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MC LC
LI CM N.........................................................................................................
MC LC........................................................................................................... 1
M U ............................................................................................................. 4
1. L do chn ti............................................................................................ 4
2. Mc tiu v nhim v nghin cu ti......................................................... 4
3. Cc phng php nghin cu......................................................................... 4
4. i tng v khch th ca ti nghin cu................................................ 5
5. Gi thuyt khoa hc ....................................................................................... 5
6. Lch s ti nghin cu............................................................................... 5
7. Gii hn ti nghin cu ............................................................................. 5
NI DUNG ........................................................................................................ 6
CHNG 1: TNG QUAN
1.1 S lc v nguyn t st .............................................................................
1.1.1 V tr v cu to ca st ................................................................... 6
1.1.2 Tnh cht vt l v tnh cht ha hc............................................... 6
1.1.3 Trng thi thin nhin v phng php iu ch ........................... 9
1.1.4 Mt s ng dng ca st................................................................. 10
1.2 S to phc ca st vi thuc th hu c ............................................... 11
1.2.1 Kh nng to phc ca Fe3+ vi thuc th axit sunfosalixilic ....... 11
1.2.2 Kh nng to phc ca Fe vi cc thuc th khc ........................ 11
1.2.2.1. Thuc th SCN- .............................................................................. 11
1.2.2.2 .Thuc th o phenantrolin ............................................................. 13
1.2.2.3 .Thuc th bato phenantrolin ........................................................ 13
1.2.2.4 .Thuc th 1 (2pyridylazo) 2naphthol (PAN) ........................... 14
1.2.2.5. Thuc th 4 (2pyridylazo) rezocxin (PAR) ............................... 14
1.2.2.6 .Thuc th trioxyazobenzen (TOAB)............................................... 15
M U
1. L do chn ti
Trong cng ngh Ha hc th ha hc phn tch khng nh c vai tr ca
mnh qua vic s dng cc phng php ha hc, vt l, ha l khi nghin cu thnh
phn ca cht. Mt trong nhng phng php t c nhng thnh tu to ln trong
khoa hc nghin cu l phng php trc quang khi xc nh hm lng ca cc
nguyn t, cc cht v hp cht.
Vi nhng thnh tu t c t phng php trc quang m ra nhng c hi
mi cho vic nghin cu, i su hn tm hiu v ng dng ca phng php ny trong
thc tin, tm ra cc yu t nh hng,. V vy m ti chn ti: Nghin cu
nh hng ca pH n s to phc ca Fe3+ vi axit sunfosalixilic (SSal) lm bi
kha lun tt nghip .
2. Mc tiu v nhim v nghin cu ti
2.1 .Mc tiu:
- Bit c vai tr ca phng php trc quang trong ha hc phn tch.
- Xc nh thnh phn ca phc st (III) vi axit sunfosalixilic bng phng php trc
quang.
- Vn dng phng php ny trong vic nghin cu nh hng ca pH n s to
phc ca Fe3+ vi axit sunfosalixilic (SSal)
2.2 .Nhim v:
ti cn thc hin cc nhim v trng tm sau:
- Nghin cu phng php trc quang trong ha hc phn tch.
- Nghin cu nh hng ca pH n s to phc ca Fe3+ vi axit sunfosalixilic (SSal)
3. Cc phng php nghin cu
+ Nghin cu l lun: nghin cu cc ti liu, cc trang web, bi vit,.c lin quan
+ Nghin cu thc nghim:
NI DUNG
: 55,847
Fe () 911
Fe () 1390
Fe () 1538
Fe lng
0
Nhng dng v c kin trc tinh th kiu lp phng tm khi nhng c kin
trc electron khc nhau nn Fe () c tnh st t v Fe () c tnh thun t, Fe () khc
vi Fe () l khng ha tan C. Dng Fe () c cu trc tinh th lp phng tm din,
dng Fe () c cu trc lp phng tm khi nh dng v nhng tn ti n nhit
nng chy.
tos (oC)
tonc (oC)
in(Hg=1)
10
2880
1536
BKNT
(Ao)
in
1,26
1,83
cng
KLR
4-5
I1
I2
I3
I4
I5
I6
7,9
16,18
30,63
56*
79*
103
ion ha
Nng lng ion
ha (eV)
* Gi tr cha tin cy.
