‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎ�ﻲ‬

‫ﻣﻌﺎﺩﻻﺕ ﺍﳊﺎﻟﺔ ‬

‫‪Equations of State‬‬
‫‪Equations of state‬‬ ‫ﻣﻌﺎﺩﻻﺕ ﺍﳊﺎﻟﺔ ‪ -‬ﺣﺎﻟﺔ ﺍﻟﻨﻈﺎﻡ ‪ -‬ﺧﺼﺎﺋﺺ ﺍﻟﻨﻈﺎﻡ‬ ‫‪1-2‬‬

‫ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﰲ ﺍﻟﺪﻳﻨﺎﻣﻴﻜﺎ ﺍﳊﺮﺍﺭﻳ‪‬ﺔ ﻫﻲ ﻣﻌﺎﺩﻟﺔ ﺭﻳﺎﺿﻴ‪‬ﺔ ﺗﺮﺑﻂ ﺑﻴ‪‬ﻦ ﻣﺘﻐﲑﺍﺕ ﻧﻈﺎﻡ ﺛﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻲ ﻣﺎ‪ .‬ﺗ‪‬ﻈﻬﺮ ﺍﻟﺘﺠﺮﺑﺔ‬

‫ﺐ ﺃ ﹾﻥ ﺗﺄﺧ ﹶﺬ ﻗﻴﻤﹰﺎ ﳏﺪ‪‬ﺩﺓ‪ ،‬ﺃﻱ‬

‫ﰲ ﺩﻳﻨﺎﻣﻴﻜﺎ ﺍﳊﺮﺍﺭﺓ ﺃ ﱠﻥ ﺗﺜﺒﻴﺖ ﺑﻌﺾ ﺍﳌﺘﻐﲑﺍﺕ ﻳﺆﺩﻱ ﺇﱃ ﺃ ﱠﻥ ﺍﳌﺘﻐﲑﺍﺕ ﺍﻟﺒﺎﻗﻴﺔ ﳚ ‪‬‬

‫ﻻﻋﺸﻮﺍﺋﻴﺔ‪ .‬ﻭﺍﳌﺜﺎﻝ ﻋﻠﻰ ﺫﻟﻚ ﻫﻮ ﻭﺿﻊ ﻏﺎ ٍﺯ ﻣﻌﲔ ﰲ ﻭﻋﺎﺀ ﻣﻐﻠﻖ ﳏﺪ‪‬ﺩ ﺍﳊﺠﻢ ‪ V‬ﻣﻮﺟﻮﺩ ﻋﻠﻰ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ‬

‫ﳏﺪ‪‬ﺩﺓ ‪ .T‬ﺗﺜﺒﻴﺖ ﺍﳊﺠﻢ ﻳﻌﲏ ﺛﺒﺎﺕ ﻛﺘﻠﺔ ﺍﻟﻐﺎﺯ ‪ m‬ﺍﳌﻤﻜﻦ ﺍﺳﺘﺨﺪﺍﻣﻬﺎ ﻭﰲ ﻫﺬﻩ ﺍﳊﺎﻟﺔ ﻭﺑﺘﺜﺒﻴﺖ ‪ T‬ﻓﺈ ﱠﻥ ﺿﻐﻂ‬

‫ﺍﻟﻐﺎﺯ ‪ P‬ﺩﺍﺧﻞ ﺍﻟﻮﻋﺎﺀ ﻳﺄﺧﺬ ﻗﻴﻤ ﹰﺔ ﳏﺪ‪‬ﺩﺓ‪.‬‬

‫ﻳ‪‬ﻤﻜﻦ ﺍﻟﺘﻌﺒﲑ ﺭﻳﺎﺿﻴﹰﺎ ﻋﻦ ﺍﻟﻌﻼﻗﺔ ﺍﻟﱵ ﺗﺮﺑﻂ ﺑ‪‬ﻴﻦ ﺍﳌﺘﻐﲑﺍﺕ ﺍﻷﺭﺑﻌﺔ ﺍﻟﺴﺎﺑﻘﺔ ﻛﻤﺎ ﻳﻠﻲ‪:‬‬

‫‪f (P,V,T,m) = 0‬‬ ‫)‪(1-2‬‬

‫ﺚ ﺗﺘﻀﻤﻨﻬﺎ‬
‫‪‬ﺗﺴﻤ‪‬ﻰ ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﺴﺎﺑﻘﺔ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻠﻨﻈﺎﻡ‪ .‬ﻗﺪ ﻳﻠﺰﻣﻨﺎ ﰲ ﺑﻌﺾ ﺍﻷﻧﻈﻤﺔ ﺇﺿﺎﻓﺔ ﻣﺘﻐﲑﺍﺕ ﺃﹸﺧﺮﻯ ﲝﻴ ﹸ‬

‫ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ‪ -‬ﻣﺜﻞ ﻣﺴﺎﺣﺔ ﻭﺳﻄﺢ ﺍﻟﺸﺪ ﰲ ﺳﻄﺢ ﺳﺎﺋﻞ‪-‬ﲞﺎﺭ‪ ،‬ﺍﳌﻐﻨﻄﺔ ﻭﻛﺜﺎﻓﺔ ﺍﻟﺘﺪﻓﻖ ﰲ ﻣﺎﺩﺓ ﻣﻐﻨﺎﻃﻴﺴﻴ‪‬ﺔ ‪-...‬‬

‫‪ .‬ﺳﻮﻑ ﻧﻌﺘﱪ ﻫﻨﺎ ﺃﻧﻈﻤﺔ ﻳ‪‬ﻤﻜﻦ ﻭﺻﻔﻬﺎ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﳌﺘﻐﲑﺍﺕ ﺍﻷﺭﺑﻌﺔ ﺍﻟﺴﺎﺑﻘﺔ‪ .‬ﻳﻤﻜﻦ‪ ،‬ﻭﻳ‪‬ﻔﻀ‪‬ﻞ‪ ،‬ﻛﺘﺎﺑﺔ ﻣﻌﺎﺩﻟﺔ‬

‫ﺍﳊﺎﻟﺔ ‪ 1-2‬ﺍﻟﺴﺎﺑﻘﺔ ﺑﺎﺳﺘﺨﺪﺍﻡ ﻣﺘﻐﲑﺍﺕ ﻣ‪‬ﺮﻛﱠﺰﺓ ﻟﻠﻨﻈﺎﻡ ﻭﺫﻟﻚ ﺑﺎﺳﺘﺒﺪﺍﻝ ﺍﳊﺠــﻢ ‪ V‬ﺑﺎﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ‪ ،‬ﺍﻟﻐﺮﺍﻣﻲ‬

‫ﺃﻭ ﺍﳌﻮﱄ‪ v ،‬ﻭﺗ‪‬ﺼﺒﺢ ﺍﳌﻌﺎﺩﻟﺔ ‪ 1-2‬ﻋﻠﻰ ﺍﻟﺼﻴﻐﺔ‪:‬‬

‫‪f (P,v,T) = 0‬‬ ‫)‪(2-2‬‬

‫ﺗﻜﻮﻥ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻋﺎﺩﺓ ﻣﻌﻘﺪﺓ ﺑﻌﺾ ﺍﻟﺸﻲﺀ؛ ﻭﻧﻠﺠﹸﺄ ﺇﱃ ﲤﺜﻴﻞ ﺍﻟﻌﻼﻗﺔ ﺑﻴ‪‬ﻦ ﺍﳌﺘﻐﲑﺍﺕ ﺑﻴﺎﻧﻴﹰﺎ ﻟﻔﻬﻤﻬﺎ‪ .‬ﺳﻮﻑ ﻧﺮﻯ‬

‫ﰲ ﺍﻟﻔﻘﺮﺓ ﺍﻟﺘﺎﻟﻴﺔ ﺗﻌﺮﻳﻔﹰﺎ ﻟﻠﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻭﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻪ‪ .‬ﹸﺛﻢ‪ ‬ﻧﺘﻄﺮ‪‬ﻕ ﳌﻌﺎﺩﻟﺔ ﺣﺎﻟﺔ ﻣﺸﻬﻮﺭﺓ ﻫﻲ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‬

‫ﻭﺃﺧﲑﹰﺍ ﳌﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﳌﺎﺩﺓ ﺣﻘﻴﻘﻴ‪‬ﺔ‪ .‬ﺳﻮﻑ ﻧﺪﺭﺱ ﺑﺎﺳﺘﻔﺎﺿﺔ ﺍﻟﺘﻤﺜﻴﻞ ﺍﻟﺒﻴﺎﱐ ﳌﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻠﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻭﻟﻠﻐﺎﺯﺍﺕ‬

‫ﺍﳊﻘﻴﻘﻴ‪‬ﺔ ﻓﻴﻤﺎ ﻳ‪‬ﺴﻤ‪‬ﻰ ﺑﺴﻄﻮﺡ ‪ PVT‬ﻛﻤﺎ ﺳﻮﻑ ﻧ‪‬ﻌﺮ‪‬ﻑ ﺍﻟﺘﻤﺪﺩﻳ‪‬ﺔ ﻭﺍﻻﻧﻀﻐﺎﻃﻴ‪‬ﺔ ﻭﻧﺘﻌﻠﻢ ﻛﻴﻒ ﺗ‪‬ﻜﺘﺐ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ‬

‫ﺑﺎﺳﺘﺨﺪﺍﻡ ﻫﺬﻳ‪‬ﻦ ﺍﳌﻔﻬﻮﻣﻴ‪‬ﻦ‪.‬‬

 ‫א‬

‫‪Equation of state for an ideal gas‬‬ ‫ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ‬ ‫‪2-2‬‬

‫‪‬ﻳﻤﺜﱢﻞ ﺍﻟﺸﻜﻞ ﺍﻟﺒﻴﺎﱐ ﺍﻟﺘﺎﱄ )‪ (1-2‬ﺍﻟﻨﺘﺎﺋﺞ ﺍﳌﺨﱪﻳ‪‬ﺔ ﺍﻟﱵ ﳓﺼﻞ ﻋﻠﻴﻬﺎ ﻋﻨﺪ ﻭﺿﻊ ﻏﺎﺯ ﺛﺎﱐ ﺃﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ﰲ‬

‫ﺣﺠﻢ ‪ V‬ﻭﲢﺖ ﺩﺭﺟﺎﺕ ﺣﺮﺍﺭﺓ ﳐﺘﻠﻔﺔ ‪ .T3 > T2 > T1‬ﻳ‪‬ﻤﺜﱢﻞ ﺍﶈﻮﺭ ﺍﻷﻓﻘﻲ ﺿﻐﻂ ﺍﻟﻐﺎﺯ ﺍﳌﻘﺎﺱ ﻭﺍﶈﻮﺭ‬

‫ﺍﻟﻌﻤﻮﺩﻱ ﻗﻴﻤﺔ ﺍﳌﺘﻐﲑ ‪) Pv/T‬ﺣﻴﺚ ‪ v‬ﺗ‪‬ﻤﺜﱢﻞ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺍﳌﻮﱄ(‪ .‬ﻧ‪‬ﻼﺣﻆ ﻣﻦ ﻫﺬﺍ ﺍﻟﺸﻜﻞ ﺃ ﱠﻥ‪:‬‬

‫ﺍﳌﻨﺤﻨﻴﺎﺕ ﺍﻟﻨﺎﲡﺔ ﻣﻠﺴﺎﺀ ‪smooth‬؛‬

‫ﺗﺆﻭﻝ ﺍﳌﻨﺤﻨﻴﺎﺕ ﺍﻟﺜﻼﺛﺔ ﺇﱃ ﻧﻔﺲ ﺍﻟﻨﻘﻄﺔ ﺃ‪‬ﻳﹰﺎ ﻛﺎﻧﺖ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻨﺪﻣﺎ ﺗﺆﻭﻝ ‪ P‬ﺇﱃ ﺍﻟﺼﻔﺮ؛‬

‫‪‬ﺗﺜﺒﺖ ﺍﻟﺘﺠﺮﺑﺔ ﺃ ﱠﻥ ﺍﳌﻨﺤﻨﻴﺎﺕ ﺍﳌﻤﺎﺛﻠﺔ ﺍﳌﺴﺘﺨﺮﺟﺔ ﺑﺎﺳﺘﺨﺪﺍﻡ ﻏﺎﺯﺍﺕ ﺃﹸﺧﺮﻯ ﺗﺆﺩﻱ ﺇﱃ ﻧﻔﺲ ﺍﳌﻼﺣﻈﺎﺕ‪ .‬ﺗ‪‬ﺴﻤ‪‬ﻰ‬

‫ﺍﻟﻘﻴﻤﺔ ﺍﻟﺜﺎﺑﺘﺔ ﺍﻟﱵ ﻳﺆﻭﻝ ﺇﻟﻴﻬﺎ ﺍﳌﺘﻐﲑ ‪ Pv/T‬ﻋﻨﺪﻣﺎ ﺗﺆﻭﻝ ‪ P‬ﺇﱃ ﺍﻟﺼﻔﺮ "ﺛﺎﺑﺖ ﺍﻟﻐﺎﺯ ﺍﻟﻜﻮﱐ" ﺃﻭ ﺛﺎﺑﺖ ﺍﻟﻐﺎﺯ ﺍﳌﺜﺎﱄ‬

‫)‪ (ideal gas constant‬ﻭﻳ‪‬ﺴﺘﺨﺪﻡ ﺍﳊﺮﻑ ‪ R‬ﻟﻠﺪﻻﻟﺔ ﻋﻠﻴﻪ‪ .‬ﺃﻱ ﺃ ﱠﻥ‪:‬‬

‫‪3v‬‬
‫‪OLP‬‬ ‫ ‪= 5 =  N- NLORPROH −  . −‬‬ ‫)‪(3-2‬‬
‫‪3→ 7‬‬

‫ﻫﺬﺍ ﻳﻌﲏ ﺃﻧ‪‬ﻪ ﻋﻨﺪ ﺿﻐﻮﻁ ﻣﻨﺨﻔﻀﺔ ﻳ‪‬ﻤﻜﻦ ﺃ ﹾﻥ ﻧﻜﺘﺐ‪:‬‬

‫‪Pv=RT‬‬ ‫)‪(4-2‬‬

‫ﺃﻭ‬

‫‪PV=nRT‬‬ ‫)‪(5-2‬‬

‫‪‬ﺗﺴﻤ‪‬ﻰ ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﺴﺎﺑﻘﺔ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻭﻳ‪‬ﻤﺜﱢﻞ ﺍﳋﻂ ﺍﳌﻨ‪‬ﻘﻂ ﰲ ﺍﻟﺸﻜﻞ )‪ (1-2‬ﺍﻟﻌﻼﻗﺔ ﺑ‪‬ﻴ ‪‬ﻦ ‪ P v / T‬ﻭ‬

‫‪ P‬ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻭﺍﻟﱵ ﺗﻌﲏ ﺃ ﱠﻥ ﺍﻟﻌﻼﻗﺔ ﺑﻴﻨﻬﻤﺎ ﺧﻄﻴﺔ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪2 -‬‬ ‫‬

 ‫א‬

‫‪T 3 > T2 > T1‬‬ ‫ﺍﻟﺸﻜﻞ ‪ P = f(Pv/T) :1-2‬ﻟﺜﺎﱐ ﺃﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ﻟﺜﻼﺙ ﺩﺭﺟﺎﺕ ﺣﺮﺍﺭﺓ‬

‫ﻣﺜﺎﻝ ‪:1-2‬‬
‫ﺃ( ﺍﺳﺘﺨﺪﻡ ﺍﻟﺸﻜﻞ ‪ 1-2‬ﻟﺘﻘﺪﻳﺮ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺍﳌﻮﱄ ﻟﺜﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ﻋﻨﺪ ﺿﻐﻂ‬

‫‪ P = 3 × 107 N.m-2‬ﻭﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ‪.T1 = 340 K‬‬

‫ﺏ( ﻣﺎ ﻫﻮ ﻋﺪﺩ ﺍﳌﻮﻻﺕ ﺍﻟﺬﻱ ﳛﻮﻳﻪ ﻭﻋﺎﺀ ﺣﺠﻤﻪ ‪ 0.5 m3‬ﲢﺖ ﺍﻟﻀﻐﻂ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﻟﺴﺎﺑﻘﻴ‪‬ﻦ؟‬

‫ﺝ( ﻛﻢ ﻛﻴﻠﻮﻣﻮﻝ ﳛﺘﻮﻱ ﺍﻟﻮﻋﺎﺀ ﺍﻟﺴﺎﺑﻖ ﻟﻮ ﻛﺎﻥ ﺍﻟﻐﺎﺯ ﻣﺜﺎﻟﻴﺎﹰ؟‬

‫ﺍﳊﻞ‪:‬‬
‫ﺃ( ﻣﻦ ﺍﻟﺸﻜﻞ ‪ 1-2‬ﳒﺪ ﺃ ﱠﻥ ﻗﻴﻤﺔ ‪ Pv/ T‬ﺍﳌﺮﺍﺩﻓﺔ ﻟﻠﻀﻐﻂ ‪ P = 3 ×107 N.m-2‬ﺗﺴﺎﻭﻱ ﺗﻘﺮﻳﺒﹰﺎ‪:‬‬

‫‪4.5×10-3 J kilomole-1 K-1‬‬

‫‪3v‬‬ ‫ﺃﻱ ﺃ ﱠﻥ‪:‬‬
‫‪(3 =  ×   ) =  N- NLORPROH − . −‬‬
‫‪7‬‬
‫ ×   × ‬
‫=‪v‬‬ ‫‬ ‫ ‪= ×    P  NLORPROH −‬‬ ‫ﻭﺑﺎﻟﺘﺎﱄ ﻓﺈ ﱠﻥ‪:‬‬
‫ × ‬
‫‪9‬‬ ‫‬
‫‪Q‬‬ ‫=‬ ‫‪=  NLORPROH‬‬ ‫ﺏ(‬
‫‪v‬‬ ‫   × ‬

‫‪39‬‬ ‫ ×   × ‬
‫*‪Q,‬‬ ‫=‬ ‫‪=  NLORPROH‬‬ ‫ﺝ( ﻟﻮ ﻛﺎﻥ ﺍﻟﻐﺎﺯ ﻣﺜﺎﻟﻴﹰﺎ ﻓﺈ ﱠﻥ‪:‬‬
‫‪57‬‬ ‫ ×   × ‬

‫ﻭﺍﻟﻔﺮﻕ ﺍﻟﺬﻱ ﻇﻬﺮ ﺑﲔ ﻋﺪﺩ ﺍﳌﻮﻻﺕ ﰲ ﺏ ﻭ ﺝ ﻳﻌﲏ ﺃ ﱠﻥ ﺍﻟﻐﺎ ‪‬ﺯ ﻟﻴﺲ ﻣﺜﺎﻟﻴﹰﺎ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪3 -‬‬ ‫‬

 ‫‪P-v-T‬‬

‫ﻟﻐﺎﺯ ﻣﺜﺎﱄ‬ ‫‪P-v-T‬‬ ‫ﺳﻄﺢ‬ ‫‪3-2‬‬

‫ﺇﺫﺍ ﻣﺜﱠﻠﻨﺎ ﺑﻴﺎﻧﻴﹰﺎ ﺍﻟﻌﻼﻗﺔ ﺑﻴ‪‬ﻦ ﺍﳌﺘﻐﲑﺍﺕ ﺍﻟﺜﻼﺛﺔ ﰲ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻨﻈﺎﻡ ‪ P-v-T‬ﰲ ﻣﺴﺘﻮﻯ ﺩﻳﻜﺎﺭﰐ ﳏﺎﻭﺭﻩ ﺍﻟﺜﻼﺛﺔ‬

‫‪P-v-T‬‬ ‫ﺗ‪‬ﻤﺜﱢﻞ ‪ P‬ﻭ ‪ v‬ﻭ ‪ T‬ﻓﺈ ﱠﻥ ﺍﻟﺸﻜﻞ ﺍﻟﻨﺎﺗﺞ ﻋﺒﺎﺭﺓ ﻋﻦ ﺳﻄﺢ‪ .‬ﰲ ﺣﺎﻟﺔ ﺍﻟﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻧ‪‬ﺴﻤ‪‬ﻲ ﻫﺬﺍ ﺍﻟﺴﻄﺢ "ﺳﻄﺢ‬

‫ﻟﻐﺎﺯ ﻣﺜﺎﱄ"‪ .‬ﻟﻜﻲ ﻧﻔﻬﻢ ﻃﺒﻴﻌﺔ ﻫﺬﺍ ﺍﻟﺴﻄﺢ ﺩﻋﻨﺎ ﻧﺮﺳﻢ ﻣﺴﻘﻄﻴﻪ ﻋﻠﻰ ﻣﺴﺘﻮﻯ ‪ P v‬ﻭﻣﺴﺘﻮﻯ ‪ P T‬ﻋﻠﻰ ﺍﻟﺘﻮﺍﱄ‪.‬‬

‫‪‬ﻳﻤﺜﱢﻞ ﺍﻟﺸﻜﻞ ‪ 2-2‬ﺍﻟﺘﺎﱄ ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻣﺜﺎﱄ‪.‬‬

‫ﺍﻟﺸﻜﻞ ‪ :2-2‬ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻣﺜﺎﱄ‪.‬‬

‫ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪P-v‬‬ ‫ﻣﺴﻘﻂ ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻣﺜﺎﱄ‬ ‫‪1-3-2‬‬

‫ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺛﺎﺑﺘﺔ ﺗ‪‬ﻜﺘﺐ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻋﻠﻰ ﺍﻟﺼﻮﺭﺓ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬
‫‪constant‬‬
‫= ‪P‬‬ ‫)‪(6-2‬‬
‫‪v‬‬

‫ﺃﻱ ﺃ ﱠﻥ ﺍﳌﻨﺤﲎ ﺍﻟﺬﻱ ﻳ‪‬ﻤﺜﱢﻞ ﺍﻟﻀﻐﻂ ﺑﺪﻻﻟﺔ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻋﺒﺎﺭﺓ ﻋﻦ "ﻗﻄﻊ ﻧﺎﻗﺺ ﻣﺘﻜﺎﻓﺊ ﺍﻷﺿﻼﻉ‬

‫)‪ - (equilateral hyperbola‬ﺃﹸﻧﻈﺮ ﺍﻟﺸﻜﻞ ‪ .2-2‬ﻛﺎﻥ ﺭﻭﺑﺮﺕ ﺑﻮﻳﻞ )‪ (Robert Boyle‬ﻫﻮ ﻣﻦ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪4 -‬‬ ‫‬

 ‫‪P-v-T‬‬

‫ﺍﻛﺘﺸﻒ )‪ (1660‬ﺃ ﱠﻥ ﺣﺎﺻﻞ ﺿﺮﺏ ﺍﻟﻀﻐﻂ ﰲ ﺍﳊﺠﻢ ﻟﻜﺘﻠﺔ ﺛﺎﺑﺘﺔ ﻣﻦ ﻏﺎﺯ ﺣﻘﻴﻘﻲ ﲢﺖ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺛﺎﺑﺘﺔ‬

‫ﻳﺒﻘﻰ ﺗﻘﺮﻳﺒﹰﺎ ﺛﺎﺑﺘﹰﺎ‪ .‬ﺃﻱ ‪ P v = R T‬ﻭﺗ‪‬ﻌﺮﻑ ﻫﺬﻩ ﺍﻟﻌﻼﻗﺔ ﺑﻘﺎﻧﻮﻥ ﺑﻮﻳﻞ‪.‬‬

‫‪P-T‬‬ ‫ﻣﺴﻘﻂ ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬ ‫‪2-3-2‬‬

‫ﻭﻋﻨﺪ ﺣﺠﻢ ﺛﺎﺑﺖ ﻓﺈ ﱠﻥ ﺍﻟﻌﻼﻗﺔ ﺑﲔ ﺍﻟﻀﻐﻂ ‪ P‬ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ‪ T‬ﺧﻄ‪‬ﻴﺔ‪:‬‬

