (log c‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ )‪(nc‬‬
‫ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(٣-٢‬‬
‫وﺗﻤﺘ ﺎز ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﺑﺘﺤﺎﺷ ﻲ اﻟﺘ ﺪاﺧﻼت اﻟﺘ ﻲ ﺗﺴ ﺒﺒﮭﺎ زﯾ ﺎدة ﺗﺮاﻛﯿ ﺰ‬
‫اﻟﻨﻮاﺗﺞ أﺛﻨ ﺎء اﻟﺘﻔﺎﻋ ﻞ‪ .‬وﯾﻄﻠ ﻖ ﻋﻠ ﻰ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (nc‬اﻟﻨﺎﺗﺠ ﺔ ﻋ ﻦ‬
‫ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ‪ ،‬اﻟﺮﺗﺒ ﺔ اﻟﺤﻘﯿﻘﯿ ﺔ )‪ (true order‬أو اﻟﺮﺗﺒ ﺔ ﺑﺪﻻﻟ ﺔ‬
‫اﻟﺘﺮﻛﯿﺰ‪.‬‬

‫)‪(370‬‬
‫ﺷ ﻜﻞ )‪ : (٢-٢‬رﺳ ﻢ ﻟﻌﻼﻗ ﺔ اﻟﺘﺮﻛﯿ ﺰ )‪ (c‬ﻣ ﻊ اﻟ ﺰﻣﻦ )‪ (t‬ﻋﻨ ﺪ ﺗﺮاﻛﯿ ﺰ اﺑﺘﺪاﺋﯿ ﺔ‬

‫ﻣﺨﺘﻠﻔﺔ وﯾﻘﺎس ﻣﯿﻞ اﻟﻤﻤﺎس ﻋﻨﺪ )‪.(t = 0‬‬
‫ﺷﻜﻞ )‪ : (٣-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪ (log rate‬ﻣﻘﺎﺑﻞ )‪ (log c‬وﻣﯿﻞ ھﺬا اﻟﺨﻂ ﯾﻤﺜﻞ‬
‫رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‬

‫)‪(371‬‬
‫ﺏ( ﻃﺮﻳﻘﺔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺍﻟﻠﺤﻈﻴﺔ‬

‫)‪(Instantaneous Rate Method‬‬
‫ﻓ ﻲ ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﯾﻘ ﺎس ﺗﻐﯿ ﺮ اﻟﺘﺮاﻛﯿ ﺰ ﻣ ﻊ اﻟ ﺰﻣﻦ ﺑﺎﺳ ﺘﺨﺪام ﺗﺮﻛﯿ ﺰ‬
‫اﺑﺘﺪاﺋﻲ ﻣﻌﯿﻦ وﻣ ﻦ اﻟﻤﻨﺤﻨ ﻰ اﻟﻨ ﺎﺗﺞ ﺗﻘ ﺎس ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ أزﻣﻨ ﺔ‬
‫ﻣﺨﺘﻠﻔﺔ وذﻟﻚ ﺑﺤﺴﺎب ﻣﯿﻞ ﻣﻤﺎس اﻟﻤﻨﺤﻨﻰ ﻋﻨ ﺪ اﻟ ﺰﻣﻦ اﻟﻤﻄﻠ ﻮب ﻛﻤ ﺎ‬
‫ﻓﻲ اﻟﺸﻜﻞ )‪ ٤-٢‬أ(‪.(٥-٢) ،‬‬
‫‪ (log‬ﻣ ﻊ‬ ‫وﺑﺮﺳ ﻢ ﻟﻮﻏﺎرﯾﺘﻤ ﺎت اﻟﺴ ﺮﻋﺎت اﻟﻠﺤﻈﯿ ﺔ )‪rate‬‬
‫ﻟﻮﻏﺎرﯾﺘﻤ ﺎت اﻟﺘﺮﻛﯿ ﺰ اﻟﻤﻘﺎﺑﻠ ﺔ )‪ (log c‬ﻟﮭ ﺎ ﻓ ﻲ اﻟﺸ ﻜﻞ )‪ ٤-٢‬ب(‬
‫واﻟﺸﻜﻞ )‪ (٦-٢‬ﯾﻨﺘﺞ ﻋﻦ ذﻟ ﻚ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ واﻟﺘ ﻲ‬
‫رﻣﺰﻧﺎ ﻟﮭﺎ ﺑﺎﻟﺮﻣﺰ )‪ (nt‬وﺗﺴﻤﻰ اﻟﺮﺗﺒﺔ ﺑﺪﻻﻟﺔ اﻟﺰﻣﻦ‪.‬‬
‫ﺷﻜﻞ )‪(٤-٢‬‬

‫)‪(372‬‬
‫ﺷ ﻜﻞ )‪ : (٥-٢‬ﻣﻨﺤﻨ ﻰ ﺗﻐﯿ ﺮ اﻟﺘﺮﻛﯿ ﺰ )‪ (c‬ﻣ ﻊ اﻟ ﺰﻣﻦ )‪ (t‬ﻋﻨ ﺪ ﺗﺮﻛﯿ ﺰ اﺑﺘ ﺪاﺋﻲ‬

‫ﻣﻌﯿﻦ‪ ،‬ﻣﯿﻞ اﻟﻤﻨﺤﻨﻰ ﻋﻨﺪ )‪ (t1, t2, t3‬ﻹﯾﺠﺎد ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ ﺗﺮاﻛﯿ ﺰ ﻣﺨﺘﻠﻔ ﺔ‬
‫)‪.(C1, C2, C3‬‬
‫ﺷ ﻜﻞ )‪ : (٦-٢‬ﻟﻮﻏ ﺎرﯾﺘﻢ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺿ ﺪ ﻟﻮﻏ ﺎرﯾﺘﻢ اﻟﺘﺮاﻛﯿ ﺰ ‪(C1, C2,‬‬

‫)…‪ C3,‬وﻣﯿﻞ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ﯾﻤﺜﻞ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫)‪(373‬‬
‫وﯾﻌﺘﺒﺮ اﻟﺘﻔﺎﻋﻞ ﺑﺴﯿﻄﺎ ً إذا ﺗﺴﺎوت ﻗ ﯿﻢ )‪ (nc‬و)‪ (nt‬وﻟﻜ ﻦ ﻗ ﺪ ﻻ ﺗﻜ ﻮن‬

‫اﻟﻘﯿﻢ ﻣﺘﺴﺎوﯾﺔ داﺋﻤﺎ ً وھﻨﺎك اﺣﺘﻤﺎﻟﯿﻦ ‪:‬‬
‫ﺍﻻﺣﺘﻤﺎﻝ ﺍﻷﻭﻝ ‪(nc ˂ nt) :‬‬
‫وﯾﻜﻮن ھﺬا اﻻﺣﺘﻤﺎل وارداً ﺣﯿﻨﻤﺎ ﺗﺘﻨﺎﻗﺺ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻊ اﻟ ﺰﻣﻦ‬

‫ﺑﺸﻜﻞ أﻛﺒﺮ ﻣﻤﺎ ﻟ ﻮ ﻛﺎﻧ ﺖ اﻟﺮﺗﺒ ﺔ اﻟﺤﻘﯿﻘﯿ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ ﺳ ﺎﺋﺪة وھ ﺬا راﺟ ﻊ‬
‫اﻟﻰ ﺗﻜﻮﯾﻦ ﻣﺮﻛﺐ وﺳﻄﻲ )‪ (intermediate‬ﯾﻌﻤﻞ ﻛﻤﺜﺒﻂ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫)‪.(inhibitor‬‬
‫ﺍﻻﺣﺘﻤﺎﻝ ﺍﻟﺜﺎﻧﻲ )‪(nc > nt‬‬
‫وﯾﻜﻮن ھﺬا اﻻﺣﺘﻤﺎل وارداً ﺣﯿﻨﻤﺎ ﯾﻜ ﻮن ﺗﻨ ﺎﻗﺺ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻊ‬

‫اﻟﺰﻣﻦ أﻗﻞ ﻣﻤﺎ ھﻮ ﻓﻲ اﻟﺤﺎﻟﺔ اﻷوﻟ ﻰ إذا ﻛﺎﻧ ﺖ اﻟﺮﺗﺒ ﺔ اﻟﺤﻘﯿﻘﯿ ﺔ ﺳ ﺎﺋﺪة‬
‫وھﺬا راﺟﻊ اﻟﻰ أن ﺑﻌﺾ اﻟﻨﻮاﺗﺞ ﻗﺪ ﺗﻨﺸﻂ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ ﻋﻤﻠﯿ ﺔ‬
‫ﺗﺴﻤﻰ اﻟﺤﻔﺰ اﻟﺬاﺗﻲ )‪.(auto-catalysis‬‬
‫س( ﻗ ﺎرن ﺑ ﯿﻦ طﺮﯾﻘﺘ ﻲ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻠﺤﻈﯿ ﺔ وﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫اﻻﺑﺘﺪاﺋﻲ‪.‬‬
‫وﺑﻤﺎ أن ﻗﯿﺎس اﻟﺴﺮﻋﺎت اﻹﺑﺘﺪاﺋﯿﺔ ﻟﯿﺴﺖ ﻣﻦ اﻟﺴﮭﻮﻟﺔ ﺑﻤﻜﺎن‪ ،‬ﻓﺈﻧﮫ ﻣﻦ‬
‫اﻷﻓﻀ ﻞ ﺗﻜﺎﻣ ﻞ ﻣﻌﺎدﻟ ﺔ اﻟﺴ ﺮﻋﺔ‪ .‬ﻓﻤﻌﺎدﻟ ﺔ اﻟﺴ ﺮﻋﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﺗﻌﻄ ﻲ‬

‫)‪(374‬‬
‫اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ وﺳ ﺮﻋﺔ اﻟﺘﻐﯿ ﺮ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﻷي ﺗﻔﺎﻋ ﻞ‪،‬‬
‫وﺗﻌﺘﻤﺪ ﺻﻮرة اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ ﻋﻠﻰ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫‪ -٢‬ﻃﺮﻳﻘﺔ ﺍﻟﺘﻜﺎﻣﻞ )‪(Integration Method‬‬
‫ﺗﻘﺘﻀ ﻲ ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﻋﻠ ﻰ اﻟﺘﻌﺒﯿ ﺮ ﻋ ﻦ ﻗ ﻮاﻧﯿﻦ اﻟﺴ ﺮﻋﺔ ﺑﺼ ﯿﻐﺘﮭﺎ‬

‫اﻟﺘﻜﺎﻣﻠﯿﺔ ﻋﻠﻰ أﺳﺎس اﻟﺼﯿﻐﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ‪.‬‬
‫ﻣﻠﺨﺺ ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﺘﻜﺎﻣﻠﻴﺔ‬
‫ﺗﺘﻠﺨﺺ ھﺬه اﻟﻄﺮﯾﻘﺔ ﺑﺎﺧﺘﯿﺎر ﻗﺎﻧﻮن اﻟﺴ ﺮﻋﺔ اﻟ ﺬي ﻧﻌﺘﻘ ﺪ أﻧ ﮫ ﻣﻨﺎﺳ ﺐ‬

‫ﻟﻠﺘﻔﺎﻋﻞ ﺛﻢ ﺗﺤﻮل اﻟﺼﯿﻐﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ اﻟﻰ اﻟﺼ ﯿﻐﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ اﻟﻤﻨﺎﺳ ﺒﺔ‬
‫اﻟﺘﻲ ﺗﻌﻄﻲ ﺧﻄﺎ ً ﻣﺴﺘﻘﯿﻤﺎ ً ﻣﯿﻠﮫ داﺋﻤﺎ ً ﯾﺴﺎوي ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ (k‬ﻟ ﺬا ﻗ ﺪ‬
‫ﻧﺠﺮب ﻋﺪة ﻗﻮاﻧﯿﻦ ﻗﺒﻞ أن ﻧﺤﺼﻞ ﻋﻠﻰ اﻟﻘﺎﻧﻮن اﻟﻤﻨﺎﺳﺐ‪.‬‬
‫وﺳﻮف ﻧﺘﻄﺮق اﻟﻰ إﺟﺮاء اﻟﺘﻜﺎﻣ ﻞ ﻟ ﺒﻌﺾ ﻗ ﻮاﻧﯿﻦ ﺳ ﺮﻋﺔ اﻟﺘﻔ ﺎﻋﻼت‬
‫اﻟﺒﺴ ﯿﻄﺔ واﻟﺘ ﻲ ﺗﻜ ﻮن ﻓﯿﮭ ﺎ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﺴ ﺎوي ﺻ ﻔﺮاً – واﺣ ﺪاً –‬
‫اﺛﻨﯿﻦ – ﺛﻼﺛﺔ ﻣﻊ ﺗﻮﺿﯿﺢ اﻟﻐﺎﯾ ﺔ ﻣ ﻦ ذﻟ ﻚ‪ ،‬وﺳ ﻮف ﻧﻨ ﺎﻗﺶ ذﻟ ﻚ ﻋﻠ ﻰ‬
‫أﺳﺎس ﻣﺎ ﯾﻠﻲ ﻣﺎ ﻟﻢ ﯾﻨﺺ ﻋﻠﻰ ﻏﯿﺮ ذﻟﻚ ‪:‬‬
‫• أن اﻟﺘﻔﺎﻋﻞ ﯾﺤﺪث ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﺔ‪ ،‬وﺑﺜﺒﺎت درﺟﺔ اﻟﺤ ﺮارة‬
‫◌‬ ‫ﯾﻜﻮن ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪ (k‬ﺛﺎﺑﺘﺎ ً‪.‬‬
‫• ﯾﺠﺮى اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ﺣﺠﻢ ﺛﺎﺑﺖ أي ﻓﻲ ﻧﻈﺎم ﺳﺎﻛﻦ‪.‬‬

‫)‪(375‬‬
‫• أن اﻟﺘﻔﺎﻋ ﻞ ﻏﯿ ﺮ ﻋﻜﺴ ﻲ ﺑﻤﻌﻨ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﻻ ﯾﺤ ﺪث ﻓ ﻲ اﻹﺗﺠ ﺎه‬

‫اﻟﻤﻌﺎﻛﺲ‪ ،‬وھﺬا ﯾﺘﺤﻘﻖ ﻓﻘ ﻂ إذا ﻛ ﺎن ﺛﺎﺑ ﺖ اﻟﺘ ﻮازن ﻛﺒﯿ ﺮاً ﺟ ﺪاً‪ ،‬أو‬
‫أن ﯾ ﺪرس اﻟﺘﻔﺎﻋ ﻞ ﺑﺎﻹﻋﺘﻤ ﺎد ﻓﻘ ﻂ ﻋﻠ ﻰ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻹﺑﺘﺪاﺋﯿ ﺔ‬
‫ﻓﻘﻂ‪.‬‬
‫• رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي اﻟﺠﺰﯾﺌﯿﺔ‪.‬‬
‫• ﺟﻤﯿﻊ اﻟﺘﻔﺎﻋﻼت ﻣﺘﺠﺎﻧﺴﺔ‪ ،‬وﺗﺠﺮى ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﺔ‪.‬‬
‫‪ (١‬ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ )‪(Zero Order Reactions‬‬
‫ﺍﳌﻌﺎﺩﻟــﺔ ﺍﻟﺘﻜﺎﻣﻠﻴــﺔ ﻟﻠﺴــﺮﻋﺔ ﻟﻠﺘﻔــﺎﻋﻼﺕ ﺫﺍﺕ ﺍﻟﺮﺗﺒــﺔ ﺻــﻔﺮ‬
‫)‪(Zero Order‬‬
‫ﺗﻌﺮﻳﻒ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ‬
‫ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ ﺻ ﻔﺮ ھ ﻲ اﻟﺘﻔ ﺎﻋﻼت اﻟﺘ ﻲ ﻻ ﺗﺘ ﺄﺛﺮ ﻓﯿﮭ ﺎ ﺳ ﺮﻋﺔ‬

‫اﻟﺘﻔﺎﻋ ﻞ ﺑ ﺎﻟﺘﻐﯿﺮ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ أي ﻣ ﻦ اﻟﻤ ﻮاد اﻟﺪاﺧﻠ ﺔ ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ‬
‫)اﻟﻤﺸﺘﺮﻛﺔ ﻓﻲ اﻟﺘﻔﺎﻋﻞ( ﻷن اﻟﻤﻌ ﺪل )ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ( ﯾﺘﺤ ﺪد ﺑ ﺒﻌﺾ‬
‫اﻟﻌﻮاﻣﻞ اﻷﺧﺮى ﻏﯿﺮ اﻟﺘﺮﻛﯿﺰ ﻣﺜﻞ ‪:‬‬
‫• ﻛﻤﯿ ﺔ اﻟﻀ ﻮء اﻟﻤﻤ ﺘﺺ ﻓ ﻲ ﺣﺎﻟ ﺔ اﻟﺘﻔ ﺎﻋﻼت اﻟﻜﯿﻤﯿ ﺎء اﻟﻀ ﻮﺋﯿﺔ‬
‫)‪.(photochemical reactions‬‬
‫• أو ﻛﻤﯿﺔ اﻟﺤﺎﻓﺰ ﻓﻲ اﻟﺘﻔﺎﻋﻼت اﻟﻤﺤﻔﺰة )‪.(catalytic reactions‬‬

‫)‪(376‬‬
‫• أو ﻣﺴ ﺎﺣﺔ ﺳ ﻄﺢ وﻋ ﺪد اﻟﻨﻘ ﺎط اﻟﻨﺸ ﻄﺔ ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت ﻏﯿ ﺮ‬

‫اﻟﻤﺘﺠﺎﻧﺴﺔ‪.‬‬
‫ﻣﻮﺍﺻﻔﺎﺕ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺫﺍﺕ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ‬
‫ﯾﻔﮭﻢ ﻣﻤﺎ ﺳﺒﻖ ﺑﺄن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻓﻲ ھﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔﺎﻋﻼت ‪:‬‬
‫• ﻋﺒﺎرة ﻋﻦ ﻛﻤﯿﺔ ﺛﺎﺑﺘﺔ ﻻ ﺗﺘﻐﯿﺮ ﻣﻊ اﻟﺰﻣﻦ‪.‬‬
‫• ﻻ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة أو اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ﻣﮭﻤﺎ ﻛﺎن اﻟﺘﺮﻛﯿﺰ‪.‬‬
‫• رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﻻ ﺗﺴﺎوي اﻟﺠﺰﯾﺌﯿﺔ‪.‬‬
‫وھ ﺬا اﻟﻨ ﻮع ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﻏﯿ ﺮ ﺷ ﺎﺋﻊ وﯾﺤ ﺪث ﻋ ﺎدة ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت‬
‫اﻟﻐﯿﺮ ﻣﺘﺠﺎﻧﺴﺔ‪.‬‬
‫ﺃﻣﺜﻠﺔ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺫﺍﺕ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ ﰲ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﻐﲑ ﻣﺘﺠﺎﻧﺴﺔ‬
‫• ﺗﻔﻜ ﻚ اﻷﻣﻮﻧﯿ ﺎ ﻋﻨ ﺪ درﺟ ﺎت ﺣ ﺮارة ﻣﺮﺗﻔﻌ ﺔ ﺑﻮﺟ ﻮد ﻣﻌ ﺪن‬

‫اﻟﻤﻮﻟﺒﺪﻧﯿﻮم )‪ (Mo‬ﻛﻌﺎﻣﻞ ﺣﺎﻓﺰ ‪:‬‬
‫‪2NH 3 ‬‬
‫‪Mo‬‬
‫‪→ N 2 + 3H 2‬‬
‫• ﺗﺤﻠ ﻞ ﯾﻮدﯾ ﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ )‪ (HI‬ﻋﻠ ﻰ ﺳ ﻄﺢ ﻛ ﻞ ﻣ ﻦ اﻟ ﺬھﺐ‬

‫واﻟﻤﻮﻟﯿﺒﺪﻧﯿﻮم ‪:‬‬
‫‪2HI ‬‬
‫‪→ H 2 + I2‬‬

‫)‪(377‬‬
‫وﻋﻨ ﺪ اﻟﻀ ﻐﻮط اﻟﻌﺎﻟﯿ ﺔ ﻟﻠﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻓ ﺈن ﺳ ﻄﺢ اﻟﻌﺎﻣ ﻞ اﻟﺤ ﺎﻓﺰ‬
‫واﻟﺬي ﯾﺤﺪث ﻋﻠﯿﮫ اﻟﺘﻔﺎﻋﻞ ﯾﺘﻐﻄﻰ ﺗﻤﺎﻣﺎ ً ﺑﺎﻟﺠﺰﯾﺌﺎت اﻟﻤﺘﻔﺎﻋﻠﺔ‪ ،‬وﻋﻠ ﻰ‬
‫ھﺬا ﻓﺈن اﻟﺰﯾﺎدة ﻓﻲ ﺿﻐﻂ )ﺗﺮﻛﯿﺰ( اﻟﻐﺎز ﻟﻦ ﯾﻜ ﻮن ﻟ ﮫ أي ﺗ ﺄﺛﯿﺮ ﻋﻠ ﻰ‬
‫ﻛﻤﯿﺔ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﻋﻠﻰ اﻟﺴﻄﺢ‪ ،‬أي أن ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻟ ﻦ‬
‫ﯾﺆﺛﺮ ﻋﻠﻰ اﻟﺴﺮﻋﺔ وﯾﺼﺒﺢ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ ﺻﻔﺮ‪.‬‬
‫ﺃﻣﺜﻠﺔ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺫﺍﺕ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ ﰲ ﺍﻟﺘﻔﺎﻋﻼﺕ ﻣﺘﺠﺎﻧﺴﺔ‬
‫وﻗ ﺪ ﺗﺤ ﺪث ھ ﺬه اﻟﺮﺗﺒ ﺔ ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت اﻟﻤﺘﺠﺎﻧﺴ ﺔ أﯾﻀ ﺎ ً ﻣﺜ ﻞ ﺗﻔﺎﻋ ﻞ‬

‫أﯾﺪﻧﺔ اﻷﺳﯿﺘﻮن ﻓﻲ وﺳﻂ ﺣﻤﻀﻲ ﻋﻨﺪ ﺗﺮﻛﯿﺰ ﻋﺎل ‪:‬‬
‫‪CH3COCH3 + I 2 ‬‬ ‫‪→ CH 3COCH 2 I + HI‬‬
‫‪+‬‬
‫‪H‬‬

‫)‪(378‬‬
‫ﻗﺎﻧﻮﻥ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻟﻠﺮﺗﺒﺔ ﺻﻔﺮ‬
‫إذا ﻛﺎن ﻟﺪﯾﻨﺎ ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ ﺻﻔﺮ ‪:‬‬

‫‪A ‬‬
‫‪→ products‬‬
‫وﻛﺎن ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ اﻹﺑﺘﺪاﺋﻲ ﯾﺴ ﺎوي )‪ ([A]0 =a‬ﻗﺒ ﻞ ﺑ ﺪء‬

‫اﻟﺘﻔﺎﻋ ﻞ‪ ،‬وﺗﺮﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻨﺎﺗﺠ ﺔ ﯾﺴ ﺎوي ﺻ ﻔﺮاً‪ ،‬وﻟ ﻮ اﻓﺘﺮﺿ ﻨﺎ أن‬
‫ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﯾﺴ ﺎوي ﺑﻌ ﺪ زﻣ ﻦ ﻣﻌ ﯿﻦ )‪ ([A] = c‬وﺗﺮﻛﯿ ﺰ‬
‫اﻟﻤﺎدة اﻟﻨﺎﺗﺠﺔ ﯾﺴﺎوي )‪ (x‬وھﻮ ﯾﺴﺎوي اﻟﺘﺮﻛﯿ ﺰ اﻟﻤﺴ ﺘﮭﻠﻚ ﻣ ﻦ اﻟﻤ ﺎدة‬
‫)‪ ،(A‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﻣ ﺎ ﺗﺒﻘ ﻰ ﻣ ﻦ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﯾﻜ ﻮن‬
‫)‪.(c = a – x‬‬
‫وﺑﺎﻹﻋﺘﻤﺎد ﻋﻠﻰ ﻣ ﺎ ﺳ ﺒﻖ ﯾﻜ ﻮن ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺪﻻﻟ ﺔ ﺗﺮﻛﯿ ﺰ‬
‫اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪dc‬‬
‫‪-‬‬ ‫‪= k c0 = k‬‬
‫‪dt‬‬
‫وﺑﺪﻻﻟﺔ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻨﺎﺗﺠﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪dx‬‬
‫‪= k (a - x ) = k‬‬
‫‪0‬‬
‫‪dt‬‬
‫‪ dc‬‬ ‫‪‬‬
‫ﺑ ﯿﻦ )‪ (c = a‬ﻋﻨ ﺪﻣﺎ = ‪(t‬‬ ‫‪0‬‬
‫‪- = k c = k‬‬ ‫وﯾﻤﻜ ﻦ ﻣﻜﺎﻣﻠ ﺔ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ dt‬‬ ‫‪‬‬
‫)‪ 0‬و )‪ (c = c‬ﻋﻨﺪﻣﺎ )‪ (t = t‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫)‪(379‬‬
‫‪dc‬‬
‫‪-‬‬ ‫‪= k c0 = k‬‬
‫‪dt‬‬
‫‪c‬‬ ‫‪t‬‬
‫‪-‬‬ ‫∫‬‫‪a‬‬
‫= ‪dc‬‬ ‫‪∫ k dt‬‬
‫‪0‬‬
‫‪-(c - a) = kt‬‬
‫‪⇒ (a - c) = kt‬‬
‫وﻣﻨﮭﺎ ﻓﺈن ‪:‬‬

‫)‪(a - c‬‬
‫=‪k‬‬
‫‪t‬‬
‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ ] ‪ [ (a - c) = kt‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪(a - c) = kt‬‬
‫‪c = - kt + a‬‬
‫وﺗﺒﯿﻦ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪c = - kt + a‬‬
‫أن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﺒﻘ ﻲ ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ ﺻ ﻔﺮ ﯾﺘﻐﯿ ﺮ ﻣ ﻊ‬
‫اﻟ ﺰﻣﻦ ﺣﺴ ﺐ ﻋﻼﻗ ﺔ ﺧﻄﯿ ﺔ‪ ،‬ﻓﻌﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ )‪ (c‬ﻣﻘﺎﺑ ﻞ )‪(t‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ ﯾﺴﺎوي )‪ (- k‬وﯾﻘﻄ ﻊ ﻣﺤ ﻮر اﻟﺼ ﺎدات‬
‫ﺑﻤﻘﺪار )‪.(a‬‬
‫وﯾﻤﻜﻦ إﯾﺠﺎد ﻋﻼﻗﺔ أﺧﺮى ﺗﻮﺿﺢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻨﺎﺗﺠ ﺔ‬
‫ﻣﻊ اﻟﺰﻣﻦ وذﻟ ﻚ إﻣ ﺎ ﻣﺒﺎﺷ ﺮة ﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ ﻗﯿﻤ ﺔ )‪ (c = a – x‬ﻓ ﻲ‬
‫ﻋﻨ ﺪ‬ ‫‪ dx‬‬ ‫‪‬‬
‫‪ = k (a - x) = k ‬‬
‫‪0‬‬
‫اﻟﻤﻌﺎدﻟﺔ ) ‪ ، ( c = - kt + a‬أو ﺑﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ dt‬‬ ‫‪‬‬

‫)‪(380‬‬
‫)‪ (x = 0‬ﻋﻨﺪ اﻟﺰﻣﻦ )‪ ،( t = 0‬وﺗﺮﻛﯿﺰ اﻟﻤ ﺎدة )‪ (x = x‬ﻋﻨ ﺪ اﻟ ﺰﻣﻦ‬

‫)‪ (t = t‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪rate = constant‬‬
‫‪dx‬‬
‫)‪= k (a - x‬‬
‫‪0‬‬
‫‪dt‬‬
‫ﺑﺎﻋﺘﺒ ﺎر أن )‪ (x‬ﺗﺴ ﺎوي ﺗﺮﻛﯿ ﺰ اﻟﻨ ﻮاﺗﺞ ﻋﻨ ﺪ اﻟﺘﻔﺎﻋ ﻞ‪ ،‬ﻓ ﺈذا ﻛﺎﻣﻠﻨ ﺎ‬
‫‪: (t = 0‬‬ ‫) ‪→ tx‬‬
‫‪‬‬ ‫اﻟﻌﻼﻗﺔ‬
‫‪x‬‬ ‫‪t‬‬
‫‪∫ dx = ∫ kdt‬‬
‫‪0‬‬ ‫‪0‬‬
‫‪x‬‬ ‫‪t‬‬
‫‪∫ dx = k ∫ dt‬‬
‫‪0‬‬ ‫‪0‬‬
‫‪x‬‬ ‫‪‬‬
‫وﻋﻨﺪ )‪ (t = 0‬ﻓ ﺈن )‪ (x = 0‬أﯾﻀ ﺎً‪ ،‬وﻋﻠﯿ ﮫ ﻓ ﺈن اﻟﻌﻼﻗ ﺔ‬
‫‪t‬‬
‫‪ ∫ dx = k ∫ dt ‬‬
‫‪0‬‬ ‫‪0‬‬ ‫‪‬‬
‫ﺗﺼﺒﺢ‬
‫‪x=kt‬‬
‫واﻟﻤﻌﺎدﻟ ﺔ ) ‪ ( x = k t‬ﺗﺒ ﯿﻦ أن )‪ (x‬ﺗﺘﻨﺎﺳ ﺐ طﺮدﯾ ﺎ ً ﻣ ﻊ اﻟ ﺰﻣﻦ )‪،(t‬‬
‫وﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻨﺎﺗﺠ ﺔ )‪ (x‬ﻣ ﻊ اﻟ ﺰﻣﻦ )‪(t‬‬
‫ﯾﻌﻄﻲ ﺧﻄ ﺎ ً ﻣﺴ ﺘﻘﯿﻤﺎ ً ﯾﻤ ﺮ ﺑﻨﻘﻄ ﺔ اﻷﺻ ﻞ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي )‪ ،(k‬ﻛﻤ ﺎ ﻓ ﻲ‬
‫اﻟﺸﻜﻞ )‪.(٧-٢‬‬

‫)‪(381‬‬
‫ﺷﻜﻞ )‪ : (٧-٢‬اﻟﻌﻼﻗﺔ اﻟﺒﯿﺎﻧﯿﺔ ﺑﯿﻦ اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ ﻓﻲ ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ ﺻﻔﺮ‬
‫وﺗﺠﺪر اﻹﺷﺎرة ھﻨﺎ اﻟﻰ أن ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (k‬اﻟﻤﺤﺴ ﻮب‬
‫ﻋ ﻦ طﺮﯾ ﻖ اﻟﻤﻌﺎدﻟ ﺔ ) ‪ ( c = - kt + a‬أو اﻟﻤﻌﺎدﻟ ﺔ ) ‪ ( x = k t‬ﯾﻤﻜ ﻦ أن‬
‫ﺗﻜ ﻮن ﺗﻠ ﻚ اﻟﻘﯿﻤ ﺔ ﺗﺎﺑﻌ ﺔ ﻟﺸ ﺪة اﻟﻀ ﻮء )‪ (intensity of light‬أو‬
‫ﺗﺮﻛﯿﺰ اﻟﺤﺎﻓﺰ‪.‬‬
‫وﻣﻦ اﻟﻤﻌﺎدﻟﺔ ) ‪ ( x = k t‬ﻓﺈن ‪:‬‬
‫‪x‬‬
‫=‪k‬‬
‫‪t‬‬
‫‪‬‬ ‫‪x‬‬
‫أن وﺣﺪات ‪ k‬ﺗﺴﺎوي ‪:‬‬ ‫‪k = ‬‬ ‫وﻧﻼﺣﻆ ﻣﻦ اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪t‬‬
‫)‪ (L-1 mol s-1‬أو )‪.(dm-3 mol s-1‬‬

‫)‪(382‬‬
‫ﻣﻠﺤﻮﻇﺔ ‪:‬‬
‫ﺑﻌﺾ اﻟﻤﺮاﺟﻊ اﻟﻌﻠﻤﯿ ﺔ ﺗﻌﺒ ﺮ ﻋ ﻦ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ‪ [A]o‬واﻟﺘﺮﻛﯿ ﺰ‬

‫ﻋﻨﺪ زﻣﻦ )‪ (t‬ﺑـ ]‪.[A‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ‪:‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪=k‬‬
‫‪dt‬‬
‫وﺑﺈﻋﺎدة ﺗﺮﺗﯿﺐ ھﺬه اﻟﻤﻌﺎدﻟﺔ ﻓﺈن ‪:‬‬

‫‪- d[A]= kdt‬‬
‫وﺑﺘﻜﺎﻣﻠﮭﺎ ﺑﯿﻦ اﻟﻨﮭﺎﯾﺘﯿﻦ ‪ t0‬و ‪: t‬‬

‫‪A‬‬ ‫‪t‬‬
‫‪- ∫ d[A] = k‬‬ ‫∫‬ ‫‪dt‬‬
‫‪A0‬‬ ‫‪t=0‬‬
‫‪- [A]AA0 = [t]tt = 0‬‬

‫‪[A]0 - [A]= kt‬‬
‫‪⇒ [ A ] = [ A ]0 - kt‬‬
‫واﻟﻌﻼﻗ ﺔ ) ‪ ([ A] = [ A]0 - kt‬ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ وﺑﺘﺮﺗﯿﺒﮭ ﺎ ﻟﺘﺼ ﺒﺢ‬

‫ﻋﻠﻰ اﻟﺼﻮرة )‪ (y = ax + b‬ﻓﺈن ‪:‬‬
‫‪[ A ] = [ A ]0 - kt‬‬
‫‪⇒ [ A ] = - kt + [ A ]0‬‬
‫وﻋﻨ ﺪ رﺳ ﻢ ھ ﺬه اﻟﻌﻼﻗ ﺔ ﺑﺘﻤﺜﯿ ﻞ ]‪ [A‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات ﻣﻘﺎﺑ ﻞ‬

‫اﻟ ﺰﻣﻦ )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﺷ ﻜﻞ‬

‫)‪(383‬‬
‫)‪ (٨-٢‬واﻟ ﺬي ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي )‪ ،(- k‬واﻟﺠ ﺰء اﻟﻤﻘﻄ ﻮع ﻣ ﻦ ﻣﺤ ﻮر‬

‫اﻟﺼﺎدات ﯾﻤﺜﻞ اﻟﺘﺮﻛﯿﺰ ) ‪. ([ A ]0‬‬
‫وﻓ ﻲ ھ ﺬه اﻟﺤﺎﻟ ﺔ ﯾﻤﻜ ﻦ أن ﯾ ﺪﺧﻞ ﻓ ﻲ ﻗﯿﻤ ﺔ اﻟﺜﺎﺑ ﺖ ‪ k‬ﺛﻮاﺑ ﺖ أﺧ ﺮى‬
‫ﻣﻘﺎﺑﻠﺔ ﻟﺸﺪة اﻟﻀﻮء أو ﻛﻤﯿﺔ اﻟﺤﺎﻓﺰ‪.‬‬
‫ﺷﻜﻞ )‪ : (٨-٢‬ﺗﻐﯿﺮ ﺗﺮﻛﯿﺰ )‪ (A‬ﺑﺪﻻﻟﺔ اﻟﺰﻣﻦ‬

‫)‪(384‬‬
‫ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ) ‪ ( t‬ﻟﺘﻔﺎﻋﻞ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ ‪:‬‬

‫‪1‬‬
‫‪2‬‬
‫‪Half life period of a zero order reaction‬‬
‫ﺗﻌﺮﻳﻒ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ‬
‫ﯾﻤﻜﻦ ﺗﻌﺮﯾﻒ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ )وھﻮ ﺷﺎﺋﻊ ﻓﻲ اﻟﻜﯿﻤﯿ ﺎء اﻹﺷ ﻌﺎﻋﯿﺔ(‬
‫ﺑﺄﻧﮫ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ )أو ﺗﻔﻜ ﻚ( ﻧﺼ ﻒ ﻛﻤﯿ ﺔ اﻟﻤ ﺎدة اﻟﺪاﺧﻠ ﺔ ﻓ ﻲ‬
‫اﻟﺘﻔﺎﻋﻞ )ﻧﺼﻒ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ( وﯾﺄﺧﺬ اﻟﺮﻣﺰ ) ‪. ( t‬‬

‫‪1‬‬
‫‪2‬‬
‫ﺣﺴﺎﺏ ﻗﻴﻤﺔ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ‬
‫وﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺘﮫ ﺑﺴﮭﻮﻟﺔ إذا ﻣﺎ ﻋﻮﺿﻨﺎ ﻋﻦ ]‪ [A‬وھ ﻮ اﻟﺘﺮﻛﯿ ﺰ (‬

‫)‪ a – x‬ﻋﻨ ﺪ زﻣ ﻦ )‪ (t‬ﺑﺎﻟﻘﯿﻤ ﺔ ‪)  [ A2] ‬واﻟﺘ ﻲ ﯾﻤﻜ ﻦ ﻛﺘﺎﺑﺘﮭ ﺎ ﻋﻠ ﻰ‬
‫‪ο‬‬
‫‪‬‬ ‫‪‬‬
‫اﻟﺼ ﻮرة ‪ (  a2 ‬ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺮﺗﺒ ﺔ ﺻ ﻔﺮ ) ‪، ([A]0 - [A]= kt‬‬

‫‪ ‬‬
‫أي أن ‪:‬‬
‫‪[A]0 - [A]= kt‬‬
‫‪[A]0‬‬
‫‪[A]0 -‬‬ ‫‪= k t1‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪2[A]0 - [A]0‬‬
‫‪= k t1‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪[A]0‬‬
‫‪= k t1‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪[A]0‬‬
‫= ‪⇒ t1‬‬
‫‪2‬‬
‫‪2k‬‬

‫)‪(385‬‬
‫وﯾﻤﻜ ﻦ ﻛﺘﺎﺑ ﺔ ﻧﻔ ﺲ اﻟﻤﻌ ﺎدﻻت ﻋﻨ ﺪ ﻛﺘﺎﺑ ﺔ اﻟﻤﻌﺎدﻟ ﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺮﺗﺒ ﺔ‬

‫ﺻﻔﺮ ﻋﻠﻰ اﻟﺼﻮرة ) ‪ ( x = k t‬ﺣﯿﺚ ) ‪: ( x = [A]0 - [A] = a - c‬‬
‫‪x = kt‬‬
‫‪a - c = kt‬‬
‫‪a‬‬
‫‪a-‬‬ ‫‪= k t1‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪2a-a‬‬
‫‪= k t1‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪a‬‬
‫‪= k t1‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪a‬‬
‫= ‪⇒ t1‬‬
‫‪2‬‬
‫‪2k‬‬
‫ﺍﻟﻌﻼﻗﺔ ﺑﲔ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ﻭﺗﺮﻛﻴﺰ ﺍﳌﺎﺩﺓ ﺍﳌﺘﻔﺎﻋﻠﺔ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ‬
‫ﯾﻤﻜ ﻦ ﺣﺴ ﺎب ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ )ﻋﻤ ﺮ ﻧﺼ ﻒ اﻟﺘﻔﺎﻋ ﻞ( إذا ﻛ ﺎن‬

‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ وﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻌﺮوﻓﯿﻦ‪.‬‬
‫‪‬‬ ‫‪a ‬‬
‫أن ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟﻠﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬ ‫= ‪ t 12‬‬ ‫‪‬‬ ‫وﺗﻮﺿ ﺢ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪2k‬‬
‫اﻟﺮﺗﺒﺔ ﺻﻔﺮ ﯾﺘﻨﺎﺳﺐ طﺮداً ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬
‫ﻣﺜﺎﻝ ﻟﻠﺘﻔﺎﻋﻞ ﺍﻟﺮﺗﺒﺔ ﺻﻔﺮ‬
‫ﻣﻦ أﻣﺜﻠﺔ اﻟﺘﻔﺎﻋﻼت اﻟﺘﻲ ﺗﺘﺒﻊ ھﺬا اﻟﻨﻮع ﻣﻦ اﻟﺮﺗﺐ )اﻟﺮﺗﺒﺔ ﺻﻔﺮ( ‪:‬‬

‫)‪(386‬‬
‫ﺗﻔﺎﻋ ﻞ اﻟﯿ ﻮد )‪ (I2‬ﻣ ﻊ اﻷﺳ ﯿﺘﻮن )‪ (CH3COCH3‬ﺑﻮﺟ ﻮد وﺳ ﻂ‬

‫ﺣﺎﻣﻀ ﻲ ﻋﻠ ﻰ أن ﯾﻜ ﻮن ﺗﺮﻛﯿ ﺰ اﻟﺤ ﺎﻣﺾ أﻋﻠ ﻰ ﺑﻜﺜﯿ ﺮ ﻣ ﻦ ﺗﺮﻛﯿ ﺰ‬
‫اﻟﯿﻮد‪.‬‬
‫• ﺗﻔﻜﻚ ﻣﺮﻛ ﺐ اﻟﻔﻮﺳ ﻔﯿﻦ )‪ (PH3‬ﻋﻠ ﻰ ﺳ ﻄﺢ ﻣﻌ ﺪن اﻟﺘﻨﻐﺴ ﺘﻦ )‪(w‬‬
‫ﻋﻨﺪ اﻟﻀﻐﻮط اﻟﻌﺎﻟﯿﺔ‪.‬‬
‫ﻣﺜﺎﻝ )‪(١-٢‬‬
‫ﻣ ﻦ اﻟﺒﯿﺎﻧ ﺎت اﻟﺘﺎﻟﯿ ﺔ‪ ،‬ﺑ ﯿﻦ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ ﺻ ﻔﺮ‪ ،‬ﺛ ﻢ اﺣﺴ ﺐ‬

‫اﻟﻤﻌﺪل وﺛﺎﺑﺖ ﻣﻌﺪل اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫)‪Time (min.‬‬ ‫‪0.000‬‬ ‫‪10.0‬‬ ‫‪20.0‬‬
‫)‪Concentration (mol dm -3‬‬ ‫‪0.035‬‬ ‫‪0.027‬‬ ‫‪0.019‬‬
‫ﺍﳊﻞ‬
‫ﻓ ﻲ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ ﺻ ﻔﺮ ﯾﺘﻐﯿ ﺮ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﺑﺼ ﻮرة‬

‫ﺧﻄﯿﺔ‪ ،‬أي أن ﻣﻌﺪل اﻟﺘﻔﺎﻋﻞ ﻻ ﯾﺘﻨﺎﻗﺺ ﻣﻊ اﻟﺰﻣﻦ‪.‬‬
‫‪[A]0 - [A] = kt‬‬
‫وﻓﻌﻼً ﻧﻼﺣﻆ ﻣﻦ اﻟﺒﯿﺎﻧﺎت اﻟﺴ ﺎﺑﻘﺔ أن اﻟﻔ ﺮق ﻓ ﻲ اﻟﺘﺮﻛﯿ ﺰ ﺑ ﯿﻦ ﻟﺤﻈ ﺔ‬

‫اﻟ ﺰﻣﻦ )‪ (0.000‬و )‪ (10.0 min.‬ھ ﻮ )‪ (0.008‬ﻣ ﻮﻻر‪ ،‬وﺑ ﯿﻦ‬
‫اﻟ ﺰﻣﻦ )‪ (10.0‬و )‪ (20.0‬دﻗﯿﻘ ﺔ ھ ﻮ ﻛ ﺬﻟﻚ )‪ (0.008‬ﻣ ﻮﻻر أي أن‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ ﺻﻔﺮ‪.‬‬

‫)‪(387‬‬
‫وﯾﻤﻜ ﻦ اﻟﺘﺄﻛ ﺪ ﻣ ﻦ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ ﺻ ﻔﺮ ﺑﺤﺴ ﺎب ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ‬

‫ﻣﻌﺪل اﻟﺘﻔﺎﻋﻞ )‪ (k‬ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪[A]0 - [A]= kt‬‬
‫]‪[A]0 - [A‬‬
‫=‪⇒k‬‬
‫‪t‬‬
‫‪[A]0 = 0.035 mol dm-3‬‬
‫)‪Time (min.‬‬ ‫‪10.0‬‬ ‫‪20.0‬‬
‫)‪[A] (mol dm-3‬‬ ‫‪0.027‬‬ ‫‪0.019‬‬
‫]‪[A]0 - [A‬‬ ‫‪0.035 - 0.027‬‬ ‫‪0.035 - 0.019‬‬
‫=‪k‬‬ ‫=‪k‬‬ ‫‪= 0.0008‬‬ ‫=‪k‬‬ ‫‪= 0.0008‬‬
‫‪t‬‬ ‫‪10‬‬ ‫‪20‬‬
‫وﻧﻼﺣﻆ ﻣﻦ اﻟﺠﺪول أﻧﻨﺎ ﺣﺼﻠﻨﺎ ﻋﻠﻰ ﻗﯿﻤﺔ ﺛﺎﺑﺘﺔ ‪:‬‬

‫ﻟ ـ )‪ (k = 0.0008 mol dm-3 min-1‬ﻋﻨ ﺪ ﻋﻮﺿ ﻨﺎ ﻓ ﻲ ﻗ ﺎﻧﻮن‬
‫‪‬‬ ‫‪[A]0 - [A] ‬‬
‫ﻣﻤﺎ ﯾﺪل ﻋﻠﻰ أن اﻟﺘﻔﺎﻋﻞ ﺻﻘﺮي اﻟﺮﺗﺒﺔ‪.‬‬ ‫= ‪k‬‬ ‫‪‬‬ ‫اﻟﺮﺗﺒﺔ ﺻﻔﺮ‬
‫‪‬‬ ‫‪t‬‬ ‫‪‬‬

‫)‪(388‬‬
‫ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ )‪(First Order Reactions‬‬
‫‪ (٢‬ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﺘﻜﺎﻣﻠﻴﺔ ﻟﻠﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺃﺣﺎﺩﻳﺔ ﺍﻟﺮﺗﺒﺔ‬
‫)‪(First Order‬‬
‫ﯾﻌﺘﺒ ﺮ ھ ﺬا اﻟﻨ ﻮع ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﺷ ﺎﺋﻌﺎ ً ‪ ،‬ﻛﻤ ﺎ ﯾﻌﺘﺒ ﺮ ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻣ ﻦ اﻟﻘ ﻮاﻧﯿﻦ اﻟﺸ ﺎﺋﻌﺔ ﻓ ﻲ اﻟﺤﺮﻛﯿ ﺔ‬
‫اﻟﻜﯿﻤﯿﺎﺋﯿ ﺔ‪ ،‬وﯾﺤ ﺪث ﻏﺎﻟﺒ ﺎ ً ﺣﯿﻨﻤ ﺎ ﯾﻜ ﻮن اﻟﻤ ﺬﯾﺐ اﻟﻤﺴ ﺘﺨﺪم أﺣ ﺪ‬
‫اﻟﻤﺘﻔﺎﻋﻼت‪.‬‬
‫ﺷﻴﻮﻉ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫ﺗﻜﺜ ﺮ ھ ﺬه اﻟﺮﺗﺒ ﺔ ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت اﻟﻐﺎزﯾ ﺔ وﺗﻔ ﺎﻋﻼت ﺗﻔﻜ ﻚ اﻟﻤ ﻮاد‬
‫اﻟﻤﺸﻌﺔ وﯾﻤﻜﻦ ﺣﺪوﺛﮭﺎ ﻓﻲ اﻟﻤﺤﺎﻟﯿﻞ اﻟﺴﺎﺋﻠﺔ‪.‬‬
‫ﺃﻣﺜﻠﺔ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ‪:‬‬
‫• ﺗﻔﻜﻚ ﻏﺎز أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ اﻟﺨﻤﺎﺳﻲ‪:‬‬

‫‪2N 2 O5 ‬‬
‫‪→ 2N 2 O 4 + O2‬‬
‫• اﻟﺘﺤﻠﻞ اﻟﺤﺮاري ﻟﻶزوﻣﯿﺜﺎن ‪:‬‬

‫‪CH 3 N=NCH 3 ‬‬
‫‪→ N 2 + C2 H 6‬‬
‫• اﻟﺘﺤﻠﻞ اﻟﺤﺮاري ﻟﻶزوأﯾﺰوﺑﺮوﺑﺎن ‪:‬‬

‫)‪(389‬‬
‫‪( CH 3 )2 CHN=NCH ( CH 3 )2 ‬‬

‫‪→ N 2 + C 6H14‬‬
‫• اﻟﺘﻜﺴ ﯿﺮ )اﻟ ﺘﺤﻄﻢ( اﻟﺤ ﺮاري ﻟﻜﻠﻮرﯾ ﺪ اﻟﻜﺒﺮوﺗﯿ ﻞ )ﻛﻠﻮرﯾ ﺪ‬

‫اﻟﺴﻠﻔﻮﻧﯿﻞ( ‪:‬‬
‫‪SO 2Cl 2 ‬‬
‫‪→ SO 2 + Cl 2‬‬
‫• اﻟﺘﻜﺴﯿﺮ اﻟﺤﺮاري ﻟﺮﺑﺎﻋﻲ ﻓﻮق أﻛﺴﯿﺪ اﻟﺒﯿﻮﺗﯿﻞ ‪:‬‬

‫‪( CH3 )3 C-O-O-C(CH 3 )3 ‬‬
‫‪→ 2CH 3COCH 3 + C 2 H 6‬‬
‫• ﺗﻔﻜﻚ اﻟﺒﺮوم ‪:‬‬

‫‪Br2 ‬‬
‫‪→ 2Br‬‬
‫‪Ra ‬‬
‫‪→ Rn + α‬‬
‫• ﺗﺤﻠﻞ اﻷﺣﻤﺎض اﻟﻌﻀﻮﯾﺔ ﻋﻠﻰ ﺳﻄﺢ ﻣ ﻦ ﻋﺎﻣ ﻞ ﺣ ﺎﻓﺰ ﻛ ﺎﻟﺒﻼﺗﯿﻦ‪،‬‬

‫ﻣﺜﻞ ﺗﺤﻠﻞ ﺣﻤﺾ اﻟﻔﻮرﻣﯿﻚ )ﺣﻤﺾ اﻟﻨﻤﻞ( ‪:‬‬
‫‪HCOOH ‬‬
‫‪Pt‬‬
‫‪→ CO + H 2 O‬‬
‫• ﺗﻔﻜﻚ ﺑﻌﺾ أﻣﻼح اﻟﺪﯾﺎزوﻧﯿﻮم ﻓﻲ اﻟﻤﺎء ﻣﺜﻞ ﺗﺤﻠﻞ ﻛﻠﻮرﯾﺪ ﺑﻨ ﺰﯾﻦ‬

‫اﻟﺪﯾﺎزوﻧﯿﻮم ‪:‬‬
‫‪C6 H 5 N 2 Cl + H 2 O ‬‬
‫‪→ C6 H5 OH + HCl + N 2‬‬

‫)‪(390‬‬
‫• ﺗﺤﻠﻞ ﺧﻼت اﻟﻤﯿﺜﯿﻞ )اﻹﺳﺘﺮ( ﻓﻲ ﻣﺤﻠﻮل ﻣﺎﺋﻲ واﻟﺬي ﯾﻜﻮن ﺑﻄﯿﺌﺎ ً‬

‫ﺟﺪاً ‪:‬‬
‫‪CH 3COOCH3 + H 2 O ‬‬
‫‪→ CH3 COOH + CH3 OH‬‬
‫وﯾﻤﻜﻦ زﯾﺎدة اﻟﺴ ﺮﻋﺔ ﺑﺎﺳ ﺘﻌﻤﺎل ﻋﺎﻣ ﻞ ﻣﺴ ﺎﻋﺪ وھ ﻮ اﻟﺤ ﺎﻣﺾ ﺣﯿ ﺚ‬
‫ﯾﺒﻘﻰ ﺗﺮﻛﯿﺰه ﺛﺎﺑﺘﺎ ً ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ‪ .‬ووﺟ ﻮد اﻟﻤ ﺎء ﻓ ﻲ ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﯾﻜ ﻮن‬
‫ﻓﻲ ﺣﺎﻟﺔ زﯾﺎدة ﻋﻦ اﻟﻜﻤﯿﺔ اﻟﻼزﻣﺔ وإن ﺗﺮﻛﯿﺰه ﯾﺒﻘﻰ ﺛﺎﺑﺘﺎ ً ﺗﻘﺮﯾﺒ ﺎ ً أﺛﻨ ﺎء‬
‫اﻟﺘﻔﺎﻋﻞ‪ ،‬وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺗﺤﺴﺐ ﻣﻦ ﺗﺮﻛﯿﺰ اﻟﺨ ﻼت ﻓﻘ ﻂ‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﯾﻌﺘﺒ ﺮ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ .‬وھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﯾ ﺪﻋﻰ‬
‫ﺑﺎﻟﺘﻔﺎﻋﻞ اﻟﻜﺎذب )‪ (pseudo reaction‬وﺳﯿﺘﻢ اﻟﺘﻨﻮﯾﮫ ﻋﻨﮫ ﻻ ﺣﻘﺎ ً‪.‬‬
‫• ﺗﺤﻠﻞ ﺳﻜﺮ اﻟﻘﺼﺐ ‪:‬‬
‫‪C12 H 22O11 + H 2O ‬‬
‫‪→ C 6 H12O 6 + C 6H12O 6‬‬
‫• اﻟﺘﻜﺴﯿﺮ اﻟﺤﺮاري ﻟﺜﻼﺛﻲ ﻧﯿﺘﺮوﺣﻤﺾ اﻟﺒﻨﺰوﯾﻚ ‪:‬‬

‫‪C6 H 2 (NO 2 )3COOH ‬‬
‫‪→ 3C6 H3 (NO 2 )3 + CO2‬‬
‫• ﺗﻜﺴﯿﺮ ﻓﻮق أﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ ﻓﻲ وﺟﻮد أﯾﻮن اﻟﯿﻮد ‪:‬‬

‫‪2H 2 O 2 ‬‬
‫‪→ 2H 2 O + O 2‬‬
‫• ﺗﻜﺴﯿﺮ ﺛﻨﺎﺋﻲ أﺳﯿﺘﻮن اﻟﻜﺤﻮل ﻓﻲ وﺟﻮد ﺣﻔﺎز ﻗﺎﻋﺪي ‪:‬‬

‫‪( CH3 )2 C(OH)CH 2 COCH3 ‬‬
‫‪→ 2CH3COCH3‬‬

‫)‪(391‬‬
‫ﻗﺎﻧﻮﻥ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺫﺍﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫ﺗﻜﻮن ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻋﻠﻰ اﻟﺸﻜﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪A ‬‬
‫)ﻧــــــﻮاﺗﺞ( ‪→ products‬‬
‫ﻓﺈذا اﻋﺘﺒﺮﻧﺎ أن اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻟـ )‪ (A‬ھ ﻮ)‪ (a‬أي )‪ ([A] = a‬و‬

‫)‪(x‬ھﻮ ﺗﺮﻛﯿﺰ اﻟﻨﻮاﺗﺞ )‪ ([products] = x‬وھﻲ ﺗﻌﺒ ﺮ ﻋ ﻦ اﻟ ﻨﻘﺺ‬
‫ﻓ ﻲ ﺗﺮﻛﯿ ﺰ )‪ (A‬ﻋﻨ ﺪ زﻣ ﻦ ﻗ ﺪره )‪ (t‬وﯾﻜ ﻮن ﻣﻘ ﺪار ﻣ ﺎ ﯾﺘﺒﻘ ﻰ ﻣ ﻦ‬
‫ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة )‪ (A‬ﯾﺴ ﺎوي )‪ .([A] = c = a – x‬وﻋﻠﯿ ﮫ ﯾﻜ ﻮن‬
‫ﺗﺮﻛﯿﺰ )‪ (A‬ﻋﻨﺪ زﻣﻦ ﻗﺪره )‪ (t‬ھﻮ )‪.(a - x‬‬
‫ﺑﻨﺎ ًء ﻋﻠﻰ ذﻟﻚ ﺗﻜﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺪﻻﻟ ﺔ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‬
‫ﻛﻤﺎ ﯾﻠﻲ‪:‬‬
‫]‪d[A‬‬ ‫‪dc‬‬
‫‪-‬‬ ‫‪=- =kc‬‬
‫‪dt‬‬ ‫‪dt‬‬
‫وﯾﻤﻜﻦ اﻟﺤﺼﻮل ﻋﻠ ﻰ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺪﻻﻟ ﺔ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻨﺎﺗﺠ ﺔ‬
‫ﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ اﻟﻤﻘ ﺪار )‪ ([A] = c = (a – x‬ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
‫]‪ d[A‬‬ ‫‪dc‬‬ ‫‪‬‬
‫‪ ،  -‬وﯾﺼﺒﺢ ﻗﺎﻧﻮن اﻟﺴﺮﻋﺔ ﺑﺼﯿﻐﺘﮫ اﻟﺘﻔﺎﺿﻠﯿﺔ ‪:‬‬ ‫‪= - = k c‬‬
‫‪ dt‬‬ ‫‪dt‬‬ ‫‪‬‬

‫)‪(392‬‬
‫)‪d(a - x‬‬
‫‪-‬‬ ‫)‪= k (a - x‬‬
‫‪dt‬‬
‫)‪d(a - x‬‬
‫‪-‬‬ ‫)‪= k (a - x‬‬
‫‪dt‬‬
‫‪da dx‬‬
‫‪⇒-‬‬ ‫)‪+ = k (a - x‬‬
‫‪dt dt‬‬
‫‪ da‬‬ ‫‪‬‬
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ ذﻟ ﻚ ﻓ ﻲ‬ ‫‪ = 0‬‬ ‫وﺣﯿﺚ أن )‪ (a‬ﻣﻘﺪار ﺛﺎﺑﺖ ﻓﺈن ‪:‬‬
‫‪ dt‬‬ ‫‪‬‬
‫‪ da dx‬‬ ‫‪‬‬

‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪-‬‬ ‫‪+ = k (a - x) ‬‬ ‫اﻟﻤﻌﺎدﻟﺔ‬
‫‪ dt dt‬‬ ‫‪‬‬
‫‪da dx‬‬
‫‪-‬‬ ‫)‪+ = k (a - x‬‬
‫‪dt dt‬‬
‫‪dx‬‬
‫‪0+‬‬ ‫)‪= k (a - x‬‬
‫‪dt‬‬
‫‪dx‬‬
‫⇒‬ ‫)‪= k (a - x‬‬
‫‪dt‬‬
‫]‪ d [A‬‬ ‫‪‬‬
‫أو‬ ‫‪-‬‬ ‫‪= k [A] ‬‬ ‫ﺮﻋﺔ‬ ‫ﻠﯿﺔ ﻟﻠﺴ‬ ‫ﺔ اﻟﺘﻔﺎﺿ‬ ‫ﺐ اﻟﻤﻌﺎدﻟ‬ ‫وﺗﻜﺘ‬
‫‪ dt‬‬ ‫‪‬‬
‫‪  - d(adt- x) = k (a - x) ‬ﻓﻲ اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪‬‬ ‫‪‬‬
‫‪dx‬‬
‫)‪= k (a - x‬‬
‫‪dt‬‬
‫وھﺬه اﻟﻤﻌﺎدﻟ ﺔ ھ ﻲ ﻣﻌﺎدﻟ ﺔ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺑﺪﻻﻟ ﺔ‬
‫اﻟﺘﺮﻛﯿ ﺰ )‪ (a‬ﻟﻠﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ ،‬واﻟﺘﺮﻛﯿ ﺰ)‪ (x‬اﻟﻤﺴ ﺘﮭﻠﻚ ﻣ ﻦ اﻟﻤ ﺎدة‬

‫)‪(393‬‬
‫اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ ،‬وھ ﻮ ﯾﺴ ﺎوي ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻨﺎﺗﺠ ﺔ‪ ،‬وأن )‪ (a – x‬ھ ﻮ‬

‫ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﻋﻨﺪ اﻟﺰﻣﻦ )‪.(t‬‬
‫وﺑﺘﺮﺗﯿﺐ اﻟﻌﻼﻗﺔ ﺑﺪﻟﯿﻞ )‪ (x‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫‪dx‬‬
‫)‪= k (a - x‬‬
‫‪dt‬‬
‫‪dx‬‬
‫‪= kdt‬‬
‫)‪(a - x‬‬
‫‪:‬‬ ‫ﻓﺈذا ﻛﺎﻣﻠﻨﺎ اﻟﻌﻼﻗﺔ ‪  (adx- x) = kdt ‬ﺑﯿﻦ ) ‪( t = 0 → t‬‬
‫‪x‬‬
‫‪xt‬‬ ‫‪x‬‬ ‫‪t‬‬

‫‪dx‬‬
‫‪∫x ( a - x ) = k ∫0 dt‬‬
‫‪ο‬‬
‫ﺗﻨﺘﺞ اﻟﻌﻼﻗﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪-ln(a - x) = kt + I‬‬
‫ﺣﯿﺚ ‪ = I‬ﺛﺎﺑﺖ اﻟﺘﻜﺎﻣﻞ )‪.(constant‬‬
‫وﻋﻨﺪ زﻣﻦ ﻗ ﺪره )‪ (t = 0‬ﺗﻜ ﻮن )‪ (x = 0‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﻗﯿﻤ ﺔ اﻟﺜﺎﺑ ﺖ‬
‫)‪ (I‬ﺗﺼﺒﺢ ‪:‬‬
‫‪-ln(a - x) = kt + I‬‬
‫‪- ln (a - 0) = k (0) + I‬‬
‫‪- ln a = I‬‬
‫‪⇒ I = - ln a‬‬

‫)‪(394‬‬
‫) ‪( -ln(a - x) = kt + I‬‬ ‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ ﻗﯿﻤﺔ )‪ (I‬ﺑـ ) ‪ ( I = - ln a‬ﻓﻲ اﻟﻌﻼﻗ ﺔ‬

‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫)‪- ln (a - x) = kt + (- ln a‬‬
‫‪⇒ - ln (a - x) = kt - ln a‬‬
‫أو‬
‫‪ln (a - x) = - kt + ln a‬‬
‫وﺑﺘﺮﺗﯿﺐ اﻟﻌﻼﻗﺔ ) ‪ ( - ln (a - x) = kt - ln a‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪- ln (a - x) = kt - ln a‬‬
‫‪- ln (a - x) + ln a = kt‬‬
‫‪ln a - ln (a - x) = kt‬‬
‫‪a‬‬
‫‪⇒ ln‬‬ ‫‪= kt‬‬
‫)‪(a - x‬‬
‫وﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ )‪ (ln(a/a-x‬واﻟ ﺰﻣﻦ )‪ (t‬ﺣﺴ ﺐ اﻟﻤﻌﺎدﻟ ﺔ‬

‫‪‬‬ ‫‪a‬‬ ‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﯾﻤﺮ ﻣﻦ ﻧﻘﻄ ﺔ اﻷﺻ ﻞ ﻣﯿﻠ ﮫ‬ ‫‪ ln‬‬ ‫‪= kt ‬‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫ﯾﺴﺎوي )‪ ،(k‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪ ٩-٢‬ب( واﻟﺸﻜﻞ )‪.(١٠-٢‬‬

‫)‪(395‬‬
‫ﺷﻜﻞ )‪: (٩ - ٢‬‬

‫أ( ﺗﻐﯿﺮ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻨﺎﺗﺠﺔ ﻣﻊ اﻟ ﺰﻣﻦ‪) .‬ب( و )ج( ‪ :‬اﻟﻌﻼﻗ ﺎت اﻟﺨﻄﯿ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺑﺪﻻﻟﺔ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻨﺎﺗﺠﺔ‪.‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬

‫ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫ﺷ ﻜﻞ )‪ : (١٠-٢‬اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻠﻤﻌﺎدﻟ ﺔ‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫اﻷوﻟﻰ ﺑﺪﻻﻟﺔ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻨﺎﺗﺠﺔ‪.‬‬

‫)‪(396‬‬
‫وﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ) ‪ ( ln (a - x) = - kt + ln a‬ﺑ ﯿﻦ )‪(ln (a – x‬‬

‫واﻟ ﺰﻣﻦ )‪ (t‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي )‪ (- k‬وﯾﻘﻄ ﻊ‬
‫ﻣﺤ ﻮر اﻟﺼ ﺎدات ﺑﺎﻟﻤﻘ ﺪار )‪ (lna‬ﻛﻤ ﺎ ﻓ ﻲ اﻟﺸ ﻜﻞ )‪ ٩-٢‬ج( واﻟﺸ ﻜﻞ‬
‫)‪.(١١-٢‬‬
‫ﺷ ﻜﻞ )‪ : (١١-٢‬اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻠﻤﻌﺎدﻟ ﺔ ) ‪ ( ln (a - x) = - kt + ln a‬ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬

‫اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺑﺪﻻﻟﺔ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻨﺎﺗﺠﺔ‪.‬‬
‫ﺘﺨﺪﻣﻨﺎ‬ ‫ﺔ إذا اﺳ‬ ‫ﺲ اﻟﻌﻼﻗ‬ ‫ﻰ ﻧﻔ‬ ‫وﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻋﻠ‬
‫) ‪ ( ln (a - x) = - kt + ln a‬ﺣﯿﺚ ‪:‬‬
‫‪ln (a - x) = - kt + ln a‬‬
‫‪ln (a - x) - ln a = - kt‬‬
‫)‪(a - x‬‬
‫‪⇒ ln‬‬ ‫‪= - kt‬‬
‫‪ln a‬‬

‫)‪(397‬‬
‫‪‬‬ ‫‪‬‬
‫ﺑ ﺪﻻً ﻣ ﻦ‬
‫‪a‬‬
‫‪ ln‬‬ ‫‪= kt ‬‬ ‫ﻟﻜﻨﻨﺎ ﻓﻲ اﻟﻐﺎﻟﺐ ﻧﺴﺘﺨﺪم اﻟﺼﻮرة اﻟﺮﯾﺎﺿ ﯿﺔ‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫)‪ (a - x‬‬ ‫‪‬‬

‫وھﻤﺎ ﯾﻤﺜﻼن اﻟﻌﻼﻗﺔ ﻧﻔﺴﮭﺎ‪.‬‬ ‫‪ ln‬‬ ‫‪= - kt ‬‬
‫‪‬‬ ‫‪ln a‬‬ ‫‪‬‬
‫وﻣﻨﮭﺎ ﯾﻤﻜﻦ ﺣﺴﺎب ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪: (k‬‬

‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫)‪(a - x‬‬
‫‪1  a ‬‬
‫=‪⇒k‬‬ ‫‪ln ‬‬ ‫‪‬‬
‫‪t a-x‬‬
‫ﻭﺣﺪﺍﺕ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫‪‬‬ ‫‪1  a ‬‬

‫ﻧﻼﺣ ﻆ أن وﺣ ﺪات ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪(k‬‬ ‫‪ k = t ln  a - x  ‬‬
‫‪‬‬ ‫‪‬‬
‫ﻣﻦ اﻟﻌﻼﻗﺔ‬
‫‪‬‬
‫ﯾﺴ ﺎوي ﻣﻘﻠ ﻮب اﻟ ﺰﻣﻦ )‪ (s-1‬وﯾﻤﻜ ﻦ إﯾﺠ ﺎد ﻗﯿﻤﺘ ﮫ ﺑﯿﺎﻧﯿ ﺎ ً ﻋ ﻦ طﺮﯾ ﻖ‬

‫ﯿﻦ ‪ ( ln (a - x) = - kt + ln a ) :‬أو‬ ‫ﺪ اﻟﻌﻼﻗﺘ‬ ‫ﻞ أﺣ‬ ‫ﺗﻤﺜﯿ‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬
‫‪.  ln‬‬ ‫‪= kt ‬‬
‫‪‬‬ ‫)‪(a - x‬‬ ‫‪‬‬

‫)‪(398‬‬
‫ً‬
‫ﺇﳚﺎﺩ ﺍﻟﺜﺎﺑﺖ )‪ (k‬ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ﺑﻴﺎﻧﻴﺎ‬
‫ً‬
‫ﺃﻭﻻ ‪ :‬ﺇﳚﺎﺩ ﺍﻟﺜﺎﺑﺖ )‪ (k‬ﻋﻦ ﻃﺮﻳﻖ ﺭﺳﻢ ﺍﻟﻌﻼﻗﺔ‬
‫) ‪: ( ln (a - x) = - kt + ln a‬‬
‫ﯾﻤﻜﻦ ﺗﻤﺜﯿﻞ ﻗﯿﻤﺔ )‪ ln(a – x‬ﻣﻊ اﻟﺰﻣﻦ )‪ (t‬ﺣﯿﺚ ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ‬

‫ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي )‪ (- k‬وﺗﻘ ﺎطﻊ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ ﻣ ﻊ ﻣﺤ ﻮر‬
‫اﻟﺼﺎدات ﯾﺴﺎوي )‪ (ln a‬ﺣﺴﺐ اﻟﺸﻜﻞ )‪.(١٢-٢‬‬
‫ﺷﻜﻞ )‪ : (١٢-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪ ln(a – x‬ﻣﻊ اﻟﺰﻣﻦ )‪ (t‬ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(399‬‬
‫ً‬
‫‪‬‬
‫‪ ln‬‬
‫‪a‬‬ ‫‪‬‬
‫‪= kt ‬‬ ‫ﺛﺎﻧﻴﺎ ‪ :‬ﺇﳚﺎﺩ ﺍﻟﺜﺎﺑﺖ )‪(k‬ﻋﻦ ﻃﺮﻳﻖ ﺭﺳﻢ ﺍﻟﻌﻼﻗﺔ‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫‪‬‬ ‫‪a ‬‬
‫ﻣ ﻊ اﻟ ﺰﻣﻦ )‪ (t‬ﺣﯿ ﺚ ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ‬ ‫‪ ln‬‬ ‫‪‬‬ ‫ﻓﯿﻤﻜﻦ رﺳ ﻢ ﺗﻐﯿ ﺮ‬
‫‪ (a - x) ‬‬
‫ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ )‪ (k‬وﯾﻤﺮ ﺑﻨﻘﻄﺔ اﻷﺻﻞ‪ ،‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(١٣-٢‬‬
‫‪‬‬ ‫‪a ‬‬

‫ﻣﻊ اﻟﺰﻣﻦ ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬ ‫‪ ln‬‬ ‫‪‬‬ ‫ﺷﻜﻞ )‪ : (١٣-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ‬
‫‪ a-x‬‬
‫ﺃﻫﻤﻴﺔ ﺍﻟﺮﺳﻢ ﺍﻟﺒﻴﺎﻧﻲ ﰲ ﺇﺛﺒﺎﺕ ﺃﻥ ﺍﻟﺘﻔﺎﻋﻞ ﻣﻦ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫إن اﻟﺮﺳ ﻢ اﻟﺒﯿ ﺎﻧﻲ اﻟﺴ ﺎﺑﻖ ﻟﻠﻌﻼﻗ ﺔ ) ‪ ( ln (a - x) = - kt + ln a‬أو ﻟﻠﻌﻼﻗ ﺔ‬

‫‪‬‬ ‫‪‬‬
‫‪ ،‬واﺳ ﺘﻘﺎﻣﺔ اﻟﺨ ﻂ اﻟﻨ ﺎﺗﺞ ﻓﯿﮭ ﺎ ھ ﻲ اﻟﻔﯿﺼ ﻞ ﻹﺛﺒ ﺎت أن‬ ‫‪ ln‬‬
‫‪a‬‬
‫‪= kt ‬‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(400‬‬
‫ﺍﻟﻄﺮﻳﻘﺔ ﺍﳊﺴﺎﺑﻴﺔ ﻹﺛﺒﺎﺕ ﺃﻥ ﺍﻟﺘﻔﺎﻋﻞ ﻣﻦ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫ھﻨﺎك طﺮﯾﻘﺔ ﺣﺴﺎﺑﯿﺔ ﻹﺛﺒﺎت أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟ ﻰ وذﻟ ﻚ ﻋ ﻦ‬

‫طﺮﯾﻖ ﺣﺴﺎب )‪ (k‬ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫)‪t (a - x‬‬
‫وﺑﺎﺳ ﺘﺨﺪام اﻟﻠﻮﻏ ﺎرﯾﺘﻢ اﻟﻌﺸ ﺮي )اﻟﻠﻮﻏ ﺎرﯾﺘﻢ ﻟﻸﺳ ﺎس ‪(10‬‬

‫)اﻟﻠﻮﻏﺎرﯾﺘﻢ اﻟﻄﺒﯿﻌﻲ( ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫‪2.303‬‬ ‫‪ a ‬‬
‫=‪k‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪t‬‬ ‫‪a-x‬‬
‫وﺑﺤﺴﺎب ﻗﯿﻤﺔ اﻟﺜﺎﺑﺖ )‪ (k‬ﻟﻌﺪة ﻗﯿﻢ ﻣﻦ اﻟ ﺰﻣﻦ )‪ ، (t‬ﻓ ﺈذا ﻛ ﺎن اﻟﻨ ﺎﺗﺞ‬
‫داﺋﻤ ﺎ ً ﻣﺘﺴ ﺎو )ﻣ ﻊ اﻷﺧ ﺬ ﺑﺎﻻﻋﺘﺒ ﺎر ﻧﺴ ﺒﺔ اﻟﺨﻄ ﺄ ﻓ ﻲ اﻟﺘﺠﺮﺑ ﺔ( ﻓﮭ ﺬا‬
‫ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬أﻣﺎ إذا ﺣﺼﻞ اﻟﻌﻜﺲ ﻓﮭﺬا ﯾﻌﻨ ﻲ‬
‫أن ﻧﺠﺮب اﻟﺤﺴﺎب ﻋﻦ طﺮﯾﻖ رﺗﺒﺔ أﺧﺮى‪.‬‬

‫)‪(401‬‬
‫ﻣﺰﻳﺪ ﻣﻦ ﺍﻟﻘﺮﺍءﺓ ﻟﻘﻮﺍﻧﲔ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫‪ (١‬ﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ ﻗ ﺎﻧﻮن اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺑﻤﻜﺎﻣﻠ ﺔ اﻟﻤﻌﺎدﻟ ﺔ‬

‫‪ dc‬‬ ‫‪‬‬
‫‪:‬‬ ‫‪- = k c‬‬
‫‪ dt‬‬ ‫‪‬‬
‫‪dc‬‬
‫‪-‬‬ ‫‪=kc‬‬
‫‪dt‬‬
‫‪dc‬‬
‫‪- = kdt‬‬
‫‪c‬‬
‫‪ dc‬‬ ‫‪‬‬
‫ﺑﯿﻦ )‪ (c = a‬ﻋﻨﺪ )‪ (t = 0‬و )‪(c = c‬‬ ‫‪ - = kdt ‬‬ ‫وﺑﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ c‬‬ ‫‪‬‬
‫ﻋﻨﺪ )‪ (t = t‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪dc‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫‪c‬‬
‫‪c dc‬‬
‫∫‪-‬‬ ‫‪= ∫ kdt‬‬
‫‪t‬‬
‫‪a c‬‬ ‫‪0‬‬
‫‪c dc‬‬
‫∫‪-‬‬ ‫‪= k ∫ dt‬‬
‫‪t‬‬
‫‪a c‬‬ ‫‪0‬‬
‫وﺣﯿﺚ إن ﺗﻜﺎﻣﻞ )‪ (dc/c = lnc‬ﻓﺈن ‪:‬‬

‫‪c‬‬ ‫‪dc‬‬ ‫‪t‬‬
‫‪-‬‬ ‫∫‬
‫‪a‬‬ ‫‪c‬‬
‫‪= k ∫ dt‬‬
‫‪0‬‬
‫‪c‬‬
‫‪ln = - kt‬‬
‫‪a‬‬
‫وﺑﺘﻄﺒﯿﻖ ﻗﻮاﻋﺪ اﻟﻠﻮﻏﺎرﯾﺘﻤﺎت ﻋﻠﻰ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫)‪(402‬‬
‫‪c‬‬
‫‪ln = - kt‬‬
‫‪a‬‬
‫‪ln c - lna = - kt‬‬
‫‪ln c = ln a - kt‬‬
‫‪⇒ c = a e - kt‬‬
‫‪ c‬‬ ‫‪‬‬
‫ﯾﻤﻜﻦ ﻛﺘﺎﺑﺘﮭﺎ ﺑﺄﺣﺪ اﻟﺼﻮرﺗﯿﻦ اﻟﺘﺎﻟﯿﺘﯿﻦ ‪:‬‬ ‫‪ ln = - kt ‬‬ ‫واﻟﻤﻌﺎدﻟﺔ‬
‫‪ a‬‬ ‫‪‬‬
‫‪c‬‬
‫‪ln = - kt‬‬
‫‪a‬‬
‫‪a‬‬
‫‪ln = k t‬‬
‫‪c‬‬
‫‪ a‬‬ ‫‪‬‬
‫ﯾﻤﻜﻦ أن ﺗﻜﺘﺐ ﻋﻠﻰ ﺻﻮرة ﻣﻌﺎدﻟﺔ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ‬ ‫‪ ln = k t ‬‬ ‫واﻟﻤﻌﺎدﻟﺔ‬
‫‪ c‬‬ ‫‪‬‬
‫‪:‬‬
‫‪a‬‬
‫‪ln = k t‬‬
‫‪c‬‬
‫‪ln a - ln c = kt‬‬
‫‪⇒ ln c = - kt + ln a‬‬
‫‪ a‬‬ ‫‪‬‬
‫ﺑ ﯿﻦ )‪ln(a/c‬‬ ‫‪ ln = k t ‬‬ ‫وﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺣﺴ ﺐ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ c‬‬ ‫‪‬‬
‫واﻟﺰﻣﻦ )‪ (t‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ ﻣ ﻦ ﻧﻘﻄ ﺔ اﻷﺻ ﻞ وﻣﯿﻠ ﮫ‬

‫ﯾﺴﺎوي )‪ (k‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪ ١٤-٢‬ب(‪.‬‬

‫)‪(403‬‬
‫أﻣ ﺎ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺣﺴ ﺐ اﻟﻤﻌﺎدﻟ ﺔ ) ‪ ( ln c = - kt + ln a‬ﺑ ﯿﻦ )‪(ln c‬‬

‫واﻟﺰﻣﻦ )‪ (t‬ﻓﺈﻧﻨﺎ ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ ﯾﺴﺎوي )‪ (- k‬وﯾﻘﻄ ﻊ‬
‫ﻣﺤﻮر اﻟﺼﺎدات ﺑﻤﻘﺪار )‪ (ln a‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪ ١٤ -٢‬ج(‪.‬‬
‫ﺷﻜﻞ )‪: (١٤-٢‬‬

‫أ( ﺗﻐﯿﺮ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﻣﻊ اﻟﺰﻣﻦ‪.‬‬
‫‪ a‬‬ ‫‪‬‬
‫ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺑﺪﻻﻟ ﺔ ﺗﺮﻛﯿ ﺰ‬ ‫‪ ln = k t ‬‬ ‫ب( اﻟﻌﻼﻗﺔ اﻟﺨﻄﯿﺔ ﻟﻠﻤﻌﺎدﻟﺔ‬
‫‪ c‬‬ ‫‪‬‬
‫اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬
‫ج( اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻠﻤﻌﺎدﻟ ﺔ ) ‪ ( ln c = - kt + ln a‬ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺑﺪﻻﻟ ﺔ‬
‫ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ‬
‫‪ a‬‬ ‫‪‬‬

‫أو‬ ‫‪ ln = k t ‬‬ ‫وﺗﺠﺪر اﻹﺷ ﺎرة ھﻨ ﺎ اﻟ ﻰ أن أي ﺗﻔﺎﻋ ﻞ ﯾﺤﻘ ﻖ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ c‬‬ ‫‪‬‬
‫اﻟﻤﻌﺎدﻟﺔ ) ‪ ( ln c = - kt + ln a‬ﯾﻌﺘﺒﺮ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(404‬‬
‫‪ (٢‬ﳝﻜﻦ ﺇﺟﺮﺍء ﺍﻟﺘﻜﺎﻣﻞ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻟﱰﺍﻛﻴﺰ ]‪ [A]0, [A‬ﻛﻤﺎ ﻳﻠﻲ ‪:‬‬
‫إذا ﻓﺮﺿﻨﺎ اﻟﺘﻔﺎﻋﻞ اﻟﺮﻣﺰي اﻟﺘﺎﻟﻲ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬

‫‪A ‬‬
‫‪→B‬‬
‫ﻓﺈن ﻣﻌﺪل ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫]‪d[A‬‬
‫‪-‬‬ ‫]‪= k [A‬‬
‫‪dt‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫]‪[A‬‬
‫]‪ d[A‬‬ ‫‪‬‬

‫ﺑﯿﻦ )‪ (t1‬و )‪: (t2‬‬ ‫‪-‬‬ ‫‪= kdt ‬‬ ‫وﺑﺘﻜﺎﻣﻞ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ‬
‫]‪ [A‬‬ ‫‪‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫]‪[A‬‬
‫‪A2‬‬ ‫‪2‬‬ ‫‪t‬‬
‫]‪d[A‬‬
‫∫‪-‬‬ ‫‪= k ∫ dt‬‬
‫‪A1‬‬
‫]‪[A‬‬ ‫‪t1‬‬
‫‪- ( ln [ A ])A = k ( t ) t 2‬‬

‫‪A2‬‬ ‫‪t‬‬
‫‪1‬‬ ‫‪1‬‬
‫) ‪- ( ln [ A ]2 - ln [ A ]1 ) = k ( t 2 - t1‬‬
‫) ‪ln [ A ]1 - ln [ A ]2 = k ( t 2 - t1‬‬
‫‪[ A ]1‬‬
‫‪ln‬‬ ‫) ‪= k ( t 2 - t1‬‬
‫‪[ A ]2‬‬
‫وﺣﯿ ﺚ أن )‪ (t1 = 0‬ﻓ ﻲ ﺑﺪاﯾ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﺈن )‪ ([A]0 = [A]1‬وﺑ ﺬﻟﻚ‬
‫‪ [ A ]1‬‬ ‫‪‬‬
‫ﻛﺎﻵﺗﻲ ‪:‬‬ ‫‪ ln‬‬ ‫‪= k ( t 2 - t1 ) ‬‬ ‫ﺗﺼﺒﺢ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ [ A ]2‬‬
‫‪‬‬
‫‪‬‬

(405)
[ A ]1
ln = k ( t 2 - t1 )
[ A ]2
[ A ]0
ln = k ( t - 0)
[A]
[ A ]0
⇒ ln = kt
[A]
 [ A ]0 
: ‫ﻓﻲ اﻟﺼﻮرة اﻵﺗﯿﺔ‬  ln = kt  ‫ﻛﻤﺎ ﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ‬
 [A]


[ A ]0
ln = kt
[A]
ln [ A ]0 - ln [ A ] = kt
⇒ ln [ A ] = - kt + ln [ A ]0
: ‫واﻟﺘﻲ ﯾﻤﻜﻦ ﻛﺘﺎﺑﺘﮭﺎ ﻋﻠﻰ اﻟﺼﻮرة‬

[ A ] = [ A ]0 e- kt
: ‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺘﮭﺎ ﺑﺎﺳﺘﺨﺪام اﻟﻠﻮﻏﺎرﯾﺘﻢ اﻟﻌﺸﺮي‬
[ A ]0
ln = kt
[A]
[ A ]0
2.303 log = kt
[A]
2.303 [ A ]0 kt
log =
2.303 [ A ] 2.303
[ A ]0 kt
log =
[ A ] 2.303
kt
log [ A ]0 − log [ A ] =
2.303

‫)‪(406‬‬
‫‪- kt‬‬
‫= ] ‪⇒ log [ A‬‬ ‫‪+ log [ A ]0‬‬
‫‪2.303‬‬
‫‪‬‬ ‫‪- kt‬‬ ‫‪‬‬

‫ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ‪ ،‬ﻓ ﺈذا‬ ‫= ] ‪ log [ A‬‬ ‫‪+ log [ A ]0 ‬‬ ‫واﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪‬‬
‫رﺳ ﻢ ﻟﻮﻏ ﺎرﯾﺘﻢ اﻟﺘﺮﻛﯿ ﺰ )] ‪ ( log [ A‬ﻣﻘﺎﺑ ﻞ اﻟ ﺰﻣﻦ )‪ (t‬ﻓﺈﻧ ﮫ ﯾﻨ ﺘﺞ ﻋﻨﮭ ﺎ‬

‫ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ )‪ ( - k/2.303‬وﺗﻘﺎطﻌ ﮫ ﻣ ﻊ ﻣﺤ ﻮر اﻟﺼ ﺎدات‬
‫واﻟﺸﻜﻞ )‪ (١٥-٢‬ﯾﻮﺿﺢ ذﻟﻚ‪.‬‬ ‫) ] ‪( log [ A‬‬
‫‪0‬‬ ‫ﯾﺴﺎوي‬
‫ﺷﻜﻞ )‪ : (١٥-٢‬ﺗﻐﯿﺮ ﻟﻮﻏﺎرﯾﺘﻢ اﻟﺘﺮﻛﯿﺰ ﺑﺪﻻﻟﺔ اﻟﺰﻣﻦ‬

‫)‪(407‬‬
‫وﻣﻦ أﻣﺜﻠﺔ ھﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔ ﺎﻋﻼت ﺗﺤﻠ ﻞ ﺧ ﺎﻣﺲ أﻛﺴ ﯿﺪ اﻟﻨﯿﺘ ﺮوﺟﯿﻦ‬
‫اﻟ ﻰ أﻛﺴ ﺠﯿﻦ وراﺑ ﻊ أﻛﺴ ﯿﺪ اﻟﻨﯿﺘ ﺮوﺟﯿﻦ اﻟ ﺬي ﯾﺘﺤﻠ ﻞ ﺑ ﺪوره ﻟﯿﻌﻄ ﻲ‬
‫ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ‪:‬‬
‫‪N 2 O5 ‬‬
‫‪→ N 2O4 + O2‬‬
‫‪‬‬
‫↓‬
‫‪2NO 2‬‬
‫ھﺬا ﻋﻨﺪﻣﺎ ﯾﻜﻮن اﻟﻀﻐﻂ ﻣﺮﺗﻔﻌﺎ ً أﻣﺎ ﻓﻲ ﺣﺎﻟﺔ اﻟﻀ ﻐﻂ اﻟﻤ ﻨﺨﻔﺾ ﻓ ﺈن‬
‫ھﺬا اﻟﺘﻔﺎﻋﻞ ﻻ ﯾﺘﺒﻊ ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(408‬‬
‫ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ﰲ ﺍﻟﻄﻮﺭ ﺍﻟﻐﺎﺯﻱ‬
‫اﻟﺘﻔ ﺎﻋﻼت ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي ﯾﻤﻜ ﻦ اﺳ ﺘﺒﺪال اﻟﺘﺮاﻛﯿ ﺰ ﻓﯿﮭ ﺎ ﺑﻀ ﻐﻂ‬
‫اﻟﻤﺎدة اﻟﻐﺎزﯾﺔ اﻟﻤﺘﻔﺎﻋﻠﺔ‪ ،‬ﻓﺈذا ﻛﺎن ﻟﺪﯾﻨﺎ ﺗﻔﺎﻋﻞ ﻣﺎ ﻣﺜﻞ ‪:‬‬
‫‪A(g) ‬‬
‫ﻓﺈﻧﮫ ﺑﺎﺳﺘﺨﺪام ﻣﻌﺎدﻟﺔ اﻟﻐﺎز اﻟﻤﺜﺎﻟﻲ ‪:‬‬

‫‪PA V = n A RT‬‬
‫‪n A PA‬‬
‫= ]‪[A‬‬ ‫=‬
‫‪V RT‬‬
‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ ]‪ [A‬ﺑﺎﻟﻤﻘ ﺪار )‪ (PA/RT‬ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬

‫‪‬‬ ‫‪[ A ]0‬‬ ‫‪‬‬
‫‪  ln [ A] = kt ‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫‪‬‬ ‫‪‬‬
‫‪[ A ]0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫]‪[A‬‬
‫‪( PA )0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪( PA )t‬‬

‫)‪(409‬‬
‫ﻣﻠﺤﻮﻇﺔ‬
‫ﻋﻨ ﺪﻣﺎ ﻧﺮﻣ ﺰ ﻟﺘﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ )‪ (CA‬ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ ‪:‬‬
‫) ‪( A → products‬‬
‫‪ dCA‬‬ ‫‪‬‬
‫ﻟﻘﯿﻤﺘ ﻲ ﺗﺮﻛﯿ ﺰ )‪ (x1‬و‬ ‫‪-‬‬ ‫‪= k CA ‬‬ ‫ﯾﻤﻜﻦ إﺟﺮاء اﻟﺘﻜﺎﻣﻞ ﻟﻠﻤﻌﺎدﻟ ﺔ‬
‫‪ dt‬‬ ‫‪‬‬
‫)‪ (x2‬وﻟﺰﻣﻨﻲ )‪ (t1‬و )‪ (t2‬ﻋﻠﻰ اﻟﺘﻮاﻟﻲ ﻟﺘﺘﺤ ﻮل اﻟﻤﻌﺎدﻟ ﺔ اﻟ ﻰ اﻟﺸ ﻜﻞ‬

‫اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪dC A‬‬
‫‪−‬‬ ‫‪= kC A‬‬
‫‪dt‬‬
‫‪dC‬‬
‫‪− A = kdt‬‬
‫‪CA‬‬
‫‪ dCA ‬‬
‫= ‪k ∫ dt‬‬ ‫∫‬
‫‪t2‬‬ ‫‪CA2‬‬
‫‪−‬‬ ‫‪‬‬
‫‪t1‬‬ ‫‪CA1‬‬
‫‪ CA ‬‬
‫‪C‬‬
‫‪k(t 2 - t1 )= - ln A2‬‬
‫‪CA1‬‬
‫‪C A1‬‬
‫‪k(t 2 - t1 ) = ln‬‬
‫‪C A2‬‬
‫‪CA1‬‬
‫‪k(t 2 - t1 ) = 2.303 log‬‬
‫‪CA2‬‬
‫‪2.303‬‬ ‫‪C‬‬
‫=‪⇒k‬‬ ‫‪log A1‬‬
‫) ‪(t 2 - t1‬‬ ‫‪C A2‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪C ‬‬

‫ﻋﻠﻰ اﻟﺼﻮرة ‪:‬‬ ‫= ‪k‬‬ ‫‪log A1 ‬‬ ‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ‬
‫‪‬‬ ‫) ‪(t 2 - t1‬‬ ‫‪CA2 ‬‬
‫‪2.303‬‬ ‫) ‪(a - x1‬‬

‫=‪k‬‬ ‫‪log‬‬
‫) ‪(t 2 - t1‬‬ ‫) ‪( a - x2‬‬

‫)‪(410‬‬
‫ﻃﺮﻕ ﺗﻌﻴﲔ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ )‪ (k‬ﰲ ﺍﻟﺘﻔﺎﻋﻼﺕ ﺃﺣﺎﺩﻳﺔ ﺍﻟﺮﺗﺒﺔ‬
‫‪ (١‬ﻃﺮﻳﻘﺔ ﺍﻟﺘﻌﻮﻳﺾ‬
‫ﯾﺘﻢ ﺗﻌﯿﯿﻦ ﻗﯿﻢ )‪ (a – x‬ﺗﺠﺮﯾﺒﯿﺎ ً ﺑﺈﺣﺪى اﻟﻄﺮق اﻟﻤﺴ ﺘﺨﺪﻣﺔ وذﻟ ﻚ ﻋﻨ ﺪ‬

‫ﻣﺨﺘﻠﻒ اﻷزﻣﻨﺔ "‪ "t‬ﻣﻦ ﺧﻼل ﺗﺠﺎرب ﻋﻠ ﻰ اﻟﻜﯿﻨﺎﺗﯿﻜﯿ ﺔ‪ .‬وھ ﺬه اﻟﻘ ﯿﻢ‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪ a ‬‬
‫وﻣﻨﮭ ﺎ ﯾﻤﻜ ﻦ ﺗﻌﯿ ﯿﻦ‬ ‫‪ k = t log  a - x  ‬‬ ‫ﯾﻌ ﻮض ﺑﮭ ﺎ ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫اﻟﻘﯿﻤﺔ اﻟﻤﺘﻮﺳﻄﺔ ﻟﺜﺎﺑﺖ اﻟﺴﺮﻋﺔ‪.‬‬
‫‪ (٢‬ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﺒﻴﺎﻧﻴﺔ‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪ a ‬‬

‫واﻟﺘ ﻲ ﯾﻤﻜ ﻦ ﺗﺮﺗﯿﺒﮭ ﺎ ﻋﻠ ﻰ‬ ‫‪ k = t log  a - x  ‬‬ ‫ﻣ ﻦ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫اﻟﺼﻮرة ‪:‬‬
‫‪ a ‬‬ ‫‪k‬‬
‫‪log ‬‬ ‫=‪‬‬ ‫‪t‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪-‬‬ ‫‪x‬‬ ‫‪‬‬ ‫‪2.303‬‬
‫‪ a ‬‬
‫ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات واﻟﺰﻣﻦ "‪ "t‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬ ‫‪log ‬‬ ‫‪‬‬ ‫وﺑﺘﻤﺜﯿﻞ‬
‫‪a-x‬‬
‫‪ k ‬‬
‫إذا ﻛ ﺎن‬ ‫‪‬‬ ‫‪‬‬ ‫اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي‬
‫‪ 2.303 ‬‬
‫اﻟﺘﻔﺎﻋﻞ اﻟﻤﺪروس أﺣﺎدي اﻟﺮﺗﺒﺔ‪.‬‬

‫‪‬‬ ‫‪ a ‬‬ ‫‪k‬‬ ‫‪‬‬
‫ﻋﻠﻰ اﻟﺼﻮرة ‪:‬‬ ‫‪ log  a - x  = 2.303 t ‬‬ ‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬

‫)‪(411‬‬
‫‪ a ‬‬ ‫‪k‬‬

‫‪log ‬‬ ‫=‪‬‬ ‫‪t‬‬
‫‪ a - x  2.303‬‬
‫‪k‬‬
‫= )‪log a - log (a - x‬‬ ‫‪t‬‬
‫‪2.303‬‬
‫‪k‬‬
‫= )‪- log (a - x‬‬ ‫‪t - log a‬‬
‫‪2.303‬‬
‫‪k‬‬
‫‪⇒ log (a - x) = -‬‬ ‫‪t + log a‬‬
‫‪2.303‬‬
‫وھﺬه اﻟﻤﻌﺎدﻟﺔ ﺗﻤﺜﻞ ﻣﻌﺎدﻟﺔ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ‪ .‬وﯾﺘﻀﺢ ﻣﻦ ھﺬه اﻟﻤﻌﺎدﻟﺔ أﻧﮫ‬

‫ﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ ) )‪ ( log (a - x‬واﻟﺰﻣﻦ )‪ (t‬ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ‬
‫‪.  -‬‬
‫‪k ‬‬
‫ﯾﻜﻮن ‪‬‬ ‫ﻣﯿﻠﮫ‬
‫‪ 2.303 ‬‬
‫وإذا أﻋﻄ ﺖ اﻟﻘ ﯿﻢ اﻟﻨﺎﺗﺠ ﺔ ﻣ ﻦ اﻟﺘﺠﺮﺑ ﺔ ﺧﻄ ﺎ ً ﻣﺴ ﺘﻘﯿﻤﺎ ً ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ‬

‫أﺣﺎدي اﻟﺮﺗﺒ ﺔ‪ ،‬وﯾﻤﻜ ﻦ ﺑﺎﻟﺘ ﺎﻟﻲ ﺗﻌﯿ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻣ ﻦ ﻣﯿ ﻞ اﻟﺨ ﻂ‬
‫اﻟﻤﺴﺘﻘﯿﻢ‪ .‬واﻟﻄﺮﯾﻘﺔ اﻟﺒﯿﺎﻧﯿ ﺔ ﻟﺘﺤﺪﯾ ﺪ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﺗﻜ ﻮن أﻛﺜ ﺮ دﻗ ﺔ‬
‫ﻣﻦ طﺮﯾﻘﺔ اﻟﺘﻌﻮﯾﺾ‪.‬‬
‫‪ (٣‬ﻃﺮﻳﻘﺔ ﺍﻟﻜﺴﺮ ﻣﻦ ﻋﻤﺮ ﺍﻟﺘﻔﺎﻋﻞ )ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ(‬

‫‪Half – life period‬‬
‫ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت أﺣﺎدﯾ ﺔ اﻟﺮﺗﺒ ﺔ ﯾﻜ ﻮن اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻹﻧﻘ ﺎص ﺗﺮﻛﯿ ﺰ‬
‫اﻟﻤﺘﻔﺎﻋﻞ ﺑﻜﺴﺮ ﻣﻦ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻻ ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘ ﺪاﺋﻲ‬
‫ﻟﺬﻟﻚ اﻟﻤﺘﻔﺎﻋﻞ‪.‬‬

‫)‪(412‬‬
‫ﻧﻔﺮض أن اﻟﺰﻣﻦ )‪ (t1/2‬ھﻮ اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﻮﺻ ﻮل ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔﺎﻋ ﻞ‬

‫اﻹﺑﺘ ﺪاﺋﻲ اﻟ ﻰ اﻟﻨﺼ ﻒ أي )‪ (0.5 a‬وﯾﻌ ﺮف ذﻟ ﻚ اﻟ ﺰﻣﻦ ﺑﺄﻧ ﮫ ﻓﺘ ﺮة‬
‫‪‬‬ ‫‪1‬‬ ‫‪a ‬‬
‫‪ k = ln‬‬ ‫‪‬‬ ‫ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟﻠﻤﺘﻔﺎﻋ ﻞ‪ .‬ﻓﺒ ﺎﻟﺘﻌﻮﯾﺾ ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪t (a - x) ‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪1‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫)‪t (a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪t 0.5 ‬‬ ‫‪a‬‬
‫‪a - ‬‬
‫‪‬‬ ‫‪2‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪t 0.5  2a - a ‬‬
‫‪‬‬ ‫‪‬‬
‫‪ 2 ‬‬
‫‪1‬‬ ‫‪a‬‬ ‫‪1‬‬
‫=‪k‬‬ ‫‪ln‬‬ ‫=‪⇒k‬‬ ‫‪ln 2‬‬
‫‪t 0.5  a ‬‬ ‫‪t 0.5‬‬
‫‪ ‬‬
‫‪2‬‬
‫‪0.693‬‬
‫=‪k‬‬
‫‪t 0.5‬‬
‫‪0.693‬‬
‫= ‪⇒ t 0.5‬‬
‫‪k‬‬
‫‪‬‬ ‫‪0.693 ‬‬

