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1460
ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
"ﺍﻟﺪﻳﻨﺎﻣﻴﻜﺎ ﺍﳊﺮﺍﺭﻳﺔ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ"
CHEMICAL THERMODYNAMICS
ﻣﻘﺪﻣﺔ
ﺗﻮﺟﺪ أﻧﻮاع ﻛﺜﯿﺮة ﻣﻦ اﻟﻄﺎﻗﺔ ﻣﺜ ﻞ اﻟﻄﺎﻗ ﺔ اﻟﺤﺮارﯾ ﺔ ،اﻟﻄﺎﻗ ﺔ اﻟﻜﮭﺮﺑﯿ ﺔ ،اﻟﻄﺎﻗ ﺔ اﻟﻤﯿﻜﺎﻧﯿﻜﯿ ﺔ،
اﻟﻄﺎﻗﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ ،اﻟﻄﺎﻗﺔ اﻟﻤﻐﻨﺎﻃﯿﺴﯿﺔ ،اﻟﻄﺎﻗﺔ اﻟﺤﺮﻛﯿﺔ واﻟﻄﺎﻗﺔ اﻟﺴﻄﺤﯿﺔ وﻏﯿﺮ ذﻟﻚ وﺗﺤ ﺖ
ﻇ ﺮوف ﻣﻌﯿﻨ ﺔ ﯾﻤﻜ ﻦ ﻟﮭ ﺬه اﻷﻧ ﻮاع ﻣ ﻦ اﻟﻄﺎﻗ ﺔ أن ﺗﺘﺤ ﻮل اﻟ ﻰ ﺑﻌ ﻀﮭﺎ اﻟ ﺒﻌﺾ ،وﺗﮭ ﺘﻢ
اﻟ ﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾ ﺔ ﺑﺎﻟﺒﺤ ﺚ ﻋ ﻦ اﻟﻌﻼﻗ ﺔ ﺑ ﯿﻦ ھ ﺬه اﻷﻧ ﻮاع اﻟﻤﺨﺘﻠﻔ ﺔ ﻣ ﻦ اﻟﻄﺎﻗ ﺔ ﻛﻤ ﺎ ﺗﮭ ﺘﻢ
ﺑﺎﻧﺘﻘﺎل اﻟﺤﺮارة وﻛﺬﻟﻚ اﻟﺸﻐﻞ اﻟﻤﺼﺎﺣﺐ ﻟﺒﻌﺾ اﻟﻌﻤﻠﯿﺎت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ واﻟﻔﯿﺰﯾﺎﺋﯿﺔ.
ﯾﺘﻜ ﻮن ﻣ ﺼﻄﻠﺢ " "Thermodynamicsﻣ ﻦ ﻣﻘﻄﻌ ﯿﻦ ،ھﻤ ﺎ ﻛﻠﻤ ﺔ " :ﺛﯿﺮﻣ ﻮ"Thermo
أي اﻟﺤ ﺮارة ،وﻛﻠﻤ ﺔ "دﯾﻨﺎﻣﯿ ﻚ "dynamicsأي اﻟﻤﺘﺤ ﺮك ،وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ھ ﺬا اﻟﻤ ﺼﻄﻠﺢ
ﯾﻌﻨﻲ اﻟﺤﺮارة اﻟﻤﺘﺤﺮﻛﺔ ،واﻟﺘﻲ ﺗﺘﺤﻮل ﻣﻦ ﺷﻜﻞ اﻟﻰ آﺧﺮ ،وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن :
اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ :ﻋﻠﻢ ﯾﮭﺘﻢ ﺑﺪراﺳﺔ اﻟﻄﺎﻗﺔ وﺗﺤﻮﻻﺗﮭﺎ ،وﯾﮭﺪف ﻧﺤﻮ ﺗﺤﻮﯾﻞ أﻛﺒﺮ ﻣﻘﺪار ﻣﻦ
اﻟﻄﺎﻗﺔ اﻟﺤﺮارﯾﺔ اﻟﻨﺎﺗﺠﺔ ﻣﻦ اﺣﺘﺮاق اﻟﻮﻗﻮد اﻟﻰ ﻃﺎﻗﺔ ﻣﯿﻜﺎﻧﯿﻜﯿﺔ ،ﺑﻤﻌﻨﻰ آﺧﺮ :ﺗﺤﺴﯿﻦ
ﻛﻔﺎءة اﻟﻤﺤﺮك.
وﺑﻨﻲ ھﺬا اﻟﻌﻠﻢ ﻋﻠﻰ أﺳﺎس اﻟﺘﺠﺮﺑﺔ اﻹﻧﺴﺎﻧﯿﺔ اﻟﻜﺒﺮى أن اﻟﻄﺎﻗﺔ ﻣﻮﺟﻮدة ،وﻻ ﯾﻤﻜﻦ ﺧﻠﻘﮭﺎ
أو ﻓﻨﺎؤھﺎ .وﻣﻦ ھﺬه اﻟﺤﻘﯿﻘﺔ أﻣﻜﻦ اﺳﺘﻨﺒﺎط ﻋﻼﻗﺎت رﯾﺎﺿﯿﺔ ﻣﺨﺘﻠﻔﺔ ﺑﯿﻦ ﺧﻮاص اﻟﻤﺎدة،
اﻟﺘﻲ ﺗﻨﻄﻮي ﻋﻠﻰ اﻣﺘﺼﺎص ﻟﻠﺤﺮارة.
وﺗﻌﺘﻤﺪ دراﺳﺔ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ أﺳﺎﺳﺎً ﻋﻠﻰ ﺛﻼﺛﺔ ﺗﻌﻤﯿﻤﺎت ،ﺗﻌﺮف ﺑﺎﻟﻘﻮاﻧﯿﻦ اﻟﺜﻼﺛﺔ
ﻟﻠﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ،وھﻲ :اﻟﻘﺎﻧﻮن اﻷول ،واﻟﻘﺎﻧﻮن اﻟﺜﺎﻧﻲ ،واﻟﻘﺎﻧﻮن اﻟﺜﺎﻟﺚ ﻟﻠﺪﯾﻨﺎﻣﯿﻜﺎ
اﻟﺤﺮارﯾﺔ .وھﺬه اﻟﻘﻮاﻧﯿﻦ اﻟﺜﻼﺛﺔ ﻻ ﺗﻌﺘﻤﺪ ﻋﻠﻰ أي ﻧﻤﻮذج أو أي ﻧﻈﺮﯾﺔ ﺧﺎﺻﺔ ﺑﺎﻟﺘﺮﻛﯿﺐ
اﻟﺬري أو اﻟﺠﺰﯾﺌﻲ أو ﺑﻄﺒﯿﻌﺔ اﻟﻤﺎدة ،وﻟﺬﻟﻚ ﻓﺈن أي ﺗﻄﻮر ﯾﺤﺪث ﻓﻲ اﻷﻓﻜﺎر واﻟﻨﻈﺮﯾﺎت
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1461
اﻟﺤﺎﻟﯿﺔ اﻟﺨﺎﺻﺔ ﺑﻄﺒﯿﻌﺔ اﻟﺠﺰﯾﺌﺎت ﻟﻦ ﯾﺆﺛﺮ ﺑﺄي ﻃﺮﯾﻘﺔ ﻋﻠﻰ ﺻﺤﺔ أي ﻧﺘﯿﺠﺔ دﯾﻨﺎﻣﯿﻜﯿﺔ
ﺣﺮارﯾﺔ.
ﺗﻠﻘﺎﺋﻴﺔ ﺍﻟﺘﻔﺎﻋﻞ
Spontaneity of Reaction
ﯾﻌﺪ ﻋﻠﻢ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ )اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ( أﺣﺪ ﻓﺮوع ﻋﻠﻢ اﻟﻜﯿﻤﯿﺎء اﻟﻤﮭﻤﺔ ،واﻟﺬي ﯾﻤﻜﻦ
ﺑﻮاﺳﻄﺘﮫ دراﺳﺔ )ﺑﺸﻜﻞ ﻧﻈﺮي( إﻣﻜﺎﻧﯿﺔ ﺣﺪوث ﺗﻔﺎﻋﻞ ﻛﯿﻤﯿﺎﺋﻲ ﻣﻦ ﻋﺪﻣﮫ ،أي أﻧﮫ دون
إﺟﺮاء اﻟﺘﺠﺮﺑﺔ اﻟﻌﻤﻠﯿﺔ ﯾﻤﻜﻦ أن ﻧﻘﺮر ﻣﺎ إذا ﻛﺎﻧﺖ ﻣﺎدﺗﺎن ﻛﯿﻤﯿﺎﺋﯿﺘﺎن ﺳﺘﺘﻔﺎﻋﻼن ﺗﻠﻘﺎﺋﯿﺎً أم
ﻻ ،ﻣﻤﺎ ﯾﻮﻓﺮ ﻛﺜﯿﺮاً ﻣﻦ اﻟﻮﻗﺖ واﻟﺠﮭﺪ واﻟﻜﻠﻔﺔ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1462
وﺑﺎﺳﺘﺨﺪام ﺟﺪاول اﻟﻜﯿﻤﻮﺣﺮارﯾﺔ ،ﯾﻤﻜﻦ اﻹﺳﺘﻨﺘﺎج أﻧﮫ ﻋﻨﺪ ﺧﻠﻂ ﻏﺎز اﻟﮭﯿﺪروﺟﯿﻦ ﻣﻊ ﻏﺎز
اﻟﻨﯿﺘﺮوﺟﯿﻦ ﺑﻨﺴﺒﺔ ) (3 : 1ﻋﻨﺪ درﺟﺔ ﺣﺮارة ) (450 °Cوﺗﺤﺖ ﺿﻐﻂ ) ،(10 atmﻓﺈن
اﻟﻀﻐﻂ اﻟﺠﺰﺋﻲ ﻟﻸﻣﻮﻧﯿﺎ ﯾﺼﻞ اﻟﻰ ) ،(0.204 atmوأن ﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﻨﺎﺗﺠﺔ ﻋﻦ ھﺬا
اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي ).(13.37 kCal
وﻟﻜﻦ ﻋﻠﻢ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﺑﻤﻔﺮده ﻻ ﯾﺒﯿﻦ – ﻣﻊ اﻷﺳﻒ – اﻟﻮﻗﺖ اﻟﻤﻄﻠﻮب ﻟﺤﺪوث
اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ .ﻓﻤﺜﻼً ،ﯾﺘﻨﺒﺄ ﻋﻠﻢ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﺑﺄن أﻛﺴﺪة أﻟﻤﺎس )ﺑﻠﻮرات ﻧﻘﯿﺔ ﻣﻦ
اﻟﻜﺮﺑﻮن( ﺗﺤﺖ ﻇﺮوف ﻋﺎدﯾﺔ ﻣﻦ اﻟﻤﻤﻜﻦ أن ﺗﺤﺪث ،أي أن اﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﻲ .وﺑﻤﻌﻨﻰ آﺧﺮ
ﯾﺘﻨﺒﺄ ﻋﻠﻢ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﺑﺄن اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ ﯾﺤﺪث ﻋﻨﺪ درﺟﺔ ﺣﺮارة اﻟﻐﺮﻓﺔ :
وﻟﻜﻨﻨﺎ ﻧﻌﻠﻢ ﺟﯿﺪاً ﺑﺄن ھﺬا اﻟﺘﻔﺎﻋﻞ ﻻ ﯾﺤﺪث ﺑﺴﺮﻋﺔ ﻣﻦ اﻟﻤﻤﻜﻦ ﻣﻼﺣﻈﺘﮭﺎ ﺗﺤﺖ اﻟﻈﺮوف
اﻟﻌﺎدﯾﺔ ،أي أن ھﺬا اﻟﺘﻔﺎﻋﻞ ﯾﺴﺘﻐﺮق وﻗﺘﺎً ﻃﻮﯾﻼً ﺟﺪاً ﻟﻜﻲ ﯾﺤﺪث.
وھﻜﺬا ﯾﻤﻜﻦ اﻟﻘﻮل ﺑﺄن اﻟﻔﺎﺋﺪة اﻟﻤﺮﺟﻮة ﻣﻦ دراﺳﺔ ﻗﻮاﻧﯿﻦ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ،
ھﻲ أﻧﮭﺎ ﺗﻤﻜﻨﻨﺎ ﻣﻦ اﻟﻘﻮل ﺑﺈﻣﻜﺎﻧﯿﺔ ﺣﺪوث ﺗﻔﺎﻋﻞ ﻛﯿﻤﯿﺎﺋﻲ ﻣﻌﯿﻦ أو ﻋﺪم ﺣﺪوﺛﮫ.
واﻟﺘﻔﺎﻋﻞ اﻟﺬي ﯾﺤﺪث ﻣﻦ ذات ﻧﻔﺴﮫ ﻓﻲ اﻟﻈﺮوف اﻟﻌﺎدﯾﺔ ﯾﻌﺮف ﺑﺎﻟﺘﻔﺎﻋﻞ اﻟﺘﻠﻘﺎﺋﻲ.
وﯾﻤﻜﻦ اﻹﺳﺘﻔﺎدة ﻣﻦ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﻓﻲ ﺗﺤﺪﯾﺪ ﻧﻮﻋﯿﺔ اﻟﺘﻔﺎﻋﻞ اﻟﺘﻠﻘﺎﺋﻲ ،وﻛﺬﻟﻚ ﻣﻮﺿﻊ
اﻹﺗﺰان ﻓﻲ اﻟﺘﻔﺎﻋﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1463
وﻓﻲ اﻟﺤﻘﯿﻘﺔ ﻓﺈن ﻋﻠﻢ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﻻ ﯾﻌﻄﯿﻨﺎ أﯾﺔ ﻣﻌﻠﻮﻣﺎت ﻛﺬﻟﻚ ﻋﻦ ﻣﯿﻜﺎﻧﯿﻜﯿﺔ
اﻟﺘﻔﺎﻋﻼت اﻟﺘﻠﻘﺎﺋﯿﺔ ،وﺗﺠﯿﺐ ﻋﻦ ﻣﺜﻞ ھﺬه اﻟﺘﺴﺎؤﻻت دراﺳﺔ ﺣﺮﻛﯿﺔ اﻟﺘﻔﺎﻋﻼت )اﻟﺤﺮﻛﯿﺔ
اﻟﻜﯿﻤﯿﺎﺋﯿﺔ( ،ﻓﮭﻨﺎك ﺑﻌﺾ اﻟﺘﻐﯿﺮات اﻟﺘﻠﻘﺎﺋﯿﺔ اﻟﺘﻲ ﺗﺤﺪث ﺑﺒﻂء ﺷﺪﯾﺪ ،ﻓﻨﺠﺪ أن اﻟﺼﻮرة
اﻟﺘﺄﺻﻠﯿﺔ اﻟﺜﺎﺑﺘﺔ ﻟﻌﻨﺼﺮ اﻟﻜﺮﺑﻮن ﻋﻨﺪ اﻟﻈﺮوف اﻟﻌﺎدﯾﺔ ھﻲ اﻟﺠﺮاﻓﯿﺖ وﻟﯿﺲ اﻷﻟﻤﺎس،
واﻟﺘﺤﻮل ﻣﻦ اﻷﻟﻤﺎس اﻟﻰ اﻟﺠﺮاﻓﯿﺖ ھﻲ ﻋﻤﻠﯿﺔ ﺗﻠﻘﺎﺋﯿﺔ ﻣﻦ اﻟﻮﺟﮭﺔ اﻟﺪﯾﻨﺎﻣﯿﻜﯿﺔ اﻟﺤﺮارﯾﺔ،
وھﺬا اﻟﺘﺤﻮل ﻣﻦ اﻟﺒﻂء ﺑﻤﻜﺎن ﺑﺤﯿﺚ ﻻ ﯾﻤﻜﻦ أن ﯾﻼﺣﻆ ﻋﻨﺪ درﺟﺎت اﻟﺤﺮارة واﻟﻀﻐﻮط
اﻟﻌﺎدﯾﺔ وﯾﺤﺘﺎج اﻟﻰ ﻣﻼﯾﯿﻦ اﻟﺴﻨﯿﻦ.
ﺗﻌﺎﺭﻳﻒ ﺃﺳﺎﺳﻴﺔ
Basic Definitions
ﺍﻟﻨﻈﺎﻡ ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻲ ﻭﺃﻧﻮﺍﻋﻪ
Thermodynamic System and its Types
ﺷﻜﻞ) : (١اﻟﻨﻈﺎم ﻛﻞ ﺷﻲء داﺧﻞ اﻟﺤﺪود )اﻟﻤﺎدة اﻟﻐﺎزﯾﺔ ،اﻟﺴﺎﺋﻠﺔ ،اﻟﺼﻠﺒﺔ( أﻣﺎ اﻟﻤﺤﯿﻂ ﻓﮭﻮ ﻛ ﻞ ﺷ ﻲء ﺧﺎرﺟﮭ ﺎ .وﺗﻤﺜ ﻞ
ﺟﺪران اﻟﺤﺎوي ﻟﻠﻨﻈﺎم اﻟﺤﺪود اﻟﻔﺎﺻﻠﺔ ﺑﯿﻦ اﻟﻨﻈﺎم واﻟﻤﺤﯿﻂ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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Fig. 2 : In thermodynamics, the world is divided into a system(the object of interest) and
the surroundings (everything else). In practice, the surrounding may be a constant
temperature water bath. The arrows represent the energy being transferred between the
system and its surroundings.
وﻗﺪ ﺗﻮﺟﺪ ﻋﻼﻗﺔ ﺑﯿﻦ اﻟﻨﻈﺎم واﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ ﺑﮫ ،ﺣﯿﺚ ﯾ ﺆﺛﺮ ﻛ ﻞ ﻣﻨﮭﻤ ﺎ ﻓ ﻲ اﻵﺧ ﺮ .وﺑﻤ ﺎ أن
أي ﻧﻈ ﺎم ﻻ ﯾﺨﻠ ﻮ ﻣ ﻦ ﻛﻮﻧ ﮫ ﻣ ﺎدة وﻃﺎﻗ ﺔ ،ﻓﺈﻧ ﮫ ﯾﻤﻜ ﻦ أن ﯾﺤ ﺪث ﺗ ﺄﺛﯿﺮ ﻣﺘﺒ ﺎدل ﺑ ﯿﻦ اﻟﻨﻈ ﺎم
ووﺳﻄﮫ اﻟﻤﺤﯿﻂ ،ﻣﻦ ﺧﻼل اﻟﻤﺎدة أو اﻟﻄﺎﻗﺔ أو ﻛﻠﯿﮭﻤﺎ.
ﺃﺻﻨﺎﻑ ﺍﻷﻧﻈﻤﺔ
System's Types
وﯾﻜﻮن اﻟﻨﻈﺎم ﻣﻔﺘﻮﺣﺎً إذا ﻛﺎن ﯾﺘﺒﺎدل اﻟﻤﺎدة واﻟﻄﺎﻗﺔ ﻣﻊ اﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ.
وﯾﻤﺜﻞ ﻟﺬﻟﻚ اﻟﻨﻈﺎم ﺑﺈﻧﺎء ﻣﻌﺪﻧﻲ ﯾﺤﺘﻮي ﻋﻠﻰ ﻣﺎء ﯾﻐﻠﻲ ،ﻓﺈﻧﮫ ﯾﻼﺣﻆ أن ﻣﺎدة اﻟﻨﻈﺎم ،وھﻲ
اﻟﻤﺎء ،ﺗﺘﺼﺎﻋﺪ ﻋﻠﻰ ھﯿﺌﺔ ﺑﺨﺎر ﯾﻨﺘﻘﻞ اﻟﻰ اﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ ﻣﻦ ﺣﻮﻟﮫ ،ﻛﻤﺎ أن ﺣﺮارة اﻟﻤﺎء
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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)ﻃﺎﻗﺔ( ﺗﺘﺴﺮب اﻟﻰ اﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ .وﯾﻘﺎل أن ھﺬا اﻟﻨﻈﺎم ﻗﺪ ﺑﺎدل ﻛﻼً ﻣﻦ ﻣﺎدﺗﮫ وﻃﺎﻗﺘﮫ ﻣﻊ
اﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ.
وﻣﻦ أﻣﺜﻠﺔ ھﺬا اﻟﻨﻈﺎم أﯾﻀﺎً ،ﺟﻤﯿﻊ اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺘﻲ ﺗﺘﻢ ﻓﻲ اﻟﻤﻌﻤﻞ ،وﺗﺠﺮى ﻓﻲ
آﻧﯿﺔ ﻣﻔﺘﻮﺣﺔ.
وﯾﻜﻮن اﻟﻨﻈﺎم ﻣﻐﻠﻘﺎً إذا ﻛﺎﻧﺖ ﺣﺪود اﻟﻨﻈﺎم ﺗﺴﻤﺢ ﺑﺘﺒﺎدل اﻟﻄﺎﻗﺔ ﻓﻘﻂ ﻋﻠﻰ ﺷﻜﻞ ﺣﺮارة
وﺷﻐﻞ ﻣﻊ اﻟﻤﺤﯿﻂ ﺑﺸﺮط أن ﻻ ﺗﺘﻐﯿﺮ ﻛﻤﯿﺔ اﻟﻤﺎدة ﻓﻲ اﻟﻨﻈﺎم.
وﯾﻤﺜﻞ ﻟﺬﻟﻚ اﻟﻨﻈﺎم ﺑﻤﺎء ﯾﻐﻠﻲ ﻣﻮﺿﻮع ﻓﻲ إﻧﺎء ﻣﻌﺪﻧﻲ ﻣﻐﻠﻖ ﺑﺈﺣﻜﺎم ،ﻓﻔﻲ ھﺬه اﻟﺤﺎﻟﺔ
ﯾﻼﺣﻆ أن ﺣﺮارة اﻟﻤﺎء ﺗﺘﺴﺮب اﻟﻰ اﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ ،ﺑﯿﻨﻤﺎ اﻟﻤﺎء )وھﻮ ﻣﺎدة اﻟﻨﻈﺎم( ﻻ ﯾﻨﺘﻘﻞ
اﻟﻰ اﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ .وﯾﻘﺎل إن ھﺬا اﻟﻨﻈﺎم ﻗﺪ ﺑﺎدل ﻃﺎﻗﺘﮫ ﻓﻘﻂ ،دون ﻣﺎدﺗﮫ ﻣﻊ اﻟﻮﺳﻂ
اﻟﻤﺤﯿﻂ.
وﻣﻦ أﻣﺜﻠﺔ ھﺬا اﻟﻨﻈﺎم أﯾﻀﺎً ،ﺟﻤﯿﻊ اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺘﻲ ﺗﺘﻢ ﻓﻲ اﻟﻤﻌﻤﻞ ،وﺗﺠﺮى ﻓﻲ
آﻧﯿﺔ ﻣﻐﻠﻘﺔ ذات ﺟﺪار ﻣﻮﺻﻞ ﻟﻠﺤﺮارة.
وﯾﻜﻮن اﻟﻨﻈﺎم ﻣﻌﺰوﻻً إذا ﻛﺎﻧﺖ ﺣﺪود اﻟﻨﻈﺎم ﻻ ﺗﺴﻤﺢ ﺑﺘﺒﺎدل اﻟﻤﺎدة أو اﻟﻄﺎﻗﺔ ﻣﻊ اﻟﻤﺤﯿﻂ
أي أن اﻟﻨﻈﺎم ﻻ ﯾﺘﺄﺛﺮ أﺑﺪاً ﺑﺎﻟﻤﺤﯿﻂ.
وﯾﻤﺜﻞ ﻟﮭﺬا اﻟﻨﻈﺎم ﺑﺎﻟﺘﺮﻣﺲ ،ﺣﯿﺚ أﻧﮫ ﯾﺤﻔﻆ ﺣﺮارة اﻟﻨﻈﺎم وﻣﺎدﺗﮫ ﻣﻦ اﻟﺘﺴﺮب اﻟﻰ اﻟﻮﺳﻂ
اﻟﻤﺤﯿﻂ.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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Fig. 4 : We classify systems into one of three kinds, according to their interactions with
their surroundings. An open system can exchange matter and energy with its surroundings.
A closed system can exchange energy but not matter. An isolated system can exchange
neither matter nor energy.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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وﻣﻦ اﻟﺠﺪﯾﺮ ﺑﺎﻟﺬﻛﺮ اﻹﺷﺎرة اﻟﻰ أن ﺗﺒﺎدل اﻟﻄﺎﻗﺔ ﺑﯿﻦ اﻟﻨﻈﺎم واﻟﻮﺳﻂ اﻟﻤﺤﯿﻂ ﯾﻤﻜﻦ أن
. اﻟﺤﺮارة واﻟﺸﻐﻞ: ﯾﺤﺪث ﻋﻠﻰ ﺻﻮرﺗﯿﻦ وھﻤﺎ
Fig. 5 : When a system is free to expand against an external pressure, some of the energy
supplied to it as heat escape back into the surroundings as work. As a result, the change in
internal energy is less than the energy supplied.
Fig. 6 : A reaction does work when it generates a gas. For example, carbon dioxide is
formed from the thermal decomposition of calcium carbonate. As the gas is formed, it
drives back the surrounding atmosphere.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻛﻤﺎ أن ﻗﻮاﻧﯿﻦ اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ذات ﻃﺒﯿﻌﺔ ﻋﺎﻣﺔ ،وﺗﻨﻄﺒﻖ ﻓﻲ ﺟﻤﯿﻊ اﻟﺤﺎﻻت ،وﻟﯿﺴﺖ
ﻣﺤﺪودة ﻋﻠﻰ ﺣﺎﻻت اﻟﺘﻮازن ﺑﺎﻟﺬات.
إذا ﻛﺎن ﻟﺪﯾﻨﺎ ﻧﻈﺎم ﻏﺎزي ﻣﺘﺠﺎﻧﺲ ) (homogeneousﯾﺘﻜﻮن ﻣﻦ ﻣﺎدة واﺣﺪة ﻓﺈن ﻣﻜﻮﻧﺎﺗﮫ
ﺑﺎﻟﻄﺒﻊ ﺛﺎﺑﺘﺔ وﻣﻦ ﺛﻢ ﻓﺈن ﺣﺎﻟﺔ اﻟﻨﻈﺎم ﺗﻌﺘﻤﺪ ﻋﻠﻰ اﻟﻀﻐﻂ واﻟﺤﺠﻢ ودرﺟﺔ اﻟﺤﺮارة ﻓﻘﻂ .وإذا
ﻛﺎﻧﺖ ﺟﻤﯿﻊ ھﺬه اﻟﻜﻤﯿﺎت ﺛﺎﺑﺘﺔ ﻓﺈن ﺟﻤﯿﻊ اﻟﺨﻮاص اﻟﻔﯿﺰﯾﺎﺋﯿﺔ اﻷﺧﺮى ﻣﺜﻞ اﻟﻜﺘﻠﺔ واﻟﻜﺜﺎﻓﺔ
واﻟﻠﺰوﺟﺔ ) ...(viscosityﯾﺠﺐ أن ﺗﻜﻮن ﺛﺎﺑﺘﺔ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﻌﺎﺩﻻﺕ ﺍﳊﺎﻟﺔ
State Equation
ھﻨﺎك ﺑﻌﺾ اﻷﻣﺜﻠﺔ اﻟﺘﻲ ﯾﻤﻜﻦ اﻟﺘﻌﺒﯿﺮ ﻓﯿﮭﺎ ﻋﻦ اﻟﻌﻼﻗﺎت اﻟﺒﯿﻨﯿ ﺔ ﺑ ﯿﻦ داﻻت اﻟﺤﺎﻟ ﺔ (T, V,
) Pﺑﻮاﺳﻄﺔ ﻣﻌﺎدﻟﺔ ﺗﺴﻤﻰ ﻣﻌﺎدﻟﺔ اﻟﺤﺎﻟﺔ equation of state
وﺑﺎﻟﺘﺎﻟﻲ ﻓﻤﻌﺎدﻟﺔ اﻟﺤﺎﻟﺔ ھﻲ ﻋﻼﻗﺎت رﯾﺎﺿﯿﺔ ﻟﺤﺴﺎب اﻟﻤﺘﻐﯿﺮات اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺔ
)(T, V, P
ﻣﺜﺎﳍﺎ
ﻣﻌﺎدﻟﺔ اﻟﺤﺎﻟﺔ ﻟﻠﻐﺎز اﻟﻤﺜﺎﻟﻲ ﺣﯿﺚ ﺗﻜﻮن ﻓﯿﮫ اﻟﻌﻼﻗﺔ ﺑﯿﻦ اﻟﻀﻐﻂ واﻟﺤﺠﻢ وﻛﻤﯿﺔ اﻟﻐﺎز
ودرﺟﺔ اﻟﺤﺮارة ﻛﻤﺎ ﯾﻠﻲ :
PV = nRT
ﻣﻠﺤﻮﻇﺔ
• ﻣﻘﺪار اﻟﺘﻐﯿﺮ ﻓﻲ ﺗﻮاﺑﻊ اﻟﺤﺎﻟﺔ ﻻ ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﻤﺴﺎر اﻟﺬي ﯾﺴﻠﻜﮫ اﻟﻨﻈﺎم ﻋﻨﺪﻣﺎ ﯾﺘﻐﯿﺮ ﻣﻦ
ﺣﺎﻟﺔ اﻟﻰ أﺧﺮى وإﻧﻤﺎ ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﺤﺎﻟﺔ اﻹﺑﺘﺪاﺋﯿﺔ واﻟﻨﮭﺎﺋﯿﺔ ﻟﻠﻨﻈﺎم.
ﻣﺜﺎﻝ ﺗﻮﺿﻴﺤﻲ :
اﻟﺤﺠ ﻢ اﻹﺑﺘ ﺪاﺋﻲ ﻟﻐ ﺎز ) (Vi = 1 Lﺛ ﻢ ﺗﻤ ﺪد ﻟﯿ ﺼﺒﺢ ) (Vf = 3 Lﻓ ﺈن اﻟﺘﻐﯿ ﺮ ﻓ ﻲ اﻟﺤﺠ ﻢ
ﯾﺴﺎوي :
ΔV = Vf - Vi ⇒ ΔV= 3 - 1 = 2 L
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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اﻟﺤﺠﻢ اﻟﻨﮭﺎﺋﻲ ھﻮ ) (3 Lﺑﻐﺾ اﻟﻨﻈﺮ ﻋﻦ اﻟﻄﺮﯾﻘﺔ اﻟﺘﻲ اﺗﺒﻌﺖ ﻹﺣﺪاث ھﺬا اﻟﺘﻐﯿﺮ.
