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MC LC

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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.

My quang ph hng ngoi bin i Fourier gm cc b phn

chnh sau ................................................................................................. 26


4.3. Chun b mu ghi ph hng ngoi .................................................... 28
5. ng dng ca ph hng ngoi trong phn tch hp cht hu c, ha
du 29
5.1 Cc tn s c trng ca hp cht hu c hydrocacbon ................. 30
5.2. Hydrocacbon khong no (olephin) ...................................................... 33
5.3. Hydrocacbon thm (Aromatic) ...................................................... 34
5.4. Hidrocacbon axetilenic .................................................................. 37
5.5. Hydrocabon lin hp ........................................................................ 37
5.6. Cc hp cht hu c vi cc nhm chc khc nhau ..................... 38
6. Phn tch nh tnh v nh lng............................................................ 53
6.1. Phn tch nh tnh ............................................................................ 53
6.2.
7.

Phng php nh lng ............................................................. 53

Cc tn s c trng ca cc hp cht hydrocacbon ......................... 55


7.1. Hydrocacbon no (Ankan) ............................................................... 55

7.2. Hydrocacbon khng no (Anken) .................................................... 56


7.3. Hp cht vng thm (Aromatic) .................................................... 57
7.4. Hp cht c kim ............................................................................... 58
7.5. Hp cht d vng............................................................................... 58
8. Cng thc thc nghim J.Brand.............................................................. 59
8.1.
Cc hng i khi gii ph hng ngoi ......................................... 60
8.2.
Mt s bi tp v d v gii ph hng ngo1. .............................. 60
9. Thc hnh phn tch hp cht hydrocacbon parafin, naphten,
hydrocacbon thm trong phn on du m bng ph hng ngoi. ........... 63
9.1. Cc cng vic chun b ................................................................. 63
9.2. Cch tin hnh th nghim ................................................................ 64
9.3. o ph hng ngoi ca mu trn my IR ......................................... 65
9.5. Tnh ton ....................................................................................... 65
10.
Cu hi v bi tp gii ph hng ngoi ............................................ 67
BI 2. QUANG PH HP THU NGUYN T (AAS) ...................................... 71
M bi. HD K2 ................................................................................................. 71
Gii thiu ..................................................................................................... 71
Mc tiu thc hin ....................................................................................... 71
Ni dung ...................................................................................................... 71
1. C s ca phng php ph hp thu nguyn t .................................... 71
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1.1. Nguyn tc v l thuyt ca ph AAS .............................................. 71


1.2. S nguyn t ha ............................................................................. 74
1.3.Mi lin h gia s hp th nh sng v mt nguyn t ............. 77
1.4.Cc loi nng trong php o AAS ................................................ 81
1.5.Mt s nh hng trong php o AAS .............................................. 82
1.6. S hp th nn .............................................................................. 87
1.7. S chen ln cu vch ph ............................................................. 88
2. Phng php nh lung bng ph AAS ................................................ 89
2.1. Phng php th chun ............................................................... 89
2.2.
Phng php thm cht chun .................................................... 90
3. ng dng ca phng php quang ph hp th nguyn t AAS xc
nh hm lung kim loi v cc nguyn t .................................................. 92
3.1.
i tng ca phng php ........................................................ 92
3.2. Nhng u im v nhc im ca php o AAS. ......................... 93
4. My o AAS ............................................................................................. 94
4.1. Cc cu kin chnh ca thit b o ph hp th nguyn t AAS ... 94
4.2. Cu to ca cc b phn trong my AAS ..................................... 96
4.3. L nguyn t ho ............................................................................ 102
4.4. My n sc (Monochromator) ...................................................... 103
5. Cc iu kin ghi ph AAS .................................................................... 105
5.1. Xy dng phng php phn tch .................................................. 105
5.2. iu kin nguyn t ho mu ..................................................... 106
5.3. Cc im cn ch khi thc hin php o..................................... 107
6. Mt s iu kin chun ghi ph AAS cho cc nguyn t ................. 114
6.1. Bc (Ag)....................................................................................... 114
6.2. Nhm (Al) .................................................................................... 115
6.3. Asen (As) ..................................................................................... 115
6.4. Bary (Ba) ..................................................................................... 116
6.5. Canxi (Ca) ....................................................................................... 116
6.6. Cadmi (Cd)...................................................................................... 117
6.7. Crom (Cr)..................................................................................... 117
6.8. ng ( Cu) ...................................................................................... 117
6.9. St (Fe) ........................................................................................... 118
6.10. Thy ngn (Hg) ............................................................................. 118
6.11. Iridi (Ir)........................................................................................... 119
6.12. Kali (K) .......................................................................................... 119
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6.13. Lantan (La).................................................................................... 120


6.14. Magie (Mg) .................................................................................... 120
6.15. Mangan (Mn)................................................................................. 121
6.16. Molipden (Mo) ............................................................................... 121
7. Mt s vch AAS chun ca cc nguyn t .......................................... 127
8. Thc hnh phn tch hm lung kim loi ph gia Ca, Ba, Zn trong du
nht bi trn bng phng php AAS ...................................................... 129
8.1 Cc cng vic chun b .................................................................... 129
8.2. Cch tin hnh th nghim .............................................................. 130
8.3. Tnh ton ......................................................................................... 131
9. Cu hi bi tp ....................................................................................... 133
9.1.
9.2.

L thuyt ...................................................................................... 133


Bi tp ......................................................................................... 133

BI 3. PH NHIU X TIA X (XRD) ............................................................. 135


M bi. HD K3 ............................................................................................... 135
Gii thiu ................................................................................................... 135
Mc tiu thc hin ..................................................................................... 135
Ni dung chnh ........................................................................................... 135
1. C s ca phng php Rnghen ................................................... 135
1.1.Mt s khi nim v vt liu rn v cu trc tinh th hc ................ 136
1.2. Cu trc v hng s mng hnh hc tinh th .................................. 136
2. Nhiu x tia X, phng trnh Vulf Bragg ........................................ 149
2.1.Khi nim nhiu x tia X .................................................................. 149
2.2. To ngun tia X ........................................................................... 149
2.3. Mt s tnh cht ca tia Rnghen ............................................... 151
2.4. nh lut Vulf-Bragg .................................................................... 152
2.5.Mng o ......................................................................................... 154
2.6. Cng nhiu x ..................................................................... 155
3. ng dng ph nhiu x tia X phn tch thnh phn cu trc tinh th157
4. nh lng thnh phn pha tinh th. ..................................................... 160
4.1.Cu to my nhiu x ...................................................................... 160
4.2. Phng php Rnghen dng bt phn tch cu trc vt liu ........ 161
4.3. Phn tch nh lng bng ph nhiu x tia X ............................ 162
4.4. o cng vch ph ................................................................... 163
4.5. Phng php inh lng da trn t l cng nhiu x .......... 164
4.6. Phng php chun ni .............................................................. 165
4

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4.7.

Phng php so snh cng nhiu x vi cht chun l

Corundum (Al2O3). (Saphia hng ngc) I/Icorundum ............................... 165


5. Phn tch cu trc pha ........................................................................... 167
5.1. Xc nh ch s Miller ...................................................................... 167
5.2. Nhn bit mng Bravais .............................................................. 169
5.3. Kch thc tinh th ...................................................................... 170
6. c trng ph XRD ca mt s vt liu ................................................ 171
6.1. Nhm vt liu khong st ............................................................... 171
6.2. Nhm vt liu zeolit ........................................................................ 174
6.3. Nhm vt liu kim loi v oxit kim loi. ........................................... 178
7. Thc hnh chp ph XRD ca vt liu xc tc phng php rnghen
bt 179
7.1. Cc cng vic chun b ................................................................... 179
7.2.
8.

Tin hnh th nghim ................................................................... 179

Cu hi bi tp gii ph nhiu x tia X .............................................. 180


8.1. Cu hi l thuyt ............................................................................. 181

8.2. Bi tp ......................................................................................... 181


P N CU HI V BI TP ..................................................................... 183
Bi 1: Ph hng ngoi (IR) ........................................................................ 183
Bi 2: Ph hp thu nguyn t (AAS) ........................................................ 184
Bi 3: Ph nhiu x tia X (XRD) ................................................................ 184
CC THUT NG CHUYN MN V CC CH VIT TT ...................... 186
TI LIU THAM KHO .................................................................................. 188

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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
-

C s l thuyt ca cc phng php quang ph IR, XRD, AAS, cc


khi nim, nh ngha, cng thc tnh ton, cc yu t nh hng
n qu trnh phn tch

Tm hiu v cc loi thit b quang ph, nguyn l cu to, cc loi


n ngun cung cp nng lung, nh sng, phn tch u nhc

im ca tng phng php.


Tm hiu v qui trnh phn tch trn my c th.
Cch t chc thc hin, cc php phn tch.

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.

tr cho tng phng php.


Thc hnh thao tc php phn tch trn thit b vi cc mu chun v

5.

mu phn tch, tm cc iu kin ti u cho php phn tch.


Tho lun kt qu thu c. Tnh ton v nh gi kt qu. Tm cc iu
kin ti u cho php phn tch.

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YU CU V NH GI HON THNH M UN

V kin thc
-

Vn dng c cc kin thc v l thuyt ca cc phng php


phn tch ph dng trong phn tch du m v cc sn phm ca
du m.

Gii thch c y cc kt lun trong php phn tch.

M t chnh xc cu hnh v nguyn l vn hnh ca cc loi thit b

phn tch IR, XRD, AAS v trang thit b ph tr trong phng th


nghim.
V k nng
-

S dng thnh tho v ng k thut phn tch bng quang ph


trong phng th nghim.
Bo qun v bo dng dng c phng th nghim.
Pha ha cht an ton.

Tnh ton d tr vt t, nguyn liu cho cc th nghim.


V thi
-

Nghim tc trong vic s dng v bo dng cc thit b my mc


v dng c.
Lun ch ng kim tra v m bo v an ton phng th nghim.
Ch ng xem xt tnh trng dng c thit b v ha cht trong
phng th nghim.
Nhc nh ng nghip m bo v an ton phng th nghim.
Cch nh gi
Chn mt trong cc hnh thc sau:
L thuyt (chim 25 % s im):
Vit tiu lun
Bi thi vit.
Thc hnh (chim 75 % s im)
Cch chun b my o v cc thit b ph tr, cch chun b mu o
Cch thc hin cc thao tc vn hnh trn my o ph.
-

X l v gii cc ph .
Vit bo co kt qa.

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BI 1. QUANG PH HNG NGOI


M bi. HD E1
Gii thiu
Phng php ph hng ngoi IR l mt trong nhng phng php vt l
rt hu hiu nghin cu cu to ca cc phn t hu c. C s ca
phng php da trn hin tng phn t ca vt cht quay xung quanh trc
ca n di tc ng ca sng in t khi c chiu bi nh sng c bc
sng t 50 m -1mm (200-10 cm-1) v s dao ng ca cc nguyn t v cc
lin kt khi c chiu sng bi nh sng c bc sng ngn hn t 0.8-50
m.
Vic ng dng phng php ph hng ngoi 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. V vy vic tip thu c s s l thuyt
ca phng php v k thut thao tc vn hnh my mc thit b o ph hng
ngoi l rt quan trng v cn thit.
Mc tiu thc hin
-

M t c s ca phng php ph hng ngai IR.


Phn tch thnh phn hydrocabon bng ph IR.

nh tnh v nh lng thnh phn Parafin, Naphten, Aromat da


theo cng thc bn thc nghim J.Brand.
Thc hnh trn my trong PTN
Ni dung chnh
1.
2.
3.
4.
5.
6.
7.
8.

Cc lai dao ng.


Tn s.
iu kin ghi ph.
ng dng ca ph hng ngoi trong ha hc v ha du.
My o ph hng ngo1.
nh tnh v nh lng.
Cng thc thc nghim brand.
Cc tn s c trng.

9. M t thit b, nguyn l lm vic ca my IR.


10. Thc hnh trn my trong phng th nghim.
1. Mt s khi nim v cc loi dao ng
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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)

l qung ng m bc x i qua sau mi dao

ng y .
biu din di sng, ngi ta dng cc n v di khc nhau,
micromet ( ), nanomet (nm) Angstron (Ao)

Hnh 1.1. Bc x in t sinh ra mt t trng H v in trng E vung gc


vi nhau.
b. Tn s
L s dao ng trong mt n v thi qian
C=
hay =

(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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i lng nghch o ca bc sng l s sng k hiu l

ch c o bng cm -1 v c gi l kaiser vit tt l K


c. Nng lng ca bc x E
Cc bc x c nng lng v ph thuc vo bc sng. Bc sng
cng nh, nng lng cng ln.
E= h. =

hc

= h c.

(1.2)

Trong h l hng s Plank


Nng lng E c tnh bng n v eV (electron von, kcal/mol, cal/mol)
Gia cc i lng E, bc sng c lin h vi nhau qua biu thc sau :
10 7
28591
1239 .81
cm 1
Kcal / mol
eV

Cc h s cho thy bc x c tn s cng ln, bc sng cng nh th


nng lng cng ln.
Theo thuyt ht bc x n sc l bc x ch gm mt loi photon c
nng lng nh nhau, cn bc x a sc bao gm cc loi photon c nng
lng khc nhau.
Bng 1.1: Phn loi cc vng bc x in t
Bc x

, 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

1.1.3. Tng tc gia bc x v phn t


Khi bc x c chiu vo cc phn t th chng c th b hp th hoc
khuch tn. Trc ht hy xem xt s hp th ca bc x bi cc phn t.
Cc phn t khi hp th bc x in t s lm quay hay dao ng cc
nguyn t trong phn t hoc lm bin dng cc m my in t trong phn
t.
Tt c cc qu trnh ny u i hi mt nng lng nht nh c tn s
ring gi l tn s quay, tn s dao ng, tn s kch thch in t.

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11

Khi xc nh trng thi nng lng ca phn t th phi k n ba s


hng sau.
a. Nng lng electron
S hng ny ph thuc vo s phn b electron t orbitan in t ny
n orbitan in t khc
b. Nng lng dao ng
c trng cho dao ng ca cc ht nhn nguyn t xung quanh v tr
cn bng ca chng trong phn t.
c. Nng lng quay
c trng cho s quay ca phn t xung quanh trc no ca phn t.
Ngi ta thng coi nng lng ca phn t l tng nng lng ca ba
s hng trn. Khi bin thin nng lng ca phn t l tng cc bin thin
ca mi dng nng lng.
E = Eel+Edd+Eqy
Bin thin nng lng electron lun ln hn bin thin ca nng lng
dao ng khong 10-100 ln cn bin thin nng lng dao ng ln hn
nng lng quay khong 100-1000 ln.
Eel >Edd >Eqy
Mun kch thch eletron cn phi c nng lng ln khong hng chc
n hng trm Kcal /mol. Nng lng ng vi vng t ngoi hoc vng
kh kin.
Cc bc x hng ngoi xa ch lm thay i trng thi quay ca
phn t khi s c ph quay thun ty gm cc vch rt st nhau v cch
u nhau ng vi tn s
qy

qy
h

(1.3)

Khi phn t hp th bc x hng ngoi th trng thi dao ng b kch


thch v bin thin nng lng dao ng lun c bin thin nng lng quay.
ph hng ngoi ta thu c cc m vch ph vi tn s

dd

qy

Khi chiu mt chm bc x in t c tn s khc nhau th phn t ch c


th hp th cc bc x in t ng vi cc tn s trn l s hp th chn
lc.
Theo qui tc chn lc ny phn t ch hp th nhng bc x tng ng
chnh xc vi bin thin gia cc mc nng lng ca chng v s chuyn
mc nng lng nht thit phi km theo s thay i ca cc trung tm in

12

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tch trong phn t tc l s thay i phn b in tch trong phn t, tc


mmen lng cc thay 1.
i vi cc phn t c mmen lng cc 0 th mmen ny s b thay
i khi phn t quay, khi phn t dao ng, v khi phn t b kch thch in
t.
2. Cc loi dao ng
C th chia ph hng ngoi ra lm ba vng chnh sau :
S sng (cm-1)

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)

Trong J l s lng t quay c gi tr :0,1,2,3..


l momen qun tnh = M.r2
M l khi lng rt gn =

m1 m2
m1 m2

r l khong cch gia hai nguyn t trong phn t


Nu chia c hai v ca phng trnh trn cho h.c ta s c biu thc sau
Eq
hc

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)

Trong M l khi lng rt gn.


14

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Hng s lc k ph thuc vo bn lin kt gia cc nguyn t cn tn


s dao ng ca nhm nguyn t ph thuc vo hng s lc v khi lng
ca nguyn t.
Bng 1.3: Tn s dao ng ca mt s phn t gm hai nguyn t
Phn t

,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

Nng lng dao ng ca ca cc nguyn t uc biu din qua


phng trnh sau :
Ed = h.

(n+

1
)
2

(1.9)

Trong n l s lng t dao ng c cc gi tr 0,1,2,3,4,5...

Hnh 1.2. ng cong th nng ca dao ng iu ha.


Nng lng dao ng c th nhy t mc thp n mc cao hoc ngc
li theo qui lut la chn. i vi dao ng iu ha th qui lut la chn

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15

1 ngha l khi dao ng iu ha th phn t ch c php thay i t

mc nng lng ny sang mc nng lng k tip n.


Khi dao ng iu ha th s sng chnh l hiu s gia hai dao ng k
nhau.
ng cong th nng ca dao ng iu ha l mt ng parabon nh
sau.
2.3. Dao ng khng iu ha
Trong thc t dao ng ca cc nguyn t trong phn t khng phi l
dao ng iu ha v bin dao ng thay 1. Khi tng khong cch gia
cc nguyn t n mt gii hn no chng s b phn ly hoc khi p hai
nguyn t li gn nhau s xut hin mt lc y v lc y ny s tng ln
mnh khi cc nguyn t cng gn nhau.
i vi cc phn t dao ng th ng biu din nng lng ca chng
khng phi l cc vch nng lng cch u nhau m cng ln cao cc vch
s cng st li gn nhau hn.
Khi b kch thch bi nng lng no phn t ang trng thi c bn
s nhy sang mc nng lng cao hn ng vi trng thi dao ng =
1,2,3. Cc gi tr cng ln cng cn mt nng lng kch thch ln.

Hnh 1.3. Mc nng lng ca phn t dao ng


Nng lng nh sng kch thch ng vi tn s s nh sng vng hng
ngo1.
V d cc di vch ph ng vi cc mc dao ng ca phn t HCl nh
sau
Bng 1.4. cc mc dao ng ca phn t HCl
16

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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

2.4. Dao ng quay


Trong thc t khng th phn bit ph quay v ph dao ng thun ty v
khi b kch thch bi mt nng lng bc x ln, trng thi dao ng thay
i th cng lm thay i trng thi quay. V vy khi phn t b kch thch bi
nh sng c th xy ra qu trnh quay v dao ng ng th1. Kt qa mi
vch ca ph dao ng l tp hp ca nhiu vch nh c tn s bng tng
ca tn s dao ng v tn s quay.
=

dd

qy

(1.10)

Nng lng tng ng vi trng thi ny l tng nng lng quay Eq v


nng lng dao ng Ed.
Eqd = Eq + Ed
(1.11)
Ph dao ng quay cn gi tt l ph dao ng hoc ph hng ngoi(IR
2.5. Dao ng ring ca phn t
Cc phn t c t ba nguyn t tr ln, ngoi dao ng ko dn v nn
dc, cn c dao ng lm thay i gc ca cc lin kt. Vic lm thay gc ca
cc lin kt thng d dng hn so vi lm thay i di lin kt cho nn
nng lng ca n thng nh hn.
Ni chung chuyn ng dao ng ca phn t nhiu nguyn t l rt
phc tp.Tuy vy lun c th phn chia mt chuyn ng phc tp thnh
nhng dao ng n gin hn gi l dao ng c bn hay dao ng chun.
Trong trng hp chung phn t c N nguyn t s c 3N-6 dao ng c
bn. Cc dao ng c bn khng suy bin s c tn s khc nhau.
i vi phn t c nhiu nguyn t th tng s dao ng s l
3N - 5 i vi phn t thng
3N 6 i vi phn t khng thng.
iu kin dao ng c th xy ra l phi cung cp mt nng lng
tng ng. Cc dao ng c cng mc nng lng gi l dao ng thoi
bin.
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17

Cc dao ng ring c th chia ra lm hai nhm sau


2.5.1. Dao ng ha tr
L nhng dao ng lm thay i chiu di lin kt ca cc nguyn t
trong phn t nhng khng lm thay i gc lin kt.
2.5.2. Dao ng bin dng
L nhng dao ng lm thay i gc lin kt nhng khng lm thay i
chiu di lin kt ca cc nguyn t trong phn t
2.5.3. Dao ng i xng v bt i xng
Xt phn t nc c ba nguyn t ca hai nguyn t khc nhau cho thy
Dao ng ha tr i xng ca lin kt OH l ko v nn ng thi k
hiu l

OH(s).

Cn dao ng ha tr bt i xng ca lin kt OH l mt bn

OH b dn ra, cn mt bn lin kt OH b nn li k hiu l

OH(as)

Dao ng bin dng ca OH l gc ha tr b thay i, lc to lc nh


thng uc k hiu l

OH.

Nh vy phn t H2O c th c cc dao ng ring nh sau :


H2O l phn t khng thng nn c 3 dao ng, trong hai dao
ng ha tr mt i xng v mt bt i xng, mt dao ng bin
dng.

Hnh 1.4 : cc kiu dao ng trong phn t nuc.


a. Dao ng ha tr i xng
b. Dao ng ha tr bt i xng
c. Dao ng bin dng
Trn ph hng ngoi ca phn t nc c xut hin hai vch hp th gn
nhau 3756 v 3652 cm-1 ng vi dao ng ha tr i xng v bt i xng
v mt vn hp th 1596 cm-1 ng vi dao ng bin dng ca lin kt OH.
CO2 l phn t thng cho nn s c 3N-5 =3.3-5 =4 dao ng ring
trong 1 dao ng ha tr i xng v 1 dao ng ha tr bt i
xng hai dao ng bin dng.

