phân tích - Khoa Hoá -
-
Vinh, tháng 05/2007.
1
Trang ................................................................................................ 2
............................................. 21
1.6.
.................................................................... 22 ...................................... 27
................................................................................. 7 1.1. Lantan và dãy các
.................................... 27
...................................... 7
...................................................... 27
................................................... 7 .................................................... 29
............................................... 7 .................................................................. 9
.............................................................. 29
.............................................................. 9
.......................................................................................... 29
............................................................................... 9
........................................................................ 29
........................... 10
.................................................................................... 29
.............................................. 11
3+
(10-2M) ................................................................. 29 -3
............................................... 12
M ......................................................... 30
............................................................................ 13
........................................................................... 30
.............................................. 13
................................................................ 30 ............................................................. 30
.................... 14 ....................... 15 .............................. 15
4+
-3
10 M........................................................... 30
2+
10-3M ........................................................... 31
............................................... 16
..................................................................... 31
................................................. 16
......................................................................... 31
................................................ 16 ........ 16 ....................................................... 16
3+
- asenazo III ........................................... 31 ............................................................... 31 .............................................................. 31
...................................... 17
....................... 32
..................................... 17
1.4.2
3+
..................... 32
............................................................... 18
........................................................... 32
............................. 19
..................................................................... 33
................................................................................. 19
....................................... 34
.............. 20
................................ 35
........ 20 2
3
3.1.5. Nghiê ............................................................................. 36 ....... 38 ..................................................................... 38 3.2.1. ......................................................................................... 38 3.2.2
........ 40 3+
- asenazo III ...... 41
4+
................................................................. 42
2+
................................................................ 42
.......................................................................................... 43 ............................................................................... 45 ............................................................................ 46
4
5
- asenazo III
-
- asenazo
III.
1
-
6s2. I2 11,06
1
5,577 0
òa). -
3
-
3+ La /La
)
T0nc
asenazo III. -
= -2,522V. : 6,16 : 9200C
T0s C 0p S
: 34700C : 27,6 : 57,3
Hnc Bán kính (nm)
I3 19,11
: 6,7 La3+ 0,104
La 0,187
La4+ 0,090
0
, 4f7, 4f14
6
7
pK = 10,04
0,1 (LiClO4)
pK = 7,4
Ion La3+
4000
trong không khí
3,0 (LiClO4)
2O3,
LaHal3, LaN, LaC,
LaH3 Oxyt La2O3 (t =20000 C ). La2O3 0
3 2O3
lantan N2
Hydroxyt La(OH)3
t=
1.10-19). {49} Theo dãy các
Do có: E0La3+/La = 3PO4
cacbona La3+ + HOH
La(OH)2+ + H+
La(NO3)3 .6H2O, La(NO3)3 .9H2O, LaBr3.6H2O, La2(SO4)3.8H2 3+ 0
3+
không màu.
T0C 0,3 (NaClO4)
4NO3La(NO3)3 ..4H2O
pK= 9,06
3)2.2La(NO3)3
250C pK = 8,53
0
i 0,05 (0
50% etanol)
pK = 9,06 8,70(25%); 8,17
0,1
pK = 8,14
3,0
pK = 10,04
8
(H2O);
-12. [27, 28]
9
7 trong La(dixet)2.2H2
2O4)4]
5-
, [La(NTA)2]3-
2 2(SO4) 3.9H2O.
+
R3 CH - COO-
R1- NH
[18]
CH - COOH R2 [4] - Antipirin C: C32H28N8S2 axit:
axetic,
xitric,
tactric,
etyldiamintetaaxetic
(EDTA),
dietyltriaminpentaaxetic (DTPA), nitilotriaxetic (NTA), asenazo III, amino -
-3 là 600nm.
735
chúng
=105 .
mg/l), Fe(III) (0.3 mg/l), Zr (0,75 mg/l), Cu(II) (1,5 mg/l), V(IV) (2,5 mg/l), -nbutyl-photphat (TBP) và diankylphotphoric (HDEHP).