‫ﻧﻼﺣ ﻆ أن زﻣ ﻦ ﻧﺼ ﻒ اﻟﻌﻤ ﺮ‬ ‫= ‪ t 0.5‬‬ ‫‪‬‬ ‫وﻣ ﻦ اﻟﻌﻼﻗ ﺔ اﻷﺧﯿ ﺮة‬
‫‪‬‬ ‫‪k ‬‬
‫ﻷي ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻻ ﯾﻌﺘﻤ ﺪ ﻋﻠ ﻰ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ‬

‫ﻟﻠﻤﺘﻔﺎﻋﻞ )ﻣﺴﺘﻘﻠﺔ ﺗﻤﺎﻣﺎ ً ﻋﻦ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ( وھ ﺬا‬
‫ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﯾﺴﺘﻐﺮق اﻟﻔﺘﺮة اﻟﺰﻣﻨﯿﺔ ﻧﻔﺴﮭﺎ ﻟﯿ ﺘﻢ‬

‫)‪(413‬‬
‫ﻧﺼﻒ اﻟﺘﻔﺎﻋ ﻞ ﺳ ﻮا ًء أﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻋﺎﻟﯿ ﺎ ً أو ﻣﻨﺨﻔﻀ ﺎ ً‪ .‬أي‬

‫أﻧﮭﺎ ﺗﺴﺘﻐﺮق ﻧﻔﺲ اﻟﻮﻗﺖ ﺳ ﻮاء اﻧﺨﻔ ﺾ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻣ ﻦ‬
‫)‪ (1 M‬اﻟ ﻰ )‪ (0.5 M‬أو ﻣ ﻦ )‪ (0.1 M‬اﻟ ﻰ )‪ (0.05 M‬ﻛﻤ ﺎ ﻓ ﻲ‬
‫اﻟﺸﻜﻞ )‪.(١٦-٢‬‬
‫ﺷ ﻜﻞ )‪ : (١٦-٢‬اﻟﺘﻐﯿ ﺮ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ ﻣ ﺎدة ﻣﺘﻔﺎﻋﻠ ﺔ ﻣ ﻊ ﻋ ﺪد ﻓﺘ ﺮات ﻧﺼ ﻒ اﻟﻌﻤ ﺮ‬

‫ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(414‬‬
‫ً‬
‫ﺗﻌﻴﲔ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ﻋﻤﻠﻴﺎ ﻟﺘﻔﺎﻋﻞ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬
‫ﺗﻌﯿﻦ ﻓﺘﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻋﻤﻠﯿ ﺎ ً ﺑﺎﺳ ﺘﺨﺪام ﻋ ﺪة ﺗﺮﻛﯿ ﺰات اﺑﺘﺪاﺋﯿ ﺔ ﻓﻠ ﻮ‬

‫ﺗﺒﯿﻦ أن )‪ (t0.5‬ﺗﺨﺘﻠﻒ ﻣﻦ ﺣﺎﻟﺔ اﻟﻰ أﺧﺮى ﻓ ﺈن ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﻻ ﯾﻌﺘﺒ ﺮ‬
‫ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺪرﺟﺔ اﻷوﻟﻰ واﻟﻌﻜﺲ ﺻﺤﯿﺢ‪.‬‬
‫وﻋﻤﻮﻣﺎ ً ﯾﻜﻮن اﻟﺰﻣﻦ ) ‪ ( t1/f‬اﻟﻼزم ﻹﻧﻘﺎص اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﺑﺎﻟﻜﺴﺮ‬
‫)‪ (1/f‬ﯾﻌﻄﻰ ﺑﺎﻟﻘﯿﻤﺔ ‪:‬‬
‫‪ln f‬‬
‫= ‪t1/f‬‬
‫‪k‬‬
‫س( وﺿ ﺢ ﻛﯿ ﻒ ﯾﻤﻜ ﻦ اﺳ ﺘﻨﺒﺎط اﻟﻤﻌﺎدﻟ ﺔ اﻟﺘﻔﺎﺿ ﻠﯿﺔ ﻟﺜﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ‬
‫ﻟﻠﺘﻔﺎﻋﻼت أﺣﺎدﯾﺔ اﻟﺮﺗﺒﺔ‪.‬‬
‫س( وﺿ ﺢ ﺑﺈﯾﺠ ﺎز اﻟﻄ ﺮق اﻟﻤﺴ ﺘﺨﺪﻣﺔ ﻟﺘﻌﯿ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻓ ﻲ‬
‫اﻟﺘﻔﺎﻋﻼت أﺣﺎدﯾﺔ اﻟﺮﺗﺒﺔ‪.‬‬

‫)‪(415‬‬
‫‪ (٤‬ﻃﺮﻳﻘــﺔ ﺟﻮﺟﻴﻨﻬــﺎﻳﻢ )‪ (Guggenheim‬ﳊﺴــﺎﺏ ﺛﺎﺑــﺖ‬

‫ﻣﻌﺪﻝ ﺍﻟﺘﻔﺎﻋﻞ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ‪:‬‬
‫اﻗﺘﺮح اﻟﻌﺎﻟﻢ ﺟﻮﺟﯿﻨﮭﺎﯾﻢ ﻋﺎم )‪ 1926‬م( طﺮﯾﻘﺔ ﻟﺤﺴﺎب ﺛﺎﺑﺖ ﻣﻌ ﺪل‬
‫اﻟﺘﻔﺎﻋ ﻞ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻓ ﻲ ﺣﺎﻟ ﺔ ﻋ ﺪم ﻣﻌﺮﻓ ﺔ اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻻﺑﺘﺪاﺋﻲ أو اﻟﺘﺮﻛﯿﺰ اﻟﻨﮭﺎﺋﻲ ﻟﻠﻤﻮاد اﻟﺪاﺧﻠﺔ ﻓﻲ اﻟﺘﻔﺎﻋﻞ وھﺬه اﻟﻤﺸ ﻜﻠﺔ‬
‫ﺗﺒﺮز ﻋﻨﺪﻣﺎ ﺗﻄﺒﻖ طﺮﯾﻘﺔ طﺒﯿﻌﯿﺔ ﻟﺘﺘﺒﻊ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫وﺗﺘﻠﺨﺺ اﻟﻄﺮﯾﻘ ﺔ ﻓ ﻲ أن ﺗﺆﺧ ﺬ ﺳﻠﺴ ﻠﺔ ﻣ ﻦ اﻟﻘ ﺮاءات ﻟﺘﺮﻛﯿ ﺰ اﻟﻨ ﺎﺗﺞ‬
‫]‪ [x‬ﻓ ﻲ أوﻗ ﺎت )‪ (t‬ﻣﻮزﻋ ﺔ ﻋﻠ ﻰ ﻓﺘ ﺮات ﺗﻜ ﻮن ﻣﺴ ﺎوﯾﺔ ﻣ ﺮﺗﯿﻦ أو‬
‫ﺛﻼﺛﺔ ﻟﻔﺘﺮات ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬
‫ﺗﺆﺧﺬ ﺳﻠﺴﻠﺔ أﺧﺮى ﻣﻦ اﻟﻘﺮاءات ]‪ [x‬ﻓﻲ أوﻗﺎت )'‪ (t + t‬ﺣﯿﺚ )'‪(t‬‬
‫ھﻲ ﻓﺘﺮة ﺣﻘﯿﻘﯿﺔ ﺛﺎﺑﺘﺔ ﺑﻌﺪ وﻗﺖ اﻟﻘ ﺮاءة اﻟﻤﻘﺎﺑﻠ ﺔ ]‪ [x‬وﻻ ﺑ ﺪ أن ﺗﻜ ﻮن‬
‫ﻟﻔﺘﺮة )'‪ (t‬ﻣﺜﻞ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻣﺮﺗﯿﻦ أو ﺛﻼﺛﺔ ﻋﻠﻰ اﻷﻗﻞ‪.‬‬
‫وإذا ﻛﺎﻧﺖ ﻗﯿﻤﺔ ‪ [A]0‬ھﻲ اﻟﻘﯿﻤﺔ اﻟﻐﯿﺮ ﻣﻌﺮوﻓﺔ ﻟ ـ )‪ (x‬ﻋﻨ ﺪ اﻟﻼﻧﮭﺎﯾ ﺔ‬
‫ﻓﺈﻧﮫ ﯾﺘﺒﻊ ﻣﻦ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻟﻘﺮاءة ﻣﻌﯿﻨﺔ ﻋﻨﺪ زﻣﻦ )‪: (t1‬‬

(416)
[ A ]0
ln = kt
[A] 1
ln [ A ]0 - ln [ A ] = kt1
ln [ A ]0 - ln ([ A ]0 - x1 ) = kt1
- ln ([ A ]0 - x1 ) = - ln [ A ]0 + kt1
ln ([ A ]0 - x1 ) = ln [ A ]0 - kt1
⇒ ([ A ]0 - x1 ) = [ A ]0 e- kt 1
‫ [( ( ﻓ ﺈن اﻟﻘ ﺮاءة ﺑﻌ ﺪ‬A ]0 - x1 ) = [ A]0 e- kt ) ‫ووﻓﻘ ﺎ ً ﻟﻠﻌﻼﻗ ﺔ اﻷﺧﯿ ﺮة‬

1
: ‫( ھﻲ‬t') ‫اﻟﻔﺘﺮة‬
([ A ] 0
- x1
'
) = [ A ]0
e - k(t1 + t')
(t2 + t') ‫( و‬t2) ‫وﻛﺬﻟﻚ اﻟﺤﺎل ﻟﻘﯿﻢ ﺣﻘﯿﻘﯿﺔ ﻓﻲ أوﻗﺎت ﻋﻨﺪ‬

‫ﻦ‬ ‫ [( ( ﻣ‬A ]
0 )
- x1 = [ A ]0 e - kt1 ) ‫وﺑﻄ ﺮح اﻟﻤﻌ ﺎدﻟﺘﯿﻦ )اﻟﻤﻌﺎدﻟ ﺔ‬
: ‫ [(( ﻧﺤﺼﻞ ﻋﻠﻰ‬A ] 0 )
- x1' = [ A ]0 e - k(t1 + t') )
([ A ] 0 ) ( )
- x1' − [ A ]0 - x1 = [ A ]0 e- k(t1 + t') − [ A ]0 e- kt1
 A  0 - x1' −  A  0 + x1 = [ A ]0 e- k(t1 + t') − [ A ]0 e- kt1
- x1' + x1 = [ A ]0 e - k(t1 + t') − [ A ]0 e - kt1
x1' − x1 = [ A ]0 e- kt1 − [ A ]0 e- k(t1 + t')
x1' - x1 = [ A ]0 e- kt1 (1- e
-kt'
)
(
ln ( x1' - x1 ) = ln [ A ]0 (1- e-kt' ) - kt1 )
⇒ kt1 + ln ( x1' - x1 ) = ln [ A ]0 (1- e-kt' ) ( )

‫)‪(417‬‬
‫اﻟﻄﺮف اﻷﯾﻤﻦ ﻣﻦ ھﺬه اﻟﻤﻌﺎدﻟﺔ ﺛﺎﺑﺖ ﺣﯿﺚ )'‪ (t‬اﺧﺘﯿﺮت ﻟﻜ ﻲ ﺗﻜ ﻮن‬

‫ﺔ أي‬ ‫ﺮاءة ﻣﻘﺎﺑﻠ‬ ‫ﻞﻗ‬ ‫ﺬا إذاً أن ﻟﻜ‬ ‫ﻦھ‬ ‫ﻊﻣ‬ ‫ﺔ ﯾﺘﺒ‬ ‫ﺛﺎﺑﺘ‬
‫)‪. ( x1' and x1 , x '2 and x 2 ...etc.‬‬
‫‪kt + ln(x ' - x) = constant‬‬
‫ورﺳﻢ ) )‪ ( ln(x ' - x‬ﻣﻘﺎﺑﻞ )‪ (t‬ﯾﻌﻄﻲ ﺧﻄﺎ ً ﻣﺴﺘﻘﯿﻤﺎ ً ﻣﯿﻠﮫ ﯾﺴﺎوي )‪.(- k‬‬
‫ﻣﺜﺎﻝ )‪(٢-٢‬‬
‫ﯾﻨﺘﻤﻲ اﻟﺘﺤﻄﻢ اﻟﺤﺮاري ﻟﻸﺳﯿﺘﻮن )‪ (CH3)2C=O‬اﻟﻰ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ‬

‫اﻷوﻟﻰ )درﺟﺔ اﻟﺤﺮارة ‪ ،(600 ºC‬وﯾﺒﻠﻎ ﻧﺼﻒ زﻣﻦ اﻟﺘﻔﺎﻋﻞ = ‪(t1/2‬‬
‫)‪80 s‬‬
‫أ( اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‬
‫ب( ﻣﺎ اﻟﺰﻣﻦ اﻟﻼزم ﻟ ﺘﺤﻄﻢ )‪ (25 %‬ﻣ ﻦ اﻟﻤ ﺎدة؟ ﺛ ﻢ ﻟ ﺘﺤﻄﻢ )‪(85 %‬‬
‫ﻣﻦ ﻧﻔﺲ اﻟﻤﺎدة؟‪.‬‬
‫ﺍﳊﻞ‬
‫أ( ﺣﺴﺎب ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ ‪:‬‬

‫‪0.693‬‬
‫= ‪t1/2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫=‪k‬‬
‫‪t1/2‬‬
‫‪0.693‬‬
‫=‪k‬‬ ‫‪= 8.66 × 10-3‬‬
‫‪80‬‬

‫)‪(418‬‬
‫ب( ﺣﺴﺎب اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﺤﻄﻢ )‪: (25 %‬‬

‫ﻟﺤﻞ ھﺬه اﻟﻤﺴﺄﻟﺔ ﻧﻔﺘﺮض أن اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻸﺳﯿﺘﻮن ‪:‬‬
‫‪[A]0 = a = 1‬‬
‫)‪(x = 0.25‬‬
‫واﻟﺘﺮﻛﯿﺰ اﻟﻤﺘﺒﻘﻲ ﻣﻦ اﻷﺳﯿﺘﻮن ‪:‬‬
‫‪[A] = (a – x) = 1 – 0.25 = 0.75‬‬
‫وﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪a‬‬
‫‪kt = 2.303 log‬‬
‫‪a-x‬‬
‫‪2.303‬‬ ‫‪ a ‬‬
‫=‪t‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪k‬‬ ‫‪a-x‬‬
‫‪2.303‬‬ ‫‪1‬‬
‫=‪t‬‬ ‫‪log‬‬
‫‪8.66 × 10-3‬‬ ‫‪0.75‬‬
‫‪t = 33.22 s‬‬
‫وﺑﺘﻄﺒﯿﻖ ﻧﻔ ﺲ اﻟﻄﺮﯾﻘ ﺔ ﻟﺤﺴ ﺎب اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟ ﺘﺤﻄﻢ )‪ (85 %‬ﻣ ﻦ‬

‫ﻣﺎدة اﻷﺳﯿﺘﻮن ‪:‬‬
‫‪a‬‬
‫‪kt = 2.303 log‬‬
‫‪a-x‬‬
‫‪2.303‬‬ ‫‪ a ‬‬
‫=‪t‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪k‬‬ ‫‪a-x‬‬
‫‪2.303‬‬ ‫‪1‬‬
‫=‪t‬‬ ‫‪log‬‬
‫‪8.66 × 10‬‬ ‫‪-3‬‬
‫‪0.15‬‬
‫‪t = 219.11 s‬‬

‫)‪(419‬‬
‫ﻣﺜﺎﻝ )‪(٣-٢‬‬
‫إذا ﻛﺎن ﻟﺪﯾﻚ ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﯾﺤﺪث ﻋﻨﺪ درﺟﺔ ﺣﺮارة ‪(70‬‬
‫)‪ ºC‬ﺗﻢ ﻣﻨﮫ )‪ (20 %‬ﻓﻲ زﻣﻦ ﻗﺪره )‪ (22 min.‬ﻓﺎﺣﺴﺐ ‪:‬‬
‫أ( ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
‫ب( ﻧﺼﻒ ﻋﻤﺮ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ج( ﻧﺴﺒﺔ ﻣﺎ ﯾﺘﺒﻘﻰ ﻣﻦ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﺑﻌﺪ ﺧﻤﺲ ﺳﺎﻋﺎت‪.‬‬
‫ﺍﳊﻞ‬
‫أ( ﺑﻤﺎ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﺈﻧﻨﺎ ﻧﻄﺒﻖ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪a‬‬
‫‪2.303 log‬‬ ‫‪= kt‬‬
‫‪a-x‬‬
‫‪2.303‬‬ ‫‪ a ‬‬
‫=‪k‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪t‬‬ ‫‪a-x‬‬
‫‪2.303‬‬ ‫‪ a ‬‬
‫=‪k‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪22‬‬ ‫‪a-x‬‬
‫ﻓﻲ اﻟﻤﺴﺄﻟﺔ ﻟﻢ ﯾﺬﻛﺮ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ )‪ ،(a‬ﻟﺬﻟﻚ ﺳﻨﻔﺮض أﻧﮫ ﯾﺴﺎوي‬

‫)‪: (100‬‬
‫‪a = 100‬‬
‫‪20‬‬
‫=‪x‬‬ ‫‪× 100 = 20‬‬
‫‪100‬‬
‫‪( a - x ) = 100 - 20 = 80‬‬

(420)
 2.303  a 
‫ﻧﺤﺼ ﻞ‬  k = 22 log  a - x   ‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﺑﮭ ﺬه اﻟﻘ ﯿﻢ ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
  
: ‫ﻋﻠﻰ‬
2.303  100 
k= log  
22  80 
2.303  100 
k= log  
22  80 
k = 1.014 × 10-2 min -1
: ‫ب( ﺣﺴﺎب ﻧﺼﻒ ﻋﻤﺮ اﻟﺘﻔﺎﻋﻞ‬

0.693
t1/2 =
k
0.693
t1/2 =
1.014 × 10-2
t1/2 = 68.34 min
‫[( ﺑﻌ ﺪ‬A]= c = a – x)‫ج( ﻧﺴ ﺒﺔ ﻣ ﺎ ﯾﺘﺒﻘ ﻰ ﻣ ﻦ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‬

: ‫ﺧﻤﺲ ﺳﺎﻋﺎت‬
a
2.303 log   = k t
c
 100 
 = 1.014 × 10 × ( 5 × 60 )
-2
2.303 log 
 c 
 100  1.014 × 10 × ( 5 × 60 )
-2
log  =
 c  2.303
 100 
log   =1.321
 c 
 100 
  = 20.94
 c 
100
c= = 4.77
20.94

‫)‪(421‬‬
‫وﯾﻤﻜﻦ اﻟﺤﺼﻮل ﻋﻠﻰ ﻧﻔﺲ اﻟﻨﺘﺎﺋﺞ إذا اﻓﺘﺮﺿ ﻨﺎ أن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ‬
‫)‪ ([A]0 = a = 1‬ﺑﺪﻻً ﻣﻦ اﻻﻓﺘﺮاض أﻧﮫ ﯾﺴﺎوي )‪.(100‬‬
‫ﻣﺜﺎﻝ )‪(٤-٢‬‬
‫إذا ﻛ ﺎن ﺗﺤ ﻮل اﻟﺒﺮوﺑ ﺎن اﻟﺤﻠﻘ ﻲ )‪ (cyclopropane‬اﻟ ﻰ ﺑﺮوﺑ ﺎن‬

‫)‪ (propane‬ﻓﻲ اﻟﻄﻮر اﻟﻐﺎزي‪:‬‬
‫‪C3H 6 ‬‬
‫‪→ CH3 -CH = CH 2‬‬
‫ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (250 ºC‬ﺗﻔ ﺎﻋﻼً ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ وﺛﺎﺑ ﺖ‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ھﺬه اﻟﺪرﺟ ﺔ ﯾﺴ ﺎوي )‪ ،(6.71 × 10-4 s-1‬وﻛ ﺎن‬
‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﺒﺮوﺑﺎن اﻟﺤﻠﻘﻲ )‪ (0.25 M‬ﻓﺎﺣﺴﺐ ‪:‬‬
‫أ( ﺗﺮﻛﯿﺰه ﺑﻌﺪ )‪.(4.5 min‬‬
‫ب( اﻟﻔﺘﺮة اﻟﺰﻣﻨﯿﺔ اﻟﻼزﻣﺔ ﻟﺨﻔﺾ اﻟﺒﺮوﺑ ﺎن اﻟﺤﻠﻘ ﻲ ﻣ ﻦ )‪(0.25 M‬‬
‫اﻟﻰ )‪.(0.15 M‬‬
‫ج( اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻣ ﻦ أﺟ ﻞ أن ﯾﺘﺤ ﻮل )‪ (72 %‬ﻣ ﻦ اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻹﺑﺘﺪاﺋﻲ‪.‬‬
‫د( ﻓﺘﺮة ﻋﻤﺮ اﻟﻨﺼﻒ‬
‫ﺍﳊﻞ‬
‫أ( ﺗﺮﻛﯿﺰه ﺑﻌﺪ )‪: (4.5 min‬‬

‫)‪(422‬‬
‫‪[ A ]0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫]‪[A‬‬
‫‪[ A ]0 kt‬‬
‫‪=e‬‬
‫]‪[A‬‬
‫‪0.25‬‬ ‫)‪( 6.71 × 10-4 × 4.5 × 60‬‬
‫‪=e‬‬
‫]‪[ A‬‬
‫‪0.25‬‬
‫‪= 1.20‬‬
‫]‪[ A‬‬
‫‪0.25‬‬
‫= ]‪[ A‬‬ ‫‪= 0.21 M‬‬
‫‪1.2‬‬
‫ب( اﻟﻔﺘﺮة اﻟﺰﻣﻨﯿﺔ اﻟﻼزﻣﺔ ﻟﺨﻔﺾ اﻟﺒﺮوﺑﺎن اﻟﺤﻠﻘﻲ ﻣﻦ )‪(0.25 M‬‬

‫اﻟﻰ )‪.(0.15M‬‬
‫‪ [ A ]0 ‬‬
‫‪ln ‬‬
‫‪ [ A ] ‬‬
‫‪= kt‬‬
‫‪‬‬ ‫‪‬‬
‫‪1 [ A ]0‬‬
‫‪t = ln‬‬
‫]‪k [A‬‬
‫‪1‬‬ ‫‪ 0.25 ‬‬
‫=‪t‬‬ ‫‪ln‬‬ ‫‪‬‬ ‫‪‬‬
‫‪6.71 × 10−4 s -1  0.15 ‬‬
‫‪t = 761.3 s‬‬
‫‪t = 12.70 min‬‬
‫ج( اﻟﺰﻣﻦ اﻟﻼزم ﻣﻦ أﺟﻞ أن ﯾﺘﺤﻮل )‪ (72 %‬ﻣﻦ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ‪:‬‬
‫ﻓﻲ ﻣﺴﺎﺋﻞ ﻣﻦ ھﺬا اﻟﻨﻮع ﻻ ﻧﺤﺘﺎج اﻟﻰ ﻣﻌﺮﻓﺔ اﻟﺘﺮﻛﯿ ﺰ اﻟﺤﻘﯿﻘ ﻲ ﺣﯿ ﺚ‬
‫ﯾﻤﻜ ﻦ اﻓﺘ ﺮاض أﻧ ﮫ ﯾﺴ ﺎوي )‪ ،(1 M‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﺗﺮﻛﯿ ﺰ اﻟﺒﺮوﺑ ﺎن‬
‫اﻟﺤﻠﻘﻲ ﺑﻌﺪ زﻣﻦ ﻗﺪره )‪ (t‬ﯾﺴﺎوي ‪:‬‬
‫‪[ A ] = 1 - 0.72 = 0.28 M‬‬

‫)‪(423‬‬
‫وﺑﺎﻟﺘ ﺎﻟﻲ ﻟﺤﺴ ﺎب اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺘﺤ ﻮل )‪ (72 %‬ﻣ ﻦ اﻟﺒﺮوﺑ ﺎن‬
‫اﻟﺤﻠﻘﻲ اﻟﻰ ﻧﻮاﺗﺞ ﻧﻄﺒﻖ ﻓﻲ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬
‫‪ [ A ]0 ‬‬
‫‪ln ‬‬
‫‪ [ A ] ‬‬
‫‪= kt‬‬
‫‪‬‬ ‫‪‬‬
‫‪1 [ A ]0‬‬
‫‪t = ln‬‬
‫]‪k [A‬‬
‫‪1‬‬ ‫‪ 1 ‬‬
‫=‪t‬‬ ‫‪−4 -1‬‬
‫‪ln ‬‬ ‫‪‬‬
‫‪6.71 × 10 s‬‬ ‫‪ 0.28 ‬‬
‫‪t = 1897.1 s‬‬
‫‪t = 31.62 min‬‬
‫وﯾﻤﻜﻦ اﻟﺤﺼﻮل ﻋﻠﻰ ﻧﻔﺲ اﻟﻨﺘﯿﺠﺔ إذا اﻓﺘﺮﺿﻨﺎ أن اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘ ﺪاﺋﻲ‬
‫ﯾﺴﺎوي )‪ (100‬وأن اﻟﺘﺮﻛﯿﺰ ﺑﻌﺪ ﺗﺤﻮل )‪ (72 %‬اﻟﻰ ﻧﻮاﺗﺞ ﯾﺴﺎوي ‪:‬‬
‫‪[ A ] = 100 - 72 = 28 M‬‬
‫د( ﺣﺴﺎب ﻧﺼﻒ زﻣﻦ اﻟﻌﻤﺮ ‪:‬‬
‫‪0.693‬‬
‫= ‪t1/2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫= ‪t1/2‬‬
‫‪6.71 × 10-4‬‬
‫‪t1/2 = 1032.8 s‬‬
‫‪t1/2 = 17.21 min‬‬

‫)‪(424‬‬
‫ﻣﺜﺎﻝ )‪(٥-٢‬‬
‫إذا ﻋﻠﻤ ﺖ أﻧ ﮫ ﻗ ﺪ ﺗﻤ ﺖ دراﺳ ﺔ ﺳ ﺮﻋﺔ ﺗﻔﻜ ﻚ ﻣﺮﻛ ﺐ اﻵزوﻣﯿﺜ ﺎن‬

‫)‪ (azomethane‬ﺣﺮارﯾ ﺎ ً ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (300 ºC‬ﻓ ﻲ‬
‫اﻟﻄ ﻮر اﻟﻐ ﺎزي‪ ،‬وذﻟ ﻚ ﺑﺘﺘﺒ ﻊ اﻟﺘﻐﯿ ﺮ اﻟﺤﺎﺻ ﻞ ﻓ ﻲ ﺿ ﻐﻄﮫ اﻟﺠﺰﺋ ﻲ‬
‫)‪ (partial pressure‬ﻣﻊ اﻟﺰﻣﻦ ‪:‬‬
‫‪CH 3 -N=N-CH 3 (g) ‬‬
‫)‪→ N 2 (g) + C 2 H 6 (g‬‬
‫وﻛﺎﻧﺖ ﻧﺘﯿﺠﺔ اﻟﺪراﺳﺔ ﻛﻤﺎ ﻓﻲ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬

‫)‪Time (s‬‬ ‫‪0‬‬ ‫‪100‬‬ ‫‪150‬‬ ‫‪200‬‬ ‫‪250‬‬ ‫‪300‬‬
‫)‪Pt (mmHg‬‬ ‫‪284‬‬ ‫‪220‬‬ ‫‪193‬‬ ‫‪170‬‬ ‫‪150‬‬ ‫‪132‬‬
‫أ( أﺛﺒﺖ ﺣﺴﺎﺑﯿﺎ ً أن ھﺬه اﻟﻤﻌﻠﻮﻣﺎت ﻣﻮاﻓﻘﺔ ﻟﺘﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‬

‫ب( أﺛﺒﺖ ﺑﺎﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ أن ھﺬه اﻟﻤﻌﻠﻮﻣ ﺎت ﻣﻮاﻓﻘ ﺔ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ‬
‫اﻷوﻟﻰ‬
‫ج( أوﺟﺪ ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻦ طﺮﯾﻖ اﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ‪.‬‬
‫د( اﺣﺴﺐ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‬
‫ﺍﳊﻞ‬
‫أ( ﻟﻜ ﻲ ﻧﺜﺒ ﺖ ﺣﺴ ﺎﺑﯿﺎ ً أن ھ ﺬه اﻟﻤﻌﻠﻮﻣ ﺎت ﻣﻮاﻓﻘ ﺔ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ‬

‫اﻷوﻟﻰ ﻓﺈﻧﻨﺎ ﻧﻌﻮض ﻓﻲ ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻷوﻟﻰ اﻟﺬي ﯾﺤﺴﺐ ﻗﯿﻤﺔ )‪: (k‬‬

‫)‪(425‬‬
‫‪P ‬‬
‫‪ln  0  = k t‬‬
‫‪ Pt ‬‬
‫‪1 P ‬‬
‫‪k = ln  0 ‬‬
‫‪t  Pt ‬‬
‫وﺑﺤﺴ ﺎب ﻗﯿﻤ ﺔ )‪ (k‬ﻣ ﻦ ﻗ ﺎﻧﻮن اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻓﺈﻧﻨ ﺎ ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﻗ ﯿﻢ‬

‫ﺛﺎﺑﺘﺔ إذا ﻛﺎن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬
‫‪P0 = 284 mmHg‬‬
‫)‪Time (s‬‬ ‫‪100‬‬ ‫‪150‬‬ ‫‪200‬‬ ‫‪250‬‬ ‫‪300‬‬
‫)‪Pt (mmHg‬‬ ‫‪220‬‬ ‫‪193‬‬ ‫‪170‬‬ ‫‪150‬‬ ‫‪132‬‬
‫‪1  P0 ‬‬
‫=‪k‬‬ ‫‪ln  ‬‬ ‫‪2.55 × 10-3‬‬ ‫‪2.57 × 10-3‬‬ ‫‪2.57 ×10-3‬‬ ‫‪2.55 × 10-3‬‬ ‫‪2.55 × 10-3‬‬
‫‪t  Pt ‬‬
‫‪k‬‬ ‫‪2.56 × 10-3 s-1‬‬
‫وﺗﻘ ﺎرب ﻗ ﯿﻢ ﻗﯿﻤ ﺔ )‪ (k‬ﯾ ﺪل ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪.‬‬

‫وﯾﺼﺒﺢ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ھﻮ ﻣﻌ ﺪل ھ ﺬه اﻟﻘ ﯿﻢ اﻟﻤﺘﻘﺎرﺑ ﺔ وﯾﺴ ﺎوي‬
‫)‪(k = 2.56 × 10-3 s-1‬‬
‫ب( ﻟﻜﻲ ﻧﺜﺒﺖ ﺑﺎﻟﺮﺳﻢ اﻟﺒﯿ ﺎﻧﻲ أن ھ ﺬه اﻟﻤﻌﻠﻮﻣ ﺎت ﻣﻮاﻓﻘ ﺔ ﻟﺘﻔ ﺎﻋﻼت‬
‫اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﺈﻧﻨﺎ ﻧﻤﺜﻞ اﻟﻌﻼﻗﺔ اﻟﺘﺎﻟﯿﺔ ﺑﯿﺎﻧﯿﺎ ً ‪:‬‬
‫‪P ‬‬
‫‪ln  0  = k t‬‬
‫‪ Pt ‬‬
‫‪ln P0 - ln Pt = kt‬‬
‫‪⇒ ln Pt = - kt + ln P0‬‬

‫)‪(426‬‬
‫‪ ( ln Pt‬ﺑﯿﺎﻧﯿﺎ ً ﺣﯿ ﺚ ﯾﻤﺜ ﻞ ‪(ln‬‬ ‫) ‪= - kt + ln P0‬‬ ‫وﺑﺘﻤﺜﯿﻞ اﻟﻌﻼﻗﺔ اﻷﺧﯿﺮة‬

‫)‪ Pt‬ﻋﻠﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات و )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت‪ .‬ﻓ ﺈذا ﺣﺼ ﻠﻨﺎ‬
‫ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻓ ﺈن ھ ﺬا ﯾ ﺪل ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫وﯾﻜ ﻮن ﻣﯿﻠ ﮫ ھ ﻮ )‪ (- k‬واﻟﺠ ﺰء اﻟﻤﻘﻄ ﻮع ﻣ ﻦ ﻣﺤ ﻮر اﻟﺼ ﺎدات ھ ﻮ‬
‫)‪.(ln P0‬‬
‫‪P0 = 284 mmHg, ln P 0 = 5.649‬‬
‫)‪Time (s‬‬ ‫‪100‬‬ ‫‪150‬‬ ‫‪200‬‬ ‫‪250‬‬ ‫‪300‬‬
‫)‪Pt (mmHg‬‬ ‫‪220‬‬ ‫‪193‬‬ ‫‪170‬‬ ‫‪150‬‬ ‫‪132‬‬
‫‪ln Pt‬‬ ‫‪5.394‬‬ ‫‪5.263‬‬ ‫‪5.136‬‬ ‫‪5.011‬‬ ‫‪4.883‬‬
‫وﺑﺘﻤﺜﯿ ﻞ )‪ (ln Pt‬ﻣﻘﺎﺑ ﻞ )‪ (t‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ اﻟﺸ ﻜﻞ )‪ (١٧-٢‬وﻣﻨ ﮫ‬

‫ﯾﺘﻀﺢ أن اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪ (ln Pt‬و )‪ (t‬ﺧﻄﯿﺔ ﻟﺬﻟﻚ ﻓﺈن اﻟﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻖ‬
‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﺷﻜﻞ )‪(١٧-٢‬‬

‫)‪(427‬‬
‫ج( ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻦ طﺮﯾﻖ اﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ‪.‬‬

‫ﯾﻤﻜﻦ اﺳ ﺘﻨﺘﺎج ﻗﯿﻤ ﺔ )‪ (k‬ﻣ ﻦ اﻟﺮﺳ ﻢ اﻟﺒﯿ ﺎﻧﻲ اﻟﺴ ﺎﺑﻖ ﻣ ﻦ ﺧ ﻼل اﯾﺠ ﺎد‬
‫اﻟﻤﯿﻞ )‪ (slope‬ﺣﯿﺚ ‪:‬‬
‫‪slope = - k‬‬
‫‪k = - slope‬‬
‫‪ 5.136 - 5.520 ‬‬
‫‪k = -‬‬ ‫‪‬‬
‫‪ 200 - 50 ‬‬
‫) ‪k = - ( - 2.56 × 10-3‬‬
‫‪k = 2.56 × 10-3s -1‬‬
‫د( ﺣﺴﺎب ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪: (k‬‬

‫‪0.693‬‬
‫= ‪t1/2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫= ‪t1/2‬‬
‫‪2.56 × 10-3‬‬
‫‪t1/2 = 270.70 s‬‬

‫)‪(428‬‬
‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ﺑﺪﻻﻟﺔ ﺍﳊﺠﻢ ﻭﺍﻟﻀﻐﻂ‬
‫ﻣﻦ ﺍﻷﻣﺜﻠﺔ ﻋﻠﻰ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ‪:‬‬

‫• ﺗﻤﯿﺆ ﺧﻼت اﻟﻤﯿﺜﯿﻞ ﻓﻲ ﻣﺤﻠﻮل ﻣﺎﺋﻲ ‪:‬‬
‫‪CH3COOCH3 + H 2 O ‬‬ ‫‪→ CH3COOH + CH3 OH‬‬
‫‪+‬‬
‫‪H‬‬
‫• ﺗﻔﻜﻚ ﻣﺮﻛﺐ اﻵزوأﯾﺰوﺑﺮوﺑﺎن )‪ (Azoisopropan‬ﺣﺮارﯾ ﺎ ً ﻓ ﻲ‬

‫اﻟﻄﻮر اﻟﻐﺎزي ‪:‬‬
‫‪( CH3 )2 CHN=NCH(CH 3 ) 2 ‬‬
‫‪→ N 2 + C 6 H14‬‬
‫وﺗﺠﺪر اﻹﺷﺎرة ھﻨﺎ اﻟﻰ أﻧﮫ ﯾﻤﻜﻦ ﺗﺤﻮﯾﻞ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﻲ ﻛﻞ‬
‫ﻣﻦ اﻟﺘﻔﺎﻋﻠﯿﻦ اﻟﺴﺎﺑﻘﯿﻦ ﺑﺪﻻﻟﺔ اﻟﺤﺠﻢ واﻟﻀﻐﻂ ﻋﻠﻰ اﻟﺘﻮاﻟﻲ ﻛﻤﺎ ﯾﺘﻀﺢ‬
‫ﻣﻦ ﻣﻨﺎﻗﺸﺔ ﻛﻞ ﻣﻨﮭﻤﺎ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪ (١‬ﻗﺎﻧﻮﻥ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ﺑﺪﻻﻟﺔ ﺍﳊﺠﻮﻡ‬
‫ﺃ( ﲤﻴﺆ ﺧﻼﺕ ﺍﳌﻴﺜﻴﻞ ﰲ ﳏﻠﻮﻝ ﻣﺎﺋﻲ )ﺍﻟﺘﺤﻠﻞ ﺍﳌﺎﺋﻲ( ‪:‬‬
‫ﺣﯿ ﺚ أن ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﺑﻄ ﻲء ﺟ ﺪاً ﻓﺈﻧ ﮫ ﯾﻀ ﺎف إﻟﯿ ﮫ ﻛﻤﯿ ﺔ ﻗﻠﯿﻠ ﺔ ﻣ ﻦ‬

‫ﺣﻤ ﺾ ﻣﻌ ﺪﻧﻲ ﯾﻌﻤ ﻞ ﻛﻤﺤﻔ ﺰ ﻟﻠﺘﻔﺎﻋ ﻞ وﯾﻤﺜ ﻞ ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﺑﺎﻟﻤﻌﺎدﻟ ﺔ‬
‫اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪CH3COOCH3 + H 2 O ‬‬ ‫‪→ CH 3COOH + CH3OH‬‬
‫‪+‬‬
‫‪H‬‬

‫)‪(429‬‬
‫ﻗﺎﻧﻮن ﺳﺮﻋﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ ھﻮ ‪:‬‬

‫‪dx‬‬
‫]‪= k [ CH3COOCH3 ][ H 2 O‬‬
‫‪dt‬‬
‫وﺣﯿ ﺚ أن اﻟﻤ ﺎء ﻣﻮﺟ ﻮد ﺑﻜﻤﯿ ﺔ ﻛﺒﯿ ﺮة ﻓ ﻲ ﺣﯿ ﺰ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﺈن ﺗﺮﻛﯿ ﺰه‬
‫ﯾﻜ ﻮن ﺧ ﻼل اﻟﺘﻔﺎﻋ ﻞ ﺛﺎﺑ ﺖ ﺗﻘﺮﯾﺒ ﺎً‪ ،‬ﺑﻨ ﺎء ﻋﻠ ﻰ ذﻟ ﻚ ﺗﺼ ﺒﺢ اﻟﻤﻌﺎدﻟ ﺔ‬
‫اﻟﺴﺎﺑﻘﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪dx‬‬
‫) ‪= k ' [ CH 3COOCH 3 ][ H 2 O ] = k ' ( a - x‬‬
‫‪dt‬‬
‫وھﺬا ﯾﻌﻨﻲ أن ﺳﺮﻋﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ ﺗﺘﺄﺛﺮ ﻓﻘﻂ ﺑﺘﺮﻛﯿﺰ اﻟﺨﻼت ﻟﺬا ﻓﺈﻧ ﮫ‬
‫ﻣﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬وﻧﺘﺎﺋﺠ ﮫ اﻟﻌﻤﻠﯿ ﺔ ﺗﺤﻘ ﻖ ﻣﻌ ﺎدﻻت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪،‬‬
‫وﯾﻌﺮف ھﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔﺎﻋﻼت ﺑﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ اﻟﻈﺎھﺮﯾ ﺔ‬
‫)‪.(Pseudo-first order reactions‬‬
‫ﺍﺷﺮﺡ ﻛﻴﻒ ﳝﻜﻦ ﺩﺭﺍﺳﺔ ﻫﺬﺍ ﺍﻟﺘﻔﺎﻋﻞ؟‬
‫• ﺗﺆﺧ ﺬ ﻛﻤﯿ ﺔ ﻣﻌﯿﻨ ﺔ ﻣ ﻦ ﻣ ﺰﯾﺞ اﻟﺘﻔﺎﻋ ﻞ اﻟ ﺬي ﯾﺤﺘ ﻮي ﻋﻠ ﻰ ﺧ ﻼت‬

‫اﻟﻤﯿﺜﯿﻞ اﻟﺬاﺋﺒﺔ ﻓﻲ اﻟﻤﺎء اﻟﺘ ﻲ ﺗﺤﺘ ﻮي ﻋﻠ ﻰ ﻛﻤﯿ ﺔ ﻗﻠﯿﻠ ﺔ ﻣ ﻦ ﺣﻤ ﺾ‬
‫اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ )‪ (HCl‬وﺗﻮﺿ ﻊ ﻓ ﻲ دورق ﻣﺨﺮوط ﻲ ﻟﻤﻌﺎﯾﺮﺗ ﮫ‬
‫ﺑﻮاﺳﻄﺔ ﻣﺤﻠﻮل ﻗﯿﺎﺳﻲ ﻣﻦ ﻣﺎدة ﻗﺎﻋﺪﯾﺔ )‪(Alkali‬‬
‫• ﺑﻌ ﺪ اﻧﺘﮭ ﺎء اﻟﻤﻌ ﺎﯾﺮة ﯾﻜ ﻮن ﺣﺠ ﻢ اﻟﻘﺎﻋ ﺪة اﻟﻤﺴ ﺘﺨﺪم ﻣﻜﺎﻓﺌ ﺎ ً ﻟﺠﻤﯿ ﻊ‬
‫ﻞ‬ ‫ﺾ اﻟﺨ‬ ‫ﺎف‪ ،‬وﺣﻤ‬ ‫ﺪروﻛﻠﻮرﯾﻚ اﻟﻤﻀ‬ ‫ﺾ اﻟﮭﯿ‬ ‫ﺣﻤ‬

‫)‪(430‬‬
‫)‪ (acetic acid‬اﻟﻨ ﺎﺗﺞ ﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ‪ .‬وﺗﻜ ﻮن ﻛﻤﯿ ﺔ ﺣﻤ ﺾ‬

‫اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ اﻟﻤﻀ ﺎﻓﺔ ﻣﻜﺎﻓﺌ ﺔ ﻟﺤﺠ ﻢ اﻟﻘﺎﻋ ﺪة اﻟﻨ ﺎﺗﺞ ﻣ ﻦ أول‬
‫ﻣﻌﺎﯾﺮة ﻋﻨﺪ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ‪ ،‬ﻓﺈذا ﻛﺎن ﺣﺠ ﻢ اﻟﻘﺎﻋ ﺪة )‪ (V0‬اﻟﻤﺴ ﺘﺨﺪم‬
‫ﻟﻤﻌﺎﯾﺮة ﺣﻤﺾ اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ ﻓ ﻲ ﺑﺪاﯾ ﺔ اﻟﺘﻔﺎﻋ ﻞ‪ ،‬و )‪ (V1‬ﺣﺠ ﻢ‬
‫اﻟﻘﺎﻋ ﺪة ﺑﻌ ﺪ زﻣ ﻦ ﻗ ﺪره )‪ (t‬ﻓ ﺈن )‪ (Vt – V0‬ھ ﻮ ﺣﺠ ﻢ اﻟﻘﺎﻋ ﺪة‬
‫اﻟ ﻼزم ﻟﻤﻌ ﺎﯾﺮة ﺣﻤ ﺾ اﻟﺨ ﻞ ﻓﻘ ﻂ ﻋﻨ ﺪ اﻟ ﺰﻣﻦ )‪ ،(t‬وھ ﺬا ﯾﻜ ﺎﻓﻲء‬
‫اﻹﻧﺨﻔﺎض ﻓ ﻲ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ اﻟ ﻮاردة ﻓ ﻲ ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ‬
‫‪ .  ln‬وإذا ﻛ ﺎن ﺣﺠ ﻢ اﻟﻘﺎﻋ ﺪة‬ ‫‪‬‬

‫‪a‬‬
‫‪= kt ‬‬ ‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫‪‬‬ ‫‪a-x‬‬ ‫‪‬‬
‫اﻟﻤﺴﺘﺨﺪم ﺑﻌ ﺪ اﻛﺘﻤ ﺎل اﻟﺘﻔﺎﻋ ﻞ ﯾﺴ ﺎوي ) ∞‪ ( V‬وھ ﺬا ﯾﻜ ﺎﻓﺊ – ﺣﺠ ﻢ‬

‫ﺣﻤﺾ اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ وﺣﻤﺾ اﻟﺨﻞ اﻟﻤﺘﻜﻮن ﻧﺘﯿﺠﺔ ﻟﺘﺤﻠﻞ ﺟﻤﯿ ﻊ‬
‫ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ – ﻓ ﺈن اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟﺨ ﻼت اﻟﻤﯿﺜﯿ ﻞ ﯾﻜ ﺎﻓﻲء‬
‫) ‪ ( V∞ - V0‬وﺗﺮﻛﯿﺰھ ﺎ )‪ (a – x‬ﻋﻨ ﺪ أي زﻣ ﻦ ﻣﻘ ﺪاره )‪ (t‬ﯾﻜ ﻮن‬
‫ﻣﻜﺎﻓﺌﺎ ً ﻟﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪( V∞ - V0 ) - ( Vt - V0 ) = V∞ − Vt‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬
‫ﯾﻤﻜﻦ ﻛﺘﺎﺑﺘﮭﺎ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫ﺑﻨﺎء ﻋﻠﻰ ذﻟﻚ ﻓﺈن اﻟﻤﻌﺎدﻟﺔ‬
‫‪ a-x‬‬ ‫‪‬‬
‫‪ln‬‬
‫‪( V∞ - V0 ) = k t‬‬
‫) ‪( V∞ − Vt‬‬
‫أو أن ‪:‬‬
‫=‪k‬‬
‫‪1‬‬
‫‪ln‬‬
‫) ‪( V∞ - V0‬‬
‫) ‪t ( V∞ − Vt‬‬

‫)‪(431‬‬
‫ﻣﺜﺎﻝ )‪(٦-٢‬‬
‫ﯾﺤﺘ ﻮي اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﻋﻠ ﻰ ﺑﻌ ﺾ اﻟﻤﻌﻠﻮﻣ ﺎت اﻟﺤﺮﻛﯿ ﺔ ﻋ ﻦ ﺗﻤﯿ ﺆ‬
‫ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (25 ºC‬ﻓ ﻲ وﺟ ﻮد )‪(0.35 M‬‬
‫ﻣﻦ ﺣﻤﺾ اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ ﻛﺤﻔﺎز‪.‬‬
‫‪Time/min‬‬ ‫‪0‬‬ ‫‪20‬‬ ‫‪75‬‬ ‫‪119‬‬ ‫∞‬
‫‪Volume of alkali used/cm 3‬‬ ‫‪24.36‬‬ ‫‪25.85‬‬ ‫‪29.43‬‬ ‫‪31.85‬‬ ‫‪47.15‬‬
‫ﺑﺎﻻﻋﺘﻤ ﺎد ﻋﻠ ﻰ اﻟﻤﻌﻠﻮﻣ ﺎت اﻟﺴ ﺎﺑﻘﺔ ﺑ ﺮھﻦ ﺑ ﺄن ﺗﻤﯿ ﺆ ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ‬

‫ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻹﺛﺒﺎت أن اﻟﺘﻔﺎﻋﻞ ﯾﺘﺒﻊ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﺈﻧﻨﺎ ﻧﻮﺟﺪ ﻗﯿﻤﺔ )‪ (k‬ﻋﻨﺪ أزﻣﻨ ﺔ‬
‫ﻣﺨﺘﻠﻔﺔ ﺑﺎﺳﺘﺨﺪام ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ اﻟﺘﻲ ﻗﺮرﻧﺎ أﻧﮭﺎ ﺗﺄﺧ ﺬ اﻟﺼ ﻮرة‬
‫اﻟﺘﺎﻟﯿﺔ ﺑﺪﻻﻟﺔ اﻟﺤﺠﻮم ‪:‬‬
‫‪ln‬‬
‫‪( V∞ - V0 ) = k t‬‬
‫) ‪( V∞ − Vt‬‬
‫وﻹﯾﺠﺎد )‪ (k‬ﺗﺆول ھﺬه اﻟﻌﻼﻗﺔ اﻟﻰ ‪:‬‬
‫) ‪1 ( V∞ - V0‬‬
‫‪k = ln‬‬
‫) ‪t ( V∞ − Vt‬‬
‫ﺣﯿﺚ ‪:‬‬
‫‪ : V0‬ﺣﺠﻢ اﻟﻘﺎﻋﺪة اﻟﻤﺴﺘﺨﺪم ﻋﻨﺪ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ‬
‫‪ : Vt‬ﺣﺠﻢ اﻟﻘﺎﻋﺪة اﻟﻤﺴﺘﺨﺪم ﻋﻨﺪ زﻣﻦ ‪ t‬ﻣﻦ اﻟﺘﻔﺎﻋﻞ‬
‫∞‪ : V‬ﺣﺠﻢ اﻟﻘﺎﻋﺪة اﻟﻤﺴﺘﺨﺪم ﻋﻨﺪ اﻛﺘﻤﺎل اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫)‪(432‬‬
‫وﺑﻌﻤﻞ اﻟﺠﺪول اﻟﻼزم ‪:‬‬

‫) ‪( V0 = 24.36 ) , ( V∞ = 47.15cm3‬‬
‫) ‪( V - V = 47.15 - 24.36 = 22.79 cm‬‬
‫∞‬ ‫‪0‬‬
‫‪3‬‬
‫‪Time/min‬‬ ‫‪20‬‬ ‫‪75‬‬ ‫‪119‬‬

‫‪Volume of alkali used/cm3‬‬ ‫‪25.85‬‬ ‫‪29.43‬‬ ‫‪31.85‬‬
‫) ‪( V∞ − Vt‬‬ ‫‪21.3‬‬ ‫‪17.72‬‬ ‫‪15.3‬‬
‫) ‪1 ( V∞ - V0‬‬
‫‪k = ln‬‬ ‫)‪(min-1‬‬ ‫‪3.38 × 10-3‬‬ ‫‪3.36 × 10-3‬‬ ‫‪3.35 × 10-3‬‬
‫) ‪t ( V∞ − Vt‬‬
‫وﻣ ﻦ اﻟﺠ ﺪول ﻓ ﺈن ﻗﯿﻤ ﺔ )‪ (k‬ﺛﺎﺑﺘ ﺔ ﺗﻘﺮﯾﺒ ﺎً‪ ،‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﺗﻤﯿ ﺆ ﺧ ﻼت‬
‫اﻟﻤﯿﺜﯿﻞ ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﺏ( ﺗﻔﻜﻚ ﺍﳌﺮﻛﺐ ﺩﻳﺎﺯﻭﻧﻴﻮﻡ ﻛﻠﻮﺭﻳﺪ ﺑﻨﺰﻳﻦ )‪ (C6H5N=NCl‬ﰲ ﺍﳌﺎء‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬

‫ﺑﺪﻻﻟ ﺔ اﻟﺤﺠ ﻮم‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫ﺗﺠ ﺪر اﻹﺷ ﺎرة اﻟ ﻰ أن ﺷ ﻜﻞ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ a-x‬‬ ‫‪‬‬
‫ﯾﺘﻐﯿ ﺮ ﺣﺴ ﺐ ﻧ ﻮع اﻟﺘﻔﺎﻋ ﻞ اﻟﻤ ﺪروس‪ ،‬ﻓﻌﻠ ﻰ ﺳ ﺒﯿﻞ اﻟﻤﺜ ﺎل ﻓ ﻲ ﺣﺎﻟ ﺔ‬

‫ﺗﻔﻜﻚ اﻟﻤﺮﻛﺐ )‪ (C6H5N=NCl‬ﻓﻲ اﻟﻤﺎء ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪C6 H 5 N=NCl + H 2O ‬‬
‫‪→ C 6 H 5OH + HCl + N 2‬‬
‫ﺣﯿﺚ درس اﻟﺘﻔﺎﻋﻞ ﻋﻦ طﺮﯾﻖ ﻗﯿﺎس ﺣﺠﻢ ﻏﺎز اﻟﻨﯿﺘ ﺮوﺟﯿﻦ اﻟﻤﺘﻜ ﻮن‬
‫ﻧﺘﯿﺠﺔ ﻟﺘﻔﻜﻚ )‪ (C6H5N=NCl‬ﻋﻨﺪ ﻓﺘﺮات زﻣﻨﯿﺔ ﻣﺨﺘﻠﻔﺔ‪ .‬وﻓ ﻲ ھ ﺬا‬
‫اﻟﺘﻔﺎﻋ ﻞ ﯾﻜ ﻮن ﺣﺠ ﻢ ﻏ ﺎز اﻟﻨﯿﺘ ﺮوﺟﯿﻦ اﻟﻤﺘﺼ ﺎﻋﺪ ﻣﻜﺎﻓﺌ ﺎ ً ﻟﻼﻧﺨﻔ ﺎض‬
‫اﻟﺤﺎﺻﻞ ﻓﻲ ﺗﺮﻛﯿﺰ اﻟﻤﺮﻛﺐ )‪ ،(C6H5N=NCl‬ﻓﺈذا ﻛﺎن ﺣﺠﻢ ﻏ ﺎز‬
‫اﻟﻨﯿﺘﺮوﺟﯿﻦ اﻟﻤﺘﺼﺎﻋﺪ ﻓﻲ ﻧﮭﺎﯾﺔ اﻟﺘﻔﺎﻋ ﻞ ﯾﺴ ﺎوي )∞‪ ،(V‬وﺣﺠﻤ ﮫ ﻋﻨ ﺪ‬

‫)‪(433‬‬
‫أي زﻣ ﻦ )‪ (t‬ﯾﺴ ﺎوي )‪ (Vt‬ﻓ ﺈن ‪ ( V∞ - Vt ) :‬ﯾﻜ ﺎﻓﻲء )‪(a – x‬‬

‫و )∞‪ (V‬ﯾﻜﺎﻓﻲء )‪.(a‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫وﺑﺘﻌﻮﯾﺾ ذﻟﻚ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ a-x‬‬ ‫‪‬‬
‫∞‪V‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪V∞ - Vt‬‬
‫أو أن ‪:‬‬
‫‪1‬‬ ‫∞‪V‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪t‬‬ ‫‪V∞ - Vt‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬

‫أﺧ ﺬت ﺷ ﻜﻠﯿﻦ ﻣﺨﺘﻠﻔ ﯿﻦ ﻋﻨ ﺪ‬ ‫‪ ln‬‬
‫‪ a-x‬‬
‫‪= kt ‬‬
‫‪‬‬
‫ﻻﺣ ﻆ أن اﻟﻤﻌﺎدﻟ ﺔ‬
‫ﺗﺤﻮﯾﻠﮭ ﺎ ﺑﺪﻻﻟ ﺔ اﻟﺤﺠ ﻮم‪ ،‬وذﻟ ﻚ ﺣﺴ ﺐ ﻧ ﻮع اﻟﺘﻔﺎﻋ ﻞ اﻟﻤ ﺪروس‪ ،‬ﻓﻔ ﻲ‬

‫) ‪ ( V∞ - V0‬‬ ‫‪‬‬
‫وﻓ ﻲ ﺗﻔﻜ ﻚ‬ ‫‪ ln‬‬ ‫‪= k t ‬‬ ‫ﺗﻤﯿ ﺆ ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ ﺗﺄﺧ ﺬ اﻟﺼ ﻮرة‬
‫) ‪ ( V∞ − Vt‬‬ ‫‪‬‬
‫‪‬‬ ‫∞‪V‬‬ ‫‪‬‬

‫‪ ln‬‬ ‫‪= kt ‬‬ ‫اﻟﻤﺮﻛﺐ )‪ (C6H5N=NCl‬أﺧﺬت اﻟﺼﻮرة‬
‫‪ V∞ - Vt‬‬ ‫‪‬‬

‫)‪(434‬‬
‫ﻣﺜﺎﻝ )‪(٧-٢‬‬
‫إذا ﻋﻠﻤﺖ أﻧﮫ ﺗﻤﺖ دراﺳﺔ ﺣﺪوث اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪C6 H5 N=NCl + H 2 O ‬‬
‫‪→ C6 H 5OH + HCl + N 2‬‬
‫ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة ﻣﻌﯿﻨ ﺔ وذﻟ ﻚ ﺑﻘﯿ ﺎس ﺣﺠ ﻢ ﻏ ﺎز اﻟﻨﯿﺘ ﺮوﺟﯿﻦ‬

‫اﻟﻤﺘﺼﺎﻋﺪ ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ وﺗﻢ اﻟﺤﺼﻮل ﻋﻠﻰ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪Time/s‬‬ ‫‪0‬‬ ‫‪1200‬‬ ‫‪3000‬‬ ‫‪4200‬‬ ‫∞‬
‫‪Volume of N 2 cm3‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪25‬‬ ‫‪33‬‬ ‫‪162‬‬
‫ﺑﺮھﻦ ﺑﺄن ھﺬا اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫ﺍﳊﻞ‬
‫ﻋﻨﺪ ﻣﻨﺎﻗﺸﺔ ﺗﻔﻜﻚ اﻟﻤﺮﻛﺐ )‪ (C6H5N=NCl‬ﺗﻮﺻﻠﻨﺎ اﻟ ﻰ أن ﻗ ﺎﻧﻮن‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺑﺪﻻﻟﺔ اﻟﺤﺠﻮم وھﻮ ﻛﺎﻟﺘﺎﻟﻲ‪:‬‬
‫∞‪V‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪V∞ - Vt‬‬
‫وﯾﻜﻮن ﻗﺎﻧﻮن ﺣﺴﺎب )‪ (k‬ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬
‫‪1‬‬ ‫∞‪V‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪t‬‬ ‫‪V∞ - Vt‬‬
‫ﺣﯿﺚ ‪:‬‬
‫‪ :‬ﺣﺠﻢ اﻟﻨﯿﺘﺮوﺟﯿﻦ ﻋﻨﺪ ﻧﮭﺎﯾﺔ اﻟﺘﻔﺎﻋﻞ‬ ‫) ∞‪( V‬‬
‫)‪ : (Vt‬ﺣﺠﻢ اﻟﻨﯿﺘﺮوﺟﯿﻦ ﻋﻨﺪ أي زﻣﻦ )‪(t‬‬

‫)‪(435‬‬
‫وﻟﻜﻲ ﻧﺒﺮھﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻻ ﺑﺪ ﻣﻦ ﺣﺴﺎب ﻗﯿﻤﺔ )‪(k‬‬

‫‪ ،  k = 1t ln‬وﺑﻌﻤ ﻞ‬ ‫‪V∞ ‬‬
‫‪‬‬ ‫ﻋﻨ ﺪ أزﻣﻨ ﺔ ﻣﺨﺘﻠﻔ ﺔ ﺑﺎﺳ ﺘﺨﺪام اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪V∞ - Vt ‬‬
‫اﻟﺠﺪول اﻟﻼزم ‪:‬‬

‫‪(V‬‬ ‫∞‬ ‫) ‪= 162 cm3‬‬
‫‪Time/s‬‬ ‫‪1200‬‬ ‫‪3000‬‬ ‫‪4200‬‬
‫‪Volume of N2 cm3‬‬ ‫‪10‬‬ ‫‪25‬‬ ‫‪33‬‬
‫) ‪( V∞ − Vt‬‬ ‫‪152‬‬ ‫‪137‬‬ ‫‪129‬‬
‫‪1‬‬ ‫∞‪V‬‬
‫=‪k‬‬ ‫‪ln‬‬ ‫)‪(s-1‬‬
‫‪t‬‬ ‫‪V∞ - Vt‬‬ ‫‪5.31 × 10-5 5.59 × 10-5 5.42 × 10-5‬‬
‫وﻣﻦ اﻟﺠ ﺪول ﻓ ﺈن ﻗﯿﻤ ﺔ )‪ (k‬ﺗﻘﺮﯾﺒ ﺎ ً ﺛﺎﺑﺘ ﺔ وھ ﺬا ﯾ ﺪل ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ‬


‫)‪(436‬‬
‫ﻣﺜﺎﻝ )‪(٨-٢‬‬
‫ﯾﺘﻔﻜﻚ دﯾﺎزوﻧﯿﻮم ﻛﻠﻮرﯾﺪ ﺑﻨﺰﯾﻦ طﺒﻘﺎ ً ﻟﻠﺪرﺟﺔ اﻷوﻟﻰ ‪:‬‬
‫)‪Time (min.‬‬ ‫‪5‬‬ ‫‪10‬‬ ‫‪15‬‬ ‫‪20‬‬ ‫∞‬
‫)‪Volume of N2 (ml‬‬ ‫‪17.5‬‬ ‫‪29.7‬‬ ‫‪38.2‬‬ ‫‪44.3‬‬ ‫‪58.3‬‬
‫أﺛﺒﺖ أن اﻟﺘﻔﺎﻋﻞ ﯾﺘﺒﻊ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ؟‬
‫ﺍﳊﻞ‬
‫ﺑﺎﻟﺘﻌﻮﯾﺾ ﺑﺎﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪1‬‬ ‫∞‪V‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪t V∞ - Vt‬‬
‫‪2.303‬‬ ‫‪58.3‬‬
‫=‪k‬‬ ‫‪log‬‬ ‫‪= 0.0713 min -1‬‬
‫‪5‬‬ ‫‪58.3 - 17.5‬‬
‫‪2.303‬‬ ‫‪58.3‬‬
‫=‪k‬‬ ‫‪log‬‬ ‫‪= 0.0712 min -1‬‬
‫‪10‬‬ ‫‪58.3 - 29.7‬‬
‫‪2.303‬‬ ‫‪58.3‬‬
‫=‪k‬‬ ‫‪log‬‬ ‫‪= 0.0713 min -1‬‬
‫‪20‬‬ ‫‪58.3 - 44.3‬‬
‫ﻧﻼﺣﻆ أن ﻗﯿﻢ )‪ (k‬ﺛﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﻣﻊ ﻣﺮور اﻟﺰﻣﻦ ﻣﻤﺎ ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ‬


‫)‪(437‬‬
‫ﺝ( ﺍﻟﺘﻔﻜﻚ ﺍﳊﺮﺍﺭﻱ ﳋﺎﻣﺲ ﺃﻛﺴﻴﺪ ﺍﻟﻨﻴﱰﻭﺟﲔ )‪(N2O5‬‬
‫ﯾﺘﻔﻜﻚ ﺧﺎﻣﺲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ﻓﻲ وﺟﻮد راﺑﻊ ﻛﻠﻮرﯾﺪ اﻟﻜﺮﺑﻮن ﻋﻨﺪ‬

‫)‪ (30 ºC‬ﻛﻤﺎ ھﻮ ﻣﺒﯿﻦ ﺑﺎﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪N 2O5 ‬‬
‫‪→ 2NO 2 + O2‬‬
‫وﺣﯿ ﺚ أن ﻛ ﻼً ﻣ ﻦ )‪ (N2O5‬و )‪ (NO2‬ﯾ ﺬوب ﻓ ﻲ راﺑ ﻊ ﻛﻠﻮرﯾ ﺪ‬

‫اﻟﻜﺮﺑ ﻮن ﺑﯿﻨﻤ ﺎ )‪ (O2‬ﯾﺘﺤ ﺮر وﯾﺨ ﺮج ﻣ ﻦ اﻟﻤ ﺬﯾﺐ‪ ،‬وﯾﻤﻜ ﻦ ﻗﯿ ﺎس‬
‫اﻷﻛﺴ ﺠﯿﻦ ﺑﻤﻘﯿ ﺎس ﻣ ﺪرج ﻣﺘﺼ ﻞ ﺑ ﺪورق اﻟﺘﻔﺎﻋ ﻞ ﻛﻤ ﺎ ﻓ ﻲ اﻟﺸ ﻜﻞ‬
‫)‪.(١-٢‬‬
‫‪Fig. (2-18) : Gas burette for measuring the rate of evolution of a gas‬‬
‫‪during a chemical reaction‬‬

‫)‪(438‬‬
‫وﺑﻤﺮور اﻟﺰﻣﻦ ﯾﻘﺎس اﻷﻛﺴﺠﯿﻦ‪ ،‬ﺣﺘ ﻰ إﺗﻤ ﺎم ﺧ ﺮوج اﻷﻛﺴ ﺠﯿﻦ‪ .‬ﻓﻠ ﻮ‬
‫ﻓﺮﺿ ﻨﺎ أن اﻟﺤﺠ ﻢ اﻟﻜﻠ ﻲ ) ∞‪ ( V‬ﻟﻸﻛﺴ ﺠﯿﻦ‪ ،‬و )‪ (Vt‬ﺣﺠ ﻢ اﻷﻛﺴ ﺠﯿﻦ‬
‫ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ‪.‬‬
‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ )‪ (a‬ھﻮ ) ∞‪( V‬‬
‫اﻟﺘﺮﻛﯿﺰ اﻟﺰﻣﻨﻲ )‪ (x‬ھﻮ ‪Vt‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪a ‬‬
‫ﻧﺤﺼ ﻞ‬ ‫‪‬‬ ‫‪k‬‬ ‫=‬ ‫‪log‬‬ ‫اﻷوﻟ ﻰ ‪‬‬ ‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ‬
‫‪‬‬ ‫‪t‬‬ ‫‪(a - x) ‬‬
‫ﻋﻠﻰ‬
‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫)‪(a - x‬‬

‫)‪(439‬‬
‫‪ (٢‬ﻗﺎﻧﻮﻥ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ﺑﺪﻻﻟﺔ ﺍﻟﻀﻐﻂ‬
‫ﺗﻔﻜﻚ ﺍﻵﺯﻭﺃﻳﺰﻭﺑﺮﻭﺑﺎﻥ )‪(Azoisopropane‬‬
‫ﯾﺘﻔﻜ ﻚ ﻣﺮﻛ ﺐ اﻵزوأﯾﺰوﺑﺮوﺑ ﺎن ﺣﺮارﯾ ﺎ ً ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي اﻟ ﻰ‬

‫ھﻜﺴﺎن وﻧﯿﺘﺮوﺟﯿﻦ ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪( CH 3 )2 CHN=NCH(CH3 )2 ‬‬
‫‪→ N 2 + C6 H14‬‬
‫وﻟﻘ ﺪ ﺗﻤ ﺖ دراﺳ ﺔ ﺗﻔﻜ ﻚ ھ ﺬا اﻟﻤﺮﻛ ﺐ ﺣﺮارﯾ ﺎ ً ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي‪،‬‬

‫وذﻟﻚ ﺑﻤﺘﺎﺑﻌﺔ ﺗﻐﯿﺮ اﻟﻀﻐﻂ ﻣﻊ اﻟ ﺰﻣﻦ‪ .‬وﻣ ﻦ اﻟﻮاﺿ ﺢ أن اﻟﻤﻌﻠﻮﻣ ﺎت‬
‫اﻟﺘﻲ ﯾﻤﻜﻦ ﻗﯿﺎﺳ ﮭﺎ ھ ﻲ اﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻠﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ ،‬واﻟﻀ ﻐﻂ‬
‫اﻟﻜﻠ ﻲ ﻓ ﻲ اﻟﻨﻈ ﺎم ﻋﻨ ﺪ ﻣﺮاﺣ ﻞ ﻣﺨﺘﻠﻔ ﺔ ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ‪ ،‬وﺳ ﻮف ﻧﻮﺿ ﺢ‬
‫ﻛﯿﻒ ﯾﻤﻜﻦ ﺣﺴﺎب ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻹﻋﺘﻤ ﺎد ﻋﻠ ﻰ ھ ﺬا اﻟﻀ ﻐﻂ‬
‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫ﻧﻔﺘ ﺮض أن اﻟﻀ ﻐﻂ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﻤﺮﻛ ﺐ )‪(Azoisopropane‬‬
‫ﯾﺴﺎوي ) ‪ ( Pο‬وھ ﻮ ﯾﻜ ﺎﻓﻲء اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ )‪ ،(a‬وأن )‪ (PA‬ﺿ ﻐﻂ‬
‫ﻣ ﺎ ﺗﺒﻘ ﻰ ﻣ ﻦ اﻟﻤﺮﻛ ﺐ )‪ (Azoisopropane‬وھ ﻮ ﯾﻜ ﺎﻓﻲء اﻟﺤ ﺪ‬
‫)‪ (a – x‬اﻟﺬي ﯾﻤﺜﻞ ﺗﺮﻛﯿ ﺰ ﻣ ﺎ ﺗﺒﻘ ﻰ ﻣ ﻦ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ .‬وﻣ ﻦ ذﻟ ﻚ‬
‫ﻧﺴﺘﻨﺘﺞ أن اﻹﻧﺨﻔﺎض ﻓﻲ اﻟﺘﺮﻛﯿﺰ )‪ (x‬ﯾﻜﺎﻓﻲء ﺿﻐﻂ اﻟﻤ ﺎدة اﻟﻤﺘﻔﻜﻜ ﺔ‬
‫) ‪. ( Pο − PA‬‬

‫)‪(440‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪‬‬

‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫ﺑﺎﻹﻋﺘﻤﺎد ﻋﻠﻰ ﻣﺎ ﺳﺒﻖ ﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ a-x‬‬ ‫‪‬‬
‫‪Pο‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪PA‬‬
‫أو أن ‪:‬‬
‫‪1 Pο‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪t PA‬‬
‫وﺗﺠﺪراﻹﺷﺎرة ھﻨﺎ اﻟﻰ أﻧﮫ ﻻ ﯾﻤﻜ ﻦ ﻗﯿ ﺎس ﺿ ﻐﻂ ﻣ ﺎ ﺗﺒﻘ ﻰ ﻣ ﻦ اﻟﻤ ﺎدة‬

‫اﻟﻤﺘﻔﺎﻋﻠ ﺔ )‪ (PA‬ﺑﻤﻔ ﺮده‪ ،‬اﻷﻣ ﺮ اﻟ ﺬي ﻻ ﯾﻤﻜ ﻦ ﻣ ﻦ اﺳ ﺘﺨﺪام اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ Pο‬‬ ‫‪‬‬
‫ﻟﺬا ﻓﺈﻧﮫ ﯾﺠﺐ إﺟﺮاء ﺗﻌﺪﯾﻞ ﻋﻠ ﻰ ھ ﺬه اﻟﻤﻌﺎدﻟ ﺔ‪ ،‬وذﻟ ﻚ‬ ‫‪، P‬‬
‫‪ln‬‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬
‫‪‬‬ ‫‪A‬‬ ‫‪‬‬
‫ﺑﺈدﺧﺎل اﻟﻤﺘﻐﯿﺮ اﻟﺬي ﯾﻤﻜﻦ ﻗﯿﺎﺳﮫ ﻓ ﻲ ﻣﺜ ﻞ ھ ﺬا اﻟﻨﻈ ﺎم‪ ،‬وھ ﻮ اﻟﻀ ﻐﻂ‬
‫اﻟﻜﻠ ﻲ )‪ (Pt‬ﻋﻨ ﺪ أي زﻣ ﻦ ﻗ ﺪره )‪ (t‬وھ ﻮ ﯾﺴ ﺎوي ﻣﺠﻤ ﻮع اﻟﻀ ﻐﻮط‬
‫اﻟﺠﺰﯾﺌﯿﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Pt = PA + PN2 + PC6 H14‬‬
‫) ‪Pt = PA + 2 (Po - PA‬‬
‫وﻟﻘﺪ ﺗﻢ ﺿﺮب اﻟﺤﺪ )‪ (Po – PA‬ﺑﺎﻟﻌﺪد اﺛﻨﯿﻦ ﻷﻧﮫ ﻛﻠﻤﺎ ﺗﻔﻜ ﻚ ﺟ ﺰيء‬
‫واﺣﺪ ﻣﻦ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﻧﺘﺞ ﻋﻨﮫ ﺟﺰﯾﺌﺎن ﻣ ﻦ اﻟﻤ ﻮاد اﻟﻨﺎﺗﺠ ﺔ ﺿ ﻐﻂ‬
‫ﻛﻞ ﻣﻨﮭﻤﺎ ﯾﺴﺎوي )‪.(Po – PA‬‬

‫)‪(441‬‬
‫ﻣ ﻦ اﻟﻤﻌﺎدﻟ ﺔ اﻟﺴ ﺎﺑﻘﺔ ﯾﻤﻜ ﻦ اﺳ ﺘﻨﺘﺎج أن ﺿ ﻐﻂ ﻣ ﺎ ﺗﺒﻘ ﻰ ﻣ ﻦ اﻟﻤ ﺎدة‬

‫اﻟﻤﺘﻔﺎﻋﻠﺔ ﺑﺪﻻﻟﺔ اﻟﻀﻐﻂ اﻟﻜﻠ ﻲ )‪ (Pt‬واﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ )‪ (Po‬ﯾﻜ ﻮن‬
‫) ‪Pt = PA + 2 (Po - PA‬‬
‫‪Pt = PA + 2Po - 2PA‬‬
‫‪Pt = - PA + 2 Po‬‬
‫‪⇒ PA = 2Po - Pt‬‬
‫‪ Pο‬‬ ‫‪‬‬

‫ﻧﺤﺼ ﻞ‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﺑ ـ ‪ ( PA = 2Po - P )t‬ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ PA‬‬ ‫‪‬‬
‫ﻋﻠﻰ ‪:‬‬
‫‪Pο‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪2Po - Pt‬‬
‫‪‬‬ ‫‪Pο‬‬ ‫‪‬‬

‫ﻗﺎﺑﻠﺔ ﻟﻠﺘﻄﺒﯿﻖ ﺣﯿﺚ أﻧﮫ ﯾﻤﻜﻦ ﻗﯿﺎس ﻛﻞ ﻣﻦ‬ ‫‪ ln‬‬ ‫‪= kt ‬‬ ‫واﻟﻤﻌﺎدﻟﺔ‬
‫‪ 2Po - Pt‬‬ ‫‪‬‬
‫اﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ )‪ (Po‬ﻟﻠﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ ،‬واﻟﻀ ﻐﻂ اﻟﻜﻠ ﻲ )‪ (Pt‬ﻓ ﻲ‬

‫اﻟﻨﻈ ﺎم‪ ،‬وذﻟ ﻚ ﻟﺤﺴ ﺎب ﻗﯿﻤ ﺔ اﻟﺜﺎﺑ ﺖ )‪ (k‬ﻋ ﻦ طﺮﯾ ﻖ رﺳ ﻢ اﻟﻌﻼﻗ ﺎت‬
‫اﻟﺒﯿﺎﻧﯿﺔ اﻟﻤﻨﺎﺳﺒﺔ ﺑﯿﻦ اﻟﻀﻐﻂ واﻟﺰﻣﻦ‪.‬‬

‫)‪(442‬‬
‫ﻣﺜﺎﻝ )‪(٩-٢‬‬
‫ﯾﺤﺘ ﻮي اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﻋﻠ ﻰ ﺑﻌ ﺾ اﻟﻤﻌﻠﻮﻣ ﺎت اﻟﺤﺮﻛﯿ ﺔ ﻋﻨ ﺪ ﺗﻔﻜ ﻚ‬

‫ﻣﺮﻛ ﺐ اﻵزوأﯾﺰوﺑﺮوﺑ ﺎن ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة‬
‫)‪ (270 ºC‬وذﻟﻚ ﺑﻤﺘﺎﺑﻌﺔ ﺗﻐﯿﺮ اﻟﻀﻐﻂ ﻣﻊ اﻟﺰﻣﻦ‪.‬‬
‫‪Time/min.‬‬ ‫‪0‬‬ ‫‪3‬‬ ‫‪6‬‬ ‫‪9‬‬ ‫‪12‬‬ ‫‪17‬‬
‫‪Pressure/ mmHg‬‬ ‫‪35.15‬‬ ‫‪46.30‬‬ ‫‪53.90‬‬ ‫‪58.85‬‬ ‫‪62.20‬‬ ‫‪65.85‬‬
‫ﺑ ﺮھﻦ ﺑﺎﻹﻋﺘﻤ ﺎد ﻋﻠ ﻰ ھ ﺬه اﻟﻤﻌﻠﻮﻣ ﺎت ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﯾﺘﺒ ﻊ ﻗ ﺎﻧﻮن‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻋﻨ ﺪ ﻣﻨﺎﻗﺸ ﺔ ﺗﻔﻜ ﻚ اﻵزوأﯾﺰوﺑﺮوﺑ ﺎن ﺗﻮﺻ ﻠﻨﺎ اﻟ ﻰ أن ﻗ ﺎﻧﻮن ﺛﺎﺑ ﺖ‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﯾﺼﺒﺢ ﺑﺪﻻﻟﺔ اﻟﻀﻐﻂ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Pο‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪2Po - Pt‬‬
‫وﻗﯿﻤﺔ )‪ (k‬ﺗﺤﺴﺐ ﻣﻨﮫ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪1‬‬ ‫‪Pο‬‬
‫‪k = ln‬‬
‫‪t 2Po - Pt‬‬

‫)‪(443‬‬
‫ﺣﯿﺚ ‪:‬‬
‫‪ : Po‬اﻟﻀﻐﻂ ﻓﻲ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ‬
‫‪ : Pt‬اﻟﻀﻐﻂ اﻟﻜﻠﻲ ﻋﻨﺪ أي زﻣﻦ )‪.(t‬‬
‫وﻟﻜ ﻲ ﻧﺒ ﺮھﻦ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻧﺤﺴ ﺐ ﻗﯿﻤ ﺔ )‪ (k‬ﻋﻨ ﺪ‬
‫أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻷوﻟﻰ اﻟﺬي ﯾﺄﺧﺬ اﻟﺼ ﻮرة‬
‫‪‬‬ ‫‪1‬‬ ‫‪Pο ‬‬
‫‪ ،  k = t ln‬وﺑﻌﻤﻞ اﻟﺠﺪول اﻟﻼزم ‪:‬‬ ‫‪‬‬
‫‪‬‬ ‫‪2Po - Pt ‬‬
‫) ‪( Po = 35.15 mmHg‬‬
‫) ‪( 2Po = 2 × 35.15 = 70.3 mmHg‬‬
‫‪Time/ min.‬‬ ‫‪3‬‬ ‫‪6‬‬ ‫‪9‬‬ ‫‪12‬‬ ‫‪17‬‬
‫‪Pt/mmHg‬‬ ‫‪46.30‬‬ ‫‪53.90‬‬ ‫‪58.85‬‬ ‫‪62.20‬‬ ‫‪65.85‬‬
‫‪2Po - Pt‬‬ ‫‪24‬‬ ‫‪16.4‬‬ ‫‪11.45‬‬ ‫‪8.1‬‬ ‫‪4.45‬‬
‫‪1‬‬ ‫‪Pο‬‬
‫‪k = ln‬‬ ‫)‪(min-1‬‬
‫‪t‬‬ ‫‪2Po - Pt‬‬ ‫‪0.1272‬‬ ‫‪0.1271‬‬ ‫‪0.1246‬‬ ‫‪0.1223‬‬ ‫‪0.1216‬‬
‫وﺣﯿ ﺚ أن ﻗﯿﻤ ﺔ )‪ (k‬ﺗﻘﺮﯾﺒ ﺎ ً ﺛﺎﺑﺘ ﺔ ﻓ ﺈن ھ ﺬا ﯾﺒ ﺮھﻦ أن ﺗﻔﻜ ﻚ ﻣﺮﻛ ﺐ‬

‫اﻵزوأﯾﺰوﺑﺮوﺑ ﺎن ﺣﺮارﯾ ﺎ ً ﯾﺘﺒ ﻊ ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬
‫اﻷوﻟﻰ‪.‬‬

‫)‪(444‬‬
‫ﻣﺜﺎﻝ )‪(١٠-٢‬‬
‫ﯾﺘﻔﻜﻚ إﯾﺜﯿﻞ اﻷﻣﯿﻦ ﻋﻨﺪ ﺿﻐﻂ اﺑﺘﺪاﺋﻲ ﻗ ﺪره )‪ (55 mmHg‬ودرﺟ ﺔ‬
‫ﺣ ﺮارة )‪ (500 ºC‬ﻓ ﻲ ﺗﻔﺎﻋ ﻞ ﻏﯿ ﺮ ﻋﻜﺴ ﻲ ﻟﯿﻨ ﺘﺞ اﻷﻣﻮﻧﯿ ﺎ واﻹﯾﺜﻠ ﯿﻦ‬
‫ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪C2 H 5 NH 2 (g) ‬‬
‫‪Δ‬‬
‫)‪→ C2 H 4 (g) + NH3 (g‬‬
‫ﻓﺈذا ﻗﯿﺲ ﺗﻐﯿﺮ اﻟﻀﻐﻂ ﻣﻊ اﻟﺰﻣﻦ ﺣﺴﺐ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬

‫)‪t (min‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫‪P‬‬ ‫‪60‬‬ ‫‪64‬‬ ‫‪72‬‬ ‫‪84‬‬ ‫‪89‬‬ ‫‪102‬‬ ‫‪107‬‬ ‫‪108.5‬‬
‫أوﺟ ﺪ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ وﻗﯿﻤ ﺔ )‪ (k‬ﺑﺎﻟﻄﺮﯾﻘ ﺔ اﻟﺤﺴ ﺎﺑﯿﺔ ﺛ ﻢ ﺑﺎﻟﻄﺮﯾﻘ ﺔ‬

‫اﻟﺒﯿﺎﻧﯿﺔ؟‬
‫ﺍﳊﻞ‬
‫‪‬‬ ‫‪‬‬
‫واﻟﺘ ﻲ ﯾﻨ ﺘﺞ ﻣﻨﮭ ﺎ اﻟﻌﻼﻗ ﺔ‬ ‫‪ ln‬‬
‫‪Pο‬‬
‫‪= kt ‬‬ ‫ﺑﺘﻄﺒﯿ ﻖ اﻟﻌﻼﻗ ﺔ‬
‫‪ 2Po - Pt‬‬ ‫‪‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪Pο ‬‬
‫ﻧﺤﺴﺐ ﻗﯿﻤﺔ )‪ (k‬ﻛﻤﺎ ﻓﻲ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬ ‫‪ k = ln‬‬ ‫‪‬‬
‫‪‬‬ ‫‪t 2Po - Pt ‬‬
‫) ‪( Po = 55 mmHg‬‬
‫) ‪( 2Po = 2 × 55 = 110 mmHg‬‬
‫‪Time/ min.‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫‪Pt/mmHg‬‬ ‫‪60‬‬ ‫‪64‬‬ ‫‪72‬‬ ‫‪84‬‬ ‫‪89‬‬ ‫‪102‬‬ ‫‪107‬‬ ‫‪108.5‬‬
‫‪2Po - Pt‬‬
‫‪1‬‬
‫‪k = ln‬‬
‫‪Pο‬‬ ‫)‪(min-1‬‬
‫‪t 2Po - Pt‬‬

‫)‪(445‬‬
‫وﺑﻌﺪ إﻛﻤ ﺎل اﻟﺠ ﺪول اﻟﺴ ﺎﺑﻖ ﺳ ﺘﺠﺪ أن ﻗﯿﻤ ﺔ )‪ (k‬ﺣﯿﻨﻤ ﺎ ﻋﻮﺿ ﻨﺎ ﺑﮭ ﺎ‬
‫ﻓﻲ ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻷوﻟﻰ وﺗﺴﺎوي ﺗﻘﺮﯾﺒﺎ ً )‪.(k = 9.53 × 10-2 min-1‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................................................. ...........‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪................................................................................................................................................. .......................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪..................................................................................................................... ...................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪................................................................................................................................................................ ........................‬‬
‫‪......................................................................................... ...............................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪.................................................................................................................................... ....................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................................................... .........‬‬
‫‪........................................................................................................ ................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬

‫)‪(446‬‬
‫ﺗﻄﺒﻴﻘﺎﺕ ﺣﺴﺎﺑﻴﺔ ﻋﻠﻰ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ‬

‫ﻣﺜﺎﻝ )‪(١١-٢‬‬
‫اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ اﻟﺘﺎﻟﻲ ﻣﻦ اﻟﻤﺮﺗﺒﺔ اﻷﺣﺎدﯾﺔ وﻟﮫ ﺛﺎﺑﺖ ﺳﺮﻋﺔ ﻣﻘﺪاره‬

‫)‪ (k = 2.2 × 10-5 s-1‬ﻋﻨﺪ درﺟﺔ ﺣﺮارة( )‪.(T = 593 K‬‬
‫‪ SO 2 + Cl 2‬‬
‫‪SO 2Cl2 ‬‬
‫ﻓﻤﺎ ﻧﺴﺒﺔ ﺗﺤﻠﻞ )‪ (SO2Cl2‬ﺑﻌ ﺪ ﺗﺴ ﺨﯿﻨﮫ اﻟ ﻰ ﻧﻔ ﺲ اﻟﺪرﺟ ﺔ اﻟﺤﺮارﯾ ﺔ‬

‫وﻟﻤﺪة ﺳﺎﻋﺘﯿﻦ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪a-x‬‬
‫‪a‬‬
‫‪= ek t‬‬
‫‪a-x‬‬
‫‪a‬‬
‫‪= e2.2 × 10 × 2 × 3600‬‬
‫‪-5‬‬
‫) ‪(a - x‬‬
‫‪a‬‬
‫‪= 1.1716‬‬
‫) ‪(a - x‬‬
‫= ) ‪(a - x‬‬ ‫‪1‬‬
‫‪a‬‬ ‫‪1.1716‬‬
‫‪( a - x ) = 0.8535‬‬
‫‪a‬‬
‫وﯾﻤﺜﻞ ھﺬا ﻧﺴﺒﺔ اﻟﺘﺤﻠﻞ ﺑﻌﺪ ﻣﺮور ﺳﺎﻋﺘﯿﻦ‪.‬‬

‫)‪(447‬‬
‫ﻣﺜﺎﻝ )‪(١٢-٢‬‬
‫ﻓ ﻲ ﺗﻔﺎﻋ ﻞ ﻣﻌ ﯿﻦ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺗﺒ ﯿﻦ أن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‬

‫ﯾﻨﺨﻔﺾ اﻟﻰ ﻧﺼﻒ ﻗﯿﻤﺘﮫ اﻹﺑﺘﺪاﺋﯿﺔ ﺑﻌﺪ )‪ (5000 s‬ﻓﻲ درﺟ ﺔ ﺣ ﺮارة‬
‫)‪ .(25 ºC‬أﻣﺎ ﻓﻲ درﺟﺔ ﺣﺮارة )‪ (37 ºC‬ﻓﺈن اﻟﺘﺮﻛﯿﺰ ﯾ ﻨﺨﻔﺾ اﻟ ﻰ‬
‫اﻟﻨﺼﻒ ﺑﻌﺪ ﻣﺮور )‪.(1000 s‬‬
‫اﺣﺴﺐ ‪:‬‬
‫أ( ﺛﺎﺑ ﺖ ﻣﻌ ﺪل ﺳ ﺮﻋﺔ )‪ (k‬اﻟﺘﻔﺎﻋ ﻞ ﺗﺤ ﺖ درﺟ ﺔ )‪ (25 ºC‬و‬
‫)‪.(37 ºC‬‬
‫ب( اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻻﻧﺨﻔ ﺎض اﻟﺘﺮﻛﯿ ﺰ اﻟ ﻰ رﺑ ﻊ اﻟﻘﯿﻤ ﺔ اﻹﺑﺘﺪاﺋﯿ ﺔ ﻓ ﻲ‬
‫درﺟﺔ )‪.(37 ºC‬‬
‫ج( طﺎﻗﺔ اﻟﺘﻨﺸﯿﻂ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫أ( ﺑﻤﺎ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﺈن ‪:‬‬

‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫‪a-x‬‬
‫وﺑﺎﺳﺘﺨﺪام زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ﻓﺈن ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ درﺟﺘﻲ اﻟﺤﺮارة‬
‫‪0.693 0.693‬‬
‫‪at 25 ο C‬‬ ‫=‪k‬‬ ‫=‬ ‫‪= 1.39 × 10-4 s -1‬‬
‫‪t1/2‬‬ ‫‪5000‬‬
‫‪0.693 0.693‬‬
‫‪at 37 ο C‬‬ ‫=‪k‬‬ ‫=‬ ‫‪= 6.93 × 10-4 s -1‬‬
‫‪t1/2‬‬ ‫‪1000‬‬

‫)‪(448‬‬
‫ب( ﻟﺤﺴﺎب اﻟﺰﻣﻦ اﻟﻼزم ﻻﻧﺨﻔﺎض اﻟﺘﺮﻛﯿﺰ اﻟﻰ رﺑﻊ ﻗﯿﻤﺘﮫ اﻹﺑﺘﺪاﺋﯿ ﺔ‬
‫ﻋﻨﺪ درﺟﺔ ﺣﺮارة )‪ (37 ºC‬ﻓﺈﻧﻨﺎ ﻧﻌﻮض ﺑﻘﯿﻤﺔ )‪ (k‬ﻋﻨﺪ ھﺬه اﻟﺪرﺟﺔ‬
‫‪‬‬ ‫‪a ‬‬
‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪ kt = 2.303 log‬‬ ‫‪‬‬ ‫ﻓﻲ اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪a-x‬‬
‫‪a‬‬
‫‪kt = 2.303 log‬‬
‫‪a-x‬‬
‫‪a‬‬
‫‪6.93 × 10-4 t1/4 = 2.303 log‬‬
‫‪0.25 a‬‬
‫‪a‬‬
‫‪2.303 log‬‬
‫‪0.25 a‬‬
‫= ‪t1/4‬‬
‫‪6.93 × 10-4‬‬
‫‪1‬‬
‫‪2.303 log‬‬
‫= ‪t1/4‬‬ ‫‪0.25‬‬
‫‪6.93 × 10-4‬‬
‫‪t1/4 = 2000.78 s‬‬
‫ج( ﻟﺤﺴ ﺎب طﺎﻗ ﺔ اﻟﺘﻨﺸ ﯿﻂ ﻧﻄﺒ ﻖ ﻣﻌﺎدﻟ ﺔ أرھﯿﻨﯿ ﻮس ﻋﻨ ﺪ درﺟﺘ ﻲ‬

‫)‪: (25 ºC, 37 ºC‬‬ ‫ﺣﺮارة‬
‫‪k2‬‬ ‫‪-ΔH  1 1 ‬‬
‫‪log‬‬ ‫=‬ ‫‪ - ‬‬
‫‪k1 2.303R  T2 T1 ‬‬
‫‪k2‬‬ ‫‪ΔE  T2 - T1 ‬‬
‫‪log‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪k1 2.303R  T2 T1 ‬‬
‫‪6.93 × 10-4‬‬ ‫‪∆E‬‬ ‫‪ 310 - 300 ‬‬
‫‪log‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪1.39 × 10‬‬ ‫‪-4‬‬
‫‪2.303 × 8.314  300 × 310 ‬‬
‫‪ΔE‬‬
‫= ‪0.698‬‬
‫‪19.15‬‬
‫(‬ ‫) ‪1.075 × 10-4‬‬
‫‪0.698 × 19.15‬‬
‫= ‪ΔE‬‬
‫) ‪(1.075 × 10-4‬‬
‫‪ΔE = 124.341 × 103 J/mol‬‬
‫‪ΔE = 124.341 kJ/mol‬‬

‫)‪(449‬‬
‫ﻣﺜﺎﻝ )‪(١٣-٢‬‬
‫ﯾﺘﺤﻠ ﻞ ﺑﯿﺮوﻛﺴ ﯿﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ )ﻓ ﻮق أﻛﺴ ﯿﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ( )‪(H2O2‬‬

‫وﻓﻘﺎ ً ﻟﻠﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪H 2O 2 (aq) ‬‬
‫)‪→ 2H 2 O(L) + O2 (g‬‬
‫وﺗﻢ دراﺳﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة ﺛﺎﺑﺘ ﺔ ‪ ،‬ﻓﻮﺟ ﺪ أن اﻧﺨﻔ ﺎض‬
‫ﺗﺮﻛﯿﺰ ﻓﻮق أﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ ﻣﻊ اﻟﺰﻣﻦ ﯾﺘﻢ وﻓﻖ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪Time, sec‬‬ ‫‪0‬‬ ‫‪300‬‬ ‫‪600‬‬ ‫‪900‬‬ ‫‪1200‬‬
‫‪[H2O2] mol/L‬‬ ‫‪0.100‬‬ ‫‪0.0776‬‬ ‫‪0.0603‬‬ ‫‪0.0468‬‬ ‫‪0.0363‬‬
‫ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻣﻦ ﺧﻼل اﻟﻤﻌﺎدﻻت واﺣﺴ ﺐ ﺛﺎﺑ ﺖ‬

‫اﻟﺴﺮﻋﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫‪a = 0.100‬‬
‫‪Time, sec‬‬ ‫‪300‬‬ ‫‪600‬‬ ‫‪900‬‬ ‫‪1200‬‬
‫‪[H2O2] = (a – x) mol/L‬‬ ‫‪0.0776‬‬ ‫‪0.0603‬‬ ‫‪0.0468‬‬ ‫‪0.0363‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪a  -1‬‬
‫= ‪k‬‬ ‫‪log‬‬ ‫‪s‬‬ ‫‪8.45 × 10-4‬‬ ‫‪8.43 × 10-4 8.44 × 10-4 8.45 × 10-4‬‬
‫‪‬‬ ‫‪t‬‬ ‫‪a-x‬‬
‫‪k = 8.443 × 10- 4‬‬
‫وﺑﻤﺎ أن اﻟﻘﯿﻢ ﺛﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟ ﻰ‪ .‬وﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ‬
‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﻌ ﺪ أﺧ ﺬ ﻣﻌ ﺪل ﺗﻠ ﻚ اﻟﻘ ﯿﻢ اﻟﻤﺘﻘﺎرﺑ ﺔ ھ ﻲ ‪:‬‬
‫)‪.(k = 8.443 × 10-4‬‬

‫)‪(450‬‬
‫ﻣﺜﺎﻝ )‪(١٤-٢‬‬
‫وﺟﺪ أن )‪ (30 %‬ﻣ ﻦ ﻣﺮﻛ ﺐ ﯾﺘﺤﻠ ﻞ ﻓ ﻲ ﻣ ﺪة )‪ (10 h‬وﺗﺤ ﺖ درﺟ ﺔ‬

‫ﺣﺮارة ﻣﻌﯿﻨﺔ‪ .‬ﻓﻜﻢ ﯾﻠﺰم ﻣﻦ اﻟﻮﻗﺖ ﻟﺘﺤﻠﻞ )‪ (99 %‬ﻣﻦ ﻧﻔ ﺲ اﻟﻤﺮﻛ ﺐ‬
‫ﻓﻲ ﺣﺎل ﻛﻮن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺪرﺟﺔ اﻷوﻟﻰ‪.‬‬
‫ﺍﳊﻞ‬
‫‪A‬‬ ‫‪‬‬
‫→‬ ‫‪B‬‬
‫‪t=0‬‬ ‫‪a‬‬ ‫‪x=0‬‬
‫‪t = 10‬‬ ‫)‪a - x = (a - 0.3a‬‬ ‫‪x = 0.3a‬‬
‫?‪t = h‬‬ ‫)‪a - x = (a - 0.99a‬‬ ‫‪x = 0.99a‬‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫) ‪( a - x1‬‬
‫) ‪( t 2 - t1 ) ( a - x 2‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫) ‪(10 × 3600 - 0 ) ( a - 0.3a‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪( 36000 - 0 ) 0.7 a‬‬
‫‪k = 9.91 × 10-6 s-1‬‬
‫إن ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (k‬ﺛﺎﺑ ﺖ ﻟﻠﺘﻔﺎﻋ ﻞ اﻟﻮاﺣ ﺪ ﻋﻨ ﺪ درﺟ ﺔ‬

‫ﺣ ﺮارة ﺛﺎﺑﺘ ﺔ‪ ،‬ﻟ ﺬﻟﻚ ﺑﺈﻋ ﺎدة ﺗﻄﺒﯿ ﻖ اﻟﻤﻌﺎدﻟ ﺔ ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﺤﺎﻟ ﺔ اﻟﺜﺎﻧﯿ ﺔ‬
‫ﻧﺴﺘﻄﯿﻊ ﺣﺴﺎب اﻟﺰﻣﻦ اﻟﻤﻄﻠﻮب ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

(451)
k=
2.303
log
( a - x1 )
( t 2 - t1 ) ( a - x 2 )
2.303 a
9.91 × 10−6 = log
( t - 0 ) ( a - 0.99 a )
2.303 a
9.91 × 10−6 = log
t 0.01 a
2.303
9.91 × 10−6 = × 2
t
t = 4.648 × 105 s
t = 129.1 h

‫)‪(452‬‬
‫ﻣﺜﺎﻝ )‪(١٥-٢‬‬
‫ﻋﻨ ﺪ ﺗﺤﻠ ﻞ إﯾﺜﯿ ﻞ ﺑﺮوﺑ ﺎﻧﻮﯾﻦ ﺑﻮﺟ ﻮد ﻋﺎﻣ ﻞ ﻣﺴ ﺎﻋﺪ ﺣﺎﻣﻀ ﻲ ﻓ ﺈن‬
‫)‪ (14.1 %‬ﻣﻦ اﻹﺳﺘﺮ ﯾﺘﺤﻠ ﻞ ﺑﻌ ﺪ )‪ ،(30 min‬و)‪ (70.3 %‬ﯾﺘﺤﻠ ﻞ‬
‫ﺑﻌﺪ )‪ .(240 min‬ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ .‬ﺛ ﻢ اﺣﺴ ﺐ ﻗﯿﻤ ﺔ‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ وزﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬
‫ﺍﳊﻞ‬
‫اﻟﺠﻮاب ‪ ، k = 8.40 × 10-5 s-1 :‬وزﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ﯾﺴﺎوي ‪.(t1/2 = 8240 s‬‬
‫ﺗﻔﺼﻴﻞ ﺍﳊﻞ‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪.................................................................................................................................................. ......................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪...................................................................................................................... ..................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪................................................................................................................................................................. .......................‬‬
‫‪.......................................................................................... ..............................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬

