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‫ﺍﻟﻤﻌﻬﺪ ﺍﻟﻌﺎﻟﻲ ﻟﻠﻌﻠﻮﻡ ﺍﻟﺘﻄﺒﻴﻘﻴ‪‬ﺔ‬
‫ﻭﺍﻟﺘﻜﻨﻮﻟﻮﺟﻴﺎ‬
‫ﻛﻴﻤﻴﺎﺀ ﺍﻟﻤﺤﺎﻟﻴﻞ ﺍﻟﻤﺎﺋﻴ‪‬ﺔ‬
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‫‪2011‬‬
‫ﻣﻨﺸﻮﺭﺍﺕ ﺍﻟﻤﻌﻬﺪ ﺍﻟﻌﺎﻟﻲ ﻟﻠﻌﻠﻮﻡ ﺍﻟﺘﻄﺒﻴﻘﻴ‪‬ﺔ ﻭﺍﻟﺘﻜﻨﻮﻟﻮﺟﻴﺎ‬

‫ ﺳﻼم ﺣﺳﯾن اﻟﮭﻼﻟﻲ‬.‫ﻣﻊ ﺗﺣﯾﺎت د‬
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Salam_Alhelali?ev=hdr_xprf
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‫‪ ٢٠١١‬ﻤ ‪ ١٤٣٢ -‬ﻫ‬

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‫‪ !" #$ %‬‬
‫‪&'()( *+ %‬‬
‫ ‪, -./‬‬
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‪01 *ّ3‬‬
‫‪4# -&5 %‬‬
‫ﺣﻘﻮﻕ ﺍﻟﻄﺒﻊ ﻭﺍﻟﻨﺸﺮ ﻭﺍﻟﺘﺮﲨﺔ ﳏﻔﻮﻇﺔ ﻟﻠﻤﻌﻬﺪ ﺍﻟﻌﺎﱄ ﻟﻠﻌﻠﻮﻡ ﺍﻟﺘﻄﺒﻴﻘﻴﺔ ﻭﺍﻟﺘﻜﻨﻮﻟﻮﺟﻴﺎ‬
‫‪6‬‬
‫ﻣﻘﺪ‪‬ﻣﺔ‬
‫ﺍﻟﻔﺼﻞ ﺍﻷﻭﻝ‬
‫ﺍﻟﺘﻮﺍﺯﻧﺎﺕ ﺍﳊﻤﻀﻴ‪‬ﺔ‪-‬ﺍﻷﺳﺎﺳﻴ‪‬ﺔ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴ‪‬ﺔ‬
‫ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺫﻴﺒ ﹰﺎ ‪6 .................................................................‬‬ ‫‪.I‬‬
‫ﺘﺫﻜﺭﺓ ﺒﺒﻌﺽ ﺍﻝﺘﻌﺎﺭﻴﻑ ‪6 ....................................................‬‬ ‫‪.1.I‬‬
‫ﺍﻝﻤﺎﺀ‪ :‬ﻤ‪‬ﺫﻴﺏ‪ ‬ﺫﻭ ﺨﻭﺍﺹ ﺘﺸﺭﻴﺩ ﻭﺇﻤﺎﻫﺔ ﻭﺘﺸﺘﻴﺕ ‪7 .............................‬‬ ‫‪.2.I‬‬
‫ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ ‪10.......................................................‬‬ ‫‪.II‬‬
‫‪ .1.II‬ﺘﻌﺎﺭﻴﻑ ‪10..................................................................‬‬
‫‪ pH‬ﻤﺤﻠﻭل ‪12.............................................................‬‬ ‫‪.2.II‬‬
‫‪ .3.II‬ﺍﻝﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪-‬ﺃﺴﺎﺱ ‪12..................................................‬‬

‫‪ .4.II‬ﺍﻝﺯﻭﺠﺎﻥ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﺨﺎﺼ‪‬ﺎﻥ ﺒﺎﻝﻤﺎﺀ ‪13....................................‬‬
‫‪ .5.II‬ﺘﻔﺎﻋل ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ ﻤﻊ ﺍﻝﻤﺎﺀ ‪14..........................................‬‬
‫‪ .6.II‬ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ‪16...........................................................‬‬
‫‪ .1.6.II‬ﺍﻝﺯﻭﺝ ‪16................................................. HA/A−‬‬
‫ﻼ ‪17...........................................‬‬
‫‪ .2.6.II‬ﺯﻭﺠﺎ ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺤ ﹰ‬
‫ﺘﺭﺘﻴﺏ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ‪18.....................................................‬‬ ‫‪.III‬‬
‫‪ .1.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﺍﻝﻀﻌﻴﻔﺔ ‪18..........................................‬‬

‫‪ .2.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﺍﻝﻘﻭﻴ‪‬ﺔ ﻭﺍﻷﺴﺱ ﺍﻝﻘﻭﻴ‪‬ﺔ ‪19......................................‬‬
‫ﻤﺨﻁﹼﻁﺎﺕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﻤﺨﻁﹼﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ‪20..........................................‬‬ ‫‪.IV‬‬
‫ﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ‪ :‬ﺩﺭﺍﺴﺔ ﻜﻤﻴ‪‬ﺔ ‪24............................................‬‬ ‫‪.V‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ‪28...................................................................‬‬ ‫‪.VI‬‬
‫‪ .VII‬ﺘﻁﺒﻴﻘﺎﺕ ‪29.........................................................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪36.................................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ‬
‫ﺣﺴﺎﺏ ‪ pH‬ﺑﻌﺾ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴ‪‬ﺔ‬
‫ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ‪42............................................‬‬ ‫‪.I‬‬
‫‪ .1.I‬ﺍﻷﻨﻭﺍﻉ ﺍﻝﻐﺎﻝﺒﺔ ﻭﺍﻝﻤﻐﻠﻭﺒﺔ ﻭﺍﻝﻤﻬﻤﻠﺔ ‪42............................................‬‬

‫‪ .2.I‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺤﻤﻀﻴﺔ ﻭﺍﻝﻤﺤﺎﻝﻴل ﺍﻷﺴﺎﺴﻴﺔ ‪43.......................................‬‬
‫‪ .3.I‬ﺍﻝﺩﻗﺔ ﻓﻲ ﻗﻴﺎﺱ ‪ pH‬ﻤﺤﻠﻭل ‪44.................................................‬‬
‫‪ .4.I‬ﺘﺤﻀﻴﺭ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻝﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ ‪45........................................‬‬
‫ﺒﻌﺽ ﺤﺴﺎﺒﺎﺕ ‪ pH‬ﻝﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ ‪46..............................................‬‬ ‫‪.II‬‬
‫‪ .1.II‬ﺍﻝﻁﺭﻴﻘﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ‪47.........................................................‬‬

‫‪ .2.II‬ﻁﺭﻴﻘﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ‪48....................................................‬‬
‫‪ .3.II‬ﺤﻤﺽ ﻗﻭﻱ‪ ،‬ﺃﺴﺎﺱ ﻗﻭﻱ‪50..................................................‬‬
‫‪ .1.3.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺤﻤﺽ ﻗﻭﻱ ‪50.....................................‬‬
‫‪ .2.3.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ ‪52......................................‬‬
‫‪ .4.II‬ﺤﻤﺽ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ‪ ،‬ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ‪54............‬‬
‫‪ .1.4.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺤﻤﺽ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ‪54...................‬‬
‫‪ .2.4.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‪57....................‬‬
‫‪ .5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﻭﺽ ﺃﻭ ﻤﺯﻴﺞ ﻤﻥ ﺃﺴﺱ ‪60.....................................‬‬
‫‪ .1.5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ﻭﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ‪60............................‬‬
‫‪ .2.5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﻀﻴﻥ ﻀﻌﻴﻔﻴﻥ ‪61...........................................‬‬
‫‪ .6.II‬ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪63...........................................‬‬
‫‪ .7.II‬ﻤﺘﺫﺒﺫﺏ ﺤﻤﻀﻲ ﺃﺴﺎﺴﻲ ‪65...................................................‬‬
‫‪ .8.II‬ﺒﻌﺽ ﻤﺯﺍﺌﺞ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ‪67...........................................‬‬
‫‪ .1.8.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ﻭﻤﻥ ﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ ‪67.........................‬‬
‫‪ .2.8.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ﻭﻤﻥ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﻏﻴﺭ ﻤﺭﺍﻓﻕ ﻝﻪ ‪68...........‬‬
‫‪ .3.8.II‬ﻤﺯﺍﺌﺞ ﻤﺨﺘﻠﻔﺔ ‪72............................................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪76.................................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻟﺚ‬
‫ﺍﳌﻌﺎﻳﺮﺍﺕ ﺍﳊﻤﻀﻴﺔ ﺍﻷﺳﺎﺳﻴﺔ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴ‪‬ﺔ‬
‫ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ‪82.....................................................‬‬ ‫‪.I‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ‪82...................................................‬‬ ‫‪.1.I‬‬
‫‪ .1.1.I‬ﺘﻌﺭﻴﻑ ‪82................................................................‬‬
‫‪ .2.1.I‬ﺍﻝﺘﻜﺎﻓﺅ ﺍﻝﺤﻤﻀﻲ‪-‬ﺍﻷﺴﺎﺴﻲ ‪83.............................................‬‬
‫‪ .3.1.I‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ‪84.....................................................‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻗﻭﻱ ﺒﺄﺴﺎﺱ ﻗﻭﻱ ‪86..........................................‬‬ ‫‪.2.I‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ ‪89.......................................‬‬ ‫‪.3.I‬‬
‫‪ .1.3.I‬ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ ‪89..............................‬‬

‫‪ .2.3.I‬ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻝﻴﺱ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ ‪92.............................‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺤﻤﺽ ﻗﻭﻱ‪93........................................‬‬ ‫‪.4.I‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪94..............................................‬‬ ‫‪.5.I‬‬
‫‪ .1.5.I‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ‪94..........................................................‬‬

‫‪ .2.5.I‬ﻋﺒﺎﺭﺍﺕ ) ‪ pH = f (x‬ﻝﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻤﻀﺎﻋﻑ ﺤﻴﺙ‬
‫‪97............................................... pK A − pK A ≥ 4‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪ .3.5.I‬ﻤﺤﺎﻜﺎﺓ ﻝﻤﻌﺎﻴﺭﺓ ﺒﻌﺽ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ‪99...............................‬‬

‫ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ‪102 ...............................................................‬‬ ‫‪.II‬‬
‫‪ .1.II‬ﺃﻤﺜﻠﺔ ‪102 ...................................................................‬‬

‫‪ .2.II‬ﺘﻌﺎﺭﻴﻑ ‪102 ................................................................‬‬
‫‪ .3.II‬ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﺠﻭﺍﺭ ﻨﻘﻁﺔ ﻤﻨﺘﺼﻑ ﻗﻴﻤﺔ ﺍﻝﺘﻜﺎﻓﺅ ‪103 ......................‬‬
‫‪ .4.II‬ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺤﻤﻀﹰﺎ ﻭﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ ‪104 .....................‬‬
‫‪ .5.II‬ﺘﻁﺒﻴﻘﺎﺕ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ‪106 ...............................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪109 ...............................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ‬
‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻟﺘﻌﻘﻴﺪ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴ‪‬ﺔ‬
‫ﺘﻤﻬﻴﺩ ‪116 ..........................................................................‬‬ ‫‪.I‬‬
‫ﻤﺸﺎﻫﺩﺍﺕ ﺘﺠﺭﻴﺒﻴ‪‬ﺔ ‪116 ......................................................‬‬ ‫‪.1.I‬‬
‫ﺘﻌﺎﺭﻴﻑ ‪116 ................................................................‬‬ ‫‪.2.I‬‬
‫ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ‪120 ........................................................‬‬ ‫‪.3.I‬‬
‫ﺜﻭﺍﺒﺕ ﻤﻤﻴ‪‬ﺯﺓ ﻝﺘﺸﻜﱡل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴ‪‬ﺔ ‪121 ...............................‬‬ ‫‪.II‬‬
‫ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ‪124 ...............................................................‬‬ ‫‪.III‬‬
‫ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﺍﻝﻤﺘﻨﺎﻓﺴﺔ ‪127 .............................................................‬‬ ‫‪.IV‬‬
‫‪ .1.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺭﺒﻴﻁﺘﻴﻥ‪ L' :‬ﻭ ‪127 ....................................... L‬‬

‫‪ .2.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﺍﻝﻤﺭﻜﺯﻴ‪‬ﺘﻴﻥ‪128 .......................................‬‬
‫ﺘﻤﺭﻴﻥ ﻤﺤﻠﻭل ‪131 ..................................................................‬‬ ‫‪.V‬‬
‫ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪ -‬ﺘﺭﻜﻴﺏ ﻤﺤﻠﻭل ‪134 ................................................‬‬ ‫‪.VI‬‬
‫‪ .1.VI‬ﺘﺸﻜﹼل ﻤﻌﻘﺩ ﻭﺤﻴﺩ ‪135 ......................................................‬‬

‫‪ .2.VI‬ﺘﺸﻜﹼل ﻋﺩﺓ ﻤﻌﻘﹼﺩﺍﺕ ﺒﺎﻝﺘﻌﺎﻗﺏ ‪137 ............................................‬‬
‫‪ .3.VI‬ﺘﺸﻜﹼل ﻋﺩﺓ ﻤﻌﻘﹼﺩﺍﺕ ﺒﺂﻥ ﻭﺍﺤﺩ ‪140 ............................................‬‬
‫‪ .VII‬ﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺘﻌﻘﻴﺩ ‪142 ................................................................‬‬
‫‪ .1.VII‬ﻤﺒﺩﺃ ﺍﻝﻤﻌﺎﻴﺭﺓ ‪142 ...........................................................‬‬
‫‪ .2.VII‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪143 ................................................ pY = f (x‬‬
‫‪ .3.VII‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ‪145 ......................................................‬‬
‫‪ .4.VII‬ﺘﻁﺒﻴﻕ ‪147 ..................................................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪148 ...............................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﳋﺎﻣﺲ‬
‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻟﺘﺮﺳﻴﺐ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ﺍﻨﺤﻼل ﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ ﻓﻲ ﺍﻝﻤﺎﺀ ؛ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ‪158 ...............................‬‬ ‫‪.I‬‬
‫ﺍﻨﺤﻼل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪158 ..............................................‬‬ ‫‪.1.I‬‬
‫ﺘﻌﻤﻴﻡ ‪159 ...................................................................‬‬ ‫‪.2.I‬‬
‫ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻭﺍﻻﻨﺤﻼﻝﻴ‪‬ﺔ ‪160 ..............................................‬‬ ‫‪.3.I‬‬
‫ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ ‪161 .................................................................‬‬ ‫‪.II‬‬
‫ﺇﻴﺠﺎﺩ ﺍﻝﺸﺭﻁ ‪161 ...........................................................‬‬ ‫‪.1.II‬‬
‫ﺘﻁﺒﻴﻕ ‪162 .................................................................‬‬ ‫‪.2.II‬‬
‫ﺃﺜﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ ‪164 ..................................................‬‬ ‫‪.3.II‬‬
‫ﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺭﺍﺴﺏ ﻤﺎ ‪169 ........................................................‬‬ ‫‪.III‬‬
‫ﺘﻨﺎﻓﺱ ﺍﻝﺭﻭﺍﺴﺏ ‪171 ................................................................‬‬ ‫‪.IV‬‬
‫‪ .1.IV‬ﺘﺠﺭﺒﺔ ‪171 .................................................................‬‬

‫‪ .2.IV‬ﺍﻝﺘﻌﻠﻴل‪171 .................................................................‬‬
‫‪ .3.IV‬ﺘﻁﺒﻴﻕ ‪172 .................................................................‬‬
‫ﺍﻻﻨﺤﻼﻝﻴﺔ ﻭﺍﻝﺘﻌﻘﻴﺩ ‪174 ..............................................................‬‬ ‫‪.V‬‬
‫ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ‪174 ...................................‬‬ ‫‪.1.V‬‬
‫‪ .1.1.V‬ﺘﺠﺭﺒﺔ ‪174 ..............................................................‬‬

‫‪ .1.2.V‬ﺘﻌﻤﻴﻡ ‪175 ...............................................................‬‬
‫ﺘﻐﻴ‪‬ﺭ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩﺍﺕ ‪176 ...............................‬‬ ‫‪.2.V‬‬
‫ﺍﻝﺘﺭﺴﻴﺏ ﻭ ‪ pH‬ﺍﻝﻭﺴﻁ‪180 .........................................................‬‬ ‫‪.VI‬‬
‫‪ .1.VI‬ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﺒﻔﻌل ﺤﻤﺽ‪180 .............................................‬‬

‫‪ .1.1.VI‬ﺘﺠﺭﺒﺔ ‪180 .............................................................‬‬
‫‪ .2.1.VI‬ﺘﻌﻤﻴﻡ ‪181 ..............................................................‬‬
‫‪ .2.VI‬ﺘﺭﺴﻴﺏ ﺴﻠﻔﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ ‪183 ...............................................‬‬
‫‪ .3.VI‬ﺘﺭﺴﻴﺏ ﻫﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ ‪185 .........................................‬‬
‫‪ .1.3.VI‬ﺘﺤﺩﻴﺩ ‪ pH‬ﺍﻝﺘﺭﺴﻴﺏ ﻝﻠﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﻌﺩﻨﻴﺔ ‪185 ......................‬‬
‫‪ .2.3.VI‬ﺤﺎﻝﺔ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﺘﺫﺒﺫﺒﺔ ‪186 ......................................‬‬
‫‪ .VII‬ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﻝﺘﺭﺴﻴﺏ ‪190 .............................................................‬‬
‫‪ .1.VII‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ ‪190 ........................................................‬‬
‫‪ .2.VII‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪192 ............................................. p Ag = f (x‬‬
‫‪ .1.2.VII‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ‪192 .....................................................‬‬
‫‪ .2.2.VII‬ﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ﻭﻨﺘﺎﺌﺠﻪ ‪193 .............................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪197 ...............................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺴﺎﺩﺱ‬
‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻷﻛﺴﺪﺓ ﻭﺍﻹﺭﺟﺎﻉ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ﺘﻌﺎﺭﻴﻑ ‪206 ........................................................................‬‬ ‫‪.I‬‬
‫ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪207 .....................................................‬‬ ‫‪.II‬‬
‫ﺘﻔﺎﻋﻼﺕ ﺍﻨﺘﻘﺎل ﺍﻝﺠﺴﻴﻤﺎﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺒﻴﻥ ﻤﺎﻨﺢ ﻭﻤﺘﻘ‪‬ﺒل ‪211 .........................‬‬ ‫‪.III‬‬
‫ﻤﻔﻬﻭﻡ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪211 .............................................................‬‬ ‫‪.IV‬‬
‫ﺨﻭﺍﺹ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ‪214 ..........................................................‬‬ ‫‪.V‬‬
‫ﺘﻁﺒﻴﻘﺎﺕ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ‪215 .........................................................‬‬ ‫‪.VI‬‬
‫‪ .1.VI‬ﺩﺭﺍﺴﺔ ﻁﺒﻴﻌﺔ ﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ ‪215 ...........................................‬‬

‫‪ .2.VI‬ﻤﻭﺍﺯﻨﺔ ﻤﻌﺎﺩﻝﺔ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ‪215 ..........................................‬‬
‫‪ .VII‬ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ‪216 .................................................................‬‬
‫‪ .1.VII‬ﺘﻌﺎﺭﻴﻑ ﻭﺍﺼﻁﻼﺤﺎﺕ ‪216 .................................................‬‬
‫‪ .1.1.VII‬ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﻭﺍﻝﻤﺴﺭﻯ ‪216 ...........................................‬‬
‫‪ .2.1.VII‬ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺃﻭ ﺍﻝﺒﻁﺎﺭﻴﺔ ‪217 ........................................‬‬
‫‪ .3.1.VII‬ﺍﻻﺘﺠﺎﻩ ﺍﻻﺼﻁﻼﺤﻲ ﻝﻠﺘﻔﺎﻋل ﺍﻝﻜﻬﺭﻜﻴﻤﻴﺎﺌﻲ ‪217 .........................‬‬
‫‪ .2.VII‬ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ‪218 ..................................‬‬
‫‪ .3.VII‬ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ﺃﻭ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪219 .............................‬‬
‫‪ .1.3.VII‬ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ‪219 .......................................‬‬
‫‪ .2.3.VII‬ﺘﻌﺭﻴﻑ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺃﻭ ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ‪219 ................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪223 ...............................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺴﺎﺑﻊ‬
‫ﻋﻼﻗﺔ ﻧﺮﻧﺴﺖ‬
‫ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ‪226 ..................................................................‬‬ ‫‪.I‬‬
‫ﻋﺭﺽ ﺍﻝﻌﻼﻗﺔ ‪226 ..........................................................‬‬ ‫‪.1.I‬‬
‫ﺃﻤﺜﻠﺔ ﻋﻥ ﺍﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ‪227 ........................................‬‬ ‫‪.2.I‬‬
‫ﺃﻨﻭﺍﻉ ﺍﻝﻤﺴﺎﺭﻱ ‪228 .........................................................‬‬ ‫‪.3.I‬‬
‫ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪230 ..............................................‬‬ ‫‪.II‬‬
‫ﺴﻠﻭﻙ ﺠﻤﻠﺔ ‪230 ............................................................‬‬ ‫‪.1.II‬‬
‫ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ ﻝﺘﻁﻭﺭ ﺠﻤﻠﺔ‪ -‬ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ‪233 ...............................‬‬ ‫‪.2.II‬‬
‫ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‪ -‬ﺘﻁﺒﻴﻕ ‪235 .............................‬‬ ‫‪.3.II‬‬
‫ﺘﻌﻴﻴﻥ )‪238 ............................................... E (Ox/Red‬‬ ‫‪.4.II‬‬
‫ﻤﻨﺎﻁﻕ ﺍﻝﻭﺠﻭﺩ ﻭﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ‪239 ...............................................‬‬ ‫‪.III‬‬
‫‪ .1.III‬ﺘﻌﺎﺭﻴﻑ ‪239 ...............................................................‬‬

‫‪ .2.III‬ﺘﻁﺒﻴﻘﺎﺕ ‪242 ...............................................................‬‬
‫ﺍﻝﻌﻭﺍﻤل ﺍﻝﻤﺅﺜﺭﺓ ﻓﻲ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪246 .................................‬‬ ‫‪.IV‬‬
‫‪ .1.IV‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﺭﻜﻴﺯ ‪246 ..........................................................‬‬

‫‪ .2.IV‬ﺘﺄﺜﻴﺭ ﺍﻝـ ‪250 ........................................................ pH‬‬
‫‪ .1.2.IV‬ﻤﺜﺎل ‪ :‬ﺍﻝﺯﻭﺝ ‪250 ....................................... O2 / H2 O‬‬
‫‪250 .................................. Mn O−‬‬
‫‪4 / Mn‬‬
‫‪2+‬‬
‫‪ .2.2.IV‬ﻤﺜﺎل ‪ :‬ﺍﻝﺯﻭﺝ‬
‫‪ .3.IV‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﻌﻘﻴﺩ ﻭﺍﻝﺘﺭﺴﻴﺏ ‪251 .................................................‬‬
‫‪ .1.3.IV‬ﺘﻁﺒﻴﻕ ) ‪252 ........................................................ ( 1‬‬
‫‪ .2.3.IV‬ﺘﻁﺒﻴﻕ ) ‪254 ........................................................ ( 2‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪257 ...............................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ‬
‫ﻣﻌﺎﻳﺮﺍﺕ ﺍﻷﻛﺴﺪﺓ ﻭﺍﻹﺭﺟﺎﻉ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ﻋﻤﻭﻤﻴﺎﺕ ﻭﺘﺫﻜﺭﺓ ‪262 ..............................................................‬‬ ‫‪.I‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺭﻴﻭﻡ )‪263 ............................ (IV‬‬ ‫‪.II‬‬
‫ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ ‪263 ........................................................‬‬ ‫‪.1.II‬‬
‫ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ﻝﻠﻤﻨﺤﻨﻲ ) ‪264 ................................... E = f (x‬‬ ‫‪.2.II‬‬
‫ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ ‪268 ............................................‬‬ ‫‪.3.II‬‬
‫ﻤﺸﻌﺭ ﻝﻭﻨﻲ ﺃﻜﺴﺩﺓ‪-‬ﺇﺭﺠﺎﻉ ‪269 .............................................‬‬ ‫‪.4.II‬‬
‫‪269 ...................... MnO−‬‬

‫ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬ ‫‪.III‬‬
‫‪ .1.III‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ ‪269 ........................................................‬‬

‫‪ .2.III‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ﻝﻠﻤﻨﺤﻨﻲ ) ‪271 ................................... E = f (x‬‬
‫‪ .3.III‬ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ ‪274 ............................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪277 ...............................................................................‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺘﺎﺳﻊ‬
‫ﺭﺳﻢ ﳐﻄﻄﺎﺕ ﻛﻤﻮﻥ‪ pH -‬ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬

‫ﻤﺨﻁﻁ ﻜﻤﻭﻥ‪ pH -‬ﻝﻠﻤﺎﺀ ‪280 ......................................................‬‬ ‫‪.I‬‬
‫ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ ‪280 ...........................................................‬‬ ‫‪.1.I‬‬
‫ﺍﺴﺘﺜﻤﺎﺭ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺎﺀ ‪282 .........................‬‬ ‫‪.2.I‬‬

‫ﻤﺨﻁﻁ ﻜﻤﻭﻥ‪ pH -‬ﻝﻠﺤﺩﻴﺩ ‪283 .....................................................‬‬ ‫‪.II‬‬
‫‪ .1.II‬ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ ‪283 ...........................................................‬‬

‫‪ .1.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe3+ / Fe2+‬ﻋﻨﺩﻤﺎ ‪284 .................... pH < 2‬‬
‫‪ .2.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe2+ / Fe‬ﻋﻨﺩﻤﺎ ‪285 ................... pH < 7.45‬‬
‫‪ .3.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)3 / Fe2 +‬ﻋﻨﺩﻤﺎ ‪286 .... 2 < pH < 7.45‬‬
‫‪ .4.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)3 / Fe(OH)2‬ﻋﻨﺩﻤﺎ ‪288 ...... pH > 7.45‬‬
‫‪ .5.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)2 / Fe‬ﻋﻨﺩﻤﺎ ‪289 ............. pH > 7.45‬‬
‫‪ .2.II‬ﺍﺴﺘﺜﻤﺎﺭ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺤﺩﻴﺩ ‪290 .......................‬‬
‫‪ .1.2.II‬ﺍﺴﺘﻘﺭﺍﺭ ﻤﺨﺘﻠﻑ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ ‪291 .................................‬‬
‫‪ .2.2.II‬ﺍﻻﺴﺘﻘﺭﺍﺭ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ‪291 .......................................‬‬
‫ﺘﻤﺭﻴﻨﺎﺕ‪293 ...............................................................................‬‬
‫ﻣﻠﺤﻖ‬
‫ﺍﻟﺜﻮﺍﺑﺖ ﺍﻟﺘﺮﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴ‪‬ﺔ ﻟﻠﺘﻮﺍﺯﻧﺎﺕ ﺍﳊﺎﺻﻠﺔ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴ‪‬ﺔ‬

‫ﺜﻭﺍﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ﻝﻸﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻋﻨﺩ ‪296 ............................ 250 C‬‬ ‫‪.I‬‬
‫ﻜﻤﻭﻨﺎﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻴﺔ ﻋﻨﺩ ‪298 ................................. 250 C‬‬ ‫‪.II‬‬
‫ﺜﻭﺍﺒﺕ ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﺩﺍﺕ ﻋﻨﺩ ‪300 .............................................. 250 C‬‬ ‫‪.III‬‬
‫ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻋﻨﺩ ‪302 ..................................................... 250 C‬‬ ‫‪.IV‬‬
‫ﺍﻝﻤﺭﺍﺠﻊ ‪305 ...............................................................................‬‬

‫ﻤﺴﺭﺩ ﺍﻝﻤﺼﻁﻠﺤﺎﺕ ﺍﻝﻌﻠﻤﻴ‪‬ﺔ‪307 .............................................................‬‬
‫ ‪ 7 8‬‬
‫ﺍﺯﺩﻴﺎﺩ ﺤﻤﻭﻀﺔ ﺍﻝﻤﺤﻴﻁﺎﺕ ‪15...............................................................‬‬

‫ﻜﻴﻑ ﻨﺤﻀ‪‬ﺭ ﺍﻝﻤﺼﺎﺒﻴﺢ ﺍﻝﺯﺠﺎﺠﻴﺔ ﺍﻝﺸﺎﻓﹼﺔ ﻝﻠﻀﻭﺀ؟ ‪27.........................................‬‬
‫ﺍﻝﻘﺭﺤﺔ ﺍﻝﻤﻌﺩﻴ‪‬ﺔ ‪57..........................................................................‬‬
‫ﻝﻤﺎﺫﺍ ﻨﺫﺭﻑ ﺍﻝﺩﻤﻊ ﻋﻨﺩ ﺘﻘﻁﻴﻊ ﺍﻝﺒﺼل؟ ‪63....................................................‬‬
‫ﻝﻤﺎﺫﺍ ﻴﻨﺒﻐﻲ ﻋﺩﻡ ﻤﺯﺝ ﺍﻝﻤﺒﻴ‪‬ﻀﺎﺕ ﻤﻊ ﺍﻝﻤﻨﻅﹼﻔﺎﺕ ﺍﻝﺤﺎﻭﻴﺔ ﻋﻠﻰ ﺍﻝﻨﺸﺎﺩﺭ ؟ ‪72....................‬‬
‫ﺍﻝﻠﺒﺎﻥ ﺍﻝﺨﺎﻝﻲ ﻤﻥ ﺍﻝﺴﻜﹼﺭ ‪86..................................................................‬‬
‫ﺍﻝﺘﺨﻔﻴﻑ ﻤﻥ ﺍﻝﺘﺄﺜﻴﺭ ﺍﻝﺴﻠﺒﻲ ﻝﻠﺤﻤﻭﺽ ﺒﺎﺴﺘﻌﻤﺎل ﺃﻤﻼﺡ ﻏﻴﺭ ﻤﺅﺫﻴﺔ ‪96.........................‬‬
‫ﺍﻝﻭﺴﻁ ﺍﻝﻤﻭﻗﻲ ﻓﻲ ﺍﻝﺩﻡ ‪102 .................................................................‬‬
‫ﻝﻤﺎﺫﺍ ﻨﻀﻴﻑ ﺃﻤﻼﺡ ﻤﺭﻜﹼﺏ ‪ EDTA‬ﺇﻝﻰ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻐﺫﺍﺌﻴﺔ ﺍﻝﻤﻌﻠﹼﺒﺔ؟ ‪118 ........................‬‬
‫ﻤﺎ ﻫﻲ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻀﺎﺩﺓ )ﺍﻝﺘﺭﻴﺎﻕ( ﻝﻤﻌﺎﻝﺠﺔ ﺍﻝﺘﺴﻤﻡ ﺒﺎﻝﺴﻴﺎﻨﻴﺩ؟ ‪131 ..............................‬‬
‫ﺘﺸﻜﹼل ﺍﻝﺼﻭﺍﻋﺩ ﻭﺍﻝﻨﻭﺍﺯل ‪163 ..............................................................‬‬
‫ﺍﻷﺸﻌ‪‬ﺔ ﺍﻝﺴﻴﻨﻴ‪‬ﺔ ﻝﻠﻤﻌﺩﺓ ﻭﺍﻷﻤﻌﺎﺀ ‪166 .........................................................‬‬
‫ﻜﻴﻑ ﺘﺨﻔﹼﻑ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭ ﻤﻥ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ؟‪168 ............................................‬‬
‫ﻜﻴﻑ ﺘﺴﺎﻫﻡ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻓﻲ ﺇﻁﻼﻕ ﺍﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﻔﻀﺎﺌﻴﺔ؟ ‪210 .................‬‬
‫ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ‪221 ...........................................................................‬‬
‫ﺤﻤﺎﻴﺔ ﺍﻝﺴﻔﻥ ﻤﻥ ﺍﻝﺼﺩﺃ ‪232 ................................................................‬‬
‫ﺃﺨﻁﺎﺀ ﻤﺭﺩ‪‬ﻫﺎ ﺠﻬل ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪245 ........................................‬‬
‫ﺘﻁﺒﻴﻕ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻓﻲ ﺍﻝﺨﻼﻴﺎ ﺍﻝﺤﻴﺔ‪256 ................................................ .‬‬
‫ﻣﻘﺪ‪‬ﻣـﺔ‬
‫ﻨﻘﺩ‪‬ﻡ ﺇﻝﻰ ﻁﻼﺒﻨﺎ ﺍﻷﻋﺯ‪‬ﺍﺀ ﻜﺘﺎﺏ ﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﺍﻝﺫﻱ ﻨﺄﻤل ﺃﻥ ﻴﻜﻭﻥ ﻤﻔﻴﺩﹰﺍ‬
‫ﻝﻁﻼﺏ ﺍﻝﻤﻌﻬﺩ ﺍﻝﻌﺎﻝﻲ ﻝﻠﻌﻠﻭﻡ ﺍﻝﺘﻁﺒﻴﻘﻴ‪‬ﺔ ﻭﺍﻝﺘﻜﻨﻭﻝﻭﺠﻴﺎ‪ ،‬ﻭﻁﻼﺏ ﻜﻠﻴﺎﺕ ﺍﻝﻌﻠﻭﻡ ﺒﻤﺨﺘﻠﻑ‬
‫ﺍﺨﺘﺼﺎﺼﺎﺘﻬﺎ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﻭﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ ﻭﺍﻝﺠﻴﻭﻝﻭﺠﻴﺔ ﻭﺍﻝﺒﻴﻭﻝﻭﺠﻴﺔ ﻭﻜﺫﻝﻙ ﻁﻼﺏ ﻜﻠﻴﺎﺕ ﺍﻝﻁﺏ‬
‫ﺏ ﺍﻷﺴﻨﺎﻥ ﻭﺍﻝﺼﻴﺩﻝﺔ ﻭﺍﻝﺯﺭﺍﻋﺔ‪.‬‬
‫ﺍﻝﺒﺸﺭﻱ ﻭﻁ ‪‬‬
‫ﹸﺘﺩﺭ‪‬ﺱ ﺍﻝﻜﻴﻤﻴﺎﺀ ﻓﻲ ﺍﻝﺴﻨﺔ ﺍﻷﻭﻝﻰ ﻓﻲ ﺍﻝﻤﻌﻬﺩ ﺍﻝﻌﺎﻝﻲ‪ ،‬ﺤﻴﺙ ﻴﺘﻌﻠﹼﻡ ﺍﻝﻁﻼﺏ ﻓﻴﻬﺎ ﻤﺒﺎﺩﺉ‬
‫ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺒﻨﻴﻭﻴﺔ ﻭﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪.‬‬
‫ﻥ ﻋﻠﻡ ﺍﻝﻜﻴﻤﻴﺎﺀ ﻋﻠﻡ ﺘﻁﺒﻴﻘﻲ ﺒﺎﻤﺘﻴﺎﺯ‪ ،‬ﻨﻠﻤﺱ ﺘﻁﺒﻴﻘﺎﺘﻪ ﻓﻲ ﻤﺨﺘﻠﻑ ﺠﻭﺍﻨﺏ ﺍﻝﺤﻴﺎﺓ ﺍﻝﺘﻲ‬
‫ﺇ‪‬‬
‫ل ﻤﻥ ﺃﻜﺜﺭ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺃﻫﻤﻴﺔ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻴﻨﺎ ﻫﻲ ﺘﻠﻙ ﺍﻝﺘﻲ ﺘﺤﺼل ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل‬
‫ﺘﺤﻴﻁ ﺒﻨﺎ‪ .‬ﻭﻝﻌ ّ‬
‫ﻥ ﻤﻌﻅﻡ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻲ ﺘﺒﻘﻴﻨﺎ ﻋﻠﻰ ﻗﻴﺩ ﺍﻝﺤﻴﺎﺓ ﺘﺠﺭﻱ ﻓﻲ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ ﻀﻤﻥ ﺠﺴﻤﻨﺎ‬
‫ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﺇﺫ ﺇ ‪‬‬
‫ﺃﻭ ﻓﻲ ﺘﻤﺎﺱ ﻤﻊ ﻭﺴﻁ ﻤﺎﺌﻲ‪ .‬ﺤﺭﺼﻨﺎ ﻓﻲ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ ﺍﻝﺫﻱ ﻴﻬﺘ ‪‬ﻡ ﺒﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﻋﻠﻰ‬
‫ﺇﻅﻬﺎﺭ ﺍﻝﺘﻁﺒﻴﻘﺎﺕ ﺍﻝﻤﺘﻌﺩﺩﺓ ﻝﻠﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻲ ﺘﺠﺭﻱ ﻓﻲ ﺍﻷﻭﺴﺎﻁ ﺍﻝﻤﺎﺌﻴﺔ ﻭﺨﺼﻭﺼﹰﺎ ﻤﻨﻬﺎ ﺘﻠﻙ ﺍﻝﺘﻲ‬
‫ﺘﺠﺭﻱ ﻓﻲ ﺍﻝﺠﺴﻡ ﺍﻝﺒﺸﺭﻱ ﺍﻝﻤﻜﻭ‪‬ﻥ ﺃﺴﺎﺴﹰﺎ ﻤﻥ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ )ﺍﻝﺩﻡ‪ ،‬ﺍﻝﻌﺼﺎﺭﺍﺕ ﺍﻝﻬﺎﻀﻤﺔ‪ ،‬ﺍﻝﺴﺎﺌل‬
‫ﺍﻝﺩﻤﺎﻏﻲ‪ .(...،‬ﻓﻬﻭ ﻤﻨﻅﻭﻤﺔ ﻤﺘﻜﺎﻤﻠﺔ ﻤﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﺘﻲ ﺘﻌﻤل ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ ﺒﺘﻨﺎﻏﻡ‬
‫ﻭﺘﻨﺴﻴﻕ‪ .‬ﻓﻨﺠﺩ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﺍﻝﺩﻡ ﺍﻝﺘﻲ ﺘﺤﺎﻓﻅ ﻋﻠﻰ ﻗﻴﻤﺔ ‪ pH‬ﺜﺎﺒﺘﺔ ﺘﺴﻤﺢ ﺒﺤﺼﻭل‬
‫ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﻓﻲ ﻅﺭﻭﻑ ﻤﺜﻠﻰ‪ ،‬ﻭﻨﺠﺩ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻓﻲ ﻋﻤﻠﻴﺎﺕ ﺍﻝﺘﻨﻔﹼﺱ‬
‫ﻭﺍﻻﺴﺘﻘﻼﺏ‪ ،‬ﻭﺍﻨﺘﻘﺎل ﺍﻝﺴﻴﺎﻻﺕ ﺍﻝﻌﺼﺒﻴﺔ‪ ،‬ﻭﻨﺠﺩ ﺩﻭﺭ ﺍﻝﺤﻤﻭﺽ ﻓﻲ ﻫﻀﻡ ﺍﻝﻁﻌﺎﻡ ﻓﻲ ﺍﻝﻤﻌﺩﺓ‬
‫ﻼ ﻋﻨﺩﻤﺎ ﻨﺘﻨﻔﹼﺱ ﺍﻷﻜﺴﺠﻴﻥ ﻴﻨﺤل ﻓﻲ ﺍﻝﺩﻡ ﻋﺒﺭ ﺍﺭﺘﺒﺎﻁﻪ‬
‫ﻭﺘﺄﺜﻴﺭﻫﺎ ﻓﻲ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ‪ .‬ﻓﻤﺜ ﹰ‬
‫ﺒﺎﻝﻬﻴﻤﻭﻏﻠﻭﺒﻴﻥ ﺍﻝﻤﻭﺠﻭﺩ ﻓﻲ ﺍﻝﻜﺭﻴﺎﺕ ﺍﻝﺤﻤﺭ‪ ،‬ﺜ ‪‬ﻡ ﻴﻨﺘﻘل ﻋﺒﺭ ﺍﻝﺩﻡ ﺇﻝﻰ ﺍﻝﺨﻼﻴﺎ ﺤﻴﺙ ﻴﺘﻔﺎﻋل ﻫﻨﺎﻙ‬
‫ﻤﻊ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺫﻱ ﺯﻭ‪‬ﺩﺕ ﺒﻪ ﻋﻥ ﻁﺭﻴﻕ ﺍﻝﻁﻌﺎﻡ ﺍﻝﺫﻱ ﻨﺘﻨﺎﻭﻝﻪ‪ .‬ﻭﺍﻝﺘﻔﺎﻋل ﺒﻴﻥ ﺍﻷﻜﺴﺠﻴﻥ ﻭﺍﻝﻭﻗﻭﺩ‬
‫ﻥ ﺍﻝﺨﻼﻴﺎ ﻝﻴﺴﺕ ﺃﻓﺭﺍﻨﹰﺎ ﺼﻐﻴﺭﺓ‪ ،‬ﺒل ﻴﺤﺼل ﺘﺒﺎﺩل ﺇﻝﻜﺘﺭﻭﻨﻲ ﺤﻴﺙ ﺘﻨﺘﻘل‬
‫ﻝﻴﺱ ﻤﺒﺎﺸﺭﹰﺍ‪ ،‬ﻷ ‪‬‬
‫ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻤﻥ ﺍﻝﻭﻗﻭﺩ ﺇﻝﻰ ﺴﻠﺴﻠﺔ ﻤﻥ ﺍﻝﺠﺯﻴﺌﺎﺕ ﺘﹸﻌﺭﻑ ﺒﺎﺴﻡ ﺍﻝﺴﻠﺴﻠﺔ ﺍﻝﺘﻨﻔﺴﻴﺔ ‪respiratory‬‬
‫‪ chain‬ﺤﺘﻰ ﺘﺼل ﺇﻝﻰ ﺍﻷﻜﺴﺠﻴﻥ‪.‬‬
‫‪1‬‬
‫ﻭﻋﻠﻴﻨﺎ ﺃﻻ ﻨﻐﻔل ﺃﻴﻀﹰﺎ ﺍﻝﺩﻭﺭ ﺍﻝﻤﻬﻡ ﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﻓﻲ ﺍﻝﻤﺠﺎﻝﻴﻥ ﺍﻝﺼﻨﺎﻋﻲ‬
‫ﻭﺍﻝﺒﻴﺌﻲ ﺒﺩﺀﹰﺍ ﻤﻥ ﺘﺤﻀﻴﺭ ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ﻭﺍﻨﺘﻬﺎﺀ ﺒﻤﻌﺎﻝﺠﺔ ﺍﻝﻤﻴﺎﻩ ﻭﺘﺨﻠﻴﺼﻬﺎ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺎﺩﻥ‬
‫ﺍﻝﺜﻘﻴﻠﺔ‪.‬‬
‫ﻴﻬﺩﻑ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ ﺇﻝﻰ ﺘﻘﺩﻴﻡ ﺍﻝﻤﻔﺎﻫﻴﻡ ﺍﻷﺴﺎﺴﻴﺔ ﺍﻝﻼﺯﻤﺔ ﻝﺩﺭﺍﺴﺔ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل‬
‫ﺍﻝﻤﺎﺌﻴﺔ‪ .‬ﻭﺘﺴﺘﺜﻤﺭ ﻋﻼﻗﺔ ﻏﻭﻝﺩﺒﺭﻍ ﻭﻓﺎﻍ ‪ Guldberg & Waage‬ﻓﻲ ﺘﻌﺭﻴﻑ ﻤﻨﺎﻁﻕ‬
‫ﺍﻝﺭﺠﺤﺎﻥ ﺃﻭ ﻤﻨﺎﻁﻕ ﺍﻝﻭﺠﻭﺩ ﻝﻠﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻲ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ‬
‫ﻭﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﺭﺴﻴﺏ ﻭﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻌﻘﻴﺩ‪ .‬ﻭﻴﻬﺩﻑ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ ﻜﺫﻝﻙ ﺇﻝﻰ ﺇﺩﺨﺎل ﻤﻔﻬﻭﻡ ﺍﻝﺘﻔﺎﻋل‬
‫ﺍﻝﺭﺍﺠﺢ ‪ Predominant Reaction P.R.‬ﻭﻜﻴﻔﻴﺔ ﻜﺘﺎﺒﺘﻪ ﻭﺘﻤﻴﻴﺯﻩ ﻭﺇﻅﻬﺎﺭ ﺩﻭﺭﻩ ﻓﻲ ﺘﺴﻬﻴل‬
‫ﻲ ﻨﺎﺘﺞ ﻋﻥ ﻤﺯﺝ ﻋﺩ‪‬ﺓ ﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ‪ .‬ﻭﺃﺨﻴﺭﹰﺍ ﻭﻝﻴﺱ ﺁﺨﺭﹰﺍ ﻴﻬﺩﻑ ﻫﺫﺍ‬
‫ﺇﻴﺠﺎﺩ ﻤﻜﻭ‪‬ﻨﺎﺕ ﻤﺤﻠﻭل ﻤﺎﺌ ‪‬‬
‫ل ﺍﻝﻌﺩﻴﺩ ﻤﻥ‬
‫ﺍﻝﻜﺘﺎﺏ ﺇﻝﻰ ﺘﻌﻠﻴﻡ ﺍﻝﻁﺎﻝﺏ ﻜﻴﻔﻴﺔ ﺍﺴﺘﺜﻤﺎﺭ ﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻝﻤﺎ ﻝﻬﺎ ﻤﻥ ﺃﻫﻤﻴﺔ ﻓﻲ ﺤ ّ‬
‫ﻤﺸﺎﻜل ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ‪.‬‬
‫ﻴﻀ ‪‬ﻡ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ ﺘﺴﻌﺔ ﻓﺼﻭل ﻤﺨﺘﻠﻔﺔ‪ ،‬ﻋﺎﻝﺠﻨﺎ ﻓﻲ ﺍﻝﻔﺼﻭل ﺍﻝﺜﻼﺜﺔ ﺍﻷﻭﻝﻰ ﻤﻨﻬﺎ‬
‫ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ‪ ،‬ﺜ ‪‬ﻡ ﺘﻨﺎﻭﻝﻨﺎ ﻓﻲ ﺍﻝﻔﺼل ﺍﻝﺭﺍﺒﻊ ﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺘﻌﻘﻴﺩ‪ ،‬ﻭﻓﻲ ﺍﻝﻔﺼل‬
‫ﺍﻝﺨﺎﻤﺱ ﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺘﺭﺴﻴﺏ‪ ،‬ﻭﺃﻓﺭﺩﻨﺎ ﺍﻝﻔﺼﻭل ﺍﻷﺭﺒﻌﺔ ﺍﻷﺨﻴﺭﺓ ﻝﺩﺭﺍﺴﺔ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ‬
‫ﻭﺍﻹﺭﺠﺎﻉ‪.‬‬
‫ﻻ ﻓﻲ ﺍﻝﻜﻴﻤﻴﺎﺀ‪،‬‬
‫ﻴﻌﺭﺽ ﺍﻝﻔﺼل ﺍﻷﻭل ﻓﻲ ﺒﺩﺍﻴﺘﻪ ﺩﻭﺭ ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﺍﻝﻤﺫﻴﺏ ﺍﻷﻜﺜﺭ ﺍﺴﺘﻌﻤﺎ ﹰ‬
‫ﻭﻴﺘﻌﺭ‪‬ﺽ ﺇﻝﻰ ﺒﻌﺽ ﺨﻭﺍﺹ ﻫﺫﺍ ﺍﻝﻤﺫﻴﺏ ﻤﻥ ﺤﻴﺙ ﻤﻘﺩﺭﺘﻪ ﻋﻠﻰ ﺍﻝﺘﺸﺭﻴﺩ ﻭﺍﻝﻔﺼل ﻨﻅﺭﹰﺍ ﻝﻤﺎ‬
‫ﻴﺘﻤﺘﻊ ﺒﻪ ﻤﻥ ﻗﻴﻡ ﻤﺭﺘﻔﻌﺔ ﻨﺴﺒﻴﹰﺎ ﻤﻥ ﻋﺯ ﹴﻡ ﺜﻨﺎﺌﻲ ﺍﻝﻘﻁﺏ ﻭﺜﺎﺒﺕ ﻋﺯل ﻜﻬﺭﺒﺎﺌﻲ‪ .‬ﺜ ‪‬ﻡ ﻴﻌﺭﺽ ﺒﻌﺽ‬
‫ﺍﻝﺘﻌﺎﺭﻴﻑ ﺍﻝﺨﺎﺼﺔ ﺒﺎﻷﺴﺱ ﻭﺍﻝﺤﻤﻭﺽ‪ ،‬ﻭﻤﻔﻬﻭﻡ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‪ ،‬ﺜ ‪‬ﻡ ﻴﻌ ‪‬ﺭﻑ ‪pH‬‬
‫ﻤﺤﻠﻭل‪ ،‬ﻭﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ‪ .‬ﻴﺘﻨﺎﻭل ﺍﻝﻔﺼل ﺒﻌﺩ ﺫﻝﻙ ﺘﺼﻨﻴﻑ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ‬
‫ﺘﺒﻌﹰﺎ ﻝﻘﻭﺘﻬﺎ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﺫﻝﻙ ﺒﻌﺩ ﺘﻌﺭﻴﻑ ﺍﻝﺯﻭﺠﻴﻥ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﺨﺎﺼﻴﻥ ﺒﺎﻝﻤﺎﺀ‪ ،‬ﺜ ‪‬ﻡ ﻴﺘﻁﺭ‪‬ﻕ‬
‫ﺍﻝﻔﺼل ﺇﻝﻰ ﻤﺨﻁﻁﺎﺕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻝﻴﺼل ﺃﺨﻴﺭﹰﺍ ﺇﻝﻰ ﺩﺭﺍﺴﺔ ﺍﻝﺘﻔﺎﻋﻼﺕ‬
‫ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ ﺒﺼﻭﺭﺓ ﻜﻤﻴﺔ ﻋﻥ ﻁﺭﻴﻕ ﻜﺘﺎﺒﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪.‬‬
‫ﻭﻴﺘﻨﺎﻭل ﺍﻝﻔﺼل ﺍﻝﺜﺎﻨﻲ ﻁﺭﺍﺌﻕ ﺤﺴﺎﺏ ‪ pH‬ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺒﺘﻔﺼﻴل ﻜﺒﻴﺭ ﻤﺴﺘﻭﻓﻴﹰﺎ ﻓﻲ ﺫﻝﻙ‬
‫ﺠﻤﻴﻊ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ ﻴﻜﻭﻥ ﻋﻠﻴﻬﺎ ﺍﻝﻤﺤﻠﻭل ﺍﺒﺘﺩﺍﺀ ﻤﻥ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻝﺤﻤﺽ ﻗﻭﻱ‪،‬‬
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‫ﻭﺍﻨﺘﻬﺎﺀ ﺒﻤﺯﻴﺞ ﻴﻀ ‪‬ﻡ ﺃﻤﻼﺤﹰﺎ ﻭﺤﻤﻭﻀﹰﺎ ﻭﺃﺴﺴﹰﺎ‪ .‬ﺃﻤﺎ ﺍﻝﻔﺼل ﺍﻝﺜﺎﻝﺙ ﻓﻘﺩ ﺘﻨﺎﻭل ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺤﻤﻀﻴﺔ‬
‫ﺍﻷﺴﺎﺴﻴﺔ ﺒﻤﺨﺘﻠﻑ ﺃﻨﻭﺍﻋﻬﺎ‪ ،‬ﻭﻤﻔﻬﻭﻡ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻭﻜﻴﻔﻴﺔ ﺘﺤﺩﻴﺩﻫﺎ‪.‬‬
‫ﻻ ﺘﻌﺭﻴﻑ ﺍﻝﻤﻌﻘﹼﺩ‬
‫ﻴﺘﻨﺎﻭل ﺍﻝﻔﺼل ﺍﻝﺭﺍﺒﻊ ﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺘﻌﻘﻴﺩ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﻓﻴﻘﺩ‪‬ﻡ ﺃﻭ ﹰ‬
‫ﻭﺍﻝﺭﺒﻴﻁﺔ‪ ،‬ﺜ ‪‬ﻡ ﻴﺤ ‪‬ﺩﺩ ﻫﻨﺩﺴﺔ ﺒﻌﺽ ﺍﻝﻤﻌﻘﺩﺍﺕ ﺒﺎﺴﺘﻌﻤﺎل ﻁﺭﻴﻘﺔ ‪ ،VSEPR‬ﻝﻨﺼل ﺒﻌﺩ ﺫﻝﻙ ﺇﻝﻰ‬
‫ﻜﺘﺎﺒﺔ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ ﻤﺎ ﻭﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﺘﻔﻜﹼﻜﻪ‪ ،‬ﻭﻜﺘﺎﺒﺔ ﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﺸﻜﹼل‬
‫ل ﻤﺭﺓ ﺒﺎﻝﺜﻭﺍﺒﺕ ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻴﺔ ﺍﻝﻤﻤﻴﺯﺓ ﻝﻜل‬
‫ﻭﺍﻝﺘﻔﻜﹼﻙ ﺍﻝﻤﺘﻌﺎﻗﺒﺔ ﻝﻤﻌﻘﹼﺩ ﻤﺎ ﻤﻊ ﺍﻝﺘﻌﺭﻴﻑ ﻓﻲ ﻜ ّ‬
‫ﺘﻭﺍﺯﻥ‪ .‬ﻴﻌﺎﻝﺞ ﺍﻝﻔﺼل ﺒﻌﺩ ﺫﻝﻙ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ‪ ،‬ﺜ ‪‬ﻡ ﺘﻨﺎﻓﺱ ﺍﻝﻤﻌﻘﺩ‪‬ﺍﺕ ﻓﻲ ﺤﺎﻝﺘﻴﻥ‪ :‬ﺍﻷﻭﻝﻰ ﻋﻨﺩ‬
‫ﺍﺸﺘﺭﺍﻙ ﻤﻌﻘﺩﻴﻥ ﺒﺎﻝﺫﺭﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ‪ ،‬ﻭﺍﻝﺜﺎﻨﻴﺔ ﻋﻨﺩ ﺍﺸﺘﺭﺍﻜﻬﻤﺎ ﺒﺎﻝﺭﺒﻴﻁﺔ‪ .‬ﻭﻴﻅﻬﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻓﻲ‬
‫ل ﻤﺭﺓ ﻋﻠﻰ ﺃﻨﻪ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﺒﻴﻥ ﺍﻝﻤﺎﻨﺢ ﺍﻷﻗﻭﻯ ﻭﺍﻝﻤﺘﻘ ‪‬ﺒل ﺍﻷﻗﻭﻯ ﻝﻠﺫﺭﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ﻓﻲ‬
‫ﻜّ‬
‫ﺍﻝﺤﺎﻝﺔ ﺍﻷﻭﻝﻰ ﻭﻝﻠﺭﺒﻴﻁﺔ ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺜﺎﻨﻴﺔ‪ .‬ﻫﺫﺍ ﻭﻴﻌﺭﺽ ﻫﺫﺍ ﺍﻝﻔﺼل ﺘﻁﺒﻴﻘﹰﺎ ﻋﻠﻰ ﺍﺴﺘﺜﻤﺎﺭ‬
‫ﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻓﻲ ﺘﺤﺩﻴﺩ ﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻝﻤﺘﻌﺎﻗﺒﺔ ﻷﺤﺩ ﻤﻌﻘﹼﺩﺍﺕ ﺍﻝﻜﺎﺩﻤﻴﻭﻡ ‪.II‬‬
‫ﺃ ‪‬ﻤﺎ ﺍﻝﻔﺼل ﺍﻝﺨﺎﻤﺱ‪ ،‬ﻓﻴﻌﺭﺽ ﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺘﺭﺴﻴﺏ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﺇﺫ ﻴﺘﻨﺎﻭل ﺍﻨﺤﻼل‬
‫ﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ ﻓﻲ ﺍﻝﻤﺎﺀ ﻭﻤﻔﻬﻭﻡ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ ﺍﻝﻤﺸﺒ‪‬ﻊ ﻤﻥ ﻫﺫﺍ ﺍﻝﻤﺭﻜﹼﺏ‪ ،‬ﺜ ‪‬ﻡ ﻴﻌﺭﻑ ﺠﺩﺍﺀ‬
‫ﺍﻻﻨﺤﻼل ﺜ ‪‬ﻡ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻝﻤﺭﻜﹼﺏ ﺃﻴﻭﻨﻲ ﻭﻴ‪‬ﻭﺠﺩ ﺍﻝﻌﻼﻗﺔ ﺍﻝﻘﺎﺌﻤﺔ ﺒﻴﻨﻬﻤﺎ‪ .‬ﻴﺘﻁﺭﻕ ﺍﻝﻔﺼل ﺒﻌﺩ ﺫﻝﻙ ﺇﻝﻰ‬
‫ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ ﻭﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺭﺍﺴﺏ ﻤﺎ‪ ،‬ﺜ ‪‬ﻡ ﻴﺘﻨﺎﻭل ﺩﺭﺍﺴﺔ ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺘﺭﺴﻴﺏ‪،‬‬
‫ﻭﻴﻌﺭﺽ ﺘﻁﺒﻴﻘﹰﺎ ﻋﻠﻰ ﺍﺴﺘﺜﻤﺎﺭ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﻓﻲ ﺘﺤﺩﻴﺩ ﺴﻠﻭﻙ ﻤﺯﻴﺞ ﻤﻥ ﻤﺤﻠﻭﻝﻴﻥ ﻤﺎﺌﻴﻴﻥ‬
‫ﻝﺸﺎﺭﺩﺘﻴﻥ ﺘﺘﻨﺎﻓﺴﺎﻥ ﻓﻴﻤﺎ ﺒﻴﻨﻬﻤﺎ ﻋﻠﻰ ﺘﺭﺴﻴﺏ ﺍﻝﻤ‪‬ﻠﺤ‪‬ﻴﻥ ﺍﻝﺨﺎﺼ‪‬ﻴﻥ ﺒﻬﻤﺎ‪ .‬ﻭﻴﺩﺭﺱ ﺍﻝﻌﻼﻗﺔ ﺒﻴﻥ‬
‫ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﺭﺴﻴﺏ ﻭ ‪ pH‬ﺍﻝﻭﺴﻁ‪ ،‬ﻭﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺘﺭﺴﻴﺏ ﻭﺍﻝﺘﻌﻘﻴﺩ ﻝﻴﻨﺘﻬﻲ ﺒﻌﺭﺽ ﺁﻝﻴﺔ‬
‫ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﻝﺘﺭﺴﻴﺏ‪.‬‬
‫ﻴﺘﻨﺎﻭل ﺍﻝﻔﺼل ﺍﻝﺴﺎﺩﺱ ﻤﻔﻬﻭﻡ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻭﺨﻭﺍﺼﻪ ﻝﻴﺼل ﺇﻝﻰ ﻜﻴﻔﻴﺔ ﻤﻭﺍﺯﻨﺔ ﺘﻔﺎﻋﻼﺕ‬
‫ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‪ ،‬ﺜ ‪‬ﻡ ﻴﻌﺭﺽ ﻤﻔﻬﻭﻡ ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ﻭﺒﻌﺩ ﺫﻝﻙ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﻭﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ‬
‫ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﺒﻁﺎﺭﻴﺔ‪.‬‬
‫ﻴﺘﻨﺎﻭل ﺒﻌﺩ ﺫﻝﻙ ﺍﻝﻔﺼل ﺍﻝﺴﺎﺒﻊ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﺍﻝﺘﻲ ﺘﻔﻴﺩ ﻓﻲ ﺇﺠﺭﺍﺀ ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ ﻝﺘﺄﺜﻴﺭ‬
‫ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ‪ ،‬ﻭﻜﺫﻝﻙ ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻌﻘﻴﺩ ﻭﺍﻝﺘﺭﺴﻴﺏ ﻋﻠﻰ ﺠﻤﻠﺔ ﺨﺎﻀﻌﺔ ﺒﺩﻭﺭﻫﺎ‬
‫ﻝﺘﻔﺎﻋﻼﺕ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ‪.‬‬
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‫ﻴﻌﺎﻝﺞ ﺍﻝﻔﺼل ﺍﻝﺜﺎﻤﻥ ﻤﻌﺎﻴﺭﺍﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﺤﻴﺙ ﻴﻘﺩ‪‬ﻡ ﻤﻌﺎﻴﺭﺓ‬
‫ل‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺭﻴﻭﻡ )‪ (IV‬ﻭﻤﻥ ﺜ ‪‬ﻡ ﻤﻌﺎﻴﺭﺘﻬﺎ ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ‪ ،‬ﻭﻓﻲ ﻜ ّ‬
‫ﻤﺭﺓ ﺘﺠﺭﻱ ﻤﻘﺎﺭﻨﺔ ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻨﻅﺭﻱ ﻝﻠﻤﻌﺎﻴﺭﺓ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ ﻭ ﹸﺘ ‪‬ﺒ ‪‬ﺭﺭ ﺍﻻﺨﺘﻼﻓﺎﺕ ﺍﻝﺤﺎﺼﻠﺔ‬
‫ﺇﻥ ﻭﺠﺩﺕ‪.‬‬
‫ل ﻤﻥ ﺍﻝﻤﺎﺀ ﻭﺍﻝﺤﺩﻴﺩ‪ ،‬ﻭﻴﻌﺭﺽ‬
‫ﻴﺘﻁﺭ‪‬ﻕ ﺍﻝﻔﺼل ﺍﻝﺘﺎﺴﻊ ﻝﺭﺴﻡ ﻤﺨﻁﻁﺎﺕ ﻜﻤﻭﻥ‪ pH -‬ﻝﻜ ّ‬
‫ﻜﻴﻔﻴﺔ ﺍﺴﺘﺜﻤﺎﺭ ﻫﺫﻩ ﺍﻝﻤﺨﻁﻁﺎﺕ ﻓﻲ ﺍﻝﺘﻨﺒ‪‬ﺅ ﺒﺎﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ‪.‬‬
‫ل‬
‫ﻫﺫﺍ ﻭﻗﺩ ﺍﺤﺘﻭﺕ ﺠﻤﻴﻊ ﻫﺫﻩ ﺍﻝﻔﺼﻭل ﻋﻠﻰ ﻤﺴﺎﺌل ﺘﻁﺒﻴﻘﻴﺔ ﻝﻴﺘﻤﺭ‪‬ﻥ ﺍﻝﻁﺎﻝﺏ ﻋﻠﻰ ﻜﻴﻔﻴﺔ ﺤ ّ‬
‫ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﺍﻝﺠﺩﻴﺩ ﻤﻥ ﺍﻝﻤﺴﺎﺌل ﻤﻥ ﻜﺘﺎﺒ ‪‬ﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺃﻭ ﻗﺭﺍﺀ ‪‬ﺓ ﻝﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﺇﻝﺦ…‪،‬‬
‫ﻭﺃﺘﺒﻌﻨﺎ ﺠﻤﻴﻊ ﻫﺫﻩ ﺍﻝﻔﺼﻭل ﺒﻌﺩﺩ ﻭﺍﻓﺭ ﻤﻥ ﺍﻝﺘﻤﺭﻴﻨﺎﺕ ﻭﺍﻝﻤﺴﺎﺌل ﻝﻴﺘﺴﻨﹼﻰ ﻝﻠﻁﺎﻝﺏ ﺘﻌﺯﻴﺯ ﺍﺴﺘﻴﻌﺎﺒﻪ‬
‫ﻥ ﺒﻌﻀﻬﺎ ﺘﻁﺒﻴﻕ‬
‫ﻝﻠﻤﻔﺎﻫﻴﻡ ﺍﻝﻨﻅﺭﻴﺔ‪ .‬ﻭﺘﺨﺘﻠﻑ ﻫﺫﻩ ﺍﻝﺘﻤﺭﻴﻨﺎﺕ ﻭﺍﻝﻤﺴﺎﺌل ﻓﻲ ﺼﻌﻭﺒﺘﻬﺎ ﺤﻴﺙ ﻨﺠﺩ ﺃ ‪‬‬
‫ﻤﺒﺎﺸﺭ ﻝﻠﺩﺭﺍﺴﺔ ﺍﻝﻨﻅﺭﻴﺔ‪ ،‬ﻓﻲ ﺤﻴﻥ ﻴﺘﻁﻠﹼﺏ ﺒﻌﻀﻬﺎ ﺍﻵﺨﺭ ﺘﻭﻅﻴﻑ ﺍﻝﻤﻔﺎﻫﻴﻡ ﺍﻝﺘﻲ ﺩﺭﺴﻬﺎ ﺍﻝﻁﺎﻝﺏ‬
‫ل ﻝﻬﺎ‪ .‬ﻭﻫﻲ ﻋﻠﻰ ﺘﻨﻭ‪‬ﻋﻬﺎ ﻫﺫﺍ ﺘﻼﺌﻡ ﺠﻤﻴﻊ ﺍﻝﻁﻼﺏ ﻋﻠﻰ ﺍﺨﺘﻼﻑ ﻤﺴﺘﻭﻴﺎﺘﻬﻡ‪.‬‬
‫ﻨﻅﺭﻴﹰﺎ ﻓﻲ ﺇﻴﺠﺎﺩ ﺤ ّ‬
‫ل ﻤﻥ ﺴﺎﻫﻡ ﻓﻲ ﺇﻨﺠﺎﺯ ﻫﺫﺍ ﺍﻝﻌﻤل‪ ،‬ﻭﺨﺼﻭﺼﹰﺎ ﺍﻝﺩﻜﺘﻭﺭ‬
‫ﻓﻲ ﺍﻝﻨﻬﺎﻴﺔ ﻻ ﺒ ‪‬ﺩ ﻤﻥ ﺸﻜﺭ ﻜ ّ‬
‫ﻋﻤﺭﺍﻥ ﻗﻭﺒﺎ ﺍﻝﺫﻱ ﺴﺎﻋﺩﻨﻲ ﻓﻲ ﺍﺴﺘﻌﻤﺎل ﺒﺭﻤﺠﻴﺎﺕ ﻤﺘﺨﺼ‪‬ﺼﺔ ﻓﻲ ﺍﻝﺤل ﺍﻝﻌﺩﺩﻱ ﻝﺠﻤل ﺍﻝﻤﻌﺎﺩﻻﺕ‬
‫ﻏﻴﺭ ﺍﻝﺨﻁﻴﺔ ﺍﻝﺘﻲ ﻨﺤﺼل ﻋﻠﻴﻬﺎ ﻋﻨﺩ ﻜﺘﺎﺒﺔ ﺠﻤﻴﻊ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﻲ ﺘﺭﺒﻁ ﺒﻴﻥ ﺘﺭﺍﻜﻴﺯ ﺍﻷﻨﻭﺍﻉ‬
‫ﺍﻝﻤﺘﻭﻓﺭﺓ ﻓﻲ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺩﻭﻥ ﺃﻱ ﺘﻘﺭﻴﺏ‪ ،‬ﻭﻤﻥ ﺜ ‪‬ﻡ ﺇﻅﻬﺎﺭ ﺍﻝﻨﺘﺎﺌﺞ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﺒﺘﺩﺍﺀ‬
‫ﻤﻥ ﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ‪ ،‬ﻭﻤﺭﻭﺭﹰﺍ ﺒﻤﺨﻁﻁﺎﺕ ‪ Flood‬ﻭﺍﻨﺘﻬﺎﺀ ﺒﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻭﺃﺸﻜﺭﻩ ﺃﻴﻀﹰﺎ‬
‫ﻋﻠﻰ ﺍﻝﻜﺜﻴﺭ ﻤﻥ ﺍﻹﻏﻨﺎﺀﺍﺕ ﻭﺍﻝﻤﻼﺤﻅﺎﺕ ﺍﻝﺒﻨﺎﺀﺓ ﺍﻝﺘﻲ ﺃﻓﺎﺩﻨﻲ ﺒﻬﺎ ﻓﻲ ﺇﺨﺭﺍﺝ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ‪.‬‬
‫ﻲ ﻝﻤﻴﺎﺀ ﻭﻤﺭﺡ ﺍﻝﻠﺘﻴﻥ ﺴﺎﻋﺩﺘﺎﻨﻲ ﻋﻠﻰ ﺘﻨﻀﻴﺩ ﺒﻌﺽ ﺃﺠﺯﺍﺀ "ﺍﻝﻜﻴﻤﻴﺎﺀ ﻤﻥ‬
‫ﻭﺃﺸﻜﺭ ﺍﺒﻨﺘ ‪‬‬
‫ﻭﺍﻗﺘﺭﺤﺘﺎ ﻏﻼﻓﹰﺎ ﻝﻠﻜﺘﺎﺏ‪.‬‬ ‫ﺤﻭﻝﻨﺎ"‬
‫ﻭﻜﻠﻲ ﺃﻤل ﺃﻥ ﻴﻜﻭﻥ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ ﺨﻴﺭ ﺩﻝﻴل ﻝﻁﻼﺒﻨﺎ ﻓﻲ ﺩﺭﺍﺴﺔ ﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪.‬‬
‫ل ﻗﺎﺭﺉ ﻴ‪‬ﺒﺩﻱ ﺍﻨﺘﻘﺎﺩﹰﺍ ﺒﻨﹼﺎﺀ ﻋﻠﻰ ﻓﺤﻭﻯ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ‪.‬‬
‫ﻭﺃﺘﻘﺩ‪‬ﻡ ﺴﻠﻔﹰﺎ ﺒﺎﻝﺸﻜﺭ ﺇﻝﻰ ﻜ ّ‬
‫ﻴ‪‬ﻤﻥ ﺍﻷﺘﺎﺴﻲ‬ ‫ﺘﺸﺭﻴﻥ ﺍﻝﺜﺎﻨﻲ ‪2010‬‬
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‫ﺍﻟﻔﺼﻞ ﺍﻷﻭﻝ‬
‫
‪ -‬‬
‫ ‬
‫‪ .I‬ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺫﻴﺒﹰﺎ‬
‫‪ .1.I‬ﺘﺫﻜﺭﺓ ﺒﺒﻌﺽ ﺍﻝﺘﻌﺎﺭﻴﻑ‬
‫‪ .2.I‬ﺍﻝﻤﺎﺀ‪ :‬ﻤﺫﻴﺏ ﺫﻭ ﺨﻭﺍﺹ ﺘﺸﺭﻴﺩ ﻭﺇﻤﺎﻫﺔ ﻭﺘﺸﺘﻴﺕ‬
‫‪ .II‬ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ‬
‫‪ .1.II‬ﺘﻌﺎﺭﻴﻑ‬
‫‪ pH .2.II‬ﻤﺤﻠﻭل‬
‫‪ .3.II‬ﺍﻝﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ‬
‫‪ .4.II‬ﺍﻝﺯﻭﺠﺎﻥ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﺨﺎﺼ‪‬ﺎﻥ ﺒﺎﻝﻤﺎﺀ‬
‫‪ .5.II‬ﺘﻔﺎﻋل ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ ﻤﻊ ﺍﻝﻤﺎﺀ‬
‫‪ .6.II‬ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‬
‫‪ .1.6.II‬ﺍﻝﺯﻭﺝ ‪H A /A−‬‬
‫ﻼ‬
‫‪ .2.6.II‬ﺯﻭﺠﺎ ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺤ ﹰ‬
‫‪ .III‬ﺘﺭﺘﻴﺏ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‬
‫‪ .1.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﺍﻝﻀﻌﻴﻔﺔ‬
‫‪ .2.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﺍﻝﻘﻭﻴﺔ ﻭﺍﻷﺴﺱ ﺍﻝﻘﻭﻴﺔ‬
‫‪ .IV‬ﻤﺨﻁﻁﺎﺕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ‬
‫‪ .V‬ﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ ‪ :‬ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ‬
‫‪ .VI‬ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‬
‫‪ .VII‬ﺘﻁﺒﻴﻘﺎﺕ‬
‫‪5‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻷﻭﻝ‬ ‫‪6‬‬
‫‪ .I‬ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺫﻴﺒ ﹰﺎ‬
‫ﻻ ﻓﻲ ﺍﻝﻜﻴﻤﻴﺎﺀ‪ ،‬ﻭﺘﻌﺘﺒﺭ ﺩﺭﺍﺴﺔ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﻋﻠﻰ ﻗﺩﺭ‬

‫ﺏ ﺍﻷﻜﺜﺭ ﺍﺴﺘﻌﻤﺎ ﹰ‬
‫‪‬ﻴﻌ ‪‬ﺩ ﺍﻝﻤﺎ ‪‬ﺀ ﺍﻝﻤﺫﻴ ‪‬‬
‫ﻜﺒﻴﺭ ﻤﻥ ﺍﻷﻫﻤﻴﺔ ﻝﻔﻬﻡ ﺍﻝﻌﺎﻝﻡ ﺍﻝﻤﺤﻴﻁ ﺒﻨﺎ‪ .‬ﻓﺜﻼﺜﺔ ﺃﺭﺒﺎﻉ ﺍﻝﻘﺸﺭﺓ ﺍﻷﺭﻀﻴﺔ ﺘﻘﺭﻴﺒﹰﺎ ﻤﻐﻁﺎﺓ ﺒﺎﻝﻤﻴﺎﻩ‪،‬‬
‫ﻥ ﺍﻝﺴﻭﺍﺌل ﺍﻝﺤﻴﻭﻴﺔ‬
‫ﺤﻴﺙ ﻴﺤﺼل ﻓﻲ ﺍﻝﻤﺤﻴﻁﺎﺕ ﻋﺩﺩ ﻫﺎﺌل ﻤﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﺎﺌﻴﺔ‪ ،‬ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺃ ‪‬‬
‫ﻥ ﺍﻵﻝﻴﺎﺕ ﺍﻝﺤﻴﻭﻴﺔ ﻓﻲ ﻫﺫﻩ ﺍﻝﻜﺎﺌﻨﺎﺕ ﺍﻝﺤﻴﺔ ﻤﺎ‬
‫ﻓﻲ ﺍﻝﻨﺒﺎﺘﺎﺕ ﻭﺍﻝﺤﻴﻭﺍﻨﺎﺕ ﺃﺴﺎﺴﻬﺎ ﺍﻝﻤﺎﺀ‪ ،‬ﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ل‬
‫ﻫﻲ ﺇﻻ ﺘﻔﺎﻋﻼﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻀﻤﻥ ﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ ﺃﻭ ﺒﺘﻤﺎﺱ ﻤﻊ ﺍﻝﻤﺎﺀ‪ .‬ﺤﺘﻰ ﻗﺒل ﺃﻥ ﻨﻭﻝﺩ ﻜﺎﻥ ﻜ ّ‬
‫ﻤﻨﺎ ﺠﻨﻴﻨﹰﺎ ﻴﻌﻴﺵ ﻀﻤﻥ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻫﺩﻓﻪ ﺤﻤﺎﻴﺘﻪ ﻭﺘﻐﺫﻴﺘﻪ ﺤﺘﻰ ﻴﺼﺒﺢ ﻗﺎﺩﺭﹰﺍ ﻋﻠﻰ ﺍﻝﺤﻴﺎﺓ ﺘﺤﺕ‬
‫ﺍﻝﻐﻼﻑ ﺍﻝﺠﻭﻱ‪.‬‬
‫ﻭﻝﺫﻝﻙ ﺴﻨﺩﺭﺱ ﺒﺩﺍﻴﺔ ﺒﻌﺽ ﻤﻤﻴ‪‬ﺯﺍﺕ ﻫﺫﺍ ﺍﻝﺴﺎﺌل ‪ ،‬ﻭﺴﻨﺫﻜﹼﺭ ﺒﺒﻌﺽ ﺍﻝﺘﻌﺎﺭﻴﻑ ﺍﻝﻤﺭﺘﺒﻁﺔ‬
‫ﺒﺎﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪.‬‬
‫‪ .1.I‬ﺘﺫﻜﺭﺓ ﺒﺒﻌﺽ ﺍﻝﺘﻌﺎﺭﻴﻑ‬
‫ﻨﺤﺼل ﻋﻠﻰ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻋﻥ ﻁﺭﻴﻕ ﺤ ّل ﺃﻭ ﺇﺫﺍﺒﺔ ﻤﺭ ﻜﹼﺏ ﺃﻭ ﺃﻜﺜﺭ ﻗﺎﺒل ﻝﻼﻨﺤﻼل ﺃﻭ‬
‫ﻝﻺﺫﺍﺒﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭ ﻴﺅ ﺩ‪‬ﻱ ﺍﻝﻤﺎﺀ ﺩﻭﺭ ﺍﻝﻤﺫﻴﺏ ﺃﻭ ﺍﻝ ‪‬ﻤﺤ‪‬ل‪ .‬ﻭﺘﻜﻭﻥ ﻋﺎﺩﺓ ﻜﻤﻴﺔ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻨﺤﻠﺔ‬
‫ﺼﻐﻴﺭﺓ ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﻜﻤﻴﺔ ﺍﻝﻤﺫﻴﺏ ﺃﻭ ﺍﻝﻤﺤل ﺍﻝﺫﻱ ﺘﻜﻭﻥ ﺠﺯﻴﺌﺎﺘﻪ ﻫﻲ ﺍﻝﻐﺎﻝﺒﺔ ‪ ،‬ﻭﻨﻌﺒ ‪‬ﺭ ﻋﻥ ﺫ ﻝﻙ‬
‫ﺒﺎﻝﻘﻭل ﺇﻥ ﺍﻝﻤﺫﻴﺏ ﻴﻜﻭ‪‬ﻥ ﺍﻝﻨﻭﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻲ‪ 1‬ﺍﻝﻐﺎﻝﺏ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻭﺘﻌﺘﺒﺭ ﻅﺎﻫﺭﺓ ﺍﻻﻨﺤﻼل ﻅﺎﻫﺭﺓ ﻤﺤﺩﻭﺩﺓ‪ :‬ﻷﻨﹼﻪ ﺒﺩﺀﹰﺍ ﻤﻥ ﻜﻤﻴﺔ ﻤﻌﻴﻨﺔ ﻤﻥ ﺍﻝﻤﺭﻜﹼﺏ ﺍﻝﻤﺫﺍﺏ‬
‫ﻱ ﻜﻤﻴﺔ ﺇﻀﺎﻓﻴﺔ ﻤﻨﻪ ﻋﻨﺩ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﻤﻌﻴﻨﺔ‪ ،‬ﻭﻨﻌﺒ‪‬ﺭ ﻋﻥ ﺫﻝﻙ ﺒﺎﻝﻘﻭل‬
‫لﺃ ‪‬‬
‫ﺃﻭ ﺍﻝﻤ‪‬ﻨﺤلّ‪ ،‬ﻻ ﻴﻤﻜﻥ ﺤ ّ‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﺃﺼﺒﺢ ﻤ‪‬ﺸﺒﻌﹰﺎ‪.‬‬
‫ﺇ‪‬‬
‫ﻜﺫﻝﻙ ﺘﻌﺯ ﻯ ﺍﻝﻨﺎﻗﻠﻴﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌ‪‬ﻴﺔ ﺇﻝﻰ ﻭﺠﻭﺩ ﺍﻝﺸﻭﺍﺭﺩ ﻓﻴﻬﺎ‪ .‬ﺇ ﺫﹾ ﻻ ﻴﺘﻤﺘﻊ‬
‫ل ﻤﺭﻜﹼﺏ ﻴﺅﺩﻱ ﺤﻠﹼﻪ ﻓﻲ ﻤﺫﻴﺏ‬
‫ﻻ ﺒﻨﺎﻗﻠ‪‬ﻴﺔ ﻜﻬﺭﺒﺎﺌﻴﺔ ﻀﻌﻴﻔﺔ ﺠﺩ ﹰﺍ‪ .‬ﻭﻨﺴﻤﻲ ﻜﻬﺭﻝﻴﺘﹰﺎ ﻜ ّ‬
‫ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ ﺇ ﹼ‬
‫ﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫‪-‬ﻭﻫﻭ ﻓﻲ ﺤﺎﻝﺘﻨﺎ ﻫﺫﻩ ﺍﻝﻤﺎﺀ‪ -‬ﺇﻝﻰ ﺍﺯﺩﻴﺎ ‪‬ﺩ ﻓﻲ ﺍﻝﻨﺎﻗﻠﻴﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ‪ .‬ﻭﻫﻜﺫﺍ ﻓﺈ ‪‬‬
‫ﻭﻜﻠﻭﺭ ﻴﺩ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻫﻤﺎ ﻜﻬﺭﻝﻴﺘﺎﻥ ﻨﻅﺭ ﹰﺍ ﻝﻜﻭﻥ ﻤﺤﺎﻝﻴﻠﻬﻤﺎ ﺘﻀ ‪‬ﻡ ﺸﻭﺍﺭ ‪‬ﺩ ﻭﺘﻜﻭ‪‬ﻥ ﻤﺎ ﻴﺴﻤﻰ‬
‫ﺒﺎﻝﻤﺤﺎﻝﻴل ﺍﻝﻜﻬﺭﻝﻴﺘﻴﺔ‪.‬‬
‫‪1‬‬
‫ﺍﻝﻨﻭﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻲ ﺤﺴﺏ ﺘﻌﺭﻴﻑ ﺍﻻﺘﺤﺎﺩ ﺍﻝﺩﻭﻝﻲ ﻝﻠﻜﻴﻤﻴﺎﺀ ﺍﻝﺒﺤﺘﺔ ﻭﺍﻝﺘﻁﺒﻴﻘﻴﺔ ﻫﻭ ﻤﺠﻤﻭﻋﺔ ﻤﻥ ﺍﻝﻜﻴﻨﻭﻨﺎﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﻤﺘﻁﺎﺒﻘﺔ )ﺫﺭﺍﺕ ﺃﻭ ﺠﺯﻴﺌﺎﺕ‬
‫ﺃﻭ ﺸﻭﺍﺭﺩ‪ ،‬ﺃﻭ ﺠﺫﻭﺭ ﺃﻭ ﺸﻭﺍﺭﺩ ﺠﺯﻴﺌﻴﺔ‪ (....،‬ﺘﺸﻐل ﺍﻝﻤﺠﻤﻭﻋﺔ ﺫﺍﺘﻬﺎ ﻤﻥ ﻤﺴﺘﻭﻴﺎﺕ ﺍﻝﻁﺎﻗﺔ ﻓﻲ ﻤﺩﺓ ﻤﺤﺩﺩﺓ ﻤﻥ ﺍﻝﺯﻤﻥ‪.‬‬
‫‪7‬‬ ‫ﺍﻟﺘﻮﺍﺯﻧﺎﺕ ﲪﺾ – ﺃﺳﺎﺱ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫‪ .2.I‬ﺍﻝﻤﺎﺀ‪ :‬ﻤﺫﻴﺏ‪ ‬ﺫﻭ ﺨﻭﺍﺹ ﺘﺸﺭﻴﺩ ﻭﺇﻤﺎﻫﺔ ﻭﺘﺸﺘﻴﺕ‬
‫ﻥ ﻋﻠﻰ ﺸﻜل ﺤﺭﻑ ‪ .V‬ﻭﻝﻤ‪‬ﺎ‬

‫ﻻ ﻴﺘﻤﺘﻊ ﺠﺯﻱﺀ ﺍﻝﻤﺎﺀ ﺒﻬﻨﺩﺴﺔ ﺨﻁﻴﺔ‪ ،‬ﻭﺇﻨﻤﺎ ﻫﻭ ﺠﺯﻱﺀ ﻤﻨﺤ ﹴ‬
‫ﻥ ﻫﺫ ﺍ ﺍﻝﺠﺯﻱ ﺀ ﺍﻝﻤﺘﺸﻜﹼل ﻤﻨﻬﻤﺎ‬
‫ﻜﺎﻨﺕ ﺫﺭﺓ ﺍﻷﻜﺴﺠﻴﻥ ﺃﻜﺜﺭ ﻜﻬﺭﺴﻠﺒﻴﺔ ﻤﻥ ﺫﺭﺓ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ‪ ،‬ﻓﺈ ‪‬‬
‫ﻲ ﻭﻝﻪ ﻋﺯﻡ ﺜﻨﺎﺌﻲ ﻗﻁﺏ ﻜﺒﻴ ﹴﺭ ﻗﻴﻤﺘﻪ ‪ µ(H2O) = 1.85 D‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪. 20 C‬‬
‫ﻗﻁﺒ ‪‬‬
‫ﺍﻨﻅﺭ ﺍﻝﺸﻜل )‪. (1‬‬
‫‪+δ‬‬ ‫‪H‬‬
‫‪−2δ‬‬ ‫‪O‬‬
‫‬
‫ﺜﻨﺎﺌﻴﺔ ﻏﻴﺭ ﺭﺍﺒﻁﺔ‬ ‫‪p‬‬
‫ﺜﻨﺎﺌﻴﺔ ﺭﺍﺒﻁﺔ‬
‫‪H‬‬
‫‪+δ‬‬
‫ﺍﻝﺸﻜل )‪ : (1‬ﺠﺯﻱﺀ ﺍﻝﻤﺎﺀ ﺍﻝﻘﻁﺒﻲ‪.‬‬
‫ﻭﻜﺫ ﻝﻙ ﻴﺘﻤﺘﻊ ﺍ ﻝﻤﺎﺀ ﺒﺜﺎﺒﺕ ﻋﺯ ل ﻜﻬﺭﺒﺎﺌﻲ ﻜﺒﻴ ﹴﺭ ﺃ ﻴﻀﹰﺎ ﺘﺼل ﻗﻴﻤﺘﻪ ﻋﻨﺩ ‪ 20 C‬ﺇ ﻝﻰ‬
‫ﻥ ﺍﻝﻘﻭﺓ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﺍﻝﺴﺎﻜﻨﺔ ﺒﻴﻥ ﺸﺎﺭﺩﺓ ﻤﻭﺠﺒﺔ ﻭﺃﺨﺭﻯ ﺴﺎﻝﺒﺔ ﺘﻜﻭﻥ‬
‫‪ . εr ≈ 80‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻥ ﺍﻝﻘﻭﺓ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﺍﻝﺴﺎﻜﻨﺔ ﻓﻲ ﺍﻝﺨﻼﺀ‬
‫ﺃﻀﻌﻑ ﺒﺜﻤﺎﻨﻴﻥ ﻤﺭﺓ ﻓﻲ ﺍﻝﻤﺎﺀ ﻤﻨﻬﺎ ﻓﻲ ﺍﻝﺨﻼﺀ ‪ ،‬ﺫﻝﻙ ﻷ ‪‬‬
‫ﺒﻴﻥ ﺸﺤﻨﺘﻴﻥ ﻨﻘﻁﻴﺘﻴﻥ ‪ q‬ﻭ ‪ q ′‬ﺘﻔﺼل ﺒﻴﻨﻬﻤﺎ ﻤﺴﺎﻓﺔ ‪ r‬ﺘﻌﻁﻰ ﺒﺎﻝﻌﻼﻗﺔ ‪:‬‬
‫‬ ‫‪qq ′‬‬
‫= ‪fv‬‬
‫‪4πε0r 2‬‬
‫ﺤﻴﺙ ‪ ε0‬ﻫﻭ ﺜﺎﺒﺕ ﺍﻝﻌﺯل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻠﺨﻼﺀ‪ .‬ﻓﻲ ﺤﻴﻥ ﺘﹸﺤﺴﺏ ﺍﻝﻘﻭﺓ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﺍﻝﺴﺎﻜﻨﺔ ﻓﻲ‬
‫ﻤﺫﻴﺏ ﻴﺘﻤﺘﹼﻊ ﺒﺜﺎﺒﺕ ﻋﺯل ﻜﻬﺭﺒﺎﺌﻲ ﻗﻴﻤﺘﻪ ‪ εr‬ﺒﺎﻝﻌﻼﻗﺔ ‪:‬‬
‫‬ ‫‪qq ′‬‬
‫= ‪fs‬‬
‫‪4 πε0εr r 2‬‬
‫ﺕ ﻤﺎ ‪‬ﺀ‪ ،‬ﻭﻫﺫﺍ ﻴﺯﻴﺩ ﻤﻥ ﺍﺴﺘﻘﺭﺍﺭﻫﺎ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪،‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﺸﻭﺍﺭﺩ ﻓﻲ ﺍﻝﻤﺎﺀ ﻤﺤﺎﻁﺔ ﺒﺠﺯﻴﺌﺎ ‪‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ‪‬ﻤﻨﺤﻠﱠﺔ ﺃﻭ ﺒﺘﺤﺩﻴﺩ ﺃﻜﺜﺭ ﻤ‪‬ﻤﻴ‪‬ﻬﺔ‪ .‬ﻭﻋﻨﺩﻤﺎ ﻨﺭﻴﺩ ﺍﻝﺘﻌﺒﻴﺭﻋﻥ‬
‫ﻭﻨﻌﺒ‪‬ﺭ ﻋﻥ ﺫﻝﻙ ﺒﻘﻭﻝﻨﺎ ﺇ ‪‬‬
‫ﻼ ﻤﻨﺤﻠﺔ ﻓﻲ ﺍﻝﻤﺎﺀ ﻓﺈﻨﻨﺎ ﻨﻜﺘﺏ ﻋﺎﺩﺓ )‪ aq) Cu2+(aq‬ﻤﻥ‬
‫ﻥ ﺸﻭﺍﺭ ‪‬ﺩ ﺍﻝﻨﺤﺎﺱ ‪ Cu2+‬ﻤﺜ ﹰ‬
‫ﺃ‪‬‬
‫ﺍﻹﻨﻜﻠﻴﺯﻴﺔ ‪ aqueous‬ﺃﻱ ﻤﺎﺌﻲ(‪ .‬ﻭﻴﺯﺩﺍﺩ ﻋﺩﺩ ﺠﺯﻴﺌﺎﺕ ﺍﻝﻤﺎﺀ ﺍﻝﺘﻲ ﺘﺤﻴﻁ ﺒﺎﻝﺸﺎﺭﺩﺓ ﻤﻊ ﺍﺯﺩﻴﺎﺩ‬
‫ﺼﻐﺭﻫﺎ ﻭﻜﺒﺭ ﺸﺤﻨﺘﻬﺎ‪.‬‬
‫ﻨﺴﺘﻁﻴﻊ ﺘﻌﻠﻴل ﺍﻨﺤﻼل ﺍﻷﺠﺴﺎﻡ ﺍﻝﺼﻠﺒﺔ ﺍﻝﺸﺎﺭﺩﻴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ ‪ ،‬ﺍﻝﺸﻜل ) ‪ ، ( 2‬ﺃﻭ ﺘﺸﺭ‪‬ﺩ‬
‫ﺠﺯﻱ ﺀ ﻗﻁﺒﻲ ﻓﻲ ﺍﻝﻤﺎﺀ ‪ ،‬ﺍﻝﺸﻜل ) ‪ ، ( 3‬ﺇﺫﺍ ﻨﻅﺭﻨﺎ ﺇﻝﻰ ﺠﺯﻴﺌﺎ ﺕ ﺍﻝﻤﺎﺀ ﻋﻠﻰ ﺃﻨﻬﺎ ﺜﻨﺎﺌﻴﺎﺕ ﻗﻁﺏ‬
‫ﻜﻬﺭﺒﺎﺌﻴﺔ ﺴﺎﻜﻨﺔ‪.‬‬
‫ﻓﻔﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﺼﻠﺒﺔ ﺍﻝﺸﺎﺭﺩﻴﺔ ﻭﺘﺤﺕ ﺘﺄﺜﻴﺭ ﺜﻨﺎﺌﻴﺎﺕ ﺍﻝﻘﻁﺏ ﺍﻝﻜﻬﺭﺒﺎﺌﻴـﺔ ﺘﺨﻀـﻊ‬
‫ﺍﻝﺸﺒﻜﺔ ﺍﻝﺒﻠﻭﺭﻴﺔ ﻻﻨﺨﻼﻋﺎﺕ ﻓﺘﺘﺤﺭ‪‬ﺭ ﺍﻝﺸﻭﺍﺭﺩ ﻤﻥ ﺍﻝﺸﺒﻜﺔ ﺍﻝﺒﻠﻭﺭﻴﺔ ﻭﺘﺘﻭﺠﻪ ﺠﺯﻴﺌﺎﺕ ﺍﻝﻤﺎﺀ ﺒﺤﻴﺙ‬
‫ﺘﺤﻴﻁ ﺫﺭﺍﺕ ﺍﻷﻜﺴﺠﻴﻥ ﺒﺎﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﺒﺔ ﻭﺘﺤﻴﻁ ﺫﺭﺍﺕ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺒﺎﻝﺸﻭﺍﺭﺩ ﺍﻝﺴﺎﻝﺒﺔ‪ ،‬ﻭﻫـﺫﺍ‬
‫ﻴﺴﺒﺏ ﺍﺴﺘﻘﺭﺍﺭ ﺍﻝﺸﻭﺍﺭﺩ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﺘﹸﻌﺭﻑ ﻫﺫﻩ ﺍﻝﻌﻤﻠﻴﺔ ﺒﺎﻹﻤﺎﻫﺔ‪ ،‬ﻭﺃﺨﻴﺭﹰﺍ ﻭﺒﻔﻀل ﺍﺭﺘﻔﺎﻉ ﻗﻴﻤـﺔ‬
‫ﺜﺎﺒﺕ ﺍﻝﻌﺯل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﺘﺘﺸﺘﹼﺕ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻤﻴﻬﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﺒﺫﻝﻙ ﻴﺘ ‪‬ﻡ ﺍﻻﻨﺤﻼل‪.‬‬
‫ﺍﻝﺸﻜل )‪ : (2‬ﻤﺭﺍﺤل ﺍﻨﺤﻼل ﻤﺭﻜﹼﺏ ﺼﻠﺏ ﺸﺎﺭﺩﻱ ﻓﻲ ﺍﻝﻤﺎﺀ ‪ :‬ﺍﻻﻨﺨﻼﻉ‪ ،‬ﺍﻹﻤﺎﻫﺔ‪ ،‬ﺍﻝﺘﺸﺘﹼﺕ‪.‬‬
‫ﺃﻤﺎ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﺠﺯﻴﺌﻴﺔ ﺍﻝﻘﻁﺒﻴﺔ ﻤﺜل ‪ HCl‬ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻓﺒﻔﻀل ﺜﻨﺎﺌﻴﺎﺕ ﻗﻁﺏ‬
‫ﺍﻝﻤﺫﻴﺏ ﻴﺯﺩﺍﺩ ﺍﺴﺘﻘﻁﺎﺏ ﺍﻝﺠﺯﻱﺀ ‪ HCl‬ﻭﺸﻴﺌﹰﺎ ﻓﺸﻴﺌﹰﺎ ﺘﺘﺤﺭﺭ ﺍﻝﺸﺎﺭﺩﺓ ‪ Cl−‬ﻭﺍﻝﺸﺎﺭﺩﺓ ‪H+‬‬
‫ﻝﺘﺘﺤﻭ‪‬ﻻ ﺇﻝﻰ ﺸﺎﺭﺩﺘﻴﻥ ﻤﻤﻴﻬﺘﻴﻥ )‪ Cl−(aq‬ﻭ ‪ . H3O+‬ﻭﺒﺴﺒﺏ ﺘﻤﺘﹼﻊ ﺍﻝﻤﺎﺀ ﺒﺜﺎﺒﺕ ﻋﺯل ﻜﻬﺭﺒﺎﺌﻲ‬
‫ﻜﺒﻴﺭ ﺘﻨﻔﺼل ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻤﻴ‪‬ﻬﺔ ﺘﺤﺕ ﺘﺄﺜﻴﺭ ﺍﻻﻫﺘﺯﺍﺯ ﺍﻝﺤﺭﺍﺭﻱ ﹸﺜ ‪‬ﻡ ﺘﺘﺸﺘﹼﺕ ﺒﻌﺩ ﺫﻝﻙ‪ ،‬ﻭﺒﺫﻝﻙ‬
‫ﻴﺤﺼل ﺍﻻﻨﺤﻼل‪.‬‬
‫)‪a‬‬ ‫)‪b‬‬ ‫)‪c‬‬
‫‪H3O+‬‬
‫‪−δ‬‬ ‫‪H3O+‬‬
‫‪+δ‬‬
‫‪Cl−‬‬ ‫‪Cl−‬‬
‫‪H‬‬
‫‪Cl‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 3‬ﺍﻨﺤﻼل ﻤﺭﻜﹼﺏ ﺠﺯﻴﺌﻲ ﻤﺜل ‪ HCl‬ﻓﻲ ﺍﻝﻤﺎﺀ ‪:‬‬

‫) ‪ : a‬ﻴﺯﺩﺍﺩ ﺍﺴﺘﻘﻁﺎﺏ ﺍﻝﺠﺯﻱﺀ ‪ HCl‬ﺒﺴﺒﺏ ﻜﻭﻥ ﺍﻝﻤﺎﺀ ﻤﺫﻴﺒﹰﺎ ﻤﺘﻤﺘﻌﹰﺎ ﺒﻘﺩﺭﺓ ﺍﺴﺘﻘﻁﺎﺒﻴﺔ‪،‬‬
‫) ‪ : b‬ﺘﺘﺸ ﹼﻜل ﺸﺎﺭﺩﺘﺎﻥ ‪‬ﻤﻤﻴﻬﺘﺎﻥ )‪ Cl−(aq‬ﻭ ‪، H3O+‬‬
‫) ‪ : c‬ﺒﺴﺒﺏ ﺘﻤﺘﹼﻊ ﺍﻝﻤﺎﺀ ﺒﺜﺎﺒﺕ ﻋﺯل ﻜﻬﺭﺒﺎﺌﻲ ‪ εr ≈ 80‬ﺘﻨﻔﺼل ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻤﻴ‪‬ﻬﺔ‬
‫ﺘﺤﺕ ﺘﺄﺜﻴﺭ ﺍﻻﻫﺘﺯﺍﺯ ﺍﻝﺤﺭﺍﺭﻱ ﹸﺜ ‪‬ﻡ ﺘﺘﺸﺘﹼﺕ ﺒﻌﺩ ﺫﻝﻙ‪.‬‬
‫ﻴ‪‬ﻅﻬﺭ ﺍﻝﺠﺩ ﻭل ﺍﻝﺘﺎﻝﻲ ﻗﻴﻡ ﺍﻝﻌﺯ ﻭ ﻡ ﺍﻝﺜﻨﺎﺌﻴﺔ ﺍﻝﻘﻁﺏ ﻭﺜﻭ ﺍﺒﺕ ﺍﻝﻌﺯل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﺒﻌﺽ‬
‫ﺍﻝﻤﺫﻴﺒﺎﺕ ﻭﻨﻼﺤﻅ ﻤﻥ ﻫﺫﺍ ﺍﻝﺠﺩﻭل ﺃﻥ ﺍﻝﻤﺎﺀ ﻴﺼﱠﻨﻑ ﻤﻊ ﺍﻝﻤﺫﻴﺒﺎﺕ ﺍﻝﺘﻲ ﺘﺘﻤﺘﻊ ﺒﺎﺭﺘﻔﺎﻉ ﻗﻴﻤﺔ ﺍﻝﻌﺯﻡ‬
‫ﻥ ﻗﺩﺭﺓ ﻤﺫﻴﺏ ﻤﺎ ﻋﻠﻰ‬
‫ﺍﻝﺜﻨﺎﺌﻲ ﺍﻝﻘﻁﺏ ﻭ ﺜﺎﺒﺕ ﺍﻝﻌﺯل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ‪ .‬ﻭﻤﻥ ﺍﻝﻤﻔﻴﺩ ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ ﺃ ‪‬‬
‫ﺍﻝﺘﺸﺭﻴﺩ ﺘﺯﺩﺍﺩ ﺒﺎﺯﺩﻴﺎﺩ ﻋﺯﻤﻪ ﺍﻝﺜﻨﺎﺌﻲ ﺍﻝﻘﻁﺏ‪ ،‬ﻓﻲ ﺤﻴﻥ ﺘﺯﺩﺍﺩ ﻗﺩﺭﺘﻪ ﻋﻠﻰ ﺍﻝﺘﻔﺭﻴﻕ ﻭﺍﻝﻔﺼل‬
‫ﺒﺎﺯﺩﻴﺎﺩ ﺜﺎﺒﺕ ﺍﻝﻌﺯل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ‪.‬‬
‫‪εr‬‬ ‫)‪p(D‬‬ ‫ﺍﻝﻤﺫﻴﺏ‬

‫‪2.3‬‬ ‫‪0.00‬‬ ‫ﺍﻝﺒﻨﺯﻥ‬
‫‪2.6‬‬ ‫‪0.00‬‬ ‫ﻜﺒﺭﻴﺕ ﺍﻝﻜﺭﺒﻭﻥ‬
‫‪4.4‬‬ ‫‪1.15‬‬ ‫ﺍﻹﻴﺜﺭ‬
‫‪24.3‬‬ ‫‪1.70‬‬ ‫ﺍﻹﻴﺜﺎﻨﻭل‬
‫‪32.6‬‬ ‫‪1.70‬‬ ‫ﺍﻝﻤﻴﺜﺎﻨﻭل‬
‫‪80.0‬‬ ‫‪1.85‬‬ ‫ﺍﻝﻤﺎﺀ‬
‫‪37.7‬‬ ‫‪2.30‬‬ ‫ﺍﻝﻐﻠﻴﻜﻭل‬
‫‪20.7‬‬ ‫‪2.90‬‬ ‫ﺍﻷﺴﻴﺘﻭﻥ‬
‫ﻥ ﺍﻝﻤﺎﺀ ﻭﺒﻔﻀل ﺍﺭﺘﻔﺎﻉ ﻗﻴﻤﺘﻲ‪ :‬ﻋﺯﻤﻪ ﺍﻝﺜﻨﺎﺌﻲ ﺍﻝﻘﻁﺏ ﻭﺜﺎﺒﺕ‬

‫ﻭﻫﻜﺫﺍ ﻨﺨﻠﺹ ﺇﻝﻰ ﺍﻝﻘﻭل ﺃ ‪‬‬
‫ﻋﺯﻝﻪ ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻴﻜﺘﺴﺏ ﺨﻭﺍﺹ ﺇﻤﺎﻫﺔ ﻭﺘﺸﺭﻴﺩ ﻭﻓﺼل ﻭﺘﺸﺘﻴﺕ‪.‬‬
‫ﻥ ﺁﻝﻴﺎﺕ ﺍﻝﺘﺸﺭﻴﺩ ﻭﺍﻝﺘﻔﺭﻴﻕ ﻭﺍﻝﺘﺸﺘﻴﺕ‬
‫ﻭﻝﻤﺎ ﻜﺎﻨﺕ ﺁﻝﻴﺔ ﺍﻹﻤﺎﻫﺔ ﻨﺎﺸﺭ ﹰﺓ ﻝﻠﺤﺭﺍﺭﺓ ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﺏ ﺸﺎﺭﺩﻱ ﺃﻭ ﺠﺯﻴﺌﻲ ﻓﻲ ﺍﻝﻤﺎﺀ ﻗﺩ ﻴﻜﻭﻥ ﻨﺎﺸﺭ ﹰﺍ ﻝﻠﺤﺭﺍﺭﺓ ﺃﻭ‬
‫ﻥ ﺍﻨﺤﻼل ﻤﺭﻜ ‪‬‬
‫ﻤﺎﺼﺔ ﻝﻠﺤﺭﺍﺭﺓ ‪ ،‬ﻓﺈ ‪‬‬
‫ﻤﺎﺼﹰﺎ ﻝﻠﺤﺭﺍﺭﺓ ﺃﻭ ﻻﺤﺭﺍﺭﻴﹰﺎ ﻭﺫﻝﻙ ﺘﺒﻌﹰﺎ ﻝﻘﻴﻡ ﺍﻷﻨﺘﺎﻝﺒﻴﺔ ﺍﻝﻨﻅﺎﻤﻴﺔ ﻝﻠﺸﺒﻜﺔ ﺍﻝﺒﻠﻭﺭﻴﺔ ﻝﻠﻤﺭﻜﺏ ﺍﻝﺸﺎﺭﺩﻱ‬
‫ﻭﺍﻷﻨﺘﺎﻝﺒﻴﺔ ﺍﻝﻨﻅﺎﻤﻴﺔ ﻹﻤﺎﻫﺔ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻜﻭﻨﺔ ﻝﻪ‪.‬‬
‫‪ .II‬ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺤﻤﺽ – ﺃﺴﺎﺱ‬
‫ﻤﺎ ﺍﻝﺨﺎﺼ‪‬ﺔ ﺍﻝﻤﺸﺘﺭﻜﺔ ﺒﻴﻥ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ‪ ،‬ﻭﺘﺸﻜﹼل ﺍﻝﺼﻭﺍﻋﺩ ﻭﺍﻝﻨﻭﺍﺯل‪ ،‬ﻭﺍﺼﻔﺭﺍﺭ ﻭﺭﻕ‬
‫ﺍﻝﻜﺘﺏ ﺍﻝﻘﺩﻴﻤﺔ‪ ،‬ﻭﻫﻀﻡ ﺍﻝﻁﻌﺎﻡ ﻓﻲ ﺍﻝﻤﻌﺩﺓ ؟ ﺇﻨﻬﺎ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻤﻥ ﺍﻝﻨﻤﻁ ﺤﻤﺽ – ﺃﺴﺎﺱ‪.‬‬
‫ﻜﺜﻴﺭﺓ ﻫﻲ ﺍﻝﺠﻤل ﺍﻝﺘﻲ ﺘﺨﻀﻊ ﻝﺘﻔﺎﻋﻼﺕ ﺤﻤﻀﻴﺔ – ﺃﺴﺎﺴﻴﺔ‪ .‬ﻓﻬﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺘﺅﺩﻱ ﺩﻭﺭﹰﺍ‬
‫ﻓﻲ ﺤﻴﺎﺓ ﻭﻨﻤﻭ ﺍﻝﻜﺜﻴﺭ ﻤﻥ ﺍﻝﻜﺎﺌﻨﺎﺕ ﺍﻝﺤﻴﺔ‪ ،‬ﻭﻜﺫﻝﻙ ﺘﺩﺨل ﻓﻲ ﺍﻝﻌﺩﻴـﺩ ﻤـﻥ ﻤﺭﺍﺤـل ﺍﻝﻌﻤﻠﻴـﺎﺕ‬
‫ﺍﻝﺼﻨﺎﻋﻴﺔ ﻭﺘﺅﺩﻱ ﺩﻭﺭﹰﺍ ﻤﻬﻤﹰﺎ ﻓﻲ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺒﻴﺌﻲ‪.‬‬
‫ﻜﺫﻝﻙ ﹸﺘﺴﺘﻌﻤل ﻫﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻜﺜﻴﺭﹰﺍ ﻓﻲ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ ﻓﻲ ﻓﺼل ﺍﻝﻤﺯﺍﺌﺞ ﻭﺘﻌـﺭ‪‬ﻑ‬
‫ﻥ ﺩﺭﺍﺴﺔ ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﻤﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻤﻬﻡ ﻭﻀﻭﺤﹰﺎ‪.‬‬
‫ﻤﻜﻭ‪‬ﻨﺎﺘﻬﺎ ﻭﻤﻌﺎﻴﺭﺘﻬﺎ‪ .‬ﻝﺫﻝﻙ ﻓﺈ ‪‬‬
‫ﺍﺴﺘﻨﺎﺩ ﹰﺍ ﺇﻝﻰ ﻨﻅﺭﻴﺔ ﺍﻝﻌﺎﻝﻡ ﺍﻝﺩﺍﻨﻤﺭﻜﻲ ﺍﻷﺼل ﺒﺭﻭﻨﺸﺘﺩ ‪، (1879 − 1947) Bronsted‬‬
‫ل ﻨﻭﻉ ﺠﺯﻴﺌﻲ ﺃﻭ ﺸﺎﺭﺩﻱ ﻗﺎﺩﺭ ﻋﻠﻰ ﺘﺤﺭﻴﺭ ﺒﺭﻭﺘﻭﻥ ‪ H+‬ﺃﻭ ﻗﺎﺩﺭ ﻋﻠﻰ ﺠﻌل‬
‫ﻨﺴﻤ‪‬ﻲ ﺤﻤﻀﹰﺎ ﻜ ّ‬
‫ل ﻴﺤﺭ‪‬ﺭ ﺒﺭﻭﺘﻭﻨﹰﺎ‪ .‬ﻭ ﻨﺴﻤ‪‬ﻲ ﺃﺴﺎﺴﹰﺎ ﻜ ّ‬
‫ل ﻨﻭﻉ ﺠﺯ ﻴﺌﻲ ﺃﻭ ﺸﺎﺭﺩ ﻱ ﻗﺎﺩﺭ ﻋﻠﻰ ﺘﺜﺒﻴﺕ ﺒﺭﻭﺘﻭﻥ‬ ‫ﺍﻝﻤﺤ ّ‬
‫‪. H+‬‬
‫ل ﺤﻤﺽ ‪ A‬ﺃﺴﺎﺴﹰﺎ ‪ B‬ﻨﺴﻤﻴﻪ‬
‫ﻭﻝﻤﹼﺎ ﻜﺎﻥ ﻫﺫﺍﻥ ﺍﻝﺘﻌﺭﻴﻔﺎﻥ ﻤﺘﻜﺎﻤﻠﻴﻥ ‪ ،‬ﻓﺈﻨﻨﺎ ﻨﻘﺭﻥ ﺒﻜ ّ‬
‫ﺍﻷﺴﺎﺱ ﺍﻝﻤﺭﺍﻓﻕ ﻭﻨﻜﺘﺏ ‪:‬‬
‫‪+‬‬
‫‪A B +H‬‬
‫ﺘﺒﻴ‪‬ﻥ ﺍﻝﻜﺘﺎﺒﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺇﻤﻜﺎﻥ ﺍﻻﻨﺘﻘﺎل ﻓﻲ ﺍﻻﺘﺠﺎﻫﻴﻥ ‪ :‬ﻤﻥ ‪ A‬ﺇﻝﻰ ‪ B‬ﻋﻥ ﻁﺭﻴﻕ ﺘﺤﺭﻴﺭ‬
‫ﻥ ﺍﻝﺤﻤﺽ ‪ A‬ﻭﺍﻷﺴﺎﺱ ‪B‬‬
‫ﺒﺭﻭﺘﻭﻥ‪ ،‬ﻭﻤﻥ ‪ B‬ﺇﻝﻰ ‪ A‬ﻋﻥ ﻁﺭﻴﻕ ﺘﺜﺒﻴﺕ ﺒﺭﻭﺘﻭﻥ‪ .‬ﻭﻨﻘﻭل ﺒﺄ ‪‬‬
‫ﺝ ) ﺤﻤﺽ‪ /‬ﺃﺴﺎﺱ( ﻭ ﻨﺭﻤﺯ ﺇﻝﻰ ﻫﺫﺍ‬

‫ﺍﻝﻤﻘﺭﻭﻥ ﺒﻪ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﺴﺎﺒﻘﺔ ﻤﺘﺭﺍﻓﻘﺎ ﻥ ﻭﻴﺸﻜﹼﻼﻥ ﺯﻭ ‪‬‬
‫ﺍﻝﺯﻭﺝ ﺒﺎﻝﺭﻤﺯ ‪. A / B :‬‬
‫ﻥ ﺍﻝﺒﺭﻭﺘﻭﻥ ‪ H+‬ﻻ ﻴﻜﻭﻥ ﺤﺭﹰﺍ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﺇﻨﻤﺎ ﻴﺘﺜﺒ‪‬ﺕ ﻋﻠﻰ‬
‫ﻭﻻ ﺒ ‪‬ﺩ ﻤﻥ ﺍﻝﺘﺫﻜﻴﺭ ﻫﻨﺎ ﺒﺄ ‪‬‬
‫ﺠﺯﻱ ﺀ ﻤﺎﺀ ﻝﻴﻜ ‪‬ﻭ ﻥ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ H3O+‬ﺃﻭ ﻤﺎ ﻴ‪‬ﻌﺭ‪‬ﻑ ﺃﻴﻀﹰﺎ ﺒﺎﺴﻡ ﺸﺎﺭﺩﺓ ﺍ ُﻷ ﻜﺴﻭﻨﻴﻭﻡ‬
‫ﻜﻤﺎ ﻴﻭﺼﻲ ﺒﺫﻝﻙ ﺍﻻﺘﺤﺎﺩ ﺍﻝﺩﻭﻝﻲ ﻝﻠﻜﻴﻤﻴﺎﺀ ﺍﻝﺒﺤﺘﺔ ﻭﺍﻝﺘﻁﺒﻴﻘﻴﺔ ‪.IUPAC‬‬
‫ﻨﻌﺭﺽ ﻓﻴﻤﺎ ﻴﻠﻲ ﺃﻤﺜﻠﺔ ﻋﻥ ﺃﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‪:‬‬
‫ ﺤﻤﺽ ﺍﻝﻨﺘﺭﻴﺕ ‪/‬ﺸﺎﺭﺩﺓ ﺍﻝﻨﺘﺭﻴﺕ ‪:‬‬
‫‪HNO2 H + NO−‬‬ ‫‪2‬‬
‫‪+‬‬
‫ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ ‪/‬ﺍﻝﻨﺸﺎﺩﺭ ‪:‬‬

‫‪NH+‬‬
‫‪4‬‬
‫‪+‬‬
‫‪ H + NH3‬‬
‫ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ‪/‬ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺤﺎﻤﻀﻴﺔ )ﺍﻝﺒﻴﻜﺭﺒﻭﻨﺎﺕ( ‪:‬‬
‫‪CO2 + H2O H+ + HCO−‬‬
‫‪3‬‬
‫ل ﺒﺭﻭﺘﻭﻨﹰﺎ‪.‬‬
‫ﺤّ‬‫ﺤﻴﺙ ﻴ‪‬ﺤﺭ‪‬ﺭ‪ ،‬ﻓﻲ ﻫﺫﺍ ﺍﻝﻤﺜﺎل‪ ،‬ﺍﻝ ‪‬ﻤ ‪‬‬
‫ ﻏﺎﺯ ﺜﺎﻨﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺒﺭﻴﺕ ‪/‬ﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﻴﺕ ﺍﻝﺤﺎﻤﻀﻴﺔ )ﺍﻝﺒﻴﺴﻠﻔﻴﺕ( ‪:‬‬
‫‪SO2 + H2O H+ + HSO−‬‬
‫‪3‬‬
‫ل ﺒﺭﻭﺘﻭﻨﹰﺎ‪.‬‬
‫ﻭﻓﻲ ﻫﺫﺍ ﺍﻝﻤﺜﺎل ﺃﻴﻀﹰﺎ‪ ،‬ﻴﺤﺭ‪‬ﺭ ﺍﻝﻤ‪‬ﺤ ّ‬
‫ ﺘﺅ ﺩ‪‬ﻱ ﺃﻴﻀﹰﺎ ﺒﻌﺽ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﻤﺜل ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ )‪ ) Fe2+ (II‬ﺃﻭ ﺒﺘﺤﺩﻴﺩ‬
‫ﺃﺩﻕ ‪ ( [ Fe(H2O)6 ]2 +‬ﺩﻭﺭ ﺤﻤﻭ ﹴ‬
‫ﺽ‪:‬‬
‫‪[ Fe(H2O)6 ]2 + ⇌ H+ + [ Fe(OH)(H2O)5 ]+‬‬
‫ﻭﻫﻭ ﻤﺎ ﻴ‪‬ﻜﺘﺏ ﻋﻠﻰ ﻨﺤﻭ ﺃﺒﺴﻁ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪Fe2+ + H2O ⇌ H+ + Fe(OH)+‬‬
‫ل ﺤﻤﺽ ﻗﺎﺩﺭ ﻋﻠﻰ ﺘﺤﺭﻴﺭ ﺃﻜﺜﺭ ﻤﻥ ﺒﺭﻭﺘﻭﻥ‪ ،‬ﻜﻤﺎ ﻓﻲ‬

‫ ﻨﺴﻤ‪‬ﻲ ﺤﻤﻀﹰﺎ ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﻭﻅﻴﻔﺔ ﻜ ّ‬
‫ﺤﺎﻝﺔ ‪. Cr2 O27−, H3 PO4 , H2 SO4 :‬‬
‫ﻼ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ﺸﺎﺭﺩﺓ ﺍﻝﺒﻴﻜﺭﻭﻤﺎﺕ‪/‬ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﻭﻤﺎﺕ ‪:‬‬
‫ﻓﻨﻜﺘﺏ ﻤﺜ ﹰ‬
‫‪Cr2O27− + H2O 2 H+ +2 CrO24−‬‬

‫ ﻭﻨﺴﻤ‪‬ﻲ ﺃﺴﺎﺴﹰﺎ ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﻭﻅﻴﻔﺔ ﻜلّ ﺃﺴﺎﺱ ﻗﺎﺩﺭ ﻋﻠﻰ ﺘﺜﺒﻴﺕ ﺃﻜﺜﺭ ﻤﻥ ﺒﺭﻭﺘﻭﻥ‪ ،‬ﻜﻤﺎ ﻓﻲ‬
‫ﺤﺎﻝﺔ ‪ CO23− :‬ﻭﺍﻹﻴﺜﻠﻴﻥ ﺜﻨﺎﺌﻲ ﺍﻷﻤﻴﻥ ‪. H2 N− CH2 − CH2 − NH2‬‬
‫ل ﺠﺯﻱﺀ ﺃﻭ ﺸﺎﺭﺩﺓ ﺘﺅ ﺩ‪‬ﻱ ﺩﻭﺭ‬
‫ ﻭﻨﺴﻤ‪‬ﻲ ﻤﺘﺫﺒﺫﺒﹰﺎ ﺤﻤﻀﻴﹰﺎ‪ -‬ﺃﺴﺎﺴﻴﹰﺎ ‪ ampholyte‬ﻜ ﱠ‬
‫ﺝ ﺁﺨﺭ ﻜﻤﺎ ﻓﻲ ﺍﻝﻤﺜﺎل ﺍﻝﺘﺎﻝﻲ ‪:‬‬
‫ﺱ ﻓﻲ ﺯﻭ ﹴ‬
‫ﺽ ﻓﻲ ﺯﻭﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻭﺩﻭﺭ ﺃﺴﺎ ﹴ‬
‫ﺤﻤ ﹴ‬
‫‪HSO−‬‬ ‫‪2−‬‬
‫‪4 / SO4‬‬
‫‪H2 SO4/ HSO−‬‬

‫‪4‬‬
‫ﺤﻴﺙ ﺘﺅﺩﻱ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺎﻤﻀﻴﺔ ﺩﻭﺭ ﺤﻤﺽ ﻓﻲ ﺍﻝﺯﻭﺝ ﺍﻷﻭل ﻭﺩﻭﺭ ﺃﺴﺎﺱ ﻓﻲ ﺍﻝﺯﻭﺝ‬
‫ﺍﻝﺜﺎﻨﻲ‪.‬‬
‫‪ pH .2.II‬ﻤﺤﻠﻭل‬
‫ﻨﻌﺭ‪‬ﻑ ‪ pH‬ﻤﺤﻠﻭل ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬

‫‪+‬‬
‫‪ [ H O ] ‬‬
‫‪pH = − log  3‬‬ ‫‪‬‬
‫‪ C 0 ‬‬
‫ﺤﻴﺙ ] ‪ [ H3O+‬ﻫﻭ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻤﻘﺩﺭ ﹰﺍ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪ mol/L‬ﻭ ‪C 0‬‬
‫ﻫﻭ ﺘﺭﻜﻴﺯ ﻤﺭﺠﻌﻲ ﻴﺴﺎﻭﻱ ‪ .C 0 = 1.00 mol/L‬ﻭﻜﺜﻴﺭﹰﺍ ﻤﺎ ﻨﻜﺘﺏ ﺘﺠﺎﻭﺯﹰﺍ ﺍﻝﺘﻌﺭﻴﻑ ﺍﻝﺴﺎﺒﻕ‬
‫ﺒﺎﻝﺼﻴﻐﺔ ] ‪ pH = − log [ H3 O+‬ﻋﻠﻰ ﺃﻥ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‬
‫ﻤﻘﺩﺭﹰﺍ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪. mol/L‬‬
‫‪ .3.II‬ﺍﻝﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ‬
‫ﻻ‬
‫ﻥ ﺤﻤﻀﹰﺎ ﻤﺎ ﻻ ﻴ‪‬ﻘ ‪‬ﺩ ﻡ ﺒﺭﻭﺘﻭﻨﻪ ﺇ ﹼ‬
‫ﻻ ﺘﻜﻭﻥ ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ ﺤﺭ‪‬ﺓ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﻝﺫﺍ ﻓﺈ ‪‬‬
‫ﺇﺫﺍ ﻭ ﺠﺩ ﺍﻷﺴﺎﺱ ﺍﻝﻘﺎﺩﺭ ﻋﻠﻰ ﺘﺜﺒﻴﺘﻪ‪ .‬ﻭﻤﻥ ﻫﻨﺎ ﻨﹸﻌﺭ‪‬ﻑ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﻤﻀﻴﺔ‪ -‬ﺍﻷﺴﺎﺴﻴﺔ ﺒﺄﻨﻬﺎ‬
‫ﺘﻔﺎﻋﻼﺕ ﺘﺒﺎﺩل ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ‪ .‬ﻓﻨﻜﺘﺏ ﻤﺜ ﹰ‬
‫ﻼ ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ‪ A1‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪ A1 / B1‬ﻤﻊ ﺍﻷﺴﺎﺱ‬
‫‪ B2‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪ A2 / B2‬ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬
‫‪A1 + B2 ⇌ A2 + B1‬‬
‫ﻨﺴﻤ‪‬ﻲ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻭﻨﻼﺤﻅ ﻋﺩﻡ ﻅﻬﻭﺭ ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ ﻓﻴﻪ‪ .‬ﻭﻤﺎ ﻫﺫﺍ‬
‫ﻻ ﺤﺼﻴﻠﺔ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ‪:‬‬
‫ﺍﻝﺘﻔﺎﻋل ﻓﻲ ﺍﻝﺤﻘﻴﻘﺔ ﺇ ﹼ‬
‫‪+‬‬
‫‪A1 ⇌ H + B1‬‬
‫‪B2 + H+ ⇌ A2‬‬
‫ﻭﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺘﺭﺍﻜﻴﺯ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻤﻤﺩﺩﺓ ﻜﺜﻴﺭﹰﺍ‬
‫ﻭﺘﺤﻘﹼﻕ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫] ‪[ A2 ][ B1‬‬
‫= ‪K‬‬
‫] ‪[ A1 ][ B2‬‬
‫ﻥ ﻜﻴﻤﻴﺎﺌﻲ ﺒﻴﻥ ﻫﺫﻩ ﺍﻷﻨﻭﺍﻉ ﺍﻷﺭﺒﻌﺔ‪.‬‬
‫ﻓﻬﺫﺍ ﻴﻌﻨﻲ ﻭﺠﻭﺩ ﺘﻭﺍﺯ ﹴ‬
‫ﻝﺘﺤﺩﻴﺩ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ‪ K‬ﻭﺍﻝﺘﻨﺒ‪‬ﺅ ﺒﻤﻨﺤﻰ ﺘﺤﻭ‪‬ل ﺍﻝﺠﻤﻠﺔ ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻴﺔ ﺍﻝﺴﺎﺒﻘﺔ‪ ،‬ﻻ ﺒ ‪‬ﺩ‬
‫ﻤﻥ ﺘﺼﻨﻴﻑ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻭﻓﻘﹰﺎ ﻝﻘﻭﺘﻬﺎ‪ ،‬ﻭﻨﻘﺼﺩ ﺒﻘﻭﺘﻬﺎ ﻗﺩﺭﺘﻬﺎ ﻋﻠﻰ ﺘﺒﺎﺩل ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ‪.‬‬
‫ﻭﻝﻤ‪‬ﺎ ﻜﺎﻨﺕ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺴﺎﺒﻘﺔ ﺘﺠﺭﻱ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﻓﺈﻨﻪ ﻴﻨﺒﻐﻲ ﺇﺠﺭﺍﺀ ﻫﺫﺍ ﺍﻝﺘﺼﻨﻴﻑ‬
‫ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ﺃﺯﻭﺍﺝ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .4.II‬ﺍﻝﺯﻭﺠﺎﻥ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﺨﺎﺼﺎﻥ ﺒﺎﻝﻤﺎﺀ‬
‫ﻴ‪‬ﻌﺘﺒﺭ ﺍﻝﻤﺎﺀ ﻤﺘﺫﺒﺫﺒﹰﺎ ﺤﻤﻀﻴﹰﺎ‪-‬ﺃﺴﺎﺴﻴﹰﺎ‪ ،‬ﺤﻴﺙ ﻴﺅﺩﻱ ﺩﻭﺭ ﺃﺴﺎﺱ ﻤﺭﺍﻓﻕ ﻝﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ‬
‫ﻓﻲ ﺍﻝﺯﻭﺝ ‪ ، H3O+/ H2O‬ﻭ ﻴﺅﺩﻱ ﺩﻭﺭ ﺤﻤﺽ ﻤﺭﺍﻓﻕ ﻝﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻓﻲ ﺍﻝﺯﻭﺝ‬
‫‪ H2O / OH−‬ﻭﺫﻝﻙ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ‪:‬‬
‫‪H3O+‬‬ ‫⇌‬ ‫‪H2O + H+‬‬
‫⇌ ‪H2O‬‬ ‫‪OH− + H+‬‬
‫ﻭﻋﻠﻴﻪ ﻨﺭﻯ ﺃﻨﹼﻪ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﺘﻜﻭﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻭﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻓﻲ ﺘﻭﺍﺯﻥ ﻤﻊ‬
‫ﺍﻝﻤﺎﺀ ﻭﻨﻜﺘﺏ ‪:‬‬
‫‪+‬‬ ‫‪−‬‬
‫‪2 H2O‬‬ ‫⇌‬ ‫‪H3O + OH‬‬
‫ﻨﺴﻤﻲ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﺒﺎﻝﺘﺤﹼﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ﻷﻨﻪ ﻴﻌﺒ‪‬ﺭ ﻋﻥ ﺍﻨﺘﻘﺎل ﺍﻝﺒﺭﻭﺘﻭﻥ ﺒﻴﻥ ﺠﺯﻱﺀ‬
‫ﻤﺎﺀ ﻭﺠﺯﻱﺀ ﻤﺎﺀ ﺁﺨﺭ ﻭﻫﻭ ﻁﺒﻌﹰﺎ ﺘﻔﺎﻋلٌ ﻤﻥ ﺍﻝﻨﻤﻁ ﺤﻤﺽ ‪ -‬ﺃﺴﺎﺱ ﺒﻴﻥ ﺠﺯﻴﺌﻲ ﻤﺎﺀ ﻴﺅﺩﻱ ﻓﻴﻪ‬
‫ﻥ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﻨﺎﺠﻡ ﻋﻥ ﺘﻔﺎﻋل‬
‫ﺃ ﺤﺩﻫﻤﺎ ﺩﻭﺭ ﺍﻝﺤﻤﺽ ﻭﻴﺅﺩﻱ ﺍﻵ ﺨﺭ ﺩﻭﺭ ﺍﻷﺴﺎﺱ‪ .‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﺯﻭﺠﻴﻥ ‪ H3O+/ H2O‬ﻭ ‪ H2O / OH−‬ﻭﻴﺘﻤﻴ‪‬ﺯ ﺒﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫] ‪[H3O+ ] [OH−‬‬
‫‪Kw‬‬ ‫=‬ ‫×‬
‫‪C0‬‬ ‫‪C0‬‬
‫ﺃﻭ ﻋﻠﻰ ﻨﺤ ﹴﻭ ﺃﺒﺴﻁ ﺇﺫﺍ ﻋﺒ‪‬ﺭﻨﺎ ﻋﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪: mol ⋅ L−1‬‬
‫] ‪K w = [H3O+ ] × [OH−‬‬
‫ﻻ ﺒﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ‪ ،‬ﻭﺘﻜﻭﻥ ﻗﻴﻤﺘﻪ‬

‫ﻨﺴﻤﻲ ﻫﺫﺍ ﺍﻝﺜﺎﺒﺕ ﺒﺎﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ ﻭﻫﻭ ﺜﺎﺒﺕﹲ ﻻ ﻴﺘﻌﻠﹼﻕ ﺇ ﹼ‬
‫ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻤﺴﺎﻭﻴﺔ ‪. K w = 10−14‬‬
‫ﻨﹸﻌﺭ‪‬ﻑ ﺃﻴﻀﹰﺎ ‪ pK w‬ﺒﺎﻝﻌﻼﻗﺔ ‪ ، pK w = − log K w :‬ﻭﻫﻜﺫﺍ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍ ﻝﺤﺭﺍﺭﺓ ‪25 C‬‬
‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫‪pK w = 14.0‬‬
‫ﻴ‪‬ﻅﻬﺭ ﺍﻝﺠﺩﻭل ﺍﻝﺘﺎﻝﻲ ﺘﻐﻴﺭﺍﺕ ﺜﺎﺒﺕ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ ﻤﻊ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪:‬‬
‫‪pK w‬‬ ‫‪Kw‬‬ ‫ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ) ‪( C‬‬

‫‪14.96‬‬ ‫‪0.11 × 10−14‬‬ ‫‪0‬‬
‫‪14.00‬‬ ‫‪1.00 × 10−14‬‬ ‫‪25‬‬
‫‪12.26‬‬ ‫‪55.00 × 10−14‬‬ ‫‪100‬‬
‫ﻥ ﻗﻴﻤﺔ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ‪ K w‬ﺘﺯﺩﺍﺩ ﻤﻊ ﺍﺭﺘﻔﺎﻉ ﺩﺭﺠﺎﺕ ﺍﻝﺤﺭﺍﺭﺓ‪ .‬ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ‪ ،‬ﺇﺫﺍ‬
‫ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ﻋﺒﺎﺭﺓ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ ﺘﺴﻤﺢ ﺒﻜﺘﺎﺒﺔ ‪:‬‬
‫ﻜﺘﺒﻨﺎ ] ‪ pX = − log[X‬ﻓﺈ ‪‬‬
‫‪pK w = pH + pOH‬‬
‫‪ .5.II‬ﺘﻔﺎﻋل ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ ﻤﻊ ﺍﻝﻤﺎﺀ‬
‫ﻋﻨﺩﻤﺎ ﻨﻀﻊ ﺤﻤﻀﹰﺎ ‪ H A‬ﺃﻭ ﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ ‪ A−‬ﻓﻲ ﺍﻝﻤﺎﺀ ‪ ،‬ﻓﺈﻨﻨﺎ ﻨﻭﺍﺠﻪ ﺇﺤﺩﻯ ﺍﻝﺤﺎﻻﺕ‬
‫ﺍﻝﺜﻼﺙ ﺍﻵﺘﻴﺔ ‪:‬‬
‫ﻤﺜﺎل‬ ‫ﻗﻭﺓ ﺍﻝﺤﻤﺽ ﺃﻭ ﺍﻷﺴﺎﺱ‬ ‫ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ﺃﻭ ﺍﻷﺴﺎﺱ ﻤﻊ‬

‫ﺍﻝﻤﺎﺀ‬
‫‪C2 H5 OH‬‬ ‫ﺤﻤﺽ ﺸﺎﻫﺩ‪ ،‬ﻏﻴﺭ ﻗﺎﺒل ﻝﻠﺘﻤﻴﻴﺯ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬ ‫‬ ‫ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬ ‫ﻻ ﻴﺘﻔﺎﻋل ‪H A‬‬ ‫‬
‫‪C2 H5 O−‬‬ ‫ ﺃﺴﺎﺱ ﻗﻭﻱ‪.‬‬ ‫ﺒﺸﺩﺓ ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬ ‫ﻴﺘﻔﺎﻋل ‪A−‬‬ ‫‬
‫‪H Cl‬‬ ‫ ﺤﻤﺽ ﻗﻭﻱ‪.‬‬ ‫ﻴﺘﻔﺎﻋل ‪ H A‬ﺒﺸﺩﺓ ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬ ‫‬
‫‪Cl−‬‬ ‫ ﺃﺴﺎﺱ ﺸﺎﻫﺩ‪ ،‬ﻏﻴﺭ ﻗﺎﺒل ﻝﻠﺘﻤﻴﻴﺯ ﻓﻲ ﺍﻝﻤﺎﺀ‬ ‫ﻻ ﻴﺘﻔﺎﻋل ‪ A−‬ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬ ‫‬
‫‪CH3 COOH / CH3 COO−‬‬ ‫ﻫﻤﺎ ﺤﻤﺽ ﻭﺃﺴﺎﺱ‬ ‫‪ H A‬ﻭ ‪A−‬‬ ‫‬ ‫ﻴﺘﻔﺎﻋل ‪ H A‬ﻭ ‪ A−‬ﻤﻊ ﺍﻝﻤﺎﺀ‬ ‫‬
‫ﻀﻌﻴﻔﺎﻥ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬ ‫ﺒﺼﻭﺭﺓ ﻤﺤﺩﻭﺩﺓ‪.‬‬
‫ﻨﺴﺘﻌﻴﻥ ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻷﺨﻴﺭﺓ ﻝﺘﻭﺼﻴﻑ ﺘﻔﺎﻋل ‪ H A‬ﺃﻭ ‪ A−‬ﻤﻊ ﺍﻝﻤﺎﺀ ﺒﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺫﻱ ﻴﺴﻤﻰ‬
‫ﻫﻨﺎ ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‪.‬‬
‫

‬
‫)‪(Chem Matters, oct. 2009, p5‬‬ ‫ﺍﺯﺩﻴﺎﺩ ﺤﻤﻭﻀﺔ ﺍﻝﻤﺤﻴﻁﺎﺕ‬
‫ﺘﺘﺴﺒﺏ ﺍﻝﺯﻴﺎﺩﺓ ﺍﻝﻜﺒﻴﺭﺓ ﻓﻲ ﻜﻤﻴﺔ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻭﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﻓﻲ ﺍﻝﻐﻼﻑ ﺍﻝﺠﻭﻱ ﻓﻲ ﺠﻌل ﻤﻴﺎﻩ ﺍﻝﻤﺤﻴﻁﺎﺕ ﺃﻜﺜﺭ‬
‫ﻓﺄﻜﺜﺭ ﺤﺎﻤﻀﻴﺔ ‪ .‬ﻓﻤﻨﺫ ﺒﺩﺍﻴﺔ ﺍﻝﺜﻭﺭﺓ ﺍﻝﺼﻨﺎﻋﻴﺔ ﺍﺯﺩﺍﺩ ﺍﺴﺘﻌﻤﺎل ﺍﻝﻭﻗﻭﺩ ﺍﻷﺤﻔﻭﺭﻱ ﻭﺍﻝﻐﺎﺯ ﺍﻝﻁﺒﻴﻌﻲ ﻭﺍﻝﻔﺤﻡ ﻭﻫﺫﺍ ﻤﺎ‬
‫ﺃﺩﻯ ﺇﻝﻰ ﻤﻀﺎﻋﻔﺔ ﻤﺴﺘﻭﻴﺎﺕ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻭﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﻓﻲ ﺍﻝﻐﻼﻑ ﺍﻝﺠﻭﻱ‪.‬‬
‫ﺘﻤﺘﺹ ﺍﻝﻤﺤﻴﻁﺎﺕ ﻜﻤﻴﺎﺕ ﻜﺒﻴﺭﺓ ﻤﻥ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻭﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺘﺼل ﺇﻝﻰ ﻗﺭﺍﺒﺔ ‪ 22‬ﻤﻠﻴﻭﻥ ﻁﻥ ﻴﻭﻤﻴﹰﺎ‪ ،‬ﻭﻫﺫﺍ‬
‫ﻴﺘﺴﺒﺏ ﻓﻲ ﺭﻓﻊ ﺤﻤﻭﻀﺔ ﻤﺎﺀ ﺍﻝﻤﺤﻴﻁﺎﺕ‪.‬‬
‫‪H2O + CO2 ⇌ H + HCO−‬‬
‫‪3‬‬
‫‪+‬‬
‫ﻴﻘﻴﺱ ﺍﻝﻌﻠﻤﺎﺀ ﺤﻤﻭﻀﺔ ﺍﻝﻤﺤﻴﻁﺎﺕ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺴﻠﱡﻡ ﺍﻝـ ‪ pH‬ﺍﻝﺫﻱ ﻴﺄﺨﺫ ﻗﻴﻤﻪ ﺒﻴﻥ ‪ 0‬ﻭ ‪. 14‬‬
‫ﻥ ﻗﻴﻤﺔ‬
‫ﺘﺼل ﺍﻵﻥ ﻗﻴﻤﺔ ‪ pH‬ﺴﻁﺢ ﺍﻝﻤﺤﻴﻁﺎﺕ ﺇﻝﻰ ‪ 8.1‬ﻭﻗﺩ ﻜﺎﻨﺕ ‪ 8.2‬ﻓﻲ ﺍﻝﻘﺭﻥ ﺍﻝﺜﺎﻤﻥ ﻋﺸﺭ‪ .‬ﻭﻴﻌﺘﻘﺩ ﺍﻝﻌﻠﻤﺎﺀ ﺃ ‪‬‬
‫‪ pH‬ﺍﻝﻤﺤﻴﻁﺎﺕ ﺴﺘﻬﺒﻁ ﺇﻝﻰ ‪ 7.8‬ﺨﻼل ﺍﻝﺨﻤﺴﻴﻥ ﺇﻝﻰ ﺍﻝﻤﺌﺔ ﻋﺎﻡ ﺍﻝﻘﺎﺩﻤﺔ‪.‬‬
‫ﻭﻴﻌﺘﻘﺩ ﺍﻝﺒﺎﺤﺜﻭﻥ ﻓﻲ ﺍﻝﻌﺎﻝﻡ ﺃﺠﻤﻊ ﺃﻥ ﻗﻴﻤﹰﺎ ﻤﻨﺨﻔﻀﺔ ﻜﻬﺫﻩ ﻝـ ‪ pH‬ﺴﻁﺢ ﺍﻝﻤﺤﻴﻁﺎﺕ ﻤﻥ ﺸﺄﻨﻬﺎ ﺃﻥ ﺘﺅﺜﺭ ﻓﻲ ﺘﻁﻭﺭ‬
‫ﻭﺘﻜﺎﺜﺭ ﺍﻝﻜﺎﺌﻨﺎﺕ ﺍﻝﺤﻴﺔ ﺍﻝﺒﺤﺭﻴﺔ ﺍﻝﺘﻲ ﺘﻌﻴﺵ ﻋﻠﻰ ﺴﻁﺢ ﺍﻝﻤﺎﺀ ﺃﻭ ﺍﻝﺘﻲ ﺘﻌﻴﺵ ﻓﻲ ﺍﻝﻤﻴﺎﻩ ﺍﻝﻀﺤﻠﺔ‪ .‬ﻭﻨﺫﻜﺭ ﻤﻥ ﻫﺫﻩ‬
‫ﺍﻝﻜﺎﺌﻨﺎﺕ ﻗﻨﺎﺩﻴل ﺍﻝﺒﺤﺭ‪ ،‬ﺍﻝﺒﻼﻨﻜﺘﻭﻥ‪ ،‬ﺍﻝﻤﺭﺠﺎﻥ ‪...‬‬
‫ﻼ ﻜﻠﺴﻴﹰﺎ ﻗﺎﺴﻴﹰﺎ ﺤﻭل‬
‫ﻓﻌﻠﻰ ﺴﺒﻴل ﺍﻝﻤﺜﺎل ﻴﻔﺭﺯ ﺍﻝﻤﺭﺠﺎﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ CaCO3‬ﻭﻫﻲ ﻤﺎﺩﺓ ﻜﻴﻤﻴﺎﺌﻴﺔ ﺘﺸﻜﹼل ﻫﻴﻜ ﹰ‬
‫ﺍﻝﻤﺭﺠﺎﻥ ﻭﺒﺎﺭﺘﻔﺎﻉ ﻤﻨﺴﻭﺏ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻭﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﻓﺈﻥ ﻫﺫﻩ ﺍﻝﻬﻴﺎﻜل ﻤﻥ ﺸﺄﻨﻬﺎ ﺃﻥ ﺘﺫﻭﺏ ﻭﻓﻕ ﺍﻵﻝﻴﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪H+ +CaCO3 ⇌ Ca2+ +HCO−‬‬
‫‪3‬‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ‪ ،‬ﻴﺅﺜﹼﺭ ﺍﻨﺨﻔﺎﺽ ﻗﻴﻡ ‪ pH‬ﻤﻴﺎﻩ ﺍﻝﻤﺤﻴﻁﺎﺕ ﻋﻠﻰ ﺴﺭﻋﺔ ﺍﻨﺘﺸﺎﺭ ﺍﻝﺼﻭﺕ ﻓﻴﻬﺎ‪ ،‬ﻭﻻ ﻴﺨﻔﻰ ﻋﻠﻰ ﺃﺤﺩ ﺃﺜﺭ‬
‫ﺍﻨﺘﺸﺎﺭ ﺍﻝﺼﻭﺕ ﻓﻲ ﺍﻝﻤﺤﻴﻁﺎﺕ ﻋﻠﻰ ﺘﻭﺍﺼل ﺒﻌﺽ ﺍﻝﺜﺩﻴﻴﺎﺕ ﺍﻝﺒﺤﺭﻴﺔ ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ‪.‬‬
‫ﺹ ﻓﻲ ﻤﺠﺎل ﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﻴﻁﺎﺕ ﻓﻲ ﻤﻌﻬﺩ ﺒﺤﻭﺙ ‪Monterey Bay‬‬
‫ﻓﻘﺩ ﻭﺠﺩ ﺍﻝﻌﺎﻝﻡ ‪ Peter Brewer‬ﻭﻫﻭ ﻤﺨﺘ ‪‬‬
‫‪ Aquarium‬ﻓﻲ ﻜﺎﻝﻴﻔﻭﺭﻨﻴﺎ ﺃﻨﻪ ﻜﻠﻤﺎ ﺍﺭﺘﻔﻌﺕ ﺤﻤﻭﻀﺔ ﻤﻴﺎﻩ ﺍﻝﻤﺤﻴﻁﺎﺕ ﺍﻨﺘﺸﺭ ﺍﻝﺼﻭﺕ ﺒﺴﺭﻋﺔ ﺃﻜﺒﺭ‪.‬‬
‫ﻴﻨﺘﺸﺭ ﺍﻝﺼﻭﺕ ﺤﺎﻝﻴ ﹰﺎ ﻓﻲ ﺍﻝﻤﺤﻴﻁﺎﺕ ﺒﺴﺭﻋﺔ ﺘﺯﻴﺩ ﻋﻤﺎ ﻜﺎﻨﺕ ﻋﻠﻴﻪ ﻗﺒل ﻨﺤﻭ ﻤﺌﺔ ﻋﺎﻡ ﺒﺤﺩﻭﺩ ‪ ، 10%‬ﻭﻤﻥ ﺍﻝﻤﻔﺘﺭﺽ‬
‫ﺃﻥ ﺘﺼل ﺍﻝﺯﻴﺎﺩﺓ ﻓﻲ ﺍﻝﺴﺭﻋﺔ ﺇﻝﻰ ‪ , 70%‬ﻭﻫﺫﺍ ﻤﺎ ﺴﻴﺴﻬل ﻋﻠﻰ ﺍﻷﺤﻴﺎﺀ ﺍﻝﺒﺤﺭﻴﺔ ﻋﻤﻠﻴﺔ ﺍﻝﺒﺤﺙ ﻋﻥ ﺍﻝﻁﻌﺎﻡ ﻭﺇﻴﺠﺎﺩ‬
‫ﺍﻝﺸﺭﻴﻙ‪ ،‬ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺃﻨﻬﺎ ﺴﺘﺴﻤﻊ ﺒﺼﻭﺭﺓ ﺃﻓﻀل ﺼﻭﺕ ﺍﻝﻘﻭﺍﺭﺏ ﻭﺍﻝﺴﻔﻥ ﺍﻝﻘﺎﺩﻤﺔ ﻤﻥ ﺒﻌﻴﺩ‪.‬‬
‫‪ .6.II‬ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‬
‫‪ .1.6.II‬ﺍﻝﺯﻭﺝ ‪HA /A−‬‬
‫ ﻝﻭ ﻭﻀﻌﻨﺎ ﺍﻝﺤﻤﺽ ‪ H A‬ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻝﺘﻔﺎﻋل ﻤﻌﻪ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪H A + H2 O ⇌ A− + H3 O+‬‬
‫ﺠﺭﻯ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﻤﻀﻲ‪-‬ﺍﻷﺴﺎﺴﻲ ﺒﻴﻥ ﺍﻝﺤﻤﺽ ‪ H A‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪ H A / A−‬ﻭﺍﻷﺴﺎﺱ‬
‫‪ H2 O‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪ H3 O+/ H2 O‬ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﺸﻜﻠﻴ‪‬ﺘﻴﻥ ‪:‬‬
‫‪H A ⇌ A− + H+‬‬
‫‪H+ + H2O ⇌ H3 O+‬‬
‫ﻥ ﺘﺭﺍﻜﻴﺯ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﻭﺍﺭﺩﺓ ﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ‬
‫ﻭﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻤﻤﺩﺩ ﹰﺍ ﺘﻤﺩﻴﺩ ﹰﺍ ﻜﺎﻓﻴﹰﺎ ‪ ،‬ﻓﺈ ‪‬‬
‫ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﺒﺎﺴﺘﺜﻨﺎﺀ ﺍﻝﻤﺎﺀ‪ ،‬ﺘﺤﻘﹼﻕ ﺸﺭﻁ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺫﻱ ﺜﺎﺒﺘﻪ ﻫﻭ ‪:‬‬
‫) ‪([H 3O+ ]/C 0 )([A− ]/C 0‬‬

‫= ‪KA‬‬
‫) ‪([H A]/C 0‬‬
‫ﺤﻴﺙ ﻴﻤﺜﹼل ‪ C 0‬ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﻤﺭﺠﻌﻲ ‪. 1.00 mol/L‬‬
‫ﻨﻌﺒ‪‬ﺭ ﻋﻥ ﻫﺫﺍ ﺍﻝﺜﺎﺒﺕ ﺒﺼﻴﻐﺔ ﺃﺒﺴﻁ ﻓﻨﻜﺘﺏ ‪:‬‬
‫] ‪[H 3O+ ] ⋅ [A−‬‬
‫= ‪KA‬‬
‫]‪[H A‬‬
‫ﻭﻝﻤﹼﺎ ﻜﺎﻥ ‪ K w‬ﻭ ‪ K A‬ﻤﻘﺩﺍﺭﻴﻥ ﻻ ﻭﺍﺤﺩﺓ ﻝﻬﻤﺎ‪ ،‬ﻓﺈﻨﻪ ﻴﺠﺭﻱ ﺍﺴﺘﻌﻤﺎﻝﻬﻤﺎ ﺒﺼﻴﻐﺘﻴﻬﻤﺎ ﺍﻝﻤﺒﺴﻁﺘﻴﻥ‬
‫ﺸﺭﻁ ﺍﻝﺘﻌﺒﻴﺭ ﻋﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪ . mol/L‬ﻭﻨﻜﺘﺏ ﺒﺎﻝﺘﻌﺭﻴﻑ‪:‬‬
‫‪pK A = − log K A‬‬
‫ﻴﺴﻤ‪‬ﻰ ‪ K A‬ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‪ ،‬ﻭﻫﻭ ﺜﺎﺒﺕ ﻻ ﻴﺘﻌﻠﹼﻕ ﺇﻻ ﺒﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ‪.‬‬
‫ﻝﻭ ﻭﻀﻌﻨﺎ ﺍﻵﻥ ﺍﻷﺴﺎﺱ ‪ A−‬ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻝﺘﻔﺎﻋل ﻤﻌﻪ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪A− + H2 O ⇌ HA + O H−‬‬
‫ﻴﺠﺭﻱ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﻤﻀﻲ‪ -‬ﺍﻷﺴﺎﺴﻲ ﺒﻴﻥ ﺍﻷﺴﺎﺱ ‪ A−‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪ H A / A−‬ﻭﺍﻝﺤﻤﺽ‬
‫‪ H2 O‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪ H2 O/ OH−‬ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﺸﻜﻠﻴ‪‬ﺘﻴﻥ‪:‬‬
‫‪H2 O ⇌ ΟH− + H+‬‬
‫‪H+ + A− ⇌ HA‬‬
‫ﻻ ﺒﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ﻴﺴﻤ‪‬ﻰ‬

‫ﻭﻴﺘﻤﻴ‪‬ﺯ ﺍﻝﺘﻭﺍﺯﻥ ﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺒﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ ﻻ ﻴﺘﻌﻠﹼﻕ ﺇ ﹼ‬
‫ﺜﺎﺒﺕ ﺍﻷﺴﺎﺴﻴﺔ‪:‬‬
‫]‪[OH− ][H A‬‬

‫= ‪KB‬‬
‫] ‪[A−‬‬
‫ﻭﻨﻌﺭ‪‬ﻑ ﻜﻤﺎ ﻓﻲ ﺍﻝﺴﺎﺒﻕ ‪. pK B = − log K B‬‬
‫ﻥ ﺍﻝﺜﺎﺒﺘﻴﻥ ‪ K A‬ﻭ ‪ K B‬ﻏﻴﺭ ﻤﺴﺘﻘﻠﹼﻴﻥ ﺇﺫ ﻴﺭﺘﺒﻁﺎﻥ ﺒﺎﻝﻌﻼﻗﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬

‫ﺇ‪‬‬
‫]‪[H 3O+ ][A− ] [OH− ][HA‬‬

‫= ‪KA ⋅ KB‬‬ ‫⋅‬
‫]‪[HA‬‬ ‫] ‪[A−‬‬
‫] ‪= [H 3O+ ] ⋅ [OH−‬‬
‫‪= Kw‬‬
‫ﻭﻫﻜﺫﺍ ﻨﻜﺘﺏ‬
‫‪pK A + pK B = pK w‬‬
‫ﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫ﻭﻫﺫﻩ ﺍﻝﻌﻼﻗﺔ ﺘﺭﺒﻁ ﺒﻴﻥ ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ﻭﺜﺎﺒﺕ ﺍﻷﺴﺎﺴﻴﺔ ﻝﺯﻭ ﹺ‬
‫ﻭﻫﻜﺫﺍ ﻨﺨﻠﺹ ﺇﻝﻰ ﺍﻝﻘﻭل ﺇﻝﻰ ﺃﻨﻪ ﻴﻤﻜﻥ ﺘﻭﺼﻴﻑ ﺯﻭﺝ ﺤﻤﺽ‪ /‬ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫‪ K A‬ﺃﻭ ‪ . pK A‬ﻴﻌﻁﻲ ﺍﻝﻤﻠﺤﻕ ﻓﻲ ﺁﺨﺭ ﺍﻝﻜﺘﺎﺏ ﻗﻴﻡ ‪pK A‬‬ ‫ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‬
‫ﻝﺒﻌﺽ ﺍﻝﺤﻤﻭﺽ ﺍﻝﻀﻌﻴﻔﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫ﻼ‬
‫ﺤ‪‬‬‫‪ .2.6.II‬ﺯﻭﺠﺎ ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ‪‬ﻤ ‪‬‬
‫ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ‪: H3O+/H2O‬‬ ‫‬
‫⇌ ‪H3O+ + H2O‬‬ ‫‪H2O + H3O+‬‬
‫ﻫﻨﺎ ﻴﻜﻭﻥ ‪ K A = 1‬ﺃﻱ ‪. pK A = 0‬‬

‫ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ‪: H2O/OH−‬‬ ‫‬
‫‪H2O + H2O ⇌ OH− + H3O+‬‬
‫ﻫﻨﺎ ﻴﻜﻭﻥ ‪ K A = K w‬ﺃﻱ ‪ ، pK A = 14‬ﻭﺫﻝﻙ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪. 25 C‬‬
‫ﻭﺒﻬﺫﺍ ﻨﺨﻠﺹ ﺇﻝﻰ ﺍﻝﻨﺘﻴﺠﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪ :‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ‪:‬‬
‫‪pK A (H 3O+ /H2O) = 0‬‬
‫‪pK A(H2O/OH− ) = 14‬‬ ‫ﻭ‬
‫‪ .III‬ﺘﺭﺘﻴﺏ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‬
‫‪ .1.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﺍﻝﻀﻌﻴﻔﺔ‬
‫ﺘﺯﺩﺍﺩ ﻗﻭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﻓﻲ ﺍﻝﻤﺎﺀ ﻜﻠﻤﺎ ﻜﺎﻥ ﺃﻗﺩﺭ ﻋﻠﻰ ﺘﻘﺩﻴﻡ ﺒﺭﻭﺘﻭﻨﻪ ‪ H+‬ﻭﻨﻜﺘﺏ ‪:‬‬
‫‪1‬‬
‫‪HA + H2O ⇌ A− + H3O+‬‬
‫‪2‬‬
‫ﺃﻱ ﺇﺫﺍ ﻜﺎﻥ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﻤﻨﺯﺍﺤﹰﺎ ﻓﻲ ﺍﻻﺘﺠﺎﻩ ‪ ، 1‬ﺃﻭ ﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ ﺇﺫﺍ ﻜﺎﻥ ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‬
‫ﻜﺒﻴﺭ ﹰﺍ ‪ ،‬ﺃﻭ ﻜﺎﻥ ﻜﺎﻥ ﺍﻝﻤﻘﺩﺍﺭ ‪ pK A‬ﺼﻐﻴﺭ ﹰﺍ‪ .‬ﻭﻫﻜﺫﺍ ﻴﻤﻜﻨﻨﺎ ﺍﻋﺘﻤﺎﺩ ﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ K A‬ﺃﻭ ‪pK A‬‬
‫ﺘﺭﺘﻴﺏ ﺍﻷﺯﻭﺍﺝ )ﺤﻤﺽ ﻀﻌﻴﻑ‪/‬ﺃﺴﺎﺱ ﻀﻌﻴﻑ( ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫ﻥ ﻗﻭﺓ ﺍﻷﺴﺎﺱ ﺍﻝﻀﻌﻴﻑ ﻓﻲ ﺍﻝﻤﺎﺀ ﺘﺯﺩﺍﺩ ﺒﺎﺯﺩﻴﺎﺩ ﻗﺩﺭﺘﻪ ﻋﻠﻰ‬

‫ﻭﺒﻁﺭﻴﻘﺔ ﻤﻤﺎﺜﻠﺔ ﻨﻘﻭل ﺇ ‪‬‬
‫ﺍﻜﺘﺴﺎﺏ ﺒﺭﻭﺘﻭﻥ ﺒﺴﻬﻭﻝﺔ‪ .‬ﻭﻫﻜﺫﺍ ﻜﻠﻤﺎ ﻜﺎﻥ ﺍﻷﺴﺎﺱ ﺍﻝﻀﻌﻴﻑ ﻗﻭﻴﹰﺎ ﻓﻲ ﺍﻝﻤﺎﺀ ﻜﺎﻥ ﺍﻝﺘﻭﺍﺯﻥ‬
‫‪1‬‬
‫‪A− + H2O ⇌ HA + OH−‬‬
‫‪2‬‬
‫ﻤﻨﺯﺍﺤﹰﺎ ﻓﻲ ﺍﻻﺘﺠﺎﻩ ‪ ،1‬ﺃﻭ ﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ ﺇﺫﺍ ﻜﺎﻨﺕ ‪ K B‬ﻜﺒﻴﺭﺓ‪ ،‬ﺃﻭ ﻜﺎﻥ ﺍﻝﻤﻘﺩﺍﺭ ‪ pK B‬ﺼﻐﻴﺭﹰﺍ‪.‬‬
‫ﻭﻝ ‪‬ﻤﺎ ﻜﺎﻥ ‪ pK A + pK B = pK w‬ﻗﻠﻨﺎ ﺃﻴﻀﹰﺎ ﺘﺯﺩﺍﺩ ﻗﻭﺓ ﺍﻷﺴﺎﺱ ﺍﻝﻀﻌﻴﻑ ﻓﻲ ﺍﻝﻤﺎﺀ ﺇﺫﺍ ﻜﺎﻥ‬
‫‪ K A‬ﺼﻐﻴﺭﹰﺍ‪ ،‬ﺃﻭ ﻜﺎﻥ ﺍﻝﻤﻘﺩﺍﺭ ‪ pK A‬ﻜﺒﻴﺭﹰﺍ‪ .‬ﺍﻝﺸﻜل ) ‪. ( 4‬‬
‫‪pK A‬‬
‫ﺤﻤﻭﺽ ﺃﻜﺜﺭ ﻓﺄﻜﺜﺭ ﻗﻭﺓ‬

‫ﺃﺴﺱ ﺃﻜﺜﺭ ﻓﺄﻜﺜﺭ ﻗﻭﺓ‬
‫‪KA‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 4‬ﻜﻠﻤﺎ ﺍﺯﺩﺍﺩﺕ ﻗﻴﻤﺔ ﺍﻝﻤﻘﺩﺍﺭ ‪ ، pK A‬ﻜﺎﻥ ﺍﻷﺴﺎﺱ ﺃﻗﻭﻯ‪ ،‬ﻭﻜﺎﻥ ﺍﻝﺤﻤﺽ ﺍﻝﻤﺭﺍﻓﻕ ﻝﻪ‬
‫ﺃﻀﻌﻑ‪.‬‬
‫‪ .2.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﺍﻝﻘﻭﻴﺔ ﻭﺍﻷﺴﺱ ﺍﻝﻘﻭﻴﺔ‬
‫ل‬ ‫ﺘﻌﺘﺒﺭ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺃﻗﻭﻯ ﺤﻤﺽ ﻴﻤﻜﻥ ﺃﻥ ﻴﻭﺠﺩ ﻓﻲ ﺍﻝﻤﺎ ﺀ‪ ،‬ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫ﻥ ﻜّ‬
‫ﺍﻝﺤﻤﻭﺽ ﺍﻝﺘﻲ ﻨﺴﻤ‪‬ﻴﻬﺎ ﻗﻭﻴﺔ ﺘﻜﻭﻥ ﺤﻤﻭﻀﹰﺎ ﺃ ﻗﻭﻯ ﻤﻥ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ ،‬ﻭﻴﻜﻭﻥ ﺘﻔﺎﻋل‬
‫ﺍﻝﺤﻤﺽ ﺍﻝﻘﻭﻱ ﻤﻊ ﺍﻝﻤﺎﺀ ﺘﺎﻤﹰﺎ‪ ،‬ﻭﻻ ﻨﺴﺘﻁﻴﻊ ﺘﺭﺘﻴﺏ ﺍﻝﺤﻤﻭﺽ ﺍﻝﻘﻭﻴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﻨﻌﺒ‪‬ﺭ ﻋﻥ ﺫﻝﻙ‬
‫ﻥ ﺍﻝﻤﺎﺀ ﻴﺴﺎﻭﻱ ﺒﻴﻥ ﻫﺫﻩ ﺍﻝﺤﻤﻭﺽ ﻤﻥ ﺤﻴﺙ ﺍﻝﻘﻭﺓ‪.‬‬
‫ﺒﻘﻭﻝﻨﺎ ﺇ ‪‬‬
‫ل‬
‫ﻥﻜّ‬
‫ﻭﻜﺫﻝﻙ ﺘﻌﺘﺒﺭ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺃﻗﻭﻯ ﺃﺴﺎﺱ ﻴﻤﻜﻥ ﺃﻥ ﻴﻭﺠﺩ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫ﺍﻷﺴﺱ ﺍﻝﺘﻲ ﻨﺴﻤ‪‬ﻴﻬﺎ ﺃﺴﺴﹰﺎ ﻗﻭﻴﺔ ﺘﻜﻭﻥ ﺃﻗﻭﻯ ﻤﻥ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ‪ ،‬ﻭﻴﻜﻭﻥ ﺘﻔﺎﻋل ﺍﻷﺴﺎﺱ‬
‫ﻥ‬
‫ﺍﻝﻘﻭﻱ ﻤﻊ ﺍﻝﻤﺎﺀ ﺘﺎﻤﹰﺎ ‪ ،‬ﻭﻻ ﻨﺴﺘﻁﻴﻊ ﺘﺭﺘﻴﺏ ﺍﻷﺴﺱ ﺍﻝﻘﻭﻴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪ .‬ﻭﻨﻌﺒ‪‬ﺭ ﻋﻥ ﺫﻝﻙ ﺒﻘﻭﻝﻨﺎ ﺇ ‪‬‬
‫ﺍﻝﻤﺎﺀ ﻴﺴﺎﻭﻱ ﺒﻴﻥ ﻫﺫﻩ ﺍﻷﺴﺱ ﻤﻥ ﺤﻴﺙ ﺍﻝﻘﻭﺓ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺨﻠﺹ ﺇﻝﻰ ﻋﺩﻡ ﺇﻤﻜﺎﻥ ﺘﺭﺘﻴﺏ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﺍﻝﻘﻭﻴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﻝﻜﻥ ﻴﻤﻜﻥ‬
‫ﺤﻼﺕ ﺃﺨﺭﻯ ﻏﻴﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫ﺘﺭﺘﻴﺒﻬﺎ ﻓﻲ ‪‬ﻤ ‪‬‬
‫ﻝﻤﺎ ﻜﺎﻥ ﺍﻝﺤﻤﺽ ‪ H3O+‬ﻫﻭ ﺍﻝﺤﻤﺽ ﺍﻷﻗﻭﻯ ﻓﻲ ﺍﻝﻤﺎﺀ ﻜﺎﻨﺕ ﻜل ﺍﻝﺤﻤﻭﺽ ﺍﻝﻀﻌﻴﻔﺔ‬
‫ﻥ ﻗﻴﻡ‬
‫ﺃﻀﻌﻑ ﻤﻥ ‪ H3O+‬ﺍﻝﺫﻱ ﻴﺅ ﺩ‪‬ﻱ ﺩﻭﺭ ﺤﻤﺽ ﻓﻲ ﺍﻝﺯﻭﺝ ‪ ، H3O+/H2O‬ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫‪ pK A‬ﺍﻝﺨﺎﺼﺔ ﺒﻬﺫﻩ ﺍﻝﺤﻤﻭﺽ ﺘﻜﻭﻥ ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﺼﻔﺭ‪ .‬ﻭﻝﻤﹼﺎ ﻜﺎﻥ ‪ OH−‬ﻫﻭ ﺍﻷﺴﺎﺱ ﺍﻷﻗﻭﻯ‬
‫ﻓﻲ ﺍﻝﻤﺎﺀ ﻜﺎﻨﺕ ﺍﻷﺴﺱ ﺍﻝﻀﻌﻴﻔﺔ ﻓﻲ ﺍﻝﻤﺎﺀ ) ﺍﻝﻤﺭﺍﻓﻘﺔ ﻝﺤﻤﻭﺽ ﻀﻌﻴﻔﺔ( ﺃﻀﻌﻑ ﻤﻥ ‪، OH−‬‬
‫ﺼﺔ ﺒﻬﺎ ﺘﻜﻭﻥ ﺃﺼﻐﺭ ﻤﻥ ‪ . 14‬ﻭﻝﻬﺫﺍ ﺘﺘﺭﺍﻭﺡ ﻗﻴﻡ ‪ p K A‬ﻝﺯﻭﺝ‬

‫ﻥ ﻗﻴﻤﺔ ‪ pK A‬ﺍﻝﺨﺎ ‪‬‬
‫ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﻓﻲ ﺍﻝﻤﺎﺀ ﺒﻴﻥ ﺍﻝﺼﻔﺭ ﻭ ‪ 14‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ‪. 25 C‬‬
‫ﻱ ﻓﻲ ﺍﻝﻤﺎﺀ‪ .‬ﻭﻜﺫﻝﻙ‬
‫ﻭﺘﻜﻭﻥ ﻗﻴﻡ ‪ pK A‬ﺍﻝﺴﺎﻝﺒﺔ ﻤﻤﻴﺯﺓ ﻝﺯﻭﺝ ﺤﻤﺽ‪ /‬ﺃﺴﺎﺱ‪ ،‬ﺤﻤﻀﻪ ﻗﻭ ‪‬‬
‫ﻱ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫ﺘﻜﻭﻥ ﻗﻴﻡ ‪ pK A‬ﺍﻷﻜﺒﺭ ﻤﻥ ‪ 14‬ﻤﻤﻴﺯﺓ ﻝﺯﻭﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‪ ،‬ﺃﺴﺎﺴﻪ ﻗﻭ ‪‬‬
‫ﻴﻠﺨﺹ ﺍﻝﺸﻜل )‪ (5‬ﻤﺨﺘﻠﻑ ﻫﺫﻩ ﺍﻝﺤﺎﻻﺕ‪.‬‬
‫‪pK A‬‬
‫‪C2H5O−‬‬
‫ﺃﺴﺱ ﻗﻭﻴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫‪C2H5OH‬‬
‫ﺤﻤﻭﺽ ﻏﻴﺭ ﻗﺎﺒﻠﺔ ﻝﻠﺘﻤﻴﻴﺯ ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫‪OH− 14.0‬‬
‫‪H2O‬‬
‫‪NH3‬‬
‫ﻓﻲ ﺍﻝﻤﺎﺀ‬ ‫ﺃﺴﺱ ﻀﻌﻴﻔﺔ‬ ‫‪NH+‬‬‫‪4‬‬ ‫ﺤﻤﻭﺽ ﻀﻌﻴﻔﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫‪−‬‬
‫‪CH3COO‬‬
‫‪CH3COOH‬‬
‫‪H2O 0.0‬‬
‫‪H3O+‬‬
‫ﺃﺴﺱ ﻏﻴﺭ ﻗﺎﺒﻠﺔ ﻝﻠﺘﻤﻴﻴﺯ ﻓﻲ ﺍﻝﻤﺎﺀ‬ ‫ﺤﻤﻭﺽ ﻗﻭﻴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫‪Cl−‬‬
‫‪HCl‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 5‬ﺘﺭﺘﻴﺏ ﻝﻤﺨﺘﻠﻑ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻓﻲ ﺍﻝﻤﺎﺀ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪. 25 C‬‬
‫‪ .IV‬ﻤﺨﻁﻁﺎﺕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ‪:‬‬
‫ل ﺯﻭﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ‪ H A / A− :‬ﻴﺘﻤﻴ‪‬ﺯ ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ‬

‫ﻥﻜّ‬
‫ﻜﻨﺎ ﻗﺩ ﺭﺃﻴﻨﺎ ﺃ ‪‬‬
‫] ‪[H3O+ ][A−‬‬
‫= ‪KA‬‬
‫]‪[HA‬‬
‫ﺃﻭ ﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ‪:‬‬
‫] ‪[A−‬‬
‫‪pH = pK A + log‬‬
‫]‪[H A‬‬
‫ ﻨﻼﺤﻅ ﺃﻨﻪ ﻓﻲ ﺤﺎﻝﺔ ‪ ، pH = pK A‬ﻴﻜﻭﻥ ] ‪. [ H A ] = [ A−‬‬
‫ﻥ ] ‪ ، [ H A ]< [ A−‬ﺃﻱ ﻴﻜﻭﻥ ﺍﻷﺴﺎﺱ ﻫﻭ ﺍﻝﻨﻭﻉ ﺍﻝﺭﺍﺠﺢ‪.‬‬

‫ ﻭﻓﻲ ﺤﺎﻝﺔ ‪ pH > pK A‬ﻓﺈ ‪‬‬
‫ﻥ ] ‪ ، [ H A ]> [ A−‬ﺃﻱ ﻴﻜﻭﻥ ﺍﻝﺤﻤﺽ ﻫﻭ ﺍﻝﻨﻭﻉ ﺍﻝﺭﺍﺠﺢ‪.‬‬

‫ ﺃﻤ‪‬ﺎ ﻓﻲ ﺤﺎﻝﺔ ‪ pH < pK A‬ﻓﺈ ‪‬‬
‫ﻭﺒﻬﺫﺍ ﻨﺤﺼل‪ ،‬ﻓﻲ ﺍﻝﺸﻜل ) ‪ ، ( 6‬ﻋﻠﻰ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﺘﺎﻝﻲ‪.‬‬
‫ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺍﻝﺤﻤﺽ‬ ‫ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺍﻷﺴﺎﺱ‬
‫‪pkA −3‬‬ ‫‪pkA −2‬‬ ‫‪pkA −1‬‬ ‫‪pkA‬‬ ‫‪pkA +1‬‬ ‫‪pkA +2‬‬ ‫‪pkA +3‬‬ ‫‪pH‬‬
‫] ‪[ HA‬‬
‫‪103‬‬ ‫‪102‬‬ ‫‪10‬‬ ‫‪1‬‬ ‫‪10 -1‬‬ ‫‪10 -2‬‬ ‫‪10 -3‬‬
‫] ‪[ A−‬‬
‫] ‪[ HA‬‬
‫‪.‬‬ ‫ﺍﻝﺸﻜل ) ‪ : ( 6‬ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺒﺩﻻﻝﺔ ‪ pH‬ﻭ‬
‫] ‪[ A−‬‬
‫ل ﻤﻥ ﺍﻝﻨﻭﻉ‬
‫ﻴﻤﻜﻨﻨﺎ ﺍﻻﺴﺘﻌﺎﻨﺔ ﺒﺒﺭﻤﺠﻴﺎﺕ ﻤﺘﺨﺼﺼﺔ ﺘﻔﻴﺩ ﻓﻲ ﺘﺤﺩﻴﺩ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻜ ّ‬
‫ﺍﻝﺤﻤﻀﻲ ﻭﺍﻝﻨﻭﻉ ﺍﻷﺴﺎﺴﻲ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﻜل ﻗﻴﻤﺔ ‪ pH‬ﻴﺄﺨﺫﻫﺎ ﺍﻝﻭﺴﻁ‪ ،‬ﻭﺒﻬﺫﺍ ﻨﺤﺼل ﻋﻠﻰ‬
‫ﻤﺎ ﻴ‪‬ﻌﺭﻑ ﺒﺎﺴﻡ ﻤﺨﻁﻁ ﺘﻭﺯﻴﻊ ﺍﻷﻨﻭﺍﻉ‪.‬‬
‫ﺘﺴﻤﺢ ﻫﺫﻩ ﺍﻝﺒﺭﻤﺠﻴﺎﺕ ﺒﺩﺭﺍﺴﺔ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻅﺭﻱ ﻝﻤﺯﻴﺞ ﻭﻤﺘﺎﺒﻌﺔ ﺘﻐﻴﺭﺍﺕ ﺍﻝﺘﺭﻜﻴﺏ ﻨﺘﻴﺠﺔ‬
‫ل ﻨﻭﻉ ﻤﻭﺠﻭﺩ ﺒﺤل‬
‫ﻝﺨﻀﻭﻉ ﻫﺫﺍ ﺍﻝﻤﺯﻴﺞ ﻝﺘﻔﺎﻋﻼﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ‪ .‬ﺇﺫ ﺘﺤﺩ‪‬ﺩ ﻫﺫﻩ ﺍﻝﺒﺭﻤﺠﻴﺎﺕ ﺘﺭﻜﻴﺯ ﻜ ّ‬
‫ﺠﻤﻠﺔ ﻤﻥ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺘﻀ ‪‬ﻡ ﻤﻌﺎﺩﻻﺕ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﻭﺜﻭﺍﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‪ .‬ﻴﺠﺭﻱ ﺇﻅﻬﺎﺭ ﻨﺘﺎﺌﺞ‬
‫ﺍﻝﺤﺴﺎﺒﺎﺕ ﻋﻠﻰ ﺸﻜل ﻤﻨﺤﻨﻴﺎﺕ ﺘﺴﻤﺢ ﺒﻤﺎ ﻴﻠﻲ‪:‬‬
‫‪ -‬ﻤﻘﺎﺭﻨﺔ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ ﻤﻊ ﺍﻝﻤﻌﻁﻴﺎﺕ ﺍﻝﻨﻅﺭﻴﺔ‪.‬‬
‫ﺍﻝﻭﺼﻭل ﺇﻝﻰ ﻤﻨﺤﻨﻴﺎﺕ ﻻ ﻴﻤﻜﻥ ﺍﻝﻭﺼﻭل ﺇﻝﻴﻬﺎ ﺘﺠﺭﻴﺒ‪‬ﻴﹰﺎ ) ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻸﻨﻭﺍﻉ‬ ‫‪-‬‬
‫ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻭﺴﻁ‪.(... ،‬‬
‫ﻭﻤﻥ ﺍﻝﻤﻤﻜﻥ ﻤﺤﺎﻜﺎﺓ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﻭﺘﺤﺩﻴﺩ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻐﺎﻝﺒﺔ ﻀﻤﻥ ﺠﻤﻠﺔ‪ ،‬ﻭﻜﺫﻝﻙ‬
‫ﺘﺤﺩﻴﺩ ﻜﻭﻥ ﻤﻌﺎﻴﺭ ‪‬ﺓ ﻤﺎ ﻜﻤﻴ ﹰﺔ ﺃﻡ ﻻ‪...،‬‬
‫ﺴﻭ ﻑ ﻨﻌﺭ ﺽ ﻓﻲ ﺩ ﺭ ﺍﺴﺘﻨﺎ ﻝﻠﻤﺤﺎ ﻝﻴل ﺍ ﻝﻤﺎ ﺌﻴﺔ ﻫﺫ ﻩ ﺍ ﻝﻤﻨﺤﻨﻴﺎ ﺕ ﻭ ﻨﺘﻌﻠﹼﻡ ﻜﻴﻔﻴﺔ ﻗﺭ ﺍ ﺀ ﺘﻬﺎ‬
‫ﻻ ﻤﺤﺎﻜﺎﺓ ﻭﻝﻡ ﺘﺄﺨﺫ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ‬
‫ﻥ ﻫﺫ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻝﻴﺴﺕ ﺇ ﹼ‬
‫ﻭﺍﺴﺘﺜﻤﺎﺭﻫﺎ‪ ،‬ﺩﻭﻥ ﺃﻥ ﻨﻨﺴﻰ ﺃ ‪‬‬
‫ﻻ ﺍﻝﺨﺼﺎﺌﺹ ﺍﻝﺘﻲ ﺍﺨﺘﺎﺭﻫﺎ ﻤﺴﺘﺜﻤﺭ ﺍﻝﺒﺭﻤﺠﻴﺔ‪.‬‬
‫ﺇﹼ‬
‫ﻥ ﺠﻤﻴﻊ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺘﻲ ﺴﺘﹸﻌﺭ ﺽ ﻓﻲ ﺍﻝﻜﺘﺎﺏ ﻗﺩ ﺒ‪‬ﺭﻤﺠﺕ‬
‫ﻤﻥ ﺍ ﻝﻤﻔﻴﺩ ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ ﺃ ‪‬‬
‫ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺒﺭﻤﺠﻴﺔ ‪.‬‬
‫‪%‬‬
‫‪← % HNO2‬‬ ‫‪← %NO−‬‬
‫‪2‬‬
‫‪90‬‬
‫‪80‬‬
‫‪70‬‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪−pK A‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3 3.2 4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪pH‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 7‬ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﺍﻝﺨﺎﺹ ﺒﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﻭﺸﺎﺭﺩﺓ ﺍﻝﻨﺘﺭﻴﺕ‬
‫ﻨﻭﻀ‪‬ﺢ ﻓﻴﻤﺎ ﻴﻠﻲ ﻜﻴﻔﻴﺔ ﺍﻝﻭﺼﻭل ﺇﻝﻰ ﻤﺨﻁﻁﺎﺕ ﺘﻭﺯﻴﻊ ﺍﻷﻨﻭﺍﻉ ﻓﻲ ﺤﺎﻝﺔ ﺤﻤﺽ ﻭﺤﻴﺩ ﺍﻝﻭﻅﻴﻔﺔ ﺜ ‪‬ﻡ‬
‫ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ‪:‬‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻴﻀ ‪‬ﻡ‪ ،‬ﻤﻥ ﺠﻤﻠﺔ ﻤﺎ ﻴﻀ ‪‬ﻡ‪ ،‬ﺍﻝﺤﻤﺽ ﺍﻝﻭﺤﻴﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪ HA‬ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ ‪c‬‬
‫ﻨﺤﻀ‪‬ﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﻭﻴﻤﺘﻠﻙ ﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪ . K A‬ﻴﺘﻌﻠﹼﻕ ‪ pH‬ﺍﻝﻭﺴﻁ ﺒﻤﺠﻤﻭﻋﺔ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺘﻭﻓﺭﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻴﺘﻭﺯ‪‬ﻉ ﺍﻝﺤﻤﺽ ‪ HA‬ﺍﻝﺫﻱ ﻭ‪‬ﻀﻊ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ ﺒﻴﻥ ﺍﻝﻨﻭﻋﻴﻥ ﺍﻝﺤﻤﻀﻲ ﻭﺍﻷﺴﺎﺴﻲ‪ ،‬ﻭﺫﻝﻙ‬
‫ﻤﻬﻤﺎ ﺘﻜﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪ .‬ﻭﻫﻜﺫﺍ ﻴﻌﻁﻲ ﺸﺭ ﹸ‬
‫ﻁ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻌﺎﺩﻝ ﹶﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫] ‪c = [ HA ] + [ A−‬‬
‫ﻥ‪:‬‬
‫ﺤﻴﺙ ‪ c‬ﻫﻭ ﺘﺭﻜﻴﺯ ﺍﻝﺤﻤﺽ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﺍﻝﺒﺩﺀ‪ ،‬ﺃﻱ ﺇ ‪‬‬
‫‪‬‬ ‫‪[A− ] ‬‬
‫‪c = [HA] ⋅  1+‬‬ ‫‪‬‬
‫‪ [HA] ‬‬
‫‪‬‬ ‫‪K ‬‬
‫‪= [HA] ⋅  1 + A ‬‬
‫‪‬‬ ‫‪h ‬‬
‫ﺤﻴﺙ ] ‪ . h = [ H3O+‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ ‪:‬‬
‫]‪[HA‬‬ ‫‪h‬‬
‫=‬
‫‪c‬‬ ‫‪h + KA‬‬
‫ﻭ‬
‫‪−‬‬
‫] ‪[A‬‬ ‫‪KA‬‬
‫=‬
‫‪c‬‬ ‫‪h + KA‬‬
‫ﺘﺭﺴﻡ ﺍﻝﺒﺭﻤﺠﻴﺔ ﺒﻌﺩ ﺫﻝﻙ ﺍﻝﻤﻘﺩﺍﺭﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ ﺒﺩﻻﻝﺔ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ‪:‬‬
‫] ‪[ HA‬‬ ‫‪10−pH‬‬ ‫] ‪[ A−‬‬ ‫‪K‬‬

‫= ‪× 100‬‬ ‫ﻭ‬ ‫‪× 100 = −pH A‬‬
‫‪c‬‬ ‫‪10−pH + K A‬‬ ‫‪c‬‬ ‫‪10‬‬ ‫‪+ KA‬‬
‫‪ . pK A (HNO2 / NO−‬ﻴ‪‬ﻅﻬﺭ‬
‫ﻝﻨﺄﺨﺫ ﻋﻠﻰ ﺴﺒﻴل ﺍﻝﻤﺜﺎل ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ‪2 ) = 3.20‬‬
‫ﺍﻝﺸﻜل ) ‪ ( 7‬ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﺍﻝﺨﺎﺹ ﺒﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﻭﺸﺎﺭﺩﺓ ﺍﻝﻨﺘﺭﻴﺕ‪.2‬‬
‫ﺃﻤﹼﺎ ﻓﻲ ﺤﺎﻝﺔ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ‪ H2A‬ﻤﺜل ﺤﻤﺽ ﺍ ﻷﻜﺴﺎﻝﻴﻙ ‪ H2 C2O4‬ﺒﺘﺭﻜﻴﺯ‬

‫‪ ، c‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﺜﺎﺒ ﹶﺘﻲ ﺤﻤﻭﻀﺔ ‪ pK A = 1.2‬ﻭ ‪ . pK A = 4.3‬ﻓﺈﻨﻨﺎ ﻨﻜﺘﺏ ﻤﻌﺎﺩﻝﺔ ﺍﻨﺤﻔﺎﻅ‬
‫‪2‬‬ ‫‪1‬‬
‫ﺍﻝﻤﺎﺩﺓ ﻜﻤﺎ ﻴﻠﻲ‪:‬‬
‫‪‬‬ ‫‪KA‬‬ ‫‪KA KA‬‬ ‫‪‬‬

‫‪‬‬
‫‪c =  H2A  +  HA−  +  A2−  =  H2A   1 + 1 + 1 2‬‬ ‫‪‬‬
‫‪‬‬
‫‪‬‬ ‫‪ ‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪h‬‬ ‫‪h2‬‬ ‫‪‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪h 2 + KA h + KA KA‬‬
‫‪c =  H2A ‬‬ ‫‪1‬‬ ‫‪1‬‬ ‫‪2‬‬
‫‪2‬‬
‫‪h‬‬
‫‪2‬‬
‫ﻻ ﻋﻠﻰ ﺤﻤﺽ ﻀﻌﻴﻑ ﻭﺤﻴﺩ ﺍﻝﻭﻅﻴﻔﺔ ﻝﺘﻭﻀﻴﺢ ﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻭﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﻤﻥ ﺍﻝﻨﻤﻁ‬
‫ﺠﺭﻯ ﺍﺴﺘﻌﻤﺎل ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﺒﺼﻔﺘﻪ ﻤﺜﺎ ﹰ‬
‫ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ ﻤﻊ ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ ﻀﻌﻑ ﺍﺴﺘﻘﺭﺍﺭ ﻫﺫﺍ ﺍﻝﺤﻤﺽ ﻓﻲ ﺍﻝﻤﺎﺀ ﺤﻴﺙ ﻴﺘﻔﻜﻙ ﺒﺴﻬﻭﻝﺔ ﻭﻓﻕ ﺃﺤﺩ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫‪2 HNO2 → NO2 + NO + H 2 O‬‬
‫‪4 HNO2 → 2 HNO 3 + N 2 O + H 2 O‬‬

‫ﻭﻤﻨﻪ‪:‬‬
‫]‪[H2A‬‬ ‫‪h2‬‬
‫=‬
‫‪c‬‬ ‫‪h 2 + KA h + KA KA‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪2‬‬
‫ﻭﺒﺎﻝﻁﺭﻴﻘﺔ ﻨﻔﺴﻬﺎ ﻨﺠﺩ ‪:‬‬