• ﺗﻢ اﻹﺗﻔﺎق ﻋﻠﻰ أن ﺗﻜﻮن رﻣﻮز ﺗﻮاﺑﻊ اﻟﺤﺎﻟﺔ ﺑﺤﺮوف ﻛﺒﯿﺮة ﻣﺜﻞ :
اﻹﻧﺜﺎﻟﺒﻲ ) ،(Hاﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ) ،(Uاﻷﻧﺘﺮوﺑﻲ ) ،(Sاﻟﻄﺎﻗﺔ اﻟﺤﺮة ).(G
ﺗﻌﺘﻤ ﺪ اﻟﺨ ﻮاص اﻟﻤﺎﻛﺮوﺳ ﻜﻮﺑﯿﺔ ﻟﻠﻨﻈ ﺎم ﻋﻠ ﻰ اﻟﺘﺮﻛﯿ ﺐ اﻟﺨ ﺎرﺟﻲ ﻟﻤﺤﺘﻮﯾ ﺎت اﻟﻨﻈ ﺎم ،ﺑﯿﻨﻤ ﺎ
ﺗﻌﺘﻤﺪ اﻟﺨﻮاص اﻟﻤﯿﻜﺮوﺳﻜﻮﺑﯿﺔ ﻋﻠﻰ اﻟﺘﺮﻛﯿﺐ اﻟﺪاﺧﻠﻲ ﻟﻠﺬرات واﻟﺠﺰﯾﺌﺎت اﻟﻤﻜﻮﻧﺔ ﻟﻠﻨﻈﺎم.
وھﻲ ﺗﺸﻤﻞ ﺟﻤﯿﻊ اﻟﺨﻮاص اﻟﺘﻲ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﻛﻤﯿﺔ اﻟﻤﺎدة أو اﻟﻤﻮاد اﻟﻤﻮﺟﻮدة ﻓﻲ اﻟﻨﻈﺎم
ﻣﺜﻞ ) :اﻟﻜﺘﻠﺔ ،اﻟﺤﺠﻢ ،اﻟﺴﻌﺔ اﻟﺤﺮارﯾﺔ ،اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ،اﻷﻧﺘﺮوﺑﻲ ،اﻟﻄﺎﻗﺔ اﻟﺤﺮة ،ﻣﺴﺎﺣﺔ
اﻟﺴﻄﺢ (... ،وﻛﻠﮭﺎ ﺧﻮاص ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﻣﻘﺪار اﻟﻤﺎدة اﻟﻤﻮﺟﻮدة ﻓﻲ اﻟﻨﻈﺎم.
وﺗﺸﻤﻞ ﺟﻤﯿﻊ اﻟﺨﻮاص اﻟﺘﻲ ﻻ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﻛﻤﯿﺔ اﻟﻤﺎدة اﻟﻤﻮﺟﻮدة ﻓﻲ اﻟﻨﻈﺎم ﻣﺜﻞ :
)اﻟﻀﻐﻂ ،درﺟﺔ اﻟﺤﺮارة ،اﻟﻜﺜﺎﻓﺔ ،اﻟﻠﺰوﺟﺔ ،اﻟﺤﺮارة اﻟﻨﻮﻋﯿﺔ ،اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ(.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻋﻨﺪﻣﺎ ﯾﺘﺤﻮل ﻧﻈﺎم دﯾﻨﺎﻣﯿﻜﻲ ﺣﺮاري ﻣﻦ ﺣﺎﻟﺔ اﻟﻰ أﺧﺮى ،ﻓﺈﻧﮫ ﯾﻄﻠﻖ ﻋﻠﻰ ذﻟﻚ اﻟﺘﺤﻮل
اﺳﻢ ﻋﻤﻠﯿﺔ ).(process
وﻓﻲ اﻟﺤﻘﯿﻘﺔ ﻓﺈن اﻟﻌﻤﻠﯿﺎت اﻟﺘﻲ ﺗﺘﻢ ﯾﺼﺎﺣﺒﮭﺎ ﺗﻐﯿﺮ ﻓﻲ ﺑﻌﺾ ﺧﻮاص اﻷﻧﻈﻤﺔ اﻟﺨﺎﺿﻌﺔ
ﻟﻠﺘﻐﯿﺮ ،ﻣﺜﻞ :اﻟﺤﺠﻢ واﻟﻀﻐﻂ ودرﺟﺔ اﻟﺤﺮارة.
وﺑﻨﺎءً ﻋﻠﻰ ھﺬه اﻟﺘﻐﯿﺮات ﯾﻤﻜﻦ ﺗﻘﺴﯿﻢ ﻋﻤﻠﯿﺎت اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ اﻟﻰ :
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺗﻌﺮف اﻟﻌﻤﻠﯿﺔ اﻟﻌﻜﺴﯿﺔ ) : (reversible processﺑﺄﻧﮭﺎ ﺗﻠﻚ اﻟﻌﻤﻠﯿﺔ اﻟﺘﻲ ﺗﺘﻢ ﺑﺒﻂء ﻣﺘﻨﺎه
ﻓﻲ اﻟﺼﻐﺮ ،واﻟﺘﻲ ﯾﻤﻜﻦ ﻋﻜﺲ اﺗﺠﺎھﮭﺎ ﻋﻨﺪ أي ﻟﺤﻈﺔ ،ﺑﺘﻐﯿﯿﺮ ﻣﺘﻨﺎه ﻓﻲ اﻟﺼﻐﺮ ﻓﻲ ﺣﺎﻟﺔ
اﻟﻨﻈﺎم ،أو ھﻲ اﻟﻌﻤﻠﯿﺔ اﻟﺘﻲ ﯾﻤﻜﻦ ﻋﻜﺴﮭﺎ ﻋﻨﺪ اﻟﻄﻠﺐ ﺑﺈﺣﺪاث ﺗﻐﯿﺮات ﻣﺘﻨﺎھﯿﺔ ﻓﻲ اﻟﺼﻐﺮ
ﻓﻲ درﺟﺔ اﻟﺤﺮارة أو اﻟﻀﻐﻂ أو أﯾﺔ ﻣﺘﻐﯿﺮات أﺧﺮى.
وﺗﻌﺮف اﻟﻌﻤﻠﯿﺔ ﻏﯿﺮ اﻟﻌﻜﺴﯿﺔ ) (irreversible processﺑﺄﻧﮭﺎ ﺗﻠﻚ اﻟﻌﻤﻠﯿﺔ ،اﻟﺘﻲ ﺗﻤﺮ
ﻣﻦ اﻟﺤﺎﻟﺔ اﻹﺑﺘﺪاﺋﯿﺔ اﻟﻰ اﻟﺤﺎﻟﺔ اﻟﻨﮭﺎﺋﯿﺔ ﻓﻲ ﺧﻄﻮة واﺣﺪة ،وﻻ ﯾﻤﻜﻦ أن ﺗﺴﯿﺮ ﻓﻲ اﻻﺗﺠﺎه
اﻟﻌﻜﺴﻲ ،أو ھﻲ اﻟﻌﻤﻠﯿﺔ اﻟﺘﻲ ﻻ ﯾﻤﻜﻦ ﻋﻜﺴﮭﺎ ﻋﻨﺪ اﻟﻄﻠﺐ ﺑﺈﺣﺪاث ﺗﻐﯿﺮات ﻣﺘﻨﺎھﯿﺔ ﻓﻲ
اﻟﺼﻐﺮ ﻓﻲ أي ﻣﻦ ﻣﺘﻐﯿﺮات اﻟﺤﺎﻟﺔ ﻟﻠﻨﻈﺎم.
ﺍﻟﻄﺎﻗﺔ ﺍﻟﺪﺍﺧﻠﻴﺔ
)Internal Energy (E
ﺗﻌﺮف اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻨﻈﺎم ﺑﺄﻧﮭﺎ ﻣﺠﻤﻮع أﺷﻜﺎل اﻟﻄﺎﻗﺔ اﻟﻤﺤﺘﻤﻠﺔ ﻣﺜﻞ ﻃﺎﻗﺔ اﻟﺘﺠﺎذب
واﻟﺘﻨﺎﻓﺮ ﺑﯿﻦ اﻹﻟﻜﺘﺮوﻧﺎت وأﻧﻮﯾﺔ اﻟﺬرات واﻟﺠﺰﯾﺌﺎت داﺧﻞ اﻟﻨﻈﺎم وﺟﻤﯿﻊ أﺷﻜﺎل اﻟﻄﺎﻗﺔ
ودوراﻧﯿﺔ )(vibrational واھﺘﺰازﯾﺔ )(transitional اﻧﺘﻘﺎﻟﯿﺔ ﻣﻦ اﻷﺧﺮى
).(rotational
واﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻷي ﻧﻈﺎم ﻣﻌﺰول ﺗﻜﻮن ﻗﯿﻤﺔ ﺛﺎﺑﺘﺔ .واﻟﻘﯿﻤﺔ اﻟﺤﻘﯿﻘﯿﺔ ﻟﻠﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ )(E
ﻷي ﻧﻈﺎم ﻏﯿﺮ ﻣﻌﺮوﻓﺔ وﻻ ﯾﻤﻜﻦ ﺣﺴﺎﺑﮭﺎ ﺑﺎﻟﻀﺒﻂ.
س( ھﻞ ﯾﻤﻜﻦ ﻗﯿﺎس اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ اﻟﻤﻄﻠﻘﺔ ) (Eﻟﻠﻨﻈﺎم ﻋﻨﺪ ﺣﺎﻟﺔ ﻣﻌﯿﻨﺔ؟
ج( ﻻ ﯾﻤﻜﻦ ذﻟﻚ ﻷن اﻟﻄﺎﻗﺔ اﻟﻤﻮﺟﻮدة ﻓﻲ اﻟﻨﻈﺎم ﻋﺪﯾﺪة )ﻃﺎﻗﺔ رواﺑﻂ ،اﻟﻄﺎﻗﺔ اﻟﺤﺮﻛﯿﺔ
ﻟﻠﺠﺰﯾﺌﺎت ،ﻃﺎﻗﺔ ﺗﺠﺎذب ﺑﯿﻦ اﻹﻟﻜﺘﺮوﻧﺎت واﻟﺒﺮوﺗﻮﻧﺎت ،ﻃﺎﻗﺔ اﻟﺘﺠﺎذب ﺑﯿﻦ اﻟﺠﺰﯾﺌﺎت،(...
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﻛﺬﻟﻚ ﻟﻌﺪم ﻣﻌﺮﻓﺘﻨﺎ ﺑﺴﺮﻋﺔ ﺣﺮﻛﺔ ﺟﺰﯾﺌﺎت اﻟﻨﻈﺎم ،وﻛﺬﻟﻚ ﻟﻌﺪم ﻣﻌﺮﻓﺘﻨﺎ ﺑﻘﻮى اﻟﺘﺠﺎذب
ﺑﯿﻦ اﻟﺠﺰﯾﺌﺎت ﻋﻠﻰ اﻟﻨﻈﺎم.
وﻟﻜﻦ ﻏﺎﻟﺒﺎً ﺗﻘﺎس ) ( ∆Eﻋﻨﺪﻣﺎ ﯾﺘﻐﯿﺮ اﻟﻨﻈﺎم ﻣﻦ ﺣﺎﻟﺔ اﻟﻰ أﺧﺮى ﺣﯿﺚ :
∆E = E 2 - E1
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﻟﺸﻐﻞ Work
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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وﺳﻨﺮﻛﺰ ﻓﻲ ھﺬا اﻟﻔﺼﻞ ﻋﻠﻰ اﻟﺸﻐﻞ اﻟﻨﺎﺗﺞ ﻋﻦ اﻟﺘﻐﯿﺮ ﻓﻲ ﺣﺠﻢ ﻛﻤﯿﺔ ﻣﻌﯿﻨﺔ ﻣﻦ ﻏﺎز ﺗﺤﺖ
.ﻇﺮوف ﻣﻌﯿﻨﺔ
: ﺍﻟﺸﻐﻞ ﺍﳌﻴﻜﺎﻧﻴﻜﻲ
إذا اﻓﺘﺮض وﺟﻮد ﻏﺎز ﻓﻲ اﺳﻄﻮاﻧﺔ ﻣﺰودة ﺑﻤﻜﺒﺲ ﻣﺘﺤﺮك ﻋﺪﯾﻢ اﻟﻮزن واﻻﺣﺘﻜﺎك ﻣﺴﺎﺣﺔ
،٩ ،٨ ،٧ : ( ﻋﻨﺪ ﻇﺮوف ﻣﻌﯿﻨﺔ ﻣﻦ اﻟﺤﺠﻢ واﻟﻀﻐﻂ ودرﺟﺔ اﻟﺤﺮارة )ﺷﻜﻞA) ﺳﻄﺤﮫ
.(١٠
Fig. 8 : The expansion in volume that occurs during a reaction forces the piston outward
against atmospheric pressure P. The amount of work done is equal to the pressure exerted
in moving the piston (the opposite of atmospheric pressure, (-P) times the volume change
( ∆V ) . The volume change is equal to the area of the piston (A) times the distance the piston
moves (d). Thus w = - P ∆V
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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Fig. 9 : The gas in the piston expands a distance, L, against a pressure, P. The volume
increase is L x A, where A is the cross-sectional area of the piston.
Fig. 10 : A system does work when it expands against an external pressure. Here we see a
gas that pushes a piston out against a pressure, P. We shall see shortly that the work done
is proportional to both the pressure and the change in volume that the system undergoes.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻓﻌﻨﺪ ﺗﻤﺪد اﻟﻐﺎز ﻓﺈﻧﮫ ﯾﺪﻓﻊ اﻟﻤﻜﺒﺲ اﻟﻰ أﻋﻠﻰ ﺿﺪ ﺿﻐﻂ ﻣﻀﺎد ) (Pﻣﻌﺎﻛﺲ ﻻ ﺗﺠﺎه اﻟﺘﻐﯿﺮ
)اﻟﻀﻐﻂ اﻟﺠﻮي ﻣﺜﻼً( ﻣﻨﺠﺰاً ﺷﻐﻼً ﺿﺪ اﻟﻤﺤﯿﻂ.
وﺑﻤﺎ أن اﻟﻀﻐﻂ ﯾﻌﺮف ﺑﺄﻧﮫ اﻟﻘﻮة اﻟﻤﺴﻠﻄﺔ ﻋﻠﻰ وﺣﺪة اﻟﻤﺴﺎﺣﺎت ﻓﺈن :
F
=P
A
F = PA
وﺑﻤﺎ أن :
w = F ∆L
وﺑﺎﻟﺘﻌﻮﯾﺾ ﻋﻦ ﻗﯿﻤﺔ Fﻣﻦ اﻟﻤﻌﺎدﻟﺔ F = PAﻓﻲ اﻟﻤﻌﺎدﻟﺔ w = F ∆L
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺣﯿﺚ:
: V1اﻟﺤﺠﻢ اﻹﺑﺘﺪاﺋﻲ ﻟﻠﻐﺎز.
: V2اﻟﺤﺠﻢ اﻟﻨﮭﺎﺋﻲ ﻟﻠﻐﺎز.
واﻹﺷﺎرة اﻟﺴﺎﻟﺒﺔ ﺗﺪل ﻋﻠﻰ أن ﻃﺎﻗﺔ اﻟﻨﻈﺎم ﺗﻨﺨﻔﺾ ﻋﻨﺪﻣﺎ ﯾﺰداد اﻟﺤﺠﻢ أي أن اﻟﻨﻈﺎم ﯾﻌﻤﻞ
ﺷﻐﻞ ﻋﻠﻰ اﻟﻤﺤﯿﻂ.
وإذا ﻛﺎﻧﺖ ﻗﯿﻤﺔ Pﻛﻤﯿﺔ ﻣﻮﺟﺒﺔ ) (+ﻓﺈن اﻟﺸﻐﻞ ﯾﻌﻄﻰ ﺣﺴﺐ اﻟﻌﻼﻗﺔ:
) ( w = - P ∆V
(١إذا ﻛﺎﻧﺖ ﻗﯿﻤﺔ اﻟﻀﻐﻂ اﻟﻤﻀﺎد أو اﻟﺨﺎرﺟﻲ ) (Pأﺻﻐﺮ ﻣﻦ ﺿﻐﻂ اﻟﻐﺎز ﻓﺈن اﻟﻐﺎز ﯾﺘﻤﺪد
وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ΔVﻣﻮﺟﺒﺔ وﺑﺬﻟﻚ ﺗﻜﻮن ﻗﯿﻤﺔ اﻟﺸﻐﻞ ) ( V2 > V1 ﺿﺪ اﻟﻤﺤﯿﻂ وﺗﻜﻮن
) (Wﺳﺎﻟﺒﺔ أي أن اﻟﻨﻈﺎم أﻧﺠﺰ ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ )اﻟﻨﻈﺎم ﻓﻘﺪ ﻃﺎﻗﺔ ﻛﺸﻐﻞ(.
(٢إذا ﻛﺎن ﺿﻐﻂ اﻟﻤﺤﯿﻂ أﻛﺒﺮ ﻣﻦ ﺿﻐﻂ اﻟﻐﺎز ﻓﺈن اﻟﻐﺎز ﯾﻨﻜﻤﺶ وﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﯾﻜﻮن
( )
اﻟﻀﻐﻂ اﻟﻤﻀﺎد ھﻮ ﺿﻐﻂ اﻟﻐﺎز ﻧﻔﺴﮫ ﻷﻧﮫ ﯾﻌﺎﻛﺲ اﺗﺠﺎه اﻟﺘﻐﯿﺮ V2 < V1وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن
ΔVﺗﺼﺒﺢ ﺳﺎﻟﺒﺔ وﺗﻜﻮن ﻗﯿﻤﺔ اﻟﺸﻐﻞ ) (wﻣﻮﺟﺒﺔ أي أن اﻟﻤﺤﯿﻂ ﯾﻌﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم
)ﺗﺰداد ﻃﺎﻗﺔ اﻟﻨﻈﺎم ﺑﺴﺒﺐ اﻟﺸﻐﻞ اﻟﺬي ﺑﺬل ﻋﻠﯿﮫ(.
وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻀﻐﻂ ) (Pھﻮ اﻟﺬي ﯾﺤﺪد ﻣﺴﺎر اﻟﻌﻤﻠﯿﺔ ،ﻣﻤﺎ ﯾﻌﻨﻲ أن اﻟﺸﻐﻞ ﻟﯿﺲ ﺗﺎﺑﻌﺎً
ﻟﻠﺤﺎﻟﺔ.
س( ﻋﻠﻞ :اﻟﺸﻐﻞ ﻟﯿﺲ ﺗﺎﺑﻊ ﻟﻠﺤﺎﻟﺔ؟
ج( ﻷن اﻟﺸﻐﻞ ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﻀﻐﻂ.
ﺟﺪول ) : (٢ﻣﻠﺨﺺ ﻹﺷﺎرات ﻗﯿﻤﺔ اﻟﺸﻐﻞ
دﻻﻟﺘﮭﺎ إﺷﺎرة ﻗﯿﻤﺔ اﻟﺸﻐﻞ
اﻟﻨﻈﺎم ﯾﻌﻤﻞ )ﯾﻨﺠﺰ( ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ. )(-
اﻟﻤﺤﯿﻂ ﯾﻌﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم. )(+
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(١
Fig. 11
ﻣﺜﺎﻝ )(٢
إذا ﺗﻤﺪد ﻏﺎز ﻣﺜﺎﻟﻲ ﻋﻨﺪ درﺟﺔ ﺣﺮارة ) (25 ºCﻣﻦ اﻟﺤﺠﻢ ) (2Lاﻟﻰ اﻟﺤﺠﻢ ) (5 Lﻋﻨﺪ
ب( ﺿﺪ أ( ﺿﺪ اﻟﻔﺮاغ ﺿﻐﻂ ﺛﺎﺑﺖ .ﻓﺎﺣﺴﺐ اﻟﺸﻐﻞ اﻟﻤﻨﺠﺰ ﻋﻨﺪﻣﺎ ﯾﺘﻤﺪد :
ﺿﻐﻂ ﺛﺎﺑﺖ ﻣﻘﺪاره )(3 atm
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٣
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1482
1 kJ
w = - 2026.5 J ×
1000 J
w = - 2.0265 kJ
وﺑﺎﺧﺘﺼﺎر ﻓﺈﻧﮫ ﻟﺘﺤﻮﯾﻞ اﻟﺠﻮل اﻟﻰ وﺣﺪة اﻟﻜﯿﻠﻮ ﺟﻮل ﻧﻘﺴﻢ ﻋﻠﻰ اﻟﻤﻌﺎﻣﻞ )،(1000
واﻟﻌﻜﺲ ﺻﺤﯿﺢ ﻓﺈﻧﮫ ﻟﺘﺤﻮﯾﻞ اﻟﻜﯿﻠﻮ ﺟﻮل اﻟﻰ ﺟﻮل ﻓﺈﻧﻨﺎ ﻧﻀﺮب اﻟﻘﯿﻤﺔ ﻓﻲ ). (1000
واﻟﻘﺎﻋﺪة اﻟﺴﺎﺑﻘﺔ ﻣﮭﻤﺔ ﻻﺳﯿﻤﺎ ﻋﻨﺪ اﺳﺘﺨﺪام اﻟﺜﺎﺑﺖ ) ، (Rاﻟﺬي وﺣﺪﺗﮫ وﻗﯿﻤﺘﮫ ھﻲ R :
= 8.314 J/K. mol
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1483
وﺑﺎﻟﺘﺎﻟﻲ ﻋﻨﺪ اﻟﺘﻌﻮﯾﺾ ﺑﮫ ﻓﻲ اﻟﻤﻌﺎدﻻت ﻓﺈن ﻗﯿﻢ اﻟﻄﺎﻗﺔ ﻻ ﺑﺪ أن ﺗﻜﻮن ﺑﺎﻟﺠﻮل ،ﻓﺈذا ﻛﺎﻧﺖ
ﺑﻐﯿﺮ اﻟﺠﻮل )أي ﺑﺎﻟﻜﯿﻠﻮ ﺟﻮل( ﻓﺈﻧﮭﺎ ﺗﺤﻮل اﻟﻰ ﺟﻮل ﺑﻀﺮب ﻗﯿﻤﺘﮭﺎ ﻓﻲ ) (1000ﻛﻤﺎ
ﺳﻨﺮى ﻓﻲ اﻟﻤﺴﺎﺋﻞ اﻟﻼﺣﻘﺔ.
ﻣﺜﺎﻝ )(٤
اﺣﺴﺐ اﻟﺸﻐﻞ ﺑﻮﺣﺪة اﻟﺠﻮل ﻋﻨﺪﻣﺎ ﯾﺘﺠﻤﺪ 2 mlﻣﻦ اﻟﻤﺎء ﻋﻨﺪ 0 ºCوﺿﻐﻂ ﺟﻮي (1
) atmﻟﯿﺼﺒﺢ ﺣﺠﻤﮫ ).(2.2 ml
ﺍﳊﻞ
ﻧﺤﺴﺐ أوﻻً اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﺤﺠﻢ ﺑﺎﻟﻮﺣﺪة اﻟﻤﻌﻄﺎة ﻓﻲ اﻟﻤﺴﺄﻟﺔ ،وھﻲ اﻟﻤﻠﻠﺘﺮ ) (mlﺛﻢ ﻧﺤﻮﻟﮭﺎ
اﻟﻰ وﺣﺪة اﻟﻠﺘﺮ ،ﺣﯿﺚ أن اﻟﻌﻼﻗﺔ ﺑﯿﻨﮭﻤﺎ:
1 L = 1000 ml
1 ml = 1 × 10-3 L
وﯾﻜﻮن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﺤﺠﻢ :
∆V = V - V
2 1
∆V = 2.2 ml - 2 ml
1L
∆V = 0.2 ml ×
1000 ml
ΔV = 2 × 10-4 L
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1484
ﻣﺜﺎﻝ )(٥
اﻧﺘﻘﻞ ﻏﺎز ﻣﻦ إﻧﺎء ﺣﺠﻤﮫ ) (8 Lاﻟﻰ إﻧﺎء ﺣﺠﻤﮫ ) (3 Lﺗﺤﺖ ﺗﺄﺛﯿﺮ ﺿﻐﻂ ﺧﺎرﺟﻲ ﻣﻘﺪاره
) .(4 atmاﺣﺴﺐ اﻟﺸﻐﻞ اﻟﻤﺒﺬول ﺧﻼل ھﺬه اﻟﻌﻤﻠﯿﺔ.
ﺍﳊﻞ
w = - P ∆V
101.3 J
× )w = - 4 atm × (3 L - 8 L
L. atm
w = + 2026 J
وﻧﻼﺣﻆ أن اﻟﺸﻐﻞ ﻟﮫ ﻗﯿﻤﺔ ﻣﻮﺟﺒﺔ ،ﻣﻤﺎ ﯾﻌﻨﻲ أن اﻟﻤﺤﯿﻂ ﺑﺬل ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم.
ﻣﺜﺎﻝ )(٦
ﻓﻲ إﻧﺎء ﺣﺠﻤﮫ ) (4 Lاﻟﻰ ﺳﺎﺋﻞ ﺣﺠﻤﮫ ) (350 cm3ﻋﻨﺪ ﺿﻐﻂ ﻗﺪره ) (5 atmواﻧﻄﻠﻘﺖ
ﺣﺮارة ﻣﻘﺪارھﺎ ،392 kJاﺣﺴﺐ اﻟﺸﻐﻞ اﻟﻤﺒﺬول.
ﺍﳊﻞ
ﻧﺤﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﺤﺠﻢ ﺑﻌﺪ ﺗﺤﻮﯾﻞ وﺣﺪة اﻟﺴﻢ ٣اﻟﻰ وﺣﺪة اﻟﻠﺘﺮ :
1 cm3 = 1 × 10-3 L
350 cm3 = VL
1L
× ) VL = (350 cm3
) (1000 cm3
VL = 0.35 L
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1485
ﻣﺜﺎﻝ )(٧
إذا ﺗﻤﺪد ﻏﺎز ﻣﺜﺎﻟﻲ ﻣﻦ ﺣﺠﻢ ) (2400 cm3اﻟﻰ ﺣﺠﻢ ﻧﮭﺎﺋﻲ ) ،(6150 cm3وﻛﺎن
اﻟﻀﻐﻂ اﻟﻨﮭﺎﺋﻲ ) (2.4 atmﻓﺎﺣﺴﺐ اﻟﺸﻐﻞ اﻟﻨﺎﺗﺞ :
أ( ﺑﻮﺣﺪات ﻟﺘﺮ -ﺿﻐﻂ ﺟﻮي
ب( ﺑﻮﺣﺪة ﻛﯿﻠﻮ ﺟﻮل )ﻋﻠﻤﺎً ﺑﺄن .(1 L . atm = 101.325 J :
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1486
ﻣﺜﺎﻝ )(٨
ﺗﻜﺜﻒ ) (1 molﻣﻦ ﻏﺎز ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻜﺒﺮﯾﺖ ) (SO2ﻓﻲ إﻧﺎء ﺣﺠﻤﮫ ) (3 Lاﻟﻰ ﺳﺎﺋﻞ
) (300 cm3ﻋﻨﺪ ﺿﻐﻂ ﻗﺪره ) (10 atmواﻧﻄﻠﻘﺖ ﺣﺮارة ﻣﻘﺪارھﺎ 393 ﺣﺠﻤﮫ
. kJ
ب( اﺣﺴﺐ اﻟﺸﻐﻞ اﻟﻤﺒﺬول. أ( أﻛﺘﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺤﺮارﯾﺔ.
ﺍﳊﻞ
ﻣﺜﺎﻝ )(٩
ﺣﺪد ﻣﻦ ﺧﻼل اﻟﺘﻔﺎﻋﻼت اﻟﺘﺎﻟﯿﺔ أي ﻣﻦ اﻟﻤﻌﺎدﻻت ﺑﺬل ﻓﯿﮫ اﻟﻨﻈﺎم ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ ﻣﻊ
اﻟﺘﻌﻠﯿﻞ
)1.........Sn(s) + 2F2 (g) → SnF4 (s
)2.........SiI 4 (g) → Si(s) + 2I 2 (g
← )3..........H 2 (g) + Cl 2 (g)→ 2HCl(g
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﳊﻞ
اﻟﻘﺎﻋﺪة :
(١ﻋﻨﺪﻣﺎ ﯾﻜﻮن ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ اﻟﻨﺎﺗﺠﺔ ) (nPأﻛﺒﺮ ﻣﻦ ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ
اﻟﻤﺘﻔﺎﻋﻠﺔ ) (nRﻓﺈن ھﺬا ﯾﻌﻨﻲ أن اﻟﻨﻈﺎم ﻗﺪ زاد ﺣﺠﻤﮫ )ﺗﻤﺪد( وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻨﻈﺎم ﻋﻤﻞ
ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ.
(٢ﻋﻨﺪﻣﺎ ﯾﻜﻮن ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ اﻟﻨﺎﺗﺠﺔ ) (nPأﺻﻐﺮ ﻣﻦ ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ
اﻟﻤﺘﻔﺎﻋﻠﺔ ) (nRﻓﺈن ھﺬا ﯾﻌﻨﻲ أن اﻟﻨﻈﺎم ﻗﺪ ﻗﻞ ﺣﺠﻤﮫ )اﻧﻜﻤﺶ( وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻤﺤﯿﻂ ﻋﻤﻞ
ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم.
(٣ﻋﻨﺪ ﺗﺴﺎوي ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ اﻟﻨﺎﺗﺠﺔ واﻟﻤﺘﻔﺎﻋﻠﺔ ﻓﺈن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﺤﺠﻢ ﯾﺴﺎوي
ﺻﻔﺮاً وﺑﺎﻟﺘﺎﻟﻲ ﻻ ﯾﺤﺪث ﺷﻐﻞ.