‫‪3‬‬ ‫=‬ ‫‪FRQVWDQW × 7‬‬ ‫‪ Q 5  7‬‬ ‫‪ 5  7‬‬

‫‪ 9 ‬‬ ‫‪Y‬‬

‫ﻭﺗﻜﻮﻥ ﺍﻟﻌﻼﻗﺔ ﺧﻄﻴ‪‬ﺔ ﺃﻳﻀﹰﺎ ﺑﲔ ‪ v‬ﻭ ‪ T‬ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ‪.‬‬

‫‪9 = FRQVWDQW × 7‬‬ ‫‪ Q 5  7‬‬

‫‪ 3 ‬‬

‫‪P-T‬‬ ‫ﻣﺴﻘﻂ ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬ ‫‪3-3-2‬‬

‫ﺍﻟﺸﻜﻞ ‪ :3-2‬ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ‪ P-v-T‬ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ﺍﻟﺸﻜﻞ ‪ :4-2‬ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ‪ P-v-T‬ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬

‫‪PT‬‬ ‫‪Pv‬‬

‫ﻛﻞ ﺣﺎﻟﺔ ﺍﺗﺰﺍﻥ ﳑﻜﻨﺔ ﻟﻠﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻣ‪‬ﻤﺜﹼﻠﺔ ﺑﻨﻘﻄﺔ ﻋﻠﻰ ﻫﺬﺍ ﺍﻟﺴﻄﺢ‪ ،‬ﻭﺗ‪‬ﻤﺜﱢﻞ ﻛﻞﱡ ﻧﻘﻄﺔ ﻋﻠﻰ ﺍﻟﺴﻄﺢ ﺣﺎﻟﺔ ﺍﺗﺰﺍﻥ‬

‫ﻂ ﻋﺒﺎﺭﺓ ﻋﻦ ﺳﻠﺴﻠﺔ ﻣﻦ ﺣﺎﻻﺕ‬

‫ﻂ ﻣﻦ ﺍﳋﻄﻮﻁ ﻋﻤﻠﻴ‪‬ﺔ ﺷﺒﻪ ﺳﺎﻛﻨﺔ‪ ،‬ﻷ ﱠﻥ ﻛ ﱠﻞ ﺧ ﱟ‬
‫ﳏﺘﻤﻠﺔ ﻟﻠﻐﺎﺯ ﺍﳌﺜﺎﱄ‪ .‬ﻳ‪‬ﻤﺜﱢﻞ ﻛﻞﱡ ﺧ ﱟ‬

‫ﺍﻻﺗﺰﺍﻥ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪5 -‬‬ ‫‬

 ‫א‬

‫ﻣﻌﺎﺩﻻﺕ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﺣﻘﻴﻘﻲ‬ ‫‪4-2‬‬

‫‪The Van der Waals equation‬‬ ‫ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‬ ‫‪1-4-2‬‬

‫ﻫﻨﺎﻙ ﻧﻮﻋﺎﻥ ﻣﻦ ﻣﻌﺎﺩﻻﺕ ﺍﳊﺎﻟﺔ ﺍﻟﱵ ﺍﻗﺘﺮﺣﺖ ﻟﺘﻔﺴﲑ ﺳﻄﻮﺡ ‪ P-v-T‬ﻟﻠﻐﺎﺯﺍﺕ ﺍﳊﻘﻴﻘﻴﺔ‪:‬‬

‫‪ -‬ﺗﻠﻚ ﺍﳌﺒﻨﻴ‪‬ﺔ ﻋﻠﻰ ﺍﻟﺘﺠﺮﺑﺔ )‪ (empirical‬ﻭﺍﻟﱵ ﺗﺴﺘﻨﺞ ﻣﻌﺎﻣﻼ‪‬ﺎ ﻣﻨﻬﺎ‪،‬‬

‫‪ -‬ﻭﺗﻠﻚ ﺍﳌﹸﺴﺘﻤﺪ‪‬ﺓ ﻣﻦ ﻧﻈﺮﻳ‪‬ﺔ ﺍﻟﻐﺎﺯ ﺃﻭ ﺍﻟﻨﻈﺮﻳ‪‬ﺔ ﺍﳊﺮﻛﻴ‪‬ﺔ ‪.kinetic theory‬‬

‫ﺐ ﺃ ﹾﻥ ﺗﺆﻭﻝ ﺇﱃ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﺣﻘﻴﻘﻲ ﻋﻨﺪ‬

‫ﻳﺸﺘﺮﻙ ﺍﻟﻨﻮﻋﺎﻥ ﰲ ﺧﺎﺻﻴ‪‬ﺔ ﻣﻬﻤﺔ ﺟﺪﹰﺍ ﻭﻫﻲ ﺃ ﱠﻥ ﻫﺬﻩ ﺍﳌﻌﺎﺩﻻﺕ ﳚ ‪‬‬

‫ﺚ ﺑﺴﺎﻃﺘﻬﺎ ﻭﰲ‬
‫ﺣﺠﻮﻡ ﻧﻮﻋﻴ‪‬ﺔ ﻛﺒﲑﺓ ﻧﺴﺒﻴﹰﺎ‪ .‬ﻣﻦ ﺑﻴ‪‬ﻦ ﻫﺬﻩ ﺍﳌﻌﺎﺩﻻﺕ ﺗﺘﻤ‪‬ﻴﺰ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺍﻟﺘﺎﻟﻴﺔ ﻣﻦ ﺣﻴ ﹸ‬

‫ﻧﻔﺲ ﺍﻟﻮﻗﺖ ﻗﺪﺭﺗ‪‬ﻬﺎ ﻋﻠﻰ ﺗﻔﺴﲑ ﻇﻮﺍﻫﺮ ﻛﺜﲑ ٍﺓ ﺧﺎﺻﺔ ﺑﺎﻟﻐﺎﺯﺍﺕ‪.‬‬

‫‪‬‬ ‫‪D ‬‬

‫‪ 3    (v − E ) = 5 7‬‬ ‫)‪(7-2‬‬
‫‪‬‬ ‫‪v ‬‬
‫ﺚ ‪ a‬ﻭ ‪ b‬ﺛﺎﺑﺘﺎﻥ ﻟﻐﺎ ٍﺯ ﻣﺎ‪ .‬ﲣﺘﻠﻒ ﻗﻴﻤﺔ ﺍﻟﺜﺎﺑﺘﻴ‪‬ﻦ ﻣﻦ ﻏﺎﺯ ﻵﺧﺮ ﻭﰲ ﺍﳉﺪﻭﻝ ‪ 1-2‬ﺍﻟﺘﺎﱄ ﻗﻴﻤﺔ ‪ a‬ﻭ ‪ b‬ﻟﺒﻌﺾ‬
‫ﺣﻴ ﹸ‬

‫ﺍﻟﻐﺎﺯﺍﺕ‪.‬‬

‫)‪b (m3 kilomole-1‬‬ ‫)‪a (J m3 kilomole-2‬‬ ‫ﺍﳌﺎﺩﺓ‬

‫‪0.0234‬‬ ‫‪3.44 × 103‬‬ ‫‪He‬‬ ‫ﺍﳍﻴﻠﻴﻮﻡ‬
‫‪0.0266‬‬ ‫‪24.8‬‬ ‫‪H2‬‬ ‫ﺍﳍﻴﺪﺭﻭﺟﲔ‬
‫‪0.0318‬‬ ‫‪138‬‬ ‫‪O2‬‬ ‫ﺍﻷﻛﺴﺠﲔ‬
‫‪0.0429‬‬ ‫‪366‬‬ ‫‪CO2‬‬ ‫ﺛﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ‬
‫‪0.0319‬‬ ‫‪580‬‬ ‫‪H2O‬‬ ‫ﺍﳌﺎﺀ‬
‫‪0.0055‬‬ ‫‪292‬‬ ‫‪Hg‬‬ ‫ﺍﻟﺰﺋﺒﻖ‬
‫ﻓﺎﻟﺲ ‪ a‬ﻭ ‪b‬‬ ‫ﺍﳉﺪﻭﻝ ‪ :1-2‬ﻗﻴﻢ ﺛﺎﺑﱵ ﻓﺎﻥ ﺩ ‪‬ﺭ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪6 -‬‬ ‫‬

 ‫א‬

‫ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺗﺆﻭﻝ ﺇﱃ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻋﻨﺪﻣﺎ ﻳ‪‬ﺼﺒﺢ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻛﺒﲑﹰﺍ‬ ‫‪2-4-2‬‬

‫ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻣﻦ ﺍﻟﻨﻮﻉ ﺍﻟﺜﺎﱐ ﺍﻟﺬﻱ ﺫﻛﺮﻧﺎﻩ ﰲ ﺑﺪﺍﻳﺔ ﻫﺬﻩ ﺍﻟﻔﻘﺮﺓ ﺃﻱ ﻣﻦ ﺍﳌﹸﻌﺎﺩﻻﺕ ﺍﻟﱵ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﺍﻟﻨﻈﺮﻳ‪‬ﺔ‬

‫ﺍﳊﺮﻛﻴ‪‬ﺔ‪ .‬ﺑﻔﻀﻞ ﺍﻟﻨﻈﺮﻳ‪‬ﺔ ﺍﳊﺮﻛﻴ‪‬ﺔ ‪-‬ﻭﰲ ﻓﻴﺰﻳﺎﺀ ﺍﳉﺰﻳﺌﺎﺕ ‪ -molecular physics‬ﻳﻈﻬﺮ ﺍﳊﺪ ‪ a/v2‬ﻋﻨﺪ‬

‫ﺃﺧﺬ ﺍﻟﻘﻮﻯ ﺑﻴ‪‬ﻦ ﺟﺰﻳﺌﺎﺕ ﺍﻟﻐﺎﺯ )‪ (intermolecular forces‬ﺑﻌﲔ ﺍﻻﻋﺘﺒﺎﺭ ﻭﺍﻟﺜﺎﺑﺖ ‪ b‬ﻳﺘﻨﺎﺳﺐ ﻃﺮﺩﻳﹰﺎ ﻣﻊ‬

‫ﺍﳊﺠﻢ ﺍﻟﺬﻱ ﲢﺘﻠﱡﻪ ﻫﺬﻩ ﺍﳉﺰﻳﺌﺎﺕ‪ .‬ﻋﻠﻰ ﺍﻟﺮﻏﻢ ﻣﻦ ﺫﻟﻚ ﻓﺈﻧ‪‬ﻨﺎ ﺳﻮﻑ ﻧﺘﻌﺎﻣﻞ ﻣﻊ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺍﻵﻥ ﻭﻛﺄﻧ‪‬ﻬﺎ‬

‫ﻼ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺤﺠﻢ‬
‫ﻣﻦ ﺍﻟﻨﻮﻉ ﺍﻷﻭﻝ ﺍﻟﺘﺠﺮﻳﱯ‪ .‬ﻋﻨﺪﻣﺎ ﻳ‪‬ﺼﺒﺢ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻛﺒﲑﹰﺍ ﻳ‪‬ﺼﺒﺢ ﺣﺠﻢ ﺍﳉﺰﻱﺀ ﻣﻬﻤ ﹰ‬

‫ﺍﻟﻜﻠﻲ ﻟﻠﻐﺎﺯ ﻭﺗﺆﻭﻝ ﺍﻟﻘﻮﻯ ﺑﻴ‪‬ﻦ ﺍﳉﺰﻳﺌﺎﺕ‪-‬ﺍﻟﱵ ﺗﺰﺩﺍﺩ ﺍﳌﺴﺎﻓﺔ ﺑﻴﻨﻬﺎ‪ -‬ﺇﱃ ﺍﻟﺼﻔﺮ ﻋﻨﺪﻣﺎ ﺗﺆﻭﻝ ‪ v‬ﺇﱃ ﻗﻴﻢ ﻛﺒﲑﺓ ﻭﻟﺬﺍ‬

‫ﻼ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﻤﺘﻐﲑ ‪ v‬ﻭﺗﺆﻭﻝ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻛﻤﺎ‬ ‫ﻓﺈ ﱠﻥ ﺍﳊ ‪‬ﺪ ‪ a/v2‬ﻳ‪‬ﺼﺒﺢ ﻣ‪‬ﻬﻤ ﹰ‬
‫ﻼ ﺃﻣﺎﻡ ‪ P‬ﻭﺍﻟﺜﺎﺑﺖ ‪ b‬ﻣ‪‬ﻬﻤ ﹰ‬

‫ﻫﻮ ﻣﺘﻮﻗﱠﻊ ﻭﻣﻄﻠﻮﺏ ﺇﱃ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ‪.P v = R T :‬‬

‫ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‬ ‫‪3-4-2‬‬

‫‪‬ﻳ‪‬ﺒﻴ‪‬ﻦ ﺍﻟﺸﻜﻞ ‪ 1-5-2‬ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻭﺍﻟﺸﻜﻞ ‪ 2-5-2‬ﻣﺴﻘﻂ ﻫﺬﺍ ﺍﻟﺴﻄﺢ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬

‫‪ P-v‬ﻟﻌﺪﺩ ﻣﻦ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺎﺕ‪ .‬ﻧﺴﺘﻄﻴﻊ ﻛﺘﺎﺑﺔ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺑﺪﻻﻟﺔ ‪ v‬ﻭ ﻗﻮﺍﻫﺎ )ﺃﻱ ‪ v2 ،v‬ﻭ ‪ ( v3‬ﻛﻤﺎ‬

‫ﻳﻠﻲ‪:‬‬

‫‪P v3 - ( P b + R T) v2 + a v - a b = 0‬‬ ‫)‪(8-2‬‬

‫ﺃﻱ ﺃ ﱠﻥ ﻫﺬﻩ ﺍﳌﻌﺎﺩﻟﺔ ﺗﻜﻌﻴﺒﻴ‪‬ﺔ ﰲ ‪ ، v‬ﻭﻟﻘﻴﻢ ‪ P‬ﻭ ‪ T‬ﻣﻌﻴ‪‬ﻨﺔ ﻓﺈ ﱠﻥ ﳍﺬﻩ ﺍﳌﹸﻌﺎﺩﻟﺔ ﺛﻼﺛﺔ ﺟﺬﻭﺭ ﻭﻭﺍﺣﺪ ﻣﻨﻬﺎ ﳚﺐ ﺃ ﹾﻥ‬

‫ﻳﻜﻮﻥ ﺣﻘﻴﻘﻴﹰﺎ‪ .‬ﻫﻨﺎﻙ ﺛﻼﺙ ﺣﺎﻻﺕ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺰﻭﺝ ‪ P‬ﻭ ‪:T‬‬

‫‪ -‬ﻋﻨﺪ ﺩﺭﺟﺎﺕ ﺍﳊﺮﺍﺭﺓ ﺍﳌﻨﺨﻔﻀﺔ‪ ،‬ﻣﺜﻞ ‪ T1‬ﰲ ﺍﻟﺸﻜﻞ ‪ 2-5-2‬ﻳﻮﺟﺪ ﺛﻼﺛﺔ ﺟﺬﻭﺭ ﺣﻘﻴﻘﻴ‪‬ﺔ ﳌﺪﻯ ﻣﻌﲔ ﻣﻦ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪7 -‬‬ ‫‬

 ‫א‬

‫ﻗﻴﻢ ﺍﻟﻀﻐﻂ‪.‬‬

‫‪ -‬ﺑﺰﻳﺎﺩﺓ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻓﺈ ﱠﻥ ﺍﳉﺬﻭﺭ ﺍﻟﺜﻼﺛﺔ ﺗﻘﺘﺮﺏ ﻣﻦ ﺑﻌﻀﻬﺎ ﺣﺘ‪‬ﻰ ﻧﺼﻞ ﺇﱃ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﳏﺪ‪‬ﺩﺓ ﻫﻲ ‪، Tc‬‬

‫ﺗ‪‬ﺴﻤ‪‬ﻰ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ ﺗ‪‬ﺼﺒﺢ ﺍﳉﺬﻭﺭ ﺍﻟﺜﻼﺛﺔ ﻋﻨﺪﻫﺎ ﻣﺘﺴﺎﻭﻳﺔ ﻭﺗ‪‬ﺴﻤ‪‬ﻰ ﻫﺬﻩ ﺍﻟﻨﻘﻄﺔ ‪ :‬ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ‬

‫)ﺍﻟﻨﻘﻄﺔ ‪- c.p‬ﻭﳘﺎ ﺍﳊﺮﻑ ﺍﻷﻭﻝ ﻣﻦ ﻛ ﱟﻞ ﻣﻦ ﺍﻟﻜﻠﻤﺘﻴ‪‬ﻦ ‪(critical point‬‬

‫‪ -‬ﻓﻮﻕ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ ﻫﺬﻩ ﻻ ﻳ‪‬ﻮﺟﺪ ﺇ ﱠﻻ ﺟﺬﺭ ﺣﻘﻴﻘﻲ ﻭﺍﺣﺪ ﻷﻳ‪‬ﺔ ﻗﻴﻤﺔ ﻟﻠﻤﺘﻐﲑ ‪.P‬‬

‫ﺍﻟﺸﻜﻞ ‪ :2-5-2‬ﻣﺴﻘﻂ ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ‬ ‫ﺍﻟﺸﻜﻞ ‪ :1-5-2‬ﺳﻄﺢ ‪ P-v-T‬ﻟﻐﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ‬

‫‪P-v‬‬ ‫ﻓﺎﻟﺲ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬ ‫ﻓﺎﻟﺲ‬

‫ﺻﻴﻐﺔ ﺃﹸﺧﺮﻯ ﳌﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﳌﺎﺩﺓ ﺣﻘﻴﻘﻴﺔ‬ ‫‪4-4-2‬‬

‫ﻣﻦ ﺻﻴﻎ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﺍﳌﺴﺘﺨﺪﻣﺔ ﻟﻠﺘﻌﺒﲑ ﻋﻦ ﺣﺎﻟﺔ ﻏﺎﺯ ﺣﻘﻴﻘﻲ ﺍﻟﺼﻴﻐﺔ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬
‫‪B C‬‬
‫‪3 v = A‬‬ ‫ ‪+  +‬‬ ‫)‪(9-2‬‬
‫‪v‬‬ ‫‪v‬‬

‫ﺚ ‪ B ،A‬ﻭ ‪ ... ،C‬ﺩﻭﺍﻝ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻭﺗ‪‬ﺪﻋﻰ " ‪."virial coefficients‬‬
‫ﺣﻴ ﹸ‬

‫ﻱ ِﻟﻤﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻳﺆﺩﻱ ﺇﱃ ﻣﻌﺎﺩﻟﺔ ﻋﻠﻰ ﺍﻟﺼﻴﻐﺔ‬

‫ﻋﻨﺪ ﺍﻓﺘﺮﺍﺽ ﻗﺎﻧﻮﻥ ﻗﻮﺓ ﺑﲔ ﺟﺰﻳﺌﺎﺕ ﺍﻟﻐﺎﺯ ﻓﺈ ﱠﻥ ﺍﻻﺷﺘﻘﺎﻕ ﺍﻟﻨﻈﺮ ‪‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪8 -‬‬ ‫‬

 ‫א‬

‫ﺍﻟﺴﺎﺑﻘﺔ‪ .‬ﻓﻠﻠﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻣﺜﻼﹰ‪ ،‬ﻣﻦ ﺍﻟﻮﺍﺿﺢ ﺃ ﱠﻥ ﺍﳌﻌﺎﻣﻞ )‪ A(T‬ﻳﺴﺎﻭﻱ ‪ RT‬ﻭﺃ ﱠﻥ ﺍﳌﻌﺎﻣﻼﺕ ﺍﻟﺒﺎﻗﻴﺔ ‪... ،C ،B‬‬

‫ﺗﺴﺎﻭﻱ ﺻﻔﺮﹰﺍ‪ .‬ﻭﰲ ﺣﺎﻟﺔ ﻏﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻓﺈ ﱠﻥ ﺑﺎﻹﻣﻜﺎﻥ ﺟﻌﻞ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻋﻠﻰ ﺍﻟﺼﻴﻐﺔ )‪، (9-2‬‬

‫ﻭﺫﻟﻚ ﺑﻜﺘﺎﺑﺘﻬﺎ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻟﻨﻈﺮﻳ‪‬ﺔ ﺍﻟﺰﻭﺟﻴ‪‬ﺔ ‪.binomial theorem‬‬

‫ﺚ ﻳﻈﻬﺮ ﺍﳊﺪ ‪ P v‬ﻋﻠﻰ ﳝﲔ ﺍﳌﻌﺎﺩﻟﺔ ﻛﺎﻟﺘﺎﱄ‪:‬‬

‫ﺳﻮﻑ ‪‬ﻧ ‪‬ﺮﺗ‪‬ﺐ ﺃﻭ ﹰﻻ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﲝﻴ ﹸ‬
‫‪−‬‬
‫‪ E‬‬ ‫‪D‬‬
‫‪3 v = 5 7   ‬‬ ‫‪−‬‬ ‫ ‬ ‫)‪(10-2‬‬
‫‪ v‬‬ ‫‪v‬‬

‫ﻭﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻟﻨﻈﺮﻳ‪‬ﺔ ﺍﻟﺰﻭﺟﻴﺔ‪:‬‬

‫‪b b2‬‬
‫‪−1‬‬
‫‪1 - b ‬‬ ‫‪= 1 + + 2 + ...‬‬
‫‪‬‬ ‫‪‬‬ ‫)‪(11-2‬‬
‫‪‬‬ ‫‪v‬‬ ‫‪v v‬‬

‫ﻓﺈﻧ‪‬ﻨﺎ ﻧﺴﺘﻄﻴﻊ ﻛﺘﺎﺑﺔ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻋﻠﻰ ﺍﻟﺼﻴﻐﺔ‪:‬‬

‫‪R T b − a R T b2‬‬
‫‪Pv = RT+‬‬ ‫‪+‬‬ ‫‪+ ...‬‬ ‫)‪(12-2‬‬
‫‪v‬‬ ‫‪v2‬‬

‫ﺃﻱ ﺃ ﱠﻥ ﺍﻟﺜﻮﺍﺑﺖ ‪ B ،A‬ﻭ ‪ C‬ﻫﻲ‪:‬‬

‫‪A(T) = R T , B(T) = R T b - a ,‬‬ ‫‪C(T) = R T b2‬‬ ‫)‪(13-2‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪9 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫ﻟﻠﻤﻮﺍﺩ ﺍﳊﻘﻴﻘﻴﺔ‬ ‫‪P-v-T‬‬ ‫ﺳﻄﻮﺡ‬ ‫‪5-2‬‬

‫ﺃﻃﻮﺍﺭ ﺍﳌﺎﺩﺓ‬ ‫‪1-5-2‬‬

‫ﺗﺘﻮﺍﺟﺪ ﺍﳌﺎﺩﺓ ﰲ ﺃﻃﻮﺍﺭ ﺛﻼﺛﺔ ﻫﻲ‪ :‬ﺍﻟﺼﻼﺑﺔ‪ ،‬ﺍﻟﺴﻴﻮﻟﺔ ﻭﺍﻟﻐﺎﺯﻳ‪‬ﺔ‪ ،‬ﻭﺗﻌﺘﻤﺪ ﻫﺬﻩ ﺍﻷﻃﻮﺍﺭ ﻋﻠﻰ ﻣﺘﻐﲑﺍﺕ‬

‫ﺛﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴ‪‬ﺔ‪ .‬ﻭﰲ ﺃﻏﻠﺐ ﺍﻷﺣﻮﺍﻝ ﻳﻜﻮﻥ ﺍﻟﻀﻐﻂ ﻭﺍﳊﺠﻢ ﳘﺎ ﺍﳌﺘﻐﲑﺍﻥ ﺍﻟﻠﺬﺍﻥ ﻳ‪‬ﺤﺪ‪‬ﺩﺍﻥ ﺣﺎﻟﺔ ﺍﳌﺎﺩﺓ‪.‬‬

