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mc
Trang
MC LC .......................................................................................................... 1
GII THIU V M UN .................................................................................. 6
V tr, ngha, vai tr m un ......................................................................... 6
Mc tiu ca mdun ...................................................................................... 6
Mc tiu thc hin ca m un ..................................................................... 6
CC HNH THC DY V HC ...................................................................... 7
YU CU V NH GI HON THNH M UN .......................................... 8
V kin thc ................................................................................................... 8
V k nng ..................................................................................................... 8
V thi ....................................................................................................... 8
Cch nh gi ................................................................................................ 8
BI 1. QUANG PH HNG NGOI.................................................................. 9
M bi. HD E1 ................................................................................................... 9
Gii thiu ....................................................................................................... 9
Mc tiu thc hin ......................................................................................... 9
Ni dung chnh ............................................................................................... 9
1. Mt s khi nim v cc loi dao ng ................................................. 9
2. Cc loi dao ng................................................................................ 13
2.1. Dao ng quay ca phn t v quang ph quay (Ph hng ngoi
xa)
13
2.2. Dao ng iu ha ........................................................................ 14
2.3. Dao ng khng iu ha ................................................................. 16
2.4. Dao ng quay ................................................................................. 17
2.5. Dao ng ring ca phn t.......................................................... 17
2.6. Dao ng nhm (hay cn gi l dao ng nhm chc) v tn s c
trng ........................................................................................................ 19
3. Tn s c trng, cc yu t nh hng ................................................ 20
3.1. nh hng ca trng thi tp hp ................................................ 21
3.2. nh hng ca lin kt hydro ni phn t .................................... 21
3.3. nh hng ca dung mi ................................................................. 23
4. My quang ph hng ngoi v cc iu kin ghi ph ............................. 24
4.1. My quang ph hng ngoi hai chm tia ...................................... 24
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4.2.
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4.7.
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GII THIU V M UN
V tr, ngha, vai tr m un
Phng php ph hng ngoi (IR), nhiu x tia X (XRD), hp thu nguyn
t (AAS) l nhng phng php vt l rt hu hiu nghin cu cu to ca
cc phn t hu c, cc nhm chc c trng, cu trc ca cc hp cht v
c lm cht xc tc, hp ph, cc nguyn t ha cht. C s ca phng
php da trn hin tng bc x in t ca phn t vt cht di tc ng
ca sng in t khi c chiu bi nh sng c bc sng khc nhau hoc
s hp th cc bc sng c trng khi nguyn t ho cc cht hu c.
Vic ng dng phng php ph ngy cng rng ri trong nhiu lnh vc
nghin cu khc nhau khng nh v tr quan trng ca phng php trong
nghin cu khoa hc cng nh trong phn tch cc hp cht ha hc c bit
l cc hp cht hu c ho du v cht xc tc trong ho du. V vy vic tip
thu uc s s l thuyt ca phng php v k thut thao tc vn hnh my
mc thit b o ph l rt quan trng v cn thit.
Mc tiu ca mdun
Hc xong modun ny hc vin cn phi :
Hiu c bn cht ca cc phng php quang ph khc nhau.
Bit cch xc nh thnh phn hydrocacbon bng ph hng ngo1.
Xc nh cc cu trc vt liu bng ph Rnghen (XRD)
Xc nh c hm lng kim loi nng c trong du m v cc
phn on nng ca du.
Mc tiu thc hin ca m un
Khi hon thnh m un ny hc vin c kh nng:
M t c bn cht ca cc phng php quang ph khc nhau:
Hng ngoi IR, nhiu x tia X (Rnghen) XRD, hp thu nguyn t
AAS. Bit cch xc nh thnh phn hydrocacbon parafin, Naphten,
Aromatic bng ph hng ngoi IR
Xc nh cu trc vt liu bng ph Rnghen XRD
Xc nh uc hm lng kim loi nng c trong sn phm du
bng phng php quang ph hp thu nguyn t AAS.
Thc hin cc th nghim trong PTN Ho du.
Bi 1. Ph hng ngoi
Bi 2. Ph nhiu x tia X (Rn nghen)
Bi 3. Ph hp thu nguyn t AAS
6
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CC HNH THC DY V HC
1. Hc trn lp v
-
2.
T nghin cu ti liu lin quan n k thut phn tch mu, trnh t tin
hnh php phn tch trong phng th nghim do gio vin hng dn.
3.
Xem trnh din v thc hnh vic s dng cc dng c, trang thit b ph
4.
5.
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YU CU V NH GI HON THNH M UN
V kin thc
-
X l v gii cc ph .
Vit bo co kt qa.
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1.1.1. Bc x in t
Bc x in t bao gm t sng v tuyn n cc bc x Rnghen v
bc x gama. Cc bc x in t ny u c bn cht sng v bn cht ht.
Bn cht sng c th hin qua hin tng nhiu x v giao thoa.
Thuyt ht cho thy bc x gm cc ht nng lng gi l photon chuyn
ng vi tc nh sng. Cc ht khc nhau th khc nhau v nng lng h
ca cc ht proton.
Nng lng bc x c biu din theo biu thc Planck nh sau :
E = h.
Trong h l hng s Planck h = 6,626 x10-27 ec.s =6,626x10-34 .J.s
1.1.2. Cc i lung o bc x in t
Bc x in t c c trng bng cc i lng o khc nhau nh :
bc sng, s sng, tn s v nng lng.
a. di sng (bc sng)
ng y .
biu din di sng, ngi ta dng cc n v di khc nhau,
micromet ( ), nanomet (nm) Angstron (Ao)
(1.1)
Trong : c l tc nh sng.
Chiu di bc sng c o bng n v o chiu di : cm, nm, Ao
10
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hc
= h c.
(1.2)
, cm-1
-11
-8
E, eV
Tia
Tia Rngen
Tia t ngoi kh kin
Hng ngoi
Vi sng
10 -10
10-8-10-6
10-6-10-4
10-4-10-2
10-1-10
~107
~105
~10
~10-1
~10-3
Sng v tuyn
>100
~10-6
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11
qy
h
(1.3)
dd
qy
12
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Bc sng ( m)
Vng
Hng ngoi gn
Hng ngoi gia
0,78 2,5
2,5 - 50
12800 - 4000
4000 - 200
Hng ngoi xa
50 - 1000
200 - 10
Vng hng ngoi thng s dng nht nm trong khong 4000 -670cm-1.
Nng lng ca bc x hng ngoi khng ln c th bt electron
ra khi qu o ca n nh bc x ca tia t ngoi U5.
S hp th bc x hng ngoi ca hp cht c th lm quay phn t
hoc dao ng cc nguyn t trong phn t ca chng.
2.1. Dao ng quay ca phn t v quang ph quay (Ph hng ngoi xa)
Cc phn t khi b chiu bi bc x in t c bc sng vng hng
ngoi xa (200-10cm-1) s quay quanh cc trc cn bng ca n.
i vi cc phn t c hai nguyn t ging nhau nh(H2,Cl2, N2) v khc
nhau (nh HCl, CO) th nu hai nguyn t c m in khc nhau momen
lng cc ca chng s khc 0. Khi b kch thch bi nh sng vi tn s thch
hp s lm quay phn t. S bc quay s ph thuc vo cu trc khng gian
ca chng.
Nng lng quay c th biu din qua phng trnh sau
Eq = nh
(J+1)
(1.4)
m1 m2
m1 m2
h
8Ic
(1.5)
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13
t :
v
Eq
= F(J) l s hng quay
hc
h
8.Ic
= B l hng s quay
Ta c
F(J) =BJ(J+1)
(1.6)
Hng s quay B s c trng cho mi phn t.
thu uc ph quay ca phn t ngi ta dng bc x hng ngoi xa
hoc bc x vi sng. Ph quay ca phn t ngoi vic nhn dng cc cht
cn cho php xc nh khong cch gia cc nguyn t v gc gia cc lin
kt (i vi cc phn t khng phc tp.)
T cc d kin ca ph quay ngi ta thu c nhng gi tr ca khong
cch nguyn t trong phn t ca mt s cht nh sau
HF
HCl
HBr
HI
CO
NO
Ro (Ao) 0,87 1,28 1,42 1,62
1,13 1,15
Bng 1.2: Gi tr hng s quay ca mt s phn t nh sau
Phn t
B, cm-1
H2
HF
LiH
CO
O2
Cl2
60,8
20,9
4,23
1,95
1,45
0,244
2.2. Dao ng iu ha
Dao ng iu ha l dao ng qu lc ngha l vt th chuyn ng
quanh v tr cn bng ca n v c hai pha vi bin khng 1.
Trong trng hp dao ng iu ha, lc n hi F t l thun vi
lch x
F = - k x (1.7)
Trong k l hng s lc.
lch x ph thuc vo thi gian.
Tn s dao ng c biu din qua phng trnh sau :
=
1
2
k
M
(1.8)
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,cm-1
k, dyn.cm-1
H2
HF
4160
3958
5,2
8,8
HCl
2885
4,8
HBr
2559
3,8
HI
N2
2230
2331
2,0
22,6
C0
O2
F2
Cl2
2143
1556
892
557
18,7
11,4
4,5
3,2
(n+
1
)
2
(1.9)
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15
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Mc dao ng
, cm-1
0-1
0-2
288,5
566,8
0-3
8347,5
0-4
0-5
10923,6
13396,5
dd
qy
(1.10)
17
OH(s).
OH(as)
OH.
18
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19
K(din/cm)
-5
5,5.10
9,610-5
15,610-5
5,1.10-5
12,1.10-5
4,7.10-5
E(kcal/mol)
84
147
194
79
176
66
Lin kt
K(din/cm)
>C=N
-C N
-CH
=C-H
C-H
C-Hthm
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10,5.10
17,7.105
4,8.105
5,3.105
5,9.105
5,0.105
E(kcal/mol)
150
215
98
104
120
109
a.
b.
Hnh 1.7 : Ph hng ngoi ca CH3I ; a - th kh ; b - th lng
trng thi tinh th mi phn t c bao quanh bi mt s phn t
cng loi sp xp theo th t xc nh. Cc tinh th khc nhau c s sp xp
khc nhau dn ti tng tc cng khc nhau lm cho thay i tn s dao
ng.
