‫ﺗﻄﻮﺭ ﲨﻠﺔ ﻛﻴﻤﻴﺎﺋﻴﺔ ﳓﻮ ﺣﺎﻟﺔ ﺍﻟﺘﻮﺍﺯﻥ‬

‫ﺍﻷﺳﺘﺎﺫ ‪ :‬ﻋﺎﻳﺐ ﻛﻤﺎﻝ ‪ /‬ﺑﻮﺳﻌﺎﺩﺓ‬

‫ﻣﺎﺋﻲ ‪:‬‬ ‫‪ PH -1‬ﳏﻠﻮﻝ‬

‫‪-1-1‬ﻣﻔﻬﻮﻡ ﺍﻟـ ‪: PH :‬‬
‫** ﻣﻦ ﺃﺟﻞ ﺍﶈﺎﻟﻴﻞ ﺍﳌﻤﺪﺩﺓ ) ‪ (  H 3O +  ≤ 5 × 10−2‬ﻓﺈﻥ ﺍﻟـ ‪ PH :‬ﳏﻠﻮﻝ ﻳﻌﺮﻑ ﻛﻤﺎﻳﻠﻲ ‪:‬‬
‫‪ H 3O +  = 10− PH‬‬ ‫ﺃﻱ‬ ‫‪PH = − log  H 3O + ‬‬
‫** ‪ : log‬ﺍﻟﻠﻮﻏﺎﺭﻳﺘﻢ ﺍﻟﻌﺸﺮﻱ ﲝﻴﺚ ‪log (1) = 0 , log (10 ) = 1 :‬‬
‫⇐ ‪PH = 2, 7 ⇐ PH = − log  H 3O + ‬‬ ‫‪{H O‬‬ ‫‪3‬‬
‫‪+‬‬
‫}‬
‫** ﻣﺜﺎﻝ ‪ ** :‬ﳏﻠﻮﻝ ‪ = 2 × 10−3 m ol .L −1 : s1‬‬
‫** ﳏﻠﻮﻝ ‪ H 3O +  = 2, 5 ×10 −9 mol .L −1 ⇐  H 3O +  = 10−8.6 ⇐ {PH = 8.6} : s 2‬‬
‫‪-2-1‬ﻗﻴﺎﺱ ﺍﻟـ ‪ : PH :‬ﻳﻘﺎﺱ ﺑﺎﺳﺘﻌﻤﺎﻝ ﻭﺭﻕ ﺍﻟـ ‪ PH‬ﺃﻭ ﺃﺣﺪ ﺍﻟﻜﻮﺍﺷﻒ ﺍﳌﻠﻮﻧﺔ ﺑﻄﺮﻳﻘﺔ ﺗﻘﺮﻳﺒﻴﺔ ﻭ ﳝﻜﻦ ﻗﻴﺎﺳﻪ ﺑﺄﻛﺜﺮ ﺩﻗﺔ‬
‫ﺑﺎﺳﺘﻌﻤﺎﻝ ﺟﻬﺎﺯ ﺍﻟـ ‪ PH‬ﻣﺘﺮ ﻣﺜﻼ ) ﺃﺧﺬ ﺃﻣﺜﻠﺔ ( ‪.‬‬
‫** ﲤﺮﻳﻦ ﺗﺪﺭﻳﱯ ‪ :‬ﻧﺬﻳﺐ ﻛﺘﻠﺔ ﻗﺪﺭﻫﺎ ‪ 0,32g‬ﻣﻦ ﻏﺎﺯ ‪ HCl‬ﰲ ﻣﻘﺪﺍﺭ ‪ 100 ml‬ﻣﻦ ﺍﳌﺎﺀ ﻋﻠﻤﺎ ﺃﻥ ﺍﻟﺘﻔﺎﻋﻞ ﻳﻜﻮﻥ ﺗﺎﻣﺎ ‪.‬‬
‫‪ -‬ﺃﻛﺘﺐ ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﰒ ﺍﺳﺘﻨﺘﺞ ‪ PH‬ﺍﶈﻠﻮﻝ ‪.‬‬
‫) ‪HCl ( g ) + H 2O ( l ) → H 3O (+aq ) + Cl (−aq‬‬ ‫** ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪no 8,76 × 10−3‬‬ ‫‪m 0,32‬‬
‫‪[ HCl ]o‬‬ ‫=‬ ‫=‬ ‫= ‪ no‬ﻭﻣﻨﻪ ‪= 8, 76 × 10−2‬‬ ‫=‬ ‫** ﺣﺴﺎﺏ ﺍﻟـ ‪= 8, 76 × 10−3 mol : PH‬‬
‫‪V‬‬ ‫‪0,1‬‬ ‫‪M 36,5‬‬
‫ﲟﺎ ﺃﻥ ﺍﻟﺘﻔﺎﻋﻞ ﺗﺎﻣﺎ ﻓﺈﻥ ‪ H 3O +  = 8, 76 × 10−2 ⇐ [ HCl ]o =  H 3O +  :‬‬
‫ﻭﻣﻦ ﺍﻟﻌﻼﻗﺔ ‪ PH = − log  H 3O + ‬ﳒﺪ ﺃﻥ ‪. PH = 1, 06 :‬‬
‫‪ -2‬ﳏﻠﻮﻝ ﲪﻀﻲ ﻭ ﳏﻠﻮﻝ ﺃﺳﺎﺳﻲ ‪:‬‬
‫‪-1-2‬ﺍﳊﻤﺾ ﺍﻟﻘﻮﻱ ﻭ ﺍﳊﻤﺾ ﺍﻟﻀﻌﻴﻒ ‪:‬‬
‫ﺗﺮﻛﻴﺰﻩ ‪ ca‬ﺃﻧﻪ ﲪﺾ ﻗﻮﻱ ﺇﺫﺍ ﺗﺸﺮﺩ ﰲ ﺍﳌﺎﺀ ﻛﻠﻴﺎ ﲝﻴﺚ ﻋﻨﺪ ﺍﻟﺘﻮﺍﺯﻥ ﻳﻜﻮﻥ ‪[ HA ]o = ca =  H O  :‬‬
‫‪3‬‬
‫‪+‬‬
‫** ﻧﻘﻮﻝ ﻋﻦ ﺍﳊﻤﺾ ‪HA‬‬
‫‪→ H 3O + + A −‬‬
‫‪. HA + H 2O ‬‬ ‫ﰲ ﺗﻔﺎﻋﻞ ﻳﻜﻮﻥ ﺗﺎﻣﺎ ‪:‬‬
‫〉 ‪[ HA ]o = ca‬‬ ‫** ﻧﻘﻮﻝ ﻋﻦ ﺍﳊﻤﺾ ‪ HA‬ﺗﺮﻛﻴﺰﻩ ‪ ca‬ﺃﻧﻪ ﲪﺾ ﺿﻌﻴﻒ ﺇﺫﺍ ﺗﺸﺮﺩ ﺟﺰﺋﻴﺎ ﰲ ﺍﳌﺎﺀ ﲝﻴﺚ ﻋﻨﺪ ﺍﻟﺘﻮﺍﺯﻥ ﻳﻜﻮﻥ ‪ H 3O  :‬‬
‫‪+‬‬

‫‪. HA + H 2O = H 3O + + A −‬‬ ‫ﰲ ﺗﻔﺎﻋﻞ ﻳﻜﻮﻥ ﻏﲑ ﺗﺎﻡ ‪:‬‬

‫** ﻣﺜﺎﻝ ‪ s 2 , s1 :‬ﲪﻀﺎﻥ ﲝﻴﺚ ‪:‬‬
‫‪.  H O  = 10− PH = 10−2 = C 1‬‬
‫‪3‬‬
‫‪+‬‬
‫‪ ⇐ {PH 1 = 2 ,C 1 = 10−2 mol .L −1} : HCl : s1 -‬ﺍﳊﻤﺾ ﻗﻮﻱ ﻷﻥ ‪:‬‬
‫‪ ⇐ {PH 2 = 3, 4 ,C 2 = 10−2 mol .L −1} : CH 3COOH : s 2 -‬ﺍﳊﻤﺾ ﺿﻌﻴﻒ ﻷﻥ ‪.  H O  = 3,98 ×10−4 〈 C 2 :‬‬
‫‪3‬‬
‫‪+‬‬

‫‪-2-2‬ﺍﻷﺳﺎﺱ ﺍﻟﻘﻮﻱ ﻭ ﺍﻷﺳﺎﺱ ﺍﻟﻀﻌﻴﻒ‪:‬‬

‫ﺃﻧﻪ ﺃﺳﺎﺱ ﻗﻮﻱ ﺇﺫﺍ ﺗﺸﺮﺩ ﰲ ﺍﳌﺎﺀ ﻛﻠﻴﺎ ﲝﻴﺚ ﻋﻨﺪ ﺍﻟﺘﻮﺍﺯﻥ ﻳﻜﻮﻥ ‪[ B ]o = OH −  :‬‬ ‫** ﻧﻘﻮﻝ ﻋﻦ ﺃﺳﺎﺱ ‪B‬‬
‫‪→ BH + + OH −‬‬
‫‪. B + H 2O ‬‬ ‫ﰲ ﺗﻔﺎﻋﻞ ﻳﻜﻮﻥ ﺗﺎﻣﺎ ‪:‬‬
‫‪[ B ]o‬‬ ‫** ﻧﻘﻮﻝ ﻋﻦ ﺃﺳﺎﺱ ‪ B‬ﺃﻧﻪ ﺃﺳﺎﺱ ﺿﻌﻴﻒ ﺇﺫﺍ ﺗﺸﺮﺩ ﰲ ﺍﳌﺎﺀ ﺟﺰﺋﻴﺎ ﲝﻴﺚ ﻋﻨﺪ ﺍﻟﺘﻮﺍﺯﻥ ﻳﻜﻮﻥ ‪〉 OH −  :‬‬
‫‪. B + H 2O = BH + + OH −‬‬ ‫ﰲ ﺗﻔﺎﻋﻞ ﻳﻜﻮﻥ ﻏﲑ ﺗﺎﻡ ‪:‬‬
‫‪12/1‬‬
‫** ﺗﻌﻄﻰ ﺍﻟﻌﻼﻗﺔ ﺑﲔ ﺍﻟﺘﺮﺍﻛﻴﺰ ‪  H O  ، OH − ‬ﰲ ) ‪ ( 25o C‬ﻛﻤﺎﻳﻠﻲ ‪ OH −  ×  H O  = 10−14‬ﺳﻨﺘﻄﺮﻕ ﳍﺎ ﺑﺎﻟﺘﻔﺼﻴﻞ ﻻﺣﻘﺎ ‪.‬‬
‫‪3‬‬
‫‪+‬‬
‫‪3‬‬
‫‪+‬‬

‫** ﻣﺜﺎﻝ ‪ s 2 , s1 :‬ﺃﺳﺎﺳﺎﻥ ﲝﻴﺚ ‪:‬‬

‫‪10−14‬‬
‫= ‪OH − ‬‬ ‫‪ :  H 3O +  = 10−12 ⇐ {PH 1 = 12 ,C 1 = 10−2 mol .L−1} : NaOH : s1 -‬ﻣﻦ ﺍﻟﻌﻼﻗﺔ ‪:‬‬
‫‪ H 3O ‬‬
‫‪+‬‬

‫ﳒﺪ ‪ ، OH −  = 10−2 mol .L−1 :‬ﻧﻼﺣﻆ ﺃﻥ ‪ OH −  = C 1‬ﻭﻣﻨﻪ ﺍﻷﺳﺎﺱ ‪ NaOH‬ﺃﺳﺎﺱ ﻗﻮﻱ ‪.‬‬
‫‪NaOH (aq ) ‬‬
‫‪H 2O‬‬
‫) ‪→ Na(+aq ) + OH (−aq‬‬ ‫ﲝﻴﺚ‬
‫‪: OH −  = 6,33 ×10−4 ⇐  H O  = 1, 58 ×10−11 ⇐ {PH 2 = 10,8 ,C 2 = 10−2 mol .L−1} : CH 3NH 2 : s 2 -‬‬
‫‪3‬‬
‫‪+‬‬

‫ﻧﻼﺣﻆ ﺃﻥ ‪ OH −  〈 C 2‬ﻭﻣﻨﻪ ﺍﻷﺳﺎﺱ ‪ CH 3NH 2‬ﺃﺳﺎﺱ ﺿﻌﻴﻒ‪.‬‬

‫) ‪CH 3NH 2 (aq ) + H 2O ( l ) = CH 3 NH 3+ (aq ) + OH (−aq‬‬ ‫ﲝﻴﺚ‬
‫‪ -3‬ﺗﻄﻮﺭ ﲨﻠﺔ ﻛﻴﻤﻴﺎﺋﻴﺔ ﳓﻮ ﺣﺎﻟﺔ ﺍﻟﺘﻮﺍﺯﻥ ‪:‬‬
‫‪-1-3‬ﻣﻘﺎﺭﻧﺔ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﻭ ﺍﻟﺘﻘﺪﻡ ﺍﻷﻋﻈﻤﻲ ‪) :‬ﻋﻤﻞ ﳐﱪﻱ(‪.‬‬
‫ﺃ‪ -‬ﺍﻟﺘﺠﺮﺑﺔ )‪ :(1‬ﰲ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﺍﻋﺘﻴﺎﺩﻳﺔ ﻧﺬﻳﺐ ‪ 0,1 mol‬ﻣﻦ ﲪﺾ ﺍﳋﻞ ﰲ ﻟﺘﺮ ﻣﻦ ﺍﳌﺎﺀ ﺍﳌﻘﻄﺮ ‪ ،‬ﻋﻨﺪ ﺍﻟﺘﻮﺍﺯﻥ ﻳﻌﻄﻲ ‪PH = 2, 9 :‬‬
‫* ﺍﻟﻜﻤﻴﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ‪no (CH 3COOH ) = 0,1 mol :‬‬
‫** ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ‪:‬‬
‫ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬ ‫) ‪CH 3COOH (aq ) + H 2O ( l ) → CH 3COO (−aq ) + H 3O (+aq‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ‬ ‫‪n 0 = 0,1‬‬ ‫ﺑﺰﻳﺎﺩﺓ‬ ‫‪0‬‬ ‫‪0‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ‬ ‫‪0,1 − x max‬‬ ‫ﺑﺰﻳﺎﺩﺓ‬ ‫‪x max‬‬ ‫‪x max‬‬