‫‪‬‬ ‫‪h‬‬ ‫‪K A ‬‬
‫‪‬‬ ‫‪2 ‬‬
‫‪c = [H2A] + [HA− ] + [A2− ]=[HA− ] 1 +‬‬ ‫‪+‬‬ ‫‪‬‬
‫‪‬‬ ‫‪KA‬‬ ‫‪h ‬‬
‫‪1‬‬
‫ﺃﻱ‬
‫] ‪[HA−‬‬ ‫‪KA h‬‬
‫=‬ ‫‪1‬‬
‫‪c‬‬ ‫‪2‬‬
‫‪h + KA h + KA KA‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪2‬‬
‫ﻥ‪:‬‬
‫ﻭﻨﺠﺩ ﺒﺎﻝﻤﺜل ﺃ ‪‬‬
‫] ‪[A2−‬‬ ‫‪KA KA‬‬
‫=‬ ‫‪1‬‬ ‫‪2‬‬
‫‪c‬‬ ‫‪2‬‬
‫‪h + KA h + KA KA‬‬
‫‪1‬‬ ‫‪1‬‬ ‫‪2‬‬
‫ﻭﻫﻜﺫﺍ ﻴﻅﻬﺭ ﻤﻨﺤﻨﻲ ﺍﻝﺘﻭﺯﻴﻊ ﺍﻝﺨﺎﺹ ﺒﺎﻝﺤﻤﺽ ﺍﻝﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ﻜﻤﺎ ﻓﻲ ﺍﻝﺸﻜل )‪:(8‬‬
‫‪%‬‬
‫‪←%H2 C2 O4‬‬ ‫‪←%HC2O−‬‬
‫‪4‬‬ ‫‪←%C2 O4‬‬
‫‪2−‬‬
‫‪90‬‬
‫‪80‬‬
‫‪70‬‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪− pK A1‬‬ ‫‪−pK A2‬‬
‫‪0‬‬ ‫‪1 1.2 2‬‬ ‫‪3‬‬ ‫‪4 4.3 5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪pH‬‬
‫‪C2O4‬‬ ‫‪2−‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 8‬ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﺍﻝﺨﺎﺹ ﺒـ ‪ H2C2O4‬ﻭ ‪ HC2O4‬ﻭ‬
‫‪−‬‬
‫‪ .V‬ﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪-‬ﺃﺴﺎﺱ‪ ،‬ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺘﻔﺎﻋل ﺍﻝﺘﺎﻝﻲ ‪:‬‬

‫‪A1 + B2 A2 + B1‬‬
‫ﻴﻤﻜﻥ ﻜﺘﺎﺒﺔ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ‪ K‬ﺒﺩﻻﻝﺔ ﺜﺎﺒ ﹶﺘﻲ ﺍﻝﺤﻤﻭﻀﺔ ﻝﻠﺯﻭﺠﻴﻥ ‪ A1 / B1‬ﻭ ‪A2 / B2‬‬
‫ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫] ‪[A2 ][B1‬‬
‫= ‪K‬‬ ‫‪= K A KA‬‬
‫] ‪[A1 ][B2‬‬ ‫‪1‬‬ ‫‪2‬‬
‫ﻭﻫﻨﺎ ﻨﻤﻴ‪‬ﺯ ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ‪.‬‬
‫ ﺍﻝﺤﺎﻝﺔ ﺍﻷﻭﻝﻰ ‪ K A > K A :‬ﺃﻭ ‪. pK A < pK A‬‬

‫‪1‬‬ ‫‪2‬‬ ‫‪1‬‬ ‫‪2‬‬
‫ل ﻤﻥ ‪ A1‬ﻭ ‪ B2‬ﻤﻨﻔﺼﻠﺘﻴﻥ ‪ ،‬ﻭﻴﻤﻜﻥ‬

‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻴﻜﻭﻥ ‪ K > 1‬ﻭﺘﻜﻭﻥ ﻤﻨﻁﻘﺘﺎ ﺭﺠﺤﺎﻥ ﻜ ﱟ‬
‫ﺘﺎﻡ(‬ ‫ﻝﻠﺘﻔﺎﻋل ﺃﻥ ﻴﺘ ‪‬ﻡ ﻭﻓﻕ ﻗﺎﻋﺩﺓ ‪ γ‬ﻜﻤﺎ ﻴﻅﻬﺭ ﻓﻲ ﺍﻝﺸﻜل ) ‪ .3 ( 9‬ﻭﻨﻌﺘﺒﺭ ﺍﻝﺘﻔﺎﻋل ﻜﻤﻴﹰﺎ )ﺃﻭ ﺸﺒﻪ‬
‫ﻓﻲ ﺤﺎﻝﺔ ‪. K > 103‬‬
‫‪pH‬‬
‫‪B2‬‬
‫‪pK A2‬‬
‫‪A2‬‬
‫‪B1‬‬
‫‪pK A1‬‬
‫‪A1‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 9‬ﻝﻠﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ ﺍﻝﻤﺘﻔﺎﻋﻠﻴﻥ ﻤﻨﻁﻘﺘﺎ ﺭﺠﺤﺎﻥ ﻤﺘﻤﺎﻴﺯﺘﺎﻥ‬
‫‪3‬‬
‫ﺒﺩﺀﹰﺍ ﻤﻥ ﺍﻷﺴﺎﺱ ﺍﻝﻤﺘﻔﺎﻋل ﺒﺎﺘﺠﺎﻩ ﺍﻝﺤﻤﺽ‬ ‫‪γ‬‬ ‫ﺘﻘﻭﻡ ﻗﺎﻋﺩﺓ ‪ γ‬ﻋﻠﻰ ﺭﺴﻡ ﻤﺨﻁﻁ ﺭﺠﺤﺎﻥ ﺸﺎﻗﻭﻝﻲ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﻤﺘﻔﺎﻋﻠﻴﻥ‪ ،‬ﺜﻡ ﻨﺭﺴﻡ ﺍﻝﺤﺭﻑ‬
‫ﻤﻘﻠﻭﺒﹰﺎ ﻭﻜﺎﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺃﺼﻐﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ‪ .‬ﺘﻔﻴﺩ ﻫﺫﻩ‬ ‫‪γ‬‬ ‫ﻻ ﻜﺎﻥ ﺍﻝﺤﺭﻑ‬
‫ﺍﻝﻤﺘﻔﺎﻋل‪ .‬ﻓﺈﺫﺍ ﺘﺤﻘﻕ ﺫﻝﻙ ﻜﺎﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ‪ ،‬ﻭﺇ ﹼ‬
‫ﺍﻝﻘﺎﻋﺩﺓ ﺍﻝﺒﺴﻴﻁﺔ ﺒﺎﻝﺘﻨﺒﺅ ﺒﻤﻘﺎﺭﻨﺔ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻤﻊ ﺍﻝﻭﺍﺤﺩ ﺩﻭﻥ ﺤﺴﺎﺒﻪ‪.‬‬
‫ﻥ‬
‫ﻤﺜﺎل ‪ :‬ﺘﻔﺎﻋل ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﻤﻊ ﺍﻝﻨﺸﺎﺩﺭ‪ ،‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫‪pK A (NH+‬‬
‫‪4 /NH 3 ) = 9.2‬‬ ‫ﻭ‬ ‫‪pK A (HNO2 / NO−‬‬
‫‪2 ) = 3.2‬‬
‫‪2‬‬ ‫‪1‬‬
‫ﺤﻴﺙ ﻨﺠﺩ ‪ . K 0 = 106‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪. ( 10‬‬

‫‪pH‬‬
‫‪NH3‬‬
‫‪pK A2‬‬
‫‪NH−‬‬
‫‪4‬‬
‫‪NO−‬‬
‫‪2‬‬
‫‪pK A1‬‬
‫‪H NO2‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 10‬ﺘﻔﺎﻋل ﺍﻝﻨﺸﺎﺩﺭ ﻤﻊ ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ‪.‬‬

‫ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺜﺎﻨﻴﺔ ‪ K A < K A :‬ﺃﻭ ‪. pK A > pK A‬‬
‫‪1‬‬ ‫‪2‬‬ ‫‪1‬‬ ‫‪2‬‬
‫ﻫﻨﺎ ﻝﺩﻴﻨﺎ ‪ K 0 < 1‬ﻭﻴﻜﻭﻥ ﻝﻤﻨﻁﻘﺘﻲ ﺭﺠﺤﺎﻥ ‪ A1‬ﻭ ‪ B2‬ﺠﺯﺀ ﻤﺸﺘﺭﻙ‪ ،‬ﻭﻴﻤﻜﻥ ﻝﻠﺘﻔﺎﻋل ﺃﻥ ﻴﺘ ‪‬ﻡ‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻤﺤﺩﻭﺩ‪ ،‬ﻜﻤﺎ‬
‫ﻭﻓﻕ ﻗﺎﻋﺩﺓ ‪ γ‬ﻤﻌﻜﻭﺴﺔ ﻜﻤﺎ ﻓﻲ ﺍﻝﺸﻜل ) ‪ . ( 11‬ﻭﻨﻘﻭل ﺇ ‪‬‬
‫ﻴﻤﻜﻥ ﺇﻫﻤﺎﻝﻪ ﻓﻲ ﺤﺎﻝﺔ ‪. K 0 < 10−3‬‬
‫‪pH‬‬
‫‪B1‬‬
‫‪pK A1‬‬
‫‪A1‬‬
‫‪B2‬‬ ‫‪pK A2‬‬

‫‪A2‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 11‬ﻝﻠﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ ﺍﻝﻤﺘﻔﺎﻋﻠﻴﻥ ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﻤﺸﺘﺭﻜﺔ‪.‬‬

‫ﻥ‬
‫ﻤﺜﺎل ‪ :‬ﺘﻔﺎﻋل ﺸﺎﺭﺩﺓ ﺍﻝﺨﻼﺕ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ‪ ،‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫‪pK A (CH3COOH/CH3COO− ) = 4.7‬‬ ‫ﻭ‬ ‫‪pK A (NH+‬‬

‫‪4 /NH 3 ) = 9.2‬‬
‫‪2‬‬ ‫‪1‬‬
‫ﻥ ‪ . K 0 = 10−4.5 = 3.2 × 10−5‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪. ( 12‬‬

‫ﺤﻴﺙ ﻨﺠﺩ ﺃ ‪‬‬
‫‪pH‬‬
‫‪NH3‬‬
‫‪9.2‬‬
‫‪NH+‬‬
‫‪4‬‬
‫‪CH3COO−‬‬ ‫‪4.7‬‬
‫‪CH3COOH‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 12‬ﺘﻔﺎﻋل ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺨﻼﺕ‪.‬‬
‫

‬
‫ﻜﻴﻑ ﻨﺤﻀ‪‬ﺭ ﺍﻝﻤﺼﺎﺒﻴﺢ ﺍﻝﺯﺠﺎﺠﻴﺔ ﺍﻝﺸﺎﻓﹼﺔ ﻝﻠﻀﻭﺀ؟‬
‫ﻥ ﺍﻝﺯﺠﺎﺝ ﻤﺎﺩﺓ ﺸﻔﺎﻓﺔ ﻴﺴﻤﺢ ﺒﻤﺭﻭﺭ ﺍﻝﻀﻭﺀ ﺨﻼﻝﻪ‪ .‬ﻓﻲ‬

‫ﻤﻥ ﺍﻝﻤﻌﻠﻭﻡ ﺃ ‪‬‬
‫ﻋﺎﻡ ‪ 1925‬ﻁﻭ‪‬ﺭﺕ ‪ Toshiba‬ﺃﻭل ﻤﺼﺎﺒﻴﺢ ﺯﺠﺎﺠﻴﺔ ﺸﺎﻓﹼﺔ ﻝﻠﻀ‪‬ﻭﺀ‪،‬‬
‫ﺃﻱ ﹸﺘﺒﻌﺜﺭ ﺍﻝﻀﻭﺀ ﻓﻲ ﺠﻤﻴﻊ ﺍﻻﺘﹼﺠﺎﻫﺎﺕ‪ ،‬ﻓﻨﺤﺼل ﺒﺫﻝﻙ ﻋﻠﻰ ﺇﻀﺎﺀﺓ‬
‫ﺃﺨﻑ ﻭﻁﺄﺓ ﻋﻠﻰ ﺍﻝﻌﻴﻥ ﻤﻥ ﺍﻝﻀﻭﺀ ﺍﻝﺼﺎﺩﺭ ﻋﻥ ﺴﻠﻙ ﻤﺘﻭﻫ‪‬ﺞ‪ .‬ﻴﺠﺭﻱ‬
‫ﺫﻝﻙ ﺒﻔﻀل ﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ ﻴﺨﻀﻊ ﻝﻪ ﺍﻝﺴﻁﺢ ﺍﻝﺩﺍﺨﻠﻲ ﻝﻠﻤﺼﺒﺎﺡ‪ ،‬ﺤﻴﺙ‬
‫ﻋﻭﻝِﺞ ﺍﻝﺯﺠﺎﺝ ﺍﻝﺫﻱ ﻫﻭ ﺃﺴﺎﺴ ﹰﺎ ﺃﻜﺴﻴﺩ ﺍﻝﺴﻴﻠﻴﺴﻴﻭﻡ ‪ Si O2‬ﺒﺤﻤﺽ‬
‫ﺍﻝﻔﻠﻭﺭ ‪ HF‬ﻓﺄﺩﻯ ﺇﻝﻰ ﺘﻜﻭ‪‬ﻥ ﻁﺒﻘﺔ ﺒﻴﻀﺎﺀ ﺘﻐﻁﻲ ﺍﻝﺴﻁﺢ ﺍﻝﺩﺍﺨﻠﻲ ‪:‬‬
‫)‪SiO2(s) +6HF(aq) → H2 SiF6(aq) +2H2O(l‬‬
‫ﻴ‪‬ﺴﺘﻌﻤل ﺍﻝﺘﻔﺎﻋل ﺫﺍﺘﻪ ﻓﻲ ﺘﺯﻴﻴﻥ ﺍﻝﺯﺠﺎﺝ ﻋﺒﺭ ﺤﻔﺭ ﺯﺨﺎﺭﻑ ﻭﺃﺸﻜﺎل‬
‫ﻋﻠﻴﻪ ﺒﻭﺍﺴﻁﺔ ﺤﻤﺽ ﺍﻝﻔﻠﻭﺭ‪ .‬ﺇﺫ ﻴﺠﺭﻱ ﻭﻀﻊ ﻗﻨﺎﻉ ﻤﻥ ﺍﻝﺒﺎﺭﺍﻓﻴﻥ ﺃﻭ‬
‫ﺍﻝﺸﻤﻊ ﻋﻠﻰ ﺍﻝﺯﺠﺎﺝ ﻴﺨﻔﻲ ﺍﻷﻤﺎﻜﻥ ﺍﻝﺘﻲ ﻻ ﻨﺭﻴﺩ ﺯﺨﺭﻓﺘﻬﺎ ﻭﻴﺨﻀﻊ‬
‫ﺍﻝﺠﺯﺀ ﺍﻝﻤﻜﺸﻭﻑ ﻤﻥ ﺍﻝﺯﺠﺎﺝ ﺇﻝﻰ ﺘﺄﺜﻴﺭ ﺤﻤﺽ ﺍﻝﻔﻠﻭﺭ‪ ،‬ﻜﻤﺎ ﻴﻅﻬﺭ ﻓﻲ‬
‫ﺍﻝﺸﻜل ﺍﻝﻤﺭﺍﻓﻕ‪.‬‬
‫‪ .VI‬ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪:‬‬
‫ﻨﺼﻨﹼﻑ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﻤﻭﺠﻭ ﺩﺓ ﻓﻲ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻓﻲ ﺜﻼﺙ ﺯﻤﺭ ﻏﺎﻝﺒﺔ ﻭ ﻤﻐﻠﻭﺒﺔ‬
‫ﻭﻨﺎﺩﺭﺓ ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻘﻴﻡ ﺍﻝﻨﺴﺒ‪‬ﻴﺔ ﻝﺘﺭﺍﻜﻴﺯﻫﺎ ‪:‬‬
‫ﻨﺎﺩﺭ[‬ ‫‪] ،‬ﻨﻭﻉ ﻏﺎﻝﺏ[ ≤ ‪] 10 000‬ﻨﻭﻉ‬ ‫ﻤﻐﻠﻭﺏ[‬ ‫]ﻨﻭﻉ ﻏﺎﻝﺏ[ ≤ ‪] 100‬ﻨﻭﻉ‬
‫ﻭﻨﻠﺠﺄ ﻜﺜﻴﺭﹰﺍ ﻋﻨﺩ ﻜﺘﺎﺒﺔ ﻤﻌﺎﺩﻝﺔ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﺇﻝﻰ ﺇﻫﻤﺎل ﺘﺭﻜﻴﺯ ﻨﻭﻉ ﻤﻐﻠﻭﺏ ﺒﻭﺠﻭﺩ ﺘﺭﻜﻴﺯ ﻨﻭﻉ‬
‫ﻏﺎﻝﺏ ‪ ،‬ﻭﺇﻫﻤﺎل ﺘﺭﻜﻴﺯ ﻨﻭﻉ ﻨﺎﺩﺭ ﺒﻭﺠﻭﺩ ﺘﺭﻜﻴﺯ ﻨﻭﻉ ﻤﻐﻠﻭﺏ‪ .‬ﻭﻗﺩ ﻨﻠﺠﺄ ﺃﺤﻴﺎﻨﺎﹰ‪ ،‬ﻭﻻﻋﺘﺒﺎﺭﺍﺕ‬
‫ﻋﻤﻠﻴﺔ‪ ،‬ﺇﻝﻰ ﺇﻫﻤﺎل ﺘﺭﻜﻴﺯ ﺍﻝﻨﻭﻉ ‪ X‬ﺒﻭﺠﻭﺩ ﺍﻝﻨﻭﻉ ‪ Y‬ﻋﻨﺩﻤﺎ ] ‪ . [X ] 10 ≤ [Y‬ﺘﺠﺩﺭ ﺍﻹﺸﺎﺭﺓ‬
‫ﻥ ﺠﺯﻴﺌﺎﺕ ﺍﻝﻤﺎﺀ ﺘﻌﺘﺒﺭ ﻨﻭﻋﹰﺎ ﻓﺎﺌﻕ ﺍﻝﻐﻠﺒﺔ ﻭﻻ ﻴﺩﺨل ﺃﺒﺩﹰﺍ ﻓﻲ ﺃﻴﺔ ﻤﻌﺎﺩﻝﺔ ﻻﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ‪.‬‬
‫ﺇﻝﻰ ﺃ ‪‬‬
‫ﻼ ﻤﺎ ﺒﺎﻝﺘﻔﺎ ﻋل ﺍﻝﺭﺍﺠﺢ ‪ P.R.‬ﻋﻨﺩﻤﺎ ﻻ ﺘﺘﻭ ﻗﹼﻑ ﺘﺭﺍﻜﻴﺯ ﺍﻷﻨﻭ ﺍﻉ ﺍﻝﻐﺎ ﻝﺒﺔ‬
‫ﻑ ﺘﻔﺎ ﻋ ﹰ‬
‫ﺼ ﹸ‬
‫ﹶﻨ ‪‬‬
‫ﻼ ﻤﻥ ﺍﻝﻨﻤﻁ‬
‫ﻥ ﺘﻔﺎﻋ ﹰ‬
‫ﻻ ﻋﻠﻰ ﺘﻘﺩﻡ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل‪ .‬ﻭﺒﻤﻘﺎﺭﺒﺔ ﺃﻭﻝﻴﺔ‪ ،‬ﻨﻘﺒل ﺃ ‪‬‬
‫ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺇ ﹼ‬
‫ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ ﻫﻭ ﺘﻔﺎﻋل ﺭﺍﺠﺢ ﺇﺫﺍ ﺘﺤﻘﻘﺕ ﻓﻴﻪ ﺍﻝﺸﺭﻭﻁ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫ﺃﻥ ﺘﺴﺎﻫﻡ ﻓﻴﻪ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺘﻲ ﺠﺭﻯ ﺇﺩﺨﺎﻝﻬﺎ ﺒﺩﺍﻴﺔ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ ﺃﻭ ﺍﻝﻤﺎﺀ‪.‬‬ ‫‬
‫ﺇﺫﺍ ﻜﺎﻥ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ ﺃﻜﺒﺭ ﺒﺄ ﻝﻑ ﻤﺭﺓ ﻋﻠﻰ ﺍﻷﻗل ﻤﻥ ﺠﻤﻴﻊ ﺜﻭﺍﺒﺕ ﺍ ﻝﺘﻔﺎ ﻋﻼﺕ‬ ‫‬
‫ﺍﻷﺨﺭﻯ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺤﺩﻭﺜﻬﺎ ﺒﻴﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﻭ ﺠﻭ ﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻭﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ‬
‫ﻴﻜﻭﻥ ﻤﻥ ﺒﻴﻨﻬﺎ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻤﻤﻜﻨﺔ ﻝﻬﺫﻩ ﺍﻷﻨﻭﺍﻉ ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬
‫ﻋﺩ ﻡ ﺩ ﺨﻭ ل ﺸﻭﺍ ﺭ ﺩ ﺍ ﻝﻬﻴﺩ ﺭﻭﻨﻴﻭ ﻡ ‪ H3O+‬ﻭ ﺍ ﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ‪ OH−‬ﻓﻲ ﺍﻝﻤﻌﺎ ﺩ ﻝﺔ‬ ‫‬
‫ﻻ ﺇﺫﺍ ﻜﺎﻨﺕ ﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﺃﻭ ﻗﺩ ﺃُﺩﺨ‪‬ﻠﺕ ﺇﻝﻴﻪ ﻤﻨﺫ‬

‫ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺇ ﹼ‬
‫ﺍﻝﺒﺩﺍﻴﺔ ﻭﻝﻴﺱ ﻤﺼﺩﺭﻫﺎ ﻓﻘﻁ ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪.‬‬
‫ﻥ ﺍﻝﻤﻜﻭ‪‬ﻨﺎﺕ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻝﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻨﺘﺞ ﻋﻥ ﻤﺯﺝ ﻋﺩﺓ ﺃﻨﻭﺍﻉ ﺤﻤﻀﻴﺔ ﻭ‪ /‬ﺃﻭ ﺃﺴﺎﺴﻴﺔ ﻤﺎ‬
‫ﺇ‪‬‬
‫ﻥ ﺍﻝﺤﺎﻝﺔ‬
‫ﻫﻲ ﺇﻻ ﺤﺼﻴﻠﺔ ﻋﺩﺓ ﺘﻔﺎﻋﻼﺕ‪ .‬ﻭﻝﺤﺴﺎﺏ ﺘﺭﺍﻜﻴﺯ ﺍﻝﻤﻜﻭ‪‬ﻨﺎﺕ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻨﻘﺒل ﺒﺄ ‪‬‬
‫ﺍﻝﻨﻬﺎﺌﻴﺔ ﻫﻲ ﻤﺤﺼﻠﺔ ﻋﺩﺓ ﺘﻔﺎﻋﻼﺕ ﻤﺘﻌﺎﻗﺒﺔ‪ ،‬ﺒﺤﻴﺙ ﺘﺩﺨل ﻓﻲ ﻫﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻷ ﻨﻭﺍﻉ‬
‫ﻼ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺃﻭ ﺘﻠﻙ ﺍﻝﺘﻲ ﻅﻬﺭﺕ ﻨﺘﻴﺠﺔ ﻝﺘﻠﻙ ﺍﻝﺘﻔﺎﻋﻼﺕ‪.‬‬
‫ﺍﻝﺘﻲ ﺃُﺩﺨ‪‬ﻠﺕ ﺃﺼ ﹰ‬
‫ﻴﺠﺭﻱ ﺍﻋﺘﻤﺎﺩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻤﺘﻌﺎﻗﺒﺔ ﻭﻓﻕ ﺍﻝﺘﺭﺘﻴﺏ ﺍﻝﻤﺘﻨﺎﻗﺹ ﻝﻘﻴﻡ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻔﺎﻋل ‪K 0‬‬
‫ﺍﻝﺨﺎﺼﺔ ﺒﻬﺎ‪ :‬ﺤﻴﺙ ﻴﻜﻭﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل ﻫﻭ ﺫﻝﻙ ﺍﻝﺫﻱ ﻴﺤﺼل ﺒﻴﻥ ﺍﻝﺤﻤﺽ ﺍﻷﻗﻭﻯ‬
‫ﻭﺍﻷﺴﺎﺱ ﺍﻷﻗﻭﻯ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .VII‬ﺘﻁﺒﻴﻘﺎﺕ‬
‫ﻥ ‪ K‬ﻫﻭ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‬

‫ﻤﻥ ﺍﻵﻥ ﻓﺼﺎﻋﺩﹰﺍ ﺴﻨﺸﻴﺭ ﺇﻝﻰ ‪ K‬ﺒﺎﻝﺭﻤﺯ ‪ ، K‬ﻤﻊ ﻤﺭﺍﻋﺎﺓ ﺃ ‪‬‬
‫ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻲ ﻓﻲ ﺍﻝﺸﺭﻭﻁ ﺍﻝﻨﻅﺎﻤﻴﺔ‪.‬‬
‫ﲤﺮﻳﻦ ﺃﻭﻝ ‪ :‬ﻝﺩﻴﻨﺎ ﺍﻝﻤﻘﺎﺩﻴﺭ ‪ p K A‬ﻝﻸﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻵﺘﻴﺔ ‪:‬‬

‫‪. pK A (HNO2 / NO−‬‬
‫‪2 ) = 3.20‬‬
‫‪. pK A (C6 H5 NH+‬‬

‫‪3 /C6 H5 NH2 ) = 4.50‬‬
‫‪. pK A (NH+‬‬
‫‪4 /NH 3 ) = 9.20‬‬
‫‪. pK A (CH3COOH / CH3COO− ) = 4.75‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﻋﻠﻰ ﻤﺤﻭﺭ ﺸﺎﻗﻭﻝﻲ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻜل ﻤﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺜﻤﺎﻨﻴﺔ ﺍﻝﻭﺍﺭﺩﺓ ﺁﻨﻔﹰﺎ‪.‬‬
‫ل ﻤﻥ ﺍﻝﺤﺎﻻﺕ ﺍﻵﺘﻴﺔ ‪:‬‬
‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻤﺤﺼ‪‬ل‪ ،‬ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ ﻓﻲ ﻜ ّ‬
‫‪ (a‬ﺤﻤﺽ ﺍﻝﺨل ﻤﻊ ﺍﻷﻨﻴﻠﻴﻥ‪.‬‬
‫‪ (b‬ﺸﺎﺭﺩﺓ ﺍﻝﻨﺘﺭﻴﺕ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ‪.‬‬
‫‪ (c‬ﺍﻷﻨﻴﻠﻴﻥ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ‪.‬‬
‫ﺍﻝﺤ ّل‬
‫‪ .1‬ﻴﺒﻴﻥ ﺍﻝﺸﻜل ) ‪ ( 13‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻜل ﻤﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺜﻤﺎﻨﻴﺔ ﺍﻝﻭﺍﺭﺩﺓ ﺁﻨﻔﹰﺎ‪:‬‬
‫‪ (a.2‬ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺤﻤﺽ ﺍﻝﺨل ﻤﻊ ﺍﻷﻨﻴﻠﻴﻥ ﻫﻲ‬
‫‪C6H5NH2 + CH3COOH ⇌ C6H5NH+‬‬
‫‪3 + CH3COO‬‬
‫‪−‬‬
‫ﺃﻤ‪‬ﺎ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ ﻓﻴ‪‬ﺤﺴﺏ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪[C6 H5 NH+‬‬ ‫‪−‬‬

‫] ‪3 ] [CH 3COO‬‬ ‫‪KA‬‬ ‫‪10−4.75‬‬
‫= ‪.K‬‬ ‫=‬ ‫‪1‬‬
‫=‬ ‫‪= 10−0.25‬‬
‫]‪[C6 H5 NH2 ] [CH 3COOH‬‬ ‫‪KA‬‬ ‫‪−4.5‬‬
‫‪2‬‬
‫‪10‬‬
‫‪ (b.2‬ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺸﺎﺭﺩﺓ ﺍﻝﻨﺘﺭﻴﺕ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ ﻫﻲ‬

‫‪NO−‬‬ ‫‪+‬‬
‫‪2 + NH 4 ⇌ NH 3 + HNO2‬‬

‫] ‪[NH 3 ][HNO2‬‬ ‫‪KA‬‬ ‫‪10−9.2‬‬
‫= ‪.K‬‬ ‫=‬ ‫‪1‬‬
‫=‬ ‫‪= 10−6.0 < 1‬‬
‫‪[NH+‬‬ ‫‪−‬‬
‫] ‪4 ][NO2‬‬
‫‪KA‬‬
‫‪2‬‬
‫‪10‬‬ ‫‪−3.2‬‬
‫‪ (c.2‬ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻷﻨﻴﻠﻴﻥ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ ﻫﻲ‬

‫‪C6 H5NH2 + NH+‬‬ ‫‪+‬‬
‫‪4 ⇌ C6 H 5 NH 3 + NH 3‬‬

‫‪[C6 H5 NH+‬‬ ‫‪KA‬‬ ‫‪10−9.2‬‬
‫] ‪3 ][NH 3‬‬
‫= ‪.K‬‬ ‫=‬ ‫‪1‬‬
‫=‬ ‫‪= 10−4.7 < 1‬‬
‫‪[C6 H5 NH2 ][NH+‬‬
‫] ‪4‬‬
‫‪KA‬‬
‫‪2‬‬
‫‪10−4.5‬‬
‫‪pH‬‬
‫‪NH3 9.20‬‬
‫‪NH+‬‬
‫‪4‬‬
‫‪CH 3COO− 4.75‬‬

‫‪CH 3COOH‬‬
‫‪C6 H5 NH2 4.50‬‬
‫‪C6 H5 NH+‬‬
‫‪3‬‬
‫‪NO−‬‬
‫‪2 3.20‬‬
‫‪HNO2‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 13‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻸﺯﻭﺍﺝ ﺍﻝﻤﻌﺘﺒﺭﺓ‬
‫ﻻ ﻤﻥ‬
‫ل ‪ 1.0 × 10−2‬ﻤﻭ ﹰ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﺒﺤﺠﻡ ‪ ، 250.0 mL‬ﻭﺫﻝﻙ ﺒﺤ ّ‬
‫ﻥ ‪ :‬ﻨﺤﻀ‪‬ﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﲤﺮﻳﻦ ﺛﺎ ‪‬‬
‫ﻥ‪:‬‬
‫ﻻ ﻤﻥ ﺤﻤﺽ ﺍﻝﻨﻤل‪ .‬ﻓﺈﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﺍﻝﻨﺸﺎﺩﺭ ﻤﻊ ‪ 3.0 × 10−2‬ﻤﻭ ﹰ‬
‫‪pK A (NH+‬‬
‫‪4 /NH 3 ) = 9.20‬‬
‫‪pK A(HCOOH / HCOO− ) = 3.80‬‬
‫‪ .1‬ﺍﺭﺴﻡ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪.‬‬

‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪ ،‬ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪.‬‬
‫‪ .3‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺠﻤﻴﻊ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻷﺨﺭﻯ ‪ ،‬ﻭﺤﺩ‪‬ﺩ ﺜﻭﺍﺒﺕ ﺘﻭﺍﺯﻨﻬﺎ‪ .‬ﻤﺎﺫﺍ‬
‫ﺘﺴﺘﻨﺘﺞ؟‬
‫ﻁ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺘﻘﺭﻴﺒﻴﺔ ﻝﻪ‪.‬‬
‫‪ .4‬ﺃﻭﺠﺩ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل‪ ،‬ﺜ ‪‬ﻡ ﺃﻋ ‪‬‬
‫ﺍﻝﺤل‬
‫‪ (NH+‬ﻭ ) ‪ (HCOOH / HCOO−‬ﻋﻠﻰ ﻤﺤﻭﺭ ‪pH‬‬
‫ﻨﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ ) ‪4 /NH 3‬‬
‫ﺸﺎﻗﻭﻝﻲ ﻭﺫﻝﻙ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ pK A‬ﻝﻜل ﻤﻨﻬﻤﺎ‪ .‬ﻭﻨﻀﻊ ﺇﻁﺎﺭﹰﺍ ﺤﻭل ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ‬
‫ﺍﻝﺘﻲ ﺃﻀﻴﻔﺕ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺃﻱ ‪ NH3‬ﻭ ‪. HCOO−‬‬
‫ﻥ ﻝﻜل ﻤﻥ‬
‫‪‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل ) ‪ ( 14‬ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪ .‬ﻭﻨﻼﺤﻅ ﻓﻴﻪ ﺃ ‪‬‬
‫ﻥ ﺜﺎﺒﺕ ﺘﻔﺎﻋﻠﻬﻤﺎ‬
‫‪ NH3‬ﻭ ‪ HCOOH‬ﻤﻨﺎﻁﻕ ﺭﺠﺤﺎﻥ ﻤﺘﺒﺎﻴﻨﺔ‪ ،‬ﻭﻋﻠﻰ ﺫﻝﻙ ﻴﻤﻜﻥ ﺃﻥ ﻨﺘﻨﺒﺄ ﺃ ‪‬‬
‫ﻤﻌﹰﺎ ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ‪.‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻲ ‪:‬‬
‫ﺇ‪‬‬
‫‪NH3 + HCOOH ⇌ NH+‬‬
‫‪4 + HCOO‬‬
‫‪−‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ‪:‬‬
‫‪[NH+‬‬ ‫‪−‬‬ ‫‪KA‬‬ ‫‪10−3.8‬‬

‫] ‪4 ][HCOO‬‬
‫= ‪K‬‬ ‫=‬ ‫‪1‬‬
‫=‬ ‫‪= 105.4 = 2.5 × 105‬‬
‫‪[NH 3 ][HCOOH] K A‬‬ ‫‪−9.2‬‬
‫‪2‬‬
‫‪10‬‬
‫ﻭﻫﻭ ﺘﻔﺎﻋل ﺸﺒﻪ ﺘﺎﻡ‪.‬‬
‫ﻭﻋﻠﻴﻪ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻜﺘﺏ ﺍﻝﺘﻔﺎﻋل ﺒﺎﺘﺠﺎﻩ ﻭﺍﺤﺩ‪:‬‬

‫‪NH3‬‬ ‫‪+ HCOOH → NH+‬‬
‫‪4‬‬ ‫‪+ HCOO−‬‬
‫‪0.04‬‬ ‫‪0.12‬‬ ‫‪0‬‬ ‫‪0‬‬
‫‪≈0‬‬ ‫‪0.08‬‬ ‫‪0.04‬‬ ‫‪0.04‬‬
‫ﻼ ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ‪:‬‬
‫ﺃﻤ‪‬ﺎ ﺍﻝﻤﺤﻠﻭل ﻓﻴﻀ ‪‬ﻡ ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺍﻝﻤﺎﺀ ﻜ ‪‬‬
‫‪. HCOOH, HCOO−, NH+‬‬ ‫‪+‬‬
‫‪4 , H 3O ,OH‬‬
‫‪−‬‬
‫‪pH‬‬
‫‪NH3‬‬
‫‪9.20‬‬
‫‪NH−‬‬
‫‪4‬‬
‫‪HCOO−‬‬ ‫‪3.80‬‬
‫‪H COOH‬‬
‫‪ (NH+‬ﻭ ) ‪(HCOOH / HCOO−‬‬

‫ﺍﻝﺸﻜل ) ‪ : ( 14‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺯﻭﺠﻴﻥ ) ‪4 /NH 3‬‬
‫ﻝﻜﺘﺎﺒﺔ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻷﺨﺭﻯ )ﻏﻴﺭ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﺭﺍﺠﺤﺔ( ﻨﻜﺘﺏ ‪:‬‬

‫‪HCOOH + HCOO− ⇌ HCOOH + HCOO− K = 1‬‬
‫‪HCOOH + H2 O‬‬ ‫‪⇌ H 3 O+‬‬ ‫‪+ HCOO− K = K A = 10−3.8‬‬
‫‪1‬‬
‫‪NH+‬‬
‫‪4‬‬ ‫‪+ H 2O‬‬ ‫‪⇌ H 3O+‬‬ ‫‪+ NH 3‬‬ ‫‪ K = K A = 10−9.2‬‬
‫‪2‬‬
‫‪HCOO− + H2O‬‬ ‫‪⇌ HCOOH + OH−‬‬ ‫‪ K = 10−10.2‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺜﻼﺜﺔ ﺍﻝﺘﻲ‬

‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل ﻻ ﺘﺄﺜﻴﺭ ﻝﻪ ﻋﻠﻰ ﻤﻜﻭ‪‬ﻨﺎﺕ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﻱ ﻤﻨﻬﺎ ﺒﺼﻭﺭﺓ ﻤﻠﺤﻭ ﻅﺔ ﻋﻠﻰ ﺘﺭﺍﻜﻴﺯ‬
‫ﺘﻠﻴﻪ ﺘﺘﻤﺘﻊ ﺒﺜﻭ ﺍ ﺒﺕ ﺘﻭﺍﺯﻥ ﺼﻐﻴﺭﺓ ﺠﺩ ﺍﹰ‪ ،‬ﻭ ﻝﻥ ﻴﺅ ﺜﹼﺭ ﺃ ‪‬‬
‫ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺘﻲ ﺃﻭﺠﺩﻨﺎﻫﺎ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﺍﻝﺘﻔﺎﻋل‪:‬‬
‫‪NH3 + HCOOH ⇌ NH+‬‬
‫‪4 + HCOO‬‬
‫‪−‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ‪ .‬ﻭﻴﻜﻭﻥ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل ﻫﻭ‪:‬‬
‫ﻭﻫﻜﺫﺍ ﻓﺈ ‪‬‬
‫‪[HCOOH] = 8 × 10−2 mol/L‬‬
‫‪[NH+‬‬ ‫‪−‬‬ ‫‪−2‬‬
‫‪4 ] = [HCOO ] = 4 × 10 mol/L‬‬
‫‪[NH+‬‬ ‫‪−‬‬
‫] ‪4 ][HCOO‬‬
‫= ] ‪[NH3‬‬ ‫‪= 8 × 10−8 mol/L‬‬
‫‪[HCOOH]K‬‬
‫ﺃﻤﺎ ﺤﺴﺎﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻴﺠﺭﻱ ﺒﺎﺴﺘﻌﻤﺎل ﺃﺤﺩ ﺍﻝﺯﻭﺠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ ﻓﻨﻜﺘﺏ ‪:‬‬
‫] ‪[HCOO−‬‬
‫‪pH = 3.8 + log‬‬ ‫‪= 3.5‬‬
‫]‪[HCOOH‬‬
‫ﺃﻭ‬
‫] ‪[ NH3‬‬
‫‪pH = 9.2 + log‬‬ ‫‪= 3.5‬‬
‫] ‪[ NH+4‬‬
‫ﻻ ﻤﻥ‬
‫ل ‪ 5.00 × 10−2‬ﻤﻭ ﹰ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﺒﺤﺠﻡ ‪ ، 250.0 mL‬ﻭﺫﻝﻙ ﺒﺤ ّ‬
‫ﲤﺮﻳﻦ ﺛﺎﻟﺚ‪ :‬ﻨﺤﻀ‪‬ﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﻥ‪:‬‬
‫ﻻ ﻤﻥ ﻨﻤﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ .‬ﻓﺈﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﻤﻊ ‪ 8.00 × 10−2‬ﻤﻭ ﹰ‬
‫‪pK A(HNO2 / NO−‬‬
‫‪2 ) = 3.20‬‬
‫‪pK A(HCOOH / HCOO− ) = 3.80‬‬
‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪ ،‬ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪.‬‬
‫‪ .3‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺠﻤﻴﻊ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻷﺨﺭﻯ‪ ،‬ﻭﺤﺩ‪‬ﺩ ﺜﻭﺍﺒﺕ ﺘﻭﺍﺯﻨﻬﺎ‪ .‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫ﻁ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺘﻘﺭﻴﺒﻴﺔ ﻝﻪ‪.‬‬
‫‪ .4‬ﺃﻭﺠﺩ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل‪ ،‬ﺜ ‪‬ﻡ ﺃﻋ ‪‬‬
‫‪ (HNO2 / NO−‬ﻭ ) ‪ (HCOOH / HCOO−‬ﻋﻠﻰ ﻤﺤﻭﺭ ‪pH‬‬
‫ﻨﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ ) ‪2‬‬
‫ﺸﺎﻗﻭﻝﻲ‪ ،‬ﻭﺫﻝﻙ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ pK A‬ﻝﻜل ﻤﻨﻬﻤﺎ‪ .‬ﻭﻨﻀﻊ ﺇﻁﺎﺭﹰﺍ ﺤﻭل ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸـﻭﺍﺭﺩ‬
‫ﺍﻝﺘﻲ ﺃﻀﻴﻔﺕ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺃﻱ ‪ NH3‬ﻭ ‪. HCOO−‬‬
‫ﻥ ﻝﻜل ﻤﻥ‬
‫‪‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل ) ‪ ( 15‬ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪ .‬ﻭﻨﻼﺤﻅ ﻓﻴﻪ ﺃ ‪‬‬
‫ﻥ ﺜﺎﺒﺕ ﺘﻔﺎﻋﻠﻬﻤﺎ‬
‫‪ HNO2‬ﻭ ‪ HCOO−‬ﻤﻨﺎﻁﻕ ﺭﺠﺤﺎﻥ ﻤﺘﺒﺎﻴﻨﺔ‪ ،‬ﻭﻋﻠﻰ ﺫﻝﻙ ﻴﻤﻜﻥ ﺃﻥ ﻨﺘﻨﺒﺄ ﺃ ‪‬‬
‫ﻤﻌﹰﺎ ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ‪.‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﻫﻲ ‪:‬‬
‫ﺇ‪‬‬
‫‪HNO2 + HCOO− ⇌ NO−‬‬
‫‪2 + HCOOH‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ‪:‬‬
‫‪[NO−‬‬ ‫‪KA‬‬ ‫‪10−3.2‬‬

‫]‪2 ][HCOOH‬‬
‫= ‪K‬‬ ‫=‬ ‫‪1‬‬
‫=‬ ‫‪= 100.6 ≃ 4‬‬
‫‪−‬‬ ‫‪KA‬‬ ‫‪−3.8‬‬
‫] ‪[HNO2 ][HCOO‬‬ ‫‪2‬‬
‫‪10‬‬
‫‪pH‬‬
‫‪HCOO−‬‬
‫‪3.80‬‬
‫‪H COOH‬‬
‫‪NO−‬‬
‫‪2‬‬ ‫‪3.20‬‬
‫‪H NO2‬‬
‫‪ (HNO2 / NO−‬ﻭ ) ‪(HCOOH / HCOO−‬‬

‫ﺍﻝﺸﻜل ) ‪ : ( 15‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺯﻭﺠﻴﻥ ) ‪2‬‬
‫ﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻔﺎﻋل ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ ﻭﻝﻜﻨﻪ ﺃﺼﻐﺭ ﺒﻜﺜﻴﺭ ﻤﻥ ‪ ، 103‬ﻭﻋﻠﻴﻪ ﻨﻜﺘﺏ ‪:‬‬
‫‪HNO2‬‬ ‫‪+‬‬ ‫‪HCOO−‬‬ ‫‪⇌ NO−‬‬

‫‪2‬‬ ‫‪+ HCOOH‬‬
‫‪0.200‬‬ ‫‪0.320‬‬ ‫‪0‬‬ ‫‪0‬‬
‫) ‪(0.200 − ξ‬‬ ‫) ‪(0.320 − ξ‬‬ ‫‪ξ‬‬ ‫‪ξ‬‬
‫ﻭﺍﺴﺘﻨﺎﺩﹰﺍ ﺇﻝﻰ ﺘﻌﺭﻴﻑ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻨﺠﺩ ‪:‬‬
‫‪2‬‬
‫‪ξ‬‬
‫= ‪K‬‬
‫) ‪(0.200 − ξ )(0.320 − ξ‬‬
‫ل ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ ﻨﺠﺩ ‪. ξ = 0.16 mol /L‬‬

‫ﺒﺤ ّ‬
‫ﻼ ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ‪:‬‬
‫ﺃﻤ‪‬ﺎ ﺍﻝﻤﺤﻠﻭل ﻓﻴﻀ ‪‬ﻡ ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺍﻝﻤﺎﺀ ﻜ ﹰ‬
‫‪. HCOOH, HCOO− , HNO 2 , NO−2 , H 3O+ ,OH− , Na +‬‬
‫ﻨﻜﺘﺏ ﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻷﺨﺭﻯ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﺤﺩ ﺙ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻤﺭﺘﺒﺔ ﺘﺒﻌﹰﺎ ﻝﻘﻴﻡ ﺜﻭﺍﺒﺕ‬
‫ﺘﻭﺍﺯﻨﻬﺎ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪HCOOH + HCOO− ⇌ HCOOH + HCOO− K = 1‬‬

‫‪HNO2‬‬ ‫‪+ NO−‬‬
‫‪2‬‬ ‫‪⇌ N O−‬‬
‫‪2‬‬ ‫‪+ HNO2‬‬ ‫‪K = 1‬‬
‫‪HCOOH + H2O‬‬ ‫‪⇌ H3O+‬‬ ‫‪+ HCOO− K = K A = 10−3.8‬‬
‫‪2‬‬
‫‪+‬‬
‫‪HNO2‬‬ ‫‪+ H 2O‬‬ ‫‪⇌ H 3O‬‬ ‫‪+‬‬ ‫‪NO−‬‬
‫‪2‬‬ ‫‪ K = K A = 10−3.2‬‬
‫‪1‬‬
‫‪−‬‬ ‫‪−‬‬ ‫‪−10.2‬‬
‫‪HCOO‬‬ ‫‪+ H 2O‬‬ ‫‪⇌ HCOOH + OH‬‬ ‫‪ K = 10‬‬
‫‪H2O‬‬ ‫‪+‬‬ ‫‪NO−‬‬
‫‪2‬‬ ‫‪⇌ OH‬‬ ‫‪−‬‬
‫‪+ HNO2‬‬ ‫‪ K = 10−10.8‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻷﻭل ﻭﺍﻝﺜﺎﻨﻲ ﻻ ﻴﻐﻴﺭﺍﻥ ﻤﻥ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ‪ ،‬ﺃﻤﺎ ﺒﻘﻴﺔ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻓﻬﻲ‬
‫ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻤﻬﻤﻠﺔ ﺒﺎﻝﻨﻅﺭ ﺇﻝﻰ ﺍﻝﺘﻔﺎﻋل‪:‬‬
‫‪HNO2 + HCOO− ⇌ NO−‬‬
‫‪2 + HCOOH‬‬
‫ﻼ ﺭﺍﺠﺤﹰﺎ‪.‬‬
‫ﻭﺒﻨﺎﺀ ﻋﻠﻴﻪ ﻨﺴﺘﻁﻴﻊ ﺍﻋﺘﺒﺎﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﺘﻔﺎﻋ ﹰ‬
‫ﻭﻴﻜﻭﻥ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل‪:‬‬

‫‪[NO−‬‬
‫]‪2‬‬ ‫‪= [ HCOOH ] = 0.16 mol/L‬‬
‫‪[HCOO− ] = 0.16 mol/L‬‬
‫‪[HNO2 ] = 4.0 × 10−2 mol/L‬‬
‫‪[Na + ] = 0.32 mol/L‬‬
‫ﺃﻤﺎ ﺤﺴﺎﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻴﺠﺭﻱ ﺒﺎﺴﺘﻌﻤﺎل ﺃﺤﺩ ﺍﻝﺯﻭﺠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ ﻭﻴﻜﻭﻥ‪:‬‬
‫] ‪[HCOO−‬‬
‫‪pH = 3.8 + log‬‬ ‫‪= 3.8‬‬
‫]‪[HCOOH‬‬
‫‬
‫ﺗﻤﺮﻳﻨﺎﺕ‬
‫ل ﻤﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻵﺘﻴﺔ‪:‬‬
‫ﻋﻠﹼل ﺍﻝﻁﺒﻴﻌﺔ ﺍﻝﺤﻤﻀﻴﺔ ﻝﻜ ّ‬ ‫‬
‫‪، HCO−‬‬
‫‪3 ، C6 H 5OH ، NH 4 ، HCOOH‬‬
‫‪+‬‬
‫‪. Cr2O27− ، Cu2+ ، SO3 ، H2O2‬‬

‫ل ﻤﻨﻬﺎ‪ ،‬ﺜ ‪‬ﻡ ﺒﻴ‪‬ﻥ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺸﻜﻠﻲ ﻝﻠﺘﺒﺎﺩل‬
‫ﺍﻜﺘﺏ ﺼﻴﻎ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻜ ّ‬
‫ﺍﻝﺒﺭﻭﺘﻭﻨﻲ‪.‬‬
‫ل ﻤﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻵﺘﻴﺔ‪:‬‬
‫ﻋﻠﹼل ﺍﻝﻁﺒﻴﻌﺔ ﺍﻷﺴﺎﺴﻴﺔ ﻝﻜ ّ‬ ‫‬
‫‪. NH2OH ، C2O24− ، CH 3O− ، CH 3COO− ، CH 3 NH2‬‬
‫ل ﻤﻨﻬﺎ‪ ،‬ﺜ ‪‬ﻡ ﺒﻴ‪‬ﻥ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺸﻜﻠﻲ ﻝﻠﺘﺒﺎﺩل‬
‫ﺍﻜﺘﺏ ﺼﻴﻎ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻜ ّ‬
‫ﺍﻝﺒﺭﻭﺘﻭﻨﻲ‪.‬‬
‫ﻴﻌﻁﻲ ﺍﺤﺘﺭﺍﻕ ﺍﻝﻜﺒﺭﻴﺕ ﻓﻲ ﺠ ‪‬ﻭ ﻤﻥ ﺍﻷﻜﺴﺠﻴﻥ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺒﺭﻴﺕ‪ ،‬ﻭﻴﺴﺒ‪‬ﺏ ﺍﻝﻤﺤﻠـﻭل‬ ‫‬
‫ﺍﻝﻨﺎﺘﺞ ﻋﻥ ﺍﻨﺤﻼل ﻫﺫﺍ ﺍﻝﻐﺎﺯ ﻓﻲ ﺍﻝﻤﺎﺀ ﺘﻐﹼﻴﺭ ﻝﻭﻥ ﺃﺯﺭﻕ ﺍﻝﺒﺭﻭﻤﻭﺘﻴﻤﻭل ﺇﻝﻰ ﺍﻷﺼﻔﺭ‪ .‬ﻋﻠﹼل‬
‫ﻫﺫﻩ ﺍﻝﻅﺎﻫﺭﺓ ﻋﻥ ﻁﺭﻴﻕ ﻜﺘﺎﺒﺔ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻼﻨﺤﻼل ﻓﻲ ﺍﻝﻤﺎﺀ ﻤﻊ ﺘﻌﻴﻴﻥ ﻤﺎ ﺘﺘﺩﺨﹼل‬
‫ﻓﻴﻬﺎ ﻤﻥ ﺃﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‪.‬‬
‫ﻤﻥ ﺠﻬﺔ ﺃﺨﺭﻯ ﻴﻌﻁﻲ ﺍﺤﺘﺭﺍﻕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻓﻲ ﺠ ‪‬ﻭ ﻤﻥ ﺍﻷﻜﺴﺠﻴﻥ ﺃﻜﺴﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‪،‬‬
‫ﻭﻴﺴﺒ‪‬ﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻋﻥ ﺍﻨﺤﻼل ﻫﺫﺍ ﺍﻝﻐﺎﺯ ﻓﻲ ﺍﻝﻤﺎﺀ ﺘﻐﻴ‪‬ﺭ ﻝﻭﻥ ﺃﺯﺭﻕ ﺍﻝﺒﺭﻭﻤﻭﺘﻴﻤﻭل‬
‫ﺇﻝﻰ ﺍﻷﺯﺭﻕ‪.‬‬
‫ ﻋﻠﹼل ﻫﺫﻩ ﺍﻝﻅﺎﻫﺭﺓ ﻋﻥ ﻁﺭﻴﻕ ﻜﺘﺎﺒﺔ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻼﻨﺤﻼل ﻓﻲ ﺍﻝﻤﺎﺀ ﻤﻊ‬
‫ﺘﻌﻴﻴﻥ ﻤﺎ ﺘﺘﺩﺨﹼل ﻓﻴﻬﺎ ﻤﻥ ﺃﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‪.‬‬
‫ ﻤﺎ ﻫﻭ ﺩﻭﺭ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻓﻲ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل؟‬
‫ﻴ‪‬ﻌﺘﺒﺭ ﺤﻤﺽ ﺍ ﻝﻤﺎ ﻝﻭ ﻨﻴﻙ ‪ HOOCCH2COOH‬ﺤﻤﻀﹰﺎ ﺜﻨﺎ ﺌﻲ ﺍ ﻝﻭ ﻅﻴﻔﺔ ‪ ،‬ﻭ ﻴﺘﻤﻴ‪‬ﺯ‬ ‫‬
‫ﺒﺎﻝﺜﺎﺒﺘﻴﻥ ‪ pK A = 2.85‬ﻭ ‪ . pK A = 5.80‬ﺴﻭﻑ ﻨﺭﻤﺯ ﺇ ﻝﻴﻪ ﻓﻴﻤﺎ ﻴﻠﻲ ﺒﺎﻝﺭﻤﺯ‬
‫‪2‬‬ ‫‪1‬‬
‫‪. H 2A‬‬
‫ل ﻤﻥ ‪ H2A‬ﻭ ‪ HA−‬ﻤﻊ ﺍﻝﻤﺎﺀ‪ ،‬ﺜ ‪‬ﻡ ﺍﺴﺘﻨﺘﺞ‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼ‪‬ﻠﺘﻴﻥ ﻝﺘﻔﺎﻋل ﻜ ّ‬
‫ﻤﻨﻬﻤﺎ ﻋﺒﺎﺭﺘﻲ ‪ K A‬ﻭ ‪ . K A‬ﺍﺭﺴﻡ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺩﺍﺨﻠﺔ‬
‫‪2‬‬ ‫‪1‬‬
‫ﻓﻲ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺃﻭ ﺍﻝﻨﺎﺠﻤﺔ ﻋﻨﻬﻤﺎ‪.‬‬

‫] ‪[HA−‬‬
‫= ‪ x‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ‪:‬‬ ‫‪ .2‬ﺍﺤﺴﺏ ﺍﻝﻨﺴﺒﺔ‬
‫]‪[H2A‬‬
‫‪pH = 1.50; 2.00; 2.85; 3.50; 5.00‬‬
‫ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ ؟‬
‫] ‪[A2−‬‬
‫= ‪ y‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ‪:‬‬ ‫‪ .3‬ﺍﺤﺴﺏ ﺍﻝﻨﺴﺒﺔ‬
‫] ‪[HA−‬‬
‫‪pH = 3.50; 5.00; 5.80; 6.50; 8.00‬‬
‫ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ ؟‬
‫‪ .4‬ﺍﺴﺘﻨﺘﺞ ﻤﻥ ﺍﻝﻁﻠﺒﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪. pH = 3.50‬‬
‫ﻴﻭﻀ‪‬ﺢ ﺍﻝﻤﺨﻁﹼﻁ ﺍﻝﺘﺎﻝﻲ ﺘﻭﺯﻴﻊ ﺍﻝﺤﻤﺽ ﺭﺒﺎﻋﻲ ﺨﻼﺕ ﺜﻨﺎﺌﻲ ﺃﻤﻴﻥ ﺍﻹﻴﺜﻠﻴﻥ ﺒﺩﻻﻝﺔ ﻗﻴﻤـﺔ‬ ‫‬
‫‪ . pH‬ﺴﻨﺭﻤﺯ ﺇﻝﻰ ﻫﺫﺍ ﺍﻝﺤﻤﺽ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﺴﺄﻝﺔ ﺒﺎﻝﺭﻤﺯ ‪. H4Y‬‬
‫‪%‬‬
‫‪90‬‬
‫
‬ ‫‬
‫‪80‬‬
‫‬
‫‪70‬‬
‫‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫ ‬
‫‪20‬‬
‫‪10‬‬
‫‪pH‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8‬‬ ‫‪9 10 11 12 13 14‬‬
‫ل ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺨﻤﺴﺔ ﻋﻠﻰ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ؟‬

‫‪ .1‬ﻤﺎﺫﺍ ﺘﻤﺜﹼل ﻜ ّ‬
‫‪ .2‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻡ ‪ pK A‬ﺍﻝﻤﺘﻌﻠﻘﺔ ﺒﺎﻷﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻠﺤﻤﺽ ‪. H4Y‬‬
‫‪i‬‬
‫‪ .3‬ﻋﻴ‪‬ﻥ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺘﻲ ﺘﺼﺒﺢ ﺒﺩﺀ ﹰﺍ ﻤﻨﻬﺎ ﺍﻝﻨﺴﺒﺔ ﺍﻝﻤﺌﻭﻴﺔ‬
‫ﺍﻝﻤﺘﻌﻠﻘﺔ ﺒﺎﻝﺸﺎﺭﺩﺓ ‪ Y 4−‬ﺃﻜﺒﺭ ﻤﻥ ‪. 90%‬‬
‫ﺽ ﺍ ﻝﻠﻴﻤﻭ ﻥ ‪ C6 H 8O7‬ﺤﻤﺽ‪ ‬ﺜﻼ ﺜﻲ ﺍ ﻝﻭ ﻅﻴﻔﺔ ﻭﺴﻨﺴﻤﻴﻪ ﻓﻴﻤﺎ ﻴﻠﻲ ‪. H3A‬‬

‫ﻥ ﺤﻤ ‪‬‬
‫ﺇ ‪‬‬ ‫‬
‫ﻴﻌﻁﻲ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﺘﻭﺯﻴﻊ ﺠﻤﻴﻊ ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺤﺎﻭﻴﺔ ﻋﻠﻰ‬
‫‪ A‬ﺒﺩﻻﻝﺔ ﺍﻝـ ‪. pH‬‬
‫‪%‬‬
‫‪90‬‬
‫‪80‬‬ ‫
‬ ‫ ‬ ‫‬ ‫‬
‫‪70‬‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪pH‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8‬‬ ‫‪9 10 11 12 13 14‬‬
‫ل ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻷﺭﺒﻌﺔ ﻋﻠﻰ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ؟‬

‫‪ .1‬ﻤﺎﺫﺍ ﻴﻤﺜﹼل ﻜ ّ‬
‫‪ .2‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻡ ﺍﻝـ ‪ pK A‬ﺍﻝﻤﺘﻌﻠﻘﺔ ﺒﺎﻷﺯﻭﺍﺝ ﺤﻤﺽ ‪/‬ﺃﺴﺎﺱ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻠﺤﻤﺽ ‪. H3A‬‬
‫‪i‬‬
‫ل ‪ 1.05 g‬ﻤﻥ ﺤﻤﺽ ﺍﻝﻠﻴﻤﻭﻥ‬

‫ﻻ ﺤﺠﻤﻪ ‪ 250.0 mL‬ﻋﻥ ﻁﺭﻴﻕ ﺤ ّ‬
‫‪ .3‬ﺤﻀ‪‬ﺭﻨﺎ ﻤﺤﻠﻭ ﹰ‬
‫ﺃﺤﺎﺩﻱ ﺍﻝﻤﺎﺀ ‪ C6 H 8O7 .H2O‬ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ‪.‬‬
‫ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺯ ﺍﻝﻤﺤﻠﻭل ‪.C‬‬ ‫‬
‫ﺤﺩ‪‬ﺩ ﺒﺎﺴﺘﻌﻤﺎل ‪ C‬ﻭﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ ﺍﻝﺤﺎﻭﻴﺔ ﻋﻠﻰ‬ ‫‬
‫‪ A‬ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪. pH = 4.50‬‬

‫ﺍﻝﻤﻌﻁﻴﺎﺕ ‪:‬‬
‫‪. m(H) = 1g/mol ، m(O) = 16 g/mol ، m(C) = 12 g/mol‬‬
‫ل ﻤﻥ ﺍ ﻝﻨﺸﺎﺩﺭ ‪ NH3‬ﻭﺍﻹﻴﺜﺎﻨﻭ ل ‪ C2 H5OH‬ﻜﺎﻝﻤﺎﺀ ﺘﻤﺎﻤﹰﺎ ﺒﺘﻔﺎﻋل ﺘﺤﻠﻴل‬

‫ﻴﺘﻤﺘﹼﻊ ﻜ ّ‬ ‫‬
‫ﺒﺭﻭﺘﻭﻨﻲ ﺫﺍﺘﻲ‪.‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎ ﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻝﺘﻲ ﺘﻌﺒ‪‬ﺭ ﻋﻥ ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪ ،‬ﺜ ‪‬ﻡ ﺍ ﻜﺘﺏ‬
‫ﻋﺒﺎﺭﺓ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻭﻋﺒﺎﺭﺓ ﺍﻝـ ‪. pH‬‬
‫‪ .2‬ﻋﻠﻰ ﺍﻝﻤﻨﻭﺍل ﺫﺍﺘﻪ‪ ،‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺘﻲ ﺘﻌﺒ‪‬ﺭ ﻋﻥ ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ‬
‫ﻝﻠﻨﺸﺎﺩﺭ‪ ،‬ﺜ ‪‬ﻡ ﺍﻜﺘﺏ ﻋﺒﺎﺭﺓ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻭﻋﺒﺎﺭﺓ ﺍﻝـ ‪ pH‬ﻓﻲ ﺍﻝﻨﺸﺎﺩﺭ‪.‬‬
‫‪ .3‬ﺃﻋﺩ ﺍﻝﺴﺅﺍل ﺍﻝﺴﺎﺒﻕ ﺫﺍﺘﻪ ﻭﻝﻜﻥ ﻓﻲ ﺤﺎﻝﺔ ﺍﻹﻴﺜﺎﻨﻭل‪.‬‬
‫ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻴﺩ ‪ H−‬ﻤﻊ ﺍﻝﻤﺎﺀ ﻝﺘﻌﻁﻲ ﺜﻨﺎﺌﻲ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻭﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪.‬‬ ‫‬
‫‪ .1‬ﺍﻜﺘﺏ ﺼﻴﻐﺔ ﻝﻭﻴﺱ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻴﺩ‪.‬‬
‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻴﺩ ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .3‬ﺒﻴ‪‬ﻥ ﺃﻨﻪ ﻴﻤﻜﻥ ﺍﻋﺘﺒﺎ ﺭ ﺍ ﻝﺘﻔﺎ ﻋل ﺍ ﻝﺴﺎﺒﻕ ﺘﻔﺎ ﻋل ﺤﻤﺽ‪ -‬ﺃﺴﺎ ﺱ ‪ ،‬ﺜ ‪‬ﻡ ﺤﺩ‪‬ﺩ ﺍﻷ ﺯﻭ ﺍﺝ‬
‫ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻴﻪ‪.‬‬
‫‪ .4‬ﺒﻴ‪‬ﻥ ﺃﻨﻪ ﻴﻤﻜﻥ ﺃﻴﻀﹰﺎ ﺍﻋﺘﺒﺎﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ‪-‬ﺇﺭﺠﺎﻉ‪ ،‬ﺜ ‪‬ﻡ ﺤﺩ‪‬ﺩ ﺍﻷﺯﻭﺍﺝ‬
‫ﻤﺅﻜﺴﺩ‪/‬ﻤﺭﺠﻊ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻴﻪ‪.‬‬
‫ﻻ ﻤﻥ ﺤﻤﺽ‬
‫ل ‪ 5.00 × 10−2‬ﻤﻭ ﹰ‬
‫ﻻ ﺒﺤﺠﻡ ‪ ، 250.0 mL‬ﻭ ﺫ ﻝﻙ ﺒﺤ ّ‬
‫ﻨﺤﻀ‪‬ﺭ ﻤﺤﻠﻭ ﹰ‬ ‫ ‬
‫ﻥ‪:‬‬
‫ﻻ ﻤﻥ ﻨﻤﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ .‬ﻓﺈﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﺍﻵﺯﻭﺘﻲ ﻤﻊ ‪ 8.00 × 10−2‬ﻤﻭ ﹰ‬
‫‪pK A (HNO2 / NO−‬‬
‫‪2 ) = 3.20‬‬
‫‪pK A(HCOOH / HCOO− ) = 3.80‬‬
‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪.‬‬
‫‪ .3‬ﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪.‬‬
‫‪ .4‬ﺍﻜﺘﺏ ﺠﻤﻴﻊ ﺍ ﻝﻤﻌﺎﺩﻻﺕ ﺍ ﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎ ﻋﻼﺕ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﺤﺩﺙ ﻓﻲ ﺍ ﻝﻤﺤﻠﻭل‬
‫ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻝﻜل ﻤﻨﻬﺎ‪ .‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .5‬ﺃﻭﺠﺩ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﻨﻬﺎﺌﻲ ﻝﺸﺎﺭﺩﺓ ﺍﻝﻨﻤﻼﺕ ‪. HCOO−‬‬
‫ﻁ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺘﻘﺭﻴﺒﻴﺔ ﻝﻠﻤﺤﻠﻭل‪.‬‬
‫‪ .6‬ﺃﻋ ‪‬‬
‫‪، C6 H5NH+‬‬
‫ﻻ ﻤﻥ ﻜﻠﻭ ﺭ ﺍﻷﻨﻴﻠﻴﻨﻴﻭ ﻡ ‪3 Cl‬‬
‫‪−‬‬
‫ل ﻤﻘﺩ ﺍ ﺭ ﹰﺍ ﻗﺩ ﺭﻩ ‪ 2.00 × 10−2‬ﻤﻭ ﹰ‬
‫ﻨﺤ ّ‬ ‫
‬
‫‪، Na + BO−‬‬
‫ﻻ ﻤﻥ ﺒﻭﺭﺍﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ‪2‬‬
‫‪ pK A = 4.50‬ﻭ ﻤﻘﺩﺍﺭ ‪ 3.00 × 10−2‬ﻤﻭ ﹰ‬
‫‪ pK A = 9.20‬ﻓﻲ ‪ 200.0 cm 3‬ﻤﻥ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ‪.‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﻋﻠﻰ ﻤﺤﻭﺭ ﺸﺎﻗﻭﻝﻲ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻤﺭﻜﱢﺒﺎﺕ ﺍﻷﺯﻭﺍﺝ ﺤﻤﺽ‪ /‬ﺃﺴﺎﺱ ﺍﻝﻭﺍﺭﺩﺓ‬
‫ﻓﻲ ﺍﻝﻤﺴﺄﻝﺔ‪.‬‬
‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪ ،‬ﻭﺤﺩ‪‬ﺩ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪ .‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .3‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋﻼﺕ ﺍﻷﺨﺭﻯ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﺤﺩﺙ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪،‬‬
‫ﻭﺤﺩ‪‬ﺩ ﺜﻭﺍﺒﺕ ﺘﻭﺍﺯﻨﻬﺎ‪ .‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .4‬ﺤﺩ‪‬ﺩ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻝﻠﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺜ ‪‬ﻡ ﺃﻭﺠﺩ ﺍﻝﻘﻴﻤﺔ‬
‫ﺍﻝﺘﻘﺭﻴﺒﻴ‪‬ﺔ ﻝـ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻻ ﻤﻥ‪:‬‬
‫ل ‪ 0.100‬ﻤﻭ ﹰ‬
‫ل ﻤﻨﻬﺎ ﺒﺤﺠﻡ ﻝﻴﺘﺭ ﻭﺍﺤ ‪‬ﺩ ﻭﺫﻝﻙ ﺒﺤ ّ‬
‫ﻨﺤﻀ‪‬ﺭ ﺜﻼﺜﺔ ﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ ﻜ ّ‬ ‫‬
‫ﺜﻨﺎﺌﻲ ﻫﻴﺩﺭﻭﺠﻴﻥ ﻓﻭﺴﻔﺎﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ ‪. NH4 H2 PO4‬‬ ‫‬
‫ﺃﺤﺎﺩﻱ ﻫﻴﺩﺭﻭﺠﻴﻥ ﻓﻭﺴﻔﺎﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ ‪. (NH 4 )2 HPO4‬‬ ‫‬
‫ﻓﻭﺴﻔﺎﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ ‪. (NH 4 )3 PO4‬‬ ‫‬
‫ﻥ ‪pK A‬‬
‫ﻥ ﻗﻴﻡ ‪ pK A‬ﻝﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ ﻫﻲ ‪ ،12.10 ،7.20 ،2.15‬ﻭﺃ ‪‬‬
‫ﻓﺈﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫‪i‬‬
‫ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ ﺘﺴﺎﻭﻱ ‪.9.20‬‬

‫‪ .1‬ﺍﺭﺴﻡ ﻤﺨﻁﻁﺎﺕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ ﺍﻝﻭﺍﺭﺩﺓ ﻓﻲ ﺍﻝﻤﺴﺄﻝﺔ‪.‬‬
‫ل ﻤﺤﻠﻭل ﻤﻥ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺜﻼﺜﺔ ﺍﻝﻤﻌﺎﺩﻝ ﹶﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﻜﻴﻤﻴﺎﺌﻲ ﺍﻝﺫﻱ‬
‫‪ .2‬ﺍﻜﺘﺏ ﻝﻜ ّ‬
‫ﺠﺭﻯ ﺒﻴﻥ ﺍﻝﻤﻭﺍﺩ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻲ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪.‬‬
‫‪ .3‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺜﺎﻨﻲ‪:‬‬
‫ل ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻷﺨﺭﻯ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﺤﺩﺙ‪.‬‬
‫)‪ (a‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻜ ّ‬
‫ل ﻤﺭﺓ ﺜﻭﺍﺒﺕ ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻻﺕ‪ ،‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫)‪ (b‬ﺤﺩ‪‬ﺩ ﻓﻲ ﻜ ّ‬
‫)‪ (c‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺘﻘﺭﻴﺒﻴﺔ ﻝﻠﻤﺤﻠﻭل‪.‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻧﻲ‬
‫ ‪

pH‬‬
‫‪ .I‬ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‬

‫‪ .1.I‬ﺍﻷﻨﻭﺍﻉ ﺍﻝﻐﺎﻝﺒﺔ ﻭﺍﻝﻤﻐﻠﻭﺒﺔ ﻭﺍﻝﻤﻬﻤﻠﺔ‬
‫‪ .2.I‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺤﻤﻀﻴﺔ ﻭﺍﻝﻤﺤﺎﻝﻴل ﺍﻷﺴﺎﺴﻴﺔ‬
‫‪ .3.I‬ﺍﻝﺩﻗﺔ ﻓﻲ ﻗﻴﺎﺱ ‪ pH‬ﻤﺤﻠﻭل‬
‫‪ .4.I‬ﺘﺤﻀﻴﺭ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻝﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ‬
‫‪ .II‬ﺒﻌﺽ ﺤﺴﺎﺒﺎﺕ ‪ pH‬ﻝﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ‬
‫‪ .1.II‬ﺍﻝﻁﺭﻴﻘﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ‬
‫‪ .2.II‬ﻁﺭﻴﻘﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‬
‫‪ .3.II‬ﺤﻤﺽ ﻗﻭﻱ‪ ،‬ﺃﺴﺎﺱ ﻗﻭﻱ‬
‫‪ .4.II‬ﺤﻤﺽ ﻀﻌﻴﻑ‪ ،‬ﺃﺴﺎﺱ ﻀﻌﻴﻑ‬
‫‪ .5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﻭﺽ ﺃﻭ ﻤﺯﻴﺞ ﻤﻥ ﺃﺴﺱ‬
‫‪ .6.II‬ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ‬
‫‪ .7.II‬ﻤﺘﺫﺒﺫﺏ ﺤﻤﻀﻲ ﺃﺴﺎﺴﻲ‬
‫‪ .8.II‬ﺒﻌﺽ ﻤﺯﺍﺌﺞ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ‬
‫‪41‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﱐ‬ ‫‪42‬‬
‫‪ .I‬ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‬
‫ﻗﺒل ﺍﻝﺩﺨﻭل ﻓﻲ ﺤﺴﺎﺒﺎﺕ ‪ pH‬ﺒﻌﺽ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﻤﻥ ﺍﻝﻤﻔﻴﺩ ﺃﻥ ﻨﻌﻴﺩ ﺍﻝﺘﺫﻜﻴﺭ ﺒﺒﻌﺽ‬
‫ﺍﻝﻔﺭﻀﻴﺎﺕ ﻭﺸﺭﻭﻁ ﺍﻝﺩﺭﺍﺴﺔ‪.‬‬
‫‪ .1.I‬ﺍﻷﻨﻭﺍﻉ ﺍﻝﻐﺎﻝﺒﺔ ﻭﺍﻝﻤﻐﻠﻭﺒﺔ ﻭﺍﻝﻤﻬﻤﻠﺔ‬
‫ﻋﻨﺩﻤﺎ ﻨﻜﺘﺏ ﻤﻌﺎﺩﻝﺔ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﻓﻲ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻓﻤﻥ ﺍﻝﻤﻌﻘﻭل ﺃﻥ ﻨﻬﻤل ﺘﺭﻜﻴﺯ ﺍﻝﻨﻭﻉ‬
‫‪ X‬ﺒﻭﺠﻭﺩ ﺍﻝﻨﻭﻉ ‪ ،Y‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ‪ X‬ﺼﻐﻴﺭ ﹰﺍ ﺒﺎﻝﻤﻘﺎﺭﻨﺔ ﻤﻊ ‪ .Y‬ﻭﻴﻜﻭﻥ ﻫﺫﺍ‬
‫ﻤﺤﻘﻘﹰﺎ ﻋﻤﻠﻴﹰﺎ ﻋﻨﺩﻤﺎ‪:‬‬
‫)‪(1‬‬ ‫‪[X ] ≤ [Y ] / 10‬‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺤﺎﻝﺔ ﺯﻭﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ‪ ، A / B‬ﻭﻝﻨﻜﺘﺏ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺘﻲ ﺘﺭﺒﻁ ﺒﻴﻥ ﺘﺭﻜﻴﺯﻱ‬
‫ﺍﻝﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ ﺒﺎﺴﺘﻌﻤﺎل ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‪:‬‬
‫] ‪[B‬‬
‫‪pH = p K A + log‬‬
‫]‪[A‬‬
‫ﻝﻨﻁﺒ‪‬ﻕ ﺍﻝﺸﺭﻁ ﺍﻝﺴﺎﺒﻕ )‪: (1‬‬

‫ﻼ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺍﻝﻨﻭﻉ ﺍﻷﺴﺎﺴﻲ ‪ B‬ﻴﻜﻭﻥ ﻤﻬﻤ ﹰ‬
‫♦ ﻋﻨﺩﻤﺎ ‪ ، pH ≤ p K A − 1‬ﻓﺈ ‪‬‬
‫ﺍﻝﻨﻭﻉ ﺍﻝﺤﻤﻀﻲ‪. [B ] ≪ [A] :‬‬
‫ﻼ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺍﻝﻨﻭﻉ ﺍﻝﺤﻤﻀﻲ ‪ A‬ﻴﻜﻭﻥ ﻤﻬﻤ ﹰ‬
‫♦ ﻋﻨﺩﻤﺎ ‪ ، pH ≥ p K A + 1‬ﻓﺈ ‪‬‬
‫ﺍﻝﻨﻭﻉ ﺍﻷﺴﺎﺴﻲ‪. [A] ≪ [B ] :‬‬
‫ﻴﻠﺨﹼﺹ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺤﻤﻀﻴﺔ ﻭﺍﻷﺴﺎﺴﻴﺔ ﺍﻝﻤﻬﻤﻠﺔ‪ ،‬ﻭﺫﻝﻙ ﺒﺩﻻﻝﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪.‬‬
‫‪pkA −3‬‬ ‫‪pkA −2‬‬ ‫‪pkA −1‬‬ ‫‪pkA‬‬ ‫‪pkA +1‬‬ ‫‪pkA +2‬‬ ‫‪pkA +3‬‬ ‫‪pH‬‬
‫] ‪[A] > [B‬‬ ‫]‪[B ] > [A‬‬
‫‪ A‬ﺭﺍﺠﺢ‬ ‫‪ B‬ﺭﺍﺠﺢ‬
‫‪ B‬ﻤﻬﻤل ﻷ ‪‬ﻥ ] ‪[A] ≫ [B‬‬ ‫]‪ [A‬ﻭ ] ‪ [B‬ﻝﻬﻤﺎ ﺍﻝﻤﺭﺘﺒﺔ ﻨﻔﺴﻬﺎ‬ ‫‪ A‬ﻤﻬﻤل ﻷ ‪‬ﻥ ]‪[B ] ≫ [A‬‬
‫] ‪[A] ≥ 100 ⋅ [B‬‬ ‫]‪[B ] ≥ 100 ⋅ [A‬‬
‫‪ A‬ﻏﺎﻝﺏ ﻭ ‪ B‬ﻤﻐﻠﻭﺏ‬ ‫‪ B‬ﻏﺎﻝﺏ ﻭ ‪ A‬ﻤﻐﻠﻭﺏ‬
‫‪43‬‬ ‫ﺣﺴﺎﺏ ‪ pH‬ﺑﻌﺾ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫‪ .2.I‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺤﻤﻀﻴﺔ ﻭﺍﻝﻤﺤﺎﻝﻴل ﺍﻷﺴﺎﺴﻴﺔ‬
‫ﺇﻥ ﺘﻁﺒﻴﻕ ﺍﻝﺸﺭﻁ )‪ (1‬ﻋﻠﻰ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻭﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻴﺴﻤﺢ ﺒﺘﺤﺩﻴﺩ ﻤﺎ ﻨﺴﻤ‪‬ﻴﻪ‬
‫ﻻ ﺤﻤﻀﻴﹰﺎ ﺒﻭﻀﻭﺡ ﺃﻭ ﺃﺴﺎﺴﻴﹰﺎ ﺒﻭﻀﻭﺡ‪:‬‬
‫ﻋﺎﺩﺓ ﻤﺤﻠﻭ ﹰ‬
‫‪ o‬ﻴﻜﻭ ﻥ ﺍ ﻝﻤﺤﻠﻭ ل ﺤﻤﻀﻴﹰﺎ ﺒﻭﻀﻭ ﺡ ﻋﻨﺩ ﻤﺎ ] ‪ ، [H 3O+ ] ≥ 10 ⋅ [OH−‬ﻭ ﺒﺎ ﻻﺴﺘﻌﺎ ﻨﺔ‬

‫ﺒﺎﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ‪ K w = [H 3O+ ] ⋅ [OH− ] :‬ﺘﺼﺒﺢ ﺍﻝﻤﺘﺭﺍﺠﺤﺔ ﺍﻝﺴﺎﺒﻘﺔ ﻜﻤﺎ‬
‫‪Kw‬‬
‫⋅ ‪. [H 3O+ ] ≥ 10‬‬ ‫ﻴﻠﻲ ‪:‬‬
‫] ‪[H3O+‬‬
‫‪1‬‬
‫≤ ‪. pH‬‬ ‫ﺃﻱ ‪ ، [H 3O+ ]2 ≥ 10 × K w‬ﺃﻭ )‪⋅ (pK w − 1‬‬
‫‪2‬‬
‫ﻭﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻴﻜﻭﻥ ‪. pH ≤ 6.5‬‬
‫‪ o‬ﻴﻜﻭ ﻥ ﺍ ﻝﻤﺤﻠﻭ ل ﺃﺴﺎﺴﻴﹰﺎ ﺒﻭﻀﻭ ﺡ ﻋﻨﺩ ﻤﺎ ] ‪ ، [OH− ] ≥ 10 ⋅ [H3O+‬ﻭ ﺒﺎ ﻻﺴﺘﻌﺎ ﻨﺔ‬
‫ﺒﺎﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ‪ ،‬ﺘﺼﺒﺢ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺴﺎﺒﻘﺔ ﻜﻤﺎ ﻴﻠﻲ‪:‬‬
‫‪Kw‬‬
‫] ‪≥ 10 ⋅ [H3O+‬‬
‫‪+‬‬
‫] ‪[H 3O‬‬
‫‪1‬‬
‫≥ ‪. pH‬‬ ‫ﺃﻱ ‪ ، [H 3O+ ]2 ≤ 0.10 × K w‬ﺃﻭ )‪⋅ (pK w + 1‬‬
‫‪2‬‬
‫ﻭﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻴﻜﻭﻥ ‪. pH ≥ 7.5‬‬
‫ﻓﻲ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪: 25 C‬‬

‫ﻼ ﺃﻤﺎﻡ ] ‪ [H 3O+‬؛‬
‫• ﺇﺫﺍ ﻜﺎﻨﺕ ‪ ، pH ≤ 6.5‬ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ] ‪ [OH−‬ﻤﻬﻤ ﹰ‬
‫ﻼ ﺃﻤﺎﻡ ] ‪. [OH−‬‬
‫• ﺇﺫﺍ ﻜﺎﻨﺕ ‪ ، pH ≥ 7.5‬ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ] ‪ [H 3O+‬ﻤﻬﻤ ﹰ‬
‫ﻫﺫﺍ ﻴﻌﻭﺩ ﻤﻥ ﻭﺠﻬﺔ ﻨﻅﺭ ﻜﻴﻤﻴﺎﺌﻴﺔ ﺇﻝﻰ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ﻤﻘﺎﺒل‬
‫ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻷﺨﺭﻯ ﺍﻝﻤﻤﻜﻨﺔ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ‪ pH ≤ 6.5‬ﺃﻭ ‪. pH ≥ 7.5‬‬
‫‪‬ﻴﺠﻤل ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﻨﺎ ﺇﻝﻴﻬﺎ‪.‬‬

‫ﻭﺳﻂ ﲪﻀﻲ‬ ‫‪6.5‬‬ ‫‪7.0‬‬ ‫‪7.5‬‬ ‫ﻭﺳﻂ ﺃﺳﺎﺳﻲ‬

‫‪pH‬‬
‫ﻭﺴﻁ ﺤﻤﻀﻲ ﺒﻭﻀﻭﺡ‪.‬‬ ‫ﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل‬ ‫ﻭﺴﻁ ﺃﺴﺎﺴﻲ ﺒﻭﻀﻭﺡ‪.‬‬
‫ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‬ ‫ﺍﻝﺒﺭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‬ ‫ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‬
‫] ‪[H3O+ ] >> [OH−‬‬ ‫] ‪[H3O+ ] ≈ [OH−‬‬ ‫] ‪[H3O+ ] << [OH−‬‬
‫‪ .3.I‬ﺍﻝﺩﻗﺔ ﻓﻲ ﻗﻴﺎﺱ ‪ pH‬ﻤﺤﻠﻭل‬
‫ﻝﻨﺤﺴﺏ ﺍﻝﺨﻁﺄ ﺍﻝﻤﺭﺘﹶﻜﺏ ﻓﻲ ﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﻴ‪‬ﺤﺩ‪‬ﺩ ﺒﻘﻴﺎﺱ‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫ﻝﺩﻴﻨﺎ ] ‪ pH = − log[H 3O+‬ﺘﻌﺭﻴﻔﹰﺎ‪ .‬ﺃﻱ ] ‪ ، 2.3 pH = − ln[H3O+‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ‬
‫ﻥ‪:‬‬
‫ﺃ‪‬‬
‫] ‪d[H3O+‬‬
‫‪2.3 × d(pH) = −d( ln[H3O+ ]) = −‬‬
‫] ‪[H3O+‬‬
‫ﻭﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫] ‪d[H3O+‬‬
‫)‪= −2.3 × d(pH‬‬
‫] ‪[H3O+‬‬
‫ﻥ ﺍﻝﻘﻴﻤﺔ‬
‫ﺒﺎﻓﺘﺭﺍﺽ ﺃﻥ ﺍﻝﺘﻔﺎﻀﻠﻴﻥ ] ‪ d[H3O+‬ﻭ )‪ d(pH‬ﻴﻤﺜﻼﻥ ﺍﻝﺨﻁﺄ‪ ،‬ﻭﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫ﻻ ﺍﺭﺘﻴﺎﺏ ﺍﻝﻘﻴﺎﺱ ] ‪ ∆[H3O+‬ﻭ )‪ ∆(pH‬ﻴﻜﻭﻥ‬
‫ﺍﻝﻌﻅﻤﻰ ﻝﻠﻘﻴﻤﺔ ﺍﻝﻤﻁﻠﻘﺔ ﻝﻜلّ ﻤﻨﻬﻤﺎ ﻤﺎ ﻫﻲ ﺇ ﹼ‬
‫ﻝﺩﻴﻨﺎ‪:‬‬
‫] ‪∆[H3O+‬‬
‫)‪= 2.3 × ∆(pH‬‬
‫] ‪[H3O+‬‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺍﻵﻥ ﺍﻝﺠﺩﻭل ﺍﻝﺘﺎﻝﻲ ﺍﻝﺫﻱ ‪‬ﻴﻅﻬﺭ ﺍﻝﺩﻗﺔ ﻓﻲ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺒﺩﻻﻝﺔ‬
‫ﺍﻻﺭﺘﻴﺎﺏ ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫)‪∆(pH‬‬ ‫] ‪∆[H 3O+‬‬
‫] ‪[H3O+‬‬
‫‪0.01‬‬ ‫‪2.3%‬‬
‫‪0.05‬‬ ‫‪11.5%‬‬
‫‪0.1‬‬ ‫‪23%‬‬
‫ﻤﻥ ﺩﺭﺍﺴﺔ ﺍﻝﺠﺩﻭل ﺍﻝﺴﺎﺒﻕ ﻨﺴﺘﻨﺘﺞ ﻤﺎ ﻴﻠﻲ ‪:‬‬

‫ﻥ ﺍﻝﺩﻗﺔ‬
‫• ﺇﺫﺍ ﻜﺎﻨﺕ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻤﻌﻠﻭﻤﺔ ﺒﺎﺭﺘﻴﺎﺏ ﻗﺩﺭﻩ ‪ ±0.05‬ﻭﺤﺩﺓ‪ ،‬ﻓﺈ ‪‬‬
‫‪. 11.5%‬‬ ‫ﻻ‬
‫ﻓﻲ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻝﻴﺴﺕ ﺇ ﹼ‬
‫• ﻭﺒﺎﻝﻌﻜﺱ ﺤﺘﻰ ﺘﻜﻭﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻤﻌﻠﻭﻤﺔ ﺒﺎﺭﺘﻴﺎﺏ ‪ ±0.05‬ﻭﺤﺩﺓ‪،‬‬
‫‪. 11.5%‬‬ ‫ﻴﻜﻔﻲ ﻤﻌﺭﻓﺔ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺒﺩﻗﹼﺔ‬
‫ﻭﻫﻜﺫﺍ ﻨﺼل ﺇﻝﻰ ﺍﻝﻨﺘﻴﺠﺘﻴﻥ ﺍﻝﻤﻬﻤﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ‪:‬‬
‫• ﻋﻨﺩﻤﺎ ﻨﺤﺴﺏ ‪ pH‬ﻤﺤﻠﻭل ﻴﻨﺒﻐﻲ ﺇﻋﻁﺎﺀ ﺍﻝﻨﺘﻴﺠﺔ ﺒﻤﺎ ﻻ ﻴﺘﺠﺎﻭﺯ ﺭﻗﻤﻴﻥ ﻋﺸﺭﻴﻴﻥ‪.‬‬
‫• ﻴﻨﺒﻐﻲ ﻋﺩﻡ ﺍﻻﻋﺘﻤﺎﺩ ﻋﻠﻰ ﻗﻴﺎﺱ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻝﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ‬
‫ﺃﻭ ﺘﺭﻜﻴﺯ ﺃﻱ ﻨﻭﻉ ﺁﺨﺭ‪ ،‬ﻭﺇﻨﻤﺎ ﻴﻠﺯﻡ ﻝﺘﺤﻘﻴﻕ ﺫﻝﻙ ﺍﻝﻠﺠﻭﺀ ﺇﻝﻰ ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫‪ .4.I‬ﺘﺤﻀﻴﺭ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻝﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ‬
‫ﻥ ﻝﺩﻴﻨﺎ ﻤﺭﻜﺒﹰﺎ ﺸﺎﺭﺩﻴﹰﺎ ‪ C x Ay‬ﻨﺴﻤﻴﻪ ﺃﺤﻴﺎﻨﹰﺎ ﻤﻠﺤﹰﺎ ) ﻨﺫﻜﹼﺭ ﺒﺄﻥ ﺍﻝﻤﻠﺢ ﻫﻭ ﻤﺭﻜﹼﺏ‬
‫ﻝﻨﻔﺘﺭﺽ ﺃ ‪‬‬
‫ﻜﻴﻤﻴﺎ ﺌﻲ ﻴﻨﺘﺞ ﻋﻥ ﺍ ﺭ ﺘﺒﺎ ﻁ ﺸﻭ ﺍ ﺭ ﺩ ﻤﻭ ﺠﺒﺔ ﻤﻊ ﺸﻭ ﺍ ﺭ ﺩ ﺴﺎ ﻝﺒﺔ ﺒﺎﺴﺘﺜﻨﺎ ﺀ ﺸﻭ ﺍ ﺭ ﺩ ﺍ ﻝﻬﻴﺩ ﺭ ﻭ ﻨﻴﻭﻡ‬
‫ﻭﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ(‪ .‬ﻋﻨﺩﻤﺎ ﻨﻀﻌﻪ ﻓﻲ ﺍﻝﻤﺎﺀ ﻓﺈﻨﻨﺎ ﻨﻘﺒل‪ ،‬ﻤﺎﺩﺍﻡ ﺍﻝﻤﺤﻠﻭل ﻏﻴﺭ ﻤﺸﺒﻊ‪ ،‬ﺃﻨﹼﻪ – ﻓﻲ ﻤﺭﺤﻠﺔ‬
‫ﺃﻭﻝﻰ‪ -‬ﻴﺤﺼل ﺘﻔﺎﻋل ﺘﻔﻜﹼﻙ ﺍﻝﻤﻠﺢ ﻭﻴﻜﻭﻥ ﺘﺎﻤﹰﺎ ‪ ،‬ﺜ ‪‬ﻡ ﻓﻲ ﺍﻝﻤﺭﺤﻠﺔ ﺍﻝﺜﺎﻨﻴﺔ ﻴﻤﻜﻥ ﻝﺸﻭﺍﺭﺩ ‪C p +‬‬
‫ﻭ ‪ Aq −‬ﺍﻝﻨﺎﺘﺠﺔ ﺃﻥ ﺘﺘﻔﺎﻋل ﻤﻊ ﺍﻝﻤﺎﺀ ﺃﻭ ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ ﻭﺫﻝﻙ ﺘﺒﻌﹰﺎ ﻝﻁﺒﻴﻌﺘﻬﺎ‪.‬‬
‫ﺃﻤﺜﻠﺔ‬
‫‪NaCl(s) → Na + + Cl−‬‬ ‫•‬

‫ﻻ ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ‪ Na +‬ﻭ ‪ Cl−‬ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪K2O(s) → 2 K+ + O2−‬‬ ‫•‬

‫ﻻ ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ‪ K+‬ﻤﻊ ﺍﻝﻤﺎﺀ‪ ،‬ﻓﻲ ﺤﻴﻥ ﺘﻌﺘﺒﺭ ﺸﺎﺭﺩﺓ ﺍﻷﻭﻜﺴﻴﺩ ‪ ) O2−‬ﺍﻝﺘﻲ ﻫﻲ‬
‫ﺍﻷﺴﺎﺱ ﺍﻝﻤﺭﺍﻓﻕ ﻝﻠﺸﺎﺭﺩﺓ ‪ (OH−‬ﺃﺴﺎﺴﹰﺎ ﻗﻭﻴﹰﺎ ﻭﺘﻔﺎﻋﻠﻬﺎ ﻤﻊ ﺍﻝﻤﺎﺀ ﺘﺎﻤﹰﺎ‪:‬‬
‫‪O2− + H2O → OH− + OH−‬‬
‫ﻝﻨﻨﻅﺭ ﺇﻝﻰ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬ ‫•‬

‫‪CH 3COONa(s) → CH 3COO− + Na +‬‬
‫‪NH4 NO2 (s) → NO−‬‬ ‫‪+‬‬
‫‪2 + NH 4‬‬
‫‪KH2PO4 (s) → H2 PO−‬‬
‫‪4+K‬‬
‫‪+‬‬
‫‪ CH 3COO‬ﻭ ‪2‬‬
‫‪NO−‬‬ ‫ﻥ‬
‫ﻻ ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ‪ Na +‬ﻭ ‪ K+‬ﻤﻊ ﺍﻝﻤﺎﺀ‪ .‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫‪−‬‬
‫‪ H2 PO−‬ﻤﺘﺫﺒﺫﺏ ﺤﻤﻀﻲ ﺃﺴﺎﺴﻲ‬

‫ﺃﺴﺎﺴﺎﻥ ﻀﻌﻴﻔﺎﻥ ﻭ ‪ NH 4‬ﺤﻤﺽ ﻀﻌﻴﻑ ﻭ ‪4‬‬
‫‪+‬‬
‫ﻼ ﻨﻜﺘﺏ‪:‬‬
‫ﻭﻫﻲ ﺘﺘﻔﺎﻋل ﻤﻊ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﺫﻝﻙ ﻭﻓﻕ ﺘﻭﺍﺯﻨﺎﺕ ﻤﺤﺩﻭﺩﺓ‪ .‬ﻓﻤﺜ ﹰ‬
‫‪CH 3COO− + H2O ⇌ CH 3COOH + OH−‬‬

‫‪NH+‬‬
‫‪4 + H2O ⇌ NH 3 + H 3O‬‬
‫‪+‬‬
‫‪ NO−‬ﻭﺫﻝﻙ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬

‫ﻜﺫﻝﻙ ﻴﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ‪ NH 4‬ﻤﻊ ﺍﻷﺴﺎﺱ ‪2‬‬
‫‪+‬‬
‫‪NO−‬‬ ‫‪+‬‬
‫‪2 + NH 4 ⇌ NH 3 + HNO2‬‬
‫‪ H2 PO−‬ﺇﻝﻰ ﺘﺤﻠل ﺒﺭﻭﺘﻭﻨﻲ ﺫﺍﺘﻲ‪:‬‬

‫ﻭﻜﺫﻝﻙ ﻴﺨﻀﻊ ﺍﻝﻤﺘﺫﺒﺫﺏ ﺍﻝﺤﻤﻀﻲ ﺍﻷﺴﺎﺴﻲ ‪4‬‬
‫‪2 H2 PO−‬‬ ‫‪2−‬‬

‫‪4 ⇌ H 3 PO4 + HPO4‬‬
‫‪ .II‬ﺒﻌﺽ ﺤﺴﺎﺒﺎﺕ ‪ pH‬ﻝﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ‬
‫ﺘﻬﺩﻑ ﻫﺫﻩ ﺍﻝﻔﻘﺭﺓ ﺇﻝﻰ ﻋﺭﺽ ﺒﻌﺽ ﺍﻝﻁﺭﺍﺌﻕ ﺍﻝﺒﺴﻴﻁﺔ ﺍﻝﺘﻲ ﺘﺴﻤﺢ ﺒﺎﻝﻭﺼﻭل ﺇﻝﻰ ﻨﺘﺎﺌﺞ‬
‫ﻤﻘﺒﻭﻝﺔ‪ ،‬ﺃﻱ ﺒﺎﺭﺘﻴﺎﺏ ﻓﻲ ﻗﻴﻡ ‪ pH‬ﻗﺩﺭﻩ ‪. ∆(pH) = 0.05‬‬
‫ﺴﻨﻌﺭﺽ ﻓﻴﻤﺎ ﻴﻠﻲ ﻁﺭﻴﻘﺘﻴﻥ ﻝﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪ :‬ﺍﻷﻭﻝﻰ ﻋﺎﻤﺔ ﻻ ﺘﻀ ‪‬ﻡ ﺃﻴﺔ‬
‫ﺘﻘﺭﻴﺒﺎﺕ ‪ ،‬ﻭﺍﻝﺜﺎﻨﻴﺔ ﺘﻌﺘﻤﺩ ﻋﻠﻰ ﺍﻝﺒﺤﺙ ﻋﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻓﻲ ﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﻭﺤﺴﺎﺏ‬
‫ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪ .‬ﻭﻤﻬﻤﺎ ﺘﻜﻥ ﺍﻝﻁﺭﻴﻘﺔ ﺍﻝﺘﻲ ﺴﻨﻌﺘﻤﺩﻫﺎ ﻓﻲ ﺍﻝﺤﺴﺎﺏ‪ ،‬ﻋﻠﻴﻨﺎ ﺍﻨﻁﻼﻗﹰﺎ ﻤﻥ ﻁﺒﻴﻌﺔ‬
‫ﺍﻷﻨﻭﺍﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﺘﻲ ﺃﻀﻴﻔﺕ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﻭﻜﻤﻴﺎﺘﻬﺎ ﺃﻥ ﻨﺼل ﺇﻝﻰ ﺘﺤﺩﻴﺩ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‬
‫ﻭﻜﺫﻝﻙ ﺇﻝﻰ ﺘﺭﺍﻜﻴﺯ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺨﺘﻠﻔﺔ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻴﻪ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪.‬‬
‫ﺒﺼﻭﺭﺓ ﻋﺎﻤﺔ‪ ،‬ﻨﻠﺠﺄ ﺇﻝﻰ ﻓﺭﻀﻴﺔ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ﻤ‪‬ﻘﺎﺒل ﺍﻝﺘﻔﺎﻋﻼﺕ‬
‫ﺍﻷﺨﺭﻯ‪ .‬ﻓﺈﺫﺍ ﻗﺎﺩﻨﺎ ﺍﻝﺤﺴﺎﺏ ﺒﺎﺴﺘﻌﻤﺎل ﻫﺫﻩ ﺍﻝﻔﺭﻀﻴﺔ ﺇﻝﻰ ﻗﻴﻤﺔ ‪ pH‬ﺒﻴﻥ ‪ 6.5‬ﻭ ‪ ، 7.5‬ﻴﺠﺏ‬
‫ﺇﻋﺎﺩﺓ ﺍﻝﺤﺴﺎﺏ ﻤﻥ ﺠﺩﻴﺩ ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪.‬‬
‫‪ .1.II‬ﺍﻝﻁﺭﻴﻘﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ‬
‫ل ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﻭﻀﻊ‬

‫ﻻ ﺒﺘﺤﺩﻴﺩ ﻜ ّ‬
‫ﺘﻌﺘﻤﺩ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻋﻠﻰ ﺍﻝﻘﻴﺎﻡ ﺃﻭ ﹰ‬
‫ﺍﻝﺘﻭﺍﺯﻥ ﺒﺤﻴﺙ ﺘﹸﻜﻭ‪‬ﻥ ﺘﺭﺍﻜﻴﺯﻫﺎ ﻤﺠﻤﻭﻋﺔ ﻤﻥ ‪ n‬ﻤﺠﻬﻭ ﹰ‬
‫ﻻ‪ .‬ﻴﻠﺯﻤﻨﺎ ﺒﻌﺩ ﺫﻝﻙ ﻝﺘﺤﺩﻴﺩ ﻫﺫﻩ ﺍﻝﻤﺠﺎﻫﻴل‬
‫ﺇﻴﺠﺎﺩ ﺠﻤﻠﺔ ﻤﻥ ‪ n‬ﻤﻌﺎﺩﻝﺔ ﻤﺴﺘﻘﻠﺔ ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ‪.‬‬
‫ﺘﻨﺘﺞ ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻻﺕ ﻋﺎﺩﺓ ﺒﻜﺘﺎﺒﺔ‪:‬‬
‫ﻤﻌﺎﺩﻻﺕ ﺍﻨﺤﻔﺎﻅ ﻜﻤﻴﺔ ﺍﻝﻤﺎﺩﺓ؛‬ ‫‬
‫ﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل؛‬ ‫‬

‫ﻤﻌﺎﺩﻻﺕ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﻤﻀﻴﺔ‪ -‬ﺍﻷﺴﺎﺴﻴﺔ ﺍﻝﺤﺎﺼﻠﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ) ‪، K A‬‬ ‫‬
‫‪. ( ...، K w‬‬

‫ﻼ ﻋﺎﺩﺓ‪ ،‬ﻭﻴﻘﻭﺩﻨﺎ ﺇﻝﻰ ﻤﻌﺎﺩﻝﺔ ﻤﻥ‬
‫ل ﺍﻝﺭﻴﺎﻀﻲ ﻝﻬﺫﻩ ﺍ ﻝﺠﻤﻠﺔ ﻤﻥ ﺍﻝﻤﻌﺎﺩﻻﺕ ﻁﻭﻴ ﹰ‬
‫ﻴﻜﻭﻥ ﺍﻝﺤ ّ‬
‫ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻝﺜﺔ ﺃﻭ ﺃﻜﺜﺭ ﺒﺎﻝﻤﺘﺤﻭل ‪ h‬ﻜﻤﺎ ﺴﻨﺭﻯ ﻓﻲ ﻤﺜﺎﻝﻨﺎ ﺍﻝﺘﻭﻀﻴﺤﻲ ﺒﻌﺩ ﻗﻠﻴل‪.‬‬
‫ﻴﻤﻜﻨﻨﺎ ﺘﺒﺴﻴﻁ ﺤل ﺠﻤﻠﺔ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺴﺎﺒﻘﺔ ‪:‬‬
‫ﺒﺈﺠﺭﺍﺀ ﺘﻘﺭﻴﺒﺎﺕ ﻨﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺘﻬﺎ ﻋﻘﺏ ﺍﻻﻨﺘﻬﺎﺀ ﻤﻥ ﺍﻝﺤﺴﺎﺏ؛‬ ‫‬
‫ل ﻤﻌﺎﺩﻝﺔ ﻜﺜﻴﺭ ﺍﻝﺤﺩﻭﺩ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ‪m‬‬

‫ﺒﺎﻝﻠﺠﻭﺀ ﺇﻝﻰ ﺒﺭﻤﺠﻴﺎﺕ ﻤﺘﺨﺼﺼﺔ ﺘﺴﻤﺢ ﺒﺤ ّ‬ ‫‬
‫ﻓﻲ ‪. h‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﺍﻝﻌﺎﻤﺔ ﻝﻴﺴﺕ ﺍﻝﻁﺭﻴﻘﺔ ﺍﻝﺘﻲ ﻴﺘﺒﻌﻬﺎ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﻭﻥ‬
‫ﻤﻥ ﺍﻝﻤﻔﻴﺩ ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ ﺃ ‪‬‬
‫ﻋﺎﺩﺓ ‪ ،‬ﻭﺇﻨﻤﺎ ﻴﻠﺠﺅﻭﻥ ﺇﻝﻰ ﻁﺭﻴﻘﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻷﻨﻬﺎ ﺃﺒﺴﻁ ﻭﺫﺍﺕ ﻤﻘﺎﺭﺒﺔ ﻜﻴﻤﻴﺎﺌﻴﺔ ﺃﻜﺜﺭ ﻤﻥ‬
‫ﻻ ﻨﻭﻀ‪‬ﺢ ﻓﻴﻪ ﻜﻴﻑ ﻨﺴﺘﻌﻤل‬
‫ل ﺍﻝﻤﺴﺄﻝﺔ‪ .‬ﻭﻝﻜﻥ ﻗﺒل ﻋﺭﺽ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻝﻨﺄﺨﺫ ﻤﺜﺎ ﹰ‬
‫ﺴﺎﺒﻘﺘﻬﺎ ﻓﻲ ﺤ ّ‬
‫ﺍﻝﻁﺭﻴﻘﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ‪.‬‬
‫ﻤﺜﺎل ﻋﻥ ﺍﻝﻁﺭﻴﻘﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ‪:‬‬
‫ﺃﻭﺠﺩ ﺠﻤﻠﺔ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﻲ ﺘﻔﻴﺩ ﻓﻲ ﺇﻴﺠﺎﺩ ﺘﺭﻜﻴﺏ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻤﻥ ﻜﻠﻭﺭ ﻴﺩ ﺍﻷﻤﻭﻨﻴﻭﻡ‬
‫ﺘﺭﻜﻴﺯﻩ ‪ c‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪. 25 C‬‬
‫ﻋﻨﺩﻤﺎ ﻨﻀﻊ ‪ NH4Cl‬ﻓﻲ ﺍﻝﻤﺎﺀ ﻴﺘﺤﻠﹼل ﺘﻤﺎﻤﹰﺎ ﻤﻌﻁﻴﹰﺎ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ‪ Cl−‬ﻭﺸﻭﺍﺭﺩ‬
‫ﺍﻷﻤﻭﻨﻴﻭﻡ ‪4‬‬
‫‪ NH+‬ﺍﻝﺘﻲ ﻫﻲ ﺒﺩﻭﺭﻫﺎ ﺤﻤﺽ ﻀﻌﻴﻑ ﻴﺘﻔﺎﻋل ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﻓﻕ ﺘﻔﺎﻋل ﻤﺤﺩﻭﺩ‪.‬‬
‫ﻴﺨﻀﻊ ﺍﻝﻤﺤﻠﻭل ﺇﺫﻥ ﻝﻠﺘﻭﺍﺯﻨﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬

‫‪NH+‬‬
‫‪4‬‬ ‫‪+ H2O ⇌ NH3 + H3O+‬‬
‫‪2 H2O ⇌ H3O+ + OH−‬‬
‫ﻴﻀ ‪‬ﻡ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ ﺍﻝﻨﺸﺎﺩﺭ ﻭﺸﻭﺍﺭﺩ ﺍﻷﻤﻭﻨﻴﻭﻡ ﻭﺍﻝﻜﻠﻭﺭ ﻭﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻭﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪.‬‬
‫ﺘﺅﻝﻑ ﺘﺭﺍﻜﻴﺯ ﻫﺫﻩ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺠﺎﻫﻴل ﺍﻝﺨﻤﺴﺔ ﺍﻝﺘﻲ ﻴﺠﺏ ﺘﺤﺩﻴﺩﻫﺎ‪ .‬ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﻲ‬
‫ﺘﺘﺤﻘﹼﻕ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪.‬‬
‫♦ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ‪:‬‬
‫)‪(1‬‬ ‫] ‪c = [Cl−‬‬
‫)‪(2‬‬ ‫‪c = [NH+‬‬
‫] ‪4 ] + [NH 3‬‬
‫♦ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل‪:‬‬
‫)‪(3‬‬ ‫‪[NH+‬‬ ‫‪+‬‬ ‫‪−‬‬ ‫‪−‬‬
‫] ‪4 ] + [H 3 O ] = [Cl ] + [OH‬‬
‫♦ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ ﺍﻝﺤﺎﺼﻠﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫)‪(4‬‬ ‫] ‪K w = [H3O+ ] × [OH−‬‬
‫] ‪[H3O+ ] × [NH 3‬‬
‫)‪(5‬‬ ‫= ‪KA‬‬
‫‪[NH+‬‬
‫] ‪4‬‬
‫ﺘﻘﻭﺩﻨﺎ ﻤﻌﺎﻝﺠﺔ ﻫﺫﻩ ﺍﻝﺠﻤﻠﺔ ﻤﻥ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺇﻝﻰ ﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻝﺜﺔ ﺒﺎﻝﻤﺠﻬﻭل ‪. h‬‬
‫‪h 3 + K A ⋅ h 2 − (K A ⋅ c + K w ) ⋅ h − K A .K w = 0‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺘﺎﺌﺞ ﺫﺍﺘﻬﺎ ﺍﻝﺘﻲ ﺘﻌﻁﻴﻬﺎ ﻁﺭﻴﻘﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪.‬‬

‫ﻭﻴﻌﻁﻲ ﺤ ّ‬
‫‪ .2.II‬ﻁﺭﻴﻘﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‬
‫ﻜﻨﹼﺎ ﻗﺩ ﻋﺭﻀﻨﺎ ﻤﺒﺩﺃ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻓﻲ ﺍﻝﻔﺼل ﺍﻝﺴﺎﺒﻕ ) ﺍﻝﻔﻘﺭﺓ ‪ ، (VI‬ﻭﺴﻨﺫﻜﹼﺭ ﺒﻤﻼﻤﺤﻬﺎ‬
‫ﺍﻝﺭﺌﻴﺴﺔ‪:‬‬
‫ﻴﻨﺘﺞ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﺠﻤﻠﺔ ﺍﻝﻨﺎﺠﻤﺔ ﻋﻥ ﻤﺯﺝ ﻋﺩﺓ ﺃﻨﻭﺍﻉ ﺤﻤﻀﻴﺔ ﻭﺃﺴﺎﺴﻴﺔ ﻤﻥ‬ ‫♦‬
‫ﺘﺭﻜﻴﺏ ﻋﺩﺓ ﺘﻔﺎﻋﻼﺕ‪.‬‬
‫ﻝﻜﻲ ﻨﺤﺩ‪‬ﺩ ﺤﺴﺎﺒﻴﹰﺎ ﺍﻝﺤﺎﻝﺔ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻝﻠﺠﻤﻠﺔ ﻨﻘﺒل ﺒﺄﻨﻬﺎ ﻨﺎﺠﻤﺔ ﻋﻥ ﺘﺘﺎﻝﻲ ﻋﺩﺓ ﺘﻔﺎﻋﻼﺕ‬ ‫♦‬
‫ﺘﺩﺨل ﻓﻴﻬﺎ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺘﻲ ﺃُﻀﻴﻔﺕ ﺒﺩﺍﻴﺔ ﺃﻭ ﺍﻝﺘﻲ ﻅﻬﺭﺕ ﺃﺜﻨﺎﺀ ﻫﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ‪.‬‬
‫ﻴﺠﺭﻱ ﺘﺭﺘﻴﺏ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻜﺄﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ‪ ،‬ﻭﺫﻝﻙ ﺒﻭﻀﻌﻬﺎ‬ ‫♦‬
‫ﻋﻠﻰ ﻤﺤﻭﺭ ﺒﺩﻻﻝﺔ ﻗﻴﻡ ‪ pK A‬ﺍﻝﻤﻭﺍﻓﻘﺔ‪ .‬ﻨﺤﺩ‪‬ﺩ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺘﻲ ﺠﺭﻯ ﺇﺩﺨﺎﻝﻬﺎ ﻓﻲ‬
‫ﺍﻝﻤﺤﻠﻭل ﻤﻊ ﺘﻤﻴﻴﺯ ﺍﻝﺤﻤﺽ ﺍﻷﻗﻭﻯ ﻭﺍﻷﺴﺎﺱ ﺍﻷﻗﻭﻯ‪.‬‬
‫ﻻ ﺘﻔﺎﻋل‬
‫ﻴﺠﺭﻱ ﺘﺭﺘﻴﺏ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺘﺒﻌﹰﺎ ﻝﺘﻨﺎﻗﺹ ﻗﻴﻡ ﺜﻭﺍﺒﺘﻬﺎ ‪ ، K 0‬ﺒﺤﻴﺙ ﻨﻀﻊ ﺃﻭ ﹰ‬ ‫♦‬
‫ﺍﻷﺴﺎﺱ ﺍﻷﻗﻭﻯ ﻤﻊ ﺍﻝﺤﻤﺽ ﺍﻷﻗﻭﻯ ﺍﻝﻠﺫﻴﻥ ﺃﻀﻴﻔﺎ ﺇﻝﻰ ﺍﻝﻭﺴﻁ ﺒﺘﺭﺍﻜﻴﺯ ﻏﻴﺭ ﻤﻬﻤﻠﺔ‬
‫ﻭﻫﻨﺎ ﻨﻤﻴ‪‬ﺯ ﺤﺎﻝﺘﻴﻥ‪:‬‬
‫‪ o‬ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل ﻜ ‪‬ﻤﻲ‪ :‬ﻨﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺏ ﺍﻝﺠﻤﻠﺔ ﺒﻌﺩ ﺤﺩﻭﺙ ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل‪ ،‬ﻭﻴﺠﺭﻱ‬
‫ﺍﻋﺘﺒﺎﺭ ﺍﻝﺠﻤﻠﺔ ﺍﻝﺘﻲ ﻨﺼل ﺇﻝﻴﻬﺎ ﻭﻜﺄﻨﻬﺎ ﻤﺤﻠﻭل ﺍﺒﺘﺩﺍﺌﻲ ﻨﺒﺤﺙ ﺍﻨﻁﻼﻗﹰﺎ ﻤﻨﻬﺎ ﻋﻥ‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪.‬‬
‫‪ o‬ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل ﻏﻴﺭ ﻜﻤ‪‬ﻲ‪ :‬ﻨﺴﺘﻌﻴﻥ ﺒﻌﺒﺎﺭﺓ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻝﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺏ ﺍﻝﺠﻤﻠﺔ‪،‬‬
‫ﻭﻗﺩ ﻨﻠﺠﺄ ﺇﻝﻰ ﺘﻘﺭﻴﺒﺎﺕ ﻴﺠﺭﻱ ﺍﻝﺘﺤﻘﻕ ﻻﺤﻘﹰﺎ ﻤﻥ ﺼﺤﺘﻬﺎ‪ .‬ﻭﻗﺩ ﻨﻀﻁﺭ ﺃﺤﻴﺎﻨﹰﺎ‬
‫ﺇﻝﻰ ﺍﻋﺘﻤﺎﺩ ﺘﻔﺎﻋل ﺭﺍﺠﺢ ﺜﺎﻨﻭﻱ ﺁﺨﺭ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ ﻤﻥ‬
‫ﻤﺭﺘﺒﺔ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻤﻌﺘﺒﺭ‪.‬‬
‫ﺴﻭﻑ ﻨﻁﺒ‪‬ﻕ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻋﻨﺩ ﺩﺭﺍﺴﺘﻨﺎ ﻝﺒﻌﺽ ﺍﻝﻤﺤﺎﻝﻴل‪.‬‬
‫ﻨﹸﺠﻤل ﻓﻲ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﻁﺭﻴﻘﺔ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪:‬‬
‫ﻨﺤﺼﻲ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺤﻤﻀﻴﺔ ﺃﻭ ﺍﻷﺴﺎﺴﻴﺔ ﺍﻝﺘﻲ ﺃُﻀﻴﻔﺕ‬

‫ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل‬
‫ﻨﺤﺩ‪‬ﺩ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻭﻨﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻏﻴﺭ ﺘﺎﻡ‬ ‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺘﺎﻡ‬
‫ﺤل ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺎﺘﺠﺔ ﻤﻊ ﺒﻌﺽ ﺍﻝﺘﻘﺭﻴﺒﺎﺕ‬ ‫ﺤﺼﻴﻠﺔ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻨﺎﺠﻤﺔ ﻋﻥ ﺍﻝﺘﻔﺎﻋل‬
‫ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﺘﻘﺭﻴﺒﺎﺕ ﺍﻝﻤﻌﺘﻤﺩﺓ‬

‫‪ .3.II‬ﺤﻤﺽ ﻗﻭﻱ‪ ،‬ﺃﺴﺎﺱ ﻗﻭﻱ‬
‫‪ .1.3.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺤﻤﺽ ﻗﻭﻱ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻝﺤﻤﺽ ﻗﻭﻱ ﺃﺤﺎﺩﻱ ﺍﻝﻭ ﻅﻴﻔﺔ ﺍﻝﺤﺎﻤﻀﻴﺔ ‪ ) HA‬ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‬
‫ﻝﻨﺄﺨﺫ ﻤﺤﻠﻭ ﹰ‬
‫ﻋﻠﻰ ﺴﺒﻴل ﺍﻝﻤﺜﺎل( ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ ‪ c‬ﻋﻨﺩ ﻝﺤﻅﺔ ﺍﻹﻀﺎﻓﺔ‪ .‬ﻴﺨﻀﻊ ﺍﻝﻤﺤﻠﻭل ﺇﻝﻰ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪HA + H2O → H3O+ + A−‬‬
‫)‪(2‬‬ ‫‪2 H2O H 3O+ + OH−‬‬
‫ ﺒﺈﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪ ،‬ﻴﻜﻭﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻭﻤﻨﻪ‬
‫ﻥ‪:‬‬
‫ﻥ‪ . [H3O+ ] = h = c :‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪pH = − log c = pc‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻌﻼﻗﺔ ﻤﺴﺘﻘﻠﺔ ﻋﻥ ﻁﺒﻴﻌﺔ ﺍﻝﺤﻤﺽ ﺍﻝﻘﻭﻱ ﺍﻷﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‪ ،‬ﻭﻫﻲ ﺼﺤﻴﺤﺔ‬
‫ﺇ‪‬‬
‫ﻥ ‪. c > 10−6.5 mol/L‬‬
‫ﻤﺎﺩﺍﻡ ‪ pH < 6.5‬ﺃﻱ ﺃ ‪‬‬
‫ﻥ ‪ ، c ≤ 10−6.5 mol/L‬ﻋﻨﺩ ﺫ ﻝﻙ ﻴﻨﺒﻐﻲ ﺃﺨﺫ ﺘﻔﺎ ﻋل‬
‫ ﺇ ﺫﺍ ﻜﺎﻥ ‪ pH ≥ 6.5‬ﺃﻱ ﺃ ‪‬‬
‫ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﻭﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎﻝﻪ ﺒﺤﻴﺙ ﻴﺅﺩﻱ ﻫﺫﺍ ﺍﻷﺨﻴﺭ‬
‫ﺩﻭﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻨﻭﻱ‪.‬‬
‫ﻝﻨﺘﺫﻜﹼﺭ ﺘﻌﺭﻴﻑ ﺩﺭﺠﺔ ﺍﻝﺘﻘﺩ‪‬ﻡ ﺍﻝﺤﺠﻤﻴﺔ ‪ x‬ﻓﻲ ﺘﻔﺎﻋل ﻤﺎ ‪:‬‬
‫)‪ni (t ) − ni (0‬‬
‫= ‪x‬‬
‫‪V ⋅ νi‬‬
‫ﺤﻴﺙ ‪ νi‬ﻫﻲ ﺍﻝﻤﺜل ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻱ ﻝﻠﻨﻭﻉ ‪ i‬ﺍﻝﺩﺍﺨل ﻓﻲ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻜﻴﻤﻴﺎﺌﻲ ﻭ )‪ni (0‬‬
‫ﻭ ) ‪ ni (t‬ﻋﺩﺩ ﻤﻭﻻﺕ ﺍﻝﻨﻭﻉ ‪ i‬ﻓﻲ ﺍﻝﻠﺤﻅﺔ ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﻭﺍﻝﻠﺤﻅﺔ ‪ ، t‬ﻭ ‪ V‬ﻫﻭ ﺤﺠﻡ‬
‫ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻓﻴﻜﻭﻥ ﻓﻲ ﺤﺎﻝﺘﻨﺎ‪:‬‬
‫)‪(1‬‬ ‫‪HA‬‬ ‫‪+ H2O ⇌ H3O+‬‬ ‫‪+ A−‬‬

‫‪t =0‬‬ ‫‪c‬‬ ‫‪−‬‬ ‫‪0‬‬ ‫‪0‬‬
‫‪teq‬‬ ‫‪c − x1‬‬ ‫‪−‬‬ ‫‪x1 + x 2‬‬ ‫‪x1‬‬
‫ﺤﻴﺙ ‪ x1‬ﻭ ‪ x 2‬ﻫﻤﺎ ﺩﺭﺠﺘﺎ ﺍﻝﺘﻘﺩ‪‬ﻡ ﺍﻝﺤﺠﻤﻴﺘﺎﻥ ﻝﻠﺘﻔﺎﻋﻠﻴﻥ )‪ (1‬ﻭ )‪. (2‬‬
‫)‪(2‬‬ ‫‪2 H2O ⇌ H 3O+‬‬ ‫‪+ O H−‬‬

‫‪t =0 −‬‬ ‫‪0‬‬
‫‪teq‬‬ ‫‪−‬‬ ‫‪x1 + x 2‬‬ ‫‪x2‬‬
‫ﻥ ﻤﺎ‬
‫ﻥ ﻤﺠﻤﻭﻋﻬﻤﺎ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻭﻤﻬﻤﺎ ﺘﻜﻥ ﺩﺭﺠﺘﺎ ﺍﻝﺘﻘﺩ‪‬ﻡ ﺍﻝﺤﺠﻤﻴﺘﺎﻥ ﻝﻠﺘﻔﺎﻋﻠﻴﻥ )‪ (1‬ﻭ )‪ (2‬ﻓﺈ ‪‬‬
‫ﻴﺘﻭﻝﹼﺩ ﻓﻲ ﺍﻝﻭﺴﻁ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ H3O+‬ﻴﺴﺎﻭﻱ ﻤﺎ ﻴﺘﻜﻭ‪‬ﻥ ﻤﻥ ﺸﻭﺍﺭﺩ‬
‫ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ‪ O H−‬ﻭ ‪ ، A−‬ﻭﻫﺫﺍ ﻤﺎ ﻴ‪‬ﻌﺭﻑ ﺃﻴﻀﹰﺎ ﺒﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل‬
‫ﺤﻴﺙ ﻨﻜﺘﺏ‪[H3O+ ] = [A− ] + [OH− ] :‬‬
‫‪K‬‬
‫ﻥ‪ h = c + w :‬ﻭﺘﻜﻭﻥ ﻝﺩﻴﻨﺎ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻵﺘﻴﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ‪:‬‬ ‫ﻭﻤﻨﻪ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪h‬‬
‫‪h2 − c ⋅ h − Kw = 0‬‬
‫ﺤﻴﺙ ] ‪ [H3O+‬ﻫﻭ ﺍﻝﺠﺫﺭ ﺍﻝﻤﻭﺠﺏ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﺴﺎﺒﻘﺔ‪.‬‬
‫‪pH‬‬
‫‪7‬‬
‫‪6‬‬
‫‪5‬‬
‫‪4‬‬
‫‪3‬‬
‫‪2‬‬
‫‪A‬‬ ‫‪B‬‬ ‫‪C‬‬
‫‪1‬‬
‫‪− logc‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8‬‬ ‫‪9‬‬ ‫‪10‬‬
‫ﺍﻝﺸﻜل )‪ pH = f (− log c ) : (1‬ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﻠﻭل ﺤﻤﺽ ﻗﻭﻱ‪ .‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : A‬ﻻ ﻴﻤﻜﻥ ﺘﻁﺒﻴﻕ ﺍﻝﻌﻼﻗﺔ‬
‫] ‪ . pH = − log[H3O+‬ﺍﻝﻤﻨﻁﻘﺔ ‪ . pH = − logc : B‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : C‬ﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ‬
‫ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ‪. h 2 − c ⋅ h − K w = 0‬‬
‫ﻤﻼﺤﻅﺔ‬
‫ﻥ ﺍ ﻝﺘﻌﺭ ﻴﻑ ﺍ ﻝﺘﻘﺭ ﻴﺒﻲ‬
‫ﻓﻲ ﺤﺎ ﻝﺔ ﻤﺤﺎ ﻝﻴل ﻋﺎ ﻝﻴﺔ ﺍ ﻝﺘﺭ ﻜﻴﺯ‪ c > 5 ⋅ 10−2 mol/L :‬ﻓﺈ ‪‬‬
‫ﻼ ﻝﻠﺘﻁﺒﻴﻕ ‪ ،‬ﻭﺍﻝﻘﻴﻡ ﺍﻝﺘﻲ ﻨﺤﺼل ﻋﻠﻴﻬﺎ ﻤﻥ ﺘﻁﺒﻴﻕ ﺍﻝﻌﻼﻗﺔ‬
‫] ‪ pH = − log[H3O+‬ﻻ ﻴﻌﻭﺩ ﻗﺎﺒ ﹰ‬
‫‪ pH = − log c = pc‬ﺘﻌﻁﻲ ﻗﻴﻤﹰﺎ ﻝﻠـ ‪ pH‬ﺃﻋﻠﻰ ﻤﻥ ﺍﻝﻘﻴﻡ ﺍﻝﻤﻘﺎﺴﺔ ﻓﻌﻠﻴﹰﺎ‪.‬‬
‫ﻴﻤﺜﹼل ﺍﻝﺸﻜل )‪ (1‬ﻤﺎ ﻴ‪‬ﻌﺭ‪‬ﻑ ﺒﺎﺴﻡ ﻤﺨﻁﻁ ‪ Flood‬ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻴﻀ ‪‬ﻡ ﺜﻼﺙ ﻤﻨﺎﻁﻕ‪ :‬ﺍﻝﻤﻨﻁﻘﺔ ‪: A‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍ ﻝﻤﻨﻁﻘﺔ ﻻ ﻴﻤﻜﻥ ﺘﻁﺒﻴﻕ ﺍ ﻝﻌﻼ ﻗﺔ ] ‪ . pH = − log[H3O+‬ﺍ ﻝﻤﻨﻁﻘﺔ ‪ : B‬ﻓﻲ ﻫﺫﻩ‬
‫ﺍﻝﻤﻨﻁﻘﺔ ﻨﺴﺘﻌﻤل ﺍﻝﻌﻼﻗﺔ ‪ pH = − log c‬ﻓﻲ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪ .‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : C‬ﻓﻲ‬
‫ﻫﺫﻩ ﺍﻝﻤﻨﻁﻘﺔ ﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ‪ ،‬ﻭﻴﻠﺯﻡ ﺤل ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ‬
‫ﺍﻝﺜﺎﻨﻴﺔ ‪ h 2 − c ⋅ h − K w = 0 :‬ﻝﺘﺤﺩﻴﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .2.3.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻷﺴﺎﺱ ﻗﻭﻱ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻷﺴﺎﺴﻴﺔ ‪ ) A−‬ﺸﺎﺭﺩﺓ ﺍﻝﻜﺤﻭﻻﺕ‬

‫‪ RO−‬ﻋﻠﻰ ﺴﺒﻴل ﺍ ﻝﻤﺜﺎ ل ( ﺒﺘﺭ ﻜﻴﺯ ﻋﻨﺩ ﻝﺤﻅﺔ ﺍ ﻹﻀﺎ ﻓﺔ ‪ . c‬ﻴﺨﻀﻊ ﺍ ﻝﻤﺤﻠﻭ ل ﺇ ﻝﻰ ﺍ ﻝﺘﻔﺎ ﻋﻠﻴﻥ‬
‫ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪A− + H2O → HA + OH−‬‬
‫)‪(2‬‬ ‫‪2 H2O H 3O+ + OH−‬‬
‫ ﺒﺈﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪ ،‬ﻴﻜﻭﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻭﻤﻨﻪ‬
‫ﻥ‪:‬‬
‫ﻥ‪ . [OH− ] = ω = c :‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪p OH = − log c = pc‬‬
‫‪pH = pK w + log c = pK w − pc‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻌﻼﻗﺔ ﻤﺴﺘﻘﻠﺔ ﻋﻥ ﻁﺒﻴﻌﺔ ﺍﻷﺴﺎﺱ ﺍﻝﻘﻭﻱ ﺍﻷﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ﻭﻫﻲ ﺼﺤﻴﺤﺔ ﻤﺎﺩﺍﻡ‬
‫ﺇ‪‬‬
‫ﻥ ‪. c > 10−6.5 mol/L‬‬
‫‪ pH > 7.5‬ﺃﻱ ﺃ ‪‬‬
‫ﻥ ‪ ، c ≤ 10−6.5 mol/L‬ﻋﻨﺩ ﺫ ﻝﻙ ﻴﻨﺒﻐﻲ ﺃ ﺨﺫ ﺘﻔﺎ ﻋل‬
‫ ﺇ ﺫ ﺍ ﻜﺎ ﻥ ‪ pH ≤ 7.5‬ﺃ ﻱ ﺃ ‪‬‬
‫ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﻭﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎﻝﻪ ﺒﺤﻴﺙ ﻴﺅﺩﻱ ﻫﺫﺍ ﺍﻷﺨﻴﺭ‬
‫ﺩﻭﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻨﻭﻱ‪.‬‬
‫ﻓﺈﺫﺍ ﺍﻋﺘﺒﺭﻨﺎ ﻤﺠﻤﻭﻉ ﺩﺭﺠﺘﻲ ﺍﻝﺘﻘﺩ‪‬ﻡ ﺍﻝﺤﺠﻤﻴﺘﻴﻥ ﻝﻠﺘﻔﺎﻋﻠﻴﻥ )‪ (1‬ﻭ )‪- (2‬ﻭﻫﺫﺍ ﻤﺎ ﻴﻜﺎﻓﺊ‬
‫ﻥ‪:‬‬
‫ﻁﺒﻌﹰﺎ ﻜﺘﺎﺒﺔ ﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل‪ -‬ﻨﺠﺩ ﺃ ‪‬‬
‫] ‪[OH− ] = [Na + ] + [H 3O+‬‬
‫ﻥ‪:‬‬
‫ﻭﻤﻨﻪ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪ω = c + K w /ω‬‬
‫‪ω2 − c ⋅ ω − K w = 0‬‬
‫ﺤﻴﺙ ] ‪ [OH−‬ﻫﻭ ﺍﻝﺠﺫﺭ ﺍﻝﻤﻭﺠﺏ‪.‬‬
‫ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﺎﻝﻴل ﻗﻠﻭﻴﺔ ﺃﻭ ﺃﺴﺎﺴﻴﺔ ﻋﺎﻝﻴﺔ ﺍﻝﺘﺭﻜﻴﺯ‪ c > 5 ⋅ 10−2 mol/L :‬ﻻ ﺘﻌﻭﺩ‬
‫ﺍﻝﻌﻼ ﻗﺔ ﺍﻝﺘﻘﺭﻴﺒ‪‬ﻴﺔ ] ‪ K w = [H 3O+ ] ⋅ [OH−‬ﻗﺎﺒﻠﺔ ﻝﻠﺘﻁﺒﻴﻕ ‪ ،‬ﻭﺍﻝﻘﻴﻡ ﺍﻝﺘﻲ ﻨﺤﺼل ﻋﻠﻴﻬﺎ ﻤﻥ‬
‫ﺘﻁﺒﻴﻕ ﺍﻝﻌﻼﻗﺔ ‪ pH = pK w − pc‬ﺘﻌﻁﻲ ﻗﻴ ‪‬ﻡ ‪ pH‬ﺃﻋﻠﻰ ﻤﻥ ﺘﻠﻙ ﺍﻝﻤﻘﺎﺴﺔ ﻓﻌﻠﻴﹰﺎ‪.‬‬
‫ﻴﻤﺜﹼل ﺍﻝﺸﻜل )‪ (2‬ﻤﺨﻁﻁ ‪ Flood‬ﺍﻝﻤﻭﺍﻓﻕ ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻴﻀ ‪‬ﻡ ﺜﻼﺙ ﻤﻨﺎﻁﻕ‪ :‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : A‬ﻓﻲ ﻫﺫﻩ‬
‫ﺍﻝﻤﻨﻁﻘﺔ ﻻ ﻴﻤﻜﻥ ﺘﻁﺒﻴﻕ ﺍﻝﻌﻼﻗﺔ ‪ . [H3O+ ] ⋅ [OH− ] = K w‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : B‬ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﻨﻁﻘﺔ‬
‫ﻨﺴﺘﻌﻤل ﺍﻝﻌﻼﻗﺔ ‪ pH = 14 + log c‬ﻓﻲ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪ .‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : C‬ﻓﻲ ﻫﺫﻩ‬
‫ﺍﻝﻤﻨﻁﻘﺔ ﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪ ،‬ﺒل ﻴﻠﺯﻡ ﺤل ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ‬
‫‪ ω 2 − c ⋅ ω − K w = 0‬ﻝﺘﺤﺩﻴﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪pH‬‬
‫‪14‬‬
‫‪13‬‬
‫‪12‬‬
‫‪11‬‬
‫‪10‬‬
‫‪9‬‬
‫‪8‬‬ ‫‪A‬‬ ‫‪B‬‬ ‫‪C‬‬

‫‪− log c‬‬
‫‪7‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8‬‬ ‫‪9‬‬ ‫‪10‬‬
‫ﺍﻝﺸﻜل )‪ pH = f (− log c ) : (2‬ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ‪ .‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : A‬ﻻ ﻴﻤﻜﻥ ﺘﻁﺒﻴﻕ ﺍﻝﻌﻼﻗﺔ‬
‫‪ . [H 3O+ ] ⋅ [OH− ] = K w‬ﺍﻝﻤﻨﻁﻘﺔ ‪ . pH = 14 + log c : B‬ﺍﻝﻤﻨﻁﻘﺔ ‪ : C‬ﻻ ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺍﻝﺘﺤﻠل‬
‫ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ ‪. ω 2 − c ⋅ ω − K w = 0‬‬
‫‪ .4.II‬ﺤﻤﺽ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‪ ،‬ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‬
‫‪ .1.4.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺤﻤﺽ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻝﺤﻤﺽ ﻀﻌﻴﻑ ﺃﺤﺎ ﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻝﺤﺎﻤﻀﻴﺔ ) ‪ HA‬ﺤﻤﺽ ﺍ ﻝﺨل‬

‫‪ CH3COOH‬ﻋﻠﻰ ﺴﺒﻴل ﺍﻝﻤﺜﺎ ل ( ﺘﺭﻜﻴﺯ ﻩ ‪ c‬ﻋﻨﺩ ﻝﺤﻅﺔ ﺍﻹﻀﺎ ﻓﺔ‪ .‬ﻴﺨﻀﻊ ﺍ ﻝﻤﺤﻠﻭل ﺇ ﻝﻰ‬
‫ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪HA + H2O H3O+ + A−‬‬
‫)‪(2‬‬ ‫‪2 H2O H 3O+ + OH−‬‬
‫ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪ h ≥ 10−6.5 mol/L‬ﻴﻤﻜﻥ ﺇﻫﻤﺎ ل ﺍﻝﺘﺤﻠل ﺍ ﻝﺒﺭﻭﺘﻭﻨﻲ ﺍ ﻝﺫ ﺍﺘﻲ ﻝﻠﻤﺎﺀ‪،‬‬
‫ﻭﻴﻜﻭﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‪ ،‬ﻭﻨﻜﺘﺏ‬
‫‪[HA] = c − [H3O+ ] = c − h‬‬ ‫ﻭ‬ ‫‪[A− ] = [H3O+ ] = h‬‬
‫ﻭﻫﻨﺎ ﻨﻭﺍﺠﻪ ﺤﺎﻝﺘﻴﻥ ﺘﺒﻌﹰﺎ ﻝﺩﺭﺠﺔ ﻗﻭﺓ ﺍﻝﺤﻤﺽ ﻭ‪/‬ﺃﻭ ﻭﻤﺩﻯ ﺘﻤﺩﻴﺩﻩ ‪:‬‬
‫ ﺍﻝﺤﻤﺽ ‪ HA‬ﻀﻌﻴﻑ ﻨﺴﺒﻴﹰﺎ ﻭ‪/‬ﺃﻭ ﻤﻤﺩ‪‬ﺩ ﻗﻠﻴﻼﹰ‪ ،‬ﻓﺘﺤﻠﹼﻠﻪ ﻤﺤﺩﻭﺩ‪:‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺸﺭﻭﻁ ﻴﻜﻭﻥ ﺘﻘﺩ‪‬ﻡ ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ‪ HA‬ﻤﻊ ﺍﻝﻤﺎﺀ ﻀﻌﻴﻔﹰﺎ ﻭﻴﻜﻭﻥ‪h ≪ c :‬‬
‫ﻥ ‪ . [HA] = c − h ≈ c‬ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ‪: K A‬‬
‫ﻭﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪[A− ] ⋅ [H 3O+ ] h 2‬‬
‫= ‪KA‬‬ ‫≈‬
‫]‪[HA‬‬ ‫‪c‬‬
‫‪p K A + pc‬‬
‫= ‪pH‬‬
‫‪2‬‬
‫ﻭﺘﻜﻭﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺤﺴﻭﺒﺔ ﺼﺤﻴﺤﺔ ﺇﺫﺍ ﻜﺎﻥ ‪، [A ] ≤ 0.1 × [HA] :‬‬
‫‪−‬‬
‫ﻭ ﻝﻤ‪‬ﺎ ﻜﺎ ﻥ ] ‪ [A− ] = [H3O+‬ﻓﺈ ﻥ ﻫﺫ ﺍ ﻴﻜﺎ ﻓﺊ ]‪ [H3O+ ] ≤ 0.1 × [HA‬ﺃ ﻱ ﺇ ‪‬‬

‫ﻥ‬
‫‪. pH ≤ p K A − 1‬‬
‫ﻥ ﺍﻝﺸﺭﻁ ﺍﻝﺴﺎﺒﻕ ﻴﻜﺎﻓﺊ‪:‬‬
‫ﻭﺒﺎﻝﻌﻭﺩﺓ ﺇﻝﻰ ﺍﻝﻌﻼﻗﺔ ‪ pH = (p K A + pc ) / 2‬ﻓﺈ ‪‬‬
‫‪p K A − pc ≥ 2‬‬
‫ ﺍﻝﺤﻤﺽ ﺍﻝﻀﻌﻴﻑ ‪ HA‬ﻗﻭﻱ ﻨﺴﺒﻴﹰﺎ ﻭ‪/‬ﺃﻭ ﻤﻤﺩ‪‬ﺩ‪ ،‬ﻭﺒﺎﻝﺘﺎﻝﻲ ﻓﺘﺤﹼﻠﻠﻪ ﻜﺒﻴﺭ‪:‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ‪: K A‬‬
‫‪−‬‬ ‫‪+‬‬
‫] ‪[A ] ⋅ [H 3O‬‬ ‫‪h2‬‬
‫= ‪KA‬‬ ‫=‬
‫]‪[HA‬‬ ‫‪c −h‬‬
‫ﻭﻫﺫﺍ ﻴﻘﻭﺩﻨﺎ ﺇﻝﻰ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ‪:‬‬

‫‪h 2 + KA ⋅ h − KA ⋅ c = 0‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻹﻴﺠﺎﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻴﻜﻔﻲ ﺤ ّ‬
‫ﻤﻥ ﻭﺠﻬﺔ ﻨﻅﺭﻋﻤﻠﻴﺔ‪ ،‬ﻝﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻝﺤﻤﺽ ﻀﻌﻴﻑ ﻴ‪‬ﻨﺼ‪‬ﺢ ﺒﻤﻘﺎﺭﻨﺔ‬
‫ﻗﻴﻡ ‪ pK A‬ﻭ ‪ pc‬ﻤﻊ ﺘﺒﺭﻴﺭ ﺍﻝﺨﻴﺎﺭ ﺍﻝﻤﺘﺨﺫ ﻤﻥ ﻭﺠﻬﺔ ﻨﻅﺭ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻻﺴﺘﻌﻤﺎل ﺇﺤﺩﻯ‬
‫ﺍﻝﻌﻼﻗﺘﻴﻥ‪:‬‬
‫‪ pH = (p K A + pc )/2‬ﻋﻨﺩﻤﺎ ‪. p K A − pc ≥ 2‬‬
‫‪ h 2 + K A ⋅ h − K A ⋅ c = 0‬ﻋﻨﺩﻤﺎ ‪. p K A − pc < 2‬‬
‫ﻭﺒﻌﺩ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﻨﺒﻐﻲ ﺍﻝﺘﺤﻘﹼﻕ ﺩﻭﻤﹰﺎ ﻤﻥ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﻤﻭﻀﻭﻋﺔ‪.‬‬
‫ﻴﻤﺜﹼل ﺍﻝﺸﻜل )‪ (3‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ )‪ ، pH = f (− log c‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﺘﺄﺨﺫ ‪ p K A‬ﻗﻴﻤﹰﺎ‬

‫ﻤﺨﺘﻠﻔﺔ‪ .‬ﻭﻴﻤﻜﻥ ﺍﺴﺘﻌﻤﺎل ﻫﺫﻩ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻝﺘﺤﺩﻴﺩ ﻗﻴﻡ ‪ pH‬ﻤﺤﻠﻭل ﺤﻤﺽ ﻀﻌﻴﻑ ﻋ‪‬ﻠﻡ‬
‫ﺜﺎﺒﺕ ﺤﻤﻭﻀﺘﻪ ‪ K A‬ﻭﺘﺭﻜﻴﺯﻩ ‪. c‬‬
‫‪pH‬‬
‫‪7‬‬
‫‪13‬‬
‫‪12‬‬
‫‪6‬‬ ‫‪11‬‬
‫‪10‬‬
‫‪9‬‬
‫‪5‬‬ ‫‪8‬‬
‫‪7‬‬
‫‪6‬‬
‫‪4‬‬
‫‪pK A =5‬‬
‫‪3‬‬ ‫‪4‬‬
‫‪3‬‬
‫‪2‬‬
‫‪2‬‬
‫‪1‬‬ ‫‪1‬‬
‫‪− log c‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪8‬‬
‫ﺍﻝﺸﻜل )‪ pH = f (− log c ) : (3‬ﺃﻭ ﻤﺨﻁﻁ ‪ Flood‬ﺍﻝﻤﻭﺍﻓﻕ ﻝﻠﺤﻤﻭﺽ ﺍﻝﻀﻌﻴﻔﺔ ﺒﺩﻻﻝﺔ ﻗﻴﻡ ﻤﺨﺘﻠﻔﺔ ﻝـ ‪p K A‬‬
‫ﺘﻁﺒﻴﻕ‬
‫ﻥ‪ p K A = 3.2 :‬ﻭﺫﻝﻙ ﻓﻲ‬
‫ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻤﻥ ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﺇﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ‪:‬‬
‫‪ .1‬ﺘﺭﻜﻴﺯ ﺍﻝﻤﺤﻠﻭل ‪. 0.10 mol/L‬‬

‫‪ .2‬ﺘﺭﻜﻴﺯ ﺍﻝﻤﺤﻠﻭل ‪. 1.0 × 10−3 mol/L‬‬
‫ﺍﻝﺤل‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻲ‪:‬‬
‫ﺇ‪‬‬
‫‪HNO2 + H2O H 3O+ + NO−‬‬
‫‪2‬‬
‫‪ .1‬ﺘﺭﻜﻴﺯ ﺍﻝﻤﺤﻠﻭل ‪ : 0.10 mol/L‬ﻝﻤﺎ ﻜﺎﻥ ‪ p K A − pc ≥ 2‬ﺃﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻁﺒ‪‬ﻕ ﺍﻝﻌﻼﻗﺔ ‪:‬‬

‫ﻥ ‪ pH = 2.1‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫‪ pH = (p K A + pc ) / 2‬ﻭﺒﺎﻝﺘﻁﺒﻴﻕ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ ﺃ ‪‬‬
‫‪، [NO−‬‬
‫‪ pH‬ﺍ ﻝﻤﺤﻠﻭ ل ﺘﺤﻘﹼﻕ ﺍ ﻝﻌﻼ ﻗﺔ ‪ pH ≤ p K A − 1‬ﺃ ﻱ ] ‪2 ] < 0.1 × [HNO2‬‬
‫ﻓﺎﻝﺘﻘﺭﻴﺏ ﺍﻝﻤﻁﺒﻕ ﺼﺤﻴﺢ‪.‬‬

‫‪ .2‬ﺘﺭ ﻜﻴﺯ ﺍ ﻝﻤﺤﻠﻭ ل ‪ : 1.0 × 10−3 mol/L‬ﻝﻤﺎ ﻜﺎ ﻥ ‪ p K A − pc < 2‬ﻭ ﺠﺏ ﺘﻁﺒﻴﻕ‬
‫ﺍﻝﻌﻼﻗﺔ ‪ . h 2 + K A ⋅ h − K A ⋅ c = 0‬ﻭﻋﺩﺩﻴﹰﺎ ﺘﺄﺨﺫ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫ﻥ ‪ . h = 5.4 × 10−4 mol/L‬ﺃﻱ‬
‫‪ ، h 2 + 10−3.2 ⋅ h − 10−6.2 = 0‬ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺘﺴﺎﻭﻱ ‪. pH = 3.3‬‬
‫ﺇ‪‬‬
‫ﻝﻭ ﻁﺒﻘﻨﺎ ﺍﻝﻌﻼﻗﺔ ) ‪ pH = 1/2 (p K A + pc‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺜﺎﻨﻲ ﻝﺤﺼﻠﻨﺎ ﻋﻠﻰ‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻘﻴﻤﺔ ﻝﻴﺴﺕ ﺃﺼﻐﺭ ﻤﻥ‬
‫ﻗﻴﻤﺔ ﻝـ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺘﺴﺎﻭﻱ ‪ pH = 3.1‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‬
‫‪ [NO−‬ﻭ ﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﻥ ] ‪2 ] > 0.1 × [HNO2‬‬
‫‪ p K A − 1‬ﺃﻱ ﺇ ‪‬‬
‫ﺍﻝﻤﺤﺴﻭﺒﺔ ﺒﻬﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻏﻴﺭ ﺼﺤﻴﺤﺔ‪.‬‬
‫‪‬ﻴﻅﻬﺭ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻭﻤﻭﻗﻌﻲ ‪ pH‬ﺍﻝﻤﺤﻠﻭﻝﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪.‬‬
‫ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺍﻝﺤﻤﺽ‬ ‫ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺍﻷﺴﺎﺱ‬

‫‪pH1‬‬
‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪pH‬‬
‫‪HNO2‬‬ ‫‪NO−‬‬
‫‪2‬‬
‫‪pH2‬‬
‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪pH‬‬
‫‪HNO2‬‬ ‫‪NO−‬‬
‫‪2‬‬
‫

‬
‫ﺍﻝﻘﺭﺤﺔ ﺍﻝﻤﻌﺩﻴﺔ‬
‫ﻥ ﺒﻌﺽ ﺃﻨﻭﺍﻉ ﺍﻝﻘﺭﺤﺔ ﺍﻝﻤﻌﺩﻴﺔ ﻴﻌﻭﺩ ﺇﻝﻰ ﺍﻝﺘﻬﺎﺏ ﻓﻲ ﻏﺸﺎﺀ ﺍﻝﻤﻌﺩﺓ ﺘﺴﺒ‪‬ﺒﻪ ﺠﺭﺍﺜﻴﻡ ﻤﻌﺭﻭﻓﺔ‬
‫ﺃﺼﺒﺢ ﻤﻥ ﺍﻝﻤﻘﺒﻭل ﺤﺎﻝﻴﹰﺎ ﺃ ‪‬‬
‫ﺒﺎﺴﻡ ‪ .Helicobacter Pylori‬ﻭﻴﻌﻭﺩ ﺍﻝﻔﻀل ﻓﻲ ﺍﻜﺘﺸﺎﻓﻬﺎ ﺇﻝﻰ ﺍﻝﻌﺎﻝﻡ ﺍﻷﺴﺘﺭﺍﻝﻲ ‪ Barry Marshall‬ﻓﻲ‬
‫ﻕ ﻋﻠﻰ ﺍﻜﺘﺸﺎﻓﻪ ﻫﺫﺍ ﺠﺎﺌﺯﺓ ﻨﻭﺒل ﻓﻲ ﺍﻝﻁﺏ ﻓﻴﻤﺎ ﺒﻌﺩ‪.‬‬
‫ﺍﻝﺜﻤﺎﻨﻴﻨﻴﺎﺕ ﻤﻥ ﺍﻝﻘﺭﻥ ﺍﻝﻤﺎﻀﻲ‪ .‬ﻭﻗﺩ ﺍﺴﺘﺤ ﹼ‬
‫ﻓﻜﻴﻑ ﺘﻨﺠﺢ ﻫﺫﻩ ﺍﻝﺠﺭﺍﺜﻴﻡ ﻓﻲ ﺍﻝﻌﻴﺵ ﻀﻤﻥ ﻭﺴﻁ ﺍﻝﻤﻌﺩﺓ ﺍﻝﻌﺎﻝﻲ ﺍﻝﺤﻤﻭﻀﺔ؛ ﺤﻴﺙ ﺘﺼل ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ ﺇﻝﻰ‬
‫ﻁ ﻭﺴﻁﹲ ﻋﻘﻴﻡ؟!‬
‫ﺤﻭﺍﻝﻲ ‪ 2.5‬ﺒﻌﺩ ﺃﻥ ﻜﺎﻥ ﺍﻝﻌﻠﻤﺎﺀ ﻴﻅﻨﻭﻥ ﺃﻥ ﻫﺫﺍ ﺍﻝﻭﺴ ﹶ‬
‫ﻓﻲ ﺍﻝﻭﺍﻗﻊ ﻴﻌﻭﺩ ﺍﻝﻔﻀل ﻓﻲ ﺘﻌﺎﻴﺵ ﻫﺫﻩ ﺍﻝﺠﺭﺍﺜﻴﻡ ﻤﻊ ﺍﻝﻭﺴﻁ ﺍﻝﺤﺎﻤﻀﻲ ﻝﻠﻤﻌﺩﺓ ﺇﻝﻰ ﺘﻤﺘﻌﻬﺎ ﺒﺄﻨﺯﻴﻡ ‪ ،urease‬ﺤﻴﺙ‬
‫ل ﻤﻥ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ‬
‫ﻴﻘﻭﻡ ﻫﺫﺍ ﺍﻷﻨﺯﻴﻡ ﺒﺘﻔﻜﻴﻙ ﺍﻝﻴﻭﺭﻴﺎ ‪ CO(NH2 )2‬ﺍﻝﻤﺘﻭﻓﺭﺓ ﻓﻲ ﺍﻝﺴﻭﺍﺌل ﺍﻝ ‪‬ﻤﻌﺩﻴﺔ ﺇﻝﻰ ﻜ ّ‬
‫‪ CO2‬ﺍﻝﺫﻱ ﻴ‪‬ﻁﺭﺡ ﻤﻊ ﻫﻭﺍﺀ ﺍﻝﺯﻓﻴﺭ ﻭﺍﻝﻨﺸﺎﺩﺭ ‪ NH3‬ﺫﻱ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻘﻠﻭﻱ ﺍﻝﺫﻱ ﻴﻌﺩ‪‬ل ﻤﻥ ﺤﻤﻭﻀﺔ ﺍﻝﻤﻌﺩﺓ ﻓﻲ‬
‫ﺍﻝﺠﻭﺍﺭ ﺍﻝﻤﺤﻴﻁ ﺒﺎﻝﺠﺭﺜﻭﻤﺔ ﻭﺒﺫﻝﻙ ﺘﻨﺠﺢ ﻓﻲ ﺍﻝﺒﻘﺎﺀ‪.‬‬
‫ﻭﻤﻥ ﺒﻴﻥ ﺍﻝﻔﺤﻭﺹ ﺍﻝﺴﺭﻴﺭﻴﺔ ﺍﻝﺘﻲ ﻴﻘﻭﻡ ﺒﻬﺎ ﺍﻷﻁﺒﺎﺀ ﻝﻠﻜﺸﻑ ﻋﻥ ﻭﺠﻭﺩ ﺠﺭﺜﻭﻤﺔ ﻜﻬﺫﻩ ﻓﻲ ﺍﻝﻤﻌـﺩﺓ ﻨـﺫﻜﺭ "ﺍﺨﺘﺒـﺎﺭ‬
‫ل ﻭﺠﻭﺩ ﻫﺫﺍ ﺍﻷﻨﺯﻴﻡ ﻋﻨﺩ ﻫﺫﻩ ﺍﻝﺠﺭﺍﺜﻴﻡ ﻝﻠﻜﺸﻑ ﻋﻨﻬﺎ‪ .‬ﻴﻘﻭﻡ ﻫﺫﺍ ﺍﻻﺨﺘﺒـﺎﺭ ﻋﻠـﻰ‬
‫ﺍﻝ ﹼﻨﻔﹶﺱ" ‪ breath test‬ﺍﻝﺫﻱ ﻴﺴﺘﻐ ّ‬
‫ﺃﻭ ﺍﻝﻨﻅﻴﺭ ‪ ، 14 C‬ﺜ ‪‬ﻡ ﻴﺠﺭﻱ ﺍﻝﺘﺤﺭ‪‬ﻱ ﻋـﻥ ﻫـﺫﻩ‬ ‫‪13‬‬
‫ﺇﻋﻁﺎﺀ ﺍﻝﻤﺭﻴﺽ ﻜﻤﻴﺔ ﻤﻥ ﺍﻝﻴﻭﺭﻴﺎ ﺍﻝﻤﻭﺴﻭﻤﺔ ﺠﺯﺌﻴﹰﺎ ﺒﺎﻝﻨﻅﻴﺭ ‪C‬‬
‫ﺍﻝﻨﻅﺎﺌﺭ ﺒﻌﺩ ﻨﺤﻭ ﻨﺼﻑ ﺴﺎﻋﺔ ﻤﻥ ﺘﻨﺎﻭل ﺍﻝﻤﺭﻴﺽ ﺍﻝﻴﻭﺭﻴﺎ ﻓﻲ ﻫﻭﺍﺀ ﺍﻝﺯﻓﻴﺭ‪ ،‬ﻭﺫﻝﻙ ﺇﻤﺎ ﺒﺎﺴﺘﻌﻤﺎل ﻤﻁﻴـﺎﻑ ﺍﻝﻜﺘﻠـﺔ‬
‫ﻥ ﻅﻬـﻭﺭ ﻫـﺫﻩ‬
‫)ﻝﻠﻜﺸﻑ ﻋﻥ ﺍﻝﻨﻅﻴﺭ ‪ ( 13 C‬ﻭﺇﻤﺎ ﺒﺎﻝﺘﺄﻝﻕ ‪) scintillation‬ﻝﻠﻜﺸﻑ ﻋﻥ ﺍﻝﻨﻅﻴﺭ ﺍﻝﻤﺸـﻊ ‪ .( 14 C‬ﺇ ‪‬‬
‫ﺍﻝﻨﻅﺎﺌﺭ ﻓﻲ ﻫﻭﺍﺀ ﺍﻝﺯﻓﻴﺭ ﻴﻌﻨﻲ ﻭﺠﻭﺩ ﺠﺭﺍﺜﻴﻡ ‪ Helicobacter Pylori‬ﻓﻲ ﺍﻝﻤﻌﺩﺓ ﺍﻝﺘﻲ ﻗﺎﻤـﺕ ﺒﺘﻔﻜﻴـﻙ ﺍﻝﻴﻭﺭﻴـﺎ‬
‫ﺍﻝﻤﻭﺴﻭﻤﺔ ﺇﻝﻰ ﻨﺸﺎﺩﺭ ﻭﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺍﻝﻤﻭﺴﻭﻡ‪.‬‬
‫‪ .2.4.II‬ﺤﺴﺎﺏ ‪ pH‬ﻝﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻷﺴﺎﺱ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ‪ ) B‬ﺍﻝﻨﺸﺎﺩﺭ ‪ NH3‬ﻋﻠﻰ ﺴﺒﻴل‬

‫ﺍﻝﻤﺜﺎل( ﺒﺘﺭﻜﻴﺯﻋﻨﺩ ﻝﺤﻅﺔ ﺍﻹﻀﺎﻓﺔ ‪ . c‬ﻴﺨﻀﻊ ﺍﻝﻤﺤﻠﻭل ﺇﻝﻰ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪B + H2O B H+ + OH−‬‬
‫)‪(2‬‬ ‫‪2 H2O H 3O+ + OH−‬‬
‫ﺘﺸﺒﻪ ﻤﻌﺎ ﻝﺠﺔ ﻤﺤﺎ ﻝﻴل ﻜﻬﺫﻩ ﻤﺎ ﻗﻤﻨﺎ ﺒﻪ ﻓﻲ ﺤﺎ ﻝﺔ ﺍ ﻝﺤﻤﻭ ﺽ ﺍ ﻝﻀﻌﻴﻔﺔ ﻤﻊ ﺍ ﻝﺘﺸﺎﺒﻪ ﻓﻲ‬
‫ﺍﻷﺩﻭﺍﺭ ﺒﻴﻥ ﺍﻝﻤﻘﺎﺩﻴﺭ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪[OH− ] = ω‬‬ ‫‪←‬‬
‫→‬ ‫‪[H3O+ ] = h‬‬
‫‪p OH = − log ω‬‬ ‫‪←‬‬
‫→‬ ‫‪pH = − log h‬‬
‫‪KB‬‬ ‫‪←‬‬
‫→‬ ‫‪KA‬‬
‫‪pK B = p K w − pK A‬‬ ‫‪←‬‬
‫→‬ ‫‪pK A‬‬
‫ ﺍﻷﺴﺎﺱ ‪ B‬ﻀﻌﻴﻑ ﻨﺴﺒﻴﹰﺎ ﻭ‪/‬ﺃﻭ ﻤﻤﺩ‪‬ﺩ ﻗﻠﻴﻼﹰ‪ ،‬ﻓﺒﺭﺘﻨﺘﻪ‪ 1‬ﻤﺤﺩﻭﺩﺓ ‪:‬‬

‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺸﺭﻭﻁ ﻴﻜﻭﻥ ﺘﻘﺩ‪‬ﻡ ﺘﻔﺎﻋل ﺍﻷﺴﺎﺱ ‪ B‬ﻤﻊ ﺍﻝﻤﺎﺀ ﻀﻌﻴﻔﹰﺎ ﻭ ﻴﻜﻭﻥ ‪ω ≪ c :‬‬
‫ﻥ ‪ . [B ] = c − ω ≈ c‬ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ‪: K B‬‬
‫ﻭﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪[BH+ ] ⋅ [OH− ] ω 2‬‬
‫= ‪KB‬‬ ‫≈‬
‫] ‪[B‬‬ ‫‪c‬‬
‫ﻭ‬
‫‪pOH = (p K B + pc ) / 2‬‬
‫‪pH = p K w − (p K B + pc) / 2‬‬
‫‪pH = (p K w + p K A − pc) / 2‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍ ﻝﻤﺤﻠﻭل‬
‫ﻭ ﺒﻤﻘﺎ ﺭ ﺒﺔ ﻤﻤﺎ ﺜﻠﺔ ﻝﻤﺎ ﺭ ﺃ ﻴﻨﺎ ﻩ ﻓﻲ ﺤﺎ ﻝﺔ ﺤﻤﺽ ﻀﻌﻴﻑ ﻨﺠﺩ ﺃ ‪‬‬
‫ﺍﻝﻤﺤﺴﻭﺒﺔ ﺘﻜﻭﻥ ﺼﺤﻴﺤﺔ ﺇﺫﺍ ﻜﺎﻥ ‪ ، pOH ≤ p K B − 1‬ﻭﻫﺫﺍ ﻤﻜﺎﻓﺊ ﻝﻠﻤﺘﺭﺍﺠﺤﺔ‬
‫‪ pH ≥ p K A + 1‬ﺃﻭ ‪. p K B − pc ≥ 2‬‬
‫ ﺍﻷﺴﺎﺱ ﺍﻝﻀﻌﻴﻑ ‪ B‬ﻗﻭﻱ ﻨﺴﺒﻴﹰﺎ ﻭ‪/‬ﺃﻭ ﻤﻤﺩ‪‬ﺩ‪ ،‬ﻓﺒﺭﺘﻨﺘﻪ ﻜﺒﻴﺭﺓ ‪:‬‬

‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ‪: K B‬‬
‫‪+‬‬ ‫‪−‬‬
‫] ‪[BH ] ⋅ [OH‬‬ ‫‪ω2‬‬
‫= ‪KB‬‬ ‫=‬
‫] ‪[B‬‬ ‫‪c−ω‬‬
‫ﻭﻫﺫﺍ ﻴﻘﻭﺩﻨﺎ ﺇﻝﻰ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ‪:‬‬
‫‪ω2 + K B ⋅ ω − K B ⋅ c = 0‬‬
‫‪1‬‬
‫ﺍﻝ ‪‬ﺒﺭ‪‬ﺘﹶﻨﺔ‪ :‬ﻫﻲ ﺇﻀﺎﻓﺔ ﺍﻝﺒﺭﻭﺘﻭﻥ ﺇﻝﻰ ﺍﻷﺴﺎﺱ‪.‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻹﻴﺠﺎﺩ ﻗﻴﻤﺔ ‪ ω‬ﻭﺘﻜﻭﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻫﻲ‬

‫ﻴﻜﻔﻲ ﺤ ّ‬
‫‪. pH = p K w + log ω‬‬
‫ﻤﻥ ﻭﺠﻬﺔ ﻨﻅﺭﻋﻤﻠﻴﺔ‪ ،‬ﻝﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻷﺴﺎﺱ ﻀﻌﻴﻑ ﻴ‪‬ﻨﺼ‪‬ﺢ ﺒﻤﻘﺎﺭﻨﺔ‬
‫ﻗﻴﻡ ‪ pK B‬ﻭ ‪ pc‬ﻤﻊ ﺘﺒﺭﻴﺭ ﺍﻝﺨﻴﺎﺭ ﺍﻝﻤﺘﺨﺫ ﻤﻥ ﻭﺠﻬﺔ ﻨﻅﺭ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻭﺍﺴﺘﻌﻤﺎل ﻜل ﻤﻥ‬
‫ﺍﻝﻌﻼﻗﺘﻴﻥ‪:‬‬
‫‪ pH = (p K w + p K A − pc ) / 2‬ﻋﻨﺩﻤﺎ ‪. p K B − pc ≥ 2‬‬
‫‪ ω 2 + K B ⋅ ω − K B ⋅ c = 0‬ﻋﻨﺩﻤﺎ ‪. p K B − pc < 2‬‬
‫ﻭﺒﻌﺩ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﻨﺒﻐﻲ ﺍﻝﺘﺤﻘﹼﻕ ﺩﻭﻤﹰﺎ ﻤﻥ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﻤﻭﻀﻭﻋﺔ‪.‬‬
‫ﻴﻤﺜﹼل ﺍﻝﺸﻜل )‪ (4‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ )‪ ، pH = f (− log c‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﺘﺄﺨﺫ ‪ p K A‬ﻗﻴﻤﹰﺎ‬
‫ﻤﺨﺘﻠﻔﺔ‪ .‬ﻭﻴﻤﻜﻥ ﺍﺴﺘﻌﻤﺎل ﻫﺫﻩ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻝﺘﺤﺩﻴﺩ ﻗﻴﻡ ‪ pH‬ﻝﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻀﻌﻴﻑ‪.‬‬
‫‪pH‬‬
‫‪14‬‬
‫‪13‬‬
‫‪12‬‬
‫‪13‬‬
‫‪11‬‬
‫‪12‬‬
‫‪10‬‬
‫‪11‬‬ ‫‪9‬‬
‫‪pK A =8‬‬
‫‪10‬‬
‫‪7‬‬
‫‪6‬‬
‫‪9‬‬ ‫‪5‬‬
‫‪4‬‬
‫‪3‬‬
‫‪8‬‬ ‫‪2‬‬
‫‪1‬‬
‫‪− log c‬‬
‫‪7‬‬
‫‪0‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪8‬‬
‫ﺍﻝﺸﻜل )‪ pH = f (− log c ) : (4‬ﺃﻭ ﻤﺨﻁﻁ ‪ Flood‬ﺍﻝﻤﻭﺍﻓﻕ ﻝﻸﺴﺱ ﺍﻝﻀﻌﻴﻔﺔ ﺒﺩﻻﻝﺔ ﻗﻴﻡ ﻤﺨﺘﻠﻔﺔ ﻝـ ‪p K A‬‬
‫ﺤ ‪‬ﺩ ﺩ ﻋﻨﺩ ﺩ ﺭ ﺠﺔ ﺍ ﻝﺤﺭ ﺍ ﺭ ﺓ ‪ 25 C‬ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭ ل ﻤﻥ ﺍ ﻝﻨﺸﺎ ﺩ ﺭ ﺒﺘﺭ ﻜﻴﺯ ﻗﺩ ﺭﻩ‬
‫‬
‫‪. pK A (NH+‬‬
‫ﻥ‪4 / NH 3 ) = 9.2 :‬‬
‫‪ 1.0 × 10−4 mol/L‬ﺇﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﺍﻝﺤل‬
‫ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻲ‪:‬‬
‫‪NH3 + H2O NH+‬‬

‫‪4 + OH‬‬
‫‪−‬‬
‫ﻥ ﺒﺭﺘﻨﺔ ﺍﻝﻨﺸﺎﺩﺭ ﻀﻌﻴﻔﺔ‪ ،‬ﻭﺍﺴﺘﻌﻤﻠﻨﺎ ‪، pOH = (p K B + pc )/2‬‬

‫ﻝﻭ ﺍﻓﺘﺭﻀﻨﺎ ﺃ ‪‬‬
‫ﻭﺠﺩﻨﺎ ‪ ، pOH = 4.4‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ‪ . pH = 9.6‬ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻘﻴﻤﺔ ﻝﻴﺴﺕ ﺃﻜﺒﺭ ﻤﻥ‬
‫‪ pK A + 1‬ﻓﻘﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﺘﻲ ﺃﻭﺠﺩﻨﺎﻫﺎ ﻝﻴﺴﺕ ﺼﺤﻴﺤﺔ ) ﻭﻗﺩ ﻜﺎﻥ ﺒﺎﻹﻤﻜﺎﻥ‬
‫ﻥ ﺒﺭﺘﻨﺔ ﺍﻝﻨﺸﺎﺩﺭ ﻝﻴﺴﺕ‬
‫‪ ، (p K B − pc < 2‬ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬ ‫ﻥ‬
‫ﺘﻭﻗﹼﻊ ﻫﺫﺍ ﻤﻨﺫ ﺍﻝﺒﺩﺍﻴﺔ ﻷ ‪‬‬
‫ﻀﻌﻴﻔﺔ‪ ،‬ﻭﻋﻠﻴﻨﺎ ﺍﺴﺘﻌﻤﺎل ﺍﻝﻤﻌﺎﺩﻝﺔ ‪: ω 2 + K B ⋅ ω − K B ⋅ c = 0‬‬
‫‪ω 2 + 10−4.8 ⋅ ω − 108.8 = 0‬‬
‫ﻥ ‪. pH = 9.5‬‬‫ل ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﺴﺎﺒﻘﺔ ﻨﺠﺩ ‪ ، pOH = 4.5‬ﺃﻱ ﺇ ‪‬‬
‫ﺒﺤ ّ‬
‫‪ .5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﻭﺽ ﺃﻭ ﻤﺯﻴﺞ ﻤﻥ ﺃﺴﺱ‬
‫‪ .1.5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ﻭﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻴﻀ ‪‬ﻡ ﻤﺯﻴﺠﹰﺎ ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ‪ HA1‬ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ ‪ c1‬ﻋﻨﺩ ﻝﺤﻅﺔ‬

‫ﺍﻹﻀﺎﻓﺔ‪ ،‬ﻭﺤﻤﺽ ﻀﻌﻴﻑ ‪ HA2‬ﺘﺭﻜﻴﺯﻩ ‪ c2‬ﻋﻨﺩ ﻝﺤﻅﺔ ﺍﻹﻀﺎﻓﺔ‪ ،‬ﻭﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪. K A‬‬
‫ﻴﺘﻔﺎﻋل ﻫﺫﺍﻥ ﺍﻝﺤﻤﻀﺎﻥ ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪HA1 + H2O → H3O+ + A1−‬‬
‫)‪(2‬‬ ‫‪HA2 + H2O H 3O+ + A2−‬‬
‫ﻝﻨﺴ ‪‬ﻡ ‪ x1‬ﻭ ‪ x 2‬ﺩ ﺭ ﺠﺘﻲ ﺍ ﻝﺘﻘﺩ ﻡ ﺍ ﻝﺤﺠﻤﻴﺘﻴﻥ ﻝﻠﺘﻔﺎ ﻋﻠﻴﻥ )‪ (1‬ﻭ )‪ (2‬؛ ﻋﻨﺩ ﺌﺫ ﻴﻜﻭ ﻥ ‪:‬‬
‫ﻥ ‪ HA1‬ﻫﻭ ﺤﻤﺽ ﻗﻭﻱ‪ ،‬ﻓﻬﻭ ﻤﺘﻔﻜﻙ ﺘﻤﺎﻤﹰﺎ‪ ،‬ﻭ ] ‪ ، x 2 = [A2−‬ﻭﺃﺨﻴﺭﹰﺍ‬
‫‪ x1 = [A1− ] = c1‬ﻷ ‪‬‬
‫‪ . [H 3O+ ] = x1 + x 2 = [A1− ] + [A2− ] = c1 + x 2‬ﻨﻌﺎﻝﺞ ﻫﻨﺎ ﺤﺎﻝﺘﻴﻥ‪:‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻭﻫﻭ‬ ‫• ﺒﻔﺭﺽ ﺃﻥ ‪ x 2‬ﻜﺎﻥ ﻤﻬﻤ ﹰ‬

‫ﻼ ﺃﻤﺎﻡ ‪ c1‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﺍﻝﺫﻱ ﻴﻔﺭﺽ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪ .‬ﻭﻫﻜﺫﺍ ﻨﻜﺘﺏ ‪. pH = − logc1‬‬
‫ﺇ ﺫ ﺍ ﻜﺎ ﻨﺕ ﻗﻴﻤﺔ ‪ pH‬ﺍ ﻝﻤﺤﻠﻭ ل ﺍ ﻝﻤﺤﺴﻭ ﺒﺔ ﻭ ﻓﻕ ﺍ ﻝﻌﻼ ﻗﺔ ﺍ ﻝﺴﺎ ﺒﻘﺔ ﺘﺤﻘﹼﻕ ﺍ ﻝﻌﻼ ﻗﺔ‬
‫ﻥ ﺍﻝﻘﻴﻤﺔ ﺍﻝﻤﺤﺴﻭﺒﺔ ﺼﺤﻴﺤﺔ‪.‬‬
‫‪ pH < p K A − 1‬ﻓﻬﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫• ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻝﻤﻌﺎﻜﺴﺔ ﺘﻌﻁﻴﻨﺎ ﻤﻌﺎﺩﻝﺔ ﺤﺼﻴﻠﺔ ﺩﺭﺠﺘﻲ ﺘﻘﺩ‪‬ﻡ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ )‪ (1‬ﻭ )‪: (2‬‬
‫‪h = [H 3O+ ] = [A1− ] + [A2− ] = c1 + x 2‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ‬
‫) ‪c2 = [A2− ] + [HA2 ] = [A2− ]( 1 + h /K A‬‬
‫ﻜﺎﻥ‬
‫‪K A ⋅ c2‬‬
‫‪h = c1 +‬‬
‫‪KA + h‬‬
‫ﻭﻫﺫﺍ ﻴﺅﺩﻱ ﺇﻝﻰ ﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ ﻴﻠﺯﻡ ﺤﻠﹼﻬﺎ‪.‬‬
‫ﻻ ﻴﻀ ‪‬ﻡ ﺤﻤﻀﹰﺎ ﻗﻭﻴﹰﺎ ‪ HA1‬ﺒﺘﺭﻜﻴﺯ ‪ c1 = 0.020 mol/L‬ﻭﺤﻤﻀﹰﺎ‬
‫ﻝﻴﻜﻥ ﻝﺩﻴﻨﺎ ﻤﺤﻠﻭ ﹰ‬
‫ﻀﻌﻴﻔﹰﺎ ‪ HA2‬ﺤﻴﺙ ‪ pK A = 2.0‬ﻭﺒﺘﺭﻜﻴﺯ ‪ c2 = 0.10 mol/L‬ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪pH‬‬
‫ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﺍﻝﺤل‬
‫ﻻ ﺒﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ﺍﻝﻘﻭﻱ‬
‫ﻼ ﻭﻝﻡ ﻨﺄﺨﺫ ﺇ ﹼ‬
‫ﺇﺫﺍ ﺍﻋﺘﺒﺭﻨﺎ ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ﺍﻝﻀﻌﻴﻑ ﻤﻊ ﺍﻝﻤﺎﺀ ﻤﻬﻤ ﹰ‬
‫ﻤﻊ ﺍﻝﻤﺎﺀ ﻨﺠﺩ‪. pH1 = − log c1 = 1.7 :‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻘﻴﻤﺔ ﻗﺭﻴﺒﺔ ﻤﻥ ﻗﻴﻤﺔ ‪ pK A‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﻬﻲ ﻏﻴﺭ ﺼﺤﻴﺤﺔ ﻭﻴﺠﺏ ﻋﺩﻡ‬‫ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫‪K ⋅c‬‬
‫ل ﺍﻝﻤﻌﺎﺩﻝﺔ ‪h = c1 + A 2‬‬ ‫ﺇﻫﻤﺎل ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ﺍﻝﻀﻌﻴﻑ ﻤﻊ ﺍﻝﻤﺎﺀ‪ .‬ﻭﻋﻠﻴﻪ ﻴﻠﺯﻤﻨﺎ ﺤ ّ‬
‫‪KA + h‬‬
‫ﺍﻝﺘﻲ ﺘﺼﺒﺢ ﺒﻌﺩ ﺍﻝﺘﻌﻭﻴﺽ ﺍﻝﺭﻗﻤﻲ‪ ، h 2 − 1.0 × 10−2 ⋅ h − 1.2 × 10−3 = 0 :‬ﻭﻫﺫﺍ‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل ‪. pH = 1.4‬‬
‫ﻴﻜﺎﻓﺊ ‪ h = 0.040 mol/L‬ﺃﻱ ﺇ ‪‬‬
‫‪‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻭﻤﻭﻗﻊ ﻗﻴﻤﺔ ‪ pH‬ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪1.0‬‬ ‫‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺩﺭﻭﺱ‬ ‫‪1.5‬‬

‫‪pH1‬‬ ‫‪2.0‬‬ ‫‪pH‬‬
‫‪pK A‬‬
‫‪ .2.5.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﻀﻴﻥ ﻀﻌﻴﻔﻴﻥ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻴﻀ ‪‬ﻡ ﻤﺯﻴﺠﹰﺎ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ‪ HA1‬ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪K A1‬‬

‫ﺒﺘﺭﻜﻴﺯ ‪ c1‬ﻭﺤﻤﺽ ﻀﻌﻴﻑ ‪ HA2‬ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪ K A2‬ﺒﺘﺭﻜﻴﺯ ‪ . c2‬ﻴﺘﻔﺎﻋل ﻫﺫﺍﻥ‬
‫ﺍﻝﺤﻤﻀﺎﻥ ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪HA1 + H2O H3O+ + A1−‬‬
‫)‪(2‬‬ ‫‪HA2 + H2O H 3O+ + A2−‬‬
‫• ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻝﻌﺎﻤﺔ‪ ،‬ﻋﻨﺩ ﺘﺤﺩﻴﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﻨﺒﻐﻲ ﺃﻥ ﻨﺄﺨﺫ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ‬
‫)‪ (1‬ﻭ )‪ . (2‬ﻭﻴﻌﻁﻴﻨﺎ ﺸﺭﻁ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ‪:‬‬
‫] ‪h = [H3O+ ] = [A1− ] + [A2−‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪K A1 ⋅ c1‬‬ ‫‪K ⋅c‬‬
‫= ‪h‬‬ ‫‪+ A2 2‬‬
‫‪K A1 + h K A2 + h‬‬
‫ل ﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻝﺜﺔ ﻝﺘﻌﻴﻴﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻭﻫﺫﺍ ﻤﺎ ﻴﻘﻭﺩ ﺇﻝﻰ ﺤ ّ‬
‫• ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺤﻤﻀﺎﻥ ﻀﻌﻴﻔﻴﻥ ﻨﺴﺒﻴﹰﺎ ﻭ ﺘﻤﺩﻴﺩﻫﻤﺎ ﻀﻌﻴﻑ ‪ ،‬ﻴﻜﻭﻥ ] ‪[A1− ] ≪ [HA1‬‬
‫ﻭ ] ‪ ، [A2− ] ≪ [HA2‬ﻭﻋﻨﺩﻫﺎ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻜﺘﺏ‪:‬‬
‫‪K ⋅c‬‬ ‫‪K ⋅c‬‬
‫‪[A2− ] = A2 2‬‬ ‫ﻭ‬ ‫‪[A1− ] = A1 1‬‬
‫‪h‬‬ ‫‪h‬‬
‫ﻭﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﺍﻝﻌﺒﺎﺭﺓ‪:‬‬
‫‪K ⋅c‬‬ ‫‪K ⋅c‬‬
‫‪h = A1 1 + A2 2‬‬
‫‪h‬‬ ‫‪h‬‬
‫ﻭﺘﹸﻜﺘﹶﺏ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺴﺎﺒﻘﺔ ﻋﻠﻰ ﺍﻝﺸﻜل‪:‬‬
‫‪h 2 = K A1 ⋅ c1 + K A2 ⋅ c2‬‬
‫ﻥ‪:‬‬
‫ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬
‫‪1‬‬
‫) ‪pH = − log(K A1 ⋅ c1 + K A2 ⋅ c2‬‬
‫‪2‬‬
‫ﻤﺜﺎل ‪ :‬ﺇ ‪‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻲ ﺤﺎﻝﺔ ﻤﺯﻴﺞ ﻤﻜﻭ‪‬ﻥ ﻤﻥ‪:‬‬
‫ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﺨل )‪(pK A1 = 2.9, c1 = 0.080 mol/L‬‬
‫ﻭﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ )‪. (pK A2 = 3.2, c2 = 0.090 mol/L‬‬
‫ﺘﹸﻌﻁﻰ ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬
‫‪1‬‬
‫‪pH = − log(10−2.9 × 0.080 + 10−3.2 × 0.090) = 1.9‬‬
‫‪2‬‬
‫• ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺠﺩﺍﺀ ﺍﻥ ‪ K A1 ⋅ c1‬ﻭ ‪ K A2 ⋅ c2‬ﻤﺨﺘﻠﻔﻴﻥ ﺘﻤﺎﻤﹰﺎ ﺒﺎﻝﻤﺭﺍﺘﺏ‪ ،‬ﻓﺈ ‪‬‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﻔﺭﻀﻬﺎ ﺍﻝﺠﺩﺍﺀ ﺍﻷﻜﺒﺭ‪.‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻲ ﺤﺎﻝﺔ ﻤﺯﻴﺞ ﻤﻥ‪:‬‬
‫ﻤﺜﺎل ‪ :‬ﺇ ‪‬‬
‫)‪HA1 (pK A1 = 3.0, c1 = 0.10 mol/L‬‬
‫ﻭ )‪. HA2 (pK A2 = 7.0, c2 = 0.10 mol/L‬‬
‫ﺘﹸﻌﻁﻰ ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬

‫‪1‬‬
‫‪pH = − log(10−3.0 × 0.10) = 2.0‬‬
‫‪2‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‬
‫• ﻋﻨﺩ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻲ ﺤﺎﻝﺔ ﻤﺯﻴﺞ ﻤﻥ ﻋﺩﺓ ﺤﻤﻭﺽ ﻓﺈ ‪‬‬
‫ﻫﻭ ﺍﻝﺫﻱ ﻴﻭﺍﻓﻕ ﺍﻝﺤﻤﺽ ﺍﻝﻤﺘﻤﺘﻊ ﺒﺎﻝﺠﺩﺍﺀ ‪ K A ⋅ c‬ﺍﻷﻋﻠﻰ ‪ ،‬ﻭﻝﻴﺱ ﺒﺎﻝﻀﺭﻭﺭﺓ ﺍﻝﺤﻤﺽ‬
‫ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ﺍﻷﻋﻠﻰ‪.‬‬
‫ﺼل ﺇﻝﻴﻪ ﻓﻲ‬
‫ﻥ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﻨﺎ ﺇﻝﻴﻬﺎ ﻓﻲ ﺤﺎﻝﺔ ﻤﺯﻴﺞ ﻤﻥ ﻋﺩﺓ ﺤﻤﻭﺽ ﺘﺸﺎﺒﻪ ﻤﺎ ﻨﺘﻭ ‪‬‬
‫• ﺇ‪‬‬
‫‪.2.4.II‬‬ ‫ﺤﺎﻝﺔ ﻤﺯﻴﺞ ﻤﻥ ﻋﺩﺓ ﺃﺴﺱ‪ ،‬ﻤﻊ ﺍﺴﺘﻌﻤﺎل ﺍﻝﺘﺸﺎﺒﻬﺎﺕ ﺍﻝﺘﻲ ﺃﺸﺭﻨﺎ ﺇﺍﻴﻬﺎ ﻓﻲ ﺍﻝﻔﻘﺭﺓ‬
‫

‬
‫ﻝﻤﺎﺫﺍ ﻨﺫﺭﻑ ﺍﻝﺩﻤﻊ ﻋﻨﺩ ﺘﻘﻁﻴﻊ ﺍﻝﺒﺼل؟‬
‫ﺘﻀﻡ ﺍﻝﺒﺼﻠﺔ ﻜﻴﻴﺴﺎﺕ ﺼﻐﻴﺭﺓ ﺠﺩﹰﺍ ﺤﺎﻭﻴﺔ ﻏﺎﺯ )‪ SO3 (g‬ﺍﻝﺫﻱ ﻴﺘﺤﺭﺭ ﻤﻨﻬﺎ ﻋﻨﺩ ﺘﻘﻁﻴﻌﻬﺎ‪ .‬ﻭﻝﻤﺎ ﻜﺎﻨﺕ ﺍﻝﻌﻴﻥ ﻤﻐﻁﺎﺓ‬
‫ل ﻏﺎﺯ )‪ SO3 (g‬ﻓﻲ ﻫﺫﺍ ﺍﻝﺩﻤﻊ ﻭﻴﺘﻜﻭﻥ‬
‫ﺒﻁﺒﻘﺔ ﺭﻗﻴﻘﺔ ﻤﻥ ﺍﻝﺩﻤﻊ ﻏﺭﻀﻬﺎ ﺘﺨﻔﻴﻑ ﺍﻻﺤﺘﻜﺎﻙ ﺒﻴﻥ ﺍﻝﻌﻴﻥ ﻭﺍﻝﺠﻔﻥ‪ ،‬ﺍﻨﺤ ّ‬
‫ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ ‪: H2SO4‬‬
‫)‪SO3 (g) + H2O(l) ⇌ H2 SO4 (aq‬‬
‫ﻓﻴﺘﺴ ‪‬ﺒﺏ ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ ﺒﻭﺨﺯ ﺍﻝﻌﻴﻥ‪ ،‬ﻭﺘﺒﺩﺃ ﺍﻝﻐﺩﺩ ﺍﻝﺩﻤﻌﻴﺔ ﺒﺈﻓﺭﺍﺯ ﺍﻝﻤﺯﻴﺩ ﻤﻥ ﺍﻝﺩﻤﻊ‪ ،‬ﻭﻨﺠﻬﺵ ﺒﺎﻝﺒﻜﺎﺀ!‬
‫‪ .6.II‬ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻝﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ‪ . H2A‬ﻴﺘﻔﺎﻋل ﻫﺫﺍ ﺍﻝﺤﻤﺽ ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﻓﻕ‬