وﺑﺘﻄﺒﯿﻖ ھﺬا اﻟﻘﻮاﻋﺪ ﻋﻠﻰ اﻟﺘﻔﺎﻋﻼت :
اﻟﺘﻔﺎﻋﻞ اﻷول :
R
n =2 n =0
P
)1.........Sn(s) + 2F2 (g) → SnF4 (s
ﺑﻤﺎ أن ) (nP < nRﻓﺈن اﻟﺤﺠﻢ ﻗﻞ وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻤﺤﯿﻂ ﻋﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم.
ﺑﻤﺎ أن ) (nP > nRﻓﺈن اﻟﺤﺠﻢ ﻗﺪ زاد ،وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻨﻈﺎم ﯾﻌﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1488
ﻣﺜﺎﻝ )(١٠
ﺳﻤﺢ ﻟﻐﺎز ﻣﺜﺎﻟﻲ ﺣﺠﻤﮫ ) (20 Lوﺿﻐﻄﮫ ) (15 atmﺑﺄن ﯾﺘﻤﺪد ﻋﻠﻰ ﻣﺮﺣﻠﺘﯿﻦ:
اﻷوﻟﻰ :ﻛﺎن اﻟﻀﻐﻂ اﻟﺨﺎرﺟﻲ ﻗﺪره )(8 atm
اﻟﺜﺎﻧﯿﺔ :ﻛﺎن اﻟﻀﻐﻂ اﻟﺨﺎرﺟﻲ )(2 atm
اﺣﺴﺐ اﻟﺸﻐﻞ اﻟﺬي ﯾﺒﺬﻟﮫ اﻟﻐﺎز.
ﺍﳊﻞ
اﻟﺤﺎﻟﺔ اﻷوﻟﻰ :ﺣﺴﺎب اﻟﺸﻐﻞ ﻋﻨﺪﻣﺎ ﯾﻜﻮن اﻟﻀﻐﻂ اﻟﺨﺎرﺟﻲ )(8 atm
اﻟﻤﺸﻜﻠﺔ ھﻨﺎ أﻧﮫ ﻟﻢ ﯾﺤﺪد اﻟﺤﺠﻢ اﻟﻨﮭﺎﺋﻲ اﻟﺬي ﺳﯿﺆول إﻟﯿﮫ اﻟﻐﺎز ﺑﻌﺪ ﺗﻤﺪده ﻓﻲ اﻟﻤﺮﺣﻠﺔ
اﻷوﻟﻰ ،ﻟﺬﻟﻚ ﻓﺤﺴﺎب اﻟﺸﻐﻞ ﻏﯿﺮ ﻣﻤﻜﻦ ﻷن اﻟﺸﻐﻞ ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﻘﺎﻧﻮن :
) w = - P(V2 - V1
وﻻ ﺳﺒﯿﻞ اﻟﻰ اﯾﺠﺎد ﺣﺠﻤﮫ اﻟﻨﮭﺎﺋﻲ إﻻ ﺑﻘﺎﻧﻮن ﺑﻮﯾﻞ ﻛﻤﺎ ﯾﻠﻲ :
P1V1 = P2 V2
15 atm × 20 L = 8 atm x V2
15 atm × 20 L
= V2
8 atm
V2 = 37.5 L
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1489
اﻟﺤﺎﻟﺔ اﻟﺜﺎﻧﯿﺔ :ﺣﺴﺎب اﻟﺸﻐﻞ ﻋﻨﺪﻣﺎ ﯾﻜﻮن اﻟﻀﻐﻂ اﻟﺨﺎرﺟﻲ ): (2 atm
وﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﻧﺠﺪ أن اﻟﺤﺠﻢ اﻹﺑﺘﺪاﺋﻲ ) (V1 = 37.5 Lﺑﯿﻨﻤﺎ اﻟﺤﺠﻢ اﻟﻨﮭﺎﺋﻲ ﻏﯿﺮ
ﻣﻌﻠﻮم ،وﺑﺎﻟﺘﺎﻟﻲ ﯾﺼﻌﺐ ﺣﺴﺎب اﻟﺸﻐﻞ.
وﺑﻨﻔﺲ اﻟﻄﺮﯾﻘﺔ ﻓﺈﻧﻨﺎ ﻧﻮﺟﺪ اﻟﺤﺠﻢ اﻟﻨﮭﺎﺋﻲ ) (V2ﻣﻦ ﻗﺎﻧﻮن ﺑﻮﯾﻞ :
P1V1 = P2 V2
8 atm × 37.5 L = 2 atm × V2
8 atm × 37.5 L
= V2
2 atm
V2 = 150 L
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1490
1490
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1491
اﻟﻘﺎﻧﻮن اﻷول ﻓﻲ اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ ﻣﺮادف ﻟﻘﺎﻧﻮن ﺣﻔﻆ اﻟﻄﺎﻗﺔ ،وﯾﻨﺺ ﻋﻠﻰ أن :
"اﻟﻄﺎﻗﺔ ﻻ ﺗﻔﻨﻰ وﻻ ﺗﺴﺘﺤﺪث )ﺗﺨﻠﻖ ﻣﻦ ﻋﺪم( وﻟﻜﻦ ﯾﻤﻜﻦ ﻓﻘﻂ ﻧﻘﻠﮭﺎ ﻣﻦ ﻣﻜﺎن اﻟﻰ آﺧﺮ
أو ﺗﺤﻮﯾﻠﮭﺎ ﻣﻦ ﺷﻜﻞ اﻟﻰ آﺧﺮ أﺛﻨﺎء اﻟﺘﻔﺎﻋﻼت أو اﻟﺘﻐﯿﺮات اﻟﻜﯿﻤﯿﺎﺋﯿﺔ "
ﺑﻤﻌﻨﻰ أن ﻃﺎﻗﺔ اﻟﻨﻈﺎم اﻟﻤﻌﺰول ﻋﻦ ﻣﺤﯿﻄﮫ ﺗﻈﻞ ﺛﺎﺑﺘﺔ .وﺑﺎﻟﺘﺎﻟﻲ ﯾﻤﻜﻦ ﺻﯿﺎﻏﺔ اﻟﻘﺎﻧﻮن
اﻷول ﻟﻠﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﻛﻤﺎ ﯾﻠﻲ :
"اﻟﻄﺎﻗﺔ اﻟﻜﻠﯿﺔ ﻟﻨﻈﺎم ﻣﻌﺰول ﺗﻈﻞ ﺛﺎﺑﺘﺔ وﯾﻤﻜﻦ ﺗﺤﻮل اﻟﻄﺎﻗﺔ ﻣﻦ ﺻﻮرة اﻟﻰ أﺧﺮى".
وھﺬا ﯾﻌﻨﻲ أن ﻣﺠﻤﻮع ﻛﻞ أﻧﻮاع اﻟﻄﺎﻗﺎت ﺛﺎﺑﺖ ﻓﻲ أي ﻣﺠﻤﻮﻋﺔ ﻣﻌﺰوﻟﺔ ،وﻣﻦ ذﻟﻚ ﯾﺄﺗﻲ
اﻟﻘﻮل اﻟﻤﻌﺮوف واﻟﻘﺎﺋﻞ ﺑﺄن ﻃﺎﻗﺔ اﻟﻜﻮن ﺛﺎﺑﺘﺔ ،ﻋﻠﻰ أﺳﺎس أن اﻟﻜﻮن ﯾﻌﺘﺒﺮ ﻧﻈﺎﻣﺎً ﻣﻌﺰوﻻً.
وﻛﺎن ﻟﻠﺘﺠﺎرب اﻟﺘﻲ أﺟﺮاھﺎ ﺟﯿﻤﺲ ﺟﻮل ) (1840 – 1849 ADأﻛﺒﺮ اﻷﺛﺮ ﻓﻲ دﻋﻢ ھﺬا
اﻟﻘﺎﻧﻮن ،ﺣﯿﺚ أﺛﺒﺖ ﺑﺘﺠﺎرﺑﮫ أن اﻟﺤﺮارة واﻟﺸﻐﻞ اﻟﻤﯿﻜﺎﻧﯿﻜﻲ ھﻤﺎ وﺟﮭﺎن ﻟﻌﻤﻠﺔ واﺣﺪة وھﻲ
اﻟﻄﺎﻗﺔ ،وأﻧﮫ ﯾﻤﻜﻦ ﺗﺤﻮﯾﻞ ﺻﻮر اﻟﻄﺎﻗﺔ اﻟﻰ ﺑﻌﻀﮭﺎ اﻟﺒﻌﺾ ،وأن اﻟﻄﺎﻗﺔ ﻻ ﺗﻔﻨﻰ.
واﻟﺘﺠﺎرب اﻟﺘﻲ ﺗﺜﺒﺖ أن اﻟﻄﺎﻗﺔ ﻻ ﺗﻔﻨﻰ وﻻ ﺗﺨﻠﻖ ﻣﻦ ﻋﺪم ،وﻟﻜﻨﮭﺎ ﺗﺘﺤﻮل ﻣﻦ ﺻﻮرة اﻟﻰ
أﺧﺮى ﻛﺜﯿﺮة ،وﻣﻨﮭﺎ :ﻋﻨﺪ ﺑﺬل ﻗﺪر ﻣﻦ اﻟﻄﺎﻗﺔ ﻓﻲ ﺿﻐﻂ ﻟﻮﻟﺐ ﻣﻦ اﻟﺼﻠﺐ ،ﺛﻢ إذاﺑﺘﮫ وھﻮ
ﻣﻀﻐﻮط ﻓﻲ ﺣﻤﺾ ،ﻓﻘﺪ ﯾﺒﺪو أن اﻟﻄﺎﻗﺔ اﻟﺘﻲ ﺑﺬﻟﺖ ﻓﻲ ﺿﻐﻂ اﻟﻠﻮﻟﺐ ﻗﺪ ﻓﻘﺪت ،وﻟﻜﻦ ﻓﻲ
اﻟﺤﻘﯿﻘﺔ إﻧﮭﺎ اﺧﺘﺰﻟﺖ ﺑﺎﻟﻠﻮﻟﺐ ،وﯾﺆﻛﺪ ذﻟﻚ أن ﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﺘﻲ ﺗﻨﺘﺞ ﻣﻦ ذوﺑﺎن اﻟﻠﻮﻟﺐ
اﻟﻤﻀﻐﻮط ،ﺗﻜﻮن أﻛﺒﺮ ﻣﻦ ﺗﻠﻚ اﻟﺘﻲ ﺗﻨﺘﺞ ﻋﻦ ذوﺑﺎن اﻟﻠﻮﻟﺐ ﻧﻔﺴﮫ وھﻮ ﻏﯿﺮ ﻣﻀﻐﻮط.
واﻟﻔﺮق ﺑﯿﻦ اﻟﻘﯿﻤﺘﯿﻦ ﯾﺴﺎوي ﻣﻘﺪار اﻟﺸﻐﻞ اﻟﻤﺒﺬول ﻓﻲ ﺿﻐﻂ اﻟﻠﻮﻟﺐ )ﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﻧﺠﺪ
أن اﻟﺸﻐﻞ ﻗﺪ ﺗﺤﻮل اﻟﻰ ﺣﺮارة(.
وﯾﻌﺒﺮ ﻋﻦ اﻟﻘﺎﻧﻮن اﻷول رﯾﺎﺿﯿﺎً :
ΔE = q + w
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺣﯿﺚ :
: ΔEﻣﻘﺪار اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻨﻈﺎم.
: qﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﻤﻤﺘﺼﺔ أو اﻟﻤﻨﺒﻌﺜﺔ ﺑﻮاﺳﻄﺔ اﻟﻨﻈﺎم.
: wاﻟﺸﻐﻞ اﻟﻤﺒﺬول ﻋﻠﻰ أو ﺑﻮاﺳﻄﺔ اﻟﻨﻈﺎم.
ﻣﻠﺤﻮﻇﺔ :
ﺑﻌﺾ اﻟﻤﺮاﺟﻊ ﺗﻜﺘﺐ اﻟﻘﺎﻧﻮن اﻷول ﻓﻲ اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ رﯾﺎﺿﯿﺎً ﻋﻠﻰ اﻟﺼﻮرة :
ΔE = q + w ﺑﺪﻻً ﻣﻦ اﻟﺼﻮرة : ΔE = q - w
وﻛﻼھﻤ ﺎ ﺻ ﺤﯿﺢ ﻷن ﻛ ﻼً ﻣﻨﮭﻤ ﺎ أﻋﻄ ﻰ اﻟ ﺸﻐﻞ اﻟﻤﺒ ﺬول ﻋﻠ ﻰ اﻟﻨﻈ ﺎم أو اﻟﻤﺒ ﺬول ﺑﻮاﺳ ﻄﺔ
اﻟﻨﻈﺎم إﺷﺎرة ﻣﺨﺎﻟﻔﺔ :
-ﻓﻔﻲ اﻟﻘﺎﻧﻮن ، ΔE = q - w :ﻓﺈن اﻟ ﺸﻐﻞ اﻟﻤﺒ ﺬول ﺑﻮاﺳ ﻄﺔ اﻟﻨﻈ ﺎم ﺗﻜ ﻮن إﺷ ﺎرﺗﮫ ﻣﻮﺟﺒ ﺔ،
أﻣﺎ إذا ﻛﺎن اﻟﺸﻐﻞ ﻣﺒﺬوﻻً ﻋﻠﻰ اﻟﻨﻈﺎم ﺗﻜﻮن إﺷﺎرﺗﮫ ﺳﺎﻟﺒﺔ.
-وﻓﻲ اﻟﻘﺎﻧﻮن ΔE = q + wﻓﺈن اﻟﺸﻐﻞ اﻟﻤﺒﺬول ﺑﻮاﺳﻄﺔ اﻟﻨﻈﺎم ﺗﻜﻮن إﺷ ﺎرﺗﮫ ﺳ ﺎﻟﺒﺔ ،أﻣ ﺎ
إذا ﻛﺎن اﻟﺸﻐﻞ ﻣﺒﺬوﻻً ﻋﻠﻰ اﻟﻨﻈﺎم ﺗﻜﻮن إﺷﺎرﺗﮫ ﻣﻮﺟﺒﺔ.
وﻓﻲ ﻣﺴﺎﺋﻠﻨﺎ اﻟﺤﺴﺎﺑﯿﺔ ﺳﻨﻌﺘﻤﺪ اﻟﻌﻼﻗﺔ :
ΔE = q + w
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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(٢إذا ﺳﻤﺢ أن ﺗﻨﺘﻘﻞ ﻛﻤﯿﺔ ﻣﻦ اﻟﻄﺎﻗﺔ اﻟﻰ اﻟﻨﻈﺎم ﻋﻠﻰ ﺷﻜﻞ ﺷﻐﻞ ) (Wﻓﺈن ﻃﺎﻗﺘﮫ اﻟﺪاﺧﻠﯿﺔ
ﻋﻨﺪ اﻟﺤﺎﻟﺔ اﻟﻨﮭﺎﺋﯿﺔ ) (Efﺗﻜﻮن :
Ef = Ei + q + w
واﻟﻤﻌﺎدﻟﺔ اﻷﺧﯿﺮة:
∆E = q + w
ھﻲ اﻟﺼﯿﻐﺔ اﻟﺮﯾﺎﺿﯿﺔ اﻟﻤﻨﺎﺳﺒﺔ ﻟﻠﻘﺎﻧﻮن اﻷول ﻟﻠﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ ﺣﯿﺚ ﺗﺒﯿﻦ ﺗﻐﯿﺮ اﻟﻄﺎﻗﺔ
اﻟﺪاﺧﻠﯿﺔ اﻟﻤﺮاﻓﻘﺔ ﻟﺘﺒﺎدل اﻟﺸﻐﻞ واﻟﺤﺮارة ﺑﯿﻦ اﻟﻨﻈﺎم واﻟﻤﺤﯿﻂ.
ﺟﺪول ) : (٣ﻣﻠﺨﺺ ﻹﺷﺎرة اﻟﺸﻐﻞ وﻛﻤﯿﺔ اﻟﺤﺮارة
w q اﻹﺷﺎرة
ﺗﻨﻄﻠﻖ ﺣﺮارة ﻣﻦ اﻟﻨﻈﺎم اﻟﻰ اﻟﻤﺤﯿﻂ )ﻋﻤﻠﯿ ﺔ اﻟﻨﻈ ﺎم ﯾﻌﻤ ﻞ ﺷ ﻐﻼً ﻋﻠ ﻰ اﻟﻤﺤ ﯿﻂ )ﺗﻨﻄﻠ ﻖ )(-
ﻛﻤﯿﺔ ﻣﻦ اﻟﻄﺎﻗﺔ(. ﻧﺎﺷﺮة ﻟﻠﺤﺮارة(.
ﯾﻤ ﺘﺺ اﻟﻨﻈ ﺎم ﺣ ﺮارة ﻣ ﻦ اﻟﻤﺤ ﯿﻂ )ﻋﻤﻠﯿ ﺔ اﻟﻨﻈ ﺎم ﯾﺤ ﺼﻞ ﻋﻠ ﻰ ﺷ ﻐﻞ ﻣ ﻦ اﻟﻤﺤ ﯿﻂ )(+
)ﺗﻤﺘﺺ ﻛﻤﯿﺔ ﻣﻦ اﻟﻄﺎﻗﺔ(. ﻣﺎﺻﺔ ﻟﻠﺤﺮارة(
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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Fig. 12 : When a reaction (such as the thermal decomposition of calcium carbonate) takes
place in a closed, constant-volume container, the gas fills the container but cannot expand
against the surrounding atmosphere. As a result, it does no work on the surroundings.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﻓﯿﮫ ﺗﻜﻮن درﺟﺔ ﺣﺮارة اﻟﻨﻈﺎم ﺛﺎﺑﺘﺔ أﺛﻨﺎء ﺗﻐﯿﺮ اﻟﻨﻈﺎم ﻣﻦ ﺣﺎﻟﺔ اﻟﻰ أﺧﺮى ،أي أن
) ، ( ∆T = 0وﯾﻜﻮن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﯾﺴﺎوي ﺻﻔﺮاً ) ( ΔE = 0وﺗﺆول ﺣﯿﻨﺌﺬ
ﻋﻨﺪ ﺛﺒﺎت Tاﻟﻰ : ∆E = q - P ∆V اﻟﻤﻌﺎدﻟﺔ
q = - w = PΔV
وﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﻻ ﯾﺤﺪث أي ﺗﺒﺎدل ﺣﺮاري ﺑﯿﻦ اﻟﻨﻈﺎم واﻟﻤﺤﯿﻂ ﺑﺤﯿﺚ ﻻ ﯾﻀﺎف اﻟﻰ
اﻟﻨﻈﺎم وﻻ ﯾﺆﺧﺬ ﻣﻨﮫ أي ﻃﺎﻗﺔ ﺣﺮارﯾﺔ أي أن ) (q = 0وﺑﺬﻟﻚ ﺗﺆول اﻟﻤﻌﺎدﻟﺔ
ΔE = q - PΔVاﻟﻰ :
∆E = w = - P ∆V
وھﺬا ﯾﻌﻨﻲ أن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﯾﺴﺎوي ﻋﻨﺪﺋﺬ اﻟﺸﻐﻞ اﻟﻤﻨﺠﺰ ،وﯾﺮاﻓﻖ ھﺬا اﻟﻨﻮع
ﻣﻦ اﻟﻌﻤﻠﯿﺎت ﺗﻐﯿﺮ ﻓﻲ درﺟﺔ اﻟﺤﺮارة.
وﻓﻲ ھﺬه اﻟﺤﺎﻟﺔ ﯾﺘﻐﯿﺮ اﻟﻨﻈﺎم وﻟﻜﻨﮫ ﻓﻲ ﻧﮭﺎﯾﺔ اﻟﻌﻤﻠﯿﺔ ﯾﺮﺟﻊ اﻟﻰ ﺣﺎﻟﺘﮫ اﻹﺑﺘﺪاﺋﯿﺔ أي أن
ﻃﺎﻗﺘﮫ اﻟﺪاﺧﻠﯿﺔ ﻻ ﺗﺘﻐﯿﺮ ) ( ΔE = 0واﻟﻤﻌﺎدﻟﺔ ∆E = q - P∆Vﺗﺆول ﺣﯿﻨﺌﺬ اﻟﻰ :
q = - w = PΔV
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(١١
إذا ﻛﺎن اﻟﺸﻐﻞ اﻟﻤﺒﺬول ﻋﻨﺪﻣﺎ ﺿﻐﻂ ﻏﺎز ﻓﻲ اﺳﻄﻮاﻧﺔ ﯾﺴﺎوي ) (299 Jوﺧﻼل ھﺬه
اﻟﻌﻤﻠﯿﺔ اﻧﺘﻘﻠﺖ ﻣﻦ اﻟﻐﺎز اﻟﻰ اﻟﻤﺤﯿﻂ ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة ﻣﻘﺪارھﺎ ) .(70.3Jﻓﺎﺣﺴﺐ اﻟﺘﻐﯿﺮ
ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻐﺎز.
ﺍﳊﻞ
ﺑﻤﺎ أن ﻛﻤﯿﺔ اﻟﺤﺮارة ﺗﻨﻄﻠﻖ ﻣﻦ اﻟﻨﻈﺎم اﻟﻰ اﻟﻤﺤﯿﻂ ﻓﺎﻟﺤﺮارة ﻣﻔﻘﻮدة وﺑﺎﻟﺘﺎﻟﻲ إﺷﺎرﺗﮭﺎ ﺗﻜﻮن
ﺑﺎﻟﺴﺎﻟﺐ أي ) .( q = - 70.3 Jوﺑﻤﺎ أن اﻟﻐﺎز ﯾﻨﻜﻤﺶ )ﯾﻌﻤﻞ ﻋﻠﯿﮫ ﺷﻐﻞ ﻣﻦ اﻟﻨﻈﺎم(
ﻓﻘﯿﻤﺘﮫ ﺑﺎﻟﻤﻮﺟﺐ ).(w = +
وﺑﺘﻄﺒﯿﻖ اﻟﻘﺎﻧﻮن اﻷول ﻓﻲ اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ :
∆E = q + w
∆E = (- 70.3 ) + (299) = 228.7 J
وﻷن ﻗﯿﻤﺔ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﺑﺎﻟﻤﻮﺟﺐ ،ﻓﺈن اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻐﺎز ﺗﺰداد ﺑﻤﻘﺪار ).(228.7 J
ﻣﺜﺎﻝ )(١٢
ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﺔ ،اﻛﺘﺴﺐ ﻏﺎز ﻛﻤﯿﺔ ﺣﺮارة ﻣﻘﺪارھﺎ 30 Jﻓﺘﻤﺪد اﻟﻐﺎز وﺑﺬل ﺷﻐﻼً
ﻋﻠﻰ اﻟﻤﺤﯿﻂ ﻣﻘﺪاره )(130 J
أ( اﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻨﻈﺎم.
ب( اﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻤﺤﯿﻂ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1498
وﻓﯿﮫ ) (qﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﺘﻲ ﻓﻘﺪھﺎ اﻟﻤﺤﯿﻂ )اﻛﺘﺴﺒﮭﺎ( اﻟﻨﻈﺎم ،وﺗﻜﻮن إﺷﺎرﺗﮭﺎ ﺑﺎﻟﺴﺎﻟﺐ (q
) = - 30 Jو ) (wھﻮ اﻟﺸﻐﻞ اﻟﺬي اﻛﺘﺴﺒﮫ اﻟﻤﺤﯿﻂ )ﺑﺬﻟﮫ اﻟﻨﻈﺎم( وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن إﺷﺎرﺗﮫ
)(w = + 130 J ﺗﻜﻮن ﺑﺎﻟﻤﻮﺟﺐ
وﺑﺎﻟﺘﻌﻮﯾﺾ ﺑﮭﺬه اﻟﻘﯿﻢ ﻧﺤﺼﻞ ﻋﻠﻰ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻤﺤﯿﻂ ﻛﻤﺎ ﯾﻠﻲ :
ΔE = q + w
)∆E = (- 30 J) + (+ 130 J
∆E = + 100 J
وﻧﻼﺣﻆ أن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻤﺤﯿﻂ ﺑﺎﻟﻤﻮﺟﺐ ،وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈﻧﮭﺎ زادت ﺑﻤﻘﺪار
) .(100 Jوﻛﻼ اﻹﺟﺎﺑﺘﯿﻦ ﻓﻲ اﻟﻔﻘﺮﺗﯿﻦ )أ( و )ب( ﺗﺆﯾﺪان ﻗﺎﻧﻮن ﺣﻔﻆ اﻟﻄﺎﻗﺔ ،ﺣﯿﺚ أن
اﻟﻨﻈﺎم ﻓﻘﺪ ) (100 Jﻣﻦ ﻃﺎﻗﺘﮫ واﻛﺘﺴﺒﮭﺎ اﻟﻤﺤﯿﻂ.
ﻣﺜﺎﻝ )(١٣
ﺿﻐﻄﺖ أﺳﻄﻮاﻧﺔ ﺗﺤﺘﻮي ﻋﻠﻰ ﻏﺎز ،ﻓﻜﺎن اﻟﺸﻐﻞ اﻟﻤﻨﺠﺰ ) ،(300 Jﻓﺎﻧﺘﻘﻠﺖ ﺣﺮارة
ﻣﻘﺪارھﺎ ) (70 Jﻣﻦ اﻟﻐﺎز اﻟﻰ اﻟﻤﺤﯿﻂ .اﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ ﻃﺎﻗﺔ اﻟﻐﺎز اﻟﺪاﺧﻠﯿﺔ.
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1499
وﺑﺎﻟﺘﻌﻮﯾﺾ ﺑﮭﺬه اﻟﻘﯿﻢ ﻓﻲ اﻟﻤﻌﺎدﻟﺔ ﻧﺤﺼﻞ ﻋﻠﻰ اﻟﺘﻐﯿﺮ ﻓﻲ ﻃﺎﻗﺔ اﻟﻐﺎز اﻟﺪاﺧﻠﯿﺔ :
ΔE = q + w
)∆E = (- 70 J) + (+ 300 J
∆E = + 230 J
وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻨﻈﺎم ﻗﺪ زادت ﺑﻤﻘﺪار 230 J
ﻣﺜﺎﻝ )(١٤
اﺣﺴﺐ ﻛﻤﯿﺔ اﻟﺤﺮارة ) (qﻟﻨﻈﺎم ﯾﻌﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ ﻗﺪره ) (20 Jوﺗﺘﻨﺎﻗﺺ ﻃﺎﻗﺘﮫ
اﻟﺪاﺧﻠﯿﺔ ﺑﻤﻘﺪار ).(30 J
ﺍﳊﻞ
ﺑﻤﺎ أن اﻟﻨﻈﺎم ﻋﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ ﻓﺈﻧﮫ ﻗﺪ ﺗﻤﺪد ﺣﺠﻤﮫ )اﻟﺘﻐﯿﺮ ﻓﻲ ﺣﺠﻤﮫ ﺑﺎﻟﻤﻮﺟﺐ(
وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﻗﯿﻤﺔ اﻟﺸﻐﻞ ﺑﺎﻟﺴﺎﻟﺐ وﻓﻘﺎً ﻟﻠﻌﻼﻗﺔ ) ، (w = - PΔV(+) = -وﯾﻤﻜﻦ اﻟﻘﻮل أن اﻟﻨﻈﺎم
ﻗﺪ ﻓﻘﺪ ) (-ﺷﻐﻼً وﺑﺎﻟﺘﺎﻟﻲ ﻓﻘﯿﻤﺔ اﻟﺸﻐﻞ ﺑﺎﻟﺴﺎﻟﺐ ). (w = - 20 J
وﺑﻤﺎ أن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﺗﻨﺎﻗﺺ ﻓﺒﺎﻟﺘﺎﻟﻲ ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﺑﺎﻟﺴﺎﻟﺐ
) ( ∆E = - 30 J
وﻣﻦ ھﻨﺎ ﯾﻤﻜﻦ اﻟﺘﻄﺒﯿﻖ ﻓﻲ اﻟﻘﺎﻧﻮن اﻟﺘﺎﻟﻲ ﻟﺤﺴﺎب ﻛﻤﯿﺔ اﻟﺤﺮارة :
ΔE = q + w
q = ∆E - w
)q = - 30 J - (- 20 J
q = - 30 J + 20 J
q = - 10 J
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1500
ﻣﺜﺎﻝ )(١٥
إذا ﺗﻢ ﺿﻐﻂ ﺣﺠﻢ ) (400 mlﻣﻦ ﻏﺎز اﻟﻰ ﺣﺠﻢ ) (200 mlﺗﺤﺖ ﺿﻐﻂ ﺧﺎرﺟﻲ ﻗﺪره
) ،(3 atmأو ﺟﺪ ﻗﯿﻢ ) ( ΔE, w, qﻟﻠﻐﺎز إذا اﻣﺘﺺ اﻟﻐﺎز ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة ) (13 Jﺛﻢ أوﺟﺪ
ﺍﳊﻞ
1500
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1501
ﺗﺼﺒﺢ :
∆E = q v
واﻟﻤﻌﺎدﻟﺔ ∆E = q vﺗﺒﯿﻦ أن ﺣﺮارة اﻟﺘﻔﺎﻋﻞ ﺗﺴﺎوي اﻟﻔﺮق ﺑﯿﻦ ﻃﺎﻗﺔ اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ
واﻟﻤﺘﻔﺎﻋﻠﺔ )أي ﺗﺴﺎوي اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﻨﻈﺎم( ،وھﺬا ﻣﺎ ﯾﺤﺪث ﻋﻨﺪ ﻗﯿﺎس ﺣﺮارة
اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ﺣﺠﻢ ﺛﺎﺑﺖ ﺑﺎﺳﺘﺨﺪام اﻟﻤﺴﻌﺮ.