‫ﻭﻫﻮ ﺍﻟﺘﻘﺪﻡ ﺍﻷﻋﻈﻤﻲ‬ ‫‪ -‬ﻧﻈﺮﻳﺎ ‪ :‬ﻋﻨﺪ ﺗﻮﻗﻒ ﺍﻟﺘﻔﺎﻋﻞ ﻳﻜﻮﻥ ‪x max = 0,1 mol ................. (1) :‬‬
‫‪x‬‬ ‫‪0,1‬‬
‫‪ H 3O +  = 0,1 mol .L −1‬‬ ‫= ‪⇐  H 3O +  = max‬‬ ‫ﻭﻣﻨﻪ ﺣﺴﺐ ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ‪⇐ n H O + = x max :‬‬
‫‪V‬‬ ‫‪1‬‬ ‫‪3‬‬

‫‪ -‬ﻋﻤﻠﻴﺎ ‪ :‬ﻟﺪﻳﻨﺎ ‪ PH = 2, 9‬ﻭﻣﻨﻪ ‪ H 3O +  = 1, 26 × 10−3 mol .L −1 ⇐  H 3O +  = 10−2.9‬‬

‫‪ x f = 1, 26 ×10−3 mol‬ﻭﻫﻮ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ‪.‬‬ ‫‪⇐ n H O + =  H 3O +  V‬‬
‫‪3‬‬
‫ﻭ ﻟﺪﻳﻨﺎ ﺣﺴﺐ ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ‪. = x f :‬‬
‫‪xf‬‬ ‫‪xf‬‬ ‫‪1, 26‬‬
‫‪.‬‬ ‫‪= 1, 26 %‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬ ‫=‬ ‫ﻻﺣﻆ ﺃﻥ ‪ x max 〉 x f‬ﺑﺎﳊﺴﺎﺏ ﳒﺪ ‪= 0, 0126 〈 1 :‬‬
‫‪x max‬‬ ‫‪x max‬‬ ‫‪0,1‬‬
‫‪. VM‬‬ ‫‪= 24 l .mol −1‬‬ ‫ﺃ‪ -‬ﺍﻟﺘﺠﺮﺑﺔ )‪ : (2‬ﻧﺬﻳﺐ ‪ 240 ml‬ﻣﻦ ﻏﺎﺯ ‪ HCl‬ﰲ ‪ 1 L‬ﻣﻦ ﺍﳌﺎﺀ ﻓﻨﺠﺪ ‪ ، PH = 2 :‬ﲝﻴﺚ‬
‫‪0, 24‬‬ ‫‪Vg‬‬
‫= ) ‪. no ( HCl‬‬ ‫‪= 0, 01 mol‬‬ ‫= ) ‪⇐ no ( HCl‬‬ ‫* ﺍﻟﻜﻤﻴﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ‪:‬‬
‫‪22, 4‬‬ ‫‪VM‬‬
‫** ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ‪:‬‬
‫ﺍﳌﻌﺎﺩﻟﺔ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‬ ‫) ‪→ H 3O (+aq ) + Cl (−aq‬‬
‫‪HCl ( g ) + H 2O ( l ) ‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ‬ ‫‪n 0 = 0, 01‬‬ ‫ﺑﺰﻳﺎﺩﺓ‬ ‫‪0‬‬ ‫‪0‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ‬ ‫‪0, 01 − x max‬‬ ‫ﺑﺰﻳﺎﺩﺓ‬ ‫‪x max‬‬ ‫‪x max‬‬

‫‪ -‬ﻧﻈﺮﻳﺎ ‪ :‬ﻋﻨﺪ ﺗﻮﻗﻒ ﺍﻟﺘﻔﺎﻋﻞ ﻳﻜﻮﻥ ‪x max = 0, 01 mol ................. (1)′ :‬‬
‫‪x‬‬ ‫‪0, 01‬‬
‫‪.  H O  = 0, 01 mol .L−1‬‬
‫‪3‬‬
‫‪+‬‬
‫= ‪⇐  H 3O +  = max‬‬ ‫ﻭﻣﻨﻪ ﺣﺴﺐ ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ‪⇐ n H O + = x max :‬‬
‫‪V‬‬ ‫‪1‬‬ ‫‪3‬‬

‫‪12/2‬‬
 ‫‪ -‬ﻋﻤﻠﻴﺎ ‪ :‬ﻟﺪﻳﻨﺎ ‪ PH = 2‬ﻭﻣﻨﻪ ‪ H 3O +  = 10−2 mol .L −1 ⇐  H 3O +  = 10−2‬‬
‫‪.‬‬ ‫‪x f = 10−2 mol‬‬ ‫‪⇐ n H O + =  H 3O +  V‬‬
‫ﻭ ﻟﺪﻳﻨﺎ ﺣﺴﺐ ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ‪. = x f :‬‬
‫‪3‬‬

‫‪x‬‬ ‫‪x‬‬ ‫‪0, 01‬‬

‫= ‪ f‬ﻭﻣﻨﻪ ‪. f = 100 % :‬‬ ‫ﻻﺣﻆ ﺃﻥ ‪ x max = x f‬ﺑﺎﳊﺴﺎﺏ ﳒﺪ ‪= 1 :‬‬
‫‪x max‬‬ ‫‪x max 0, 01‬‬
‫‪xf‬‬ ‫) ‪x (t‬‬
‫= ‪.τ f‬‬ ‫= ) ‪، τ (t‬ﻭ ﺍﻟﻨﺴﺒﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ ﻟﻠﺘﻘﺪﻡ‬ ‫ﺃ‪ -‬ﻣﻌﺪﻝ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﻟﻠﺘﻔﺎﻋﻞ ‪ :‬ﻧﺴﺒﺔ ﺍﻟﺘﻘﺪﻡ ﰲ ﺃﻱ ﳊﻈﺔ ﺗﻌﺮﻑ ﻛﻤﺎﻳﻠﻲ‬
‫‪x max‬‬ ‫‪x max‬‬
‫** ﳌﺎ ‪ τ = 100 % ← τ = 1‬‬
‫‪ ←‬ﺍﻟﺘﺤﻮﻝ ﺗﺎﻡ ‪.‬‬
‫** ﳌﺎ ‪ τ 〈 100 % ← τ 〈 1‬‬
‫‪ ←‬ﺍﻟﺘﺤﻮﻝ ﻏﲑ ﺗﺎﻡ ‪.‬‬
‫‪-2-3‬ﻣﻔﻬﻮﻡ ﺣﺎﻟﺔ ﺍﻟﺘﻮﺍﺯﻥ ‪:‬‬
‫ﺃ‪ -‬ﲡﺮﺑﺔ )‪ : (1‬ﻧﻀﻊ ﻣﻘﺪﺍﺭ ‪ 50 ml‬ﻣﻦ ﳏﻠﻮﻝ ﲪﺾ ﺍﳋﻞ ) ‪ ( PH = 2,9‬ﰲ ﻛﺄﺱ ﰒ ﻧﻀﻴﻒ ﻟﻪ ﻗﻄﺮﺗﲔ ﻣﻦ ﳏﻠﻮﻝ ﲪﺾ ﺍﳋﻞ ﺍﳌﺮﻛﺰ‬
‫ﺗﺮﻛﻴﺰﻩ ‪ C = 0,1 mol .L−1‬ﻓﻨﻼﺣﻆ ﺑﻌﺪ ﺍﻟﺘﻮﺍﺯﻥ ﺃﻥ ﻣﻘﻴﺎﺱ ‪ PH‬ﻣﺘﺮ ﻳﺸﲑ ﺇﱃ ﺍﻟﻘﻴﻤﺔ ‪. PH = 2, 7‬‬
‫)‪(1‬‬
‫

↽ ) ‪CH 3COOH (aq ) + H 2O ( l‬‬
‫⇀


‬
‫
)‪( 2‬‬
‫) ‪CH 3COO (−aq ) + H 3O (+aq‬‬ ‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫** ﺍﻟﺘﻔﺴﲑ ‪ :‬ﺗﻨﺎﻗﺺ ‪ PH‬ﺍﶈﻠﻮﻝ ) ‪ ( 2, 7 ← 2, 9‬ﻧﺘﻴﺠﺔ ﺯﻳﺎﺩﺓ ﺍﻟﺘﺮﻛﻴﺰ ‪  H 3O + ‬ﻓﻴﻪ ﺃﻱ ﺯﻳﺎﺩﺓ ‪ x f‬ﻓﺎﻟﺘﻮﺍﺯﻥ ﻳﱰﺍﺡ ﰲ ﺍﻹﲡﺎﻩ ﺍﳌﺒﺎﺷﺮ )‪. (1‬‬
‫(‬ ‫)‬
‫ﺏ‪ -‬ﲡﺮﺑﺔ )‪ : (2‬ﻧﻌﻴﺪ ﻧﻔﺲ ﺍﻟﺘﺠﺮﺑﺔ ﺑﺈﺿﺎﻓﺔ ‪ 0,5 g‬ﻣﻦ ﺍﻳﺜﺎﻧﻮﺍﺕ ﺍﻟﺼﻮﺩﻳﻮﻡ ‪ CH 3COO − + Na +‬ﺇﱃ ﺍﻟﻜﺄﺱ ﺍﻟﺴﺎﺑﻖ ﻓﻴﺸﲑ‬
‫‪- PH‬ﻣﺘﺮ ﻟﻠﻘﻴﻤﺔ ‪. PH = 5‬‬
‫** ﺍﻟﺘﻔﺴﲑ ‪ :‬ﺗﺮﺗﻔﻊ ﻗﻴﻤﺔ ‪ PH‬ﺍﶈﻠﻮﻝ ) ‪ ( 5 ← 2,9‬ﻧﺘﻴﺠﺔ ﻧﻘﺼﺎﻥ ﺍﻟﺘﺮﻛﻴﺰ ‪  H 3O + ‬ﺃﻱ ﺗﻨﺎﻗﺺ ‪ x f‬ﻓﺎﻟﺘﻔﺎﻋﻞ ﰲ ﺍﻹﲡﺎﻩ ﺍﳌﻌﺎﻛﺲ ) ‪. ( 2‬‬
‫** ﻫﺬﺍ ﻳﻌﲏ ﺃﻥ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﻟﻠﺠﻤﻠﺔ ﻳﺘﻌﻠﻖ ﺑﺎﻟﺘﺮﺍﻛﻴﺰ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ‪.‬‬
‫‪ -3-3‬ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫)‪(1‬‬
‫

↽ ) ‪α A (aq ) + β B (aq‬‬
‫⇀


‬
‫
)‪( 2‬‬
‫ﻟﻴﻜﻦ ﺍﻟﺘﻔﺎﻋﻞ ﺍﻟﺬﻱ ﻳﺆﺩﻱ ﺇﱃ ﺗﻮﺍﺯﻥ ﻛﻴﻤﻴﺎﺋﻲ ‪γ C (aq ) + λ D (aq ) :‬‬

‫‪[C ] .[ D ]t‬‬
‫‪γ‬‬ ‫‪λ‬‬

‫‪. Q r (t ) = αt‬‬ ‫ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ﰲ ﺃﻱ ﳊﻈﺔ ﻳﻌﺮﻑ ﻛﻤﺎﻳﻠﻲ ‪:‬‬

‫‪[ A ]t .[ B ]t‬‬
‫‪β‬‬

‫‪1‬‬
‫ﲝﻴﺚ ‪ : Q1‬ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ﺍﳌﺒﺎﺷﺮ ‪ : Q 2 ،‬ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ﺍﻟﻌﻜﺴﻲ ‪.‬‬ ‫= ‪Q1‬‬ ‫** ﻣﻼﺣﻈﺔ ‪ :‬ﻧﻼﺣﻆ ﺑﺄﻥ‬
‫‪Q2‬‬
‫** ﺃﻣﺜﻠﺔ ‪:‬‬
‫‪CH 3COO − t .  H 3O + t‬‬
‫= ) ‪. Q r (t‬‬ ‫ﻳﻜﻮﻥ ‪:‬‬ ‫) ‪CH 3COOH ( aq ) + H 2O ( l ) = CH 3COO (−aq ) + H 3O (+aq‬‬ ‫‪ -1‬ﻟﻴﻜﻦ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫] ‪[CH COOH‬‬
‫‪3‬‬ ‫‪t‬‬

‫ﻧﺄﺧﺬ ﺍﺻﻄﻼﺣﺎ ‪ [ H 2O ] = 1 :‬ﰲ ﺣﺎﻟﺔ ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ ‪.‬‬