18

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Hnh 1.5: cc kiu dao ng trong phn t CO2


a.
Dao ng ha tr i xng
b.
Dao ng ha tr bt i xng
c.
Dao ng bin dng
Tuy vy trong thc t cc dao ng ha tr v bin dng khng hon ton
bin dng hay ha tr m chng cng c t nhiu nh hng ln nhau.
2.6. Dao ng nhm (hay cn gi l dao ng nhm chc) v tn s c
trng
Vic qui kt v gii thch tng vn hp th trn ph hng ngoi ca phn
t nhiu nguyn t khng n gin v d dng v cc cc dao ng trong
phn t tng tc ln nhau lm bin i nhng tn s ca dao ng c bn.
V vy ngi ta a vo quan nim dao ng nhm, xem mt vi dao ng
ca cc lin kt ring r hoc ca cc nhm chc nh c lp vi cc dao
ng khc trong ton b phn t. Dao ng ny xut hin khong tn s rt
hp v c trng trong ph ca tt c cc cht cha nhm chc ny.
Theo quan nim dao ng nhm, nhng nhm nguyn t ging nhau
trong cc phn t c cu trc khc nhau s c nhng dao ng nh v th
hin nhng khong tn s ging nhau. Nhng tn s ny c gi l tn s
c trng. V d dao ng ca nhm C-H, O-H,N-H, C=C, C=N, C=O, N=N...
Trong cc nhm nguyn t ny ca phn t hng s lc lin kt hoc
khi lng khc bit nhau so vi cc phn khc ca phn t.

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19

Hnh 1.6.Tn s c trng cho dao ng ca cc nhm chc.


3. Tn s c trng, cc yu t nh hng
Dao ng ca cc nhm nguyn t trong phn t khng hon ton l dao
ng nh v m chu tng tc ca cc dao ng khc trong ton phn t.
Tuy vy nh hng ny thng khng ln lm khong 5%, nhng tr s v
hng dch chuyn tn s th li c mt ngha quan trng trong vic phn
tch cu trc ca phn t.
Tn s c trng ph thuc rt nhiu vo hng s lc lin kt ca cc
nguyn t v khi lng ca chng. Khi hng s lc khc nhau khong 25%
th tn s c trng ca chng khc nhau rt r. Khi lng ca cc nguyn
t khc nhau cng s cho tn s c trng khc nhau
V d.
Nhm OH c tn s c trng 1600 cm-1
Trong khi nhm OD cho tn s c trng 2650cm-1
Tn s c trng ca mt s nhm chc
C-H ~3000 cm-1
C-C ~ 1100-900 cm-1
C-Br ~ 600cm-1
Bng 1.5. Hng s lc ha tr ca mt s lin kt
Lin kt
-C-C>C=C<
-C=C-C-O-C=O
-C-N20

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

3.1. nh hng ca trng thi tp hp


Cc cht trng thi khc nhau (kh lng rn) c th s cho cc tn s
c trng ca nhm chc khc nhau. Nguyn nhn ca hin tng ny l do
s tng tc gia cc phn t trng thi khc nhau s khc nhau.
V d axeton trng thi kh c dao ng ha tr vi tn s c trng ca
nhm C=O l 1742 cm-1, trong khi trng thi lng th tn s c trng
dch chuyn v 1718 cm-1.
Cn ph hng ngoi ca CH3I th kh v th lng c dng nh sau

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

Trong : X, Y thng l cc nguyn t F, O, N. cn A, B l phn cn li


ca phn t. Y phi c t nht mt cp electron t do.
Nu c hai hp phn AX-H v YB u cng trong mt phn t th ta c
lin kt hydro ni phn t. Cn nu l thuc hai phn t khc nhau ta c lin
kt hydro lin phn t.
Khc vi dao ng ha tr lin kt hydro lm kh khn cho dao ng bin
dng ca lin kt XH cho nn lm tng tn s ca dao ng bin dng.
Trong ni b phn t lin kt cu hydro ch c th to thnh khi yu t
khng gian thun l1.
Th nht khong cch gia chng phi nm trong gii hn no .
Th hai lin kt hydro ni phn t s bn vng hn khi chng to ra
vng 5 cnh hoc 6 cnh.
Cc nhm OH, NH, c kh nng to cu hydro trong cc dung mi khc
nhau hoc nng khc nhau.
V d:
Dao ng ha tr ca nhm OH t do (khng lin hp) l 3590 3650 cm-1
Trong khi dao ng ha tr ca nhm OH lin kt (to cu hydro) l
3350cm-1. Cc lin kt cu hydro ni phn t v ngoi phn t th hin rt r
trong ph hng ngo1.
Lin kt cu hydro ni phn t c th nhn din nu khi pha long dung
dch ca n m tn s c trng khng thay 1.
Lin kt cu hydro ngoi phn t th tn s c trng thay i rt mnh.
V d:
Tn s c trng ca nhm OH trong phn t xiclohexanol trong CCl 4 vi
nng khc nhau 1,0 mol v 0,01 mol c th hin trong hnh sau :

22

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Hnh 1.8.Tn s c trng ca dung dch hexanol


trong CCl4 vi nng khc nhau
th lng tinh khit cc phn t tng i linh ng v khng b nh v
cht ch nh th rn. Tuy nhin tng tc lng cc gia cc nhm phn
cc mnh v c bit l lin kt hydro vn gi cho cc phn t vo mt trt
t nht nh no . V th khi so snh tn s cc vch hp th ca cc cht
khi o ph dng lng tinh khit xt on v cu trc thng gp kh
khn nht nh.
loi tr nh hng ca cc tng tc mnh gia cc phn t ngi
ta s dng dung dch long vi cc dung mi tr trong vng hng ngoi nh :
n-hexan, xiclohexan, cacbon tetraclorua, cacbon disunfua....Ph thu c t
cc dung dch long ny thng p ng c yu cu xt on v cu
trc ca cc phn t

Hnh 1.9. nh hng ca lin kt hydro ni phn t n tn s c trng


ca nhm OH v CO.
3.3. nh hng ca dung mi
Khi nghin cu ph hng ngoi ca cc cht trong dung dch cn phi
tnh n bn cht ca dung mi v nng ca cht tan. Khi pha long dung
dch cng ca cc vch hp th tham gia lin kt hydro gim i cn
cng ca vch lin kt hydro t do tng ln
Bn cht ca dung mi t nh hng n tn s dao ng ca cc nhm
khng phn cc nhng li nh hng rt ln n tn s ca cc nhm phn
cc. V d Khi chuyn t dung mi ny sang dung mi khc tn s dao ng
ca cc nhm C-H ankan, anken, aren, C=C hoc C C bin i khng ng

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23

k, ngc li tn s hp th ca cc nhm C-H ankin, OH, NH, C=O... li thay


i rt nhiu.
Bng 1.6. nh hng ca dung mi n tn s c trng nhm (cm-1)
Hp cht
C6H5 CH
Pyrol
C6H5OH
C6H5COCH3
C6H5COOH
C6H5COOCH3

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

Bng trn cho thy ngay c vi dung mi tr nh n-hexan, tn s dao


ng ha tr ca nhiu nhm nguyn t cng gim so vi th kh. Mc
nhiu hay t ph thuc vo tng tc gia phn t dung mi v cht tan.
S to lin kt hydro khng nhng lm chuyn dch tn s hp th m
cn lm rng cc vch hp th.
Trong dung dch cng nh trong th lng nguyn cht cc phn t c th
tham gia vo cc cn bng nh cn bng monome-dime (i vi axit
cacboxylic) hoc cn bng (xeto-enol). Nu thi gian tn ti ca mi dng
ln th trong ph hng ngoi ta s thu uc cc vch ph tng ng.
i vi axit cacboxylic nng nh trong dung mi n-hexan cn bng
monome-dime chuyn dch v pha to ra monome. Khi trn ph hng
ngoi quan st thy vch 1750 cm-1 c trng cho dao ng ha tr ca
C=O(

C=O)

khi nng ca axit tng hoc thay i dung mi vch ny chuyn

dch v 1720 cm-1. l vn hp th ca nhm COOH tham gia lin kt hydro.


4. My quang ph hng ngoi v cc iu kin ghi ph
4.1. My quang ph hng ngoi hai chm tia
My o ph hng ngoi ph bin nht hin nay l loi my gm cc b
phn chnh sau:
B cp ngun sng,
B tch nh sng n sc,
B phn nhn tn hiu v khuch i tn hiu
-

24

B phn x l tn hiu .

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Ngy nay cc th h my IR mi c hon thin v t ng ha rt


nhiu gip cho cc nh phn tch thun li hn trong thao tc v vn hnh
my.
S nguyn l my o ph hng ngoi hai chm tia c m t nh
sau:
Ngun bc x 1 pht ra chm tia hng ngoi vi mi tn s trong vng
cn kho st. Chm tia ny c chia lm hai phn, mt phn i qua mu (2),
phn khc i qua mi trng o 2 (dung mi). B to n sc 3 s tch tng
tn s a qua b phn phn tch (detect) 4. Detect s so snh cng
hai chm tia cho ra nhng tn hiu c cng t l vi phn bc x b
hp th bi mu. My t ghi 6 s nhn tn hiu in do detect cung cp di
dng nhng ng cong ph thuc vo % bc x truyn qua vo s sng cm-

.
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

n ny cng pht bc x hng ngoi lin tc v cng thuc loi n t


nng vt en. Cu to ca n l mt thanh silicacbua di 40-60 mm v c
ng knh khong 4-6 mm, nhit t nng khong 1300-1500 oK.
4.1.2. Nhn tn hiu
Cc bc x hng ngoi c cng v nng lng thp nn thng
c s dng detect nhit da trn hiu ng nhit pht hin tt c cc
vng sng hng ngoi.
Detect ha in thng c dng trong thit b ph hng ngo1. l
mt thanh mng cht ha in nm gia hai in cc to ra mt t in.
Cc cht ha in thng dng l triglixin sunfat (TGS) c bin tnh
vi dteri (DTGS).
Tia sng sau khi i qua mu o s b hp th mt phn cn li c a
qua b phn nhn tn hiu bin tn hiu nh sng thnh tn hiu in vi dng
rt nh. Cng dng in ph thuc vo nh sng b hp th nhiu hay t.
Thng thng dng in ny rt nh nn phi c b phn khuch i
dng in mnh ln v sau a vo my tnh v ph v x l s liu
V d : mt s vt liu lng knh cc bc sng
Vt liu
Chiu di sng
LiF

2-6 m

CaF2

1-8 m

NaCl

2,5 15 m

KBr

12,5 25 m

CsI

25 50 m

Hin nay cc my ph hng ngoi th h mi c ch to theo kiu


bin i Furie FTIR (Fourier Transformation Infared Spectrophotometer).
Trong my o FTIR ngi ta khng dng b to n sc m dng b to
giao thoa gm mt gng c nh v mt gng di ng v b phn chia
chm tia sng.
4.2. My quang ph hng ngoi bin i Fourier gm cc b phn chnh
sau

26

Ngun sng (1)


Giao thoa k (2)

Detect (6)
My tnh (7)

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Hnh 1.11: S ph k bin i Fourier FT-IR


1. Ngun sng; 2. Gng c nh; 3. Gng di ng.
4. Chia chm sng; 5. mu o; 6. Detect; 7. My tnh
4.2.1. Ngun sng
Ngun sng cho ph k FT-IR cng l n Nernst, n global, pht ra
bc x hng ngai lin tc
4.2.2. Giao thoa k
Gm mt gung c nh, mt gng di ng v b tch quang. B tch
quang c ch to t mt s vt liu khc nhau ty thuc vo vng hng
ngoi xa hay gn, mi loi vt liu c s dng cho mt vng gii hn bc
sng
Bng 1.7: Vt liu ch to b phn tch quang.
Vt liu

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

Nguyn tc c bn ca detect l khi mt photon p vo mt ca mt


cht rn s lm bt ra cc electron, sau cc electron ny chuyn ng v
p vo b mt cht rn v li lm bt ra electron vi s lng ln hn nhiu
ln. Cht rn phi l nhng cht bn dn v mi cht tng ng vi mt
vng bc x hng ngoi khc nhau.
Bng 1.8: Mt s cht bn dn lm detect
v vng ph hng ngoi tng ng
Vt liu detect

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

My ph hng ngoi bin i Fourier thun tin hn my ph hng ngoi


thng. Vic dng giao thoa k cho php lm khe sng rng hn do lng
nh sng thu c trn giao thoa k s ln hn nhiu so vi b to n sc.
Ngoi ra n cn gim c nhiu, tng tn hiu v t ng ha mc cao.
Trong qu trnh lm vic thang tn s ca my c th b x dch v vy
phi iu chnh li theo cht chun nh amoniac, hi nc hoc polistiren.
4.3. Chun b mu ghi ph hng ngoi
Mu phn tch c th dng kh, lng, rn. Mi loi mu u c cuvet
ring v chun b theo phng php thch hp.
4.3.1. Mu dng kh
C loi cuvet ring vi di 10cm trong c t gng phn chiu
tng chiu di ng i ca nh sng v tng hp th nh sng ca phn
t kh. Hai u cuvet c bt bng tm NaCl
4.3.2. Mu dng lng
Nu l cht lng tinh khit th dng hai tm NaCl v nh mt git cht
lng vo gia hai tm NaCl to thnh lp mng cht lng p gia tai tm
.hoc cng c th o bng cuvet ring khi cht tan trong dung m1.
Dung mi pha long mu thng s dng l CCl4 hoc CHCl3.
Cn phi ch l mu v dung mi phi tuyt i khan nu khng s lm
hng cc tm ca s bng tinh th KBr hay NaCl.
Dung dch mu uc chun b nh sau
Ha tan cht nghin cu vo dung mi thch hp vi nng 1-5 %, sau
cho vo cuvt th nht. dy ca cuvt l 0,1 mm. Cho dung mi vo
28

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cuvt th hai ging ht cuvt th nht v dy v vt liu ch to. Nh so


snh hai chm tia i qua dung dch v dung mi ngi ta c th loi vch hp
th ca dung m1.
Nng cht ghi ph IR ca mu lng trong khong t 10-2 n 1 mol /l.
ghi ph cho nhng mu c tinh kim, axit, hoc dung dch nc th phi
dng cc cuvet khng tan trong nc nh fluorit, silic, germany l nhng vt
liu khng hp th trong vng nh sng hng ngo1.
dy ca cuvt cng c nh hng ln kh nng hp th nh sng ca
dung mi.
V d : CCl4 cuvt c dy =0,1 mm c coi l trong sut vng
4000-820 v 720-650 cm-1 nhng cuvt c dy 1mm n hp th ng k
1600-1550 1270-1200, 1020-960 cm-1.
4.3.3. Mu dng rn
C nhiu cch o mu dng rn nhng n gin v thun tin nht l
p vin vi KBr.
Nghin mu tht mn sau p vi KBr vi mt lng KBr ln hn t 10100 ln trn my nn p thnh nhng vin dt vi chiu dy khong 0,1 mm.
Vin dt thu c hu nh trong sut v cc cht phn tch c phn tn
ng u.
Lng mu cn thit p mng khong 2-5 mg.
Cn ch l KBr c tnh ht m rt mnh nn trong ph thng xut hin
vch ph hp th ca nc 3450 cm-1. Ngoi ra dng KBr cn c th xy ra
phn ng trao i cation hoc anion vi cc cht nghin cu l mui v c
hoc cc phc v c
5. ng dng ca ph hng ngoi trong phn tch hp cht hu c, ha
du
Quang ph hng ngoi dng xc nh cc nhm chc, nh danh
cc hp cht hu c v nghin cu cu trc ca chng.
xc nh cc nhm chc cn phi s dng mt lot cc vch hp th
c trng ca nhm ny.
V d nh danh cc hydrocacbon thm c th da vo cc vch ph
c trng trong vng 3000 cm-1 c trng cho dao ng ha tr ca lin kt CHarom., 1600-1500 cm-1 c trng cho dao ng ha tr ca lin kt C=C arom v
900-700 cm-1 c trng cho dao ng bin dng ca lin kt C-H.
S thay i tn s hp th lin quan n trng thi tn ti ca cc phn
t hp cht. trng thi lng v kh mt s hp cht hu c c th c nhiu
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29

cu trc ng phn. trng thi rn th thng thng ch tn ti mt ng


phn.
V d: ph hng ngoi ca ca cloaxeton c hai vch ph ca hai ng
phn vng dao ng ca lin kt C-Cl 673 v 728 cm-1 trong khi
trng thi rn ch c mt vch ph hp th 761 cm-1.
5.1 Cc tn s c trng ca hp cht hu c hydrocacbon
5.1.1. Hydroccbon bo ha (Parafin)
Quang ph hng ngoi ca cc hydrocacbon bo ha c trng bi s
xut hin cc vng hp th c trng ca cc lin kt trong cc nhm chc
metyl -CH3, metylen -CH2-, metyliden -CH
Cc nhm chc ny c tn s dao ng ba vng hp th l 3000-2800,
1400-1300 v 700 cm-1.
Ph hp ph vng 3000-2800 cm-1 c trng cho dao ng ha tr ca
lin kt C-H trong cc nhm chc -CH3 v -CH2-. Trong vng ny nhng nh
2962 v 2872 cm-1 l dao ng i xng v bt i xng ca lin kt C-H.
V d sau th hin nhng vch ph c trng ca cc nhm k trn
(h.1.12)

Hnh 1.12: Ph hng ngoi ca 2-metylbutan


5.1.2. Nhm Metyl [-CH3]
C ba dao ng ha tr v ba dao ng bin dng, ngoi ra cn c dao
ng qu lc v dao ng xon.
Dao ng ha tr i xng ca CH3 2872 10cm-1
Dao ng ha tr bt i xng ca CH3 mch thng hp th
2962 10cm-1 cn ca nhm CH3 mch nhnh 2930 cm-1.
cc hp cht thm nhm CH3 hp th 295 v 185 cm-1.
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Dao ng bin dng bt i xng nhm CH3 gn 1465 cm-1


V dao ng bin dng i xng 1375 cm-1.
Khi nhm CH3 gn vi cc d nguyn t O, P, N, S.. th tn s dao ng
ha tr v bin dng c thay i cht t.
Dao ng qu lc ca nhm CH3 hp ph mnh 1150-1120 cm-1 v
900-890 cm-1.
Nhm isopropyl hp th 922-919 cm-1.
Nhm t-butyl 932-926 cm-1,
Nhm CH3 cc hp cht thm hp th 1040.
Nhm S-CH3 l 950 cm-1.
Nhm P-CH3 hp th gn 880 cm-1.
5.1.3. Nhm metylen CH2
Dao ng ca nhm metylen bao gm 2 dao ng ha tr v 4 dao ng
bin dng sau
-

Dao ng ha tr bt i xng (a)


Dao ng ha tr i xng.(b)

Dao ng bin dng hnh ko (c)


Dao ng bin dng qut (d).
Dao ng bin dng xon.(e)
Dao ng bin dng u a (f).

Hnh 1.13: Cc kiu dao ng ca nhm CH2


i vi hydrocacbon mch thng dao ng ha tr bt i xng ca nhm
CH2 nm vng 2390 cm-1. cn dao ng ha tr i xng 2850 cm-1
Cc dao ng bin dng ca nhm CH2 cng c dao ng bin dng i
xng 1380 cm-1 v bt i xng 1460 cm-1.

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31

Trong hydrocacbon mch thng nu s ccbon n >5 ph IR ca nhm


CH3 xut hin nh mt vi ph c trng cho dao ng bin dng ca nhm
CH2.
Khi nhm CH2 vi ni i hoc ni ba ca n 1440 cm-1 cn ni vi
nhm CO cacbonyl th 1425 cm-1.
Dao ng bin dng qa lc ca nhm metylen vng 790-720cm-1. V tr
ca cc mi ph thuc vo di ca mch cacbon.
V d : C2H5 790-770 cm-1. C3H7 743-734 cm-1
Dao ng qu lc ca nhm CH2 cn c th dng pht hin mch
polymetylen. Cc dao ng bin dng khc ca nhm metylen nm vng
1300 cm-1 vi cng yu.
Thc nghim ch ra rng khi trong phn t cht hu c cha nhm propyl
th trong ph IR s xut hin hai vng hp th 1170 v 1145 cm-1, nhm tertbutyl 1255 v 1210 cm-1, v nu c nhm cha cacbon bc bn
(tetracacbon) s c cc nh 1215 v 1195 cm-1.
51.4. Cc xicloankan
Nhm CH2 c dao ng ha tr bt i xng vng su cnh l 2930
cn vng ba cnh l 3080 cm-1.
Dao ng ha tr i xng 3030-2840 cm-1.
Dao ng bin dng ca nhm CH2 vng 1470-1450 cm-1.
Ni chung khi di ca cnh cng ln th cng ca cc vch hp
th cng tng, s ph thuc ny c th biu din qua th sau.

Hnh 1.14. S ph thuc ca cng hp th vo s nhm CH2


5.1.5. Nhm metyliden CH

32

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Nhm C-H bo ha c dao ng ha tr 2900 cm-1, cn dao ng bin


dng ca n 1350-1315 cm-1, khi nhm C-H gn trc tip vi vi cc d
nguyn t th tn s dao ng c th b thay 1.
V d : CHCO c dao ng bin dng 1420-1370 cm-1.
Nhm CH khng no v thm c th phn bit vi nhm CH no tn s
hp th thng >3000 cm-1, cn no < 3000 cm-1. Tuy nhin do cng ca
vch khng no nh hn nn chng thng b che ph bi vch ph ca CH
no hoc cc vch ca nhm NH v OH c cng ln hn rt nhiu.
5.2. Hydrocacbon khong no (olephin)
Cc olephin l nhng hp cht hu c cha trong mch ca n cc lin
kt 1. i din u tin ca dy ng ng ny l etylen c coi l olephin
cha th. Cc ng ng cao ca n l cc olephin th gc hydrocacbon bao
gm cc dng th sau :
-

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

Nh trong bng trn khi tng s th tn s dao ng lin kt C=C tng.


Mt khc cu trc hnh hc ca phn t cng lm thay i tn s nh cu
trc ng phn trans tn s cao hn so vi ng phn cis, tuy vy cng
vch hp th li thp hn
Bng 1.10. cng vch hp th ca cc cht
Hp cht

, 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

Trong phn t olephin tn ti dao ng ha tr v bin dng ca lin kt


C-H, dao ng qu lc, dao ng qut l dao ng ha tr ca lin kt C=C.
-

Dao ng ha tr ca =CH nm 3100-3000 cm-1.