-
- 560 nm và
3 580 = (22 - 25). 10 .
ion là: pK0 = -3,2; pK1 = 0,66 La3
xLan+3
dãy: photphat < photphonat < photphinat < photphioxyt. [21]
10
pK4 = 8,02
0,10; pK5 = 9,50
0,14; pK2 = 3,50 0,09; pK6 = 10,62
C23H15N5O12S2 -
11
0,26; pK3 = 6,52 0,32; pK7 = 13,2
0,36; 0,08.
xác
- Alizarin S: C14H5(OH)2SO3Na.H2
nóng, không tan
49 1/2
2O3,
La(NO3)2
Asenazo III : C22H18O14N4S2As2 AsO3H2
N
CeO2, Nb2O3 2(màu
vàng chanh), Eu2O3
2O3
OH
N
N
-
xyl naphtalin-3,6-
(2-
12
N
SO 3H
O3SH
dùng
AsO3H2
OH
13
-2,7-bis
-
cto n+ 3
O
2CO3
.
As
O
OH
(n-2) Me
sau: O
+
.
O
.
N
NaCl bão hòa.
O
As
N
. .
N
+
(n-3) Me O
. N .
. (II)
(I)
n+
và hai nhóm
AsO3H2; -
1=660
665nm ;
2=610nm.
nào. O-aseno-oxylazo. Nhóm này có HO
AsO3H2 .
. N
N .
.
- Zr - Hf - U(IV) - Pu4+ - Np4+ - Th m
asenazo III. c
AsO3H2 và -OH.
14
15
[6], [8],[17]
m 3
(10 )
mg/ml 700C,
(nm) Th
665
130
HCl 8N
0.01
U
670
130
HCl 4N
Ce
665
47
PH = 3
0.02
Cu
665
10
PH = 6
0.02
0.05
0.1 xilenol da cam.
A + 24 = 100G/V
= 580 nm. a -
QUANG [12]
16
17
M + qHR M + qHR + pHR '
'
MRq
+ qH+
(1)
KCb
MRqR'P
+ (q+p)H
(2)
Kcb
là các ligan. A
M
(3)
-
(1) 4,
(2)
KNO3 q
MRqR'P
t(phút)
và
MRqvà MRqR'P '
HR
max
1.4.2 A MRqR'p
MRq
-
HR
HR'
4
MR'p
max
trong h
A E C A
F (2)
D B (1)
pH
18
19
hay NH3
4
-
Xร C 4+
; V5+; Zr4+
-5
-4
-3
-
phรกp sau: -
-
(
A=f(C A (1) (2) M
CT .THรถ CM n
20
21
/ CR
R/
CM
M
R
=const; CR R/ CM.
Ai
=const; CM M/ CR.
CR=b2
CM=a2
CR=b1
CM=a1
CM CR
CR CM
)
mRn.
1.6).
M+VR
= const
CM+CR
Dãy 1: CM+CR = a1 Dãy 2: CM+CR = a2 R/CM
hay A=f(CR/(CR+ CM)) MmRn
22
23
); A=f(VR/VR)
Ai CM+ CR =a1 CM+ CR =a2
M(OH)i + qHmR Kp =
M(OH)i(Hm-nR)q +qn H Kp qn
( M (OH ) i ( H m n R) q . H M (OH ) i . H m R
q
(1)
.
M(OH)i(Hm-nR)q ] = CK; [H+] =h CR n ( ) CM m
M + H2O [M(OH) ] =K1
M(OH)
+
H
K1
M(OH)2 + H
K2
-1
M(OH) + H2O [ M(OH)2 ] = K1
-2
2
M(OH)i-1 + H2O
a hai
[M(OH)i ] = K1
2
M(OH)i i
CM = [M] + [M(OH) ] +[ M(OH)2 ]
khรกc nh
CM
[ M] = [M(OH)i]=
(1
-1
h . K 1'
-2
h . K 1 '.K 2 '
CM (1
1
h- . K 1 '
+H
[M(OH)i ] +CK CK .... h- i . K 1 '.K 2 '.....K i ' )
CK
h- 2 . K 1 '.K 2 '
.... h- i . K 1 '.K 2 '.....K i ' )
1.6.
m
Hm+1 R HmR [Hm+1 R ] = [HmR].h/ K0 -
24
+
H
Ko
HmR Hm-1 R + [Hm-1 R ] = K1. [HmR].h-1
H
K1
Hm-2 R + Hm-1R [Hm-2 R ] = K1. K2 [HmR].h-2
H
K2
25
Ki
-i
.