‫‪. Q r (t ) =  Pb 2+ t .  I − t‬‬
‫‪2‬‬
‫ﻳﻜﻮﻥ‬ ‫) ‪PbI 2 (s ) = Pb(2aq+ ) + 2I (−aq‬‬ ‫‪ -2‬ﻟﻴﻜﻦ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫ﻧﺄﺧﺬ ﺍﺻﻄﻼﺣﺎ ‪ , [ A ] = 1 :‬ﲝﻴﺚ ) ‪ : A (S‬ﺟﺴﻢ ﺻﻠﺐ‪.‬‬
‫‪ ،‬ﲝﻴﺚ ﳚـﺮﻱ ﺗﻄـﻮﺭ‬ ‫‪C 3 H 7OH‬‬ ‫ﻭ ﻛﺤﻮﻝ ﺍﻟﱪﻭﺑﺎﻧﻮﻝ‬ ‫‪CH 3COOH‬‬ ‫** ﲤﺮﻳﻦ ﺗﺪﺭﻳﱯ ‪ :‬ﻧﺴﺨﻦ ‪ 1 L‬ﻣﻦ ﺧﻠﻴﻂ ﻣﻜﻮﻥ ﻣﻦ ﲪﺾ ﺍﳋﻞ‬
‫‪CH 3COOH + C 3 H 7OH = CH 3COO − C 3 H 7 + H 2O‬‬ ‫ﺍﻟﺘﻔﺎﻋﻞ ﻛﻤﺎﻳﻠﻲ ‪:‬‬
‫ﲟﻌﺎﻳﺮﺓ ﺍﳊﻤﺾ ﺍﳌﺘﺒﻘﻲ ﰲ ﺍﳌﺰﻳﺞ ﲢﺼﻠﻨﺎﻋﻠﻰ ﺍﻟﻨﺘﺎﺋﺞ ﺍﻟﺘﺎﻟﻴﺔ ‪:‬‬
‫‪ -‬ﰲ ﺍﻟﻠﺤﻈﺔ ‪n (CH 3COO − C 3 H 7 ) = n ( H 2O ) = 0,58 mol ، n (CH 3COOH ) = n (C 3 H 7OH ) = 0, 42 mol : t 1‬‬
‫‪n (CH 3COO − C 3 H 7 ) = n ( H 2O ) = 0, 66 mol‬‬ ‫‪ -‬ﰲ ﺍﻟﻠﺤﻈﺔ ‪، n (CH 3COOH ) = n (C 3 H 7OH ) = 0, 34 mol : t 2‬‬
‫‪ -‬ﺃﺣﺴﺐ ﺍﻟﻜﺴﻮﺭ ) ‪ Q r (t 2 ) ، Q r (t 1 ) ، Q r ( 0‬ﻟﻠﺘﻔﺎﻋﻞ ﺍﳌﺬﻛﻮﺭ ‪ ،‬ﻭﺍﺳﺘﻨﺘﺞ ﺟﻬﺔ ﺗﻄﻮﺭ ﺍﻟﺘﻔﺎﻋﻞ ﺑﲔ ﺍﻟﻠﺤﻈﺘﲔ ‪ t1‬ﻭ ‪. t 2‬‬
‫‪12/3‬‬
 ‫] ‪[CH COO − C H ] [ H O‬‬
‫‪.‬‬ ‫= ) ‪Q r (t‬‬ ‫** ﺍﳊﻞ ‪ :‬ﺣﺴﺎﺏ‬
‫‪3‬‬ ‫‪3‬‬ ‫‪7‬‬ ‫‪t‬‬ ‫‪2‬‬ ‫‪t‬‬

‫] ‪[CH COOH ] .[C H OH‬‬‫‪3‬‬ ‫‪t‬‬ ‫‪3‬‬ ‫‪7‬‬ ‫‪t‬‬

‫‪no (CH 3COO − C 3 H 7 ) = no ( H 2O ) = 0‬‬ ‫‪ -‬ﳌﺎ ‪، no (CH 3COOH ) = no (C 3 H 7OH ) = 1 mol : t = 0‬‬
‫‪. Qr (0) = 0‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬
‫‪0,58 0,58‬‬
‫‪.‬‬
‫‪. Q r (t1 ) = 1,9‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬ ‫‪Q r (t 1 ) = V‬‬ ‫‪V‬‬ ‫‪ -‬ﳌﺎ ‪: t = t1‬‬
‫‪0, 42 0, 42‬‬
‫‪.‬‬
‫‪V‬‬ ‫‪V‬‬
‫‪. Q r (t 2 ) = 3,76‬‬ ‫‪ -‬ﳌﺎ ‪ t = t 2‬ﺑﻨﻔﺲ ﺍﻟﻄﺮﻳﻘﺔ ﳒﺪ‬
‫ﻓﺎﻟﺘﻔﺎﻋﻞ ﳚﺮﻱ ﰲ ﺍﳉﻬﺔ ﺍﳌﺒﺎﺷﺮﺓ ﺑﲔ ﺍﳊﻈﺘﲔ ‪ t 1‬ﻭ ‪. t 2‬‬ ‫ﻧﻼﺣﻆ ﺃﻥ ‪Q r (t 2 ) 〉 Q r (t 1 ) :‬‬
‫‪ -4-3‬ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﺍﻟﻜﻴﻤﻴﺎﺋﻲ ‪: K‬‬
‫ﺃ‪ -‬ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ﰲ ﺣﺎﻟﺔ ﺍﻟﺘﻮﺍﺯﻥ ‪ :‬ﳓﻀﺮ ﳏﻠﻮﻟﲔ ‪ s 2 , s1‬ﳊﻤﺾ ﺍﻹﻳﺜﺎﻧﻮﻳﻚ ﲝﻴﺚ ‪:‬‬
‫{‬
‫* ‪. PH = 3,56 , C 2 = 5 × 10−3 mol .L−1 : s 2‬‬ ‫}‬ ‫‪{PH = 3, 4 , C‬‬ ‫‪1‬‬ ‫* ‪= 10−2 mol .L−1 : s 1‬‬ ‫}‬
‫‪CH 3COO −  f .  H 3O +  f‬‬
‫= ‪Qr f‬‬ ‫) ‪CH 3COOH ( aq ) + H 2O ( l ) → CH 3COO ( aq ) + H 3O ( aq‬‬
‫‪−‬‬ ‫‪+‬‬
‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫] ‪[CH COOH‬‬ ‫‪3‬‬ ‫‪f‬‬
‫‪−‬‬ ‫‪+‬‬ ‫‪−‬‬
‫)ﺑﻘﻠﺔ(‬ ‫) ‪OH (aq‬‬ ‫‪،‬‬ ‫) ‪H 3O ( aq‬‬ ‫‪،‬‬ ‫) ‪H 2O ( l‬‬ ‫‪،‬‬ ‫) ‪CH 3COO ( aq‬‬ ‫‪،‬‬ ‫) ‪CH 3COOH ( aq‬‬ ‫** ﺣﺴﺎﺏ ﺗﺮﺍﻛﻴﺰ ﺍﻷﻓﺮﺍﺩ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ ﺍﳌﺘﻮﺍﺟﺪﺓ ‪:‬‬
‫ﺣﺴﺐ ﻣﺒﺪﺃ ﺍﳓﻔﺎﻅ ﺍﻟﺸﺤﻨﺔ ‪:‬‬
‫)‪.  H 3O +  = CH 3COO −  = 10− PH ............... (1‬‬ ‫)ﻣﻬﻤﻠﺔ( ‪⇐  H 3O +  = CH 3COO −  + OH − ‬‬
‫ﺣﺴﺐ ﻣﺒﺪﺃ ﺍﳓﻔﺎﻅ ﺍﳌﺎﺩﺓ ‪:‬‬
‫‪[CH COOH ] = C − CH COO − ‬‬
‫‪3‬‬
‫‪⇐ [CH COOH ]o = C‬‬ ‫‪3‬‬ ‫‪3‬‬
‫‪= [CH 3COOH ] + CH 3COO − ‬‬
‫) ‪[CH COOH ] = C − 10− PH ...................( 2‬‬
‫‪3‬‬
‫ﻣﻦ ﺍﻟﻌﻼﻗﺔ )‪ (1‬ﳒﺪ‬
‫) ‪(10‬‬‫‪− PH‬‬ ‫‪2‬‬

‫= ‪Qr f‬‬ ‫ﻳﺼﺒﺢ ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ‬

‫‪(C‬‬ ‫‪1‬‬ ‫‪− 10 − PH‬‬ ‫)‬
‫ﺗﻄﺒﻴﻖ ﻋﺪﺩﻱ ﳒﺪ ‪:‬‬
‫‪[CH COOH ] = 9, 6 ×10−3 mol .L−1 ،‬‬
‫‪3‬‬
‫‪ -‬ﺍﶈﻠﻮﻝ ‪ H 3O +  = CH 3COO −  = 3, 98 × 10 −4 mol .L −1 : s1‬‬
‫‪Q r f 1 = 1, 65 × 10−5‬‬ ‫ﻭﻣﻨﻪ ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ‬
‫‪[CH COOH ] = 4, 72 ×10−3 mol .L−1 ،‬‬
‫‪3‬‬
‫‪ -‬ﺍﶈﻠﻮﻝ ‪ H 3O +  = CH 3COO −  = 2, 75 × 10−4 mol .L−1 : s 2‬‬
‫‪Q r f 2 = 1, 65 × 10−5‬‬ ‫ﻭﻣﻨﻪ ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ‬
‫** ﻧﻼﺣﻆ ﺃﻥ ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ﺍﻟﻨﻬﺎﺋﻲ ﻳﻜﻮﻥ ﻧﻔﺴﻪ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻠﺠﻤﻠﺘﲔ ﺍﳌﺘﻮﺍﺯﻳﺘﲔ ﻭ ﻫﻮ ﻻ ﻳﺘﻌﻠﻖ ﺑﺎﻟﺘﺮﺍﻛﻴﺰ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ﻟﻠﻤﺤﻠﻮﻟﲔ ‪.‬‬
‫] ‪[C ] .[ D‬‬
‫‪γ‬‬ ‫‪λ‬‬

‫‪.K‬‬ ‫‪= Qr‬‬ ‫=‬ ‫‪f‬‬

‫ﻗﻴﻤﺘﻪ ﺗﺴﺎﻭﻱ ‪ Q r f‬ﻭ ﻳﻜﺘﺐ ﻛﻤﺎﻳﻠﻲ ‪:‬‬
‫‪f‬‬
‫ﺏ‪ -‬ﻣﻔﻬﻮﻡ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ‪ : K‬ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﺭﻣﺰﻩ ‪K‬‬
‫] ‪[ A ] .[ B‬‬
‫‪f‬‬ ‫‪α‬‬ ‫‪β‬‬
‫‪f‬‬ ‫‪f‬‬

‫ﺟـ‪ -‬ﺗﺄﺛﲑ ﺍﳊﺎﻟﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ﳉﻤﻠﺔ ﻛﻴﻤﻴﺎﺋﻴﺔ ﻋﻠﻰ ﺣﺎﻟﺔ ﺍﻟﺘﻮﺍﺯﻥ ‪:‬‬
‫** ﲡﺮﺑﺔ ‪ :‬ﻧﻘﻴﺲ ﺍﻟﻨﺎﻗﻠﻴﺔ ﺍﻟﻨﻮﻋﻴﺔ ﶈﻠﻮﻟﲔ ﳊﻤﺾ ﺍﻟﱪﻭﺑﺎﻧﻮﻳﻚ ‪. C 2 H 5COOH :‬‬
‫‪{σ‬‬ ‫‪2‬‬
‫* ‪= 43 × 10−4 sm −1 , C 2 = 10−3 mol .L−1 : s 2‬‬ ‫}‬ ‫‪{σ‬‬ ‫‪1‬‬
‫* ‪= 1, 43 × 10 −4 sm −1 , C 1 = 10−2 mol .L−1 : s 1‬‬ ‫}‬
‫‪. { λH O‬‬ ‫‪3‬‬
‫‪+‬‬ ‫‪= 35 ms m 2 .mol −1 , λC‬‬
‫‪2 H 5COO‬‬
‫‪−‬‬ ‫‪= 3, 58 ms m 2 .mol −1‬‬ ‫ﲝﻴﺚ ﺍﻟﻨﺎﻗﻠﻴﺔ ﺍﻟﻨﻮﻋﻴﺔ ﺍﻟﺸﺎﺭﺩﻳﺔ ﻟﻠﺸﻮﺍﺭﺩ ﺍﳌﺘﻮﺍﺟﺪﺓ ‪} :‬‬
‫‪−‬‬ ‫‪+‬‬
‫) ‪C 2 H 5COOH ( aq ) + H 2O ( l ) → C 2 H 5COO ( aq ) + H 3O ( aq‬‬ ‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪12/4‬‬
 ‫‪) OH (−aq ) ،‬ﺑﻘﻠﺔ( ‪.‬‬ ‫) ‪H 3O ( aq‬‬
‫‪+‬‬
‫‪،‬‬ ‫) ‪H 2O ( l‬‬
‫‪−‬‬
‫** ﺍﻷﻓﺮﺍﺩ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ ﺍﳌﺘﻮﺍﺟﺪﺓ ﻫﻲ ‪، C 2H 5COO(aq ) ، C 2 H 5COOH (aq ) :‬‬
‫ﻟﺪﻳﻨﺎ ‪σ = λH O  H O  + λC H COO C 2 H COO  :‬‬
‫‪+‬‬ ‫‪3‬‬
‫‪+‬‬
‫‪−‬‬ ‫‪5‬‬
‫‪−‬‬
‫** ﺣﺴﺎﺏ ﺗﺮﺍﻛﻴﺰ ﺍﻷﻓﺮﺍﺩ ‪:‬‬
‫‪3‬‬ ‫‪2‬‬ ‫‪5‬‬

‫(‬
‫‪σ = λH O + λC H COO  H O ‬‬
‫‪3‬‬
‫‪+‬‬
‫‪2‬‬ ‫‪5‬‬
‫‪−‬‬ ‫)‬ ‫‪3‬‬
‫‪+‬‬
‫ﺣﺴﺐ ﻣﺒﺪﺃ ﺍﳓﻔﺎﻅ ﺍﻟﺸﺤﻨﺔ ‪⇐  H 3O +  = CH 3COO −  :‬‬
‫‪σ‬‬
‫= ‪ H 3O + ‬‬ ‫⇐‬
‫‪(λ‬‬ ‫‪H 3O‬‬ ‫‪+‬‬ ‫‪+ λC‬‬
‫‪2 H 5COO‬‬
‫‪−‬‬ ‫)‬
‫‪. [C 2 H COOH ]f = C −  H O +  f‬‬
‫‪5‬‬ ‫‪3‬‬
‫⇐‬ ‫‪[C‬‬ ‫‪2‬‬
‫‪H 5COOH‬‬ ‫‪]f‬‬ ‫ﻭ ﺣﺴﺐ ﻣﺒﺪﺃ ﺍﳓﻔﺎﻅ ﺍﳌﺎﺩﺓ ‪= C − C 2 H 5COO −  :‬‬
‫‪f‬‬

‫‪ H 3O + ‬‬ ‫‪xf‬‬

‫= ‪. τf‬‬ ‫‪f‬‬
‫= ‪⇐ τf‬‬ ‫** ﺍﻟﻨﺴﺒﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ ﻟﺘﻘﺪﻡ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪C‬‬ ‫‪x max‬‬
‫** ﺗﻄﺒﻴﻖ ﻋﺪﺩﻱ ‪:‬‬
‫‪ -‬ﺍﶈﻠﻮﻝ ‪. τ f = 3, 7 % ، [C 2 H COOH ]f = 9, 63 ×10−2 mol .L−1 ،  H O  = C 2 H COO  = 3, 71×10−3 mol .L−1 : s1‬‬
‫‪5‬‬ ‫‪3‬‬
‫‪+‬‬
‫‪5‬‬
‫‪−‬‬