‫)‪(453‬‬
‫ﻣﺜﺎﻝ )‪(١٦-٢‬‬
‫ﻣﻦ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ﻟﺘﺤﻠﻞ ﺑﯿﺮوﻛﺴﯿﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ )‪ (H2O2‬ﻓ ﻲ ﻣﺤﻠ ﻮل‬
‫ﻣ ﺎﺋﻲ‪ ،‬ﺑ ﯿﻦ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ‪ ،‬واﺣﺴ ﺐ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ‬
‫)‪.(k‬‬
‫‪Time, s‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫‪V KMnO4, cm3‬‬ ‫‪25‬‬ ‫‪20‬‬ ‫‪15.7‬‬ ‫‪12.5‬‬ ‫‪9.6‬‬
‫‪ : V‬ھﻲ ﺣﺠﻢ ﺑﺮﻣﻨﺠﻨﺎت اﻟﺒﻮﺗﺎﺳ ﯿﻮم اﻟﻼزﻣ ﺔ ﻟﺘﺤﻠ ﻞ ﺣﺠ ﻢ ﻣﻌ ﯿﻦ ﻣ ﻦ‬

‫ﺑﯿﺮوﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ )ﻓﻮق أﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ(‪.‬‬
‫ﺍﳊﻞ‬
‫ﻛﻤﯿ ﺔ ﺣﺠ ﻢ )‪ (KMnO4‬اﻟﻤﺴ ﺘﺨﺪﻣﺔ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ ﻛﻤﯿ ﺔ ﻓ ﻮق أﻛﺴ ﯿﺪ‬

‫اﻟﮭﯿ ﺪروﺟﯿﻦ ﻏﯿ ﺮ اﻟﻤﺘﺤﻠﻠ ﺔ أي أن ))‪ (V = (a –x‬ﻟ ﺬﻟﻚ ﻓ ﺈن ﺣﺠ ﻢ‬
‫)‪ (KMnO4‬اﻟﻤﺴﺘﺨﺪم ﻓﻲ زﻣ ﻦ ﺻ ﻔﺮ ﯾﻤﺜ ﻞ اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ )‪،(a‬‬
‫واﻟﺤﺠﻢ اﻟﻤﺴﺘﺨﺪم ﺑﻌﺪ زﻣﻦ )‪ (t‬ﯾﻤﺜﻞ )‪.(a – x‬‬
‫‪Vt = 0 = a = 25‬‬
‫‪time, s‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫)‪V KMnO4, cm3 = ( a – x‬‬ ‫‪20‬‬ ‫‪15.7‬‬ ‫‪12.5‬‬ ‫‪9.6‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪a ‬‬
‫= ‪k‬‬ ‫‪log‬‬ ‫‪‬‬ ‫‪min-1‬‬ ‫‪0.0223 0.0233 0.0231 0.0239‬‬
‫‪‬‬ ‫‪t‬‬ ‫‪a-x‬‬

‫)‪(454‬‬
‫وﺑﻤﺎ أن ﻗﯿﻤﺔ اﻟﺜﺎﺑﺖ ﺛﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﻓﺈن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬وأن‬
‫ﻣﺘﻮﺳﻂ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﺘﺤﻠﻞ )‪ (H2O2‬ﻓﻲ وﺳﻂ ﻣﺎﺋﻲ ھﻮ ‪:‬‬
‫=‪k‬‬
‫) ‪( 0.0223 + 0.0233 + 0.0231 + 0.0239‬‬
‫‪4‬‬
‫‪-1‬‬
‫‪k = 0.02315 min‬‬
‫‪k = 3.86 × 10-4 s -1‬‬
‫ﻣﺜﺎﻝ )‪(١٧-٢‬‬
‫إن ﺗﺤﻠ ﻞ ﻧﺘﺮﯾ ﺖ اﻷﻣﻮﻧﯿ ﻮم )‪ (NH4NO2‬ﻓ ﻲ وﺳ ﻂ ﻣ ﺎﺋﻲ ﯾﺘﺒ ﻊ‬

‫اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ‬
‫‪NH 4 NO 2 ‬‬
‫‪→ 2H 2O + N 2‬‬
‫ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻣﺴﺘﻔﯿﺪاً ﻣﻦ ﻧﺘ ﺎﺋﺞ اﻟﺠ ﺪول‬

‫اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪Time, min‬‬ ‫‪10‬‬ ‫‪15‬‬ ‫‪20‬‬ ‫‪25‬‬ ‫∞‬
‫‪V (N2) cm3‬‬ ‫‪6.25‬‬ ‫‪9.0‬‬ ‫‪11.40‬‬ ‫‪13.65‬‬ ‫‪35.05‬‬
‫ﺍﳊﻞ‬
‫إن ﺣﺠ ﻢ اﻟﻨﯿﺘ ﺮوﺟﯿﻦ اﻟﻤﺘﺠﻤ ﻊ ﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ زﻣ ﻦ )‪ (t‬ھ ﻮ ﻣﻘﯿ ﺎس‬

‫ﻟﻜﻤﯿ ﺔ ﻧﺘﺮﯾ ﺖ اﻷﻣﻮﻧﯿ ﻮم اﻟﻤﺘﺤﻠﻠ ﺔ أي )‪ .(x‬وإن ﺣﺠ ﻢ اﻟﻨﯿﺘ ﺮوﺟﯿﻦ‬
‫اﻟﻜﻠ ﻲ اﻟﻤﺘﺠﻤ ﻊ ﻓ ﻲ ﻧﮭﺎﯾ ﺔ اﻟﺘﻔﺎﻋ ﻞ )أي ﺑﻌ ﺪ زﻣ ﻦ ∞( ﯾﻤﺜ ﻞ اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻟﻜﻠﻲ ﻟﻨﺘﺮﯾﺖ اﻷﻣﻮﻧﯿﻮم اﻹﺑﺘﺪاﺋﻲ أي )‪.(a‬‬

‫)‪(455‬‬

‫∞‪a = V‬‬
‫‪x = Vt‬‬
‫∞‪( a - x ) =V‬‬ ‫‪- Vt‬‬
‫‪a = V∞ = 35.05‬‬
‫‪Time, min‬‬ ‫‪10‬‬ ‫‪15‬‬ ‫‪20‬‬ ‫‪25‬‬
‫‪x = Vt (N2) cm3‬‬ ‫‪6.25‬‬ ‫‪9.0‬‬ ‫‪11.40‬‬ ‫‪13.65‬‬
‫∞‪( a - x ) =V‬‬ ‫‪- Vt‬‬ ‫‪28.8‬‬ ‫‪26.05‬‬ ‫‪23.65‬‬ ‫‪21.4‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪a ‬‬ ‫‪min-1‬‬ ‫‪0.01964 0.01979‬‬ ‫‪0.01967‬‬ ‫‪0.01974‬‬
‫= ‪k‬‬ ‫‪log‬‬ ‫‪‬‬
‫‪‬‬ ‫‪t‬‬ ‫‪a-x‬‬
‫=‪k‬‬
‫) ‪( 0.01964 + 0.01979 + 0.01967 + 0.01974‬‬
‫‪4‬‬
‫‪k = 19.71 × 10-2 min -1‬‬
‫‪k = 32.85 × 10-5 s -1‬‬
‫ﻣﺜﺎﻝ )‪(١٨-٢‬‬
‫أﺿﯿﻒ )‪ (5 cm3‬ﻣ ﻦ ﺧ ﻼت اﻹﯾﺜﯿ ﻞ إﻟ ﻰ إﻧ ﺎء ﯾﺤﺘ ﻮي ﻋﻠ ﻰ ‪(100‬‬

‫)‪ cm3‬ﻣﻦ ) ‪ (0.1 N‬ﺣﺎﻣﺾ اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ )‪ (HCl‬ﻣﻮﺿ ﻮع ﻓ ﻲ‬
‫ﺣﻤﺎم ﻣﺎﺋﻲ ﺛﺎﺑﺖ درﺟﺔ ﺣﺮارﺗ ﮫ ﻋﻨ ﺪ )‪ .(30 ºC‬وأﻧ ﮫ ﯾ ﺘﻢ ﺳ ﺤﺐ ‪(5‬‬
‫)‪ cm3‬ﻣﻦ ﺧﻠﯿﻂ اﻟﺘﻔﺎﻋﻞ ﻓﻲ أزﻣﻨﺔ ﻣﺨﺘﻠﻔ ﺔ وﺑﻌ ﺪ ﺗﺒﺮﯾ ﺪه ﯾ ﺘﻢ ﺗﺴ ﺤﯿﺤﮫ‬
‫ﻣﻊ ﻗﺎﻋﺪة ﻗﯿﺎﺳﯿﺔ‪ ،‬ﻓﺘﻢ اﻟﺤﺼﻮل ﻋﻠﻰ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪time, min‬‬ ‫‪0‬‬ ‫‪75‬‬ ‫‪119‬‬ ‫‪183‬‬ ‫∞‬
‫‪V (NaOH), ml‬‬ ‫‪9.62‬‬ ‫‪12.10‬‬ ‫‪13.10‬‬ ‫‪14.75‬‬ ‫‪21.05‬‬

‫)‪(456‬‬
‫ﺑﯿﻦ ﻣﻦ ﺧ ﻼل ھ ﺬه اﻟﻨﺘ ﺎﺋﺞ أن اﻟﺘﺤﻠ ﻞ اﻟﻤ ﺎﺋﻲ ﻟﺨ ﻼت اﻹﯾﺜﯿ ﻞ ھ ﻮ ﻣ ﻦ‬

‫ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻋﻠﻤﺎ ً ﺑﺄن ﻣﻌﺎدﻟﺔ اﻟﺘﻔﺎﻋﻞ ھﻲ ‪:‬‬
‫→‪CH 3COOC 2 H 5 + H 2 O ‬‬
‫‪HCl‬‬
‫‪CH 3COOH + C 2 H 5OH‬‬
‫ﺍﳊﻞ‬
‫إن ﻛﻤﯿ ﺔ اﻟﻘﺎﻋ ﺪة اﻟﻤﺴ ﺘﺨﺪﻣﺔ ﺗﻜ ﺎﻓﻲء اﻟﻜﻤﯿ ﺔ اﻟﻜﻠﯿ ﺔ ﻟﺤ ﺎﻣﺾ‬

‫اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ )اﻟﺬي ﯾﺴﺘﺨﺪم ﻛﻤﺎدة ﺣﺎﻓﺰة ﻟﻠﺘﻔﺎﻋ ﻞ( وﻛﻤﯿ ﺔ ﺣ ﺎﻣﺾ‬
‫اﻟﺨﻠﯿﻚ اﻟﻤﺘﻜﻮﻧﺔ ﻣﻦ اﻟﺘﻔﺎﻋﻞ‪ .‬وﯾﻤﻜﻦ ﺣﺴﺎب ﻛﻤﯿﺔ اﻟﻘﺎﻋ ﺪة اﻟﻤﺴ ﺘﺨﺪﻣﺔ‬
‫ﻟﻤﻜﺎﻓﺌ ﺔ ﺣ ﺎﻣﺾ اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ اﻟﻜﻠ ﻲ اﻟﻤﺴ ﺘﺨﺪم ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ وﻣﻨ ﮫ‬
‫أﯾﻀﺎ ً ﯾﻤﻜﻦ ﻣﻌﺮﻓﺔ ﻛﻤﯿﺔ ﺣﺎﻣﺾ اﻟﺨﻠﯿﻚ اﻟﻤﺘﻜﻮن )‪ (x‬ﻣﻦ زﻣﻦ )‪.(t‬‬
‫إن ﻛﻤﯿ ﺔ ﺣ ﺎﻣﺾ اﻟﺨﻠﯿ ﻚ اﻟﻤﺘﻜﻮﻧ ﺔ ﻓ ﻲ ﻧﮭﺎﯾ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﻜ ﺎﻓﺊ ) ∞‪( V‬‬
‫اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ )‪ (a‬ﻟﺨﻼت اﻹﯾﺜﯿﻞ‪ .‬وإن ﻛﻤﯿ ﺔ )‪ (NaOH‬اﻟﻤﻌﺎدﻟ ﺔ‬

‫ﻟـ )‪ (HCl‬ھﻲ )‪ .(V0‬ﻟﺬا ﻓﺈن ‪:‬‬
‫‪x = Vt - V0‬‬
‫‪a = V∞ - V0 = 21.05 - 9.62 = 11.43‬‬
‫‪a - x = ( V∞ - V0 ) - ( Vt - V0 ) = V∞ - V0 - Vt + V0 = V∞ - Vt‬‬

‫)‪(457‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪a ‬‬

‫اﻟ ﺬي ﯾ ﺆول ﻓ ﻲ‬ ‫= ‪k‬‬ ‫‪log‬‬ ‫‪‬‬ ‫وﺑﺎﺳﺘﺨﺪام ﻗﺎﻧﻮن اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫‪‬‬ ‫‪t‬‬ ‫‪a-x‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪V - V0 ‬‬

‫ﯾﻤﻜ ﻦ ﺗﻌﺒﺌ ﺔ‬ ‫= ‪k‬‬ ‫∞ ‪log‬‬ ‫‪‬‬ ‫ھ ﺬه اﻟﻤﺴ ﺄﻟﺔ اﻟ ﻰ اﻟﺼ ﻮرة‬
‫‪‬‬ ‫‪t‬‬ ‫‪V∞ - Vt ‬‬
‫اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪V0 = 9.62‬‬
‫‪V∞ = 21.05‬‬
‫‪a = V∞ - V0 = 21.05 - 9.62 = 11.43‬‬
‫‪time, min.‬‬ ‫‪75‬‬ ‫‪119‬‬ ‫‪183‬‬ ‫∞‬
‫)‪Vt (NaOH), ml = V(HCl) + V(CH3COOH‬‬ ‫‪12.10‬‬ ‫‪13.10‬‬ ‫‪14.75‬‬ ‫‪21.05‬‬
‫)‪[CH3COOH]t = x = (V t – V0‬‬ ‫‪2.48‬‬ ‫‪3.48‬‬ ‫‪5.13‬‬ ‫‪11.43‬‬
‫) ‪[CH3COOC2H5]t = ( a - x ) = ( V∞ - Vt‬‬ ‫‪8.95‬‬ ‫‪7.95‬‬ ‫‪6.3‬‬ ‫‪0‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪V - V0 ‬‬
‫= ‪k‬‬ ‫∞ ‪log‬‬ ‫‪‬‬
‫‪‬‬ ‫‪t‬‬ ‫‪V∞ - Vt ‬‬ ‫‪3.26 × 10-3‬‬ ‫‪3.05 × 10-3‬‬ ‫‪3.26 × 10-3‬‬
‫وﺑﻤ ﺎ أن ﻗ ﯿﻢ اﻟﺜﺎﺑ ﺖ ﻣﺘﻘﺎرﺑ ﺔ ﺟ ﺪاً ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ‬

‫اﻷوﻟﻰ‪.‬‬
‫ﻣﺜﺎﻝ )‪(١٩-٢‬‬
‫ﺗﻢ ﺗﺤﻠ ﻞ ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ ﻓ ﻲ ﻣﺤﻠ ﻮل ﻣ ﺎﺋﻲ وﺑﻮﺟ ﻮد )‪(0.05 mol/L‬‬

‫ﻣﻦ ﺣﺎﻣﺾ اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ ﻓﻲ درﺟﺔ ﺣﺮارة )‪.(25 ºC‬‬
‫‪CH3COOCH3 + H 2 O ‬‬
‫‪→ CH3COOH + CH3OH‬‬
‫ﻓﻌﻨﺪ إزاﻟﺔ )‪ (25 cm3‬ﻣﻦ ﺧﻠﯿﻂ اﻟﺘﻔﺎﻋﻞ ﻓﻲ أزﻣﺎن ﻣﺨﺘﻠﻔﺔ وﺗﺴﺤﯿﺤﮫ‬

‫ﻣ ﻊ ﻣﺤﻠ ﻮل اﻟﺼ ﻮدا اﻟﻜﺎوﯾ ﺔ )‪ (NaOH‬ﻓ ﺈن ﺣﺠ ﻢ اﻟﻘﺎﻋ ﺔ اﻟﻼزﻣ ﺔ‬
‫ﻟﺘﻌﺎدﻟﮫ ﻓﻲ زﻣﻦ )‪ (t‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫)‪(458‬‬
‫‪Time, min‬‬ ‫‪0‬‬ ‫‪21‬‬ ‫‪75‬‬ ‫‪119‬‬ ‫∞‬

‫‪V (NaOH) cm3‬‬ ‫‪24.4‬‬ ‫‪25.8‬‬ ‫‪29.3‬‬ ‫‪31.7‬‬ ‫‪47.2‬‬
‫ﺑ ﯿﻦ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬ﺛ ﻢ اﺣﺴ ﺐ ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ‬

‫ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻣﻦ ﺧﻼل ﻣﻌﺎدﻟﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫→‪CH 3COOCH 3 + H 2O ‬‬
‫‪HCl‬‬
‫‪CH 3COOH + CH 3OH‬‬
‫ﯾﺒﺪو أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬

‫]‪rate = k [ CH3COOCH 3 ][ HCl‬‬
‫وﻗﺪ وﺟﺪ أن ﺗﺮﻛﯿﺰ اﻟﺤﺎﻣﺾ ﯾﻜﻮن ﻛﺒﯿﺮاً ﺑﺤﯿﺚ أن اﻟﺘﻐﯿﺮ ﻓﻲ ﺗﺮﻛﯿﺰه‬

‫ﻗﻠﯿﻞ ﺟﺪاً ﻟﺬا ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﺗﺤﻮﯾﻞ ﻣﻌﺪل ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻟﻠﺸﻜﻞ اﻟﺘﺎﻟﻲ ‪:‬‬
‫] ‪rate = k' [ CH 3COOCH 3‬‬
‫ﺣﯿﺚ )'‪ (k‬ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﺎذب واﻟﺬي ﯾﻤﺜﻞ ‪:‬‬

‫]‪k' = k [HCl‬‬
‫إن ﻛﻤﯿ ﺔ ﺣ ﺎﻣﺾ اﻟﺨﻠﯿ ﻚ اﻟﻤﺘﻜﻮﻧ ﺔ ﻓ ﻲ ﻧﮭﺎﯾ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﻜ ﺎﻓﻲء ) ∞‪( V‬‬
‫اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ )‪ (a‬ﻟﺨﻼت اﻟﻤﯿﺜﯿﻞ‪ .‬وإن ﻛﻤﯿ ﺔ )‪ (NaOH‬اﻟﻤﻌﺎدﻟ ﺔ‬
‫ﻟـﻜﻤﯿﺔ )‪ (HCl‬اﻟﻜﻠﯿﺔ ھﻲ )‪ .(V0‬ﻟﺬا ﻓﺈن ‪:‬‬

‫)‪(459‬‬
‫‪x = Vt - V0‬‬
‫‪a = V∞ - V0 = 47.2 - 24.4 = 22.8‬‬
‫‪a - x = ( V∞ - V0 ) - ( Vt - V0 ) = V∞ - V0 - Vt + V0 = V∞ - Vt‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪a ‬‬

‫اﻟ ﺬي ﯾ ﺆول ﻓ ﻲ‬ ‫= ‪k‬‬ ‫‪log‬‬ ‫‪‬‬ ‫وﺑﺎﺳﺘﺨﺪام ﻗﺎﻧﻮن اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫‪‬‬ ‫‪t‬‬ ‫‪a-x‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪V - V0 ‬‬

‫واﻟﺘ ﻲ ﻧﺠﻌﻠﮭ ﺎ ﻋﻠ ﻰ‬ ‫= ‪k‬‬ ‫∞ ‪log‬‬ ‫‪‬‬ ‫ھﺬه اﻟﻤﺴﺄﻟﺔ اﻟﻰ اﻟﺼﻮرة‬
‫‪‬‬ ‫‪t‬‬ ‫‪V∞ - Vt ‬‬
‫ﺻﻮرة ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬

‫‪2.303‬‬ ‫‪V - V0‬‬
‫=‪k‬‬ ‫∞ ‪log‬‬
‫‪t‬‬ ‫‪V∞ - Vt‬‬
‫‪ k ‬‬ ‫‪2.303‬‬ ‫‪V - V0‬‬
‫‪‬‬ ‫= ‪t‬‬ ‫∞ ‪log‬‬
‫‪ 2.303 ‬‬ ‫‪t‬‬ ‫‪V∞ - Vt‬‬
‫‪k‬‬
‫) ‪t = log ( V∞ - V0 ) − log ( V∞ - Vt‬‬
‫‪2.303‬‬
‫‪ -k ‬‬
‫‪⇒ log ( V∞ - Vt ) = ‬‬ ‫) ‪ t + log ( V∞ - V0‬‬
‫‪ 2.303 ‬‬
‫‪‬‬ ‫‪ -k ‬‬ ‫‪‬‬

‫ﺑﺘﻤﺜﯿ ﻞ‬ ‫‪ log ( V∞ - Vt ) =  2.303  t + log ( V∞ - V0 ) ‬‬ ‫وﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫) ) ‪ ( log ( V∞ - Vt‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات‪ ،‬واﻟ ﺰﻣﻦ )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬

‫اﻟﺴﯿﻨﺎت ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ ﯾﺴﺎوي )‪ .(- k/2.303‬وﺑﻌﻤﻞ‬

(460)
V0 = 24.4
V∞ = 47.2
a = V∞ - V0 = 47.2 - 24.4 = 22.8
time, min. 0 21 75 119 ∞
Vt (NaOH), ml = V(HCl) + V(CH3COOH) 24.4 25.8 29.3 31.7 47.2
[CH3COOH]t = x = (Vt – V0) 0 1.4 4.9 7.3 22.8
[CH3COOCH3]t = ( a - x ) = ( V∞ - Vt ) 22.8 21.4 17.9 15.5 0
log ( V∞ - Vt ) 1.358 1.330 1.253 1.190
 2.303 V - V0  3.02 3.23 3.24
k = log ∞  × × ×
 t V∞ - Vt 
10-3 10-3 10-3
‫( اﻟﺜﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﻣﻦ اﻟﺠ ﺪول اﻟﺴ ﺎﺑﻖ ﯾﻈﮭ ﺮ ﺟﻠﯿ ﺎ ً أن اﻟﺘﻔﺎﻋ ﻞ‬k) ‫ﻣﻦ ﻗﯿﻢ‬
.‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‬
‫( ﻧﺤﺼ ﻞ ﻋﻠ ﻰ اﻟﺸ ﻜﻞ‬t) ‫ﻣﻘﺎﺑ ﻞ اﻟ ﺰﻣﻦ‬ log ( V∞ - Vt ) ‫وﻋﻨ ﺪ ﺗﻤﺜﯿ ﻞ‬
.(١٩-٢)
(١٩-٢) ‫ﺷﻜﻞ‬

‫)‪(461‬‬
‫وﺑﻤﺎ أن اﻟﻌﻼﻗﺔ ھﻲ ﻋﻼﻗﺔ ﺧﻄﯿﺔ ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬وأن‬

‫اﻟﻤﯿﻞ ﯾﺴﺎوي ‪ ،(- 1.46 × 10-3) :‬وﻣﻨﮫ ﯾﻤﻜ ﻦ ﺣﺴ ﺎب ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋﻞ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪ -k ‬‬
‫‪slope = ‬‬ ‫‪‬‬
‫‪ 2.303 ‬‬
‫)‪k = slope × ( - 2.303‬‬
‫)‪k = ( - 1.46 × 10-3 ) × ( - 2.303‬‬
‫‪k = 3.36 × 10-3 min -1‬‬
‫‪k = 5.60 × 10-5 s-1‬‬
‫أﻣ ﺎ ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﯾﻨ ﺘﺞ ﻧﺼ ﻒ اﻟﻜﻤﯿ ﺔ أي‬

‫وﺗﺼﺒﺢ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬ ‫) ‪0.5 ( V∞ - V0‬‬
‫‪2.303‬‬ ‫‪V - V0‬‬

‫=‪k‬‬ ‫∞ ‪log‬‬
‫‪t‬‬ ‫‪V∞ - Vt‬‬
‫= ‪5.60 × 10-5‬‬
‫‪2.303‬‬ ‫) ‪( V - V0‬‬
‫∞ ‪log 1‬‬
‫‪t1/2‬‬ ‫) ‪2 ( V∞ - V0‬‬
‫‪2.303‬‬
‫= ‪t1/2‬‬ ‫‪log 2‬‬
‫‪5.60 × 10-5‬‬
‫‪t1/2 = 112.38 × 103 s‬‬
‫‪t1/2 = 206.33 min‬‬

‫)‪(462‬‬
‫ﻣﺜﺎﻝ )‪(٢٠-٢‬‬
‫ﺗﺘﻤﯿﺄ ﺧﻼت اﻟﻤﯿﺜﯿﻞ ﻓﻲ ﺣﺎﻣﺾ اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ ﻋﯿ ﺎري )‪ (1 N‬ﻋﻨ ﺪ‬

‫درﺟ ﺔ ﺣ ﺮارة )‪ .(25 ºC‬وﺗ ﻢ أﺧ ﺬ أﺟ ﺰاء ﻣﺨﺘﻠﻔ ﺔ ﻣ ﻦ اﻟﻤﺤﻠ ﻮل‬
‫ﻣﻘ ﺪارھﺎ )‪ (5 cm3‬ﻓ ﻲ ﻓﺘ ﺮات زﻣﻨﯿ ﺔ ﻣﺨﺘﻠﻔ ﺔ وﺳ ﺤﺤﺖ ﻣ ﻊ ﻣﺤﻠ ﻮل‬
‫ھﯿﺪروﻛﺴ ﯿﺪ اﻟﺼ ﻮدﯾﻮم )‪ (NaOH‬ﺗﺮﻛﯿ ﺰه )‪ .(0.1852 N‬اﺣﺴ ﺐ‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻣﻦ اﻟﺒﯿﺎﻧﺎت اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪time, s‬‬ ‫‪339‬‬ ‫‪1242‬‬ ‫‪2745‬‬ ‫‪4546‬‬ ‫∞‬
‫‪Volume, ml‬‬ ‫‪26.34‬‬ ‫‪27.80‬‬ ‫‪29.70‬‬ ‫‪31.81‬‬ ‫‪39.81‬‬
‫ﺍﳉﻮﺍﺏ ‪k = 1.26 × 10-4 s-1 :‬‬

‫ﺍﻟﺘﻔﺼﻴﻞ‬
‫‪....................................................................................................................................................................... .................‬‬
‫‪................................................................................................ ........................................................................................‬‬
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‫)‪(463‬‬
‫ﻣﺜﺎﻝ )‪(٢١-٢‬‬
‫ﯾﺤﺘﻮي اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﻋﻠ ﻰ ﻧﺘ ﺎﺋﺞ ﺗﺤﻄ ﻢ ﺗ ﺮاي أوﻛﺴ ﺎن )ﻏ ﺎز( ﻋﻨ ﺪ‬
‫درﺟﺔ ﺣﺮارة )‪ (260 ºC‬ﻹﻋﻄﺎء ﻓﻮرﻣﺎﻟﺪھﯿﺪ ‪:‬‬
‫‪C3H 6 O3 (g) ‬‬
‫)‪→ 3H 2 CO(g‬‬
‫اﻟﺰﻣﻦ ‪/‬ﺳﺎﻋﺔ‬ ‫‪0.00‬‬ ‫‪1.00‬‬ ‫‪2.00‬‬ ‫‪3.00‬‬ ‫‪4.00‬‬ ‫∞‬

‫ﺿﻐﻂ اﻟﻐﺎز ‪mmHg‬‬ ‫‪100.0‬‬ ‫‪173.0‬‬ ‫‪218.0‬‬ ‫‪248.0‬‬ ‫‪266.0‬‬ ‫‪300.0‬‬
‫أ( ﻣﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ؟‬

‫ب( ﻣﺎ ﺛﺎﺑﺖ ﺳﺮﻋﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ )‪(k‬؟‬
‫ج( ﻣﺎ ﻧﺼﻒ زﻣﻦ اﻟﺘﻔﺎﻋﻞ )‪(t1/2‬؟‬
‫د( ﻣﺎ ﺿﻐﻂ ﺗﺮاي أوﻛﺴﺎن ﻋﻨﺪﻣﺎ ﯾﺘﺤﻄﻢ ﻧﺼﻔﮫ؟‬
‫ﺍﳉﻮﺍﺏ ‪:‬‬
‫ج( ‪ t1/2 = 1.55 h‬د( ‪P = 200 mmHg‬‬ ‫ب( ‪k = 0.448 h-1‬‬ ‫أ( رﺗﺒﺔ أوﻟﻰ‬
‫ﺍﻟﺘﻔﺼﻴﻞ ﻟﻠﺤﻞ ﺍﻟﻨﻬﺎﺋﻲ‬

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(464)
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‫)‪(465‬‬
‫ﻣﺜﺎﻝ )‪(٢٢-٢‬‬
‫ﯾ ﺘﺤﻄﻢ اﻷﺳ ﯿﺘﻮن )‪ (CH3COCH3‬ﺑﻔﻌ ﻞ اﻟﺤ ﺮارة ﻟﯿﻌﻄ ﻲ اﻟﻤﯿﺜ ﺎن‬

‫)‪ (CH4‬و ﻛﯿﺘﯿﻦ )‪: (C2H2O‬‬
‫‪C3 H 6 O(g) ‬‬
‫)‪→ CH 4 (g) + C2 H2 O(g‬‬
‫‪( CH COCH‬‬ ‫‪3‬‬ ‫‪3‬‬ ‫) ‪→ CH 4 (g) + H 2 C = C = O‬‬
‫‪‬‬
‫وھ ﻮ ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ .‬ﻓ ﺈذا ﺑﻠ ﻎ ﺿ ﻐﻂ اﻷﺳ ﯿﺘﻮن ﻓ ﻲ ﺑﺪاﯾ ﺔ‬

‫اﻟﺘﻔﺎﻋ ﻞ )‪) (0.100 atm‬ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة ﻣﻌﯿﻨ ﺔ( وﺑﻌ ﺪ ﻣ ﺮور‬
‫)‪ (60 s‬ارﺗﻔﻊ اﻟﻀ ﻐﻂ داﺧ ﻞ اﻹﻧ ﺎء اﻟ ﻰ )‪ (0.160‬ﺑﯿﻨﻤ ﺎ ظ ﻞ اﻟﺤﺠ ﻢ‬
‫◌‬ ‫ﺛﺎﺑﺘﺎ ً‪.‬‬
‫أ( اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪(k‬‬
‫ب( ﻣﺎ ﻋﺪد اﻟﺜﻮاﻧﻲ اﻟﻼزﻣﺔ ﻟﻜﻲ ﯾﺮﺗﻔﻊ اﻟﻀ ﻐﻂ اﻟ ﻰ )‪(0.181 atm‬‬
‫ﺛﻢ اﻟﻰ )‪(0.190 atm‬؟‬
‫ب( ‪150 s, 110 s‬‬ ‫ﺍﳉﻮﺍﺏ أ( ‪k = 1.5 × 10-2 s-1‬‬

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(466)
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‫)‪(467‬‬
‫ﻣﺜﺎﻝ )‪(٢٣-٢‬‬
‫ﯾﺒﻠﻎ ﻧﺼﻒ زﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ )‪ (123 min‬ﻋﻨ ﺪ درﺟ ﺔ )‪ (15 ºC‬وذﻟ ﻚ‬

‫ﻋﻨ ﺪﻣﺎ ﯾ ﺘﺤﻄﻢ ﻧﺘﺮاﻣﯿ ﺪ )‪ (NH2NO2‬اﻟ ﻰ أﻛﺴ ﯿﺪ ﻧﯿﺘ ﺮوز )‪(N2O‬‬
‫وﻣﺎء )‪: (H2O‬‬
‫‪NH 2 NO2 ‬‬
‫‪→ N 2 O + H2 O‬‬
‫ﻓﺈذا ﻋﻠﻤﻨﺎ أن ھﺬا اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫أ( اﺣﺴﺐ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ (k‬ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ب( ﻣ ﺎ اﻟﻤ ﺪة اﻟﻼزﻣ ﺔ ﻟﻜﻤﯿ ﺔ ﺗﺒﻠ ﻎ ﻣ ﻦ )‪ (NH2NO2‬ﺣﺘ ﻰ ﺗ ﺘﺤﻄﻢ‬
‫وﯾﺒﻘﻰ ﻣﻨﮭﺎ ﻓﻘﻂ )‪ ،(0.20 g‬وﻛﻢ ﻣﻦ اﻟﺰﻣﻦ ﯾﻤﺮ ﻟﻜﻲ ﯾﺘﺒﻘﻰ ‪(0.020‬‬
‫)‪ g‬ﻣﻦ ﺗﻠﻚ اﻟﻤﺎدة؟‬
‫ب( ‪818 min, 409 min.‬‬ ‫ﺍﳉﻮﺍﺏ ‪ :‬أ( ‪5.63 × 10-3 min-1‬‬
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(468)
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‫)‪(469‬‬
‫ﻣﺜﺎﻝ )‪(٢٤-٢‬‬
‫ﺗﺘﺤﻄﻢ ﻣﺎدة )‪ (SO2Cl2‬ﺑﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟ ﻰ ﻟﺘﻌﻄ ﻲ )‪ (SO2‬و‬

‫)‪ (Cl2‬ﻓﺈذا ﻋﻠﻤﻨﺎ أن زﻣﻦ ﻧﺼﻒ اﻟﺘﻔﺎﻋﻞ ﯾﺒﻠﻎ )‪ (8.75 h‬ﻋﻨ ﺪ درﺟ ﺔ‬
‫)‪.(320 ºC‬‬
‫أ( اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ب( إذا ﺑ ﺪأ اﻟﺘﻔﺎﻋ ﻞ ﺑﻜﻤﯿ ﺔ ﺗﺒﻠ ﻎ )‪ (2.5 g‬ﻣ ﻦ )‪ (SO2Cl2‬ﻓﻜ ﻢ ﯾﺘﺒﻘ ﻰ‬
‫ﻣﻨﮭﺎ ﺑﻌﺪ ﻣﺮور )‪.(3.00 h‬‬
‫ب( ‪1.97 g‬‬ ‫ﺍﳉﻮﺍﺏ ‪ :‬أ( ‪k = 7.92 × 10-2 h-1‬‬

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(470)
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‫)‪(471‬‬
‫ﻣﺜﺎﻝ )‪(٢٥-٢‬‬
‫ﯾ ﺘﺤﻄﻢ ﻓ ﻮق أﻛﺴ ﯿﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ )‪ (H2O2‬ﻓ ﻲ وﺟ ﻮد ﺣ ﺎﻓﺰ ﻟﯿﻌﻄ ﻲ‬

‫ﻣﺎء وأﻛﺴﺠﯿﻦ ﻓﻲ ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟ ﻰ‪ ،‬وﻗ ﺪ ﻋ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ‬
‫ﻋﻨﺪ أﺣﺪ درﺟﺎت اﻟﺤﺮارة ﻓﻜﺎﻧﺖ ﻗﯿﻤﺘﮫ )‪(2.40 × 10-4 s-1‬‬
‫أ( اﺣﺴﺐ ﻧﺼﻒ زﻣﻦ اﻟﺘﻔﺎﻋﻞ )‪ (t1/2‬ﺑﻮﺣﺪات )ﺛﺎﻧﯿﺔ(‪.‬‬
‫ب( ﻣﺎ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﺤﻄﻢ )‪) (75.0 %‬ﺛﻼث أرﺑﺎع اﻟﻤﺎدة(؟‬
‫ج( ﻣﺎ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﺤﻄﻢ )‪ (87.5 %‬ﻣﻦ اﻟﻤﺎدة )ﺳﺒﻊ أﺛﻤﺎن(‪.‬‬
‫د( أذﻛﺮ اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪.(t1/2, t3/4, t7/8‬‬
‫ب( ‪5.78 × 103 s‬‬ ‫أ( ‪2.89 × 103 s‬‬

‫د( )‪t1/2 = 1/2 (t3/4) = 1/3 (t7/8‬‬ ‫ج( ‪8.67 × 103 s‬‬

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(472)
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‫)‪(473‬‬
‫ﻣﺜﺎﻝ )‪(٢٦-٢‬‬
‫‪ ( A‬ﺑﻌﺸ ﺮة ﺟﺮاﻣ ﺎت ﻣ ﻦ‬ ‫)‪→ B + C‬‬

‫‪‬‬ ‫إذا ﺑ ﺪأ ﺗﻔﺎﻋ ﻞ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫)‪ (A‬ﻓﻜﻢ ﯾﺒﻘﻰ ﻣﻦ ﺗﻠﻚ اﻟﻤﺎدة ﺑﻌﺪ ﻣﺮور ﺛﻼﺛﺔ أﻧﺼ ﺎف )‪ (3t1/2‬وﺳ ﺘﺔ‬
‫أﻧﺼﺎف )‪ (6t1/2‬أزﻣﻨﺔ‪ .‬وأﺧﯿﺮاً ﻛﻢ ﯾﺒﻘﻰ ﻣﻦ اﻟﻤﺎدة ﺑﻌﺪ ﻣ ﺮور ﻋﺸ ﺮة‬
‫أﻧﺼﺎف )‪ (10t1/2‬ﻣﻦ زﻣﻦ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫‪(0.0098 g,‬‬ ‫‪0.156 g,‬‬ ‫ﺍﳉﻮﺍﺏ ‪1.25 g :‬‬

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(474)
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‫)‪(475‬‬
‫ﻣﺜﺎﻝ )‪(٢٧-٢‬‬
‫ﺗ ﺘﺤﻄﻢ ﻣ ﺎدة ﻛﻠﻮرﯾ ﺪ اﻹﯾﺜﯿ ﻞ )‪ (C2H5Cl‬ﻹﻋﻄ ﺎء إﯾﺜﯿﻠ ﯿﻦ )‪(C2H4‬‬

‫وﻛﻠﻮرﯾﺪ اﻟﮭﯿﺪروﺟﯿﻦ )‪ (HCl‬ﻓﻲ ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫‪C 2 H 5Cl(g) ‬‬
‫)‪→ H 2 C=CH 2 (g) + HCl(g‬‬
‫ﻓ ﺈذا ﻋﻠﻤﻨ ﺎ أن ﻧﺼ ﻒ زﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ ﯾﺒﻠ ﻎ )‪ (90 min‬ﻋﻨ ﺪ درﺟ ﺔ‬

‫ﺣﺮارة )‪.(200 ºC‬‬
‫أ( إﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪(k‬‬
‫ب( ﻣﺎ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﺤﻄﻢ )‪ (75 %‬ﻣﻦ ﻛﻠﻮرﯾﺪ اﻹﯾﺜﯿﻞ؟‬
‫ب( ‪180 min‬‬ ‫ﺍﳉﻮﺍﺏ ‪ :‬أ( ‪k = 7.70 × 10-3 min-1‬‬

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(476)
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‫)‪(477‬‬
‫ﻣﺜﺎﻝ )‪(٢٨-٢‬‬
‫ﯾ ﺘﺤﻄﻢ ﻏ ﺎز ﻛﻠﻮرﯾ ﺪ اﻹﯾﺜﯿ ﻞ )‪ (C2H5Cl‬ﻟﯿﻌﻄ ﻲ إﯾﺜﻠ ﯿﻦ )‪(C2H4‬‬

‫وﻛﻠﻮرﯾ ﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ )‪ (HCl‬ﻓ ﻲ ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ وﻋﻨ ﺪ‬
‫درﺟﺔ ﺣﺮارة )‪.(200 ºC‬‬
‫‪C2 H5 Cl(g) ‬‬
‫)‪→ H 2C = CH 2 (g) + HCl(g‬‬
‫ﺳ ﻨﻔﺘﺮض أﻧ ﻚ ﻋﯿﻨ ﺖ ﺑﺘﺠﺮﺑ ﺔ اﻟﺴ ﺮﻋﺔ )‪ (k‬وﻧﺼ ﻒ زﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ‬

‫)‪ (t1/2‬وﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )ﺗﻠﻘﺎﺋﯿ ﺎ( ﻋﻨ ﺪ ﺗﺤﻄ ﻢ )‪ (25 %‬وﻋﻨ ﺪ درﺟ ﺔ‬
‫)‪ (200 ºC‬وﺗﺤﺖ ﺿﻐﻂ ﺛﺎﺑﺖ ﯾﺒﻠﻎ )‪ .(1.0 atm‬ﻣﺎذا ﺳﯿﻜﻮن ﺗ ﺄﺛﯿﺮ‬
‫ازدﯾﺎد اﻟﻀﻐﻂ اﻟﻰ اﻟﻀﻌﻒ )‪ (2 atm‬ﻋﻠﻰ ﻣﺎ ﯾﻠﻲ ‪:‬‬
‫أ( ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ‪k‬‬
‫ب( ﻧﺼﻒ زﻣﻦ اﻟﺘﻔﺎﻋﻞ )‪.(t1/2‬‬
‫ج( ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪﻣﺎ ﯾ ﺘﺤﻄﻢ )‪ (25 %‬ﻣ ﻦ اﻟﻤ ﺎدة وﻋﻨ ﺪ درﺟ ﺔ‬
‫ﺣﺮارة )‪.(200 ºC‬‬
‫ج( ﺗﺄﺛﯿﺮه ﻣﻀﺎﻋﻒ‪.‬‬ ‫ب( ﻻ ﺗﺄﺛﯿﺮ‬ ‫ﺍﳉﻮﺍﺏ ‪ :‬أ( ﻻ ﺗﺄﺛﯿﺮ‬

(478)

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‫)‪(479‬‬
‫ﻣﺜﺎﻝ )‪(٢٩-٢‬‬
‫أﻛﺘ ﺐ ﻣﻌﺎدﻟ ﺔ اﻟﺴ ﺮﻋﺔ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬وﺑ ﯿﻦ ﻛﯿ ﻒ ﺗﺴ ﺘﻨﺘﺞ‬
‫‪.  k = 0.693‬‬ ‫‪‬‬
‫ﻣﻨﮭﺎ اﻟﻌﻼﻗﺔ ‪‬‬
‫‪‬‬ ‫‪t‬‬ ‫‪1/2‬‬ ‫‪‬‬
‫‪........................................................... .............................................................................................................................‬‬
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‫)‪(480‬‬
‫ﻣﺜﺎﻝ )‪(٣٠-٢‬‬
‫ﻓﻲ ﺗﻔﺎﻋﻞ ﺗﺤﻠﻞ ﻛﻠﻮرﯾﺪ اﻟﺴﻠﻔﻮﻧﯿﻞ ‪:‬‬

‫‪SO 2 Cl 2 ‬‬
‫‪→ SO 2 + Cl2‬‬
‫ﻛﺎن اﻟﺘﻔﺎﻋﻞ أﺣﺎدي اﻟﺮﺗﺒﺔ وﻛﺎن ﺛﺎﺑﺖ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ )‪ (320 ºC‬ھ ﻮ‬
‫)‪ (2.0 × 10-5 s-1‬ﻣﺎ اﻟﻨﺴﺒﺔ اﻟﻤﺌﻮﯾﺔ ﻟﺘﺤﻠ ﻞ ﻛﻠﻮرﯾ ﺪ اﻟﺴ ﻠﻔﻮﻧﯿﻞ ﺑﺘﺴ ﺨﯿﻨﮫ ﻋﻨ ﺪ‬
‫)‪ (320 ºC‬ﻟﻤﺪة )‪ (90‬دﻗﯿﻘﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻓﻲ ھﺬه اﻟﻤﺴﺄﻟﺔ ﻟﻢ ﻧﻌﻂ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻟﻠﺴﻠﻔﻮﻧﯿﻞ‪ ،‬ﻟ ﺬﻟﻚ ﺳﻨﻔﺮﺿ ﮫ ﺑﺄﻧ ﮫ ﯾﺴ ﺎوي‬
‫)‪ ،(1‬وﺳﻨﻔﺮض أن اﻟﺠﺰء اﻟﻤﻨﺤﻞ ﻣﻨﮫ )اﻟﻨﺎﺗﺞ( ﯾﺴﺎوي )‪.(x‬‬
‫وﺑﻤ ﺎ أن اﻟﺘﻔﺎﻋ ﻞ أﺣ ﺎدي اﻟﺮﺗﺒ ﺔ ﻛﻤ ﺎ أﺷ ﺎر اﻟﺴ ﺆال ﻓﺈﻧﻨ ﺎ ﻧﻄﺒ ﻖ اﻟﻌﻼﻗ ﺔ اﻟﺨﺎﺻ ﺔ‬
‫ﺑﻤﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ ﻟﺘﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬
‫‪ a ‬‬
‫‪2.303log ‬‬ ‫‪= k t‬‬
‫‪a-x‬‬
‫‪ 1 ‬‬
‫)‪ = 2.0 × 10 × (90 × 60‬‬
‫‪-5‬‬
‫‪2.303 log ‬‬
‫‪1 - × ‬‬
‫‪ 1 ‬‬ ‫)‪2.0 × 10-5 × (90 × 60‬‬
‫‪log ‬‬ ‫=‪‬‬
‫‪1 - × ‬‬ ‫‪2.303‬‬
‫‪ 1 ‬‬
‫‪log ‬‬ ‫‪ = 0.047‬‬
‫‪1 - × ‬‬
‫‪ 1 ‬‬
‫‪ 1 -  = 1.114‬‬
‫‪‬‬ ‫‪×‬‬
‫)‪1= 1.114 (1 - x‬‬
‫‪1=1.114 - 1.114 x‬‬
‫‪1.114 x = 1.114 - 1‬‬
‫‪1.114 x = 0.114‬‬
‫‪0.114‬‬
‫=‪x‬‬ ‫‪= 0.102‬‬
‫‪1.114‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻨﺴﺒﺔ اﻟﻤﺌﻮﯾﺔ ﻟﺘﺤﻠﻞ ‪ SO2Cl2‬ھﻲ )‪(10.2 %‬‬

‫)‪(481‬‬
‫ﻣﺜﺎﻝ )‪(٣١-٢‬‬
‫اﻟﻨﺘ ﺎﺋﺞ اﻟﺘﺎﻟﯿ ﺔ ﺣﺼ ﻠﻨﺎ ﻋﻠﯿﮭ ﺎ ﻻﻧﺤ ﻼل ﺳ ﻜﺮ اﻟﺠﻠﻮﻛ ﻮز ﻓ ﻲ اﻟﻤﺤﻠ ﻮل‬

‫اﻟﻤﺎﺋﻲ ‪:‬‬
‫‪Glucose concentration mmol. dm-3‬‬ ‫‪56.0‬‬ ‫‪55.3‬‬ ‫‪54.2‬‬ ‫‪52.5‬‬ ‫‪49.0‬‬
‫‪Time/min.‬‬ ‫‪0‬‬ ‫‪45‬‬ ‫‪120‬‬ ‫‪240‬‬ ‫‪480‬‬
‫أﺛﺒﺖ أن اﻟﺘﻔﺎﻋﻞ أﺣﺎدي اﻟﺮﺗﺒﺔ‪ ،‬ﺛﻢ اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ وﻛﺬا‬
‫ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﺘﺤﻠﻞ اﻟﺠﻠﻮﻛﻮز ﻋﻨﺪ ھﺬه اﻟﻈﺮوف‪.‬‬
‫ﺍﳊﻞ‬
‫ﻣ ﻦ اﻟﻘ ﺮاءات اﻟﺴ ﺎﺑﻘﺔ ﻓ ﺈن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﺠﻠﻮﻛ ﻮز ھ ﻮ‬

‫)‪ (a = 56.0 mmol. dm-3‬وﻣﺎ ﯾﻠ ﻲ ھ ﺬا اﻟﺘﺮﻛﯿ ﺰ ﻣ ﻦ اﻟﺘﺮﻛﯿ ﺰات‬
‫اﻷﺧﺮى ﯾﻌﺒﺮ ﻋﻦ ﺗﺮﻛﯿﺰ اﻟﺠﻠﻮﻛﻮز ﺑﻌﺪ اﺳ ﺘﮭﻼك ﻛﻤﯿ ﺔ ﻣﻨ ﮫ ﻣﻘ ﺪارھﺎ‬
‫)‪ (x‬ﻟﺬﻟﻚ ھﻮ ﯾﻌﺒﺮ ﻋﻦ اﻟﻘﯿﻤﺔ )‪: (a – x‬‬
‫)‪(a = 56.0 mmol. dm-3‬‬
‫‪Time/min.‬‬ ‫‪45‬‬ ‫‪120‬‬ ‫‪240‬‬ ‫‪480‬‬
‫)‪(a – x‬‬ ‫‪55.3‬‬ ‫‪54.2‬‬ ‫‪52.5‬‬ ‫‪49.0‬‬
‫)‪log (a – x‬‬ ‫‪1.743‬‬ ‫‪1.734‬‬ ‫‪1.720‬‬ ‫‪1.690‬‬
‫‪‬‬ ‫‪k‬‬ ‫‪‬‬

‫ﺑ ﺄن ﻧﺮﺳ ﻢ‬ ‫‪ log (a - x) = -‬‬
‫‪‬‬ ‫‪2.303‬‬
‫‪t + log a ‬‬
‫‪‬‬
‫وﺑﺘﻤﺜﯿ ﻞ اﻟﻌﻼﻗ ﺔ‬
‫)‪ log (a – x‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات واﻟ ﺰﻣﻦ )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬

‫اﻟﺴﯿﻨﺎت ﻧﺤﺼﻞ ﻋﻠﻰ اﻟﺸﻜﻞ )‪.(٢٠-٢‬‬

‫)‪(482‬‬
‫ﺷﻜﻞ )‪ : (٢٠-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ ﻟﺘﺤﻠﻞ ﺳﻜﺮ اﻟﺠﻠﻮﻛﻮز‬

‫وﺣﯿﺚ إﻧﻨﺎ ﺣﺼﻠﻨﺎ ﻣﻦ ھﺬه اﻟﻌﻼﻗﺔ ﻋﻠﻰ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ دل ذﻟ ﻚ ﻋﻠ ﻰ أن‬
‫اﻟﺘﻔﺎﻋﻞ أﺣﺎدي اﻟﺮﺗﺒﺔ‪ ،‬وﯾﻜﻮن ﻣﯿﻞ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ھﻮ ‪:‬‬
‫‪-k‬‬
‫= ‪slope‬‬ ‫‪= - 1.18 × 10-4‬‬
‫‪2.303‬‬
‫‪- k = - 1.18 × 10- 4 × 2.303‬‬
‫‪k = 2.72 × 10-4 min -1‬‬
‫وﻟﺤﺴﺎب زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ﻧﺘﺒﻊ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪0.693‬‬
‫= ‪t 0.5‬‬
‫‪k‬‬
‫‪0.693‬‬
‫= ‪t 0.5‬‬
‫‪2.72 × 10-4‬‬
‫‪t 0.5 = 2547.8 min.‬‬

‫)‪(483‬‬
‫ﻣﻠﺤﻮﻇﺔ ‪:‬‬
‫ﯾﻤﻜ ﻦ ﺣ ﻞ اﻟﻤﺴ ﺎﻟﺔ اﻟﺤﺴ ﺎﺑﯿﺔ ﺑﺎﺳ ﺘﺨﺪام ﻗ ﺎﻧﻮن اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻋﻠ ﻰ‬
‫اﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫)‪(a - x‬‬
‫‪a‬‬
‫‪2.303 log‬‬ ‫‪= kt‬‬
‫)‪(a - x‬‬
‫‪a‬‬ ‫‪k‬‬
‫‪⇒ log‬‬ ‫=‬ ‫‪t‬‬
‫‪(a - x) 3.303‬‬
‫)‪(a = 56.0 mmol. dm-3‬‬

‫‪Time/min.‬‬ ‫‪45‬‬ ‫‪120‬‬ ‫‪240‬‬ ‫‪480‬‬
‫)‪(a – x‬‬ ‫‪55.3‬‬ ‫‪54.2‬‬ ‫‪52.5‬‬ ‫‪49.0‬‬
‫‪a‬‬
‫‪log‬‬
‫)‪(a - x‬‬
‫‪5.5 × 10-3‬‬ ‫‪14.2 × 10-3‬‬ ‫‪28 × 10-3‬‬ ‫‪58 × 10-3‬‬
‫‪‬‬ ‫‪a ‬‬

‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات و )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬ ‫‪ log‬‬ ‫‪‬‬ ‫وﻋﻨ ﺪ ﺗﻤﺜﯿ ﻞ‬
‫‪‬‬ ‫‪(a - x) ‬‬
‫اﻟﺴﯿﻨﺎت ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﯾﻤﺮ ﺑﻨﻘﻄﺔ اﻷﺻﻞ وﻣﯿﻠﮫ ھﻮ اﻟﺜﺎﺑﺖ‬

‫"‪. "k/2.303‬‬
‫‪....................................................................................................................................................... .................................‬‬
‫‪................................................................................ ........................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................... .............................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬

‫)‪(484‬‬
‫ﻣﺜﺎﻝ )‪(٣٢-٢‬‬
‫ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ اﻟﻨﺘ ﺎﺋﺞ اﻟﺘﺎﻟﯿ ﺔ ﻟﻠﺘﺤﻠ ﻞ اﻟﻤ ﺎﺋﻲ ﻟﻠﺴ ﻜﺮوز ﻋﻨ ﺪ‬

‫)‪: (27 ºC‬‬
‫‪Time, min‬‬ ‫‪0‬‬ ‫‪60‬‬ ‫‪130‬‬ ‫‪180‬‬
‫)‪Sugar conc. (mol/L‬‬ ‫‪1‬‬ ‫‪0.807‬‬ ‫‪0.630‬‬ ‫‪0.531‬‬
‫ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺛﻢ اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‪.‬‬

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‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................... .........................................‬‬
‫‪........................................................................................................................................................................................‬‬

‫)‪(485‬‬
‫ﻣﺜﺎﻝ )‪(٣٣-٢‬‬
‫ﯾﻌﺘﺒﺮ ﺗﺤﻠﻞ ﻛﻠﻮرﯾﺪ اﻟﺴﻠﻔﻮﻧﯿﻞ اﻟﻰ ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻜﺒﺮﯾ ﺖ وﻏ ﺎز اﻟﻜﻠ ﻮر‬
‫ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪SO 2Cl 2 ‬‬
‫‪→ SO 2 + Cl2‬‬
‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬وﺛﺎﺑﺖ ﺳﺮﻋﺘﮫ )‪ (k‬ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة )‪(320 ºC‬‬
‫)‪ .(k = 2.2 × 10-5 s-1‬اﺣﺴ ﺐ ﻧﺴ ﺒﺔ ﺗﺤﻠﻠ ﮫ ﻓ ﻲ‬ ‫ھﻮ‬
‫درﺟﺔ اﻟﺤﺮارة اﻟﻤﺬﻛﻮرة ﺑﻌﺪ ﻣﻀﻲ )‪(90 min.‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿﻖ ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬

‫‪a‬‬ ‫‪kt‬‬
‫‪log‬‬ ‫=‬
‫‪(a - x) 3.303‬‬
‫‪a‬‬ ‫‪2.2 × 10-5 × 90 × 60‬‬
‫‪log‬‬ ‫=‬
‫)‪(a - x‬‬ ‫‪3.303‬‬
‫‪a‬‬
‫‪log‬‬ ‫‪= 0.0516‬‬
‫)‪(a - x‬‬
‫‪a‬‬
‫‪=1.126‬‬
‫)‪(a - x‬‬
‫)‪a = 1.126 (a - x‬‬
‫‪a = 1.126a - 1.126 x‬‬
‫‪a - 1.126a + 1.126 x = 0‬‬
‫‪- 0.126a + 1.126 x = 0‬‬
‫‪0.126a = 1.126 x‬‬
‫‪0.126‬‬
‫=‪x‬‬ ‫‪= 0.112‬‬
‫‪1.126‬‬
‫‪% x = 0.119 × 100 = 11.2‬‬

(486)
ً‫[ ﺑ ﺪﻻ‬A] ،[A]0 ‫ واﻟﺮﻣ ﻮز‬log ‫ ﺑ ﺪﻻً ﻣ ﻦ‬ln ‫وﯾﻤﻜﻦ اﻟﺤﻞ ﺑﺎﺳ ﺘﺨﺪام‬
: ‫( ﺣﯿﺚ‬a –x) ‫ و‬a ‫ﻣﻦ‬
[A]0 = a, [A] = ([A]0 – x)
[ A ]0
ln = kt
[A]
[ A ]0
ln = 2.2 × 10-5 × ( 90 × 60 )
[A]
[ A ]0
ln = 0.1188
[A]
[ A ]0
= e0.1188
[A]
[ A ]0
= 1.126
[A]
[ A ]0
= 1.126
[ A ]0 - x
[ A ]0 =1.126 [ A ]0 -1.126x
[ A ]0 - 1.126 [ A ]0 +1.126x = 0
0.126 [ A ]0 =1.126x
0.126
x= = 0.112
1.126
% x = 0.112 × 100 = 11.2 %

‫)‪(487‬‬
‫ﻣﺜﺎﻝ )‪(٣٤-٢‬‬
‫ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺗﻢ ﻣﻦ )‪ (30 %‬ﻓﻲ زﻣ ﻦ ﻗ ﺪره )‪(35 min.‬‬

‫ﻓﺎﺣﺴﺐ ﻣﺎ ﯾﻠﻲ ‪:‬‬
‫أ( ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
‫ب( ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‬
‫ج( اﻟﺰﻣﻦ اﻟﻼزم ﻹﺗﻤﺎم )‪ (80 %‬ﻣﻦ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫أ( ‪k = 1.70 × 10-4 s-1‬‬
‫ب( زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ‪t1/2 = 68.0 min.‬‬
‫ج( اﻟﺰﻣﻦ اﻟﻼزم ﻹﺗﻤﺎم )‪ (80 %‬ﻣﻦ اﻟﺘﻔﺎﻋﻞ ‪t = 157.8 min‬‬
‫ﺍﳊﻞ ﺍﻟﺘﻔﺼﻴﻠﻲ‬
‫‪........................................................................................................................................................................................‬‬
‫‪................................................................................................................................ ........................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................... .............‬‬
‫‪.................................................................................................... ....................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................... .........................................‬‬

(488)
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........................................................................................................................................................................................

‫)‪(489‬‬
‫ﻣﺜﺎﻝ )‪(٣٥-٢‬‬
‫إذا ﻛﺎﻧﺖ ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ )‪(k = 6.71 × 10-4 s-1‬‬
‫ﻓﺎﺣﺴﺐ ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪6.71 × 10-4 s-1‬‬
‫‪t 1 = 1032.79 s‬‬
‫‪2‬‬
‫ﻣﺜﺎﻝ )‪(٣٦-٢‬‬
‫ﯾﻌﺘﺒﺮ ﺗﻔﻜﻚ اﻟﺒﯿﻮﺗﺎن ﺗﻔﺎﻋﻼً ﻣﻦ اﻟﺪرﺟﺔ اﻷوﻟ ﻰ‪ ،‬ﻓ ﺈذا ﻋﻠﻤ ﺖ أن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ ﺗﺴ ﺎوي )‪ (9.2 × 10-3 min-1‬وأن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﺒﯿﻮﺗ ﺎن ھ ﻮ‬
‫)‪ . (0.5 M‬اﺣﺴﺐ اﻟﺰﻣﻦ اﻟﻼزم ﻻﺳﺘﮭﻼك )‪ (80 %‬ﻣﻦ ھﺬا اﻟﺘﺮﻛﯿﺰ‪.‬‬
‫ﺍﳊﻞ‬
‫‪ = [ A ]0 = a = 0.5 M‬اﻟﺘﺮﻛـــــــــﯿﺰ اﻷوﻟـــــــــﻲ‬
‫‪80‬‬
‫= ‪ = x‬اﻟﺘﺮﻛــــــــــــﯿﺰ اﻟﻤﺴــــــــــــﺘﮭﻠﻚ )اﻟﻨــــــــــــﺎﺗﺞ(‬
‫‪× 0.5 = 0.4 M‬‬
‫‪100‬‬
‫‪ = [A]= (a - x) = 0.5 - 0.4 = 0.1 M‬اﻟﺘﺮﻛـــــــــــــﯿﺰ اﻟﻤﺘﻠﻘـــــــــــــﻲ‬
‫‪[ A ]0‬‬ ‫‪a‬‬
‫‪kt = ln‬‬ ‫‪= ln‬‬
‫]‪[ A‬‬ ‫)‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫) ‪k (a - x‬‬
‫‪1‬‬ ‫‪0.5‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪9.2 × 10 min‬‬
‫‪-3‬‬ ‫‪-1‬‬
‫‪0.1‬‬
‫‪t = 175.0 s‬‬

‫)‪(490‬‬
‫ﻣﺜﺎﻝ )‪(٣٧-٢‬‬
‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﻜ ﻚ )‪ (N2O5‬ھ ﻮ )‪(8.1 × 10-3 min-1‬‬

‫ﻓﺎﺣﺴ ﺐ اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺨﻔ ﺾ ﺗﺮﻛﯿ ﺰه ﻣ ﻦ )‪ (0.03 M‬إﻟ ﻰ‬
‫)‪ (0.02 M‬ﺑﻮﺣﺪة )‪.(min‬‬
‫ﺍﳊﻞ‬
‫‪ = [ A ]0 = a = 0.03 M‬اﻟﺘﺮﻛــــــــــــﯿﺰ اﻹﺑﺘــــــــــــﺪاﺋﻲ‬
‫= ] ‪ [ A‬اﻟﺘﺮﻛـــــﯿﺰ ﻋﻨـــــﺪ زﻣـــــﻦ ‪t‬‬ ‫‪( a - x ) = 0.02 M‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫) ‪k (a - x‬‬
‫‪1‬‬ ‫‪0.03‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪8.1 × 10-3 0.02‬‬
‫‪t = 50.1 min‬‬
‫ﻣﺜﺎﻝ )‪(٣٨-٢‬‬
‫ﺗﺘﻔﻜﻚ ﻣﺎدة ﻣﺎ ﺗﻔﻜﻜﺎ ً ﻣﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬ﻓ ﺈذا اﺳ ﺘﻐﺮق ﺗﻐﯿ ﺮ ﺗﺮﻛﯿﺰھ ﺎ‬
‫ﻣ ﻦ )‪ (0.705 M‬اﻟ ﻰ )‪ (0.173 M‬أرﺑ ﻊ دﻗ ﺎﺋﻖ‪ ،‬ﻓﺎﺣﺴ ﺐ ﺛﺎﺑ ﺖ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﻮﺣﺪة )‪.(s-1‬‬

‫)‪(491‬‬
‫ﺍﳊﻞ‬
‫‪ = [ A ]0 = a = 0.705 M‬اﻟﺘﺮﻛــــــــــــﯿﺰ اﻹﺑﺘــــــــــــﺪاﺋﻲ‬
‫= ] ‪ [ A‬اﻟﺘﺮﻛـــــﯿﺰ ﻋﻨـــــﺪ زﻣـــــﻦ ‪t‬‬ ‫‪( a - x ) = 0.173 M‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫)‪t (a - x‬‬
‫‪1‬‬ ‫‪0.705‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪( 4 × 60 ) s 0.173‬‬
‫‪k = 5.85 × 10-3 s-1‬‬
‫ﻣﺜﺎﻝ )‪(٣٩-٢‬‬
‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﯾﺴ ﺎوي )‪ (5 × 10-4 s-1‬ﻓﺎﺣﺴ ﺐ‬

‫اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺘﺤ ﻮل )‪ (60 %‬ﻣ ﻦ ھ ﺬا اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻠﻤ ﺎدة‬
‫اﻟﻤﺘﻔﺎﻋﻠﺔ اﻟﻰ ﻧﻮاﺗﺞ ﺑﻮﺣﺪة اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻓﻲ ھﺬه اﻟﻤﺴﺄﻟﺔ ﻟﻢ ﯾ ﺬﻛﺮ ﻗﯿﻤ ﺔ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ‪ ،‬ﻟ ﺬﻟﻚ ﺳ ﻨﻔﺮض أﻧ ﮫ‬
‫ﯾﺴﺎوي )‪.(a = 1‬‬

‫)‪(492‬‬
‫‪ = [ A ]0 = a = 1 M‬اﻟﺘﺮﻛــــــــﯿﺰ اﻷوﻟــــــــﻲ‬
‫‪60‬‬
‫= ‪ = x‬اﻟﺘﺮﻛــــــــــﯿﺰ اﻟﻤﺴــــــــــﺘﮭﻠﻚ )اﻟﻨــــــــــﺎﺗﺞ(‬ ‫‪× 1 = 0.6 M‬‬
‫‪100‬‬
‫‪ = [A]= (a - x) = 1 - 0.6 = 0.4 M‬اﻟﺘﺮﻛــــــــــــﯿﺰ اﻟﻤﺘﻠﻘــــــــــــﻲ‬
‫‪[ A ]0‬‬ ‫‪a‬‬
‫‪kt = ln‬‬ ‫‪= ln‬‬
‫]‪[A‬‬ ‫) ‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫) ‪k (a - x‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‪t‬‬ ‫‪− 4 -1‬‬
‫‪ln‬‬
‫‪5 × 10 s‬‬ ‫‪0.4‬‬
‫‪t = 1832.58 s‬‬
‫ﻣﺜﺎﻝ )‪(٤٠-٢‬‬
‫اﻛﺘﻤ ﻞ )‪ (35.5 %‬ﻣ ﻦ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻓ ﻲ زﻣ ﻦ ﻗ ﺪره‬

‫)‪ (4.9 min‬وذﻟﻚ ﻋﻨﺪ )‪ (25 ºC‬ﻓﻤﺎ ھﻮ ﺛﺎﺑﺖ ﻣﻌ ﺪل ﺳ ﺮﻋﺘﮫ ﺑﻮﺣ ﺪة‬
‫)‪(s-1‬؟‬
‫ﺍﳊﻞ‬
‫ﻟﻢ ﯾﺤﺪد اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻓﻲ اﻟﻤﺴﺄﻟﺔ ﻟﺬﻟﻚ ﺳﻨﻔﺮض أﻧﮫ ﯾﺴﺎوي )‪.( a = 1‬‬

‫)‪(493‬‬
‫‪ = [ A ]0 = a = 1 M‬اﻟﺘﺮﻛـــــــــﯿﺰ اﻷوﻟـــــــــﻲ‬
‫‪35.5‬‬
‫= ‪ = x‬اﻟﺘﺮﻛـــــــــــﯿﺰ اﻟﻤﺴـــــــــــﺘﮭﻠﻚ )اﻟﻨـــــــــــﺎﺗﺞ(‬
‫‪× 1 = 0.355 M‬‬
‫‪100‬‬
‫‪ = [A]= (a - x) = 1 - 0.355 = 0.645 M‬اﻟﺘﺮﻛــــــــــــﯿﺰ اﻟﻤﺘﻠﻘــــــــــــﻲ‬
‫‪[ A ]0‬‬ ‫‪a‬‬
‫‪kt = ln‬‬ ‫‪= ln‬‬
‫]‪[A‬‬ ‫) ‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪k = ln‬‬
‫) ‪t (a - x‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪( 4.9 × 60 ) 0.645‬‬
‫‪k = 1.49 × 10- 3 s -1‬‬
‫ﻣﺜﺎﻝ )‪(٤١-٢‬‬
‫إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ھ ﻮ )‪ (k = 3 × 10-3 s-1‬ﻓﻤ ﺎ اﻟ ﺰﻣﻦ‬

‫اﻟﺬي ﯾﺴﺘﻐﺮﻗﮫ ﺗﻐﯿﺮ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻣ ﻦ )‪ (2 M‬اﻟ ﻰ ‪(0.92‬‬
‫)‪ M‬ﺑﻮﺣﺪة )‪.(s‬‬
‫ﺍﳊﻞ‬
‫‪ = [ A ]0 = a = 2 M‬اﻟﺘﺮﻛـــــــــﯿﺰ اﻷوﻟـــــــــﻲ‬
‫‪ = [A]= (a - x) = 0.92 M‬اﻟﺘﺮﻛــــــــــــﯿﺰ اﻟﻤﺘﻠﻘــــــــــــﻲ‬
‫‪[ A ]0‬‬ ‫‪a‬‬
‫‪kt = ln‬‬ ‫‪= ln‬‬
‫]‪[A‬‬ ‫) ‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫) ‪k (a - x‬‬
‫‪1‬‬ ‫‪2‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪3 × 10 −3 s -1 0.92‬‬
‫‪t = 258.84 s‬‬

‫)‪(494‬‬
‫ﻣﺜﺎﻝ )‪(٤٢-٢‬‬
‫ﯾﻌﺘﺒﺮ ﺗﻔﻜﻚ )‪ (CH2N2‬ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪CH 2 N 2 ‬‬
‫‪→ CH 2 + N 2‬‬
‫ﺗﻔ ﺎﻋﻼً ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ‪ ،‬وﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟ ﮫ ﺗﺴ ﺎوي‬

‫)‪ (17.3 min‬ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﺔ‪ ،‬وﻛﺎن ﺗﺮﻛﯿ ﺰ )‪ (CH2N2‬ﺑﻌ ﺪ‬
‫ﻣﻀﻲ ﺧﻤﺲ دﻗﺎﺋﻖ ﯾﺴﺎوي )‪.(0.076 M‬‬
‫‪ (١‬اﺣﺴﺐ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻟـ )‪(CH2N2‬‬
‫‪ (٢‬اﺣﺴﺐ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ )‪ (40 %‬ﻣﻦ ﺗﺮﻛﯿﺰه اﻹﺑﺘﺪاﺋﻲ‪.‬‬
‫‪ (٣‬ﻣﺎ ﺗﺄﺛﯿﺮ زﯾﺎدة ﺗﺮﻛﯿﺰ )‪ (CH2N2‬ﻋﻠﻰ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻧﺤﺴﺐ أوﻻً ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ ﻗﯿﻤﺔ زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫=‪k‬‬
‫‪t1‬‬
‫‪2‬‬
‫‪0.693‬‬
‫=‪k‬‬ ‫‪= 0.04 min −1‬‬
‫‪17.3 min‬‬

(495)
: CH2N2 ‫( ﺣﺴﺎب اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻟـ‬١

[A]0 = a = ?
[A] = (a - x) = 0.076 M
t = 5 min.
a
kt = ln
a-x
kt = lna - ln(a - x)
lna = kt + ln(a - x)
lna = ( 0.04 min -1 × 5min ) + ln 0.076
ln a = - 2.377
a = 0.093 M
: ً ‫وﯾﻤﻜﻦ ﺣﻠﮭﺎ ﺑﺸﻜﻞ أﺑﺴﻂ ﺣﺴﺎﺑﯿﺎ‬

a
ln = kt
a-x
a
= ekt
a-x
a
= e 0.04 × 5
0.076
a = 0.076 × e 0.04 × 5
a = 0.093 M
: ‫( ﻛﻤﺎ ﯾﻠﻲ‬ekt) ‫ﺣﯿﺚ ﺗﺤﺴﺐ‬

(ekt = ( k × t ) then shift ln)
(k) ‫وﺗﻌﻨ ﻲ أن ﺗﻀ ﺮب ﺑﺎﻵﻟ ﺔ اﻟﺤﺎﺳ ﺒﺔ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬

ln ‫ ﺗﻠﯿﮭﺎ‬shift ‫( ﺛﻢ ﺗﻀﻐﻂ ﻛﻠﻤﺔ‬t) ‫ﺑﺎﻟﺰﻣﻦ‬

‫)‪(496‬‬
‫‪ (٢‬ﺣﺴﺎب اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ )‪ (40 %‬ﻣﻦ ﺗﺮﻛﯿﺰه ‪:‬‬

‫‪[ A ]0 = a = 0.093 M‬‬
‫‪40‬‬
‫=‪x‬‬ ‫‪× 0.093 = 0.0372‬‬
‫‪100‬‬
‫‪[A] = a - x = 0.093 - 0.0372 = 0.0558‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫‪a-x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫‪k a-x‬‬
‫‪1‬‬ ‫‪0.093‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪0.04 0.0558‬‬
‫‪t = 12.77 min‬‬
‫‪ (٣‬زﯾﺎدة ﺗﺮﻛﯿﺰ )‪ (CH2N2‬ﻻ ﯾﺆﺛﺮ ﻋﻠﻰ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬
‫ﻣﺜﺎﻝ )‪(٤٣-٢‬‬
‫إذا ﻋﻠﻤﺖ أن اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬

‫‪A + B ‬‬
‫‪→C‬‬
‫وأن )‪ (t1/2 = 200 s‬ﻓﺎﺣﺴ ﺐ اﻟ ﺰﻣﻦ ﺑ ﺎﻟﺜﻮاﻧﻲ اﻟ ﻼزم ﻻ ﺳ ﺘﮭﻼك‬

‫ﺧﻤﺲ اﻟﻜﻤﯿﺔ اﻷﺻﻠﯿﺔ ﻣﻦ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫أوﻻ ﻧﺤﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ﺑﻮﺣﺪة )‪(s-1‬‬

‫)‪(497‬‬
‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫=‪k‬‬
‫‪t1‬‬
‫‪2‬‬
‫‪0.693‬‬
‫=‪k‬‬ ‫‪= 3.465 × 10−3 s -1‬‬
‫‪200 s‬‬
‫وﻧﻔ ﺮض أن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﯾﺴ ﺎوي )‪ (a = 1 M‬وﻟﺤﺴ ﺎب‬

‫اﻟﺰﻣﻦ اﻟﻼزم ﻻﺳﺘﮭﻼك ﺧﻤﺲ اﻟﻜﻤﯿﺔ اﻷﺻﻠﯿﺔ ﻣﻦ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ‪:‬‬
‫‪[ A ]0 = a = 1 M‬‬
‫‪1‬‬
‫=‪x‬‬ ‫‪× 1 = 0.2‬‬
‫‪5‬‬
‫‪[A] = a - x = 1 - 0.2 = 0.8‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫‪a-x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫‪k a-x‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪3.465 × 10-3 s −1 0.8‬‬
‫‪t = 64.4 s‬‬
‫ﻣﺜﺎﻝ )‪(٤٤-٢‬‬
‫اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ﻣﻦ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬

‫‪4PH 3 (g) ‬‬
‫)‪→ P4 (g) + 6H 2 (g‬‬
‫ﻓﺈذا ﻛﺎﻧﺖ )‪ (t1/2 = 35 s‬ﻋﻨﺪ )‪(680 ºC‬‬

‫)‪(498‬‬
‫اﺣﺴﺐ ‪:‬‬
‫‪ (١‬ﺛﺎﺑﺖ ﻣﻌﺪل ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫‪ (٢‬اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﻜﻚ )‪ (5 %‬ﻣﻦ )‪(PH3‬‬
‫ﺍﳊﻞ‬
‫‪ (١‬ﺣﺴﺎب ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫=‪k‬‬
‫‪t1‬‬
‫‪2‬‬
‫‪0.693‬‬
‫=‪k‬‬ ‫‪= 1.98 × 10-2 s -1‬‬
‫‪35 s‬‬
‫‪ (٢‬اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﻜﻚ )‪ (5 %‬ﻣﻦ )‪(PH3‬‬

‫ﻧﻔﺮض أن اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﯾﺴﺎوي )‪: (1 M‬‬
‫‪[ A ]0 = a = 1 M‬‬
‫‪5‬‬
‫=‪x‬‬ ‫‪× 1 = 0.05‬‬
‫‪100‬‬
‫‪[A] = a - x = 1 - 0.05 = 0.95‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫‪a-x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫‪k a-x‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‪t‬‬ ‫‪−2 −1‬‬
‫‪ln‬‬
‫‪1.98 × 10 s‬‬ ‫‪0.95‬‬
‫‪t = 2.59 s‬‬

‫)‪(499‬‬
‫ﻣﺜﺎﻝ )‪(٤٥-٢‬‬
‫ﯾﻌﺪ ﺗﺤﻠﻞ )‪ (N2O5‬ﺗﻔﺎﻋﻼً ﻣﻦ اﻟﺪرﺟﺔ اﻷوﻟﻰ‪ ،‬ﻓﺈذا ﻛﺎﻧﺖ ﻓﺘﺮة ﻧﺼﻒ‬

‫اﻟﻌﻤﺮ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي )‪ (1114 s‬ﻓﺎﺣﺴﺐ اﻟﺰﻣﻦ اﻟ ﻼزم ﻟﺨﻔ ﺾ‬
‫اﻟﺘﺮﻛﯿﺰ ﻣﻦ )‪ (0.1 M‬اﻟﻰ )‪.(0.01 M‬‬
‫ﺍﳊﻞ‬
‫ﻣﻦ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻧﺤﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫=‪k‬‬
‫‪t1‬‬
‫‪2‬‬
‫‪0.693‬‬
‫=‪k‬‬ ‫‪= 6.221 × 10-4 s-1‬‬
‫‪1114 s‬‬
‫وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺨﻔ ﺾ اﻟﺘﺮﻛﯿ ﺰ ﻣ ﻦ )‪ (0.1 M‬إﻟ ﻰ‬

‫)‪: (0.01 M‬‬
‫‪[ A ]0 = a = 0.1 M‬‬
‫‪[A] = a - x = 0.01‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫‪a-x‬‬
‫‪1‬‬ ‫‪a‬‬
‫‪t = ln‬‬
‫‪k a-x‬‬
‫‪1‬‬ ‫‪0.1‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪6.221 × 10-4 s −1 0.01‬‬
‫‪t = 3701.3 s‬‬

‫)‪(500‬‬
‫ﻣﺜﺎﻝ )‪(٤٦-٢‬‬
‫ﯾﺘﻔﻜﻚ ﻛﻠﻮرﯾﺪ اﻹﯾﺜﯿﻞ ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﻣﻌﯿﻨﺔ ﺣﺴﺐ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪C 2 H 5Cl ‬‬
‫‪→ C 2 H 4 + HCl‬‬
‫ﻓ ﺈذا ﻋﻠﻤ ﺖ أن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﯾﺴ ﺎوي )‪(1.6 × 10-6 s-1‬‬

‫واﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻜﻠﻮرﯾﺪ اﻹﯾﺜﯿﻞ ﯾﺴﺎوي )‪.(0.165 mol L-1‬‬
‫‪ (١‬ﻣﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫‪ (٢‬ﻣﺎ ﺗﺮﻛﯿﺰ )‪ (C2H5Cl‬ﺑﻌﺪ ﻣﻀﻲ )‪(125 h‬؟‬
‫‪ (٣‬ﻣﺎ ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﻠﺘﻔﺎﻋﻞ؟‬
‫ﺍﳊﻞ‬
‫‪ (١‬رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ھﻲ اﻷوﻟﻰ ﺑﺴﺒﺐ أن وﺣﺪة ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ھﻲ )‪.(s-1‬‬

‫‪ (٢‬ﺣﺴﺎب ﺗﺮﻛﯿﺰ )‪ (C2H5Cl‬ﺑﻌﺪ ﻣﻀﻲ )‪: (125 h‬‬
‫‪[ A ]0 = a = 0.165 mol L-1‬‬
‫? = ) ‪[A] = ( a - x‬‬
‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫) ‪(a - x‬‬
‫‪a‬‬
‫‪= e kt‬‬
‫) (‬
‫‪a‬‬ ‫‪-‬‬ ‫‪x‬‬
‫‪a‬‬
‫= ) ‪(a - x‬‬
‫‪e kt‬‬
‫‪0.165‬‬
‫= ) ‪(a - x‬‬ ‫‪-6‬‬
‫‪e125 × 3600 × 1.6 × 10‬‬
‫‪0.165‬‬
‫= ) ‪(a - x‬‬ ‫‪= 0.080 mol L-1‬‬
‫‪2.054‬‬

‫)‪(501‬‬
‫‪ (٣‬ﺣﺴﺎب ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ‪:‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪1.6 × 10-6‬‬
‫‪t 1 = 433125 s‬‬
‫‪2‬‬
‫‪t 1 = 120.3 h‬‬

‫‪2‬‬
‫ﻣﺜﺎﻝ )‪(٤٧-٢‬‬
‫ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬

‫‪A ‬‬
‫‪→B‬‬
‫ﯾﺴ ﺎوي )‪ ،(k = 1.2 × 10-2 s-1‬ﻓ ﺈذا ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻷﺻ ﻠﻲ ﻟﻠﻤ ﺎدة‬
‫ﯾﺴﺎوي )‪ (2 M‬ﻓﻤﺎ اﻟﻤﺘﺒﻘﻲ ﻣﻨﮭﺎ ﺑﻌﺪ ﻣﺮور )‪(200 s‬؟‬
‫ﺍﳊﻞ‬
‫‪[ A ]0 = a = 0.165 mol L-1‬‬
‫? = ) ‪[A] = ( a - x‬‬
‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫)‪(a - x‬‬
‫‪a‬‬
‫‪= e kt‬‬
‫)‪(a - x‬‬
‫‪a‬‬
‫) ‪(a - x‬‬ ‫=‬
‫‪e kt‬‬
‫‪2‬‬
‫= ) ‪(a - x‬‬ ‫‪1.2 × 10-2 × 200‬‬
‫‪e‬‬
‫‪2‬‬
‫= ) ‪(a - x‬‬ ‫‪= 0.181 mol L-1‬‬
‫‪11.02‬‬

‫)‪(502‬‬
‫ﻣﺜﺎﻝ )‪(٤٨-٢‬‬
‫إذا ﻛ ﺎن ﺗﻔﻜ ﻚ )‪ (N2O5 (g‬اﻟﻤ ﺬاب ﻓ ﻲ راﺑ ﻊ ﻛﻠﻮرﯾ ﺪ اﻟﻜﺮﺑ ﻮن ھ ﻮ‬

‫ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪2N 2 O5 (g) ‬‬
‫)‪→ 4NO 2 (g) + O 2 (g‬‬
‫ﻓ ﺈذا ﺑ ﺪأ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (45 ºC‬ﺑﺘﺮﻛﯿ ﺰ )‪ (N2O5‬ﻗ ﺪره‬

‫)‪ (9.00 mol L-1‬واﻧﺨﻔﺾ ﺗﺮﻛﯿﺰه ﺑﻌ ﺪ )‪ (3 h‬إﻟ ﻰ )‪،(1.21 × 10-3‬‬
‫ﻓﻤﺎ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻟـ )‪ (N2O‬ﻣﻌﺒﺮاً ﻋﻨﮭﺎ ﺑﺎﻟﺪﻗﺎﺋﻖ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻧﺤﺴﺐ أوﻻ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪[ A ]0 = a = 9.00 mol L-1‬‬
‫‪[A] = (a - x) = 1.21 × 10-3 mol L-1‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫)‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫) ‪t (a - x‬‬
‫‪1‬‬ ‫‪9‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫‪3 × 60 1.21 × 10-3‬‬
‫‪k = 0.0495 min −1‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈﻧﮫ ﻟﺤﺴﺎب ﻧﺼﻒ اﻟﻌﻤﺮ ﻧﺘﺒﻊ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪0.0495 min −1‬‬
‫‪t 1 = 14 min‬‬
‫‪2‬‬

‫)‪(503‬‬
‫ﻣﺜﺎﻝ )‪(٤٩-٢‬‬
‫ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻋﻨﺪ )‪: (45 ºC‬‬

‫‪2N 2 O5 (g) ‬‬
‫)‪→ 4NO2 (g) + O2 (g‬‬
‫ھﻮ )‪ (k = 4.8 × 10-4 s-1‬وﻛﺎن اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﻤ ﺎدة )‪(N2O5‬‬
‫ھﻮ )‪ (1.6 × 10-2 mol/L‬اﺣﺴﺐ ‪:‬‬
‫‪ (١‬ﺗﺮﻛﯿﺰ )‪ (N2O5‬ﺑﻌﺪ ﻣﺮور )‪(10 min‬‬
‫‪ (٢‬ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‬
‫‪ (٣‬اﻟﺰﻣﻦ اﻟﻼزم ﻣﻦ أﺟﻞ أن ﯾﺘﺤﻮل )‪ (70 %‬ﻣﻦ اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ‬
‫ﻟـ )‪.(N2O5‬‬
‫ﺍﳊﻞ‬
‫‪ (١‬ﺗﺮﻛﯿﺰ )‪ (N2O5‬ﺑﻌﺪ ﻣﺮور )‪(10 min‬‬

‫‪[ A ]0 = a = 1.6 × 10-2 mol L-1‬‬
‫? = ) ‪[A] = ( a - x‬‬
‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫) ‪(a - x‬‬
‫‪a‬‬
‫‪= e kt‬‬
‫) ‪(a - x‬‬
‫‪a‬‬
‫) ‪(a - x‬‬ ‫=‬
‫‪e kt‬‬
‫‪1.6 × 10-2‬‬
‫= ) ‪(a - x‬‬ ‫‪−4‬‬
‫‪e 4.8 × 10 × 10 × 60‬‬
‫‪1.6 × 10-2‬‬
‫) (‬
‫‪a‬‬ ‫‪-‬‬ ‫‪x‬‬ ‫=‬ ‫‪= 0.012 mol L-1‬‬
‫‪1.33‬‬

‫)‪(504‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪4.8 × 10- 4 s -1‬‬
‫‪t 1 = 1443.75 s‬‬
‫‪2‬‬
‫‪ (٣‬اﻟﺰﻣﻦ اﻟﻼزم ﻣﻦ أﺟﻞ أن ﯾﺘﺤﻮل )‪ (70 %‬ﻣﻦ اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ‬

‫ﻟـ )‪(N2O5‬‬
‫× ‪[ A ]0 = a = 1.6‬‬ ‫‪10- 2 mol L-1‬‬
‫‪70‬‬
‫=‪x‬‬ ‫‪× 1.6 × 10- 2 = 0.0112‬‬
‫‪100‬‬
‫‪[A] = ( a - x ) = (1.6 × 10- 2 − 1.12 × 10− 2 ) = 4.8 × 10-3‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫) ‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫) ‪k (a - x‬‬
‫‪1‬‬ ‫‪1.6 × 10- 2‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪4.8 × 10- 4 4.8 × 10- 3‬‬
‫‪t = 2508.28 s‬‬
‫‪t = 41.80 min‬‬
‫ﻣﺜﺎﻝ )‪(٥٠-٢‬‬
‫إذا ﻛ ﺎن ﺗﺤ ﻮل اﻟﺒﺮوﺑ ﺎن اﻟﺤﻠﻘ ﻲ اﻟ ﻰ ﺑ ﺮوﺑﯿﻦ ﻓ ﻲ اﻟﺤﺎﻟ ﺔ اﻟﻐﺎزﯾ ﺔ ﯾ ﺘﻢ‬
‫ﻋﻨ ﺪ )‪ (250 ºC‬ﻓ ﺈذا ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ وﻛ ﺎن ﺛﺎﺑ ﺖ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ھﻮ )‪ ،(k = 6.71 × 10-4 s-1‬اﺣﺴﺐ ‪:‬‬
‫‪ (١‬ﺗﺮﻛﯿﺰ اﻟﺒﺮوﺑﺎن اﻟﺤﻠﻘﻲ ﺑﻌ ﺪ ﻣ ﺮور )‪ (4.5 min‬إذا ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻹﺑﺘﺪاﺋﻲ ﻟﻠﺒﺮوﺑﺎن اﻟﺤﻠﻘﻲ )‪.(0.25 mol /L‬‬

‫)‪(505‬‬

‫‪ (٣‬اﻟﺰﻣﻦ اﻟﻼزم ﻣﻦ أﺟ ﻞ أن ﯾﺘﺤ ﻮل )‪ (72 %‬ﻣ ﻦ اﻟﺘﺮﻛﯿ ﺰ اﻟﻤﺒ ﺪﺋﻲ‬
‫ﻟﻠﺒﺮوﺑﺎن‪.‬‬
‫ﺍﳊﻞ‬
‫‪ (١‬ﺗﺮﻛﯿﺰ اﻟﺒﺮوﺑﺎن اﻟﺤﻠﻘﻲ ﺑﻌ ﺪ ﻣ ﺮور )‪ (4.5 min‬إذا ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ‬

‫اﻹﺑﺘﺪاﺋﻲ ﻟﻠﺒﺮوﺑﺎن اﻟﺤﻠﻘﻲ )‪.(0.25 mol /L‬‬
‫‪[ A ]0 = a = 0.25 mol L-1‬‬
‫? = ) ‪[A] = ( a - x‬‬
‫‪a‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫) ‪(a - x‬‬
‫‪a‬‬
‫‪= ekt‬‬
‫) ‪(a - x‬‬
‫‪a‬‬
‫)‪(a - x‬‬ ‫=‬
‫‪e kt‬‬
‫‪0.25‬‬
‫= )‪(a - x‬‬ ‫‪6.71 × 10-4 × 4.5 × 60‬‬
‫‪e‬‬
‫‪0.25‬‬
‫= )‪(a - x‬‬ ‫‪= 0.21 mol L-1‬‬
‫‪1.2‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪6.71 × 10- 4 s -1‬‬
‫‪t 1 = 1032.8 s‬‬
‫‪2‬‬

‫)‪(506‬‬
‫‪ (٣‬اﻟﺰﻣﻦ اﻟﻼزم ﻣﻦ أﺟ ﻞ أن ﯾﺘﺤ ﻮل )‪ (72 %‬ﻣ ﻦ اﻟﺘﺮﻛﯿ ﺰ اﻟﻤﺒ ﺪﺋﻲ‬

‫ﻟﻠﺒﺮوﺑﺎن‪.‬‬
‫‪[ A ]0 = a = 0.25 mol L-1‬‬
‫‪72‬‬
‫=‪x‬‬ ‫‪× 0.25 = 0.18‬‬
‫‪100‬‬
‫‪[A] = ( a - x ) = ( 0.25 − 0.18 ) = 0.07‬‬
‫‪a‬‬
‫‪kt = ln‬‬
‫) ‪(a - x‬‬
‫‪1‬‬ ‫‪a‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫) ‪k (a - x‬‬
‫‪1‬‬ ‫‪0.25‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪6.71 × 10‬‬ ‫‪-4‬‬
‫‪0.07‬‬
‫‪t = 1897.12 s‬‬
‫‪t = 31.62 min‬‬
‫ﻣﺜﺎﻝ )‪(٥١-٢‬‬
‫ﯾﻤﻜ ﻦ ﺗﺤﻮﯾ ﻞ اﻵزوﻣﯿﺜ ﺎن اﻟ ﻰ إﯾﺜ ﺎن وﻧﯿﺘ ﺮوﺟﯿﻦ ﻋﻨ ﺪ )‪(300 ºC‬‬

‫ﺣﺴﺐ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ اﻟﺬي ھﻮ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬
‫‪CH3 -N=N-CH3 ‬‬
‫‪→ CH3 -CH3 + N2‬‬
‫ووﺟﺪ أن ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨ ﺪ ھ ﺬه اﻟﺪرﺟ ﺔ )‪ (k = 2.56 × 10-3 s-1‬وﻛ ﺎن‬

‫اﻟﻀﻐﻂ اﻟﺠﺰﺋﻲ ﻟﻶﯾﺰوﻣﯿﺜﺎن )‪ (284 mmHg‬ﻓﺎﺣﺴﺐ ‪:‬‬
‫‪ (١‬اﻟﻀﻐﻂ اﻟﺠﺰﺋﻲ ﻟﻶﯾﺰوﻣﯿﺜﺎن ﺑﻌﺪ )‪.(3 min‬‬
‫‪ (٢‬اﻟﻔﺘ ﺮة اﻟﺰﻣﻨﯿ ﺔ ﻟﺨﻔ ﺾ اﻟﻀ ﻐﻂ اﻟﺠﺰﺋ ﻲ ﻟﻶﯾﺰوﻣﯿﺜ ﺎن ﻣ ﻦ‬
‫)‪ (248 mmHg‬اﻟﻰ )‪.(100 mmHg‬‬
‫‪ (٣‬ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬

‫)‪(507‬‬
‫ﺍﳊﻞ‬
‫اﻟﻀ ﻐﻂ اﻻﺑﺘ ﺪاﺋﻲ )‪ (P0‬ﯾﻘﺎﺑ ﻞ اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ‪ ،[A]0‬واﻟﻀ ﻐﻂ‬

‫)‪(Pt‬ﻋﻨﺪ زﻣﻦ )‪ (t‬ﯾﻘﺎﺑﻞ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ]‪ [A‬ﻋﻨﺪ زﻣﻦ )‪.(t‬‬
‫وﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﯾﻤﻜﻦ أن ﯾﺼﺎغ ﻓﻲ ﺣﺎﻟﺔ اﻟﻀﻐﻮط ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪P0‬‬
‫‪kt = ln‬‬
‫‪Pt‬‬
‫‪ (١‬اﻟﻀﻐﻂ اﻟﺠﺰﺋﻲ ﻟﻶﯾﺰوﻣﯿﺜﺎن ﺑﻌﺪ )‪.(3 min‬‬

‫‪P0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫‪Pt‬‬
‫‪P0‬‬
‫‪= e kt‬‬
‫‪Pt‬‬
‫‪P0‬‬
‫= ‪Pt‬‬
‫‪e kt‬‬
‫‪284 mmHg‬‬
‫= ‪Pt‬‬
‫‪e 2.56 × 10 × 3 × 60‬‬
‫‪-3‬‬
‫‪284 mmHg‬‬
‫= ‪Pt‬‬
‫‪1.585‬‬
‫‪Pt = 179.2 mm Hg‬‬
‫‪ (٢‬اﻟﻔﺘ ﺮة اﻟﺰﻣﻨﯿ ﺔ ﻟﺨﻔ ﺾ اﻟﻀ ﻐﻂ اﻟﺠﺰﺋ ﻲ ﻟﻶﯾﺰوﻣﯿﺜ ﺎن ﻣ ﻦ‬

‫)‪ (248 mmHg‬اﻟﻰ )‪.(100 mmHg‬‬

‫)‪(508‬‬
‫‪P0 = 284 mmHg‬‬

‫‪P = 100 mmHg‬‬
‫‪P‬‬
‫‪kt = ln 0‬‬
‫‪Pt‬‬
‫‪1 P0‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪k Pt‬‬
‫‪1‬‬ ‫‪284‬‬
‫=‪t‬‬ ‫‪ln‬‬
‫‪2.56 × 10‬‬ ‫‪-3‬‬
‫‪100‬‬
‫‪t = 407.74 s‬‬
‫‪ (٣‬ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬

‫‪0.693‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪2.56 × 10− 3 s-1‬‬
‫‪t 1 = 271.7 s‬‬
‫‪2‬‬
‫ﻣﺜﺎﻝ )‪(٥٢-٢‬‬
‫إذا ﻋﻠﻤ ﺖ أن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﻜ ﻚ اﻟﻤ ﺎدة )‪ (AB‬ﯾﺴ ﺎوي )‪(3.2 × 10-2‬‬
‫ﻓﺎﺣﺴﺐ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺨﻔﺾ ﺗﺮﻛﯿﺰه اﻟﻰ اﻟﻨﺼﻒ ﺑﻮﺣﺪة )‪.(s‬‬
‫ﺍﳉﻮﺍﺏ ‪21.65 s :‬‬
‫‪........................................................................................................................................................................ ................‬‬
‫‪................................................................................................. .......................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................ ............................................‬‬

‫)‪(509‬‬
‫ﻣﺜﺎﻝ )‪(٥٣-٢‬‬
‫إذا ﻋﻠﻤ ﺖ أن )‪ (t1/2 = 80 min‬وذﻟ ﻚ ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬

‫ﻓﺎﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﻮﺣﺪة )‪.(min-1‬‬
‫ﺍﳉﻮﺍﺏ ‪k = 8.66 × 10-3 min-1 :‬‬

‫‪.................................................................................. ......................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................. ...........................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................ ................‬‬
‫‪................................................................................................. .......................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................ ............................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪....................................................................................................................................................................................... .‬‬
‫‪................................................................................................................ ........................................................................‬‬
‫‪................................................................................................................ ........................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬

‫)‪(510‬‬
‫ﻣﺜﺎﻝ )‪(٥٤-٢‬‬
‫ﯾﻌﺘﺒﺮ ﺗﻔﻜﻚ اﻟﻔﻮﺳﻔﯿﻦ ﺗﻔﺎﻋﻼً ﻣﻦ اﻟﺪرﺟﺔ اﻷوﻟﻰ ‪:‬‬

‫‪4 PH3 ‬‬
‫‪→ P4 + 6 H 2‬‬
‫ﻓﺈذا اﺳﺘﻐﺮﻗﺖ ﻋﻤﻠﯿﺔ ﺗﻔﻜﻚ ﻧﺼﻒ ﻛﻤﯿﺔ ﻣﻌﯿﻨﺔ ﻣﻨﮫ زﻣﻨﺎ ً ﻗ ﺪره )‪(35 s‬‬
‫ﻓﺎﺣﺴﺐ ‪:‬‬
‫‪ (١‬ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
‫‪ (٢‬اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﻜﻚ رﺑﻊ اﻟﻜﻤﯿﺔ ﻋﻨﺪ ﻧﻔﺲ اﻟﻈﺮوف‪.‬‬
‫‪ (١‬ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪k = 0.02 s-1 :‬‬
‫‪ (٢‬اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﻜﻚ رﺑﻊ اﻟﻜﻤﯿﺔ ‪t = 14.4 s :‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪....................................................................................................................... .................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪.................................................................................................................................................................. ......................‬‬
‫‪........................................................................................... .............................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪...................................................................................................................................... ..................................................‬‬

