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Chng V

PHN NG TO PHC &


CHUN
(Complexometric Reactions

& Titrations)

Ts. Phm Trn Nguyn Nguyn


ptnnguyen@hcmus.edu.vn

1. Phc cht v hng s bn


2. Phng php chun phc
3. Cn bng EDTA
4. nh hng pH ln cn bng
EDTA
5. c im ca phn ng chun
bng EDTA
6. Chun mt s ion kim loi
thng dng bng EDTA
7. ng cong chun ion kim
loi- EDTA
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Gii thiu:
PP chun to phc c dng ph bin trong cc phng
TN nh my cng nh trong cc phng TN nghin cu KH
xc nh chnh xc phn ln kim loi trong mu
1. Phc cht v hng s bn
Phc cht c hnh thnh t:
Ion KL trung tm ( KL chuyn
tip, c ph tng d cn trng):
ng vai tr acid Lewis, nhn i e Ligand hay phi t l nhng
phn t hay ion: ng vai tr
baz Lewis, cho i in t: tc
nhn to phc
Lin kt phi tr hay lin kt CHT
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Amonia l mt tc nhn to phc n gin nht, c i et do s to phc vi cc ion kim loi

Cu + 4:NH 3
2+

AgCl + 2:NH3

s phi tr

[Cu(NH3 )4 ]
+
[ Ag(NH3 )2 ] + Cl2+

s phi tr

[ Ag(NH3 )2 ]

AgCl + 2NH 3

[ Ag(NH3 )]

Ag + NH 3

[ Ag(NH3 )]

[ Ag(NH3 )]
=

K f1

[ Ag(NH3 )2 ]

+ NH 3

K f =K f1

[Ag ][NH3 ]

= 2,5 103

[ Ag(NH3 )2 ] = 1,0104
+
[ Ag(NH3 )] [NH3 ]
+

Kf2 =

[ Ag(NH3 )2 ] , K f
+
Ag(NH 3 ) 2 ]
[
K =
= 2,5 107
+

Ag + + 2NH 3

+ Cl- K f

f2

[Ag + ][NH 3 ]2

Kf , hng s to phc Ks, hng s bn

[ Ag(NH3 )2 ]

Ag + + 2NH 3 K i hay K d

Ki , hng s khng bn Kd, hng s phn ly = 1/Kf

1) Mt kim loi ha tr 2 phn ng vi ligand L hnh


thnh phc theo t l 1:1. Tnh [M2+] trong dd c pha
bi 2 lng th tch bng nhau ca dd M2+ 0,20M v dd L
0,20M, cho Kf = 1,0x108

M +L
2+

[ ML]

2+

[ ML]

2+

Kf =

[M +2 ][ L]

x = [M 2+ ] = 3, 2 105 M
6

2) Ion Ag hnh thnh phc bn theo t l 1:1 vi


triethylenetetraamine (trien). Tnh [Ag+] cb khi cho 25
mL dd AgNO3 0,010M tc dng vi 50mL dd trien 0,015M
cho Kf = 5,0x107

Ag + trien
+

[ Ag(trien)]

Ag(trien) +
Kf = +
[Ag ][trien]

x = [Ag + ] = 9,8.109 M
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2. PP chun to phc

C+M

CM

Kf

- dd chun C: dd ligand to phc vi kim loi M


- cb c tnh nh lng dd C to phc MC c Kf kh ln
dd to phc NH3 him khi c dng lm dd chun C
EDTA c dng ph bin nh 1 dd chun C to phc
v chun c phn ln cc ion kim loi
H
H
=> H4EDTA => H4Y
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3. Cn bng EDTA (H4Y)


EDTA phn ly cho 4 nc acid:
pKa1= 1.99, pKa2= 2.67, pKa3= 6,16, pKa4= 10.26
5 dng ca EDTA, (H4Y, H3Y-, H2Y2-, HY3-, Y4-)
EDTA kt hp c hu ht ion kim loi theo t l 1:1
ethylenediaminetetraacetate anion
EDTA-4 => Y-4
+n cation

Y -4 + M n+

K MY =

MY (4-n)

[MY (4-n) ]
[Y -4 ][M n+ ]