‫ﺍﻝﺘﻭﺍﺯﻨﻴﻥ ﺍﻝﻤﺘﻌﺎﻗﺒﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪H2A + H2O HA− + H 3O+‬‬ ‫‪: K A1‬‬

‫)‪(2‬‬ ‫‪HA− + H2O A2− + H3O+‬‬ ‫‪: K A2‬‬
‫ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺤﻤﺽ ‪ H2A‬ﻀﻌﻴﻔﹰﺎ ﻭﻗﻠﻴل ﺍﻝﺘﻤﺩﻴﺩ ﻤﻊ ﻓﺭﻕ ﻓﻲ ‪pK A2 − pK A1‬‬

‫ﺃﻜﺒﺭ ﻤﻥ ‪ 2‬ﻴﻜﻔﻲ ﺃﻥ ﻨﻘﺘﺼﺭ ﻋﻠﻰ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻷﻭل‪ ،‬ﻭﺒﺫﻝﻙ ﻴﻌﻭﺩ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪pH‬‬
‫ﺍﻝﻤﺤﻠﻭل ﺇﻝﻰ ﺤﺎﻝﺔ ﺤﻤﺽ ﻭﺤﻴﺩ ﺍﻝﻭﻅﻴﻔﺔ‪.‬‬
‫ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﻔﺭﻕ ‪ pK A2 − pK A1‬ﺃﺼﻐﺭ ﻤﻥ ‪ ، 2‬ﻴﺠﺏ ﺃﺨﺫ ﺍﻝﺘﻭﺍﺯﻨﻴﻥ‬

‫ﺍﻝﺴﺎﺒﻘﻴﻥ‪ .‬ﻭﺘﺴﻤﺢ ﻤﻌﺎﺩﻻﺕ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﻭﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل ﺒﺎﻝﻭﺼﻭل‬
‫ﺇﻝﻰ ﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻝﺜﺔ‪ .‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل )‪ (5‬ﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻓﻲ ﺤﺎﻝﺔ ﺤﻤﺽ‬
‫ﺜﻨﺎﺌﻲ ﺍﻝﻔﻭﺴﻔﻭﺭ ‪ H4 P2O7‬ﺤﻴﺙ ﻝﺩﻴﻨﺎ ) ‪، pK A = 1.8 ، pK A = 1.5‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪ .( pK A4 = 8.2 ، pK A = 6.0‬ﻨﻼﺤﻅ ﺃﻥ ﺍﻝﺤﻤﺽ ‪ H4 P2O7‬ﻤﺘﺸﺭ‪‬ﺩ ﺘﻤﺎﻤﹰﺎ‪،‬‬

‫‪3‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻻ ﺘﻨﺘﺞ ﻓﻘﻁ ﻤﻥ ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ﻤﻊ ﺍﻝﻤﺎﺀ‪ ،‬ﻭﻝﻜﻥ ﻤﻥ‬

‫ﺃﻱ ﺇ ‪‬‬
‫ﻥ ‪. pH = 1.4‬‬
‫ل ﺍﻝﻤﻌﺎﺩﻝﺔ ﻨﺠﺩ ﺃ ‪‬‬
‫‪ H3 P2O−‬ﻤﻊ ﺍﻝﻤﺎﺀ ﺃﻴﻀﹰﺎ‪ .‬ﻭﺒﺤ ّ‬
‫ﺘﻔﺎﻋل ‪7‬‬
‫ ﻤﻥ ﻭﺠﻬﺔ ﻨﻅﺭ ﻋﻤﻠﻴﺔ‪ ،‬ﻴ‪‬ﻨﺼﺢ ﺒﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ‬
‫ﺍﻝﺘﻭﺍﺯﻥ ﺍﻷﻭل ﻓﻘﻁ‪ ،‬ﺜ ‪‬ﻡ ﻨﻘﺎﺭﻥ ﺍﻝﻘﻴﻤﺔ ﺍﻝﺘﻲ ﺤﺼﻠﻨﺎ ﻋﻠﻴﻬﺎ ﻤﻊ ﻗﻴﻤﺔ ‪ pK A2‬ﻭﻨﻘﺭﺭ ﺒﻌﺩ‬
‫ﺫﻝﻙ ‪ :‬ﻫل ﻜﺎﻥ ﺘﻘﺭﻴﺒﻨﺎ ﺼﺤﻴﺤﹰﺎ ﺃﻡ ﻻ ؟‬
‫ ﻓﻲ ﺤﺎﻝﺔ ﺃﺴﺎﺱ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ ﻨﻌﺎﻝﺞ ﺍﻝﻤﺴﺄﻝﺔ ﺒﻁﺭﻴﻘﺔ ﻤﺸﺎﺒﻬﺔ ﻝﺤﺎﻝﺔ ﺍﻝﺤﻤﺽ ﻤﺘﻌﺩ‪‬ﺩ‬
‫‪.2.4.II‬‬ ‫ﺍﻝﻭﻅﻴﻔﺔ ﻤﻊ ﺍﺴﺘﻌﻤﺎل ﺍﻝﺘﺸﺎﺒﻬﺎﺕ ﺍﻝﺘﻲ ﺃﺸﺭﻨﺎ ﺇﻝﻴﻬﺎ ﻓﻲ ﺍﻝﻔﻘﺭﺓ‬
‫ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻤﻥ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺒﺘﺭﻜﻴﺯ ‪، 1.0 × 10−2 mol/L‬‬
‫ﺤﻴﺙ ‪ pK A1 = 6.4‬ﻭ ‪. pK A2 = 10.3‬‬
‫ﺍﻝﺤل‬
‫ﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﻠﺫﻴﻥ ﺴﻨﻌﺘﺒﺭﻫﻤﺎ ﻫﻤﺎ‪:‬‬
‫ﺇ‪‬‬
‫)‪(3‬‬ ‫‪CO2 + 2 H2O H 3O+ + HCO−‬‬
‫‪3‬‬
‫)‪(4‬‬ ‫‪HCO−‬‬ ‫‪+‬‬ ‫‪2−‬‬

‫‪3 + H2O H 3O + CO3‬‬
‫ﻴﻌﺘﺒﺭ ‪ CO2‬ﺤﻤﻀﹰﺎ ﻀﻌﻴﻔﹰﺎ ﻭﺘﻔﺎﻋﻠﻪ ﻤﻊ ﺍﻝﻤﺎﺀ ﻤﺤﺩﻭﺩﹰﺍ ﻭﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻜﺘﺏ‪:‬‬
‫‪. [CO2 ] = c − h ≈ c‬‬ ‫ﻭ‬ ‫‪[H 3O+ ] = [HCO−‬‬ ‫‪3]= h‬‬
‫‪1‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪. pH = (p K A1 + pc ) = 4.2 :‬‬
‫‪2‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺸﺭﻭﻁ ﻴﻜﻭﻥ‪:‬‬
‫] ‪[CO23−‬‬ ‫‪K A2‬‬
‫= ‪−‬‬ ‫‪= 10−6.1‬‬
‫] ‪[HCO3‬‬ ‫‪h‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل )‪ (4‬ﻤﻬﻤل ﺘﻤﺎﻤﹰﺎ‪.‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪1.0‬‬
‫‪H 4 P2 O7‬‬ ‫‪H 2 P2 O27 −‬‬
‫‪ւ‬‬ ‫‪ւ‬‬ ‫‪HP O73 − P O4 −‬‬
‫‪ւ2‬‬ ‫‪2 7‬‬
‫‪ւ‬‬
‫‪0.8‬‬
‫‪α1 = p K A‬‬
‫‪0.6‬‬ ‫‪1‬‬
‫‪α2 = pK A‬‬
‫‪2‬‬
‫‪α 3 = pK A‬‬
‫‪0.4‬‬ ‫‪H 3 P2 O−‬‬
‫‪7‬‬
‫‪3‬‬
‫‪α 4 = pK A‬‬
‫‪ւ‬‬ ‫‪4‬‬
‫‪0.2‬‬
‫‪α1‬‬ ‫‪α2‬‬ ‫‪α3‬‬ ‫‪α4‬‬

‫‪ց‬‬ ‫‪ւ‬‬ ‫‪ց‬‬ ‫‪ւ‬‬
‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪12‬‬ ‫‪14‬‬
‫ﺍﻝﺸﻜل )‪ : (5‬ﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻓﻲ ﺤﺎﻝﺔ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻔﻭﺴﻔﻭﺭ ‪. H 4 P2O7‬‬
‫‪ .7.II‬ﻤﺘﺫﺒﺫﺏ ﺤﻤﻀﻲ ﺃﺴﺎﺴﻲ‬
‫ﻥ ﺍﻝﺘﻔﻜﻙ ﺍﻝﻜﻠﻲ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻝﻤﻠﺢ ‪ NaHA‬ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ ‪ c‬ﻋﻨﺩ ﺍﻹﻀﺎﻓﺔ‪ .‬ﺇ ‪‬‬
‫ﻝﻠﻤﻠﺢ ﻴﺨﻀﻊ ﻝﻠﻤﻌﺎﺩﻝﺔ‪:‬‬
‫‪NaHA(s) → Na + + HA−‬‬
‫ﻴ‪‬ﻌﺘﺒ‪‬ﺭ ‪ HA−‬ﻤﺘﺫﺒﺫﺒﹰﺎ ﺤﻤﻀﻴﹰﺎ‪-‬ﺃﺴﺎﺴﻴﹰﺎ ﻭﺫﻝﻙ ﻷﻨﻪ ﻴﺅﺩﻱ ﺩﻭﺭ ﺤﻤﺽ ﻓﻲ ﺍﻝﺯﻭﺝ ‪HA− / A2−‬‬
‫ﻭﻴﺅﺩﻱ ﺩﻭﺭ ﺃﺴﺎﺱ ﻓﻲ ﺍﻝﺯﻭﺝ ‪ . H2A / HA−‬ﻭﻫﻜﺫﺍ ﻴﺩﺨل ‪ HA−‬ﻓﻲ ﺜﻼﺜﺔ ﺘﻭﺍﺯﻨﺎﺕ ﺫﺍﺕ‬
‫ﺜﻭﺍﺒﺕ ‪ K 20 ، K10 :‬ﻭ ‪. K 30‬‬
‫)‪(1‬‬ ‫‪2 H A− H2A + A2−‬‬ ‫‪: K10 = K A2 /K A1‬‬

‫)‪(2‬‬ ‫‪H A− + H2O A2− + H 3O+‬‬ ‫‪: K 20 = K A2‬‬
‫)‪(3‬‬ ‫‪H A− + H2O H2A + OH−‬‬ ‫‪: K 30 = K B1 = K w /K A1‬‬
‫ﻓﻲ ﻜﺜﻴﺭ ﻤﻥ ﺍﻷﺤﻴﺎﻥ ﻴﻜﻭﻥ ‪ K10‬ﺃﻜﺒﺭ ﺒﻜﺜﻴﺭ ﻤﻥ ‪ K 20‬ﻭ ‪ K 30‬ﻭﻴﻜﻭﻥ ﻤﻥ ﹶﺜ ‪‬ﻡ ﺍﻝﺘﻔﺎﻋل‬
‫)‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻭﻫﻭ ﺍﻝﺫﻱ ﻴﻔﺭﺽ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻭﺒﻨﺎﺀ ﻋﻠﻴﻪ ﻨﻜﺘﺏ ] ‪ . [H2A] = [A2−‬ﻭﻨﻜﺘﺏ ﺍﻝﺠﺩﺍﺀ ‪ K A2 ⋅ K A1‬ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫] ‪h ⋅ [A2− ] h ⋅ [HA− ] h 2 ⋅ [A2−‬‬
‫= ‪K A2 ⋅ K A1‬‬ ‫⋅‬ ‫=‬
‫] ‪[HA−‬‬ ‫]‪[H2A‬‬ ‫]‪[H2A‬‬
‫ﻥ ‪. K A2 ⋅ K A1 = h 2 :‬‬
‫ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪1‬‬
‫= ‪. pH‬‬ ‫) ‪(p K A1 + p K A2‬‬
‫‪2‬‬
‫ﻥ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻻ ﻴﺘﻌﻠﹼﻕ ﺒﺘﺭﻜﻴﺯ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫• ﻨﻼﺤﻅ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺃ ‪‬‬
‫• ﻨﺠﺩ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺃﻴﻀﺎﹰ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل ﺃﺜﻨﺎﺀ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ‪ ،‬ﻭﻜﺫﻝﻙ‬
‫ﻨﺠﺩ ﻫﺫﻩ ﺍﻝﻌﻼﻗﺔ ﻋﻨﺩﻤﺎ ﻨﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﻝﻤﺯﻴﺞ ﻤﺘﺴﺎﻭﻱ ﺍﻝﻤﻭﻝﻴﺔ ﻤﻥ ﺤﻤﺽ ﻤﻥ ﺯﻭﺝ‬
‫ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪ K A1‬ﻤﻊ ﺃﺴﺎﺱ ﻤﻥ ﺯﻭﺝ ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪. K A2‬‬
‫ل ﻴﺄﺨﺫ ﻓﻲ‬
‫ﻥ ﺍﻝﺤ ّ‬
‫• ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺘﻲ ﻻ ﻴﻜﻭﻥ ﻓﻴﻬﺎ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻓﺈ ‪‬‬
‫ﺍﻝﺤﺴﺒﺎﻥ ﺃﻴﻀﹰﺎ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺜﺎﻨﻲ ﻭﺍﻝﺜﺎﻝﺙ‪ .‬ﻭﺒﻜﺘﺎﺒﺔ ﺸﺭﻁ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﻭﺍﻻﻋﺘﺩﺍل‬
‫ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻨﺤﺼل ﻋﻠﻰ ﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ ﻓﻲ ‪ . h‬ﻭﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻴﺘﻌﻠﹼﻕ ‪pH‬‬
‫ﺍﻝﻤﺤﻠﻭل ﺒﺎﻝﺘﺭﻜﻴﺯ‪.‬‬
‫ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻭﺤﻴﺩ ﺓ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺃﻭ ) ﻜﺭﺒﻭﻨﺎﺕ‬
‫ﻥ‪:‬‬
‫ﺍﻝﺼﻭﺩﻴﻭﻡ ﺍﻝﺤﺎﻤﻀﻴﺔ( ﺒﺘﺭﻜﻴﺯ ‪. c = 0.10 mol/L‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫‪. pK A2 (HCO−‬‬
‫ﻭ ‪3 / CO3 ) = 10.3‬‬
‫‪2−‬‬
‫‪pK A1(CO2 / HCO−‬‬
‫‪3 ) = 6.4‬‬
‫ﺍﻝﺤل‬
‫ﻀﻤﻥ ﻤﺤﻠﻭل ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺍﻝﺤﺎﻤﻀﻴﺔ ﺘﺠﺭﻱ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ‬
‫ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫)‪(1‬‬ ‫‪2 HCO−‬‬ ‫‪2−‬‬
‫‪3 CO2 + CO3 + H2O‬‬ ‫‪K10 = K A2 / K A1 = 10−3.9‬‬
‫‪(2)HCO−‬‬ ‫‪2−‬‬
‫‪3 + H2O CO3 + H 3O‬‬
‫‪+‬‬
‫‪K 20 = 10−10.3‬‬
‫‪(3)HCO−‬‬ ‫‪−‬‬
‫‪3 + H2O CO2 + OH + H2O‬‬ ‫‪K 30 = 10−7.6‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻭﻫﻭ ﺍﻝﺫﻱ ﺴﻴﻔﺭﺽ‬
‫ﻭﺒﺎﻝﻨﻅﺭ ﺇﻝﻰ ﻗﻴﻡ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﻓﺈ ‪‬‬
‫ﻥ‪:‬‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل‪ .‬ﺃﻱ ﺇ ‪‬‬
‫‪1‬‬
‫= ‪pH‬‬ ‫‪(p K A1 + p K A2 ) = 8.35‬‬
‫‪2‬‬
‫ﻭﻴﺠﺭﻱ ﺘﺤﺩﻴﺩ ] ‪ [CO2‬ﻭ ] ‪ [CO23−‬ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﺜﺎﺒﺕ ‪: K10‬‬

‫‪[CO2 ] = [CO23− ] = (K10 ⋅ [HCO−‬‬ ‫‪2 1/2‬‬
‫) ]‪3‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻤﺘﻘﺩ‪‬ﻤﹰﺎ ﻋﻠﻰ ﻨﺤﻭ ﺒﺴﻴﻁ ﻨﻅﺭﹰﺍ ﻝﻘﻴﻤﺔ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪ ،‬ﻨﺴﺘﻁﻴﻊ ﺃﻥ ﻨﻜﺘﺏ‪:‬‬
‫ﻥ‪:‬‬
‫‪ . [HCO−‬ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃ ‪‬‬
‫‪3]≈c‬‬
‫‪[CO2 ] = [CO23− ] = 1.1 × 10−3 mol/L‬‬

‫ل ﻤﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ )‪(2‬‬
‫ﻥ ﺘﻘﺩ‪‬ﻡ ﻜ ّ‬
‫ﻥ ] ‪ h ≪ [CO23−‬ﻭ ] ‪ . ω ≪ [CO2‬ﺃﻱ ﺃ ‪‬‬
‫ﻨﺘﺤﻘﹼﻕ ﻤﻥ ﺃ ‪‬‬
‫ﻭ )‪ (3‬ﻤﻬﻤل ﻭﺍﻝﺤﺴﺎﺏ ﺼﺤﻴﺢ‪.‬‬
‫‪ .8.II‬ﺒﻌﺽ ﺍﻝﻤﺯﺍﺌﺞ ﺍﻝﺤﻤﻀﻴﺔ ﻭﺍﻷﺴﺎﺴﻴﺔ‬
‫‪ .1.8.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ﻭﻤﻥ ﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ‪ HA‬ﺒﺘﺭﻜﻴﺯ ﻋﻨﺩ ﺍﻹﻀﺎﻓﺔ ‪ ca‬ﻭﻤﻥ ﺃﺴﺎﺴﻪ‬

‫ﺍﻝﻤﺭﺍﻓﻕ ‪ A−‬ﺒﺘﺭﻜﻴﺯ ‪ cb‬ﻋﻨﺩ ﺍﻹﻀﺎﻓﺔ‪ .‬ﻭﻝﻴﻜﻥ ‪ K A‬ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ﻝﻠﺯﻭﺝ ‪. HA / A−‬‬
‫ﻴﺴﺎﻫﻡ ﺍﻝﺯﻭﺝ ‪ HA / A−‬ﺒﺎﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺜﻼﺜﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫)‪(1‬‬ ‫‪H A + A− A− + H A‬‬ ‫‪K10 = 1‬‬
‫)‪(2‬‬ ‫‪H A + H2O A− + H 3O+‬‬ ‫‪K 20 = K A‬‬
‫)‪(3‬‬ ‫‪A− + H2O HA + OH−‬‬ ‫‪K 30 = K B = K w / K A‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ‬
‫• ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺜﺎﺒﺘﺎﻥ ‪ K A‬ﻭ ‪ K B‬ﺼﻐﻴﺭﻴﻥ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ﺍﻝﻭﺍﺤﺩ‪ ،‬ﻓﺈ ‪‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ ﺍﻝﺫﻱ ﻴﺠﺏ ﺃﺨﺫﻩ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﻭﻫﻭ ﻻ ﻴﻐﻴ‪‬ﺭ ﻤﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ‬
‫‪c‬‬
‫ﺍﻻﺒﺘﺩﺍﺌﻴﺔ‪ .‬ﻭﻋﻠﻴﻪ ﻨﻜﺘﺏ‪. pH = p K A + log b :‬‬
‫‪ca‬‬
‫• ﺇﺫﺍ ﻜﺎﻥ ﺃﺤﺩ ﺍﻝﺜﺎﺒﺘﻴﻥ ﻭﻝﻨﻔﺘﺭﺽ ‪ K A‬ﻝﻴﺱ ﺼﻐﻴﺭﹰﺍ ﺒﺎﻝﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻭﺍﺤﺩ ﻓﻌﻨﺩﻫﺎ ﻴﻨﺒﻐﻲ ﺃﻥ‬
‫ﻨﺄﺨﺫ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ )‪ (1‬ﻭ )‪ (2‬ﻓﻲ ﺤﺴﺎﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻥ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل ‪ CHCl2COOH‬ﻴﺘﻤﺘﻊ ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪pK A = 1.3‬‬
‫ﺇ‪‬‬
‫ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻨﺤﺼل ﻋﻠﻴﻪ ﻤﻥ ﻤﺯﺝ ‪ 10 mL‬ﻤﻥ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل‬
‫ﺒﺘﺭﻜﻴﺯ ‪ 2.0 × 10−2 mol/L‬ﻤﻊ ‪ 30 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫ﺒﺘﺭﻜﻴﺯ ‪. 1.0 × 10−2 mol/L‬‬
‫ﺍﻝﺤل‬
‫ل ﻤﻥ ﺍﻝﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ‪:‬‬
‫ﻝﻴﻜﻥ ‪ ca‬ﻭ ‪ cb‬ﺍﻝﺘﺭﻜﻴﺯﻴﻥ ﻋﻨﺩ ﺍﻹﻀﺎﻓﺔ ﻝﻜ ّ‬
‫‪10 × 2.0 × 10−2‬‬
‫= ‪ca‬‬ ‫‪= 5.0 × 10−3 mol/L‬‬
‫‪40‬‬
‫‪30 × 1.0 × 10−2‬‬
‫= ‪cb‬‬ ‫‪= 7.5 × 10−3 mol/L‬‬
‫‪40‬‬
‫ﻥ‪:‬‬
‫ﻻ ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل )‪ (1‬ﻜﺘﻔﺎﻋل ﺭﺍﺠﺢ‪ ،‬ﻨﺠﺩ ﺃ ‪‬‬
‫ﺇﺫﺍ ﻝﻡ ﻨﻌﺘﺒﺭ ﺇ ﹼ‬
‫‪c‬‬
‫‪pH = p K A + log b = 1.5‬‬
‫‪ca‬‬
‫ﻥ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل ﻫﻭ ﺤﻤﺽ ﻗﻭﻱ ﻭﺘﻔﺎﻋﻠﻪ ﻤﻊ ﺍﻝﻤﺎﺀ ﻴﺘﻤﺘﻊ ﺒﺜﺎﺒﺕ‬
‫ﻭﻝﻜ ‪‬‬
‫‪ ، pK A = 1.3‬ﻭﻴﺠﺏ ﺃﺨﺫﻩ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ‪:‬‬
‫‪CHCl2COOH‬‬ ‫‪+ H2O ⇌ CHCl2COO−‬‬ ‫‪+ H 3O+‬‬

‫‪t = 0 5.0 × 10−3‬‬ ‫‪−‬‬ ‫‪7.5 × 10−3‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪5.0 × 10−3 − h‬‬ ‫‪−‬‬ ‫‪7.5 × 10−3 + h‬‬ ‫‪h‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﺎﺴﺘﻌﻤﺎل ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﻨﺠﺩ ﺃ ‪‬‬
‫‪−3‬‬
‫‪(7.5 × 10 + h ) ⋅ h‬‬
‫= ‪KA‬‬ ‫‪−3‬‬ ‫‪= 10−1.3‬‬
‫) ‪(5.0 × 10 − h‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻴﻌﻁﻲ ‪ h = 4.1 × 10−3 mol/L‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ‪. pH = 2.4‬‬
‫ﻭﺤ ّ‬
‫‪ .2.8.II‬ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ﻭﻤﻥ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﻏﻴﺭ ﻤﺭﺍﻓﻕ ﻝﻪ‬
‫ﻝﻨﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻨﺤﺼل ﻋﻠﻴﻪ ﻤﻥ ﻤﺯﺝ ‪ 100 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﻨﺸﺎﺩﺭ ﺒﺘﺭﻜﻴﺯ‬
‫‪ cb‬ﻤﻊ ‪ 100 mL‬ﻤﻥ ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ﺒﺘﺭﻜﻴﺯ ‪ ca‬ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ‪:‬‬
‫‪. cb = 6.0 × 10−2 mol/L ، ca = 2.0 × 10−2 mol/L .a‬‬
‫‪ca = cb = 2.0 × 10−2 mol/L .b‬‬
‫ﻥ‪:‬‬
‫ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫‪pK A1 = pK A (NH+‬‬
‫‪4 / NH 3 ) = 9.2‬‬
‫‪pK A2 = pK A (HNO2 / NO−‬‬
‫‪2 ) = 3.2‬‬
‫‪ (NH+‬ﻋﻠﻰ ﻤﺤﻭﺭ ‪ pH‬ﺸﺎﻗﻭﻝﻲ‪،‬‬
‫ﻨﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ ) ‪ (HNO2 / NO2‬ﻭ ) ‪4 / NH 3‬‬
‫‪−‬‬
‫ﻭﺫﻝﻙ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ pK A‬ﻝﻜل ﻤﻨﻬﻤﺎ‪ .‬ﻜﻤﺎ ﻨﻀﻊ ﺇﻁﺎﺭﹰﺍ ﺤﻭل ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺘﻲ‬
‫ﺃﻀﻴﻔﺕ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺃﻱ ‪ NH3‬ﻭ ‪. HNO2‬‬
‫‪pH‬‬
‫‪NH3‬‬
‫‪9.20‬‬
‫‪NH+‬‬
‫‪4‬‬
‫‪NO−‬‬
‫‪2‬‬ ‫‪3.20‬‬
‫‪H NO2‬‬
‫ﺇﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻭ‪:‬‬

‫‪NH3 + HNO2 NH+‬‬ ‫‪−‬‬
‫‪4 + NO2‬‬ ‫‪K 0 = 10(pKA1 −pKA2 ) = 1.0 × 106‬‬
‫ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ‪ .‬ﻝﻨﺩﺭﺱ ﺤﺼﻴﻠﺔ ﺍﻝﺘﻔﺎﻋل ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﻤﻁﻠﻭﺒﺘﻴﻥ ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺘﺄﺜﻴﺭ‬
‫ﺍﻝﺘﻤﺩﻴﺩ‪.‬‬
‫‪.a‬‬
‫‪NH 3‬‬ ‫‪+ HNO2‬‬ ‫‪ NH+‬‬
‫‪4‬‬ ‫‪+ NO−‬‬
‫‪2‬‬
‫‪t = 0 3.0 × 10−2‬‬ ‫‪1.0 × 10−2‬‬ ‫‪−‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪2.0 × 10−2‬‬ ‫‪ε‬‬ ‫‪1.0 × 10−2‬‬ ‫‪1.0 × 10−2‬‬
‫ل ﻤﻥ ‪ NH 3‬ﻭ ‪ NH 4‬ﻭ ‪2‬‬

‫‪ NO−‬ﻤﻊ ﺍﻝﻤﺎﺀ ﻤﺤﺩﻭﺩﺓ ﺠﺩﹰﺍ‪ .‬ﻭﻫﻲ ﻻ ﺘﻐﻴ‪‬ﺭ ﻜﺜﻴﺭﹰﺍ‬ ‫‪+‬‬
‫ﻥ ﺘﻔﺎﻋﻼﺕ ﻜ ّ‬
‫ﺇ‪‬‬
‫ﺍﻝﺤﺎﻝﺔ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻝﻠﺠﻤﻠﺔ ﻭﻴﻤﻜﻥ ﺇﻫﻤﺎﻝﻬﺎ‪.‬‬
‫ﻼ‪:‬‬
‫‪ NH+‬ﻤﺜ ﹰ‬
‫ﻭﻴﻤﻜﻥ ﻭﺒﺴﻬﻭﻝﺔ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﺯﻭﺝ ‪4 / NH 3‬‬
‫] ‪[NH 3‬‬
‫‪pH = p K A1 + log‬‬ ‫‪= 9.5‬‬
‫‪[NH+‬‬
‫] ‪4‬‬
‫‪.b‬‬
‫‪NH 3‬‬ ‫‪+ HNO2‬‬ ‫‪ NH+‬‬
‫‪4‬‬ ‫‪+ NO−‬‬
‫‪2‬‬
‫‪t = 0 1.0 × 10−2‬‬ ‫‪1.0 × 10−2‬‬ ‫‪−‬‬ ‫‪−‬‬

‫‪teq‬‬ ‫‪ε‬‬ ‫‪ε‬‬ ‫‪1.0 × 10−2‬‬ ‫‪1.0 × 10−2‬‬
‫ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪ [NH 3 ] = [HNO2 ] :‬ﻭ ] ‪4 ] = [NO2‬‬

‫‪[NH+‬‬ ‫‪−‬‬
‫ﻭﻴﻜﺘﺏ ﺍﻝﺠﺩﺍﺀ ‪ K A1 ⋅ K A2 = h 2‬ﺒﺎﻝﺸﻜل‪:‬‬

‫‪[NH3 ] ⋅ [NO−‬‬ ‫‪2 ]⋅h‬‬
‫‪2‬‬
‫= ‪K A1 ⋅ K A2‬‬ ‫‪= h2‬‬
‫‪[NH+‬‬‫‪4‬‬ ‫]‬ ‫⋅‬ ‫‪[HNO‬‬ ‫‪2‬‬ ‫]‬
‫‪1‬‬
‫‪pH = (p K A1 + p K A2 ) = 6.2‬‬
‫‪2‬‬
‫ﻝﻨﺤﺩ‪‬ﺩ ﺍﻵﻥ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻨﺤﺼل ﻋﻠﻴﻪ ﻤﻥ ﻤﺯﺝ ‪ 100 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ‬
‫ﺍﻷﻤﻭﻨﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ ca′‬ﻤﻊ ‪ 100 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻨﺘﺭﻴﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ cb′‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ‬
‫‪ ca′ = 2.0 × 10−2 mol/L‬ﻭ ‪. cb′ = 6.0 × 10−2 mol/L‬‬
‫‪ (NH+‬ﻋﻠﻰ ﻤﺤﻭﺭ ‪ pH‬ﺸﺎﻗﻭﻝﻲ‪،‬‬
‫ﻨﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ ) ‪ (HNO2 / NO2‬ﻭ ) ‪4 / NH 3‬‬
‫‪−‬‬
‫ﻭﺫﻝﻙ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ pK A‬ﻝﻜل ﻤﻨﻬﻤﺎ‪ .‬ﻭﻨﻀﻊ ﺇﻁﺎﺭﹰﺍ ﺤﻭل ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺘﻲ ﺃﻀﻴﻔﺕ ﺇﻝﻰ‬
‫‪. NO−‬‬
‫ﺍﻝﻤﺤﻠﻭل ﺃﻱ ‪ NH 4‬ﻭ ‪2‬‬
‫‪+‬‬
‫‪pH‬‬
‫‪NH3‬‬
‫‪9.2‬‬
‫‪NH+‬‬
‫‪4‬‬
‫‪NO−‬‬
‫‪2‬‬ ‫‪3.2‬‬
‫‪HNO2‬‬
‫ﺇﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﺒﻴﻥ ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ ﻭﺸﺎﺭﺩﺓ ﺍﻝﻨﺘﺭﻴﺕ‪:‬‬
‫‪NH+‬‬ ‫‪−‬‬
‫‪4 + NO2 ⇌ NH 3 + HNO2‬‬ ‫‪K 0 = 10(pKA2 −pKA1 ) = 1.0 × 10−6‬‬
‫ﻥ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻤﺤﺩﻭﺩ ﺠﺩﹰﺍ‪ .‬ﻝﻨﺩﺭﺱ ﺤﺼﻴﻠﺔ ﺍﻝﺘﻔﺎﻋل ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺘﺄﺜﻴﺭ‬
‫ﺍﻝﺘﻤﺩﻴﺩ‪.‬‬
‫‪NH+‬‬
‫‪4‬‬ ‫‪+‬‬ ‫‪NO−‬‬
‫‪2‬‬ ‫‪
NH 3‬‬ ‫‪+ HNO2‬‬
‫‪−2‬‬ ‫‪−2‬‬
‫‪t = 0 1.0 × 10‬‬ ‫‪3.0 × 10‬‬ ‫‪−‬‬ ‫‪−‬‬
‫‪−2‬‬ ‫‪−2‬‬
‫‪teq‬‬ ‫‪1.0 × 10‬‬ ‫‪−x‬‬ ‫‪3.0 × 10‬‬ ‫‪−x‬‬ ‫‪x‬‬ ‫‪x‬‬
‫ﻭﻨﻜﺘﺏ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‬
‫‪2‬‬
‫‪x‬‬
‫= ‪K0‬‬ ‫‪= 10−6‬‬
‫) ‪(0.010 − x )(0.030 − x‬‬
‫ﻥ‪:‬‬
‫ﺒﺈﻫﻤﺎل ‪ x‬ﻤ‪‬ﻘﺎﺭﻨﺔ ﺒﺎﻝﻤﻘﺩﺍﺭﻴﻥ ‪ 0.010‬ﻭ ‪ 0.030‬ﻨﻅﺭﹰﺍ ﻝﻘﻴﻤﺔ ‪ ، K 0‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪. x = 1.7 × 10−5 mol/L‬‬
‫ﺃﻤ‪‬ﺎ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻬﻲ ﺘﻌﻁﻰ ﺒﺎﻝﻌﻼﻗﺔ‪:‬‬
‫] ‪[NH 3‬‬ ‫‪[NO−‬‬
‫]‪2‬‬
‫‪pH = p K A1 + log‬‬ ‫‪= p K A2 + log‬‬
‫‪[NH+‬‬
‫] ‪4‬‬ ‫] ‪[HNO2‬‬
‫ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﺍﻝﺭﻗﻤﻲ ﻨﺠﺩ ﺃﻥ‪. pH = 6.45 :‬‬
‫ﻤﻼﺤﻅﺔ‪:‬‬
‫ﻴﻤﻜﻥ ﺘﺤﺩﻴﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺒﺎﺴﺘﻌﻤﺎل ﺃﺤﺩ ﺍﻝﺯﻭﺠﻴﻥ‪ ،‬ﻭﺩﻭﻥ ﺤﺴﺎﺏ ‪ . x‬ﺇﺫ ﻝﻤ‪‬ﺎ‬
‫ﻥ‪:‬‬
‫ﻜﺎﻨﺕ ‪ x‬ﻤﻬﻤﻠﺔ ﺃﻤﺎﻡ ‪ ca′ /2‬ﻭ ‪ cb′ /2‬ﻓﺈ ‪‬‬
‫] ‪[NH 3‬‬ ‫‪x‬‬
‫‪pH = p K A1 + log‬‬ ‫‪= p K A1 + log‬‬
‫‪[NH+‬‬‫] ‪4‬‬
‫‪ca′ /2‬‬
‫‪[NO−‬‬‫] ‪2‬‬ ‫‪c ′ /2‬‬
‫‪pH = p K A2 + log‬‬ ‫‪= p K A2‬‬ ‫‪+ log b‬‬
‫] ‪[HNO2‬‬ ‫‪x‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﺤﺫﻑ ‪ x‬ﺒﻴﻥ ﺍﻝﻌﺒﺎﺭﺘﻴﻥ ﺍﻝﺴﺎﺒﻘﺘﻴﻥ ﻨﺠﺩ ﺃ ‪‬‬
‫‪cb′‬‬
‫‪pH = 1/2(p K A1 + p K A2 + log‬‬ ‫‪) = 6.45‬‬
‫‪ca′‬‬
‫ﺘﻔﻴﺩ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻓﻲ ﺇﻴﺠﺎﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺩﻭﻥ ﺤﺴﺎﺏ ‪. x‬‬
‫

‬
‫ﻝﻤﺎﺫﺍ ﻴﻨﺒﻐﻲ ﻋﺩﻡ ﻤﺯﺝ ﺍﻝﻤﺒﻴ‪‬ﻀﺎﺕ ﻤﻊ ﺍﻝﻤﻨﻅﻔﺎﺕ ﺍﻝﺤﺎﻭﻴﺔ ﻋﻠﻰ ﺍﻝﻨﺸﺎﺩﺭ؟‬
‫ﻨﺴﺘﻌﻤل ﻓﻲ ﻤﻨﺎﺯﻝﻨﺎ ﺍﻝﻤﻨﻅﻔﺎﺕ ﻭﺍﻝﻤﺒﻴﻀﺎﺕ ﻝﺘﻨﻅﻴﻑ ﺍﻝﺴﻁﻭﺡ ﻭﺘﻁﻬﻴﺭﻫﺎ ﻭﺘﻌﻘﻴﻤﻬﺎ‪ ،‬ﻭﻨﻘﺭﺃ ﺩﺍﺌﻤ ﹰﺎ ﻋﻠﻰ ﻋﺒﻭﺍﺕ ﺍﻝﺘﺒﻴﻴﺽ‬
‫ﺘﺤﺫﻴﺭﺍﺕ ﺒﻌﺩﻡ ﻤﺯﺝ ﺍﻝﻤﺒﻴﻀﺎﺕ ﻤﻊ ﻤﻨﻅﻔﺎﺕ ﺃﺨﺭﻯ ﺘﺤﻭﻱ ﺍﻝﻨﺸﺎﺩﺭ‪ ،‬ﻓﻤﺎ ﺍﻝﺴ ‪‬ﺭ ﻭﺭﺍﺀ ﺫﻝﻙ؟‬
‫ﻥ ﺍﻝﻤﻨﻅﻔﺎﺕ‬
‫ل ﻋﻥ ‪ ، 5%‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﻻ ﻤﺎﺌﻴ ﹰﺎ ﻤﻥ ﺘﺤﺕ ﻜﻠﻭﺭﻴﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ﻻ ﻴﻘ ّ‬
‫ﺘﻀ ‪‬ﻡ ﺍﻝﻤﺒﻴﻀﺎﺕ ﻤﺤﻠﻭ ﹰ‬
‫ﺍﻝﺤﺎﻭﻴﺔ ﻋﻠﻰ ﺍﻝﻨﺸﺎﺩﺭ )ﻜﺘﻠﻙ ﺍﻝﺘﻲ ﻨﺴﺘﻌﻤﻠﻬﺎ ﻓﻲ ﺘﻨﻅﻴﻑ ﺍﻝﺯﺠﺎﺝ ﻭﺍﻝﻨﻭﺍﻓﺫ ﻭﻤﻨﻅﻔﺎﺕ ﺍﻷﻓﺭﺍﻥ ﻭ‪ (...‬ﻫﻲ ﻤﺤﺎﻝﻴل ﻤﺎﺌﻴﺔ‬
‫ﺒﺘﺭﻜﻴﺯ ‪ 5 − 10%‬ﻤﻥ ﺍﻝﻨﺸﺎﺩﺭ‪ .‬ﻭﻝﻭ ﺘﺄﻤﻠﻨﺎ ﺠﻴﺩﹰﺍ ﻫﺫﻩ ﺍﻝﻤﺤﺎﻝﻴل ﻝﻼﺤﻅﻨﺎ ﺃﻨﻬﺎ ﺫﺍﺕ ﺘﻔﺎﻋل ﻗﻠﻭﻱ‪ ،‬ﻭﻝﻴﺱ ﻜﻤﺎ ‪‬ﻴﻅﻥ‬
‫ﺨﻁﺄ ﺃﻨﻨﺎ ﺒﻤﺯﺠﻬﺎ ﻗﺩ ﻗﻤﻨﺎ ﺒﺘﻌﺩﻴل ﺤﻤﺽ ﺒﺄﺴﺎﺱ‪ .‬ﻓﻲ ﻭﺍﻗﻊ ﺍﻷﻤﺭ ﻋﻨﺩ ﻤﺯﺝ ﺍﻝﻤﺒﻴﺽ ﻤﻊ ﺍﻝﻤﻨﻅﻑ ﺍﻝﺤﺎﻭﻱ ﻋﻠﻰ‬
‫ﺍﻝﻨﺸﺎﺩﺭ ﺘﺘﻜﻭ‪‬ﻥ ﻋﺎﺌﻠﺔ ﻤﻥ ﺍﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﻐﺎﺯﻴﺔ ﺍﻝﺴﺎﻤﺔ ﺍﻝﺘﻲ ﺘﺤﻤل ﺍﺴﻡ ﺍﻝﻜﻠﻭﺭ ﺃﻤﻴﻥ‪:‬‬
‫ﺃﺤﺎﺩﻱ ﻜﻠﻭﺭ ﺍﻷﻤﻴﻥ ‪OCl− + NH 3 → OH− + NH2Cl‬‬
‫ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻷﻤﻴﻥ ‪OCl− + NH2Cl → OH− + NHCl2‬‬
‫ﺜﻼﺜﻲ ﻜﻠﻭﺭ ﺍﻷﻤﻴﻥ ‪OCl− + NHCl2 → OH− + NCl3‬‬
‫ﻭﻫﺫﻩ ﺍﻝﻐﺎﺯﺍﺕ ﺫﺍﺕ ﺭﺍﺌﺤﺔ ﻭﺨﹼﺎﺯﺓ ﺘﺸﺒﻪ ﺭﺍﺌﺤﺔ ﻏﺎﺯ ﺍﻝﻜﻠﻭﺭ ﻭﺘﺤﺭﻕ ﺍﻷﻏﺸﻴﺔ ﺍﻝﻤﺨﺎﻁﻴﺔ‪ .‬ﻓﺈﺫﺍ ﺯﺍﺩ ﺍﻝﻨﺸﺎﺩﺭ ﺘﻜﻭ‪‬ﻥ‬
‫ﺍﻝﻬﻴﺩﺭﺍﺯﻴﻥ‪ ،‬ﻭﻫﻲ ﻤﺎﺩﺓ ﺴﺎﻤﺔ ﺃﻴﻀﹰﺎ ﻭﻗﺎﺒﻠﺔ ﻝﻼﻨﻔﺠﺎﺭ‪:‬‬
‫‪NH2Cl + NH 3 + OH → Cl− + N2 H 4 + H2O‬‬
‫‪−‬‬
‫‪ .3.8.II‬ﻤﺯﺍﺌﺞ ﻤﺨﺘﻠﻔﺔ‬
‫ﻝﻨﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﻨﺤﺼل ﻋﻠﻴﻪ ﻤﻥ ﻤﺯﺝ ‪ 20 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ‬
‫‪ 0.10 mol/L‬ﻭ ‪ 30 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺴﻠﻔﻴﺩ )ﻜﺒﺭﻴﺘﻴﺩ( ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪0.40 mol/L‬‬
‫ﻭ ‪ 50 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺴﻠﻔﻴﺩ )ﻜﺒﺭﻴﺘﻴﺩ( ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺒﺘﺭﻜﻴﺯ ‪ . 0.20 mol/L‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫‪pK A (HS− /S2− ) = 13.0 ، pK A (H2S/HS− ) = 7.0‬‬

‫‪2‬‬ ‫‪1‬‬
‫ل‪:‬‬
‫ﺍﻝﺤ ّ‬
‫ﻨﻀﻊ ﻋﻠﻰ ﻤﺤﻭﺭ ‪ pH‬ﺸﺎﻗﻭﻝﻲ ﺍﻝﺯﻭﺠﻴﻥ ) ‪ (H2S/HS−‬ﻭ ) ‪ (HS− /S2−‬ﺍﻋﺘﻤﺎﺩﹰﺍ‬
‫ﻋﻠﻰ ﻗﻴﻡ ‪ pK A‬ﻝﻜل ﻤﻨﻬﻤﺎ ﻭﻜﺫﻝﻙ ﻨﻀﻊ ﺯﻭﺠﻲ ﺍﻝﻤﺎﺀ‪ .‬ﻭﻨﻀﻊ ﺇﻁﺎﺭﹰﺍ ﺤﻭل ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻷﻭل ‪ PR1‬ﻫﻭ ﺍﻝﺫﻱ ﻴﺠﺭﻱ ﺒﻴﻥ‬

‫ﺍﻝﺘﻲ ﺃﻀﻴﻔﺕ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻓﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﺤﻤﺽ ﺍﻷﻗﻭﻯ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺃﻱ ‪ H2S‬ﻭﺍﻷﺴﺎﺱ ﺍﻷﻗﻭﻯ ﺃﻱ ‪: OH−‬‬
‫‪pH‬‬
‫‪OH−‬‬
‫‪14‬‬
‫‪H2O‬‬
‫‪S2−‬‬ ‫‪13‬‬
‫‪HS−‬‬
‫‪HS−‬‬ ‫‪7‬‬
‫‪H2 S‬‬
‫‪H2O‬‬
‫‪0‬‬
‫‪H3O+‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻷﻭل‬
‫) ‪(pK w −pK A‬‬

‫‪H2S + OH− HS− + H2O‬‬ ‫‪K10 = 10‬‬ ‫‪1‬‬ ‫‪= 1.0 × 107‬‬
‫ﻭﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ‪ .‬ﻝﻨﺩﺭﺱ ﺤﺼﻴﻠﺔ ﺍﻝﺘﻔﺎﻋل ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺘﺄﺜﻴﺭ ﺍﻝﺘﻤﺩﻴﺩ‪:‬‬
‫‪H2 S‬‬ ‫‪+ OH−‬‬ ‫‪ HS−‬‬ ‫‪+ H 2O‬‬

‫‪−2‬‬ ‫‪−2‬‬
‫‪t =0‬‬ ‫‪10.0 × 10‬‬ ‫‪2.0 × 10‬‬ ‫‪−‬‬ ‫‪−‬‬
‫‪−2‬‬ ‫‪−2‬‬
‫‪teq (PR1) 8.0 × 10‬‬ ‫‪ε‬‬ ‫‪2.0 × 10‬‬
‫ﺒﻌﺩ ﺫﻝﻙ‪ ،‬ﻴﺠﺭﻱ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻨﻲ ‪ PR2‬ﺒﻴﻥ ‪ H2S‬ﻭ ‪: S2−‬‬
‫) ‪(pK A −pK A‬‬

‫‪H2S + S2− 2 HS−‬‬ ‫‪K 20 = 10‬‬ ‫‪2‬‬ ‫‪1‬‬ ‫‪= 1.0 × 106‬‬
‫‪pH‬‬
‫‪S2−‬‬
‫‪13‬‬
‫‪HS−‬‬
‫‪HS−‬‬ ‫‪7‬‬
‫‪H2 S‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻨﻲ‬
‫ﻭﻨﻼﺤﻅ ﺃﻥ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ‪ .‬ﻝﻨﺩﺭﺱ ﺤﺼﻴﻠﺔ ﺍﻝﺘﻔﺎﻋل ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺘﺄﺜﻴﺭ ﺍﻝﺘﻤﺩﻴﺩ‪:‬‬
‫‪H2 S‬‬ ‫‪+ S2−‬‬ ‫‪ 2 HS−‬‬
‫‪t =0‬‬ ‫‪8.0 × 10−2‬‬ ‫‪12.0 × 10−2‬‬ ‫‪2.0 × 10−2‬‬
‫‪teq (PR2) ε‬‬ ‫‪4.0 × 10−2‬‬ ‫‪18.0 × 10−2‬‬
‫ﺘﻌﺘﺒﺭ ﺸﺎﺭﺩﺓ ﺍﻝﺴﻠﻔﻴﺩ ﺃﺴﺎﺴﹰﺎ ﻗﻭﻴﹰﺎ ﻨﺴﺒﻴﹰﺎ )‪ . (pK B = pK w − pK A = 1.0‬ﻭﻤﻥ‬

‫‪2‬‬ ‫‪2‬‬
‫ﻼ‪ ،‬ﻭﻫﻭ ﻴﺸﻜﹼل ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻝﺙ ‪:PR3‬‬

‫ﻥ ﺘﻔﺎﻋﻠﻬﺎ ﻤﻊ ﺍﻝﻤﺎﺀ ﻝﻴﺱ ﻤﻬﻤ ﹰ‬
‫ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫‪S2−‬‬ ‫‪+ H2O HS−‬‬ ‫‪+ OH−‬‬
‫‪t =0‬‬ ‫‪4.0 × 10−2‬‬ ‫‪18.0 × 10−2‬‬ ‫‪−‬‬
‫‪teq (PR3) 4.0 × 10−2 − ω‬‬ ‫‪18.0 × 10−2 + ω‬‬ ‫‪ω‬‬
‫ﻥ‪:‬‬
‫ﺒﺎﺴﺘﻌﻤﺎل ﺜﺎﺒﺕ ﺍﻝﺘﻔﺎﻋل ﻨﺠﺩ ﺃ ‪‬‬
‫‪(18.0 × 10−2 + ω) ⋅ ω‬‬
‫= ‪KB‬‬ ‫‪= 1.0 × 10−1‬‬
‫‪2‬‬ ‫‪−2‬‬
‫‪(4.0 × 10‬‬ ‫)‪− ω‬‬
‫ﻥ ‪. pH = 12.1‬‬
‫ﻥ ‪ . ω = 1.4 × 10−2 mol/L :‬ﺃﻱ ﺇ ‪‬‬
‫‪pH‬‬
‫‪OH−‬‬ ‫‪14‬‬
‫‪H2 O‬‬
‫‪S2−‬‬
‫‪13‬‬
‫‪HS−‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻝﺙ‬
‫ﻭﻓﻲ ﺍﻝﺨﺘﺎﻡ ﻤﻥ ﺍﻝﻤﻔﻴﺩ ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ ﺃﻨﹼﻪ ﻴﻤﻜﻥ ﺘﻌﻤﻴﻡ ﺍﻝﻁﺭﻴﻘﺔ ﺍﻝﺘﻲ ﺍﺘﺒﻌﻨﺎﻫﺎ ﻓﻲ ﺩﺭﺍﺴﺔ‬
‫ﺍﻝﻤﺯﻴﺞ ﺍﻝﺴﺎﺒﻕ ﻋﻠﻰ ﺃﻱ ﻨﻭﻉ ﺁﺨﺭ ﻤﻥ ﺍﻝﻤﺯﺍﺌﺞ‪.‬‬
‫‬
‫‪ pH‬ﻤﺤﺎﻝﻴل ﺤﻤﺽ ﻗﻭﻱ ﻭﺃﺴﺎﺱ ﻗﻭﻱ‬ ‫‬
‫‪ .1‬ﺍﺤﺴﺏ ‪ pH‬ﻤﺤﻠﻭل ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺒﺘﺭﻜﻴﺯ ‪ C‬ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺜﻼﺙ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪،C 2 = 1.0 × 10−7 mol/L ،C 1 = 1.0 × 10−3 mol/L‬‬
‫‪.C 3 = 1.0 × 10−9 mol/L‬‬
‫‪ .2‬ﻨﻌﻴﺩ ﺍﻝﺴﺅﺍل ﺍﻝﺴﺎﺒﻕ ﻨﻔﺴﻪ ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﻠﻭل ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻋﻨﺩ ﺩﺭﺠﺔ‬
‫ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻝﻪ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﺴﺎﺒﻘﺔ ﺫﺍﺘﻬﺎ‪.‬‬
‫‪ pH‬ﻭﻤﻌﺎﻤل ﺍﻝﺘﺤﻠﹼل ﻝﺤﻤﺽ ﻀﻌﻴﻑ‬ ‫‬

‫‪ .1‬ﺍﺤﺴﺏ ‪ pH‬ﻤﺤﻠﻭل ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ‪ HNO2‬ﺒﺘﺭﻜﻴﺯ ‪ C‬ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪،C 1 = 0.10 mol/L‬‬ ‫‪(a‬‬
‫‪،C 2 = 1.0 × 10−2 mol/L‬‬ ‫‪(b‬‬
‫‪.C 3 = 1.0 × 10−5 mol/L‬‬ ‫‪(c‬‬

‫‪ .2‬ﺍﺤﺴﺏ ﻤﻌﺎﻤل ﺍﻝﺘﺤﻠﹼل ﻝﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ ‪ HNO2‬ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺜﻼﺙ ﺍﻝﺴﺎﺒﻘﺔ‪ .‬ﻤﺎﺫﺍ‬
‫‪. pK A (HNO2 / NO−‬‬
‫ﺘﺴﺘﻨﺘﺞ؟ ‪2 ) = 3.2‬‬
‫‪ pH‬ﻭﻤﻌﺎﻤل ﺍﻝﺒﺭﺘﻨﺔ ﻷﺴﺎﺱ ﻀﻌﻴﻑ‬ ‫‬

‫‪ .1‬ﺍﺤﺴﺏ ‪ pH‬ﻤﺤﻠﻭل ﺜﻨﺎﺌﻲ ﻤﻴﺜﻴل ﺍﻷﻤﻴﻥ ‪ (CH 3 )2NH‬ﺒﺘﺭﻜﻴﺯ ‪ C‬ﻓﻲ ﺍﻝﺤﺎﻻﺕ‬
‫ﺍﻝﺜﻼﺙ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪،C 1 = 0.10 mol/L‬‬ ‫‪(a‬‬
‫‪،C 2 = 1.0 × 10−2 mol/L‬‬ ‫‪(b‬‬
‫‪.C 3 = 1.0 × 10−5 mol/L‬‬ ‫‪(c‬‬

‫‪ .2‬ﺍﺤﺴﺏ ﻤﻌﺎﻤل ﺍﻝﺒﺭﺘﻨﺔ ﻝﺜﻨﺎﺌﻲ ﻤﻴﺜﻴل ﺍﻷﻤﻴﻥ ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺜﻼﺙ ﺍﻝﺴﺎﺒﻘﺔ‪ .‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪. p K A ((CH3 )2 NH2+ / (CH 3 )2 NH) = 11.0‬‬
‫ﻤﺯﻴﺞ ﺤﻤﺽ ﻗﻭﻱ ‪ -‬ﺤﻤﺽ ﻀﻌﻴﻑ‬ ‫‬

‫‪ V1 = 40.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ‬ ‫ﻨﻤﺯﺝ‬
‫‪ C 1 = 0.10 mol/L‬ﻭ ‪ V2 = 60.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل‬
‫‪ CHCl2COOH‬ﺒﺘﺭﻜﻴﺯ ‪ ،C 2 = 0.10 mol/L‬ﻭﻝﻴﻜﻥ ‪ S‬ﻫﺫﺍ ﺍﻝﻤﺯﻴﺞ‪.‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ‪ S‬ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ‪:‬‬
‫‪ .a‬ﺒﺈﻫﻤﺎل ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ ﺍﻝﺘﻲ ﻴﻘﺩﻤﻬﺎ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل ‪. CHCl2COOH‬‬
‫‪ .b‬ﺒﺈﻫﻤﺎل ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ ﺍﻝﺘﻲ ﻴﻘﺩﻤﻬﺎ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .2‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻔﻌﻠﻴﺔ ﻝﻠﻤﺤﻠﻭل ‪. S‬‬
‫‪ .3‬ﺍﺤﺴﺏ ﻤﻌﺎﻤل ﺘﺤﻠﹼل ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل ﻓﻲ ﺍﻝﺤﺎﻝﺔ ‪ .b.1‬ﻭﻓﻲ ﺍﻝﺤﺎﻝﺔ ‪ ، .2‬ﻤﺎﺫﺍ‬
‫ﺘﺴﺘﻨﺘﺞ ؟‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪. p K A (CHCl2COOH / CHCl2COO− ) = 1.3 :‬‬
‫ﻤﺯﺍﺌﺞ ﺤﻤﻭﺽ ﻀﻌﻴﻔﺔ‬ ‫‬
‫ل ﻜﻤﻴﺔ ﻗﺩﺭﻫﺎ ‪ n1‬ﻤﻥ ﺤﻤﺽ ﺍﻝﻨﻤل ‪HCOOH‬‬

‫ﻻ ﺤﺠﻤﻪ ‪ 250 mL‬ﺒﺤ ّ‬
‫ﻭﻜﻤﻴﺔ ﻗﺩﺭﻫﺎ ‪ n2‬ﻤﻥ ﺤﻤﺽ ﺍﻷﺴﻜﻭﺭﺒﻴﻙ ‪ . C6 H8O6‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻲ‬
‫ﺍﻝﺤﺎﻻﺕ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪ n1 = 4.0 × 10−2 mol .a‬ﻭ ‪. n2 = 2.0 × 10−4 mol‬‬
‫‪ n1 = 2.0 × 10−2 mol .b‬ﻭ ‪. n2 = 4.0 × 10−2 mol‬‬
‫‪ n1 = 2.0 × 10−4 mol .c‬ﻭ ‪. n2 = 4.0 × 10−2 mol‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪pK A (HCOOH/HCOO− ) = 3.75 :‬‬

‫‪1‬‬
‫‪pK A (C6 H8O6 /C6 H7O−‬‬

‫‪6 ) = 4.05‬‬
‫‪2‬‬
‫ﻤﺯﺍﺌﺞ ﺃﺴﺱ ﻀﻌﻴﻔﺔ‬ ‫‬

‫ﻗﺩﺭﻩ‬ ‫ﺒﺘﺭﻜﻴﺯ‬ ‫‪N2 H 4‬‬ ‫ﺍﻝﻬﻴﺩﺭﺍﺯﻴﻥ‬ ‫ﻤﺤﻠﻭل‬ ‫‪ V1 = 20.0 mL‬ﻤﻥ‬ ‫ﻨﻤﺯﺝ‬
‫‪ ،C 1 = 8.0 × 10−2 mol/L‬ﻭ ‪ V2 = 30.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﻨﺸﺎﺩﺭ ‪NH3‬‬
‫ﺒﺘﺭﻜﻴﺯ ‪.C 2 = 1.0 × 10−2 mol/L‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪. N2 H +‬‬
‫‪ .2‬ﺍﺤﺴﺏ ﺘﺭﺍﻜﻴﺯ ‪ NH 3‬ﻭ ‪ N2 H 4‬ﻭ ‪ NH 4‬ﻭ ‪5‬‬
‫‪+‬‬
‫‪. pK A (N2H+‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪5 / N2 H 4 ) = 8.5 ، pK A (NH 4 / NH 3 ) = 9.2 :‬‬
‫‪+‬‬
‫‪ pH‬ﺍﻝﺤﻤﻭﺽ ﺍﻝﻤﺘﻌﺩﺩﺓ ﺍﻝﻭﻅﻴﻔﺔ‬ ‫‬

‫ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﺤﻤﺽ ﺍﻝﺴﻴﻠﻴﻨﻴﻭﻡ ‪ H2SeO3‬ﺒﺘﺭﻜﻴﺯ ‪ C‬ﻓﻲ ﺍﻝﺤﺎﻻﺕ‬
‫ﺍﻝﺜﻼﺙ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪،C 1 = 0.10 mol/L‬‬ ‫‪(a‬‬
‫‪،C 2 = 1.0 × 10−2 mol/L‬‬ ‫‪(b‬‬
‫‪.C 3 = 1.0 × 10−5 mol/L‬‬ ‫‪(c‬‬

‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪. pK A = 8.3 ، pK A = 2.6 :‬‬
‫‪2‬‬ ‫‪1‬‬
‫ﻤﺤﺎﻝﻴل ﺤﻤﺽ ﺍﻷﻭﻜﺴﺎﻝﻴﻙ‬ ‫‬

‫‪ .1‬ﺃﻭﺠﺩ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭل ﺘﺭﻜﻴﺯﻩ ‪ C 1 = 0.10 mol/L‬ﻤﻥ ﺤﻤﺽ ﺍﻷﻭﻜﺴﺎﻝﻴﻙ‬
‫ﺫﻱ ﺍﻝﺼﻴﻐﺔ ‪. H2C2O4‬‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺤﺠﻡ ﻗﺩﺭﻩ ‪ V1 = 20.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺤﻤﺽ ﺍﻷﻭﻜﺴﺎﻝﻴﻙ ﺍﻝﺫﻱ‬
‫ﺘﺭ ﻜﻴﺯ ﻩ ‪ ، C 1‬ﺤﺠﻤﹰﺎ ﻗﺩ ﺭ ﻩ ‪ V2 = 5.0 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﺍ ﻝﺼﻭ ﺩ ﺍ ﻝﺫ ﻱ ﺘﺭ ﻜﻴﺯ‬
‫‪.C 2 = 0.20 mol/L‬‬
‫‪ .a‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ‪.‬‬
‫‪ .b‬ﻓﺴ‪‬ﺭ ﺍﻝﻨﺘﻴﺠﺔ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﺕ ﺇﻝﻴﻬﺎ‪.‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪ :‬ﺤﻤﺽ ﺍﻷﻭﻜﺴﺎﻝﻴﻙ ‪. pK A2 = 4.3 ، pK A1 = 1.2‬‬
‫‪ pH‬ﻤﺤﺎﻝﻴل ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ‬ ‫ ‬

‫ﺃﻭﺠﺩ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺘﺎﻝﻴﺔ ﺫﺍﺕ ﺍﻝﺘﺭﺍﻜﻴﺯ ‪: 1.0 × 10−2 mol/L‬‬
‫‪. pK A (Cu2+ /Cu(OH)+ ) = 7.00‬‬ ‫‪ .1‬ﻨﺘﺭﺍﺕ ﺍﻝﻨﺤﺎﺱ )‪، (II‬‬

‫‪. pK A (Al 3+ /Al(OH)2 + ) = 4.95‬‬ ‫‪ .2‬ﻜﻠﻭﺭ ﺍﻷﻝﻤﻨﻴﻭﻡ‪،‬‬
‫‪. pK A (Zn2+ /Zn(OH)+ ) = 9.60‬‬ ‫‪ .3‬ﻨﺘﺭﺍﺕ ﺍﻝﺘﻭﺘﻴﺎﺀ‪،‬‬
‫‪. pK A (Fe2+ /Fe(OH)+ ) = 8.45‬‬ ‫‪ .4‬ﻜﻠﻭﺭ ﺍﻝﺤﺩﻴﺩ )‪، (II‬‬
‫‪. pK A (Fe3+ /Fe(OH)2 + ) = 2.15‬‬ ‫‪ .5‬ﻜﻠﻭﺭ ﺍﻝﺤﺩﻴﺩ )‪، (III‬‬
‫‪ .6‬ﻜﻠﻭﺭ ﺍﻝﺼﻭﺩﻴﻭﻡ‪.‬‬
‫‪ pH‬ﻤﺤﺎﻝﻴل ﺸﻭﺍﺭﺩ ﺍﻝﻔﻭﺴﻔﺎﺕ ﻭﺍﻷﻤﻭﻨﻴﻭﻡ‬ ‫

‬
‫‪ .1‬ﺍﺤﺴﺏ ‪ pH‬ﻤﺤﻠﻭل ﺘﺭﻜﻴﺯﻩ ‪ 0.100 mol/L‬ﻤﻥ ﻫﻴﺩﺭﻭﺠﻴﻥ ﻓﻭﺴﻔﺎﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ‬
‫ﻭﺍﻝﺼﻭﺩﻴﻭﻡ ‪. Na(NH4 )HPO4‬‬
‫‪ .2‬ﺃﻋﺩ ﺍﻝﺴﺅﺍل ﺍﻝﺴﺎﺒﻕ ﻨﻔﺴﻪ ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﻠﻭل ﻤﻥ ﻓﻭﺴﻔﺎﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ ‪(NH 4 )3 PO4‬‬
‫ﺒﺎﻝﺘﺭﻜﻴﺯ ﻨﻔﺴﻪ‪.‬‬
‫ﻻ ﻤﻥ ﺍﻝﺼﻭﺩ ﺍﻝﺼﻠﺏ‬
‫‪ .3‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻷﺨﻴﺭ ﺩﻭﻥ ﺘﻤﺩﻴﺩ ﻜﻤﻴﺔ ﻗﺩﺭﻫﺎ ‪ n‬ﻤﻭ ﹰ‬
‫ﺒﺤﻴﺙ ﺘﺼﺒﺢ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻤﺴﺎﻭﻴﺔ ‪ . 9.5‬ﺍﺤﺴﺏ ‪ n‬ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﻠﻭل ﺤﺠﻤﻪ‬
‫‪. 1L‬‬
‫‪ . pK A = 9.2 : NH+‬ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ ‪: H3 PO4‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪ :‬ﺍﻝﺯﻭﺝ ‪4 /NH 3‬‬
‫‪. pK A = 12.1 ، pK A = 7.2 ، pK A = 2.15‬‬

‫‪3‬‬ ‫‪2‬‬ ‫‪1‬‬
‫‪ pH‬ﺍﻝﻤﺯﺍﺌﺞ )‪(1‬‬ ‫‬

‫ﻻ ﻤﻥ ﺤﻤﺽ ﺍ ﻝﺨل‪،‬‬
‫ﺍ ﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﻤﺤﻠﻭ ل ﻤﺎ ﺌﻲ ﺤﺠﻤﻪ ‪ 1L‬ﻴﻀ ‪‬ﻡ ‪ 0.30‬ﻤﻭ ﹰ‬
‫ﻻ ﻤﻥ‬
‫ﻻ ﻤﻥ ﺴﻴﺎﻨﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ‪ ،‬ﻭ ‪ 0.20‬ﻤﻭ ﹰ‬ ‫ﻭ ‪ 0.20‬ﻤﻭ ﹰ‬
‫ﻻ ﻤﻥ ﺍﻝﺼﻭﺩ ‪ ،‬ﻭ ‪ 0.05‬ﻤﻭ ﹰ‬
‫ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‪.‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪:‬‬
‫‪. pK A (CH 3COOH / CH3COO− ) = 4.75‬‬
‫‪. pK A (HCN / CN− ) = 9.30‬‬
‫‪ pH‬ﺍﻝﻤﺯﺍﺌﺞ )‪(2‬‬ ‫‬

‫ﻻ ﻤﻥ ﺤﻤﺽ ﺍﻝﻔﻠﻭﺭ ‪HF‬‬
‫ﻻ ﺤﺠﻤﻪ ‪ 1.00 L‬ﺒﺈﺫﺍﺒﺔ ﻜﻤﻴﺔ ﻗﺩﺭﻫﺎ ‪ n1‬ﻤﻭ ﹰ‬
‫ﻻ ﻤﻥ ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ‪. CH 3COONa‬‬
‫ﻭ ‪ n2‬ﻤﻭ ﹰ‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻝﻨﺎﺘﺠﺔ ﻭﺤﺩ‪‬ﺩ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻬﺎ‪.‬‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺜﻼﺙ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪ n1 = 0.20 mol .a‬ﻭ ‪. n2 = 0.40 mol‬‬
‫‪ n1 = 0.30 mol .b‬ﻭ ‪. n2 = 0.30 mol‬‬
‫‪ n1 = 0.40 mol .c‬ﻭ ‪. n2 = 0.20 mol‬‬
‫‪. pK A (CH 3COOH / CH3COO− ) = 4.75‬‬
‫‪. pK A (HF / F− ) = 3.20‬‬
‫‪ pH‬ﺍﻝﺴﻠﻔﻴﺩﺍﺕ‬ ‫‬
‫‪ 1.0 × 10‬ﺍ ﻷ ﻭ ل )‪ (A‬ﻴﻀ ‪‬ﻡ ﺴﻠﻔﻴﺩ‬ ‫‪−2‬‬
‫ل ﻤﻨﻬﻤﺎ ﺒﺘﺭ ﻜﻴﺯ ‪mol/L‬‬
‫ﻝﺩ ﻴﻨﺎ ﻤﺤﻠﻭ ﻻ ﻥ ﻜ ّ‬
‫ﺍ ﻝﻬﻴﺩ ﺭ ﻭ ﺠﻴﻥ ‪ ،‬ﻭ ﺍ ﻝﺜﺎ ﻨﻲ ) ‪ (B‬ﻴﻀ ‪‬ﻡ ﺴﻠﻔﻴﺩ ﺍ ﻝﺼﻭ ﺩ ﻴﻭ ﻡ ‪ . Na 2S‬ﺍ ﻨﻁﻼ ﻗﹰﺎ ﻤﻥ ﻫﺫ ﻴﻥ‬
‫ﺍﻝﻤﺤﻠﻭﻝﻴﻥ ﻨﺤﻀ‪‬ﺭ ﺜﻼﺜﺔ ﻤﺤﺎﻝﻴل ) ‪: (E ) ، (D ) ، (C‬‬
‫ﺍﻝﻤﺤﻠﻭل ) ‪ 100 mL : (C‬ﻤﻥ )‪ (A‬ﻭ ‪ 50 mL‬ﻤﻥ ) ‪. (B‬‬
‫ﺍﻝﻤﺤﻠﻭل ) ‪ 100 mL : (D‬ﻤﻥ )‪ (A‬ﻭ ‪ 100 mL‬ﻤﻥ ) ‪. (B‬‬
‫ﺍﻝﻤﺤﻠﻭل ) ‪ 50 mL : (E‬ﻤﻥ )‪ (A‬ﻭ ‪ 100 mL‬ﻤﻥ ) ‪. (B‬‬
‫ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺨﻤﺴﺔ‪.‬‬
‫‪ pK A (H2S / HS− ) = 7.0‬ﻭ ‪. pK A (HS− / S2− ) = 13.0‬‬
‫‪2‬‬ ‫‪1‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻟﺚ‬
‫
‬
‫ ‬
‫‪ .I‬ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ‬

‫‪ .1.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ‬
‫‪ .2.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻗﻭﻱ ﺒﺄﺴﺎﺱ ﻗﻭﻱ‬
‫‪ .3.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ‬
‫‪ .4.I‬ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺤﻤﺽ ﻗﻭﻱ‬
‫‪ .5.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﻭﻅﻴﻔﺔ‬
‫‪ .II‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‬
‫‪ .1.II‬ﺃﻤﺜﻠﺔ‬
‫‪ .3.II‬ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﺠﻭﺍﺭ ﻨﻘﻁﺔ ﻤﻨﺘﺼﻑ ﻗﻴﻤﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫‪ .4.II‬ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺤﻤﻀﹰﺎ ﻭﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ‬
‫‪ .5.II‬ﺘﻁﺒﻴﻘﺎﺕ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‬
‫‪81‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻟﺚ‬ ‫‪82‬‬
‫‪ .I‬ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ‬
‫ﺘﹸﺩﺭﺱ ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ ﺒﺼﻭﺭﺓ ﺭﺌﻴﺴﺔ ﻓﻲ ﺍﻝﻤﺨﺘﺒﺭﺍﺕ‪ ،‬ﻭﻝﻜﻥ ﺴﻨﻘﺘﺼﺭ ﻫﻨﺎ‬
‫ﻋﻠﻰ ﺇ ﻴﺠﺎ ﺩ ﺒﻌﺽ ﺍ ﻝﻌﻼ ﻗﺎ ﺕ ﺍ ﻝﺘﻲ ﺘﺭ ﺒﻁ ﺒﻴﻥ ‪ pH‬ﺍ ﻝﻭﺴﻁ ﻭ ﺤﺠﻡ ﺍ ﻝﺴﺎ ﺌل ﺍ ﻝﻤﻌﺎ ﻴ‪‬ﺭ ‪:V‬‬
‫) ‪. pH = f (V‬‬
‫‪ .1.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ‬
‫‪ .1.1.I‬ﺘﻌﺭﻴﻑ‬
‫ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﺤﻤﻀﻲ )ﺃﻭ ﺃﺴﺎﺴﻲ( ﻫﻲ ﺘﻌﻴﻴﻥ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻲ ﻝﻤﺤﻠﻭل ﻫﺫﺍ ﺍﻝﺤﻤﺽ‬
‫)ﺃﻭ ﺍﻷﺴﺎﺱ(‪.‬‬
‫ﺘﻭﺠﺩ ﻋﺩﺓ ﻁﺭﺍﺌﻕ ﻝﺘﺤﺩﻴﺩ ﺍﻝﺘﺭﻜﻴﺯ ‪ ،‬ﻭﻝﻜﻨﻨﺎ ﺴﻨﻌﺭﺽ ﻤﻨﻬﺎ ﺘﻠﻙ ﺍﻝﺘﻲ ﺘﻌﺘﻤﺩ ﻋﻠﻰ ﺩﺭﺍﺴﺔ‬
‫ﺘﻐﻴﺭﺍﺕ ‪ pH‬ﺍﻝﻭﺴﻁ ‪ ،‬ﻭﺫﻝﻙ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺇﻤﺎ ﺒﻤﻘﻴﺎﺱ ‪ pH‬ﺃﻭ ﺒﺎﺴﺘﻌﻤﺎل ﺘﻐﻴ‪‬ﺭ ﻝﻭﻥ ‪‬ﻤﺸﹾ ‪‬ﻌﺭ ﻝﻭﻨﻲ‬
‫ﺤﻤﻀﻲ ﺃﺴﺎﺴﻲ‪.‬‬
‫ﻥ ﺍﻝﻤﺸﻌﺭ ﺍﻝﻠﻭﻨﻲ ‪ H In‬ﻫﻭ ﺤﻤﺽ ﻀﻌﻴﻑ ﻤﻥ ﺯﻭﺝ ﺤﻤﺽ‪ /‬ﺃﺴﺎﺱ ﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ‬
‫ﺇ‪‬‬
‫‪ K Ai‬ﺒﺤﻴﺙ ﻴﻜﻭﻥ ﻝﻠﻨﻭﻋﻴﻥ ﺍﻝﻤﺘﺭﺍﻓﻘﻴﻥ ﻝﻭﻨﺎﻥ ﻤﺘﺨﺘﻠﻔﺎﻥ‪ .‬ﻭﺒﺘﻐﻴﺭ ﻨﺴﺏ ‪ H In‬ﻭ ‪ In −‬ﺘﺒﻌﹰﺎ ﻝﻘﻴﻤﺔ‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﺘﻐﻴﺭ ﻝﻭﻥ ﺍﻝﻤﺤﻠﻭل‪ .‬ﻭﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻌﺘﺒﺭ ﺃﻥ ﺍﻝﻤﺸﻌﺭ ﻴﺄﺨﺫ ﻝﻭﻨﻪ ﺍﻝﺤﻤﻀﻲ ﻋﻨﺩﻤﺎ‬
‫ﻴﻜﻭ ﻥ ‪ ، pH ≤ pK A − 1‬ﻓﻲ ﺤﻴﻥ ﻴﺄ ﺨﺫ ﺍ ﻝﻤﺸﻌﺭ ﻝﻭ ﻨﻪ ﺍ ﻷﺴﺎﺴﻲ ﻋﻨﺩ ﻤﺎ ﻴﺯ ﻴﺩ ‪ pH‬ﻋﻥ‬
‫‪i‬‬
‫‪ ، pK A + 1‬ﺍﻝﺸﻜل )‪. (1‬‬

‫‪i‬‬
‫ﻤﻨﻁﻘﺔ ﺘﻐﻴﺭ ﻝﻭﻥ ﺍﻝﻤﺸﻌﺭ‬

‫ﻝﻭﻥ ‪HIn‬‬ ‫ﻝﻭﻥ ‪In −‬‬
‫ﺍﻝﻠﻭﻨﻲ‬
‫‪pKA‬‬ ‫‪pH‬‬
‫‪i‬‬
‫‪p K A −1‬‬ ‫‪p K A +1‬‬

‫‪i‬‬ ‫‪i‬‬
‫ﺍﻝﺸﻜل )‪ : (1‬ﺍﻝﻤﺸﻌﺭﺍﺕ ﺍﻝﻠﻭﻨﻴﺔ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ‪.‬‬

‫‪83‬‬ ‫ﺍﳌﻌﺎﻳﺮﺍﺕ ﺍﳊﻤﻀﻴﺔ ﺍﻷﺳﺎﺳﻴﺔ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ﻭﻓﻴﻤﺎ ﻴﻠﻲ ﺠﺩﻭل ﺒﺒﻌﺽ ﺍﻝﻤﺸﻌﺭﺍﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ ﻭﻤﺠﺎﻻﺕ ﺘﻐﻴﺭﺍﺕ ﺍﻝﻠﻭﻥ ﻝﻜل‬
‫ﻤﻨﻬﺎ‪:‬‬
‫ﺍﻝﻠﻭﻥ ﺍﻷﺴﺎﺴﻲ‬ ‫ﻤﺠﺎل ﺘﺤﻭ‪‬ل ﺍﻝﻠﻭﻥ‬ ‫ﺍﻝﻠﻭﻥ ﺍﻝﺤﻤﻀﻲ‬ ‫ﺍﻝﻤﺸﻌﺭ‬
‫ﺃﺨﻀﺭ‬ ‫‪0.1 − 2.0‬‬ ‫ﺃﺼﻔﺭ‬ ‫)ﺍﻝﺘﺤﻭل ﺍﻷﻭل(‬ ‫ﺃﺨﻀﺭ ﺍﻝﻤﺎﻻﺸﻴﺕ‬
‫ﺃﺼﻔﺭ‬ ‫‪1.9 − 3.3‬‬ ‫ﺃﺤﻤﺭ‬ ‫ﺃﺼﻔﺭ ﺍﻷﻝﻴﺯﺍﺭﻴﻥ ‪) R‬ﺍﻝﺘﺤﻭل ﺍﻷﻭل(‬
‫ﺃﺼﻔﺭ‬ ‫‪3.1 − 4.4‬‬ ‫ﺃﺤﻤﺭ‬ ‫ﺍﻝﻬﻠﻴﺎﻨﺘﻴﻥ‬
‫ﺃﺯﺭﻕ‬ ‫‪3.0 − 4.6‬‬ ‫ﺃﺼﻔﺭ‬ ‫ﺃﺯﺭﻕ ﺍﻝﺒﺭﻭﻤﻭﻓﻴﻨﻭل‬
‫ﺒﻨﻔﺴﺠﻲ‬ ‫‪3.7 − 5.2‬‬ ‫ﺃﺼﻔﺭ‬ ‫ﺃﺤﻤﺭ ﺍﻷﻝﻴﺯﺍﺭﻴﻥ ‪) S‬ﺍﻝﺘﺤﻭل ﺍﻷﻭل(‬
‫ﺃﺯﺭﻕ‬ ‫‪3.8 − 5.4‬‬ ‫ﺃﺼﻔﺭ‬ ‫ﺃﺨﻀﺭ ﺍﻝﺒﺭﻭﻤﻭﻜﺭﻴﺯﻭل‬
‫ﺃﺼﻔﺭ‬ ‫‪4.2 − 6.2‬‬ ‫ﺃﺤﻤﺭ‬ ‫ﺃﺤﻤﺭ ﺍﻝﻤﻴﺜﻴل‬
‫ﺃﺯﺭﻕ‬ ‫‪6.0 − 7.6‬‬ ‫ﺃﺼﻔﺭ‬ ‫ﺃﺯﺭﻕ ﺍﻝﺒﺭﻭﻤﻭﺜﻴﻤﻭل‬
‫ﺃﺤﻤﺭ‬ ‫‪7.2 − 8.8‬‬ ‫ﺃﺼﻔﺭ‬ ‫ﺃﺤﻤﺭ ﺍﻝﻜﺭﻴﺯﻭل‬
‫ﺯﻫﺭﻱ‬ ‫‪8.2 − 10.0‬‬ ‫ﻋﺩﻴﻡ ﺍﻝﻠﻭﻥ‬ ‫ﺍﻝﻔﻴﻨﻭل ﻓﺘﺎﻝﺌﻴﻥ‬
‫ﺃﺼﻔﺭ‬ ‫‪10.0 − 12.0‬‬ ‫ﺒﻨﻔﺴﺠﻲ‬ ‫ﺃﺤﻤﺭ ﺍﻷﻝﻴﺯﺍﺭﻴﻥ ‪) S‬ﺍﻝﺘﺤﻭل ﺍﻝﺜﺎﻨﻲ(‬
‫ﺒﻨﻔﺴﺠﻲ‬ ‫‪10.1 − 12.1‬‬ ‫ﺃﺼﻔﺭ‬ ‫ﺃﺼﻔﺭ ﺍﻷﻝﻴﺯﺍﺭﻴﻥ ‪) R‬ﺍﻝﺘﺤﻭل ﺍﻝﺜﺎﻨﻲ(‬
‫ﻋﺩﻴﻡ ﺍﻝﻠﻭﻥ‬ ‫‪11.5 − 13.2‬‬ ‫ﺃﺨﻀﺭ‬ ‫)ﺍﻝﺘﺤﻭل ﺍﻝﺜﺎﻨﻲ(‬ ‫ﺃﺨﻀﺭ ﺍﻝﻤﺎﻻﺸﻴﺕ‬
‫ﺃﺼﻔﺭ‬ ‫‪11.6 − 14.0‬‬ ‫ﺃﺯﺭﻕ‬ ‫ﻨﻴﻠﺔ ﻗﺭﻤﺯﻴﺔ‬
‫‪ .2.1.I‬ﺍﻝﺘﻜﺎﻓﺅ ﺍﻝﺤﻤﻀﻲ‪-‬ﺍﻷﺴﺎﺴﻲ‬
‫ﻥ ﺍﻝﻤﻌﺎﺩ ﻝﺔ‬
‫ ﻝﻨﺘﺄ ﻤ‪‬ل ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﻤﻥ ﺤﻤﺽ ﻭﺤﻴﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪ HA‬ﺒﺎﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‪ .‬ﺇ ‪‬‬
‫ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻲ‪:‬‬
‫‪H A + OH− A− + H2O‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻴﻜﻭﻥ ﺍﻝﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ ﻤﻤﺯﻭﺠﻴﻥ ﻭﻓﻕ ﺍﻝﻨﺴﺏ ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ‪ ،‬ﺃﻱ‬
‫ﺘﻜﻭﻥ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻀﺎﻓﺔ ﻤﺴﺎﻭﻴﺔ ﻜﻤﻴﺔ ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ ﺍﻝﻤﺤﺭﺭﺓ ﺃﻭ ﺍﻝﻘﺎﺒﻠﺔ‬
‫ﻝﻠﺘﺤﺭﺭ ﻤﻥ ﺍﻝﺤﻤﺽ ‪ HA‬ﻜﺎﻤﻠﺔ‪ ،‬ﻭﻨﻜﺘﺏ‪:‬‬
‫) ‪n0 (HA) = n eqv (OH−‬‬
‫ﻨﻘﺼﺩ ﺒﺎﻝﺩﻝﻴل ‪ eqv‬ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ‬
‫ ﻝﻨﺘﺄ ﻤ‪‬ل ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﻤﻥ ﺤﻤﺽ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪ H p A‬ﺒﺎﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‪ .‬ﺇ ‪‬‬
‫ﺍﻝﻤﺤﺼﻠﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻲ‪:‬‬
‫‪H p A + p OH− A p − + p H2O‬‬
‫ﻭﻨﻌﺭ‪‬ﻑ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺘﻜﺎﻓﺅﹰﺍ ﺇﺠﻤﺎﻝﻴﹰﺎ ﻭﺘﻜﺎﻓﺅﺍﺕ ﻤﺘﻌﺎﻗﺒﺔ )ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل‪ ،‬ﺍﻝﺘﻜﺎﻓﺅ ﺍﻝﺜﺎﻨﻲ‪:(...،‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻹﺠﻤﺎﻝﻲ‪ ،‬ﻴﻜﻭﻥ ﺍﻝﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ ﻤﻤﺯﻭﺠﻴﻥ ﻭﻓﻕ ﺍﻝﻨﺴﺏ‬
‫ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ‪ ،‬ﺃﻱ ﺘﻜﻭﻥ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‬
‫ﺍﻝﻤﻀﺎﻓﺔ ﻤﺴﺎﻭﻴﺔ ﻜﻤﻴﺔ ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ ﺍﻝﻤﺤﺭﺭﺓ ﺃﻭ ﺍﻝﻘﺎﺒﻠﺔ ﻝﻠﺘﺤﺭﺭ ﻤﻥ ﺍﻝﺤﻤﺽ ﺍﻝﻤﺘﻌﺩﺩ‬
‫ﺍﻝﻭﻅﻴﻔﺔ ‪ ، H p A‬ﻭﻨﻜﺘﺏ‪:‬‬
‫) ‪p ⋅ n 0 (H p A) = n eqv (OH−‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭﻝﻰ ﻴﻜﻭﻥ ﻜل ﻤﻥ ﺍﻝﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ ﻤﻤﺯﻭﺠﻴﻥ ﺒﻜﻤﻴﺎﺕ ﻤﺘﺴﺎﻭﻴﺔ‬
‫ﺍﻝﻤﻭﻝﻴﺔ‪. n0 (H p A) = neqv(1)(OH− ) :‬‬
‫ﻓﻲ ﺒﻌﺽ ﺍﻝﺤﺎﻻﺕ‪ ،‬ﻻ ﺘﻭﺍﻓﻕ ﺍﻝﺘﻜﺎﻓﺅﺍﺕ ﺍﻝﻤﺘﻌﺎﻗﺒﺔ ﻗﻔﺯﺍﺕ ﻓﻲ ﻗﻴﻡ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﻤﻜﻥ‬
‫ﻤﻼﺤﻅﺘﻬﺎ‪ ،‬ﻭﻜﺫﻝﻙ ﻓﻲ ﺒﻌﺽ ﺍﻝﺘﻜﺎﻓﺅﺍﺕ ﺍﻹﺠﻤﺎﻝﻴﺔ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﺘﻔﺎﻋﻼﺕ ﻏﻴﺭ ﺘﺎﻤﺔ ﻴﺼﻌﺏ‬
‫ﺘﻤﻴﻴﺯ ﻗﻔﺯﺍﺕ ﻓﻲ ﻗﻴﻡ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .3.1.I‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫ﻝﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ ،‬ﻴﻤﻜﻥ ﺍﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﻤﻨﺤﻨﻲ ) ‪ ، pH = f (V‬ﺤﻴﺙ ‪ V‬ﻫﻭ ﺤﺠﻡ‬

‫ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻌﺎﻴ‪‬ﺭﺓ ﺍﻝﻤﻀﺎﻓﺔ‪ .‬ﺇﺫ ﻴﺠﺭﻱ ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺒﺎﺴﺘﻌﻤﺎل ﻁﺭﻴﻘﺔ ﺍﻝﻤﻤﺎﺴﺎﺕ‪ ،‬ﺍﻝﺸﻜل )‪(2‬‬
‫ﺃﻭ ﻋﺒﺭ ﺍﺸﺘﻘﺎﻕ ﻤﻨﺤﻨﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ ‪ ، d pH /dV‬ﺍﻝﺸﻜل )‪. (3‬‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ‪ ،‬ﻴﻤﻜﻨﻨﺎ ﺍﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﻤﺸﻌﺭﺍﺕ ﺍﻝﻠﻭﻨﻴﺔ ﻝﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻋﻥ ﻁﺭﻴﻕ‬
‫ﺍﺨﺘﻴﺎﺭ ﻤﺸﻌﺭ ﻝﻭﻨﻲ ﻤﻨﺎﺴﺏ ﻴﻜﻭﻥ ﻤﺠﺎل ﺘﺤﻭ‪‬ل ﺍﻝﻠﻭﻥ ﻓﻴﻪ ﺤﺎﻭﻴﹰﺎ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻫﺫﻩ‪ ،‬ﺍﻝﺸﻜل )‪. (4‬‬
‫ﺘﺯﺩﺍﺩ ﺍﻝﺩﻗﺔ ﻓﻲ ﺍﻝﺘﺤﺩﻴﺩ ﺍﻝﺘﺠﺭﻴﺒﻲ ﻝﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺇﺫﺍ ﻜﺎﻥ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻜﻤﻴﹰﺎ ﻭﺇﺫﺍ ﻜﺎﻨﺕ‬
‫ﺍﻝﻤﺤﺎﻝﻴل ﻏﻴﺭ ﻤﻤﺩﺩﺓ ﻜﺜﻴﺭﹰﺍ‪.‬‬
‫ﻤﻥ ﺍﻝﻤﺘﻌﺎﺭﻑ ﻋﻨﺩ ﺇﺠﺭﺍﺀ ﺍﻝﺩﺭﺍﺴﺔ ﺍﻝﻨﻅﺭﻴﺔ ﻝﻠﻤﻌﺎﻴﺭﺓ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ ﺍﺴﺘﻌﻤﺎل‬

‫ﺍﻝﻤﺘﺤﻭل ‪ x‬ﺍﻝﻤﻌﺭ‪‬ﻑ ﺒﺎﻝﺼﻴﻐﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪V‬‬
‫= ‪x‬‬
‫‪Veqv‬‬
‫ﺤﻴﺙ ‪ V‬ﻫﻭ ﺤﺠﻡ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻌﺎ ‪‬ﻴِﺭﺓ‪ ،‬ﻭ ‪ Veqv‬ﺤﺠﻡ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻌﺎ ‪‬ﻴِﺭﺓ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫‪pH‬‬
‫‪E‬‬
‫‪Veqv‬‬ ‫‪V‬‬
‫ﺍﻝﺸﻜل )‪ : (2‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﻨﺤﻨﻲ ) ‪ pH = f (V‬ﺒﻁﺭﻴﻘﺔ ﺍﻝﻤﻤﺎﺴﺎﺕ‪.‬‬
‫ﻓﻌﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻓﻲ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻭﺤﻴﺩ ﺍﻝﻭﻅﻴﻔﺔ ﺃﻭ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل ﻓﻲ ﻤﻌﺎﻴﺭﺓ‬
‫ﺤﻤﺽ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ ﻴﻜﻭﻥ ‪. x = 1‬‬
‫‪pH‬‬
‫‪dpH‬‬
‫‪dV‬‬
‫‪E‬‬
‫‪Veqv‬‬ ‫‪V‬‬
‫ﺍﻝﺸﻜل )‪ : (3‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺒﺎﺴﺘﻌﻤﺎل ﻤﻨﺤﻨﻲ ﺍﻝﻤﺸﺘﻕ ‪. d pH/ dV‬‬
‫‪pH‬‬
‫ﻝﻭﻥ ﺍﻝﺸﻜل ‪In‬‬

‫‪−‬‬
‫‪pH eqv‬‬ ‫ﻤﺠﺎل ﺘﺤﻭل ﻝﻭﻥ ﺍﻝﻤﺸﻌﺭ ‪E‬‬

‫ﻝﻭﻥ ﺍﻝﺸﻜل ‪H In‬‬
‫‪Veqv‬‬ ‫‪V‬‬
‫ﺍﻝﺸﻜل )‪ : (4‬ﻴﻤﻜﻥ ﺍﺴﺘﻌﻤﺎل ﻤﺸﻌﺭ ﻝﻭﻨﻲ ﻤﺎ ﻓﻲ ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫ﺇﺫﺍ ﻭﻗﻌﺕ ﺘﻠﻙ ﺍﻝﻨﻘﻁﺔ ﻀﻤﻥ ﻤﻨﻁﻘﺔ ﺘﺤﻭ‪‬ل ﻝﻭﻥ ﺍﻝﻤﺸﻌﺭ‪.‬‬
‫ ‬
‫ﺍﻝﱡﻠﺒﺎﻥ ﺍﻝﺨﺎﻝﻲ ﻤﻥ ﺍﻝﺴﻜﹼﺭ‬
‫ﻋﻨﺩ ﺘﻨﺎﻭﻝﻨﺎ ﺍﻝﻤﻭﺍﺩ ﺍﻝﺴﻜﺭﻴﺔ ﻴﺘﺤﻭ‪‬ل ﺍﻝﺴﻜﺭ ﺇﻝﻰ ﺤﻤﺽ )ﻤﺜل ﺤﻤﺽ ﺍﻝﻠﺒﻥ( ﺒﻔﻌل ﺍﻝﺠﺭﺍﺜﻴﻡ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻔﻡ‪ .‬ﻴﺅﺜﹼﺭ‬
‫ﻫﺫﺍ ﺍﻝﺤﻤﺽ ﻋﻠﻰ ﻤﻴﻨﺎﺀ ﺍﻷﺴﻨﺎﻥ ﻭﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻝﻨﺨﺭ‪ .‬ﻭﻝﻜﻥ ﺒﺎﺴﺘﻌﻤﺎﻝﻨﺎ ﻝﻠﺒﺎﻥ ﺍﻝﺨﺎﻝﻲ ﻤﻥ ﺍﻝﺴﻜﺭ ﻨﺤﺭ‪‬ﺽ ﺍﻝﻐﺩﺩ ﺍﻝﻠﻌﺎﺒﻴﺔ‬
‫ﻋﻠﻰ ﻓﺭﺯ ﻜﻤﻴﺎﺕ ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻠﻌﺎﺏ ﺍﻝﺫﻱ ﻫﻭ ﺒﻁﺒﻴﻌﺘﻪ ﻗﻠﻭﻱ ﺍﻝﺘﻔﺎﻋل ﺒﻌﺽ ﺍﻝﺸﻲﺀ ‪ ، pH = 7.4‬ﻓﻴﻌﺩ‪‬ل ﻤﻥ‬
‫ﻥ‬
‫ﺤﻤﻭﻀﺔ ﺍﻝﻭﺴﻁ ﺍﻝﻤﺤﻴﻁ ﺒﺎﻷﺴﻨﺎﻥ ﻭﻴﻤﻨﻊ ﺍﻝﻨﺨﺭ‪ .‬ﻫﺫﺍ ﺍﻝﺴﺒﺏ ﻴﻔﺴ‪‬ﺭ ﻝﻨﺎ ﺃﻴﻀﹰﺎ ﻀﺭﻭﺭﺓ ﺘﻨﻅﻴﻑ ﺍﻷﺴﻨﺎﻥ ﻗﺒل ﺍﻝﻨﻭﻡ‪ ،‬ﻷ ‪‬‬
‫ﺇﻓﺭﺍﺯ ﺍﻝﻠﻌﺎﺏ ﻴﻘل ﺃﺜﻨﺎﺀ ﺍﻝﻨﻭﻡ ﻓﻴﺯﺩﺍﺩ ﺃﺜﺭ ﺍﻝﺤﻤﺽ ﻋﻠﻰ ﺍﻷﺴﻨﺎﻥ‪.‬‬
‫‪ .2.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻗﻭﻱ ﺒﺄﺴﺎﺱ ﻗﻭﻱ‬
‫ﻼ( ﺒﺤﺠﻡ ‪ Va‬ﻭﺒﺘﺭﻜﻴﺯ ‪C a‬‬

‫ﻝﻴﻜﻥ ﻝﺩﻴﻨﺎ ﻤﺤﻠﻭ لٌ ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ) ‪ H3O+ + Cl−‬ﻤﺜ ﹰ‬
‫ﻏﻴﺭ ﻤﻌﻠﻭ ﻡ‪ .‬ﻨﻀﻴﻑ ﺇ ﻝﻰ ﺍ ﻝﻤﺤﻠﻭ ل ﺍ ﻝﺴﺎ ﺒﻕ ﺘﺩ ﺭ ﻴﺠﻴﹰﺎ ﺤﺠﻤﹰﺎ ‪ Vb‬ﻤﻥ ﻤﺤﻠﻭ ل ﺃﺴﺎ ﺱ ﻗﻭﻱ‬
‫ﻼ( ﺒﺘﺭﻜﻴﺯ ﻤﻌﻠﻭﻡ ‪ .C b‬ﺘﻜﻭﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻲ‪:‬‬
‫) ‪ Na + + OH−‬ﻤﺜ ﹰ‬
‫‪H3O+ + OH− ⇌ 2 H2O‬‬
‫ﻥ‬
‫ﻭﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ‪ K 0 = 1.0 × 1014‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ . 25 C‬ﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ‪ .‬ﻭﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫)‪C a ⋅ Va = C b ⋅ Vb(eqv‬‬
‫ﻝﻨﻭﺠﺩ ﺍﻝﻌﺒﺎﺭﺍﺕ ) ‪ pH = f (x‬ﺍﻝﺨﺎﺼﺔ ﺒﻬﺫﻩ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﺤﻴﺙ‪:‬‬

‫‪Vb‬‬ ‫‪C b ⋅ Vb‬‬ ‫‪C ⋅V‬‬
‫= ‪x‬‬ ‫=‬ ‫‪= b b‬‬
‫)‪Vb(eqv‬‬ ‫)‪C b ⋅ Vb(eqv‬‬ ‫‪C a ⋅ Va‬‬
‫ﻭﻨﻤﻴ‪‬ﺯ ﺒﻴﻥ ﻋﺩﺓ ﺤﺎﻻﺕ ﻭﻓﻘﹰﺎ ﻝﻘﻴﻤﺔ ‪: x‬‬
‫ﻥ ‪.Vb = 0‬‬
‫‪ x = 0 o‬ﺃﻱ ﺇ ‪‬‬
‫‪ [H 3O+ ] = C a‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ‪. pH = − log C a‬‬
‫ﻥ )‪Vb < Vb(eqv‬‬
‫‪ 0 < x < 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻝﻨﺴﺘﻌﻤل ﻜﻤﻴﺔ ﺍﻝﻤﺎﺩﺓ ﻝﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫‪+‬‬
‫‪H 3O‬‬ ‫‪+ OH−‬‬ ‫‪ 2 H2 O‬‬
‫‪t = 0 C a .Va‬‬ ‫‪C b .Vb‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪C a .Va − C b .Vb‬‬ ‫‪ε‬‬ ‫‪−‬‬
‫ﻭﻋﻠﻴﻪ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ‪:‬‬
‫‪C .V − C b .Vb‬‬ ‫‪C a .Va‬‬ ‫‪C .V‬‬
‫‪[ H 3O+ ] = a a‬‬ ‫=‬ ‫) ‪(1 − b b‬‬
‫‪Va + Vb‬‬ ‫‪Va + Vb‬‬ ‫‪C a .Va‬‬
‫‪C a .Va‬‬
‫= ] ‪. [ H 3O+‬‬ ‫) ‪(1 − x‬‬ ‫ﺃﻱ‬
‫‪Va + Vb‬‬
‫‪C .V‬‬
‫) ‪. pH = − log a a − log(1 − x‬‬ ‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ‬
‫‪Va + Vb‬‬
‫ﻥ )‪) Vb = Vb(eqv‬ﺍﻝﺘﻜﺎﻓﺅ(‬
‫‪ x = 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﺘﻜﻭ ﻥ ﺸﻭ ﺍ ﺭ ﺩ ﺍ ﻝﻬﻴﺩ ﺭ ﻭ ﻨﻴﻭ ﻡ ﻭ ﺍ ﻝﻬﻴﺩ ﺭ ﻭ ﻜﺴﻴﺩ ﻓﻲ ﻫﺫ ﻩ ﺍ ﻝﺤﺎ ﻝﺔ ﻤﻤﺯ ﻭ ﺠﺔ ﻭ ﻓﻕ ﺍ ﻝﻨﺴﺏ‬
‫ﻥ‪:‬‬
‫ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ‪ .‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪+‬‬ ‫‪−‬‬
‫‪[H 3O ]eqv = [OH ]eqv‬‬
‫ﻭ ‪ pHeqv = 7.0‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪. 25 C‬‬
‫ﻥ )‪Vb > Vb(eqv‬‬

‫‪ x > 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﻓﺎﺌﺽ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻗﺩﺭﻩ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻀﺎﻓﺔ‬
‫‪ n(OH− )added‬ﻤﻁﺭﻭﺤﹰﺎ ﻤﻨﻪ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻼﺯﻤﺔ ﻝﻠﻭﺼﻭل ﺇﻝﻰ ﻨﻘﻁﺔ‬
‫ﺍﻝﺘﻜﺎﻓﺅ ‪: n(OH− )eqv‬‬
‫‪n(OH− ) = n(OH− )added − n(OH− )eqv‬‬

‫ﻥ‪:‬‬
‫)‪C b .Vb − C b .Vb(eqv‬‬
‫= ] ‪[OH−‬‬
‫‪Va + Vb‬‬
‫)‪C b .Vb(eqv‬‬ ‫‪C a .Va‬‬
‫=‬ ‫= )‪(x − 1‬‬ ‫)‪(x − 1‬‬
‫‪Va + Vb‬‬ ‫‪Va + Vb‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ‪ ، pK w = pH + pOH‬ﻭﺠﺩﻨﺎ ﺃﻨﹼﻪ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻝﺩﻴﻨﺎ ‪:‬‬
‫‪C .V‬‬
‫)‪pH = 14 + log a a + log(x − 1‬‬
‫‪Va + Vb‬‬
‫ﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪ pH = f (x‬ﺘﺘﻌﻠﹼﻕ ﺒﺎﻝﺘﺭﺍﻜﻴﺯ‪ ،‬ﺍﻝﺸﻜل )‪. (5‬‬
‫ﻭﻫﻜﺫﺍ ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻴﻤﻜﻨﻨﺎ ﺃﻴﻀﹰﺎ ﻭﻋﻠﻰ ﻨﺤﻭ ﻤﺸﺎﺒﻪ ﻝﻤﺎ ﺴﺒﻕ ﺃﻥ ﻨﺩﺭﺱ ﺘﻐﻴﺭﺍﺕ ‪ pH‬ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻷﺴﺎﺱ‬
‫ﻗﻭﻱ‪ ،‬ﻭﺫﻝﻙ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ﺇﻝﻴﻪ‪ .‬ﺃﻱ ﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ ﺩﺭﺍﺴﺔ ﻤﻨﺤﻨﻲ‬
‫ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻗﻭﻱ ﺒﺤﻤﺽ ﻗﻭﻱ‪ ،‬ﺍﻝﺸﻜل )‪. (6‬‬
‫‪pH‬‬ ‫‪1 C =C = 1.0 × 10‬‬

‫‪−1‬‬
‫‪mol/L‬‬
‫‪a‬‬ ‫‪b‬‬
‫‪−2‬‬
‫‪14‬‬ ‫‪2 C =C = 1.0 × 10‬‬
‫‪a‬‬ ‫‪b‬‬
‫‪mol/L‬‬
‫‪3 C =C = 1.0 × 10‬‬
‫‪−3‬‬
‫‪mol/L‬‬ ‫‪1‬‬
‫‪12‬‬ ‫‪a‬‬ ‫‪b‬‬
‫‪−4‬‬ ‫‪2‬‬
‫‪4 C =C = 1.0 × 10‬‬ ‫‪mol/L‬‬ ‫‪3‬‬
‫‪10‬‬ ‫‪a‬‬ ‫‪b‬‬
‫‪4‬‬
‫‪8‬‬
‫‪E‬‬
‫‪6‬‬
‫‪4‬‬
‫‪2‬‬
‫‪x‬‬
‫‪0.2‬‬ ‫‪0.4‬‬ ‫‪0.6‬‬ ‫‪0.8‬‬ ‫‪1.0‬‬ ‫‪1.2‬‬ ‫‪1.4‬‬
‫ﺍﻝﺸﻜل )‪ : (5‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪ x = Vb /Vb(eqv) ، pH = f (x‬ﺒﺩﻻﻝﺔ ﺘﺭﺍﻜﻴﺯ ﻤﺨﺘﻠﻔﺔ ﻝﻠﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ‬
‫ﻭﺫﻝﻙ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ ﺇﻝﻰ ﻤﺤﻠﻭل ﺤﻤﺽ ﻗﻭﻱ ﻝﻬﻤﺎ ﺍﻝﺘﺭﻜﻴﺯ ﻨﻔﺴﻪ‪.‬‬
‫ﺘﺴﻤﺢ ﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺸﻜل )‪ (5‬ﺒﺎﺨﺘﻴﺎﺭ ﺍﻝﻤﺸﻌﺭ ﺍﻝﻠﻭﻨﻲ ﺍﻝﻤﻨﺎﺴﺏ ﻋﻨﺩ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻗﻭﻱ‬
‫ﺒﺄﺴﺎﺱ ﻗﻭﻱ‪ ،‬ﻭﺫﻝﻙ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﺠﺩﻭل ﺍﻝﻤﻌﻁﻰ ﻓﻲ ﺍﻝﻔﻘﺭﺓ ‪ ..1.1.I‬ﻭﻜﺫﻝﻙ ﹸﺘﻅﻬﺭ ﻫﺫﻩ‬
‫ﻥ ﺩﻗﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺘﻜﻭﻥ ﺃﻓﻀل ﻜﻠﻤﺎ ﻜﺎﻨﺕ ﺍﻝﻤﺤﺎﻝﻴل ﺃﻜﺜﺭ ﺘﺭﻜﻴﺯﹰﺍ‪ .‬ﻷﻥ ﻗﻔﺯﺓ‬
‫ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺃ ‪‬‬
‫‪ pH‬ﺍﻝﻭﺴﻁ ﺘﻜﻭﻥ ﺃﻜﺒﺭ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻨﺤﺩ‪‬ﺩ ﺒﺩﻗﺔ ﺃﻜﺒﺭ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫‪pH‬‬
‫‪14‬‬
‫‪12‬‬
‫‪10‬‬
‫‪8‬‬
‫‪E‬‬
‫‪6‬‬ ‫‪1 C =C = 1.0 × 10‬‬
‫‪a‬‬ ‫‪b‬‬
‫‪−1‬‬
‫‪mol/L‬‬
‫‪4‬‬ ‫‪2 C =C = 1.0 × 10‬‬
‫‪a‬‬ ‫‪b‬‬
‫‪−2‬‬
‫‪mol/L‬‬ ‫‪4‬‬
‫‪−3‬‬ ‫‪3‬‬
‫‪3 C =C = 1.0 × 10‬‬ ‫‪mol/L‬‬ ‫‪2‬‬
‫‪2‬‬ ‫‪a‬‬ ‫‪b‬‬
‫‪4 C =C = 1.0 × 10‬‬

‫‪a‬‬ ‫‪b‬‬
‫‪−4‬‬
‫‪mol/L‬‬ ‫‪1‬‬
‫‪0.2‬‬ ‫‪0.4‬‬ ‫‪0.6‬‬ ‫‪0.8‬‬ ‫‪1.0‬‬ ‫‪1.2‬‬ ‫‪1.4 x‬‬
‫ﺍﻝﺸﻜل )‪ : (6‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪ x = Va /Va(eqv) ، pH = f (x‬ﺒﺩﻻﻝﺔ ﺘﺭﺍﻜﻴﺯ ﻤﺨﺘﻠﻔﺔ ﻝﻠﺤﻤﺽ ﻭﺍﻷﺴﺎﺱ‬
‫ﻭﺫﻝﻙ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﺤﻤﺽ ﻗﻭﻱ ﺇﻝﻰ ﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ ﻝﻬﻤﺎ ﺍﻝﺘﺭﻜﻴﺯ ﻨﻔﺴﻪ‪.‬‬
‫‪ .3.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ‬
‫ﻼ( ﺒﺤﺠﻡ ‪Va‬‬

‫ﻝﻴﻜﻥ ﻝﺩ ﻴﻨﺎ ﻤﺤﻠﻭ ل ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ‪ CH 3COOH ) HA‬ﻤﺜ ﹰ‬
‫ﻭﺒﺘﺭﻜﻴﺯ ‪ C a‬ﻏﻴﺭ ﻤﻌﻠﻭﻡ ﻭﺒﺜﺎﺒﺕ ﺤﻤﻭﻀﺔ ‪ . K A‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺤﺠﻤﹰﺎ‬
‫ﻼ( ﺒﺘﺭﻜﻴﺯ ﻤﻌﻠﻭﻡ ‪ .C b‬ﻴﺠﺭﻱ ﺩﺍﺨل ﺒﻴﺸﺭ‬
‫‪ Vb‬ﻤﻥ ﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ ) ‪ Na + + OH−‬ﻤﺜ ﹰ‬
‫ﺍﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﺘﻔﺎﻋﻼﻥ ﺍﻝﺘﺎﻝﻴﺎﻥ‪:‬‬
‫♦ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﺫﻭ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪HA + OH− A− + H2O‬‬ ‫)‪(1‬‬ ‫) ‪K10 = 10(pK w −pK A‬‬
‫♦ ﺘﻔﺎﻋل ﺍﻝﺤﻤﺽ ‪ HA‬ﻤﻊ ﺍﻝﻤﺎﺀ‪:‬‬
‫‪HA + H2O A− + H 3O+‬‬ ‫)‪(2‬‬ ‫‪K 20 = 10−pK A‬‬
‫ﻥ ‪ pK A‬ﻜﺒﻴﺭ ﺒﻤﺎ ﻴﻜﻔﻲ‬
‫ﻑ‪ ،‬ﺃﻱ ﺇ ‪‬‬
‫ﻭ ﻋﻨﺩ ﻤﺎ ﻴﻜﻭ ﻥ ﺍ ﻝﺜﺎ ﺒﺕ ‪ K A‬ﺼﻐﻴﺭ ﹰﺍ ﺇ ﻝﻰ ﺤ ‪‬ﺩ ﻜﺎ ‪‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل )‪ (1‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻭﺤﻴﺩ ﺍﻝﺫﻱ ﻴﻨﺒﻐﻲ ﺃﺨﺫﻩ ﻓﻲ‬
‫ﻭﺍﻝﻤﺤﻠﻭل ﻝﻴﺱ ﻤﻤﺩﺩ ﹰﺍ ﻜﺜﻴﺭ ﺍﹰ‪ ،‬ﻓﺈ ‪‬‬
‫ﺍﻝﺤﺴﺒﺎﻥ‪ .‬ﻭﻋﻤﻠﻴﹰﺎ ﻫﺫﻩ ﻫﻲ ﺍﻝﺤﺎل ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﻤﻌﺎﻤل ﺘﻔﻜﻙ ﺍﻝﺤﻤﺽ ﻓﻲ ﺍﻝﺒﺩﺍﻴﺔ ﺃﺼﻐﺭ ﻤﻥ‬
‫‪. 10%‬‬
‫‪ .1.3.I‬ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻲ‪:‬‬

‫ﺇ‪‬‬
‫‪HA + OH− A− + H2O‬‬ ‫) ‪K10 = 10(pK w −pK A‬‬
‫ﻭﻜﻠﻤﺎ ﻜﺎﻥ ‪ pK A‬ﺼﻐﻴﺭﹰﺍ ﻜﺎﻥ ﺍﻝﺘﻔﺎﻋل ﺃﻜﺜﺭ ﻜﻤﻴﺔ ﻭﺍﺯﺩﺍﺩﺕ ﺩﻗﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫ﻥ‪:‬‬
‫ﻭﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ n0 (HA) = n eqv (OH− ) :‬ﺃﻱ ﺇ ‪‬‬
‫)‪C a ⋅ Va = C b ⋅ Vb(eqv‬‬
‫ﻝﻨﻭﺠﺩ ﺍﻝﻌﺒﺎﺭﺍﺕ ) ‪ pH = f (x‬ﺍﻝﺨﺎﺼﺔ ﺒﻬﺫﻩ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﺤﻴﺙ ‪ x‬ﻤﻌﺭ‪‬ﻑ ﻓﻲ ﺍﻝﻔﻘﺭﺓ‬
‫‪..3.1.I‬‬
‫ﻥ ‪Vb = 0‬‬
‫‪ x = 0 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻴﻀﻡ ﺍ ﻝﻤﺤﻠﻭ ل ﻓﻘﻁ ﺤﻤﻀﹰﺎ ﻀﻌﻴﻔﹰﺎ‪ .‬ﻭ ﻴﺠﺭ ﻱ ﺘﺤﺩ ﻴﺩ ‪ pH‬ﺍ ﻝﻭﺴﻁ ﺒﺎﺴﺘﻌﻤﺎ ل ﺍ ﻝﻌﻼ ﻗﺔ‬
‫‪1‬‬
‫ﻥ ﺍﻝﺤﻤﺽ ﻀﻌﻴﻑ ﺍﻝﺘﻔﻜﻙ ‪ ،‬ﻭﺒﺈﻫﻤﺎل‬
‫) ‪ ، pH = (pK A + pC a‬ﻭﺫﻝﻙ ﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫‪2‬‬
‫ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪.‬‬
‫‪ 0 < x < 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻝﻨﺴﺘﻌﻤل ﻜﻤﻴﺔ ﺍﻝﻤﺎﺩﺓ ﻝﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫‪HA‬‬ ‫‪+ OH−‬‬ ‫‪ A−‬‬ ‫‪+ H2 O‬‬
‫‪t = 0 C a .Va‬‬ ‫‪C b .Vb‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪C a .Va − C b .Vb‬‬ ‫‪ε‬‬ ‫‪C b .Vb‬‬
‫ﻭﻋﻠﻴﻪ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯﺍ ﺍﻝﺤﻤﺽ ‪ HA‬ﻭﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ ‪ A−‬ﻫﻤﺎ‪:‬‬
‫‪  HA  = C a .Va − C b .Vb‬ﻭ ‪ A−  = C b .Vb‬‬

‫‪‬‬ ‫‪ V + V‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪Va + Vb‬‬
‫‪a‬‬ ‫‪b‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ‬
‫] ‪[A−‬‬ ‫‪C b .Vb‬‬
‫‪pH = pK A + log‬‬ ‫‪= pK A + log‬‬
‫]‪[HA‬‬ ‫‪C a .Va − C b .Vb‬‬
‫ﺃﻱ‬
‫‪x‬‬
‫‪1−x‬‬
‫ﻋﻨﺩﻤﺎ ‪ x = 0.5‬ﻨﻜﻭﻥ ﻋﻨﺩ ﻨﺼﻑ ﺍﻝﺘﻜﺎﻓﺅ‪ ،‬ﻭﻨﻜﺘﺏ‪. pH = pK A :‬‬
‫ﻥ )‪) Vb = Vb(eqv‬ﺍﻝﺘﻜﺎﻓﺅ(‬
‫‪ x = 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻴﻜﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻤﻜﺎﻓﺌﹰﺎ ﻫﻨﺎ ﻝﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻀﻌﻴﻑ ‪ A−‬ﺒﺘﺭﻜﻴﺯ‪:‬‬
‫)‪C b .Vb(eqv‬‬ ‫‪C a .Va‬‬
‫= ‪.c′‬‬ ‫=‬
‫)‪Va + Vb(eqv‬‬ ‫)‪Va + Vb(eqv‬‬
‫ﻭﻴﺠﺭﻱ ﺘﺤﺩﻴﺩ ‪ pH‬ﺍﻝﻭﺴﻁ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻌﻼﻗﺔ‪:‬‬

‫‪1‬‬
‫= ‪pOH‬‬ ‫)‪(pK B + pc ′‬‬
‫‪2‬‬
‫ﺃﻱ‬
‫‪1‬‬
‫)‪pHeqv = (pK w + pK A − pc ′‬‬
‫‪2‬‬
‫ﻥ ﺒﺭﺘﻨﺔ ﺍﻷﺴﺎﺱ ﻀﻌﻴﻔﺔ ﻭﺒﺈﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪.‬‬
‫ﻭﺫﻝﻙ ﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫ﻥ )‪Vb > Vb(eqv‬‬

‫‪ x > 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﺘﻤﺎﻤﹰﺎ ﻜﻤﺎ ﻭﺠﺩﻨﺎ ﻓﻲ ﺍﻝﻔﻘﺭﺓ ‪ .2.I‬ﻓﺎﺌﺽ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻗﺩﺭﻩ ﻜﻤﻴﺔ‬
‫‪ n(OH− )added‬ﻤﻁﺭﻭﺤﹰﺎ ﻤﻨﻪ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ‬ ‫ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻀﺎﻓﺔ‬
‫ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻼﺯﻤﺔ ﻝﻠﻭﺼﻭل ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ‪: n(OH )eqv‬‬
‫‪−‬‬
‫‪n(OH− ) = n(OH− )added − n(OH− )eqv‬‬
‫ﻥ‪:‬‬
‫)‪C b .Vb − C b .Vb(eqv‬‬ ‫)‪C b .Vb(eqv‬‬

‫= ] ‪[OH−‬‬ ‫=‬ ‫)‪(x − 1‬‬
‫‪Va + Vb‬‬ ‫‪Va + Vb‬‬
‫‪C a .Va‬‬
‫=‬ ‫)‪(x − 1‬‬
‫‪Va + Vb‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ‪ ، pK w = pH + pOH‬ﻓﺈﻨﻨﺎ ﻨﺠﺩ ﺃﻨﹼﻪ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻴﻜﻭﻥ‪:‬‬
‫‪C a .Va‬‬
‫‪pH = 14 + log‬‬ ‫)‪+ log(x − 1‬‬
‫‪Va + Vb‬‬
‫‪‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل )‪ (7‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪ pH = f (x‬ﻓﻲ ﺤﺎﻝﺔ ﺘﺭﺍﻜﻴﺯ ﻤﺨﺘﻠﻔﺔ ﻤﻥ ﺤﻤﺽ ﺍﻝﺨل‪.‬‬

‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻓﻲ ﺠﻭﺍﺭ ‪ x = 0.5‬ﺘﻨﻁﺒﻕ ﺠﻤﻴﻊ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻭﺘﻜﻭﻥ ﺸﺒﻪ ﻤﺴﺘﻘﻴﻤﺔ‪ .‬ﻨﺴﻤﻲ ﻫﺫﻩ‬
‫ﺍﻝﻤﻨﻁﻘﺔ ﻤﻨﻁﻘﺔ ﻫﻨﺩﺭﺴﻭﻥ ‪ ،Henderson‬ﻭﻨﺴﻤﻲ ﺍﻝﺠﺯﺀ ﺸﺒﻪ ﺍﻝﺨﻁﻲ ﻤﺴﺘﻘﻴﻡ ﻫﻨﺩﺭﺴﻭﻥ‪.‬‬
‫‪pH‬‬
‫‪14‬‬ ‫‪C a =C b = 0.1 mol/L‬‬
‫‪C a =C b = 0.01 mol/L‬‬
‫‪12‬‬ ‫‪C a =C b = 0.001 mol/L‬‬ ‫‬
‫‬
‫‪10‬‬ ‫‬
‫‪8‬‬
‫‪6‬‬
‫‪4‬‬
‫‪2‬‬
‫‪0‬‬ ‫‪x‬‬
‫‪0‬‬ ‫‪0.5‬‬ ‫‪1‬‬
‫ﺍﻝﺸﻜل )‪ : (7‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪ x = Vb /Vb(eqv) ، pH = f (x‬ﻭﺫﻝﻙ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ ﺇﻝﻰ‬
‫ﻤﺤﻠﻭل ﺤﻤﺽ ﻀﻌﻴﻑ ﻝﻬﻤﺎ ﺍﻝﺘﺭﻜﻴﺯ ﻨﻔﺴﻪ‪ .‬ﺘﺼﺒﺢ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻤﺴﺘﻘﻴﻤﺔ ﻭﻤﻨﻁﺒﻘﺔ ﻋﻨﺩﻤﺎ ‪. 0.3 < x < 0.8‬‬
‫‪ .2.3.I‬ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻝﻴﺱ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ‬
‫ﻨﻘﻊ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺤﻤﺽ ﺍﻝﻀﻌﻴﻑ ﺍﻝﻤﻌﺎ ‪‬ﻴﺭ ﻗﻭﻴﹰﺎ ﻨﺴﺒﻴﹰﺎ ﺃﻭ ﻤﻤﺩﺩﹰﺍ ﻋﻠﻰ ﻨﺤﻭ‬
‫ﻜﺎﻑ‪ .‬ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻴﺠﺏ ﺃﻥ ﻨﺄﺨﺫ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪HA + OH− A− + H2O‬‬ ‫) ‪: K10 = 10(pK w −pK A‬‬
‫)‪(2‬‬ ‫‪HA + H2O A− + H3O+‬‬ ‫‪: K 20 = 10−pK A‬‬
‫ﻝﻴﺱ ﻤﻥ ﺍﻝﺴﻬل ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺘﻌﺒﻴﺭ ﻋﻥ ‪ pH‬ﺍﻝﻭﺴﻁ ﺒﺩﻻﻝﺔ ‪ . x‬ﻭﻴﺠﺭﻱ ﻫﻨﺎ ﺘﺤﺩﻴﺩ‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺒﺩﻻﻝﺔ ﺍﻝﻌﻼﻗﺎﺕ ﺍﻝﺘﻲ ﺩﺭﺴﻨﺎﻫﺎ ﻓﻲ ﺍﻝﻔﺼل ﺍﻝﺴﺎﺒﻕ‪.‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬
‫‪12‬‬ ‫‪A−‬‬ ‫‪80‬‬
‫‪10‬‬
‫‪AH‬‬ ‫‪60‬‬
‫‪8‬‬
‫‪6‬‬ ‫‪40‬‬
‫‪pK A =4‬‬
‫‪4‬‬ ‫‪pK A =2.5‬‬
‫‪pK A =1‬‬
‫‪20‬‬
‫‪2‬‬
‫‪0‬‬ ‫‪x‬‬
‫‪0‬‬ ‫‪0.5‬‬ ‫‪1‬‬
‫ﺍﻝﺸﻜل )‪ : (8‬ﺘﺄﺜﻴﺭ ‪ p K A‬ﺍﻝﺤﻤﺽ ﺍﻝﻤﻌﺎﻴ‪‬ﺭ ﻋﻠﻰ ﺃﺸﻜﺎل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪pH = f (x‬‬
‫ﻭ ) ‪ %(HA) = f (x‬ﻭ ) ‪.( C a = 5.0 × 10−2 mol/L ) %(A− ) = f (x‬‬
‫ﺘﺘﻴﺢ ﺍﻻﺴﺘﻌﺎﻨﺔ ﺒﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﻤﺤﺎﻜﺎﺓ ﺇﻅﻬﺎﺭ ﺘﺄﺜﻴﺭ ﻗﻴﻤﺔ ‪ p K A‬ﺍﻝﻭﺴﻁ ﻭﺍﻝﺘﺭﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻲ‬
‫ﻝﻠﺤﻤﺽ ﻋﻠﻰ ﺃﺸﻜﺎل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ) ‪ pH = f (x‬ﻭﻋﻠﻰ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻠﺤﻤﺽ ﻭﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ‬
‫ﺃﺜﻨﺎﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﺍﻝﺸﻜل )‪ (8‬ﻭﺍﻝﺸﻜل )‪. (9‬‬
‫ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺤﻤﺽ ﻤﺘﻔﻜﻜﹰﺎ ﺒﺸﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻨﺘﻴﺠﺔ ﻻﻨﺨﻔﺎﺽ ﻗﻴﻤﺔ ‪ p K A‬ﺃﻭ‬
‫ﻥ ﺍﻝﻌﻼﻗﺔ ‪ pH = p K A‬ﻻ ﺘﻌﻭﺩ ﻤﺤﻘﻘﺔ ﻋﻨﺩ ﺍﻝﻭﺼﻭل‬
‫ﻨﺘﻴﺠﺔ ﻝﺘﻤﺩﻴﺩﻩ ﺍﻝﺸﺩﻴﺩ‪ ،‬ﻓﺈ ‪‬‬
‫ﺇﻝﻰ ﻤﻨﺘﺼﻑ ﻗﻴﻤﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬ ‫‪A−‬‬
‫‪12‬‬
‫‬ ‫‪80‬‬
‫‬
‫‪10‬‬
‫‪AH‬‬ ‫‬ ‫‪60‬‬
‫‪8‬‬
‫‪6‬‬ ‫‪40‬‬
‫‪C a = 0.1 mol/L‬‬
‫‪4‬‬
‫‪C a = 0.001 mol/L‬‬ ‫‪20‬‬
‫‪2‬‬ ‫‪C a = 0.0003 mol/L‬‬
‫‪0‬‬ ‫‪x‬‬
‫‪0‬‬ ‫‪0.5‬‬ ‫‪1‬‬
‫ﺍﻝﺸﻜل )‪ : (9‬ﺘﺄﺜﻴﺭ ﺘﺭﻜﻴﺯ ﺍﻝﺤﻤﺽ ﺍﻝﻤﻌﺎﻴ‪‬ﺭ ‪ p K A = 4.0‬ﻋﻠﻰ ﺃﺸﻜﺎل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ‬
‫) ‪ pH = f (x‬ﻭ ) ‪ %(HA) = f (x‬ﻭ ) ‪ %(A− ) = f (x‬ﺤﻴﺙ ﻭ ‪. C a = C b‬‬
‫‪ .4.I‬ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺤﻤﺽ ﻗﻭﻱ‬
‫ﻴﻤﻜﻨﻨﺎ ﻤﻌﺎﻝﺠﺔ ﻤﻨﺤﻨﻴﺎﺕ ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺤﻤﺽ ﻗﻭﻱ ﻋﻠﻰ ﻨﺤﻭ ﻤﺸﺎﺒﻪ ﻝﻤﺎ ﻓﻌﻠﻨﺎﻩ‬
‫ﻓﻲ ﺍﻝﻔﻘﺭﺓ ﺍﻝﺴﺎﺒﻘﺔ ﻋﻨﺩ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ‪ ،‬ﻭﺫﻝﻙ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﻘﺎﺭﺒﺎﺕ ﺍﻝﺘﺎﻝﻴﺔ‬
‫ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺍﻝﺘﺸﺎﺒﻪ ﻓﻲ ﺍﻷﺩﻭﺍﺭ ﺒﻴﻥ ﺍﻝﻤﻘﺎﺩﻴﺭ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺤﻤﺽ ﻗﻭﻱ‬ ‫↔‬ ‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ‬
‫‪[OH− ] = ω‬‬ ‫↔‬ ‫‪[H3O+ ] = h‬‬
‫‪p OH = − log ω‬‬ ‫↔‬ ‫‪pH = − log h‬‬
‫‪KB‬‬ ‫↔‬ ‫‪KA‬‬
‫‪pK B = pK w − p K A‬‬ ‫↔‬ ‫‪pK A‬‬
‫ﻭﻝﺩﻴﻨﺎ ‪. pH + pOH = pK w‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ‪:‬‬

‫‪B + H3O+ BH+ + H2O‬‬
‫‪1‬‬
‫= ‪ . K‬ﻭﻜﻠﻤﺎ ﻜﺎﻨﺕ ﻗﻴﻤﺔ ‪ pK A‬ﻜﺒﻴﺭﺓ‪،‬‬ ‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ‪= 10pK A‬‬
‫‪KA‬‬
‫ﺃﻱ ﻜﺎﻥ ﺍﻷﺴﺎﺱ ﻗﻭﻴﹰﺎ ﺃﻜﺜﺭ‪ ،‬ﻜﺎﻥ ﺍﻝﺘﻔﺎﻋل ﻜﻤﻴﹰﺎ ﺃﻜﺜﺭ‪ .‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل )‪ (10‬ﺍﻝﻤﻨﺤﻨﻴﺎﺕ‬
‫) ‪ pH = f (x‬ﺍﻝﻤﻭﺍﻓﻘﺔ‪.‬‬
‫‪pH‬‬
‫‪14‬‬ ‫‪C a =C b = 0.1 mol/L‬‬
‫‪C a =C b = 0.01 mol/L‬‬
‫‪12‬‬ ‫‪C a =C b = 0.001 mol/L‬‬
‫‪10‬‬
‫‪8‬‬
‫‪6‬‬
‫‪4‬‬
‫‬
‫‪2‬‬ ‫‬
‫‬
‫‪0‬‬ ‫‪x‬‬
‫‪0‬‬ ‫‪0.5‬‬ ‫‪1‬‬
‫ﺍﻝﺸﻜل )‪ : (10‬ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺎﺴﺘﻌﻤﺎل ﺤﻤﺽ ﻗﻭﻱ‪ :‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﻤﺩﻴﺩ‪.‬‬
‫‪ .5.I‬ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ‬
‫‪ .1.5.I‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ‬
‫ﻝﻴﻜﻥ ﻝﺩﻴﻨﺎ ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ‪ H2A‬ﺒﺤﺠﻡ ‪ Va‬ﻭﺒﺘﺭﻜﻴﺯ ‪ C a‬ﻏﻴﺭ ﻤﻌﻠﻭﻡ‪ .‬ﻨﻀﻴﻑ‬
‫ﻼ(‬
‫ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺤﺠﻤﹰﺎ ‪ Vb‬ﻤﻥ ﻤﺤﻠﻭل ﺃﺴﺎﺱ ﻗﻭﻱ ) ‪ Na + + OH−‬ﻤﺜ ﹰ‬
‫ﺒﺘﺭﻜﻴﺯ ﻤﻌﻠﻭ ﻡ ‪ .C b‬ﻭ ﻝﻴﻜﻥ ‪ K A‬ﻭ ‪ K A‬ﺜﺎﺒﺘﻲ ﺍ ﻝﺤﻤﻭﻀﺔ ﻝﻠﺤﻤﺽ ‪ . H2A‬ﻋﻨﺩ ﺇﻀﺎ ﻓﺔ‬
‫‪2‬‬ ‫‪1‬‬
‫ﺍﻝﺼﻭﺩ‪ ،‬ﻴﺤﺩﺙ ﺩﺍﺨل ﺒﻴﻜﺭ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﺘﻔﺎﻋﻼﻥ ﺍﻝﺘﺎﻝﻴﺎﻥ‪:‬‬

‫) ‪(pK w −pK A‬‬
‫)‪(1‬‬ ‫‪H2A + OH− HA− + H2O‬‬ ‫‪: K10 = 10‬‬ ‫‪1‬‬
‫) ‪(pK w −pK A‬‬

‫)‪(2‬‬ ‫‪HA− + OH− A2− + H2O‬‬ ‫‪: K 20 = 10‬‬ ‫‪2‬‬
‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻴﻤﻜﻨﻨﺎ ﺘﻌﺭﻴﻑ ﺘﻜﺎﻓﺅﻴﻥ‪:‬‬

‫♦ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل‪، n(OH− )added = n 0 (H2A) :‬‬
‫♦ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻝﺜﺎﻨﻲ‪. n(OH− )added = 2n 0 (H2A) :‬‬
‫ﻴﻤﻜﻨﻨﺎ ﻋﻠﻰ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ ، pH = f (V‬ﺤﻴﺙ ‪ V‬ﻫﻭ ﺤﺠﻡ ﺍﻝﺼﻭﺩ ﺍﻝﻤﻀﺎﻑ‪ ،‬ﺘﻤﻴﻴﺯ ﻗﻔﺯﺓ‬
‫ﻭﺤﻴﺩﺓ ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ ﺃﻭ ﻗﻔﺯﺘﻴﻥ ﻭﺫﻝﻙ ﺘﺒﻌﹰﺎ ﻝﻠﻘﻴﻡ ﺍﻝﻌﺩﺩﻴﺔ ﻝﻜل ﻤﻥ ‪ K A‬ﻭ ‪. K A‬‬
‫‪2‬‬ ‫‪1‬‬
‫ﻋﻨﺩﻤﺎ ﻴﻤﻜﻨﻨﺎ ﺍﻝﺘﻤﻴﻴﺯ ﻋﻠﻰ ﻤﻨﺤﻨﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻗﻔﺯﺘﻴﻥ ﻓﻲ ﻗﻴﻡ ‪ pH‬ﺍﻝﻭﺴﻁ‪ ،‬ﻓﻬﺫﺍ ﻴﻌﻨﻲ‬
‫ﺤﺼﻭل ﺍﻝﺘﻔﺎﻋﻠﻴﻥ )‪ (1‬ﻭ )‪ (2‬ﻋﻠﻰ ﻨﺤﻭ ﻤﻨﻔﺼل ﻭﺒﺼﻭﺭﺓ ﻤﺘﻌﺎﻗﺒﺔ‪ .‬ﻭﻴﻜﻭﻥ ﺫﻝﻙ ﻋﻨﺩﻤﺎ‬
‫‪ ، K A ≫ K A‬ﺍﻝﺸﻜل )‪. (11‬‬
‫‪1‬‬ ‫‪2‬‬
‫‪pH‬‬
‫‪14‬‬ ‫‪ pK A2 = 5.0: ∆pK A = 1‬‬
‫‪ pK A2 = 6.5: ∆pK A = 2.5‬‬
‫‪12‬‬ ‫‪ pK A2 = 8.0: ∆pK A = 4‬‬
‫‪10‬‬
‫‬
‫‪8‬‬
‫‬
‫‪6‬‬ ‫‬
‫‪4‬‬
‫‪2‬‬
‫‪0‬‬ ‫‪x‬‬
‫‪0‬‬ ‫‪1.0‬‬ ‫‪2.0‬‬
‫ﺍﻝﺸﻜل )‪ : (11‬ﺘﺄﺜﻴﺭ ﺍﻝﻔﺭﻕ ﺒﻴﻥ ﻗﻴﻤﺘﻲ ‪ pK A‬ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ﻋﻠﻰ ﺃﺸﻜﺎل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ‬
‫) ‪) pH = f (x‬ﺭ‪‬ﺴﻤﺕ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻓﻲ ﺤﺎﻝﺔ ‪ pK A = 4.0‬ﻭ ‪( C a = 1.0 × 10−2 mol/L‬‬
‫‪1‬‬
‫ﺇﺫﺍ ﺃﺭﺩﻨﺎ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل ﺃﻥ ﻴﺘﻔﺎﻋل ﺃﻜﺜﺭ ﻤﻥ ‪ 99%‬ﻤﻥ ‪ H2A‬ﻭﺃﻗل ﻤﻥ ‪ 1%‬ﻤﻥ‬
‫‪ ، HA−‬ﻓﻬﺫﺍ ﻴﻌﻨﻲ ﺃﻨﹼﻪ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ‪ E‬ﻝﺩﻴﻨﺎ‪:‬‬
‫‪ pHE ≥ pK A + 2‬ﻭ ‪pHE ≤ pK A − 2‬‬
‫‪2‬‬ ‫‪1‬‬
‫)ﺍﻝﺸﻜل )‪ ،( (12‬ﻭﻫﺫﺍ ﻴﺘﺤﻘﹼﻕ ﻋﻨﺩﻤﺎ‪:‬‬

‫‪∆p K A = p K A − p K A ≥ 4‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪H2 A‬‬ ‫‪HA−‬‬ ‫‪A2 −‬‬
‫‪pK A‬‬ ‫‪p KA +2‬‬ ‫‪p KA −2‬‬ ‫‪pK A‬‬ ‫‪pH‬‬

‫‪1‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪2‬‬
‫ﺍﻝﺸﻜل )‪ : (12‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻸﻨﻭﺍﻉ ﺍﻝﻤﺘﻭﻓﺭﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻭﺸﺭﻁ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﻤﻨﻔﺼﻠﺔ‪.‬‬

‫ ‬
‫ﺍﻝﺘﺨﻔﻴﻑ ﻤﻥ ﺍﻝﺘﺄﺜﻴﺭ ﺍﻝﺴﻠﺒﻲ ﻝﻠﺤﻤﻭﺽ ﺒﺎﺴﺘﻌﻤﺎل ﺃﻤﻼﺡ ﻏﻴﺭ ﻤﺅﺫﻴﺔ‬
‫ﻨﻠﻤﺱ ﺍﻷﺜﺭ ﺍﻝﺴﻠﺒﻲ ﻝﻠﺤﻤﻭﺽ ﻓﻲ ﻜﺜﻴﺭ ﻤﻥ ﻤﻨﺎﺤﻲ ﺍﻝﺤﻴﺎﺓ ﺍﺒﺘﺩﺍﺀ ﻤﻥ ﺍﺼﻔﺭﺍﺭ ﺃﻭﺭﺍﻕ ﺍﻝﻜﺘﺏ ﺍﻝﻘﺩﻴﻤﺔ ﻤﺭﻭﺭﹰﺍ ﺒﺎﻝﺸﻌﻭﺭ‬
‫ﺒﺤﺭﻗﺔ ﻓﻲ ﺍﻝﻤﻌﺩﺓ ﻭﺍﻨﺘﻬﺎﺀ ﺒﺘﻠﻭﺙ ﺍﻝﺒﻴﺌﺔ ﺍﻝﻨﺎﺠﻡ ﻋﻥ ﺍﻝﻤﻁﺭ ﺍﻝﺤﺎﻤﻀﻲ ﺃﻭﻤﺨﻠﹼﻔﺎﺕ ﺒﻁﺎﺭﻴﺎﺕ ﺍﻝﺴﻴﺎﺭﺍﺕ‪ ،‬ﻭﺍﻝﻘﺎﺌﻤﺔ‬
‫ﺘﻁﻭل‪....‬‬
‫ل ﺍﻷﻤﺜل ﻝﺘﻌﺩﻴل ﻓﺎﺌﺽ ﺍﻝﺤﻤﻭﻀﺔ ﻴﻜﻭﻥ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‪ ،‬ﻭﻝﻜﻥ ﻓﻲ ﺍﻝﻭﺍﻗﻊ‬
‫ﻗﺩ ﻨﻅﻥ ﻝﻠﻭﻫﻠﺔ ﺍﻷﻭﻝﻰ ﺃ ‪‬‬
‫ﻼ ﻝﻭﺠﺩﻨﺎ ﺃﻥ ﻫﻨﺎﻙ ﺍﻝﻌﺩﻴﺩ ﻤﻥ ﺍﻝﻤﺭﻜﹼﺒﺎﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﺘﻲ ﻻ ﺘﻘل ﻓﻌﺎﻝﻴﺔ ﻋﻥ ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ ﻓﻲ ﺘﻌﺩﻴل‬
‫ﻝﻭ ﻓﻜﹼﺭﻨﺎ ﻗﻠﻴ ﹶ‬
‫ﺍﻝﺤﻤﺽ ﻭﻝﻴﺱ ﻝﻬﺎ ﺍﻝﻤﺨﺎﻁﺭ ﺍﻝﺘﻲ ﻴﺨﻠﻔﻬﺎ ﺍﺴﺘﻌﻤﺎل ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‪ .‬ﻭﻫﺫﻩ ﺍﻝﻤﺭﻜﺒﺎﺕ ﻫﻲ ﻓﻲ ﺍﻝﻭﺍﻗﻊ ﺍﻷﻤﻼﺡ ﺍﻝﻨﺎﺘﺠﺔ‬
‫ﻋﻥ ﺘﻔﺎﻋل ﺤﻤﺽ ﻀﻌﻴﻑ ﻤﻊ ﺃﺴﺎﺱ ﻗﻭﻱ‪ .‬ﺘﺴﺘﻁﻴﻊ ﻫﺫﻩ ﺍﻷﻤﻼﺡ ﺘﻌﺩﻴل ﺍﻝﺤﻤﺽ‪ ،‬ﻷﻥ ﺘﻔﺎﻋل ﺤﻠﻤﻬﺘﻬﺎ ﺒﺎﻝﻤﺎﺀ ﻴﻌﻁﻲ‬
‫ﻤﺤﺎﻝﻴل ﺃﺴﺎﺴﻴﺔ ﺃﻭ ﻗﻠﻭﻴﺔ‪.‬‬
‫ﻼ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻭﺤﻴﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ‪ (Baking soda) NaHCO3‬ﻝﺘﻌﺩﻴل ﺤﻤﺽ‬
‫ﻓﺈﺫﺍ ﺍﺴﺘﻌﻤﻠﻨﺎ ﻤﺜ ﹰ‬
‫ﺍﻝﻜﺒﺭﻴﺕ ﺍﻝﻨﺎﺘﺞ ﻋﻥ ﻤﺨﻠﻔﺎﺕ ﺒﻁﺎﺭﻴﺎﺕ ﺍﻝﺴﻴﺎﺭﺍﺕ ﻋﻭﻀ ﹰﺎ ﻋﻥ ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‪ ،‬ﻓﺈﻨﻨﺎ ﻝﻥ ﻨﻘﻠﻕ ﻋﻠﻰ ﺍﻝﺒﻴﺌﺔ ﺇﺫﺍ ﺒﻘﻲ‬
‫ﺍﻝﻘﻠﻴل ﻤﻥ ‪ NaHCO3‬ﺒﻌﺩ ﺍﻝﺘﻌﺩﻴل ﻋﻠﻰ ﺍﻷﺭﺽ‪ .‬ﻓﻲ ﺤﻴﻥ ﺃﻥ ﺒﻘﺎﺀ ﺍﻝﻔﺎﺌﺽ ﻤﻥ ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ ﺒﻌﺩ ﺍﻝﺘﻌﺩﻴل ﻴﻌﺘﺒﺭ‬
‫ل ﺨﻁﻭﺭﺓ ﻋﻥ ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ‪.‬‬
‫ﻤﻠﻭﺜﹰﺎ ﻻ ﻴﻘ ّ‬
‫ﻭﻴﻨﻁﺒﻕ ﺍﻷﻤﺭ ﻨﻔﺴﻪ ﻋﻨﺩ ﻤﻌﺎﻝﺠﺔ ﻋﺴﺭ ﺍﻝﻬﻀﻡ ﺍﻝﻨﺎﺘﺞ ﻋﻥ ﻓﺭﻁ ﺤﻤﻭﻀﺔ ﺍﻝﻤﻌﺩﺓ‪ .‬ﺇﺫ ﻝﻴﺱ ﻤﻥ ﺍﻝﻤﻌﻘﻭل ﺘﻨﺎﻭل ﺍﻝﺼﻭﺩ‬
‫ﺍﻝﻜﺎﻭﻱ ﺃﻭ ﻏﻴﺭﻩ ﻤﻥ ﺍﻷﺴﺱ ﺍﻝﻘﻭﻴﺔ ﻝﺘﻌﺩﻴل ﻓﺭﻁ ﺤﻤﻭﻀﺔ ﺍﻝﻤﻌﺩﺓ‪ .‬ﻭﺇﻨﻤﺎ ﻴﻠﺠﺄ ﺍﻝﻨﺎﺱ ﺇﻝﻰ ﻤﻀﺎﺩﺍﺕ ﺍﻝﺤﻤﻭﻀﺔ‬
‫‪ antacids‬ﻭﻫﻲ ﻋﺎﺩﺓ ﻤﺭﻜﺒﺎﺕ ﺘﻀ ‪‬ﻡ ﺃﻤﻼﺤ ﹰﺎ ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺃﻭ ﺒﻴﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻭﻜﺭﺒﻭﻨﺎﺕ‬
‫ﺍﻝﻤﻐﻨﺯﻴﻭﻡ‪ ،‬ﻭﻫﺫﻩ ﺠﻤﻴﻌﻬﺎ ﺃﻤﻼﺡ ﻝﺤﻤﻭﺽ ﻀﻌﻴﻔﺔ ﺤﻴﺙ ﺘﺘﺤﻠﻤﻪ ﻝﺘﻭﻝﹼﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺘﻲ ﺘﻘﻭﻡ ﺒﺘﺨﻔﻴﻑ ﺩﺭﺠﺔ‬
‫ﺤﻤﻭﻀﺔ ﺍﻝﻤﻌﺩﺓ‪.‬‬
‫ﺍﺴﺘﻌﻤﻠﺕ ﺃﻴﻀﹰﺎ ﻫﺫﻩ ﺍﻷﻤﻼﺡ ﻝﻤﻘﺎﻭﻤﺔ ﺘﻘﺎﺩﻡ ﺃﻭﺭﺍﻕ ﺍﻝﻜﺘﺏ ﻭﺍﻝﻤﺨﻁﻭﻁﺎﺕ ﻓﻲ ﺍﻝﻤﻜﺘﺒﺎﺕ ﺍﻝﻜﺒﺭﻯ ﺍﻝﺘﻲ ﺘﺨﺴﺭ ﺴﻨﻭﻴﹰﺎ‬
‫ﺁﻻﻑ ﺍﻝﻜﺘﺏ ﺍﻝﻘﺩﻴﻤﺔ ﻨﺘﻴﺠﺔ ﻝﺘﻔﻜﻙ ﺍﻝﻭﺭﻕ ﺍﻝﻘﺩﻴﻡ‪ .‬ﺇﺫ ﻴﺘﺭﺍﻭﺡ ﻋﻤﺭ ﺍﻝﻭﺭﻕ ﺒﻴﻥ ‪ 25‬ﻭ‪ 40‬ﻋﺎﻤﹰﺎ‪ .‬ﻭﻴﺘﻘﺎﺩﻡ ﺍﻝﻭﺭﻕ ﺒﺴﺒﺏ‬
‫ﺤﻠﻤﻬﺔ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻷﻝﻤﻨﻴﻭﻡ ﺍﻝﺫﻱ ﺠﺭﺕ ﺇﻀﺎﻓﺘﻪ ﺇﻝﻰ ﺍﻝﻭﺭﻕ ﻋﻨﺩ ﺘﺼﻨﻴﻌﻪ ﻭﺫﻝﻙ ﻭﻓﻕ ﺘﻘﻨﻴﺔ ﺃُﺩﺨﻠﺕ ﺇﻝﻰ ﺼﻨﺎﻋﺔ ﺍﻝﻭﺭﻕ‬
‫ﻤﻨﺫ ﻋﺎﻡ ‪ 1850‬ﺒﻬﺩﻑ ﺘﺜﺒﻴﺕ ﺤﺒﺭ ﺍﻝﻁﺒﺎﻋﺔ ﻋﻠﻰ ﺍﻝﻭﺭﻕ ﻭﻤﻨﻌﻪ ﻤﻥ ﺍﻻﻨﺘﺸﺎﺭ‪ .‬ﻭﻜﺒﺭﻴﺘﺎﺕ ﺍﻷﻝﻤﻨﻴﻭﻡ ﻫﻲ ﻓﻲ ﻭﺍﻗﻊ‬
‫ﻥ ﺤﻠﻤﻬﺘﻪ ﺒﺎﻝﻤﺎﺀ ﺍﻝﻤﻭﺠﻭﺩ‬
‫ﺍﻷﻤﺭ ﻤﻠﺢ ﻨﺎﺘﺞ ﻋﻥ ﺘﻔﺎﻋل ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﻏﻴﺭ ﻤﻨﺤل ﺒﺎﻝﻤﺎﺀ ﻤﻊ ﺤﻤﺽ ﻗﻭﻱ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﻓﻲ ﺍﻝﻭﺭﻕ )‪ (4-7%‬ﺘﻌﻁﻲ ﻭﺴﻁ ﹰﺎ ﺤﻤﻀﻴ ﹰﺎ‪ .‬ﻴﻘﻭﻡ ﻫﺫﺍ ﺍﻝﻭﺴﻁ ﺍﻝﺤﺎﻤﻀﻲ ﺒﺄﻜل ﺃﻝﻴﺎﻑ ﺍﻝﺴﻴﻠﻠﻭﺯ ﻭﺸﻴﺌ ًﹶﺎ ﻓﺸﻴﺌﹰﺎ ﻴﺼﻔﺭ‬
‫ﺍﻝﻭﺭﻕ ﻭﻴﺘﺤﻠﹼل‪ .‬ﻝﻬﺫﺍ ﻝﺠﺄﺕ ﺒﻌﺽ ﺍﻝﻤﻜﺘﺒﺎﺕ ﺍﻝﻜﺒﺭﻯ ﺇﻝﻰ ﻤﻌﺎﻝﺠﺔ ﺘﻘﺎﺩﻡ ﻜﺘﺒﻬﺎ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﺎﻝﻴل ﺍﻷﻤﻼﺡ ﺫﺍﺕ ﺍﻝﺘﻔﺎﻋل‬
‫ﺍﻝﻘﻠﻭﻱ ﻭﺍﻝﻨﺎﺘﺠﺔ ﻋﻥ ﺘﻔﺎﻋل ﺤﻤﺽ ﻀﻌﻴﻑ ﻤﻊ ﺃﺴﺎﺱ ﻗﻭﻱ‪ .‬ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﺘﺘﺼﺩﻯ ﺼﻨﺎﻋﺔ ﺍﻝﻭﺭﻕ ﺍﻝﺤﺎﻝﻴﺔ ﻝﻤﺴﺄﻝﺔ‬
‫ﺍﻝﺘﻘﺎﺩﻡ ﻋﻥ ﻁﺭﻴﻕ ﻤﺤﺎﻭﻝﺔ ﺘﺼﻨﻴﻊ ﻭﺭﻕ ﺃﺴﺎﺴﻲ ﺍﻝﺘﻔﺎﻋل ‪ alkaline paper‬ﻭﺫﻝﻙ ﺒﺈﻀﺎﻓﺔ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫ﻭﻫﻭ ﺍﻝﻤﺭﻜﹼﺏ ﺫﺍﺘﻪ ﺍﻝﺫﻱ ﻨﺠﺩﻩ ﻓﻲ ﺒﻌﺽ ﻤﻘﺎﻭﻤﺎﺕ ﺤﻤﻭﻀﺔ ﺍﻝﻤﻌﺩﺓ‪ .‬ﺘﺴﻤﺢ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺒﺭﻓﻊ ‪ pH‬ﺍﻝﻭﺭﻕ‬
‫ﺇﻝﻰ ﺤﺩﻭﺩ ‪. 7.5 − 8.5‬‬
‫ﻭﻤﻥ ﺍﻝﻤﻔﺘﺭﺽ ﺃﻥ ﻴﺼل ﻋﻤﺭ ﻫﺫﺍ ﺍﻝﻭﺭﻕ ﺍﻝﻘﻠﻭﻱ ﺇﻝﻰ ﺯﻫﺎﺀ ‪ 300‬ﻋﺎﻤﹰﺎ‪.‬‬
‫‪ .2.5.I‬ﻋﺒﺎﺭﺍﺕ ) ‪ pH = f (x‬ﻝﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻤﻀﺎﻋﻑ ﺤﻴﺙ ‪pK A − pK A ≥ 4‬‬

‫‪2‬‬ ‫‪1‬‬
‫ﺇﺫﺍ ﻜﺎﻥ ﺘﻔﺎﻋﻼ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻤﺎ ﻓﻘﻁ ﺍﻝﺘﻔﺎﻋﻼﻥ ﺍﻝﺭﺍﺠﺤﺎﻥ ﻓﻲ ﻫﺫﺍ ﺍﻝﻭﺴﻁ ﺍﻝﺘﻔﺎﻋﻠﻲ‪ ،‬ﻭﺇﺫﺍ ﻜﺎﻥ‬
‫ﻥ ﻤﻥ ﺍﻝﻤﻤﻜﻥ ﺍﻝﺘﻌﺒﻴﺭ‬
‫ﻥ ‪ ، ∆pK A ≥ 4‬ﻓﺈ ‪‬‬
‫ﻫﺫﺍﻥ ﺍﻝﺘﻔﺎﻋﻼﻥ ﻴﺠﺭﻴﺎﻥ ﺒﺼﻭﺭﺓ ﻤﺘﻌﺎﻗﺒﺔ ﺃﻱ ﺇ ‪‬‬
‫ﺒﺒﺴﺎﻁﺔ ﻋﻥ ﺍﻝﻌﺒﺎﺭﺍﺕ ) ‪ pH = f (x‬ﺤﻴﺙ ‪. x = V /Veqv‬‬
‫ﻥ ‪Vb = 0‬‬
‫‪ x = 0 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻴﻀﻡ ﺍﻝﻤﺤﻠﻭل ﻓﻘﻁ ﺤﻤﻀﹰﺎ ﻀﻌﻴﻔﹰﺎ‪ .‬ﻭﻴﺠﺭﻱ ﺘﺤﺩﻴﺩ ‪ pH‬ﺍﻝﻭﺴﻁ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻌﻼﻗﺔ‪:‬‬
‫‪1‬‬
‫ﻥ ﺍﻝﺤﻤﺽ ﻀﻌﻴﻑ ﺍﻝﺘﻔﻜﻙ ‪ ،‬ﻭﺒﺈﻫﻤﺎل‬
‫) ‪ pH = (pK A + pC a‬ﻭﺫﻝﻙ ﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫‪2‬‬ ‫‪1‬‬
‫ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪.‬‬

‫‪ 0 < x < 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ ﻫﻨﺎ ﻫﻭ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﺫﻭ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪H2A + OH− HA− + H2O‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﺼﻭﺭﺓ ﻤﺸﺎﺒﻬﺔ ﻝﻤﺎ ﺭﺃﻴﻨﺎﻩ ﻓﻲ ﺍﻝﻔﻘﺭﺓ ‪ .1.3.I‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪x‬‬
‫‪1‬‬
‫‪1−x‬‬
‫‪. pH = pK A‬‬ ‫ﻋﻨﺩﻤﺎ ‪ x = 0.5‬ﻨﻜﻭﻥ ﻗﺩ ﻭﺼﻠﻨﺎ ﺇﻝﻰ ﻨﺼﻑ ﺍﻝﺘﻜﺎﻓﺅ ﻭﻨﻜﺘﺏ‪:‬‬
‫‪1‬‬
‫ﻥ )‪) Vb = Vb(eqv1‬ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل(‬

‫‪ x = 1 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻴﻜﻭ ﻥ ﺍ ﻝﻤﺤﻠﻭ ل ﻫﻨﺎ ﻤﺘﺫ ﺒﺫ ﺒﹰﺎ ﺤﻤﻀﻴﹰﺎ‪ -‬ﺃﺴﺎﺴﻴﹰﺎ ﻭ ﻴﺠﺭ ﻱ ﺘﺤﺩ ﻴﺩ ‪ pH‬ﺍ ﻝﻭﺴﻁ ﺒﺎﺴﺘﻌﻤﺎل‬
‫ﺍﻝﻌﻼﻗﺔ‪:‬‬
‫‪1‬‬
‫) ‪pHeqv1 = (pK A + pK A‬‬
‫‪2‬‬ ‫‪1‬‬ ‫‪2‬‬
‫‪1<x <2 o‬‬

‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻨﺎ ﻫﻲ‪:‬‬
‫ﺇ‪‬‬
‫‪HA− + OH− A2− + H2O‬‬
‫ﻨﻌﺭ‪‬ﻑ‬
‫)‪Vb − Vb(eqv1‬‬
‫= ‪x′‬‬
‫)‪Vb(eqv1‬‬
‫ﺃﻱ ‪. x ′ = x − 1‬‬
‫ﻥ ﺘﻔﺎ ﻋل‬
‫ﻭﺘﻤﺎﻤﹰﺎ ﻜﻤﺎ ﻓﻲ ﺤﺎﻝﺔ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﻭﺤﻴﺩ ﺍ ﻝﻭﻅﻴﻔﺔ‪ ،‬ﻭﺒﺎ ﻓﺘﺭ ﺍ ﺽ ﺃ ‪‬‬
‫ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ‪ ،‬ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫‪x′‬‬
‫‪2‬‬
‫‪1 − x′‬‬
‫ﺃﻱ‬
‫‪x −1‬‬
‫‪2‬‬
‫‪2−x‬‬
‫‪. pH = pK A‬‬ ‫ﻋﻨﺩﻤﺎ ‪ x ′ = 0.5‬ﺃﻱ ‪ ، x = 1.5‬ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‬
‫‪2‬‬
‫ﻥ ‪) x ′ = 1‬ﺍﻝﺘﻜﺎﻓﺅ ﺍﻝﺜﺎﻨﻲ(‬
‫‪ x = 2 o‬ﺃﻱ ﺇ ‪‬‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺫﻱ ﻨﺤﺼل ﻋﻠﻴﻪ ﻴﻜﻭﻥ ﻤﻜﺎﻓﺌﹰﺎ ﻷﺴﺎﺱ ﻀﻌﻴﻑ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ‪A2−‬‬
‫ﺇ‪‬‬
‫ﺒﺘﺭﻜﻴﺯ‪:‬‬
‫)‪C b .Vb(eqv1‬‬ ‫‪C a .Va‬‬
‫= ‪C b′‬‬ ‫=‬
‫)‪Va + Vb(eqv2) Va + Vb(eqv2‬‬
‫ﻭﻴﺠﺭﻱ ﺘﺤﺩﻴﺩ ‪ pH‬ﺍﻝﻭﺴﻁ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻌﻼﻗﺔ‪:‬‬
‫‪1‬‬
‫)‪pOH = (pK B + pc ′‬‬
‫‪2‬‬ ‫‪2‬‬
‫ﺃﻱ‬
‫‪1‬‬
‫)‪pHeqv2 = (pK w + pK A2 − pc ′‬‬
‫‪2‬‬
‫ﻥ ﺒﺭﺘﻨﺔ ﺍﻷﺴﺎﺱ ﻀﻌﻴﻔﺔ ﻭﺒﺈﻫﻤﺎل ﺍﻝﺘﺤﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‪.‬‬
‫‪x >2 o‬‬

‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﻓﺎﺌﺽ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪ ،‬ﻭﻨﻜﺘﺏ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪: 25 C‬‬
‫)‪C b .Vb(eqv1‬‬
‫‪pH = 14 + log‬‬ ‫)‪+ log(x − 2‬‬
‫‪Va + Vb‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬ ‫‪H2TeO3‬‬ ‫‪HTeO−‬‬
‫‪3‬‬ ‫‪TeO23−‬‬
‫‪ւ‬‬ ‫‪ւ‬‬ ‫‪ւ‬‬
‫‪12‬‬ ‫‪80‬‬
‫‪10‬‬
‫‪60‬‬
‫‪8‬‬ ‫‪տ‬‬
‫‪pH‬‬
‫‪6‬‬ ‫‪40‬‬
‫‪4‬‬
‫‪20‬‬
‫‪2‬‬
‫‪x‬‬
‫‪0.5‬‬ ‫‪1.0‬‬ ‫‪1.5‬‬ ‫‪2.0‬‬ ‫‪2.5‬‬ ‫‪3.0‬‬
‫ﺍﻝﺸﻜل )‪ : (13‬ﻤﺤﺎﻜﺎﺓ ﻤﻌﺎﻴﺭﺓ ﺍﻝﺤﻤﺽ ‪. H2 TeO3‬‬
‫‪‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل )‪ (13‬ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﺫﻱ ﻨﺤﺼل ﻋﻠﻴﻪ ﻋﻨﺩ ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﺤﻤﺽ ﺍﻝﺘﻴﻠﻴﺭﻴﻭﻡ‬
‫‪ H2 TeO3‬ﺍﻝﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ ) ‪ pK A = 2.6‬ﻭ ‪ ( pK A = 7.7‬ﺒﺘﺭﻜﻴﺯ ‪. 0.5 mol/L‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪ .3.5.I‬ﻤﺤﺎﻜﺎﺓ ﻝﻤﻌﺎﻴﺭﺓ ﺒﻌﺽ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ‬
‫ﻨﻌﺭﺽ ﻓﻴﻤﺎ ﻴﻠﻲ ﻤﺤﺎﻜﺎﺓ ﻝﻤﻌﺎﻴﺭﺓ ﺤﻤﻀﻴﻥ ﻜل ﻤﻨﻬﻤﺎ ﺜﻼﺜﻲ ﺍﻝﻭﻅﻴﻔﺔ ﻫﻤﺎ ‪ :‬ﺤﻤﺽ‬
‫ﺍﻝﻔﻭﺴﻔﻭﺭ ‪ H3 PO4‬ﺍﻝﺫﻱ ﻨﺠﺩﻩ ﻓﻲ ﺍﻝﻌﺩﻴﺩ ﻤﻥ ﺍﻝﻤﺸﺭﻭﺒﺎﺕ ﺍﻝﻐﺎﺯﻴﺔ‪ ،‬ﻭﺤﻤﺽ ﺍﻝﻠﻴﻤﻭﻥ‬
‫‪ C6 H 8O7‬ﺍﻝﺫﻱ ﻨﺠﺩﻩ ﻓﻲ ﻋﺼﻴﺭ ﺍﻝﺤﻤﻀﻴﺎﺕ‪.‬‬
‫ﻨﻼﺤﻅ ﺃﻥ ﻤﻨﺤﻨﻲ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ ﻴﻅﻬﺭ ﻗﻔﺯﺘﻴﻥ ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪ ،‬ﺍﻝﺸﻜل‬
‫)‪ ، (14‬ﻓﻲ ﺤﻴﻥ ﻴ‪‬ﻅﻬﺭ ﻤﻨﺤﻨﻲ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺍﻝﻠﻴﻤﻭﻥ ﻗﻔﺯﺓ ﻭﺍﺤﺩﺓ ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪،‬‬
‫ﺍﻝﺸﻜل )‪. (15‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ﺤﻤﺽ ﺍﻝﻠﻴﻤﻭﻥ ) ‪: ( pK A = 6.4 ، pK A = 4.8 ، pK A = 3.1‬‬
‫‪3‬‬ ‫‪2‬‬ ‫‪1‬‬
‫ﻥ ﺍﻝﺤﻤﺽ ﻀﻌﻴﻑ ﺍﻝﺘﻔﻜﹼﻙ‬

‫ﻝﻤ‪‬ﺎ ﻜﺎﻨﺕ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﻭﻝﻰ ﻝﻴﺴﺕ ﻗﻭﻴﺔ ﻜﺜﻴﺭﺍﹰ‪ ،‬ﺃﻱ ﺇ ‪‬‬
‫ﺒﺩﺍﻴﺔ‪ ،‬ﻴﻜﻭﻥ ‪ pH ≈ pK A‬ﻋﻨﺩ ﻨﻘﻁﺔ ﻤﻨﺘﺼﻑ ﻗﻴﻤﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل‪ .‬ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ‬
‫‪1‬‬
‫ﻥ‬
‫ﻝﻤﺎ ﻜﺎﻨﺕ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻝﺜﺎﻝﺜﺔ ﻝﻴﺴﺕ ﻀﻌﻴﻔﺔ ﻜﺜﻴﺭﺍﹰ‪ ،‬ﻭﻗﻴﻡ ‪ pK A‬ﻤﺘﻘﺎﺭﺒﺔ‪ ،‬ﻓﺈ ‪‬‬
‫‪i‬‬
‫ﻗﻔﺯﺓ ‪ pH‬ﺍﻝﻭﺴﻁ ﺘﻌﻭﺩ ﺇﻝﻰ ﻤﻌﺎﻴﺭﺓ ﺍﻝﻭﻅﺎﺌﻑ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻝﺜﻼﺙ ﻭﻫﺫﺍ ﻤﺎ ﺘﺅﻜﹼﺩﻩ ﺃﻴﻀﹰﺎ‬
‫ﺘﺤﻭﻻﺕ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﺘﺭﺍﻜﻴﺯ ﺍﻷﻨﻭﺍﻉ ‪ . HA2− ، H2 A− ، H3 A‬ﻭﻫﻜﺫﺍ ﻨﻜﺘﺏ ﻋﻨﺩ‬

‫ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻹﺠﻤﺎﻝﻲ )‪. n(OH− ) = 3 ⋅ n 0 (H 3 A‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬ ‫‪H2PO−4‬‬
‫‪ց‬‬ ‫‪HPO24−‬‬
‫‪12‬‬ ‫‪ց‬‬ ‫‪80‬‬
‫‪տ‬‬
‫‪10‬‬ ‫‪pH‬‬
‫‪60‬‬
‫‪8‬‬ ‫‪H3PO4‬‬
‫‪ւ‬‬ ‫‪pK A‬‬
‫‪6‬‬ ‫‪2‬‬ ‫‪40‬‬
‫‪4‬‬
‫‪20‬‬
‫‪տ‬‬
‫‪2‬‬ ‫‪PO34−‬‬
‫‪pK A‬‬
‫‪1‬‬ ‫‪x‬‬
‫‪0.5‬‬ ‫‪1.0‬‬ ‫‪1.5‬‬ ‫‪2.0‬‬ ‫‪2.5‬‬ ‫‪3.0‬‬ ‫‪3.5‬‬
‫ﺍﻝﺸﻜل )‪ : (14‬ﻤﺤﺎﻜﺎﺓ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ‪. c = 0.05 mol/L ،‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ ) ‪: ( pK A = 12.1 ، pK A = 7.2 ، pK A = 2.1‬‬

‫‪3‬‬ ‫‪2‬‬ ‫‪1‬‬
‫ﻝﻤ‪‬ﺎ ﻜﺎﻨﺕ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻝﺜﺎﻝﺜﺔ ﻀﻌﻴﻔﺔ‪ ،‬ﺃﻱ ﺇﻥ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ ﺘﻔﺎﻋل ﻤﻌﺎﻴﺭﺘﻬﺎ ﺼﻐﻴﺭ‬
‫ﻨﺴﺒﻴﹰﺎ‪ ،‬ﻭﻫﺫﺍ ﻤﺎ ﺘﺅﻜﹼﺩﻩ ﺃﻴﻀﹰﺎ ﺘﺤﻭﻻﺕ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻨﻭﻋﻴﻥ ‪، HPO24−‬‬
‫‪ ، PO34−‬ﻓﺈﻨﻨﺎ ﻨﻠﺤﻅ ﻗﻔﺯﺘﻴﻥ ﻓﻘﻁ ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪.‬‬
‫ﻥ ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﻝﻤﺎ ﻜﺎﻨﺕ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﻭﻝﻰ ﻗﻭﻴﺔ ﻨﺴﺒﻴ ﹰﺎ ﻓﺈ ‪‬‬
‫ﻤﺘﻔﻜﹼﻙ ﺒﺩﺍﻴﺔ ﺒﺼﻭﺭﺓ ﻜﺒﻴﺭﺓ‪ ،‬ﻭﻋﻨﺩ ﻨﻘﻁﺔ ﻤﻨﺘﺼﻑ ﻗﻴﻤﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل ﻻ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻌﻼﻗﺔ‬
‫‪. pH ≈ pK A‬‬
‫‪1‬‬
‫ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﺩﺭﺱ ﺃﻴﻀﹰﺎ ﻤﻨﺤﻨﻲ ﻤﺤﺎﻜﺎﺓ ﺃﺴﺎﺱ ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﻭﻅﻴﻔﺔ‪ .‬ﻴﻅﻬﺭ ﺍﻝﺸﻜل )‪(16‬‬
‫ﻤﻨﺤﻨﻲ ﻤﻌﺎﻴﺭﺓ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﺒﻭﻨﺎﺕ ‪ ( pK A = 10.3 ، pK A = 6.4 ) CO23−‬ﺤﻴﺙ ﻨﻼﺤﻅ‬
‫‪2‬‬ ‫‪1‬‬
‫ﻗﻔﺯﺘﻴﻥ ﻭﺍﻀﺤﺘﻴﻥ ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪ ،‬ﻭﻫﺫﺍ ﻤﺎ ﻴﺘﻤﺎﺸﻰ ﻤﻊ ﻗﻴﻤﺘﻲ ‪ pK A‬ﻤﺘﺒﺎﻋﺩﺘﻴﻥ ﻨﺴﺒﻴﹰﺎ‪.‬‬

‫‪i‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬
‫‪H3Cit‬‬ ‫‪Cit3−‬‬
‫‪ւ‬‬ ‫‪HCit2−‬‬
‫‪12‬‬ ‫‪ց‬‬ ‫‪ց‬‬ ‫‪80‬‬
‫‪10‬‬ ‫‪տ‬‬
‫‪H2Cit−‬‬ ‫‪60‬‬
‫‪8‬‬
‫‪տ‬‬
‫‪pH‬‬
‫‪6‬‬ ‫‪p K A3‬‬ ‫‪40‬‬
‫‪pK A2‬‬
‫‪4‬‬
‫‪20‬‬
‫‪pK A‬‬
‫‪1‬‬
‫‪2‬‬
‫‪x‬‬
‫‪0.5‬‬ ‫‪1.0‬‬ ‫‪1.5‬‬ ‫‪2.0‬‬ ‫‪2.5‬‬ ‫‪3.0‬‬ ‫‪3.5‬‬ ‫‪4.0‬‬
‫ﺍﻝﺸﻜل )‪ : (15‬ﻤﺤﺎﻜﺎﺓ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺍﻝﻠﻴﻤﻭﻥ‪. c = 0.05 mol/L ،‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬
‫‪CO23−‬‬ ‫‪HCO−‬‬
‫‪3‬‬ ‫‪CO2‬‬
‫‪ւ‬‬ ‫‪ւ‬‬ ‫‪ւ‬‬
‫‪12‬‬ ‫‪80‬‬
‫‪pK A2‬‬
‫‪10‬‬
‫‪pH‬‬ ‫‪60‬‬
‫‪8‬‬ ‫‪ւ‬‬
‫‪6‬‬ ‫‪pK A‬‬ ‫‪40‬‬

‫‪1‬‬
‫‪4‬‬
‫‪20‬‬
‫‪2‬‬
‫‪x‬‬
‫‪0.5‬‬ ‫‪1.0‬‬ ‫‪1.5‬‬ ‫‪2.0‬‬ ‫‪2.5‬‬ ‫‪3.0‬‬
‫ﺍﻝﺸﻜل )‪ : (16‬ﻤﺤﺎﻜﺎﺓ ﻤﻌﺎﻴﺭﺓ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﺒﻭﻨﺎﺕ‪. c = 0.05 mol/L ،‬‬

‫‪ .II‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‬
‫‪ .1.II‬ﺃﻤﺜﻠﺔ‬
‫ﺇﻥ ﻤﻼﺤﻅﺔ ﻤﻨﺤﻨﻴﺎﺕ ) ‪ pH = f (x‬ﻓﻲ ﺤﺎﻝﺔ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺩﻻﻝﺔ ﺃﺴﺎﺱ‬
‫ﻗﻭﻱ ﺃﻭ ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺒﺩﻻﻝﺔ ﺤﻤﺽ ﻗﻭﻱ ﺘﻅﻬﺭ ﻤﺎ ﻴﻠﻲ‪:‬‬
‫ﻼ ﻓﻲ ﺠﻭﺍﺭ ﺍﻝﻘﻴﻤﺔ ‪ x = 0.5‬؛‬
‫♦ ﻴﺘﻐﻴﺭ ‪ pH‬ﺍﻝﻭﺴﻁ ﻗﻠﻴ ﹰ‬
‫♦ ﻓﻲ ﺠﻭﺍﺭ ﺍﻝﻘﻴﻤﺔ ‪ x = 0.5‬ﻻ ﺘﺘﻌﻠﹼﻕ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ ﺒﺘﺭﺍﻜﻴﺯ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻌﺘﺒﺭﺓ‪.‬‬
‫ﻥ ‪ pH‬ﻫﺫﻩ ﺍﻝﻤﺤﺎﻝﻴل ﻻ ﻴﺘﺄﺜﹼﺭ ﻜﺜﻴﺭﹰﺍ ﺒﺎﻝﺘﻤﺩﻴﺩ‪.‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻴﻤﻜﻥ ﺍﻋﺘﺒﺎﺭ ﻫﺫﻩ ﺍﻝﻤﺤﺎﻝﻴل ﺃﻤﺜﻠﺔ ﻋﻥ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‪.‬‬
‫ﻼ ﻫﻭ ﻤﺤﻠﻭل‬
‫ﻜﺜﻴﺭ ﹰﺍ ﻤﺎ ﻨﺠﺩ ﺃﻤﺜﻠﺔ ﻋﻥ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﺍﻷﻭﺴﺎﻁ ﺍﻝﺤﻴﻭﻴﺔ‪ ،‬ﻓﺎ ﻝﺩﻡ ﻤﺜ ﹰ‬
‫ﻕ ﻋﻨﺩ ‪ pH = 7.4‬ﻋﻨﺩ ﺩ ﺭ ﺠﺔ ﺍ ﻝﺤﺭ ﺍ ﺭ ﺓ ‪ 25 C‬ﻭ ﺫ ﻝﻙ ﺒﻔﻀل ﺍ ﻝﺯ ﻭ ﺠﻴﻥ‬
‫ﻤﻭ ‪‬‬
‫‪. CO2 / HCO−‬‬
‫‪ H2 PO4 / HPO4‬ﻭ ‪3‬‬
‫‪−‬‬ ‫‪2−‬‬
‫ ‬
‫ﺍﻝﻭﺴﻁ ﺍﻝﻤﻭﻗﻲ ﻓﻲ ﺍﻝﺩﻡ‬
‫ﺃﺤﺩ ﺃﻫﻡ ﺍﻝﻔﺭﻭﻕ ﺒﻴﻥ ﻤﺤﻠﻭل ﻤﻭﻕ ﻤﺤﻀ‪‬ﺭ ﻓﻲ ﺍﻝﻤﺨﺒﺭ ﻭﺒﻴﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻭﻗﻲ ﻓﻲ ﺍﻝﺩﻡ ﻫﻭ ﺘﻠﻙ ﺍﻵﻝﻴﺔ ﺍﻝﺘﻲ ﻴﺴﺎﻋﺩ‬
‫ﻓﻴﻬﺎ ﺍﻝﺠﺴﻡ ﺍﻝﺩﻡ ﻋﻠﻰ ﻤﻘﺎﻭﻤﺔ ﺘﻐﻴﺭﺍﺕ ‪ pH‬ﺍﻝﻭﺴﻁ‪ .‬ﺇﺫ ﺘﻘﻭﻡ ﺍﻝﺭﺌﺘﺎﻥ ﺒﺘﻨﻅﻴﻡ ﻜﻤﻴﺔ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺍﻝﺘﻲ‬
‫ﺘﺩﺨل ﺃﻭ ﺘﺨﺭﺝ ﻤﻨﻬﺎ‪ .‬ﻭﺘﺴﻬﻡ ﺍﻝﻜﻠﻴﺘﺎﻥ ﻓﻲ ﺘﻨﻅﻴﻡ ‪ pH‬ﺍﻝﺩﻡ ﻋﻥ ﻁﺭﻴﻕ ﺭﻓﻊ ﺃﻭ ﺨﻔﺽ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ‬
‫ﺍﻝﺘﻲ ﺘﻁﺭﺤﻬﺎ ﻓﻲ ﺍﻝﺒﻭل‪.‬‬
‫ﻼ ﺠﺩﹰﺍ ﻋﻨﺩ‪:‬‬
‫ﻻ ﺘﻐﻴﺭﹰﺍ ﻀﺌﻴ ﹰ‬
‫ﻕ ﺇﺫﺍ ﻝﻡ ﻴﺘﻐﻴﺭ ‪ pH‬ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل ﺇ ﹼ‬
‫ﻴﻜﻭﻥ ﻝﻤﺤﻠﻭل ﻤﺎ ﺃﺜﺭ ﻤﻭ ‪‬‬
‫♦ ﺇﻀﺎﻓﺔ ﻜﻤﻴﺎﺕ ﻗﻠﻴﻠﺔ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺃﻭ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﻭﻜﺴﻴﺩ ﻋﻥ‬
‫ﻁﺭﻴﻕ ﺤﻤﻭﺽ ﺃﻭ ﺃﺴﺱ ﻗﺩ ﺘﻜﻭﻥ ﻗﻭﻴﺔ‪.‬‬
‫♦ ﺘﻤﺩﻴﺩ ﺍﻝﻤﺤﻠﻭل ﻋﻠﻰ ﻨﺤﻭ ﻤﻘﺒﻭل‪.‬‬
‫ﻕ ﻗﺩﺭﺓ ﻤﻭﻗﻴﺔ ‪ β‬ﺘﹸﻌﺭ‪‬ﻑ ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬

‫ﻭﻝﻜل ﻤﺤﻠﻭل ﻤﻭ ‪‬‬
‫‪dC b‬‬ ‫‪dC a‬‬
‫=‪β‬‬ ‫=‬
‫‪dpH‬‬ ‫‪dpH‬‬
‫ﺤﻴﺙ ‪ dC a‬ﻭ ‪ dC b‬ﻫﻤﺎ ﻋﻠﻰ ﺍﻝﺘﺭﺘﻴﺏ ﺘﻐﻴﺭ ﺘﺭﻜﻴﺯ ﺍﻝﺤﻤﺽ ﺍﻝﻘﻭﻱ ﺃﻭ ﺍﻷﺴﺎﺱ ﺍﻝﻘﻭﻱ‬
‫ﺍﻝﺫﻱ ﻴﻭﻝﹼﺩ ﺒﺩﻭﺭﻩ ﺘﻐﻴﺭﹰﺍ ﻗﺩﺭﻩ ‪ dpH‬ﻓﻲ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪.‬‬
‫ﻭﻜﻠﻤﺎ ﻜﺎﻨﺕ ﻗﻴﻤﺔ ‪ β‬ﻜﺒﻴﺭﺓ ﻜﺎﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻭﻗﻲ ﺃﻜﺜﺭ ﻓﻌﺎﻝﻴﺔ‪ .‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ‪ β‬ﺘﺘﻌﻠﹼﻕ‬
‫ﺒﺎﻷﻨﻭﺍﻉ ﺍﻝﺤﻤﻀﻴﺔ ﺃﻭ ﺍﻷﺴﺎﺴﻴﺔ ﺍﻝﻤﻌﺘﺒﺭﺓ ﻭﺘﺭﺍﻜﻴﺯﻫﺎ‪ .‬ﻝﻨﺤﺩ‪‬ﺩ ‪ β‬ﻓﻲ ﺤﺎﻝﺘﻴﻥ ﺒﺴﻴﻁﺘﻴﻥ‪:‬‬
‫‪ .3.II‬ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﺠﻭﺍﺭ ﻨﻘﻁﺔ ﻤﻨﺘﺼﻑ ﻗﻴﻤﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫ﻥ ‪ pH‬ﻫﺫﺍ ﺍﻝﻭﺴﻁ ﻻ ﺘﺘﻐﻴﺭ ﻜﺜﻴﺭﹰﺍ ﻓﻲ‬

‫ﻋﻨﺩ ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ ﻻﺤﻅﻨﺎ ﺃ ‪‬‬
‫ﺠﻭﺍﺭ ‪. pH = pK A‬‬
‫ﻥ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺘﻲ ﺘﻌﻁﻲ ﺘﻐﻴﺭﺍﺕ‬
‫ﻓﺈﺫﺍ ﻜﺎﻥ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻭﺤﻴﺩ ﺍﻝﺭﺍﺠﺢ‪ ،‬ﻓﺈ ‪‬‬
‫‪ pH‬ﻫﺫﺍ ﺍﻝﻭﺴﻁ ﻤﻊ ﺤﺠﻡ ﺍﻷﺴﺎﺱ ﺍﻝﻘﻭﻱ ﺍﻝﻤﻀﺎﻑ ﻫﻲ ‪:‬‬
‫‪x‬‬
‫‪1−x‬‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻨﺘﻴﺠﺔ ﻹﻀﺎﻓﺔ ﺍﻷﺴﺎﺱ ﺍﻝﻘﻭﻱ‬
‫ﺇ‪‬‬
‫)ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ( ﻴ‪‬ﻌﻁﻰ ﺒﺎﻝﻌﻼﻗﺔ‪:‬‬
‫‪C b .Vb‬‬ ‫)‪x .C b .Vb(eqv‬‬
‫= ‪C b′‬‬ ‫=‬
‫‪Va + Vb‬‬ ‫‪Va + Vb‬‬
‫ﻥ ‪ C b′‬ﺘﺘﻐﻴﺭ ﺒﻤﻘﺩﺍﺭ ‪ ، dC b′‬ﻭﻴﺘﻐﻴﺭ ‪ pH‬ﺍﻝﻭﺴﻁ‬‫ﻋﻨﺩﻤﺎ ﺘﺘﻐﻴﺭ ‪ x‬ﺒﻤﻘﺩﺍﺭ ‪ ، dx‬ﻓﺈ ‪‬‬
‫ﺒﻤﻘﺩﺍﺭ ‪ dpH‬ﺃﻱ ‪:‬‬
‫)‪C b .Vb(eqv‬‬
‫= ‪dC b′‬‬ ‫‪⋅ dx‬‬
‫‪Va + Vb‬‬
‫‪dx‬‬
‫= ‪d pH‬‬
‫) ‪2.3 × x (1 − x‬‬
‫ﻭﻴﻜﻭﻥ‬
‫‪dC b′‬‬ ‫)‪C b .Vb(eqv‬‬
‫=‪β‬‬ ‫× ‪= 2.3‬‬ ‫) ‪× x (1 − x‬‬
‫‪dpH‬‬ ‫‪Va + Vb‬‬
‫ﻥ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﺘﺄﺨﺫ ﻗﻴﻤﺔ ﻋﻅﻤﻰ ﻋﻨﺩﻤﺎ ‪ x = 0.5‬ﺃﻱ ﻓﻲ ﺤﺎﻝﺔ‬
‫‪ ، pH = pK A‬ﻭﻫﺫﺍ ﻤﺎ ﻴﺘﻭﺍﻓﻕ ﻤﻊ ﺍﻝﻤﻼﺤﻅﺎﺕ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ‪.‬‬
‫‪ .4.II‬ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺤﻤﻀﹰﺎ ﻭﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ‬
‫ﻝﻴﻜﻥ ﻝﺩﻴﻨﺎ ﻤﺤﻠﻭل ‪ S‬ﻴﻀ ‪‬ﻡ‪:‬‬

‫ﻼ‬
‫♦ ﺤﻤﻀﹰﺎ ‪ HA‬ﻭﺃﺴﺎﺴﻪ ﺍﻝﻤﺭﺍﻓﻕ ‪ A−‬ﻭﺫﻝﻙ ﺒﺈﻀﺎﻓﺔ ﺍﻝﻤﻠﺢ ﺍﻝﻤﻭﺍﻓﻕ ﻝﻸﺴﺎﺱ‪ ،‬ﺃﻱ ﻤﺜ ﹰ‬
‫‪ K+ + A−‬ﺒﺤﻴﺙ ﻨﻜﺘﺏ ] ‪. c = [HA] + [A−‬‬
‫ﻼ ‪ HX‬ﺒﺤﻴﺙ ﻴﻜﻭﻥ ‪ [X − ] = C a‬؛‬
‫♦ ﺤﻤﻀﹰﺎ ﻗﻭﻴﺎﹰ‪ ،‬ﻤﺜ ﹰ‬
‫ﻼ ‪ MOH‬ﺒﺤﻴﺙ ﻴﻜﻭﻥ ‪. [M + ] = C b‬‬
‫♦ ﺃﺴﺎﺴﹰﺎ ﻗﻭﻴﺎﹰ‪ ،‬ﻤﺜ ﹰ‬
‫ﻤﺎ ﻫﻲ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻬﺫﺍ ﺍﻝﻤﺤﻠﻭل؟‬
‫ﻝﻺﺠﺎﺒﺔ ﻋﻥ ﻫﺫﺍ ﺍﻝﺴﺅﺍل ﻨﻜﺘﺏ ﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻝﻬﺫﺍ ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫] ‪[K+ ] + [M + ] + [H3O+ ] = [A− ] + [X − ] + [OH−‬‬
‫ﺃﻱ‬
‫‪KA ⋅ c‬‬
‫= ‪[K+ ] + C b + h‬‬ ‫‪+ Ca + ω‬‬
‫‪KA + h‬‬
‫ﻝﻨﻔﺘﺭﺽ ﺇﻀﺎﻓﺔ ﺍﻝﻘﻠﻴل ﻤﻥ ﺃﺴﺎﺱ ﻗﻭﻱ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻋﻨﺩﻫﺎ ﺘﺘﻐﻴﺭ ‪ C b‬ﺒﻤﻘﺩﺍﺭ ‪. dC b‬‬
‫ﻭﺒﺈﻫﻤﺎل ﺍﻝﺘﻤﺩﻴﺩ ﺍﻝﻨﺎﺠﻡ ﻋﻥ ﻫﺫﻩ ﺍﻹﻀﺎﻓﺔ ﻨﻜﺘﺏ‪:‬‬
‫‪K A ⋅ c ⋅ dh‬‬ ‫‪Kw‬‬
‫‪dC b = −‬‬ ‫‪− dh −‬‬ ‫‪dh‬‬
‫‪(K A + h )2‬‬ ‫‪h2‬‬
‫ﻭﺒﺎﻝﻌﻭﺩﺓ ﺇﻝﻰ ﺘﻌﺭﻴﻑ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻤﺤﻠﻭل ﻨﻜﺘﺏ‪:‬‬