‫‪ -‬ﺍﶈﻠﻮﻝ ‪. τ f = 11 % ، [C 2 H COOH ]f = 8,89 × 10−4 mol .L −1 ،  H O  = C 2 H COO  = 1,11×10 −4 mol .L−1 : s1‬‬
‫‪5‬‬ ‫‪3‬‬
‫‪+‬‬
‫‪5‬‬
‫‪−‬‬

‫** ﻭﻣﻨﻪ ﺍﻟﻨﺴﺒﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ ﻟﺘﻘﺪﻡ ﺍﻟﺘﻔﺎﻋﻞ ﺗﺘﻌﻠﻖ ﺑﺎﳊﺎﻟﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ﻟﻠﺠﻤﻠﺔ ‪.‬‬
‫ﺩ‪ -‬ﺍﻟﻨﺴﺒﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ ﻟﺘﻘﺪﻡ ﺍﻟﺘﻔﺎﻋﻞ ﻭ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ‪:‬‬
‫ﳓﻀﺮ ﳏﻠﻮﻟﲔ ﳍﻤﺎ ﻧﻔﺲ ﺍﻟﺘﺮﻛﻴﺰ ‪: C = 10−2 mol .L−1‬‬
‫** ﺍﶈﻠﻮﻝ ‪ : s1‬ﲪﺾ ﺍﳋﻞ ) ‪. {PH = 3, 4 , K 1 = 1, 6 ×10−5 mol .L−1} : (CH COOH‬‬ ‫‪3‬‬

‫** ﺍﶈﻠﻮﻝ ‪ : s 2‬ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ) ‪. {PH = 2, 9 , K 2 = 1, 6 ×10−4 mol .L−1} : ( HCOOH‬‬

‫ﻣﻌﺎﺩﻟﺘﺎ ﺍﻟﺘﻔﺎﻋﻞ ‪. HCOOH (aq ) + H 2O ( l ) → HCOO (−aq ) + H 3O (+aq ) ، CH 3COOH (aq ) + H 2O ( l ) → CH 3COO (−aq ) + H 3O (+aq ) :‬‬
‫‪ H 3O + ‬‬ ‫‪xf‬‬
‫= ‪ τ f‬ﻭﻣﻨﻪ ‪:‬‬ ‫‪f‬‬
‫= ‪⇐ τf‬‬ ‫ﻧﺴﺒﺔ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ‪:‬‬
‫‪C‬‬ ‫‪x max‬‬
‫‪3, 98 × 10 −4‬‬
‫= ‪* τf‬‬ ‫⇒ ‪= 0, 04‬‬ ‫‪τf = 4 %‬‬
‫‪10−2‬‬
‫‪1, 26 ×10 −3‬‬
‫= ‪* τf‬‬ ‫⇒ ‪= 0,126‬‬ ‫‪τ f = 12, 6 %‬‬
‫‪10−2‬‬
‫** ﻧﻼﺣﻆ ﺃﻥ ‪ τ 1 ≠ τ 2 :‬ﻷﻥ ‪ K 1 ≠ K 2‬ﺭﻏﻢ ﺃﻥ ‪. C 1 = C 2‬‬
‫ﲝﻴـﺚ ‪:‬‬ ‫‪AH + H 2O → A − + H 3O +‬‬ ‫** ﻳﺘﻌﻠﻖ ﻣﻌﺪﻝ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨـﻬﺎﺋﻲ ﻟﻠﺘﻔﺎﻋـﻞ ﺍﻟﻜﻴﻤﻴـﺎﺋﻲ ﺑﺜﺎﺑـﺖ ﺍﻟﺘـﻮﺍﺯﻥ ﰲ ﺍﻟﺘﻔﺎﻋـﻞ ‪:‬‬
‫‪‬‬ ‫‪ H O  ‬‬ ‫‪ A −  f .  H 3O +  f‬‬ ‫‪+‬‬

‫= ‪[ AH ] = C −  H O  = C − C ⋅ τ = C (1 − τ ) ;  H O  = τ ⋅ C ⇐ τ‬‬ ‫= ‪ K‬ﻭ ﻟﺪﻳﻨﺎ ‪‬‬

‫‪+‬‬ ‫‪+‬‬ ‫‪3‬‬

‫‪‬‬
‫‪3‬‬
‫‪C ‬‬ ‫‪‬‬
‫‪3‬‬
‫‪[ AH ]f‬‬
‫) ‪(τ ⋅C‬‬
‫‪2‬‬
‫‪τ2‬‬
‫= ‪K‬‬ ‫‪C‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬ ‫‪K‬‬ ‫=‬ ‫⇐‬
‫) ‪(1 − τ‬‬ ‫) ‪C (1 − τ‬‬
‫ﻫـ‪ -‬ﺣﺎﻟﺔ ﺍﻟﺘﻮﺍﺯﻥ ﺍﻟﺪﻳﻨﺎﻣﻴﻜﻲ ﳉﻤﻠﺔ ﻛﻴﻤﻴﺎﺋﻴﺔ ‪ ) :‬ﺍﻟﺘﻔﺴﲑ ﺍ‪‬ﻬﺮﻱ(‬
‫ﺣﱴ ﳛﺪﺙ ﺗﻔﺎﻋﻞ ﻛﻴﻤﻴﺎﺋﻲ ﺑﲔ ﻣﺘﻔﺎﻋﻠﲔ ‪ A‬ﻭ ‪ B‬ﰲ ﺩﺭﺟﺔ ﺣﺮﺍﺭﺓ ﻣﻌﻴﻨﺔ ﻓﺈﻧﻪ ﻻﺑﺪ ﺃﻥ ﳛﺪﺙ ﺗﺼﺎﺩﻡ ﻓﻌﺎﻝ ﺑﲔ ﺍﳉﺰﻳﺌﺎﺕ ﻳﺆﺩﻱ ﺇﱃ ﺗﻜـﺴﺮ‬
‫ﺭﻭﺍﺑﻂ ﻭﺗﺸﻜﻴﻞ ﺃﺧﺮﻯ ‪ ،‬ﻟﻨﺤﺼﻞ ﻋﻠﻰ ﺃﺟﺴﺎﻡ ﺃﺧﺮﻯ )ﻧﻮﺍﺗﺞ( ‪ C‬ﻭ ‪. D‬‬
‫** ﺗﺒﻠﻎ ﺍﳉﻤﻠﺔ ﺗﻮﺍﺯ‪‬ﺎ ﺍﻟﺪﻳﻨﺎﻣﻴﻜﻲ ﻋﻨﺪﻣﺎ ﻳﺼﺒﺢ ﺳﺮﻋﺔ ﺍﺧﺘﻔﺎﺀ ﺍﳌﺘﻔﺎﻋﻼﺕ ﻣﺴﺎﻭﻳﺔ ﲤﺎﻣﺎ ﻟﺴﺮﻋﺔ ﻇﻬﻮﺭ ﺍﻟﻨﻮﺍﺗﺞ ‪:‬‬
‫‪A + B ⇌C + D‬‬

‫‪12/5‬‬
 ‫‪ -4‬ﺍﻟﺘﺤﻮﻻﺕ ﲪﺾ ‪ -‬ﺃﺳﺎﺱ ‪:‬‬
‫‪-1-4‬ﺍﶈﺎﻟﻴﻞ ﺍﳌﺎﺋﻴﺔ ‪:‬‬
‫) ‪2H 2O ( l ) = H 3O (+aq ) + OH (−aq‬‬ ‫ﺃ‪ -‬ﺍﻟﺘﻔﻜﻚ ﺍﻟﺬﺍﰐ ﻟﻠﻤﺎﺀ ‪ :‬ﺍﳌﺎﺀ ﺍﳌﻘﻄﺮ ﻳﺘﻔﻜﻚ ﺫﺍﺗﻴﺎ ﺣﺴﺐ ﺍﳌﻌﺎﺩﻟﺔ ‪:‬‬
‫‪+‬‬ ‫‪−‬‬ ‫‪−7‬‬
‫ﲝﻴﺚ ﺗﻜﻮﻥ ﺗﺮﺍﻛﻴﺰ ﺷﻮﺍﺭﺩﻩ ﰲ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ‪ H 3O  = OH  = 10 mol .L : 25 C‬‬
‫‪−1‬‬ ‫‪o‬‬

‫ﺏ‪ -‬ﺍﳉﺪﺍﺀ ﺍﻟﺸﺎﺭﺩﻱ ﻟﻠﻤﺎﺀ ‪ : Ke‬ﻫﻮ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﻟﻠﻤﻌﺎﺩﻟﺔ ﺍﻟﺴﺎﺑﻘﺔ ‪ ،‬ﲝﻴﺚ ‪. Ke =  H 3O +  × OH − ‬‬
‫ﻣﻦ ﺃﺟﻞ ‪ 25o C‬ﻳﻜﻮﻥ ‪ ، Ke = 10−14‬ﻧﻌﺮﻑ ‪ pKe‬ﻛﻤﺎﻳﻠﻲ ‪. pKe = 14 ⇐ pKe = − log Ke‬‬
‫ﻳﺰﺩﺍﺩ ﺑﺎﺭﺗﻔﺎﻉ ﺩﺭﺟﺔ ﺍﳊﺮﺍﺭﺓ ﻭ ﻳﻘﻞ ﺑﺎﳔﻔﺎﻇﻬﺎ ‪.‬‬
‫ﺍﶈﻠﻮﻝ ﺍﳌﺎﺋﻲ ﻳﻜﻮﻥ ‪:‬‬ ‫‪25o C‬‬ ‫ﺟـ‪-‬ﺳﻠﻢ ﺍﻟـ ‪ : PH‬ﻋﻨﺪ‬
‫‪.‬‬ ‫‪PH 〈 7 ←‬‬
‫‪  H 3O +  〉 OH − ‬‬ ‫‪ ** .‬ﲪﻀﻴﺎ ﳌﺎ ‪:‬‬ ‫‪PH = 7 ←‬‬
‫‪  H 3O +  = OH − ‬‬ ‫** ﻣﻌﺘﺪﻻ ﳌﺎ ‪:‬‬
‫‪.‬‬ ‫‪PH 〉 7 ←‬‬
‫‪  H 3O +  〈 OH − ‬‬ ‫** ﺃﺳﺎﺳﻴﺎ ﳌﺎ ‪:‬‬
‫‪-2-4‬ﺛﺎﺑﺖ ﺍﳊﻤﻮﺿﺔ ‪ PKa, Ka‬ﻟﻠﺜﻨﺎﺋﻴﺔ ﲪﺾ ‪ -‬ﺃﺳﺎﺱ ‪:‬‬
‫‪.‬‬ ‫‪A H + H 2O → A − + H 3O +‬‬ ‫ﻣﻊ ﺍﳌﺎﺀ‬ ‫‪AH‬‬ ‫ﺃ‪ -‬ﺛﺎﺑﺖ ﺍﳊﻤﻮﺿﺔ ‪ Ka‬ﻟﻠﺜﻨﺎﺋﻴﺔ ﲪﺾ – ﺃﺳﺎﺱ ‪ :‬ﻣﻌﺎﺩﻟﺔ ﺗﻔﺎﻋﻞ ﺍﳊﻤﺾ‬
‫‪ A −  f .  H 3O +  f‬‬
‫= ‪Ka = K‬‬ ‫ﺇﻥ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﳌﻌﺎﺩﻟﺔ ﺗﻔﺎﻋﻞ ﲪﺾ ﺗﺪﻋﻰ ﺑﺜﺎﺑﺖ ﺍﳊﻤﻮﺿﺔ ﻟﻠﺜﻨﺎﺋﻴﺔ ) ‪: ( A H / A −‬‬
‫] ‪[ AH‬‬ ‫‪f‬‬

‫‪ PKa = − log Ka‬ﻭ ‪. Ka = 10− PKa‬‬ ‫ﲝﻴﺚ ‪:‬‬

‫** ﻛﻠﻤﺎ ﻛﺎﻥ ‪ Ka‬ﺃﻛﱪ ﻛﺎﻥ ‪ pKa‬ﺃﺻﻐﺮ ← ﺍﳊﻤﺾ ﺃﻗﻮﻯ ﻭ ﺍﻷﺳﺎﺱ ﺃﺿﻌﻒ ﻭ ﺍﻟﻌﻜﺲ ‪.‬‬
‫‪ A −  f .  H 3O +  f‬‬
‫= ‪Ka‬‬ ‫‪ . A H + H 2O → A − + H 3O +‬ﻳﻜﻮﻥ‬ ‫ﺏ‪ -‬ﺍﻟﻌﻼﻗﺔ ﺑﲔ ‪ PH‬ﻭ ‪ : PKa‬ﰲ ﺍﳌﻌﺎﺩﻟﺔ‬
‫] ‪[ AH‬‬ ‫‪f‬‬

‫] ‪[A‬‬‫‪−‬‬
‫‪.‬‬ ‫] ‪[A‬‬ ‫‪−‬‬
‫‪.‬‬
‫‪.‬‬ ‫‪PKa = PH − log‬‬ ‫‪f‬‬
‫ﻭﻣﻨﻪ‬ ‫‪log Ka = log  H 3O +  + log‬‬ ‫‪f‬‬
‫ﺑﺎﺩﺧﺎﻝ ﺍﻟﻠﻮﻏﺎﺭﻳﺘﻢ ﺗﺼﺒﺢ ‪:‬‬
‫] ‪[ AH‬‬ ‫‪f‬‬
‫‪f‬‬
‫] ‪[ AH‬‬ ‫‪f‬‬