‫‪ -‬ﻃﻮﺭ ﺍﻟﺼﻼﺑﺔ‪ -‬ﺃﻭ ﺍﳊﺎﻟﺔ ﺍﻟﺼﻠﺒﺔ ﻟﻠﻤﺎﺩﺓ‪ :‬ﺘﺰ ﺍﻟﺬﱠﺭﺍﺕ ﺣﻮﻝ ﻧﻘﺎﻁ ﺛﺎﺑﺘﺔ ﺗﻮﺯﻳﻌﻬﺎ ﻣﻨﺘﻈﻢ )ﻛﻤﺎ ﰲ ﺍﳊﺎﻟﺔ‬

‫ﺍﻟﺒﻠﻮﺭﻳ‪‬ﺔ ‪ (crystals‬ﺃﻭ ﻋﺸﻮﺍﺋﻲ ﻏﲑ ﻣﻨﺘﻈﻢ )‪ .(amorphous‬ﻳﻜﻮﻥ ﺷﻜﻞ ﺍﳌﺎﺩﺓ ﻭﺍﳊﺠﻢ ﺍﻟﺬﻱ‬

‫ﲢﺘﻠﻪ ﺛﺎﺑﺘﺎﻥ ﰲ ﻫﺬﻩ ﺍﳊﺎﻟﺔ‪.‬‬

‫‪ -‬ﻃﻮﺭ ﺍﻟﺴﻴﻮﻟﺔ‪ -‬ﺃﻭ ﺍﳊﺎﻟﺔ ﺍﻟﺴﺎﺋﻠﺔ ﻟﻠﻤﺎﺩﺓ‪ :-‬ﻭﻓﻴﻬﺎ ﻻ ﻳﻜﻮﻥ ﻟﻠﻤﺎﺩﺓ ﺷﻜ ﹲﻞ ﺛﺎﺑﺖ ﺇ ﹾﺫ ﺗﺄﺧﺬ ﺷﻜﻞ ﺍﻟﻮﻋﺎﺀ ﺍﻟﺬﻱ‬

‫ﳛﻮﻳﻬﺎ ﻭﻟﻜﻦ ﻳﺒﻘﻰ ﺍﳊﺠﻢ ﺛﺎﺑﺘﹰﺎ‪.‬‬

‫‪ -‬ﻃﻮﺭ ﺍﻟﻐﺎﺯﻳ‪‬ﺔ‪ -‬ﺃﻭ ﺍﳊﺎﻟﺔ ﺍﻟﻐﺎﺯﻳ‪‬ﺔ ﻟﻠﻤﺎﺩﺓ‪ :-‬ﻭﻓﻴﻬﺎ ﺗﻜﻮﻥ ﺍﳌﺎﺩﺓ ﻣﺎﺋﻌﺔ ﻗﺎﺑﻠﺔ ﻟﻺﻧﻀﻐﺎﻁ ﻭﺍﻟﺘﻤﺪ‪‬ﺩ‪ .‬ﻳﺘﻐﲑ ﺍﳊﺠﻢ ﻫﻨﺎ‬

‫ﺣﺴﺐ ﺣﺠﻢ ﺍﻟﻮﻋﺎﺀ ﺍﻟﺬﻱ ﳛﻮﻱ ﺍﻟﻐﺎﺯ‪ .‬ﰲ ﻫﺬﻩ ﺍﻟﻔﻘﺮﺓ ﺳﻮﻑ ﻧﻌﺘﱪ ﺍﻟﻐﺎﺯﺍﺕ ﻭﻧﺪﺭﺱ ﺳﻄﻮﺡ‬

‫‪ P v T‬ﳍﺎ‪.‬‬

‫ﺍﳋﺼﺎﺋﺺ ﺍﻟﻌﺎﻣﺔ ﻟﺴﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺣﻘﻴﻘﻴﺔ‬ ‫‪2-5-2‬‬

‫ﻳ‪‬ﻤﺜﱢ ﹸﻞ ﺍﻟﺸﻜﻼﻥ ‪ 1-6-2‬ﻭ ‪ ،2-6-2‬ﻋﻠﻰ ﺍﻟﺘﺮﺗﻴﺐ‪ ،‬ﻣﻘﻄﻌﹰﺎ ﻭﺻﻔﻴﹰﺎ ﻣﻦ ﺳﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺗﺘﻘﻠﺺ ﺑﺎﻟﺘﱪﻳﺪ‬

‫)ﻣﺜﻞ ﺛﺎﱐ ﺃﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ‪ .(CO2‬ﻭﳌﺎﺩﺓ ﺗﺘﻤﺪ‪‬ﺩ ﺑﺎﻟﺘﱪﻳﺪ )ﻣﺜﻞ ﺍﳌﺎﺀ ‪.(H2O‬‬

‫ﺑﺸﻜﻞ ﻋﺎﻡ ﻳ‪‬ﻤﻜﻦ ﻣﻼﺣﻈﺔ ﻣﺎ ﻳﻠﻲ‪:‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪10 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫‪ -‬ﺗﺘﻮﺍﺟﺪ ﺍﳌﺎﺩﺓ ﺍﳊﻘﻴﻘﻴ‪‬ﺔ ﰲ ﻃﻮﺭ ﺍﻟﻐﺎﺯ ﻋﻨﺪ ﺩﺭﺟﺎﺕ ﺣﺮﺍﺭﺓ ﻋﺎﻟﻴﺔ ﺟﺪﹰﺍ ﻭﺿﻐﻮﻁ ﻣﻨﺨﻔﻀﺔ ﻓﻘﻂ‪ .‬ﻋﻨﺪ ﺩﺭﺟﺎﺕ‬

‫ﺣﺮﺍﺭﺓ ﻋﺎﻟﻴﺔ ﺟﺪﹰﺍ ﻭﺿﻐﻮﻁ ﻋﺎﻟﻴﺔ ﺗﺘﺤﻮﻝ ﺍﳌﺎﺩﺓ ﺇﱃ ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ ﺃﻭ ﻃﻮﺭ ﺍﻟﺼﻠﺐ‪.‬‬

‫‪ -‬ﰲ ﺑﻌﺾ ﻣﻨﺎﻃﻖ ﺍﻟﺴﻄﺢ‪ ،‬ﺃﻱ ﺿﻤﻦ ﻣﺪﻯ ﳏﺪ‪‬ﺩ ﻟﻠﻤﺘﻐﲑﺍﺕ ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴ‪‬ﺔ ﻻ ﺗﻮﺟﺪ ﺍﳌﺎﺩﺓ ﺇ ﱠﻻ ﰲ ﻃﻮﺭ‬

‫ﻭﺍﺣﺪ‪ :‬ﺻﻠﺐ‪ ،‬ﺳﺎﺋﻞ ﺃﻭ ﻏﺎﺯ )ﺃﻭ ﲞﺎﺭ(‪.‬‬

‫‪ -‬ﰲ ﻣﻨﺎﻃﻖ ﺃﹸﺧﺮﻯ ﻣﻦ ﺍﻟﺴﻄﺢ ﺗﺘﻮﺍﺟﺪ ﺍﳌﺎﺩﺓ ﰲ ﻃﻮﺭﻳ‪‬ﻦ ﰲ ﺣﺎﻟﺔ ﺍﺗﺰﺍﻥ ﰲ ﺁ ٍﻥ ﻭﺍﺣﺪ‪ :‬ﺻﻠﺐ‪-‬ﺳﺎﺋﻞ‪ ،‬ﺳﺎﺋﻞ‪-‬‬

‫ﻏﺎﺯ ﻭﻏﺎﺯ‪-‬ﺻﻠﺐ‪.‬‬

‫ﺍﻟﺸﻜﻞ ‪ :2-6-2‬ﺳﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺗﺘﻤﺪ‪‬ﺩ ﺑﺎﻟﺘﱪﻳﺪ‬ ‫ﺍﻟﺸﻜﻞ ‪ :1-6-2‬ﺳﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺗﺘﻘﻠﱠﺺ‬

‫)ﻣﺜﻞ ﺍﳌﺎﺀ ‪(H2O‬‬ ‫ﺑﺎﻟﺘﱪﻳﺪ )ﻣﺜﻞ ‪(CO2‬‬

‫ﻂ ﻭﺣﻴ ٍﺪ ﻳ‪‬ﺴﻤ‪‬ﻰ ﺍﳋﻂ ﺍﻟﺜﻼﺛﻲ ﺗﺘﻌﺎﻳﺶ ﺃﻃﻮﺍﺭ ﺍﳌﺎﺩﺓ ﺍﻟﺜﻼﺛﺔ ﻣﻌﹰﺎ‪.‬‬

‫ﻭﻋﻠﻰ ﻃﻮﻝ ﺧ ﱟ‬

‫ﻂ ﻣﻦ ﺍﳋﻄﻮﻁ ‪‬ﻳﻤﺜﱢ ﹸﻞ ﻋﻤﻠ‪‬ﻴ ﹰﺔ ﺷﺒ ‪‬ﻪ ﺳﺎﻛﻨﺔ ﺃﻭ ﺳﻠﺴﻠ ﹰﺔ ﻣﻦ ﺣﺎﻻﺕ ﺍﻻﺗﺰﺍﻥ‪.‬‬

‫ﻛﻤﺎ ﰲ ﺣﺎﻟﺔ ﺍﻟﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻓﺈ ﱠﻥ ﻛ ﱠﻞ ﺧ ﱟ‬

‫ﻭﺗ‪‬ﻤﺜﱢﻞ ﺍﳋﻄﻮﻁ ﺍﳌﺘﺼﻠﺔ ﰲ ﺍﻟﺸﻜﻠﻴ‪‬ﻦ ‪ 1-6-2‬ﻭ ‪ 2-6-2‬ﻋﻤﻠﻴﺎﺕ ﺃﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺔ‪.‬‬

‫‪‬ﺗﻤﺜﱢﻞ ﺍﳌﻨﺎﻃﻖ ﺍﳌﻈﻠﱠﻠﺔ ﻣﺎ ﻳ‪‬ﺴﻤ‪‬ﻰ ﺑﺎﻟﺴﻄﻮﺡ ﺍﳌﺴﻄﱠﺮﺓ ‪ ruled surfaces‬ﻭﺍﻟﺴﺒﺐ ﰲ ﻫﺬﻩ ﺍﻟﺘﺴﻤﻴﺔ ﻫﻮ ﺃﻧ‪‬ﻪ ﺇﺫﺍ‬

‫ﻭﺿﻌﻨﺎ ﺣﺎﻓﺔ ﻣﺴﺘﻮﻳﺔ )ﺣﺎﻓﺔ ﻣﺴﻄﺮﺓ( ﺑﺸﻜ ٍﻞ ﻣﻮﺍ ٍﺯ ﻟﻠﻤﺤﻮﺭ ‪ v‬ﻓﺈﻧ‪‬ﻬﺎ ﺳﺘﻼﻣﺲ ﺍﻟﺴﻄﺢ ﰲ ﲨﻴﻊ ﻧﻘﺎﻁ ﻫﺬﻩ‬

‫ﺍﻟﺴﻄﻮﺡ ﺍﳌﺴﻄﱠﺮﺓ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪11 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫‪P-T‬‬ ‫ﻣﺴﻘﻂ ﺳﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺣﻘﻴﻘﻴ‪‬ﺔ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬ ‫‪3-5-2‬‬

‫ﻳ‪‬ﻤﺜﱢﻞ ﺍﻟﺸﻜﻼﻥ ‪ 3-6-2‬ﻭ ‪ 4-6-2‬ﻣﺴﻘﻄﺎ ﺍﻟﺸﻜﻠﲔ ‪ 1-6-2‬ﻭ ‪ 2-6-2‬ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪ P-T‬ﻭﻧﻼﺣﻆ ﻣﺎ‬

‫ﻳﻠﻲ‪:‬‬

‫‪ -‬ﲤﻴﻞ ﺍﳋﻄﻮﻁ ﺍﻟﱵ ﺗ‪‬ﻤﺜﱢﻞ ﺗﻌﺎﻳﺶ ﺍﻟﻄﻮﺭﻳ‪‬ﻦ ﺻﻠﺐ‪-‬ﻏﺎﺯ ﻭ ﺍﻟﻄﻮﺭﻳ‪‬ﻦ ﺳﺎﺋﻞ‪-‬ﻏﺎﺯ ﺇﱃ ﺍﻟﻴﻤﲔ ﻭﺇﱃ ﺍﻷﻋﻠﻰ ﰲ‬

‫ﺍﳊﺎﻟﺘﻴ‪‬ﻦ )ﺍﻟﺘﻘﻠﺺ ﻭﺍﻟﺘﻤﺪ‪‬ﺩ ﺑﺎﻟﺘﱪﻳﺪ(‪.‬‬

‫ﺍﻟﺸﻜﻞ ‪2-6-2‬‬ ‫ﺍﻟﺸﻜﻞ ‪ :3-6-2‬ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ﰲ ﺍﻟﺸﻜﻞ ‪ 1-6-2‬ﺍﻟﺸﻜﻞ ‪ :4-6-2‬ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ﰲ‬

‫ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪PT‬‬ ‫ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪PT‬‬
‫‪ -‬ﲤﻴﻞ ﺍﳋﻄﻮﻁ ﺍﻟﱵ ﺗ‪‬ﻤﺜﱢﻞ ﺗﻌﺎﻳﺶ ﺍﻟﻄﻮﺭ‪‬ﻳﻦ ﺻﻠﺐ‪-‬ﺳﺎﺋﻞ ﺇﱃ ﺍﻷﻋﻠﻰ ﻭﺇﱃ ﺍﻟﻴﻤﲔ ﰲ ﺣﺎﻟﺔ ﺍﳌﻮﺍﺩ ﺍﻟﱵ ﺗﺘﻘﻠﺺ‬

‫ﺑﺎﻟﺘﱪﻳﺪ ﻭﺇﱃ ﺍﻷﻋﻠﻰ ﻭﺇﱃ ﺍﻟﻴﺴﺎﺭ ﰲ ﺣﺎﻟﺔ ﺍﳌﻮﺍﺩ ﺍﻟﱵ ﺗﺘﻤﺪ‪‬ﺩ ﺑﺎﻟﺘﱪﻳﺪ‪ .‬ﳓﺘﺎﺝ ﻟﺘﻔﺴﲑ ﻫﺬﻩ ﺍﳋﺎﺻﻴ‪‬ﺔ ﺇﱃ ﻣﻔﺎﻫﻴﻢ‬

‫ﻣﺘﻘﺪﻣﺔ ﺳﻨﺮﺍﻫﺎ ﻻﺣﻘﹰﺎ‪.‬‬

‫ﻳﻜﻮﻥ ﻣﺴﻘﻂ ﺍﳋﻂ ﺍﻟﺜﻼﺛﻲ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪ P-T‬ﻋﺒﺎﺭﺓ ﻋﻦ ﻧﻘﻄﺔ ﻭﺣﻴﺪﺓ ﺗ‪‬ﺴ ‪‬ﻤﻰ ﺍﻟﻨﻘﻄﺔ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ‬

‫‪ .triple point‬ﻭﻛﻨ‪‬ﺎ ﻗﺪ ﺫﻛﺮﻧﺎ ﰲ ﺍﻟﻔﺼﻞ ﺍﻷﻭﻝ ﺃ ﱠﻥ ﻧﻘﻄﺔ ﺍﳌﺎﺀ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ ﻫﻲ ﺍﻟﻨﻘﻄﺔ ﺍﳌﻌﻴﺎﺭﻳ‪‬ﺔ ﺍﻟﺜﺎﺑﺘﺔ ﺍﻟﱵ ﺃﹸﻋﻄﻴﺖ‬

‫ﳍﺎ ﺍﻟﻘﻴﻤﺔ ‪.273.16 K‬‬

‫‪‬ﻳ‪‬ﺒﻴ‪‬ﻦ ﺍﳉﺪﻭﻝ ‪ 2-2‬ﺍﻟﺘﺎﱄ ﺇﺣﺪﺍﺛﻴﺎﺕ ﺍﻟﻨﻘﻄﺔ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ ﻟﺒﻌﺾ ﺍﳌﻮﺍﺩ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪12 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫‪Torr‬‬ ‫ﺍﻟﻀﻐﻂ‬ ‫)‪T(K‬‬ ‫ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﻨﻘﻄﺔ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ‬ ‫ﺍﳌﺎﺩﺓ‬

‫‪38.3‬‬ ‫‪2.186‬‬ ‫)‪He (4‬‬ ‫ﺍﳍﻴﻠﻴﻮﻡ ‪4‬‬
‫‪52.8‬‬ ‫‪13.84‬‬ ‫‪H2‬‬ ‫ﺍﳍﻴﺪﺭﻭﺟﲔ‬
‫‪128‬‬ ‫‪18.63‬‬ ‫‪D2‬‬ ‫ﺍﻟﺪﻭﺗﲑﻳﻮﻡ‬
‫‪324‬‬ ‫‪24.57‬‬ ‫‪Ne‬‬ ‫ﺍﻟﻨﻴﻮﻥ‬
‫‪1.14‬‬ ‫‪54.36‬‬ ‫‪O2‬‬ ‫ﺍﻷﻛﺴﺠﲔ‬
‫‪45.57‬‬ ‫‪195.40‬‬ ‫‪NH3‬‬ ‫ﺍﻷﻣﻮﻧﻴﺎ‬
‫‪3880‬‬ ‫‪216.55‬‬ ‫‪CO2‬‬ ‫ﺛﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ‬
‫‪1.256‬‬ ‫‪197.68‬‬ ‫‪SO2‬‬ ‫ﺛﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﱪﻳﺖ‬
‫‪4.58‬‬ ‫‪273.15‬‬ ‫‪H2O‬‬ ‫ﺍﳌﺎﺀ‬
‫ﺍﳉﺪﻭﻝ ‪ :2-2‬ﺇﺣﺪﺍﺛﻴﺎﺕ ﺍﻟﻨﻘﻄﺔ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ ﻟﺒﻌﺾ ﺍﳌﻮﺍﺩ‬

‫ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪P-v‬‬ ‫ﻣﺴﻘﻂ ﺳﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺣﻘﻴﻘﻴ‪‬ﺔ‬ ‫‪4-5-2‬‬

‫ﳌﺰﻳ ٍﺪ ﻣﻦ ﺍﻟﺘﻮﺿﻴﺢ‪ ،‬ﻳ‪‬ﻤﺜﱢﻞ ﺍﻟﺸﻜﻼﻥ ‪ 5-6-2‬ﻭ ‪ 6-6-2‬ﻣﺴﻘﻄﺎ ﺍﻟﺸﻜﻠﲔ ‪ 1-6-2‬ﻭ ‪ 2-6-2‬ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ‬

‫‪ P-v‬ﻭﺍﳌﻼﺣﻈﺎﺕ ﺍﻟﺼﺎﳊﺔ ﰲ ﺣﺎﻟﺔ ﺍﳌﺴﻘﻂ ﻋﻠﻰ ﺍﳌﺴﺘﻮﻯ ‪ P-T‬ﻫﻲ ﻧﻔﺴﻬﺎ ﻛﺎﻣﻠ ﹰﺔ‪.‬‬

‫ﺍﻟﺸﻜﻞ ‪2-6-2‬‬ ‫ﺍﻟﺸﻜﻞ ‪ :5-6-2‬ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ﰲ ﺍﻟﺸﻜﻞ ‪ 1-6-2‬ﺍﻟﺸﻜﻞ ‪ :6-6-2‬ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ﰲ‬

‫ﺍﳌﺴﺘﻮﻯ ‪Pv‬‬ ‫ﻋﻠﻰ‬ ‫ﺍﳌﺴﺘﻮﻯ ‪Pv‬‬ ‫ﻋﻠﻰ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪13 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫ﲢﻮﻻﺕ ﺍﳌﺎﺩﺓ )ﺗﻐﲑﺍﺕ ﺣﺎﻟﺔ ﺍﳌﺎﺩﺓ(‬ ‫‪5-5-2‬‬

‫ﺱ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺍﻟﱵ ﲡﻌﻞ ﺍﻟﻨﻈﺎﻡ ﻳﺘﺤﻮﻝ ﻣﻦ ﺍﳊﺎﻟﺔ ﺍﳌﻌﺮ‪‬ﻓﺔ ﺑﺎﻟﻨﻘﻄﺔ ‪ a‬ﺣﺘ‪‬ﻰ ﺍﻟﻨﻘﻄﺔ ‪ f‬ﻋﻠﻰ‬
‫ﻟﻨﺄﺧﺬ ﺍﻟﺸﻜﻞ ‪ 1-6-2‬ﻭﻧﺪﺭ ‪‬‬

‫ﻃﻮﻝ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ ‪ .T2‬ﻟﻨﺘﺨﻴﻞ ﺍﳌﺎﺩﺓ ﳏﺼﻮﺭﺓ ﰲ ﺃﺳﻄﻮﺍﻧﺔ ﻣﻐﻠﻘﺔ ﲟﻜﺒﺲ ﻣﺘﺤﺮﻙ‪ .‬ﺗﻜﻮﻥ ﺍﳌﺎﺩﺓ ﰲ ﻃﻮﺭ ﺍﻟﻐﺎﺯ )ﺃﻭ‬

‫ﺍﻟﺒﺨﺎﺭ(‪ .‬ﺇﺫﺍ ﺑﺪﺃﻧﺎ ﺑﺰﻳﺎﺩﺓ ﺍﻟﻀﻐﻂ ﺭﻭﻳﺪﹰﺍ ﻓﺈ ﱠﻥ ﺍﳊﺠﻢ ﺳﻮﻑ ﻳﺘﻨﺎﻗﺺ‪-‬ﺑﺸﻜﻞ ﳑﺎﺛﻞ ﻟﺘﺼﺮﻑ ﻏﺎﺯ ﻣﺜﺎﱄ ﺗﻘﺮﻳﺒﹰﺎ‪.-‬‬

‫ﻋﻨﺪﻣﺎ ﻧﺼﻞ ﺇﱃ ﺍﻟﻨﻘﻄﺔ ‪ b‬ﺗﺒﺪﹸﺃ ﻗﻄﺮﺍﺕ )ﻣﻦ ﺍﻟﺴﺎﺋﻞ( ﺳﺎﺋﻠﺔ ﺑﺎﻟﻈﻬﻮﺭ ﰲ ﺍﻷﺳﻄﻮﺍﻧﺔ ﻭﻫﻨﺎ ﺗﺒﺪﺃ ﺍﳌﺎﺩﺓ ﺑﺎﻻﻧﻔﺼﺎﻝ ﺇﱃ‬

‫ﻃﻮﺭﻳ‪‬ﻦ‪ -‬ﳍﻤﺎ ﻛﺜﺎﻓﺘﺎﻥ ﳐﺘﻠﻔﺘﺎﻥ ﻋﻠﻰ ﺍﻟﺮﻏﻢ ﻣﻦ ﻛﻮ‪‬ﻤﺎ ﲢﺖ ﻧﻔﺲ ﺍﻟﻀﻐﻂ ﻭﻧﻔﺲ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ‪ .‬ﻳﻜﻮﻥ ﺍﳊﺠﻢ‬

‫ﺍﻟﻨﻮﻋﻲ ﺍﳌﺮﺍﺩﻑ ﰲ ﻃﻮﺭ ﺍﻟﺒﺨﺎﺭ ﻫﻮ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ‪ b‬ﻭﰲ ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ‪.c‬‬

‫ﻣﻊ ﺗﻨﺎﻗﺺ ﺍﳊﺠﻢ ﻋﻠﻰ ﻃﻮﻝ ﺍﳋﻂ ‪ bc‬ﻳﺒﻘﻰ ﺍﻟﻀﻐﻂ ﺛﺎﺑﺘﺎﹰ‪ ،‬ﺗﺘﻨﺎﻗﺺ ﻧﺴﺒﺔ ﺍﳌﺎﺩﺓ ﰲ ﻃﻮﺭ ﺍﻟﻐﺎﺯ ﺑﺎﺳﺘﻤﺮﺍﺭ ﻭﺗﺘﺰﺍﻳﺪ‬