(٢أﻣﺎ ﻋﻨﺪ إﺟﺮاء اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ،وﺣﺪوث ﺗﻐﯿﺮ ﻣﻠﺤﻮظ ﻓﻲ اﻟﺤﺠﻢ
ﻧﺘﯿﺠﺔ اﺷﺘﺮاك ﺑﻌﺾ اﻟﻤﻮاد اﻟﻐﺎزﯾﺔ ﺳﻮاء ﻛﺎﻧﺖ ﻣﺘﻔﺎﻋﻠﺔ أو ﻧﺎﺗﺠﺔ أو ﻛﻼھﻤﺎ ،ﺑﺎﻟﺘﺎﻟﻲ ﻻ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1502
( )
) q P = E + PVP - ( E R + PVR
P
) q P = ( E P + PVP ) - ( E R + PVR
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺣﯿﺚ :
: HPاﻧﺜﺎﻟﺒﻲ اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ : HR ،اﻧﺜﺎﻟﺒﻲ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ.
: ΔHﺗﻤﺜﻞ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ وھﻮ ﯾﺴﺎوي اﻟﻔﺮق ﺑﯿﻦ اﻧﺜﺎﻟﺒﻲ اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ وإﻧﺜﺎﻟﺒﻲ
اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ.
واﻟﻤﻌﺎدﻟﺔ q P = ∆H :ﺗﺒﯿﻦ أن ﺣﺮارة اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ﺗﺴﺎوي اﻟﺘﻐﯿﺮ ﻓﻲ
اﻹﻧﺜﺎﻟﺒﻲ.
وﺑﺪﻣﺞ اﻟﻤﻌﺎدﻟﺘﯿﻦ :
q P = ∆E + P∆V
q P = ∆H
وﻓﯿﮭﺎ ﺗﻜﻮن ﺗﻐﯿﺮات اﻟﺤﺠﻢ ﻛﺒﯿﺮة وﻻ ﯾﻤﻜﻦ إھﻤﺎﻟﮭﺎ ،وﺑﻔﺮض ﺳﻠﻮك اﻟﻐﺎزات ﺳﻠﻮﻛﺎً ﻣﺜﺎﻟﯿﺎً
ﻓﺈن :
PVR = n R RT
PVP = n P RT
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺣﯿﺚ:
: nPﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ اﻟﻨﺎﺗﺠﺔ.
: nRﻋﺪد ﻣﻮﻻت اﻟﻤﻮاد اﻟﻐﺎزﯾﺔ اﻟﻤﺘﻔﺎﻋﻠﺔ )ﻋﻨﺪ ﺿﻐﻂ ودرﺟﺔ ﺣﺮارة ﺛﺎﺑﺘﯿﻦ(.
: Rﺛﺎﺑﺖ اﻟﻐﺎزات اﻟﻌﺎم ) : T ،(8.314 J/K. molدرﺟﺔ اﻟﺤﺮارة ﺑﺎﻟﻜﺎﻟﻔﻦ ).(K
وﻣﻦ اﻟﻤﻌﺎدﻟﺔ :
∆ H = ∆ E + P ∆V
ﻛﻤﺎ ﯾﻠﻲ : P ∆V ﻓﺈﻧﻨﺎ ﺳﻨﺠﺮي ﺗﺤﻮﯾﺮاً ﻋﻠﻰ اﻟﻘﯿﻤﺔ
) P∆V = P (VP - VR
P∆V = PVP - PVR
P∆V = n P RT - n R RT
) P∆V = RT (n P - n R
P∆V = ∆n (g) RT
ﺣﯿﺚ ) : Δn (gاﻟﺘﻐﯿﺮ ﻓ ﻲ ﻋ ﺪد اﻟﻤ ﻮﻻت اﻟﻐﺎزﯾ ﺔ ،وﯾﻤﺜ ﻞ اﻟﻔ ﺮق ﺑ ﯿﻦ ﻋ ﺪد اﻟﻤ ﻮﻻت اﻟﻐﺎزﯾ ﺔ
اﻟﻨﺎﺗﺠﺔ واﻟﻤﺘﻔﺎﻋﻠﺔ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1505
(٢ﺗﻔﺎﻋﻼﺕ ﺗﺸﱰﻙ ﻓﻴﻬﺎ ﻏﺎﺯﺍﺕ ﻣﺘﻔﺎﻋﻠﺔ ﻭﻧﺎﲡﺔ ﺣﻴﺚ ): (nR = nP
(٣ﺗﻔﺎﻋﻼﺕ ﺗﺸﱰﻙ ﻓﻴﻬﺎ ﻣﻮﺍﺩ ﺻﻠﺒﺔ ﺃﻭ ﺳﺎﺋﻠﺔ ﻓﻘﻂ )ﻻ ﺗﺸﱰﻙ ﻓﻴﻬﺎ ﻣﻮﺍﺩ ﻏﺎﺯﻳﺔ( :
ﺗﻜﻮن ﻓﯿﮭﺎ ﺗﻐﯿﺮات اﻟﺤﺠﻢ ﺻﻐﯿﺮة ) ( ΔV ≈ 0وﺑﺎﻟﺘﺎﻟﻲ ﯾﻤﻜﻦ إھﻤﺎﻟﮭﺎ ،ﺣﯿﻨﺌﺬ ﺗﺆول اﻟﻤﻌﺎدﻟﺔ
اﻟﻰ : ∆H = ∆E + P∆V
ΔH = ΔE + P∆V
∆n = 0
⇒ ∆H = ∆ E
ﺟﺪول ) : (٥ﻣﻠﺨﺺ ﻟﻠﻌﻼﻗﺔ اﻟﺮﯾﺎﺿﯿﺔ ﺑﯿﻦ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ واﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ
ﻟﺘﻔﺎﻋﻼت ﺗﺸﺘﺮك ﻓﯿﮭﺎ ﻏﺎزات وأﺧﺮى ﻻ ﺗﺸﺎرك ﺑﮭﺎ ﻏﺎزات.
ﺗﻔﺎﻋﻼت ﺗﺸﺘﺮك ﻓﯿﮭﺎ ﺗﻔﺎﻋﻼت ﺗﺸﺘﺮك ﻓﯿﮭﺎ ﺗﻔﺎﻋﻼت ﺗﺸﺘﺮك ﻓﯿﮭﺎ
ﻣﻮاد ﻏﺎزﯾﺔ ) (nP ≠nRﻣﻮاد ﻏﺎزﯾﺔ = (nPﻣﻮاد ﺻﻠﺒﺔ أو ﺳﺎﺋﻠﺔ ﻓﻘﻂ
)nR اﻟﻤﻌﺎدﻟﺔ اﻷﺳﺎﺳﯿﺔ
∆H = ∆E ∆H = ∆E ΔH = ΔE + Δn (g) RT ΔH = ΔE + P ∆V
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1506
ﻣﺜﺎﻝ )(١٦
إذا ﻋﻠﻤﺖ أن اﻟﺘﻐﯿﺮات اﻟﻜﯿﻤﯿﺎﺋﯿﺔ واﻟﻔﯿﺰﯾﺎﺋﯿﺔ اﻟﺘﺎﻟﯿﺔ ﺗﺤﺪث ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ،ﻓﺤﺪد ﻓﻲ ﻛﻞ
ﻣﺮة ھﻞ اﻟﺸﻐﻞ ﯾﻌﻤﻞ ﻣﻦ ﻗﺒﻞ اﻟﻨﻈﺎم ﻋﻠﻰ اﻟﻤﺤﯿﻂ أو ﯾﻌﻤﻞ ﻣﻦ ﻗﺒﻞ اﻟﻤﺤﯿﻂ ﻋﻠﻰ اﻟﻨﻈﺎم ،أو
أن ﻛﻤﯿﺔ اﻟﺸﻐﻞ ﻣﮭﻤﻠﺔ.
ﺍﳊﻞ
(١
n =2 n =0
R P
)Sn(s) + 2F2 (g) → SnF4 (s
∆n = n P - nR = 0 - 2 = - 2
)(nP = 0, nR = 2 mol
ﻓﺎﻟﻨﻈﺎم ﺣﺠﻤﮫ ﺳﯿﻘﻞ ﻟﺬﻟﻚ ﻓﺈن اﻟﻤﺤﯿﻂ ﯾﻌﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم.
(٢
n =0 n =0
R
P
)AgNO 3 (aq) + NaCl(aq) → AgCl(s) + NaNO 3 (aq
∆n = n P - n R = 0 - 0 = 0
ﺣﯿﺚ أﻧﮫ ﻻ ﯾﻮﺟﺪ ﻣﻮاد ﻏﺎزﯾﺔ ﻣﺘﻔﺎﻋﻠﺔ أو ﻧﺎﺗﺠﺔ ﻣﺸﺘﺮﻛﺔ ﻓﺈﻧﮫ ﯾﻤﻜﻦ إھﻤﺎل اﻟﺸﻐﻞ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1507
(٣
n =1 n =1
R
P
)→ C O 2 (g
)C(s) + O 2 (g
Δn = n P - n R = 1 - 1 = 0
) ، (nR = 1mol, nP = 2 molﺣﯿﺚ أن ﻣﻮل واﺣﺪ ﻣﻦ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ﯾﻨﺘﺞ ﻣﻮﻟﯿﻦ ﻣﻦ
اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ اﻟﻐﺎزﯾﺔ ﻓﺈن ﺣﺠﻢ اﻟﻨﻈﺎم ﯾﺰداد وﻟﺬﻟﻚ ﻓﺈن اﻟﻨﻈﺎم ﯾﻌﻤﻞ ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ.
ﻣﺜﺎﻝ )(١٧
إذا ﻛﺎن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﯾﺴﺎوي ) (-333 kJﻟﻠﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ :
)NH 4 Cl(aq) + NaNO 2 (aq) → N 2 (g) + 2H 2O(L) + NaCl(aq
ﻋﻨﺪﻣﺎ ﯾﻨﺘﺞ ﻣﻮل واﺣﺪ ﻣﻦ ،N2ﻓﺈذا ﻛﺎن إﻧﺘﺎج ﻣﻮل واﺣﺪ ﻣﻦ اﻟﻨﯿﺘﺮوﺟﯿﻦ ﯾﺠﻌﻞ اﻟﻨﻈﺎم
ﯾﺰداد ﺑﻤﻘﺪار ) ،(22.4 Lﻋﻨﺪ ﺿﻐﻂ ﺟﻮي واﺣﺪ .ﻓﺎﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ إﻧﺜﺎﻟﺒﻲ ھﺬا اﻟﺘﻔﺎﻋﻞ.
ﺍﳊﻞ
3
Δ E = - 333 × 10 J, P = 1 atm , Δ V = 2 2 .4 L
P ∆ V = 1 atm × 2 2 .4 L = 2 2 .4 L . atm
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1508
وﻟﺘﺤﻮﯾﻞ اﻟﻘﯿﻤﺔ 22.4 L.atmاﻟﻰ وﺣﺪة اﻟﺠﻮل ﻧﻀﺮب ھﺬه اﻟﻘﯿﻤﺔ ﺑـ : 101.3
101.325 J
× 22.4 L . atm = 2269.68 J
L . atm
وﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ :
∆H = ∆E + P∆V
ﻣﺜﺎﻝ )(١٨
إذا ﻛﺎﻧﺖ اﻟﺤﺮارة اﻟﻤﺼﺎﺣﺒﺔ ﻻﺣﺘﺮاق ﻣﻮل واﺣﺪ ﻣﻦ اﻟﺒﻨﺰﯾﻦ ﺗﺴﺎوي ) (- 3264.3 kJﻋﻨﺪ
ﺣﺠﻢ ﺛﺎﺑﺖ ودرﺟﺔ ﺣﺮارة ) (298 Kﻓﺎﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ) ( ∆Hﻟﻠﺘﻔﺎﻋﻞ ،إذا
ﻋﻠﻤﺖ أن اﻟﺒﻨﺰﯾﻦ ﯾﺤﺘﺮق ﺑﻮﺟﻮد اﻷﻛﺴﺠﯿﻦ ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ :
)C 6 H 6 (L) + 7.5 O 2 (g) → 6CO 2 (g) + 3H 2O(L
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1509
ﻣﻠﺤﻮﻇﺔ :
ﻣﺜﺎﻝ )(١٩
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1510
ﺍﳊﻞ
ﻣﺜﺎﻝ )(٢٠
إذا ﻛﺎﻧﺖ اﻟﺤﺮارة اﻟﻤﺘﺼﺎﻋﺪة ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ ﺗﺤﺖ ﺣﺠﻢ ﺛﺎﺑ ﺖ ھ ﻲ 57507 Calﻋﻨ ﺪ درﺟ ﺔ
ﺣﺮارة )) .(0 °Cﻋﻠﻤﺎً ﺑﺄن (R = 2 Cal/mol K :
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1511
ﺍﳊﻞ
ΔH = ΔE + ΔnRT
q P = q V + ΔnRT
)q P = ( - 57507) + (- 0.5 × 2 × (0 + 273
q P = - 57780 Cal
ﻣﺜﺎﻝ )(٢١
ﺗﻤﺪدت ) (3 molﻣﻦ ﻏﺎز ﻣﺜﺎﻟﻲ ﻋﻨﺪ اﻟﻀﻐﻂ اﻟﺠﻮي ،وﻛﺎﻧﺖ ﻋﻤﻠﯿﺔ اﻟﺘﻤﺪد ﻋﻜﺴﯿﺔ ﻣﻦ
) (40 Lاﻟﻰ ﺣﺠﻢ ﻧﮭﺎﺋﻲ ) ،(60 Lﻓﺈذا ﻛﺎﻧﺖ اﻟﺤﺮارة اﻟﻤﻤﺘﺼﺔ ﺗﺴﺎوي ﺣﺠﻢ أوﻟﻲ
∆H ج( ب( ΔE أ( w ) (21.6 kJﻓﺎﺣﺴﺐ ﻛﻼً ﻣﻦ:
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1512
∆E = q P + w
3
)∆E = (+ 21.6 × 10 J) + (- 2026.5 J
∆E = 19573.5 J
∆E = 19.6 kJ
ج( ﺣﺴﺎب ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ :
ﺑﻤﺎ أن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﺤﺠﻢ ﺗﻢ ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ،ﻓﺈن ﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﻤﻤﺘﺼﺔ ﺗﻌﺒﺮ ﻋﻦ اﻟﺘﻐﯿﺮ
ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ.
ΔH = q P
ΔH = 21.6 kJ
ﻣﺜﺎﻝ )(٢٢
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1513
ﻣﺜﺎﻝ )(٢٣
← )4................3H 2 (g) + N2 (g)→ 2NH3 (g
← )5.................H 2 (g) + Cl 2 (g)→ 2HCl(g
ﺍﳊﻞ
اﻟﻤﻌﺎدﻟﺔ اﻟﺘﻲ ﺗﻜﻮن ﻓﯿﮭﺎ ) ( ∆n = 0ھﻲ اﻟﺘﻲ ﺗﺤﻘﻖ اﻟﻌﻼﻗﺔ ) ( ∆H = ∆Eوﻓﻘﺎً ﻟﻠﻘﺎﻧﻮن :
ΔH = ΔE + ΔnRT
ﻟﺬﻟﻚ ﻧﺤﺴﺐ ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ ﻋﺪد اﻟﻤﻮﻻت ﻛﻤﺎ ﯾﻠﻲ :
اﻟﻤﻌﺎدﻟﺔ اﻷوﻟﻰ :
n =3 n =2
R
P
)1.............. 2H2 (g) + O2 (g) → 2H2 O(g
∆n = 2 - 3 = - 1
وﺑﺎﻟﺘﺎﻟﻲ ﻻ ﺗﺤﻘﻖ ھﺬه اﻟﻤﻌﺎدﻟﺔ اﻟﻤﺴﺎواة ) ( ∆H = ∆Eﻷن اﻟﺘﻐﯿﺮ ﻓﻲ ﻋﺪد اﻟﻤﻮﻻت ﻻ ﯾﺴﺎوي
اﻟﺼﻔﺮ :
1513
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1514
ΔH = ΔE + ΔnRT
ΔH = ΔE + (- RT)
ΔH = ΔE - RT
⇒ ∆H ≠ ∆E
: اﻟﻤﻌﺎدﻟﺔ اﻟﺜﺎﻧﯿﺔ
n =1 nP = 1
R
2..............1/2Cl2 (g) + 1/2F2 (g) → ClF(g)
∆n = 1 - 1 = 0
n
R =7 n =8
P
3............... 4NH 3 (g) + 3O 2 (g) → 2N 2 (g) + 6H 2 O(g)
∆n = 8 - 7 = 1
ΔH = ΔE + ΔnRT
ΔH = ΔE + ( RT)
ΔH = ΔE + RT
⇒ ∆H ≠ ∆E
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1515
: اﻟﻤﻌﺎدﻟﺔ اﻟﺮاﺑﻌﺔ
n =4 n =2
R
P
4................3H 2 (g) + N 2 (g) ←→ 2NH 3 (g)
Δn = 2 - 4 = - 2
ΔH = ΔE + ΔnRT
ΔH = ΔE + (- 2 RT)
ΔH = ΔE - 2 RT
⇒ ∆H ≠ ∆E
: اﻟﻤﻌﺎدﻟﺔ اﻟﺨﺎﻣﺴﺔ
n =2 n =2
R
P
←→ 2HCl(g)
5................. H 2 (g) + Cl 2 (g)
∆n = 2 - 2 = 0
ΔH = ΔE + ΔnRT
ΔH = ΔE + (0 × RT)
ΔH = ΔE
: اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎدﺳﺔ
n =6 n = 12
R
P
6..................C 6 H12O 6 (S) + 6O 2 (g) → 6H 2O(g) + 6CO 2 (g)
∆n = 12 - 6 = 6
ΔH = ΔE + ΔnRT
ΔH = ΔE + (6 × RT)
ΔH = ΔE + 6 RT
⇒ ∆H ≠ ∆E
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1516
ﻣﺜﺎﻝ )(٢٤
ﺍﳊﻞ
ﺣﻮﻟﺖ ﻣﻦ اﻟﻜﯿﻠﻮ ﺟﻮل اﻟﻰ اﻟﺠﻮل )(ΔH = 164 kJ وﻧﻼﺣﻆ أن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ
ﺑﺎﻟﻀﺮب ﻓﻲ اﻟﻤﻌﺎﻣﻞ ) (1000وذﻟﻚ ﺑﺴﺒﺐ أن اﻟﻤﻌﺎدﻟﺔ ΔH = ΔE + ΔnRTﺗﺤﻮي ﺛﺎﺑﺖ
) (R = 8.314 J/K. molﻓﻨﻼﺣﻆ أن ﻣﻦ وﺣﺪاﺗﮫ اﻟﺠﻮل ،ﻟﺬﻟﻚ ﻟﺰم اﻟﻐﺎزات
أن ﺗﻜﻮن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ﺗﺤﻮي ﻧﻔﺲ اﻟﻮﺣﺪة.
1516
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1517
ﻣﺜﺎﻝ )(٢٥
ﺍﳊﻞ
ﻣﺜﺎﻝ )(٢٦
إذا ﻋﻠﻤﺖ أﻧﮫ ﻋﻨﺪ ) (18 ºCﯾﺤﺘﺮق اﻟﺒﻨﺰﯾﻦ وﻓﻖ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ :
)C 6 H 6 (L) + 15/2O 2 (g) → 6CO 2 (g) + 3H 2O(L ΔH = - 3290 kJ
اﺣﺴﺐ ) ( ∆Eﻟﻠﺘﻔﺎﻋﻞ.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1518
ﺍﳊﻞ
n = 7.5 n =6
R
P
C6 H 6 (L) + 15/2O 2 (g) → 6CO 2 (g) + 3H 2 O(L) ΔH = - 3290 kJ
∆n = 6 - 7.5 = - 1.5
: وﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ
ΔH = ΔE + ΔnRT
ΔE = ΔH - ΔnRT
3
∆E = (- 3290 × 10 J) - (-1.5 × 8.314 J/K.mol × 291 K)
∆E = - 3286370.939 J
∆E = - 3286.37 kJ
(٢٧) ﻣﺜﺎﻝ
ﻓﺈﻧﮫ ﺗﻨﻄﻠﻖ ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة ﻣﻘﺪارھﺎ،C3H8 إذا اﺣﺘﺮق ﻣﻮل واﺣﺪ ﻣﻦ ﻏﺎز اﻟﺒﺮوﺑﺎن
:(1 atm, 25 ºC) ( ﻋﻨﺪ2198.7 kJ)
C3 H 8 (g) + 5O 2 (g) → 3CO 2 (g) + 4H 2 O(L) ΔH = - 2198.7 kJ
ﺍﳊﻞ
n =6 n =3
R
P
C3H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2 O(L) ΔH = - 2198.7 kJ
∆n = 3 - 6 = - 3
: وﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ
1518
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1519
ﻣﺜﺎﻝ )(٢٨
إذا ﻛﺎﻧﺖ اﻟﺤﺮارة اﻟﻤﺼﺎﺣﺒﺔ ﻻ ﺣﺘﺮاق ﻣﻮل واﺣﺪ ﻣﻦ اﻟﺒﻨﺰﯾﻦ ﺗﺴﺎوي )(- 3264.3 kJ
ﻋﻨﺪ ﺣﺠﻢ ﺛﺎﺑﺖ ودرﺟﺔ ﺣﺮارة ) (298 Kﻓﺎﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ) ( ∆Hﻟﻠﺘﻔﺎﻋﻞ ،إذا
ﻋﻠﻤﺖ أن اﻟﺒﻨﺰﯾﻦ ﯾﺤﺘﺮق ﺑﻮﺟﻮد اﻷﻛﺴﺠﯿﻦ ﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ :
)C6 H6 (L) + 7.5 O2 (g) → 6CO2 (g) + 3H 2O(L
ﺍﳊﻞ
1519
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1520
ﻣﺜﺎﻝ )(٢٩
ﯾﺤﺘﺮق ﻏﺎز اﻟﻤﯿﺜﺎن ) (CH4ﻓﻲ ﺟﻮ ﻣﻦ اﻷﻛﺴﺠﯿﻦ اﺣﺘﺮاﻗﺎً ﺗﺎﻣﺎً ،وﺗﻨﻄﻠﻖ ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة
ﻗﺪرھﺎ ) (890 kJ/molﻓﻲ اﻟﻈﺮوف اﻟﻘﯿﺎﺳﯿﺔ .اﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻋﻨﺪ
25 ºC
ﻣﻌﺎدﻟﺔ اﻟﺘﻔﺎﻋﻞ ھﻲ :
)CH 4 (g) + 2O 2 (g
)→ CO 2 (g) + 2H 2 O(L
ﻣﺜﺎﻝ )(٣٠
ﺍﳊﻞ
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1521
: اﻟﻄﺮﯾﻘﺔ اﻷوﻟﻰ
: وﯾﻤﻜﻦ ﺗﻄﺒﯿﻖ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ
ΔH = ∆E + PΔV
∆E = ∆H - P∆V
∆E = (164 × 103 J ) - (1 atm x 22.4 L × 101.3 J/L.atm )
∆E = 161730.88J
∆E = 161.73 kJ
: اﻟﻄﺮﯾﻘﺔ اﻟﺜﺎﻧﯿﺔ
n
=2
R
n
=3
P
2NO 2 (g)
→ 2NO(g) + O 2 (g)
Δn = 3 - 2 = 1
: وﺑﺘﻄﺒﯿﻖ اﻟﻌﻼﻗﺔ
∆H = ∆E + ∆nRT
∆E = ∆H - ∆nRT
∆E = (164 × 103 ) - (1 × 8.314 J/K.mol × 298 K)
∆E = + 161522.428 J
∆E = 161.52 kJ
: اﻟﻄﺮﯾﻘﺔ اﻟﺜﺎﻟﺜﺔ
: ﺑﻤﺎ أن اﻟﻀﻐﻂ ﺛﺎﺑﺖ ﻓﺈن
q P = ΔH
q P = 164 × 103 J
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1522
ﻣﺜﺎﻝ )(٣١
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1523
ﻣﺜﺎﻝ )(٣٢
إذا ﻛﺎن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺪاﺧﻠﯿﺔ ﻟﻠﺘﻔﺎﻋﻞ 2NO 2 (g) → 2NO(g) + O 2 (g) :
ﯾﺴﺎوي ) (-161.73 kJﯾﺠﻌﻞ اﻟﻨﻈﺎم ﯾﺰداد ﺣﺠﻤﮫ ﺑﻤﻘﺪار ) (22.4 Lﻋﻨﺪ ﺿﻐﻂ ﺟﻮي
واﺣﺪ ،ﻓﺎﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ.
ﺍﳊﻞ
ﻣﺜﺎﻝ )(٣٣
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1524
ﺍﳊﻞ
ο
ΔH = - 136 kJ
ο
: ΔE ب( ﺣﺴﺎب
R n =0 n =1
P
2Na 2 O2 (s) + 2H2 O(L) → 4NaOH(s) + O2 (g)
∆n = 1 - 0 = 1
ΔH ο = ∆Eο + ΔnRT
∆E ο = ΔH ο − ΔnRT
∆E ο = (- 136 × 103 J) - (1 × 8.314 J/K mol × 298 K)
∆E ο = - 138477.572 J
∆E ο = - 138.48 kJ
: ج( اﻟﻤﻌﺎدﻟﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺤﺮارﯾﺔ
2Na 2 O2 (S) + 2H 2O(L) → 4NaOH(s) + O2 (g) ∆H = - 136 kJ
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1525
m Na O
2 2
n Na O =
2 2 Mw Na O
2 2
25 g
n Na O = = 0.320 mol
2 2 78 g/ mol
( 2 mol) Na 2 O2 → -136 kJ
( 0.320 mol) Na 2 O 2 → ΔH
(- 136 kJ) × (0.320 mol)
ΔH =
2 mol
ΔH = - 21.76 kJ
(٣٤) ﻣﺜﺎﻝ
ﺍﳊﻞ
– 559.16 kJ (ب – 560.4 kJ (أ
1525
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1526
ﻣﻦ اﻟﻘﺎﻧﻮن اﻷول ﻟﻠﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﻋﻠﻤﻨﺎ أﻧﮫ إذا ﻛﺎن ھﻨﺎك ﺟﺴﻤﺎن أﺣﺪھﻤﺎ ﺳﺎﺧﻦ
واﻵﺧﺮ أﻗﻞ ﻣﻨﮫ ﻓﻲ درﺟﺔ اﻟﺤﺮارة ﻓﺈذا ﻓﻘﺪ أﺣﺪ اﻷﺟﺴﺎم ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة ﻓﻼ ﺑﺪ ﻣﻦ أن
ﯾﻜﺘﺴﺐ اﻟﺠﺴﻢ ﻧﻔﺲ ھﺬه اﻟﻜﻤﯿﺔ ،وﻟﻢ ﯾﺤﺪد اﻟﻘﺎﻧﻮن اﻷول أي اﻟﺠﺴﻤﯿﻦ ﯾﻔﻘﺪ اﻟﺤﺮارة وأﯾﮭﻤﺎ
ﯾﻜﺘﺴﺒﮭﺎ.
واﻟﻘﺎﻧﻮن اﻟﺜﺎﻧﻲ )ﻛﻤﺎ ﺳﻨﺮى ﻻﺣﻘﺎً( ﯾﻠﺨﺺ اﻟﻌﻼﻗﺎت ﺑﯿﻦ اﻛﺘﺴﺎب وﻓﻘﺪان اﻟﺤﺮارة وﺑﯿﻦ
اﻟﺸﻐﻞ اﻟﺬي ﯾﺒﺬل ﺧﻼل اﻟﺘﺤﻮﯾﻼت اﻟﻤﺨﺘﻠﻔﺔ ﻛﻤﺎ ﯾﻤﻜﻨﻨﺎ ﻣﻦ ﺗﺤﺪﯾﺪ أي اﻟﻌﻤﻠﯿﺎت ﯾﻤﻜﻦ
ﺣﺪوﺛﮫ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1527
• اﻧﺘﻘﺎل اﻟﺤﺮارة ﻣﻦ ﺟﺴﻢ ﺣﺎر اﻟﻰ ﺟﺴﻢ ﺑﺎرد ،وﻟﻜﻦ ﻋﻜﺲ ذﻟﻚ ﻻ ﯾﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً أﺑﺪاً.
• ﺗﺘﺪﺣﺮج اﻷﺟﺴﺎم ﻣﻦ اﻟﻤﻮاﻗﻊ اﻟﻤﺮﺗﻔﻌﺔ اﻟﻰ اﻟﻤﻨﺨﻔﻀﺔ وﻟﻜﻨﮭﺎ ﻻ ﯾﻤﻜﻦ أن ﺗﺼﻌﺪ اﻟﻰ
اﻟﻤﻮاﻗﻊ اﻟﻤﺮﺗﻔﻌﺔ ﺗﻠﻘﺎﺋﯿﺎً.
• ذوﺑﺎن اﻟﺴﻜﺮ ﻓﻲ اﻟﻘﮭﻮة ﺗﻠﻘﺎﺋﯿﺎً وﻟﻜﻦ اﻟﺴﻜﺮ اﻟﻤﺬاب ﻻ ﯾﺘﺠﻤﻊ ﺗﻠﻘﺎﺋﯿﺎً ﻓﻲ ﺷﻜﻠﮫ اﻹﺑﺘﺪاﺋﻲ.
• ﯾﺘﺠﻤﺪ اﻟﻤﺎء ﺗﻠﻘﺎﺋﯿﺎً ﺗﺤﺖ درﺟﺔ اﻟﺤﺮارة ) ،(0 °Cﻛﻤﺎ ﯾﻨﺼﮭﺮ اﻟﺜﻠﺞ ﺗﻠﻘﺎﺋﯿﺎً ﻓﻮق درﺟﺔ
)) (0 °Cﻋﻨﺪ ﺿﻐﻂ .(1 atm اﻟﺤﺮارة
• ﻣﺮور اﻟﺘﯿﺎر اﻟﻜﮭﺮﺑﻲ ﻣﻦ اﻟﺠﮭﺪ اﻟﻌﺎﻟﻲ اﻟﻰ اﻟﺠﮭﺪ اﻟﻤﻨﺨﻔﺾ.