‫] أ[‬
‫‪.‬‬ ‫‪PH = PKa + log‬‬ ‫ﺑﺼﻔﺔ ﻋﺎﻣﺔ ‪ :‬ﺗﻜﻮﻥ ﺍﻟﻌﻼﻗﺔ ﺑﲔ ‪ PH‬ﻭ ‪PKa‬‬
‫] ح[‬
‫] أ[‬
‫‪.‬‬ ‫‪PH = PKa + log‬‬
‫] ح[‬
‫(‬ ‫)‬
‫ﺟـ‪ -‬ﳎﺎﻻﺕ ﺗﻐﻠﺐ ﺍﻟﺼﻔﺔ ﺍﳊﻤﻀﻴﺔ ﻭ ﺍﻷﺳﺎﺳﻴﺔ ﻟﻠﺜﻨﺎﺋﻴﺔ ‪ : AH / A −‬ﻣﻦ ﺍﻟﻌﻼﻗﺔ ‪:‬‬
‫] أ[‬
‫‪ ←‬ﻻ ﺗﻮﺟﺪ ﺻﻔﺔ ﻏﺎﻟﺒﺔ ‪.‬‬‫‪‬‬ ‫‪= 1 ←‬‬‫** ﺍﳊﺎﻟﺔ )‪ PH = PKa : (1‬‬
‫] ح[‬
‫] أ[‬ ‫] أ[‬
‫‪ ←‬ﺍﻟﺼﻔﺔ ﺍﻟﻐﺎﻟﺒﺔ ﻫﻲ ﺍﻷﺳﺎﺳﻴﺔ ‪.‬‬‫‪‬‬ ‫‪〉 1 ←‬‬‫‪ log‬‬ ‫‪〉 0 ←‬‬ ‫** ﺍﳊﺎﻟﺔ ) ‪ PH 〉 PKa : ( 2‬‬
‫] ح[‬ ‫] ح[‬
‫] أ[‬ ‫] أ[‬
‫‪ ←‬ﺍﻟﺼﻔﺔ ﺍﻟﻐﺎﻟﺒﺔ ﻫﻲ ﺍﳊﻤﻀﻴﺔ ‪.‬‬ ‫‪‬‬ ‫‪〈 1 ←‬‬
‫‪ log‬‬ ‫‪〈 0 ←‬‬ ‫** ﺍﳊﺎﻟﺔ )‪ PH 〈 PKa : ( 3‬‬
‫] ح[‬ ‫] ح[‬
‫] ‪[A ] 〉 [B‬‬ ‫] ‪[A ] = [B‬‬ ‫] ‪[A ] 〈 [B‬‬ ‫‪PH‬‬
‫ﲪﻀﻲ‬ ‫‪PKa = PH‬‬ ‫ﺃﺳﺎﺳﻲ‬
‫‪en %‬‬ ‫** ﳐﻄﻂ ﺗﻮﺯﻳﻊ ﺍﻟﺼﻔﺔ ﺍﻟﻐﺎﻟﺒﺔ ‪:‬‬
‫‪100%‬‬ ‫ﰲ ﻣﺜﺎﻝ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ﻋﻨﺪ ﺗﻘﺎﻃﻊ ﺍﳌﻨﺤﻨﻴﲔ‬
‫‪HCOOH % = HCOO − %‬‬ ‫ﻳﻜﻮﻥ ‪:‬‬
‫‪PH = PKa = 4,8‬‬
‫‪50%‬‬
‫ﳒﺪ ﺃﻥ ‪:‬‬

‫‪PH‬‬
‫‪PKa = 4, 8‬‬
‫‪12/6‬‬
 ‫ﺩ‪ -‬ﺗﻄﺒﻴﻖ ﻋﻠﻰ ﺍﻟﻜﺎﺷﻒ ﺍﳌﻠﻮﻥ ‪:‬‬
‫ﺍﻟﻜﻮﺍﺷﻒ ﺍﳌﻠﻮﻧﺔ ﻫﻲ ﺃﻧﻮﺍﻉ ﻛﻴﻤﻴﺎﺋﻴﺔ ﻣﻌﻘﺪﺓ ﺍﻟﺘﺮﻛﻴﺐ ﻏﺎﻟﺒﺎ ﻣﺎ ﺗﻜﻮﻥ ﺃﲪﺎﺿﺎ ﺿﻌﻴﻔﺔ ﻧﺮﻣﺰ ﳍﺎ ﻣﺜﻼ ‪ HInd :‬ﻋﻨـﺪ ﻭﺿـﻌﻬﺎ ﰲ ﺍﶈﻠـﻮﻝ‬
‫‪HInd + H 2O = Ind − + H 3O +‬‬ ‫ﺗﺘﻮﺍﺯﻥ ﺍﻟﺜﻨﺎﺋﻴﺔ ‪ HInd / Ind −‬ﻛﻤﺎﻳﻠﻲ ‪:‬‬
‫] ‪[ Ind‬‬
‫‪−‬‬
‫‪ Ind  .  H 3O ‬‬
‫‪−‬‬ ‫‪+‬‬

‫‪. PH = PKai + log‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬ ‫‪Kai = ‬‬ ‫ﻓﻴﻜﻮﻥ ‪:‬‬

‫] ‪[ HInd‬‬ ‫] ‪[ HInd‬‬

‫‪.‬‬ ‫‪PH 〈 PKai − 1 :‬‬ ‫( ﺇﺫﺍ ﻛﺎﻥ‬ ‫‪HInd‬‬ ‫** ﻳﺄﺧﺬ ﺍﻟﻜﺎﺷﻒ ﻟﻮﻥ ﺍﳊﻤﺾ )ﻟﻮﻥ‬
‫‪−‬‬
‫‪.‬‬ ‫‪PH 〉 PKai − 1 :‬‬ ‫( ﺇﺫﺍ ﻛﺎﻥ‬ ‫‪Ind‬‬ ‫** ﻳﺄﺧﺬ ﺍﻟﻜﺎﺷﻒ ﻟﻮﻥ ﺍﻷﺳﺎﺱ )ﻟﻮﻥ‬

‫‪−‬‬
‫‪HInd‬‬ ‫ﻟﻮﻥ ﺍﳉﺰﻳﺌﺎﺕ‬ ‫ﻣﻨﻄﻘﺔ ﺍﻻﻧﻌﻄﺎﻑ‬ ‫‪Ind‬‬ ‫ﻟﻮﻥ ﺍﻟﺸﻮﺍﺭﺩ‬ ‫‪PH‬‬

‫‪PKai − 1‬‬ ‫‪PKai‬‬ ‫‪PKai + 1‬‬

‫ﻭ ﻫﺬﻩ ﺑﻌﺾ ﺍﻷﻣﺜﻠﺔ ‪:‬‬

‫ﺍﻟﻮﺳﻂ ﺍﻷﺳﺎﺳﻲ‬ ‫ﺍﻟﻮﺳﻂ ﺍﳌﻌﺘﺪﻝ‬ ‫ﺍﻟﻮﺳﻂ ﺍﳊﻤﻀﻲ‬ ‫‪PH‬‬ ‫ﳎﺎﻝ ﲢﻮﻝ ﺍﻟـ‬ ‫‪PKai‬‬ ‫‪.‬‬ ‫‪Kai‬‬ ‫‪.‬‬ ‫ﺍﻟﻜﺎﺷﻒ‬
‫ﺃﺻﻔﺮ‬ ‫ﺑﺮﺗﻘﺎﱄ‬ ‫ﻭﺭﺩﻱ‬ ‫‪. 3,1 − 4, 4‬‬ ‫‪. 3, 74‬‬ ‫‪1,8 × 10 −4 .‬‬ ‫ﺍﳍﻠﻴﺎﻧﺘﲔ‬
‫ﺃﺻﻔﺮ‬ ‫ﺑﺮﺗﻘﺎﱄ‬ ‫ﺃﲪﺮ‬ ‫‪. 4, 2 − 6, 2‬‬ ‫‪.5‬‬ ‫‪10−5 .‬‬ ‫ﺃﲪﺮ ﺍﳌﻴﺜﻴﻞ‬
‫ﺃﺯﺭﻕ‬ ‫ﺑﻨﻔﺴﺠﻲ‬ ‫ﺃﲪﺮ‬ ‫‪.5 − 8‬‬ ‫ﻋﺒﺎﺩ ﺍﻟﺸﻤﺲ‬
‫ﺃﺯﺭﻕ‬ ‫ﺃﺧﻀﺮ‬ ‫ﺃﺻﻔﺮ‬ ‫‪. 6, 2 − 7, 6‬‬ ‫‪. 6,8‬‬ ‫‪1, 6 × 10−7 .‬‬ ‫ﺃﺯﺭﻕ ﺍﻟﱪﻭﻣﻮﺗﻴﻤﻮﻝ‬
‫ﺃﲪﺮ ﻗﺮﻣﻴﺪﻱ‬ ‫ﻋﺪﱘ ﺍﻟﻠﻮﻥ‬ ‫ﻋﺪﱘ ﺍﻟﻠﻮﻥ‬ ‫‪. 8, 2 − 10‬‬ ‫‪. 9, 7‬‬ ‫‪. 2 ×10−10‬‬ ‫ﺍﻟﻔﻴﻨﻮﻝ ﻓﺘﺎﻟﲔ‬

‫‪ -3-4‬ﺍﳌﻌﺎﻳﺮﺓ ‪ PH‬ﻣﺘﺮﻳﺔ ‪) :‬ﻋﻤﻞ ﳐﱪﻱ(‬

‫‪PH‬‬ ‫ﺃ‪ -‬ﻣﻌﺎﻳﺮﺓ ﲪﺾ ﺿﻌﻴﻒ ﺑﻮﺍﺳﻄﺔ ﺃﺳﺎﺱ ﻗﻮﻱ ‪ HCOOH ) :‬ﻣﻊ ‪. ( NaOH‬‬
‫‪PH‬‬ ‫‪b‬‬ ‫•‬ ‫ﻧﻀﻊ ﰲ ﺑﻴﺸﺮ ﳏﻠﻮﻝ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ‬
‫‪Q‬‬
‫‪{V a = 20ml‬‬ ‫‪, C a } : HCOOH‬‬
‫‪P‬‬
‫•‬
‫‪10‬‬
‫ﻭ ﻧﺴﻜﺐ ﻋﻠﻴﻪ ﺗﺪﺭﳛﻴﺎ ﺣﺠﻢ ‪ V b‬ﻣﻦ ﳏﻠﻮﻝ ﺃﺳﺎﺱ‬
‫‪PH‬‬ ‫‪E‬‬ ‫‪= 8, 4‬‬
‫•‬
‫ﺍﻟﻔﻴﻨﻮﻝ ﻓﺘﺎﻟﲔ‬
‫}‬ ‫‪8, 2‬‬ ‫‪{V‬‬ ‫‪b‬‬ ‫}‬
‫‪, C b = 0, 2 mol .L −1 : NaOH‬‬
‫ﻭﻧﺮﺳﻢ ﺍﳌﻨﺤﲎ ) ‪ PH = f (V b‬ﻓﻨﺠﺪ ‪:‬‬
‫ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ‪E‬‬
‫• ‪N‬‬ ‫) ‪HCOOH (aq ) + OH (−aq ) = HCOO (−aq ) + H 2O ( l‬‬
‫‪PKa‬‬
‫•‬ ‫ﻋﻨﺪ ﺍﻟﺘﻜﺎﻓﺆ )ﺃﻱ ‪ ( V b =V bE‬ﻳﻜﻮﻥ ‪:‬‬
‫‪PH‬‬ ‫‪M‬‬ ‫‪Aib Kamel‬‬
‫‪a‬‬
‫‪C a ×V a = C b ×V bE‬‬ ‫⇐‬ ‫‪n ( HCOOH ) = n OH −‬‬
‫(‬ ‫)‬
‫‪C b ×V bE‬‬
‫‪1‬‬ ‫) ‪V b ( ml‬‬ ‫= ‪Ca‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬
‫‪Va‬‬
‫‪2‬‬ ‫‪VE / 2‬‬ ‫‪V bE = 12, 4ml‬‬
‫) ‪E ( PH E = 8.4 ;V bE = 12.4ml‬‬ ‫ﻣﻦ ﺧﻼﻝ ﺍﻟﺒﻴﺎﻥ ﺍﺣﺪﺍﺛﻴﺎﺕ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ‬
‫‪0, 2 × 12, 4‬‬
‫‪. C a = 12, 4 ×10−2 mol .L−1‬‬ ‫= ‪ C a‬ﻭﻣﻨﻪ‬ ‫ﳒﺪ ﺃﻥ‬
‫‪20‬‬
‫(‬
‫‪PKa HCOOH / HCOO − = 4,8‬‬ ‫)‬ ‫‪ PH = PKa ←‬ﻭﻣﻨﻪ ﺑﻴﺎﻧﻴﺎ ﳒﺪ ﺍﻥ‬ ‫** ﳌﺎ ‪ V = V E / 2‬‬