1.1.2.2. Tnh cht ha hc:
St l kim loi c hot tnh ha hc trung bnh. iu kin thng nu khng c
hi m, chng khng tc dng r rt vi nhng nguyn t khng kim loi in hnh
nh O2 , S , Cl2 , Br2 v c mng oxit bo v. Nhng khi un nng, phn ng xy ra
mnh lit, nht l khi kim loi trng thi chia nh.
Khi un nng trong khng kh kh, st to nn Fe2O3 v nhit cao hn, to nn
Fe3O4:
3Fe + 2O2
Fe3O4
2Fe
+ 3Cl2 2FeCl3
+ 3O2 2Fe3O4
FeO + H2
O
570 C
3Fe + 4H2O
Fe3O4 + 4H2
0
St to thnh hai dy hp cht Fe2+ v Fe3+. Mui Fe2+ c to thnh khi ha tan
st trong dung dch axit long tr axit HNO3. Mui ca Fe2+ vi axit mnh nh: HCl,
H2SO4, d tan trong nc, cn mui ca cc axit yu nh: FeS, FeCO3, kh tan.
Khi tan trong nc, mui st dng [Fe(H2O)6]2+ mu lc nht. Mu lc ca
[Fe(H2O)6]2+ rt yu nn thc t dung dch ca mui Fe2+ khng c mu. Mui FeSO4
l cht tinh th mu trng, d ht m v d tan trong nc. Khi kt tinh t dung dch
nc nhit thng, thu c tinh th hidrat FeSO4.7H2O. Tinh th FeSO4.7H2O
c mu lc nht, nng chy nhit 640C, d tan trong nc v ru. Khi un nng
tinh th FeSO4.7H2O mt dn nc v tr thnh mui khan FeSO4. nhit cao hn
(>5800C) mui khan b phn hu thnh oxit:
580 C
FeSO4
Fe2O3 + SO3 + SO2
0
2FeCl2 + I2 + 2HCl
Ion Fe3+ trong dung dch tc dng vi ion SCN- to nn mt s phc thioxianat. Ho
phn tch thng s dng phn ng ny nh tnh v nh lng Fe3+ ngay c trong
dung dch long.
Kaliferixianua (K3[Fe(CN)6]) l mt trong cc phc bn nht ca st. Kaliferixianua
l cht dng tinh th n t, mu thng c gi l mui mu. Phc ny d tan
trong nc, cho dung dch mu vng v rt c. Kaliferixianua l mt thuc th thng
dng trong phng th nghim nhn bit Fe2+ trong dung dch:
FeCl2 + K3[Fe(CN)6] KFe[Fe(CN)6] + 2KCl
KFe[Fe(CN)6] kt ta mu xanh chm v c gi l xanh Tuabin. Kaliferixianua
khi un nng trong dung dch kim chuyn thnh Kaliferoxianua:
4K3[Fe(CN)6] + 4KOH 4K4[Fe(CN)6] + 2H2O + O2
1.1.3. Trng thi thin nhin v phng php iu ch
St l mt trong nhng nguyn t ph bin nht, ng th 4 sau O, Si, Al. St
trng thi t do trong cc mnh thin thch v cc khong vt,
Trong t nhin st c bn ng v bn: 54Fe (5,8%) , 56Fe (91,8%) , 57Fe (2,15%) ,
58
(=8,27 gi),
53
Fe (=258,8 ngy) ,
(=1,5.106 nm) ,
61
55
Fe (=2,7 nm) ,
Fe (=182,5 ngy) ,
62
51
59
Fe (=0,25 giy) ,
52
Fe
Fe (=44,6 ngy) ,
60
Fe
trng ca st l manhetit (Fe3O4) cha n 72,42 % st, hematit (Fe2O3) cha 60% st,
pirit (FeS2) cha 46,67 % st v xiderit (FeCO3) cha 35% st. Ngoi nhng m ln
tp trung, st cn phn tn trong khong vt ca nhng nguyn t ph bin nh
nhm, titan, mangan, St cn c trong nc thin nhin, trong cc thin thch t
khng gian v tr ri xung tri t. Trung bnh trong 20 thin thch ri xung th c
mt thin thch st (cha 90% st).