K 1 '.K 2 '....K i ' hi
[ M (OH)i ].( CHm R Hm-(n-1)R [Hm-n R ] =
Hm-n R + H
K1.K2
Kn
CK ( 1
[HmR].h-n
n
Q = ( K1.K2
CHR = [Hm+1 R ] + [HmR] + [Hm-1
[HmR] =
[Hm-nR ] =
(CHmR (1
h . Ko
-1
-1
h . K1
(CHm R (1
h .Ko
-1
m-nR],
m-n
n)
q
R ] +q.CK
qCK ) .... h- n . K 1 .K 2 .....K n )
qCK )(K 1 .K 2 ....K n ) -1
h . K1
.... h- n . K 1.K 2 .....K n ).hn
[ M(OH)i(Hm-nR)q ] = CK; [H+] =h
( M (OH) i (H m n R) q . H
Kp =
-1
h .Ko
M (OH) i . H mR
q
qn
.
1
=
CK .hqn.(1 h.K o h 1.K 1 .... h n .K 1.K 2 .K n )q [ M (OH)i ]( CHmR q.CK )q
M(OH)i(Hm-nR)q
M(OH)i + q Hm-nR
KH
H
q
KH
M (OH) i . H m n R ( M (OH) i (H m n R) q m-n
R ] vào (2) ta có:
[ M (OH)i ].( CHm R
KH =
CK ( 1
h
(2)
-1 .Ko
-1
h . K1
26
qCK )q (K 1.K 2 ....K n )q -n
q
.... h . K 1.K 2 .....K n ) .h
qn
=
1
27
h-1. K 1
qCK )q
.... h- n . K 1.K 2 .....K n )q
KH =
B.Q. h qn
lgB =f(pH): -lgB
K - lg B = qn. pH - lg H (3) Q. tg
M(OH)i(Hm-nR)q
1
n tg
2
pH
lgB vào pH
Hình 1.8: HR,
CK= CM.
q, Ko, K1, K2
n
Ai . A gh
-
lgB =f(pH ) có tg < 0 và không
pH
Ai
CK
(CHmR - qCK)
M
M(OH) M(OH)2
M(OH)3
i=o
i=1
i=3
i=2
lgB =f(pH ) có tg i
pH1 pH2
i
lgB= f(pH) PH
-lgBM
-lgBM(OH)
-lgBM(OH)
2
-lgBM(OH)3
Kp
KH
pH1
- lg
-
pH2
[ M (OH)i ].( CHm R
= KP
KH
(1 và Q= ( K1.K2
28
T Q.
h . Ko n)
q
-1
h-1. K 1
. 29
qCK )q
.... h- n . K 1.K 2 .....K n ) q
S2 n
nh SX
[15]
=tp;k. SX
-
-
p;k
Ai = (a
a)
+ (b
b)
Ci
X-
-
X+
a
X 2
Ci . A i Ci Ci A i 2 n. Ci ( Ci )2
a=
-
n Ci . A i Ci A i b= = 2 n. Ci ( Ci )2
a
= tp,k.Sa
b
= tp,k.Sb
a
a t p,k .Sa
b
b
b t p,k .Sb
1, n
X
-
C i 1
-
2
=
So sánh ttn
p;k
tn
(x i
X2, X3
X
i
yi n
X )2
n 1
30
=
< tp;k thì X
-
a a b
tn
31
X a SX a là d
.100
t p; k .SX X
.100
th
3) 3 .6H2 -3
M)
Trong C22H18O14N4S2As2Na2
-
. asenazo III 10-3M. -3
M)
C
-3
ác
M.
0,01mg. 3
-
ch
3
3
-
4+ 3+
-2
(10 M)
(10-3M)
Cân chính xác trên cân phân tích 0,13053 gam Th(NO3)4 4H2O theo
Cân chính xác 0,81226 gam La(NO 3)3.6H2
4+ 3+
32
33
trình Data -
3)4 4H2 3(10
-3
MS-Excel
M)
Pascal.
it HNO3 (1 : 5).