‫‪12/6‬‬
 ‫ﺏ‪ -‬ﻣﻌﺎﻳﺮﺓ ﺃﺳﺎﺱ ﺿﻌﻴﻒ ﺑﻮﺍﺳﻄﺔ ﲪﺾ ﻗﻮﻱ ‪ NH 3 ) :‬ﻣﻊ ‪. ( HCl‬‬

‫‪PH‬‬
‫‪{V b‬‬ ‫ﻧﻀﻊ ﰲ ﺑﻴﺸﺮ ﳏﻠﻮﻝ ﺃﺳﺎﺳﻲ ‪= 20ml , C b } NH 3‬‬
‫‪A ib Kamel‬‬
‫‪PH‬‬ ‫‪b‬‬
‫ﻭ ﻧﺴﻜﺐ ﻋﻠﻴﻪ ﺗﺪﺭﳛﻴﺎ ﺣﺠﻢ ‪ V a‬ﻣﻦ ﳏﻠﻮﻝ ﲪﻀﻲ‬
‫‪ {V a , C a = 4 ×10−2 mol .L−1} : HCl‬ﻭﻧﺮﺳﻢ ﺍﳌﻨﺤﲎ‬
‫) ‪ PH = f (V a‬ﻓﻨﺠﺪ ‪:‬‬
‫) ‪NH 3(aq ) + H 3O (+aq ) = NH 4(+aq ) + H 2O ( l‬‬
‫ﻋﻨﺪ ﺍﻟﺘﻜﺎﻓﺆ )ﺃﻱ ‪ ( V a =V aE‬ﻳﻜﻮﻥ ‪:‬‬
‫‪PH‬‬ ‫‪= 5, 6‬‬ ‫‪6, 2‬‬
‫‪C a ×V aE = C b ×V b‬‬ ‫) ‪⇐ n ( NH 3 ) = n ( HCl‬‬
‫‪E‬‬
‫‪•E‬‬ ‫ﺃﲪﺮ ﺍﳌﻴﺜﻴﻞ‬ ‫}‬ ‫‪4, 2‬‬
‫= ‪Cb‬‬
‫‪C a ×V aE‬‬
‫ﻭﻣﻨﻪ ‪:‬‬
‫‪Vb‬‬
‫‪PH a‬‬ ‫ﻣﻦ ﺧﻼﻝ ﺍﻟﺒﻴﺎﻥ ﺍﺣﺪﺍﺛﻴﺎﺕ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ‬
‫‪1‬‬ ‫) ‪V a ( ml‬‬ ‫) ‪E ( PH E = 5, 6 ;V aE 11 ml‬‬
‫‪2‬‬ ‫‪V b = 1 1m l‬‬ ‫‪0, 04 × 11‬‬
‫‪. C b = 2, 2 ×10−2 mol .L−1‬‬ ‫= ‪ C a‬ﻭﻣﻨﻪ‬ ‫ﳒﺪ ﺃﻥ‬
‫‪20‬‬
‫** ﻋﻤﻮﻣﺎ ﺍﻟﺒﻴﺎﻥ ﻳﺼﻒ ﺗﻔﺎﻋﻞ ﻣﻌﺎﻳﺮﺓ ﺃﺳﺎﺱ ﺿﻌﻴﻒ ﲝﻤﺾ ﻗﻮﻱ )ﺩﺭﺍﺳﺔ ﻣﺮﺍﺣﻞ ﺗﻄﻮﺭ ﺍﻟﺒﻴﺎﻥ( ‪.‬‬
‫‪PH‬‬ ‫ﺟـ‪ -‬ﻛﻴﻔﻴﺔ ﺗﻌﻴﲔ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ﻋﻠﻰ ﻣﻨﺤﲎ ﺍﳌﻌﺎﻳﺮﺓ ‪:‬‬
‫‪A ib Kamel‬‬
‫** ﻃﺮﻳﻘﺔ ﺍﳌﻤﺎﺳﲔ ﺍﳌﺘﻮﺍﺯﻳﲔ ‪:‬‬
‫ﺍﻟﺒﻴﺎﻥ ﺍﳌﻘﺎﺑﻞ ﻳﻌﱪ ﻋﻦ ﺗﻔﺎﻋﻞ ﻣﻌﺎﻳﺮﺓ ﲪﺾ ﻗﻮﻱ‬
‫‪ {V a = 10 ml , C a } : HCl‬ﺑﺄﺳﺎﺱ ﻗﻮﻱ‬

‫‪PH‬‬ ‫‪= 7‬‬ ‫• ‪E‬‬ ‫‪7, 6‬‬ ‫‪{V‬‬ ‫‪b‬‬ ‫}‬

‫‪, C b = 0,1 mol .L −1 : NaOH‬‬
‫‪E‬‬
‫‪BBT‬‬ ‫}‬ ‫‪6, 2‬‬ ‫ﻓﻴﻜﻮﻥ ﻋﻨﺪ ﺍﻟﺘﻜﺎﻓﺆ ‪C a ×V a = C b ×V bE :‬‬
‫‪C b ×V bE‬‬
‫= ‪Ca‬‬ ‫ﻭﻣﻨﻪ ‪:‬‬
‫‪Va‬‬
‫ﻣﻦ ﺧﻼﻝ ﺍﻟﺒﻴﺎﻥ ﺍﺣﺪﺍﺛﻴﺎﺕ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ‬
‫) ‪E ( PH E = 7 ;V bE = 10ml‬‬
‫‪1‬‬ ‫‪V‬‬ ‫‪b‬‬ ‫) ‪(m l‬‬ ‫‪0,1× 10‬‬
‫‪2‬‬ ‫‪V b = 10m l‬‬ ‫= ‪ C a‬ﻭﻣﻨﻪ ‪. C a = 0,1 mol .L−1‬‬ ‫ﳒﺪ ﺃﻥ‬
‫‪10‬‬
‫ﻹﳚﺎﺩ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ﻧﺮﺳﻢ ﺍﳌﺴﺘﻘﻴﻢ ﺍﻟﺬﻱ ﻳﻮﺍﺯﻱ ﳑﺎﺳﻲ ﺍﳌﻨﺤﲎ ﰲ ﺟﻬﺘﲔ ﳐﺘﻠﻔﺘﲔ ﲝﻴﺚ ﻳﻜﻮﻥ ﻣﺘﻨﺎﻇﺮﺍ ﺑﺎﻟﻨﺴﺒﺔ ﳍﺎ ﻓﺘﻜﻮﻥ ﻧﻘﻄﺔ‬
‫ﺍﻟﺘﻜﺎﻓﺆ ﻫﻲ ﻧﻘﻄﺔ ﺗﻘﺎﻃﻌﻪ ﻣﻊ ﺍﳌﻨﺤﲎ )ﻛﻤﺎ ﰲ ﺍﻟﺸﻜﻞ( ‪.‬‬
‫‪PH‬‬
‫** ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﻠﻮﻧﻴﺔ ‪ :‬ﻋﻨﺪ ﺑﺪﺍﻳﺔ ﺍﳌﻌﺎﻳﺮﺓ ﻧﻀﻴﻒ ﺑﻀﻊ ﻗﻄﺮﺍﺕ‬
‫‪A ib Kamel‬‬
‫ﻣﻦ ﻛﺎﺷﻒ ﻣﻠﻮﻥ ﺇﱃ ﺍﶈﻠﻮﻝ ﺍﳌﻌﺎﻳﺮ ﳓﺼﻞ ﻋﻠﻰ ﺍﻟﺘﻜﺎﻓﺆ ﻋﻨﺪﻣﺎ‬
‫‪PH E‬‬
‫‪E‬‬ ‫ﻳﻐﲑ ﺍﻟﻜﺎﺷﻒ ﻟﻮﻧﻪ ﲝﻴﺚ ﳔﺘﺎﺭ ﺍﻟﻜﺎﺷﻒ ﺍﻟﺬﻱ ﳎﺎﻝ ﺗﻐﲑ ﻟﻮﻧﻪ‬
‫ﳛﺘﻮﻱ ﻋﻠﻰ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ) ‪. ( E‬‬

‫‪dPH‬‬
‫‪dV‬‬

‫‪V‬‬ ‫) ‪(m l‬‬

‫‪VE‬‬
‫‪12/8‬‬
 ‫) ‪σ ( ms / cm‬‬ ‫** ﺍﳌﻌﺎﻳﺮﺓ ﻋﻦ ﻃﺮﻳﻖ ﻗﻴﺎﺱ ﺍﻟﻨﺎﻗﻠﻴﺔ ‪:‬‬
‫‪A ib Kamel‬‬
‫ﳝﻜﻦ ﺍﺳﺘﻌﻤﺎﻝ ﺟﻬﺎﺯ ﻗﻴﺎﺱ ﺍﻟﻨﺎﻗﻠﻴﺔ ﺍﻟﻨﻮﻋﻴﺔ ‪ σ‬ﰲ ﻋﻤﻠﻴﺔ ﺍﳌﻌﺎﻳﺮﺓ ﻣﻦ ﺃﺟﻞ‬
‫‪ σ = f (V‬ﻧﺴﺘﻨﺘﺞ ‪V E‬‬ ‫ﺍﳊﺠﻢ ﺍﳌﺴﻜﻮﺏ ‪ ،‬ﺑﻌﺪ ﺭﺳﻢ ﺍﳌﻨﺤﲎ )‬
‫ﻛﻤﺎ ﰲ ﺍﻟﺸﻜﻞ ‪:‬‬

‫‪VE‬‬ ‫) ‪V ( ml‬‬

‫‪ -5‬ﺗﻄﺒﻴﻘﺎﺕ ‪:‬‬
‫‪ -1‬ﺍﻟﺘﻤﺮﻳﻨﺎﻷﻭﻝ ‪:‬‬
‫ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ‪ ،‬ﺍﳌﻌﺮﻭﻑ ﻋﺎﺩﺓ ﺑﺎﺳﻢ ﲪﺾ ﺍﻟﻨﻤﻞ‪ ،‬ﻫﻮ ﺳﺎﺋﻞ ﺷﻔﺎﻑ ﻟﻪ ﺭﺍﺋﺤﺔ ﺍﳋﻞ ﻫﺬﺍ ﺍﳊﻤﺾ ﻳﻔﺮﺯﻩ ﺍﻟﻨﻤﻞ‪.‬‬
‫ﺇﱃ ﺍﻟﻘﻴﻤﺔ ‪. 2,9‬‬ ‫‪ 10mL‬ﻣﻦ ﳏﻠﻮﻝ ﲪﺾ ﺍﻟﻨﻤﻞ‪ ،‬ﺫﻱ ﺍﻟﺘﺮﻛﻴﺰ ‪ ، C = 1,0 × 10 −2 mol.L−1‬ﻓﻴﺸﲑ ﻣﻘﻴﺎﺳﺎﻟ ‪pH‬‬ ‫ﻝ‬ ‫ﻧﻘﻴﺲ ﺍﻟ ‪pH‬‬
‫‪ -1‬ﺃﻛﺘﺐ ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﲪﺾ‪-‬ﺃﺳﺎﺱ ﺑﲔ ﺍﳊﻤﺾ ﻭ ﺍﳌﺎﺀ‪.‬‬
‫‪ -2‬ﻋﲔ ﻛﻤﻴﺔ ﺍﳌﺎﺩﺓ ﺍﻻﺑﺘﺪﺍﺋﻴﺔ ﳊﻤﺾ ﺍﻟﻨﻤﻞ ﻭ ﺃﳒﺰ ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ﻟﻠﺠﻤﻠﺔ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‪.‬‬
‫‪ -3‬ﻋﲔ ﺍﻟﺘﺮﻛﻴﺰ ﺍﳌﻮﱄ ﺍﻟﻨﻬﺎﺋﻲ ﻟﻠﻤﺤﻠﻮﻝ ﺑﺸﻮﺍ ﺭﺩ ﺍﳍﻴﺪﺭﻭﻧﻴﻮﻡ )ﺍﻷﻛﺴﻮﻧﻴﻮﻡ(‪.‬‬
‫ﺗﻌﻄﻰ ﺍﻟﺜﻨﺎﺋﻴﺔ ﲪﺾ‪/‬ﺃﺳﺎﺱ‪HCO2 H / HCO2− :‬‬ ‫‪ -4‬ﻋﲔ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﻟﻠﺘﻔﺎﻋﻞ ﻭ ﺍﺳﺘﻨﺘﺞ ﻧﺴﺒﺔ ﺗﻘﺪﻣﻪ ﺍﻟﻨﻬﺎﺋﻲ ‪.‬‬
‫** ﺣﻞ ﺍﻟﺘﻤﺮﻳﻦ ﺍﻟﺜﺎﱐ ‪:‬‬
‫) ‪H 3O (+aq ) / H 2O ( l‬‬ ‫‪ -1‬ﺍﻟﺜﻨﺎﺋﻴﺘﺎﻥ ﺍﳌﺸﺎﺭﻛﺘﺎﻥ ﰲ ﺍﻟﺘﻔﺎﻋﻞ ﳘﺎ‪، HCOOH (aq ) / HCOO (−aq ) :‬‬
‫) ‪HCOOH (aq ) = HCOO (−aq ) + H (+aq‬‬ ‫ﺍﳌﻌﺎﺩﻟﺘﺎﻥ ﺍﻟﻨﺼﻔﻴﺘﺎﻥ ﺍﳌﻮﺍﻓﻘﺘﺎﻥ ﳍﻤﺎ‪:‬‬
‫) ‪H 2O ( l ) + H (+aq ) = H 3O (+aq‬‬
‫) ‪HCOOH (aq ) + H 2O ( l ) = HCOO (−aq ) + H 3O (+aq‬‬ ‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﻫﻲ‪:‬‬
‫‪ .2‬ﻛﻤﻴﺔ ﺍﳌﺎﺩﺓ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ ﳊﻤﺾ ﺍﻟﻨﻤﻞ‪n ( HCOOH ) = 1, 0 ×10−4 mol ⇐ n ( HCOOH ) = CV = 1, 0 ×10−2 ×10, 0 ×10−3 :‬‬
‫** ﺟﺪﻭﻝ ﺍﻟﺘﻘﺪﻡ ﻟﻠﺠﻤﻠﺔ ﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ‪:‬‬
‫ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ‬ ‫ﺍﻟﺘﻘﺪﻡ‬ ‫) ‪HCOOH (aq‬‬ ‫‪+‬‬ ‫) ‪H 2O ( l‬‬ ‫=‬ ‫) ‪HCOO (−aq‬‬ ‫‪+‬‬ ‫) ‪H 3O (+aq‬‬

‫ﺍﳊﺎﻟﺔ ﺍﻹﺑﺘﺪﺍﺋﻴﺔ‬ ‫‪0‬‬ ‫‪1,0 × 10 −4 mol‬‬ ‫ﺑﺎﻟﺰﻳﺎﺩﺓ‬ ‫‪0‬‬ ‫‪0‬‬

‫ﺍﳊﺎﻟﺔ ﺍﻹﻧﺘﻘﺎﻟﻴﺔ‬ ‫‪x‬‬ ‫‪1,0 × 10 −4 mol − x‬‬ ‫ﺑﺎﻟﺰﻳﺎﺩﺓ‬ ‫‪x‬‬ ‫‪x‬‬
‫‪−4‬‬
‫ﺍﳊﺎﻟﺔ ﺍﻟﻨﻬﺎﺋﻴﺔ‬ ‫‪xf‬‬ ‫‪1,0 × 10 mol − x f‬‬ ‫ﺑﺎﻟﺰﻳﺎﺩﺓ‬ ‫‪xf‬‬ ‫‪xf‬‬