‫)‪(511‬‬
‫ﻣﺜﺎﻝ )‪(٥٥-٢‬‬
‫إذا ﻛﺎن ﺛﺎﺑﺖ ﺳﺮﻋﺔ ﺗﻔﻜ ﻚ ﻏ ﺎز )‪ (N2O5‬ھ ﻮ )‪(k = 8.1 × 10-3 min-1‬‬
‫ﻓﺎﺣﺴﺐ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺨﻔﺾ ﺗﺮﻛﯿ ﺰه ﻣ ﻦ )‪ (0.03 M‬إﻟ ﻰ )‪(0.003 M‬‬
‫ﺑﻮﺣﺪة )‪.(min‬‬
‫ﺍﳉﻮﺍﺏ ‪t = 284.27 min :‬‬

‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................................................................ ............‬‬
‫‪..................................................................................................... ...................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
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‫)‪(512‬‬
‫ﻣﺜﺎﻝ )‪(٥٦-٢‬‬
‫ﺗﺘﻔﻜ ﻚ ﻣ ﺎدة ﻣﻌﯿﻨ ﺔ ﺗﻔﻜﻜ ﺎ ً ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬ﻓ ﺈذا اﺳ ﺘﻐﺮق ﺗﻐﯿ ﺮ‬
‫ﺗﺮﻛﯿﺰھﺎ ﻣﻦ )‪ (0.705 mol/L‬اﻟﻰ )‪ (0.173 mol/L‬أرﺑﻊ دﻗ ﺎﺋﻖ‪،‬‬
‫ﻓﺎﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﻮﺣﺪة )‪.(s-1‬‬
‫ﺍﳉﻮﺍﺏ ‪k = 5.85 × 10-3 s-1 :‬‬

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‫)‪(513‬‬
‫ﻣﺜﺎﻝ )‪(٥٧-٢‬‬
‫إذا ﻋﻠﻤ ﺖ أن ﺗﻔﻜ ﻚ )‪ (C2H5Cl‬ﺗﻔ ﺎﻋﻼً ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ وﻛ ﺎن‬

‫ﺗﺮﻛﯿﺰ )‪ (C2H5Cl‬ﺑﻌﺪ ﻣﺮور دﻗﯿﻘﺔ واﺣﺪة ھﻮ )‪ .(0.01 mol/L‬ﻓﻤﺎ‬
‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﮭﺬه اﻟﻤﺎدة؟ ﻋﻠﻤﺎ ً ﺑﺄن )‪.(t1/2 = 22 s‬‬
‫ﺍﳉﻮﺍﺏ ‪ :‬اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ‪[A] = a = 0.066 mol/L :‬‬

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‫)‪(514‬‬
‫ﻣﺜﺎﻝ )‪(٥٨-٢‬‬
‫ﯾﺘﻔﻜﻚ ﻛﻠﻮرﯾﺪ اﻹﯾﺜﯿﻞ ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﻣﻌﯿﻨﺔ ﺣﺴﺐ اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪C 2 H 5Cl ‬‬
‫‪→ C 2 H 4 + HCl‬‬
‫ﻓﺈذا ﻋﻠﻤﺖ أن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﯾﺴ ﺎوي )‪(k = 1.6 × 10-6 s-1‬‬
‫واﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻟﻜﻠﻮرﯾﺪ اﻹﯾﺜﯿﻞ ﯾﺴﺎوي )‪.(0.165 mol/L‬‬
‫‪ (١‬ﻣﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ؟‬
‫‪ (٢‬ﻣﺎ ﺗﺮﻛﯿﺰ ‪ C2H5Cl‬ﺑﻌﺪ ﻣﻀﻲ )‪(125 h‬‬
‫‪ (٣‬ﻣﺎ ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫‪ (١‬رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ھﻲ اﻷوﻟﻰ‬
‫‪ (٢‬اﻟﺘﺮﻛﯿﺰ ﺑﻌﺪ ﻣﻀﻲ )‪ (125 h‬ﯾﺴﺎوي )‪(0.08 mol/L‬‬
‫‪ (٣‬ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﻠﺘﻔﺎﻋﻞ ‪t1/ 2 = 120.3 h :‬‬
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(515)
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‫)‪(516‬‬
‫ﻣﺜﺎﻝ )‪(٥٩-٢‬‬
‫اﻟﺘﻔﻜﻚ اﻟﺤﻔﺰي ﻟﻔﻮق أﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ ﻓﻲ ﻣﺤﻠﻮل ﻣﺎﺋﻲ أﻣﻜﻦ ﺗﺘﺒﻌﮫ‬

‫وذﻟﻚ ﺑﻤﻌﺎﯾﺮة ﻋﯿﻨﺎت ﻣﻨﮫ ﻣﻊ ‪ KMnO4‬ﻋﻨﺪ ﻣﺨﺘﻠﻒ اﻷزﻣﻨﺔ وذﻟ ﻚ‬
‫ﻟﺘﻌﯿ ﯿﻦ ﺗﺮﻛﯿ ﺰ ﻓ ﻮق أﻛﺴ ﯿﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ اﻟﻐﯿ ﺮ ﻣﺘﻔﺎﻋ ﻞ‪ ،‬ﺗﺒﻌ ﺎ ً ﻟﻠﻨﺘ ﺎﺋﺞ‬
‫اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪time/min‬‬ ‫‪5‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪50‬‬
‫‪3‬‬
‫‪Volume of KMnO4/cm‬‬ ‫‪37.1‬‬ ‫‪29.8‬‬ ‫‪19.6‬‬ ‫‪12.3‬‬ ‫‪5.0‬‬
‫وﺿ ﺢ ﺑﺎﻟﺮﺳ ﻢ اﻟﺒﯿ ﺎﻧﻲ أن اﻟﺘﻔﺎﻋ ﻞ أﺣ ﺎدي اﻟﺮﺗﺒ ﺔ‪ ،‬ﺛ ﻢ اﺣﺴ ﺐ ﺛﺎﺑ ﺖ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
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(517)
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‫)‪(518‬‬
‫ﻣﺜﺎﻝ )‪(٦٠-٢‬‬
‫اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ﻟﺘﻤﯿﺆ اﻟﺴﻜﺮ ﻓﻲ ﻣﺤﻠﻮل ﻣﺎﺋﻲ ﻋﻨﺪ )‪: (23 ºC‬‬
‫‪time/min‬‬ ‫‪0‬‬ ‫‪60‬‬ ‫‪130‬‬ ‫‪180‬‬
‫‪Sugar concentration mol dm -3‬‬ ‫‪1.000‬‬ ‫‪0.807‬‬ ‫‪0.630‬‬ ‫‪0.531‬‬
‫ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ أﺣﺎدي اﻟﺮﺗﺒﺔ واﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻤﯿﺆ‪.‬‬
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(519)
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‫)‪(520‬‬
‫ﻣﺜﺎﻝ )‪(٦١-٢‬‬
‫ﯾﺘﻔﻜﻚ )‪ (40 %‬ﻣﻦ اﻟﻤﺘﻔﺎﻋﻼت ﻟﺘﻔﺎﻋﻞ ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ ﻓ ﻲ ﻣ ﺪة‬

‫ﻗﺪرھﺎ )‪ ،(70 s‬ﻣﺎ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﻜﻚ )‪ (90%‬؟‬
‫ﺍﳉﻮﺍﺏ ‪t = 315.42 s :‬‬

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(521)
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‫)‪(522‬‬
‫ﻣﺜﺎﻝ )‪(٦٢-٢‬‬
‫ﯾﺘﺒﻊ ﺗﻤﯿﺆ ﻣﯿﺜﯿﻞ اﻟﺒﺮوﻣﯿﺪ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬وﯾﻤﻜﻦ ﺗﺘﺒﻌﮫ ﺑﻤﻌﺎﯾﺮة ﻋﯿﻨ ﺎت‬
‫ﻣﻦ ﺧﻠﯿﻂ اﻟﺘﻔﺎﻋﻞ ﻣﻊ ﻧﺘﺮات اﻟﻔﻀ ﺔ‪ .‬وﻗ ﺪ وﺟ ﺪ ﻓ ﻲ ﺗﺠﺮﺑ ﺔ ﺗﻘﻠﯿﺪﯾ ﺔ أن‬
‫اﻟﺤﺠ ﻢ اﻟﻤﻄﻠ ﻮب ﻣ ﻦ ﻧﺘ ﺮات اﻟﻔﻀ ﺔ ﻟﻌﯿﻨ ﺎت ﺗﺘﻜ ﻮن ﻣ ﻦ )‪10‬‬
‫ﻣﻠﻠﯿﺘﺮات( ﻓﻲ درﺟﺔ ﺣﺮارة )‪ (330 K‬ھﻮ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫)‪Time (min.‬‬ ‫‪0‬‬ ‫‪88‬‬ ‫‪300‬‬ ‫‪412‬‬ ‫∞‬
‫)‪V(AgNO3 ) (ml‬‬ ‫‪0‬‬ ‫‪5.4‬‬ ‫‪17.3‬‬ ‫‪22.1‬‬ ‫‪49.5‬‬
‫اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
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(523)
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‫)‪(524‬‬
‫ﻣﺜﺎﻝ )‪(٦٣-٢‬‬
‫اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿ ﺔ ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿﮭ ﺎ ﻣ ﻦ ﺗﺤﻠ ﻞ )‪ (17 %‬ﻣ ﻦ اﻟﺴ ﻜﺮوز‬

‫ﻓ ﻲ )‪ (0.099 N‬ﻣ ﻦ ﻣﺤﻠ ﻮل ﺣﻤ ﺾ اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ )‪ (HCl‬ﻓ ﻲ‬
‫درﺟﺔ ﺣﺮارة )‪.(T = 308 K‬‬
‫‪Time, min.‬‬ ‫‪0.00 9.82 59.60 93.18 142.9 249.8 589.4‬‬
‫‪2‬‬
‫‪[Sucrose] × 10 , mol/L‬‬ ‫‪99.00 96.5 80.3 71.3 59.8 32.8 11.1‬‬
‫ﻓﻤﺎ درﺟﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺴﻜﺮوز‪ ،‬وﻣﺎ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻧﻔﺘ ﺮض أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ .‬وﻧﺘﺄﻛ ﺪ ﺑﺤﺴ ﺎب ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﻓﺈذا ﺣﺼﻠﻨﺎ ﻋﻠﻰ ﻗﯿﻤ ﺔ ﺛﺎﺑﺘ ﺔ ﻟ ـ )‪(k‬‬
‫ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ﺑﺎﻟﻔﻌﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟ ﻰ‪ .‬أﻣ ﺎ إذا ﺣﺼ ﻠﻨﺎ ﻋﻠ ﻰ ﻗ ﯿﻢ‬
‫ﻏﯿﺮ ﺛﺎﺑﺘﺔ )أو ﻏﯿﺮ ﻣﺘﻘﺎرﺑﺔ( ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ﻣﻦ رﺗﺒﺔ ﻏﯿ ﺮ اﻷوﻟ ﻰ‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻧﺤﺎول ﻣﻊ ﻗﻮاﻧﯿﻦ رﺗﺐ أﺧﺮى‪.‬‬
‫وﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ )‪ (k‬ﺑﻄﺮﯾﻘﺘﯿﻦ ‪:‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫)‪(a - x‬‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫) ‪( a - x1‬‬
‫) ‪( t 2 - t1 ) ( a - x 2‬‬

‫)‪(525‬‬
‫‪a × 103 = 99.00‬‬

‫‪Time, min.‬‬ ‫‪9.82‬‬ ‫‪59.60‬‬ ‫‪93.18‬‬ ‫‪142.9‬‬ ‫‪249.8‬‬ ‫‪589.4‬‬
‫‪[Sucrose] × 103 N‬‬ ‫‪96.5‬‬ ‫‪80.3‬‬ ‫‪71.3‬‬ ‫‪59.8‬‬ ‫‪32.8‬‬ ‫‪11.1‬‬
‫‪= (a – x) × 103‬‬
‫‪ a ‬‬ ‫‪1.026‬‬ ‫‪1.233‬‬ ‫‪1.388‬‬ ‫‪1.655‬‬ ‫‪3.018‬‬ ‫‪8.919‬‬
‫‪‬‬ ‫‪‬‬
‫‪a -x‬‬
‫‪ a ‬‬ ‫‪0.0111‬‬ ‫‪0.0910 0.1424 0.2188 0.4797‬‬ ‫‪0.950‬‬
‫‪log ‬‬ ‫‪‬‬
‫‪a -x‬‬
‫‪2.303‬‬ ‫‪a‬‬ ‫‪2.614‬‬ ‫‪3.515 3.519‬‬ ‫‪3.526‬‬ ‫‪4.423‬‬ ‫‪3.713‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫)‪(a - x‬‬ ‫‪× 10‬‬‫‪-3‬‬
‫‪× 10-3 × 10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-3‬‬
‫‪k = 3.552 × 10-3‬‬
‫وﻧﻼﺣﻆ أن اﻟﻘ ﯿﻢ ﻣﺘﻘﺎرﺑ ﺔ ﺟ ﺪاً وأن ﻣﺘﻮﺳ ﻂ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ‪:‬‬
‫)‪ (k = 3.552 ×10-3 min-1‬ﻣﻤﺎ ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫وﯾﻤﻜ ﻦ ﺣﺴ ﺎب ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺎﻟﻌﻼﻗ ﺔ اﻷﺧ ﺮى‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫) ‪( a - x1‬‬
‫‪:‬‬ ‫) ‪( t 2 - t1 ) ( a - x 2‬‬
‫‪a × 103 = 99.00‬‬
‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬
‫‪Time, min.‬‬ ‫‪9.82‬‬ ‫‪59.60‬‬ ‫‪93.18‬‬ ‫‪142.9‬‬ ‫‪249.8‬‬ ‫‪589.4‬‬
‫‪(a – x) × 103‬‬ ‫‪96.5‬‬ ‫‪80.3‬‬ ‫‪71.3‬‬ ‫‪59.8‬‬ ‫‪32.8‬‬ ‫‪11.1‬‬
‫ﻓﻤ ﺜﻼً ﻧﺄﺧ ﺬ اﻟ ﺰﻣﻦ )‪ (t1 = 9.82 min‬واﻟ ﺬي ﯾﻘﺎﺑﻠ ﮫ اﻟﺘﺮﻛﯿ ﺰ‬

‫)‪(a – x1 = 96.5 × 10-3‬‬
‫‪ (t2‬واﻟ ﺬي ﯾﻘﺎﺑﻠ ﮫ اﻟﺘﺮﻛﯿ ﺰ‬ ‫=‬ ‫‪59.60‬‬ ‫واﻟ ﺰﻣﻦ )‪min‬‬
‫)‪(a – x2 = 80.3 × 10-3‬‬

‫)‪(526‬‬
‫وﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ ‪:‬‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫) ‪( a - x1‬‬
‫) ‪( t 2 - t1 ) ( a - x 2‬‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫(‬ ‫) ‪96.5 × 10-3‬‬
‫(‬ ‫‪59.60‬‬ ‫‪-‬‬ ‫‪9.82‬‬ ‫) ‪) (80.3 × 10-3‬‬
‫‪k = 3.692 × 10 -3‬‬
‫وﻟﻨﺄﺧﺬ اﻟﻨﻘﻄﺔ اﻷوﻟﻰ واﻷﺧﯿﺮة وﻧﻄﺒﻖ ﻋﻠﯿﮭﺎ ﻧﻔﺲ اﻟﻘﺎﻧﻮن ‪:‬‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫) ‪( a - x1‬‬
‫) ‪( t 2 - t1 ) ( a - x 2‬‬
‫=‪k‬‬
‫‪2.303‬‬
‫‪log‬‬
‫(‬ ‫) ‪96.5 × 10-3‬‬
‫(‬ ‫‪589.4‬‬ ‫‪-‬‬ ‫‪9.82‬‬ ‫) ‪) (11.1 × 10-3‬‬
‫‪k = 3.732 × 10-3‬‬
‫واﻟﻘﯿﻤﺘ ﺎن ﻟﺜﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣﺘﻘﺎرﺑ ﺔ‪ ،‬ﻣﻤ ﺎ ﯾﻌﻨ ﻲ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬

‫اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﻣﺜﺎﻝ )‪(٦٤-٢‬‬
‫ﯾﺘﻤﯿ ﺆ )‪ (57%‬ﻣ ﻦ ﻣﺤﻠ ﻮل اﻟﺴ ﻜﺮوز اﻟﺤﻤﻀ ﻲ ﺑﻌ ﺪ )‪(66 min.‬‬

‫ﻓﺒﻔﺮض أن اﻟﺘﻔﺎﻋﻞ أﺣﺎدي اﻟﺠﺰﯾﺌﯿﺔ ﻓﺎﺣﺴﺐ ‪:‬‬
‫أ( اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻤﯿﺆ )‪.(75 %‬‬
‫ب( درﺟﺔ اﻟﺘﻤﯿﺆ ﺑﻌﺪ ﺳﺎﻋﺘﯿﻦ‪.‬‬

(527)
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‫)‪(528‬‬
‫ﻣﺜﺎﻝ )‪(٦٥-٢‬‬
‫وﺟﺪ أن ﻣﺤﻠﻮل ﻟﮫ اﻟﺘﺮﻛﯿﺰات اﻟﺘﺎﻟﯿﺔ ﺑﻌﺪ ﻋﻤﻠﮫ ‪:‬‬
‫‪-3‬‬
‫) ‪Time (mol cm‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪50‬‬ ‫‪100‬‬ ‫‪150‬‬
‫)‪Conc. (mol cm-3‬‬ ‫‪1.0000‬‬ ‫‪0.9616‬‬ ‫‪0.8235‬‬ ‫‪0.6776‬‬ ‫‪0.5572‬‬
‫أوﺟﺪ ‪:‬‬
‫أ( رﺗﺒﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ب( اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﺤﻠﻞ )‪ (50 %‬ﻣﻦ اﻟﻤﺤﻠﻮل‪.‬‬
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‫‪........................................................................................................................................................................................‬‬
‫‪................................................................................................................................ ........................................................‬‬

(529)
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‫)‪(530‬‬
‫ﻣﺜﺎﻝ )‪(٦٦-٢‬‬
‫اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﯾﻌﻄ ﻲ ﻣﻌﻠﻮﻣ ﺎت ﻋﻠ ﻰ اﻟﺘﻔﺎﻋ ﻞ اﻟﺮﻣ ﺰي‬

‫) ‪ ( A → products‬ﻋﻨﺪ درﺟﺔ ﺣﺮارة )‪ (25 ºC‬ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬
‫)‪Time (Sec.‬‬ ‫‪0‬‬ ‫‪5‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬
‫‪[A] mol/dm3‬‬ ‫‪0.461‬‬ ‫‪0.371‬‬ ‫‪0.298‬‬ ‫‪0.196‬‬ ‫‪0.123‬‬
‫ﺑ ﯿﻦ ﻋ ﻦ طﺮﯾ ﻖ اﻟﺘﻌ ﻮﯾﺾ ﻓ ﻲ اﻟﻘ ﺎﻧﻮن وﻛ ﺬﻟﻚ ﻋ ﻦ طﺮﯾ ﻖ اﻟﺮﺳ ﻢ‬

‫اﻟﺒﯿﺎﻧﻲ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬واﺣﺴﺐ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‪.‬‬
‫‪........................................................................................................................................................................................‬‬
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(531)
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‫)‪(532‬‬
‫ﻣﺜﺎﻝ )‪ : (٦٧-٢‬ﺍﺧﱰ ﺍﻹﺟﺎﺑﺔ ﺍﻟﺼﺤﻴﺤﺔ ﻓﻴﻤﺎ ﻳﻠﻲ ‪:‬‬

‫‪ (١‬ﺗﺆدي زﯾﺎدة درﺟﺔ اﻟﺤﺮارة ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ اﻟﻰ ‪:‬‬
‫د( زﯾﺎدة ‪Ea‬‬ ‫ج( ﻧﻘﺺ ‪Ea‬‬ ‫ب( زﯾﺎدة ‪t1/2‬‬ ‫أ( ﻧﻘﺺ ‪t1/2‬‬
‫‪ (٢‬ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﺘﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬

‫ب( ﺗﺘﻨﺎﺳﺐ ﻋﻜﺴﯿﺎ ً ﻣﻊ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬ ‫أ( ﺗﺘﻨﺎﺳﺐ طﺮدﯾﺎ ً ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬
‫د( ﺗﺘﻨﺎﺳﺐ ﻋﻜﺴﯿﺎ ً ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬ ‫ج( ﺗﺘﻨﺎﺳﺐ طﺮدﯾﺎ ً ﻣﻊ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
‫‪ (٣‬ﻓﻲ ﺗﻔﺎﻋﻞ )‪ ( A → B‬ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﺈن ﻣﻀﺎﻋﻔﺔ ﺗﺮﻛﯿﺰ )‪(A‬‬
‫ب( ﺗﻨﻘﺺ ﻗﯿﻤﺔ ‪ t1/2‬اﻟﻰ اﻟﻨﺼﻒ‬ ‫أ( ﺗﺰﯾﺪ ﻗﯿﻤﺔ ‪ t1/2‬اﻟﻰ اﻟﻀﻌﻒ‬
‫ج( ﺗﺰﯾﺪ ﻗﯿﻤﺔ ‪ t1/2‬ﺑﻤﻘﺪار ‪ 0.693‬ﻣﻦ اﻟﻘﯿﻤﺔ اﻷﺻﻠﯿﺔ د( ﻻ ﺗﻮﺟﺪ إﺟﺎﺑﺔ ﺻﺤﯿﺤﺔ‬
‫‪ (٤‬ﺗﺘﺄﺛﺮ ﻗﯿﻤﺔ )‪ (t1/2‬ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺪرﺟﺔ اﻷوﻟﻰ ﺑـ ‪:‬‬

‫ب( اﻟﻀﻐﻂ‬ ‫أ( ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪(k‬‬
‫د( زﯾﺎدة اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‪.‬‬ ‫ج( ﻧﻘﺺ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬
‫‪ (٥‬ﯾﺘﻨﺎﺳﺐ ﻋﻤﺮ اﻟﻨﺼﻒ ﻣﻊ اﻟﺘﺮﻛﯿﺰ ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺗﻨﺎﺳﺒﺎ ً ‪:‬‬

‫ج( ﻋﻜﺴﯿﺎ ً ﻣﻊ ﻣﺮﺑﻊ اﻟﺘﺮﻛﯿﺰ د( ﻻ ﺗﻮﺟﺪ إﺟﺎﺑﺔ ﺻﺤﯿﺤﺔ‬ ‫ب( ﻋﻜﺴﯿﺎ ً‬ ‫أ( طﺮدﯾﺎ ً‬
‫‪ (٦‬ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ )‪(k = 6.71 × 10-4 s-1‬‬
‫ﻓﻌﻤﺮ اﻟﻨﺼﻒ ﻟﻠﺘﻔﺎﻋﻞ ھﻮ ‪:‬‬
‫د( ﻻ ﺗﻮﺟﺪ إﺟﺎﺑﺔ ﺻﺤﯿﺤﺔ‬ ‫ج( ﻋﻜﺴﯿﺎ ً ﻣﻊ ﻣﺮﺑﻊ اﻟﺘﺮﻛﯿﺰ‬ ‫ب( ﻋﻜﺴﯿﺎ ً‬ ‫أ( طﺮدﯾﺎ ً‬
‫‪ (٧‬ﯾﻌﺘﺒﺮ ﺗﻔﻜﻚ )‪ (CH2N2‬ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪CH 2 N 2 ‬‬
‫‪→ CH 2 + N 2‬‬
‫ﺗﻔﺎﻋﻼً ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ وﻓﺘ ﺮة ﻋﻤ ﺮ اﻟﻨﺼ ﻒ ﺗﺴ ﺎوي )‪ (17.3 min‬ﻋﻨ ﺪ‬
‫درﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﺔ وﻛﺎن ﺗﺮﻛﯿﺰ )‪ (CH2N2‬ﺑﻌﺪ ﻣﻀﻲ ﺧﻤ ﺲ دﻗ ﺎﺋﻖ ﯾﺴ ﺎوي‬
‫)‪ (0.076 M‬ﻓﺈن اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﯾﺴﺎوي ‪:‬‬
‫د( ﻻ ﺗﻮﺟﺪ إﺟﺎﺑﺔ ﺻﺤﯿﺤﺔ‪.‬‬ ‫ج( ‪0.093 M‬‬ ‫ب( ‪10.77 M‬‬ ‫أ( ‪0.039 M‬‬

‫)‪(533‬‬
‫‪ (٨‬إذا ﻛﺎﻧﺖ ﻓﺘ ﺮة ﻋﻤ ﺮ اﻟﻨﺼ ﻒ ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺪرﺟ ﺔ اﻷوﻟ ﻰ ﺗﺴ ﺎوي‬

‫)‪ (38.5 min‬ﻓﺈن ﺛﺎﺑﺖ ﺳﺮﻋﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ ﺑﻮﺣﺪة )‪ (s-1‬ﺗﺴﺎوي ‪:‬‬
‫د( ‪7 × 10-5‬‬ ‫ج( ‪3 × 10-4‬‬ ‫ب( ‪5 × 104‬‬ ‫أ( ‪2 × 10-3‬‬
‫‪ (٩‬إذا ﻛﺎن ﻋﻤﺮ اﻟﻨﺼﻒ ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﯾﺴ ﺎوي )‪(2.5 h‬‬
‫ﻓﺈن ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي ‪:‬‬
‫د( ‪4.6 × 10-5 min-1‬‬ ‫ج( ‪4.6 ×10-3 s-1‬‬ ‫ب( ‪0.77 s-1‬‬ ‫أ( ‪7.7 × 10-5 s-1‬‬
‫‪ (١٠‬إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﻜ ﻚ )‪ (N2O5‬ھ ﻮ ‪(k = 8.1 × 10-3‬‬

‫)‪ min-1‬ﻓ ﺈن اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺨﻔ ﺾ ﺗﺮﻛﯿ ﺰه ﻣ ﻦ )‪ (0.03 M‬اﻟ ﻰ‬
‫)‪ (0.02 M‬ﺑﻮﺣﺪة )‪ (min‬ﯾﺴﺎوي ‪:‬‬
‫د( ‪60‬‬ ‫ج( ‪55‬‬ ‫ب( ‪45‬‬ ‫أ( ‪50‬‬
‫‪ (١١‬إذا ﻛ ﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﯾﺴ ﺎوي ) ‪(k = 5 × 10 s‬‬
‫‪-4‬‬ ‫‪-1‬‬
‫ﻓﺈن اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﺤﻮل )‪ (60 %‬ﻣﻦ ھﺬا اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻠﻤ ﺎدة‬
‫اﻟﻤﺘﻔﺎﻋﻠﺔ اﻟﻰ ﻧﻮاﺗﺞ ﺑﻮﺣﺪة )‪ (s‬ﯾﺴﺎوي ‪:‬‬
‫د( ‪102‬‬ ‫ج( ‪5000‬‬ ‫ب( ‪1021.6‬‬ ‫أ( ‪1832.6‬‬
‫‪ (١٢‬إذا ﻋﻠﻤ ﺖ أن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ ﺗﻔﻜ ﻚ )‪ (C2H5Cl‬ھ ﻮ‬
‫)‪ (k = 3.2 × 10-2 s-1‬ﻓ ﺈن اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺨﻔ ﺾ ﺗﺮﻛﯿ ﺰه اﻟ ﻰ‬
‫اﻟﻨﺼﻒ ﯾﺴﺎوي ﺑﻮﺣﺪة )‪(s‬‬
‫د( ‪3050‬‬ ‫ج( ‪3.2‬‬ ‫ب( ‪0.693‬‬ ‫أ( ‪21.66‬‬

‫)‪(534‬‬
‫‪ ( A ‬ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﯾﺴ ﺎوي‬

‫‪ (١٣‬ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ) ‪→ B‬‬
‫)‪ (k = 1.2 × 10-2 s-1‬ﻓ ﺈذا ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻷﺻ ﻠﻲ ﻟﻠﻤ ﺎدة ﯾﺴ ﺎوي‬
‫)‪ (2 M‬ﻓﺈن اﻟﻤﺘﺒﻘﻲ ﻣﻨﮭﺎ ﺑﻌﺪ ﻣﺮور )‪ (200 s‬ﯾﺴﺎوي ‪:‬‬
‫د( ‪1.7 M‬‬ ‫ج( ‪0.18 M‬‬ ‫ب( ‪1.0 M‬‬ ‫أ( ‪0.55 M‬‬

‫)‪(535‬‬
‫ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ‬

‫)‪(Second Order Reactions‬‬
‫ﻣﻌﺎﺩﻻﺕ ﺍﻟﺴﺮﻋﺔ ﺍﻟﺘﻜﺎﻣﻠﻴﺔ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺛﻨﺎﺋﻴﺔ ﺍﻟﺮﺗﺒﺔ‬
‫ﺗﻌﺘﺒ ﺮ ھ ﺬه اﻟﺮﺗﺒ ﺔ اﻷﻛﺜ ﺮ ﺷ ﯿﻮﻋﺎ ً ﺣﯿ ﺚ ﺗﻜﺜ ﺮ ﻓ ﻲ ﺗﻔ ﺎﻋﻼت اﻟﺤﺎﻟ ﺔ‬

‫اﻟﻐﺎزﯾﺔ واﻟﻤﺤﺎﻟﯿﻞ اﻟﺴﺎﺋﻠﺔ وﺧﺼﻮﺻﺎ ً ﻓﻲ اﻟﺘﻔﺎﻋﻼت اﻟﻌﻀﻮﯾﺔ‪.‬‬
‫ﺃﻣﺜﻠﺔ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ﰲ ﺍﳊﺎﻟﺔ ﺍﻟﻐﺎﺯﻳﺔ‬
‫• ﺗﻔﺎﻋﻞ ﺗﻜﻮﯾﻦ أو ﺗﻔﻜﻚ ﺣﻤﺾ اﻟﯿﻮد )ﯾﻮدﯾﺪ اﻟﮭﯿﺪروﺟﯿﻦ( ‪:‬‬

‫‪2HI ‬‬
‫ﺗﻔﻜـــــــــﻚ‬
‫‪→ H 2 + I2‬‬
‫‪H 2 + I2 ‬‬
‫ﺗﻜــــــــﻮﯾﻦ‬
‫‪→ 2HI‬‬
‫• اﻟﺘﻜﺴﯿﺮ اﻟﺤﺮاري ﻟﻸوزون ‪:‬‬
‫‪2O3 ‬‬
‫‪→ 3O 2‬‬
‫ﺃﻣﺜﻠﺔ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ﰲ ﺍﳊﺎﻟﺔ ﺍﻟﺴﺎﺋﻠﺔ‬

‫أﻣﺎ ﺗﻔﺎﻋﻼت اﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ ﻓﺎﻷﻣﺜﻠﺔ ﻛﺜﯿﺮة ﻣﻨﮭﺎ ‪:‬‬
‫• ﺗﺼﺒﻦ ﺧﻼت اﻹﯾﺜﯿﻞ )ﺗﺤﻠﻞ اﻹﺳﺘﺮ( ﻓﻲ وﺳﻂ ﻗﺎﻋﺪي ‪:‬‬
‫‪CH 3COOC 2 H 5 + NaOH ‬‬
‫‪→ CH 3COONa + C 2H 5OH‬‬
‫• ﺗﻔﺎﻋ ﻞ ﺑﺮوﻣﯿ ﺪ اﻹﯾﺜﯿﻠ ﯿﻦ )‪ (C2H4Br‬وﯾﻮدﯾ ﺪ اﻟﺒﻮﺗﺎﺳ ﯿﻮم )‪(KI‬‬

‫ﺑﻮﺟﻮد ﻣﺤﻠﻮل ﺗﺮﻛﯿﺰه )‪ (99 %‬ﻣﻦ اﻟﻜﺤﻮل اﻟﻤﯿﺜﯿﻠﻲ‪.‬‬

‫)‪(536‬‬
‫‪C2 H 4 Br2 + 3KI ‬‬

‫‪→ C2 H 4 + 2KBr + KI3‬‬
‫وﻓ ﻲ ھ ﺬا اﻟﻨ ﻮع ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﺗﻌﺘﻤ ﺪ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻠ ﻰ ﺣ ﺪﯾﻦ‬

‫ﻣﺘﻐﯿ ﺮﯾﻦ ﻟﻠﺘﺮﻛﯿ ﺰ)‪ ،(a, b‬ھ ﺬان اﻟﺤ ﺪان ﯾﻤﻜ ﻦ أن ﯾﻜﻮﻧ ﺎ ﻣﺘﺴ ﺎوﯾﯿﻦ‬
‫)‪) (a = b‬ﺣﺎﻟ ﺔ ﻣﺘﺠﺎﻧﺴ ﺔ( أو ﻣﺨﺘﻠﻔ ﯿﻦ )‪) (a ≠ b‬ﺣﺎﻟ ﺔ ﻏﯿ ﺮ‬
‫ﻣﺘﺠﺎﻧﺴ ﺔ(‪ ،‬وﯾﻤﻜ ﻦ أن ﯾﻜ ﻮن ﺣ ﺪ اﻟﺘﺮﻛﯿ ﺰ ﺗﺎﺑﻌ ﺎ ً ﻟﻤ ﺎدة )‪ (A + A‬أو‬
‫ﻣﺎدﺗﯿﻦ ﻣﺨﺘﻠﻔﺘﯿﻦ )‪.(A + B‬‬
‫ً‬
‫ﺃﻭﻻ ‪ :‬ﺍﳊﺎﻟﺔ ﺍﳌﺘﺠﺎﻧﺴﺔ ‪ :‬ﺗﺮﻛﻴﺰ ﺍﳌﻮﺍﺩ ﺍﳌﺘﻔﺎﻋﻠﺔ ﻣﺘﺴﺎﻭﻱ‬
‫ﯾﻌﻨﻰ ﺑﺎﻟﺤﺎﻟﺔ اﻟﻤﺘﺠﺎﻧﺴﺔ ھﻨﺎ أن اﻟﺠﺰﯾﺌﺎت ﺗﻜﻮن ﻣ ﻦ ﻧﻔ ﺲ اﻟﻤ ﺎدة وﻓ ﻲ‬

‫ھ ﺬه اﻟﺤﺎﻟ ﺔ ﯾﺘﻨﺎﺳ ﺐ ﻣﻌ ﺪل ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻊ ﻣﺮﺑ ﻊ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة‬
‫اﻟﻤﺘﻔﺎﻋﻠﺔ ﻛﻤﺎ ھﻮ اﻟﺤﺎل ﻓﻲ ﺗﺨﺜ ﺮ اﻟﻐﺮواﻧﯿ ﺎت‪ .‬وﺗﻨﻄﺒ ﻖ ﻧﻔ ﺲ اﻟﺼ ﯿﻎ‬
‫اﻟﺘﻜﺎﻣﻠﯿﺔ ﻓﻲ اﻟﺤﺎﻟﺘﯿﻦ اﻟﺘﺎﻟﯿﺘﯿﻦ ‪:‬‬
‫‪) (١‬ﺗﻔﺎﻋﻼت ﺗﺸﺘﻤﻞ ﻋﻠﻰ ﺟﺰﯾﺌﯿﻦ ﻣﻦ ﻣﺘﻔﺎﻋ ﻞ واﺣ ﺪ )ﻣ ﺜﻼً ‪ (A‬أي‬
‫أن اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ واﺣﺪة‬
‫وﯾﻜﻮن ﻟﮭﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔﺎﻋﻼت اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪A + A ‬‬
‫أو ﺗﻜﺘﺐ اﺧﺘﺼﺎراً ‪:‬‬
‫‪2A ‬‬

‫)‪(537‬‬
‫ﺑﺤﯿ ﺚ أن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﺘﻨﺎﺳ ﺐ طﺮدﯾ ﺎ ً ﻣ ﻊ ﺗﺮﻛﯿ ﺰ ھ ﺬه اﻟﻤ ﺎدة‬

‫ﻣﺮﻓﻮﻋﺎ ً ﻷس اﺛﻨﯿﻦ‪.‬‬
‫ب( أو ﻣﺘﻔﺎﻋﻠﯿﻦ )‪ (A, B‬ﻟﮭﻤﺎ ﻧﻔﺲ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ‪:‬‬
‫ﺣﯿﺚ ‪ [A] =a, [B] = b‬ﻟﻜﻦ )‪(a = b‬‬
‫وﯾﻜﻮن ﻟﮭﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔﺎﻋﻼت اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪A + B ‬‬
‫وﻟﮭﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔﺎﻋﻼت اﻟﻌﻼﻗﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪dx‬‬
‫‪= k (a - x) 2‬‬
‫‪dt‬‬
‫‪dx‬‬
‫⇒‬ ‫‪2‬‬
‫‪= k dt‬‬
‫)‪(a - x‬‬
‫‪ dx‬‬ ‫‪‬‬
‫ﻋﻨ ﺪ زﻣ ﻦ‬ ‫‪‬‬ ‫‪2‬‬
‫‪= k dt ‬‬ ‫وﺑﻤﻜﺎﻣﻠ ﺔ اﻟﻌﻼﻗ ﺔ اﻟﺘﻔﺎﺿ ﻠﯿﺔ‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫‪(t = 0‬‬ ‫) ‪→ tx‬‬

‫‪‬‬
‫)ﺣﯿﺚ ‪ x = 0‬ﻋﻨﺪﻣﺎ ‪ t = 0‬و ‪ x = x‬ﻋﻨﺪﻣﺎ ‪: (t = t‬‬

‫ﻓﺘﺼﺒﺢ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪xt‬‬ ‫‪t‬‬
‫‪dx‬‬
‫)‪∫ (a - x‬‬ ‫‪2‬‬
‫‪= k ∫ dt‬‬
‫‪0‬‬
‫‪0‬‬

(538)
: ‫أو ﺑﻤﻌﻨﻰ آﺧﺮ‬

1
= kt + I
( )
a - x
. (constant) ‫ = ﺛﺎﺑﺖ اﻟﺘﻜﺎﻣﻞ‬I ‫ﺣﯿﺚ‬
: ‫( ﺗﺴﺎوي‬I) ‫( وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﻗﯿﻤﺔ‬x = 0) ‫ ( ﻓﺈن‬t = 0) ‫وﻋﻨﺪ زﻣﻦ‬
1
= kt + I
(a - x)
1
= k(0) + I
( a - 0)
1
⇒I=
a
 1   1
: ‫ ﯾﻨﺘﺞ‬ ( a - x ) = kt + I  ‫ﻓﻲ اﻟﻌﻼﻗﺔ‬ I = 
 a
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ‬
 
1 1
= kt +
(a - x ) a
: ‫وﺑﺘﺮﺗﯿﺐ اﻟﻌﻼﻗﺔ ﺑﺪﻻﻟﺔ اﻟﺘﺮﻛﯿﺰ‬

1 1
= kt +
(a - x ) a
1 1
kt = -
(a - x) a
a - (a - x)
kt =
a (a - x)
a-a+x
kt =
a (a - x)
x
⇒ kt =
a (a - x)

‫)‪(539‬‬
‫‪‬‬ ‫‪x ‬‬

‫= ‪ kt‬‬ ‫‪‬‬ ‫وﯾﻤﻜ ﻦ إﯾﺠ ﺎد ﻗﯿﻤ ﺔ اﻟﺜﺎﺑ ﺖ ﺣﺴ ﺎﺑﯿﺎ ً ﺑﺘﺮﺗﯿ ﺐ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪a (a - x) ‬‬
‫ﺑﺤﯿﺚ ﺗﺼﺒﺢ‬
‫‪1‬‬ ‫‪x‬‬ ‫‪‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪t  a ( a - x ) ‬‬
‫واﻟﺘﻲ ﯾﻤﻜﻦ ﻛﺘﺎﺑﺘﮭﺎ ﻋﻠﻰ اﻟﺼﻮرة ‪:‬‬

‫‪1 1‬‬ ‫‪1‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪- ‬‬
‫‪ta-x a‬‬
‫‪or‬‬
‫‪1 1‬‬ ‫‪1 ‬‬
‫‪k= ‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪t  [ A ]t [ A ]0 ‬‬
‫وﻣﻦ ﺛﻢ ﺗﻮﺟﺪ اﻟﻘﯿﻤﺔ اﻟﺤﺴﺎﺑﯿﺔ ﻟﻠﺜﺎﺑﺖ )‪ (k‬ﻋﻨﺪ أزﻣﻨﺔ )‪ (t‬ﻣﺨﺘﻠﻔﺔ‪ ،‬ﻓﺈذا‬

‫ﻛ ﺎن اﻟﻨ ﺎﺗﺞ ﻣﺘﺴ ﺎوﯾﺎ ً )ﻣ ﻊ اﻷﺧ ﺬ ﺑﻌ ﯿﻦ اﻻﻋﺘﺒ ﺎر ﻧﺴ ﺒﺔ اﻟﺨﻄ ﺄ ﻓ ﻲ‬
‫اﻟﺘﺠﺮﺑﺔ( ﻓﺈن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ أﻣ ﺎ إذا ﺣ ﺪث اﻟﻌﻜ ﺲ ﻓﯿﺠ ﺐ‬
‫ﺗﻄﺒﯿﻖ رﺗﺒﺔ أﺧﺮى‪.‬‬
‫‪‬‬ ‫‪x‬‬ ‫‪‬‬
‫ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي ﺛﺎﺑ ﺖ‬ ‫‪‬‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬ ‫واﻟﻌﻼﻗ ﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫‪‬‬ ‫‪x‬‬ ‫‪‬‬

‫اﻟﺴ ﺮﻋﺔ ‪ ،k‬وﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻋﻠﯿ ﮫ ﻣ ﻦ ﺗﻤﺜﯿ ﻞ ‪  a (a - x) ‬ﻋﻠ ﻰ‬
‫‪‬‬ ‫‪‬‬
‫ﻣﺤﻮر اﻟﺼﺎدات و )‪ (t‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(٢١-٢‬‬

‫)‪(540‬‬
‫‪‬‬ ‫‪x‬‬ ‫‪‬‬

‫‪ ‬ﻣﻊ اﻟﺰﻣﻦ ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬ ‫ﺷﻜﻞ )‪ : (٢١-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ ‪‬‬
‫‪ a (a - x) ‬‬
‫ﻭﺣﺪﺍﺕ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ ﺍﻟﺮﺗﺒﺔ‬
‫‪‬‬ ‫‪1  x ‬‬

‫ﻧﻼﺣ ﻆ أن وﺣ ﺪات ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪(k‬‬ ‫‪ k = at  a - x  ‬‬ ‫ﻣ ﻦ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫ﯾﺴﺎوي ﻣﻘﻠﻮب اﻟﺘﺮﻛﯿﺰ ﻣﻀﺮوﺑﺎ ً ﻓﻲ ﻣﻘﻠﻮب اﻟﺰﻣﻦ ﻓﺈذا ﻗﯿﺲ اﻟﺘﺮﻛﯿ ﺰ‬

‫ﺑﺎﻟﻮﺣﺪات )‪ (mol dm-3‬واﻟﺰﻣﻦ ﺑﺎﻟﺜﻮاﻧﻲ ﻓﺈن وﺣﺪات ﺛﺎﺑﺖ اﻟﺴ ﺮﻋﺔ‬
‫ﺗﻜ ﻮن )‪ .(dm3 mol-1 s-1‬وإذا ﻗ ﯿﺲ اﻟﺘﺮﻛﯿ ﺰ ﺑﻮﺣ ﺪة )‪(mol L-1‬‬
‫واﻟ ﺰﻣﻦ ﺑﺎﻟ ﺪﻗﺎﺋﻖ ﻣ ﺜﻼً ﻓ ﺈن وﺣ ﺪات ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﺗﻜ ﻮن‬
‫)‪ .(L. mol-1 min-1‬ﻋﻠﻤﺎ ً ﺑﺄن )‪(1 L = 1 dm3‬‬

‫)‪(541‬‬
‫‪ x‬‬ ‫‪‬‬ ‫‪ 1‬‬ ‫‪1‬‬

‫اﻟﻤﻌ ﺎدﻻت‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫و‬ ‫‪‬‬ ‫=‬ ‫‪kt‬‬ ‫‪+‬‬ ‫‪‬‬
‫‪a ‬‬
‫وﺗﻤﺜ ﻞ اﻟﻌﻼﻗﺘ ﺎن‬
‫)‪ a (a - x‬‬ ‫‪‬‬ ‫) ‪ (a - x‬‬
‫اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﺴ ﺘﻮي ﺗﺮاﻛﯿ ﺰ‬

‫اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻞ‪.‬‬
‫ً‬ ‫‪ 1‬‬ ‫‪1‬‬
‫) ‪  ( a - x‬ﺑﻴﺎﻧﻴﺎ‬ ‫‪= kt +‬‬ ‫‪‬‬
‫‪a ‬‬
‫ﺭﺳﻢ ﺍﻟﻌﻼﻗﺔ‬
‫‪‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1‬‬

‫) ‪  ( a - x‬ﺑ ﯿﻦ )‪ (1/(a – x‬واﻟ ﺰﻣﻦ )‪(t‬‬ ‫‪= kt +‬‬ ‫‪‬‬
‫‪a ‬‬
‫ﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي)‪ (k‬وﯾﻘﻄ ﻊ ﻣﺤ ﻮر اﻟﺼ ﺎدات‬

‫ﺑﻤﻘﺪار )‪ (1/a‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(٢٢-٢‬‬
‫‪ 1‬‬ ‫‪1‬‬

‫ﻟﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒ ﺔ‬ ‫‪‬‬ ‫‪= kt + ‬‬ ‫ﺷﻜﻞ )‪ : (٢٢-٢‬اﻟﻌﻼﻗﺔ اﻟﺨﻄﯿﺔ ﻟﻠﻤﻌﺎدﻟﺔ‬
‫) ‪ (a - x‬‬ ‫‪a‬‬
‫اﻟﺜﺎﻧﯿﺔ ﻓﻲ ﺣﺎﻟﺔ ﺗﺴﺎوي ﺗﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬

‫)‪(542‬‬
‫ً‬ ‫‪ x‬‬ ‫‪‬‬

‫ﺑﻴﺎﻧﻴﺎ‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫ﺭﺳﻢ ﺍﻟﻌﻼﻗﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫‪ x‬‬ ‫‪‬‬

‫ﺑ ﯿﻦ )‪ (x/a(a-x‬واﻟ ﺰﻣﻦ )‪(t‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫ﻛﻤﺎ أن رﺳﻢ اﻟﻌﻼﻗ ﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫ﯾﻌﻄﻲ ﺧﻄﺎ ً ﻣﺴﺘﻘﯿﻤﺎ ً ﯾﻤﺮ ﻣﻦ ﻧﻘﻄ ﺔ اﻷﺻ ﻞ‪ ،‬وﻣﯿﻠ ﮫ ﯾﺴ ﺎوي )‪ (k‬ﻛﻤ ﺎ‬

‫ﻓﻲ اﻟﺸﻜﻞ )‪.(٢٣-٢‬‬
‫‪ x‬‬ ‫‪‬‬

‫ﻟﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫ﺷ ﻜﻞ )‪ : (٢٣-٢‬اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻠﻤﻌﺎدﻟ ﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫اﻟﺜﺎﻧﯿﺔ ﻓﻲ ﺣﺎﻟﺔ ﺗﺴﺎوي ﺗﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‬

‫)‪(543‬‬
‫ﻣﻠﺤﻮﻇﺔ‬
‫ﯾﻤﻜ ﻦ إﺟ ﺮاء اﻟﺘﻜﺎﻣ ﻞ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓ ﻲ اﻟﺤﺎﻟ ﺔ اﻟﻤﺘﺠﺎﻧﺴ ﺔ‬
‫ﺑﺪﻻﻟ ﺔ ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔ ﺎﻋﻼت ﺣﯿ ﺚ ‪ [A]0‬ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ زﻣ ﻦ‬
‫)‪ (t = 0‬ﺑﻤﻌﻨﻰ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ‪ ،‬و ]‪ [A‬ﺗﺮﻛﯿﺰ اﻟﻤﺘﻔﺎﻋﻞ ﻋﻨﺪ زﻣ ﻦ‬
‫)‪: (t‬‬
‫‪A + A ‬‬
‫ﻣﻌﺪل ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= k[A]2‬‬
‫‪dt‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫‪[A]2‬‬
‫وﺑﺈﺟﺮاء اﻟﺘﻜﺎﻣﻞ ‪:‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫‪[A]2‬‬
‫] ‪[A‬‬
‫]‪d [ A‬‬ ‫‪t‬‬
‫‪-‬‬ ‫]‪∫ [A‬‬ ‫‪2‬‬
‫‪=k‬‬ ‫∫‬ ‫‪dt‬‬
‫‪[ A ]0‬‬ ‫‪t=0‬‬
‫] ‪[A‬‬ ‫‪t‬‬
‫]‪∫ [A‬‬ ‫‪d [ A ]= k‬‬ ‫∫‬

‫‪-2‬‬
‫‪-‬‬ ‫‪dt‬‬
‫‪[ A ]0‬‬ ‫‪t=0‬‬
‫]‪[A‬‬
‫‪ 1 ‬‬
‫‪ =k ( t )t = 0‬‬
‫‪t‬‬
‫‪-‬‬
‫‪ - [ A ]  [A]0‬‬
‫‪ 1‬‬ ‫‪1 ‬‬
‫‪-‬‬ ‫‪-‬‬ ‫)‪ = k ( t - 0‬‬
‫‪ - [ A ] - [ A ]0 ‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ A ] [ A ]ο‬‬
‫‪or‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‬ ‫‪+ kt‬‬
‫‪[ A ] [ A ]ο‬‬

‫)‪(544‬‬
‫‪ 1 ‬‬ ‫‪ 1‬‬ ‫‪1 ‬‬

‫ﺑﺪﻻﻟ ﺔ )‪ (t‬ﻛﻤ ﺎ ﻓ ﻲ‬ ‫‪‬‬ ‫‪‬‬ ‫ﺑﺮﺳ ﻢ‬ ‫‪‬‬ ‫‪= kt +‬‬ ‫‪‬‬ ‫وﺑﺘﻤﺜﯿ ﻞ اﻟﻌﻼﻗ ﺔ‬
‫‪ [A] ‬‬ ‫]‪ [A‬‬ ‫‪[ A ]ο ‬‬
‫‪. ‬‬ ‫‪1 ‬‬

‫‪‬‬ ‫اﻟﺸﻜﻞ )‪ (٢٤-٢‬ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ )‪ (k‬وﺗﻘﺎطﻌﮫ‬
‫‪ [ A ]ο ‬‬
‫ﺷﻜﻞ )‪ : (٢٤-٢‬ﺗﻐﯿﺮ )‪ (1/A‬ﺑﺪﻻﻟﺔ اﻟﺰﻣﻦ‪.‬‬
‫وﯾﻤﺜ ﻞ اﻟﺘﺤﻠ ﻞ )اﻟﺘﻔﻜ ﻚ‪ ،‬اﻟ ﺘﺤﻄﻢ( اﻟﺤ ﺮاري ﻟﻸﺳ ﯿﺘﺎﻟﺪھﯿﺪ اﻟ ﻰ ﻣﯿﺜ ﺎن‬
‫وأول أﻛﺴﯿﺪ اﻟﻜﺮﺑﻮن ھﺬا اﻟﻨﻮع ﻣﻦ اﻟﺘﻔﺎﻋﻼت‪.‬‬
‫‪2CH3CHO ‬‬
‫‪→ 2CH 4 + 2CO‬‬

‫)‪(545‬‬
‫ﻣﺜﺎﻝ ﺗﻮﺿﻴﺤﻲ ﻟﺘﻔﺎﻋﻞ ﻣﻦ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ﻣﻦ ﺍﻟﻨﻮﻉ )‪(a = b‬‬
‫اﻟﺘﺤﻠﻞ ﺑﺎﻟﻤﺎء ﻹﺳﺘﺮ ﺧﻼت اﻹﯾﺜﯿﻞ ﻓ ﻲ وﺟ ﻮد ﻗﺎﻋ ﺪة ﺣﯿ ﺚ )‪.(a = b‬‬

‫واﻟﺠﺪول اﻟﺘﺎﻟﻲ ﯾﺒﯿﻦ ﻧﺘﺎﺋﺞ ﺗﺠﺮﺑﺔ ﻋﻦ ھﺬا اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‬ ‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‬
‫)اﻟﺮﺗﺒﺔ اﻷوﻟﻰ(‬ ‫)اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ(‬ ‫= ]‪[OH-‬‬
‫‪(k) s-1‬‬ ‫‪(k) L mol-1 s-1‬‬ ‫]‪[CH3COOC2H5‬‬ ‫اﻟﺰﻣﻦ‬
‫‪2.303‬‬ ‫‪ [ A ]0 ‬‬ ‫‪1 1‬‬ ‫‪1 ‬‬ ‫‪= [A]t‬‬ ‫)‪(s‬‬
‫‪log ‬‬
‫‪ [ A ] ‬‬ ‫‪‬‬ ‫‪‬‬
‫=‪k‬‬ ‫=‪k‬‬ ‫‪-‬‬
‫‪t‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪t  [ A ] [ A ]ο ‬‬
‫‪-‬‬ ‫‪-‬‬ ‫‪0.0500‬‬ ‫‪0‬‬
‫‪5.23‬‬ ‫‪1.12‬‬ ‫‪0.0441‬‬ ‫‪240‬‬
‫‪4.79‬‬ ‫‪1.09‬‬ ‫‪0.0386‬‬ ‫‪540‬‬
‫‪4.38‬‬ ‫‪1.07‬‬ ‫‪0.0337‬‬ ‫‪900‬‬
‫‪4.05‬‬ ‫‪1.10‬‬ ‫‪0.0279‬‬ ‫‪1440‬‬
‫‪3.54‬‬ ‫‪1.07‬‬ ‫‪0.0228‬‬ ‫‪2220‬‬
‫‪3.13‬‬ ‫‪1.07‬‬ ‫‪0.0185‬‬ ‫‪3180‬‬
‫‪2.61‬‬ ‫‪1.07‬‬ ‫‪0.0136‬‬ ‫‪4980‬‬
‫‪2.00‬‬ ‫‪1.07‬‬ ‫‪0.00895‬‬ ‫‪8580‬‬
‫ﯾﻼﺣﻆ ﺛﺒﺎت ﻗﯿﻢ )‪ (k‬اﻟﻤﺤﺘﻮﯾﺔ ﻓ ﻲ اﻟﺠ ﺪول )اﻟﻌﻤ ﻮد اﻟﺮأﺳ ﻲ اﻟﺜﺎﻟ ﺚ(‬
‫ﻣﺆﻛﺪة ﺑﺬﻟﻚ اﻧﺘﻤﺎء اﻟﺘﻔﺎﻋﻞ اﻟﻰ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿ ﺔ‪ .‬ﻛﻤ ﺎ ﯾﻼﺣ ﻆ أﯾﻀ ﺎ ً ﻋ ﺪم‬
‫ﺛﺒﺎت ﻗﯿﻢ )‪) (k‬اﻟﻌﻤﻮد اﻟﺮأﺳﻲ اﻟﺮاﺑﻊ( ﻋﻨ ﺪﻣﺎ طﺒﻘ ﺖ ﻣﻌﺎدﻟ ﺔ اﻟﺴ ﺮﻋﺔ‬
‫ﻟﺘﻔﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ وھ ﻮ دﻟﯿ ﻞ ﺛ ﺎن ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬
‫اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(546‬‬
‫‪‬‬ ‫‪1 1‬‬ ‫‪1 ‬‬

‫أن ﻣﻘﻠﻮب ﺗﺮﻛﯿﺰ اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ‬ ‫‪k = ‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪t  [ A ]t [ A ]ο  ‬‬
‫وﺗﺒﯿﻦ اﻟﻤﻌﺎدﻟﺔ‬
‫‪‬‬
‫‪ 1‬‬ ‫‪‬‬

‫ﯾﺘﻐﯿ ﺮ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣ ﻊ اﻟ ﺰﻣﻦ‪ .‬وﯾﺴ ﺘﻔﺎد ﻣ ﻦ اﻟﺮﺳ ﻢ‬ ‫‪‬‬ ‫‪‬‬ ‫وھﻮ‬
‫‪ [ A ]t‬‬ ‫‪‬‬
‫‪ 1‬‬ ‫‪‬‬

‫ﻟﺤﺴ ﺎب ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪ ،(k‬ﺣﯿ ﺚ‬ ‫‪‬‬ ‫=‬
‫‪1‬‬
‫‪+ kt ‬‬ ‫اﻟﺒﯿ ﺎﻧﻲ ﻟﻠﻌﻼﻗ ﺔ‬
‫‪ [ A ] [ A ]ο‬‬
‫‪‬‬
‫‪‬‬
‫ﻣﯿﻞ اﻟﺨﻂ اﻟﺒﯿﺎﻧﻲ ﯾﻤﺜﻞ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫وﯾﺤﺴﺐ ﻣﯿﻞ اﻟﺨﻂ اﻟﻤﺴﺘﻘﯿﻢ ﻟﺘﻔﺎﻋﻼت ﺧﻼت اﻹﯾﺜﯿﻞ ﻣ ﻊ ھﯿﺪروﻛﺴ ﯿﺪ‬
‫اﻟﺼﻮدﯾﻮم ﻣﻦ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة ﻋﻨﺪ ﻓﺘﺮات زﻣﻨﯿﺔ ﺣﺪدت ﻓ ﻲ ھ ﺬا اﻟﻤﺜ ﺎل‬
‫ﻋﻨﺪ )‪ (t = 0‬و )‪: (t = 6000 s‬‬
‫=‪k‬‬
‫× ‪(84.0 - 20.0 ) L . mol-1 = 1.07‬‬ ‫‪10-2 L mol-1s-1‬‬
‫)‪( 6000 - 0 ) (s‬‬
‫ﺣﺴﺎﺏ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ﻟﺘﻔﺎﻋﻞ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ﻟﻠﻤﻮﺍﺩ‬
‫ﺍﳌﺘﻔﺎﻋﻠﺔ ﺍﳌﺘﺴﺎﻭﻳﺔ ﺍﻟﱰﻛﻴﺰ‬
‫وﻟﺤﺴﺎب ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ ﻧﻄﺒﻖ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪1‬‬
‫= ‪t1/2‬‬
‫‪k [ A ]0‬‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪1.07 × 10-2 × 0.0500‬‬
‫‪t1/2‬‬ ‫‪= 1869.16 s‬‬

‫)‪(547‬‬
‫‪‬‬ ‫‪1 ‬‬

‫ﻋﻠ ﻰ‬ ‫= ‪ t1/2‬‬ ‫‪‬‬
‫‪k [ A ]0 ‬‬
‫وﯾﻼﺣ ﻆ اﺣﺘ ﻮاء ﻣﻌﺎدﻟ ﺔ ﻧﺼ ﻒ زﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ‬
‫‪‬‬
‫ﺗﺮﻛﯿﺰ اﻟﻤﺎدة اﻟﻤﺘﻔﺎﻋﻠﺔ ﻋﻠﻰ ﻋﻜﺲ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬إذ ﺗﺘﻨﺎﺳ ﺐ ﻋﻜﺴ ﯿﺎ ً‬
‫ﻣﻊ ﺗﺮﻛﯿﺰ اﻟﻤﺎدة ﻓﯿﻜﻮن اﻟﺘﻔﺎﻋﻞ أﻛﺜﺮ ﺳﺮﻋﺔ ﻋﻨﺪ زﯾ ﺎدة اﻟﺘﺮﻛﯿ ﺰ‪ .‬وﻗ ﺪ‬
‫وﺟ ﺪ ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ اﻟﺴ ﺎﺑﻖ أن )‪ (t1/2 = 1869.16 s‬ﻋﻨ ﺪﻣﺎ ﯾﻜ ﻮن‬
‫اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ )‪ ،([A]0 = 0.0500 M‬ﻟﻜﻨ ﮫ ﻋﻨ ﺪ ﺗﺮﻛﯿ ﺰ اﺑﺘ ﺪاﺋﻲ‬
‫)‪ ([A]0 = 0.0250 M‬ﯾﺼﺒﺢ ‪:‬‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪k [ A ]0‬‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪1.07 × 10‬‬ ‫‪-2‬‬
‫‪× 0.0250‬‬
‫‪t1/2‬‬ ‫‪= 3738.32 s‬‬
‫ﻣﺜﺎﻝ )‪(٦٨-٢‬‬
‫اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ (k‬ﻟﺘﺤﻠ ﻞ ﺧ ﻼت اﻹﯾﺜﯿ ﻞ ﻓ ﻲ اﻟﻤ ﺎء ﻓ ﻲ وﺟ ﻮد‬
‫ﻗﺎﻋﺪة‪ ،‬ﻣﺴﺘﻌﯿﻨﺎ ً ﺑﺘﺮاﻛﯿﺰ اﻟﻤﺎدة ﺑﺎﻟﺠﺪول اﻟﺴﺎﺑﻖ ﻓﻲ اﻷوﻗﺎت اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫)‪(t = 2220 s, t = 0‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪1 1‬‬ ‫‪1 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪t  [ A ] [ A ]ο ‬‬
‫‪1  1‬‬ ‫‪1 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪2220  0.0228 0.0500 ‬‬
‫‪k = 0.0107 L mol-1 s-1‬‬

‫)‪(548‬‬
‫ﻣﺜﺎﻝ ﺗﻮﺿﻴﺤﻲ‬
‫ﯾﺘﻔﻜﻚ اﻷﺳﯿﺘﺎﻟﺪھﯿﺪ ﺣﺮارﯾﺎ ً وﻓﻘﺎ ً ﻟﻠﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪2CH 3CHO(g) ‬‬
‫)‪→ 2CH 4 (g) + 2CO(g‬‬
‫وﻓﻲ ھﺬا اﻟﺘﻔﺎﻋﻞ ﻧﻼﺣﻆ ازدﯾﺎد اﻟﻀ ﻐﻂ ﻋﻨ ﺪ ﺣﺠ ﻢ ﺛﺎﺑ ﺖ أﺛﻨ ﺎء ﻋﻤﻠﯿ ﺔ‬

‫اﻟﺘﺤﻠﻞ ھﺬه‪ ،‬وﻣﻦ ﺗﻐﯿﺮ اﻟﻀﻐﻂ ھﺬا ﯾﻤﻜﻨﻨﺎ ﺣﺴﺎب ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪(k‬‬
‫ﺑﺎﻟﻄﺮﯾﻘﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫ﻧﻔﺮض أن )‪ (P0‬ﯾﻤﺜﻞ اﻟﻀﻐﻂ اﻻﺑﺘﺪاﺋﻲ ﻟﻸﺳﯿﺘﺎﻟﺪھﯿﺪ‬
‫و )‪ (x‬ﯾﻤﺜﻞ اﻻﻧﺨﻔﺎض ﻓﻲ اﻟﻀﻐﻂ ﺑﻌﺪ ﻣﻀﻲ زﻣﻦ )‪.(t‬‬
‫وأن ﺿﻐﻂ اﻟﻤﺘﻔﺎﻋﻼت ﺑﺰﻣﻦ )‪ (t‬ھﻮ )‪.(P0 – x‬‬
‫وﻓ ﻲ ﺣﺎﻟ ﺔ اﻧﺨﻔ ﺎض ﺿ ﻐﻂ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ ﺑﻤﻘ ﺪار )‪ (x‬ﻓ ﺈن ﺿ ﻐﻂ‬
‫اﻟﻤﯿﺜﺎن وأول أﻛﺴﯿﺪ اﻟﻜﺮﺑﻮن ﯾﺰداد ﺑﻤﻘﺪار )‪ (x‬وﺑﺎﻟﺘﺎﻟﻲ ﻓ ﺈن اﻟﻀ ﻐﻂ‬
‫اﻟﻜﻠﻲ ﻟﻠﻨﻈﺎم ھﻮ ‪:‬‬
‫‪P = PCH3CHO + PCH 4 + PCO‬‬
‫‪P = ( P0 - x ) + x + x‬‬
‫‪P = P0 - x + x + x‬‬
‫‪P = P0 + x‬‬
‫‪⇒ x = P - P0‬‬

‫)‪(549‬‬
‫وﺣﯿﺚ أن ‪:‬‬
‫)‪( P0 - x ) α (a - x‬‬
‫‪P0 α a‬‬
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ ﻣﻌﺎدﻟﺔ اﻟﺪرﺟﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬

‫‪1 x ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪at  a - x ‬‬
‫‪1  x ‬‬
‫=‪⇒k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪P0 t  P0 - x ‬‬
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﺑﻘﯿﻤﺔ ) ‪( x = P - P0‬‬

‫‪1  x ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪P0 t  P0 - x ‬‬
‫‪1  P - P0 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪P0 t  P0 - ( P - P0 ) ‬‬
‫‪1  P - P0 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪P0 t  P0 - P + P0 ‬‬
‫‪1  P - P0 ‬‬
‫=‪⇒k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪P0 t  2P0 - P ‬‬
‫واﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﯾﺒ ﯿﻦ ﻧﺘ ﺎﺋﺞ ﺗﺠﺮﺑ ﺔ ﺗﻔﻜ ﻚ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ ﻋﻨ ﺪ درﺟ ﺔ‬
‫ﺣﺮارة )‪ (791 K‬وﺿﻐﻂ اﺑﺘﺪاﺋﻲ ﻣﻘﺪاره‬
‫)‪(P0 = 0.47 × 106 N/m2 = 0.47 × 10º Pa‬‬

‫)‪(550‬‬
‫‪1  x ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪(x = P – P0) N/m2‬‬ ‫اﻟﺰﻣﻦ )ﺛﺎﻧﯿﺔ(‬
‫‪P0 t  P0 - x ‬‬
‫‪8.934 × 10-4‬‬ ‫‪4.47 × 103‬‬ ‫‪42‬‬
‫‪8.67 × 10-4‬‬ ‫‪7.11 × 103‬‬ ‫‪73‬‬
‫‪8.82 × 10-4‬‬ ‫‪9.74 × 103‬‬ ‫‪105‬‬
‫‪8.74 × 10-4‬‬ ‫‪1.5 × 103‬‬ ‫‪190‬‬
‫‪8.76 × 10-4‬‬ ‫‪1.76 × 103‬‬ ‫‪242‬‬
‫‪8.62 × 10-4‬‬ ‫‪2.03 × 103‬‬ ‫‪310‬‬
‫‪8.70 × 10-4‬‬ ‫‪2.29 × 103‬‬ ‫‪384‬‬
‫‪8.67 × 10-4‬‬ ‫‪2.55 × 103‬‬ ‫‪480‬‬
‫‪8.79 × 10-4‬‬ ‫‪2.95 × 103‬‬ ‫‪665‬‬
‫‪8.84 × 10-4‬‬ ‫‪3.21 × 103‬‬ ‫‪840‬‬
‫‪9.03 × 10-4‬‬ ‫‪3.47 × 103‬‬ ‫‪1070‬‬
‫‪9.05 × 10-4‬‬ ‫‪3.74 × 103‬‬ ‫‪1440‬‬
‫‪k = 8.802 × 10-4 m2 N-1 s-1‬‬
‫ﻛﻤﺎ وأن رﺳﻢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ ﻣﻌﻜﻮس اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ ﺗﻜﻮن ﺧﻄﯿﺔ ﻟﮭ ﺬا‬
‫اﻟﻨﻮع ﻣﻦ ﺗﻔﺎﻋﻼت اﻟﻤﺮﺗﺒﺔ اﻟﺜﻨﺎﺋﯿﺔ‪.‬‬

‫)‪(551‬‬
‫ً‬
‫ﺛﺎﻧﻴﺎ ‪ :‬ﺍﳊﺎﻟﺔ ﺍﻟﻐﲑ ﻣﺘﺠﺎﻧﺴﺔ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ )‪(a ≠ b‬‬
‫وﯾﻌﻨ ﻰ ﺑﺎﻟﺤﺎﻟ ﺔ ﻏﯿ ﺮ اﻟﻤﺘﺠﺎﻧﺴ ﺔ ھﻨ ﺎ ھ ﻮ أن اﻟﺠﺰﯾﺌ ﺎت ﺗﻜ ﻮن ﻟﻤ ﺎدﺗﯿﻦ‬

‫ﻣﺨﺘﻠﻔﺘﯿﻦ )‪ (A, B‬ﻣﺨﺘﻠﻔﺘﻲ اﻟﺘﺮﻛﯿﺰ )‪([A] = a, [B] = b , a ≠ b‬‬
‫ﺗﻔﺎﻋﻞ ﻣﺎﺩﺗﲔ )‪ (A, B‬ﳐﺘﻠﻔﺘﻲ ﺍﻟﱰﻛﻴﺰ )]‪: ([A] ≠ [B‬‬

‫ﺣﻴﺚ ))‪([A] = a, [B] = b‬‬
‫ﻧﻔﺮض أن ﻟﺪﯾﻨﺎ ﺗﻔﺎﻋﻼً ﻣﻤﺜﻼً ﺑﺎﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪A + B ‬‬
‫وﺣﯿﺚ أن اﻟﺘﺮﻛﯿﺰات اﻹﺑﺘﺪاﺋﯿﺔ ﻟﻠﻤﺘﻔﺎﻋﻠﯿﻦ )‪ (A, B‬ھﻤﺎ )‪ (a, b‬ﻋﻠﻰ‬

‫اﻟﺘ ﻮاﻟﻲ‪ .‬و)‪ (x‬ﺳﻨﺴ ﺘﺨﺪﻣﮭﺎ ﻟﻠﺘﻌﺒﯿ ﺮ ﻋ ﻦ اﻟ ﻨﻘﺺ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ ﻛ ﻞ ﻣ ﻦ‬
‫)‪ (B, A‬ﻋﻨﺪ زﻣﻦ ﻗﺪره "‪."t‬‬
‫وﯾﻜ ﻮن ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺪﻻﻟ ﺔ ﺗﺮﻛﯿ ﺰي اﻟﻤ ﺎدﺗﯿﻦ اﻟﻤﺘﻔ ﺎﻋﻠﺘﯿﻦ‬
‫ﯾﻜﻮن ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫]‪d [A‬‬ ‫]‪d[B‬‬
‫‪-‬‬ ‫‪=-‬‬ ‫]‪= k [A][B‬‬
‫‪dt‬‬ ‫‪dt‬‬
‫]‪ d [A‬‬ ‫]‪d[B‬‬ ‫‪‬‬
‫ﺳﻮف ﯾﻌﺒ ﺮ ﻋ ﻦ ]‪[A‬‬ ‫‪-‬‬ ‫‪=-‬‬ ‫‪= k [A][B] ‬‬ ‫وﻟﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ dt‬‬ ‫‪dt‬‬ ‫‪‬‬
‫و ]‪ [B‬ﺑﺪﻻﻟﺔ ﻣﺘﻐﯿﺮ واﺣ ﺪ وھ ﻮ ﻋﺒ ﺎرة ﻋ ﻦ اﻟﻨﻘﺼ ﺎن ﻓ ﻲ ﺗﺮﻛﯿ ﺰ ﻛ ﻞ‬

‫ﻣﻦ اﻟﻤﺎدﺗﯿﻦ اﻟﺬي اﻋﺘﺪﻧﺎ أن ﻧﺮﻣﺰ ﻟﮫ ﺑ ﺎﻟﺤﺮف )‪ .(x‬ﻓ ﺈذا اﻓﺘﺮﺿ ﻨﺎ أن‬

‫)‪(552‬‬
‫)‪ (a‬و)‪ (b‬ھﻤﺎ اﻟﺘﺮﻛﯿﺰان اﻹﺑﺘﺪاﺋﯿﺎن ﻋﻨﺪﻣﺎ )‪ (t = 0‬ﻟﻠﻤ ﺎدﺗﯿﻦ )‪ (A‬و‬

‫)‪ (B‬ﻋﻠ ﻰ اﻟﺘ ﻮاﻟﻲ‪ ،‬وﺑﻌ ﺪ ﻣ ﺮور ﻓﺘ ﺮة زﻣﻨﯿ ﺔ ﻣﻘ ﺪارھﺎ )‪ (t‬ﯾﺘﻔﺎﻋ ﻞ‬
‫ﺗﺮﻛﯿﺰ ﻣﻘﺪاره )‪ (x‬ﻣﻦ اﻟﻤﺎدة )‪ (A‬ﻣ ﻊ ﺗﺮﻛﯿ ﺰ ﻣﻘ ﺪاره )‪ (x‬ﻣ ﻦ اﻟﻤ ﺎدة‬
‫)‪ (B‬ﻟﺘﺘﺤﻮل اﻟﻰ ﻧﻮاﺗﺞ ﻓﺈن ﺗﺮﻛﯿﺰ ﻛ ﻞ ﻣ ﻦ اﻟﻤ ﺎدﺗﯿﻦ اﻟﻤﺘﻔ ﺎﻋﻠﺘﯿﻦ ﻋﻨ ﺪ‬
‫اﻟﺰﻣﻦ )‪ (t‬ﯾﺼﺒﺢ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪[A] = a - x‬‬
‫‪[B] = b - x‬‬
‫ﺔ‬ ‫ﺔ اﻟﻤﻌﺎدﻟ‬ ‫ﻦ ﻛﺘﺎﺑ‬ ‫ﺒﻖ ﯾﻤﻜ‬ ‫ﺎﺳ‬ ‫ﻰﻣ‬ ‫ﺎد ﻋﻠ‬ ‫وﺑﺎﻹﻋﺘﻤ‬
‫]‪ d [A‬‬ ‫‪‬‬
‫ﺑﺎﻟﻌﻼﻗﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬ ‫‪-‬‬ ‫‪=-‬‬
‫]‪d[B‬‬
‫‪= k [A][B] ‬‬
‫‪ dt‬‬ ‫‪dt‬‬ ‫‪‬‬
‫‪dx‬‬
‫)‪= k (a - x) (b - x‬‬
‫‪dt‬‬
‫وﺑﺘﻨﻈﯿﻢ ھﺬه اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪dx‬‬
‫‪= k dt‬‬
‫)‪(a - x) (b - x‬‬
‫وﺑﺎﺳ ﺘﺨﺪام طﺮﯾﻘ ﺔ ﺗﺠ ﺰأة اﻟﻜﺴ ﻮر )‪ (partial fractions‬ﻓ ﺈن‬

‫اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ ﺗﺼﺒﺢ ‪:‬‬
‫‪1  1‬‬ ‫‪1 ‬‬
‫‪‬‬ ‫‪-‬‬ ‫‪ dx = k dt‬‬
‫‪(a - b)  ( b - x) ( a - x) ‬‬

(553)
   
: ‫ وﻣﻜﺎﻣﻠﺘﮭﺎ‬ ( a 1- b )  ( b 1- x ) - ( a 1- x )  dx = k dt  ‫وﺑﺘﺮﺗﯿﺐ اﻟﻌﻼﻗﺔ‬
   
1  1 1  t
x
( a - b )  ( b - x ) ( a - x )  x∫0
 -  dx = k dt
ln (a - x) - ln (b - x)
⇒ + I = kt
( a - b)
: (x = 0) ‫( و‬t = 0) ‫( ﻋﻨﺪ‬I) ‫وﺗﻜﻮن ﻗﯿﻤﺔ‬

ln (a - x) - ln (b - x)
+ I = kt
( a - b)
 ln (a - x) - ln (b - x) 
I = kt -  
 ( a - b) 
 ln (a - 0) - ln (b - 0) 
I = k (0) -  
 ( a - b) 
 ln a - ln b 
I=-  
 ( a - b) 
- ln a + ln b
I=
(a - b)
ln b - ln a
I=
(a - b)
ln ( b/a )
⇒I=
a-b
 ln (a - x) - ln (b - x) 
 + I = kt  ‫( ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬I) ‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ ﻗﯿﻤ ﺔ‬
 ( a - b) 
: ‫وﺗﺮﺗﯿﺒﮭﺎ‬

(554)
ln (a - x) - ln (b - x)
+ I = kt
( a - b)
ln (a - x) - ln (b - x) ln (b/a)
+ = kt
( a - b) (a - b)
ln (a - x) - ln (b - x) + ln (b/a)
= kt
( a - b)
1  b (a - x) 
⇒
(a - b)  a (b - x) 
ln  = kt
: ‫وﻋﻨﺪ اﻟﺘﻌﺒﯿﺮ ﺑﺎﻟﻠﻮﻏﺎرﯾﺘﻢ اﻟﻌﺸﺮي )اﻟﻄﺒﯿﻌﻲ( ﺗﺆوول ھﺬه اﻟﻌﻼﻗﺔ اﻟﻰ‬

2.303  b (a - x) 
log   = kt
(a - b)  a (b - x) 
1  b (a - x)  k
⇒ log   = t
(a - b)  a (b - x)  2.303

‫)‪(555‬‬
‫ﻣﺰﻳﺪ ﻣﻦ ﺍﻟﻘﺮﺍءﺓ‬
‫‪ 1‬‬ ‫‪ b (a - x) ‬‬ ‫‪‬‬

‫ﻣ ﻦ ﻣﻜﺎﻣﻠ ﺔ‬ ‫‪‬‬ ‫‪ln ‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫ﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ اﻟﻌﻼﻗ ﺔ‬
‫‪ (a - b)  a (b - x) ‬‬ ‫‪‬‬
‫‪‬‬ ‫‪dx‬‬ ‫‪‬‬
‫ﺑﻮﺿ ﻊ ﺣ ﺪود اﻟﺘﻜﺎﻣ ﻞ‬ ‫‪‬‬ ‫‪= k dt ‬‬ ‫اﻟﻌﻼﻗ ﺔ اﻟﺘﻔﺎﺿ ﻠﯿﺔ‬
‫)‪ (a - x) (b - x‬‬ ‫‪‬‬
‫)‪ (x = 0‬ﻋﻨﺪﻣﺎ )‪ (t = 0‬و )‪ (x = x‬ﻋﻨﺪﻣﺎ )‪: (t = t‬‬
‫‪x‬‬ ‫‪dx‬‬ ‫‪t‬‬
‫∫‬‫‪0‬‬ ‫)‪(a - x) (b - x‬‬
‫=‬ ‫∫‬ ‫‪0‬‬
‫‪k dt‬‬
‫‪ x‬‬ ‫‪dx‬‬ ‫‪‬‬

‫‪ ∫0‬‬ ‫∫‬
‫‪t‬‬
‫ﺑﺎﺳ ﺘﺨﺪام‬ ‫=‬ ‫‪k dt ‬‬ ‫وﯾﻤﻜ ﻦ ﻣﻜﺎﻣﻠ ﺔ اﻟﻤﻌﺎدﻟ ﺔ ‪:‬‬
‫‪‬‬ ‫‪(a‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪(b‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪0‬‬
‫‪‬‬
‫طﺮﯾﻘﺔ ﺗﺠﺰﺋﺔ اﻟﻜﺴﻮر ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪x‬‬ ‫‪dx‬‬ ‫‪x‬‬ ‫‪ I‬‬ ‫‪J ‬‬ ‫‪t‬‬
‫∫‬‫‪0‬‬ ‫)‪(a - x) (b - x‬‬
‫=‬ ‫∫‬‫‪0‬‬ ‫= ‪ (a - x) + (b - x)  dx‬‬
‫‪‬‬ ‫‪‬‬
‫‪∫ k dt‬‬
‫‪0‬‬
‫ﺑﺤﻞ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺜﺎﺑﺘﯿﻦ )‪ (I, J‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪1‬‬
‫=‪I‬‬
‫‪b-a‬‬
‫‪1‬‬
‫=‪J‬‬
‫‪a-b‬‬
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ )‪ (I, J‬ﻓﻲ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪ I‬‬ ‫‪J ‬‬
‫∫ وإﺟ ﺮاء اﻟﺘﻜﺎﻣ ﻞ ﻟﮭ ﺎ‬ ‫‪x‬‬ ‫‪dx‬‬
‫=‬ ‫∫‬
‫‪x‬‬
‫= ‪ (a - x) + (b - x)  dx‬‬ ‫‪∫ k dt‬‬
‫‪t‬‬
‫‪0‬‬ ‫)‪(a - x) (b - x‬‬ ‫‪0‬‬

‫‪‬‬ ‫‪‬‬ ‫‪0‬‬
‫‪ b (a - x) ‬‬
‫‪1‬‬
‫‪(a - b)  a (b - x) ‬‬
‫‪ln ‬‬ ‫‪= kt‬‬ ‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫)‪(556‬‬
‫‪ 1‬‬ ‫‪ b (a - x) ‬‬ ‫‪‬‬

‫ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ‬ ‫‪‬‬ ‫‪ln ‬‬ ‫‪‬‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬ ‫واﻟﻌﻼﻗ ﺔ‬
‫‪ (a - b)  a (b - x) ‬‬ ‫‪‬‬
‫)‪.(k‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪b(a - x) ‬‬
‫وﯾﻤﻜ ﻦ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ )‪ (k‬ﺑﺘﻤﺜﯿ ﻞ ‪  ( a - b ) ln a(b - x) ‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬
‫‪‬‬ ‫‪‬‬
‫اﻟﺼﺎدات واﻟﺰﻣﻦ )‪ (t‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(٢٥-٢‬‬
‫‪ 1‬‬ ‫‪ b (a - x) ‬‬ ‫‪‬‬

‫ﻟﺘﻔ ﺎﻋﻼت‬ ‫‪‬‬ ‫‪ln ‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫ﺷ ﻜﻞ )‪ : (٢٥-٢‬اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻠﻤﻌﺎدﻟ ﺔ‬
‫‪ (a - b)  a (b - x) ‬‬ ‫‪‬‬
‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﻓﻲ ﺣﺎﻟﺔ ﻋﺪم ﺗﺴﺎوي اﻟﺘﺮاﻛﯿﺰ‬

(557)
 1  b (a - x)  k 
‫ﻛ ﺬﻟﻚ ﺑ ﻨﻔﺲ‬  log  a (b - x)  2.303 
= t ‫وﯾﻤﻜ ﻦ ﺗﻤﺜﯿ ﻞ اﻟﻌﻼﻗ ﺔ‬
 (a - b)   
 1  b (a - x)  
‫( ﻋﻠ ﻰ‬t) ‫ و‬، ‫ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات‬  log   : ‫اﻟﻄﺮﯾﻘﺔ‬
 (a - b)  a (b - x)  
.(k/2.303) ‫ﻣﺤﻮر اﻟﺴﯿﻨﺎت ﻓﻨﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ‬

 1  b (a - x)  
: ‫ﯾﻤﻜﻦ ﻛﺘﺎﺑﺘﮭﺎ ﻋﻠﻰ اﻟﺼﻮرة‬  ln   = kt  ‫واﻟﻌﻼﻗﺔ‬
 (a - b)  a (b - x)  
1  b (a - x) 
(a - b)  a (b - x) 
ln  = kt
1 b 1 (a - x)
ln + ln = kt
(a - b) a (a - b) (b - x)
1 (a - x) 1 b
ln = kt - ln
(a - b) (b - x) (a - b) a
1 (a - x) 1 a
⇒ ln = kt + ln
(a - b) (b - x) (a - b) b
 1 a
‫ﺑﯿﻦ‬  ln
(a - x)
= kt +
1
ln  ‫وﻋﻨﺪ رﺳﻢ اﻟﻌﻼﻗﺔ وﻓﻘﺎ ً ﻟﻠﻤﻌﺎدﻟﺔ‬
 (a - b) (b - x) (a - b) b 
 1 (a - x) 
‫( ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ‬t) ‫واﻟ ﺰﻣﻦ‬  ln  ‫اﻟﺤ ﺪ‬
 (a - b) (b - x) 
 1 a
‫ﻛﻤ ﺎ ﻓ ﻲ‬  ln  ‫( وﯾﻘﻄ ﻊ ﻣﺤ ﻮر اﻟﺼ ﺎدات ﺑﺎﻟﻤﻘ ﺪار‬k) ‫ﯾﺴ ﺎوي‬
 (a - b) b 
.(٢٦-٢) ‫اﻟﺸﻜﻞ‬

‫)‪(558‬‬
‫‪ 1‬‬ ‫)‪(a - x‬‬ ‫‪1‬‬ ‫‪a‬‬

‫‪‬‬ ‫‪ln‬‬ ‫‪= kt +‬‬ ‫‪ln ‬‬ ‫ﺷ ﻜﻞ )‪ : (٢٦-٢‬اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻠﻤﻌﺎدﻟ ﺔ‬
‫)‪ (a - b) (b - x‬‬ ‫‪(a - b) b ‬‬
‫ﻟﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﻓﻲ ﺣﺎﻟﺔ ﻋﺪم ﺗﺴﺎوي اﻟﺘﺮاﻛﯿﺰ‪.‬‬
‫‪ 2.303‬‬ ‫‪ b (a - x) ‬‬ ‫‪‬‬

‫ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬ ‫‪‬‬ ‫‪log ‬‬ ‫‪‬‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬ ‫وﯾﻤﻜﻦ إﯾﺠﺎد "‪ "k‬ﻣﻦ اﻟﻌﻼﻗﺔ ‪:‬‬
‫)‪ (a - b‬‬ ‫‪ a (b - x) ‬‬ ‫‪‬‬
‫‪2.303‬‬ ‫)‪b (a - x‬‬

‫=‪k‬‬ ‫‪log‬‬
‫)‪t ( a - b‬‬ ‫)‪a (b - x‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪b (a - x) ‬‬

‫أن وﺣ ﺪات‬ ‫= ‪ k‬‬
‫)‪t (a - b‬‬
‫‪log‬‬ ‫‪‬‬
‫‪a (b - x) ‬‬ ‫وﯾﻤﻜﻦ أن ﻧﻼﺣﻆ ﻣﻦ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ (k‬ھﻲ ﻣﻘﻠ ﻮب اﻟ ﺰﻣﻦ ﻣﻀ ﺮوﺑﺎ ً ﻓ ﻲ ﻣﻘﻠ ﻮب اﻟﺘﺮﻛﯿ ﺰ‬

‫وھﺬا ﯾﺘﻮاﻓﻖ ﻣﻊ اﻟﺤﺎﻟﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(559‬‬
‫ﺇﺛﺒﺎﺕ ﺃﻥ ﺍﻟﺘﻔﺎﻋﻞ ﻣﻦ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ‬
‫وﯾﻤﻜ ﻦ إﺛﺒ ﺎت أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﺑﺈﯾﺠ ﺎد ﻗﯿﻤ ﺔ )‪ (k‬ﻋﻨ ﺪ‬

‫أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﻣﻦ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪2.303‬‬ ‫)‪b (a - x‬‬
‫=‪k‬‬ ‫‪log‬‬
‫)‪t (a - b‬‬ ‫)‪a (b - x‬‬
‫أو اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪1‬‬ ‫)‪b (a - x‬‬
‫=‪k‬‬ ‫‪ln‬‬
‫)‪t ( a - b ) a (b - x‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪b(a - x) ‬‬

‫ﺔ ‪  ( a - b ) ln a(b - x)  = kt‬أو‬ ‫ﺔ اﻟﻜﯿﻤﯿﺎﺋﯿ‬ ‫ﺮ اﻟﻤﻌﺎدﻟ‬ ‫وﺗﻌﺘﺒ‬
‫‪‬‬ ‫‪‬‬
‫‪ 2.303‬‬ ‫‪b(a - x) ‬‬

‫‪  ( a - b ) log a(b - x)  = kt‬اﻟﺤﺎﻟ ﺔ اﻟﻤﺜﺎﻟﯿ ﺔ ﻟﺘﻔﺎﻋ ﻞ ﻣ ﺎدﺗﯿﻦ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬
‫‪‬‬ ‫‪‬‬
‫اﻟﺜﺎﻧﯿﺔ ﺣﯿﺚ أن ﻧﺴﺐ اﻹﺗﺤﺎد اﻟﻌﻨﺼﺮي ﻣﻦ اﻟﻤﺘﻔﺎﻋﻼت ﻣﺘﺴﺎو‪.‬‬

‫)‪(560‬‬
‫ﻣﺜﺎﻝ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ‬
‫وﻣ ﻦ اﻷﻣﺜﻠ ﺔ اﻟﻤﻌﺮوﻓ ﺔ ﻋﻠ ﻰ ھ ﺬه اﻟﺘﻔ ﺎﻋﻼت ﺗﻤﯿ ﺆ أو ﺗﺼ ﺒﻦ‬

‫)‪ (saponification‬ﺧﻼت اﻹﯾﺜﯿﻞ )‪ (Ethyl Acetate‬ﻣﻊ ﻗﺎﻋﺪة‬
‫ﻗﻮﯾ ﺔ ﻣﺜ ﻞ ھﯿﺪروﻛﺴ ﯿﺪ اﻟﺼ ﻮدﯾﻮم ﻓ ﻲ ﺣﺎﻟ ﺔ ﻋ ﺪم ﺗﺴ ﺎوي ﺗﺮﻛﯿ ﺰ‬
‫اﻟﺨﻼت ﻣﻊ ھﯿﺪروﻛﺴﯿﺪ اﻟﺼﻮدﯾﻮم‪.‬‬
‫‪ CH3COO- + C2 H5 OH‬‬
‫‪CH 2 COOC2 H5 + OH - ‬‬
‫وﻓ ﻲ ﺣﺎﻟ ﺔ اﺧ ﺘﻼف ﺗﺮﻛﯿ ﺰي اﻹﺳ ﺘﺮ واﻟﻘﺎﻋ ﺪة)‪ (a, b‬ﻓ ﺈن ﺗﺮاﻛﯿ ﺰ‬
‫اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ﺗﺨﺘﻠﻒ ﻣﻊ اﻟﺰﻣﻦ وﺑ ﺬﻟﻚ ﺗ ﺆﺛﺮ ﻋﻠ ﻰ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫وﯾﻤﻜ ﻦ ﺗﺘﺒ ﻊ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﻄ ﺮق ﻋﺪﯾ ﺪة ﻣﻨﮭ ﺎ إزاﻟ ﺔ اﻟﮭﯿﺪروﻛﺴ ﯿﺪ‬
‫وإﺑ ﺪاﻟﮭﺎ ﺑﺄﯾﻮﻧ ﺎت اﻹﺳ ﺘﺮ واﻟﻤﺼ ﺤﻮﺑﺔ ﺑﺎﻧﺨﻔ ﺎض ﻓ ﻲ اﻟﺘﻮﺻ ﯿﻠﯿﺔ‬
‫اﻟﻜﮭﺮﺑﯿ ﺔ ﻟﻠﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ .‬وﻣ ﻦ ھ ﺬا اﻹﻧﺨﻔ ﺎض ﯾﻤﻜ ﻦ ﺑﯿ ﺎن ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ‪ ،‬أو أن ﯾ ﺘﻢ ﺳ ﺤﺐ ﻛﻤﯿ ﺎت ﻣﺤ ﺪدة ﻣ ﻦ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ وﻣ ﻦ‬
‫وﻗ ﺖ ﻵﺧ ﺮ وإن ﻛﻤﯿ ﺔ اﻟﻘﺎﻋ ﺪة اﻟﻤﺘﺒﻘﯿ ﺔ )‪ (b – x‬ﺗﺤﺴ ﺐ ﻣ ﻦ ﻋﻤﻠﯿ ﺔ‬
‫اﻟﺘﺴﺤﯿﺢ اﻹﻋﺘﯿﺎدﯾﺔ‪ .‬وﻓﻲ ﺣﺎﻟﺔ ﻣﻌﺮﻓﺔ اﻟﺘﺮاﻛﯿﺰ اﻹﺑﺘﺪاﺋﯿﺔ ﻹﯾﺴ ﺘﺮ )‪(a‬‬
‫و اﻟﮭﯿﺪروﻛﺴ ﯿﺪ )‪ (b‬ﻓ ﺈن ﻗ ﯿﻢ )‪ (a – x‬ﯾﻤﻜ ﻦ ﺣﺴ ﺎﺑﮭﺎ وﻣﻨ ﮫ ﻧﺤﺴ ﺐ‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ اﻟﻨﻮﻋﯿﺔ‪.‬‬

‫)‪(561‬‬
‫واﻟﺠﺪول اﻟﺘﺎﻟﻲ ﯾﺒﯿﻦ ﺑﻌﺾ اﻟﻘﯿﻢ اﻟﻤﺨﺒﺮﯾﺔ ﻟﺘﻔﺎﻋﻞ ﺧﻼت اﻹﯾﺜﯿﻞ )‪(A‬‬
‫ﻣ ﻊ ھﯿﺪروﻛﺴ ﯿﺪ اﻟﺼ ﻮدﯾﻮم )‪ (NaOH‬واﻟﻤﻤﺜﻠ ﺔ ﺑ ﺎﻟﺮﻣﺰ )‪ (B‬وﻋﻨ ﺪ‬
‫اﻟﺪرﺟﺔ )‪.(288.8 K‬‬
‫ﺟﺪول )‪ : (٢-٢‬ﺗﺤﻠﻞ ﺧﻼت اﻹﯾﺜﯿﻞ ﺑﻮﺟﻮد ﻗﺎﻋﺪة وﻋﻨﺪ درﺟﺔ )‪(288.8 K‬‬
‫)‪(a = 0.01211 mol/L, b = 0.02578 mol/L‬‬
‫‪2.303‬‬ ‫)‪b (a - x‬‬
‫=‪k‬‬ ‫‪log‬‬
‫)‪t (a - b‬‬ ‫)‪a (b - x‬‬ ‫)‪(b – x‬‬ ‫)‪(a – x‬‬ ‫اﻟﺰﻣﻦ )ﺛﺎﻧﯿﺔ(‬
‫‪-1‬‬ ‫‪-1‬‬
‫‪L. mol s‬‬
‫‪5.74 × 10-2‬‬ ‫‪0.02256‬‬ ‫‪0.00889‬‬ ‫‪224‬‬
‫‪5.74 × 10-2‬‬ ‫‪0.02101‬‬ ‫‪0.00734‬‬ ‫‪337‬‬
‫‪5.68 × 10-2‬‬ ‫‪0.01921‬‬ ‫‪0.00554‬‬ ‫‪629‬‬
‫‪5.68 × 10-2‬‬ ‫‪0.01821‬‬ ‫‪0.00454‬‬ ‫‪816‬‬
‫وﺗﺠ ﺪر اﻟﻤﻼﺣﻈ ﺔ أن ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ اﻟﺴ ﺎﺑﻘﺔ ﺗﻨﻄﺒ ﻖ ﻓﻘ ﻂ‬

‫ﻋﻨﺪﻣﺎ ﯾﺘﻔﺎﻋﻞ ﺟﺰيء ﻣﻦ اﻟﻤﺎدة )‪ (A‬ﻣﻊ ﺟﺰيء ﻣﻦ اﻟﻤﺎدة )‪.(B‬‬

‫)‪(562‬‬
‫ﻗﻮﺍﻧﲔ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ﰲ ﺣﺎﻟﺔ ﺍﺧﺘﻠﻔﺖ ﻧﺴﺐ ﺍﻹﲢﺎﺩ‬
‫ﺍﻟﻌﻨﺼﺮﻱ ﺣﺴﺐ ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﺘﺎﻟﻴﺔ ‪:‬‬

‫‪A + qB ‬‬
‫ﻓﺴﺘﻜﻮن اﻟﻌﻼﻗﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ ﻟﻠﺴﺮﻋﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪dx‬‬
‫)‪= k (a - x)(b - qx‬‬
‫‪dt‬‬
‫وﺳﺘﻜﻮن اﻟﻌﻼﻗﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ اﻟﻨﮭﺎﺋﯿﺔ ﻟﮭﺎ ﻣﺴﺎوﯾﺔ ‪:‬‬
‫‪1‬‬ ‫)‪b(a - x‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫)‪( qa - b ) a(b - qx‬‬
‫وﺑﻨﻔﺲ اﻟﻄﺮﯾﻘﺔ إذا ﻛﺎﻧﺖ اﻟﻤﻌﺎدﻟﺔ ﻣﻦ اﻟﻨﻮع اﻟﺜﺎﻧﻲ ‪:‬‬
‫‪qA + B ‬‬
‫ﻓﺴﺘﻜﻮن اﻟﻌﻼﻗﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ ﻟﻠﺴﺮﻋﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪dx‬‬
‫)‪= k (a - qx)(b - x‬‬
‫‪dt‬‬
‫وﺳﺘﻜﻮن اﻟﻌﻼﻗﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ اﻟﻨﮭﺎﺋﯿﺔ ﻟﮭﺎ ﻣﺴﺎوﯾﺔ ‪:‬‬

‫‪1‬‬ ‫)‪b (a - qx‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫)‪( a - qb ) a(b - x‬‬

‫)‪(563‬‬
‫ﻋﻨﺪﻣﺎ ﯾﺘﻔﺎﻋﻞ ﺟ ﺰيء ﻣ ﻦ اﻟﻤ ﺎدة )‪ (A‬ﻣ ﻊ ﺛ ﻼث ﺟﺰﯾﺌ ﺎت ﻣ ﻦ اﻟﻤ ﺎدة‬

‫)‪ (B‬ﻣﺜﻞ ‪:‬‬
‫‪A + 3B ‬‬
‫ﻓﺈن ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ‪:‬‬

‫]‪d[A‬‬ ‫]‪1 d[B‬‬
‫‪-‬‬ ‫‪=-‬‬ ‫]‪= k[A][B‬‬
‫‪dt‬‬ ‫‪3 dt‬‬
‫وﺣﯿﺚ أﻧﮫ إذا اﺧﺘﻔﻰ )‪ (x‬ﻣﻦ )‪ (A‬ﯾﺨﺘﻔﻲ )‪ (3 x‬ﻣﻦ )‪ (B‬ﻓﺈن ‪:‬‬

‫‪dx‬‬
‫) ‪= k ( a - x )( b - 3 x‬‬
‫‪dt‬‬
‫‪ dx‬‬ ‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪ = k ( a - x )( b - 3 x ) ‬‬ ‫وﺑﺈﺟﺮاء اﻟﺘﻜﺎﻣﻞ ﻟﻠﻤﻌﺎدﻟﺔ‬
‫‪ dt‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪ b (a - x) ‬‬