‫ﺚ ﻳﺘﻮﺍﺟﺪ ﺍﻟﻐﺎﺯ ﻭﺍﻟﺴﺎﺋﻞ ﰲ ﺣﺎﻟﺔ ﺍﺗﺰﺍﻥ ﻳ‪‬ﺴﻤ‪‬ﻰ‬

‫ﻧﺴﺒﺘﻬﺎ ﰲ ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ ﺑﺎﺳﺘﻤﺮﺍﺭ‪ .‬ﰲ ﻫﺬﺍ ﺍﳉﺰﺀ ﻣﻦ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺣﻴ ﹸ‬

‫ﺍﻟﺒﺨﺎ ‪‬ﺭ ﺍﻟﺒﺨﺎ ‪‬ﺭ ﺍﳌﹸﺸﺒﻊ ﻭﺍﻟﺴﺎﺋ ﹸﻞ ﺍﻟﺴﺎﺋ ﹶﻞ ﺍﳌﺸﺒﻊ ‪ ،‬ﻭﻳ‪‬ﺴﻤ‪‬ﻰ ﺿﻐﻄﻬﻤﺎ ﺿﻐﻂ ﺍﻟﺒﺨﺎﺭ ﺍﳌﺸﺒﻊ ﻭﺍﻟﺬﻱ ﻳﻌﺘﻤﺪ ﻋﻠﻰ ﺩﺭﺟﺔ‬

‫‪L-V‬‬ ‫ﺍﳊﺮﺍﺭﺓ ﻭﻳﺰﺩﺍﺩ ﺑﺎﺯﺩﻳﺎﺩﻫﺎ‪ .‬ﻳ‪‬ﻄﻠﻖ ﺍﺳﻢ ﻣﻨﺤﲎ ﺿﻐﻂ ﺍﻟﺒﺨﺎﺭ ‪ vapor pressure curve‬ﻋﻠﻰ ﺍﳌﻨﺤﲎ‬

‫ﰲ ﺍﻟﺸﻜﻞ ‪ 3-6-2‬ﻭﺍﻟﺬﻱ ﻫﻮ ﻣﺴﻘﻂ ﺍﻟﺴﻄﺢ ﺳﺎﺋﻞ‪-‬ﻏﺎﺯ‪ .‬ﻳﻜﻮﻥ ﺍﻟﺸﻜﻞ ﺍﻟﻌﺎﻡ ﳍﺬﺍ ﺍﳌﻨﺤﲎ ﻭﺍﺣﺪﹰﺍ ﳉﻤﻴﻊ ﺍﳌﻮﺍﺩ‬

‫ﻭﻟﻜﻦ ﺿﻐﻂ ﺍﻟﺒﺨﺎﺭ ﳜﺘﻠﻒ ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﻣﻌﻴ‪‬ﻨﺔ ﻣﻦ ﻣﺎﺩﺓ ﺇﱃ ﺃﹸﺧﺮﻯ ﻭﺑﺸﻜ ٍﻞ ﻣﻠﻤﻮﺱ‪ .‬ﻓﻀﻐﻂ ﺍﻟﺒﺨﺎﺭ ﻟﻠﺰﺋﺒﻖ‬

‫‪42.960 Torr‬‬ ‫‪‬ﻳﺴﺎﻭﻱ ‪ 1.2 mTorr‬ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ‪ 20 0C‬ﻳ‪‬ﺴﺎﻭﻱ ‪ 0.0012 Torr‬ﻣﻘﺎﺑﻞ‬

‫ﻟﺜﺎﱐ ﺃﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ﻋﻨﺪ ﻧﻔﺲ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ‪.‬‬

‫ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ‪ c‬ﺗﻜﻮﻥ ﺍﳌﺎﺩﺓ ﺳﺎﺋﻠ ﹰﺔ ﲤﺎﻣﹰﺎ‪ .‬ﻟﺘﺨﻔﻴﺾ ﺍﳊﺠﻢ ﻣﻦ ‪ vc‬ﺇﱃ ‪ vd‬ﻓﺈﻧ‪‬ﻪ ﻳﻠﺰ ‪‬ﻡ ﺿﻐﻂ ﻋﺎ ٍﻝ ﺟﺪﹰﺍ ﻷ ﱠﻥ ﺍﻟﺴﻮﺍﺋﻞ‬

‫ﺻﻌﺒﺔ ﺍﻻﻧﻜﻤﺎﺵ‪ .‬ﺗﻨﻔﺼﻞ ﺍﳌﺎﺩﺓ ﺇﱃ ﻃﻮﺭﻳ‪‬ﻦ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ‪ d‬ﻭﺗﺒﺪﹸﺃ ﺑﻠﹼﻮﺭﺍﺕ ﺍﻟﺼﻠﺐ ﺑﺎﻟﺘﺸﻜﻞ ﻭﻳﺒﻘﻰ ﺍﻟﻀﻐﻂ ﺛﺎﺑﺘﹰﺎ‬

‫ﺑ‪‬ﻴ ‪‬ﻦ ‪ d‬ﻭ ‪ e‬ﺛﺎﺑﺘﹰﺎ )ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺃﻳﺰﻭﺑﺎﺭﻳ‪‬ﺔ(‪ .‬ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ‪ e‬ﺗ‪‬ﺼﺒﺢ ﺍﳌﺎﺩﺓ ﺻﻠﺒﺔ ﲤﺎﻣﹰﺎ ﻭﻳﺒﺪﹸﺃ ﺍﳊﺠﻢ ﺑﺎﻟﺘﻨﺎﻗﺺ ﺑﺸﻜﻞ ﺑﺴﻴﻂ‬

‫ﻣﻊ ﺯﻳﺎﺩﺓ ﺍﻟﻀﻐﻂ ﺇ ﱠﻻ ﺇﺫﺍ ﻛﺎﻥ ﻫﻨﺎﻙ ﺃﻛﺜﺮ ﻣﻦ ﺷﻜﻞ ﻟﻠﺼﻠﺐ‪ .‬ﺍﳉﻠﻴﺪ ﻣﺜﺎﻝ ﻋﻠﻰ ﻣﺎﺩﺓ ﺻﻠﺒﺔ ﺫﺍﺕ ﺃﺷﻜﺎﻝ ﻣﺘﻌﺪﺩﺓ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪14 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫ﺚ ﺷ‪‬ﻮﻫﺪﺕ ﺳﺒﻌﺔ ﻣﻦ ﻫﺬﻩ ﺍﻷﺷﻜﺎﻝ ﲢﺖ ﺿﻐﻂ ﻋﺎ ٍﻝ ﺟﺪﹰﺍ‪ .‬ﺇﺫﺍ ﺯﻳﺪ ﺣﺠﻢ ﺍﻟﻨﻈﺎﻡ ﺍﻵﻥ )ﺍﺑﺘﺪﺍ ًﺀ ﻣﻦ ﺍﻟﻨﻘﻄﺔ ‪(f‬‬
‫ﺣﻴ ﹸ‬

‫ﻓﺈ ﱠﻥ ﺍﻟﺘﻐﲑﺍﺕ ﺍﻟﺴﺎﺑﻘﺔ ﲢﺪﺙ ﰲ ﺍﻻﲡﺎﻩ ﺍﳌﻌﺎﻛﺲ‪.‬‬

‫‪Critical point‬‬ ‫ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ‬ ‫‪6-5-2‬‬

‫ﺇﺫﺍ ﺍﻋﺘﱪﻧﺎ ﻧﻔﺲ ﺍﻟﻌﻤﻠﻴﺎﺕ ﺍﻟﺴﺎﺑﻘﺔ ﻋﻠﻰ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺃﻋﻠﻰ ‪ T3 > T2‬ﻓﺈ ﱠﻥ ﺍﻟﺘﺤﻮﻝ ﻣﻦ ﻃﻮﺭ ﺍﻟﺒﺨﺎﺭ ﺇﱃ ﺍﻟﺴﻴﻮﻟﺔ‬

‫)ﻣﻜﺎﻓﺊ ﺍﻟﻨﻘﻄﺔ ‪ (b‬ﻳﺴﺘﻮﺟﺐ ﺣﺠﻤﹰﺎ ﻧﻮﻋﻴﹰﺎ ﺃﻗ ﹼﻞ ﻭﺿﻐﻄﹰﺎ ﺃﻛﱪ ﰲ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ )‪ ،(a-b‬ﻭﻳﻜﻮﻥ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻋﻨﺪ‬

‫'‪ c‬ﺃﻛﱪ ﻣﻨﻪ ﻋﻨﺪ ‪ .c‬ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﻣﻌﻴﻨﺔ ‪ ، Tc‬ﻭﺍﻟﱵ ﺗ‪‬ﺴﻤ‪‬ﻰ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ‪ ،‬ﻳ‪‬ﺼﺒﺢ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ‬

‫ﻟﻠﺴﺎﺋﻞ ﺍﳌﺸﺒﻊ ﻭﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻟﻠﺒﺨﺎﺭ ﺍﳌﺸﺒﻊ ﻣﺘﺴﺎﻭﻳﻴ‪‬ﻦ‪.‬‬

‫ﺑﻌﺪ ‪ Tc‬ﻻ ﻳﻮﺟﺪ ﻓﺼﻞ ﺑﻴ‪‬ﻦ ﻃﻮﺭﻳ‪‬ﻦ ﳐﺘﻠﻔﻲ ﺍﻟﻜﺜﺎﻓﺔ ﰲ ﻋﻤﻠﻴ‪‬ﺔ ﺿﻐﻂ ﺣﺠﻢ ﻛﺒﲑ ﺃﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺔ‪ ،‬ﲟﻌﲎ ﺃﻧ‪‬ﻪ ﻻ ﻳ‪‬ﻤﻜﻦ‬

‫ﻓﺼﻞ ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ‪ .‬ﳛﺼﻞ ﺍﻟﻔﺼﻞ ﺇﱃ ﻃﻮﺭ ﺍﻟﻐﺎﺯ ﻭﺍﻟﺼﻠﺐ ﻋﻨﺪ ﺿﻐﻮﻁ ﻋﺎﻟﻴﺔ ﺟﺪﹰﺍ‪ .‬ﺗ‪‬ﺴﻤ‪‬ﻰ ﺍﻟﻘﻴﻤﺔ ﺍﳌﺸﺘﺮﻛﺔ‬

‫ﻟﻠﺤﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻟﻠﺴﺎﺋﻞ ﺍﳌﺸﺒﻊ ﻭﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻟﻠﺒﺨﺎﺭ ﺍﳌﺸﺒﻊ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺍﳊﺮﺝ ‪ vc‬ﻭﺍﻟﻀﻐﻂ ﺍﳌﺮﺍﺩﻑ ﺍﻟﻀﻐﻂ‬

‫ﺍﳊﺮﺝ ‪ .Pc‬ﺗﻌﺮ‪‬ﻑ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ ﺑﺄﻧ‪‬ﻬﺎ ﺍﻟﻨﻘﻄﺔ ﻋﻠﻰ ﺳﻄﺢ ‪ P-v-T‬ﺍﻟﱵ ﺇﺣﺪﺍﺛﻴﺎ‪‬ﺎ ﻫﻲ )‪. (Pc , vc , Tc‬‬

‫ﻳ‪‬ﻌﻄﻲ ﺍﳉﺪﻭﻝ ‪ 3-2‬ﺍﻟﺘﺎﱄ ﺍﻟﻘﻴﻢ ﺍﳊﺮﺟﺔ ﻟﺒﻌﺾ ﺍﳌﻮﺍﺩ‪ .‬ﹾﱂ ﺗ‪‬ﺸﺎﻫﺪ ﻧﻘﺎﻁ ﺣﺮﺟﺔ ﻟﻠﺴﻄﺢ ﺳﺎﺋﻞ‪-‬ﺻﻠﺐ ﺃﻱ ﺃ ﱠﻥ ﻫﻨﺎﻙ‬

‫ﺩﻭﻣﹰﺎ ﻓﺮﻗﹰﺎ ﳏ ‪‬ﺪﺩﹰﺍ ﺑﻴ‪‬ﻦ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ )ﺃﻭ ﺍﻟﻜﺜﺎﻓﺔ( ﺑﻴ‪‬ﻦ ﺍﻟﺴﺎﺋﻞ ﻭﺍﻟﺼﻠﺐ ﻋﻨﺪ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻧﻔﺴﻬﺎ ﻭﺍﻟﻀﻐﻂ ﻧﻔﺴﻪ‪.‬‬

‫ﻻ ﻳ‪‬ﻠﻐﻲ ﻫﺬﺍ ﺍﺣﺘﻤﺎﻝ ﻭﺟﻮﺩ ﻣﺜﻞ ﻫﻜﺬﺍ ﻧﻘﺎﻁ ﺣﺮﺟﺔ ﻋﻨﺪ ﺩﺭﺟﺎﺕ ﺣﺮﺍﺭﺓ ﻋﺎﻟﻴﺔ‪.‬‬

‫ﺗﺴﻴﻴﻞ ﻏﺎﺯ ‪ -‬ﺩﺭﺍﺳﺔ ﻣﺴﺘﻔﻴﻀﺔ‬ ‫‪7-5-2‬‬

‫ﻟﻨﻌﺪ ﺇﱃ ﺍﻟﻨﻘﻄﺔ ‪ a‬ﻭﻟﻨﻌﺘﱪ ﻋﻤﻠﻴ‪‬ﺔ ﺿﻐﻂ ﺍﻟﻐﺎﺯ ﺃﻳﺰﻭﺣﺮﺍﺭ‪‬ﻳﹰﺎ‪ .‬ﺇﺫﺍ ﻛﺎﻧﺖ ﺟﺪﺭﺍﻥ ﺍﻷﺳﻄﻮﺍﻧﺔ ﺷﻔﱠﺎﻓﺔ ﻓﺈﻧ‪‬ﻨﺎ ﺳﻮﻑ ﻧﺮﻯ‬

‫ﺍﻟﺘﻜﺜﻴﻒ ﺇﱃ ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ‪ ،b‬ﻋﻨﺪﻣﺎ ﻳﻠﺘﻘﻲ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ ﻣﻊ ﺍﻟﺴﻄﺢ )ﲞﺎﺭ‪-‬ﺳﺎﺋﻞ( ﻭﻧﺮﻯ ﳕﻮ ﻃﻮﺭ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪15 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫ﺍﻟﺴﺎﺋﻞ ﻭﺗﻼﺷﻲ ﻃﻮﺭ ﺍﻟﺒﺨﺎﺭ‪.‬‬

‫ﻋﻨﺪ ‪ b‬ﻳﻜﻮﻥ ﻛﻞ ﺍﻟﺒﺨﺎﺭ ﻗﺪ ﲢﻮ‪‬ﻝ ﺇﱃ ﺳﺎﺋﻞ‪ .‬ﺍﻵﻥ ﻳ‪‬ﻤﻜﻨﻨﺎ ﺇﺟﺮﺍﺀ ﻧﻔﺲ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ "ﺑﺎﻟﻠﹼﻒ" ﻣﻦ ﻭﺭﺍﺀ ﺍﻟﻨﻘﻄﺔ‬

‫ﺍﳊﺮﺟﺔ‪ -‬ﻫﺬﻩ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﻟﻴﺴﺖ ﺃﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺔ ﻷﻧ‪‬ﻨﺎ ﻧﻨﺘﻘﻞ ﻣﻦ ﺃﻳﺰﻭﺣﺮﺍﺭﻱ ﺇﱃ ﺃﻳﺰﻭﺣﺮﺍﺭﻱ ﺁﺧﺮ‪.‬‬

‫ﺗﻜﻮﻥ ﺍﳊﺎﻟﺔ ﺍﻟﻨﻬﺎﺋﻴ‪‬ﺔ ﻟﻠﻨﻈﺎﻡ ﻭﺍﺣﺪ ﹰﺓ ﰲ ﺍﳊﺎﻟﺘﻴ‪‬ﻦ ﻟﻜﻦ ﺑﻔﺼﻞ ﺍﻟﻨﻈﺎﻡ ﺇﱃ ﻃﻮﺭﻳ‪‬ﻦ ﰲ ﺍﳊﺎﻟﺔ ﺍﻷﻭﱃ ﻭﺑﺪﻭﻥ ﻫﺬﺍ ﺍﻟﻔﺼﻞ‬

‫ﰲ ﺍﳊﺎﻟﺔ ﺍﻟﺜﺎﻧﻴﺔ‪ ،‬ﻭﺗﻜﻮﻥ ﺧﻮﺍﺹ ﺍﻟﻨﻈﺎﻡ ﺧﻮﺍﺹ ﻣﺎﺋﻊ ﺗﺎﻡ ﰲ ﺍﻟﻨﻘﻄﺔ ‪ b‬ﰲ ﺍﳊﺎﻟﺘﻴ‪‬ﻦ‪ .‬ﻳ‪‬ﻤﻜﻦ ﲢﻮﻳﻞ ﺍﻟﺒﺨﺎﺭ ﺇﱃ ﺳﺎﺋﻞ‬

‫ﺩﻭﻥ ﺍﳌﺮﻭﺭ ﺑﺎﻟﺘﻜﺜﻴﻒ ﻭﻟﻜﻦ ﻟﻴﺲ ﻫﻨﺎﻙ ﺧﻂ ﻓﺎﺻﻞ ﻭﺍﺿﺢ ﺑﻴ‪‬ﻦ ﺟﺰﺋﻲ ﺍﻟﺴﻄﺢ )ﺍﻟﺴﺎﺋﻞ ﻭ"ﺍﻟﺒﺨﺎﺭ"(‪.‬‬

‫ﺍﻟﻔﺮﻕ ﺑﻴ‪‬ﻦ ﻛﻠﻤﱵ ﲞﺎﺭ ﻭﻏﺎﺯ ﻣﺼﻄﻨﻊ ﻭﻏﲑ ﺿﺮﻭﺭﻱ؛ ﻓﻜﻼﳘﺎ ﳍﻤﺎ ﻧﻔﺲ ﺍﳋﺼﺎﺋﺺ‪ .‬ﺍﻟﺒﺨﺎﺭ ﻳ‪‬ﺴﺘﺨﺪﻡ ﻟﻠﺘﻌﺒﲑ ﻋﻦ‬

‫ﻭﺿﻊ ﺍﻻﺗﺰﺍﻥ ﺑﻴ‪‬ﻦ ﻏﺎﺯ ﻭﺳﺎﺋﻠﻪ )ﺍﻟﺒﺨﺎﺭ ﺍﳌﺸﺒﻊ( ﺃﻭ ﻟﻠﺘﻌﺒﲑ ﻋﻦ ﻏﺎﺯ ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺗﻪ ﺍﳊﺮﺟﺔ‪.‬‬

‫ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺍﳊﺮﺝ‬ ‫ﺍﻟﻀﻐﻂ ﺍﳊﺮﺝ‬ ‫ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ‬

‫ﺍﳌﺎﺩﺓ‬
‫)‪vc (m3 kilomole-1‬‬ ‫)‪Pc (N.m-2‬‬ ‫)‪Tc (K‬‬
‫‪0.0726‬‬ ‫‪1.15‬‬ ‫‪3.34‬‬ ‫)‪He(3‬‬ ‫ﺍﳍﻴﻠﻴﻮﻡ ‪3‬‬
‫‪0.0578‬‬ ‫‪1.16×105‬‬ ‫‪5.25‬‬ ‫)‪He(4‬‬ ‫ﺍﳍﻴﻠﻴﻮﻡ ‪4‬‬
‫‪0.091‬‬ ‫‪33.6‬‬ ‫‪126.2‬‬ ‫‪N2‬‬ ‫ﺍﻟﻨﻴﺘﺮﻭﺟﲔ‬
‫‪0.078‬‬ ‫‪50.2‬‬ ‫‪154.8‬‬ ‫‪O2‬‬ ‫ﺍﻷﻛﺴﺠﲔ‬
‫‪0.094‬‬ ‫‪73.0‬‬ ‫‪304.2‬‬ ‫‪CO2‬‬ ‫ﺛﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ‬
‫‪0.056‬‬ ‫‪209.0‬‬ ‫‪647.4‬‬ ‫‪H2O‬‬ ‫ﺍﳌﺎﺀ‬
‫ﺍﳉﺪﻭﻝ ‪ :3-2‬ﺇﺣﺪﺍﺛﻴﺎﺕ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ ﻟﺒﻌﺾ ﺍﳌﻮﺍﺋﻊ‪.‬‬

‫ﻋﻨﺪﻣﺎ ﺗﻜﻮﻥ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﻏﺎﺯ ﲢﺖ ﺿﻐﻂ ﻣﻌﲔ ﺃﻛﱪ ﻣﻦ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻹﺷﺒﺎﻉ ﻋﻨﺪ ﻫﺬﺍ ﺍﻟﻀﻐﻂ ﻓﺈﻧ‪‬ﻨﺎ ﻧﻘﻮﻝ ﺃ ﱠﻥ‬

‫ﺍﻟﻐﺎﺯ "ﻓﻮﻕ ﻣ‪‬ﺴﺨ‪‬ﻦ" ‪ superheated‬ﻭﺍﻟﺒﺨﺎﺭ ﻳ‪‬ﺴﻤ‪‬ﻰ "ﲞﺎﺭﹰﺍ ﻓﻮﻕ ﻣ‪‬ﺴﺨ‪‬ﻦ"‪ .‬ﻟﻴﺲ ﺑﺎﻟﻀﺮﻭﺭﺓ ﺃ ﹾﻥ ﺗﻜﻮﻥ ﺩﺭﺟﺔ‬

‫ﺣﺮﺍﺭﺓ ﻏﺎﺯ ﻓﻮﻕ ﻣ‪‬ﺴﺨ‪‬ﻦ ﻋﺎﻟﻴﺔ‪ .‬ﻳﻜﻮﻥ ﺍﻟﻨﻴﺘﺮﻭﺟﲔ ﺍﳌﻮﺟﻮﺩ ﰲ ﺍﳍﻮﺍﺀ "ﻓﻮﻕ ﻣ‪‬ﺴﺨ‪‬ﻦ " ﺩﻭﻣﹰﺎ ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﳉﻮ‬

‫ﺍﻟﻌﺎﺩ‪‬ﻳﺔ ﺇ ﹾﺫ ﺃ ﱠﻥ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺇﺷﺒﺎﻉ ﺍﻟﻨﻴﺘﺮﻭﺟﲔ ﻋﻨﺪ ﺿﻐﻂ ﻗﻴﻤﺘﻪ ‪) P = 0.8 bar‬ﺍﻟﻀﻐﻂ ﺍﳉﺰﺋﻲ ﺍﳉﻮﻱ‬

‫ﻟﻠﻨﻴﺘﺮﻭﺟﲔ ﺍﻟﺬﻱ ﻳ‪‬ﺸﻜﱢﻞ ‪ 7%‬ﻣﻦ ﺍﳍﻮﺍﺀ( ﺗ‪‬ﺴﺎﻭﻱ ‪.-197.9 °C‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪16 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫ﺗﻐﲑ ﺍﳊﺎﻟﺔ ﰲ ﻋﻤﻠﻴ‪‬ﺔ ﺃﻳﺰﻭﺑﺎﺭﻳ‪‬ﺔ‪ :‬ﺍﻟﻐﻠﻴﺎﻥ ﻭﺍﻟﺘﺠﻤﺪ‬ ‫‪8-5-2‬‬

‫ﻟﻨﻌﺪ ﺇﱃ ﺳﻄﺢ ‪ P-V-T‬ﳌﺎﺩﺓ ﺗﺘﻘﻠﺺ ﺑﺎﻟﺘﱪﻳﺪ ﻭﻧﺘﺎﺑﻊ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺍﻷﻳﺰﻭﺑﺎﺭﻳ‪‬ﺔ ﻋﻨﺪ ﺍﻟﻀﻐﻂ ‪ P1‬ﺍﻟﱵ ﳜﻀﻊ ﳍﺎ ﺍﻟﻨﻈﺎﻡ‬