3+
3.1. NGHIÊN
Cd(NO)3 10-3.
Casenazo III = 8.10-5
-
3
h. 3+
khác nhau (l = 1.001 cm,
- asenazo III
(nm)
3+ 3
= 0.1M). A
(nm)
450
0.145
570
0.400
470
0.205
580
0.305
520
0.475
590
0.200
540
0.520
600
0.115
560
0.460
710
0.015
M
Pascal MS-Excel Matlab.
34
A
35
0.6
0.6
0.5 0.4
A
0.4 0.3 0.2
0.2
0.1 0 0
200
400
600
800
0 610
620
630
640
650
660
670
680
690
700
710(nm)
La3+ - asenazo III
max
3+
= 540 nm.
-
-3
asenazo III 10-3
3
1M,
3+ 3+
-
max
max
max 3+ 3+
khác nhau (l = 1.001 cm,
.
-
3+
-
= 0.1M).
625
630
640
645
650
655
680
700
0.026
0.076
0.221
0.299
0.380
0.429
0.128
0.041
(nm) 3+
Ai
4.10 M ; Casenazo III = 8.10 M, CNaNO3 -5
-5
Ai La3+ hình 3.3.
36
37
3+
là
3+
- asenazo III vào
t (phút) 0.55 0.5
t(phút)
5
10
15
20
30
60
90
120
150
180 0.45
Ai
0,424 0,424 0,423 0,424 0,424 0,422 0,422 0,421 0,421 0,421
0.4 0.35 0.3 0
50
100
150
200
i
ôi 3+
3+
-
-
La3+
= 4.10-5M, Casenazo III = 8.10-5M,
CNaNO3 3+
3.4 và hình 3.4. 3+
- asenazo
III vào pH pH 1,50 1,71 2,00
2,20
2,52 3,00 3,20 3,50
4,00 4,51 5,06
A 0,210 0,345 0,420 0,422 0,425 0,430 0,400 0,351 0,301 0,240 0,200
38
39
Ai 0.5
0.4 0.3
STT
VLa(III) (ml)
VasenazoIII (ml)
CasenazoIII.10-5M
Ai
0.2
1
1.0
1,00
1,60
0,170
0.1
2
1,0
2,00
3,20
0,210
0
3
1,0
3,00
4,80
0,257
4
1,0
4,00
6,40
0,320
5
1,0
5,00
8,00
0,425
6
1,0
6,00
9,60
0,425
7
1,0
7,00
11,20
0,424
8
1,0
8,00
12,80
0,425
9
1,0
10,00
16,00
0,425
10 1,0 asenazo III và o
12,00
19,20
0,425
1.5
2.03
3+
2.52
3.2
4
5.06
pH
-
10-5 -3
-3 -4
40
Ai 0.45 0.4 0.35
41
C AsenazoIII C La 3
-5
asenazo III asenazo III
C AsenazoIII C La 3
8,00.10 4,00.10
= 5,00
= 8,00.10-5
C AsenazoIII ( l =1,001 cm, C AsenazoIII C La 3
5 5
2 -4
M trong các
3
DD1
DD2
DD3
DD4
DD5
DD6
DD7
La3+.10-3 M(ml)
1,0
1,0
1,0
1,0
1,0
1,0
1,0
-3
2,0
2,0
2,0
2,0
2,0
2,0
2,0
1,25
2,5
3,75
5,0
7,5
10,0
11,25
Asenazo III. 10 M(ml)
NaNO3 1M(ml)
Ai
3+
0,423 0,424 0,425 0,424 0,425
= 0,1M, pH = 3,0,
= 655nm)
C La3+ . 10-5
CAsenazoIII.10-
9,00
0,32
2,88
0,9
0,309
2,00
8,00
0,64
2,56
0,8
0,600
3,00
7,00
0,96
2,24
0,7
0,950
3,50
6,50
1,12
2,08
0,65
1,021
4,00
6,00
1,28
1,92
0,6
0,920
5,00
5,00
1,60
1,60
0,5
0,681
6,00
4,00
1,92
1,28
0,4
0,520
7,00
3,00
2,24
0,96
0,3
0,345
8,00
2,00
2,56
0,64
0,2
0,220
9,00
1,00
2,88
0,32
0,1
0,113
V La3+ (ml)
VAsenazoIII(ml)
1,00
5
Ai
0,424 0,424
= 0,1.