‫‪(3a - b)  a (b - 3x) ‬‬
‫‪ln ‬‬ ‫‪= kt‬‬
‫‪1‬‬ ‫‪ b (a - x) ‬‬

‫‪(3a - b)  a (b - 3x) ‬‬
‫‪ln ‬‬ ‫‪= kt‬‬ ‫وﻣ ﻦ اﻷﻣﺜﻠ ﺔ اﻟﻤﻌﺮوﻓ ﺔ اﻟﺘ ﻲ ﺗﺘﺒ ﻊ اﻟﻤﻌﺎدﻟ ﺔ‬
‫ﺗﻔﺎﻋ ﻞ ﺑﺮوﻣﯿ ﺪ اﻹﯾﺜﯿﻠ ﯿﻦ ﻣ ﻊ ﯾﻮدﯾ ﺪ اﻟﺒﻮﺗﺎﺳ ﯿﻮم ﻓ ﻲ وﺟ ﻮد اﻟﻜﺤ ﻮل‬

‫اﻟﻤﯿﺜﯿﻠﻲ اﻟﻨﻘﻲ ‪:‬‬
‫‪C2 H 4 Br2 + 3KI ‬‬
‫‪→ C 2 H 4 + 2KBr + KI3‬‬

‫)‪(564‬‬
‫ﯾﺘﻀ ﺢ ﻣﻤ ﺎ ﺳ ﺒﻖ أن اﻟﻤﻌ ﺎدﻻت اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‬

‫ﺗﺨﺘﻠﻒ ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫ﺗﻔﺎﻋ ﻞ ﺑﺮوﻣﯿ ﺪ اﻹﯾﺜﯿﻠ ﯿﻦ وﯾﻮدﯾ ﺪ اﻟﺒﻮﺗﺎﺳ ﯿﻮم ﺑﻮﺟ ﻮد ﻣﺤﻠ ﻮل ﺗﺮﻛﯿ ﺰه‬
‫)‪ (99 %‬ﻣﻦ اﻟﻜﺤﻮل اﻟﻤﯿﺜﯿﻠﻲ ﯾﻤﺜﻞ ﺗﻔﺎﻋﻼً ﻣﻦ اﻟﺪرﺟﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫‪C2 H 4 Br2 + 3KI ‬‬
‫‪→ C2 H 4 + 2KBr + KI3‬‬
‫وﺗﻜﻮن ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ ﻋﻠﻰ اﻟﺼﻮرة ‪:‬‬

‫‪1‬‬ ‫‪ b (a - x) ‬‬
‫‪(3a - b)  a (b - 3x) ‬‬
‫= ‪kt‬‬ ‫‪ln ‬‬
‫س( اﺳ ﺘﻨﺘﺞ ﻣﻌﺎدﻟ ﺔ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔ ﺎﻋﻼت ﺛﻨﺎﺋﯿ ﺔ اﻟﺮﺗﺒ ﺔ ﻓ ﻲ اﻟﺤ ﺎﻻت‬
‫أ‪ -‬إذا ﻛﺎن اﻟﻤﺘﻔﺎﻋﻠﯿﻦ ﻣﺨﺘﻠﻔﻲ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬
‫ب‪ -‬إذا ﻛﺎن ﻟﻠﻤﺘﻔﺎﻋﻠﯿﻦ ﻧﻔﺲ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‪.‬‬

‫)‪(565‬‬
‫ﯾﻤﻜﻦ اﻟﺤﺼﻮل ﻋﻠﻰ اﻟﺼﻮرة اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﺘﻔ ﺎﻋﻼت اﻟﺪرﺟ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓ ﻲ‬

‫اﻟﺤﺎﻟﺔ اﻟﻐﯿﺮ ﻣﺘﺠﺎﻧﺴﺔ ﺑﻄﺮﯾﻘﺔ أﺧﺮى ‪:‬‬
‫‪A + B ‬‬
‫‪→ product‬‬
‫]‪d[A‬‬
‫‪ν=-‬‬ ‫]‪= k [A][B‬‬
‫‪dt‬‬
‫ﻟﻮ أﺧﺬﻧﺎ ‪ B‬ﻛﺪاﻟﺔ ﻟـ ]‪ [A‬ﻓﺈن ‪:‬‬

‫]‪[ A ]ο - [A] = [ B]ο - [B‬‬
‫وﺗﺼﺒﺢ ‪:‬‬
‫]‪[ B] = [ B]0 - [A]0 + [A‬‬
‫أي أن اﻟﻤﻌﺪل ‪:‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫]‪= k [A] [ B‬‬
‫‪dt‬‬
‫]‪ [ B] = [ B]0 - [A]0 + [A‬‬
‫‪⇒-‬‬
‫]‪d[A‬‬
‫‪dt‬‬
‫(‬
‫]‪= k [A] [ B]0 - [A]0 + [A‬‬ ‫)‬
‫وﺑﺎﻟﺘﺮﺗﯿﺐ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫‪-‬‬
‫]‪d[A‬‬
‫‪dt‬‬
‫(‬
‫]‪= k [A] [ B]0 - [A]0 + [A‬‬ ‫)‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= k dt‬‬
‫(‬
‫]‪[A] [ B]0 - [A]0 + [A‬‬ ‫)‬

(566)
‫( ﻟﺘﺴ ﮭﯿﻞ‬Partial Fraction) ‫وﺑﺎﺳ ﺘﻌﻤﺎل طﺮﯾﻘ ﺔ اﻟﻜﺴ ﺮ اﻟﺠﺰﺋ ﻲ‬

 
‫اﻟﺼ ﻌﺒﺔ‬ -
d[A]
 [A] ([ B] - [A]0 + [A])
= k dt 

‫ﻋﻤﻠﯿ ﺔ اﻟﺘﻜﺎﻣ ﻞ ﺑﺘﺤﻮﯾ ﻞ اﻟﻤﻌﺎدﻟ ﺔ‬
 0 
: ‫اﻟﻰ ﻣﻌﺎدﻟﺘﯿﻦ ﺳﮭﻠﺘﯿﻦ ﻛﻤﺎ ﯾﻠﻲ‬

1 P q
= +
[A] ([ B]0 - [A]0 + [A]) [ A ] ([ B]0 - [A]0 + [A])
.‫ ھﻤﺎ ﺛﻮاﺑﺖ‬q ‫ و‬P ‫ﺣﯿﺚ‬

‫ﻓﻲ‬ 

1
=
P
+
q 
 ‫وﺑﻀ ﺮب طﺮﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
 [A] ([ B] - [A]0 + [A]) [ A ] ([ B] - [A]0 + [A]) 
 0 0 
: ‫[( ﻧﺤﺼﻞ ﻋﻠﻰ‬A] ([B] - [A] + [A])) 0 0
( (
1 [A] [ B]0 - [A]0 + [A]) ) = P ([A] ([ B] - [A] + [A]) ) + q ([A] ([ B] - [A] + [A]) )
0 0 0 0
[A] ([ B] - [A] + [A])

0 0
 A  ([ B] - [A] + [A])
0 0
⇒ 1= P ( ([ B] - [A] + [A]) ) + q [ A ]
0 0
: ‫وﺑﺄﺧﺬ‬
[ A ] = [ A ]0 - [ B]0
: ‫ﺗﺼﺒﺢ‬
⇒ 1= P ( ([ B] - [A] + [A])) + q [ A ]
0 0
 [ A ] = [ A ]0 - [ B]0
((
1= P  B 0 - [A]0 +  A  0 -  B 0 ) ) + q ([ A ] - [ B] )
0 0
(
1= P ( 0 ) + q [ A ]0 - [ B]0 )
(
⇒ 1= q [ A ]0 - [ B]0 )

(567)
: ‫أي‬
(
1= q [ A ]0 - [ B]0 )
1
⇒q=
( [ A ]0 - [ B]0 )
‫وﺑﺄﺧﺬ‬
[A] = 0
: ‫ﻓﺈن‬
1
P=
([ B] - [ A ] )
0 0
‫ﺔ‬ ‫ﻲ اﻟﻤﻌﺎدﻟ‬ ‫ﻓ‬p‫و‬q‫ﻦ‬ ‫ﺎﻟﺘﻌﻮﯾﺾ ﻋ‬ ‫وﺑ‬

 
: ‫ﻧﺤﺼﻞ ﻋﻠﻰ‬ 
1
=
P
+
q

 [A] ([ B] - [A]0 + [A]) [ A ] ([ B] - [A]0 + [A]) 
 0 0 
1 P q
= +
[A] ([ B]0 - [A]0 + [A]) [ A ] ([ B]0 - [A]0 + [A])
1 1
q = and P =
([ A ]0 - [ B]0 ) ([ B]0 - [ A ]0 )
1 1
1
=
([ A ]0 - [ B]0 ) +
([ B]0 - [ A ]0 )
[A] ([ B]0 - [A]0 + [A]) [A] ([ B] 0
- [A]0 + [A])
1 1 1
⇒ = +
[A] ([ B]0 - [A]0 + [A]) [ A ] ([ A ]0 - [ B]0 ) ([ B]0 - [ A ]0 ) ([ B]0 - [A]0 + [A])
 1  [A ] d [ A ]  1  [A ] d [A] t
  ∫ -
 ∫
 = k ∫ dt
 [ A ]0 - [ B]0  [ A]0 [ A ]  [ A ]0 - [ B]0  [ A]0 ([ A ] + [ B]0 - [ A ]0 )

t=0
1
ln
[ A ] - 1 ln [ A ] + [ B]0 - [ A ]0 = kt
[ A ]0 - [ B]0 [ A ]0 [ A ]0 - [ B]0 [ B]0

‫)‪(568‬‬
‫أي ‪:‬‬
‫‪1‬‬
‫‪ln‬‬
‫‪[ A ] - 1 ln [ A ] + [ B]0 - [ A ]0 = kt‬‬
‫‪[ A ]0 - [ B]0 [ A ]0 [ A ]0 - [ B]0‬‬ ‫‪[ B]0‬‬
‫‪1‬‬ ‫‪[ A ][ B]0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫) ‪[ A ]0 - [ B]0 [ A ]0 ([ A ] + [ B]0 - [ A ]0‬‬
‫‪[ A ] + [ B] - [ A ]0 = [ B]0‬‬
‫‪1‬‬ ‫‪[ A ][ B]0‬‬
‫⇒‬ ‫‪ln‬‬ ‫‪= kt‬‬
‫]‪[ A ]0 - [ B]0 [ A ]0 [ B‬‬
‫ھﺬا وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ ﺑﺼﻮرة ﻋﺎﻣﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪aA + bB ‬‬
‫أي أن ‪:‬‬
‫‪ν = k [A]a [B]b‬‬
‫وﺗﻜﺎﻣﻠﮭﺎ ﯾﻌﻄﻲ ‪:‬‬

‫‪a‬‬ ‫‪[ A ][ B]0‬‬
‫‪.ln‬‬ ‫‪= kt‬‬
‫(‬ ‫‪b [ A ]0 - a [ B]0‬‬ ‫)‬ ‫]‪[ A ]0 [ B‬‬
‫وﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﻻ ﻧﺮﺳﻢ اﻟﻌﻼﻗﺔ وإﻧﻤﺎ ﻧﻌﻮض ﺑﺎﻷرﻗﺎم ﻟﻨﺤﺼ ﻞ ﻋﻠ ﻰ‬

‫ﻗﯿﻤﺔ ﺛﺎﺑﺘﺔ ﻟﺜﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ إذا ﻣﺎ ﻛﻨﺎ ﻧﺮﯾﺪ ﻣﻌﺮﻓﺔ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫)‪(569‬‬
‫ﻣﺜﺎﻝ )‪(٦٩-٢‬‬
‫ﻗﺎﻧﻮن ﻣﻌﺪل اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫‪A + B ‬‬
‫]‪ν = k [A] [B‬‬

‫ھﻮ ‪:‬‬
‫وﺛﺎﺑ ﺖ ﻣﻌﺪﻟ ﮫ ﯾﺴ ﺎوي )‪ (0.521 dm-3 mol-1 min-1‬ﻓ ﺈذا ﻣ ﺎ ﻛ ﺎن‬
‫ﺗﺮﻛﯿﺰ )‪ (A‬اﻻﺑﺘ ﺪاﺋﻲ ھ ﻮ )‪ (0.1 mol dm-3‬وﺗﺮﻛﯿ ﺰ)‪ (B‬اﻻﺑﺘ ﺪاﺋﻲ‬
‫ﺿﻌﻒ ﺗﺮﻛﯿﺰ )‪ (A‬ﻓﺒﻌﺪ ﻛﻢ ﻣﻦ اﻟﻮﻗﺖ ﯾﻜ ﻮن ﻗ ﺪ ﺗﺒﻘ ﻰ )‪ (70 %‬ﻣ ﻦ‬
‫)‪ (A‬دون أن ﯾﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺣﯿﺚ أن اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﻤﺘﻔ ﺎﻋﻠﯿﻦ ﻛ ﺎن ﻣﺨﺘﻠﻘ ﺎ ً ﻣ ﻦ اﻟﺒﺪاﯾ ﺔ ﻓﯿﺠ ﺐ‬

‫أن ﻧﺴﺘﻌﻤﻞ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪a‬‬ ‫‪[ A ][ B]0‬‬
‫‪.ln‬‬ ‫‪= kt‬‬
‫(‬ ‫‪b [ A ]0 - a [ B]0‬‬‫)‬ ‫]‪[ A ]0 [ B‬‬
‫وﺣﯿﺚ أن ﻣﻌﺎﻣﻞ ‪ = A‬ﻣﻌﺎﻣﻞ ‪ 1 = B‬إذا ﻣﻦ اﻟﻤﻤﻜ ﻦ ﻛﺘﺎﺑ ﺔ اﻟﻤﻌﺎدﻟ ﺔ‬
‫ﻛﺎﻵﺗﻲ‬
‫‪1‬‬ ‫‪[ A ][ B]0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫]‪[ A ]0 - [ B]0 [ A ]0 [ B‬‬

‫)‪(570‬‬
‫ﻣﻦ اﻟﺴﺆال ‪:‬‬

‫‪[ A ]0 = 0.1 mol dm-3‬‬
‫‪[ B]0 = 2 [ A ]0 = 2 × 0.1= 0.2 mol dm-3‬‬
‫‪70‬‬
‫= ]‪[A‬‬ ‫‪× 0.1= 0.07 mol dm -3‬‬
‫‪100‬‬
‫‪[ B] =0.2 - 0.03= 0.170 mol dm-3‬‬
‫ﻛﻤﯿﺔ )‪ (A‬اﻟﻤﺘﺒﻘﯿﺔ ھﻲ )‪ (0.07 mol dm-3‬وھﺬا ﯾﻌﻨﻲ أﻧﮫ ﻗﺪ ﺗﻔﺎﻋ ﻞ‬
‫ﻣﻨﮭﺎ ‪:‬‬
‫) ‪(0.1 – 0.07 = 0.03 mol dm-3‬‬
‫وﺑﺴ ﺒﺐ أﻧ ﮫ ﯾﺘﻔﺎﻋ ﻞ واﺣ ﺪ ﻣ ﻮل ﻣ ﻦ )‪ (A‬ﻣ ﻊ واﺣ ﺪ ﻣ ﻮل ﻣ ﻦ )‪، (B‬‬
‫ﻟ ﺬﻟﻚ ﻓﺈﻧ ﮫ ﯾﺘﻔﺎﻋ ﻞ )‪ (0.03 mol‬ﻣ ﻦ )‪ (A‬ﻣ ﻊ )‪ (0.03 mol‬ﻣ ﻦ‬
‫)‪ ،(B‬وھﺬا ﯾﻌﻨﻲ أن ‪[B] = 0.03 mol dm-3‬‬
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪1‬‬ ‫‪[ A ][ B]0‬‬
‫‪ln‬‬ ‫‪= kt‬‬
‫]‪[ A ]0 - [ B]0 [ A ]0 [ B‬‬
‫‪1‬‬ ‫‪0.07 × 0.2‬‬
‫‪ln‬‬ ‫‪= (0.521) t‬‬
‫‪0.1- 0.2 0.1 × 0.170‬‬
‫‪1.942 = 0.521 t‬‬
‫‪t = 3.73 min.‬‬

‫)‪(571‬‬
‫ﻣﺜﺎﻝ )‪(٧٠-٢‬‬
‫وﺟﺪ أن ﺗﺼﺒﻦ ﺧﻼت اﻹﯾﺜﯿﻞ ﻓﻲ ﻣﺤﻠﻮل ﻗﻠ ﻮي ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﯾ ﺘﻢ‬

‫ﻋﻨﺪ درﺟﺔ ﺣﺮارة )‪ (30 ºC‬ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪CH 3COOC2 H5 + NaOH ‬‬
‫‪→ CH3COONa + C2 H5 OH‬‬
‫ﻓ ﺈذا ﻋﻠﻤ ﺖ أن ﺗﺮﻛﯿ ﺰ ﻋﯿﻨ ﺔ ﻣ ﻦ اﻟﺨ ﻼت واﻟﻤﺤﻠ ﻮل اﻟﻘﻠ ﻮي ﯾﺴ ﺎوي‬

‫)‪ (0.05 M‬وﻛﺎن ﺗﺮﻛﯿﺰ ﺧﻼت اﻟﺼﻮدﯾﻮم ﯾﺰداد ﻣﻊ اﻟ ﺰﻣﻦ ﻛﻤ ﺎ ﻓ ﻲ‬
‫اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪Time/min.‬‬ ‫‪4‬‬ ‫‪9‬‬ ‫‪15‬‬ ‫‪24‬‬ ‫‪37‬‬ ‫‪53‬‬
‫)‪[CH3COONA] × 103 (M‬‬ ‫‪5.91‬‬ ‫‪11.42‬‬ ‫‪16.3‬‬ ‫‪22.07‬‬ ‫‪27.17‬‬ ‫‪31.47‬‬
‫ﻓﺎﺣﺴﺐ ‪:‬‬
‫ب( ﻋﻤﺮ ﻧﺼﻒ اﻟﺘﻔﺎﻋﻞ‬ ‫أ( ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‬
‫ﺍﳊﻞ‬
‫ﺑﻤﺎ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ وﺗﺮﻛﯿﺰ اﻟﻤﺎدﺗﯿﻦ اﻟﻤﺘﻔﺎﻋﻠﺘﯿﻦ ﻣﺘﺴﺎوﯾﺎ ُ‬

‫ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ ﺣﺴ ﺎب ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ‬
‫‪ 1‬‬ ‫‪1‬‬
‫ﺑﺘﻤﺜﯿ ﻞ )‪ (1/(a – x‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات واﻟ ﺰﻣﻦ‬ ‫‪‬‬ ‫‪= kt + ‬‬
‫) ‪ (a - x‬‬ ‫‪a‬‬
‫)‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت‪ ،‬ﻓﻨﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻘﻄ ﻊ ﻣﺤ ﻮر‬

‫اﻟﺼﺎدات ﺑﻤﻘﺪار )‪ (1/a‬وﻣﯿﻠﮫ ﯾﺴﺎوي ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪.(k‬‬

‫)‪(572‬‬
‫ﻛﻤ ﺎ ﯾﻤﻜ ﻦ إﯾﺠ ﺎد ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻣ ﻦ اﻟﺮﺳ ﻢ اﻟﺒﯿ ﺎﻧﻲ ﻟﻠﻌﻼﻗ ﺔ‬
‫‪ x‬‬ ‫‪‬‬
‫ﺑﺘﻤﺜﯿﻞ )‪ (x/a(a – x‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات واﻟ ﺰﻣﻦ‬ ‫‪‬‬ ‫‪= kt ‬‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫)‪ (t‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ﻓﻨﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﯾﻤﺮ ﺑﻨﻘﻄﺔ اﻷﺻﻞ‬
‫وﻣﯿﻠﮫ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ .(k‬وﻧﺤﺼﻞ ﻋﻠﻰ ﻗﯿﻤﺔ )‪ (x‬ﻣﻦ اﻟﻌﻼﻗﺔ ‪:‬‬
‫]‪( x = [A‬‬ ‫‪o‬‬
‫) ‪- [A]t‬‬
‫إﻻ أﻧ ﮫ ﻓ ﻲ ﻣﺜ ﻞ ھ ﺬا اﻟﺴ ﺆال ﻻ ﻧﺤﺘ ﺎج ﻟﻤﺜ ﻞ ھ ﺬه اﻟﻤﻌﺎدﻟ ﺔ‬

‫) ‪ ( x = [ A ]o - [A]t‬ﻷن ﻗﯿﻤ ﺔ )‪ (x‬ﻣﻌﻄ ﺎة ﻓ ﻲ اﻟﺠ ﺪول ﺣﯿ ﺚ‬
‫)‪([CH3COONA] = x‬‬
‫‪ x‬‬ ‫‪‬‬ ‫‪ 1‬‬ ‫‪1‬‬
‫‪:‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫و‬ ‫‪‬‬ ‫‪= kt + ‬‬ ‫وﺑﻌﻤﻞ اﻟﺠﺪول اﻟﻼزم ﻟﺘﻤﺜﯿﻞ‬
‫)‪ a (a - x‬‬ ‫‪‬‬ ‫) ‪ (a - x‬‬ ‫‪a‬‬
‫‪[A]o = a = 0.05 M‬‬

‫‪1‬‬ ‫‪1‬‬
‫=‬ ‫‪= 20‬‬
‫‪a 0.05‬‬
‫‪Time/min.‬‬ ‫‪4‬‬ ‫‪9‬‬ ‫‪15‬‬ ‫‪24‬‬ ‫‪37‬‬ ‫‪53‬‬
‫× ]‪[CH3COONA‬‬ ‫‪5.91‬‬ ‫‪11.42‬‬ ‫‪16.3‬‬ ‫‪22.07‬‬ ‫‪27.17‬‬ ‫‪31.47‬‬
‫‪103 (M) = x‬‬
‫) ‪(a – x‬‬ ‫‪0.0441 0.03858 0.0337 0.02793 0.02283 0.01853‬‬
‫‪ 1 ‬‬
‫‪‬‬ ‫‪‬‬
‫‪a-x‬‬ ‫‪22.68‬‬ ‫‪25.92‬‬ ‫‪29.67‬‬ ‫‪35.80‬‬ ‫‪43.80‬‬ ‫‪53.97‬‬
‫)‪a (a - x‬‬
‫‪2.205‬‬ ‫‪1.929‬‬ ‫‪1.685‬‬ ‫‪1.3965‬‬ ‫‪1.1415‬‬ ‫‪9.265‬‬
‫‪× 10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-4‬‬
‫‪ x ‬‬
‫‪‬‬ ‫‪‬‬ ‫‪2.68‬‬ ‫‪5.92‬‬ ‫‪9.67‬‬ ‫‪15.80‬‬ ‫‪23.80‬‬ ‫‪33.97‬‬
‫‪ a (a - x) ‬‬

‫)‪(573‬‬
‫‪ 1‬‬ ‫‪1‬‬

‫‪‬‬ ‫‪= kt + ‬‬ ‫وﻣﻦ اﻟﺠﺪول ﯾﻤﻜﻦ أن ﻧﻤﺜﻞ ﻛﻼ اﻟﻤﻌﺎدﻟﺘﯿﻦ‬
‫)‪ (a - x‬‬ ‫‪a‬‬
‫‪ x‬‬ ‫‪‬‬

‫‪:‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫و‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫‪ 1 ‬‬ ‫‪ 1‬‬ ‫‪1‬‬

‫اﻟﺘﺎﻟﯿﺔ ﻋﻠﻰ‬ ‫‪‬‬ ‫‪‬‬ ‫ﺑﺘﻤﺜﯿﻞ ﻗﯿﻢ‬ ‫‪‬‬ ‫‪= kt + ‬‬ ‫وﻟﻨﺄﺧﺬ اﻟﻤﻌﺎدﻟﺔ اﻷوﻟﻰ‬
‫‪a-x‬‬ ‫) ‪ (a - x‬‬ ‫‪a‬‬
‫ﻣﺤﻮر اﻟﺼﺎدات ‪:‬‬

‫‪ 1 ‬‬
‫‪‬‬ ‫‪‬‬ ‫‪22.68 25.92 29.67 35.80‬‬
‫‪a-x‬‬ ‫‪43.80‬‬ ‫‪53.97‬‬
‫وﺗﻤﺜﯿﻞ ﻗﯿﻢ اﻟﺰﻣﻦ ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ‪:‬‬

‫‪Time/min.‬‬ ‫‪4‬‬ ‫‪9‬‬ ‫‪15‬‬ ‫‪24‬‬ ‫‪37‬‬ ‫‪53‬‬
‫ﻓﻨﺤﺼﻞ ﻋﻠﻰ اﻟﺸﻜﻞ )‪.(٢٧-٢‬‬
‫ﺷﻜﻞ )‪(٢٧-٢‬‬

‫)‪(574‬‬
‫وﻣﻨﮫ ﻓﺈن اﻟﻤﯿﻞ ‪:‬‬

‫‪46 - 20‬‬
‫= ‪slope‬‬ ‫‪= 0.65‬‬
‫‪40 - 0‬‬
‫‪⇒ k = 0.65 M -1 min -1‬‬
‫ب( ﺣﺴﺎب ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻣﻦ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪1‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪ak‬‬
‫‪1‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪0.05 × 0.65‬‬
‫‪t 1 = 30.77 min.‬‬
‫‪2‬‬
‫وﻣ ﻦ اﻷﻣﺜﻠ ﺔ اﻟﻤﺸ ﮭﻮرة ﻋﻠ ﻰ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﺗﻔﺎﻋ ﻞ ﺧ ﻼت‬

‫اﻹﯾﺜﯿﻞ ﻣﻊ ﻗﺎﻋﺪة ﻗﻮﯾﺔ )وأﺧﺬﻧﺎ ﻟﮭﺎ ﻣﺜﺎﻻً أﻋ ﻼه( وﻛ ﺬﻟﻚ ﺗﻔﻜ ﻚ ﻣﺮﻛ ﺐ‬
‫اﻷﺳﯿﺘﺎﻟﺪھﯿﺪ )‪ (acetaldehyde‬ﺣﺮارﯾﺎ ً ﻓﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي وﺳ ﻮف‬
‫ﻧﻨ ﺎﻗﺶ ھ ﺬﯾﻦ اﻟﺘﻔ ﺎﻋﻠﯿﻦ ﺑﺸ ﻲء ﻣ ﻦ اﻟﺘﻔﺼ ﯿﻞ‪ ،‬وذﻟ ﻚ ﺑﺎﻹﻋﺘﻤ ﺎد ﻋﻠ ﻰ‬
‫اﻟﺤﺠﻢ واﻟﻀﻐﻂ ﻋﻠﻰ اﻟﺘﻮاﻟﻲ ﻛﻤﺎ ﻓﻌﻠﻨﺎ ﻓﻲ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(575‬‬
‫ﺃ( ﻗﺎﻧﻮﻥ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ‪  a (a - x) = kt ‬ﺑﺪﻻﻟﺔ ﺍﳊﺠﻢ‬

‫‪‬‬ ‫‪x‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫ﺗﻔﺎﻋﻞ ﺧﻼﺕ ﺍﳌﻴﺜﻴﻞ ﻣﻊ ﻗﺎﻋﺪﺓ ﻗﻮﻳﺔ‬

‫ﺳﻮف ﻧﻨﺎﻗﺶ ھﺬا اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪﻣﺎ ﯾﺤ ﺪث اﻟﺘﻔﺎﻋ ﻞ ﻧﺘﯿﺠ ﺔ ﻟﻤ ﺰج ﺗﺮاﻛﯿ ﺰ‬
‫ﻣﺘﺴﺎوﯾﺔ ﻣﻦ اﻟﺨﻼت واﻟﻘﺎﻋﺪة‪.‬‬
‫ﻛﻴﻒ ﳝﻜﻦ ﻣﺘﺎﺑﻌﺔ ﻫﺬﺍ ﺍﻟﺘﻔﺎﻋﻞ؟‬
‫ﯾﻤﻜﻦ ﻣﺘﺎﺑﻌﺔ ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﺑﺄﺧ ﺬ ﻋﯿﻨ ﺔ ﻣﺤ ﺪدة ﻣ ﻦ ﻣ ﺰﯾﺞ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ‬

‫ﻓﺘ ﺮات زﻣﻨﯿ ﺔ ﻣﺨﺘﻠﻔ ﺔ وﻣﻌﺎﯾﺮﺗﮭ ﺎ ﺑﻮاﺳ ﻄﺔ ﺣﻤ ﺾ ﻗﯿﺎﺳ ﻲ‪ ،‬ﻓ ﻲ ھ ﺬه‬
‫اﻟﺤﺎﻟﺔ ﯾﻜﻮن ﺣﺠ ﻢ اﻟﺤ ﺎﻣﺾ )‪ (Vt‬اﻟﻤﺴ ﺘﺨﺪم ﻓ ﻲ اﻟﻤﻌ ﺎﯾﺮة ﻣﻜﺎﻓﺌ ﺎ ً ﻟﻤ ﺎ‬
‫ﺗﺒﻘﻰ ﻣﻦ ﺗﺮﻛﯿﺰ اﻟﻘﺎﻋﺪة ﻓﻲ اﻟﻌﯿﻨﺔ‪ ،‬ﻓﺈذا ﻛ ﺎن ﺗﺮﻛﯿ ﺰ اﻟﻘﺎﻋ ﺪة اﻹﺑﺘ ﺪاﺋﻲ‬
‫ﯾﺴ ﺎوي )‪ (a‬و )‪ (x‬ﻣﻘ ﺪار اﻹﻧﺨﻔ ﺎض ﻓ ﻲ اﻟﺘﺮﻛﯿ ﺰ ﻓ ﺈن ﻣ ﺎ ﯾﺘﺒﻘ ﻰ ﻣ ﻦ‬
‫ﺗﺮﻛﯿﺰ اﻟﻘﺎﻋﺪة )‪ (a – x‬ﯾﻜﻮن ﻣﻜﺎﻓﺌﺎ ً ﻟﺤﺠﻢ اﻟﺤﻤﺾ اﻟﻤﺴ ﺘﺨﺪم )‪،(Vt‬‬
‫أﻣﺎ ﺣﺠﻢ اﻟﺤﻤﺾ اﻟﻤﺴ ﺘﺨﺪم ﻓ ﻲ ﺑﺪاﯾ ﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (Vo‬ﻋﻨ ﺪﻣﺎ )‪(t = 0‬‬
‫ﺗﻘﺮﯾﺒﺎ ً ﻓﺈﻧﮫ ﯾﻜﺎﻓﻲء اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ )‪ (a‬ﻟﻠﻘﺎﻋﺪة‪.‬‬
‫ﻣﻦ ذﻟﻚ ﻧﺴﺘﻨﺘﺞ أن اﻹﻧﺨﻔﺎض ﻓﻲ اﻟﺘﺮﻛﯿ ﺰ )‪ (x‬ﯾﻜ ﺎﻓﻲء )‪،(Vo – Vt‬‬
‫‪ x‬‬ ‫‪‬‬
‫ﺗﺘﺤ ﻮل ﺑﺪﻻﻟ ﺔ‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫وإذا ﻋﻮﺿﻨﺎ ذﻟﻚ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫اﻟﺤﺠﻮم اﻟﻰ ﻣﺎ ﯾﻠﻲ ‪:‬‬

‫)‪(576‬‬
‫‪ x‬‬ ‫‪‬‬

‫‪‬‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫‪V - Vt‬‬
‫‪⇒ o‬‬ ‫‪=kt‬‬
‫) ‪Vo (Vt‬‬
‫وﻣﻨﮭﺎ ﯾﻤﻜﻦ ﺣﺴﺎب ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪1 Vo - Vt‬‬
‫= ‪k‬‬
‫) ‪t Vo (Vt‬‬
‫‪ Vo - Vt‬‬ ‫‪‬‬

‫اﻟﻤﻌﺎدﻟ ﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‬ ‫‪‬‬ ‫‪= k t‬‬ ‫وﺗﻤﺜ ﻞ اﻟﻤﻌﺎدﻟ ﺔ‬
‫) ‪ Vo (Vt‬‬ ‫‪‬‬
‫ﻟﮭ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﺑﺪﻻﻟ ﺔ ﺣﺠ ﻮم اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ .‬ﻛﻤ ﺎ ﻧﺆﻛ ﺪ أن ﺷ ﻜﻞ‬

‫اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ ﺑﺪﻻﻟﺔ اﻟﺤﺠ ﻮم ﯾﻤﻜ ﻦ أن ﯾﺨﺘﻠ ﻒ ﺑ ﺎﺧﺘﻼف اﻟﺘﻔﺎﻋ ﻞ‬
‫اﻟﻤﺪروس ﻛﻤﺎ ھﻮ اﻟﺤﺎل ﻓﻲ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﻣﺜﺎﻝ )‪(٧١-٢‬‬
‫ﯾﺤﺘ ﻮي اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﻋﻠ ﻰ ﺑﻌ ﺾ اﻟﻤﻌﻠﻮﻣ ﺎت اﻟﺤﺮﻛﯿ ﺔ ﻋ ﻦ ﺗﻤﯿ ﺆ‬

‫ﺧ ﻼت اﻹﯾﺜﯿ ﻞ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (25 ºC‬ﻓ ﻲ وﺟ ﻮد ﺗﺮاﻛﯿ ﺰ‬
‫ﻣﺘﺴﺎوﯾﺔ ﻣﻦ اﻹﺳﺘﺮ واﻟﮭﯿﺪروﻛﺴﯿﺪ ‪:‬‬
‫‪Time/min.‬‬ ‫‪0‬‬ ‫‪5‬‬ ‫‪15‬‬ ‫‪25‬‬ ‫‪35‬‬
‫‪Volume of acid used cm3‬‬ ‫‪16.0‬‬ ‫‪10.24‬‬ ‫‪6.13‬‬ ‫‪4.32‬‬ ‫‪3.41‬‬
‫ﺑﺮھﻦ ﻣﺴﺘﻌﯿﻨﺎ ً ﺑﺎﻟﻤﻌﻠﻮﻣﺎت اﻟﺴﺎﺑﻘﺔ ﻋﻠﻰ أن ﺗﻤﯿﺆ ﺧﻼت اﻹﯾﺜﯿﻞ ﺗﻔﺎﻋﻞ‬

‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(577‬‬
‫ﺍﳊﻞ‬
‫ﺗﻮﺻﻠﻨﺎ ﻋﻨﺪ ﻣﻨﺎﻗﺸﺔ ﺗﻤﯿﺆ ﺧﻼت اﻹﯾﺜﯿﻞ اﻟﻰ أن ﻗﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫‪ Vo - Vt‬‬ ‫‪‬‬
‫‪،  k = 1t VV‬‬
‫‪o‬‬ ‫‪- Vt ‬‬
‫‪‬‬ ‫وأﻧﮫ ﯾﻤﻜﻦ ﺣﺴﺎب ﺛﺎﺑﺖ اﻟﺴ ﺮﻋﺔ ﻣﻨ ﮫ‬ ‫‪‬‬ ‫‪= k t‬‬
‫‪‬‬ ‫‪o‬‬ ‫‪(Vt ) ‬‬ ‫) ‪ Vo (Vt‬‬ ‫‪‬‬
‫وﺑﺤﺴ ﺎب )‪ (k‬ﻋﻨ ﺪ أزﻣﻨ ﺔ ﻣﺨﺘﻠﻔ ﺔ ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ إﺛﺒ ﺎت أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬

‫اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ إذا ﺣﺼ ﻠﻨﺎ ﻋﻠ ﻰ ﻗﯿﻤ ﺔ ﺛﺎﺑﺘ ﺔ )ﺗﻘﺮﯾﺒ ﺎ ً( ﻟﻘ ﯿﻢ )‪ ،(k‬ﺑﻌﻤ ﻞ‬
‫‪Vo = 16.0 cm3‬‬
‫‪Time/min.‬‬ ‫‪5‬‬ ‫‪15‬‬ ‫‪25‬‬ ‫‪35‬‬
‫)‪Volume of acid used cm3 (Vt‬‬ ‫‪10.24‬‬ ‫‪6.13‬‬ ‫‪4.32‬‬ ‫‪3.41‬‬
‫‪Vo - Vt‬‬ ‫‪5.76‬‬ ‫‪9.87‬‬ ‫‪11.68‬‬ ‫‪12.59‬‬
‫‪VoVt‬‬ ‫‪163.84‬‬ ‫‪98.08‬‬ ‫‪69.12‬‬ ‫‪54.56‬‬
‫‪ Vo - Vt ‬‬
‫‪‬‬ ‫‪‬‬ ‫‪0.0352‬‬ ‫‪0.1006‬‬ ‫‪0.1690‬‬ ‫‪0.2310‬‬
‫‪ Vo (Vt ) ‬‬
‫‪1‬‬
‫‪ ‬‬ ‫‪0.2‬‬ ‫‪0.067‬‬ ‫‪0.04‬‬ ‫‪0.029‬‬
‫‪t‬‬
‫‪ 1   V - Vt ‬‬ ‫× ‪7.04‬‬ ‫× ‪6.74‬‬ ‫× ‪6.76‬‬ ‫× ‪6.70‬‬

‫‪k =   o‬‬ ‫‪‬‬
‫‪ t   Vo (Vt ) ‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬
‫وﺣﯿﺚ أن ﻗﯿﻤﺔ )‪ (k‬ﺗﻘﺮﯾﺒ ﺎ ً ﺛﺎﺑﺘ ﺔ‪ ،‬ﻓ ﺈن ھ ﺬا ﯾ ﺪل ﻋﻠ ﻰ أن ﺗﻔﺎﻋ ﻞ ﺗﻤﯿ ﺆ‬

‫ﺧﻼت اﻹﯾﺜﯿﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(578‬‬
‫ﺏ( ﻗﺎﻧﻮﻥ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ ‪  a (a - x) = kt ‬ﺑﺪﻻﻟﺔ ﺍﻟﻀﻐﻂ‬

‫‪‬‬ ‫‪x‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫ً‬
‫ﻣﺜﺎﻟﻪ ‪ :‬ﺗﻔﻜﻚ ﺍﻷﺳﻴﺘﺎﻟﺪﻫﻴﺪ ﺣﺮﺍﺭﻳﺎ‬
‫ﯾﺘﻔﻜﻚ ﻣﺮﻛﺐ اﻷﺳﯿﺘﺎﻟﺪھﯿﺪ ﺣﺮارﯾﺎ ً ﻓﻲ اﻟﻄﻮر اﻟﻐﺎزي ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪2CH 3CHO ‬‬
‫‪→ 2CH 4 + 2CO‬‬
‫ﻟﻘﺪ أﺟﺮي ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ ﺣﺠ ﻢ ﺛﺎﺑ ﺖ‪ ،‬وﺗﻤ ﺖ ﻣﺘﺎﺑﻌ ﺔ ﺗﻐﯿ ﺮ اﻟﻀ ﻐﻂ‬

‫‪ x‬‬ ‫‪‬‬
‫‪‬‬ ‫‪= kt ‬‬ ‫اﻟﻜﻠ ﻲ )‪ (Pt‬ﻣ ﻊ اﻟ ﺰﻣﻦ‪ ،‬وﻟﺘﺤﻮﯾ ﻞ اﻟﻤﻌﺎدﻟ ﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫ﺑﺪﻻﻟﺔ اﻟﻀﻐﻮط ﻧﻔﺘﺮض أن ‪:‬‬

‫‪ : Po‬اﻟﻀﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻸﺳ ﯿﺘﺎﻟﺪھﯿﺪ وھ ﻮ ﯾﻜ ﺎﻓﻲء اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ‬
‫)‪.(a‬‬
‫‪ : PA‬ﺿﻐﻂ ﻣﺎ ﺗﺒﻘﻰ ﻣﻦ اﻷﺳﯿﺘﺎﻟﺪھﯿﺪ وھﻮ ﯾﻜﺎﻓﻲء ﻣﺎ ﺗﺒﻘﻰ ﻣﻦ ﺗﺮﻛﯿﺰ‬
‫اﻷﺳﯿﺘﺎﻟﺪھﯿﺪ )‪(a – x‬‬
‫‪ : Pt‬اﻟﻀﻐﻂ اﻟﻜﻠﻲ ﻟﻠﻨﻈﺎم ﻋﻨﺪ أي زﻣﻦ )‪(t‬‬
‫)‪ : (Po – PA‬ﻣﻘﺪار اﻹﻧﺨﻔﺎض ﻓﻲ اﻟﺘﺮﻛﯿﺰ وﯾﻜﺎﻓﻲء )‪(x‬‬
‫‪ x‬‬ ‫‪‬‬
‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫ﺑﻨﺎء ﻋﻠﻰ ﻣﺎ ﺳﺒﻖ ﺗﺼﺒﺢ اﻟﻤﻌﺎدﻟﺔ‬
‫)‪ a (a - x‬‬ ‫‪‬‬
‫‪x‬‬
‫‪= kt‬‬
‫)‪a (a - x‬‬
‫‪P -P‬‬
‫‪⇒ o A = kt‬‬
‫) ‪Po (PA‬‬

‫)‪(579‬‬
‫وﺣﯿ ﺚ أﻧ ﮫ ﻻ ﯾﻤﻜ ﻦ ﻗﯿ ﺎس ﺿ ﻐﻂ ﻣ ﺎ ﺗﺒﻘ ﻰ ﻣ ﻦ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ ﺑﻤﻔ ﺮده‬

‫)‪ (PA‬ﻓﺈﻧﮫ ﻻ ﺑﺪ ﻣﻦ اﺳﺘﺨﺪام اﻟﻀﻐﻂ اﻟﻜﻠﻲ ﺣﯿﺚ ﯾﻤﻜﻦ ﻗﯿﺎﺳﮫ ﺑﺴﮭﻮﻟﺔ‬
‫ﻟﻤﺘﺎﺑﻌﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ‪ ،‬ﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﯾﻜﻮن ‪:‬‬
‫‪2CH 3CHO ‬‬
‫‪→ 2CH 4 + 2CO‬‬
‫‪PA‬‬ ‫‪PCH 4‬‬ ‫‪PCO‬‬
‫‪Pt = PA + PCH 4 + PCO‬‬
‫‪ ‬‬
‫‪‬‬‫‪x‬‬
‫‪‬‬ ‫‪x‬‬
‫‪2x‬‬
‫‪Pt = PA + 2x‬‬
‫وﺣﯿﺚ أن )‪ (x = Po – PA‬ﻓﺈن اﻟﻤﻌﺎدﻟﺔ ) ‪ ( Pt = PA + 2x‬ﺗﺆول اﻟﻰ ‪:‬‬

‫‪Pt = PA + 2x‬‬
‫) ‪Pt = PA + 2 (Po - PA‬‬
‫‪Pt = PA + 2Po - 2PA‬‬
‫‪Pt = - PA + 2Po‬‬
‫‪⇒ PA = 2Po − Pt‬‬
‫وﺑﺎﻟﺘ ﺎﻟﻲ أوﺟ ﺪﻧﺎ ﻋﻼﻗ ﺔ ﻟﺤﺴ ﺎب ‪ PA‬اﻟﺘ ﻲ ﯾﺼ ﻌﺐ ﺣﺴ ﺎﺑﮭﺎ ﻣﺒﺎﺷ ﺮة‪.‬‬
‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﺑﮭ ﺎ ﻓ ﻲ اﻟﻘﯿﻤ ﺔ ) ‪ ( Po - PA‬اﻟﻤﻮﺟ ﻮدة ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬
‫‪ Po - PA‬‬ ‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪‬‬ ‫‪= kt ‬‬
‫) ‪ Po (PA‬‬ ‫‪‬‬
‫) ‪Po - PA = Po - ( 2Po − Pt‬‬

‫‪Po - PA = Po - 2Po + Pt‬‬
‫‪Po - PA = - Po + Pt‬‬
‫‪⇒ Po - PA = Pt - Po‬‬

‫)‪(580‬‬
‫ﻓ ﻲ‬ ‫‪Po - PA = Pt - Po‬‬ ‫و‬ ‫‪PA = 2Po − Pt‬‬ ‫وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﺑﮭ ﺬه اﻟﻘ ﯿﻢ ‪:‬‬
‫‪ Po - PA‬‬ ‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫اﻟﻤﻌﺎدﻟﺔ‬
‫) ‪ Po (PA‬‬ ‫‪‬‬
‫‪PA = 2Po − Pt‬‬

‫‪Po - PA = Pt - Po‬‬
‫‪Po - PA‬‬
‫‪= kt‬‬
‫) ‪Po (PA‬‬
‫‪Pt - Po‬‬
‫⇒‬ ‫‪= kt‬‬
‫) ‪Po (2Po − Pt‬‬
‫‪‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬

‫ﻣﻌﺎدﻟﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ ﺑﻨﻘﻄ ﺔ اﻷﺻ ﻞ‬ ‫‪‬‬ ‫‪= kt ‬‬ ‫واﻟﻤﻌﺎدﻟﺔ‬
‫) ‪ Po (2Po − Pt‬‬ ‫‪‬‬
‫‪‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬

‫ﻋﻠ ﻰ ﻣﺤ ﻮر‬ ‫‪‬‬ ‫‪‬‬ ‫وﻣﯿﻠ ﮫ )‪ (k‬وﯾﻤﻜ ﻦ رﺳ ﻤﮫ ﺑﺘﻤﺜﯿ ﻞ ﻗ ﯿﻢ‬
‫‪ Po (2Po − Pt ) ‬‬
‫اﻟﺼﺎدات ﻣﻘﺎﺑﻞ اﻟﺰﻣﻦ )‪ (t‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت‪.‬‬

‫‪‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬
‫‪  P‬ﻓﺈن ‪:‬‬ ‫) ‪(2Po − Pt‬‬
‫‪= kt ‬‬ ‫وﻟﺤﺴﺎب ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻣﻦ اﻟﻤﻌﺎدﻟﺔ‬
‫‪‬‬ ‫‪o‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬

‫‪k =  ‬‬ ‫‪‬‬
‫‪ t   Po (2Po − Pt ) ‬‬
‫‪( 2CH CHO → 2CH‬‬

‫‪3‬‬ ‫‪4‬‬ ‫) ‪+ 2CO‬‬ ‫وھ ﺬه ھ ﻲ اﻟﻤﻌﺎدﻟ ﺔ اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫ﺑﺪﻻﻟﺔ اﻟﻀﻐﻂ ﺣﯿﺚ ﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ )‪ (k‬ﻋﻦ طﺮﯾﻖ ﻗﯿﺎس اﻟﻀﻐﻂ‬
‫اﻟﻜﻠ ﻲ)‪ ،(Pt‬وﻣﻌﺮﻓ ﺔ اﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ )‪ (Po‬ﻟﻤﺮﻛ ﺐ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ‪،‬‬

‫)‪(581‬‬
‫وذﻟ ﻚ ﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺎت اﻟﺒﯿﺎﻧﯿ ﺔ اﻟﻤﻨﺎﺳ ﺒﺔ ﺑ ﯿﻦ اﻟﻀ ﻐﻂ واﻟ ﺰﻣﻦ أو‬

‫ﺑﺎﻟﺤﺴﺎب‪.‬‬
‫ﻣﺜﺎﻝ )‪(٧٢-٢‬‬
‫ﺑﺎﻻﻋﺘﻤﺎد ﻋﻠﻰ اﻟﻤﻌﻠﻮﻣﺎت اﻟﻮاردة ﻓﻲ اﻟﺠﺪول اﻟﺘ ﺎﻟﻲ ﺑ ﺮھﻦ أن ﺗﻔﻜ ﻚ‬

‫ﻣﺮﻛ ﺐ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ ﺣﺮارﯾ ﺎ ً ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة‬
‫)‪ (518 ºC‬ﺗﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫‪Time/ min.‬‬ ‫‪0‬‬ ‫‪42‬‬ ‫‪73‬‬ ‫‪105‬‬ ‫‪190‬‬
‫‪Pressure mmHg‬‬ ‫‪363‬‬ ‫‪397‬‬ ‫‪417‬‬ ‫‪437‬‬ ‫‪477‬‬
‫ﺍﳊﻞ‬
‫ﻋﻨ ﺪ ﻣﻨﺎﻗﺸ ﺔ ﺗﻔﻜ ﻚ ﻣﺮﻛ ﺐ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ ﺣﺮارﯾ ﺎ ً ﺗﻮﺻ ﻠﻨﺎ اﻟ ﻰ ﻗ ﺎﻧﻮن‬
‫ﺣﺴﺎب ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪ (k‬ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﺑﺪﻻﻟﺔ اﻟﻀﻐﻂ ﻛﻤ ﺎ‬
‫ﯾﻠﻲ ‪:‬‬
‫‪1‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬
‫‪k =  ‬‬ ‫‪‬‬
‫‪ t   Po (2Po − Pt ) ‬‬
‫ﺣﯿﺚ ‪:‬‬
‫‪ : Po‬اﻟﻀﻐﻂ ﻓﻲ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ أي ﻋﻨﺪ )‪(t = 0‬‬
‫‪ : Pt‬اﻟﻀﻐﻂ اﻟﻜﻠﻲ )ﻟﻠﻤﺘﻔﺎﻋﻼت واﻟﻨﻮاﺗﺞ( ﻋﻨﺪ زﻣﻦ )‪.(t‬‬

‫)‪(582‬‬
‫وﻟﻜﻲ ﻧﺜﺒﺖ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﻧﺤﺴﺐ ﻗﯿﻤﺔ )‪ (k‬ﻋﻨ ﺪ أزﻣﻨ ﺔ‬

‫‪‬‬ ‫‪‬‬
‫‪ . k =  1t   P‬وﺑﻌﻤ ﻞ اﻟﺠ ﺪول‬ ‫‪Pt - Po‬‬
‫‪‬‬
‫‪(2Po − Pt ) ‬‬
‫ﻣﺨﺘﻠﻔ ﺔ ﺑﺎﺳ ﺘﺨﺪام اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ ‬‬ ‫‪o‬‬
‫اﻟﻼزم ﻟﻠﺤﺴﺎﺑﺎت ﺳﻨﻼﺣﻆ أن إن ﻗﯿﻤﺔ )‪ (k‬اﻟﺜﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﺗ ﺪل ﻋﻠ ﻰ أن‬

‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫) ‪( Po = 363 mmHg‬‬
‫) ‪( 2Po = 2 × 363 = 726 mmHg‬‬
‫‪Time/ min.‬‬ ‫‪42‬‬ ‫‪73‬‬ ‫‪105‬‬ ‫‪190‬‬
‫)‪Pressure mmHg (Pt‬‬ ‫‪397‬‬ ‫‪417‬‬ ‫‪437‬‬ ‫‪477‬‬
‫) ‪( Pt - Po‬‬ ‫‪34‬‬ ‫‪54‬‬ ‫‪74‬‬ ‫‪114‬‬
‫) ‪(2Po − Pt‬‬ ‫‪329‬‬ ‫‪309‬‬ ‫‪289‬‬ ‫‪249‬‬
‫) ‪Po (2Po − Pt‬‬ ‫‪119427‬‬ ‫‪112167‬‬ ‫‪104907‬‬ ‫‪90387‬‬
‫‪‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬ ‫‪2.85 × 10-4‬‬ ‫‪4.81 × 10-4‬‬ ‫‪7.05 × 10-4‬‬ ‫‪12.6 × 10-4‬‬
‫‪ Po (2Po − Pt ) ‬‬
‫‪1‬‬ ‫‪0.0238‬‬ ‫‪0.0137‬‬ ‫‪0.0095‬‬ ‫‪0.0053‬‬
‫‪ ‬‬
‫‪t‬‬
‫‪ 1‬‬ ‫‪Pt - Po‬‬ ‫‪‬‬
‫‪k =  ‬‬ ‫‪‬‬ ‫‪6.78 × 10-6‬‬ ‫‪6.59 ×10-6‬‬ ‫‪6.70 ×10-6‬‬ ‫‪6.68 × 10-6‬‬
‫‪ t   Po (2Po − Pt ) ‬‬

‫)‪(583‬‬
‫ﻃﺮﻕ ﺗﻌﻴﲔ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ ﺍﻟﺮﺗﺒﺔ‬
‫‪ (١‬ﻃﺮﻳﻘﺔ ﺍﻟﺘﻌﻮﻳﺾ ‪:‬‬
‫ﯾﻤﻜﻦ ﺗﻌﯿﯿﻦ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ ﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻋ ﻦ اﻟﻘ ﯿﻢ اﻟﺘ ﻲ ﺣﺼ ﻠﻨﺎ‬

‫ﻋﻠﯿﮭ ﺎ ﺑﺎﻟﺘﺠﺮﺑ ﺔ ﻋ ﻦ ﻛ ﻞ ﻣ ﻦ )‪ (b – x) ، (a – x‬ﻋﻨ ﺪ ﻣﺨﺘﻠ ﻒ‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪b (a - x) ‬‬
‫أو اﻟﻤﻌﺎدﻟ ﺔ‬ ‫= ‪ k‬‬
‫)‪t (a - b‬‬
‫‪log‬‬ ‫‪‬‬
‫‪a (b - x) ‬‬
‫اﻷزﻣﻨ ﺔ وذﻟ ﻚ ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪b (a - x) ‬‬

‫‪ .  k = t ( a - b ) ln a (b - x) ‬وإذا ﻛﺎﻧﺖ ﻗﯿﻢ )‪ (k‬اﻟﻤﺤﺴﻮﺑﺔ ﺛﺎﺑﺘ ﺔ ﻓ ﻲ ﻣ ﺪى‬
‫‪‬‬ ‫‪‬‬
‫ﻣﻦ اﻟﺨﻄﺄ اﻟﺘﺠﺮﯾﺒﻲ اﻟﻤﺴﻤﻮح ﺑ ﮫ ﻟﻤﺠﻤﻮﻋ ﺔ اﻟﺘﺠ ﺎرب ﯾﻜ ﻮن اﻟﺘﻔﺎﻋ ﻞ‬

‫ﺛﻨ ﺎﺋﻲ اﻟﺮﺗﺒ ﺔ وﺗﻜ ﻮن ﻣﺘﻮﺳ ﻂ اﻟﻘﯿﻤ ﺔ ﻟﻠﺜﺎﺑ ﺖ )‪ (k‬ھ ﻲ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ‬
‫ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫‪ (٢‬ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﺒﻴﺎﻧﻴﺔ ‪:‬‬
‫ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت ﺛﻨﺎﺋﯿ ﺔ اﻟﺮﺗﺒ ﺔ )‪ (a ≠ b‬ﯾﻤﻜ ﻦ ﻛﺘﺎﺑ ﺔ اﻟﻤﻌﺎدﻟ ﺔ‬

‫‪‬‬ ‫‪2.303‬‬ ‫‪b (a - x) ‬‬
‫ﻓﻲ ﺻﻮرة ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬ ‫‪‬‬ ‫‪k‬‬ ‫=‬
‫)‪t (a - b‬‬
‫‪log‬‬ ‫‪‬‬
‫‪a (b - x) ‬‬
‫‪‬‬

‫)‪(584‬‬
‫‪2.303‬‬ ‫)‪b (a - x‬‬

‫=‪k‬‬ ‫‪log‬‬
‫)‪t (a - b‬‬ ‫)‪a (b - x‬‬
‫‪2.303‬‬ ‫)‪b (a - x‬‬
‫=‪kt‬‬ ‫× ‪log‬‬
‫)‪( a - b ) a (b - x‬‬
‫‪2.303‬‬ ‫‪b‬‬ ‫)‪(a - x‬‬
‫=‪kt‬‬ ‫‪log + log‬‬
‫‪(a - b) a‬‬ ‫)‪(b - x‬‬
‫)‪(a - x) k (a - b‬‬ ‫‪b‬‬
‫‪⇒ log‬‬ ‫=‬ ‫‪t - log‬‬ ‫‪ ‬‬
‫)‪(b - x‬‬ ‫‪2.303‬‬ ‫‪a‬‬
‫‪‬‬ ‫‪(a - x) ‬‬ ‫‪‬‬ ‫)‪(a - x) k(a - b‬‬ ‫‪ b ‬‬

‫‪ log‬‬ ‫‪‬‬ ‫ﻧﺮﺳ ﻢ‬ ‫‪ log‬‬ ‫=‬ ‫‪t - log‬‬ ‫‪ ‬‬ ‫وﻣ ﻦ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪(b - x) ‬‬ ‫‪‬‬ ‫‪(b‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪2.303‬‬ ‫‪ a ‬‬
‫ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات واﻟﺰﻣﻦ )‪ (t‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت‪ ،‬ﻧﺤﺼﻞ ﻋﻠﻰ‬

‫‪ ،  k2.303‬وﻣﻨﮭﺎ ﯾﻤﻜﻦ ﺗﻌﯿﯿﻦ ﻗﯿﻤﺔ )‪.(k‬‬
‫‪(a - b) ‬‬
‫ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﯾﻜﻮن ﻣﯿﻠﮫ ھﻮ ‪ :‬‬
‫‪‬‬ ‫‪‬‬
‫‪ (٣‬ﻃﺮﻳﻘﺔ ﺍﻟﻜﺴﺮ ﻣﻦ ﻋﻤﺮ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻻ ﯾﻤﻜ ﻦ اﺳ ﺘﺨﺪاﻣﮭﺎ ﻓ ﻲ‬

‫ﺣﺎﻟ ﺔ ﻋ ﺪم ﺗﺴ ﺎوي ﺗﺮﻛﯿ ﺰي اﻟﻤ ﺎدﺗﯿﻦ )‪ (A‬و )‪ (B‬ﻷن ﻛ ﻼً ﻣﻨﮭﻤ ﺎ‬
‫ﯾﺤﺘ ﺎج وﻗﺘ ﺎ ً ﯾﺨﺘﻠ ﻒ ﻋ ﻦ اﻵﺧ ﺮ ﻟﻜ ﻲ ﯾﻜﺘﻤ ﻞ ﺗﻔﻜ ﻚ ﻧﺼ ﻒ ﺗﺮﻛﯿ ﺰ ﻛ ﻞ‬
‫ﻣﻨﮭﻤ ﺎ‪ ،‬وﻟﻜ ﻦ ﯾﻤﻜ ﻦ اﺳ ﺘﺨﺪام ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ إذا ﻛﺎﻧ ﺖ اﻟﺘﺮاﻛﯿ ﺰ‬
‫ﻣﺘﺴ ﺎوﯾﺔ )‪ (a = b‬ﻟﻠﻤ ﺎدﺗﯿﻦ اﻟﻤﺨﺘﻠﻔﺘ ﯿﻦ أو ﻓ ﻲ ﺣﺎﻟ ﺔ وﺟ ﻮد ﻣ ﺎدة‬
‫◌‬ ‫ﻣﺘﻔﺎﻋﻠﺔ واﺣﺪة )‪ (A‬ﻣﺜﻼً‪.‬‬
‫إن ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ھ ﻲ اﻟﻔﺘ ﺮة اﻟﺰﻣﻨﯿ ﺔ اﻟﻼزﻣ ﺔ ﻹﻧﻘ ﺎص ﺗﺮﻛﯿ ﺰ‬
‫اﻟﻤﺘﻔﺎﻋ ﻞ اﻟ ﻰ ﻧﺼ ﻒ ﻗﯿﻤﺘ ﮫ اﻹﺑﺘﺪاﺋﯿ ﺔ ﻓﯿﻜ ﻮن ﺣﯿﻨﺌ ﺬ)‪(t = t1/2‬‬

‫)‪(585‬‬
‫‪‬‬ ‫‪1  x ‬‬

‫ﻧﺤﺼ ﻞ‬ ‫‪ k = at  a - x  ‬‬
‫‪‬‬ ‫‪‬‬
‫و )‪ (x = a/2‬وﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻓ ﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬
‫ﻋﻠﻰ ‪:‬‬
‫‪1 x ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪at  a - x ‬‬
‫‪1  x ‬‬
‫=‪t‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ka a-x‬‬
‫‪1  a/2 ‬‬
‫‪t1/2‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫‪k a  a - a/2 ‬‬
‫‪1  a/2 ‬‬
‫= ‪t1/2‬‬ ‫‪‬‬ ‫‪‬‬
‫‪k a  a - a/2 ‬‬
‫‪1  a/2 ‬‬
‫‪k a  a/2 ‬‬
‫= ‪t1/2‬‬
‫‪1‬‬
‫= ‪⇒ t1/2‬‬
‫‪ka‬‬
‫وﺑﺎﻟﺘ ﺎﻟﻲ ﻓﻔ ﻲ ھ ﺬا اﻟﻨ ﻮع ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﺗﺘﻨﺎﺳ ﺐ ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ‬

‫ﻋﻜﺴﯿﺎ ً ﻣﻊ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻠﻤﺘﻔﺎﻋ ﻞ‪ .‬وﯾﻤﻜ ﻦ ﺗﻌﯿ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ‬
‫ﻣﺒﺎﺷ ﺮة ﻣ ﻦ ﻗﯿ ﺎس ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ وﺑﻤﻌﻠﻮﻣﯿ ﺔ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ‬
‫ﻟﻠﻤﺘﻔﺎﻋﻞ‪.‬‬
‫وإذا أﻣﻜ ﻦ ﺗﻌﯿ ﯿﻦ ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻓ ﻲ ﺗﺠ ﺮﺑﺘﯿﻦ ﻣﺨﺘﻠﻔﺘ ﯿﻦ ﺣﯿ ﺚ‬
‫ﺗﻜ ﻮن اﻟﺘﺮﻛﯿ ﺰات اﻹﺑﺘﺪاﺋﯿ ﺔ ﻣﺨﺘﻠﻔ ﺔ أي ﻋﻨ ﺪ )‪ (a2 ،a1‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ‬
‫اﻟﻌﻼﻗﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫)‪(586‬‬
‫‪ 1‬‬ ‫‪‬‬

‫‪( t1/2 )1‬‬ ‫‪ ka‬‬ ‫‪‬‬
‫‪=‬‬ ‫‪1‬‬
‫‪‬‬
‫‪( t1/2 )2‬‬ ‫‪ 1‬‬ ‫‪‬‬
‫‪ka‬‬ ‫‪‬‬
‫‪‬‬ ‫‪2‬‬ ‫‪‬‬
‫‪( t1/2 )1‬‬ ‫‪1‬‬ ‫‪k a2‬‬
‫=‬ ‫×‬
‫‪( t1/2 )2 k a1 1‬‬
‫‪(t ) a‬‬
‫‪⇒ 1/2 1 = 2‬‬
‫‪( t1/2 )2 a1‬‬
‫ﻃﺮﻳﻘﺔ ﺃﺧﺮﻯ ﳊﺴﺎﺏ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ‬
‫ﺍﻟﺜﺎﻧﻴﺔ ﺫﺍﺕ ﺍﳊﺎﻟﺔ ﺍﳌﺘﺠﺎﻧﺴﺔ‬

‫ﺑﻤﺎ أن ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ھﻲ اﻟﺰﻣﻦ اﻟﺬي ﺗﺼﺒﺢ ﻓﯿﮫ ﻗﯿﻤﺔ ‪:‬‬
‫‪[ A ]ο‬‬
‫= ]‪[A‬‬
‫‪2‬‬
‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬

‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ A ] [ A ]ο‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ ]ο [ A ]ο 12‬‬
‫‪A‬‬
‫‪2‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ A ]ο [ A ]ο 12‬‬
‫‪2‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪−‬‬ ‫‪= kt 1‬‬
‫‪[ A ]ο [ A ]ο‬‬ ‫‪2‬‬
‫‪1‬‬
‫‪= kt 1‬‬
‫‪[ A ]ο‬‬ ‫‪2‬‬
‫‪1‬‬
‫= ‪⇒ t1‬‬
‫‪2‬‬
‫‪[ A ]ο k‬‬

‫)‪(587‬‬
‫ﻣﺜﺎﻝ )‪(٧٣-٢‬‬
‫واﺣ ﺪاً‬ ‫إذا ﻛ ﺎن ﺗﺮﻛﯿ ﺰ )‪ (A‬و )‪ (B‬ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ ) ‪( A + B → C‬‬

‫وﯾﺴ ﺎوي )‪ (0.5 M‬وﺑﻌ ﺪ )‪ (25 Min.‬ﻣ ﻦ ﺧﻠ ﻂ اﻟﻤ ﺎدﺗﯿﻦ ﻛ ﺎن‬
‫اﻟﺘﻔﺎﻋ ﻞ )‪ (25 %‬ﺗﺎﻣ ﺎً‪ ،‬اﺣﺴ ﺐ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ وﻓﺘ ﺮة ﻧﺼ ﻒ‬
‫اﻟﻌﻤ ﺮ؟ وإذا ﻣ ﺎ ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ اﻟﺴ ﺎﺑﻖ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻓ ﻲ ﻛ ﻞ ﻣ ﻦ‬
‫)‪ (A‬و )‪ (B‬ﻓﻜ ﻢ ﻣ ﻦ اﻟ ﺰﻣﻦ ﯾﻤﻀ ﻲ ﺣﺘ ﻰ ﯾﺘﺒﻘ ﻰ )‪ (25 %‬ﻣ ﻦ‬
‫اﻟﻤﺘﻔﺎﻋﻼت‪.‬‬
‫ﺍﳊﻞ‬
‫ﺣﯿﺚ أن اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻣﺘﺴﺎو ﻓﯿﺠﺐ إذا اﺳﺘﻌﻤﺎل اﻟﻘﺎﻧﻮن ‪:‬‬

‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ A ] [ A ]ο‬‬
‫وﺑﻤ ﺎ أن اﻟﺘﻔﺎﻋ ﻞ )‪ (25 %‬ﺗ ﺎم إذاً )‪ ([A] = 75 %‬ﻣ ﻦ اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻷﺻﻠﻲ اﻟﺬي ھﻮ )‪ (0.5 M‬وﯾﺴﺎوي ‪:‬‬
‫‪75‬‬
‫= ]‪[A‬‬ ‫‪× 0.5 = 0.375 M‬‬
‫‪100‬‬
‫‪ 1‬‬ ‫‪‬‬
‫‪: ‬‬ ‫‪-‬‬
‫‪1‬‬
‫‪= kt ‬‬ ‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ ‪ [A] = 0.375‬ﻓﻲ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ [ A ] [ A ]ο‬‬
‫‪‬‬
‫‪‬‬

‫)‪(588‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ A ] [ A ]ο‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫)‪= k × (25 × 60‬‬
‫‪0.375 0.500‬‬
‫‪0.500 - 0.375‬‬
‫‪= 1500 k‬‬
‫‪0.375 × 0.500‬‬
‫‪0.125‬‬
‫‪= 1500 k‬‬
‫‪0.1875‬‬
‫‪0.125‬‬
‫=‪k‬‬
‫‪0.1875 × 1500‬‬
‫‪k = 4.44 × 10 -4dm -3mol -1s -1‬‬
‫ﺣﺴﺎﺏ ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ‪:‬‬
‫وﺣﯿﺚ أن ﻣﻌﺎدﻟﺔ ﻧﺼﻒ اﻟﻌﻤﺮ ھﻲ ‪:‬‬

‫‪1‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪[ A ]ο k‬‬
‫‪1‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪0.500 × 4.44 × 10- 4‬‬
‫‪t 1 = 4.504 × 103 s‬‬
‫‪2‬‬
‫ﺣﺴﺎﺏ ﺍﻟﺰﻣﻦ ﺍﻟﺬﻱ ﳝﻀﻲ ﺣﱴ ﻳﺘﺒﻘﻰ )‪ (25 %‬ﻣﻦ ﺍﳌﺘﻔﺎﻋﻼﺕ ‪:‬‬

‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪[ A ] [ A ]ο‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= 4.44 × 10-4 t‬‬
‫‪0.125 0.500‬‬
‫‪0.500 - 0.125‬‬
‫‪= 4.44 × 10-4 t‬‬
‫‪0.125 × 0.500‬‬
‫‪0.375‬‬
‫‪= 4.44 × 10-4 t‬‬
‫‪0.0625‬‬
‫‪0.375‬‬
‫=‪t‬‬
‫‪0.0625 × 4.44 × 10- 4‬‬
‫‪t = 1.35 × 104 s‬‬

‫)‪(589‬‬
‫وﯾﻤﻜﻦ ﺗﻄﺒﯿﻖ اﻟﻜﺴﺮ اﻟﻌﻤﺮي ﻟﻠﺘﻔﺎﻋ ﻞ ﻣ ﻦ أي رﺗﺒ ﺔ ﺑﺸ ﺮط أن ﺗﻜ ﻮن‬

‫اﻟﻤﺘﻔ ﺎﻋﻼت ﻟﮭ ﺎ ﻧﻔ ﺲ اﻟﺘﺮﻛﯿ ﺰات اﻹﺑﺘﺪاﺋﯿ ﺔ ‪ .‬وﻋﻤﻮﻣ ﺎ ً ﺗ ﺮﺗﺒﻂ ﻓﺘ ﺮة‬
‫ﻧﺼﻒ اﻟﻌﻤﺮ )ﻟﺘﻔﺎﻋﻞ رﺗﺒﺘﮫ ‪ (n‬ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﺑﺎﻟﻌﻼﻗﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪1‬‬
‫‪t1/2 α‬‬
‫‪an - 1‬‬
‫‪k‬‬
‫‪t1/2‬‬ ‫‪= n-1‬‬
‫‪a‬‬
‫‪‬‬ ‫‪k ‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪ t1/2 = n - 1 ‬‬ ‫وﺑﺄﺧﺬ ﻟﻮﻏﺎرﯾﺘﻤﺎت اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪a ‬‬
‫‪k‬‬
‫= ‪t1/2‬‬
‫‪an - 1‬‬
‫‪k‬‬
‫‪log t1/2 = log‬‬
‫‪an - 1‬‬
‫‪log t1/2‬‬ ‫‪= log k + log a n - 1‬‬
‫‪log t1/2 = log k + ( n - 1) log a‬‬
‫‪⇒ log t1/2 = ( n - 1) log a + log k‬‬
‫واﻟﻌﻼﻗ ﺔ ) ‪ ( log t1/2 = ( n - 1) log a + log k‬ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ‪.‬‬

‫وﺑﺮﺳﻤﮭﺎ ﺑﯿﺎﻧﯿ ﺎ ً ﺑﺘﻤﺜﯿ ﻞ ) ‪ ( log t1/2‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات‪ ،‬و )‪(log a‬‬
‫ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي )‪(n – 1‬‬
‫واﻟﺠ ﺰء اﻟﻤﻘﻄ ﻮع ﻣ ﻦ اﻟﻤﺤ ﻮر اﻟﺼ ﺎدي ھ ﻮ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫)‪.(k‬‬

‫)‪(590‬‬
‫‪‬‬ ‫‪k ‬‬

‫= ‪ ،  t1/2‬ﻓ ﺈذا اﻓﺘﺮﺿ ﻨﺎ أﻧ ﮫ ﻟ ﺪﯾﻨﺎ ‪( t1/2 )1‬‬ ‫‪‬‬ ‫وﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪an - 1 ‬‬
‫ﻋﻨ ﺪﻣﺎ ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ )‪ ،(a1‬وأن ‪ ( t1/2 )2‬ھ ﻲ ﻓﺘ ﺮة ﻧﺼ ﻒ‬

‫اﻟﻌﻤﺮ ﻋﻨﺪﻣﺎ ﯾﻜﻮن اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ )‪ ،(a2‬وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ‪:‬‬
‫‪k‬‬
‫‪( t1/2 )1‬‬ ‫=‬
‫) ‪(a‬‬‫‪n-1‬‬
‫‪1‬‬
‫‪k‬‬
‫‪( t1/2 )2‬‬ ‫=‬
‫) ‪(a‬‬ ‫‪n-1‬‬
‫‪2‬‬
‫وﺑﻘﺴﻤﺔ )‪ (a1‬ﻋﻠﻰ )‪ (a2‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪k‬‬
‫‪( t1/2 )1‬‬
‫=‬
‫) ‪(a‬‬
‫‪n-1‬‬
‫‪1‬‬
‫‪( t1/2 )2‬‬ ‫‪k‬‬

‫) ‪(a‬‬
‫‪n-1‬‬
‫‪2‬‬
‫‪( t1/2 )1‬‬

‫=‬
‫‪k‬‬
‫×‬
‫) ‪(a‬‬ ‫‪n-1‬‬
‫‪2‬‬
‫) ‪(a‬‬
‫‪( t1/2 )2‬‬ ‫‪n-1‬‬
‫‪1‬‬
‫‪k‬‬
‫) ‪( t ) (a‬‬
‫‪1/2 1‬‬
‫‪n-1‬‬
‫‪2‬‬
‫=‬
‫) ‪(t‬‬
‫‪1/2 2‬‬‫) ‪(a‬‬ ‫‪n-1‬‬
‫‪1‬‬
‫) ‪(t‬‬
‫‪n-1‬‬
‫‪a ‬‬
‫‪⇒ 1/2 1‬‬ ‫‪= 2 ‬‬
‫‪( t1/2 )2‬‬ ‫‪ a1 ‬‬
‫) ‪ ( t1/2‬‬ ‫‪ a2  ‬‬

‫‪n-1‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪‬‬

‫‪ ( t1/2 )2  a1  ‬‬
‫‪1‬‬
‫=‬ ‫‪‬‬ ‫وﺑﺄﺧﺬ اﻟﻠﻮﻏﺎرﯾﺘﻤﺎت ﻟﻠﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪‬‬

‫)‪(591‬‬
‫‪( t1/2 )1  a 2 ‬‬

‫‪n-1‬‬
‫‪( t1/2 )2  a1 ‬‬

‫=‬
‫‪( t1/2 )1‬‬

‫‪n-1‬‬
‫‪ a2 ‬‬
‫‪log‬‬ ‫‪= log  ‬‬
‫‪( 1/2 )2‬‬
‫‪t‬‬ ‫‪ a1 ‬‬
‫‪( t1/2 )1‬‬ ‫‪a ‬‬
‫‪⇒ log‬‬ ‫‪= (n - 1) log  2 ‬‬
‫‪( t1/2 )2‬‬ ‫‪ a1 ‬‬
‫وﻣﻨﮭﺎ ﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ اﻟﺮﺗﺒﺔ )‪.(n‬‬

‫س( ﻋﺮف ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ )‪ (t0.5‬ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫س( ﺗﻜﻠ ﻢ ﺑﺈﯾﺠ ﺎز ﻋ ﻦ طﺮﯾﻘ ﺔ اﻟﻜﺴ ﺮ ﻣ ﻦ ﻋﻤ ﺮ اﻟﺘﻔﺎﻋ ﻞ واﻟﻤﺴ ﺘﺨﺪﻣﺔ‬
‫ﻟﺘﻌﯿﯿﻦ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(592‬‬
‫ﻣﺜﺎﻝ )‪(٧٤-٢‬‬
‫‪،A‬‬ ‫‪‬‬
‫‪→B‬‬ ‫ﻋﻨﺪﻣﺎ ﺗﻐﯿﺮ اﻟﺘﺮﻛﯿﺰ اﻻﺑﺘﺪاﺋﻲ ﻟﻠﻤﺘﻔﺎﻋﻞ )‪ (A‬ﻓﻲ اﻟﺘﻔﺎﻋ ﻞ‬
‫ﻣ ﻦ )‪ (0.51 mol L-1‬اﻟ ﻰ )‪ ،(1.03 mol L-1‬ﻓ ﺈن ﻓﺘ ﺮة ﻧﺼ ﻒ‬
‫اﻟﻌﻤ ﺮ ﻟﻠﺘﻔﺎﻋ ﻞ ﺗﻐﯿ ﺮت ﻣ ﻦ )‪ (150 s‬اﻟ ﻰ )‪ (75 s‬ﻋﻨ ﺪ )‪.(25 ºC‬‬
‫اﺣﺴﺐ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ وﻛﺬﻟﻚ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ )‪.(25 ºC‬‬
‫ﺍﳊﻞ‬
‫اﻟﻤﻌﻄﯿﺎت ‪:‬‬
‫‪(a‬‬ ‫‪1‬‬ ‫) ‪= 0.51 mol/L, a 2 = 1.03 mol/L, ( t0.5 )1 = 150 s, ( t 0.5 )2 = 75 s‬‬
‫‪‬‬ ‫‪( t1/2 )1‬‬ ‫‪ a ‬‬

‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪ log‬‬
‫‪( t1/2 )2‬‬
‫‪= (n - 1) log  2  ‬‬ ‫ﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪‬‬ ‫‪ a1  ‬‬
‫‪( t1/2 )1‬‬ ‫‪a ‬‬

‫‪log‬‬ ‫‪=(n - 1)log  2 ‬‬
‫‪( t1/2 )2‬‬ ‫‪ a1 ‬‬
‫‪150‬‬ ‫‪ 1.03 ‬‬
‫‪log‬‬ ‫‪= (n - 1)log ‬‬ ‫‪‬‬
‫‪75‬‬ ‫‪ 0.5 ‬‬
‫‪log2 = (n - 1)log 2.06‬‬
‫‪log 2‬‬
‫‪=n-1‬‬
‫‪log 2.06‬‬
‫‪0.959 + 1= n‬‬
‫‪n = 1.959  2‬‬

‫)‪(593‬‬
‫وﻣﻦ ھﻨﺎ ﻓﺈن اﻟﺘﻔﺎﻋ ﻞ ﺛﻨ ﺎﺋﻲ اﻟﺮﺗﺒ ﺔ ‪ ،‬وﺑﺎﻟﺘ ﺎﻟﻲ ﯾﻤﻜ ﻦ ﺣﺴ ﺎب )‪ (k‬ﻣ ﻦ‬
‫‪‬‬ ‫‪1 ‬‬
‫‪:‬‬ ‫= ‪ t1/2‬‬ ‫‪‬‬ ‫اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪ka‬‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪ka‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪t1/2 a‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪150 × 0.51‬‬
‫‪k = 0.0131 L mol-1 s -1‬‬
‫وﯾﻤﻜ ﻦ ﺣ ﻞ اﻟﻤﺴ ﺄﻟﺔ ﻛ ﺬﻟﻚ ﻋﻨ ﺪ اﻟﺘﻌ ﻮﯾﺾ ﺑﻘﯿﻤ ﺔ اﻟﺘﺮﻛﯿ ﺰ‬

‫)‪ (1.03 mol/L‬اﻟﺬي ﻟﮫ ﻧﺼﻒ ﻋﻤﺮ )‪: (75 s‬‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪ka‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪t1/2 a‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪75 × 1.03‬‬
‫‪k = 0.013 L mol-1 s-1‬‬

‫)‪(594‬‬
‫ﻣﺜﺎﻝ )‪(٧٥-٢‬‬
‫ﺣﺼ ﻠﻨﺎ ﻋﻠ ﻰ اﻟﻨﺘ ﺎﺋﺞ اﻟﺘﺎﻟﯿ ﺔ ﻟﺘﻔﻜ ﻚ اﻷﻣﻮﻧﯿ ﺎ ﻋﻠ ﻰ ﺳ ﻄﺢ اﻟﺘﻨﺠﺴ ﺘﻦ‬

‫اﻟﺴﺎﺧﻦ‪.‬‬
‫‪Initial pressure /torr‬‬ ‫‪65‬‬ ‫‪105‬‬ ‫‪150‬‬ ‫‪185‬‬
‫‪Half life/s‬‬ ‫‪290‬‬ ‫‪460‬‬ ‫‪670‬‬ ‫‪820‬‬
‫اﺣﺴﺐ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................... .............................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪...................................................................................................................................................................... ..................‬‬
‫‪............................................................................................... .........................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪.......................................................................................................................................... ..............................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪..................................................................................................................................................................................... ...‬‬
‫‪.............................................................................................................. ..........................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪......................................................................................................................................................... ...............................‬‬

‫)‪(595‬‬
‫‪ (٤‬ﻃﺮﻳﻘﺔ ﺍﻟﻌﺰﻝ‬
‫ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﺗﺴ ﺘﺨﺪم ﻹﯾﺠ ﺎد رﺗﺒ ﺔ اﻟﻤﺘﻔﺎﻋ ﻞ‪ ،‬وذﻟ ﻚ ﺑ ﺎﻟﺘﺤﻜﻢ ﻓ ﻲ‬

‫ظﺮوف اﻟﺘﻔﺎﻋﻞ ﺑﺤﯿﺚ أن واﺣﺪاً ﻓﻘﻂ ﻣﻦ اﻟﻤﺘﻔﺎﻋﻼت ھﻮ اﻟ ﺬي ﯾﺘﻐﯿ ﺮ‬
‫ﺗﺮﻛﯿﺰه ﻣﻊ اﻟﺰﻣﻦ ﻟﻤﺠﻤﻮﻋﺔ واﺣﺪة ﻣﻦ اﻟﺘﺠﺎرب‪ .‬وﯾﻤﻜ ﻦ أﺧ ﺬ اﻟﻤﺜ ﺎل‬
‫اﻟﺘ ﺎﻟﻲ ﻓ ﻲ اﻹﻋﺘﺒ ﺎر‪ ،‬وﯾﺘﻀ ﻤﻦ أﻛﺴ ﺪة اﻟﯿﻮدﯾ ﺪ ﺑﻮاﺳ ﻄﺔ ﻓ ﻮق أﻛﺴ ﯿﺪ‬
‫اﻟﮭﯿﺪروﺟﯿﻦ ﻓﻲ ﻣﺤﻠﻮل ﺣﺎﻣﺾ ﻛﻤﺎ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪H 2 O 2 + 2I- + 2H3O+ ‬‬
‫‪→ I2 + 4H 2 O‬‬
‫وﺗﻌﻄﻰ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫] ‪d[I 2‬‬
‫=‪V‬‬ ‫‪= k[H 2O 2 ]a [I - ]b [H 3O + ]c‬‬
‫‪dt‬‬
‫ﺣﯿ ﺚ )‪ (c, b, a‬ھ ﻲ اﻟﺮﺗ ﺐ ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﻤﺘﻔ ﺎﻋﻼت‪ (k) ،‬ھ ﻲ ﺛﺎﺑ ﺖ‬
‫اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ ﻛﻜ ﻞ‪ .‬وﻓ ﻲ وﺟ ﻮد زﯾ ﺎدة ﻣ ﻦ اﻟﺤﻤ ﺾ ﯾﻜ ﻮن ﺗﺮﻛﯿ ﺰ‬
‫اﻟﺤﻤﺾ ]‪ [H3O+‬ﺛﺎﺑﺘﺎً‪ ،‬وإذا أﺿﯿﻔﺖ ﺛﯿﻮﻛﺒﺮﯾﺘﺎت اﻟﺼﻮدﯾﻮم ﻟﺘﺤﻮﯾﻞ‬
‫اﻟﯿﻮد اﻟﻤﺘﻜﻮن اﻟﻰ اﻟﯿﻮدﯾﺪ ﻓ ﺈن ]‪ [I-‬ﺗﻜ ﻮن أﯾﻀ ﺎ ً ﻗﯿﻤﺘﮭ ﺎ ﺛﺎﺑﺘ ﺔ‪ .‬وﺗﺤ ﺖ‬
‫ھﺬه اﻟﻈﺮوف ﺗﺼﯿﺮ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬
‫‪ν = k [H 2 O 2 ]a‬‬
‫ﻓﺈذا ﻛﺎﻧﺖ )‪ (a = 2‬ﻛﺎن اﻟﻤﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒ ﺔ‪ ،‬وإذا ﻛﺎﻧ ﺖ )‪(a = 1‬‬
‫ﻛ ﺎن اﻟﻤﺘﻔﺎﻋ ﻞ أﺣ ﺎدي اﻟﺮﺗﺒ ﺔ‪ .‬وإذا ﻛﺮرﻧ ﺎ اﻟﺘﺠﺮﺑ ﺔ وﻛﺎﻧ ﺖ اﻟﻈ ﺮوف‬

‫)‪(596‬‬
‫ﻣﮭﯿﺄة ﺑﺤﯿﺚ ﻛﺎن ﺗﺮﻛﯿﺰ )‪ (H2O2‬ﻋﺎﻟﯿﺎ ً ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﺣﺴ ﺎب ﻗﯿﻤ ﺔ )‪.(b‬‬

‫وﺑﻄﺮﯾﻘﺔ ﻣﺸﺎﺑﮭﺔ ﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ )‪.(c‬‬
‫س( ﺗﻜﻠﻢ ﺑﺈﯾﺠﺎز ﻋﻦ طﺮﯾﻘﺔ اﻟﻌﺰل اﻟﻤﺴ ﺘﺨﺪﻣﺔ ﻟﺘﻌﯿ ﯿﻦ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ‬
‫ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(597‬‬
‫ﺗﻄﺒﻴﻘﺎﺕ ﺇﺿﺎﻓﻴﺔ ﻋﻠﻰ ﺣﺴﺎﺑﺎﺕ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻧﻴﺔ‬
‫ﻣﺜﺎﻝ )‪(٧٦-٢‬‬
‫ﻓﻲ ﺗﻔﺎﻋﻞ اﻟﻨﯿﺘﺮوإﯾﺜﺎن ﻣﻊ اﻟﻘﺎﻋﺪة ﻛﻤﺎ ﻓﻲ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪CH 3CH 2 NO 2 + OH - ‬‬
‫‪→ CH 3CH 2 NO -2 + H 2O‬‬
‫ﻓﻘﺪ وﺟﺪ أﻧﮫ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﻨﺎﺋﯿﺔ وﻓﯿﮫ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻋﻨﺪ اﻟﺼﻔﺮ اﻟﻤﺌﻮي‬
‫‪ (39.1‬ﻓ ﻲ ﻣﺤﻠ ﻮل ﻣﻜ ﻮن ﻣ ﻦ‬ ‫‪L‬‬ ‫‪mol-1‬‬ ‫ھ ﻮ )‪min-1‬‬
‫)‪ (0.004 mol L-1‬ﻣ ﻦ اﻟﻨﯿﺘ ﺮو إﯾﺜ ﺎن‪ ،‬و )‪ (0.005 mol L-1‬ﻣ ﻦ‬
‫ھﯿﺪروﻛﺴ ﯿﺪ اﻟﺼ ﻮدﯾﻮم ﻓﻜ ﻢ اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺘﻔﺎﻋ ﻞ )‪ (90 %‬ﻣ ﻦ‬
‫اﻟﻨﯿﺘﺮوإﯾﺜﺎن‪.‬‬
‫ﺍﳊﻞ‬
‫ﺗﺮﻛﯿﺰ اﻟﻨﯿﺘﺮوإﯾﺜﺎن اﻟﻤﺘﻔﺎﻋﻞ ھﻮ ‪:‬‬

‫‪90‬‬
‫× ‪0.004‬‬ ‫‪= 0.0036 mol/L‬‬
‫‪100‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻜﻤﯿﺔ ﻏﯿﺮ اﻟﻤﺘﻔﺎﻋﻠﺔ ﻣﻦ اﻟﻨﯿﺘﺮوإﯾﺜﺎن ‪:‬‬
‫‪0.004 − 0.0036 = 0.0004 mol/L‬‬
‫وﺗﺼﺒﺢ ﻛﻤﯿﺔ اﻟﻘﺎﻋﺪة ﻏﯿﺮ اﻟﻤﺘﻔﺎﻋﻠﺔ ھﻲ ‪:‬‬
‫‪0.005 − 0.0036 = 0.0014 mol/L‬‬

‫)‪(598‬‬
‫وﯾﻤﻜﻦ ﺗﻮﺿﯿﺢ ذﻟﻚ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪CH 3CH 2 NO 2‬‬ ‫‪+‬‬ ‫‪OH - ‬‬
‫‪t=0‬‬ ‫‪b = 0.004‬‬ ‫‪a = 0.005‬‬
‫‪t=t‬‬ ‫‪(b - x) = 0.0004‬‬ ‫‪(a - x) = 0.0014‬‬
‫وﺑﺘﻄﺒﯿﻖ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪2.303‬‬ ‫)‪b (a - x‬‬
‫= ‪kt‬‬ ‫‪log‬‬
‫)‪( a - b ) a (b - x‬‬
‫‪2.303‬‬ ‫)‪b (a - x‬‬
‫=‪t‬‬ ‫‪log‬‬
‫)‪k (a - b‬‬ ‫)‪a (b - x‬‬
‫‪2.303‬‬ ‫) ‪0.004 ( 0.0014‬‬
‫=‪t‬‬ ‫‪log‬‬
‫) ‪39.1( 0.005 - 0.004‬‬ ‫) ‪0.005 ( 0.0004‬‬
‫‪t = 26.34 min.‬‬
‫ﻣﺜﺎﻝ )‪(٧٧-٢‬‬
‫ﺗﻢ ﺧﻠﻂ ﻣﺤﻠﻮل ﻣ ﻦ )‪ (A‬ﻣ ﻊ ﺣﺠ ﻢ ﻣﺴ ﺎو ﻟ ﮫ ﻣ ﻦ )‪ (B‬وﯾﺤﺘ ﻮي ﻋﻠ ﻰ‬

‫ﻧﻔﺲ ﻋﺪد ﻣﻮﻻﺗﮫ‪ .‬وﻗﺪ وﺟﺪ أﻧ ﮫ ﺑﻌ ﺪ ﻣ ﺮور ﺳ ﺎﻋﺔ ﻓ ﺈن )‪ (75 %‬ﻣ ﻦ‬
‫)‪ (A‬ﻗ ﺪ ﺗﻔﺎﻋ ﻞ‪ .‬ﻓﻜ ﻢ ﯾﺒﻘ ﻰ ﻣ ﻦ )‪ (A‬ﻏﯿ ﺮ ﻣﺘﻔﺎﻋ ﻞ ﻓ ﻲ ﻧﮭﺎﯾ ﺔ اﻟﺴ ﺎﻋﺔ‬
‫اﻟﺜﺎﻧﯿﺔ ﻓﻲ ﺣﺎل ﻛﻮن اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫أ( ﻣﺮﺗﺒﺔ أﺣﺎدﯾﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟـ )‪ (A‬وﻣﺮﺗﺒﺔ ﺻﻔﺮﯾﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟـ )‪(B‬‬
‫ب( ﻣﺮﺗﺒﺔ أﺣﺎدﯾﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻜﻠﯿﮭﻤﺎ‬
‫ج( ﻣﺮﺗﺒﺔ ﺻﻔﺮﯾﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻜﻠﯿﮭﻤﺎ‪.‬‬

‫)‪(599‬‬
‫ﺍﳊﻞ‬
‫أ( اﻟﺘﻔﺎﻋﻞ ھﻮ ‪:‬‬

‫‪A‬‬ ‫‪+‬‬ ‫‪B‬‬ ‫‪‬‬
‫‪t=0‬‬ ‫‪a‬‬ ‫‪0‬‬
‫‪t=1h‬‬ ‫)‪(a - x1 ) = ( a - 0.75 a‬‬ ‫‪x1 = 0.75a‬‬
‫‪t=2h‬‬ ‫) ‪( a - x2‬‬ ‫‪x2‬‬
‫وﺑﻤﺎ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷﺣﺎدﯾ ﺔ ﺑﺎﻟﻨﺴ ﺒﺔ ﻟ ـ )‪ (A‬وﻣﺮﺗﺒ ﺔ ﺻ ﻔﺮﯾﺔ‬

‫ﺑﺎﻟﻨﺴﺒﺔ ﻟـ )‪ (B‬ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ .‬وﺑﺘﻄﺒﯿﻖ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ‬
‫اﻷوﻟﻰ ﻓﻲ زﻣﻦ )‪: (t = 1‬‬
‫‪2.303‬‬ ‫) ‪(a - x1‬‬
‫=‪k‬‬ ‫‪log‬‬
‫) ‪(t 2 - t1‬‬ ‫) ‪( a - x2‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪(1 - 0 ) 0.25a‬‬
‫‪2.303‬‬ ‫‪1‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪1‬‬ ‫‪0.25‬‬
‫‪k =1.3865h-1‬‬
‫وﺑﺘﻄﺒﯿﻖ اﻟﻤﻌﺎدﻟﺔ ﻣﺮة ﺛﺎﻧﯿﺔ ﻟﺤﺴ ﺎب ﻛﻤﯿ ﺔ اﻟﻤ ﺎدة ﻏﯿ ﺮ اﻟﻤﺘﻔﺎﻋﻠ ﺔ ﻣ ﻦ‬
‫)‪ (A‬ﻓﻲ ﻧﮭﺎﯾﺔ اﻟﺴﺎﻋﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬

‫)‪(600‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫)‪( a - x‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫= ‪1.3865‬‬ ‫‪log‬‬
‫‪2‬‬ ‫)‪(a - x‬‬
‫‪a‬‬
‫‪log‬‬ ‫‪= 1.2041‬‬
‫) (‬
‫‪a‬‬ ‫‪-‬‬ ‫‪x‬‬
‫‪a‬‬
‫‪= 16.0‬‬
‫) ‪(a - x‬‬
‫وﺑﻔﺮض أن ﺗﺮﻛﯿﺰ )‪ (a = 1 mol/L‬ﻓﺈن ﻛﻤﯿﺔ اﻟﻤﺎدة ﻏﯿﺮ اﻟﻤﺘﻔﺎﻋﻠﺔ‬
‫)‪: (a – x‬‬
‫‪a‬‬
‫‪= 16.0‬‬
‫) ‪(a - x‬‬
‫‪1‬‬
‫= )‪(a - x‬‬ ‫‪= 0.0625 mol/L‬‬
‫‪16‬‬
‫ب( ﺑﻤ ﺎ أن اﻟﺘﻔﺎﻋ ﻞ ﻣﺮﺗﺒ ﺔ أﺣﺎدﯾ ﺔ ﻟﻜﻠﯿﮭﻤ ﺎ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ رﺗﺒﺘ ﮫ اﻟﻜﻠﯿ ﺔ‬

‫ھﻲ اﻟﺜﻨﺎﺋﯿﺔ‪ ،‬وﺑﺘﻄﺒﯿﻖ ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ اﻟﺜﻨﺎﺋﯿﺔ ﻣﻊ اﻓﺘ ﺮاض أن ‪( a = 1‬‬
‫)‪: mol/L‬‬
‫‪1 1‬‬ ‫‪1 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪t  ( a - x ) (a) ‬‬
‫‪1 1‬‬ ‫‪1‬‬
‫‪k = ‬‬ ‫‪- ‬‬
‫‪1  ( 0.25 ) 1 ‬‬
‫‪k = 3 L mol-1h -1‬‬

‫)‪(601‬‬
‫وﻟﺤﺴﺎب ﻗﯿﻤﺔ اﻟﻤﺘﺒﻘ ﻲ ﻣ ﻦ )‪) (A‬ﻏﯿ ﺮ اﻟﻤﺘﻔﺎﻋ ﻞ( وھ ﻮ )‪ (a – x‬ﺑﻌ ﺪ‬

‫زﻣﻦ )‪: (2 h‬‬
‫‪ 1‬‬ ‫‪1 ‬‬
‫‪kt = ‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪‬‬ ‫(‬ ‫‪a‬‬ ‫‪-‬‬ ‫‪x‬‬ ‫)‬ ‫)‪(a‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪1‬‬
‫= ‪3 ×2‬‬ ‫‪-‬‬
‫‪(a - x) 1‬‬
‫‪1‬‬
‫=‪6‬‬ ‫‪-1‬‬
‫)‪(a - x‬‬
‫‪1‬‬
‫‪=7‬‬
‫)‪(a - x‬‬
‫‪1‬‬
‫‪(a - x) = = 0.1428‬‬
‫‪7‬‬
‫ج( وﻓﻲ ﺣﺎﻟﺔ اﻟﺮﺗﺒﺔ اﻟﺼﻔﺮﯾﺔ ﻟﻜﻼ اﻟﻤﺘﻔﺎﻋﻠﯿﻦ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ اﻟﻌ ﺎم ﻣ ﻦ‬

‫اﻟﺮﺗﺒﺔ اﻟﺼﻔﺮﯾﺔ وﻗﺎﻧﻮﻧﮭﺎ ھﻮ ‪:‬‬
‫) ‪k t = a - (a - x‬‬
‫) ‪k t = a - ( a - 0.74a‬‬
‫)‪k × 1=1 - (1 - 0.75‬‬
‫‪k = 1 - 0.25‬‬
‫‪k = 0.75 mol /L‬‬
‫وﺑﺈﻋﺎدة ﺗﻄﺒﯿﻖ اﻟﻤﻌﺎدﻟﺔ ) ) ‪ ( k t = a - ( a - x‬ﻹﯾﺠﺎد ﺗﺮﻛﯿ ﺰ )‪ (A‬ﻏﯿ ﺮ‬

‫اﻟﻤﺘﻔﺎﻋﻞ )‪ (a – x‬ﻓﻲ ﻧﮭﺎﯾﺔ اﻟﺴﺎﻋﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬

‫)‪(602‬‬
‫)‪k t = a - ( a - x‬‬
‫)‪0.75 × 2 =1 - (a - x‬‬
‫‪(a - x) = - ( 0.75 × 2) + 1‬‬
‫‪( a - x ) = - 0.5 mol/L‬‬
‫وﺑﺎﻟﻄﺒﻊ ﻻ ﯾﻮﺟ ﺪ ﺗﺮﻛﯿ ﺰ ﺑﺎﻟﺴ ﺎﻟﺐ‪ ،‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ھ ﺬا ﯾﻌﻨ ﻲ أن ﺟﻤﯿ ﻊ‬
‫اﻟﻤﺮﻛ ﺐ )‪ (A‬ﯾﺘﻔﺎﻋ ﻞ ﻗﺒ ﻞ اﻟﻮﺻ ﻮل اﻟ ﻰ ﻧﮭﺎﯾ ﺔ اﻟﺴ ﺎﻋﺔ اﻟﺜﺎﻧﯿ ﺔ‪.‬‬
‫وﻟﻤﻌﺮﻓﺔ اﻟﺰﻣﻦ اﻟﻼزم ﻻﻧﺘﮭﺎء اﻟﻤﺎدة )‪ (A‬أي ﻋﻨﺪ )‪ (a – x = 0‬ﻓﺈن ‪:‬‬
‫)‪k t = a - (a - x‬‬
‫‪0.75 × t = 1- 0‬‬
‫‪1‬‬
‫=‪t‬‬
‫‪0.75‬‬
‫‪t = 1.33 h‬‬
‫وھﻮ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ اﻟﻤﺎدة )‪.(A‬‬
‫ﻣﺜﺎﻝ )‪(٧٨-٢‬‬
‫وﺟ ﺪ أﻧ ﮫ ﻋﻨ ﺪ ﺗﺤﻠ ﻞ )‪ (HI‬اﻟ ﻰ )‪ (H2‬و )‪ (I2‬ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة‬