‫ﺑﲔ ﺍﻟﻨﻘﻄﺘﻴ‪‬ﻦ ‪ a‬ﻭ ‪) ،b‬ﺍﻟﺸﻜﻞ ‪ .(7-2‬ﺍﻓﺘﺮﺽ ﺃ ﱠﻥ ﻟﺪﻳﻨﺎ ﻭﻋﺎ ًﺀ ﺑﻪ ﺳﺎﺋﻞ ﻣﻔﺘﻮﺣﹰﺎ ﻭﺃ ﱠﻥ ‪ P1‬ﺗﺴﺎﻭﻱ ﺍﻟﻀﻐﻂ ﺍﳉﻮﻱ‬

‫)ﺍﻟﻨﻘﻄﺔ ‪ .(a‬ﺇﺫﺍ ﺯﺩ‪‬ﻧﺎ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﲢﺖ ﺿﻐﻂ ﺛﺎﺑﺖ ﻓﺈﻧ‪‬ﻨﺎ ﺳﻮﻑ ﻧﺘﺤﺮﻙ ﳓﻮ ﺍﻟﻨﻘﻄﺔ ‪ b‬ﻋﻠﻰ ﻧﻔﺲ ﺍﻷﻳﺰﻭﺑﺎﺭ‪.‬‬

‫ﻋﻨﺪﻣﺎ ﻧﺼﻞ ﺍﻟﻨﻘﻄﺔ ‪ b‬ﻳﻨﻔﺼﻞ ﺍﻟﻨﻈﺎﻡ ﺇﱃ ﻃﻮﺭﻳ‪‬ﻦ ﻭﺍﺣﺪ ﰲ ﺍﻟﻨﻘﻄﺔ ‪ b‬ﻭﺍﻵﺧﺮ ﰲ ﺍﻟﻨﻘﻄﺔ ‪ .c‬ﻳ‪‬ﺼﺒﺢ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ‬

‫ﻟﻄﻮﺭ ﺍﻟﺒﺨﺎﺭ ﺃﻛﺒ‪‬ﺮ ﺑﻜﺜﲑ ﻣﻨﻪ ﻟﻠﻄﻮﺭ ﺍﻟﺴﺎﺋﻞ ﻭﻳﺘﺰﺍﻳﺪ ﺣﺠﻢ ﺍﻟﻨﻈﺎﻡ ﺑﺸﻜﻞ ﻛﺒﲑ ﻣﻠﻤﻮﺱ ﻭﻫﺬﺍ ﻫﻮ ﺍﻟﻐﻠﻴﺎﻥ‪.‬‬

‫ﺇﺫﺍ ﻛﺎﻥ ﺍﻟﻮﻋﺎﺀ ﻣﻔﺘﻮﺣﹰﺎ ﻓﺈ ﱠﻥ ﺍﻟﺒﺨﺎﺭ ﺳﻴﻨﺘﺸﺮ ﰲ ﺍﳉﻮ‪ .‬ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﻐﻠﻴﺎﻥ ‪ Tb‬ﺍﻟﱵ ﻳﺘﺴﺎﻭﻯ ﻋﻨﺪﻫﺎ ﺿﻐﻂ‬

‫ﺍﻟﺒﺨﺎﺭ ﻣﻊ ﺍﻟﻀﻐﻂ ﺍﳋﺎﺭﺟﻲ ﻳ‪‬ﻤﻜﻦ ﺍﻋﺘﺒﺎﺭ ﺍﻟﺸﻜﻞ ‪ 3-6-2‬ﺑﺄﻧ‪‬ﻪ ﻣﻨﺤﲎ ﻧﻘﻄﺔ ﺍﻟﻐﻠﻴﺎﻥ‪ .‬ﰲ ﺣﺎﻟﺔ ﺍﳌﺎﺀ ﺣﻴ ﹸ‬
‫ﺚ ﻣﻴﻞ‬

‫ﺍﳋﻂ ﺍﳌﹸﻤﺜﱢﻞ ﻟﻠﻄﻮﺭ ﺻﻠﺐ‪-‬ﺳﺎﺋﻞ ﰲ ﺍﻻﲡﺎﻩ ﺍﳌﻌﺎﻛﺲ ﻭﻋﻨﺪ ‪ P1 = 1 atm‬ﺗﻜﻮﻥ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻨﺪ ‪ b‬ﻫﻲ‬

‫ﺚ ﺃ ﱠﻥ ﺍﻟﺰﻳﺎﺩﺓ ﰲ ﺍﻟﻀﻐﻂ ﺍﳋﺎﺭﺟﻲ ﺗﺰﻳ ‪‬ﺪ ﻣﻦ ﺩﺭﺟﺔ‬

‫‪ .Tb = 373 K‬ﳝﻴ ﹸﻞ ﻣﻨﺤﲎ ﺿﻐﻂ ﺍﻟﺒﺨﺎﺭ ﺇﱃ ﺍﻟﻴﻤﲔ ﲝﻴ ﹸ‬

‫ﺣﺮﺍﺭﺓ ﺍﻟﻐﻠﻴﺎﻥ ﻭﺑﺎﻟﻌﻜﺲ ﺃﻱ ﺃ ﱠﻥ ﺧﻔﺾ ﺍﻟﻀﻐﻂ ﻳ‪‬ﻘﻠﱢﻞ ﻣﻦ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﻐﻠﻴﺎﻥ‪.‬‬

‫ﺍﻟﺸﻜﻞ ‪ :1-7-2‬ﻋﻤﻠﻴ‪‬ﺔ ﺃﻳﺰﻭﺑﺎﺭﻳ‪‬ﺔ ﰲ ﺳﻄﺢ ‪ P-v-T‬ﳌﺎﺩﺓ ﺗﺘﻘﻠﱠﺺ ﺑﺎﻟﺘﱪﻳﺪ‪.‬‬

‫ﺇﺫﺍ ﺧﻔﱠﻀﻨﺎ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻨﺪ ‪ a‬ﻓﺈ ﱠﻥ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺗﻘﻮﺩﻧﺎ ﺇﱃ ﺍﻟﻨﻘﻄﺔ ‪ d‬ﻋﻠﻰ ﺍﻷﻳﺰﻭﺑﺎﺭ ‪ .P1‬ﻋﻨﺪ ‪ d‬ﻳﻨﻔﺼﻞ ﺍﻟﻨﻈﺎﻡ ﺇﱃ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪17 -‬‬ ‫‬

 ‫א א‬ ‫‪P-v-T‬‬

‫ﻃﻮﺭﻳ‪‬ﻦ ‪ d‬ﻭ ‪) e‬ﰲ ﺍﻟﺸﻜﻞ ﻳﻜﻮﻥ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻟﻠﺼﻠﺐ ﺃﻗﱠﻞ ﻣﻦ ﺍﻟﺴﺎﺋﻞ( ﻭﻳﺘﻨﺎﻗﺺ ﺍﳊﺠﻢ ﻭﻫﺬﺍ ﻫﻮ ﺍﻟﺘﺠﻤﻴﺪ‪-‬‬

‫ﺑﻨﻔﺲ ﺍﻟﻄﺮﻳﻘﺔ ﻳ‪‬ﻤﺜﱢﻞ ﻣﻨﺤﲎ ﻋﻤﻠﻴ‪‬ﺔ ﺍﻟﺘﺠﻤﻴﺪ ﻋﻨﺪ ‪ P1‬ﻭﲢﺖ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﺘﺠﻤﻴﺪ ‪ .Tf‬ﺇﺫﺍ ﻛﺎﻥ ﺍﳋﻂ ﺍﻟﺬﻱ‬

‫ﻳ‪‬ﻤﺜﱢﻞ ﺍﺗﺰﺍﻥ ﺍﻟﻄﻮﺭﻳ‪‬ﻦ ﺻﻠﺐ‪-‬ﺳﺎﺋﻞ ﳝﻴ ﹸﻞ ﺇﱃ ﺍﻷﻋﻠﻰ ﻭﺍﱃ ﺍﻟﻴﻤﲔ ﻓﺈ ﱠﻥ ﺍﻟﻀﻐﻂ ﻳﺮﺗﻔﻊ ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﺘﺠﻤﻴﺪ‬

‫ﻭﺑﺎﻟﻌﻜﺲ‪.‬‬

‫‪Sublimatin‬‬ ‫ﺍﻟﺘﺴﺎﻣﻲ‬ ‫‪9-5-2‬‬

‫ﻻ ﻳﺘﻮﺍﺟﺪ ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺃﻗﻞ ﻣﻦ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﻨﻘﻄﺔ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ ﺃﻭ ﺿﻐﻂ ﺃﻗﻞ ﻣﻦ ﺿﻐﻂ ﻫﺬﻩ‬

‫ﺍﻟﻨﻘﻄﺔ‪ .‬ﻭﻻ ﺗﻈﻬﺮ ﺍﳌﺎﺩﺓ ﺇ ﱠﻻ ﰲ ﻃﻮﺭﻳ‪‬ﻦ ﻋﻨﺪ ﻫﺬﻩ ﺍﻟﻨﻘﻄﺔ‪ :‬ﺍﻟﻐﺎﺯ ﻭﺍﻟﺼﻠﺐ‪ .‬ﻭﻳﺘﻢ ﺍﻟﺘﺤﻮﻝ ﻣﻦ ﻃﻮﺭ ﺇﱃ ﺁﺧﺮ ﺑﺪﻭﻥ‬

‫ﺍﳌﺮﻭﺭ ﰲ ﺣﺎﻟﺔ ﺍﻟﺴﻴﻮﻟﺔ ﻋﻨﺪ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺗ‪‬ﺴﻤ‪‬ﻰ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﺘﺴﺎﻣﻲ‪ .‬ﻻ ﻳ‪‬ﻤﻜﻦ ﻣﺸﺎﻫﺪﺓ ﻋﻤﻠﻴ‪‬ﺔ ﺍﻟﺘﺴﺎﻣﻲ ﰲ‬

‫ﺣﺎﻟﺔ ﺍﳌﺎﺀ ﰲ ﺍﻟﻈﺮﻭﻑ ﺍﳉﻮﻳ‪‬ﺔ ﺍﻟﻄﺒﻴﻌﻴﺔ‪ ،‬ﻭﻻ ﻳ‪‬ﻤﻜﻦ ﺍﳊﺼﻮﻝ ﻋﻠﻰ ‪ CO2‬ﺍﻟﺴﺎﺋﻞ ﲢﺖ ﺍﻟﻀﻐﻂ ﺍﳉﻮﻱ ﻷ ﱠﻥ ﺩﺭﺟﺔ‬

‫ﺣﺮﺍﺭﺓ ﻭﺿﻐﻂ ﺍﻟﻨﻘﻄﺔ ﺍﻟﺜﻼﺛﻴ‪‬ﺔ ﳘﺎ ﻋﻠﻰ ﺍﻟﺘﻮﺍﱄ ‪ T3=-56.6 °C‬ﻭ ‪.P3=5.2 bar‬‬

‫ﻋﻨﺪ ﺗﺴﺨﲔ ‪ CO2‬ﺍﻟﺼﻠﺐ )ﺍﳉﻠﻴﺪ ﺍﳉﺎﻑ( ﻋﻨﺪ ﺍﻟﻀﻐﻂ ﺍﳉﻮﻱ ﻓﺈﻧ‪‬ﻪ ﻳﺘﺴﺎﻣﻰ ﻭﻳﺘﺤﻮﻝ ﺇﱃ ﺍﻟﺒﺨﺎﺭ ﻣﺒﺎﺷﺮ ﹰﺓ‪ .‬ﻭﺇﺫﺍ‬

‫ﺃﺭﺩﻧﺎ ﺍﳊﺼﻮﻝ ﻋﻠﻰ ‪ CO2‬ﺍﻟﺴﺎﺋﻞ ﲢﺖ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﻟﻌﺎﺩﻳ‪‬ﺔ )ﺍﻟﻐﺮﻓﺔ( ﻓﺈﻧ‪‬ﻪ ﻳﻠﺰﻣﻨﺎ ﺿﻐﻮﻁ ﻋﺎﻟﻴﺔ ﺟﺪﹰﺍ ﻭﺗ‪‬ﺴﺘﺨﺪﻡ‬

‫ﺗﻨﻜﺎﺕ ﺧﺎﺻﺔ ﻟﻨﻘﻞ ﺛﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ﺍﻟﺴﺎﺋﻞ ﻭﺍﻟﱵ ﲢﻮﻱ ﻛﻤﻴ‪‬ﺔ ﻛﺒﲑﺓ ﻣﻦ ﺍﻟﺴﺎﺋﻞ ﳐﻠﻮﻃﺔ ﺑﺒﻌﺾ ﺍﻟﺒﺨﺎﺭ‪.‬‬

‫ﺗ‪‬ﺴﺘﺨﺪﻡ ﺍﻷﺣﺮﻑ ﺍﻟﺜﻼﺛﺔ ‪ NTP‬ﻭﻫﻲ ﺍﺧﺘﺼﺎﺭ ﻟﹻ ‪ Normal Temperature & Pressure‬ﻋﻨﺪ‬

‫ﺍﳊﺪﻳﺚ ﻋﻦ ﺍﻟﻈﺮﻭﻑ ﺍﳉﻮﻳ‪‬ﺔ ﺍﻟﻄﺒﻴﻌﻴﺔ ‪ T = 20 0C‬ﻭ ‪.P = 1 atm‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪18 -‬‬ ‫‬

 ‫א‬ ‫א‬

‫‪Expansivity and Compressibility‬‬ ‫ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ ﻭﺍﻹﻧﻀﻐﺎﻃﻴ‪‬ﺔ‬ ‫‪6-2‬‬

‫‪P-V-T‬‬ ‫ﻣﻘﺪﻣﺔ‪ :‬ﺩﺭﺍﺳﺔ ﺭﻳﺎﺿﻴ‪‬ﺔ ﻟﺴﻄﺢ‬ ‫‪1-6-2‬‬

‫‪‬ﻧﺬﻛﱢﺮ ﺑﺄ ﱠﻥ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻨﻈﺎﻡ ﺛﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻲ ‪ PVT‬ﻫﻲ ﻋﻼﻗﺔ ﺑﻴ‪‬ﻦ ﺍﻟﻀﻐﻂ‪ ،‬ﺍﳊﺠﻢ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻷﻳ‪‬ﺔ ﺣﺎﻟﺔ‬

‫ﺍﺗﺰﺍﻥ ﳍﺬﺍ ﺍﻟﻨﻈﺎﻡ‪ .‬ﻭﻧ‪‬ﺬﻛﱢﺮ ﺃﻳﻀﹰﺎ ﺑﺄ ﱠﻥ ﻫﺬﻩ ﺍﳌﻌﺎﺩﻟﺔ ﺗ‪‬ﻤﺜﱢﻞ ﰲ ﻧﻈﺎﻡ ﺇﺣﺪﺍﺛﻴﺎﺕ ﻗﺎﺋﻢ )ﺩﻳﻜﺎﺭﰐ( ﺑﺴﻄﺢ ﻭﺍﻟﺸﻜﻞ ﺍﻟﺘﺎﱄ‬

‫ﻳ‪‬ﺒﻴ‪‬ﻦ ﻣﺜﻞ ﻫﻜﺬﺍ ﺳﻄﺢ ﻟﺼﻠﺐ ﺃﻭ ﻟﺴﺎﺋﻞ‪-‬ﺍﶈﻮﺭ ﺍﻟﻌﻤﻮﺩﻱ ‪ V‬ﻣ‪‬ﺒﺎﻟ ﹲﻎ ﻓﻴﻪ ﻟﻠﺘﻮﺿﻴﺢ‪.-‬‬

‫ﺍﻟﺸﻜﻞ ‪ :2-7-2‬ﺳﻄﺢ ‪ P-v-T‬ﻟﺼﻠﺐ ﺃﻭ ﻟﺴﺎﺋﻞ‬

‫ﻳﺰﺩﺍﺩ ﺍﳊﺠﻢ ﻋﻨﺪ ﺯﻳﺎﺩﺓ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺇﺫﺍ ﻛﺎﻥ ﺍﻟﻀﻐﻂ ﺛﺎﺑﺘﹰﺎ‪ .‬ﺇﺫﺍ ﻧﻈﺮﻧﺎ ﺇﱃ ﺍﻷﻳﺰﻭﺑﺎﺭ ‪ P1‬ﺍﻟﺬﻱ ﺗﻨﺘﻤﻲ ﻟﻪ ﺍﻟﻨﻘﻄﺘﺎﻥ‬

‫‪ 1‬ﻭ ‪ (T2 > T1) 2‬ﻓﺈﻧ‪‬ﻨﺎ ﻧﺮﻯ ﺃ ﱠﻥ ‪.V2 > V1‬‬

‫ﻳﺘﻨﺎﻗﺺ ﺍﳊﺠﻢ ﻋﻨﺪ ﺯﻳﺎﺩﺓ ﺍﻟﻀﻐﻂ ﺑﺜﺒﻮﺕ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ‪ .‬ﺇﺫﺍ ﻧﻈﺮﻧﺎ ﺇﱃ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ ‪ T2‬ﺍﻟﺬﻱ ﺗﻨﺘﻤﻲ ﺇﻟﻴﻪ‬

‫ﺍﻟﻨﻘﻄﺘﺎﻥ ‪ 2‬ﻭ ‪ (P3 > P2) 3‬ﻓﺈﻧ‪‬ﻨﺎ ﻧﺮﻯ ﺃ ﱠﻥ ‪.V3 > V2‬‬

‫ﻋﻨﺪ ﺣﻞ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ‪ f (P,V,T,m) = 0‬ﺑﺈﳚﺎﺩ ﺟﺬﻭﺭﻫﺎ ﻓﺈ ﱠﻥ ﻭﺍﺣﺪﹰﺍ ﻣﻦ ﺍﳌﺘﻐﲑﺍﺕ ﺍﻟﺜﻼﺛﺔ )ﺍﳊﺠﻢ ﻣﺜ ﹰ‬
‫ﻼ(‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪19 -‬‬ ‫‬

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‫ﻱ ﺯﻭﺝ ﻣﻦ ﻗﻴﻢ ‪ P‬ﻭ ‪.T‬‬

‫ﻳ‪‬ﻌﻄﻰ ﺑﺪﻻﻟﺔ ﺍﳌﺘﻐﲑﻳ‪‬ﻦ ‪ P‬ﻭ ‪ T‬ﻭﻗﻴﻤﺔ ‪ V‬ﻟﻴﺴﺖ ﺇ ﱠﻻ ﺍﺭﺗﻔﺎﻉ ﺍﻟﺴﻄﺢ ﻋﻦ ﻣﺴﺘﻮﻯ ‪ P-T‬ﻷ ‪‬‬

‫ﺑﺪ ﹰﻻ ﻣﻦ ﺍﻻﺭﺗﻔﺎﻉ ﺍﻟﺴﺎﺑﻖ‪ ،‬ﻳ‪‬ﻤﻜﻦ ﻭﺻﻒ ﺍﻟﺴﻄﺢ ﲟﻴﻠﻪ ﰲ ﺃﻳ‪‬ﺔ ﻧﻘﻄﺔ‪ .‬ﻫﺬﺍ ﻳﻌﲏ ﺭﻳﺎﺿﻴﹰﺎ ﲢﺪﻳﺪ ﻣﻴﻞ ﺧﻄﻮﻁ ﺗﻘﺎﻃﻊ‬

‫ﺍﻟﺴﻄﺢ‪-‬ﰲ ﺃﻳ‪‬ﺔ ﻧﻘﻄﺔ‪ -‬ﻣﻊ ﻣﺴﺘﻮﻳﺎﺕ ﺫﺍﺕ ﺿﻐﻂ ﺛﺎﺑﺖ ﻭﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺛﺎﺑﺘﺔ‪ .‬ﻳ‪‬ﻤﺜﱢﻞ ﺍﻟﺸﻜﻞ ‪ 8-2‬ﺍﻟﺘﺎﱄ ﺗﻘﺎﻃﻊ‬

‫ﺍﻟﺴﻄﺢ ﰲ ﺍﻟﺸﻜﻞ ﺍﻟﺴﺎﺑﻖ ﻣﻊ ﺍﳌﺴﺘﻮﻯ ﺍﳌﻌﺮ‪‬ﻑ ﺑﺎﻟﻀﻐﻂ ﺍﻟﺜﺎﺑﺖ ‪ .P1‬ﺑﻌﺒﺎﺭﺓ ﺃﹸﺧﺮﻯ‪ ،‬ﻳ‪‬ﻤﺜﱢﻞ ﺍﻟﺸﻜﻞ ﺗﻐﲑ ‪ V‬ﻛﺪﺍﻟﺔ‬

‫ﻟﺪﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻟﻠﻤﻨﺤﲎ ﺍﻷﻳﺰﻭﺑﺎﺭﻱ ‪.P1‬‬

‫ﺍﻟﺸﻜﻞ ‪ :8-2‬ﺗﻘﺎﻃﻊ ﺳﻄﺢ ‪ P-v-T‬ﻣﻊ ﺍﳌﺴﺘﻮﻯ ﺍﳌﻌﺮ‪‬ﻑ ﺑﺎﻟﻀﻐﻂ ﺍﻟﺜﺎﺑﺖ ‪.P1‬‬

‫ﺇﺣﺪﺍﺛﻴﺎﺕ ﺍﻟﻨﻘﻄﺘﻴ‪‬ﻦ ‪ 1‬ﻭ ‪ 2‬ﻫﻲ )‪ (V1 , P1 , T1‬ﻭ )‪ (V2 , P1 , T2‬ﻋﻠﻰ ﺍﻟﺘﺮﺗﻴﺐ‬

‫ﻣﻴﻞ ﺍﳌﻨﺤﲎ ﰲ ﺃﻳ‪‬ﺔ ﻧﻘﻄﺔ ﻳﻌﲏ ﻣﻴﻞ ﺍﳌﻤﺎﺱ ﻟﻠﻤﻨﺤﲎ ﻋﻨﺪ ﺗﻠﻚ ﺍﻟﻨﻘﻄﺔ ﺃﻱ ﻇﻞ ﺍﻟﺰﺍﻭﻳﺔ ‪ θ‬ﰲ ﺍﻟﺸﻜﻞ ﻭﺍﻟﺬﻱ ﻳﺴﺎﻭﻱ‬

‫‪∂V‬‬
‫ﻫﻨﺎ ‪  ‬ﻭﺍﻟﱵ ﻫﻲ ﺍﳌﹸﺸﺘﻘﱠﺔ ﺍﳉﺰﺋﻴ‪‬ﺔ ﻟﻠﺤﺠﻢ ﺑﺎﻟﻨﺴﺒﺔ ﻟﺪﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ‪.‬‬
‫‪ ∂ T P‬‬

‫‪ ∂ V  = n R = cons tan t‬‬ ‫ﺚ ‪ P V = n R T‬ﻓﺈ ﱠﻥ‪:‬‬

‫ﻼ ﺣﻴ ﹸ‬
‫ﰲ ﺣﺎﻟﺔ ﺍﻟﻐﺎﺯ ﺍﳌﺜﺎﱄ ﻣﺜ ﹰ‬
‫‪‬‬ ‫‪‬‬
‫‪ ∂ T P‬‬ ‫‪P‬‬

‫ﻛﻤﺎ ﻗﻠﻨﺎ ﺳﺎﺑﻘﹰﺎ ﻓﺈ ﱠﻥ ﺍﻟﺮﻣﺰ ﺍﻟﺴﻔﻠﻲ ) ‪ P‬ﻫﻨﺎ( ﻳﻌﲏ ﺃ ﱠﻥ ﺍﳌﹸﺸﺘﻘﱠﺔ ﺍﳉﺰﺋﻴ‪‬ﺔ ﻣﺄﺧﻮﺫﺓ ﻋﻨﺪ ﺿﻐﻂ ﺛﺎﺑﺖ ﻭﺃ ﱠﻥ ﺍﳊﺠﻢ ﻣﻌﺮ‪‬ﻑ‬