Dao dng bin dng =CH 1400-1000 trong mt phng v ngoi mt


phng 1000-600 cm-1.
Dao ng ha tr n ca C=C 1680-1640 v lin hp 1650-

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

mnh c th nhn bit nhm chc ny.


i vi cc hp cht olephin vng (xicloanken) tn s dao ng C=C c
th thay i theo ln ca vng v cc nhm th ca chng.
5.3. Hydrocacbon thm (Aromatic)
Hyrocacbon thm c cc dao ng ba vng sau:
Dao ng ha tr ca lin kt C-H 3100-3000 cm-1.
Dao ng ha tr C-C vng 2000-1650 cm-1
Dao ng bin dng C-H vng 900-650 cm-1.
Dao ng ha tr C-H c cng vch ph trung bnh v thng l mt
nhm vch ph. Khi c nhm alkyl th vch hp th ca nhm C-H trong vng
thm th hin nh mt vai trn vch ph ca lin kt C-H bo ha.
Khi c mt cc nhm th th tn s dao ng ha tr thay i cht t.
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Cc dn xut th mt ln ca benzen C6H5X trong X l nhm, halogen,


ankyl, amin NH2, Andehit CHO..
S hp th ca cc hp cht thm trong vng 1600-1500 cm-1 gm cc
vch ph 1600,1580, 1500, 1450 cm-1.
Cng ca cc vch ny thay i rt rng. Vch 1500 cm-1 c
cng ln hn so vi vch 1600 cm-1.
Vch 1580 ch xut hin khi vng benzen lin hp vi nhm khng no.
S lin hp s lm tng cng cc vch ph nhng t lm thay i v tr
ca n.
Cng vch ph vng < 900 cm-1 - 670cm-1 ca hydrocacbon thm
rt mnh c trng cho dao ng bin dng ngoi mt phng ca lin kt C-H
ca vng thm
Bng 1.11. Tn s c trng cho dao ng bin dng ngoi mt phng ca CH trong benzen th. (cm-1)
Tn s dao ng

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

i vi vng benzen dao ng bin dng ny vch 671 cm-1, cn


vng benzen th tn s ca dao ng bin dng ca lin kt C-H ph thuc
vo s v v tr ca nhm th.
Theo s lng v v tr vch ph c th xc nh loi th ca vng
benzen.(para, octo, hay meta...).
Loi th ca vng benzen cn c th xc nh theo vch ph vng
2000-1600cm-1.
vng ph ny xut hin dao ng bin dng t hp ca lin kt C-H vi
cng yu ( =5) v vy mun thy c vch ny cn phi ghi ph ca
mu vi nng cao hn gp 10 ln.
Khi phn t benzen th th tnh i xng ca n cng thay i do s
dao ng c bn cng thay 1.
Bng 1.12: Dao ng bin dng ca C-H trong mt phng ca benzen th
(cm-1)
Th mono

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

Dao ng ha tr ca lin kt C=C trong vng benzen th c vch hp th


bn nh sau :1450, 1500, 1580, 1600 cm-1.Cng ca cc vch hp th
ph thuc vo m in ca cc nhm th. Cng ca cc vch mnh
hay yu ty theo nhm th l y in t hay ht in t

36

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Hnh 1.15: Ph hng ngoi ca 1.m- xylen, 2:o-xylen ;3 : p-xylen


5.4. Hidrocacbon axetilenic
Khi trong phn t cha lin kt ba C C trong ph hng ngoi s xut
hin tn s hp th c trng 2300-2100 cm-1.
Dao ng ha tr

CH

ca axetylen khng th ch hp th 3287 cm-1 v

729 cm-1. Cn vch hp thu ng vi C C th khng xut hin v b cm.


Axetilen th
Axetilen th cho dao ng ha tr

C-H (th mono) 3320 - 3300 cm-1.

Dao ng ha tr th hai ln C C 2140-2100 cm-1.


Dao ng bin dng ca nhm C C-H 650-610 cm-1.
Dao ng t hp 1250-1220 cm-1.
5.5. Hydrocabon lin hp
Cc lin kt i lin hp C=C s c hai vng hp ph 1650 -1600 cm-1.
S lung cc ni i lin hp tng ph hp th s chuyn dch v pha c tn
s nh hn.
Khi ni i lin hp vi vng thm th s chuyn dch tn s thng nh
hn khi lin hp vi cc lin kt bo ha. Cng hp th tng mnh cng
vi s tng cng ca ca dao ng khung ca vng thm trong khong
1600-1500 cm-1.
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37

5.6. Cc hp cht hu c vi cc nhm chc khc nhau


5.6.1. Cc hp cht cha oxy (ancol, phenol, ete)
Nhng hp cht cha nhm hydroxyl OH s c cc ph c trng ca
dao ng cc lin kt O-H v C-O. Cc vch ph c trng nht vng 36003000 cm-1 l dao ng ha tr ca nhm O-H 1400-1000 cm-1 l dao ng
bin dng ca lin kt CO H
Dao ng ha tr ca nhm O-H l rt c trng hp th vng tn s rt
rng t 3600-2500 cm-1 v trong c hydro linh ng tham gia do vic to
thnh lin kt cu ni hydro gia cc phn t.
V tr ca vch ph hp th c th thay i thy theo nng dung dch
v ty loi dung mi ha tan v n lm thay i s lng cu ni hydro.
Nhm O-H t do ca phenol v v ru c vch hp th vng rt hp
3670-3580 cm-1 v rt d dng xc nh.
Bng 1.13: Tn s hp th ca cc nhm OH ca ancol v phenol
Nhm

Tn s
cm-1

Dng dao
ng

Ghi ch

-OH t do

3650-3590

Ha tr OH

Thng nhn

-OH lin kt hidro

3600-3200

Ha tr OH

Thng t. Lin kt
hidro cng mnh,
tn s cng gim

-OH lin kt hydro


ni phn t

3200-2500

Ha tr OH

Hay ln vi dao
dng OH ca axit

H2O trong dung


dch

3710,
3600-3100

Ha tr OH

Vch ph rng

H2O kt tinh trong


mu rn
H2O m

1640-1615

Bin dng OH

3500-3450

Ha tr OH

-O-H
-C-OH

1410-1260
1150-1040

Bin dngOH
Ha tr C-O

Tng khi c lin kt


hidro

Mt c trng quan trng ca s to thnh lin kt hydro gia cc phn


t l s thay i v tr vch ph vng 3600-3200 cm-1 khi thay i nng
ca hp cht trong dung mi.
Khi nng thp cc vch ph c vng hp th rt hp ni ln nhm
OH t do.

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Hnh 1.16 : Ph hng ngoi ca mt s hp cht cha nhm OH


1:6-clo -1-hexanol ;2: o-crezol ;3:pyrocatechol.
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39

Khi tng nng dn n to thnh cc dimer v polymer. Trong ph IR


ngoi vch ph c trng cho nhm OH t do cn xut hin cc vch ph
vng c bc sng di hn. Nu tip tc tng nng ca hp cht s lm
tng cng hp th ca cc nhm OH lin kt v gim cng ca
nhm OH t do.
Nhm OH vi lin kt cu hydro ni phn t c vch hp th rt hp
trong khong 3590-3420 cm-1.
Khc vi nhng hp cht c lin kt cu hydro gia cc phn t, vch
hp th c trng ca chng trong dung mi khng ph thuc vo nng
ca chng.
Nh vy trong vng ph IR t 3600-3000 cm-1 cho php kho st cc loi
lin kt hydro ca cc hp cht hu c bng cch thay i nng ca chng
trong dung mi v quan st s ph thuc ca cng v v tr cch vch
ph c trng ca chng theo nng .
Bng 1.14: Dao ng ha tr ca nhm O-H (cm-1)
Tn s (cm-1)

Hp cht
O-H t do

3670-3580

Cu hydro ngoi phn t

2550-3200

Cu hydro ni phn t

3590-3420

Vng cng cua

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

3632- khng lin hp


3615 lin hp.

C6H5CH2CH2-O-H

3634 khng lin hp

Dao ng bin dng ca nhm O-H trong phn t phenol v ancol nm


trong vng 1400-1200 cm-1 ph thuc vo bc ca ancol.

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Bng 1.15 : Dao ng bin dng ca nhm O-H ca hp cht


phenol v ancol
Hp cht

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

Bng 1.17: Cc vch hp th ca hp cht ete.


Tn cht

tn s cm-1

Ete mch thng


Ete thm

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

vng hp cho nn c th dng cc ph ny nhn bit nh danh v s c mt


ca hp cht cacbonyl.

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

Bng 1.18: Tn s c trng ca nhm C=O v C=C


trong cc hp cht khc nhau.
Hp cht

C=O

cm-1

C=C

cm-1

C6H6-CHO

1705 (lng)

CH2=CH-CHO
CH2C-CHO

1722 (pha hi)


1703
1702

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

Tn s dao ng ca andehit mch thng vng 1740-1720 cm-1 ca


andhit thm vng 1740-1685 cm-1. Cc andehit cha no kiu ,
C=CH-CHO
C vch hp th ca C=O nm vng 1700-1660 cm-1 v lin kt C=C
1640-1560 cm-1.Thng thng cng vch hp th C=C yu hn so vi
vch hp th C=O.
Dao ng ha tr C-H nhm cacbonyl hp th vng 2900-2700 cm-1
v thng cho hai nh 2810 v 2720 cm-1 vi cng mnh.
b. Keton bo ha
Ph hp th c trng ca nhm C=O vng 1725-1705 cm-1. Axeton
trng thi hi c vch ph 1742, cn trong dung mi th vch ph vng
1728-1718 cm-1.
c. Xeton bo ha
Xeton bo ha c vch hp th 1742-1738 cho dng hi ng vi dao
ng ha tr ca nhm C=O cn th lng c vch hp th 1725-1705
cm-1. Nhm CH3 gn cnh nhm C-O cho vch hp th 1370-1350 cm-1 c
trng cho dao ng bin dng ca lin kt C-H.
Nhm CH2 gn cnh nhm C=O cho nh hp th 1440-1405 ng vi
dao ng bin dng ca ca lin kt C-H.

Hnh 1.18. Ph hng ngoi ca axeton


d. Xeton khng bo ha
Cho vch hp th tng ng vi dao ng ha tr C=O v C=C. Do hiu
ng truyn in t lin hp lm chuyn dch tn s hp th ca C=O v
C=C so vi hp cht bit lp.
Tn s hp th ca C=O lin hp s gim di t 30-50 cm-1 v ca C=C
cng gim i khong cm-1.
44

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Bng 1.19. Tn s hp thu C=O v C=C ca xeton khng bo ha


Cng thc

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

Bng 1.20: Tn s c trng ca nhm C=O trong xeton vng thm.


Hp cht

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

Bng 1.21: Tn s c trng C=O ca xeton vng bo ha


(cm-1)

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

Cc xeton vng bo ha c tn s hp th C=O thay i theo ln ca


vng
C3 > C 4 > C 5 > C 6 > C 7

C8

Cc xeton vng c c trng dao ng C-H vng nm vng 1460


1400 cm-1 vi nhiu nh hp th khc nhau.

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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Anion ca axit cacbocylic [ COO- ] c hai vch ph vng 1680-1610 v


1400-1300 cm-1 c trng cho dao ng i xng v bt i xng ca nhm
COO-.
Nhm C=O c th lm thay i tn s ca dao ng ca nhm ankyl st
cnh n
V d. Tn s dao ng bin dng ca nhm metyl CH3 trong keton dch
chuyn v vng 1360-1355 cm-1. Cn trong este ca axit cacbonoic chng hp
th vng 1440-1435 cm-1
Nhm cacboxyl COOH gm hai nhm C=O v O-H
V c s dch chuyn electron trong nhm cacboxyl nn n tn ti hai
dng mesome khi tn s c trng ca

C=O

ancol v phenol.Tn s dao ng ha tr ca

C=O

OH

s khc so vi andehit,

trong axit v andehit, xeton

khc nhau do hiu ng chuyn dch electron.

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

Vch hp th dao ng ha tr ca C=O rt nhy vi s thay i trng


thi vt l ca hp cht, thng thng tn s

C=O

ca hp cht th hi l

cao nht, sau trong dung mi phn cc yu nh CS 2, CCl4 hoc khng


phn cc nh CHCl3 hoc CHBr3. Cn tn s C=O th rn l thp nht do
c s tng tc gia cc phn t v thng gim khong 15 45 cm-1.
Axit cacboxylic c cc vch hp th sau:
Bng 1.22: Cc vch hp th cc axit cacboxylic
Cu to

C=O

OH

Monome (axit bo ha)


Dime (bo ha)

1800 1740 3570 3500


1720 1680 3000 2500

Axit cacboxylic thm

1760 1730 3560 3520

Monome
dime

1715 1680 3000 2500

Axit cha bo ha
> C=CH-COOH

1710 1680

> C C-COOH

1690 1670

Hnh 1.21.Tn s dao ng ca C=O trong axit propionic trong cc dung mi


khc nhau
a - th hi; b mng mng; c- trong dung mi CCl4 0,5 M; d- trong dung mi
dioxan
5.6.4. Cc hp cht cha Nit
a. Axit amit
i vi amit bc 1 v bc 2 c dao ng ha tr N-H c trng vng
3500 v 3400 cm-1 i vi axit bc 1 trong dung mi khng phn cc
Amit bc 2 c 1 vch hp th ca nhm NH t do vng 3440 3420
cm (cu trc cis) v 3460 3340 cm-1 (cu trc trans)
Dao ng ha tr ca nhm N-H trong hp cht amit c vch hp th
1690 1630 cm-1 trong dung mi long
-1

48

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Dao ng bin dng ca nhm NH c vch ph c trng vng 1620


1590 cm-1 i vi amit bc 1 v 1550 1510 cm-1 i vi amit bc 2.

Hnh 1.22. Ph hng ngoi ca N - metylaxetamit


b. Cc Amin
Trong ph IR c cc vch c trng cho dao ng ca nhm N-H v C-N
Dao ng ha tr ca nhm N-H nm vng 3500 3300 cm-1 (amin bc
I v II). Amin bc III khng c vch hp th ny. Ging nh nhm OH, nhm
amin cng c xu hng to thnh lin kt hydro gia cc phn t, khi tn
s s dch chuyn v pha tn s nh hn. Dao ng bin dng ca nhm
NH2- c vch hp th 900 650 cm-1 i vi amin bc 1.
Trong vng 1360 1000 cm-1 tt c cc amin u xut hin vch ph c
trng cho dao ng ca lin kt C-N trong mch.
Cc mui ca axit amin c vch hp thu ca cc ion COO- v NH3+.
Dao ng ha tr ca NH3 tn s 3100 2600 cm-1 v 2200 2000 cm-1.
Dao ng bin dng bt i xng ca NH3+ 1530 1490 cm-1.
Dao ng ha tr bt i xng ca COO- 1605 1555 cm-1.
Dao ng ha tr bt i xng ca CO2 1425 1393 cm-1.
Dao ng bin dng i xng NH3+ 1530 1490 cm-1.
Dao ng bin dng ca C-H 340 1315 cm-1.
Nhm amin nh hng n dao ng ha tr v bin dng ca cc gc
hydrocacbon (N-CH3, N-CH2-...) ni lin vi nit
i vi lin kt N=C- dng R-CH=N-R
Trong R: Alkyl, Aromatic, OH th vch hp th trong khong 1690
1625cm-1. trng thi rn, tn s hp th thp hn khong 20 30cm-1
Cng hp th ca nhm C=N- kh mnh v ph thuc vo c tnh
ca nhm lin kt vi n.
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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

ca amin bc 1 c vch 1650 1580 cm-1 cn

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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Mui amin bc 2 NH2 v bc 3 NH c vch hp th 2550 2700cm-1 v


1600 cm-1.
Mui amin bc 4 R4N+ khng hp th vng hng ngoi
c. Nitril
C vng hp th c trng 2260 2215 cm-1 ng vi dao ng ca
nhm nitril C N. tn s hp th ca C N ca cc nitril mch bo ha (mono-,
di- nitril) 2260 2240 cm-1. Cc ni i lin hp v vng thm lm gim tn
s ca nitril khong 20 30 cm-1. Cng hp th thay i nhiu c th tng
gp i khi c ni i lin hp.
Nhm nitro NO2 c hai vch ph cng mnh vng 1650 1500 v
1390 1250 cm-1 c trng cho dao ng i xng v bt i xng ca nhm
NO2 trong cc hp cht mch thng.
Nhm nitro lin hp vi ni i dn n gim tn s hp th ca c hai
vch ph.
Trong hp cht nitro vng thm tn s hp th ca dao ng ha tr
vng 1550 1520 v 1360 1345 cm-1.
5.6.5. Hp cht c kim
Nhng lin kt cacbon kim loi C-Me c ph hp th vng tn s thp
trong khong 800 400 cm-1 ph thuc vo kim loi v gc hu c.
i vi gc Alkyl (-CH3) ni vi nguyn t kim loi (Me-CH3) dao ng
bin dng nm vng 1180 1140 cm-1 v tn s ny khng khc nhiu so
vi cc hp cht hu c khng c kim loi thm vo.
Phc ca kim loi vi hp cht cha no do c s to thnh lin kt hydro
lm gim tn s ca dao ng ha tr lin kt C=C i rt nhiu, c th gim
n 100 cm-1.
V d: s to thnh phc KPt(C2H4)Cl3 tn s

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

776, 696, 604, 563

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

V d: vi phc C5H5Cr tn s dao ng

C-H

c gi tr 668 cm-1 i vi

dibenzolcrom c cc vch ph sau:


Dao ng bin dng ngoi mt phng 794, 839 cm-1
Dao ng vng thm 1426 cm-1
Dao ng ha tr

C-H

S to thnh lin kt

= 3037 cm-1
vi kim loi dn n s gim tn s dao ng ca

vng thm v tng tn s dao ng ngoi mt phng ca C-H.


5.6.6. Phc cacbonyl
Tn s dao ng ha tr ca nhm

C=O

vng 2150 cm-1. Khi to phc

vi kim loi, tn s ny gim i thay i trong khong 2120 2020 cm-1. Cn


tn s dao ng ca lin kt Me-C vng 550 360 cm-1 i vi hp cht
nhm cacbonyl ch lin kt vi 1 nguyn t kim loi th ph thuc vo bn cht
ca kim loi v tnh cht ca cc nhm th khc m tn s hp th c th nm
vng 1900 2100 cm-1.
i vi cu ni lin kt mt lc 2 nguyn t kim loi th tn s hp th
gim n 1700 1400cm-1. V vy c th phn bit nhm cacbonyl cu ni
hoc cacbonyl cui mch.

52

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Cng vch hp th ca dao ng ha tr

C=O

thng rt cao. Phc

cacbonyl a nhn nh Fe2(CO)9, Fe3(CO)12, Co2(CO)8, Co4(CO)4 cho hp th


CO 2100 2000 cm-1 cn nhm CO to cu hp th 1900 1800 cm-1.
Bng 1.26. Tn s hp th

C=O

Hp cht

ca mt s phc cacbonyl cm-1


C=O

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

1826 (lin kt cu)


2043, 2020
1833 (lin kt cu)

441

6. Phn tch nh tnh v nh lng


6.1. Phn tch nh tnh
Bng phng php ph hng ngoi c kt qu kh chnh xc v s c
mt ca cc nhm chc trong phn t v c tnh ca lin kt cng nh cu
trc v v tr cc nhm th trong hp cht.
phn tch nh tnh v nh danh hp cht ha hc, cn phi nm
c cc tn s dao ng c trng ca cc nhm chc v ca cc lin kt
gia cc nguyn t.
Nhng tn s ny c xc nh bi cc nh khoa hc v c
a vo bng tra cu. Khi c c cc ph hng ngoi ca mt cht cha
bit no ngi ta c th so snh v tra cu tn s cc dao ng c lu
trong th vi tra cu v nh danh cc hp cht ha hc.
Ngoi ra ngi ta cn kt hp vi cc phng php khc nh ph
Raman nh danh chnh xc cc hp cht.
6.2. Phng php nh lng
Phn tch nh lng bng ph hng ngoi t chnh xc hn so vi cc
phng php khc (nh ph t ngoi kh kin UV-Vis). i vi hp cht
dng dung dch th phn tch nh lng cho kt qu chnh xc hn so vi
mu dng rn.
C s ca phng php nh lng cng da trn nh lut Lamber-Bia.
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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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V l thuyt ng biu din ca hm trn l mt ng thng tuyn tnh


qua gc ta , nhng thc nghim thng nhn c ng thng b un
cong u. V vy phi tin hnh xc nh nh lng tng khong nng
tuyn tnh on thng ca ng chun.
Ngoi phng php ng chun cng c mt s phng php khc
c s dng l phng php o hiu s hp th.
6.2.2. Phn tch nh lng thnh phn hn hp
Nguyn tc chung da vo tnh cht hp th ca hn hp bng tng
hp th ca tng hp phn cng mt bc sng.
DTS = D1 + D2 + D3 + D4 +... + Dn
Hay DTS =

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

ci: nng ca mi hp phn trong dung dch


: chiu dy lp dung dch (cuvet)
xc nh hm lng mi cht (nh lng) cn phi lp h phng
trnh vi n hp phn trong hn hp.
V d: dung dch hn hp ca ba hp phn cn phi xc nh hm lng
ca chng, h phng trnh c xy dng nh sau:
DTs1

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

nhau ph thuc vo cht cha trong hn hp.


T cc ph hp th ca cht chun c th tm c
ti mi tn s xc nh. Thay cc gi tr

ca mi hp phn

vo phng trnh c th tnh c

nng C1, C2 v C3 ca mi cht trong hn hp.


7. Cc tn s c trng ca cc hp cht hydrocacbon
7.1. Hydrocacbon no (Ankan)
Nhm chc
-CH3

(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-

mnh (35 75)


mnh (15 21)
Tb (<15)

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

7.2. Hydrocacbon khng no (Anken)


C nhng dao ng c trng ca cc lin kt sau. Dao ng nhm C-H.

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

Dao ng lin kt i C=C


1680 1620
Thay i
1695 1640
1660 1640
1665 1635
1675 1665

Tb (40)
Tb (35)
Tb
yu

1690 1670
1650-1600
1650
1625

Thay i

1660 1586

mnh

mnh

7.3. Hp cht vng thm (Aromatic)


Dao ng vng benzen
Hp cht
Vng thm

(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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Cc hp cht d vng 5 cnh v 6 cnh trong cc phn on du m v


hp cht hu c rt a dng v phong ph. Nhng quan trng nht l nhm
vng 5 cnh cha cc d nguyn t S, N, O (thiophen, furan, pirol) v d vng 6
cnh (piridin)
Tn s dao ng ca nhm d vng 5 cnh v 6 cnh ca cc lin kt
nm vng 3000 3200 cm-1, cn lin kt
vng

vng
-1

NH

vng 3400 cm-1, dao ng

1300 1600 cm-1, dao ng bin dng ca lin kt

800 cm v

NH

CH

CH

700

1620 cm-1.

Cc hp cht d vng su cnh ngng t nh quinolin v acridin


C cc dao ng ha tr
dng

CH

CH

vng 3100 3050 cm-1 v dao ng bin

1350 800 cm-1.