‫‪dC b‬‬ ‫‪dC b dh‬‬
‫=‪β‬‬ ‫=‬ ‫⋅‬
‫‪dpH‬‬ ‫‪dh dpH‬‬
‫ﺤﻴﺙ‬
‫‪dh‬‬ ‫‪1‬‬
‫‪= −2.3 × h‬‬ ‫ﻭ‬ ‫‪pH = −‬‬ ‫‪ln h‬‬
‫‪dpH‬‬ ‫‪2.3‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻬﺫﺍ ﺍﻝﻤﺤﻠﻭل ﻤﻌﻁﺎﺓ ﺒﺎﻝﻌﻼﻗﺔ‪:‬‬
‫‪ K ⋅c ⋅h‬‬ ‫‪K ‬‬
‫‪β = 2.3 ×  A‬‬ ‫‪+ h + w ‬‬
‫‪ (K A + h )2‬‬ ‫‪h ‬‬
‫ﻥ ﺇﻀﺎﻓﺔ ﺤﻤﺽ ﻗﻭﻱ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺘﺅﺩﻱ ﺇﻝﻰ ﺘﻐﻴﻴﺭ ‪ C a‬ﺒﻤﻘﺩﺍﺭ ‪ dC a‬ﻭﺒﻤﻘﺎﺭﺒﺔ‬
‫ﺇ‪‬‬
‫ﻤﻤﺎﺜﻠﺔ ﻝﻤﺎ ﻓﻌﻠﻨﺎﻩ ﺁﻨﻔﹰﺎ‪ ،‬ﻨﺼل ﺇﻝﻰ ﺍﻝﻨﺘﻴﺠﺔ ﺫﺍﺘﻬﺎ‪.‬‬
‫ﻥ ‪ β‬ﺘﺯﺩﺍﺩ ﺒﺎﺯﺩﻴﺎﺩ ﺍﻝﺘﺭﻜﻴﺯ ‪. c‬‬

‫‪dβ‬‬
‫‪ h = K A‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ‬ ‫ﻥ‬
‫ﻤﻌﺩﻭﻤﺔ‪ .‬ﺃﻱ ﺇ ‪‬‬ ‫ﺘﺄﺨﺫ ‪ β‬ﻗﻴﻤﺔ ﻋﻅﻤﻰ ﻋﻨﺩﻤﺎ‬
‫‪dh‬‬
‫‪ ، pH = pK A‬ﺍﻝﺸﻜل )‪. (17‬‬
‫ﻝﻤﺎ ﻜﺎﻨﺕ ﻤﺤﺎﻝﻴل ﺍﻝﺤﻤﻭﺽ ﺍﻝﻘﻭﻴﺔ ﺃﻭ ﺍﻷﺴﺱ ﺍﻝﻘﻭﻴﺔ ﺘﺘﻤﺘﻊ ﺒﻘﻴﻤﺔ ‪ pH‬ﻻ ﺘﺘﻐﻴﺭ‬
‫ﻜﺜﻴﺭﹰﺍ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﺍﻝﻘﻠﻴل ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺃﻭ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪ -‬ﻓﻲ ﺤﻴﻥ ﻴﺘﻌﻠﻕ‬
‫ﻻ ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ﺃﻭ ﻤﻥ ﺃﺴﺎﺱ‬
‫ﻥ ﻤﺤﻠﻭ ﹰ‬
‫‪ pH‬ﻫﺫﻩ ﺍﻝﻤﺤﺎﻝﻴل ﺒﺸﺩﺓ ﺒﺎﻝﺘﻤﺩﻴﺩ‪ -‬ﻓﺈ ‪‬‬
‫ﻗﻭﻱ‪ ،‬ﻴﺤﻘﻕ ﺃﺤﺩ ﺸﺭﻁﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻭﻗﻲ‪ .‬ﻭﻋﻠﻴﻪ ﻓﻬﻲ ﺘﻜﻭ‪‬ﻥ ﻤﺎ ﻴ‪‬ﺴﻤ‪‬ﻰ ﻋﺎﺩﺓ ﺃﺸﺒﺎﻩ‬
‫ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‪.‬‬
‫ﻋﻨﺩﻤﺎ ﻻ ﻴﻜﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻤﻤﺩﺩﹰﺍ ﻜﺜﻴﺭﹰﺍ ﻴﻤﻜﻨﻨﺎ ﺇﻫﻤﺎل ‪ h‬ﻭ ‪ ω‬ﻓﻲ ﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل‬
‫ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻠﻤﺤﻠﻭل ﺍﻝﻤﺩﺭﻭﺱ‪:‬‬
‫‪KA ⋅ c ⋅ h‬‬
‫× ‪β = 2.3‬‬
‫‪(K A + h )2‬‬
‫‪β‬‬
‫ﺸﺒﻪ ﻤﻭﻕ ﻴﻌﻭﺩ ﺇﻝﻰ ﺍﻝﺯﻭﺝ‬ ‫ﺸﺒﻪ ﻤﻭﻕ ﻴﻌﻭﺩ ﺇﻝﻰ ﺍﻝﺯﻭﺝ‬
‫‪+‬‬
‫‪H3O /H2O‬‬ ‫‪H2O/HO−‬‬
‫‪2.3c‬‬
‫‪4‬‬ ‫ﻤﻭﻕ ﻴﻌﻭﺩ ﺇﻝﻰ ﺍﻝﺯﻭﺝ ‪HA/A−‬‬
‫‪pH‬‬
‫‪0‬‬ ‫‪pK A‬‬ ‫‪14‬‬
‫ﺍﻝﺸﻜل )‪ : (17‬ﺘﻐﻴﺭﺍﺕ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻠﻤﺯﻴﺞ ‪ HA/A−‬ﺒﺩﻻﻝﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬

‫‪ .5.II‬ﺘﻁﺒﻴﻘﺎﺕ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‬
‫ل ﻤﺭﺓ ﻨﺭﻏﺏ ﻓﻴﻬﺎ ﺍﻝﻘﻴﺎﻡ ﺒﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ ﻋﻨﺩ‬

‫ﻨﺴﺘﻌﻤل ﻓﻲ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﻜ ّ‬
‫‪ pH‬ﺜﺎﺒﺘﺔ‪ ،‬ﻭﻝﻭ ﻜﺎﻥ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻴﺴﺘﻬﻠﻙ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺃﻭ ﻴﻭﻝﹼﺩﻫﺎ‪.‬‬
‫ﻜﺫﻝﻙ ﻨﺴﺘﻌﻤل ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ﺒﺼﻔﺘﻬﺎ ﻤﺤﺎﻝﻴل ﻤﻌﻴﺎﺭﻴﺔ ﻝﻤﻌﺎﻴﺭﺓ ﺃﺠﻬﺯﺓ ﻗﻴﺎﺱ ‪pH‬‬
‫ﺍﻝﻤﺤﺎﻝﻴل‪.‬‬
‫ﻻ ﺘﻁﺒﻴﻘﻴﹰﺎ ﻴﻅﻬﺭ ﺃﻫﻤﻴﺔ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ ﻓﻲ ﺍﻝﺠﺴﻡ ﺍﻝﺒﺸﺭﻱ‪:‬‬

‫ﻭﻝﻨﺫﻜﺭ ﺍﻵﻥ ﻤﺜﺎ ﹰ‬
‫ﺇﻥ ﺤﻤﺽ ﺍﻷﺴﺘﻴل ﺴﺎﻝﻴﺴﻴﻠﻴﻙ ‪) C9 H8O4‬ﺃﻱ ﺍﻷﺴﺒﻴﺭﻴﻥ( ﻤﻌﺭﻭﻑ ﻤﻨﺫ ﺃﻜﺜﺭ ﻤﻥ ﻤﺌﺔ ﻋﺎﻡ‬
‫ل ﻤﻨﻬﺎ ‪325 mg‬‬
‫ﻥ ﺍﻝﺠﺭﻋﺔ ﺍﻝﻤﻭﺼﻰ ﺒﻬﺎ ﻤﻨﻪ ﻫﻲ ﻤﻀﻐﻭﻁﺘﺎﻥ ﺘﻀ ‪‬ﻡ ﻜ ّ‬
‫ﻋﻠﻰ ﺃﻨﻪ ﻤﺨﻔﹼﻑ ﻝﻸﻝﻡ‪ .‬ﻭﺇ ‪‬‬
‫ل ﺃﺭﺒﻊ ﺴﺎﻋﺎﺕ‪.‬‬
‫ﻭﺫﻝﻙ ﻜ ّ‬
‫ﻝﻨﺤﺴﺏ ‪ pH‬ﺍﻝﺩﻡ ﺒﻌﺩ ﺘﻨﺎﻭل ﺠﺭﻋﺔ ﻤﻥ ﺍﻷﺴﺒﻴﺭﻴﻥ ﻭﺍﻤﺘﺼﺎﺼﻬﺎ ﻜﻠﻴﹰﺎ ﻤﻥ ﻗﺒل ﺍﻝﺩﻡ ﺇﺫﺍ‬
‫ﻥ ﺤﺠﻡ ﺍﻝﺩﻡ ‪ ، 5 L‬ﻭﺃﻨﻪ ﺒﺩﺍﻴﺔ ﻻ ﻴﺴﻠﻙ ﺴﻠﻭﻙ ﻤﺤﻠﻭل ﻤﻭﻕ‪ ،‬ﻜﻤﺎ ﺃﻨﹼﻪ ﻻ ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ‬
‫ﺍﻓﺘﺭﻀﻨﺎ ﺃ ‪‬‬
‫‪. 3.5‬‬ ‫ﻥ ‪ pK A‬ﺤﻤﺽ ﺍﻝﺴﺎﻝﻴﺴﻴﻠﻴﻙ‬
‫ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ ، H3O+‬ﻭﺃ ‪‬‬
‫ﻻ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻲ ‪ c‬ﻝﺤﻤﺽ ﺍﻝﺴﺎﻝﻴﺴﻴﻠﻴﻙ ‪ HA‬ﻓﻲ ﺍﻝﺩﻡ ﺁﺨﺫﻴﻥ ﺒﺎﻻﻋﺘﺒﺎﺭ‬

‫ﻝﻨﺤﺴﺏ ﺃﻭ ﹰ‬
‫ﺍﻝﻜﺘﻠﺔ ﺍﻝﻤﻭﻝﻴﺔ ﻝﻸﺴﺒﻴﺭﻴﻥ ﻭﺤﺠﻡ ﺍﻝﺩﻡ‪:‬‬
‫‪2 × 325 × 10−3‬‬
‫=‪c‬‬ ‫‪= 7.22 × 10−4 mol / L‬‬
‫‪180 × 5‬‬
‫ﻨﺴﺘﻌﻤل ﻋﺒﺎﺭﺓ ‪ K A‬ﺍﻝﻭﺍﺭﺩﺓ ﻓﻲ ﺍﻝﻔﻘﺭﺓ ‪ 1.4.II‬ﻤﻥ ﺍﻝﻔﺼل ﺍﻝﺜﺎﻨﻲ‪:‬‬
‫‪h2‬‬
‫= ‪KA‬‬
‫‪c −h‬‬
‫ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﻨﺠﺩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪h2‬‬
‫= ‪10−3.5‬‬
‫‪7.22 × 10−4 − h‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺇﻝﻰ ﻗﻴﻤﺔ ‪ pH‬ﻗﺩﺭﻫﺎ ‪. 3.46‬‬
‫ﻴﻘﻭﺩ ﺤ ّ‬
‫ﻥ ﺍﻝﻘﻴﻤﺔ ﺍﻝﺘﻲ ﺤﺼﻠﻨﺎ ﻋﻠﻴﻬﺎ ﺃﺨﻔﺽ ﺒﻜﺜﻴﺭ ﻤﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺩﻡ ﺍﻝﺘﻲ ﻫﻲ ‪ . 7.4‬ﻝﻬﺫﺍ‬
‫ﺇ‪‬‬
‫ﺒﻐﻴﺎﺏ ﺴﻠﻭﻙ ﻤﺤﻠﻭل ﻤﻭﻕ ﻝﻠﺩﻡ ﻴﺅﺩﻱ ﺘﻨﺎﻭل ﺠﺭﻋﺔ ﺍﻷﺴﺒﻴﺭﻴﻥ ﺇﻝﻰ ﺘﻐﻴﻴﺭ ﻜﺒﻴﺭ ﻓﻲ ‪pH‬‬
‫ﺍﻝﺩﻡ ﻭﻗﺩ ﻴﻘﻭﺩ ﺫﻝﻙ ﺇﻝﻰ ﺍﻝﻤﻭﺕ‪.‬‬
‫ﻝﻨﺤﺴﺏ ﺍﻵﻥ ‪ pH‬ﺍﻝﺩﻡ ﺒﻌﺩ ﺘﻨﺎﻭل ﺠﺭﻋﺔ ﻤﻥ ﺍﻷﺴﺒﻴﺭﻴﻥ ﻭﺍﻤﺘﺼﺎﺼﻬﺎ ﻜﻠﻴﹰﺎ ﻤﻥ ﻗﺒل ﺍﻝﺩﻡ‬
‫ﻥ‬ ‫ﺇﺫﺍ ﺍﻓﺘﺭﻀﻨﺎ ﻭﺠﻭﺩ ﺍﻝﻤﻔﻌﻭل ﺍﻝﻤﻭﻗﻲ ﻓﻲ ﺍﻝﺩﻡ ﺒﻔﻀل ﺍﻝﺯﻭﺝ ‪3‬‬
‫‪ . CO2 / HCO−‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ‬
‫‪ pK A(CO2 / HCO−‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﺠﺴﻡ ﻭﺃ ‪‬‬
‫‪3 ) = 6.1‬‬
‫ﺍﻝﺒﻴﻜﺭﺒﻭﻨﺎﺕ ﻓﻲ ﺍﻝﺩﻡ ﻫﻭ ‪ 2.66 × 10−2 mol / L‬ﻭﺘﺭﻜﻴﺯ ﺜﻨﺎﺌﻲ ﺃﻭﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ‬

‫ﺍﻝﻤﻨﺤل ﺒﺎﻝﻤﺎﺀ ‪. 1.40 × 10−3 mol / L‬‬
‫‪ (CO2 / HCO−‬ﻭ ) ‪ (HA / A−‬ﻋﻠﻰ ﻤﺤﻭﺭ ‪ pH‬ﺸﺎﻗﻭﻝﻲ‪،‬‬
‫ﻨﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ ) ‪3‬‬
‫ﻭﺫﻝﻙ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ pK A‬ﻝﻜل ﻤﻨﻬﻤﺎ‪ .‬ﻜﻤﺎ ﻨﻀﻊ ﺇﻁﺎﺭﹰﺍ ﺤﻭل ﺍﻝﺠﺯﻴﺌﺎﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ‬
‫‪ HCO−‬ﻭ ‪. CO2‬‬
‫ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﺩﻡ ﺃﻱ ‪ HA‬ﻭ ‪3‬‬
‫‪pH‬‬
‫‪HCO−‬‬
‫‪3‬‬
‫‪6.1‬‬
‫‪CO2‬‬
‫‪A−‬‬ ‫‪3.5‬‬
‫‪HA‬‬
‫ﺇﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﻫﻭ‪:‬‬

‫‪HCO−‬‬ ‫‪−‬‬
‫‪3 + HA A + H2CO3‬‬ ‫‪K 0 = 10(6.1−3.5) = 102.6‬‬
‫ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻤﺒﺎﺸﺭ ﻭﺸﺒﻪ ﺘﺎﻡ‪.‬‬
‫ﻝﻨﺩﺭﺱ ﺤﺼﻴﻠﺔ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل‪:‬‬
‫‪HCO−‬‬
‫‪3‬‬ ‫‪+ HA‬‬ ‫‪ A−‬‬ ‫‪+ H2CO3‬‬
‫‪−2‬‬ ‫‪−4‬‬
‫‪t = 0 2.66 × 10‬‬ ‫‪7.22 × 10‬‬ ‫‪−‬‬ ‫‪1.4 × 10−3‬‬
‫‪teq‬‬ ‫‪2.66 × 10−2 − x‬‬ ‫‪7.22 × 10−4 − x‬‬ ‫‪x‬‬ ‫‪1.4 × 10−3 + x‬‬
‫ﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻴ‪‬ﻜﺘﺏ ﻋﻠﻰ ﺍﻝﺸﻜل‪:‬‬

‫ﺃﻱ ﺇ ‪‬‬
‫) ‪x (1.4 × 10−3 + x‬‬
‫= ‪102.6‬‬
‫) ‪(2.66 × 10−2 − x )(7.22 × 10−4 − x‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ ﺍﻝﺜﺎﻨﻴﺔ ﺒﺈﻴﺠﺎﺩ ‪x = 7.2185 × 10−4 mol / L‬‬
‫ﻭﻴﺴﻤﺢ ﺤ ّ‬
‫ﻭﻴﻤﻜﻥ ﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺩﻡ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺄﺤﺩ ﺍﻝﺯﻭﺠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪ ،‬ﻜﺄﻥ ﻨﺄﺨﺫ ﺍﻝﺯﻭﺝ‬
‫ﻼ‪:‬‬
‫‪ (CO2 / HCO−‬ﻤﺜ ﹰ‬
‫)‪3‬‬
‫‪[HCO−‬‬
‫]‪3‬‬
‫‪pH = p K A (CO2 /‬‬ ‫‪HCO−‬‬
‫)‪3‬‬ ‫‪+ log‬‬ ‫‪= 7.19‬‬
‫] ‪[CO2‬‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻓﻲ ﺍﻝﺩﻡ ﻗﺩ ﺍﻨﺨﻔﺽ ﻜﺜﻴﺭﹰﺍ ﺒﻭﺠﻭﺩ ﺍﻝﺯﻭﺝ‬
‫ﻨﻼﺤﻅ ﻫﻨﺎ ﺃ ‪‬‬
‫ﺍﻝﻤﻭﻗﻲ ﺒﺤﻭﺍﻝﻲ ﻋﺸﺭﺓ ﺁﻻﻑ ﻤﺭﺓ ﻋﻤﺎ ﻜﺎﻥ ﻋﻠﻴﻪ ﺍﻝﺤﺎل ﻓﻲ ﻏﻴﺎﺒﻪ‪.‬‬
‫ﻤﺎﺯﺍﻝﺕ ﻁﺒﻌﹰﺎ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺩﻡ ﺃﻗل ﺒﻘﻠﻴل ﻤﻥ ﺍﻝﻘﻴﻤﺔ ﺍﻝﻁﺒﻴﻌﻴﺔ ﻝﻬﺎ‪ .‬ﻭﻝﻜﻨﻨﺎ ﻨﺫﻜﹼﺭ ﺒﻭﺠﻭﺩ‬
‫‪ H2 PO−‬ﻭﻜﺫﻝﻙ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻷﺨﺭﻯ ﺍﻝﻤﻜﻭ‪‬ﻨﺔ ﻝﻠﺩﻡ ﺒﻭﺼﻔﻪ‬ ‫‪2−‬‬
‫‪4 / HPO4‬‬ ‫ﺯﻭﺝ ﻤﻭﻕ ﺁﺨﺭ ﻫﻭ‬
‫ﻭﺴﻁﹰﺎ ﺤﻴﻭﻴﹰﺎ ﻤﻤﺎ ﻴﺴﻬ‪‬ل ﺘﻌﺩﻴل ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﺩﻡ ﻭﺇﻋﺎﺩﺘﻬﺎ ﺇﻝﻰ ﻗﻴﻤﺘﻬﺎ ﺍﻝﻁﺒﻴﻌﻴﺔ ‪. 7.4‬‬
‫‬
‫ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ‬ ‫‬
‫ﻨﻌﺎﻴﺭ ‪ V1 = 20.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﻤﻴﺜﻴل ﺃﻤﻴﻥ ﺒﺘﺭﻜﻴﺯ ‪C 1 = 0.100 mol/L‬‬
‫ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﻤﻥ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺒﺘﺭﻜﻴﺯ ‪.C 2 = 0.200 mol/L‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺍﻝﺤﺠﻡ ‪ V2E‬ﻤﻥ ﺍﻝﺤﻤﺽ ﺍﻝﻼﺯﻡ ﺇﻀﺎﻓﺘﻪ ﻝﻠﻭﺼﻭل ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫‪ .2‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩﻤﺎ ‪ V2 = 0‬ﻭ ‪.V2 = V2E‬‬
‫ﻥ ‪ . x = V2 /V2E‬ﺍﻜﺘﺏ ﻋﺒﺎ ﺭ ﺍﺕ ) ‪ pH = f (x‬ﻋﻨﺩﻤﺎ‪:‬‬
‫‪ .3‬ﺒﻔﺭﺽ ﺃ ‪‬‬
‫‪ 0 < x < 1‬ﻭ ‪. 1 < x < 1.5‬‬
‫‪ .4‬ﺍﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ pH = f (x‬ﻋﻨﺩﻤﺎ ‪. 0 < x < 1.5‬‬
‫ﻭ ‪x = 0.50‬‬ ‫ﻕ ﻋﻨﺩﻤﺎ ‪x = 0.40‬‬
‫‪ .5‬ﺍﺤﺴﺏ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻤﺤﻠﻭل ﻤﻭ ‪‬‬
‫ﻭ ‪ . x = 0.60‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪. pK A(CH 3 NH+‬‬
‫) ‪3 /CH 3 NH2‬‬ ‫‪= 10.70‬‬
‫ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﻭﻗﻴﺔ‬ ‫‬

‫‪ .1‬ﺤ ‪‬ﺩ ﺩ ﺍ ﻝﺤﺠﻡ ‪ V‬ﺍ ﻝﻼﺯ ﻡ ﺇﻀﺎ ﻓﺘﻪ ﻤﻥ ﺍ ﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ ‪ 0.50 mol/L‬ﺇ ﻝﻰ ﺍ ﻝﺤﺠﻡ‬
‫‪ V0 = 30 mL‬ﻤﻥ ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ ﺒﺘﺭﻜﻴﺯ ‪ 0.10 mol/L‬ﻭﺫﻝﻙ ﻝﻠﻭﺼﻭل ﺇﻝﻰ‬
‫ﻕ ﻝﻪ ‪ pH = 7.5‬ﻭ ‪. pH = 6.9‬‬
‫ﻤﺤﻠﻭل ﻤﻭ ‪‬‬
‫‪ .2‬ﺍﺤﺴﺏ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻬﺫﻴﻥ ﺍﻝﻤﺤﻠﻭﻝﻴﻥ‪.‬‬
‫ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ‪. pK A3 = 12.1 ، pK A2 = 7.2 ، pK A1 = 2.15 :‬‬
‫ﻨﻤﺫﺠﺔ ﻤﻌﺎﻴﺭﺓ ﺍﻝﺤﻤﺽ ﺍﻷﻭﺭﺘﻭ‪-‬ﻓﺘﺎﻝﻴﻙ‬ ‫‬

‫‪ C8 H6O4‬ﺤﻤﻀﹰﺎ ﻤﻀﺎﻋﻔﹰﺎ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ‪ ،‬ﺴﻨﺴﻤﻴﻪ‬ ‫ﻴﻌﺘﺒﺭ ﺍﻝﺤﻤﺽ ﺍﻷﻭﺭﺘﻭ‪-‬ﻓﺘﺎﻝﻴﻙ‬
‫‪ H2A‬ﻓﻴﻤﺎ ﻴﻠﻲ‪ .‬ﻨﻌﺎﻴﺭ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ ‪ 0.050 mol/L‬ﺤﺠﻤﹰﺎ ﻗﺩﺭﻩ‬
‫‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻝﻬﺫﺍ ﺍﻝﺤﻤﺽ‪ .‬ﻴﻤﺜﹼل ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﺘﺎﻝﻲ ﻨﻤﺫﺠﺔ ﻝﻬﺫﻩ ﺍﻝﻤﻌﺎﻴﺭﺓ‪:‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺍﻝﺤﺠﻭﻡ ﺍﻝﻼﺯﻤﺔ ﻝﻠﻭﺼﻭل ﺇﻝﻰ ﻨﻘﻁﺘﻲ ﺍﻝﺘﻜﺎﻓﺅ‪ ،‬ﻭﺍﺴﺘﻨﺘﺞ ﻤﻨﻬﺎ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻲ‬
‫ﻝﻠﻤﺤﻠﻭل ﺍﻝﻤﻌﺎﻴ‪‬ﺭ‪.‬‬
‫‪ .2‬ﺍﺤﺴﺏ ﻗﻴﻤﺘﻲ ‪ pK A‬ﻝﺤﻤﺽ ﺍﻷﻭﺭﺘﻭ‪-‬ﻓﺘﺎﻝﻴﻙ‪.‬‬
‫‪ .3‬ﺃﻭﺠﺩ ﺒﺎﻝﺤﺴﺎﺏ ﻗﻴﻡ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﻭﺘﻠﻙ ﺍﻝﺘﻲ ﻴﺼل ﺇﻝﻴﻬﺎ ﺒﻌﺩ ﺇﻀﺎﻓﺔ‬
‫‪ 3 mL‬ﻭ ‪ 12 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ‪.‬‬
‫‪ .4‬ﻋﻠﹼل ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﻘﺭﻭﺀﺓ ﻋﻠﻰ ﺍﻝﻤﻨﺤﻨﻲ ﻋﻨﺩﻤﺎ ‪. v = 6 mL‬‬
‫‪pH‬‬ ‫‪%‬‬
‫‪100‬‬
‫‪14‬‬
‫‪12‬‬ ‫‪80‬‬
‫‪10‬‬
‫‪60‬‬
‫‪8‬‬
‫‪6‬‬ ‫‪40‬‬
‫‪4‬‬
‫‪20‬‬
‫‪2‬‬
‫)‪V (mL‬‬
‫‪15‬‬
‫‪3‬‬ ‫‪6‬‬ ‫‪9‬‬ ‫‪12‬‬ ‫‪15‬‬
‫ﻤﻌﺎﻴﺭﺓ ﻤﺯﻴﺞ ﻤﻥ ﺤﻤﻀﻴﻥ‬ ‫‬

‫‪ .1‬ﻨﻤﺯ ﺝ ‪ 20.0 mL‬ﻤﻥ ﺤﻤﺽ ﺍ ﻝﺨل ﺒﺘﺭﻜﻴﺯ ‪ 0.010 mol/L‬ﻭ ‪ 20.0 mL‬ﻤﻥ‬
‫ﺤﻤﺽ ﺍﻝﺒﻭﺭ ‪ HBO2‬ﺒﺎﻝﺘﺭﻜﻴﺯ ﻨﻔﺴﻪ‪ .‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺯﻴﺞ‪.‬‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ﻫﺫﺍ ﺍﻝﻤﺯﻴﺞ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺍﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ ‪ . 0.040 mol/L‬ﺃﻭﺠﺩ ﺍﻝﻤﻨﺤﻨﻲ‬
‫) ‪ pH = f (V‬ﺤﻴﺙ ‪ V‬ﻫﻭ ﺤﺠﻡ ﺍﻝﺼﻭﺩ ﺍﻝﻤﻀﺎﻑ ﻭﻴﻘﻊ ﺒﻴﻥ ‪ 0‬ﻭ ‪. 15 mL‬‬
‫‪ .3‬ﺍﺤﺴﺏ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻠﻤﺯﺍﺌﺞ ﺍﻝﺘﻲ ﻨﺤﺼل ﻋﻠﻴﻬﺎ ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ‪V = 2.5 mL :‬‬
‫ﻭ ‪ .V = 7.5 mL‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫‪. pK A (HBO2/BO−‬‬ ‫‪−‬‬
‫‪2 ) = 9.2 pK A (CH 3COOH/CH 3COO ) = 4.7‬‬
‫ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﻤﻥ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺒﺭﻴﺕ‬ ‫‬

‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻝﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺒﺭﻴﺕ ﻨﺭﻤﺯ ﻝﻪ ﺒﺎﻝﺭﻤﺯ ‪ . H2SO3‬ﺘﺠـﺭﻱ ﻤﻌـﺎﻴﺭﺓ‬
‫ﻨﻌﺎﻴﺭ ﻤﺤﻠﻭ ﹰ‬
‫‪ 10.0 mL‬ﻤﻥ ﺍﻝﻤﺤﻠﻭل ﺒﻭﺠﻭﺩ ﺍﻝﻔﻴﻨﻭل ﻓﺘﺎﻝﺌﻴﻥ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠـﻭل ﺍﻝﺼـﻭﺩ ﺒﺘﺭﻜﻴـﺯ‬
‫‪ . 1.0 × 10−2 mol/L‬ﻴﺴﺎﻭﻱ ﺤﺠﻡ ﺍﻝﺼﻭﺩ ﺍﻝﻼﺯﻡ ﺤﺘﻰ ﻴﺘﻐﻴﺭ ﻝﻭﻥ ﺍﻝﻤﺸﻌﺭ ﺍﻝﻠـﻭﻨﻲ‬
‫‪. 20.0 mL‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺯ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻌﺎﻴ‪‬ﺭ ﻭﻜﺫﻝﻙ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻻﺒﺘﺩﺍﺌﻲ؟‬
‫‪ .2‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺤﺠﻡ ﺍﻝﺼﻭﺩ ﺍﻝﻤﻀﺎﻑ ‪، 20 ، 15 ، 10 ، 5‬‬
‫‪ . 25 mL‬ﺍﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ) ‪. pH = f (V‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ ‪. pK A2 = 7.6 ، pK A1 = 2.2 : H2SO3‬‬
‫ﻤﺤﻠﻭل ﻤﻭﻕ ﻤﻥ ﺍﻝﺒﻭﺭﺍﻜﺱ‬ ‫‬

‫ل ﺍﻝﺒﻭﺭﺍﻜﺱ ﻓﻲ ﺍﻝﻤﺎﺀ ‪ Na 2 B4O7‬ﻓﺈﻨﻪ ﻴﺘﺸﺭ‪‬ﺩ ﻤﻌﻁﻴﹰﺎ ﺸﻭﺍﺭﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫ﻋﻨﺩﻤﺎ ﻴﻨﺤ ّ‬
‫‪ HBO2/BO−‬ﻫﻲ ‪. 9.2‬‬
‫ﻥ ‪ pK A‬ﺍﻝﺯﻭﺝ ‪2‬‬
‫‪ BO−‬ﻭ ‪ . HBO2‬ﺇ ‪‬‬
‫‪ Na‬ﻭ ‪2‬‬
‫‪+‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﺎﺀ ﻤﻊ ﺍﻝﺒﻭﺭﺍﻜﺱ؟‬

‫‪ .2‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻋﻥ ﺍﻨﺤﻼل ‪ 0.010 mol‬ﻤﻥ ﺍﻝﺒﻭﺭﺍﻜﺱ ﻓﻲ‬
‫‪ 1.00 L‬ﻤﻥ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .3‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺘﻲ ﻨﺤﺼل ﻋﻠﻴﻬﺎ ﻋﻨﺩﻤﺎ ﻨﻀﻴﻑ ﺇﻝﻰ ‪ 100 mL‬ﻤﻥ‬
‫ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ‪:‬‬
‫‪ 0.20 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ ‪ 1.00 mol/L‬؛‬ ‫‬
‫‪ 0.10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺒﺘﺭﻜﻴﺯ ‪. 1.00 mol/L‬‬ ‫‬
‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺍﻝﺴﻜﺴﻴﻨﻴﻙ‬ ‫‬

‫ﻴﻌﺘﺒﺭ ﺤﻤﺽ ﺍﻝﺴﻜﺴﻴﻨﻴﻙ ‪ HOOC-CH2 -CH2 -COOH‬ﺤﻤﻀﹰﺎ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ‬
‫ﻨﺭﻤﺯ ﻝﻪ ﺒﺎﻝﺭﻤﺯ ‪ . H2A‬ﻭﻝﻪ ﺜﺎﺒﺘﺎ ﺤﻤﻭﻀﺔ ‪. pK A2 = 5.6 ، pK A1 = 4.2‬‬
‫ﻼ‬
‫‪ .1‬ﻨﻘﺒل ﺃﻨﻪ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻌﺎﻴﺭ ﻋﻠﻰ ﻨﺤﻭ ﻤﻨﻔﺼل ) ﺃﻱ ﻋﻠﻰ ﺍﻝﺘﺘﺎﻝﻲ ﻭﺒﺼﻭﺭﺓ ﻤﺴﺘﻘﻠﺔ( ﻜ ﹰ‬
‫ﻤﻥ ﺍﻝﻭﻅﻴﻔﺘﻴﻥ ﺍﻝﺤﻤﻀﻴﺘﻴﻥ ﻝﻠﺤﻤﺽ ‪ ، H2A‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﻨﻌﺎﻴﺭ ‪ 99%‬ﻤﻥ ‪H2A‬‬
‫ل ﻤﻥ ‪ 1%‬ﻤﻥ ‪ HA−‬ﻭﺫﻝﻙ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ ﺍﻷﻭل‪.‬‬
‫ﻭﺃﻗ ّ‬
‫‪ (a‬ﺤﺩ‪‬ﺩ ﺍﻝﺸﺭﻁ ﺍﻝﺫﻱ ﻴﺠﺏ ﺃﻥ ﻴﺤﻘﹼﻘﻪ ‪ ∆pK A‬ﻝﻴﺘ ‪‬ﻡ ﺫﻝﻙ‪.‬‬

‫‪ (b‬ﺤ ‪‬ﺩ ﺩ ﻋﺩ ﺩ ﻗﻔﺯ ﺍﺕ ‪ pH‬ﺍ ﻝﻤﺤﻠﻭ ل ﺍ ﻝﺘﻲ ﺴﺘﻅﻬﺭ ﻓﻲ ﺍ ﻝﻤﻨﺤﻨﻲ ) ‪ pH = f (V‬ﻋﻨﺩ‬
‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺍﻝﺴﻜﺴﻴﻨﻴﻙ ﺒﺄﺴﺎﺱ ﻗﻭﻱ ﻤﻊ ﺍﻝﺘﻌﻠﻴل‪.‬‬
‫‪ .2‬ﻨﻌﺎ ﻴﺭ ﺤﺠﻤ ﹰﺎ ﻤﻘﺩ ﺍ ﺭ ﻩ ‪ V0 = 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﺤﻤﺽ ﺍ ﻝﺴﻜﺴﻴﻨﻴﻙ ‪ ،‬ﺘﺭ ﻜﻴﺯﻩ‬
‫‪ ، C 0 = 0.10 mol/L‬ﻭﺫﻝﻙ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﻤﺭ ﻜﹼﺯ ﻤﻥ ﺍﻝﺼﻭﺩ ) ﺒﺘﺭﻜﻴﺯ ‪C‬‬
‫ﻭﺤﺠﻡ ﻤﻀﺎﻑ ‪ .(V‬ﻨﻜﺘﺏ ‪ x = C .V / C 0 .V0‬ﻭﻨﻬﻤل ﺍﻝﺘﻤﺩﻴﺩ‪.‬‬
‫‪ (a‬ﻋﻨﺩﻤﺎ ‪ x = 0‬ﻭ ‪ x = 2‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ (b‬ﻋﻨﺩﻤﺎ ‪ 0 < x < 2‬ﻭﺒﺈﻫﻤﺎل ﺸﻭﺍﺭﺩ ﺍﻝﻤﺎﺀ‪ ،‬ﺃﺜﺒﺕ ﺼﺤﺔ ﺍﻝﻌﻼﻗﺔ‪:‬‬
‫‪2K A ⋅ K A + K A ⋅ h‬‬
‫= )‪x = f (pH‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪1‬‬
‫‪KA ⋅ KA + KA ⋅ h + h 2‬‬
‫‪1‬‬ ‫‪2‬‬ ‫‪1‬‬
‫ﺤﻴﺙ ] ‪. h = [H 3O+‬‬
‫ﺍﺤﺴﺏ ‪ x‬ﻋﻨﺩﻤﺎ ‪. 7.5 ،...، 4 ، 3.5 ، 3 = pH‬‬
‫ﻥ ﻓﺎﺌﺽ ﺍﻝﺼﻭﺩ ﺴﻴﻔﺭﺽ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪ .‬ﻭﺍﺤﺴﺏ ‪pH‬‬
‫‪ (c‬ﻋﻨﺩﻤﺎ ‪ x > 2‬ﻋﻠﹼل ﺃ ‪‬‬
‫ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩﻤﺎ ‪ 2.5 ، 2.3 ، 2.1 ، 2.01 = x‬ﻭ ‪. 3‬‬
‫‪ (d‬ﺍﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ ، pH = f (x‬ﻤﺎﺫﺍ ﺘﻼﺤﻅ؟‬
‫ﺩﺭﺍﺴﺔ ﺍﻝﺤﻤﺽ ﺍﻷﻤﻴﻨﻲ‪ :‬ﺍﻝﻐﻠﻴﺴﻴﻥ‬ ‫‬

‫ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪ ،‬ﻋﻨﺩ ‪ ، pH = 6‬ﻴﺄﺨﺫ ﺍﻝﻐﻠﻴﺴﻴﻥ ﺍﻝﺼﻴﻐﺔ‪:‬‬
‫‪H3 N+ − CH2 − COO−‬‬
‫ﻱ ﻤﻨﻬﺎ ﺘﻌﻭﺩ ﻗﻴﻡ‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ ﻝﻠﻐﻠﻴﺴﻴﻥ ﻓﻲ ﺍﻝﻤﺎﺀ ﻭﺤﺩ‪‬ﺩ ﺇﻝﻰ ﺃ ‪‬‬
‫‪ pK A = 2.34 : pK A‬ﻭ ‪. pK A = 9.60‬‬
‫‪2‬‬ ‫‪1‬‬
‫ل ‪ 1.50 g‬ﻤﻥ ﺍﻝﻐﻠﻴﺴﻴﻥ ﻓﻲ ‪ 100.0 mL‬ﺍﻝﻤﺎﺀ‪ ،‬ﻓﻨﺤﺼل ﻋﻠﻰ ﺍﻝﻤﺤﻠﻭل ‪. A‬‬

‫‪ .2‬ﻨﺤ ّ‬
‫ﺍﻜﺘﺏ ﺍﻝﺸﻜل ﺃﻭ ﺍﻷﺸﻜﺎل ﺍﻝﺭﺍﺠﺤﺔ ﻤﻥ ﺍﻝﻐﻠﻴﺴﻴﻥ ﻓﻲ ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﺍﺤﺴﺏ ‪pH‬‬
‫ﺍﻝﻤﺤﻠﻭل ‪. A‬‬
‫‪ HCOO − CH2 − NH+‬ﻓﻲ‬
‫ل ‪ 2.23 g‬ﻤﻥ ﻜﻠﻭﺭﻫﻴﺩﺭﺍﺕ ﺍﻝﻐﻠﻴﺴﻴﻥ ‪3 Cl‬‬
‫‪−‬‬
‫‪ .3‬ﻨﺤ ّ‬
‫‪ 100.0 mL‬ﺍﻝﻤﺎﺀ‪ ،‬ﻓﻨﺤﺼل ﻋﻠﻰ ﺍﻝﻤﺤﻠﻭل ‪ . B‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ‪. B‬‬
‫‪ .4‬ﻨﻤﺯ ﺝ ﺍ ﻝﻤﺤﻠﻭ ﻝﻴﻥ ﺍ ﻝﺴﺎ ﺒﻘﻴﻥ ‪ A‬ﻭ ‪ B‬ﻓﻨﺤﺼل ﻋﻠﻰ ﺍ ﻝﻤﺤﻠﻭ ل ‪ .C‬ﺍ ﺤﺴﺏ ‪pH‬‬
‫ﺍﻝﻤﺤﻠﻭل ‪.C‬‬
‫ﻻ ﻤﻥ ﺸﻭ ﺍ ﺭﺩ‬
‫‪ .5‬ﻨﺩ ﺨل ﺇ ﻝﻰ ﺍ ﻝﻤﺤﻠﻭ ل ‪ C‬ﻭ ﺩ ﻭ ﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍ ﻝﺤﺠﻡ ‪ 5 ⋅ 10−3‬ﻤﻭ ﹰ‬
‫ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ . H3O+‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺒﻌﺩ ﺘﻠﻙ ﺍﻹﻀﺎﻓﺔ‪ .‬ﻋﻠﹼﻕ ﻋﻠﻰ ﻫﺫﻩ‬
‫ﺍﻝﻨﺘﻴﺠﺔ‪ ،‬ﻭﺍﺤﺴﺏ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﻭﻗﻴﺔ ﻝﻠﻤﺤﻠﻭل ‪.C‬‬
‫‪ .6‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ‪ C‬ﻤﻥ ﺍﻝﺴﺅﺍل ‪ .4‬ﺤﺠﻤﹰﺎ ﻗﺩﺭﻩ ‪ 4.0 mL‬ﻤﻥ ﺍﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ‬
‫‪ 10.0 mol/L‬ﻝﻠﻭﺼﻭل ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ‪. D‬‬
‫‪ (a‬ﺍﻜﺘﺏ ﺍﻝﺸﻜل ﺃﻭ ﺍﻷﺸﻜﺎل ﺍﻝﺭﺍﺠﺤﺔ ﻤﻥ ﺍﻝﻐﻠﻴﺴﻴﻥ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ‪ . D‬ﺍﺤﺴﺏ ‪pH‬‬
‫ﺍﻝﻤﺤﻠﻭل ‪. D‬‬
‫‪ (b‬ﺃَﻝﻬﺫﺍ ﺍﻝﻤﺤﻠﻭل ﺨﺼﺎﺌﺹ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻭﻗﻲ؟ ﻭﺇﺫﺍ ﻜﺎﻥ ﺍﻝﺠﻭﺍﺏ ﻨﻌﻡ‪ ،‬ﻓﺎﺤﺴﺏ ﻗﺩﺭﺘﻪ‬
‫ﺍﻝﻤﻭﻗﻴﺔ‪.‬‬
‫‪ .7‬ﺍﺤﺴﺏ ﺤﺠﻡ ﺍﻝﺼﻭﺩ ﺒﺘﺭﻜﻴﺯ ‪ 10.0 mol/L‬ﺍﻝﺫﻱ ﻴﻨﺒﻐﻲ ﺇﻀﺎﻓﺘﻪ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ‪A‬‬
‫ﺤﺘﻰ ﻨﺼل ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ .‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﻬﺎﺌﻲ‪.‬‬
‫ﺍﻨﺤﻼﻝﻴﺔ ﺍﻷﻭﻜﺴﻴﻥ‬ ‫ ‬
‫ﻴﺴﺎﻫﻡ ﻫﻴﺩﺭﻭﻜﺴﻲ‪-8-‬ﻜﻴﻨﻭﻝﻴﻥ ﺃﻭ ﺍﻷﻭﻜﺴﻴﻥ ‪ HOx‬ﻓﻲ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﻤﻀﻴﺔ‪-‬ﺍﻷﺴﺎﺴﻴﺔ‬
‫‪H2Ox + + H2O HOx + H 3O+‬‬ ‫‪pK A = 5.0‬‬
‫‪1‬‬
‫‪HOx + H2O Ox − + H 3O+‬‬ ‫‪pK A = 9.8‬‬

‫‪2‬‬
‫ﻥ ﻗﻴﻤﺔ ﺍﻻﻨﺤﻼﻝﻴﺔ‬
‫ﺇﻥ ﺍﻝﺸﻜل ﺍﻝﻤﻌﺘﺩل ‪ HOx‬ﻗﻠﻴل ﺍﻻﻨﺤﻼل ﻓﻲ ﺍﻝﻤﺎﺀ ﺤﻴﺙ ﺇ ‪‬‬
‫‪ . s 0 = 1.0 × 10−3 mol/L‬ﻋﻨﺩ ﺤﺴﺎﺒﻨﺎ ﻝﻘﻴﻡ ‪ pH‬ﻤﺤﻠﻭل‪ ،‬ﻨﻌﺘﺒﺭ ﻨﻭﻋﹰﺎ ﻜﻴﻤﻴﺎﺌﻴ ﹰﺎ‬
‫ﻼ ﺃﻤﺎﻡ ﻨﻭﻉ ﺁﺨﺭ ﺇﺫﺍ ﻜﺎﻥ ﺘﺭﻜﻴﺯﻩ ﺃﻗل ﺒﻌﺸﺭ ﻤﺭﺍﺕ ﻤﻥ ﺘﺭﻜﻴﺯ ﺍﻝﻨﻭﻉ ﺍﻵﺨﺭ‪ .‬ﻭﻨﺴﻤﻲ‬
‫ﻤﻬﻤ ﹰ‬
‫ﺍﻻﻨﺤﻼﻝﻴﺔ ﺍﻝﻅﺎﻫﺭﻴﺔ ﻜﻤﻴﺔ ﺍﻷﻭﻜﺴﻴﻥ ﺍﻝﻜﻠﻴﺔ ﺍﻝﺘﻲ ﻴﻜﻭﻥ ﻓﻴﻬﺎ ﺍﻷﻭﻜﺴﻴﻥ ﺘﺤﺕ ﺃﻱ ﺸﻜل ﻤﻥ‬
‫ﻼ ﻓﻲ ‪ 1.00 L‬ﻤﻥ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﺃﺸﻜﺎﻝﻪ ﻤﻨﺤ ﹰ‬
‫‪ .1‬ﺍ ﻜﺘﺏ ﻋﺒﺎ ﺭ ﺓ ﺍ ﻻ ﻨﺤﻼ ﻝﻴﺔ ﺍ ﻝﻅﺎ ﻫﺭ ﻴﺔ ﻝﻸ ﻭ ﻜﺴﻴﻥ ‪ s‬ﺒﺩ ﻻ ﻝﺔ ‪ ) h‬ﺘﺭ ﻜﻴﺯ ﺸﻭ ﺍ ﺭﺩ‬
‫‪.( H3O+‬‬
‫‪ .2‬ﺍﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ )‪ log s = f (pH‬ﻤﻊ ﺇﻅﻬﺎﺭ ﻤﺨﺘﻠﻑ ﺍﻝﻤﻘﺎﺭﺒﺎﺕ‪.‬‬
‫ﻻ ﻤﻥ‬
‫ل ﻓﻲ ‪ 1.00 L‬ﻤﻥ ﺍ ﻝﻤﺎ ﺀ ﻭ ﺘﺤﺕ ﺍ ﻝﺘﺤﺭ ﻴﻙ ﺍ ﻝﻤﺴﺘﻤﺭ ‪ 8.0 × 10−4‬ﻤﻭ ﹰ‬
‫‪ .3‬ﻨﺤ ّ‬
‫ﺍﻷﻭﻜﺴﻴﻥ‪ ،‬ﻓﻨﺤﺼل ﻋﻠﻰ ﺍﻝﻤﺤﻠﻭل ‪. A‬‬
‫‪ (a‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ‪ A‬؟‬
‫ﻻ ﻤﻥ ﺍﻝﺼﻭﺩ‪ ،‬ﺍﺤﺴﺏ‬
‫‪ (b‬ﻨﻀﻴﻑ ﻭﻤﻥ ﺩﻭﻥ ﺃﻱ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍﻝﺤﺠﻡ ‪ 8.0 × 10−4‬ﻤﻭ ﹰ‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل ‪ B‬ﺍﻝﻨﺎﺘﺞ‪.‬‬
‫‪ .6‬ﻨﻌﻭ ﺩ ﺜﺎ ﻨﻴﺔ ﺇ ﻝﻰ ﺍ ﻝﻤﺤﻠﻭ ل ‪ A‬ﻭ ﻨﻀﻴﻑ ﺇ ﻝﻴﻪ ﻤﻥ ﺩ ﻭ ﻥ ﺃ ﻱ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍ ﻝﺤﺠﻡ‬
‫ﻻ ﻤﻥ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﻓﻨﺤﺼل ﻋﻠﻰ ﺍﻝﻤﺤﻠﻭل ‪ C‬ﺍﻝﺫﻱ ﻨﻘﻭﻡ‬
‫‪ 8.0 × 10−4‬ﻤﻭ ﹰ‬
‫ﺒﻤﻌﺎﻴﺭﺘﻪ ﺒﻤﺤﻠﻭل ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺍﻝﻤﺭﻜﺯ‪.‬‬
‫ﻝﺘﻜﻥ ‪ ) = x‬ﻜﻤﻴﺔ ﺍﻝﺼﻭﺩ ﺍﻝﻤﻀﺎﻓﺔ(‪ )/‬ﺍﻝﻜﻤﻴﺔ ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﻤﻥ ﺍﻷﻭﻜﺴﻴﻥ(‪ .‬ﺍﺭﺴﻡ‬
‫ﺍﻝﻤﻨﺤﻨﻲ ) ‪ pH = f (x‬ﻭﺤﺩ‪‬ﺩ ﻋﻠﻴﻬﺎ ﻗﻴﻡ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ‪، 0 = x‬‬
‫‪. 2 ، 1.5 ، 1 ، 0.5‬‬
‫ﻁﺭﻴﻘﺔ ﻏﺭﺍﻥ‬ ‫
‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻤﻥ ﺤﻤﺽ ﻀﻌﻴﻑ ‪ HA‬ﺒﺘﺭﻜﻴﺯ ‪ C a‬ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‬
‫ﻨﻌﺎﻴﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﺒﺘﺭﻜﻴﺯ ‪ .C b‬ﻝﺘﺤﻘﻴﻕ ﺫﻝﻙ ﻨﻀﻴﻑ ﺍﻝﺤﺠﻡ ‪ V‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ ﺇﻝﻰ ﺍﻝﺤﺠﻡ ‪ V0‬ﻤﻥ‬
‫ﺍﻝﻤﺤﻠﻭل ﺍﻝﺤﻤﻀﻲ‪ .‬ﻓﻴﻤﺎ ﻴﻠﻲ ﻝﻥ ﻨﻬﻤل ﺍﻝﺘﻤﺩﻴﺩ ﻭﺴﻨﻬﺘﻡ ﺒﺩﺭﺍﺴﺔ ﺠﺯﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻗﺒل ﻨﻘﻁﺔ‬
‫ﺍﻝﺘﻜﺎﻓﺅ ﺍﻝﺘﻲ ﻨﺼل ﺇﻝﻴﻬﺎ ﻋﻨﺩ ﺤﺠﻡ ‪ Ve‬ﻤﻥ ﺍﻝﺼﻭﺩ‪.‬‬
‫‪ .1‬ﺍﺴﺘﺨﺭﺝ ﺍﻝﻌﻼﻗﺔ ) ‪ h ⋅ V = K A ⋅ (V − Ve‬ﻤﻊ ﺘﺤﺩﻴﺩ ﺍﻝﺘﻘﺭﻴﺒﺎﺕ ﺍﻝﺘﻲ ﻗﻤﺕ ﺒﻬﺎ‪.‬‬
‫ﻼ ﻫﻨﺩﺴﻴﹰﺎ ﻴﺴﻤﺢ ﺒﺘﺤﺩﻴﺩ ‪ Ve‬ﻭ ‪ K A‬؟‬
‫‪ .2‬ﺍﻗﺘﺭﺡ ﺘﻤﺜﻴ ﹰ‬
‫‪ .3‬ﻨﻌﺎﻴﺭ ‪ 50 mL‬ﻤﻥ ﺤﻤﺽ ﺍﻝﺨل ﺒﻤﺤﻠﻭل ﺘﺭﻜﻴﺯﻩ ‪C b = 1.0 × 10−2 mol/L‬‬
‫ﻤﻥ ﺍﻝﺼﻭﺩ‪ .‬ﻓﻨﺤﺼل ﻋﻠﻰ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫)‪V (mL‬‬ ‫‪3‬‬ ‫‪9‬‬ ‫‪11‬‬ ‫‪15‬‬ ‫‪19‬‬ ‫‪23‬‬ ‫‪27‬‬

‫‪pH‬‬ ‫‪3.95‬‬ ‫‪4.49‬‬ ‫‪4.63‬‬ ‫‪4.92‬‬ ‫‪5.26‬‬ ‫‪5.87‬‬ ‫‪10.22‬‬
‫ل ‪.C a‬‬
‫‪ (a‬ﺤﺩ‪‬ﺩ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺭﺴﻡ ﺤﺠﻡ ﺍﻝﺘﻜﺎﻓﺅ ‪ ،Ve‬ﺜ ‪‬ﻡ ﺍﺴﺘﻨﺘﺞ ﺘﺭﻜﻴﺯ ﺤﻤﺽ ﺍﻝﺨ ّ‬
‫ل‪.‬‬
‫‪ (b‬ﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ‪ K A‬ﻝﺤﻤﺽ ﺍﻝﺨ ّ‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ‬
‫
‬
‫

‬
‫‪ .I‬ﺘﻤﻬﻴﺩ‬
‫‪ .1.I‬ﻤﺸﺎﻫﺩﺍﺕ ﺘﺠﺭﻴﺒﻴﺔ‬
‫‪ .2.I‬ﺘﻌﺎﺭﻴﻑ‬
‫‪ .3.I‬ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‬
‫‪ .II‬ﺜﻭﺍﺒﺕ ﻤﻤﻴ‪‬ﺯﺓ ﻝﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‬
‫‪ .III‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ‬
‫‪ .IV‬ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﺍﻝﻤﺘﻨﺎﻓﺴﺔ‬
‫‪ .1.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺭﺒﻴﻁﺘﻴﻥ‪ L ′ :‬ﻭ ‪L‬‬
‫‪ .2.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﺍﻝﻤﺭﻜﺯﻴﺘﻴﻥ‬
‫‪ .V‬ﺘﻤﺭﻴﻥ ﻤﺤﻠﻭل‬
‫‪ .VI‬ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪-‬ﺘﺭﻜﻴﺏ ﻤﺤﻠﻭل‬
‫‪ .1.VI‬ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ ﻭﺤﻴﺩ‬
‫‪ .2.VI‬ﺘﺸﻜﹼل ﻋﺩﺓ ﻤﻌﻘﹼﺩﺍﺕ ﺒﺎﻝﺘﻌﺎﻗﺏ‬
‫‪ .3.VI‬ﺘﺸﻜﹼل ﻋﺩﺓ ﻤﻌﻘﹼﺩﺍﺕ ﺒﺂﻥ ﻭﺍﺤﺩ‬
‫‪ .VII‬ﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺘﻌﻘﻴﺩ‬
‫‪ .1.VII‬ﻤﺒﺩﺃ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫‪ .2.VII‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪pY = f (x‬‬
‫‪ .3.VII‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫‪ .4.VII‬ﺘﻁﺒﻴﻕ‬
‫‪115‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺮﺍﺑﻊ‬ ‫‪116‬‬
‫‪ .I‬ﺘﻤﻬﻴﺩ‬
‫ﻤﻥ ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻌﻘﻴﺩ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﻨﺫﻜﺭ‪ :‬ﺍﻨﺘﻘﺎل ﺍﻷﻜﺴﺠﻴﻥ ﻭﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﻋﻨﺩ‬
‫ﺍﻝﻜﺎﺌﻨﺎﺕ ﺍﻝﺤﻴﺔ‪ ،‬ﻭﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻀﻭﺌﻲ ﻋﻨﺩ ﺍﻝﻨﺒﺎﺕ‪ ،‬ﻭﻜﺫﻝﻙ ﺘﺨﻠﻴﺹ ﺍﻝﻤﺎﺀ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻴﻪ ﺒﺎﺴﺘﻌﻤﺎل ﺒﻌﺽ ﺍﻝﻤﻨﻅﹼﻔﺎﺕ‪.‬‬
‫‪ .1.I‬ﻤﺸﺎﻫﺩﺍﺕ ﺘﺠﺭﻴﺒﻴﺔ‬
‫ﻨﻀﻴﻑ ﻋﺩﺓ ﻨﻘﺎﻁ ﻤﻥ ﻤﺤﻠﻭل ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ‪ 0.1 mol/L‬ﺍﻝﻌﺩﻴﻤﺔ ﺍﻝﻠﻭﻥ ﺇﻝﻰ‬
‫ﺃﻨﺒﻭﺏ ﺍﺨﺘﺒﺎﺭ ﺤﺎ ﹴﻭ ﻋﻠﻰ ﺍﻝﻘﻠﻴل ﻤﻥ ﻤﺤﻠﻭل ﺒﺭﺘﻘﺎﻝﻲ ﺍﻝﻠﻭﻥ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺤﺩﻴﺩ ‪ Fe Cl3‬ﺒﺘﺭﻜﻴﺯ‬
‫ﻥ ﻝﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻴﺼﺒﺢ ﺃﺤﻤﺭ ﻗﺎﻨﺌﹰﺎ ﻭﻴﺒﻘﻰ ﺍﻝﻤﺤﻠﻭل ﺸﻔﺎﻓﹰﺎ‪ .‬ﻴﻌﻭﺩ ﻫﺫﺍ‬
‫‪ . 0.1 mol/L‬ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﻠﻭﻥ ﺍﻷﺤﻤﺭ ﺍﻝﻘﺎﻨﺊ ﺇﻝﻰ ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﺤﺩﻴﺩ ‪ [ Fe(SCN) ]2+ III‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ‬
‫ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ‪:‬‬
‫‪Fe3+ + SCN− ⇌ [ Fe(SCN) ]2 +‬‬
‫ﻻ ﻤﺭ ﻜﹼﺯ ﹰﺍ ﻭﻋﺩﻴﻡ ﺍﻝﻠﻭﻥ ﻤﻥ ﺃﻭﻜﺴﺎﻻﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ‪،‬‬
‫ﻨﻀﻴﻑ ﺒﻌﺩ ﺫﻝﻙ ﻭﺒﺎﻝﺘﺩﺭﻴﺞ ﻤﺤﻠﻭ ﹰ‬
‫ﻓﻨﻼﺤﻅ ﺍﺨﺘﻔﺎﺀ ﺍﻝﻠﻭﻥ ﺍﻷﺤﻤﺭ ﺍﻝﻘﺎﻨﺊ ﻝﻴﻅﻬﺭ ﻤﻜﺎﻨﻪ ﻝﻭﻥ ﺃﺨﻀﺭ ﺒﺎﻫﺕ ﻴﻌﻭﺩ ﺇﻝﻰ ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ‬
‫ﺃﻭﻜﺴﺎﻻﺕ ﺍﻝﺤﺩﻴﺩ ‪ [ Fe(C2O4 ) ]+ III‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ‪:‬‬
‫‪. [ Fe(SCN) ]2 + + C2O24− ⇌ [ Fe(C2O4 ) ]+ + SCN−‬‬
‫ﹶﻨﺼ‪‬ﻑ ﺍﻝﺸﻭﺍﺭﺩ ‪ [ Fe(SCN) ]2+‬ﻭ ‪ [ Fe(C2O4 ) ]+‬ﺒﺎﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﻘﹼﺩﺓ ﺃﻭ ﺒﻤﺭ ﻜﹼﺒﺎﺕ‬
‫ﺍﻝﺘﺴﺎﻨﺩ‪.‬‬
‫‪ .2.I‬ﺘﻌﺎﺭﻴﻑ‬
‫ل ﻨﻭﻉ ﻜﻴﻤﻴﺎﺌﻲ ﻤﺘﻌﺩﺩ ﺍﻝﺫﺭﺍﺕ ﻤﻜﻭ‪‬ﻥ ﻤﻥ ﺫﺭﺓ ﺃﻭ ﺸﺎﺭﺩﺓ ﻤﻭﺠﺒﺔ ﻤﺭﻜﺯﻴﺔ‬

‫ﻨﺴﻤﻲ ﻤﻌﻘﹼﺩ ﹰﺍ ﻜ ّ‬
‫ﺘﺭﺘﺒﻁ ﺒﻬﺎ ﺒﺠﺯﻴﺌﺎﺕ ﺃﻭ ﺸﻭﺍﺭﺩ ﻨﺴﻤﻴﻬﺎ ﺍﻝﺭﺒﻴﻁﺎﺕ ﺃﻭ ﺍﻝﻤﺴﺎﻨ‪‬ﺩﺍﺕ‪.‬‬
‫ﺃﻣﺜﻠﺔ ﻋﻦ ﺍﳌﻌﻘﺪﺍﺕ‬ ‫‬
‫‪3+‬‬ ‫‪2+‬‬ ‫‪+‬‬
‫] ‪…، [ Fe(CO)5 ] ، [ Fe(H2O)6‬‬ ‫] ‪، [ Zn(NH3 )4‬‬ ‫] ‪، [ Ag(NH3 )2‬‬
‫ﺃﻣﺜﻠﺔ ﻋﻦ ﺍﻟﺬﺭﺍﺕ ﺃﻭ ﺍﻟﺸﻮﺍﺭﺩ ﺍﳌﺮﻛﺰﻳﺔ‬ ‫‬
‫‪Cu2+ ، Fe ، Fe2+ ، Fe3 + ، Co ، Co2+ ، Ni ، Ni2 +‬‬

‫‪117‬‬ ‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻟﺘﻌﻘﻴﺪ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ﻨﻼﺤﻅ ﺃ ﻥ‪ ‬ﺠﻤﻴﻊ ﺍﻝﺫﺭﺍﺕ ﻭﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﺭﻜﺯﻴﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺘﻀ ‪‬ﻡ ﺤﺠﻴﺭﺍﺕ ﺇﻝﻜﺘﺭﻭﻨﻴﺔ ﻓﺎﺭﻏﺔ‪ ،‬ﻭﺒﺫﻝﻙ‬
‫ﻓﻬﻲ ﺘﺴﺘﻁﻴﻊ ﺃﻥ ﺘﺴﺘﻘﺒل ﺃﺯﻭﺍﺠﹰﺎ ﺇﻝﻜﺘﺭﻭﻨﻴﺔ ﻤﻥ ﺠﺯﻴﺌﺎﺕ ﻭﺸﻭﺍﺭﺩ ﺃﺨﺭﻯ‪.‬‬
‫ﻻ ﺃﻨﻪ ﻤﻥ‬
‫ﻏﺎﻝﺒﹰﺎ ﻤﺎ ﺘﻜﻭﻥ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺃﻭ ﺍﻝﺫﺭﺍﺕ ﺍﻝﻤﺭﻜﺯﻴﺔ ﻤﻥ ﺍﻝﻌﻨﺎﺼﺭ ﺍﻻﻨﺘﻘﺎﻝﻴﺔ‪ ،‬ﺇ ﹼ‬
‫ﺍﻝﻤﻤﻜﻥ ﺃﻥ ﻨﺠﺩ ﺸﻭﺍﺭﺩ ﻤﻥ ﻏﻴﺭ ﺍﻝﻌﻨﺎﺼﺭ ﺍﻻﻨﺘﻘﺎﻝﻴﺔ ﻤﺜل ‪ Ag+ ، Mg 2+ ، Ca 2+‬ﻗﺎﺩﺭﺓ ﺃﻴﻀﹰﺎ‬
‫ﻋﻠﻰ ﺘﺸﻜﻴل ﻤﻌﻘﹼﺩﺍﺕ‪.‬‬
‫ل ﺠﺯﻱ ﺀ ﺃﻭ ﺸﺎﺭﺩﺓ ﻜﻴﻤﻴﺎﺌﻴﺔ ﺘﺘﻤﺘﹼﻊ ﺒﺯﻭﺝ‬

‫ﻤﻥ ﺠﻬﺔ ﺃﺨﺭﻯ ﻨﺴﻤﻲ ﺭﺒﻴﻁﺔ ‪ Ligand‬ﻜ ّ‬
‫ﺇﻝﻜﺘﺭﻭﻨﻲ ﺤ ‪‬ﺭ ﻋﻠﻰ ﺍﻷﻗل‪ ،‬ﻭﺒﺫﻝﻙ ﻓﻬﻲ ﺘﺴﺘﻁﻴﻊ ﺃﻥ ﺘﻤﻨﺤﻪ ﻝﺠﺯﻱﺀ ﺃﻭ ﺸﺎﺭﺩﺓ ﺃﺨﺭﻯ ﺤﺎﻭﻴﺔ ﻋﻠﻰ‬
‫ﺤﺠﻴﺭﺓ ﻓﺎﺭﻏﺔ ﻓﻲ ﻁﺒﻘﺘﻬﺎ ﺍﻝﺴﻁﺤﻴﺔ ﻝﺘﺸﻜﻴل ﺭﺍﺒﻁﺔ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻓﻴﻤﺎ ﺒﻴﻨﻬﻤﺎ‪.‬‬
‫ﻥ ﺍﻝﺭﺒﻴﻁﺔ ﻭﺤﻴﺩﺓ ﺍﻝﺴﻥ ﺇﺫﺍ ﺍﺭﺘﺒﻁﺕ ﻤﻊ ﺍﻝﺫﺭﺓ ﺃﻭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ﺒﺭﺍﺒﻁﺔ‬

‫ﻭﻨﻘﻭل ﺇ ‪‬‬
‫ﻭﺤﻴﺩﺓ ﻜﻤﺎ ﻫﻭ ﺤﺎل‪:‬‬
‫••‬ ‫••‬
‫‪→ •• N H3,‬‬ ‫‪→ •• O 2 H,‬‬ ‫‪→−•• O‬‬
‫••‬
‫‪H,‬‬ ‫⋯⋯ ‪→−•• CN,‬‬
‫ﻴﺸﻴﺭ ﺍﻝﺴﻬﻡ ﺇﻝﻰ ﺍﻝﺜﻨﺎﺌﻴﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻤﺴﺘﻌﻤﻠﺔ ﺒﺼﻔﺘﻬﺎ ﺴﻨﹰﺎ ﻝﻼﺭﺘﺒﺎﻁ‪.‬‬
‫ﻥ ﺍﻝﺭﺒﻴﻁﺔ ﺜﻨﺎﺌﻴﺔ ﺍﻝﺴﻥ ﺇﺫﺍ ﺍﺭﺘﺒﻁﺕ ﻤﻊ ﺍﻝﺫﺭﺓ ﺃﻭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ﺒﺭﺍﺒﻁﺘﻴﻥ‬
‫ﻜﻤﺎ ﻫﻭ ﺤﺎل ﺍﻝﺠﺯﻱﺀ ﺜﻨﺎﺌﻲ ﺃﻤﻴﻥ ﺍﻹﻴﺜﻠﻴﻥ ﺍﻝﺘﻲ ﻨﺭﻤﺯ ﺇﻝﻴﻬﺎ ﺒﺎﻝﺭﻤﺯ ‪ en‬ﻭﻨﺒﻴ‪‬ﻨﻬﺎ ﻓﻴﻤﺎ ﻴﻠﻲ ‪:‬‬
‫← ••‪→ •• NH2 −CH2 −CH2 −H2N‬‬
‫ﻥ ﺍﻝﺭﺒﻴﻁﺔ ﺴﺩﺍﺴﻴﺔ ﺍﻝﺴﻥ ﺇﺫﺍ ﺍﺭﺘﺒﻁﺕ ﻤﻊ ﺍﻝﺫﺭﺓ ﺃﻭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ﺒﺴﺕ‬
‫ﺭﻭﺍﺒﻁ ﻜﻤﺎ ﻫﻭ ﺤﺎل ﺸﺎﺭﺩﺓ ﺭﺍﺒﻊ ﺨﻼﺕ ﺜﻨﺎﺌﻲ ﺃﻤﻴﻥ ﺍﻹﻴﺜﻠﻴﻥ ‪ EDTA‬ﺍﻝﺘﻲ ﻨﺭﻤﺯ ﺇﻝﻴﻬﺎ ﺒﺎﻝﺭﻤﺯ‬
‫‪ ،Y 4 −‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪. ( 1‬‬
‫•‬ ‫•‬
‫•‬ ‫‪•O‬‬
‫‪•O‬‬
‫•‬ ‫•‬
‫•‬
‫‪H2C‬‬ ‫‪CH2‬‬
‫•‬
‫•‬ ‫•‬
‫••‬ ‫••‬
‫••‪• • •O‬‬
‫•‬
‫• ••‪••O‬‬
‫‪••O‬‬
‫•‬ ‫⊖‬ ‫‪N−CH2 −CH2 −N‬‬ ‫•‪⊖ • O‬‬
‫•‬
‫‪H2C‬‬ ‫‪CH2‬‬
‫•‬
‫•‬ ‫•‬
‫•‪•O‬‬ ‫•‬
‫⊖ ••‬ ‫••‪••O‬‬
‫⊖‬
‫ﺍﻝﺸﻜل )‪ : (1‬ﺼﻴﻐﺔ ‪EDTA‬‬
‫ﻨﺴﻤ‪‬ﻲ ﺩﻝﻴل ﺍﻝﺭﺒﻴﻁﺔ ﺃﻭ ﺩﻝﻴل ﺍﻝﺘﺴﺎﻨﺩ ﻋﺩﺩ ﺍﻝﺭﻭﺍﺒﻁ ﺍﻝﺒﺴﻴﻁﺔ ﺍﻝﺘﻲ ﺘﺘﺸﻜﹼل ﺒﻴﻥ ﺍﻝﺫﺭﺓ ﺃﻭ‬
‫ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ﻭﺍﻝﺭﺒﻴﻁﺎﺕ ﻭﻫﻭ ﻴﺴﺎﻭﻱ ﻋﺎﺩﺓ ﻋﺩﺩ ﺍﻝﺭﺒﻴﻁﺎﺕ ‪ ،‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﻫﺫﻩ‬
‫ﺍﻝﺭﺒﻴﻁﺎﺕ ﻭﺤﻴﺩﺓ ﺍﻝﺴﻥ‪ ،‬ﻜﻤﺎ ﻫﻭ ﻤﻭﻀ‪‬ﺢ ﻓﻲ ﺍﻝﺠﺩﻭل ﺍﻝﺘﺎﻝﻲ ‪:‬‬
‫ﺩﻝﻴل ﺍﻝﺭﺒﻴﻁﺔ‬ ‫ﺼﻴﻐﺔ ﺍﻝﻤﻌﻘﺩ‬
‫‪2‬‬ ‫‪[ Ag(NH3 )2 ]+‬‬
‫‪4‬‬ ‫‪[ Zn(NH3 )4 ]2+‬‬
‫‪4‬‬ ‫‪[ Cu(CN)4 ]2−‬‬
‫‪5‬‬ ‫] ‪[ Fe(CO)5‬‬
‫‪6‬‬ ‫‪[ Fe(H2O)6 ]3+‬‬
‫‪6‬‬ ‫‪[ Ni(en)3 ]2 +‬‬
‫ﻭ ﻨﺫﻜﺭ ﻫﻨﺎ ﺃﻤﺜﻠﺔ ﻋﻥ ﺒﻌﺽ ﺍﻝﻤﻌﻘﺩﺍﺕ ﺍﻝﻁﺒﻴﻌﻴﺔ ﻤﺜل ﺍﻝﻬﻴﻤﻭﻏﻠﻭﺒﻴﻥ ‪ ،‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل )‪، (2‬‬
‫ﻭﺍﻝﻜﻠﻭﺭﻭﻓﻴل ‪ ،‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل )‪ ، (3‬ﺍﻝﺘﻲ ﺘﺸﺘﺭﻙ ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ ﺒﺎﻝﺭﺒﻴﻁﺔ ﺫﺍﺘﻬﺎ ﻭﻫﻲ ﺍﻝﺒﻭﺭﻓﻴﺭﻴﻥ‬
‫‪ Porphyrine‬ﺍﻝﺘﻲ ﺘﻀ ‪‬ﻡ ﺃﺭﺒﻊ ﺤﻠﻘﺎﺕ ﺒﻴﺭﻭل ﻤﺭﺘﺒﻁﺔ ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ ﺒﺠﺴﻭﺭ ﻜﺭﺒﻭﻨﻴﺔ‪ .‬ﻭﻓﻲ ﺤﻴﻥ‬
‫ﺘﺅﺩﻱ ﺸﺎﺭﺩﺓ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ‪ II‬ﺩﻭﺭ ﺍﻝﻤﺘﻘﺒ‪‬ل ﻝﻠﺭﺒﻴﻁﺔ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻜﻠﻭﺭﻭﻓﻴل‪ ،‬ﻨﺠﺩ ﺃ ‪‬‬
‫ﻥ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ‬
‫ﺘﺅﺩﻱ ﻫﺫﺍ ﺍﻝﺩﻭﺭ ﻓﻲ ﺍﻝﻬﻴﻤﻭﻏﻠﻭﺒﻴﻥ‪.‬‬ ‫‪II‬‬
‫

‬
‫ﻝﻤﺎﺫﺍ ﻨﻀﻴﻑ ﺃﻤﻼﺡ ﻤﺭﻜﹼﺏ ‪ E.D.T.A.‬ﺇﻝﻰ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻐﺫﺍﺌﻴﺔ ﺍﻝﻤﻌﻠﺒﺔ‪ :‬ﺍﻝﻤـﺎﻴﻭﻨﻴﺯ‪ ,‬ﺍﻝﻔﻭﺍﻜـﻪ‬
‫ﻭﺍﻝﺨﻀﺎﺭ ﺍﻝﻤﻌﻠﺒﺔ‪ ,‬ﺍﻝﺯﻴﻭﺕ‪ ،‬ﺍﻝﻤﺎﺭﻏﺭﻴﻥ؟‬
‫ﻝﻭ ﺘﻤﻌ‪‬ﻨﺕ ﺠﻴﺩﹰﺍ ﺒﺎﻝﻤﻜﻭﻨﺎﺕ ﺍﻝﺘﻲ ﺘﺠﺩﻫﺎ ﻋﻠﻰ ﻋﺒﻭﺓ ﺍﻝﻤﺎﻴﻭﻨﻴﺯ ﻓﻲ ﻤﻁﺒﺦ ﺒﻴﺘﻙ ﻝﻭﺠﺩﺕ ﻤﻥ ﺒﻴﻥ ﻤﻜﻭ‪‬ﻨﺎﺘﻬﺎ ﻤﺎﺩﺓ ﺍﻝـ‬
‫ﻼ( ﻭﻗﺩ ﺃﻀﻴﻔﺕ ﻫﺫﻩ ﺍﻝﻤﺎﺩﺓ ﺒﺴﺒﺏ ﻤﻴﻠﻬﺎ ﺍﻝﺸﺩﻴﺩ ﻝﺘﺸﻜﻴل ﻤﻌﻘﺩﺍﺕ ﻤﻊ ﺒﻌﺽ‬
‫‪ EDTA‬ﺒﺼﻴﻐﺔ ) ‪ Na2CaY‬ﻤﺜ ﹰ‬
‫ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﻤﺜل ‪ ..، Fe ، Cu‬ﺍﻝﺘﻲ ﻭﺼﻠﺕ‪ ،‬ﻭﻝﻭ ﺒﻜﻤﻴﺎﺕ ﺼﻐﻴﺭﺓ ﺠﺩﹰﺍ‪ ،‬ﺇﻝﻰ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻐﺫﺍﺌﻴﺔ ﻤﻥ ﺍﻝﺘﺭﺒﺔ ﺃﻭ ﻤﻥ‬
‫ﺨﻼل ﻋﻤﻠﻴﺎﺕ ﺍﻝﺘﺤﻀﻴﺭ ﻭﺍﻝﺘﺼﻨﻴﻊ‪.‬‬
‫ﺇﺫ ﹸﺘﺤﻔﹼﺯ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﺘﻔﺎﻋل ﺍﻷﻜﺴﺠﻴﻥ ﻤﻊ ﺍﻝﺩﺴﻡ ﻏﻴﺭ ﺍﻝﻤﺸﺒﻌﺔ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻐﺫﺍﺌﻴـﺔ‪ ،‬ﻭﻫـﺫﺍ‬
‫ﻴﺅﺩﻱ ﺇﻝﻰ ﺘﻐﻴﺭ ﻓﻲ ﻝﻭﻥ ﺍﻝﻁﻌﺎﻡ ﻭﻅﻬﻭﺭ ﻁﻌﻡ ﺤﺎﻤﺽ ﻏﻴﺭ ﻤﺴﺘﺴﺎﻍ ﻓﻴﻪ‪.‬‬
‫ﻥ ﺇﻀﺎﻓﺔ ﺍﻝـ ‪ E.D.T.A.‬ﺘﺒﻁﺊ ﺍﻝﺩﻭﺭ ﺍﻝﻤﺤﻔﺯ ﻝﻬﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﻓﻲ ﺇﻓﺴﺎﺩ ﺍﻝﻁﻌﺎﻡ‪.‬‬
‫‪N‬‬
‫‪N‬‬
‫‪Fe‬‬
‫‪N‬‬
‫‪N‬‬
‫‪OH‬‬
‫‪O‬‬
‫‪O‬‬ ‫‪OH‬‬
‫ﺍﻝﺸﻜل )‪ : (2‬ﺠﺯﻱﺀ ﺍﻝﻬﻴﻤﻭﻏﻠﻭﺒﻴﻥ‬
‫‪N‬‬
‫‪N‬‬
‫‪Mg‬‬
‫‪N‬‬
‫‪N‬‬
‫‪O‬‬
‫‪CH3‬‬
‫‪H‬‬
‫‪H‬‬
‫‪R O2CCH2CH2 H‬‬ ‫‪CO2 CH3‬‬
‫=‪R‬‬
‫ﺍﻝﺸﻜل )‪ : (3‬ﺠﺯﻱﺀ ﺍﻝﻜﻠﻭﺭﻭﻓﻴل‬

‫‪ .3.I‬ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪:‬‬
‫ﻝﻨﺄﺨﺫ ﺍﻵﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Zn(NH3 )4 ]2+‬ﻭﻝﻨﺤﺎﻭل ﺃﻥ ﻨﻔﺴ‪‬ﺭ ﺘﺸﻜﹼﻠﻪ‪ :‬ﺘﺘﻤﺘﻊ ﺫﺭﺓ ﺍﻝﺘﻭﺘﻴﺎﺀ‬
‫ﻥ ﻝﺸﺎﺭﺩﺓ ﺍﻝﺘﻭﺘﻴﺎﺀ ‪ Zn2+‬ﻋﺩﺩ ﹰﺍ ﻤﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ‬
‫ﻱ ‪ ، Z = 30‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫‪ Zn‬ﺒﻌﺩﺩ ﺫﺭ ‪‬‬
‫ﻴﺴﺎﻭﻱ ‪ . 28‬ﺃ ﻤ‪‬ﺎ ﺍﻝﻜﺭﻴﺒﺘﻭﻥ ﻭﻫﻭ ﺍﻝﻐﺎﺯ ﺍﻝﻨﺒﻴل ﺍﻝﺫﻱ ﻴﻘﻊ ﻓﻲ ﺴﻁﺭ ﺍﻝﺘﻭﺘﻴﺎﺀ ﻓﻠﻪ ‪ 36‬ﺇﻝﻜﺘﺭﻭﻨﺎﹰ‪،‬‬
‫ﻥ ﺸﺎﺭﺩﺓ ‪ Zn2+‬ﺘﺴﺘﻁﻴﻊ ﻀ ‪‬ﻡ ‪ 4‬ﺜﻨﺎﺌﻴﺎﺕ ﺇﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﺘﺄﺨﺫ ﺒﻨﻴﺔ ﻏﺎﺯ ﺍﻝﻜﺭﻴﺒﺘﻭﻥ‪.‬‬
‫ﻭ ﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ل ﻤﻨﻬﺎ ﺩﻭﺭ ﺭﺒﻴﻁﺔ ﻭﺤﻴﺩﺓ ﺍﻝﺴﻥ‪ ،‬ﻤﻊ‬
‫ﻭﻫﻜﺫﺍ ﹸﺘﺸﻜﹼل ﺃﺭﺒﻊ ﺠﺯﻴﺌﺎﺕ ﻨﺸﺎﺩﺭ ‪ ، : NH3‬ﺘﺅﺩﻱ ﻜ ّ‬
‫ﺸﺎﺭﺩﺓ ﺍﻝﺘﻭﺘﻴﺎﺀ ‪ Zn2+‬ﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩ ‪. [ Zn(NH3 )4 ]2+‬‬
‫ﺃ ﻤ‪‬ﺎ ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩ ﺍ ﻝﺴﺎﺒﻕ ﺍﻝﺫﻱ ﻫﻭ ﻤﻥ ﺍﻝﻨﻤﻁ ‪ AX 4‬ﻓﻬﻲ ﺒﺤﺴﺏ ﺍﻝﻘﺎﻋﺩﺓ ‪VSEPR‬‬
‫ﺭﺒﺎﻋﻴﺔ ﺍﻝﻭﺠﻭﻩ ﺒﺤﻴﺙ ﺘﺘﻭﻀﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺘﻭﺘﻴﺎﺀ ﻓﻲ ﻤﺭﻜﺯ ﺭﺒﺎﻋﻲ ﺍﻝﻭﺠﻭﻩ ﻭﺘﻘﻊ ﺠﺯﻴﺌﺎﺕ ﺍﻝﻨﺸﺎﺩﺭ‬
‫ﻋﻠﻰ ﺭﺅﻭﺴﻪ‪ ،‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل )‪.(4‬‬
‫‪NH3‬‬ ‫‪2+‬‬
‫‪Zn‬‬
‫‪H3 N‬‬
‫‪NH3‬‬
‫‪NH3‬‬
‫ﺍﻝﺸﻜل )‪ : ( 4‬ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩ‬

‫‪2+‬‬
‫] ‪[Zn(NH3 )4‬‬
‫ﻓﻲ ﺤﻴﻥ ﻴﺘﻤﺘﻊ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Ag(NH3 )2 ]+‬ﺒﻬﻨﺩﺴﺔ ﺨﻁﻴﺔ ﻷﻨﻪ ﻤﻥ ﺍﻝﺸﻜل ‪: AX 2‬‬
‫‪[ H3N-Ag-NH3 ]+‬‬
‫ﻭﻴﺘﻤﺘﹼﻊ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Cu(CN)4 ]2−‬ﺒﻬﻨﺩﺴﺔ ﻤﺴﺘﻭﻴﺔ ﺤﻴﺙ ﺘﻘﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻨﺤﺎﺱ ﻓﻲ ﻤﺭﻜﺯ‬
‫ﻤﺭ‪‬ﺒﻊ ﻭﺘﻘﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺎﻨﻴﺩ ﻋﻠﻰ ﺭﺅﻭﺴﻪ‪ ،‬ﺍﻝﺸﻜل ) ‪: ( 5‬‬
‫‪NC‬‬ ‫‪CN 2 −‬‬
‫‪Cu‬‬
‫‪NC‬‬ ‫‪CN‬‬
‫ﺍﻝﺸﻜل )‪ : (5‬ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩ‬
‫‪2−‬‬
‫] ‪[Cu(CN)4‬‬
‫ﻓﻲ ﺤﻴﻥ ﻴﺘﻤﺘﹼﻊ ﺍﻝﻤﻌﻘﹼﺩ ] ‪ [ Fe(CO)5‬ﺒﻬﻨﺩﺴﺔ ﻫﺭﻤﻴﻥ ﺒﻘﺎﻋﺩﺓ ﺜﻼﺜﻴﺔ ﻤﺸﺘﺭﻜﺔ ﺒﺤﻴﺙ ﺘﻘﻊ‬
‫ﺫﺭﺓ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﻤﺭﻜﺯ ﺍﻝﻤﺜﻠﹼﺙ‪ ،‬ﺍﻝﺸﻜل ) ‪: ( 6‬‬
‫‪CO‬‬
‫‪CO‬‬ ‫‪Fe‬‬
‫‪CO‬‬
‫‪CO‬‬
‫‪CO‬‬
‫ﺍﻝﺸﻜل )‪ : (6‬ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩ ] ‪[ Fe(CO)5‬‬
‫‪  Fe(H2O)6 ‬ﺒﻬﻨﺩﺴﺔ ﺜﻤﺎﻨﻲ ﻭﺠﻭﻩ‪ ،‬ﺃﻱ ﻫﺭﻤﻴﻥ ﺒﻘﺎ ﻋﺩﺓ ﻤﺭ ﺒ‪‬ﻌﺔ‬ ‫ﻭﻴﻤﺘﻠﻙ ﺍﻝﻤﻌﻘﹼﺩ‬
‫‪2+‬‬
‫ﻤﺸﺘﺭﻜﺔ ﺒﺤﻴﺙ ﺘﻘﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﻤﺭﻜﺯ ﺍﻝﻤﺭﺒ‪‬ﻊ‪ ،‬ﺍﻝﺸﻜل ) ‪: ( 7‬‬

‫‪OH2‬‬ ‫‪2+‬‬
‫‪H2O‬‬ ‫‪Fe‬‬ ‫‪OH2‬‬
‫‪H2O‬‬ ‫‪OH2‬‬
‫‪OH2‬‬
‫] ‪. [ Fe(H2O)6‬‬ ‫ﺍﻝﺸﻜل )‪ : (7‬ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩ‬
‫‪2+‬‬
‫‪ .II‬ﺜﻭﺍﺒﺕ ﻤﻤﻴ‪‬ﺯﺓ ﻝﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﺩﺍﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‬
‫ﻝﺘﻜﻥ ﻝﺩﻴﻨﺎ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ‪ M‬ﻭﺍﻝﺘﻲ ﺘﻀ ‪‬ﻡ ﻋﺩﺩﹰﺍ ﻤﻥ ﺍﻝﺤﺠﻴﺭﺍﺕ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻔﺎﺭﻏﺔ‪،‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ M‬ﺘﺴﺘﻁﻴﻊ ﺘﺜﺒﻴﺕ ‪ n‬ﺭﺒﻴﻁﺔ‬
‫ﻭﻝﺘﻜﻥ ﻝﺩﻴﻨﺎ ﺍﻝﺭﺒﻴﻁﺔ ﻭﺤﻴﺩ ﺓ ﺍﻝﺴﻥ ‪ . L‬ﻭﻝﻨﻔﺘﺭﺽ ﺃ ‪‬‬
‫ﻭﺤﻴﺩﺓ ﺍﻝﺴﻥ ‪ L‬ﻝﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩ ‪ ، MLn‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ‪:‬‬
‫‪M + nL ⇌ MLn‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ M‬ﺘﺅﺩﻱ ﺩﻭﺭ ﻤﺘﻘﺒ‪‬ل ﻝﻠﺭﺒﻴﻁﺎﺕ ﻓﻲ ﺤﻴﻥ‬

‫ﻭﻨﻼﺤﻅ ﻓﻲ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﺃ ‪‬‬
‫ﻴﺅﺩﻱ ﺍﻝﻤﻌﻘﹼﺩ ‪ MLn‬ﺩﻭﺭ ﻤﺎﻨﺢ ﻝﻠﺭﺒﻴﻁﺎﺕ‪ .‬ﻭ ﻴ‪‬ﺫ ﻜﹼﺭﻨﺎ ﺩﻭﺭ ﺍﻝﻤﻌ‪‬ﻘﺩ ﺒﺎﻝﺩﻭﺭ ﺍﻝﺫﻱ ﻴﺅﺩﻴﻪ ﺤﻤﺽ‬
‫ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪ AHn‬ﺒﺼﻔﺘﻪ ﻤﺎﻨﺤﹰﺎ ﻝﻠﺒﺭﻭﺘﻭﻨﺎﺕ ‪ H+‬ﻭﻝﻬﺫﺍ ﻨﻌﺭ‪‬ﻑ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻭﺒﺼﻭﺭﺓ‬
‫ﻤﺸﺎﺒﻬﺔ ﻝﻤﺎ ﺭﺃﻴﻨﺎﻩ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﺍﻷﺯﻭﺍﺝ ‪ :‬ﻤﺘﻘﺒ‪‬ل ﻝﻠﺭﺒﻴﻁﺔ‪/‬ﻤﺎﻨﺢ ﻝﻠﺭﺒﻴﻁﺔ ﻓﻨﻜﺘﺏ‪:‬‬
‫‪. M / MLn‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺘﺘﻤﺘﻊ ﺒﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ ﻨﺴﻤﻴﻪ ﺜﺎﺒﺕ ﺍﺴﺘﻘﺭﺍﺭ ﺍﻝﻤﻌﻘﹼﺩ‬
‫ﺃﻭ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻹﺠﻤﺎﻝﻲ ﻝﻠﻤﻌﻘﹼﺩ‪ ،‬ﻭﻏﺎﻝﺒﹰﺎ ﻤﺎ ﻨﺭﻤﺯ ﺇﻝﻴﻪ ﺒﺎﻝﺭﻤﺯ ‪ βn‬ﻓﻨﻜﺘﺏ ‪:‬‬
‫‪[MLn ]/C 0‬‬

‫= ‪βn‬‬
‫‪([M ]/C 0 ) ⋅ ([L ]/C 0 )n‬‬
‫ﺤﻴﺙ ‪ .C 0 = 1.00 mol/L‬ﻭﺒﺫﻝﻙ ﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ‪: βn‬‬
‫] ‪[ MLn‬‬
‫= ‪βn‬‬
‫‪[ M ] [ L ]n‬‬
‫ﻥ ﺍﻝﺜﺎﺒﺕ ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻲ ‪ βn‬ﻻ ﻭﺍﺤﺩﺓ ﻝﻪ‪ ،‬ﺸﺭﻁ ﺍﻝﺘﻌﺒﻴﺭ ﻋﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺒﺎﻝﻭﺍﺤﺩﺓ‬

‫ﻻ ﺒﺩﺭﺠﺎﺕ ﺍﻝﺤﺭﺍﺭﺓ‪.‬‬
‫‪ ، mol / L‬ﻭﻫﻭ ﻻ ﻴﺘﻌﻠﹼﻕ ﺇ ﹼ‬
‫ﺕ ﺍﻝﺘﻔﻜﻙ ﺍﻹﺠﻤﺎﻝﻲ ﻝﻠﻤﻌﻘﹼﺩ ﻭﻨﺭﻤﺯ ﺇﻝﻴﻪ ﺒﺎﻝﺭﻤﺯ ‪ ، Kd‬ﻭﻨﻜﺘﺏ ‪:‬‬

‫ﻭﻨﺴﻤ‪‬ﻲ ﻤﻘﻠﻭﺏ ﺍﻝﺜﺎﺒﺕ ﺍﻝﺴﺎﺒﻕ ﺜﺎﺒ ﹶ‬
‫‪1‬‬
‫= ‪Kd‬‬
‫‪βn‬‬
‫ﻥ‬
‫‪pKd = log βn‬‬
‫♣ ﻋﻨﺩﻤﺎ ﻨﻀﻴﻑ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺤﺎ ﹴﻭ ﻋﻠﻰ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ‪ M‬ﺍﻝﺭﺒﻴﻁﺔ ‪L‬‬
‫ﻴﺘﺸﻜﹼل ﻝﺩﻴﻨﺎ ﻋﻠﻰ ﺍﻝﺘﻌﺎﻗﺏ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪. MLn ،…، MLi ،…، ML3 ، ML2 ، ML‬‬
‫ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪‬‬ ‫‪M +L‬‬ ‫‪⇌ ML‬‬

‫‪‬‬
‫‪ ML + L‬‬ ‫‪⇌ ML2‬‬
‫‪‬‬
‫‪‬‬ ‫‪:‬‬
‫‪‬‬
‫‪‬‬ ‫‪:‬‬
‫‪‬‬
‫‪ MLi −1 + L‬‬ ‫‪⇌ MLi‬‬
‫‪‬‬
‫‪‬‬ ‫‪:‬‬
‫‪‬‬ ‫‪:‬‬
‫‪‬‬
‫‪ ML‬‬
‫‪‬‬ ‫‪n −1 + L‬‬ ‫‪⇌ MLn‬‬
‫ﺘﻭﺍﺯﻥ ﺨﺎﺼﹰﺎ ﺒﻪ ﻨﺴﻤﻴﻪ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻝﺘﻌﺎﻗﺒﻲ‬ ‫ل ﻤﻥ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺴﺎﺒﻘﺔ ﺜﺎﺒﺕ‬
‫ﻭﻨﻌﺭ‪‬ﻑ ﻝﻜ ّ‬
‫‪: K fi‬‬
‫] ‪[ MLi‬‬
‫= ‪K fi‬‬
‫] ‪[ MLi −1 ] [ L‬‬
‫ﻭﻜﻠﹼﻤﺎ ﻜﺎﻥ ‪ K fi‬ﻜﺒﻴﺭﺍﹰ‪ ،‬ﻜﺎﻥ ﺘﻔﺎﻋل ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩ ‪ MLi‬ﺘﺎﻤﹰﺎ‪ ،‬ﻭﻜﺎﻥ ﺍﻝﻤﻌﻘﹼﺩ ﺃﻜﺜﺭ ﺍﺴﺘﻘﺭﺍﺭﹰﺍ‪.‬‬
‫ﺕ ﺍﻝﺘﻔﻜﹼﻙ ﺍﻝﺘﻌﺎﻗﺒﻲ ‪: Kd‬‬

‫ﻭﻨﺴﻤﻲ ﻤﻘﻠﻭﺏ ﺍﻝﺜﺎﺒﺕ ﺍﻝﺴﺎﺒﻕ ﺜﺎﺒ ﹶ‬
‫‪i‬‬
‫‪1‬‬
‫= ‪Kdi‬‬
‫‪K fi‬‬
‫ﺃﻭ ﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ‪:‬‬
‫‪pKdi = log K fi‬‬
‫ﻭﺒﻬﺫﺍ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‬ ‫♣‬

‫‪n‬‬
‫= ‪βn‬‬ ‫‪∏Kf‬‬ ‫‪i‬‬
‫‪i =1‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪n‬‬
‫= ‪log βn‬‬ ‫) ‪∑ log ( K f‬‬ ‫‪i‬‬
‫‪i =1‬‬
‫ﻥ‪:‬‬
‫ﻤﻥ ﻨﺎﺤﻴﺔ ﺜﺎﻨﻴﺔ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪n‬‬
‫= ‪Kd‬‬ ‫‪∏ Kd‬‬ ‫‪i‬‬
‫‪i =1‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪n‬‬
‫= ‪pKd‬‬ ‫‪∑ pKd‬‬ ‫‪i‬‬
‫‪i =1‬‬
‫ﻭﻴﻤﻜﻥ ﺘﺤﺩﻴﺩ ‪ K fk‬ﻭ ‪ Kdk‬ﺍﻨﻁﻼﻗﹰﺎ ﻤﻥ ‪ βk‬ﻭ ‪ ، βk −1‬ﺇﺫ ﺇ ‪‬‬

‫ﻥ‪:‬‬ ‫♣‬
‫‪k −1‬‬ ‫‪k‬‬
‫= ‪βk −1‬‬ ‫= ‪ βk‬ﻭ ‪∏ K f‬‬
‫‪i‬‬
‫‪∏Kf‬‬ ‫‪i‬‬
‫‪i =1‬‬ ‫‪i =1‬‬
‫ﻭﺒﻬﺫﺍ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬

‫‪1‬‬ ‫‪β‬‬
‫= ‪K fk‬‬ ‫‪= k‬‬
‫‪Kdk‬‬ ‫‪βk −1‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪log K fk = pKdk = log βk − log βk −1‬‬
‫‪ .III‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ‬
‫ﻝﻨﻔﺘﺭﺽ ﺃﻨﻨﺎ ﻨﻀﻴﻑ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺍﻝﺭﺒﻴﻁﺔ ‪ L‬ﺇﻝﻰ ﻤﺤﻠﻭل ﺤﺎ ﹴﻭ ﻋﻠﻰ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ‬
‫‪ ، M‬ﻭﻝﻨﻔﺘﺭﺽ ﺃﻨﻪ ﺘﺘﺸﻜﹼل ﺘﺩﺭﻴﺠﻴﹰﺎ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ‪. MLn ،…، MLi ،…، ML3 ، ML2 ، ML :‬‬
‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩ ‪ MLi‬ﺒﺩﺀﹰﺍ ﻤﻥ ﺍﻝﻤﻌﻘﹼﺩ ﺍﻝﺫﻱ ﻴﺴﺒﻘﻪ‪:‬‬
‫‪MLi −1 + L ⇌ MLi‬‬
‫ﻭﻨﻜﺘﺏ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻝﺘﻌﺎﻗﺒﻲ ﻝﻠﻤﻌﻘﹼﺩ ﺍﻝﺴﺎﺒﻕ ‪:‬‬
‫] ‪[ MLi‬‬
‫= ‪K fi‬‬
‫] ‪[ MLi −1 ][ L‬‬
‫ﻥ‪:‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫] ‪− log K fi = − log [ MLi ] + log [ L ] + log [ MLi −1‬‬
‫ﻭﻋﻠﻴﻪ ﻨﻜﺘﺏ ‪:‬‬
‫] ‪[ MLi −1‬‬
‫‪pL = log K fi + log‬‬
‫] ‪[ MLi‬‬
‫ﻭﻨﻼﺤﻅ ﻤﺎ ﻴﻠﻲ ‪:‬‬
‫ﻥ ] ‪. [ MLi ] = [ MLi −1‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ‪ pL = log K fi = pKdi‬ﻓﺈ ‪‬‬
‫ﻥ ﺍﻝﻤﻌﻘﹼﺩ‬
‫ﻥ ] ‪ ، [ MLi −1 ] > [ MLi‬ﺃﻱ ﺇ ‪‬‬
‫ ﻭﻓﻲ ﺤﺎﻝﺔ ‪ pL > log K fi = pKdi‬ﻓﺈ ‪‬‬
‫‪ MLi −1‬ﻫﻭ ﺍﻝﺭﺍﺠﺢ‪.‬‬
‫ﻥ‬
‫ﻥ ] ‪ ، [ MLi −1 ] < [ MLi‬ﺃﻱ ﺇ ‪‬‬
‫ﻭﺃﺨﻴﺭﺍﹰ‪ ،‬ﻓﻲ ﺤﺎﻝﺔ ‪ pL < log K fi = p Kdi‬ﻓﺈ ‪‬‬ ‫‬
‫ﺍﻝﻤﻌﻘﹼﺩ ‪ MLi‬ﻫﻭ ﺍﻝﺭﺍﺠﺢ‪.‬‬
‫ﻭﻫﺫﺍ ﻤﺎ ﻨﻌﺒ‪‬ﺭ ﻋﻨﻪ ﺒﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﻤﺒﻴﻥ ﻓﻲ ﺍﻝﺸﻜل ) ‪ ( 8‬ﺍﻝﺘﺎﻝﻲ ‪:‬‬
‫ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ‪MLi‬‬ ‫ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ‪MLi− 1‬‬

‫‪log K fi‬‬ ‫‪pL‬‬
‫ﺍﻝﺸﻜل )‪ : (8‬ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺯﻭﺝ ‪MLi −1 / MLi‬‬
‫ﻼ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Cu(NH3 )4 ]2+‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻝﺘﻌﺎﻗﺒﻴﺔ ﺍﻵﺘﻴﺔ ‪:‬‬

‫ﻓﻠﻭ ﺃﺨﺫﻨﺎ ﻤﺜ ﹰ‬
‫‪log K f4 = 2.1 ، log K f3 = 2.9 ، log K f2 = 3.5 ، log K f1 = 4.1‬‬
‫ﻝﺤﺼﻠﻨﺎ ﻋﻠﻰ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﺘﺎﻝﻲ‪ ،‬ﺍﻝﺸﻜل ) ‪: ( 9‬‬
‫‪[Cu(NH 3 )4 ]2 +‬‬ ‫‪[Cu(NH3 )3 ]2 +‬‬ ‫‪[Cu(NH 3 )2 ]2+‬‬ ‫‪[Cu(NH 3 )]2 +‬‬ ‫‪Cu 2 +‬‬
‫‪2.1‬‬ ‫‪2.9‬‬ ‫‪3.5‬‬ ‫‪4.1‬‬ ‫‪pNH 3‬‬
‫‪ Cu‬ﻤﻊ ﺍﻝﻨﺸﺎﺩﺭ‪.‬‬ ‫‪2+‬‬
‫ﺍﻝﺸﻜل )‪ : (9‬ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻤﻌﻘﺩﺍﺕ ﺸﺎﺭﺩﺓ ﺍﻝﻨﺤﺎﺱ‬
‫ل ﺘﻌﻘﹼﺩ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ‬

‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻜﻠﻤﺎ ﻜﺎﻥ ‪ pL‬ﻜﺒﻴﺭ ﺍﹰ‪ ،‬ﻜﺎﻥ ﺘﺭﻜﻴﺯ ﺍﻝﺭﺒﻴﻁﺔ ﺼﻐﻴﺭ ﹰﺍ‪ ،‬ﻭﻗ ّ‬
‫‪ . Cu2+‬ﻭﻝﻬﺫﺍ ﻨﺠﺩ ﺃﻴﻀﹰﺎ ﺭﺠﺤﺎﻥ ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﺩﻨﻴﺔ ﻋﻨﺩ ﺍﻝﻘﻴﻡ ﺍﻝﻌﻠﻴﺎ ﻝـ ‪. pL‬‬
‫ﺘﺘﻤﺘﻊ ﺍﻝﻤﻌﻘﺩﺍﺕ ﻓﻲ ﻤﺜل ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺒﺜﻭﺍﺒﺕ ﺍﺴﺘﻘﺭﺍﺭ ﻤﺘﻌﺎﻗﺒﺔ ‪ K fi‬ﺘﺘﻨﺎﻗﺹ ﻤﻊ ﺘﺯﺍﻴﺩ ‪. i‬‬
‫ﻻ ﺃﻨﻨﺎ ﻨﺠﺩ ﺍﺴﺘﺜﻨﺎﺀ ﻝﻬﺫﻩ ﺍﻝﻘﺎﻋﺩﺓ ﻓﻲ ﺒﻌﺽ ﺍﻝﺤﺎﻻﺕ ﻜﻤﺎ ﻫﻭ ﺤﺎل ﻤﻌﻘﺩﺍﺕ ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ ﻤﻊ‬
‫ﺇﹼ‬
‫ﺍﻝﻨﺸﺎﺩﺭ ﺤﻴﺙ ﻨﺠﺩ ‪ ، log K f1 = 3.3‬ﻭ ‪ ، log K f2 = 3.9‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪: ( 10‬‬
‫‪+‬‬
‫]) ‪[Ag(NH 3‬‬ ‫‪Ag+‬‬ ‫‪3.9‬‬ ‫‪pNH 3‬‬
‫‪3.3‬‬ ‫‪[Ag(NH 3 )2 ]+‬‬ ‫‪[Ag(NH 3 )]+‬‬

‫ﺍﻝﺸﻜل )‪ : (10‬ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻤﻌﻘﺩﺍﺕ ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ ‪ Ag+‬ﻤﻊ ﺍﻝﻨﺸﺎﺩﺭ‪.‬‬
‫ﻓﻔﻲ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻨﻼﺤﻅ ﻭﺠﻭﺩ ﻤﻨﻁﻘﺘﻴﻥ ﻤﻨﻔﺼﻠﺘﻴﻥ ﻝﺭﺠﺤﺎﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪. [ Ag(NH3 ) ]+‬‬
‫ﻥ ﻫﺫﺍ ﺍﻝﻤﻌﻘﹼﺩ ﺴﻭﻑ ﻴﺘﻔﻜﹼﻙ )ﻜﻤﺎ ﺴﻨﺭﻯ ﺒﻌﺩ ﻗﻠﻴل( ﻭﻝﻥ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯﻩ ﺃﺒﺩﹰﺍ ﺭﺍﺠﺤﹰﺎ‬
‫ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻨﻅﺭﹰﺍ ﺇﻝﻰ ﻜﻭﻨﻪ ﻏﻴﺭ ﻤﺴﺘﻘﺭ‪.‬‬
‫ﻨﺴﺘﻁﻴﻊ ﺒﺎﺴﺘﻌﻤﺎل ﺒﺭﻤﺠﻴﺎﺕ ﻝﻠﻤﺤﺎﻜﺎﺓ ﺃﻥ ﻨﺤﺼل ﻋﻠﻰ ﻤﺨﻁﻁﺎﺕ ﺍﻝﺘﻭﺯﻴﻊ ﺘﻤﺎﻤﹰﺎ ﻤﺜﻠﻤﺎ‬
‫ﻓﻌﻠﻨﺎ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﻤﻀﻴﺔ‪ -‬ﺍﻷﺴﺎﺴﻴﺔ‪ .‬ﻴ‪‬ﻅﻬﺭ ﺍﻝﺸﻜل ) ‪ ( 11‬ﺍﻝﺘﺎﻝﻲ ﻤﺨﻁﻁﺎﺕ ﺘﻭﺯﻴﻊ‬
‫ﻤﻌﻘﺩﺍﺕ ﺍﻝﻨﺸﺎﺩﺭ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻨﺤﺎﺱ ‪ Cu2+‬ﺒﺩﻻﻝﺔ ‪. pNH3‬‬
‫‪%‬‬
‫‪90‬‬ ‫‪[ Cu(NH 3 )4 ]2 +‬‬ ‫‪Cu 2+‬‬
‫‪ւ‬‬ ‫‪ց‬‬
‫‪80‬‬
‫‪70‬‬
‫‪60‬‬ ‫‪[ Cu(NH 3 )2 ]2 +‬‬
‫‪50‬‬
‫↓‬
‫‪40‬‬
‫‪[ Cu(NH 3 ) ]2 +‬‬
‫‪ւ‬‬
‫‪30‬‬
‫‪[ Cu(NH 3 )3 ]2 +‬‬
‫‪20‬‬ ‫‪ց‬‬
‫‪10‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪pNH 3‬‬
‫‪ Cu‬ﺒﺩﻻﻝﺔ ‪pNH3‬‬ ‫‪2+‬‬
‫ﺍﻝﺸﻜل )‪ : (11‬ﻤﺨﻁﻁﺎﺕ ﺘﻭﺯﻴﻊ ﻤﻌﻘﺩﺍﺕ ﺍﻝﻨﺸﺎﺩﺭ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻨﺤﺎﺱ‬
‫ﻭﻴﺒﻴ‪‬ﻥ ﺍﻝﺸﻜل ) ‪ ( 12‬ﻤﺨﻁﻁﺎﺕ ﺘﻭﺯﻴﻊ ﻤﻌﻘﺩﺍﺕ ﺍﻝﻨﺸﺎﺩﺭ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ ‪ Ag+‬ﺒﺩﻻﻝﺔ‬

‫‪. pNH3‬‬
‫‪%‬‬
‫‪90‬‬
‫‪80‬‬ ‫‪ր‬‬ ‫‪տ‬‬
‫‪[ Ag(NH 3 )2 ]+‬‬ ‫‪Ag +‬‬
‫‪70‬‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬ ‫‪[ Ag(NH 3 ) ]+‬‬
‫‪10‬‬ ‫‪ց‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5 pNH 3‬‬
‫‪ Ag‬ﺒﺩﻻﻝﺔ ‪pNH3‬‬ ‫‪+‬‬
‫ﺍﻝﺸﻜل )‪ : (12‬ﻤﺨﻁﻁﺎﺕ ﺘﻭﺯﻴﻊ ﻤﻌﻘﺩﺍﺕ ﺍﻝﻨﺸﺎﺩﺭ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ‬
‫‪ .IV‬ﺍﻝﻤﻌﻘﺩﺍﺕ ﺍﻝﻤﺘﻨﺎﻓﺴﺔ‪:‬‬
‫ﺴﻭﻑ ﻨﻘﺘﺼﺭ ﻋﻠﻰ ﺤﺎﻝﺘﻴﻥ ﺒﺴﻴﻁﺘﻴﻥ ‪:‬‬

‫♣ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ‪ M‬ﻗﺎﺩﺭﺓ ﻋﻠﻰ ﺍﻝﺘﻔﺎﻋل ﻤﻊ ﺍﻝﺭﺒﻴﻁﺘﻴﻥ ‪ L ′ :‬ﻭ ‪. L‬‬
‫♣ ﺍﻝﺭﺒﻴﻁﺔ ‪ L‬ﻗﺎﺩﺭﺓ ﻋﻠﻰ ﺍﻝﺘﻔﺎﻋل ﻤﻊ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﺍﻝﻤﺭﻜﺯﻴﺘﻴﻥ ‪ M ′ :‬ﻭ ‪. M‬‬
‫‪ .1.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺭﺒﻴﻁﺘﻴﻥ ‪ L ′ :‬ﻭ ‪L‬‬
‫ﻥ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ ‪ III‬ﻓﻲ‬

‫ﻝﻨﻌﺩ ﺇﻝﻰ ﺍﻝﺘﺠﺭﺒﺔ ﺍﻝﺘﻲ ﻭﺼﻔﻨﺎﻫﺎ ﻓﻲ ﺒﺩﺍﻴﺔ ﺍﻝﻔﺼل‪ ،‬ﻭﻝﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺘﻔﺎﻋﻠﻬﺎ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺘﻴﻭﺴﻴﺎﻨﺎﺕ ‪ SCN−‬ﺘﻌﻁﻲ ﻤﻌﻘﹼﺩ ﹰﺍ ﺃﺤﻤﺭ ﻫﻭ ﺸﺎﺭﺩﺓ ‪[ Fe(SCN) ]2 +‬‬
‫ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ‪:‬‬
‫‪Fe3+ + SCN− ⇌ [ Fe(SCN) ]2+‬‬
‫ﺤﻴﺙ ‪ K fa = 1.0 × 103‬ﺃﻱ ‪. logK fa = 3.0‬‬
‫ﻭﺘﻌﻁﻲ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ ‪ III‬ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Fe(C2O4 ) ]+‬ﺒﺘﻔﺎﻋﻠﻬﺎ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷ ﻭﻜﺴﺎﻻﺕ‬
‫‪ C2O24−‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪Fe3 + + C2O24− ⇌ [ Fe(C2O4 ) ]+‬‬
‫ﺤﻴﺙ ‪ K fb = 2.5 × 109‬ﺃﻱ ‪. logK fb = 9.4‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ [ Fe(C2O4 ) ]+‬ﻫﻲ ﻤﻌﻘﹼﺩ ﺃﻜﺜﺭ ﺍﺴﺘﻘﺭﺍﺭ ﹰﺍ ﻤﻥ ‪[ Fe(SCN) ]2 +‬‬
‫ﻤﻥ ﺍﻝﻭﺍﻀﺢ ﺃ ‪‬‬
‫ﻥ ‪ ، K fb > K fa‬ﺤﻴﺙ ﺘﺅﺩﻱ ﺇﻀﺎﻓﺔ ﺸﺎﺭﺩﺓ ﺍﻷﻭﻜﺴﺎﻻﺕ ﺇﻝﻰ ﻤﺤﻠﻭل ﺤﺎ ﹴﻭ ﻋﻠﻰ ﺸﻭﺍﺭﺩ‬
‫ﻭﺫﻝﻙ ﻷ ‪‬‬
‫ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﺤﺩﻴﺩ ‪ III‬ﺇﻝﻰ ﺍﺨﺘﻔﺎﺀ ﺍﻝﻤﻌﻘﹼﺩ ﺍﻷﺨﻴﺭ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪[ Fe(SCN) ]2 + + C2O24− ⇌ [ Fe(C2O4 ) ]+ + SCN−‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ‪:‬‬
‫‬ ‫] ‪[[Fe(C2O4 )]+ ] ⋅ [SCN−‬‬

‫= ‪K‬‬
‫] ‪[[Fe(SCN)]2 + ] ⋅ [C2O24−‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫] ‪[[Fe(C2O4 )]+ ] ⋅ [SCN− ] ⋅ [Fe3 +‬‬ ‫‪Kf‬‬
‫‬
‫= ‪K‬‬ ‫=‬ ‫‪b‬‬
‫‪= 2.5 × 106‬‬
‫] ‪[[Fe(SCN)]2+ ] ⋅ [Fe3 + ] ⋅ [C2O24−‬‬ ‫‪Kf‬‬
‫‪a‬‬
‫ﻭﻴﻤﻜﻨﻨﺎ ﻫﻨﺎ ﺇﺫﻥ ﺃﻥ ﻨﻌﺘﺒﺭ ﺍﻝﺘﻔﺎﻋل ﺘﺎﻤﹰﺎ‪.‬‬

‫‪pFe‬‬
‫‪K = 2.5 × 106‬‬

‫‪C2O24−‬‬
‫‪log K fb‬‬
‫‪+‬‬
‫]) ‪[Fe(C2O4‬‬
‫‪SCN−‬‬
‫‪log K fa‬‬
‫‪2+‬‬
‫])‪[Fe(SCN‬‬
‫ﺍﻷﻗﻭﻯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ‪ C2O24− :‬ﻤﻊ ﺍﻝﻤﺎﻨ‪‬ﺢ ﺍﻷﻗﻭﻯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ‬ ‫ﺍﻝﺸﻜل )‪ : (13‬ﺘﻔﺎﻋل ﺍﻝﻤﺘﻘﺒ‪‬ل‬
‫])‪ . [ Fe(SCN‬ﻴﻤﻜﻥ ﺍﻝﻭﺼﻭل ﺇﻝﻰ ﺍﻝﻨﺘﻴﺠﺔ ﺒﺭﺴﻡ ﺤﺭﻑ ‪. γ‬‬
‫‪2+‬‬
‫ﻨﺴﺘﻁﻴﻊ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎ ﻝﺔ ﺍﻝﺨﺎﺼﺔ ﺤﻴﺙ ﻜﺎﻥ ﻝﻠﻤﻌﻘﺩﻴﻥ ﺍﻝﺼﻴﻐﺔ ﺍ ﻝﻌﺎﻤﺔ ] ‪ [ ML‬ﺍ ﻝﺘﻨﺒﺅ‬
‫ﺒﺎﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﺒﺎﺴﺘﻌﻤﺎل ﻤﺨﻁﻁ ) ﻤﺘﻘﺒ‪‬ل ‪ / Fe3 +‬ﻤﺎﻨﺢ ‪ ( Fe3 +‬ﺤﻴﺙ ﻨﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ‬
‫ﺍﻝﺴﺎﺒﻘﻴﻥ ﻋﻠﻰ ﻤﺤﻭﺭ ‪ pFe‬ﺘﺒﻌﹰﺎ ﻝﻘﻴﻤﺘﻲ ‪ ، log K f‬ﻭﻴﺤﺼل ﺍﻝﺘﻔﺎﻋل ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ‬
‫ﻴﻔﻭﻕ ﺍﻝﻭﺍﺤﺩ ﺒﻴﻥ ﺍﻝﻤﺘﻘﺒ‪‬ل ﺍﻷﻜﺜﺭ ﻗﻭﺓ ﻭﺍﻝﻤﺎﻨﺢ ﺍﻷﻜﺜﺭ ﻗﻭﺓ‪ .‬ﻭﻴﻤﻜﻥ ﺇﻴﺠﺎﺩ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺒﺎﺴﺘﻌﻤﺎل‬
‫ﻗﺎﻋﺩﺓ ‪ ، γ‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل )‪.(13‬‬
‫‪ .2.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﺍﻝﻤﺭﻜﺯﻴﺘﻴﻥ‪:‬‬
‫ﻨﺄﺨﺫ ﺃﻨﺒﻭﺏ ﺍﺨﺘﺒﺎﺭ ﻴﺤﻭﻱ ‪ 1 mL‬ﺘﻘﺭﻴﺒﹰﺎ ﻤﻥ ﻤﺤﻠﻭل ﺃﺯﺭﻕ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻨﺤﺎﺱ ‪II‬‬
‫ﺒﺘﺭﻜﻴﺯ ‪ . 0.1 mol/L‬ﻭﻨﻀﻴﻑ ﺇﻝﻴﻪ ﺒﻀﻊ ﻨﻘﺎﻁ ﻤﻥ ﻤﺤﻠﻭل ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬
‫ﻼ‪ .‬ﻭﻴﻌﻭﺩ ﻫﺫﺍ ﺍﻝﻠﻭﻥ ﺇﻝﻰ ﺘﺸﻜﹼل‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻴﺄﺨﺫ ﻝﻭﻨﹰﺎ ﺃﺨﻀﺭ ﺠﻤﻴ ﹰ‬
‫‪ . 0.1 mol/L‬ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩﺓ ‪ [ Cu(SCN) ]+‬ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ‪:‬‬
‫‪Cu2+ + SCN− ⇌ [ Cu(SCN) ]+‬‬
‫ﺤﻴﺙ ‪. K fc = 50‬‬
‫ﻨﻀﻴﻑ ﺍﻵﻥ ﺇﻝﻰ ﺃﻨﺒﻭﺏ ﺍﻻﺨﺘﺒﺎﺭ‪ ،‬ﻨﻘﻁﺔ ﻨﻘﻁﺔ‪ ،‬ﻤﺤﻠﻭل ﻜﻠﻭﺭ ﺍﻝﺤﺩﻴﺩ ‪ III‬ﺒﺘﺭﻜﻴﺯ ‪0.1 mol/L‬‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻴﺘﺤﻭ‪‬ل ﺇﻝﻰ ﺍﻝﻠﻭﻥ ﺍﻷﺤﻤﺭ ﺍﻝﻤﻤﻴ‪‬ﺯ ﻝﻠﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩﺓ ‪[ Fe(SCN) ]2 +‬‬
‫ﻓﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﻤﺘﺸﻜﹼﻠﺔ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ‪:‬‬
‫‪Fe3+ + [ Cu(SCN) ]+ ⇌ [ Fe(SCN) ]2 + + Cu2+‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‬
‫] ‪[[Fe(SCN)]2 + ] ⋅ [Cu2 +‬‬

‫= ‪K0‬‬
‫] ‪[Fe3 + ] ⋅ [[Cu(SCN)]+‬‬
‫ﺃﻭ ﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ‬
‫] ‪[[Fe(SCN)]2 + ] ⋅ [Cu2 + ] ⋅ [SCN−‬‬ ‫‪Kf‬‬

‫= ‪K0‬‬ ‫=‬ ‫‪a‬‬
‫‪= 20‬‬
‫] ‪[Fe3 + ] ⋅ [SCN− ] ⋅ [[Cu(SCN)]+‬‬ ‫‪Kf‬‬
‫‪c‬‬
‫ﻥ ﺸﺎﺭﺩﺓ ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﺤﺩﻴﺩ ‪ III‬ﻫﻲ ﻤﻌﻘﺩ ﺃﻜﺜﺭ ﺍﺴﺘﻘﺭﺍﺭﹰﺍ ﻤﻥ ﺸﺎﺭﺩﺓ ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﻨﺤﺎﺱ ‪. II‬‬
‫ﺇ‪‬‬
‫ﻴﻔﻴﺩ ﺍﺴﺘﻌﻤﺎل ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻤﺘﻘﺒ‪‬ل ﻝﻠﺭﺒﻴﻁﺔ‪ /‬ﻤﺎﻨﺢ ﻝﻠﺭﺒﻴﻁﺔ‪ ،‬ﻭ ﺫﻝﻙ ﺒﻭﻀﻊ ﺍﻝﺯﻭﺠﻴﻥ‬
‫ﺍﻝﺴﺎﺒﻘﻴﻥ ﻋﻠﻰ ﻤﺤﻭﺭ ‪ ، pSCN‬ﻓﻲ ﺇﻴﺠﺎﺩ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل‪ ،‬ﻷﻨﻨﺎ ﻫﻨﺎ ﺃﻴﻀﹰﺎ ﺃﻤﺎﻡ ﺤﺎﻝﺔ ﺨﺎﺼﺔ ﺇﺫ‬
‫ﻴﺘﻤﺘﻊ ﻜﻼ ﺍﻝﻤﻌﻘﹼﺩﻴﻥ ﺒﺎﻝﺼﻴﻐﺔ ﺍﻝﻌﺎﻤﺔ ]‪ .[ML‬ﻭﻴﺠﺭﻱ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺫﻱ ﻴﻤﺘﻠﻙ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ ﺃﻜﺒﺭ ﻤﻥ‬
‫ﺍﻝﻭﺍﺤﺩ ﺒﻴﻥ ﺍﻝﻤﺘﻘﺒ‪‬ل ﺍﻷﻗﻭﻯ ﻝﻠﺭﺒﻴﻁﺔ ﻭﺍﻝﻤﺎﻨﺢ ﺍﻷﻗﻭﻯ ﻝﻬﺎ‪ ،‬ﻭﻴﻤﻜﻥ ﺍﻝﺘﻨﺒ‪‬ﺅ ﺒﺠﻬﺔ ﺍﻝﺘﻔﺎﻋل ﺒﺎﺴﺘﻌﻤﺎل‬
‫ﻗﺎﻋﺩﺓ ‪ ، γ‬ﺍﻝﺸﻜل ) ‪. ( 14‬‬
‫‪pSCN‬‬
‫‪K = 20‬‬
‫‪Fe3+‬‬ ‫‪log K fa‬‬
‫‪[ Fe(SCN) ]2 +‬‬
‫‪Cu2+‬‬ ‫‪log K fc‬‬

‫‪[ Cu(SCN) ]+‬‬
‫ﺍﻝﺸﻜل )‪ : (14‬ﺘﻔﺎﻋل ‪) Fe3+‬ﻤﺘﻘﺒ‪‬ل ﺭﺒﻴﻁﺔ ﺍﻝﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻷﻗﻭﻯ( ﻤﻊ ﻤﺎﻨﺤﻬﺎ ﺍﻷﻗﻭﻯ ])‪[Cu(SCN‬‬

‫‪+‬‬
‫ﻭ ﻴﻤﻜﻥ ﺒﺎﻝﻁﺭﻴﻘﺔ ﺫﺍﺘﻬﺎ ﺍﻝﺘﻨﺒ‪‬ﺅ ﺒﺘﻔﻜﹼﻙ ﻤﻌﻘﹼﺩ ﻤﺎ ﻤﺘﻤﺘﻊ ﺒﻤﻨﺎﻁﻕ ﺭﺠﺤﺎﻥ ﻤﺘﻤﺎﻴﺯﺓ ﻜﻤﺎ ﻫﻭ‬
‫ﺤﺎل ﺍﻝﻤﻌﻘﹼﺩ ‪ ، [ Ag(NH3 ) ]+‬ﺍﻝﺸﻜل )‪.(15‬‬
‫‪2 [ Ag(NH3 ) ]+ ⇌ Ag+ + [ Ag(NH3 )2 ]+‬‬
‫‪pNH3‬‬
‫‪[ Ag(NH3 ) ]+‬‬

‫‪3.9‬‬
‫‪[ Ag(NH3 )2 ]+‬‬
‫‪Ag+‬‬
‫‪3.3‬‬
‫‪[ Ag(NH3 ) ]+‬‬
‫ﺍﻝﺸﻜل )‪ : (15‬ﻅﻬﻭﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﺩﺓ ]) ‪ [ Ag(NH3‬ﻜﺄﻗﻭﻯ ﻤﺎﻨﺢ ﻭﺃﻗﻭﻯ ﻤﺘﻘﺒ‪‬ل ﻝﻠﺭﺒﻴﻁﺔ ‪. NH3‬‬
‫‪+‬‬
‫

‬
‫ﻤﺎ ﻫﻲ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻀﺎﺩﺓ )ﺍﻝﺘﺭﻴﺎﻕ( ﻝﻤﻌﺎﻝﺠﺔ ﺍﻝﺘﺴﻤﻡ ﺒﺎﻝﺴﻴﺎﻨﻴﺩ؟‬
‫ﺇﻥ ﺍﻝﺴﻤﻴﺔ ﺍﻝﻌﺎﻝﻴﺔ ﻝﻠﻤﺭﻜﺒﺎﺕ ﺍﻝﺤﺎﻭﻴﺔ ﻋﻠﻰ ﻤﺎﺩﺓ ﺍﻝﺴﻴﺎﻨﻴﺩ ﺘﺘﻁﻠﺏ ﺘﻁﺒﻴﻘﹰﺎ ﻓﻭﺭﻴ ﹰﺎ ﻝﻤﺎﺩﺓ ﻁﺒﻴﺔ ﺘﹸﻌﺭ‪‬ﻑ ﺒﺎﺴﻡ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻀﺎﺩﺓ‬
‫ﺃﻭ ﺍﻝﺘﺭﻴﺎﻕ ‪ ،Antidote‬ﻓﻤﺎ ﻫﻭﺍﻝﻤﺒﺩﺃ ﺍﻝﻜﻴﻤﻴﺎﺌﻲ ﺍﻝﺫﻱ ﻜﺎﻥ ﻭﺭﺍﺀ ﺴ ‪‬ﻤﻴ‪‬ﺔ ﺍﻝﺴﻴﺎﻨﻴﺩ‪ ،‬ﻭﻜﻴﻑ ﻨﺴﺘﻁﻴﻊ ﺒﻨﺎﺀ ﻋﻠﻰ ﺫﻝﻙ‬
‫ﺇﻴﺠﺎﺩ ﻤﺎﺩﺓ ﻤﻀﺎﺩﺓ ﻝﺴﻤﻴﺔ ﺍﻝﺴﻴﺎﻨﻴﺩ؟‬
‫ﻥ ﻋﻤﻠﻴﺔ ﺍﻝﺘﻨﻔﺱ‪ ،‬ﺍﻝﺘﻲ ﺘﻌﺘﻤﺩ ﻋﻠﻰ ﻨﻘل ﺍﻷﻜﺴﺠﻴﻥ ‪ O2‬ﻋﺒﺭ ﺍﻝﺩﻡ ﻤﻥ ﺍﻝﺭﺌﺘﻴﻥ ﺇﻝﻰ ﺍﻝﺨﻼﻴﺎ ﺜ ‪‬ﻡ ﻨﻘل ﻏﺎﺯ‬
‫ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ‪ CO2‬ﻤﻥ ﺍﻝﺨﻼﻴﺎ ﺇﻝﻰ ﺍﻝﺭﺌﺘﻴﻥ‪ ،‬ﺘﺘ ‪‬ﻡ ﺒﻭﺍﺴﻁﺔ ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩﺍﺕ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ‬
‫ل ﻤﻥ ﻫﺫﻴﻥ ﺍﻝﻐﺎﺯﻴﻥ‪ .‬ﻭﻫﺫﻩ ﺍﻝﻤﻌﻘﺩﺍﺕ ﻗﺎﺒﻠﺔ ﻝﻠﺘﻔﻜﻙ ﻭﻫﻲ ﻝﻴﺴﺕ ﺫﺍﺕ ﺜﺎﺒﺕ ﺘﺸﻜﹼل ﻤﺭﺘﻔﻊ‪.‬‬
‫ﺨﻀﺎﺏ ﺍﻝﺩﻡ ﻤﻊ ﻜ ّ‬
‫ﺘﻌﻭﺩ ﺴ ‪‬ﻤﻴ‪‬ﺔ ﺸﺎﺭﺩﺓ ﺍﻝﺴﻴﺎﻨﻴﺩ ﺇﻝﻰ ﻗﺎﺒﻠﻴﺘﻬﺎ ﺍﻝﺸﺩﻴﺩﺓ ﺇﻝﻰ ﺘﺸﻜﻴل ﻤﻌﻘﹼﺩﺍﺕ ﻋﺎﻝﻴﺔ ﺍﻻﺴﺘﻘﺭﺍﺭ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ‬
‫ﻓﻲ ﺨﻀﺎﺏ ﺍﻝﺩﻡ‪ ,‬ﻓﻼ ﺘﻌﻭﺩ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺠﺎﻫﺯﺓ ﻝﻠﻘﻴﺎﻡ ﺒﻌﻤﻠﻬﺎ ﻓﻲ ﺘﺸﻜﻴل ﻤﻌﻘﺩﺍﺕ ﻋﻜﻭﺴﺔ ﻤﻊ ﺍﻷﻜﺴﺠﻴﻥ ﻭﻏﺎﺯ‬
‫ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻻ ﺘﻘﻭﻡ ﻜﺭﻴﺎﺕ ﺍﻝﺩﻡ ﺍﻝﺤﻤﺭﺍﺀ ﺒﻭﻅﻴﻔﺘﻬﺎ ﻓﻲ ﻋﻤﻠﻴﺔ ﺍﻝﺘﻨﻔﺱ‪ ،‬ﻓﺘﺘﻭﻗﹼﻑ ﺍﻝﺨﻼﻴﺎ ﻋﻥ ﻋﻤﻠﻬﺎ‬
‫ﻋﻨﺩ ﺘﻭﻗﹼﻑ ﺘﻨﻔﺴﻬﺎ‪ ،‬ﻭﻫﺫﺍ ﻴﺅﺩﻱ ﺇﻝﻰ ﻤﻭﺘﻬﺎ‪.‬‬
‫ﻭﻝﺫﻝﻙ ﻋﻨﺩ ﺒﺤﺜﻨﺎ ﻋﻥ ﻤﺎﺩﺓ ﻤﻀﺎﺩﺓ ﻝﻠﺴﻴﺎﻨﻴﺩ ﻋﻠﻴﻨﺎ ﺃﻥ ﻨﺒﺤﺙ ﻋﻥ ﻤﺎﺩﺓ ﺘﺸﻜﹼل ﻤﻊ ﺍﻝﺴﻴﺎﻨﻴﺩ ﻤﻌﻘﺩﺍﺕ ﺃﻜﺜﺭ ﺍﺴﺘﻘﺭﺍﺭﹰﺍ ﻤﻥ‬
‫ﺍﻝﻤﻌﻘﹼﺩ ﺍﻝﺫﻱ ﺘﺸﻜﻠﻪ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﻝﺘﺘﺤﺭ‪‬ﺭ ﻤﻥ ﺠﺩﻴﺩ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﻝﺘﻘﻭﻡ ﺒﻭﻅﻴﻔﺘﻬﺎ ﻓﻲ ﺍﻝﺘﻨﻔﹼﺱ‪ .‬ﻭﺃﺤﺩ ﻫﺫﻩ ﺍﻝﻤﻭﺍﺩ‬
‫ﺍﻝﻤﻀﺎﺩﺓ ﻴﺤﻤل ﺍﻻﺴﻡ ﺍﻝﺘﺠﺎﺭﻱ ‪ Kelocyamor‬ﺤﻴﺙ ﺘﻀﻡ ﺍﻝﻌﺒﻭﺓ ﻤﻨﻪ ‪ 300 mg‬ﻤﻥ ‪ Co3 EDTA‬ﺃﻱ‬
‫‪ CoY2−‬ﻭﻫﻭ ﻤﻌﻘﺩ ﻝﺸﻭﺍﺭﺩ ﺍﻝﻜﻭﺒﺎﻝﺕ ﻤﻊ ﺍﻝـ ‪: EDTA‬‬
‫‪Co2+ +Y 4 − ⇌ CoY 2−‬‬
‫ﻴﻘﻭﻡ ﺍﻝﻌﻤل ﺍﻝﻤﻘﺎﻭﻡ ﻝﻠﺴﻤﻴﺔ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﺎﺩﺓ ﻋﻠﻰ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻜﺒﻴﺭﺓ ﻝﺸﺎﺭﺩﺓ ﺍﻝﻜﻭﺒﺎﻝﺕ ﻋﻠﻰ ﺍﻝﺘﻔﺎﻋل ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺎﻨﻴﺩ‪:‬‬
‫‪Co2+ (aq) + 6 CN− (aq) [Co(CN)6 ]4 −‬‬ ‫‪K f = 1.2×1019‬‬
‫ﺇﺫ ﺘﺘﺸﻜل ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﺩﺓ ‪ [Co(CN)6 ]4 −‬ﻏﻴﺭ ﺍﻝﺴﺎﻤﺔ ﻭﺍﻝﻌﺎﻝﻴﺔ ﺍﻻﺴﺘﻘﺭﺍﺭ ﻓﻴﺘﻔﻜﻙ ﺘﺩﺭﻴﺠﻴ ﹰﺎ ﺍﻝﻤﻌﻘﺩ ﺍﻝﺫﻱ ﺘﺸﻜﹼل‬
‫ﺒﻴﻥ ﺸﺎﺭﺩﺓ ﺍﻝﺴﻴﺎﻨﻴﺩ ﻭﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﺍﻝﺩﻡ‪ ،‬ﻝﺘﻌﻭﺩ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﻭﺘﺯﺍﻭل ﻭﻅﻴﻔﺘﻬﺎ ﻓﻲ ﺍﻝﺘﻨﻔﺱ‪ .‬ﻭﻫﻜﺫﺍ ﺘﺅﺩﻱ‬
‫ﺸﻭﺭﺩ ﺍﻝﻜﻭﺒﺎﻝﺕ ‪ Co2+‬ﺩﻭﺭ ﻤﺼﻴﺩﺓ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺎﻨﻴﺩ ‪ CN−‬ﺍﻝﺴﺎﻤﺔ‪ ،‬ﻭﻋﻤﻠﻬﺎ ﻴﻘﻭﻡ ﻜﻤﺎ ﺭﺃﻴﻨﺎ ﻋﻠﻰ ﻤﺒﺩﺃ ﺍﻝﺘﻨﺎﻓﺱ‬
‫ﺒﻴﻥ ﺸﺎﺭﺩﺘﻴﻥ ﻤﻌﺩﻨﻴﺘﻴﻥ ﻓﻲ ﺘﺸﻜﻴل ﻤﻌﻘﺩﻴﻥ‪.‬‬
‫‪ .V‬ﺘﻤﺭﻴﻥ ﻤﺤﻠﻭل‬
‫‪‬ﻴﺒﻴ‪‬ﻥ ﺍﻝﺸﻜل ) ‪ ( 16‬ﻨﻤﺫﺠ ﹰﺔ ﻝﺘﺠﺭﺒﺔ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻤﻥ ﻤﺭ ﻜﹼﺏ ﺃ ﻭ ﻜﺴﺎﻻﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‬

‫ﺒﺘﺭ ﻜﻴﺯ ‪ c1 = 1.00 mol/L‬ﺇ ﻝﻰ ﺤﺠﻡ ‪ V2 = 10.0 mL‬ﻤﻥ ﻤﺭ ﻜﹼﺏ ﻨﺘﺭ ﺍ ﺕ ﺍ ﻝﻜﺎ ﺩ ﻤﻴﻭﻡ‬
‫ﺒﺘﺭﻜﻴﺯ ‪. c2 = 0.10 mol/L‬‬
‫‪%‬‬
‫‪90‬‬
‫‪80‬‬
‫‬ ‫‬
‫‪70‬‬
‫‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪pC2 O4‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬
‫ﺍﻝﺸﻜل )‪ : (16‬ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﺍﻝﻨﺎﺘﺞ ﻋﻥ ﻨﻤﺫﺠﺔ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻤﻥ ﺃﻭﻜﺴﺎﻻﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻜﺎﺩﻤﻴﻭﻡ‪.‬‬
‫ﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺜﻼﺙ ﻓﻲ ﻫﺫﺍ ﺍﻝﺸﻜل ﺘﻤﺜﹼل ﺘﻐ‪‬ﻴﺭﺍﺕ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻜل ﻤﻥ ‪Cd2+‬‬
‫ﻨﻌﻠﻡ ﺃ ‪‬‬
‫ﻭ ] ‪ [ Cd C2O4‬ﻭ ‪ [ Cd ( C2O4 )2 ]2−‬ﺒﺩﻻﻝﺔ ‪ p C2O4‬ﺍﻝﻤﻁﻠﻭﺏ‪:‬‬
‫‪ .1‬ﻤﺎ ﻫﻭ ﺍﻝﻤﺭﻜﺏ ﺍﻝﻜﻴﻤﻴﺎﺌﻲ ﺍﻝﺫﻱ ﺘﻤﺜﹼﻠﻪ ﻜل ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺜﻼﺜﺔ ﺍﻝﺴﺎﺒﻘﺔ؟‬
‫‪ .2‬ﺍ ﺤﺴﺏ ﺜﻭ ﺍﺒﺕ ﺍ ﻝﺘﺸﻜﹼل ﺍ ﻝﻤﺘﻌﺎ ﻗﺒﺔ ﺜ ‪‬ﻡ ﺍﺴﺘﻨﺘﺞ ﺜﺎ ﺒﺕ ﺍ ﻝﺘﺸﻜﹼل ﺍ ﻹ ﺠﻤﺎ ﻝﻲ‪ .‬ﺍ ﺭﺴﻡ ﻤﺨﻁﻁ‬
‫ﺍﻝﺭﺠﺤﺎﻥ ﻝﻜل ﻤﻥ ‪ Cd2+‬ﻭ ] ‪ [ Cd C2O4‬ﻭ ‪ [ Cd ( C2O4 )2 ]2−‬ﺒﺩﻻﻝﺔ ‪. p C2O4‬‬
‫ل ﻤﻥ ‪ Cd2+‬ﻭ ] ‪ [ Cd C2O4‬ﻭ ‪ [ Cd ( C2O4 )2 ]2−‬ﺒﺈﻫﻤﺎل ﻤﻌﺎﻤل‬

‫‪ .3‬ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺯ ﻜ ّ‬
‫ﺍﻝﺘﻤﺩﻴﺩ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ‪. [ C2O24− ] = 10−2 mol/L‬‬
‫ﺍﻝﺤل‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ ﻝﺘﺸﻜﻴل ﺍﻝﻤﻌﻘﺩﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ ﻫﻤﺎ ‪:‬‬
‫‪ .1‬ﺇ ‪‬‬
‫] ‪Cd2 + + C2O24− ⇌ [ Cd C2O4‬‬ ‫)‪(α‬‬

‫‪[ Cd (C2O4 ) ] + C2O24− ⇌ [ Cd(C2O4 )2 ]2−‬‬ ‫) ‪(β‬‬
‫ﻥ ] ‪ [C2O24−‬ﻴﻜﻭ ﻥ ﺼﻐﻴﺭ ﹰﺍ ‪ ،‬ﻭ ﻤﻥ ﹶﺜ ‪‬ﻡ ﻻ ﻴﻜﻭ ﻥ ﺍ ﻝﺘﻔﺎ ﻋﻼﻥ‬

‫ﻋﻨﺩﻤﺎ ﻴﻜﻭ ﻥ ‪ p C2O4‬ﻜﺒﻴﺭ ﹰﺍ ﻓﺈ ‪‬‬
‫ﻥ ‪ Cd2+‬ﻴﻜﻭﻥ ﻏﻴﺭ ﻤﻌﻘﹼﺩ ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯﻩ ﺭﺍﺠﺤﹰﺎ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﺍﻝﺴﺎﺒﻘﺎﻥ ﻤﺤﺒ‪‬ﺫﻴﻥ‪ .‬ﺃﻱ ﺇ ‪‬‬
‫ل ﻤﻥ ﺍﻝﻤﻌﻘﹼﺩﻴﻥ ] ‪[ Cd C2O4‬‬
‫ﻋﻨﺩﻤﺎ ﻴﺘﻨﺎﻗﺹ ‪ p C2O4‬ﻴﺒﺩﺃ ﺍﻝﺘﻔﺎﻋﻼﻥ ﺍﻝﺴﺎﺒﻘﺎﻥ ‪ ،‬ﻭﻴﺘﺸﻜﹼل ﻜ ﱞ‬
‫ﻭ ‪ . [ Cd ( C2O4 )2 ]2−‬ﻓﻴﻌﻭﺩ ﺍﻝﻤﻨﺤﻨﻲ ﺭ ﻗﻡ ﺇﻝﻰ ﺍﻝﻤﻌﻘﹼﺩ ‪ ، [ Cd ( C2O4 )2 ]2−‬ﻭ ﻴﻌﻭﺩ‬
‫ﺍﻝﻤﻨﺤﻨﻲ ﺭﻗﻡ ﺇﻝﻰ ] ‪ ، [ Cd C2O4‬ﻓﻲ ﺤﻴﻥ ﻴﻌﻭﺩ ﺍﻝﻤﻨﺤﻨﻲ ﺭﻗﻡ ﺇﻝﻰ ‪. Cd2+‬‬
‫ﻥ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻝﺘﻌﺎﻗﺒﻲ ﻝﻠﺘﻔﺎﻋل )‪ (α‬ﻫﻭ‪:‬‬

‫‪ .2‬ﺇ ‪‬‬
‫] ] ‪[ [ Cd C2O4‬‬
‫‪K f1‬‬ ‫=‬
‫] ‪[ Cd2+ ] ⋅ [ C2O24−‬‬
‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻋﻨﺩ ﻨﻘﻁﺔ ﺘﻘﺎﻁﻊ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ ﻭ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺴﺎﻭﺍﺓ‬
‫] ‪[ [ Cd C2O4 ] ] = [ Cd2+‬‬
‫ﻭﻴﻜﻭﻥ ﻋﻨﺩﻫﺎ ‪ . p C2O4 = log K f1‬ﻭﻤﻨﻪ‬
‫‪. K f1 = 6.3 × 102‬‬ ‫ﺃﻱ‬ ‫‪log K f1 = 2.8‬‬
‫ﻥ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻝﺘﻌﺎﻗﺒﻲ ﻝﻠﺘﻔﺎﻋل ) ‪ ( β‬ﻫﻭ‪:‬‬
‫ﻭﺇ ‪‬‬
‫‪2‬‬
‫‪ [ Cd ( C2O4 )2 ] ‬‬‫‪−‬‬
‫‪K f2‬‬ ‫=‬ ‫‪‬‬ ‫‪‬‬
‫] ‪[ [ Cd C2O4 ] ] ⋅ [ C2O24−‬‬
‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻋﻨﺩ ﻨﻘﻁﺔ ﺘﻘﺎﻁﻊ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ ﻭ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺴﺎﻭﺍﺓ‬
‫‪[ [ Cd C2O4 ] ] =  [ Cd ( C2O4 )2 ]2− ‬‬
‫ﻭﻴﻜﻭﻥ ﻋﻨﺩﻫﺎ ‪ . p C2O4 = log K f2‬ﻭﻤﻨﻪ ﻨﺠﺩ‬
‫‪ log K f2 = 1.8‬ﺃﻱ ‪. K f2 = 63‬‬
‫ﺃﻤﺎ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻹﺠﻤﺎﻝﻲ ﻓﻬﻭ ﻴﺴﺎﻭﻱ ‪:‬‬
‫‪β = K f1 × K f2 ≃ 40000‬‬
‫ﻭﻴﺄﺨﺫ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ ‪:‬‬
‫‪[ Cd(C2O4 )2 ]2 −‬‬ ‫] ) ‪[ Cd(C 2O 4‬‬ ‫‪Cd 2+‬‬
‫‪1.8‬‬ ‫‪2.8‬‬ ‫‪pC 2O 4‬‬

‫ل ﻤﻥ ‪Cd2+‬‬
‫‪ .3‬ﻓﻲ ﺍ ﻝﺤﺎ ﻝﺔ ﺍ ﻝﺘﻲ ﻴﻜﻭ ﻥ ﻓﻴﻬﺎ ‪ p C2O4 = 2‬ﺘﹸﻘﺭ ﺃ ﺍ ﻝﻨﺴﺏ ﺍ ﻝﻤﺌﻭ ﻴﺔ ﻝﻜ ﱟ‬
‫ﻭ ] ‪ [ Cd C2O4‬ﻭ ‪ [ Cd ( C2O4 )2 ]2−‬ﻤﻥ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﻓﻨﺠﺩ ‪:‬‬
‫‪[ Cd ( C2O4 )2 ]2−‬‬ ‫] ‪[ Cd C2O4‬‬ ‫‪Cd2+‬‬
‫‪36%‬‬ ‫‪55%‬‬ ‫‪9%‬‬
‫ﻭﺒﺈﻫﻤﺎل ﺍﻝﺘﻤﺩﻴﺩ ﻴ‪‬ﻜﺘﹶﺏ ﺸﺭﻁ ﺍﻨﺤﻔﺎﻅ ﻋﻨﺼﺭ ﺍﻝﻜﺎﺩﻤﻴﻭﻡ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪[ Cd2+ ] + [ [ Cd C2O4 ] ] +  [ Cd ( C2O4 )2 ]2−  = 0.1 mol/L‬‬

‫ﻥ‪:‬‬
‫‪[ Cd2+ ] = 9.0 × 10−3 mol/L‬‬
‫‪[ [ Cd C2O4 ] ] = 5.5 × 10−2‬‬ ‫‪mol/L‬‬
‫‪‬‬ ‫‪2− ‬‬ ‫‪−2‬‬
‫‪ [ Cd ( C2O4 )2 ]  = 3.6 × 10‬‬ ‫‪mol/L‬‬
‫‪ .VI‬ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪ -‬ﺘﺭﻜﻴﺏ ﻤﺤﻠﻭل‬
‫ﻝﻨﺒﻴ‪‬ﻥ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﺒﻌﺽ ﺍﻷﻤﺜﻠﺔ ﻜﻴﻔﻴﺔ ﺇﻴﺠﺎﺩ ﺘﺭﻜﻴﺏ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﻤﻌﻘﺩﺍﺕ ﺍﻨﻁﻼﻗﹰﺎ ﻤﻥ‬
‫ﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﻴل ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﻬﺫﻩ ﻝﻤﻌﻘﺩﺍﺕ ﻭﺍﻝﺘﺭﻜﻴﺏ ﺍﻻﺒﺘﺩﺍﺌﻲ ﻝﻠﻤﺤﻠﻭل‪ .‬ﻭﺴﻴﻘﻭﻡ ﻋﻤﻠﻨﺎ ﻜﻤﺎ ﻓﻌﻠﻨﺎ‬
‫ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻤﻥ ﺍﻝﻨﻭﻉ ﺤﻤﺽ – ﺃﺴﺎﺱ ﻋﻠﻰ ﺍﺘﺒﺎﻉ ﺍﻝﺨﻁﻭﺍﺕ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫ ﺘﺤﺩﻴﺩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺭﺍﺠﺤﺔ ﺍﻝﻤﺘﻌﺎﻗﺒﺔ‪.‬‬
‫ ﻭﻀﻊ ﺒﻌﺽ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﺘﺒﺴﻴﻁﻴﺔ ﻋﻨﺩ ﺍﻝﻠﺯﻭﻡ‪.‬‬
‫ ﺤل ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺎﺘﺠﺔ‪.‬‬
‫ ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﻤﻭﻀﻭﻋﺔ ﺒﺎﻝﻠﺠﻭﺀ ﺇﻝﻰ ﻤﺨﻁﻁﺎﺕ ﺍﻝﺭﺠﺤﺎﻥ ﻋﻠﻰ ﺴﺒﻴل‬
‫ﺍﻝﻤﺜﺎل‪.‬‬
‫‪ .1.VI‬ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ ﻭﺤﻴﺩ‬
‫ﻫﺫﺍ ﻫﻭ ﺍﻝﺤﺎل ﻋﻨﺩ ﺩﺭﺍﺴﺔ ﺍﻝﻤﻌﻘﺩﺍﺕ ﺍﻝﻤﺘﺸﻜﹼﻠﺔ ﻤﻊ ﺍﻝﺭﺒﻴﻁﺔ ﺍﻝﺴﺩﺍﺴﻴﺔ ﺍﻝﺴﻥ ﻝﺸﺎﺭﺩﺓ‬
‫‪ E.D.T.A‬ﺍﻝﺘﻲ ﻨﺭﻤﺯ ﻝﻬﺎ ﻋﺎﺩﺓ ﺒﺎﻝﺭﻤﺯ ‪.Y 4−‬‬
‫ﻤﺜﺎل‪ :‬ﻝﻨﺤﻀ‪‬ﺭ ﻝﻴﺘﺭﹰﺍ ﻤﻥ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ‪ 0.10 mol‬ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﻜﻤﻴﺔ ‪ n‬ﻤﻥ‬
‫ﺇﻴﺜﻠﻴﻥ ﺜﻨﺎﺌﻲ ﺃﻤﻴﻥ ﺭﺒﺎﻋﻲ ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ) ‪ . (4 Na + + Y 4−‬ﺃﻭﺠﺩ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ‬

‫ﻝﻠﻤﺤﻠﻭل ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺜﻼﺙ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫)‪n = 0.15 mol (c‬‬ ‫)‪n = 0.10 mol (b‬‬ ‫)‪n = 0.02 mol (a‬‬
‫ﻥ ﻗﻴﻤﺔ ‪log β1‬‬
‫ﻥ ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻌﻘﻴﺩ ﻫﻲ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻭﺤﻴﺩﺓ ﺍﻝﻤﻌﺘﺒﺭﺓ‪ ،‬ﻭﺃ ‪‬‬
‫ﺘﺴﺎﻭﻱ ‪. 10.7‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﻭﺤﻴﺩ ﺍﻝﺫﻱ ﺴﻴﺠﺭﻱ ﺍﻝﻨﻅﺭ ﻓﻴﻪ ﻫﻭ ﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ Ca 2 +‬ﻤﻊ ﺸﺎﺭﺩﺓ‬
‫‪ E.D.T.A.‬ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪Ca 2 + + Y 4− ⇌ [CaY ]2−‬‬ ‫)‪(1‬‬
‫ﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﻫﻭ ‪ K 0 = β1 = 5.0 × 1010‬ﻭﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ‪ .‬ﻝﻨﺩﺭﺱ ﺍﻝﺤﺎﻻﺕ‬

‫ﺇ‪‬‬
‫ﺍﻝﺜﻼﺙ‪:‬‬
‫• )‪n = 0.02 mol (a‬‬
‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﻫﻨﺎ ﻓﺎﺌﺽ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪ ،‬ﻭﻨﻜﺘﺏ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﺜ ‪‬ﻡ ﺍﻝﺘﺭﺍﻜﻴﺯ ﻋﻨﺩ ﻭﻀﻊ‬
‫ﺍﻝﺘﻭﺍﺯﻥ ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﺍﻝﺘﻔﺎﻋل‪:‬‬
‫‪Ca 2 +‬‬ ‫‪+ Y 4−‬‬ ‫‪ [CaY ]2−‬‬
‫‪t = 0 0.10‬‬ ‫‪0.02‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪0.08‬‬ ‫‪ε‬‬ ‫‪0.02‬‬
‫ﻭﻨﺤﺴﺏ ‪ ε‬ﺒﺎﺴﺘﻌﻤﺎل ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‪:‬‬
‫] ‪[[CaY ]2−‬‬
‫= ] ‪[Y 4−‬‬ ‫‪= 5.0 × 10−12 mol / L‬‬
‫‪2+‬‬
‫‪β1 ⋅ [Ca‬‬ ‫]‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪. pY = − log[Y 4- ] = 11.3‬‬
‫• )‪n = 0.10 mol (b‬‬

‫ﺘﻜﻭﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺸﻭﺍﺭﺩ ‪ .E.D.T.A‬ﻭﻓﻕ ﺍﻝﻨﺴﺏ ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﻭﻨﻜﺘﺏ‪:‬‬
‫‪Ca 2 +‬‬ ‫‪+ Y 4−‬‬ ‫‪ [CaY ]2−‬‬
‫‪t = 0 0.10‬‬ ‫‪0.10‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪ε‬‬ ‫‪0.10‬‬
‫‪ [[CaY ]2− ] 0.5‬‬
‫‪[Ca‬‬ ‫‪2+‬‬
‫‪] = [Y‬‬ ‫‪4−‬‬
‫‪] = ‬‬ ‫‪ = 1.4 × 10−6 mol / L‬‬
‫‪‬‬ ‫‪β‬‬ ‫‪1‬‬
‫‪‬‬
‫‪1‬‬
‫ﻥ‪. pY = − log[Y 4− ] = (log β1 − log[[CaY ]2− ]) = 5.85 :‬‬
‫‪2‬‬
‫• )‪n = 0.15 mol (c‬‬
‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﻫﻨﺎ ﻓﺎﺌﺽ ﻤﻥ ﺸﻭﺍﺭﺩ ‪ E.D.T.A‬ﻭﻨﻜﺘﺏ‪:‬‬
‫‪Ca 2 +‬‬ ‫‪+ Y 4−‬‬ ‫‪ [CaY ]2−‬‬

‫‪t = 0 0.10‬‬ ‫‪0.15‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪0.05‬‬ ‫‪0.10‬‬
‫] ‪[[CaY ]2−‬‬
‫= ] ‪[Ca 2 +‬‬ ‫‪= 4.0 × 10−11 mol / L‬‬
‫‪4−‬‬
‫‪β1 ⋅ [Y‬‬ ‫]‬
‫ﻥ‪. pY = 1.3 :‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃ ‪‬‬
‫ﺍﻝﺘﺤﻘﹼﻕ‪ :‬ﻝﻨﻀﻊ ﻋﻠﻰ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﻤﺩﺭﺝ ﺒﺩﻻﻝﺔ ‪ pY‬ﺍﻝﻘﻴﻡ ﺍﻝﺜﻼﺙ ﺍﻝﺘﻲ ﻭﺠﺩﻨﺎﻫﺎ ﻋﻨﺩ‬
‫ﺩﺭﺍﺴﺔ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺜﻼﺜﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺒﻐﻴﺔ ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﺘﻲ ﺍﻋﺘﻤﺩﻨﺎﻫﺎ ﻭﺍﻝﺘﻲ ﻗﺎﺩﺘﻨﺎ‬
‫ﺇﻝﻰ ﺍﻝﻘﻴﻡ ﺍﻝﻤﺨﺘﻠﻔﺔ ﻝﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل‪:‬‬
‫‪[CaY ]2−‬‬ ‫‪Ca 2 +‬‬

‫‪1.3‬‬ ‫‪5.85‬‬ ‫‪10.7‬‬ ‫‪11.3‬‬ ‫‪pY‬‬
‫ﺍﻝﻤﺤﻠﻭل ‪c‬‬ ‫ﺍﻝﻤﺤﻠﻭل ‪b‬‬ ‫ﺍﻝﻤﺤﻠﻭل ‪a‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pY = 11.3‬ﺍﻝﺘﻲ ﻭﺠﺩﻨﺎﻫﺎ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻷﻭل )‪ (a‬ﺘﻭﺍﻓﻕ ﺭﺠﺤﺎﻥ ﺘﺭﻜﻴﺯ‬

‫‪ pY = 5.85‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل )‪ (b‬ﻭ ‪ pY = 1.3‬ﻓﻲ‬ ‫ﻥ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪ ،‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﺍﻝﻤﺤﻠﻭل )‪ (c‬ﺘﻭﺍﻓﻘﺎﻥ ﺭﺠﺤﺎﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪ ، [CaY ]2−‬ﻭﻫﺫﺍ ﻤﺎ ﺘﻭﺼ‪‬ﻠﻨﺎ ﺇﻝﻴﻪ ﺴﺎﺒﻘﹰﺎ‪.‬‬
‫‪ .2.VI‬ﺘﺸﻜﹼل ﻋﺩ‪‬ﺓ ﻤﻌﻘﹼﺩﺍﺕ ﺒﺎﻝﺘﻌﺎﻗﺏ‬
‫ﺴﻨﻭﻀ‪‬ﺢ ﺫﻝﻙ ﺒﺩﺭﺍﺴﺔ ﺍﻝﻤﻌﻘﺩﺍﺕ ﺍﻝﺘﻲ ﺘﺘﺸﻜﹼل ﺒﻴﻥ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ )‪ Fe3 + (III‬ﻭﺸﺎﺭﺩﺓ‬
‫ﺍﻷﻭﻜﺴﺎﻻﺕ ‪. C2O24−‬‬
‫ﻤﺜﺎل‬
‫ل ‪ 0.10 mol‬ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺤﺩﻴﺩ )‪ (III‬ﻭﻜﻤﻴﺔ ‪ n‬ﻤﻥ‬

‫ﻨﺤﻀ‪‬ﺭ ﻝﻴﺘﺭﹰﺍ ﻤﻥ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺒﺤ ّ‬
‫ﺃﻭﻜﺴﺎﻻﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ) ‪ . (2 Na + + C2O24−‬ﺤﺩ‪‬ﺩ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ‬

‫ﺍﻵﺘﻴﺘﻴﻥ‪:‬‬
‫)‪n = 0.20 mol (b‬‬ ‫)‪n = 0.10 mol (a‬‬
‫ﻥ‪:‬‬
‫‪. log β2 ([Fe(C2O4 )2 ]− ) = 14.2‬‬ ‫ﻭ‬ ‫‪log β1([Fe C2O4 ]+ ) = 9.2‬‬
‫ﺍﻝﺤل‬
‫ﻴﻤﻜﻥ ﺃﻥ ﻴﺘﺸﻜﹼل ﻤﻌﻘﺩﺍﻥ ﺒﺎﻝﺘﻌﺎﻗﺏ ﻭﺫﻝﻙ ﺤﺴﺏ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ ﺍﻵﺘﻴﺘﻴﻥ‪:‬‬
‫)‪(1‬‬ ‫‪Fe3 + + C2O24− ⇌ [Fe(C2O4 )]+‬‬ ‫‪K f = β1 = 109.2‬‬

‫‪1‬‬
‫‪(2) [Fe(C2O4 )]+ + C2O24− ⇌ [Fe(C2O4 )2 ]−‬‬ ‫‪K f = β2 /β1 = 105‬‬

‫‪2‬‬
‫ﻥ ﻜﻼ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺘﺎ ‪‬ﻤﺎﻥ‪ .‬ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﻴﻤﻜﻨﻨﺎ ﻓﻲ ﻓﺭﻀﻴﺔ ﺃﻭﻝﻰ ﺍﻋﺘﺒﺎﺭ ﺃﻥ ﻫﺫﻴﻥ‬
‫ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﻤﺘﻌﺎﻗﺒﺎﻥ ﻷﻥ ‪ . ∆ log K f ≥ 4‬ﻝﻨﺤﺩ‪‬ﺩ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﻤﺤﻠﻭل ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ‬
‫‪i‬‬
‫ﺍﻝﻤﻌﻁﺎﺘﻴﻥ ﻓﻲ ﺍﻝﻤﺴﺄﻝﺔ‪.‬‬
‫• )‪n = 0.10 mol (a‬‬
‫ﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪[Fe(C2O4 )2 ]−‬‬

‫ﻥ ﻝﺩﻴﻨﺎ ﻤﺯﻴﺠﹰﺎ ﺃﻭﻝﻴﹰﺎ ﻤﺘﺴﺎﻭﻱ ﺍﻝﻤﻭﻝﻴﺔ‪ ،‬ﻭﻴﻤﻜﻨﻨﺎ ﺍﻋﺘﺒﺎﺭ ﺃ ‪‬‬
‫ﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻴﺘﺸﻜﹼل ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻷﻭﻝﻰ‪:‬‬
‫‪Fe3 + + C2O24− [Fe(C2O4 )]+‬‬

‫‪t = 0 0.10‬‬ ‫‪0.10‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪ε‬‬ ‫‪0.10‬‬
‫ﻥ‪:‬‬
‫‪[[Fe(C2O4 )2 ]− ] = 0.10 mol / L‬‬
‫‪ [[Fe(C O )]− ] 1/2‬‬

‫‪ε = ‬‬ ‫‪2 4‬‬ ‫‪ = 7.9 × 10−6 mol / L‬‬
‫‪‬‬ ‫‪β1‬‬ ‫‪‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻨﻲ ﺍﻝﺫﻱ ﻴﺠﺏ ﺍﻋﺘﺒﺎﺭﻩ ﺒﻌﺩ ﺫﻝﻙ ﻫﻭ ﺘﻔﺎﻋل ﺍﻝﺘﻔﻜﻙ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﻌﻘﹼﺩ ﺍﻝﻤﺘﺸﻜﹼل‪:‬‬
‫‪2[Fe(C2O4 )]+ ⇌ Fe3 + + [Fe(C2O4 )2 ]−‬‬
‫ﻭﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‬
‫] ‪[Fe3 + ] ⋅ [[Fe(C2O4 )2 ]−‬‬ ‫‪Kf‬‬ ‫‪β2‬‬
‫= ‪K0‬‬ ‫=‬ ‫‪2‬‬
‫=‬ ‫‪= 6.3 × 10−5 mol / L‬‬
‫‪+ 2‬‬
‫] ]) ‪[[Fe(C2O4‬‬ ‫‪Kf‬‬
‫‪1‬‬
‫‪β12‬‬
‫ﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﺃﺼﻐﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ ﺇﺫﺍ ﺭﺴﻤﻨﺎ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻤﺨﺘﻠﻑ‬
‫ﻭﻴﻤﻜﻨﻨﺎ ﺍﻝﺘﻨﺒﺅ ﺒﺄ ‪‬‬
‫ﺍﻝﻤﻌﻘﺩﺍﺕ ﺒﺩﻻﻝﺔ ‪ pC2O4‬ﻜﻤﺎ ﻴﻅﻬﺭ ﻤﻥ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫‪pC2O4‬‬
‫‪Fe3 +‬‬ ‫‪9.2‬‬
‫‪[Fe(C2O4 )]+‬‬
‫‪[Fe(C2O4 )]+‬‬ ‫‪5.0‬‬
‫‪[Fe(C2O4 )2 ]−‬‬
‫ﻥ ‪ K 0‬ﺼﻐﻴﺭ‬
‫ﻨﺼل ﺇﻝﻰ ﺘﺭﺍﻜﻴﺯ ‪ Fe3 +‬ﻭ ‪ [Fe(C2O4 )2 ]−‬ﺒﺈﻫﻤﺎل ﻗﻴﻤﺔ ‪ ε‬ﻭﺒﻤﻼﺤﻅﺔ ﺃ ‪‬‬
‫ﻥ ﺘﻔﻜﹼﻙ ﺍﻝﻤﻌﻘﹼﺩ ﻴﻜﻭﻥ ﻀﻌﻴﻔﹰﺎ ﻝﻠﻐﺎﻴﺔ ﻭﻨﻜﺘﺏ‪:‬‬
‫ﺠﺩﹰﺍ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫‪[Fe3 + ] = [[Fe(C2O4 )2 ]− ] = (K 0 × [[Fe(C2O4 )]+ ]2 )1/2‬‬

‫‪[Fe3 + ] = [[Fe(C2O4 )2 ]− ] = 7.9 × 10−4 mol / L‬‬
‫ﺃﻤﺎ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪ C2O24−‬ﻓﻨﺤﺩ‪‬ﺩﻩ ﺍﺒﺘﺩﺍﺀ ﻤﻥ ﻗﻴﻤﺔ ‪: β1‬‬

‫] ‪[[Fe(C2O4 )]+‬‬
‫= ] ‪[C2O24−‬‬ ‫‪= 7.9 × 10−8 mol / L‬‬
‫‪3+‬‬
‫‪β1 ⋅ [Fe‬‬ ‫]‬
‫ﻭﻫﺫﺍ ﻴﻭﺍﻓﻕ ‪. pC2O4 = − log[C2O24− ] = 7.1‬‬
‫ﻭﻴﻤﻜﻨﻨﺎ ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﺘﻲ ﻭﻀﻌﻨﺎﻫﺎ ﺒﺭﺴﻡ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻭﺘﺤﺩﻴﺩ ﺍﻝﻘﻴﻤﺔ‬
‫‪ pC2O4 = 7.1‬ﻋﻠﻴﻪ‪ ،‬ﻓﻨﻼﺤﻅ ﺃﻨﻨﺎ ﻨﻘﻊ ﻓﻲ ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ [Fe(C2O4 )]+‬ﻓﻲ‬
‫ﻥ ‪ Fe3 +‬ﻭ ‪ [Fe(C2O4 )2 ]−‬ﻫﻲ ﺸﻭﺍﺭﺩ ﻨﺎﺩﺭﺓ‪.‬‬
‫ﺤﻴﻥ ﺃ ‪‬‬
‫‪[Fe(C2O4 )2 ]−‬‬ ‫‪[Fe(C2O4 )]+‬‬ ‫‪Fe3 +‬‬

‫‪5.0‬‬ ‫‪7.1‬‬ ‫‪9.2‬‬ ‫‪pC2O4‬‬
‫ﺍﻝﻤﺤﻠﻭل ‪a‬‬
‫• )‪n = 0.20 mol (b‬‬
‫ﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪ [Fe(C2O4 )2 ]−‬ﻴﺘﺸﻜﹼل‬

‫ﻝﻤ‪‬ﺎ ﻜﺎﻥ ) ‪ n 0 (C2O24− ) = 2 n 0 (Fe3 +‬ﻓﻴﻤﻜﻨﻨﺎ ﺍﻝﻘﻭل ﺒﺄ ‪‬‬
‫ﻨﺘﻴﺠﺔ ﻝﺘﻌﺎﻗﺏ ﺘﻔﺎﻋﻠﻴﻥ ﺭﺍﺠﺤﻴﻥ ﺘﺎﻤ‪‬ﻴﻥ ﻫﻤﺎ )‪ (1‬ﻭ )‪. (2‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻷﻭل ﻫﻲ‪:‬‬
‫‪Fe3 +‬‬ ‫‪+ C2O24− [Fe(C2O4 )]+‬‬
‫‪t = 0 0.10‬‬ ‫‪0.20‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪0.10‬‬ ‫‪0.10‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﺜﺎﻨﻲ ﻫﻲ‪:‬‬
‫‪[Fe(C2O4 )]+‬‬ ‫‪+ C2O24− [Fe(C2O4 )2 ]−‬‬
‫‪t = 0 0.10‬‬ ‫‪0.10‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪ε′‬‬ ‫‪ε′‬‬ ‫‪0.10‬‬
‫ل ﻤﻥ ‪ C2O24−‬ﻭ ‪ [Fe(C2O4 )]+‬ﺒﺎﺴﺘﻌﻤﺎل ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‬

‫ﻴﻤﻜﻨﻨﺎ ﺘﺤﺩﻴﺩ ﺘﺭﺍﻜﻴﺯ ﻜ ﱟ‬
‫‪: K f = β2 /β1 = 105‬‬
‫‪2‬‬
‫= ] ]) ‪[[Fe(C2O4‬‬ ‫‪+‬‬
‫] ‪[C2O24−‬‬ ‫‪= ([[Fe(C2O4 )2 ] ] / K f )1/2‬‬
‫‪−‬‬
‫‪2‬‬
‫= ] ‪[[Fe(C2O4 )]+‬‬ ‫] ‪[C2O24−‬‬ ‫‪= 1.0 × 10−3 mol / L‬‬

‫ﻥ ‪. pC2O4 = − log[C2O24− ] = 3.0‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻭﻨﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﺒﺎﻻﻋﺘﻤﺎﺩ ﻋﻠﻰ ‪: β1‬‬

‫] ‪[[Fe(C2O4 )]+‬‬
‫= ] ‪[Fe3 +‬‬ ‫‪= 6.3 × 10−10 mol / L‬‬
‫] ‪β1 ⋅ [C2O24−‬‬
‫ﻭﻴﻤﻜﻨﻨﺎ ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﻨﺎ ﺇﻝﻴﻬﺎ ﺒﻭﻀﻊ ﺍﻝﻘﻴﻤﺔ ‪ pC2O4 = 3.0‬ﻋﻠﻰ‬
‫ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﻭﺍﻝﺘﺤﻘﻕ ﺃﻨﻨﺎ ﻓﻲ ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪: [Fe(C2O4 )2 ]−‬‬
‫‪[Fe(C2O4 )2 ]−‬‬ ‫‪[Fe(C2O4 )]+‬‬ ‫‪Fe3 +‬‬

‫‪3.0‬‬ ‫‪5.0‬‬ ‫‪9.2‬‬ ‫‪pC2O4‬‬
‫ﺍﻝﻤﺤﻠﻭل ‪b‬‬
‫‪ .3.VI‬ﺘﺸﻜﹼل ﻋﺩ‪‬ﺓ ﻤﻌﻘﹼﺩﺍﺕ ﺒﺂﻥ ﻭﺍﺤﺩ‬
‫ﻫﺫﺍ ﻫﻭ ﺍﻝﺤﺎل ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺘﻔﺎﻋﻼﺕ ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻏﻴﺭ ﻜﻤﻴﺔ ﻭ‪/‬ﺃﻭ ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ‬
‫ﻝﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﹼل ﻗﻴﻡ‪ ‬ﻤﺘﻘﺎﺭﺒﺔ ‪ . ∆ log K f < 4‬ﻝﻨﻭﻀ‪‬ﺢ ﺫﻝﻙ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﻌﻘﺩﺍﺕ ﺍﻝﻤﺘﺸﻜﻠﺔ ﺒﻴﻥ‬
‫‪i‬‬
‫ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ )‪ (III‬ﻭﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‪.‬‬

‫ﻤﺜﺎل‪:‬‬
‫ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ Fe3 + (III‬ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ‪ SO24−‬ﻝﺘﻌﻁﻲ ﻤﻌﻘﹼﺩﻴﻥ‪:‬‬
‫ﺘﺸﻜﻴل‬ ‫ﺒﺜﺎﺒﺕ‬ ‫ﻭ ‪[Fe(SO4 )2 ]−‬‬ ‫‪log β1 = 4.2‬‬ ‫ﺘﺸﻜﻴل‬ ‫ﺒﺜﺎﺒﺕ‬ ‫‪[Fe SO4 )]+‬‬
‫‪. log β2 = 7.4‬‬
‫ﻨﻀﻴﻑ ‪ 12.5 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ‪ Na 2SO4‬ﺒﺘﺭﻜﻴﺯ ‪ 0.10 mol / L‬ﺇﻝﻰ‬
‫‪ 10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﺤﺩﻴﺩ )‪ Fe Cl3 (III‬ﺒﺘﺭﻜﻴﺯ ‪ . 0.10 mol / L‬ﺤﺩ‪‬ﺩ ﺍﻝﺘﺭﻜﻴﺏ‬
‫ﺍﻝﻨﻬﺎﺌﻲ‪.‬‬
‫ﻻ ﺍﻝﺘﺭﺍﻜﻴﺯ‬
‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻤﺨﺘﻠﻑ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺭﺍﺠﺤﺔ ﺍﻝﺘﻲ ﺘﺘ ‪‬ﻡ‪ ،‬ﻭﻝﻜﻥ ﻝﻨﺤﺴﺏ ﺃﻭ ﹰ‬
‫ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﺁﺨﺫﻴﻥ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺍﻝﺘﻤﺩﻴﺩ‪.‬‬
‫‪0.10 × 10‬‬
‫= ‪[Fe3 + ]0‬‬ ‫‪= 0.044 mol / L‬‬
‫‪22.5‬‬
‫‪0.10 × 12.5‬‬
‫= ‪[SO24− ]0‬‬ ‫‪= 0.056 mol / L‬‬
‫‪22.5‬‬
‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻷﻭل ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺒﻴﻥ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ )‪ (III‬ﻭﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﺤﺴﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ‬
‫ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪Fe3 +‬‬ ‫‪+ SO24−‬‬ ‫‪ [Fe SO4 ]+‬‬
‫‪t = 0 0.044‬‬ ‫‪0.056‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪0.044 − x‬‬ ‫‪0.056 − x‬‬ ‫‪x‬‬
‫ﺘﺘﻔﺎﻋل ﺒﻌﺩ ﺫﻝﻙ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩﺓ ‪ [Fe SO4 ]+‬ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﺤﺴﺏ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ‬
‫ﺍﻝﺜﺎﻨﻲ‪:‬‬
‫‪[Fe SO4 ]+ + SO24−‬‬ ‫‪ [Fe(SO4 )2 ]−‬‬
‫‪t =0 x‬‬ ‫‪0.056 − x‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪x −y‬‬ ‫‪0.056 − x − y‬‬ ‫‪y‬‬
‫ﻥ ﺘﺭﻜﻴﺯ‬
‫ﻨﺴﺘﻌﻴﻥ ﺒﻌﺩ ﺫﻝﻙ ﺒﻌﺒﺎﺭﺘﻲ ‪ K f‬ﻭ ‪ K f‬ﻤﻊ ﺍﻻﻨﺘﺒﺎﻩ ﻋﻨﺩ ﻜﺘﺎﺒﺔ ﻋﺒﺎﺭﺓ ‪ K f‬ﺇﻝﻰ ﺃ ‪‬‬
‫‪1‬‬ ‫‪2‬‬ ‫‪1‬‬
‫ﻫﻭ ‪ 0.056 − x − y‬ﻭﻝﻴﺱ‬ ‫ﺘﺭﻜﻴﺯ ‪SO24−‬‬ ‫‪ [Fe SO4 ]+‬ﻫﻭ ‪ x − y‬ﻭﻝﻴﺱ ‪ x‬ﻭﻜﺫﻝﻙ‬
‫‪ 0.056 − x‬ﻷﻥ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺭﺍﺠﺤﻴﻥ ﺍﻷﻭل ﻭﺍﻝﺜﺎﻨﻲ ﻴﺤﺼﻼﻥ ﻓﻲ ﺁﻥ ﻭﺍﺤﺩ‪.‬‬
‫‪x −y‬‬
‫= ‪Kf‬‬
‫‪1‬‬
‫) ‪(0.044 − x )(0.056 − x − y‬‬
‫‪y‬‬
‫‪Kf‬‬ ‫=‬
‫‪2‬‬
‫) ‪(x − y )(0.056 − x − y‬‬
‫ﻨﺤﺼل ﺒﻌﺩ ﺫﻝﻙ ﻋﻠﻰ ﺠﻤﻠﺔ ﺘﻀﻡ ﻤﻌﺎﺩﻝﺘﻴﻥ ﺒﻤﺠﻬﻭﻝﻴﻥ ﻨﺤﻠﹼﻬﺎ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺒﺭﻤﺠﻴﺔ ﻤﺘﺨﺼ‪‬ﺼﺔ‬
‫ﻓﻨﺠﺩ ﺠﻤﻠﺔ ﺍﻝﺤﻠﻭل ﺍﻵﺘﻴﺔ‪:‬‬
‫)‪(y = −0.033066, x = 0.0892366‬‬
‫= ‪(y‬‬ ‫)‪0.0155038, x = 0.0400984‬‬
‫= ‪(y‬‬ ‫)‪0.0448598, x = 0.0439983‬‬
‫ﺍﻝﺤل ﺍﻷﻭل ﻤﺭﻓﻭﺽ ﻷﻨﻪ ﻴﻌﻁﻲ ﻗﻴﻤﹰﺎ ﺴﺎﻝﺒﺔ ﻝﻠﺘﺭﻜﻴﺯ‪ ،‬ﻭﺍﻝﺤل ﺍﻝﺜﺎﻝﺙ ﻤﺭﻓﻭﺽ ﻷﻨﻪ ﻴﻌﻁﻲ ﻗﻴﻤﺔ‬
‫ل ﺍﻝﻭﺤﻴﺩ‬
‫ل ﺍﻝﺜﺎﻨﻲ ﻫﻭ ﺍﻝﺤ ّ‬
‫ﻝـ ‪ y‬ﺘﻔﻭﻕ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻲ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ . (III‬ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫ﺍﻝﻤﻘﺒﻭل ﻓﻴﺯﻴﺎﺌﻴﹰﺎ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ‪:‬‬
‫‪[[Fe(SO4 )2 ]− ] = 1.5 × 10−2 mol / L‬‬
‫‪[[Fe SO4 ]+ ] = 2.5 × 10−2 mol / L‬‬
‫‪[Fe3+ ] = 4.0 × 10−3 mol / L‬‬
‫‪[SO24− ] = 4.0 × 10−4 mol / L‬‬
‫‪ .VII‬ﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺘﻌﻘﻴﺩ‬
‫ﺴﻭﻑ ﻨﻘﺘﺼﺭ ﻋﻠﻰ ﻋﺭﺽ ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﻤﻥ‬
‫‪ E.D.T.A‬ﻭﺘﺴﺘﻌﻤل ﻫﺫﻩ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻓﻲ ﺘﺤﺩﻴﺩ ﻗﺴﺎﻭﺓ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .1.VII‬ﻤﺒﺩﺃ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫ﻻ ﻤﻥ ‪ E.D.T.A‬ﺒﺘﺭﻜﻴﺯ ﻤﻌﻠﻭﻡ ‪ C 1‬ﺇﻝﻰ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ‬

‫ﻨﻀﻴﻑ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺴﺤﺎﺤﺔ ﻤﺤﻠﻭ ﹰ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺤﺠﻤﻪ ‪ V2‬ﻤﺤﺩ‪‬ﺩ ﺒﺩﻗﺔ ﻭﺘﺭﻜﻴﺯﻩ ‪ C 2‬ﻴﻠﺯﻡ ﺘﺤﺩﻴﺩﻩ‪.‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻲ‪:‬‬
‫ﺇ‪‬‬
‫‪2−‬‬
‫‪Ca 2 + + Y 4− ⇌  CaY ‬‬
‫ﻴﺘﻤﺘﻊ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﺒﺜﺎﺒﺕ ‪ K 0 = β = 1010.6 = 4.0 × 1010‬ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﺘﻔﺎﻋل ﺘﺎﻡ‪.‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻨﻜﻭﻥ ﻗﺩ ﺃﻀﻔﻨﺎ ﻋﺩﺩﹰﺍ ﻤﻥ ﺸﻭﺍﺭﺩ ‪ Y 4−‬ﻴﺴﺎﻭﻱ ﻋﺩﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪ ،‬ﻭﻨﻌﺒ‪‬ﺭ‬
‫ﻋﻥ ﺫﻝﻙ ﺒﺎﻝﻜﺘﺎﺒﺔ‪:‬‬
‫‪n 0 (Ca 2 + ) = n(Y 4− )added‬‬
‫‪eqv‬‬
‫ﻨﻘﺼﺩ ﺒﺎﻝﺩﻝﻴل ‪ eqv‬ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ .‬ﻭﻴﻤﻜﻥ ﻜﺘﺎﺒﺔ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺘﺭﺍﻜﻴﺯ‪:‬‬
‫‪C 2V2 = C 1V1eqv‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻨﺕ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﻭﺍﻝﻤﻭﺍﺩ ﺍﻝﻨﺎﺘﺠﺔ ﻋﻥ ﺍﻝﺘﻔﺎﻋل ﻋﺩﻴﻤﺔ ﺍﻝﻠﻭﻥ‪ ،‬ﻓﺈﻨﻨﺎ ﻨﺴﺘﻌﻴﻥ‬
‫ﺒﻤﺸﻌﺭ ﻝﻭﻨﻲ ﻴﺩﻝﹼﻨﺎ ﻋﻠﻰ ﻨﻬﺎﻴﺔ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻭﺴﻨﺄﺘﻲ ﻋﻠﻰ ﺘﺤﺩﻴﺩﻩ ﺒﻌﺩ ﻗﻠﻴل‪.‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ Y 4−‬ﻫﻲ ﺃﺴﺎﺱ ﺭﺒﺎﻋﻲ ﺍﻝﻭﻅﻴﻔﺔ ﺤﻤﻀﻪ ﺍﻝﻤﺭﺍﻓﻕ ﻫﻭ ‪ H4Y‬ﻭﻴﺘﻤﺘﻊ ﺒﺜﻭﺍﺒﺕ‬
‫ﺇ‪‬‬
‫ﺍﻝﺤﻤﻭﻀﺔ ﺍﻝﺘﺎﻝﻴﺔ‪ . pK A = 2.0, 2.7, 6.2, 10.2 :‬ﻴﻅﻬﺭ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﻤﻨﺎﻁﻕ ﺭﺠﺤﺎﻥ‬
‫‪i‬‬
‫ﺍﻝﺤﻤﺽ ‪. H4Y‬‬
‫‪H 4Y‬‬ ‫‪H 3Y −‬‬ ‫‪H 2Y 2 −‬‬ ‫‪HY 3 −‬‬ ‫‪Y 4−‬‬
‫‪0‬‬ ‫‪2.0‬‬ ‫‪2.7‬‬ ‫‪6.2‬‬ ‫‪10.2‬‬ ‫‪14 pH‬‬
‫ﻭﺤﺘﻰ ﻻ ﺘﺘﺄﺜﺭ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺘﻔﺎﻋﻼﺕ ﺫﺍﺕ ﻁﺒﻴﻌﺔ ﺤﻤﻀﻴﺔ ﺃﺴﺎﺴﻴﺔ ﺘﺸﺎﺭﻙ ﺒﻬﺎ ﺍﻝﺸﺎﺭﺩﺓ‬
‫ﻕ ﻴﺠﻌل ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻌﺎﻴ‪‬ﺭ ﺜﺎﺒﺘﹰﺎ‪.‬‬
‫‪ Y 4−‬ﻓﺈﻨﻨﺎ ﻨﺴﺘﻌﻴﻥ ﺒﻤﺤﻠﻭل ﻤﻭ ‪‬‬
‫ﻥ‬
‫ﻥ ﺍﻝﺘﺠﺭﺒﺔ ﻗﺩ ﺒﺭﻫﻨﺕ ﺃ ‪‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ﺍﻝﻤﺸﻌﺭ ﺍﻝﻠﻭﻨﻲ ﻴﺘﺄﺜﺭ ﺒﺩﻭﺭﻩ ﺒﺤﻤﻭﻀﺔ ﺍﻝﻭﺴﻁ‪ ،‬ﻓﺈ ‪‬‬
‫ﻥ‬
‫ﺘﺜﺒﻴﺕ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﺍﻝﻘﻴﻤﺔ ‪ 10‬ﺘﻭﻓﺭ ﺍﻝﺩﻗﺔ ﺍﻝﻔﻀﻠﻰ ﻝﻠﻤﻌﺎﻴﺭﺓ‪ .‬ﺴﻨﻘﺒل‪ ،‬ﺘﺒﺴﻴﻁﹰﺎ ﻝﻠﺩﺭﺍﺴﺔ‪ ،‬ﺃ ‪‬‬
‫ﺍﻝﻤﺤﻠﻭل ﻴﻜﻭﻥ ﻤﻭﻗﻴﹰﺎ ﻋﻨﺩ ‪. pH = pK A = 10.2‬‬
‫‪i‬‬
‫ﻝﻨﺩﺭﺱ ﻜﻴﻑ ﻴﺘﻐﻴﺭ ] ‪ pY = − log[Y 4−‬ﻓﻲ ﻭﺴﻁ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻌﺎ ‪‬ﻴﺭ ﻋﻨﺩﻤﺎ ﻨﻀﻴﻑ‬
‫ﺇﻝﻴﻪ ‪ ،Y 4−‬ﻭﻝﻬﺫﺍ ﺴﻭﻑ ﻨﺩﺭﺱ‪ ،‬ﻭﻋﻠﻰ ﻨﺤﻭ ﻤﺸﺎﺒﻪ ﻝﻤﺎ ﻓﻌﻠﻨﺎﻩ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﺤﻤﻀﻴﺔ‬
‫ﺍﻷﺴﺎﺴﻴﺔ‪ ،‬ﺘﻐﻴﺭﺍﺕ ) ‪ pY = f (x‬ﺤﻴﺙ ‪. x = V1 / V1eqv‬‬
‫‪ .2.VII‬ﺍﻝﻤﻨﺤﻨﻲ )‪pY = f(x‬‬
‫ﻝﺩﻴﻨﺎ ﻋﺩﺓ ﺤﺎﻻﺕ ﻭﻓﻘﹰﺎ ﻝﻘﻴﻤﺔ ‪: x‬‬