‫ﺑﺪﻻﻟﺔ ‪ P‬ﻭ ‪ .T‬ﰲ ﺍﻟﺪﻳﻨﺎﻣﻴﻜﺎ ﺍﳊﺮﺍﺭﻳ‪‬ﺔ ﻗﺪ ﳓﺘﺎﺝ ﻻﺳﺘﺨﺪﺍﻡ ﻣﺘﻐﲑﺍﺕ ﺃﹸﺧﺮﻯ ﺑﺎﻹﺿﺎﻓﺔ ﻟﻠﻀﻐﻂ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪20 -‬‬ ‫‬

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‫ﻭﺍﳊﺠﻢ ﻭﳍﺬﺍ ﻧﺴﺘﺨﺪﻡ ﺍﻟﺮﻣﺰ ﺍﻟﺴﻔﻠﻲ )ﺍﻟﺬﻱ ﻻ ﺣﺎﺟﺔ ﻟﻪ ﻣﻦ ﻭﺟﻬﺔ ﻧﻈﺮ ﺭﻳﺎﺿﻴﺔ(‪.‬‬

‫ﻻ ﻳﻨﻄﺒﻖ ﻣﻴﻞ "ﺍﳊﺒﻞ" ﺍﻟﻮﺍﺻﻞ ﺑﻴ‪‬ﻦ ﺍﻟﻨﻘﻄﺘﻴ‪‬ﻦ ‪ 1‬ﻭ ‪ 2‬ﻋﻠﻰ ﻣﻴﻞ ﺍﳌﻤﺎﺱ ﻟﻠﻤﻨﺤﲎ ﻭﻟﻜﻨﻬﻤﺎ ﻳﻘﺘﺮﺑﺎﻥ ﺟﺪﹰﺍ ﻣﻦ‬

‫ﺑﻌﻀﻬﻤﺎ ﺇﺫﺍ ﻛﺎﻥ ‪ ∆TP‬ﻳﺆﻭﻝ ﺇﱃ ﺍﻟﺼﻔﺮ ﺃﻱ ﺃ ﱠﻥ ﻣﻴﻞ ﺍﳌﻨﺤﲎ ﺍﻟﺬﻱ ﻧﺮﻳﺪ ﻫﻮ‪:‬‬

‫‪∆ VP‬‬ ‫‪ ∂V ‬‬

‫‪lim‬‬ ‫‪= ‬‬ ‫‪‬‬ ‫)‪(14-2‬‬
‫‪∆TP → 0‬‬ ‫‪∆TP‬‬ ‫‪ ∂T  P‬‬

‫ﺃﻭ‬

‫‪ ∂V ‬‬
‫‪lim ‬‬ ‫‪ ∆TP = ∆ VP‬‬ ‫)‪(15-2‬‬
‫‪∆T → 0  ∂ T ‬‬
‫‪P‬‬ ‫‪P‬‬

‫ﺇﺫﺍ ﻛﺎﻧﺖ ‪ dVP‬ﻭ ‪ dTP‬ﺗ‪‬ﻤﺜﱢﻼﻥ ‪ lim ∆VP‬ﻭ ‪ lim ∆TP‬ﻓﺈ ﱠﻥ‪:‬‬

‫‪∆T → 0‬‬ ‫‪∆T → 0‬‬
‫‪P‬‬ ‫‪P‬‬

‫‪ ∂V ‬‬
‫‪(dV )P‬‬ ‫‪= ‬‬ ‫‪ dTP‬‬ ‫)‪(16-2‬‬
‫‪ ∂T  P‬‬

‫ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ‬ ‫‪2-6-2‬‬

‫‪‬ﺗﻌﺮ‪‬ﻑ ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ ‪ β‬ﺃﻭ ﻣﻌﺎﻣﻞ ﲤﺪ‪‬ﺩ ﺍﳊﺠﻢ ﺑﺎﻟﻌﻼﻗﺔ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬

‫‪1‬‬ ‫‪ dV  = 1  dv ‬‬

‫= ‪β‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫)‪(17-2‬‬
‫‪V‬‬ ‫‪ dT P‬‬ ‫‪v  dT P‬‬

‫ﱄ ﻓﺈ ﱠﻥ ‪ β‬ﺗ‪‬ﻌﻄﻰ ﺑﺎﻟﻌﻼﻗﺔ‪:‬‬
‫ﻭﺣﺪﺓ ‪ β‬ﻫﻲ ‪ ، K-1‬ﻭﺑﺎﻟﻨﺴﺒﺔ ﻟﻐﺎ ٍﺯ ﻣﺜﺎ ﱟ‬

‫‪1‬‬ ‫‪ d(R T P‬‬ ‫‪) ‬‬ ‫‪R‬‬ ‫‪1‬‬

‫=‪β‬‬ ‫‪‬‬ ‫‪ =P V = T‬‬ ‫)‪(18-2‬‬
‫‪V‬‬ ‫‪‬‬ ‫‪dT‬‬ ‫‪P‬‬

‫ﻭﺍﻟﱵ ﺗﻌﲏ ﺃ ﱠﻥ ‪ β‬ﺗﻌﺘﻤﺪ ﻓﻘﻂ ﻋﻠﻰ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻭﺗﺴﺎﻭﻱ ﻣﻌﻜﻮﺱ ‪ .T‬ﻧﺴﺘﻄﻴﻊ ﻛﺘﺎﺑﺔ ﺍﻟﻌﻼﻗﺔ ‪ 17-2‬ﻋﻠﻰ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪21 -‬‬ ‫‬

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‫ﺍﻟﺼﻮﺭﺓ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬

‫‪ G9 9 ‬‬
‫‪β =‬‬ ‫‪‬‬ ‫)‪(19-2‬‬
‫‪ G7  3‬‬

‫ﻭﺍﻟﱵ ﺗﻌﲏ ﺃ ﱠﻥ ﺍﻟﺘﻤ ‪‬ﺪﺩﻳ‪‬ﺔ ﻟﻴﺴﺖ ﺇ ﱠﻻ ‪‬ﺎﻳﺔ "ﻧﺴﺒﺔ ﺍﻟﺘﻤﺪ‪‬ﺩ ﰲ ﺍﳊﺠﻢ" ﻟﺘﻐﲑ ﰲ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻣﻘﺪﺍﺭﻩ ﻭﺣﺪﺓ ﻭﺍﺣﺪﺓ ﻋﻨﺪ‬

‫ﺿﻐﻂ ﺛﺎﺑﺖ‪.‬‬

‫‪∆T = T2 - T1‬‬ ‫ﻯ ﻣﻨﺘ ٍﻪ‬

‫ﻋﻨﺪﻣﺎ ﺗﻮﺟﺪ ﺻﻌﻮﺑﺔ ﰲ ﲢﺪﻳﺪ ﺍﳌﻴﻞ ﻓﺈﻧ‪‬ﻨﺎ ﻧﻌﺮ‪‬ﻑ "ﺍﻟﻘﻴﻤﺔ ﺍﳌﺘﻮﺳﻄﺔ ﻟﻠﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ" ﳌﺪ ‪‬‬

‫ﻛﺎﻟﺘﺎﱄ‪:‬‬

‫‪ V − V1 V1 ‬‬ ‫‪1 ∆ VP‬‬

‫‪β =  2‬‬ ‫= ‪‬‬ ‫)‪(20-2‬‬
‫‪ T2 −T1  P‬‬ ‫‪V1 ∆TP‬‬

‫ﻭﺍﻟﱵ ‪‬ﺗﺴﺎﻭﻱ ﻣﻴﻞ ﺍﳋﻂ ﺍﳌﺴﺘﻘﻴﻢ ﺍﻟﻮﺍﺻﻞ ﺑﻴ‪‬ﻦ ﺍﻟﻨﻘﻄﺘ‪‬ﻴﻦ ‪ 1‬ﻭ ‪ 2‬ﻣﻘﺴﻮﻣﹰﺎ ﻋﻠﻰ ‪.V‬‬

‫ﲟﺎ ﺃ ﱠﻥ ﻣﻴﻞ ﺍﻷﻳﺰﻭﺑﺎﺭ ﻭﺍﳊﺠﻢ ﻳﺘﻐﲑﺍﻥ ﻣﻦ ﻧﻘﻄﺔ ﻷُﺧﺮﻯ ﻓﺈ ﱠﻥ ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﻛ ﱟﻞ ﻣﻦ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻭﺍﻟﻀﻐﻂ‪.‬‬

‫‪0-1200‬‬ ‫‪‬ﻳﺒﻴ‪‬ﻦ ﺍﻟﺸﻜﻞ ‪ 9-2‬ﺍﻟﺘﺎﱄ ﻛﻴﻒ ﺗﺘﻐﲑ ﲤﺪ‪‬ﺩﻳ‪‬ﺔ ﺍﻟﻨﺤﺎﺱ ﻣﻊ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻋﻨﺪ ‪ P = 1 atm‬ﻟﻠﻤﺪﻯ‬

‫‪ .K‬ﺗﺆﻭﻝ ‪ β‬ﺇﱃ ﺍﻟﺼﻔﺮ ﻋﻨﺪﻣﺎ ﺗﺆﻭﻝ ‪ T‬ﺇﱃ ﺍﻟﺼﻔﺮ ﻟﻠﻤﻌﺎﺩﻥ‪.‬‬

‫ﺍﻟﻨﺤﺎﺱ ﻋﻨﺪ ‪ P = 1 atm‬ﻟﻠﻤﺪﻯ ‪0-1200 K‬‬ ‫ﺍﻟﺸﻜﻞ ‪ :9-2‬ﲤﺪ‪‬ﺩﻳ‪‬ﺔ‬

‫ﻭﻳ‪‬ﺒﻴ‪‬ﻦ ﺍﻟﺸﻜﻞ ‪ 10-2‬ﺍﻟﺘﺎﱄ ﺗﻐﲑ ‪ β‬ﻟﻠﺰﺋﺒﻖ ﻣﻊ ﺍﻟﻀﻐﻂ ﻋﻨﺪ ‪.T = 0 0C‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪22 -‬‬ ‫‬

 ‫א‬ ‫א‬

‫ﺍﻟﺰﺋﺒﻖ ﻋﻨﺪ ‪T = 0 °C‬‬ ‫ﺍﻟﺸﻜﻞ ‪ :10-2‬ﺗﻐﲑ ﲤﺪ‪‬ﺩﻳ‪‬ﺔ‬

‫ﻻﺣﻆ ﺃ ﱠﻥ ﻧﻘﻄﺔ ﺍﻷﺻﻞ ﻻ ﺗﻈﻬﺮ ﻋﻠﻰ ﺍﻟﺸﻜﻞ ﻭﺃ ﹼﻥ ‪ β‬ﻻ ﺗﺘﻐﲑ ﺇ ﹼﻻ ﻗﻠﻴ ﹰ‬

‫ﻼ ﺑﺘﻐﻴﲑ ﺍﻟﻀﻐﻂ ﺣﺘ‪‬ﻰ ‪.7000 atm‬‬

‫ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ ﰲ ﺣﺎﻟﺔ ﺍﳌﺎﺀ ﻭﻟﻠﻤﻮﺍﺩ ﺍﻟﺼﻠﺒﺔ‬ ‫‪3-6-2‬‬

‫ﳝﻠﻚ ﺍﳌﺎﺀ ﺍﻟﺴﺎﺋﻞ ﻛﺜﺎﻓ ﹰﺔ ﻗﺼﻮﻯ ﻭﺣﺠﻤﹰﺎ ﻧﻮﻋﻴﹰﺎ ﺃﺩﱏ ﻋﻨﺪ ‪ .T = 4 °C‬ﻳﺘﻨﺎﻗﺺ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺑ‪‬ﻴ ‪‬ﻦ ‪ 0 °C‬ﻭ‬

‫‪ 4 °C‬ﻋﻨﺪ ﺯﻳﺎﺩﺓ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻭﺗﻜﻮﻥ ﲤﺪ‪‬ﺩﻳ‪‬ﺔ ﺍﳌﺎﺀ ﻫﻨﺎ ﺳﺎﻟﺒﺔ ﰲ ﺣﲔ ﺗﻜﻮﻥ ﺗﺴﺎﻭﻱ ﺻﻔﺮﹰﺍ ﻋﻨﺪ ‪.T = 4 °C‬‬

‫ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﻤﻮﺍﺩ ﺍﻟﺼﻠﺒﺔ ﻓﺈ ﱠﻥ ﺟﺪﺍﻭﻝ ﺧﻮﺍﺹ ﺍﳌﻮﺍﺩ ﺗ‪‬ﻌﻄﻲ ﻗﻴ ‪‬ﻢ ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ ﺍﳋﻄﻴ‪‬ﺔ ﻟﻠﻤﻮﺍﺩ ﺍﻟﺼﻠﺒﺔ ﻭﺭﻣﺰﻫﺎ ‪ α‬ﻭﺍﳌﻌـﺮ‪‬ﻓﺔ‬

‫ﺑﺎﻟﻌﻼﻗﺔ‪:‬‬

‫‪α = 3β‬‬ ‫)‪(21-2‬‬

‫ﻭﻫﺬﻩ ﺍﻟﻘﻴﻢ ﺗﻜﻮﻥ ﻋﺎﺩ ﹰﺓ ﻣﺘﻮﺳﻄﺔ ﳌﺪﻯ )ﻟﻔﺘﺮﺓ( ﰲ ‪ T‬ﻗﺮﻳﺒﺔ ﻣﻦ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻟﻐﺮﻓﺔ ﻭﻋﻨﺪ ﺿﻐﻂ ﻳﺴﺎﻭﻱ ﺍﻟﻀﻐﻂ‬

‫ﺍﳉﻮﻱ ﻭﻻ ﺗ‪‬ﻌﻄﻲ ﻓﻜﺮ ﹰﺓ ﺗﻔﺼﻴﻠﻴ‪‬ﺔ ﻛﺎﻣﻠ ﹰﺔ ﻋﻦ ﺍﻟﻌﻼﻗﺔ ﺍﳌﹸﻌﻘﱠﺪﺓ ﺍﻟﱵ ﺗﺼﻒ ﺍﻋﺘﻤﺎﺩ ﺍﳊﺠﻢ ﻋﻠﻰ ﺍﳊﺮﺍﺭﺓ ﻭﺍﻟﻀﻐﻂ‪.‬‬

‫‪Isothermal compressibility‬‬ ‫ﺍﻻﻧﻀﻐﺎﻃﻴ‪‬ﺔ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺔ‬ ‫‪4-6-2‬‬

‫ﻟﻨﻌﺘﱪ ﺗﻐﻴ‪‬ﺮﹰﺍ ﰲ ﺍﳊﺠﻢ ﳌﺎﺩﺓ ﻋﻨﺪ ﺗﻐﻴﲑ ﺍﻟﻀﻐﻂ ﲢﺖ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺛﺎﺑﺘﺔ‪ ،‬ﻛﺎﻟﻌﻤﻠﻴ‪‬ﺔ ﺍﻟﱵ ﺗﻨﻘﻞ ﺍﻟﻨﻈﺎﻡ ﰲ ﺍﻟﺸﻜﻞ ﻣﻦ‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪23 -‬‬ ‫‬

 ‫א‬ ‫א‬

‫ﺍﻟﻨﻘﻄﺔ ‪ 2‬ﺇﱃ ﺍﻟﻨﻘﻄﺔ ‪ 3‬ﻋﱪ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ ‪ .T2‬ﻧﺴﺘﻄﻴﻊ ﺃ ﹾﻥ ﻧﻜﺘﺐ ﻫﻨﺎ ﻣﻌﺎﺩﻟ ﹰﺔ ﺷﺒﻴﻬ ﹰﺔ ﺑﺎﳌﻌﺎﺩﻟﺔ ‪ 9-2‬ﺑﻮﺿﻊ ﺍﻟﺮﻣﻮﺯ‬

‫ﺍﳌﻨﺎﺳﺒﺔ ﻭﻳ‪‬ﻌﺒ‪‬ﺮ ﺑﺎﳌﻌﺎﺩﻟﺔ ﺍﻟﺘﺎﻟﻴﺔ ﻋﻦ ﺍﻟﺘﻐﲑ ﰲ ﺍﳊﺠﻢ ﰲ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺔ ﺍﻟﱵ ﳜﻀﻊ ﳍﺎ ﺍﻟﻨﻈﺎﻡ ﻣﻦ ﺍﻟﻨﻘﻄﺔ ‪ 2‬ﺇﱃ‬

‫ﺍﻟﻨﻘﻄﺔ ‪:3‬‬

‫‪ ∂ V  ∆P = ∆ V‬‬
‫‪lim ‬‬ ‫‪‬‬ ‫‪T‬‬ ‫‪T‬‬ ‫)‪(22-2‬‬
‫‪∆P → 0  ∂ P  T‬‬
‫‪T‬‬

‫ﺇﺫﺍ ﻛﺎﻧﺖ ‪ dVT‬ﻭ ‪ dPT‬ﺗ‪‬ﻤﺜﱢﻼﻥ ‪ lim ∆VT‬ﻭ ‪ lim ∆PT‬ﻓﺈ ﱠﻥ‪:‬‬

‫‪∆PT → 0‬‬ ‫‪∆PT → 0‬‬

‫‪∂V‬‬
‫‪(dV ) T = ‬‬ ‫‪ dPT‬‬ ‫)‪(23-2‬‬
‫‪ ∂ P T‬‬

‫‪‬ﻧﻌﺮ‪‬ﻑ ﻛﻤﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻟﹻ ‪ ،β‬ﺍﻻﻧﻀﻐﺎﻃﻴ‪‬ﺔ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻳ‪‬ﺔ ‪ κ‬ﺑﺄ‪‬ﻧﻬﺎ ﻣﻴﻞ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ ﻋﻨﺪ ﺃﻳ‪‬ﺔ ﻧﻘﻄﺔ ﻣﻘﺴﻮﻣﹰﺎ ﻋﻠﻰ‬

‫ﺍﳊﺠﻢ ﺃﻱ‪:‬‬

‫‪1  dV ‬‬ ‫‪1  dv ‬‬

‫‪κ = −‬‬ ‫‪‬‬ ‫‪ = −  ‬‬ ‫)‪(24-2‬‬
‫‪V  dP  T‬‬ ‫‪v  dP  T‬‬

‫ﺗﺄﺧﺬ ﺍﻹﺷﺎﺭﺓ ﺍﻟﺴﺎﻟﺒﺔ ﰲ ﺗﻌﺮﻳﻒ ‪ κ‬ﰲ ﺍﻻﻋﺘﺒﺎﺭ ﺃ ﱠﻥ ﺍﳊﺠﻢ ﻳﺘﻨﺎﻗﺺ ﺑﺰﻳﺎﺩﺓ ﺍﻟﻀﻐﻂ ﻋﻨﺪ ‪ T‬ﺛﺎﺑﺘﺔ‪ ،‬ﻭﺑﺎﻟﺘﺎﱄ ﻓﺈ ﱠﻥ‬

‫‪ .κ > 0‬ﻭﺣﺪﺓ ‪ κ‬ﻫﻲ ﻣﻌﻜﻮﺱ ﻭﺣﺪﺓ ﺍﻟﻀﻐﻂ ﺃﻱ ‪ .N-1 m2‬ﺑﺎﻟﻨﺴﺒﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﻓﺈ ﱠﻥ ﺍﻹﻧﻀﻐﺎﻃﻴ‪‬ﺔ ﻫﻲ‪:‬‬

‫‪1  d(R T P ) ‬‬ ‫‪RT‬‬ ‫‪1‬‬

‫‪κ = −‬‬ ‫‪‬‬ ‫= ‪ = 2‬‬ ‫)‪(25-2‬‬
‫‪V‬‬ ‫‪dP‬‬ ‫‪T‬‬ ‫‪P‬‬ ‫‪P‬‬

‫ﻭﺑﻨﻔﺲ ﺍﻟﻄﺮﻳﻘﺔ ﻧ‪‬ﻌﺮ‪‬ﻑ ﺍﻹﻧﻀﻐﺎﻃﻴ‪‬ﺔ ﺍﳌﺘﻮﺳﻄﺔ ﺑﺎﻟﺘﺎﱄ‪:‬‬

‫‪1 ∆ VT‬‬
‫‪κ = −‬‬ ‫)‪(26-2‬‬
‫‪V1 ∆PT‬‬

‫ﺗﻌﺘﻤﺪ ﺍﻹﻧﻀﻐﺎﻃﻴ‪‬ﺔ‪-‬ﻣﺜﻞ ﺍﻟﺘﻤﺪ‪‬ﺩﻳﺔ‪ -‬ﻋﻠﻰ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻭﺍﻟﻀﻐﻂ‪ .‬ﻳ‪‬ﺒ‪‬ﻴ ‪‬ﻦ ﺍﻟﺸﻜﻞ ‪ 9-2‬ﺃﻳﻀﹰﺎ ﺗﻐﲑ ‪ κ‬ﻣﻊ ‪ T‬ﻟﻠﻨﺤﺎﺱ‬

‫ﻭﺍﻟﺸﻜﻞ ‪ 10-2‬ﺗﻐﲑ ‪ κ‬ﻣﻊ ‪ P‬ﻟﻠﺰﺋﺒﻖ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪24 -‬‬ ‫‬

 ‫א‬ ‫‪−κ β‬א‬

‫ﺃﳘﻴ‪‬ﺔ ‪ β‬ﻭ ‪ - κ‬ﺍﺷﺘﻘﺎﻕ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ‬ ‫‪7-2‬‬

‫ﺙ ﲢﺖ ﺿﻐﻂ ﺛﺎﺑﺖ )ﻣﻦ ﺍﻟﻨﻘﻄﺔ ‪ 1‬ﺇﱃ ﺍﻟﻨﻘﻄﺔ ‪ 2‬ﰲ ﺍﻟﺸﻜﻞ ‪ (7-2‬ﺃﻭ ﻋﻨﺪ ﺩﺭﺟﺔ‬
‫ﺣﺘ‪‬ﻰ ﺍﻵﻥ ﺍﻋﺘﱪﻧﺎ ﻋﻤﻠﻴﺎﺕ ﲢﺪ ﹸ‬

‫ﺣﺮﺍﺭﺓ ﺛﺎﺑﺘﺔ )ﻣﻦ ﺍﻟﻨﻘﻄﺔ ‪ 2‬ﺇﱃ ﺍﻟﻨﻘﻄﺔ ‪ 3‬ﰲ ﻧﻔﺲ ﺍﻟﺸﻜﻞ(‪ .‬ﻟﻨﻌﺘﱪ ﺍﻵﻥ ﺃ ﱠﻥ ﺣﺎﻟﱵ ﺍﻟﻨﻈﺎﻡ ﻟﻴﺴﺘﺎ ﻋﻠﻰ ﻧﻔﺲ ﺍﻟﻀﻐﻂ‬

‫ﻭﻻ ﲢﺖ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻛﺎﳊﺎﻟﺘﻴ‪‬ﻦ ‪ 1‬ﻭ ‪ .3‬ﻳﻌﺘﻤﺪ ﻓﺮﻕ ﺍﳊﺠﻢ ﺑﻴ‪‬ﻦ ﺍﳊﺎﻟﺘﻴ‪‬ﻦ ﻋﻠﻰ ﺍﳊﺎﻟﺘﻴ‪‬ﻦ ﻧﻔﺴﻬﻤﺎ ﻓﻘﻂ ﻭﻻ‬