8. Cng thc thc nghim J.Brand


xc nh thnh phn ha hc ca cc phn on du m gm cc
hydrocacbon parafin Cp, naphten CN, aromatic CA. Tc gi J Brand a ra
cng thc thc nghim da vo kt qu phn tch ph hng ngoi ca cc
hydrocabon trong cc phn on du m.
Cc cng thc uc biu din nh sau:
1- CA =1,2 +9,8

(1600 cm-1)

2- CA = 3,0+6,6

(813 cm-1)

Cng thc ny p dng cho gii hn CA = 60 %


3- CA = 36,2 +6,6

(720 cm-1)

Cng thc ny p dng cho gii hn CA <10 %


4- Cp 29,9 +6,6

(720cm-1)

Cng thc ny p dng cho gii hn CA 10-25% ; Cp =40-70 %


5- Cn 240 lg lg [ 100

(970 cm-1) ] -25,5. Cng thc 5 thng t s dng

hn v vch ph 970 cm-1 yu v khng n nh.


Cng thc sau thng c s dng nhiu hn. Bng cch ly 100 tr
i tng ca hm lng CA v CP
6- CN = 100 -(Cp+CA)
Trong cc cng thc trn

l cng cc vch ph ti bc sng xc

nh v c biu din qua cng thc sau.

lg

Trong : dy ca cuvt (thng l 1 mm)


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59

: cng tia n sc ban u trc khi truyn qua lp vt


liu

:Cng tia n sc sau khi qua khi lp vt liu.


T cc cng thc trn c th tnh c hm lng cc hydrocacbon
tng ng.
8.1. Cc hng i khi gii ph hng ngoi
i vi mt cht cha bit c th xc nh cc nhm chc c trng
c trong hp cht cn phi nh hng xem trong cc gii ph c cng
hp th v v tr cc vch ph cng nh hnh dng ca chng gip cc nh
phn tch nh hng gii cc ph hng ngoi ca cht cha bit. i khi
ngi ta cng quan tm n cc thng tin v s vng mt ca cc di ph
c trng bn cnh nhng thng tin v s c mt ca cc di ph vi cng
mnh.
Mt s vch ph c trng ca cc nhm chc nh sau:
Ancol v amin c vch ph c trng cho lin kt OH v NH vng 3400
3100 cm-1
Anken v Ankyn c vch ph c trng ca lin kt CH vng 3000
3100 cm-1. S khng nh ca vng thm cn c th quan st bi cc nhm
vch 1600 1500 cm-1 v vch < 900 cm-1
Cc vch 1640 1680 cm-1 vi cng trung bnh c trng cho lin
kt C=C, cn vch 3000 2850 cm-1 l lin kt CH trong CH3 bo ha.
Nhm cacbonyl (C=O) c vch ph vi cng mnh 1690 1760
-1
cm , th hin s c mt ca andehit, keton, cacboxylic axit, este, amit,
anhydrit
Ngoi ra nu l hp cht andehit th cn c vch ph ca lin kt CH
vng 1840 2720 cm-1.
Nhm ester C-O c vch ph vng 1080 1300 cm-1. Hu nh tt c
cc cacboxylic axit, ester, ancol, andehit u cha vch ph ny nn cn thn
trong khi gii ph.
Nhm C C v C N u c vch ph vng 2100 2260 cm-1 nhng
cng yu v trung bnh.
Nhm metyl CH3 c vch ph vng 1380 cm-1. gii ph ny c th
thy hai vch ph b phn chia i vi nhm dimetyl ca isopropyl.
8.2. Mt s bi tp v d v gii ph hng ngo1.
V d 1: Ph hng ngoi ca 4-metylbenzenaldehit

60

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Cc vch ph trn c trng cho cac nhm chc sau ;


3080cm-1 nhm CH vng thm
2760cm-1 nhm CH ca andehit
1735cm-1 nhm andehit CO
1610cm-1 nhm cacbonyl lin hp vi vng thm
1414cm -1 nhm metyl (dao ng bin dng)
820cm-1 dao ng bin dng ca CH vng thm
V d 2: Ph hng ngoi ca 2-hydroxylbenzaldehit

Cc vch ph trn c trng cho cc nhm chc sau ;


3250cm-1 nhm OH
3120 nhm CH vng thm
2820
nhm CH andehit
1690
nhm C=O
1600-1500 vng thm
1200
hp th ca phenol C-O
1050 cm-1 hp th ca ancol bc 1
1100 hp th ca ancol bc 2
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61

1150 hp th ca ancol bc 4, 760-720 dao ng ca hydro trong vng


thm.
V d 3: ph hng ngoi ca diphenyl metan

Cc vch ph trn c trng cho cc nhm chc sau :


3060 cm-1 -nhm CH vng thm
2960 &2890 nhm CH bo ha khng i xng v i xng
1610&1510 - nhn thm
1470
1471
nhm CH2 bo ha
745 & 705 nhm H vng thm
V d 4: ph hng ngoi ca dietyl malonat

Cc vch ph trn c trng cho cc nhm chc sau :


2995 cm-1 - nhm CH no i xng v bt i xng
1765&1740 - vch p c trng cho hai nhm CO
1380 - nhm CH3dao ng bin dng
1280 - c trng do dao ng ha tr ca nhm C-O-C este
1045 Dao ng ha tr i xng ca C-O-C trong este.
V d 5: Ph hng ngoi ca squalan (C30H62)
62

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Cc vch ph c trng cho cc nhm chc sau :


2960 & 2980 cm-1 dao ng ha tr ca nhm CH bt i xng v i
xng.
1480 - nhm CH2
1395 dao ng bin dng ca nhm CH3
9. Thc hnh phn tch hp cht hydrocacbon parafin, naphten,
hydrocacbon thm trong phn on du m bng ph hng ngoi.
Mc ch ca bi thc hnh ny gip hc vin nm c cc thao tc,
vn hnh trn my o ph IR mt cch thnh tho v 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.
9.1. Cc cng vic chun b
9.1.1. My o ph hng ngoi vi cc cu hnh sau
-

B cp ngun sng,

B tch nh sng n sc,


B phn nhn tn hiu v khuch i tn hiu
B phn x l tn hiu
9.1.2. Cc loi dng c v ho cht cn thit cho th nghim
-

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

9.2. Cch tin hnh th nghim


9.2.1. Mu dng lng
Nu l cht lng tinh khit th dng hai tm KBr c dy khong 0.1 mm
v nh mt git cht lng vo gia hai tm KBr to thnh lp mng mng cht
lng p gia hai tm .
9.2.2. Tm KBr c chun b nh sau
Ly khong 300-500 mg KBr tinh khit cho vo ci nghin mn, sau
cho bt nghin vo khun p, san u v a vo my p thu lc.
Ni khun mu vi h thng ht chn khng, to chn khng n khong
1.3.10-4 kPa.
p sut chn khng ny trong khong 2 pht rt ht khng kh ra
khi h.
Tng p sut my p ln khong 15 tn v yn trong khong 1 pht
Sau nh chn khng t t n p sut thng.
Ly tm KBr ra khi khun mu cn thn sao cho khng b b v a
vo gi (ch trnh ng tay vo b mt tm p KBr). Nu thc hin cc
thao tc tt tm p KBr phi trong sut v ng u.
Dung dch mu c chun b nh sau
Ha tan cht nghin cu vo dung mi thch hp vi nng 1-5 % sau
cho vo gia haitm KBr th nht, sau cho dung mi vo gia hai tm
KBr th hai ging ht hai tm th nht v dy v vt liu ch to. Nh so
snh hai chm tia i qua dung dch v dung mi ngi ta c th loi vch hp
th ca dung m1.
Nng cht ghi ph IR ca mu lng trong khong t 10-2 n 1mol /l.
ghi ph cho nhng mu c tinh kim, axit, hoc dung dch nc th phi
dng cc vt liu khng tan trong nc nh fluorit, silic, germany,...
9.2.3. Mu dng rn
C nhiu cch o mu dng rn nhng n gin v thun tin nht l
p vin vi KBr.
Mu phn tch c nghin tht mn vi KBr vi t l khong 2-5 mg mu
trong 300-500 mg KBr sau p trn my p thnh nhng vin trn dt vi
chiu dy khong 0,1 mm nh m t phn trn. Vin dt thu c hu
nh trong sut v cc cht phn tch c phn tn ng u trong KBr.
Cn ch l KBr c tnh ht m rt mnh nn trong ph thng xut hin
vch ph hp th ca nuc 3450 cm-1. Ngoi ra dng KBr cn c th xy ra

64

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phn ng trao i cation hoc anion vi cc cht nghin cu l mui v c


hoc cc phc v c.
9.3. o ph hng ngoi ca mu trn my IR
9.3.1. Chun b thit b IR
-

Xem xt tnh trng ca my, cc ng in, kh


Bt my vo ch lm vic.

Ci t cc iu kin phn tch.


n nh my, n nh nhit .

Pha ch cht chun vi nng khc nhau


p cc tm KBr.
Pha ch mu phn tch trong cc dung mi thch hp (nu cn thit)
9.3.2. Trnh t phn tch
-

Nh mt git dung mi vo hai tm KBr chun b sn, p li thnh


mng mng dung mi (thao tc tht nhanh trnh ht m)

a tm KBr c dung mi vo gi ca my.


o ph hng ngoi ca dung mi

Ch n khi my qut ht cc bc sng khi kt thc php o.


Ly hai tm KBr ra khi gi .
Nh mt git mu pha sn trong dung mi chun b trc vo hai
tm KBr mi.
a hai tm KBr vo gi .
o ph hng ngoi ca mu vi cng mt iu kin nh vi dung
m1. Kt thc php o.
i vi cc cht chun cng lp li trnh t php o nh trn.

So snh kt qu ca ph v tm cc vch ph chun cho tng


nhm chc v cc lin kt theo cc bng chun v cc ph ca
nhng cht chun c o trong cng mt iu kin.
9.5. Tnh ton
Da vo cng mnh nht ca cc vch ph c trng c th dng
cng thc thc nghim Brand tnh ton hm lng cc hydrocacbon trong
phn on du m.
Cc cng thc nh sau
Tnh cho hydrocacbon thm
1. CA = 1,2 + 9,8

(1600 cm-1)

2. CA = 3,0 + 6,6

(813 cm-1)

Cng thc ny p dng cho gii hn CA = 60 %


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65

3. CA = 36,2 + 6,6

(720 cm-1)

Cng thc ny p dng cho gii hn CA <10 %.


Tnh cho hydrocacbon parafin
4. Cp = 29,9 + 6,6

(720cm-1)

Cng thc ny p dng cho gii hn CA10-25% ; Cp =40-70 %


Tnh cho hydrocacbon naphten.
5. CN = 240 lg lg [ 100

(970 cm-1) ] - 25,5

Cng thc 5 thng t s dng hn v vch ph 970 cm-1 yu v khng


n nh.
Cng thc sau thng c s dng nhiu hn bng cch ly 100 tr i
tng ca hm lng CA v CP
6. CN = 100 - (CP + CA)
Trong : CA - Hydrocacbon thm
Cn - Hydrocacbon naphten.
Cp- Hydrocacbon parafin.
Trong cc cng thc trn

l cng cc vch ph ti bc sng xc

nh v c biu din qua cng thc sau:


=

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

Trnh t tin hnh hot t


ng

Khng
t

Tiu
chun
hot ng

Kim tra tnh trng my


Ch dn an ton

Theo hng
dn qui nh

Cc cng vic chun b:


dng c, ha cht, cht
chun

Theo yu cu
k thut cho
tng bi

Chun b cc phiu theo


di v nh gi kt qu

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

my trong thi gian phn

, iu chnh

tch

kp thi

Lp li php phn tch khi


cn thit

Ghi nhn xt

Ch n nh v tr my

Ghi nhn xt

v li trng thi ban u


Kt thc bi thc hnh v
tnh ton kt qu

Np phiu bo
co, bn giao
my

Bng tng kt thc hnh phn tch


Nhm
hydrocacbon

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.

Cc bc sng sau nm trong min no ca bc x in t: 1 cm,


0,8 m, 10 m, 100 nm, 10 nm?

2.

Cc tn s sau nm trong min bc x no ca sng in t: 983 cm-1,


5,0 cm-1, 8,7.104 cm-1.

3.

Hy tnh nng lng ca photon c bc sng bng 0.05 nm.

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67

4.

Trong s cc lin kt C-C, C=C v C C , lin kt no c hng s lc ln


hn? Ti sao? Lin kt no c c khong cch nng lng dao ng gn
nht.

5.

Gii cc ph hng ngoi ca cc cht c cng thc ho hc di y v


vit cng thc cu to.

5.1. Gii ph hng ngoi ca cht c cng thc sau C5H10O

5.2. Gii ph hng ngai ca cht c cng thc C8H8O

5.3. Gii ph hng ngai ca hp cht c cng thc C7H8O.

5. 4.Gii ph hng ngai ca cht c cng thc C8H7N

68

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5.5. Gii ph hng ngai ca cht c cng thc C4H8O2

5.6.Gii ph hng ngai ca cht c cng thc C3H10NO

5.7. Gii ph hng ngoi ca hp cht c cng thc C6H6S

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69

5.8. Gii ph hng ngai cacht c cng thc C7H6O

70

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BI 2. QUANG PH HP THU NGUYN T (AAS)


M bi. HD K2
Gii thiu
Phng php o ph hp th nguyn t l mt k thut phn tch ho l
v ang c pht trin v pht trin rng ri trong nhiu ngnh khoa hc
k thut, trong sn xut cng nghip, nng nghip, y dc, a cht, ho hc.
Nht l cc nc pht trin,phng php phn tch theo ph hp th
nguyn t l mt phng php tiu chun phn tch lng vt kim loi
trong nhiu i tng mu khc nhau nh: t, nc, khng kh, thc phm,
v.v
nc ta k thut phn tch bng ph hp phu nguyn t AAS cng
c ch v pht trin trong nhng nm gn y c bit l trong cc
trng i hc vin nghin cu hu nh c trang b kh tt nhng thit b
ny phc v cho nghin cu ging dy v dch v phn tch.
Hin nay trong lnh vc bo v mi trng, phng php ny l mt trong
nhng cng c c lc xc nh hm lng cc kim loi nng v nhng
nguyn t c hi trong t nhin v trong cc sn phm khc nhau
Mc tiu thc hin
Hc xong bi ny hc sinh s c kh nng
M t bn cht ca ph AAS, my o AAS.
Xc nh hm lng kim loi trong du nhn bng ph hp th
nguyn t.
Tnh ton nh lng hm lng kim loi
Thc hin th nghim trong phng th nghim
Ni dung
1.
2.

C s ca phng php hp th nguyn t


ng dng ca ph hp th nguyn t xc nh hm lng kim
loi c trong du.
3. My o
4. iu kin ghi ph
5. Mt s vch AAS chun
1. C s ca phng php ph hp thu nguyn t
1.1. Nguyn tc v l thuyt ca ph AAS
Nhng vn c bn ca php o ph hp th nguyn t c th c
nhn mnh v tm gn trong ba chnh sau:
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71

Tt c cc nguyn t u c th hp th nh sng

Mi mt nguyn t hp th nh sng vi bc sng c trng.


Nguyn l
Nguyn t l phn t c bn nh nht cn gi c tnh cht ca
nguyn t ho hc. trng thi c bn nguyn t khng thu, cng khng pht
ra cc nng lung di dng bc x. Nhng khi nguyn t trng thi hi t
do nu ta chiu mt chm tia sng c nhng bc sng xc nh vo m hi
nguyn t th chng s b hp thu bi cc nguyn t t do v chuyn ln
trng thi kch thch c nng lng cao hn.Trng thi kch thch rt khng
bn nguyn t s mau chng quay tr li trng thi c bn v pht ra cc tia
bc x c bc sng ng vi tia chiu. Qa trnh gi l qu trnh hp thu
nng lung.
Ph sinh ra gi l ph hp th nguyn t AAS.
Nng lung E b hp thu bi nguyn t th hin qua biu thc sau:
E= h.c /

(2.1)

Trong h: hng s Plank


C ; Vn tc nh sng
: di sng ca vch ph hp th
Nu:

E <0 qu trnh pht x


E >0 qu trnh hp th

Trong phng php phn tch ph trc ht phi to ra c m hi


nguyn t t do. Cc nguyn t t do c to ra khi phun dung dch phn
tch cha cht kho st M trng thi aerosol nhit cao. Khi cht
kho st M b phn hu, chuyn thnh cc nguyn t t do.
iu ny c ngha l sau khi nguyn t ha, nu a mt chm tia bc
x in t c tn s bng tn s cng hng, cc nguyn t t do c th hp
th cc bc x cng hng ny v lm gim cng ca chm bc x in
t ca chm tia chiu.
Phn cng ca chm bc x in t b gim l do b hp th t l vi
s nguyn t t do trng thi c bn.
Phng php quang ph pht x nguyn t lin quan n cc nguyn t
trng thi kch thch trong khi phng php quang ph hp th nguyn t li
lin quan n cc nguyn t trng thi c bn v y chnh l nguyn nhn
lm cho phng php quang ph hp th c chnh xc v nhy cao hn
nhiu so vi phng php quang ph pht x

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i vi mt s nguyn t phng php hp th nguyn t c th xc


nh n 0,1-0,005ppm, trong khi nhy ca phng php pht x ch
khong 1ppm.
Trong phn tch bng phng php ph hp thu nguyn t AAS ty
thuc vo k thut nguyn t ha mu dng ngn la (F-AAS) hay khng
ngn la (ETA-AAS) nhy ca phng php s tng ln rt nhiu. K thut
khng ngn la tuy ra i sau nhng c p dng rt hiu qu trong
phn tch v nhy ca n cao hn.
Bng 2.1: nhy ca cc nguyn t theo php o AAS
S th

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

nhy( g/mL) nhy(ng/mL)

Ghi ch: AA: Ngn la( Khng kh + Acetylen)


NA: Ngn la( Kh N2O + Acetylen)
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73

Tt c cc nguyn t c th hp th nh sng ti mt bc sng ring


bit tng ng vi mt nng lng theo yu cu ca tng nguyn t c th.
Nhng nguyn t ca cc nguyn t khc nhau c nng lng yu cu
cho chng cng khc nhau.
Di y l mt vi trng thi nng lng c th c ca nguyn t Natri
khi b kch thch.

Hnh 2.1: Trng thi nng lng c th c ca nguyn t Natri


1.2. S nguyn t ha
Qa trnh chuyn t nguyn t lin kt sang nguyn t khng lin kt
c gi l qa trnh nguyn t ha.
V d:
Ta c tinh th NaCl
Na0 + Cl0

NaCl nng chy

NaCl hi

Na+, Cl-

nguyn t ha ngi ta dng nhit cao ca ngn la n kh.


C rt nhiu hn hp kh nhin liu c th cho nhit cao kh chy,
nhng trong phng php ph AAS hn hp kh chy c dng ph bin
nht l kh axetylen, nito dioxit N2O, hydro H2 vi khng kh cc t l khc
nhau.
Ty thuc vo mc ch phn tch v nguyn t cn xc nh m chn
hn hp kh chy t yu cu v nhit .
V d: Ngn la ca hn hp khng kh-Axetylen c nhit n 20000C;
Cn hn hp N2O + Axetylen cho nhit n 30000C
Nguyn t ha mu phn tch l mt cng vic ht sc quan trng cu php
o ph hp th nguyn t. Bi v ch c cc nguyn t t do trng thi hi l
yu t quyt nh cng vch ph hp th v qu trnh nguyn t ha mu

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thc hin tt hay khng tt u c nh hng trc tip n kt qu phn tch


mt nguyn t.
2.2.1. Nguyn t ha mu bng ngn la
Theo k thut ny ngi ta dng nng lng nhit ca ngn la n kh
ha hi v nguyn t ha mu phn tch. V th mi qu trnh xy ra trong
khi nguyn t ha mu l ph thuc vo cc c trng v tnh cht ca ngn
la n kh. Nhng ch yu l nhit ca ngn la. N l yu t quyt nh
hiu sut nguyn t ha mu phn tch,
Ngn la n kh mun dng vo mc ch ha hi v nguyn t ha mu
phn tch n cn phi tha mn mt s yu cu nht nh sau y:
Ngn la n kh phi bao qut v cp nhit u c mu phn
-

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.

Tiu tn t mu phn tch.


to ra ngn la, ngi ta c th t chy nhiu hn hp kh khc
nhau, bao gm mt kh oxy ho v mt kh chy, Mt s v d v nhit ca
ngn la ca mt s n kh c dng trong php o AAS(Ox: Cht oxy
ha; Ch: Cht chy; kk: Khng kh).
Bng 2.2: Quan h gia nhit v loi kh t
Loi kh

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

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75

N2O

Axetylen

2/1,8

3000

Bng 2.3: Thnh phn kh v nhit ngn la


Loi kh

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

Hnh 2.2: S khi ca mt my ph hp th nguyn t

Hnh 2.3: Cu to ca mt n catot rng(HCL)

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Hnh 2.4. Phn b nhit ca ngn la


Trong h thng nguyn t ho mu c hai b phn chnh l du t
(Burner head) v bung phun sng p lc aerosol ha (nebulizer)
to cc ht sol kh t dung dch mu ngi ta dng cc k thut khc
nhau nh k thut phun kh mao dn(pneumatic) v k thut siu m
(ultrasonic). Thng ch khong 10% dung dch mu c to thnh bi kh
vi kch thc t yu cu khong t 5-7 m, ti a l 20 m,
Trong k thut phun kh dung dch mu c nh mnh to thnh cc ht bi
nh li ti bi mt qu bi v cnh qut ri trn u vi hn hp kh t v a
ln bung t nguyn t ha.
Trong k thut ny tc dn mu nh hng nhiu n cng ca
vch ph v ph thuc vo nht ca dung dch mu.
Bng 2.4. nh hng ca tc dn mu n cng vch ph.
Tc dn
mu l/ph

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

Tuy vy thong thng nu tng tc dn n qu gii hn >6ml/ph th


cng vch ph s khng tng tuyn tnh na c th dn n hin tng
nhiu ha hc.
1.3.Mi lin h gia s hp th nh sng v mt nguyn t
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77

Khi c ngun sng vi cng bit trc cho cc nguyn t trng


thi nng lng c bn, mt phn ngun sng ny b hp th bi nhng
nguyn t. T l s hp th c xc nh bi mt cu cc nguyn t.

Hnh 2.5. Minh ha c bn v s hp th nguyn t


Khi ngun sng c cng bit trc l I0 i qua lp dung dch c nng
l N v c b dy , Ngun sng s b hp th v cng s b yu i
thnh I. khi cng thc lin h gia I v I0 l:
I = Io e.(K.N )
(2.2)
Trong k: h s hp th nguyn t ca vch ph c trng cho mi
nguyn t.
N:Nng ca nguyn t trong m hi nguyn t.
: chiu dy ca ca lp dung dch.
Nu gi D l cng ca vch ph AAS ta c:
D = log Io/I = 2.303 K.N.