‫‪ x = 0‬ﺃﻱ ‪V1 = 0‬‬
‫ﻥ ‪ pY‬ﻏﻴﺭ ﻤﻌﺭ‪‬ﻑ‪.‬‬
‫ﻻ ﻴﻭﺠﺩ ‪ E.D.T.A.‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫‪ 0 < x < 1‬ﺃﻱ ‪0 < V1 < V1eqv‬‬

‫ل ﺇﻀﺎﻓﺔ ﺒﻌﺩ ﺍﻝﻭﺼﻭل ﺇﻝﻰ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‬
‫ﻴﺤﺼل ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ‪ .‬ﻝﻨﺤﺴﺏ ﻋﺩﺩ ﺍﻝﻤﻭﻻﺕ ﻋﻨﺩ ﻜ ّ‬
‫‪2−‬‬
‫‪Ca 2 +‬‬ ‫‪+ Y 4−‬‬ ‫‪  CaY ‬‬
‫‪t = 0 C 2V2‬‬ ‫‪C 1V1‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪C 2V2 − C 1V1‬‬ ‫‪ε‬‬ ‫‪C 1V1‬‬
‫ﻴﺘ ‪‬ﻡ ﺘﺤﺩﻴﺩ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪ Y 4−‬ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﺜﺎﺒﺕ ‪: β‬‬
‫] ‪[[CaY ]2−‬‬
‫= ] ‪[Y 4−‬‬
‫] ‪β ⋅ [Ca 2+‬‬
‫] ‪[[CaY ]2−‬‬
‫‪pY = log β − log‬‬
‫] ‪[Ca 2 +‬‬
‫ﻥ‬
‫‪C 2V2 − C 1V1‬‬ ‫‪C 1V1eqv − C 1V1‬‬
‫‪pY = log β + log‬‬ ‫‪= log β + log‬‬
‫‪C 1V1‬‬ ‫‪C 1V1‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪1−x‬‬
‫‪pY = log β + log‬‬
‫‪x‬‬
‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ﻋﻨﺩﻤﺎ ‪ x = 0.5‬ﻝﺩﻴﻨﺎ‬
‫‪. pY = log β = 10.6‬‬
‫‪ x = 1‬ﺃﻱ ‪V1 = V1eqv‬‬
‫ﻨﺼل ﻫﻨﺎ ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻭﻋﻨﺩﻫﺎ ﺘﻜﻭﻥ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﻤﻤﺯﻭﺠﺔ ﻭﻓﻕ ﺍﻝﻨﺴﺏ ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺍﻝﺸﺎﺭﺩﺓ ‪ [CaY ]2−‬ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯﻫﺎ‬
‫‪C 1V1eqv‬‬ ‫‪C 2V2‬‬
‫= ‪[[CaY ]2− ] = C ′‬‬ ‫=‬
‫‪V1eqv + V2‬‬ ‫‪V1eqv + V2‬‬
‫ﻴﺨﻀﻊ ﻫﺫﺍ ﺍﻝﻤﻌﻘﺩ ﻝﺘﻔﻜﹼﻙ ﻀﻌﻴﻑ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ‪:‬‬
‫‪ CaY  2− ⇌ Ca 2 + + Y 4 −‬‬
‫‪‬‬ ‫‪‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ‪ E.D.T.A.‬ﻏﻴﺭ ﺍﻝﻤﻌﻘﹼﺩﺓ ﺴﻭﻑ‬‫ﻭﻝﻤ‪‬ﺎ ﻜﺎﻥ ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل ﻤﻭﻗﻰ ﻋﻨﺩ ‪ pH = 10.2‬ﻓﺈ ‪‬‬
‫ﺘﺘﻭﺯ‪‬ﻉ ﻭﺒﻜﻤﻴﺎﺕ ﻤﺘﺴﺎﻭﻴﺔ ﺒﻴﻥ ﺍﻝﺸﻜﻠﻴﻥ‪ HY 3− :‬ﻭ ‪ Y 4−‬ﻭﻫﻜﺫﺍ ﻨﻜﺘﺏ‪:‬‬
‫] ‪[Ca 2+ ] = [HY 3− ] + [Y 4− ] = 2[Y 4−‬‬
‫ﻭﻋﻠﻴﻪ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪:Y 4−‬‬
‫‪ [[CaY ]2− ] 0.5‬‬ ‫‪ C ′ 0.5‬‬
‫‪[Y‬‬ ‫‪4−‬‬ ‫‪‬‬
‫‪] = ‬‬ ‫‪ =  ‬‬
‫‪ 2 ⋅ β ‬‬ ‫‪ 2β ‬‬
‫‪1‬‬
‫))‪pY = (log β − log(C ′/2‬‬
‫‪2‬‬
‫‪ x > 1‬ﺃﻱ ‪V1 > V1eqv‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ﻓﺎﺌﺽ ﻤﻥ ﺸﻭﺍﺭﺩ ‪ E.D.T.A.‬ﻭﻨﻜﺘﺏ‪:‬‬
‫‪C 1V1 − C 1V1eqv‬‬ ‫‪C 1V1eqv‬‬

‫= ] ‪[HY 3− ] + [Y 4−‬‬ ‫=‬ ‫)‪(x − 1‬‬
‫‪V1 + V2‬‬ ‫‪V1 + V2‬‬
‫ﻭﻋﻨﺩ ‪ pH = 10.2‬ﻴﻜﻭﻥ‬
‫] ‪[HY 3− ] = [Y 4−‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪C 1V1eqv‬‬
‫= ] ‪[Y 4−‬‬ ‫)‪(x − 1‬‬
‫) ‪2(V1 + V2‬‬
‫ﻥ‬
‫‪ C 1V1eqv ‬‬
‫‪pY = − log ‬‬ ‫)‪ − log(x − 1‬‬
‫‪ 2(V1 + V2 ) ‬‬
‫ﻝﻨﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻤﻭﺍﻓﻕ ﻝﻬﺫﻩ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪ C 1 =C 2 =0.10 mol / L‬ﻭﺍﻝﺤﺠﻡ‬
‫‪.V2 =10.0 mL‬‬
‫‪4−‬‬
‫‪pY = − log[Y‬‬ ‫]‬
‫‪14‬‬
‫‪13‬‬
‫‪12‬‬
‫‪11‬‬
‫‪10 10.6‬‬
‫‪9‬‬
‫‪8‬‬
‫‪7‬‬
‫‪pYeqv = 6.1‬‬
‫‪6‬‬ ‫‪E‬‬
‫‪5‬‬
‫‪4‬‬
‫‪3‬‬
‫‪2‬‬
‫‪1‬‬
‫‪0‬‬ ‫‪0.5‬‬ ‫‪1‬‬

‫‪x = V1 /V1eqv‬‬
‫ﺍﻝﺸﻜل )‪ : (1‬ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﻝﺘﻌﻘﻴﺩ ﻝﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺒﺸﻭﺍﺭﺩ ‪.Y 4 − ،E.D.T.A.‬‬
‫‪ .3.VII‬ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫ﻴﺴﺘﻌﻤل ﻤﺸﻌﺭ ﺃﺴﻭﺩ ﺍﻹﻴﺭﻴﻭﻜﺭﻭﻡ ﻤﻥ ﺍﻝﻨﻭﻉ "ﺕ"‪ eriochrome T :‬ﺒﺼﻔﺘﻪ ﻤﺸﻌﺭﹰﺍ ﻓﻲ‬
‫ﻨﻬﺎﻴﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻝﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ .‬ﻭﻫﻭ ﺤﻤﺽ ﺜﻼﺜﻲ ﺍﻝﻭﻅﻴﻔﺔ ‪ H3Ind‬ﺘﻜﻭﻥ ﺍﻝﻭﻅﻴﻔﺔ‬
‫ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﻭﻝﻰ ﻗﻭﻴﺔ ﻓﻲ ﺤﻴﻥ ﺘﻜﻭﻥ ﺍﻝﻭﻅﻴﻔﺘﺎﻥ ﺍﻝﺒﺎﻗﻴﺘﺎﻥ ﻀﻌﻴﻔﺘﻴﻥ ‪. pK A : 6.3, 11.5‬‬
‫‪i‬‬
‫ﻴﺘﻌﻠﹼﻕ ﻝﻭﻥ ﻫﺫﺍ ﺍﻝﻤﺸﻌﺭ ﺒﻤﻘﺩﺍﺭ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬

‫ﻋﻨﺩ ‪ pH = 10.2‬ﻴﻜﻭﻥ ﻝﻭﻥ ﺃﺴﻭﺩ ﺍﻹﻴﺭﻴﻭﻜﺭﻭﻡ ﻤﻥ ﺍﻝﻨﻭﻉ "ﺕ" ﺃﺯﺭﻕ ﺍﻝﻠﻭﻥ ﻭﻫﺫﺍ ﻫﻭ ﺍﻝﻠﻭﻥ‬
‫ﺍﻝﻤﻤﻴ‪‬ﺯ ﻝﻠﺸﻜل ‪. HInd 2−‬‬
‫‪H2 Ind−‬‬ ‫‪HInd 2 −‬‬ ‫‪Ind 3−‬‬
‫‪0‬‬ ‫ﻟﻮﻥ ﺯﻫﺮﻱ‬ ‫‪6.3‬‬ ‫ﻟﻮﻥ ﺃﺯﺭﻕ‬ ‫‪10.2‬‬ ‫‪11.5‬‬ ‫ﻟﻮﻥ ﺑﺮﺗﻘﺎﱄ‬ ‫‪14 pH‬‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ‪ ،‬ﻴﻌﻁﻲ ﻫﺫﺍ ﺍﻝﻤﺸﻌﺭ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻤﻌﻘﺩﹰﺍ ﻝﻭﻨﻪ ﺃﺤﻤﺭ ﺒﻨﻔﺴﺠﻲ‪:‬‬
‫‪−‬‬
‫‪Ca 2 + + HInd 2− + OH− ⇌  CaInd  + H2O‬‬
‫ﺃﺯﺭﻕ‬ ‫ﺃﺤﻤﺭ ﺒﻨﻔﺴﺠﻲ‬
‫ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ‪. K 0 = β ′ = 1.0 × 107‬‬

‫ﻝﺘﺤﻘﻴﻕ ﻫﺫﻩ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻨﺄﺨﺫ ﺒﺩﺍﻴﺔ ﺤﺠﻤﹰﺎ ﻤﺤﺩﺩﹰﺍ ﻗﺩﺭﻩ ‪ V2‬ﻤﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺤﺎﻭﻱ ﺸﻭﺍﺭﺩ‬
‫ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ Ca 2 +‬ﺍﻝﻼﺯﻡ ﻤﻌﺎﻴﺭﺘﻬﺎ‪ ،‬ﻭﺤﺠﻤﹰﺎ ‪ V‬ﻤﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻭﻗﻲ ﻋﻨﺩ ‪pH = 10.2‬‬
‫ﻭﺒﻀﻌﺔ ﻨﻘﺎﻁ ﻤﻥ ﺃﺴﻭﺩ ﺍﻹﻴﺭﻴﻭﻜﺭﻭﻡ ﻤﻥ ﺍﻝﻨﻭﻉ "ﺕ"‪ ،‬ﻓﻴﺘﻜﻭ‪‬ﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ CaInd ]−‬ﻭﻴﺼﺒﺢ ﻝﻭﻥ‬
‫ﺍﻝﻤﺤﻠﻭل ﺃﺤﻤﺭ ﺒﻨﻔﺴﺠﻴﹰﺎ‪.‬‬
‫‪ Y‬ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺍﻝﺤﺭﺓ‬ ‫‪4−‬‬
‫ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻌﺎ ِ‪‬ﻴﺭ ﻤﻥ ‪ E.D.T.A.‬ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ‬
‫ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪2+‬‬ ‫‪4−‬‬ ‫‪2−‬‬
‫‪Ca‬‬ ‫‪+Y‬‬ ‫] ‪ [ CaY‬‬ ‫‪β = 4.0 × 1010‬‬
‫ﻭﺒﻌﺩ ﺃﻥ ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ‪ Y 4−‬ﻤﻊ ﻜل ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺍﻝﺤﺭﺓ ﺘﺘﻔﺎﻋل ﺒﻌﺩﺌﺫ ﻤﻊ ﺍﻝﻤﻌﻘﹼﺩ‬
‫‪ [ CaInd ]−‬ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫ ‪ CaInd  − + Y 4−‬‬ ‫‪ CaY  2− + HInd 2− + OH−‬‬

‫‪‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪‬‬
‫ﻻ ﻝﻭﻥ ﻝﻪ ﺃﺤﻤﺭ ﺒﻨﻔﺴﺠﻲ‬ ‫ﻻ ﻝﻭﻥ ﻝﻪ‬ ‫ﺃﺯﺭﻕ‬
‫ﻭ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ‪. K = 5.0 × 103‬‬
‫ﻭﻋﻨﺩﻤﺎ ﻴﺼﺒﺢ ] ‪ [HInd 2− ] > 10 ⋅ [[CaInd ]−‬ﻴﺘﺤﻭ‪‬ل ﻝﻭﻥ ﺍﻝﻤﺤﻠﻭل ﺇﻝﻰ ﺃﺯﺭﻕ‪ ،‬ﻭﻴﻤﻜﻨﻨﺎ‬
‫ل ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺍﻝﺘﻲ ﻜﺎﻨﺕ ﺒﺩﺍﻴﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻗﺩ ﺘﻔﺎﻋﻠﺕ ﻭﺃﻨﻨﺎ ﻭﺼﻠﻨﺎ ﺇﻝﻰ‬
‫ﻥ ﻜّ‬
‫ﺃﻥ ﻨﻌﺘﺒﺭ ﺃ ‪‬‬
‫ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫‪ .4.VII‬ﺘﻁﺒﻴﻕ‬
‫ﻕ ﻋﻨﺩ ‪ pH = 10.2‬ﺤﺠﻤﹰﺎ ﻗﺩﺭﻩ ‪ V1‬ﻤﻥ ﺍﻝﻤﻴﺎﻩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﺍﻝﺘﻲ‬

‫ﻨﻌﺎﻴﺭ ﺒﻭﺠﻭﺩ ﻤﺤﻠﻭل ﻤﻭ ‪‬‬
‫ﺘﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﻭﺫﻝﻙ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﻤﻥ ‪ E.D.T.A.‬ﺘﺭﻜﻴﺯﻩ‬
‫‪ .C 2 = 1.0 × 10−2 mol / L‬ﻨﺼل ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻋﻨﺩ ﺍﻝﺤﺠﻡ ‪.V2eqv = 8.6 mL‬‬
‫‪. log β([ CaY ]2− ) = 10.6,‬‬ ‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪log β([ MgY ]2− ) = 8.7 :‬‬
‫‪ .1‬ﻤﺎ ﻫﻭ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻹﺠﻤﺎﻝﻲ ‪ C 1‬ﻝﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﻴﺎﻩ؟‬
‫‪ .2‬ﺘﹸﻌﺭ‪‬ﻑ ﻗﺴﺎﻭﺓ ﺍﻝﻤﻴﺎﻩ ﺇﻤﺎ ﺒﺄﻨﻬﺎ ﺘﺴﺎﻭﻱ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﻭﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ S‬ﻤﻌﺒﺭﹰﺍ‬
‫ﻁﻰ ﺒﻌﺩﺩ ﻻ ﻭﺍﺤﺩﺓ ﻝﻪ ﻴﺴﺎﻭﻱ ‪ S×10‬ﻋﻠﻰ ﺃﻥ‬
‫ﻋﻨﻬﺎ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪ ، mmol / L‬ﻭﺇﻤﺎ ﹸﺘﻌ ﹶ‬
‫ﹸﺘﻜﻭﻥ ‪ S‬ﻤﻘﺩ‪‬ﺭﺓ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪ . mmol / L‬ﺍﺤﺴﺏ ﻗﺴﺎﻭﺓ ﺍﻝﻤﺎﺀ ﺍﻝﻤﺩﺭﻭﺱ‪.‬‬
‫ﺍﻝﺤل‬
‫ﻥ‬
‫‪ .1‬ﺒﺎﻝﻨﻅﺭ ﺇﻝﻰ ﺜﺎﺒﺘﻲ ﺘﻜﻭ‪‬ﻥ ﺍﻝﻤﻌﻘﺩﻴﻥ ﺍﻝﺨﺎﺼﻴﻥ ﺒﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﻴﻤﻜﻨﻨﺎ ﺍﻝﻘﻭل ﺇ ‪‬‬
‫ﻫﺎﺘﻴﻥ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﺴﻭﻑ ﺘﺘﻌﺎﻴﺭﺍﻥ ﻤﻌﹰﺎ‪ .‬ﻭﻨﻜﺘﺏ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪:‬‬
‫‪n 0 (Ca 2 + ) + n0 (Mg2 + ) = n(Y 4− )added‬‬
‫‪eqv‬‬
‫ﺃﻱ‬
‫‪C 1V1 = C 2V2eqv‬‬
‫ﻥ‪:‬‬
‫‪C 2V2eqv‬‬
‫= ‪C1‬‬ ‫‪= 1.7 × 10-3 mol / L‬‬
‫‪V1‬‬
‫‪ .2‬ﺘﻜﻭﻥ ﻗﺴﺎﻭﺓ ﺍﻝﻤﻴﺎﻩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﺍﻝﻤﻌﺎﻴ‪‬ﺭﺓ ‪ 1.7 mmol / L‬ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺍﻝﻤﻐﻨﺯﻴﻭﻡ‬
‫ﺃﻭ ﺘﹸﻌﻁﻰ ﺒﺎﻝﺭﻗﻡ ‪ 17‬ﻭﻓﻕ ﺍﻝﺘﻌﺭﻴﻑ ﺍﻝﺜﺎﻨﻲ ﻝﻘﺴﺎﻭﺓ ﺍﻝﻤﺎﺀ‪.‬‬
‫‬
‫ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺍﻝﺯﺌﺒﻕ )‪ (II‬ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺘﻴﻭﺴﻴﺎﻨﺎﺕ ‪ SCN−‬ﻤﻌﻘﹼﺩ ﹰﺍ ﺭﺒﺎﻋﻲ ﺍﻝﺭﺒﻴﻁﺔ‬ ‫‬
‫ﺒﺜﺎﺒﺕ ﺘﺸﻜﹼل ﺇﺠﻤﺎﻝﻲ ‪ ، β4 = 1021.7‬ﻓﻲ ﺤﻴﻥ ﺘﺸﻜﹼل ﻫﺫﻩ ﺍﻝﺸﺎﺭﺩﺓ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺎﻨﻴﺩ‬
‫‪ CN−‬ﻤﻌﻘﹼﺩﹰﺍ ﺭﺒﺎﻋﻲ ﺍﻝﺭﺒﻴﻁﺔ ﺒﺜﺎﺒﺕ ﺘﺸﻜﹼل ﺇﺠﻤﺎﻝﻲ ‪. β4′ = 1042.5‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ ﻝﺘﻔﺎﻋﻠﻲ ﺘﺸﻜﹼل ﻫﺫﻴﻥ ﺍﻝﻤﻌﻘﹼﺩﻴﻥ‪.‬‬
‫‪ .2‬ﻨﻤﺯﺝ ‪ 50.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻨﺘﺭﺍﺕ ﺍﻝﺯﺌﺒﻕ ﺒﺘﺭﻜﻴﺯ ‪ 1.00 × 10−2 mol/L‬ﻤﻊ‬
‫‪ 50.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺘﻴﻭﺴﻴﺎﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭ ﻡ ﺒﺘﺭﻜﻴﺯ ‪. 5.00 × 10−2 mol/L‬‬

‫ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ )ﺃﻱ ﺘﺭﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ(‪.‬‬
‫‪ .3‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ‪ 100.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺴﻴﺎﻨﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬
‫‪. 5.00 × 10−2 mol/L‬‬

‫)‪ (a‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﻨﺎﺘﺞ ﻭﺤﺩ‪‬ﺩ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪.‬‬
‫)‪ (b‬ﺍﺴﺘﻨﺘﺞ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺠﺩﻴﺩ‪.‬‬
‫ﺍﻝﻤﻌﻘﹼﺩ‬ ‫‪Ag+‬‬ ‫ﺍﻝﻔﻀﺔ‬ ‫ﺸﺎﺭﺩﺓ‬ ‫ﻤﻊ‬ ‫ﺍﻝﺘﻴﻭﻜﺒﺭﻴﺘﺎﺕ ‪S2O23−‬‬ ‫ﺸﺎﺭﺩﺓ‬ ‫ﺘﺸﻜﹼل‬ ‫‬
‫] ‪ ، [ Ag(S2O3 )2‬ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻹﺠﻤﺎﻝﻲ ‪ ، β = 1013.5‬ﻭﺘﺸﻜﹼل ﻫﺫﻩ‬ ‫‪3−‬‬
‫ﺍﻝﺸﺎﺭﺩﺓ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺯﺌﺒﻕ ‪ Hg 2+‬ﻤﻌﻘﹼﺩﹰﺍ ‪ [ Hg(S2O3 )2 ]2−‬ﺒﺜﺎﺒﺕ ﺘﺸﻜﹼل ﺇﺠﻤﺎﻝﻲ‬

‫ﺒﺘﺭﻜﻴﺯ‬ ‫ﺍﻝﻔﻀﺔ‬ ‫ﻨﺘﺭﺍﺕ‬ ‫ﻤﺤﻠﻭل‬ ‫ﻤﻥ‬ ‫‪20.0 mL‬‬ ‫ﻨﻤﺯﺝ‬ ‫‪. β ′ = 1029‬‬
‫‪ 2.00 × 10−2 mol/L‬ﻤﻊ ‪ 30.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺘﻴﻭﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬
‫‪. 5.00 × 10−2 mol/L‬‬

‫‪ .1‬ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺯﻴﺞ ﺍﻝﻨﻬﺎﺌﻲ ﻤﻊ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻨﻬﺎﺌﻴﺔ‪.‬‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺯﻴﺞ ﺍﻝﺴﺎﺒﻕ ‪ 50.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻨﺘﺭﺍﺕ ﺍﻝﺯﺌﺒﻕ )‪ (II‬ﺒﺘﺭﻜﻴﺯ‬
‫‪ . 4.00 × 10−2 mol/L‬ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻭﻗﻴﻡ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻨﻬﺎﺌﻴﺔ‪.‬‬

‫ﺘﺩﺨل ﺸﺎﺭﺩﺓ ﺍﻝـ ‪ E .D.T .A‬ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﻓﻲ ﺘﻔﺎﻋﻼﺕ ﺘﻌﻘﻴﺩ‬ ‫‬
‫ﻝﺘﺸﻜﹼل ﺍ ﻝﻤﻌﻘﹼﺩ ﻴﻥ ‪ [ CaY ]2− :‬ﻭ ‪ . [ MgY ]2−‬ﻨﻀﻴﻑ ‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭل‬
‫ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ 0.2 mol/L‬ﺇﻝﻰ ‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺤﺎ ﹴﻭ ﻋﻠﻰ ﻤﻌﻘﹼﺩ‬
‫‪ [ MgY ]2−‬ﺒﺘﺭﻜﻴﺯ ‪. 0.2 mol/L‬‬
‫‪ .2‬ﺃﻭﺠﺩ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‪.‬‬
‫‪ .3‬ﻫل ﻴﻤﻜﻥ ﺍﻋﺘﺒﺎﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﻜﻤﻴﹰﺎ ) ﺃﻱ ﺘﺎﻤﹰﺎ( ﻭﻝﻤﺎﺫﺍ؟‬
‫‪ .4‬ﺃﻭﺠﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪ ) .‬ﺃﻱ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﻋﻨﺩ ﻭﻀﻊ‬
‫ﺍﻝﺘﻭﺍﺯﻥ(‪.‬‬
‫‪ .5‬ﺤﺩ‪‬ﺩ ﻋﻠﻰ ﻤﺤﻭﺭ ﺃﻓﻘﻲ ﻤﺩ ﺭ‪‬ﺝ ﺘﺒﻌﹰﺎ ﻝﻘﻴﻡ ‪ pY‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ‬
‫ﻭﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .6‬ﺍﺴﺘﻌﻥ ﺒﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﺴﺎﺒﻕ ﻓﻲ ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﺕ ﺇﻝﻴﻬﺎ‬
‫ﻓﻲ ﺍﻝﻁﻠﺏ ‪.4‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ ‪ log β([ CaY ]2− ) = 10.6 :‬ﻭ ‪. log β([ MgY ]2− ) = 8.7‬‬
‫ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷﻭﻜﺴﻴﻨﺎﺕ ‪ Ox −‬ﻤﻌﻘﹼﺩﹰﺍ ‪  MgOx ‬ﻭﻫﻲ ﺘﺸﻜﹼل‬

‫‪+‬‬
‫‬
‫ﻤﻊ ﺸﺎ ﺭ ﺩ ﺓ ﺍ ﻝـ ‪ Y 4− : E .D.T .A‬ﺍ ﻝﻤﻌﻘﹼﺩ ‪ . [ MgY ]2−‬ﻨﻀﻴﻑ ‪ 10.0 mL‬ﻤﻥ‬
‫ﻤﺤﻠﻭل ﺍﻝـ ‪ E .D.T .A‬ﺒﺘﺭﻜﻴﺯ ‪ 0.2 mol/L‬ﺇﻝﻰ ‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻴﺤﻭﻱ ﻤﻌﻘﹼﺩ‬
‫ﺃﻭﻜﺴﻴﻨﺎﺕ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ‪  MgOx ‬ﺒﺘﺭﻜﻴﺯ ‪. 0.2 mol/L‬‬

‫‪+‬‬

‫‪ .3‬ﻫل ﻴﻤﻜﻥ ﺍﻋﺘﺒﺎﺭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﻜﻤﻴﹰﺎ ) ﺃﻱ ﺘﺎﻤﹰﺎ( ﻭﻝﻤﺎﺫﺍ؟‬
‫‪ .4‬ﺃﻭﺠﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪) .‬ﺃﻱ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﻋﻨﺩ ﻭﻀﻊ‬
‫ﺍﻝﺘﻭﺍﺯﻥ(‪.‬‬
‫‪ .5‬ﺤﺩ‪‬ﺩ ﻋﻠﻰ ﻤﺤﻭﺭ ﺃﻓﻘﻲ ﻤﺩ ﺭ‪‬ﺝ ﺘﺒﻌﹰﺎ ﻝﻘﻴﻡ ‪ pY‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ‬
‫ﻭﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .6‬ﺍﺴﺘﻌﻥ ﺒﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﺴﺎﺒﻕ ﻝﻠﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﺕ ﺇﻝﻴﻬﺎ ﻓﻲ‬
‫ﺍﻝﻁﻠﺏ ‪.4‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪ log β( MgY  ) = 8.7 :‬ﻭ ‪. log β( MgOx  ) = 4.7‬‬
‫‪+‬‬ ‫‪2−‬‬
‫ﻨﻀﻴﻑ ‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﻜﺒﺭ ﻴﺘﺎ ﺕ ﺍ ﻝﺴﻴﺭ ﻴﻭ ﻡ )‪ Ce2(SO4 )3 : (III‬ﺒﺘﺭ ﻜﻴﺯ‬ ‫‬
‫‪ 0.1 mol/L‬ﺇ ﻝﻰ ‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﻓﻠﻭ ﺭ ﻴﺩ ﺍ ﻝﺼﻭ ﺩ ﻴﻭ ﻡ ‪ Na F‬ﺒﺘﺭ ﻜﻴﺯ‬
‫‪ . 0.2 mol/L‬ﻨﻀﻴﻑ ﺒﻌﺩ ﺫﻝﻙ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻭﻤﻊ ﺇﻫﻤﺎل ﺍﻝﺘﻐﻴ‪‬ﺭ ﻓﻲ ﺍﻝﺤﺠﻡ ﻜﻤﻴ ﹰﺔ‬
‫‪ n‬ﻤﻥ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ‪ HCl‬ﺒﺤﻴﺙ ﻴﺘﻌﻘﹼﺩ ﻓﻘﻁ ‪ 50%‬ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺭﻴﻭﻡ )‪. (III‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻭﺍﺯﻥ ﺍﻝﺤﺎﺼل ﻗﺒل ﺇﻀﺎﻓﺔ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .2‬ﺃﻭﺠﺩ ﺘﺭﺍﻜﻴﺯ ‪ [ CeF ]2 + ، F - ، Ce3+‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﻗﺒل ﺇﻀﺎﻓﺔ ﺤﻤـﺽ‬
‫ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .3‬ﺤﺩ‪‬ﺩ ﻋﻠﻰ ﻤﺤﻭﺭ ﺃﻓﻘﻲ ﻤﺩﺭ‪‬ﺝ ﺘﺒﻌﹰﺎ ﻝﻘﻴﻡ ‪ pF‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ‬
‫‪ .4‬ﺍﺴﺘﻌﻥ ﺒﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺍﻝﺴﺎﺒﻕ ﻝﻠﺘﺤﻘﹼﻕ ﻤﻥ ﺼﺤﺔ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﺕ ﺇﻝﻴﻬﺎ ﻓـﻲ‬
‫ﺍﻝﻁﻠﺏ ‪.2‬‬
‫‪ .5‬ﻤﺎ ﺘﺄﺜﻴﺭ ﺇﻀﺎﻓﺔ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﻋﻠﻰ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭﻴﺩ ﺍﻝﺤﺭﺓ ﺃﻭﻻﹰ‪ ،‬ﺜ ‪‬ﻡ ﻋﻠﻰ ﻤﻨﺤﻰ‬
‫ﺘﻭﺍﺯﻥ ﺍﻝﺘﻌﻘﻴﺩ ﺍﻝﺴﺎﺒﻕ ﺜﺎﻨﻴﺎﹰ؟‬
‫‪ .6‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﻘﹼﺩ ﻤﻊ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .8‬ﺤﺩ‪‬ﺩ ﺘﺭﺍﻜﻴﺯ ‪ Ce3+‬ﻭ ‪ F−‬ﻭ ‪ [ CeF ]2 +‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺒﻌﺩ ﺇﻀﺎﻓﺔ ﻤﺎ ﻴﻜﻔـﻲ ﻤـﻥ‬
‫ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﻹﺯﺍﺤﺔ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﻭﻓﻕ ﺍﻝﻤﻨﺤﻰ ﺍﻝﻤﻁﻠﻭﺏ‪.‬‬
‫‪ .9‬ﺍﻜﺘﺏ ﻤﻌﺎﺩﻝﺔ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﻝﻌﻨﺼﺭ ﺍﻝﻔﻠﻭﺭ‪ ،‬ﻭﺍﺴﺘﻨﺘﺞ ﻤﻨﻬﺎ ﺘﺭﻜﻴﺯ ﺍﻝﺤﻤﺽ ‪. HF‬‬
‫‪ .10‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .11‬ﺃﻭﺠﺩ ﻗﻴﻤﺔ ‪. n‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ ‪ log β([ CeF ]2 + ) = 4.1 :‬ﻭ ‪. pK A (HF/F− ) = 3.2‬‬
‫ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺍﻝﻔﻠﻭﺭ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ )‪ Fe3+ (III‬ﺃﺭﺒﻌﺔ ﻤﻌﻘﹼﺩﺍﺕ ﻤﺘﻌﺎﻗﺒﺔ ﺒﺄﺩﹼﻝﺔ ﺘﺴﺎﻨﺩ‬ ‫‬
‫‪ 1‬ﻭ ‪ 2‬ﻭ ‪ 3‬ﻭ ‪ . 4‬ﻭﺘﻜﻭﻥ ﻗﻴﻡ ﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻹﺠﻤﺎﻝﻴﺔ ‪ βi‬ﻝﻬﺫﻩ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻫﻲ‪:‬‬
‫‪. log β4 = 16.1 ، log β3 = 13.7 ، log β2 = 10.7 ، log β1 = 6.0‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﻋﺒﺎﺭﺍﺕ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻔﻜﹼﻙ ﺍﻝﻤﺘﻌﺎﻗﺒﺔ ﻝﻬﺫﻩ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﺍﻷﺭﺒﻌﺔ ‪ ، Kdi‬ﺜ ‪‬ﻡ ﺍﺤﺴﺒﻬﺎ‬
‫ﻋﺩﺩﻴﹰﺎ‪.‬‬
‫‪ .2‬ﺍﺭﺴﻡ ﻤﺨﻁﹼﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺒﺩﻻﻝﺔ ] ‪. pF = −log [ F−‬‬
‫ﻻ ﺤﺼﻠﻨﺎ ﻋﻠﻴﻪ ﺒﻤﺯﺝ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ )‪ (III‬ﻤﻊ ﻤﺤﻠﻭل‬
‫‪ .3‬ﻝﻨﻌﺘﺒﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﻤﻥ ﻓﻠﻭﺭﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ .‬ﺤﺩ‪‬ﺩ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺭﺍﺠﺤﺔ ﻋﻨﺩﻤﺎ‪:‬‬
‫)‪. pF = 4.1 (a‬‬
‫)‪. [F− ] = 3.5 × 10−3 mol/L (b‬‬
‫ﻴﻌﻁﻲ ﺍ ﻝﺸﻜل ﺍ ﻝﺘﺎ ﻝﻲ ﻤﺨﻁﻁ ﺍ ﻝﺘﻭ ﺯ ﻴﻊ ﻝﻠﺸﻭ ﺍ ﺭ ﺩ ﻓﻲ ﺤﺎ ﻝﺔ ﻤﻌﻘﺩ ﺍ ﺕ ﺃ ﻤﻴﻥ ﺍ ﻝﻜﻭ ﺒﺎ ﻝﺕ‬ ‫‬
‫ﺍﻝﺜﻼ ﺜﻲ )‪ (III‬ﻭﺫﻝﻙ ﺒﺩﻻﻝﺔ ] ‪ ، pNH3 = −log [ NH3‬ﻭﺍﻝﺘﻲ ﺘﻘﻊ ﻓﻴﻬﺎ ﺃ ﺩﻝﺔ ﺍﻝﺘﺴﺎﻨﺩ‬
‫ل ﺸﺎﺭﺩﺓ ﺤﺎﻭﻴﺔ‬
‫ﺒﻴﻥ ‪ 1‬ﻭ ‪ . 6‬ﺘﻤﺜﹼل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﻤﺭﺴﻭﻤﺔ ﻓﻲ ﺍﻝﻤﺨﻁﻁ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻜ ّ‬
‫ﻋﻠﻰ ﺍﻝﻜﻭﺒﺎﻝﺕ )‪ (III‬ﻭﺫﻝﻙ ﻤﻊ ﺘﻐﻴ‪‬ﺭ ‪. pNH3‬‬
‫‪%‬‬
‫‪90‬‬
‫‬
‫‪80‬‬ ‫
‬
‫‪70‬‬
‫‪60‬‬ ‫‬
‫‪50‬‬
‫‪40‬‬ ‫‬
‫‪30‬‬
‫‪20‬‬
‫‬ ‫‬ ‫ ‬
‫‪10‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8 pNH 3‬‬
‫ﻥ ﺍﻝﻌﺩﺩ ﺍﻝﺫﺭﻱ ﺍﻝﺨﺎﺹ ﺒﺎﻝﻜﻭﺒﺎﻝﺕ ﻫﻭ ‪. Z = 27‬‬

‫‪ .1‬ﺇﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫)‪ (a‬ﻋﻠﹼل ﺴﺒﺏ ﻭﺠﻭﺩ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Co(NH3 )6 ]3+‬ﺒﺎﺴﺘﻌﻤﺎل ﻗﺎﻋﺩﺓ ﺍﻝﺜﻤﺎﻨﻴﺔ ﻋﺸﺭ‬
‫ﺇﻝﻜﺘﺭﻭﻨﹰﺎ‪.‬‬
‫)‪ (b‬ﺤﺩ‪‬ﺩ ﺍﻝﺒﻨﻴﺔ ﺍﻝﻔﺭﺍﻏﻴﺔ ﻝﻬﺫﺍ ﺍﻝﻤﻌﻘﹼﺩ‪.‬‬
‫ﻱ ﺸﺎﺭﺩﺓ ﺘﻌﻭﺩ ﻤﺨﺘﻠﻑ ﻫﺫﻩ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﻤﺭﺴﻭﻤﺔ‪.‬‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ﺇﻝﻰ ﺃ ‪‬‬
‫‪ .3‬ﺤﺩ‪‬ﺩ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺴﺎﺒﻘﺔ‪ ،‬ﻤﻊ ﺘﻌﻠﻴل ﺍ ﻝﻁﺭﻴﻘﺔ ﺍﻝﻤﺴﺘﻌﻤﻠﺔ ‪ ،‬ﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﹼل‬
‫ل ﻤﻥ ﻫﺫﻩ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪.‬‬
‫ﺍﻝﻤﺘﻌﺎﻗﺒﺔ ‪ ، K fi‬ﺜ ‪‬ﻡ ﺍﺴﺘﻨﺘﺞ ﻤﻨﻬﺎ ﺜﻭﺍﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﻜ ّ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﺤﺼﻠﻨﺎ ﻋﻠﻴﻪ ﺒﻤﺯﺝ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﻭﺒﺎﻝﺕ )‪ (III‬ﻤﻊ‬
‫‪ .4‬ﻝﻨﺘﺄﻤل ﻤﺤﻠﻭ ﹰ‬
‫ﻤﺤﻠﻭل ﻤﻥ ﺍﻝﻨﺸﺎﺩﺭ‪ .‬ﺤﺩ‪‬ﺩ ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﺴﺎﺒﻘﺔ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩﻤﺎ‪:‬‬
‫)‪. pNH3 = 5.0 (a‬‬
‫)‪. [NH3 ] = 3.5 × 10−4 mol/L (b‬‬
‫ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺍﻝﻜﻭﺒﺎﻝﺕ )‪ (III‬ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻷ ﻭ ﻜﺴﺎﻻﺕ ‪ C2O24−‬ﻤﻌﻘﺩ ﹰﺍ ﺴﺩﺍﺴﻲ ﺍﻝﺘﺴﺎﻨﺩ‬ ‫‬
‫‪ [ Co(C2O4 )3 ]4−‬ﺒﺤﻴﺙ ﻴﻜﻭ ﻥ ‪ . log β3 = 19.2‬ﻤﻥ ﺠﻬﺔ ﺃ ﺨﺭ ﻯ ‪ ،‬ﺘﺸﻜﹼل ﻫﺫﻩ‬
‫ﺍﻝﺸﺎﺭﺩﺓ ﻤﻊ ﺜﻨﺎﺌﻲ ﺃﻤﻴﻥ ﺍﻹﻴﺜﻠﻴﻥ ‪ H2NCH2CH2NH2‬ﺍﻝﺫﻱ ﻨﺭﻤﺯ ﺇ ﻝﻴﻪ ﻋﺎﺩﺓ ﺒﺎﻝﺭﻤﺯ‬
‫‪ en‬ﻤﻌﻘﺩﹰﺍ ﺴﺩﺍﺴﻲ ﺍﻝﺘﺴﺎﻨﺩ ‪ [ Co(en)3 ]2+‬ﺒﺤﻴﺙ ﻴﻜﻭﻥ ‪. log β3′ = 13.9‬‬
‫‪ .1‬ﻋﻠﹼل ﺒﺎﺴﺘﻌﻤﺎل ﺒﻨﻴﺔ ﺸﺎﺭﺩﺓ ﺍﻷ ﻭ ﻜﺴﺎﻻﺕ ‪ C2O24−‬ﻭ ﻜﺫﻝﻙ ﺒﻨﻴﺔ ﺜﻨﺎﺌﻲ ﺃﻤﻴﻥ ﺍﻹﻴﺜﻠﻴﻥ‬
‫‪ H2NCH2CH2NH2‬ﻜﻭﻥ ﺍﻝﻤﻌﻘﺩﻴﻥ ﺍﻝﻤﺘﺸﻜﹼﻠﻴﻥ ﺴﺩﺍﺴﻴ‪‬ﻲ ﺍﻝﺘﺴﺎﻨﺩ‪.‬‬
‫‪ .2‬ﺍﺭﺴﻡ ﺍﻝﺒﻨﻴﺔ ﺍﻝﻬﻨﺩﺴﻴﺔ ﺍﻝﻔﺭﺍﻏﻴﺔ ﻝﻬﺎﺘﻴﻥ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﺍﻝﻤﻌﻘﺩﺘﻴﻥ‪ .‬ﻫل ﻫﻤﺎ ﺸﺎﺭﺩﺘﺎﻥ‬
‫ﻜﻴﺭﺍﻝﻴﺘﺎﻥ؟‬
‫ل ﻝﻠﻤﻌﻘﺩ ‪ [ Co(en)3 ]2+‬ﺘﺭ ﻜﻴﺯ ﻩ ﻴﺴﺎ ﻭﻱ‬
‫‪ .3‬ﻨﻀﻴﻑ ﺇ ﻝﻰ ‪ 100 mL‬ﻤﻥ ﻤﺤﻠﻭ ﹴ‬
‫‪ 2.0 × 10−2 mol/L‬ﻭ ﺩ ﻭ ﻥ ﺘﻤﺩ ﻴﺩ ﻤﻘﺩ ﺍ ﺭ ‪ 1.0 × 10−2 mol‬ﻤﻥ ﺃ ﻭ ﻜﺴﺎ ﻻﺕ‬
‫ﺍﻝﺼﻭﺩﻴﻭﻡ ‪. Na 2 C2O4‬‬
‫)‪ (a‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺫﻱ ﺠﺭﻯ‪.‬‬
‫)‪ (b‬ﺍﺤﺴﺏ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل‪.‬‬
‫)‪ (c‬ﺍﺴﺘﻨﺘﺞ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ل ﺘ ‪‬ﻡ ﺍﻝﺤﺼﻭل ﻋﻠﻴﻪ‬

‫ﻴﻤﺜﹼل ﺍﻝﺭﺴﻡ ﺍﻝﺒﻴﺎﻨﻲ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﻝﻠﺸﻭﺍﺭﺩ ﺍﻝﻤﻭ ﺠﻭ ﺩﺓ ﻓﻲ ﻤﺤﻠﻭ ﹴ‬ ‫ ‬
‫ﺒﺎ ﻹﻀﺎ ﻓﺔ ﺍ ﻝﺘﺩ ﺭ ﻴﺠﻴﺔ ﻝﻤﺤﻠﻭ ل ‪ EDTA‬ﺍ ﻝﺤﺎ ﻭ ﻱ ﻋﻠﻰ ﺍ ﻝﺸﻭ ﺍ ﺭ ﺩ ﺍ ﻝﻤﻌﻘﱢﺩ ﺓ ‪Y 4 −‬‬
‫)ﺍﻝﺭﺒﻴﻁﺎﺕ( ﺇﻝﻰ ﻤﺤﻠﻭل ﺤﺎ ﹴﻭ ﻋﻠﻰ ﻤﺯﻴﺞ ﻤﺘﺴﺎﻭﻱ ﺍﻝﺘﺭﻜﻴﺯ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ ‪Ba 2+‬‬
‫ﻭﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ ، Ca 2+‬ﺒﺤﻴﺙ ﺘﻤﺜﹼل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﻤﻌﻁﺎﺓ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻜل ﻤﻥ‬
‫‪ Ca 2+‬ﻭ ‪ Ba 2+‬ﻭ ‪ [ CaY ]2−‬ﻭ ‪ [ BaY ]2−‬ﺒﺩﻻﻝﺔ ] ‪. pY = − log [Y 4 −‬‬
‫‪%‬‬
‫‪90‬‬
‫‬
‫‪80‬‬
‫‪70‬‬ ‫‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‬
‫‪20‬‬
‫‬
‫‪10‬‬
‫‪pY‬‬
‫‪0‬‬
‫‪0‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬ ‫‪4‬‬ ‫‪5‬‬ ‫‪6‬‬ ‫‪7‬‬ ‫‪8‬‬ ‫‪9‬‬ ‫‪10 11 12‬‬
‫ﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ CaY ]2−‬ﺃﻜﺜﺭ ﺍﺴﺘﻘﺭﺍﺭﹰﺍ ﻤﻥ ﺍﻝﻤﻌﻘﹼﺩ ‪. [ BaY ]2−‬‬

‫ل ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻷﺭﺒﻌﺔ؟‬
‫ﻱ ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﻤﻌﻘﺩﺍﺕ ﺍﻝﻭﺍﺭﺩﺓ ﺁﻨﻔﹰﺎ ﻴﻌﻭﺩ ﻜ ّ‬
‫‪ .1‬ﺇﻝﻰ ﺃ ‪‬‬
‫‪ .2‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻡ ﺜﺎﺒﺘﻲ ﺍﻝﺘﺸﻜﹼل ﻝﻠﻤﻌﻘﹼﺩﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪.‬‬
‫‪ .3‬ﻤﺎ ﻫﻲ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺭﺍﺠﺤﺔ ﻋﻨﺩ ‪ pY =7‬ﻭ ‪ pY =10‬؟‬
‫‪ .4‬ﻴﻤﻜﻥ ﺍﻻﺴﺘﻌﺎﻨﺔ ﺒﺘﻔﺎﻋﻠﻲ ﺍﻝﺘﻌﻘﻴﺩ ﺍﻝﺴﺎﺒﻘﻴﻥ ﻓﻲ ﻤﻌﺎﻴﺭﺓ ﻤﺯﻴﺞ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬

‫ﻭﺍﻝﺒﺎﺭﻴﻭﻡ‪ :‬ﻝﻬﺫﺍ ﺴﻭﻑ ﻨﺄﺨﺫ ﻤﺯﻴﺠﹰﺎ ﻤﺘﺴﺎﻭﻱ ﺍﻝﻤﻭﻝﻴﺔ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﺍﻝﺒﺎﺭﻴﻭﻡ‪،‬‬
‫ﻻ ﺤﺎﻭﻴﹰﺎ ﻋﻠﻰ ﺍﻝﺸﺎﺭﺩﺓ ‪.Y 4 −‬‬
‫ﻨﻀﻴﻑ ﺇﻝﻴﻪ ﻤﺤﻠﻭ ﹰ‬
‫)‪ (a‬ﻤﺎ ﻫﻲ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺘﻲ ﺴﺘﹸﻌﺎ ‪‬ﻴﺭ ﺃﻭﻻﹰ؟‬
‫)‪ (b‬ﻫل ﻤﻥ ﺍﻝﻤﻤﻜﻥ ﻤﻌﺎﻴﺭﺓ ‪ 95%‬ﻤﻥ ﻫﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﻤﻥ ﺩﻭﻥ ﺃﻥ ﻨﻌﺎﻴﺭ ﺃﻜﺜﺭ ﻤﻥ‬
‫‪ 5%‬ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻷﺨﺭﻯ؟‬
‫‪ .5‬ﻨﻀﻴﻑ ﺇ ﻝﻰ ‪ 100 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﻴﺤﺘﻭ ﻱ ﻋﻠﻰ ﻤﻘﺩ ﺍ ﺭ ‪ 1.0 × 10−3 mol‬ﻤﻥ‬
‫‪ [ BaY ]2−‬ﺒﺩ ﻭ ﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍ ﻝﺤﺠﻡ ﻤﻘﺩ ﺍ ﺭ ‪ 1.5 × 10−3 mol‬ﻤﻥ ﻜﻠﻭ ﺭ ﻴﺩ‬
‫ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪ ،‬ﻤﺎ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻝﻜل ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ‪ Ca 2+‬ﻭ ‪ Ba 2+‬ﻭ ‪[ CaY ]2−‬‬
‫ﻭ ‪. [ BaY ]2−‬‬
‫ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ )‪ (I‬ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻐﻠﻴﺴﻴﻨﺎﺕ ‪ gly−‬ﻤﻌﻘﹼﺩﻴﻥ‪:‬‬ ‫

‬
‫)‪ [ Ag(gly) ](log β1 = 3.5‬ﻭ )‪. [ Ag(gly)2 ]− (log β2 = 8.4‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻔﻜﹼﻙ ﺍﻝﺘﻌﺎﻗﺒﻴﺔ ﻝﻜﻼ ﺍﻝﻤﻌﻘﺩﻴﻥ‪.‬‬
‫‪ .2‬ﺍﺭﺴﻡ ﻤﺨﻁﻁ ﺍﻝﺭﺠﺤﺎﻥ ﺒﺩﻻﻝﺔ ] ‪. p gly = − log [ gly−‬‬
‫ﻥ ﺃﺤﺩ ﻫﺫﻴﻥ ﺍﻝﻤﻌﻘﹼﺩﻴﻥ ﺴﻭﻑ ﻴﺘﻔﻜﹼﻙ ﺘﻠﻘﺎﺌﻴﹰﺎ ﻝﻴﻌﻁﻲ ﺸﺎﺭﺩﺘﻴﻥ ﺇﺤﺩﺍﻫﻤﺎ ﺒﺩﻝﻴل‬
‫‪ .3‬ﺍﺴﺘﻨﺘﺞ ﺃ ‪‬‬
‫ﺘﺴﺎﻨﺩ ﺃﻗل ﻤﻥ ﺩﻝﻴل ﺘﺴﺎﻨﺩ ﻩ ‪ ،‬ﻭﺍﻷﺨﺭﻯ ﺒﺩﻝﻴل ﺘﺴﺎﻨﺩ ﺃﻋﻠﻰ ﻤﻥ ﺩﻝﻴل ﺘﺴﺎﻨﺩﻩ‪ .‬ﺍﺤﺴﺏ‬
‫ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‪.‬‬
‫ﻨﻤﺯ ﺝ ‪ 50.0 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﻨﺘﺭ ﺍ ﺕ ﺍ ﻝﺤﺩ ﻴﺩ )‪ (III‬ﺒﺘﺭ ﻜﻴﺯ ‪ 0.100 mol/L‬ﻤﻊ‬ ‫‬
‫‪ 50.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪. 0.100 mol/L‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺯﻴﺞ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪.‬‬
‫ﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺯﻴﺞ ﺍﻝﺴﺎﺒﻕ ﻭﻤﻥ ﺩﻭﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍﻝﺤﺠﻡ ﺤﻤ ‪‬‬
‫ﺼﻑﹾ ﺍﻝﻅﺎﻫﺭﺓ ﺍﻝﺘﻲ ﺴﺘﺤﺩﺙ‪.‬‬
‫)‪ (a‬‬
‫)‪ (b‬ﺤ ‪‬ﺩ ﺩ ﻋﺩ ﺩ ﻤﻭﻻﺕ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺍﻝﺘﻲ ﻴﻨﺒﻐﻲ ﺇﻀﺎ ﻓﺘﻬﺎ ﺤﺘﻰ ﻴﺘﻌﻘﹼﺩ ﻤﻥ‬
‫ل ﻤﻥ ‪. 1%‬‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (III‬ﺃﻗ ّ‬
‫)‪ (c‬ﺤﺩ‪‬ﺩ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ‪.‬‬
‫‪2+‬‬
‫‪log β( Fe(CH 3COO) ‬‬ ‫‪) = 3.2‬‬
‫‪pK A (CH 3COOH/CH3COO− ) = 4.8‬‬
‫ل ‪ 1.0 × 10−2 mol‬ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﺯﺌﺒﻕ‬

‫ﻻ ﺒﺴﻌﺔ ‪ 1.00 L‬ﻋﻥ ﻁﺭﻴﻕ ﺤ ّ‬
‫ﻨﺤﻀ‪‬ﺭ ﻤﺤﻠﻭ ﹰ‬ ‫‬
‫)‪ (II‬ﻭ ‪ 1.0 mol‬ﻤﻥ ﺍﻝﻨﺸﺎﺩﺭ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫ل ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﺍﺴﺘﻨﺘﺞ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﺘﺭﺍﻜﻴﺯ ﻜ ّ‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ﻭﻤﻥ ﺩﻭﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍﻝﺤﺠﻡ ﻋﺩﺩ ﹰﺍ ‪ n‬ﻤﻥ ﺍﻝﻤﻭﻻﺕ ﻤﻥ‬
‫ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪.‬‬
‫)‪ (a‬ﺼ‪‬ﻑ ﺍﻝﻅﺎﻫﺭﺓ ﺍﻝﺘﻲ ﺴﺘﺤﺩﺙ‪.‬‬
‫)‪ (b‬ﺤﺩ‪‬ﺩ ‪ n‬ﻋﺩﺩ ﻤﻭﻻﺕ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺍﻝﺘﻲ ﻴﻨﺒﻐﻲ ﺇﻀﺎﻓﺘﻬﺎ ﺤﺘﻰ ﻴﻜﻭﻥ‬
‫] ‪. [[Hg(NH3 )2 ]2+ ] = [[Hg(NH 3 )3 ]2+‬‬
‫)‪ (c‬ﺤﺩ‪‬ﺩ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﺠﺩﻴﺩ‪.‬‬
‫‪2+‬‬
‫‪log β2 ( Hg(NH3 )2 ‬‬ ‫‪) = 18‬‬
‫‪2+‬‬
‫‪log β3 ( Hg(NH3 )3  ) = 20‬‬
‫‪pK A (NH+‬‬
‫‪4 /NH 3 ) = 9.2‬‬
‫‪ S2O2-‬ﻤﻌﻘﹼﺩﻴﻥ ﻫﻤﺎ ‪[ Ag(S2O3 ) ]−‬‬

‫ﺘﺸﻜﹼل ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ ‪ I‬ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﺘﻴﻭﻜﺒﺭﻴﺘﺎﺕ ‪3‬‬ ‫‬
‫ﻭ ‪ [ Ag(S2O3 )2 ]3−‬ﺒﺤﻴﺙ ﻴﻜﻭ ﻥ ‪ . log β2 = 13.5 ، log β1 = 8.80‬ﻨﻀﻴﻑ‬
‫ﺇ ﻝﻰ ‪ 10.0 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﻨﺘﺭ ﺍ ﺕ ﺍ ﻝﻔﻀﺔ ﺒﺘﺭ ﻜﻴﺯ ‪C 0 = 0.050 mol/L‬‬
‫ﻭ ﺒﺎﺴﺘﻌﻤﺎ ل ﺍ ﻝﺴﺤ‪‬ﺎ ﺤﺔ ﺤﺠﻤﹰﺎ ‪ V‬ﻤﻥ ﻤﺤﻠﻭ ل ﺘﻴﻭ ﻜﺒﺭ ﻴﺘﺎ ﺕ ﺍ ﻝﺼﻭ ﺩ ﻴﻭ ﻡ ﺒﺘﺭ ﻜﻴﺯ‬
‫‪ .C = 0.050 mol/L‬ﻓﺈﺫﺍ ﻗﺒﻠﻨﺎ ﺃﻨﻪ ‪-‬ﻀﻤﻥ ﻫﺫﻩ ﺍﻝﺸﺭﻭﻁ‪ -‬ﻴﺠﺭﻱ ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﻴﻥ‬
‫ﺒﺎﻝﺘﻌﺎﻗﺏ‪ ،‬ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺃﻨﻨﺎ ﺴﻨﻜﺘﺏ ] ‪: pL = − log [ S2O23−‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﺤﺠﻤﻲ ﺍﻝﺘﻜﺎﻓﺅ ‪.VE2 ،VE1‬‬
‫‪ .2‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﺎﺼﻠﺔ‪:‬‬
‫)‪. 0 < V < VE1 (a‬‬
‫)‪.VE1 < V < VE2 (b‬‬
‫ل ﻤﻥ ﺍﻝﺤﺎﻻﺕ ﺍﻵﺘﻴﺔ‪:‬‬
‫‪ .3‬ﺇﺤﺴﺏ ‪ pL‬ﺇﻥ ﻜﺎﻥ ﻫﺫﺍ ﻤﻤﻜﻨﹰﺎ ﻓﻲ ﻜ ّ‬
‫ﻭ ‪.V = VE2‬‬ ‫‪ V = 0‬ﻭ ‪V = VE1‬‬
‫‪ .4‬ﺍﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ pL = f (V‬ﺒﻌﺩ ﺇﻴﺠﺎﺩ ﻋﺒﺎﺭﺘﻪ ﻓﻲ ﺍﻝﺤﺎﻻﺕ‪:‬‬

‫)‪. 0 < V < VE1 (a‬‬
‫)‪.VE1 < V < VE2 (b‬‬
‫)‪.V > VE2 (c‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺨﺎﻣﺲ‬
‫
‬
‫ ‬
‫‪ .I‬ﺍﻨﺤﻼل ﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ ﻓﻲ ﺍﻝﻤﺎﺀ ؛ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل‬
‫‪ .1.I‬ﺍﻨﺤﻼل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫‪ .2.I‬ﺘﻌﻤﻴﻡ‬
‫‪ .3.I‬ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻭﺍﻻﻨﺤﻼﻝﻴﺔ‬
‫‪ .II‬ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ‬
‫‪ .1.II‬ﺇﻴﺠﺎﺩ ﺍﻝﺸﺭﻁ‬
‫‪ .2.II‬ﺘﻁﺒﻴﻕ‬
‫‪ .3.II‬ﺃﺜﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ‬
‫‪ .III‬ﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺭﺍﺴﺏ ﻤﺎ‬
‫‪ .IV‬ﺘﻨﺎﻓﺱ ﺍﻝﺭﻭﺍﺴﺏ‬
‫‪ .1.IV‬ﺘﺠﺭﺒﺔ‬
‫‪ .2.IV‬ﺍﻝﺘﻌﻠﻴل‬
‫‪ .3.IV‬ﺘﻁﺒﻴﻕ‬
‫‪ .V‬ﺍﻻﻨﺤﻼﻝﻴﺔ ﻭﺍﻝﺘﻌﻘﻴﺩ‬
‫‪ .1.V‬ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸ ﹼﻜل ﻤﻌﻘﹼﺩ‬
‫‪ .2.V‬ﺘﻐﻴ‪‬ﺭ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸ ﹼﻜل ﻤﻌﻘﹼﺩﺍﺕ‬
‫‪ .VI‬ﺍﻝﺘﺭﺴﻴﺏ ﻭ ‪ pH‬ﺍﻝﻭﺴﻁ‬
‫‪ .1.VI‬ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﺒﻔﻌل ﺤﻤﺽ‬
‫‪ .2.VI‬ﺘﺭﺴﻴﺏ ﺴﻠﻔﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ‬
‫‪ .3.VI‬ﺘﺭﺴﻴﺏ ﻫﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ‬
‫‪ .VII‬ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﻝﺘﺭﺴﻴﺏ‬
‫‪ .1.VII‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫‪ .2.VII‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪p Ag = f (x‬‬
‫‪157‬‬
‫ﺍﻟﻔﺼﻞ ﺍﳋﺎﻣﺲ‬ ‫‪158‬‬
‫ﻤﻘﺩﻤﺔ‬
‫ﻜﺜﻴﺭﺓ ﻫﻲ ﺍﻷﻤﺜﻠﺔ ﻋﻠﻰ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻲ ﻴﺘﻜﻭ‪‬ﻥ ﻓﻴﻬﺎ ﺭﺍﺴﺏ‪ :‬ﺘﺭﺍﻜﻡ ﺍﻝﻜﻠﺱ ﺩﺍﺨل ﺍﻝﺘﻤﺩﻴﺩﺍﺕ‬
‫ﺍﻝﺼﺤﻴﺔ ﻭﺍﻝﺫﻱ ﻗﺩ ﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻨﺴﺩﺍﺩﻫﺎ ﺃﺤﻴﺎﻨﹰﺎ‪ ،‬ﻭﺍﻝﺘﺭﺴﻴﺏ ﺍﻻﻨﺘﻘﺎﺌﻲ ﻝﻤﺨﺘﻠﻑ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ‬
‫ﺍﻝﻤﻭﺠﻭﺩﺓ ﻀﻤﻥ ﻓﻠﺯ ﻭﺍﻝﺫﻱ ﻴﺴﻤﺢ ﺒﻔﺼل ﺍﻝﻤﻌﺎﺩﻥ ﺒﻌﻀﻬﺎ ﻋﻥ ﺒﻌﺽ‪ ،‬ﻭﺘﻨﻤﻴﺔ ﺍﻝﺒﻠﻭﺭﺍﺕ‪،‬‬
‫ﻭﺍﻝﻤﻌﺩﻨﺔ ﺍﻝﺒﻴﻭﻝﻭﺠﻴﺔ ﻝﻤﻴﻨﺎﺀ ﺍﻷﺴﻨﺎﻥ ﺒﺎﺴﺘﻌﻤﺎل ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭ‪ ،‬ﻭﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻀﻤﻥ‬
‫ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻭﻏﻴﺭﻫﺎ ﻜﺜﻴﺭ‪.‬‬
‫‪ .I‬ﺍﻨﺤﻼل ﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ ﻓﻲ ﺍﻝﻤﺎﺀ ؛ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل‬

‫‪ .1.I‬ﺍﻨﺤﻼل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫ﻝ ﹸﻨﻀ‪‬ﻑ ﺇﻝﻰ ﺇﻴﺭﻝﻴﻨﺔ ﺤﺎﻭﻴﺔ ﻋﻠﻰ ‪ 50mL‬ﻤﻥ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ ﺍﻝﻘﻠﻴل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫ﻥ ﺍﻝﺠﺴﻡ ﺍﻝﺼﻠﺏ ﻗﺩ ﺫﺍﺏ ﻜﻠﻴﹰﺎ‪ .‬ﻝ ﹸﻨﻀ‪‬ﻑ‬
‫‪ Ca SO4‬ﺒﺭﺃﺱ ﺍﻝﺴﺒﺎﺘﻭﻻ ﺜ ‪‬ﻡ ﻝﻨﺤﺭ‪‬ﻙ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻓﻨﺠﺩ ﺃ ‪‬‬
‫ﺽ‬
‫ﺏ ﺃﺒﻴ ‪‬‬
‫ﺍﻵﻥ ﺴﺒﺎﺘﻭﻝﺘﻴﻥ ﻜﺎﻤﻠﺘﻴﻥ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺜ ‪‬ﻡ ﻝﻨﺤﺭ‪‬ﻙ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻓﻨﻼﺤﻅ ﺒﻘﺎﺀ ﺭﺍﺴ ﹴ‬
‫ﻓﻲ ﻗﻌﺭ ﺍﻹﻴﺭﻝﻴﻨﺔ ﺒﻌﺩ ﺍﻝﺘﺤﺭﻴﻙ‪ .‬ﻨﻘﻭل ﺇﻨﹼﻨﺎ ﺤﺼﻠﻨﺎ ﻋﻠﻰ ﻤﺤﻠﻭل ﻤ‪‬ﺸﺒ‪‬ﻊ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪.‬‬
‫ﻝﻨﻘﻡ ﺍﻵﻥ ﺒﺘﺭﺸﻴﺢ ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﻝﻨﻀﻊ ﺍﻝﻘﻠﻴل ﻤﻥ ﺍﻝﺭﺸﺎﺤﺔ ﻓﻲ ﺃﻨﺒﻭﺒﻲ ﺍﺨﺘﺒﺎﺭ ﺍﻝﺸﻜل )‪:(1‬‬
‫ﻤﺤﻠﻭل ﻤﻥ ﻜﻠﻭﺭﻴﺩ‬ ‫ﻤﺤﻠﻭل ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ‬

‫ﺍﻝﺒﺎﺭﻴﻭﻡ‬ ‫ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫ﺍﻝﺭﺸﺎﺤﺔ‬ ‫ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ‬ ‫ﺍﻝﺭﺸﺎﺤﺔ‬ ‫ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ‬

‫ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ‬ ‫ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫ﺍﻝﺸﻜل ) ‪ : ( 1‬ﺍﻝﺘﺠﺎﺭﺏ ﺍﻝﻤﺠﺭﺍﺓ ﻋﻠﻰ ﺭﺸﺎﺤﺔ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺸﺒﻊ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪.‬‬

‫‪159‬‬ ‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻟﺘﺮﺳﻴﺐ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ ﻝ ﹸﻨﻀ‪‬ﻑ ﺇﻝﻰ ﺍﻷﻨﺒﻭﺏ ﺍﻷﻭل ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ ‪ BaCl2‬ﻓﻨﻼﺤﻅ ﺘﻜﻭ‪‬ﻥ ﺭﺍﺴﺏ ﺃﺒﻴﺽ‬
‫ﻥ ﺍﻝﺭﺸﺎﺤﺔ ﺘﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ‪. SO24−‬‬
‫ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ ‪ . BaSO4‬ﻫﺫﺍ ﻴ‪‬ﺜﺒﹺﺕ ﺃ ‪‬‬
‫ ﻝ ﹸﻨﻀ‪‬ﻑ ﺇﻝﻰ ﺍﻷﻨﺒﻭﺏ ﺍﻝﺜﺎﻨﻲ ﺍﻝﻘﻠﻴل ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ‪ ، Na 2CO3‬ﻓﻨﻼﺤﻅ ﺘﻜـﻭ‪‬ﻥ‬
‫ﻥ ﺍﻝﺭﺸﺎﺤﺔ ﺘﻀ ‪‬ﻡ ﺸـﻭﺍﺭﺩ‬
‫ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ . CaCO3‬ﻫﺫﺍ ﻴﺜﺒﺕ ﺃ ‪‬‬
‫ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﻴﺘﻜﻭ‪‬ﻥ ﺍﻝﺨﻠﻴﻁ ﺍﻝﺴﺎﺒﻕ ﻋﻨﺩ ﺍﻹﺸﺒﺎﻉ ﻤﻥ ﻁﻭﺭﻴﻥ ‪ :‬ﻁﻭﺭ ﺼﻠﺏ ) ‪ (s‬ﺃﻭ ﺭﺍﺴﺏ‬
‫ﻥ ﻤﻊ ﺸﻭﺍﺭﺩﻩ ﻓﻲ ﺍﻝﻁﻭﺭ ﺍﻝﺴﺎﺌل ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ‬
‫ﻭ ﻁﻭﺭ ﺴﺎﺌل ‪ ،‬ﻭﻴﻜﻭﻥ ﺍﻝﻁﻭﺭ ﺍﻝﺼﻠﺏ ﻓﻲ ﺘﻭﺍﺯ ﹴ‬
‫ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ‪:‬‬
‫‪2+‬‬
‫‪CaSO4 (s) ⇌ Ca‬‬ ‫‪+‬‬ ‫‪SO24−‬‬
‫ﻴﻭﺼﻑ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﺒﺎﺴﺘﻌﻤﺎل ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ‪ K s‬ﺍﻝﺫﻱ ﻴﺭﺒﻁ ﺒﻴﻥ ﺘﺭﺍﻜﻴﺯ ﻤﺨﺘﻠﻑ‬
‫ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻨﺤﻠﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺸﺒﻊ‪.‬‬
‫] ‪[Ca 2 + ] [SO24− ] [Ca 2 + ][SO24−‬‬
‫= ‪Ks‬‬ ‫⋅‬ ‫=‬
‫‪C0‬‬ ‫‪C0‬‬ ‫‪C 02‬‬
‫ﺤﻴﺙ ‪ C 0‬ﻫﻭ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﻤﺭﺠﻌﻲ ‪ .C 0 = 1.00 mol/L :‬ﻭﻏﺎﻝﺒﹰﺎ ﻤﺎ ﻨﻜﺘﺏ ﺍﻝﻌﻼﻗﺔ ﺍﻝﺴﺎﺒﻘﺔ‬
‫ﺒﺎﻝﺼﻴﻐﺔ ﺍﻝﻤﺒﺴﻁﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪ K s = [ Ca 2+ ][ SO24− ] :‬ﺸﺭﻁ ﺃﻥ ﻨﻌﺒ‪‬ﺭ ﻋﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺒﺎﻝﻭﺍﺤﺩﺓ‬
‫ﻥ ‪ K s (CaSO4 ) = 7.9 × 10−6‬ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ‬
‫‪ . mol/L‬ﻭ ﻗﺩ ﻭ‪‬ﺠﺩ ﺒﺎﻝﺘﺠﺭﺒﺔ ﺃ ‪‬‬
‫‪. 25o C‬‬
‫‪ .2.I‬ﺘﻌﻤﻴﻡ‬
‫ﻻ ﻤﺸﺒﻌﹰﺎ ﺤﺎﻭﻴﹰﺎ ﻋﻠﻰ ﻤﺭﻜﺏ ﺸﺎﺭﺩﻱ ﻀﻌﻴﻑ ﺍﻻﻨﺤﻼل ﻓﻲ ﺍﻝﻤﺎﺀ ﺒﺼﻴﻐﺔ‬

‫‪ C x Ay‬ﻓﻲ ﺘﻭﺍﺯﻥ ﻤﻊ ﺸﻭﺍﺭﺩﻩ ‪ C p +‬ﻭ ‪ Aq −‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ‪:‬‬
‫‪C x Ay ⇌ x C p + + y Aq −‬‬
‫ﺼﻑ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﺒﺜﺎﺒﺕ ﻴﺴﻤ‪‬ﻰ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻭﻨﺭﻤﺯ ﺇﻝﻴﻪ ﺒﺎﻝﺭﻤﺯ ‪ ، K s‬ﻭﻫﻭ ﻻ ﻴﺘﺒﻊ‬
‫‪‬ﻴﻭ ‪‬‬
‫ﻻ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺩﺍﺨﻠﺔ ﻓﻲ ﺍﻝﺘﻭﺍﺯﻥ ‪ ،‬ﻭﻫﻭ ﻜﺴﺎﺌﺭ ﺍﻝﺜﻭﺍﺒﺕ ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻴﺔ ﻻ ﻴﺘﻌﻠﹼﻕ ﺇﻻ‬
‫ﺇﹼ‬
‫ﺒﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ﻭﻨﻜﺘﺏ ‪:‬‬
‫‪ [C p + ] x‬‬ ‫‪ [Aq − ] y‬‬ ‫‪[C p + ]x [Aq − ]y‬‬
‫‪Ks = ‬‬ ‫‪‬‬ ‫‪‬‬
‫‪⋅ ‬‬ ‫= ‪‬‬
‫‪ C ‬‬‫‪0‬‬
‫‪ C 0 ‬‬ ‫‪C 0x +y‬‬
‫ﺤﻴﺙ ‪.C 0 = 1.00 mol/ L‬‬

‫ﻴﻤﻜﻥ ﺘﺒﺴﻴﻁ ﺍﻝﻌﺒﺎﺭﺓ ﺍﻝﺴﺎﺒﻘﺔ ﺒﺄﻥ ﻨﻜﺘﺏ‪:‬‬
‫‪x‬‬
‫‪K s = [C p + ] [ Aq − ]y‬‬
‫ﺸﺭﻁ ﺘﻘﺩﻴﺭ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪. mol/L‬‬
‫ﻭﻜﻤﺎ ﻓﻌﻠﻨﺎ ﺴﺎﺒﻘﹰﺎ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﻭﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻓﺈﻨﻨﺎ ﻨﻌﺭ‪‬ﻑ ‪:‬‬
‫‪p K s = − log K s‬‬
‫ ﺃﻤﺜﻠﺔ ‪:‬‬
‫ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ ‪. K s (Ag Cl ) = [ Ag+ ] ⋅ [ Cl− ] = 1.9 × 10−10‬‬
‫ﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ ‪. K s (Ag 2 Cr O4 ) = [ Ag + ] ⋅ [ Cr O24− ] = 1.6 × 10−12‬‬
‫‪2‬‬
‫‪ .3.I‬ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻭﺍﻻﻨﺤﻼﻝﻴﺔ‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻤﺸﺒﻌﹰﺎ ﻤﻥ ﻤﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ‪ .‬ﻨﺴﻤ‪‬ﻲ ﺍﻨﺤﻼﻝﻴﺔ ﻫﺫﺍ ﺍﻝﻤﺭﻜﹼﺏ ﻭﻨﺭﻤﺯ‬

‫ﻝﻴﻜﻥ ‪ V‬ﻤﺤﻠﻭ ﹰ‬
‫ﺞ ﻗﺴﻤﺔ ﻜﻤﻴﺔ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻤﻨﺤﻠﺔ ﻤﻥ ﻫﺫﺍ ﺍﻝﻤﺭﻜﹼﺏ ﻋﻠﻰ ﺤﺠﻡ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺸﺒﻊ ‪V‬‬
‫ﺇﻝﻴﻬﺎ ﺒﺎﻝﺭﻤﺯ ‪ s‬ﻨﺎﺘ ‪‬‬
‫ﻭﺫﻝﻙ ﻋﻨﺩ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﻤﻌﻴﻨﺔ‪ .‬ﻭﺘﻘﺩ‪‬ﺭ ﺍﻻﻨﺤﻼﻝﻴﺔ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪. mol/L‬‬
‫ﻓﻠﻭ ﺃﺨﺫﻨﺎ ﺍﻝﻤﺭ ﻜﹼﺏ ﺍ ﻝﺸﺎﺭﺩﻱ ‪ C x Ay‬ﺍﻝﺫﻱ ﻴﻨﺤل ﻓﻲ ﺍﻝﻤﺎﺀ ﻝﻴﻌﻁﻲ ﺍﻝﺸﻭﺍﺭﺩ ‪C p +‬‬
‫ﻭ ‪ Aq −‬ﺍﻝﺘﻲ ﻨﻔﺘﺭﺽ ﺃﻨﻬﺎ ﻻ ﺘﺘﻔﺎﻋل ﻤﻊ ﺍﻝﻤﺎﺀ‪ ،‬ﻓﺈﻨﻨﺎ ﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻬﺫﺍ ﺍﻻﻨﺤﻼل ﻜﻤﺎ‬
‫ﻴﻠﻲ ‪:‬‬
‫‪p+‬‬ ‫‪q−‬‬
‫‪C x Ay ⇌ x C‬‬ ‫‪+yA‬‬
‫ﺤﻴﺙ‬
‫‪ [C p + ] = x ⋅ s‬ﻭ ‪. [ Aq − ] = y ⋅ s‬‬
‫ﻭﻝﻤﹼﺎ ﻜﺎﻥ ‪ ، K s = [C p + ] [ Aq − ]y‬ﻜﺎﻥ ﻝﺩﻴﻨﺎ ‪:‬‬

‫‪x‬‬
‫‪K s = (sx )x ⋅ (sy )y = x x ⋅ y y ⋅ s x +y‬‬
‫ﻥ‪:‬‬
‫ﻭﻤﻨﻪ ﻨﺴﺘﻨﺘﺞ ﺃ ‪‬‬
‫‪1‬‬
‫‪ K x +y‬‬
‫‪s =  x s y ‬‬
‫‪x ⋅y ‬‬
‫ﻥ‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﻓﻲ ﺤﺎﻝﺔ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ ﺃ ‪‬‬
‫‪s = [ Ag + ] = [ Cl− ] = ( K s )1/2 = 1.4 × 10−5 mol/L‬‬
‫ﻥ‬
‫ﻭﻓﻲ ﺤﺎﻝﺔ ﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ ﻨﺠﺩ ﺃ ‪‬‬
‫‪1‬‬ ‫‪ K s′ 1/3‬‬

‫= ‪s′‬‬ ‫‪[ Ag ] = [ CrO4 ] =   = 7.4 × 10−5 mol/L‬‬
‫‪+‬‬ ‫‪2−‬‬
‫‪2‬‬ ‫‪ 4 ‬‬
‫‪ .II‬ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ‬
‫‪ .1.II‬ﺇﻴﺠﺎﺩ ﺍﻝﺸﺭﻁ‬
‫ﺼﻠﺏ ﺍﻝﺸﺎﺭﺩﻱ ‪ C x Ay‬ﻭﺍﻝﺸﻭﺍﺭﺩ ‪C p +‬‬

‫ﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺠﻤﻠﺔ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﻤﺅﻝﻔﺔ ﻤﻥ ﺍﻝﻤﺭﻜﺏ ﺍﻝ ‪‬‬
‫ﻭ ‪ Aq −‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ‪ .‬ﻭﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ ‪:‬‬
‫ ﺍﻝﻤﺭﻜﺏ ﺍﻝﺼﻠﺏ ‪ C x Ay‬ﻭﺍﻝﺸﻭﺍﺭﺩ ‪ C p +‬ﻭ ‪ Aq −‬ﻓﻲ ﺤﺎﻝﺔ ﺘﻭﺍﺯﻥ ﻓﻴﻤﺎ ﺒﻴﻨﻬﺎ‪ .‬ﻋﻨﺩﺌﺫ‬
‫ﻨﺼﻑ ﺍﻝﻤﺤﻠﻭل ﺒﺄﻨﻪ ﻤﺸﺒﻊ ﻭ ﹸﺘﺤﻘﹼﻕ ﺍﻝﺘﺭﺍﻜﻴﺯ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ‪ [C p + ]e‬ﻭ ‪[ Aq − ]e‬‬
‫ﺍﻝﻌﻼﻗﺔ‪:‬‬
‫‪x‬‬
‫‪K s = [C p + ]e [ Aq − ]ey‬‬
‫ ﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ ‪ ،‬ﻓﻴﻜﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻏﻴﺭ ﻤﺸﺒﻊ ‪ ،‬ﻭﺘﻜﻭﻥ ﺍﻝﺠﻤﻠﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺨﺎﺭﺝ ﻭﻀﻊ‬
‫ﺍﻝﺘﻭﺍﺯﻥ‪.‬‬
‫ﻫﻨﺎ ﻨﺘﺄﻤ‪‬ل ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﺍﻝﻤﻌﺭ‪‬ﻑ ﺒﺎﻝﺼﻴﻐﺔ‪:‬‬

‫‪x‬‬
‫‪Qr = [C p + ] [ Aq − ]y‬‬
‫ﻭﻨﻼﺤﻅ ﺃﻨﻪ ‪:‬‬
‫ﻥ ‪.Qr < K s‬‬
‫‪ å‬ﻋﻨﺩﻤﺎ ﻻ ﻴﻜﻭﻥ ﻫﻨﺎﻝﻙ ﺭﺍﺴﺏ‪ ،‬ﻓﺈ ‪‬‬
‫‪ å‬ﻋﻨﺩﻤﺎ ﻴﺒﺩﺃ ﺍﻝﺭﺍﺴﺏ ﺒﺎﻝﺘﻜﻭ‪‬ﻥ ‪ .Qr = K s‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪. ( 2‬‬
‫] ‪[C p +‬‬
‫ﺘﺭﺴﻴﺏ‬
‫ﻤﺤﻠﻭل ﻤﺸﺒﻊ‬
‫ﻻ ﺭﺍﺴﺏ‬
‫‪Qr = K s‬‬
‫‪Qr < K s‬‬
‫ﻤﺤﻠﻭل ﻏﻴﺭ ﻤﺸﺒﻊ‬
‫] ‪[ Aq −‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 2‬ﺸﺭﻁ ﺘﺭﺴ‪‬ﺏ ﺍﻝﺠﺴﻡ ﺍﻝﺼﻠﺏ ‪ C x Ay‬ﺒﺩﻻﻝﺔ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ‪ C p +‬ﻭ ‪. Aq −‬‬
‫ل ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫ﻥ ﻫﺫﺍ ﺍﻝﻤﺭ ﻜﹼﺏ ﻴﻨﺤ ّ‬
‫ﻭﻫﻜﺫﺍ ﻋﻨﺩﻤﺎ ﻨﻀﻴﻑ ﻤﺭﻜﺒﹰﺎ ﺸﺎﺭﺩﻴﹰﺎ ﺇﻝﻰ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪ ،‬ﻓﺈ ‪‬‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻏﻴﺭ‬
‫ﻤﺎﺩﺍﻡ ﺍﻝﺠﺩﺍﺀ ‪ Qr‬ﺃﺼﻐﺭ ﻤﻥ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ‪ ، K s‬ﻭﻨﻘﻭل ﺇ ‪‬‬
‫ﻤﺸﺒﻊ‪.‬‬
‫ﻥ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻴﺤﺘﻭﻱ ﻋﻠﻰ ﺍﻝﺸﻭﺍﺭﺩ ‪ C p +‬ﺇﻝﻰ ﻤﺤﻠﻭل ﺁﺨﺭ ﻴﺤﺘﻭﻱ ﻋﻠﻰ‬
‫ﻜﺫﻝﻙ ﻓﺈ ‪‬‬
‫ﺍﻝﺸﻭﺍﺭﺩ ‪ Aq −‬ﻴﺅﺩﻱ ﺇﻝﻰ ﺒﺩﺀ ﻅﻬﻭﺭ ﺭﺍﺴﺏ ﻤﻥ ‪ C x Ay‬ﻋﻨﺩﻤﺎ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺴﺎﻭﺍﺓ ‪:‬‬
‫‪x‬‬
‫‪Qr = [C p + ] [ Aq − ]y = K s‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃﻨﻪ ﻴﻤﻜﻨﻨﺎ ﺍﻨﻁﻼﻗﹰﺎ ﻤﻥ ﻗﻴﻡ ‪ Qr‬ﺍﻝﺘﻨﺒﺅ ﺒﻭﺠﻭﺩ ﺭﺍﺴﺏ ﻓﻲ ﺘﻭﺍﺯﻥ ﻤﻊ ﺸﻭﺍﺭﺩﻩ‬
‫ﺍﻝﻤﻜﻭ‪‬ﻨﺔ ﻓﻲ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺃﻭ ﻻ‪.‬‬
‫‪ .2.II‬ﺘﻁﺒﻴﻕ‬
‫ﻨﻤﺯ ﺝ ‪ 10 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ﻜﺒﺭ ﻴﺘﺎ ﺕ ﺍ ﻝﺼﻭ ﺩ ﻴﻭ ﻡ ﺒﺘﺭ ﻜﻴﺯ ‪ 8 × 10−2 mol/L‬ﻤﻊ‬
‫‪ 10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ ﺒﺎﻝﺘﺭﻜﻴﺯ ﺫﺍﺘﻪ‪ .‬ﻫل ﻨﺤﺼل ﻋﻠﻰ ﺭﺍﺴﺏ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻔﻀﺔ‬
‫ﻥ ‪ K s (Ag 2SO4 ) = [ Ag + ] ⋅ [ SO24− ] = 1.5 × 10−5‬؟‬
‫ﺇﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫‪2‬‬
‫ﺍﻝﺤل‬
‫ﻝﻨﺤﺴﺏ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﺠﺩﻴﺩﺓ ﺒﻌﺩ ﺍﻝﻤﺯﺝ ﻝﻜل ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻭﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‪ ،‬ﻓﻨﺠﺩ‬
‫‪[ Ag+ ] = 4 × 10−2 mol/L‬‬
‫‪[ SO24− ] = 4 × 10−2 mol/L‬‬
‫ﻥ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺘﺸﺎﺭﺩﻱ ‪ Qr‬ﻴﺴﺎﻭﻱ ‪:‬‬
‫ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫‪Qr = [Ag+ ]2 ⋅ [SO24− ] = 6.4 × 10−5‬‬
‫ﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻔﻀﺔ ﺴﻭﻑ ﺘﺘﺭﺴ‪‬ﺏ‪ .‬ﺃﻤﺎ ﻜﻤﻴﺔ ﺍﻝﺭﺍﺴﺏ‬

‫ﻥ ‪ Qr > K s‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻭ ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﻤﺘﻜﻭﻨﺔ ﻓﻬﻲ ﺘﻠﻙ ﺍﻝﺘﻲ ﺘﺠﻌل ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﺍﻝﺠﺩﻴﺩ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ‪ Qr′‬ﻤﺴﺎﻭﻴﹰﺎ ﻝﺠﺩﺍﺀ‬
‫ﺍﻻﻨﺤﻼل ‪. K s‬‬
‫

‬
‫ﺘﺸﻜﹼل ﺍﻝﺼﻭﺍﻋﺩ ﻭﺍﻝﻨﻭﺍﺯل‬
‫ﺇﺫﺍ ﻜﻨﺕ ﻗﺩ ﺯﺭﺕ ﻤﻐﺎﺭﺓ ﺠﻌﻴﺘﺎ ﻓﻲ ﻝﺒﻨﺎﻥ‪ ،‬ﻓﻼ ﺒ ‪‬ﺩ ﺃﻨﻙ ﻓﹸﺘﻨﺕ ﺒﺭﻭﻋﺔ ﺍﻝﻤﺸﻬﺩ ﺍﻝﺫﻱ ﺭﺃﻴﺕ‪ .‬ﻓﻬل ﺘﺴﺎﺀﻝﺕ ﻜﻴﻑ ﺘﺘﺸـﻜﹼل‬
‫ﺍﻝﺼﻭﺍﻋﺩ ﻭﺍﻝﻨﻭﺍﺯل؟!‬
‫ﺘﺘﺸﻜل ﺍﻝﺼﻭﺍﻋﺩ ﻭﺍﻝﻨﻭﺍﺯل ﻓﻲ ﺍﻝﻜﻬﻭﻑ ﺍﻝﻜﻠﺴﻴﺔ ﺍﻝﻤﻜﻭﻨﺔ ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ CaCO3‬ﻭﻫﻭ ﻤﺭﻜﺏ ﺸﺎﺌﻊ‬
‫ﺍﻻﻨﺘﺸﺎﺭ ﻓﻲ ﺍﻝﻁﺒﻴﻌﺔ ﺇﺫ ﻨﺠﺩﻩ ﺫﺍﺘﻪ ﻓﻲ ﺍﻝﻤﺭﺠﺎﻥ ﻭﺍﻝﺼﺩﻑ ﺍﻝﺒﺤﺭﻱ ﻭﻗﺸﺭﺓ ﺍﻝﺒﻴﺽ ﻭﺍﻝﺼﺨﻭﺭ ﺍﻝﻜﻠﺴﻴﺔ ﻭﺍﻝﺭﺨﺎﻤﻴﺔ‪.‬‬
‫ﻭﻓﻲ ﺤﺎﻝﺘﻨﺎ ﻫﺫﻩ ﺘﺤﻔﺭ ﺍﻝﻤﻴﺎﻩ ﺍﻝﺒﺎﻁﻨﻴﺔ ﺍﻝﺼﺨﻭﺭ ﺍﻝﻜﻠﺴﻴﺔ ﺍﻝﻤﻼﻤﺴﺔ ﻝﻬﺎ ﻷﻨﻬﺎ ﻤﻴﺎﻩ ﺤﺎﻤﻀﻴﺔ ﻨﺘﻴﺠﺔ ﻻﻨﺤﻼل ﻏﺎﺯ ﺜﻨﺎﺌﻲ‬
‫ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺍﻝﺠﻭﻱ ﻓﻴﻬﺎ ﻋﻨﺩﻤﺎ ﻜﺎﻨﺕ ﻤﻁﺭﹰﺍ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ‪:‬‬
‫‪+‬‬ ‫‪1‬‬ ‫‪−‬‬
‫↽ )‪CO2 (g) + H2O(l‬‬‫)‪ H (aq) + HCO3 (aq‬‬
‫⇀‬ ‫)‪(1‬‬
‫‪2‬‬
‫ﺘﻘﻭﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺍﻝﻨﺎﺘﺠﺔ ﺒﺤل ﺍﻝﻜﻠﺱ ﻭﺘﺸﻜﻴل ﺍﻝﻜﻬﻭﻑ ﺍﻝﻜﻠﺴﻴﺔ‪:‬‬

‫‪1‬‬
‫↽ )‪CaCO3 (s) + H+ (aq‬‬ ‫‪2+‬‬ ‫‪−‬‬
‫)‪ Ca (aq) + HCO3 (aq‬‬
‫⇀‬ ‫)‪(2‬‬
‫‪2‬‬
‫ﻭﻴﺭﺸﺢ ﺍﻝﻤﺎﺀ ﺍﻝﺤﺎﻭﻱ ﻋﻠﻰ ﺍﻝﻜﻠﺱ ﺍﻝﻤﻨﺤل ﻤﻥ ﺴﻘﻑ ﺍﻝﻜﻬﻑ‪ ،‬ﻭﻤﺎ ﺇﻥ ﺘﺘﺸﻜﹼل ﻗﻁﺭﺓ ﺍﻝﻤﺎﺀ ﺤﺘﻰ ﺘﻔﻘﺩ ﺠﺯﺀﹰﺍ ﻤﻥ ﻏﺎﺯ‬
‫ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺍﻝﻤﻨﺤل ﻓﻴﻬﺎ )ﺤﺴﺏ ﻗﺎﻨﻭﻥ ﻫﻨﺭﻱ ﻓﻲ‬
‫ﺍﻝﺘﻭﺍﺯﻥ‬ ‫ﺇﺯﺍﺤﺔ‬ ‫ﺇﻝﻰ‬ ‫ﻴﺅﺩﻱ‬ ‫ﻭﻫﺫﺍ‬ ‫ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻙ(‪.‬‬
‫‪2‬‬ ‫ﻓﻲ ﺍﻻﺘﺠﺎﻩ ﺍﻝﻌﻜﺴﻲ‬ ‫ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻲ ﺍﻷﻭل )‪(1‬‬
‫ﻝﻠﺘﻌﻭﻴﺽ ﻋﻥ ﻓﻘﺩ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ‪ ،‬ﻭﻫﺫﺍ ﺒﺩﻭﺭﻩ‬
‫ﻴﺨﻔﺽ ﻤﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ‪ .‬ﻓﻴﻨﺯﺍﺡ ﺍﻝﺘﻭﺍﺯﻥ‬
‫‪2‬‬ ‫ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻲ ﺍﻝﺜﺎﻨﻲ )‪ (2‬ﻓﻲ ﺍﻻﺘﺠﺎﻩ ﺍﻝﻌﻜﺴﻲ‬
‫ﻝﻠﺘﻌﻭﻴﺽ ﻋﻥ ﻓﻘﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻭﻴﺘﺭﺴ‪‬ﺏ ﻤﻥ ﺠﺩﻴﺩ‬
‫ﺍﻝﻜﻠﺱ ﻭﺘﺒﺩﺃ ﺍﻝﻨﻭﺍﺯل ﺒﺎﻝﺘﺸﻜﹼل ﻤﻥ ﺍﻝﺴﻘﻑ‪ .‬ﺃﻤﺎ ﺍﻝﻤﺎﺀ ﺍﻝﺫﻱ‬
‫ﻴﺼل ﺇﻝﻰ ﺍﻷﺭﺽ ﻗﺒل ﺃﻥ ﻴﻔﻘﺩ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ ﺍﻝﻤﻨﺤل ﻓﻴﻪ ﻓﻬﻭ ﻴﺴﺎﻫﻡ ﻓﻲ ﺘﺸﻜﻴل ﺍﻝﺼﻭﺍﻋﺩ ﺒﺎﺘﺠﺎﻩ‬
‫ﺍﻝﺴﻘﻑ‪.‬‬
‫‪ .3.II‬ﺃﺜﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ‬
‫ﻴﻅﻬﺭ ﺃﺜﺭ ﻝﻠﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ ﻓﻲ ﺇﺤﺩﻯ ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ‪:‬‬

‫ﻼ ﻓﻲ ﻤﺤﻠﻭل ﻴﺤﻭﻱ ﺒﺩﺍﻴﺔ ﺸﻭﺍﺭﺩ ‪ C p +‬ﺃﻭ‬
‫• ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺠﺴﻡ ﺍﻝﺼﻠﺏ ‪ C x Ay‬ﻤﻨﺤ ﹰ‬
‫‪. Aq −‬‬
‫ﻻ ﻴﺤﻭﻱ ﺸﻭﺍﺭﺩ ‪ C p +‬ﺃﻭ ‪ Aq −‬ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﺤﻀ‪‬ﺭ ﻤﻥ ﺍﻨﺤﻼل‬
‫• ﻋﻨﺩﻤﺎ ﻨﻀﻴﻑ ﻤﺤﻠﻭ ﹰ‬
‫ﺍﻝﺠﺴﻡ ﺍﻝﺼﻠﺏ ‪.C x Ay‬‬
‫ﻻ ﻤﺸﺒﻌﹰﺎ ﻨﺘﺞ ﻋﻥ ﺍﻨﺤﻼل ﺍﻝﻤﺭﻜﺏ ﺍﻝﺼﻠﺏ ‪ C x Ay‬ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪.‬‬
‫ﻝﻨﺘﺄﻤل ﺍﻵﻥ ﻤﺤﻠﻭ ﹰ‬
‫ﻴﺘﺤﻘﹼﻕ ﺒﻴﻥ ﺍﻝﻤﺤﻠﻭل ﻭﺍﻝﺠﺴﻡ ﺍﻝﺼﻠﺏ ‪ C x Ay‬ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻲ ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫‪1‬‬ ‫‪p+‬‬ ‫‪q−‬‬
‫)‪(1‬‬ ‫↽ )‪C x Ay (s‬‬‫‪ xC + y A‬‬
‫⇀‬
‫‪2‬‬
‫= ‪. Ks‬‬ ‫‪[C p + ]ex‬‬ ‫ﻭﻴﺘﻤﻴﺯ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﺒﺠﺩﺍﺀ ﺍﻨﺤﻼل‪[ Aq − ]ey :‬‬
‫ﻝﻨﻀﻑ ﺇﻝﻰ ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل ﺸﻭﺍﺭﺩ ‪ Aq −‬ﻤﻊ ﺇﻫﻤﺎل ﺍﻝﺘﻤﺩﻴﺩ‪ .‬ﻴﻤﻜﻥ ﺇﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ‪Aq −‬‬
‫ﻫﺫﻩ ﺇﻤﺎ ﺒﺈﻀﺎﻓﺔ ﺍ ﻝﻤﺭ ﻜﹼﺏ ﺍ ﻝﺼﻠﺏ ‪ Naq A‬ﻭ ﺇﻤﺎ ﺒﺈﻀﺎﻓﺔ ﻤﺤﻠﻭ ل ﻤﺭ ﻜﹼﺯ ﻝﻠﻤﺭ ﻜﹼﺏ ﺍ ﻝﺼﻠﺏ‬
‫‪. Naq A‬‬
‫ﻴﺼﺒﺢ ﺘﺭﻜﻴﺯ ﺍ ﻝﺸﻭﺍﺭﺩ ‪ Aq −‬ﻤﺒﺎﺸﺭﺓ ﺒﻌﺩ ﺍﻹﻀﺎﻓﺔ ‪ . [Aq − ] > [Aq − ]e :‬ﻭﻴﻜﻭﻥ‬
‫ﺍﻝﺠﺩﺍﺀ ﺍﻝﺘﺸﺎﺭﺩﻱ ‪ Qr = [C p + ]ex ⋅ [Aq − ]y‬ﺃﻜﺒﺭ ﺘﻤﺎﻤﹰﺎ ﻤﻥ ‪ ، Ks‬ﻓﻴﻨﺯﺍﺡ ﺍﻝﺘﻭﺍﺯﻥ )‪ (1‬ﻓﻲ‬
‫ﺍ ﻻﺘﺠﺎ ﻩ ‪ 2‬ﻭ ﻴﺘﺭﺴ‪‬ﺏ ﺍ ﻝﻤﺯﻴﺩ ﻤﻥ ﺍ ﻝﻤﺭ ﻜﹼﺏ ﺍ ﻝﺼﻠﺏ ‪ C x Ay‬ﺤﺘﻰ ﺘﺘﺤﻘﹼﻕ ﻤﻥ ﺠﺩﻴﺩ ﺍ ﻝﻤﺴﺎ ﻭ ﺍﺓ‬
‫‪ .Qr = Ks‬ﻭﻫﺫﺍ ﺒﺩﻭﺭﻩ ﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻨﺨﻔﺎﺽ ﺍﻻﻨﺤﻼﻝﻴﺔ‪.‬‬
‫ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ‪ Aq −‬ﺃﻭ ‪ C p +‬ﻤﻥ ﻏﻴﺭ ﺘﻤﺩﻴﺩ ﻤﻠﺤﻭﻅ‪ ،‬ﺘﻨﺨﻔﺽ ﺍﻨﺤﻼﻝﻴﺔ‬
‫ﺍﻝﻤﺭﻜﺏ ﺍﻝﺸﺎﺭﺩﻱ ‪.C x Ay‬‬
‫‪ .a‬ﺘﻁﺒﻴﻕ ﺃﻭ‪‬ل‬
‫ﺍﺤﺴﺏ ﺍﻨﺤﻼﻝﻴﺔ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻔﻀﺔ ﻓﻲ ﺍﻝﺤﺎﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ‪:‬‬

‫‪ .a‬ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪.‬‬
‫‪ .b‬ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ ‪ ، C = 1.0 mol/L‬ﹸﺜ ‪‬ﻡ ﺒﺘﺭﻜﻴﺯ‬
‫ﻗﺩﺭﻩ ‪ .C = 2 × 10−2 mol/L‬ﺍﻝﻤﻌﻁﻴﺎﺕ‪. pKs (Ag2SO4 ) = 4.8 :‬‬

‫ﺍﻝﺤل‬
‫ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻔﻀﺔ ﻫﻲ‪:‬‬
‫‪Ag2 SO4 (s) ⇌ 2Ag+ + SO24−‬‬
‫ﺇﻥ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﻫﻲ ﺃﺴﺎﺱ ﻀﻌﻴﻑ ﺠﺩﹰﺍ‪ ،‬ﻭﺴﻨﻬﻤل ﺘﻔﺎﻋﻠﻬﺎ ﻤﻊ ﺍﻝﻤﺎﺀ‪.‬‬
‫‪ .a‬ﻝﺘﻜﻥ ‪ s 0‬ﺍﻨﺤﻼﻝﻴﺔ )‪ Ag2SO4 (s‬ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪ ،‬ﻓﻴﻜﻭﻥ ‪:‬‬
‫‪[SO24− ] = s 0‬‬ ‫ﻭ‬ ‫‪[Ag+ ] = 2s 0‬‬
‫ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ‪:‬‬
‫‪Ks = [Ag+ ]2 ⋅ [SO24− ] = 4 s 02‬‬
‫‪ Ks 1/3‬‬
‫‪. s 0 =   = 1.6 × 10−2 mol/L‬‬
‫‪ 4 ‬‬
‫‪ .b‬ﻝﺘﻜﻥ ‪ s‬ﺍﻨﺤﻼﻝﻴﺔ ﺍﻝﻤﺭﻜﹼﺏ ﺍﻝﺸﺎﺭﺩﻱ )‪ Ag2SO4 (s‬ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫ﺒﺘﺭﻜﻴﺯ ‪ .C‬ﻭﻴﺼﺒﺢ ﺘﻔﺎﻋل ﺍﻨﺤﻼل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻔﻀﺔ ﻓﻲ ﻤﺤﻠﻭل ﻴﻀﻡ ﺒﺩﺍﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‬
‫ﺒﺘﺭﻜﻴﺯ ‪ C‬ﻜﻤﺎ ﻴﻠﻲ‪:‬‬
‫‪Ag2SO4 (s) 2Ag+‬‬ ‫‪+ SO24−‬‬

‫‪t =0‬‬ ‫‪0‬‬ ‫‪C‬‬
‫‪teq‬‬ ‫‪2s‬‬ ‫‪C +s‬‬
‫ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل‪. Ks = 4 s 2 (C + s ) :‬‬

‫ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺤﻠﻭل ﺫﻱ ﺍﻝﺘﺭﻜﻴﺯ ‪.C = 1.0 mol/L‬‬
‫ﻨﻅﺭﹰﺍ ﺇﻝﻰ ﻗﻴﻤﺘﻲ ‪ C‬ﻭ ‪ s 0‬ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻬﻤل ﺍﻻﻨﺤﻼﻝﻴﺔ ‪ s‬ﻤﻘﺎﺒل ‪. s ≪ C :C‬‬
‫ﻭﺒﻬﺫﺍ ﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل‪. Ks ≈ 4 s 2 ⋅ C :‬‬
‫ﻥ‪:‬‬
‫‪1/2‬‬
‫‪K‬‬ ‫‪ = 2.0 × 10−3 mol/L‬‬
‫‪s ≈  s‬‬ ‫‪‬‬
‫‪ 4C‬‬ ‫‪‬‬
‫ﻭﺘﺅﻜﺩ ﻫﺫﻩ ﺍﻝﻨﺘﻴﺠﺔ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺔ ﺍﻝﺘﻲ ﻭﻀﻌﻨﺎﻫﺎ‪.‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺤﻠﻭل ﺫﻱ ﺍﻝﺘﺭﻜﻴﺯ ‪.C = 2 × 10−2 mol/L‬‬

‫ل ﺍﻝﻤﻌﺎﺩﻝﺔ ﻤﻥ ﺍﻝﺩﺭﺠﺔ‬
‫ﻻ ﻴﻤﻜﻨﻨﺎ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺇﻫﻤﺎل ﺍﻻﻨﺤﻼﻝﻴﺔ ‪ s‬ﻤﻘﺎﺒل ‪ .C‬ﻭﻴﺠﺏ ﺤ ّ‬
‫ﺍﻝﺜﺎﻝﺜﺔ‪:‬‬
‫) ‪Ks = 4 s 2 (C + s‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺒﺎﺴﺘﻌﻤﺎل ﺇﺤﺩﻯ ﺍﻝﺒﺭﻤﺠﻴﺎﺕ ﺍﻝﻤﺘﺨﺼﺼﺔ ﻨﺠﺩ‪:‬‬
‫ﻭﺒﺤ ّ‬
‫‪. s = 1.1 × 10−2 mol/L‬‬
‫

‬
‫ﺍﻷﺸﻌﺔ ﺍﻝﺴﻴﻨﻴﺔ ﻝﻠﻤﻌﺩﺓ ﻭﺍﻷﻤﻌﺎﺀ‬
‫ﻥ ﺍﻝﻨﺴﺞ ﺍﻝﻁﺭﻴﺔ ﻓﻲ ﺍﻝﺠﺴﻡ ﻜﺘﻠﻙ ﺍﻝﺘﻲ ﻓﻲ ﺍﻝﻤﻌﺩﺓ ﻭﺍﻷﻤﻌﺎﺀ‬

‫ﻻﺘﻤﺘﺹ ﺠﻴﺩﹰﺍ ﺍﻷﺸﻌﺔ ﺍﻝﺴﻴﻨﻴﺔ‪ ،‬ﻭﻝﺫﻝﻙ ﻓﻌﻨﺩﻤﺎ ﻴﻠﺯﻡ ﺃﺨﺫ ﺼﻭﺭﺓ ﺒﺎﻷﺸﻌﺔ‬
‫ﻻ ﻤﻌﻠﹼﻘ ﹰﺎ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ‬
‫ﺍﻝﺴﻴﻨﻴﺔ ﻝﻠﻤﻌﺩﺓ ﻭﺍﻷﻤﻌﺎﺀ‪ ،‬ﻴ‪‬ﻌﻁﻰ ﺍﻝﻤﺭﻴﺽ ﻓﻤﻭﻴ ﹰﺎ ﻤﺤﻠﻭ ﹰ‬
‫ﺍﻝﺒﺎﺭﻴﻭﻡ ‪ Ba SO4‬ﺍﻝﻀﻌﻴﻔﺔ ﺍﻻﻨﺤﻼل ﻓﻲ ﺍﻝﻤﺎﺀ ‪ Ks = 10−9.9‬ﻗﺒل‬
‫ﺹ ﺠﻴﺩﹰﺍ ﺍﻷﺸﻌﺔ ﺍﻝﺴﻴﻨﻴﺔ‪،‬‬
‫ﻥ ﺫﺭﺍﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ ﺘﻤﺘ ‪‬‬
‫ﺃﺨﺫ ﺍﻝﺼﻭﺭﺓ‪ ،‬ﻨﻅﺭﹰﺍ ﻷ ‪‬‬
‫ﻭﻝﺫﻝﻙ ﻓﻬﻲ ﺘﺴﺎﻫﻡ ﻓﻲ ﺇﻅﻬﺎﺭ ﺍﻝﻌﻀﻭ ﺍﻝﻤﺭﺍﺩ ﺘﺼﻭﻴﺭﻩ‪ .‬ﻭﻋﻠﻰ ﺍﻝﺭﻏﻡ ﻤﻥ‬
‫ﻥ ﻫﺫﺍ ﻻ ﻴﻤﻨﻊ ﻤﻥ ﺍﺴﺘﻌﻤﺎل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ‬
‫ﻻ ﺃ‪‬‬
‫ﺴﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ ﺇ ﹼ‬
‫ﻷﻨﻬﺎ ﻻﺘﻨﺤل ﺠﻴﺩﹰﺍ ﺒﺎﻝﻤﺎﺀ ‪. s = 1.1 × 10−5 mol/L‬‬
‫ﻭﻝﻠﺘﺨﻔﻴﻑ ﻤﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ ﻓﻲ ﺍﻝﺠﺴﻡ ﻴ‪‬ﺴﺘﻌﻤل ﺘﺄﺜﻴﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ ﻓﻲ ﺇﺯﺍﺤﺔ ﺘﻭﺍﺯﻥ ﺍﻻﻨﺤﻼل ﺇﺫ‬
‫ﻴﻀﺎﻑ ﺇﻝﻰ ﺍﻝﻤﻌﻠﹼﻕ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ‪ Na 2 SO4‬ﺒﺘﺭﻜﻴﺯ ‪ 0.1mol/L‬ﺍﻝﺘﻲ ﺘﺤﺭ‪‬ﺭ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﻭﺘﺯﻴﺢ‬
‫ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺘﺎﻝﻲ ﻓﻲ ﺍﻻﺘﺠﺎﻩ ‪: 2‬‬

‫‪1‬‬ ‫‪2+‬‬
‫‪→ Ba‬‬
‫‪Ba SO4 ←‬‬ ‫‪+‬‬ ‫‪SO24−‬‬
‫‪2‬‬
‫ﻓﻴﻨﺨﻔﹼﺽ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ ﻝﻴﺼﺒﺢ ‪ ، s ′ = 1.3 × 10−9 mol/L‬ﺃﻱ ﺃﻨﻪ ﻴﻨﺨﻔﺽ ﺒﺤﺩﻭﺩ ‪ 104‬ﻤﺭﺓ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﺘﻤﺭ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ ﻓﻲ ﺍﻷﻨﺒﻭﺏ ﺍﻝﻬﻀﻤﻲ ﻜﻤﺎ ﻫﻲ‪ ،‬ﺜ ‪‬ﻡ ﺘﹸﻁﺭﺡ ﺨﺎﺭﺝ ﺍﻝﺠﺴﻡ ﻋﻘﺏ ﺍﻝﺘﺼﻭﻴﺭ ﺒﺎﻷﺸﻌﺔ‬
‫ﺍﻝﺴﻴﻨﻴﺔ‪.‬‬
‫‪ .b‬ﺘﻁﺒﻴﻕ ﺜﺎﻥ‬
‫ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﺤﺠﻡ ‪ V1 = 50 mL‬ﻤﻥ ﺍﻝﻤﺤﻠﻭل ‪ S1‬ﺍﻝﻤﺸﺒﻊ ﺒﻜﻠﻭﺭﻴﺩ ﺍﻝﺭﺼﺎﺹ )‪(II‬‬

‫ﺤﺠﻤﹰﺎ ﻗﺩ ﺭ ﻩ ‪ V2 = 50 mL‬ﻤﻥ ﻤﺤﻠﻭ ل ‪ S 2‬ﻤﻥ ﻜﻠﻭ ﺭ ﻴﺩ ﺍ ﻝﺼﻭ ﺩ ﻴﻭ ﻡ ﺒﺘﺭ ﻜﻴﺯ ﻗﺩ ﺭﻩ‬
‫‪ .C 2 = 0.10 mol/L‬ﻝﻨﺴ ‪‬ﻡ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ‪ . S 3‬ﺍﺤﺴﺏ ﺍﻨﺤﻼﻝﻴﺔ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺭﺼﺎﺹ )‪(II‬‬
‫ل ﻤﻥ ﺍﻝﻤﺤﻠﻭﻝﻴﻥ ‪ S1‬ﻭ ‪. S 3‬‬
‫ﻓﻲ ﻜ ﱟ‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪. pKs (PbCl2 ) = 4.7 :‬‬
‫ﺍﻝﺤل‬
‫‪ .a‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ‪ S1‬ﻴﺘﺤﻘﹼﻕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫‪PbCl2 (s) ⇌ Pb2 + + 2 Cl−‬‬
‫ﻝﺘﻜﻥ ‪ s 0‬ﺍﻨﺤﻼﻝﻴﺔ ‪ PbCl2‬ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪ ،‬ﻓﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫ﻭ ‪[Cl− ] = 2s 0‬‬ ‫‪[Pb2 + ] = s 0‬‬
‫ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل‪:‬‬
‫‪. Ks = [Pb2 + ] ⋅ [Cl− ]2 = 4 s 02‬‬
‫ﻥ‪:‬‬
‫) ‪. s 0 = ( Ks /4‬‬
‫‪1/3‬‬
‫‪= 1.7 × 10−2 mol/L‬‬
‫‪ .b‬ﻝﺘﻜﻥ ‪ s‬ﺍﻨﺤﻼﻝﻴﺔ ﺍﻝﻤﺭ ﻜﹼﺏ ﺍﻝﺘﺸﺎﺭﺩﻱ )‪ PbCl2 (s‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ‪ . S 3‬ﻨﺴﺘﻁﻴﻊ ﺍﻝﻨﻅﺭ ﺇﻝﻰ‬
‫ﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺭﺼﺎﺹ ﻴﻨﺤل ﻓﻲ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ﻗﺩﺭﻩ ‪:‬‬
‫ﺍﻝﻤﺴﺄﻝﺔ ﻭﻜﺄ ‪‬‬
‫‪C 2 ⋅ V2‬‬
‫= ‪C‬‬ ‫‪= C 2 /2‬‬
‫‪V1 + V2‬‬
‫ﻭﻨﻜﺘﺏ ﺍﻝﺘﻭﺍﺯﻥ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪PbCl2 (s) Pb2 +‬‬ ‫‪+ 2 Cl−‬‬
‫‪t =0‬‬ ‫‪0‬‬ ‫‪C‬‬
‫‪teq‬‬ ‫‪s‬‬ ‫‪C + 2s‬‬
‫ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل‪. Ks = s(C + 2 s )2 :‬‬

‫ﺃﻱ‬
‫‪. 4 s 3 + 4 C ⋅ s 2 + C 2s − Ks = 0‬‬
‫ﻥ‪:‬‬
‫ل ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺒﺎﺴﺘﻌﻤﺎل ﺒﺭﻤﺠﻴﺔ ﻤﺘﺨﺼﺼﺔ ﻨﺠﺩ ﺃ ‪‬‬
‫ﻭﺒﺤ ّ‬
‫‪. s = 5.4 × 10−3 mol/L‬‬
‫ﻥ ‪ ، s < s 0‬ﻓﻭﺠﻭﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﺃﺩﻯ ﺇﻝﻰ ﺍﻨﺨﻔﺎﺽ ﺍﻨﺤﻼﻝﻴﺔ ‪. PbCl2‬‬
‫

‬
‫ﻜﻴﻑ ﺘﺨﻔﹼﻑ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭ ﻤﻥ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ؟‬
‫ﺨﻼل ﺍﻝﻨﺼﻑ ﺍﻷﺨﻴﺭ ﻤﻥ ﺍﻝﻘﺭﻥ ﺍﻝﻤﺎﻀﻲ ﺍﻨﺨﻔﺽ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ ﺒﺼﻭﺭﺓ ﻤﻠﺤﻭﻅﺔ ﻓﻲ ﺍﻝﻌﺎﻝﻡ‪ ،‬ﻭﺫﻝﻙ ﺒﺈﻀﺎﻓﺔ ﻜﻤﻴﺎﺕ‬
‫ﺼﻐﻴﺭﺓ ﺠﺩﹰﺍ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭ ﺇﻝﻰ ﻤﻴﺎﻩ ﺍﻝﺸﺭﺏ ‪ 6 × 10−5 mol/L‬ﺃﻭ ﺇﻝﻰ ﻤﻌﺎﺠﻴﻥ ﺍﻷﺴﻨﺎﻥ ﻋﻠﻰ ﺸﻜل ﻓﻠﻭﺭﻴﺩ‬
‫ﻼ‪ ،‬ﺤﻴﺙ ﺘﺼل ﻨﺴﺒﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﻌﺎﺠﻴﻥ ﺇﻝﻰ ﺤﺩﻭﺩ ‪ . 1450 ppm‬ﻓﻜﻴﻑ ﻴﺴﺎﻫﻡ ﺍﻝﻔﻠﻭﺭ‬
‫ﺍﻝﺼﻭﺩﻴﻭﻡ ﻤﺜ ﹰ‬
‫ﻓﻲ ﺍﻝﺘﺨﻔﻴﻑ ﻤﻥ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ؟‬

‫ﺘﺘﻜﻭ‪‬ﻥ ﺍﻝﻤﻴﻨﺎﺀ‪ ،‬ﻭﻫﻲ ﺃﻗﺴﻰ ﻁﺒﻘﺔ ﻓﻲ ﺍﻝﺴﻥ‪ ،‬ﻭﺘﻜﻭ‪‬ﻥ ﺍﻝﻁﺒﻘﺔ ﺍﻝﺨﺎﺭﺠﻴﺔ ﺍﻝﻭﺍﻗﻴﺔ ﻝﻪ‪ ،‬ﻤﻥ ﻤﺎﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻲ ﺁﺒﺎﺘﻴﺕ‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻤﺎﺩﺓ ﻏﻴﺭ ﻗﺎﺒﻠﺔ ﻝﻼﻨﺤﻼل ﻨﻅﺭﹰﺍ‬
‫‪ (Ca 5 (PO4 )3OH) Hydroxyapatite‬ﻭﺫﻝﻙ ﺒﻨﺴﺒﺔ ‪ . 98%‬ﻭﻤﻊ ﺃ ‪‬‬
‫ﻝﻠﻘﻴﻤﺔ ﺍﻝﻤﺘﺩﻨﻴﺔ ﻝﺠﺩﺍﺀ ﺍﻨﺤﻼﻝﻬﺎ ﻓﻲ ﺍﻝﻤﺎﺀ ‪ ، Ks = 6.8 × 10−37‬ﻓﺈ ‪‬‬
‫ﻥ ﻋﻤﻠﻴﺔ ﺍﻨﺤﻼﻝﻬﺎ ﻭﺍﻝﺘﻲ ﺘﺤﻤل ﺍﺴﻡ‬
‫‪) demineralization‬ﻨﺯﻉ ﺍﻝﻤﻌﺎﺩﻥ ﻤﻥ ﺍﻝﻤﻴﻨﺎﺀ( ﺘﺤﺼل ﻋﻨﺩﻤﺎ ﻴﺤﻭﻱ ﺍﻝﻠﻌﺎﺏ ﺤﻤﻀ ﹰﺎ ﻨﺘﺞ ﻋﻥ ﺘﻔﻜﹼﻙ ﺍﻝﻤﻭﺍﺩ‬
‫ﺍﻝﺴﻜﺭﻴﺔ ﺒﻔﻌل ﺒﻜﺘﺭﻴﺎ ﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻔﻡ ﻫﻲ ﺍﻝﻤﺘﺴﺒﺒﺔ ﻓﻲ ﻨﺨﺭ ﺍﻷﺴﻨﺎﻥ‪.‬‬
‫ﻝﻤﻨﻊ ﺍﻝﻨﺨﺭ ﻴﻨﺒﻐﻲ ﺇﻴﺠﺎﺩ ﺁﻝﻴﺔ ﺘﺤﺭ‪‬ﺽ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻌﻜﻭﺱ ﻝﻌﻤﻠﻴﺔ ﺍﻻﻨﺤﻼل ﻭﺍﻝﺘﻲ ﺘﹸﻌﺭﻑ ﺒﺎﺴﻡ ‪remineralization‬‬
‫)ﺇﻋﺎﺩﺓ ﺍﻝﻤﻌﺎﺩﻥ ﺇﻝﻰ ﺍﻝﻤﻴﻨﺎﺀ( ﺒﺤﻴﺙ ﻴﺠﺭﻱ ﻓﻴﻬﺎ ﺘﺭﺴﻴﺏ ﻤﻴﻨﺎﺀ ﺍﻝﺴﻥ ﻤﻥ ﺠﺩﻴﺩ‪ ،‬ﻓﻜﻴﻑ ﻨﺤﻘﹼﻕ ﺫﻝﻙ؟‬
‫ل ﺸﻭﺍﺭﺩ‬
‫ل ﻤﺤ ّ‬
‫ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻲ ﺁﺒﺎﺘﻴﺕ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻠﻭﺭ‪ ،‬ﻴﻤﻜﻥ ﻝﻬﺫﻩ ﺍﻝﺸﻭﺍﺭﺩ ﺃﻥ ﺘﺤ ّ‬
‫ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻭﺘﺸﻜﹼل ﻓﻠﻭﺭﻴﺩ ﺍﻵﺒﺎﺘﻴﺕ )‪ (Ca 5 (PO4 )3 F‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﺠﺩﺍﺀ ﺍﻨﺤﻼل ‪ Ks = 1 × 10−60‬ﺃﺼﻐﺭ‬
‫ﺒﻜﺜﻴﺭ ﻤﻥ ﺠﺩﺍﺀ ﺍﻨﺤﻼل ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻲ ﺁﺒﺎﺘﻴﺕ‪ ،‬ﻭﺍﻝﺫﻱ ﺴﻴﺘﺭﺴ‪‬ﺏ ﻋﻠﻰ ﺍﻝﻤﻴﻨﺎﺀ‪ .‬ﻴﻘﻭﻡ ﻓﻠﻭﺭﻴﺩ ﺍﻵﺒﺎﺘﻴﺕ ﺒﺈﻋﺎﺩﺓ ﺍﻝﻤﻌﺎﺩﻥ‬
‫ﺇﻝﻰ ﻤﻴﻨﺎﺀ ﺍﻝﺴﻥ ﺒﺈﺯﺍﺤﺔ ﻫﻴﺩﺭﻭﻜﺴﻲ ﺍﻵﺒﺎﺘﻴﺕ ﻭﻝﻭ ﺠﺯﺌﻴ ﹰﺎ‪.‬‬
‫ﻥ ﻋﻤﻠﻴﺔ ﻨﺯﻉ ﺍﻝﻤﻌﺎﺩﻥ ﻤﻥ ﺍﻝﻤﻴﻨﺎﺀ‬
‫ﻻ ﻓﻲ ﺍﻝﻤﺎﺀ ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻲ ﺁﺒﺎﺘﻴﺕ‪ ،‬ﻓﺈ ‪‬‬
‫ل ﺍﻨﺤﻼ ﹰ‬
‫ﻭﻨﻅﺭﹰﺍ ﻝﻜﻭﻥ ﻓﻠﻭﺭﻴﺩ ﺍﻵﺒﺎﺘﻴﺕ ﺃﻗ ّ‬
‫ﻓﻴﻤﺎ ﺒﻌﺩ ﺴﺘﺼﺒﺢ ﺃﺼﻌﺏ ﻭﺒﻬﺫﺍ ﻨﻘﻲ ﺍﻝﺴﻥ ﻤﻥ ﺍﻝﻨﺨﺭ‪.‬‬
‫ل ﻤﺩﺓ ﺘﻨﻅﻴﻑ ﺍﻷﺴﻨﺎﻥ ﻋﻥ ﺜﻼﺜﺔ ﺩﻗﺎﺌﻕ ﺤﺘﻰ ﺘﺘ ‪‬ﻡ ﻋﻤﻠﻴﺔ ﺇﻋﺎﺩﺓ ﺍﻝﻤﻌﺎﺩﻥ ﺇﻝﻰ ﺍﻝﻤﻴﻨﺎﺀ ﻭﺘﻜﻭ‪‬ﻥ ﻁﺒﻘﺔ‬
‫ﻝﻬﺫﺍ ﻴ‪‬ﻨﺼﺢ ﺒﺄﻻ ﺘﻘ ّ‬
‫ﻭﺍﻗﻴﺔ‪.‬‬
‫‪ .III‬ﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺭﺍﺴﺏ ﻤﺎ‬
‫ﻴﺴﻤﺢ ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ ﺍﻝﺴﺎﺒﻕ ﺒﺭﺴﻡ ﻤﺨﻁﻁ ﺍﻝﻭﺠﻭﺩ ﻝﺭﺍﺴﺏ ﻤﺎ ؛ ﺇﺫ ﺇ ﻨﻪ ﻨﻅﺭ ﹰﺍ ﻝﻜﻭﻥ‬
‫ﻥ ﻤﻔﻬﻭﻡ ﺍﻝﺭﺠﺤﺎﻥ ﻴﻔﻘﺩ ﻤﻌﻨﺎﻩ‪ ،‬ﻓﺎﻝﺭﺍﺴﺏ ﺇﻤﺎ ﺃﻥ ﻴﻜﻭﻥ ﻤﻭﺠﻭﺩﹰﺍ ﻭﺇﻤﺎ‬
‫ﺍﻝﺭﺍﺴﺏ ﻭﺤﻴﺩﹰﺍ ﻓﻲ ﻁﻭﺭﻩ‪ ،‬ﻓﺈ ‪‬‬
‫ﻻ‪.‬‬
‫ﻻ ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ ﺘﺭﻜﻴﺯﻩ ‪ 0.1 mol/L‬ﻭﻝﻨﻀﻑ ﺇﻝﻴﻪ ﺩﻭﻥ ﺘﻐﻴﻴﺭ‬

‫ ﻤﺜﺎل ‪ :‬ﻝﻨﺄﺨﺫ ﻤﺤﻠﻭ ﹰ‬
‫ﻻ ﻤﻥ ﻴﻭﺩﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ‪ .‬ﻭﺍﻝﻤﻁﻠﻭﺏ ﺘﺤﺩﻴﺩ ﺍﻝﻘﻴﻤﺔ ] ‪pI = −log [ I−‬‬
‫ﻓﻲ ﺍﻝﺤﺠﻡ ﻤﺤﻠﻭ ﹰ‬
‫ﻥ ‪. pK s (AgI) = 16.2‬‬
‫ﺍﻝﺘﻲ ﻴﺘﺭﺴ‪‬ﺏ ﻋﻨﺩﻫﺎ ﻴﻭﺩﻴﺩ ﺍﻝﻔﻀﺔ ‪ ، AgI‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫ﻓﻲ ﺍ ﻝﺤﻘﻴﻘﺔ ﻨﺤﺼل ﻋﻠﻰ ﺭ ﺍﺴﺏ ﻋﻨﺩ ﻤﺎ ﻴﻜﻭ ﻥ )‪ ، Qr = K s (AgI‬ﺤﻴﺙ ‪ Qr‬ﻫﻭ‬

‫ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ‪ ، Qr = [ Ag+ ][ I− ]pr‬ﻭﺘﻤﺜﹼل ‪ [ I− ]pr‬ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻴﻭﺩ ﻋﻨﺩ ﺒﺩﺀ‬
‫ﻥ‪:‬‬
‫ﺍﻝﺘﺭﺴﻴﺏ‪ .‬ﻭﻋﻠﻴﻪ ﻨﺭﻯ ﺃ ‪‬‬
‫)‪K s (AgI‬‬
‫= ‪[ I− ]pr‬‬
‫] ‪[ Ag+‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪pI pr = pK s (Ag I) − pAg‬‬
‫ﻭ ﻫﻜﺫﺍ ﻴﺘﺸﻜﹼل ﺭﺍﺴﺏ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪ . [ I− ] ≥ [ I− ]pr‬ﻭﻝﻤﹼﺎ ﻜﺎﻥ ‪ pI‬ﺘﺎﺒﻌﹰﺎ ﻤﺘﻨﺎﻗﺼﹰﺎ ﻝﻠﺘﺭﻜﻴﺯ‬
‫ﻥ ﺍﻝﺭﺍﺴﺏ ﻴﺘﻜﻭ‪‬ﻥ ﻋﻨﺩﻤﺎ ‪. pI pr ≥ pI‬‬
‫] ‪ [ I−‬ﻓﺈ ‪‬‬
‫ﻓﻔﻲ ﺍﻝﻤﺜﺎ ل ﺍﻝﻤﺩ ﺭﻭﺱ ‪ pAg = 1‬ﻭ ‪ . pI pr = 16.2 − 1 = 15.2‬ﻭﺒﻬﺫ ﺍ ﻨﺭﺴﻡ‬

‫ﻝﻴﻭﺩﻴﺩ ﺍﻝﻔﻀﺔ ‪ Ag I‬ﺍﻝﻤﺨﻁﻁ ﺍﻵﺘﻲ‪:‬‬
‫ﻴﻭﺠﺩ ﺭﺍﺴﺏ ﻤﻥ ﻴﻭﺩ ﻴﺩ ﺍﻝﻔﻀﺔ ‪Ag I‬‬ ‫ﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ ﻤﻥ ﻴﻭﺩ ﻴﺩ ﺍﻝﻔﻀﺔ ‪Ag I‬‬
‫‪15.2‬‬ ‫‪pI‬‬
‫ﻴﻤﻜﻥ ﺒﺎﺴﺘﻌﻤﺎل ﺒﺭﻤﺠﻴﺎﺕ ﻤﺤﺎﻜﺎﺓ ﺭﺴﻡ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﻝﻠﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﺩﻨﻴﺔ ] ‪[ Ag+‬‬
‫ﺍﻝﺸﻜل ) ‪ . ( 3‬ﻭﻴﻅﻬﺭ ﺒﻭﻀﻭﺡ ﻋﻠﻰ ﻤﺨﻁﻁ ﺍﻝﺘﻭﺯﻴﻊ ﺤﺩﻭﺩ ﺘﻜﻭ‪‬ﻥ ﺍﻝﺭﺍﺴﺏ ﺍﻝﺘﻲ ﺘﺘﻌﻠﹼﻕ ﺒﺩﻭﺭﻫﺎ‬
‫ﺒﺎﻝﺘﺭﺍﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﻝﻠﺸﺎﺭﺩﺓ ﺍﻝﻤﻭﺠﺒﺔ‪.‬‬
‫ﻴ‪‬ﻅﻬﺭ ﺍﻝﺸﻜل ) ‪ ( 3‬ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﺒﺩﻻﻝﺔ ‪ pI‬ﻭﺫﻝﻙ ﻋﻨﺩ ﺇﻀﺎﻓﺔ‬
‫ﻤﺤﻠﻭل ﻴﻭﺩﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺇﻝﻰ ﻤﺤﻠﻭل ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ ﺒﺘﺭﻜﻴﺯ ‪ . c‬ﻭﻨﻼﺤﻅ ﺃﻥ ﺍﻝﺘﺭﺴﻴﺏ ﻴﺒﺩﺃ ﻋﻨﺩﻤﺎ‬
‫ﻴﺘﺤﻘﹼﻕ ﺍﻝﺸﺭﻁ ‪ ، pI pr ≥ pI‬ﺤﻴﺙ‬
‫‪pI pr = pK s (AgI) − pAg = pK s (AgI) − pc‬‬
‫ﻥ‬
‫ﻭﻴﻅﻬﺭ ﻫﺫﺍ ﻋﻠﻰ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﻋﻨﺩ ﻨﻘﺎﻁ ﺍﻻﻨﻌﺭﺍﺝ ‪ E‬ﻭ ‪ F‬ﻭ ‪ .G‬ﻭﻨﺘﺤﻘﹼﻕ ﺒﺴﻬﻭﻝﺔ ﺃ ‪‬‬
‫ﺒﺩﺀ ﺍﻝﺘﺭﺴﻴﺏ ﻴﺘﻌﻠﹼﻕ ﺒﺎﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﺒﺩﺍﺌﻴﺔ ‪ c‬ﻝﻠﺸﺎﺭﺩﺓ ﺍﻝﻤﻭﺠﺒﺔ‪.‬‬
‫‪E‬‬ ‫‪F‬‬ ‫‪G‬‬

‫‪%‬‬
‫‪90‬‬ ‫‪ [Ag + ]0 =1.0 ⋅ 10−3 mol/L‬‬
‫‪ [Ag + ]0 =1.0 ⋅ 10−2 mol/L‬‬
‫‪80‬‬ ‫‪+‬‬ ‫‪−1‬‬
‫‪ [Ag ]0 =1.0 ⋅ 10 mol/L‬‬
‫‪70‬‬
‫‪60‬‬
‫‬ ‫‬ ‫‬
‫‪50‬‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪0‬‬
‫‪10‬‬ ‫‪11‬‬ ‫‪12‬‬ ‫‪13‬‬ ‫‪14‬‬ ‫‪15‬‬ ‫‪pI‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 3‬ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﺒﺩﻻﻝﺔ ‪، pI‬‬
‫ﻭﺫﻝﻙ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻴﻭﺩﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺇﻝﻰ ﻤﺤﻠﻭل ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ‪.‬‬
‫‪ .IV‬ﺘﻨﺎﻓﺱ ﺍﻝﺭﻭﺍﺴﺏ‬
‫‪ .1.IV‬ﺘﺠﺭﺒﺔ‬
‫ﻝﻨﻀﻊ ﻓﻲ ﺃﻨﺒﻭﺏ ﺍ ﺨﺘﺒﺎ ﺭ ‪ 1 mL‬ﺘﻘﺭﻴﺒﹰﺎ ﻤﻥ ﻤﺤﻠﻭ ل ﻨﺘﺭ ﺍﺕ ﺍ ﻝﺭﺼﺎ ﺹ ‪ II‬ﺒﺘﺭ ﻜﻴﺯ‬

‫‪ 0.1 mol/L‬ﻭ ﻝﻨﻀﻑ ﺇ ﻝﻴﻪ ﺒﻀﻊ ﻗﻁﺭ ﺍ ﺕ ﻤﻥ ﻤﺤﻠﻭ ل ﻜﻠﻭ ﺭ ﻴﺩ ﺍ ﻝﺼﻭ ﺩ ﻴﻭ ﻡ ﺒﺘﺭ ﻜﻴﺯ‬
‫‪ 0.1 mol/L‬ﻓﻨﻼ ﺤﻅ ﺘﻜ ‪‬ﻭ ﻥ ﺭ ﺍﺴﺏ ﺃ ﺒﻴﺽ ﻤﻥ ﻜﻠﻭ ﺭ ﻴﺩ ﺍ ﻝﺭﺼﺎ ﺹ ‪ Pb Cl2‬ﻭ ﺫ ﻝﻙ ﻭ ﻓﻘﹰﺎ‬
‫ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪Pb2+ + 2Cl− ⇌ Pb Cl2‬‬
‫ﺤﻴﺙ ‪. pK s (PbCl2 ) = 4.6‬‬
‫ﻻ ﻤﻥ ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ ،‬ﻓﻨﻼﺤﻅ‬

‫ﻝ ﹸﻨﻌ‪‬ﺩ ﺍﻝﺘﺠﺭﺒﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺒﺎﺴﺘﻌﻤﺎل ﻴﻭﺩ ﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺩ ﹰ‬
‫ﺘﻜﻭ‪‬ﻥ ﺭﺍﺴﺏ ﺃﺼﻔﺭ ﻤﻥ ﻴﻭﺩﻴﺩ ﺍﻝﺭﺼﺎﺹ ‪ Pb I2‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ‪:‬‬
‫‪Pb2+ + 2I− ⇌ Pb I2‬‬
‫ﺤﻴﺙ ‪. pK s (PbI2 ) = 8.2‬‬
‫ﻝ ﹸﻨﻀ‪‬ﻑ ﺍﻵﻥ ﺇﻝﻰ ﺃﻨﺒﻭﺏ ﻤﺤﺘ ﹴﻭ ﻋﻠﻰ ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﺭﺼﺎﺹ ﻗﻁﺭ ﺍﺕ ﻤﻥ‬
‫ﻥ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺒﻴﺽ ﻗﺩ ﺍﺨﺘﻔﻰ ﻭ ﺘﻜﻭ‪‬ﻥ ﻤﻜﺎﻨﻪ‬
‫ﻤﺤﻠﻭل ﻴﻭﺩ ﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﻗﻁﺭﺓ ﻗﻁﺭﺓ‪ .‬ﻓﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺭﺍﺴﺏ ﺃﺼﻔﺭ ﻤﻥ ﻴﻭﺩﻴﺩ ﺍﻝﺭﺼﺎﺹ‪ ،‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ‪:‬‬
‫‪Pb Cl2 + 2I− ⇌ Pb I2 + 2Cl−‬‬
‫ﻻ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺭﺼﺎﺹ‪ ،‬ﻭﻫﺫﺍ‬
‫ﻥ ﻴﻭﺩﻴﺩ ﺍﻝﺭﺼﺎﺹ ﺃﻗل ﺍﻨﺤﻼ ﹰ‬
‫ﻴﻅﻬﺭ ﻤﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﺃ ‪‬‬
‫ﻤﺎ ﻨﺭﺍﻩ ﺠﻠﻴﹰﺎ ﺒﻤﻘﺎﺭﻨﺔ ﻗﻴﻤﺘﻲ ‪ K s‬ﻭ ‪ ) K s′‬ﺤﻴﺙ ﺘﻜﻭﻥ ﺍﻝﻤﻘﺎﺭﻨﺔ ﻫﻨﺎ ﺼﺤﻴﺤﺔ ﻝﻜﻭﻥ ﺍﻝﺭﺍﺴﺒﻴﻥ‬
‫ﻴﺘﻤﺘﻌﺎﻥ ﺒﺼﻴﻐﺘﻴﻥ ﻤﺘﻁﺎﺒﻘﺘﻴﻥ ﻤﻥ ﺍﻝﺸﻜل ‪.( MX2‬‬
‫‪ .2.IV‬ﺍﻝﺘﻌﻠﻴل‬
‫ﻴﻤﻜﻥ ﻭﺼﻑ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺜﺎﺒﺕ ‪ K‬ﺍﻝﺫﻱ ﻴ‪‬ﺩﺨ‪‬ل ﺘﺭﺍﻜﻴﺯ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﻨﺤﻠﺔ‪:‬‬
‫‪[ Cl− ]2‬‬

‫= ‪K‬‬
‫‪[ I− ]2‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪− 2‬‬ ‫‪2+‬‬
‫‪[ Cl ] [ Pb‬‬ ‫]‬ ‫‪Ks‬‬
‫= ‪K‬‬ ‫‪− 2‬‬
‫=‬ ‫‪= 4 × 103‬‬
‫‪[ I ] [ Pb‬‬ ‫‪2+‬‬
‫]‬ ‫‪K s′‬‬
‫ﺇﺫﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﺘﺎﻡ ﻭﻴﻤﻜﻥ ﺍﻝﺘﻨﺒﺅ ﺒﻪ ﺒﺎﺴﺘﻌﻤﺎل ﻗﺎﻋﺩﺓ ‪ ، γ‬ﺤﻴﺙ ﻴﺘﻔﺎﻋل ‪ ، I−‬ﻭﻫﻭ‬
‫ﺍﻝﻤﺘﻘ‪‬ﺒل ﺍﻷﻗﻭﻯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ ﻤﻊ ‪ PbCl2‬ﻭﻫﻭ ﺍﻝﻤﺎﻨﺢ ﺍﻷﻗﻭﻯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ‪ ،‬ﻜﻤﺎ‬
‫ﻫﻭ ﻤﻭﻀ‪‬ﺢ ﻓﻲ ﺍﻝﺸﻜل ) ‪. ( 4‬‬
‫‪pI‬‬
‫‪K = 4.0 × 103‬‬
‫‪I−‬‬
‫‪3.6‬‬
‫‪PbI2‬‬
‫‪PbI2‬‬ ‫‪1.8‬‬
‫‪PbCl2‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 4‬ﺘﻔﺎﻋل ‪ I−‬ﻭﻫﻭﺍﻝﻤﺘﻘ ‪‬ﺒل ﺍﻷﻗﻭﻯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ ﻤﻊ ‪ PbCl2‬ﻭﻫﻭ‬

‫ﺍﻝﻤﺎﻨﺢ ﺍﻷﻗﻭﻯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ﺍﻝﻤﺨﻁﹼﻁ ﻗﺩ ‪‬ﺭﺴ‪‬ﻡ ﻓﻲ ﺤﺎﻝﺔ ﺘﺭﻜﻴ ﹴﺯ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ ﻗﺩﺭﻩ‬
‫‪[ Pb2+ ] = 0.10 mol/L‬‬

‫ﻓﺈﻨﻨﺎ ﻨﺠﺩ ﺍﻝﻘﻴﻡ ﺍﻝﺘﺎﻝﻴﺔ ﻝﻭﺠﻭﺩ ﺍﻝﺭﺍﺴﺒﻴﻥ ‪ PbCl2‬ﻭ ‪. PbI2‬‬
‫‪1‬‬ ‫‪1‬‬
‫= ‪pCl‬‬ ‫‪(pK s − pPb) = (4.6 − 1) = 1.8‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪1‬‬ ‫‪1‬‬
‫= ‪pI‬‬ ‫‪(pK s′ − pPb) = (8.2 − 1) = 3.6‬‬
‫‪2‬‬ ‫‪2‬‬
‫‪ .3.IV‬ﺘﻁﺒﻴﻕ‪:‬‬
‫ﻴ‪‬ﻅﻬﺭ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ ﻨﻤﺫﺠﺔ ﻝﺘﺠﺭﺒﺔ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬
‫‪ 1.0 mol/L‬ﺇﻝﻰ ‪ 10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ ، 0.1 mol/L‬ﻭﻨﺘﺭﺍﺕ ﺍﻝﺭﺼﺎﺹ‬
‫‪. 0.1 mol/L‬‬
‫‪%‬‬
‫‪90‬‬
‫‪80‬‬
‫‪70‬‬
‫‪60‬‬
‫‬
‫‪50‬‬
‫‬
‫‪40‬‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪0‬‬
‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪pSO4‬‬
‫ﺘﹸﻅﻬﺭ ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺘﻐﻴﺭﺍﺕ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ Ca 2+‬ﻭﺍﻝﺭﺼﺎﺹ ‪Pb2+‬‬

‫ل‬
‫ﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺭﺼﺎﺹ ﺃﻗ ّ‬
‫ﺃﺜﻨﺎﺀ ﺍﻹﻀﺎﻓﺔ ﺒﺩﻻﻝﺔ ] ‪ . pSO4 = − log [ SO24−‬ﺘﺅﻜﹼﺩ ﺍﻝﺘﺠﺭﺒﺔ ﺃ ‪‬‬
‫ﻻ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‪.‬‬
‫ﺍﻨﺤﻼ ﹰ‬
‫ل ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ؟‬
‫‪ .1‬ﺇﻝﻰ ﺃﻱ ﺸﺎﺭﺩﺓ ﻴﻌﻭﺩ ﻜ ﱞ‬
‫ل ﻤﻥ ‪CaSO4‬‬
‫‪ .2‬ﺒﺈﻫﻤﺎل ﺍ ﻝﺘﻤﺩﻴﺩ ﺍﻝﺤﺎﺼل ﺃﺜﻨﺎﺀ ﺍﻹﻀﺎﻓﺔ‪ ،‬ﺍﺴﺘﻨﺘﺞ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻝﻜ ّ‬
‫ﻭ ‪. PbSO4‬‬
‫ﺍﻝﺤل‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ ﻝﺘﻔﺎﻋﻠﻲ ﺍﻝﺘﺭﺴﻴﺏ ﻫﻤﺎ‪:‬‬
‫‪ .1‬ﺇ ‪‬‬
‫)‪Pb2+ + SO24− ⇌ PbSO4 (s‬‬ ‫)‪(α‬‬
‫)‪Ca 2+ + SO24− ⇌ CaSO4 (s‬‬ ‫) ‪(β‬‬
‫ﻴﻀ ‪‬ﻡ ﺍﻝﻤﺤﻠﻭل ﺒﺩﺍﻴﺔ‬
‫‪[ Pb2+ ] = [ Ca 2+ ] = 0.10 mol/L‬‬
‫ﺘﹸﺘﺭﺠ‪‬ﻡ ﺇﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﺒﺘﻨﺎﻗﺹ ﺍﻝﻤﻘﺩﺍﺭ ] ‪ ، pSO4 = − log [ SO24−‬ﻭﻋﻨﺩﻤﺎ‬
‫ﻥ ﺍﻝﻨﺴﺒﺔ ﺍﻝﻤﺌﻭﻴﺔ ﺍﻝﺨﺎﺼﺔ ﺒﻬﺫﻩ ﺍﻝﺸﺎﺭﺩﺓ ﻻ ﺘﺒﻘﻰ ‪ 100%‬ﺒل‬
‫ﻴﺒﺩﺃ ﺘﺭﺴ‪‬ﺏ ﻤﻠﺢ ﺇﺤﺩﻯ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﻓﺈ ‪‬‬
‫ﺘﺄﺨﺫ ﺒﺎﻻﻨﺨﻔﺎﺽ ﻭﻴ‪‬ﻅﻬﹺﺭ ﺍﻝﻤﻨﺤﻨﻲ ﻨﻘﻁﺔ ﺍﻨﻌﺭﺍﺝ‪.‬‬
‫ﻻ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﻭﻜﺎﻥ ﻝﻠﺸﺎﺭﺩﺘﻴﻥ‬
‫ل ﺍﻨﺤﻼ ﹰ‬
‫ﻭﻝﻤﺎﹼ ﻜﺎﻨﺕ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺭﺼﺎﺹ ﺃﻗ ّ‬
‫ﻥ ﺘﺭﺴ‪‬ﺒﻬﺎ ﻴﺒﺩﺃ‬
‫ﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺭﺼﺎﺹ ﻫﻲ ﺍﻝﺘﻲ ﺘﺘﺭﺴ‪‬ﺏ ﻓﻲ ﺍﻝﺒﺩﺍﻴﺔ‪ .‬ﺃﻱ ﺇ ‪‬‬
‫ﺘﺭﺍﻜﻴﺯ ﺍﻝﺒﺩﺀ ﺫ ﺍﺘﻬﺎ ‪ ،‬ﻓﺈ ‪‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻻﻨﻌﺭﺍﺝ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻠﻘﻴﻤﺔ ﺍﻝﺘﻲ ﻫﻲ ﺃﺩﻨﻰ ﻤﻥ ] ‪ [ SO24−‬ﺃﻭ ﻝﻠﻘﻴﻤﺔ ﺍﻝﺘﻲ ﻫﻲ ﺃﻋﻠﻰ ﻤﻥ‬
‫ﻥ ﺍﻝﻤﻨﺤﻨﻲ ﻴﻭﺍﻓﻕ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ Ca 2+‬ﻭﺍﻝﻤﻨﺤﻨﻲ ﻴﻭﺍﻓﻕ ﺇﻝﻰ‬
‫‪ . pSO4‬ﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ ‪. Pb2+‬‬
‫ﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺭﺼﺎﺹ ﺘﺘﺭﺴ‪‬ﺏ ﻋﻨﺩ‪:‬‬
‫‪ .2‬ﻨﻘﺭﺃ ﻤﻥ ﺍﻝﻤﻨﺤﻨﻲ ﺃ ‪‬‬
‫‪pSO4 = 6.8‬‬
‫ﻥ‪:‬‬
‫ﻭﻫﺫﺍ ﻴﻭﺍﻓﻕ ﺍﻝﺘﺭﻜﻴﺯ ‪ ، [ SO24− ] = 1.6 × 10−7 mol/L‬ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬
‫‪K s = [ Pb2+ ] ⋅ [ SO24− ] = 1.6 × 10−8‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪. pK s (PbSO4 ) = 7.8‬‬
‫ﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺘﺘﺭﺴ‪‬ﺏ ﻋﻨﺩﻤﺎ‪:‬‬
‫ﻭﺒﺎﻝﻁﺭﻴﻘﺔ ﺫﺍﺘﻬﺎ ﻨﺠﺩ ﺃ ‪‬‬
‫‪pSO4 = 4.0‬‬
‫ﻭﻫﺫﺍ ﻴﻭﺍﻓﻕ ﺍﻝﺘﺭﻜﻴﺯ ‪. [ SO24− ] = 1.0 × 10−4 mol/L‬‬
‫ﻥ ‪ ، [ Ca 2+ ] = 0.10 mol/L‬ﻭﺘﺒﺩﺃ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ‬
‫ﻭﺒﺈﻫﻤﺎل ﺍﻝﺘﻤﺩﻴﺩ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻌﺘﺒﺭ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫ﺒﺎﻝﺘﺭﺴ‪‬ﺏ ﻋﻨﺩﻤﺎ ‪ ، K s = [ Ca 2+ ] ⋅ [ SO24− ] = 1.0 × 10−5‬ﺃﻱ ﺇ ‪‬‬
‫‪. pK s (CaSO4 ) = 5.0‬‬
‫‪ .V‬ﺍﻻﻨﺤﻼﻝﻴﺔ ﻭﺍﻝﺘﻌﻘﻴﺩ‬
‫‪ .1.V‬ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸ ﹼﻜل ﻤﻌﻘﹼﺩ‬
‫‪ .1.1.V‬ﺘﺠﺭﺒﺔ‬
‫ﻻ ﻤﻤﺩﺩﹰﺍ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ ،‬ﻭﻝﻨﻀﻑ ﺇﻝﻴﻪ ﺒﻀﻌﺔ‬

‫ﻝﻨﻀﻊ ﻓﻲ ﺃﻨﺒﻭﺏ ﺍﺨﺘﺒﺎﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﻗﻁﺭﺍﺕ ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ‪ ،‬ﻓﻴﻅﻬﺭ ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ ‪ . AgCl‬ﻝﻨﻀﻑ ﺍﻵﻥ‬
‫ﻥ ﺍﻝﺭﺍﺴﺏ ﻴﺨﺘﻔﻲ‪ .‬ﻭﻨﻔﺴ‪‬ﺭ ﺫﻝﻙ ﺒﺘﺸﻜﹼل‬
‫ﻗﻁﺭﺓ ﻗﻁﺭﺓ ﻤﻥ ﻤﺤﻠﻭل ﻤﺭﻜﹼﺯ ﻤﻥ ﺍﻝﻨﺸﺎﺩﺭ‪ ،‬ﻓﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩﺓ ‪ [Ag(NH 3 )2 ]+‬ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪AgCl(s) + 2 NH 3 ⇌ [Ag(NH 3 )2 ]+ + Cl−‬‬

‫‪ .2.1.V‬ﺘﻌﻤﻴﻡ‬
‫ل ﺍﻝﻤﺭﻜﺏ ﺍﻝﺼﻠﺏ ﺍﻝﺸـﺎﺭﺩﻱ )‪C x Ay (s‬‬

‫ﻻ ﻤﺸﺒﻌﹰﺎ ‪ S‬ﺘ ‪‬ﻡ ﺍﻝﻭﺼﻭل ﺇﻝﻴﻪ ﺒﺤ ّ‬
‫ﻝﻨﺘﺄﻤل ﻤﺤﻠﻭ ﹰ‬
‫ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪ .‬ﻴﻬﻴﻤﻥ ﻋﻠﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫‪1‬‬ ‫‪p+‬‬ ‫‪q−‬‬
‫↽ )‪C x Ay (s‬‬‫‪ xC + y A‬‬
‫⇀‬ ‫)‪(1‬‬
‫‪2‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ C p +‬ﺘﻌﻁﻲ ﻤﻊ ﺍﻝﺭﺒﻴﻁﺔ ‪ L‬ﻤﻌﻘﺩﹰﺍ ‪ [CLn ]p +‬ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ‬

‫ﻻﺃ‪‬‬
‫ ﻝﻨﻔﺘﺭﺽ ﺃﻭ ﹰ‬
‫‪C p + + n L ⇌ [CLn ]p +‬‬ ‫)‪(2‬‬
‫ﻥ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺍﻝﺭﺒﻴﻁﺔ ‪ L‬ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ‪ S‬ﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻨﺯﻴﺎﺡ ﺍﻝﺘﻭﺍﺯﻥ )‪ (1‬ﻓﻲ‬
‫ﺇ‪‬‬
‫ﺍﻻﺘﺠﺎﻩ ‪ ، 1‬ﻫﺫﺍ ﻴﺅﺩﻱ ﺇﻝﻰ ﺯﻴﺎﺩﺓ ﺍﻨﺤﻼﻝﻴﺔ )‪.C x Ay (s‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ Aq −‬ﺘﻌﻁﻲ ﻤﻊ ﺍﻝﺸﺎﺭﺩﺓ ‪ M r +‬ﻤﻌﻘﺩﹰﺍ ‪ [MA](r −q )+‬ﻭﻓﻕ‬
‫ ﻝﻨﻔﺘﺭﺽ ﺍﻵﻥ ﺃ ‪‬‬
‫ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪Aq − + M r + ⇌ [MA](r −q )+‬‬
‫ﻥ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺍﻝﺸﺎﺭﺩﺓ ‪ M r +‬ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ‪ S‬ﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻨﺯﻴﺎﺡ ﺍﻝﺘﻭﺍﺯﻥ )‪(1‬‬
‫ﺇ‪‬‬
‫ﻓﻲ ﺍﻻﺘﺠﺎﻩ ‪ ، 1‬ﻫﺫﺍ ﻴﺅﺩﻱ ﺇﻝﻰ ﺯﻴﺎﺩﺓ ﺍﻨﺤﻼﻝﻴﺔ )‪.C x Ay (s‬‬
‫ﺇﻥ ﻤﺴﺎﻫﻤﺔ ﺇﺤﺩﻯ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ‪ Aq −‬ﺃﻭ ‪ C p +‬ﻓﻲ ﺘﻜﻭﻴﻥ ﻤﻌﻘﹼﺩ ﺘﺅﺩﻱ ﺇﻝﻰ ﺯﻴﺎﺩﺓ‬
‫ﺍﻨﺤﻼﻝﻴﺔ )‪.C x Ay (s‬‬
‫ﻝﻨﻔﺘﺭﺽ ﺃ ﻨﹼﻨﺎ ﺃﻀﻔﻨﺎ‪ ،‬ﺃﺜﻨﺎﺀ ﺍﻝﺘﺤﺭﻴﻙ ﺍﻝﻤﺴﺘﻤﺭ‪ n = 1.0 × 10−3 mol ،‬ﻤﻥ ﻜﻠﻭﺭ ﻴﺩ‬
‫ل ﻋﺩﺩ ﻤﻥ ﻤﻭﻻﺕ‬
‫ﺍﻝﻔﻀﺔ ﺇﻝﻰ ﺍﻝﺤﺠﻡ ‪ V = 0.500 L‬ﻤﻥ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ‪ .‬ﻤﺎ ﻫﻭ ﺃﻗ ّ‬
‫ﻼ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﺇﺫﺍ‬
‫ﺍﻝﻨﺸﺎﺩﺭ ﺍﻝﻼﺯﻡ ﺇﻀﺎﻓﺘﻪ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ﻝﻴﺼﺒﺢ ﺍﻝﺭﺍﺴﺏ ﺒﻜﺎﻤﻠﻪ ﻤﻨﺤ ﹰ‬
‫ﻥ ﺇﻀﺎﻓﺔ ﺍﻝﻨﺸﺎﺩﺭ ﻝﻥ ﺘﺴﺒ‪‬ﺏ ﺘﻐﻴﺭﹰﺍ ﻤﻠﺤﻭﻅﹰﺎ ﻓﻲ ﺍﻝﺤﺠﻡ؟‬
‫‪p K s (Ag Cl) = 9.7‬‬
‫‪+‬‬
‫] ‪log β2 ( [ Ag ( NH3 )2‬‬ ‫‪) = 7.2‬‬
‫ﺍﻝﺤل‪:‬‬
‫‪ .1‬ﻴﺨﻀﻊ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ ﺇﻝﻰ ﺠﻤﻠﺔ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻤﺤﺼﻠﺘﻴﻥ‪:‬‬
‫‪1‬‬
‫‪→ Ag+ + Cl−‬‬
‫‪Ag Cl ←‬‬ ‫‪Ks‬‬ ‫)‪(1‬‬
‫‪2‬‬
‫‪+‬‬
‫‪→  Ag ( NH3 ) ‬‬
‫‪Ag+ + 2 NH 3 ←‬‬ ‫‪β2‬‬ ‫)‪(2‬‬
‫‪‬‬ ‫‪2‬‬
‫ﻓﻌﻨﺩ ﺇﻀﺎﻓﺔ ﺍﻝﻨﺸﺎﺩﺭ ﻴﺤﺼل ﺘﻔﺎﻋل ﺍﻝﺘﻌﻘﻴﺩ )‪ (2‬ﺍﻝﺫﻱ ﻴﺅﺩﻱ ﺇﻝﻰ ﺇﺯﺍﺤﺔ ﺘﻭﺍﺯﻥ ﺍﻝﺘﺭﺴﻴﺏ )‪(1‬‬
‫ﺒﺎﻻﺘﺠﺎﻩ ‪ 1‬ﺃﻱ ﺘﺯﺩﺍﺩ ﺍﻨﺤﻼﻝﻴﺔ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﻜﻠﻤﺎ ﺍﻨﺤﻠﹼﺕ ﺸﺎﺭﺩﺓ ﻜﻠﻭﺭ‪ ،‬ﺍﻨﺤﻠﹼﺕ ﻤﻌﻬﺎ ﺸﺎﺭﺩﺓ ﻓﻀﺔ ﺤﻴﺙ ﺘﺒﻘﻰ ﺇﻤ‪‬ﺎ ﺤ ‪‬ﺭﺓ ﺃﻤﺎ ﻤﻌﻘﹼﺩﹰﺍ‬
‫ﻭﻨﻜﺘﺏ‪. s = [Ag+ ] + [[Ag ( NH3 )2 ]+ ] = [Cl− ] :‬‬
‫ ﻋﻨﺩﻤﺎ ﺘﻨﺤل ﻜﺎﻤل ﺍﻝﻜﻤﻴﺔ ‪ n = 1.0 × 10−3 mol‬ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ‪ ،‬ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪. [Cl− ] = 2.0 × 10−3 mol/L :‬‬
‫‪Ks‬‬
‫= ] ‪. [Ag+‬‬ ‫ ﻋﻨﺩ ﺤﺩﻭﺩ ﺍﻻﻨﺤﻼل ﻴﻜﻭﻥ‪= 1.0 × 10−7 mol/L :‬‬
‫‪−‬‬
‫] ‪[Cl‬‬
‫ﻥ‪:‬‬
‫‪[[Ag ( NH 3 )2 ]+ ] = [Cl− ] − [Ag+ ] ≈ [Cl− ] ≈ 2.0 × 10−3 mol/L‬‬
‫ ﻭﻴﺘﻌﻴ‪‬ﻥ ﺘﺭﻜﻴﺯ ﺍﻝﻨﺸﺎﺩﺭ ﺍﻝﺤ ‪‬ﺭ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺜﺎﺒﺕ ﺘﺸﻜﻴل ﺍﻝﻤﻌﻘﹼﺩ ‪. β2‬‬
‫‪ [[Ag ( NH ) ]+ ] 0.5‬‬
‫‪‬‬ ‫‪3 2‬‬ ‫‪ = 3.6 × 10−2 mol/L‬‬
‫‪[NH 3 ] = ‬‬
‫‪ β ⋅ [Ag+ ] ‬‬
‫‪‬‬ ‫‪2‬‬ ‫‪‬‬
‫ل ﻋﺩﺩ ﻤﻥ ﻤﻭﻻﺕ ﺍﻝﻨﺸﺎﺩﺭ ﺍﻝﻼﺯﻡ ﺇﻀﺎﻓﺘﻪ ﻴﺘ ‪‬ﻡ ﺘﺤﺩﻴﺩﻩ ﺒﻜﺘﺎﺒﺔ ﺸﺭﻁ ﺍﻨﺤﻔﺎﻅ‬
‫ﻥ ﺃﻗ ّ‬
‫)] ‪n = V × (2 × [[Ag ( NH 3 )2 ]+ ] + [NH 3‬‬ ‫ﺍﻝﻨﺸﺎﺩﺭ‪:‬‬
‫ﺃﻱ ﺇ ‪‬ﻥ ‪. n = 2.0 × 10−2 mol‬‬
‫‪ .2.V‬ﺘﻐ ‪‬ﻴﺭ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸ ﹼﻜل ﻤﻌﻘﹼﺩﺍﺕ‬
‫ﻓﻲ ﺒﻌﺽ ﺍﻝﺤﺎﻻﺕ ﻴﻤﻜﻥ ﻝﻠﺸﺎﺭﺩﺓ ‪ Aq −‬ﺃﻥ ﺘﻌﻁﻲ ﺒﺘﻔﺎﻋﻠﻬﺎ ﻤﻊ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻭﺠﺒﺔ ‪C p +‬‬
‫ﺭﺍﺴﺒﹰﺎ ﻭﻤﻌﻘﺩﹰﺍ ﺃﻭ ﻋﺩﺩﹰﺍ ﻤﻥ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪ .‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﺘﺘﻐﻴﺭ ﺍﻨﺤﻼﻝﻴﺔ ‪ C x Ay‬ﺒﺼﻭﺭﺓ ﻜﺒﻴﺭﺓ ﻤﻊ ﻜﻤﻴﺔ‬
‫ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺴﺎﻝﺒﺔ ﺍﻝﻤﻀﺎﻓﺔ‪.‬‬
‫ﻝﻨﺩﺭﺱ ﻋﻠﻰ ﺴﺒﻴل ﺍﻝﻤﺜﺎل ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﺎﺼﻠﺔ ﺒﻴﻥ ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ ‪ Ag+‬ﻭﺸﺎﺭﺩﺓ‬
‫ﺍﻝﺴﻴﺎﻨﻴﺩ ‪. CN−‬‬
‫ﻻ ﻤﺭ ﻜﹼﺯ ﹰﺍ ﻤﻥ ﺴﻴﺎﻨﻴﺩ ﺍﻝﺼﻭ ﺩﻴﻭﻡ ) ‪ (Na + + CN−‬ﺇﻝﻰ ﻤﺤﻠﻭل‬

‫ﻨﻀﻴﻑ ﺘﺩﺭﻴﺠﻴﹰﺎ ﻤﺤﻠﻭ ﹰ‬
‫‪ (Ag+ + NO−‬ﺒﺘﺭﻜﻴﺯ ‪. c = 1.0 × 10−2 mol/L‬‬
‫ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ ) ‪3‬‬
‫ﻱ ﻗﻴﻤﺔ‬
‫‪ .1‬ﻋﻴ‪‬ﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﺤﺼل‪ .‬ﻴﺒﺩﺃ ﺘﺭﺴ‪‬ﺏ ﺴﻴﺎﻨﻴﺩ ﺍﻝﻔﻀﺔ ﻋﻨﺩ ﺃ ‪‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﻘﹼﺩ ﺘﻜﻭﻥ ﻋﻨﺩﻫﺎ ﻤﻐﻠﻭﺒﺔ‬
‫ﻝﻠﻤﻘﺩﺍﺭ ] ‪ p CN = − log[CN−‬؟ ﺘﺤﻘﹼﻕ ﺃ ‪‬‬
‫ﻤﻘﺎﺒل ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ )‪. (I‬‬
‫‪ .2‬ﻋﺭ‪‬ﻑ ﺍﻨﺤﻼﻝﻴﺔ ﺴﻴﺎﻨﻴﺩ ﺍﻝﻔﻀﺔ ﺒﻭﺠﻭﺩ )‪ ، AgCN(s‬ﻭﻋﺒ‪‬ﺭ ﻋﻨﻪ ﺒﺩﻻﻝﺔ ] ‪[CN−‬‬

‫ﻭ ‪ Ks‬ﻭ ‪. β2‬‬
‫‪ .3‬ﺃﺜﺒﺕ ﺃ ﻨﹼﻪ ﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﻌﺒ‪‬ﺭ ﺒﺒﺴﺎﻁﺔ ﻋﻥ ‪ log s‬ﺒﺩﻻﻝﺔ ‪ p CN‬ﻭﺫﻝﻙ ﻋﻨﺩ ﻤﻨﺎﻁﻕ‬
‫ﻤﺤﺩ‪‬ﺩﺓ ﻴ‪‬ﻁﻠﺏ ﺘﺤﺩﻴﺩﻫﺎ‪.‬‬
‫ﻥ‬
‫ﻼ ﺘﻤﺎ ﻤﹰﺎ ؟ ﺘﺤﻘﹼﻕ ﻤﻥ ﺃ ‪‬‬
‫‪ .4‬ﻋﻨﺩ ﺃ ﻴ‪‬ﺔ ﻗﻴﻤﺔ ﻝﻠﻤﻘﺩ ﺍ ﺭ ‪ p CN‬ﻴﺼﺒﺢ ﺴﻴﺎ ﻨﻴﺩ ﺍ ﻝﻔﻀﺔ ﻤﻨﺤ ﹰ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ )‪ (I‬ﺘﺼﺒﺢ ﻋﻨﺩﻫﺎ ﻤﻐﻠﻭﺒﺔ ﻤﻘﺎﺒل ﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﻘﹼﺩ‪.‬‬
‫‪ .5‬ﺍﺭﺴﻡ )‪. log s = f (p CN‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ ‪. log β2 ([Ag(CN)2 ]− ) = 21.0 ، pKs (AgCN) = 15.9 :‬‬
‫ﻥ ﺍﻝﺘﻤﺩﻴﺩ ﻤﻬﻤل‪.‬‬
‫ﻨﻔﺘﺭﺽ ﺃ ‪‬‬
‫ﺍﻝﺤل‬
‫ﻻ‪-‬ﻭﺤﺴﺏ ﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﺍﻝﺘﻔﺎﻋﻼﺕ‪ -‬ﺭﺍﺴﺏ‬

‫‪ .1‬ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل ﺴﻴﺎﻨﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻴﺘﻜﻭ‪‬ﻥ ﺃﻭ ﹰ‬
‫ﻤﻥ ﺴﻴﺎﻨﻴﺩ ﺍﻝﻔﻀﺔ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪1‬‬
‫)‪(1‬‬ ‫‪Ag+ + CN− ←‬‬
‫)‪→ AgCN(s‬‬
‫‪2‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻫﻭ ‪. K1 = 1/Ks = 1015.9 = 7.9 × 1015 :‬‬
‫ل ﺍﻝﺭﺍﺴﺏ ﺠﺯﺌﻴﹰﺎ ﺒﺘﻜﻭﻥ ﺍﻝﻤﻌﻘﹼﺩ ﺤﺴﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬

‫ﻴﻨﺤ ّ‬
‫‪1‬‬
‫)‪(2‬‬ ‫‪AgCN(s) + CN− ←‬‬
‫‪→[Ag(CN)2 ]−‬‬
‫‪2‬‬
‫ﻥ‪:‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ‪ K 20‬ﺒﺤﻴﺙ ﺃ ‪‬‬
‫] ‪[[Ag(CN)2 ]−‬‬ ‫] ‪[[Ag(CN)2 ]− ] [CN− ] ⋅ [Ag+‬‬

‫‪K 2‬‬ ‫=‬ ‫=‬ ‫⋅‬ ‫‪= β2 ⋅ Ks‬‬
‫] ‪[CN−‬‬ ‫] ‪[CN−‬‬ ‫] ‪[CN− ] ⋅ [Ag+‬‬
‫ﻥ ‪. K 2 = 105.1 = 1.3 × 105‬‬

‫ﺃﻱ ﺇ ‪‬‬
‫ﻋﻨﺩﻤﺎ ﻴﺒﺩﺃ ﺍﻝﺭﺍﺴﺏ ﺒﺎﻝﻅﻬﻭﺭ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ‪[Ag+ ] = 1.0 × 10−2 mol/L :‬‬
‫ﻥ‪:‬‬
‫‪Ks‬‬
‫= ] ‪[CN−‬‬ ‫‪= 1.3 × 10−14 mol/L‬‬
‫‪+‬‬
‫] ‪[Ag‬‬
‫ﻭﻫﺫﺍ ﻴﻭﺍﻓﻕ ‪ . p CN = 13.9‬ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩﺓ ‪:‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﻘﹼﺩ‬
‫‪ [[Ag(CN)2 ]− ] = K 2 ⋅ [CN− ] = 1.3 × 10−9 mol/L‬ﻭﻨﻼﺤﻅ ﻫﻨﺎ ﺃ ‪‬‬
‫ﺘﻜﻭﻥ ﻤﻐﻠﻭﺒﺔ ﻤﻘﺎﺒل ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ )‪. (I‬‬
‫ل ﺴﻴﺎﻨﻴﺩ ﺍﻝﻔﻀﺔ ﻋﻥ ﻁﺭﻴﻕ ﺘﻔﻜﻜﻪ )ﺍﻻﺘﺠﺎﻩ ‪ 2‬ﻤﻥ ﺍﻝﺘﻔﺎﻋل )‪ ( (1‬ﻭﻋﻥ ﻁﺭﻴﻕ ﺍﻝﺘﻌﻘﻴﺩ‬
‫‪ .2‬ﻴﻨﺤ ّ‬
‫ﻥ‪:‬‬
‫)ﺍﻻﺘﺠﺎﻩ ‪ 1‬ﻤﻥ ﺍﻝﺘﻔﺎﻋل )‪ ( (2‬ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬
‫)‪(3‬‬ ‫] ‪s = [Ag+ ] + [[Ag(CN)2 ]−‬‬
‫ﻥ ﺍﻝﺘﻭﺍﺯﻨﻴﻥ )‪ (1‬ﻭ )‪ (2‬ﻴﻜﻭﻨﺎﻥ ﻤﺤﻘﻘﻴﻥ‪ ،‬ﻭ ﻨﻜﺘﺏ‪:‬‬

‫ﻤﺎ ﺩﺍﻡ ﻫﻨﺎﻝﻙ ﺴﻴﺎﻨﻴﺩ ﺍﻝﻔﻀﺔ ﺍﻝﺼﻠﺒﺔ‪ ،‬ﻓﺈ ‪‬‬
‫‪Ks‬‬
‫] ‪[[Ag(CN)2 ]− ] = β2 ⋅ Ks ⋅ [CN−‬‬ ‫ﻭ‬ ‫= ] ‪[Ag+‬‬
‫] ‪[CN−‬‬
‫ﻥ‪:‬‬
‫ﺒﺎﻝﺘﻌﻭﻴﺽ ﻓﻲ ﺍﻝﻌﻼﻗﺔ )‪ (3‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪Ks‬‬
‫)‪(4‬‬ ‫= ‪s‬‬ ‫] ‪+ β2 ⋅ Ks ⋅ [CN−‬‬
‫‪−‬‬
‫] ‪[CN‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃﻨﹼﻪ ﺒﺈﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺎﻨﻴﺩ ﻴﻨﺯﺍﺡ ﺍﻝﺘﻭﺍﺯﻥ )‪ (2‬ﺒﺎﻻﺘﺠﺎﻩ ‪ 1‬ﺤﺘﻰ ﻨﺼل ﺇﻝﻰ‬
‫ﺍﻻﻨﺤﻼل ﺍﻝﺘﺎﻡ ﻝﻠﺭﺍﺴﺏ‪.‬‬
‫‪ .3‬ﻓﻲ ﺍﻝﻌﻼﻗﺔ )‪ (3‬ﻴﻤﻜﻨﻨﺎ ﺇﻫﻤﺎل ] ‪ [[Ag(CN)2 ]−‬ﻤﻘﺎﺒل ﺘﺭﻜﻴﺯ ] ‪ [Ag+‬ﻋﻨﺩﻤﺎ‬
‫] ‪[[Ag(CN)2 ]− ] ≤ 0.1 × [Ag+‬‬

‫ﺃﻱ ﺇﺫﺍ ﻜﺎﻥ‬
‫‪Ks‬‬
‫× ‪β2 ⋅ Ks ⋅ [CN− ] ≤ 0.1‬‬
‫] ‪[CN−‬‬
‫≤ ] ‪ ، [CN−‬ﺃﻱ ‪ ، [CN− ] ≤ 1.0 × 10−11‬ﺃﻭ ‪. p CN ≥ 11‬‬ ‫ﺃﻭ ‪0.1/β2‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ‪ p CN ≥ 11‬ﻴﻜﻭﻥ‬
‫‪Ks‬‬
‫≈ ] ‪s ≈ [Ag+‬‬
‫] ‪[CN−‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ‪ ، log s ≈ logKs + p CN‬ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ‬
‫‪. log s ≈ −15.9 + p CN‬‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﻴﻤﻜﻥ ﺇﻫﻤﺎل ﺘﺭﻜﻴﺯ ] ‪ [Ag+‬ﻤﻘﺎﺒل ﺘﺭﻜﻴﺯ ] ‪ [[Ag(CN)2 ]−‬ﻓﻲ ﻋﺒﺎﺭﺓ‬
‫ﺍﻻﻨﺤﻼﻝﻴﺔ ﻋﻨﺩﻤﺎ‬
‫] ‪[Ag+ ] ≤ 0.1 × [[Ag(CN)2 ]−‬‬
‫ﺃﻱ ﺇﺫﺍ ﻜﺎﻥ‬
‫‪Ks‬‬
‫‪.‬‬ ‫] ‪≤ 0.1 × β2 ⋅ Ks ⋅ [CN−‬‬
‫‪−‬‬
‫] ‪[CN‬‬
‫≥ ] ‪ [CN−‬ﺃﻱ ‪ ، [CN− ] ≥ 1.0 × 10−10‬ﺃﻭ ‪. p CN ≤ 10‬‬ ‫ﺃﻭ ‪10/β2‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ‪ p CN ≤ 10‬ﻴﻜﻭﻥ‬
‫] ‪s ≈ [[Ag(CN)2 ]− ] ≈ β2 ⋅ Ks ⋅ [CN−‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ‪ ، log s ≈ log(β2 ⋅ Ks ) − p CN‬ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ‬
‫‪. log s ≈ 5.1 − p CN‬‬
‫ل ﺍﻝﺭﺍﺴﺏ ﺘﻤﺎﻤﹰﺎ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﻘﹼﺩﺓ‪ [[Ag(CN)2 ]− ] :‬ﻤﺴﺎﻭﻴ ﹰﺎ‬
‫‪ .4‬ﻋﻨﺩﻤﺎ ﻴﻨﺤ ّ‬
‫‪ ، 1.0 × 10−2 mol/L‬ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﺎﺭﺩﺓ ﺍﻝﺴﻴﺎﻨﻴﺩ‪:‬‬
‫‪−‬‬ ‫] ‪[[Ag(CN)2 ]−‬‬

‫= ] ‪[CN‬‬ ‫‪= 7.7 × 10−8 mol/L‬‬
‫‪K 20‬‬
‫ﻭﻤﻨﻪ ‪. p CN = 7.1‬‬
‫‪Ks‬‬
‫= ] ‪. [Ag+‬‬ ‫ﻋﻨﺩ ﺤﺩﻭﺩ ﺍﻻﻨﺤﻼل‪= 1.6 × 10−9 mol/L :‬‬
‫‪−‬‬
‫] ‪[CN‬‬
‫‪ds‬‬
‫‪ ،‬ﻓﺘﺼﺒﺢ ﺍﻝﻌﺒﺎﺭﺓ )‪: (4‬‬ ‫‪ .5‬ﺘﺒﻠﻎ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻨﻬﺎﻴﺔ ﺤﺩﻴﺔ ﺼﻐﺭﻯ ﻋﻨﺩﻤﺎ ‪= 0‬‬
‫] ‪d[CN−‬‬
‫‪−Ks‬‬
‫‪+ β2 ⋅ Ks = 0‬‬
‫‪[CN− ]2min‬‬
‫ﻥ ‪. p CNmin = (logβ2 )/2 = 10.5‬‬
‫ﻭﻤﻨﻪ ‪ ، s min = 2Ks β2 = 8.0 × 10−6 mol/L‬ﻭ ‪. log s min = −5.1‬‬
‫‪log s‬‬
‫‪5‬‬ ‫‪10‬‬ ‫‪15‬‬ ‫‪pCN‬‬
‫‪0‬‬
‫‪−1‬‬ ‫ﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ‬ ‫ﻤﻨﻁﻘﺔ ﺘﺭﺴ‪‬ﺏ ‪AgCN‬‬ ‫ﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ‬
‫‪−2‬‬
‫‪−3‬‬
‫‪−4‬‬ ‫‪[Ag(CN)2 ]−‬‬ ‫‪Ag+‬‬
‫‪−5‬‬ ‫ﺭﺍﺠﺤﺔ ﺒﺎﻝﻤﻘﺎﺭﻨﺔ ﻤﻊ‬ ‫ﺭﺍﺠﺤﺔ ﺒﺎﻝﻤﻘﺎﺭﻨﺔ ﻤﻊ‬
‫‪−6‬‬ ‫‪Ag+‬‬ ‫‪[Ag(CN)2 ]−‬‬
‫‪−7‬‬
‫‪.VI‬ﺍﻝﺘﺭﺴﻴﺏ ﻭ ‪ pH‬ﺍﻝﻭﺴﻁ‬
‫‪ .1.VI‬ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﺒﻔﻌل ﺤﻤﺽ‬
‫‪ .1.1.VI‬ﺘﺠﺭﺒﺔ‬
‫ﻻ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ‪ ،‬ﻭﻝﻨﻀﻑ ﺇﻝﻴﻪ ﺒﻀﻌﺔ ﻗﻁﺭﺍﺕ ﻤﻥ‬

‫ﻝﻨﻀﻊ ﻓﻲ ﺃﻨﺒﻭﺏ ﺍﺨﺘﺒﺎﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﻤﺤﻠﻭل ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ ،‬ﻓﻴﻅﻬﺭ ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ ﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ ‪ . BaCO3‬ﻝﻨﻀﻑ‬
‫ﻥ ﺍﻝﺭﺍﺴﺏ ﻴﺨﺘﻔﻲ‪ .‬ﻭﻨﻔﺴ‪‬ﺭ‬
‫ﺍﻵﻥ ﻗﻁﺭﺓ ﻗﻁﺭﺓ ﻤﻥ ﻤﺤﻠﻭل ﻤﺭﻜﹼﺯ ﻤﻥ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ‪ ،‬ﻓﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ H3O+‬ﺘﺘﻔﺎﻋل ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﺒﻭﻨﺎﺕ ‪ CO23−‬ﺍﻝﺘﻲ ﻫﻲ ﺃﺴﺎﺱ‬
‫ﺫﻝﻙ ﺒﺄ ‪‬‬
‫ﻀﻌﻴﻑ‪ ،‬ﻭﻫﺫﺍ ﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻨﺤﻼل ﺍﻝﺭﺍﺴﺏ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪BaCO3 + H 3O+ Ba 2+ + HCO−‬‬
‫‪3 + H2O‬‬
‫‪ .2.1.VI‬ﺘﻌﻤﻴﻡ‬
‫ﻝﺘﻜﻥ ﻝﺩﻴﻨﺎ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺴﺎﻝﺒﺔ ‪ A−‬ﺍﻝﺘﻲ ﺘﻌﻁﻲ ﺭﺍﺴﺒﹰﺎ ‪ CA‬ﻤﻊ ﺍﻝﺸـﺎﺭﺩﺓ ﺍﻝﻤﻭﺠﺒـﺔ ‪.C +‬‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺴﺎﻝﺒﺔ ‪ A−‬ﻫﻲ ﺃﺴﺎﺱ ﻀﻌﻴﻑ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﻬﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﻀ ‪‬ﻡ ﺒﺭﻭﺘﻭﻨﹰﺎ‪ .‬ﺇﺫﺍ‬
‫ﻝﻨﻔﺘﺭﺽ ﺃ ‪‬‬
‫ﻻ ﻤﻥ ﺤﻤﺽ ﻗﻭﻱ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﺸﺒﻊ ﻤﻥ ‪ CA‬ﻴﺤﺼل ﺍﻝﺘﻔﺎﻋل ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫ﺃﻀﻔﻨﺎ ﻤﺤﻠﻭ ﹰ‬
‫‪CA + H 3O+ C + + AH + H2O‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل‪:‬‬
‫‪+‬‬ ‫‪+‬‬ ‫‪−‬‬
‫] ‪[AH] ⋅ [C‬‬ ‫] ‪[AH] ⋅ [C ] [A‬‬ ‫‪K‬‬
‫= ‪K‬‬ ‫=‬ ‫⋅‬ ‫‪= s‬‬
‫] ‪[H3O+‬‬ ‫‪[H3O+ ] [A− ] K A‬‬
‫ﻥ‬
‫ﺇﺫﺍ ﻜﺎﻨﺕ ‪ K‬ﺃﻜﺒﺭ ﺒﻜﺜﻴﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ ﻭﺇﺫﺍ ﻜﺎﻥ ﻫﻨﺎﻝﻙ ﻓﺎﺌﺽ ﻤﻥ ﺍﻝﺤﻤﺽ ﺍﻝﻘﻭﻱ‪ ،‬ﻓﺈ ‪‬‬
‫ل ﺍﻷﺤﻭﺍل ﺴﻴﺼﺎﺤﺏ ﺫﻝﻙ‬
‫ﻻ ﺴﻴﺘﺤﻘﹼﻕ ﺘﻭﺍﺯﻥ ﺒﻴﻥ ﺍﻝﺭﺍﺴﺏ ﻭﺍﻝﻤﺤﻠﻭل‪ .‬ﻓﻲ ﻜ ّ‬
‫ﺍﻝﺭﺍﺴﺏ ﺴﻴﺫﻭﺏ ﻭﺇ ﹼ‬
‫ﺍﺭﺘﻔﺎﻉ ﻓﻲ ﻗﻴﻤﺔ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻭﻫﺫﻩ ﺍﻝﻨﺘﻴﺠﺔ ﻋﺎﻤﺔ‪.‬‬
‫ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪ A−‬ﺃﺴﺎﺴﹰﺎ ﻀﻌﻴﻔﺎﹰ‪ ،‬ﺘﺯﺩﺍﺩ ﺍﻨﺤﻼﻝﻴﺔ ﺍﻝﻤﺭﻜﹼﺏ ﺍﻝﺸﺎﺭﺩﻱ ‪ CA‬ﻤﻊ‬

‫ﺍﻨﺨﻔﺎﺽ ‪ pH‬ﺍﻝﻭﺴﻁ‪.‬‬
‫‪ .1‬ﻨﻀﻴﻑ ﺩ ﻭ ﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍ ﻝﺤﺠﻡ ﻜﻤﻴﺔ ﻗﺩ ﺭ ﻫﺎ ‪ n 0 = 1.0 × 10−2 mol‬ﻤﻥ ﺨﻼﺕ‬
‫ﺍﻝﻔﻀﺔ ﺇﻝﻰ ﺤﺠﻡ ‪ V = 50.0 mL‬ﻤﻥ ﺍﻝﻤﺎﺀ ﺍﻝﻨﻘﻲ‪.‬‬
‫‪ .a‬ﺤﺩ‪‬ﺩ ﺘﺭ ﺍﻜﻴﺯ ﺸﻭﺍ ﺭﺩ ﺍﻝﻔﻀﺔ )‪ (I‬ﻭﺸﻭﺍ ﺭﺩ ﺍﻝﺨﻼﺕ ﻓﻲ ﻫﺫ ﺍ ﺍﻝﻤﺤﻠﻭل‪ .‬ﻫل ﻫﺫﺍ‬
‫ﺍﻝﻤﺤﻠﻭل ﻤﺸﺒﻊ؟‬
‫‪ .b‬ﺤﺩ‪‬ﺩ ‪ pH‬ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻥ ﻨﺼﻑ ﻜﻤﻴﺔ ﺨﻼﺕ ﺍﻝﻔﻀﺔ‬
‫‪ .2‬ﻨﻀﻴﻑ ﺩﻭﻥ ﺘﻤﺩﻴﺩ ﻜﻤﻴﺔ ‪ n‬ﻤﻥ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﺒﺤﻴﺙ ﺃ ‪‬‬
‫ﺍﻝﺘﻲ ﺃﻀﻴﻔﺕ ﺴﺎﺒﻘﹰﺎ ﻗﺩ ﺍﻨﺤﻠﹼﺕ‪.‬‬
‫‪ .a‬ﺤﺩ‪‬ﺩ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﺎﺘﺞ‪.‬‬
‫‪ .b‬ﺤﺩ‪‬ﺩ ﺍﻝﻜﻤﻴﺔ ‪ n‬ﻤﻥ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﺍﻝﻼﺯﻤﺔ‪.‬‬
‫‪. pK A (CH 3COOH/CH 3COO− ) = 4.8 ، pKs (CH 3COOAg) = 2.6‬‬