‫ﻳﻌﺘﻤﺪ ﺇﻃﻼﻗﹰﺎ ﻋﻠﻰ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﺍﻟﱵ ﻣ ‪‬ﺮ ‪‬ﺎ ﺍﻟﻨﻈﺎﻡ ﺑﻴ‪‬ﻦ ﻫﺎﺗﻴ‪‬ﻦ ﺍﳊﺎﻟﺘﻴ‪‬ﻦ‪.‬‬

‫ﻣﻦ ﺍﻟﻮﺍﺿﺢ ﺃ ﱠﻥ ﺗﻐﲑ ﺍﳊﺠﻢ ‪ ∆V‬ﻣﻦ ‪ 1‬ﺇﱃ ‪ 3‬ﻳﺴﺎﻭﻱ ﺍﻟﺘﻐﲑ ﰲ ﺍﳊﺠﻢ ﻣﻦ ‪ 1‬ﺇﱃ ‪.2‬‬

‫‪∆T‬‬ ‫‪ ∆VP‬ﺯﺍﺋﺪﹰﺍ ﺍﻟﺘﻐﲑ ﰲ ﺍﳊﺠﻢ ﻣﻦ ‪ 2‬ﺇﱃ ‪ ∆VT 3‬ﺃﻱ ﺃ ﱠﻥ ‪ ∆V = ∆VP + ∆VT‬ﻭﻋﻨﺪﻣﺎ ﺗﺆﻭﻝ ‪ ∆P‬ﻭ‬

‫ﺐ ﺗﻔﺎﺿﻞ ﺍﻟﺘﻐﲑ ﰲ ﺍﳊﺠﻢ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﳌﻌﺎﺩﻟﺘﻴ‪‬ﻦ ‪ 9-2‬ﻭ ‪ 14-2‬ﻛﻤﺎ ﻳﻠﻲ‪:‬‬

‫ﺇﱃ ﺍﻟﺼﻔﺮ ﻓﺈﻧ‪‬ﻨﺎ ﻧﺴﺘﻄﻴﻊ ﺃ ﹾﻥ ﻧﻜﺘ ‪‬‬

‫‪∂V ‬‬ ‫‪ ∂ V  dP‬‬

‫‪dV = ‬‬ ‫‪ dT + ‬‬ ‫‪‬‬ ‫)‪(27-2‬‬
‫‪ ∂ T P‬‬ ‫‪ ∂P  T‬‬

‫ﺃﻭ‬

‫‪dV = β V dT - κ V dP‬‬ ‫)‪(28-2‬‬

‫ﺃﻭ‬

‫‪dV‬‬
‫‪= β dT - κ dP‬‬ ‫)‪(29-2‬‬
‫‪V‬‬
‫‬ ‫‬
‫= ‪ . κ‬ﺑﺎﻟﺘﻌﻮﻳﺾ ﰲ ﺍﳌﹸﻌﺎﺩﻟﺔ ‪ 29-2‬ﻟﺪﻳﻨﺎ ﰲ ﻫﺬﻩ ﺍﳊﺎﻟﺔ‪:‬‬ ‫= ‪ β‬ﻭﺃ ﱠﻥ‬ ‫ﻟﻨﻔﺮﺽ ﺃﻧ‪‬ﻨﺎ ﻭﺟﺪﻧﺎ ﳐﱪﻳﹰﺎ ﺃ ﱠﻥ‬
‫‪3‬‬ ‫‪7‬‬

‫‪dV‬‬ ‫‪dT dP‬‬

‫=‬ ‫‪-‬‬ ‫)‪(30-2‬‬
‫‪V‬‬ ‫‪T‬‬ ‫‪P‬‬

‫ﺃﻭ‬

‫‪dV‬‬ ‫‪dT dP‬‬

‫‪−‬‬ ‫‪+‬‬ ‫‪=0‬‬ ‫)‪(31-2‬‬
‫‪V‬‬ ‫‪T‬‬ ‫‪P‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪25 -‬‬ ‫‬

 ‫א‬ ‫‪−κ β‬א‬

‫ﻭﺑﺘﻜﺎﻣﻞ ﺍﻟﻄﺮﻓﲔ ﳒﺪ‪:‬‬

‫‪ln V - ln T + ln P = ln A = constant‬‬ ‫)‪(32-2‬‬

‫ﺃﻭ‬

‫‪PV‬‬
‫)‪= n R = (exp A‬‬ ‫)‪(33-2‬‬
‫‪T‬‬

‫ﺍﻟﺜﺎﺑﺖ )‪A = ln (nR‬‬ ‫ﻭﻫﺬﻩ ﻟﻴﺴﺖ ﺇ ﱠﻻ ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﻐﺎﺯ ﻣﺜﺎﱄ ﺑﺄﺧﺬ‬

‫ﺑﺎﺳﺘﺨﺪﺍﻡ ‪ β‬ﻭ ‪κ‬‬ ‫ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﺼﻠﺐ ﺃﻭ ﻟﺴﺎﺋﻞ‬

‫)‪(P, V, T‬‬ ‫ﺑﺘﻜﺎﻣﻞ ﻃﺮﰲ ﺍﳌﹸﻌﺎﺩﻟﺔ ‪ dV = β V dT - κ V dP‬ﺑﻴ‪‬ﻦ ﻧﻘﻄﺘﻴ‪‬ﻦ )‪ (P0, V0, T0‬ﻭ‬

‫ﺗﻨﺘﻤﻴﺎﻥ ﻟﻠﺴﻄﺢ ‪ P-V-T‬ﳒﺪ ﺃ ﱠﻥ‪:‬‬

‫‪V‬‬ ‫‪T‬‬ ‫‪P‬‬

‫‪∫ dV = V - V‬‬
‫‪V0‬‬
‫‪0‬‬ ‫=‬
‫‪∫ β V dT - ∫ κ V dP‬‬
‫‪T0‬‬ ‫‪P0‬‬
‫)‪(34-2‬‬

‫ﺇﺫﺍ ﺍﻋﺘﱪﻧﺎ ﺍﳊﻘﻴﻘﺔ ﺍﻟﻔﻴﺰﻳﺎﺋﻴ‪‬ﺔ )ﺍﳌﺨﱪﻳﺔ( ﺃ ﱠﻥ ﺗﻐﲑ ﺣﺠﻢ ﺻﻠﺐ ﺃﻭ ﺳﺎﺋﻞ ﺑﺘﻐﻴﲑ ﺍﻟﻀﻐﻂ ﺃﻭ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺻﻐﲑ ﻭﺃﻧ‪‬ﻪ‬

‫ﺐ ﺃﻭﱄ ﻳ‪‬ﻤﻜﻦ ﺍﻋﺘﺒﺎﺭ ‪ V‬ﺛﺎﺑﺘﹰﺎ ﻭﻳﺴﺎﻭﻱ ‪ V0‬ﰲ ﺍﻟﻄﺮﻑ ﺍﻷﻳﺴﺮ ﻭﺇﺫﺍ ﺍﻋﺘﱪﻧﺎ ‪ β‬ﻭ ‪ κ‬ﺛﺎﺑﺘﻴ‪‬ﻦ ﻓﺈ ﱠﻥ‪:‬‬
‫ﻟِﺘﻘﺮﻳ ٍ‬

‫])‪V = V0 [1 + β (T - T0) - κ (P - P0‬‬ ‫)‪(35-2‬‬

‫ﻭﺑﺎﻟﺘﺎﱄ ﻓﺈ ﱠﻥ ﻗﻴﺎﺱ ﺍﻟﺘﻤﺪ‪‬ﺩ‪‬ﻳﺔ ﻭﺍﻹﻧﻀﻐﺎﻃﻴ‪‬ﺔ ﻭﻣﻌﺮﻓﺔ ﺍﻟﻈﺮﻭﻑ )ﺍﻟﺸﺮﻭﻁ( ﺍﻻﺑﺘﺪﺍﺋﻴ‪‬ﺔ ‪ P0 , V0 , T0‬ﻛﺎﻓﻴﺔ ﻟﺘﺤﺪﻳﺪ‬

‫ﻣﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﻟﺼﻠﺐ ﻭﺳﺎﺋﻞ ﲢﺖ ﺍﻟﺘﻘﺮﻳﺐ ﺍﻟﺴﺎﺑﻖ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪26 -‬‬ ‫‬

 ‫א‬ ‫א‬ ‫א‬

‫ﺗﻄﺒﻴﻖ ﺁﺧﺮ‪ :‬ﺇﳚﺎﺩ ﺍﻟﺜﻮﺍﺑﺖ ﺍﳊﺮﺟﺔ ﻟﻐﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‬ ‫‪8-2‬‬

‫ﻋﻠﻰ ﺍﻟﺮﻏﻢ ﻣﻦ ﺑﺴﺎﻃﺔ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‪ ،‬ﻓﺈ ﱠﻥ ﻏﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻟﻪ ﻧﻘﻄﺔ ﺣﺮﺟﺔ ﻭﺳﻄﺢ ‪ P-v-T‬ﻟﻪ‬

‫ﺧﺼﺎﺋﺺ ﺗ‪‬ﺮﺍﺩﻑ ﻣﻨﻄﻘﺔ ﺳﺎﺋﻞ‪-‬ﲞﺎﺭ ﻟﻐﺎﺯ ﺣﻘﻴﻘﻲ‪ .‬ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ ﻫﻲ ﻧﻘﻄﺔ ﺍﻟﺘﻘﺎﺀ ﺍﳉﺬﻭﺭ ﺍﻟﺜﻼﺛﺔ ﺍﳊﻘﻴﻘﻴ‪‬ﺔ‬

‫ﻟﻠﻤﻌﺎﺩﻟﺔ‪ .‬ﻋﻨﺪ ﺩﺭﺟﺎﺕ ﺣﺮﺍﺭﺓ ﲢﺖ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ ﻻ ﻳﻈﻬﺮ ﺍﳉﺰﺀ ﺍﻷﻓﻘﻲ‪-‬ﻭﺍﻟﺬﻱ ﻳ‪‬ﻤﻜﻦ ﺃ ﹾﻥ ﻳﺘﻌﺎﻳﺶ ﻓﻴﻪ‬

‫ﻃﻮﺭ ﺍﻟﺴﺎﺋﻞ ﻭﻃﻮﺭ ﺍﻟﺒﺨﺎﺭ ﻟﻐﺎﺯ ﺣﻘﻴﻘﻲ‪ -‬ﰲ ﺃﻳﺰﻭﺣﺮﺍﺭﻳﺎﺕ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‪.‬‬

‫ﻭﻣﻊ ﺫﻟﻚ ﻓﻴ‪‬ﻤﻜﻨﻨﺎ ﺗﱪﻳﺮ ﺍﳋﻂ ﺍﻷﻓﻘﻲ ‪ abc‬ﰲ ﺍﻟﺸﻜﻞ ‪ 1-6-2‬ﺑﺮﲰﻪ ﻛﻀﻐﻂ ﲝﻴ ﹸ‬
‫ﺚ ﺗﻜﻮﻥ ﺍﳌﻨﺎﻃﻖ ﺍﳌﹸﻈﻠﱠﻠﺔ‬

‫ﻣﺘﺴﺎﻭﻳﺔ‪ .‬ﺗ‪‬ﻤﺜﱢﻞ ﺍﻟﻨﻘﻄﺘﺎﻥ ‪ a‬ﻭ ‪ c‬ﻋﻨﺪﻫﺎ ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻟﻠﺴﺎﺋﻞ ﺍﳌﺸﺒﻊ ﻭﻟﻠﺒﺨﺎﺭ ﺍﳌﺸﺒﻊ ﻋﻠﻰ ﺍﻟﺘﻮﺍﱄ‪.‬‬

‫‪∂P ‬‬
‫‪1-6-2‬‬ ‫‪ . ‬ﻭﺑﺎﻟﻨﻈﺮ ﺇﱃ ﺍﻟﺸﻜﻞ‬ ‫ﺑﺎﻟﻌﻼﻗﺔ ‪‬‬ ‫ﺇ ﱠﻥ ﻣﻴﻞ ﻣﺴﻘﻂ ﻣﻨﺤﲎ ﺃﻳﺰﻭﺣﺮﺍﺭﻱ ﻋﻠﻰ ﻣﺴﺘﻮﻯ ‪ P-v‬ﻳ‪‬ﻌﻄﻰ‬
‫‪ ∂ v T‬‬

‫ﻓﺈﻧ‪‬ﻨﺎ ﻧﺮﻯ ﺃﻧ‪‬ﻪ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ ﻻ ﻳﻜﻮ ﹸﻥ ﺍﳌﻴﻞ ﻓﻘﻂ ﻳﺴﺎﻭﻱ ﺻﻔﺮﹰﺍ ﻭﺇﻧ‪‬ﻤﺎ ﺗﻜﻮﻥ ﺍﻟﻨﻘﻄﺔ ﻧﻘﻄﺔ ﺍﻧﻌﻄﺎﻑ ﺃﻳﻀﺎﹰ‪،‬‬

‫ﺚ ﻳﺘﺠﻪ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ ﺇﱃ ﺍﻷﻋﻠﻰ )ﻭﻳﻜﻮﻥ ﻣﻘﻌ‪‬ﺮﹰﺍ( ﻭﺇﱃ ﻳﺴﺎﺭ ﺍﻟﻨﻘﻄﺔ ﻭﻳﺘﻘﻌ‪‬ﺮ ﺇﱃ ﺍﻷﺳﻔﻞ ﺇﱃ ﳝﻴﻨﻬﺎ ﻭﻫﺬﺍ ﻳﻌﲏ‬
‫ﺣﻴ ﹸ‬

‫ﺃ ﱠﻥ ﺍﳌﺸﺘﻘﺔ )ﺍﳉﺰﺋﻴﺔ( ﺍﻷﻭﱃ ﻭﺍﳌﺸﺘﻘﺔ ﺍﻟﺜﺎﻧﻴﺔ ﻟﻠﻤﺘﻐﲑ ‪ P‬ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﻤﺘﻐﲑ ‪ v‬ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ ﺗﺴﺎﻭﻱ ﻛ ﱞﻞ ﻣﻨﻬﻤﺎ‬

‫ﺻﻔﺮﹰﺍ ﺃﻱ‪:‬‬

‫‪∂P = 0‬‬
‫‪‬‬ ‫‪‬‬ ‫)‪(36-2‬‬
‫‪ ∂ v T‬‬

‫ﺇ ﱠﻥ ﺇﺣﺪﻯ ﺧﺼﺎﺋﺺ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺍﻟﻌﻤﻠﻴ‪‬ﺔ ﻫﻮ ﺃﻧ‪‬ﻪ ﻳ‪‬ﻤﻜﻦ ﺣﻠﱡﻬﺎ ﻟﹻ ‪ P‬ﻭﺑﺎﻟﺘﺎﱄ ﻓﺈﻧ‪‬ﻪ ﻳ‪‬ﻤﻜﻦ ﺣﺴﺎﺏ‬

‫ﺍﳌﺸﺘﻘﺎﺕ ﺍﳉﺰﺋﻴ‪‬ﺔ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﻀﻐﻂ ‪ P‬ﺑﺴﻬﻮﻟﺔ‪ .‬ﻓﻠﺪﻳﻨﺎ‪:‬‬

‫‪RT‬‬ ‫‪a‬‬
‫=‪P‬‬ ‫‪− 2‬‬ ‫)‪(1-37-2‬‬
‫‪v -b v‬‬

‫ﺃﻱ ﺃ ﱠﻥ‪:‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪27 -‬‬ ‫‬

 ‫א‬ ‫א‬ ‫א‬

‫‪ ∂P  = − R T + 2a‬‬
‫‪ ‬‬ ‫‪2‬‬ ‫)‪(2-37-2‬‬
‫‪ ∂v  T‬‬ ‫)‪(v - b‬‬ ‫‪v3‬‬

‫‪ ∂2P ‬‬ ‫‪2R T 6 a‬‬

‫= ‪ 2 ‬‬ ‫‪3‬‬
‫‪− 4‬‬ ‫)‪(3-37-2‬‬
‫‪ ∂ v T‬‬ ‫)‪(v - b‬‬ ‫‪v‬‬

‫ﻋﻨﺪ ‪ T = Tc‬ﻭ ‪) v = vc‬ﺃﻱ ﻋﻨﺪ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ ﻭﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺍﳊﺮﺝ( ﻓﺈ ﱠﻥ ﺍﳌﻌﺎﺩﻟﺘﻴ‪‬ﻦ ﺍﻟﺴﺎﺑﻘﺘﻴ‪‬ﻦ‬

‫ﺗﺴﺎﻭﻳﺎﻥ ﺻﻔﺮﺍﹰ‪ ،‬ﺃﻱ ﺃ ﱠﻥ‪:‬‬

‫‪R Tc‬‬ ‫‪2a‬‬

‫‪−‬‬ ‫‪2‬‬
‫‪+‬‬ ‫‪3‬‬
‫‪= 0‬‬ ‫)‪(1-38-2‬‬
‫) ‪( vc - b‬‬ ‫‪vc‬‬

‫‪2 R Tc‬‬ ‫‪6a‬‬

‫‪3‬‬
‫‪−‬‬ ‫‪4‬‬
‫‪= 0‬‬ ‫)‪(2-38-2‬‬
‫) ‪( vc - b‬‬ ‫‪vc‬‬
‫‪5 7F‬‬ ‫‪D‬‬
‫ﻭﺑﻮﺿﻊ ﻫﺬﻩ ﺍﻟﻘﻴﻤﺔ ﰲ ﺍﳌﻌﺎﺩﻟﺔ ‪ b-36-2‬ﳓﺼﻞ ﻋﻠﻰ‪:‬‬ ‫=‬ ‫ﻣﻦ ﺍﳌﻌﺎﺩﻟﺔ ‪ 1-38-2‬ﳒﺪ ﺃ ﱠﻥ‪:‬‬
‫ ) ‪( vF  E‬‬ ‫ ‪vF‬‬

‫‪2‬‬ ‫‪2a‬‬ ‫‪6a‬‬

‫‪× 3 = 4‬‬ ‫)‪(39-2‬‬
‫‪( vc - b ) vc‬‬ ‫‪vc‬‬

‫ﺃﻱ ﺃ ﱠﻥ‪ 2vC = 3vC - 3b :‬ﻭﺑﺎﻟﺘﺎﱄ ﺃ ﱠﻥ‪:‬‬

‫‪vc = 3 b‬‬ ‫)‪(40-2‬‬

‫ﻭﺑﺘﻌﻮﻳﺾ ﻗﻴﻤﺔ ‪ vc‬ﰲ ﺍﳌﻌﺎﺩﻟﺔ ‪ 1-38-2‬ﳒﺪ ‪ Tc‬ﺑﺪﻻﻟﺔ ‪ R‬ﻭﺛﺎﺑﱵ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ‪ a‬ﻭ ‪:b‬‬

‫‪2a‬‬ ‫‪4 b2‬‬ ‫‪8a‬‬

‫= ‪Tc‬‬ ‫×‬ ‫=‬ ‫)‪(41-2‬‬
‫‪27 b3‬‬ ‫‪R‬‬ ‫‪27 R b‬‬

‫ﻭﻣﻦ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﳒﺪ ﻗﻴﻤﺔ ﺍﻟﻀﻐﻂ ﺍﳊﺮﺝ ﻭﺍﻟﺬﻱ ﻳ‪‬ﺴﺎﻭﻱ‪:‬‬

‫‪8 a 27 b‬‬ ‫‪a‬‬ ‫‪a‬‬

‫= ‪Pc‬‬ ‫‪−‬‬ ‫‪2‬‬
‫=‬ ‫)‪(42-2‬‬
‫‪2b‬‬ ‫‪9b‬‬ ‫‪27 b 2‬‬

‫‪‬ﺗﺴﺘﺨﺪﻡ ﺍﻟﻌﻼﻗﺎﺕ ﺍﻟﺜﻼﺙ ﺍﻟﺴﺎﺑﻘﺔ ﻟﺘﺤﺪﻳﺪ ﻗﻴﻤﺔ ﻛ ﱟﻞ ﻣﻦ ‪ a‬ﻭ ‪ b‬ﻟﻐﺎﺯ ﻣﺎ ﺑﺪﻻﻟﺔ ﻗﻴﻢ ﺍﻟﺜﻮﺍﺑﺖ ﺍﳊﺮﺟﺔ ﺍﳌﻘﺎﺳﺔ‬

‫ﳐﱪﻳﹰﺎ‪.‬‬

‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ ‪28 -‬‬ ‫‬

 ‫ﻣﻘﺎﺭﻧﺔ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﲟﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ﳌﺎﺩﺓ ﺣﻘﻴﻘﻴ‪‬ﺔ‬ ‫‪-‬‬

‫ﻣﻊ ﺫﻟﻚ ﻭﻷ ﱠﻥ ﻟﺪﻳﻨﺎ ﺛﻼﺙ ﻣﻌﺎﺩﻻﺕ ﲟﺠﻬﻮﻟﻴ‪‬ﻦ ‪ a‬ﻭ ‪ b‬ﻓﺈ ﱠﻥ ﺍﻷﺧﲑﻳ‪‬ﻦ ﻗﺪ ﻳﺄﺧﺬﺍﻥ ﺃﻛﺜﺮ ﻣﻦ ﻗﻴﻤﺔ ﻓﺒﻘﺴﻤﺔ ﺍﳌﻌﺎﺩﻟﺔ‬

‫‪ 41-2‬ﻋﻠﻰ ﺍﳌﻌﺎﺩﻟﺔ ‪) 42-2‬ﻭﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﳌﻌﺎﺩﻟﺔ ‪ 40-2‬ﳒﺪ ﺃ ﱠﻥ ‪ ( b = vc/3‬ﳒﺪ ﺃ ﱠﻥ‪:‬‬

‫‪5 7F‬‬
‫= ‪E‬‬
‫‪ 3F‬‬

‫ﻭﻫﺬﺍ ﻳﻌﲏ ﺃﻧ‪‬ﻨﺎ ﻻ ﳓﺼﻞ ﻋﻠﻰ ﻧﻔﺲ ﺍﻟﻘﻴﻤﺔ ﻟﻠﺜﺎﺑﺖ ‪ b‬ﺑﺘﻌﻮﻳﺾ ﻗﻴﻢ ‪ Tc ،vc‬ﻭ ‪ Pc‬ﰲ ﺍﻟﻌﻼﻗﺘﻴ‪‬ﻦ ﺍﻟﺴﺎﺑﻘﺘﻴ‪‬ﻦ‪ ،‬ﺃﻱ‬

‫ﺃﻧ‪‬ﻨﺎ ﻻ ﻧﺴﺘﻄﻴﻊ ﺃ ﹾﻥ "ﻧ‪ ‬ﹾﻄِﺒ ‪‬ﻖ" ﺳﻄﺢ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻋﻠﻰ ﺳﻄﺢ ﻣﺎﺩﺓ ﺣﻘﻴﻘﻴ‪‬ﺔ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ‪ .‬ﻭﺑﻄﺮﻳﻘﺔ ﻣﻜﺎﻓﺌﺔ‬

‫ﻳ‪‬ﻤﻜﻦ ﺃ ﹾﻥ ﺗﻨﻄﺒﻖ ﻗﻴﻤﺔ ﺍﺛﻨﻴ‪‬ﻦ ﻣﻦ ﺍﳌﺘﻐﲑﺍﺕ ﻭﻟﻜ ‪‬ﻦ ﻟﻴﺲ ﺍﻟﺜﻼﺛﺔ ﻣﻌﹰﺎ! ﻫﻨﺎﻙ ﻃﺮﻳﻘ ﹲﺔ ﺃﹸﺧﺮﻯ ﻟﻠﻤﻘﺎﺭﻧﺔ ﺑﲔ ﺳﻄﺢ ﻓﺎﻥ ﺩ ‪‬ﺭ‬