(2.3)

Trong : K l h s hp th nguyn t c trng ring cho tng nguyn


t( c th tra cu trong cc bng)
D l gim cng ca chm tia khi qua mi trng hp th v ph
thuc vo nng ( N) ca nguyn t trong mi trng.
Khi o hp th ca mt mu khng bit v da vo th chun
chng ta c th xc nh c nng ca chng.
Trong php o ph hp th nguyn t, mi quan h gia cng ca
mt vch ph hp th ca mt nguyn t phn tch v nng ca n trong
mi trng hp th cng tun theo nh lut hp th quang Lambert-Beer.
Ngha l nu chm tia sng n sc cng I0 i qua mt mi trng cha
mt loi nguyn t t do nng N v c b dy l cm, th mi quan h gia
I0 v phn cng sng I i qua mi trng c tnh theo cng thc
trn.
V d Khi hp th c o trn mu c nng l 1, 2 v 3 ppm v
th biu din s tng quan gia hp th v nng l mt ng thng.

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th ny l th chun.

Hnh 2.6: th chun


Cng thc ny cho chng ta bit mi quan h gia cng ca mt
vch ph hp th v nng ca nguyn t trng thi hi trong mi trng
hp th. Nhng n cha cho bit mi quan h gia cng ca vch ph
v nng ca nguyn t trong mu phn tch.
Nh vy nu gi nng ca nguyn t trong mu phn tch l C th
chng ta cn phi tm mi quan h gia C v N v ri t s suy ra c
mi quan h gia C v D.
Tuy c phc tp, nhng t nhng kt qa thc nghim v trong mt
phm vi nht nh ca nng C mi quan h gia C v N c xc nh
theo cng thc:
N = k. Cb
(2.4)
Trong k l hng s thc nghim,
Cn b l mt hng s, c gi l hng s bn cht, n ph thuc vo
nng C, tnh cht hp th ph ca mi nguyn t v tng vch ph ca
nguyn t .
Hng s b c gi tr 0< b

1. khi nng C ca nguyn t phn tch l

nh, th b lun lun bng 1.


Khi C tng th b nh dn xa gi tr 1, tin v 0,
T cng thc trn cho thy, cng D ca mt vch ph hp th l
ph thuc vo 3 thng s K, , C. Nh trong mt php o th K lun lun l
hng s, L l chiu di ca ngn la trong php o F-AAS hay chiu di ca
cuvet cng khng i.
Do D ch cn ph thuc vo nng C ca nguyn t cn xc nh
trong mu phn tch. Do vy, mt cc tng qut chng ta c:
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79

D = a. Cb

(2.5)

y chnh l phng trnh c s ca phng php phn tch nh lng


da theo vic o ph hp th ca mt nguyn t xc nh nng ( hm
lng) ca n v mi quan h ny c minh ha trong hnh sau.

Hnh 2.7:Mi quan h ca D vi C


a: Dng bnh thng; b: Dng c bit
Nu b bng 1 th mi quan h gia D v C l tuyn tnh theo phng
trnh c dng y = a.10. khi ng biu din mi quan h ny l mt ng
thng i qua gc ta .
Nh thc nghim cho thy rng trng hp ny l ch c trong mt vng
nng nh. y l trng hp l tng
Ph bin nht l trng hp trong hnh 2.7a. l trng hp chung
cho cho hu ht cc vch ph hp th ca cc nguyn t. N gm mt on
tuyn tnh (b=1) v mt on khng tuyn tnh (b<1).
Ni chung trong trng hp ny thng lun lun c mt on thng ca
ng biu din mi quan h gia D v C vng nng nh cu nguyn t
phn tch, l on OA. Vi cc vch ph nhy th on OA ny cng ngn.

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Tc l vng nng ng vi on tuyn tnh l hp. Vng nng ng vi


on OA c gi l vng tuyn tnh cu php o AAS.
Trng hp th ba cn li l mt dng phc tp. Trong trng hp ny
mi quan h gia D v C l khng tuyn tnh bc nht trong bt k vng nng
no.
Trong phn tch, nu gp phi trng hp ny cn phi ht sc ch khi
lp ng chun. Ngha l dng nhiu mu u c nng gn nhau
dng ng chun v ch c nh th chng ta mi xc nh c chnh xc v
tr ca ng chun. Vch ph hp th Na-589,0 nm l i din trong trng
hp ny.
1.4.Cc loi nng trong php o AAS
Trong php o ph hp th nguyn t, ngi ta thng biu din nng
ca nguyn t phn tch theo my cch sau y:
1.4.1. Nng phn trm(%)
y l khi nim thng thng, n c biu th bng s gam ca cht
phn tch c trong 100g mu em phn tch. Nng ny c tnh theo cng
thc:
C%

mx
m

x 100

(2.6)

Trong mx l s gam cht phn tch c trong mu ly phn tch, cn


m l s gam mu phn tch. V d, nu vit dung dch NaOH 0,1% ngha l
trong 100 gam dung dch c 0,1 gam NaOH.
1.4.2. Nng micrgam/lt.(ppb), hoc mg/ml( ppm)
Loi nng ny c dng ph bin trong phn tch lng vt v
thng c biu th theo hai cch:
-

S micrgam ca cht phn tch c trong mt lt dung dch mu


( g/l)
Hay (ppb) hoc micrgam cht phn tch c trong mt mililit dung
dch mu ( g/ml) hay (ppm).
V d, nu vit CPb = 1,2 ( g/l) th c ngha l c trong 1 lt dung dch
mu s c 1,2 micrgam ca Pb.

S micrgam ca cht phn tch c trong mt gam mu ( g/g), hay


s micrgam ca cht phn tch c trong mt kg mu ( g/kg).(ppb)
V d nu CPb=2, 5( g/g) th c ngha l c trong 1 gam mu s c
2,5 micrgam ca Pb (ppm)

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81

Cng hon ton tng t, ngi ta cn dng cc n v c s ca g.


l nanogam (ng), picrgam (pg). Do cng c cc khi nim nng
ng/l, ng/ml, ng/g, pg/l, pg/ml, pg/g. Cc n v

g, ng v pg u km nhau

1000 ln v mi tng quan ca chng c ch ra trong bng sau.


Bng 2.5: Mi quan h gia cc loi n v nng (vi l=1)
n v gc
1000 ppm
1 ppm
1 ppb
1 ppp
1 ppf
1 ppa
n v gc
1 mg
1 g
1 ng
1 pg
1 fg
1 ag

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

1.5.Mt s nh hng trong php o AAS


Cc yu t nh hng n kt qu phn tch trong php o ph hp ph
nguyn t l rt a dng v phc tp. Cc yu t c th c chia thnh 6
nhm nh sau:
Nhm 1: L cc thng s cu h my o ph. Cc thng s ny cn
-

82

c kho st v chn cho tng trng hp c th.


Nhm 2: L cc iu kin nguyn t ho mu. Cc yu t ny th
hin rt khc nhau ty thuc vo k thut c chn thc hin
qu trnh nguyn t ho mu
Nhm 3: L k thut v phng php c chn x l mu.
Trong cng vic ny nu khng lm cn thn s c th lm tht
thot hoc lm nhim bn thm nguyn t phn tch vo mu. Do
, dn n sai s trong kt qu phn tch mu. V th vi mi loi
mu ta phi nghin cu v chn ra mt quy trnh x l ph hp nht.
Nhm 4: Cc nh hng v ph.
Nhm 5: Cc nh hng ca yu t vt l.
Nhm 6: Cc yu t ho hc.
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1.5.1. nhy ca php o


nhy l mt i lng ch ra kh nng ca mt phng php phn
tch theo mt k thut o no c p dng cho phng php phn tch
. Phng php phn tch c nhy cao tc l nng gii hn di c
th phn tch c l nh.
a. nhy tuyt i
Trong php o AAS, nhy tuyt i l lng gam(khi lng) nh
nht ca nguyn t cn phn tch phi c trong mi trng hp th cn thu
c cng ca vch ph hp th chn chim 1% ton bng hp th,
hay bng 3 ln tn hiu nn
b. nhy tng i
nhy tng i cn c gi l nhy nng . nhy ny c
nh ngha l nng nh nht ca nguyn t phn tch c trong mu cn
c th pht hin c tn hiu hp th ca n theo mt vch ph nht nh
chn v tn hiu ny phi bng 1% ca bng hp ton phn hoc bng 3 ln
dao ng ca ga tr nn. Loi nhy ny c dng ph bin trong php o
AAS hn khi nim v nhy tuyt i
Bng 2.6: nhy ca mt s nguyn t.
Nguyn t
Vch ph(nm)
309,30
396,20
Al
308,20
394,40
357,90
Cr
359,40
425,40
324,80
Cu
327,40
216,50
248,30
248,80
Fe
302,10
252,30

nhy theo ETA-AAS


( g/l)
0,04
0,07
0,10
1,20
0,05
0,10
0,20
0,008
0,015
0,050
0,005
0,007
0,025
0,030

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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

Bng 2.7: nhy, gii hn pht hin v khong xc nh


ca cc nguyn t theo AAS
Cc c trng ca AAS

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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1.5.2.Gii hn pht hin


Bn cnh khi nim v nhy, ngi ta cn s dng v gii hn pht
hin i vi mt nguyn t khi dng mt vch ph chng minh n. Gii hn
pht hin cng c hai khi nim tng t nh nhy. l gii hn pht
hin tuyt i v tng i.
a. Gii hn pht hin tng i ca mt nguyn t theo mt vch ph nht
nh c th xem l nng nh nht ca nguyn t trong mu phn tch
cn c th pht hin c tn hiu hp th ca n theo vch ph
trong mt iu kin nht nh chn.
b. Gii hn pht hin tuyt i ca mt nguyn t l khi lng ti thiu ca
nguyn t cn c trong mi trng hp th cn c th pht hin c
tn hiu hp th ca n cng trong mt iu kin nht nh chn.
Bng 3.8: Gii hn pht hin ca m s nguyn t.
F-AAS

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

Nh vy, vi mi mt nguyn t v mi vch ph cng c giihn pht


hin khc nhau. Trong mt nguyn t, th vch ph no c kh nng hp th
mnh s c gii hn pht hin lng nh hay nng nh.
1.5.3. Khong xc nh
Trong php o ph hp th nguyn t, vic nh lng mt nguyn t l
da vo phng trnh c bn sau:
D = K.Cb

(3.7)

Nh chng ta nghin cu trn(mc I.1), trong mi quan h ny, D


ch ph thuc tuyn tnh vo C khi b=1. Ngha l khi nng C rt nh.
D = K. C

(3.8)

Ngha l ch trong mt khong nng C nht nh v nh, th mi quan


h gia D v C l tuyn tnh, ng ng vi phng trnh(5.8). Khong nng
C ca nguyn t phn tch ng ng vi phng trnh(5.8) ny c gi l
khong xc nh(hay l khang tuyn tnh) ca nguyn t theo phng
php nu. Trong khong nng ny th quan h gia D v C l c dng
ca phng trnh tan hc y = a10. Thc nghim cho thy rng khang xc
nh i vi mi nguyn t l khc nhau, mi vch ph khc nhau l rt khc
nhau.
Bng sau l mt v d v khong xc nh ca mt s nguyn t theo cc
vch ph ca n trong php o AAS.

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Bng 2.9.Vng tuyn tnh ca php o


Nguyn t
Vch(nm)

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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87

S nhiu nn c th gy ra s gim v cng c th lm tng tn hiu


phn tch. S nhiu nn xy ra khi cc tnh cht vt l( nht, c tnh chy,
sc cng b mt) ca mu phn tch v cht chun khc nhau. iu ny c
th xy ra khi dung dch mu c cha mui ha tan hoc axit vi nng cao,
dung mi c dng cho mu phn tch v cht chun khng ging nhau.
nhit ban u ca cc dung dch khng ging nhau.
V d khi xc nh Pb trong mu sinh hc th s hp th nn l khng
ng k. Nhng khi xc nh Pb trong nc bin( nn 2.9% NaCl) th nh
hng ny l rt ln. Do trong mi trng hp c th phi xem xt tm
bin php loi tr.
loi tr ph nn, ngy nay ngi ta lp thm vo my quang ph hp
th nguyn t h thng b chnh nn.

Hnh 2.8: Minh ha s nhiu nn do nh hng ca nht.


1.7. S chen ln cu vch ph
Yu t ny thng thy khi cc nguyn t th ba trong mu phn tch
c nng cao v thng l nguyn t c s cu mu.
V th trong mi mc ch phn tch c th cn phi nghin cu v chn
nhng vch phn tch ph hp loi tr s chen ln cu cc vch ph cu
nguyn t khc. Mc d ph hp thu nguyn t l rt n gin nhng cng c
nhng trng hp b trng lp vch ph, mt vi trng hp c th c cho
trong bng sau:
Bng 2.10: S chen ln v s trng vch ph ca cc nguyn t

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

Trong mi trng hp th, c bit l trong ngn la n kh, nhiu khi


cn c cha c cc ht rn rt nh li ti ca vt cht mu cha b ho hi v
nguyn t ha, hay cc ht mui cacbon cu nhin liu cha c t chy
hon ton.
Cc ht loi ny thng c th c lp v ngn la. Cc ht ny hoc
hp th hoc chn ng i cu chm sng t n chiu vo mi trng hp
th. Do cng gy ra nhng sai s cho kt qu o cng vch ph thc.
Yu t ny th hin rt r khi chn khng ng chiu cao cu n nguyn
t ho mu v khi hn hp kh chy khng c t chy tt, hay do thnh
phn cu hn hp kh chy khng c chn ph hp(thng l qu d
Acetylen).
2. Phng php nh lung bng ph AAS
xc nh nng (hm lng ca mt nguyn t) trong mu phn tch
theo php o ph hp th nguyn t ngi ta thng thc hin theo cc
phng php sau y,
1. Phng php ng chun.
2. Phng php thm cht chun.
2.1. Phng php th chun
Trc ht ngi ta phi chun b mt dy mu u, dy mu chun(
thng thng l 5 mu u) v cc mu phn tch trong cng mt iu kin.
V d cc mu u c nng ca nguyn tc X cn xc nh l C1, C2, C3,
C4, C5, v mu phn tch l C1x, C2x,... Sau chn cc iu kin ph hp v
o cng cu mt vch ph hp th cu nguyn t phn tch trong tt c
cc mu u v mu phn tch c chun b trn.

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89

Hnh 2.9: phng php th chun


Phng php ny n gin, d thc hin v rt thch hp vi mc ch
phn tch hng lot mu cu cng mt nguyn t, nh trong kim tra cht
lng thnh phm, kim tra nguyn liu sn xut.
V mi khi dng mt ng chun chng ta c th xc nh c nng
cu mt nguyn t trong hng trm mu phn tch.
2.2. Phng php thm cht chun
Trong thc t phn tch, c bit l xc nh lng vt kim loi, khi gp
phi cc i tng phn tch c thnh phn phc tp v khng th chun b
c mt dy mu u(mu chun) ph hp v thnh phn vi mu phn
tch, th tt nht l dng phng php thm cht chun. Ch nh th mi loi
tr c yu t nh hng v thnh phn cu mu(Matrix effect).
Nguyn tc cu phng php ny l ngi ta dng ngay mu phn tch
lm nn chun b mt dy mu u, bng cch ly mt lng mu phn
tch nht nh v cho thm vo nhng lng nht nh cu nguyn t cn
xc nh theo tng bc nng (theo cp s cng).
V d lng thm vo l C1 C2, C3, C4,...nh th chng ta s c mt
dy mu chun l:
C0 = C x
C1 =(Cx + C1)
C2 =(Cx + C2)
C3 =(Cx + C3)
C4 =(Cx + C4)
Trong Cx l nng cu nguyn t cn xc nh trong mu phn tch.

90

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Tip cng chn cc iu kin th nghim ph hp v mt vch ph


cu nguyn t phn tch, tin hnh ghi cng hp th cu vch ph
theo tt c dy mu u, chng ta thu c cc gi tr tng ng l D0, D1,
D2, D3 v D4. By gi t cc gi tr cng ny v ng vi cc nng
thm vo cu nguyn t phn tch, dng mt ng chun theo h ta D C.
chnh l ng chun cu phng php thm cht chun. ng
chun ny ct trc tung D ti im c to (D0,0). Sau xc nh nng
Cx cha bit chng ta lm nh sau:
Ko di ng chun v pha tri, n ct trc honh ti im C0, on OC0 chnh bng nng nng Cx cn tm.
Hoc cng c th xc nh Cx bng cch t gc to k mt ng
song song vi ng chun v t im D0 k ng song song vi trc
honh, hai ng ny ct nhau ti im M, t im M h ng vung gc
vi trc honh, ng ny ct trc honh ti im C0. Chnh on O C0 l
bng gi tr Cx phi tm (hnh 2.10).

Hnh 2.10: phng php thm cht chun


Phng php ny c u im l qu trnh chun b mu d dng, khng
cn nhiu ha cht tinh khit cao chun b dy mu u nhn to. Mt
khc li loi tr c hon ton nh hng v thnh phn cu mu cng nh
cu trc vt l cu cc cht to thnh mu. Nhng phi ch rng, nng
thm vo cu nguyn t phn tch phi theo tng bc v khong cch cu cc
bc phi xp x bng nng Cx phi tm. C nh th th phn ni suy
tuyn tnh mi c ngha chnh xc.
im thun li cu phng php thm cht chun l hn ch c nhiu
sai s phn tch gy ra bi nhng yu t gy nhiu do s khc nhau v thnh
phn vt l v ha hc cu mu v cht chun.
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91

Phng php ny c s dng rt nhiu trong phn tch lng vt v


lng cc nh cc nguyn t kim loi trong cc loi mu khc nhau, c bit
l cc loi mu c thnh phn vt l v ha hc phc tp, cc mu qung a
kim loi.

Hnh 2.11: V d minh ha phng php thm cht chun


3. ng dng ca phng php quang ph hp th nguyn t AAS
xc nh hm lung kim loi v cc nguyn t
3.1. i tng ca phng php
i tng chnh ca phng php phn tch theo ph hp th nguyn t
l phn tch lng nh(lng vt) cc kim loi trong nhiu i tng mu
khc nhau ca cc cht v c v hu c v c bit l hm lung cc kim loi
c trong du m v cc phn on du m.
Vi cc trang b k thut hin nay, bng phng php phn tch ny
ngi ta c th nh lng c hu ht cc kim loi(khong 65 nguyn t)
v mt s kim n gii hn nng c ppm bng k thut F-AAS, v n
nng ppb bng k thut ETA-AAS vi sai s phn tch dao ng trong
khong 3-10%.
Trong khong hai n ba thp k nay, phng php phn tch ph hp
th nguyn t c s dng kh ph bin xc nh cc kim loi trong
cc mu qung, t, , nc khong, du m v cc phn on du m, cc
mu y hc, sinh hc, cc sn phm nng nghip, rau qu, thc phm, nc
ung,cc nguyn t vi lng trong phn bn, thc n gia sc,

92

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nhiu nc trn th gii, nht l cc nc pht trin, phng php


ph hp th nguyn t tr thnh mt phng php tiu chun nh
lng nhiu kim loi.
Bn cnh cc kim loi, mt vi kim nh Si, P, S, Se, Te, cng c xc
nh bng phng php phn tch AAS.
Cn cc anion, cc kim, cc cht hu c, khng c ph hp th nguyn
t nguyn t phi xc nh theo cch gin tip thng qua mt kim loi c ph
hp th nguyn t nh mt phn ng ha hc trung gian c tnh cht nh
lng,nh phn ng to kt ta khng tan, to phc, y kim loi, hay ha
tan kim loi,... gia kim loi o ph v cht cn phn tch. y l mt i
tng mi, phong ph ang c nghin cu v pht trin.
Phng php o ph hp th nguyn t ang c pht trin rt nhanh,
khng nhng phn tch cc kim loi, m phng hng ang pht trin
nht hin nay l nghin cu xc nh cc cht hu c, nh cc hp cht hu
c halogen, lu hunh, photpho. N cng v ang c s dng nh l
mt cng c phn tch cho nhiu ngnh khoa hc v kinh t.
3.2. Nhng u im v nhc im ca php o AAS.
Cng nh cc phng php phn tch khc, phng php phn tch ph
hp th nguyn t cng c nhng u im v nhc im nht nh. Cc u
im v nhc im l:
Php o ph hp th nguyn t c nhy v chn lc tng i
cao. Gn 60 nguyn t ha hc c th c xc nh bng phng php ny
vi nhy t 1.10-4 n 1.10-5. c bit, nu s dng k thut nguyn t
ha khng ngn la th c th t n nhy 10-7%. Chnh v c nhy
cao, nn phng php phn tch ny c s dng rt rng ri trong nhiu
lnh vc xc nh lng vt cc kim loi. c bit l trong phn tch cc
nguyn t vi lng trong cc i tng mu y hc, sinh hc, nng nghip,
kim tra cc ha cht c tinh khit cao.
Do c nhy cao nn trong nhiu trng hp khng phi lm giu mu
nguyn t cn xc nh trc khi phn tch, do tn t nguyn liu mu, tn
t thi gian khng cn phi dng nhiu ha cht tinh khit cao khi lm giu
mu. Mt khc cng trnh c s nhim bn mu khi x l qua cc giai
on phc tp.
u im th ba cu phng php ny l cc ng tc thc hin nh
nhng. Cc kt qu phn tch li c th c lu li trn my tnh. ng thi

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93

c th xc nh ng thi ho lin tip nhiu nguyn t trong mt mu. Cc


kt qu phn tch rt n nh, sai s nh.
Trong nhiu trng hp sai s khng qu 15% vi vng nng c 12ppm.
Bn cnh nhng u im, php o ph hp th nguyn t cng c mt
s hn ch v nhc im nht nh.
Mt khc cng chnh do php o c nhy cao, cho nn s nhim bn
rt c ngha i vi kt qu phn tch hm lng vt. V th mi trng
khng kh phng th nghim phi khng c bi. Cc dng c, ha cht dng
trong php o phi c tinh khit cao.
Nhc im chnh ca phng php phn tch ny l ch cho ta bit
thnh phn nguyn t ca cht trong mu phn tch, m khng ch ra trng
thi lin kt ca nguyn t trong mu. V th n ch l phng php phn
tch thnh phn ha hc ca nguyn t m thi.
4. My o AAS
Cu trc v tnh nng k thut ca cc thit b phn tch d trn ph
nguyn t ch yu ty thuc vo loi k thut c p dng s nguyn t ha
mu phn tch. Mi loi k thut to ra mt l phn ng ring bit, gi l l
nguyn t ha.
Cn c c im ca tng loi l nguyn t ha ngi ta thit k ra loi
thit b o hp th A(phng php AAS)
Hin nay s dng 4 loi l nguyn t ha sau y:
Ngn la n kh: Phng php F-AAS v phng php F-AES(
Flame Atomic Emission Spectroscopy).
L Graphit: Phng php GF-AAS(Graphite Furnace)
L ghp cp cm ng: Phng php ICP-AES
H quang v tia in: Phng php AES chp nh.
Trong s cc l trn th hai loi l ngn la v l Grafit l ph bin nht.
4.1. Cc cu kin chnh ca thit b o ph hp th nguyn t AAS
Ni chung, my hp th nguyn t bao gm 5 cu kin chnh:
Ngun bc x kch thch
L nguyn t ha(Ngn la, l Graphit)
-

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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C hai kiu c bn cu my hp th nguyn t: loi mt chm tia(single


beam) v loi hai chm tia(doublebeam).
4.1.1. My quang ph hp th mt chm(single beam)

Hnh 2.12: S hot ng ca my hp th nguyn t loi mt chm tia


Ngun sng(t n Catot rng hoc n EDL) pht bc x mt ph c trng
cho tng nguyn t truyn xuyn qua bung mu i vo my n sc.
4.1.2. My quang ph hp th hai chm(double beam)

Hnh 2.13: S hot ng ca my hp th nguyn t loi hai chm tia


Ngun nh sng t n c chia thnh hai chm, chm mu c hi t
chuyn qua bung mu v chm i chng c hi t v c chuyn trc
tip vng qua bung mu. Trong h my hai chm, tn hiu ghi li tiu biu
cho t l ca chm mu v chm i chng. Do , s thay i(tng gim)
cng ngun khng gy ra s thay i(tng gim) thit b ghi tn hiu, v
v vy lm tng tnh n nh.
Di y l mt vi lai my hp th nguyn t ca cc hng sn xut
thit b phn tch tiu biu trn th gii:

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95

Hnh 2.14: My hp th nguyn t hiu Shimatzu AA 6300

Hnh 2.15: My hp th nguyn t kiu ngn la GBC PAL 4000(c)

Hnh 2.16: My hp th nguyn t kiu l Graphit GBC PAL 4000(c)


4.2. Cu to ca cc b phn trong my AAS
Mun thc hin c php o ph hp th nguyn t ngi ta cn phi
c mt ngun pht tia bc x n sc(tia pht x cng hng) cu nguyn t
cn phn tch chiu qua mi trng hp th.
Ngun pht tia bc x n sc trong php o ph hp th nguyn t
thng l cc n catt rng(HCL),cc n phng in cc(EDL), v cc n
ph lin tc c bin iu( c n sc ho).