‫ﺍﻝﺤل‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻤﺸﺒﻊ‪ :‬ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺴﻭﻑ ﻴﺘﺤﻘﻕ ﺍﻝﺘﻭﺍﺯﻨﺎﻥ‪:‬‬
‫‪ .a .1‬ﻝﻨﻔﺘﺭﺽ ﺃ ‪‬‬
‫)‪(1‬‬ ‫‪CH 3COOAg(s) CH 3COO− + Ag+‬‬ ‫‪K1 = Ks = 10−2.6‬‬
‫‪K‬‬
‫‪(2) CH 3COO− + H2O CH 3COOH + OH−‬‬ ‫‪K 20 = e = 10−9.2‬‬
‫‪KA‬‬
‫ﻭﻨﻜﺘﺏ ﺍﻻﻨﺤﻼﻝﻴﺔ ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬
‫] ‪s = [Ag+ ] = [CH 3COOH] + [CH 3COO−‬‬
‫ﻥ ﺍﻨﺤﻼل ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻴﺅﺩﻱ ﺇﻝﻰ ﺘﺤﺭﻴﺭ ﺸﺎﺭﺩﺓ ﺍﻝﺨﻼﺕ ﺍﻝﺘﻲ ﻫﻲ ﺃﺴﺎﺱ ﻀﻌﻴﻑ‬
‫ﺇ‪‬‬
‫ﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ ﺴﺘﻜﻭﻥ ﺃﻜﺒﺭ ﻤﻥ ‪ . 7‬ﻭﺒﻌﺒﺎﺭﺓ ﺃﺨﺭﻯ ﺴﻴﻜﻭﻥ‬
‫ﻭﺴﻴﺼﺒﺢ ﺍﻝﻭﺴﻁ ﻗﻠﻭﻴﹰﺎ‪ .‬ﺃﻱ ﺃ ‪‬‬
‫‪ pH ≫ pK A‬ﻭﺴﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺤﻤﺽ ﺍﻝﺨل ]‪ [CH 3COOH‬ﻭﺘﺼﺒﺢ ﻋﺒﺎﺭﺓ ﺍﻻﻨﺤﻼﻝﻴﺔ‪:‬‬
‫‪s = [Ag+ ] ≈ [CH 3COO− ] ≈ (Ks )1/2‬‬
‫ﻭﻤﻨﻪ‬
‫‪s = 5.0 × 10−2 mol/L‬‬
‫ل ﺨﻼﺕ ﺍﻝﻔﻀﺔ ﺍﻝﻤﻀﺎﻓﺔ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﻗﺩ‬
‫ﻥﻜّ‬
‫ﻼ ﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫ﻓﺈﺫﺍ ﺤﺴﺒﻨﺎ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻤﺜ ﹰ‬
‫ﺍﻨﺤﻠﺕ ﺘﻤﺎﻤﹰﺎ ﻭﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ ﻝﻭﺠﺩﻨﺎ‪ . n 0/V = 0.20 mol/L :‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ‪ s‬ﺃﺼﻐﺭ‬
‫ﻼ ﻭﻓﺭﻀﻴﺘﻨﺎ ﻜﺎﻨﺕ ﺼﺤﻴﺤﺔ‪.‬‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻤﺸﺒﻊ ﻓﻌ ﹰ‬
‫ﻤﻥ ‪ ، n 0/V‬ﺃﻱ ﺇ ‪‬‬
‫ﻥ‪:‬‬
‫‪ . b.1‬ﻝﺤﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻴﻜﻔﻲ ﺃﻥ ﻨﺘﺄﻤل ﺍﻝﺘﻭﺍﺯﻥ )‪ (2‬ﺤﻴﺙ ﻨﻼﺤﻅ ﺃ ‪‬‬
‫‪[CH 3COOH]=[OH− ] = ω‬‬
‫‪ω2‬‬
‫ﻥ ‪ω = 5.6 × 10−6 mol/L‬‬ ‫≈ ‪ K 20 = K B‬ﺃﻱ ﺇ ‪‬‬ ‫ﻤﻥ ﺠﻬﺔ ﺃﺨﺭﻯ ﻝﺩﻴﻨﺎ‬
‫‪s‬‬
‫ﻥ ﺍﻝﻘﻴﻤﺔ ﺍﻝﺘﻲ ﻭﺠﺩﻨﺎﻫﺎ ﺘﺅﻜﹼﺩ ﺼﺤﺔ ﺍﻝﻔﺭﻀﻴﺎﺕ ﺍﻝﺘﻲ ﻭﻀﻌﻨﺎﻫﺎ‪.‬‬
‫ﻭ ‪ . pH = 8.7‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ ﺇﻀﺎﻓﺔ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﻴﺅﺩﻱ ﺇﻝﻰ ﺍﻻﻨﺤﻼل ﺍﻝﺠﺯﺌﻲ ﻝﻠﺭﺍﺴﺏ ﻭﺫﻝﻙ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ‬
‫‪ .2‬ﺇ ‪‬‬
‫‪CH 3COOAg(s) + H 3O+ CH3COOH + Ag+ + H2O‬‬
‫‪K 30 = Ks /K A = 102.2‬‬
‫ل ﻨﺼﻑ ﻜﻤﻴﺔ ﺨﻼﺕ ﺍﻝﻔﻀﺔ ﺍﻝﻤﻀﺎﻓﺔ ﻴﻜﻭﻥ‪:‬‬
‫‪ .a.2‬ﻋﻨﺩﻤﺎ ﺘﻨﺤ ّ‬
‫‪n(Ag+ ) = n 0/2 = 5.0 × 10−3 mol‬‬
‫‪n‬‬
‫ﻭﻫﺫﺍ ﻴﻭﺍﻓﻕ ﺍﻝﺘﺭﻜﻴﺯ ‪[Ag+ ] = 0 = 0.10 mol/L‬‬
‫‪2 ⋅V‬‬
‫ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﺨﻼﺕ‪:‬‬

‫‪Ks‬‬
‫= ] ‪[CH 3COO−‬‬ ‫‪= 2.5 × 10−2 mol/L‬‬
‫] ‪[Ag+‬‬
‫ﺘﻌﻁﻲ ﻤﻌﺎﺩﻝﺔ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩﺓ ﻝﺤﻤﺽ ﺍﻝﺨل ﻭﺸﺎﺭﺩﺓ ﺍﻝﺨﻼﺕ‪:‬‬
‫‪n‬‬
‫‪[CH 3COOH] + [CH3COO− ] = 0‬‬
‫‪2 ⋅V‬‬
‫ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺤﻤﺽ ﺍﻝﺨل‪. [CH 3COOH] = 7.5 × 10 mol/L :‬‬
‫‪−2‬‬
‫ﻭﺘﻜﻭﻥ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪:‬‬

‫‪−‬‬
‫] ‪[CH3COO‬‬
‫‪pH = pK A + log‬‬ ‫‪= 4.3‬‬
‫]‪[CH 3COOH‬‬
‫‪ .b.2‬ﻜﻤﻴﺔ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ‪ n‬ﺍﻝﻼﺯﻤﺔ ﻻﻨﺤﻼل ﻨﺼﻑ ﻜﻤﻴﺔ ﺨﻼﺕ ﺍﻝﻔﻀﺔ ﺘﺴﺎﻭﻱ ﻜﻤﻴﺔ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻨﺘﺭﺍﺕ ﻓﻲ ﺍﻝﻭﺴﻁ‪ .‬ﻭﻹﻴﺠﺎﺩ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺘﺭﺍﺕ ﻨﻜﺘﺏ ﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ‪:‬‬
‫‪[CH 3COO− ] + [NO−‬‬ ‫‪−‬‬ ‫‪+‬‬ ‫‪+‬‬

‫] ‪3 ] + [OH ] = [Ag ] + [H 3O‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﺈﻫﻤﺎل ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﻭﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻤﻘﺎﺒل ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻷﺨﺭﻯ ﻨﺠﺩ ﺃ ‪‬‬
‫‪[NO−‬‬ ‫‪+‬‬ ‫‪−‬‬

‫‪3 ] = [Ag ] − [CH 3COO ] = 7.5 × 10‬‬
‫‪−2‬‬
‫‪mol/L‬‬
‫ﻭﺘﻜﻭﻥ ﻜﻤﻴﺔ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ‪: n‬‬
‫‪n =V‬‬ ‫‪⋅ [NO−‬‬
‫]‪3‬‬ ‫‪= 3.8 × 10‬‬ ‫‪−3‬‬
‫‪mol‬‬
‫ﻴﻤﻜﻥ ﺃﻴﻀﹰﺎ ﺤﺴﺎﺏ ﻜﻤﻴﺔ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ‪ n‬ﻤﻥ ﺍﻝﻌﻼﻗﺔ‪:‬‬
‫‪. n(H 3O+ )added = n(CH3COOH) + n(H 3O+ )free‬‬
‫‪ .2.VI‬ﺘﺭﺴﻴﺏ ﻜﺒﺭﻴﺘﻴﺩﺍﺕ )ﺴﻠﻔﻴﺩﺍﺕ( ﺍﻝﻤﻌﺎﺩﻥ‬
‫ﺘﻌﻁﻲ ﺍﻝﻜﺜﻴﺭ ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﺭﻭﺍﺴﺏ ﺒﻭﺠﻭﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﻴﺩ ‪ S2−‬ﺍﻝﺘـﻲ ﻫـﻲ‬
‫ﺃﺴﺎﺱ ﺜﻨﺎﺌﻲ ﺍﻝﻭﻅﻴﻔﺔ‪ .‬ﻭﻋﻠﻴﻪ ﻓﺈﻥ ﺘﺭﺴﻴﺏ ﻜﺒﺭﻴﺘﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ ﻴﺘﻌﻠﹼﻕ ﺒـ ‪ pH‬ﺍﻝﻭﺴﻁ‪ .‬ﻴﺠـﺭﻱ‬
‫ل ﻫـﺫﺍ‬
‫ﻋﺎﺩﺓ ﺍﺴﺘﺜﻤﺎﺭ ﻫﺫﻩ ﺍﻝﺨﺎﺼﻴﺔ ﻝﻔﺼل ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻀﻤﻥ ﻓﻠ ‪‬ﺯ ﻤﻌﺩﻨﻲ ﺒﻌﺩ ﺤ ّ‬
‫ﺍﻝﻔﻠ ‪‬ﺯ ﻓﻲ ﻭﺴﻁ ﻤﺎﺌﻲ ﺜ ‪‬ﻡ ﺍﻝﺘﺤﻜﹼﻡ ﺒـ ‪ pH‬ﻫﺫﺍ ﺍﻝﻭﺴﻁ‪ .‬ﻭﺴﻨﻭﻀ‪‬ﺢ ﻫﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﺒﺎﻝﻤﺜﺎل ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫ﻝﺩﻴﻨﺎ ﻤﺤﻠﻭل ﻤﺸﺒ‪‬ﻊ ﺒﻜﺒﺭﻴﺕ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ‪ . H2S‬ﻨﺜ‪‬ﺒﺕ ﺘﺭﻜﻴﺯ ‪ H2S‬ﺒﺤﻴﺙ‪:‬‬
‫‪[H2S] = c = 1.0 × 10−2 mol/L‬‬
‫ﻨﻐﻴ‪‬ﺭ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ ﻋﻥ ﻁﺭﻴﻕ ﺍﺴﺘﻌﻤﺎل ﻤﺤﺎﻝﻴل ﻤﻭﻗﻴﺔ‪ .‬ﺤﺩ‪‬ﺩ ﻗﻴﻡ ‪ pH‬ﺍﻝﺘﻲ ﻴﺘﺭﺴ‪‬ﺏ‬
‫ﻥ‪:‬‬
‫ل ﻤﻥ ‪ CoS ، FeS ، MnS‬ﺇﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﻋﻨﺩﻫﺎ ﻜ ّ‬
‫‪[Mn2 + ]0 = [Fe2+ ]0 = [Co2 + ]0 = c ′ = 1.0 × 10−4 mol/L‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪pK A2 (HS− /S2− ) = 13 ، pK A1(H2S/HS− ) = 7.0 :‬‬
‫‪pKs (CoS) = 20.4 ، pKs (FeS) = 17.2 ، pKs (MnS) = 9.6‬‬
‫ﺍﻝﺤل‬
‫‪ .1‬ﻝﻨﺭﻤﺯ ﺇﻝﻰ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﻨﻴﺔ ﺒﺎﻝﺭﻤﺯ ‪ . M 2 +‬ﻴﺘﻜﻭ‪‬ﻥ ﺭﺍﺴﺏ ﺇﺫﺍ ﺘﺤﻘﹼﻕ ﺍﻝﺸﺭﻁ‪:‬‬
‫‪[M 2 + ] ⋅ [S2− ] ≥ Ks‬‬
‫‪Ks‬‬
‫≥ ] ‪. [S2−‬‬ ‫ﺃﻱ ﻋﻨﺩﻤﺎ‪:‬‬
‫‪c′‬‬
‫ﻝﻨﻌﺒ‪‬ﺭ ﻋﻥ ] ‪ [S2−‬ﺒﺩﻻﻝﺔ ‪ K A1‬ﻭ ‪ K A2‬ﻭ ‪ c‬ﻭ ‪: [H3O+ ] = h‬‬
‫‪[S2− ] ⋅ h 2‬‬
‫= ‪K A1 ⋅ K A2‬‬
‫]‪[H2S‬‬
‫ﻥ‪:‬‬
‫]‪K A1 ⋅ K A2 ⋅ [H2S‬‬
‫= ] ‪[S2−‬‬
‫‪h2‬‬
‫ﻭﻝﻜﻲ ﻴﺘﻜﻭ‪‬ﻥ ﺭﺍﺴﺏ ﻴﺠﺏ ﺃﻥ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺘﺭﺍﺠﺤﺔ‪:‬‬
‫‪K A1 ⋅ K A2 ⋅ c‬‬ ‫‪Ks‬‬

‫≥‬
‫‪h2‬‬ ‫‪c′‬‬
‫ﻭﻨﻌﻴﺩ ﺼﻴﺎﻏﺔ ﺍﻝﺸﺭﻁ ﺍﻝﺴﺎﺒﻕ ﻜﻤﺎ ﻴﻠﻲ‪:‬‬
‫‪K A1 ⋅ K A2 ⋅ c ⋅ c ′‬‬
‫≤ ‪h2‬‬
‫‪Ks‬‬
‫ﻥ‪:‬‬
‫‪pK A1 + pK A2 − log(c ⋅ c ′) − pKs‬‬

‫≥ ‪pH‬‬
‫‪2‬‬
‫ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﺍﻝﻌﺩﺩﻱ ﻴﺼﺒﺢ ﺍﻝﺸﺭﻁ‪. pH ≥ 13 − pKs /2 :‬‬
‫• ﻴﺘﺭﺴ‪‬ﺏ ‪ MnS‬ﻋﻨﺩﻤﺎ ‪. pH ≥ 8.2‬‬
‫• ﻴﺘﺭﺴ‪‬ﺏ ‪ FeS‬ﻋﻨﺩﻤﺎ ‪. pH ≥ 4.4‬‬
‫• ﻴﺘﺭﺴ‪‬ﺏ ‪ CoS‬ﻋﻨﺩﻤﺎ ‪. pH ≥ 2.8‬‬
‫‪‬ﻴﻠﺨﺹ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﻨﺎ ﺇﻝﻴﻬﺎ‪:‬‬
‫‪CoS‬‬ ‫‪MnS‬‬
‫‪2.8‬‬ ‫‪4.4‬‬ ‫‪FeS‬‬ ‫‪8.2‬‬ ‫‪pH‬‬
‫ﺘﺭﺴﻴﺏ ﻜﺒﺭﻴﺘﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ ﺫﻝﻙ ﻋﻨﺩﻤﺎ‪:‬‬
‫‪ [H2 S] = 1.0 × 10−2 mol/L‬ﻭ ‪. [M 2 + ]0 = 1.0 × 10−4 mol/L‬‬
‫‪ .3.VI‬ﺘﺭﺴﻴﺏ ﻫﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﻌﺎﺩﻥ‬
‫‪ .1.3.VI‬ﺘﺤﺩﻴﺩ ‪ pH‬ﺍﻝﺘﺭﺴﻴﺏ ﻝﻠﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﻌﺩﻨﻴﺔ‬
‫ﺘﻌﻁﻲ ﺍﻝﻜﺜﻴﺭ ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ‪، Fe3 + ، Fe2 + ، Ca 2 + ، Zn2 + ، Al3 +‬‬

‫‪ ...، Cu2 +‬ﺭﻭﺍﺴﺏ ﺒﻭﺠﻭﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪.‬‬
‫ﻓﻲ ﺤﺎﻝﺔ ﺸﺎﺭﺩﺓ ﻤﻭﺠﺒﺔ ‪ M n +‬ﺘﻜﻭﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﺘﺭﺴﻴﺏ ﻫﻲ‪:‬‬
‫)‪M n + + n OH− M (OH)n (s‬‬
‫ﻱ ﻗﻴﻤﺔ ‪ pH‬ﻴﺒﺩﺃ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﻴﺎ ﺘﹸﺭﻯ؟‬

‫ﻝﻴﻜﻥ ‪ c‬ﺘﺭﻜﻴﺯ ﻤﺤﻠﻭل ﺍﻝﺸﺎﺭﺩﺓ ‪ ، M n +‬ﻋﻨﺩ ﺃ ‪‬‬
‫ﻋﻨﺩﻤﺎ ﻴﻅﻬﺭ ﺍﻝﺭﺍﺴﺏ ‪‬ﻴﺤﻘﹼﻕ ﺘﺭﻜﻴﺯﺍ ﺸﻭﺍﺭﺩ ‪ M n +‬ﻭ ‪ OH−‬ﺍﻝﻤﺴﺎﻭﺍﺓ ‪:‬‬

‫‪[M n + ] ⋅ [OH− ]n = Ks‬‬
‫ﻭﻤﻨﻪ‬
‫‪ K 1/n‬‬
‫‪[OH ] = ‬‬
‫‪−‬‬ ‫‪s ‬‬
‫‪ [M + ] ‬‬
‫‪n‬‬
‫ﻭﻨﻜﺘﺏ‪ pOH = (pKs + log[M n + ])/n :‬ﻭﺒﺎﻝﺘﺎﻝﻲ ﻴﻜﻭﻥ ‪ pH‬ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ‪:‬‬

‫‪pH = pKe − (pKs + log[M n + ])/n‬‬
‫ﻥ‪:‬‬
‫ﻋﻨﺩﻤﺎ ‪ [M n + ] = 1.0 × 10−2 mol/L‬ﻭﻓﻲ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪. pH = 4.0 ، pKs = 32‬‬ ‫• ﻓﻲ ﺤﺎﻝﺔ ‪، Al(OH)3‬‬
‫• ﻓﻲ ﺤﺎﻝﺔ ‪. pH = 6.8 ، pKs = 16.4 ، Zn(OH)2‬‬
‫• ﻓﻲ ﺤﺎﻝﺔ ‪. pH = 12.4 ، pKs = 5.2 ، Ca(OH)2‬‬
‫ﻴﻅﻬﺭ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ ﻗﻴﻡ ‪ pH‬ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻅﻬﻭﺭ ﺭﻭﺍﺴﺏ ﻝﻌﺩﺩ ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﻌﺩﻨﻴﺔ ﻓﻲ‬
‫ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪ 25 C‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻌﺩﻨﻴﺔ‪ [M n + ]0 :‬ﻤﺴﺎﻭﻴﹰﺎ‬
‫‪. 1.0 × 10−2 mol/L‬‬
‫‪Ce(OH)4‬‬ ‫‪Zn(OH)2 AgOH‬‬ ‫‪Ba(OH)2‬‬
‫‪0‬‬ ‫‪7‬‬ ‫‪14‬‬ ‫‪pH‬‬

‫‪Fe(OH)3‬‬ ‫‪Pb(OH)2‬‬ ‫‪Fe(OH)2‬‬
‫‪ .2.3.VI‬ﺤﺎﻝﺔ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﺍﻝﻤﺘﺫﺒﺫﺒﺔ‬
‫ﺘﻌﺘﺒﺭ ﺒﻌﺽ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﻤﺜل ‪ Al(OH)3‬ﻭ ‪ Zn(OH)2‬ﻫﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ﻤﺘﺫﺒﺫﺒﺔ‪،‬‬

‫ﺒﻤﻌﻨﻰ ﺃﻨﻬﺎ ﻴﻤﻜﻥ ﺃﻥ ﺘﺴﻠﻙ ﺴﻠﻭﻙ ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ‪ .‬ﻭﻫﻜﺫﺍ ﻨﻜﺘﺏ‪:‬‬
‫‪Al(OH)3 (s) + 3 H 3O+ Al 3 + + 6 H2O‬‬
‫ﺃﺴﺎﺱ‬ ‫ﺤﻤﺽ‬
‫‪Al(OH)3 (s) + OH−‬‬ ‫‪ [Al(OH)4 ]−‬‬

‫ﺤﻤﺽ‬ ‫ﺃﺴﺎﺱ‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ [Al(OH)4 ]−‬ﻫﻲ ﻤﻌﻘﹼﺩ ﺘﺅﺩﻱ ﻓﻴﻪ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺩﻭﺭ‬

‫ﺍﻝﺭﺒﻴﻁﺔ‪.‬‬
‫ﻥ ﺍﻹﻀﺎﻓﺔ ﺍﻝﺘﺩﺭﻴﺠﻴـﺔ‬
‫ﻭﻫﻜﺫﺍ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻌﺩﻨﻲ ‪ M (OH)n‬ﻤﺘﺫﺒﺫﺒﹰﺎ ﻓﺈ ‪‬‬
‫ﻝﻠﺼﻭﺩ ﺇﻝﻰ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ‪ M n +‬ﻴﺅﺩﻱ ﺒﺩﺍﻴﺔ ﺇﻝﻰ ﻅﻬﻭﺭ ﺭﺍﺴﺏ ‪ M (OH)n‬ﺜ ‪‬ﻡ ﺍﻨﺤﻼﻝﻪ‬
‫ﻋﻥ ﻁﺭﻴﻕ ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ‪ .‬ﻭﻫﻜﺫﺍ ﺘﺘﻌﻠﹼﻕ ﺍﻨﺤﻼﻝﻴﺔ ‪ M (OH)n‬ﺒﻘﻴﻤﺔ ‪ pH‬ﺍﻝﻭﺴﻁ‪.‬‬
‫ﻴﻭﻀ‪‬ﺢ ﺍﻝﺘﻁﺒﻴﻕ ﺍﻝﺘﺎﻝﻲ ﺘﻐﻴﺭ ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ ‪ Al(OH)3‬ﺒﺘﻐﻴـﺭ ﻗﻴﻤـﺔ‬
‫‪ pH‬ﺍﻝﻭﺴﻁ‪.‬‬
‫ﻻ ﻤﺭﻜﹼـﺯﹰﺍ‬
‫ﻨﻀﻴﻑ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ c = 1, 0 ⋅ 10−2 mol/L‬ﻤﺤﻠﻭ ﹰ‬
‫ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ‪ ،‬ﻭﻫﺫﺍ ﻤﺎ ﻴﺘﻴﺢ ﺇﻫﻤﺎل ﺍﻝﺘﻤﺩﻴﺩ‪.‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺍﻝﻘﻴﻤﺘﻴﻥ ‪ pH1‬ﻭ ‪ pH2‬ﺍﻝﻠﺘﻴﻥ ﻴﺤﺼل ﻋﻨﺩﻫﻤﺎ ﻋﻠﻰ ﺍﻝﺘﺭﺘﻴﺏ‪:‬‬
‫‪ .i‬ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ‪.‬‬
‫‪ .ii‬ﺍﺨﺘﻔﺎﺀ ﺍﻝﺭﺍﺴﺏ ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ‪.‬‬
‫‪ .2‬ﻋﺒ‪‬ﺭ ﻋﻥ ﺍﻨﺤﻼﻝﻴﺔ ‪ Al(OH)3‬ﺒﺩﻻﻝﺔ ] ‪ h = [H 3O+‬ﻓﻲ ﺍﻝﻤﺠﺎل ] ‪. [pH1, pH2‬‬
‫ﻼ ﺍﻝﺘﻘﺭﻴﺒﺎﺕ ﺍﻝﻤﺴﺘﻌﻤﻠﺔ‪ ،‬ﻋﺒﺎﺭﺍﺕ )‪. log s = f (pH‬‬
‫ﻭﺍﺴﺘﻨﺘﺞ‪ ،‬ﻤ‪‬ﻌﹼﻠ ﹰ‬
‫‪ .3‬ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ﺍﻝـ ‪ pH‬ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺍﻻﻨﺤﻼﻝﻴﺔ ﺃﺼﻐﺭ ﻤﺎ ﻴﻤﻜﻥ ﻭﺍﻝﻘﻴﻤﺔ ‪ s‬ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻬﺎ‪.‬‬
‫‪ .4‬ﺍﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ )‪. log s =f (pH‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪. log β4 ([Al(OH)4 ] ) = 34.0 ، pK s (Al(OH)3 ) = 32.0 :‬‬
‫‪−‬‬
‫ﺍﻝﺤل‬
‫‪ Al‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ‬ ‫‪3+‬‬
‫‪ . i.1‬ﻝﻴﻜﻥ ‪ [Al ]0‬ﺍﻝﺘﺭﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻲ ﻝﺸﻭﺍﺭﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ‬
‫‪3+‬‬
‫ﻴﻅﻬﺭ ﺭﺍﺴﺏ ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ ﻋﻨﺩﺌﺫ ‪. [Al 3+ ]0 ⋅ [OH− ]3 = K s‬‬

‫ﻥ‪:‬‬
‫‪ K 1/3‬‬
‫‪[OH− ] = ‬‬ ‫‪s‬‬ ‫‪−10‬‬
‫‪ = 1.0 × 10 mol .L‬‬
‫‪−1‬‬
‫‪ [Al 3+ ]0 ‬‬
‫ﻥ ‪. pH1 = 4.0‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪ . ii.1‬ﺘﻌﻭﺩ ﺍﻨﺤﻼﻝﻴﺔ ﺍﻝﺭﺍﺴﺏ ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ ﺇﻝﻰ ﺍﻝﺘﻔﺎﻋل ﺫﻱ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪−‬‬
‫] ‪Al(OH)3 + OH− ⇌ [ Al(OH)4‬‬
‫ﻴﻤﺘﻠﻙ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﺜﺎﺒﺕ ﺘﻭﺯﻥ ‪ K 0‬ﻴ‪‬ﺤﻘﹼﻕ ﻤﺎ ﻴﻠﻲ ‪:‬‬

‫‪0‬‬ ‫] ‪[[Al(OH)4 ]−‬‬
‫= ‪K‬‬
‫] ‪[OH−‬‬
‫‪[[Al(OH)4 ]− ] [Al 3+ ] ⋅ [OH− ]3‬‬
‫=‬ ‫⋅‬
‫] ‪[OH−‬‬ ‫‪[Al 3+ ] ⋅ [OH− ]3‬‬
‫ﻥ ‪ . K 0 = β4 ⋅ K s‬ﻓﻲ ﺍﻝﻠﺤﻅﺔ ﺍﻝﺘﻲ ﻴﺨﺘﻔﻲ ﻓﻴﻬﺎ ﺭﺍﺴﺏ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ‪ ،‬ﻴﻜﻭﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻋﻨﺼﺭ ﺍﻷﻝﻤﻨﻴﻭﻡ ﺒﻤﻌﻅﻤﻪ ﻋﻠﻰ ﺸﻜل ﺸﻭﺍﺭﺩ ﺃﻝﻭﻤﻴﻨﺎﺕ‪:‬‬
‫‪[[Al(OH)4 ] ] = 1.0 × 10−2 mol / L‬‬
‫‪−‬‬
‫ﻭﻋﻠﻴﻪ ﻴﺼﺒﺢ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪:‬‬

‫‪[Al(OH)4 ]−‬‬
‫= ] ‪[OH−‬‬ ‫‪= 1.0 × 10−4 mol / L‬‬
‫‪K s ⋅ β4‬‬
‫ﻥ ‪. pH2 = 10.0‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃﻨﻪ ﻓﻲ ﺤﺎﻝﺔ ‪ pH ≤ 4.0‬ﻴﻜﻭﻥ ‪. [Al 3+ ] = 1.0 × 10−2 mol / L‬‬
‫ﻭﻓﻲ ‪ pH ≥ 10.0‬ﻴﻜﻭﻥ ‪. [[Al(OH)4 ]− ] = 1.0 × 10−2 mol / L‬‬
‫‪ .2‬ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﻗﻴﻤﺔ ﺍﻝـ ‪ pH‬ﺃﺼﻐﺭ ﻤﻥ ‪ pH1‬ﺃﻭ ﺃﻜﺒﺭ ﻤﻥ ‪ pH2‬ﻴﻜﻭﻥ ‪:‬‬
‫] ‪s = [Al 3+ ] + [[Al(OH)4 ]−‬‬
‫ﺃﻱ‬
‫‪Ks‬‬
‫=‪s‬‬ ‫‪− 3‬‬
‫] ‪+ Ks .β4 .[OH−‬‬
‫] ‪[OH‬‬
‫ﻥ‪:‬‬
‫ﺒﺎﺴﺘﻌﻤﺎل ﻋﺒﺎﺭﺓ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ‪ ،‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪Ks ⋅ h 3‬‬ ‫‪K s ⋅ β4 ⋅ K w‬‬
‫=‪s‬‬ ‫‪3‬‬
‫‪+‬‬
‫‪K‬‬ ‫‪w‬‬
‫‪h‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ ﺃ ‪‬‬
‫‪−12‬‬
‫‪10‬‬
‫‪s = 1010 ⋅ h 3 +‬‬
‫‪h‬‬
‫] ‪ [Al ] ≥ 10[[Al(OH)4 ]−‬ﻴﻜﻭﻥ ‪ ، pH ≤ 5.2‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻴﻤﻜﻥ‬
‫‪3+‬‬
‫ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ‬
‫ﻥ‪s ≈ [Al 3+ ] ≈ 1010 h 3 :‬‬
‫ﺇﻫﻤﺎل ] ‪ [[Al(OH)4 ]−‬ﻤﻘﺎﺒل ] ‪ ، [Al 3+‬ﻭﻋﻠﻴﻪ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪. log s = 10 − 3 pH‬‬ ‫ﻥ‪:‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻴﻤﻜﻥ‬ ‫] ‪ [[Al(OH)4 ]− ] ≥ 10[Al 3+‬ﻴﻜﻭﻥ ‪pH ≥ 5.8‬‬ ‫ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ‬
‫ﺇﻫﻤﺎل ] ‪ [Al 3+‬ﻤﻘﺎﺒل ] ‪ [[Al(OH)4 ]−‬ﻭﻋﻠﻴﻪ ﻨﻜﺘﺏ‪:‬‬
‫‪−‬‬ ‫‪10−12‬‬
‫≈ ‪s ≈ [Al(OH)4 ] ‬‬
‫‪h‬‬
‫‪. log s = −12 + pH‬‬ ‫ﻥ‪:‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪ds‬‬
‫‪ ،‬ﺃﻱ‬ ‫‪ .3‬ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺍﻻﻨﺤﻼﻝﻴﺔ ﺃﺼﻐﺭﻴﺔ ﻴﻜﻭﻥ ‪= 0‬‬
‫‪dh‬‬
‫‪10−12‬‬
‫‪3 ⋅ 1010 ⋅ h 2 − 2 = 0‬‬
‫‪h‬‬
‫ﻭﻤﻨﻪ‬
‫‪h = hmin = 2.4 × 10−6 mol / L‬‬
‫ﻥ‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪pH min = 5.6‬‬
‫ﻭ‬
‫‪. log s min = −6.3‬‬ ‫ﺃﻭ‬ ‫‪s min = 5.6 × 10−7 mol / L‬‬
‫‪‬ﻴﺒﻴﻥ ﺍﻝﺸﻜﻼﻥ ﺍﻝﺘﺎﻝﻴﺎﻥ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ )‪ s = f (pH‬ﻭ )‪. log s = f (pH‬‬
‫) ‪S ( mol.L−1‬‬
‫‪10−2‬‬
‫‪Al3+‬‬ ‫‪Al ( OH )3‬‬ ‫‪[ Al ( OH )4 ]−‬‬
‫‪10−5‬‬ ‫‪pH‬‬
‫‪0‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪12‬‬ ‫‪14‬‬
‫‪log S‬‬
‫‪0‬‬ ‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪12‬‬ ‫‪14‬‬

‫‪0‬‬ ‫ﺭﺍﺴﺏ ‪Al ( OH )3‬‬ ‫‪pH‬‬
‫‪−1‬‬
‫‪−2‬‬
‫ﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ‬ ‫ﻻ ﻴﻭﺠﺩ ﺭﺍﺴﺏ‬
‫‪−3‬‬
‫‪−4‬‬
‫‪−5‬‬
‫‪−6‬‬
‫‪ Al3+‬ﺭﺍﺠﺢ ﺒﺎﻝﻨﺴﺒﺔ‬
‫‪−7‬‬ ‫‪ Al ( OH )−4‬ﺭﺍﺠﺢ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ‪Al 3+‬‬
‫ﺇﻝﻰ ‪Al ( OH )4‬‬
‫‪−‬‬
‫‪−8‬‬
‫‪ .VII‬ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﻝﺘﺭﺴﻴﺏ‬
‫ﺘﻌﺘﻤﺩ ﺍﻝﻌﺩﻴﺩ ﻤﻥ ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﻋﻠﻰ ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﺭﺴﻴﺏ‪ .‬ﻭﻜﻤﺎ ﻫﻭ ﺍﻝﺤﺎل ﻓﻲ ﺴﺎﺌﺭ ﺘﻔﺎﻋﻼﺕ‬
‫ﻥ ﺘﻔﺎﻋل ﺍﻝﺘﺭﺴﻴﺏ ﻴﻨﺒﻐﻲ ﺃﻥ ﻴﻜﻭﻥ ﺘﺎﻤﹰﺎ ﻭﺴﺭﻴﻌﹰﺎ ﻭﻭﺤﻴﺩﹰﺍ‪ .‬ﻤﻥ ﺠﻬﺔ ﺃﺨـﺭﻯ ﻭﻤـﻥ‬
‫ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻓﺈ ‪‬‬
‫ﻭﺠﻬﺔ ﻨﻅﺭ ﻋﻤﻠﻴﺔ ﻴﻨﺒﻐﻲ ﺃﻥ ﻨﺘﻤﻜﻥ ﺒﺴﻬﻭﻝﺔ ﻤﻥ ﺘﺤﺭ‪‬ﻱ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫ﻝﻨﺩﺭﺱ ﻋﻠﻰ ﺴﺒﻴل ﺍﻝﻤﺜﺎل ﻤﻌﺎﻴﺭﺓ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﻤﻌﻠـﻭﻡ‬
‫ﺍﻝﺘﺭﻜﻴﺯ ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ‪.‬‬
‫‪ .1.VII‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫ﻝﻴﻜﻥ ﻝﺩﻴﻨﺎ ﺍﻝﺤﺠﻡ ‪ V1‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ﻤﺠﻬﻭل ‪ .C 1‬ﻨﻀﻴﻑ ﺇﻝﻴﻪ‬
‫ﺘﺩﺭﻴﺠﻴﹰﺎ ﺤﺠﻤﹰﺎ ‪ V2‬ﻤﻥ ﻤﺤﻠﻭل ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ ﺫﻱ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﻤﻌﻠﻭﻡ ‪.C 2‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ‪:‬‬
‫ﺇ‪‬‬
‫)‪Ag+ + Cl− AgCl(s‬‬
‫ﻭﻴﻜﻭﻥ ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻫﻭ‪:‬‬
‫‪K = 1/Ks = 1/([Ag+ ] ⋅ [Cl− ]) = 5.0 × 109‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ‪.‬‬
‫♦ ﻝﻨﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ‪ V2‬ﺍﻝﺘﻲ ﻴﻅﻬﺭ ﻋﻨﺩﻫﺎ ﺍﻝﺭﺍﺴﺏ‪.‬‬
‫‪V2 ⋅ C 2‬‬ ‫‪V ⋅C‬‬

‫= ] ‪[Ag+‬‬ ‫‪ [Cl− ] = 1 1‬ﻭ‬
‫‪V1 + V2‬‬ ‫‪V1 + V2‬‬
‫ﻥ ‪: Ks ≪ 1‬‬
‫ﻥ ‪ V1 ≫ V2‬ﻷ ‪‬‬
‫ﺒﻔﺭﺽ ﺃ ‪‬‬
‫‪V2 ⋅ C 2‬‬
‫≈ ] ‪[Ag+‬‬ ‫‪ [Cl− ] ≈ C 1‬ﻭ‬
‫‪V1‬‬
‫‪V2 ⋅ C 2‬‬
‫ﻥ‪:‬‬
‫⋅ ‪ . Ks = C 1‬ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬ ‫ﻭﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‬
‫‪V1‬‬
‫‪Ks ⋅ V1‬‬
‫= ‪V2‬‬
‫‪C1 ⋅ C 2‬‬
‫ﻥ‪:‬‬
‫ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺤﻴﺙ ‪ C 1 = C 2 ≈ 0.10 mol / L‬ﻭ ‪ V1 = 10.0 mL‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪V2 = 2.0 × 10−7 mL‬‬
‫ﻥ ﺍﻝﺭﺍﺴﺏ ﻴﻅﻬﺭ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﺃﻭل ﻗﻁﺭﺓ )ﺤﻭﺍﻝﻲ ‪ ( 5.0 × 10−2 mL‬ﻤﻥ ﻤﺤﻠﻭل‬
‫ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ‪ .‬ﻭﻴﻤﻜﻥ ﺍﻝﺘﺤﻘﹼﻕ ﻤﻥ ﺫﻝﻙ ﺒﺴﻬﻭﻝﺔ ﺘﺠﺭﻴﺒﻴﹰﺎ‪.‬‬
‫♦ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺘﻜﻭﻥ ﻜﻤﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻭﺍﻝﻔﻀﺔ ﺍﻝﻤﻀﺎﻓﺔ ﻤﺘﺴﺎﻭﻴﺔ‪:‬‬
‫‪n 0 (Cl− ) = n(Ag+ )added‬‬
‫ﻥ‪:‬‬
‫ﺃﻱ ﺃ ‪‬‬
‫‪C 1 ⋅ V1 = C 2 ⋅ V2eqv‬‬
‫ﻭﻜﻤﺎ ﻓﻌﻠﻨﺎ ﻓﻲ ﺍﻝﻤﻌﺎﻴﺭﺍﺕ ﺍﻝﺴﺎﺒﻘﺔ‪ ،‬ﻨﻌﺭ‪‬ﻑ ﺍﻝﻤﻘﺩﺍﺭ ‪ x‬ﻜﻤﺎ ﻴﻠﻲ‪:‬‬
‫‪V‬‬
‫‪x = 2‬‬
‫‪V2e‬‬
‫ﺒﺤﻴﺙ ﺃﻨﻪ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻴﻜﻭﻥ ‪. x = 1.0‬‬
‫ﻝﻨﺩﺭﺱ ﻓﻴﻤﺎ ﻴﻠﻲ ﻜﻴﻑ ﻴﺘﻐﻴﺭ ﺍﻝﺘﺎﺒﻊ ) ‪ p Ag = − log[Ag ] = f (x‬ﺃﺜﻨﺎﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫‪+‬‬
‫‪ .2.VII‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪p Ag = f (x‬‬
‫‪ .1.2.VII‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ‬
‫ﻥ ﺍﻝﻤﺤﻠﻭل ﻻ ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ‪ ،‬ﻭﻓﻲ ﻫـﺫﻩ‬

‫ﻥ ‪ V2 = 0‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ ‪ x = 0‬ﺃﻱ ﺃ ‪‬‬
‫ﺍﻝﺤﺎﻝﺔ ‪ p Ag‬ﻏﻴﺭ ﻤﻌﺭ‪‬ﻑ‪.‬‬
‫ﻥ ‪ 0 < V2 < V2eqv‬ﻭﺘﻜﻭﻥ ﻤﻌﺎﺩﻝﺔ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ‬

‫ ‪ 0 < x < 1‬ﺃﻱ ﺃ ‪‬‬
‫ﺍﻝﺭﺍﺠﺤﺔ‪:‬‬
‫‪Ag+‬‬ ‫‪+ Cl−‬‬ ‫‪

AgCl‬‬
‫‪t = 0 C 1 ⋅ V1‬‬ ‫‪C 2 ⋅ V2‬‬ ‫‪−‬‬
‫‪teq‬‬ ‫‪C 1 ⋅ V1 − C 2 ⋅ V2‬‬ ‫‪ε‬‬ ‫‪C 2 ⋅ V2‬‬
‫‪V2‬‬ ‫‪CV‬‬ ‫‪CV‬‬

‫= ‪x‬‬ ‫ﻥ ‪= 2 2 = 2 2‬‬ ‫ﻭﺒﻤﻼﺤﻅﺔ ﺃ ‪‬‬
‫‪V2e‬‬ ‫‪C 2V2e‬‬ ‫‪C 1V1‬‬
‫ﻨﺠﺩ ﺃﻨﹼﻪ ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ‪:‬‬
‫‪C 1V1 − C 2V2‬‬ ‫‪C 1V1‬‬

‫= ] ‪[Cl−‬‬ ‫=‬ ‫) ‪(1 − x‬‬
‫‪V1 + V2‬‬ ‫‪V1 + V2‬‬
‫‪Ks‬‬ ‫) ‪Ks ⋅ (V1 + V2‬‬

‫= ] ‪[Ag+‬‬ ‫= ‪−‬‬
‫] ‪[Cl‬‬ ‫) ‪C 1V1 ⋅ (1 − x‬‬
‫‪C 1V1‬‬
‫‪p Ag = pKs + log‬‬ ‫ﻭﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ) ‪(1 − x‬‬
‫‪V1 + V2‬‬
‫ﻥ ‪ V2 = V2eqv‬ﻭﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺘﻜﻭﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻭﺍﻝﻜﻠﻭﺭ ﻗﺩ‬

‫ ‪ x = 1.0‬ﺃﻱ ﺃ ‪‬‬
‫ﻤ‪‬ﺯﺠﺕ ﺒﻜﻤﻴﺎﺕ ﻤﺘﺴﺎﻭﻴﺔ‪:‬‬
‫= ‪[Ag+ ]eqv = [Cl− ]eqv‬‬ ‫‪Ks = 1.4 × 10−5 mol/L‬‬
‫ﻭﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ ‪p Ag = pKs /2 = 4.9‬‬

‫ﻥ ﻫﻨﺎﻝﻙ ﻓﺎﺌﻀﹰﺎ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ‪:‬‬

‫ﻥ ‪ V2 > V2eqv‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ ‪ x > 1‬ﺃﻱ ﺃ ‪‬‬
‫‪C 2V2 − C 2V2eqv‬‬ ‫‪C 1V1‬‬

‫= ] ‪[Ag+‬‬ ‫=‬ ‫)‪(x − 1‬‬
‫‪V1 + V2‬‬ ‫‪V1 + V2‬‬
‫‪C 1V1‬‬
‫‪. p Ag = − log‬‬ ‫ﻭﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ )‪(x − 1‬‬
‫‪V1 + V2‬‬
‫‪+‬‬
‫ﳏﻠﻮﻝ ‪Ag‬‬ ‫‪715‬‬
‫‪COM‬‬ ‫‪V‬‬
‫ﻣﺴﺮﻯ ﻓﻀﺔ‬
‫ﻣﺴﺮﻯ ﻣﺮﺟﻌﻲ‬
‫‪Hg 2 SO 4 /Hg‬‬
‫‪−‬‬
‫ﳏﻠﻮﻝ ‪Cl‬‬
‫‪ON‬‬
‫‪OFF‬‬
‫ﺍﻝﺸﻜل )‪ : (1‬ﺍﻹﻨﺸﺎﺀ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﻤﺴﺘﻌﻤل ﻝﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ‪ Cl−‬ﺒﺸﻭﺍﺭﺩ ‪. Ag+‬‬
‫‪ .2.2.VII‬ﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ﻭﻨﺘﺎﺌﺠﻪ‬
‫ﻴﻤﻜﻨﻨﺎ ﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ ، p Ag = f (x‬ﻭﻨﻼﺤﻅ ﺃﻨﻨﺎ ﺤﺼﻠﻨﺎ ﻋﻠﻰ ﻤﻨﺤﻥ ﻤﺸﺎﺒﻪ ﺒﺎﻝﺸﻜل‬
‫ﻝﻤﻨﺤﻨﻲ ﻤﻌﺎﻴﺭﺓ ﺃﺴﺎﺱ ﺒﺤﻤﺽ‪.‬‬
‫ﻴﻤﻜﻨﻨﺎ ﺃﻴﻀﹰﺎ ﺘﺘﺒﻊ ﺘﻐﻴﺭﺍﺕ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ‪ ،‬ﻭﺫﻝﻙ ﺒﻘﻴﺎﺱ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ‬
‫ﻯ ﻤﺭﺠﻌﻴﹰﺎ ﺃﻭ ﻤﺴﺭﻯ ﻤﻥ‬
‫ﻝﺒﻁﺎﺭﻴﺔ ﻨﺴﺘﻌﻤل ﻓﻴﻬﺎ ﻤﺴﺭﻯ ﻤﻥ ‪ Hg2SO4 /Hg‬ﺒﺼﻔﺘﻪ ﻤﺴﺭ ‪‬‬
‫ﺍﻝﻜﺎﻝﻭﻤﻴل ﺍﻝﻤﺸﺒﻊ ﺒﻌﺩ ﺃﻥ ﻨﻀﻴﻑ ﺇﻝﻴﻪ ﺇﺼﺒﻊ ﺤﻤﺎﻴﺔ‪ ،‬ﻭﻤﺴﺭﻯ ﻤﺅﺸﹼﺭ ﻤﻥ ﺍﻝﻔﻀﺔ‪ .‬ﻭﻴﻤﻜﻥ ﻋﻨﺩﻫﺎ‬
‫ﺍﻝﺘﻌﺒﻴﺭ ﻋﻥ ﺍﻝﻜﻤﻭﻥ ‪ E‬ﺒﺩﻻﻝﺔ ‪ . p Ag‬ﻭﺘﺤﺼل ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻗﻔﺯﺓ ﺒﺎﻝﻜﻤﻭﻥ‪.‬‬
‫ﻤﻥ ﺍﻝﻤﻤﻜﻥ ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺒﺄﻥ ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﻤﻨﺫ ﺍﻝﺒﺩﺍﻴﺔ ﺸﺎﺭﺩﺓ ﺘﻌﻁﻲ ﺭﺍﺴﺒﹰﺎ‬
‫ﻥ ﻫﺫﺍ ﺍﻝﺭﺍﺴﺏ ﻻ ﻴﻅﻬﺭ ﺇﻻ ﺒﻌﺩ ﺃﻥ ﻨﻨﺘﻬﻲ ﻤـﻥ‬
‫ﺒﻠﻭﻥ ﻤﻐﺎﻴﺭ ﻝﻠﻭﻥ ﺭﺍﺴﺏ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ ﺒﺤﻴﺙ ﺃ ‪‬‬
‫ﻤﻌﺎﻴﺭﺓ ﻜﺎﻤل ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻓﻲ ﺍﻝﻭﺴﻁ‪ .‬ﻨﺴﺘﻌﻤل ﻋﺎﺩ ﹰﺓ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﻭﻤﺎﺕ ‪ CrO24−‬ﺍﻝﺘﻲ ﺘﻌﻁﻲ‬
‫ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻔﻀﺔ ﺭﺍﺴﺒﹰﺎ ﺃﺤﻤﺭ‪-‬ﻗﺭﻤﻴﺩﻴﹰﺎ ﻤﻥ ‪ . Ag2CrO4‬ﻭﺘﹸﻌﺭ‪‬ﻑ ﻫﺫﻩ ﺍﻵﻝﻴﺔ ﻓﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﺴﻡ‬
‫ﻁﺭﻴﻘﺔ ﻤﻭﺭ‪.‬‬
‫ﻨﻀﻊ ﻓﻲ ﺒﻴﻜﺭ ﺤﺠﻤﹰﺎ ﻗﺩﺭﻩ ‪ V1 = 10.0 ml‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬
‫ﻤﺠﻬﻭل ‪ C 1‬ﻭﺤﺠﻤﹰﺎ ﻗﺩﺭﻩ ‪ v = 0.50 ml‬ﻤﻥ ﻤﺤﻠﻭل ﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬
‫ﻻ ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ‬
‫‪ .C = 0.050 mol/L‬ﻨﻀﻴﻑ ﺇﻝﻴﻪ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺴﺤﺎﺤﺔ ﻤﺤﻠﻭ ﹰ‬
‫ﺍﻝﺤﺠﻡ‬ ‫ﻋﻨﺩ‬ ‫ﺁﺠ ‪‬ﺭﻱ‬ ‫ﺃﺤﻤﺭ‬ ‫ﺭﺍﺴﺏ‬ ‫ﻴﻅﻬﺭ‬ ‫‪.C 2 = 1.0 × 10−2 mol/L‬‬ ‫ﺒﺘﺭﻜﻴﺯ‬
‫‪.V2eqv = 7.8 mL‬‬
‫‪ .1‬ﻤﺎ ﻫﻭ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻌﺎﻴ‪‬ﺭ؟‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ )‪ (I‬ﻓﻲ ﺍﻝﺒﻴﻜﺭ ﻋﻨﺩ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺤﻤﺭ ﺍﻵﺠ ‪‬ﺭﻱ‪.‬‬
‫‪ .3‬ﺍﺴﺘﻨﺘﺞ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﺍﻝﻤﺘﺒﻘﻴﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ‪ C ′‬ﻋﻨﺩ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺤﻤﺭ‬
‫ﺍﻵﺠ ‪‬ﺭﻱ‪ .‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪pKs′(Ag2CrO4 ) = 11.8 ، pKs (AgCl) = 9.7 :‬‬
‫ﺍﻝﺤل‬
‫‪ .1‬ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺘﻜﻭﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻭﺍﻝﻜﻠﻭﺭ ﻗﺩ ﻤ‪‬ﺯﺠﺕ ﺒﻜﻤﻴﺎﺕ ﻤﺘﺴﺎﻭﻴﺔ‪:‬‬
‫‪n 0 (Cl− ) = n(Ag+ )added‬‬
‫ﻥ‪:‬‬
‫ﺃﻱ ﺃ ‪‬‬
‫‪C 1 ⋅ V1 = C 2 ⋅ V2eqv‬‬
‫‪C ⋅V‬‬
‫ﻥ ‪.C 1 = 2 2eqv = 7.8 × 10−3 mol/L‬‬
‫‪V1‬‬
‫‪ .2‬ﻋﻨﺩ ﻅﻬﻭﺭ ﺭﺍﺴﺏ ﻤﻥ ﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ‪ Ag2CrO4‬ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫‪. [Ag+ ]2 ⋅ [CrO24− ] = Ks′‬‬
‫‪ Ks′ 1/2‬‬

‫‪[Ag+ ] = ‬‬
‫‪ [CrO24− ] ‬‬
‫ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺭﻭﻤﺎﺕ‪:‬‬

‫‪C ⋅v‬‬
‫= ] ‪[CrO24−‬‬ ‫‪= 1.4 × 10−3 mol/L‬‬
‫‪V1 + V2eqv + v‬‬
‫ﻭﻫﻜﺫﺍ ﻴﺼﺒﺢ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ‪. p Ag = 4.5 ، [Ag+ ] = 3.4 × 10−5 mol/L :‬‬
‫ﻥ ﺍﻝﻘﻴﻤﺔ ‪ p Ag = 4.5‬ﺘﻌﻨﻲ ﺃﻨﻪ ﻴﻤﻜﻨﻨﺎ ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺒﺩﻗﺔ‬
‫ﻨﻼﺤﻅ ﻤﻥ ﻤﻨﺤﻨﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺃ ‪‬‬
‫ﻭﻫﺫﺍ ﻤﺎ ﺴﻨﺘﺤﻘﹼﻕ ﻤﻨﻪ ﺃﻴﻀﹰﺎ ﺒﺎﻝﺤﺴﺎﺏ‪.‬‬
‫‪ .3‬ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﺍﻝﻤﺘﺒﻘﻴﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ‪ C ′‬ﻋﻨﺩ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺤﻤﺭ ﺍﻵﺠ ‪‬ﺭﻱ ﻫﻭ‪:‬‬
‫‪Ks‬‬
‫= ] ‪C ′ = [Cl−‬‬ ‫‪−6‬‬
‫‪+ = 5.9 × 10 mol/L‬‬
‫] ‪[Ag‬‬
‫ﻱ ﺘﻜﻭﻥ ﺍﻝﻨﺴﺒﺔ ﺍﻝﻤﺌﻭﻴﺔ ﻝﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻏﻴﺭ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫ﻋﻨﺩ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺤﻤﺭ ﺍﻵﺠﺭ ‪‬‬
‫‪: %Cl−‬‬
‫) ‪n(Cl−‬‬
‫⋅ ‪%Cl− = 100‬‬
‫) ‪n 0 (Cl−‬‬
‫‪(V1 + V2eqv + v ) ⋅ C ′‬‬
‫⋅ ‪= 100‬‬
‫‪V1 ⋅ C 1‬‬
‫ﻥ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺤﻤﺭ ﺍﻵﺠﺭﻱ ﻴﻌﻁﻲ ﻁﺭﻴﻘﺔ ﺩﻗﻴﻘﺔ‬

‫ﻥ‪ ، %Cl− < 0.2% :‬ﺃﻱ ﺇ ‪‬‬
‫ﻝﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻓﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫ﻤﻼﺤﻅﺔ‪ :‬ﻴﺠﺏ ﺍﺴﺘﻌﻤﺎل ﻁﺭﻴﻘﺔ ﻤﻭﺭ ﻝﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺘﻲ ﺘﻜﻭﻥ ﻓﻴﻬﺎ ﻗﻴﻤﺔ‬
‫‪ pH‬ﺍﻝﻤﺤﻠﻭل ﻗﺭﻴﺒﺔ ﻤﻥ ‪ . 7‬ﻓﻲ ﺍﻝﻭﺍﻗﻊ‪:‬‬
‫♦ ﻓﻲ ﻭﺴﻁ ﺤﻤﻀﻲ‪ ،‬ﺘﺘﻔﺎﻋل ﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﻭﻤﺎﺕ ﺍﻝﺘﻲ ﻫﻲ ﺃﺴﺎﺱ ﻤﻊ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ‬

‫ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪2 CrO24− + 2 H3O+

Cr2O27− + 3 H2O‬‬
‫ﻻ ﺒﻭﺠﻭﺩ ﻓﺎﺌﺽ ﻤﻥ‬

‫ﻥ ﺘﻜﻭ‪‬ﻥ ﺭﺍﺴﺏ ﻤﻥ ﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻻ ﻴﻜﻭﻥ ﺇ ﹼ‬
‫ﺇ‪‬‬
‫ﻥ ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻴﻜﻭﻥ ﻤﻊ ﺨﻁﺄ ﺘﻜﺭﺍﺭﻱ ﺒﺎﻝﺯﻴﺎﺩﺓ‪.‬‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ‪ .‬ﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫♦ ﻓﻲ ﻭﺴﻁ ﻗﻠﻭﻱ‪ ،‬ﺘﻌﻁﻲ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﺭﺍﺴﺒﹰﺎ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ‬
‫‪2 Ag+ + 2 OH−

Ag2O + H2O‬‬
‫ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃﻥ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻝﻡ ﻴﻌﺩ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻭﺤﻴﺩ ﺍﻝﺫﻱ ﻴﺴﺘﻬﻠﻙ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ )‪، (I‬‬
‫ﻭﺘﺼﺒﺢ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻤﺴﺘﺤﻴﻠﺔ‪.‬‬
‫‬
‫ﺘﻌﻁﻲ ﺸﻭﺍﺭﺩ ﺍﻝﺭﺼﺎﺹ ‪ Pb2+‬ﺭﺍﺴﺒﹰﺎ ﺃﺼﻔﺭ ﺒﻭﺠﻭﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻴﻭﺩ ‪ ، I−‬ﻓﻲ ﺤﻴﻥ‬ ‫‬
‫ﺘﻌﻁﻲ ﺸﻭﺍﺭﺩ ﺍﻝﺯﺌﺒﻕ ‪ Hg 2+‬ﺭﺍﺴﺒﹰﺎ ﺃﺤﻤﺭ ﺒﺭﺘﻘﺎﻝﻴﹰﺎ‪ .‬ﻋﻨﺩﻤﺎ ﻨﻀﻴﻑ ﺇﻝﻰ ﺃﻨﺒﻭﺏ ﺍﺨﺘﺒﺎﺭ‬
‫ﺤﺎ ﹴﻭ ﻋﻠﻰ ﺭﺍﺴﺏ ﻤﻥ ﻴﻭﺩ ﻴﺩ ﺍﻝﺭﺼﺎﺹ‪ ،‬ﻗﻁﺭﺓ ﻗﻁﺭﺓ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺯﺌﺒﻕ ‪ ، Hg 2+‬ﻓﺈ ‪‬‬
‫ﻥ‬
‫ﻝﻭﻥ ﺍﻝﺭﺍﺴﺏ ﻴﺼﺒﺢ ﺃﺤﻤﺭ ﺒﺭﺘﻘﺎﻝﻴﹰﺎ ﻤﻨﺫ ﺍﻝﻘﻁﺭﺍﺕ ﺍﻷﻭﻝﻰ‪.‬‬
‫‪ .1‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ ﻤﻥ ﻫﺫﻩ ﺍﻝﻤﻼﺤﻅﺔ؟‬
‫‪ .2‬ﻴﻤﺜﹼل ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻤﻌﻁﻰ ﻓﻲ ﺁﺨﺭ ﺍﻝﻤﺴﺄﻝﺔ ﻨﻤﺫﺠﺔ ﻹﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻴﻭﺩ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﻥ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺯﺌﺒﻕ ‪ Hg 2+‬ﺒﺘﺭﻜﻴﺯ ‪ 0.1 mol/L‬ﻭﺸﻭﺍﺭﺩ ﺍ ﻝﺭﺼﺎﺹ ‪ Pb2+‬ﺒﺘﺭﻜﻴﺯ‬
‫‪ ، 0.1 mol/L‬ﺤﻴﺙ ﺘﻤﺜﹼل ﺍﻝﻤﻨﺤﻨﻴﺎﺕ ﺍﻝﻨﺴﺏ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻠﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻨﻴﺔ ﺍﻝﻤﻭﺠﻭ ﺩﺓ‬
‫ﺒﺩﻻﻝﺔ ‪. pI = − log I−‬‬
‫ل ﻤﻥ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ؟‬
‫ﻱ ﻤﻥ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ﻴﻌﻭﺩ ﻜ ّ‬
‫)‪ (a‬ﺍﺴﺘﻨﺎﺩﹰﺍ ﺇﻝﻰ ﺍﻝﺴﺅﺍل ﺍﻷﻭل‪ ،‬ﺒﻴ‪‬ﻥ ﺇﻝﻰ ﺃ ‪‬‬
‫‪ B‬ﻋﻠﻰ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ ﺍﻷﻭل ﻭﺍﻝﺜﺎﻨﻲ ﺒﺎﻝﺘﺭﺘﻴﺏ؟ ﺍﺴﺘﻨﺘﺞ‬ ‫)‪ (b‬ﻤﺎﺫﺍ ﺘﻤﺜﹼل ﺍﻝﻨﻘﻁﺘﺎﻥ ‪، A‬‬
‫ل ﻤﻥ ‪ PbI2‬ﻭ ‪. HgI2‬‬
‫ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻝﻜ ﱟ‬
‫‪ Hg‬ﺇﻝﻰ ﺭﺍﺴﺏ‬ ‫‪2+‬‬
‫)‪ (c‬ﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺫﻱ ﻴﺘ ‪‬ﻡ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ﺍﻝﺯﺌﺒﻕ‬
‫ﻤﻥ ﻴﻭﺩﻴﺩ ﺍﻝﺭﺼﺎﺹ‪.‬‬
‫‪%‬‬
‫‪A‬‬ ‫‪B‬‬
‫‪90‬‬
‫‪80‬‬
‫‪70‬‬
‫‪60‬‬
‫‪50‬‬
‫‪40‬‬
‫‬ ‫‬
‫‪30‬‬
‫‪20‬‬
‫‪10‬‬
‫‪pI‬‬
‫‪0‬‬
‫‪2‬‬ ‫‪4‬‬ ‫‪6‬‬ ‫‪8‬‬ ‫‪10‬‬ ‫‪12‬‬ ‫‪14‬‬
‫ﺘﻬﺩﻑ ﻫﺫﻩ ﺍﻝﻤﺴﺄﻝﺔ ﺇﻝﻰ ﻤﻘﺎﺭﻨﺔ ﺍﻨﺤﻼﻝﻴﺔ ﻭﺠﺩﺍﺀ ﺍﻨﺤﻼل ﻜل ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ ﻭﻴﻭﺩﻴـﺩ‬ ‫‬
‫ﺍﻝﻔﻀﺔ ﻭﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ‪.‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﺍﻨﺤﻼﻝﻴﺔ ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﻔﻀﺔ ﻭﻴﻭﺩ ﻴﺩ ﺍﻝﻔﻀﺔ ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ‪ ،‬ﺜ ‪‬ﻡ ﺍﺴﺘﻨﺘﺞ ﺃ ﻴ‪‬ﻬﻤﺎ‬
‫ﺃﻜﺜﺭ ﺍﻨﺤﻼﻻﹰ؟‬
‫‪ .2‬ﻗﺎﺭﻥ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻭﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻝﻜﻼ ﺍﻝﻤﺭﻜﹼﺒﻴﻥ‪ ،‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .3‬ﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺫﻱ ﻴﺘ ‪‬ﻡ ﺒﺈﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻴﻭﺩ ﺇﻝﻰ ﺭﺍﺴﺏ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻔﻀﺔ‪.‬‬
‫‪ .4‬ﺤﺩ‪‬ﺩ ﺍﻨﺤﻼﻝﻴﺔ ﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ ﺜ ‪‬ﻡ ﻗﺎﺭﻥ ﺍﻨﺤﻼﻝﻴﺔ ﻭﺠﺩﺍﺀ ﺍﻨﺤﻼل‬
‫ﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ ﻤﻊ ﺍﻨﺤﻼﻝﻴﺔ ﻭﺠﺩﺍﺀ ﺍﻨﺤﻼل ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﻔﻀﺔ‪ .‬ﻫل ﺘﻭﺼ‪‬ﻠﺕ ﺇﻝﻰ‬
‫ﺍﻝﻨﺘﻴﺠﺔ ﻨﻔﺴﻬﺎ ﺍﻝﺘﻲ ﺘﻭﺼ‪‬ﻠﺕ ﺇﻝﻴﻬﺎ ﻓﻲ ﺍﻝﺴﺅﺍل ﺍﻝﺜﺎﻨﻲ؟‬
‫‪ .5‬ﺤﺩ‪‬ﺩ ﺜﺎﺒﺕ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺫﻱ ﻴﺘ ‪‬ﻡ ﺒﺈﻀﺎﻓﺔ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﺇﻝﻰ ﺭﺍﺴﺏ ﻤﻥ ﻜﺭﻭﻤﺎﺕ ﺍﻝﻔﻀﺔ‪.‬‬
‫‪pK s (Ag Cl) = 9.7‬‬
‫‪pK s (Ag I) = 16.2‬‬
‫‪pK s (Ag 2 Cr O4 ) = 11.8‬‬
‫ﻥ‬
‫ﻴﺤﻭﻱ ﻝﻴﺘﺭ ﻭﺍﺤﺩ ﻤﻥ ﻤﺤﻠﻭل ﻤ‪‬ﺸﺒ‪‬ﻊ ﺒﻜﺭﺒﻭﻨﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪ 16 mg‬ﻤﻨﻬﺎ‪ ،‬ﻓﺈﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬ ‫‬
‫ﻥ‬
‫ﻭﺃ ‪‬‬ ‫) ‪، p Ka1 ( CO2 aq/ H CO−3‬‬ ‫ﻥ ‪= 6.3‬‬
‫‪ ، K s ( Ca CO3 ) = 10‬ﻭﺃ ‪‬‬ ‫‪−8.3‬‬
‫‪. p Ka2 ( H CO−‬‬ ‫‪2−‬‬

‫‪3 /CO3 ) = 10.3‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﻋﺒﺎﺭﺓ ‪ s‬ﺒﺩﻻﻝﺔ ‪. [ H3O+ ] ، K a ، K a ، K s‬‬

‫‪2‬‬ ‫‪1‬‬
‫‪ .2‬ﺍﺤﺴﺏ ‪ s‬ﻤﻘﺩ‪‬ﺭﺓ ﺒﺎﻝﻭﺍﺤﺩﺓ ‪. mol/L‬‬

‫‪ .3‬ﺍﺤﺴﺏ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤ‪‬ﺸﺒ‪‬ﻊ‪.‬‬
‫‪m(Ca) = 40 g/mol‬‬
‫‪m(C) = 12 g/mol‬‬
‫‪m(O) = 16 g/mol‬‬
‫ﻝﻨﻔﺘﺭ ﺽ ﺃ ﻨﹼﻨﺎ ﺃﻀﻔﻨﺎ ‪ ،‬ﻤﻊ ﺍ ﻝﺘﺤﺭﻴﻙ ﺍ ﻝﻤﺴﺘﻤ ‪‬ﺭ ‪ n = 1.0 × 10−3 mol ،‬ﻤﻥ ﻜﻠﻭ ﺭ ﻴﺩ‬ ‫‬
‫ل ﻋﺩﺩ ﻤﻥ ﻤﻭﻻﺕ‬
‫ﺍﻝﻔﻀﺔ ﺇﻝﻰ ﺍﻝﺤﺠﻡ ‪ V = 0.500 L‬ﻤﻥ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ‪ .‬ﻤﺎ ﻫﻭ ﺃﻗ ّ‬
‫ﻼ ﻓﻲ ﺍﻝﻤﺎﺀ‪ ،‬ﺇﺫﺍ‬
‫ﺍﻝﻨﺸﺎﺩﺭ ﺍﻝﻼﺯﻡ ﺇﻀﺎﻓﺘﻪ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ﻝﻴﺼﺒﺢ ﺍﻝﺭﺍﺴﺏ ﺒﻜﺎﻤﻠﻪ ﻤﻨﺤ ﹰ‬
‫ﻥ ﺇﻀﺎﻓﺔ ﺍﻝﻨﺸﺎﺩﺭ ﻝﻥ ﺘﺴﺒ‪‬ﺏ ﺘﻐﻴﺭﹰﺍ ﻤﻠﺤﻭﻅﹰﺎ ﻓﻲ ﺍﻝﺤﺠﻡ؟‬
‫‪p K s (Ag Cl) = 9.7‬‬
‫‪+‬‬
‫] ‪log β2 ( [ Ag ( NH3 )2‬‬ ‫‪) = 7.2‬‬
‫ﺘﻬﺩﻑ ﻫﺫﻩ ﺍﻝﻤﺴﺄﻝﺔ ﺇﻝﻰ ﻤﻌﺎﻴﺭﺓ ﺍﻝﻨﻴﻜل ﺍﻝﺩﺍﺨل ﻓﻲ ﺘﺭﻜﻴﺏ ﺴﺒﻴﻜﺔ ﻤﻌﺩﻨﻴﺔ‪ :‬ﻨﻌﺎﻝﺞ ‪1.05 g‬‬ ‫‬
‫ﻤﻥ ﺍﻝﺴﺒﻴﻜﺔ ﺒﻤﻘﺩﺍﺭ ‪ 50 cm3‬ﻤﻥ ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﻭﻨﺤﺼل ﻋﻠﻰ ﻤﺤﻠﻭل ﺤﺎ ﹴﻭ ﻋﻠﻰ‬
‫ﺸﻭﺍﺭﺩ ‪ Ni2+‬ﺍﻝﻭﺍﺠﺏ ﻤﻌﺎﻴﺭﺘﻬﺎ‪ .‬ﻝﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ‪ Ni2+‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ‪:‬‬
‫ ﻨﻀﻴﻑ ﺇ ﻝﻴﻪ ‪ 10 cm3‬ﻤﻥ ﻤﺤﻠﻭ ل ﻨﺘﺭ ﺍ ﺕ ﺍ ﻝﻔﻀﺔ ﺒﺘﺭ ﻜﻴﺯ ‪1.0 mol/L‬‬
‫ﻭ ‪ 10 cm3‬ﻤﻥ ﻤﺤﻠﻭ ل ﻴﻭ ﺩ ﻴﺩ ﺍ ﻝﺒﻭ ﺘﺎﺴﻴﻭ ﻡ ﺒﺘﺭ ﻜﻴﺯ ‪ ، 0.1 mol/L‬ﺜ ‪‬ﻡ ﻨﺘﻤ‪‬ﻡ ﺤﺠﻡ‬
‫ﺍﻝﻤﺤﻠﻭل ﺇﻝﻰ ‪ 100 cm3‬ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ‪ ،‬ﻓﻨﺤﺼل ﻋﻠﻰ ﺭﺍﺴﺏ‪.‬‬
‫ﻻ ﻤﻥ ﺴﻴﺎﻨﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ‬
‫
ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺴﺤﺎﺤﺔ ﻤﺤﻠﻭ ﹰ‬
‫ﻥ ﺍ ﻝﻤﺤﻠﻭ ل ﻗﺩ ﺃﺼﺒﺢ ﺭ ﺍ ﺌﻘﹰﺎ ) ﺃ ﻱ ﻴﺯ ﻭل‬
‫‪ KCN‬ﺒﺘﺭ ﻜﻴﺯ ‪ 1 mol/L‬ﻓﻨﻼ ﺤﻅ ﺃ ‪‬‬
‫ﺍﻝﺭﺍﺴﺏ( ﻋﻨﺩ ﺇﻀﺎﻓﺔ ‪ 25 cm3‬ﻤﻥ ﺴﻴﺎﻨﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ‪.‬‬
‫ﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻔﻜﹼﻙ ﺍﻹﺠﻤﺎﻝﻲ‬
‫ﻥ ﺍﻝﻜﺘﻠﺔ ﺍﻝﻐﺭﺍﻤﻴﺔ ﻝﻠﻨﻴﻜل ﻫﻲ ‪ 58.7 g/mol‬ﻭﺃ ‪‬‬
‫ﻥ ﺜﺎ ﺒﺕ ﺍ ﻝﺘﻔﻜﹼﻙ ﺍ ﻹ ﺠﻤﺎ ﻝﻲ ﻝﻠﻤﻌﻘﹼﺩ‬
‫ﻝﻠﻤﻌﻘﹼﺩ ‪ Ni(CN)24−‬ﻫﻭ ‪ K D1 = 10−30‬ﻭ ﺃ ‪‬‬
‫‪ Ag(CN)−‬ﻫﻭ ‪ K D2 = 10−21‬ﻭﺠﺩﺍﺀ ﺍﻻﻨﺤﻼﻝﻴﺔ ﻝـ ‪ AgI‬ﻫﻭ ‪. K s = 10−16‬‬
‫‪2‬‬
‫‪ .1‬ﺃﻭﺠﺩ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻻﺒﺘﺩﺍﺌﻴﺔ ﻝﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻭﺍﻝﻴﻭﺩ ﻓﻲ ﺍﻝﻤﺭﺤﻠﺔ ﺍﻷﻭﻝﻰ‪.‬‬

‫‪ .2‬ﻋﻠﹼل ﺘﻜﻭ‪‬ﻥ ﺍﻝﺭﺍﺴﺏ ‪. AgI‬‬
‫‪ .3‬ﺍﻜﺘﺏ ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺍﻝﺤﺎﺼﻠﺔ ﻋﻨﺩ ﺇﻀﺎﻓﺔ ﺴﻴﺎﻨﻴﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﻓﻲ ﺍﻝﻤﺭﺤﻠﺔ
ﻭﺤﺩ‪‬ﺩ‬
‫ﺜﻭﺍﺒﺘﻬﺎ‪.‬‬
‫‪ .4‬ﺤﺩ‪‬ﺩ ﺍﺴﺘﻨﺎﺩﹰﺍ ﺇﻝﻰ ﻗﻴﻡ ﺜﻭﺍﺒﺕ ﺍﻝﺘﻔﻜﹼﻙ ﺍﻝﻤﻌﻁﺎﺓ ﺍﻝﻤﻌ ﹼﻘ ‪‬ﺩ ﺍﻝﺫﻱ ﻴﺘﺸﻜﹼل ﻓﻲ ﺍﻝﺒﺩﺍﻴﺔ‪.‬‬
‫‪ .5‬ﻋﻠﹼل ﻝﻤﺎﺫﺍ ﻨﻜﻭﻥ ﻗﺩ ﻋﺎﻴﺭﻨﺎ ﺸﻭﺍﺭﺩ ‪ Ni2+‬ﻭ ‪ Ag+‬ﻋﻨﺩ ﺍﺨﺘﻔﺎﺀ ﺍﻝﺭﺍﺴﺏ؟‬
‫‪ .6‬ﺍﺤﺴﺏ ﺍﻝﻨﺴﺒﺔ ﺍﻝﻤﺌﻭﻴﺔ ﻝﻜﺘﻠﺔ ﺍﻝﻨﻴﻜل ﻓﻲ ﺍﻝﺴﺒﻴﻜﺔ‪.‬‬

‫‪ .7‬ﺍﺸﺭﺡ ﺩﻭﺭ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻓﻲ ﻋﻤﻠﻴﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫ﺍﻨﺤﻼﻝﻴﺔ ﺨﻼﺕ ﺍﻝﻔﻀﺔ‪.‬‬ ‫‬

‫‪ .1‬ﺍﺤﺴﺏ ﺍﻝﺘﺭﺍﻜﻴﺯ ﻭﺍﻝـ ‪ pH‬ﻓﻲ ﻤﺤﻠﻭل ﻤ‪‬ﺸﺒ‪‬ﻊ ﻤﻥ ﺨﻼﺕ ﺍﻝﻔﻀﺔ ‪. AgCH3COO‬‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ‪ 100 cm3‬ﻤﻥ ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل ‪ n = 0.10 mol‬ﻤﻥ ﺨﻼﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ‬
‫ﺍﻝﺼﻠﺒﺔ‪ .‬ﺤﺩ‪‬ﺩ ﻜﺘﻠﺔ ﺨﻼﺕ ﺍﻝﻔﻀﺔ ﺍﻝﻤﺘﺭﺴ‪‬ﺒﺔ ﻋﻨﺩﺌﺫ‪.‬‬
‫‪pK s(AgCH3COO) = 2.60‬‬
‫) ‪. pK A (CH 3COOH/CH 3COO−‬‬ ‫‪= 4.75‬‬
‫ﻻ ﻤﻥ‬
‫ﻨﻀﻴﻑ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺤﺠﻤﻪ ﻝﻴﺘﺭ ﹰﺍ ﻭﺍﺤﺩ ﹰﺍ ﻤﺤﺘ ﹴﻭ ﻋﻠﻰ ‪ n = 1 × 10−2‬ﻤﻭ ﹰ‬ ‫‬
‫ﻻ‬
‫ﻻ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺴﺘﺭﻭﻨﺴﻴﻭﻡ‪ ،‬ﻤﻘﺩﺍﺭ ‪ 0.10‬ﻤﻭ ﹰ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺒﺎﺭﻴﻭﻡ ﻭ ‪ n ′ = 1 × 10−2‬ﻤﻭ ﹰ‬
‫ﻤﻥ ﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ‪ . K2CrO4‬ﻋﻴ‪‬ﻥ ﺤﺩ‪‬ﻴﻥ ﻴﺠﺏ ﺍﻝﻤﺤﺎﻓﻅﺔ ﻋﻠﻰ ‪ pH‬ﺍﻝﻤﺯﻴﺞ‬
‫ﺒﻴﻨﻬﻤﺎ ﺤﺘﻰ ﻴﺘﺭﺴﺏ ﻋﻠﻰ ﺍﻷﻗل ‪ 99%‬ﻤﻥ ﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﺎﺭﻴﻭﻡ ﻭﺫﻝﻙ ﺩﻭﻥ ﺃﻥ ﻴﺘﺭﺴ‪‬ﺏ‬
‫ﺃﻜﺜﺭ ﻤﻥ ‪ 1%‬ﻤﻥ ﻜﺭﻭﻤﺎﺕ ﺍﻝﺴﺘﺭﻭﻨﺴﻴﻭﻡ؟‬
‫‪pK s (Ba Cr O4 ) = 9.7‬‬
‫‪pK s (Sr Cr O4 ) = 4.4‬‬
‫‪pK A (HCrO−‬‬ ‫‪2−‬‬
‫‪4 /CrO4 ) = 6.4‬‬
‫ﻨﻀﻴﻑ ﺇﻝﻰ ‪ 25 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ ، 0.40 mol/L‬ﻤﻘﺩﺍﺭ‬ ‫‬
‫‪ 25 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺃﻭﻜﺴﺎﻻﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪. 0.40 mol/L‬‬
‫‪ .1‬ﻤﺎ ﻫﻲ ﻨﺴﺒﺔ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ﺍﻝﻤﺘﺭﺴﺏ؟‬
‫‪ .2‬ﻤﺎ ﻫﻭ ‪ pH‬ﺍﻝﻤﺯﻴﺞ؟‬
‫ﻱ ﺃﺤﺎﺩﻱ ﺍﻝﻭﻅﻴﻔﺔ ﺍﻝﺘﻲ ﻴﻨﺒﻐﻲ ﺇﺩﺨﺎﻝﻬﺎ ﺇﻝﻰ‬
‫ﺽ ﻗﻭ ‪‬‬
‫‪ .3‬ﻤﺎ ﻫﻭ ﻋﺩﺩ ﺍﻝﻤﻭﻻﺕ ﻤﻥ ﺤﻤ ﹴ‬
‫ﺍﻝﻤﺤﻠﻭل ﻤﻥ ﺩﻭﻥ ﺃﻥ ﻴﺠﺭﻱ ﺘﻤﺩﻴﺩﻩ ﻭﺘﺅﺩﻱ ﺇﻝﻰ ﺇﺫﺍﺒﺔ ﺍﻝﺭﺍﺴﺏ؟‬
‫‪pKs (Ca C2O4 ) = 8.7‬‬
‫‪pK A (HC2O−‬‬ ‫‪2−‬‬
‫‪4 /C2O4 ) = 4.3‬‬
‫‪pK A(H2C2O4 /HC2O−‬‬
‫‪4 ) = 1.25‬‬
‫ل ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﺜﻴﻭﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﺤﻴﺙ ﻴﺸﻜﹼل ﻤﻌﻘﺩﹰﺍ‬

‫ﻴﻤﻜﻥ ﻝﺒﺭﻭﻤﻴﺩ ﺍﻝﻔﻀﺔ ﺃﻥ ﻴﻨﺤ ّ‬ ‫ ‬
‫ﻻ ﺒﺘﺭﻜﻴﺯ ‪.C 0 mol/L‬‬
‫ﻫﻭ‪ . [ Ag(S2O3 )2 ]3− :‬ﻨﺸﺒﻊ ﺒﺒﺭﻭﻤﻴﺩ ﺍﻝﻔﻀﺔ ﻤﺤﻠﻭ ﹰ‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﻲ ﺘﺭﺒﻁ ﺍﻨﺤﻼﻝﻴﺔ ﺒﺭﻭﻤﻴﺩ ﺍﻝﻔﻀﺔ ‪ s‬ﺒﺘﺭﺍﻜﻴﺯ ﻤﺨﺘﻠﻑ ﺍﻝﺸﻭﺍﺭﺩ ﻓﻲ‬
‫‪ .2‬ﺍﺤﺴﺏ ‪ [ Ag+ ] ، [ S2O23− ] ، s‬ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪.C 0 =0.10 mol/L‬‬
‫‪pK s(Ag Br) = 12.3‬‬
‫‪log β([ Ag (S2O3 )2 ]3− ) = 13.3‬‬
‫ﺘﻜ ‪‬ﻭ ﻥ ﺸﻭ ﺍ ﺭ ﺩ ﺍ ﻷ ﻝﻤﻨﻴﻭ ﻡ )‪ (III‬ﻤﻊ ﺸﻭ ﺍ ﺭ ﺩ ﺍ ﻝﻬﻴﺩ ﺭ ﻭ ﻜﺴﻴﺩ ﺭ ﺍﺴﺒﹰﺎ ﺠﺩ ﺍ ﺀ ﺍ ﻨﺤﻼ ﻝﻪ‬ ‫

‬
‫‪ . pKs = 33‬ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ‪ ،‬ﺘﻜﻭ‪‬ﻥ ﺸﻭﺍﺭﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ )‪ (III‬ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻷﻭﻜﺴﺎﻻﺕ‬
‫‪ C2O24−‬ﻭﺍﻝﺘﻲ ﺴﻨﺭﻤﺯ ﻝﻬﺎ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﺴﺄﻝﺔ ‪ ox 2−‬ﺍﻝﻤﻌﻘﹼﺩ ‪ [Al(ox )3 ]3−‬ﺒﺜﺎﺒﺕ ﺘﺸﻜﹼل‬
‫ﻻ ﻤﺎ ﺌﻴﹰﺎ ﻴﻀ ‪‬ﻡ ﺸﻭ ﺍ ﺭ ﺩ ﺍ ﻷ ﻝﻤﻨﻴﻭ ﻡ )‪ (III‬ﺒﺘﺭ ﻜﻴﺯ‬
‫ﺇ ﺠﻤﺎ ﻝﻲ ‪ . log β = 13‬ﻝﻨﺄ ﺨﺫ ﻤﺤﻠﻭ ﹰ‬
‫‪: 0.10 mol/L‬‬
‫‪ .1‬ﺍﺤﺴﺏ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺫﻱ ﻴﺒﺩﺃ ﻋﻨﺩﻩ ﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺏ ﻭﺫﻝﻙ ﺒﻐﻴﺎﺏ‬
‫ﺸﻭﺍﺭﺩ ﺍﻷﻭﻜﺴﺎﻻﺕ‪.‬‬
‫‪ .2‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻤﺔ ﺍﻝـ ‪ pH‬ﺍﻝﺘﻲ ﻴﺒﺩﺃ ﻋﻨﻬﺎ ﺍﻝﺭﺍﺴﺏ ﺒﺎﻝﻅﻬﻭﺭ‪.‬‬
‫‪ .3‬ﺒﻴ‪‬ﻥ ﺃﻨﻪ ﻭﺒﻭﺠﻭﺩ ﺸﻭﺍﺭﺩ ﺍﻷﻭﻜﺴﺎﻻﺕ ﺒﺘﺭﻜﻴﺯ ‪ ، 1.0 mol/L‬ﻓﺈﻨﻪ ﻻ ﻴﻅﻬﺭ ﺭﺍﺴﺏ‬
‫ل ﻫﺫﺍ ﺍﻝﺴﺅﺍل ﻴ‪‬ﻁﻠﺏ ﻤﻨﻙ ﻤﺎ ﻴﻠﻲ‪:‬‬
‫ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ ﻋﻨﺩ ‪ ، pH = 6.3‬ﻭﻝﺤ ّ‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺸﺎﺭﺩﺓ ﺍﻷﻭﻜﺴﺎﻻﺕ ﻴﻜﻭﻥ ﺭﺍﺠﺤﹰﺎ ﻋﻠـﻰ‬
‫‪ .1.3‬ﺒﻴ‪‬ﻥ ﺃﻨﻪ ﻋﻨﺩ ‪ pH = 6.3‬ﻓﺈ ‪‬‬
‫‪ HC2O−‬ﻭ ‪. H2C2O4‬‬
‫ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ‪4‬‬
‫‪ .2.3‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩ ‪ [Al(ox )3 ]3−‬ﻭﺍﺴﺘﻨﺘﺞ ﺘﺭﻜﻴﺯ ﺸـﻭﺍﺭﺩ‬

‫ﺍﻷﻝﻤﻨﻴﻭﻡ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ .3.3‬ﺍﺤﺴﺏ ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ‪ Q‬ﻋﻨﺩ ‪ ، pH = 6.3‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .4‬ﺍﺤﺴﺏ ﺍﻝﻘﻴﻤﺔ ﺍﻝﺩﻨﻴﺎ ﻝﻠـ ‪ pH‬ﺍﻝﺘﻲ ﻴﺒﺩﺃ ﻋﻨﺩﻫﺎ ﺍﻝﺭﺍﺴﺏ ﺒﺎﻝﻅﻬﻭﺭ ﻭﺫﻝﻙ ﺒﻭﺠﻭﺩ‬
‫ﺸﻭﺍﺭﺩ ﺍﻷﻭﻜﺴﺎﻻﺕ ﺒﺘﺭﻜﻴﺯ ‪. 1.0 mol/L‬‬
‫ﻥ ﺸﺎﺭﺩﺓ ﺍﻷ ﻭ ﻜﺴﺎﻻﺕ ﺜﻨﺎﺌﻴﺔ‬

‫‪ .5‬ﻤﺎ ﺍﻝﺸﻜل ﺍﻝﻬﻨﺩﺴﻲ ﻝﻠﻤﻌﻘﹼﺩ ‪ [Al(ox )3 ]3−‬ﺇﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﺍﻝﺴﻥ؟‬
‫‪. pK A(HC2O−‬‬
‫‪4 / C2O4 ) = 4.3 ، pK A (H2C2O4 / HC2O4 ) = 1.25‬‬
‫‪2−‬‬ ‫‪−‬‬
‫ﻴﻀ ‪‬ﻡ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﺸﻭﺍﺭﺩ ‪ Cd2+‬ﻭ ‪ Cu2 +‬ﻭ ‪ Mn2+‬ﻭﺠﻤﻴﻌﻬﺎ ﻝﻬﺎ ﺍﻝﺘﺭﻜﻴﺯ ﻨﻔﺴﻪ‬ ‫‬
‫ﺦ ﺒﺎﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ ﺍﻝﺴﺎﺒﻕ ﻏﺎﺯ ﻜﺒﺭﻴﺕ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ‪H2S‬‬
‫ﻭﻫﻭ ‪ . 0.01mol/L‬ﻨﻀ ﹼ‬
‫ﺒﺤﻴﺙ ﻴﺒﻘﻰ ﺘﺭﻜﻴﺯ ‪ H2S‬ﺍﻝﻤﻨﺤل ﻫﻭ ‪ 0.10 mol/L‬ﻭﺍﻝﻤﻁﻠﻭﺏ‪:‬‬
‫‪ .1‬ﺃﻭﺠﺩ ] ‪ [S2−‬ﺒﺩﻻﻝﺔ ] ‪ [H3O+‬ﻭ ) ‪K A (H2S/HS−‬‬

‫‪1‬‬
‫ﻭ ) ‪ K A (HS− /S2−‬ﻭ ﺘﺭﻜﻴﺯ ‪ H2S‬ﺍﻻﺒﺘﺩﺍﺌﻲ‪.‬‬

‫‪2‬‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ﺍﻷﻤﻼﺡ ﺍﻝﺘﻲ ﺴﺘﺘﺭﺴ‪‬ﺏ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪. pH = 4‬‬

‫‪، pKs (Cd S) = 28.4 ، pK A (HS− /S2− ) = 13 ، pK A (H2S/HS− ) = 7‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪. pKs (Mn S) = 9.6 ، pKs (Cu S) = 44‬‬
‫ﺘﺄﺜﻴﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ‪:‬‬ ‫‬

‫ﻝﻨﺄﺨﺫ ‪ 1L‬ﻤﻥ ﻤﺤﻠﻭل ﻤﺸﺒﻊ ﻤﻥ ‪ AgCl‬ﺍﻨﺤﻼﻝﻴﺘﻪ ‪. s = 1.3 × 10−5 mol/L‬‬
‫ﻭﻝﻨﻀﻑ ﺇﻝﻴﻪ ﺩﻭﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍﻝﺤﺠﻡ ‪ 0.1 mol‬ﻤﻥ ‪. NaCl‬‬
‫ﺍﺤﺴﺏ ﺍﻻﻨﺤﻼﻝﻴﺔ ﺍﻝﺠﺩﻴﺩﺓ ‪ s ′‬ﻝﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ‪. Ag+‬‬
‫ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺘﻭﺘﻴﺎﺀ‪:‬‬ ‫‬

‫ﻨﻀﻴﻑ ﺇﻝﻰ ‪ 1.00 L‬ﻤﻥ ﺍﻝﻤﺎﺀ ‪ n = 1.0 × 10−2 mol‬ﻤﻥ ‪ . Zn(OH)2‬ﺍﺩﺭﺱ‬
‫ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺘﻭﺘﻴﺎﺀ ﺒﺩﻻﻝﺔ ﺍﻝـ ‪. pH‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪. log β( Zn(OH)4  ) = 15.4 ، pKs (Zn(OH)2 ) = 16.4 :‬‬
‫‪2−‬‬
‫ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻨﺤﺎﺱ‪:‬‬ ‫‬
‫‪ .1‬ﺘﺴﺎﻭﻱ ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻨﺤﺎﺱ )‪ (II‬ﻓﻲ ﺍﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﹼﺭ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ‬
‫‪. 9.75 × 10−6 g/L : 25 C‬‬
‫‪ .a‬ﺤﺩ‪‬ﺩ ‪ pH‬ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺸﺒﻊ ﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻨﺤﺎﺱ‪.‬‬
‫‪ .b‬ﺍﺤﺴﺏ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻨﺤﺎﺱ )‪.(II‬‬
‫‪ .2‬ﻝﺩﻴﻨﺎ ‪ 5.0 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻨﺤﺎﺱ)‪ (II‬ﺘﺭﻜﻴﺯﻩ ‪ C 0‬ﻴﺴﺎﻭﻱ‬

‫‪ 0.010 mol/L‬ﻭﻴﺘﻤﺘﻊ ﺒـ ‪ pH‬ﻴﺴﺎﻭﻱ ‪ . 1.0‬ﻨﻀﻴﻑ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺴﺎﺒﻕ‬
‫ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ ﺒﺘﺭﻜﻴﺯ ‪.C B = 2.0 mol/L‬‬
‫‪ .a‬ﺤﺩ‪‬ﺩ ‪ pH‬ﺒﺩﺍﻴﺔ ﺍﻝﺘﺭﺴﻴﺏ‪.‬‬
‫‪ .b‬ﺍﺤﺴﺏ ﺍﻝﺤﺠﻡ ‪ v B‬ﻤﻥ ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ ﺍﻝﻼﺯﻡ ﺇﻀﺎﻓﺘﻪ ﻝﺒﺩﺀ ﺍﻝﺘﺭﺴﻴﺏ‪.‬‬
‫‪ .c‬ﺍﺤﺴﺏ ﺤﺠﻡ ﺍﻝﺼﻭﺩ ﺍﻝﻼﺯﻡ ﺍﺴﺘﻌﻤﺎﻝﻪ ﺤﺘﻰ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺤﺎﺱ )‪ (II‬ﺃﻗل‬
‫ﻤﻥ ‪ . 1.0× 10−6 mol/L‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﻝﻤﻭﺍﻓﻘﺔ‪.‬‬
‫ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ‪:‬‬ ‫‬
‫‪ . 1‬ﻝﺘﻜﻥ ‪ s‬ﺍﻨﺤﻼﻝﻴﺔ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ‪ .‬ﺃﻭﺠﺩ ﺍﻝﻌﻼﻗﺔ )‪ log(s ) = f (pH‬ﻭﺫﻝﻙ‬

‫ﻓﻲ ﺤﺎﻝﺔ ﻤﺤﻠﻭل ﻤﺸﺒﻊ ﻤﻥ ‪ . Mg(OH)2‬ﺍﺤﺴﺏ ‪ s‬ﻋﻨﺩ ‪ pH = 8.0‬ﻭ ‪. 11.0‬‬
‫‪ .2‬ﻨﻐﻴ‪‬ﺭ ‪ pH‬ﻤﺤﻠﻭل ﻤﻥ ﻜﻠﻭﺭ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ C = 0.20 mol/L‬ﻭﺫﻝﻙ‬

‫ﺒﺈﻀﺎﻓﺔ ﻤﺤﻠﻭل ﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ‪ .‬ﺍﺤﺴﺏ ﻗﻴﻤﺔ ‪ pH‬ﺒﺩﺍﻴﺔ ﺍﻝﺘﺭﺴﻴﺏ‪.‬‬
‫ﺦ ﻏﺎﺯ ﺍﻝﻨﺸﺎﺩﺭ ﻓﻲ ‪ 1.00 L‬ﻤﻥ ﻤﺤﻠﻭل ﻤﺎﺌﻲ ﻝﻜل ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ‬

‫‪ .3‬ﻨﻀ ﹼ‬
‫ﺒﺘﺭﻜﻴﺯ ‪ C = 0.20 mol/L‬ﻭﻜﻠﻭﺭﻴﺩ ﺍﻷﻤﻭﻨﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪C ′ = 1.0 mol/L‬‬
‫ﺩﻭﻥ ﺘﻐﻴﻴﺭ ﻓﻲ ﺍﻝﺤﺠﻡ‪ .‬ﺤﺩ‪‬ﺩ ﻜﻤﻴﺔ ﺍﻝﻨﺸﺎﺩﺭ ﺍﻝﺘﻲ ﻴﻨﺒﻐﻲ ﺇﻀﺎﻓﺘﻬﺎ ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل ﺤﺘﻰ‬
‫ﻴﺒﺩﺃ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﺒﺎﻝﺘﺭﺴ‪‬ﺏ‪.‬‬
‫‪. pK A (NH+‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ‪4 / NH 3 ) = 9.2 ، pK s (Mg(OH)2 ) = 11 :‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺴﺎﺩﺱ‬
‫
‬
‫ ‬
‫ﺘﻌﺎﺭﻴﻑ‬ ‫‪.I‬‬
‫‪ .II‬ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪ .III‬ﺘﻔﺎﻋﻼﺕ ﺍﻨﺘﻘﺎل ﺍﻝﺠﺴﻴﻤﺎﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺒﻴﻥ ﻤﺎﻨﺤﺎﺕ ﻭﻤﺘﻘ‪‬ﺒﻼﺕ‬
‫‪ .IV‬ﻤﻔﻬﻭﻡ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ‬
‫‪ .V‬ﺨﻭﺍﺹ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ‬
‫‪ .VI‬ﺘﻁﺒﻴﻘﺎﺕ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ‬
‫‪ .1.VI‬ﺩﺭﺍﺴﺔ ﻁﺒﻴﻌﺔ ﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ‬
‫‪ .2.VI‬ﻤﻭﺍﺯﻨﺔ ﻤﻌﺎﺩﻝﺔ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ‬
‫‪ .VII‬ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ‬
‫‪ .1.VII‬ﺘﻌﺎﺭﻴﻑ ﻭﺍﺼﻁﻼﺤﺎﺕ‬
‫‪ .2.VII‬ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ‬
‫‪ .3.VII‬ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ﺃﻭ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪205‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺴﺎﺩﺱ‬ ‫‪206‬‬
‫ﻤﻘﺩﻤﺔ‬
‫ﻤﺎ ﺍﻝﺭﺍﺒﻁ ﺒﻴﻥ ﺤﺭﺍﺌﻕ ﺍﻝﻐﺎﺒﺎﺕ‪ ،‬ﻭﺼﺩﺃ ﺍﻝﺤﺩﻴﺩ‪ ،‬ﻭﺍﺤﺘﺭﺍﻕ ﺍﻝﻭﻗﻭﺩ ﻓﻲ ﻤﺤﺭﻙ ﺍﻝﺴﻴﺎﺭﺓ‪،‬‬
‫ل ﻫﺫﻩ ﺍﻵﻝﻴﺎﺕ ﺍﻝﻤﺨﺘﻠﻔﺔ ﻤﺎ ﻫﻲ ﺇﻻ ﺘﻔﺎﻋﻼﺕ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ‪.‬‬
‫ﻥﻜّ‬
‫ﻭﺍﺴﺘﻘﻼﺏ ﺍﻝﻐﺫﺍﺀ ﻓﻲ ﺍﻝﺠﺴﻡ؟! ﺇ ‪‬‬
‫ﻥ ﺠﻤﻴﻊ ﺍﻵﻝﻴﺎﺕ ﺍﻝﺘﻲ ﺘﺴﻤﺢ ﺒﺘﻭﻝﻴﺩ ﺍﻝﻁﺎﻗﺔ ﻝﺘﺩﻓﺌﺔ ﺍﻝﺒﻴﻭﺕ ﻭﺇﻁﻼﻕ ﻤﺭﻜﺒﺔ ﻓﻀﺎﺌﻴﺔ ﻭﻤ ‪‬ﺩ‬
‫ﻭﺍﻝﻭﺍﻗﻊ ﺃ ‪‬‬
‫ﺍﻝﺠﺴﻡ ﺒﺎﻝﺤﻴﻭﻴﺔ ﻭﺍﻝﻨﺸﺎﻁ ﻤﺎ ﻫﻲ ﺇﻻ ﺘﻔﺎﻋﻼﺕ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ‪.‬‬
‫ل ﻤﺭﺓ ﺘﺸ ﹼﻐل ﻓﻴﻬﺎ ﺁﻝﺘﻙ ﺍﻝﺤﺎﺴﺒﺔ ﺃﻭ ﺘﺴﺘﻌﻤل ﺠﻬﺎﺯ ﻫﺎﺘﻔﻙ ﺍﻝﻤﺤﻤﻭل ﺃﻭ ﺘﻨﻅﺭ ﺇﻝﻰ‬
‫ﻭﻓﻲ ﻜ ّ‬
‫ﺴﺎﻋﺘﻙ ﺍﻝﺭﻗﻤﻴﺔ ﻝﺘﻘﺭﺃ ﺍﻝﻭﻗﺕ ﻓﺈﻨﻙ ﺘﻌﺘﻤﺩ ﻋﻠﻰ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻓﻲ ﻋﻤل ﺍﻝﺒﻁﺎﺭﻴﺎﺕ‬
‫ﺍﻝﺘﻲ ﺘﺴﻴ‪‬ﺭ ﻜل ﺍﻝﺘﺠﻬﻴﺯﺍﺕ ﺍﻝﺴﺎﺒﻘﺔ‪.‬‬
‫ﻥ ﺍﻝﺘﺤﻀﻴﺭ ﺍﻝﺼﻨﺎﻋﻲ ﻝﻠﻌﺩﻴﺩ ﻤﻥ ﺍﻝﻤﻭﺍﺩ ﻭﺍﻝﻤﺭﻜﺒﺎﺕ ﻤﺜل ﺍﻝﻜﻠﻭﺭ‬
‫ﻭﺃﺨﻴﺭﹰﺍ ﻭﻝﻴﺱ ﺁﺨﺭﹰﺍ ﻓﺈ ‪‬‬
‫ﻭﺍﻝﺼﻭﺩ ﺍﻝﻜﺎﻭﻱ ﻭﺍﻝﺘﻭﺘﻴﺎﺀ ﻭﺍﻷﻝﻤﻨﻴﻭﻡ‪ ،...‬ﻭﻜﺫﻝﻙ ﺩﺭﺍﺴﺔ ﻅﺎﻫﺭﺓ ﺍﻝﺘﺂﻜل ﻓﻲ ﺍﻝﻤﻌﺎﺩﻥ ﻭﺘﻔﻜﹼﻙ‬
‫ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺠ‪‬ﺭﺓ ﻴﻌﺘﻤﺩ ﻋﻠﻰ ﺩﺭﺍﺴﺔ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‪.‬‬
‫ﻝﻬﺫﺍ ﻭﻨﻅﺭﹰﺍ ﻷﻫﻤﻴﺔ ﻫﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻭﺘﻁﺒﻴﻘﺎﺘﻬﺎ ﺍﻝﻭﺍﺴﻌﺔ‪ ،‬ﻓﻘﺩ ﺃﻓﺭﺩﻨﺎ ﺍﻝﻔﺼﻭل ﺍﻷﺭﺒﻌﺔ‬
‫ﺍﻝﺘﺎﻝﻴﺔ ﻝﺩﺭﺍﺴﺔ ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﻤﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ‪.‬‬
‫‪ .I‬ﺘﻌﺎﺭﻴﻑ‬
‫ل ﻨﻭﻉ ﻜﻴﻤﻴﺎﺌﻲ ﺠﺯﻴﺌﻲ ﺃﻭ ﺸﺎﺭﺩﻱ ﻗﺎﺩﺭ ﻋﻠﻰ ﺘﻘﺩﻴﻡ ﺇﻝﻜﺘﺭﻭﻥ ﺃﻭ ﺃﻜﺜﺭ‪.‬‬

‫ ﻨﺴﻤ‪‬ﻲ ‪‬ﻤﺭﺠﻌﹰﺎ ﻜ ّ‬
‫ل ﻨﻭﻉ ﻜﻴﻤﻴﺎﺌﻲ ﺠﺯﻴﺌﻲ ﺃﻭ ﺸﺎﺭﺩﻱ ﻗﺎﺩﺭ ﻋﻠﻰ ﺍﻜﺘﺴﺎﺏ ﺇﻝﻜﺘﺭﻭﻥ ﺃﻭ‬
‫ﺴﺩ ًﹰﺍ ﻜ ّ‬
‫ ﻨﺴﻤ‪‬ﻲ ‪‬ﻤﺅﻜ ‪‬‬
‫ﺃﻜﺜﺭ‪.‬‬
‫ﻥ ﻫﺫﻴﻥ ﺍﻝﺘﻌﺭﻴﻔﻴﻥ ﻤﺘﻜﺎﻤﻼﻥ‪ .‬ﺇﺫ ﻴﻭﺍﻓﻕ ﻜل ﻤﺅﻜﺴﺩ ‪ Ox‬ﻤﺭﺠﻌﹰﺎ ‪ Red‬ﻭﺫﻝﻙ ﻭﻓﻕ‬
‫ﺍﻝﻤﺨﻁﻁ ﺍﻝﺸﻜﻠﻲ‪:‬‬
‫↽ ‪Ox + n e−‬‬
‫⇀‬
‫‪ Red‬‬
‫ﹸﺘﺘﺭﺠﻡ ﻫﺫﻩ ﺍﻝﻜﺘﺎﺒﺔ ﺇﻤﻜﺎﻨﻴﺔ ﺍﻝﻤﺭﻭﺭ ﻤﻥ ‪ Ox‬ﺇﻝﻰ ‪ Red‬ﻭﺒﺎﻝﻌﻜﺱ ﻭﺫﻝﻙ ﻋﺒﺭ ﺍﻨﺘﻘﺎل‬
‫ﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻻ ﺘﻭﺠﺩ ﻋﺎﺩﺓ ﺒﺤﺎﻝﺔ ﺤﺭﺓ‪.‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻜﺘﺎﺒﺔ ﺸﻜﻠﻴﺔ ﻷ ‪‬‬
‫ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ‪ .‬ﺇ ‪‬‬
‫ﻥ ﺍﻝﻤﺅﻜﺴﺩ ﻭﺍﻝﻤﺭﺠﻊ ﺍﻝﻤﺭﺘﺒﻁﻴﻥ ﺒﺎﻝﻤﺨﻁﻁ ﺍﻝﺸﻜﻠﻲ ﺍﻝﺴﺎﺒﻕ ﻤﺘﺭﺍﻓﻘﺎﻥ ‪ ،‬ﻭﺇﻨﻬﻤﺎ‬
‫ﻨﻘﻭل ﺇ ‪‬‬
‫ﻴﺸﻜﹼﻼﻥ ﺯﻭﺠﹰﺎ ﻤﺅﻜﺴﺩﹰﺍ‪-‬ﻤﺭﺠﻌﹰﺎ ﻨﻜﺘﺒﻪ ‪. Ox/Red‬‬
‫‪207‬‬ ‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻷﻛﺴﺪﺓ ﻭ ﺍﻹﺭﺟﺎﻉ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫ﻻ ﺒﺩﺭﺠﺔ‬
‫ل ﺯﻭﺝ ‪ Ox/Red‬ﻴﺘﻤﻴ‪‬ﺯ ﺒﺜﺎﺒﺕ ﻻ ﻴﺘﻌﻠﹼﻕ ﺇ ﹼ‬
‫ﻥ ﻜّ‬
‫ﻭﻜﻤﺎ ﺴﻨﺭﻯ ﻓﻴﻤﺎ ﺒﻌﺩ‪ ،‬ﻓﺈ ‪‬‬
‫ﺍﻝﺤﺭﺍﺭﺓ ﻨﺴﻤﻴ‪‬ﻪ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻲ ﻭﻨﺭﻤﺯ ﺇ ﻝﻴﻪ ﺒﺎﻝﺭﻤﺯ ‪ ، E‬ﻭ ﻴﻘﺎﺱ ﻋﺎﺩﺓ‬
‫ﺒﺎﻝﻔﻭﻝﺕ ‪. V‬‬
‫ ﺃﻤﺜﻠﺔ‪:‬‬
‫ﻴﺴﺎﻫﻡ ﻋﻨﺼﺭ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﺍﻝﺯﻭﺠﻴﻥ ‪ Ox/Red‬ﺍﻝﺘﺎﻝﻴﻴﻥ‪:‬‬
‫↽ ‪Fe3+ + e−‬‬‫‪ Fe2+‬‬
‫⇀‬ ‫ ﺍﻝﺯﻭﺝ ‪: Fe3+ / Fe2+‬‬
‫↽ ‪Fe2+ + 2e−‬‬
‫⇀‬
‫‪ Fe‬‬ ‫ ﺍﻝﺯﻭﺝ ‪: Fe2+ / Fe‬‬
‫ﻭﻴﺴﺎﻫﻡ ﻋﻨﺼﺭ ﺍﻝﻜﺒﺭﻴﺕ ﻓﻲ ﺍﻷﺯﻭﺍﺝ ‪ Ox/Red‬ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫↽ ‪S + 2 e−‬‬‫‪ S2−‬‬

‫⇀‬ ‫ ﺍﻝﺯﻭﺝ ‪: S / S2−‬‬
‫ﺸﺎﺭﺩﺓ ﺍﻝﺴﻠﻔﻴﺩ‬
‫↽ ‪S4O26− + 2e−‬‬‫‪ 2S2O23−‬‬

‫⇀‬ ‫ﺍﻝﺯﻭﺝ ‪: S4O26−/S2O23−‬‬ ‫‬
‫ﺸﺎﺭﺩﺓ ﺭﺒﺎﻋﻲ ﺍﻝﺘﻴﻭﻨﺎﺕ‬ ‫ﺸﺎﺭﺩﺓ ﺍﻝﺘﻴﻭﻜﺒﺭﻴﺘﺎﺕ‬
‫↽ ‪S2O28− + 2 e−‬‬‫‪ 2 SO24−‬‬

‫⇀‬ ‫ﺍﻝﺯﻭﺝ ‪: S2O28−/SO24−‬‬ ‫‬
‫ﺸﺎﺭﺩﺓ ﺒﻴﺭﻭﻜﺴﻲ ﺜﻨﺎﺌﻲ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‬ ‫ﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‬
‫‪ .II‬ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫ﻥ‬
‫ﻼ ﻤﻥ ﻤﺴﺤﻭﻕ ﺍﻝﺘﻭﺘﻴﺎﺀ‪ ،‬ﻓﻨﻼﺤﻅ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺃ ‪‬‬
‫ﻝﻨﻀﻑ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻨﺤﺎﺱ ﻗﻠﻴ ﹰ‬
‫ﻻ ﻻ ﻝﻭﻥ ﻝﻪ ﻜﻤﺎ ﻨﻼﺤﻅ ﺘﺭﺴ‪‬ﺏ‬
‫ﻝﻭﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻷﺯﺭﻕ ﻗﺩ ﺃﺨﺫ ﺒﺎﻻﺨﺘﻔﺎﺀ ﺘﺩﺭﻴﺠﻴﹰﺎ ﻝﻴﺼﺒﺢ ﻤﺤﻠﻭ ﹰ‬
‫ﺍﻝﻨﺤﺎﺱ ﺍﻷﺤﻤﺭ ﻓﻭﻕ ﻤﺴﺤﻭﻕ ﺍﻝﺘﻭﺘﻴﺎﺀ‪.‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻬﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﻫﻲ ‪:‬‬

‫ﺇ‪‬‬
‫‪Cu2+ + Zn ⇌ Cu + Zn2+‬‬
‫)‪E (V‬‬
‫‪Cu2+‬‬
‫‪Cu‬‬
‫‪Zn 2+‬‬
‫‪Zn‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 1‬ﻴﺘﻔﺎﻋل ﻤﺘﻘ ‪‬ﺒل ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻷﻗﻭﻯ ‪ Cu2+‬ﻤﻊ ﻤﺎﻨﺢ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻷﻗﻭﻯ ‪. Zn‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﺒﻴﻥ ‪ Cu2+‬ﻭ ‪ Zn‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺘﻠﻘﺎﺌﻲ ﺍﻝﻁﺒﻴﻌﻲ‪ ،‬ﻭﻨﺤﺼل ﻋﻠﻴﻪ‬
‫ﺇ‪‬‬
‫ﺒﺘﻁﺒﻴﻕ ﻗﺎﻋﺩﺓ ‪. γ‬‬
‫ﺘﻌﺒ‪‬ﺭ ﻫﺫﻩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻋﻥ ﺍﻨﺘﻘﺎل ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻤﻥ ﺍﻝﻤﺭﺠﻊ ‪ Zn‬ﻤﻥ ﺍﻝﺯﻭﺝ ‪Zn2 + / Zn‬‬
‫ﺫ ﻱ ﺍ ﻝﻜﻤﻭ ﻥ ﺍ ﻷ ﺨﻔﺽ ﻜﻤﺎ ﺴﻨﺭ ﻯ ﺫ ﻝﻙ ﻓﻴﻤﺎ ﺒﻌﺩ ‪ ،‬ﺇ ﻝﻰ ﺍ ﻝﻤﺅ ﻜﺴﺩ ‪ Cu2+‬ﻤﻥ ﺍ ﻝﺯ ﻭﺝ‬
‫ﻥ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻫﻭ ﻤﺜﺎل ﻋﻠﻰ ﺘﻔﺎﻋﻼﺕ‬
‫‪ Cu 2+ / Cu‬ﺫﻱ ﺍﻝﻜﻤﻭﻥ ﺍﻷﻋﻠﻰ ‪ ،‬ﺍﻝﺸﻜل ) ‪ . ( 1‬ﺇ ‪‬‬
‫ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‪.‬‬
‫ﻭ ﺒﺼﻭ ﺭ ﺓ ﻋﺎ ﻤﺔ ﻴﻨﺸﺄ ﺒﻴﻥ ﺍ ﻝﺯ ﻭ ﺠﻴﻥ ‪ Ox1/Red1‬ﻭ ‪ Ox2/Red2‬ﺘﻭ ﺍ ﺯ ﻥ ﺃ ﻜﺴﺩﺓ‬

‫ﻭﺇﺭﺠﺎﻉ ﺤﻴﺙ‪:‬‬
‫↽ ‪Ox1 +n1 e−‬‬

‫⇀‬
‫‪ Red1‬‬
‫↽ ‪Ox2 +n2 e−‬‬
‫⇀‬
‫‪ Red2‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻬﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‪:‬‬
‫⇀‬
‫↽ ‪n2 Ox1 +n1 Red2‬‬‫‪ n2 Red1 + n1 Ox 2‬‬
‫ﻴﻌﺒ‪‬ﺭ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ ﻋﻥ ﺍﻨﺘﻘﺎل ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺒﻴﻥ ﻫﺫﻴﻥ ﺍﻝﺯﻭﺠﻴﻥ ‪ ،‬ﻭ ﻴﺘﻤﻴ‪‬ﺯ ﺒﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ‬
‫ﻴ‪‬ﻜﺘﺏ ) ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺠﻤﻴﻊ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﻤﻨﻬﺎ ﻭﺍﻝﻨﺎﺘﺠﺔ ﻋﻥ ﺍﻝﺘﻔﺎﻋل ﻤﻨﺤﻠﺔ ﻓﻲ ﻤﺤﻠﻭل(‬
‫ﺒﺎﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫‬ ‫‪[ Red1 ]n2 ⋅ [ Ox 2 ]n1‬‬

‫‪K‬‬ ‫=‬
‫‪[ Ox1 ]n2 ⋅ [ Red2 ]n1‬‬
‫ﻴﻜﻭﻥ ﻫﺫﺍ ﺍﻝﺜﺎﺒﺕ ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻭﺍﺤﺩ ﻋﻨﺩﻤﺎ ﻴﺘﻔﺎﻋل ﻤﺘﻘ‪‬ﺒل ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻷﻗﻭﻯ ) ﺃﻱ‬
‫ﺍﻝﻤﺅﻜﺴﺩ ﺍﻷﻗﻭﻯ ( ﻤﻊ ﻤﺎﻨﺢ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻷﻗﻭﻯ ) ﺃﻱ ﺍﻝﻤﺭﺠﻊ ﺍﻷﻗﻭﻯ ( ‪ ،‬ﺍﻝﺸﻜل )‪ .(2‬ﻭﺴﻨﺭﻯ‬
‫ﻓﻴﻤﺎ ﺒﻌﺩ ﻜﻴﻑ ﻴﻤﻜﻨﻨﺎ ﺍﻝﺘﻨﺒ‪‬ﺅ ﺒﺫﻝﻙ ﺍﻋﺘﻤﺎﺩ ﹰﺍ ﻋﻠﻰ ﻗﻴﻡ ‪ . E‬ﻭﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺃﻜﺒﺭ ﻤﻥ‬
‫ﻲ‪ .‬ﻭﺴﻨﺩﺭﺱ ﻓﻴﻤﺎ ﺒﻌﺩ ﻜﻴﻑ ﻴﻤﻜﻨﻨﺎ ﺘﺤﺩﻴﺩ ﻫﺫﺍ ﺍﻝﺜﺎﺒﺕ ﻭﺇﻴﺠﺎﺩ‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﻁﺒﻴﻌ ‪‬‬
‫ﺍﻝﻭﺍﺤﺩ ﻨﻘﻭل ﺒﺄ ‪‬‬
‫ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﺍﻝﻭﺠﻭﺩ ﻝﻬﺫﻩ ﺍﻷﺯﻭﺍﺝ‪.‬‬
‫)‪E (V‬‬
‫‪Ox1‬‬
‫‪Red1‬‬
‫‪Ox 2‬‬
‫‪Red2‬‬
‫‪ Ox1‬ﻤﻊ ﻤﺎﻨﺢ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻷﻗﻭﻯ ‪. Red2‬‬ ‫ﺍﻝﺸﻜل ) ‪ : ( 2‬ﻴﺘﻔﺎﻋل ﻤﺘﻘ ‪‬ﺒل ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻷﻗﻭﻯ‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﺒﻴﻥ ‪ Ox1‬ﻭ ‪ Red2‬ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺘﻠﻘﺎﺌﻲ ﺍﻝﻁﺒﻴﻌﻲ‪ ،‬ﻭﻨﺤﺼل‬

‫ﺇ‪‬‬
‫ﻋﻠﻴﻪ ﺒﺘﻁﺒﻴﻕ ﻗﺎﻋﺩﺓ ‪. γ‬‬
‫

‬
‫ﻜﻴﻑ ﺘﺴﺎﻫﻡ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻓﻲ ﺇﻁﻼﻕ ﺍﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﻔﻀﺎﺌﻴﺔ؟‬
‫ﻥ ﺇﻁﻼﻕ ﻤﺭﻜﺒﺔ ﻓﻀﺎﺌﻴﺔ ﺘﺯﻥ ﻤﻼﻴﻴﻥ ﺍﻝﻜﻴﻠﻭﻏﺭﺍﻤﺎﺕ ﻴﺘﻁﻠﺏ ﻜﻤﻴﺔ ﻜﺒﻴﺭﺓ ﻤﻥ ﺍﻝﻁﺎﻗﺔ‪ ،‬ﺘﺴﺎﻫﻡ ﻓﻲ ﺘﻭﻝﻴﺩﻫﺎ ﺘﻔﺎﻋﻼﺕ‬
‫ﺇ‪‬‬
‫ﺘﺭﺘﺒﻁ ﺒﺎﻝﺴﻔﻴﻨﺔ ﺍﻝﻔﻀﺎﺌﻴﺔ ﺜﻼﺜﺔ ﺨﺯﺍﻨﺎﺕ ﺃﺴﻁﻭﺍﻨﻴﺔ ﺍﻝﺸﻜل‪ .‬ﺍﻝﻤﺭﻜﺯﻱ ﻤﻨﻬﺎ ﻭﻫﻭ ﺍﻷﻜﺒﺭ ﻴﺼل ﻗﻁﺭﻩ ﺇﻝﻰ ﺜﻤﺎﻨﻴﺔ ﺃﻤﺘﺎﺭ‬
‫ﻭﻁﻭﻝﻪ ‪ 47‬ﻤﺘﺭﹰﺍ ﻴﻀ ‪‬ﻡ ﺍﻷﻜﺴﺠﻴﻥ ﺍﻝﺴﺎﺌل ﻭﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﺴﺎﺌل ﻓﻲ ﻋﺒﻭﺘﻴﻥ ﻤﻨﻔﺼﻠﺘﻴﻥ‪ .‬ﻴﻐﺫﻱ ﻫﺫﺍ ﺍﻝﺨﺯﺍﻥ ﺍﻝﻤﺤﺭﻜﺎﺕ‬
‫ﺍﻝﺭﺌﻴﺴﻴﺔ ﻓﻲ ﺍﻝﻤﺭﻜﺒﺔ ﺍﻝﻔﻀﺎﺌﻴﺔ ﺤﻴﺙ ﻴﺘﻔﺎﻋل ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻤﻊ ﺍﻷﻜﺴﺠﻴﻥ ﻝﻴﺘﺸﻜﹼل ﺍﻝﻤﺎﺀ ﻭﺘﻨﻁﻠﻕ ﻁﺎﻗﺔ ﻜﺒﻴﺭﺓ ‪:‬‬
‫‪2 H2 + O2 → 2 H2O+ Energy‬‬
‫ﻭﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﻤﺎ ﻫﻭ ﺇﻻ ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﺤﻴﺙ ﺘﺠﺭﻱ ﺃﻜﺴﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻭﺇﺭﺠﺎﻉ ﺍﻷﻜﺴﺠﻴﻥ‪.‬‬
‫ﺃ ‪‬ﻤﺎ ﺨﺯ‪‬ﺍﻨﺎ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺼﻠﺏ ﺍﻝﻭﺍﻗﻌﺎﻥ ﻋﻠﻰ ﺠﺎﻨﺒﻲ ﺍﻝﻤﺭﻜﺒﺔ ﻓﻬﻤﺎ ﻴﻘﺩ‪‬ﻤﺎﻥ ﻝﻠﻤﺭﻜﺒﺔ ﺤﻭﺍﻝﻲ ‪ 72%‬ﻤﻥ ﻗﻭﺘﻬﺎ ﺍﻝﺭﺍﻓﻌﺔ‬
‫ﺍﻝﺸﺎﻗﻭﻝﻴﺔ ﻋﻨﺩ ﺍﻹﻁﻼﻕ ﻭﻝﻬﺫﺍ ﻴ‪‬ﻁﻠﻕ ﻋﻠﻴﻬﻤﺎ ﺍﺴﻡ ‪ Solid Rocket Boosters :‬ﺃﻱ ﺼﺎﺭﻭﺨﹶﻲ ﺍﻝﺩﻓﻊ ﺒﺎﻝﻭﻗﻭﺩ‬
‫ﺍﻝﺼﻠﺏ‪ .‬ﻗﻁﺭ ﻜل ﻤﻨﻬﻤﺎ ﻨﺤﻭ ﺜﻼﺜﺔ ﺃﻤﺘﺎﺭ ﻭﻨﺼﻑ‬
‫ﺨﺯ‪‬ﺍﻥ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺨﺎﺭﺠﻲ‬
‫ﺍﻝﻤﺘﺭ‪ ،‬ﻭﺍﺭﺘﻔﺎﻉ ﻜل ﻤﻨﻬﻤﺎ ‪ 45‬ﻤﺘﺭﹰﺍ ﻭﻫﻤﺎ ﺃﻴﻀ ﹰﺎ‬
‫ل ﺼﺎﺭﻭﺥ‬
‫ﻤﺭﺘﺒﻁﺎﻥ ﺒﺎﻝﻤﺭﻜﺒﺔ ﺍﻝﻔﻀﺎﺌﻴﺔ‪ .‬ﻴﺤﺘﻭﻱ ﻜ ّ‬
‫ﻋﻠﻰ ‪ 49500‬ﻜﻎ ﻤﻥ ﺍﻝﻤﺘﻔﺠﺭﺍﺕ ﺃﻭ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺼﻠﺏ‬
‫ﺍﻝﺼﺎﺭﻭﺥ ﺍﻝﻴﺴﺎﺭﻱ‬ ‫ﺍﻝﺼﺎﺭﻭﺥ ﺍﻝﻴﻤﻴﻨﻲ‬ ‫ﻭﻫﻭ ﻤﺯﻴﺞ ﻤﻥ ﺒﺭﻜﻠﻭﺭﺍﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ ‪NH4 ClO4‬‬
‫ﺫﻭ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺼﻠﺏ‬ ‫ﺫﻭ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺼﻠﺏ‬
‫ﻥ‬
‫ﻭﻤﺴﺤﻭﻕ ﺍﻷﻝﻤﻨﻴﻭﻡ ﻭﺫﻝﻙ ﺒﻭﺠﻭﺩ ﻤﺎﺩﺓ ﺭﺍﺒﻁﺔ‪ .‬ﻭﻷ ‪‬‬
‫ﻫﺫﻩ ﺍﻝﺼﻭﺍﺭﻴﺦ ﻀﺨﻤﺔ ﺍﻝﺤﺠﻡ ﻓﻬﻲ ﺘﺤﻀ‪‬ﺭ ﻋﻠﻰ‬
‫ل‬
‫ﺃﺠﺯﺍﺀ ﻴﺘ ‪‬ﻡ ﺘﺠﻤﻴﻌﻬﺎ ﻋﻨﺩ ﻤﻭﻗﻊ ﺍﻹﻁﻼﻕ‪ ،‬ﺤﻴﺙ ﻴ‪‬ﻌﺒ‪‬ﺄ ﻜ ّ‬
‫ﺍﻝﻤﺭﻜﺒﺔ ﺍﻝﻤﺩﺍﺭﻴ‪‬ﺔ‬ ‫ﺍﻝﻤﺤﺭﻜﺎﺕ ﺍﻝﺭﺌﻴﺴﺔ‬
‫ﺠﺯﺀ ﻋﻠﻰ ﺤﺩﺓ ﺒﺎﻝﻭﻗﻭﺩ ﺍﻝﺩﺍﻓﻊ ﺍﻝﺫﻱ ﻴﻜﻭﻥ ﻫﻼﻤﻴ ﹰﺎ ﺒﺩﺍﻴﺔ‬
‫ﻝﻤﻜﻭﻙ ﺍﻝﻔﻀﺎﺀ‬
‫ﺜ ‪‬ﻡ ﻴﺘﺠﻤ‪‬ﺩ ﻝﻴﺄﺨﺫ ﻗﻭﺍﻤ ﹰﺎ ﻴﺸﺒﻪ ﻗﻭﺍﻡ ﺍﻝﻤﻤﺤﺎﺓ ﺍﻝﻤﻁﺎﻁﻴﺔ‪.‬‬
‫ﻭﻗﻭﺩ ﺩﺍﻓﻊ ﺼﻠﺏ‬
‫‪24 m‬‬
‫ﻴﺤﺼل ﺘﻔﺎﻋﻼ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﻓﻲ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺼﻠﺏ ﻫﻤﺎ‪:‬‬
‫‪2 NH4 ClO4 (s) + 2 Al(s) → Al2O3 (s) + 2 HCl (g) + 2 NO(g) + 3 H2O(g) + Energy‬‬
‫‪6 NH 4ClO4 (s) + 10 Al(s) → 5 Al2O3 (s) + 6 HCl(g) + 3 N2 (g) + 9 H2O(g) + Energy‬‬
‫ﻥ ﻤﺴﺤﻭﻕ ﺃﻜﺴﻴﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ ﺍﻷﺒﻴﺽ ﺍﻝﻤﺘﺒﻌﺜﺭ ﻀﻤﻥ ﺍﻝﻐﺎﺯﺍﺕ ﺍﻝﻤﻨﻁﻠﻘﺔ ﻫﻭ ﺍﻝﺫﻱ ﻴﻌﻁﻲ ﺍﻝﺩﺨﺎﻥ ﺍﻷﺒﻴﺽ ﺍﻝﻤﻤﻴﺯ‬
‫ﺇ‪‬‬
‫ﺍﻝﺫﻱ ﻨﺭﺍﻩ ﻋﻨﺩ ﺇﻁﻼﻕ ﺍﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﻔﻀﺎﺌﻴﺔ‪.‬‬
‫‪ .III‬ﺘﻔﺎﻋﻼﺕ ﺍﻨﺘﻘﺎل ﺍﻝﺠﺴﻴﻤﺎﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺒﻴﻥ ﻤﺎﻨﺢ ﻭﻤﺘﻘﺒ‪‬ل‬
‫ﺴﻨﻘﺩ‪‬ﻡ ﻓﻴﻤﺎ ﻴﻠﻲ ﻋﺭﻀﹰﺎ ﺠﺎﻤﻌﹰﺎ ﻝﻠﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻲ ﺩﺭﺴﻨﺎﻫﺎ ﻓﻲ ﺍﻝﻔﺼﻭل ﺍﻝﺴﺎﺒﻘﺔ‪ .‬ﻓﻲ ﺍﻝﺤﻘﻴﻘﺔ‬
‫ل ﺯﻭﺝ ﻤﺅﻝﹼﻑ ﻤﻥ‪:‬‬
‫ﻤﺎ ﻴﺠﻤﻊ ﺘﻠﻙ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻫﻭ ﺍﻨﺘﻘﺎل ﺠﺴﻴﻤﺎﺕ ﺒﻴﻥ ﺯﻭﺝ ﻤﻥ ﺍﻝﻤﺭﻜﺒﺎﺕ‪ .‬ﻜ ﱡ‬
‫ ﻤﺎﻨﺢ ﺠﺴﻴﻤﺎﺕ‪ :‬ﺍﻝﺤﻤﺽ ‪ ، AHn‬ﺍﻝﻤﻌﻘﹼﺩ ‪ ، MLn‬ﺍﻝﺭﺍﺴﺏ ‪ ، MXn‬ﺍﻝﻤﺭﺠﻊ ‪. Red‬‬
‫ ﻤﺘﻘ ‪‬ﺒل ﺠﺴﻴﻤﺎﺕ‪ :‬ﺍﻷﺴﺎﺱ ‪ ، An −‬ﺍﻝﺫﺭﺓ ﺃﻭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺭﻜﺯﻴﺔ ‪ ) M‬ﺃﻭ ﺍﻝﺭﺒﻴﻁﺔ ‪، (L‬‬
‫ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﻭﺠﺒﺔ ‪ ) C p +‬ﺃﻭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺴﺎﻝﺒﺔ ‪ ، (Aq −‬ﺍﻝﻤﺅﻜﺴﺩ ‪. Ox‬‬
‫ﺃﻤ‪‬ﺎ ﺍﻝﺠﺴﻴﻤﺎﺕ ﺍﻝﻤﺘﺒﺎ ‪‬ﺩ ﻝﺔ ﻓﻬﻲ ﻋﻠﻰ ﺍﻝﺘﺭﺘﻴﺏ‪ :‬ﺍﻝﺒﺭﻭﺘﻭﻨﺎﺕ‪ ،‬ﺍﻝﺭﺒﻴﻁﺎﺕ ) ﺃﻭ ﺍﻝﺫﺭﺍﺕ ﺃﻭ ﺍﻝﺸﻭﺍﺭﺩ‬
‫ﺍﻝﻤﺭﻜﺯﻴﺔ ‪ ، (M‬ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺴﺎﻝﺒﺔ ) ﺃﻭ ﺍﻝﻤﻭﺠﺒﺔ ( ‪ ،‬ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ‪.‬‬
‫ﻭﺃﻤ‪‬ﺎ ﺍﻝﻜﺘﺎﺒﺔ ﺍﻝﺸﻜﻠﻴﺔ ﻝﻬﺫﻩ ﺍﻷﺯﻭﺍﺝ ﻓﻤﺘﺸﺎﺒﻬﺔ‪:‬‬
‫‪An − + n Hn + ⇌ AHn‬‬ ‫ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﻤﻀﻴﺔ ﺍﻷﺴﺎﺴﻴﺔ ‪:‬‬
‫‪M‬‬ ‫‪+ nL‬‬ ‫‪⇌ MLn‬‬ ‫ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻌﻘﻴﺩ ‪:‬‬
‫‪C n + + nX − ⇌ CX n‬‬ ‫ﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﺭﺴﻴﺏ ‪:‬‬
‫‪Ox + n e− ⇌ Red‬‬ ‫ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪:‬‬
‫ﻤﺎﻨﺢ ⇌ ﺠﺴﻴﻡ ‪ +‬ﻤﺘﻘ‪‬ﺒل‬ ‫ﻭﺒﺼﻭﺭﺓ ﻋﺎﻤﺔ ﻨﻜﺘﺏ ‪:‬‬
‫‪ .IV‬ﻤﻔﻬﻭﻡ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ‬
‫ﻴﺴﻤﺢ ﻤﻔﻬﻭﻡ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪ on‬ﺒﺘﺤﺩﻴﺩ ﺤﺎﻝﺔ ﺃﻜﺴﺩﺓ ﻋﻨﺼﺭ ﺴﻭﺍﺀ ﺃﻜﺎﻥ ﻫﺫﺍ ﺍﻝﻌﻨﺼﺭ ﺤ ‪‬ﺭﹰﺍ‬
‫ﻥ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻫﻭ ﻋﺩﺩ ﺼﺤﻴﺢ‬
‫ﻱ‪ .‬ﺇ ‪‬‬
‫ﻲ ﺃﻭ ﺸﺎﺭﺩ ‪‬‬
‫ﺃﻭ ﻤﺭﺘﺒﻁﹰﺎ ﻤﻊ ﺫﺭ‪‬ﺍﺕ ﺃﺨﺭﻯ ﻀﻤﻥ ﺒﻨﻴﺎﻥ ﺠﺯﻴﺌ ‪‬‬
‫ﺠﺒﺭﻱ ﻨﻜﺘﺒﻪ ﻋﺎﺩﺓ ﺒﺎﺴﺘﻌﻤﺎل ﺃﺭﻗﺎﻡ ﺭﻭﻤﺎﻨﻴﺔ‪ .‬ﻭﻓﻴﻤﺎ ﻴﻠﻲ ﺍﻝﻘﻭﺍﻋﺩ ﺍﻝﺘﻲ ﺘﻔﻴﺩ ﻓﻲ ﺘﺤﺩﻴﺩﻩ‪:‬‬
‫ﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﻋﻨﺼﺭ ﻓﻲ ﺸﺎﺭﺩﺓ ﻭﺤﻴﺩﺓ ﺍﻝﺫﺭ‪‬ﺓ ﻴﺴﺎﻭﻱ ﻋﺩﺩ ﺍﻝﺸﺤﻨﺎﺕ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ‬
‫ﺍﻟﻘﺎﻋﺪﺓ ﺍﻷﻭﱃ ‪ :‬ﺇ ‪‬‬
‫ﺍﻝﺘﻲ ﺘﺤﻤﻠﻬﺎ ﻫﺫﻩ ﺍﻝﺸﺎﺭﺩﺓ ﻤﺄﺨﻭﺫﺓ ﻤﻊ ﺇﺸﺎﺭﺘﻬﺎ‪.‬‬
‫‪Na+‬‬ ‫‪on(Na + ) = +I‬‬
‫‪Cl−‬‬ ‫‪on(Cl− ) = −I‬‬
‫‪Fe3 +‬‬ ‫‪on(Fe3+ ) = +III‬‬
‫‪O2−‬‬ ‫‪on(O2− ) = −II‬‬
‫ﻥ‬
‫ﺍﻟﻘﺎﻋﺪﺓ ﺍﻟﺜﺎﻧﻴﺔ ‪ :‬ﻓﻲ ﺤﺎﻝﺔ ﻭﺠﻭﺩ ﺭﺍﺒﻁﺔ ﺘﺸﺎﺭﻜﻴﺔ ﺒﻴﻥ ﻋﻨﺼﺭﻴﻥ ﻀﻤﻥ ﺒﻨﻴﺎﻥ ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﺫﺭﺍﺕ‪ ،‬ﻓﺈ ‪‬‬
‫ل‬
‫ﻥ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻝﻜ ّ‬
‫ﺇﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﺭﺍﺒﻁﺔ ﺘﹸﺴﻨﹶﺩ ﺇﻝﻰ ﺍﻝﻌﻨﺼﺭ ﺍﻷﻜﺜﺭ ﻜﻬﺭﺴﻠﺒﻴﺔ‪ .‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﻋﻨﺼﺭ ﻤﻥ ﺍﻝﻌﻨﺎﺼﺭ ﺍﻝﻤﺸﻜﹼﻠﺔ ﻝﻬﺫﺍ ﺍﻝﺒﻨﻴﺎﻥ ﻴﺴﺎﻭﻱ ﻋﺩﺩ ﺍﻝﺸﺤﻨﺎﺕ ﺍﻻﻋﺘﺒﺎﺭﻴﺔ ﺍﻝﻤﺴﻨﺩﺓ ﺇﻝﻴﻪ‪.‬‬
‫ﻥ‪:‬‬
‫ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻝﻠﻌﻨﺎﺼﺭ ﻓﻲ ﺍﻷﺠﺴﺎﻡ ﺍﻝﺒﺴﻴﻁﺔ ﻴﺴﺎﻭﻱ ﺍﻝﺼﻔﺭ‪.‬‬
‫‪H  H‬‬ ‫‪O  O‬‬
‫‪on ( H ) = 0‬‬ ‫‪on ( O ) = 0‬‬
‫ ﻹﻴﺠﺎﺩ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﻋﻨﺼﺭ ﻓﻲ ﺒﻨﻴﺎﻥ ﻤﺘﻌﺩ‪‬ﺩ ﺍﻝﺫﺭﺍﺕ‪:‬‬
‫‪ .1‬ﻨﻜﺘﺏ ﺘﻤﺜﻴل ﻝﻭﻴﺱ ﻝﻬﺫﺍ ﺍﻝﺒﻨﻴﺎﻥ‪.‬‬
‫ل ﺭﺍﺒﻁﺔ ﺒﻴﻥ ﺫﺭﺘﻴﻥ ﺇﻝﻰ ﺍﻝﺫﺭ‪‬ﺓ ﺍﻷﻜﺜﺭ ﻜﻬﺭﺴﻠﺒﻴﺔ‪.‬‬
‫‪ .2‬ﻨﺴﻨﺩ ﺜﻨﺎﺌﻴ‪‬ﺔ ﻜ ّ‬
‫‪ .3‬ﻨﺄﺨﺫ ﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺸﺤﻨﺎﺕ‪.‬‬
‫ﻥ ﻴﻜﻭﻥ ﺍﻝﻤﺠﻤﻭﻉ ﺍﻝﺠﺒﺭﻱ ﻷﺭﻗﺎﻡ‬
‫ﺍﻟﻘﺎﻋﺪﺓ ﺍﻟﺜﺎﻟﺜﺔ ‪ :‬ﻴﻘﻀﻲ ﺍﻨﺤﻔﺎﻅ ﺍﻝﺸﺤﻨﺔ ﻓﻲ ﺒﻨﻴﺎﻥ ﺘﺸﺎﺭﻜﻲ ﺒﺄ ‪‬‬
‫ﺍﻷﻜﺴﺩﺓ ﻤﻀﺭﻭﺒﹰﺎ ﺒﻌﺩﺩ ﺍﻝﺫﺭﺍﺕ ﻝﻬﺫﻩ ﺍﻝﻌﻨﺎﺼﺭ ﻓﻲ ﺍﻝﺼﻴﻐﺔ ﻤﺴﺎﻭﻴﹰﺎ ﻋﺩﺩ ﺍﻝﺸﺤﻨﺎﺕ ﺍﻝﻜﻠﹼﻴﺔ‬
‫ﻝﻠﺒﻨﻴﺎﻥ‪.‬‬
‫ﺃﻤﺜﻠﺔ ‪:‬‬
‫ ﺍﻝﻤﺎﺀ ﻭﺍﻝﻤﺎﺀ ﺍﻷﻜﺴﺠﻴﻨﻲ ‪:‬‬
‫‪O‬‬
‫‪− II‬‬
‫‪H‬‬ ‫‪H‬‬
‫‪+I‬‬ ‫‪+I‬‬
‫‪H  O  O  H‬‬
‫‪+I‬‬ ‫‪−I‬‬ ‫‪−I‬‬ ‫‪+I‬‬
‫ ﺸﺎﺭﺩﺓ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‪:‬‬
‫‪− II‬‬ ‫‪− II‬‬

‫‪O‬‬ ‫‪O‬‬
‫‪S‬‬
‫‪− II‬‬ ‫‪+VI‬‬
‫‪− II‬‬
‫‪O‬‬ ‫‪O‬‬
‫⊖‬ ‫⊖‬
‫ﻥ ‪ −8 + x = −2‬ﻭﻤﻨﻪ ‪. x = 6‬‬
‫ﻹﻴﺠﺎﺩ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﺫﺭﺓ ﺍﻝﻜﺒﺭﻴﺕ ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ ﺸﺎﺭﺩﺓ ﺍﻝﺜﻴﻭﻜﺒﺭﻴﺘﺎﺕ‪:‬‬
‫∖‪∕S‬‬
‫⊖‬ ‫‪+ IV‬‬ ‫⊖‬

‫‪− II‬‬ ‫‪O‬‬ ‫‪S‬‬ ‫‪O − II‬‬
‫∕‪− II ∖O‬‬
‫ﻥ ﺫﺭﺓ ﺍﻝﻜﺒﺭﻴﺕ ﺍﻝﻤﺤﻴﻁﻴﺔ ﺘﺘﻤﺘﹼﻊ ﺒﺭﻗﻡ ﺃﻜﺴﺩﺓ ﻴﺴﺎﻭﻱ ﺍﻝﺼﻔﺭ‪ .‬ﺃﻤﺎ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﺫﺭﺓ‬
‫ﺍﻝﻜﺒﺭﻴﺕ ﺍﻝﻤﺭﻜﺯﻴﺔ ﻓﻴ‪‬ﺤﺴﺏ ﻜﻤﺎ ﻴﻠﻲ ‪ x − 6 = −2 :‬ﺃﻱ ‪. x = 4‬‬
‫ ﺸﺎﺭﺩﺓ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪: MnO−4‬‬
‫‪− II‬‬
‫∖‪∕O‬‬
‫∕‬ ‫‪+ VII‬‬ ‫⊖‬

‫‪− II‬‬ ‫‪O‬‬
‫∖‬ ‫‪Mn‬‬ ‫‪O − II‬‬
‫∕‪− II ∖O‬‬
‫ﻹﻴﺠﺎﺩ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﺫﺭﺓ ﺍﻝﻤﻨﻐﻨﻴﺯ‪ ،‬ﻨﻜﺘﺏ ‪ x − 8 = −1‬ﻭﻤﻨﻪ ‪. x = 7‬‬

‫ﺤﺎﻻﺕ ﺨﺎﺼ‪‬ﺔ‪:‬‬
‫ل ﻤﻨﻪ ﻜﻬﺭﺴﻠﺒﻴ‪‬ﺔ‪.‬‬
‫ﻴﺭﺘﺒﻁ ﺍﻷﻜﺴﺠﻴﻥ ﻓﻲ ﻤﻌﻅﻡ ﺍﻝﻤﺭﻜﹼﺒﺎﺕ ﺍﻝﺘﻲ ﻴﺩﺨل ﻓﻴﻬﺎ ﻤﻊ ﺫﺭﺍﺕ ﺃﻗ ّ‬ ‫‬
‫ﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ ﻫﻭ ) ‪ ( − II‬ﺒﺎﺴﺘﺜﻨﺎﺀ ﺍﻝﻭﻀﻊ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺎﺀ ﺍﻷﻜﺴﺠﻴﻨﻲ‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﺤﻴﺙ ﻴﻜﻭﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ ﻤﺴﺎﻭﻴﹰﺎ ) ‪ ( − I‬ﻭﻓﻠﻭﺭﻴﺩ ﺍﻷﻜﺴﺠﻴﻥ ﺤﻴﺙ ﻴﻜﻭﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ‬
‫ﻤﺴﺎﻭﻴ ﹰﺎ ) ‪: ( + II‬‬
‫‪F  O  F‬‬
‫‪on ( O ) = + II‬‬
‫ﻴﺭﺘﺒﻁ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻓﻲ ﻤﻌﻅﻡ ﺍﻝﻤﺭﻜﹼﺒﺎﺕ ﺍﻝﺘﻲ ﻴﺩﺨل ﻓﻴﻬﺎ ﻤﻊ ﺫﺭﺍﺕ ﺃﻜﺜﺭ ﻤﻨﻪ‬ ‫‬
‫ﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ ﻫﻭ ) ‪ ( + I‬ﺒﺎﺴﺘﺜﻨﺎﺀ ﺍﻝﻭﻀﻊ ﻓﻲ ﺤﺎﻝﺔ‬
‫ﻜﻬﺭﺴﻠﺒﻴ‪‬ﺔ‪ .‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﺍﻝﻬﻴﺩﺭﻴﺩﺍﺕ ﺍﻝﻤﻌﺩﻨﻴﺔ ) ‪ ( Na H, Li H‬ﺤﻴﺙ ﻴﻜﻭﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ ﻤﺴﺎﻭﻴﹰﺎ ) ‪: ( − I‬‬
‫‪Li  H‬‬
‫‪on ( H ) = − I‬‬
‫‪ .V‬ﺨﻭﺍﺹ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ‬
‫ﻝﻨﺄﺨﺫ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻻﺤﺘﺭﺍﻕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻓﻲ ﺠ ‪‬ﻭ ﻤﻥ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺍﻷﻜﺴﺠﻴﻥ‪.‬‬

‫ﺇﺭﺠﺎﻉ‬
‫‪0‬‬ ‫‪− II‬‬
‫↑‬ ‫↑‬
‫‪2 Na +‬‬ ‫‪1O‬‬
‫‪2 2‬‬ ‫‪→ 2 Na‬‬ ‫‪+‬‬
‫‪+ O2−‬‬
‫↓‬ ‫↓‬
‫‪0‬‬ ‫ﺃﻜﺴﺩﺓ‬ ‫‪+I‬‬
‫ﻥ‬
‫ﻥ ﺍﻷﻜﺴﺠﻴﻥ ﻗﺩ ﺃُﺭﺠﻊ ﻷ ‪‬‬
‫ﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ ﻗﺩ ﺍﺯﺩﺍﺩ‪ ،‬ﻭﺃ ‪‬‬
‫ﻥ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻗﺩ ﺘﺄﻜﹼﺴﺩ ﻷ ‪‬‬
‫ﺭﻗﻡ ﺃﻜﺴﺩﺘﻪ ﻗﺩ ﺘﻨﺎﻗﺹ‪ .‬ﻭﻤﻨﻪ ﻨﺼل ﺇﻝﻰ ﺍﻝﻨﺘﻴﺠﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫ﻋﻨﺩﻤﺎ ﻴﺘﺄﻜﺴﺩ ﻋﻨﺼﺭ ﻴﺯﺩﺍﺩ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ‪ ،‬ﻓﻲ ﺤﻴﻥ ﻴﺘﻨﺎﻗﺹ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻋﻨﺩﻤﺎ ﻴ‪‬ﺭﺠ‪‬ﻊ‬
‫ﻫﺫﺍ ﺍﻝﻌﻨﺼﺭ‪.‬‬
‫ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻨﺼﻔﻴﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻨﺼﻔﻴ‪‬ﺘﻴﻥ ﺍﻝﺨﺎﺼﺘﻴﻥ ﺒﺎﻝﺯ‪‬ﻭﺠﻴﻥ ) ‪ ( Ox/Red‬ﺍﻝﻠﹼﺫﻴﻥ ﻅﻬﺭﺍ ﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ‬

‫ﺇ‪‬‬
‫ﺍﻝﺴﺎﺒﻘﺔ ﻫﻤﺎ‪:‬‬
‫↽ ‪Na+ + e−‬‬

‫⇀‬
‫‪ Na‬‬ ‫‪1O‬‬
‫‪2 2‬‬ ‫↽ ‪+ 2e−‬‬‫‪ O2−‬‬
‫⇀‬
‫‪n(e − ) = ∆on ( Na ) = +I‬‬ ‫‪n(e − ) = ∆on ( O ) = +II‬‬
‫ل ﻋﻨﺼﺭ ﺘﺴﺎ ﻭ ﻱ ﻋﺩﺩ‬

‫ﻥ ﺍ ﻝﻘﻴﻤﺔ ﺍ ﻝﻤﻁﻠﻘﺔ ﻝﺘﻐﻴ‪‬ﺭ ﺍ ﺕ ﺭ ﻗﻡ ﺍ ﻷ ﻜﺴﺩ ﺓ ﻝﻜ ّ‬
‫ﻭ ﻫﻜﺫ ﺍ ﻨﺠﺩ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﻤﺘﺒﺎﺩﻝﺔ‪ .‬ﻭﻨﻼﺤﻅ ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﺃ ‪‬‬
‫‪2∆on ( Na ) + ∆on ( O ) = 0‬‬
‫ل‬
‫ﺇﺫﻥ ﻓﻲ ﻜل ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭ ﺇﺭﺠﺎﻉ ﻴﻜﻭﻥ ﻤﺠﻤﻭﻉ ﺘﻐﻴﺭﺍﺕ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ﺒﻌﺩ ﺘﺜﻘﻴل ﻜ ّ‬
‫ﻤﻨﻬﺎ ﺒﺎﻷﻤﺜﺎل ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ) ﺍﻷﻤﺜﺎل ﺍﻝﺘﻔﺎﻋﻠﻴﺔ( ﺍﻝﻤﻭﺍﻓﻘﺔ ﻴﺴﺎﻭﻱ ﺍﻝﺼﻔﺭ‪ .‬ﻭﺴﻭﻑ ﻨﺴﺘﺜﻤﺭ ﻫﺫﻩ‬
‫ﺍﻝﺨﺎﺼﺔ ﻻﺤﻘﹰﺎ ﻋﻨﺩ ﻤﻭﺍﺯﻨﺔ ﻤﻌﺎﺩﻻﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‪.‬‬
‫‪ .VI‬ﺘﻁﺒﻴﻘﺎﺕ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ‬
‫‪ .1.VI‬ﻁﺒﻴﻌﺔ ﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ‬
‫ل ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ‬
‫ﻼ ﻜﻴﻤﻴﺎﺌﻴﹰﺎ ﻴﺘﻐﻴ‪‬ﺭ ﻓﻴﻪ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻝﻌﻨﺼﺭ ﻭﺍﺤﺩ ﻋﻠﻰ ﺍﻷﻗ ّ‬
‫ﻨﺴﻤ‪‬ﻲ ﺘﻔﺎﻋ ﹰ‬
‫ﻭﺇﺭﺠﺎﻉ‪ .‬ﺍﻝﺘﻔﺎﻋﻼﻥ ﺍﻝﺘﺎﻝﻴﺎﻥ ﻴﻌﻁﻴﺎﻥ ﺃﻤﺜﻠﺔ ﻋﻥ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪:‬‬
‫‪0‬‬ ‫‪+II‬‬
‫‪C O2 +2 Mg → C +2 Mg O‬‬
‫‪+IV‬‬ ‫‪0‬‬
‫‪0‬‬ ‫‪−I‬‬ ‫‪−I‬‬
‫‪C H 4 + Br2 → C H3 Br +H Br‬‬
‫‪−IV‬‬ ‫‪−II‬‬
‫‪ .2.VI‬ﻤﻭﺍﺯﻨﺔ ﻤﻌﺎﺩﻝﺔ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ‬
‫ﻝﻨﺘﺫﻜﹼﺭ ﻤﻌﹰﺎ ﺍﻝﻁﹼﺭﻴﻘﺔ ﺍﻝﻌﺎﻤ‪‬ﺔ ﺍﻝﻤﺘﹼﺒﻌﺔ ﻓﻲ ﻤﻭﺍﺯﻨﺔ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ‬
‫ﺒﺄﺨﺫﻨﺎ ﻝﻤﺜﺎل ﺘﻔﺎﻋل ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﻤﻊ ﺍﻝﻨﺤﺎﺱ‪ .‬ﻴﺠﺭﻱ ﻓﻲ ﺃﺜﻨﺎﺀ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺇﺭﺠﺎﻉ ﺸﺎﺭﺩﺓ‬
‫‪ NO−‬ﺇﻝﻰ ﺃﻭل ﺃﻜﺴﻴﺩ ﺍﻵﺯﻭﺕ ‪ ، NO‬ﻜﻤﺎ ﻴﺠﺭﻱ ﺃﻜﺴﺩﺓ ﺍﻝﻨﺤﺎﺱ ‪ Cu‬ﺇﻝﻰ ﺸﺎﺭﺩﺓ‬
‫ﺍﻝﻨﺘﺭﺍﺕ ‪3‬‬
‫ﺍﻝﻨﺤﺎﺱ ﺍﻝﺜﻨﺎﺌﻴﺔ ‪. Cu2+‬‬
‫ ﻨﻜﺘﺏ ﻨﺼﻔﻲ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺘﻴﻥ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﺩﺍﺨﻠﻴﻥ ﻓﻲ ﺘﻔﺎﻋل ﺍﻷﻜﺴﺩﺓ ﻭ ﺍﻹﺭﺠﺎﻉ‬

‫ﺍﻝﻤﻭﺍﻓﻕ‪.‬‬
‫‪NO−‬‬ ‫ ‪−‬‬
‫↽ ‪3 + 3e‬‬‫⇀‬‫‪ NO‬‬
‫‪ Cu2+ + 2e−‬‬
‫⇀‬
‫↽ ‪Cu‬‬
‫ﻼ ﻤﻥ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﺴﺎﺒﻘﺘﻴﻥ ﺒﺎﻷﻤﺜﺎل ‪ ν‬ﻭ ‪ ν ′‬ﺒﺤﻴﺙ‬
‫ ﻨﻀﺭﺏ ﻜ ﹰ‬
‫‪ν ⋅ ∆on ( NO−‬‬

‫‪3 ) +ν ′ ⋅ ∆on ( Cu ) = 0‬‬
‫ﺜ ‪‬ﻡ ﻨﺠﻤﻌﻬﻤﺎ ﺒﻤﻌﺎﺩﻝﺔ ﺭﻤﺯﻴﺔ ﻻ ﺘﺤﻭﻱ ﺇﻝﻜﺘﺭﻭﻨﺎﺕ‬

‫‪2 NO−‬‬
‫‪3 + 3 Cu → 2 NO + 3 Cu‬‬
‫‪2+‬‬
‫ ﻨﻭﺍﺯﻥ ﺍﻝﺸﺤﻨﺎﺕ ﺒﻴﻥ ﻁﺭﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺒﺎﺴﺘﻌﻤﺎل ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ﺃﻭ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﻭﺫﻝﻙ‬
‫ﺤﺴﺏ ‪ pH‬ﺍﻝﻭﺴﻁ‪ .‬ﻭﻫﻭ ﻓﻲ ﺤﺎﻝﺘﻨﺎ ﺤﻤﻀﻲ‪ ،‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ‪:‬‬
‫‪8 H3O+ + 2 NO−‬‬
‫‪3 + 3 Cu → 2 NO + 3 Cu‬‬
‫‪2+‬‬
‫ ﻨﻭﺍﺯﻥ ﺫﺭﺍﺕ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺒﻴﻥ ﻁﺭﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻭﺒﺎﻝﻨﺘﻴﺠﺔ ﺴﺘﺘﻭﺍﺯﻥ ﺫﺭﺍﺕ ﺍﻷﻜﺴﺠﻴﻥ ﺒﻴﻥ‬
‫ﻁﺭ ﻓﻲ ﺍ ﻝﻤﻌﺎﺩ ﻝﺔ ﻭ ﺫﻝﻙ ﺒﺎﻻﺴﺘﻌﺎﻨﺔ ﺒﺎﻝﻤﺫﻴﺏ ﺍ ﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺎﺩﺓ ﻤﺘﻔﺎ ﻋﻠﺔ ﺃﻭ ﻨﺎﺘﺠﺔ ﻋﻥ‬
‫ﺍﻝﺘﻔﺎﻋل‪.‬‬
‫‪8 H3O+ + 2 NO−‬‬
‫‪3 + 3 Cu → 2 NO + 3 Cu‬‬
‫‪2+‬‬
‫‪+ 12 H2O‬‬
‫‪ .VII‬ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ‬
‫‪ .1.VII‬ﺘﻌﺎﺭﻴﻑ ﻭﺍﺼﻁﻼﺤﺎﺕ‬
‫‪ .1.1.VII‬ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﻭﺍﻝﻤﺴﺭﻯ‬
‫ل ﺍﺠﺘﻤﺎﻉ ﻝﻨﻭﻋﻴﻥ ‪ Ox‬ﻭ ‪ Red‬ﻤﻥ ﺯﻭﺝ ‪ Ox/Red‬ﺇﻀﺎﻓﺔ‬

‫ﻨﺴﻤ‪‬ﻲ ﻨﺼﻑ ﺨﻠﻴﺔ ﻜ ّ‬
‫ﺇﻝﻰ ﻤﺤﻠﻭل ﻜﻬﺭﻝﻴﺘﻲ ﻴﻜﻭﻥ ﻓﻲ ﺘﻤﺎﺱ ﻤﻊ ﻨﺎﻗل‪ .‬ﻴﻤﻜﻥ ﺃﻥ ﻴﻜﻭﻥ ﺍﻝﻨﺎﻗل ﺃﺤﺩ ﻨﻭﻋﻲ ﺍﻝﺯﻭﺝ‬
‫‪ . Ox/Red‬ﻭﻴﻤﻜﻥ ﻝﻠﻨﻭ ﻋﻴﻥ ‪ Ox‬ﻭ ‪ Red‬ﺃﻥ ﻴﻜﻭﻨﺎ ﺼﻠﺒﻴﻥ‪ ،‬ﺃﻭ ﻏﺎ ﺯﻴﻴﻥ ﺃﻭ ﻤﻨﺤﻠﹼﻴﻥ ﻓﻲ‬
‫ﺍﻝﻜﻬﺭﻝﻴﺕ‪.‬‬
‫ﺃﻤﺜﻠﺔ‪:‬‬
‫ ﺴﻠﻙ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﻓﻲ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ‪ Fe3 +‬ﻭ ‪ Fe2+‬ﻤﻥ ﺯﻭﺝ ‪. Fe3+ / Fe2 +‬‬
‫ ﺼﻔﻴﺤﺔ ﺒﻼﺘﻴﻥ ﻋﻠﻴﻬﺎ ﺒﻼﺘﻴﻥ ﺤﺒﻴﺒﻲ ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ‪ HCl‬ﻭﻴ‪‬ﻨﻔﹶﺦ ﻓﻴﻬﺎ‬
‫ﻏﺎﺯ ‪ ) H2‬ﺍﻝﺯﻭﺝ ‪. (H3O+ / H2‬‬
‫ ﺼﻔﻴﺤﺔ ﻤﻥ ﺍﻝﻔﻀﺔ ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀﺔ ) ﺍﻝﺯﻭﺝ ‪. (Ag +/Ag‬‬
‫ل ﺍﻝﺫﻱ ﻴﺤﻘﹼﻕ ﺍﻝﺭﺒﻁ ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻤﻊ ﺩﺍﺭﺓ ﺨﺎﺭﺠﻴﺔ‪.‬‬

‫ﻭﻨﺴﻤ‪‬ﻲ ﻋﺎﺩﺓ ﻤﺴﺭﻯ )ﺇﻝﻜﺘﺭﻭﺩ( ﺍﻝﻨﺎﻗ َ‬
‫ﻭﻝﻜﻨﻨﺎ ﺃﺤﻴﺎﻨﹰﺎ ﻨﻌﻤ‪‬ﻡ ﻫﺫﻩ ﺍﻝﺘﺴﻤﻴﺔ ﻋﻠﻰ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﻭﻨﺴﻤ‪‬ﻴﻪ ﻤﺴﺭﻯ ‪ ،‬ﻜﻤﺎ ﺴﻨﺭﻯ ﺫﻝﻙ ﻓﻲ ﺤﺎﻝﺔ‬
‫ﻨﺴﻤﻲ ﺍﻝﻤﺴﺭﻯ ﻤﺼﻌﺩ ﹰﺍ ﻋﻨﺩﻤﺎ ﻴﺤﺼل ﻋﻨﺩﻩ ﺘﻔﺎﻋل‬ ‫ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻭ ﻤﺴﺭﻯ ﺍﻝﻜﺎﻝﻭﻤﻴل‪.‬‬
‫ﺃﻜﺴﺩﺓ‪ ،‬ﻭﺒﺎﻝﻤﻘﺎﺒل ﻨﺴﻤﻲ ﺍﻝﻤﺴﺭﻯ ﻤﻬﺒﻁﹰﺎ ﻋﻨﺩﻤﺎ ﻴﺤﺼل ﻋﻨﺩﻩ ﺘﻔﺎﻋل ﺇﺭﺠﺎﻉ‪.‬‬
‫‪ .2.1.VII‬ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺃﻭ ﺍﻝﺒﻁﺎﺭﻴﺔ‬
‫ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺃﻭ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻜﻬﺭﻜﻴﻤﻴﺎﺌﻴﺔ ﻫﻲ ﺍﺠﺘﻤﺎﻉ ﻨﺼﻔﻲ ﺨﻠﻴﺔ ﻤﺭﺒﻭﻁﻴﻥ ﺒﻭﺼﻠﺔ‬

‫ﻜﻬﺭﻝﻴﺘﻴﺔ‪ .‬ﻴﻤﻜﻥ ﺃﻥ ﺘﻜﻭﻥ ﻫﺫﻩ ﺍﻝﻭﺼﻠﺔ ﺍﻝﻜﻬﺭﻝﻴﺘﻴﺔ ﻏﺸﺎ ‪‬ﺀ ﻤﺴﺎﻤﻴﹰﺎ ﺃﻭ ﻜﻬﺭﻝﻴﺘﹰﺎ ﻤﺜﺒ‪‬ﺘ ﹰﺎ ﻀﻤﻥ ﻫﻼﻡ‪،‬‬
‫ﺍﻝﺸﻜل ) ‪ . ( 3‬ﻨﺴﻤ‪‬ﻲ ﺒﺼﻭﺭﺓ ﻋﺎﻤﺔ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺒﻁﺎﺭﻴﺔ ﻋﻨﺩﻤﺎ ﺘﻌﻤل ﻋﻤل ﻤﻭﻝﹼﺩ ﻜﻬﺭﺒﺎﺌﻲ‪.‬‬
‫ﺘﻤﺜﻴل ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ‪:‬‬
‫ﺘﹸﻤﺜﹼل ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺒﻜﺘﺎﺒﺔ ﺴﻠﺴﻠﺔ ﺍﻝﻨﻭﺍﻗل ﺍﻝﺘﻲ ﻨﺠﺩﻫﺎ ﻓﻲ ﺍﻝﺨﻠﻴﺔ ﻋﻠﻰ ﺃﻥ ﻨﻀﻊ ﻋﻤﻭﺩﹰﺍ‬
‫ﺸﺎﻗﻭﻝﻴﹰﺎ ﻝﻴﻤﺜﹼل ﺍﻝﻭﺼل ﺒﻴﻥ ﻁﻭﺭﻴﻥ ﻤﺨﺘﻠﻔﻴﻥ ﻭﻭﻀﻊ ﻋﻤﻭﺩﻴﻥ ﻤﻨﻘﹼﻁﻴﻥ ﻝﺘﻤﺜﻴل ﺍﻝﻭﺼل ﺍﻝﻜﻬﺭﻝﻴﺘﻲ‬
‫ﻥ ﺍﻝﻁﻭﺭﻴﻥ ﺍﻝﻤﻔﺼﻭﻝﻴﻥ ﻋﺒﺭ ﻫﺫﻩ ﺍﻝﻭﺼﻠﺔ ﻝﻬﻤﺎ‬
‫ﻱ ﻜﻤﻭﻥ ﻭﺼل )ﻷ ‪‬‬
‫ﺍﻝﺫﻱ ﻻ ﻴﺘﻤﺘﹼﻊ ﻫﻭ ﺒﺩﻭﺭﻩ ﺒﺄ ‪‬‬
‫ﺍﻝﻜﻤﻭﻥ ﺫﺍﺘﻪ(‪.‬‬
‫ﺍﻋﺘﻤﺎﺩﹰﺍ ﻋﻠﻰ ﻤﺎ ﺴﺒﻕ ﻨﻤﺜﹼل ﺒﻁﺎﺭﻴﺔ ﺩﺍﻨﻴﻴل ‪ Daniell‬ﺃﻭ ﺨﻠﻴﺔ ﺩﺍﻨﻴﻴل ﻜﻤﺎ ﻴﻠﻲ‪:‬‬
‫) ‪Zn(s ) Zn2 + SO24− ⋮⋮ SO24− Cu2+ Cu(s‬‬

‫ﺗﻮﺗﻴﺎﺀ‬ ‫ﳓﺎﺱ‬ ‫)‪(b‬‬
‫ﺗﻮﺗﻴﺎﺀ‬ ‫ﳓﺎﺱ‬ ‫)‪(a‬‬
‫ﳏﻠﻮﻝ ﻛﱪﻳﺘﺎﺕ‬ ‫ﳏﻠﻮﻝ ﻛﱪﻳﺘﺎﺕ‬

‫ﺍﻟﺘﻮﺗﻴﺎﺀ‬ ‫ﺍﻟﻨﺤﺎﺱ‬
‫ﻏﺸﺎﺀ ﻣﺴﺎﻣﻲ‬
‫ﳏﻠﻮﻝ ﻛﱪﻳﺘﺎﺕ ﺍﻟﺘﻮﺗﻴﺎﺀ‬ ‫ﳏﻠﻮﻝ ﻛﱪﻳﺘﺎﺕ ﺍﻟﻨﺤﺎﺱ‬
‫ﺍﻝﺸﻜل ) ‪ : ( 3‬ﻤﺜﺎل ﻋﻠﻰ ﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ‪ :‬ﺨﻠﻴﺔ ﺩﺍﻨﻴﻴل )‪ (a‬ﺒﻭﺠﻭﺩ ﻏﺸﺎﺀ ﻤﺴﺎﻤﻲ ﺃﻭ‬
‫)‪ (b‬ﻜﻬﺭﻝﻴﺕ ﻤﺜﺒ‪‬ﺕ ﻀﻤﻥ ﻫﻼﻡ‪.‬‬
‫‪ .3.1.VII‬ﺍﻻﺘﺠﺎﻩ ﺍﻻﺼﻁﻼﺤﻲ ﻝﻠﺘﻔﺎﻋل ﺍﻝﻜﻬﺭﻜﻴﻤﻴﺎﺌﻲ‬
‫ﻥ ﺍﻻﺘﺠﺎﻩ ﺍﻻﺼﻁﻼﺤﻲ ﻝﻠﺘﻔﺎﻋل ﺍﻝﻜﻬﺭﻜﻴﻤﻴﺎﺌﻲ ﻀﻤﻥ ﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ ﻫﻭ ﺒﺤﻴﺙ ﺘﺨﺭﺝ‬

‫ﺇ‪‬‬
‫ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻤﻥ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻴﺴﺎﺭﻱ ﻨﺤﻭ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻴﻤﻴﻨﻲ ﻭﺫﻝﻙ ﻤﻥ ﺨﻼل ﻨﺎﻗل ﻴﺼل ﺒﻴﻥ‬
‫ﻥ ﺍﻷﻜﺴﺩﺓ ﺘﺠﺭﻱ ﻋﻠﻰ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻴﺴﺎﺭﻱ ﺃﻱ ﺍﻝﻤﺼﻌﺩ ﻓﻲ‬
‫ﺍﻝﻤﺴﺭﻴﻴﻥ ﺨﺎﺭﺝ ﺍﻝﺨﻠﻴﺔ‪ .‬ﻭﻫﻜﺫﺍ ﻓﺈ ‪‬‬
‫ﻥ ﺍﻹﺭﺠﺎﻉ ﻴﺠﺭﻱ ﻋﻠﻰ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻴﻤﻴﻨﻲ ﺃﻱ ﺍﻝﻤﻬﺒﻁ‪ .‬ﻭﺒﺫﻝﻙ ﻨﻜﺘﺏ ﺨﻠﻴﺔ ﺩﺍﻨﻴﻴل ﻋﻠﻰ ﺍﻝﻨﺤﻭ‬
‫ﺤﻴﻥ ﺃ ‪‬‬
‫ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫) ‪− Zn(s‬‬ ‫) ‪Zn 2+ SO24− ⋮⋮ SO24− Cu2+ Cu(s‬‬ ‫‪+‬‬ ‫ﺑﻄﺎﺭﻳﺔ‬

‫‪e−‬‬ ‫‪i‬‬ ‫ﺩﺍﺭﺓ ﺧﺎﺭﺟﻴﺔ‬
‫‪ .2.VII‬ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ‪:‬‬
‫ﻨﻌﺭ‪‬ﻑ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ ﻭﻓﻕ ﺍﻝﻌﻼﻗﺔ ‪:‬‬

‫‪E = VR − VL‬‬
‫ﺤﻴﺙ ‪ VR‬ﻭ ‪ VL‬ﻫﻤﺎ ﺍﻝﻜﻤﻭﻨﺎﻥ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺎﻥ ﻝﻠﻤﺴﺭﻯ ﺍﻝﻴﻤﻴﻨﻲ ﻭﺍﻝﻴﺴﺎﺭﻱ ﻋﻠﻰ ﺍﻝﺘﺭﺘﻴﺏ‬
‫ﻥ ‪ E‬ﻫﻲ ﻤﻘﺩﺍﺭ ﺠﺒﺭﻱ‪ .‬ﻭﻴﻘﺎﺱ ‪E‬‬
‫ﻓﻲ ﺩﺍﺭﺓ ﻤﻔﺘﻭﺤﺔ ﺃﻱ ‪ . i = 0‬ﻭﺤﺴﺏ ﺍﻝﺘﻌﺭﻴﻑ ﺍﻝﺴﺎﺒﻕ ﻓﺈ ‪‬‬
‫ﻋﺎﺩﺓ ﺒﺎﺴﺘﻌﻤﺎل ﻤﻘﻴﺎﺱ ﭭﻭﻝﺕ ﺫﻱ ﻤﻤﺎﻨﻌﺔ ﻋﺎﻝﻴﺔ‪.‬‬
‫ﻭﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﻜﻭ‪‬ﻨﺔ ﻝﻠﺨﻠﻴﺔ ﻤﺄﺨﻭﺫﺓ ﻀﻤﻥ ﺍﻝﺸﺭﻭﻁ ﺍﻝﻨﻅﺎﻤﻴﺔ‪ ،‬ﻓﺈﻨﹼﻨﺎ ﻨﺴﻤ‪‬ﻲ ﺍﻝﻘﻭﺓ‬
‫ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻋﻨﺩﺌﺫ ﺒﺎﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﺍﻝﻨﻅﺎﻤﻴﺔ ﻭﻨﺭﻤﺯ ﺇﻝﻴﻬﺎ ﺒﺎﻝﺭﻤﺯ ‪. E‬‬
‫⊖‬ ‫⊕‬
‫ﺗﻮﺗﻴﺎﺀ‬ ‫ﳓﺎﺱ‬
‫↑‬ ‫↑‬
‫‪Zn2+ + SO24−‬‬ ‫‪Cu2 + + SO24−‬‬
‫‪Zn | Zn2+‬‬ ‫‪Cu2 + | Cu‬‬
‫‪Zn → Zn2+ + 2 e−‬‬ ‫‪Cu2 + + 2 e− → Cu‬‬
‫‪Zn + Cu2 + → Zn2+ + Cu‬‬
‫ﺍﻝﺸﻜل ) ‪ : ( 4‬ﺍﻻﺘﺠﺎﻩ ﺍﻻﺼﻁﻼﺤﻲ ﻝﻠﺘﻴﺎﺭ ﻭﻝﻠﺘﻔﺎﻋل ﺍﻝﻜﻴﻤﻴﺎﺌﻲ ﻓﻲ ﺤﺎﻝﺔ ﺒﻁﺎﺭﻴﺔ ﺩﺍﻨﻴﻴل‪.‬‬
‫ﺘﺘﺤﺭﻙ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻓﻲ ﺍﺘﺠﺎﻩ ﻤﻌﺎﻜﺱ ﻝﻠﺠﻬﺔ ﺍﻻﺼﻁﻼﺤﻴﺔ ﻝﻠﺘﻴﺎﺭ ‪ i‬ﺍﻝﺫﻱ ﻴﻨﺘﻘل ﻓﻲ ﺍﻝﺩﺍﺭﺓ‬
‫ﺍﻝﺨﺎﺭﺠﻴﺔ ﻤﻥ ﺍﻝﻘﻁﺏ ⊕ ﺇﻝﻰ ﺍﻝﻘﻁﺏ ⊖ ‪.‬‬
‫‪ .3.VII‬ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ﺃﻭ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪ .1.3.VII‬ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ‬
‫ﻻ ﻓﺭﻭﻕ ﺍﻝﻜﻤﻭﻥ ﻓﻘﻁ‪ .‬ﻝﺫﻝﻙ ﻻ ﻴﻤﻜﻥ ﻗﻴﺎﺱ ﻜﻤﻭﻥ ﻤﺴﺭﻯ‬

‫ﻨﻌﻠﻡ ﺃﻨﻨﺎ ﻻ ﻨﺴﺘﻁﻴﻊ ﺃﻥ ﻨﻘﻴﺱ ﺇ ﹼ‬
‫ﻻ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ﻤﺴﺭﻯ ﻤﺭﺠﻌﻲ‪.‬‬
‫ﺇﹼ‬
‫ﻯ ﻤﺭﺠﻌﻴﹰﺎ ﻴﺴﺎﻫﻡ ﻓﻴﻪ ﺍﻝﺯﻭﺝ‬
‫ﻝﻘﺩ ﺠﺭﻯ ﺍﺨﺘﻴﺎﺭ ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ ﺒﺼﻔﺘﻪ ﻤﺴﺭ ‪‬‬
‫‪. H3O+ / H2‬‬
‫ﻴﺘﺄﻝﻑ ﻫﺫﺍ ﺍﻝﻤﺴﺭﻯ ﻤﻥ ﺼﻔﻴﺤﺔ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﺍﻝﻤﻐﻁﺎﺓ ﺒﻁﺒﻘﺔ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﺍﻹﺴﻔﻨﺠﻲ‬

‫ﻭ ﻤﻐﻤﻭﺴﺔ ﻓﻲ ﻤﺤﻠﻭل ﺤﻤﻀﻲ ﻴﺤﻘﹼﻕ ‪ pH = 0‬ﻭﻴﺴﻠﻙ ﺴﻠﻭﻙ ﻤﺤﻠﻭل ﻤﻤﺩ‪‬ﺩ ﺇﻝﻰ ﺍﻝﻼﻨﻬﺎﻴﺔ‬
‫ﺦ ﻓﻴﻪ ﻏﺎﺯ ﺜﻨﺎﺌﻲ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻋﻨﺩ ﺍﻝﻀﻐﻁ ‪ ، P = 1 bar‬ﺍﻝﺸﻜل ) ‪ . ( 5‬ﻭﻋﺎﺩﺓ ﻤﺎ ﻨﺭﻤﺯ‬
‫ﻀﹼ‬‫ﻭ ‪‬ﻴ ‪‬‬
‫ﺇﻝﻰ ﻫﺫﺍ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻤﺭﺠﻌﻲ ﺒﺎﻝﺭﻤﺯ ‪.E.S.H.‬‬
‫ل ﻤﺎ ﻨﺴﺘﻁﻴﻊ ﺍﻝﻘﻴﺎﻡ ﺒﻪ ﻫﻭ‬

‫ﺒﺎﻝﻁﺒﻊ ﻫﺫﺍ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻤﺭﺠﻌﻲ ﻏﻴﺭ ﻗﺎﺒل ﻝﻠﺘﺤﻘﻴﻕ ﻋﻤﻠﻴﺎﹰ‪ ،‬ﻭﻜ ّ‬
‫ﺘﻘﺭﻴﺏ ﻝﻬﺫﺍ ﺍﻝﻤﺴﺭﻯ‪.‬‬
‫ﺇ ﻥ‪ ‬ﺍﺴﺘﺤﺎﻝﺔ ﺘﺤﻘﻴﻕ ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ ﺘﻔﺴ‪‬ﺭ ﻝﻨﺎ ﻝﻤﺎﺫﺍ ﻨﺴﺘﻌﻴﻥ ﻋﺎﺩﺓ ﺒﻤﺴﺎﺭﻱ‬
‫ﺃﺨﺭﻯ ﻤﺭﺠﻌﻴﺔ ﻨﺴﻤﻴﻬﺎ ﺒﺎﻝﻤﺴﺎﺭﻱ ﺍﻝﻤﺭﺠﻌﻴﺔ ﺍﻝﺜﺎﻨﻭﻴﺔ‪.‬‬
‫ﻏﺎﺯ ﻫﻴﺪﺭﻭﺟﲔ‬
‫‪Pt‬‬
‫)‪(PH2 =1 bar‬‬ ‫ﺑﻼﺗﲔ‬
‫ﳏﻠﻮﻝ ‪ pH=0‬ﳑﺪ‪‬ﺩ‬
‫ﲤﺪﻳﺪﹰﺍ ﻻ‪‬ﺎﺋﻴ‪‬ﹰﺎ‬
‫ﺍﻝﺸﻜل ) ‪ : ( 5‬ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ‬
‫‪ .2.3.VII‬ﺘﻌﺭﻴﻑ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺃﻭ ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ‪:‬‬
‫ﻥ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻝﺯﻭﺝ ﻤﺅﻜﺴﺩ‪/‬ﻤﺭﺠﻊ ﺃﻭ ﻤﺎ ﻴﺴﻤ‪‬ﻰ ﺃﻴﻀﹰﺎ ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ﺃﻭ‬
‫ﺇ‪‬‬
‫ﺍﺨﺘﺼﺎﺭ ﹰﺍ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ ﻫﻭ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﺨﻠﻴﺔ ﻴﻜﻭﻥ ﻓﻴﻬﺎ ﺍﻝﻤﺴﺭﻯ‬
‫ﺍﻝﻴﺴﺎﺭﻱ ﻫﻭ ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻤﺭﺠﻌﻲ ﻭﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻤﻌﺘﺒﺭ ﻫﻭ ﺍﻝﻤﺴﺭﻯ ﺍﻝﻴﻤﻴﻨﻲ ﻭﺫﻝﻙ‬
‫ﻭﻓﻕ ﺍﻝﻤﺨﻁﻁ ﺍﻝﻤﻤﺜﹼل ﻝﻠﺨﻠﻴﺔ‪.‬‬
‫‬ ‫‪+0.74‬‬ ‫‬ ‫‪-0.79‬‬
‫ﻏﺎﺯ ﻫﻴﺪﺭﻭﺟﲔ‬ ‫ﻏﺎﺯ ﻫﻴﺪﺭﻭﺟﲔ‬

‫)‪(PH2 =1 bar‬‬ ‫‪COM‬‬ ‫‪V‬‬ ‫)‪(PH2 =1 bar‬‬ ‫‪COM‬‬ ‫‪V‬‬
‫ﻣﺴﺮﻯ ﺑﻼﺗﲔ‬ ‫ﻣﺴﺮﻯ ﻓﻀ‪‬ﺔ‬ ‫ﻣﺴﺮﻯ ﺑﻼﺗﲔ‬ ‫ﻣﺴﺮﻯ ﺗﻮﺗﻴﺎﺀ‬
‫ﳏﻠﻮﻝ ‪pH=0‬‬ ‫ﳏﻠﻮﻝ ﻧﺘﺮﺍﺕ ﺍﻟﻔﻀ‪‬ﺔ‬ ‫ﳏﻠﻮﻝ ‪pH=0‬‬ ‫ﳏﻠﻮﻝ ﻛﱪﻳﺘﺎﺕ ﺍﻟﺘﻮﺗﻴﺎﺀ‬
‫ﺍﻝﺸﻜل ) ‪ : ( 6‬ﺘﺒﻌﹰﺎ ﻝﻁﺒﻴﻌﺔ ﺍﻝﻘﻁﺏ ﺍﻝﻤﺘﺸﻜﹼل ﻋﻨﺩ ﻤﺴﺭﻯ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻤﺼﺎﺤﺒﺔ ﻝﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ‬
‫ﻥ )‪ E (Ox/Red‬ﺘﻜﻭﻥ ﻤﻭﺠﺒﺔ ﺃﻭ ﺴﺎﻝﺒﺔ ‪.‬‬
‫ﺍﻝﻨﻅﺎﻤﻲ‪ ،‬ﻓﺈ ‪‬‬
‫ﻥ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ ﺍﻝﻤﻌﺭ‪‬ﻑ ﺒﻬﺫﻩ ﺍﻝﻁﺭﻴﻘﺔ ﻫﻭ ﻜﻤﻭﻥ ﻨﺴﺒﻲ ﻤﺭﺘﺒﻁ ﺒﻜﻤﻭﻥ‬
‫ﺇ‪‬‬
‫ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ‪ .‬ﻓﺈﺫﺍ ﻜﺎﻨﺕ ﺍﻝﻌﻨﺎﺼﺭ ﺍﻝﻤﺸﻜﹼﻠﺔ ﻝﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻴﻤﻴﻨﻲ ﻤﺄﺨﻭﺫﺓ ﻓﻲ‬
‫ﻻ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ‬
‫ﻥ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﺨﻠﻴﺔ ﻤﺎ ﻫﻲ ﺇ ﹼ‬
‫ﺤﺎﻝﺘﻬﺎ ﺍﻝﻤﻌﻴﺎﺭﻴﺔ ﻓﺈ ‪‬‬
‫ﺍ ﻝﻨﻅﺎ ﻤﻲ ﻝﻠﺯ ﻭ ﺝ ‪ Ox/Red‬ﺍ ﻝﻤﻌﺘﺒﺭ ﻋﻨﺩ ﺩ ﺭ ﺠﺔ ﺍ ﻝﺤﺭ ﺍ ﺭ ﺓ ﺍ ﻝﻤﻘﺎ ﺱ ﻓﻴﻬﺎ ﻭ ﻨﺭ ﻤﺯ ﺇ ﻝﻴﻪ‬
‫)‪ . E (Ox/Red‬ﻭ ﻫﻜﺫ ﺍ ﻨﻜﺘﺏ‪ E (Cu2+ /Cu) = 0.34 V :‬ﻋﻨﺩ ﺩ ﺭ ﺠﺔ ﺍ ﻝﺤﺭ ﺍ ﺭﺓ‬
‫‪. 25 C‬‬
‫ﻥ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ ﻝﻠﺯﻭﺝ ‪ H3O+/H2‬ﻋﻨﺩ‬
‫ﻭﻤﻥ ﺍﻝﺘﻌﺭﻴﻑ ﺍﻝﺴﺎﺒﻕ ﻨﺴﺘﻨﺘﺞ ﺃ ‪‬‬
‫ﻜ ّل ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﻫﻭ‪E (H 3O+ /H2 ) = 0 V :‬‬
‫ﻝﻨﺄﺨﺫ ﻨﺼﻑ ﺨﻠﻴﺔ ﻴﺴﺎﻫﻡ ﻓﻴﻬﺎ ﺍﻝﺯﻭﺝ ‪ Ox/Red‬ﻭﻝﻨﺭﺒﻁ ﺒﻬﺎ ﻨﺼﻑ ﺨﻠﻴﺔ ﺃﺨﺭﻯ ﺘﻀ ‪‬ﻡ‬
‫ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ ﻋﻠﻰ ﺃﻥ ﻴﻜﻭﻥ ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻫﻭ ﺍﻝﻴﺴﺎﺭﻱ‪.‬‬
‫ﻼ ﺍﻝﻘﻁﺏ ﺍﻝﻤﻭﺠﺏ ﻝﻠﺨﻠﻴﺔ ) ﺃﻱ ﻤﻬﺒﻁﹰﺎ‬
‫ ﻓﺈﺫﺍ ﻜﺎﻥ ﻤﺴﺭﻯ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻤﺩﺭﻭﺱ ﻫﻭ ﻓﻌ ﹰ‬
‫ﻭﻴﺤﺼل ﻋﻨﺩﻩ ﺘﻔﺎﻋل ﺇﺭﺠﺎﻉ ( ﻜﺎﻥ ‪ ، E (Ox/Red) > 0‬ﺍﻝﺸﻜل )‪.(6-‬‬
‫ ﻭﺇﺫﺍ ﻜﺎﻥ ﻤﺴﺭﻯ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻤﺩﺭﻭﺱ ﻫﻭ ﺍﻝﻘﻁﺏ ﺍﻝﺴﺎﻝﺏ ﻝﻠﺨﻠﻴﺔ ) ﺃﻱ ﻤﺼﻌﺩﹰﺍ‬
‫ﻭﻴﺤﺼل ﻋﻨﺩﻩ ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ( ﻜﺎﻥ ‪ ، E (Ox/Red) < 0‬ﺍﻝﺸﻜل )‪.(6-‬‬
‫

‬ ‫ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ‪fuel cells‬‬
‫ﻼ ﻓﻲ ﺍﻝﺴﻴﺎﺭﺓ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ‪ ،‬ﻭﻝﻜﻥ‬