‫‪x f = x max = 1, 0 ×10−4 mol‬‬ ‫ﻳﻨﺘﻬﻲ ﺍﻟﺘﻔﺎﻋﻞ ﻋﻨﺪﻣﺎ ﻳﻜﻮﻥ‪:‬‬

‫‪ H 3O +  = 1,3 ×10−3 mol‬‬ ‫‪-3‬ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﻟﻠﺘﺤﻮﻝ‪  H 3O +  = 10− PH = 10−2,9 :‬‬
‫‪←‬‬
‫‪f‬‬ ‫‪f‬‬

‫‪x f =  H 3O +  ×V = 1,3 × 10−3 ×10, 0 × 10−3 = 1,3 × 10−5 mol 1, 0 × 10−4 mol‬‬ ‫‪ -4‬ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ‪:‬‬
‫ﻫﺬﻩ ﺍﻟﻜﻤﻴﺔ ﻫﻲ ﺃﺻﻐﺮ ﻣﻦ ﺍﻟﺘﻘﺪﻡ ﺍﻷﻋﻈﻤﻲ ﻟﻠﺘﻔﺎﻋﻞ ) ‪. (1, 0 ×10−4 mol‬‬
‫‪xf‬‬ ‫‪1,3 × 10 −5‬‬
‫=‪ τ‬‬
‫‪τ = 0,13 ←‬‬ ‫=‬ ‫ﺍﻟﺘﺤﻮﻝ ﺍﳌﺪﺭﻭﺱ ﻫﻮ ﺇﺫﻥ ﳏﺪﻭﺩ‪ .‬ﻭ ﻣﻨﻪ ﻧﺴﺒﺔ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﻫﻲ ﺇﺫﻥ‪.:‬‬
‫‪x max 1, 0 × 10−4‬‬
‫ﻭ ﻫﺬﺍ ﻳﻌﲏ ﺃﻥ ‪ 13 %‬ﻣﻦ ﲪﺾ ﺍﻟﻨﻤﻞ ﺗﻔﺎﻋﻠﺖ ﻣﻊ ﺍﳌﺎﺀ‪.‬‬

‫‪12/9‬‬
 ‫‪ -2‬ﺍﻟﺘﻤﺮﻳﻦ ﺍﻟﺜﺎﱐ ‪:‬‬
‫ﺗﺪﺍﻓﻊ ﺍﻟﻨﻤﻞ ﻋﻦ ﻧﻔﺴﻬﺎ ﺑﻮﺍﺳﻄﺔ ﻓﻜﻬﺎ ﻭ ﺑﻘﺬﻓﻬﺎ ﳊﻤﺾ ﺍﻟﻨﻤﻞ ‪ .‬ﺗﺜﺒﺖ ﻋﺪﻭﻫﺎ ﺑﻮﺍﺳﻄﺔ ﻓﻜﻬﺎ ﰒ ﲢﺮﻗﻪ ﺑﺎﳊﻤﺾ ﻭﳝﻜﻨﻬﺎ ﺃﻥ ﺗﻘﺬﻑ ﲝﻤﻀﻬﺎ‬
‫ﺇﱃ ﺃﻛﺜﺮ ﻣﻦ ‪. 30cm‬‬
‫ﻧﻮﺩ ﺩﺭﺍﺳﺔ ﺑﻌﺾ ﺧﻮﺍﺹ ﺍﶈﻠﻮﻝ ﺍﳌـﺎﺋﻲ ﳊﻤﺾ ﺍﻟﻨﻤﻞ ﺃﻭ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ﺫﻱ ﺍﻟﺼﻴﻐﺔ ‪. HCOOH‬‬
‫‪-1‬ﻧﻀﻊ ﺣﺠﻤﺎ ‪ V0 = 2mL‬ﻣﻦ ﲪﺾ ﺍﻟﻨﻤﻞ ﺫﻱ ﺍﻟﺘﺮﻛﻴﺰ ‪ C0‬ﻓـﻲ ﺣﻮﺟﻠـﺔ ﺣﺠﻤﻬﺎ ‪ V = 100mL‬ﰒ ﳕﻠﺌﻬﺎ ﺑﺎﳌﺎﺀ ﺍﻟﻨﻘﻲ ﺣﱴ ﺧﻂ‬
‫ﺍﳌﻌﻴﺎﺭﻱ ﻭ ﳓﺮﻛﻬﺎ ﻟﻨﺤﺼﻞ ﻋﻠﻰ ﳏﻠﻮﻝ ﻣﺘﺠﺎﻧﺲ ‪ S A‬ﺫﻱ ﺗﺮﻛﻴﺰ ‪ C A‬ﻭ ﻧﺎﻗﻠﻴﺘﻪ ﺍﻟﻨﻮﻋﻴﺔ ‪ . σ = 0.25 S / m‬ﻳﻌﻄﻰ ‪:‬‬
‫‪(λ‬‬ ‫‪H 3O +‬‬
‫‪= 35 x10 −3 S .m 2 / mol , λHCOO − = 5.46 x10 −3 S .m 2 / mol‬‬ ‫)‬
‫‪ -1-1‬ﺃﻛﺘﺐ ﻣﻌﺎﺩﻟﺔ ﲢﻮﻝ ﲪﺾ ﺍﻟﻨﻤﻞ ﺑﻮﺟﻮﺩ ﺍﳌﺎﺀ ‪.‬‬
‫‪ -2-1‬ﺣﺪﺩ ﺍﻟﻌﻼﻗﺔ ﺑﲔ ﺍﻟﺘﺮﻛﻴﺰﻳﻦ ‪ C0‬و ‪. C A‬‬
‫‪ -3-1‬ﺃﺣﺴﺐ ﻗﻴﻤﺔ ‪ pH‬ﺍﶈﻠﻮﻝ ‪. S A‬‬
‫‪ -4-1‬ﺃﻭﺟﺪ ﻧﺴﺒﺔ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ﺑﺪﻻﻟﺔ ﺗﺮﻛﻴﺰ ﺷﻮﺍﺭﺩ ﺍﳍﻴﺪﺭﻭﻧﻴﻮﻡ ﻋﻨﺪ‬
‫ﺍﻟﺘﻮﺍﺯﻥ ﻭ ﺍﻟﺘﺮﻛﻴﺰ ‪. C0‬‬
‫‪ -2‬ﻧﻌﺎﻳﺮ ﺣﺠﻤﺎ ‪ VA = 20cm3‬ﻣﻦ ﳏﻠﻮﻝ ‪ S A‬ﺑﻮﺍﺳﻄﺔ ﳏﻠﻮﻝ ﻣﺎﺀﺍﺕ‬
‫ﺍﻟﺼﻮﺩﻳﻮﻡ ﺗﺮﻛﻴﺰﻩ ‪  CB = 0.1mol / L‬ﺍﳌﻨﺤﲏ ﺗﻐﲑﺍﺕ‬
‫‪ pH‬ﺑﺪﻻﻟﺔ ﺍﳊﺠﻢ ‪ Vb‬ﶈﻠﻮﻝ ﻣﺎﺀﺍﺕ ﺍﻟﺼﻮﺩﻳـﻮﻡ ﺍﳌﻀﺎﻑ ‪.‬‬
‫‪ -1-2‬ﺃﺭﺳﻢ ﺍﻟﺘﺮﻛﻴﺐ ﺍﻟﺘﺠﺮﻳﱯ ﺍﻟﺬﻱ ﳝﻜﻦ ﻣﻦ ﺇﳒﺎﺯ ﻫﺬﻩ ﺍﳌﻌﺎﻳﺮﺓ ‪.‬‬
‫‪ -2-2‬ﺃﻛﺘﺐ ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺍﳊﺎﺻﻞ ‪.‬‬
‫‪ -3-2‬ﺣﺪﺩ ﺑﻴﺎﻧﻴﺎ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ﰒ ﺍﺳﺘﻨﺘﺞ ﻗﻴﻤﺔ ﺍﻟﺘﺮﻛﻴﺰﻳﻦ ‪ C0‬و ‪. C A‬‬
‫‪ -4-2‬ﺑﺎﺳﺘﻌﻤﺎﻝ ﺍﳉﺪﻭﻝ ﺃﺳﻔﻠﻪ ) ﺍﳌﻠﺤﻖ ( ﺣﺪﺩ ﺍﻟﻜﺎﺷﻒ ﺍﳌﻨﺎﺳﺐ ﻟﺘﺤﺪﻳﺪ ﻧﻘﻄﺔ ﺍﻟﺘﻌﺪﻳﻞ ‪.‬‬
‫‪ -5-2‬ﺃﻭﺟﺪ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﳍﺬﺍ ﺍﻟﺘﻔﺎﻋﻞ ‪ .‬ﻣﺎﺫﺍ ﺗﺴﺘﻨﺘﺞ ؟ ﻓﻴﻤﺎ ﳜﺺ ﺗﻔﺎﻋﻞ ﺍﳌﻌﺎﻳﺮﺓ ‪.‬‬
‫‪ -3‬ﻗﺎﺭﻥ ﻗﻮﺓ ﲪﺾ ﺍﻟﻨﻤﻞ ﺑﺎﻷﲪﺎﺽ ﺍﳌﻮﺟﻮﺩﺓ ﰲ ﺍﳉﺪﻭﻝ ﺃﺳﻔﻠﻪ ) ﺍﳌﻠﺤﻖ ( ﻋﻠﻞ ﺇﺟﺎﺑﺘﻚ ‪.‬‬
‫ﺍﳌﻌﻄﻴﺎﺕ ‪:‬‬
‫‪PKa‬‬ ‫ﺍﻟﺼﻴﻐﺔ‬ ‫ﺍﳊﻤﺾ‬ ‫ﻣﻨﻄﻘﺔ ﺍﻹﻧﻌﻄﺎﻑ‬ ‫ﺍﻟﻜﺎﺷﻒ ﺍﳌﻠﻮﻥ‬
‫‪3,8‬‬ ‫‪HCOOH‬‬ ‫ﺍﻟﻨﻤﻞ )ﺍﳌﻴﺜﺎﻧﻮﻳﻚ(‬ ‫‪4, 4 − 3,1‬‬ ‫ﺍﳍﻴﻠﻴﺎﻧﺘﲔ‬
‫‪4,8‬‬ ‫‪CH 3COOH‬‬ ‫ﺍﳋﻞ)ﺍﻹﻳﺜﺎﻧﻮﻳﻚ‬ ‫‪7, 6 − 6‬‬
‫‪3, 3‬‬ ‫‪HNO 2‬‬ ‫ﺍﻟﻨﺘﺮﻭ‬ ‫‪8,8 − 7, 2‬‬ ‫ﺍﲪﺮ ﺍﻟﻜﺮﻳﺰﻭﻝ‬
‫‪4, 2‬‬ ‫‪C 6 H 5 − COOH‬‬ ‫ﺍﻟﺒﱰﻭﻳﻚ‬ ‫‪10 − 8‬‬ ‫ﺍﻟﻔﻴﻨﻮﻟﻔﺘﺎﻟﲔ‬
‫** ﺣﻞ ﺍﻟﺘﻤﺮﻳﻦ ﺍﻟﺜﺎﱐ ‪:‬‬
‫‪ -1 – 1‬ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ‪HCOOH + H 2O = HCOO − + H 3O + :‬‬
‫‪ - 2 –1‬ﺍﻟﻌﻼﻗﺔ ﺑﲔ ‪ C0‬و ‪: C A‬‬
‫‪C0‬‬ ‫‪C0 V‬‬ ‫‪100‬‬
‫‪= 50‬‬ ‫‪←‬‬
‫‪ C 0V‬‬
‫‪. 0 =CAV‬‬
‫⇒ ‪.‬‬ ‫=‬ ‫=‬ ‫ﻟﺪﻳﻨﺎ ﻣﻦ ﻗﺎﻧﻮﻥ ﺍﻟﺘﻤﺪﻳﺪ ‪:‬‬
‫‪CA‬‬ ‫‪CA V 0‬‬ ‫‪2‬‬
‫‪-3 – 1‬ﺣﺴﺎﺏ ﻗﻴﻤﺔ ‪ pH‬ﺍﶈﻠﻮﻝ ‪: S A‬‬
‫‪ ،‬ﻭ ﻟﺪﻳﻨﺎ ‪σ = λH O [H 3O + ]f + λHCOO [HCOO − ]f → (2) :‬‬
‫‪3‬‬
‫‪+‬‬ ‫‪−‬‬ ‫[‬
‫‪pH = − log H 3O +‬‬ ‫]‬ ‫‪f‬‬
‫)‪→ (1‬‬ ‫ﻟﺪﻳﻨﺎ ‪:‬‬
‫ﻭ ﺣﺴﺐ ﻗﺎﻧﻮﻥ ﺍﳓﻔﺎﻅ ﺍﻟﺸﻮﺍﺭﺩ ﻟﺪﻳﻨﺎ ‪ ) [H 3O + ]f ≈ [HCOO − ]f :‬ﻤﻞ ﺗﺮﻛﻴﺰ ﺷﻮﺍﺭﺩ ‪. ( HO −‬‬
‫‪12/10‬‬
 ‫(‬
‫‪σ =  H 3O +  f λH O + λHCOO‬‬
‫‪3‬‬
‫‪+‬‬ ‫‪−‬‬ ‫)‬ ‫ﻭ ﺑﺎﻟﺘﻌﻮﻳﺾ ﰲ ﺍﻟﻌﻼﻗﺔ )‪: (2‬‬
‫‪σ‬‬
‫‪[H O ] = (λ‬‬
‫‪3‬‬
‫‪+‬‬
‫‪f‬‬
‫‪+ λHCOO −‬‬ ‫)‬ ‫=‬
‫‪0.25‬‬
‫‪(35 + 5.46 )x10‬‬ ‫‪−3‬‬
‫ﻭ ﻣﻨﻪ ‪= 6.18mol / m3 = 6.18 x10 − 3 mol / L :‬‬
‫‪H 3O +‬‬