3.2. nh hng ca lin kt hydro ni phn t
Lin kt hydro l lin kt yu c hnh thnh khi nguyn t hydro
tham gia lin kt cng ha tr vi nguyn t ca nguyn t m in mnh li
tng tc vi mt nguyn t m in khc. C th biu din nh sau
AX-H....YB
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21
22
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23
Dao
Th
ng
hi
CH
NH
OH
vCO
CO
CO
Hexan
CCl4
CS2
CHCl2
Ete
3337
3530
3323
3506
3313
3500
3300
3481
3309
3486
3250
3352
3654
3622
3611
3593
3695
3344
1709
1697
1692
1690
1683
1694
1750
1753
1744
1730
1741
1728
1734
1720
1726
1730
C=O)
24
B phn x l tn hiu .
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.
Hnh1.10 :.S nguyn tc v my hng ngoi hai chm tia
4.1.1. Ngun sng
Thng dng trong thit b IR l n Nernst cha oxit kim loi t him
hoc cacbit silic c kh nng t nng n nhit cao v pht ra tia hng
ngai.
Chm tia ny t ngun sng thng l tia a sc cho nn phi qua b
phn lc tch nh sng n sc gm nhng lng knh c ch to t cc
tinh th mui lm vt liu nh LiF, CaF2, NaCl, KBr..,
Cc cch t ny ch cho nh sng vi khong buc sng nht nh i
qua.
Cu to ca n Nernst gm mt ng thy tinh c ng knh khong 12mm, di khong 20-50 mm. Trong ng ng oxit ZrO2 v Y2O3 c cc si
platin gn vo hai u ng ni vi mch in. Nhit t nng khong
1200-2200 oK
n Globar.
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25
2-6 m
CaF2
1-8 m
NaCl
2,5 15 m
KBr
12,5 25 m
CsI
25 50 m
26
Detect (6)
My tnh (7)
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Vng bc x hng
ngoi cm
Si thch anh
Si/CaF2
Si/CaF2
Ge/CsI, NaCl, KBr
Mylar 3,5
Mylar 6,5
Mylar 12,5
Ghi ch
-1
20.000-3000
10.000-2000
5000-300
5000-400
700-100
500-100
250-50
IR gn
IR gn
IR trung bnh
IR trung bnh
IR xa
IR xa
IR xa
4.2.3. Detect
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27
Vng ph IR cm-1
Diod Si
20000-8000
PbS (N2)
DTGS (detet triglycin sunfat)
10000-4000
5000-400
CsL
MCT (N2)
5000-200
5000-500
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29
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31
32
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Th mono
Th cis-di
Th trans-di
Th gemi-di
Th tri
Th tetra
i vi hp cht m phn t olephin i xng tm th dao ng ha tr
C=C khng xut hin v dao ng ny khng lm thay i momen lng cc.
Cn trong cc hp cht khng i xng th cng hp th ca lin kt ny
tng khi lin kt i dch chuyn v pha u mch.
V tr nh hp th ca dao ng ha tr lin kt C=C trong 1680-1640
cm-1 v n ph thuc vo cu trc hnh hc v mc th ca lin kt.
Bng 1.9: Dao ng ca C=C olephin
Cu to ha hc
, cm-1.
RCH=CH2(th mono)
R1R2C=CH2(th gemi)
R1CH=CHR2 (th cis, trans)
Cis
Trans
1648-1638
1658-1648
R1R2C=CHR3(th tri)
R1R2C=CR3R4 (th tetra)
1675-1665
1675-1665.
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1662-1652
1678-1668
33
, cm-1
Hexen-1
1642
42
Pentadien-1,4
1642
40
3,3 dimetylbyten-1
1645
46
2,dimetylpenten-1
cis-penten -2
1653
1658
33
10
trans-penten -2
1670
Cung
1600cm-1
Dao ng ca ni i lin hp vi nhm cacbonyl nm vng 16401590 cm-1.
Dao ng bin dng ngoi mt phng ca nhm H-C=C-H trong
phn t olephin rt c trng tn s 1000-800 cm-1 v c cng
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Loi th
bin dng
Cng
C-H
770-730
710-690
770-735
Mnh
Mnh
Mnh
Th hai ln 1,4 v bn ln
1,2,3,4
900-860
810-750
725-680
860-800
800-770
Mnh
Trung bnh
Mnh
Mnh
Mnh
Th ba ln 1,2,3
720-685
Trung bnh
Th ba ln 1,3,5
Th bn ln 1,2,3,5 v
1,2,4,5.
860-800
900-860
900-860
865-810
730-675
860-800
Mnh
Trung bnh
Trung bnh
Mnh
Mnh
Trung bnh
Th nm ln
900-860
Trung bnh
Th mt ln
Th hai ln 1,2
Th hai ln 1,3
Th ba ln 1,2,4
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35
Th orto
Th meta
Th para
1027 3
1033 11
1076 7
1013 5
1073 4
1125 14
1076 7
1117 7
1156 5
1160 4
1157 5
1175 6
1177 6
1269 17
1278 12
1258 11
1240 8
36
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CH
37
Tn s
cm-1
Dng dao
ng
Ghi ch
-OH t do
3650-3590
Ha tr OH
Thng nhn
3600-3200
Ha tr OH
Thng t. Lin kt
hidro cng mnh,
tn s cng gim
3200-2500
Ha tr OH
Hay ln vi dao
dng OH ca axit
3710,
3600-3100
Ha tr OH
Vch ph rng
1640-1615
Bin dng OH
3500-3450
Ha tr OH
-O-H
-C-OH
1410-1260
1150-1040
Bin dngOH
Ha tr C-O
38
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39
Hp cht
O-H t do
3670-3580
2550-3200
Cu hydro ni phn t
3590-3420
3200-2500
CH2=CH-CH2-OH
3631-khng lin hp
3618 -lin hp
CH C-CH2-OH
C6H5OH
3620-khng lin hp
3617-3590 khng lin hp
3250-3200 lin hp
C6H5-CH2-OH
C6H5CH2CH2-O-H
40
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Tn s cm-1
Ancol bc I
1420,1330
Ancol bc II
1430,1320,1225
Ancol bc III
Phenol
1410, 1320
1390-1330
1260-1180
2-ankylphenol
1321-1319
1256-1242
1171-1160
3-ankylphenol
4-ankylphenol
1285-1269
1188-1180
1260-1248
1171-1166
a. Dao ng ha tr ca nhm C-OLin kt C-O l lin kt khng phn cc c vch ph cng mnh
vng 1200-1000 cm-1, c trng cho dao ng ha tr ca mch. Ngoi ra cn
xut hin cc vch ph cng mnh vng 1400-1000 cm-1 c trng cho
dao ng bin dng trong mt phng.
Bng 1.16: Dao ng ha tr ca nhm C-O- trong ancol
ty thuc vo bc ca ancol
Hp cht
Tn s cm-1
Ancol bc I
1075-1000
Ancol bc II thng
1125-1090
Ancol bc II thm
1075-1000
Ancol bc III
1210-1100
Phenol
1260-1180
b. Cc hp cht ete
Trong phn t ca hp cht ete c nhm C-O-C hp th vng sau
Khi c mt oxy trong phn t th tn s dao ng ha tr ca nhm CH 3
v CH2 ni trc tip vi nguyn t oxy s b thay 1.
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41
tn s cm-1
1140-1085
1310-1210
1050-1010
Vinyl ete
Epoxy
1225-1200
1270-1250
950-810
840-750
V d
Dao ng ha tr ca nhm metyl trong ete mch thng
(ROCH3)chuyn dch n vng 2830-2815 cm-1 cn trong ete vng
(ArOCH3) th chuyn v vng 2850 cm-1.
Dao ng ha tr ca nhm CH trong , -ete khng no 3150-3050 cm-1.
5.6.3. Cc hp cht Ccbonyl C=O
Ph hp th ca tt c cc cht cha nhm C=O nh andehi, keton,
quinon, cacboxilic axit, anhidrit, clorua axit... c vch ph hp th vi cng
mnh ( =300-2000) trong vng 1900-1580 cm-1, vch ph ny c trng
cho dao ng ca nhm C=O.
V tr v cng cu vch ph ny ph thuc vo cu trc ca cc phn
t hp cht (cu to hnh hc, khi lng nguyn t lin kt vi nhm C=O,
cm ng v hiu ng meso...)
Ngoi ra tn s hp th cn ph thuc vo trng thi tn ti ca hp cht
trong dung mi (s to thnh lin kt cu hydro hoc tng tc tnh in. i
vi mt s hp cht cacbonyl vch ph c trng cho dao ng ha tr
C=O
a.
42
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b.
c.
Hnh 1.17. Ph hng ngoi ca mt s hp cht cha nhm cacbonyl CO
a) n-propyl phenyl xeton; b) 2-metyl-1,4-naphtoquinon; c) Axit valeric
a. Andehit mch thng
Vch ph hp th ca nhm C=O vng 1740-1720 cm-1 trng thi
kh tn s hp th s cao hn khong 20 cm-1.
Nhm chc ca andehit ngoi nhm C=O cn c mt lin kt hydro vi
nguyn t ccbon ca nhm cacbonyl, do s chuyn dch cc in t
nhm C=O c th tn ti dng mesome sau: RHC=O
RHC O
ca
C=O
cm-1
C=C
cm-1
C6H6-CHO
1705 (lng)
CH2=CH-CHO
CH2C-CHO
1620
1638
1700 (1685)
1677
1674
1673
1664
1692
1644
1642
1615
1592
1570
-
CH3CH=CH-CHO
CH3(CH=CH)2CHO
CH3(CH=CH)3CHO
CH3(CH=CH)4CHO
CH3(CH=CH)5CHO
HC C-CHO
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43
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C=O
C=C
CH3-CO-CH2=CH2
1723
1639
CH3-CO-CH2-C(CH3)=CH2
CH3-CO-CH2-CH=CH2
CH3-CO-CH2-C(CH3)=CH2
1718
1718
1706
1651
1683
1618
CH3-CO-CH=CH-CH3
1686
1630
CH3-CO-CH=CH-CH(CH3)2
1684
1619
1707
1690
1634
1626
1701, 1682
1702
1622
1621
C=O
(cm-1)
C6H5-CO-CH3
C6H5-CO-CH2-CH3
p-CH3-C6H4-CO-CH3
1691
1692
1691
p-NO2-C6H4-CO-CH3
1700
1685
1685
1664
-Naphtyl-CO-CH3
-Naphtyl-CO-CH3
C6H5-CO-C6H5
1661
1667
1651
p-CH3-C6H4-CO-C6H5
p-Cl-C6H4-CO-C6H5
p-NH2-C6H4-CO-C6H5
Hp cht
Gc vng
()
Xiclobutanon
82
1788
Xiclopentanon
Xiclohexanon
Xicloheptanon
101
116
121
1746
1715
1703
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C=O
45
Xiclooctanon
133
1702
C8
a)
b)
Hnh 1.19: Ph hng ngoi ca mt s xeton khng bo ha
a) trans-2-hexanal ; b) 3-penten 2-on
e. Axt cacboxylic
Axit cacboxylic trng thi hi v trong dung mi khng phn cc vi
nng thp c ph hp th ca nhm C=O vng 1790-1770 cm-1. trng
thi rn vch hp th s chuyn dch v pha bc sng di hn khong 30
cm-1.