• ﺗﺘﻤﺪد اﻟﻐﺎزات ﻣﻦ اﻟﻀﻐﻂ اﻟﻌﺎﻟﻲ اﻟﻰ اﻟﻀﻐﻂ اﻟﻤﻨﺨﻔﺾ .ﻛﺬﻟﻚ ﯾﺘﻤﺪد اﻟﻐﺎز ﺗﻠﻘﺎﺋﯿﺎً ﻓﻲ
اﻹﻧﺎء اﻟﻤﻔﺮغ ﻣﻦ اﻟﮭﻮاء ،واﻟﻌﻤﻠﯿﺔ اﻟﻌﻜﺴﯿﺔ ﻟﮭﺬه اﻟﻌﻤﻠﯿﺔ ﻻ ﺗﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً.
Fig. 13 : When the stopcock is opened, the gas in bulb A expands spontaneously into
evacuated bulb b to fill all the available volume. The reverse process, compression of the
gas, is nonspontaneous.
1527
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1528
Fig. 15 : The combustion of natural gas (mainly CH4) in air is a spontaneous, exothermic
reaction.
1528
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1529
Fig. 16 :
a) The rusting of this car is a spontaneous reaction, but it occurs slowly.
b) A spontaneous reaction occurs slowly if it has a high activation energy Ea.
1529
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1530
• ﺗﻜﻮن راﺳﺐ ﻣﻦ ﻛﻠﻮرﯾﺪ اﻟﻔﻀﺔ ﻋﻨﺪ إﺿﺎﻓﺔ ﻣﺤﻠﻮل ﻛﻠﻮرﯾﺪ اﻟﺼﻮدﯾﻮم NaClاﻟﻰ
ﻣﺤﻠﻮل ﻧﺘﺮات اﻟﻔﻀﺔ AgNO3
واﻟﻌﻤﻠﯿﺎت اﻟﺴﺎﺑﻘﺔ ﺗﺴﻤﻰ ﺑﺎﻟﻌﻤﻠﯿﺎت اﻟﺘﻠﻘﺎﺋﯿﺔ ،أي ﻟﮭﺎ ﻗﻮة دﻓﻊ ﺗﻠﻘﺎﺋﯿﺔ.
وﺗﻮﺿﺢ ھﺬه اﻷﻣﺜﻠﺔ وﻏﯿﺮھﺎ أن اﻟﻌﻤﻠﯿﺎت اﻟﺘﻲ ﺗﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً ﻓﻲ اﺗﺠﺎه ﻣﺤﺪد ﻻ ﯾﻤﻜﻦ أن
ﺗﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً ﻓﻲ اﻹﺗﺠﺎه اﻟﻤﻌﺎﻛﺲ.
س( ﻣﺎ اﻟﺴﺒﺐ اﻟﺬي ﯾﺠﻌﻞ ﺑﻌﺾ اﻟﻌﻤﻠﯿﺎت ﺗﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً؟
ﻣﻦ اﻹﺟﺎﺑﺎت ﻋﻠﻰ ھﺬا اﻟﺴﺆال ھﻮ اﻓﺘﺮاض أن اﻟﻌﻤﻠﯿﺎت اﻟﺘﻠﻘﺎﺋﯿﺔ ھﻲ ﺗﻠﻚ اﻟﻌﻤﻠﯿﺎت اﻟﺘﻲ
ﯾﺮاﻓﻘﮭﺎ اﻧﺨﻔﺎض ﻓﻲ ﻃﺎﻗﺔ اﻟﻨﻈﺎم ﻟﻠﻮﺻﻮل اﻟﻰ وﺿﻊ أﻗﻞ ﻓﻲ اﻟﻄﺎﻗﺔ )أﻛﺜﺮ اﺳﺘﻘﺮاراً( أي
أن ﻃﺎﻗﺔ اﻟﻨﻮاﺗﺞ أﻗﻞ ﻣﻦ ﻃﺎﻗﺔ اﻟﻤﺘﻔﺎﻋﻼت.
وھﺬا ﯾﺴﺎﻋﺪ ﻓﻲ ﺗﻮﺿﯿﺢ ﻟﻤﺎذا ﺗﻨﺘﻘﻞ اﻟﺤﺮارة ﻣﻦ اﻟﺠﺴﻢ اﻟﺴﺎﺧﻦ اﻟﻰ اﻟﺠﺴﻢ اﻟﺒﺎرد ،وﻟﻤﺎذا
ﺗﺘﺪﺣﺮج اﻷﺟﺴﺎم ﻣﻦ اﻟﻤﻮاﻗﻊ اﻟﻤﺮﺗﻔﻌﺔ اﻟﻰ اﻟﻤﻮاﻗﻊ اﻟﻤﻨﺨﻔﻀﺔ.
وﺑﻌﺾ اﻟﺘﻔﺎﻋﻼت ﯾﺮاﻓﻘﮭﺎ اﻧﺨﻔﺎض ﻓﻲ اﻟﻄﺎﻗﺔ أو اﻹﻧﺜﺎﻟﺒﻲ ﻛﻤﺎ ھﻮ اﻟﺤﺎل ﻓﻲ اﻟﺘﻔﺎﻋﻼت
اﻟﻄﺎردة ﻟﻠﺤﺮارة اﻟﺘﻲ ﺗﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً ﻋﻨﺪ درﺟﺔ ﺣﺮارة اﻟﻐﺮﻓﺔ ﻣﺜﻞ :
• اﺣﺘﺮاق اﻟﻤﯿﺜﺎن : CH4
)CH 4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(L
ο
ΔH = - 890 kJ
وﻟﻜﻦ ھﻞ اﻻﻓﺘﺮاض اﻟﺴﺎﺑﻖ ﯾﻘﻮدﻧﺎ اﻟﻰ اﻟﻘ ﻮل أن أي ﺗﻔﺎﻋ ﻞ ﺗﻠﻘ ﺎﺋﻲ ﯾﺠ ﺐ أن ﯾﻜ ﻮن ﻃ ﺎرداً
ﻟﻠﺤﺮارة؟
1530
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1531
ﻻ ،وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻓﺘﺮاض أن اﻟﻌﻤﻠﯿﺎت اﻟﺘﻠﻘﺎﺋﯿﺔ ﺗﻘﻠﻞ ﻣﻦ ﻃﺎﻗﺔ اﻟﻤﻨﻈﻮﻣﺔ ﻓﻲ ﺑﻌﺾ اﻟﺤﺎﻻت
ھﻮ اﻓﺘﺮاض ﻗﺪ ﺛﺒﺖ ﻓﺸﻠﮫ .وﺑﺎﻟﺘﺎﻟﻲ ﻓﮭﻮ اﻓﺘﺮاض ﻻ ﯾﻤﻜﻦ ﺗﻌﻤﯿﻤﮫ ﻋﻠﻰ اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ
ﻷن ھﻨﺎك ﺑﻌﺾ اﻟﺘﻐﯿﺮات اﻟﻔﯿﺰﯾﺎﺋﯿﺔ أو اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺘﻲ ﺗﻜﻮن ﻣﺎﺻﺔ ﻟﻠﺤﺮارة وﺗﺤﺪث
وﻣﻨﮭﺎ اﻟﺘﻐﯿﺮات اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺘﺎﻟﯿﺔ :
• ذوﺑﺎن ﻛﻠﻮرﯾﺪ اﻷﻣﻮﻧﯿﻮم ) (NH4Clﻓﺈﻧﮫ ﯾﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً ﻓﻲ اﻟﻤﺎء ﺑﺎﻟﺮﻏﻢ ﻣﻦ أﻧﮫ ﻣﺎص
ﻟﻠﺤﺮارة :
-
)NH 4 Cl(s) → NH 4 (aq) + Cl (aq
+ ο
ΔH = + 14.0 kJ
• ﺗﺘﻔﻜﻚ ﺑﻠﻮرة ﺧﺎﻣﺲ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ) (N2O5ﺗﻠﻘﺎﺋﯿﺎً ﻣﻊ اﻣﺘﺼﺎص ﻣﻘﺪار ﺟﯿﺪ ﻣﻦ
اﻟﺤﺮارة :
• ﺗﻔﻜﻚ أﻛﺴﯿﺪ اﻟﺰﺋﺒﻖ :ﻋﻤﻠﯿﺔ ﺗﺤﻠﻞ أﻛﺴﯿﺪ اﻟﺰﺋﺒﻖ ﺗﺤﺪث ﻓﻲ ﺗﻔﺎﻋﻞ ﻣﺎص ﻟﻠﺤﺮارة ﻏﯿﺮ
ﺗﻠﻘﺎﺋﻲ ﻋﻨﺪ درﺟﺔ ﺣﺮارة اﻟﻐﺮﻓﺔ وﻟﻜﻨﮫ ﯾﺼﺒﺢ ﺗﻠﻘﺎﺋﯿﺎً ﻋﻨﺪﻣﺎ ﺗﺮﺗﻔﻊ درﺟﺔ اﻟﺤﺮارة :
∆
HgO(s) )→ Hg(L) + 1/2O 2 (g ΔH = + 90.7 kJ
أو ﻣﻦ اﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ اﻟﻰ اﻟﺤﺎﻟﺔ اﻟﻐﺎزﯾﺔ ﺗﻜﻮن أﯾﻀﺎً ﻋﻤﻠﯿﺔ ﺗﻠﻘﺎﺋﯿﺔ :
ﺣﯿﺚ أن اﻟﺘﺠﺮﺑﺔ أوﺿﺤﺖ ﻟﻨﺎ أن اﻟﺜﻠﺞ ﯾﻨﺼﮭﺮ ﺗﻠﻘﺎﺋﯿﺎً ﻋﻨﺪ درﺟﺔ ﺣﺮارة أﻋﻠ ﻰ ﻣ ﻦ )(0 °C
ﻋﻠﻰ اﻟﺮﻏﻢ ﻣﻦ أن اﻟﻌﻤﻠﯿﺔ ﺗﻜﻮن ﻣﺎﺻﺔ ﻟﻠﺤﺮارة ،ﻛﺬﻟﻚ ﺗﺤﻮل اﻟﺴﺎﺋﻞ اﻟﻰ ﺑﺨﺎر.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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• ﻛﺬﻟﻚ اﻟﺘﺒﺮﯾﺪ اﻟﺬي ﯾﺤﺪث ﻋﻨﺪ إذاﺑﺔ ﻧﺘﺮات اﻷﻣﻮﻧﯿﻮم ) (NH4NO3ﻓﻲ اﻟﻤﺎء :
H 2O
NH 4 NO 3 (s) )→ NH +4 (aq) + NO 3- (aq ΔH ο = 25 kJ
ﻣﻦ ھﻨﺎ ﯾﻤﻜﻦ أن ﺗﻜﻮن اﻟﺘﻔﺎﻋﻼت اﻟﻄﺎردة ﻟﻠﺤﺮارة ﺗﻠﻘﺎﺋﯿﺔ ،وﻟﻜﻦ ﻟﯿﺲ ﻛﻞ ﺗﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﻲ
ﻃﺎرد ﻟﻠﺤﺮارة ،ﺣﯿﺚ ﯾﻤﻜﻦ أن ﯾﻜﻮن ﻃﺎرداً ﻟﻠﺤﺮارة وﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ ،ﻛﻤﺎ ﯾﻤﻜﻦ أن ﯾﻜﻮن
ﻣﺎﺻﺎً ﻟﻠﺤﺮارة وﺗﻠﻘﺎﺋﻲ.
س( ﻣﻢ ﺳﺒﻖ ھﻞ ﯾﻤﻜﻦ أن ﻧﺴﺘﻨﺘﺞ أن ﺗﻐﯿﺮات اﻟﻄﺎﻗﺔ )اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻤﺤﺘﻮى اﻟﺤﺮاري
)اﻹﻧﺜﺎﻟﺒﻲ( ﻟﻮﺣﺪھﺎ ﻛﺎﻓﯿﺔ ﻟﻠﺘﻨﺒﺆ ﺑﺘﻠﻘﺎﺋﯿﺔ ﻋﻤﻠﯿﺔ ﻣﻦ ﻋﺪﻣﮭﺎ وﻣﺎذا ﯾﺠﺐ ﺣﯿﺎل ذﻟﻚ.
ج( ﻻ ﯾﻤﻜﻦ اﻻﻋﺘﻤﺎد ﻓﻘﻂ ﻋﻠﻰ ﺗﻐﯿﺮات اﻟﻄﺎﻗﺔ ﻓﻲ اﻟﺘﻨﺒﺆ ﺑﺘﻠﻘﺎﺋﯿﺔ ﻋﻤﻠﯿﺔ ﻣﻦ ﻋﺪﻣﮭﺎ ﻛﻤﺎ
اﺗﻀﺢ ﻓﻲ اﻷﻣﺜﻠﺔ اﻟﺴﺎﺑﻘﺔ ،وﯾﺠﺐ ﺣﯿﻨﺌﺬ اﻟﺒﺤﺚ ﻋﻦ ﺧﺎﺻﯿﺔ ﺛﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺔ أﺧﺮى
ﺑﺎﻹﺿﺎﻓﺔ اﻟﻰ اﻟﻄﺎﻗﺔ ﻟﻠﻤﺴﺎﻋﺪة ﻓﻲ اﻟﺘﻨﺒﺆ ﻓﻲ إﻣﻜﺎﻧﯿﺔ ﺣﺪوث اﻟﺘﻔﺎﻋﻼت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ .وﺳﻤﯿﺖ
ھﺬه اﻟﺨﺎﺻﯿﺔ ﺑﺎﻷﻧﺘﺮوﺑﻲ entropyوﯾﺮﻣﺰ ﻟﮫ ﺑﺎﻟﺮﻣﺰ )(S
س( ھﻞ ﯾﺠﺐ أن ﺗﺤﺪث اﻟﺘﻔﺎﻋﻼت اﻟﺘﻠﻘﺎﺋﯿﺔ ﺑﺴﺮﻋﺔ ﻣﻠﺤﻮﻇﺔ؟
ج( ﻟﯿﺲ ﺷﺮﻃﺎً ﻟﻠﺘﻔﺎﻋﻼت اﻟﺘﻠﻘﺎﺋﯿﺔ أن ﺗﻜﻮن ﺳﺮﯾﻌﺔ ،ﻓﻘﺪ ﺗﻜﻮن ﺳﺮﯾﻌﺔ ﻛﻤﺎ ﻓﻲ ﺗﻔﺎﻋﻞ
اﻷﺣﻤﺎض ﻣﻊ اﻟﻘﻮاﻋﺪ ،أو ﺑﻄﯿﺌﺔ ﺟﺪاً ﻛﻤﺎ ﻓﻲ ﺣﺎﻟﺔ ﺻﺪأ اﻟﺤﺪﯾﺪ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﻷﻧﱰﻭﺑﻲ ENTROPY
ﺗﻌﺮﯾﻔﮫ :اﻷﻧﺘﺮوﺑﻲ واﻟﺬي ﯾﺮﻣﺰ ﻟﮫ ﺑﺎﻟﺮﻣﺰ ) (Sھﻮ :ﻣﻘﯿﺎس ﻣﺒﺎﺷﺮ ﻟﺨﺎﺻﯿﺔ ﻋﺪم
اﻻﻧﺘﻈﺎم )درﺟﺔ اﻟﻔﻮﺿﻰ -اﻟﻌﺸﻮاﺋﯿﺔ( ﺑﯿﻦ اﻟﺠﺴﯿﻤﺎت )أﯾﻮﻧﺎت ،ذرات أو ﺟﺰﯾﺌﺎت(
اﻟﻤﻜﻮﻧﺔ ﻟﻠﻨﻈﺎم .أو ﺑﺎﺧﺘﺼﺎر :اﻷﻧﺘﺮوﺑﻲ ھﻮ ﻣﻘﯿﺎس ﻟﻠﻌﺸﻮاﺋﯿﺔ )ﻣﻘﯿﺎس ﻟﻌﺪم اﻹﻧﺘﻈﺎم(.
Fig. 17 : As particles leave a crystal to go into solution, they become more disordred. This
increase in disorder favors the dissolution of the crystal.
Δ 1
)N 2 O 5 (s → 2NO 2 (g) + )O 2 (g
ο
ΔH = 109.6 kJ/mol
2
وھﺬه اﻟﺬاﺋﺒﯿﺔ ﺑﺎﻟﺮﻏﻢ ﻣﻦ أﻧﮫ ﯾﺼﺎﺣﺒﮭﺎ زﯾﺎدة ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ) (ΔH = + 14 kJإﻻ أن اﻟﺬوﺑﺎن
ﺗﻠﻘﺎﺋﻲ ،وﯾﻤﻜﻦ ﺗﻔﺴﯿﺮ ذﻟﻚ ﺑﺄن أﯾﻮﻧﺎت اﻟﻜﻠﻮر واﻷﻣﻮﻧﯿﻮم ﻓﻲ اﻟﻤﺤﻠﻮل أﻗﻞ اﻧﺘﻈﺎﻣ ﺎً ﻣﻨﮭ ﺎ ﻓ ﻲ
ﺑﻠﻮرة ﻛﻠﻮرﯾﺪ اﻷﻣﻮﻧﯿﻮم.
Δ Δ
H 2 O(s)
→ H2 O(L)
)→ H 2O(g
ﺟﺰﯾﺌﺎت اﻟﻤﺎء ﻓﻲ اﻟﺤﺎﻟﺔ اﻟﺒﺨﺎرﯾﺔ أﻗﻞ اﻧﺘﻈﺎﻣﺎً ﻣﻦ ﺟﺰﯾﺌﺎت اﻟﻤﺎء ﻓﻲ اﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ،
وﺟﺰﯾﺌﺎت اﻟﻤﺎء اﻟﻤﺘﺠﻤﺪة ﻓﻲ اﻟﺤﺎﻟﺔ اﻟﺼﻠﺒﺔ ،وﺑﺸﻜﻞ ﻋﺎم ﻓﺈن اﻟﺤﺎﻟﺔ اﻟﻐﺎزﯾﺔ أﻗﻞ اﻧﺘﻈﺎﻣﺎً ﻣﻦ
اﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ ،واﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ أﻗﻞ اﻧﺘﻈﺎﻣﺎً ﻣﻦ اﻟﺤﺎﻟﺔ اﻟﺼﻠﺒﺔ )ﻛﻤﺎ ﯾﺘﻀﺢ ﻣﻦ اﻟﺸﻜﻞ .(١٨
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺷﻜﻞ ) : (١٨زﯾﺎدة اﻷﻧﺘﺮوﺑﻲ ) ﺧﺎﺻﯿﺔ ﻋﺪم اﻹﻧﺘﻈﺎم( ﻋﻨﺪ اﻟﺘﺤﻮل ﻣ ﻦ اﻟﺤﺎﻟ ﺔ اﻟ ﺼﻠﺒﺔ اﻟ ﻰ اﻟﺤﺎﻟ ﺔ اﻟ ﺴﺎﺋﻠﺔ ﺛ ﻢ اﻟ ﻰ
اﻟﺤﺎﻟﺔ اﻟﻐﺎزﯾﺔ.
وﻣﻦ اﻟﺠﺪول ) (٦ﯾﻼﺣﻆ أن ﻗﯿﻢ اﻷﻧﺘﺮوﺑﻲ ﻓﻲ اﻟﺤﺎﻟﺔ اﻟﻐﺎزﯾﺔ ﻟﺠﻤﯿﻊ ھﺬه اﻟﻤﻮاد أﻛﺒﺮ ﻣﻨﮭﺎ
ﻟﻠﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ أو اﻟﺤﺎﻟﺔ اﻟﺼﻠﺒﺔ :
) : S(sأﻧﺘﺮوﺑ ﻲ اﻟﻤ ﺎدة اﻟ ﺼﻠﺒﺔ : S(L) ،أﻧﺘﺮوﺑ ﻲ اﻟﻤ ﺎدة اﻟ ﺴﺎﺋﻠﺔ : S(g) ،أﻧﺘﺮوﺑ ﻲ اﻟﻤ ﺎدة
اﻟﻐﺎزﯾﺔ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻻﺗﺠﺎه اﻟﻤﻔﻀﻞ ﻟﻠﺘﻐﯿﺮ ھﻮ اﻹﺗﺠﺎه اﻟﺬي ﺗﺰداد ﻓﯿﮫ درﺟﺔ اﻟﻔﻮﺿﻰ أو ﻋﺪم
اﻹﻧﺘﻈﺎم.
واﻟﺸﻜﻞ ) (٢٠ﯾﻮﺿﺢ ﺑﻌﺾ اﻟﻌﻤﻠﯿ ﺎت اﻟﺘ ﻲ أدت ﻟﺰﯾ ﺎدة اﻷﻧﺘﺮوﺑ ﻲ ﺣﯿ ﺚ أﻧ ﮫ ﻓ ﻲ ﻛ ﻞ ﺣﺎﻟ ﺔ
ﺗﺘﻐﯿﺮ اﻟﻤﻨﻈﻮﻣﺔ ﻣﻦ ﺣﺎﻟﺔ أﻛﺜﺮ ﺗﻨﻈﯿﻤﺎً اﻟﻰ أﺧﺮى أﻗﻞ ﺗﻨﻈﯿﻤﺎً .وﻣﻦ اﻟﻮاﺿﺢ أن ﻛ ﻼ ﻋﻤﻠﯿﺘ ﻲ
اﻹﻧ ﺼﮭﺎر واﻟﺘﺒﺨ ﺮ ﺗﻘ ﻮدان ﻟﺘﻐﯿ ﺮ ﻓ ﻲ اﻷﻧﺘﺮوﺑ ﻲ أﻛﺒ ﺮ ﻣ ﻦ اﻟ ﺼﻔﺮ ) . ( ∆S > 0ﻋﻨ ﺪﻣﺎ
ﺗ ﺬوب اﻟﻤ ﺎدة اﻟ ﺼﻠﺒﺔ اﻷﯾﻮﻧﯿ ﺔ ﻓ ﻲ اﻟﻤ ﺎء ﻓ ﺈن اﻟﺒﻨ ﺎء اﻟﺒﻠ ﻮري ﻋ ﺎﻟﻲ اﻟﺘﻨﻈ ﯿﻢ ﻟﻠﻤ ﺎدة اﻟ ﺼﻠﺒﺔ
واﻟﺒﻨﯿ ﺔ اﻟﻤﻨﺘﻈﻤ ﺔ ﻟﻠﻤ ﺎء ﯾﺘﺤﻄﻤ ﺎن .ﻛﻨﺘﯿﺠ ﺔ ﻟ ﺬﻟﻚ ﻓ ﺈن اﻟﻤﺤﻠ ﻮل ﯾﻤﺘﻠ ﻚ ﻋ ﺪم ﺗﻨﻈ ﯿﻢ أﻛﺒ ﺮ ﻣ ﻦ
اﻟﻤﺬاب اﻟﻨﻘﻲ أو اﻟﻤﺬﯾﺐ اﻟﻨﻘﻲ .ﻛﺬﻟﻚ ﻓﺈن اﻟﺘﺴﺨﯿﻦ ﯾﺰﯾﺪ ﻣﻦ أﻧﺘﺮوﺑ ﻲ اﻟﻤﻨﻈﻮﻣ ﺔ ﺣﯿ ﺚ ﺗﺰﯾ ﺪ
ﻃﺎﻗﺔ اﻟﺤﺮﻛﺎت اﻟﺠﺰﯾﺌﯿﺔ اﻟﻤﺨﺘﻠﻔﺔ ﺑﺰﯾﺎدة درﺟﺔ اﻟﺤﺮارة .وھﺬا ﯾﻌﻨ ﻲ أن اﻟﺰﯾ ﺎدة ﻓ ﻲ اﻟﺘﺒﻌﺜ ﺮ
ﻋﻠﻰ اﻟﻤﺴﺘﻮى اﻟﺠﺰﯾﺌﻲ ﺗﺰﯾﺪ ﻣﻦ اﻷﻧﺘﺮوﺑﻲ.
س( ھﻞ اﻷﻧﺘﺮوﺑﻲ داﻟﺔ ﻟﻠﺤﺎﻟﺔ؟
ج( ﻧﻌﻢ ،اﻷﻧﺘﺮوﺑﻲ داﻟﺔ ﻟﻠﺤﺎﻟﺔ )أي ﯾﻌﺘﻤﺪ ﻋﻠﻰ اﻟﺤﺎﻟﺔ اﻹﺑﺘﺪاﺋﯿﺔ واﻟﺤﺎﻟﺔ اﻟﻨﮭﺎﺋﯿﺔ وﻻ ﯾﻌﺘﻤﺪ
ﻋﻠﻰ اﻟﻤﺴﺎر اﻟﺬي ﯾﺴﻠﻜﮫ اﻟﻨﻈﺎم( ،ﻟﺬا ﻓﺈﻧﮫ ﯾﻘﺎس اﻟﺘﻐﯿﺮ ﻓﯿﮫ ) (ΔSﻷي ﻋﻤﻠﯿﺔ ﯾﺘﻢ ﻓﯿﮭﺎ ﺗﻐﯿﺮ
اﻟﻨﻈﺎم ﻣﻦ ﺣﺎﻟﺘﮫ اﻹﺑﺘﺪاﺋﯿﺔ اﻟﻰ ﺣﺎﻟﺘﮫ اﻟﻨﮭﺎﺋﯿﺔ :
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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∆S = Sf - Si
ﺑﺸﺮط أن ﺗﺘﻢ ﻋﻤﻠﯿﺔ اﻣﺘﺼﺎص اﻟﺤﺮارة ﺑﺒﻂء ﻟﺘﺤﺎﺷﻲ أي ﻓﺮق ﻓﻲ اﻟﻀﻐﻂ أو درﺟﺔ
اﻟﺤﺮارة ﺑﯿﻦ اﻟﻨﻈﺎم وﻣﺤﯿﻄﮫ.
وﺣﺪات اﻷﻧﺘﺮوﺑﻲ :
q
ﻓﺈن اﻷﻧﺘﺮوﺑﻲ ﯾﻘﺎس ﺑﻮﺣﺪة ) (J/Kوﻟﻤﻮل واﺣﺪ ﻣﻦ اﻟﻤﺎدة ﺑﻮﺣﺪات = ΔS ﻣﻦ اﻟﻤﻌﺎدﻟﺔ
T
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﻠﺤﻮﻇﺔ
اﻟﺘﻐﯿﺮ ﻓﻲ أﻧﺘﺮوﺑﻲ اﻟﻨﻈﺎم دون اﻟﻤﺤﯿﻂ ﯾﻤﻜﻦ أن ﯾﻜﻮن ﺳﺎﻟﺒﺎً أو ﻣﻮﺟﺒﺎً ﺣﺴﺐ ﻧﻮع اﻟﺘﻔﺎﻋﻞ.
س( ﻣﻢ ﺗﻘﺪم ھﻞ ﻣﻌﺮﻓﺔ ﺗﻐﯿﺮ اﻷﻧﺘﺮوﺑﻲ )ﻣﻮﺟﺒﺎً أو ﺳﺎﻟﺒﺎً( ﻟﻨﻈﺎم ﻣﺎ ﯾﺘﯿﺢ اﻟﺘﻨﺒﺆ ﺑﺤﺘﻤﯿﺔ
ﺗﻠﻘﺎﺋﯿﺔ ھﺬا اﻟﺘﻐﯿﺮ؟
ج( ﻻ ،ﻻ ﯾﺘﯿﺢ اﻷﻧﺘﺮوﺑﻲ ﻟﻨﻈﺎم ﻣﺎ ﺑﺤﺘﻤﯿﺔ ﺗﻠﻘﺎﺋﯿﺔ اﻟﺘﻔﺎﻋﻞ.
وﺑﺎﻟﺘﺎﻟﻲ ﻣﺎدام اﻹﻧﺨﻔﺎض ﻓﻲ اﻟﻄﺎﻗﺔ ،وﺗﻐﯿﺮ اﻷﻧﺘﺮوﺑﻲ ﻻ ﯾﺤﺪدان ﺑﺸﻜﻞ ﻣﺆﻛﺪ ﺗﻠﻘﺎﺋﯿﺔ
ﻋﻤﻠﯿﺔ ﻣﺎ ﻓﺈﻧﮫ ﻻ ﺑﺪ ﻣﻦ ﺧﺎﺻﯿﺔ ﺛﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺔ أﺧﺮى ﺗﺠﻤﻊ ﺑﯿﻦ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ
واﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ وھﺬه اﻟﺨﺎﺻﯿﺔ ھﻲ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة وﯾﺮﻣﺰ ﻟﮭﺎ ﺑﺎﻟﺮﻣﺰ
) . ( ∆G
ﺻﯿﻐﺔ ﻛﻠﻔﻦ " :ﻣﻦ اﻟﻤﺴﺘﺤﯿﻞ اﺳﺘﻌﻤﺎل اﻟﻌﻤﻠﯿﺔ اﻟﺪاﺋﺮﯾﺔ ﻟﻨﻘﻞ اﻟﺤﺮارة ﻣﻦ ﻣﺴﺘﻮدع ﺣﺮاري
وﺗﺤﻮﯾﻞ ھﺬه اﻟﺤﺮارة اﻟﻰ ﺷﻐﻞ وﺑﺪون ﻧﻘﻞ ﻛﻤﯿﺔ ﻣﻌﯿﻨﺔ ﻣﻦ اﻟﺤﺮارة ﻣﻦ ﺟﺴﻢ ذي درﺟﺔ
ﺣﺮارﯾﺔ ﻋﺎﻟﯿﺔ اﻟﻰ ﺟﺴﻢ ذي درﺟﺔ ﺣﺮارﯾﺔ ﻣﻨﺨﻔﻀﺔ وﺑﻨﻔﺲ اﻟﻮﻗﺖ".
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺻﯿﻐﺔ ﻛﻼﺳﯿﻮس " :ﻣﻦ اﻟﻤﺴﺘﺤﯿﻞ اﺳﺘﻌﻤﺎل اﻟﻌﻤﻠﯿﺎت اﻟﺪاﺋﺮﯾﺔ ﻟﻨﻘﻞ اﻟﺤﺮارة ﻣﻦ ﺟﺴﻢ ذي
درﺟﺔ ﺣﺮارﯾﺔ ﻣﻨﺨﻔﻀﺔ اﻟﻰ ﺟﺴﻢ آﺧﺮ درﺟﺔ ﺣﺮارﺗﮫ ﻋﺎﻟﯿﺔ ﺑﺪون ﺗﺤﻮﯾﻞ ﻛﻤﯿﺔ ﻣﻌﯿﻨﺔ ﻣﻦ
اﻟﺸﻐﻞ اﻟﻰ ﺣﺮارة.