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Nhng d l loi no, ngun pht tia bc x n sc trong php o ph


AAS cng phi tha mn nhng iu kin sau y.
Ngun pht tia bc x n sc phi to ra c cc tia pht x
nhy(cc vch pht x nhy, c trng) cu nguyn t cn phn
tch. Chm tia pht x phi c cng n nh, phi lp li
c trong nhiu ln o khc nhau trong cng iu kin, phi iu
-

chnh c vi cng mong mun cho mi php o.


Ngun pht tia bc x phi cung cp c mt chm tia pht x

thun khit ch bao gm mt s vch nhy c trng ca nguyn t


phn tch.
Chm tia pht x n sc do ngun cung cp phi c cng
cao. Nhng li phi bn vng theo thi gian, v phi khng b cc
yu t vt l khc nhiu lon

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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97

Hnh 2.17: n Catot rng (HCL)


n pht tia bc x n sc c dng sm nht v ph bin nht trong
php o AAS l n Catot rng (HCL).
n ny ch pht ra nhng tia bc x nhy ca nguyn t kim loi lm catot
rng. Cc vch pht x nhy cu mt nguyn t thng l cc vch cng
hng.
a. Thn v v
Thn n gm c v n, ca s v b cc in cc anot v catot. B
bng nha PVC. Thn v v n bng thy tinh hay thch anh.
Ca s ca n c th l pyrex hay thch anh trong sut trong vng UV hay
VIS l ty thuc vo loi n ca tng nguyn t pht ra chm tia pht x nm
trong vng ph no. Ngha l vch pht x cng hng o ph hp th
vng no th nguyn liu lm ca s S phi trong sut vng .
b. in cc
in cc ca n l Catot v Anot.
Anot c ch to bng kim loi tr v bn nhit nh W hay Pt. Catot
c ch to c dng hnh xylanh hay hnh ng rng c ng knh t 3-5
mm, di 5-6 mm v chnh bng kim loi cn phn tch vi tinh khit cao(t
nht 99.9%).
Dy dn ca catot cng l kim loi W hay Pt. C hai in cc c gn
cht trn b ca thn n v cc catot phi nm ng trc xuyn tm ca
n. Anot t bn cnh catot hay l mt vng bao quanh catot. Hai u ca
hai in cc c ni ra hai cc gn cht trn n, cm vo ngun in
nui cho n lm vic.
Ngun nui l ngun mt chiu c th 220-2405.
c. Kh trong n
Trong n phi ht ht khng kh v np thay vo l mt kh tr vi p
sut t(1-5 torr) 5-15mmHg.
98

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Kh tr l Argon, Hli hay Nit nhng phi c sch cao hn


99.99%. Kh np vo n phi khng pht ra ph lm nh hng n chm tia
pht x ca n v khi lm vic trong mt iu kin nht nh th t s gia
cc nguyn t b ion ha v cc nguyn t trung ha phi l khng i.
d. Ngun nui n
n c t nng pht chm tia pht x cng hng nh mt
ngun in mt chiu n nh. Th lm vic ca n HCL thng l t 250220 V ty thuc vo tng loi n ca tng hng ch to v ty thuc vo
tng nguyn t kim loi lm catot rng.
Cng lm vic ca cc n catot rng thng l 3-50mA v cng ty
thuc vo mi loi n HCL ca mi nguyn t do mi hng ch to ra n.
Th v cng dng in lm vic ca n HCL c lin quan cht ch vi
cng tch kim loi ra khi b mt catot rng to ra hi kim loi sinh ra
chm tia pht x ca n HCL.
Dng in qua n HCL ca mi nguyn t l rt khc nhau. Mi n
HCL u c dng in gii hn cc i m n c th chu ng c v gi
tr ny c ghi trn v n.
Theo l thuyt v thc nghim ca thc t phn tch theo k thut o ph
hp th nguyn t, ch nn dng cng dng trong vng 60-85% dng gii
hn cc i ghi trn n HCL l tt nht.
Cc n catot rng c cu to nh m t trn l nhng n HCL
n mt nguyn t, ngha l mi n HCL ch phc v cho phn tch mt
nguyn t..
Ngy nay ngoi cc n HCL n, ngi ta cng ch to c mt
s n kp i, kp ba hay kp su nguyn t.
V d cc n kp i l (Ca+Mg), (Cu+Mn), (Cu+Cr), (Co+Ni), (K+Na),
(Cu+Pb); Cc n kp ba nh (Cu+Pb+Zn) v n kp su l
(Cu+Mn+Cr+Fe+Co+Ni).
ch to cc loi n kp ny, catot ca n HCL phi l hp kim ca
cc nguyn t . Hp kim ny phi c thnh phn ph hp, sao cho
cng pht x ca cc nguyn t ny l gn tng ng nhau
Xt v nhy, ni chung cc n kp thng c nhy km hn cc n
n tng ng,
4.2.2. n phng in khng in cc (EDL)
Ngun pht tia bc x th hai c dng trong php o ph hp th
nguyn t l n phng in khng in cc. Loi n ny cng nh n HCL
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u c nhim v cung cp chm tia pht x c trng ca nguyn t phn


tch, c bit l cc kim, th n EDL cho nhy cao hn, n nh hn n
HCL
Bng 2.11. So snh nhy v gii hn pht hin ca n HCL v EDL
Nguyn t

nhy( g/ml)

Gii hn pht hin( 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

V cu to, n EDL thc cht cng l mt ng phng in trong mi


trng kh tr c cha nguyn t cn phn tch vi mt nng nht nh ph
hp to ra chm tia pht x ch bao gm mt s vch ph nhy c trng
ca nguyn t phn tch. n EDL cng bao gm cc b phn nh n catt
rng.

Hnh 2.18: n phng in khng in cc


a. Thn n
L mt ng thch anh chu nhit, di 18-15cm, ng knh 6-5 cm. Mt
u ca n EDL cng c ca s S. Ca s cho chm sng i qua cng phi
trong sut vi chm sng . Ngoi ng thch anh l cun cm bng ng.
Cun cm c cng sut t 800-400W ty loi n ca tng nguyn t, v
c ni vi ngun nng lng cao tn HF ph hp nui cho n EDL lm
vic.Ngoi cng l v chu nhit.
b. Cht trong n

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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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Cc lai n ny c u im hn en HCL v nhy, v vng tuyn


tnh, v gii hn pht hin. Nhng cc lai n ny kh ch to v t tin
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.
4.2.3. n ph lin tc c bin iu
l cc loi n pht ph lin tc trong vng t ngoi v vng kh
kin(UV-VIS).
n ny tuy pht ra ph lin tc, nhng nh h thng bin iu v h lc
giao thoa, nn chm sng pht x b bin iu v lng t ha thnh
chm sng khng lin tc coi nh l mt tia n sc.
Ngun pht ph lin tc c u im l d ch to, r tin v c bn tng
i cao.
Do n rt u vit i vi cc my ph hp th nhiu knh v xc nh
ng thi hay lin tc nhiu nguyn t trong cng mt mu phn tch m
khng phi thay n HCL cho vic o ph ca mi nguyn t.
4.3. L nguyn t ho
Trong l nguyn t ha xy ra qu trnh nguyn t ha ton phn hay
mt phn ng k ca nguyn t cn xc nh ca mu phn tch.
Tng t nh cc l phn ng, l nguyn t ha c th phn chia thnh hai
loi: L lin tc v l gin on
4.3.1. L lin tc
Mu phn tch phi c chuyn thnh dng tan trong dung dch(dung
mi s dng thng l nc v i khi l dung mi hu c) ri dng mt b
phun p lc(nebulizer) to thnh dng sol kh v lin tc cp vo l nguyn
t ha.
y l loi l nguyn t ha c dng rt ph bin trong cc phng
php F-AAS, F-AES v c ICP-AES.
4.3.2. L grafit( HGA)
Loi l ny thng dung xc dnh cc nguyn t trong mu dng vt
v yu cu mt lng mu rt nh c vi microlit.
Vi l grafit gii hn pht in c th nh hn c 1000 ln so vi loi l ngn
la.
Thng thng khi dung l grafit thng c b phn bm mu t ng
Trong loi l gin on l;oi grafit, ch ly mt th tch c nh (khong vi
chc L) ca dung dch mu phn tch ri a thng vo l nguyn t ha.

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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.

Hnh 2.19: L grafit


4.4. My n sc (Monochromator)
Bc x sau khi ra khi l nguyn t ha c hng vo mt thit b
quang hc gi l my n sc phn gii thnh tng tia n sc ring bit.
Hu ht cc thit b o ph hp th v ph pht x nguyn t hin nay u
dng loi my n sc cch t. Bng cch xoay cch t ta la chn khe ra
ca my n sc mt tia n sc c trng ca nguyn t ha hc cn xc
nh. Thng thng l tia cng hng v c lc dao ng t ln nht.
Cch t l b phn quan trng ca my AAS. N c ch to t nhng
vt liu c bit v c cc rnh c khang cch nht nh
Trong cc cch t hin i ngi ta la chn mt gc nghing thch hp
tp trung phn ln nng lng ca chm tia ti vo mt bc no . a s
cc cch t lm vic bc nhiu x m=1 c hiu qu tp trung nng lng
cao v khi gc nhiu x ng bng gc nghing ca cch t
4.4.1. Nhng c trng c bn ca my n sc cch t
a. Nng sut phn gii
c trng quan trng nht l nng sut phn gii ca my v c biu
din qua cng thc sau:
R = Dk.e /f
(2.10)
hay c th vit gn ng nh sau:
Rm= m.n.e
Trong : e - l khu tc dng ca cch t(mm)
f - di ca tiu c
Dk tn x di(nm/nmm)
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(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.

Hnh 2.20: Nhn quang in kiu ng


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H s khuch i ca lai detector ny thng n 106, i khi c lai ln


n 107.
5. Cc iu kin ghi ph AAS
5.1. Xy dng phng php phn tch
Mun xc nh mt nguyn t theo mt k thut no , chng ta cn
phi c mt quy trnh phn tch c th theo k thut . Ngha l phi c mt
phng php phn tch n nh. Cc thng s cn phi c chun ha l
nhng thng s sau:
Bc sng hp th. rng ti u ca khe o.
Nng c trng Nng kim tra
Khong tuyn tnh
5.1.1. Bc sng hp th (Vch ph)
Vch ph c chn xc nh nguyn t m mnh mong mun. Vch
ph ny phi tha mn cc iu kin:
-

Khng b cc vch khc chen ln gy nhiu hay trng lp.


Phi r rng v nt, c di sng chnh xc.

Cng vch ph hp th D phi ph thuc tuyn tnh vo nng


C trong mt vng nng nht nh.
Mt vi bc sng ca ph s c a ra. Ty thuc vo mc ch v
nng ca mu m chn cc bc sng thch hp. Nu mu c nng
nguyn t cn xc nh l qa nh th thng chn bc sng c nhy
cao, cn nu nng ln th chn bc sng c nhy nh hn.
5.1.2. Cng n HCL
Cng dng in lm vic cu n Catot rng (HCL). Ni chung nn
chn cng dng nm trong vng t 60% n 85% so vi cng cc
i ghi trn n HCL. Khi cn nhy cao th chn cn di, cn khi cn n
nh cao th chn cn trn.
5.1.3. Khe o cu my quang ph
Khe o (khe vo v khe ra cu chm tia) c nh hng n nhy v
vng tuyn tnh cu php o.
Ni chung nhiu my quang ph hp th thng c khe o thay i c
theo cc gi tr t 0.2 n 10nm
V d: 0,2; 0,4; 0,8; 1; 2 v 10nm. Bao gm 5 bc vi nhiu vch ph th
khe o ph hp l nm trong vng t 0,2 n 1nm. Do cn phi chn ch
mt gi tr ph hp nht cho php o nh lng mt nguyn t theo vch ph
c chn, sao cho ch cho va vch ph cn o vo khe o l tt nht.
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105

5.1.4. Chiu cao n nguyn t ha mu


Nu chn khng ng ta s khng nhng thu c nhy km v tn
hiu o khng n nh, m ng thi b nhiu yu t nh hng.
5.1.5. Thi gian o
Yu t ny ph thuc vo c trng k thut cu tng my quang ph v
ty thuc vo k thut nguyn t ha mu.
Vi php o F-AAS th l thi gian thu c tn hiu hp th n nh,
vi php o ETA-AAS th li l thi gian nguyn t ha mu
5.1.7. Nng c trng
L nng cn thit ca nguyn t to ra mt tn hiu bng 0.0044
n v hp th( khong 1% hp th).
Nng ny c th tra theo cc bng tra cu.
5.1.8. Nng kim tra.
L nng chun c th c c 0.2 n v hp th bc sng v
rng khe h trong iu kin tiu chun.
Nng ny rt quan trng cho php chn nhng iu kin v tc kh v
ha hi dung dch cn phn tch
5.1.9. Vng tuyn tnh
Yu t ny cng cn c xc nh chnh xc cho tng vch ph
chn nh lng nguyn t phn tch. V phn ln l nhng vch ph c
nhy cao. C nh th mi c th chun b mt dy mu chun ph hp
cho php o cu mnh.
5.1.10.B chnh nn khi o
Yu t ny c thc hin hay khng l ph thuc vo vch ph c chn
o. Nu nn cu ph c nh hng th phi thc hin php o c b chnh
nn loi tr nh hng v ngc li, nu khng nh hng th khng
cn thit.
5.2. iu kin nguyn t ho mu
Vn ny ty thuc vo k thut c chn nguyn t ha mu.
5.2.1. Vi php o F-AAS
Cn phi chn cc thng s sau y:
Chn thnh phn kh chy to ra ngn la c nhit ph hp.
Chiu cao cu n nguyn t ha mu(burner head).
Tc kh mang v tc dn mu vo bung aerosol ha.
B dy cu lp hp th,
5.2.2. Grafit AAS
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Bao gm nhng iu kin:


-

Thi gian, nhit cu cc giai on sy mu, tro ha,


Kh mi trng cho qu trnh nguyn t ha mu.

Cng sut t nng cuvet graphit nguyn t ha mu.


Lm sch cuvet graphit.
Lng mu a vo cuvet nguyn t ha.
5.3. Cc im cn ch khi thc hin php o
Cc ng chun tt nht l c dng trc khi phn tch mi ngy s
hn ch c nhng sai s. C th s dng li cc ng chun c sau khi
kim tra vi im trc khi phn tch, nu thy sai s trong phm vi cho php.
Nn tin hnh cc th nghim v s nhiu ca cc yu t khc nh
nng cc ion gy nhiu. nhy ca phng php, gii hn pht
hin ca my.
-

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.

Khi o ph AAS bng phng php nguyn t ha bng l grafit.


Phng php ny c chnh xc cao v gii hn pht hin rt nh v
vy dng phn tch cc nguyn t dng vt hoc vi lng. C th c nhiu
yu t nh hng kt qu o do vy phi lun hiu chnh. Ngy nay cc
loi l Grafit thng c tht k cu to vi cc b iu khin nhit v t
ng ha cao.
Trc khi tin hnh o trn my mu phn tch phi c x l theo cc
phng php c th cho tng i tng loi tr s nhiu ph.
Trnh t phn tch c c th ha trn mi my v c hng dn ring
v vy phi c k trc khi thao tc trn my.
5.3.1. S chen ln cu vch ph

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107

Yu t ny thng thy khi cc nguyn t th ba trong mu phn tch


c nng cao v thng l nguyn t c s cu mu. Tuy cc nguyn t
ny c vch ph khng nhy nhng do nng ln, nn cc vch ny xut
hin vi rng ln.
Nu n li nm cnh cc vch ph phn tch th cc vch ph ny s
chen ln cc vch ph phn tch, lm cho vic o cng cu vch ph
phn tch gp nhiu kh khn v thiu chnh xc, nht l vi cc my c
phn gii khng cao.
V th trong mi mc ch phn tch c th cn phi nghin cu v chn
nhng vch phn tch ph hp loi tr s chen ln cu cc vch ph cu
nguyn t khc.
S nh hng v ph ch yu l do thit b v tnh cht ca ngn la.
S nhiu v ph xy ra khi cc vch ph c chn phn tch khng tch
hon ton vi cc vch ph k cn hoc khi cc vch ph phn tch ny trng
vi vch ph ca mt cht khc.
Mc d ph hp thu nguyn t l rt n gin nhng cng c nhng
trng hp b trng lp vch ph, mt vi trng hp c th c cho trong
bng sau:
Bng 2.13: S chen ln v s trng vch ph ca cc nguyn t
Nguyn t

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

Nhng s cn tr kiu ny c th trnh c bng cch chn cc vch


ph phn tch khng b chn(nhiu). V d s cn tr ca Zn(213.8-56A) khi
xc nh Fe(213.8-58.9 A) trong thp nu khng ch n s nhiu v ph
ny th kt qu phn tch hn nhin l sai s rt ln.
Trong mi trng hp th, c bit l trong ngn la n kh, nhiu khi
cn c cha c cc ht rn rt nh li ti ca vt cht mu cha b ho hi v

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nguyn t ha, hay cc ht mui cacbon cu nhin liu cha c t chy


hon ton.
Cc ht ny hoc hp th hoc chn ng i cu chm sng t n
HCL chiu vo mi trng hp th.
Yu t ny th hin rt r khi chn khng ng chiu cao cu n nguyn
t ho mu v khi hn hp kh chy khng c t chy tt, hay do thnh
phn cu hn hp kh chy khng c chn ph hp(thng l qu d
Acetylen).
5.3.2. nh hng ca cc yu t vt l
nh hng ca cc yu t vt l ch yu l do li khi a mu vo ngn
la bi nh hng v cc tnh cht vt l ca mu nh nht, sc cng b
mt.
a. nht v sc cng b mt cu dung dch mu
Trong php o AAS, vi k thut nguyn t ho mu trong ngn la, yu
t ny nh hng n tc dn mu v bung Aerosol ho v hiu sut
aerosol ha cu mu v t m nh hng n kt qu phn tch.
Ni chung, tc dn mu l t l nghch vi nht cu dung dch mu.

Hnh 2.21: nh hng ca nht n tc dn mu


Chnh s khc nhau v nng axit v loi axit, nng cht nn cu
mu, thnh phn cu cc cht c trong dung dch mu l nguyn nhn gy ra
s khc nhau v nht cu dung dch.
V th trong mi qu trnh phn tch nguyn t, nht thit phi m bo
sao cho mu phn tch v mu u phi c cng nng axit, loi axit v
thnh phn ho hc, vt l cu tt c cc nguyn t khc, nht l cht nn cu
mu. Yu t ny thng th hin nhiu trong php o F-AAS.
loi tr nh hng ny chng ta c th dung cc bin php sau:
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109

o v xc nh theo phng php thm cht chun.

Pha long mu bng mt dung mi hoc mt dung dch nn ph


hp.

Thm vo mu mt cht m c nng ln.