Mt khc trng thi rn v lng th vch hp th nhm C=O ca axit
cacboxylic hu nh trng hp vi keton v andehit nhng cng ca
chng cao hn khong 2-3 ln ( =1500 so vi keton l 300-600).
Este phc c vch ph ca nhm C=O 1750-7-1735 cm-1. Cng ging
nh axit trong ph ca este phc xut hin vch ph vng 1300-1050 cm-1
c trng cho nhm C-O-C, nhng c cng mnh hn v rng hn, i
khi b chia tch thnh nhng vch nh.
46
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C=O
C=O
OH
s khc so vi andehit,
a)
b)
Hnh 1.20. Ph hng ngoi ca mt s axit hu c
1- axit phenyl axetic; 2- axit benzoic ;
Cc axit cacboxylic c th to lin kt cu hydro gia hai phn t to ra
dimer lm thay i tn s c trng ca
C=O
OH
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v thng c hai nh
47
C=O
ca hp cht th hi l
C=O
OH
Monome
dime
Axit cha bo ha
> C=CH-COOH
1710 1680
> C C-COOH
1690 1670
48
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49
V d:
Oxim xiclohexanon c cng hp th ( = 20) trong khi i vi hp
cht dng Ar-CH=N-Ar th cng tng ln rt cao ( = 100)
Bng 1.23: tn s hp th ca lin kt N-H ca nhm amin (cm-1)
Cht
Dung dch
Hi
Metyl amin
3398
3425
3344
3360
n-butylamin
3398
3412
3344
3447
anilin
3398
3407
3344
3416
Trong cc amin thm, nu bn cnh nhm NH 2 cn c cc nhm OH, COOR, NO2 c th hnh thnh cu ni hydro ni phn t cho nn tn s
N-H
gim
V d:
Vng 1650 1500 v 960 650 cm-1 c trng cho dao ng bin dng
N-H ca amin bc 1 v 2,
N-H
vch 1600 1500 cm-1 c cng yu c trng cho dao ng bin dng
ca amin bc 2.
Lin kt cu hydro lm tng tn s hp th. Nhm CH3-N v CH3-NH-R
hp th tn s thp hn nhm CH3 ca hydrocacbon
Bng 1.24: Tn s hp th
R
Ankyl
Aryl
CH3
ArylN(CH3)
CH3
ca amin
CH3
1805 2780
2820 2815
2825 2810
2725 2765,
2800
Mui ca amin: nhm NH3 trong mui amin hp th vng 3020 cm-1 c
trng cho dao ng ha tr ca NH3
Dao ng bin dng ca NH3 hp th vng 1600 1570 cm-1
50
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C=C
gim t 1263 n
1516 cm-1
Trong cc hp cht Aryl-Me th tn s hp th Me-C 1120 -1050 cm-1
Hp cht c kim ca cc vng khng no 5 cnh v 6 cnh c nhng vch
ph c trng 3100 cm-1 (dao ng ha tr ca C-H), 1950 cm-1 dao ng
i xng ca vng v 1005 cm-1, 814 cm-1 dao ng bin dng trong mt
phng v ngoi mch thng ca lin kt C-H. Khi trong vng c nhm th th
vch ph 1005 v 1150 cm-1 s bin mt v c th da vo hin tng ny
phn bit vng c nhm th hay khng. Khi lin kt kim loi-vng gim th tn
s dao ng C-H ngoi mt phng cng gim theo.
Bng 1.25: Tn s c trng ca mt s phc c kim
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C-Me
51
Hp cht
C-Me
(cm-1)
Al2(CH3)6
Al2(CH3)4Cl2
Al2(C2H5)6
720, 585
662, 545, 477
Cd(CH3)2
Cd(CH3)4
Hg(CH3)2
538
602
550
LiCH3
514, 417
LiC6H5
421, 378
Pb(CH3)4
PtCl2C3H6
478
563
Sn(C6H5)4
(CH3)3SnCl
(C6H5)3SnCl
(CH3)2Zn
(C5H5)2Fe
1062
513, 545
1066
615
478
C-H
c gi tr 668 cm-1 i vi
C-H
S to thnh lin kt
= 3037 cm-1
vi kim loi dn n s gim tn s dao ng ca
C=O
52
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C=O
C=O
Hp cht
Me-C
Ni(CO)4
2057
422
Fe(CO)5
[Mn(CO)5]Cr(CO)6
2028, 1994
1898 1863
2000
472, 430
Mo(CO)6
Fe2(CO)9
2004
2080, 2034
368
Fe3(CO)12
441
53
lg
Io
I
.c.
Trong :
D: mt quang
: h s hp th
c: nng
: chiu dy lp dung dch
Theo phng trnh trn, i vi mi mt cht trong cc iu kin nht
nh v bc sng v cng mt loi cuvet th mt quang t l vi nng
dung dch. S ph thuc tuyn tnh ny ch ng trong khong nng thp
ca dung dch. Nu nng qu cao s xut hin nh hng ca s phn x
v tn x nh sng trong dung dch. Ngoi ra ca s ca cuvet c ch
bng tinh th KBr, NaCl rt d b ht m v b m cho nn d gy sai s.
6.2.1. nh lng mu tinh khit
nh lng mu tinh khit cn phi ghi ph v thit lp mi quan h
gia t s hp th (Io/I) vi nng cht khc nhau bc sng nht nh.
T s (Io/I) c th xc nh da trn ph vi ng nn c s.
Cch thc hin: lp bng
Pha mu vi cc nng khc nhau C1, C2, C3, C4,... Cn
o ph ca mu v xc nh gi tr mt quang tng ng bng t s
hp th (Io/I) trn cc ph .
Ch chn ng nn sao cho xc nh Io mt cch chnh xc.
V th ng cong chun ph thuc gia D v f(c) t gi tr thc
nghim
mu
54
STT
[c] mg/l
1
2
3
4
5
6
7
8
9
10
2
4
6
8
10
12
14
16
18
20
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
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1c1
2c2
3c3
4c4l
+... +
ncn
Trong :
DTS: mt quang ca dung dch o
Di: mt quang ca mi hp phn
i:
h s hp th ca mi hp phn
1
1
DTs2
2
1
.c1 .
2
2
.c 2 .
2
3
DTs3
3
1
.c1 .
3
2
.c 2 .
3
3
.c1 .
1
2
.c 2 .
1
3
.c3 .
.c3 .
.c3 .
2
trong D1Ts , D Ts
, D 3Ts l mt quang ca ba bc sng c trng khc
ca mi hp phn
(cm-1)
2975 2950
2885 2860
( m)
3,36 3,39
3,47 3,50
Cng
mnh (70)
mnh (30)
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Ghi ch
as-CH3: bt
i xng
s-CH3: i
xng
55
O-CH3
N-CH3
-C(CH3)2
2830 2815
2820 2730
1470 1435
1385 1370
1385 1370
1370 1365
1175 1165
1170 1140
840 790
6,80 6,97
7,22 7,30
7,22 7,30
7,30 7,33
8,51 8,58
8,55 8,77
11,90 12,66
1395 1385
1365
1255 1245
1250 1200
2940 2915
2870 2845
7,17 7,22
7,33
7,97 8,03
8,00 8,33
3,40 3,45
3,49 3,52
mnh (15)
mnh
mnh
mnh
mnh
Tb
Tb
mnh
mnh
mnh
mnh (75)
mnh (45)
-CH2- trong
vng 3 cnh
xiclopropan
3080 3040
1020 1000
3,25 3,29
9,80 10,00
Tb
Tb
-(CH2)n-
750 720
1350 1180
13,33 13,89
7,40 8,48
mnh
yu
2900 2880
1340
3,45 3,47
7,46
yu
yu
-C(CH3)3
-CH2-
as-CH3
s-CH3
dao ng
mnh
dao ng
mnh
dao ng
mnh
Dao ng
trong mch
Nt
bt i
xng
CH2 i xng
CH2 bt i
xng
dao ng
mch
CH2
56
Nhm chc
-CHR=CH
(cm-1)
3095 3010
2975
1420 1410
1300 1290
995 985
915 905
Cng
Trung bnh
(30)
Trung bnh
Trung bnh
Thay i
mnh (50)
mnh (110)
RRC=CH2
3095 3075
1800 1750
Trung bnh
Tb (30)
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Ghi ch
CH2: bt i
xng
CH2: i xng
CH2 trong mt
phng
CH trong mt
phng
CH2 ngoi mt
phng
CH ngoi mt
phng
CH2
1420 1410
895 885
Tb (10 20)
mnh (100
150)
3040 3010
1420 1400
730 665
Tb
Tb (10 20)
Tb (40)
CHR=CHR
Trans
3040 3010
1310 1290
980 960
Tb
yu
mnh (100)
CRR=CHR
3040 3010
850 790
Tb
mnh
CHR=CHR
C=C khng
lin hp
CHR=CH2
CRR=CH2
CHR=CHR cis
CHR=CHR
trans
CRR=CRR
Dien
Polydien
C=C lin hp
vi phenol
C=C lin hp
vi CO
trong mt
phng
CH2 ngoi mt
phng
CH2
CH
CH trong mt
phng
CH ngoi mt
phng
CH
trong mt
phng
CH ngoi mt
phng
CH
CH
CH ngoi mt
phng
Tb (40)
Tb (35)
Tb
yu
1690 1670
1650-1600
1650
1625
Thay i
1660 1586
mnh
mnh
(cm-1)
1625 1575
1525 1475
1590 1375
1465 1440
Thay
i
Thay
i
Thay
i
Thay
i
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Ghi ch
Thng gn vi 1600
gn vi 1500
mnh i vi h lin
hp
57
Dao ng ha tr C-H
3080 3030
Tb
Thng c vi vch
(<60)
ph
Dao ng bin dng CH trong mt phng
Mt nhm th
1175 1125
yu
1,3 ; 1,2,3
1110 1070
yu
v1,3,5 nhm
1070 1000
yu
th
Dao ng bin dng CH ngoi mt phng
Mt nhm th
770 730
mnh
1,2 nhm th
710 690
mnh
1,3 nhm th
770 735
mnh
900 860
tb
810 750
mnh
725 680
tb
1,4 v 1,2,3,4
860 800
mnh
nhm th
800 770
mnh
1,2,3 nhm th
720 685
tb
860 800
mnh
1,2,4 nhm th
900 860
tb
Trong vng 2000 1600 cm-1, tt c hp cht thm u c nhm vch
ph yu, s lng v v tr vch ph c xc nh bi loi th ca vng
thm.