وﻣﺜﻞ ھﺬه اﻟﺼﯿﺎﻏﺎت ﻟﻠﻘﺎﻧﻮن اﻟﺜﺎﻧﻲ ﻻ ﯾﻤﻜﻦ ﺗﻄﺒﯿﻘﮭﺎ ﻣﺒﺎﺷﺮة ﻓﻲ اﻹﺟﺎﺑﺔ ﻋﻠﻰ اﻟﺴﺆال ﻓﯿﻤﺎ
إذا ﻛﺎن ﻣﻦ اﻟﻤﻤﻜﻦ ﺣﺪوث ﺗﻔﺎﻋﻞ ﻛﯿﻤﯿﺎﺋﻲ ﻣﻌﯿﻦ أو ﻋﻤﻠﯿﺔ ﻓﯿﺰﯾﺎﺋﯿﺔ ﻣﻌﯿﻨﺔ ﺗﻠﻘﺎﺋﯿﺎً أم ﻻ .ﻟﺬﻟﻚ
ﯾﻠﺰم ﺗﻘﺪﯾﻢ داﻟﺔ ﺛﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺔ ﺟﺪﯾﺪة ﻟﮭﺬا اﻟﻐﺮض وھﺬه اﻟﺪاﻟﺔ ھﻲ اﻷﻧﺘﺮوﺑﻲ ). (S
ً
ﻧﺺ ﺍﻟﻘﺎﻧﻮﻥ ﺍﻟﺜﺎﻧﻲ ﰲ ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﻭﻓﻘﺎ ﻟﺪﺍﻟﺔ ﺍﻷﻧﱰﻭﺑﻲ :
ﯾﺮﺗﺒﻂ اﻟﻘﺎﻧﻮن اﻟﺜﺎﻧﻲ ﻟﻠﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ ﺑﻤﻔﮭﻮﻣﻨﺎ ﻋﻦ اﻟﺘﻐﯿﺮات ﻓﻲ اﻷﻧﺘﺮوﺑﻲ وﯾﻘﻮل إن
اﻟﻜﻤﯿﺔ اﻟﻜﻠﯿﺔ ﻻﻧﺘﺮوﺑﻲ اﻟﻜﻮن ﻓﻲ ازدﯾﺎد .وﯾﻤﻜﻨﻨﺎ ﺗﻌﺮﯾﻒ اﻟﻜﻮن ﺑﺄﻧﮫ ﻣﺆﻟﻒ ﻣﻦ ﻧﻈﺎم
ﻛﯿﻤﯿﺎﺋﻲ ﻣﻌﯿﻦ ﺗﺤﺖ اﻹﺧﺘﺒﺎر واﻟﺠﺰء اﻟﺒﺎﻗﻲ ﻣﻦ اﻟﻤﺤﯿﻂ اﻟﻜﻮﻧﻲ .وﯾﻨﺺ اﻟﻘﺎﻧﻮن اﻟﺜﺎﻧﻲ وﻓﻘﺎً
ﻟﻸﻧﺘﺮوﺑﻲ ﻋﻠﻰ :
"ﻛﻞ ﺗﻐﯿﺮ ﺗﻠﻘﺎﺋﻲ ﻻ ﺑﺪ وأن ﺗﺮاﻓﻘﮫ زﯾﺎدة ﻓﻲ اﻷﻧﺘﺮوﺑﻲ وﺗﺒﻘﻰ ﺛﺎﺑﺘﺔ ﻓﻲ ﺣﺎﻟﺔ اﻟﺘﻮازن".
أو ﺑﻌﺒﺎرة أﺧﺮى :
"ﻋﻨﺪﻣﺎ ﯾﺘﻢ أي ﺗﻐﯿﺮ ﺗﻠﻘﺎﺋﻲ ﻓﻲ ﻧﻈﺎم ﻣﻌﯿﻦ ﺗﻜﻮن ھﻨﺎك زﯾﺎدة ﻓﻲ أﻧﺘﺮوﺑﻲ اﻟﻜﻮن".
ﺑﻤﻌﻨﻰ أن اﻟﺘﻐﯿﺮ اﻟﻜﻠﻲ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ) ( ∆Stھﻮ اﻟﺬي ﯾﺤﺪد ﻛﻮن اﻟﻌﻤﻠﯿﺔ ﺗﻠﻘﺎﺋﯿﺔ أم ﻻ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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Fig. 22 :
a) When an exothermic reaction occurs in the system ( ∆H < 0 ) , the surroundings gain heat
and their entropy increases ( ∆Ssurr > 0 ) .
b) When an endothermic reaction occurs in the system ( ΔH > 0 ) , the surroundings lose
) heat and their entropy decreases ( ΔSsurr < 0
ﺍﻟﻄﺎﻗﺔ ﻭﺍﻷﻧﱰﻭﺑﻲ
اﻟﻄﺎﻗﺔ ﻻ ﺗﻔﻨﻰ وﻻ ﺗﺴﺘﺤﺪث أي ﺗﺒﻘﻰ ﺛﺎﺑﺘﺔ ﺣﺴﺐ ﻗﺎﻧﻮن ﺣﻔﻆ اﻟﻄﺎﻗﺔ ﺧﻼل اﻟﺘﻐﯿﺮات
اﻟﻜﯿﻤﯿﺎﺋﯿﺔ أو اﻟﻔﯿﺰﯾﺎﺋﯿﺔ ،ﺑﯿﻨﻤﺎ ﺗﺼﺎﺣﺐ ھﺬه اﻟﺘﻐﯿﺮات زﯾﺎدة ﻓﻲ ﻗﯿﻤﺔ اﻷﻧﺘﺮوﺑﻲ.
ً
ﺍﻟﻘﺎﻧﻮﻥ ﺍﻟﺜﺎﻧﻲ ﺭﻳﺎﺿﻴﺎ :
وﺣﺴﺐ اﻟﻘﺎﻧﻮن اﻟﺜﺎﻧﻲ ﻓﺈن اﻟﺘﻐﯿﺮ اﻟﻜﻠﻲ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ΔStﻛﻤﯿﺔ ﻣﻮﺟﺒﺔ ﻷي ﻋﻤﻠﯿﺔ ﺗﻠﻘﺎﺋﯿﺔ :
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻧﻔﺮض أن ﻟﺪﯾﻨﺎ ﻧﻈﺎﻣﺎً ﺛﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺎً ﻻ ﯾﺤﺪث ﻓﯿﮫ ﺗﻐﯿﺮ ﻛﯿﻤﯿﺎﺋﻲ أو ﻓﯿﺰﯾﺎﺋﻲ )ﺑﻤﺎ ﻓﻲ ذﻟﻚ
اﻟﻀﻐﻂ أو اﻟﻤﺰج( وﺗﻨﺴﺎب إﻟﯿﮫ ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة ﻣﻘﺪارھﺎ ) (qﻓﺈن أﻧﺘﺮوﺑﻲ اﻟﻨﻈﺎم ﺳﻮف
ﯾﺰداد ﺑﻤﻘﺪار :
q
= ΔSs
TS
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﯾﻜﻮن اﻟﺘﻐﯿﺮ اﻟﻜﻠﻲ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ) ( ∆Stھﻮ ﻣﺠﻤﻮع ﺣﺎﺻﻞ ﺟﻤﻊ اﻟﺘﻐﯿﺮ ﻓﻲ أﻧﺘﺮوﺑﻲ
اﻟﻨﻈﺎم أو اﻟﺘﻐﯿﺮ ﻓﻲ أﻧﺘﺮوﺑﻲ اﻟﻤﺤﯿﻂ :
q q
ΔSt = +-
s Tr
T
ﻓﺈن ) ( ∆Stﯾﻜﻮن ﻣﻮﺟﺒﺎً ) ،(+أي أن اﻟﺤﺮارة ﺗﻨﺴﺎب ﻣﻦ اﻟﻤﻨﻄﻘﺔ اﻟﺴﺎﺧﻨﺔ اﻟﻰ اﻟﺒﺎردة
)أي ﻣﻦ اﻟﻤﺤﯿﻂ اﻟﻰ اﻟﻨﻈﺎم(.
• أﻣﺎ إذا ﻛﺎﻧﺖ ) (Tsأﻛﺒﺮ ﻣﻦ ): (Tr
Ts > Tr
ﻓﺈن اﻟﺘﻐﯿﺮ اﻟﻜﻠﻲ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ) ( ΔStﯾﻜﻮن ﺳﺎﻟﺒﺎً ،وھﺬا ﯾﻌﻨﻲ أن اﻟﺤﺮارة ﻻ ﯾﻤﻜﻦ أن
ﺗﻨﺴﺎب ﻣﻦ اﻟﻤﻨﻄﻘﺔ اﻟﺒﺎردة اﻟﻰ اﻟﺴﺎﺧﻨﺔ ﺑﺸﻜﻞ ﺗﻠﻘﺎﺋﻲ.
وﯾﺴﺘﻨﺘﺞ ﻣﻤﺎ ﺳﺒﻖ أن :
• ﻗﯿﻤﺔ اﻷﻧﺘﺮوﺑﻲ اﻟﻤﻮﺟﺒﺔ ﺗﻌﻨﻲ أن اﻟﻌﺸﻮاﺋﯿﺔ زادت وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻌﻤﻠﯿﺔ ﺗﻠﻘﺎﺋﯿﺔ.
• ﻗﯿﻤﺔ اﻷﻧﺘﺮوﺑﻲ اﻟﺴﺎﻟﺒﺔ ﺗﻌﻨﻲ أن اﻹﻧﺘﻈﺎم ﻗﺪ زاد وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن اﻟﻌﻤﻠﯿﺔ ﻏﯿﺮ ﺗﻠﻘﺎﺋﯿﺔ.
q q
• ﻣﻦ اﻟﻌﻼﻗﺔ : ΔSt = T + - T
s r
ﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﻤﻔﻘﻮدة ﻣﻦ اﻟﻨﻈﺎم ) (qSﺗﺴﺎوي ﻛﻤﯿﺔ اﻟﺤﺮارة اﻟﻤﻜﺘﺴﺒﺔ ﺑﻮاﺳﻄﺔ اﻟﻤﺤﯿﻂ
) (qrوﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن درﺟﺔ اﻟﺤﺮارة اﻟﻤﻄﻠﻘﺔ ﻟﻠﻤﺤﯿﻂ واﻟﻨﻈﺎم ھﻤﺎ ﻓﻘﻂ اﻟﻠﺬان ﯾﺘﺤﻜﻤﺎن ﻓﻲ
ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ اﻟﻜﻠﻲ ﻟﻸﻧﺘﺮوﺑﻲ ) . ( ΔSt
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺗﻐﯿﺮ اﻷﻧﺘﺮوﺑﻲ ﺑﺎﻹﺿﺎﻓﺔ اﻟﻰ ﻣﺮاﻓﻘﺘﮫ اﻟﺘﻐﯿﺮ ﻓﻲ درﺟﺔ ﺣﺮارة اﻟﻨﻈﺎم ،ﻓﺈﻧﮫ ﯾﺮاﻓﻖ أﯾﻀﺎً
اﻟﺘﺤﻮﻻت اﻟﻔﯿﺰﯾﺎﺋﯿﺔ ﻣﺜﻞ اﻹﻧﺼﮭﺎر أو اﻟﺘﺒﺨﺮ أو اﻟﺘﺤﻮل ﻣﻦ ﺷﻜﻞ ﺑﻠﻮري اﻟﻰ آﺧﺮ.
وﯾﻜﻮن اﻷﻧﺘﺮوﺑﻲ ﻓﻲ ھﺬه اﻟﺘﺤﻮﻻت اﻟﻔﯿﺰﯾﺎﺋﯿﺔ :
∆S = Sf - Si
ﻋﻨﺪ ذوﺑﺎن ﻣﺎدة ﺻﻠﺒﺔ أو ﺗﺒﺨﺮ ﺳﺎﺋﻞ ﻓﺈن درﺟﺔ ﺣﺮارة اﻟﻨﻈﺎم ﺗﺒﻘﻰ ﺛﺎﺑﺘﺔ وﻟﻜﻦ اﻷﻧﺘﺮوﺑﻲ
ﯾﺰداد )ﻋﻠﻞ( ﻷﻧﮫ أﺻﺒﺢ ﻟﺪى اﻟﺠﺴﯿﻤﺎت اﻟﻤﻜﻮﻧﺔ ﻟﻠﻨﻈﺎم ﺣﺮﯾﺔ أﻛﺒﺮ ﻟﻜﻲ ﺗﺘﺤﺮك.
إذا ﺣﺪث ﺗﻐﯿﺮ ﻓﯿﺰﯾﺎﺋﻲ ﻧﺘﯿﺠﺔ اﻣﺘﺼﺎص أو اﻧﻄﻼق ﻣﻘﺪار ) ( ∆Hﻣﻦ اﻟﺤﺮارة ﻣﻦ ﻗﺒﻞ
ﻛﻤﯿﺔ ﻣﻌﯿﻨﺔ ﻣﻦ ﻣﺎدة ﻓﺈن اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ﻟﻤﺜﻞ ھﺬه اﻟﻌﻤﻠﯿﺎت :
q
= ΔS
T
:q P
= ∆H وﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ﻓﺈن :
qP ΔH
= ΔS =
T T
أي أن اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ﯾﻌﻄﻲ ﻧﺘﯿﺠﺔ ﻟﺤﺎﺻﻞ ﻗﺴﻤﺔ اﻟﺤﺮارة اﻟﻼزﻣﺔ ﻹﻧﺠﺎز ھﺬا
اﻟﺘﺤﻮل ﻋﻠﻰ درﺟﺔ اﻟﺤﺮارة اﻟﺘﻲ ﺣﺪث ﻋﻨﺪھﺎ اﻟﺘﺤﻮل )درﺟﺔ اﻟﻐﻠﯿﺎن أو اﻹﻧﺼﮭﺎر(.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﻠﺤﻮﻇﺔ
اﻟﻤﻌﺎدﻟﺔ:
ΔH
= ΔS
T
ﺗﻜﻮن ﺳﺎرﯾﺔ اﻟﻤﻔﻌﻮل ﻓﻘﻂ إذا ﻛﺎﻧﺖ ﺣﺎﻟﺔ اﻟﺘﻮازن ﻣﺴﺘﻤﺮة ﺧﻼل اﻟﺘﺤﻮل )ﻣﺜﻞ اﻹﻧﺼﮭﺎر،
اﻟﻐﻠﯿﺎن ،اﻟﺘﺴﺎﻣﻲ ،اﻟﺘﺒﺨﺮ( ،أو أن اﻟﺘﻮازن ﻣﻮﺟﻮد ﺑﯿﻦ اﻟﺤﺎﻟﺘﯿﻦ.
ﺣﯿﺚ أﻧﮫ ﻋﻨﺪ اﻟﺘﻮازن ﻓﺈن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ ﻃﺎﻗﺔ ﺟﺒﺲ اﻟﺤﺮة ﺗﺴﺎوي ﺻﻔﺮاً ) ( ∆G = 0
وﻣﻦ اﻟﻌﻼﻗﺔ :
ΔG = ΔH - TΔS
0 = ΔH - TΔS
TΔS = ΔH
ΔH
= ⇒ ΔS
T
ﻣﺜﺎﻝ )(٣٥
ﻋﻨﺪ ﺿﻐﻂ ﺟﻮي واﺣﺪ ،ودرﺟﺔ ﻏﻠﯿﺎن اﻟﻤﺎء اﻟﻌﺎدﯾﺔ )(100 ºC
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ΔH
= ΔS
T
40617.1
= ΔS = 108.9 J/K.mol
100 + 273
ﻣﺜﺎﻝ )(٣٦
اﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ اﻟﻤﺮاﻓﻖ ﻟﺘﺒﺨﺮ ﻣﻮل واﺣﺪ ﻣﻦ ﻏﺎز ) (Arإذا ﻋﻠﻤﺖ أن اﻟﺘﻐﯿﺮ
ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ) ( ∆Hﻟﻠﺘﺒﺨﯿﺮ ﯾﺴﺎوي ) (6519 J/molﻋﻨﺪ درﺟﺔ ﻏﻠﯿﺎن اﻵرﺟﻮن
اﻹﻋﺘﯿﺎدﯾﺔ ) (- 185.7 ºCوھﻞ ھﺬا اﻟﺘﻐﯿﺮ زﯾﺎدة ﻓﻲ اﻷﻧﺘﺮوﺑﻲ أو ﻧﻘﺺ؟
ﺍﳊﻞ
ﻣﺜﺎﻝ )(٣٧
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ΔH
= ΔS
T
ΔH
=T
ΔS
3
16.2 × 10 J/mol
=T
88.5 J/mol K
T = 183.05 K
ο
T = - 89.95 C
أي أن CO2ﯾﺼﺒﺢ ﻏﺎزاً ﻋﻨﺪ درﺟﺔ ﺣﺮارة ﺗﺤﺖ اﻟﺼﻔﺮ )(- 89.95 ºC
ﻣﺜﺎﻝ )(٣٨
إذا ﻛﺎﻧﺖ ﺣﺮارة اﻧﺼﮭﺎر اﻟﺒﻨﺰﯾﻦ ﺗﺴﺎوي ) ، (11 kJ/molاﺣﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ
) ( ∆Sﻋﻨﺪﻣﺎ ﯾﺘﺤﻮل اﻟﺒﻨﺰﯾﻦ ﻣﻦ اﻟﺤﺎﻟﺔ اﻟﺼﻠﺒﺔ اﻟﻰ اﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ ،ﻋﻠﻤﺎً ﺑﺄن درﺟﺔ اﻧﺼﮭﺎر
اﻟﺒﻨﺰﯾﻦ ).(5.5 ºC
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٣٩
ﺍﳊﻞ
ﺍﻷﻧﱰﻭﺑﻲ ﺍﻟﻘﻴﺎﺳﻲ
Standard Entropy
اﻟﻨﺺ :
"اﻷﻧﺘﺮوﺑﻲ ﻷي ﻣﺎدة ﻧﻘﯿﺔ ﻣﺘﺒﻠﻮرة ﻋﻨﺪ درﺟﺔ اﻟﺼﻔﺮ اﻟﻤﻄﻠﻖ ) (0 Kﯾﺴﺎوي ﺻﻔﺮاً" وھﺬا
اﻓﺘﺮاض ﻣﺒﻨﻲ ﻋﻠﻰ أن اﻟﺠﺰﯾﺌﺎت ﺗﻜﻮن ﻣﻨﺘﻈﻤﺔ ﺗﻤﺎﻣﺎً ﻋﻨﺪ درﺟﺔ اﻟﺼﻔﺮ اﻟﻤﻄﻠﻖ وﻟﯿﺲ
ﻟﺪﯾﮭﺎ أي ﺣﺮﻛﺔ ﺣﺮارﯾﺔ.
وﯾﻤﻜﻦ أن ﯾﺼﺎغ اﻟﻘﺎﻧﻮن اﻟﺜﺎﻟﺚ ﺑﺄﻧﮫ " :ﻻ ﯾﻤﻜﻦ ﺧﻔﺾ درﺟﺔ اﻟﺤﺮارة ﻷي ﻧﻈﺎم اﻟﻰ
درﺟﺔ اﻟﺼﻔﺮ اﻟﻤﻄﻠﻖ ﻓﻲ ﻋﺪد ﻣﺤﺪود ﻣﻦ اﻟﺨﻄﻮات(.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﻋﻨﺪﻣﺎ ﺗﺮﺗﻔﻊ درﺟﺔ اﻟﺤﺮارة ﻋﻦ اﻟﺼﻔﺮ اﻟﻤﻄﻠﻖ ﻓﺴﻮف ﯾﺨﺘﻞ اﻟﻨﻈﺎم ﺑﺴﺒﺐ اﻹﺛﺎرة
اﻟﺤﺮارﯾﺔ ﻟﻠﺠﺴﯿﻤﺎت اﻟﻜﻠﯿﺔ .وﯾﻌﺮف أﻧﺘﺮوﺑﻲ اﻟﻤﺎدة ﻋﻨﺪ ھﺬه اﻟﺪرﺟﺔ ﺑﺎﻷﻧﺘﺮوﺑﻲ اﻟﻤﻄﻠﻖ
) (S°وﯾﻌﻨﻲ ذﻟﻚ أن اﻷﻧﺘﺮوﺑﻲ اﻟﻤﻄﻠﻖ ) (S°ﻷي ﻣﺎدة ﻓﻲ درﺟﺔ ﺣﺮارة أﻋﻠﻰ ﻣﻦ اﻟﺼﻔﺮ
اﻟﻤﻄﻠﻖ ذات ﻗﯿﻤﺔ ﻣﻮﺟﺒﺔ ﺑﺴﺒﺐ ﻓﻘﺪان ﺣﺎﻟﺔ اﻟﻨﻈﺎم اﻟﺘﻲ ﺗﺴﻮد ﻓﻘﻂ ﻋﻨﺪ اﻟﺼﻔﺮ اﻟﻤﻄﻠﻖ .إذ
أﻧﮫ ﻛﻠﻤﺎ ارﺗﻔﻌﺖ درﺟﺔ اﻟﺤﺮارة ازداد ﻣﻌﮭﺎ اﻷﻧﺘﺮوﺑﻲ اﻟﻤﻄﻠﻖ ﻟﻠﻤﺎدة.
ﻗﯿﻢ اﻷﻧﺘﺮوﺑﻲ اﻟﻘﯿﺎﺳﻲ ) (Sοﻟﺒﻌﺾ اﻟﻤﻮاد ﻣﺤﺴﻮﺑﺔ ﻋﻠﻰ أﻧﮭﺎ اﻟﺰﯾﺎدة اﻟﺤﺎﺻﻠﺔ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ
ﻋﻨﺪﻣﺎ ﯾﺴﺨﻦ ﻣﻮل واﺣﺪ ﻣﻦ اﻟﻤﺎدة ﺑﺪءاً ﻣﻦ ﺣﺎﻟﺔ ﻣﺘﺒﻠﻮرة ﺗﻤﺎﻣﺎً ﻋﻨﺪ اﻟﺼﻔﺮ اﻟﻤﻄﻠﻖ
وﻣﺮوراً ﺑﺘﻐﯿﺮات ﻋﺪة ﻣﺜﻞ اﻹﻧﺼﮭﺎر واﻟﺘﺒﺨﺮ ﺣﺘﻰ ﺗﺼﻞ اﻟﻤﺎدة اﻟﻰ ﺣﺎﻟﺘﮭﺎ اﻟﻘﯿﺎﺳﯿﺔ ﻋﻨﺪ
درﺟﺔ ﺣﺮارة ) (298 Kوﺿﻐﻂ ﺟﻮي واﺣﺪ.
اﻟﺸﻜﻞ ) (٢٣ﯾﻮﺿﺢ أﻧﺘﺮوﺑﻲ اﻷﻛﺴﺠﯿﻦ ﻛﺘﺎﺑﻊ ﻟﺪرﺟﺔ اﻟﺤﺮارة اﺑﺘﺪاءً ﻣﻦ اﻟﺤﺎﻟﺔ اﻟﻤﻨﺘﻈﻤﺔ
ﺗﻤﺎﻣﺎً ﻟﻸﻛﺴﺠﯿﻦ .ﻓﺒﺰﯾﺎدة درﺟﺔ اﻟﺤﺮارة ﻓﺈن اﻟﺠﺰﯾﺌﺎت ﺗﺒﺪأ ﻓﻲ اﻹھﺘﺰاز ﺣﻮل أﻣﺎﻛﻨﮭﺎ وﺗﺒﺪأ
ﺣﺮﻛﺘﮭﺎ اﻟﺤﺮارﯾﺔ ﺗﺰداد وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن أﻧﺘﺮوﺑﻲ اﻷﻛﺴﺠﯿﻦ ﯾﺰداد.
• ﻋﻨﺪ ﻧﻘﻄﺔ اﻹﻧﺼﮭﺎر ﻓﺈن اﻟﺸﻜﻞ اﻟﻤﻨﺘﻈﻢ ﻟﻠﺠﺰﯾﺌﺎت ﻓﻲ اﻟﻤﺎدة اﻟﺼﻠﺒﺔ ﺗﺘﻐﯿﺮ اﻟﻰ ﺷﻜﻞ
ﯾﻜﻮن ﻓﯿﮫ أﻗﻞ اﻧﺘﻈﺎﻣﺎً ﻓﻲ اﻟﺤﺎﻟﺔ اﻟﺴﺎﺋﻠﺔ ﻟﺬﻟﻚ ﻓﺈﻧﮫ ﯾﺤﺪث زﯾﺎدة ﻣﻔﺎﺟﺌﺔ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ.
• ﺗﺒﺪأ ﺑﻌﺪ ذﻟﻚ اﻷﻧﺘﺮوﺑﻲ ﺗﺰداد ﺑﺸﻜﻞ ﺗﺪرﯾﺠﻲ ﻣﻊ ارﺗﻔﺎع درﺟﺔ اﻟﺤﺮارة ﺣﺘﻰ ﯾﻐﻠﻲ
اﻟﺴﺎﺋﻞ .وﯾﺤﺪث زﯾﺎدة ﻛﺒﯿﺮة ﻓﻲ ﺣﺠﻢ اﻷﻛﺴﺠﯿﻦ وﻛﺬﻟﻚ ﻓﻲ ﻋﺪم اﻧﺘﻈﺎم اﻟﺠﺰﯾﺌﺎت
وﯾﺮاﻓﻖ ذﻟﻚ زﯾﺎدة ﻣﻔﺎﺟﺌﺔ وﻛﺒﯿﺮة ﻓﻲ ﻗﯿﻤﺔ اﻷﻧﺘﺮوﺑﻲ ،وﺗﺴﺘﻤﺮ أﻧﺘﺮوﺑﻲ ﻏﺎز اﻷﻛﺴﺠﯿﻦ
ﻓﻲ اﻟﺰﯾﺎدة ﺑﺒﻂء ﻣﻊ زﯾﺎدة درﺟﺔ اﻟﺤﺮارة.
وﺣﺪات ﻗﯿﻢ اﻷﻧﺘﺮوﺑﻲ ھﻲ J/K molوﻟﯿﺲ kJ/K molﻧﻈﺮاً ﻟﺼﻐﺮھﺎ.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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Temperature (K)
أﻧﺘﺮوﺑﻲ اﻷﻛﺴﺠﯿﻦ ﻛﺘﺎﺑﻊ ﻟﺪرﺟﺔ اﻟﺤﺮارة: (٢٣) ﺷﻜﻞ
Fig. 24 : Entropy increase of a substance as the temperature rises from absolute zero.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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Fig. 25 :
a) A substance at a higher temperature has greater molecular motion, more disorder , and
greater entropy than, (b) the same substance at a lower temperature.
Fig. 26 : The entropy of a pure substance, equal to zero at 0 K, shows a steady increase
with rising temperature, punctuated by discontinuous jumps in entropy at the temperatures
of the phase transitions.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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(1 atm) ( وﺿﻐﻂ ﺟﻮي واﺣﺪ25 °C) اﻷﻧﺘﺮوﺑﻲ اﻟﻘﯿﺎﺳﻲ ﻟﺒﻌﺾ اﻟﻌﻨﺎﺻﺮ واﻟﻤﺮﻛﺒﺎت ﻋﻨﺪ: (٧) ﺟﺪول
Sº Sº Sº
Formula (J/mol.K) Formula (J/mol.K) Formula (J/mol.K)
H+(aq) 0 HCN(g) 201.7 H2S(g) 205.6
H2(g) 130.6 CCl4(g) 309.7 F-(aq) - 9.6
Na+(aq) 60.2 CCl4(L) 214.4 F2(g) 207.7
Na(s) 51.4 CH3CHO(g) 266 HF(g) 173.7
NaCl(s) 72.1 C2H5OH(L) 161 Cl-(aq) 55.1
NaHCO3(s) 102 Si(s) 18.5 Cl2(g) 223.0
Na2CO3(s) 139 SiO2(s) 41.5 HCl(g) 186.8
Ca2+(aq) - 55.2 SiF4(g) 285 Br-(aq) 80.7
Ca(s) 41.6 Pb(s) 64.8 Br2(L) 152.2
CaO(s) 38.2 PbO(s) 66.5 I-(aq) 109.4
CaCO3(s) 92.9 PbS(s) 91.3 I2(s) 116.1
C(graphite) 5.7 N2(g) 191.5 Ag+(aq) 73.9
C(diamond) 2.4 NH3(g) 193 Ag(s) 42.7
CO(g) 197.5 NO2(g) 240.5 AgF(s) 84
CO2(g) 213.7 N2O4(g) 304.3 AgCl(s) 96.1
HCO3- (aq) 95.0 O2(g) 205.0 AgBr(s) 107.1
CH4(g) 186.1 O3(g) 238.8 AgI(s) 114
C2H4(g) 219.2 OH- (aq) - 10.5
C2H6(g) 229.5 H2O(g) 188.7
C6H6(L) 172.8 H2O(L) 69.9
HCHO(g) 219 S2(g) 228.1
CH3OH(L) 127 S(rhombic) 31.9
CS2(g) 237.8 S(monoclinic) 32.6
CS2(L) 151.0 SO2(g) 248.1
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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Fig. 27 : The standard reaction enthalpy is the difference in enthalpy between the pure
products, each at 1 atm, and the pure reactants at the same pressure and the specified
temperature (which is commonly but not necessarily 25 °C). The scheme here is for the
combustion of methane.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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(٤٠) ﻣﺜﺎﻝ
4Fe(s) + 3O 2 (g) ←→ 2Fe 2 O3 (s)
ο
ΔS = - 549.4 J/K
(ب
CaCO3 (s) ←→ CaO(s) + CO2 (g)
ο ο ο
ΔS = ∑ n P (S ) P - ∑ n R (S ) R
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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(n R = 0, n P = 1 ⇒ 0
)→1
(٢ﯾﻜﻮن اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ﺳﺎﻟﺒﺎً )ﻟﻠﻨﻈﺎم( إذا ﻧﻘﺺ ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ ﺧﻼل اﻟﺘﻔﺎﻋﻞ :
→
← )4Fe(s) + 3O2 (g) 2Fe2 O3 (s ΔSο = - 549.4 J/K
)(n R = 3, n P = 0 ⇒ 3 → 0
(٣إذا ﻟﻢ ﯾﺤﺪث ﺗﻐﯿﺮ ﻓﻲ ﻋﺪد اﻟﻤﻮﻻت اﻟﻐﺎزﯾﺔ اﻟﻜﻠﻲ ﺧﻼل اﻟﺘﻔﺎﻋﻞ ﻛﻤﺎ ﻓﻲ اﻟﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ:
H 2 (g) + I 2 (g)
)→ 2HI(g
(n R )→ 2
= 2, n P = 2, ⇒ 2
ﻓﺈن اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ ﯾﻤﻜﻦ أن ﯾﻜﻮن ﺳﺎﻟﺒﺎً أو ﻣﻮﺟﺒﺎً ﺣﺴﺐ ﻗﯿﻢ أﻧﺘﺮوﺑﻲ اﻟﻤﻮاد
اﻟﻤﺸﺘﺮﻛﺔ ﻓﻲ اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ﺣﺴﺎﺑﮭﺎ ﻣﻦ اﻟﻤﻌﺎدﻟﺔ :
وﺑﻨﻲ اﻟﺘﻨﺒﺆ ﻓﻲ اﻟﻔﻘﺮﺗﯿﻦ ) (٢ ،١ﻋﻠﻰ أن أﻧﺘﺮوﺑﻲ اﻟﻤﻮاد اﻟﻐﺎزﯾﺔ دون اﺳﺘﺜﻨﺎء أﻛﺒﺮ ﺑﻜﺜﯿﺮ
ﻣﻦ أﻧﺘﺮوﺑﻲ اﻟﻤﻮاد اﻟﺴﺎﺋﻠﺔ واﻟﻤﻮاد اﻟﺼﻠﺒﺔ.