Nhiu nc trn th gii c giu qung st nh: Thy in, Nga, Php, Ty Ban
Nha, Trung Quc, M, Canada, Cuba, Brazin, Nam Phi, Cch y hn 4000 nm,
loi ngi bit luyn st t qung. St luyn c cng v bn hn bronz nn l
10
11
max ( nm )
1,5
500
460
Mi trng
Phc
Mu
max (nm)
1,8 - 2,5
axit
Fe[SSal] +
tm
510
4-8
m axetat
[Fe(SSal)2] -
da cam
490
9 - 11
m amoni
> 12
Ba z
420 - 430
Phn hy
12
13
Fe2+
N
N
N
Fe2+/3
14
N=N
N
HO
PAR l cht bt mu thm, tan tt trong nc, ancol v axton. Khi tan trong
nc dung dch c mu vng. Trong thng mi, thuc th PAR thng c s dng
di dng mui c cng thc phn t C11H8N3O2Na.H2O.
Cc cn bng ca thuc th PAR trong dung mi nc:
15
K 0 =10 -3,1
N
OH
+
N
OH
N
HO
HO
H 3 R + (pH<2,1)
H2R (pH=2,1-4,2)
K2=10-11,9
K1=10-5,6
N
O-
O-
N
-
HO
HR- (pH= 4,2- 9)
O
R (pH= 10,5- 13,5)
2-
gi tr khc nhau nh
O
N
Fe
N
N
O
H
O-
16
; KLPT: 254,2
OH
OH
COOH
COO
SO 3H
2-hydroxy-5-sulfobenzoic acid
COOH
SO 3H
2-hydroxy-5-sulfobenzoate
SO 3
2-hydroxy-5-sulfobenzoic acid
17
nhy max
pH xc
nh hng
(nm)
nh
mu
thuc th d
,-dipyridyl
0,007
522
39
1 nm
Khng
2,2,2-terpyridyl
0,005
552
3 10
1 nm
khng
Disodium-1,2-
0.009
Vi thng
Vi thng
3,5-disunfonyl ferron
0,015
610
2,7-3,7
1-2 tun
Khng
4-hidroxylbiPhenyl-3-
0.003
575
1 ngy
dihirobenzen
cacboxylic axit
18
0,014
540
7-12
Vi gi
Khng
Mui nitro-R
0,0023
720
3,9-5,1
6 gi
Khng
o-Phenantrolin
0,007
508
2-9
1 ngy
Khng
Axit salixilic
0,03
520
2,5-2,7
2-3 ngy
Axit sunfosalixilic
0,01
430
Hn 1 ngy
Khng
Thioxianat
0,008
480
Axit
Gim
Thioxiant/nc -
0,004
482
axit
Bin i theo t
axeton
1.4.3.Phng php chun pemanganat
Phn ng oxi ha bng ion pemanganat MnO4- l c s ca phng php
pemanganat. Phng php ny c th thc hin trong mi trng axit, kim v trung
tnh. Khi thc hin trong mi trng axit, mangan (VII) b kh ti mangan (II) v mu
tm ca dung dch b mt.
Thc hin chun mui st (II) bng kalipemanganat: Axit ha dung dch bng dung
dch axit sunfuric v chun ti im cui. St (II) b oxi ha thnh St (III):
5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
Bit nng ng lng v th tch cn chun ca KMnO4 d dng tnh c
lng st trong dung dch.