7.4. Hp cht c kim
Cc lin kt kim loi-cacbon Me-C trong cc hp cht c kim cho hp th
c trng trong quang ph hng ngoi tn s 800 400 cm-1 ty theo gc
hu c v kim lo1.
Dao ng bin dng ca nhm CH3 lin kt vi kim loi (Me-CH3) c vch
ph vng 1180 1140 cm-1.
Dao ng bin dng ca -CH2- lin kt vi kim loi (Me-CH2-) hp th
vng 1430 1415 cm-1 i vi phc ca Hg, Zn, Cd, Sn.
Trong cc hp cht Aryl-Me th tn s c trng vng 1120 1050 cm-1
V d:
Si(C6H5)4 - vch ph 1100 cm-1
Ge(C6H5)4 - vch ph 1080 cm-1
Sn(C6H5)4 - vch ph 1152 cm-1
Pb(C6H5)4 - vch ph 1052 cm-1
7.5. Hp cht d vng
58
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vng
-1
NH
800 cm v
NH
CH
CH
700
1620 cm-1.
CH
CH
(1600 cm-1)
2- CA = 3,0+6,6
(813 cm-1)
(720 cm-1)
(720cm-1)
lg
59
60
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61
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B cp ngun sng,
Cn phn tch.
Thit b chun b mu rn. KBr
T sy chn khng.
Bnh ng mu cc loi.
Bnh ht m
Dung mi cho tng bi c th.CCl4, CHCl3...
Cc mu hydrocacbon chun.(n-parafin C6-C10, cyclohexan, benzen,
toluen, xylen,...)
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63
64
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(1600 cm-1)
2. CA = 3,0 + 6,6
(813 cm-1)
65
3. CA = 36,2 + 6,6
(720 cm-1)
(720cm-1)
lg
Trong :
: dy ca cuvt (thng l 1 mm)
0 : cng tia n sc ban u trc khi truyn qua lp vt liu
:Cng tia n sc sau khi qua khi lp vt liu.
Phiu nh gi thc hnh xc nh hm lung hydrocacbon trong phn
on du m bng ph hng ngoi.
C
thc
hin
66
Khng
thc
hin
Khng
t
Tiu
chun
hot ng
Theo hng
dn qui nh
Theo yu cu
k thut cho
tng bi
Theo hng
dn
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Thao tc m my v ci
ng qui trnh
t cc thng s theo yu
cu phn tch
thao tc k
thut
Ch cc thng s n nh
ng trnh t,
v tin hnh o ph ca
k thut chnh
cc mu chun, mu
phn tch
xc
Theo di hot ng ca
Ghi chp y
, iu chnh
tch
kp thi
Ghi nhn xt
Ch n nh v tr my
Ghi nhn xt
Np phiu bo
co, bn giao
my
Vch ph
c trng
Cng
Hm lng
%
Parafin
Naphten
Hydrocacbon
thm
Nhn xt bi thc hnh v cc ch thch cc kt qu thc nghim.
10. Cu hi v bi tp gii ph hng ngoi
1.
2.
3.
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67
4.
5.
68
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http://www.ebook.edu.vn
69
70
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71
Tt c cc nguyn t u c th hp th nh sng
(2.1)
72
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F-AAS
Nguyn t
ETA-AAS
(nm)
Ngn la
01
Ag-328,10
AA
0,05
0,10
02
Al-309,30
NA
0,10
0,50
03
Au-242,80
AA
0,05
0,05
04
Ba-553,50
NA
0,10
0,50
05
Be-234,90
NA
0,10
0,30
06
Bi-223,10
AA
0,10
1,00
07
Ca-422,70
AA
0,05
0,05
08
Cd-228,80
AA
0,03
0,04
09
Co-240,70
AA
0,10
1,00
10
Cr-357,50
AA
0,10
0,80
11
Cu-324,70
AA
0,04
0,05
12
Fe-248,30
AA
0,08
0,10
13
K-766,50
AA
0,05
0,10
14
Mg-285,20
AA
0,03
0,10
15
Mn-279,50
AA
0,05
0,06
16
Na-589,60
AA
0,03
0,05
17
Ni-232,00
AA
0,10
0,10
18
Pb-283,30
AA
0,10
0,20
19
Sr-466,70
AA
0,08
0,20
20
Si-251,60
NA
0,30
1,00
21
Zn-213,90
AA
0,03
0,10
73
NaCl hi
Na+, Cl-
74
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tch
Nng lng(nhit ) ca ngn la phi ln v c th iu chnh
c ty theo tng mc ch phn tch mi nguyn t. ng thi li
phi n nh theo thi gian v c th lp li c trong cc ln phn
tch khc nhau m bo cho php phn tch t kt qu ng
n.
Ngn la phi thun khit. Ngha l khng sinh ra cc vch ph ph
lm kh khn cho php o hay to ra ph nn qu ln gy nhiu cho
php o.
Qu trnh ion ha v pht x phi khng ng k.
Ngn la phi c b dy ln lm tng nhy ca php o..
Trong cc my hin nay, b dy ny c th thay i c t 2cm
n 10 cm.
T l kh
Nhit (0C)
6/1,4
2200
Khng kh
Propan
Khng kh
Axetylen
4,2/1,2
2450
Khng kh
Hydrogen
4/3
2050
Oxy
Axetylen
1/1
2900
http://www.ebook.edu.vn
75
N2O
Axetylen
2/1,8
3000
Thnh
phn(V/V)(lt/pht)
Nhit (0C)
Khng kh
Axetylen
4,2/0,7
1800
Khng kh
Axetylen
4,2/0,9
2000
Khng kh
Axetylen
4,2/1,1
2300
Khng kh
Axetylen
4,2/1,2
2450
Khng kh
Axetylen
4,2/1,5
2400
Khng kh
Axetylen
4,2/1,6
2300
76
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Cng vch ph
1,00
0,15
2,00
0,18
3,00
0,206
4,00
0,225
5,00
0,235
6,00
0,230
77
(2.3)
78
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th ny l th chun.
79
D = a. Cb
(2.5)
80
http://www.ebook.edu.vn
mx
m
x 100
(2.6)
http://www.ebook.edu.vn
81
g, ng v pg u km nhau
Tng ng vi
Tng ng vi
1mg/ml
10-3g/ml
1g/ml
10-6g/ml
1ng/ml
10-9g/ml
1pg/ml
10-12g/ml
1fg/ml
10-15g/ml
1ag/ml
10-18g/ml
Tng ng vi cc n v sau
g
mg
g
ng
pg
fg
-3
10
10-6
10-3
10-9
10-6
10-3
10-12 10-9
10-6
10-3
10-15 10-12 10-9
10-6
10-3
-18
-15
-12
-9
10
10
10
10
10-6
10-3
82
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(pg/l)
45,0
60,0
80,0
120,0
15,0
23,0
45,0
27,0
54,0
162,0
20,0
35,0
72,0
100,0
83
84
Nguyn t
n kh
vch o(nm)
nguyn t
Gii hn
pht
nhy(g/mL) hin(g/mL)
Khong xc
nh(g/mL)
Al-309.3
N2O - C2H2
1,0
0,2
2-200
Sb-217,6
As-193,7
KK - C2H2
Ar H2
0,4
0,5
0,1
0,2
1-60
1-50
As 193,7
Ba-553,6
KK - C2H2
N2O - C2H2
1-2
0,3
2,0
0,2
10-100
0,6-60
Be-234,9
Bi-223,1
B - 249,7
N2O - C2H2
KK - C2H2
N2O - C2H2
0,02
0,3
12,0
0,01
0,2
10,0
0-04-4
1-50
25-1500
Cd 228,8
KK - C2H2
0,01
0,003
0,02-2
Cs 852,1
Ca 422,7
Ca 422,7
Cr 357,9
KK - C2H2
KK - C2H2
N2O - C2H2
KK - C2H2
0,1
0,05
0,03
0,08
0,03
0,006
0,008
0,02
0,2-10
0,1-8
0,05-4
0,2-15
Cr 357,9
Co 240,7
Cu - 324,8
Ga 287,4
Ge - 265,2
Au - 242,8
Hf 307,3
In 303,9
Ir 208,9
Ir 208,9
Fe - 248,3
Pb - 217,0
N2O - C2H2
KK - C2H2
KK - C2H2
KK - C2H2
N2O - C2H2
KK - C2H2
N2O - C2H2
KK - C2H2
KK - C2H2
N2O - C2H2
KK - C2H2
KK - C2H2
0,15
0,1
0,04
1,0
1,5
0,2
15,0
0,4
1,0
8,0
0,1
0,15
0,15
0,02
0,01
0,1
0,4
0,5
10,0
0,2
0,6
3,0
0,02
0,05
0,4-25
0,2-20
0,1-10
2-150
3-200
0,5-20
30-2000
1-100
2,5-200
20-1500
0,2-20
0,3-25
Pb - 283,3
Li 670,8
KK - C2H2
KK - C2H2
0,3
0,02
0,07
0,005
0,75-50
0,05-4
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Nguyn t
ETA-AAS
Vch
o(nm)
Tng
i(g/mL)
Tuyt
i(pg)
Tng
i(g/mL)
Tuyt
i(pg)
Ag 328,10
Al 309,30
AS 193,70
Au - 242,80
Ba 553,50
0,002
0,02
0,15
0,01
0,01
5.000
20.000
25.000
100.000
20.000
0,000001
0,00002
0,0001
0,0001
0,0005
1
2
20
10
50
Be 234,90
Bi 223,10
Ca 422,70
0,002
0,003
0,003
1.000
500.000
1.000
0,00003
0,0002
0,00001
3
20
1
Cd 228,80
Co 240,70
0,001
0,01
1.000
10.000
0,000001
0,00005
0,1
5
C 357,90
Cu 324,70
Fe 248,30
K 766,50
Li 670,80
0,003
0,001
0,01
0,001
0,0003
3.000
2.000
10.000
5.000
10.000
0,0001
0,00002
0,00003
0,000001
0,0001
10
2
3
0,1
10
Mg 285,20
0,001
100
0,00001
Mn 279,50
Mo 313,30
Na 589,00
0,002
0,02
0,0002
2.000
200.000
2.000
0,000002
0,00003
0,000005
0,2
3
0,3
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85
Ni 232,00
0,002
10.000
0,0001
10
Pb 217,00
0,01
20.000
0,00002
Pt 265,90
Sb 217,60
0,1
0,04
100.000
250.000
0,002
0,0001
200
10
Se 196,00
0,2
250.000
0,0005
50
Si 251,60
0,05
80.000
0,0005
50
Sn 235,50
0,02