(٤ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻼت اﻟﺘﻲ ﯾﺸﺘﺮك ﻓﯿﮭﺎ ﻣﻮاد ﺻﻠﺒﺔ وﺳﺎﺋﻠﺔ ﻓﻘﻂ ﻓﯿﻜﻮن اﻟﺘﻨﺒﺆ ﻋﻦ ﻛﯿﻔﯿﺔ
ﺗﻐﯿﺮ اﻷﻧﺘﺮوﺑﻲ ﺻﻌﺒﺎً .وﺑﺸﻜﻞ ﻋﺎم ﯾﻤﻜﻦ اﻟﻘﻮل ﺑﺄن اﻟﺰﯾﺎدة ﻓﻲ اﻟﻌﺪد اﻟﻜﻠﻲ ﻟﻠﺠﺰﯾﺌﺎت
و /أو اﻷﯾﻮﻧﺎت ﺧﻼل اﻟﺘﻔﺎﻋﻞ ﯾﻜﻮن ﻣﺼﺤﻮﺑﺎً ﺑﺰﯾﺎدة ﻓﻲ أﻧﺘﺮوﺑﻲ اﻟﻨﻈﺎم.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٤١
ﺍﳊﻞ
أ( ﻷﯾﻮﻧﺎن ) (Ag+, Cl-ﺣﺮﯾﺔ اﻟﺤﺮﻛ ﺔ ﻓ ﻲ اﻟﻤﺤﻠ ﻮل ﺑﯿﻨﻤ ﺎ ﻧﺠ ﺪ أن AgClﺻ ﻠﺐ ،إﺿ ﺎﻓﺔ
إﻟﻰ أن ﻋﺪد اﻟﺠﺴﯿﻤﺎت ﯾﻨﻘﺺ ﻣﻦ اﻟﯿﺴﺎر اﻟﻰ اﻟﯿﻤﯿﻦ ،إذاً ∆Sﺗﻜﻮن ﺳﺎﻟﺒﺔ.
ب( ﺑﻤﺎ أن اﻟﻤﺎدة اﻟﺼﻠﺒﺔ ﺗﺘﺤﻮل اﻟﻰ ﻧﺎﺗﺠﯿﻦ ﻏﺎزﯾﯿﻦ ﻓﺈن ∆Sﺗﻜﻮن ﻣﻮﺟﺒﺔ.
ج( ﻧﻔﺲ ﻋﺪد اﻟﻤﻮﻻت ﻓﻲ اﻟﻤﺘﻔﺎﻋﻼت واﻟﻨ ﻮاﺗﺞ ﻟ ﺬﻟﻚ ﻻ ﻧ ﺴﺘﻄﯿﻊ اﻟﺘﻨﺒ ﺆ ﺑﺈﺷ ﺎرة ∆Sوﻟﻜ ﻦ
ﻧﻌﻠﻢ أن اﻟﺘﻐﯿﺮ ﯾﺠﺐ أن ﯾﻜﻮن ﺻﻐﯿﺮاً ﺟﺪاً.
ﻣﺜﺎﻝ )(٤٢
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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ﺍﳊﻞ
: اﻟﻤﻌﺎدﻟﺔ اﻷوﻟﻰ
1................2SO 2 (g) + O 2 (g)
→ 2SO 3 (g)
ΔS =
ο
∑n S - ∑n S
P
ο
P R
ο
R
ΔS = 2S (SO 3 ) - 2S (SO 2 ) + S (O 2 )
ο ο ο ο
ο
ΔS = - 187.8 J/K
: اﻟﻤﻌﺎدﻟﺔ اﻟﺜﺎﻧﯿﺔ
2................N 2 O 4 (g)
→ 2NO 2 (g)
ΔS =
ο
∑n S - ∑n P
ο
P R
ο
SR
ΔS = 2S (NO 2 ) - S (N 2 O 4 )
ο ο ο
ΔS = [ 2 (240.2) ] − [ (303.8) ]
ο
ο
ΔS = + 176.6 J/K
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﺑﻤﺎ أن ) (S, Hﺗﺎﺑﻌﺎن ﻟﻠﺤﺎﻟﺔ ،ﻓﺈن Gﺗﺎﺑﻊ ﻟﻠﺤﺎﻟﺔ أﯾﻀﺎً ،أي أﻧﮭﺎ ﺗﻌﺘﻤﺪ ﻓﻘﻂ ﻋﻠﻰ اﻟﺤﺎﻟﺔ
اﻹﺑﺘﺪاﺋﯿﺔ واﻟﻨﮭﺎﺋﯿﺔ ﻟﻠﻨﻈﺎم أي أن :
∆G = G f - G i
وﻟﻜﻲ ﯾﻜﻮن ﺗﻔﺎﻋﻞ ﻣﺎ ﺗﻠﻘﺎﺋﯿﺎً ﯾﺠﺐ أن ﺗﻜﻮن ﻗﯿﻤﺔ ) (Gfأﺻﻐﺮ ﻣﻦ ﻗﯿﻤﺔ ) (Giأي أن ﻗﯿﻤﺔ
) ( ∆Gﺳﺎﻟﺒﺔ.
ﻛﯿﻒ ﯾﻤﻜﻦ اﻟﺘﻨﺒﺆ ﺑﺘﻠﻘﺎﺋﯿﺔ اﻟﺘﻔﺎﻋﻞ ﻣﻦ ∆G = ∆H - T∆S س( ﺑﺎﻹﻋﺘﻤﺎد ﻋﻠﻰ اﻟﻤﻌﺎدﻟﺔ :
ﻋﺪﻣﮭﺎ ؟
ﺝ(
وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن ﻗﯿﻤﺔ ∆Gﺗﻜﻮن ﺳﺎﻟﺒﺔ ،وھﺬا ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ ﺳﻮف ﯾﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً ﻋﻨﺪ
ﺟﻤﯿﻊ درﺟﺎت اﻟﺤﺮارة.
أي ) ، ( ∆H = +واﻧﺨﻔﺎض ﻓﻲ ∆H ( (٢إذا ﻛﺎن اﻟﺘﻔﺎﻋﻞ ﻣﺼﺤﻮﺑﺎً ﺑﺰﯾﺎدة ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ
ﻓﺈن : )( ∆S = - اﻷﻧﺘﺮوﺑﻲ ∆Sأي أن
أ( ﻋﻨﺪ درﺟﺎت اﻟﺤﺮارة اﻟﻤﻨﺨﻔﻀﺔ اﻟﺘﻲ ﺗﺠﻌﻞ اﻟﻘﯿﻤﺔ ) ( ∆H < T∆Sﻓﺈن ∆G < 0 :أي
ﺑﺎﻟﺴﺎﻟﺐ وﯾﻜﻮن اﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﯿﺎً.
ب( ﻋﻨﺪ درﺟﺎت اﻟﺤﺮارة اﻟﻌﺎﻟﯿﺔ ﺑﺤﯿﺚ ﺗﺠﻌﻞ اﻟﻘﯿﻤﺔ ) ( ∆H > T∆Sﻓﺈن∆G > 0 :
ﺗﻜﻮن ﻣﻮﺟﺒﺔ وﯾﻜﻮن اﻟﺘﻔﺎﻋﻞ ﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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(٥إذا ﻛﺎﻧﺖ ﻗﯿﻤﺔ ∆G = 0ﻓﺈن ھﺬا ﯾﻌﻨﻲ أن اﻟﺘﻔﺎﻋﻞ ﻟﯿﺲ ﻟﺪﯾﮫ اﻟﻘﺎﺑﻠﯿﺔ أن ﯾﺤﺪث ﺳﻮاء
ﻓﻲ اﻹﺗﺠﺎه اﻟﻤﺒﺎﺷﺮ أو اﻹﺗﺠﺎه اﻟﻤﻌﺎﻛﺲ ،أي أن اﻟﺘﻔﺎﻋﻞ ﻓﻲ ﺣﺎﻟﺔ ﺗﻮازن.
س( ﻣﺎ اﻟﻌﺎﻣﻼن اﻟﻮاﺟﺐ ﺗﻮﻓﺮھﻤﺎ ﺣﺘﻰ ﺗﻜﻮن ﻋﻤﻠﯿﺔ ﻣﺎ ﺗﻠﻘﺎﺋﯿﺔ ،ﺑﻐﺾ اﻟﻨﻈﺮ ﻋﻦ درﺟﺔ
ﺣﺮارﺗﮭﺎ؟
أن ﺗﻜﻮن ( ∆H < 0, ∆S > 0 ) :
ΔG = ∑ n P ΔG f
ο
( ο
) ) - ∑ n ( ΔG
P R
ο
f R
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1562
وﻣﻨﮫ ﻓﺈن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻟﺘﻔﺎﻋﻞ ﻣﺎ ﯾﺴﺎوي ﻣﺠﻤﻮع ﻗﯿﻢ ﻃﺎﻗﺎت اﻟﺘﻜﻮﯾﻦ
اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻟﻠﻤﻮاد اﻟﻨﺎﺗﺠﺔ ﻣﻄﺮوﺣﺎً ﻣﻨﮫ ﻣﺠﻤﻮع ﻗﯿﻢ ﻃﺎﻗﺎت اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ
ﻟﻠﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ.
ج( ﻃﺎﻗﺔ اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻟﻤﺮﻛﺐ ﻣﺎ :ﻋﺒﺎرة ﻋﻦ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻤﺼﺎﺣﺐ
ﻟﺘﻜﻮن ﻣﻮل واﺣﺪ ﻣﻦ ﻣﺮﻛﺐ ﻣﺎ ﻣﻦ ﻋﻨﺎﺻﺮه اﻷوﻟﯿﺔ وھﻲ ﻓﻲ ﺣﺎﻟﺘﮭﺎ اﻟﻘﯿﺎﺳﯿﺔ .وﺗﻜﻮن ﻃﺎﻗﺔ
اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻷي ﻋﻨﺼﺮ ﻓﻲ ﺣﺎﻟﺘﮫ اﻟﻘﯿﺎﺳﯿﺔ ﺗﺴﺎوي ﺻﻔﺮاً.
أﯾﻀﺎً ﻣﻦ اﻟﻌﻼﻗﺔ : ΔG
ο
وﯾﻤﻜﻦ ﺣﺴﺎب
ο ο
وﯾﺤﺴﺐ ΔHﻣﻦ ﻗﯿﻢ ﺣﺮارة اﻟﺘﻜﻮﯾﻦ اﻟﻘﯿﺎﺳﯿﺔ ΔH fﻣﻦ اﻟﻌﻼﻗﺔ :
(
ΔH = ∑ n P ΔH f
ο ο
) ) - ∑ n ( ΔH
P R
ο
f R
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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(25 °C) ﻗﯿﻢ ﻃﺎﻗﺔ اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻋﻨﺪ: (٩) ﺟﺪول
∆G ο ∆G ο ∆G ο
Formula (kJ/mol) Formula (kJ/mol) Formula (kJ/mol)
H+(aq) 0 HCN(g) 125 H2S(g) - 33
H2(g) 0 CCl4(g) - 53.7 F-(aq) - 276.5
Na+(aq) - 261.9 CCl4(L) - 68.6 F2(g) 0
Na(s) 0 CH3CHO(g) - 133.7 HF(g) - 275
NaCl(s) - 348.0 C2H5OH(L) - 174.8 Cl-(aq) - 131.2
NaHCO3(s) - 851.9 Si(s) 0 Cl2(g) 0
Na2CO3(s) - 1048.1 SiO2(s) - 856.5 HCl(g) - 95.3
Ca2+(aq) - 553.0 SiF4(g) - 1506 Br-(aq) - 102.8
Ca(s) 0 Pb(s) 0 Br2(L) 0
CaO(s) - 603.5 PbO(s) - 189 I-(aq) - 51.7
CaCO3(s) - 1128.8 PbS(s) - 96.7 I2(s) 0
C(graphite) 0 N2(g) 0 Ag+(aq) 77.1
C(diamond) 2.9 NH3(g) - 16.4 Ag(s) 0
CO(g) - 137.2 N2O (g) 103.6 AgF(s) - 185
CO2(g) - 394.4 AgCl(s) - 109.7
HCO3- (aq) - 587.1 O2(g) 0 AgBr(s) - 95.9
CH4(g) - 50.8 O3(g) 163 AgI(s) - 66.3
C2H4(g) 68.4 OH- (aq) - 157.3
C2H6(g) - 32.9 H2O(g) - 228.6
C6H6(L) 124.5 H2O(L) - 237.2
HCHO(g) - 110 S2(g) 80.1
CH3OH(L) - 166.2 S(rhombic) 0
CS2(g) 66.9 S(monoclinic) 0.10
CS2(L) 63.6 SO2(g) - 300.2
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1564
ﺳﻨﻨﺎﻗﺶ ﺗﺤﻀﯿﺮ أﻛﺴﯿﺪ اﻟﻜﺎﻟﺴﯿﻮم ﻣﻦ ﺗﺤﻠﻞ ﻛﺮﺑﻮﻧﺎت اﻟﻜﺎﻟﺴﯿﻮم ﻋﻨﺪ درﺟﺎت اﻟﺤﺮارة
اﻟﻌﺎﻟﯿﺔ:
)→ CaO(s) + CO2 (g
CaCO3 (s) ←
ﺗﺘﺤﻠ ﻞ ﻛﺮﺑﻮﻧ ﺎت اﻟﻜﺎﻟ ﺴﯿﻮم ﻓ ﻲ ﺗﻔﺎﻋ ﻞ اﻧﻌﻜﺎﺳ ﻲ ﺣﯿ ﺚ ﯾﺘﺤ ﺪ أﻛ ﺴﯿﺪ اﻟﻜﺎﻟ ﺴﯿﻮم )(CaO
ﺑﺴﮭﻮﻟﺔ ﻣﻊ ﻏﺎز ﺛﺎﻧﻲ أﻛﺴﯿﺪ اﻟﻜﺮﺑ ﻮن ﻟﯿﻜ ﻮن ﻛﺮﺑﻮﻧ ﺎت اﻟﻜﺎﻟ ﺴﯿﻮم .إن ﺿ ﻐﻂ CO2اﻟﻤﺘ ﺰن
ﻣﻊ CaOو CaCO3ﯾﺰﯾﺪ ﺑﺰﯾﺎدة درﺟﺔ اﻟﺤﺮارة .وﺑﺎﻟﺘﺎﻟﻲ ﻓﻺﻧﺘﺎج ﻛﻤﯿﺎت أﻛﺒﺮ ﻣ ﻦ أﻛ ﺴﯿﺪ
اﻟﻜﺎﻟﺴﯿﻮم ﯾﺴﺤﺐ ﻏﺎز CO2داﺋﻤﺎً ﻣﻦ وﺳﻂ اﻟﺘﻔﺎﻋﻞ اﻷﻣ ﺮ اﻟ ﺬي ﯾﺠﻌ ﻞ اﻹﺗ ﺰان ﯾﻨ ﺰاح ﻣ ﻦ
اﻟﯿﺴﺎر )اﻟﻤﺘﻔﺎﻋﻼت( اﻟﻰ اﻟﯿﻤﯿﻦ )اﻟﻨﻮاﺗﺞ(.
وأھﻢ ﻣﻌﻠﻮﻣﺔ ھﻨﺎ ﺗﻜﻤﻦ ﻓﻲ ﻣﻌﺮﻓﺔ درﺟﺔ ﻟﺤﺮارة اﻟﺘﻲ ﺗﺘﺤﻠﻞ ﻓﯿﮭ ﺎ أﻛﺒ ﺮ ﻛﻤﯿ ﺔ ﻣ ﻦ ﻛﺮﺑﻮﻧ ﺎت
اﻟﻜﺎﻟﺴﯿﻮم ،أو ﺑﻤﻌﻨﻰ آﺧﺮ ﻣﺎ ھﻲ درﺟﺔ اﻟﺤﺮارة اﻟﺘﻲ ﯾﻜﻮن ﻓﯿﮭﺎ اﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﯿﺎً؟.
ο
ﻟﺘﻘﺪﯾﺮ درﺟﺔ اﻟﺤﺮارة ھﺬه ﻓﺈﻧﻨﺎ ﻧﺤﺴﺐ ΔH , ΔSﺑﺎﺳﺘﺨﺪام اﻟﻤﻌﺎدﻟﺘﯿﻦ:
ο
ο
= ΔH rxn )∑ nΔH (Products) - ∑ nΔH (Reactants
ο
f
ο
f
ο
= ΔSrxn )∑ nS (Products) - ∑ nS (Reactants
ο ο
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1565
1. ΔH = ∑ n P ΔH f
ο
( ο
) - ∑ n ( ΔH )
P R
ο
f R
ΔH = ΔH f ( CaO ) + ΔH f ( CO 2 ) - ΔH f ( CaCO 3 )
ο ο ο ο
2. ΔS = ∑ n P (S ) P - ∑n
ο ο ο
R
(S ) R
ΔS = S
ο ο
( CaO ) + S ( CO ) - S ( CaCO )
ο
2
ο
3
ΔS =
ο
[39.8 + 213.6 ] − [92.9 ] = 160.5 J/K
: وﺑﺎﻟﻨﺴﺒﺔ ﻟﺘﻔﺎﻋﻞ ﯾﺤﺪث ﻋﻨﺪ اﻟﺤﺎﻟﺔ اﻟﻘﯿﺎﺳﯿﺔ ﻓﺈن
ο ο ο
ΔG = ΔH - TΔS
ΔG = + 177.8 × 10 - 298 × 160.5
ο 3
ο
ΔG = 130 000 J
ο
ΔG = 130.0 kJ
ﻛﺒﯿ ﺮة وﻣﻮﺟﺒ ﺔ ﻓ ﯿﻤﻜﻦ اﺳ ﺘﻨﺘﺎج أن ھ ﺬا اﻟﺘﻔﺎﻋ ﻞ ﻏﯿ ﺮ ﻣﺮﻏ ﻮب ﻓﯿ ﮫ ﻋﻨ ﺪΔG ο ﺑﻤﺎ أن ﻗﯿﻤ ﺔ
ﺳ ﺎﻟﺒﺔ ﯾﺠ ﺐ ﻋﻠﯿﻨ ﺎ أوﻻً أن ﻧﻮﺟ ﺪ درﺟ ﺔ ΔG ο وﻟﻜ ﻲ ﻧﺠﻌ ﻞ. (25 °C) درﺟ ﺔ اﻟﺤ ﺮارة
. اﻟﺼﻔﺮΔG ο اﻟﺤﺮارة اﻟﺘﻲ ﺗﻌﺎدل ﻓﯿﮭﺎ ﻗﯿﻤﺔ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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=T ο
=
ΔS
-1
160.5 J K
T = 1108 K
ο
T = 1108 - 273 = 835 C
ﺗ ﺼﺒﺢ ﺳ ﺎﻟﺒﺔ، ΔG ο وھﺬا ﯾﻌﻨﻲ أﻧﮫ ﻋﻨﺪ أي درﺟ ﺔ ﺣ ﺮارة أﻋﻠ ﻰ ﻣ ﻦ ) (849 °Cﻓ ﺈن ﻗﯿﻤ ﺔ
اﻷﻣ ﺮ اﻟ ﺬي ﯾﻌﻨ ﻲ أن ﺗﺤﻠ ﻞ اﻟﻜﺮﺑﻮﻧ ﺎت ﺳ ﻮف ﯾﻜ ﻮن ﺗﻠﻘﺎﺋﯿ ﺎً .ﻓﻤ ﺜﻼً ﻋﻨ ﺪ درﺟ ﺔ ﺣ ﺮارة
) (855 °C = 1128 Kﻧﺠﺪ أن :
ο ο ο
ΔG = ΔH - TΔS
)ΔG = 178.3 × 10 - (1128 × 158.9
ο 3
ο
ΔG = - 939.2 J
ο
ΔG = - 0.94 kJ
ﺗﻮﺟﺪ ﻣﻼﺣﻈﺘﺎن ﻣﮭﻤﺘﺎن ﯾﺠﺐ اﻹﺷﺎرة إﻟﯿﮭﻤﺎ ﻓﻲ ﻣﺜﻞ ھﺬه اﻟﺤﺴﺎﺑﺎت:
ο ο
أوﻻً :ﻟﻘﺪ اﺳﺘﺨﺪﻣﻨﺎ ﻗﯿﻢ ΔH , ΔSﻋﻨﺪ درﺟﺔ اﻟﺤ ﺮارة 25 °Cﻟﺤ ﺴﺎﺑﺎت اﻟﺘﻐﯿ ﺮات اﻟﺘ ﻲ
ﯾﺘﻐﯿ ﺮان ﻣ ﻊ ﺗﻐﯿ ﺮ درﺟ ﺔ اﻟﺤ ﺮارة ΔS
ο
و ΔH
ο
ﺗﺤﺪث ﻋﻨﺪ ، 855 °Cوﺣﯿ ﺚ أن ﻛ ﻼً ﻣ ﻦ
ﻓﺈن ھﺬا اﻟﺘﻌﺎﻣﻞ ﻻ ﯾﻌﻄ ﻲ ﻗﯿﻤ ﺎً ﺻ ﺤﯿﺤﺔ ﻟﻠﺘﻐﯿ ﺮ ﻓ ﻲ اﻟﻄﺎﻗ ﺔ اﻟﺤ ﺮة ΔGوﻟﻜﻨ ﮫ ﯾﻤﺜ ﻞ ﺧﻄ ﻮة
ο
ο
ﻋﻈﯿﻤﺔ ﻓﻲ ﺳﺒﯿﻞ ﺗﻘﺪﯾﺮ . ΔG
ﺛﺎﻧﯿ ﺎً :ﯾﺠ ﺐ أن ﻻ ﺗﻌﺘﻤ ﺪ ﻋﻠ ﻰ أﻧ ﮫ ﻻ ﯾﺤ ﺪث ﺷ ﻲء ﺗﺤ ﺖ درﺟ ﺔ اﻟﺤ ﺮارة 835 °Cوأن
ﻛﺮﺑﻮﻧ ﺎت اﻟﻜﺎﻟ ﺴﯿﻮم ﻓﺠ ﺄة ﺗﺘﺤﻠ ﻞ ﻋﻨ ﺪ . 835 °Cﻓﮭﺎﺗ ﺎن اﻟﻌﻤﻠﯿﺘ ﺎن اﻻﺗﺤﺎدﯾﺘ ﺎن ﻻ ﺗﺤ ﺪﺛﺎن
أﺑﺪاً.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1567
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1568
واﻟ ﺸﻜﻞ ) ٢٨و (٢٩ﯾﻈﮭ ﺮ إن ﺿ ﻐﻂ CO2ﯾﺰﯾ ﺪ أوﻻً ﺑ ﺒﻂء ﺷ ﺪﯾﺪ ﻣ ﻊ زﯾ ﺎدة درﺟ ﺔ
اﻟﺤ ﺮارة ﺣﺘ ﻰ ﯾ ﺼﺒﺢ ﻣ ﻦ اﻟﻤﻤﻜ ﻦ ﻗﯿﺎﺳ ﮫ ﻓ ﻮق درﺟ ﺔ اﻟﺤ ﺮارة .700 °Cإن أھﻤﯿ ﺔ درﺟ ﺔ
اﻟﺤﺮارة 835 °Cﺗﻜﻤﻦ ﻓﻲ أﻧﮭﺎ درﺟ ﺔ اﻟﺤ ﺮارة اﻟﺘ ﻲ ﯾ ﺼﻞ ﻓﯿﮭ ﺎ ﺿ ﻐﻂ CO2اﻟ ﻰ ﺿ ﻐﻂ
ﺟﻮي ). (1 atm
ﻣﺜﺎﻝ )(٤٣
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1569
ﻣﺜﺎﻝ )(٤٤
ﺍﳊﻞ
ο
ΔG = + 34918.4 J/mol
ο
ΔG = + 34.918 kJ/mol
وﻣﻦ ھﻨﺎ ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ ﻋﻨﺪ درﺟﺔ ﺣﺮارة ) (25 ºCﻷن إﺷﺎرة ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ
اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﺑﺎﻟﻤﻮﺟﺐ ) ( ∆G = +
ο
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٤٥
ﺍﳊﻞ
وﺑﻤﺎ أن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﺑﺎﻟﻤﻮﺟﺐ ) ( ΔG = +ﻓﺎﻟﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻖ ﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ
).(25 ºC ﻋﻨﺪ
ب( ﺣﺴﺎب اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﻋﻨﺪ درﺟﺔ ﺣﺮارة ): (200 ºC
∆G = ∆H - T∆S
)∆G = (25.9 × 103 J/mol) - (473 K × 82.4 J/K
∆G = - 13075.2 J/mol
∆G = - 13.1 kJ/mol
وﺑﻤﺎ أن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﺑﺎﻟﺴﺎﻟﺐ ) ( ΔG = -ﻓﺎﻟﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻖ ﯾﻜﻮن ﺗﻠﻘﺎﺋﯿﺎً ﻋﻨﺪ
درﺟﺔ ﺣﺮارة ). (200 ºC
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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(٤٦) ﻣﺜﺎﻝ
CaCO 3 (s)
→ CaO(s) + CO 2 (g) (أ
N 2 (g) + 3H 2 (g)
→ 2NH 3 (g) (ب
: ﻋﻠﻤﺎً ﺑﺄن
( ΔH ( NH ) = - 46 kJ/mol, ΔH ( N ) = 0, ΔH ( H ) = 0 )
ο
f 3
ο
f 2
ο
f 2
( ∆G ( NH ) = - 14.4 kJ/mol, ∆G ( N ) = 0, ∆G ( H ) = 0 )
ο
f 3
ο
f 2
ο
f 2
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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ﺍﳊﻞ
CaCO3 (s)
→ CaO(s) + CO 2 (g) (أ
1. ΔH ο = ∑ n P ( ΔH οf ) - ∑ n R ( ΔH οf )
P R
ΔH ο = [ (- 635.1) + (- 393.5) ] - [(-1206.9 ] = + 178.3 kJ
2. ΔS =
ο
∑n P
ο
(S ) P - ∑n R
ο
(S ) R
ΔS = S
ο ο
( CaO ) ( CO ) - S ( CaCO )
+S
ο
2
ο
3
ΔS =
ο
[38.1 + 213.7 ] − [92.9 ] = 158.9 J/K
3. ΔG =
ο
∑ n ( ΔG ) - ∑ n ( ΔG )
P
ο
f P R
ο
f R
ΔG = ΔG
ο ο
( CaO ) ( CO ) - ΔG ( CaCO )
+ ΔG
ο
2
ο
3
ο
: ﺑﺎﺳﺘﺨﺪام اﻟﻌﻼﻗﺔΔG وﯾﻤﻜﻦ ﺣﺴﺎب اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة
ο ο ο
ΔG =ΔH - TΔS
ΔG = [178.3] - (298) (158 × 10 )
ο -3
ο
ΔG = 131.2 kJ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1573
وﺗﺪل ﻗﯿﻤﺘﮭﺎ اﻟﻤﻮﺟﺒﺔ ﻋﻠﻰ أن اﻟﺘﻔﺎﻋﻞ ﻟﯿﺲ ﻟﺪﯾﮫ اﻟﻘﺎﺑﻠﯿﺔ ﻷن ﯾﺤﺪث ﺗﻠﻘﺎﺋﯿﺎً ﻋﻨﺪ اﻟﻈﺮوف
اﻟﻘﯿﺎﺳﯿﺔ )(25 ºC, 1 atm
ﻣﺜﺎﻝ )(٤٧
اﺣﺴﺐ ﻃﺎﻗﺔ اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ) ( ΔGﻟﻤﻮل ﻣﻦ ﻏﺎز اﻟﻨﺸﺎدر إذا ﻋﻠﻤﺖ أن :
ο
ﺍﳊﻞ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1574
= ΔS
ο
∑n S - ∑n S
P
ο
P R
ο
R
ο
ΔS = - 197.8 J/K
ﺛﺎﻧﯿﺎً :ﻧﺤﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ ﻛﻤﺎ ﯾﻠﻲ :
= ΔH
ο
) ∑ n ( ∆H ) - ∑ n ( ∆H
P
ο
f P R
ο
f R
ο
ΔH = - 92.4 kJ
ﺛﺎﻟﺜﺎً :ﻟﺤﺴﺎب اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ :
ΔG ο = ΔH ο - TΔSο
])ΔG ο = (- 92.4 × 103 J) - [ 298 K × (-197.8 J/K
ΔG ο = - 33455.6 J
ΔG ο = - 33.46 kJ
ο
وھﺬه اﻟﻘﯿﻤﺔ ) (ΔG = - 33.46 kJﺗﻌﺒﺮ ﻋﻦ ﻃﺎﻗﺔ اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة ﻟﻤﻮﻟﯿﻦ ﻣﻦ اﻟﻨﺸﺎدر ﻛﻤﺎ
ﻓﻲ اﻟﻤﻌﺎدﻟﺔ اﻟﺴﺎﺑﻘﺔ ،وﻟﺬﻟﻚ ﻟﻠﺤﺼﻮل ﻋﻠﻰ ﻃﺎﻗﺔ اﻟﺘﻜﻮﯾﻦ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻟﻤﻮل ﻣﻦ ﻏﺎز
اﻟﻨﺸﺎدر ﻧﻘﺴﻢ ھﺬه اﻟﻘﯿﻤﺔ ﻋﻠﻰ ): (2
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
1575
(٤٨) ﻣﺜﺎﻝ
ﺍﳊﻞ
ο
ΔH = ∑n P
ο
(ΔH f ) P - ∑n R
ο
(ΔH f ) R
ο
[ ο ο
ΔH = ΔH f (Ti) + 2ΔH f (CO) - ΔH f (TiO 2 ) + 2ΔH f (C) ][ ο ο
]
ΔH = [ 0 + 2(- 110.5) ] − [ ( − 943.9) + 2(0) ]
ο
ΔH = ( - 221) - ( - 943.9 )
ο
ο
ΔH = + 722.9 kJ
ΔH = + 722.9 × 10 J
ο 3
( ∆S )
ο
ﻧﺤﺴﺐ اﻟﺘﻐﯿﺮ ﻓﻲ اﻷﻧﺘﺮوﺑﻲ اﻟﻘﯿﺎﺳﻲ: ًﺛﺎﻧﯿﺎ
ο
ΔS = ∑n S - ∑n S
P
ο
P R
ο
R
ο
ΔS = + 363.9 J/K
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
1576
ΔG ο = ΔH ο - TΔSο
] )ΔG ο = (+ 722.9 × 103 J) - [ 298 K ( + 363.9 J/K
ΔG ο = 614457.8 J
ΔG ο = 614.46 kJ
وﺣﯿﺚ أن ﻗﯿﻤﺔ اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﺑﺎﻟﻤﻮﺟﺐ ،ﻟﺬﻟﻚ ﻓﺎﻟﺘﻔﺎﻋﻞ اﻟﺴﺎﺑﻖ ﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ ﻋﻨﺪ درﺟﺔ
ﺣﺮارة 298 K
ﻣﺜﺎﻝ )(٤٩
ο
ج( ΔG ΔS
ο
ب( ΔH
ο
أ( اﺣﺴﺐ :
ο ο
د( ΔGﻋﻨﺪ درﺟﺔ ﺣﺮارة ) (100 ºCﺑﺎﻓﺘﺮاض أن (ΔH = ΔH, ΔS = ΔS) :
ﺍﳊﻞ
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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ΔH =
ο
∑n P
(ΔH f ) P - ∑ n R (ΔH f ) R
ο ο
ΔH = ( - 1644.4 ) - ( - 277.6 )
ο
ο
ΔH = - 1366.8 kJ
ο
ΔH = - 1366.8 x 10 J
3
ΔS = ( 637.1) - ( 776 )
ο
ο
ΔS = - 138.9 J
ο
: ΔG ج( ﺣﺴﺎب اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ
ΔG ο =ΔH ο - TΔSο
ΔG ο = (-1366.8 × 103 J) - [ 298 K (-138.9 J/K) ]
ΔG ο = - 1325407.8 J
ΔG ο = - 1325.41 kJ
.(25 ºC) ( ﺑﺎﻟﺴﺎﻟﺐ ﻓﺎﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﻲ ﻋﻨﺪΔ G ο = -) ﺑﻤﺎ أن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ
ΔG = ∆H - T∆S
] )ΔG = (-1366.8 × 10 ) - [ 373 K(-138.9 J/K
3
وﺑﻤﺎ أن ﻗﯿﻤﺔ اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﺑﺎﻟﺴﺎﻟﺐ ﻓﺎﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﻲ ﻋﻨﺪ درﺟﺔ اﻟﺤﺮارة ).(100 °C
ﻣﺜﺎﻝ )(٥٠
ﺍﳊﻞ
وﺑﻤﻘﺎرﻧﺔ ﻓﻘﺮة ج ﺑﻔﻘﺮة د ﯾﺘﻀﺢ أن رﻓﻊ درﺟﺔ اﻟﺤﺮارة ﯾﻘﻠﻞ ﻣﻦ ﺗﻠﻘﺎﺋﯿﺘﮫ )أي ﯾﻘﻠﻞ ﻣﻦ ﺳﯿﺮه
ﻓﻲ اﻹﺗﺠﺎه اﻟﻤﺒﺎﺷﺮ ﻣﻦ اﻟﯿﺴﺎر )اﻟﻤﺘﻔﺎﻋﻼت( اﻟﻰ اﻟﯿﻤﯿﻦ )اﻟﻨﻮاﺗﺞ(.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٥١
ب( وإذا ﻛﺎن اﻟﺘﻔﺎﻋﻞ ﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ ،ﻓﻤﺎ درﺟﺔ اﻟﺤﺮارة اﻟﺘﻲ ﯾﻜﻮن ﻋﻨﺪھﺎ اﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﯿﺎً.