Hng s to phc EDTA


Cation

KMY

Log KMY

Cation

KMY

Log KMY

Ag+

2.1 x 107

7.32

Cu2+

6.3 x 1018

18.80

Mg2+

4.9 x 108

8.69

Zn2+

3.2 x 1016

16.50

Ca2+

5.0 x 1010

10.70

Cd2+

2.9 x 1016

16.46

Sr2+

4.3 x 108

8.63

Hg2+

6.3 x 1021

21.80

Ba2+

5.8 x 107

7.76

Pb2+

1.1 x 1018

18.04

Mn2+

6.2 x 1013

13.79

Al3+

1.3 x 1016

16.13

Fe2+

2.1 x 1014

14.33

Fe3+

1.3 x 1025

25.1

Co2+

2.0 x 1016

16.31

V3+

7.9 x 1025

25.9

Ni2+

4.2 x 1018

18.62

Th4+

1.6 x 1023

23.2
10

4. nh hng pH ln cn bng EDTA

Y -4 + M n+

MY (4-n)

K MY

Y4- : ph thuc vo pH
+

[MY (4-n) ]
= -4
[Y ][M n+ ]
+

H
H
H
H

HY3-

H2Y2-

H3Y-

H4Y
Y-4

nh ngha: 4 = [Y4-]/CH4Y : t l tn ti Y4- trong dd EDTA


CH4Y = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]
Hng s bn iu kin, KMY

K MY =

[MY (4-n) ]
[MY (4-n) ]

K
K

=
=
MY
4 MY
[M n+ ]i 4 C H4 Y
[M n+ ][C H4 Y ]

KMY ph thuc vo hay pH

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nh hng ca pH ln Kf

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3) Tnh pCa ca dd khi cho 100 mL dd Ca2+ c nng


0,100M pH=10 tc dng vi 100mL dd EDTA 0,100M.
Cho 4 ca EDTA = 0,35 v Kf = 5,0x1010
mmol Ca2+ = 100mL x 0,100mmol/mL = 10,0mmol
mmol EDTA = 100mL x 0,100mmol/mL = 10,0mmol
mmol CaY2- hnh thnh = 10,0mmol/ 200mL = 0,0500M
Ti cb: Gi x = [Ca+] x <<

Ca 2+ + EDTA
x
x

CaY 2
0, 0500 - x 0, 0500

CaY 2-
0, 0500
=
= 5, 0 1010
Kf=
2+
[Ca ] 4 [CH4 Y ] x 0,35 x
'

2+
x = 1, 7 106 M pCa = log[Ca ] = 5, 77
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5. c im ca phn ng chun bng EDTA

M n+ + H 2 Y 2-

MY n 4 + 2H +

EDTA v ion kim loi to phc theo t l mol 1:1


bn ca phc to thnh trong cb chu nh hng bi [H+]
khi thc hin chun cn s dng dd m pH to mi
trng chun n nh v hng s bn iu kin Kf ln cho
yu cu nh lng.
K ca p. chun :
- Phc MYn-4 bn (Kf 108) pH chun
- Chn cht ch th to phc bn vi KL nhng phi km bn
hn phc MYn-4
- Chn cht ch th to phc bn vi KL nhng phi km bn
hn phc MYn-4
- Loi b nh hng ca cc KL khc c trong dd
- CB phc thng chm, cn chun chm hay un nh dd
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trc khi chun

Mt s ch th ion kim loi thng dng

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6. Chun mt s ion kim loi thng dng bng EDTA


6.1 Chun Mg2+
Thng c chun trc tip pH =10, vi ch th
crom xanh en (Eriochrome black T)
Phn ng chun

MgY 2

Mg 2+ + Y 4 Phn ng vi ch th

Mg2+ c cha trong bnh erlen

MgY 2 + In

MgIn + Y 4-

(ho^`ng)

(xanh)

Mg2+ c cha trn buret

In + Mg
(xanh)

MgIn
(ho^`ng)

Ca2+

cng to phc vi EDTA pH =10, khng c


php c mt Ca2+ khi chun Mg2+.