‫ﻝﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺘﻁﺒﻴﻘﺎﺕ ﻭﺍﻋﺩﺓ ﻓﻲ ﺘﺄﻤﻴﻥ ﻤﺼﺩﺭ ﻝﻠﻁﺎﻗﺔ ﺍﻝﻨﻅﻴﻔﺔ ﻻﺴﺘﻌﻤﺎﻝﻬﺎ ﻤﺜ ﹰ‬
‫ل ﺒﻌﺽ ﺍﻝﻤﺸﺎﻜل ﺍﻝﺘﻘﻨﻴﺔ ﺍﻝﻤﺘﻌﻠﻘﺔ ﺒﺘﺨﺯﻴﻥ ﺍﻝﻭﻗﻭﺩ ﺍﻝﻼﺯﻡ ﻝﺘﺸﻐﻴﻠﻬﺎ‪ .‬ﺘﺴﺘﻌﻤل‬
‫ﺍﻷﺒﺤﺎﺙ ﻤﺎﺯﺍﻝﺕ ﻗﺎﺌﻤﺔ ﺤﺘﻰ ﺍﻵﻥ ﻝﺤ ّ‬
‫ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺤﺎﻝﻴﹰﺎ ﻓﻲ ﺘﺄﻤﻴﻥ ﺍﻝﻜﻬﺭﺒﺎﺀ ﻭﺍﻝﻤﺎﺀ ﻝﻤﺭﻜﺒﺎﺕ ﺍﻝﻔﻀﺎﺀ‪ ،‬ﺤﻴﺙ ﺘﻀ ‪‬ﻡ ﺍﻝﻤﺭﻜﺒﺔ ﺍﻝﻔﻀﺎﺌﻴﺔ ﺜﻼﺙ ﺨﻼﻴﺎ ﻭﻗﻭﺩ‬
‫ل ﻤﻨﻬﺎ ﻨﺤﻭ ﻤﺌﺔ ﻜﻴﻠﻭﻏﺭﺍﻡ‪ ،‬ﻭﺃﺒﻌﺎﺩﻫﺎ ﺒﺤﺩﻭﺩ ‪100 × 40 × 35 cm 3‬‬
‫ﺘﻭﻀﻊ ﻓﻲ ﺍﻝﺠﺯﺀ ﺍﻝﻤﺨﺼﺹ ﻝﻠﺸﺤﻥ‪ .‬ﺘﺯﻥ ﻜ ّ‬
‫‪.‬‬
‫ﺘﻴﺎﺭ ﻜﻬﺭﺒﺎﺌﻲ‬
‫‪e−‬‬
‫‪−‬‬
‫ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﺩﺍﺨل‬ ‫‪e‬‬ ‫ﺍﻷﻭﻜﺴﺠﻴﻥ ﺍﻝﺩﺍﺨل‬
‫‪−‬‬
‫‪H2‬‬ ‫‪e‬‬ ‫‪O2‬‬
‫‪e−‬‬
‫‪e−‬‬
‫‪−‬‬
‫‪OH− e‬‬
‫‪H 2O‬‬ ‫‪e−‬‬
‫‪e−‬‬ ‫‪e−‬‬
‫ﻤﺎﺀ ﻭﺤﺭﺍﺭﺓ‬
‫‪e−‬‬ ‫‪e−‬‬
‫ﻤﺼﻌﺩ‬ ‫ﻜﻬﺭﻝﻴﺕ‬ ‫ﻤﻬﺒﻁ‬
‫ﻭﻤﺜﻠﻬﺎ ﻤﺜل ﺃﻱ ﺒﻁﺎﺭﻴﺔ ﻋﺎﺩﻴﺔ ﻓﺈﻥ ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺘﺤﻭ‪‬ل ﺍﻝﻁﺎﻗﺔ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻝﻨﺎﺠﻤﺔ ﻋﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺇﻝﻰ‬
‫ﻻ ﺃﻨﻪ ﻭﻋﻠﻰ ﻋﻜﺱ ﺍﻝﺒﻁﺎﺭﻴﺔ ﺍﻝﻌﺎﺩﻴﺔ ﺍﻝﺘﻲ ﺘﺘﻭﻗﹼﻑ ﻋﻥ ﺍﻝﻌﻤل ﻋﻨﺩﻤﺎ ﺘﹸﺴﺘﻬﻠﹶﻙ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﺍﻝﻤﻜﻭ‪‬ﻨﺔ ﻝﻬﺎ‪،‬‬
‫ﻜﻬﺭﺒﺎﺀ‪ .‬ﺇ ﹼ‬
‫ﻥ ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺘﺴﺘﻤﺭ ﻓﻲ ﺍﻝﻌﻤل ﻤﺎ ﺩﺍﻤﺕ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﺘﹸﻀﺎﻑ ﺇﻝﻴﻬﺎ ﻤﻥ ﺍﻝﺨﺎﺭﺝ‪ .‬ﻭﻴﺘﺸﻜﹼل ﺒﺨﺎﺭ ﺍﻝﻤﺎﺀ‬
‫ﻓﺈ ‪‬‬
‫ﺒﺎﻋﺘﺒﺎﺭﻩ ﺃﺤﺩ ﺍﻝﻨﻭﺍﺘﺞ ﺍﻝﺜﺎﻨﻭﻴﺔ ﻤﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺍﻝﺘﻲ ﺘﺠﺭﻱ ﻓﻲ ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ‪ ،‬ﺤﻴﺙ ﻴﺠﺭﻱ ﺘﻜﺜﻴﻔﻪ ﻭﺤﻔﻅﻪ‪.‬‬
‫ﻓﻲ ﺨﻠﻴﺔ ﺍﻝﻭﻗﻭﺩ ﺍﻝﻤﺴﺘﻌﻤﻠﺔ ﻓﻲ ﺍﻝﻤﺭﻜﺒﺔ ﺍﻝﻔﻀﺎﺌﻴﺔ‪ ،‬ﺘﺘﻭﻝﹼﺩ ﺍﻝﻜﻬﺭﺒﺎﺀ ﻨﺘﻴﺠﺔ ﻝﻨﺼﻔﻲ ﺍﻝﺘﻔﺎﻋل ﺍﻹﻝﻜﺘﺭﻭﻨﻴﻴﻥ ﺍﻝﻠﺫﻴﻥ ﻴﺠﺭﻴﺎﻥ‬
‫ﻓﻲ ﺍﻝﻭﻗﺕ ﺫﺍﺘﻪ ﺒﺎﻝﻘﺭﺏ ﻤﻥ ﺍﻝﻤﺼﻌﺩ ﻭﺍﻝﻤﻬﺒﻁ‪.‬‬
‫‪‬ﻴﺯ ‪‬ﻭﺩ ﺍﻝﻤﺼﻌﺩ ﺒﻐﺎﺯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ‪ ، H2‬ﻓﻲ ﺤﻴﻥ ﻴﺠﺭﻱ ﺘﺯﻭﻴﺩ ﺍﻝﻤﻬﺒﻁ ﺒﻐﺎﺯ ﺍﻷﻜﺴﺠﻴﻥ ‪. O2‬‬
‫ﺒﺠﻭﺍﺭ ﺍﻝﻤﺼﻌﺩ‪ ،‬ﻴﺘﻔﺎﻋل ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ )ﺍﻝﻘﺎﺩﻤﺔ ﻤﻥ ﺍﻝﻤﻬﺒﻁ( ﻝﻴﺸﻜﹼل ﺍﻝﻤﺎﺀ ﻭﺇﻝﻜﺘﺭﻭﻨﺎﺕ‪:‬‬
‫‪H2 + 2 OH− → 2 H2O + 2 e−‬‬
‫

‬
‫ﺒﺠﻭﺍﺭ ﺍﻝﻤﻬﺒﻁ‪ ،‬ﻴﺘﻔﺎﻋل ﺍﻷﻜﺴﺠﻴﻥ ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻝﻴﺸﻜﹼل ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪:‬‬
‫‪O2 + 2 H2O + 4 e− → 4 OH−‬‬
‫ﺘﺘﺤﺭ‪‬ﻙ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﻤﺘﺸﻜﹼﻠﺔ ﺒﺎﺘﺠﺎﻩ ﺍﻝﻤﺼﻌﺩ ﻭﺘﺘﻜﺭ‪‬ﺭ ﻤﻥ ﺠﺩﻴﺩ ﺴﻠﺴﻠﺔ ﺍﻝﺘﻔﺎﻋﻼﺕ‪ .‬ﺘﹸﻘﺎﺩ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ‬
‫ﺍﻝﻤﺘﻭﻝﺩﺓ ﻋﻨﺩ ﺍﻝﻤﺼﻌﺩ ﻀﻤﻥ ﺩﺍﺭﺓ ﻜﻬﺭﺒﺎﺌﻴﺔ ﺘﻐﺫﹼﻱ ﺍﻝﻤﺭﻜﺒﺔ ﺍﻝﻔﻀﺎﺌﻴﺔ‪.‬‬
‫ﻭﻝﻭﺤﺎﻭﻝﻨﺎ ﻜﺘﺎﺒﺔ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﺒﺩﺀﹰﺍ ﻤﻥ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﻨﺼﻔﻴﺘﻴﻥ ﻝﻭﺠﺩﻨﺎ‪:‬‬
‫‪2 H2 + O2 → 2 H2O‬‬
‫ﻑ ﻝﺘﺯﻭﻴﺩ ﺭﻭﺍﺩ ﺍﻝﻔﻀﺎﺀ ﺒﺤﺎﺠﺘﻬﻡ‬
‫ﻭﺘﻭﻝﹼﺩ ﺨﻼﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺍﻝﺜﻼﺙ ﺤﻭﺍﻝﻲ ‪ 11 kg‬ﺒﺎﻝﺴﺎﻋﺔ ﻤﻥ ﺍﻝﻤﺎﺀ ﻭﻫﺫﺍ ﺃﻜﺜﺭ ﻤﻥ ﻜﺎ ‪‬‬
‫ﻤﻥ ﺍﻝﻤﺎﺀ‪.‬‬
‫
‬
‫ﺍﻜﺘﺏ ﺼﻴﻐﺔ ﻝﻭﻴﺱ ﻝﻠﺸﻭﺍﺭﺩ ﺍﻝﺘﺎﻝﻴﺔ ﺒﻌﺩ ﺘﺴﻤﻴﺘﻬﺎ ﺜﻡ ﺍﺴﺘﻨﺘﺞ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ﻝﻠﻌﻨﺎﺼﺭ ﺍﻝﻤﺸﻜﱢﻠﺔ‬ ‫‬
‫‪، NO−‬‬
‫‪ ، ClO‬ﺍﻝﻜﻠﻭﺭﺍﺕ ‪ ، Cl O3‬ﺍﻝﻨﺘﺭﻴﺕ ‪ ، NO2‬ﺍﻝﻨﺘﺭﺍﺕ ‪3‬‬
‫‪−‬‬ ‫‪−‬‬ ‫‪−‬‬
‫ﻝﻬﺎ‪ :‬ﻫﻴﺒﻭﻜﻠﻭﺭﻴﺕ‬
‫ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪ ، Mn O−4‬ﺍﻝﻤﻨﻐﻨﺎﺕ ‪ ، Mn O24−‬ﺍﻝﻔﻭﺴﻔﺎﺕ ‪. PO34−‬‬
‫ﺃﺯﻭﺍﺝ ﺍﻝﻜﺭﻭﻡ‪.‬‬ ‫‬

‫ﺃﻭﺠﺩ ﺼﻴﻐﺔ ﻝﻭﻴﺱ ﻝﺸﺎﺭﺩﺓ ﺍﻝﻜﺭﻭﻤﺎﺕ ‪ Cr O24−‬ﻭﺸﺎﺭﺩﺓ ﺜﻨﺎﺌﻲ ﺍﻝﻜﺭﻭﻤـﺎﺕ ‪Cr2 O27−‬‬
‫ﻥ ﺘﺘﺎﻝﻲ ﺍﻝﺫﺭﺍﺕ ﻓﻴﻬﺎ ﻤﻤﺜﹼل ﺒﺎﻝﺼﻴﻐﺔ ‪. (O3 Cr OCr O3 )2− :‬‬
‫ل ﻤﻥ ﺍﻷﺯﻭﺍﺝ ‪ Cr2 O72−/Cr3 +‬ﻭ ‪. Cr2 O72− / Cr O24−‬‬
‫ﺤﺩ‪‬ﺩ ﻨﻭﻉ ﻜ ﱟ‬
‫ﻭﺍﺯﻥ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ ‪:‬‬ ‫‬

‫‪Cl O−4 + I− → H I O+ Cl−‬‬ ‫‬
‫‪Cl O− + Fe ( OH )2 → Cl− + Fe ( OH )3‬‬ ‫‬
‫ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻨﺼﻔﻴﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﻸﺯﻭﺍﺝ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬ ‫‬

‫] ‪. [Pt Cl 4‬‬
‫‪2−‬‬
‫‪ Zn‬ﻭ )‪ Hg Cl2 (s)/ Hg (L‬ﻭ )‪/ Pt (s‬‬ ‫‪2+‬‬
‫)‪/ Zn (s‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺴﺎﺑﻊ‬
‫ ‪Nernst -‬‬
‫ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‬ ‫‪.I‬‬

‫‪ .1.I‬ﻋﺭﺽ ﺍﻝﻌﻼﻗﺔ‬
‫‪ .2.I‬ﺃﻤﺜﻠﺔ ﻋﻥ ﺍﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‬
‫‪ .3.I‬ﺃﻨﻭﺍﻉ ﺍﻝﻤﺴﺎﺭﻱ‬
‫‪ .II‬ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪ .1.II‬ﺴﻠﻭﻙ ﺠﻤﻠﺔ‬
‫‪ .2.II‬ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ ﻝﺘﻁﻭﺭ ﺠﻤﻠﺔ ‪ -‬ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‬
‫‪ .3.II‬ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪ -‬ﺘﻁﺒﻴﻕ‬
‫‪ .4.II‬ﺘﻌﻴﻴﻥ )‪E (Ox/Red‬‬
‫‪ .III‬ﻤﻨﺎﻁﻕ ﺍﻝﻭﺠﻭﺩ ﻭﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ‬
‫‪ .1.III‬ﺘﻌﺎﺭﻴﻑ‬
‫‪ .2.III‬ﺘﻁﺒﻴﻘﺎﺕ‬
‫‪ .IV‬ﺍﻝﻌﻭﺍﻤل ﺍﻝﻤﺅﺜﹼﺭﺓ ﻋﻠﻰ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪ .1.IV‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﺭﻜﻴﺯ‬
‫‪ .2.IV‬ﺘﺄﺜﻴﺭ ﺍﻝـ ‪pH‬‬
‫‪ .3.IV‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﻌﻘﻴﺩ ﻭﺍﻝﺘﺭﺴﻴﺏ‬
‫‪225‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺴﺎﺑﻊ‬ ‫‪226‬‬
‫‪ .I‬ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‬
‫‪ .1.I‬ﻋﺭﺽ ﺍﻝﻌﻼﻗﺔ‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺍﻝﻤﻌﺭ‪‬ﻓﺔ ﻭﻓﻕ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ‪:‬‬

‫‪Pt‬‬ ‫)‪H2(g‬‬ ‫‪H3O+ ⋮⋮ Ox, Red‬‬ ‫‪Pt‬‬
‫ﺍﻝﻨﺎﺸﺌﺔ ﻋﻥ ﺍﺠﺘﻤﺎﻉ ﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪ -‬ﻤﺴﺭﻯ ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻨﻅﺎﻤﻲ ‪ P(H2 ) = 1 bar‬ﻭ ‪. pH = 0‬‬
‫‪ -‬ﻤﺴﺭﻯ ﻴﺴﺎﻫﻡ ﻓﻴﻪ ﺍﻝﺯﻭﺝ ‪ Ox/Red‬ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ‪:‬‬
‫‪α Ox + n e− ⇌ β Red‬‬
‫ﻥ ﺍ ﻝﻘﻭ ﺓ ﺍ ﻝﻤﺤ ‪‬ﺭ ﻜﺔ ﺍ ﻝﻜﻬﺭ ﺒﺎ ﺌﻴﺔ ﻝﻬﺫ ﻩ ﺍ ﻝﺨﻠﻴﺔ‬
‫ﻝﻤﹼﺎ ﻜﺎ ﻥ ‪ E (H3O+/H2 ) = 0 V‬ﻓﺈ ‪‬‬
‫ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺘﺴﺎﻭﻱ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ ﻝﻠﺯﻭﺝ ‪ Ox/Red‬ﺍﻝﻤﺩﺭﻭﺱ‪ .‬ﻭ ﺘﹸﻌﻁﻰ ﻗﻴﻤﺔ ﻫﺫﺍ‬
‫ﺍﻝﻜﻤﻭﻥ ﺒﻌﻼﻗﺔ ﺘﹸﻌﺭﻑ ﺒﺎﺴﻡ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ‪ Nernst‬ﻭﻫﻲ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪RT‬‬ ‫‪(a(Ox))α‬‬
‫‪E (Ox/Red) = E (Ox/Red) +‬‬ ‫‪ln‬‬
‫‪nF (a(Red))β‬‬
‫ﺤﻴﺙ‪:‬‬
‫)‪ : E (Ox/Red‬ﻫﻭ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻨﻅﺎﻤﻲ ﻝﻠﺯﻭﺝ ﺍﻝﻤﻌﺘﺒ‪‬ﺭ ﻋﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪.T‬‬ ‫‬
‫ ‪ : R‬ﻫﻭ ﺜﺎﺒﺕ ﺍﻝﻐﺎﺯﺍﺕ ﺍﻝﻤﺜﺎﻝﻴﺔ‪R = 8.314 J.K -1.mol−1 :‬‬
‫‪ :T‬ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ﺒﺎﻝﻜﻴﻠﻔﻥ ‪. K‬‬ ‫‬
‫‪ : F‬ﺜﺎﺒﺕ ﻓﺎﺭﺍﺩﺍﻱ ‪F = 96500 C.mol−1 :‬‬ ‫‬
‫ )‪ a(Ox‬ﻭ )‪ a(Red‬ﻴﻤﺜﹼﻼﻥ ﻓﻌﺎﻝﻴ‪‬ﺔ ﺍﻝﻨﻭﻋﻴﻥ ‪ Ox‬ﻭ ‪ ، Red‬ﻭﻫﻨﺎ ﻤﻥ ﺍﻝﻤﻔﻴﺩ ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ‬
‫ﻥ )‪ a(Ox‬ﻭ )‪ a(Red‬ﻫﻤﺎ ﻤﻘﺩﺍﺭﺍﻥ ﻻ ﻭﺍﺤﺩﺓ ﻝﻬﻤﺎ‪ ،‬ﻭﺘﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ﻫﺫﻩ ﺍﻝﻔﻌﺎﻝﻴﺎﺕ ﺘﺒﻌ ﹰﺎ‬
‫ﺃ‪‬‬
‫ﻝﻁﺒﻴﻌﺔ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺅﻜﺴﺩﺓ ﻭﺍﻝﻤﺭﺠﻌﺔ ﻭﻓﻕ ﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪ å‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺫﻴﺏ‪ ،‬ﻭﻫﻭ ﻫﻨﺎ ﺍﻝﻤﺎﺀ ‪. a(H2O) = 1‬‬
‫‪ å‬ﻓﻲ ﺤﺎﻝﺔ ﺠﺴﻡ ﺼﻠﺏ ‪ X‬ﺃﻭ ﺴﺎﺌل ‪ X‬ﻭﺤﻴﺩ ﻓﻲ ﻁﻭﺭﻩ‪. a (X ) = 1 ،‬‬
‫‪ å‬ﻓﻲ ﺤﺎﻝﺔ ﻏﺎﺯ ‪ X‬ﻴﺴﻠﻙ ﺴﻠﻭﻙ ﺍﻝﻐﺎﺯ ﺍﻝﻤﺜﺎﻝﻲ‪،‬‬
‫) ‪P (X‬‬
‫= ) ‪a (X‬‬ ‫‪P‬‬
‫ﺤﻴﺙ ‪. P = 1 bar‬‬
‫‪227‬‬ ‫ﻋﻼﻗﺔ ﻧﺮﻧﺴﺖ‬
‫‪ å‬ﻓﻲ ﺤﺎﻝﺔ ﻤﺎﺩﺓ ﻤﻨﺤﻠﹼﺔ ﻭﻤﻤﺩ‪‬ﺩﺓ ‪ a (X ) = [CX ] ، X‬ﺤﻴﺙ ‪.C = 1 mol/L‬‬

‫ﻭﻋﻨﺩﻤﺎ ﺘﻀ ‪‬ﻡ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺼﻔﻴﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻤﺭﻜﺒﺎﺕ ﺇﻀﺎﻓﻴﺔ ﻏﻴﺭ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺅﻜﺴﺩﺓ‬
‫ﻭﺍﻝﻤﺭﺠﻌﺔ‪ ،‬ﻓﻴﻨﺒﻐﻲ ﺃﻥ ﺘﻅﻬﺭ ﺃﻴﻀﹰﺎ ﻓﻲ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻜﻤﺎ ﺴﻨﺭﻯ ﻻﺤﻘﹰﺎ‪.‬‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﻭﻨﻅﺭﹰﺍ ﻝﻘﻠﺔ ﺍﺴﺘﻌﻤﺎل ﺍﻝﻠﻭﻏﺎﺭﻴﺘﻡ ﺍﻝﻨﻴﺒﺭﻱ ﻭﻜﺜﺭﺓ ﺍﺴﺘﻌﻤﺎل ﺍﻝﻠﻭﻏﺎﺭﻴﺘﻡ‬
‫ﺍﻝﻌﺸﺭﻱ ﻓﻲ ﺍﻝﻜﻴﻤﻴﺎﺀ‪ ،‬ﻨﻌﻴﺩ ﺼﻴﺎﻏﺔ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪RT‬‬ ‫‪(a(Ox))α‬‬
‫‪E (Ox/Red) = E (Ox/Red) +‬‬ ‫‪ln(10) ⋅ log‬‬
‫‪nF‬‬ ‫‪(a(Red))β‬‬
‫ﻭﻋﻨﺩ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﻐﺭﻓﺔ ‪ T = 298K = 25 C‬ﻴﺼﺒﺢ ﻝﺩﻴﻨﺎ‬

‫‪RT‬‬ ‫‪8.314 × 298‬‬
‫= )‪ln(10‬‬ ‫‪× 2.303 ≈ 0.05916 V‬‬
‫‪F‬‬ ‫‪96500‬‬
‫ﻥ ﻗﻴﻡ )‪ E (Ox/Red‬ﺘﹸﻌﻁﻰ ﻋﺎﺩﺓ‬

‫ﻨﻅﺭﹰﺍ ﺇﻝﻰ ﺃ ‪‬‬ ‫‪RT‬‬
‫‪F‬‬ ‫ﻨﻜﺘﻔﻲ ﺒﺎﻝﺘﻘﺭﻴﺏ ‪ln(10) ≈ 0.06 V‬‬
‫ﺒﺭﻗﻤﻴﻥ ﻤﻌﻨﻭﻴﻴﻥ‪ .‬ﻭﻨﺼل ﺇﻝﻰ ﺍﻝﺼﻴﻐﺔ ﺍﻝﺘﺎﻝﻴﺔ ﻝﻌﻼﻗﺔ ﻨﺭﻨﺴﺕ ‪:‬‬
‫‪0.06‬‬ ‫‪(a(Ox))α‬‬
‫‪E ( Ox/Red ) = E ( Ox/Red ) +‬‬ ‫‪log‬‬
‫‪n‬‬ ‫‪(a(Red))β‬‬
‫‪ .2.I‬ﺃﻤﺜﻠﺔ ﻋﻠﻰ ﺍﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‬
‫‪. Fe3 +/Fe2 +‬‬ ‫ ﺍﻝﺯﻭﺝ‬

‫‪Fe3+ + e− ⇌ Fe2 +‬‬
‫‪ [Fe3 + ] ‬‬
‫‪E (Fe3 + /Fe2+ ) = E (Fe3 + /Fe2+ ) + 0.06 log ‬‬ ‫‪‬‬
‫‪ [Fe2 + ] ‬‬
‫‪. Cu 2+/Cu‬‬ ‫ ﺍﻝﺯﻭﺝ‬

‫)‪Cu2 + + 2e − ⇌ Cu(s‬‬
‫‪ [Cu2 + ] ‬‬
‫‪E (Cu2+ /Cu) = E (Cu2+ /Cu) + 0.03 log ‬‬ ‫‪‬‬
‫‪ 1 ‬‬
‫ ﺍﻝﺯﻭﺝ ‪. Cl2/Cl−‬‬
‫‪Cl2( g )+ 2 e− ⇌ 2 Cl−‬‬
‫‪ P (Cl ) ‬‬
‫‪E (Cl2 /Cl− ) = E (Cl2 /Cl− ) + 0.03 log ‬‬ ‫‪2 ‬‬
‫‪ [Cl - ]2 ‬‬
‫‪. H3O+/H2‬‬ ‫ ﺍﻝﺯﻭﺝ‬

‫‪2H 3O+ + 2e− ⇌ H2 + 2H2O‬‬
‫‪0.06‬‬ ‫‪ [H O+ ]2 ‬‬
‫‪E (H 3O+ /H2 ) = E (H 3O+ /H2 ) +‬‬ ‫‪log  3‬‬ ‫‪‬‬
‫‪2‬‬ ‫‪ P (H2 ) ‬‬
‫‪ [H O+ ]2 ‬‬
‫‪= 0.03 log  3‬‬ ‫‪‬‬
‫‪ P (H2 ) ‬‬
‫‪. Mn O−‬‬
‫‪4 /Mn‬‬
‫‪2+‬‬
‫ ﺍﻝﺯﻭﺝ‬
‫‪Mn O−‬‬ ‫‪−‬‬ ‫‪+‬‬ ‫‪2+‬‬
‫‪4 + 5 e + 8 H 3 O ⇌ Mn + 12 H2 O‬‬
‫‪0.06‬‬ ‫‪ [Mn O− ][H O+ ]8 ‬‬

‫‪E ( Mn O−‬‬ ‫‪/Mn‬‬ ‫‪2+‬‬
‫)‬ ‫=‬ ‫‪E‬‬ ‫‬
‫(‬ ‫‪Mn‬‬ ‫‪O‬‬‫‪−‬‬
‫‪/Mn‬‬ ‫‪2+‬‬
‫)‬ ‫‪+‬‬ ‫‪log‬‬ ‫‪‬‬ ‫‪4‬‬ ‫‪3‬‬ ‫‪‬‬
‫‪4‬‬ ‫‪4‬‬
‫‪5‬‬ ‫‪‬‬ ‫‪2+‬‬ ‫‪‬‬
‫‪‬‬ ‫] ‪[Mn‬‬
‫‪ .3.I‬ﺃﻨﻭﺍﻉ ﺍﻝﻤﺴﺎﺭﻱ‬
‫ﻨﻤ‪‬ﻴﺯ ﺜﻼﺜﺔ ﺃﻨﻭﺍﻉ ﻤﻥ ﺍﻝﻤﺴﺎﺭﻱ ﻭﺫﻝﻙ ﺘﺒﻌﹰﺎ ﻝﻁﺒﻴﻌﺔ ﺍﻝﻨﺎﻗل ﺍﻝﻤﻌﺩﻨﻲ ﻭﻁﺒﻴﻌﺔ ﺍﻷﻨﻭﺍﻉ‬
‫ﺍﻝﻤﺅﻜﺴﺩﺓ ﻭﺍﻝﻤﺭﺠﻌﺔ ﺍﻝﻤﺩﺭﻭﺴﺔ‪.‬‬
‫ ﻤﺴﺎﺭﻱ ﺍﻝﻨﻭﻉ ﺍﻷﻭل‬
‫ﻨﻘﺼﺩ ﺒﻬﺫﻩ ﺍﻝﺘﺴﻤﻴﺔ ﻭﺍﺤﺩﹰﺍ ﻤﻤﺎ ﻴﻠﻲ ‪:‬‬

‫ ﻤﻌﺩﻥ ﻤﻐﻤﻭﺱ ﻓﻲ ﻤﺤﻠﻭل ﻴﻀﻡ ﺃﺤﺩ ﺸﻭﺍﺭﺩﻩ ﺒﺤﻴﺙ ﻴﺘﺸﻜﱢل ﻝﺩﻴﻨﺎ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ‬
‫‪ ، Mn + / M‬ﻤﺜل ﺼﻔﻴﺤﺔ ﻤﻥ ﺍﻝﻨﺤﺎﺱ ﻤﻐﻤﻭﺴﺔ ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻨﺤﺎﺱ‪.‬‬
‫ ﺼﻔﻴﺤﺔ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﻤﻐﻁﹼﺎﺓ ﺒﺎﻝﺒﻼﺘﻴﻥ ﺍﻝﺤﺒﻴﺒﻲ ﻭﻤﻐﻤﻭﺴﺔ ﻓﻲ ﻤﺤﻠﻭل ﻴﻀ ‪‬ﻡ ﺃﺤﺩ ﺍﻝﻨﻭﻋﻴﻥ‬
‫ﺦ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫‪ Ox‬ﺃﻭ ‪ Red‬ﻤﻥ ﺯﻭﺝ ﻤﺅﻜﺴﺩ‪ -‬ﻤﺭﺠﻊ‪ ،‬ﻭﺍﻝﺸﻜل ﺍﻵﺨﺭ ﻫﻭ ﻏﺎﺯ ﻴ‪‬ﻀ ﹼ‬
‫ﻜﻤﺎ ﻫﻭ ﺍﻝﺤﺎل ﻓﻲ ﻤﺴﺭﻯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ‪.‬‬
‫ ﻤﺴﺎﺭﻱ ﺍﻝﻨﻭﻉ ﺍﻝﺜﺎﻨﻲ‬

‫ﻴﺘﺄﻝﹼﻑ ﻫﺫ ﺍﻝﻤﺴﺭﻯ ﻤﻥ ﻤﻌﺩﻥ ﻓﻲ ﺘﻤﺎﺱ ﻤﻊ ﻤﺭﻜﱠﺏ ﺸﺎﺭﺩﻱ ﻀﻌﻴﻑ ﺍﻻﻨﺤﻼل ﻴﻀﻡ ﺃﺤﺩ‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻤﻌﺩﻥ ﺒﺤﻴﺙ ﻴﺘﺸﻜﹼل ﻝﺩﻴﻨﺎ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ‪.C x Ay /C‬‬
‫ﻭﻤﺜﺎل ﻋﻠﻰ ﺫﻝﻙ ﻫﻭ ﻤﺴﺭﻯ ﺍﻝﻜﺎﻝﻭﻤﻴل ) ‪: Hg2 Cl2/Hg ( calomel electrode‬‬
‫‪Hg 2 Cl2(s) + 2 e− ⇌ 2 Hg( ℓ )+ 2 Cl−‬‬
‫ﺤﻴﺙ ‪ Hg 2Cl2‬ﺼﻠﺏ‪ ،‬ﻭ ‪ Hg‬ﺴﺎﺌل ﻨﻘﻲ‪ ،‬ﻭﺘﻜﺘﺏ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪1‬‬
‫‪Ecal ( Hg 2 Cl2/Hg) = E ( Hg 2 Cl2/Hg) + 0.03 log − 2‬‬
‫] ‪[Cl‬‬
‫ﻓﺈﺫﺍ ﻜﺎﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪ Cl−‬ﺜﺎﺒﺘﺎﹰ‪ ،‬ﻜﺎﻥ ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ ﺜﺎﺒﺘﹰﺎ ‪ Ecal = cte‬ﻭﻫﺫﺍ ﻤﺎ ﻴﻔﺴ‪‬ﺭ‬
‫ﻯ ﻤﺭﺠﻌﻴﹰﺎ ﺜﺎﻨﻭﻴﹰﺎ‪ ،‬ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪: ( 1‬‬
‫ﺍﺴﺘﻌﻤﺎﻝﻪ ﺒﺼﻔﺘﻪ ﻤﺴﺭ ‪‬‬
‫ﺭﺃﺱ ﻋﺎﺯﻝ‬
‫ﺳﺪ‪‬ﺍﺩﺓ‬
‫ﻓﺘﺤﺔ ﺍﳌﻞﺀ‬
‫ﺳﺪ‪‬ﺍﺩﺓ ﺃﻧﺒﻮﺏ ﺍﳊﻤﺎﻳﺔ‬
‫ﳏﻠﻮﻝ ‪ KCl‬ﻣﺸﺒﻊ‬ ‫ﺍﳉﺴﻢ‬
‫ﺯﺋﺒﻖ ‪Hg‬‬
‫ﺳﺪ‪‬ﺍﺩﺓ ﻣﺴﺎﻣﻴ‪‬ﺔ ﻣﻐﻤ‪‬ﺴﺔ‬
‫‪Hg2 Cl2‬‬
‫ﲟﻠﺢ ‪ KCl‬ﺍﳌﺸﺒﻊ‬
‫ﺑﻠﹼﻮﺭﺍﺕ ‪ KCl‬ﺑﺎﻟﺰﻳﺎﺩﺓ‬
‫ﻗﺮﺹ ﻣﺴﺎﻣﻲ‬
‫ﺍﻝﺸﻜل ) ‪ : ( 1‬ﻤﺴﺭﻯ ﺍﻝﻜﺎﻝﻭﻤﻴل‬

‫ﻓﻌﻨﺩ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ ‪، 250 C‬‬

‫ﻴﻜﻭﻥ ‪ Ecal = 0.337V‬ﻓﻲ ﺤﺎﻝﺔ ‪. [Cl− ] = 0.100 mol/L‬‬ ‫‪å‬‬
‫ﻭﻴﻜﻭﻥ ‪ Ecal = 0.283V‬ﻓﻲ ﺤﺎﻝﺔ ‪. [Cl− ] = 1.00 mol/L‬‬ ‫‪å‬‬
‫ﻭﻴﻜﻭﻥ ‪ Ecal = 0.244V‬ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ﺜﺎﺒﺘﹰﺎ ﺒﺴﺒﺏ ﺇﻀﺎﻓﺔ ﻤﺤﻠﻭل‬ ‫‪å‬‬
‫ﻤﺸﺒﻊ ﻤﻥ ‪. KCl‬‬
‫ ﻤﺴﺎﺭﻱ ﺍﻝﻨﻭﻉ ﺍﻝﺜﺎﻝﺙ‬
‫ﻴﺘﺸﻜﱠل ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﻤﻥ ﺍﻝﻤﺴﺎﺭﻱ ﻤﻥ ﻤﻌﺩﻥ ﺨﺎﻤل )ﻋﺎﺩﺓ ﺍﻝﺒﻼﺘﻴﻥ( ﻓﻲ ﺘﻤﺎﺱ ﻤﻊ ﻤﺤﻠﻭل‬
‫ﻴﻀﻡ ﺍﻷﻨﻭﺍﻉ ‪ Ox‬ﻭ ‪ Red‬ﻤﻥ ﺯﻭﺝ ‪. Ox/Red‬‬
‫ﻜﻤﺎ ﻫﻭ ﺍﻝﺤﺎل ﻋﻨﺩﻤﺎ ﻨﻐﻤﺱ ﺴﻠﻜﹰﺎ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﻓﻲ ﻤﺤﻠﻭل ﻴﻀﻡ ﺸﻭﺍﺭﺩ ‪Fe3 +‬‬
‫ﻭ ‪ Fe2+‬ﺃﻭ ﻋﻨﺩﻤﺎ ﻨﻐﻤﺱ ﺴﻠﻜﹰﺎ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﻓﻲ ﻤﺤﻠﻭل ﻴﻀﻡ ﺸﻭﺍﺭﺩ ‪ MnO−4‬ﻭ ‪. Mn 2 +‬‬
‫‪ .II‬ﺍﻝﺘﻨﺒ‪‬ﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪ .1.II‬ﺴﻠﻭﻙ ﺠﻤﻠﺔ‬
‫ﻝﻨﺄﺨﺫ ﺍﻝﺯﻭﺝ ‪ Ox1/Red1‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪ ، E1‬ﻭﺍﻝﺯﻭﺝ‬

‫‪ Ox2/Red2‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪: E 2‬‬
‫‪Ox1 + n1 e− ⇌ Red1‬‬
‫‪Ox 2 + n2 e− ⇌ Red2‬‬
‫ﻭﻝﻨﺸﻜﹼل ﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ ﻤﻥ ﻫﺫﻴﻥ ﺍﻝﺯﻭﺠﻴﻥ‪ ،‬ﻭﻝﻨﻘﺱ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻬﺫﻩ ﺍﻝﺨﻠﻴﺔ‬
‫ﻭﻝﺘﻜﻥ ﺍﻝﻘﻴﻤﺔ ﺍﻝﻤﻘﺎﺴﺔ ‪. E = E1 − E 2‬‬
‫ﻨﻤﻴ‪‬ﺯ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺘﺎﻝﻴﺔ ‪‬ﺘﺒﻌﹰﺎ ﻝﻘﻴﻡ ‪ E1‬ﻭ ‪. E 2‬‬

‫ ﺍﻝﺤﺎﻝﺔ ﺍﻷﻭﻝﻰ ‪ E ≠ 0 :‬ﻭ ‪. E1 < E 2‬‬
‫ﻥ ‪ ، E > 0‬ﻋﻨﺩﻤﺎ ﻨﻐﻠﻕ ﺍﻝﺩﺍﺭﺓ ﺘﻨﺘﻘل ﺍﻹﻝﻜﺘﺭ ﻭﻨﺎﺕ ﻤﻥ ﺍﻝﻤﺴﺭﻯ ﺍﻷﻭل ﺇﻝﻰ‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻥ ﺍﻝﻤﺭﺠﻊ ‪ Red1‬ﻗﺩ ﺃُﻜﺴﺩ ﻭﺍﻝﻤﺅﻜﺴﺩ ‪ Ox 2‬ﻗﺩ ﺃُﺭﺠﻊ‪.‬‬
‫ﺍﻝﻤﺴﺭﻯ ﺍﻝﺜﺎﻨﻲ‪ .‬ﺃﻱ ﺃ ‪‬‬
‫‪Red1 → Ox1 + n1 e−‬‬
‫‪Ox2 + n2 e− ⇌ Red2‬‬
‫ﻭﻤﻨﻪ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪n1Ox 2 + n2Red1 ⇌ n1Red2 + n2Ox1‬‬
‫ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺜﺎﻨﻴﺔ ‪ E ≠ 0 :‬ﻭ ‪. E1 > E 2‬‬

‫ﻥ ‪ ، E < 0‬ﻋﻨﺩﻤﺎ ﻨﻐﻠﻕ ﺍﻝﺩﺍﺭﺓ ﺘﻨﺘﻘل ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻤﻥ ﺍﻝﻤﺴﺭﻯ ﺍﻝﺜﺎﻨﻲ ﺇﻝﻰ‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﻥ ﺍﻝﻤﺭﺠﻊ ‪ Red2‬ﻗﺩ ﺃُﻜﺴﺩ ﻭﺍﻝﻤﺅﻜﺴﺩ ‪ Ox1‬ﻗﺩ ﺃُﺭﺠﻊ‪.‬‬
‫ﺍﻝﻤﺴﺭﻯ ﺍﻷﻭل‪ .‬ﺃﻱ ﺃ ‪‬‬
‫‪−‬‬
‫‪Red2 → Ox 2 + n2 e‬‬
‫‪Ox1 + n1 e− ⇌ Red1‬‬
‫ﻭﻤﻨﻪ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪n2Ox1 + n1Red2 ⇌ n2Red1 + n1Ox 2‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻁﺒﻴﻌﻲ ﺍﻝﺫﻱ ﻴﺤﺼل ﻫﻭ ﺫﺍﻙ ﺍﻝﺫﻱ ﻴﺠﺭﻱ ﺒﻴﻥ ﺍﻝﻤﺅﻜﺴﺩ ﺍﻷﻗﻭﻯ ﺍﻝﻤﻭﺍﻓﻕ‬
‫ﺇ‪‬‬
‫ﻝﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻷﻋﻠﻰ ﻤﻊ ﺍﻝﻤﺭﺠﻊ ﺍﻷﻗﻭﻯ ﺍﻝﻤﻭﺍﻓﻕ ﻝﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ‬
‫ﻭﺍﻹﺭﺠﺎﻉ ﺍﻷﺩﻨﻰ‪.‬‬
‫ﻥ ﺃﺤﺩ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﻝﻡ ﻴ‪‬ﺴﺘﻬﻠﻙ ﻜﻠ‪‬ﻴﹰﺎ‪.‬‬

‫ﻭﻴﺴﺘﻤ ‪‬ﺭ ﺍﻝﺘﻔﺎﻋل ﻤﺎﺩﺍﻡ ﺍﻝﻜﻤﻭﻨﺎﻥ ﻤﺨﺘﻠﻔﻴﻥ ﺃﻭ ﺃ ‪‬‬
‫ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺜﺎﻝﺜﺔ ‪. E1 = E 2 :‬‬
‫ﺘﻜﻭﻥ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﺨﻠﻴﺔ ﻤﺴﺎﻭﻴﺔ ﺍﻝﺼﻔﺭ‪ .‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻝﻥ ﻴﺠﺭﻱ ﺘﻴﺎﺭ ﻜﻬﺭﺒﺎﺌﻲ‬
‫ﻥ ﺍﻝﺠﻤﻠﺔ ﻓﻲ ﺘﻭﺍﺯﻥ‬
‫ﻓﻲ ﺍﻝﺩ‪‬ﺍﺭﺓ‪ ،‬ﻭﻝﻥ ﻴﺤﺼل ﺃﻱ ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﻓﻲ ﺍﻝﺠﻤﻠﺔ‪ .‬ﺃﻱ ﺃ ‪‬‬
‫ﻭ ‪ Eeq = E1 = E 2‬ﻫﻭ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻤﺸﺘﺭﻙ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﻤﻭﺠﻭﺩﻴﻥ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫

‬
‫ﺤﻤﺎﻴﺔ ﺍﻝﺴﻔﻥ ﻤﻥ ﺍﻝﺼﺩﺃ‬
‫)‪E (V‬‬ ‫ﺘﺠﺭﻱ ﺤﻤﺎﻴﺔ ﺍﻝﺴﻔﻥ ﻤﻥ ﺍﻝﺼﺩﺃ ﺒﺈﻀﺎﻓﺔ ﻗﻁﻊ ﻤﻥ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﺃﻭ‬
‫‪O2‬‬ ‫‪1.23‬‬ ‫ﺍﻝﺘﻭﺘﻴﺎﺀ ﺇﻝﻰ ﻫﻴﻜل ﺍﻝﺴﻔﻴﻨﺔ‪ ،‬ﺤﻴﺙ ﻴﺘﺄﻜﺴﺩ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ ﺃﻭ ﺍﻝﺘﻭﺘﻴﺎﺀ ﺇﻝﻰ‬
‫‪−‬‬
‫‪OH‬‬ ‫ﺸﻭﺍﺭﺩ ‪) Mg2 +‬ﺃﻭ ‪ ( Zn2 +‬ﻋﻭﻀ ﹰﺎ ﻋﻥ ﺍﻝﺤﺩﻴﺩ ﺍﻝﺫﻱ ﻴﺒﻘﻰ ﻓﻲ‬
‫ﺩﺭﺠﺔ ﺍﻷﻜﺴﺩﺓ ﺼﻔﺭ‪ ،‬ﻭﻫﺫﺍ ﻤﺎ ﻨﺴﻤﻴﻪ ﺍﻝﺤﻤﺎﻴﺔ ﺍﻝﻤﻀﺤﻴﺔ‬
‫‪Fe‬‬ ‫‪2+‬‬
‫‪−0.44‬‬ ‫‪.sacrificial protection‬‬
‫‪Fe‬‬ ‫‪، E (Zn / Zn) = −0.76 V‬‬
‫‪o‬‬ ‫‪2+‬‬
‫ﻥ‬
‫ﻓﺈ ‪‬‬ ‫ﺃﻜﺒﺭ‬ ‫ﻭﺒﺘﻔﺼﻴل‬
‫‪2+‬‬
‫‪Zn‬‬ ‫‪−0.76‬‬ ‫ﻥ ﺍﻷﻭﻜﺴﺠﻴﻥ‬
‫‪ E o (Fe2 +/ Fe) = −0.44 V‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫‪Zn‬‬
‫ﺍﻝﻤﻨﺤل ﻓﻲ ﺍﻝﻤﺎﺀ ﻴﺅﻜﺴﺩ ﺍﻝﺘﻭﺘﻴﺎﺀ )ﺍﻝﺫﻱ ﻴﺅﺩﻱ ﺩﻭﺭ ﺍﻝﻤﺼﻌﺩ(‬
‫ﻋﻭﻀﹰﺎ ﻋﻥ ﺍﻝﺤﺩﻴﺩ )ﺍﻝﺫﻱ ﻴﺅﺩﻱ ﺩﻭﺭ ﺍﻝﻤﻬﺒﻁ( ﻭﺘﻤ ‪‬ﺭ ﻤﻥ ﺨﻼل‬
‫ﺍﻝﺤﺩﻴﺩ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﺘﻲ ﺨﺴﺭﻫﺎ ﺍﻝﺘﻭﺘﻴﺎﺀ ﻝﻴﻜﺘﺴﺒﻬﺎ ﺍﻷﻜﺴﺠﻴﻥ‬
‫ﺍﻝﻤﻨﺤل ﺒﺎﻝﻤﺎﺀ ﻭﻴﺘﺤﻭ‪‬ل ﺇﻝﻰ ﺸﻭﺍﺭﺩ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‪.‬‬
‫ ﻋﻨﺩ ﺍﻝﻤﺼﻌﺩ ‪. Zn → Zn2 + + 2 e− :‬‬
‫ ﻋﻨﺩ ﺍﻝﻤﻬﺒﻁ ‪O2 + 4 e− + 2 H2O → 4 OH− :‬‬
‫ﻴﻅﻬﺭ ﺍﻝﺸﻜل ﺍﻝﻤﺠﺎﻭﺭ ﺤﻤﺎﻴﺔ ﻝﻠﺤﺩﻴﺩ ﻓﻲ ﻫﻴﻜل ﺴﻔﻴﻨﺔ ﺒﺎﻝﻁﻼﺀ‬
‫ﺍﻝﻭﺍﻗﻲ ﻤﻥ ﺍﻝﺘﺂﻜل ﻭﺒﺎﺴﺘﻌﻤﺎل ﻗﻁﻌﺔ ﻤﻥ ﺍﻝﻤﻐﻨﺯﻴﺯﻡ ﺘﹸﺴﺘﺒﺩل ﻋﻨﺩ‬
‫ﺘﺂﻜﻠﻬﺎ‪.‬‬
‫ﻓﻲ ﺤﻴﻥ ﻴﻅﻬﺭ ﺍﻝﺸﻜل ﺍﻝﺘﺎﻝﻲ ﺤﻤﺎﻴﺔ‬

‫ﺘﺭﺒﺔ ﺭﻁﺒﺔ‬
‫ﺃﻨﺒﻭﺏ ﻤﻥ ﺍﻝﻔﻭﻻﺫ ﻝﻨﻘل ﺍﻝﻨﻔﻁ ﺃﻭ ﺍﻝﻐﺎﺯ‬
‫‪O 2 + 4 e− + 2 H 2O → 4 O H −‬‬
‫ﺒﺎﺴﺘﻌﻤﺎل ﻗﻀﻴﺏ ﻤﻥ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ‬
‫ﺃﻨﺒﻭﺏ ﻝﻨﻘل ﺍﻝﻨﻔﻁ‬
‫ﻤﻥ ﺍﻝﻔﻭﻻﺫ‬
‫ﻗﻀﻴﺏ ﻤﻥ ﺍﻝﻤﻐﻨﺯﻴﻭﻡ‬
‫‪e‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺼل ﺇﻝﻰ ﺍﻝﻨﺘﻴﺠﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫ﺇﺫﺍ ﻜﺎﻥ ﻝﺩﻴﻨﺎ ﺍﻝﺯﻭﺠﺎﻥ‪ Ox1/Red1 :‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﻜﻤﻭﻥ ﺃﻜﺴﺩﺓ ﻭ ﺇﺭﺠﺎﻉ ‪، E1‬‬
‫ﻭﺍﻝﺯﻭﺝ ‪ Ox2/Red2‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﻜﻤﻭﻥ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ‪ ، E 2‬ﺒﺤﻴﺙ ﻴﺘﻔﺎﻋﻼﻥ ﻭﻓﻕ‬
‫ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫)‪(1‬‬
‫‬
‫↽ ‪n1Ox2 + n2Red1‬‬ ‫⇀‬
‫‪ n1Red2 + n2Ox1‬‬
‫)‪(2‬‬
‫ ﻓﺈﺫﺍ ﻜﺎﻥ ‪ ، E1 < E 2‬ﺠﺭﻯ ﺍﻝﺘﻔﺎﻋل ﻭﻓﻕ ﺍﻻﺘﺠﺎﻩ ) ‪. ( 1‬‬

‫ ﻭﺇﺫﺍ ﻜﺎﻥ ‪ ، E1 > E 2‬ﺠﺭﻯ ﺍﻝﺘﻔﺎﻋل ﻭﻓﻕ ﺍﻻﺘﺠﺎﻩ ) ‪. ( 2‬‬
‫ ﻭﺇﺫﺍ ﻜﺎﻥ ‪ ، E1 = E 2‬ﻜﺎﻨﺕ ﺍﻝﺠﻤﻠﺔ ﻓﻲ ﺤﺎﻝﺔ ﺘﻭﺍﺯﻥ‪.‬‬
‫ﻥ ﻫﺫ ﻩ ﺍ ﻝﻨﺘﺎ ﺌﺞ ﺍ ﻝﺘﻲ ﺤﺼﻠﻨﺎ ﻋﻠﻴﻬﺎ ﻓﻲ ﺤﺎ ﻝﺔ ﺠﻤل ﺘﻜﻭ ﻥ ﻓﻴﻬﺎ ﺍ ﻷ ﺯ ﻭ ﺍ ﺝ ‪Ox1/Red1‬‬

‫ﺇ ‪‬‬
‫‪ Ox2/Red2‬ﻤﻔﺼﻭﻝﺔ ﺒﻌﻀﻬﺎ ﻋﻥ ﺒﻌﻀﻬﺎ‪ ،‬ﺘﻜﻭﻥ ﺼﺤﻴﺤﺔ ﺃﻴﻀﹰﺎ ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺍﻷﺯﻭﺍﺝ‬ ‫ﻭ‬
‫ﺍﻝﺴﺎﺒﻘﺔ ﻓﻲ ﺘﻤﺎﺱ ﺒﻌﻀﻬﺎ ﻤﻊ ﺒﻌﻀﻬﺎ ﻀﻤﻥ ﺍﻝﻤﺤﻠﻭل ﺫﺍﺘﻪ‪ .‬ﻭﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻴﺠﺭﻱ ﺍﻨﺘﻘﺎل‬
‫ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻤﺒﺎﺸﺭﺓ ﺒﻴﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺅﻜﺴﺩﺓ ﻭﺍﻝﻤﺭﺠﻌﺔ‪.‬‬
‫ﻴﻜﻭﻥ ﻝﺠﻤﻴﻊ ﺍﻷﺯﻭﺍﺝ ‪ Ox/Red‬ﻓﻲ ﺠﻤﻠﺔ ﻤﻭﺠﻭﺩﺓ ﻀﻤﻥ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻜﻤﻭﻥ‬
‫ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﺫﺍﺘﻪ‪.‬‬
‫‪ .2.II‬ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ ﻝﺘﻁﻭ‪‬ﺭ ﺠﻤﻠﺔ‪ -‬ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‬
‫ﻝﻨﺄﺨﺫ ﺍﻝﺯﻭﺝ ‪ Ox1/Red1‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﻜﻤﻭﻥ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ‪ E1‬ﺒﺤﻴﺙ‪:‬‬

‫‪Ox1 + n1 e− ⇌ Red1‬‬
‫‪0.06‬‬ ‫‪ a(Ox1 ) ‬‬
‫‪E1 = E1 +‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪n1‬‬ ‫‪ a(Red ) ‬‬
‫‪1‬‬
‫ﻭﺍﻝﺯﻭﺝ ‪ Ox2/Red2‬ﺍﻝﺫﻱ ﻴﺘﻤﺘﻊ ﺒﻜﻤﻭﻥ ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ‪: E 2‬‬

‫‪Ox2 + n2 e− ⇌ Red2‬‬
‫‪0.06‬‬ ‫‪ a(Ox2 ) ‬‬
‫‪E2 = E2 +‬‬ ‫‪log ‬‬ ‫‪‬‬
‫‪n2‬‬ ‫‪ a(Red2 ) ‬‬
‫ﹸﺜ ‪‬ﻡ ﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺘﻔﺎﻋل ﺒﻴﻥ ﺍﻝﻤﺅﻜﺴﺩ ‪ Ox 2‬ﻭﺍﻝﻤﺭﺠﻊ ‪ Red1‬ﻭﺫﻝﻙ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ‪:‬‬
‫‪n1Ox 2 + n2Red1 ⇌ n1Red2 + n2Ox1‬‬
‫ﻥ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺴﺎﺒﻕ ﻫﻭ‪:‬‬
‫ﺇ‪‬‬
‫‪n1‬‬ ‫‪n2‬‬
‫) ‪(a(Red2 )eq ) (a(Ox1 )eq‬‬
‫= ‪K‬‬
‫‪(a(Ox 2 )eq )n1 (a(Red1 )eq )n2‬‬
‫ﻥ ﺍﻝﺠﻤﻠﺔ ﻓﻲ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪ .‬ﻝﻨﺭﺒﻁ ﺍﻝﻤﻘﺩﺍﺭ ‪ K‬ﺒﻜﻤﻭﻨﺎﺕ‬
‫ﺤﻴﺙ ﻴﺸﻴﺭ ﺍﻝﺩﻝﻴل ‪ eq‬ﺇﻝﻰ ﺃ ‪‬‬
‫ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻴﺔ‪ .‬ﻨﻌﻠﻡ ﺃﻨﹼﻪ ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻴﻜﻭﻥ ﻝﺠﻤﻴﻊ ﺍﻷﺯﻭﺍﺝ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ‬
‫ﻭﺍﻹﺭﺠﺎﻉ ﻨﻔﺴﻪ ﺃﻱ ‪ ، E1eq = E 2eq‬ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫‪0.06‬‬ ‫‪ a(Ox2 )eq‬‬ ‫‪‬‬ ‫‪0.06‬‬ ‫‪ a(Ox1 )eq‬‬ ‫‪‬‬
‫‪E2 +‬‬ ‫‪log ‬‬ ‫‪‬‬ ‫=‬ ‫‪E‬‬ ‫‬
‫‪1‬‬ ‫‪+‬‬ ‫‪log‬‬ ‫‪‬‬
‫) ‪ a(Red‬‬ ‫‪‬‬
‫‪n2‬‬ ‫‪ a(Red2 )eq‬‬ ‫‪‬‬ ‫‪n1‬‬ ‫‪‬‬ ‫‪1 eq‬‬
‫‪‬‬
‫ﻭﺒﻀﺭﺏ ﺍﻝﻁﺭﻓﻴﻥ ﺒﺎﻝﻤﻘﺩﺍﺭ ‪ n1n 2‬ﻨﺠﺩ‬

‫‪(a(Ox 2 )eq )n1‬‬ ‫‪(a(Ox1 )eq )n2‬‬
‫‪n1n2E 2 + 0.06 log‬‬ ‫=‬ ‫‪n‬‬ ‫‪n‬‬ ‫‪E‬‬
‫‪1 2 1‬‬
‫‬
‫‪+‬‬ ‫‪0.06‬‬ ‫‪log‬‬
‫‪(a(Red2 )eq )n1‬‬ ‫‪(a(Red1 )eq )n2‬‬
‫ﻥ‪:‬‬
‫‪‬‬ ‫‪(a(Ox1 )eq )n2‬‬ ‫‪(a(Ox 2 )eq )n1‬‬ ‫‪‬‬
‫‪‬‬
‫‪n1n2 (E2 − E1 ) = 0.06  log‬‬ ‫‪− log‬‬ ‫‪‬‬
‫‪‬‬ ‫‪(a(Red1 )eq )n2‬‬ ‫‪(a(Red2 )eq )n1‬‬ ‫‪‬‬
‫‪‬‬
‫‪(a(Ox1 )eq n2 (a(Red2 )eq )n1‬‬
‫‪= 0.06 log‬‬
‫‪(a(Red1 )eq )n2 (a(Ox2 )eq )n1‬‬
‫ ‪n1n2(E 2 − E1 ) = 0.06 log K‬‬
‫ﺃﻱ‬
‫) ‪n1n2(E 2 − E1‬‬
‫= ‪log K‬‬
‫‪0.06‬‬
‫ﻭﺃﺨﻴﺭﹰﺍ‬
‫) ‪n1n2 (E 2 −E1‬‬
‫‪K = 10‬‬ ‫‪0.06‬‬
‫ل ﻗﻴﻤﺔ ﻤﻤﻜﻨﺔ ﻝﻬﺫﺍ ﺍﻝﺠﺩﺍﺀ ( ﻨﺠﺩ ﺍﻝﻘﻴﻡ ﺍﻝﺨﺎﺼ‪‬ﺔ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬

‫ﻼ ﻓﻲ ﺤﺎﻝﺔ ‪ ) n1n2 = 1‬ﻭﻫﻲ ﺃﻗ ّ‬
‫ﻓﻤﺜ ﹰ‬
‫‪E 2 − E1 = 0.25 V,‬‬ ‫‪K = 1.5 × 10 4‬‬

‫‪E 2 − E1 = −0.25 V,‬‬ ‫‪K = 6.8 × 10−5‬‬
‫ﻭﻤﻨﻪ ﻨﺴﺘﻨﺘﺞ ﺃﻨﹼﻪ ﻓﻲ ﺠﻤﻠﺔ ﺘﻀ ‪‬ﻡ ﺍﻝﻤﺅﻜﺴﺩ ‪ Ox 2‬ﻭﺍﻝﻤﺭﺠﻊ ‪ Red1‬ﻴﺘﺤﻘﹼﻕ ﻤﺎ ﻴﻠﻲ ‪:‬‬
‫• ﺇﺫﺍ ﻜﺎﻥ ‪ ، E 2 − E1 > 0.25‬ﻜﺎﻥ ‪ ، K 0 > 10 4‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻜﺎﻥ ﺍﻝﺘﻔﺎﻋل ﺘﺎ ‪‬ﻤﹰﺎ‪.‬‬
‫• ﺇﺫﺍ ﻜﺎﻥ ‪ ، E 2 − E1 < −0.25‬ﻜﺎﻥ ‪ ، K 0 < 10−4‬ﻭﻝﻥ ﺘﺒﺘﻌﺩ ﺍﻝﺠﻤﻠﺔ ﻋﻥ ﻭﻀﻌﻬﺎ‬
‫ﺍﻝﺫﻱ ﻫﻲ ﻓﻴﻪ‪.‬‬
‫• ﺇﺫﺍ ﻜﺎﻥ ‪ ، −0.25 < E 2 − E1 < 0.25‬ﻴﺤﺼل ﺘﻔﺎﻋل ﻭﻝﻜﻨﹼﻪ ﻝﻴﺱ ﺘﺎﻤﹰﺎ‪.‬‬
‫‪ .3.II‬ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪ -‬ﺘﻁﺒﻴﻕ‬
‫ﺃ ‪‬ﻭ ﹰﻻ ‪ :‬ﻨﻤﺯﺝ ‪ V1 = 10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﻘﺼﺩﻴﺭ ‪ II‬ﺒﺘﺭﻜﻴﺯ ‪ 0.1 mol/L‬ﻤﻊ ﻤﻘﺩﺍﺭ‬
‫‪ III‬ﺒﺘﺭﻜﻴﺯ ‪ . 0.1 mol/L‬ﻤﺎ ﻫﻭ‬ ‫‪ V2 = 10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﻠﻭﺭﻴﺩ ﺍﻝﺤﺩﻴﺩ‬
‫ﺘﺭﻜﻴﺏ ﺍﻝﻤﺯﻴﺞ ﺍﻝﻨﻬﺎﺌﻲ؟ ﺍﺴﺘﻨﺘﺞ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻝﻸﺯﻭﺍﺝ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﺜﺎﻨﻴﹰﺎ ‪ :‬ﻨﻐﻤﺱ ﺴﻠﻜﹰﺎ ﻤﻥ ﺍﻝﻔﻀﺔ ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺤﺩﻴﺩ ‪ III‬ﺒﺘﺭﻜﻴﺯ ‪ . 0.05 mol/L‬ﻤﺎ‬
‫ﻫﻭ ﺍﻝﺘﺭﻜﻴﺏ ﺍﻝﻨﻬﺎﺌﻲ ﻝﻠﺠﻤﻠﺔ ﺍﻝﻨﺎﺸﺌﺔ‪ .‬ﺍﺴﺘﻨﺘﺞ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻝﻸﺯﻭﺍﺝ‪.‬‬
‫‪E (Sn 4 +/Sn2 + ) = 0.15 V‬‬
‫‪E (Fe3 +/Fe2 + ) = 0.77 V‬‬
‫‪E (Ag+/Ag) = 0.80 V‬‬
‫ﺍﻝﺤل‬
‫ﻻ ‪ :‬ﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻨﺼﻔﻴﺔ ‪:‬‬
‫ﺃ ‪‬ﻭ ﹰ‬
‫‪4+‬‬ ‫‪−‬‬ ‫‪2+‬‬
‫‪Sn‬‬ ‫‪+ 2e‬‬ ‫‪→ Sn‬‬ ‫) ‪(1‬‬
‫‪Fe3+ + e−‬‬ ‫‪→ Fe2 +‬‬ ‫)‪(2‬‬
‫ﻭﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ‪:‬‬

‫‪2 Fe3 + + Sn2 + → Sn 4 + + 2 Fe2 +‬‬
‫ﻭﻨﺴﺘﻨﺘﺞ ﻤﻥ ﺫﻝﻙ ﻋﻼﻗﺘﻲ ﻨﺭﻨﺴﺕ ﺍﻝﺘﺎﻝﻴﺘﻴﻥ ‪:‬‬

‫‪0.06‬‬ ‫] ‪[Sn 4 +‬‬
‫‪E1 = E (Sn 4 +/Sn2 + ) +‬‬ ‫‪log‬‬
‫‪2‬‬ ‫] ‪[Sn2 +‬‬
‫‪0.06‬‬ ‫‪[Fe3+ ]2‬‬
‫‪E 2 = E (Fe3+/Fe2 + ) +‬‬ ‫‪log‬‬
‫‪2‬‬ ‫‪[Fe2+ ]2‬‬
‫ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺴﺎﻭﺍﺓ ‪ ، E1eq = E 2eq = Eeq‬ﺃﻱ‬
‫‪0.06‬‬ ‫‪[Sn 4 + ][Fe2 + ]2‬‬

‫= ) ‪−E (Sn 4 +/Sn2 + ) + E (Fe3 +/Fe2+‬‬ ‫‪log‬‬
‫‪2‬‬ ‫‪[Sn2 + ][Fe3+ ]2‬‬
‫ﻭﻤﻨﻪ ﻨﺴﺘﻨﺘﺞ ﻗﻴﻤﺔ ‪: K‬‬
‫‪2‬‬
‫‪K = 4.6 × 1020‬‬ ‫= ‪ log K‬ﺃﻭ‬ ‫)‪(0.77 − 0.15‬‬
‫‪0.06‬‬
‫ﻭﺍﻝﺘﻔﺎﻋل ﺘﺎ ‪‬ﻡ‪ ،‬ﻭﻝﺤﺴﺎﺏ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻤﺨﺘﻠﻔﺔ ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﻨﻜﺘﺏ ‪:‬‬
‫‪2 Fe3 +‬‬ ‫‪+ Sn2 +‬‬ ‫‪→ Sn 4 +‬‬ ‫‪+ 2 Fe2+‬‬
‫‪t = 0 0.05‬‬ ‫‪0.05‬‬ ‫‪0‬‬ ‫‪0‬‬
‫‪teq‬‬ ‫‪≈0‬‬ ‫‪0.025‬‬ ‫‪0.025‬‬ ‫‪0.05‬‬
‫ﻓﻌﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‬
‫‪ [Sn2 + ] = [Sn 4 + ] = 0.025 mol/L‬ﻭ ‪[Fe2+ ] = 0.05 mol/L‬‬
‫ﻥ‬
‫ﻭﺇﺫﺍ ﺍﺴﺘﻌﻤﻠﻨﺎ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ﻭﺠﺩﻨﺎ ﺃ ‪‬‬
‫‪. [Fe3+ ] = 2.3 × 10−12 mol/L‬‬

‫ﺃﻤﺎ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻝﻸﺯﻭﺍﺝ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻓﻴﻤﻜﻥ ﺤﺴﺎﺒﻪ ﻤﻥ ﺃﺤﺩ ﺍﻝﺯﻭﺠﻴﻥ ) ﻭﻴﺴﺘﺤﺴﻥ‬
‫ﺍﺴﺘﻌﻤﺎل ﺍﻝﺯﻭﺝ ﺍﻝﺫﻱ ﻻ ﻴﻀﻡ ﺃﻨﻭﺍﻋﹰﺎ ﻓﺎﺌﻘﺔ ﺍﻝﻨﺩﺭﺓ ( ‪.‬‬
‫‪0.06‬‬ ‫] ‪[Sn 4 +‬‬

‫‪Eeq = E (Sn 4 +/Sn2 + ) +‬‬ ‫‪log‬‬
‫‪2‬‬ ‫] ‪[Sn2 +‬‬
‫‪0.025‬‬
‫‪= 0.15 + 0.03 log‬‬ ‫‪= 0.15 V‬‬
‫‪0.025‬‬
‫) ‪. ( 2, a‬‬ ‫ﺍﻨﻅﺭ ﺍﻝﺸﻜل‬
‫ﺜﺎﻨﻴﹰﺎ ‪ :‬ﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻨﺼﻔﻴﺔ ‪:‬‬

‫‪3+‬‬ ‫‪−‬‬ ‫‪2+‬‬
‫‪Fe‬‬ ‫‪+ e → Fe‬‬ ‫) ‪(1‬‬
‫‪Ag+ + e− → Ag‬‬ ‫)‪(2‬‬
‫ﻭﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ‪:‬‬

‫‪Fe3 + + Ag → Fe2+ + Ag +‬‬
‫ﻥ‬
‫ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺴﺎﻭﺍﺓ ‪ ، E1eq = E 2eq = Eeq‬ﺃﻱ ﺃ ‪‬‬
‫] ‪[Fe3 +‬‬
‫‪E (Ag+/Ag) − E (Fe3+/Fe2+ ) = 0.06 log‬‬
‫] ‪[Fe2+ ][Ag+‬‬
‫ﻭﻤﻨﻪ ﻨﺴﺘﻨﺘﺞ ﻗﻴﻤﺔ ‪: K‬‬
‫‪0.03‬‬ ‫‪1‬‬
‫‪K = 10−0.5 = 0.32‬‬ ‫ﺃﻭ‬ ‫‪log K = −‬‬ ‫‪=−‬‬
‫‪0.06‬‬ ‫‪2‬‬
‫ﺇﺫﻥ ﺍﻝﺘﻔﺎﻋل ﻏﻴﺭ ﺘﺎ ‪‬ﻡ‪ .‬ﻝﻨﻌﻴ‪‬ﻥ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻤﺨﺘﻠﻔﺔ ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ‪:‬‬
‫‪Fe3 +‬‬ ‫‪+ Ag → Fe2 +‬‬ ‫‪+ Ag+‬‬

‫‪t = 0 0.05‬‬ ‫∞‬ ‫‪0‬‬ ‫‪0‬‬
‫‪teq‬‬ ‫‪0.05 − ξ‬‬ ‫∞‬ ‫‪ξ‬‬ ‫‪ξ‬‬
‫ﺇﺫﻥ ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‬
‫‪ξ2‬‬
‫= ‪K‬‬ ‫‪= 0.32‬‬
‫) ‪(0.05 − ξ‬‬
‫ل ﻨﺠﺩ ‪ ، ξ = 4.4 × 10−2 mol/L‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ‬
‫ﻭﺒﺎﻝﺤ ّ‬
‫‪[Fe2+ ] = [Ag + ] = 4.4 × 10−2 mol/L‬‬
‫ﻭ‬
‫‪[Fe3+ ] = 6.0 × 10−3 mol/L‬‬
‫ﻭﻝﺤﺴﺎﺏ ‪ Eeq‬ﻨﺴﺘﻌﻤل ﺃﺤﺩ ﺍﻝﺯﻭﺠﻴﻥ‪.‬‬
‫‪−3‬‬
‫‪6 × 10‬‬
‫‪Eeq = 0.77 + 0.06 log‬‬ ‫‪= 0.72 V‬‬ ‫ﻤﻥ ﺍﻝﺯﻭﺝ ‪ Fe3 +/Fe2 +‬ﻨﺠﺩ‬
‫‪4.4 × 10−2‬‬
‫‪4.4 × 10−2‬‬
‫‪Eeq‬‬ ‫‪= 0.80 + 0.06 log‬‬ ‫‪≈ 0.72 V‬‬ ‫ﻭﻤﻥ ﺍﻝﺯﻭﺝ ‪ Ag + Ag‬ﻨﺠﺩ‬
‫‪1‬‬
‫ﺍﻨﻅﺭ ﺍﻝﺸﻜل ) ‪. ( 2, b‬‬
‫)‪E (V‬‬ ‫)‪E (V‬‬
‫‪Ag+‬‬ ‫‪Fe3+‬‬
‫‪0.80‬‬ ‫‪0.77‬‬
‫‪Ag‬‬ ‫‪Fe2+‬‬
‫‪Fe 3+‬‬ ‫‪0.77‬‬ ‫‪Sn 4+‬‬

‫‪0.15‬‬
‫‪Fe‬‬ ‫‪2+‬‬ ‫‪Sn2+‬‬
‫‪K < 1‬‬ ‫‪K ≫ 1‬‬

‫ﺍﻝﺸﻜل ) ‪ : ( 2, b‬ﺍﻝﺘﻔﺎﻋل ﺒﻴﻥ ﺸﻭﺍﺭﺩ ‪Fe3+‬‬ ‫ﺍﻝﺸﻜل ) ‪ : ( 2, a‬ﺍﻝﺘﻔﺎﻋل ﺒﻴﻥ ﺸﻭﺍﺭﺩ ‪Fe3+‬‬
‫ﻭﻤﻌﺩﻥ ﺍﻝﻔﻀ‪‬ﺔ ﺘﻔﺎﻋلٌ ﻏﻴﺭ ﺘﺎﻡ‪.‬‬ ‫ﻭﺸﻭﺍﺭﺩ ‪ Sn 2+‬ﺘﻔﺎﻋلٌ ﺘﺎﻡ‪.‬‬
‫‪ .4.II‬ﺘﻌﻴﻴﻥ )‪E 0 (Ox/Red‬‬
‫ﻨﻠﺠﺄ ﻓﻲ ﺒﻌﺽ ﺍﻷﺤﻴﺎﻥ ﺇﻝﻰ ﺘﺤﺩﻴﺩ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻨﻅﺎﻤﻲ ﻝﺯﻭﺝ ‪ Ox/Red‬ﺍﺒﺘﺩﺍ ‪‬ﺀ ﻤﻥ‬
‫ﺍﻝﻜﻤﻭﻨﺎﺕ ﺍﻝﻨﻅﺎﻤﻴﺔ ﺍﻝﻤﻌﺭﻭﻓﺔ ﻷﺯﻭﺍﺝ ‪ Ox/Red‬ﺃﺨﺭﻯ‪.‬‬
‫ﻤﺜﺎل ‪ :‬ﺍﻝﻨﺤﺎﺱ ﺒﺩﺭﺠﺘﻲ ﺍﻷﻜﺴﺩﺓ ‪ I‬ﻭ ‪. II‬‬

‫ﻨﺠﺩ ﻓﻲ ﺍﻝﺠﺩﺍﻭل‬
‫)‪E 2(Cu+/Cu‬‬ ‫‪ E1(Cu2+/Cu+ ) = 0.16 V‬ﻭ ‪= 0.52 V‬‬
‫ﻭﻨﻬﺩﻑ ﻓﻲ ﻫﺫﺍ ﺍﻝﻤﺜﺎل ﺇﻝﻰ ﺤﺴﺎﺏ ﻗﻴﻤﺔ )‪. E 3(Cu2+/Cu‬‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺠﻤﻠﺔ ﺍﻝﺘﻲ ﺘﻀﻡ ‪ Cu ، Cu+ ، Cu2+‬ﻭﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻨﺼﻔﻴﺔ‬

‫ﻭﻋﻼﻗﺎﺕ ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻬﺎ‪.‬‬
‫‪2+‬‬
‫] ‪[Cu‬‬
‫‪E1 = E1 + 0.06 log‬‬ ‫‪Cu2 + + e− ⇌ Cu+‬‬ ‫) ‪(1‬‬
‫] ‪[Cu+‬‬
‫] ‪E 2 = E 2 + 0.06 log [Cu+‬‬ ‫) ‪Cu+ + e− ⇌ Cu(s) ( 2‬‬
‫‪0.06‬‬
‫‪E 3 = E 3 +‬‬ ‫] ‪log [Cu+‬‬ ‫) ‪Cu2 + + 2 e− ⇌ Cu(s) ( 3‬‬
‫‪2‬‬
‫ﻥ ﻭﺤﺩﺍﻨﻴﺔ ﻜﻤﻭﻥ ﺠﻤﻴﻊ ﺍﻷﺯﻭﺍﺝ ‪ Ox/Red‬ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﺘﻘﺘﻀﻲ ﺃﻥ ﻴﻜﻭﻥ‬
‫ﺇ‪‬‬
‫‪E1eq = E 2eq = E 3eq‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ‪ ، 2 E 3eq = E1eq + E 2eq‬ﺃﻱ‬
‫] ‪2E 3 + 2 × 0.03 log[Cu2+ ] = E1 + E 2 + 0.06 log[Cu2+‬‬
‫ﻥ‬
‫ ‪1‬‬
‫= ‪E 3‬‬ ‫) ‪(E + E 2‬‬
‫‪2 1‬‬
‫ﻥ‬
‫ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﻨﺠﺩ ﺃ ‪‬‬
‫‪1‬‬ ‫‪0.68‬‬
‫= ‪E 3‬‬ ‫= )‪(0.16 + 0.52‬‬ ‫‪= 0.34 V‬‬
‫‪2‬‬ ‫‪2‬‬
‫ﻥ ﻫﺫﻩ ﺍﻝﻌﻼﻗﺔ ﺘﺸﺒﻪ ﺇﻝﻰ ﺤ ‪‬ﺩ ﺒﻌﻴﺩ ﻨﻤﻁ ﺍﻝﻌﻼﻗﺎﺕ ﺍﻝﺘﻲ ﻨﺤﺴﺏ ﺒﻬﺎ ﻤﺭﻜﺯ ﺍﻝﺜﻘل‪.‬‬
‫ﻻ ﺤﻅ ﺃ ‪‬‬
‫‪ .III‬ﻤﻨﺎﻁﻕ ﺍﻝﻭﺠﻭﺩ ﻭﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ‬
‫‪ .1.III‬ﺘﻌﺎﺭﻴﻑ‬
‫ﻓﻴﻤﺎ ﻴﻠﻲ ﻋﺭﺽ ﻝﻤﻔﻬﻭﻡ ﻤﻨﻁﻘﺔ ﺍﻝﺭﺠﺤﺎﻥ ﺃﻭ ﻤﻨﻁﻘﺔ ﺍﻝﻭﺠﻭﺩ ﻤﻥ ﺨﻼل ﻋﺭﻀﻨﺎ ﻝﻌﺩﺩ ﻤﻥ‬
‫ﺍﻷﻤﺜﻠﺔ ﺍﻝﻤﻭﻀ‪‬ﺤﺔ‪.‬‬
‫ﻼ ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ‪. Fe3 +/Fe2 +‬‬

‫ﻼﻥ‪ .‬ﻨﺄﺨﺫ ﻤﺜ ﹰ‬
‫ ﺍﻝﻨﻭﻋﺎﻥ ‪ Red‬ﻭ ‪ Ox‬ﻤﻨﺤ ﹼ‬
‫ﻝﻨﻜﺘﺏ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺜﻡ ﻤﻌﺎﺩﻝﺔ ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻬﺎ‪:‬‬
‫‪Fe3 + + e− ⇌ Fe2 +‬‬
‫] ‪[Fe3+‬‬
‫‪E = 0.77 + 0.06 log‬‬
‫] ‪[Fe2+‬‬
‫ﻥ‬
‫ ﺇﺫﺍ ﻜﺎﻥ ﻜﻤﻭﻥ ﺍﻷﺯﻭﺍﺝ ‪ E‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺃﻜﺒﺭ ﻤﻥ ﺍﻝﻤﻘﺩﺍﺭ ‪ 0.77 V‬ﻓﻬﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫] ‪ ، [Fe3+ ] > [Fe2+‬ﻭﺘﻜﻭﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ Fe3+‬ﻫﻲ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺭﺍﺠﺤﺔ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ‬
‫ﺍﻝﺸﺎﺭﺩﺓ ‪. Fe2 +‬‬
‫ﻥ‬
‫ ﺇﺫﺍ ﻜﺎﻥ ﻜﻤﻭﻥ ﺍﻷﺯﻭﺍﺝ ‪ E‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺃﺼﻐﺭ ﻤﻥ ﺍﻝﻤﻘﺩﺍﺭ ‪ 0.77 V‬ﻓﻬﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫] ‪ ، [Fe3+ ] < [Fe2 +‬ﻭﺘﻜﻭﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ Fe2+‬ﻫﻲ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﺭﺍﺠﺤﺔ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ‬
‫ﺍﻝﺸﺎﺭﺩﺓ ‪ ، Fe3+‬ﺍﻝﺸﻜل )‪. (3‬‬
‫ ﻝﻌﻨﺼﺭ ﺍﻝﺤﺩﻴﺩ ﺍﻝﺫﱠﺭﻴ‪‬ﺔ ﻨﻔﺴﻬﺎ ﻓﻲ ﺍﻝﺸﺎﺭﺩﺘﻴﻥ ‪ Fe2 +‬ﻭ ‪ ، Fe3+‬ﺤﻴﺙ ﺘﻌﺎﺩل ﺍﻝﺫﱠﺭﻴ‪‬ﺔ ﻫﻨﺎ‬
‫ﻥ ﺍﻝﻜﻤﻭﻥ ﻝﻠﺤﺩ ﺍﻝﻔﺎﺼل ﺒﻴﻥ ﻤﻨﻁﻘﺘﻲ ﺍﻝﺭﺠﺤﺎﻥ ﻻ ﻴﺘﻌﻠﹼﻕ‬
‫ﺍﻝﻭﺍﺤﺩ‪ .‬ﻭﻴﻨﺠﻡ ﻋﻥ ﺫﻝﻙ ﺃ ‪‬‬
‫ﺒﺎﻝﺘﺭﻜﻴﺯ ﺍﻝﻜﻠﻲ ﻝﻸﻨﻭﺍﻉ ﺍﻝﻤﻌﺘﺒﺭﺓ‪ .‬ﻻ ﻴﻜﻭﻥ ﺍﻷﻤﺭ ﻜﺫﻝﻙ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ‬
‫‪. Cr2 O27− /Cr3 +‬‬
‫)‪E (V‬‬
‫‪Fe 3 +‬‬
‫‪0.77‬‬
‫‪Fe2 +‬‬
‫ﺍﻝﺸﻜل )‪ : (3‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﺸﻭﺍﺭﺩ ‪ Fe3 +‬ﻭ ‪Fe2 +‬‬
‫ﻼ ﺤﺎﻝﺔ ‪. Fe2 + /Fe‬‬

‫ ﺃﺤﺩ ﺍﻝﻨﻭﻋﻴﻥ ‪ Red‬ﺃﻭ ‪ Ox‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻭﺍﻵﺨﺭ ﺼﻠﺏ‪ .‬ﻨﺄﺨﺫ ﻤﺜ ﹰ‬
‫ﻻ ﻴﻤﻜﻨﻨﺎ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺘﻌﺭﻴﻑ ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﻷﻥ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺼﻠﺒﺔ‪ ،‬ﻭﺘﺴﺎﻭﻱ‬
‫ﻓﻌﺎﻝﻴﺘﻪ ﺍﻝﻭﺍﺤﺩ‪ .‬ﻭﻨﻌﺭ‪‬ﻑ ﻫﻨﺎ ﺘﻤﺎﻤﹰﺎ ﻜﻤﺎ ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺭﻭﺍﺴﺏ ﻤﻨﻁﻘﺔ ﻭﺠﻭﺩ ﻝﻠﺤﺩﻴﺩ ﻭﺫﻝﻙ ﻨﺴﺒﺔ ﺇﻝﻰ‬
‫ﺘﺭﻜﻴﺯ ﺤﺩ‪‬ﻱ ‪ C lim‬ﺃﻋﻅﻤﻲ ﻝﻠﺸﺎﺭﺩﺓ ‪. Fe2+‬‬
‫)‪Fe2+ + 2 e− ⇌ Fe(s‬‬
‫] ‪E = −0.44 + 0.03 log [Fe2+‬‬
‫ﻥ ‪ C lim‬ﻫﻭ ﺘﺭﻜﻴﺯ ‪ Fe2+‬ﺒﻐﻴﺎﺏ ﺍﻝﺤﺩﻴﺩ‪ .‬ﺘﺤﺕ ﺘﺄﺜﻴﺭ ﻤﺭﺠﹺﻊ ﻋﻠﻰ ‪Fe2+‬‬

‫ﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫ﺴﻴﻅﻬ‪‬ﺭ ﺍﻝﻤﻌﺩﻥ ‪ Fe‬ﻋﻨﺩﻤﺎ ‪ . [Fe2+ ] < C lim‬ﻭﻋﻠﻴﻪ ﻴﻤﺜﹼل ﺍﻝﻜﻤﻭﻥ‬
‫‪E = −0.44 + 0.03 log C lim‬‬

‫ﻥ ﻫﺫﺍ ﺍﻝﺤ ‪‬ﺩ ﺍﻝﻔﺎﺼل ﻴﺘﻌﻠﹼﻕ ﻫﻨﺎ ﺒﺎﻝﺘﺭﻜﻴﺯ ‪ C lim‬ﻝﻤﺤﻠﻭل‬

‫ﺤ ‪‬ﺩ ﻭﺠﻭﺩ ﻤﻌﺩﻥ ﺍﻝﺤﺩﻴﺩ‪ .‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ ، (II‬ﺍﻝﺸﻜل )‪. (4‬‬
‫ﻓﻌﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪ [Fe2 + ]lim = 0.1mol/ L‬ﻴﻜﻭﻥ‪:‬‬
‫‪E = −0.44 + 0.03 × (−1) = −0.47 V‬‬
‫)‪E (V‬‬
‫‪Fe2 +‬‬
‫‪−0.47‬‬
‫)‪Fe (s‬‬
‫ﺍﻝﺸﻜل )‪ : (4‬ﻤﻨﻁﻘﺔ ﻭﺠﻭﺩ ﻤﻌﺩﻥ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﺤﺎﻝﺔ ‪[Fe2 + ]lim = 0.1 mol/ L‬‬
‫ﻼ ﺤﺎﻝﺔ ‪. Cl2 (g)/Cl−‬‬

‫ ﺃﺤﺩ ﺍﻝﻨﻭﻋﻴﻥ ‪ Red‬ﺃﻭ ‪ Ox‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻭﺍﻵﺨﺭ ﻏﺎﺯﻱ‪ .‬ﻨﺄﺨﺫ ﻤﺜ ﹰ‬
‫‪Cl2 (g) + 2 e− ⇌ 2Cl−‬‬

‫‪ P (Cl ) ‬‬
‫‪E = 1.36 + 0.03 log ‬‬ ‫‪2 ‬‬
‫‪ [Cl ]2 ‬‬
‫‪−‬‬
‫ﻨﻌﺭ‪‬ﻑ ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ﺒﺘﺤﺩﻴﺩ ﺍﻝﻀﻐﻁ ) ‪ P (Cl2‬ﻭﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ ] ‪ [Cl−‬ﻓﻲ‬

‫ﻭﻫﻜﺫﺍ ﻓﻲ ﺤﺎﻝﺔ ‪ P (Cl2 ) = 1bar‬ﻭ ‪ [Cl− ] = 0.1mol/ L‬ﻴﻜﻭﻥ ﻜﻤﻭﻥ ﺍﻝﺤ ‪‬ﺩ‬
‫ﺍﻝﻔﺎﺼل‪ ، E = 1.42 V :‬ﺍﻝﺸﻜل )‪. (5‬‬
‫)‪E (V‬‬
‫)‪Cl2 (g‬‬
‫‪1.42‬‬
‫‪Cl−‬‬
‫ﺍﻝﺸﻜل )‪ : (5‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻜل ﻤﻥ ‪ Cl2‬ﻭ ‪Cl−‬‬

‫ﻓﻲ ﺤﺎﻝﺔ ‪ P (Cl2 ) = 1 bar‬ﻭ ‪[Cl− ] = 0.1 mol/ L‬‬
‫‪ .2.III‬ﺘﻁﺒﻴﻘﺎﺕ‬
‫ ﻤﻨﺎﻁﻕ ﺍﻻﺴﺘﻘﺭﺍﺭ ﻝﺩﺭﺠﺎﺕ ﺍﻷﻜﺴﺩﺓ ‪ III ، II ، 0‬ﻝﻠﺤﺩﻴﺩ‪.‬‬

‫ﻝﻨﺭﺴﻡ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺸﻭﺍﺭﺩ ‪ Fe2 +‬ﻭ ‪ Fe3+‬ﻭﻤﻨﻁﻘﺔ ﺍﻝﻭﺠﻭﺩ ﻝﻤﻌﺩﻥ ﺍﻝﺤﺩﻴﺩ ﻓﻲ‬
‫ﺍﻝﺤﺎﻝﺔ ‪. [Fe2 + ]lim = 0.1mol/ L‬‬
‫ل ﻋﻥ‬
‫ل ﻤﻥ ‪ Fe2 +‬ﻭ ‪ Fe3+‬ﻤﺴﺘﻘ ّ‬
‫ﻥ ﻜﻤﻭﻥ ﺍﻝﺤ ‪‬ﺩ ﺍﻝﻔﺎﺼل ﺒﻴﻥ ﻤﻨﻁﻘﺘﻲ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻜ ّ‬
‫ﺇ‪‬‬
‫ﺍﻝﺘﺭﻜﻴﺯ ﻭﻴﺴﺎﻭﻱ ‪. E1 = E (Fe3 + /Fe2 + ) = 0.77 V‬‬
‫ﺃﻤﺎ ﻓﻴﻤﺎ ﻴﺘﻌﻠﹼﻕ ﺒﻜﻤﻭﻥ ﺍﻝﺤ ‪‬ﺩ ﺍﻝﻔﺎﺼل ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ‪ Fe2 + /Fe‬ﻓﻬﻭ ﻴﺘﻌﻠﹼﻕ ﺒﺎﻝﺘﺭﻜﻴﺯ‬
‫‪ C lim‬ﻭﻴﺴﺎﻭﻱ ‪. E2 = E (Fe2+ /Fe) + 0.03 log C lim = −0.47 V‬‬
‫ﻴﺠﻤل ﺍﻝﺸﻜل )‪ (6‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﺍﻝﻭﺠﻭﺩ ﺍﻝﺨﺎﺼﺔ ﺒﻜل ﻤﻥ ‪ Fe2 +‬ﻭ ‪ Fe3+‬ﻭ ‪Fe‬‬
‫ﻥ ﻝﻜل ّﻤﻥ ‪ Fe2 +‬ﻭ ‪ Fe3+‬ﻭ ‪Fe‬‬
‫ﺍﻝﺘﻲ ﻭﺠﺩﻨﺎﻫﺎ ﻓﻲ ﺍﻝﻔﻘﺭﺓ ﺍﻝﺴﺎﺒﻘﺔ‪ .‬ﻴﻅﻬﺭ ﻤﻥ ﺍﻝﺸﻜل ﺃ ‪‬‬
‫ﻤﻨﻁﻘﺔ ﺍﺴﺘﻘﺭﺍﺭ‪.‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ‪ Fe3+‬ﻴﻤﻜﻨﻬﺎ ﺃﻥ ﺘﺘﻔﺎﻋل ﻤﻊ ﻤﻌﺩﻥ ﺍﻝﺤﺩﻴﺩ‬
‫ﻴﺴﻤﺢ ﺍﻝﻤﺨﻁﻁ ﺒﺎﻝﺘﻨﺒ‪‬ﺅ ﺃ ‪‬‬
‫ﻝﺘﻌﻁﻲ ﺸﻭﺍﺭﺩ ‪ Fe2 +‬ﻭﺫﻝﻙ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪2 Fe3+ + Fe(s) 3 Fe2 +‬‬
‫ﺘﺅﻜﹼﺩ ﺍﻝﺘﺠﺭﺒﺔ ﻫﺫﺍ ﺍﻝﺘﻨﺒ‪‬ﺅ‪ .‬ﻨﺴﻤ‪‬ﻲ ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﻤﻥ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﺫﻱ ﻴﻜﻭﻥ‬
‫ﻓﻴﻪ ﻨﺎﺘﺞ ﺍﻝﺘﻔﺎﻋل ‪ Fe2 +‬ﻫﻭ ﺍﻝﻤﺅﻜﺴ‪‬ﺩ ﻓﻲ ﺍﻝﺯﻭﺝ )‪ (Fe2+ /Fe‬ﻭﺍﻝﻤﺭﺠﹺﻊ ﻓﻲ ﺍﻝﺯﻭﺝ‬
‫) ‪ (Fe3+ /Fe2 +‬ﺘﻔﺎﻋل ﺘﺫﺒﺫﺏ ﻤﺅﻜﺴﺩ‪-‬ﻤﺭﺠﻊ ‪.amphoterization‬‬
‫)‪E (V‬‬
‫‪Fe3 +‬‬
‫‪0.77‬‬
‫‪Fe2 +‬‬
‫‪Fe2 +‬‬
‫‪−0.47‬‬
‫‪Fe‬‬
‫ﺍﻝﺸﻜل )‪ : (6‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﺸﻭﺍﺭﺩ ‪ Fe3 +‬ﻭ ‪ Fe2 +‬ﻭﻤﻨﻁﻘﺔ ﻭﺠﻭﺩ ﻤﻌﺩﻥ ﺍﻝﺤﺩﻴﺩ ﻓﻲ ﺤﺎﻝﺔ‬
‫‪ . [Fe2 + ]lim = 0.1 mol/ L‬ﺘﺘﻔﺎﻋل ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ‪ Fe3 +‬ﻤﻊ ﻤﻌﺩﻥ ﺍﻝﺤﺩﻴﺩ ﻴﺤﺼل ﺘﺫﺒﺫﺏ‪.‬‬
‫ ﻤﻨﺎﻁﻕ ﺍﻻﺴﺘﻘﺭﺍﺭ ﻝﺩﺭﺠﺎﺕ ﺍﻷﻜﺴﺩﺓ ‪ II ، I ، 0‬ﻝﻠﻨﺤﺎﺱ‪.‬‬

‫)‪E (V‬‬
‫‪+‬‬
‫‪Cu‬‬
‫‪0.46‬‬
‫‪Cu‬‬
‫‪Cu2 +‬‬
‫‪0.16‬‬
‫‪Cu+‬‬
‫ﺍﻝﺸﻜل )‪ : (7‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﺸﻭﺍﺭﺩ ‪ Cu2 +‬ﻭ ‪ Cu+‬ﻭﻤﻨﻁﻘﺔ ﻭﺠﻭﺩ ﻤﻌﺩﻥ ﺍﻝﻨﺤﺎﺱ ﻓﻲ ﺤﺎﻝﺔ‬
‫‪. [Cu+ ]lim = 0.1 mol/ L‬‬
‫ﻝﻨﺭﺴﻡ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻠﺸﻭﺍﺭﺩ ‪ Cu2 +‬ﻭ ‪ Cu+‬ﻭﻤﻨﻁﻘﺔ ﺍﻝﻭﺠﻭﺩ ﻝﻤﻌﺩﻥ ﺍﻝﻨﺤﺎﺱ ﻓﻲ‬
‫ﺍﻝﺤﺎﻝﺔ ‪. [Cu+ ]lim = C lim = 0.1mol/ L‬‬
‫ل ﻋﻥ‬
‫ل ﻤﻥ ‪ Cu2 +‬ﻭ ‪ Cu+‬ﻤﺴﺘﻘ ّ‬
‫ﻥ ﻜﻤﻭﻥ ﺍﻝﺤ ‪‬ﺩ ﺍﻝﻔﺎﺼل ﺒﻴﻥ ﻤﻨﻁﻘﺘﻲ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻜ ّ‬
‫ﺇ‪‬‬
‫ﺍﻝﺘﺭﻜﻴﺯ ﻭﻴﺴﺎﻭﻱ ‪. E1 = E (Cu2 + /Cu+ ) = 0.16 V‬‬
‫ﺃﻤﺎ ﻓﻴﻤﺎ ﻴﺘﻌﻠﹼﻕ ﺒﻜﻤﻭﻥ ﺍﻝﺤ ‪‬ﺩ ﺍﻝﻔﺎﺼل ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ‪ Cu+ /Cu‬ﻓﻬﻭ ﻴﺘﻌﻠﹼﻕ ﺒﺎﻝﺘﺭﻜﻴﺯ‬
‫‪ C lim‬ﻭﻴﺴﺎﻭﻱ ‪. E 2 = E (Cu2 + /Cu) + 0.03 log C lim = 0.46 V‬‬
‫ﻴﺠﻤل ﺍﻝﺸﻜل )‪ (7‬ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﻭﺍﻝﻭﺠﻭﺩ ﺍﻝﺨﺎﺼﺔ ﺒﻜل ﻤﻥ ‪ Cu2 +‬ﻭ ‪ Cu+‬ﻭ ‪Cu‬‬
‫ﻥ ﻝﺸﻭﺍﺭﺩ ‪ Cu+‬ﻤﻨﻁﻘﺘﻲ ﺭﺠﺤﺎﻥ‬
‫ﺍﻝﺘﻲ ﻭﺠﺩﻨﺎﻫﺎ ﻓﻲ ﺍﻝﻔﻘﺭﺓ ﺍﻝﺴﺎﺒﻘﺔ‪ .‬ﻴﻅﻬﺭ ﻤﻥ ﺍﻝﺸﻜل ﺃ ‪‬‬
‫ﻤﻨﻔﺼﻠﺘﻴﻥ‪ .‬ﻭﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﻻ ﻴﻤﻜﻥ ﻝﻠﻜﻤﻭﻥ ﺃﻥ ﻴﻜﻭﻥ ﺒﺂﻥ ﻭﺍﺤﺩ ﺃﻜﺒﺭ ﻤﻥ ‪0.46 V‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ‪ Cu+‬ﻝﻴﺴﺕ ﻤﺴﺘﻘﺭﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ .‬ﻭﻨﻘﻭل‬

‫ﻭﺃﺼﻐﺭ ﻤﻥ ‪ . 0.16 V‬ﻫﺫﺍ ﻴﻌﻨﻲ ﺃ ‪‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ‪ Cu+‬ﺘﺘﻔﻜﹼﻙ ﺫﺍﺘﻴﹰﺎ ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺇ ‪‬‬
‫)‪2 Cu+ Cu2 + + Cu(s‬‬
‫ﻭﻴﻜﻭﻥ ﺘﺭﻜﻴﺯﻫﺎ ﺃﺼﻐﺭ ﺩﻭﻤﹰﺎ ﻤﻥ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﺤﺩﻱ ﺍﻷﻋﻅﻤﻲ ‪ .C lim‬ﻨﺴﻤ‪‬ﻲ ﻫﺫﺍ ﺍﻝﻨﻭﻉ‬
‫ﻤﻥ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﺫﻱ ﺘﻜﻭﻥ ﻓﻴﻪ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ‪ Cu+‬ﻫﻲ ﺍﻝﻤﺅﻜﺴ‪‬ﺩ ﻓﻲ‬
‫ﺍﻝﺯﻭﺝ )‪ (Cu+ /Cu‬ﻭﺍﻝﻤﺭﺠﹺﻊ ﻓﻲ ﺍﻝﺯﻭﺝ ) ‪ (Cu2 + /Cu+‬ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﺫﺍﺘﻲ‬
‫)‪ dismutation‬ﺃﻭ ‪.(disproportionation‬‬
‫)‪E (V‬‬
‫‪Cu2 +‬‬
‫‪0.31‬‬
‫)‪Cu (s‬‬
‫ﺍﻝﺸﻜل )‪ : (8‬ﻤﻨﻁﻘﺔ ﺭﺠﺤﺎﻥ ﺸﻭﺍﺭﺩ ‪ Cu2 +‬ﻭﻤﻨﻁﻘﺔ ﻭﺠﻭﺩ ﻤﻌﺩﻥ ﺍﻝﻨﺤﺎﺱ ﻓﻲ ﺤﺎﻝﺔ‬
‫‪. [Cu2 + ]lim = 0.1 mol/ L‬‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺤﺎﺱ )‪ (I‬ﻻ ﻴﻤﻜﻥ ﺃﻥ ﺘﻜﻭﻥ ﺃﺒﺩﹰﺍ ﺭﺍﺠﺤﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﻋﻠﻴﻪ‬

‫ﻻ ﺸﻭﺍﺭﺩ ‪Cu2 +‬‬
‫ﻴﻠﺯﻡ ﺘﻌﺩﻴل ﺍﻝﻤﺨﻁﻁ ﺍﻝﺫﻱ ﺭﺴﻤﻨﺎﻩ ﻓﻲ ﺍﻝﺸﻜل )‪ (7‬ﺒﺤﻴﺙ ﻻ ﺘﻅﻬﺭ ﻓﻴﻪ ﺇ ﹼ‬
‫ﻭﻤﻌﺩﻥ ﺍﻝﻨﺤﺎﺱ‪ ،‬ﻜﻤﺎ ﻴﻅﻬﺭ ﻫﺫﺍ ﻤﻥ ﺍﻝﺸﻜل )‪ . (8‬ﻓﻲ ﺍﻝﺤﺎﻝﺔ ﺍﻝﺘﻲ ﻴﻜﻭﻥ ﻓﻴﻬﺎ‬
‫ﻴﺴﺎﻭﻱ‬ ‫ﺍﻝﻔﺎﺼل‬ ‫ﺍﻝﺤ ‪‬ﺩ‬ ‫ﻋﻨﺩ‬ ‫ﺍﻝﻜﻤﻭﻥ‬ ‫ﻥ‬

‫ﻓﺈ ‪‬‬ ‫‪[Cu2 + ]lim = C lim = 0.1 mol/ L‬‬
‫‪. E2 = E (Cu2 + /Cu) + 0.03 log C lim = 0.31 V‬‬
‫

‬
‫ﺃﺨﻁﺎﺀ ﻤﺭﺩ‪‬ﻫﺎ ﺍﻝﺠﻬل ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫ﻤﺄﺴﺎﺓ ﺘﺸﺭﻨﻭﺒﻴل ‪1986‬‬

‫ﻥ ﺤﺎﺩﺜﺔ ﺍﻝﻤﻔﺎﻋل ﺍﻝﻨﻭﻭﻱ ﻓﻲ ﺘﺸﺭﻨﻭﺒﻴل ﻓﻲ ﺃﻭﻜﺭﺍﻨﻴﺎ ﻋﺎﻡ ‪ 1986‬ﻭﻗﺒﻠﻬﺎ ﺤﺎﺩﺜﺔ ﺍﻝﻤﻨﺸﺄﺓ ﺍﻝﻨﻭﻭﻴﺔ ﺜﺭﻱ ﻤﺎﻴل ﺁﻴﻠﻨﺩ ﻓﻲ‬
‫ﺇ‪‬‬
‫ﻭﻻﻴﺔ ﺒﻨﺴﻠﻔﺎﻨﻴﺎ ﺍﻷﻤﺭﻴﻜﻴﺔ ﻋﺎﻡ ‪ 1979‬ﻜﺎﻥ ﻤﺭﺩﻫﻤﺎ ﺘﻔﺎﻋﻼﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻝﻡ ﺘﻜﻥ ﻤﺘﻭﻗﻌﺔ‪ .‬ﻓﻔﻲ ﻜﻠﺘﺎ ﺍﻝﺤﺎﺩﺜﺘﻴﻥ ﺤﺼل‬
‫ﻋﻁل ﻓﻲ ﻤﻀﺨﺎﺕ ﺍﻝﺘﺒﺭﻴﺩ ﺃﺩ‪‬ﻯ ﺇﻝﻰ ﺍﺭﺘﻔﺎﻉ ﻓﻲ ﺩﺭﺠﺎﺕ ﺍﻝﺤﺭﺍﺭﺓ ﺇﻝﻰ ‪ 350C‬ﺘﻘﺭﻴﺒﹰﺎ‪ .‬ﺃﺩﻯ ﻫﺫﺍ ﺍﻻﺭﺘﻔﺎﻉ ﻓﻲ‬
‫ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﻤﻔﺎﻋل ﺇﻝﻰ ﺘﻔﻜﹼﻙ ﺍﻝﻁﺒﻘﺔ ﺍﻝﻭﺍﻗﻴﺔ ﻤﻥ ﺍﻷﻜﺴﻴﺩ ﺍﻝﻤﻌﺩﻨﻲ ﺍﻝﺘﻲ ﺘﺤﻤﻲ ﺴﻁﺢ ﺍﻝﻤﻔﺎﻋل ﺍﻝﻤﺒﻨﻲ ﻤﻥ ﺍﻷﻝﻤﻨﻴﻭﻡ‬
‫ﻭﺍﻝﺯﻜﻭﻨﻴﻭﻡ‪ ،‬ﺤﻴﺙ ﻴﺘﻔﺎﻋل ﺍﻝﺯﺭﻜﻭﻨﻴﻭﻡ ﻤﻊ ﺒﺨﺎﺭ ﺍﻝﻤﺎﺀ ﻭﻴﺘﺸﻜﹼل ﻏﺎﺯ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺤﺴﺏ ﻤﻌﺎﺩﻝﺔ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫)‪Zr(s) + 2H2O(g) → ZrO2 (s) + 2H2 (g‬‬
‫ﻭﻨﺘﻴﺠﺔ ﻝﺫﻝﻙ ﺘﺸﻜﹼل ﻓﻲ ﺤﺎﻝﺔ ﻤﻔﺎﻋل ﺒﻨﺴﻠﻔﺎﻨﻴﺎ ﻗﺭﺍﺒﺔ ‪ 300m 3‬ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻐﺎﺯﻱ ﺍﻝﺫﻱ ﻴﺸﺘﻌل ﺒﺄﻗل ﺸﺭﺍﺭﺓ‪.‬‬
‫ﻭﻴﻤﻜﻨﻨﺎ ﺃﻥ ﻨﺘﺨﻴل ﺒﻌﺩ ﺫﻝﻙ ﺤﺠﻡ ﺍﻝﻤﺄﺴﺎﺓ ﺍﻝﺘﻲ ﺘﻠﺕ ﺫﻝﻙ‪.‬‬
‫ﺃﺨﻁﺎﺀ ﻓﻲ ﻭﺼل ﺃﻨﺎﺒﻴﺏ ﻨﻘل ﺍﻝﻐﺎﺯ ﺃﻭ ﺍﻝﻨﻔﻁ‬

‫ﻋﻨﺩﻤﺎ ﻴﺠﺭﻱ ﺨﻁ ًﺄ ﻭﺼل ﺃﻨﺎﺒﻴﺏ ﺤﺩﻴﺩ ﻤﻐﻠﻔﻨﺔ )ﺃﻱ ﺤﺩﻴﺩ ﻤﻁﻠﻲ ﺒﺎﻝﺘﻭﺘﻴﺎﺀ( ﻤﻊ ﺃﻨﺎﺒﻴﺏ ﻨﺤﺎﺱ‪ ،‬ﺘﻘﻭﻡ ﻓﻲ ﺍﻝﺒﺩﺍﻴﺔ ﺸﻭﺍﺭﺩ‬
‫ﺍﻝﻨﺤﺎﺱ ﺒﺄﻜﺴﺩﺓ ﻁﻼﺀ ﺍﻝﺘﻭﺘﻴﺎﺀ ﻝﺘﺼﺒﺢ ﺃﻨﺎﺒﻴﺏ ﺍﻝﺤﺩﻴﺩ ﺸﻴﺌ ﹰﺎ ﻓﺸﻴﺌ ﹰﺎ ﺒﺩﻭﻥ ﺤﻤﺎﻴﺔ ﻭﻤﻌﺭ‪‬ﻀﺔ ﻝﻠﺼﺩﺃ‪:‬‬
‫‪Zn + Cu 2+ → Zn2+ + Cu‬‬
‫ﻭﻤﺎ ﺃﻥ ﺘﻨﺯﺍﺡ ﻁﺒﻘﺔ ﺍﻝﺘﻭﺘﻴﺎﺀ ﺍﻝﻭﺍﻗﻴﺔ ﺤﺘﻰ ﻴﺤﺼل ﺼﺩﺃ ﻤﺘﺴﺎﺭﻉ ﻓﻲ ﺃﻨﺎﺒﻴﺏ ﺍﻝﺤﺩﻴﺩ ﻷﻨﻪ ﺃﻜﺜﺭ ﻨﺸﺎﻁ ﹰﺎ ﻤﻥ ﺍﻝﻨﺤﺎﺱ‬
‫ﻭﻴﺅﺩﻱ ﺍﻝﺤﺩﻴﺩ ﺩﻭﺭ ﺍﻝﻤﺼﻌﺩ ﺍﻝﻤﻀﺤﻲ‪ .‬ﻭﻨﺴﻤﻊ ﺒﻌﺩ ﺫﻝﻙ ﺃﺨﺒﺎﺭﹰﺍ ﻋﻥ ﺘﺴﺭﺒﺎﺕ ﻓﻲ ﺨﻁﻭﻁ ﻨﻘل ﺍﻝﻐﺎﺯ ﺃﻭ ﺍﻝﻨﻔﻁ‪.‬‬
‫ﺃﺨﻁﺎﺀ ﻓﻲ ﻤﺠﺎل ﺼﻨﺎﻋﺔ ﺍﻝﺴﻴﺎﺭﺍﺕ‬

‫ﻅﻬﺭﺕ ﻓﻲ ﺍﻝﺴﺒﻌﻴﻨﺎﺕ ﻤﻥ ﺍﻝﻘﺭﻥ ﺍﻝﻤﺎﻀﻲ ﺒﻌﺽ ﺃﻨﻭﺍﻉ ﻤﻥ ﺍﻝﺴﻴﺎﺭﺍﺕ ﺍﻝﺘﻲ ﻋﺎﻨﺕ ﻤﻥ ﺒﻌﺽ ﺍﻝﻤﺸﺎﻜل ﺍﻝﺘﻘﻨﻴﺔ ﺇﺫ‬
‫ﻜﺎﻨﺕ ﺍﻝﻤﻴﺎﻩ ﺘﺘﺴﺭ‪‬ﺏ ﻤﻥ ﻤﻀﺨﺔ ﺍﻝﻤﺎﺀ‪ .‬ﻭﻓﻲ ﻤﺤﺎﻭﻝﺔ ﻝﻔﻬﻡ ﻤﺎ ﻜﺎﻥ ﻴﺤﺼل ﻭﺠﺩ ﺍﻝﻤﻬﻨﺩﺴﻭﻥ ﺃﻥ ﻤﻀﺨﺔ ﺍﻝﻤﺎﺀ ﻗﺩ‬
‫ﺼ‪‬ﻨﻌﺕ ﻤﻥ ﺍﻷﻝﻤﻨﻴﻭﻡ ﻭﺒﺘﻤﺎﺱ ﻤﻊ ﺠﺴﻡ ﺍﻝﻤﺤﺭ‪‬ﻙ ﺍﻝﻤﺼﻨﻭﻉ ﻤﻥ ﺍﻝﺤﺩﻴﺩ ﺍﻝﺼﺏ‪ ،‬ﻭﻝﻤﹼﺎ ﻜﺎﻥ ﺍﻷﻝﻤﻨﻴﻭﻡ ﺃﻜﺜﺭ ﻨﺸﺎﻁ ﹰﺎ ﻤﻥ‬
‫ﺍﻝﺤﺩﻴﺩ ﻓﻘﺩ ﺘﻔﺎﻋل ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ﺍﻝﻤﺘﺸﻜﻠﺔ ﻤﻥ ﺘﺄﺜﻴﺭ ﺃﻜﺴﺠﻴﻥ ﺍﻝﻬﻭﺍﺀ ﻝﻴﻌﻁﻲ ﺸﻭﺍﺭﺩ ﺍﻷﻝﻤﻨﻴﻭﻡ‪ ،‬ﻓﺄﺩﻯ ﺫﻝﻙ ﺇﻝﻰ‬
‫ﺍﻝﺘﺴﺭﺏ‪:‬‬
‫‪3+‬‬ ‫‪3+‬‬
‫‪Al + Fe‬‬ ‫‪→ Al‬‬ ‫‪+ Fe‬‬
‫‪ .IV‬ﺍﻝﻌﻭﺍﻤل ﺍﻝﻤﺅﺜﹼﺭﺓ ﻓﻲ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫ل ﺍﻝﻌﻭﺍﻤل ﺍﻝﺘﻲ ﻤﻥ ﺸﺄﻨﻬﺎ ﺘﻐﻴﻴﺭ ﺍﻝﻔﻌﺎﻝﻴﺔ ﻝﻭﺍﺤﺩ ﻋﻠﻰ ﺍﻷﻗل ﻤﻥ‬

‫ﻨﺄﺨﺫ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﻜ ّ‬
‫ﺍﻷﻨﻭﺍﻉ ﺍﻝﺘﻲ ﺘﺩﺨل ﻓﻲ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻭﺍﻝﺫﻱ ﻤﻥ ﺸﺄﻨﻪ ﺘﻐﻴﻴﺭ ﺍﻝﻤﻘﺩﺍﺭ ﺍﻝﻭﺍﻗﻊ ﻀﻤﻥ‬
‫ﺍﻝﻠﻭﻏﺎﺭﻴﺘﻡ ‪ log‬ﻓﻲ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﺘﻐﻴﻴﺭ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻝﻠﺯﻭﺝ ﺍﻝﻤﻌﺘﺒﺭ‪.‬‬
‫ﻭﻝﻨﺩﺭﺱ ﻓﻴﻤﺎ ﻴﻠﻲ ﺃﻤﺜﻠﺔ ﻋﻥ ﺒﻌﺽ ﺃﻫﻡ ﻫﺫﻩ ﺍﻝﻌﻭﺍﻤل‪:‬‬
‫‪ .1.IV‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﺭﻜﻴﺯ‬
‫ﻝﻨﺩﺭﺱ ﺘﺄﺜﻴﺭ ﺘﺭﻜﻴﺯ ﺃﺤﺩ ﺍﻷﻨﻭﺍﻉ ﻋﻠﻰ ﺍﻝﻜﻤﻭﻥ ﻭﺫﻝﻙ ﻤﻥ ﺨﻼل ﺘﺤﻠﻴﻠﻨﺎ ﻝﻌﻤل ﺍﻝﺨﻠﻴﺔ‬
‫ﺍﻝﻤﻌﺭﻭﻓﺔ ﺒﺎﺴﻡ ﺨﻠﻴﺔ ﺍﻝﺘﺭﻜﻴﺯ‪.‬‬
‫ل ﻨﺼﻑ ﻤﻥ ﺴﻠﻙ ﻤﻥ ﺍﻝﻨﺤﺎﺱ‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺍﻝﺨﻠﻴﺔ ﺍﻝﻤﺅﻝﹼﻑ ﻤﻥ ﺘﺠﻤﻴﻊ ﻨﺼﻔﻲ ﺨﻠﻴﺔ‪ ،‬ﻴﺘﺄﻝﻑ ﻜ ّ‬
‫ﻤﻐﻤﻭﺱ ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻨﺤﺎﺱ ﺒﺤﺠﻡ ‪ V = 50.0 mL‬ﺍﻷﻭل ﺒﺘﺭﻜﻴﺯ‬
‫‪) 0.100 mol/L‬ﺍﻝﻨﺼﻑ ﺍﻷﻭل ﻝﻠﺨﻠﻴﺔ( ﻭﺍﻝﺜﺎﻨﻲ ﺒﺘﺭﻜﻴﺯ ‪) 1.00 × 10−2 mol/L‬ﺍﻝﻨﺼﻑ‬
‫ﺍﻝﺜﺎﻨﻲ ﻝﻠﺨﻠﻴﺔ( ﻭﻴﺴﻤﺢ ﻫﻼﻡ ﻤﺤﻀﺭ ﻤﻥ ﻤﺤﻠﻭل ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻷﻤﻭﻨﻴﻭﻡ ﺒﺘﺤﻘﻴﻕ ﺍﻝﻭﺼل ﺒﻴﻥ‬
‫ﻨﺼﻔﻲ ﺍﻝﺨﻠﻴﺔ‪ ،‬ﺍﻝﺸﻜل )‪ . (9‬ﻴﻜﻭﻥ ﻤﻌﺩﻥ ﺍﻝﻨﺤﺎﺱ ﻓﺎﺌﻀﹰﺎ ﻓﻲ ﻜﻼ ﻨﺼﻔﻲ ﺍﻝﺨﻠﻴﺔ‪.‬‬
‫‪. E 0 (Cu2+/ Cu) = 0.34 V‬‬
‫‪mV‬‬ ‫‪+‬‬ ‫‪−‬‬

‫‪NH 4 +NO3‬‬
‫ﰲ ﻫﻼﻡ‬
‫‪Cu‬‬ ‫‪M1‬‬ ‫‪M2‬‬ ‫‪Cu‬‬

‫‬ ‫‬
‫‪2+‬‬ ‫‪2+‬‬
‫‪ Cu‬ﺑﺘﺮﻛﻴﺰ ﻗﺪﺭﻩ‬ ‫‪ Cu‬ﺑﺘﺮﻛﻴﺰ ﻗﺪﺭﻩ‬
‫‪−1‬‬ ‫‪−1‬‬
‫‪0.1 mol⋅ L‬‬ ‫‪0.01 mol⋅ L‬‬
‫‪2+‬‬ ‫‪2−‬‬ ‫‪2+‬‬ ‫‪2−‬‬

‫‪Cu‬‬ ‫‪+SO 4‬‬ ‫‪Cu‬‬ ‫‪+SO 4‬‬
‫ﺍﻝﺸﻜل )‪ : (9‬ﻤﺨﻁﻁ ﻝﻠﺒﻴل‬
‫ل‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﻗﻁﺒﻲ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ‪ ،‬ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺤﺼﻠﺔ ﺍﻝﺘﻲ ﺘﺤﺼل ﻓﻲ ﻜ ّ‬
‫ﻨﺼﻑ ﺨﻠﻴﺔ‪ ،‬ﻭﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ﺍﻝﺘﻲ ﺘﻌﺒ‪‬ﺭ ﻋﻥ ﻋﻤل ﺍﻝﺨﻠﻴﺔ‪.‬‬
‫ل ﺠﺯﺀ ﻤﻥ ﺍﻝﺨﻠﻴﺔ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﺘﺘﻭﻗﹼﻑ ﺍﻝﺨﻠﻴﺔ ﻋﻥ ﺘﻭﻝﻴﺩ‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﻨﻬﺎﺌﻴﺔ ﻓﻲ ﻜ ّ‬
‫ﺍﻝﺘﻴﺎﺭ ﺍﻝﻜﻬﺭﺒﺎﺌﻲ‪ .‬ﺍﺴﺘﻨﺘﺞ ﻤﻥ ﺫﻝﻙ ﻜﻤﻴﺔ ﺍﻝﻜﻬﺭﺒﺎﺀ ﺍﻝﺘﻲ ﻤﺭ‪‬ﺕ ﻓﻲ ﺍﻝﺩﺍﺭﺓ‪.‬‬
‫‪ .3‬ﺤﺩ‪‬ﺩ ﺤﺭﻜﺔ ﺍﻝﺸﺤﻨﺎﺕ ﺩﺍﺨل ﺠﺴﺭ ﺍﻝﻭﺼل ﺒﻴﻥ ﻨﺼﻔﻲ ﺍﻝﺨﻠﻴﺔ‪.‬‬
‫ﺍﻝﺤل‬
‫ﻥ ﺍﻝﺯﻭﺝ ‪ Ox/Red‬ﺍﻝﺫﻱ ﻨﺠﺩﻩ ﻓﻲ ﻨﺼﻔﻲ ﺍﻝﺨﻠﻴﺘﻴﻥ ﻫﻭ ‪: Cu2+/ Cu‬‬
‫‪ .1‬ﺇ ‪‬‬
‫‪. Cu2+ + 2e−
Cu‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ﻤﺴﺭﻯ ﺍﻝﻨﺤﺎﺱ ﺍﻷﻭل ﻨﻜﺘﺏ ‪:‬‬
‫‪E1 = 0.34 + 0.03 log [ Cu2+ ]1 = 0.31 V‬‬
‫ ﻓﻲ ﺤﺎﻝﺔ ﻤﺴﺭﻯ ﺍﻝﻨﺤﺎﺱ ﺍﻝﺜﺎﻨﻲ ﻨﻜﺘﺏ ‪:‬‬
‫‪2+‬‬
‫‪E 2 = 0.34 + 0.03 log [ Cu‬‬ ‫‪]2 = 0.28 V‬‬
‫ﺇﺫﻥ ‪ E 2 < E1‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺎﻝﻤﺴﺭﻯ ‪ M 1‬ﻴﺸﻜﹼل ﺍﻝﻘﻁﺏ ﺍﻝﻤﻭﺠﺏ ⊕ ﻭﺍﻝﻤﺴﺭﻯ ‪ M 2‬ﻴﺸﻜﹼل‬
‫ﺍﻝﻘﻁﺏ ﺍﻝﺴﺎﻝﺏ ⊖ ‪ ،‬ﺍﻝﺸﻜل )‪ . (10‬ﻭﻝﻨﺴ ‪‬ﻡ ‪ E‬ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻬﺫﻩ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ‪:‬‬
‫‪E = E1 − E 2 = 0.03 V‬‬
‫‪e−‬‬
‫‪mV‬‬
‫‪i‬‬
‫‪M1‬‬ ‫‪M2‬‬
‫‬ ‫‬
‫‪E1 > E 2‬‬

‫ﺍﻝﺸﻜل )‪ : (10‬ﻤﺨﻁﻁ ﻋﻤل ﺍﻝﺨﻠﻴﺔ‪.‬‬
‫ﻨﻼﺤﻅ ﺃﻥ ﺍﻝﺯﻭﺝ ‪ Cu 2+/ Cu‬ﻫﻭ ﻨﻔﺴﻪ ﺍﻝﺫﻱ ﻴﺩﺨل ﻓﻲ ﻋﻤل ﻨﺼﻔﻲ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻠﺫﻴﻥ‬
‫ﻻ ﺒﺎﻝﺘﺭﻜﻴﺯ‪ .‬ﻭﻝﻬﺫﺍ ﻓﺈﻨﻨﺎ ﻨﺴﻤ‪‬ﻲ ﻫﺫﻩ ﺍﻝﺨﻠﻴﺔ ﺒﺨﻠﻴﺔ ﺍﻝﺘﺭﻜﻴﺯ‪.‬‬
‫ﻻﻴﺨﺘﻠﻑ ﺃﺤﺩﻫﻤﺎ ﻋﻥ ﺍﻵﺨﺭ ﺇ ﹼ‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃﻥ ﺍﻝﺘﻴﺎﺭ ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﺨﺎﺭﺝ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﻴﺨﺭﺝ ﻤﻥ ﺍﻝﻘﻁﺏ ﺍﻝﻤﻭﺠﺏ ⊕‬
‫ﺒﺎﺘﺠﺎﻩ ﺍﻝﻘﻁﺏ ﺍﻝﺴﺎﻝﺏ ⊖ ‪ ،‬ﺃﻤﺎ ﺤﺭﻜﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻓﺘﻜﻭﻥ ﻓﻲ ﺍﺘﺠﺎﻩ ﻤﻌﺎﻜﺱ ﻤﻥ ﺍﻝﻤﺴﺭﻯ ﺍﻝﺜﺎﻨﻲ‬
‫ﺒﺎﺘﺠﺎﻩ ﺍﻝﻤﺴﺭﻯ ﺍﻷﻭل‪.‬‬
‫ﺃﻤﹼﺎ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﻠﺘﻔﺎﻋﻼﺕ ﺍﻝﺤﺎﺼﻠﺔ ﻓﻲ ﻨﺼﻔﻲ ﺍﻝﺨﻠﻴﺔ ﻓﻬﻲ‪:‬‬
‫ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﺜﺎﻨﻴﺔ ‪:‬‬

‫ﺃﻜﺴﺩﺓ‬ ‫‪Cu(2)
Cu 2+(2) + 2e−‬‬
‫ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻷﻭﻝﻰ ‪:‬‬
‫ﺇﺭﺠﺎﻉ‬ ‫)‪Cu2+(1) + 2e−
Cu(1‬‬
‫ﻭﺘﻜﻭﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ﻝﻌﻤل ﺍﻝﺨﻠﻴﺔ ‪:‬‬
‫)‪Cu2+(1) + Cu(2)
Cu(1) + Cu2+(2‬‬
‫ﻥ ﺍﻝﺨﻠﻴﺔ ﺴﺘﺘﻭﻗﻑ ﻋﻥ ﺘﻭﻝﻴﺩ ﺍﻝﺘﻴﺎﺭ ﺍﻝﻜﻬﺭﺒﺎﺌﻲ ﻭﺘﻨﻌﺩﻡ ﺍﻝﻘﻭﺓ‬

‫‪ .2‬ﻝﻤﺎ ﻜﺎﻥ ﻤﻌﺩﻥ ﺍﻝﻨﺤﺎﺱ ﻓﺎﺌﻀﺎﹰ‪ ،‬ﻓﺈ ‪‬‬
‫ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﺨﻠﻴﺔ‪ ،‬ﺃﻱ ﻋﻨﺩﻤﺎ ﺘﺼﺒﺢ ﺍﻝﺠﻤﻠﺔ ﺍﻝﻜﻬﺭﻜﻴﻤﻴﺎﺌﻴﺔ ﻓﻲ ﺘﻭﺍﺯﻥ‪ ،‬ﻋﻨﺩﻫﺎ ﻨﻜﺘﺏ‪:‬‬
‫‪ E1eq = E2eq‬ﺃﻱ ﻋﻨﺩﻤﺎ ‪[ Cu2+ ]1eq = [ Cu2+ ]2eq‬‬
‫)‪Cu2+ (1‬‬ ‫)‪+ Cu(2) ⇌ Cu(1) + Cu2 + (2‬‬

‫‪t = 0 0.100‬‬ ‫‪0.010‬‬
‫‪teq‬‬ ‫‪0.100 − x‬‬ ‫‪0.010 + x‬‬
‫ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻴﻜﻭﻥ‬

‫‪0.100 − x = 0.010 + x‬‬
‫ﻭﻤﻨﻪ ﻨﺠﺩ‪:‬‬
‫‪[ Cu2+ ]1eq = [ Cu2+ ]2eq = 0.055 mol/L‬‬

‫ﻝﺘﻜﻥ ‪ Q‬ﻜﻤﻴﺔ ﺍﻝﻜﻬﺭﺒﺎﺀ ﺍﻝﺘﻲ ﻤﺭ‪‬ﺕ ﺒﺎﻝﺩﺍﺭﺓ‪:‬‬
‫‪Q = ∆n(e− ) ⋅ F‬‬
‫ﻥ‪:‬‬
‫‪Q = 2∆n(Cu2 + ) ⋅ F = 2∆ ( [ Cu2+ ]) ⋅ V ⋅ F‬‬
‫ﻭﻫﻜﺫﺍ ﻨﻜﺘﺏ‪:‬‬
‫‪Q = 2 × 0.045 × 50 × 10−3 × 69500 = 4300 C‬‬
‫ﻥ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﺒﺔ ﺴﻭﻑ ﺘﺘﺤﺭﻙ ﻓﻲ ﺍﻝﺠﻬﺔ ﺍﻝﺘﻲ ﻴﺘﺤﺭﻙ ﺒﻬﺎ ﺍﻝﺘﻴﺎﺭ‪،‬‬

‫‪ .3‬ﻋﻨﺩﻤﺎ ﺘﻌﻤل ﺍﻝﺨﻠﻴﺔ ﻓﺈ ‪‬‬
‫ﻓﻲ ﺤﻴﻥ ﺘﺘﺤﺭﻙ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺴﺎﻝﺒﺔ ﻓﻲ ﺍﻻﺘﺠﺎﻩ ﺍﻝﻤﻌﺎﻜﺱ‪ ،‬ﺍﻝﺸﻜل )‪. (11‬‬
‫ ﻓﻔﻲ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻷﻭل‪ :‬ﺘﺘﺭﻙ ﺸﻭﺍﺭﺩ ﺍﻷﻤﻭﻨﻴﻭﻡ ﺍﻝﺠﺴﺭ ﻭﺘﺩﺨل ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻓﻲ ﺤﻴﻥ‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﺘﺩﺨل ﺇﻝﻰ ﺍﻝﺠﺴﺭ‪.‬‬
‫ﺃ‪‬‬
‫ ﻭﻓﻲ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﺜﺎﻨﻲ‪ :‬ﺘﺘﺭﻙ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺘﺭﺍﺕ ﺍﻝﺠﺴﺭ ﻭﺘﺩﺨل ﺇﻝﻰ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻓﻲ ﺤﻴﻥ‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺤﺎﺱ ﺘﺩﺨل ﺇﻝﻰ ﺍﻝﺠﺴﺭ‪.‬‬
‫ﺃ‪‬‬
‫ل ﻝﺤﻅﺔ ﻴﻜﻭﻥ ﻨﺼﻔﺎ ﺍﻝﺨﻠﻴﺔ ﻭﺍﻝﺠﺴﺭ ﻤﻌﺘﺩﻝﻴﻥ ﻜﻬﺭﺒﺎﺌﻴﹰﺎ‪.‬‬

‫ﻭﻓﻲ ﻜ ّ‬
‫)‪(a‬‬ ‫)‪(b‬‬
‫‬ ‫‬
‫‪i‬‬ ‫‪i‬‬
‫‬ ‫‬ ‫‬ ‫‬
‫‪NH+‬‬
‫‪4‬‬ ‫‪NO−‬‬
‫‪3‬‬ ‫‪NH+‬‬
‫‪4‬‬ ‫‪NO−‬‬
‫‪3‬‬
‫‪Cu2 +‬‬ ‫‪SO24 −‬‬ ‫‪Cu2 +‬‬ ‫‪SO24 −‬‬
‫ﺍﻝﺸﻜل ) ‪ (a) : ( 11‬ﺤﺭﻜﺔ ﺍﻝﺸﺤﻨﺎﺕ ﺩﺍﺨل ﺍﻝﺠﺴﺭ‪،‬‬

‫)‪ (b‬ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﺠﺴﺭ ﺒﻌﺩ ﻤﺭﻭﺭ ﺯﻤﻥ ﻋﻠﻰ ﻋﻤل ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ‪.‬‬
‫‪ .2.IV‬ﺘﺄﺜﻴﺭ ﺍﻝـ ‪pH‬‬
‫‪ .1.2.IV‬ﻤﺜﺎل‪ :‬ﺍﻝﺯﻭﺝ ‪. O2 / H2 O‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺼﻔﻴﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻠﺯﻭﺝ ‪ O2/ H2 O‬ﻫﻲ‪:‬‬

‫ﺇ‪‬‬
‫‪O2 + 4e− + 4 H3 O+ ⇌ 6 H2 O‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﺘﹸﻜﺘﺏ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬

‫‪0.06‬‬ ‫‪4‬‬
‫‪E = E (O2/ H2 O) +‬‬ ‫) ] ‪log ( P(O2 ).[ H3 O+‬‬
‫‪4‬‬
‫ﻥ ﻓﻌﺎﻝﻴﺔ ﺍﻝﻤﺎﺀ ﺘﺴﺎﻭﻱ ﺍﻝﻭﺍﺤﺩ ‪ ، a(H2 O) = 1‬ﻓﺈﺫﺍ ﺃﺨﺫﻨﺎ ‪P (O2 ) = 1 bar‬‬

‫ﻭﺫﻝﻙ ﻷ ‪‬‬
‫ﻭﺠﺩﻨﺎ ‪:‬‬
‫‬
‫‪E = E (O2/ H2 O) − 0.06 pH = 1.23 − 0.06 pH‬‬
‫ﻥ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﺅﻜﺴﺩﺓ ﻝﻸﻜﺴﺠﻴﻥ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﺘﺘﻨﺎﻗﺹ ﻤﻊ ﺍﺭﺘﻔﺎﻉ ﺍﻝــ ‪pH‬‬
‫ﻜﻤﺎ ﻴﻅﻬﺭ ﻫﺫﺍ ﺠﻠﻴﹰﺎ ﻓﻲ ﺍﻝﺸﻜل )‪. (12‬‬
‫)‪E (V‬‬
‫‪1‬‬ ‫‪O2‬‬
‫‪0.5‬‬ ‫‪H2O‬‬
‫‪0‬‬
‫‪7‬‬ ‫‪14‬‬ ‫‪pH‬‬
‫ﺍﻝﺸﻜل )‪ : (12‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺯﻭﺝ ‪ O2/H2O‬ﻴﺘﻌﻠﹼﻕ ﺍﻝﻜﻤﻭﻥ ﺒﻘﻴﻤﺔ ‪pH‬‬
‫‪. Mn O−‬‬
‫‪4 / Mn‬‬
‫‪2+‬‬
‫‪ .2.2.IV‬ﻤﺜﺎل‪ :‬ﺍﻝﺯﻭﺝ‬
‫‪ Mn O−‬ﻫﻲ‪:‬‬
‫‪4 / Mn‬‬
‫‪2+‬‬
‫ﻥ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺼﻔﻴﺔ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻠﺯﻭﺝ‬
‫ﺇ‪‬‬
‫‪Mn O−‬‬ ‫‪−‬‬ ‫‪+‬‬ ‫‪2+‬‬
‫‪4 + 5e + 8 H 3 O ⇌ Mn + 12 H2 O‬‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﺘﹸﻜﺘﺏ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻜﻤﺎ ﻴﻠﻲ‪:‬‬

‫‪8‬‬
‫‪0.06‬‬ ‫‪[ Mn O−‬‬ ‫‪+‬‬
‫] ‪4 ][ H 3 O‬‬
‫‪E = E (Mn O−4 / Mn2+ ) +‬‬ ‫‪log‬‬
‫‪5‬‬ ‫] ‪[ Mn2+‬‬
‫ﻥ‪:‬‬
‫ﺃﻱ ﺃ ‪‬‬
‫‪0.06‬‬ ‫‪0.06‬‬ ‫‪[ Mn O−‬‬‫] ‪4‬‬
‫‪E = E (Mn O−4 / Mn 2+ ) −‬‬ ‫‪× 8 pH +‬‬ ‫‪log‬‬ ‫‪2+‬‬
‫‪5‬‬ ‫‪5‬‬ ‫] ‪[ Mn‬‬
‫ﻥ‪:‬‬
‫ﻨﻔﺘﺭﺽ ﺃ ‪‬‬
‫‪0.06‬‬
‫‪E ′ = E (Mn O−‬‬ ‫‪2+‬‬
‫‪4 / Mn ) −‬‬ ‫‪× 8 pH‬‬
‫‪5‬‬
‫‪= E (Mn O−‬‬ ‫‪2+‬‬
‫‪4 / Mn ) − 0.096 pH‬‬
‫ﻭﻫﻭ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻨﻅﺎﻤﻲ ﺍﻝﻅﺎﻫﺭﻱ ﺒﺩﻻﻝﺔ ﺍﻝـ ‪ . pH‬ﻭﻫﻭ ﻴﺘﺭﺠﻡ ﺍﻝﻁﺭﻴﻘﺔ ﺍﻝﺘﻲ ﻴﺘﻐﻴﺭ ﻓﻴﻬﺎ ﺍﻝﻜﻤﻭﻥ‬
‫ل ﻤﻥ ﺍﻝﻤﺅﻜﺴﺩ ﻭﺍﻝﻤﺭﺠﻊ ﻤﺴﺎﻭﻴﺔ ﻝﻠﻭﺍﺤﺩ‪.‬‬
‫‪ E‬ﺒﺩﻻﻝﺔ ﺍﻝـ ‪ pH‬ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﺍ ﻝﻔﻌﺎﻝﻴﺔ ﻝﻜ ﱟ‬
‫ﻥ ﺍﻝﻘﺩﺭﺓ ﺍﻝﻤﺅﻜﺴﺩﺓ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﺘﺘﻨﺎﻗﺹ ﻤﻊ ﺍﺭﺘﻔﺎﻉ ﺍﻝـ ‪. pH‬‬
‫‪ .3.IV‬ﺘﺄﺜﻴﺭ ﺍﻝﺘﻌﻘﻴﺩ ﻭﺍﻝﺘﺭﺴﻴﺏ‬
‫ﻝﻨﺘﺄﻤ‪‬ل ﺯﻭﺠﹰﺎ ‪ Ox / Red‬ﺒﺤﻴﺙ ﺘﻜﻭﻥ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻪ‪:‬‬
‫‪0.06‬‬ ‫] ‪[ Ox‬‬
‫‪E (Ox / Red) = E (Ox / Red) +‬‬ ‫‪log‬‬
‫‪n‬‬ ‫] ‪[ Red‬‬
‫ﻥ‬
‫ﻥ )‪ E (Ox / Red‬ﺘﺘﻨﺎﻗﺹ‪ ،‬ﻭ ﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫
ﺇﺫﺍ ﺘﻨﺎﻗﺹ ﺘﺭﻜﻴﺯ ﺍﻝﻤﺅﻜﺴﺩ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻓﺈ ‪‬‬
‫ﻥ ﻗﺩﺭﺓ ﺍﻹﺭﺠﺎﻉ ﻋﻨﺩ ﺍﻝﻤﺭﺠﻊ ﺘﺘﺯﺍﻴﺩ‪.‬‬
‫ﻗﺩﺭﺓ ﺍﻷﻜﺴﺩﺓ ﻋﻨﺩ ﺍﻝﻤﺅﻜﺴﺩ ﺘﺘﻨﺎﻗﺹ‪ ،‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﻭﻨﺼل ﺇﻝﻰ ﻫﺫ ﺍ ﺍ ﻝﻭﻀﻊ ﻋﻠﻰ ﺴﺒﻴل ﺍ ﻝﻤﺜﺎ ل ﺇ ﺫ ﺍ ﺴﺎﻫﻡ ﺍ ﻝﻤﺅﻜﺴﺩ ﻓﻲ ﺘﻔﺎﻋﻼﺕ ﺘﻌﻘﻴﺩ ﺃﻭ‬
‫ﺘﺭﺴﻴﺏ‪ ،‬ﺍﻝﺸﻜل ))‪. (13 − (a‬‬
‫ﻥ‬
‫ﻥ )‪ E (Ox / Red‬ﻴﺯﺩﺍﺩ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫
ﻤﻥ ﺠﻬﺔ ﺃﺨﺭﻯ‪ ،‬ﺇﺫﺍ ﺍﻨﺨﻔﺽ ﺘﺭﻜﻴﺯ ﺍﻝﻤﺭﺠﻊ‪ ،‬ﻓﺈ ‪‬‬
‫ﻥ ﻗﺩﺭﺓ ﺍﻹﺭﺠﺎﻉ ﻋﻨﺩ ﺍﻝﻤﺭﺠﻊ ﺘﺘﻨﺎﻗﺹ‪.‬‬
‫ﻗﺩﺭﺓ ﺍﻷﻜﺴﺩﺓ ﻋﻨﺩ ﺍﻝﻤﺅﻜﺴﺩ ﺘﺯﺩﺍﺩ‪ ،‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﻭ ﻨﺼل ﺇ ﻝﻰ ﻫﺫ ﺍ ﺍ ﻝﻭﻀﻊ ﻋﻠﻰ ﺴﺒﻴل ﺍ ﻝﻤﺜﺎ ل ﺇ ﺫ ﺍ ﺴﺎ ﻫﻡ ﺍ ﻝﻤﺭ ﺠﻊ ﻓﻲ ﺘﻔﺎ ﻋﻼﺕ ﺘﻌﻘﻴﺩ ﺃﻭ‬
‫ﺘﺭﺴﻴﺏ‪ ،‬ﺍﻝﺸﻜل ))‪. (13 − (b‬‬
‫)‪E ( V‬‬ ‫)‪E ( V‬‬ ‫)‪E ( V‬‬ ‫)‪E ( V‬‬
‫)‪E (Ox/Red‬‬ ‫)‪E (Ox/Red‬‬

‫ ‪∆E‬‬ ‫ ‪∆E‬‬
‫‪Ox‬‬ ‫‪Ox‬‬
‫(‬
‫‪ Red‬ﻤﻌﻘﺩ ‪E‬‬ ‫)‬ ‫(‬
‫‪ Red‬ﻤﻌﻘﺩ ‪E‬‬ ‫)‬
‫‪∆E < 0‬‬ ‫‪∆E < 0‬‬
‫)‪ (b‬ﺤﺎﻝﺔ ﺍﻝﻤﺭﺠﻊ‬ ‫) ‪ (a‬ﺤﺎﻝﺔ ﺍﻝﻤﺅﻜﺴﺩ‬
‫ﺍﻝﺸﻜل )‪ : (13‬ﺘﻐﻴﺭ ﺍﻝﻘﺩﺭﺓ ﻋﻠﻰ ﺍﻷﻜﺴﺩﺓ ﺃﻭ ﺍﻹﺭﺠﺎﻉ ﻝﺯﻭﺝ ﺒﺴﺏ ﺍﻝﺘﻌﻘﻴﺩ ﺃﻭ ﺍﻝﺘﺭﺴﻴﺏ‪.‬‬
‫ﻝﻨﺩﺭﺱ ﻓﻴﻤﺎ ﻴﻠﻲ ﺒﻌﺽ ﺍﻷﻤﺜﻠﺔ ﺍﻝﺘﻲ ﺘﻅﻬﺭ ﺘﺄﺜﻴﺭ ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﻤﻥ ﺍﻝﺘﻔﺎﻋﻼﺕ ﻋﻠﻰ ﺘﻔﺎﻋﻼﺕ‬
‫‪ .1.3.IV‬ﺘﻁﺒﻴﻕ ﺃﻭ‪‬ﻝ‬
‫ﻨﺸﻜﹼل ﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ ﻤﻥ ﻤﺴﺭﻯ ﻤﺭﺠﻌﻲ ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻭﻨﺼﻑ ﺨﻠﻴﺔ ﻤﺅﻝﻔﺔ ﻤﻥ ﺴﻠﻙ‬
‫ﻤﻥ ﺍ ﻝﻨﺤﺎ ﺱ ﻤﻐﻤﻭ ﺱ ﻓﻲ ﻤﺤﻠﻭ ل ﺤﺠﻤﻪ ‪ V = 40.0 mL‬ﻤﻥ ﻜﺒﺭ ﻴﺘﺎ ﺕ ﺍ ﻝﻨﺤﺎ ﺱ ﺒﺘﺭ ﻜﻴﺯ‬
‫‪ ، 1.00 × 10−2 mol / L‬ﺃُﻀﻴﻑ ﺇﻝﻴﻪ ‪ 10.0 mL‬ﻤﻥ ﺍﻝﻨﺸﺎﺩﺭ ﺒﺘﺭﻜﻴﺯ ‪. 0.50 mol / L‬‬
‫‪ N H+‬ﻤﻬﻤل ﺃﻤﺎﻡ‬
‫ﻥ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪4‬‬
‫ﻻ ﺍﻝﻤﻌﻘﹼﺩ ‪ [ Cu(N H3 )4 ]2+‬ﻭﺃ ‪‬‬
‫ﻨﻘﺒل ﺃﻨﻪ ﻝﻥ ﻴﺘﺸﻜﹼل ﺇ ﹼ‬
‫ﺘﺭﻜﻴﺯ ‪. N H3‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺒﺩﺀﹰﺍ ﻤﻥ )‪. E (Cu / Cu‬‬
‫‬ ‫‪2+‬‬
‫‪ .2‬ﺍﺤﺴﺏ )‪. E ([Cu(N H 3 )4 ]2 + /Cu‬‬

‫‪. log β4([ Cu(N H3 )4 ] ) = 13.2 ، E (Cu2+ / Cu) = 0.34 V‬‬
‫‪2+‬‬
‫ﺍﻝﺤل‬
‫ﻭ ‪S O24−‬‬ ‫‪Cu‬‬ ‫‪2+‬‬
‫‪ H3 O‬ﻭ ‪ O H‬ﺍ ﻝﺸﻭ ﺍ ﺭ ﺩ‬
‫‪−‬‬ ‫‪+‬‬
‫ﻴﻀ ‪‬ﻡ ﺍ ﻝﻤﺤﻠﻭ ل ﺇﻀﺎ ﻓﺔ ﺇ ﻝﻰ ﺸﻭ ﺍ ﺭ ﺩ‬
‫ﻥ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ‬
‫‪ N H+‬ﻭ ‪ [ Cu(N H3 )4 ]2 +‬ﻭﺍﻝﻨﺸﺎﺩﺭ‪ .‬ﻭﺘﺒﻌﹰﺎ ﻝﻁﺒﻴﻌﺔ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﻓﺈ ‪‬‬
‫ﻭ ‪4‬‬
‫ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﺘﺴﺎﻭﻱ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪ E‬ﻝﻸﺯﻭﺍﺝ ﺍﻝﻤﺅﻜﺴﺩﺓ ﻭﺍﻝﻤﺭﺠﻌﺔ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪،‬‬

‫ﻥ‪:‬‬
‫)‪E (Cu2+/ Cu) = E ([ Cu(N H3 )4 ]2+ / Cu‬‬
‫‪ .1‬ﻝﻨﺄﺨﺫ ﺍﻝﺯﻭﺝ ‪: Cu2+/ Cu‬‬
‫)‪Cu2+ + 2e−
Cu(s‬‬
‫ﺤﻴﺙ ﻨﻜﺘﺏ‪:‬‬
‫] ‪E (Cu2+/ Cu) = E (Cu 2+/ Cu) + 0.03 log [ Cu2+‬‬
‫ﻨﺘﺄﻤ‪‬ل ﺘﻔﺎﻋل ﺍﻝﺘﻌﻘﻴﺩ ﺍﻝﺫﻱ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ ‪ K = β4 = 1.6 × 1013‬ﻭﺍﻝﺫﻱ ﻴﻤﻜﻥ ﺍﻋﺘﺒﺎﺭﻩ‬
‫ﺘﺎﻤﹰﺎ‪ ،‬ﻭﺫﻝﻙ ﺒﻬﺩﻑ ﺤﺴﺎﺏ ﺘﺭﻜﻴﺯ ﺸﻭﺍﺭﺩ ‪: Cu2+‬‬
‫‪2+‬‬
‫‪Cu2+‬‬ ‫‪+ 4 N H 3 ⇌  Cu(N H 3 )4 ‬‬
‫‪t =0 8‬‬ ‫‪100‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪68‬‬ ‫‪8‬‬
‫ﻥ‪:‬‬
‫‪2+‬‬
‫] ‪[ Cu(N H3 )4‬‬
‫= ] ‪ε = [ Cu2+‬‬ ‫‪= 2.4 × 10−11 mol / L‬‬
‫‪β4 [ N H3 ]4‬‬
‫ﻭﻋﻠﻴﻪ ﻨﻜﺘﺏ‬
‫‪E (Cu2+/ Cu) = 0.34 + 0.03 log 2.4 × 10−11 = 0.02 V‬‬
‫ﻭﻤﻨﻪ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻬﺫﻩ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﻫﻲ‪:‬‬
‫‪E = 0.02 V‬‬
‫‪ .2‬ﻝﻨﺩﺭﺱ ﺍﻵﻥ ﺍﻝﺯﻭﺝ )‪. ([ Cu(N H3 )4 ]2+ /Cu‬‬
‫‪[ Cu(N H3 )4 ]2+ + 2e−
Cu(s) + 4 N H3‬‬
‫ﻥ‪:‬‬
‫ﻭﻫﻨﺎ ﻨﻜﺘﺏ ﺃ ‪‬‬
‫‪ [ Cu(NH3 )4 ]2+ ‬‬
‫‪E ([ Cu(NH3 )4 ] /Cu) = E ([ Cu(NH3 )4 ] /Cu) + 0.03 log ‬‬
‫‪2+‬‬ ‫‬ ‫‪2+‬‬ ‫‪‬‬
‫‪[ NH3 ]4‬‬
‫ﻥ‪:‬‬
‫ﻝﺤﺴﺎﺏ )‪ E 0 ([ Cu(N H3 )4 ]2 + / Cu‬ﻨﻼﺤﻅ ﺃ ‪‬‬
‫)‪E = E (Cu 2+/Cu) = E ([ Cu(N H3 )4 ]2+ /Cu‬‬
‫ﻥ‪:‬‬‫ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬

‫‪2+‬‬
‫] ‪ [ Cu(N H3 )4‬‬ ‫‪‬‬
‫‪E ([ Cu(N H3 )4 ]2 + / Cu) + 0.03 log ‬‬ ‫‪‬‬
‫‪[ N H3 ]4‬‬
‫] ‪= E (Cu2 +/ Cu) + 0.03 log [ Cu2+‬‬
‫ﻥ‪:‬‬
‫‪ [ Cu(N H3 )4 ]2+ ‬‬
‫‪E ([ Cu(N H3 )4 ] / Cu) = E (Cu / Cu) − 0.03 log ‬‬
‫‬ ‫‪2+‬‬ ‫‬ ‫‪2+‬‬
‫‪4‬‬ ‫‪2+‬‬
‫‪‬‬
‫] ‪[ N H3 ] [ Cu‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﻬﺫﺍ ﻨﺠﺩ ﺃ ‪‬‬
‫‪E ([ Cu(N H3 )4 ]2 + / Cu) = E (Cu2 +/ Cu) − 0.03 log β4 = −0.06 V‬‬
‫ﻥ‬
‫ﻭﺒﺎﻝﻨﺘﻴﺠﺔ ﻨﺠﺩ ﺃ ‪‬‬
‫)‪E ([ Cu(N H3 )4 ]2+ / Cu) < E (Cu2+/ Cu‬‬
‫ﻥ ﺘﻌﻘﻴﺩ ﺍﻝﻤﺅﻜﺴﺩ ‪ Cu2+‬ﻴﺨﻔﹼﺽ ﻤﻥ ﻗﺩﺭﺘﻪ ﻋﻠﻰ ﺍﻷﻜﺴﺩﺓ‪.‬‬

‫ﺃﻱ ﺇ ‪‬‬
‫‪ .2.3.IV‬ﺘﻁﺒﻴﻕ ﺜﺎﻥ‬
‫ﺤﺩ‪‬ﺩ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹ ﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻲ ﻝﻠﺯﻭﺝ ‪ Ag Cl/ Ag‬ﺒﺩﺀﹰﺍ ﻤﻥ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ‬
‫ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻲ ﻝﻠﺯﻭﺝ ‪ Ag+/ Ag‬ﻭﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻝـ ‪. Ag Cl‬‬
‫‪ E (Ag+/ Ag) = 0.80 V‬ﻭ ‪. pK s (Ag Cl) = 9.7‬‬
‫ﺍﻝﺤل‬
‫ﻻ ﻤﺸﺒﻌﹰﺎ ﻤﻥ ﻜﻠﻭﺭ ﻴﺩ ﺍﻝﻔﻀﺔ‪ .‬ﻭ ﻝﻨﻐﻤﺱ ﺴﻠﻜﹰﺎ ﻤﻥ ﺍﻝﻔﻀﺔ ﻓﻲ ﻫﺫﺍ ﺍﻝﻤﺤﻠﻭل‪،‬‬
‫ﻓﻴﺤﺼل ﺍﻝﺘﻭﺍﺯﻥ ﺍﻝﺘﺎﻝﻲ‪:‬‬
‫‪Ag Cl(s) ⇌ Ag+ + Cl−‬‬
‫ﻴﻀ ‪‬ﻡ ﺍﻝﻤﺤﻠﻭل ﺇﻀﺎﻓﺔ ﺇﻝﻰ ﺸﻭﺍﺭﺩ ‪ H3 O+‬ﻭ ‪ O H−‬ﺍﻝﺸﻭﺍﺭﺩ ‪ Ag+‬ﻭ ‪ Cl−‬ﻭﻜﻠﻭﺭ ﺍﻝﻔﻀﺔ‬
‫ﺍﻝﺼﻠﺏ‪ .‬ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﺴﻴﻜﻭﻥ ﻝﺠﻤﻴﻊ ﺍﻷﺯﻭﺍﺝ ﺍﻝﻤﺅﻜﺴﺩﺓ – ﺍﻝﻤﺭﺠﻌﺔ ﺍﻝﻜﻤﻭﻥ ﺫﺍﺘﻪ‪ .‬ﻫﺫﻩ‬
‫ﺍﻷﺯﻭﺍﺝ ﻫﻲ‪ Ag Cl/ Ag ، Ag+/ Ag :‬ﻭﺍﻝﺘﻲ ﺘﻭﺍﻓﻕ ﺍﻝﻤﻌﺎﺩﻻﺕ ﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪Ag Cl + e− ⇌ Ag(s) + Cl−‬‬
‫)‪Ag + + e− ⇌ Ag(s‬‬
255 ‫ﻋﻼﻗﺔ ﻧﺮﻧﺴﺖ‬
:‫ﻭﺘﻜﻭﻥ ﻤﻌﺎﺩﻝﺘﺎ ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺘﺎﻥ‬
E (Ag +/ Ag) = E (Ag+/ Ag) + 0.06 log [ Ag+ ]

E (Ag Cl/ Ag) = E (Ag Cl/ Ag) + 0.06 log 1 [ Cl− ]
= E (Ag Cl/ Ag) − 0.06 log [ Cl− ]
‫ﻭﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ ﻴﻜﻭﻥ‬
E (Ag Cl/ Ag) = E (Ag+/ Ag)
‫ﻥ‬
 ‫ﺃﻱ ﺇ‬
E (Ag Cl/ Ag) − 0.06 log [ Cl− ] = E (Ag+/ Ag) + 0.06 log [ Ag+ ]
‫ﻭﻤﻨﻪ‬
E (Ag Cl/ Ag) = E (Ag+/ Ag) + 0.06 log ( [ Ag+ ][ Cl− ])
‫ﺇﺫﻥ‬
E (Ag Cl/ Ag) = E (Ag+/ Ag) − 0.06 pKs
‫ﻥ‬
 ‫ﻭﺒﺎﻝﺘﻁﺒﻴﻕ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ ﺃ‬
E (Ag Cl/ Ag) = 0.22 V
‫ﻥ ﺘﺭﺴﻴﺏ ﺸﻭﺍﺭﺩ ﺍﻝﻔﻀﺔ ﻗﺩ‬

 ‫ ﺃﻱ ﺇ‬. E (Ag Cl/ Ag) < E (Ag+/ Ag) ‫ﻥ‬
 ‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺃ‬
.‫ﺨﻔﹼﺽ ﻤﻥ ﻗﺩﺭﺘﻬﺎ ﺍﻝﻤﺅﻜﺴﺩﺓ‬
‫

‬ ‫ﺘﻁﺒﻴﻕ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻓﻲ ﺍﻝﺨﻼﻴﺎ ﺍﻝﺤﻴﺔ‬
‫ﻥ ﻏﺸﺎﺀ ﺍﻝﺨﻠﻴﺔ ﺍﻝﺤﻴﺔ ﻫﻭ ﻤﺜﺎل ﻋﻥ ﺍﻷﻏﺸﻴﺔ ﻨﺼﻑ ﺍﻝﻨﻔﻭﺫﺓ ﺤﻴﺙ ﻴﺅﺩﻱ ﺍﺨﺘﻼﻑ ﺘﺭﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ‬
‫ﻫل ﺘﻌﻠﻡ ﺃ ‪‬‬
‫ﺒﻴﻥ ﻁﺭﻓﻲ ﺍﻝﻐﺸﺎﺀ ﺇﻝﻰ ﺘﻭﻝﻴﺩ ﻓﺭﻕ ﻓﻲ ﺍﻝﻜﻤﻭﻥ ﺒﻴﻥ ﻁﺭﻓﻲ ﺍﻝﻐﺸﺎﺀ ﻴ‪‬ﻌﺭ‪‬ﻑ ﺒﺎﺴﻡ ﻜﻤﻭﻥ ﺍﻝﻐﺸﺎﺀ‪ .‬ﻭﻴﻤﻜﻥ ﺃﻥ ﻨﺤﺴﺏ ﻫﺫﺍ‬
‫ﺍﻝﻜﻤﻭﻥ ﺒﺎﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﺸﺒﻴﻬﺔ ﺒﻌﻼﻗﺔ ﻨﺭﻨﺴﺕ‪:‬‬
‫‪RT‬‬ ‫] ‪[y‬‬
‫‪ve,y‬‬ ‫=‬ ‫) ‪ln( o‬‬
‫‪FZ y‬‬ ‫] ‪[y i‬‬
‫ﺤﻴﺙ ‪ ve,y‬ﻫﻭ ﻜﻤﻭﻥ ﺍﻝﺘﻭﺍﺯﻥ ﻝﻠﺸﺎﺭﺩﺓ ‪ y‬ﻭ ‪ R‬ﻫﻭ ﺜﺎﺒﺕ ﺍﻝﻐﺎﺯﺍﺕ ﺍﻝﻤﺜﺎﻝﻴﺔ ﻭ ‪ T‬ﻫﻲ ﺩﺭﺠﺔ ﺍﻝﺤﺭﺍﺭﺓ‬
‫ﻤﻘﺩ‪‬ﺭﺓ ﺒﺎﻝﻜﻴﻠﻔﻥ ﻭ ‪ F‬ﻫﻲ ﺍﻝﻔﺎﺭﺍﺩﻱ ﻭ ‪ Z y‬ﻫﻭ ﺍﻝﺸﺤﻨﺔ ﺍﻝﻤﺤﻤﻭﻝﺔ ﻋﻠﻰ ﺍﻝﺸﺎﺭﺩﺓ ‪ y‬ﻭ ] ‪ [y o‬ﻫﻭ ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺓ ‪y‬‬
‫ﺨﺎﺭﺝ ﺍﻝﺨﻠﻴﺔ ﻭ ] ‪ [y i‬ﻫﻭ ﺘﺭﻜﻴﺯ ﺍﻝﺸﺎﺭﺩﺓ ﺩﺍﺨل ﺍﻝﺨﻠﻴﺔ‪.‬‬
‫ﻭﻤﻥ ﺃﻫﻡ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﺘﻲ ﻨﺠﺩﻫﺎ ﻓﻲ ﺍﻝﻭﺴﻁ ﺍﻝﻤﺤﻴﻁ ﺒﺎﻝﺨﻠﻴﺔ ﺸﻭﺍﺭﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻭﺍﻝﻜﻠﻭﺭ ﺤﻴﺙ ﻴﻜﻭﻥ ﺘﺭﻜﻴﺯﻫﺎ‬
‫ﺨﺎﺭﺝ ﺍﻝﺨﻠﻴﺔ ﺃﻋﻠﻰ ﻤﻥ ﺘﺭﻜﻴﺯﻫﺎ ﺩﺍﺨل ﺍﻝﺨﻠﻴﺔ‪ .‬ﻓﻲ ﺤﻴﻥ ﻴﻨﻌﻜﺱ ﺍﻝﻭﻀﻊ ﻓﻴﻤﺎ ﻴﺘﻌﻠﹼﻕ ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ‪ ،‬ﻜﻤﺎ ﻴﻅﻬﺭ‬
‫ﻫﺫﺍ ﺠﻠﻴ ﹰﺎ ﻓﻲ ﺍﻝﺠﺩﻭل ﺍﻝﺘﺎﻝﻲ ﺍﻝﺨﺎﺹ ﺒﺎﻝﺨﻼﻴﺎ ﺍﻝﻌﺼﺒﻴﺔ‪:‬‬
‫ﻜﻤﻭﻥ ﺍﻝﺘﻭﺍﺯﻥ ‪mV‬‬ ‫ﺍﻝﺘﺭﻜﻴﺯ ‪mmol / L‬‬ ‫ﺍﻝﺸﺎﺭﺩﺓ‬
‫ﺨﺎﺭﺝ ﺍﻝﺨﻠﻴﺔ‬ ‫ﺩﺍﺨل ﺍﻝﺨﻠﻴﺔ‬
‫‪+60‬‬ ‫‪150.0‬‬ ‫‪15.0‬‬ ‫‪Na +‬‬
‫‪−90‬‬ ‫‪5.5‬‬ ‫‪150.0‬‬ ‫‪K+‬‬
‫‪−70‬‬ ‫‪125.0‬‬ ‫‪9.0‬‬ ‫‪Cl−‬‬
‫ﻭﻴﺅﺩﻱ ﻜﻤﻭﻥ ﺍﻝﻐﺸﺎﺀ ﺩﻭﺭﹰﺍ ﻤﻬﻤﹰﺎ ﻓﻲ ﺍﻝﺨﻼﻴﺎ ﺍﻝﻤﺜﺎﺭﺓ ﻜﻬﺭﺒﺎﺌﻴ ﹰﺎ ﻤﺜل ﺍﻝﺨﻼﻴﺎ ﺍﻝﻌﺼﺒﻴﺔ ﻋﺒﺭ ﻨﻘﻠﻪ ﻝﻺﺸﺎﺭﺓ ﺒﻴﻥ‬
‫ﺍﻝﺨﻼﻴﺎ ﺍﻝﻌﺼﺒﻴﺔ )ﺍﻝﺴﻴﺎﻝﺔ ﺍﻝﻌﺼﺒﻴﺔ( ﻭﺫﻝﻙ ﻋﺒﺭ ﻓﺘﺢ ﺃﻭ ﺇﻏﻼﻕ ﻤﺎ ﻴ‪‬ﻌﺭﻑ ﺒﺎﺴﻡ ﻗﻨﻭﺍﺕ ﺍﻝﺸﻭﺍﺭﺩ ﻓﻲ ﻨﻘﻁﺔ ﻤﻌﻴﻨﺔ ﻤﻥ‬
‫ﺍﻝﻐﺸﺎﺀ ﻓﻴﺘﻐﻴﺭ ﺘﺭﻜﻴﺯ ﺸﺎﺭﺩﺓ ﻤﻌﻴﻨﺔ ﺒﻴﻥ ﻁﺭﻓﻲ ﺍﻝﻐﺸﺎﺀ ﻤﻤﺎ ﻴﺅﺩﻱ ﺒﺩﻭﺭﻩ ﺇﻝﻰ ﺘﻐﻴ‪‬ﺭ ﻤﻭﻀﻌﻲ ﻓﻲ ﻜﻤﻭﻥ ﺍﻝﻐﺸﺎﺀ ﻓﻴﺘﻭﻝﹼﺩ‬
‫ﺘﻴﺎﺭ ﻜﻬﺭﺒﺎﺌﻲ ﻴﻨﺘﻘل ﻋﻠﻰ ﻁﻭل ﺍﻝﻐﺸﺎﺀ‪.‬‬
‫‪Ann Saterbak, Bioengineering Fundamentals, Prentice Hall, 2004‬‬
‫ﻜﻤﻭﻥ ﺍﻝﻤﺴﺭﻯ‪.‬‬ ‫‬
‫ل ﻤﻥ ﺍﻹﻝﻜﺘﺭﻭﺩﺍﺕ‬
‫ﺤﺩ‪‬ﺩ ﺍﻝﻜﻤﻭﻥ ﺍﻝﺫﻱ ﻴﺄﺨﺫﻩ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ﻤﺴﺭﻯ ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻜ ﱡ‬
‫‪ .1‬ﻓﻀﺔ ﻓﻲ ﻤﺤﻠﻭل ﻤﻥ ﻨﺘﺭﺍﺕ ﺍﻝﻔﻀ‪‬ﺔ ‪. E (Ag +/Ag) = 0.8 V ، 0.10 mol/L‬‬
‫ل ﺤﺎ ﹴﻭ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ ‪ 0.1 mol/L II‬ﻭﻜﻠﻭﺭ ﻴﺩ ﺍﻝﺤﺩﻴﺩ )‪(III‬‬
‫‪ .2‬ﺒﻼﺘﻴﻥ ﻓﻲ ﻤﺤﻠﻭ ﹴ‬
‫‪. E (Fe3+/Fe2 + ) = 0.77 V ، 0.5 mol/L‬‬
‫ل ﺤﺎ ﹴﻭ ﻋﻠﻰ ﺜﻨﺎﺌﻲ ﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪10−2 mol/L‬‬
‫‪ .3‬ﺒﻼﺘﻴﻥ ﻓﻲ ﻤﺤﻠﻭ ﹴ‬
‫ﻭﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺭﻭﻡ )‪ (III‬ﺒﺘﺭﻜﻴﺯ ‪ 0.2 mol/L‬ﻭﻓﻲ ﺤﺎﻝﺔ ‪ pH‬ﺍﻝﻭﺴﻁ ﻴﺴﺎﻭﻱ ‪،2‬‬
‫‪. E (Cr2 O27−/Cr3+ ) = 1.33 V‬‬
‫ﺍﻹﻨﺩﻴﻭﻡ ﻭﺸﻭﺍﺭﺩﻩ‪.‬‬ ‫‬
‫ﻥ‪ E (In /In) = −0.14 V :‬ﻭ ‪. E (In /In ) = −0.44 V‬‬
‫‬ ‫‪3+‬‬ ‫‪+‬‬ ‫‬ ‫‪+‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻤﺭﺠﻌﻲ )‪. E (In 3+/In‬‬
‫ﻥ‬
‫ل ﻤﻥ ‪ In ، In+ ، In 3+‬ﻭﺫﻝﻙ ﺒﺎﻓﺘﺭﺍﺽ ﺃ ‪‬‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﺃﻭ ﺍﻝﻭﺠﻭﺩ ﻝﻜ ّ‬
‫‪ ، [In+ ]lim = 0.10 mol/L‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫ﻥ ﺍﻝﺸﺎﺭﺩﺓ ‪ In+‬ﻝﻴﺴﺕ ﻤﺴﺘﻘﺭﺓ‪ ،‬ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻔﺎﻋل ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬
‫‪ .3‬ﺍﺴﺘﻨﺘﺞ ﺃ ‪‬‬
‫ﺍﻝﺫﻱ ﺘﺘﻔﻜﻙ ﻓﻴﻪ ﻫﺫﻩ ﺍﻝﺸﺎﺭﺩﺓ )ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﺫﺍﺘﻲ ‪.(dismutation‬‬
‫ﺍﻝﻘﺼﺩﻴﺭ ﻭﺸﻭﺍﺭﺩﻩ‪.‬‬ ‫‬
‫ﻥ‪ E (Sn2+/Sn) = −0.14 V :‬ﻭ ‪E 0 (Sn 4+/Sn2+ ) = 0.15 V‬‬
‫ل ﻤﻥ ‪ Sn ، Sn2+ ، Sn 4+‬ﻭﺫﻝﻙ ﺒﺎ ﻓﺘﺭ ﺍﺽ‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﺃﻭ ﺍﻝﻭﺠﻭﺩ ﻝﻜ ّ‬
‫ﻥ ‪ ، [Sn2+ ]lim = 0.10 mol/L‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫ﺃ‪‬‬
‫‪ .2‬ﻨﻀﻴﻑ ﻓﺎﺌﻀﹰﺎ ﻤﻥ ﻤﻌﺩﻥ ﺍﻝﻘﺼﺩﻴﺭ ﺇﻝﻰ ﻤﺤﻠﻭل ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﻘﺼﺩﻴﺭ ﺍﻝﺭﺒﺎﻋﻲ )‪(IV‬‬
‫ﺒﺘﺭﻜﻴﺯ ‪. 0.10 mol/L‬‬
‫)‪ (a‬ﺼﻑ ﻤﺎﺫﺍ ﻴﺤﺩﺙ ﻓﻲ ﺍﻝﻤﺤﻠﻭل؟‬
‫)‪ (b‬ﺃﻭﺠﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﻬﺎﺌﻲ ﻤﻊ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻴﻪ‪.‬‬
‫ﻤﺭﻜﺒﺎﺕ ﺍﻝﻤﻨﻐﻨﻴﺯ‪.‬‬ ‫‬

‫ﻨﻌﻁﻰ ﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪ E (MnO−4 /MnO2 ) = 1.70 V‬ﻭ ‪E (MnO2/Mn2+ ) = 1.23 V‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﻗﻴﻤﺔ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻤﺭﺠﻌﻲ ) ‪. E (MnO−4 /Mn2+‬‬
‫‪ .2‬ﻨﻤﺯﺝ ‪ 10 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻤﻨﻐﻨﻴﺯ ﺒﺘﺭﻜﻴﺯ ‪ 0.10 mol/L‬ﻭ ‪10 mL‬‬
‫ﻤﻥ ﻤﺤﻠﻭل ﺒﺭﻤﻨﻐﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ . 0.10 mol/L‬ﺃﻭﺠﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل‬
‫ﺍﻝﻨﻬﺎﺌﻲ ﻤﻊ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭ ﺩﺓ ﻓﻴﻪ ﻭﻜﺫﻝﻙ ﻜﺘﻠﺔ ﺍﻝﺭﺍﺴﺏ ﺍﻝﺤﺎﺼل ﻋﻨﺩ ﻗﻴﻤﺔ‬
‫‪. pH = 0‬‬
‫ﺨﻠﻴﺔ ﺩﺍﻨﻴﻴل ﻭﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪.‬‬ ‫‬
‫ﻨﺤﻀ‪‬ﺭ ﺨﻠﻴﺔ ﺩﺍﻨﻴﻴل ﻭﻓﻕ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﺘﺎﻝﻴﺔ‪. [Cu2 + ] = [Zn2 + ] = 10−2 mol/L :‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻬﺫﻩ ﺍﻝﺨﻠﻴﺔ‪ ،‬ﻭﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﻋﻤﻠﻪ‪.‬‬
‫ل ﺤﺠﻴﺭﺓ ﻭﺩﻭﻥ ﺃﻱ ﺘﻤﺩﻴﺩ ﻜﻤﻴﺔ ﻤﻥ ﺍﻝﻨﺸﺎﺩﺭ ﺒﺤﻴﺙ ﻴﻜﻭﻥ ﺒﻌﺩ ﺍﻹﻀﺎﻓﺔ‬
‫‪ .2‬ﻨﻀﻴﻑ ﺇﻝﻰ ﻜ ّ‬
‫‪ . [NH3 ] = 1 mol/L‬ﺍﺤﺴﺏ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻠﺨﻠﻴﺔ ﺍﻝﻨﺎﺘﺠﺔ ‪ ،‬ﻭﺍﻜﺘﺏ‬
‫ﺼﻠﺔ ﻝﺘﻔﺎﻋل ﻋﻤﻠﻬﺎ‪.‬‬
‫ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤ ‪‬‬
‫ﺍﻝﻤﻌﻁﻴﺎﺕ ‪ E (Zn2 +/Zn) = −0.76 V :‬ﻭ ‪E (Cu2+/Cu) = 0.34 V‬‬
‫‪ log β4[Cu(NH3 )4 ]2+ = 12‬ﻭ ‪log β4[Zn(NH3 )4 ]2+ = 8.7‬‬
‫ﺘﺤﺩﻴﺩ ﺜﺎﺒﺕ ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ‪.‬‬ ‫‬
‫ﻝﻨﺄﺨﺫ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻐﻠﻔﺎﻨﻴﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫⊖‬ ‫‪Ag Ag+ + NO−‬‬ ‫‪+‬‬ ‫‪−‬‬ ‫‪+‬‬ ‫‪−‬‬
‫‪3 + K + CN ⋮⋮ Ag + NO3 Ag‬‬ ‫⊕‬
‫ﺒﺤﻴﺙ ﺘﻜﻭﻥ ﺘﺭﺍﻜﻴﺯ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻴﺴﺎﺭﻱ‪:‬‬
‫‪−‬‬
‫‪[ CN ] = 4.0 × 10‬‬ ‫‪−2‬‬
‫‪ [ Ag + ] = 4.0 × 10−3 mol/L‬ﻭ ‪mol/L‬‬
‫ﻭﺘﺭﻜﻴﺯ ﻨﺼﻑ ﺍﻝﺨﻠﻴﺔ ﺍﻝﻴﻤﻴﻨﻲ‪:‬‬
‫‪[ Ag+ ] = 4.0 × 10−2 mol/L‬‬
‫ﻥ ﺍﻝﻘﻭﺓ ﺍﻝﻤﺤﺭ‪‬ﻜﺔ ﺍﻝﻜﻬﺭﺒﺎﺌﻴﺔ ﻝﻬﺫﺍ ﺍﻝﺨﻠﻴﺔ ﺘﺴﺎﻭﻱ ‪ ، 1.08 V‬ﺍﺴﺘﻨﺘﺞ ﻗﻴﻤﺔ‬
‫ﺜﺎﺒﺕ ﺍﻝﺘﺸﻜﹼل ﺍﻹﺠﻤﺎﻝﻲ ﻝﻠﻤﻌﻘﹼﺩ ‪. [ Ag(CN)2 ]−‬‬
‫ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﻭﺍﻝﺘﺭﺴﻴﺏ‪.‬‬ ‫‬

‫ﺤﺩ‪‬ﺩ ﻜﻤﻭﻨﻲ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﻤﺭﺠﻌﻴﻴﻥ ﻝﻠﺯﻭﺠﻴﻥ‪ PbSO4/Pb :‬ﻭ ‪. AgI/Ag +‬‬
‫‬ ‫‪2+‬‬ ‫‬ ‫‪+‬‬
‫‪E (Pb /Pb) = −0.13 V, E (Ag /Ag) = 0.80 V‬‬
‫‪p K s(Pb SO4 ) = 7.8,‬‬ ‫‪p K s(Ag I) = 15.3‬‬
‫ﺸﺎﺭﺩﺓ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬ ‫‬
‫ﻻ ﻤﺎﺌﻴﹰﺎ ﻤﻥ ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺘﺭﻜﻴﺯ ‪ . 0.5 mol/L‬ﻭﻝﻨﺜﺒ‪‬ﺕ ‪pH‬‬
‫ﻝﻨﺤﻀ‪‬ﺭ ﻤﺤﻠﻭ ﹰ‬
‫ﻥ ﺘﻴﺎﺭﹰﺍ ﻤﻥ ﺍﻝﻬﻭﺍﺀ ﻴﻤ ‪‬ﺭ‬
‫ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﻗﻴﻤﺔ ﺍﻝﺼﻔﺭ ﺒﺈﻀﺎﻓﺔ ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ‪ .‬ﻓﺈﺫﺍ ﻋﻠﻤﺕ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻭﺃ ‪‬‬
‫‪ E (Fe3+/Fe2+ ) = −0.77 V‬ﻭ ‪E (O2/H2O) = 1.23 V‬‬
‫ﻤﻥ ﻏﺎﺯ ﺍﻷﻜﺴﺠﻴﻥ‪،‬‬ ‫‪1‬‬
‫‪5‬‬ ‫ﻤﻥ ﻏﺎﺯ ﺍﻵﺯﻭﺕ ﻭ‬ ‫‪4‬‬
‫‪5‬‬ ‫ﻥ ﺍﻝﻬﻭﺍﺀ ﻤﻜﻭ‪‬ﻥ ﺤﺠﻤﻴﹰﺎ ﻤﻥ‬
‫ﻭ ﺃﺨﻴﺭ ﹰﺍ ﺃ ‪‬‬
‫ﺍﻝﻤﻁﻠﻭﺏ‪:‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل‪ ،‬ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺘﻭﺍﺯﻨﻪ‪ ،‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .2‬ﺃﻭﺠﺩ ﺘﺭﻜﻴﺏ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻨﻬﺎﺌﻲ ﻤﻊ ﺘﺭﺍﻜﻴﺯ ﺍﻝﺸﻭﺍﺭﺩ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻴﻪ‪.‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ‬
‫
‬
‫ ‬
‫‪ .I‬ﻋﻤﻭﻤﻴﺎﺕ ﻭﺘﺫﻜﺭﺓ‬
‫‪ .II‬ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺭﻴﻭﻡ )‪(IV‬‬
‫‪ .1.II‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫‪ .2.II‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ﻝﻠﻤﻨﺤﻨﻲ ) ‪E = f (x‬‬
‫‪ .3.II‬ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﺒﺔ‬
‫‪ .4.II‬ﻤﺸﻌﺭ ﻝﻭﻨﻲ ﺃﻜﺴﺩﺓ‪-‬ﺇﺭﺠﺎﻉ‬
‫‪ .III‬ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬

‫‪Mn O−‬‬
‫‪ .1.III‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫‪ .2.III‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ﻝﻠﻤﻨﺤﻨﻲ ) ‪E = f (x‬‬
‫‪ .3.III‬ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ‬
‫‪261‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺜﺎﻣﻦ‬ ‫‪262‬‬
‫‪ .I‬ﻋﻤﻭﻤﻴﺎﺕ ﻭﺘﺫﻜﺭﺓ‬
‫ﻝﻨﻜﺘﺏ ﺘﻔﺎﻋل ﻤﻌﺎﻴﺭﺓ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺒﺭﻴﺕ ﺒﺸﺎﺭﺩﺓ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬
‫‪2 Mn O−‬‬ ‫‪2+‬‬ ‫‪2−‬‬
‫‪4 + 5 SO2 + 6 H2 O → 2 Mn + 5 SO4 + 3 H 3 O‬‬
‫‪+‬‬
‫ﺃﻭ ﻤﻌﺎﻴﺭﺓ ﺍﻝﻴﻭﺩ ﺒﺸﺎﺭﺩﺓ ﺍﻝﺜﻴﻭﺴﻠﻔﺎﺕ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬

‫‪I2 + 2 S2 O23− → 2I− + S4O26−‬‬
‫ﻥ ﻜﻼ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ ﺘﺎﻡ ﻭﺴﺭﻴﻊ ﻭﻻ ﺘﻭﺠﺩ ﺘﻔﺎﻋﻼﺕ ﺜﺎﻨﻭﻴﺔ ﺃﺨﺭﻯ ﻤﺭﺍﻓﻘﺔ ﻝﻪ‪ .‬ﻭﻋﻨﺩ‬
‫ﺇ‪‬‬
‫ﻥ ﻋﺩﺩ‬
‫ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺘﻜﻭﻥ ﺍﻝﻤﻭﺍ ‪‬ﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ ﻤﻤﺯﻭﺠﺔ ﻭﻓﻕ ﺍﻝﻨﺴﺏ ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ؛ ﺃﻱ ﺇ ‪‬‬
‫ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﺘﻲ ﺍﻜﺘﺴﺒﻬﺎ ﺍﻝﻤﺅﻜﺴ‪‬ﺩ ﻴﺴﺎﻭﻱ ﻋﺩﺩ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﺘﻲ ﻗﺩ‪‬ﻤﻬﺎ ﺍﻝﻤﺭﺠﹺﻊ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﻓﺈﻥ ﻋﺩﺩ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﻤﻨﺘﻘﻠﺔ ﻓﻲ ﺍﻝﺘﻔﺎﻋﻠﻴﻥ ﺍﻝﺴﺎﺒﻘﻴﻥ‪:‬‬
‫‪RT‬‬ ‫‪(a(Ox))α‬‬
‫‪E (Ox/Red) = E (Ox/Red) +‬‬ ‫‪ln‬‬
‫‪nF (a(Red))β‬‬
‫‪n(e− ) = 2n 0 (SO2 ) = 5neq (MnO−‬‬
‫)‪4‬‬
‫) ‪n(e− ) = 2n 0 (I2‬‬ ‫) ‪= neq (S2O23−‬‬
‫ﺍﻝﺩﻝﻴل ‪ eq‬ﻨﻘﺼﺩ ﺒﻪ ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫ﻭﺍﻝﺩﻝﻴل ‪ 0‬ﻨﻘﺼﺩ ﺒﻪ ﺤﺎﻝﺔ ﺍﻝﺒﺩﺀ ﻗﺒل ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫ﺘﻤﺘﺎﺯ ﻫﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺒﺄﻥ ﺇﺤﺩﻯ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺘﻔﺎﻋﻠﺔ‪ ،‬ﺃﻭ ﺇﺤﺩﻯ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻨﺎﺘﺠﺔ ﻤﻥ ﺍﻝﺘﻔﺎﻋل‪،‬‬
‫ﻥ ﻤﺤﺩ‪‬ﺩ‪ ،‬ﻭﻫﺫﺍ ﻴ‪‬ﺴﻬ‪‬ل ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫ﺘﻅﻬﺭ ﺒﻠﻭ ﹴ‬
‫ﻥ‬
‫‪ Mn O−‬ﺒﻨﻔﺴﺠﻴﺔ ﺍﻝﻠﻭﻥ‪ ،‬ﻓﻲ ﺤﻴﻥ ﺃ ‪‬‬
‫ﻓﻔﻲ ﺍﻝﺘﻔﺎﻋل ﺍﻷﻭل ﺘﻜﻭﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﻤﻨﻐﻨﻴﺯ )‪ (II‬ﻋﺩﻴﻤﺔ ﺍﻝﻠﻭﻥ‪ .‬ﻭﻓﻲ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺜﺎﻨﻲ ﻴﻜﻭﻥ ﻤﺤﻠﻭل ﺍﻝﻴﻭﺩ ﺃﺼﻔﺭ ﺒﻨﹼﻴﹰﺎ ﻓﻲ ﺤﻴﻥ‬
‫ﻥ ﺸﻭﺍﺭﺩ ﺍﻝﻴﻭﺩ ﻋﺩﻴﻤﺔ ﺍﻝﻠﻭﻥ‪.‬‬
‫ﺃ‪‬‬
‫ﻭﻨﺴﻤ‪‬ﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﺴﺎﺒﻘﺔ ﺒﺎﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﻠﻭﻨﻴﺔ ﻷﻨﹼﻨﺎ ﻨﻌﺘﻤﺩ ﻋﻠﻰ ﺘﻐﻴ‪‬ﺭ ﺍﻝﻠﻭﻥ ﻓﻲ ﺘﺤﺩﻴﺩ ﻨﻘﻁﺔ‬
‫ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫ﻓﻲ ﺍﻝﺤﺎﻻﺕ ﺍﻝﺘﻲ ﻴﺘﻌﺫﹼﺭ ﻋﻠﻴﻨﺎ ﺫﻝﻙ ﻨﻠﺠﺄ ﺇﻝﻰ ﻁﺭﻴﻘﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺒﺎﺴﺘﻌﻤﺎل ﻤﻘﻴﺎﺱ ﺍﻝﻜﻤﻭﻥ‬
‫ﺤﻴﺙ ﻨﻘﻴﺱ ﺘﻐﻴﺭﺍﺕ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ )‪ E (Ox/Red‬ﺃﺜﻨﺎﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ‪.‬‬
‫‪263‬‬ ‫ﻣﻌﺎﻳﺮﺍﺕ ﺍﻷﻛﺴﺪﺓ ﻭﺍﻹﺭﺟﺎﻉ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫‪ .II‬ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ Fe2+ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺴﻴﺭﻴﻭﻡ )‪Ce 4+ (IV‬‬
‫‪ .1.II‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫ﻨﺴﺘﻌﻤل ﺍﻹﻨﺸﺎﺀ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﻤﻭﻀ‪‬ﺢ ﻓﻲ ﺍﻝﺸﻜل )‪ (1‬ﺍﻝﺘﺎﻝﻲ ‪:‬‬
‫ﳏﻠﻮﻝ ‪Ce 4 +‬‬ ‫‪620‬‬
‫‪COM‬‬ ‫‪V‬‬
‫ﻣﺴﺮﻯ ﺑﻼﺗﲔ‬
‫ﳏﻠﻮﻝ ‪Fe 2 +‬‬
‫‪ON‬‬
‫‪OFF‬‬
‫ﺍﻝﺸﻜل )‪ : (1‬ﺍﻹﻨﺸﺎﺀ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﻤﺴﺘﻌﻤل ﻝﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ‪ Fe2 +‬ﺒﺸﻭﺍﺭﺩ ‪. Ce4 +‬‬
‫ﻥ‪:‬‬
‫ﻨﻌﻠﻡ ﻤﻥ ﺍﻝﺠﺩﺍﻭل ﺃ ‪‬‬
‫‪ E (Fe3 + /Fe2 + ) = 0.77 V‬ﻭ ‪E 0 (Ce4 + /Ce3 + ) = 1.7 V‬‬
‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺘﻴﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺘﻴﻥ ﺍﻝﻨﺼﻔﻴﺘﻴﻥ‪:‬‬
‫‪Fe3+ + e− ⇌ Fe2 +‬‬
‫‪Ce4 + + e− ⇌ Ce2 +‬‬

‫ﻭﻤﻨﻪ ﻨﺠﺩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل‪:‬‬
‫‪Ce4 + + Fe2 + Ce3 + + Fe3 +‬‬
‫ﺘﻅﻬﺭ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﺍﻝﺴﺎﺒﻘﺔ ﺃﻨﻪ ﻴﺠﺭﻱ ﺘﺒﺎﺩل ﻤﻭل ﻤﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﻋﻨﺩﻤﺎ ﻴﺘﻔﺎﻋل ﻤﻭل ﻤﻥ‬
‫‪ Ce4 +‬ﻤﻊ ﻤﻭل ﻤﻥ ‪ . Fe2 +‬ﻝﻨﺤﺴﺏ ‪ K‬ﺜﺎﺒﺕ ﻫﺫﺍ ﺍﻝﺘﻭﺍﺯﻥ‪:‬‬
‫] ‪[Fe3 +‬‬
‫‪E1 = E (Fe3 + /Fe2 + ) + 0.06 log‬‬
‫] ‪[Fe2 +‬‬
‫‬ ‫‪4+‬‬ ‫‪3+‬‬ ‫] ‪[Ce4 +‬‬
‫‪E2 = E (Ce /Ce ) + 0.06 log‬‬
‫] ‪[Ce3 +‬‬
‫ﻭﻝﻜﻥ ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﺘﺘﺤﻘﹼﻕ ﺍﻝﻤﺴﺎﻭﺍﺓ ‪ ، E1 = E2 = Eeq :‬ﺇﺫﻥ‬

‫] ‪[Fe3+ ][Ce3 +‬‬
‫‪E (Ce4 + /Ce3 + ) − E (Fe3 + /Fe2+ ) = 0.06 log‬‬
‫] ‪[Fe2 + ][Ce4 +‬‬
‫‬
‫‪K‬‬
‫‪ 0.94 = 0.06 log K‬ﺃﻭ‬ ‫‬

‫ﻭﺒﺎﻝﺘﻌﻭﻴﺽ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ‬
‫‪0.94/0.06‬‬
‫‪K = 10‬‬ ‫‪= 1015.67 = 4.6 × 1015 > 103‬‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺤﺎﺼل ﻫﻭ ﺘﻔﺎﻋل ﺘﺎ ‪‬ﻡ‪ .‬ﻭﺍﻝﺘﺠﺭﺒﺔ ﺘﺜﺒﺕ ﺃﻨﹼﻪ ﺘﻔﺎﻋل ﺴﺭﻴﻊ‪ ،‬ﻭﻝﻴﺱ ﻫﻨﺎﻝﻙ ﺘﻔﺎﻋﻼﺕ‬
‫ﺃﻱ ﺇ ‪‬‬
‫ﺜﺎﻨﻭﻴﺔ ﻤﺼﺎﺤﺒﺔ ﻝﻪ‪.‬‬
‫ﻨﻀﻴﻑ ﺤﺠﻤﹰﺎ ‪ V2‬ﻤﻥ ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺴﻴﺭﻴﻭﻡ ‪ IV‬ﺒﺘﺭﻜﻴﺯ ‪ C 2‬ﺇﻝﻰ ﺤﺠﻡ ‪ V1‬ﻤﻥ‬
‫ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺫﺍﺕ ﺍﻝﺘﺭﻜﻴﺯ ‪.C 1‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻴﺤﻘﹼﻕ ﻋﺩﺩ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ ﺍﻝﻤﺘﺒﺎﺩﻝﺔ ﺍﻝﻤﺴﺎﻭﺍﺓ‬