‫(‬
‫‪pH = − log 6.18x 10 −3 ≈ 2.2‬‬ ‫)‬ ‫ﻭ ﻣﻦ ﺍﻟﻌﻼﻗﺔ )‪ (1‬ﳒﺪ ‪:‬‬
‫‪ ( 4 – 1‬ﻧﺴﺒﺔ ﺍﻟﺘﻘﺪﻡ ﺍﻟﻨﻬﺎﺋﻲ ‪:‬‬

‫= ‪τf‬‬
‫‪ H 3O +  x 50‬‬
‫‪f‬‬
‫ﻓﺈﻥ ‪:‬‬
‫‪C‬‬
‫‪، CA = 0‬‬ ‫ﻭ ﺣﻴﺚ ﺃﻥ ‪:‬‬ ‫= ‪τf‬‬
‫‪xf‬‬
‫⇒‬
‫] ‪[H O ] xV = [H O‬‬
‫‪3‬‬
‫‪+‬‬
‫‪f‬‬ ‫‪3‬‬
‫‪+‬‬
‫‪f‬‬
‫ﻟﺪﻳﻨﺎ ‪:‬‬
‫‪C0‬‬ ‫‪50‬‬ ‫‪xmax‬‬ ‫‪C A .V‬‬ ‫‪CA‬‬
‫‪ ( 1 – 2‬ﺭﺳﻢ ﺍﻟﺘﺮﻛﻴﺐ ﺍﻟﺘﺠﺮﻳﱯ ‪ :‬ﺍﻷﺟﻬﺰﺓ ﺍﳌﺴﺘﻌﻤﻠﺔ ‪ :‬ﳐﻼﻁ ﻣﻐﻨﺎﻃﻴﺴﻲ ‪ ،‬ﺳﺤﺎﺣﺔ ﻣﺪﺭﺟﺔ ‪ ،‬ﻛﺄﺱ ﺑﻴﺸﺮ ‪ ،‬ﻣﻘﻴﺎﺱ ‪ - PH‬ﻣﺘﺮ‬
‫ﺑﺎﻹﺿﺎﻓﺔ ﺇﱃ ﳏﻠﻮﱄ ﺍﻟﺼﻮﺩ ﻭ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ‪.‬‬
‫‪ ( 2 – 2‬ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺍﳊﺎﺩﺙ ‪HCOOH + HO − → HCOO − + H 2O :‬‬
‫‪ ( 3 – 2‬ﲢﺪﻳﺪ ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ‪ :‬ﺑﻴﺎﻧﻴﺎ ‪ ) E (V bE = 20mL , pH E = 8.2 ) :‬ﺑﺎﺳﺘﻌﻤﺎﻝ ﻃﺮﻳﻖ ﺍﳌﻤﺴﺎﺕ ( ‪.‬‬
‫‪CB .VbE 0.1x 20‬‬
‫= ‪ C AVA = CB .VbE ⇒ C A‬ﻭ ﻣﻨﻪ ‪C 0 = 0.1x 50 = 5mol / L :‬‬ ‫=‬ ‫* ﻋﻨﺪ ﺍﻟﺘﻜﺎﻓﺆ ‪= 0.1mol / L :‬‬
‫‪VA‬‬ ‫‪20‬‬
‫‪ ( 4 – 2‬ﺍﻟﻜﺎﺷﻒ ﺍﳌﻨﺎﺳﺐ ﻫﻮ ‪ :‬ﺍﻟﻔﻴﻨﻮ ﻟﻔﺘﺎﻟﲔ ﻷﻥ ‪ pH‬ﻧﻘﻄﺔ ﺍﻟﺘﻜﺎﻓﺆ ﺗﻨﺘﻤﻲ ‪‬ﺎﻝ ﲢﻮﻝ ﻫﺬﺍ ﺍﻟﻜﺎﺷﻒ ‪.‬‬
‫‪ HCOO − ‬‬
‫= ‪K‬‬ ‫‪f‬‬
‫‪ ( 5 – 2‬ﺣﺴﺎﺏ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﻟﺘﻔﺎﻋﻞ ﺍﳌﻌﺎﻳﺮﺓ ‪ :‬ﻟﺪﻳﻨﺎ ‪:‬‬
‫‪[ HCOOH ]f x  HO −  f‬‬
‫=‪K‬‬
‫] ‪[HCOO‬‬ ‫] ‪[H O‬‬
‫‪−‬‬
‫‪f‬‬ ‫‪3‬‬
‫‪+‬‬
‫‪f‬‬
‫=‪⇒K‬‬
‫‪Ka‬‬ ‫‪H 3o +‬‬ ‫[‬ ‫]‬ ‫‪f‬‬

‫] ‪[HCOOH ] x[HO ] f [H O‬‬ ‫[‬ ‫]‬

‫‪x‬‬ ‫‪−‬‬ ‫‪+‬‬
‫ﳒﺪ ‪:‬‬ ‫ﺑﺎﻟﻀﺮﺏ ﰲ ﺍﻟﻨﺴﺒﺔ‬
‫‪f‬‬ ‫‪3‬‬ ‫‪f‬‬
‫‪Ke‬‬ ‫‪H 3O +‬‬ ‫‪f‬‬

‫‪10−3.8‬‬
‫= ‪K‬‬ ‫‪−14‬‬
‫ﺣﻴﺚ ‪ K a = 10 − pKa :‬و ‪ ) pKa = 3.8‬ﻣﻦ ﺍﻟﺒﻴﺎﻥ ﻭ ﻋﻨﺪ ﻧﻘﻄﺔ ﻧﺼﻒ ﺍﻟﺘﻜﺎﻓﺆ ( ﻭ ﻣﻨﻪ ‪= 10+10.2 :‬‬
‫‪10‬‬
‫ﻭ ﻣﻨﻪ ﻧﺴﺘﻨﺘﺞ ﺃﻥ ﺗﻔﺎﻋﻞ ﺍﳌﻌﺎﻳﺮﺓ ﺗﻔﺎﻋﻞ ﺗﺎﻡ ﻷﻥ ‪. K 〉104 :‬‬
‫‪ – 5‬ﲟﻘﺎﺭﻧﺔ ﻗﻴﻢ ‪ pKa‬ﻧﻼﺣﻆ ﺃﻥ ‪ :‬ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ﺃﻗﻮﻯ ﻣﻦ ﲪﺾ ﺍﻹﻳﺜﺎﻧﻮﻳﻚ ﻭ ﲪﺾ ﺍﻟﺒﱰﻭﻳﻚ‬
‫ﻭ ﻫﻮ ﺃﻗﻞ ﻗﻮﺓ ﻣﻦ ﲪﺾ ﺍﻟﻨﺘﺮﻭ ﻷﻧﻪ ﻛﻠﻤﺎ ﻛﺎﻧﺖ ﺍﻟـ ‪ pKa‬ﺻﻐﲑ ﻛﻠﻤﺎ ﻛﺎﻥ ﺍﳊﻤﺾ ﺃﻗﻮﻯ ‪.‬‬

‫‪ -3‬ﺍﻟﺘﻤﺮﻳﻦ ﺍﻟﺜﺎﻟﺚ ‪:‬‬

‫ﳓﻘﻖ ﺧﻠﻴﻄﺎ ﻣﺘﺴﺎﻭﻱ ﺍﳌﻮﻻﺕ ﳛﺘﻮﻱ ﻋﻠﻰ ‪ 2,0 × 10 −2 mol‬ﻣﻦ ﻛﻞ ﻣﻦ ﺍﶈﺎﻟﻴﻞ ﺍﻟﺘﺎﻟﻴﺔ‪ :‬ﲪﺾ ﺍﻹﻳﺜﺎﻧﻮﻳﻚ‪ ،‬ﲪﺾ ﺍﻝﻤﻴﺜﺎﻨﻭﻴﻙ‪،‬‬
‫ﺇﻳﺜﺎﻧﻮﺍﺕ ﺍﻟﺼﻮﺩﻳﻮﻡ ﻭ ﻣﻴﺜﺎﻧﻮﺍﺕ ﺍﻟﺼﻮﺩﻳﻮﻡ ﻣﻦ ﺃﺟﻞ ﺍﳊﺼﻮﻝ ﻋﻠﻰ ﳏﻠﻮﻝ ﺣﺠﻤﻪ ‪. V = 100mL‬‬
‫‪ -1‬ﺃﻛﺘﺐ ﺍﳌﻌﺎﺩﻟﺘﲔ ﺍﻟﻨﺼﻔﻴﺘﲔ ﺍﻟﱪﻭﺗﻮﻧﻴﺘﲔ ﺍﳌﻮﺍﻓﻘﺘﲔ ﻟﻠﺜﻨﺎﺋﻴﺘﲔ ﲪﺾ‪/‬ﺃﺳﺎﺱ ﺍﻟﺘﲔ ﻳﺸﺎﺭﻙ ﻓﻴﻬﻤﺎ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ﻭ ﲪﺾ ﺍﻹﻳﺜﺎﻧﻮﻳﻚ‪.‬‬
‫‪ -2‬ﺃﻛﺘﺐ ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺑﲔ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ﻭ ﺷﻮﺍﺭﺩ ﺍﻹﻳﺜﺎﻧﻮﺍﺕ ‪.‬‬
‫‪ -3‬ﺃﺣﺴﺐ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﺍﳌﻮﺍﻓﻖ ﳌﻌﺎﺩﻟﺔ ﻫﺬﺍ ﺍﻟﺘﻔﺎﻋﻞ ‪.‬‬
‫‪ -4‬ﺃﺣﺴﺐ ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ‪ Qr ,i‬ﰲ ﺍﳊﺎﻟﺔ ﺍﻻﺑﺘﺪﺍﺋﻴﺔ‪.‬‬
‫‪ -5‬ﻫﻞ ﺍﳉﻤﻠﺔ ﺗﺘﻄﻮﺭ ﰲ ﺍﲡﺎﻩ ﺗﺸﻜﻞ ﲪﺾ ﺍﻹﻳﺜﺎﻧﻮﻳﻚ ﺃﻡ ﰲ ﺍﲡﺎﻩ ﺗﻔﻜﻜﻪ؟‬
‫(‬ ‫)‬
‫ﻳﻌﻄﻰ ‪pKa2 CH 3COOH / CH 3COO − = 4, 7 , pKa1 HCOOH / HCOO − = 3,8 :‬‬ ‫(‬ ‫)‬

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 ‫** ﺣﻞ ﺍﻟﺘﻤﺮﻳﻦ ﺍﻟﺜﺎﻟﺚ ‪:‬‬
‫‪ -1‬ﺍﻟﺜﻨﺎﺋﻴﺘﺎﻥ ﺍﳌﺸﺎﺭﻛﺘﺎﻥ ﰲ ﺍﻟﺘﻔﺎﻋﻞ ﳘﺎ‪HCOOH / HCOO − ; CH 3COOH / CH 3COO − :‬‬
‫) ‪CH 3COOH ( aq ) = CH 3COO − ( aq ) + H + (aq‬‬ ‫ﺍﳌﻌﺎﺩﻟﺘﺎﻥ ﺍﻟﻨﺼﻔﻴﺘﺎﻥ ﺍﳌﻮﺍﻓﻘﺘﺎﻥ ﳍﻤﺎ‪:‬‬
‫) ‪HCOOH ( aq ) = HCOO − ( aq ) + H + (aq‬‬
‫‪ -2‬ﳓﺼﻞ ﻋﻠﻰ ﻣﻌﺎﺩﻟﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺑﲔ ﲪﺾ ﺍﳌﻴﺜﺎﻧﻮﻳﻚ ﺷﻮﺍﺭﺩ ﺍﻹﻳﺜﺎﻧﻮﺍﺕ ﺍﻧﻄﻼﻗﺎ ﻣﻦ ﺍﳌﻌﺎﺩﻟﺘﲔ ﺍﻟﻨﺼﻔﻴﺘﲔ ﺍﻟﱪﻭﺗﻮﻧﻴﺘﲔ‪:‬‬
‫) ‪CH 3COO − ( aq ) + HCOOH ( aq ) = HCOO − ( aq ) + CH 3COOH ( aq‬‬

‫‪10−3,8‬‬ ‫) ‪Ka1 ( HCOOH / HCOO −‬‬ ‫‪10− pka1‬‬

‫‪K = −4,7 = 7,9‬‬ ‫‪←‬‬
‫= ‪ K‬‬ ‫=‬ ‫‪ -3‬ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ‪:‬‬
‫‪10‬‬ ‫) ‪Ka2 (CH 3COOH / CH 3COO −‬‬ ‫‪10− pka2‬‬

‫‪ 2, 0 × 10 −2   2, 0 × 10−2 ‬‬

‫‪‬‬ ‫‪⋅‬‬ ‫‪‬‬ ‫‪ HCOO −  ⋅ [CH 3COOH ]i‬‬
‫‪‬‬ ‫‪V‬‬ ‫‪‬‬ ‫‪‬‬ ‫‪V‬‬ ‫‪‬‬
‫‪Q r ,i‬‬ ‫=‬ ‫= ‪= 1 ⇐ Q r ,i‬‬ ‫‪i‬‬
‫‪ -4‬ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ‪:‬‬
‫‪ 2, 0 × 10−2   2, 0 × 10−2 ‬‬ ‫‪CH 3COO −  ⋅ [ HCOOH ]i‬‬
‫‪‬‬ ‫‪⋅‬‬ ‫‪‬‬ ‫‪i‬‬
‫‪ V‬‬ ‫‪  V‬‬ ‫‪‬‬
‫‪.‬‬ ‫‪ : Qr ,i < K -5‬ﻳﻨﺘﻬﻲ ﻛﺴﺮ ﺍﻟﺘﻔﺎﻋﻞ ﳓﻮ ﺛﺎﺑﺖ ﺍﻟﺘﻮﺍﺯﻥ ﻭ ﻳﺰﺩﺍﺩ ﺇﱃ ﺃﻥ ﻳﺒﻠﻎ ﻗﻴﻤﺔ ‪K‬‬
‫ﺗﺘﻄﻮﺭ ﺍﳉﻤﻠﺔ ﰲ ﺍﻻﲡﺎﻩ ﺍﳌﺒﺎﺷﺮ‪ ،‬ﺇﺫﻥ ﻳﺘﺸﻜﻞ ﲪﺾ ﺍﻹﻳﺜﺎﻧﻮﻳﻚ‬

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