100.000
0,0001
10
Sr 460,70
0,002
10.000
0,00005
Ti 364,30
0,05
100.000
0,002
2000
V - 318,50
W 255,10
0,05
0,5
20.000
10000.000
0,001
0,01
100
10000
(3.7)
(3.8)
86
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nhy
Vng tuyn
(( g/ml)
tnh( g/ml)
309,3
0,2
0,5-15,
396,2
237,3
257,4
0,5
1,2
2,5
1,-20,
2,-30,
4,-50,
553,6
455,4
0,08
0,1
0,1-10,
0,5-15,
350,1
48,0
50,-500,
357,9
359,4
0,03
0,06
0,1-10,
0,2-15,
425,4
429,0
0,3
0,6
1,-25,
1,2-30,
248,3
252,3
0,05
0,15
0,1-10,
0,3-15,
271,9
372,0
0,25
0,5
0,5-25,
0,8-30,
Mn
279,5
279,8
280,1
403,1
0,02
0,04
0,1
0,3
0,1-10,
0,2-8,
0,4-15,
0,8-30,
Ni
230,0
331,1
0,04
0,1
0,1-10,
0,2-16,
234,6
341,5
0,25
0,3
0,5-25,
0,6-30,
Cu
324,7
327,4
217,9
216,5
0,01
0,02
0,5
0,7
0,1-5,
0,3-8,
0,8-20,
1,-25,
Si
251,6
250,7
0,06
1,2
0,2-12,
2,-12,
288,2
8,0
10,-80,
Al
Ba
Cr
Fe
1.6. S hp th nn
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88
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Bc sng
Nguyn t
Bc sng
hp thu
cn tr
hp thu
Al
Cu
308.33
324.75
V
Eu
308.21
324.76
Fe
271.90
Pt
271.90
Ga
Hg
403.30
253.65
Mn
Co
403.31
253.65
Mn
403.31
Ga
403.30
Si
250.69
250.69
Nguyn t
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89
90
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91
92
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93
94
My n sc
B d quang in o cng nh sng v khuch i tn hiu
Thit b in t lm b x l tn hiu phn tch v ghi o hp th
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95
96
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Xut pht t nhng nhim v v yu cu phi tho mn, hin nay trong
php o ph hp th nguyn t, ngi ta thng dng ch yu ba loi ngun
pht tia bc x n sc. l:
n Catot rng (HCL-Hollow Cathode Lamp)
n phng khng in cc (EDL-Electrodeless Discharge Lamp)
n pht ph lin tc c bin iu (D2-Lamp, W-Lamp).
Trong ba loi , n catt rng HCL c dng ph bin
4.2.1. n Catot rng(HCL)
n catot rng l kiu n phng in c hnh dng v cu to nguyn
tc nh sau.
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99
nhy( g/ml)
HCL
EDL
HCL
EDL
As-193,70
1,10
0,80
0,80
0,400
Cd- 228,80
0,03
0,02
0,01
0,008
Pb- 283,80
0,10
0,07
0,05
0,030
Hg- 253,60
6,00
4,50
0,50
0,200
Sn- 286,30
2,50
1,60
0,20
0,100
Zn- 213,90
0,03
0,02
0,02
0,018
100
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L vi miligam kim loi hay mui kim loi d bay hi ca nguyn t phn
tch, lm sao khi ton b cht ha hi bo m cho p sut hi ca kim
loi trong n iu kin nhit 800-5500C l khong 1-1,5mmHg.
Cht ny thay cho catot trong n HCL, n chnh l ngun cung cp
chm tia pht x ca nguyn t phn tch, khi chng b kch thch, trong qu
trnh n EDL hot ng.
c. Kh trong n
Trong n EDL cng phi ht ht khng kh v np thay vo l mt kh
tr Ar, He hay Nit c p sut thp, vi mmHg, khi u cho s lm vic
ca n EDL.
d. Ngun nui n lm vic
Ngun nng lng cao tng nui n EDL lm vic c ch to theo
hai tn s: Tn s sng ngn 450 MHz v tn s sng radio 27,12 MHz c
cng sut di 1KW.
Do ngun nui l nng lng cm ng in t vi hai tn s khc nhau,
nn n EDL cng c chia thnh hai loi:
n EDL sng ngn, ngun nui tn s 450 MHz v
n EDL sng radio, ngun nui tn s sng radio 27,12 MHz.
Khi n lm vic, di tc dng ca nng lng cao tn cm ng n
c nung nng , kim loi hay mui kim loi trong n c ha hi v b
nguyn t ha.
Cc nguyn t t do c sinh ra s b kch thch v pht ra ph pht
x ca n di tc dng nhit. chnh l ph vch ca kim loi cha trong
n EDL.
Ngoi u im v nhy v gii hn pht hin, n EDL ca cc kim
hay bn kim thng c bn cao hn n HCL. ng thi vng tuyn tnh
ca php o mt nguyn t khi dng n EDL cng thng rng hn so vi
vic dng n HCL.
Tuy c nhiu lai n kiu EDL c sn xut nhng tt v c
dng nhiu ch c 12 nguyn t kim v bn kim l As, Bi, Cd, Hg, P, Pb,
Se, Sn, Te, Tl v Zn.
Ngoi n Catot rng v n phng in khng in cc, ngi ta cng
ch to ra c nhiu lai n pht tia bc x n sc ca cc nguyn t
nh n catot rng cng cao(High intensity emission lamp HIEL), n
gradient nhit (Controlled temperature-gradient lamp CTGL).
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101
102
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y l loi l nguyn t ha c dng ph bin trong phng php GFAAS. L nguyn t ha l mt ng rng c ch to bng than Graphit v
c nung nng bng in trong dng kh quyn Argon.
(2.11)
103
m - bc phn x
n - s rnh = 1/b
Khi mun bit mt my n sc c kh nng phn gii c hai vch k
nhau hay khng th phi tnh c nng sut thc t ca my bng cng thc
sau:
Ry/c = /
Trong =(1 +2) /2 v = 1 - 2, mun tch c hai vch lin k
th Rm >Ry/c.
b. Chiu rng ph ca khe sk
Thng th chiu rng ca khe vo v khe ra(s) bng nhau c tnh
bng(mm) theo cng thc sau:
sp = s /Dk (nm)
Trong cc ti liu tra cu thng s dng gi tr chiu rng ph ca khe
sk; v d khe 0,2,0,7, 2,0 nm
4.4.2. B d (Detector)
L mt lai dng c quang hc dng thu nhn v pht hin tn hiu
quang hc theo hiu ng quang in ca n.
Vi s pht trin ca khoa hc v k thut, ngy nay ngi a ch to
ra c nhiu lai detector quang hc kiu ng c th khuch i tn hiu o
c ln n c triu ln
Nhn quang in kiu ng l mt lai dng c thu nhn tn hiu quang
hc c tnh cht vn nng, n c nhy v chn lc cao. Vng ph hat
ng ca cc detector lai ny thng l 190-900nm,
Thng s di ph hat ng ph thuc vo bn cht ca nguyn liu
ch to bn catot ca n.
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C th s dng phng php thm trong hai dung dch phn tch
c ly vi lng th tch nh nhau sau cho thm vo mt mu
th nht lng th tch dung dch chun vi nng bit cn
dng dch mu th hai cho thm lng th tch dung mi nh trn.
Tn hiu o trn my c hiu chnh vi ng nn. khi nng
cha bit ca nguyn t s c tnh ton nh sau:
Cx= Sb.Vs.Cs/(Sa-Sb)Vx
(2.12)
Trong :
Sa, Sb l hai tn hiu o
Vs, Cs th tch v nng ca cht chun cho thm.
Vx, th tch mu phn tch.
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107
Bc sng
hp thu
Nguyn t
cn tr
Bc sng
hp thu
Al
308.33
308.21
Cu
Fe
324.75
271.90
Eu
Pt
324.76
271.90
Ga
Hg
Mn
Si
403.30
253.65
403.31
250.69
Mn
Co
Ga
V
403.31
253.65
403.30
250.69
108
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109
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0
ion S % b ion ha nhit ( C)
Th
ha(eV)
2000
3000
4000
Na
5,21
0,30
5,00
26,00
4,32
2,10
22,00
82,00
Rb
4,16
9,00
34,00
90,00
Cs
3,87
28,00
70,00
96,00
Ca
6,11
0,20
1,50
17,00
Ba
5,31
1,00
6,00
23,00
111
O
Th kch thch( T s Ni/N0 nhit ( C)
eV)
2000
3000
4000
Cs-852,10
1,76
4,00. 10-4
7,00. 10-3
3,00. 10-2
Na-589,00
2,12
1,00. 10-5
6,00. 10-4
4,00. 10-3
Ca-422,70
2,95
1,10. 10-7
4,10. 10-5
6,00. 10-4
Zn-213,90
5,86
7,00. 10-13
6,00. 10-10
1,10. 10-7
5.3.3. nh hng ca yu t ha hc
Trong php o ph hp th nguyn t cc nh hng ha hc cng rt
a dng v phc tp. N xut hin cng rt khc nhau trong mi trng hp
c th v cng nhiu trng hp khng xut hin. Cc nh hng ha hc
thng c th dn n kt qu sau y:
Lm gim cng ca vch ph ca ca nguyn t phn tch, do
s to thnh cc hp cht bn nhit, kh ha hi v kh nguyn t
ha.
Lm tng cng ca vch ph, do s to thnh cc hp cht d
ha hi v d nguyn t ha.