ﺍﳊﻞ
ο
أوﻻً :ﺣﺴﺎب اﻟﺘﻐﯿﺮ ﻓﻲ اﻹﻧﺜﺎﻟﺒﻲ اﻟﻘﯿﺎﺳﻲ ΔH
ο
= ΔH ∑n P
(ΔH f ) P - ∑ n R (ΔH f ) R
ο ο
ο
ΔH = + 178.4 kJ
ο
ΔH = + 178.4 x 10 J
3
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ΔG = ΔH - TΔS
0 = ΔH - TΔS
ΔH = TΔS
ΔH
=T
ΔS
178.4 × 103
=T = 1111.53K
160.5
وﺑﺎﻟﺘﺎﻟﻲ ﻓﺈﻧﮫ ﻋﻨﺪ اﻟﺪرﺟﺔ ) (1111.53 Kﺗﻜﻮن ) ( ∆G = 0وﯾﻜﻮن اﻟﺘﻔﺎﻋﻞ ﻣﺘﺰﻧﺎً ،وﺗﻜﻮن
اﻟﺪرﺟﺔ ﻣﻦ اﻟﺤﺮارة اﻟﺘﻲ ﯾﻜﻮن ﻓﯿﮭﺎ اﻟﺘﻔﺎﻋﻞ :
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺣﯿﺚ :
: Rھﻲ ﺛﺎﺑﺖ اﻟﻐﺎزات اﻟﻌﺎم وﻗﯿﻤﺘﮫ ).(8.314 J/mol K
: Qراﺋ ﺰ )ﻛ ﺴﺮ اﻟﺘﻔﺎﻋ ﻞ( واﻟ ﺬي ﯾﻨ ﺘﺞ ﻣ ﻦ ﺗﻌ ﻮﯾﺾ اﻟﺘﺮاﻛﯿ ﺰ اﻹﺑﺘﺪاﺋﯿ ﺔ ﻓ ﻲ ﺗﻌﺒﯿ ﺮ ﺛﺎﺑ ﺖ
اﻹﺗﺰان : K
] [ Productsο
=K
] [ Reactants
ο
ﺣﺘﻰ ﯾﺘﻜﻮن ﻛﻤﯿﺔ ﻻ ﺑﺄس ﺑﮭﺎ ﻣﻦ ﻓﯿﮫ اﻟﻜﻔﺎﯾﺔ ﺑﺤﯿﺚ ﺗﻨﺎﻓﺲ اﻟﻘﯿﻤﺔ اﻟﻤﻄﻠﻘﺔ ﻟﻠﺤﺪ ) ( ∆G
ο
اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ ،وھﺬا ﯾﻌﻨﻲ ﺗﺤﻮل اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ اﻟﻰ ﻣﻮاد ﻧﺎﺗﺠﺔ ﻛﻠﻤﺎ اﺗﺠﮫ اﻟﺘﻔﺎﻋﻞ
ﻧﺤﻮ اﻹﺗﺰان.
ب( إذا ﻛﺎﻧﺖ ﻗﯿﻤﺔ ) ( ∆Gﺑﺎﻟﻤﻮﺟﺐ ﻓﺈن ﻗﯿﻤﺔ ) (RT lnQﺳﻮف ﺗﻜﻮن أﻛﺜﺮ ﺳﺎﻟﺒﯿﺔ ﻣﻦ
ο
ﻃﺎﻟﻤﺎ أﻧﮫ ﯾﻨﺘﺞ ﻛﻤﯿﺔ ﻗﻠﯿﻠﺔ ﻣﻦ اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ ،وھﺬا ﯾﻌﻨﻲ أن ﺗﺮاﻛﯿﺰ ) ( ∆G
ο
ﻗﯿﻤﺔ اﻟﺤﺪ
اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ ﺳﻮف ﯾﺒﻘﻰ ﻋﺎﻟﯿﺎً إذا ﻗﻮرن ﺑﺘﺮاﻛﯿﺰ اﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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( ∆Gوﻗﯿﻤﺔ راﺋﺰ اﻟﺘﻔﺎﻋﻞ ) (Q = Kوﺑﺎﻟﺘﺎﻟﻲ ﻓﺈن )= 0 ج( ﻋﻨﺪ اﻟﺘﻮازن ﻓﺈن ﻗﯿﻤﺔ
اﻟﻤﻌﺎدﻟﺔ ﺗﺼﺒﺢ :
ο
ΔG = ΔG + RT lnQ
ο
0 = ΔG + RT lnK
ο
ΔG = - RT lnK
وﺗﻌﺘﺒﺮ اﻟﻤﻌﺎدﻟﺔ :
ο
ΔG = - RT lnK
ﻣﻦ أھﻢ اﻟﻤﻌﺎدﻻت ﻓﻲ ﻋﻠﻢ اﻟﺜﯿﺮﻣﻮدﯾﻨﺎﻣﯿﻚ )اﻟﺪﯾﻨﺎﻣﯿﻜﺎ اﻟﺤﺮارﯾﺔ( ﻟﺮﺑﻄﮭﺎ ﺛﺎﺑﺖ اﻟﺘﻮازن
. ( ΔG ο
ﻟﻠﺘﻔﺎﻋﻞ ) (Kﺑﺎﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ )
ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺘﻔﺎﻋﻼت اﻟﺘﻲ ﻟﮭﺎ ﻗﯿﻤﺎً ﻛﺒﯿﺮة ﺟﺪاً أو ﺻﻐﯿﺮة ﺟﺪاً ﻟﺜﺎﺑﺖ اﻹﺗﺰان ھﻨﺎك ﺻﻌﻮﺑﺔ
ﺷﺪﯾﺪة ،إذا ﻟﻢ ﺗﻜﻦ اﺳﺘﺤﺎﻟﺔ ،ﻓﻲ ﺣﺴﺎب ﻗﯿﻢ Kﻣﻦ ﺗﺮاﻛﯿﺰ اﻟﻤﺘﻔﺎﻋﻼت.
ﻓﻤﺜﻼً ﻟﺘﻜﻮﯾﻦ أﻛﺴﯿﺪ اﻟﻨﯿﺘﺮوﺟﯿﻦ ) (NOﻣﻦ اﻷﻛﺴﺠﯿﻦ اﻟﺠﺰﯾﺌﻲ واﻟﻨﯿﺘﺮوﺟﯿﻦ اﻟﺠﺰﯾﺌﻲ :
)→ 2NO(g
N 2 (g) + O2 (g) ←
] [ NO 2
=K
] [ N ] .[ O2 2
إن ﻗﯿﻤﺔ ) (Kcاﻟﻤﻨﺨﻔﻀﺔ ﺟﺪاً ﺗﻌﻨﻲ أن ﺗﺮﻛﯿﺰ NOﻋﻨﺪ اﻹﺗﺰان ﺳﻮف ﯾﻜﻮن ﻗﻠﯿﻼً ﺟﺪاً.
ﻗ ﺪ ﯾﻜ ﻮن ﻣ ﻦ اﻷﺳ ﮭﻞ ﻓ ﻲ ھ ﺬه اﻟﺤﺎﻟ ﺔ اﺳ ﺘﺨﺮاج ﻗﯿﻤ ﺔ Kcﻣ ﻦ اﻟﺘﻐﯿ ﺮ ﻓ ﻲ اﻟﻄﺎﻗ ﺔ اﻟﺤ ﺮة
اﻟﻘﯿﺎﺳﯿﺔ ) ( ∆G οﻟﻠﺘﻔﺎﻋﻞ.
ﺑﺎﻟﻤﻘﺎﺑﻞ ﻧﺠ ﺪ أن ﺛﺎﺑ ﺖ اﻹﺗ ﺰان ﻟﺘﻜ ﻮن ﯾﻮدﯾ ﺪ اﻟﮭﯿ ﺪروﺟﯿﻦ ) (HIﻣ ﻦ اﻟﮭﯿ ﺪروﺟﯿﻦ اﻟﺠﺰﯾﺌ ﻲ
واﻟﯿﻮد اﻟﺠﺰﯾﺌﻲ ﯾﻘﺘﺮب ﻣﻦ اﻟﻮﺣﺪة ﻋﻨﺪ درﺟﺔ ﺣﺮارة اﻟﻐﺮﻓﺔ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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)→ 2HI(g
H 2 (g) + I 2 (g) ←
ﺳ ﻮف ο
ΔG = - RT lnK وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن ﻗﯿ ﺎس Kﻟﻠﺘﻔﺎﻋ ﻞ ﺛ ﻢ ﺣ ﺴﺎب ) ( ∆G οﻣ ﻦ اﻟﻤﻌﺎدﻟ ﺔ
ﻟﻠﺘﻔﺎﻋﻞ. ) ( ΔH , ΔS
ο ο
ﯾﻜﻮن أﺳﮭﻞ ﻣﻦ ﻗﯿﺎس
ً
ﻭﻓﻘﺎ ﻟﻘﻴﻢ ) ( ΔG
ο
K ﻗﻴﻢ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ
ο
ΔG = - RT lnK
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﯾﻮﺿﺢ اﻟﺸﻜﻞ ) (٣٢ ،٣١ ،٣٠ﻣﻨﺤﻨﯿﺎت اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﻟﻤﻨﻈﻮﻣﺔ ﻣﺘﻔﺎﻋﻠﺔ ،ﻣﻊ ﻣﺪى اﻟﺘﻔﺎﻋ ﻞ
ﻟﻨﻮﻋﯿﻦ ﻣﻦ اﻟﺘﻔﺎﻋﻼت.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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Fig. 32 : Variation in total free energy for a reversible reaction carried at constant T.
The standard free energy change, ( ∆Gο ) , represents the free energy change for the
standard reaction – the complete conversion of reactants into products. In (a) this
change is negative, indicating that the standard reaction is product-favored
(spontaneous); the collection of just products would be more stable than the collection
of just reactants. The mixture of reactants and products corresponding to the minimum
of the curve is even more stable, however, and represents the equilibrium mixture.
Because ( ∆Gο ) is negative , K > 1 , and the equilibrium mixture contains more
products than reactants. At any point on the curve, comparing Q and K indicates the
direction in which the reaction must proceed to approach equilibrium, that is, which
way is 'downhill' in free energy. The plot an (b) is for positive ( ∆Gο ) (the standard
reaction is reactant-favored). In this case K < 1 , and the equilibrium mixture contains
more reactants than products.
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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Fig. 33 : The total free energy of a reaction mixture as a function of the progress of the
reaction. Beginning with either pure reactants or pure products, the free energy
decreases ( ΔG is negative ) as the system moves toward equilibrium. The graph is
drawn assuming that the pure reactants and pure products in their standard states and
the ΔG ο for the reaction is negative so the equilibrium composition is rich in products.
(٥٢) ﻣﺜﺎﻝ
→ HCl(g) + CHCl3 (L)
CCl 4 (L) + H 2 (g) ←
.(R = 8.314 J/K. mol) ﻋﻠﻤﺎً ﺑﺄن، 25 ºC أ( اﺣﺴﺐ ﺛﺎﺑﺖ اﻟﺘﻮازن ﻋﻨﺪ
ﺛﻢ ﺣﺪد (PH2
= 10 atm, PHCl = 0.1 atm ) ∆ ( ﻟﻠﺘﻔﺎﻋﻞ ﻋﻨﺪﻣﺎ ﯾﻜﻮن ﺿﻐﻂG ) ب( اﺣﺴﺐ
.اﺗﺠﺎه اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ھﺬه اﻟﻈﺮوف
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ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ:ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ
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ﺍﳊﻞ
ln K =
( -103.72 × 10 J ) 3
= 41.864
- [ (8.314 J/K mol) × (298 K) ]
41.864 18
K=e = 1.52 x 10
(PH2
= 10 atm, PHCl = 0.1 atm )
: ﻧﺘﺒﻊ اﻟﻌﻼﻗﺔ
ο
ΔG = ΔG + RT lnQ
PHCl
ΔG = ΔG + RT ln
ο
H
P 2
PHCl
ΔG = (- 103.72 × 10 J) + (8.314 J/K mol)(298 K) ln
3
H
P 2
10
ΔG = - 115129.64 J
ΔG = - 115.13 kJ
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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وﺑﻤﺎ أن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤ ﺮة ﺑﺎﻟ ﺴﺎﻟﺐ ) ( ΔG = -ﻓ ﺈن اﻟﺘﻔﺎﻋ ﻞ ﯾﻜ ﻮن ﺗﻠﻘﺎﺋﯿ ﺎً وﯾ ﺴﯿﺮ
ﺑﺎﻟﺘﺎﻟﻲ ﻣﻦ اﻟﯿﺴﺎر )اﻟﻤﺘﻔﺎﻋﻼت( اﻟﻰ اﻟﯿﻤﯿﻦ )اﻟﻨﻮاﺗﺞ(.
ﻣﺜﺎﻝ )(٥٣
ﻋﻨﺪ درﺟﺔ ﺣﺮارة .25 ºCاﺣﺴﺐ ) ( ΔGﻟﮭﺪرﺟﺔ اﻹﯾﺜﻠﯿﻦ C2H4ﻋﻨﺪ ھﺬه اﻟﺪرﺟﺔ ﻣﻦ
ο
اﻟﺤﺮارة.
ﺍﳊﻞ
ο
ΔG = - RT lnK
ο
) ΔG = - (8.314 J/K. mol) (298 K) (ln 5.04 x 10
17
ο
ΔG = - 100989.186 J
ο
ΔG = - 100.989 kJ
ﻣﺜﺎﻝ )(٥٤
اﺣﺴﺐ ) ( ΔG οﻟﻜﻠﻮرﯾﺪ اﻟﻔﻀﺔ ) (AgClﻋﻨﺪ درﺟﺔ ﺣﺮارة ) (25 °Cإذا ﻋﻠﻤ ﺖ أن ﺛﺎﺑ ﺖ
اﻟﺬوﺑﺎﻧﯿﺔ )) . (Ksp = 1.6 x 10-10ﺣﯿﺚ )(R = 8.314 J/K. mol
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﳊﻞ
اﻟﻤﻮﺟﺒﺔ اﻟﻌﺎﻟﯿﺔ ﺗﺘﻔﻖ ﻣﻊ ﺣﻘﯿﻘ ﺔ أن AgClﯾ ﺬوب ﺑﻘﻠ ﺔ وﺑﺎﻟﺘ ﺎﻟﻲ ﻓ ﺈن اﻹﺗ ﺰان وﻗﯿﻤﺔ ) ( ΔG
ο
ﻣﺜﺎﻝ )(٥٥
)→ 2NH 3 (g
N 2 (g) + 3H 2 (g) ←
إن اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة اﻟﻘﯿﺎﺳﯿﺔ ﻟﻠﺘﻔﺎﻋﻞ :
ھ ﻮ ) (- 33.2 kJوإن ﺛﺎﺑ ﺖ اﻹﺗ ﺰان ) (Kp = 6.59 × 105ﻋﻨ ﺪ درﺟ ﺔ اﻟﺤ ﺮارة (25
) . °Cوﻛﺎﻧﺖ اﻟﻀﻐﻮط اﻹﺑﺘﺪاﺋﯿﺔ ﻛﺎﻵﺗﻲ :
(P H2
= 0.25 atm, PN = 0.870 atm, PNH = 12.9 atm
2 3
)
اﺣﺴﺐ ∆Gﻟﮭﺬا اﻟﺘﻔﺎﻋﻞ ﻋﻨﺪ ﺗﻠﻚ اﻟﻀﻐﻮط وﺗﻨﺒﺄ ﺑﺎﺗﺠﺎه اﻟﺘﻔﺎﻋﻞ.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﺍﳊﻞ
وﺑﻤﺎ أن اﻟﻘﯿﻤﺔ ﺑﺎﻟﺴﺎﻟﺐ ﻓﺈن اﻟﺘﻔﺎﻋﻞ ﺗﻠﻘﺎﺋﻲ وﯾﺴﯿﺮ ﻣﻦ اﻟﯿﺴﺎر اﻟﻰ اﻟﯿﻤﯿﻦ.
ﻣﺜﺎﻝ )(٥٦
ﻣﺴﺘﺨﺪﻣﺎً اﻟﻨﺘﺎﺋﺞ ﻟﻘﯿﻢ ﺣﺮارة اﻟﺘﻜﻮﯾﻦ اﻟﻘﯿﺎﺳﯿﺔ اﺣﺴﺐ ﺛﺎﺑﺖ اﻹﺗﺰان ﻟﻠﺘﻔﺎﻋﻞ اﻟﺘﺎﻟﻲ :
)→ 2H 2 (g) + O2 (g
2H 2 O(L) ←
و R = 8.314 J/mol ) 25ﻋﻠﻤ ﺎً ﺑ ﺄن K ﻋﻨ ﺪ درﺟ ﺔ اﻟﺤ ﺮارة °C
) ( ΔG (H O) = - 237.2 kJ/mol
ο
2
ﺍﳊﻞ
وﺑﻤﺎ أن ﻗﯿﻤﺔ اﻟﺘﻐﯿﺮ ﻓﻲ اﻟﻄﺎﻗﺔ اﻟﺤﺮة ﺑﺎﻟﻤﻮﺟﺐ ﻓﺈن ھﺬا اﻟﺘﻔﺎﻋﻞ ﻏﯿﺮ ﺗﻠﻘﺎﺋﻲ.
وﻟﺤﺴﺎب ﻗﯿﻢ ﺛﺎﺑﺖ اﻹﺗﺰان Kﻧﺘﺒﻊ اﻟﻌﻼﻗﺔ :
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ΔG ο = - RT lnK
474.4 × 103 J = - (8.314) × (298 K) ln K
ln K = - 191.478
K = e - 191.478
K= 6.95 × 10-84
ﻗﯿﻤﺔ Kاﻟﻤﻨﺨﻔﻀﺔ ﺗﺪل ﻋﻠﻰ أن ﺗﺤﻮل اﻟﻤﺎء اﻟ ﻰ ﻏ ﺎزي اﻟﮭﯿ ﺪروﺟﯿﻦ واﻷﻛ ﺴﺠﯿﻦ ﻣ ﻨﺨﻔﺾ
ﺟﺪاً اﻟﻰ ﻗﯿﻤﺔ ﯾﻤﻜﻦ إھﻤﺎﻟﮭﺎ واﻟﻘﻮل ﺑﺄن ھﺬا اﻟﺘﻔﺎﻋﻞ ﻻ ﯾﺤﺪث.
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٥٧
ﻣﺜﺎﻝ )(٥٨
إذا اﻣﺘﺺ ﻧﻈﺎم ﻣﺎ ﻛﻤﯿﺔ ﻣﻦ اﻟﺤﺮارة ﻋﻨﺪ ﺛﺒﻮت اﻟﺤﺠﻢ ﻗﺪرھﺎ ) (50 Jﻓﺈن :
ب( اﻟﻤﺤﯿﻂ ﺑﺬل ﺷﻐﻼً ﻋﻠﻰ اﻟﻨﻈﺎم أ( اﻟﻨﻈﺎم ﺑﺬل ﺷﻐﻼً ﻋﻠﻰ اﻟﻤﺤﯿﻂ
د( ﻻ ﺗﻮﺟﺪ إﺟﺎﺑﺔ ﺻﺤﯿﺤﺔ ﻓﯿﻤﺎ ﺳﺒﻖ. ج( اﻟﻨﻈﺎم واﻟﻤﺤﯿﻂ ﻟﻢ ﯾﺒﺬﻻ أي ﺷﻐﻞ
ﻣﺜﺎﻝ )(٥٩
0.6 mlﻣﻦ اﻟﻤﺎء اﻟﺴﺎﺋﻞ ﺗﺠﻤﺪ ﻓﺄﺻﺒﺢ ﺣﺠﻤﮫ 0.7 mlﻋﻨﺪ ) (1 atmﻓ ﺈن اﻟ ﺸﻐﻞ ﺑﻮﺣ ﺪة
اﻟﺠﻮل ﺗﺴﺎوي :
د( – 1 × 10-4 ج( 101.3 ب( – 9 × 104 أ( – 0.01
ﻣﺜﺎﻝ )(٦٠
اﻟﺸﻐﻞ اﻟﺬي ﯾﺘﻢ اﻧﺠﺎزه ﺑﻮاﺳﻄﺔ ﺗﻔﺎﻋﻞ ﻛﯿﻤﯿﺎﺋﻲ داﺧﻞ ﻗﻨﺒﻠﺔ ﻣﺴﻌﺮﯾﺔ ﺗﺴﺎوي :
د( W > 0 ج( zero ب( 101300 أ( 101.3
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٦١
ﻏ ﺎز ﻣﺜ ﺎﻟﻲ ﺣﺠﻤ ﮫ 2.5 Lﺗﻤ ﺪد ﻓﺄﺻ ﺒﺢ ﺣﺠﻤ ﮫ 4 Lﻋﻨ ﺪ 25 °Cﻓ ﺈن اﻟ ﺸﻐﻞ اﻟ ﺬي ﯾ ﺘﻢ
اﻧﺠﺎزه ﻋﻨﺪﻣﺎ ﯾﺘﻤﺪد اﻟﻐﺎز ﺿﺪ اﻟﻔﺮاغ ﯾﺴﺎوي :
د( W > 0 ج( zero ب( 101300 أ( 101.3
ﻣﺜﺎﻝ )(٦٢
ﻋﻨﺪ ﺛﺒﻮت اﻟﺤﺠﻢ ﻓﺈن ﻛﻤﯿﺔ اﻟﺤﺮارة ) (qVاﻟﻤﻌﻄﺎة ﻟﺘﻔﺎﻋﻞ ﻛﯿﻤﯿﺎﺋﻲ ﻣﻌﯿﻦ ﺗﺴﺎوي :
د( W ج( ∆E ب( T أ( ΔH
ﻣﺜﺎﻝ )(٦٤
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٦٧
ﻣﺜﺎﻝ )(٦٨
ﺣﯿﻨﻤﺎ ﺗﻜﻮن ﺟﻤﯿﻊ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ واﻟﻨﺎﺗﺠﺔ ﻣﻦ ﺗﻔﺎﻋﻞ ﻣﺎ ﻋﺒ ﺎرة ﻋ ﻦ ﺳ ﻮاﺋﻞ وﻛ ﺎن اﻟﺘﻔﺎﻋ ﻞ
ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ﻓﺈن اﻟﻔﻘﺮات اﻟﺘﺎﻟﯿﺔ ﺻﺤﯿﺤﺔ ﻋﺪا :
ج( ΔH = ∆E + ∆nRT ب( ΔH = q P أ( ΔH = ΔE
ﻣﺜﺎﻝ )(٦٩
ﻋﻨﺪ ﺣﺮق ﻣﻮل واﺣﺪ ﻣﻦ اﻟﺒﻨﺰﯾﻦ ﺣﺮﻗﺎً ﺗﺎﻣﺎً ﻓﻲ ﺟﻮ ﻣﻦ اﻷﻛﺴﺠﯿﻦ ﻋﻨﺪ 25 °Cوﺿﻐﻂ 1
C 6 H 6 (L) + 15/2O 2 (g)
atmﺣﺴﺐ اﻟﻤﻌﺎدﻟﺔ اﻟﺘﺎﻟﯿﺔ → 6CO 2 (g) + 3H 2 O(g) :
د( W = 0 ج( ΔH > ΔE ب( ΔH < ΔE أ( ΔH = ΔE
ﻣﺜﺎﻝ )(٧٠
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ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ :ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻚ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ
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ﻣﺜﺎﻝ )(٧٢
أي اﻟﺤﺎﻻت اﻟﺘﺎﻟﯿﺔ ﯾﻜﻮن ﻓﯿﮭﺎ اﻟﺘﻔﺎﻋﻞ ﻣﻤﻜﻨﺎً ﻣﮭﻤﺎ ﻛﺎﻧﺖ درﺟﺔ اﻟﺤﺮارة :
د( ∆H > 0, ∆S > 0 ∆H < 0, ج( ∆S < 0 ∆H > 0, ب( ∆S < 0 ∆H < 0, أ( ∆S > 0
ﻣﺜﺎﻝ )(٧٧
أي اﻟﺤﺎﻻت اﻟﺘﺎﻟﯿﺔ ﻻ ﯾﻜﻮن اﻟﺘﻔﺎﻋﻞ ﻓﯿﮭﺎ ﻣﻤﻜﻨﺎً ﻣﮭﻤﺎ ﻛﺎﻧﺖ درﺟﺔ اﻟﺤﺮارة :
د( ∆H > 0, ∆S > 0 ∆H < 0, ج( ∆S < 0 ∆H > 0, ب( ∆S < 0 ∆H < 0, أ( ∆S > 0
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