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6.2 Chun Ca2+


Chun trc tip pH =12,5, vi ch th

i Murexide: CaIn (red) In (blue)


i Fluorescein: CaIn (yellow) In (orange)
Khi chun Ca2+, Mg2+ khng gy nh hng (ta Mg(OH)2)

Chun th pH =10, ch th crom xanh en


Thm vo dd 1 lng MgY2- trc khi cho EDTA

MgY + Ca
2-

2+

CaY + Mg

2+

(K MgY <K CaY )

lng Mg2+ sinh ra s to phc mu hng vi ch th (MgIn)


Khi chun bng EDTA, Ca2+ cn li tc dng trc

Ca

2+

+ Y 4-

CaY

Khi ht Ca2+ t do, n cn bng to phc ca Mg2+

Mg

2+

+ Y 4-

MgY

Ti im tng ng: MgIn + Y 4 dd chuyn mu xanh ca In

MgY

+ In

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7. ng cong chun kim loi - EDTA


dng ng cong pM (-log[Mn+]) theo th tch EDTA
4) Hng s bn iu kin ca s hnh thnh CaY2- l 1,8.10-10.
Tnh pCa trong 100 mL dd Ca2+ 0,100M pH=10 khi thm a) 0
mL, b) 50mL, c)100mL v d)150 mL dd EDTA 0,100M.

a) pCa trc im tng (thm 0 mL dd EDTA)

pCa = log[Ca 2 + ] = log(0,100) = log(1, 00 10 1 ) = 1, 00


b) pCa trc im tng (thm 50 mL dd EDTA)
mmol Ca2+ = 100mL x 0,100mmol/mL = 10,0mmol
mmol EDTA = 50mL x 0,100mmol/mL = 5,0mmol
mmol Ca2+ t do = 5,0mmol/ 150mL = 0,033M

pCa = log[Ca 2 + ] = log(3, 3 10 2 ) = 1, 48


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7. ng cong chun kim loi - EDTA


dng ng cong pM (-log [Mn+]) theo th tch EDTA
4) Hng s bn iu kin ca s hnh thnh CaY2- l 1,8.10-10.
Tnh pCa trong 100 mL dd Ca2+ 0,100M pH=10 khi thm a) 0
mL, b) 50mL, c)100mL v d)150 mL dd EDTA 0,100M.

c) pCa ti im tng (thm 100 mL dd EDTA)


mmol Ca2+ = 100mL x 0,100mmol/mL = 10,0mmol
mmol EDTA = 100mL x 0,100mmol/mL = 10,0mmol
mmol CaY2- hnh thnh = 10,0mmol/ 200mL = 0,0500M
Ti cb: Gi x = [Ca+] x <<
2

Ca + EDTA
CaY
0, 0500 - x 0, 0500
x 2x
[CaY ]
0, 0500
K 'f =
=
= 1,8 1010
2+
[Ca ][C H4 Y ]
xx
2+

2+

x=1,710-6 M=[Ca 2+ ] pCa = log[Ca ] = 5, 7720

7. ng cong chun kim loi - EDTA


dng ng cong pM (-log[Mn+]) theo th tch EDTA
4) Hng s bn iu kin ca s hnh thnh CaY2- l 1,8.10-10.
Tnh pCa trong 100 mL dd Ca2+ 0,100M pH=10 khi thm a) 0
mL, b) 50mL, c)100mL v d)150 mL dd EDTA 0,100M.

d) pCa sau im tng (thm 150 mL dd EDTA)


mmol Ca2+ = 100mL x 0,100mmol/mL = 10,0mmol
mmol EDTA = 150mL x 0,100mmol/mL = 15,0mmol
[CaY2- ] hnh thnh = 10,0mmol/ 250mL = 0,0400M
[H4Y] tha = 5,0mmol/ 250mL = 0,0200M

[CaY 2- ]
0, 0400
=
= 1,8 1010
Kf=
2+
2+
[Ca ][C H4 Y ] [Ca ] 0, 0200
'

2+

[Ca 2+ ] = 1,110-10 M pCa = log[Ca ] = 9, 95


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Ca + EDTA
2+

CaY

Tng pH, CB dch sang phi

ng cong chun 100 mL dd Ca2+ 0,1M


= dd Na2EDTA 0,1 M pH 7 v 10.

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3 vng
chun
ca
EDTA

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5) Xy dng ng cong chun (pMg theo th tch

EDTA) cho chun 50,0 mL dd Mg2+ 0,00500 M vi dd


EDTA 0,1000M trong mt dd m c pH = 10

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