19
php Oxtromxlenko-Job )
Chun b hai dy dung dch c nng hng nh.
Dy dung dch 1: CFe3+ + CSSal
=aM
=bM
CFe3+ = const
CSSal thay i
CFe3+ thay i
CSSal = const
Tin hnh o mt quang bc sng max , ta cng thu c dy cc A
Suy ra thnh phn phc: [Fe(SSal)m](3-2m)+
1.6.Cc phng php xc nh h s hp th phn t ca phc
1.6.1.Phng php h ng phn t gam
Phng php ny c s dng rt ph bin xc nh thnh phn ca phc mu.
Pha mt dy dung dch: CFe3+ = CSSal v c CFe3+ + CSSal = const ( cng cc iu
kin ti u) .
o mt quang ca cc dung dch , ta c th:
A
CSSal
20
a=
n Ci .Ai Ci . Ai
n. Ci2 ( Ci ) 2
= phc
C . A C . C .A
b=
n. C ( C )
2
i
2
i
, Kcb
21
Xi
n
Phng sai: S
(X
=
n 1
S2
n
tin cy: = t p; k .S X
X a
SX
So snh ttn vi tp;k nu ttn < tp;k th X a l do nguyn nhn ngu nhin hay kt qu
phn tch l tin cy v chp nhn c.
-
Sai s tng i:
q% =
.100 =
t p ; k .S X
X
.100
22
23
+ Dung dch thuc th axit SSal 10-3 M: cn mt lng chnh xc axit SSal
(C7H6O6S.2H2O), ri thm nc ct n vch ca bnh nh mc 250 ml, ta s thu
c dung dch SSal c nng 10-3 M .
+ Dung dch m axetat: pH = 4,2 4,5
Ho 60 ml axt axetic m c vo 300 400 ml nc, thm 100 ml NaOH 10 %,
thm nc thnh 1 lt, khuy u.
Hoc pha t:Axit CH3COOH m c v CH3COONa tinh th.
+ Dung dch HCl ( nng 0,01M ) to mi trng c pH khong 1,8 2,5
+ Dung dch m amoni: pH = 9,5 10,5
Ho tan 54 g amoni clorua vo 500 ml nc, thm 350 ml NH3 m c, thm nc
thnh 1 lt, khuy u.
+ Dung dch NaNO3 1M: cn mt lng chnh xc NaNO3 ri cho nc n vch
nh mc, dng c nh lc ion.
2.3 Cch tin hnh
Ht mt th tch xc nh thuc th SSal, thm mt th tch xc nh NaNO3 gi
lc ion, thm m, sau ht mt th tch chnh xc Fe3+ , thm nc ct n vch
nh mc.
20 pht ri o mt quang ca phc to thnh.
2.4 Phng php nghin cu
Dng phng php trc quang xc nh cc iu kin ti u cho s to phc
(
24
3+
bng m axetat .
o mt quang ca dung dch v phc cht to thnh.T ta xc nh c cc
bc sng (max ) ca phc.
Ta xc nh c max ca phc pH =2,0 v pH = 4,5. Thu c kt qu nh sau:
Bc sng (nm)
A (pH = 2,0)
A (pH = 4,5)
400
0,194
0,224
410
0,211
0,241
420
0,224
0,263
430
0,260
0,296
440
0,284
0,336
450
0,311
0,362
460
0,345
0,382
470
0,368
0,400
480
0,390
0,404
490
0,400
0,414
500
0,404
0,392
25
510
0,394
0,369
520
0,390
0,347
530
0,373
0,316
540
0,348
0,288
550
0,327
0,256
560
0,296
0,236
570
0,274
0,199
580
0,240
0,173
590
0,218
0,166
600
0,194
0,154
th:
Biu xc nh bc sng ti u
0.44
490 nm
500 nm
Mt quang (A)
0.39
0.34
pH = 2
pH = 4.5
0.29
0.24
0.19
0.14
370
400
430
460
490
520
550
580
610
Bc sng
T th trn nhn thy c hai khong max hai khong pH. pH = 2,0 ta o
c max = 500 nm ; cn khong pH = 4,5 ta o c max = 490 nm. Nh vy, ti
s chn hai khong pH hai buc sng ny xc nh thnh phn phc.