‫) ‪n(e- ) = n 0 (Fe2+ ) = neq (Ce4 +‬‬
‫‪C 1V1 = C 2V2eq‬‬
‫ﻨﻌﺭ‪‬ﻑ ﺇﺫﻥ ﺍﻝﻤﻘﺩﺍﺭ ‪ x‬ﺒﺎﻝﺼﻴﻐﺔ ‪ ، x = V2 /V2eq‬ﻭﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻥ‬
‫‪V2C 2‬‬ ‫‪VC‬‬
‫= ‪x‬‬ ‫‪= 2 2‬‬
‫‪V2eqC 2‬‬ ‫‪V1C 1‬‬
‫‪ .2.II‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ﻝﻠﻤﻨﺤﻨﻲ ) ‪E = f (x‬‬
‫ﻝﻨﺩﺭﺱ ﺘﻐﻴ‪‬ﺭ ﻜﻤﻭﻥ ﺍﻷﻜﺴﺩﺓ‪/‬ﺇﺭﺠﺎﻉ ﻝﻠﺯﻭﺠﻴﻥ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ ﺒﺩﻻﻝﺔ ‪. x‬‬
‫ ﺤﺎﻝﺔ ‪ x = 0‬ﺃﻭ ‪.V2 = 0‬‬
‫ﻨﻅﺭﻴﹰﺎ ﻻ ﻴﻀ ‪‬ﻡ ﺍﻝﻤﺤﻠﻭل ﺇﻻ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻻ ﻴﻤﻜﻥ ﺘﻁﺒﻴﻕ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‬
‫ﻝﺤﺴﺎﺏ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ ‪ . Fe3+ /Fe2 +‬ﻭﻝﻜﻥ ﻋﻤﻠﻴﹰﺎ ﻴﻀﻡ ﺍﻝﻤﺤﻠﻭل ﺇﻀﺎﻓﺔ ﺇﻝﻰ ‪ Fe2 +‬ﺁﺜﺎﺭﹰﺍ‬
‫ﻗﻠﻴﻠﺔ ﺠ ‪‬ﺩﹰﺍ ﻤﻥ ‪ Fe3 +‬ﻤﺭﺩ‪‬ﻫﺎ ﺃﻜﺴﺩﺓ ﺍﻷﻜﺴﺠﻴﻥ ﺍﻝﻤﻨﺤل ﻓﻲ ﺍﻝﻤﺎﺀ ﻝﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩﻱ‪ .‬ﻭﺒﺫﻝﻙ ﻴﻤﻜﻨﻨﺎ‬
‫ﻗﻴﺎﺱ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ ‪ Fe3+ /Fe2 +‬ﻭﺘﺘﻐﻴ‪‬ﺭ ﺍﻝﻘﻴﻤﺔ ﺍﻝﻤﻘﺎﺴﺔ ﺘﺒﻌﹰﺎ ﻝﻤﺩﻯ ﻜﻭﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﻌﺎ ‪‬ﻴﺭ‬
‫"ﻁﺎﺯﺠﹰﺎ"‪.‬‬
‫ ﺤﺎﻝﺔ ‪ 0 < x < 1‬ﺃﻱ ‪. 0 < V2 < Veq‬‬
‫ﻓﻲ ﻜل ﻝﺤﻅﺔ ﻤﻥ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﺘﻘﻀﻲ ﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﺍﻝﺘﻔﺎﻋل ﺒﺄﻥ ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫) ‪n(Ce3 + ) = n(Fe3 +‬‬
‫ﻥ ] ‪ ، [Fe3 + ] = [Ce3+‬ﻭﻤﻨﻪ ﻨﻜﺘﺏ‪:‬‬

‫ﺃﻱ ﺇ ‪‬‬
‫‪Ce4 +‬‬ ‫‪+ Fe2 +‬‬ ‫‪ Ce3 + + Fe3 +‬‬

‫‪t = 0 C 2V2‬‬ ‫‪C 1V1‬‬ ‫‪0‬‬ ‫‪0‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪C 1V1 − C 2V2‬‬ ‫‪C 2V2‬‬ ‫‪C 2V2‬‬
‫ﻭﻴﺘﺤﺩﺩ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺠﻴﻥ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻓﻲ ﻜل ﻝﺤﻅﺔ ﺒﺘﻁﺒﻴﻕ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻋﻠﻰ ﺃﺤﺩ‬
‫ﺍﻝﺯﻭﺠﻴﻥ‪ .‬ﻭﻗﺒل ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻴﻜﻭﻥ ﻤﻥ ﺍﻷﺴﻬل ﺘﻁﺒﻴﻕ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻋﻠﻰ ﺍﻝﺯﻭﺝ‬
‫‪: Fe 3+ Fe 2+‬‬
‫] ‪[Fe3 +‬‬
‫‪E = E (Fe3+ /Fe2 + ) + 0.06 log‬‬
‫] ‪[Fe2 +‬‬
‫‪C 2V2‬‬
‫‪E = E (Fe3+ /Fe2 + ) + 0.06 log‬‬
‫‪C 1V1 − C 2V2‬‬
‫ﻭﺒﻘﺴﻤﺔ ﺍﻝﺒﺴﻁ ﻭﺍﻝﻤﻘﺎﻡ ﺩﺍﺨل ﺍﻝﻠﻭﻏﺎﺭﻴﺘﻡ ﻋﻠﻰ ‪ ، C1V1‬ﻨﺠﺩ‬

‫‪x‬‬
‫‪E = E (Fe3+ /Fe2 + ) + 0.06 log‬‬
‫‪1−x‬‬
‫‪C 2V2‬‬
‫= ‪ x‬ﻝﺩﻴﻨﺎ‪:‬‬ ‫‪1‬‬
‫‪2‬‬
‫= ‪ ، x‬ﻭﻨﻼﺤﻅ ﺃﻨﹼﻪ ﻋﻨﺩ ﻨﻘﻁﺔ ﻨﺼﻑ ﺍﻝﺘﻜﺎﻓﺅ‪ ،‬ﺃﻱ‬ ‫ﻷﻥ‬
‫‪C 1V1‬‬
‫) ‪E = E (Fe3+ /Fe2 +‬‬
‫ ﻋﻨﺩﻤﺎ ‪ x = 1‬ﺃﻱ ‪.V2 = V2eq‬‬
‫ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ ،‬ﺘﻜﻭﻥ ﺸﻭﺍﺭﺩ ‪ Ce4 +‬ﻭﺸﻭﺍﺭﺩ ‪ Fe2 +‬ﻤﻤﺯﻭﺠﺔ ﻭﻓﻕ ﺍﻝﻨﺴﺏ‬
‫ﻥ‪:‬‬
‫ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ‪ ،‬ﺃﻱ ﺃ ‪‬‬
‫) ‪neq (Ce4 + ) + neq (Ce3 + ) = neq (Fe2 + ) + neq (Fe3 +‬‬
‫ﻥ‪:‬‬
‫ﻓﺈﺫﺍ ﺘﺫﻜﹼﺭﻨﺎ ﺃﻨﻪ ﻓﻲ ﻜل ﻝﺤﻅﺔ ﻤﻥ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻴﻜﻭﻥ ‪ n(Ce3 + ) = n(Fe3 + ) :‬ﺍﺴﺘﻨﺘﺠﻨﺎ ﺃ ‪‬‬
‫) ‪neq (Ce4 + ) = neq (Fe2 +‬‬
‫ﻥ ‪ ، [Ce4 + ]eq = [Fe2 + ]eq‬ﻭﻋﻠﻴﻪ‪:‬‬

‫ﺃﻱ ﺇ ‪‬‬
‫‬ ‫‪3+‬‬ ‫‪2+‬‬

‫‪[Fe3 + ]eq‬‬
‫‪Eeq = E (Fe‬‬ ‫‪/Fe ) + 0.06 log‬‬
‫‪[Fe2 + ]eq‬‬
‫‬ ‫‪4+‬‬ ‫‪3+‬‬
‫‪[Ce4 + ]eq‬‬
‫‪Eeq = E (Ce‬‬ ‫‪/Ce‬‬ ‫‪) + 0.06 log‬‬
‫‪[Ce3 + ]eq‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﺠﻤﻊ ﺍﻝﻌﻼﻗﺘﻴﻥ ﺍﻝﺴﺎﺒﻘﺘﻴﻥ ﻨﺠﺩ ﺃ ‪‬‬
‫‬ ‫‪3+‬‬ ‫‪2+‬‬ ‫‬ ‫‪4+‬‬ ‫‪3+‬‬

‫‪[Fe3 + ]eq [Ce4 + ]eq‬‬
‫‪2Eeq = E (Fe‬‬ ‫‪/Fe ) + E (Ce‬‬ ‫‪/Ce‬‬ ‫‪) + 0.06 log‬‬
‫‪[Fe2 + ]eq [Ce3 + ]eq‬‬
‫ﻥ‪:‬‬
‫ﻭﺒﻌﺩ ﺍﻻﺨﺘﺯﺍل ﻨﺠﺩ ﺃ ‪‬‬
‫) ‪E (Fe3 + /Fe2+ ) + E (Ce4 + /Ce3 +‬‬

‫= ‪Eeq‬‬
‫‪2‬‬
‫ﻥ‪. Eeq = 1.27 V :‬‬
‫ﻭﺒﺎﻝﺘﻁﺒﻴﻕ ﺍﻝﻌﺩﺩﻱ ﻨﺠﺩ ﺃ ‪‬‬
‫ ﻋﻨﺩﻤﺎ ‪ x > 1‬ﺃﻱ ‪.V2 > V2eq‬‬
‫ﻻ ﺁﺜﺎﺭ ﻗﻠﻴﻠﺔ ﻝﻠﻐﺎﻴﺔ‪ .‬ﻭﻴﺼﺒﺢ ﻤﻥ ﺍﻷﺴﻬل‬

‫ﻻ ﺘﻭﺠﺩ ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﻤﻥ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩﻱ ﺇ ﹼ‬
‫ﺤﺴﺎﺏ ﻜﻤﻭﻥ ﺍﻝﻤﺤﻠﻭل ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺯﻭﺝ ‪: Ce 4 + /Ce 3+‬‬
‫‪C 2V2 − C 2V2eq‬‬ ‫‪C ⋅V‬‬
‫= ] ‪[ Ce4 +‬‬ ‫‪ [ Ce3 + ] = 2 2eq‬ﻭ‬
‫‪V2 + V1‬‬ ‫‪V2 + V1‬‬
‫ﻭﻤﻨﻪ ﻨﻜﺘﺏ ﺒﺎﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‪:‬‬
‫‬ ‫‪4+‬‬ ‫‪3+‬‬ ‫] ‪[Ce4 +‬‬

‫‪E = E (Ce‬‬ ‫‪/Ce‬‬ ‫‪) + 0.06 log‬‬
‫] ‪[Ce3+‬‬
‫ﺃﻱ‬
‫‪ C V − C 2V2eq‬‬ ‫‪C 2V2eq ‬‬

‫‪E = E (Ce4 + /Ce3+ ) + 0.06 log  2 2‬‬ ‫‪‬‬
‫‪ V2 + V1‬‬ ‫‪V + V ‬‬
‫‪2‬‬ ‫‪1‬‬
‫‪C V − C 1V1‬‬
‫‪= E (Ce4 + /Ce3+ ) + 0.06 log 2 2‬‬
‫‪C 2V2eq‬‬
‫)‪E = E (Ce4 + /Ce3 + ) + 0.06 log(x − 1‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ E = f (x‬ﺍﻝﻤﺒﻴﻥ ﻓﻲ ﺍﻝﺸﻜل ))‪ (2 − (a‬ﺍﻝﺘﺎﻝﻲ ‪:‬‬
‫)‪E (V‬‬
‫‪2‬‬
‫‬ ‫‪4+‬‬ ‫‪3+‬‬
‫‪E (Ce‬‬ ‫‪/Ce‬‬ ‫)‬ ‫)‪(a‬‬
‫)‪(b‬‬
‫‬ ‫‬
‫‪(E 1 + E 2 )/2‬‬
‫‪1‬‬
‫‬ ‫‪3+‬‬ ‫‪2+‬‬
‫‪E (Fe‬‬ ‫‪/Fe‬‬ ‫)‬
‫‪x‬‬
‫‪0.5‬‬ ‫‪1 1.5‬‬ ‫‪2‬‬
‫ﺍﻝﺸﻜل )‪ (2‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪ E = f (x‬ﻋﻨﺩ ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ‪ Fe2+‬ﺒﻭﺍﺴﻁﺔ ﺸﻭﺍﺭﺩ ‪Ce4 +‬‬
‫)‪ (a‬ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻨﻅﺭﻱ )‪ (b‬ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﺘﺠﺭﻴﺒﻲ‬
‫ﻤﻼﺤﻅﺎﺕ‬
‫ﺃﻭ ﹰﻻ‪ .‬ﻋﻨﺩ ‪ x = 2‬ﻝﺩﻴﻨﺎ ) ‪. E = E 0 (Ce4 + /Ce3+‬‬

‫ﺜﺎﻨﻴﹰﺎ‪ .‬ﻓﻲ ﺠﻭﺍﺭ ‪ x = 0.5‬ﻭ ‪ x = 2‬ﻻ ﻴﺘﻐﻴﺭ ﻜﻤﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻜﺜﻴﺭﺍﹰ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﺘﹸﻌ ‪‬ﺩ ﺍﻝﻤﺤﺎﻝﻴل‬
‫ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻬﺎ ﻤﺤﺎﻝﻴل ﻤﻭﻗﻴﺔ ﻤﺅﻜﺴﺩﺓ‪-‬ﻤﺭﺠﻌﺔ‪.‬‬
‫ﺜﺎﻝﺜﹰﺎ‪ .‬ﻝﻨﻭﺠﺯ ﻓﻴﻤﺎ ﻴﻠﻲ ﺘﻐﻴﺭﺍﺕ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺍﻝﺘﻲ ﺃﺘﺎﺤﺕ ﻝﻨﺎ ﺇﻴﺠﺎﺩ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﻤﺨﺘﻠﻔﺔ ﻓﻲ ﻜل ﻤﻨﻁﻘﺔ‬
‫ﻤﻥ ﻤﻨﺎﻁﻕ ﺍﻝﻤﻌﺎﻴﺭﺓ‪:‬‬
‫ﻋﺩﺩ ﺍﻝﻤﻭﻻﺕ‬
‫‪Ce4 +‬‬ ‫‪+‬‬ ‫ ‪Fe2 +‬‬ ‫‪Ce3 +‬‬ ‫‪+‬‬ ‫‪Fe3 +‬‬
‫‪C 2V2‬‬ ‫‪C 1V1‬‬ ‫ﻓﻲ ﺍﻝﺒﺩﺀ ‪:‬‬
‫‪0‬‬ ‫‪0‬‬
‫ﻋﻨﺩ ﺍﻝﺘﻭﺍﺯﻥ‪:‬‬
‫‪C 2V2‬‬ ‫‪ .1‬ﻗﺒل ﺍﻝﺘﻜﺎﻓﺅ‬
‫‪ε‬‬ ‫‪C 1V1 − C 2V2‬‬ ‫‪C 2V2‬‬
‫‪C 2V2eq‬‬ ‫‪C 2V2eq‬‬ ‫‪ .2‬ﻋﻨﺩ ﺍﻝﺘﻜﺎﻓﺅ‬
‫‪ε′‬‬ ‫‪ε′‬‬
‫‪C 2V2 − C 1V1‬‬ ‫‪C 2V2eq‬‬ ‫‪C 2V2eq‬‬ ‫‪ .3‬ﺒﻌﺩ ﺍﻝﺘﻜﺎﻓﺅ‬
‫‪ε′′‬‬
‫‪ .3.II‬ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﺒﺔ‬
‫ﻝﻨﺭﺴﻡ ﻋﻠﻰ ﺍﻝﻭﺭﻗﺔ ﻨﻔﺴﻬﺎ ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻨﻅﺭﻱ ) ‪ E = f (x‬ﻭﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﺫﻱ‬

‫ﻥ‬
‫ﻨﺤﺼل ﻋﻠﻴﻪ ﻤﻥ ﻗﻴﺎﺱ ﻜﻤﻭﻥ ﺍﻷﺯﻭﺍﺝ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ . (2 − (b)) ،‬ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻝﻠﻤﻨﺤﻨﻴﻴﻥ ﺍﻝﺸﻜل ﺫﺍﺘﻪ ﻭﻝﻜﻨﻬﻤﺎ ﻏﻴﺭ ﻁﺒﻭﻗﻴﻥ‪ .‬ﻓﻠﻤﺎﺫﺍ ؟‬
‫ﻓﻲ ﺍﻝﺤﻘﻴﻘﺔ‪ ،‬ﻝﻤﺎ ﻜﺎﻥ ﻭﺴﻁ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻭﺴﻁﹰﺎ ﺤﻤﻀﻴﹰﺎ ﺒﺴﺒﺏ ﺇﻀﺎﻓﺔ ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ‪ ،‬ﻓﻬﻭ‬
‫ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‪ ،‬ﻭﻫﻲ ﺸﻭﺍﺭﺩ ﺘﺴﻌﻰ ﺇﻝﻰ ﺘﻜﻭﻴﻥ ﻤﻌﻘﹼﺩﺍﺕ ﻤﻊ ﺍﻝﺸﻭﺍﺭﺩ ‪ Fe3 +‬ﻭ ‪Ce4 +‬‬
‫ﻥ ﺘﻌﻘﻴﺩ ﺃﻱ ﺸﺎﺭﺩﺓ‬
‫ﻫﻲ ‪ [ Fe(SO4 )2 ]−‬ﻭ ‪ . [ Ce(SO4 ) ]2+‬ﻭﻜﻤﺎ ﺘﻌﻠﹼﻤﻨﺎ ﻤﻥ ﺍﻝﺒﺤﺙ ﺍﻝﺴﺎﺒﻕ ﻓﺈ ‪‬‬
‫ﻤﺅﻜﺴ‪‬ﺩﺓ ﻴﺅﺩﻱ ﺇﻝﻰ ﺘﺨﻔﻴﺽ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ ﺍﻝﻤﺩﺭﻭﺱ‪.‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﻓﻲ ﺤﺎﻝﺔ ‪ [SO24− ] = 1 mol/L‬ﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪E (Ce(IV)/Ce(III)) = 1.44 V‬‬
‫‪E (Fe(III)/Fe(II)) = 0.68 V‬‬ ‫ﻭ‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻴﻜﻭﻥ ‪. Eeq ≈ 1.06 V‬‬

‫‪ .4.II‬ﻤﺸﻌﺭ ﻝﻭﻨﻲ ﺃﻜﺴﺩﺓ‪-‬ﺇﺭﺠﺎﻉ‬
‫ﻥ ﺃﻱ ﺯﻭﺝ‬
‫ﻨﻼﺤﻅ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺍﺭﺘﻔﺎﻋﹰﺎ ﻤﻔﺎﺠﺌﹰﺎ ﻝﻠﻜﻤﻭﻥ )ﻗﻔﺯﺓ ﻓﻲ ﺍﻝﻜﻤﻭﻥ(‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﻤﺅﻜﺴﺩ‪/‬ﻤﺭﺠﻊ ﻴﻜﻭﻥ ﻝﻠﻤﺅﻜﺴﺩ ﻭﺍﻝﻤﺭﺠﻊ ﻓﻴﻪ ﻝﻭﻨﺎﻥ ﻤﺨﺘﻠﻔﺎﻥ‪ ،‬ﻭﻴﻘﻊ ﻜﻤﻭﻨﻪ ﺒﺠﻭﺍﺭ ﻜﻤﻭﻥ ﺍﻝﺘﻜﺎﻓﺅ‪،‬‬
‫ﻴﻤﻜﻥ ﺍﺴﺘﻌﻤﺎﻝﻪ ﺒﺼﻔﺘﻪ ﻤﺸﻌﺭﹰﺍ ﻴﺸﻴﺭ ﺇﻝﻰ ﻨﻬﺎﻴﺔ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ .‬ﻭﻫﺫﺍ ﻫﻭ ﺤﺎل ﻤﻌﻘﺩﺍﺕ ﺍﻝﻤﺸﻌﺭ‬
‫ﺍﻷﻭﺭﺘﻭﻓﻴﻨﺎﻨﺘﺭﻭﻝﻴﻥ ﻤﻊ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ‪ Fe3 +‬ﻭ ‪ Fe2 +‬ﺤﻴﺙ ﺘﺄﺨﺫ ﺍﻝﻠﻭﻥ ﺍﻷﺯﺭﻕ ﺒﻭﺠﻭﺩ‬
‫‪ Fe3 +‬ﻭﺍﻷﺤﻤﺭ ﺒﻭﺠﻭﺩ ‪ ، Fe2 +‬ﺍﻝﺸﻜل )‪. (3‬‬
‫)‪E (V‬‬
‫‪[Fe(phen )3 ]3 +‬‬
‫ﻨﻅﺭﻱ ‪ւ Eeq‬‬
‫ﺃﺯﺭﻕ‬ ‫ﺘﺠﺭﻴﺒﻲ‬
‫‪ւ Eeq‬‬
‫‪1.04‬‬
‫‪[Fe(phen )3 ]2 +‬‬
‫ﺃﺤﻤﺭ‬
‫‪Fe2 +‬‬ ‫ﺍﻝﺸﻜل )‪ : (3‬ﻴ‪‬ﺴﺘﻌﻤل ﺍﻷﻭﺭﺘﻭﻓﻴﻨﺎﻨﺘﺭﻭﻝﻴﻥ ﺒﺼﻔﺘﻪ ﻤ‪‬ﺸﻌ‪‬ﺭ ﻨﻬﺎﻴﺔ ﺍﻝﺘﻔﺎﻋل ﻋﻨﺩ ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ‬
‫ﺒﺸﻭﺍﺭﺩ ‪ . Ce4 +‬ﺘﺸﻴﺭ ‪ phen‬ﺇﻝﻰ ﻤﺸﻌﺭ ﺍﻷﻭﺭﺘﻭﻓﻴﻨﺎﻨﺘﺭﻭﻝﻴﻥ ﺍﻝﻤﻌﻁﺎﺓ ﺼﻴﻐﺘﻪ ﺃﻋﻠﻰ ﺍﻝﺸﻜل‪.‬‬
‫‪ Fe‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬ ‫‪ .III‬ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪(II‬‬

‫‪2+‬‬
‫‪MnO−‬‬
‫‪ .1.III‬ﻋﺭﺽ ﺍﻝﻤﻌﺎﻴﺭﺓ‬
‫ﻴﻭﻀﺢ ﺍﻝﺸﻜل )‪ (4‬ﺍﻹﻨﺸﺎﺀ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﻤﺴﺘﻌﻤل ﻓﻲ ﺍﻝﻤﻌﺎﻴﺭﺓ‪:‬‬

‫‪MnO−‬‬
‫ﳏﻠﻮﻝ ‪4‬‬
‫‪620‬‬
‫‪COM‬‬ ‫‪V‬‬
‫ﻣﺴﺮﻯ ﺑﻼﺗﲔ‬
‫ﳏﻠﻮﻝ ‪ Fe 2 +‬ﺣﺎﻣﻀﻲ‬
‫‪ON‬‬
‫‪OFF‬‬
‫‪ Fe‬ﺒﺸﻭﺍﺭﺩ ‪4‬‬ ‫ﺍﻝﺸﻜل )‪ : (4‬ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ‬

‫‪2+‬‬
‫‪Mn O−‬‬
‫ﺘﻌﻁﻴﻨﺎ ﺍﻝﺠﺩﺍﻭل‪:‬‬
‫‪ E (Fe‬ﻭ ‪4 Mn ) = 1.51 V‬‬

‫‪E (MnO−‬‬ ‫‪2+‬‬ ‫‪3+‬‬
‫‬
‫‪Fe2+ ) = 0.77 V‬‬
‫ﺍﻝﻤﻌﺎﺩﻝﺘﺎﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺘﺎﻥ ﺍﻝﻨﺼﻔﻴﺘﺎﻥ ﻝﻠﺯﻭﺠﻴﻥ ﺍﻝﻤﺩﺭﻭﺴﻴﻥ ﻫﻤﺎ‪:‬‬
‫‪Fe3 + + e− ⇌ Fe2+‬‬
‫‪Mn O−‬‬ ‫‪−‬‬ ‫‪+‬‬ ‫‪2+‬‬
‫‪4 + 5 e + 8 H 3 O ⇌ 2 Mn + 12 H2 O‬‬
‫ﻭﻤﻨﻪ ﻨﺠﺩ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ ﻝﻠﺘﻔﺎﻋل‪:‬‬
‫‪Mn O−‬‬ ‫‪2+‬‬ ‫‪+‬‬ ‫‪2+‬‬ ‫‪3+‬‬

‫‪4 + 5 Fe + 8 H 3 O ⇌ Mn + 5 Fe + 12 H2 O‬‬
‫ﺤﻴﺙ ﻴﺠﺭﻱ ﺘﺒﺎﺩل ‪ 5‬ﻤﻭﻻﺕ ﻤﻥ ﺍﻹﻝﻜﺘﺭﻭﻨﺎﺕ‪.‬‬
‫ﺃﻤﺎ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ‪ K‬ﻓﻴﻌﻁﻰ ﺒﺎﻝﺼﻴﻐﺔ ‪:‬‬

‫)‪5(1.51−0.77‬‬
‫‬
‫= ‪K‬‬ ‫‪10 0.06‬‬ ‫‪= 4.6 × 1061‬‬
‫ﻭﻫﻭ ﺘﻔﺎﻋل ﺘﺎﻡ‪ .‬ﻭﺘﻅﻬﺭ ﺍﻝﺘﺠﺭﺒﺔ ﺃﻴﻀﹰﺎ ﺃﻨﹼﻪ ﺘﻔﺎﻋل ﺴﺭﻴﻊ ﻭﻭﺤﻴﺩ‪.‬‬
‫ﻨﻀﻴﻑ ﺤﺠﻤﹰﺎ ‪ V2‬ﻤﻥ ﻤﺤﻠﻭل ﺒﺭﻤﻨﻐﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ C 2‬ﺇﻝﻰ ﺤﺠﻡ ‪ V1‬ﻤﻥ‬
‫ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺍﻝﻤﺤﻤ‪‬ﺽ ﺒﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ ﻭﺒﺘﺭﻜﻴﺯ ‪ .C 1‬ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‬
‫ﻴﻜﻭﻥ ﻝﺩﻴﻨﺎ‪:‬‬
‫‪C 1V1 = 5 C 2V2eq‬‬
‫‪V2‬‬
‫= ‪ x‬ﻓﻴﻜﻭﻥ‬ ‫ﻭﻫﻨﺎ ﻨﻌﺭ‪‬ﻑ ﻤﻥ ﺠﺩﻴﺩ ﺍﻝﻤﻘﺩﺍﺭ ‪ x‬ﺒﺎﻝﺼﻴﻐﺔ‬
‫‪V2eq‬‬
‫‪V2‬‬ ‫‪CV‬‬ ‫‪5C 2V2‬‬
‫= ‪x‬‬ ‫= ‪= 2 2‬‬
‫‪V2eq‬‬ ‫‪C 2V2eq‬‬ ‫‪C 1V1‬‬
‫‪ .2.III‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ﻝﻠﻤﻨﺤﻨﻲ ) ‪E = f (x‬‬
‫ﻝﻨﺩﺭﺱ ﺘﻐﻴﺭﺍﺕ ﻜﻤﻭﻥ ﺍﻷﺯﻭﺍﺝ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﻋﻨﺩ ﻭﻀﻊ ﺍﻝﺘﻭﺍﺯﻥ‪ ،‬ﺃﻱ ﻝﻨﺩﺭﺱ ﺘﻐﻴـﺭﺍﺕ‬
‫‪ E‬ﺒﺩﻻﻝﺔ ‪. x‬‬
‫ ﺤﺎﻝﺔ ‪ x = 0‬ﺃﻭ ‪.V2 = 0‬‬
‫ﻻ ﺸﻭﺍﺭﺩ ‪ ، Fe2 +‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻻ ﻴﻤﻜﻨﻨﺎ ﺘﻁﺒﻴﻕ ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ‬

‫ﻨﻅﺭﻴﹰﺎ ﻻ ﻴﻀﻡ ﺍﻝﻤﺤﻠﻭل ﺇ ﹼ‬
‫ﻋﻠﻰ ﺍﻝﺯﻭﺝ ‪ . Fe3+ / Fe2+‬ﻭﻝﻜﻥ ﻓﻲ ﺍﻝﻭﺍﻗﻊ ﻴﻀﻡ ﺍﻝﻤﺤﻠﻭل ﺁﺜﺎﺭﹰﺍ ﺼﻐﻴﺭﺓ ﺠﺩﹰﺍ ﻤﻥ ﺸﻭﺍﺭﺩ‬
‫‪ Fe3 +‬ﻨﺎﺠﻤﺔ ﻋﻥ ﺃﻜﺴﺩﺓ ﺸﻭﺍﺭﺩ ‪ Fe2 +‬ﺒﺄﻜﺴﺠﻴﻥ ﺍﻝﻬﻭﺍﺀ ﺍﻝﻤﻨﺤل ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻴﻤﻜﻨﻨﺎ‬
‫ﻗﻴﺎﺱ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ ‪ Fe3+ / Fe2+‬ﻭﺍﻝﻘﻴﻤﺔ ﺍﻝﺘﻲ ﻨﺤﺼل ﻋﻠﻴﻬﺎ ﺘﺘﻌﻠﻕ ﺒﻤﺩﻯ ﻜﻭﻥ ﺍﻝﻤﺤﻠﻭل‬
‫ﺍﻝﻤﺤﻀ‪‬ﺭ ﻁﺎﺯﺠﹰﺎ‪.‬‬
‫ ﺤﺎﻝﺔ ‪ 0 < x < 1‬ﺃﻭ ‪. 0 < V2 < V2eq‬‬
‫ﻋﻨﺩ ﻜل ﻝﺤﻅﺔ ﻤﻥ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺘﻘﻀﻲ ﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﺍﻝﺘﻔﺎﻋل ﺃﻥ ﻴﻜﻭﻥ ‪:‬‬
‫] ‪5 [Mn2 + ] = [Fe3 +‬‬

‫ﻭﻤﻨﻪ ﻨﻜﺘﺏ‪:‬‬
‫‪Mn O−‬‬
‫‪4 + 5 Fe‬‬
‫‪2+‬‬
‫‪+ 8 H3 O+ ⇌ Mn2 + + 5 Fe3 +‬‬ ‫‪+ 12 H2 O‬‬
‫‪t = 0 C 2V2‬‬ ‫‪C 1V1‬‬ ‫‪0‬‬ ‫‪0‬‬
‫‪teq‬‬ ‫‪ε‬‬ ‫‪5C 2V2‬‬ ‫‪C 2V2‬‬ ‫‪C 1V1 − 5C 2V2‬‬
‫ﻭﻤﻥ ﺍﻷﺴﻬل‪ ،‬ﻗﺒل ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪ ،‬ﺤﺴﺎﺏ ‪ E‬ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺯﻭﺝ ‪: Fe 3+ /Fe2 +‬‬
‫] ‪[Fe3 +‬‬
‫‪E = E (Fe 3+ /Fe2 + ) + 0.06 log‬‬
‫] ‪[Fe2 +‬‬
‫‪5C 2V2‬‬
‫‪= E (Fe 3+ /Fe2 + ) + 0.06 log‬‬
‫‪C 1V1 − 5C 2V2‬‬
‫‪x‬‬
‫‪E = E (Fe 3+ /Fe2 + ) + 0.06 log‬‬
‫‪1−x‬‬
‫ﻤﻼﺤﻅﺔ ‪ :‬ﻋﻨﺩ ﻨﻘﻁﺔ ﻨﺼﻑ ﺍﻝﺘﻜﺎﻓﺅ ‪ ، x = 0.5‬ﻨﺠﺩ ﻤﺠﺩﺩﹰﺍ ) ‪. E = E (Fe 3+ /Fe2 +‬‬
‫ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ‪ x = 1‬ﺃﻱ ‪.V2 = V2eq‬‬
‫‪ Mn O−‬ﻭﻓﻘﹰﺎ ﻝﻠﻨﺴﺏ ﺍﻝﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴﺔ ﻭﻤﻥ ﹶﺜ ‪‬ﻡ‪:‬‬

‫‪ Fe‬ﻭ ‪4‬‬
‫‪2+‬‬
‫ﺴﻭﻑ ﺘﻤﺘﺯﺝ ﻋﻨﺩ ﻫﺫﻩ ﺍﻝﻨﻘﻁﺔ ﺸﻭﺍﺭﺩ‬
‫‪5[Mn O−‬‬ ‫‪2+‬‬

‫‪4 ]eq = [Fe ]eq‬‬
‫ﻭﻨﻜﺘﺏ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ ‪: Fe3+ /Fe2 +‬‬
‫‬ ‫‪3+‬‬ ‫‪2+‬‬

‫‪[Fe3 + ]eq‬‬
‫)∗(‬ ‫‪Eeq = E (Fe‬‬ ‫‪/Fe ) + 0.06 log‬‬
‫‪[Fe2 + ]eq‬‬
‫‪: MnO−‬‬
‫‪4 /Mn‬‬
‫‪2+‬‬
‫ﻭﻜﺫﻝﻙ ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ‬
‫] ‪[MnO4- ]eq [H 3O+‬‬

‫)†(‬ ‫‪Eeq = E (MnO−‬‬ ‫‪2+‬‬
‫‪4 /Mn ) + 0.012 log‬‬
‫‪[Mn2 + ]eq‬‬
‫ﻨﻀﺭﺏ ﺍﻝﻌﻼﻗﺔ )†( ﺒﺎﻝﻌﺩﺩ ‪ 5‬ﺜﻡ ﻨﺠﻤﻊ ﺍﻝﻨﺎﺘﺞ ﺇﻝﻰ )∗( ﻓﻨﺠﺩ ‪:‬‬
‫‪6Eeq = E (Fe3+ /Fe2 + ) + 5 E (MnO−‬‬ ‫‪2+‬‬ ‫‪+ 8‬‬

‫] ‪4 /Mn ) + 0.06 log[H 3O‬‬
‫‪E 0 (Fe3 + /Fe2 + ) + 5E (MnO−‬‬ ‫‪2+‬‬

‫) ‪4 /Mn‬‬
‫‪Eeq‬‬ ‫=‬ ‫‪− 0.08 pH‬‬
‫‪6‬‬
‫ﻥ ﻜﻤﻭﻥ ﺍﻝﺘﻜﺎﻓﺅ ﻴﺘﻌﻠﻕ ﺒﻘﻴﻤﺔ ‪. pH‬‬

‫ ﺤﺎﻝﺔ ‪ x > 1‬ﺃﻭ ‪.V2 > V2eq‬‬
‫ﻓﻲ ﻫﺫﻩ ﺍﻝﺤﺎﻝﺔ ﺘﺼﺒﺢ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﻫﻲ ﺍﻝﺭﺍﺠﺤﺔ ‪:‬‬
‫) ‪C 2 (V2 − V2eq‬‬
‫‪[ Mn O−‬‬
‫=]‪4‬‬
‫‪V1 + V2‬‬
‫‪C 2V2eq‬‬
‫= ] ‪[Mn2 +‬‬
‫‪V1 + V2‬‬
‫ﻭﻋﻠﻴﻪ ﻴﻜﻭﻥ ‪:‬‬
‫‪C 2 (V2 − V2eq )[H 3O+ ]8‬‬

‫‪E =E‬‬ ‫‬
‫‪(MnO−‬‬ ‫‪2+‬‬
‫) ‪4 /Mn‬‬ ‫‪+ 0.012 log‬‬
‫‪C 2V2eq‬‬
‫ﻥ‪:‬‬
‫ﺃﻱ ﺇ ‪‬‬
‫‪E = E (MnO−‬‬ ‫‪2+‬‬

‫‪4 /Mn ) + 0.012 log(x − 1) − 0.096 pH‬‬
‫ﻭﻫﻜﺫﺍ ﻨﺠﺩ ﺍﻝﻤﻨﺤﻨﻲ ) ‪ E = f (x‬ﺍﻝﻤﺒﻴﻥ ﻓﻲ ﺍﻝﺸﻜل ))‪ (5 − (a‬ﺍﻝﺫﻱ ﻴﻅﻬﺭ ﻤﻌﺎﻴﺭﺓ‬

‫‪ Mn O−‬ﻤﺭﺴﻭﻤﹰﺎ ﻓﻲ ﺤﺎﻝﺔ ‪. pH = 0‬‬
‫ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ (II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬
‫)‪E (V‬‬
‫‪2‬‬
‫‬ ‫‪−‬‬ ‫‪2+‬‬

‫‪E (MnO4 /Mn‬‬ ‫)‬ ‫)‪(a‬‬
‫)‪Eeq (th‬‬ ‫)‪(b‬‬
‫‪1‬‬
‫‬ ‫‪3+‬‬ ‫‪2+‬‬
‫‪E (Fe‬‬ ‫‪/Fe‬‬ ‫)‬
‫‪x‬‬
‫‪0.5‬‬ ‫‪1 1.5‬‬ ‫‪2‬‬
‫‪Mn O−‬‬
‫‪4‬‬ ‫ﺸﻭﺍﺭﺩ‬ ‫ﺒﻭﺍﺴﻁﺔ‬ ‫‪Fe‬‬ ‫‪2+‬‬
‫ﺸﻭﺍﺭﺩ‬ ‫ﻤﻌﺎﻴﺭﺓ‬ ‫ﻋﻨﺩ‬ ‫‪E‬‬ ‫=‬ ‫ﺍﻝﺸﻜل )‪ : (5‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪f (x‬‬
‫)‪ (a‬ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻨﻅﺭﻱ )‪ (b‬ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﺘﺠﺭﻴﺒﻲ‬
‫‪ .3.III‬ﻤﻘﺎﺭﻨﺔ ﻤﻊ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﺠﺭﻴﺒﻴﺔ‬
‫ﻝﻨﺭﺴﻡ ﻋﻠﻰ ﺍﻝﻭﺭﻗﺔ ﻨﻔﺴﻬﺎ ﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﻨﻅﺭﻱ ) ‪ ، E = f (x‬ﺍﻝﺸﻜل ))‪(5 − (a‬‬

‫ﻭﺍﻝﻤﻨﺤﻨﻲ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﺫﻱ ﻨﺤﺼل ﻋﻠﻴﻪ ﻤﻥ ﻗﻴﺎﺱ ﻜﻤﻭﻥ ﺍﻷﺯﻭﺍﺝ ﺍﻝﻤﻭﺠﻭﺩﺓ ﻓﻲ ﺍﻝﻤﺤﻠﻭل‪،‬‬
‫ﻥ ﻝﻠﻤﻨﺤﻨﻴﻴﻥ ﺍﻝﺸﻜل ﺫﺍﺘﻪ ﻭﻝﻜﻨﻬﻤﺎ ﻏﻴﺭ ﻁﺒﻭﻗﻴﻥ‪ .‬ﻓﻠﻤﺎﺫﺍ ؟‬
‫ﺍﻝﺸﻜل ))‪ . (5 − (b‬ﻨﻼﺤﻅ ﺃ ‪‬‬
‫ﻓﻲ ﺍﻝﺤﻘﻴﻘﺔ‪ ،‬ﻝﻤﺎ ﻜﺎﻥ ﻭﺴﻁ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻭﺴﻁﹰﺎ ﺤﺎﻤﻀﻴﹰﺎ ﺒﺈﻀﺎﻓﺔ ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ‬
‫ﻓﻬﻭ ﻴﻀ ‪‬ﻡ ﺸﻭﺍﺭﺩ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‪ ،‬ﻭﻫﻲ ﺸﻭﺍﺭﺩ ﺘﺴﻌﻰ ﺇﻝﻰ ﺘﺸﻜﻴل ﻤﻌﻘﹼﺩﺍﺕ ﻤﻊ ﺍﻝﺸﻭﺍﺭﺩ ‪: Fe3 +‬‬
‫‪ . [ Fe(SO4 )2 ]−‬ﻭﻫﺫﺍ ﻤﺎ ﻴﻔﺴ‪‬ﺭ ﺍﻨﺨﻔﺎﺽ ﺍﻝﻜﻤﻭﻥ ﺍﻝﺘﺠﺭﻴﺒﻲ ﺍﻝﻤﻘﺎﺱ ﻋﻨﺩ ‪ x < 1‬ﻋﻥ ﺍﻝﻜﻤﻭﻥ‬
‫ﺍﻝﻨﻅﺭﻱ ﻷﻥ ‪-‬ﻜﻤﺎ ﺘﻌﻠﹼﻤﻨﺎ ﻤﻥ ﺍﻝﺒﺤﺙ ﺍﻝﺴﺎﺒﻕ‪ -‬ﺘﻌﻘﻴﺩ ﺃﻱ ﺸﺎﺭﺩﺓ ﻤﺅﻜﺴ‪‬ﺩﺓ ﻴﺅﺩﻱ ﺇﻝﻰ ﺘﺨﻔﻴﺽ‬
‫ﻜﻤﻭﻥ ﺍﻝﺯﻭﺝ ﺍﻝﻤﻌﺘﺒﺭ‪.‬‬
‫ﻥ ﺘﻔﺴﻴﺭ ﺍﻻﻨﺯﻴﺎﺡ ﺒﻴﻥ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ ﺍﻝﻨﻅﺭﻱ ﻭﺍﻝﺘﺠﺭﻴﺒﻲ ﻴﻌﻭﺩ ﺇﻝﻰ‬
‫ﺃﻤ‪‬ﺎ ﻓﻲ ﺤﺎﻝﺔ ‪ x > 1‬ﻓﺈ ‪‬‬
‫ﻅﺎﻫﺭﺓ ﺘﹸﻌﺭﻑ ﺒﺎﺴﻡ ﻅﺎﻫﺭﺓ ﺍﻝﻜﻤﻭﻥ ﺍﻝﻤﺨﺘﻠﹶﻁ ﺍﻝﺘﻲ ﺘﺨﺭﺝ ﻋﻥ ﻨﻁﺎﻕ ﻋﺭﺽ ﻫﺫﺍ ﺍﻝﻜﺘﺎﺏ‪.‬‬
‫ﻤﻼﺤﻅﺎﺕ‬
‫ﺃﻭ ﹰﻻ‪ .‬ﻓﻲ ﺠﻭﺍﺭ ‪ x = 0.5‬ﻭ ‪ x = 2‬ﻻ ﻴﺘﻐﻴﺭ ﻜﻤﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻜﺜﻴﺭﺍﹰ‪ ،‬ﻭﺒﺎﻝﺘﺎﻝﻲ ﺘﹸﻌ ‪‬ﺩ ﺍﻝﻤﺤﺎﻝﻴل‬
‫ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻬﺎ ﻤﺤﺎﻝﻴل ﻤﻭﻗﻴﺔ ﻤﺅﻜﺴﺩﺓ‪-‬ﻤﺭﺠﻌﺔ‪.‬‬
‫ﺜﺎﻨﻴﹰﺎ‪ .‬ﻴﺠﺏ ﺘﺤﻤﻴﺽ ﻤﺤﻠﻭل ﺍﻝﺤﺩﻴﺩ )‪ ، (II‬ﻭﻝﻜﻥ ﻻ ﻴﻤﻜﻨﻨﺎ ﺍﺴﺘﻌﻤﺎل ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﺃﻭ‬
‫ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﻓﻲ ﺠﻌل ﺍﻝﻭﺴﻁ ﺤﻤﻀﻴﹰﺎ‪ ،‬ﻭﺫﻝﻙ ﻹﻤﻜﺎﻨﻴﺔ ﺤﺼﻭل ﺘﻔﺎﻋﻼﺕ ﺜﺎﻨﻭﻴﺔ ﻜﻤﺎ‬
‫ﻴﻅﻬﺭ ﻫﺫﺍ ﺠﻠﻴﹰﺎ ﻓﻲ ﺍﻝﺸﻜل )‪ ، (6‬ﺤﻴﺙ ﺘﺅﻜﺴﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺘﺭﺍﺕ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ‪ ، II‬ﻭ‬
‫ﺘﺅﻜﺴﺩ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ‪.‬‬
‫)‪E (V‬‬
‫‪Mn O−‬‬
‫‪4‬‬
‫‪1.51‬‬
‫‪Mn 2+‬‬
‫) ‪Cl2 ( g‬‬
‫‪1.36‬‬
‫‪Cl−‬‬
‫‪NO−‬‬
‫‪3‬‬
‫‪0.96‬‬
‫‪NO‬‬
‫‪Fe3+‬‬
‫‪0.77‬‬
‫‪Fe2+‬‬
‫ﺍﻝﺸﻜل )‪ : (6‬ﺘﺅﻜﺴﺩ ﺸﻭﺍﺭﺩ ﺍﻝﻨﺘﺭﺍﺕ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ )‪ ، (II‬ﻭ ﺘﺅﻜﺴﺩ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﺸﻭﺍﺭﺩ ﺍﻝﻜﻠﻭﺭ‪:‬‬
‫ﺇﺫﻥ ﻻ ﻴﻤﻜﻥ ﺍﺴﺘﻌﻤﺎل ﺤﻤﺽ ﺍﻵﺯﻭﺕ ﺃﻭ ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﻤﺎﺀ ﻝﻠﻌﻤل ﻓﻲ ﻭﺴﻁ ﺤﺎﻤﻀﻲ‪ ،‬ﻭﺇﻻ ﻓﻠﻥ ﻴﻜﻭﻥ‬
‫ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﻭﺤﻴﺩ ﺍﻝﺫﻱ ﻴﺠﺭﻱ‪.‬‬
‫ﺜﺎﻝﺜﹰﺎ‪ .‬ﻓﻲ ﺃﺜﻨﺎﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻴﻤﻜﻥ ﻝﻠﻤﺤﻠﻭل ﺍﻝﻤﻌﺎ ‪‬ﻴِﺭ ﺃﻥ ﻴﻜﻭﻥ ﺇﻤﺎ ﻓﻲ ﺍﻝﺒﻴﻜﺭ ﻭﺇﻤﺎ ﻓﻲ ﺴﺤﺎﺤﺔ‬
‫‪ ، MnO−‬ﻴﺠﺏ‬
‫‪ Fe‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬
‫‪2+‬‬
‫ﺍﻝﻤﻌﺎﻴﺭﺓ‪ .‬ﻭﻝﻜﻥ ﻓﻲ ﺤﺎﻝﺔ ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ‬
‫ﻻ ﺘﻔﺎﻋﻠﺕ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ‬
‫ﺃﻥ ﻴﻜﻭﻥ ﻤﺤﻠﻭل ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﻓﻲ ﺍﻝﺴﺤﺎﺤﺔ ﺤﺼﺭﹰﺍ ﻭﺇ ﹼ‬
‫‪ MnO−‬ﻓﻲ ﺍﻝﺒﻴﻜﺭ ﻤﻊ ﺸﻭﺍﺭﺩ ‪ Mn2+‬ﺍﻝﺘﻲ ﺘﺘﺸ ﹼﻜل ﺘﺩﺭﻴﺠﻴﹰﺎ ﻤﻊ ﺘﻘﺩ‪‬ﻡ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻭﺫﻝﻙ‬
‫‪4‬‬
‫ﻭﻓﻘﹰﺎ ﻝﻠﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼﻠﺔ‪:‬‬

‫‪2 Mn O−‬‬ ‫‪2+‬‬
‫‪4 + 3 Mn + 6 H2 O → 5 Mn O2 + 4 H 3 O‬‬
‫‪+‬‬
‫ﻼ ﺜﺎﻨﻭﻴﹰﺎ ﻤﻥ ﺸﺄﻨﻪ ﺃﻥ ﻴﺠﻌل ﻨﺘﺎﺌﺞ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺨﺎﻁﺌﺔ‪ .‬ﻤﻥ ﺍﻝﻤﻔﻴﺩ‬

‫ﻭﻴﻌﺘﺒﺭ ﻫﺫﺍ ﺍﻝﺘﻔﺎﻋل ﺘﻔﺎﻋ ﹰ‬
‫ﻥ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺴﺎﺒﻕ ﺃﺒﻁﺄ ﻤﻥ ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻴﻤﻜﻥ ﺇﻫﻤﺎﻝﻪ ﻋﻨﺩﻤﺎ‬
‫ﺍﻹﺸﺎﺭﺓ ﺇﻝﻰ ﺃ ‪‬‬
‫ﻴﻜﻭﻥ ﻤﺤﻠﻭل ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﻓﻲ ﺍﻝﺴﺤﺎﺤﺔ‪ ،‬ﻭﻝﻜﻥ ﻫﺫﺍ ﻏﻴﺭ ﻤﻤﻜﻥ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﻤﺤﻠﻭل‬
‫ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﻓﻲ ﺍﻝﺒﻴﻜﺭ‪ ،‬ﺍﻝﺸﻜل )‪. (7‬‬
‫‬
‫)‪E (V‬‬
‫‪Mn O−‬‬
‫‪4‬‬
‫‪1.69‬‬
‫‪MnO2‬‬
‫‪MnO2‬‬
‫‪1.23‬‬
‫‪Mn 2+‬‬
‫ﺍﻝﺘﻲ ﺘﺘﺸﻜﹼل ﺘﺩﺭﻴﺠﻴﹰﺎ ﻤﻊ ﺘﻘﺩ‪‬ﻡ ﺍﻝﻤﻌﺎﻴﺭﺓ‬ ‫ﺍﻝﺸﻜل )‪ : (7‬ﺘﺅﻜﺴﺩ ﺸﻭﺍﺭﺩ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﺸﻭﺍﺭﺩ ﺍﻝﻤﻨﻐﻨﻴﺯ ‪Mn2+‬‬
‫ﻭﻫﺫﺍ ﻤﻥ ﺸﺄﻨﻪ ﺃﻥ ﻴﺠﻌل ﻨﺘﺎﺌﺞ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺨﺎﻁﺌﺔ‪.‬‬
‫ﺭﺍﺒﻌﹰﺎ‪ .‬ﻋﻨﺩﻤﺎ ﻻ ﻴﻜﻭﻥ ﻝﻌﻨﺼﺭ ﻤﺎ ﺍﻝ ﱠﺫﺭﻴ‪‬ﺔ ﻨﻔﺴﻬﺎ ﻓﻲ ﻭﻀﻌﻴﻪ ﺍﻝﻤﺅﻜﺴﺩ ﻭﺍﻝﻤﺭﺠﻊ‬

‫)‪ ، ( Cr2 O27− /Cr 3+, I2 /I−,...‬ﺃﻭ ﻋﻨﺩﻤﺎ ﻻ ﻴﻜﻭﻥ ﺍﻝﻤﺅﻜﺴﺩ ﺃﻭ ﺍﻝﻤﺭﺠﻊ ﻝﻌﻨﺼﺭ ﻤﺎ‬
‫ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺎﺌﻲ )‪ ، (Cu2 + /Cu2O, O2 /H2 O2 ,...‬ﻴﺼﺒﺢ ﺤﺴﺎﺏ ﻜﻤﻭﻥ‬

‫ﺍﻷﺯﻭﺍﺝ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﺃﻤﺭﹰﺍ ﻏﻴﺭ ﺴﻬل ﻜﻤﺎ ﺭﺃﻴﻨﺎ ﻓﻲ ﺍﻷﻤﺜﻠﺔ ﺍﻝﺘﻲ ﻋﺭﻀﻨﺎﻫﺎ‪ .‬ﻓﻲ‬
‫ﻭﺍﻗﻊ ﺍﻷﻤﺭ ﻴﻜﻭﻥ ﺍﻝﻜﻤﻭﻥ ﻋﻨﺩ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ ﻝﻴﺱ ﺘﺎﺒﻌﹰﺎ ﻓﻘﻁ ﻝﻠـ ‪ pH‬ﻭﺇﻨﻤﺎ ﺃﻴﻀﹰﺎ‬
‫ﻝﺘﺭﺍﻜﻴﺯ ﺒﻌﺽ ﺍﻷﻨﻭﺍﻉ ﺃﻭ ﻝﻀﻐﻭﻁﻬﺎ ﺍﻝﺠﺯﺌﻴﺔ‪ ،‬ﻭﺴﻭﻑ ﻨﻌﺎﻝﺞ ﻫﺫﻩ ﺍﻝﺤﺎﻻﺕ ﻓﻲ ﺍﻝﺘﻤﺎﺭﻴﻥ‪.‬‬
‫‬
‫ﻤﻌﺎﻴﺭﺓ ﺸﻭﺍﺭﺩ ﺍﻝﺤﺩﻴﺩ ‪ II‬ﺒﺸﻭﺍﺭﺩ ﺍﻝﺒﻴﻜﺭﻭﻤﺎﺕ‪.‬‬ ‫‬

‫ﻻ ﺤﻤﻀﻴﹰﺎ ﻤﻥ‬
‫ﻨﻀﻴﻑ ﺇﻝﻰ ‪ 25 mL‬ﻤﻥ ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ ‪ II‬ﺒﺘﺭﻜﻴﺯ ‪ ، C‬ﻤﺤﻠﻭ ﹰ‬
‫ﺒﻴﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ ‪ .C ′ = 4 × 10−2 mol/L‬ﻨﺼل ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜـﺎﻓﺅ‬
‫ﺒﻌﺩ ﺇﻀﺎﻓﺔ ﺤﺠﻡ ﻤﻥ ﺍﻝﻤﺤﻠﻭل ﺍﻝﻤﺅﻜﺴ‪‬ﺩ ﻗﺩﺭﻩ ‪.Veq′ = 12 mL‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻭﺍﺤﺴﺏ ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ‪ ،‬ﻤﺎﺫﺍ ﺘﺴﺘﻨﺘﺞ؟‬
‫‪ .2‬ﺍﺤﺴﺏ ﺘﺭﻜﻴﺯ ﻤﺤﻠﻭل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺩﻴﺩ )‪.(II‬‬
‫‪ .3‬ﻝﻴﻜﻥ ‪ E‬ﻜﻤﻭﻥ ﺇﻝﻜﺘﺭﻭﺩ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﻤﻐﻤﻭﺱ ﻓﻲ ﺍﻝﻤﺤﻠﻭل ﺃﺜﻨﺎﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻭﺫﻝﻙ‬
‫ﺒﺎﻝﻨﺴﺒﺔ ﻹﻝﻜﺘﺭﻭﺩ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻤﺭﺠﻌﻲ‪ .‬ﺃﻭﺠﺩ ﺍﻝﺘﺎﺒﻊ )‪ ، E = f (V ′‬ﺤﻴﺙ ‪V ′‬‬
‫ﻫﻭ ﺤﺠﻡ ﻤﺤﻠﻭل ﺒﻴﻜﺭﻭﻤﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺍ ﻝﻤﻀﺎﻓﺔ ﻤﻘﺩﺭ ﹰﺍ ﺒﺎ ﻝـ ‪ mL‬ﻭ ﺫﻝﻙ ﻋﻨﺩ‬
‫‪. pH = 0‬‬
‫)‪ (a‬ﻓﻲ ﺤﺎﻝﺔ ‪. 0 < V ′(mL) < 12‬‬
‫)‪ (b‬ﻓﻲ ﺤﺎﻝﺔ ‪. 12 < V ′(mL) < 25‬‬
‫‪ .4‬ﺍﺤﺴﺏ ‪ E‬ﻋﻨﺩﻤﺎ ‪ .V ′ = 12mL‬ﺍﺭﺴﻡ ﺘﻐﻴﺭﺍﺕ ﺍﻝﻤﻨﺤﻨﻲ )‪. E = f (V ′‬‬
‫‪ E (Cr2O27− /Cr3+ ) = 1.33 V‬ﻭ ‪. E (Fe3 + /Fe2 + ) = 0.77 V‬‬
‫ﻤﻌﺎﻴﺭﺓ ﺍﻝﻤﺎﺀ ﺍﻷﻜﺴﺠﻴﻨﻲ‪.‬‬ ‫‬
‫ﻨﺩﺭﺱ ﻤﻌﺎﻴﺭﺓ ‪ V0 = 100 mL‬ﻤﻥ ﻤﺤﻠﻭل ﺍﻝﻤﺎﺀ ﺍﻷﻜﺴﺠﻴﻨﻲ ﺒﺘﺭﻜﻴﺯ ‪ C 0‬ﻴﺴﺎﻭﻱ‬
‫‪ ، 9 × 10−3 mol/L‬ﻭﺫﻝﻙ ﺒﺎﺴﺘﻌﻤﺎل ﻤﺤﻠﻭل ﻤﻥ ﺒﺭﻤﻨﻐﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ ﺒﺘﺭﻜﻴﺯ‬

‫ﻥ ‪pH‬‬
‫ﻥ ﻀﻐﻁ ﺍﻝﻬﻭﺍﺀ ﻫﻭ ﺘﻘﺭﻴﺒﹰﺎ ‪ 1 bar‬ﻭﺃ ‪‬‬
‫‪ .C = 10−1 mol/L‬ﻭﻨﻌﻠﻡ ﺃ ‪‬‬
‫ﺍﻝﻤﺤﻠﻭل ﻜﺎﻥ ﻤﺜﺒﺘﹰﺎ ﻋﻨﺩ ﻗﻴﻤﺔ ﺍﻝﺼﻔﺭ‪ .‬ﻝﻴﻜﻥ ‪ E‬ﻜﻤﻭﻥ ﺇﻝﻜﺘﺭﻭﺩ ﻤﻥ ﺍﻝﺒﻼﺘﻴﻥ ﻤﻐﻤﻭﺱ ﻓﻲ‬
‫ﺍﻝﻤﺤﻠﻭل ﺃﺜﻨﺎﺀ ﺍﻝﻤﻌﺎﻴﺭﺓ‪ ،‬ﻭﺫﻝﻙ ﺒﺎﻝﻨﺴﺒﺔ ﻹﻝﻜﺘﺭﻭﺩ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﺍﻝﻤﺭﺠﻌﻲ‪.‬‬
‫‪ .1‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ‪ .‬ﻫل ﺍﻝﺘﻔﺎﻋل ﺘﺎﻡ ﻭﻝﻤﺎﺫﺍ؟‬
‫‪ .2‬ﺍﺤﺴﺏ ﺤﺠﻡ ﻤﺤﻠﻭل ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ﺍﻝﻭﺍﺠﺏ ﺇﻀﺎﻓﺘﻪ ﻝﻠﻭﺼﻭل ﺇﻝﻰ ﻨﻘﻁﺔ ﺍﻝﺘﻜﺎﻓﺅ‪.‬‬
‫‪ .3‬ﺃﻭﺠﺩ ﻋﺒﺎﺭﺓ ) ‪ E = f (V‬ﻋﻨﺩﻤﺎ‪:‬‬

‫‪. 0 < V < Veq‬‬ ‫)‪(a‬‬
‫‪.V > Veq‬‬ ‫)‪(b‬‬
‫‪ .4‬ﺍﺤﺴﺏ ‪ E‬ﻋﻨﺩﻤﺎ ‪ .V = Veq‬ﺍﺭﺴﻡ ﺘﻐﻴﺭﺍﺕ ﺍﻝﻤﻨﺤﻨﻲ ) ‪. E = f (V‬‬
‫‪ E (MnO−‬ﻭ ‪E (O2 /H2O2 ) = 0.68 V‬‬ ‫‪2+‬‬
‫‪4 /Mn ) = 1.51 V‬‬
‫ﻤﻥ ﻏﺎﺯ ﺍﻷﻜﺴﺠﻴﻥ‪.‬‬ ‫‪1‬‬

‫‪5‬‬
‫ﻤﻥ ﻏﺎﺯ ﺍﻵﺯﻭﺕ ﻭ‬ ‫‪4‬‬
‫‪5‬‬
‫ﻥ ﺍﻝﻬﻭﺍﺀ ﻤﻜﻭ‪‬ﻥ ﺤﺠﻤﻴﹰﺎ ﻤﻥ‬
‫ﻭﻨﺫﻜﹼﺭ ﺃ ‪‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺘﺎﺳﻊ‬
‫
‪pH-‬‬
‫ ‬
‫‪ .I‬ﻤﺨﻁﻁ ﻜﻤﻭﻥ‪ pH -‬ﻝﻠﻤﺎﺀ‬

‫‪ .1. I‬ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ‬
‫‪ .2.II‬ﺍﺴﺘﺜﻤﺎﺭ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺎﺀ‬
‫‪ .II‬ﻤﺨﻁﻁ ﻜﻤﻭﻥ‪ pH -‬ﻝﻠﺤﺩﻴﺩ‬
‫‪ .1.II‬ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ‬
‫‪ .2.II‬ﺍﺴﺘﺜﻤﺎﺭ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺤﺩﻴﺩ‬
‫‪279‬‬
‫ﺍﻟﻔﺼﻞ ﺍﻟﺘﺎﺳﻊ‬ ‫‪280‬‬
‫ﻴﻬﺩﻑ ﻫﺫﺍ ﺍﻝﺒﺤﺙ ﺇﻝﻰ ﺘﺤﺩﻴﺩ ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ﺃﻭ ﺍﻝﻭﺠﻭﺩ ﻝﻤﺨﺘﻠﻑ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﺘﺄﻜﺴﺩﺓ ﻭﺍﻝﻤﺭﺠﻌ‪‬ﺔ‬
‫ﺒﺩﻻﻝﺔ ﻜﻤﻭﻥ ﺍﻝﻤﺤﻠﻭل ﻭ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﻴﺠﺭﻱ ﺘﺤﺩﻴﺩ ﺍﻝﺤﺩﻭﺩ ﺍﻝﻔﺎﺼﻠﺔ ﺒﻤﺭﺍﻋﺎﺓ ﺍﻻﺼﻁﻼﺤﺎﺕ ﺍﻝﺘﻲ ﺘﺤﺩ‪‬ﺜﻨﺎ ﻋﻨﻬﺎ ﻓﻲ ﺍﻝﻔﺼل ﺍﻝﺴﺎﺒﻕ‪.‬‬
‫‪ .I‬ﻤﺨﻁﻁ ﻜﻤﻭﻥ‪ pH -‬ﻝﻠﻤﺎﺀ‬
‫‪ .1.I‬ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ‬
‫ﻴﺴﺎﻫﻡ ﺍﻝﻤﺎﺀ ﻓﻲ ﺯﻭﺠﻲ ﺃﻜﺴﺩﺓ‪-‬ﺇﺭﺠﺎﻉ ‪ :‬ﺍﻷﻭل ﻫﻭ ‪ H2O/H2‬ﺤﻴﺙ ﻴﺅﺩﻱ ﻓﻲ ﻫﺫﺍ‬

‫ﺍﻝﺯﻭﺝ ﺩﻭﺭ ﻤﺅﻜﺴ‪‬ﺩ ﻭﺍﻝﺜﺎﻨﻲ ﻫﻭ ‪ O2 /H2O‬ﻭﻫﻨﺎ ﻴﺅﺩﻱ ﺍﻝﻤﺎﺀ ﺩﻭﺭ ﻤﺭﺠﹺﻊ‪.‬‬
‫• ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺅﻜﺴ‪‬ﺩﹰﺍ‪ :‬ﺍﻝﺯﻭﺝ ‪: H2O/H2‬‬

‫ﻥ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﻋﻨﺼﺭ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ ﻓﻲ ﺍﻝﻤﺎﺀ ‪ ، +I‬ﻭﻴﺼﺒﺢ ‪ 0‬ﻓﻲ ‪ . H 2‬ﻭﻨﺠﺩ ﺃﻴﻀﹰﺎ ﺭﻗﻡ‬
‫ﺇ‪‬‬
‫ﺍﻷﻜﺴﺩﺓ ‪ +I‬ﻝﻠﻬﻴﺩﺭﻭﺠﻴﻥ ﻓﻲ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ H3O+‬ﻭﻓﻲ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ‬
‫‪ . OH−‬ﻭﺒﺎﻝﺘﺎﻝﻲ ﻨﺠﺩ ﺘﻌﺒﻴﺭﻴﻥ ﺁﺨﺭﻴﻥ ﻝﻠﺯﻭﺝ ‪ H2O/H2‬ﻫﻤﺎ ‪H3O+ /H2‬‬
‫ﻭ ‪. OH− /H2‬‬
‫ﻭﺒﺼﻭﺭﺓ ﻋﻤﻠﻴﺔ ﻨﺴﺘﻌﻤل ﺍﻝﺯﻭﺝ ‪ H3O+ /H2‬ﻭﻨﻜﺘﺏ‪:‬‬
‫‪2H 3O+ + 2e− ⇌ H2 + 2H2O‬‬
‫ﻭﺘﹸﻜ ﹶﺘﺏ ﻤﻌﺎﺩﻝﺔ ﻨﺭﻨﺴﺕ ﻝﻬﺫﺍ ﺍﻝﺯﻭﺝ ﺒﺎﻝﺸﻜل‪:‬‬
‫‪0‬‬ ‫‪+‬‬ ‫‪0.06‬‬ ‫‪[H 3O+ ]2‬‬

‫‪E = E (H3O /H2 ) +‬‬ ‫‪log‬‬
‫‪2‬‬ ‫) ‪P(H2‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ‪ ، E 0 (H 3O+ /H2 ) = 0 V‬ﻓﺈﻨﻨﺎ ﻨﺠﺩ‪:‬‬
‫) ‪E = − 0.06 pH − 0.03 log P(H2‬‬
‫ﻥ ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ﺒﻴﻥ‬

‫ﻓﺈﺫﺍ ﺭﺴﻤﻨﺎ ﺍﻝﻤﺨﻁﻁ )‪ E = f ( pH‬ﻋﻨﺩﻤﺎ ‪ P(H2 ) = 1bar‬ﻓﺈ ‪‬‬
‫‪ H2‬ﻭ ‪ H2O‬ﻴﻘﺒل ﺍﻝﻤﻌﺎﺩﻝﺔ‪:‬‬
‫‪E1 = −0.06 pH‬‬
‫‪281‬‬ ‫ﺭﺳﻢ ﺍﳌﺨﻄﻄﺎﺕ ﻛﻤﻮﻥ‪pH -‬‬
‫• ﺍﻝﻤﺎﺀ ﺒﺼﻔﺘﻪ ﻤﺭﺠﹺﻌ ﹰﺎ ‪ :‬ﺍﻝﺯﻭﺝ ‪: O 2 H 2 O‬‬
‫ﻓﻲ ﻫﺫﺍ ﺍﻝﺯﻭﺝ ﻴﺘﻐﻴ‪‬ﺭ ﺭﻗﻡ ﺃﻜﺴﺩﺓ ﻋﻨﺼﺭ ﺍﻷﻜﺴﺠﻴﻥ ﻤﻥ ‪ −II‬ﻓﻲ ‪ H2O‬ﺇﻝﻰ ‪ 0‬ﻓﻲ‬
‫‪ . O2‬ﻭﻨﺠﺩ ﺃﻴﻀﹰﺎ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪ −II‬ﻝﻸﻜﺴﺠﻴﻥ ﻓﻲ ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻨﻴﻭﻡ ‪ H3O+‬ﻭﻓﻲ‬
‫ﻥ ﺍﻝﺯﻭﺠﻴﻥ ‪ H3O+ /O2‬ﻭ ‪ O2 /OH−‬ﻫﻤﺎ‬
‫ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ‪ ، OH−‬ﻭﻋﻠﻴﻪ ﻓﺈ ‪‬‬
‫ﺘﻌﺒﻴﺭﺍﻥ ﻤﺨﺘﻠﻔﺘﺎﻥ ﻝﻠﺯﻭﺝ ‪. O2 /H2O‬‬
‫ﻭﻝﻜﻨﻨﺎ ﻤﻥ ﻨﺎﺤﻴﺔ ﻋﻤﻠﻴﺔ ﻨﻘﺘﺼﺭ ﻋﻠﻰ ﺍﻝﻜﺘﺎﺒﺔ ‪O2 /H2O‬‬

‫‪4H3O+ + O2 + 4e− ⇌ 6H2O‬‬
‫ﻭﺘﹸﻜﺘﹶﺏ ﻤﻌﺎﺩﻝﺔ ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺔ‪:‬‬
‫‪0.06‬‬ ‫‪P(O2 )[H3O+ ]4‬‬
‫‪E = E 0 (O2 /H2O) +‬‬ ‫‪log‬‬
‫‪4‬‬ ‫‪1‬‬
‫ﻥ‪:‬‬
‫ﻭﻝﻤﺎ ﻜﺎﻥ ‪ E 0 (O2 /H2O) = 1.23 V‬ﻨﺠﺩ ﺃ ‪‬‬
‫) ‪E = 1.23 − 0.06 pH + 0.015 log P(O2‬‬
‫ﻥ ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ﺒﻴﻥ ‪O2‬‬
‫ﻓﺈﺫﺍ ﺭﺴﻤﻨﺎ ﻫﺫﺍ ﺍﻝﻤﺨﻁﻁ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ‪ ، P(O2 ) = 1bar‬ﻓﺈ ‪‬‬
‫ﻭ ‪ H2O‬ﻴﻘﺒل ﺍﻝﻤﻌﺎﺩﻝﺔ‪:‬‬
‫‪E2 = 1.23 − 0.06 pH‬‬
‫ﻴ‪‬ﻅﻬﹺﺭ ﺍﻝﺸﻜل )‪ (1‬ﺭﺴﻡ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ )‪ E1 = f (pH‬ﻭ )‪ ، E2 = f (pH‬ﻭﻨﻼﺤﻅ ﻭﺠﻭﺩ ﺜﻼﺙ‬
‫ﻤﻨﺎﻁﻕ ﺴﻨﻘﻭﻡ ﺒﺩﺭﺍﺴﺘﻬﺎ‪.‬‬
‫)‪E (V‬‬
‫ﺍﻝﻤﺎﺀ ﻤ‪‬ﺭﺠﻊ ‪O2‬‬

‫‪1.0‬‬
‫‪0.5‬‬ ‫ﺍﻝﻤﺎﺀ ﻤ‪‬ﺴﺘﻘﺭ‬

‫‪H2O‬‬
‫‪pH‬‬
‫‪0‬‬
‫‪7‬‬ ‫‪14‬‬
‫‪−0.5‬‬
‫‪H2‬‬
‫ﺍﻝﻤﺎﺀ ﻤ‪‬ﺅﻜﺴﺩ ‪−1.0‬‬
‫ﺍﻝﺸﻜل )‪ (1‬ﺍﻝﻤﻨﺤﻨﻲ ) ‪ E = f ( pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺎﺀ ﻋﻨﺩﻤﺎ‬

‫‪P ( H2 ) = P ( O2 ) = 1.0 bar‬‬
‫‪ .2.I‬ﺍﺳﺘﺜﻤﺎﺭ ﺍﳌﺨﻄﻂ )‪ E = f (pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﻤﺎﺀ‪:‬‬
‫♦ ﻴﻜﻭﻥ ﺍﻝﻤﺎﺀ ﻤﺴﺘﻘ ‪‬ﺭﹰﺍ )ﻤﻥ ﻨﺎﺤﻴﺔ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ( ﻓﻲ ﺍﻝﻤﻨﻁﻘﺔ ﺍﻝﻭﺍﻗﻌﺔ ﺒﻴﻥ ﺍﻝﻤﺴﺘﻘﻴﻤﻴﻥ‪،‬‬
‫ﻥ ﺃﻱ ﻤﺤﻠﻭل ﺘﻜﻭﻥ ﺍﻝﻨﻘﻁﺔ ﺍﻝﻤﻤﺜﱢﻠﺔ ﻝﻪ )‪ (E , pH‬ﻭﺍﻗﻌﺔ ﻓﻲ ﻫﺫﻩ ﺍﻝﻤﻨﻁﻘﺔ ﻝﻥ‬
‫ﻭﻤﻥ ﹶﺜ ‪‬ﻡ ﻓﺈ ‪‬‬
‫ﻴﺨﻀﻊ ﻝﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﺇﺭﺠﺎﻉ ﻴﺩﺨل ﻓﻴﻪ ﺃﺤﺩ ﺯﻭﺠﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫♦ ﻓﻲ ﺍﻝﻤﻨﻁﻘﺔ ‪ E < −0.06 pH‬ﻴﻜﻭﻥ ﺍﻝﻤﺎﺀ ﻤﺅﻜﺴ‪‬ﺩﺍﹰ؛ ﺃﻱ ﻴﻤﻜﻥ ﺃﻥ ﻴ‪‬ﺭﺠ‪‬ﻊ ﺇﻝﻰ ‪: H2‬‬
‫ﻥ ﺒﻌﺽ ﺍﻝﻤﻌﺎﺩﻥ ﻤﺜل ﺍﻝﺤﺩﻴﺩ ﻭﺍﻷﻝﻤﻨﻴﻭﻡ ﻭﺍﻝﺼﻭﺩﻴﻭﻡ ﺘﹸﺭﺠﹺﻊ ﺍﻝﻤﺎﺀ‪ .‬ﻭﻤﻥ‬
‫ﻭﻝﻬﺫﺍ ﻨﺠﺩ ﺃ ‪‬‬
‫ﺍﻝﺴﻬل ﺍﻝﺘﺤﻘﻕ ﻤﻥ ﺫﻝﻙ‪:‬‬
‫‪ -‬ﻴﺘﻔﺎﻋل ﺍﻝﺘﻭﺘﻴﺎﺀ ﻤﻊ ﺍﻝﻤﺎﺀ ﻓﻲ ﻭﺴﻁ ﺤﻤﻀﻲ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ‪:‬‬
‫‪Zn + 2H 3O+ → Zn2+ + H2 + 2H2O‬‬
‫‪ -‬ﻴﺘﻔﺎﻋل ﺍﻝﺼﻭﺩﻴﻭﻡ ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪2Na + 2H2O → 2Na + + OH− + H2‬‬
‫♦ ﻓﻲ ﺍﻝﻤﻨﻁﻘﺔ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝـ ‪ E 2 > 1.23 − 0.06 pH‬ﻴﻜﻭﻥ ﺍﻝﻤﺎﺀ ﻤ‪‬ﺭﺠﻌﺎﹰ‪ ،‬ﺃﻱ ﺇﻨﹼﻪ‬
‫ﻴﻤﻜﻥ ﺃﻜﺴﺩﺓ ﺍﻝﻤﺎﺀ ﺇﻝﻰ ﺃﻜﺴﺠﻴﻥ‪ ،‬ﻭﻨﺫﻜﺭ ﺃﻤﺜﻠﺔ ﻋﻥ ﻤﺅﻜﺴﺩﺍﺕ ﺍﻝﻤﺎﺀ ﺜﻨﺎﺌﻲ ﺍﻝﻜﻠﻭﺭ ‪Cl2‬‬
‫‪ Mn O−‬ﻭﺸﺎﺭﺩﺓ ﺍﻝﺒﻴﻜﺭﻭﻤﺎﺕ‬
‫ﻭﺍﻝﻤﺎﺀ ﺍﻷﻜﺴﺠﻴﻨﻲ ‪ H2O2‬ﻭﺸﺎﺭﺩﺓ ﺍﻝﺒﺭﻤﻨﻐﻨﺎﺕ ‪4‬‬
‫‪ Cr2 O27−‬ﻭﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺒﻭﻜﻠﻭﺭﻴﺕ ‪ Cl O−‬ﻭﺸﺎﺭﺩﺓ ﺍﻝﺒﻴﺭﻭﻜﺴﻲ ﺜﻨﺎﺌﻲ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ‬

‫ﻻ‬
‫ﻥ ﻤﻌﻅﻡ ﻫﺫﻩ ﺍﻝﺘﻔﺎﻋﻼﺕ ﺒﻁﻴﺌﺔ ﺠﺩﹰﺍ‪ .‬ﻭﻝﺫﻝﻙ ﺇﺫﺍ ﺤﻔﻅﻨﺎ ﻤﺩﺓ ﻁﻭﻴﻠﺔ ﻤﺤﻠﻭ ﹰ‬
‫ﻻﺃ‪‬‬
‫‪ ، S2 O28−‬ﺇ ﹼ‬
‫ﻤﻥ ﺒﺭﻤﻨﻐﻨﺎﺕ ﺍﻝﺒﻭﺘﺎﺴﻴﻭﻡ‪ ،‬ﻨﺠﺩ ﺃﻥ‪ ‬ﺍﻝﻤﺤﻠﻭل ﻻ ﻴﻌﻭﺩ ﺭﺍﺌﻘﹰﺎ ﻭﺘﻅﻬﺭ ﻓﻴﻪ ﻤﻌﻠﹼﻘﺎﺕ ﻤﻥ ﺜﻨﺎﺌﻲ‬
‫ﺃﻜﺴﻴﺩ ﺍﻝﻤﻨﻐﻨﻴﺯ ‪ Mn O2‬ﻭﺫﻝﻙ ﻷﻨﻪ ﺘﻔﺎﻋل ﻤﻊ ﺍﻝﻤﺎﺀ ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ‪:‬‬
‫‪4 MnO−‬‬
‫‪4 + 2 H2O → 4 MnO2 + 3 O2 + 4 OH‬‬
‫‪−‬‬
‫‪ .II‬ﻤﺨﻁﻁ ﻜﻤﻭﻥ‪ pH -‬ﻝﻠﺤﺩﻴﺩ‬
‫‪ .1.II‬ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ‬
‫ﺴﻨﻘﺘﺼﺭﻋﻠﻰ ﺩﺭﺍﺴﺔ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ‪ III ، II ، 0‬ﻝﻠﺤﺩﻴﺩ ﺘﺤﺕ ﺍﻷﺸﻜﺎل ﺍﻵﺘﻴﺔ‪:‬‬

‫‪Fe, Fe2+, Fe3+, Fe(OH)2 , Fe(OH)3‬‬
‫ﻤﻥ ﺠﻬﺔ ﺜﺎﻨﻴﺔ ﺘﻌﻁﻴﻨﺎ ﺍﻝﺠﺩﺍﻭل ﺍﻝﻘﻴﻡ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫‪pKs (Fe(OH)2 ) = pKs = 15.1‬‬
‫‪pKs (Fe(OH)3 ) = pKs′ = 38.0‬‬
‫‪E 0 (Fe2+ / Fe) = −0.44 V‬‬
‫‪E 0 (Fe3+ / Fe2+ ) = 0.77 V‬‬
‫ﻓﻲ ﺤﺎﻝﺔ ﺘﺭﻜﻴﺯ ﻜﻠﹼﻲ ﻝﻌﻨﺼﺭ ﺍﻝﺤﺩﻴﺩ‬ ‫)‪E = f (pH‬‬ ‫ﻭﺴﻨﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ‬
‫‪ .C 0 = 10−2 mol/ L‬ﻭﻤﻥ ﺍﻝﻤﻔﻴﺩ ﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ ﺘﺩﺭﻴﺠﻴﹰﺎ ﺒﺼﻭﺭﺓ ﻤﺘﺭﺍﻓﻘﺔ ﻤﻊ ﺇﻴﺠﺎﺩ‬
‫ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺤﺩﻴﺔ‪.‬‬
‫ﻗﻴﻤﺔ ‪ pH‬ﻋﻨﺩ ﻅﻬﻭﺭ ﺭﺍﺴﺏ‪:‬‬ ‫‪.a‬‬
‫ ﻴﺘﻜﻭ‪‬ﻥ ‪ Fe(OH)2‬ﻋﻨﺩﻤﺎ ‪ [Fe2 + ][OH− ]2 ≥ Ks‬ﺃﻱ ﻋﻨﺩﻤﺎ‬
‫‪Ks‬‬
‫≥ ] ‪[OH−‬‬
‫] ‪[Fe2 +‬‬
‫ﻭﻤﻊ ‪ [Fe2 + ] =C 0 = 10−2 mol/L‬ﻨﺠﺩ ﺃ ‪‬‬
‫ﻥ ‪[OH− ] ≥ 3 × 10−7 mol/ L‬‬
‫‪pH1 ≥ 7.45‬‬
‫ ﻴﺘﻜﻭ‪‬ﻥ ‪ Fe(OH)3‬ﻋﻨﺩﻤﺎ ‪  [Fe2+ ]  [OH− ]3 ≥ Ks′‬ﺃﻱ ﻋﻨﺩﻤﺎ‬
‫‪‬‬ ‫‪‬‬
‫‪ OH−  ≥ 3 Ks′‬‬
‫‪‬‬ ‫‪‬‬
‫] ‪[Fe2+‬‬
‫ﻥ ‪[OH− ] ≥ 3 × 10−12 mol/ L‬‬
‫ﻭﻤﻊ ‪ [Fe3 + ] =C 0 = 10−2 mol/L‬ﻨﺠﺩ ﺃ ‪‬‬
‫‪pH2 ≥ 2‬‬
‫ﻭﺘﺤﺩ‪‬ﺩ ﺍﻝﻘﻴﻤﺘﺎﻥ ‪ pH1‬ﻭ ‪ pH2‬ﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺍﻝﺭﺍﺴﺒﻴﻥ ‪ Fe(OH)2‬ﻭ ‪، Fe(OH)3‬‬
‫ﻭﺫﻝﻙ ﻜﻤﺎ ﻴﺘﹼﻀﺢ ﻤﻥ ﺍﻝﺸﻜل ))‪. (2 − (a‬‬
‫ﺩﺭﺍﺴﺔ ﺍﻝﻤﻨﺎﻁﻕ ﺍﻝﺤﺩﻴﺔ )‪E = f (pH‬‬ ‫‪.b‬‬

‫ﺘﺴﻤﺢ ﻗﻴﻡ ‪ pH‬ﺍﻝﺘﻲ ﺤﺼﻠﻨﺎ ﻋﻠﻴﻬﺎ ﺴﺎﺒﻘﹰﺎ ﺒﺎﻝﻭﺼﻭل ﺇﻝﻰ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺘﺎﻝﻲ‪.‬‬
‫‪pH‬‬ ‫‪2.0‬‬ ‫‪7.45‬‬

‫ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪III‬‬ ‫‪Fe3 +‬‬ ‫‪Fe(OH)3‬‬
‫ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪II‬‬ ‫‪Fe2+‬‬ ‫‪Fe(OH)2‬‬
‫ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪0‬‬ ‫‪Fe‬‬
‫ﻤﻥ ﺍﻝﺠﺩﻭل ﺍﻝﺴﺎﺒﻕ ﻨﻼﺤﻅ ﻅﻬﻭﺭ ﺍﻝﻤﻨﺎﻁﻕ ﺍﻝﺤﺩﻴﺔ ﺍﻝﺘﺎﻝﻴﺔ ﺍﻝﺘﻲ ﻴﻠﺯﻡ ﺇﻴﺠﺎﺩ ﺍﻝﻤﻌﺎﺩﻝﺔ‬
‫ل ﻤﻨﻬﺎ‪:‬‬
‫)‪ E = f (pH‬ﻝﻜ ّ‬
‫• ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe3+ / Fe2+‬ﻋﻨﺩﻤﺎ ‪pH < 2‬‬
‫• ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe2+ / Fe‬ﻋﻨﺩﻤﺎ ‪pH < 7.45‬‬
‫• ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)3 / Fe2 +‬ﻋﻨﺩﻤﺎ ‪2 < pH < 7.45‬‬
‫• ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)3 / Fe(OH)2‬ﻋﻨﺩﻤﺎ ‪pH > 7.45‬‬
‫• ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)2 / Fe‬ﻋﻨﺩﻤﺎ ‪pH > 7.45‬‬
‫‪ .1.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe3+ / Fe2+‬ﻋﻨﺩﻤﺎ ‪: pH < 2‬‬
‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﻠﺯﻭﺝ ‪ Fe3+ / Fe2+‬ﻭﻜـﺫﻝﻙ ﻤﻌﺎﺩﻝـﺔ ﻨﺭﻨﺴـﺕ‬

‫ﺍﻝﻤﻭﺍﻓﻘﺔ‪:‬‬
‫‪Fe3+ + e− ⇌ Fe2 +‬‬
‫] ‪[Fe3 +‬‬
‫‪E = E 0 (Fe3+ / Fe2+ ) + 0.06 log‬‬
‫] ‪[Fe2 +‬‬
‫ﻨﻼﺤﻅ ﺃﻨﻪ ﻋﻨﺩ ﺍﻝﻤﻨﻁﻘﺔ ﺍﻝﺤﺩﻴﺔ ﻴﻜﻭﻥ ] ‪ [Fe3 + ] = [Fe2 +‬ﻭﻤﻨﻪ‪ ،‬ﺍﻝﺸﻜل ))‪: (2 − (b‬‬
‫‪. E1 = 0.77 V‬‬

‫)‪(a‬‬
‫)‪E (V‬‬
‫‪3+‬‬
‫‪1 Fe Fe(OH)3‬‬
‫‪2+‬‬
‫‪Fe‬‬ ‫‪Fe(OH)2‬‬
‫‪7‬‬ ‫‪14‬‬
‫‪0‬‬ ‫‪pH 2‬‬ ‫‪pH 1‬‬ ‫‪pH‬‬
‫)‪(b‬‬
‫)‪E (V‬‬
‫‪3+‬‬
‫‪1 Fe Fe(OH)3‬‬
‫‪E1‬‬
‫‪2+‬‬
‫‪Fe‬‬ ‫‪Fe(OH)2‬‬
‫‪7‬‬ ‫‪14‬‬
‫‪0‬‬ ‫‪pH 2‬‬ ‫‪pH 1‬‬ ‫‪pH‬‬
‫ﺍﻝﺸﻜل )‪ (2‬ﺍﻝﺭﺴﻡ ﺍﻝﻤﺘﺩﺭﺝ ﻝﻠﻤﺨﻁﹼﻁ ) ‪. E = f ( pH‬‬

‫)‪ (a‬ﺍﻝﺤﺩﻭﺩ ‪ Fe3+/ Fe ( OH )3‬ﻭ ‪Fe / Fe ( OH )2‬‬
‫‪2+‬‬
‫)‪ (b‬ﺍﻝﺤﺩﻭﺩ ‪Fe3+/ Fe2+‬‬
‫‪ .2.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe2+ / Fe‬ﻋﻨﺩﻤﺎ ‪: pH < 7.45‬‬

‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﻠﺯﻭﺝ ‪ Fe2+ / Fe‬ﻭﻤﻌﺎﺩﻝﺔ ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺔ‪:‬‬
‫‪Fe2+ + 2 e− ⇌ Fe‬‬
‫] ‪E = E 0 (Fe2+ / Fe) + 0.03 log[Fe2 +‬‬

‫ﻥ‪:‬‬
‫‪ [Fe2 + ] = C 0 = 10−2 mol/L‬ﻭﻤﻨﻪ ﻨﺠﺩ ﺃ ‪‬‬ ‫ﻭﻋﻨﺩ ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ﻨﻜﺘﺏ‬
‫‪E2 = −0.50 V‬‬
‫ﻻﺤﻅ ﺍﻝﺸﻜل ))‪. (2 − (c‬‬
‫‪ .3.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)3 / Fe2 +‬ﻋﻨﺩﻤﺎ ‪: 2 < pH < 7.45‬‬

‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﻠﺯﻭﺝ ‪ Fe(OH)3 / Fe+2‬ﻭﻜﺫﻝﻙ ﻤﻌﺎﺩﻝﺔ ﻨﺭﻨﺴﺕ‬
‫‪Fe(OH)3 + e− + 3 H3O+ ⇌ Fe2 + + 6 H2O‬‬
‫‪[H3O+ ]3‬‬
‫‪E 3 = E 0 (Fe(OH)3 / Fe2+ )) + 0.06 log‬‬
‫] ‪[Fe2+‬‬
‫) ‪(I‬‬ ‫] ‪E 3 = E 0 (Fe(OH)3 / Fe2 + ) − 0.18 pH − 0.06 log[Fe2 +‬‬
‫ﻴﻠﺯﻤﻨﺎ ﺤﺴﺎﺏ ) ‪: E 0 (Fe(OH)3 / Fe2 +‬‬

‫ل ﻤﻥ ‪ Fe(OH)3‬ﻭ ‪ Fe3 +‬ﻭ ‪ Fe2 +‬ﻤﺘﻭﺍﺯﻨﺔ ﺒﻌﻀﻬﺎ ﻤﻊ ﺒﻌﺽ‬
‫ﻋﻨﺩﻤﺎ ﺘﻜﻭﻥ ﻜ ّ‬
‫ﻴﻜﻭﻥ‪:‬‬
‫) ‪E (Fe(OH)3 / Fe2 + ) = E (Fe3 + / Fe2+‬‬
‫ﺒﺎﻝﺘﻌﻭﻴﺽ ﺒﺎﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ﻨﺠﺩ‪:‬‬
‫‪h3‬‬
‫‪E 0 (Fe(OH)3 /Fe2 + ) + 0.06 log‬‬
‫] ‪[Fe2 +‬‬
‫] ‪[Fe3+‬‬
‫‪= E 0 (Fe3 + /Fe2+ ) + 0.06 log‬‬
‫] ‪[Fe2+‬‬
‫ﻭﻤﻨﻪ ﻨﺠﺩ‬
‫] ‪[Fe3 +‬‬ ‫] ‪[Fe2 +‬‬
‫‪E 0 (Fe(OH)3 / Fe2 + ) = 0.77 + 0.06 log‬‬ ‫‪+ 0.06 log‬‬
‫] ‪[Fe2 +‬‬ ‫‪h3‬‬
‫] ‪[Fe3 +‬‬
‫‪= 0.77 + 0.06 log‬‬
‫‪h3‬‬
‫‪Ks′‬‬
‫‪= 0.77 + 0.06 log‬‬
‫‪Ke 3‬‬
287 pH -‫ﺭﺳﻢ ﺍﳌﺨﻄﻄﺎﺕ ﻛﻤﻮﻥ‬
(c)
E (V)
1 Fe3 + Fe(OH)3
2+
Fe Fe(OH)2
7 14
0 pH 2 pH 1 pH
E2
(d)
E (V)
1 Fe3 + Fe(OH)3
E3
2+
Fe 7 14
0 pH 2 pH 1 pH
Fe(OH)2
Fe
. E = f ( pH ) ‫( ﺍﻝﺭﺴﻡ ﺍﻝﻤﺘﺩﺭﺝ ﻝﻠﻤﺨﻁﹼﻁ‬2) ‫ﺍﻝﺸﻜل‬

Fe2+/ Fe ‫( ﺍﻝﺤﺩﻭﺩ‬c)
Fe(OH)3 / Fe2+ ‫( ﺍﻝﺤﺩﻭﺩ‬d)
E 0 (Fe(OH)3 / Fe2 + ) = 0.77 − 0.06 pks + 0.18 pke
E 0 (Fe(OH)3 / Fe2 + ) = 1.01 V
‫ﺍﻟﻔﺼﻞ ﺍﻟﺘﺎﺳﻊ‬ 288
،‫ ﺒﻘﻴﻤﺘﻬﺎ ﻨﺠﺩ‬E 0 (Fe(OH)3 / Fe2 + ) ‫( ﻭﺘﻌﻭﻴﺽ‬I ) ‫ﺒﺎﻝﻌﻭﺩﺓ ﺇﻝﻰ ﺍﻝﻤﻌﺎﺩﻝﺔ‬

: (2 − (d)) ‫ﺍﻝﺸﻜل‬
E 3 = 1.01 + 0.06 × 2 − 0.18 pH = 1.13 − 0.18 pH
. E 3 (7.45) = −0.21 V ‫ﻥ‬
 ‫ ﻨﺠﺩ ﺃ‬pH = 7.45 ‫ﻭﻋﻨﺩﻤﺎ‬
pH > 7.45 : ‫ ﻋﻨﺩﻤﺎ‬Fe(OH)3 / Fe(OH)2 ‫ ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل‬.4.1.II
‫ ﻭﻜﺫﻝﻙ ﻤﻌﺎﺩﻝﺔ‬Fe(OH)3 / Fe(OH)2 ‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﻠﺯﻭﺝ‬

:‫ﻨﺭﻨﺴﺕ ﺍﻝﻤﻭﺍﻓﻘﺔ‬
Fe(OH)3 + 3 H 3O+ + e− ⇌ Fe(OH)2 + 2 H2O
E = E 0 (Fe(OH)3 / Fe(OH)2 ) + 0.06 log[H3O+ ]
E 4 = E 0 (Fe(OH)3 / Fe(OH)2 ) − 0.06 pH
: E 0 (Fe(OH)3 / Fe(OH)2 ) ‫ﻴﻠﺯﻤﻨﺎ ﺤﺴﺎﺏ‬
‫ ﻓﻨﺠﺩ‬، Fe(OH)3 / Fe(OH)2 ‫ ﻓﻲ ﺘﻭﺍﺯﻥ ﻤﻊ ﺍﻝﺯﻭﺝ‬Fe3+ /Fe2 + ‫ﻥ ﺍﻝﺯﻭﺝ‬

 ‫ﻝﻨﻔﺘﺭﺽ ﺃ‬
‫ﻥ‬
‫ﺃ‬
[Fe3 + ]
E (Fe3 + /Fe2+ ) + 0.06 log =
[Fe2 + ]
E (Fe(OH)3 /Fe(OH)2 ) + 0.06 log[H 3O+ ]
0 0 3+ 2+ [Fe3 + ]
E (Fe(OH)3 / Fe(OH)2 ) = E (Fe / Fe ) + 0.06 log
[Fe2 + ][H 3O+ ]
[Fe3 + ][OH - ]3 Ks′
=
[Fe2 + ][OH - ]2[OH - ][H3O+ ] K s Ke
Ks′
E 0 (Fe(OH)3 /Fe(OH)2 ) = E 0 (Fe3 + /Fe2 + ) + 0.06 log
Ks Ke
10−38
= 0.77 + 0.06 log
10−15.1 × 10−14
= 0.24 V
‫ﻥ‪:‬‬
‫‪E 4 = 0.24 − 0.06 pH‬‬
‫ﺍﻝﺸﻜل ))‪. (2 − (e‬‬ ‫ﻻﺤﻅ‬
‫ﻥ ‪. E 4 (14) = −0.60 V‬‬
‫ﻭﻴﻤﻜﻥ ﺃﻥ ﻨﺤﺴﺏ ﺍﻝﻘﻴﻤﺔ ‪ E 4‬ﻋﻨﺩ ‪ pH = 14‬ﻓﻨﺠﺩ ﺃ ‪‬‬
‫‪ .5.1.II‬ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ‪ Fe(OH)2 /Fe‬ﻋﻨﺩﻤﺎ ‪: pH > 7.45‬‬
‫ﻝﻨﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻨﺼﻑ ﺍﻹﻝﻜﺘﺭﻭﻨﻴﺔ ﻝﻠﺯﻭﺝ ‪ Fe(OH)2 / Fe‬ﻭﻜﺫﻝﻙ ﻤﻌﺎﺩﻝﺔ ﻨﺭﻨﺴﺕ‬

‫‪Fe(OH)2 + 2e− + 2 H 3O+ ⇌ Fe + 4H2O‬‬
‫‪E = E 0 (Fe(OH)2 / Fe) + 0.03 log[H 3O+ ]2‬‬
‫‪E 5 = E 0 (Fe(OH)2 / Fe) − 0.06 pH‬‬
‫ﻴﻠﺯﻤﻨﺎ ﺤﺴﺎﺏ )‪: E 0 (Fe(OH)2 / Fe‬‬
‫ﻥ ﺍﻝﻤﻨﺤﻨﻴﻴﻥ‬
‫ﻴﻤﻜﻥ ﺍﺴﺘﺜﻤﺎﺭ ﺘﻭﺍﺯﻥ ﺯﻭﺠﻴﻥ ‪ Ox/Red‬ﻜﻤﺎ ﻓﻌﻠﻨﺎ ﺴﺎﺒﻘﺎﹰ‪ ،‬ﺃﻭ ﺃﻥ ﻨﻘﻭل ﺇ ‪‬‬
‫)‪ E2 = f (pH‬ﻭ )‪ E 5 = g (pH‬ﻴﺘﻘﺎﻁﻌﺎﻥ ﻋﻨﺩ ‪ pH = 7.45‬ﺒﺎﻝﻘﻴﻤﺔ‬
‫‪E = −0.50 V‬‬
‫ﻥ‪:‬‬
‫ﻭﻤﻨﻪ ﻨﺠﺩ ﺒﺎﻝﺘﻌﻭﻴﺽ ﻓﻲ ﻤﻌﺎﺩﻝﺔ ‪ E 5‬ﺃ ‪‬‬
‫‪−0.5 = E 0 (Fe(OH)2 / Fe) − 0.06 × 7.45‬‬
‫‪E 0 (Fe(OH)2 / Fe) = −0.05 V‬‬
‫ﻻﺤﻅ ﺍﻝﺸﻜل ))‪. (2 − (f‬‬
‫ﻭﺘﺼﺒﺢ ﺍﻝﻤﻌﺎﺩﻝﺔ ﻜﻤﺎ ﻴﻠﻲ ‪:‬‬
‫‪E 5 = −0.05 − 0.06 pH‬‬
‫ﻭﻋﻨﺩ ‪ pH = 14‬ﻨﺠﺩ ﺃ ‪‬‬

‫ﻥ ‪. E 5 (14) = −0.89 V‬‬
‫)‪(e‬‬
‫)‪E (V‬‬
‫‪1 Fe3 +‬‬ ‫‪Fe(OH)3‬‬
‫‪2+‬‬
‫‪Fe‬‬ ‫‪7‬‬ ‫‪14‬‬
‫‪0‬‬ ‫‪pH 2‬‬ ‫‪pH 1‬‬ ‫‪pH‬‬
‫‪E4‬‬
‫‪Fe‬‬ ‫‪Fe(OH)2‬‬
‫)‪(f‬‬
‫)‪E (V‬‬
‫‪1 Fe3 +‬‬ ‫‪Fe(OH)3‬‬
‫‪2+‬‬
‫‪Fe‬‬ ‫‪7‬‬ ‫‪14‬‬
‫‪0‬‬ ‫‪pH 2‬‬ ‫‪pH1‬‬ ‫‪pH‬‬
‫‪Fe(OH)2‬‬
‫‪Fe‬‬ ‫‪E5‬‬
‫ﺍﻝﺸﻜل )‪ (2‬ﺍﻝﺭﺴﻡ ﺍﻝﻤﺘﺩﺭﺝ ﻝﻠﻤﺨﻁﹼﻁ ) ‪. E = f ( pH‬‬
‫)‪ (e‬ﺍﻝﺤﺩﻭﺩ ‪Fe(OH)3 / Fe(OH)2‬‬
‫)‪ (f‬ﺍﻝﺤﺩﻭﺩ ‪Fe(OH)2 / Fe‬‬
‫‪ .2.II‬ﺍﺴﺘﺜﻤﺎﺭ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻓﻲ ﺤﺎﻝﺔ ﺍﻝﺤﺩﻴﺩ‬
‫‪ .1.2.II‬ﺍﺴﺘﻘﺭﺍﺭ ﻤﺨﺘﻠﻑ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ‪:‬‬
‫ﻝﻤ‪‬ﺎ ﻜﺎﻥ ﻝﻜل ﻤﻥ ‪ Fe(OH)3 ، Fe(OH)2 ، Fe3 + ، Fe2 + ، Fe‬ﻤﻨﻁﻘﺔ ﻭﺠﻭﺩ ﺃﻭ‬
‫ﺭﺠﺤﺎﻥ ﺨﺎﺼﺔ ﻨﺴﺘﻨﺘﺞ ﺍﻝﻨﻘﺎﻁ ﺍﻝﺘﺎﻝﻴﺔ ‪:‬‬
‫‪ .1‬ﻴﻤﻜﻥ ﺍﻋﺘﺒﺎﺭ ﻜل ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ﻭﺍﻝﺠﺯﻴﺌﺎﺕ ﺍﻝﺴﺎﺒﻘﺔ ﻤﺴﺘﻘﺭﺓ ﻭﺒﺎﻝﺘﺎﻝﻲ ﻻ ﻴﺨﻀﻊ ‪Fe2 +‬‬
‫ﺃﻭ ‪ Fe(OH)2‬ﺇﻝﻰ ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﺫﺍﺘﻲ‪.‬‬
‫‪ .2‬ﻴﺨﻀﻊ ﺍﻝﺤﺩﻴﺩ ﺒﺩﺭﺠﺘﻲ ﺍﻷﻜﺴﺩﺓ ‪ 0‬ﻭ ‪ ، 3‬ﻭﻓﻕ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺘﺎﻝﻴﺔ‪ ،‬ﺇﻝﻰ ﺘﻔﺎﻋل ﺃﻜﺴـﺩﺓ‬
‫ﻭﺇﺭﺠﺎﻉ ﺫﺍﺘﻲ ﺭﺠﻌﻲ )‪:1(retrodismutation‬‬
‫ﻋﻨﺩﻤﺎ ‪pH < 2‬‬

‫‪2Fe3 + + Fe → 3Fe2 +‬‬
‫ﻋﻨﺩﻤﺎ ‪2 < pH < 7.45‬‬
‫‪Fe + 2 Fe(OH)3 + 6 H 3O+ ⇌ 3 Fe2+ + 12 H2O‬‬
‫ﻋﻨﺩﻤﺎ ‪pH > 7.45‬‬
‫‪2Fe(OH)3 + Fe → 3Fe(OH) 2‬‬
‫‪ .2.2.II‬ﺍﻻﺴﺘﻘﺭﺍﺭ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ‪:‬‬
‫ﺇﺫﺍ ﺭﺴﻤﻨﺎ ﻓﻭﻕ ﺍﻝﻤﺨﻁﻁ ﺍﻝﺴﺎﺒﻕ ﻤﺨﻁﻁ )‪ E = f (pH‬ﻝﻠﻤﺎﺀ‪ ،‬ﺍﻝﺸﻜل )‪ ، (3‬ﻨﺠﺩ ﺃ ‪‬‬
‫ﻥ‪:‬‬
‫ﻕ ﻭﺠﻭﺩ ﻭﺍﻗﻌﺔ ﺘﻤﺎﻤﹰﺎ ﻓﻲ ﺍﻝﻤﻨﻁﻘﺔ ﺍﻝﺘﻲ ﻴﻜﻭﻥ ﻓﻴﻬﺎ ﺍﻝﻤﺎﺀ‬
‫• ﻝﻠﺤﺩﻴﺩ ﺒﺼﻔﺘﻪ ﻤﻌﺩﻨﹰﺎ ﻤﻨﺎﻁ ﹸ‬
‫ﻤﺅﻜﺴﺩﹰﺍ‪ ،‬ﻭﻫﺫﺍ ﻴﻌﻨﻲ ﺃﻥ ﻗﻁﻌﺔ ﻤﻥ ﺍﻝﺤﺩﻴﺩ ﻤﻐﻤﻭﺴﺔ ﻓﻲ ﺍﻝﻤﺎﺀ ﺴﻭﻑ ﺘﺘﺄﻜﺴﺩ‪ .‬ﻭﺴﺘﺘﺒﻊ‬
‫ﻁﺒﻴﻌﺔ ﻨﻭﺍﺘﺞ ﺍﻷﻜﺴﺩﺓ ‪ pH‬ﺍﻝﻭﺴﻁ ﻭﻜﻤﻴﺔ ‪ O2‬ﺍﻝﻤﻨﺤﻠﺔ ﻓﻲ ﺍﻝﻤﺎﺀ‪.‬‬
‫• ﻴﻜﻭﻥ ﻝﻜل ﻤﻥ ﺍﻝﺸﻭﺍﺭﺩ ‪ Fe3 +‬ﻭ ‪ Fe2 +‬ﻭﻜﺫﻝﻙ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩﺍﺕ ‪Fe(OH)2‬‬
‫ﻭ ‪ Fe(OH)3‬ﻤﻨﺎﻁﻕ ﺍﺴﺘﻘﺭﺍﺭ ﺘﻐﻁﻲ ﺠﺯﺌﻴ ﹰﺎ ﻤﻨﺎﻁﻕ ﺍﺴﺘﻘﺭﺍﺭ ﺍﻝﻤﺎﺀ ‪ . H2O‬ﻭﺒﺫﻝﻙ‬
‫ﻥ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﺍﻝﻨﺎﺠﻤﺔ ﻋﻥ ﺍﻨﺤﻼل ﺃﻤﻼﺡ ﺍﻝﺤﺩﻴﺩ ﺍﻝﺜﻨﺎﺌﻲ ﻭﺍﻝﺜﻼﺜﻲ ﻓﻲ ﺍﻝﻤﺎﺀ‬
‫ﻓﺈ ‪‬‬
‫ﺍﻝﻨﻘﻲ ﻴﻤﻜﻥ ﺃﻥ ﺘﻜﻭﻥ ﻤﺴﺘﻘﺭﺓ‪ .‬ﻓﻲ ﺤﻴﻥ ﺃﻥ ﻭﺠﻭﺩ ﺒﻌﺽ ﺍﻷﻜﺴﺠﻴﻥ ﺍﻝﻤﻨﺤل ﻓﻲ‬
‫ﺍﻝﻤﺎﺀ‪ ،‬ﻴﺅﺩﻱ ﺇﻝﻰ ﺃﻜﺴﺩﺓ ﺍﻝﺤﺩﻴﺩ ﺍﻝﺜﻨﺎﺌﻲ ﺇﻝﻰ ﺤﺩﻴﺩ ﺜﻼﺜﻲ ﺃﻭ ﺇﻝﻰ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ‬
‫ﺍﻝﺤﺩﻴﺩ ‪ III‬ﺘﺒﻌﹰﺎ ﻝﻘﻴﻤﺔ ‪ pH‬ﺍﻝﻤﺤﻠﻭل‪.‬‬
‫ﺘﻔﺎﻋل ﺃﻜﺴﺩﺓ ﻭﺇﺭﺠﺎﻉ ﺫﺍﺘﻲ ﺭﺠﻌﻲ )‪ retrodismutation‬ﺃﻭ ‪ (comproportionation‬ﻫﻭ ﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ ﻴﺘﻔﺎﻋل‬ ‫‪1‬‬
‫ﺒﻤﻭﺠﺒﻪ ﻤﺭﻜﺒﺎﻥ ﻴﻀﻤﺎﻥ ﺍﻝﻌﻨﺼﺭ ﻨﻔﺴﻪ ﻭﻝﻜﻥ ﺒﺭﻗﻤﻲ ﺃﻜﺴﺩﺓ ﻤﺨﺘﻠﻔﻴﻥ ﻭﻴﺸﻜﹼﻼﻥ ﻨﺎﺘﺠﹰﺎ ﻴﻀﻡ ﺍﻝﻌﻨﺼﺭ ﺒﺭﻗﻡ ﺃﻜﺴﺩﺓ ﺒﻴﻥ ﺍﻝﺭﻗﻤﻴﻥ‬
‫ﺍﻝﺴﺎﺒﻘﻴﻥ‪ ،‬ﻤﺜﺎل‪:‬‬
‫‪3+‬‬ ‫‪2+‬‬
‫‪2Fe‬‬ ‫‪+ Fe → 3Fe‬‬
‫)‪E (V‬‬
‫‪3+‬‬
‫‪1‬‬ ‫‪Fe‬‬
‫‪Fe(OH)3‬‬
‫‪2+‬‬
‫‪Fe‬‬
‫‪pH‬‬
‫‪0‬‬
‫‪Fe(OH)2‬‬
‫‪Fe‬‬
‫‪−1‬‬
‫ﺍﻝﺸﻜل )‪ : (3‬ﻤﺨﻁﻁ )‪ E = f (pH‬ﻝﻠﻤﺎﺀ ﻭﺍﻝﺤﺩﻴﺩ‪.‬‬
‫‬
‫ﻤﺨﻁﻁ )‪ E = f (pH‬ﻝﻠﺴﻴﺭﻴﻭﻡ‪:‬‬ ‫‬
‫ﺍﺭﺴﻡ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻝﻌﻨﺼﺭ ﺍﻝﺴﻴﺭﻴﻭﻡ ﻋﻨﺩﻤﺎ ﻴﻜﻭﻥ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﻜﻠﻲ ﻝﻌﻨﺼﺭ‬
‫ﻥ‪:‬‬
‫ﺍﻝﺴﻴﺭﻴﻭﻡ ﻤﺴﺎﻭﻴﹰﺎ ‪ . 10−2 mol/L‬ﻋﻠﻤﹰﺎ ﺃ ‪‬‬
‫‪، E 0 (Ce4+ / Ce3+ ) = 1.74 V ، E 0 (Ce3+ / Ce) = −2.33 V‬‬
‫‪Ce(OH)4 : pK s = 50 ، Ce(OH)3 : pK s = 21‬‬
‫‪1‬‬ ‫‪2‬‬
‫ﻨﻘﺘﺼﺭ ﻓﻲ ﻫﺫﻩ ﺍﻝﺩﺭﺍﺴﺔ ﻋﻠﻰ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ‪ VI ،III ،0‬ﻝﻌﻨﺼﺭ ﺍﻝﺴﻴﺭﻴﻭﻡ ﺒﺎﻷﻨﻭﺍﻉ‬
‫ﺍﻝﺘﺎﻝﻴﺔ‪. Ce ، Ce3+ ، Ce4+ ، Ce(OH)3 ، Ce(OH)4 :‬‬
‫‪ .1‬ﺍﺤﺴﺏ ‪ pH2 ، pH1‬ﺍﻝﻤﻭﺍﻓﻘﻴﻥ ﻝﻅﻬﻭﺭ ﺍﻝﺭﺍﺴﺒﻴﻥ‪.‬‬
‫ﻻ ﺘﻅﻬﺭ ﻓﻴﻪ ﻝﻜل ﺩﺭﺠﺔ ﺃﻜﺴﺩﺓ‬
‫‪ .2‬ﺍﺴﺘﻨﺎﺩﹰﺍ ﺇﻝﻰ ﻗﻴﻤﺘﻲ ‪ pH‬ﺍﻝﻤﺤﺴﻭﺒﺘﻴﻥ ﺴﺎﺒﻘﺎﹰ‪ ،‬ﺍﺭﺴﻡ ﺠﺩﻭ ﹰ‬
‫ﻝﻠﺴﻴﺭﻴﻭﻡ ﻤﻨﺎﻁﻕ ﺍﻝﻭﺠﻭﺩ ﺃﻭ ﺍﻝﺭﺠﺤﺎﻥ ﻝﻸﻨﻭﺍﻉ ﺍﻝﻤﻭﺍﻓﻘﺔ ﻝﻬﺫﻩ ﺍﻝﺩﺭﺠﺔ‪.‬‬
‫ﻼ ﻤﻤﺎ ﻴﻠﻲ ) ‪ ، E (Ce(OH)4 /Ce3+‬ﻭ ) ‪، E (Ce(OH)4 /Ce(OH)3‬‬
‫‪ .3‬ﺍﺤﺴﺏ ﻜ ﹰ‬
‫ﻭ )‪. E (Ce(OH)3 /Ce‬‬
‫‪ .4‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻻﺕ ﺍﻝﺨﻤﺱ ﻝﻠﺤﺩﻭﺩ ﺍﻝﻔﺎﺼﻠﺔ ﺒﻴﻥ ﺃﻨﻭﺍﻉ ﺍﻝﺴﻴﺭﻴﻭﻡ )‪. E = f (pH‬‬
‫ﻗﺭﺍﺀﺓ ﺍﻝﻤﺨﻁﹼﻁ )‪ E = f (pH‬ﻝﻌﻨﺼﺭ ﺍﻝﺯﺌﺒﻕ‪:‬‬ ‫‬
‫ﻴ‪‬ﻅﻬﹺﺭ ﺍﻝﺸﻜل ﺍﻝﻤﺭﺍﻓﻕ ﺍﻝﻤﺨﻁﻁ )‪ E = f (pH‬ﻝﻌﻨﺼﺭ ﺍﻝﺯﺌﺒﻕ ﻋﻨﺩ ﺩﺭﺠـﺔ ﺤـﺭﺍﺭﺓ‬
‫‪ . 25 C‬ﻭﻫﻭ ﻤﺭﺴﻭﻡ ﻭﻓﻘﹰﺎ ﻝﻼﺼﻁﻼﺤﺎﺕ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫ل‬
‫‪ C tra‬ﻤﺤﺴﻭﺒﹰﺎ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ﺫﺭﺍﺕ ﺍﻝﺯﺌﺒﻕ ﺍﻝﻤﻨﺤ ّ‬ ‫• ﻴﺴﺎﻭﻱ ﺍﻝﺘﺭﻜﻴﺯ ﺍﻝﻜﻠﻲ‬
‫‪ 10 mmol.L−1‬ﻭﺫﻝﻙ ﺒﻐﻴﺎﺏ ﺍﻝﻁﻭﺭ ﺍﻝﺼﻠﺏ‪.‬‬
‫• ﻴﻭﺍﻓﻕ ﺍﻝﺤﺩ ﺍﻝﻔﺎﺼل ﺒﻴﻥ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻤﻨﺤﻠﹼﺔ ﹶﺘﺴﺎﻭﻱ ﺍﻝﺘﺭﺍﻜﻴﺯ ﺒﺎﻝﻨﺴﺒﺔ ﺇﻝﻰ ﺫﺭﺍﺕ ﺍﻝﺯﺌﺒﻕ‪.‬‬
‫• ﻝﻡ ﻨﺄﺨﺫ ﻓﻲ ﺍﻝﺤﺴﺒﺎﻥ ﺴﻭﻯ ﺍﻷﻨﻭﺍﻉ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﺔ ﺍﻷﺭﺒﻌﺔ ﺍﻝﺘﺎﻝﻴﺔ‪:‬‬
‫ ﺍﻝﺯﺌﺒﻕ ﺍﻝﻤﻌﺩﻨﻲ ‪) Hg‬ﺴﺎﺌل ﻨﻘﻲ ﺼﺭﻑ(‪.‬‬
‫ ﺃﻜﺴﻴﺩ ﺍﻝﺯﺌﺒﻕ )‪) HgO (II‬ﺠﺴﻡ ﺼﻠﺏ ﻨﻘﻲ(‪.‬‬
‫ ﺸﺎﺭﺩﺓ ﺍﻝﺯﺌﺒﻕ )‪) Hg2 + (II‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل(‪.‬‬
‫ ﺸﺎﺭﺩﺓ ﺍﻝﺯﺌﺒﻕ )‪) Hg22 + (I‬ﻓﻲ ﺍﻝﻤﺤﻠﻭل(‪.‬‬
‫ﻥ ‪(RT /F ) ⋅ ln 10 = 0.06V‬‬
‫• ﺍﻓﺘﺭﻀﻨﺎ ﺃ ‪‬‬
‫)‪E (V‬‬
‫‪1.0‬‬
‫‪A‬‬ ‫‪3‬‬
‫‪D‬‬
‫‪0.9‬‬
‫‪0.8‬‬ ‫‪B‬‬ ‫‪4‬‬

‫‪0.73‬‬
‫‪0.7‬‬
‫‪0.6‬‬
‫‪C‬‬ ‫‪5‬‬
‫‪0.5‬‬
‫‪0.4‬‬ ‫‪pH‬‬
‫‪1‬‬ ‫‪3‬‬ ‫‪5‬‬ ‫‪7‬‬

‫‪0.3‬‬ ‫‪C‬‬
‫‪ .1‬ﺤﺩ‪‬ﺩ ﺍﻝﻨﻭﻉ ﺍﻝﺫﻱ ﺘﻌﻭﺩ ﺇﻝﻴﻪ ﻜل ﻤﻥ ﺍﻝﻤﻨﺎﻁﻕ ‪ . A − B − C − D‬ﻫل ﻴﺘﻌﻠﹼﻕ ﻫﺫﺍ‬

‫ﺒﻤﻨﺎﻁﻕ ﺍﺴﺘﻘﺭﺍﺭ ﺃﻭ ﺭﺠﺤﺎﻥ ﻝﻠﻨﻭﻉ ﺍﻝﻤﺩﺭﻭﺱ ؟‬
‫ﻓﻴﻤﺎ ﻴﻠﻲ ﻨﺭﻤﺯ ﻝﻜل ﻨﻭﻉ ﻜﻴﻤﻴﺎﺌﻲ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﺤﺭﻑ ﺍﻝﻤﻤﺜﱢل ﻝﻤﻨﻁﻘﺘﻪ‪.‬‬
‫‪ .2‬ﺤﺩ‪‬ﺩ ﺒﻤﺴﺎﻋﺩﺓ ﺍﻝﻤﺨﻁﹼﻁ ﺍﻝﻜﻤﻭﻨﻴﻥ ﺍﻝﻤﺭﺠﻌﻴﻴﻥ ‪ E 2 ، E1‬ﺍﻝﻤﻭﺍﻓﻘﻴﻥ ﻝﻠﺯﻭﺠﻴﻥ ‪:‬‬
‫)‪ Hg(II)/Hg(I‬ﻭ )‪. Hg(II)/Hg(0‬‬
‫‪ .3‬ﺍﻜﺘﺏ ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‪‬ﻠﺔ ﻝﻠﺘﻔﺎﻋل ‪ A → D‬ﻭﺤﺩ‪‬ﺩ ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﺍﻝﻤﻭﺍﻓﻕ‪.‬‬
‫‪ .4‬ﻤﺎ ﻫﻭ ﻤﻴل ﻜل ﻤﻥ ﺍﻝﻘﻁﻌﺘﻴﻥ ﺍﻝﻤﺴﺘﻘﻴﻤﺘﻴﻥ ‪ 4‬ﻭ‪ 5‬؟ ﺘﺤﻘﻕ ﻤﻥ ﺍﻝﺘﻁﺎﺒﻕ ﻤﻊ ﺍﻝﻤﺨﻁﹼﻁ‪.‬‬
‫‪ .5‬ﻭﺍﺯﻥ ﻤﻌﺎﺩﻝﺔ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪ ، B = C + D‬ﻭﺍﺤﺴﺏ ﺒﻤﺴﺎﻋﺩﺓ ﺍﻝﻤﺨﻁﹼﻁ ﺜﺎﺒﺕ‬
‫ﺘﻭﺍﺯﻨﻬﺎ‪.‬‬
‫‪ .6‬ﻤﺜﱢل ﺍﻝﻤﺴﺘﻘﻴﻤﻴﻥ ∆ ﻭ ‪ ∆ ′‬ﺍﻝﻤﺤﺩ‪‬ﺩﻴﻥ ﻝﻤﺠﺎل ﺍﺴﺘﻘﺭﺍﺭ ﺍﻝﻤﺎﺀ ﻤﺴﺘﻌﻴﻨﹰﺎ ﺒﺎﻻﺼﻁﻼﺡ‬
‫ ‪. p(H2 ) = p(O2 ) = P‬‬
‫‪ (a‬ﻫل ﻴﺘﺄﺜﹼﺭ ﻤﻌﺩﻥ ﺍﻝﺯﺌﺒﻕ ﺒﺤﻤﺽ ﻗﻭﻱ ﻏﻴﺭ ﻤﺅﻜﺴ‪‬ﺩ ﻤﺜل ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ ﺍﻝﻤﻤﺩ‪‬ﺩ؟‬
‫‪ (b‬ﻫل ﻴﻭﺠﺩ ﻨﻭﻉ ﻜﻴﻤﻴﺎﺌﻲ ﻝﻠﺯﺌﺒﻕ ﻴﺴﺘﻁﻴﻊ ﺃﻜﺴﺩﺓ ﺍﻝﻤﺎﺀ ؟‬
‫‪ (c‬ﻤﺎ ﻫﻲ ﺍﻷﻨﻭﺍﻉ ﺍﻝﺘﻲ ﺘﻘﺒل ﺍﻷﻜﺴﺩﺓ ﺒﺄﻜﺴﺠﻴﻥ ﺍﻝﻬﻭﺍﺀ؟ ﺍﻜﺘﺏ ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ‬
‫ﺍﻝﻤﺘﻭﻗﹼﻌﺔ ﻭﺫﻝﻙ ﻋﻨﺩﻤﺎ ‪. pH = 5‬‬
‫ﻣﻠﺤﻖ‬
‫

‬
‫
‬
‫‪250 C‬‬ ‫ﺜﻭﺍﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ﻝﻸﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻋﻨﺩ‬ ‫‪.I‬‬
‫‪250 C‬‬ ‫‪ .II‬ﻜﻤﻭﻨﺎﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻴﺔ ﻋﻨﺩ‬
‫‪250 C‬‬ ‫‪ .III‬ﺜﻭﺍﺒﺕ ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﺩﺍﺕ ﻋﻨﺩ‬
‫‪250 C‬‬ ‫‪ .IV‬ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻋﻨﺩ‬
‫‪295‬‬
‫ﺍﳌﻠﺤﻖ‬ ‫‪296‬‬
‫‪ .I‬ﺜﻭﺍﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ ﻝﻸﺯﻭﺍﺝ ﺤﻤﺽ‪/‬ﺃﺴﺎﺱ ﻋﻨﺩ ﺍﻝﺩﺭﺠﺔ ‪250 C‬‬
‫‪pK Ai‬‬ ‫ﺍﻝﺼﻴﻐﺔ‬ ‫ﺍﺴﻡ ﺍﻝﺤﻤﺽ‬

‫‪4.3 ، 1.2‬‬ ‫‪H2C2O4‬‬ ‫ﺤﻤﺽ ﺍﻷﻭﻜﺴﺎﻝﻴﻙ‬
‫‪1.3‬‬ ‫‪CHCl2COOH‬‬ ‫ﺤﻤﺽ ﺜﻨﺎﺌﻲ ﻜﻠﻭﺭ ﺍﻝﺨل‬
‫‪1.9‬‬ ‫‪HSO−‬‬
‫‪4‬‬ ‫ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﺤﺎﻤﻀﻴﺔ‬
‫‪7.6 ، 2.0‬‬ ‫‪SO2‬‬ ‫ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺒﺭﻴﺕ‬
‫‪10.3 ، 6.2 ، 2.8 ، 2.0‬‬ ‫‪H 4Y‬‬ ‫‪E.D.T.A.‬‬
‫‪12.1 ، 7.2 ، 2.15‬‬ ‫‪H 3 PO4‬‬ ‫ﺤﻤﺽ ﺍﻝﻔﻭﺴﻔﻭﺭ‬
‫‪11.5 ، 7.0 ، 2.19‬‬ ‫‪H 3 AsO4‬‬ ‫ﺤﻤﺽ ﺍﻝﺯﺭﻨﻴﺦ‬
‫‪5.8 ، 2.8‬‬ ‫‪CH2 (COOH)2‬‬ ‫ﺤﻤﺽ ﺍﻝﻤﺎﻝﻭﻨﻴﻙ‬
‫‪7.7 ، 2.6‬‬ ‫‪H2 TeO3‬‬ ‫ﺤﻤﺽ ﺍﻝﺘﻴﻠﻴﺭﻴﻭﻤﻲ‬
‫‪2.9‬‬ ‫‪CH2ClCOOH‬‬ ‫ﺤﻤﺽ ﻜﻠﻭﺭ ﺍﻝﺨل‬
‫‪4.3 ، 3.0‬‬ ‫‪(CH(OH)COOH)2‬‬ ‫ﺤﻤﺽ ﺍﻝﺘﺎﺭﺘﺭﻴﻙ‬
‫‪6.4 ، 4.8 ، 3.1‬‬ ‫‪H 3Cit‬‬ ‫ﺤﻤﺽ ﺍﻝﻠﻴﻤﻭﻥ‬
‫‪3.2‬‬ ‫‪HF‬‬ ‫ﺤﻤﺽ ﺍﻝﻔﻠﻭﺭ‬
‫‪3.3‬‬ ‫‪HNO2‬‬ ‫ﺤﻤﺽ ﺍﻵﺯﻭﺘﻲ‬

‫‪3.5‬‬ ‫‪C8 O2 H7 COOH‬‬ ‫ﺤﻤﺽ ﺍﻷﺴﺘﻴل ﺴﺎﻝﻴﺴﻴﻠﻙ‬
‫‪3.8‬‬ ‫‪HCOOH‬‬ ‫ﺤﻤﺽ ﺍﻝﻨﻤل‬
‫‪3.9‬‬ ‫‪CH 3CHOHCOOH‬‬ ‫ﺤﻤﺽ ﺍﻝﻠﺒﻥ‬
‫‪4.05‬‬ ‫‪C6 H 8O6‬‬ ‫ﺤﻤﺽ ﺍﻷﺴﻜﻭﺭﺒﻴﻙ‬

‫‪4.2‬‬ ‫‪C6 H5COOH‬‬ ‫ﺤﻤﺽ ﺍﻝﺒﻨﺯﻭﻴﻙ‬
‫‪4.4‬‬ ‫‪C6 H 4 OHCOOH‬‬ ‫ﺤﻤﺽ ﺍﻝﺴﺎﻝﻴﺴﻴﻠﻙ‬
‫‪4.5‬‬ ‫‪C6 H5 NH+‬‬
‫‪3‬‬ ‫ﺸﺎﺭﺩﺓ ﺍﻷﻨﻴﻠﻴﻨﻴﻭﻡ‬
‫‪4.7‬‬ ‫‪CH 3COOH‬‬ ‫ﺤﻤﺽ ﺍﻝﺨل‬
‫‪4.8‬‬ ‫‪C2 H5COOH‬‬ ‫ﺤﻤﺽ ﺍﻝﺒﺭﻭﺒﺎﻨﻭﻴﻙ‬
‫‪5.2‬‬ ‫‪C5 H6 N‬‬ ‫‪+‬‬ ‫ﺸﺎﺭﺩﺓ ﺍﻝﺒﻴﺭﻴﺩﻴﻨﻴﻭﻡ‬
‫‪6.1‬‬ ‫‪NH3OH+‬‬ ‫ﺸﺎﺭﺩﺓ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴل ﺃﻤﻭﻨﻴﻭﻡ‬
‫‪10.3 ، 6.4‬‬ ‫‪CO2‬‬ ‫ﺜﻨﺎﺌﻲ ﺃﻜﺴﻴﺩ ﺍﻝﻜﺭﺒﻭﻥ‬
‫‪13.0 ، 7.0‬‬ ‫‪H2 S‬‬ ‫ﺤﻤﺽ ﻜﺒﺭﻴﺕ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ‬
‫‪7.5‬‬ ‫‪HClO‬‬ ‫ﺤﻤﺽ ﺘﺤﺕ ﺍﻝﻜﻠﻭﺭ‬
‫‪297‬‬ ‫ﺍﻟﺜﻮﺍﺑﺖ ﺍﻟﺘﺮﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴﺔ ﻟﻠﺘﻮﺍﺯﻧﺎﺕ ﺍﳊﺎﺻﻠﺔ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
‫‪pK Ai‬‬ ‫ﺍﻝﺼﻴﻐﺔ‬ ‫ﺍﺴﻡ ﺍﻝﺤﻤﺽ‬

‫‪9.1‬‬ ‫‪H 3 AsO3‬‬ ‫ﺤﻤﺽ ﺍﻝﺯﺭﻨﻴﺨﻲ‬
‫‪9.2‬‬ ‫‪NH+‬‬
‫‪4‬‬ ‫ﺸﺎﺭﺩﺓ ﺍﻷﻤﻭﻨﻴﻭﻡ‬
‫‪9.2‬‬ ‫‪HBO2‬‬ ‫ﺤﻤﺽ ﺍﻝﺒﻭﺭ‬
‫‪9.3‬‬ ‫‪HCN‬‬ ‫ﺤﻤﺽ ﺴﻴﺎﻨﻴﺩ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻥ‬
‫‪9.9‬‬ ‫‪(CH 3 )3 NH+‬‬ ‫ﺸﺎﺭﺩﺓ ﺜﻼﺜﻲ ﻤﻴﺘﻴل ﺍﻷﻤﻭﻨﻴﻭﻡ‬
‫‪10.0‬‬ ‫‪C6 H5OH‬‬ ‫ﺍﻝﻔﻴﻨﻭل‬
‫‪10.7‬‬ ‫‪CH 3 NH+‬‬ ‫‪3‬‬ ‫ﺸﺎﺭﺩﺓ ﺍﻝﻤﻴﺘﻴل ﺃﻤﻭﻨﻴﻭﻡ‬
‫‪11.0‬‬ ‫‪(CH 3 )2 NH2+‬‬ ‫ﺸﺎﺭﺩﺓ ﺜﻨﺎﺌﻲ ﻤﻴﺘﻴل ﺍﻷﻤﻭﻨﻴﻭﻡ‬

‫ﺍﳌﻠﺤﻖ‬ 298
250 C ‫ ﻜﻤﻭﻨﺎﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ﺍﻝﻨﻅﺎﻤﻴﺔ ﻋﻨﺩ ﺍﻝﺩﺭﺠﺔ‬.II
E 0 (V) ‫ﺍﻝﻤﺭﺠﹺﻊ‬ ‫ﺩ‬‫ﺍﻝﻤﺅﻜﺴ‬
2.87 F− F2 (g)
2.08 O2 (g) O3 (g)

2.01 SO24− S2O28−
1.77 H2O H2O2
3+
1.71 Ce Ce4 +
1.51 Mn2 + MnO−
4
1.36 Cl− Cl2 (g)

1.33 Cr3 + Cr2O27−
1.23 Mn2 + MnO2

1.23 H2O O2 (g)
1.19 I2 (aq) IO−

3
1.09 Br− Br2 (l)

0.96 NO(g) NO−
3
0.91 Hg22 + Hg2 +

0.85 Hg(l) Hg2 +
0.80 Ag Ag+
0.79 Hg(l) Hg22 +
0.77 Fe2 + Fe3 +
0.68 H2O2 O2 (g)
0.62 I − I2 (aq)
0.34 Cu Cu2 +
0.17 SO2 (g) SO24−
0.15 Sn2 + Sn4 +
0.14 H2 S S
0.09 S2O23− S4O26−
0.05 C2 H5OH CH 3COOH
0.00 H2 (g) H+
−0.13 Pb Pb2 +
‫)‪E 0 (V‬‬ ‫ﺍﻝﻤﺭﺠﹺﻊ‬ ‫ﺍﻝﻤﺅﻜﺴ‪‬ﺩ‬
‫‪−0.14‬‬ ‫‪Sn‬‬ ‫‪Sn2 +‬‬

‫‪−0.26‬‬ ‫‪Ni‬‬ ‫‪Ni2 +‬‬
‫‪−0.40‬‬ ‫‪Cd‬‬ ‫‪Cd2 +‬‬
‫‪−0.44‬‬ ‫‪Fe‬‬ ‫‪Fe2 +‬‬
‫‪−0.49‬‬ ‫‪H2C2O4‬‬ ‫)‪CO2 (g‬‬
‫‪−0.76‬‬ ‫‪Zn‬‬ ‫‪Zn2 +‬‬
‫‪−1.68‬‬ ‫‪Al‬‬ ‫‪Al3 +‬‬
‫‪−2.26‬‬ ‫‪H−‬‬ ‫)‪H2 (g‬‬
‫‪−2.36‬‬ ‫‪Mg‬‬ ‫‪Mg2 +‬‬
‫‪−2.71‬‬ ‫‪Na‬‬ ‫‪Na +‬‬
‫‪−3.04‬‬ ‫‪Li‬‬ ‫‪Li+‬‬
‫ﺍﳌﻠﺤﻖ‬ 300
250 C ‫ ﺜﻭﺍﺒﺕ ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻋﻨﺩ‬.III
log βi ‫ﺍ ﻝﺸﺎ ﺭ ﺩﺓ‬ ‫ﺍﻝﺭﺒﻴﻁﺔ‬
i =6 i =5 i =4 i =3 i =2 i =1 ‫ﺍﻝﻤﺭﻜﺯﻴﺔ‬
7.2 3.3 Ag+
34.8 30.5 25.3 19.8 14.0 7.2 Co 3 +

NH3
12.6 10.5 7.6 4.1 Cu2 +
20 18 9.0 Hg2 +
8.2 8.1 7.5 6.4 4.8 2.6 Ni2 +

8.7 6.7 4.4 2.2 Zn2 +
21 20 Ag+
27.3 Cu2 + CN−
24 16 Fe2 +
31 Fe3 +
6.5 5.2 3.6 1.7 Cu2 + SCN−
4.6 4.3 3.0 Fe3 +
13.9 10.7 5.8 Co2 +

19.7 10.6 Cu2 +
NH2 (CH2 )2 NH2
9.6 7.6 4.3 Fe2 +
16.5 12.8 7.5 Ni2 +
13.5 8.8 Ag+
6.8 6.3 5.0 2.1 Fe3 + S2O23−
33.6 32.3 29.8 Hg2 +
4.6 2.8 Cd2 +

C2O24−
20.2 14.2 9.4 Fe3 +
5.3 3.8 Mn2 +

‫‪log βi‬‬ ‫ﺍ ﻝﺸﺎ ﺭ ﺩﺓ‬ ‫ﺍﻝﺭﺒﻴﻁﺔ‬

‫‪i =6‬‬ ‫‪i =5‬‬ ‫‪i =4‬‬ ‫‪i =3‬‬ ‫‪i =2‬‬ ‫‪i =1‬‬ ‫ﺍﻝﻤﺭﻜﺯﻴﺔ‬
‫‪21.2‬‬ ‫‪5.1‬‬ ‫‪Fe2 +‬‬ ‫ﺍﻷﻭﺭﺘﻭﻓﻴﻨﺎﻨﺘﺭﻭﻝﻴﻥ‬
‫‪14.0‬‬ ‫‪Fe3 +‬‬
‫‪7.8‬‬ ‫‪Ba2 +‬‬

‫‪10.7‬‬ ‫‪Ca 2 +‬‬
‫‪E.D.T.A.‬‬
‫‪8.7‬‬ ‫‪Mg2 +‬‬
‫) ‪(Y 4−‬‬
‫‪14.3‬‬ ‫‪Fe2 +‬‬
‫‪25.1‬‬ ‫‪Fe3 +‬‬
‫‪16.3‬‬ ‫‪Zn2 +‬‬
‫‪2.3‬‬ ‫‪Fe2 +‬‬

‫‪SO24−‬‬
‫‪7.4‬‬ ‫‪4.2‬‬ ‫‪Fe3 +‬‬
‫‪3.3‬‬ ‫‪Ce4 +‬‬
‫‪4.1‬‬ ‫‪Ce3 +‬‬
‫‪16.1‬‬ ‫‪13.7‬‬ ‫‪9.7‬‬ ‫‪5.5‬‬ ‫‪Fe3 +‬‬ ‫‪F−‬‬
‫‪20.7‬‬ ‫‪20.2‬‬ ‫‪18.5‬‬ ‫‪15.8‬‬ ‫‪12.0‬‬ ‫‪7.1‬‬ ‫‪Al3 +‬‬
‫‪29.8‬‬ ‫‪27.6‬‬ ‫‪23.8‬‬ ‫‪12.9‬‬ ‫‪Hg2 +‬‬ ‫‪I−‬‬

‫ﺍﳌﻠﺤﻖ‬ ‫‪302‬‬
‫‪ .IV‬ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻋﻨﺩ ‪250 C‬‬

‫‪pK s‬‬ ‫ﺍﻝﺼﻴﻐﺔ‬ ‫‪pK s‬‬ ‫ﺍﻝﺼﻴﻐﺔ‬
‫‪4.0‬‬ ‫‪Co(IO3 )2‬‬ ‫‪ 10.7‬ﺃﺒﻴﺽ‬ ‫‪Mg(OH)2‬‬

‫‪7.8‬‬ ‫‪Ni(IO3 )2‬‬ ‫ﺃﺒﻴﺽ‬ ‫‪5.2‬‬ ‫‪Ca(OH)2‬‬
‫‪7.1‬‬ ‫‪Cu(IO3 )2‬‬ ‫ﺃﺒﻴﺽ‬ ‫‪2.3‬‬ ‫‪Ba(OH)2‬‬
‫‪5.4‬‬ ‫‪Zn(IO3 )2‬‬ ‫ﺃﺨﻀﺭ‬ ‫‪31‬‬ ‫‪Cr(OH)3‬‬

‫‪7.5‬‬ ‫‪AgIO3‬‬ ‫‪ 12.8‬ﺯﻫﺭ‬ ‫‪Mn(OH)2‬‬
‫‪7.1‬‬ ‫‪Cd(IO3 )2‬‬ ‫‪ 15.1‬ﺃﺨﻀﺭ‬ ‫‪Fe(OH)2‬‬
‫‪ 17.9‬ﺃﺒﻴﺽ‬ ‫‪Hg2 (IO3 )2‬‬ ‫‪ 38‬ﺒﻨﻲ ﻤﺤﻤﺭ‬ ‫‪Fe(OH)3‬‬
‫‪ 18.7‬ﺃﺒﻴﺽ‬ ‫‪Hg(IO3 )2‬‬ ‫‪ 15.6‬ﺃﺯﺭﻕ‬ ‫‪Co(OH)2‬‬
‫‪ 12.5‬ﺃﺒﻴﺽ‬ ‫‪Pb(IO3 )2‬‬ ‫‪ 14.7‬ﺃﺨﻀﺭ‬ ‫‪Ni(OH)2‬‬
‫‪ 22.5‬ﺃﺨﻀﺭ‬ ‫‪Ni(CN)2‬‬ ‫‪ 19.7‬ﺃﺯﺭﻕ‬ ‫‪Cu(OH)2‬‬
‫‪ 12.6‬ﺃﺒﻴﺽ‬ ‫‪Zn(CN)2‬‬ ‫‪ 17.2‬ﺃﺒﻴﺽ‬ ‫‪Zn(OH)2‬‬
‫‪ 15.9‬ﺃﺒﻴﺽ‬ ‫‪AgCN‬‬ ‫‪ 7.7‬ﺴﻜﹼﺭﻱ‬ ‫‪AgOH‬‬
‫‪8.0‬‬ ‫‪Cd(CN)2‬‬ ‫ﺭﻤﺎﺩﻱ‬ ‫‪14‬‬ ‫‪Cd(OH)2‬‬
‫‪ 39‬ﺭﻤﺎﺩﻱ‬ ‫‪Hg2 (CN)2‬‬ ‫‪ 23.5‬ﺃﺴﻭﺩ‬ ‫‪Hg2 (OH)2‬‬
‫‪ 35.1‬ﺃﺒﻴﺽ‬ ‫‪Hg(CN)2‬‬ ‫‪ 25.3‬ﺒﺭﺘﻘﺎﻝﻲ‬ ‫‪Hg(OH)2‬‬
‫‪14.3‬‬ ‫‪Cu(SCN)2‬‬ ‫‪ 15.3‬ﺃﺒﻴﺽ‬ ‫‪Pb(OH)2‬‬
‫‪ 12.0‬ﺃﺒﻴﺽ‬ ‫‪AgSCN‬‬ ‫ﺃﺒﻴﺽ‬ ‫‪32‬‬ ‫‪Al(OH)3‬‬
‫‪ 19.5‬ﺭﻤﺎﺩﻱ‬ ‫‪Hg2 (SCN)2‬‬ ‫‪ 9.7‬ﺃﺒﻴﺽ‬ ‫‪AgCl‬‬
‫‪4.7‬‬ ‫‪Pb(SCN)2‬‬ ‫‪ 17.9‬ﺃﺒﻴﺽ‬ ‫‪Hg2Cl2‬‬
‫‪ 9.6‬ﺯﻫﺭ‬ ‫‪Mn S‬‬ ‫‪ 4.6‬ﺃﺒﻴﺽ‬ ‫‪PbCl2‬‬
‫‪ 17.2‬ﺃﺴﻭﺩ‬ ‫‪Fe S‬‬ ‫‪ 12.3‬ﻤﺎﺌل ﻝﻠﺼﻔﺭﺓ‬ ‫‪AgBr‬‬
‫‪ 85‬ﺃﺴﻭﺩ‬ ‫‪Fe2 S3‬‬ ‫‪ 22.2‬ﻤﺎﺌل ﻝﻠﺼﻔﺭﺓ‬ ‫‪Hg2 Br2‬‬
‫‪ 20.4‬ﺃﺴﻭﺩ‬ ‫‪Co S‬‬ ‫‪ 4.4‬ﺴﻜﹼﺭﻱ‬ ‫‪PbBr2‬‬
‫‪ 22‬ﺃﺴﻭﺩ‬ ‫‪Ni S‬‬ ‫‪ 16.2‬ﺃﺼﻔﺭ‬ ‫‪AgI‬‬
‫‪ 35.2‬ﺃﺴﻭﺩ‬ ‫‪Cu S‬‬ ‫‪ 28.3‬ﺃﺼﻔﺭ‬ ‫‪Hg2 I2‬‬
‫‪ 23.8‬ﺃﺒﻴﺽ‬ ‫‪Zn S‬‬ ‫‪ 28.3‬ﺃﺤﻤﺭ‬ ‫‪HgI2‬‬
‫‪ 49.2‬ﺃﺴﻭﺩ‬ ‫‪Ag2 S‬‬ ‫‪ 8.2‬ﺃﺼﻔﺭ‬ ‫‪PbI2‬‬
‫‪ 26.1‬ﺃﺼﻔﺭ‬ ‫‪Cd S‬‬ ‫‪2.5‬‬ ‫‪Mg(IO3 )2‬‬
‫‪ 37‬ﺃﺴﻭﺩ‬ ‫‪Hg2S2‬‬ ‫‪6.2‬‬ ‫‪Ca(IO3 )2‬‬
‫‪ 52‬ﺃﺴﻭﺩ‬ ‫‪Hg S‬‬ ‫‪ 8.8‬ﺃﺒﻴﺽ‬ ‫‪Ba(IO3 )2‬‬
‫‪ 26.6‬ﺃﺴﻭﺩ‬ ‫‪Pb S‬‬ ‫‪6.3‬‬ ‫‪Mn(IO3 )2‬‬
303 ‫ﺍﻟﺜﻮﺍﺑﺖ ﺍﻟﺘﺮﻣﻮﺩﻳﻨﺎﻣﻴﻜﻴﺔ ﻟﻠﺘﻮﺍﺯﻧﺎﺕ ﺍﳊﺎﺻﻠﺔ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬
pK s ‫ﺍﻝﺼﻴﻐﺔ‬ pK s ‫ﺍﻝﺼﻴﻐﺔ‬
‫ ﺃﺤﻤﺭ‬8.7 Hg2 CrO4 ‫ ﺃﺒﻴﺽ‬2.5 Mg SO3
‫ ﺃﺼﻔﺭ‬13.4 Pb CrO4 ‫ ﺃﺒﻴﺽ‬4.0 Ca SO3
4.1 Mg C2O4 ‫ ﺃﺒﻴﺽ‬8.0 Ba SO3

‫ ﺃﺒﻴﺽ‬8.6 Ca C2O4 ‫ ﺃﺒﻴﺽ‬13.8 Ag2 SO3
7.0 Ba C2O4 ‫ ﺃﺒﻴﺽ‬2.3 Mg SO4
5.3 Mn C2O4 ‫ ﺃﺒﻴﺽ‬4.6 Ca SO4

6.7 Fe C2O4 ‫ ﺃﺒﻴﺽ‬9.9 Ba SO4
5.4 Co C2O4 ‫ ﺃﺒﻴﺽ‬4.8 Ag2 SO4

7.0 Ni C2O4 ‫ ﺃﺼﻔﺭ‬6.2 Hg2 SO4
7.5 Cu C2O4 ‫ ﺃﺒﻴﺽ‬7.8 Pb SO4
8.8 Zn C2O4 ‫ ﺃﺒﻴﺽ‬3.0 Ag NO2

‫ ﺃﺒﻴﺽ‬11 Ag2 C2O4 ‫ ﺃﺒﻴﺽ‬6.6 Ca HPO4
7.8 Cd C2O4 ‫ ﺃﺒﻴﺽ‬7.6 Ba HPO4
13 Hg2 C2O4 12.4 Hg2 HPO4

‫ ﺃﺒﻴﺽ‬10.5 Pb C2O4 9.9 Pb HPO4
‫ ﺃﺒﻴﺽ‬6.0 Mg CO3 ‫ ﺃﺒﻴﺽ‬27.2 Mg3 ( PO4 )2
‫ ﺃﺒﻴﺽ‬8.2 Ca CO3 ‫ ﺃﺒﻴﺽ‬26.0 Ca 3 (PO4 )2
‫ ﺃﺒﻴﺽ‬8.3 Ba CO3 ‫ ﺃﺒﻴﺽ‬29.0 Ba 3 (PO4 )2
‫ ﺯﻫﺭ‬10.7 Mn CO3 ‫ ﺃﺒﻴﺽ‬22.0 Cr3 (PO4 )2
‫ ﺃﺨﻀﺭ‬10.5 Fe CO3 ‫ ﺃﺒﻴﺽ‬22.0 Mn 3 (PO4 )2
‫ ﻨﻬﺩﻱ‬12.8 Co CO3 ‫ ﺃﺼﻔﺭ‬22.0 Fe PO4
‫ ﺃﺨﻀﺭ‬8.2 Ni CO3 ‫ ﺃﺼﻔﺭ‬32.0 Zn 3 (PO4 )2
‫ ﺃﺯﺭﻕ ﻤﺨﻀﺭ‬9.6 Cu CO3 ‫ ﺃﺼﻔﺭ‬15.8 Ag3 PO4
‫ ﺃﺒﻴﺽ‬10.8 Zn CO3 42 Pb3 (PO4 )2
‫ ﺃﺒﻴﺽ‬11 Ag2 CO3 ‫ ﺃﺒﻴﺽ‬18 Al PO4
‫ ﺃﺒﻴﺽ‬13.6 Cd CO3 3.2 Ca CrO4
‫ ﺃﺼﻔﺭ‬16 Hg2 CO3 ‫ ﺃﺼﻔﺭ‬9.9 Ba CrO4
‫ ﺃﺒﻴﺽ‬13.5 Pb CO3 5.4 Cu CrO4
‫ ﺃﺒﻴﺽ‬2.7 Ag CH 3CO2 ‫ ﺃﺤﻤﺭ‬12 Ag2 CrO4
‫ﺩ‪ .‬ﺸﻜﻴﺏ ﻴﺠﺭ‪‬ﺏ ﺘﺄﺜﻴﺭ ﺤﻤﺽ ﺍﻝﻜﺒﺭﻴﺕ‬
‫ﺍﻝﻤﺭﻜﹼﺯ ﻋﻠﻰ ﻤﻌﻁﻔﻪ ﺍﻝﺠﺩﻴﺩ !‬
‫‪304‬‬
‫ﺍﻟﻤﺮﺍﺟﻊ‬
1. “Chimie II, première année PCSI”, André Durupthy, André

Casalot, Alain Jaubert et Claude Mesnil, Collection H prépa,
Hachette Supérieur, Paris, 1996.
2. “Chimie Générale”, Maurice Ravaille et René Didier,

Collection de Sciences Physiques, J.-B. Baillière, Paris, 1979.
3. “Introduction à la Chimie Organique”, Hart & Conia,

InterEdition, Paris, 1987.
4. “World of Chemistry”, S.S. Zumdahl, S.L. Zumdahl and D.J.

DeCoste, McDougal Littell, A Houghton Mifflin Company,
USA, 2007.
5. “Chemistry Connection, The chemical basis of everyday

phenomena”, K.K. Karukstis and J. R. Van Heche,
Complementary Science Series, Elsevier Science &
Technology, 2007.
6. “Physical Chemistry, Understanding our chemical world”, P.

Monk, John Wiley & Sons Ltd, West Sussex, 2004.
305
‫ﺔ‬‫ﺮﺩ ﺍﻟﻤﺼﻄﻠﺤﺎﺕ ﺍﻟﻌﻠﻤﻴ‬‫ﺴ‬‫ﻣ‬
‫ﺔ‬‫ﺍﻹﻨﻜﻠﻴﺯﻴ‬ ‫ﺔ‬‫ﺍﻝﻌﺭﺒﻴ‬ ‫ﺔ‬‫ﺍﻝﻔﺭﻨﺴﻴ‬
A
Acid ‫ﺤﻤﺽ‬ Acide
Conjugate Acid ‫ﻕ‬‫ﺭﺍﻓ‬‫ﺤﻤﺽ ﻤ‬ Acide Conjugué
Weak Acid ‫ﺤﻤﺽ ﻀﻌﻴﻑ‬ Acide Faible
Strong Acid ‫ﺤﻤﺽ ﻗﻭﻱ‬ Acide Fort
Spectator Acid in Acide Indifférent dans
‫ﺩ ﻓﻲ ﺍﻝﻤﺎﺀ‬‫ﺤﻤﺽ ﺸﺎﻫ‬
Water l’eau
Polyacid ‫ﺩ ﺍﻝﻭﻅﻴﻔﺔ‬‫ﺤﻤﺽ ﻤﺘﻌﺩ‬ Polyacide
Acidity ‫ﺤﻤﻭﻀﺔ‬ Acidité
‫ ﺃﺴﺎﺴﻲ‬-‫ﺏ ﺤﻤﻀﻲ‬‫ﻤﺘﺫﺒﺫ‬
Amphoteric Amphotère
(‫)ﺃﻤﻔﻭﻝﻴﺕ‬
Anion ‫ ﺃﻴﻭﻥ ﺴﺎﻝﺏ‬-‫ﺸﺎﺭﺩﺓ ﺴﺎﻝﺒﺔ‬ Anion
Anode ‫ﻤﺼﻌﺩ‬ Anode
Self-Ionization of -‫ﺍﻝﺘﺤﹼﻠل ﺍﻝﺒﺭﻭﺘﻭﻨﻲ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‬
Auto-Protolyse de l'eau
Water ‫ﻥ ﺍﻝﺫﺍﺘﻲ ﻝﻠﻤﺎﺀ‬‫ﺍﻝﺘﺄﻴ‬
Avancement de la
Extent of Reaction ‫ﻡ ﺍﻝﺘﻔﺎﻋل‬‫ﺘﻘﺩ‬
Réaction
B
Base ‫ﺃﺴﺎﺱ‬ Base
Conjugate Base ‫ﻕ‬‫ﺭﺍﻓ‬‫ﺃﺴﺎﺱ ﻤ‬ Base Conjuguée
Weak Base ‫ﺃﺴﺎﺱ ﻀﻌﻴﻑ‬ Base Faible
Strong Base ‫ﺃﺴﺎﺱ ﻗﻭﻱ‬ Base Forte
307
Spectator Base in Base Indifférente dans
‫ﺩ ﻓﻲ ﺍﻝﻤﺎﺀ‬‫ﺃﺴﺎﺱ ﺸﺎﻫ‬
Water l'eau
Polybase ‫ﺩ ﺍﻝﻭﻅﻴﻔﺔ‬‫ﺃﺴﺎﺱ ﻤﺘﻌﺩ‬ Polybase
Basicity (‫ﺔ )ﻗﺎﻋﺩﻴﺔ‬‫ﺃﺴﺎﺴﻴ‬ Basicité
C
-‫ﺸﺎﺭﺩﺓ ﻤﻭﺠﺒﺔ‬
Cation Cation
‫ﺃﻴﻭﻥ ﻤﻭﺠﺏ‬
Cathode ‫ﻤﻬﺒﻁ‬ Cathode
Cell ‫ﺨﻠﻴﺔ‬ Cellule
Cellule
Electrochemical Cell ‫ﺨﻠﻴﺔ ﻜﻬﺭﻜﻴﻤﻴﺎﺌﻴﺔ‬
Electrochimique
Galvanic Cell ‫ﺨﻠﻴﺔ ﻏﻠﻔﺎﻨﻴﺔ‬ Cellule Galvanique
Classification ‫ﺘﺼﻨﻴﻑ‬ Classification
Competition ‫ﺘﻨﺎﻓﺱ‬ Compétition
Competitive Complexations
‫ﻤﻌﻘﹼﺩﺍﺕ ﻤﺘﻨﺎﻓﺴﺔ‬
Complexations Compétitives
Competitive Précipitations
‫ﺭﻭﺍﺴﺏ ﻤﺘﻨﺎﻓﺴﺔ‬
Precipitations Compétitives
Complex ‫ﻤﻌﻘﱠﺩ‬ Complexe
Gaseous Compound ‫ﺭﻜﱠﺏ ﻏﺎﺯﻱ‬‫ﻤ‬ Composé Gazeux
Ionic Compound ‫ﺭﻜﹼﺏ ﺸﺎﺭﺩﻱ‬‫ﻤ‬ Composé Ionique
Liquid Compound ‫ﺭﻜﱠﺏ ﺴﺎﺌل‬‫ﻤ‬ Composé Liquide
Solid Compound ‫ﺭﻜﱠﺏ ﺼﻠﺏ‬‫ﻤ‬ Composé Solide
Concentration ‫ﺘﺭﻜﻴﺯ‬ Concentration, Titre
Molar Concentration ‫ﺘﺭﻜﻴﺯ ﻤﻭﻝﻲ‬ Concentration Molaire
Concentration de
Solution Concentration ‫ﺘﺭﻜﻴﺯ ﻤﺤﻠﻭل‬
Solution
Constant ‫ﺜﺎﺒﺕ‬ Constante
Acid Dissociation
‫ﺜﺎﺒﺕ ﺍﻝﺤﻤﻭﻀﺔ‬ Constante d'Acidité
Constant- Acidity
308
Constant
Basicity Constant ‫ﺔ‬‫ﺜﺎﺒﺕ ﺍﻷﺴﺎﺴﻴ‬ Constante de Basicité
Dielectric Constant ‫ﺜﺎﺒﺕ ﺍﻝﻌﺯل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ‬ Constante Diélectrique
Constante de
Complex Dissociation
‫ﺜﺎﺒﺕ ﺘﻔﻜﱡﻙ ﻤﻌﻘﱠﺩ‬ Dissociation d’un
Constant
Complexe
Stepwise Dissociation Constante de
‫ﺜﺎﺒﺕ ﺘﻔﻜﱡﻙ ﺘﻌﺎﻗﺒﻲ‬
Constant Dissociation Successive
Cumulative Constante de
‫ﺜﺎﺒﺕ ﺘﻔﻜﱡﻙ ﺇﺠﻤﺎﻝﻲ‬
Dissociation Constant Dissociation Globale
Equilibrium Constant ‫ﺜﺎﺒﺕ ﺘﻭﺍﺯﻥ‬ Constante d'Equilibre
Constante de
Complex Formation
‫ﺜﺎﺒﺕ ﺘﺸﻜﱡل ﻤﻌﻘﹼﺩ‬ Formation d’un
Constant
Complexe
Stepwise Formation Constante de
‫ﺜﺎﺒﺕ ﺘﺸﻜﹼل ﺘﻌﺎﻗﺒﻲ‬
Constant Formation Successive
Cumulative Formation Constante de
‫ﺜﺎﺒﺕ ﺘﺸﻜﹼل ﺇﺠﻤﺎﻝﻲ‬
Constant Formation globale
Reaction Constant ‫ل‬‫ﺜﺎﺒﺕ ﺘﻔﺎﻋ‬ Constante de Réaction
Complex Stability Constante de Stabilité
‫ﻌ ﱠﻘﺩ‬‫ﺔ ﻤ‬‫ﺜﺎﺒﺕ ﺍﺴﺘﻘﺭﺍﺭﻴ‬
Constant d'un Complexe
Thermodynamic Constante
‫ﺜﺎﺒﺕ ﺘﺭﻤﻭﺩﻴﻨﺎﻤﻴﻜﻲ‬
Constant Thermodynamique
Coordination ‫ﺘﺴﺎﻨﺩ‬ Coordination
Coordination Composés de
‫ﺭﻜﱠﺒﺎﺕ ﺘﺴﺎﻨﺩﻴﺔ‬‫ﻤ‬
Compounds Coordination
Coordination number ‫ﺩﻝﻴل ﺍﻝﺘﺴﺎﻨﺩ‬ Indice de Coordination
Couple ‫ﺯﻭﺝ‬ Couple
Conjugate Acid-Base Couple Acido-Basique
‫ ﺃﺴﺎﺱ ﻤﺘﺭﺍﻓﻕ‬/ ‫ﺯﻭﺝ ﺤﻤﺽ‬
pair Conjugué
Couple Rédox
Redox Couple ‫ﺭﺠﹺﻊ‬‫ ﻤ‬/ ‫ﺩ‬‫ﺯﻭﺝ ﻤﺅﻜﺴ‬
(Ox/Red)
309
D
Diagramme de
Distribution Diagram ‫ﻤﺨﻁﻁ ﺘﻭﺯﻴﻊ‬
Distribution
Dislocation ‫ﺍﻨﺨﻼﻉ‬ Dislocation
Dispersion ‫ﺘﺸﺘﱡﺕ‬ Dispersion
Dissolution ‫ﺫﻭﺒﺎﻥ‬-‫ﺍﻨﺤﻼل‬ Dissolution
E
Leveling Effect ‫ﻤﻔﻌﻭل ﺍﻝﺘﺴﻭﻴﺔ‬ Effet de Nivellement
Electrode ‫ﻤﺴﺭﻯ‬ Electrode
Electrolyte ‫ﻜﻬﺭﻝﻴﺕ‬ Electrolyte
Electrolytic Solution ‫ﻤﺤﻠﻭل ﻜﻬﺭﻝﻴﺕ‬ Solution Electrolytique
Electronegativity ‫ﺔ‬‫ﻜﻬﺭﺴﻠﺒﻴ‬ Electronégativité
Equation ‫ﻤﻌﺎﺩﻝﺔ‬ Equation
Overall Equation ‫ﻠﺔ‬‫ﺍﻝﻤﻌﺎﺩﻝﺔ ﺍﻝﻤﺤﺼ‬ Equation Bilan
Equation of Matter Equation Bilan de
‫ﺓ‬‫ﻤﻌﺎﺩﻝﺔ ﺍﻨﺤﻔﺎﻅ ﺍﻝﻤﺎﺩ‬
Conservation Matière
Electrical
Equation de
Neutralization ‫ﻤﻌﺎﺩﻝﺔ ﺍﻻﻋﺘﺩﺍل ﺍﻝﻜﻬﺭﺒﺎﺌﻲ‬
l’électro-neutralité
Equation
Formal Equation ‫ﺔ‬‫ﻤﻌﺎﺩﻝﺔ ﺸﻜﻠﻴ‬ Equation Formelle
Balancing Chemical Equilibrage d'une
‫ﻤﻭﺍﺯﻨﺔ ﻤﻌﺎﺩﻝﺔ ﻜﻴﻤﻴﺎﺌﻴﺔ‬
Equation Equation Chimique
Equilibrium ‫ﺘﻭﺍﺯﻥ‬ Equilibre
Equilibre Acido-
Acid-Base Equilibrium ‫ﻲ‬
 ‫ﺃﺴﺎﺴ‬-‫ﻲ‬
 ‫ﺘﻭﺍﺯﻥ ﺤﻤﻀ‬
Basique
Chemical Equilibrium ‫ﺘﻭﺍﺯﻥ ﻜﻴﻤﻴﺎﺌﻲ‬ Equilibre Chimique
Precipitation Equilibre de
‫ﺘﻭﺍﺯﻥ ﺍﻝﺘﺭﺴﻴﺏ‬
Equilibrium Précipitation
Oxidation- reduction ‫ﺘﻭﺍﺯﻥ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‬ Equilibre
310
Equilibrium d'oxydoréduction
Out of Equilibrium
‫ﺠﻤﻠﺔ ﺨﺎﺭﺝ ﺍﻝﺘﻭﺍﺯﻥ‬ Système Hors Equilibre
System
Equivalence ‫ﺘﻜﺎﻓﺅ‬ Equivalence
Equivalence Point ‫ﻨﻘﻁﺔ ﺘﻜﺎﻓﺅ‬ Point d'Equivalence
Chemical Specie ‫ﻨﻭﻉ ﻜﻴﻤﻴﺎﺌﻲ‬ Espèce Chimique
Qualitative Study ‫ﺔ‬‫ﺩﺭﺍﺴﺔ ﻜﻴﻔﻴ‬ Etude Qualitative
Quantitative Study ‫ﺔ‬‫ﺩﺭﺍﺴﺔ ﻜﻤﻴ‬ Etude Quantitative
F
Filtrate ‫ﺸﺎﺤﺔ‬‫ﺭ‬ Filtrat
Filtration ‫ﺘﺭﺸﻴﺢ‬-‫ﻓﻠﺘﺭﺓ‬ Filtration, Filtrage
H
Hydration ‫ﺇﻤﺎﻫﺔ‬ Hydratation
I
Ion ‫ ﺃﻴﻭﻥ‬-‫ﺸﺎﺭﺩﺓ‬ Ion
Complex Ion ‫ﺸﺎﺭﺩﺓ ﻤﻌﻘﱠﺩﺓ‬ Ion Complexe
Hydrated Ion (‫ﻬﺔ‬‫ﺸﺎﺭﺩﺓ ﻤﻨﺤﻠﱠﺔ ﻓﻲ ﺍﻝﻤﺎﺀ )ﻤﻤﻴ‬ Ion Hydraté
Solvated Ion ‫ﺸﺎﺭﺩﺓ ﻤﻨﺤﻠﱠﺔ‬ Ion Solvaté
Major Ion ‫ﺸﺎﺭﺩﺓ ﻏﺎﻝﺒﺔ ﺍﻝﺘﺭﻜﻴﺯ‬ Ion Majoritaire
Minor Ion ‫ﺸﺎﺭﺩﺓ ﻤﻐﻠﻭﺒﺔ ﺍﻝﺘﺭﻜﻴﺯ‬ Ion Minoritaire
Ultramajor Ion ‫ﺸﺎﺭﺩﺓ ﻓﺎﺌﻘﺔ ﺍﻝﻐﻠﺒﺔ‬ Ion Ultramajoritaire
Ultraminor Ion ‫ﺸﺎﺭﺩﺓ ﻨﺎﺩﺭﺓ ﺍﻝﺘﺭﻜﻴﺯ‬ Ion Ultraminoritaire
311
Ligand ‫ﺭﺒﻴﻁﺔ‬ Ligand
Donor of Ligands ‫ﻤﺎﻨﺢ ﺭﺒﻴﻁﺎﺕ‬ Donneur de Ligands
Acceptor of Ligands ‫ﺒل ﺭﺒﻴﻁﺎﺕ‬ ‫ﺘﻘ‬‫ﻤ‬ Accepteur de Ligands
Simulation Programs ‫ﺎﺕ ﻤﺤﺎﻜﺎﺓ‬‫ﺒﺭﻤﺠﻴ‬ Logiciels de Simulation
M
Medium ‫ﻭﺴﻁ‬ Milieu
Acidic Medium ‫ﻭﺴﻁ ﺤﻤﻀﻲ‬ Milieu Acide
Basic Medium ‫ﻭﺴﻁ ﺃﺴﺎﺴﻲ‬ Milieu Basique
Dipole Moment ‫ﻋﺯﻡ ﺜﻨﺎﺌﻲ ﺍﻝﻘﻁﺏ‬ Moment Dipolaire
N
Neutralization ‫ﺘﻌﺩﻴل‬ Neutralisation
Oxidation Number
‫ﺭﻗﻡ ﺃﻜﺴﺩﺓ‬ Nombre d'oxydation
Oxidation State
O
Oxidant ‫ﺅﻜﺴﺩ‬‫ﻤ‬ Oxydant
Oxidation ‫ﺃﻜﺴﺩﺓ‬ Oxydation
P
Battery ‫ﺒﻁﺎﺭﻴﺔ‬ Pile
Daniell Cell ‫ ﺨﻠﻴﺔ ﺩﺍﻨﻴل‬-‫ﺒﻁﺎﺭﻴﺔ ﺩﺍﻨﻴل‬ Pile Daniell
Polar ‫ﻗﻁﺒﻲ‬ Polaire
Polar Molecule ‫ﻲ‬
 ‫ﺠﺯﻱﺀ ﻗﻁﺒ‬ Molécule Polaire
Potential ‫ﻜﻤﻭﻥ‬ Potentiel
Electrode Potential ‫ﻜﻤﻭﻥ ﻤﺴﺭﻯ‬ Potentiel d'électrode
312
Ability ‫ﻗﺩﺭﺓ‬ Pouvoir
Ability of Dissociation ‫ل‬‫ﻗﺩﺭﺓ ﻓﺼ‬ Pouvoir Dissociant
Ability of Ionization ‫ﻗﺩﺭﺓ ﺘﺸﺭﻴﺩ‬ Pouvoir Ionisant
Buffer Capacity ‫ﻗﺩﺭﺓ ﻤﻭﻗﻴﺔ‬ Pouvoir Tampon
Predominance ‫ﺭﺠﺤﺎﻥ‬ Prédominance
Diagram of Diagramme de
‫ﺨﻁﱠﻁ ﺭﺠﺤﺎﻥ‬‫ﻤ‬
Predominance Prédominance
Regions of Domaines de
‫ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ‬
Predominance Prédominance
Preponderant ‫ﺭﺍﺠﺢ‬ Prépondérant
Precipitation ‫ﺍﻝﺘﺭﺴﻴﺏ‬ Précipitation
Precipitation Condition de
‫ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ‬
Condition Précipitation
Precipitate ‫ﺭﺍﺴﺏ‬ Précipité
Diagramme
Precipitate Existence
‫ﻤﺨﻁﹼﻁ ﻭﺠﻭﺩ ﺭﺍﺴﺏ‬ d’Existence d'un
Diagram
Précipité
Precipitate Existence Domaines d’Existence
‫ﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺭﺍﺴﺏ‬
Regions d'un Précipité
Ion Product ‫ﺠﺩﺍﺀ ﺸﺎﺭﺩﻱ‬ Produit Ionique
Produit Ionique de
Water Ionic Product ‫ﺍﻝﺠﺩﺍﺀ ﺍﻝﺸﺎﺭﺩﻱ ﻝﻠﻤﺎﺀ‬
l'Eau
R
Reaction ‫ل‬‫ﺘﹶﻔﺎﻋ‬ Réaction
Réactions Acido-
Acid-Base Reactions ‫ﺔ‬‫ﺔ ﺃﺴﺎﺴﻴ‬‫ﻼﺕ ﺤﻤﻀﻴ‬‫ﺘﻔﺎﻋ‬
Basiques
Complete, Réaction Complète,
‫ﻡ‬ ‫ل ﻜﻤﻲ ﺘﺎ‬‫ﺘﻔﺎﻋ‬
Quantitative Reaction Quantitative, Totale
Complexation Réactions de
‫ﺘﻔﺎﻋﻼﺕ ﺘﻌﻘﻴﺩ‬
Reactions Complexation
Precipitation Reactions ‫ﺘﻔﺎﻋﻼﺕ ﺘﺭﺴﻴﺏ‬ Réactions de
313
Précipitation
Oxidation-Reduction Réactions
‫ﺇﺭﺠﺎﻉ‬-‫ﺘﻔﺎﻋﻼﺕ ﺃﻜﺴﺩﺓ‬
Reaction d'oxydoréduction
Réaction
Predominant Reaction ‫ﺘﻔﺎﻋل ﺭﺍﺠﺢ‬
Prépondérante
Reversible Reactions ‫ﻼﺕ ﻋﻜﻭﺴﺔ‬‫ﺘﻔﺎﻋ‬ Réactions Réversibles
Irreversible Reactions ‫ﻼﺕ ﻏﻴﺭ ﻋﻜﻭﺴﺔ‬‫ﺘﻔﺎﻋ‬ Réactions Irréversibles
Reducer ‫ﺠﻊ‬
‫ﺭ ﹺ‬‫ﻤ‬ Réducteur
Reduction ‫ﺇﺭﺠﺎﻉ‬ Réduction
S
Saturation ‫ﺇﺸﺒﺎﻉ‬ Saturation
Soluble ‫ﻗﺎﺒل ﻝﻼﻨﺤﻼل‬ Soluble
Solubilization ‫ﺍﻨﺤﻼل‬ Solubilisation
Solubility ‫ﺔ‬‫ﺍﻨﺤﻼﻝﻴ‬ Solubilité
Solubility Product ‫ﺠﺩﺍﺀ ﺍﻨﺤﻼل‬ Produit de Solubilité
Slightly Soluble ‫ﻀﻌﻴﻑ ﺍﻻﻨﺤﻼل‬ Peu Soluble
Solute ‫ﺓ ﻤﺫﺍﺒﺔ‬‫ﻤﺎﺩ‬ Soluté
Solution ‫ﻤﺤﻠﻭل‬ Solution
Aqueous Solutions ‫ﺔ‬‫ﻤﺤﺎﻝﻴل ﻤﺎﺌﻴ‬ Solutions Aqueuses
Concentrated Solution ‫ﻤﺤﻠﻭل ﻤﺭﻜﹼﺯ‬ Solution Concentrée
Diluted Solution ‫ﺩ‬‫ﻤﺤﻠﻭل ﻤﻤﺩ‬ Solution Diluée
Saturated Solution ‫ﻊ‬‫ﻤﺤﻠﻭل ﻤﺸﺒ‬ Solution Saturée
Buffer Solution ‫ﻤﺤﻠﻭل ﻤﻭﻕ‬ Solution Tampon

Solvent ‫ﺫﻴﺏ‬‫ﻤ‬ Solvant
Dispersing Solvent ‫ﺫﻴﺏ ﻤﺸﺘﹼﺕ‬‫ﻤ‬ Solvant Dispersant
Ionizing Solvent ‫ﺩ‬‫ﺫﻴﺏ ﻤﺸﺭ‬‫ﻤ‬ Solvant Ionisant
Solvatation ‫ﺏ‬‫ﺘﺫﻭ‬ Solvatation
Stability ‫ﺔ‬‫ﺍﺴﺘﻘﺭﺍﺭﻴ‬ Stabilité
Stoichiometry ‫ ﺃﻤﺜﺎل ﺍﻝﺘﻔﺎﻋل‬،‫ﺔ‬‫ﺴﺘﻭﻜﻴﻭﻤﺘﺭﻴ‬ Stœchiométrie
Out of Equilibrium
‫ﺠﻤﻠﺔ ﺨﺎﺭﺝ ﺍﻝﺘﻭﺍﺯﻥ‬ Système Hors Equilibre
System
314
T
Titration ‫ﻤﻌﺎﻴﺭﺓ‬ Titrage-Dosage

Acid-Base Titration ‫ﺔ‬‫ ﺃﺴﺎﺴﻴ‬-‫ﺔ‬‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﻀﻴ‬ Titrage Acido-Basique
Oxidation-reduction Titrage d'oxydo-
‫ ﺇﺭﺠﺎﻉ‬-‫ﻤﻌﺎﻴﺭﺓ ﺃﻜﺴﺩﺓ‬
titration réduction
315
316
Higher Institute For Applied Sciences
And Technology
Chemistry Of
A q u e o u s S o lu t io n s
Dr.
Yomen Atassi
2011

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‫ﺍﻟﻤﻌﻬﺪ ﺍﻟﻌﺎﻟﻲ ﻟﻠﻌﻠﻮﻡ ﺍﻟﺘﻄﺒﻴﻘﻴ‪‬ﺔ‬

‫ﻛﻴﻤﻴﺎﺀ ﺍﻟﻤﺤﺎﻟﻴﻞ ﺍﻟﻤﺎﺋﻴ‪‬ﺔ‬

‫ﻣﻨﺸﻮﺭﺍﺕ ﺍﻟﻤﻌﻬﺪ ﺍﻟﻌﺎﻟﻲ ﻟﻠﻌﻠﻮﻡ ﺍﻟﺘﻄﺒﻴﻘﻴ‪‬ﺔ ﻭﺍﻟﺘﻜﻨﻮﻟﻮﺟﻴﺎ‬

‫‪ ٢٠١١‬ﻤ ‪ ١٤٣٢ -‬ﻫ‬

‫ ‪&'()( *+  %‬‬

‫  ‪, - ./‬‬

‫ﺘﺫﻜﺭﺓ ﺒﺒﻌﺽ ﺍﻝﺘﻌﺎﺭﻴﻑ ‪6 ....................................................‬‬ ‫‪.1.I‬‬

‫ﺍﻝﻤﺎﺀ‪ :‬ﻤ‪‬ﺫﻴﺏ‪ ‬ﺫﻭ ﺨﻭﺍﺹ ﺘﺸﺭﻴﺩ ﻭﺇﻤﺎﻫﺔ ﻭﺘﺸﺘﻴﺕ ‪7 .............................‬‬ ‫‪.2.I‬‬

‫ﺍﻝﺘﻭﺍﺯﻨﺎﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ ‪10.......................................................‬‬ ‫‪.II‬‬

‫‪ .3.II‬ﺍﻝﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪-‬ﺃﺴﺎﺱ ‪12..................................................‬‬

‫‪ .1.III‬ﺤﺎﻝﺔ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ﺍﻝﻀﻌﻴﻔﺔ ‪18..........................................‬‬

‫ﺘﻔﺎﻋﻼﺕ ﺤﻤﺽ‪ -‬ﺃﺴﺎﺱ‪ :‬ﺩﺭﺍﺴﺔ ﻜﻤﻴ‪‬ﺔ ‪24............................................‬‬ ‫‪.V‬‬

‫ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ‪28...................................................................‬‬ ‫‪.VI‬‬

‫‪ .1.I‬ﺍﻷﻨﻭﺍﻉ ﺍﻝﻐﺎﻝﺒﺔ ﻭﺍﻝﻤﻐﻠﻭﺒﺔ ﻭﺍﻝﻤﻬﻤﻠﺔ ‪42............................................‬‬

‫‪ .1.II‬ﺍﻝﻁﺭﻴﻘﺔ ﺍﻹﺠﻤﺎﻝﻴﺔ ‪47.........................................................‬‬

‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﺃﻭ ﺃﺴﺎﺱ‪82...................................................‬‬ ‫‪.1.I‬‬

‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻀﻌﻴﻑ ﺒﺄﺴﺎﺱ ﻗﻭﻱ ‪89.......................................‬‬ ‫‪.3.I‬‬

‫‪ .1.3.I‬ﺘﻔﺎﻋل ﺍﻝﻤﻌﺎﻴﺭﺓ ﻫﻭ ﺍﻝﺘﻔﺎﻋل ﺍﻝﺭﺍﺠﺢ ﺍﻝﻭﺤﻴﺩ ‪89..............................‬‬

‫ﻤﻌﺎﻴﺭﺓ ﺤﻤﺽ ﻤﺘﻌﺩﺩ ﺍﻝﻭﻅﻴﻔﺔ ‪94..............................................‬‬ ‫‪.5.I‬‬

‫‪ .1.5.I‬ﺩﺭﺍﺴﺔ ﻨﻅﺭﻴﺔ ‪94..........................................................‬‬

‫‪ .3.5.I‬ﻤﺤﺎﻜﺎﺓ ﻝﻤﻌﺎﻴﺭﺓ ﺒﻌﺽ ﺍﻝﺤﻤﻭﺽ ﻭﺍﻷﺴﺱ ‪99...............................‬‬

‫‪ .1.II‬ﺃﻤﺜﻠﺔ ‪102 ...................................................................‬‬

‫ﻤﺸﺎﻫﺩﺍﺕ ﺘﺠﺭﻴﺒﻴ‪‬ﺔ ‪116 ......................................................‬‬ ‫‪.1.I‬‬

‫ﺘﻌﺎﺭﻴﻑ ‪116 ................................................................‬‬ ‫‪.2.I‬‬

‫ﻫﻨﺩﺴﺔ ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ‪120 ........................................................‬‬ ‫‪.3.I‬‬

‫ﺜﻭﺍﺒﺕ ﻤﻤﻴ‪‬ﺯﺓ ﻝﺘﺸﻜﱡل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﻓﻲ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴ‪‬ﺔ ‪121 ...............................‬‬ ‫‪.II‬‬

‫ﻤﻨﺎﻁﻕ ﺍﻝﺭﺠﺤﺎﻥ ‪124 ...............................................................‬‬ ‫‪.III‬‬

‫ﺍﻝﻤﻌﻘﹼﺩﺍﺕ ﺍﻝﻤﺘﻨﺎﻓﺴﺔ ‪127 .............................................................‬‬ ‫‪.IV‬‬

‫‪ .1.IV‬ﺍﻝﺘﻨﺎﻓﺱ ﺒﻴﻥ ﺍﻝﺭﺒﻴﻁﺘﻴﻥ‪ L' :‬ﻭ ‪127 ....................................... L‬‬

‫ﺘﺸﻜﹼل ﺍﻝﻤﻌﻘﹼﺩﺍﺕ‪ -‬ﺘﺭﻜﻴﺏ ﻤﺤﻠﻭل ‪134 ................................................‬‬ ‫‪.VI‬‬

‫‪ .1.VI‬ﺘﺸﻜﹼل ﻤﻌﻘﺩ ﻭﺤﻴﺩ ‪135 ......................................................‬‬

‫ﺍﻨﺤﻼل ﻜﺒﺭﻴﺘﺎﺕ ﺍﻝﻜﺎﻝﺴﻴﻭﻡ ‪158 ..............................................‬‬ ‫‪.1.I‬‬

‫ﺘﻌﻤﻴﻡ ‪159 ...................................................................‬‬ ‫‪.2.I‬‬

‫ﺠﺩﺍﺀ ﺍﻻﻨﺤﻼل ﻭﺍﻻﻨﺤﻼﻝﻴ‪‬ﺔ ‪160 ..............................................‬‬ ‫‪.3.I‬‬

‫ﺸﺭﻁ ﺍﻝﺘﺭﺴﻴﺏ ‪161 .................................................................‬‬ ‫‪.II‬‬

‫ﺇﻴﺠﺎﺩ ﺍﻝﺸﺭﻁ ‪161 ...........................................................‬‬ ‫‪.1.II‬‬

‫ﺘﻁﺒﻴﻕ ‪162 .................................................................‬‬ ‫‪.2.II‬‬

‫ﺃﺜﺭ ﺍﻝﺸﺎﺭﺩﺓ ﺍﻝﻤﺸﺘﺭﻜﺔ ‪164 ..................................................‬‬ ‫‪.3.II‬‬

‫ﻤﻨﺎﻁﻕ ﻭﺠﻭﺩ ﺭﺍﺴﺏ ﻤﺎ ‪169 ........................................................‬‬ ‫‪.III‬‬

‫ﺘﻨﺎﻓﺱ ﺍﻝﺭﻭﺍﺴﺏ ‪171 ................................................................‬‬ ‫‪.IV‬‬

‫‪ .1.IV‬ﺘﺠﺭﺒﺔ ‪171 .................................................................‬‬

‫ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﻋﻥ ﻁﺭﻴﻕ ﺘﺸﻜﹼل ﻤﻌﻘﹼﺩ‪174 ...................................‬‬ ‫‪.1.V‬‬

‫‪ .1.1.V‬ﺘﺠﺭﺒﺔ ‪174 ..............................................................‬‬

‫ﺍﻝﺘﺭﺴﻴﺏ ﻭ ‪ pH‬ﺍﻝﻭﺴﻁ‪180 .........................................................‬‬ ‫‪.VI‬‬

‫‪ .1.VI‬ﺍﻨﺤﻼل ﺭﺍﺴﺏ ﺒﻔﻌل ﺤﻤﺽ‪180 .............................................‬‬

‫ﺗﻮﺍﺯﻧﺎﺕ ﺍﻷﻛﺴﺪﺓ ﻭﺍﻹﺭﺟﺎﻉ ﰲ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ‬

‫ﺘﻌﺎﺭﻴﻑ ‪206 ........................................................................‬‬ ‫‪.I‬‬

‫ﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪207 .....................................................‬‬ ‫‪.II‬‬

‫ﻤﻔﻬﻭﻡ ﺭﻗﻡ ﺍﻷﻜﺴﺩﺓ ‪211 .............................................................‬‬ ‫‪.IV‬‬

‫ﺨﻭﺍﺹ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ‪214 ..........................................................‬‬ ‫‪.V‬‬

‫ﺘﻁﺒﻴﻘﺎﺕ ﺃﺭﻗﺎﻡ ﺍﻷﻜﺴﺩﺓ ‪215 .........................................................‬‬ ‫‪.VI‬‬

‫‪ .1.VI‬ﺩﺭﺍﺴﺔ ﻁﺒﻴﻌﺔ ﺘﻔﺎﻋل ﻜﻴﻤﻴﺎﺌﻲ ‪215 ...........................................‬‬

‫ﻋﺭﺽ ﺍﻝﻌﻼﻗﺔ ‪226 ..........................................................‬‬ ‫‪.1.I‬‬

‫ﺃﻤﺜﻠﺔ ﻋﻥ ﺍﺴﺘﻌﻤﺎل ﻋﻼﻗﺔ ﻨﺭﻨﺴﺕ ‪227 ........................................‬‬ ‫‪.2.I‬‬

‫ﺃﻨﻭﺍﻉ ﺍﻝﻤﺴﺎﺭﻱ ‪228 .........................................................‬‬ ‫‪.3.I‬‬

‫ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ ‪230 ..............................................‬‬ ‫‪.II‬‬

‫ﺴﻠﻭﻙ ﺠﻤﻠﺔ ‪230 ............................................................‬‬ ‫‪.1.II‬‬

‫ﺩﺭﺍﺴﺔ ﻜﻤﻴﺔ ﻝﺘﻁﻭﺭ ﺠﻤﻠﺔ‪ -‬ﺜﺎﺒﺕ ﺍﻝﺘﻭﺍﺯﻥ ‪233 ...............................‬‬ ‫‪.2.II‬‬

‫ﺍﻝﺘﻨﺒﺅ ﺒﺘﻔﺎﻋﻼﺕ ﺍﻷﻜﺴﺩﺓ ﻭﺍﻹﺭﺠﺎﻉ‪ -‬ﺘﻁﺒﻴﻕ ‪235 .............................‬‬ ‫‪.3.II‬‬

‫‪&'()( *+ %‬‬

‫ ‪, -./‬‬