S tng cng vch ph khi nguyn t phn tch tn ti trong
-
112
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113
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rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
328,1
338,3
0,7
0,7
2,5
5,0
4,0
10,0
rng khe h
(nm)
Nng kim
tra
(mg/L)
Khong tuyn
tnh mg/L
309,3
396,2
308,2
394,4
0,7
0,7
0,7
0,7
50,0
55,0
70,0
100,0
100,0
150,0
150,0
-
237,3
236,7
257,5
256,8
0,2
0,7
0,2
0,2
150,0
200,0
300,0
350,0
115
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
193,7
0,7
45,0
100,0
189,0
0,7
40,0
180,0
197,2
0,7
90,0
250,0
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
553,6
350,1
0,2/0,4
0,2
20,0
250,0
20,0
--
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
422,7
239,9
116
0,7
0,7
4,0
600,0
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5,0
800,0
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
228,8
0,7
1,5
2,0
326,1
0,7
500,0
--
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
357,9
359,4
360,5
425,4
427,5
429,0
0,7
0,7
0,7
0,7
0,7
0,7
4,0
5,0
7,0
12,0
15,0
20,0
5,0
7,0
7,0
7,0
7,0
5,0
6.8. ng ( Cu)
Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - Cu(NO3)2 1000 mg/l theo Cu.
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rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
324,8
327,4
0,7
0,7
4,0
8,0
5,0
5,0
216,5
0,2
20,0
20,0
222,6
0,2
50,0
50,0
249,2
224,4
0,7
0,2
300,0
650,0
100,0
-
244,2
0,7
1000,0
6.9. St (Fe)
Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - Fe(NO3)3, 1000 mg/l theo Fe
Chun b - Ha tan 1,000 g Fe trong 50ml HNO3 sau nh mc n 1l
bng nc ct kh ion.
Ion gy nhiu bao gm Co, Cu v Ni. gim nh hng ca cc ion
ny cho thm CaCl2 vo mu chun v mu phn tch.
Cc iu kin ghi ph.
Bc sng
(nm)
248,3
252,3
248,8
302,1
296,7
246,3
305,9
346,6
rng khe h
(nm)
0,2
0,2
0,2
0,2
0,2
0,2
0,2
0,2
Nng kim
tra(mg/L)
6,0
8,0
9,0
20,0
40,0
65,0
100,0
500,0
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Khong tuyn
tnh mg/L
6,0
10,0
10,0
10,0
20,0
20,0
-
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
253,7
0,7
200,0
300,0
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
264,0
266,5
285,0
237,3
0,2
0,2
0,2
0,2
12,0
13,0
15,0
18,0
250,3
254,4
351,4
0,2
0,2
0,2
22,0
29,0
91,0
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119
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
766,5
0,7/1,4
2,0
2,0
769,9
0,7/1,4
4,0
20,0
404,4
0,7
350,0
600,0
rng khe h
(nm)
Nng kim
tra(mg/L)
550,1
0,2/0,4
2,5
418,7
495,0
403,7
392,8
357,4
365,0
0,2
0,2/0,4
0,2
0,2
0,2
0,2
3,0
35,0
80,0
100,0
1000,0
9000,0
120
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Khong tuyn
tnh mg/L
3,0
6,0
50,0
100,0
200,0
3000,0
-
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
285,2
0,7
0,30
0,50
202,6
0,7
9,0
10,0
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
279,5
279,8
280,1
0,2
0,2
0,2
2,5
3,0
5,0
2,0
5,0
5,0
403,1
0,2
25,0
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121
Bc sng
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
313,3
317,0
0,7
0,7
30,0
50,0
40,0
50,0
319,4
0,7
65,0
65,0
390,3
315,8
0,7
0,7
150,0
150,0
320,9
0,7
350,0
311,2
0,7
850,0
rng khe h
(nm)
0,2/0,4
0,7
Nng kim
tra(mg/L)
0,50
80,0
Khong tuyn
tnh mg/L
1,0
-
122
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rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
32,0
231,1
0,2
0,2
7,0
10,0
10,0
15,0
352,5
0,2
20,0
25,0
341,5
0,2
20,0
25,0
305,1
346,2
0,2
0,2
25,0
40,0
25,0
40,0
351,5
303,8
337,0
323,3
294,4
0,2
0,2
0,2
0,2
0,2
50,0
80,0
100,0
200,0
350,0
247,7
0,2
1500,0
rng khe h
(nm)
0,2
0,2
Nng kim
tra(mg/L)
14000,0
20000,0
Khong tuyn
tnh mg/L
14000,0
20000,0
6.20. Ch (Pb)
Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - Pb(NO3)2 1000 mg/l theo Pb
Chun b- Ha tan 1,598 g Pb(NO3)2 trong HNO3 1% v nh mc n 1l
bng HNO31%.
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123
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
283,3
217,0
0,7
0,7
20,0
9,0
20,0
20,0
205,3
0,7
250,0
202,2
0,7
350,0
261,4
368,3
0,7
0,7
500,0
1200,0
364,0
0,7
3000,0
124
Bc sng
(nm)
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
265,9
306,5
262,8
238,0
293,0
0,7
0,7
0,7
0,2
0,7
100,0
200,0
250,0
300,0
350,0
160,0
-
273,4
299,8
270,2
0,2
0,2
0,2
350,0
450,0
500,0
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244,0
0,2
850,0
271,9
304,3
0,2
0,7
1200,0
1400,0
rng khe h
Nng kim
Khong tuyn
(nm)
(nm)
tra(mg/L)
tnh mg/L
196,0
2,0
30,0
200,0
204,0
0,7
150,0
206,3
207,5
0,7
0,7
600,0
2000,0
6.23. Silic(Si)
Ngn la: Hn hp Axetylen + N2O.
n catot rng hoc n khng in cc
Dung dch chun - 1000 mg/l theo Si
Chun b ; Nng chy 0,2139g SiO2 vi 2g Na2CO3 trong chn platin. Ha
tan phn nng chy vi nc ct kh ion sau nh mc n 100ml bng
nc ct kh ion.
Ion Si rt d kt ta trong dung dch axit, gim nh hng ny cn
thm vo HF 1%.
Cc iu kin ghi ph.
Bc sng
(nm)
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
251,6
0,2
100,0
150,0
251,9
250,7
252,9
0,2
0,7
0,2
150,0
250,0
300,0
200,0
-
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125
252,4
0,2
350,0
221,7
221,1
220,8
0,2
0,2
0,2
350,0
650,0
1000,0
288,2
0,7
1500,0
rng khe h
(nm)
Nng kim
tra(mg/L)
Khong tuyn
tnh mg/L
268,3
0,7
150,0
400,0
224,6
235,5
270,7
303,4
219,9
300,9
233,5
254,7
0,2
0,7
0,7
0,7
0,2
0,7
0,7
0,7
80,0
100,0
200,0
200,0
350,0
400,0
450,0
450,0
300,0
-
266,1
0,7
1500,0
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rng khe h
(nm)
Nng kim
Tra(mg/L)
Khong tuyn
tnh mg/L
364,3
0,2
80,0
100,0
365,4
0,2
80,0
100,0
320,0
363,5
0,2
0,2
90,0
100,0
200,0
200,0
335,5
0,2
100,0
100,0
319,2
0,2
100,0
200,0
334,2
399,9
0,2
0,2
150,0
150,0
150,0
250,0
375,3
399,0
395,6
394,8
337,8
0,2
0,2
0,2
0,2
0,2
150,0
150,0
200,0
350,0
750,0
150,0
-
6.26. Km (Zn)
Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - ZnCl2 500 mg/l theo Zn
Chun b; Ha tan 0,500 g Zn trong mt th tch ti thiu HCl(1 -1) v
nh mc n 1l bng HCl(1-1).
Cc iu kin ghi ph.
Bc sng
(nm)
213,9
307,6
rng khe h
(nm)
0,7
0,7
Nng kim
tra(mg/L)
1,0
3500,0
Khong tuyn
tnh mg/L
1,0
-
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127
Nguyn t
Al
Vch ph(nm)
309,30
396,20
308,20
394,40
357,90
Cr
359,40
425,40
324,80
Cu
327,40
216,50
248,30
Fe
128
248,80
302,10
252,30
Sb
217,6
As
193,7
Ba
553,6
Be
234,9
Ag
328,1
Cr
357,9
Cr
452,4
Cr
428,9
Cu
324,7
327,4
217,9
218,2
Mg
285,2
202,5
Na
589,6
Ni
232,0
341,5
352,4
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351,5
Pb
Si
217,0
283,0
251,6
235,5
Ti
364,3
Zn
398,8
Bi
223,1
249,7
Cd
228,8
Ca
422,7
Co
240,7
Ga
287,4
Ge
265,5
In
303,9
Ir
208,9
Li
670,8
La
550,0
Si
251,6
Sn
286,3
Th
432,6
Te
261,4
318,4
8. Thc hnh phn tch hm lung kim loi ph gia Ca, Ba, Zn trong du
nht bi trn bng phng php AAS
Mc ch ca bi thc hnh ny gip hc vin nm c:
Cc thao tc, vn hnh trn my o ph AAS mt cch thnh tho.
Cch chun b mu phn tch thch tu theo tnh cht ca mu.
Gii c cc ph phn tch mu c th.
Bit nhn xt nh gi kt qu phn tch.
8.1 Cc cng vic chun b
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129
B phn x l tn hiu.
8.1.2. Cc loi dng c v ho cht ngun lc cn thit cho th nghim
-
Cn phn tch.
Thit b chun b mu v c ha mu bng phng php vi sng
T sy chn khng.
Bnh ng mu cc loi.
Bnh ht m.
Van gim p.
Dung mi cho tng bi c th, xylen toluen, hexan.
Cc mu dung dch chun chun cha kim loi khc nhau( Dung
dch v c v cc cht phc c kim).
Ha cht tinh khit dng cho phn tch( kalixiclohexanbutyrat
C10H15O2K, axit 2-etylhexanoic).
Axit nitric tinh khit HNO3, axit clohydric HCl tinh khit.
Khi axetylen tinh khit, kh N2O tinh khit.
B lc khng kh.
Ti liu tra cu, ti liu hng dn thao tc vn hnh ca tng my
8.2. Cch tin hnh th nghim
8.2.1. Chun b mu phn tch
a. Mu dng lng
Nu l mu lng nh nc mt, nc ngm. nc thi phi c x l
s b, qua h thng lc cc cht l lng v cn phn tch ring sau
mi a vo my AAS.