‫)‪ ،(781 K‬ﺑﺄن ﻓﺘﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ھ ﻲ )‪ (135 min.‬ﻋﻨ ﺪﻣﺎ ﯾﻜ ﻮن‬
‫اﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ ﻟ ـ )‪ (HI‬ھ ﻮ )‪ ،(1 × 104 N/m2‬وﻓﺘ ﺮة ﻧﺼ ﻒ‬
‫اﻟﻌﻤ ﺮ ھ ﻲ )‪ (1.3.5 min‬ﻋﻨ ﺪﻣﺎ ﯾﻜ ﻮن اﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ ﻟ ـ )‪(HI‬‬
‫ﻣﺴﺎوﯾﺎ ً ﻟﻠﻀﻐﻂ اﻟﺠﻮي اﻹﻋﺘﯿﺎدي‪.‬‬
‫أ( ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(603‬‬
‫ب( اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪ (k‬ﺑﻮﺣﺪة )‪(m3 mol-1 s-1‬‬
‫ﺍﳊﻞ‬
‫أ( ﻟﻜ ﻲ ﻧﺜﺒ ﺖ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓﺈﻧﻨ ﺎ ﻧﺤﺴ ﺐ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ‬

‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻟﻠﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﺑﺪﻻﻟ ﺔ زﻣ ﻦ ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻓ ﻲ ﻛ ﻼ‬
‫اﻟﻀﻐﻄﯿﻦ‪ ،‬ﻓﺈذا ﻛﺎن اﻟﻨﺎﺗﺞ واﺣ ﺪاً ﻓ ﺈن ھ ﺬا ﯾ ﺪل ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬
‫اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫ﻋﻨﺪﻣﺎ ﯾﻜ ﻮن اﻟﻀ ﻐﻂ )اﻟﺘﺮﻛﯿ ﺰ( ﻣﺴ ﺎوﯾﺎ ً )‪(PHI = 1 × 104 N/m2‬‬
‫وزﻣﻦ ﻧﺼ ﻒ اﻟﻌﻤ ﺮ)‪ (134 min‬ﻓ ﺈن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﯾﺤﺴ ﺐ‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪ka‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪t1/2 a‬‬
‫‪1‬‬
‫=‪k‬‬
‫× ‪(135‬‬ ‫) ‪60 s ) × (1 × 10 4 N/m 2‬‬
‫‪k = 1.234 × 10-8 m 2 N -1 s -1‬‬
‫ﻋﻨﺪﻣﺎ ﯾﻜﻮن اﻟﻀﻐﻂ )اﻟﺘﺮﻛﯿ ﺰ( ﻣﺴ ﺎوﯾﺎ ً ‪(PHI = 1.01325 × 105‬‬

‫)‪ N/m2‬وزﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ)‪ (13.5 min‬ﻓﺈن ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫ﯾﺤﺴﺐ ﻛﻤﺎ ﯾﻠﻲ‬

‫)‪(604‬‬
‫‪1‬‬
‫= ‪t1/2‬‬
‫‪ka‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪t1/2 a‬‬
‫‪1‬‬
‫=‪k‬‬
‫) ‪(13.5 × 60 s ) × (1.01325 × 10 5 N/m 2‬‬
‫‪k = 1.218 × 10 -8 m 2 N -1 s -1‬‬
‫ب( ﺣﺴﺎب ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﻮﺣﺪة )‪: (m3 N-1 s-1‬‬
‫ﺑﻔﺮض أن اﻟﻐﺎز ﻣﺜﺎﻟﻲ اﻟﺴﻠﻮك‪ ،‬وﺑﺎﺳﺘﺨﺪام ﻗﺎﻧﻮن اﻟﻐﺎز اﻟﻤﺜﺎﻟﻲ ‪:‬‬
‫‪PV = nRT‬‬
‫‪n‬‬
‫=‪P‬‬ ‫‪RT‬‬
‫‪V‬‬
‫‪P = CRT‬‬
‫‪P‬‬
‫=‪C‬‬
‫‪RT‬‬
‫‪1.01325 × 105 N m - 2‬‬
‫=‪C‬‬
‫‪8.314 J K -1mol-1 × 781 K‬‬
‫‪1.01325 × 105 N m - 2‬‬
‫=‪C‬‬
‫‪8.314 N. m K -1mol-1 × 781 K‬‬
‫‪C = 15.605 mol/m 3‬‬
‫وﺑﺘﻄﺒﯿﻖ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﻟﺤﺴﺎب ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ ‪:‬‬

‫‪1‬‬
‫=‪k‬‬
‫‪t1/2a‬‬
‫‪1‬‬
‫=‪k‬‬
‫‪135 × 60 × 15.605‬‬
‫‪k = 7.9 × 10-6 m3 mol-1s -1‬‬

‫)‪(605‬‬
‫ﻣﺜﺎﻝ )‪(٧٩-٢‬‬
‫إن اﻟﺘﻔﺎﻋﻞ ﺑﯿﻦ ﺛﻼﺛﻲ ﻣﯿﺜﯿﻞ أﻣﯿﻦ وﺑﺮوﻣﻮﺑﺮوﺑﺎن ﻓﻲ ﻣﺤﻠﻮل ﺣ ﺎﻣﺾ‬
‫اﻟﺨﻠﯿﻚ ﺗﻤﺜﻠﮫ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪( CH 3 )3 N (acid) + C3H 7Br(acid) ‬‬
‫)‪→ ( CH 3 )3 N +C 3H 7(acid) + Br - (acid‬‬
‫ﺣﯿ ﺚ ﺗﻤ ﺖ ﻣﺘﺎﺑﻌ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة ﺛﺎﺑﺘ ﺔ‪ ،‬وﻛﺎﻧ ﺖ اﻟﻤ ﻮاد‬

‫اﻟﻤﺘﻔﺎﻋﻠﺔ ﻣﻮﺟﻮدة ﻓﻲ ﻧﻔﺲ اﻟﺘﺮﻛﯿﺰ وﻛﺎن اﺳﺘﮭﻼﻛﮭﺎ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Time , sec.‬‬ ‫‪0‬‬ ‫‪780‬‬ ‫‪2040‬‬ ‫‪3540‬‬ ‫‪7200‬‬
‫‪C = [A]t = (a – x) mol/L‬‬ ‫‪0.100 0.0888 0.0743 0.0633 0.0448‬‬
‫أﺛﺒ ﺖ ﻣ ﻦ ﺧ ﻼل اﻟﻤﻌ ﺎدﻻت أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‪ ،‬واﺣﺴ ﺐ‬

‫ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺑﺘﻄﺒﯿ ﻖ ﻗ ﺎﻧﻮن اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﺴ ﺎوي اﻟﺘﺮاﻛﯿ ﺰ اﻹﺑﺘﺪاﺋﯿ ﺔ‬

‫) ‪ ( 2A → products‬ﻟﻠﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ‪:‬‬
‫‪1 1‬‬ ‫‪1‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪- ‬‬
‫‪ta-x a‬‬
‫)‪a - (a - x‬‬
‫=‪⇒k‬‬
‫)‪a t (a - x‬‬
‫‪a = 0.100‬‬
‫‪Time , sec.‬‬ ‫‪780‬‬ ‫‪2040‬‬ ‫‪3540‬‬ ‫‪7200‬‬
‫‪C = (a – x) mol/L‬‬ ‫‪0.0888‬‬ ‫‪0.0743‬‬ ‫‪0.0633‬‬ ‫‪0.0448‬‬
‫)‪a - (a - x‬‬
‫=‪k‬‬ ‫‪1.62 × 10-3‬‬ ‫‪1.70 ×10-3‬‬ ‫‪1.64 ×10-3‬‬ ‫‪1.71 × 10-3‬‬
‫)‪a t (a - x‬‬

‫)‪(606‬‬
‫وﺑﻤ ﺎ أن اﻟﻘ ﯿﻢ ﻣﺘﻘﺎرﺑ ﺔ ﺟ ﺪاً ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ‪ ،‬وﺛﺎﺑ ﺖ‬

‫اﻟﺴﺮﻋﺔ ﯾﻤﺜﻞ ﻣﻌﺪل اﻟﻘﺮاءات أﻋﻼه‬
‫ﻣﺜﺎﻝ )‪(٨٠-٢‬‬
‫إن اﻟﻨﺘ ﺎﺋﺞ اﻟﺘﺎﻟﯿ ﺔ ﻗ ﺪ ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿﮭ ﺎ ﻟﺼ ﻮﺑﻨﺔ ﺧ ﻼت اﻹﯾﺜﯿ ﻞ‬

‫ﺑﺎﺳﺘﺨﺪام ﺗﺮاﻛﯿﺰ ﻣﺘﺴﺎوﯾﺔ ﻣﻦ اﻹﺳﺘﺮ واﻟﻘﺎﻋﺪة ‪:‬‬
‫‪CH 3COOC 2 H 5 + NaOH ‬‬
‫‪→ CH 3COONa + C 2 H 5OH‬‬
‫‪time, min‬‬ ‫‪0‬‬ ‫‪4.89‬‬ ‫‪10.07‬‬ ‫‪23.66‬‬ ‫∞‬

‫‪V acid cm3‬‬ ‫‪47.65‬‬ ‫‪38.92‬‬ ‫‪32.62‬‬ ‫‪22.58‬‬ ‫‪11.84‬‬
‫ﺑﯿﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ؟‬
‫ﺍﳊﻞ‬
‫ﻣﻦ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪CH 3COOC2 H5 + NaOH ‬‬
‫‪→ CH3 COONa + C2 H5 OH‬‬
‫ﻓ ﺈن ﻣ ﻮل ﻣ ﻦ اﻟﻘﺎﻋ ﺪة )‪ (NaOH‬ﺗﺨﺘﻔ ﻲ ﻣ ﻊ ﻛ ﻞ ﻣ ﻮل ﻣ ﻦ اﻹﺳ ﺘﺮ‬

‫اﻟﻤﺘﻔﺎﻋ ﻞ )‪ (CH3COOC2H5‬ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ ﺗﺘﺒ ﻊ اﻟﺘﻔﺎﻋ ﻞ ﺑﺴ ﺤﺐ‬
‫ﻛﻤﯿﺎت ﺑﺴﯿﻄﺔ ﻣﻦ اﻟﻤﺤﻠ ﻮل ﺑﻔﺘ ﺮات ﻣﺨﺘﻠﻔ ﺔ وﺗﺴ ﺤﯿﺤﮭﺎ ﻣ ﻊ ﺣ ﺎﻣﺾ‪.‬‬
‫إن ﻛﻤﯿﺔ اﻟﺤﺎﻣﺾ اﻟﻤﺴﺘﺨﺪم ﻓﻲ اﻟﺘﺴ ﺤﯿﺢ ﯾﻤﺜ ﻞ ﻣﻘﯿﺎﺳ ﺎ ً ﻟﻜﻤﯿ ﺔ اﻟﻘﺎﻋ ﺪة‬
‫ﻏﯿﺮ اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬

‫)‪(607‬‬
‫ﻟ ﺬا ﻓ ﺈن اﻹﻧﺨﻔ ﺎض ﻓ ﻲ ﻛﻤﯿ ﺔ اﻟﺤ ﺎﻣﺾ اﻟﻤﺴ ﺘﺨﺪم ﻓ ﻲ أي زﻣ ﻦ )‪(t‬‬

‫ﯾﻤﺜﻞ اﻟﻘﯿﻤﺔ )‪ .(x‬وإن ﺗﺮﻛﯿﺰ اﻟﺤﺎﻣﺾ ﻓﻲ زﻣ ﻦ ﺻ ﻔﺮ ﯾﻤﺜ ﻞ اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻹﺑﺘﺪاﺋﻲ )‪.(a‬‬
‫‪1‬‬ ‫‪x‬‬ ‫‪‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪:‬‬
‫‪t  a ( a - x ) ‬‬
‫وﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‬
‫ﺣﯿ ﺚ اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﺨ ﻼت اﻹﯾﺜﯿ ﻞ ﯾﻜ ﺎﻓﻲء اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ‬

‫ﻟﻘﺎﻋ ﺪة )‪ (NaOH‬ﻗﺒ ﻞ ﺑ ﺪء اﻟﺘﻔﺎﻋ ﻞ أي ﻋﻨ ﺪ زﻣ ﻦ )‪ (t = 0‬وﺣﺠ ﻢ‬
‫اﻟﺤﻤﺾ اﻟﻤﻜﺎﻓﺊ ﻟﻠﻘﺎﻋﺪة ﻗﺒﻞ ﺗﻔﺎﻋﻠﮭﺎ ﯾﻌﺒ ﺮ ﻋ ﻦ ﺗﺮﻛﯿ ﺰ اﻹﺳ ﺘﺮ‪ ،‬وﻣ ﻦ‬
‫اﻟﺠﺪول ﻓﺈن ‪.(a = 47.65) :‬‬
‫وﻋﻨﺪ اﻟﻤﻌﺎﯾﺮة ﺑﺎﻟﺤﻤﺾ ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﻓ ﺈن اﻟﺤﺠ ﻢ اﻟﻤﻜ ﺎﻓﻲء ﻣ ﻦ‬
‫اﻟﺤﻤ ﺾ ﯾﻌﺒ ﺮ ﻋ ﻦ ﻛﻤﯿ ﺔ )‪ (NaOH‬اﻟﻐﯿ ﺮ ﻣﺘﻔﺎﻋﻠ ﺔ أي ﯾﻌﺒ ﺮ ﻋ ﻦ‬
‫)‪.( a – x‬‬
‫وﺑﺎﻟﺘ ﺎﻟﻲ ﻟﺤﺴ ﺎب ﻗﯿﻤ ﺔ )‪ (x‬ﻧﺘﺒ ﻊ اﻟﻌﻼﻗ ﺔ ‪.(x = a – (a – x)) :‬‬
‫وﯾﻤﻜﻦ ﻋﻤﻞ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪a = [CH3COOC2H5] = [NaOH] = Vt = 0 = 47.65‬‬
‫‪time, min‬‬ ‫‪4.89‬‬ ‫‪10.07‬‬ ‫‪23.66‬‬
‫)‪(a – x) = [CH3COOC2H5]t = [NaOH]t = Vt (HCl‬‬ ‫‪38.92‬‬ ‫‪32.62‬‬ ‫‪22.58‬‬
‫)‪x = a – (a – x‬‬ ‫‪8.73‬‬ ‫‪15.03‬‬ ‫‪25.07‬‬
‫‪1‬‬ ‫‪x‬‬ ‫‪‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪9.63 × 10-4‬‬ ‫‪9.60 × 10-4‬‬ ‫‪9.85 ×10-4‬‬
‫‪t  a ( a - x ) ‬‬
‫وﺑﻤﺎ أن ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﺛﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ‪.‬‬

‫)‪(608‬‬
‫ﻣﺜﺎﻝ )‪(٨١-٢‬‬
‫ﻣﺎدﺗﺎن )‪ (A‬و )‪ (B‬ﺗﺘﺒﻊ ﺗﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒ ﺔ‪ .‬واﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﯾﻌﻄ ﻲ‬
‫ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة )‪ (A‬ﺑﺄزﻣ ﺎن ﻣﺨﺘﻠﻔ ﺔ واﻟﺘ ﻲ ﺟ ﺮت ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة‬
‫ﺛﺎﺑﺘﺔ ﻣﻘﺪارھﺎ )‪.(17 ºC‬‬
‫‪time, min.‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫‪Conc. A × 104 mol/L‬‬ ‫‪10.0‬‬ ‫‪7.94‬‬ ‫‪6.31‬‬ ‫‪5.01‬‬ ‫‪3.98‬‬
‫واﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟ ـ )‪ (B‬ھ ﻮ )‪ .(2.5 mol/L‬اﺣﺴ ﺐ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ‬

‫اﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫اﻟﺠﻮاب ‪k = (1.54 × 10-4 L mol-1 s-1) :‬‬
‫ﻃﺮﻳﻘﺔ ﺍﳊﻞ‬
‫‪........................................................................................................................................................................................‬‬
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‫)‪(609‬‬
‫ﻣﺜﺎﻝ )‪(٨٢-٢‬‬
‫إن ﻋﻤﻠﯿﺔ ﺻﻮﺑﻨﺔ ﺧ ﻼت اﻹﯾﺜﯿ ﻞ ﺑﻮﺟ ﻮد ھﯿﺪروﻛﺴ ﯿﺪ اﻟﺼ ﻮدﯾﻮم ﻋﻨ ﺪ‬

‫درﺟﺔ ﺣﺮارة )‪ (30 ºC‬ھﻲ ‪:‬‬
‫‪CH3COOC2 H5 + NaOH ‬‬
‫‪→ CH3COONa + C2 H5OH‬‬
‫ﻓﺈذا ﻛﺎن اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻺﺳﺘﺮ )ﺧﻼت اﻹﯾﺜﯿ ﻞ( واﻟﻘﺎﻋ ﺪة ﻣﺘﺴ ﺎوﯾﺎ ً‬
‫)‪ (0.05 mol/L‬وإن اﻻﻧﺨﻔ ﺎض ﻓ ﻲ ﺗﺮﻛﯿ ﺰ اﻹﺳ ﺘﺮ )‪ (x‬ﻗ ﺪ ﺗ ﻢ‬
‫دراﺳﺘﮫ ﻓﻲ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪time, min.‬‬ ‫‪4‬‬ ‫‪9‬‬ ‫‪15‬‬ ‫‪24‬‬ ‫‪37‬‬ ‫‪53‬‬ ‫‪83‬‬
‫‪x × 103, mol/L‬‬ ‫‪5.91 11.42 16.30 22.07 27.17 31.47 36.44‬‬
‫اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬

‫ﺍﳉﻮﺍﺏ ‪(k = 1.08 ×10-2 L mol-1 s-1) :‬‬
‫‪...................................................................................................................................................................... ..................‬‬
‫‪............................................................................................... .........................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
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‫‪..................................................................................................................................................................................... ...‬‬

‫)‪(610‬‬
‫ﻣﺜﺎﻝ )‪(٨٣-٢‬‬
‫أﻛﺘﺐ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋ ﻞ‪ ( 2A → products ) ،‬ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﺛ ﻢ‬

‫اﺳﺘﻨﺘﺞ ﻣﻌﺎدﻟﺔ ﺗﻌﺒﺮ ﺑﮭﺎ ﻋﻦ ﻧﺼﻒ زﻣﻦ اﻟﺘﻔﺎﻋﻞ )‪.(t1/2‬‬
‫‪........................................................................................................................................................................................‬‬
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‫‪........................................................................................................................................................................................‬‬
‫ﻣﺜﺎﻝ )‪(٨٤-٢‬‬
‫ﯾﺘﺤﻄﻢ ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ﺑﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬

‫‪2NO2 ‬‬
‫‪→ 2NO + O2‬‬
‫وﯾﺒﻠﻎ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪ ،(k = 2.00 × 10-8 L mol-1 s-1‬ﻓ ﺈذا ﻛ ﺎن‬
‫ﺗﺮﻛﯿﺰ )‪ (NO2‬ﻓﻲ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ )‪ ،(0.500 M‬ﻓﻜ ﻢ ﺛﺎﻧﯿ ﺔ ﺗﻠ ﺰم ﻟﻜ ﻲ‬
‫ﯾﻨﻘﺺ ﺗﺮﻛﯿﺰ )‪ (NO2‬اﻟﻰ )‪(0.12 M‬؟‬
‫ﺍﳉﻮﺍﺏ ‪3.00 × 108 s :‬‬

‫)‪(611‬‬
‫‪........................................................................................................................................................................................‬‬
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‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫ﻣﺜﺎﻝ )‪(٨٥-٢‬‬
‫ﯾﺘﻔﺎﻋ ﻞ اﻟﯿ ﻮد )‪ (I2‬واﻟﮭﯿ ﺪروﺟﯿﻦ )‪ (H2‬ﻹﻋﻄ ﺎء ﯾﻮدﯾ ﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ‬

‫)‪ .(HI‬وﯾﺘﺒﻊ اﻟﺘﻔﺎﻋﻞ ﻗﺎﻧﻮن اﻟﺴﺮﻋﺔ اﻟﺘﺎﻟﻲ ‪:‬‬
‫] ‪rate = k [H2 ][I2‬‬
‫وﺑﻠﻐﺖ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪(k = 2.0 × 10-6 L. mol-1 s-1‬‬

‫أ( ﻣﺎ ھﻮ ﻧﺼﻒ زﻣﻦ اﻟﺘﻔﺎﻋﻞ )‪ (t1/2‬إذا ﻛﺎن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ‬
‫ﻓﻲ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ )‪ (0.50 M‬ﻟﻜﻞ ﻣﻨﮭﺎ‪.‬‬
‫ب( ﻣ ﺎ اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻟﺘﻔﺎﻋ ﻞ )‪ (75 %‬ﻣ ﻦ )‪ (H2‬و)‪ (I2‬ﻹﻋﻄ ﺎء‬
‫)‪(HI‬؟‬
‫ج( ﻣﺎ اﻟﻌﻼﻗﺔ ﺑﯿﻦ )‪ (t1/2‬و )‪(t3/4‬؟‬

(612)
t3/4 = 3t1/2 (‫ج‬ 3.0 × 106 s (‫ ب‬1.0 × 106 s (‫أ‬ : ‫ﺍﳉﻮﺍﺏ‬
......................................................................................................................... ...............................................................
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‫)‪(613‬‬
‫ﻣﺜﺎﻝ )‪(٨٦-٢‬‬
‫ﯾﺤﺪث ﺗﻔﺎﻋﻞ ﺗﺼﺒﻦ ﺧﻼت اﻹﯾﺜﯿﻞ ﺑﺎﻟﺼﻮرة اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪CH 3COOC 2 H 5 + OH - ‬‬
‫‪→ CH 3COO - + C 2 HOH‬‬
‫ﻓ ﺈذا ﺑﻠ ﻎ ﻧﺼ ﻒ زﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ )‪ (t1/2 = 925 s‬ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة‬

‫)‪ (30 ºC‬وﺗﺮﻛﯿﺰ ﻣﻦ ﺧﻼت اﻹﯾﺜﯿﻞ و )‪ (OH-‬ﻣﺴﺎوﯾﺎ ً )‪.(0.100 M‬‬
‫ﻓﻤﺎ ھﻮ ﻋﺪد اﻟﺜﻮاﻧﻲ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ )‪ (75 %‬ﻣﻦ ﺧﻼت اﻹﯾﺜﯿﻞ؟‬
‫ﺍﳉﻮﺍﺏ ‪2780 s :‬‬

‫‪........................................................................................................................................................................................‬‬
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‫)‪(614‬‬
‫ﻣﺜﺎﻝ )‪(٨٧-٢‬‬
‫إذا ﻛﺎن ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫‪2HI ‬‬
‫‪→ H 2 + I2‬‬
‫ھﻮ ﻋﺒﺎرة ﻋﻦ ‪:‬‬

‫‪r = k [HI]2‬‬
‫ﻓﻜﯿ ﻒ ﺗﺘﻐﯿ ﺮ ﺳ ﺮﻋﺔ ﺗﻔﺎﻋﻠ ﮫ ﻋﻨ ﺪﻣﺎ ﯾ ﻨﺨﻔﺾ ﺗﺮﻛﯿ ﺰ )‪ (HI‬اﻟ ﻰ ﺛﻠ ﺚ‬

‫ﻗﯿﻤﺘﮫ اﻷﺻﻠﯿﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺑﻔ ﺮض أن ﺗﺮﻛﯿ ﺰ ]‪ [HI‬ﯾﺴ ﺎوي واﺣ ﺪ وﺗﺮﻛﯿ ﺰه اﻟﺜ ﺎﻧﻲ )‪.(1/3‬‬

‫وﺑﻘﺴﻤﺔ ﻗﺎﻧﻮﻧﻲ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪2‬‬
‫‪1 ‬‬
‫‪k ‬‬
‫'‪r‬‬
‫=‬ ‫‪3‬‬
‫‪r‬‬ ‫‪k [1]2‬‬
‫‪1‬‬
‫'‪r‬‬ ‫‪1‬‬
‫=‪= 9‬‬
‫‪r‬‬ ‫‪1 9‬‬
‫‪1‬‬
‫‪r' = r‬‬
‫‪9‬‬
‫'‪r = 9 r‬‬
‫ﺗﺘﻐﯿ ﺮ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﻨﺴ ﺒﺔ ‪ 9 : 1‬أي ‪ r'/r = 1/9‬ﺣﯿ ﺚ )'‪ (r‬ھ ﻲ‬

‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪﻣﺎ ﯾﻨﺨﻔﺾ اﻟﺘﺮﻛﯿﺰ‪.‬‬

‫)‪(615‬‬
‫ﻣﺜﺎﻝ )‪(٨٨-٢‬‬
‫ﺗﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‪ ،‬ﯾ ﺘﻢ ﻣﻨ ﮫ )‪ (20 %‬ﻓ ﻲ زﻣ ﻦ ﻗ ﺪره )‪(40‬‬

‫دﻗﯿﻘﺔ ﻋﻨﺪﻣﺎ ﺑﺪأ اﻟﺘﻔﺎﻋﻞ ﺑﺘﺮﻛﯿﺰ ﯾﺴﺎوي )‪ (0.1 M‬اﺣﺴﺐ ﻣﺎ ﯾﻠﻲ ‪:‬‬
‫أ( ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ب( ﻓﺘﺮة ﻋﻤﺮ اﻟﻨﺼﻒ‪.‬‬
‫ج( اﻟﻮﻗﺖ اﻟﻼزم ﻹﺗﻤﺎم )‪ (20 %‬ﻣﻦ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪﻣﺎ ﯾﻜ ﻮن اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻻﺑﺘﺪاﺋﻲ ﯾﺴﺎوي )‪(0.01 M‬‬
‫أ( ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ‪k = 6.25 × 10-2 dm3 mol-1 min-1.‬‬
‫ب( ﻋﻤﺮ اﻟﻨﺼﻒ ‪(t1/2 = 160 min) :‬‬
‫ج( اﻟﻮﻗﺖ اﻟﻼزم ﻹﺗﻤﺎم )‪ (20 %‬ﻣﻦ اﻟﺘﻔﺎﻋﻞ )‪(t = 400 min.‬‬
‫‪........................................................................................................................................................................................‬‬
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(616)
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‫)‪(617‬‬
‫ﻣﺜﺎﻝ )‪(٨٩-٢‬‬
‫إذا ﻣ ﺰج ﺗﺮﻛﯿ ﺰان ﻣﺘﺴ ﺎوﯾﺎن ﻣ ﻦ ﺧ ﻼت اﻹﯾﺜﯿ ﻞ وھﯿﺪروﻛﺴ ﯿﺪ‬

‫اﻟﺼ ﻮدﯾﻮم وﺗ ﻢ )‪ (25 %‬ﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ ﺑﻌ ﺪ زﻣ ﻦ ﻗ ﺪره )‪(5 min.‬‬
‫ﻓﺄﺛﺒ ﺖ أن )‪ (50 %‬ﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ ﯾ ﺘﻢ ﺑﻌ ﺪ )‪ ،(15 min‬ﺛ ﻢ اﺣﺴ ﺐ‬
‫اﻹﻧﺨﻔﺎض ﻓﻲ ﺗﺮﻛﯿﺰ ﻛﻞ ﻣﻦ اﻟﺨ ﻼت واﻟﮭﯿﺪروﻛﺴ ﯿﺪ ﺑﻌ ﺪ زﻣ ﻦ ﻗ ﺪره‬
‫)‪.(10 min‬‬
‫ﺍﳉﻮﺍﺏ‬
‫اﻻﻧﺨﻔﺎض ﻓﻲ اﻟﺘﺮﻛﯿﺰ ﺑﻌﺪ ﻋﺸﺮ دﻗﺎﺋﻖ ﯾﺴ ﺎوي )‪ (40 %‬ﻣ ﻦ ﺗﺮﻛﯿ ﺰ‬

‫ﻛﻞ ﻣﻦ اﻟﺨﻼت واﻟﮭﯿﺪروﻛﺴﯿﺪ‪.‬‬
‫ﻣﺜﺎﻝ )‪(٩٠-٢‬‬
‫إذا ﻛﺎن ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑ ﯿﻦ ﻣﺮﻛ ﺐ اﻟﻨﯿﺘﺮوإﯾﺜ ﺎن وھﯿﺪروﻛﺴ ﯿﺪ‬

‫اﻟﺼﻮدﯾﻮم ‪:‬‬
‫‪CH 3CH 2 NO 2 + OH - ‬‬
‫‪→ H 2 O + CH 3CH=NO-2‬‬
‫ﯾﺴ ﺎوي )‪ (k = 39.1 dm3 mol-1 min-1‬ﻋﻨ ﺪ درﺟ ﺔ اﻟﺼ ﻔﺮ‬

‫اﻟﻤﺌﻮي‪ ،‬وﻛﺎﻧﺖ اﻟﺘﺮاﻛﯿﺰ اﻹﺑﺘﺪاﺋﯿﺔ ﻟﮭﻤﺎ ‪:‬‬
‫‪[CH3CH2NO2] = 0.004 M,‬‬ ‫‪[OH-] = 0.005 M‬‬
‫ﻓﺎﺣﺴﺐ اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ )‪ (90%‬ﻣﻦ ﻣﺮﻛﺐ اﻟﻨﯿﺘﺮوإﯾﺜﺎن‪.‬‬

‫)‪(618‬‬
‫اﻟﺰﻣﻦ اﻟﻼزم ﻟﺘﻔﺎﻋﻞ )‪ (90 %‬ﻣﻦ اﻟﻨﯿﺘﺮوإﯾﺜﺎن ‪t = 26.33 min.‬‬
‫‪............................................................................................................................... .........................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪.......................................................................................................................................................................... ..............‬‬
‫‪................................................................................................... .....................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
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‫‪.............................................................................................................................................. ..........................................‬‬
‫‪........................................................................................................................................................................................‬‬
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‫‪........................................................................................................................................................................................‬‬
‫‪.................................................................................................................. ......................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
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‫‪............................................................................................................................................................. ...........................‬‬
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‫)‪(619‬‬
‫ﻣﺜﺎﻝ )‪(٩١-٢‬‬
‫ﻓﻲ ﺗﻔﺎﻋﻞ ﺑ ﯿﻦ ﺛﯿﻮﻛﺒﺮﯾﺘ ﺎت اﻟﺼ ﻮدﯾﻮم )‪ (Na2S2O3‬وﯾﻮدﯾ ﺪ اﻟﻤﯿﺜﯿ ﻞ‬

‫)‪ (CH3I‬ﻋﻨ ﺪ )‪ (25 ºC‬ﻛﺎﻧ ﺖ ﺗﺮﻛﯿ ﺰات اﻟﻤﺘﻔ ﺎﻋﻼت ﻋﻨ ﺪ ﻣﺨﺘﻠ ﻒ‬
‫اﻷزﻣﻨﺔ ﻛﺎﻟﺘﺎﻟﻲ ﺑﺎﻟﻮﺣﺪات اﻟﻤﻌﺮوﻓﺔ ‪:‬‬
‫‪Time/min.‬‬ ‫‪0.00‬‬ ‫‪4.75‬‬ ‫‪10.00‬‬ ‫‪20.00‬‬ ‫‪35.00‬‬ ‫‪55.00‬‬ ‫∞‬
‫‪[Na2S2O3] a = 35.35 30.50‬‬ ‫‪27.00‬‬ ‫‪23.20‬‬ ‫‪20.30‬‬ ‫‪18.60‬‬ ‫‪17.10‬‬
‫]‪[CH3I‬‬ ‫‪b = 18.25 13.40‬‬ ‫‪9.90‬‬ ‫‪6.10‬‬ ‫‪3.20‬‬ ‫‪1.50‬‬ ‫‪0.00‬‬
‫أﺛﺒﺖ أن اﻟﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒﺔ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺑﺴ ﺒﺐ أن ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔ ﺎﻋﻼت اﻹﺑﺘﺪاﺋﯿ ﺔ ﻣﺨﺘﻠﻔ ﺔ‪ ،‬ﻓ ﺈذا ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ‬

‫‪‬‬ ‫)‪(a - x) k(a - b‬‬ ‫‪ b ‬‬
‫ﺗﻜ ﻮن‬ ‫‪ log‬‬ ‫=‬ ‫‪t - log   ‬‬ ‫ﺛﻨ ﺎﺋﻲ اﻟﺮﺗﺒ ﺔ ﻓ ﺈن اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪(b - x) 2.303‬‬ ‫‪ a ‬‬
‫)‪ (a – x‬ھ ﻲ ﺗﺮﻛﯿ ﺰ ]‪ [Na2S2O3‬و – ‪(b‬‬ ‫ﺻ ﺤﯿﺤﺔ‪ ،‬وﺗﻜ ﻮن‬

‫)‪ x‬ھﻲ ﺗﺮﻛﯿﺰ ]‪ .[CH3I‬وﺑﺎﻟﺘﺎﻟﻲ ﯾﻤﻜﻦ ﻋﻤﻞ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪Time/min.‬‬ ‫‪4.75‬‬ ‫‪10.00‬‬ ‫‪20.00‬‬ ‫‪35.00‬‬ ‫‪55.00‬‬
‫)‪[Na2S2O3] = (a – x‬‬ ‫‪30.50‬‬ ‫‪27.00‬‬ ‫‪23.20‬‬ ‫‪20.30‬‬ ‫‪18.60‬‬
‫)‪[CH3I] = (b – x‬‬ ‫‪13.40‬‬ ‫‪9.90‬‬ ‫‪6.10‬‬ ‫‪3.20‬‬ ‫‪1.50‬‬
‫)‪(a - x‬‬
‫‪log‬‬ ‫‪0.357‬‬ ‫‪0.436‬‬ ‫‪0.580‬‬ ‫‪0.802‬‬ ‫‪1.093‬‬
‫)‪(b - x‬‬

‫)‪(620‬‬
‫‪‬‬ ‫‪(a - x) ‬‬

‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات‪ ،‬و )‪ (t‬ﻋﻠ ﻰ‬ ‫‪ log‬‬ ‫‪‬‬ ‫وﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ ﺑ ﯿﻦ‬
‫‪‬‬ ‫‪(b - x) ‬‬
‫ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻛﻤ ﺎ ﻓ ﻲ اﻟﺸ ﻜﻞ )‪،(٢٨-٢‬‬

‫وﺑﺬﻟﻚ ﯾﻜﻮن اﻟﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒﺔ‪.‬‬
‫ﺷ ﻜﻞ )‪ : (٢٨-٢‬اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ اﻟﺘﺮﻛﯿ ﺰ واﻟ ﺰﻣﻦ ﻟﺘﻔﺎﻋ ﻞ ﺛﯿﻮﻛﺒﺮﯾﺘ ﺎت اﻟﺼ ﻮدﯾﻮم ﻣ ﻊ ﯾﻮدﯾ ﺪ‬

‫اﻟﻤﯿﺜﯿﻞ‬

‫)‪(621‬‬
‫ﻣﺜﺎﻝ )‪(٩٢-٢‬‬
‫ﻓﻲ ﻋﻤﻠﯿﺔ ﺗﺼﺒﻦ ﺧﻼت اﻹﯾﺜﯿﻞ ﺑﻤﺤﻠ ﻮل ھﯿﺪروﻛﺴ ﯿﺪ اﻟﺼ ﻮدﯾﻮم ﻋﻨ ﺪ‬

‫)‪: (30 ºC‬‬
‫‪CH3COOC2 H5 + NaOH ‬‬
‫‪→ CH3COONa + C2 H5 OH‬‬
‫ﻓ ﺈذا ﻋﻠﻤ ﺖ أن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻜ ﻞ ﻣ ﻦ اﻹﺳ ﺘﺮ واﻟﻘﻠ ﻮي ھ ﻮ‬

‫)‪ (0.05 mol dm-3‬وﻛ ﺎن اﻟ ﻨﻘﺺ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ اﻹﺳ ﺘﺮ ﻋﻨ ﺪ أزﻣﻨ ﺔ‬
‫ﻣﺨﺘﻠﻔﺔ ھﻮ‬
‫)‪Time (min.‬‬ ‫‪4‬‬ ‫‪9‬‬ ‫‪15‬‬ ‫‪24‬‬ ‫‪37‬‬ ‫‪53‬‬ ‫‪83‬‬
‫‪x × 10-3 mol L-1‬‬ ‫‪5.91 11.42‬‬ ‫‪16.30‬‬ ‫‪22.07 27.17 31.47‬‬ ‫‪36.44‬‬
‫اﺣﺴﺐ ﻗﯿﻤﺔ )‪ (k‬ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺎو‬ ‫ﺎﻋﻼت ﻣﺘﺴ‬ ‫ﺰ اﻟﻤﺘﻔ‬ ‫ﺎ أن ﺗﺮﻛﯿ‬ ‫ﺑﻤ‬

‫‪[CH3COOC2H5] = [NaOH] = a‬وإذا ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ ﺛﻨ ﺎﺋﻲ‬
‫‪ 1 ‬‬ ‫‪ 1‬‬ ‫‪1‬‬
‫‪‬‬ ‫‪‬‬ ‫ﺑﺘﻤﺜﯿ ﻞ‬ ‫‪‬‬ ‫‪= kt + ‬‬ ‫اﻟﺮﺗﺒ ﺔ ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ ﺗﻄﺒﯿ ﻖ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪ (a - x ) ‬‬ ‫)‪ (a - x‬‬ ‫‪a‬‬
‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات واﻟ ﺰﻣﻦ )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت‪ ،‬وﻧﺤﺼ ﻞ‬

‫ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ )‪ (k‬وﯾﻘﻄﻊ ﻣﺤﻮر اﻟﺼﺎدات ﻋﻨﺪ اﻟﻨﻘﻄﺔ ‪.  1a ‬‬
‫‪ ‬‬

‫)‪(622‬‬
‫‪[CH3COOC2H5] = [NaOH] = a = 0.05 mol L-1‬‬

‫‪Time‬‬ ‫‪4‬‬ ‫‪9‬‬ ‫‪15‬‬ ‫‪24‬‬ ‫‪37‬‬ ‫‪53‬‬ ‫‪83‬‬
‫)‪(min.‬‬
‫‪x × 10-3‬‬ ‫‪5.91‬‬ ‫‪11.42‬‬ ‫‪16.30‬‬ ‫‪22.07‬‬ ‫‪27.17‬‬ ‫‪31.47‬‬ ‫‪36.44‬‬
‫‪mol dm-3‬‬
‫)‪( a – x‬‬ ‫‪0.044 0.0386 0.0337 0.0279 0.0228 0.0185 0.01356‬‬
‫‪1‬‬
‫) ‪(a - x‬‬ ‫‪22.73‬‬ ‫‪25.91‬‬ ‫‪29.67‬‬ ‫‪35.84‬‬ ‫‪43.86‬‬ ‫‪54.05‬‬ ‫‪73.75‬‬
‫واﻟ ﺰﻣﻦ )‪ (t‬ﻛﻤ ﺎ ھ ﻮ ﻣﻮﺿ ﺢ ﺑﺎﻟﺸ ﻜﻞ‬ ‫‪1‬‬

‫وﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ‬
‫) ‪(a - x‬‬
‫)‪.(٢٩-٢‬‬
‫ﺷﻜﻞ )‪ : (٢٩-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ ﻟﺘﻔﺎﻋﻞ ﺗﺼﺒﻦ ﺧﻼت اﻹﯾﺜﯿﻞ‬
‫وﺣﯿ ﺚ ﺣﺼ ﻠﻨﺎ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﯾﻜ ﻮن ﺛﻨ ﺎﺋﻲ اﻟﺮﺗﺒ ﺔ‪،‬‬

‫وﻣﯿﻠﮫ ھﻮ ‪:‬‬
‫‪slope = k = 0.640 dm3 mol-1 min-1‬‬

‫)‪(623‬‬
‫ﻣﺜﺎﻝ )‪(٩٣-٢‬‬
‫ﻓ ﻲ ﺗﻔﺎﻋ ﻞ ﺑ ﯿﻦ ﺛﻼﺛ ﻲ إﯾﺜﯿ ﻞ اﻷﻣ ﯿﻦ وﯾﻮدﯾ ﺪ اﻟﻤﯿﺜﯿ ﻞ ﺗﻜ ﻮن رﺑ ﺎﻋﻲ‬

‫اﻷﻣﯿﻦ ‪:‬‬
‫‪(C2 H5 )3 N + CH3 I ‬‬
‫‪→ CH3 (C2 H5 )3 NI‬‬
‫وﻋﻨﺪ )‪ (20 ºC‬ﻛﺎﻧﺖ اﻟﺘﺮﻛﯿﺰات اﻹﺑﺘﺪاﺋﯿﺔ ﻛﺎﻵﺗﻲ ‪:‬‬

‫‪[amine]0 = [CH3I]0 = 0.224 mol dm-3‬‬
‫وذﻟﻚ ﻓﻲ ﻣﺤﻠﻮل راﺑﻊ ﻛﻠﻮرﯾﺪ اﻟﻜﺮﺑﻮن‪ .‬وﻗﺪ أﻣﻜﻦ ﺗﺘﺒﻊ اﻟﺘﻔﺎﻋﻞ وذﻟﻚ‬
‫ﻣﻦ ﺧﻼل ﺗﻘﺪﯾﺮ ﺗﺮﻛﯿﺰ اﻷﻣﯿﻦ اﻟﻐﯿﺮ ﻣﺘﻔﺎﻋﻞ ﻋﻦ طﺮﯾﻖ ﻣﻘﯿﺎس اﻟﺠﮭ ﺪ‬
‫ووﺟﺪت اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪time/min‬‬ ‫‪10‬‬ ‫‪40‬‬ ‫‪90‬‬ ‫‪150‬‬ ‫‪300‬‬
‫‪Amine conc./mol dm -3‬‬ ‫‪0.212‬‬ ‫‪0.183‬‬ ‫‪0.149‬‬ ‫‪0.122‬‬ ‫‪0.084‬‬
‫أﺛﺒﺖ أن اﻟﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒﺔ ﺛﻢ اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻞ‪.‬‬

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(624)
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‫)‪(625‬‬
‫ﻣﺜﺎﻝ )‪(٩٤-٢‬‬
‫ﺗﻔﺎﻋ ﻞ ﻛ ﻞ ﻣ ﻦ )‪ (A, B‬ﻓ ﻲ ﺧﻄ ﻮة ﺛﻨﺎﺋﯿ ﺔ اﻟﺠﺰﯾﺌﯿ ﺔ واﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ‬

‫ﯾﺒﯿﻦ ﺗﺮﻛﯿ ﺰات )‪ (A‬ﻋﻨ ﺪ ﻣﺨﺘﻠ ﻒ اﻷزﻣﻨ ﺔ وذﻟ ﻚ ﻓ ﻲ ﺗﺠﺮﺑ ﺔ أﺟﺮﯾ ﺖ‬
‫ﻋﻨﺪ )‪(17 ºC‬‬
‫‪10 [A]/mol dm-3‬‬ ‫‪10.00‬‬ ‫‪7.94‬‬ ‫‪6.31‬‬ ‫‪5.01‬‬ ‫‪3.98‬‬
‫‪time/min‬‬ ‫‪0‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫ﻓ ﺈذا ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﻤﺘﻔﺎﻋ ﻞ )‪ (B‬ھ ﻮ )‪، (25 mol dm-3‬‬
‫ﻓﺎﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻟﻠﺘﻔﺎﻋﻞ ﺛﻨﺎﺋﻲ اﻟﺮﺗﺒﺔ‪.‬‬
‫‪....................................................................................................................... .................................................................‬‬
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‫)‪(626‬‬
‫ﻣﺜﺎﻝ )‪(٩٥-٢‬‬
‫ﻓ ﻲ ﺗﻔﺎﻋ ﻞ ﺛﻨ ﺎﺋﻲ اﻟﺮﺗﺒ ﺔ ﺑ ﯿﻦ ﺑﺮوﻣﯿ ﺪ اﻷﯾﺰوﺑﯿﻮﺗﯿ ﻞ وأﯾﺜﻮﻛﺴ ﯿﺪ‬

‫اﻟﺼ ﻮدﯾﻮم ﻋﻨ ﺪ )‪ ،(95 ºC‬ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﺒﺮوﻣﯿ ﺪ ھ ﻮ‬
‫)‪ (0.0505 mol dm-3‬واﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻸﯾﺜﻮﻛﺴ ﯿﺪ ھ ﻮ‬
‫)‪ ، (0.0762 mol dm-3‬وﻛ ﺎن اﻟ ﻨﻘﺺ )‪ (x‬ﻓ ﻲ ﺗﺮﻛﯿ ﺰ ﻛ ﻞ ﻣ ﻦ‬
‫اﻟﻤﺘﻔﺎﻋﻠﯿﻦ ﻓﻲ ﻣﺨﺘﻠﻒ اﻷزﻣﻨﺔ ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬
‫‪10 x mol dm-3‬‬ ‫‪0‬‬ ‫‪5.9‬‬ ‫‪10.7 16.6 23.0 27.7 33.5‬‬
‫‪time/min‬‬ ‫‪0‬‬ ‫‪5‬‬ ‫‪10‬‬ ‫‪17‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪60‬‬
‫اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

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‫)‪(627‬‬
‫ﻣﺜﺎﻝ )‪(٩٦-٢‬‬
‫ﯾﺘﻔﻜ ﻚ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ )‪ (CH3CHO‬ﻋﻨ ﺪ )‪ (500 ºC‬ﻣﻌﻄﯿ ﺎ ً ﻏ ﺎزي‬

‫اﻟﻤﯿﺜﺎن وﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻜﺮﺑﻮن ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪ο‬‬
‫‪CH3CHO ‬‬
‫‪500 C‬‬
‫‪→ CH 4 + CO 2‬‬
‫ﺗﻌﺘﻤﺪ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻠﻰ ﻧﺴﺒﺔ اﻟﺘﻔﻜﻚ ﺣﺴﺐ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫ﻧﺴﺒﺔ اﻟﺘﻔﻜﻚ‬ ‫‪0‬‬ ‫‪5‬‬ ‫‪10 15 20‬‬ ‫‪25‬‬ ‫‪30‬‬ ‫‪35‬‬ ‫‪40‬‬ ‫‪45‬‬ ‫‪50‬‬
‫‪ 8.53 7.49 6.74 5.9 5.14 4.69 4.31 3.75 3.11 2.67 2.29‬ﺳﺮﻋﺔ اﻟﺘﻔﻜﻚ‬
‫‪mmHg. min-1‬‬
‫أوﺟﺪ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ؟‬
‫ﺍﳉﻮﺍﺏ ‪ :‬اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

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‫)‪(628‬‬
‫ﻣﺜﺎﻝ )‪(٩٧-٢‬‬
‫درﺳ ﺖ ﻓﺎﻋﻠﯿ ﺔ اﻷﻧ ﺰﯾﻢ )‪ (A‬ﺑﻮﺟ ﻮد ﺗﺮاﻛﯿ ﺰ ﻣﺨﺘﻠﻔ ﺔ ﻣ ﻦ اﻟﻤ ﺎدة )‪(B‬‬
‫ﺣﺴﺐ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪[B-] M‬‬
‫)‪t (min‬‬ ‫‪50‬‬ ‫‪100‬‬ ‫‪200‬‬ ‫‪300‬‬
‫ﻓﺎﻋﻠﯿﺔ ‪A‬‬
‫‪0‬‬ ‫‪100‬‬ ‫‪100‬‬ ‫‪100‬‬ ‫‪100‬‬
‫‪10‬‬ ‫‪97‬‬ ‫‪94‬‬ ‫‪89‬‬ ‫‪84‬‬
‫‪20‬‬ ‫‪94‬‬ ‫‪89‬‬ ‫‪79‬‬ ‫‪71‬‬
‫‪40‬‬ ‫‪89‬‬ ‫‪79‬‬ ‫‪63‬‬ ‫‪50‬‬
‫‪60‬‬ ‫‪84‬‬ ‫‪71‬‬ ‫‪50‬‬ ‫‪35‬‬
‫‪80‬‬ ‫‪79‬‬ ‫‪63‬‬ ‫‪40‬‬ ‫‪25‬‬
‫‪100‬‬ ‫‪75‬‬ ‫‪56‬‬ ‫‪31‬‬ ‫‪18‬‬
‫‪150‬‬ ‫‪64‬‬ ‫‪42‬‬ ‫‪18‬‬ ‫‪7.5‬‬
‫‪200‬‬ ‫‪56‬‬ ‫‪31‬‬ ‫‪10‬‬ ‫‪3‬‬
‫اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ؟‬

‫ﺍﳉﻮﺍﺏ ‪k = 5.75 × 10-2 mol-1 L min-1 :‬‬
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‫)‪(629‬‬
‫ﻣﺜﺎﻝ )‪(٩٨-٢‬‬
‫أﺟﺮي اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪CH3CH 2 NO2 + OH- ‬‬
‫‪→ CH3CHNO-2 + H 2 O‬‬
‫ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة )‪ (273 K‬ﺣﯿ ﺚ ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻜ ﻼ‬

‫اﻟﻤﺘﻔﺎﻋﻠﯿﻦ ﯾﺴﺎوي )‪ .(0.005 mol dm-3‬وﻗﺪ وﺟ ﺪ أن ﺗﺮﻛﯿ ﺰ أﯾ ﻮن‬
‫اﻟﮭﯿﺪروﻛﺴﯿﺪ ﯾﺘﻐﯿﺮ ﻣﻊ اﻟﺰﻣﻦ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫)‪Time(second‬‬ ‫‪5‬‬ ‫‪10‬‬ ‫‪15‬‬
‫‪[OH-] mol dm-3‬‬ ‫‪2.60 × 10-3‬‬ ‫‪1.7 × 10-3‬‬ ‫‪1.3 ×10-3‬‬
‫ﺑ ﯿﻦ ﻋ ﻦ طﺮﯾ ﻖ اﻟﺮﺳ ﻢ اﻟﺒﯿ ﺎﻧﻲ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ وأوﺟ ﺪ‬

‫ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
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‫)‪(630‬‬
‫ﻣﺜﺎﻝ )‪(٩٩-٢‬‬
‫ﺣﺼ ﻞ ﻋﻠ ﻰ اﻟﻤﻌﻠﻮﻣ ﺎت اﻟﺘﺎﻟﯿ ﺔ ﻣ ﻦ ﺗﻔﺎﻋ ﻞ ﻣ ﺎ ﺑ ﯿﻦ ﺛﻼﺛ ﻲ إﯾﺜﯿ ﻞ أﻣ ﯿﻦ‬

‫وﻣﯿﺜﯿ ﻞ اﻟﯿ ﻮد ﻓ ﻲ ﻣﺤﻠ ﻮل اﻟﻨﯿﺘﺮوﺑﻨ ﺰﯾﻦ‪ .‬وﻗ ﺪ ﻛﺎﻧ ﺖ ﻛ ﻞ ﻣ ﻦ اﻟﻤ ﺎدﺗﯿﻦ‬
‫ﻣﻮﺟﻮدة ﺑﺘﺮﻛﯿﺰ اﺑﺘﺪاﺋﻲ ﻗﺪره )‪.(0.02 mol dm-3‬‬
‫)‪Time (Sec.‬‬ ‫‪325‬‬ ‫‪1295‬‬ ‫‪1530‬‬ ‫‪1975‬‬
‫اﻟﻤﺘﻔﺎﻋﻞ ‪%‬‬ ‫‪31.4‬‬ ‫‪64.9‬‬ ‫‪68.8‬‬ ‫‪73.7‬‬
‫اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻟﻠﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ﺑﺎﺳﺘﻌﻤﺎل طﺮﯾﻘﺔ اﻟﺘﻜﺎﻣﻞ‪.‬‬
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‫)‪(631‬‬
‫ﻣﺜﺎﻝ )‪(١٠٠-٢‬‬
‫ﺛﺎﺑﺖ ﻣﻌﺪل اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫‪H + + OH - ‬‬
‫‪→ H 2O‬‬
‫ﯾﺴﺎوي )‪.(k = 1.3 × 1011 dm3 mol-1 s-1‬‬

‫اﺣﺴﺐ ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ إذا ﻋﻠﻤﺖ أن ‪:‬‬
‫أ( ‪[H+] = [OH-] = 10-1 mol dm-3‬‬
‫ب( ‪[H+] = [OH-] = 10-4 mol dm-3‬‬
‫‪........................................................................................................................................................ ................................‬‬
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‫)‪(632‬‬
‫ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻟﺜﺔ )‪(third order‬‬

‫ﺍﳌﻌﺎﺩﻻﺕ ﺍﻟﺘﻜﺎﻣﻠﻴﺔ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺛﻼﺛﻴﺔ ﺍﻟﺮﺗﺒﺔ‬
‫ﯾﻌﺘﺒ ﺮ ھ ﺬا اﻟﻨ ﻮع ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﻧ ﺎدر اﻟﺤ ﺪوث ﻓ ﻲ اﻟﺤﺎﻟ ﺔ اﻟﻐﺎزﯾ ﺔ‬

‫ﻟﺼ ﻌﻮﺑﺔ إﺻ ﻄﺪام ﺛ ﻼث ﺟﺰﯾﺌ ﺎت ﻓ ﻲ ﻧﻔ ﺲ اﻟﻮﻗ ﺖ وﯾﺤ ﺪث ﺑﻘﻠ ﺔ ﻓ ﻲ‬
‫ﺣﺎﻟﺔ اﻟﻤﺤﺎﻟﯿﻞ )اﻟﻄﻮر اﻟﺴﺎﺋﻞ( ﻣﺜﻞ ‪:‬‬
‫• أﻛﺴﺪة ﻛﺒﺮﯾﺘﺎت اﻟﺤﺪﯾﺪوز ﻓﻲ اﻟﻤﺎء‬
‫• ﺗﻔﺎﻋﻞ أﯾﻮﻧﺎت اﻟﯿﻮد ﻣﻊ أﯾﻮﻧﺎت اﻟﺤﺪﯾﺪﯾﻚ ﻓﻲ اﻟﻤﺤﻠﻮل اﻟﻤﺎﺋﻲ‪.‬‬
‫• وﻣﻦ أﻣﺜﻠﺔ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻟﺜ ﺔ ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي ﺗﻔ ﺎﻋﻼت أول أﻛﺴ ﯿﺪ‬
‫اﻟﻨﯿﺘ ﺮوﺟﯿﻦ )أﻛﺴ ﯿﺪ اﻟﻨﯿﺘﺮﯾ ﻚ ‪ (NO‬ﻣ ﻊ ﺑﻌ ﺾ اﻟﻐ ﺎزات ﻣﺜ ﻞ‬
‫اﻷﻛﺴ ﺠﯿﻦ واﻟﻜﻠ ﻮر واﻟﺒ ﺮوم واﻟﮭﯿ ﺪروﺟﯿﻦ ﻓ ﻲ اﻟﻄ ﻮر اﻟﻐ ﺎزي‬
‫اﻟﻤﺘﺠ ﺎﻧﺲ ﺣﯿ ﺚ ﯾﺘﻔﺎﻋ ﻞ ﺟﺰﯾﺌ ﺎن ﻣ ﻦ أﻛﺴ ﯿﺪ اﻟﻨﯿﺘﺮﯾ ﻚ ﻣ ﻊ ﺟ ﺰيء‬
‫آﺧﺮ ﻣﻦ أي ﻣﻦ اﻟﻐﺎزات اﻟﺴﺎﺑﻘﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪2NO + X 2 ‬‬
‫‪→ 2NOX‬‬
‫‪2NO + H 2 ‬‬
‫‪→ N2O + H2O‬‬
‫‪2NO + O 2 ‬‬
‫‪→ 2NO 2‬‬
‫‪2NO + Cl 2 ‬‬
‫‪→ 2NOCl‬‬
‫‪2NO + Br2 ‬‬
‫‪→ 2NOBr‬‬
‫ﺣﯿﺚ )‪(X = H2, Br2, Cl2, O2‬‬

‫)‪(633‬‬
‫وﯾﻜﻮن ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻓﻲ ﻛﻞ ﺣﺎﻟﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫]‪1 d[NO‬‬ ‫] ‪d[X 2‬‬
‫‪-‬‬ ‫‪=-‬‬ ‫] ‪= k [NO]2 [X 2‬‬
‫‪2 dt‬‬ ‫‪dt‬‬
‫• وﻣ ﻦ اﻷﻣﺜﻠ ﺔ أﯾﻀ ﺎ ً ﻟﺘﻔﺎﻋ ﻞ ﺛﻼﺛ ﻲ اﻟﺮﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑ ﯿﻦ ﻛﻠﻮرﯾ ﺪ‬
‫اﻟﺤﺪﯾﺪﯾﻚ وﻛﻠﻮرﯾﺪ اﻟﻘﺼﺪﯾﺮوز ﻓﻲ وﺳﻂ ﻣﺎﺋﻲ ‪:‬‬
‫‪SnCl2 + 2FeCl3 ‬‬
‫‪→ SnCl 4 + 2FeCl2‬‬

‫)‪(634‬‬
‫ﻗﻮﺍﻧﲔ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻟﺜﺔ‬
‫ﺍﳊﺎﻟﺔ ﺍﻷﻭﱃ ‪ :‬ﰲ ﺣﺎﻟﺔ ﺗﺮﺍﻛﻴﺰ ﺍﳌﻮﺍﺩ ﺍﳌﺘﻔﺎﻋﻠﺔ ﺍﳌﺘﺴﺎﻭﻳﺔ‬
‫وﺗﻌﺪ ھﺬه أﺑﺴﻂ اﻟﺤﺎﻻت‪ ،‬وھﻲ اﻟﺤﺎﻟﺔ اﻟﺘﻲ ﯾﻜﻮن ﺣﺪوث اﻟﻨﻮاﺗﺞ ﻓﯿﮭ ﺎ‬
‫ﻣﻦ ﻣﺎدة ﻣﺘﻔﺎﻋﻠﺔ واﺣﺪة ﻛﻤﺎ ﻓﻲ اﻟﺘﻔﺎﻋﻞ‬
‫‪3A ‬‬
‫أو أﻛﺜ ﺮ ﻣ ﻦ ﻣ ﺎدة )]‪ ([A], [B], [C‬ﻟﻜ ﻦ ﻟﮭ ﺎ ﺟﻤﯿﻌ ﺎ ً ﻧﻔ ﺲ اﻟﺘﺮﻛﯿ ﺰ‬

‫وھﻮ )‪ (a‬ﺣﯿﺚ ‪.(a = b = c) :‬‬
‫وﯾﻜﻮن ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﺒﺎرة ﻋﻦ اﻟﺼﻮرة اﻟﺘﻔﺎﺿﻠﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪dx‬‬
‫‪= k(a - x)3‬‬
‫‪dt‬‬
‫‪ dx‬‬ ‫‪3‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪ = k(a - x) ‬‬
‫‪ dt‬‬ ‫‪‬‬
‫وﺑﺘﻨﻈﯿﻢ اﻟﻤﻌﺎدﻟﺔ‬
‫‪dx‬‬
‫⇒‬ ‫‪= k dt‬‬
‫‪(a - x)3‬‬
‫‪‬‬ ‫‪‬‬
‫‪(t = 0‬‬ ‫‪ ‬ﺑﯿﻦ ) ‪→ t x‬‬
‫‪dx‬‬
‫‪‬‬ ‫‪3‬‬
‫وﺑﻤﻜﺎﻣﻠﺔ اﻟﻌﻼﻗﺔ ‪= k dt ‬‬
‫‪‬‬ ‫‪(a‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪‬‬
‫)ﺑﯿﻦ )‪ (x = 0‬ﻋﻨﺪﻣﺎ )‪ (t = 0‬و )‪ (x = x‬ﻋﻨﺪﻣﺎ )‪ (t = t‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫)‪(635‬‬
‫‪x‬‬ ‫‪t‬‬
‫‪dx‬‬
‫)‪∫ (a - x‬‬
‫‪0‬‬
‫‪3‬‬
‫‪= ∫ kdt‬‬
‫‪0‬‬
‫‪x‬‬ ‫‪t‬‬
‫‪dx‬‬
‫)‪∫ (a - x‬‬
‫‪0‬‬
‫‪3‬‬
‫‪= k ∫ dt‬‬
‫‪0‬‬
‫وﻧﺘﯿﺠﺔ اﻟﺘﻜﺎﻣﻞ ﺗﻜﻮن ‪:‬‬

‫‪1‬‬
‫‪= kt + I‬‬
‫‪2(a - x)2‬‬
‫وﺗﻜﻮن ﻗﯿﻤﺔ اﻟﺜﺎﺑﺖ )‪ (I‬ﻋﻨﺪ )‪: (x = 0, t = 0‬‬

‫‪1‬‬
‫=‪I‬‬
‫‪2a 2‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬ ‫‪‬‬ ‫‪2‬‬
‫=‬ ‫‪kt‬‬ ‫‪+‬‬ ‫‪I‬‬ ‫‪‬‬ ‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ )‪ (I‬ﻓﻲ اﻟﻌﻼﻗﺔ‬
‫)‪ 2(a - x‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‬ ‫‪kt‬‬ ‫‪+‬‬
‫‪2(a - x)2‬‬ ‫‪2a 2‬‬
‫وﺑﺘﺮﺗﯿﺐ اﻟﻌﻼﻗﺔ ﺑﺪﻟﯿﻞ اﻟﺘﺮاﻛﯿﺰ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪2(a - x)2 2a 2‬‬
‫أو‬
‫‪1 1‬‬ ‫‪1‬‬
‫‪2  (a - x)2 a 2 ‬‬
‫‪-‬‬ ‫‪= kt‬‬

‫)‪(636‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪‬‬

‫ﯾﻤﻜﻦ أن ﺗﺆول ﺑﻌ ﺪ ﺗﻮﺣﯿ ﺪ اﻟﻤﻘﺎﻣ ﺎت‬ ‫‪‬‬ ‫‪2‬‬
‫‪-‬‬ ‫‪2‬‬
‫‪= kt ‬‬ ‫واﻟﻤﻌﺎدﻟﺔ‬
‫‪ 2(a - x) 2a‬‬ ‫‪‬‬
‫اﻟﻰ ‪:‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪= kt‬‬
‫‪2(a - x) 2 2a 2‬‬
‫) ‪2 ( a 2 − (a - x) 2‬‬
‫‪= kt‬‬
‫‪2 a 2 × 2(a - x) 2‬‬
‫) ‪a 2 - (a 2 - 2 ax + x 2‬‬
‫‪= kt‬‬
‫‪2a 2 (a - x) 2‬‬
‫‪a 2 - a 2 + 2 ax - x 2‬‬
‫‪= kt‬‬
‫‪2a 2 (a - x) 2‬‬
‫‪2 ax - x 2‬‬
‫‪= kt‬‬
‫‪2a 2 (a - x) 2‬‬
‫) ‪x ( 2a - x‬‬
‫⇒‬ ‫‪= kt‬‬
‫‪2a 2 (a - x) 2‬‬
‫‪‬‬ ‫‪‬‬
‫)‪،  12  (a -1x‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪1‬‬
‫‪-‬‬ ‫‪2‬‬
‫‪= kt ‬‬ ‫)‪،  2(a - x‬‬ ‫‪2‬‬
‫‪-‬‬ ‫‪2‬‬
‫‪= kt ‬‬ ‫ﺎدﻻت ‪:‬‬ ‫إن اﻟﻤﻌ‬
‫‪‬‬ ‫‪2a‬‬ ‫‪‬‬
‫‪2‬‬
‫‪ ‬‬ ‫‪a ‬‬ ‫‪‬‬
‫) ‪ x ( 2a - x‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪1‬‬ ‫‪1 ‬‬

‫ﺗﻤﺜ ﻞ اﻟﻤﻌ ﺎدﻻت اﻟﺘﻜﺎﻣﻠﯿ ﺔ‬ ‫‪‬‬ ‫‪2‬‬ ‫‪2‬‬
‫‪= kt ‬‬ ‫)‪،  2(a - x‬‬ ‫‪2‬‬
‫‪= kt +‬‬ ‫‪‬‬
‫‪2a 2 ‬‬
‫)‪ 2a (a - x‬‬ ‫‪‬‬ ‫‪‬‬
‫ﻟﻠﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ ﻓﻲ ﺣﺎﻟﺔ ﺗﺴﺎوي ﺗﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‪،‬‬

‫وھﻲ ﺗﻤﺜﻞ ﺻﻮراً ﻣﺨﺘﻠﻔﺔ ﻟﻤﻌﺎدﻟﺔ واﺣﺪة ‪.‬‬

‫)‪(637‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1 ‬‬

‫واﻟﻤﻌﺎدﻟﺔ ‪  2(a - x)2 = kt + 2a 2 ‬ھﻲ ﻣﻌﺎدﻟﺔ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠ ﮫ )‪(k‬‬
‫‪‬‬ ‫‪‬‬
‫‪ 1 ‬‬
‫واﻟﺠﺰء اﻟﻤﻘﻄﻮع ﻣﻦ ﻣﺤﻮر اﻟﺼﺎدات ھﻮ ‪ ،  2a 2 ‬وﯾﻤﻜﻦ اﻟﺤﺼ ﻮل‬
‫‪‬‬ ‫‪1‬‬ ‫‪‬‬

‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات و )‪ (t‬ﻋﻠ ﻰ‬ ‫‪‬‬ ‫‪2 ‬‬ ‫ﻋﻠﻰ ھﺬا اﻟﺨﻂ ﺑﺘﻤﺜﯿﻞ‬
‫‪ 2(a - x) ‬‬
‫ﻣﺤﻮر اﻟﺴﯿﻨﺎت )ﺷﻜﻞ ‪.(٣٠-٢‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1 ‬‬

‫‪ ‬ﻟﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬ ‫‪2‬‬
‫‪= kt +‬‬ ‫ﺷ ﻜﻞ )‪ : (٣٠-٢‬اﻟﻌﻼﻗ ﺔ اﻟﺨﻄﯿ ﺔ ﻟﻤﻌﺎدﻟ ﺔ ‪‬‬
‫)‪ 2(a - x‬‬ ‫‪2a 2 ‬‬
‫اﻟﺜﺎﻟﺜﺔ ﻓﻲ ﺣﺎﻟﺔ ﺗﺴﺎوي ﺗﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬

‫)‪(638‬‬
‫‪ x ( 2a - x ) ‬‬ ‫) ‪ x ( 2a - x‬‬ ‫‪‬‬

‫ﻋﻠﻰ ﻣﺤﻮر‬ ‫‪‬‬ ‫‪2‬‬ ‫‪2 ‬‬ ‫‪ ‬ﺑﺘﻤﺜﯿﻞ‬ ‫‪2‬‬ ‫‪2‬‬
‫‪= kt ‬‬ ‫ورﺳﻢ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ 2a (a - x) ‬‬ ‫)‪ 2a (a - x‬‬ ‫‪‬‬
‫اﻟﺼﺎدات واﻟﺰﻣﻦ )‪ (t‬ﻋﻠﻰ ﻣﺤﻮر اﻟﺴﯿﻨﺎت ﻓﺘﻌﻄﻲ ﺧﻄﺎ ً ﻣﺴﺘﻘﯿﻤﺎ ً ﯾﻤ ﺮ‬

‫ﺑﻨﻘﻄﺔ اﻷﺻﻞ ﻣﯿﻠﮫ ﯾﺴﺎوي )‪ (k‬ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(٣١-٢‬‬
‫) ‪ x ( 2a - x‬‬ ‫‪‬‬
‫‪ ‬ﻟﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜ ﺔ‬ ‫‪2‬‬
‫ﺷﻜﻞ )‪ : (٣١-٢‬اﻟﻌﻼﻗﺔ اﻟﺨﻄﯿﺔ ﻟﻤﻌﺎدﻟﺔ ‪= kt ‬‬
‫‪2‬‬
‫)‪ 2a (a - x‬‬ ‫‪‬‬
‫ﻓﻲ ﺣﺎﻟﺔ ﺗﺴﺎوي ﺗﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪‬‬

‫ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪-‬‬ ‫‪2‬‬
‫‪= kt ‬‬ ‫وﯾﻤﻜﻦ ﺣﺴﺎب )‪ (k‬وﻓﻘﺎ ً ﻟﻠﻌﻼﻗﺔ‬
‫‪ 2(a - x) 2a‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬

‫=‪k‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪t  2(a - x)2 2a 2 ‬‬

‫)‪(639‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬

‫أو اﻟﻌﻼﻗ ﺔ‬ ‫‪k = ‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪t  2(a - x) 2 2a 2  ‬‬ ‫وﻧﻼﺣ ﻆ ﻣ ﻦ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬
‫‪‬‬ ‫‪1 x ( 2a - x ) ‬‬

‫ﺪات اﻟﺜﺎﺑ ﺖ )‪ (k‬ھ ﻲ ﻣﺮﺑ ﻊ ﻣﻘﻠ ﻮب‬ ‫‪ ‬أن وﺣ‬ ‫‪k‬‬ ‫=‬ ‫‪‬‬
‫‪t 2a 2 (a - x) 2 ‬‬
‫‪‬‬
‫اﻟﺘﺮﻛﯿﺰ ﻣﻀﺮوﺑﺎ ً ﻓﻲ ﻣﻘﻠﻮب اﻟﺰﻣﻦ ‪:‬‬

‫‪(concentration)-2 (time)-1‬‬
‫ﻓﺈذا ﻗﯿﺲ اﻟﺘﺮﻛﯿﺰ ﺑﻮﺣﺪات )‪ (mol dm-3‬واﻟ ﺰﻣﻦ ﺑ ﺎﻟﺜﻮاﻧﻲ )‪ (s‬ﻓ ﺈن‬
‫وﺣﺪات ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ ﺗﻜﻮن ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪(concentration)-2 (time)-1‬‬
‫‪(mol dm-3 )-2 (s)-1 = (dm3 ) 2 mol-2 s-1 = dm 6 mol -2 s -1‬‬
‫وھ ﺬه أﯾﻀ ﺎ ً ﺗﺨﺘﻠ ﻒ ﻋ ﻦ وﺣ ﺪات ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻓ ﻲ ﺣﺎﻟ ﺔ‬

‫اﻟﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ واﻟﺜﺎﻧﯿﺔ‪.‬‬
‫ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﺎﻟﺜﺔ‬
‫ﰲ ﺣﺎﻟﺔ ﺗﺴﺎﻭﻱ ﺗﺮﺍﻛﻴﺰ ﺍﳌﻮﺍﺩ ﺍﳌﺘﻔﺎﻋﻠﺔ‬
‫ﻛﻤﺎ ھ ﻲ اﻟﺤ ﺎل ﻓ ﻲ اﻟﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻻ ﻧﺴ ﺘﻄﯿﻊ اﺳ ﺘﻨﺘﺎج‬

‫ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ )أو ﻓﺘ ﺮة ﻋﻤ ﺮ اﻟﻨﺼ ﻒ( ﻓ ﻲ ﺣﺎﻟ ﺔ ﻋ ﺪم ﺗﺴ ﺎوي‬
‫ﺗﺮاﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ‪ ،‬وﻟﻜ ﻦ ﯾﻤﻜ ﻦ اﺳ ﺘﻨﺘﺎﺟﮭﺎ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﺴ ﺎوي‬

(640)
 x ( 2a - x )   1 1 
 2 2
= kt  ‫أو‬  2
- 2
= kt  ‫اﻟﺘﺮاﻛﯿ ﺰ ﻣ ﻦ اﻟﻤﻌﺎدﻟ ﺔ‬
 2a (a - x)   2(a - x) 2a 
: ‫وذﻟﻚ ﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ‬

 3 
. t 1 =  ‫( ﻟﻨﺤﺼﻞ ﻋﻠﻰ‬t = t1/2) ‫( ﻋﻨﺪﻣﺎ‬x = a/2)
 2
2a 2 k 
: ‫ﺍﻹﺛﺒﺎﺕ‬
1 1
- = kt
2(a - x) 2a 2
2
1 1 1 
t=  - 
k  2(a - x)2 2a 2 
1 1 1 
t1 =  - 
2
k  2(a - a/2)2 2a 2 
1 1 1 
t1 =  - 
2
k  2(a/2) 2 2a 2 
 
 
1 1 1 
t1 = -
2
k   2a 2  2a 2 
  
  4  
1 4 1 
t1 =  2 - 2 
2
k  2a 2a 
1 3 
t1 =  
2
k  2a 2 
3
⇒ t1 =
2
2 ka 2

‫)‪(641‬‬
‫ﻭﳝﻜﻦ ﺣﺴﺎﺏ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ )‪ (k‬ﳍﺬﻩ ﺍﳊﺎﻟﺔ ﺇﻣﺎ ﺑـ ‪:‬‬

‫‪ (١‬اﻟﺘﻌ ﻮﯾﺾ ﻋ ﻦ اﻟﻘ ﺮاءات اﻟﺘﺠﺮﯾﺒﯿ ﺔ ﻓ ﻲ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪1 x ( 2a - x ) ‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫ﻟﻨﺤﺼ ﻞ‬ ‫‪‬‬ ‫‪k‬‬ ‫=‬ ‫‪‬‬
‫‪t 2a 2 (a - x) 2 ‬‬
‫‪ ،‬أو اﻟﻌﻼﻗ ﺔ‬ ‫=‪k‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬
‫‪t  2(a - x) 2a ‬‬
‫‪‬‬
‫ﻋﻠﻰ ﻗﯿﻤﺔ ﺛﺎﺑﺘﺔ ﺗﻘﺮﯾﺒﺎ ً ﻧﺄﺧﺬ ﻣﺘﻮﺳﻄﮭﺎ ﺑﻌﺪ ذﻟﻚ واﻟ ﺬي ﯾﻌﺒ ﺮ ﻋ ﻦ ﺛﺎﺑ ﺖ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪1 ‬‬
‫‪‬‬
‫‪1‬‬
‫‪2 ‬‬ ‫ﺑﯿﺎﻧﯿﺎ ً وذﻟﻚ ﺑﺘﻤﺜﯿﻞ‬ ‫‪‬‬
‫‪1‬‬
‫‪2‬‬
‫‪= kt +‬‬ ‫‪‬‬
‫‪2a 2 ‬‬
‫‪ (٢‬ﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ‬
‫‪ 2(a - x) ‬‬ ‫)‪ 2(a - x‬‬
‫‪ 1 ‬‬
‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت ﻓﻨﺤﺼ ﻞ ﻋﻠ ﻰ‬ ‫‪ 2‬‬ ‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات و‬
‫‪ 2a ‬‬
‫ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ ﯾﻤﺜﻞ )‪.(k‬‬

‫وﯾﻤﻜ ﻦ ﻛ ﺬﻟﻚ اﻟﺤﺼ ﻮل ﻋﻠ ﻰ ﻗﯿﻤ ﺔ )‪ (k‬ﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺔ‬
‫‪ x ( 2a - x ) ‬‬ ‫) ‪ x ( 2a - x‬‬ ‫‪‬‬
‫ً‬
‫‪  2a 2 (a - x)2‬ﺑﯿﺎﻧﯿ ﺎ وذﻟ ﻚ ﺑﺘﻤﺜﯿ ﻞ ‪  2a 2 (a - x)2 ‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫اﻟﺼﺎدات ﻣﻘﺎﺑﻞ اﻟﺰﻣﻦ )‪ (t‬ﻋﻠﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت‪ .‬ﻓﻨﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ‬
‫ﻣﺴﺘﻘﯿﻢ ﯾﻤﺮ ﻣﻦ ﻧﻘﻄﺔ اﻷﺻﻞ وﻣﯿﻠﮫ ﯾﺴﺎوي )‪.(k‬‬
‫‪ -٣‬ﻣ ﻦ ﻗﯿ ﺎس ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟﻠﺘﻔﺎﻋ ﻞ وذﻟ ﻚ ﺑ ﺎﻟﺘﻌﻮﯾﺾ ﻓ ﻲ‬
‫اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪3‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪2 k a2‬‬
‫‪3‬‬
‫=‪⇒k‬‬
‫‪2 t 1a2‬‬
‫‪2‬‬

‫)‪(642‬‬
‫ﻃﺮﻳﻘﺔ ﺗﻜﺎﻣﻞ ﺃﺧﺮﻯ ﻟﺘﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﺜﻼﺛﺔ ﺫﺍﺕ ﺍﳌﺘﻔﺎﻋﻼﺕ‬
‫ﺍﳌﺘﺴﺎﻭﻳﺔ ﺍﻟﱰﻛﻴﺰ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺗﺮﺍﻛﻴﺰ ﺍﳌﺘﻔﺎﻋﻼﺕ‬
‫ﺑﻔﺮض ﺗﻔﺎﻋ ﻞ ﺛﻼﺛ ﺔ ﺟﺰﯾﺌ ﺎت ﻣ ﻦ ﻣ ﺎدة واﺣ ﺪة أو ﺛﻼﺛ ﺔ ﺟﺰﯾﺌ ﺎت ﻣ ﻦ‬

‫ﺛﻼﺛ ﺔ ﻣ ﻮاد ﻣﺨﺘﻠﻔ ﺔ وﻟﻜﻨﮭ ﺎ ﺑ ﻨﻔﺲ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ‪ ،‬وﻧﻤﺜﻠﮭ ﺎ‬
‫ﺑﺎﻟﻤﻌﺎدﻻت اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪A + A + A ‬‬
‫‪A + B + C ‬‬
‫ﻓﺈن ﻣﻌﺪل اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ‪:‬‬

‫]‪d[A‬‬
‫]‪= k [A‬‬
‫‪3‬‬
‫‪-‬‬
‫‪dt‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫]‪[A‬‬
‫‪3‬‬
‫وﺑﺎﻟﺘﻜﺎﻣﻞ ﻣﺎ ﺑﯿﻦ )‪ (t = 0‬و ‪: t‬‬

‫]‪d[A‬‬
‫‪-‬‬ ‫‪= kdt‬‬
‫]‪[A‬‬
‫‪3‬‬
‫‪A‬‬ ‫‪t‬‬
‫]‪d[A‬‬
‫‪-‬‬ ‫]‪∫ [A‬‬
‫‪A0‬‬
‫‪3‬‬
‫‪=k‬‬
‫‪t=0‬‬
‫∫‬ ‫‪dt‬‬
‫‪A‬‬ ‫‪t‬‬
‫‪- ∫ [ A ] d[A] = k‬‬ ‫∫‬

‫‪-3‬‬
‫‪dt‬‬
‫‪A0‬‬ ‫‪t=0‬‬
‫] ‪[A‬‬
‫‪ 1 ‬‬
‫‪= k [ t ]0‬‬
‫‪t‬‬
‫‪-‬‬ ‫‪2‬‬
‫] ‪ - 2 [ A ]  [A‬‬
‫‪0‬‬
‫‪1 1‬‬ ‫‪1 ‬‬

‫⇒‬ ‫‪‬‬ ‫‪-‬‬ ‫‪= k t‬‬
‫]‪2 [A‬‬‫‪2‬‬
‫[‬ ‫‪A‬‬ ‫]‬
‫‪2‬‬
‫‪‬‬
‫‪‬‬ ‫‪0 ‬‬

‫)‪(643‬‬
‫أو‬
‫‪1 1‬‬ ‫‪1 ‬‬
‫‪‬‬ ‫‪-‬‬ ‫‪= k t‬‬
‫‪2  [ A ]2 [ A ]2 ‬‬
‫‪‬‬ ‫‪0‬‬
‫‪1‬‬ ‫‪1‬‬
‫⇒‬ ‫‪-‬‬ ‫‪=kt‬‬
‫]‪2 [ A‬‬ ‫‪2 [ A ]0‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪ 1‬‬ ‫‪‬‬

‫ﻟﺘﺄﺧ ﺬ ﻣﻌﺎدﻟ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ‬ ‫‪‬‬
‫]‪ 2[A‬‬
‫‪-‬‬
‫‪1‬‬
‫‪= k t‬‬ ‫وﺑﺘﺮﺗﯿ ﺐ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪2 [ A ]0‬‬ ‫‪‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪‬‬ ‫‪‬‬
‫ﻛﺎﻟﺘﺎﻟﻲ ‪:‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪=kt+‬‬
‫]‪2 [A‬‬ ‫‪2 [ A ]0‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪ 1 ‬‬ ‫‪ 1‬‬ ‫‪1 ‬‬

‫ﺑﺪﻻﻟﺔ )‪ (t‬ﯾﻌﻄ ﻲ‬ ‫‪‬‬ ‫‪‬‬
‫‪ 2 [ A ]2 ‬‬
‫ﺑﺮﺳﻢ‬ ‫‪‬‬
‫‪ 2 [ A ]2‬‬
‫=‬ ‫‪k‬‬ ‫‪t‬‬ ‫‪+‬‬ ‫‪‬‬ ‫وﺗﻤﺜﯿﻞ اﻟﻤﻌﺎدﻟﺔ‬
‫[‬ ‫]‬ ‫‪‬‬
‫‪2‬‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪2‬‬ ‫‪A‬‬ ‫‪0 ‬‬
‫‪ 1 ‬‬
‫ﻛﻤﺎ ﻓﻲ اﻟﺸﻜﻞ )‪.(٣٢-٢‬‬ ‫‪‬‬ ‫‪‬‬
‫‪ 2 [ A ]2 ‬‬
‫ﺧﻄﺎ ً ﻣﺴﺘﻘﯿﻤﺎ ً ﻣﯿﻠﮫ ﯾﺴﺎوي )‪ (k‬وﺗﻘﺎطﻌﮫ‬
‫‪‬‬ ‫‪0 ‬‬
‫‪1‬‬
‫ﺑﺪﻻﻟﺔ اﻟﺰﻣﻦ‬ ‫ﺷﻜﻞ )‪ : (٣٢-٢‬ﺗﻐﯿﺮ‬
‫]‪2[A‬‬
‫‪2‬‬

(644)
‫ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ‬

Half-life period
: ‫ ﻓﻲ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‬ [ A2]  ‫[ ﺑـ‬A] ‫ﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ‬
0
 
1 1
- =kt
2[A] 2 [ A ]0
2 2
1 1
-
= k t1
[A]  2 [ A ]0
2 2 2
2 0

 2 
1 1
- = k t1
2 [ A ]0 2 [ A ]0
2 2 2
4
4 1
- = k t1
2 [ A ]0 2 [ A ]0
2 2 2
4 -1
= k t1
2 [ A ]0
2 2
3
= k t1
2 [ A ]0
2 2
3
⇒ t1 =
2 k [ A ]0
2
2

‫)‪(645‬‬
‫ﻣﺜﺎﻝ )‪(١٠١-٢‬‬
‫وﺟﺪ ﻋﻤﻠﯿﺎ ً أن اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪2NO + Cl2 ‬‬
‫‪→ 2NOCl‬‬
‫ﯾﺘﺒﻊ ﻣﻌﺪل ﯾﺘﻨﺎﺳﺐ ﻣﻊ ]‪ .[NO]2[Cl‬ﻛﯿﻒ ﯾﻤﻜ ﻦ اﻟﺘﻌﺒﯿ ﺮ ﻋ ﻦ ﻣﻌ ﺪل‬

‫‪ d[NO] d[Cl2 ] ‬‬
‫‪ ،  -‬أو ﺑﻈﮭ ﻮر‬ ‫‪,-‬‬ ‫‪‬‬ ‫اﺧﺘﻔ ﺎء اﻟﻤ ﻮاد اﻟﺪاﺧﻠ ﺔ ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ‬
‫‪‬‬ ‫‪dt‬‬ ‫‪dt ‬‬
‫‪ d[NOCl] ‬‬

‫‪‬‬
‫‪‬‬ ‫‪dt‬‬
‫‪‬‬
‫‪‬‬
‫اﻟﻨﺎﺗﺞ‬
‫ﺍﳊﻞ‬
‫‪ ( 2NO + Cl2 ‬ﯾﻤﻜ ﻦ أن‬

‫ﻣ ﻦ اﻟﻤﻌﺎدﻟ ﺔ اﻟﻤﻮزوﻧ ﺔ ‪→ 2NOCl ) :‬‬
‫ﻧﻜﺘﺐ اﻵﺗﻲ ‪:‬‬

‫‪2NO + Cl 2 ‬‬
‫‪→ 2NOCl‬‬
‫]‪d[NO‬‬ ‫]‪d[Cl2 ] d[NOCl‬‬
‫‪-‬‬ ‫‪=-2‬‬ ‫=‬
‫‪dt‬‬ ‫‪dt‬‬ ‫‪dt‬‬
‫وﺑﻤ ﺎ أن اﻟﻤﻌ ﺪل ﯾﺘﻨﺎﺳ ﺐ ﻣ ﻊ ]‪ [NO]2[Cl‬إذاً ﻓﺎﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬

‫اﻟﺜﺎﻟﺜﺔ‪.‬‬

‫)‪(646‬‬
‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ ﻣﻌﺎدﻟﺔ اﻟﻤﻌﺪل ﺑﺈﺣﺪى اﻟﻄﺮق اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫]‪d[NO‬‬
‫‪-‬‬ ‫] ‪= k NO [NO]2 [Cl2‬‬
‫‪dt‬‬
‫] ‪d[Cl2‬‬
‫‪-‬‬ ‫] ‪= k Cl2 [NO]2 [Cl 2‬‬
‫‪dt‬‬
‫]‪d[NOCl‬‬
‫‪+‬‬ ‫] ‪= k NOCl [NO]2 [Cl 2‬‬
‫‪dt‬‬
‫ھ ﻲ ﺛﻮاﺑ ﺖ ﻣﻌ ﺪل اﻟﺘﻔﺎﻋ ﻞ اﻟﻤﻘﺎﺑﻠ ﺔ ﻟﻠﻄ ﺮق‬ ‫‪(k‬‬ ‫‪NOCl‬‬ ‫‪, k Cl2 , k NO‬‬ ‫)‬ ‫ﺣﯿﺚ‬
‫اﻟﻤﺨﺘﻠﻔ ﺔ ﻟﻜﺘﺎﺑ ﺔ ﻣﻌ ﺪل اﻟﺘﻔﺎﻋ ﻞ‪ .‬وﺗ ﺮﺗﺒﻂ ﺛﻮاﺑ ﺖ ﻣﻌ ﺪل اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻊ‬
‫ﺑﻌﻀﮭﺎ ﻛﺎﻵﺗﻲ ‪:‬‬
‫‪k NO = 2k Cl2 = k NOCl‬‬
‫ﻣﺜﺎﻝ )‪(١٠٢-٢‬‬
‫ﯾﺘﻔﺎﻋ ﻞ ﻛﻠﻮرﯾ ﺪ اﻟﺤﺪﯾ ﺪﯾﻚ )‪ (FeCl3‬ﻣ ﻊ ﻛﻠﻮرﯾ ﺪ اﻟﻘﺼ ﺪﯾﺮوز‬

‫)‪ (SnCl2‬طﺒﻘﺎ ً ﻟﻠﻤﻌﺎدﻟﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪2FeCl3 + SnCl2 ‬‬
‫‪→ 2FeCl2 + SnCl4‬‬
‫ﻓﺈذا ﻋﻠﻤﺖ أن ﺗﺮﻛﯿﺰ ﻛﻞ ﻣﻨﮭﻤﺎ ﻋﻨﺪ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ ﯾﺴ ﺎوي ‪(0.0625‬‬

‫)‪ M‬وﻛﺎن ﺗﺮﻛﯿﺰ ﻛﻠﻮرﯾﺪ اﻟﺤﺪﯾﺪوز )‪ (FeCl2‬ﯾﺘﻐﯿ ﺮ ﻣ ﻊ اﻟ ﺰﻣﻦ ﻛﻤ ﺎ‬
‫ﯾﻠﻲ ‪:‬‬
‫‪Time‬‬ ‫‪0‬‬ ‫‪1‬‬ ‫‪3‬‬ ‫‪7‬‬ ‫‪11‬‬ ‫‪40‬‬
‫‪[FeCl2] / M‬‬ ‫‪0‬‬ ‫‪0.01434 0.02664 0.03612 0.04102 0.05058‬‬

‫)‪(647‬‬
‫أ( أﺛﺒﺖ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‪.‬‬

‫ب( اﺣﺴﺐ ﻋﻤﺮ ﻧﺼﻒ اﻟﺘﻔﺎﻋﻞ )ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ(‬
‫ﺍﳊﻞ‬
‫ﻟﻜﻲ ﻧﺜﺒ ﺖ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻟﺜ ﺔ ﻧﺤﺴ ﺐ ﻗ ﯿﻢ )‪ (k‬ﻋﻨ ﺪ أزﻣﻨ ﺔ‬

‫ﻣﺨﺘﻠﻔﺔ ﺑﺎﻟﺘﻌﻮﯾﺾ ﻓﻲ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬
‫‪t  2(a - x) 2a ‬‬
‫أو اﻟﻌﻼﻗﺔ‬
‫‪1 1‬‬ ‫‪1 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬
‫‪2t  (a - x) a ‬‬
‫‪‬‬ ‫‪1  x ( 2a - x )  ‬‬

‫‪ k =  2‬‬ ‫‪‬‬
‫‪‬‬ ‫‪t  2a (a - x)2  ‬‬
‫‪1‬‬ ‫‪1 ‬‬

‫ﻣﺜﻼً ﻓﺈن ﻗﯿﻢ )‪ (k‬ﯾﺠ ﺐ أن‬
‫‪1‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬
‫‪t  2(a - x) 2a ‬‬
‫وإذا اﺧﺘﺮﻧﺎ اﻟﻌﻼﻗﺔ‬
‫ﺗﻜ ﻮن ﻣﺘﺴ ﺎوﯾﺔ أو ﻋﻠ ﻰ اﻷﻗ ﻞ ﻣﺘﻘﺎرﺑ ﺔ ﺣﺘ ﻰ ﻧﺤﻜ ﻢ ﻋﻠ ﻰ اﻟﺘﻔﺎﻋ ﻞ أﻧ ﮫ‬

‫ﺛﻼﺛﻲ اﻟﺮﺗﺒﺔ‪.‬‬
‫ﺑﻌﻤﻞ اﻟﺠﺪول اﻟﻼزم ‪:‬‬

‫)‪(648‬‬
‫‪a = 0.0625 M‬‬

‫‪1‬‬ ‫‪1‬‬
‫‪2‬‬
‫=‬ ‫‪= 128‬‬
‫‪2a‬‬ ‫‪2(0.0625) 2‬‬
‫‪Time/min.‬‬ ‫‪1‬‬ ‫‪3‬‬ ‫‪7‬‬ ‫‪11‬‬ ‫‪40‬‬
‫‪[FeCl2] / M = x‬‬ ‫‪0.01434‬‬ ‫‪0.02664‬‬ ‫‪0.03612‬‬ ‫‪0.04102‬‬ ‫‪0.05058‬‬
‫)‪(a – x‬‬ ‫‪0.04816‬‬ ‫‪0.03586‬‬ ‫‪0.02638‬‬ ‫‪0.02148‬‬ ‫‪0.01192‬‬
‫‪(a – x)2‬‬ ‫× ‪2.319‬‬ ‫‪1.286‬‬ ‫‪6.959‬‬ ‫× ‪4.614‬‬ ‫‪1.421‬‬
‫‪10-3‬‬ ‫‪× 10-3‬‬ ‫‪× 10-4‬‬ ‫‪10-4‬‬ ‫‪× 10-4‬‬
‫‪2(a – x)2‬‬ ‫× ‪4.638‬‬ ‫× ‪2.572‬‬ ‫× ‪1.392‬‬ ‫× ‪9.228‬‬ ‫× ‪2.842‬‬
‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬
‫‪1‬‬
‫‪215.61‬‬ ‫‪388.80‬‬ ‫‪718.390‬‬ ‫‪1083.66‬‬ ‫‪3518.65‬‬
‫‪2 (a - x)2‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬ ‫‪87.61‬‬ ‫‪260.8‬‬ ‫‪590.39‬‬ ‫‪955.66‬‬ ‫‪3390.65‬‬
‫‪ 2(a - x) 2a ‬‬
‫‪1‬‬
‫‪ ‬‬ ‫‪1‬‬ ‫‪0.333‬‬ ‫‪0.143‬‬ ‫‪0.091‬‬ ‫‪0.025‬‬
‫‪t‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬ ‫‪87.61‬‬ ‫‪86.85‬‬ ‫‪84.43‬‬ ‫‪86.96‬‬ ‫‪84.80‬‬
‫‪t  2 (a - x)2 2a 2 ‬‬
‫ﻣﺘﻮﺳﻂ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﯾﺴﺎوي )‪(k = 86.13 M-1 min-1‬‬
‫وﺣﯿﺚ أن ﻗﯿﻢ )‪ (k‬ﺗﻘﺮﯾﺒﺎ ً ﺛﺎﺑﺘﺔ ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‪.‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫وﯾﻤﻜﻦ اﺳﺘﺨﺪام اﻟﻌﻼﻗﺔ اﻷﺧﺮى ‪ k = 2t  (a - x) 2 - a 2 ‬وھﻲ ﻧﻔﺴ ﮭﺎ ﻟﻜﻨﮭ ﺎ‬
‫‪‬‬ ‫‪‬‬
‫أﻗﻞ ﻓﻲ اﻟﺤﺴﺎﺑﺎت ﻛﻤﺎ ﯾﻈﮭﺮ ﻣﻦ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪a = 0.0625 M‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪2‬‬
‫=‬ ‫‪= 256‬‬
‫‪a‬‬ ‫‪(0.0625) 2‬‬
‫‪Time/min.‬‬ ‫‪1‬‬ ‫‪3‬‬ ‫‪7‬‬ ‫‪11‬‬ ‫‪40‬‬
‫‪[FeCl2] / M = x‬‬ ‫‪0.01434 0.02664 0.03612‬‬ ‫‪0.04102‬‬ ‫‪0.05058‬‬
‫)‪(a – x‬‬ ‫‪0.04816 0.03586 0.02638‬‬ ‫‪0.02148‬‬ ‫‪0.01192‬‬
‫‪(a – x)2‬‬ ‫× ‪2.319‬‬ ‫‪1.286‬‬ ‫‪6.959‬‬ ‫× ‪4.614‬‬ ‫‪1.421‬‬
‫‪10-3‬‬ ‫‪×10-3‬‬ ‫‪×10-4‬‬ ‫‪10-4‬‬ ‫‪×10-4‬‬
‫‪1‬‬
‫‪(a - x)2‬‬ ‫‪431.22‬‬ ‫‪777.6‬‬ ‫‪1436.78‬‬ ‫‪2167.32‬‬ ‫‪7037.3‬‬
‫‪ 1‬‬ ‫‪1‬‬
‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬
‫‪175.22‬‬ ‫‪521.6‬‬ ‫‪1180.78‬‬ ‫‪1911.32‬‬ ‫‪6781.3‬‬
‫‪‬‬ ‫‪(a‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪a‬‬ ‫‪‬‬
‫‪1‬‬
‫‪ ‬‬ ‫‪0.5‬‬ ‫‪0.1665‬‬ ‫‪0.0715‬‬ ‫‪0.0455‬‬ ‫‪0.0125‬‬
‫‪ 2t ‬‬
‫‪1 1‬‬ ‫‪1 ‬‬ ‫‪87.61‬‬ ‫‪86.85‬‬ ‫‪84.43‬‬ ‫‪86.96‬‬ ‫‪84.8‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪- 2‬‬
‫‪2t  (a - x) a ‬‬
‫ﻣﺘﻮﺳﻂ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﯾﺴﺎوي )‪(k = 86.13 M-1 min-1‬‬

‫)‪(649‬‬
‫ب( ﻟﺤﺴﺎب ﻋﻤﺮ ﻧﺼﻒ اﻟﺘﻔﺎﻋﻞ ﻧﺴﺘﺨﺪم اﻟﻌﻼﻗﺔ ‪:‬‬

‫‪3‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪2 k a2‬‬
‫‪3‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪2 × 86.13 × (0.0625) 2‬‬
‫‪t 1 = 4.46 min.‬‬
‫‪2‬‬

‫)‪(650‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻟﺜﺎﻧﻴﺔ‬
‫ﺃ( ﻋﻨﺪﻣﺎ ﻳﻜﻮﻥ ﺗﺮﻛﻴﺰ ﺍﳌـﺎﺩﺓ )‪ (A‬ﻣﺴـﺎﻭ ﻟﱰﻛﻴـﺰ ﺍﳌـﺎﺩﺓ )‪(B‬‬
‫ﻭﳜﺘﻠﻒ ﻋﻦ ﺗﺮﻛﻴﺰ ﺍﳌﺎﺩﺓ )‪ (C‬ﺣﻴﺚ ‪a = b ≠ c‬‬
‫وﺗﻤﺜﻠﮫ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪A + B + C ‬‬
‫ﺃﻭ‬
‫‪( 2A + B → products,‬‬ ‫) ‪→ products‬‬

‫‪A + 2B ‬‬
‫وﺗﻜﻮن اﻟﺼﻮرة اﻟﺘﻔﺎﺿﻠﯿﺔ ﻟﻘﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ھﻲ ‪:‬‬

‫‪dx‬‬
‫)‪= k(a - x) (b - x)(c - x‬‬
‫‪dt‬‬
‫‪ a=b‬‬
‫)‪⇒ (a - x) = (b - x‬‬
‫‪⇒ (a - x)(b - x) = (a - x)2‬‬
‫‪dx‬‬
‫∴‬ ‫)‪= k(a - x) (b - x)(c - x) = k(a - x)2 (c - x‬‬
‫‪dt‬‬
‫‪dx‬‬
‫∴‬ ‫)‪= k(a - x) 2 (c - x‬‬
‫‪dt‬‬
‫‪ dx‬‬ ‫‪‬‬
‫‪:‬‬ ‫‪‬‬ ‫‪= k(a - x)2 (c - x) ‬‬ ‫ﺑﺘﻨﻈﯿﻢ اﻟﻤﻌﺎدﻟﺔ اﻷﺧﯿﺮة‬
‫‪ dt‬‬ ‫‪‬‬