26
1,0
0,404
1,5
0,528
2,0
0,542
2,5
0,540
3,5
0,450
4,0
0,390
4,5
0,381
5,0
0,380
5,5
0,375
6,0
0,380
7,0
0,379
8,0
0,230
9,0
0,040
9,5
0,030
10
0,034
10,5
0,030
11
0,035
12
0,033
13
0,008
14
0,004
27
th:
Biu xc nh pH ti u
0.6
Mt quang (A)
0.5
0.4
0.3
0.2
0.1
0
0
10
11
12
13
14
15
pH
28
Kt qu:
Thi gian
(pht)
1
5
10
20
40
60
80
100
120
140
160
180
A
(pH=2)
0,155
0,158
0,160
0,170
0,170
0,171
0,170
0,172
0,169
0,170
0,170
0,171
A
(pH=4,5)
0,162
0,167
0,173
0,178
0,178
0,177
0,178
0,178
0,177
0,178
0,178
0,178
th:
0.18
0.175
0.17
pH=4,5
0.165
pH=2
0.16
0.155
0.15
0
20
40
60
80
100
120
140
160
180
200
Thi gian
Nhn xt: phc c mt quang n nh v t cc i v n nh 20 pht, do
ti quyt nh ly khong thi gian ny tin hnh cc th nghim tip theo.
29
C . 10-5 (M)
V (ml)
Fe 3+
SSal
Fe 3+
SSal
0,00
2,50
10
0,060
0,50
2,00
0,420
0,75
1,75
0,639
1,00
1,50
0,860
1,25
1,25
0,990
1,50
1,00
0,870
1,75
0,75
0,650
2,00
0,50
0,438
2,25
0,25
0,220
10
2,50
0,00
10
0,100
30
Mt quang (A)
th:
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10
11
-5
C (Fe) . 10
Nhn xt:
Ta thy, mt quang t cc i V(Fe3+ ) = V( SSal ) , tc l thnh phn phc c t
[Fe ] = 5.10
3+
l l
[SSal ]
5.10
5
5
1
. Nh vy khong pH = 2,0 ta xc nh c thnh phn
1
phc c t l 1: 1 .
Xc nh h s hp th phn t gam theo phng php ng phn t gam:
CFe3+ ( M )
CSSal (M )
Cphc M
=A/l.Cphc
0,060
///
0,420
1 = 2,10.104
0.10-5
10.10-5
2.10-5
8.10-5
3.10-5
7.10-5
0,639
2 = 2,13.104
4.10-5
6.10-5
0,860
3 = 2,15.104
5.10-5
5.10-5
0,990
4 = 1,98.104
6.10-5
4.10-5
0,870
5 = 2,18.104
7.10-5
3.10-5
0,650
6 = 2,17.104
Cphc = CFe3+
Cphc = CSSal
31
8.10-5
2.10-5
0,438
7 = 2,19.104
9.10-5
1.10-5
0,220
8 = 2,20.104
10.10-5
0.10-5
0,100
///
V Fe 3+ (ml)
V SSal (ml)
A
1,0
0,2
0,4
0,6
0,8
1,0
1,5
1,7
1,9
2,0
2,5
0,182 0,363 0,495 0,670 0,856 0,855 0,856 0,857 0,856 0,856
th:
1
Mt quang (A)
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.5
1.5
2.5
V (SSal)
32
Nhn xt: da vo th ta nhn thy, tng t nh trn ta cng c thnh phn phc
VFe 3+
VSSal
= 1 :1 .