Dng bm y mu vi mt tc xc nh m ta mong mun.
b. Hiu ng lu li
Yu t ny th hin r rng c bit trong php o ph khng ngn la,
v cng ln khi mu phn tch c nng ln. ng thi cng ph thuc vo
bn cht cu cc nguyn t, hp cht n tn ti trong mu, cng nh loi
cuvet Graphit c dng nguyn t ho mu.
Ni chung cc nguyn t kh bay hi v d sinh ra hp cht bn nhit
lun lun gy ra nh hng ny ln. Cc cuvet c ch to t graphit
hot ho thng hn ch c hiu ng ny.
Ngha l b mt cuvet cng mn th nh hng cng nh, b mt cng
xp th nh hng cng ln. Do tnh cht ny m khi nguyn t ho mu
o cng vch ph, th mt lng nh ca nguyn t phn tch khng b
nguyn t ho, chng c lu li trn b mt cuvet v c th tch t li qua
mt s ln nguyn t ho mu.
Nhng n mt ln no th n li b nguyn t ho theo v do to
ra s nguyn t t do ca nguyn t phn tch tng t ngt khng theo nng
ca n trong mu, ngha l lm tng cng ca vch ph v dn n
lm sai lch kt qu phn tch.
loi tr nh hng ny chng ta c th theo cc cch sau:
Lm sch cuvet mi ln nguyn t ho mu, lm bay hi ht cc
cht cn li trong cuvet. V vy phi thc hin nhit cao hn
nhit nguyn t ho nguyn t phn tch.
Dng cc loi cuvet c ch to t cc loi graphit c hot
ho ton phn, c b mt chc v mn.
Khi phn tch nn o cc mu c nng nh trc.
Thm vo mu nhng cht m c nng ph hp.
Trng b mt trong ca cuvet graphit bng mt lp cc cht bn
nhit.
c. S Ion ho
y l yu t vt l th ba nh hng n kt qu phn tch. V qu trnh
ion ho thng lm gim s nguyn t t do cu nguyn t phn tch trong
mi trng hp th to ra ph.
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Nhng mc b ion ho cu mi nguyn t l khc nhau v ph thuc vo


nhit cu mi trng hp th.
Vi mt nguyn t, th khi nhit cu mi trng hp th cng cao, th
nguyn t cng b ion ho nhiu hn
S nhiu ion ho xy ra khi nhit ngn la c nng lng kch
thch nguyn t kim loi bc x in t v to ra ion. Khi nhng in t ny
sp xp li s lm gim s lng cc nguyn t trng thi c bn, do s
hp th b gim.
Bng 2.14: Mc ion ho cu mt s nguyn t
Nguyn t

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

loi tr s ion ho cu mt nguyn t phn tch chng ta c th dng


cc bin php sau y:
C th kim sot s nhiu ion ha bng cch thm mt lng tha
cc cht(nguyn t) d b ion ha vo trong mu trng, cht chun
cng nh mu phn tch. Cc kim loi kim nh K, Na, Rb, Cs l
thch hp cho mc ch ny
Chn iu kin nguyn t ho c nhit thp, m trong iu kin
nguyn t phn tch hu nh khng b ion ho.
Thm vo mu phn tch mt cht m cho s ion ho. l cc
mui halogen cu kim loi kim c th ion ho thp hn th ion ho
cu nguyn t phn tch vi mt nng ph hp. nh vy trong
iu kin nguyn t phn tch s khng b ion ha na.
d. S kch thch ph pht x
Yu t ny xut hin thng lm gim nng ca cc nguyn t trung
ha c kh nng hp th bc x trong mi trng hp th. Do cng lm
gim cng ca vch ph hp th.
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111

loi tr nh hng ca s pht x ca nguyn t phn tch chng ta


c th dng cc bin php sau y:
Chn nhit nguyn t ha mu thp ph hp m ti nhit

s kch thch ph pht x l khng ng k hoc khng xy ra i


vi nguyn t phn tch.
Thm vo mu cc cht m hn ch s pht x ca nguyn t
phn tch. chnh l cc mui halogen ca kim loi kim, c th
kch thch ph pht x thp hn th kch thch ph pht x ca

nguyn t phn tch.


Chnh gim rng ca khe, tng cng dng ca n v pha
long mu.

Bng 2.15: Mc b kch thch ph pht x ca cc nguyn t trong cc iu


kin khc nhau
Nguyn t

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

nn ca mu l nhng hp hp cht d ha hi.


S gim cng ca vch ph khi nguyn t phn tch tn ti
trong nn ca mu l nhng hp cht bn nhit, kh ha hi. Lc
ny cc nguyn t nn km hm s ha hi ca nguyn t phn tch.
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S gy nhiu do yu t ha hc l vn ph bin nht trong xc

nh bng phng php hp th nguyn t.


Yu t gy nhiu ha hc thng c hn ch hoc kim sot chng
bng hai cch:
S dng ngn la c nhit cao hn hoc thm tc cht cnh
tranh(cation cnh tranh) vo dung dch mu(hoc dung dch cht chun).
V d: nh hng ca Photphat trn canxi nu dng ngn la khng khAcetylen, canxi photphat khng phn ly hon ton.
Khi nng Photphat tng th s hp th ca Canxi gim. Gii php
y l cho mt lng ln Lanthan vo hoc dng ngn la c nhit cao
hn l N2O-Acetylen

Hnh 2.22: S gy nhiu ca Photphat ln Canxi


Khi Lanthan c thm vo, n s kt hp vi Photphat v gii phng
Canxi, lm cho hp th ca Canxi khng ph thuc vo nng ca
photphat hin din trong dung dch.
Nu dng ngn la(N2O-Acetylen) nng hn m khng cn s nhiu ha
hc na th khng cn thit phi thm Lanthan vo.
a. Nng axit v loi axit trong dung dch mu
Ni chung nng axit trong dung dch mu lun lun c nh hng n
cng ca vch ph cu nguyn t phn tch.
nh hng ny thng gn lin vi loi anion ca axit. Cc axit cng
kh bay hi thng cng lm gim nhiu cng vch ph.

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113

Hnh 2.23: nh hng ca lai axit n cng vch ph Ca 422.7 nm


trong php o F-AAS(khng kh + C2H2).
Ni chung cc axit lm gim cng vch ph theo th t:
HClO4<HCl<HNO3<H2SO4<H3PO4<HF.
Ngha l axit HClO4, HCl v HNO3 gy nh hng nh nht trong vng nng
nh.
Chnh v th trong thc t phn tch ca php o ph hp th nguyn
t(AAS) ngi ta thng dng mi trng l axit HCl hay HNO 3 vi nng
1% hay 2%. V nng ny nh hng ca 2 axit ny l khng ng k(
nh hn 5%)
b. nh hng ca cc cation
Dung dch mu phn tch, ngoi nguyn t cn xc nh, thng cn
cha cc nguyn t khc. Cc nguyn t ny tn ti di dng cc cation hay
anion tan trong dung dch mu. Cc ion ny c th lm tng, cng c th lm
gim,cng vch ph ca nguyn t phn tch.
Khi c nh hng th mc nh hng ca mi ion cng rt khc nhau
trong tng trng hp c th.
6. Mt s iu kin chun ghi ph AAS cho cc nguyn t
xc nh cc nguyn t bng phng php AAS a ra mt s cc
iu kin chun c cho l ti u v cc ch thch cho tng nguyn t. Sau
y l nhng iu kin chun ghi ph ca mt s nguyn t ch yu sau:
6.1. Bc (Ag)
iu kin chun bng phng php hp th nguyn t AAS.
Ngn la: hn hp Axetylen- khng kh
Mu chun v mu phn tch c axit ha vi HNO3(5% v/v)
114

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Dung dch chun - AgNO3 500 mg/l theo Ag


Ch : dung dch chun AgNO3 rt nhy vi nh sng v vy phi lu tr
trong bnh mu nu
Bc sng

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

Cc ion gy nhiu - Clo, Brom, iot, pemanganat.


Mt lng ln nhm hoc axit v c c th lm gim cng ca vch
ph.
6.2. Nhm (Al)
Ngn la: Hn hp kh axetylen v nit dioxit.
Dung dch chun - AlCl3 1000mg/l theo Al(axit ha bng HCl 1%)
gim cc tn hiu nhiu v kim sot qu trnh ion ha ngi ta cho
thm dung dch KCl hay LaCl3( 1 %) vo mu chun v mu phn tch
Cc iu kin ghi ph.
Bc sng
(nm)

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

6.3. Asen (As)


Ngn la: Axetylen khng kh
n khng in cc
Dung dch chun - Kali asenat K 3 AsO4,1000 mg/l theo As
C th iu ch theo cch sau ;Ha tan 1,320 g As2O3 vi 25 ml dung
dch KOH 20 % sau trung ha bng H2SO4 20%( th li vi pheolphtalein).
nh mc n 1l vi dung dch 1% H2SO4.
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115

Cc iu kin ghi ph.


Bc sng
(nm)

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

6.4. Bary (Ba)


Ngn la: Hn hp kh axetylen v nit dioxit. n Catot rng.
Dung dch chun -BaCl2 1000 mg/l theo Ba
Chun b mu chun -Ha tn 1,437 g BaCO3 trong dung dich HCl t l
1-1. Sau nh mc thnh 1lt bng dung dch 1% HCl.
Qa trnh ion ha c th kim sot bng cch thm mui KCl vo mu
phn tch v mu chun. Nu c mt Ca c th vch ph 553,6 nm b nhiu
Cc iu kin ghi ph.
Bc sng

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
--

6.5. Canxi (Ca)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng.
Dung dch chun - CaCl2 500 mg/l theo Ca
Chun b: Ha tan 1,249 g CaCO3 trong 50 ml nc ct deion ha sau
cho thm 10 ml HCl ha tan hon ton. nh mc n 1l bng nc ct
deion ha.Qa trnh ion ha c th kim sot bng cch thm mui KCl vo
mu phn tch v mu chun. Cc ion nguyn t gy nhiu bao gm - Be, P,
Si, Ti, Zr. lm gim hiu ng nh hng ca cc nguyn t ny cn thm
0,1 - 1,0% ion La hoc Sr.
Cc iu kin ghi ph.
Bc sng

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

6.6. Cadmi (Cd)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - CdCl2 1000 mg/l theo Cd
Chun b; Ha tan 1,0 g Cd trong dung dch HCl t l 1-1. Sau nh
mc n 1l bng dung dch 1 % HCl.Nu mu cha nhiu silicat c th gy
nhiu cho cc vch ph ca Cd
Cc iu kin ghi ph.
Bc sng
(nm)

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

--

6.7. Crom (Cr)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc.
Dung dch chun - K2CrO4 1000 mg/l theo Cr.
Chun b; Ha tan 3,735 g K2CrO4 nc ct kh ion sau nh mc
n 1l bng nc ct.
Ion gy nhiu bao gm Fe v Ni. gim nh hng ca cc ion ny
cho thm NH4Cl vo mu chun v mu phn tch. Nu c nhiu photpho
cng lm gim cng ca Cr.
Cc iu kin ghi ph.
Bc sng

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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Chun b; Ha tan 1,000 g Cu trong mt th tch ti thiu HNO3(1-1) sau


nh mc n 1l bng HNO3 1%.
Cc iu kin ghi ph.
Bc sng

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

6.10. Thy ngn (Hg)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
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Khong tuyn
tnh mg/L
6,0
10,0
10,0
10,0
20,0
20,0
-

Dung dch chun - HgCl2 1000 mg/l theo Hg


Chun b: Ha tan 1,080 g HgO trong mt th tch ti thiu HCl(1-1) sau
nh mc n 1l bng nc ct kh ion.
Ion gy nhiu l Co. gim nh hng ca cc ion ny cho thm
ascorbic axit, SnCl2 hay cc cht c th lm gim s hin din ca Hg(I) hay
Hg vo mu chun v mu phn tch.
Cc iu kin ghi ph.
Bc sng

rng khe h

Nng kim

Khong tuyn

(nm)

(nm)

tra(mg/L)

tnh mg/L

253,7

0,7

200,0

300,0

6.11. Iridi (Ir)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun -(NH4)2IrCl6, 500 mg/l theo Ir
Chun b ; Ha tan 1,147g(NH4)2IrCl6 trong mt th tch ti thiu HCl 1%
sau nh mc n 1l bng HCl 1%.
Cc iu kin ghi ph.
Bc sng
(nm)

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

6.12. Kali (K)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - KCl 1000 mg/l theo K
Chun b ; Ha tan 1,907 g KCl trong nc ct kh ion sau nh mc
n 1l bng nc ct kh ion.

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119

Gim nh hng ca cc ion gy nhiu bng cch cho thm mui ca


kim loi kim vo mu chun v mu phn tch. S c mt ca cc axit v c
vi nng ln cng c th gy nhiu.
Cc iu kin ghi ph.
Bc sng

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

6.13. Lantan (La)


Ngn la: Hn hp Axetylen + N2O.
n catot rng hoc n khng in cc
Dung dch chun LaCl3, 50 mg/l theo La
Chun b;Thm t 0,5864g La2O3 vi 50ml nc ct kh ion, thm t
t v cn thn 250ml HCl m c vo ha tan La2O3 sau nh mc
n 1l bng nc ct kh ion.
Gim nh hng ca cc ion gy nhiu bng cch cho thm mui ca
kim loi kim vo mu chun v mu phn tch.
Cc iu kin ghi ph.
Bc sng
(nm)

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

6.14. Magie (Mg)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - MgCl2 1000 mg/l theo Mg

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Khong tuyn
tnh mg/L
3,0
6,0
50,0
100,0
200,0
3000,0
-

Chun b; Ha tan cn thn 1,000 g Mg trong mt th tch ti thiu HCl


sau nh mc n 1l bng HCl 1%.
Ion gy nhiu l Al, Si, Ti, P. gim nh hng ca cc ion ny cho
thm LaCl2 1% vo mu chun v mu phn tch.
Cc iu kin ghi ph.
Bc sng

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

6.15. Mangan (Mn)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - MnCl2 1000 mg/l theo Mn
Chun b; Ha tan 1,000 g Mn trong mt th tch ti thiu HNO3 sau
nh mc n 1l bng HCl 1%.
Ion gy nhiu l Si. gim nh hng ca cc ion ny cho thm CaCl 2
0,2% vo mu chun v mu phn tch.
Cc iu kin ghi ph.
Bc sng
(nm)

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

6.16. Molipden (Mo)


Ngn la: Hn hp Axetylen + N2O.
n catot rng hoc n khng in cc
Dung dch chun -(NH4)6Mo7O24.4H2O 1000 mg/l theo Mo
Chun b; Ha tan 1,840 g(NH4)6Mo7O24.4H2O trong 1l NH4OH 1%.
Ion gy nhiu l Ca, Sr, Fe, SO42-. gim nh hng ca cc ion ny
cho thm AlCl3 0,5%, NH4Cl 2%, Na2SO4 0,1% vo mu chun v mu
phn tch.
Cc iu kin ghi ph.

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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

6.17. Natri (Na)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - NaCl 1000 mg/l theo Na.
Chun b; Ha tan 2,542 g NaCl trong nc kh ion v nh mc n 1l
bng nc ct kh ion.(rt kh chun khng b nhim bn)
Gim nh hng ca cc ion gy nhiu bng cch cho thm mui ca
kim loi kim vo mu chun v mu phn tch. S c mt ca cc axit v c
vi nng ln cng c th gy nhiu.
Cc iu kin ghi ph.
Bc sng
(nm)
589,0
330,0

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
-

6.18. Niken (Ni)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - Ni(NO3)3 1000 mg/l theo Ni
Chun b; Ha tan 1,000 g Ni trong mt th tch ti thiu HNO3 sau
nh mc n 1l bng HNO31%.

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Ion gy nhiu l Fe, Cr. gim nh hng ca cc ion ny bng cch


s dng ngn la N2O + axetylen nhng nhy ca Ni s thp hn
Cc iu kin ghi ph.
Bc sng

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

6.19. Photpho (P)


Ngn la: Hn hp Axetylen + N2O.
n catot rng hoc n khng in cc
Dung dch chun -(NH4)2HPO4 50 mg/l theo P
Chun b; Ha tan 21,32 g(NH4)2HPO4 trong nc ct kh ion sau
nh mc n 1000 ml bng nc kh ion.
Cc iu kin ghi ph.
Bc sng
(nm)
213,6
214,9

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

Mt lng ln cc nguyn t khc( Vd- 10,0mg/l Fe) c th nh hng


n kt qu.
Cc iu kin ghi ph.
Bc sng

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

6.21. Platin (Pt)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - PtCl4 1000 mg/l
Chun b - Ha tan 1 g Pt trong mt lng ti thiu nc cng toan,
bay hi n kh. Thm vo 5ml HCl v 0,1g NaCl tip tc cho bay hi n
kh. Ha tan phn rn thu c trong 20ml HCl v nh mc n 1l bng
nc ct kh ion.
Ion gy nhiu l Li, Na, K, Mg, Ca, Pb, Sr, Ba, Cr, Fe, Co, Ni, Ru, Rh, Ir,
Pd, H2SO4, H3PO4, HClO4, HBr, NH4+, Zn v Hg. gim nh hng ca cc
ion ny cho thm 0,2% La trong HCl 1% vo mu chun v mu phn tch.
Cc iu kin ghi ph.

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

6.22. Selen (Se)


Ngn la: Hn hp Axetylen + khng kh.
n catot rng hoc n khng in cc
Dung dch chun - Se(NO3)6 1000 mg/l theo Se
Chun b; Ha tan 1,000 g Se trong mt lng ti thiu HNO 3 m c,
bay hi n kh. Thm vo 2ml nc v cng bay hi n kh, tin
hnh 2 hoc 3 ln. Ha tan trong HCl 10% v nh mc n 1l bng HCl 10%.
Cc iu kin ghi ph.
Bc sng

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

6.24. Thic (Sn)


Ngn la: Hn hp Axetylen + N2O.
n catot rng hoc n khng in cc
Dung dch chun - SnCl4 1000 mg/l theo Sn
Chun b; Ha tan 1,000 g Sn trong 100ml HCl m c v nh mc n
1l bng nc ct kh ion. Dung dch thic chun nn cha 10% HCl.
Cc iu kin ghi ph.
Bc sng
(nm)

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

6.25. Titan (Ti)


Ngn la: Hn hp Axetylen + N2O.
n catot rng hoc n khng in cc
Dung dch chun - TiCl4 1000 mg/l theo Ti
Chun b; Ha tan 1,0 g Ti trong 100ml HCl(1 -1) sau lm lnh v nh
mc n 1l bng HCl(1-1). Lu - dung dch Ti chun nn cha 10% HCl.
Ion gy nhiu l Al, Co, K, Mn, Na, Cu, Ca, Cr, Fe, Li, Mg, Mo, P, Cd, Sb,
ZN, BA, Ni, Sn, Sr, Pb, V, F v NH4+. gim nh hng ca cc ion ny cho
thm mui ca kim loi kim(KCl 0,1% hay nhiu hn) vo mu chun v mu
phn tch.
126

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Cc iu kin ghi ph.


Bc sng
(nm)

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
-

7. Mt s vch AAS chun ca cc nguyn t


Cc nguyn t kim loi ch yu u c th xc nh bng phng php
ph hp th nguyn t. Mi nguyn t u c cc vch chun c trng bng
di dy gii thiu mt s vch ph chun ca cc nguyn t
Bng 2.12. Mt s vch ph chun ca cc nguyn t

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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

8.1.1. My o ph AAS vi cc cu hnh sau


-

B cp ngun tia 10.


B phn nguyn t ha mu(ngn la, l grafit.).

B tch nh sng n sc.


Cc loi n catt rng cho tng nguyn t.
B phn nhn tn hiu v khuch i tn hiu Detector.

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.

Dng c thy tinh, pipet vi lng, bnh nh mc 10 ml, 20 ml, 50 ml.

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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b. Cc mu du nht trc khi phn tch c x l nh sau:


v

Ly lng mu 200 ml khuy u trong 5 pht sau cn mu chnh xc


cho vo cc thy tinh cho thm khong,3 ml dung dch

kalixiclohexabutyrat(%). Ha lang mu bng dung mi xylen sao cho nng


ca cc kim loi trong khong gi hn nng pht hin c.Thng thm
khong 25 ml cho 0,1 g mu.
Dung dch mui hu c kali 1 % c chun b nh sau:
Ha tan 5,3 g xiclohexanbutyrat v 10 ml axit 2-Etyhexanoic trong 30 ml
xylen, un nng cho tan ht hon ton v nh mc n 100 ml bng dung
mi xylen.
c. Mu dng rn
Mu dng rn c v c ha bng axit hoc tch chit bng cc dung
mi thch hp trn cc thit b chuyn dng. Cc mu c ngun gc hu c
du khong c than ha trc trn bp in sau mi nung trong l nung
nhit 500-600 oC tro ha hon ton.
Sau khi v c ha mu c ha tn trong dung dch axit v nh mc
n th tch nht nh.
8.2.2. o ph hp thu nguyn t ca mu trn my AAS
a. Chun b thit b AAS
Xem xt tnh trng ca my, cc ng in, kh axetylen, N2O.
Bt my vo ch lm vic.
Chn cc iu kin ti u( t l kh t N2O+axetylen dng in...).
Ci t cc iu kin phn tch theo hng dn ca tng my.
n nh my, n nh nhit trong vng 15 pht.
b. Trnh t phn tch
Dng ng chun.
Pha ch dung dch cht cht chun cha cc nguyn t cn xc
nh t cht chun phc c kim tng ng vi nng khc nhau
trong dung mi dng ng chun cho tng nguyn t phn tch
trn my AAS iu kin ti u tham kho trong cc hng dn.
o ph AAS ca mu phn tch pha trong dung mi vi t l tng
ng nh i vi cht chun.
-

Ghi chp kt qu th hin trn my tnh.


Sau khi kt thc cc php o a my v trng thi ban u, sau
kha cc ng kh v tt my.
8.3. Tnh ton
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131

Sau khi nhn c cc s liu kt qu trn my. Nng cc nguyn


t cn xc nh c tnh ton theo cng thc sau:
Cho mu lng( mg/L)
Me =

A(C B)
( mg/L)
C

Trong : A - nng kim loi c xc nh theo ng chun mg/L.


B - lng dung mi pha long( ml)
C - nh mc mu phn tch( ml)
Hoc cng thc sau cho mu rn (mg/kg)
Me =

AV
.
W

Trong : V nh mc mu( ml)


W- Khi lng mu(g)
A. Nng cht phn tch theo ng chun mg/l
Tnh ton nng nguyn t trong mu phn tch bng phng php l
Grafit theo cng thc sau.
Z (C B)
(mg/L)
C

Trong : C - nh mc mu phn tch(ml)


B - Th tch dung mi pha long(ml)
Z - Nng nguyn t theo ng chun.(mg/L)
Phiu nh gi thc hnh xc nh hm lung hydrocacbon trong phn
on du m bng ph AAS
C

Khng

Trnh t tin hnh hot

thc
hin

thc
hin

ng

132

Khng

Tiu chun

hot ng

Kim tra tnh trng my


Ch dn an ton

Theo hng
dn qui nh

Cc cng vic chun b:


dng c, ha cht, cht
chun

Theo yu cu
k thut cho
tng bi

Chun b cc phiu theo


di v nh gi kt qu

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

Lp li php phn tch khi


cn thit

Ghi nhn xt

Ch n nh v tr my
v li trng thi ban u

Ghi nhn xt

Kt thc bi thc hnh v

Np phiu bo

tnh ton kt qu

co, bn giao
my

Bng tng kt thc hnh phn tch


Nguyn t

Vch ph c trng

Hm lung %

Nhn xt bi thc hnh v cc ch thch cc k hiu. Tho lun kt qu


thu c, vit bo co tng kt.
9. Cu hi bi tp
9.1. L thuyt
1. Hy nu nguyn l ca phng php ph hp thu nguyn t.
2. M t cc lai n to tia n sc.
3. Cc b phn chnh ca my AAS.
4. Nguyn l hot ng ca n Catot rng.
5. Cc yu t ha hc v vt l nh hng n php o ph AAS.
9.2. Bi tp
1.

2.