Dung dch mu uc chun b nh sau.
Ly mt lng nht nh dung dch chun vi nng bit trc(5-10
ml ty theo tnh ton khong nng cn thit) sau pha thm dung mi
t n vch nh mc trong bnh nh mc.
Pha dung dch chun vi nng khc nhau trong khong tuyn tnh cho
php v o ph AAS cng mt iu kin ti u cho mu phn tch.
130
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131
A(C B)
( mg/L)
C
AV
.
W
Khng
thc
hin
thc
hin
ng
132
Khng
Tiu chun
hot ng
Theo hng
dn qui nh
Theo yu cu
k thut cho
tng bi
Theo
dn
Thao tc m my v ci
t cc thng s theo yu
ng qui trnh
thao tc k
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hng
cu phn tch
thut
Ch cc thng s n nh
ng trnh t,
v tin hnh o ph ca
cc mu chun, mu
k thut chnh
xc
phn tch
Theo di hot ng ca
my trong thi gian phn
Ghi chp y
, iu chnh
tch
kp thi
Ghi nhn xt
Ch n nh v tr my
v li trng thi ban u
Ghi nhn xt
Np phiu bo
tnh ton kt qu
co, bn giao
my
Vch ph c trng
Hm lung %
2.
133
Gc nghing
Bc nhiu x lm vic m = 1
Hy tnh
2 cho
2 = 597 nm
134
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135
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n gin
Tm khi
Tm mt
Tm y
c trng hnh hc
a=b=c
= = = 90o
a=bc
= = = 90o
abc
= = = 90o
Ba phng
(orhombohechal)
Su phng
(hexagoral)
Mt nghing
(monoclinic)
Ba nghing
(Triclinic)
a=b=c
= = 90o
Su phng n gin
a=bc
o
o
= = 90 , = 120
Mt nghing n gin
abc
Mt nghing tm y
=
Ba nghing n gin
abc
90o
Hu ht cc kim loi (khong 90%) kt tinh trn s ha rn thnh ba cu
trc tinh th xp cht l:
Lp phng tm khi (LPTK)
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137
Lp phng tm mt (LPTM)
1.2.3. H s xp v s sp xp
i vi kim loi mi nguyn t u c mt s lng nguyn t tip xc
hoc cch u gn nht, gi l s sp xp (s phi t). S phi t cng ln
mng tinh th cng dy c.
Trong cu trc ca tinh th lp phng tm khi mi quan h gia chiu
di cnh lp phng (a) v bn knh nguyn t (R) c biu din nh sau:
a
4R
(3.1)
4R
(3.2)
138
V1
V
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(3.3)
LPTK
LPTM
Kim loi
Hng s mng
a (nm)
Bn knh nguyn
t R (nm)
Crom (Cr)
0,289
0,125
St (Fe)
Molipden (Mo)
0,287
0,315
0,124
0,136
Kali (K)
Natri (Na)
Tantal (Ta)
Vonfram (W)
Vanadi (V)
0,533
0,429
0,330
0,316
0,304
0,231
0,186
0,143
0,137
0,132
Nhm (Al)
ng (Cu)
Vng (Au)
Ch (Pb)
Niken (Ni)
Platin (Pt)
Bc (Ag)
0,405
0,361
0,408
0,495
0,352
0,393
0,409
0,143
0,128
0,144
0,175
0,125
0,139
0,144
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139
Bn knh
nguyn t
T s
c/a
% lch
khi gi tr
Cadimi (Cd)
0,2973
0,5618
0,149
1,890
+15,7
Km (Zn)
0,2665
0,4947
0,133
1,856
+13,6
Magie (Mg)
Coban (Co)
0,3209
0,2507
0,5204
0,4069
0,160
0,125
1,623
1,623
-0,61
-0,61
Ziriconi (Zr)
Titan (Ti)
Benili
0,3231
0,2950
0,2286
0,5148
0,4683
0,3584
0,160
0,147
0,113
1,593
1,587
1,568
-2,45
-2,82
-3,98
R (nm)
140
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141
142
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Ta im ct
Ly nghch o
Trit tiu phn s
1/3
3
6
2/3
3/2
3
1
1
2
Tiu ch
Ta im ct
Ly nghch o
Trit tiu phn s
1
1
1
0
0
0
0
Ch s Miller s l (6 3 2)
Tnh ton
h2
k2
a2
l2
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(3.4)
143
-a1
+a3
-a2
+a2
o
120 C
+a1
-c
-a3
144
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Hnh 3.10: Cc loi l hng trong mng LPTM (a) v LPTK (b)
1.2.9.Tnh th hnh
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145
tn ti t
t 1394oC
1394oC c cu trc
s mng ln hn st .
Bng 3.5. Dng tinh th th hnh ca mt s kim lo1.
Kim loi
Cu trc tinh th
o
T phng
To khc
Ca
LPTM
Co
Fe
SPXC
LPTK
1394oC)
Li
Na
LPTK
LPTK
Ti
Y
Zr
SPXC
SPXC
SPXC
N * exp(
Q
)
RT
(3.5)
Trong : N S nt mng.
Q Nng lng to thnh l trng.
146
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k Hng s Boltzmann.
T nhit tuyt i (K).
Theo phng trnh trn th s lng tng rt nhanh theo nhit .
Vacancy trong kim loi cng c th c to thnh khi c s bin dng n
hi, ngui nhanh hoc bn ph bng cc ht nng lng cao nh ntron.
Vacancy khng cn bng c xu hng to thnh cc m vacancy. i khi
nguyn t trong tinh th chim mt v tr ngoi nt gia cc nguyn t xung
quanh to ra khuyt tt ngoi nt hay nguyn t xen k.
Tronh thc t khng c vt liu hoc kim loi no sch tuyt i 100%
m ch t 99,9999%. V vy mt lng rt nh nguyn t pha tp thay th
trong silic nguyn cht c th nh hng rt ln n tnh dn in ca silic.
Khuyt tt ng lch trong tinh th c to thnh bi bin dng
thng xuyn hoc bin dng n hi hoc trong qu trnh ho rn ca tinh
th.
Khuyt tt mt l s sai lch mt trong vt liu a tinh th gm nhiu ht
vi nh hng tinh th khc nhau.
1.2.11. n tinh th
n tinh th l vt tinh h c mng ng nht v nh hng khng i
trong ton b th tch.
Trong t nhin hu nh n tinh th kim loi khng tn ti, phn ln n
c to ra bng cng ngh tng hp. Cc loi n tinh th c ng dng
nhiu trong cng nghip bn dn v vt liu in t.
1.2.12. a tinh th
Trong thc t hu nh ch gp vt liu a tinh th gm rt nhiu tinh th
nh (c 1 m) c gi l ht c cng cu trc mng nhng vi nh hng
khc nhau mang tnh ngu nhin v lin kt vi nhau bng bin gii ht.
147
(3.6)
Trong :
N - l s ht trn mt . vung b mt phng i cao.
n - l s nguyn c gi l cp ht ASTM.
C 16 cp ht khc nhau theo th t ht nh dn.
Nh vy mt cp ht tng ng vi s lng ht trn mt n v din
tch. Ngi ta thng xc nh cp ht bng cch so snh cng mt
phng i (thng l 100) gia vt liu nghin cu vi thang nh cp ht
chun ASTM vi kch thc ht khc nhau.
Siu ht c cu trc tinh th kh hon chnh v c kch thc rt nh
(nm).
C cu trc tinh th kh hon chnh nh hng lnh nhau mt gc rt
nh (1-2 o0)v ngn cch nhau bng bin gii siu ht.Bin gi7i nu thc
cht l nhng lnh bin c chiu dy nh hn so vi bin gi7i ht a tinh th.
Trong khi a tinh th c cu trc hng chc m, thm ch hng trm m.
Bng 3.6: Cp ht theo ASTM.
Cp ht
148
S ht trong
S ht trong
in2, x 100
1 mm2 x 1
ca 1 ht (mm2)
1
2
3
4
5
6
7
1,0
2,0
4,0
8,0
16,0
32,0
64,0
15,5
31,0
62,0
124,0
248
496
992
0,0645
0,0323
0,0161
0,00807
0,00403
0,00202
0,001008
8
9
10
128
256
512
1980
3970
7940
0,000504
0,000252
0,000126
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Din
tch
tht
ca n:
E = h.
Mt khc tn s
(3.7)
theo cng thc sau:
(3.8)
Trong :
h - hng s Plank, h = 4,136. 10-15 e5.s hay 6,626.10-34 J.s.
c tc nh sng c = 2,998. 10-8 m/s.
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149
150
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151
I o10
(3.9)
Trong :
I, Io cng ca tia X ti v tia X truyn qua.
- h s hp thu khi,
=Z .
L - dy lp vy cht.
Z - th t nguyn t.
- bc sng nh sng ti.
2.4. nh lut Vulf-Bragg
nh lut Vulf-Bragg c a ra nm 1913 th hin mi quan h gia
bc sng tia X v khong cch gia cc mt phng nguyn t.
Theo l thuyt v cu to tinh th, nhng nguyn t hay ion phn b mt cch
trt t u n trong khng gian theo mt quy lut xc nh. Khong cch
gia cc nguyn t (ion) khong vi Ao v gn tng ng vi bc sng
tia 10.
Khi chm tia X p vo tinh th th xut hin cc tia nhiu x vi cng
v cc hng khc nhau.
nh lut Bragg gi thit rng mi mt phng nguyn t phn x sng ti
c lp nh phn x gng,
Gi s c hai mt phng song song AA v BB (hnh 10). C cng ch s
Miller h, k, l, v cch nhau bi khong cch gia cc mt phng nguyn t
dhkl.
Gi thit rng tia ti l tia n sc song song v cng pha vi bc sng
chiu vo hai mt phng ny vi mt gc . Hai tia 1 v 2 b tn x bi
nguyn t Q v P cho hai tia phn x 1 v 2 cng vi mt gc
mt phng A, B.
152
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so vi cc
(3.10)
(3.11)
(3.12)
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153
1
d hkl
(3.13)
Trong dhkl l khong cch gia cc mt phng (hkl) trong mng tinh
th.
Mng o xc nh mt khong cch v tr mng c kh nng dn n s
nhiu x.
154
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Hnh 3.15: Quan h gia trc mng thun a, b, c v mng o a*, b*, c*.
Mi cu trc tinh th c hai mng lin hp vi n, mng tinh th v mng
o v nh nhiu x ca tinh th l mt bc tranh mng o ca tinh th.