42
- asenazo III vào
43
C AsenazoIII C AsenazoIII C La 3
Ai
5
4,00
8,00
2,00
0,425
6
4,00
8,60
2,15
0,425
7
4,00
10,00
2,50
0,425
8
4,00
12,00
3,00
0,425
9
4,00
14,00
3,50
0,425
10
4,00
16,00
4,00
0,425
1.2 1 0.8 0.6 0.4 0.2 0 0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
1
C AsenazoIII C AsenazoIII C La 3
C AsenazoIII C AsenazoIII C La 3
La3+ : asenazo III = 1 : 2. C 3+
La 16.10-5M, CNaNO3
-5
-5
3+
- asenazo III và o
C AsenazoIII ( = 655 nm, l = 1,001 cm, = 0,1M) C La 3
STT
C La3+ . 10-5
CAsenazoIII.10-5
C AsenazoIII C La 3
1
4,00
1,60
0,40
0,105
2
4,00
3,20
0,80
0,180
3
4,00
4,80
1,20
0,258
4
4,00
6,40
1,60
0,335
44
Ai
45
Ai
4+
0.45 3+
0.4 -5
0.35
-5
4.10
4+
0.3
3
100.10-5
0.25 0.2 0.15 0.1
4+
khác nha
0.05 0.4
0.8
1.2
1.6
2
2.15
2.5
3
3.5
C AsenazoIII C La 3
4
= 655 nm).
4
4
4
4
4
4
4
CTh4+.10-5
0
10
20
40
60
80
100
0,428
0,315
0,301
0,273
0,213
0,182
0,068
CLa3+.10
0
(l = 1,001 cm,
-5
Ai
C AsenazoIII C La 3
4+
3+
:
ion Th4+ 2+
y hoàn toàn phù 3+ 3+
-
-5
-5
4.10
2+
ASENAZO III
3+
4+
âsenazo III
= 2.C La3+
(l = 1,001 cm,
= 655 nm)
CLa3+.10-5
4
4
4
4
4
4
4
CCd2+.10-5
0
10
20
40
60
80
100
0,428
0,428
0,427
0,428
0,576
0,620
0,698
Ai
46
100.10
và Cd2+. 2+
3+
3 -5
47
10
- Ion Cd2+ asenazo III.
1.056
AI 1.2 2+
CCd 2
là :
40 4
C La3 - Ion Th asenazo III.
5,0
1 0.8
10
0.6
4+
0.4 0.2 0 0
1
2
3
4
5
6
CLA3+.10-5
4,0). 10-5M. asenazo III
= 2.CLa3+. Ai = (1,9189
cm,
= 0,1, pH = 3,0,
= 655 nm).
= (1,9189
STT
CLa3+.10-5
1
0,5
0,125
2
1,0
0,210
3
1,5
0,308
4
2,0
0,390
5
2,5
0,481
6
3,0
0,550
7
3,5
0,621
8
4,0
0,702
9
4,5
0.910
48
0,2780) .104 . CLa3+ + (0,0076
0,2780) .104.
Ai
49
0,0863).
1. 2. 3. max
= 655 nm;
- Hà
4.
pH = 3,0; t = 30 phút,
= 0,1. 3+
- asenazo III là:
5.
3+
La : asenazo III = 1: 2 6. 3+
Ai = (1,9189
3+
-
:
0,2780) .104 . CLa3+ + (0,0076
0,0863).
7.
2+
La(III) là:
CCd 2 C La 3
40 4
8.
-
10 9.
(2-Pyridilazo)-Rezoxin (PAR) và HX (HX: CH3COOH, CH2ClCOOH,
Còn ion Th4+
CHCl2COOH, CCl3
La(III). 10. 11.
0
1.tr. 80-82 (1982).
12. 13. 50
51
14. 15. 16.
-
17.
-
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