‫ﺐ ﺍﻟﻘﻴﻤﺔ ‪ Pv/RT‬ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ‪ .‬ﺑﺎﻟﻨﺴﺒﺔ ﻟﻐﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻟﺪﻳﻨﺎ‪:‬‬
‫ﻓﺎﻟﺲ ﻭﺳﻄﺢ ﻣﺎﺩﺓ ﺣﻘﻴﻘﻴﺔ‪ .‬ﻟﻨﺤﺴ ‪‬‬

‫‪Pc vc‬‬ ‫‪a‬‬ ‫‪27 b‬‬ ‫‪3‬‬

‫=‬ ‫×‬ ‫‪3‬‬ ‫‪b‬‬ ‫×‬ ‫=‬ ‫‪= 0.375‬‬ ‫)‪(43-2‬‬
‫‪R Tc‬‬ ‫‪27 b 2‬‬ ‫‪8a‬‬ ‫‪8‬‬

‫ﻭﻫﺬﻩ ﺍﻟﻌﻼﻗﺔ ﺻﺎﳊﺔ ﻷﻳ‪‬ﺔ ﻣﺎﺩﺓ ﻣﻦ "ﻃﺮﺍﺯ" ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ‪ .‬ﻳ‪‬ﺒﻴ‪‬ﻦ ﺍﳉﺪﻭﻝ ‪ 4-2‬ﺍﻟﺘﺎﱄ ﻗﻴﻢ‬

‫ﺍﻟﻨﺴﺒﺔ ‪ Pc vc / R Tc‬ﻟﺒﻌﺾ ﺍﳌﻮﺍﺩ‪ .‬ﻻ ﺗ‪‬ﻄﺎﺑﻖ ﻫﺬﻩ ﺍﻟﻘﻴﻢ ﺍﻟﻘﻴﻤﺔ ﺍﳌﺘﻮﻗﻌﺔ ﺣﺴﺐ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺇ ﱠﻻ ﺃﻧ‪‬ﻬﺎ ﻟﻴﺴﺖ‬

‫ﺑﻌﻴﺪﺓ ﻋﻨﻬﺎ ﻭﳍﺬﺍ ﺗ‪‬ﻌﺘ ‪‬ﱪ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺗﻘﺮﻳﺒﹰﺎ ﺟﻴﺪﹰﺍ ﻟﻮﺻﻒ ﺣﺎﻟﺔ ﺍﳌﺎﺩﺓ‪.‬‬

‫‪Pc vc / R Tc‬‬ ‫ﺍﳌﺎﺩﺓ‬

‫‪0.327‬‬ ‫‪He‬‬ ‫ﺍﳍﻴﻠﻴﻮﻡ‬
‫‪0.306‬‬ ‫‪H2‬‬ ‫ﻏﺎﺯ ﺍﳍﻴﺪﺭﻭﺟﲔ‬
‫‪0.292‬‬ ‫‪O2‬‬ ‫ﻏﺎﺯ ﺍﻷﻛﺴﺠﲔ‬
‫‪0.277‬‬ ‫‪CO2‬‬ ‫ﺛﺎﱐ ﺃﹸﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ‬
‫‪0.233‬‬ ‫‪H2O‬‬ ‫ﺍﳌﺎﺀ‬
‫‪0.909‬‬ ‫‪Hg‬‬ ‫ﺍﻟﺰﺋﺒﻖ‬
‫ﺍﳉﺪﻭﻝ ‪ Pc vc / R Tc :4-2‬ﻟﺒﻌﺾ ﺍﳌﻮﺍﺩ‬

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‫ﺻﻴﻐﺔ ﺃﹸﺧﺮﻯ ﻟِﻤﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﳊﺠﻢ ﻭﺍﻟﻀﻐﻂ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ‬ ‫‪9-2‬‬

‫ﻋﻨﺪ ﺍﻟﻨﻘﻄﺔ ﺍﳊﺮﺟﺔ‬

‫ﺑﺎﻹﻣﻜﺎﻥ ﻛﺘﺎﺑﺔ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺩﻭ ﹶﻥ ﺃ ﹾﻥ ﻳﻈﻬﺮ ﺍﻟﺜﺎﺑﺘﺎﻥ ‪ a‬ﻭ ‪ ،b‬ﻭﺫﻟﻚ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻟﻜﻤﻴ‪‬ﺎﺕ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬

‫ﺼﻐ‪‬ﺮ ‪ ،‬ﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ‬

‫‪ vr = v / vc ، Pr = P / Pc‬ﻭ ‪ Tr = T / Tc‬ﻭﺍﻟﱵ ﺗ‪‬ﺴﻤ‪‬ﻰ ﺍﻟﻀﻐﻂ ﺍ ﹸﳌ ‪‬‬

‫‪(Reduced Pressure, specific volume and‬‬ ‫ﺼﻐ‪‬ﺮﺓ‬

‫ﺼﻐ‪‬ﺮ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍ ﹸﳌ ‪‬‬
‫ﺍ ﹸﳌ ‪‬‬

‫)‪ .temperature‬ﻭﺗ‪‬ﻜﺘﺐ ﻣﻌﺎﺩﻟﺔ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ ﺑﺪﻻﻟﺔ ﺍﳌﺘﻐﲑﺍﺕ ﺍﳉﺪﻳﺪﺓ ﻋﻠﻰ ﺍﻟﺼﻮﺭﺓ‪:‬‬

‫‪‬‬ ‫‪3 ‬‬

‫‪ Pr + 2  (3 vr − 1) = 8 Tr‬‬ ‫)‪(44-2‬‬
‫‪‬‬ ‫‪vr ‬‬

‫ﻱ ﻏﺎﺯ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‪ .‬ﺗﻜﻮﻥ ﺇﺣﺪﺍﺛﻴﺎﺕ ﺍﻟﻨﻘﻄﺔ‬

‫ﻭﻫﻜﺬﺍ ﺍﺧﺘﻔﻰ ﺍﻟﺜﺎﺑﺘﺎﻥ ‪ a‬ﻭ ‪ b‬ﻭﺃﺻﺒﺤﺖ ﺍﻟﻌﻼﻗﺔ ﺻﺎﳊﺔ ﻷ ‪‬‬

‫ﺍﳊﺮﺟﺔ ﰲ ﺳﻄﺢ ‪ Pr-vr-Tr‬ﻫﻲ )‪ .(1,1,1‬ﺗ‪‬ﺴﻤ‪‬ﻰ ﺍﻟﻌﻼﻗﺔ ‪ 44-2‬ﻗﺎﻧﻮﻥ ﺍﳊﺎﻻﺕ ﺍﳌﺘﺮﺍﺩﻓﺔ‪ ،‬ﺑﺎﻓﺘﺮﺍﺽ ﺃ ﱠﻥ‬

‫ﺍﻟﻐﺎﺯﺍﺕ ﺍﳊﻘﻴﻘﻴ‪‬ﺔ ﺧﺎﺿﻌﺔ ﻟﺘﻘﺮﻳﺐ ﻓﺎﻥ ﺩ ‪‬ﺭ ﻓﺎﻟﺲ‪ .‬ﻧﻘﻮﻝ ﺃ ﱠﻥ ﻣﺎﺩﺗﻴ‪‬ﻦ ﻣﻮﺟﻮﺩﺗﺎﻥ ﰲ ﺣﺎﻟﺘﻴ‪‬ﻦ ﻣﺘﺮﺍﺩﻓﺘﻴ‪‬ﻦ ﺇﺫﺍ ﻛﺎﻥ‬

‫ﺍﻟﻀﻐﻂ ﻭﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻟِﻜ ﱟﻞ ﻣﻨﻬﻤﺎ ﻳﺴﺎﻭﻱ ﻧﻔﺲ ﺍﻟﻨﺴﺒﺔ )ﺃﻭ ﺍﳌﹸﻀﺎﻋﻒ( ﻣﻦ ﺍﻟﻀﻐﻂ ﺍﳊﺮﺝ‬

‫ﻭﺍﳊﺠﻢ ﺍﻟﻨﻮﻋﻲ ﺍﳊﺮﺝ ﻭﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﺍﳊﺮﺟﺔ ﻟﻠﻤﺎﺩﺗﻴ‪‬ﻦ‪.‬‬

‫ﺍﻟﻌﻼﻗﺔ ﺑ ‪‬ﻴ ‪‬ﻦ ﺍﳌﹸﺸﺘﻘﹼﺎﺕ ﺍﳉﺰﺋﻴﺔ‬ ‫‪10-2‬‬

‫ﻟﻘﺪ ﺭﺃﻳﻨﺎ ﺃ ﱠﻥ ﻓﺮﻕ ﺍﳊﺠﻢ ﺑﲔ ﺣﺎﻟﱵ ﺍﺗﺰﺍﻥ ﻣﺘﺠﺎﻭﺭﺗﻴ‪‬ﻦ ﻟﻨﻈﺎ ٍﻡ ﻣﺎ ﻳ‪‬ﻜﺘﺐ ﻋﻠﻰ ﺍﻟﺼﻮﺭﺓ‪:‬‬

‫‪∂V‬‬ ‫‪∂V‬‬
‫‪dV = ‬‬ ‫‪ dT + ‬‬ ‫‪ dP‬‬ ‫)‪(45-2‬‬
‫‪ ∂ T P‬‬ ‫‪ ∂ P T‬‬

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‫‪V‬‬ ‫ﻭﻫﺬﻩ ﺍﻟﻌﻼﻗﺔ ﺗﻔﺘﺮﺽ ﺃ ﱠﻥ ‪ V‬ﺩﺍﻟﺔ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ‪ P‬ﻭ ‪ .T‬ﻭﺑﻨﻔﺲ ﺍﻟﻄﺮﻳﻘﺔ ﻭﺑﺎﻋﺘﺒﺎﺭ ﺃ ﱠﻥ ‪ P‬ﺩﺍﻟﺔ ﺗﻌﺘﻤﺪ ﻋﻠﻰ ﺍﳊﺠﻢ‬

‫ﻭﻋﻠﻰ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ‪ T‬ﻓﺈ ﱠﻥ‪:‬‬

‫‪ ∂P ‬‬ ‫‪ ∂P ‬‬

‫‪d P = ‬‬ ‫‪ dT + ‬‬ ‫‪ dV‬‬ ‫)‪(46-2‬‬
‫‪ ∂ T V‬‬ ‫‪ ∂ V T‬‬

‫ﺑﺘﻌﻮﻳﺾ ‪ dP‬ﺍﻟﺴﺎﺑﻘﺔ ﰲ ﺍﳌﻌﺎﺩﻟﺔ ‪ 45-2‬ﳒﺪ ﺃ ﱠﻥ‪:‬‬

‫‪∂V‬‬ ‫‪ ∂ V   ∂ P  dT + ∂ V   ∂ P  dV‬‬

‫‪dV = ‬‬ ‫‪ dT + ‬‬ ‫‪ ‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪ ‬‬ ‫‪‬‬ ‫)‪(1-47-2‬‬
‫‪ ∂ T P‬‬ ‫‪ ∂ P T  ∂ T V‬‬ ‫‪ ∂ P T  ∂ V T‬‬

‫‪ ∂9‬‬ ‫‪ ∂3  ‬‬ ‫‪ ∂ 9 ‬‬ ‫‪ ∂ 9   ∂3  ‬‬

‫‪ −  ∂ 3 ‬‬ ‫‪‬‬ ‫‪  G9 = ‬‬ ‫‪ ‬‬ ‫‪ ‬‬ ‫‪  G7‬‬ ‫)‪(2-47-2‬‬
‫‪ ‬‬ ‫‪7‬‬ ‫‪ ∂ 9 7 ‬‬ ‫‪ ∂ 7  3  ∂ 3  7  ∂ 7  9 ‬‬

‫ﻫﺬﻩ ﺍﳌﻌﺎﺩﻟﺔ ﺻﺎﳊﺔ ﻷﻳ‪‬ﺔ ﺣﺎﻟﺘﻴ‪‬ﻦ ﻣﺘﺠﺎﻭﺭﺗﻴ‪‬ﻦ‪ ،‬ﻭﺧﺎﺻ ﹰﺔ ﳊﺎﻟﺘﻴ‪‬ﻦ ﻋﻨﺪ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻧﻔﺴﻬﺎ ‪-‬ﺃﻱ ﺣﺎﻟﺘﺎﻥ ﺗﻨﺘﻤﻴﺎﻥ‬

‫ﻟﻨﻔﺲ ﺍﻷﻳﺰﻭﺣﺮﺍﺭﻱ‪ -‬ﻭﻟﻜ ‪‬ﻦ ﳍﻤﺎ ﺣﺠﻤﺎﻥ ﳐﺘﻠﻔﺎﻥ ﺃﻱ ﺇﺫﺍ ﻛﺎﻥ ‪ dT= 0‬ﻭ ‪ dV ≠ 0‬ﻭﰲ ﻫﺬﻩ ﺍﳊﺎﻟﺔ ﻓﺈ ﱠﻥ‬

‫ﺍﻟﻄﺮﻑ ﺍﻷﻳﺴﺮ ﻣﻦ ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﺴﺎﺑﻘﺔ ﻳ‪‬ﺴﺎﻭﻱ ﺻﻔﺮﹰﺍ ﻭﻟﺪﻳﻨﺎ ﺍﻟﻌﻼﻗﺔ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬

‫‪  ∂ V   ∂P  ‬‬
‫‪1 −  ∂ P   ∂ V   dV = 0‬‬ ‫)‪(1-48-2‬‬
‫‪T‬‬ ‫‪T‬‬

‫ﺃﻭ‪:‬‬

‫‪  ∂ V   ∂P  ‬‬ ‫‪∂V‬‬ ‫‪1‬‬

‫‪1 −  ∂ P   ∂ V   = 0 ⇒  ∂ P  =  ∂ P ‬‬ ‫)‪(2-48-2‬‬
‫‪T‬‬ ‫‪T‬‬ ‫‪T‬‬
‫‪‬‬ ‫‪‬‬
‫‪ ∂ V T‬‬

‫ﻭﺑﻄﺮﻳﻘﺔ ﻣﺸﺎ‪‬ﺔ ﲤﺎﻣﹰﺎ ﻭﻋﻨﺪﻣﺎ ﺗﻜﻮﻥ ‪ dV= 0‬ﻭ ‪ ،dT ≠ 0‬ﺃﻱ ﻋﻨﺪﻣﺎ ﻳﻜﻮﻥ ﺍﻟﻄﺮﻑ ﺍﻷﳝﻦ ‪‬ﻳﺴﺎﻭﻱ ﺻﻔﺮﺍﹰ‪،‬‬

‫ﺐ ﺃ ﹾﻥ ﺗﻜﻮﻥ ﺻﺤﻴﺤﺔ‪:‬‬
‫ﻓﺈ ﱠﻥ ﺍﻟﻌﻼﻗﺔ ﺍﻟﺘﺎﻟﻴﺔ ﳚ ‪‬‬

‫‪∂ V  ∂P  + ∂ V = 0‬‬
‫‪‬‬ ‫‪ ‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫)‪(3-48-2‬‬
‫‪ ∂ P  T  ∂ T  V  ∂ T P‬‬

‫ﻭﺑﻮﺿﻊ ﺍﳌﻌﺎﺩﻟﺔ ‪ 2-48-2‬ﰲ ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﱵ ﺗﻠﻴﻬﺎ‪ ،‬ﺃﻱ ‪ ،3-48-2‬ﳒﺪ ﺍﻟﻌﻼﻗﺔ ﺍﻟﺘﺎﻟﻴﺔ‪:‬‬

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‫‪∂9‬‬ ‫‪ ∂3 ‬‬ ‫‪∂7‬‬

‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫ ‪ = −‬‬ ‫)‪(49-2‬‬
‫‪‬‬ ‫∂‬ ‫‪3‬‬ ‫‪7‬‬ ‫‪‬‬ ‫∂‬ ‫‪7‬‬ ‫‪9‬‬ ‫‪‬‬ ‫∂‬ ‫‪9‬‬ ‫‪3‬‬

‫‪‬ﺗﺴﻤ‪‬ﻰ ﺍﳌﻌﺎﺩﻟﺔ ‪ 49-2‬ﺍﻟﺴﺎﺑﻘﺔ "ﻗﺎﻋﺪﺓ ﺍﻟﺴﻠﺴﻠﺔ ‪ ." Chain rule‬ﺗﺮﺑﻂ ﻫﺬﻩ ﺍﻟﻘﺎﻋﺪﺓ ﺑ‪‬ﻴ ‪‬ﻦ ﺍﳌﹸﺸﺘﻘﺎﺕ ﺍﳉﺰﺋﻴ‪‬ﺔ‬

‫ﳌﺘﻐﲑﺍﺕ ﺍﳊﺎﻟﺔ ﺍﻟﱵ ﺗﺮﺗﺒﻂ ﻣﻌﹰﺎ ﲟﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ‪.f(P,V,T) = 0 :‬‬

‫‪ -‬ﺗﻄﺒﻴﻖ‬

‫ﻟﻨﻔﺮﺽ ﺃﻧ‪‬ﻨﺎ ﻧﺮﻳﺪ ﺣﺴﺎﺏ ﺯﻳﺎﺩﺓ ﺍﻟﻀﻐﻂ ﺍﻟﻨﺎﲡﺔ ﻋﻦ ﺯﻳﺎﺩﺓ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻟﻨﻈﺎﻡ ﺣﺠﻤﻪ ﺛﺎﺑﺖ‪ ،‬ﺃﻱ ﺃﻧ‪‬ﻨﺎ ﻧﺮﻳﺪ ﺣﺴﺎﺏ‬

‫‪∂P ‬‬
‫‪ . ‬ﻣﻦ ﺍﻟﻌﻼﻗﺔ ‪:46-2‬‬ ‫‪‬‬ ‫ﺍﳌﺸﺘﻘﺔ ﺍﳉﺰﺋﻴ‪‬ﺔ‬
‫‪ ∂ T V‬‬

‫‪∂ V‬‬
‫‪‬‬ ‫‪‬‬
‫‪ ∂P ‬‬ ‫‪ ∂ T P‬‬ ‫‪βV‬‬ ‫‪β‬‬
‫‪‬‬ ‫‪‬‬ ‫‪= −‬‬ ‫‪= −‬‬ ‫=‬ ‫)‪(50-2‬‬
‫‪ ∂ T V‬‬ ‫‪∂ V‬‬ ‫‪−κV‬‬ ‫‪κ‬‬
‫‪‬‬ ‫‪‬‬
‫‪ ∂ P T‬‬
‫‪∂P‬‬
‫ﺃﻱ ﺃ ﱠﻥ ﲟﻌﺮﻓﺘﻨﺎ ﻟﻠﻨﺴﺒﺔ ﺑ‪‬ﻴ ‪‬ﻦ ﺍﻟﺘﻤﺪ‪‬ﺩﻳ‪‬ﺔ ﻭﺍﻻﻧﻀﻐﺎﻃﻴ‪‬ﺔ‪ ،‬ﻭﳘﺎ ﻛﻤﻴ‪‬ﺘﺎﻥ ﺗﻘﺎﺳﺎﻥ ﳐﱪ‪‬ﻳﺎﹰ‪ ،‬ﻧﺴﺘﻄﻴﻊ ﻣﻌﺮﻓﺔ ‪ .  ‬ﺇ ﱠﻥ‬
‫‪ ∂ T V‬‬

‫‪β‬‬ ‫ﺍﻟﻌﻼﻗﺔ ﺍﻟﺴﺎﺑﻘﺔ ﺗﻌﲏ ﺃ ﱠﻥ ﺯﻳﺎﺩﺓ ﺍﻟﻀﻐﻂ ﺍﻟﻨﺎﲡﺔ ﻋﻦ ﺯﻳﺎﺩﺓ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻟﻨﻈﺎﻡ ﺣﺠﻤﻪ ﺛﺎﺑﺖ ﺗﺘﻨﺎﺳﺐ ﻃﺮﺩ‪‬ﻳﹰﺎ ﻣﻊ‬

‫ﻭﻋﻜﺴﻴﹰﺎ ﻣﻊ ‪ .κ‬ﺑﺎﺳﺘﺨﺪﺍﻡ ﻣﻔﺎﻫﻴﻢ ﺍﳌﺸﺘﻘﺎﺕ ﺍﳉﺰﺋﻴ‪‬ﺔ ﺍﻟﺮﻳﺎﺿﻴ‪‬ﺔ‪ ،‬ﺗ‪‬ﻌﻤ‪‬ﻢ ﺍﻟﻌﻼﻗﺘﺎﻥ ﺍﻟﺴﺎﺑﻘﺘﺎﻥ ﻷﻱ ﻧﻈﺎﻡ‬

‫ﺛﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻲ ﻣﺘﻐﲑﺍﺕ ﺍﳊﺎﻟﺔ ﻟﻪ ﻫﻲ ‪ z,y,x‬ﻭﺍﻟﱵ ﺗﺮﺗﺒﻂ ﲟﻌﺎﺩﻟﺔ ﺍﳊﺎﻟﺔ ‪ f(x,y,z) = 0‬ﻭﺗ‪‬ﻜﺘﺒﺎﻥ ﻋﻠﻰ‬

‫ﺍﻟﺼﻴﻐﺘﻴ‪‬ﻦ ﺍﻟﺘﺎﻟﻴﺘﻴ‪‬ﻦ‪:‬‬

‫= ‪∂x‬‬ ‫‪1‬‬
‫‪‬‬ ‫‪‬‬
‫‪ ∂ y z‬‬ ‫‪∂ y ‬‬ ‫)‪(51-2‬‬
‫‪‬‬ ‫‪‬‬
‫‪ ∂ x z‬‬

‫‪∂ x  ∂ y  ∂ z = −1‬‬
‫‪‬‬ ‫‪ ‬‬ ‫‪ ‬‬ ‫‪‬‬ ‫)‪(52-2‬‬
‫‪ ∂ y z  ∂ z x  ∂ x y‬‬

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 ‫א‬ ‫א‬ ‫א‬

‫ﺗﻌﻤﻴﻢ ﺗﻌﺮﻳﻒ ﺍﳋﺎﺻﻴ‪‬ﺔ ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴ‪‬ﺔ‬

‫ﺇ ﱠﻥ ﺗﻔﺎﺿﻞ ﺃﻱ ﻣﺘﻐﲑ )ﺧﺎﺻﻴ‪‬ﺔ( ﻟﻨﻈﺎﻡ ﺛﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻲ )ﻣﺜﻞ ‪ dV‬ﺃﻭ ‪ dT‬ﺃﻭ ‪ (dP‬ﺗﻔﺎﺿ ﹲﻞ ﺗﺎ ‪‬ﻡ‪ .‬ﻭﺑﺸﻜﻞ ﻋﺎﻡ‪ ،‬ﻭﻫﺬﺍ‬

‫ﺗﻌﻤﻴﻢ ﻟﺘﻌﺮﻳﻒ ﺍﳋﺎﺻﻴ‪‬ﺔ ﺍﻟﺜﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴ‪‬ﺔ‪ ،‬ﻧﻘﻮﻝ ﺃ ﱠﻥ ﻣﺘﻐﻴ‪‬ﺮﹰﺍ ﻣﺎ ﻫﻮ ﺧﺎﺻﻴ‪‬ﺔ ﻟﻨﻈﺎﻡ ﺛﲑﻣﻮﺩﻳﻨﺎﻣﻴﻜﻲ ﺇﺫﺍ ﻭﻓﻘﻂ ﺇﺫﺍ ﻛﺎﻥ‬

‫ﻼ ﺗﺎ ‪‬ﻣﹰﺎ‪) .‬ﺍﻧﻈﺮ ﺍﳌﻠﺤﻖ ‪ A2‬ﺣﻮﻝ ﺍﻟﺘﻔﺎﺿﻞ ﺍﻟﺘﺎﻡ ﻭﺍﻟﺪﻳﻨﺎﻣﻴﻜﺎ ﺍﳊﺮﺍﺭﻳ‪‬ﺔ(‬

‫ﺗﻔﺎﺿﻠﻪ ﺗﻔﺎﺿ ﹰ‬

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