(651)
dx
∴ = kdt
(a - x)2 (c - x)
 dx 
:  2
= kdt  ‫وﺑﺘﻜﺎﻣﻞ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ‬
 (a - x) (c - x) 
dx
= kdt
(a - x)2 (c - x)
dx
∫0 (a - x)2 (c - x) ∫0 kdt
x t
=
dx
∫0 (a - x)2 (c - x) ∫0 dt
x t
= k
 dx 
‫ ﺑﻄﺮﯾﻘﺔ ﺗﺠﺰﺋ ﺔ اﻟﻜﺴ ﻮر‬ ∫0 (a - x)2 (c - x) = k ∫0 dt  ‫وﺑﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟﺔ‬
x t
 
: ‫ﻧﺤﺼﻞ ﻋﻠﻰ‬
1  x(c - a)  c(a - x)  
 + ln    = kt
(c - a )
2
 a(a - x)  a(c - x) 
 1  x(c - a)  c(a - x)   
‫ﺗﻤﺜ ﻞ اﻟﻤﻌ ﺎدﻻت‬ 
 ( c - a )2  + ln    = kt  ‫واﻟﻤﻌﺎدﻟ ﺔ‬
  a(a - x)  a(c - x)   
‫اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻟﺜ ﺔ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﺴ ﺎوي ﺗﺮﻛﯿ ﺰ‬

.‫ﻣﺎدﺗﯿﻦ ﻣﻦ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‬

‫)‪(652‬‬
‫ﺏ( ﺗﻔﺎﻋﻞ ﺑﲔ ﺟﺰﻳﺌﲔ ﻣﻦ ﻧﻔﺲ ﺍﻟﻨﻮﻉ ﻭﺟﺰﻱء ﺛﺎﻟﺚ ﳜﺘﻠﻒ‪.‬‬
‫اﻟﺬي ﺗﻤﺜﻠﮫ اﻟﻤﻌﺎدﻟﺔ اﻟﺮﻣﺰﯾﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪2A + B ‬‬
‫وﺧﯿ ﺮ ﻣﺜ ﺎل ﻋﻠ ﻰ ھ ﺬا اﻟﻨ ﻮع ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ھ ﻮ ﺗﻔﺎﻋ ﻞ أﻛﺴ ﯿﺪ‬

‫اﻟﻨﯿﺘﺮوﺟﯿﻦ واﻷﻛﺴﺠﯿﻦ ﻟﺘﻜﻮﯾﻦ ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ‪:‬‬
‫‪2NO + O2 ‬‬
‫‪→ 2NO2‬‬
‫وﻋﻠﻰ اﻟﺮﻏﻢ ﻣﻦ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ وﺛﻼﺛﻲ اﻟﺠﺰﯾﺌﯿ ﺔ إﻻ أن‬

‫ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﯾﺨﺘﻠﻒ ﻋﻤﺎ ﺳﺒﻖ‪ ،‬ﺣﯿﺚ أﻧﻨﺎ ﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﻧﺠ ﺪ‬
‫أن اﻧﺨﻔ ﺎض ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة )‪ (B‬ﺑﻤﻘ ﺪار )‪ (x‬ﯾﺮاﻓﻘ ﮫ اﻧﺨﻔ ﺎض ﻓ ﻲ‬
‫ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة )‪ (A‬ﺑﻤﻘ ﺪار )‪ ،(2x‬اﻷﻣ ﺮ اﻟ ﺬي ﯾﺠﻌﻠﻨ ﺎ ﻧﻜﺘ ﺐ ﻗ ﺎﻧﻮن‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﻋﻠﻰ اﻟﺼﻮرة اﻟﺘﻔﺎﺿﻠﯿﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪dx‬‬
‫)‪= k(a - 2x) 2 (b - x‬‬
‫‪dt‬‬
‫ﺑﻌ ﺪ زﻣ ﻦ )‪ (t‬ﺗﻜ ﻮن ﺗﺮاﻛﯿ ﺰ اﻟﻨ ﻮاﺗﺞ ھ ﻲ )‪ (x‬واﻟﻤﺘﻔ ﺎﻋﻼت )‪ (A‬و‬
‫)‪ (B‬ﺗﺮاﻛﯿﺰھ ﺎ ﺑﻌ ﺪ ذﻟ ﻚ اﻟ ﺰﻣﻦ ﺗﺴ ﺎوي )‪ (a – 2x‬و )‪ (b – x‬ﻋﻠ ﻰ‬
‫اﻟﺘﻮاﻟﻲ‪.‬‬
‫‪ dx‬‬ ‫‪‬‬
‫ﺗﺼﺒﺢ ‪:‬‬ ‫‪‬‬ ‫‪= k(a - 2x)2 (b - x) ‬‬ ‫وﺑﺘﻨﻈﯿﻢ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪ dt‬‬ ‫‪‬‬

‫)‪(653‬‬
‫‪dx‬‬
‫‪= kdt‬‬
‫)‪(a - 2x) 2 (b - x‬‬
‫‪‬‬ ‫‪dx‬‬ ‫‪‬‬

‫ﺑﯿﻦ )‪ (t = 0‬ﻋﻨﺪ )‪(x = 0‬‬ ‫‪‬‬ ‫‪2‬‬
‫‪= kdt ‬‬ ‫وﺑﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟﺔ‬
‫)‪ (a - 2x) (b - x‬‬ ‫‪‬‬
‫و )‪ (x = x‬ﻋﻨﺪ )‪: (t = t‬‬

‫‪dx‬‬
‫‪= kdt‬‬
‫)‪(a - 2x)2 (b - x‬‬
‫‪dx‬‬
‫‪∫0 (a - 2x)2 (b - x) ∫0 kdt‬‬
‫‪x‬‬ ‫‪t‬‬
‫=‬
‫‪dx‬‬
‫‪∫0 (a - 2x)2 (b - x) ∫0 dt‬‬
‫‪x‬‬ ‫‪t‬‬
‫=‬ ‫‪k‬‬
‫‪‬‬ ‫‪dx‬‬ ‫‪‬‬

‫وﺑﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟﺔ ‪  ∫0 (a - 2x)2 (b - x) = k ∫0 dt ‬ﺑﻄﺮﯾﻘﺔ ﺗﺠﺰﺋﺔ اﻟﻜﺴ ﻮر‬
‫‪x‬‬ ‫‪t‬‬
‫‪‬‬ ‫‪‬‬
‫وﺑﻌﺪ اﻟﺘﺮﺗﯿﺐ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪1‬‬ ‫)‪ 2x(2b - a‬‬ ‫‪ b(a - 2x)  ‬‬
‫‪‬‬ ‫‪+ ln ‬‬ ‫‪  = kt‬‬
‫) ‪( 2b - a‬‬
‫‪2‬‬
‫‪‬‬ ‫‪a‬‬ ‫‪(a‬‬ ‫‪-‬‬ ‫)‪2x‬‬ ‫‪‬‬ ‫‪a(b‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪‬‬
‫وﺑﺎﻹﻣﻜﺎن إﯾﺠﺎد ﻗﯿﻤﺔ اﻟﺜﺎﺑﺖ )‪ (k‬ﺑﯿﺎﻧﯿ ﺎ ً ﻛﻤ ﺎ ﺳ ﺒﻖ وﻛ ﺬﻟﻚ إﯾﺠ ﺎد ﻗﯿﻤ ﺔ‬

‫)‪ (k‬ﺣﺴﺎﺑﯿﺎ ً‪.‬‬
‫‪‬‬ ‫‪1‬‬ ‫)‪ 2x(2b - a‬‬ ‫‪ b(a - 2x)  ‬‬ ‫‪‬‬
‫ھ ﻲ‬ ‫‪‬‬
‫‪ ( 2b - a )2‬‬ ‫‪‬‬ ‫‪+‬‬ ‫‪ln‬‬ ‫‪‬‬ ‫‪‬‬ ‫=‬ ‫‪kt‬‬ ‫‪‬‬
‫‪‬‬ ‫ﺣﯿ ﺚ أن اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪a‬‬ ‫‪(a‬‬ ‫‪-‬‬ ‫)‪2x‬‬ ‫‪‬‬ ‫‪a(b‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪‬‬ ‫‪‬‬
‫ﻞ‬ ‫ﺎ ً ﺑﺘﻤﺜﯿ‬ ‫ﻤﮭﺎ ﺑﯿﺎﻧﯿ‬ ‫ﺘﻘﯿﻢ وﺑﺮﺳ‬ ‫ﻂ ﻣﺴ‬ ‫ﺔﺧ‬ ‫ﻋﻼﻗ‬

(654)
  2x(2b - a)  b(a - 2x)   

‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات واﻟ ﺰﻣﻦ‬ 
1
 ( 2b - a )2  + ln   
  a (a - 2x)  a(b - x)   
‫( ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ ﻣ ﻦ ﻧﻘﻄ ﺔ‬t)

.(k) ‫اﻷﺻﻞ وﻣﯿﻠﮫ ﯾﺴﺎوي‬
: ‫اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‬

2NO + H 2 
→ N2O + H2O
: ‫( ﻣﻦ اﻟﻌﻼﻗﺔ‬k) ‫وﯾﻤﻜﻦ ﺣﺴﺎب ﻗﯿﻤﺔ‬

1  2x(2b - a)  b(a - 2x)  
kt =  + ln  
( 2b - a )
2
 a (a - 2x)  a(b - x)  
1  2x(2b - a)  b(a - 2x)  
⇒k=  + ln  
t ( 2b - a )
2
 a (a - 2x)  a(b - x)  
(x = a/2) ‫( ﯾﺴ ﺘﮭﻠﻚ ﻧﺼ ﻔﮫ أي‬NO) ‫( ﻓ ﺈن‬t) ‫وﻋﻨ ﺪ زﻣ ﻦ ﻣﻘ ﺪاره‬

 1  2x(2b - a)  b(a - 2x)   
k =  + ln     ‫وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن اﻟﻤﻌﺎدﻟ ﺔ‬
 t ( 2b - a )
2
 a (a - 2x)  a(b - x)  

: ‫ﺗﺆول اﻟﻰ‬
1  2x(2b - a)  b(a - 2x)  
k=  + ln  
t ( 2b - a )
2
 a (a - 2x)  a(b - x)  
1  2b - a 2b 
⇒k=  a +
t ( 2b - a )
2
4b - a 

‫)‪(655‬‬
‫ﺣﯿﺚ ﯾﻤﻜﻦ ﻗﯿ ﺎس ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (k‬ﻣ ﻦ اﻟﻀ ﻐﻮط اﻹﺑﺘﺪاﺋﯿ ﺔ‬

‫اﻟﻤﺨﺘﻠﻔ ﺔ ﻷﻛﺴ ﯿﺪ اﻟﻨﯿﺘ ﺮوﺟﯿﻦ )‪ (a = PNO‬وﻟﻠﮭﯿ ﺪروﺟﯿﻦ ) ‪( b = P‬‬
‫‪H2‬‬
‫وﻋﻨﺪ اﻟﺰﻣﻦ )‪ (t‬ﻟﻨﺼﻒ ﺗﺤﻠﻞ )‪ (NO‬ﻓ ﺈن اﻟﻨﺘ ﺎﺋﺞ ﻣﺒﯿﻨ ﺔ ﻓ ﻲ اﻟﺠ ﺪول‬
‫اﻟﺘ ﺎﻟﻲ وﻣ ﻦ ﻗ ﯿﻢ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ ﻧﺴ ﺘﺪل ﻋﻠ ﻰ أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬
‫اﻟﺜﺎﻟﺜﺔ ‪:‬‬
‫‪ ( 2NO + H 2 ‬ﻋﻨﺪ درﺟﺔ‬
‫ﺟﺪول ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ) ‪→ N 2O + H 2O‬‬
‫ﺣﺮارة )‪.(1099 K‬‬
‫‪k‬‬ ‫‪t sec‬‬ ‫‪PH 2‬‬ ‫‪PNO‬‬
‫‪1.76 × 10-9‬‬ ‫‪270‬‬ ‫‪4.16 × 104‬‬ ‫‪1.45 × 104‬‬
‫‪1.6 × 10-9‬‬ ‫‪204‬‬ ‫‪5.32 × 104‬‬ ‫‪2 × 104‬‬
‫‪-‬‬ ‫‪89‬‬ ‫‪5.26 × 104‬‬ ‫‪4.72 × 104‬‬
‫‪-‬‬ ‫‪227‬‬ ‫‪4.26 × 104‬‬ ‫‪1.89 × 104‬‬
‫‪-‬‬ ‫‪264‬‬ ‫‪2.7 × 104‬‬ ‫‪2.38 × 104‬‬
‫‪-‬‬ ‫‪92‬‬ ‫‪4.95 × 104‬‬ ‫‪4.87 × 104‬‬
‫‪-‬‬ ‫‪100‬‬ ‫‪5.32 × 104‬‬ ‫‪3.95 × 104‬‬
‫‪-‬‬ ‫‪152‬‬ ‫‪4.12 × 104‬‬ ‫‪3.05 × 104‬‬
‫ﻭﳝﻜﻦ ﺇﺟﺮﺍء ﺍﻟﺘﻜﺎﻣﻞ ﺑﺼﻮﺭﺓ ﺃﺧﺮﻯ ﻛﺎﻟﺘﺎﱄ ‪:‬‬

‫اﻟﻤﻌﺎدﻟﺔ اﻟﺮﻣﺰﯾﺔ ‪:‬‬
‫‪2A + B ‬‬
‫ﺗﺄﺧﺬ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ اﻟﺸﻜﻞ ‪:‬‬
‫]‪d[A‬‬
‫‪−‬‬ ‫]‪= k [ A ] [ B‬‬
‫‪2‬‬
‫‪dt‬‬
‫وﺑﺘﻜﺎﻣﻞ ھﺬه اﻟﻤﻌﺎدﻟﺔ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

(656)
 2  1 1  2 [ B]0 [ A ]
  -  + ln = kt
 2 [ B]0 - [ A ]0  [ A ] [ A ]0  2 [ B]0 - [ A ]0 [ A ]0 [ B]

( )
2
1  2(2 [ B] - [ A] )  [ B]0 [ A]  
⇒  + ln   = kt
 [ A ] [ B]  
0 0
( 2[B]0 - [ A]0 )  [ A]0 [ A]  0 

‫)‪(657‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻟﺜﺎﻟﺜﺔ‬
‫ﺇﺫﺍ ﻛﺎﻧﺖ ﺗﺮﺍﻛﻴﺰ ﺍﳌﻮﺍﺩ ﺍﳌﺘﻔﺎﻋﻠﺔ ﳐﺘﻠﻔﺔ ‪:‬‬
‫‪[A] = a, [B] = b, [C] = c‬‬
‫ﺣﻴﺚ ‪a ≠ b ≠ c‬‬
‫وﯾﻤﻜﻦ أن ﺗﻤﺜﻠﮫ اﻟﻤﻌﺎدﻟﺔ اﻟﺮﻣﺰﯾﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫‪A + B + C ‬‬
‫وﺗﻜﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻜﻞ ﻣﻨﮭﺎ ﻋﻨﺪ ﻛﻞ ﻟﺤﻈﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫]‪d[A‬‬ ‫]‪d[B‬‬ ‫]‪d[C‬‬
‫‪-‬‬ ‫‪=-‬‬ ‫‪=-‬‬ ‫]‪= k [A] [B] [C‬‬
‫‪dt‬‬ ‫‪dt‬‬ ‫‪dt‬‬
‫وإذا ﻛﺎﻧﺖ )‪ (b) ،(a‬و)‪ (c‬ھﻲ اﻟﺘﺮاﻛﯿ ﺰ اﻹﺑﺘﺪاﺋﯿ ﺔ ﻟﻠﻤ ﻮاد )‪(B) ،(A‬‬
‫و )‪ (C‬ﻋﻠﻰ اﻟﺘﻮاﻟﻲ‪ ،‬و)‪ (x‬ھﻲ ﻣﻘﺪار اﻹﻧﺨﻔﺎض ﻓﻲ ﺗﺮﻛﯿﺰ ﻛﻞ ﻣﻨﮭ ﺎ‬
‫ﻋﻨ ﺪ أي زﻣ ﻦ ﻣﻘ ﺪاره )‪ (t‬ﻓ ﺈن ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬
‫]‪ d[A‬‬ ‫]‪d[B‬‬ ‫]‪d[C‬‬ ‫‪‬‬
‫ﯾﻤﻜﻦ أن ﯾﺨﺘﺰل اﻟﻰ ‪:‬‬ ‫‪-‬‬ ‫‪=-‬‬ ‫‪=-‬‬ ‫‪= k [A] [B] [C] ‬‬
‫‪ dt‬‬ ‫‪dt‬‬ ‫‪dt‬‬ ‫‪‬‬
‫‪dx‬‬
‫)‪= k (a - x)(b - x)(c - x‬‬
‫‪dt‬‬
‫‪‬‬ ‫‪dx‬‬ ‫‪‬‬
‫وﺑﺘﻨﻈﯿﻢ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻔﺎﺿﻠﯿﺔ ‪  dt = k (a - x)(b - x)(c - x) ‬ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫‪‬‬ ‫‪‬‬
‫‪dx‬‬
‫)‪= k (a - x)(b - x)(c - x‬‬
‫‪dt‬‬
‫‪dx‬‬
‫‪= k dt‬‬
‫)‪(a - x)(b - x)(c - x‬‬

‫)‪(658‬‬
‫‪‬‬ ‫‪dx‬‬ ‫‪‬‬

‫وﺑﻤﻜﺎﻣﻠﺔ اﻟﻤﻌﺎدﻟﺔ ‪  (a - x)(b - x)(c - x) = k dt ‬ﺑﯿﻦ ‪:‬‬
‫‪‬‬ ‫‪‬‬
‫)‪ (t = 0, x = 0‬و )‪: (t = t, x = x‬‬

‫‪dx‬‬
‫‪= k dt‬‬
‫)‪(a - x)(b - x)(c - x‬‬
‫‪dx‬‬
‫‪∫0 (a - x)(b - x)(c - x) ∫0 k dt‬‬
‫‪x‬‬ ‫‪t‬‬
‫=‬
‫‪dx‬‬
‫‪∫0 (a - x)(b - x)(c - x) ∫0 dt‬‬
‫‪x‬‬ ‫‪t‬‬
‫‪=k‬‬
‫‪‬‬ ‫‪x‬‬ ‫‪dx‬‬ ‫‪t‬‬ ‫‪‬‬

‫‪  ∫0 (a - x)(b - x)(c - x) = k ∫0‬ﺑﻄﺮﯾﻘ ﺔ ﺗﺠﺰﺋ ﺔ‬ ‫‪dt ‬‬ ‫وﺑﻤﻜﺎﻣﻠ ﺔ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪‬‬
‫اﻟﻜﺴﻮر ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫)‪ 1  x(c - a‬‬ ‫‪ c(a - x)  ‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫)‪ ( c - a )2  a(a - x‬‬ ‫‪‬‬ ‫‪‬‬
‫‪+‬‬ ‫‪ln‬‬ ‫=‬ ‫‪kt‬‬
‫‪‬‬ ‫‪a(c‬‬ ‫‪-‬‬ ‫)‪x‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪a-x‬‬ ‫‪1‬‬ ‫‪b-x‬‬ ‫‪1‬‬ ‫‪c-x‬‬
‫‪( a - b )( c - a )  a  ( a - b )( b - c )  b  ( c - a )( b - c )  c ‬‬
‫‪ln ‬‬ ‫‪+‬‬ ‫‪ln ‬‬ ‫‪+‬‬ ‫‪ln ‬‬ ‫‪= kt‬‬
‫وھﺬه اﻟﻤﻌﺎدﻟﺔ ھﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻜﺎﻣﻠﯿﺔ ﻟﻠﺘﻔﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻟﺜ ﺔ ﻓ ﻲ‬

‫ﺣﺎﻟﺔ اﺧﺘﻼف ﺗﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ‬
‫س( اﺳﺘﻨﺘﺞ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ ﻟﻠﺘﻔﺎﻋﻼت ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‪ ،‬ﻋﻠﻰ ﻓ ﺮض‬
‫أن اﻟﻤﺘﻔﺎﻋﻼت ﻟﮭﺎ ﻧﻔﺲ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‪.‬‬

‫)‪(659‬‬
‫ﺗﻄﺒﻴﻘﺎﺕ ﺷﺎﻣﻠﺔ‬
‫ﻋﻠﻰ ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻷﻭﱃ ﻭﺍﻟﺜﺎﻧﻴﺔ ﻭﺍﻟﺜﺎﻟﺜﺔ‬
‫ﻣﺜﺎﻝ )‪(١٠٣-٢‬‬
‫إن ﺣﺮﻛﯿ ﺎت اﻟﺘﻔﺎﻋ ﻞ ﺑ ﯿﻦ )‪(methyl p-toluene sulphonate‬‬

‫وﯾﻮدﯾ ﺪ اﻟﺼ ﻮدﯾﻮم )‪ (NaI‬ﻓ ﻲ ﻣﺤﻠ ﻮل اﻷﺳ ﯿﺘﻮن ﻓ ﻲ درﺟ ﺔ ﺣ ﺮارة‬
‫)‪ (26.5 ºC‬ﯾﻤﻜ ﻦ ﺗﺘﺒﻌ ﮫ ﺑﻮاﺳ ﻄﺔ اﻟﺘﺴ ﺤﯿﺢ‪ .‬ﻓﻔ ﻲ ﺣﺎﻟ ﺔ اﺳ ﺘﻌﻤﺎل‬
‫ﺗﺮاﻛﯿ ﺰ أوﻟﯿ ﺔ ﻣﺘﺴ ﺎوﯾﺔ ﻟﻜ ﻞ ﻣ ﺎدة ﻣﺘﻔﺎﻋﻠ ﺔ ﺗﻐﯿ ﺮت ھ ﺬه اﻟﺘﺮاﻛﯿ ﺰ ﻣ ﻊ‬
‫اﻟﺰﻣﻦ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪time, h‬‬ ‫‪0‬‬ ‫‪0.5‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8‬‬
‫‪[A] × 102‬‬ ‫‪5‬‬ ‫‪4.85 4.72 4.48 4.26 4.03 3.86 3.70 3.55 3.40‬‬
‫‪mol/L‬‬
‫ﻣﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪ ،‬وﻣﺎ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ؟‬
‫ﺍﳊﻞ‬
‫ﺑﻤﺎ أن ﺗﺮاﻛﯿﺰ اﻟﻤﺎدﺗﯿﻦ اﻟﻤﺘﻔﺎﻋﻠﺘﯿﻦ ﻗﺪ ﺗﻐﯿﺮت ﻣﻊ اﻟﺰﻣﻦ ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ‬

‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪ .‬وﻣﻌﺎدﻟﺔ اﻟﺘﻔﺎﻋﻞ ﻟﮭﺎ ھﻲ ‪:‬‬
‫‪1‬‬ ‫‪1‬‬
‫=‪kt‬‬ ‫‪-‬‬
‫‪a-x a‬‬
‫‪1‬‬ ‫‪1‬‬
‫⇒‬ ‫‪=kt+‬‬
‫‪a-x‬‬ ‫‪a‬‬

‫)‪(660‬‬
‫‪ 1 ‬‬
‫ﻣﻘﺎﺑ ﻞ اﻟ ﺰﻣﻦ )‪ (t‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﻋﻼﻗ ﺔ‬ ‫‪‬‬ ‫‪‬‬ ‫وﺑﺮﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ‬
‫‪a-x‬‬
‫ﺧﻄﯿ ﺔ ﻓ ﻲ ﺣﺎﻟ ﺔ ﻛ ﻮن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‪ ،‬ﺣﯿ ﺚ أن اﻟﺘﺮﻛﯿ ﺰ‬

‫اﻟﻤﻌﻄ ﻰ ﻓ ﻲ اﻟﻤﺴ ﺄﻟﺔ ﻋﻨ ﺪ اﻟ ﺰﻣﻦ )‪ (t‬ﯾﻤﺜ ﻞ )‪ ،(a – x‬واﻟﺘﺮﻛﯿ ﺰ ﻋﻨ ﺪ‬
‫اﻟﺰﻣﻦ )‪ (t = 0‬ﯾﻤﺜﻞ )‪.(a‬‬
‫وﺑﻌﻤﻞ اﻟﺠﺪول اﻟﻼزم ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬
‫‪1‬‬ ‫‪ 1 ‬‬ ‫)‪[A]= (a – x‬‬ ‫‪time, h‬‬
‫‪‬‬ ‫‪‬‬
‫‪a‬‬ ‫‪a-x‬‬ ‫‪mol/L‬‬
‫‪0.2‬‬ ‫‪20‬‬ ‫‪0.05‬‬ ‫‪0‬‬
‫‪20.62‬‬ ‫‪0.0485‬‬ ‫‪0.5‬‬
‫‪21.19‬‬ ‫‪0.0472‬‬ ‫‪1‬‬
‫‪22.32‬‬ ‫‪0.0448‬‬ ‫‪2‬‬
‫‪23.47‬‬ ‫‪0.0426‬‬ ‫‪3‬‬
‫‪24.81‬‬ ‫‪0.0403‬‬ ‫‪4‬‬
‫‪25.91‬‬ ‫‪0.0386‬‬ ‫‪5‬‬
‫‪27.03‬‬ ‫‪0.0370‬‬ ‫‪6‬‬
‫‪28.17‬‬ ‫‪0.0355‬‬ ‫‪7‬‬
‫‪29.41‬‬ ‫‪0.0340‬‬ ‫‪8‬‬
‫‪ 1 ‬‬
‫ﻣﻘﺎﺑ ﻞ اﻟ ﺰﻣﻦ )‪ (t‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ اﻟﺸ ﻜﻞ‬ ‫‪‬‬ ‫‪‬‬ ‫وﺑﺘﻤﺜﯿ ﻞ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ‬
‫‪a-x‬‬
‫)‪(٣٣-٢‬‬

‫)‪(661‬‬
‫ﺷﻜﻞ )‪(٣٣-٢‬‬
‫وﺑﻤﺎ أن اﻟﻌﻼﻗﺔ ھﻲ ﻋﻼﻗﺔ ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿ ﺔ‪.‬‬

‫وﻟﺤﺴﺎب ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻓﺈن اﻟﻤﯿﻞ ﻣﻦ اﻟﺸﻜﻞ ‪:‬‬
‫‪slope = k = 1.177 L. mol -1 h -1‬‬
‫‪slope = k = 3.27 × 10 - 4 L mol -1 s -1‬‬
‫ﻣﺜﺎﻝ )‪(١٠٤-٢‬‬
‫اﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﯾﻌﻄ ﻲ ﻣ ﺪى ﺗﻔﻜ ﻚ ﻓﯿﻨﯿ ﻞ أﺛﯿ ﻞ إﯾﺜ ﺮ ﻓ ﻲ درﺟ ﺔ‬
‫)‪ (389 ºC‬ﻓﻲ أزﻣﺎن ﻣﺨﺘﻠﻔﺔ وﻟﻀﻐﻂ اﺑﺘﺪاﺋﻲ ﻗﺪره )‪.(51 torr‬‬
‫)ﺗﺤﻠﻞ( ‪% decompose‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬
‫‪Time, s‬‬ ‫‪264‬‬ ‫‪424‬‬ ‫‪609‬‬ ‫‪820‬‬

‫)‪(662‬‬
‫ﻣﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪ ،‬ﺛﻢ اﺣﺴﺐ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻧﻔ ﺮض أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ اﻟﺘ ﻲ ﻟﮭ ﺎ ﻣﻌﺎدﻟ ﺔ‬

‫اﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪ a ‬‬
‫‪kt = 2.303log ‬‬ ‫‪‬‬
‫‪a-x‬‬
‫‪ a   k ‬‬
‫‪log ‬‬ ‫‪=‬‬ ‫‪t‬‬
‫‪ a - x   2.303 ‬‬
‫‪ a ‬‬
‫و اﻟ ﺰﻣﻦ )‪ (t‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ‬ ‫‪log ‬‬ ‫‪‬‬ ‫وﻋﻨ ﺪ رﺳ ﻢ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ‬
‫‪a -x‬‬
‫ﻣﺴﺘﻘﯿﻢ ﯾﻤﺮ ﺑﻨﻘﻄﺔ اﻷﺻﻞ وﻣﯿﻠﮫ ﯾﺴﺎوي )‪.(k/2.303‬‬

‫وﻧﻈﺮاً ﻷن اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ )‪ (a‬ﻏﯿﺮ ﻣﻌﻠﻮم‪،‬ﻓﺴﻨﻔﺮﺿﮫ ﺑﺄﻧﮫ ﯾﺴ ﺎوي‬
‫)‪ ،(a = 1‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﻗﯿﻤ ﺔ‪ .‬وﺗﻜ ﻮن ﻧﺴ ﺐ اﻟﻨﺴ ﺐ اﻟﻤﺌﻮﯾ ﺔ ﻟﻠﺘﺤﻠ ﻞ‬
‫‪: log  a a- x  =  2.303‬‬
‫‪k ‬‬
‫ﺗﻌﺒﺮ ﻋﻦ )‪ .(x‬وﺗﺼﺒﺢ اﻟﻌﻼﻗﺔ ‪ t‬‬
‫‪‬‬ ‫‪ ‬‬ ‫‪‬‬
‫‪ 1   k ‬‬
‫‪log ‬‬ ‫‪=‬‬ ‫‪t‬‬
‫‪ 1 - x   2.303 ‬‬

‫‪a=1‬‬
‫‪time, s‬‬ ‫‪264‬‬ ‫‪424‬‬ ‫‪609‬‬ ‫‪820‬‬
‫)ﺗﺤﻠﻞ( ‪% decompose‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬ ‫‪50‬‬
‫‪x‬‬ ‫‪0.20‬‬ ‫‪0.30‬‬ ‫‪0.40‬‬ ‫‪0.50‬‬

(663)
 a 
log   0.097 0.155 0.222 0.301
a -x
 a 
‫( ﻧﺤﺼ ﻞ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ ﺑﻨﻘﻄ ﺔ‬t) ‫ﻣﻘﺎﺑ ﻞ‬ log   ‫وﺑﺮﺳ ﻢ‬
a-x
.(٣٤-٢ ‫اﻷﺻﻞ )ﺷﻜﻞ‬
(٣٤-٢) ‫ﺷﻜﻞ‬
slope = 3.67 × 10-4 s-1

k
slope =
2.303
k = slope × 2.303
k = 3.67 × 10-4 × 2.303
k = 8.45 × 10-4 s -1

‫)‪(664‬‬
‫ﻣﺜﺎﻝ )‪(١٠٥-٢‬‬
‫إن ﻓﺘ ﺮات ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟﻠﺘﺤﻠ ﻞ اﻟﺤ ﺮاري ﻟﻠﻔﻮﺳ ﻔﯿﻦ ﻓ ﻲ ﺿ ﻐﻮط‬

‫ﻣﺨﺘﻠﻔﺔ ﺛﻼﺛﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Initial Pressure, mmHg‬‬ ‫‪707‬‬ ‫‪79‬‬ ‫‪37.5‬‬
‫)‪t1/2 (s‬‬ ‫‪84‬‬ ‫‪84‬‬ ‫‪83.5‬‬
‫ﻓﻤﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ؟‬

‫ﺍﳊﻞ‬
‫ﺑﻤﺎ أن ﻓﺘﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ )‪ (t1/2‬ﺛﺎﺑﺘ ﺔ ﺗﻘﺮﯾﺒ ﺎ ً ﻻ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ اﻟﺘﺮﻛﯿ ﺰ‬

‫)اﻟﻀﻐﻂ ھﻨﺎ( اﻹﺑﺘﺪاﺋﻲ ﻓﺈن اﻟﺘﻔﺎﻋﻞ ھﻮ ﻣﻦ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﻣﺜﺎﻝ )‪(١٠٦-٢‬‬
‫ﻓ ﻲ درﺟ ﺔ ﺣﺮارﯾ ﺔ ﻣﻌﯿﻨ ﺔ ﻓ ﺈن ﻓﺘ ﺮات ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻟﺘﺤﻠ ﻞ اﻷﻣﻮﻧﯿ ﺎ‬

‫ﺑﻮﺟﻮد اﻟﻌﺎﻣﻞ اﻟﻤﺴﺎﻋﺪ )اﻟﻤﺤﻔﺰات( ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪Pressure, mmHg‬‬ ‫‪50‬‬ ‫‪100‬‬ ‫‪200‬‬
‫‪Half time (t1/2), h‬‬ ‫‪3.52‬‬ ‫‪1.92‬‬ ‫‪1.00‬‬
‫أوﺟﺪ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫)‪(665‬‬
‫ﺍﳊﻞ‬
‫ﺑﻤ ﺎ أن ﻧﺼ ﻒ اﻟﺘﻔﺎﻋ ﻞ ﯾﺨﺘﻠ ﻒ ﺑ ﺎﺧﺘﻼف اﻟﺘﺮﻛﯿ ﺰ )اﻟﻀ ﻐﻂ( ﻓ ﺈن‬

‫اﻟﺘﻔﺎﻋﻞ ﻟ ﯿﺲ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬ﻷن ﻧﺼ ﻒ زﻣ ﻦ اﻟﻌﻤ ﺮ ﻓ ﻲ ﺗﻔﺎﻋ ﻞ‬
‫اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﺛﺎﺑﺖ ﻻ ﯾﺘﻐﯿﺮ ﺑﺘﻐﯿﺮ اﻟﺘﺮﻛﯿﺰ ﻷﻧﮫ ﻻ ﯾﻌﺘﻤﺪ ﻋﻠﯿﮫ‪.‬‬
‫وﻣﻦ أﺟﻞ ﻣﻌﺮﻓﺔ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﻧﻄﺒﻖ اﻟﻌﻼﻗﺔ ‪:‬‬
‫‪( t1/2 )1  a 2 ‬‬
‫‪n-1‬‬ ‫‪n-1‬‬
‫‪P ‬‬
‫‪= ‬‬ ‫‪= 2 ‬‬
‫‪( 1/2 )2  a1 ‬‬
‫‪t‬‬ ‫‪ P1 ‬‬
‫‪n-1‬‬
‫‪3.52  100 ‬‬
‫‪=‬‬ ‫‪‬‬
‫‪1.92  50 ‬‬
‫) ‪1.833 = ( 2‬‬
‫‪n-1‬‬
‫‪log 1.83 = ( n - 1) log 2‬‬

‫‪log1.83‬‬
‫=‪n-1‬‬
‫‪log 2‬‬
‫‪log 1.83‬‬
‫=‪n‬‬ ‫‪+1‬‬
‫‪log 2‬‬
‫‪n = 1.872  2‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺎﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(666‬‬
‫وﻟﻤﺰﯾﺪ ﻣﻦ اﻟﺘﺄﻛﺪ ﻧﺄﺧﺬ ﻗﯿﻤﺘﻲ ﺿﻐﻂ وﻧﺼﻔﻲ ﻋﻤﺮ آﺧﺮﯾﻦ ‪:‬‬

‫‪( t1/2 )1  a 2 ‬‬
‫‪n-1‬‬ ‫‪n-1‬‬
‫‪P ‬‬
‫‪( t1/2 )2  a1 ‬‬
‫=‬ ‫‪= 2 ‬‬
‫‪ P1 ‬‬
‫‪n-1‬‬
‫‪1.92  200 ‬‬
‫‪=‬‬ ‫‪‬‬
‫‪1‬‬ ‫‪ 100 ‬‬
‫) ‪1.92 = ( 2‬‬
‫‪n-1‬‬
‫‪log 1.92 = ( n - 1) log 2‬‬

‫‪log1.92‬‬
‫=‪n-1‬‬
‫‪log 2‬‬
‫‪log 1.92‬‬
‫=‪n‬‬ ‫‪+1‬‬
‫‪log 2‬‬
‫‪n = 1.94  2‬‬
‫وھﺬا ﯾﺆﻛﺪ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫ﻣﺜﺎﻝ )‪(١٠٧-٢‬‬
‫ﻓﻲ اﻟﺘﻔﺎﻋﻞ اﻟﺒﺴﯿﻂ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪A ‬‬
‫‪→B‬‬
‫ﻓﻌﻨﺪﻣﺎ ﯾﺘﻐﯿﺮ ﺗﺮﻛﯿﺰ)‪ (A‬ﻣﻦ )‪ (0.502‬اﻟﻰ )‪ (1.007‬ﻣ ﻮل‪/‬ﻟﺘ ﺮ ﻓ ﺈن‬

‫ﻓﺘﺮة ﺗﺼﻒ اﻟﻌﻤﺮ ﺗﺘﻐﯿﺮ ﻣﻦ )‪ (51‬اﻟﻰ )‪ (26‬ﺛﺎﻧﯿﺔ ﻋﻨﺪ درﺟﺔ ﺣ ﺮارة‬
‫)‪ ،(26 °C‬ﻓﻤﺎ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪ ،‬وﻣﺎ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‪.‬‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪ ،‬وﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪(k = 0.039 L mol-1 s-1‬‬

(667)
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‫)‪(668‬‬
‫ﻣﺜﺎﻝ )‪(١٠٨-٢‬‬
‫إن ﺗﺤﻠ ﻞ ﻣﺮﻛ ﺐ ﻣﻌ ﯿﻦ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ (57.4‬أﻋﻄ ﻰ اﻟﻨﺘ ﺎﺋﺞ‬

‫زﻣﻦ ﻧﺼﻒ اﻟﺘﺤﻠﻞ‪ ،‬ﺛﺎﻧﯿﺔ‬ ‫‪4280‬‬ ‫‪885‬‬ ‫‪174‬‬
‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬
‫‪Initial Concentration‬‬ ‫‪0.50‬‬ ‫‪1.10‬‬ ‫‪2.48‬‬
‫‪mol/cm3‬‬
‫اﺣﺴﺐ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ وﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻣﻦ ﻗﯿﻢ زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ‪ ،‬ﻓﺈﻧ ﮫ ﯾﻈﮭ ﺮ ﺟﻠﯿ ﺎ ً أن اﻟﺘﻔﺎﻋ ﻞ ﻟ ﯿﺲ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬
‫اﻷوﻟﻰ‪ ،‬ﺑﺴﺒﺐ أن زﻣﻦ ﻧﺼﻒ اﻟﻌﻤ ﺮ ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺛﺎﺑ ﺖ وﻻ‬
‫ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﺘﺮﻛﯿﺰ‪ .‬ﻋﻠﻰ ﻛﻞ ﺣﺎل ﻓﺈﻧﻨﺎ ﻓﻲ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ﺳﻨﺤﺴ ﺐ ﺛﺎﺑ ﺖ‬
‫ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ وﻓﻘ ﺎ ً ﻟﻨﺼ ﻒ زﻣ ﻦ اﻟﻌﻤ ﺮ اﻟﻤﻌﻄ ﻰ ﻓ ﻲ اﻟﺠ ﺪول‪ ،‬واﻟ ﺬي‬
‫ﯾﻌﻄﻲ ﻗﯿﻤﺔ )‪ (k‬ﺛﺎﺑﺘﺔ ﯾﻤﺜﻞ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬
‫‪Initial Concentration mol/cm 3‬‬ ‫‪0.50‬‬ ‫‪1.10‬‬ ‫‪2.48‬‬
‫زﻣﻦ ﻧﺼﻒ اﻟﺘﺤﻠﻞ‪ ،‬ﺛﺎﻧﯿﺔ‬ ‫‪4280‬‬ ‫‪885‬‬ ‫‪174‬‬
‫‪0.693‬‬
‫= ‪k1‬‬
‫‪t1/2‬‬
‫‪1.62 × 10-4‬‬ ‫‪7.83 × 10-4‬‬ ‫‪39.8 × 10-4‬‬
‫‪1‬‬
‫= ‪k2‬‬
‫‪a t1/2‬‬
‫‪4.67 × 10-4‬‬ ‫‪10.27 ×10-4 23.17 × 10-4‬‬
‫‪3‬‬
‫= ‪k3‬‬ ‫‪2‬‬
‫‪2a t1/2‬‬
‫‪1.40 × 10-3‬‬ ‫‪1.40 × 10-3‬‬ ‫‪1.40 × 10-3‬‬

‫)‪(669‬‬
‫وﺑﻤﺎ أن ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺛﺎﺑﺘﺔ ﻓﻲ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‪ ،‬ﻓﺈذا اﻟﺘﻔﺎﻋﻞ‬
‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ وﯾﺴﺎوي )‪.(k = 1.4 × 10-3 L2 mol-2 s-1‬‬
‫ﻣﺜﺎﻝ )‪(١٠٩-٢‬‬
‫ﯾﺘﺤﻠﻞ اﻹﯾﺜﯿﻞ أﻣﯿﻦ ﻓﻲ ﻋﻤﻠﯿﺔ ﻏﯿﺮ ﻋﻜﺴﯿﺔ ﻟﺘﻜﻮﯾﻦ اﻷﻣﻮﻧﯿ ﺎ واﻹﯾﺜﯿﻠ ﯿﻦ‬
‫ﻛﻤﺎ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪C 2 H 5 NH 2 (g) ‬‬
‫)‪→ C 2 H 4 (g) + NH 3 (g‬‬
‫ﻓﺈذا ﻋﻠﻤﺖ أن اﻟﻀﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ )‪ (a = P0‬ﯾﺴ ﺎوي )‪.(55 mmHg‬‬

‫ودرﺟﺔ اﻟﺤﺮارة )‪ .(500 ºC‬وﻗﺪ ﺗﻢ اﻟﺤﺼﻮل ﻋﻠﻰ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪Time, min‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫‪x = ∆P, mmHg‬‬ ‫‪5‬‬ ‫‪9‬‬ ‫‪17‬‬ ‫‪29‬‬ ‫‪34‬‬ ‫‪47‬‬ ‫‪52‬‬ ‫‪53.5‬‬
‫اﺣﺴﺐ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ وﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﺑﺎﺳﺘﺨﺪام اﻟﻤﻌﺎدﻻت‪.‬‬

‫ﺍﳊﻞ‬
‫‪P0 = 55 mmHg‬‬
‫‪Time, min‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪20‬‬ ‫‪30‬‬ ‫‪40‬‬
‫‪x = ∆P, mmHg‬‬ ‫‪5‬‬ ‫‪9‬‬ ‫‪17‬‬ ‫‪29‬‬ ‫‪34‬‬ ‫‪47‬‬ ‫‪52‬‬ ‫‪53.5‬‬
‫)‪(a - x‬‬ ‫=‬ ‫‪( P0‬‬ ‫‪- ∆P ) , mmHg‬‬ ‫‪50‬‬ ‫‪46‬‬ ‫‪38‬‬ ‫‪26‬‬ ‫‪21‬‬ ‫‪8‬‬ ‫‪3‬‬ ‫‪1.5‬‬
‫اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬ ‫‪9.53‬‬ ‫‪8.95‬‬ ‫‪9.24‬‬ ‫‪9.37‬‬ ‫‪9.62‬‬ ‫‪9.63‬‬ ‫‪9.70‬‬ ‫‪9.01‬‬
‫‪2.303‬‬ ‫‪ a  2.303‬‬ ‫‪ P0 ‬‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬
‫= ‪k1‬‬ ‫‪log ‬‬ ‫=‪‬‬ ‫‪log ‬‬ ‫‪‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬ ‫‪10-2‬‬
‫‪t‬‬ ‫‪‬‬ ‫‪a‬‬ ‫‪-‬‬ ‫‪x‬‬ ‫‪‬‬ ‫‪t‬‬ ‫‪ P0 - ΔP ‬‬
‫اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ ‪:‬‬ ‫‪1.82‬‬ ‫‪1.78‬‬ ‫‪2.03‬‬ ‫‪2.54‬‬ ‫‪2.94‬‬ ‫‪5.34‬‬ ‫‪10.51‬‬ ‫‪16.21‬‬
‫‪1‬‬ ‫‪x‬‬ ‫‪ 1‬‬ ‫‪ΔP‬‬ ‫‪‬‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬
‫‪k2 = ‬‬ ‫‪ = ‬‬ ‫‪‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬ ‫‪10-3‬‬
‫‪t  a ( a - x) ‬‬ ‫‪t  P0 ( P0 - ΔP ) ‬‬
‫اﻟﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‬ ‫‪0.35‬‬ ‫‪0.36‬‬ ‫‪0.45‬‬ ‫‪0.72‬‬ ‫‪0.97‬‬ ‫‪3.82‬‬ ‫‪18.5‬‬ ‫‪55.5‬‬
‫‪1 1‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪1 ‬‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬
‫‪k3 = ‬‬ ‫‪- = ‬‬ ‫‪-‬‬ ‫‪‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬ ‫‪10-4‬‬
‫‪2t  ( a - x )2 a 2  2t  ( P0 - ΔP )2 P02 ‬‬

‫)‪(670‬‬
‫ﻣﻤﺎ ﺳﺒﻖ ﯾﺘﻀﺢ أن ﻗﯿﻢ )‪ (k1‬ﺗﻜﺎد ﺗﻜﻮن ﻣﺘﻘﺎرﺑﺔ ﺟﺪاً ﻟ ﺬا ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ‬

‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬وأن ﻣﺘﻮﺳﻂ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ھﻮ ‪:‬‬
‫‪k1‬‬ ‫=‬
‫(‬ ‫‪9.53 + 8.95 + 9.24 + 9.37 + 9.62 + 9.63 + 9.70 + 9.01) ×10 −2‬‬
‫‪8‬‬
‫‪k1 = 9.38 × 10 min‬‬ ‫‪-2‬‬ ‫‪-1‬‬
‫ﻣﺜﺎﻝ )‪(١١٠-٢‬‬
‫اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿ ﺔ ﺗ ﻢ اﻟﺤﺼ ﻮل ﻋﻠﯿﮭ ﺎ ﻣ ﻦ ﺗﺤﻠ ﻞ )‪ (17 %‬ﻣ ﻦ اﻟﺴ ﻜﺮوز‬

‫ﻓ ﻲ )‪ (0.099 N‬ﻣ ﻦ ﻣﺤﻠ ﻮل ﺣ ﺎﻣﺾ اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ )‪ (HCl‬ﻓ ﻲ‬
‫)‪: (308 ºC‬‬
‫‪[C12H22O11]t = 0 = [A]0= a = 0.099 N‬‬
‫‪Time, min‬‬ ‫‪9.82‬‬ ‫‪59.60‬‬ ‫‪93.18‬‬ ‫‪142.9‬‬ ‫‪294.8‬‬ ‫‪589.4‬‬
‫‪[C12H22O11]t = [A]t = (a – x) × 103‬‬ ‫‪96.5‬‬ ‫‪80.3‬‬ ‫‪71.3‬‬ ‫‪59.8‬‬ ‫‪32.8‬‬ ‫‪11.1‬‬
‫ﻣﺎ درﺟﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺴﻜﺮوز وﻣﺎ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ؟‬

‫ﺍﳊﻞ‬
‫‪[C12H22O11]t = 0 = [A]0 = a = 0.099 N‬‬
‫‪Time, min‬‬ ‫‪9.82‬‬ ‫‪59.60‬‬ ‫‪93.18‬‬ ‫‪142.9‬‬ ‫‪294.8‬‬ ‫‪589.4‬‬
‫‪[C12H22O11]t = [A]t = (a 0.0965‬‬ ‫‪0.0803‬‬ ‫‪0.0713‬‬ ‫‪0.0598‬‬ ‫‪0.0328‬‬ ‫‪0.0111‬‬
‫)‪– x‬‬
‫‪x = [A]0 – [A] = a – ( a – 0.0025‬‬ ‫‪0.0187‬‬ ‫‪0.0277‬‬ ‫‪0.0392‬‬ ‫‪0.0662‬‬ ‫‪0.0879‬‬
‫)‪x‬‬
‫‪2.303‬‬ ‫‪ a  min-1‬‬ ‫‪0.00260‬‬ ‫‪0.00351 0.00352 0.00353 0.00375 0.00371‬‬
‫= ‪k1‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪t‬‬ ‫‪a-x‬‬
‫‪1‬‬ ‫‪x‬‬ ‫‪‬‬ ‫‪0.02665‬‬ ‫‪0.0395‬‬ ‫‪0.0421‬‬ ‫‪0.0463‬‬ ‫‪0.0691‬‬ ‫‪0.1357‬‬
‫= ‪k2‬‬ ‫‪‬‬ ‫‪‬‬
‫‪t  a ( a - x) ‬‬
‫‪1 1‬‬ ‫‪1‬‬ ‫‪0.273‬‬ ‫‪0.445‬‬ ‫‪0.508‬‬ ‫‪0.621‬‬ ‫‪1.403‬‬ ‫‪6.7986‬‬
‫= ‪k3‬‬ ‫‪‬‬ ‫‪- 2‬‬
‫‪2t  ( a - x ) a ‬‬
‫‪2‬‬

‫)‪(671‬‬
‫ﻣﻤﺎ ﺳﺒﻖ ﯾﺘﻀﺢ أن ﻗﯿﻢ )‪ (k1‬ﺗﻜﺎد ﺗﻜﻮن ﻣﺘﻘﺎرﺑﺔ ﺟﺪاً ﻟ ﺬا ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ‬

‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪ ،‬وأن ﻣﺘﻮﺳﻂ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ھﻮ ‪:‬‬
‫‪ 0.00260 + 0.00351 + 0.00352 + 0.00353 + 0.00375 + 0.00371 ‬‬
‫‪k1 = ‬‬ ‫‪‬‬
‫‪‬‬ ‫‪6‬‬ ‫‪‬‬
‫‪k1 = 0.00344‬‬
‫ﻣﺜﺎﻝ )‪(١١١-٢‬‬
‫‪ (326‬ﻓ ﺈن ﻋﻤﻠﯿ ﺔ ازدواج اﻟﺼ ﯿﻐﺔ‬ ‫ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة )‪ºC‬‬

‫)‪ (dimerization‬ﻟﻠﺒﯿﻮﺗ ﺎداﯾﯿﻦ ﺗﺤ ﺪث ﺑﺸ ﻜﻞ ﻏﯿ ﺮ ﻣﺘﺠ ﺎﻧﺲ ﻓ ﻲ‬
‫اﻟﻄﻮر اﻟﻐﺎزي‪ .‬واﻟﺠﺪول اﻟﺘﺎﻟﻲ ﯾﺒﯿﻦ اﻟﻌﻼﻗﺔ ﺑﯿﻦ اﻟﺰﻣﻦ )‪ (t‬واﻟﻀﻐﻂ‬
‫اﻟﻜﻠﻲ )‪.(P‬‬
‫‪t, min.‬‬ ‫‪0‬‬ ‫‪20.78‬‬ ‫‪49.50‬‬ ‫‪77.57‬‬ ‫‪103.58‬‬
‫)‪total pressure, Pt (mmHg‬‬ ‫‪632.0‬‬ ‫‪556.9‬‬ ‫‪498.1‬‬ ‫‪464.1‬‬ ‫‪442.6‬‬
‫ﻓﻤ ﺎ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ؟ وﻣ ﺎ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ؟ أﺟ ﺐ ﻋﻠ ﻰ اﻟﺴ ﺆال ﺑﺪﻻﻟ ﺔ‬

‫اﻟﻤﻌﺎدﻻت واﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ‪.‬‬
‫ﺍﳊﻞ‬
‫ﻣﻌﺎدﻟﺔ ﻋﻤﻠﯿﺔ ازدواج اﻟﺼﯿﻐﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪Butadiene ‬‬
‫‪→ 12 Dimer‬‬

‫)‪(672‬‬
‫واﻟﻀﻐﻮط اﻟﺠﺰﺋﯿﺔ ﻟﻠﺒﯿﻮﺗﺎداﯾﯿﻦ )‪ (PB‬واﻟﺪاﯾﻤﺮ )‪ (PD‬ﻣﺠﻤﻮﻋﮭﺎ ﯾﻤﺜﻞ‬

‫اﻟﻀﻐﻂ اﻟﻜﻠﻲ )‪: (P‬‬
‫‪P = PB + PD‬‬
‫وإذا ﻛ ﺎن اﻟﻀ ﻐﻂ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻠﺒﯿﻮﺗ ﺎداﯾﯿﻦ ھ ﻮ )‪ (P0‬ﻓ ﺈن اﻟﻀ ﻐﻂ ﺑﻌ ﺪ‬

‫زﻣﻦ )‪: (t‬‬
‫‪ ‬‬
‫‪Butadiene‬‬ ‫‪→ 12 Dimer‬‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫‪P -x‬‬
‫‪o‬‬ ‫‪1x‬‬
‫‪2‬‬
‫‪PB = Po - x‬‬
‫‪1‬‬
‫= ‪PD‬‬ ‫‪2‬‬ ‫‪x‬‬
‫‪P = PB + PD‬‬
‫‪P = ( Po - x ) + 12 x‬‬
‫‪P = Po - x + 12 x‬‬
‫‪1‬‬
‫‪P = Po -‬‬ ‫‪2‬‬ ‫‪x‬‬
‫‪⇒ 12 x = Po − P‬‬
‫) ‪x = 2 ( Po − P‬‬
‫‪x = 2Po − 2P‬‬
‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﺿﻐﻂ )‪ (PB‬واﻟﺬي ﯾﻤﺜﻞ )‪ (a- x‬ﯾﻤﻜﻦ أن ﯾﺤﺴ ﺐ ﻛﻤ ﺎ‬

‫ﯾﻠﻲ ‪:‬‬
‫‪PB = Po - y‬‬
‫) ‪PB = Po - ( 2Po − 2P‬‬
‫‪PB = Po - 2Po + 2P‬‬
‫) ‪PB = 2P - Po = ( a - x‬‬

‫)‪(673‬‬
‫‪‬‬ ‫‪a ‬‬

‫ﺗﺆول اﻟﻰ ‪:‬‬ ‫= ‪k‬‬
‫‪2.303‬‬
‫‪log‬‬ ‫‪‬‬ ‫وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‬
‫‪‬‬ ‫‪t‬‬ ‫‪a-x‬‬
‫‪2.303‬‬ ‫‪ Po ‬‬

‫=‪k‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪t‬‬ ‫‪ 2P - Po ‬‬
‫‪‬‬ ‫‪ Po  ‬‬
‫ﯾﻤﻜﻦ إﺛﺒﺎت أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ‬ ‫= ‪ k‬‬
‫‪2.303‬‬
‫‪log ‬‬ ‫‪ ‬‬ ‫وﻣﻦ اﻟﻌﻼﻗﺔ‬
‫‪‬‬ ‫‪t‬‬ ‫‪ 2P - Po  ‬‬
‫اﻷوﻟﻰ أو ﻻ ﺑﻄﺮﯾﻘﺘﻲ اﻟﺤﺴﺎب واﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ‪.‬‬

‫أوﻻً طﺮﯾﻘ ﺔ ﺣﺴ ﺎب ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ )‪ (k‬ﻋﻠ ﻰ اﻓﺘ ﺮاض أن‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫‪(Po)t = 0 = 632 mmHg‬‬
‫‪t, min‬‬ ‫‪0‬‬ ‫‪20.78‬‬ ‫‪49.50‬‬ ‫‪77.57 103.58‬‬
‫)‪total pressure, P (mmHg‬‬ ‫‪632.0‬‬ ‫‪556.9‬‬ ‫‪498.1‬‬ ‫‪464.1 442.6‬‬
‫‪ Po ‬‬
‫‪log ‬‬ ‫‪‬‬ ‫‪0.118 0.2394 0.3291 0.3972‬‬
‫‪ 2P - Po ‬‬
‫‪2.303‬‬ ‫‪ Po ‬‬
‫=‪k‬‬ ‫‪log ‬‬ ‫‪‬‬ ‫‪0.0131 0.0111 0.0098 0.0088‬‬
‫‪t‬‬ ‫‪ 2P - Po ‬‬
‫ﻧﻼﺣﻆ أن ﻗﯿﻢ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻏﯿﺮ ﻣﺘﺴﺎوﯾﺔ أو ﻣﺘﻘﺎرﺑ ﺔ وﺑﺎﻟﺘ ﺎﻟﻲ‬
‫ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻻ ﯾﻤﻜﻦ أن ﯾﻜﻮن ﻣﻦ ﺗﻔﺎﻋﻼت اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫واﻟﺘ ﻲ‬ ‫‪‬‬
‫= ‪ k‬‬
‫‪2.303‬‬ ‫‪ Po  ‬‬
‫‪log ‬‬ ‫‪ ‬‬ ‫ﺛﺎﻧﯿ ﺎ ً ‪ :‬طﺮﯾﻘ ﺔ اﻟﺮﺳ ﻢ اﻟﺒﯿ ﺎﻧﻲ ﻟﻠﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪t‬‬ ‫‪ 2P - Po  ‬‬
‫‪ Po‬‬ ‫‪  k ‬‬

‫واﻟﺘ ﻲ ﯾﻤﻜ ﻦ ﺗﻤﺜﯿﻠﮭ ﺎ‬ ‫‪log ‬‬ ‫‪=‬‬ ‫‪t‬‬ ‫ﯾﻤﻜ ﻦ ﺗﺤﻮﯾﺮھ ﺎ اﻟ ﻰ ‪:‬‬
‫‪ 2P - Po‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪2.303‬‬ ‫‪‬‬
‫‪ Po ‬‬
‫ﻣﻘﺎﺑ ﻞ )‪ (t‬ﻓﻨﺤﺼ ﻞ إذا ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬ ‫‪log ‬‬ ‫‪‬‬ ‫ﺑﺮﺳ ﻢ‬
‫‪ 2P - Po ‬‬

‫)‪(674‬‬
‫‪ k ‬‬
‫‪‬‬ ‫‪‬‬ ‫اﻷوﻟ ﻰ ﻋﻠ ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ ﺑﻨﻘﻄ ﺔ اﻷﺻ ﻞ ﻣﯿﻠ ﮫ‬
‫‪ 2.303 ‬‬
‫)ﺷﻜﻞ ‪.(٣٥-٢‬‬
‫وﺑﻤﺎ أن اﻟﻌﻼﻗﺔ ﻏﯿﺮ ﺧﻄﯿﺔ ﻓﺎﻟﺘﻔﺎﻋﻞ ﻟﯿﺲ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﺷﻜﻞ )‪(٣٥-٢‬‬
‫واﻵن ﻧﻔ ﺮض أن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ اﻟﺘ ﻲ ﻟﮭ ﺎ اﻟﻌﻼﻗ ﺔ ‪:‬‬

‫‪1 x ‬‬
‫‪ ( x = 2P‬و )‪ ( a - x = 2P - P‬و )‪(a = Po‬‬ ‫‪o‬‬ ‫) ‪− 2P‬‬ ‫وﺣﯿ ﺚ أن‬ ‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪at  a - x ‬‬
‫‪‬‬ ‫‪1  x ‬‬

‫إﻟﻰ ‪:‬‬ ‫‪ k = at  a - x  ‬‬ ‫ﺗﺆول اﻟﻤﻌﺎدﻟﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬

‫)‪(675‬‬
‫‪1  2Po − 2P ‬‬

‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪Po t  2P - Po ‬‬
‫وﺑﺤﺴﺎب ﻗﯿﻢ )‪ (k‬ﻋﻨﺪ أزﻣﻨﺔ ﻣﺨﺘﻠﻔﺔ ‪:‬‬

‫‪(Po)t = 0 = 632 mmHg‬‬
‫‪t, min‬‬ ‫‪0‬‬ ‫‪20.78‬‬ ‫‪49.50‬‬ ‫‪77.57‬‬ ‫‪103.58‬‬
‫)‪total pressure, P (mmHg‬‬ ‫‪632.0‬‬ ‫‪556.9‬‬ ‫‪498.1‬‬ ‫‪464.1‬‬ ‫‪442.6‬‬
‫‪2Po − 2P‬‬ ‫‪150.2‬‬ ‫‪267.8‬‬ ‫‪335.8‬‬ ‫‪378.8‬‬
‫‪2P - Po‬‬ ‫‪481.8‬‬ ‫‪364.2‬‬ ‫‪296.2‬‬ ‫‪253.2‬‬
‫‪ 2Po − 2P ‬‬ ‫‪0.3117‬‬ ‫‪0.7353‬‬ ‫‪1.1337‬‬ ‫‪1.4960‬‬
‫‪‬‬ ‫‪‬‬
‫‪ 2P - Po ‬‬
‫‪1  2Po − 2P ‬‬ ‫‪2.37‬‬ ‫‪2.35‬‬ ‫‪2.31‬‬ ‫‪2.30‬‬
‫=‪k‬‬ ‫‪‬‬ ‫‪‬‬
‫‪Po t  2P - Po ‬‬ ‫×‬ ‫×‬ ‫×‬ ‫×‬
‫‪10-5‬‬ ‫‪10-5‬‬ ‫‪10-5‬‬ ‫‪10-5‬‬
‫وﻣ ﻦ ﺣﺴ ﺎب ﻗﯿﻤ ﺔ )‪ (k‬ﻋﻤﻠﯿ ﺎ ً ﯾﻈﮭ ﺮ ﺗﻘ ﺎرب اﻟﻘ ﯿﻢ ﺟ ﺪاً ﻋﻨ ﺪ أزﻣﻨ ﺔ‬

‫ﻣﺨﺘﻠﻔﺔ‪ ،‬ﻣﻤﺎ ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪ .‬وﻣﻌ ﺪل ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋﻞ ھﻮ ‪:‬‬
‫=‪k‬‬
‫) ‪( 2.37 + 2.35 + 2.31 + 2.30‬‬ ‫‪× 10-5‬‬
‫‪4‬‬
‫‪k = 2.332 × 10 mmHg-1 min -1‬‬
‫‪-5‬‬
‫‪2.332 × 10-5‬‬
‫=‪k‬‬
‫‪‬‬ ‫‪‬‬
‫) ‪ 760 mmHg atm-1  × (101325 N m atm‬‬ ‫) ‪(1 min × 60 s min‬‬
‫‪1 mmHg‬‬ ‫‪-2‬‬ ‫‪-1‬‬ ‫‪-1‬‬
‫‪‬‬ ‫‪‬‬
‫‪k = 2 × 10-9 m 2 N -1s -1‬‬
‫ﺑﯿﺎﻧﯿﺎ ً ﺑﻌﺪ ﺗﺤﻮﯾﺮھﺎ ﻟﺘﺼﺒﺢ ﻋﻠ ﻰ‬ ‫=‪k‬‬

‫‪1  2Po − 2P ‬‬
‫‪‬‬ ‫‪‬‬
‫‪Po t  2P - Po ‬‬
‫وﯾﻤﻜﻦ رﺳﻢ اﻟﻌﻼﻗﺔ‬
‫اﻟﺼﻮرة ‪:‬‬

‫)‪(676‬‬
‫‪ 2Po − 2P ‬‬

‫‪‬‬ ‫‪ = ( k Po ) t‬‬
‫‪‬‬ ‫‪2P‬‬ ‫‪-‬‬ ‫‪P‬‬‫‪o ‬‬
‫وھ ﻲ ﺗﻤﺜ ﻞ ﻣﻌﺎدﻟ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ ﺑﻨﻘﻄ ﺔ اﻷﺻ ﻞ‪ ،‬ﻣﯿﻠ ﮫ ﯾﺴ ﺎوي‬

‫)‪.(slope = k Po‬‬
‫‪ 2Po − 2P ‬‬
‫ﻋﻠ ﻰ ﻣﺤ ﻮر اﻟﺼ ﺎدات‪ ،‬ﻣﻘﺎﺑ ﻞ )‪ (t‬ﻋﻠ ﻰ ﻣﺤ ﻮر‬ ‫‪‬‬ ‫‪‬‬ ‫وﺑﺘﻤﺜﯿﻞ‬
‫‪ 2P - Po ‬‬
‫ﺎوي‬ ‫ﮫ ﯾﺴ‬ ‫ﻰ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ‬ ‫ﻞ ﻋﻠ‬ ‫اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ‬

‫)‪) (slope = k Po = k (632‬ﺷﻜﻞ ‪.(٣٦-٢‬‬
‫وﻣﻦ اﻟﺸﻜﻞ )‪ (٣٦-٢‬ﯾﻈﮭ ﺮ أن اﻟﻌﻼﻗ ﺔ ھ ﻲ ﻋﻼﻗ ﺔ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ ﯾﻤ ﺮ‬
‫ﺑﻨﻘﻄ ﺔ اﻷﺻ ﻞ‪ ،‬ﻣﻤ ﺎ ﯾﺜﺒ ﺖ أن اﻟﺘﻔﺎﻋ ﻞ ﺣﻘ ﺎ ً ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‪ .‬وﻣﯿ ﻞ‬
‫اﻟﺨﻂ ﻣﻦ ھﺬا اﻟﻤﺴﺘﻘﯿﻢ ‪:‬‬
‫‪slope = 0.014min -1‬‬
‫‪slope = k Po‬‬
‫‪slope‬‬
‫=‪k‬‬
‫‪Po‬‬
‫‪0.014 min -1‬‬
‫=‪k‬‬
‫‪632 mmHg‬‬
‫‪k = 2.215 × 10-5 mmHg -1 min -1‬‬

‫)‪(677‬‬
‫ﺷﻜﻞ )‪(٣٦-٢‬‬
‫وﺑﺘﺤﻮﯾ ﻞ وﺣ ﺪة اﻟﺘﺮﻛﯿ ﺰ )وﺣ ﺪة اﻟﻀ ﻐﻂ ‪ (mm Hg‬اﻟ ﻰ )‪(N/m2‬‬

‫واﻟﺰﻣﻦ ﺑﺎﻟﺜﺎﻧﯿﺔ ﻧﺘﺒﻊ ﻣﺎ ﯾﻠﻲ ‪:‬‬
‫‪2.215 × 10-5‬‬
‫=‪k‬‬
‫‪‬‬ ‫‪‬‬
‫)‪ 760(mmHg/atm)  × (101325 N m atm ) (60 s‬‬
‫‪1 mmHg‬‬ ‫‪-2‬‬ ‫‪-1‬‬
‫‪‬‬ ‫‪‬‬
‫‪k = 2 × 10-9 m 2 N -1s -1‬‬

‫)‪(678‬‬
‫ﺗﻔﺎﻋﻼﺕ ﺍﻟﺮﺗﺒﺔ ﺍﻟﻈﺎﻫﺮﻳﺔ‬

‫‪Pseudo Order Reactions‬‬
‫ﯾﻮﺟﺪ ﺗﻔﺎﻋﻼت ﻛﯿﻤﯿﺎﺋﯿﺔ ﻛﺜﯿﺮة ﺗﺤﻘﻖ ﻋﻠﻰ ﺳ ﺒﯿﻞ اﻟﻤﺜ ﺎل ﻗ ﺎﻧﻮن ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻋﻠ ﻰ اﻟ ﺮﻏﻢ ﻣ ﻦ أﻧﮭ ﺎ ﺛﻨﺎﺋﯿ ﺔ أو ﺛﻼﺛﯿ ﺔ‬
‫اﻟﺠﺰﯾﺌﯿﺔ ﺣﯿﺚ ﺗﺒ ﺪو وﻛﺄﻧﮭ ﺎ ﻣ ﻦ رﺗﺒ ﺔ أﺧ ﺮى‪ ،‬وھ ﺬا ﯾﻌﻨ ﻲ أن ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋ ﻞ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ ﺗﺮﻛﯿ ﺰ إﺣ ﺪى اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ وﻣﺴ ﺘﻘﻠﺔ ﻋ ﻦ‬
‫ﺗﺮاﻛﯿ ﺰ اﻟﻤ ﻮاد اﻷﺧ ﺮى‪ ،‬وﻟﻘ ﺪ دﻟ ﺖ اﻟﺘﺠ ﺎرب ﻋﻠ ﻰ أن وﺟ ﻮد ﺗﺮﻛﯿ ﺰ‬
‫ﻣﺎدة أو أﻛﺜﺮ ﻣﻦ اﻟﻤﻮاد اﻟﻤﺸ ﺘﺮﻛﺔ ﻓ ﻲ اﻟﺘﻔﺎﻋ ﻞ ﺑﻜﻤﯿ ﺔ زاﺋ ﺪة ﻓ ﻲ ﺣﯿ ﺰ‬
‫اﻟﺘﻔﺎﻋﻞ ﯾﺒﻘﻲ ﺗﺮﻛﯿﺰھﺎ )أو ﺗﺮاﻛﯿﺰھﺎ( ﺛﺎﺑﺘ ﺎ ً ﺗﻘﺮﯾﺒ ﺎ ً ﺧ ﻼل اﻟﺘﻔﺎﻋ ﻞ ﻣﻤ ﺎ‬
‫ﯾﺆدي اﻟﻰ أن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻻ ﺗﺘ ﺄﺛﺮ ﺑﺸ ﻜﻞ ﻣﻠﺤ ﻮظ ﺑﮭ ﺬا اﻟﺘﺮﻛﯿ ﺰ أو‬
‫اﻟﺘﺮاﻛﯿﺰ‪ ،‬وﺳﻮف ﺗﻈﮭﺮ ﻗﯿﻤﺔ ﺗﺮﻛﯿﺰ ھ ﺬه اﻟﻤ ﺎدة أو ﻗ ﯿﻢ ھ ﺬه اﻟﺘﺮاﻛﯿ ﺰ‬
‫ﺿﻤﻦ ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ )‪.(k‬‬
‫ﻛﻤﺎ ھﻮ اﻟﺤﺎل ﻓﻲ ﺗﺤﻠﻞ ﻛﺒﺮﯾﺘﯿﺪ اﻟﻜﺮﺑﻮﻧﯿﻞ )‪: (Carbonyl Sulfide‬‬
‫‪COS + H 2 O ‬‬
‫‪→ CO 2 + H 2S‬‬
‫وﺗﻤﯿﺆ اﻹﺳﺘﺮ ‪:‬‬

‫‪CH 3COOC2 H 5 + H 2 O ‬‬
‫‪→ CH 3COOH + C2 H5 OH‬‬
‫وﻣﻦ اﻟﻮاﺿﺢ أن ﻛﻼً ﻣﻦ ھﺬﯾﻦ اﻟﺘﻔﺎﻋﻠﯿﻦ ﯾﺘﻜﻮن ﻣﻦ ﻣﺘﻔﺎﻋﻠﯿﻦ أﺣﺪھﻤﺎ‬

‫اﻟﻤﺎء وھﺬا ﯾﻌﻨﻲ أن ھﺬﯾﻦ اﻟﺘﻔﺎﻋﻠﯿﻦ ﺛﻨﺎﺋﯿﻲ اﻟﺠﺰﯾﺌﯿﺔ ﻟﻜﻦ وﺟ ﻮد اﻟﻤ ﺎء‬

‫)‪(679‬‬
‫ﺑﻜﻤﯿ ﺔ ﻛﺒﯿ ﺮة ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﻤﺘﻔﺎﻋ ﻞ اﻵﺧ ﺮ أﻣ ﺮ ﯾﺠﻌ ﻞ اﻟﺘﻐﯿ ﺮ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ‬

‫اﻟﻤﺎء طﻔﯿﻔﺎ ً ﺟﺪاً أﺛﻨ ﺎء اﻟﺘﻔﺎﻋ ﻞ وﺑ ﺬﻟﻚ ﯾﻤﻜ ﻦ اﻋﺘﺒ ﺎر ﺗﺮﻛﯿ ﺰه ﺛﺎﺑﺘ ﺎ ً ﻣ ﻦ‬
‫اﻟﻨﺎﺣﯿﺔ اﻟﻌﻤﻠﯿﺔ ﻣﻤﺎ ﯾﺠﻌ ﻞ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ وإذا ﻣ ﺎ رﺟﻌﻨ ﺎ‬
‫اﻟﻰ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪COS + H 2 O ‬‬
‫‪→ CO2 + H 2S‬‬
‫ورﻣﺰﻧﺎ ﻟﻜﺒﺮﯾﺘﯿﺪ اﻟﻜﺮﺑﻮﻧﯿﻞ ﺑﺎﻟﺮﻣﺰ )‪ (A‬وﻟﻠﻤﺎء ﺑﺎﻟﺮﻣﺰ )‪ (B‬ﻓﺈن ‪:‬‬

‫‪aA + bB ‬‬
‫‪→ cC + dD‬‬
‫‪a-x b-x‬‬ ‫‪c+x d+x‬‬
‫أي أن ‪:‬‬
‫‪dx‬‬
‫‪-‬‬ ‫)‪= k 2 (a - x)(b - x‬‬
‫‪dt‬‬
‫وﺣﯿ ﺚ أن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎء ﯾﻌﺘﺒ ﺮ ﺛﺎﺑﺘ ﺎ ً ﻓ ﺈن )‪ b = (b – x‬وﺗﺼ ﺒﺢ‬

‫اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪dx‬‬
‫‪-‬‬ ‫)‪= k 2 (a - x)(b‬‬
‫‪dt‬‬
‫‪ dx‬‬ ‫‪‬‬
‫‪:‬‬ ‫‪ - = k 2 (a - x)(b) ‬‬ ‫وﺑﺈﻋﺎدة ﺗﺮﺗﯿﺐ اﻟﻤﻌﺎدﻟﺔ‬
‫‪ dt‬‬ ‫‪‬‬
‫‪dx‬‬
‫‪-‬‬ ‫‪= k 2 b dt‬‬
‫)‪(a - x‬‬
‫‪ dx‬‬ ‫‪‬‬

‫‪:‬‬ ‫‪-‬‬ ‫‪= k 2 b dt ‬‬ ‫وﺑﺘﻜﺎﻣﻞ اﻟﻤﻌﺎدﻟﺔ‬
‫)‪ (a - x‬‬ ‫‪‬‬

‫)‪(680‬‬
‫‪dx‬‬
‫‪-‬‬ ‫‪= k 2 b dt‬‬
‫)‪(a - x‬‬
‫‪a-x‬‬ ‫‪t‬‬
‫‪dx‬‬
‫‪-‬‬ ‫∫‬‫‪a‬‬
‫)‪(a - x‬‬
‫‪= k 2 b ∫ dt‬‬
‫‪t=0‬‬
‫أي أن ‪:‬‬
‫‪2.303‬‬ ‫‪a‬‬
‫= ‪k = k 2b‬‬ ‫‪log‬‬
‫‪t‬‬ ‫) ‪(a - x‬‬
‫وھﺬه ھﻲ ﻧﻔﺴﮭﺎ ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬
‫‪2.303‬‬ ‫‪[ A ]0‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫]‪[A‬‬
‫وإذا أﺧﺬﻧﺎ ﻋﻠﻰ ﺳﺒﯿﻞ اﻟﻤﺜﺎل ﺗﻤﯿﺆ ﺧﻼت اﻹﯾﺜﯿﻞ ‪:‬‬

‫‪CH3COOC2 H5 + H2 O ‬‬
‫‪→ CH3 COOH + C2 H5 OH‬‬
‫ﺣﯿﺚ ﯾﺴﺘﺨﺪم اﻟﻤﺎء ﻛﻤ ﺎدة ﻣﺘﻔﺎﻋﻠ ﺔ وﻛﻤ ﺬﯾﺐ ﻓ ﻲ اﻟﻮﻗ ﺖ ﻧﻔﺴ ﮫ‪ .‬وﯾﺒ ﺪو‬
‫أن ﻗﺎﻧﻮن ﺳﺮﻋﺔ ھﺬا اﻟﺘﻔﺎﻋﻞ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫] ‪d[CH 3COOC 2 H 5‬‬
‫‪-‬‬ ‫]‪= k [CH3COOC2 H5 ][H2 O‬‬
‫‪dt‬‬
‫ﻓﻠ ﻮ اﻓﺘﺮﺿ ﻨﺎ أن اﻟﺘﻔﺎﻋ ﻞ ﺑ ﺪأ ﺑﺘﺮاﻛﯿ ﺰ اﺑﺘﺪاﺋﯿ ﺔ ﻟﻠﻤ ﺎء وﺧ ﻼت اﻹﯾﺜﯿ ﻞ‬

‫ﺗﺴﺎوي )‪ (55.6 M‬و )‪ (0.1 M‬ﻋﻠﻰ اﻟﺘﻮاﻟﻲ‪ ،‬وﺗﺤﻠﻠﺖ ﺟﻤﯿﻊ ﺧ ﻼت‬
‫اﻹﯾﺜﯿ ﻞ ﻓ ﺈن ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎء ﺳ ﻮف ﯾ ﻨﺨﻔﺾ ﺑﻤﻘ ﺪار )‪ ،(0.1 M‬وھ ﺬا‬

‫)‪(681‬‬
‫اﻻﻧﺨﻔﺎض ﯾﻌﺘﺒﺮ ﻗﻠﯿﻞ ﺟ ﺪاً ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻠﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ﻟﻠﻤ ﺎء‪ ،‬ﻟ ﺬا ﻓﺈﻧ ﮫ‬
‫ﯾﻤﻜ ﻦ اﻋﺘﺒ ﺎر ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎء ﺛﺎﺑﺘ ﺎ ً ﺗﻘﺮﯾﺒ ﺎ ً ﺧ ﻼل اﻟﺘﻔﺎﻋ ﻞ‪ ،‬وﯾﻤﻜ ﻦ ﺿ ﻢ‬
‫ﻗﯿﻤﺘﮫ ﻣﻊ اﻟﺜﺎﺑﺖ )‪ (k‬أي أن ‪:‬‬
‫]‪K = k' [H2O‬‬
‫] ‪ d[CH 3COOC 2 H 5‬‬ ‫‪‬‬
‫‪-‬‬ ‫‪= k [CH 3COOC 2 H 5 ][H 2O] ‬‬ ‫وﺑﺘﻌﻮﯾﺾ ذﻟﻚ ﻓﻲ اﻟﻤﻌﺎدﻟ ﺔ‬
‫‪‬‬ ‫‪dt‬‬ ‫‪‬‬
‫ﻓﺈﻧﮭﺎ ﺗﺆول اﻟﻰ ‪:‬‬

‫] ‪d[CH 3COOC 2 H 5‬‬
‫‪-‬‬ ‫] ‪= k' [CH 3COOC 2 H 5‬‬
‫‪dt‬‬
‫ﺔ‬ ‫ﺎ ً ﻟﻠﻤﻌﺎدﻟ‬ ‫ﻞ طﺒﻘ‬ ‫ﺬا اﻟﺘﻔﺎﻋ‬ ‫ﺮھ‬ ‫وﯾﻌﺘﺒ‬

‫] ‪ d[CH3COOC2 H5‬‬ ‫‪‬‬
‫ﺗﻔ ﺎﻋﻼً ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬ ‫‪-‬‬ ‫‪= k' [CH3COOC2 H5 ] ‬‬
‫‪‬‬ ‫‪dt‬‬ ‫‪‬‬
‫ﻋﻠ ﻰ اﻟ ﺮﻏﻢ ﻣ ﻦ أﻧ ﮫ ﯾﺒ ﺪو ﻛﺄﻧ ﮫ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ وﻓﻘ ﺎ ً ﻟﻠﻤﻌﺎدﻟ ﺔ‬

‫‪ ،  - d[CH COOC‬وﯾﻄﻠﻖ ﻋﻠ ﻰ ھ ﺬا اﻟﻨ ﻮع‬ ‫] ‪H‬‬
‫‪3‬‬ ‫‪2‬‬ ‫‪5‬‬ ‫‪‬‬
‫‪= k [CH COOC H ][H O] ‬‬
‫‪3‬‬ ‫‪2‬‬ ‫‪5‬‬ ‫‪2‬‬
‫‪‬‬ ‫‪dt‬‬ ‫‪‬‬
‫ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ اﻟﻈﺎھﺮﯾ ﺔ‪ ،‬أﻣ ﺎ اﻟﺜﺎﺑ ﺖ )'‪(k‬‬

‫ﻓﯿﺴﻤﻰ ﺑﺜﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺠﺮﯾﺒﻲ‪ ،‬أو ﺛﺎﺑﺖ ﺳﺮﻋﺔ ﺗﻔﺎﻋﻞ اﻟﺮﺗﺒ ﺔ‬
‫اﻷوﻟ ﻰ اﻟﻈ ﺎھﺮي‪ ،‬ووﺣﺪاﺗ ﮫ ھ ﻲ وﺣ ﺪات ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬
‫ﺔ‬ ‫ﻲ اﻟﻤﻌﺎدﻟ‬ ‫ﺖ )‪ (k‬ﻓ‬ ‫ﺎ اﻟﺜﺎﺑ‬ ‫ﻰ‪ .‬أﻣ‬ ‫ﺔ اﻷوﻟ‬ ‫اﻟﺮﺗﺒ‬
‫] ‪ d[CH 3COOC2 H5‬‬ ‫‪‬‬
‫ﻓﯿﺴ ﻤﻰ ﺑﺜﺎﺑ ﺖ اﻟﺘﻔﺎﻋ ﻞ‬ ‫‪-‬‬ ‫‪= k [CH3COOC2 H5 ][H2 O]‬‬
‫‪‬‬ ‫‪dt‬‬ ‫‪‬‬

‫)‪(682‬‬
‫اﻟﺤﻘﯿﻘ ﻲ‪ ،‬وﻗﯿﻤﺘ ﮫ ﺗﺴ ﺎوي ﺣﺎﺻ ﻞ ﻗﺴ ﻤﺔ ﻗﯿﻤ ﺔ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬

‫اﻟﻈﺎھﺮي )'‪ (k‬ﻋﻠﻰ اﻟﺘﺮﻛﯿﺰ اﻟﻤﻮﻻري ﻟﻠﻤﺎء أي أن ‪:‬‬
‫'‪k‬‬
‫=‪k‬‬ ‫‪dm3 mol-1 s -1‬‬
‫]‪[H 2 O‬‬
‫وﯾﺘﻀﺢ ﻣﻦ ذﻟﻚ أن وﺣﺪات ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﺤﻘﯿﻘ ﻲ ھ ﻲ ﻧﻔ ﺲ‬

‫وﺣﺪات ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬
‫ﺗﻔﺎﻋﻞ ﻋﻨﺼﺮ ﻗﻠﻮي )‪ (M‬ﻣﻊ اﻟﻨﺸﺎدر اﻟﺴﺎﺋﻞ وھﻮ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ‪:‬‬
‫‪M + NH3 ‬‬
‫‪→ MNH 2 +1/2H 2‬‬
‫وﻷن اﻟﻨﺸﺎدر ﯾﻘﻮم ﺑﺪور اﻟﻤ ﺬﯾﺐ ﻓﮭ ﻮ ﻣﻮﺟ ﻮد ﺑﻜﻤﯿ ﺔ ﻛﺒﯿ ﺮة وﻻ ﯾﺘ ﺄﺛﺮ‬
‫ﺗﺮﻛﯿﺰه أﺛﻨﺎء اﻟﺘﻔﺎﻋﻞ‪ ،‬ﺑﯿﻨﻤﺎ ﺗﻌﺘﻤﺪ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻠ ﻰ ﺗﺮﻛﯿ ﺰ ]‪.[M‬‬
‫وﻓ ﻲ ﺣﺎﻟ ﺔ ﻋﻨﺼ ﺮ اﻟﺒﻮﺗﺎﺳ ﯿﻮم )‪ (K‬ﻧﺠ ﺪ أن اﻟﺘﺮﻛﯿ ﺰ اﻟﻤﻨﺎﺳ ﺐ ھ ﻮ‬
‫)‪ (1 × 10-3 M‬ﻷﻧﮫ اﻟﻤﺆﺛﺮ اﻟﻮﺣﯿﺪ ﻓﻲ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺣﯿ ﺚ ﻧﺠ ﺪ أن‬
‫ﺗﺮﻛﯿﺰ اﻟﻨﺸﺎدر ﻏﯿﺮ ﻣﺘﻐﯿﺮ‪ .‬وﺗﻜﺘﺐ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ ﺑﺎﻟﺼﯿﻐﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫] ‪rate = k' [ M ][ NH 3‬‬
‫وﻧﻈ ﺮاً ﻷن ﻗﯿﻤ ﺔ ]‪ [NH3‬ﺛﺎﺑﺘ ﺔ ﻟ ﺬا ﻧﺠ ﺪ أن )] ‪ ( k'[ NH3‬ﯾﻜ ﻮن ﺛﺎﺑﺘ ﺎ ً‬
‫وﯾﺮﻣﺰ ﻟﮫ ﺑﺎﻟﺜﺎﺑﺖ ‪ k‬وﺗﻜﺘﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ ﺑﺎﻟﺼﯿﻐﺔ ‪:‬‬

‫] ‪rate = k [ M‬‬

‫)‪(683‬‬
‫وﻋﻠ ﻰ اﻟ ﺮﻏﻢ ﻣ ﻦ أن ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ ،‬إﻻ أﻧ ﮫ ﺣ ﺪث‬

‫ﻧﺘﯿﺠﺔ ﺗﻔﺎﻋﻞ ﻣﺎدﺗﯿﻦ وھﻤ ﺎ ﻓ ﻲ ھ ﺬه اﻟﺤﺎﻟ ﺔ اﻟﺒﻮﺗﺎﺳ ﯿﻮم )‪ (K‬واﻟﻨﺸ ﺎدر‬
‫)‪ ،(NH3‬وﻟﺬﻟﻚ ﯾﻄﻠﻖ ﻋﻠﯿﮫ ﺑﺘﻔﺎﻋﻞ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ اﻟﻈ ﺎھﺮي دون أن‬
‫ﯾﻐﯿﺮ ذﻟﻚ ﻣﻦ ﺻﯿﻐﺔ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ اﻷﺧﯿﺮة )]‪.(rate = k [M‬‬
‫وﯾﻤﻜﻦ ﻣﺘﺎﺑﻌﺔ ﺗﻔﺎﻋﻞ اﻟﺒﻮﺗﺎﺳﯿﻮم ﻣﻊ اﻟﻨﺸﺎدر ﺑﻘﯿﺎس اﻟﺘﻐﯿﺮ ﻓﻲ ﻟ ﻮن‬
‫اﻟﻤﺤﻠﻮل ﻋﻨﺪ ﻓﺘﺮات زﻣﻨﯿﺔ ﻣﻌﯿﻨﺔ‪ .‬ﻓﻔﻲ ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ﻟﻠﻤﺤﻠﻮل‬
‫ﻟﻮﻧﺎ ً أزرﻗﺎ ً داﻛﻨﺎ ً ﻟﻜﻨﮫ ﯾﺨﺘﻔﻲ ﺗ ﺪرﯾﺠﯿﺎ ً ﻓﯿﺼ ﺒﺢ ﻻ ﻟ ﻮن ﻟ ﮫ ﻋﻨ ﺪ ﻧﮭﺎﯾ ﺔ‬
‫اﻟﺘﻔﺎﻋﻞ‪ .‬وﺗﻘﺎس ﻛﻤﯿﺔ اﻟﺒﻮﺗﺎﺳﯿﻮم اﻟﺒﺎﻗﯿﺔ دون ﺗﻔﺎﻋﻞ ﻓ ﻲ أي وﻗ ﺖ ﻣ ﻦ‬
‫ﺷﺪة ﻟﻮن اﻟﻤﺤﻠﻮل ﺑﻮاﺳﻄﺔ ﻣﻘﯿﺎس طﯿﻒ اﻹﻣﺘﺼﺎص‪.‬‬
‫وﻟﻘ ﺪ رﺻ ﺪت ﺑﺎﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﻧﺘ ﺎﺋﺞ ﻗﯿﺎﺳ ﺎت اﻻﻣﺘﺼ ﺎص اﻟﻀ ﻮﺋﻲ‬
‫ﻟﻠﻤﺤﻠ ﻮل ﻋﻘ ﺐ ذوﺑ ﺎن ﻋﻨﺼ ﺮ اﻟﺒﻮﺗﺎﺳ ﯿﻮم ﻓ ﻲ ﺳ ﺎﺋﻞ اﻟﻨﺸ ﺎدر‪،‬‬
‫‪‬‬ ‫‪2.303‬‬ ‫‪[ A ]0 ‬‬
‫= ‪  k‬ﻟﺘﻌﯿﯿﻦ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‬ ‫‪t‬‬
‫‪log‬‬ ‫‪‬‬
‫‪[ A ] ‬‬ ‫واﺳﺘﺨﺪﻣﺖ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ‬
‫‪‬‬
‫)‪ (k‬ﻟﺘﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ اﻋﺘﻤ ﺎداً ﻋﻠ ﻰ ﻗﯿﺎﺳ ﺎت اﻻﻣﺘﺼ ﺎص‬
‫وﺷﺪﺗﮫ‪.‬‬

‫)‪(684‬‬
‫ﺟﺪول )‪ (٣-٢‬ﺗﻐﯿﺮ اﻟﺘﺮﻛﯿﺰ اﻟﻤﻮﻻري ﻟﻠﺒﻮﺗﺎﺳﯿﻮم ﻣﻊ اﻟﺰﻣﻦ أﺛﻨﺎء اﻟﺘﻔﺎﻋﻞ‬

‫‪K + NH 3 ‬‬
‫‪→ K + + NH -2 +‬‬ ‫‪1‬‬
‫‪2‬‬ ‫‪H2‬‬
‫اﻟﺰﻣﻦ‬
‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ‬ ‫ﻟﻮﻏﺎرﯾﺘﻢ‬
‫‪‬‬ ‫‪‬‬ ‫اﻟﺘﺮﻛﯿﺰ‬ ‫اﻟﺘﺮﻛﯿﺰ‬ ‫ﺷﺪة‬
‫= ‪k‬‬
‫‪‬‬
‫‪2.303‬‬
‫‪t‬‬
‫(‬ ‫)‬
‫‪log [K ]0 − log [K ] ‬‬
‫‪‬‬ ‫اﻟﻤﻮﻻري‬ ‫اﻟﻤﻮﻻري‬ ‫اﻟﻠﻮن‬ ‫اﻟﺰﻣﻦ ﺑﻌﺪ ﺟﻤﻊ‬ ‫دﻗﯿﻘﺔ‬ ‫ﺳﺎﻋﺔ‬
‫‪h‬‬‫‪-1‬‬ ‫اﻟﺪﻗﺎﺋﻖ واﻟﺴﺎﻋﺔ‬
‫‪h‬‬
‫‪-‬‬ ‫‪- 2.947‬‬ ‫‪[K]0 = 1.13 × 10-3‬‬ ‫‪1.702‬‬ ‫‪0‬‬ ‫‪0‬‬ ‫‪0‬‬
‫‪5.59 × 10-2‬‬ ‫‪- 3.009‬‬ ‫‪[K] = 9.80 ×10-4‬‬ ‫‪1.476‬‬ ‫‪2.55‬‬ ‫‪33‬‬ ‫‪2‬‬
‫‪5.55 × 10-2‬‬ ‫‪- 3.057‬‬ ‫‪[K] = 8.77 × 10-4‬‬ ‫‪1.322‬‬ ‫‪4.57‬‬ ‫‪34‬‬ ‫‪4‬‬
‫‪5.35 × 10-2‬‬ ‫‪- 3.100‬‬ ‫‪[K] = 7.94 × 10-4‬‬ ‫‪1.196‬‬ ‫‪6.6‬‬ ‫‪36‬‬ ‫‪6‬‬
‫‪5.55 × 10-2‬‬ ‫‪- 3.179‬‬ ‫‪[K] = 6.62 × 10-4‬‬ ‫‪0.996‬‬ ‫‪9.63‬‬ ‫‪38‬‬ ‫‪9‬‬
‫‪5.62 × 10-2‬‬ ‫‪- 3.253‬‬ ‫‪[K] = 5.59 × 10-4‬‬ ‫‪0.841‬‬ ‫‪12.52‬‬ ‫‪31‬‬ ‫‪12‬‬
‫‪5.66 × 10-2‬‬ ‫‪- 3.474‬‬ ‫‪[K] = 3.36 × 10-4‬‬ ‫‪0.506‬‬ ‫‪21.35‬‬ ‫‪26‬‬ ‫‪21‬‬
‫ﻣﺜﺎﻝ )‪(١١٢-٢‬‬
‫إذا ﻋﻠﻤﺖ أن ﺗﻤﯿﺆ ﺧﻼت اﻹﯾﺜﯿﻞ ﻓﻲ ﻣﺤﻠﻮل ﻣ ﺎﺋﻲ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬

‫ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺨﻼت ‪:‬‬
‫‪CH 3COOC2 H 5 + H 2O ‬‬
‫‪→ CH 3COOH + C 2 H5OH‬‬
‫وﻋﻨﺪ ﺗﻐﯿﯿﺮ ﻗﺎﻋﺪﯾ ﺔ اﻟﻤﺤﻠ ﻮل )‪ (pH‬ﯾﺘﻐﯿ ﺮ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬

‫اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪[H+] mol dm-3‬‬ ‫‪0.001‬‬ ‫‪0.01‬‬ ‫‪0.1‬‬
‫‪k /10-4 s-1‬‬ ‫‪1.1‬‬ ‫‪11‬‬ ‫‪110‬‬
‫أ( اﺣﺴﺐ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻨﺴﺒﺔ ﻷﯾﻮن اﻟﮭﯿﺪروﺟﯿﻦ)‪(H+‬‬

‫ب( اﺣﺴﺐ ﻗﯿﻤﺔ ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﺤﻘﯿﻘﻲ‪.‬‬

‫)‪(685‬‬
‫أ( رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺎﻟﻨﺴﺒﺔ ﻷﯾﻮن اﻟﮭﯿﺪروﺟﯿﻦ ھﻲ اﻷوﻟﻰ‬
‫ب( ﺛﺎﺑﺖ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﺤﻘﯿﻘﻲ ‪kn = k2 = 1.10 × 10-1 dm3 mol-1 s-1 :‬‬
‫ﺗﻔﺼﻞ ﺍﳊﻞ‬
‫‪............................................................................................... .........................................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪.......................................................................................................................................... ..............................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪..................................................................................................................................................................................... ...‬‬
‫‪.............................................................................................................. ..........................................................................‬‬
‫‪........................................................... .............................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪......................................................................................................................................................... ...............................‬‬
‫‪.................................................................................. ......................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪............................................................................................................................. ...........................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................................‬‬
‫‪........................................................................................................................................................................ ................‬‬
‫‪................................................................................................. .......................................................................................‬‬

‫)‪(686‬‬
‫ﺍﻟﺮﺗﺐ ﺍﻷﺧﺮﻯ‬
‫ﺗﻔﺎﻋﻼﺕ ﻣﻦ ﺍﻟﺮﺗﺒﺔ )‪(n‬‬
‫‪nth Order Reaction‬‬
‫ﻟﻘﺪ ﻟﻮﺣﻆ إﻣﻜﺎﻧﯿﺔ وﺟﻮد رﺗﺐ ﻛﺴﺮﯾﺔ ﻣﺜﻞ اﻟﻨﺼ ﻒ واﻟﺜﻼﺛ ﺔ أﻧﺼ ﺎف‬
‫ﻛﻤ ﺎ وﺟ ﺪ ﻣ ﻦ اﻟﺘﺠﺮﺑ ﺔ ﻋ ﺪد ﻗﻠﯿ ﻞ ﻣ ﻦ اﻟﺘﻔ ﺎﻋﻼت ذات اﻟﺮﺗﺒ ﺔ اﻟﺮاﺑﻌ ﺔ‬
‫ﻣﺜﻞ ﺗﻔﺎﻋﻞ اﻟﺒﺮوﻣﯿﺪ ﻣﻊ اﻟﺒﺮوﻣﺎت ﻓﻲ وﺳﻂ ﺣﺎﻣﻀﻲ ‪:‬‬
‫‪5Br - + BrO3- + 6H + ‬‬
‫‪→ 2Br2 + 3H 2 O‬‬
‫ﺣﯿﺚ ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي ‪:‬‬

‫‪2‬‬
‫‪Rate = k  Br -   BrO 3-   H + ‬‬
‫وﺳﻮف ﻧﺴﺘﻨﺘﺞ ﻓﻲ ھ ﺬا اﻟﻘﺴ ﻢ ﻣﻌﺎدﻟ ﺔ ﺗﻜﺎﻣﻠﯿ ﺔ ﻣﮭﻤ ﺔ ﺗﻜ ﻮن ﻓﯿﮭ ﺎ رﺗﺒ ﺔ‬

‫اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي )‪ (n‬ﺣﯿﺚ ﺗﺄﺧﺬ )‪ (n‬أﯾﺔ ﻗﯿﻤﺔ ﻓﯿﻤﺎ ﻋﺪا اﻟﻮاﺣ ﺪ‪ ،‬أي أن‬
‫)‪ ،(n ≠1‬ﻣﻌﻨ ﻰ ذﻟ ﻚ أﻧ ﮫ ﯾﻤﻜ ﻦ ﻋ ﻦ طﺮﯾ ﻖ ھ ﺬه اﻟﻤﻌﺎدﻟ ﺔ اﺳ ﺘﻨﺘﺎج‬
‫اﻟﻤﻌ ﺎدﻻت اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻣ ﻦ أي رﺗﺒ ﺔ ﻏﯿ ﺮ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﺳ ﻮا ًء ﻛﺎﻧ ﺖ‬
‫ﻗﯿﻤﺔ )‪ (n‬ﻋﺪداً ﺻﺤﯿﺤﺎ ً أو ﻛﺴﺮاً‪.‬‬
‫ﻟ ﺬا ﯾﻤﻜ ﻦ إﯾﺠ ﺎد اﻟﻌﻼﻗ ﺔ اﻟﺘﻔﺎﺿ ﻠﯿﺔ واﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ اﻟﺒﺴ ﯿﻂ ﻟﻠﺮﺗﺒ ﺔ‬
‫)‪ (n‬ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬
‫‪nA ‬‬