2.6. Cng nhiu x
C th tnh ton c cng nhiu x bng cch cng sng hnh sin
vi pha v bin khc nhau. Hng ca tia nhiu x khng b nh hng
bi loi nguyn t tng v tr ring bit v hai mng n v c cng kch
thc nhng vi s sp xp nguyn t khc nhau s nhiu x tia X trn cng
mt hng. Tuy nhin cng ca cc tia nhiu x ny khc nhau.
xc nh cng nhiu x thng tin hnh theo 3 bc sau:
Nhiu x tia X bi in t t do.
Nhiu x tia X bi nguyn t.
Nhiu x bi mng c bn.
2.6.1. Cng nhiu x bi in t t do
c xc nh theo cng thc sau:
e4
I Io
sin 2 2
2
2
4
r m ec
(3.14)
155
bd1
bd 2
(3.15)
Aei
Trong :
fe 2
i ( hu k
l )
(3.16)
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1 cos2 2
p
sin 2 cos
e 2
(3.17)
157
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Hnh 3.20: Nhiu x tia X ca SiO2 tinh th (a) v SiO2 v nh hnh (b).
http://www.ebook.edu.vn
159
B phn mu.
160
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161
P
i
i
i m
(3.18)
Trong :
Ki- hng s (Xc nh bng thc nghim)
Pi - t l trng lng pha.
i - mt pha
m - h s suy gim khi lng ca hn hp
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nhy ca mu o
nhy ca php o
K e K ( hkl ) X
(3.19)
( / )s
Trong :
K e - h s ph thuc vo iu kin th nghim.
K ( hkl ) - tha s cu trc cho pha
- t trng pha
( / ) s - h s hp ph khi, h s ny l mt hm ca nhiu cc
yu t.
C th lit k nhng thng s nh hng nh sau:
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163
( / )
( / )s
o
( hkl )
(3.20)
Trong :
I o - cng ca pc trong pha tinh khit.
I ( hkl )
I o ( hkl )
(3.21)
164
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( I ( hkl ) / I o ( hkl ) )( / )
( / ) ( I ( hkl ) / I o ( hkl ) ) ( / )
( / )
(3.22)
Trong :
pha
X
X
(3.23)
- l pha cn xc nh.
- l pha chun.
k - h s hiu chnh xc nh t th I ( hkl ) / I ( hkl )
X /X .
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165
X (
I ( hkl )
I ( hkl )
RIR
I ( hkl )
I rel ( hkl )
I
rel
( hkl )
X
X
(3.24)
I ( hkl )
RIR I
rel
(3.25)
phakhac
( hkl )
I ( hkl ) j / RIR
rel
( hkl ) s
j 1
Cng thc ny cho php tnh ton khi lng pha m khng cn c
cht chun ni. Tuy vy trong thc t ph XRD ca hn hp cht thng c
cc pic l khng c xc nh cho nn nu dng cng thc ny dn n sai
s ng k.
Phn tch nh lng nguyn t bng ph XRD da vo t l cng
ca cc vch c trng trong mu vi nng ca nguyn t nghin cu
166
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Cnc
Cch
(3.26)
Trong :
I nc , I ch - cng vch nghin cu v vch chun.
Cnc , Cch - nng nguyn t nghin cu v nguyn t chun.
h2
k2
a2
l2
(3.27)
1
d2
T ta c: sin 2 Q
k2
a2
l2
k2
l2
4sin 2 Q
2
4a 2
h2
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(3.28)
(3.29)
167
Tha s
4a 2
Khi gc
h12
h2 2
k12 l12
k2 2 l2 2
(3.30)
Tng ng vi tng h 2
l 2 = 1, 2, hoc 3.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
168
l2
hkl
100
110
111
200
210
211
220
300, 221
310
311
222
320
321
400
410, 322
411, 330
331
420
421
332
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Mng
LPG
LPG, LPTK
LPG, LPTM
LPG, LPTK, LPTM
LPG
LPG, LPTK
LPG
LPG, LPTK, LPTM
LPG
LPG, LPTK
LPG, LPTM
LPG, LPTK, LPTM
LPG
LPG, LPTK
LPG
LPG, LPTK, LPTM
LPG
LPG, LPTK
LPG, LPTM
LPG, LPTK, LPTM
LPG
LPG, LPTK
23
24
LPG
LPG, LPTK, LPTM
422
l 2 trong nh nhiu x.
C phn x
n gin
Tm khi
Tt c cc mt
Tm mt
Khng c phn x
Khng
l - chn
2
l 2 - l
h, k, l hn hp
l
nh nhiu x t vt liu c cu trc lp phng c th phn bit c
ngay vi nh nhiu x t vt liu khng phi lp phng c tnh i xng
thp. Trong cu trc lp phng n gin v LPTK khong cch gia cc pic
gn bng nhau.
Thng s mng a c th tnh ton theo cng thc sau:
a
2sin
h2
l2
169
Ta c th t
4a 2
Gi tr A tng ng vi h2 + k2 +l2 = 1
V d: Xc nh ch s nh nhiu x ca vt liu c cu trc lp phng
nh sau (nh ghi nhn vi bc x CuK) thu c 9 pc vi cc gc 2 nh
sau:
Bng 3.9.Cc thng s mng ca Al-Cu- (K 1) = 0,254056nm
S
Sin2
Sin 2
Sin 2 min
Sin 2
x3
Sin 2 min
h2+k2+l2
hkl
a (nm)
38,52
0,1088
1,000
3,000
111
0,4044
2
3
44,76
65,14
0,1450
0,2898
1,333
2,664
3,999
7,992
4
8
200
220
0,4045
0,4047
4
5
6
7
78,26
82,47
99,11
112,03
0,3983
0,4345
0,5792
0,6876
3,661
3,994
5,324
6,320
10,983
11,982
15,912
18,960
11
12
16
19
311
222
400
331
0,4048
0,4048
0,4049
0,4049
8
9
116,60
137,47
0,7238
0,8684
6,653
7,982
19,958
23,945
20
24
420
422
0,4049
0,4049
pic
Trong :
K
D cos
- chiu rng na pc
170
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(3.31)
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171
Hnh 3.27: Ph XRD ca vt liu khong cao lanh t nhin, ngun pht CuK
172
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173
174
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175
Thng s mng c s:
a =13,711Ao
b=12,731 Ao
c= 18,570 Ao
Gc: alpha = 90, beta =90,01, gama =90 o
176
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177
c= 20.178 Ao
Gc alpha =90o, beta =90,o gama =90 o
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179
Trc tin phi kim tra an ton v tnh trng hot ng ca my,
= 1,54
X l cc ph .
7.2.3. Tnh ton thnh phn pha
-
Thnh phn pha mi vt liu c tnh ton theo cng thc trong ti
A (nm)
h2 + k2 + l2
hkl
180
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8.1. Cu hi l thuyt
Cu 1. Mng khng gian v c bn. M s cu trc tinh th in hnh.
Cu 2. Ch s Miller ca mt tinh th v cch xc nh.
Cu 3. Bn cht ca phng php nhiu x tia 10. S to thnh tia X v tnh
cht ca n.
Cu 4. C s ca phng php nh tnh v nh lng thnh phn pha tinh
th
8.2. Bi tp
1.
2.
=67.1 o
l
4.
5.
c. NaCl d=2.820
Tnh th vn hnh ti thiuu kch thch cc vch sau y:
a. Vch K ca Ca (3.064 A)
b. Vch ca L As (9.370 A)
c. Vch L ca U (0.592 A)
6.
7.
d. Vch K ca Na (0.496 A)
Chiu di sng cc tiu khi cc electron lp K ca Zirconi l 0.7 A 0. Tnh
th cc tiu cn thit kch thch cc electron lp K trong ng pht tia
10.
Xc nh thng s mng v ch s Miller ca kim loi Zn c ph XRD nh
sau.
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181
S pic
1
2
3
36.31
38.98
43.21
4
5
6
7
8
54.32
70.08
70.64
77.04
82.09
83.72
182
Sin
Sin 2
Sin 2 min
Sin 2
x3
Sin 2 min
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h2+k2+l2
hkl
a (nm)
P N CU HI V BI TP
Bi 1: Ph hng ngoi (IR)
Cu 1
1 cm vi sng
0,8 m -kh kin
10 m -hng ngoi
100 nm- t ngoi
10nm ta 10. (Rnghen)
Cu 2
893 cm-1 hng ngoi
3.104 cm-1 kh kin
5,0 cm-1 vi sng
8,7.10 -4 cm-1 t ngo1.
Cu 3
E=h
= hc/
Cu 5.2
Cu 5.3
Cu 5.4
Cu 5.5
Cu 5.6
Cu 5.7
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183
Cu 5.8
2=
24,3
23,4
21,0
17,5
sin
d(nm)
0,4115
0,3971
0,3583
0,3007
1,87
1,94
2,15
2,56
Cu 3
a
Cu 4
a.
d 2
2 2
2, 828A o
184
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i vi Ag: 2 = 21,10
b.
c.
Fe = 36,40
Se = 20,30
Ag = 10,10
Cu 5
12400
min x103
12400
3, 064
4046, 99V
4, 04699KV
12400
9, 370
1323, 4V
12400
0, 592
20945, 9V
12400
0, 496
25000V
12400
0, 7
12400
0, 7
20, 9459 KV
25 KV
Cu 6
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185
in tch in t
Ch s Miller
:
:
Gc
Cng
Hng s Plank
:
:
H s hp ph
Khong cch
Khi lng
:
:
Mt
Mt phng mng
Nhit
:
:
h, k, l
T
Nguyn t s
Nng nguyn t
c bn
S Avogadro
:
:
:
:
Z
Xi
a, b, c
NA
Tn s
Th
Tha s cu trc
Vch c trng
Vn tc
Vn tc nh sng
Cng dng in
:
:
:
:
:
:
186
e
h, k, l
I
h
d
M
V
F
K, L, M
v
C
A
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Nng lng
Jun
Lc
in p
:
:
N (Niuton)
V (vn)
Cng in trng :
V/m
in tr
cm ng t
T (tesla).
Nng lng bc x
Mt quang
:
:
E (eV)
D
H s hp th
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187
3.
4.
5.
6.
B.C .Smith - Fundamental of Fourier Transform IR Spectroscopy CRC press. FL., 1996
G. Socrates - Infared Characteristic Group frequences Tables and Charts
- Wiley Chichester, 1994
7.
8.
188
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