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Log 1 0, Log 10 1: PH HO HO
Log 1 0, Log 10 1: PH HO HO
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
+
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
-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
[C ] .[ D ]t
γ λ
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
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
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
-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
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 ﺍﻬﺮﻱ(
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 ﺗﻮﺍﺯﺎ 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
] [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 − 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
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
dPH
dV
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
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
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 .
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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
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