‫)‪(687‬‬
‫وأن )‪ (a‬ﺗﻤﺜ ﻞ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻟﮭ ﺬه اﻟﻤ ﺎدة‪ ،‬و )‪ (x‬ھ ﻲ ﻣﻘ ﺪار‬
‫اﻹﻧﺨﻔﺎض ﻓﻲ ﺗﺮﻛﯿ ﺰ ھ ﺬه اﻟﻤ ﺎدة ﻋﻨ ﺪ أي زﻣ ﻦ ﻗ ﺪره )‪ (t‬ﻓ ﺈن ﻗ ﺎﻧﻮن‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ )‪ (n‬ﯾﻜﻮن ‪:‬‬
‫‪dx‬‬
‫‪= k(a - x) n‬‬
‫‪dt‬‬
‫وﺑﺘﻨﻈﯿﻢ ھﺬه اﻟﻤﻌﺎدﻟﺔ ‪:‬‬

‫‪dx‬‬
‫⇒‬ ‫‪= k dt‬‬
‫‪(a - x)n‬‬
‫‪ dx‬‬ ‫‪‬‬

‫‪(t = 0‬‬ ‫) ‪→tx‬‬
‫‪‬‬ ‫ﻋﻨ ﺪ‬ ‫‪‬‬ ‫‪n‬‬
‫‪= k dt ‬‬ ‫وﻋﻨﺪ ﻣﻜﺎﻣﻠﺔ اﻟﻌﻼﻗ ﺔ اﻟﺘﻔﺎﺿ ﻠﯿﺔ‬
‫)‪ (a - x‬‬ ‫‪‬‬
‫)إﺟﺮاء اﻟﺘﻜﺎﻣﻞ ﻟﮭﺎ ﺑ ﯿﻦ )‪ (x = 0‬ﻋﻨ ﺪﻣﺎ )‪ (t = 0‬و )‪ (x = x‬ﻋﻨ ﺪﻣﺎ‬

‫)‪ ،(t = t‬ﻟﺘﺼﺒﺢ ‪:‬‬
‫‪dx‬‬
‫=‬
‫‪(a - x) n‬‬
‫‪dx‬‬
‫‪∫0 (a - x)n ∫0 k dt‬‬
‫‪x‬‬ ‫‪t‬‬
‫=‬
‫‪dx‬‬
‫‪∫0 (a - x)n ∫0 dt‬‬
‫‪x‬‬ ‫‪t‬‬
‫=‬ ‫‪k‬‬
‫‪1‬‬
‫⇒‬ ‫‪= kt + I‬‬
‫‪( n - 1) (a - x) n -1‬‬
‫وﻋﻨﺪ )‪ (t = 0‬و )‪ (x = 0‬ﺗﺼﺒﺢ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺘﻜﺎﻣﻞ )‪: (I‬‬
‫‪1‬‬
‫=‪I‬‬
‫‪( n - 1) a n-1‬‬

‫)‪(688‬‬
‫‪‬‬ ‫‪‬‬
‫ﯾﻨﺘﺞ ‪:‬‬ ‫‪‬‬
‫‪1‬‬
‫‪= kt + I ‬‬ ‫وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ )‪ (I‬ﻓﻲ اﻟﻌﻼﻗﺔ‬
‫)‪ ( n - 1) (a - x‬‬
‫‪n -1‬‬
‫‪‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪= kt +‬‬
‫) ‪( n - 1)( a - x‬‬
‫‪n-1‬‬
‫‪( n -1) a n-1‬‬
‫‪‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪‬‬
‫ﺑﺪﻻﻟ ﺔ اﻟﺘﺮﻛﯿ ﺰ‬ ‫‪‬‬
‫‪ ( n - 1)( a - x )n-1‬‬
‫=‬ ‫‪kt‬‬ ‫‪+‬‬
‫(‬ ‫‪n‬‬ ‫‪-1‬‬‫)‬ ‫‪a‬‬ ‫‪n-1‬‬
‫‪‬‬
‫‪‬‬
‫وﺑﺘﺮﺗﯿ ﺐ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬
‫ﺗﺼﺒﺢ ‪:‬‬
‫‪1 ‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫‪‬‬ ‫‪-‬‬ ‫‪ = kt‬‬
‫‪(n - 1)  ( a - x )n-1 a n-1 ‬‬
‫‪ 1 ‬‬ ‫‪1‬‬ ‫‪1 ‬‬ ‫‪‬‬

‫ﺗﻌﺘﺒ ﺮ ﻣﮭﻤ ﺔ ﻓ ﻲ اﺳ ﺘﻨﺘﺎج‬ ‫‪‬‬ ‫‪‬‬ ‫‪-‬‬ ‫‪‬‬
‫‪ (n - 1)  ( a - x )n-1 a n-1 ‬‬
‫=‬ ‫‪kt‬‬ ‫‪‬‬
‫‪‬‬
‫واﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫اﻟﻤﻌ ﺎدﻻت اﻟﺘﻜﺎﻣﻠﯿ ﺔ ﻟﻠﺘﻔ ﺎﻋﻼت ﻣ ﻦ اﻟﺮﺗ ﺐ اﻟﺒﺴ ﯿﻄﺔ اﻟﺴ ﺎﺑﻘﺔ أو أي‬
‫رﺗﺒﺔ أﺧﺮى ﺣﯿﺚ ﺗﻨﻄﺒﻖ ﻋﻠﻰ ﺟﻤﯿﻊ اﻟﺮﺗﺐ ﻓﯿﻤﺎ ﻋﺪا اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬

‫)‪(689‬‬
‫ﻓﱰﺓ ﻧﺼﻒ ﺍﻟﻌﻤﺮ‬

‫)‪(Half Life Method‬‬
‫ﯾﻌ ﺮف ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻋﻠ ﻰ أﻧ ﮫ اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻻﺧﺘﻔ ﺎء ﻧﺼ ﻒ اﻟﻜﻤﯿ ﺔ‬
‫)اﻟﺘﺮاﻛﯿ ﺰ( اﻹﺑﺘﺪاﺋﯿ ﺔ ﻣ ﻦ اﻟﻤﺘﻔ ﺎﻋﻼت‪ ،‬وﺗﻌﺘﻤ ﺪ ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﻋﻠ ﻰ‬
‫ﻗﯿﺎس ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة ﺛﺎﺑﺘ ﺔ وﻋﻨ ﺪ ﺗﺮاﻛﯿ ﺰ اﺑﺘﺪاﺋﯿ ﺔ‬
‫ﻣﺨﺘﻠﻔ ﺔ ﻋﻠ ﻰ أن ﺗﻜ ﻮن ﺗﺮاﻛﯿ ﺰ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﺔ )إذا وﺟ ﺪ أﻛﺜ ﺮ ﻣ ﻦ‬
‫ﻣﺎدة ﻣﺘﻔﺎﻋﻠ ﺔ( داﺋﻤ ﺎ ً ﻣﺘﺴ ﺎوﯾﺔ ﺣﺘ ﻰ ﯾﻨﻄﺒ ﻖ ﻋﻠ ﻰ اﻟﺘﻔﺎﻋ ﻞ أﺣ ﺪ ﻗ ﻮاﻧﯿﻦ‬
‫اﻟﺴﺮﻋﺔ اﻟﺴﺎﺑﻖ ذﻛﺮھﺎ‪.‬‬
‫وﻣﻤ ﺎ ﺳ ﺒﻖ اﺗﻀ ﺢ أن ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻻ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ اﻟﺘﺮﻛﯿ ﺰ‬
‫‪‬‬ ‫‪0.693 ‬‬
‫‪ ،  t‬وﯾﺘﻨﺎﺳ ﺐ‬ ‫= ‪1‬‬ ‫‪‬‬ ‫اﻷﺻ ﻠﻲ ﻓ ﻲ ﺣﺎﻟ ﺔ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫‪ 2‬‬ ‫‪k ‬‬
‫‪‬‬ ‫‪‬‬
‫ﻋﻜﺴﯿﺎ ً ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻷﺻﻠﻲ ﻓ ﻲ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‬
‫‪1‬‬
‫‪،  t‬‬ ‫=‬ ‫‪‬‬
‫‪[ A ]0 k ‬‬
‫‪1‬‬
‫‪2‬‬
‫‪‬‬
‫وﯾﺘﻨﺎﺳ ﺐ ﻋﻜﺴ ﯿﺎ ً ﻣ ﻊ ﻣﺮﺑ ﻊ اﻟﺘﺮﻛﯿ ﺰ ﻓ ﻲ ﺗﻔ ﺎﻋﻼت اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻟﺜ ﺔ‬

‫‪‬‬ ‫‪3 ‬‬
‫= ‪ t1‬‬ ‫‪‬‬
‫‪ 2 2k [ A ]2 ‬‬
‫‪‬‬ ‫‪0 ‬‬
‫ﺗﺮﺳﻢ اﻟﻨﺴﺒﺔ اﻟﻤﺌﻮﯾﺔ ﻟﺘﻜﻤﻠﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻊ اﻟﺰﻣﻦ ﺛﻢ ﯾﻮﺟ ﺪ ﻧﺼ ﻒ اﻟﻌﻤ ﺮ‬

‫اﻟﻤﺴﺎوﯾﺔ ﻟﻨﺴﺒﺔ )‪.(50 %‬‬

‫)‪(690‬‬
‫ﻛﻤﺎ ﯾﻤﻜﻦ اﺳﺘﻨﺘﺎج ﻗﺎﻧﻮن ﻋﺎم ﻟﻔﺘﺮة ﻋﻤﺮ اﻟﻨﺼﻒ‪ ،‬وذﻟﻚ ﺑ ﺎﻟﺘﻌﻮﯾﺾ‬
‫ﻋﻦ ‪:‬‬
‫)‪(t = t1/2, x = a/2‬‬
‫‪1 ‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫‪‬‬ ‫‪-‬‬ ‫‪ = kt‬‬
‫‪(n - 1)  ( a - x )n-1 a n-1 ‬‬
‫‪‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫‪1 ‬‬ ‫‪1‬‬ ‫‪1 ‬‬
‫= ‪t1‬‬ ‫‪- n-1‬‬
‫‪2‬‬
‫‪(n - 1)k  ‬‬ ‫‪a‬‬
‫‪n-1‬‬
‫‪a ‬‬
‫‪a - ‬‬ ‫‪‬‬
‫‪‬‬ ‫‪2‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫‪‬‬ ‫‪‬‬
‫‪1  1‬‬ ‫‪1 ‬‬
‫= ‪t1‬‬ ‫‪-‬‬
‫‪2‬‬
‫‪(n - 1)k   a  n-1 a n-1 ‬‬
‫‪ ‬‬ ‫‪‬‬
‫‪ 2 ‬‬ ‫‪‬‬
‫)‪1  ( 2‬‬ ‫‪1 ‬‬
‫‪n-1‬‬
‫= ‪t1‬‬ ‫‪ n-1 - n-1 ‬‬

‫‪2‬‬
‫) ‪(n - 1)k  ( a‬‬ ‫‪a ‬‬
‫)‪( 2‬‬ ‫‪−1‬‬

‫‪n-1‬‬
‫= ‪⇒ t1‬‬
‫) ‪(n - 1)k ( a‬‬
‫‪2‬‬
‫‪n-1‬‬
‫‪‬‬ ‫(‬ ‫‪2) −1 ‬‬

‫‪n-1‬‬
‫ﻋﻠﻰ أن ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﺗﺘﻨﺎﺳ ﺐ‬ ‫= ‪t1‬‬ ‫‪‬‬

‫‪ 2 (n - 1)k ( a )n-1 ‬‬ ‫ﺗﺪل اﻟﻤﻌﺎدﻟﺔ‬
‫‪‬‬ ‫‪‬‬
‫ﻋﻜﺴ ﯿﺎ ً ﻣ ﻊ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ ﻣﺮﻓﻮﻋ ﺎ ً ﻟ ﻸس )‪ (n – 1‬ﻋﻠ ﻰ ﺷ ﺮط‬

‫أﯾﻀﺎ ً أن )‪.(n ≠1‬‬
‫وﺣﯿﺚ ﯾﺘﻨﺎﺳﺐ ﻧﺼﻒ اﻟﻌﻤﺮ طﺮدﯾﺎ ً ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻤﺘﻔﺎﻋﻼت‬
‫ﻣﺮﻓﻮﻋﺎ ً اﻟﻰ )‪: (1 – n‬‬

‫)‪(691‬‬
‫‪t 1 α a n-1‬‬
‫‪2‬‬
‫‪t 1 = k . a n-1‬‬
‫‪2‬‬
‫وﺑﺄﺧﺬ اﻟﻠﻮﻏﺎرﯾﺘﻢ اﻟﻌﺸﺮي )أو اﻟﻄﺒﯿﻌﻲ( ﻟﻠﻄﺮﻓﯿﻦ ﻧﺤﺼﻞ ﻋﻠﻰ ‪:‬‬

‫‪t 1 = k . a n-1‬‬
‫‪2‬‬
‫‪log t 1 = log k + (1 - n) a‬‬

‫‪2‬‬
‫و ‪ log a‬ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ ‪(1‬‬ ‫‪log t 1‬‬

‫‪2‬‬
‫ﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ ﺑﯿﻦ‬
‫)‪ – n‬وﺗﻜﻮن رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺣﺴﺐ اﻟﺠﺪول )‪.(٤-٢‬‬
‫ﺟﺪول )‪(٤-٢‬‬
‫ﻋﻼﻗﺔ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻊ اﻟﻤﯿﻞ ﻟﻌﻼﻗﺔ ﻧﺼﻒ اﻟﻌﻤﺮ‬
‫اﻟﻤﯿﻞ‬ ‫رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ )‪(n‬‬
‫‪1‬‬ ‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬
‫‪-1‬‬ ‫‪2‬‬
‫‪-2‬‬ ‫‪3‬‬
‫ﺗﻨﻄﺒﻖ طﺮﯾﻘﺔ ﻧﺼﻒ اﻟﻌﻤﺮ ﻋﻠﻰ اﻟﺘﻔﺎﻋﻼت اﻟﺒﺴﯿﻄﺔ ﻣﻦ اﻟﻨﻮع ‪:‬‬

‫‪nA ‬‬
‫ﺣﯿﺚ ﺗﻜﻮن اﻟﺮﺗﺒﺔ ﻋﺪداً ﺻﺤﯿﺤﺎ ً‪.‬‬

‫)‪(692‬‬
‫ﯾﻌﺘﻤ ﺪ زﻣ ﻦ ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻋﻠ ﻰ اﻟﺘﺮﻛﯿ ﺰ وﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪ (k‬ﺣﺴ ﺐ‬

‫رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ‪ n‬وﻓﻘﺎ ً ﻟﻠﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪2n-1 - 1‬‬
‫= ‪t1‬‬
‫‪2‬‬
‫‪( n - 1) k a n-1‬‬
‫‪‬‬ ‫‪2n-1 - 1 ‬‬
‫ﻋﻠ ﻰ اﻟﺮﺗ ﺐ )‪ (0, 2, 3‬وﻻ ﺗﻨﻄﺒ ﻖ‬ ‫= ‪ t 12‬‬ ‫‪‬‬ ‫وﺗﻨﻄﺒ ﻖ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪( n - 1) k a n-1 ‬‬
‫ﻋﻠ ﻰ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻷﺳ ﺒﺎب رﯾﺎﺿ ﯿﺔ وﯾﺒ ﯿﻦ اﻟﺠ ﺪول )‪( t ) (٥-٢‬‬
‫‪1‬‬
‫‪2‬‬
‫ﻟﺠﻤﯿﻊ اﻟﺮﺗﺐ ‪:‬‬

‫ﻟﺮﺗﺐ اﻟﺘﻔﺎﻋﻼت‬ ‫ﺟﺪول )‪( t ) : (٥-٢‬‬
‫‪1‬‬
‫‪2‬‬
‫زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ) ‪( t‬‬

‫‪1‬‬
‫‪2‬‬
‫اﻟﺮﺗﺒﺔ‬
‫‪a‬‬
‫= ‪t1‬‬ ‫‪0‬‬
‫‪2‬‬
‫‪2k‬‬
‫‪0.693‬‬
‫= ‪t1‬‬ ‫‪1‬‬
‫‪2‬‬
‫‪k‬‬
‫‪1‬‬
‫= ‪t1‬‬ ‫‪2‬‬
‫‪2‬‬
‫‪ka‬‬
‫‪3‬‬
‫= ‪t1‬‬ ‫‪3‬‬
‫‪2‬‬
‫‪2 k a2‬‬
‫ﻋﻨ ﺪ ﺗﺮﻛﯿ ﺰﯾﻦ اﺑﺘ ﺪاﺋﯿﯿﻦ‬ ‫‪t1‬‬

‫‪2‬‬
‫وﯾﻤﻜ ﻦ إﯾﺠ ﺎد رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ إذا ﻋﻠﻤﻨ ﺎ ﻗ ﯿﻢ‬
‫ﻣﺨﺘﻠﻔﯿﻦ ﺑﻤﻌﺎﻟﺠﺔ اﻟﻌﻼﻗﺔ ) ‪ ( t α a‬ﺑﺤﯿﺚ ﺗﺼﺒﺢ ﻋﻨﺪ اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ‬
‫‪1‬‬
‫‪2‬‬
‫‪n-1‬‬
‫اﻷول ‪ a1‬ﻣﺴﺎوﯾﺎ ً ‪:‬‬
‫‪( t ) α a1‬‬
‫‪1‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪n-1‬‬
‫‪1‬‬

(693)
: ً ‫ ﻣﺴﺎوﯾﺎ‬a2 ‫وﻋﻨﺪ اﻟﺘﺮﻛﯿﺰ اﻟﺜﺎﻧﻲ‬
( t ) α a1
1
2 2
n-1
2
: ‫ ( ﯾﻨﺘﺞ‬t )
1
2 2
α
1
a n-1
‫ ( ﻋﻠﻰ اﻟﻌﻼﻗﺔ‬t ) α a1 ‫وﺑﻘﺴﻤﺔ اﻟﻌﻼﻗﺔ‬
1
2 1
n-1
2 1
(t ) 1
2 1
a 
=  2
n-1
(t )
1
2 2
 a1 
: ‫أي أن‬
  
  t1  
 2 1   a2 
log  = ( n - 1) log  
    a1 
  t1  
 
  2 2 
: ‫( ﺗﺼﺒﺢ‬n) ‫أي أن رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‬

 
log  t 1 (1) / t 1 (2) 
n=1+  2 2 
log ( a 2 /a1 )

(694)
n ‫ﻃﺮﻳﻘﺔ ﺃﺧﺮﻯ ﻹﺛﺒﺎﺕ ﻧﺼﻒ ﺍﻟﻌﻤﺮ ﻟﺘﻔﺎﻋﻞ ﻣﻦ ﺍﻟﺮﺗﺒﺔ‬
‫( وﺟ ﺪ أن ﻓﺘ ﺮة ﻧﺼ ﻒ‬n) ‫ﻓﻲ اﻟﺤﺎﻟﺔ اﻟﻌﺎﻣﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ‬

: ‫اﻟﻌﻤﺮ‬
1  2( n - 1) - 1 
t1 =  
2
(n - 1)k n  [ A ]( n - 1) 
 0 
2( ) - 1  1 
n-1
t1 =  
( n - 1) 
2
(n - 1) k n [ A ]

 0 
: ‫وﺑﺄﺧﺬ اﻟﻠﻮﻏﺎرﯾﺘﻢ ﻟﻄﺮﻓﻲ اﻟﻤﻌﺎدﻟﺔ‬

2( n - 1) - 1  1 
t1 =  
2
(n - 1)k n  [ A ]( n - 1) 
 0 
2( ) - 1  1 
n-1
log t 1 = log  
2
(n - 1)k n  [ A ]( n - 1) 
 0 
 2( n - 1) - 1   1 
log t 1 = log   + log  
 ( n - 1) 
 [ A ]0 
2
 (n - 1)k n 

 2( n - 1) - 1  ( n - 1)
log t 1 = log   + log(1) − log [ A]0
 (n - 1)k n 
2
 2( n - 1) - 1  ( n - 1)
log t 1 = log  
 − log [ A]0
 (n - 1)k n 
2
 2( n - 1) - 1 
⇒ log t 1 = log   − ( n - 1) log [ A ]0
 (n - 1)k n 
2

‫)‪(695‬‬
‫‪‬‬ ‫‪ 2( n - 1) - 1 ‬‬ ‫‪‬‬

‫ﻋﻠ ﻰ ﺻ ﻮرة‬ ‫‪log t 12 = log ‬‬ ‫‪ − ( n - 1) log [ A ]0 ‬‬ ‫وﺗﺮﺗﯿ ﺐ اﻟﻌﻼﻗ ﺔ‬
‫‪‬‬ ‫‪ (n - 1)k n ‬‬ ‫‪‬‬
‫ﻣﻌﺎدﻟﺔ ﺧﻂ ﻣﺴﺘﻘﯿﻢ‬
‫‪ 2( n - 1) - 1 ‬‬
‫‪log t 1 = − ( n - 1) log [ A]0‬‬ ‫‪+ log ‬‬ ‫‪‬‬
‫‪2‬‬
‫‪‬‬ ‫‪(n‬‬ ‫‪-‬‬ ‫‪1)k‬‬ ‫‪n‬‬ ‫‪‬‬
‫‪ 2( n - 1) - 1 ‬‬
‫‪⇒ log t 1 = (1 - n ) log [ A ]0‬‬ ‫‪+ log ‬‬ ‫‪‬‬
‫‪ (n - 1)k n ‬‬
‫‪2‬‬
‫‪‬‬ ‫‪ 2( n - 1) - 1  ‬‬

‫‪log t 1‬‬ ‫ﺑﺘﻤﺜﯿ ﻞ‬ ‫‪log t 12 = (1 - n ) log [ A ]0 + log ‬‬ ‫‪ ‬‬ ‫وﺑﺮﺳﻢ اﻟﻌﻼﻗﺔ‬
‫‪2‬‬
‫‪‬‬ ‫‪ (n - 1)k n  ‬‬
‫ﻋﻠﻰ ﻣﺤ ﻮر اﻟﺴ ﯿﻨﺎت ﻧﺤﺼ ﻞ ﻋﻠ ﻰ‬ ‫‪log [ A ]0‬‬ ‫ﻋﻠﻰ ﻣﺤﻮر اﻟﺼﺎدات و‬

‫ﺧﻂ ﻣﺴﺘﻘﯿﻢ ﻣﯿﻠﮫ )‪. (1 – n‬‬
‫ﻛﻤ ﺎ ﯾﻤﻜ ﻦ ﺗﺤﺪﯾ ﺪ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺘﺤﺪﯾ ﺪ ﻓﺘ ﺮات ﻧﺼ ﻒ اﻟﻌﻤ ﺮ ﻋﻨ ﺪ ﺗﺮﻛﯿ ﺰﯾﻦ‬
‫اﺑﺘ ﺪاﺋﯿﯿﻦ ﻣﺨﺘﻠﻔ ﯿﻦ )‪ [A]0(1), [A]0(2‬واﻟﺘﻌ ﻮﯾﺾ ﻓ ﻲ اﻟﻌﻼﻗ ﺔ اﻟﺘﺎﻟﯿ ﺔ‬
‫واﻟﺘﻲ ﺗﺮﺑﻂ ﺑﯿﻦ ﻓﺘﺮﺗﻲ ﻧﺼﻒ اﻟﻌﻤﺮ ‪:‬‬
‫(‪2‬‬
‫)‪n - 1‬‬
‫‪-1‬‬
‫= )‪t 1 (1‬‬ ‫)‪( n - 1‬‬
‫‪2‬‬
‫)‪(n - 1) k n [ A ]0(1‬‬
‫(‪2‬‬
‫)‪n - 1‬‬
‫‪-1‬‬
‫= )‪t 1 (2‬‬ ‫)‪( n - 1‬‬
‫‪2‬‬
‫)‪(n - 1) k n [ A ]0(2‬‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬

‫= ‪ t1‬‬ ‫‪2( ) - 1‬‬
‫‪n-1‬‬
‫‪‬‬ ‫= ‪ t1‬‬ ‫‪2( n - 1) - 1‬‬ ‫‪‬‬
‫‪:‬‬ ‫‪ 2 (2) (n - 1) k n [ A ]( n - 1) ‬‬
‫ﻋﻠﻰ‬ ‫‪ 2 (1) (n - 1) k n [ A]( n - 1) ‬‬
‫وﺑﻘﺴﻤﺔ‬
‫‪‬‬ ‫‪0(2) ‬‬ ‫‪‬‬ ‫‪0(1) ‬‬

(696)
( 2( n - 1)
-1)
( n - 1)
t 1 (1) (n - 1) k n [ A ]0(1)
=
( 2( )
2
n - 1)
t 1 (2) -1
2
( n - 1)
(n - 1) k n [ A ]0(2)
t 1 (1)
=
( 2( n - 1)
-1 ) ×
(n - 1) k n [ A ]0(2)
( n - 1)
( 2( )
2
( n - 1)
(n - 1) k n [ A ]0(1)
n - 1)
t 1 (2) -1
2
[ A ](0(2) )
n-1
t 1 (1)
2
=
[ A ](0(1) )
n-1
t 1 (2)
2
 [A] 
n-1
t 1 (1)
⇒ = 
2 0(2)
t 1 (2)  [A] 
2  0(1) 
t  [A]  
n-1
:  2 =
1 (1)
 t1
0(2)
 

‫وﺑﺄﺧﺬ ﻟﻮﻏﺎرﯾﺘﻢ اﻟﻄﺮﻓﯿﻦ ﻟﻠﻌﻼﻗﺔ‬
 2 (2)  [ A ]0(1)  

 
 t 1 (1)   [ A ]0(2) 
n-1
 2 = 
 t 1 (2)   [ A ] 
 2   0(1) 
 [A] 
n-1
 t 1 (1) 
log  2  = log  0(2)

 t 1 (2)   [A] 
 2   0(1) 
 t 1 (1)   [A] 
log  2  = ( n - 1) log  0(2)

 t 1 (2)   [A] 
 2   0(1) 
 t 1 (1) 
log  2 
 t 1 (2) 
 2 
( )
n - 1 =
 [A] 
 0(2)

 [ A ]0(1) 
 

‫)‪(697‬‬
‫‪⇒ n = 1+‬‬
‫(‬
‫)‪log t 1 (1) / t 1 (2‬‬
‫‪2‬‬ ‫‪2‬‬
‫)‬
‫] ‪([ A‬‬‫)‪0(2‬‬
‫)‪/ [ A ]0(1‬‬ ‫)‬
‫وھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﯾﻤﻜ ﻦ أن ﺗﻌﻄ ﻲ ﻧﺘ ﺎﺋﺞ ﻣﻤﻮھ ﺔ إذا ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ‬
‫ﻣﺮاﺗ ﺐ ﻟﯿﺴ ﺖ ﺑﺴ ﯿﻄﺔ أو إذا ﻛﺎﻧ ﺖ ھﻨ ﺎك ﺗﻌﻘﯿ ﺪات ﻛ ﺎﻟﺘﺜﺒﯿﻂ ﺑ ﺎﻟﻨﻮاﺗﺞ‬
‫◌‬ ‫ﻣﺜﻼً‪.‬‬

‫)‪(698‬‬
‫ﻣﺜﺎﻝ )‪(١١٣-٢‬‬
‫درس ﻓﺎرﻛ ﺎس )‪ (Farkas‬ﻋﻤﻠﯿ ﺔ ﺗﺤﻮﯾ ﻞ ﺑﺎراھﯿ ﺪروﺟﯿﻦ اﻟ ﻰ‬

‫اﻷورﺛﻮھﯿﺪروﺟﯿﻦ ﻓﻲ درﺟﺔ ﺣﺮارة )‪ (650 ºC‬وﺗﺤﺼﻞ ﻋﻠ ﻰ اﻟﻘ ﯿﻢ‬
‫اﻟﺘﺎﻟﯿﺔ ﻟﻔﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ ‪:‬‬
‫)‪P (mmHg‬‬ ‫‪50‬‬ ‫‪100‬‬ ‫‪200‬‬ ‫‪400‬‬
‫اﻟﻀﻐﻂ اﻻﺑﺘﺪاﺋﻲ‬
‫‪(t1/2) min.‬‬ ‫‪10.8‬‬ ‫‪7.5‬‬ ‫‪5.3‬‬ ‫‪3.7‬‬
‫ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‬
‫أوﺟﺪ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ وذﻟﻚ ﺑﺎﺳﺘﻌﻤﺎل طﺮﯾﻘﺔ اﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ‪.‬‬
‫ﺍﳊﻞ‬
‫ﺣﯿ ﺚ أن اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﻓﺘ ﺮة ﻧﺼ ﻒ اﻟﻌﻤ ﺮ واﻟﺘﺮﻛﯿ ﺰ اﻻﺑﺘ ﺪاﺋﻲ ھ ﻲ‬
‫‪‬‬ ‫‪ 2( n - 1) - 1  ‬‬
‫ﺔ‬ ‫ﺑﺪﻻﻟ‬ ‫‪log t 1 ‬‬
‫‪‬‬ ‫‪2 ‬‬
‫ﻢ‬ ‫وﺑﺮﺳ‬ ‫‪log t 12 = (1 - n ) log [ A ]0 + log ‬‬ ‫‪ ‬‬
‫‪‬‬ ‫‪ (n - 1)k n  ‬‬
‫ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴ ﺘﻘﯿﻢ ﻣﯿﻠ ﮫ )‪ (1 – n‬وﺣﯿ ﺚ أن اﻟﻀ ﻐﻂ‬ ‫‪log [ A ]0‬‬
‫اﻹﺑﺘﺪاﺋﻲ ﯾﺘﻨﺎﺳ ﺐ ﻣ ﻊ اﻟﺘﺮﻛﯿ ﺰ اﻹﺑﺘ ﺪاﺋﻲ إذاً ﺑﺄﺧ ﺬ اﻟﻠﻮﻏ ﺎرﯾﺘﻢ ﻧﺤﺼ ﻞ‬
‫ﻋﻠﻰ ‪:‬‬
‫)‪P (mmHg‬‬ ‫‪50‬‬ ‫‪100‬‬ ‫‪200‬‬ ‫‪400‬‬
‫اﻟﻀﻐﻂ اﻻﺑﺘﺪاﺋﻲ‬
‫‪(t1/2) min.‬‬ ‫‪10.8‬‬ ‫‪7.5‬‬ ‫‪5.3‬‬ ‫‪3.7‬‬
‫ﻓﺘﺮة ﻧﺼﻒ اﻟﻌﻤﺮ‬
‫‪log t1/2‬‬ ‫‪1.70‬‬ ‫‪2.00‬‬ ‫‪2.30‬‬ ‫‪2.60‬‬
‫‪log P0‬‬ ‫‪1.03‬‬ ‫‪0.875‬‬ ‫‪0.724‬‬ ‫‪0.568‬‬

‫)‪(699‬‬
‫وﺑﺎﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ ﻧﺤﺼﻞ ﻋﻠﻰ اﻟﺸﻜﻞ )‪.(٣٧-٢‬‬
‫ﺷﻜﻞ )‪(٣٧-٢‬‬
‫وﻣﻦ اﻟﺮﺳﻢ ﻓﺈن ‪:‬‬
‫‪slope = - 0.5‬‬
‫‪ slope = 1 - n‬‬
‫‪n = 1 - slope‬‬
‫‪n = 1 - (- 0.5) = 1.5‬‬
‫أي أن اﻟﺮﺗﺒﺔ ھﻲ ‪1.5‬‬
‫ﻣﺜﺎﻝ )‪(١١٤-٢‬‬
‫ﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﺗﺮاﻛﯿ ﺰ ﻛ ﻞ ﻣ ﻦ اﻟﻤﺘﻔ ﺎﻋﻼت اﻹﺑﺘﺪاﺋﯿ ﺔ ﻓﯿ ﮫ‬

‫ﯾﺴ ﺎوي )‪ (0.1 mol L-1‬وﺟ ﺪ أﻧ ﮫ ﯾﺴ ﺘﻐﺮق ‪ 30 min‬ﻟﯿﺘﻔﺎﻋ ﻞ ‪20‬‬
‫‪ %‬ﻣﻨﮫ أوﺟﺪ ‪:‬‬

‫)‪(700‬‬
‫أ( ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺘﻔﺎﻋﻞ )‪(k‬‬

‫ب( ﻧﺼﻒ اﻟﻌﻤﺮ )‪(t0.5‬‬
‫ج( اﻟ ﺰﻣﻦ اﻟ ﻼزم ﻹﺗﻤ ﺎم ‪ 20 %‬ﻣ ﻦ اﻟﺘﻔﺎﻋ ﻞ ﻋﻨ ﺪﻣﺎ ﯾﻜ ﻮن اﻟﺘﺮﻛﯿ ﺰ‬
‫اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻤﺘﻔﺎﻋﻼت ﯾﺴﺎوي ‪0.01 mol L-1‬‬
‫أ( ‪k = 8.3 × 10-2 mol-1 L min-1‬‬
‫ب( ‪t0.5 = 120.5 min‬‬
‫ج( ‪t = 300 min.‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
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‫‪...................................................................................................... ..................................................................................‬‬

(701)
...................................................................................................... ..................................................................................
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‫)‪(702‬‬
‫ﻣﺜﺎﻝ )‪(١١٥-٢‬‬
‫ﯾﺘﻔﻜ ﻚ اﻷﺳ ﯿﺘﺎﻟﺪھﯿﺪ )‪ (CH3CHO‬ﻋﻨ ﺪ )‪ (500 ºC‬ﻣﻌﻄﯿ ﺎ ً ﻏ ﺎزي‬

‫اﻟﻤﯿﺜﺎن وﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻜﺮﺑﻮن ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫‪ο‬‬
‫‪CH3CHO ‬‬
‫‪500 C‬‬
‫‪→ CH 4 + CO 2‬‬
‫وﻟﻘ ﺪ وﺟ ﺪ أن )‪ (t1/2‬وﻋﻤ ﺮ ﺛﻼﺛ ﺔ أرﺑ ﺎع )‪ (t3/4‬ﺑﻮﺣ ﺪة اﻟﺜﺎﻧﯿ ﺔ ﯾﻌﺘﻤ ﺪ‬

‫ﻋﻠﻰ اﻟﻀﻐﻂ اﻻﺑﺘﺪاﺋﻲ ) ‪ ( Pο‬ﺑﻮﺣﺪة )‪ (mmHg‬ﺣﺴﺐ اﻟﺠﺪول اﻟﺘﺎﻟﻲ ‪:‬‬
‫) ‪(P‬‬ ‫‪ο‬‬
‫‪420‬‬ ‫‪363‬‬ ‫‪290‬‬ ‫‪225‬‬ ‫‪184‬‬
‫‪t1/2‬‬ ‫‪385‬‬ ‫‪420‬‬ ‫‪492‬‬ ‫‪572‬‬ ‫‪665‬‬
‫‪t3/4‬‬ ‫‪1135‬‬ ‫‪1210‬‬ ‫‪1400‬‬ ‫‪1710‬‬ ‫‪1920‬‬
‫أوﺟﺪ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ وﻗﯿﻤﺔ )‪ (k‬ﺣﺴﺎﺑﯿﺎ ً ﺛﻢ ﺑﯿﺎﻧﯿﺎ ً‪.‬‬
‫اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ وﻗﯿﻤﺔ ‪k = 6.69 × 10-6 mmHg s-1‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
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‫‪...................................................................................................... ..................................................................................‬‬

(703)
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‫)‪(704‬‬
‫ﻃﺮﻕ ﺇﳚﺎﺩ ﺭﺗﺒﺔ ﺍﻟﺘﻔﺎﻋﻞ‬
‫‪ (١‬ﻃﺮﻳﻘﺔ ﺍﶈﺎﻭﻟﺔ )‪(Trial Method‬‬
‫أ( اﻟﺘﺤﻘ ﻖ ﻣ ﻦ ﺛﺒ ﻮت ﻗ ﯿﻢ ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪ (k‬ﻋﻨ ﺪ اﻟﺘﻌ ﻮﯾﺾ ﻋ ﻦ ﻗ ﯿﻢ‬

‫‪ a‬و )‪ (a – x‬ﻓ ﻲ ﻣﻌﺎدﻟ ﺔ اﻟﺴ ﺮﻋﺔ اﻟﻤﻨﺎﺳ ﺒﺔ‪ .‬ﻓ ﺈذا ﻛﺎﻧ ﺖ ﻗ ﯿﻢ )‪(k‬‬
‫ﻣﺘﺸ ﺎﺑﮭﺔ أو ﻣﺘﻘﺎرﺑ ﺔ ﺟ ﺪاً ﻋﻨ ﺪ اﻟﺘﻌ ﻮﯾﺾ ﻓ ﻲ ﻣﻌﺎدﻟ ﺔ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‬
‫‪ ،  k = 1t ln  a a- x  ‬ﻓﺈﻧ ﮫ ﯾﺴ ﺘﺪل ﺑ ﺄن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ‪ .‬أﻣ ﺎ إذا‬
‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫ﻛﺎﻧ ﺖ ﻗ ﯿﻢ )‪ (k‬ﻣﺨﺘﻠﻔ ﺔ ﻓﻨﺤ ﺎول اﻟﺘﻌ ﻮﯾﺾ ﻓ ﻲ ﻣﻌﺎدﻟ ﺔ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ‬

‫‪ 1‬‬ ‫‪1‬‬
‫أو ‪ . k = at1  a x- x ‬وﯾﺴ ﺘﺪل ﻣ ﻦ ﺛﺒ ﻮت ﻗ ﯿﻢ ‪ k‬ﻋﻠ ﻰ أن‬ ‫‪‬‬ ‫‪= kt + ‬‬
‫‪‬‬ ‫‪‬‬ ‫) ‪ (a - x‬‬ ‫‪a‬‬
‫)‪. k = 2t1  (a -1x‬‬ ‫‪2‬‬

‫‪-‬‬
‫‪1 ‬‬
‫‪‬‬
‫‪a2 ‬‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪ ،‬وھﻜﺬا ﻟﻠﺮﺗﺒﺔ اﻟﺜﺎﻟﺜﺔ‬
‫‪‬‬
‫‪ (٢‬ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﺘﻔﺎﺿﻠﻴﺔ )‪(The Differential Method‬‬
‫ﻣﻦ اﻟﺸﻜﻞ )‪ (٣٨-٢‬ﻧﺠﺪ أن اﻟﻤﯿﻞ ﻓﻲ اﻟﻨﻘﻄ ﺔ اﻷوﻟ ﻰ اﻟﻤﻘﺎﺑ ﻞ ﻟﻠﺘﺮﻛﯿ ﺰ‬
‫)‪ (C1‬ھ ﻮ )‪ (-dC1/dt‬واﻟﻤﯿ ﻞ ﻓ ﻲ اﻟﻨﻘﻄ ﺔ اﻟﺜﺎﻧﯿ ﺔ اﻟﻤﻘﺎﺑ ﻞ ﻟﻠﺘﺮﻛﯿ ﺰ‬
‫)‪ (C2‬ھﻮ )‪ .(-dC2/dt‬وﺑﻔﺮض أن رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ھ ﻲ )‪ ،(n‬ﻓﺎﻟﻌﻼﻗ ﺔ‬
‫اﻟﺘﻲ ﺗﺮﺑﻂ ﺑﯿﻦ اﻟﻤﯿﻞ )ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ( واﻟﺘﺮﻛﯿﺰ ﻋﻨﺪ ذﻟﻚ اﻟﻤﯿﻞ ھﻲ ‪:‬‬

(705)
dC1
- = k C1n
dt
dC
- 2 = k Cn2
dt
: ‫وﺑﻘﺴﻤﺔ اﻟﻤﻌﺎدﻟﺔ اﻟﺜﺎﻧﯿﺔ ﻋﻠﻰ اﻷوﻟﻰ‬

 dC 2 
-  n
 dt  = k C 2
 dC1  k C1n
- 
 dt 
 dC2 
-   C n
⇒ = 2
dt
 
 dC1   C1 
- 
 dt 
 ( - dC dt )  C  n 
‫( ﺑﻌﺪ إدﺧ ﺎل ﻛ ﻞ‬n) ‫ﻧﺤﺼﻞ ﻋﻠﻰ‬  2
= 2   ‫وﻣﻦ اﻟﻤﻌﺎدﻟﺔ‬
 ( - dC1 dt )  C1  
.‫ﻣﻦ اﻟﻤﯿﻞ واﻟﺘﺮﻛﯿﺰ ﻓﯿﮭﺎ‬
(٣٨-٢) ‫ﺷﻜﻞ‬

(706)
‫( ﲤﺜﻴـﻞ ﻣﻌﺎﺩﻟـﺔ ﺍﻟﺮﺗﺒـﺔ ﺍﻟﺘﻜﺎﻣﻠﻴـﺔ )ﺍﻟﻄﺮﻳﻘـﺔ ﺍﻟﺘﻜﺎﻣﻠﻴــﺔ‬٣
(Method of integration)
‫ ﻓ ﺈذا ﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ‬،ً‫وﻓﻲ ھﺬه اﻟﻄﺮﯾﻘﺔ ﻧﻤﺜﻞ ﻣﻌﺎدﻟﺔ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺑﯿﺎﻧﯿ ﺎ‬
.‫ﯾﺘﺒﻊ اﻟﺮﺗﺒﺔ اﻟﺘﻲ ﻣﺜﻠﻨﺎھﺎ ﺑﯿﺎﻧﯿﺎ ً ﻓﺈﻧﻨﺎ ﻧﺤﺼﻞ ﻋﻠﻰ ﺧﻂ ﻣﺴﺘﻘﯿﻢ‬
‫اﻟﺮﺳﻢ اﻟﺒﯿﺎﻧﻲ‬ ‫ﻣﻌﺎدﻟﺔ اﻟﺮﺗﺒﺔ‬ ‫اﻟﺮﺗﺒﺔ‬
a
ln = kt
(a - x)
( ln (a - x) = - kt + ln a ) 1
 x 
 = kt 
 a (a - x) 
 1 1 a=b 2
 = kt + 
 (a - x ) a
 1  b (a - x)   a≠b
 ln   = kt 
 (a - b)  a (b - x)  
 x ( 2a - x ) 
 2 2
= kt 
 2a (a - x) 
 1 1  3
 2
= kt +  a=b=c
 2(a - x) 2a 2 
1 1 1 
  2
- 2  = kt 
 2  (a - x) a  
 1  x(c - a)  c(a - x)    a = b ≠c
  + ln    = kt 
 ( c - a )2  a(a - x)  a(c - x)   
 
1 a-x 1 b-x 1 c-x a ≠ b ≠

( a - b )( c - a )  a  ( a - b )( b - c )  b  ( c - a )( b - c )  c 
ln  + ln  + ln  = kt
c

‫)‪(707‬‬
‫‪ (٤‬ﻃﺮﻳﻘﺔ ﻓﱰﺓ ﻋﻤﺮ ﺍﻟﻨﺼﻒ )‪(Method of Half-life‬‬
‫ﻛﻤﺎ ﺳﺒﻖ ﻣﻦ ﻗﯿﻤﺘﮫ ﻧﺼﻒ اﻟﻌﻤﺮ أﻧ ﮫ إذا ﻛﺎﻧ ﺖ اﻟﻘﯿﻤ ﺔ ﺗﺘﻨﺎﺳ ﺐ طﺮدﯾ ﺎ ً‬
‫‪‬‬ ‫‪a ‬‬
‫ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﯾﻜ ﻮن ﻣ ﻦ اﻟﺮﺗﺒ ﺔ ﺻ ﻔﺮ ‪ ،‬وإذا‬ ‫= ‪ t 12‬‬ ‫اﻟﺘﺮﻛﯿ ﺰ ‪‬‬ ‫ﻣﻊ‬
‫‪‬‬ ‫‪2k‬‬
‫‪‬‬ ‫‪0.693 ‬‬

‫ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ‬ ‫= ‪ t 12‬‬ ‫‪‬‬ ‫ﻛﺎﻧ ﺖ ﻻ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ اﻟﺘﺮﻛﯿ ﺰ‬
‫‪‬‬ ‫‪k ‬‬
‫‪‬‬ ‫‪1 ‬‬

‫ﻓﺈن‬ ‫= ‪ t1/2‬‬ ‫‪‬‬ ‫اﻷوﻟﻰ‪ ،‬وإذا ﻛﺎﻧﺖ ﺗﺘﻨﺎﺳﺐ ﻋﻜﺴﯿﺎ ً ﻣﻊ اﻟﺘﺮﻛﯿﺰ اﻷوﻟﻲ‬
‫‪‬‬ ‫‪ka‬‬
‫اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪ ،‬وإذا ﻛﺎن ﯾﺘﻨﺎﺳﺐ ﻋﻜﺴﯿﺎ ً ﻣﻊ ﻣﺮﺑﻊ اﻟﺘﺮﻛﯿ ﺰ‬

‫‪‬‬ ‫‪3 ‬‬
‫ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ﺛﻼﺛﻲ اﻟﺮﺗﺒﺔ‪.‬‬ ‫= ‪ t 12‬‬ ‫‪‬‬ ‫اﻷوﻟﻲ‬
‫‪‬‬ ‫‪2a 2 k ‬‬
‫رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ )‪(n‬‬ ‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬

‫‪‬‬ ‫‪a ‬‬ ‫‪‬‬ ‫‪0.693 ‬‬ ‫‪‬‬ ‫‪1 ‬‬ ‫‪‬‬ ‫‪3 ‬‬
‫ﻓﺘﺮة ﻋﻤﺮ اﻟﻨﺼﻒ ‪t1/2‬‬ ‫= ‪ t 12‬‬ ‫‪‬‬ ‫= ‪ t 12‬‬ ‫‪‬‬ ‫= ‪ t1/2‬‬ ‫‪‬‬ ‫= ‪ t 12‬‬ ‫‪‬‬
‫‪‬‬ ‫‪2k‬‬ ‫‪‬‬ ‫‪k ‬‬ ‫‪‬‬ ‫‪ka‬‬ ‫‪‬‬ ‫‪2a 2 k ‬‬
‫وﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻤﻌﺎدﻟﺔ اﻟﻌﺎﻣﺔ ﻛﻤﺎ ﯾﻠﻲ ‪:‬‬

‫‪1‬‬
‫‪t1/2 α‬‬
‫‪a n-1‬‬
‫ﻓ ﺈذا ﻛ ﺎن اﻟﺘﺮﻛﯿ ﺰ اﻷوﻟ ﻲ ﻓ ﻲ ﺗﺠ ﺮﺑﺘﯿﻦ ﻣﺨﺘﻠﻔﺘ ﯿﻦ ھ ﻮ )‪ (a1‬و )‪(a2‬‬

‫واﻟﻔﺘﺮات اﻟﻤﻘﺎﺑﻠﺔ ﻟﻌﻤ ﺮ اﻟﻨﺼ ﻒ ھ ﻲ ‪ (t1/2)1‬و ‪ (t1/2)2‬ﻋﻠ ﻰ اﻟﺘ ﻮاﻟﻲ‬
‫ﻓﺈﻧﮫ ﯾﻤﻜﻦ ﻛﺘﺎﺑﺔ ‪:‬‬

(708)
 1 
( t1/2 )1  a n-1 
= 1 
( t1/2 )2  1 
 a n-1 
 2 
( t1/2 )1  a n-1 
=  2n-1 
( t1/2 )2  a1 
( t1/2 )1  a 2 
n-1
=
( t1/2 )2  a1 
( t1/2 )1
n-1
 a2 
log = log  
( t1/2 )2  a1 
( t1/2 )1 a 
log = ( n - 1) log  2 
( t1/2 )2  a1 
log ( t1/2 )1 − log ( t1/2 )2 = ( n - 1)( log a 2 − log a1 )
log ( t1/2 )1 − log ( t1/2 )2
= ( n - 1)
( log a 2 − log a1 )
log ( t1/2 )1 - log ( t1/2 ) 2
n=1+
( log a 2 - log a1 )

‫)‪(709‬‬
‫‪ (٥‬ﻃﺮﻳﻘﺔ ﺍﻟﻌﺰﻝ )‪(Isolation Method‬‬
‫ﻟﻠﺘﻔﺎﻋﻼت ﻣﺘﻌﺪدة اﻟﺠﺰﯾﺌﯿﺔ ﻗﺪ ﯾﺼﻌﺐ اﺳﺘﺨﺪام اﻟﻄﺮق اﻟﺴﺎﺑﻘﺔ ﻹﯾﺠﺎد‬

‫رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ وﻛ ﺬﻟﻚ ﺣﯿﻨﻤ ﺎ ﯾﻜ ﻮن إﯾﺠ ﺎد رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺎﻟﻨﺴ ﺒﺔ‬
‫ﻟﻠﻤﺘﻔﺎﻋﻼت ﻛﻞ ﻋﻠﻰ ﺣ ﺪة ﻣﮭﻤ ﺎ ً ﻟ ﺬا ﻧﻠﺠ ﺄ اﻟ ﻰ اﺳ ﺘﺨﺪام ﺗﺮاﻛﯿ ﺰ ﻋﺎﻟﯿ ﺔ‬
‫ﻣ ﻦ اﻟﻤﺘﻔ ﺎﻋﻼت ﻋ ﺪا اﻟﻤ ﺎدة اﻟﻤﺘﻔﺎﻋﻠ ﺔ اﻟﻤ ﺮاد دراﺳ ﺘﮭﺎ وﺗﺴ ﻤﻰ ھ ﺬه‬
‫اﻟﻄﺮﯾﻘ ﺔ "طﺮﯾﻘ ﺔ اﻟﻌ ﺰل"‪ .‬ﻓ ﺈذا ﻛﺎﻧ ﺖ اﻟﻤﻌﺎدﻟ ﺔ اﻟﺤﺮﻛﯿ ﺔ ﻟﻠﺘﻔﺎﻋ ﻞ‬
‫ﺗﺘﻀﻤﻦ ﻛﺜﺮ ﻣﻦ ﺗﺮﻛﯿﺰ واﺣﺪ ﻓﺈﻧﮫ ﻣﻦ اﻟﻤﻤﻜﻦ ﻋﺰل واﺣﺪ أو أﻛﺜﺮ ﻣﻦ‬
‫اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ وذﻟﻚ ﺑﺎﺳﺘﻌﻤﺎل زﯾﺎدة ﻣ ﻦ ﺗﺮﻛﯿ ﺰه‪ .‬وﻓ ﻲ ھ ﺬه اﻟﺤﺎﻟ ﺔ‬
‫ﻓ ﺈن اﻟﻤ ﺎدة اﻟﻤﻮﺟ ﻮدة ﺑﺘﺮﻛﯿ ﺰ ﻛﺒﯿ ﺮ ﺳ ﻮف ﺗﻈ ﻞ ﺛﺎﺑﺘ ﺔ ط ﻮل اﻟﺘﻔﺎﻋ ﻞ‬
‫وﻋﻠﻰ ھﺬا ﻓﺈن اﻟﺮﺗﺒﺔ اﻟﻜﻠﯿﺔ ﻟﻠﺘﻔﺎﻋﻞ ﺳﻮف ﺗﻘﻞ‪.‬‬
‫ﺗﺘﻜﺮر ھﺬه اﻟﻌﻤﻠﯿﺔ ﻓﻲ اﻟﺘﻔﺎﻋﻼت اﻟﻤﺎﺋﯿ ﺔ ﺣﯿ ﺚ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎء ﻻ ﯾﺘﻐﯿ ﺮ‬
‫ﻓﻲ اﻟﺘﻔﺎﻋﻞ إﻻ ﺑﺸﻜﻞ طﻔﯿﻒ‪ .‬ﻓﺈذا ﻛﺎن ﻟﺪﯾﻨﺎ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬
‫‪A + B + C ‬‬
‫ﻓﺈن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻟﮫ ‪:‬‬

‫]‪Rate = k [ A ] [ B‬‬
‫‪n‬‬ ‫‪m‬‬
‫ﻓﺈذا اﺳﺘﺨﺪﻣﻨﺎ ﺗﺮاﻛﯿﺰ ﻋﺎﻟﯿﺔ ﻣﻦ )‪) (B‬ﻋﺸﺮة أﺿﻌﺎف ﺗﺮﻛﯿﺰ ‪ A‬ﻋﻠﻰ‬

‫اﻷﻗﻞ( ﻓﺈن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﺳﺘﺼﺒﺢ ‪:‬‬
‫]‪Rate = k' [ A‬‬
‫‪n‬‬

‫)‪(710‬‬
‫ﺣﯿﺚ )'‪ (k‬ﺗﺴﺎوي ‪:‬‬

‫]‪k' = k [ B‬‬
‫‪m‬‬
‫ﺑﺎﺳ ﺘﺨﺪام إﺣ ﺪى اﻟﻄ ﺮق اﻟ ﺜﻼث اﻟﺴ ﺎﺑﻘﺔ ﻧﻮﺟ ﺪ رﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ )‪(n‬‬
‫ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﻤﺘﻔﺎﻋﻞ )‪ (A‬وﻗﯿﻤﺔ اﻟﺜﺎﺑﺖ )‪ (k‬ﻣﻦ اﻟﻌﻼﻗﺔ ]‪: k' = k [ B‬‬
‫‪m‬‬
‫]‪log k' = log k - m log [ B‬‬
‫وﺑﺮﺳ ﻢ ﺗﻐﯿ ﺮ )'‪ (log k‬ﻣ ﻊ ﺗﻐﯿ ﺮ ﺗﺮﻛﯿ ﺰ )‪ (B‬ﻧﺤﺼ ﻞ ﻋﻠ ﻰ رﺗﺒ ﺔ‬

‫اﻟﺘﻔﺎﻋﻞ ﻛﻤﺎ ﻓﻲ طﺮﯾﻘﺔ اﻟﺘﻔﺎﺿﻞ‪ ،‬وﻣﻦ ﺗﻼﻗ ﻲ اﻟﺨ ﻂ اﻟﻤﺴ ﺘﻘﯿﻢ ﻧﺤﺼ ﻞ‬
‫ﻋﻠﻰ )‪ (log k‬وﻣﻨﮫ ﻗﯿﻤﺔ )‪ ،(k‬ﻓﺈذا ﻛﺎﻧﺖ اﻟﺮﺗﺒﺔ اﻟﻨﺎﺗﺠﺔ ﻟﻠﻤﺎدة اﻟﻤﺮاد‬
‫دراﺳ ﺘﮭﺎ رﺗﺒ ﺔ أوﻟ ﻰ ﻓﺮﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﻠﯿ ﺔ ﺗﻜ ﻮن ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﻮھﻤﯿ ﺔ‬
‫اﻷوﻟ ﻰ )‪ (Pseudo First Order‬وﻣﺜﺎﻟ ﮫ ﺗﻤﯿ ﺆ أﻧﮭﯿﺪرﯾ ﺪ ﺣﻤ ﺾ‬
‫اﻟﺨﻞ ‪:‬‬
‫‪( CH 3CO )2 CO + H 2O ‬‬
‫‪→ 2CH 3CO 2 H‬‬
‫وﻛﺬﻟﻚ إذا ﻛﺎﻧﺖ اﻟﺮﺗﺒﺔ اﻟﻨﺎﺗﺠ ﺔ رﺗﺒ ﺔ ﺛﺎﻧﯿ ﺔ ﻓﺮﺗﺒ ﺔ اﻟﺘﻔﺎﻋ ﻞ ﺗﺼ ﺒﺢ ﻣ ﻦ‬

‫اﻟﺮﺗﺒﺔ اﻟﻮھﻤﯿﺔ اﻟﺜﺎﻧﯿﺔ )‪ (Pseudo-Second Order‬وﻣﺜﺎﻟﮫ ﺗﻔﺎﻋﻞ‬
‫اﻟﯿ ﻮد اﻟ ﺬري ‪ I‬ﻣ ﻊ ﻟﺘﻜ ﻮﯾﻦ ﻏ ﺎز اﻟﯿ ﻮد ‪ I2‬ﺑﻮﺟ ﻮد ﻛﻤﯿ ﺔ ﻣ ﻦ ﻏ ﺎز‬
‫اﻵرﺟﻮن ‪:‬‬
‫‪I + I + Ar ‬‬
‫‪→ I2 + Ar‬‬

‫)‪(711‬‬
‫ﻣﺜﺎﻝ )‪(١١٦-٢‬‬
‫ﻟﻮ ﻓﺮﺿﻨﺎ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ‪:‬‬

‫‪A + B ‬‬
‫وﺷﻜﻞ ﻗﺎﻧﻮن رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫‪rate = k[A]n [B]m‬‬
‫واﻟﺠﺪول اﻟﺘﺎﻟﻲ ﯾﻮﺿﺢ ﻗﺮاءات ﻟﺴﻠﺴﻠﺔ ﻣﻦ ﺧﻤﺲ ﺗﺠﺎرب ‪:‬‬

‫]‪[A‬‬ ‫‪0.10‬‬ ‫‪0.20‬‬ ‫‪0.30‬‬ ‫‪0.30‬‬ ‫‪0.30‬‬
‫]‪[B‬‬ ‫‪0.10‬‬ ‫‪0.10‬‬ ‫‪0.10‬‬ ‫‪0.20‬‬ ‫‪0.30‬‬
‫)‪ (mol dm-3 s-1‬اﻟﻤﻌﺪل اﻹﺑﺘﺪاﺋﻲ‬ ‫‪0.20‬‬ ‫‪0.40‬‬ ‫‪0.60‬‬ ‫‪2.40‬‬ ‫‪5.40‬‬
‫وﻓﻲ اﻟﻘﺮاءات اﻟﺜﻼث اﻷوﻟﻰ ﻧﺮى أن ]‪ [B‬ﺛﺎﺑﺖ وﺑﺬﻟﻚ ﯾﻜ ﻮن اﻟﺘﻐﯿ ﺮ‬

‫ﻓﻲ اﻟﻤﻌ ﺪل ﻧ ﺎﺗﺞ ﻋ ﻦ اﻟﺘﻐﯿ ﺮ ﻓ ﻲ ]‪ .[A‬وﺑﻔﺤ ﺺ اﻟﻤﻌﻠﻮﻣ ﺎت اﻟﻤﻌﻄ ﺎة‬
‫ﻧﺠﺪ أﻧﮫ ﻋﻨﺪﻣﺎ ﺿﻮﻋﻒ ]‪ [A‬زاد اﻟﻤﻌ ﺪل اﻟ ﻰ اﻟﻀ ﻌﻒ‪ ،‬وﻋﻨ ﺪﻣﺎ زاد‬
‫]‪ [A‬اﻟﻰ ﺛﻼث أﺿﻌﺎف زاد اﻟﻤﻌﺪل اﻟﻰ ﺛﻼﺛﺔ أﺿﻌﺎف وﺑﺬﻟﻚ ﻧﺴﺘﻨﺘﺞ‬
‫أن اﻟﻤﻌﺪل ﯾﺘﻨﺎﺳﺐ ﺗﻨﺎﺳﺒﺎ ً طﺮدﯾﺎ ً ﻣﻊ ]‪ [A‬وھﺬا ﯾﻌﻨﻲ أن أس ]‪ [A‬ﻓﻲ‬
‫ﻗﺎﻧﻮن اﻟﺮﺗﺒﺔ ھﻮ ‪.1‬‬

‫)‪(712‬‬
‫ﺍﻹﺛﺒﺎﺕ ‪:‬‬

‫‪0.2 = k ( 0.1) (0.1)m‬‬
‫‪n‬‬
‫‪0.40 = k ( 0.2 ) (0.1) m‬‬

‫‪n‬‬
‫وﺑﻘﺴﻤﺔ ﻣﻌﺪﻟﻲ اﻟﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻘﯿﻦ ﻋﻠﻰ ﺑﻌﻀﮭﻤﺎ ‪:‬‬

‫‪k ( 0.1) (0.1) m‬‬
‫‪n‬‬
‫‪0.2‬‬
‫=‬
‫‪k ( 0.2 ) (0.1) m‬‬
‫‪n‬‬
‫‪0.40‬‬
‫)‪( 0.1‬‬
‫‪n‬‬
‫= ‪0.5‬‬
‫) ‪( 0.2‬‬
‫‪n‬‬
‫‪n‬‬
‫‪ 0.1 ‬‬
‫‪0.5 = ‬‬ ‫‪‬‬
‫‪ 0.2 ‬‬
‫‪n‬‬
‫‪ 0.1 ‬‬
‫‪log 0.5 = log ‬‬ ‫‪‬‬
‫‪ 0.2 ‬‬
‫‪ 0.1 ‬‬
‫‪log 0.5 = n log ‬‬ ‫‪‬‬
‫‪ 0.2 ‬‬
‫‪log 0.5‬‬
‫=‪n‬‬ ‫‪=1‬‬
‫) ‪log ( 0.1/0.2‬‬
‫أﻣﺎ ﻓﻲ اﻟﻘ ﺮاءات اﻟﺜﻼﺛ ﺔ اﻷﺧﯿ ﺮة ﻛ ﺎن ]‪ [A‬ﺛﺎﺑ ﺖ و]‪ [B‬ﻣﺘﻐﯿ ﺮ وھ ﻮ‬

‫اﻟ ﺬي ﯾ ﺆﺛﺮ ﻋﻠ ﻰ اﻟﻤﻌ ﺪل‪ .‬ﻓﻌﻨ ﺪﻣﺎ ﺿ ﻮﻋﻒ ]‪ [B‬زاد اﻟﻤﻌ ﺪل اﻟ ﻰ ‪4‬‬
‫ﻣﺮات‪ ،‬وﻋﻨﺪﻣﺎ زاد ]‪ [B‬اﻟﻰ ﺛﻼﺛﺔ أﺿﻌﺎف )ﻣﻦ ‪ 0.1‬اﻟﻰ ‪ (0.3‬زاد‬

‫)‪(713‬‬
‫اﻟﻤﻌﺪل اﻟﻰ ‪ 9‬ﻣﺮات ‪ .‬ﻣﻤﺎ ﯾﻌﻨﻲ أن ]‪ [B‬ﻓ ﻲ ﻗ ﺎﻧﻮن اﻟﻤﻌ ﺪل ﯾﺠ ﺐ أن‬

‫ﺗﺮﻓﻊ اﻟﻰ اﻷس ‪.2‬‬
‫ﺍﻹﺛﺒﺎﺕ‬

‫‪0.6 = k ( 0.3) (0.1)m‬‬
‫‪n‬‬
‫‪2.40 = k ( 0.3) (0.2)m‬‬

‫‪n‬‬
‫وﺑﻘﺴﻤﺔ ﻣﻌﺪﻟﻲ اﻟﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻘﯿﻦ ﻋﻠﻰ ﺑﻌﻀﮭﻤﺎ ‪:‬‬

‫‪k ( 0.3 ) (0.1) m‬‬
‫‪n‬‬
‫‪0.6‬‬
‫=‬
‫‪2.40 k ( 0.3 )n (0.2) m‬‬
‫‪(0.1)m‬‬
‫= ‪0.25‬‬
‫‪(0.2)m‬‬
‫‪m‬‬
‫‪ 0.1 ‬‬
‫‪0.25 = ‬‬ ‫‪‬‬
‫‪ 0.2 ‬‬
‫‪m‬‬
‫‪ 0.1 ‬‬
‫‪log 0.25 = log ‬‬ ‫‪‬‬
‫‪ 0.2 ‬‬
‫‪ 0.1 ‬‬
‫‪log 0.25 = m log ‬‬ ‫‪‬‬
‫‪ 0.2 ‬‬
‫‪log 0.25‬‬
‫=‪m‬‬
‫) ‪log ( 0.1/0.2‬‬
‫‪m=2‬‬
‫وﺑﻌﺪ أن ﺣﺪدﻧﺎ أﺳﺲ ﺣﺪود اﻟﺘﺮﻛﯿﺰ أﺻﺒﺢ ﻣﻦ اﻟﻤﻤﻜﻦ ﻛﺘﺎﺑﺔ اﻟﻘﺎﻧﻮن ‪:‬‬
‫‪rate = k[A]1[B]2‬‬

‫)‪(714‬‬
‫إذاً ﻓﺎﻟﺘﻔﺎﻋ ﻞ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻗ ﻲ ‪ ،A‬وﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓ ﻲ ‪.B‬‬

‫ورﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻜﻠﯿﺔ ھﻲ ‪:‬‬
‫‪n+m=1+2=3‬‬
‫ﻣﺜﺎﻝ )‪(١١٧-٢‬‬
‫‪ ( A + B ‬ﺑﻘﯿ ﺎس ﻣﻌ ﺪﻻت اﺑﺘﺪاﺋﯿ ﺔ ﻟﺘﺮﻛﯿ ﺰات‬ ‫درس اﻟﺘﻔﺎﻋ ﻞ ) ‪→ C‬‬
‫اﺑﺘﺪاﺋﯿﺔ ﻣﺨﺘﻠﻔﺔ ﻟﻜﻞ ﻣ ﻦ ‪ A‬و ‪ B‬واﻟﺠ ﺪول اﻟﺘ ﺎﻟﻲ ﯾﺒ ﯿﻦ ﻗ ﯿﻢ اﻟﻤﻌ ﺪﻻت‬
‫اﻹﺑﺘﺪاﺋﯿﺔ اﻟﻤﻘﺎﺳﺔ‬
‫]‪[A‬‬ ‫]‪[B‬‬ ‫) ‪(ν‬‬
‫‪0.01‬‬ ‫‪0.05‬‬ ‫‪0.0031‬‬
‫‪0.05‬‬ ‫‪0.05‬‬ ‫‪0.0155‬‬
‫‪0.05‬‬ ‫‪0.10‬‬ ‫‪0.0155‬‬
‫‪0.07‬‬ ‫‪0.02‬‬ ‫‪0.0217‬‬
‫‪0.10‬‬ ‫‪0.01‬‬ ‫‪0.031‬‬
‫‪0.10‬‬ ‫‪0.05‬‬ ‫‪0.031‬‬
‫‪0.07‬‬ ‫‪0.10‬‬ ‫‪0.0217‬‬
‫ﻓﻤﺎ ھﻲ ﻣﺮاﺗ ﺐ اﻟﺘﻔﺎﻋ ﻞ ﺑﺎﻟﻨﺴ ﺒﺔ ﻟﻜ ﻞ ﻣ ﻦ )‪ (A‬و )‪ (B‬وﻛ ﺬﻟﻚ اﻟﺮﺗﺒ ﺔ‬

‫اﻟﻜﻠﯿﺔ‪.‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬
‫‪...................................................................................................... ..................................................................................‬‬

‫)‪(715‬‬
‫ﻣﻘﺎﺭﻧﺔ ﺑﲔ ﺍﻟﻄﺮﻕ ﺍﻟﺴﺎﺑﻘﺔ‬
‫ﺗﻌﺘﺒﺮ طﺮﯾﻘﺔ اﻟﺘﻜﺎﻣﻞ ھﻲ اﻟﻄﺮﯾﻘﺔ اﻟﺸﺎﺋﻌﺔ اﻻﺳﺘﺨﺪام ﻟﺴﮭﻮﻟﺔ ﺗﻄﺒﯿﻘﮭ ﺎ‬

‫ﻓ ﻲ اﻟﻤﺨﺘﺒ ﺮ ﺣﯿ ﺚ ﯾﻌﻤ ﻞ اﻟﺘﻔﺎﻋ ﻞ ﻟﻤ ﺮة واﺣ ﺪة ﻓﻘ ﻂ وﻣ ﻦ اﻟﻤﻌﻠﻮﻣ ﺎت‬
‫اﻟﻨﺎﺗﺠ ﺔ ﻣ ﻦ ﺗﻐﯿ ﺮ اﻟﺘﺮاﻛﯿ ﺰ ﻣ ﻊ ﺗﻐﯿ ﺮ اﻟ ﺰﻣﻦ ﯾﻤﻜ ﻦ ﺣﺴ ﺎب ﺳ ﺮﻋﺔ‬
‫اﻟﺘﻔﺎﻋﻞ‪ .‬إﻻ أﻧﮫ ﯾﻌﺎب ﻋﻠﻰ ھﺬه اﻟﻄﺮﯾﻘﺔ أﻧﮫ ﯾﺠﺐ أن ﯾﻜﻮن ﻟﺪﯾﻨﺎ ﻓﻜﺮة‬
‫أﺳﺎﺳﯿﺔ ﻋﻦ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺤﯿﺚ ﯾﺠﺐ ﺗﺠﺮﯾﺐ اﻟﻤﻌﻄﯿﺎت اﻟﻨﺎﺗﺠ ﺔ ﻋ ﻦ‬
‫اﻟﺘﻔﺎﻋ ﻞ ﻋﻠ ﻰ أﺣ ﺪ ﻗ ﻮاﻧﯿﻦ اﻟﺴ ﺮﻋﺔ ﺣﺘ ﻰ ﯾﺘﻜ ﻮن ﻟ ﺪﯾﻨﺎ ﺧ ﻂ ﻣﺴ ﺘﻘﯿﻢ‬
‫ﻧﺤﺴﺐ ﻣﻨﮫ ﻗﯿﻤﺔ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ )‪(k‬‬
‫وھﻨﺎك ﻣﺄﺧﺬان ﻋﻠﻰ ﻧﺘﺎﺋﺞ ھﺬه اﻟﻄﺮﯾﻘﺔ ‪:‬‬
‫ً‬
‫ﺃﻭﻻ ‪:‬‬
‫ﻗﺪ ﺗﻜﻮن رﺗﺒﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻨﺎﺗﺠ ﺔ ﻋ ﻦ ﺗﻄﺒﯿ ﻖ ﻗ ﺎﻧﻮن اﻟﺴ ﺮﻋﺔ ﺑﻌ ﺪ إﯾﺠ ﺎد‬
‫ﺛﺎﺑ ﺖ اﻟﺴ ﺮﻋﺔ )‪ (k‬ﻗﺮﯾﺒ ﺔ ﻣ ﻦ اﻟﺮﺗﺒ ﺔ اﻟﻤﺨﺘ ﺎرة ﻓﻤ ﺜﻼً ﻗ ﺪ ﺗﻨ ﺘﺞ رﺗﺒ ﺔ‬
‫ﻣﺴﺎوﯾﺔ )‪ (1.8‬ﻟﺬا ﻧﻘﺮب اﻟﺮﻗﻢ اﻟﺼﺤﯿﺢ ﻟﯿﺼﺒﺢ )‪ (2‬وﯾﺼﺒﺢ اﻟﺘﻔﺎﻋ ﻞ‬
‫ﻣﻦ اﻟﺮﺗﺒﺔ اﻟﺜﺎﻧﯿﺔ‪.‬‬

‫)‪(716‬‬
‫ً‬
‫ﺛﺎﻧﻴﺎ ‪:‬‬
‫ﺑﻤﺎ أﻧﻨﺎ ﻧﻘﯿﺲ ﺗﻐﯿﺮ اﻟﺘﺮﻛﯿﺰ ﻣﻊ اﻟﺰﻣﻦ ﻟﺬا ﻓﺈن اﻟﺮﺗﺒﺔ اﻟﻨﺎﺗﺠ ﺔ ﻣ ﻦ ﻧ ﻮع‬
‫اﻟﺮﺗﺒ ﺔ ﺑﺪﻻﻟ ﺔ اﻟ ﺰﻣﻦ )‪ (nc‬ﻣﻤ ﺎ ﯾﻨ ﺘﺞ ﻋ ﻦ ذﻟ ﻚ ﺛﺎﺑ ﺖ ﺳ ﺮﻋﺔ )‪ (k‬ﻗ ﺪ‬
‫ﺗﺨﺘﻠﻒ ﻗﯿﻤﺘﮫ ﻟﺪى ﻗﯿﺎﺳﮫ ﻋﻨﺪ ﺗﺮاﻛﯿﺰ اﺑﺘﺪاﺋﯿﺔ ﻣﺨﺘﻠﻔﺔ‪.‬‬
‫ﻓ ﺈذا أﺧ ﺬ ھ ﺬا اﻟﻤﺄﺧ ﺬ ﺑﻌ ﯿﻦ اﻹﻋﺘﺒ ﺎر ﺗﻜ ﻮن ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ھ ﻲ اﻷﻣﺜ ﻞ‬
‫ﻟﺤﺴﺎب ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ورﺗﺒﺘﮫ وﺛﺎﺑﺘﮫ‪.‬‬
‫• طﺮﯾﻘﺔ اﻟﺘﻔﺎﺿﻞ ‪:‬‬
‫وﺗﻤﺘ ﺎز طﺮﯾﻘ ﺔ اﻟﺘﻔﺎﺿ ﻞ ﺑﺄﻧﮭ ﺎ ﻣﺒﺎﺷ ﺮة واﻟﻤﺄﺧ ﺬ اﻟﻮﺣﯿ ﺪ ﻋﻠ ﻰ ھ ﺬه‬
‫اﻟﻄﺮﯾﻘﺔ ھﻮ إﯾﺠﺎد اﻟﻤﻤﺎس ﻟﻠﻤﻨﺤﻨﻰ اﻟﻨﺎﺗﺞ ﺑﺸﻜﻞ دﻗﯿﻖ ﻣﻤﺎ ﯾ ﺆﺛﺮ ﻋﻠ ﻰ‬
‫اﻟﻨﺎﺗﺞ ﺑﺸﻜﻞ ﻛﺒﯿﺮ وﻟﻜﻨﮭﺎ ﺗﻤﺘﺎز ﺑﺈﯾﺠﺎد اﻟﺮﺗﺒﺔ اﻟﺤﻘﯿﻘﯿﺔ ‪.nt‬‬
‫• طﺮﯾﻘﺔ زﻣﻦ ﻧﺼﻒ اﻟﻌﻤﺮ ‪:‬‬
‫ﯾﻌﺎب ﻋﻠﯿﮭﺎ ﺣﺼﺮ ﺗﻄﺒﯿﻘﺎﺗﮭﺎ ﻋﻠﻰ اﻟﺘﻔﺎﻋﻼت اﻟﺒﺴﯿﻄﺔ اﻟﺘ ﻲ ﻻ ﺗﺤﺘ ﻮي‬
‫ﻋﻠ ﻰ ﺗﻔ ﺎﻋﻼت ﺟﺎﻧﺒﯿ ﺔ ﻟ ﺬا ﻓ ﺈن ھ ﺬه اﻟﻄﺮﯾﻘ ﺔ ﺗﺴ ﺘﺨﺪم ﻓﻘ ﻂ ﻛﻄﺮﯾﻘ ﺔ‬
‫ﻣﻜﻤﻠﺔ ﻟﻠﻄﺮﯾﻘﺘﯿﻦ اﻟﺴﺎﺑﻘﺘﯿﻦ‪.‬‬
‫• طﺮﯾﻘﺔ اﻟﻌﺰل‬
‫وﺗﻌﺘﺒﺮ ھﺬه اﻟﻄﺮﯾﻘﺔ اﻟﻤﺜﻠﻰ ﻟﻠﺘﺨﻠﺺ ﻣﻦ ﺗﻌﻘﯿﺪات ﺗ ﺄﺛﯿﺮ ﺑﻌ ﺾ اﻟﻤ ﻮاد‬
‫ﻋﻠ ﻰ اﻟﺘﻔﺎﻋ ﻞ أي ﺑﻤﻌﻨ ﻰ آﺧ ﺮ ﺗﺒﺴ ﯿﻂ ﻗ ﺎﻧﻮن اﻟﺴ ﺮﻋﺔ وﯾﻔﻀ ﻞ داﺋﻤ ﺎ ً‬
‫اﺳﺘﺨﺪام طﺮﯾﻘﺔ اﻟﺘﻔﺎﺿﻞ ﻹﯾﺠﺎد رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬

‫)‪(717‬‬
‫ﻣﺜﺎﻝ )‪(١١٨-٢‬‬
‫اﻟﺠﺪول اﻟﺘﺎﻟﻲ ﯾﻮﺿﺢ ﺑﯿﺎﻧﺎت ﻋﻦ ﺗﺤﻮﯾ ﻞ ﺳ ﻜﺮ اﻟﻘﺼ ﺐ )‪(sucrose‬‬

‫اﻟﻰ ﺟﻠﻮﻛﻮز )‪ (Glucose‬وﻓﺮﻛﺘﻮز )‪: (Frextose‬‬
‫‪C12 H 22 O11 + H2 O ‬‬
‫‪→ C6 H12 O6 + C6 H12 O6‬‬
‫اﻟﺰﻣﻦ )دﻗﯿﻘﺔ(‬ ‫‪0‬‬ ‫‪7.20‬‬ ‫‪18.00‬‬ ‫‪27.00‬‬ ‫∞‬

‫) ‪ ( α‬زاوﯾﺔ اﻟﺪوران‬ ‫‪+ 24.04º‬‬ ‫‪+ 21.40º‬‬ ‫‪+ 17.73º‬‬ ‫‪+ 15.00º‬‬ ‫‪- 10.74º‬‬
‫أﺛﺒﺖ أن ھﺬا اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﺍﳊﻞ‬
‫∞ ( ﻣ ﻊ اﻟﺘﺮﻛﯿ ﺰ‬ ‫‪0‬‬ ‫) ∞∞ ‪−‬‬ ‫ﯾﺘﻨﺎﺳ ﺐ اﻟﺘﻐﯿ ﺮ اﻟﻜﻠ ﻲ ﻓ ﻲ زاوﯾ ﺔ اﻟ ﺪوران‬

‫اﻷﺻﻠﻲ ﻟﺴﻜﺮ اﻟﻘﺼﺐ‪ .‬ﻛﺬﻟﻚ ﯾﺘﻨﺎﺳﺐ اﻟﺘﻐﯿﺮ ﻓﻲ زاوﯾ ﺔ اﻟ ﺪوران ﻋﻨ ﺪ‬
‫اﻟ ﺰﻣﻦ ‪ ( ∞0 − ∞ t ) t‬ﻣ ﻊ اﻟ ﻨﻘﺺ ﻓ ﻲ ﺗﺮﻛﯿ ﺰ ﺳ ﻜﺮ اﻟﻘﺼ ﺐ ﻋﻨ ﺪ ھ ﺬا‬
‫اﻟ ﺰﻣﻦ‪ .‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﺗﺮﻛﯿ ﺰ ﺳ ﻜﺮ اﻟﻘﺼ ﺐ اﻟﻤﺘﺒﻘ ﻲ ﻋﻨ ﺪ اﻟ ﺰﻣﻦ )‪(t‬‬
‫ﯾﺘﻨﺎﺳﺐ ﻣﻊ ‪:‬‬
‫) ∞∞ ‪( ∞0 − ∞∞ ) − ( ∞0 − ∞ t ) = ( ∞ t −‬‬
‫وأﻣﺎ إذا ﻛﺎن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ ﻓﺈﻧﮫ ﺳﯿﺘﺒﻊ اﻟﻤﻌﺎدﻟﺔ ‪:‬‬
‫‪2.303‬‬ ‫‪[ A ]0‬‬
‫=‪k‬‬ ‫‪log‬‬
‫‪t‬‬ ‫]‪[A‬‬

‫)‪(718‬‬
‫ﺣﯿ ﺚ ‪ [A]0‬ھ ﻮ اﻟﺘﺮﻛﯿ ﺰ اﻷﺻ ﻠﻲ و ]‪ [A‬اﻟﺘﺮﻛﯿ ﺰ ﻋﻨ ﺪ زﻣ ﻦ )‪(t‬‬

‫وﺑﺘﻌﻮﯾﺾ اﻟﻤﻌﻠﻮﻣﺎت اﻟﺴﺎﺑﻘﺔ ﺑﺪﻻً ﻣﻦ ‪ [A]0‬و ]‪ [A‬ﺗﻌﻄﻲ ‪:‬‬
‫=‪k‬‬
‫‪2.303‬‬ ‫) ∞∞ ‪( ∞ −‬‬
‫‪log 0‬‬
‫‪t‬‬ ‫) ∞∞ ‪( ∞ t −‬‬
‫∞(‬ ‫∞‬ ‫) ‪= - 10.74ο , ∞ 0 = + 24.04ο‬‬
‫‪( ∞0 − ∞∞ ) = 24.04 − (−10.74) = 34.78‬‬
‫اﻟﺰﻣﻦ )دﻗﯿﻘﺔ(‬ ‫‪7.20‬‬ ‫‪18.00‬‬ ‫‪27.00‬‬ ‫∞‬
‫) ‪ ( α‬زاوﯾﺔ اﻟﺪوران‬ ‫‪+ 21.40º‬‬ ‫‪+ 17.73º‬‬ ‫‪+ 15.00º‬‬ ‫‪- 10.74º‬‬
‫) ∞∞ ‪( ∞t −‬‬ ‫‪32.14‬‬ ‫‪28.47‬‬ ‫‪25.74‬‬ ‫‪0‬‬
‫‪2.303‬‬ ‫) ∞∞ ‪( ∞ −‬‬
‫‪log 0‬‬
‫=‪k‬‬ ‫‪0.011‬‬ ‫‪0.011‬‬ ‫‪0.011‬‬
‫‪t‬‬ ‫) ∞∞ ‪( ∞t −‬‬
‫وﻛﻤ ﺎ ھ ﻮ واﺿ ﺢ أن ﻗ ﯿﻢ ‪ k‬ﻋﻨ ﺪ اﻷزﻣﻨ ﺔ اﻟﻤﺨﺘﻠﻔ ﺔ ھ ﻮ ﻣﻘ ﺪار ﺛﺎﺑ ﺖ‬

‫)‪ (k = 0.011 min-1‬ﻣﻤﺎ ﯾﺪل ﻋﻠﻰ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ‪.‬‬
‫ﯾﺘﺤﻠﻞ اﻹﺳﺘﺮ ﻓﻲ اﻟﻤﺤﺎﻟﯿ ﻞ اﻟﻤﺎﺋﯿ ﺔ ﺑﺼ ﻮرة ﺑﻄﯿﺌ ﺔ ﺟ ﺪاً وﯾﻤﻜ ﻦ ﻗﯿ ﺎس‬

‫ﻣﻌﺪل اﻟﺘﺤﻠﻞ ﺑﺈﺿﺎﻓﺔ ﺣﻔﺎز ﻣﻦ اﻷﺣﻤﺎض اﻟﻤﻌﺪﻧﯿﺔ ‪:‬‬
‫‪CH 3COOC 2 H 5 + H 2 O ‬‬
‫‪cat‬‬
‫‪→ CH 3COOH + CH 3OH‬‬
‫ﻣ ﻦ اﻟﻮاﺿ ﺢ أن اﻟﻤ ﺎء ﻣﻮﺟ ﻮد ﺑﻜﻤﯿ ﺔ ﻛﺒﯿ ﺮة‪ ،‬وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﻣﺜ ﻞ ھ ﺬا‬

‫اﻟﺘﻔﺎﻋ ﻞ ﺗﻔﺎﻋ ﻞ ﻛ ﺎذب‪ ،‬وﯾﻌﺘﻤ ﺪ ﻓﻘ ﻂ ﻋﻠ ﻰ ﺗﺮﻛﯿ ﺰ ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ‬
‫وﺑﺘﻄﺒﯿﻖ اﻟﻘﺎﻧﻮن ‪:‬‬

‫)‪(719‬‬
‫‪2.303‬‬ ‫‪T - T0‬‬

‫=‪k‬‬ ‫∞ ‪log‬‬
‫‪t‬‬ ‫‪T∞ - Tt‬‬
‫ﺣﯿ ﺚ ) ‪ ( T∞ - Tt‬ﺗﻤﺜ ﻞ ﻗﯿﻤ ﺔ )‪ (x‬ﻛﻤﯿ ﺔ اﻹﺳ ﺘﺮ اﻟﺘ ﻲ ﺗﺤﻠﻠ ﺖ ‪ ،‬و‬

‫) ‪ ( T∞ - T0‬ﺗﻤﺜﻞ )‪ (a‬اﻟﺘﺮﻛﯿﺰ اﻹﺑﺘﺪاﺋﻲ ﻟﻺﺳﺘﺮ‪.‬‬
‫ﻣﺜﺎﻝ )‪(١١٩-٢‬‬
‫وﺿ ﻊ واﺣ ﺪ ﻣﻠﻠﺘ ﺮ ﻣ ﻦ ﺧ ﻼت اﻟﻤﯿﺜﯿ ﻞ ﻓ ﻲ دورق ﯾﺤﺘ ﻮي )‪(40 ml‬‬

‫ﻣ ﻦ ﻛﻠﻮرﯾ ﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ ﺗﺮﻛﯿ ﺰه )‪ (N/20‬ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة ‪(25‬‬
‫)‪ .ºC‬ﺳ ﺤﺒﺖ )‪ (2 ml‬ﻣ ﻦ اﻟﻤﺨﻠ ﻮط ﻋﻨ ﺪ أزﻣﻨ ﺔ ﻣﺨﺘﻠﻔ ﺔ‪ ،‬ﻟﻘﯿ ﺎس‬
‫ﺗﺮﻛﯿﺰه ﺑﻮاﺳﻄﺔ ھﯿﺪروﻛﺴﯿﺪ اﻟﺼﻮدﯾﻮم ﻓﺤﺼﻠﻨﺎ ﻋﻠﻰ اﻟﻨﺘﺎﺋﺞ اﻟﺘﺎﻟﯿﺔ ‪:‬‬
‫)‪Time (s‬‬ ‫‪0‬‬ ‫‪1200‬‬ ‫‪4500‬‬ ‫‪7140‬‬ ‫∞‬
‫‪NaOH used‬‬ ‫‪24.36‬‬ ‫‪25.85‬‬ ‫‪29.32‬‬ ‫‪31.72‬‬ ‫‪47.15‬‬
‫أﺛﺒﺖ أن اﻟﺘﻔﺎﻋﻞ ﻣﻦ اﻟﺮﺗﺒﺔ اﻷوﻟﻰ؟‬
‫ﺍﳊﻞ‬
‫‪Methyl acetate (a) = T∞ - T0 = 47.15 - 24.36 = 22.79 ml‬‬
‫‪Methyl acetate (a - x) = T∞ - Tt = 47.15 − Tt‬‬
‫‪2.303‬‬ ‫‪22.79‬‬
‫=‪k‬‬ ‫‪log‬‬ ‫‪= 5.635 × 10-5‬‬
‫‪1200‬‬ ‫)‪( 47.15 − 25.85‬‬
‫‪2.303‬‬ ‫‪22.79‬‬
‫=‪k‬‬ ‫‪log‬‬ ‫‪= 5.455 × 10-5‬‬
‫‪4500‬‬ ‫) ‪( 47.15 − 29.32‬‬
‫‪2.303‬‬ ‫‪22.79‬‬
‫=‪k‬‬ ‫‪log‬‬ ‫‪= 5.463 × 10-5‬‬
‫‪7140‬‬ ‫(‬ ‫‪47.15‬‬ ‫‪−‬‬ ‫‪31.72‬‬ ‫)‬

‫)‪(720‬‬
‫ﻣﺜﺎﻝ )‪(١٢٠-٢‬‬
‫ﺿﻊ ﻋﻼﻣﺔ ﺻﺢ أو ﺧﻄﺄ أﻣﺎم اﻟﻌﺒﺎرات اﻟﺘﺎﻟﯿﺔ ‪:‬‬

‫أ( طﺎﻗﺔ ﺗﻨﺸﯿﻂ ﺗﻔﺎﻋﻞ ﺗﺘﺴﺎوى ﻣﻊ طﺎﻗﺔ ﺗﻨﺸﯿﻂ اﻟﺘﻔﺎﻋﻞ اﻟﻤﻀﺎد‪.‬‬
‫ب( ارﺗﻔ ﺎع درﺟ ﺔ اﻟﺤ ﺮارة ﯾﺰﯾ ﺪ ﻣ ﻦ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻷﻣ ﺎﻣﻲ وﻣ ﻦ‬
‫ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻤﻀﺎد‪.‬‬
‫ج( ﻣ ﻦ اﻟﺼ ﻌﺐ اﺳ ﺘﻘﺮاء رﺗﺒ ﺔ ﺗﻔﺎﻋ ﻞ أي اﻷﺳ ﺲ اﻟﺘ ﻲ ﺗﺮﻓ ﻊ ﻟﮭ ﺎ‬
‫اﻟﺘﺮاﻛﯿﺰ ﻣﻦ ﻣﻌﺎدﻟﺘﮫ اﻟﻤﻮزوﻧﺔ‪.‬‬
‫ﻣﺘﻨﺎھﯿ ﺔ اﻟﺼ ﻐﺮ ﻛ ﺎن ﻣﺘﻮﺳ ﻂ اﻟﺴ ﺮﻋﺔ ﻟﺘﻔﺎﻋ ﻞ‬ ‫) ‪( Δt‬‬ ‫د( ﻋﻨ ﺪﻣﺎ ﯾﻜ ﻮن‬
‫ﻣﺴﺎوﯾﺎ ً ﻟﺴﺮﻋﺘﮫ اﻟﻠﺤﻈﯿﺔ‪.‬‬
‫ھـ( ﯾﺘﻐﯿﺮ ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻛﻠﻤﺎ ﺗﻐﯿﺮت ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫و( ﯾﻌﺘﻤ ﺪ ﻧﺼ ﻒ زﻣ ﻦ ﺗﻔﺎﻋ ﻞ اﻟﺮﺗﺒ ﺔ اﻷوﻟ ﻰ ﻋﻠ ﻰ ﺗﺮﻛﯿ ﺰ اﻟﻤ ﺎدة ﻓ ﻲ‬
‫ﺑﺪاﯾﺔ اﻟﺘﻔﺎﻋﻞ‪.‬‬
‫ز( ﺗﺘﻨﺎﺳ ﺐ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ طﺮدﯾ ﺎ ً ﻣ ﻊ اﻟﺘﺮﻛﯿ ﺰ اﻟﻤ ﻮﻻري ﻟﻠﻤ ﻮاد‬
‫اﻟﻤﺘﻔﺎﻋﻠﺔ‪.‬‬
‫ح( ﺣﯿﻨﻤﺎ ﯾﺰداد ﺗﺮﻛﯿﺰ اﻟﻤﻮاد اﻟﻤﺸﺘﺮﻛﺔ ﻓﻲ ﺗﻔﺎﻋ ﻞ اﻟﺮﺗﺒ ﺔ اﻟﺜﺎﻧﯿ ﺔ ﻓ ﺈن‬
‫ﻧﺼﻒ ﻋﻤﺮ اﻟﺘﻔﺎﻋﻞ ﯾﻨﻘﺺ‪.‬‬

02- قانون سرعة التفاعل - رتب التفاعل

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02- قانون سرعة التفاعل - رتب التفاعل

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‫ ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬: ‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ‬

‫ ﺍﳍﺰﺍﺯﻱ‬‫ ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‬.‫ ﺩ‬/‫ﺇﻋﺪﺍﺩ‬

‫ﻗﺎﻧﻮﻥ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺗﻐﲑ ﺗﺮﻛﻴﺰ ﺍﳌﺎﺩﺓ ﺍﳌﺘﻔﺎﻋﻠﺔ ﻣﻊ ﺍﻟﺰﻣﻦ‬

‫ﺗﻮﺿ ﺢ ﻣﻌﺎدﻟ ﺔ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﻛﯿ ﻒ ﺗﺘﻐﯿ ﺮ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ ﺑﺘﻐﯿ ﺮ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﻧﻌﺘﺒﺮ ﺗﻔ ﺎﻋﻼً ﻛﯿﻤﯿﺎﺋﯿ ﺎ ً ﯾﻨﺤ ﻞ ﻓﯿ ﮫ اﻟﻤﺘﻔﺎﻋ ﻞ )‪ (A‬ﻣﻌﻄﯿ ﺎ ً ﻧ ﺎﺗﺠﯿﻦ ھﻤ ﺎ ‪:‬‬

‫وﻓ ﻲ أﺛﻨ ﺎء ﺳ ﯿﺮ اﻟﺘﻔﺎﻋ ﻞ ﯾﻘ ﻞ ﺗﺮﻛﯿ ﺰ اﻟﻤﺘﻔﺎﻋ ﻞ )‪ (A‬ﻓ ﻲ ﺣ ﯿﻦ ﯾ ﺰداد‬

‫ﺷﻜﻞ )‪ : (١-٢‬اﻟﻌﻼﻗﺔ ﺑﯿﻦ اﻟﺘﺮﻛﯿﺰ واﻟﺰﻣﻦ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫وﺗﻌﯿﻦ اﻟﺴﺮﻋﺔ ﺑﺎﻟﺘﻐﯿﺮ ﻓﻲ ﻛﻤﯿﺔ ﻣﻘﺎﺳﺔ ﻣﻊ اﻟﺘﻐﯿﺮ ﻓ ﻲ اﻟ ﺰﻣﻦ‪ .‬وﺗﻘ ﺎس‬

‫ﻓﯿﻌﺒ ﺮ ﻋ ﻦ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﯿﻤﯿ ﺎﺋﻲ ﺑﻤﻌ ﺪل اﺧﺘﻔ ﺎء اﻟﻤﺘﻔﺎﻋ ﻞ أو‬

‫ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻭﺍﻋﺘﻤﺎﺩﻫﺎ ﻋﻠﻰ ﺗﺮﻛﻴﺰ ﺍﳌﺘﻔﺎﻋﻼﺕ‬

‫ﺣﯿﺚ )‪ (n‬ﺛﺎﺑﺖ ﯾﺴﻤﻰ رﺗﺒﺔ اﻟﻤﺘﻔﺎﻋﻞ‪ .‬واﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ﺳ ﺮﻋﺔ اﻟﺘﻔﺎﻋ ﻞ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﻭﺣﺪﺍﺕ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ )‪(k‬‬

‫وﺗﻌﺘﻤﺪ وﺣﺪات اﻟﺜﺎﺑﺖ ﻟﺴﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ ﻋﻠﻰ رﺗﺒﺔ اﻟﺘﻔﺎﻋﻞ‬

‫وﺑﺬا ﺗﻜﻮن ‪:‬‬

‫ﻟﺬا ﻓﺈﻧ ﮫ ﻟﺠﻤﯿ ﻊ اﻟﻌﻤﻠﯿ ﺎت أﺣﺎدﯾ ﺔ اﻟﺮﺗﺒ ﺔ ﺗﻜ ﻮن وﺣ ﺪات اﻟﺜﺎﺑ ﺖ "‪'k‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫• أﻣﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻼت ﺛﻨﺎﺋﯿﺔ اﻟﺮﺗﺒﺔ‪ ،‬ﺗﺄﺧﺬ ﻣﻌﺎدﻟﺔ اﻟﺴﺮﻋﺔ‬

‫ﻭﺣﺪﺓ ﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ ﺑﺸﻜﻞ ﻋﺎﻡ‬

‫ﺛﺎﺑﺖ اﻟﺴﺮﻋﺔ ﻟﺘﻔﺎﻋﻞ ذي رﺗﺒﺔ )‪ (n‬ﯾﺄﺧﺬ اﻟﻮﺣﺪات ‪:‬‬

‫وﯾﻤﻜﻦ ﺗﻄﺒﯿﻖ ھﺬه اﻟﻘﺎﻋﺪة ﻋﻠﻰ اﻟﺮﺗﺐ ﻛﻤﺎ ﻓﻲ اﻟﺠﺪول )‪ (١-٢‬أدﻧﺎه‪.‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﺗﻌﻴﲔ ﺭﺗﺒﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻭﺛﺎﺑﺖ ﺍﻟﺴﺮﻋﺔ‬

‫ﻣﻦ ﻗﺎﻧﻮن ﺳﺮﻋﺔ اﻟﺘﻔﺎﻋﻞ اﻟﻌﺎم ‪:‬‬

‫ﻧﺮى أن اﻟﻘﺎﻧﻮن ﻣﻜﻮن ﻣﻦ ‪:‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﻃﺮﻕ ﺇﳚﺎﺩ ﺛﺎﺑﺖ ﺍﻟﺘﻔﺎﻋﻞ ﻭﺭﺗﺒﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻟﻠﺘﻔﺎﻋﻼﺕ ﺍﻟﺒﺴﻴﻄﺔ‬

‫‪ (١‬ﻃﺮﻳﻘﺔ ﺍﻟﺘﻔﺎﺿﻞ )‪(Differential Method‬‬

‫ﻗﻮاﻧﯿﻦ اﻟﺴﺮﻋﺔ اﻟﻤﺴ ﺘﺨﺪﻣﺔ ھ ﻲ ﻋﺒ ﺎرة ﻋ ﻦ ﻣﻌ ﺎدﻻت ﺗﻔﺎﺿ ﻠﯿﺔ‪ .‬وﻟﻘ ﺪ‬

‫اﻗﺘﺮح ھﺬه اﻟﻄﺮﯾﻘﺔ اﻟﻌﺎﻟﻢ ﻓﺎﻧﺖ ھﻮف )‪ (Van't Hoff‬ﻋ ﺎم )‪1884‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫اﻟﻨﻘ ﺎط وﻧﺤﺼ ﻞ ﻋﻠ ﻰ اﻟﻘﯿﻤ ﺔ )‪ .(- dc/dt‬وﯾﻌﻄ ﻲ اﻟﻤﯿ ﻞ اﻹﺑﺘ ﺪاﺋﻲ‬

‫واﻟﻌﻼﻗ ﺔ اﻟﻨﺎﺗﺠ ﺔ ) ‪ ( log rate = n log c + log k‬ﺗﻤﺜ ﻞ ﻣﻌﺎدﻟ ﺔ ﺧ ﻂ‬

‫ﺇﳚﺎﺩ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ )‪(rate‬‬

‫ﻟﻜﻲ ﻧﻮﺟﺪ )‪ (rate‬ﻟﻠﺘﻔﺎﻋ ﻞ ﯾﻘ ﺎس ﺗﻐﯿ ﺮ اﻟﺘﺮاﻛﯿ ﺰ )اﻟﻨ ﻮاﺗﺞ ﻋ ﺎدة( ﻣ ﻊ‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﺇﻋﺪﺍﺩ‪ /‬ﺩ‪ .‬ﻋﻤﺮ ﺑﻦ ﻋﺒﺪ ﺍ‪ ‬ﺍﳍﺰﺍﺯﻱ‬

‫ﻃﺮﻕ ﺣﺴﺎﺏ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬

‫ﻫﻨﺎﻙ ﻃﺮﻳﻘﺘﺎﻥ ﳊﺴﺎﺏ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬

‫)‪(Initial Rate Method‬‬

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‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ ‪ :‬ﻗﻮﺍﻧﲔ ﺳﺮﻋﺔ ﺍﻟﺘﻔﺎﻋﻞ‬