Dy 2:
VSSal ml
2,0
VFe3+ ml
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5 5,0
0,12
0,47
0,98
1,70
1,70
1,72
1,71
1,7
1,70 1,71
th:
2
Mt quang (A)
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
V (Fe) 3
Nhn xt: da vo th ta nhn thy, tng t nh trn ta cng c thnh phn phc
VFe 3+
VSSal
33
C . 10-5 (M)
V (ml)
Fe 3+
SSal
Fe 3+
SSal
0,0
5,0
0,0
20
0,270
0,5
4,5
2,0
18
0,562
1,0
4,0
40
16
1,136
1,5
3,5
6,0
14
1,710
2,0
3,0
8,0
12
1,680
2,5
2,5
10
10
1,435
3,0
2,0
12
8,0
1,150
3,5
1,5
14
6,0
0,865
4,0
1,0
16
4,0
0,579
10
4,5
0,5
18
2,0
0,294
11
5,0
0,0
20
0,0
0,120
34
th:
1.8
Mt quang (A)
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
10
12
-5
14
16
18
20
22
C (SSal) . 10
Nhn xt:
Ta nhn thy mt quang t cc i khong
VSSal 12 14
= :
.
VFe 3+
8 6
VSSal 2
= (do n nguyn dng v
VFe 3+ 1
VSSal 2
3+
= . T cho thy thnh phn phc c t l Fe : SSal = 1: 2
VFe 3+ 1
CFe3+ (M)
CSSal (M)
Cphc (M)
= A/l.Cphc
0,0.10-5
20.10-5
Cphc = CFe3+
0,270
///
2,0.10-5
18.10-5
0,562
1 = 2,810.104
4,0.10-5
16.10-5
1,136
2 = 2,840.104
6,0.10-5
14.10-5
1,710
3 = 2,850.104
8,0.10-5
12.10-5
1,680
4 = 2,700.104
35
10.10-5
10.10-5
1,435
5 = 2,870.104
12.10-5
8,0.10-5
1,150
6 = 2,875.104
14.10-5
6,0.10-5
0,865
7 = 2,883.104
16.10-5
4,0.10-5
0,579
8 = 2,890.104
18.10-5
2,0.10-5
0,294
9 = 2,940.104
20
0,0
0,120
Cphc =
1
CSSal
2
///
CSSal thay i
Kt qu:
Dy 1:
VSSal(ml)
2,0
VFe3+(ml) 0,1
A
0,5
0,8
1,0
1,5
1,7
2,0
2,1
2,3
2,5
0,200 0,590 0,910 1,140 1,143 1,144 1,147 1,150 1,150 1,151
36
th
1.4
Mt quang (A)
1.2
1
0.8
0.6
0.4
0.2
0
0
0.5
1.5
2.5
V (Fe)
l:
VFe 3+
VSSal
1
. Hay thnh phn phc Fe (III): SSal = 1: 2
2
Dy 2:
VFe3+(ml)
VSSal(ml)
A
VSSal 2
= , thnh phn ca phc t t
VFe 3+ 1
1,0
0,2
0,6
0,8
1,0
1,6
2,0
2,2
2,4
2,5
37
th:
Mt quang (A)
1.2
1
0.8
0.6
0.4
0.2
0
0
0.5
1.5
2.5
V (SSal)
VFe 3+
VSSal
1
, nh vy thnh phn phc gia Fe(III) : SSal = 1 : 2 .
2
38
KT LUN
Nh vy, cc khong pH khc nhau m thnh phn phc gia Fe (III) vi SSal c
t l 1:1 hoc 1:2
pH
Mi trng
Phc
Mu
max (nm)
1,8 - 2,5
axit
[FeSSal] +
1: 1
tm
500
4,0 7,0
m axetat
[Fe(SSal)2] -
1: 2
da cam
490
>12
Ba z
Phn hy
39
A. T. Pilipenko
V. Ia. Pochinoc
I. P. Xeraa
Ph. . Sepchenko