Mt my n sc cch t 1180 rnh / mm lm vic vi iu kin gc ti


i=0. Hy tnh gc nhiu x r thu c tia n sc = 300nm. Cho bc
m=1
Mt my AAS c s dng cch t kp, tc l cho php lm vic vi 2
gc nghing(la chn ty thuc vng lm vic) c cc tnh nang sau:
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133

Vng ph lm vic: 189 860 nm

Cch t n = 1800 rnh / mm


Kch thc 64 mm x 72 mm

Gc nghing

Bc nhiu x lm vic m = 1

Hy tnh

cho 1 = 236 nm, gc nghing

2 cho

2 = 597 nm

Bit rng my n sc ca Model ny lp theo thit k lun lun tha


iu kin i = r v tia ti nm cng vi tia nhiu x mt bn ca php tuyn
vi cch t(du +)
3. Mt my AAS c tn x di nghch o D l 1 = 1,6 nm/mm.
Hy c lng di tiu c f ? Cho m = 1

134

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BI 3. PH NHIU X TIA X (XRD)


M bi. HD K3
Gii thiu
Phng php ph Rnghen l phng php vt l rt hu hiu
nghin cu cu trc, thnh phn pha ca cc tinh th cht rn. C s ca
phng php da trn hin tng bc x in t t ngun pht cc tia m
cc (tia X) c kh nng xuyn qua mt s tm chn thng thng lm en
phim, knh nh.
Cc ngun pht tia m cc c tnh cht c bit ny gi l nhng ng
pht tia X c nh khoa hc Ronghen pht hin v to ra t nhng nm cui
ca th k 19 c cu to gm c hai b phn chnh l catt v ant.Chm tia
in t pht ra t catt s c gia tc do in p ln ant s bay v ant
vi vn tc ln c ng nng ln va p vo ant bin thnh nhit nng v
mt phn c pht ra di dng bc x tia 10.
Vic ng dng phng php ph Rnghen 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 cu trc
pha tinh th ca cc vt liu rn, cc hn hp oxit kim loi, cc cht xc tc
rn, cc cht khong v c, t ...V vy vic tip thu c c s l thuyt
ca phng php v k thut thao tc vn hnh my mc thit b o ph
Ronghen l rt quan trng v cn thit.
Mc tiu thc hin
Hc xong bi ny hc vin s c kh nng
M t c s ca phng php ph Rnghen, my o ph
Phn tch cu trc tinh th ca Zeolit bng ph XRD
nh tnh v nh lng thnh phn pha ca zeolit
Th nghim, thc hnh o trn my trong phng th nghim.
Ni dung chnh
1.
2.
3.

C s ca phng php ph Rnghen


Phng trnh nhiu x Bragg-Vulf.
ng dng ph Rnghen phn tch thnh phn pha ca tinh th

4. nh lng thnh phn pha.


5. Phn tch cu trc pha.
6. Mt s ph Rnghen ca vt liu cht rn.
1. C s ca phng php Rnghen
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135

1.1.Mt s khi nim v vt liu rn v cu trc tinh th hc


Cu trc ca vt liu rn ph thuc vo s sp xp cc nguyn t, ion
hoc cc phn t v lc lin kt gia chng.
Vt liu rn c th c cu trc tinh th khi cc nguyn t hoc ion sp
xp mt cch c trn t trong mt mu hnh lp li trong khng gian ba chiu.
Vt liu rn c sinh ra trong t nhin hoc c ch to bi con
ngi, c cc tnh cht c bit v ha hc v vt l.
Vic ch to cc loi vt liu mi ang c pht trin rt nhanh nhm
p ng c cho nhu cu ca khoa hc k thut, do vic hiu bit v cu
trc v cc tnh cht ca chng l v cng quan trng v cn thit.
Trong cc nhm vt liu th vt liu kim loi v vt liu gm l hai i tng
nghin cu ch yu ca phng php Rnghen.
Vt liu kim loi c cu trc tinh th, trong cc nguyn t c sp
xp mt cch trt t.
Vt liu gm c th c cu trc tinh th hoc khng tinh th hoc hn
hp ca c hai cu trc trn.
Vt liu gm l vt liu v c bao gm nguyn t kim loi v phi kim lin
kt ha hc vi nhau.
1.2. Cu trc v hng s mng hnh hc tinh th
1.2.1.Mng khng gian v c s
Cc nguyn t hoc ion nu c sp xp mt cch trt t lp i lp li
trong khng gian ba chiu th chng to thnh vt rn cu trc tinh th v
c gi l vt liu tinh th. S sp xp cc nguyn t trong vt rn c th
c m t bng mt mng li 3 chiu m nt mng l cc nguyn t (hoc
ion), v c gi l ma trn im ba chiu v hn.
Trong tinh th l tng tp hp cc nt mng quanh bt k mt nt no
cho cng ging nh cc nt mng xung quanh. Nh vy mi mng khng
gian c th c m t bi cc v tr nguyn t xc nh trong mt n v (
c bn). Kch thc v hnh dng ca n v c th c biu din bng 3
vect c s a, b, c xut pht t 1 gc ca n v. Chiu di ca ba vect
ny v gc gia chng , , c gi l hng s mng.
1.2.2. Mng Bravais
Cc nh tinh th hc a ra by kiu n v xy dng cc mng
im ca tinh th.
A.J.Bravais a ra 14 kiu mng tinh th ca cht rn v 4 kiu n
v:
136

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n gin

Tm khi
Tm mt

Tm y

Hnh 3.1: Mng khng gian ca tinh th rn l tng, n v v hng s


mng
T cc kiu n v c th phn lp mng khng gian theo h tinh th
nh sau:
Bng 3.1: Mng khng gian ca h tinh th
H tinh th
Lp phng
(Cubic)
Bn phng
(Tetragoral)
Trc thoi
(Orthorombic)

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)

Kiu mng Bravais


Lp phng n gin
Lp phng tm khi
Lp phng tm mt
Bn phng n gin
Bn phng tm khi
Trc thoi n gin
Trc thoi tm khi
Trc thoi tm mt
Trc thoi tm y
Ba phng n gin

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)

Su phng xp cht (SPXC)

Hnh 3.2: Cu trc tinh th ca vt liu rn


Cc cu trc ny c lin kt nguyn t cht ch hn v c nng lng
thp hn. n v c kch thc v cng nh ch c nonamet (nm). V d kim
loi Fe c cu trc lp phng tm khi nhit phng l 0,287 nm c th
tnh ton c s lng n v trong 1 mm
1nm.106
1x
nm 3.48 x106
0.287 nm

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)

i vi cu trc lp phng tm mt, quan h gia chiu di cnh (a) v


bn knh nguyn t (R) nh sau:
a

4R

(3.2)

H s xp (HSX) l phn th tch chim ch bi cc qu cu nguyn t


trong n v:
HSX

138

V1
V

http://www.ebook.edu.vn

(3.3)

Trong : V1: s nguyn t trong n v x th tch nguyn t.


V: Th tch n v.
Cu trc lp phng tm mt c HSX cao nht bng 0,74 v c gi l
cu trc xp cht. Cc cu trc lp phng khc l khng xp cht.
Bng 3.2. Quan h gia hng s mng v bn knh nguyn t ca kim loi c
cu trc tinh th lp phng tm mt v lp phng tm khi.
Loi cu trc
tinh th

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

Cu trc su phng xp cht (SPXC): trong cu trc ny tng s


nguyn t trong mt n v l 6.
T s chiu cao ca lng tr v cnh y c gi l t s c/a. c bn ca
SPXC l khi lng tr lc gic gm 6 lng tr tam gic u.

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139

Hnh 3.3: V tr cc nguyn t trong mng c s:


a.- LPTK , b LPTM , c - SPXC
Bng 3.3. Hng s mng v bn knh nguyn t ca mt s kim loi c cu
trc tinh th SPXC (To = 200C)
Hng s mng
Kim loi

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)

1.2.4. Cch k hiu v tr nguyn t trong c bn lp phng


S dng h ta vung gc x, y, z. V tr nguyn t trong c bn
c xc nh bng khong cch n v dc theo trc x, y, z.
Th d: ta v tr ca tm nguyn t gc trong c bn lp phng
tm khi c th biu din nh hnh sau: nguyn t tm (, , )

140

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Hnh 3.4: Cc mt phng ca tinh th lp phng n gin


1.2.5. Phng tinh th trong mng lp phng
i vi tinh th lp phng ch s phng tinh th l cc thnh phn
vect ca phng cn tm dc theo cc trc ta x y z v gim n s
nguyn nh nht. K hiu chung cho cc ch s phng l [ u v w ]. Ch s
phng m k hiu l mt gch ngang trn ch s, v d [ 1 ]. Mi vect ch
phng song song u c ch s phng nh nhau.

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141

Hnh 3.5: Trc ta vung gc xyz


1.2.6. Ch s Miller
xc nh mt phng tinh th trong cu trc lp phng, thng s
dng ch s Miller.
a. Ch s Miller c nh ngha nh sau
Ch s Miller l i lng nghch o giao im phn s ca mt tinh th
ct trn trc tinh th x, y, z ca ba cnh khng song song ca c bn lp
phng.
Cnh lp phng ca c bn l n v o chiu di v v tr ct ca mt
tinh th c o theo thnh phn ca chiu di n v ny.
b. xc nh ch s Miller cn phi theo trnh t sau:
-

Chn mt mt phng khng qua gc ta .


Xc nh cc ta giao im ca mt phng vi cc trc x, y, z
(ta c th l phn s).
Ly nghch o ca cc ta ny.
Trit tiu cc phn s v xc nh tp s nguyn nh nht, cc s
ny chnh l ch s Miller ca mt phng tinh th v c k hiu
bng cc ch sau h, k, l theo trc x, y, z tng ng. S m c
vit bng mt gch ngang trn [ hkl ]

142

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Hnh 3.6: Ch s Miller ca mt s mt tinh th lp phng quan trng.

Hnh 3.7: Mt tinh th lp phng c cc im ct.


V d: Xc nh ch s Miller ca mt s mt tinh th lp phng quan
trng sau.
Bng 3.4
Tiu ch

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

Ch s Miller ca mt phng s l (1 0 0).


Bng cch tng t c th xc nh c ch s Miller ca cc i lng
trn.
Trong cu trc tinh th lp phng khong cch (d) gia cc mt phng
song song gn nhau nht c cng ch s Miller c k hiu l dhkl v c
tnh ton theo cng thc sau:
1
d2

h2

k2
a2

l2

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(3.4)

143

Trong : a l hng s mng.


1.2.7.Ch s mt tinh th trong mng su phng xp cht (SPXC)
Ch s ny cn c gi l ch s Miller- Bravais v c k hiu bng 4
ch h, k, i, l, (h k i l) v c thit lp trong h ta 4 trc trong c bn.
+c

-a1

+a3

-a2

+a2
o

120 C
+a1

-c

-a3

Hnh 3.8: Bn trc ta ca tinh th SPXC.


Ba trc c s l a1, a2, a3 hp vi nhau tng i, mt gc 1200, trc th 4
(c) t ti tm ca c bn.
Nghch o ca cc giao im ca mt phng tinh th vi trc a1, a2, a3, c
s c cc ch s h, k, i, v l.
Mt y ca cc c bn ca SPXC c k hiu l (0001).
Mt bn hay mt lng knh ty theo v tr ca n m c cc ch s, cc k
hiu khc nhau v to thnh h mt { 1010 }

144

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Hnh 3.9: Ch s Miller- Bravais ca mt tinh th SPXC


1.2.8.L hng trong cu trc mng.
L hng l khng gian trng b gii hn bi hnh khi nhiu mt m mi
khi l tm nguyn t hoc ion nt mng. Kch thc l hng c nh gi
bng bn knh ca qu cu ln nht c th t lt vo khng gian trng .
Hnh dng, kch thc l hng ph thuc vo kiu cu trc mng.
L hng thng gp c dng khi bn mt hoc tm mt nh m t trong
hnh sau:

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

Nhiu nguyn t c th tn ti cc dng tinh th khc nhau ph thuc


vo nhit v p sut.
V d: St tn ti c hai cu trc tinh th LPTK v LPTM trong sut
thang nhit t nhit phng n Tnc = 1539oC. St
-273oC

tn ti t

912oC c cu trc tinh th LPTK; st t 912oC

tinh th LPTM; st delta

t 1394oC

1394oC c cu trc

1539oC cu trc LPTK nhng c hng

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

LPTK (> 447OC)

Co
Fe

SPXC
LPTK

LPTM (> 427OC)


LPTM (912oC

1394oC)

Li
Na

LPTK
LPTK

LPTK (> 1394oC)


SPXC (< -193oC)
SPXC (< -233oC)

Ti
Y
Zr

SPXC
SPXC
SPXC

LPTK (> 880OC)


LPTK (> 1481OC)
LPTK (> 872OC)

1.2.10. Sai lch mng tinh th


Trong thc t tinh th khng hon chnh m thng cha cc dng
khuyt tt khc nhau dn n tnh cht c hc v vt l nh tnh dn in, n
mn kim loi....
Sai lch mng tinh th c th tn ti 3 dng chnh sau:
Khuyt tt im.
Khuyt tt ng lch.
Khuyt tt mt.
Khuyt tt im n gin nht l v tr khuyt nguyn t to thnh l trng
(vacancy) trong qu trnh to tinh th.
Nng lng hnh thnh cc khuyt tt cn bng c 1ev v s lng cc
khuyt tt cn bng ph thuc vo nhit theo hm m:
Nv

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.

Hnh 3.11: M hnh n tinh th v a tinh th


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147

AA - M hnh n tinh th; b - a tinh th, c - Vi hp kim a tinh th


1.2.13. Kch thc ht
Kch thc ht ca vt liu a tinh th c ngha quan trng v nh
hng nhiu n tnh cht ca kim lo1. Mt trong nhng phng php o
kch thc ht thng dng theo ASTM trong cp ht n c xc nh theo
cng thc sau:
N = 2 n-1

(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

2. Nhiu x tia X, phng trnh Vulf Bragg


2.1.Khi nim nhiu x tia X
Nhiu x l c tnh chung ca cc sng b thay i khi tng tc vi vt
cht v l s giao thoa tng cng ca nhiu hn mt sng tn x. Qu trnh
hp th v ti pht bc x in t cn gi l tn x.
Mi photon c nng lng E t l vi tn s

ca n:

E = h.
Mt khc tn s

lin quan ti bc sng


hc
E

(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.

Theo tnh ton bc sng tia X khong 0,2 nm (2Ao).


m t hin tng nhiu x ngi ta a ra ba thut ng sau:
Tn x (Scattering): l qu trnh hp thu v ti bc x th cp theo cc

hng khc nhau.


Giao thoa (Interference): l s chng cht ca hai hoc nhiu sng tn x
to thnh sng tng hp.
Nhiu x (Diffraction): l s giao thoa tng cng ca nhiu sng tn x.
2.2. To ngun tia X
Tia X c to ra khi cc in t vi tc ln b km hm bi mt vt
chn. Rnghen pht hin ch pht tia X chnh l ch c chm in t p
vo, v ng to ra ng pht tia Rnghen. Ngy nay, ng pht tia Rnghen
ngy cng c hon thin hn nhng chng u c nhng b phn chnh
sau:
Hai in cc Catot v Anot t trong ng thy tinh bng thch anh c
chn khng cao (10-6 10-7 mmHg).
Catot K thng c lm bng dy Vonfram v pht ra chm in t khi
c t nng.
Anot l mt a cng c lm bng Vonfram hay Platin. Ngi ta t
vo anot mt in p rt cao (hng trm kV).
Chm tia in t pht ra t catot c gia tc do in p ln Anot s
bay v pha anot vi vn tc ln. Khi cc in t c ng nng ln va p vo
anot phn ln nng lng s bin thnh nhit nng, ch c mt phn rt nh <

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149

1% c chuyn thnh tia 10. Do vy cn phi lm ngui ng pht Rnghen


bng nc.
Tia Rnghen pht ra t cc ng pht thng l cc bc x lin tc gm
nhiu bc sng khc nhau do cc in t mt nng lng trong mt lot va
chm vi cc nguyn t anot, v mi mt in t mt nng lng theo cch
khc nhau cho nn cc bc sng tia x cng khc nhau.
Ty theo tng iu kin nht nh (in th anot, cht liu lm anot) c
th thu c cc bc x hu nh n sc gi l cc tia Rnghen c trng.

Hnh 3.12: S nguyn tc ng pht tia Rnghen.


Cc vch c trng khc nhau s tng ng vi cc dch chuyn in t
gia cc mc nng lng v c k kiu l K, L, M theo m hnh cu trc
nguyn t ca Bohr.

150

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Hnh 3.13: M hnh nguyn t v s to thnh tia X c trng. K K , L


Mt s kim loi lm vt liu anot s cho cc vch c trng sau:
Mg - K = 0,95 Ao.
Fe - K = 1,7 Ao.
Cu - K = 1,5 Ao.
Ag - K = 0,7 Ao.
W - K = 0,5 Ao.
Trong nghin cu bng nhiu x tia X thng chn tia c trng l K v
tia K Cu l bc x thng c s dng rng ri nht.
Cc vch K c nng lng ln hn so vi L v khng b hp th mnh
bi vt liu nghin cu.
2.3. Mt s tnh cht ca tia Rnghen
Tia X c nhng tnh cht c bn sau:
Kh nng xuyn thu: tia Rnghen c kh nng xuyn qua mt s
tm chn sng thng thng, lm en phim nh.
Kh nng gy hin tng pht quang (ph hunh quanh tia X).
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151

Gy s ion ha ca cht kh.

Hin tng nhiu x


Nhiu x l s thay i ca cc tia sng hoc cc sng do s tng tc
ca chng vi vt cht.
Khi chm tia X chiu vo vt cht s xy ra tng tc vi cc in t
trong nguyn t (hoc ht nhn nguyn t nu chm tia X c nng lng
ln). Khi tng tc vi vt cht chm tia X c th mt mt phn nng lng
do cc hiu ng hiu ng hp th: xy ra khi tia X truyn qua vt liu. Chng
s b hp th v cng chm tia s gim. S gim ny tun theo nh lut
c bn ca s hp ph sng in t nh sau:
I

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

Hnh 3.14: Nhiu x tia X bi cc mt phng ca nguyn t (A-A - B-B).


iu kin nhiu x l:
n = SQ + QT = 2dhklSin

(3.10)

Qung ng 1-P-1 v 2-Q-2 bng s nguyn ln bc sng.


Trong :
n = 1, 2, 3,gi l bc phn x.
Phng trnh Bragg c dng sau:
n = 2dhklSin

(3.11)

Phng trnh ny biu th mi quan h gia gc cc tia nhiu x

bc sng tia ti, khong cch gia cc mt phng nguyn t. Nu nh lut


Bragg khng c tha mn th s khng xy ra hin tng giao thoa.
Khi n > 1 cc phn x c coi l phn x bc cao v phng trnh
Bragg c th vit nh sau:
= 2(dhkl/n) Sin

(3.12)

Thng s d/n l khong cch gia cc mt phng hkl v nh, nk, nl l cc


ch s Miller c khong cch bng l/n cch khong gia cc mt h, k, l.
nh lut Bragg l iu kin cn nhng cha cho nhiu x tia X, v
nhiu x ch c th chc chn xy ra vi cc n v c cc nguyn t
gc mng. Cn cc nguyn t khng gc mng m trong cc v tr khc,
chng hot ng nh cc tm tn x ph lch pha vi cc gc Bragg no ,
kt qu l mt i mt s tia nhiu x theo phng trnh phi c mt.

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153

Hnh 3.14: Nhiu x tia X t cc mt ca mng tinh th.


2.5.Mng o
Mt phng trong khng gian thc c th biu din bng mt nt mng
trong khng gian o. c bn ca mng o c xc nh bi cc vect
a*, b*, c* tha mn h thc sau:
a*a = b*b = c*c = 1
a*b = b*c = c*a = 0
Trong a, b, c l cc vect n v tinh th.
Mng o c nhng tnh cht sau:
-

Mi nt mng o tng ng vi mt mt (hkl) ca tinh th.


Vect mng o ghkl = ha* + kb* + lc* vung gc vi mt phng mang
(hkl) ca mng tinh th v
Ghkl = 1/d hkl g hkl

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)

Trong : Io Cng tia t1.


e in tch in t.
me Khi lng ca in t.
c Tc nh sng.
r Khong cch gia tn x in t n u d (detect).
Biu thc trn cho thy nng lng tn x t cc in t n l rt nh.
2.6.2. Nhiu x bi mt nguyn t
Nguyn t c nhiu m my in t quay xung quanh ht nhn. Tia ti
b tn x bi in t v ht nhn. Nhng ht nhn ca nguyn t rt ln cho
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155

nn c th b qua tn x bi ht nhn, do tn x ton phn ch yu bi


cc in t ring bit.
Cc in t quay quanh ht nhn cc v tr khc nhau s sinh ra sng
tn x vi pha khc nhau v s giao thoa vi nhau.
i lng tha s tn x nguyn t f m t hiu xut tn x trn mt
hng ring bit c xc nh bng t s sau:
f = bd1/bd2 f

bd1
bd 2

(3.15)

bd1 Bin sng tn x bi mt nguyn t.


bd2 Bin sng tn x bi mt in t.

Hnh 3.16: Tn x tia X bi mt nguyn t gi tr f bng s in t trong


nguyn t khi
0 hay f = Z (nguyn t s).
2.6.3. Nhiu x bi mng c bn
mng c bn l phn nh nht lp li tun hon to thnh tinh th.
Thng trong tinh th c cha cc nguyn t khc nhau sp xp cc v tr
khc nhau do cc sng c bin khc nhau s t hp li cho cng
tng cng v c biu din nh mt hm m phc nh sau:

Aei
Trong :

fe 2

i ( hu k

l )

(3.16)

- l s chnh lch pha gia sng tn x bi nguyn t B v

sng tn x bi nguyn t A i vi mt phn x hkl.


Cng nhiu x c d on bi nh lut Bragg v t l vi bnh
2

phng tha s cu trc F .


Tha s cu trc khng ph thuc vo hnh dng v kch thc c
bn.
Tuy vy cng nhiu x khng ch ph thuc vo tha s cu trc m
cn vo cc tha s khc. V c th biu din bng biu thc tng qut sau:
156

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1 cos2 2
p
sin 2 cos

e 2

(3.17)

Trong : p L tha s lp.


e-2 L tha s nhit.
1+ cos2 2
Tha s Lorent.
sin2cos

3. ng dng ph nhiu x tia X phn tch thnh phn cu trc tinh th


Nhiu x tia X c s dng phn tch cu trc vt liu rn, mc
tinh th ha ca vt liu. Vt liu c th c cu trc tinh th, v nh hnh, thy
tinh hoc vt liu polymer. Trong mt s polymer, c bit l cc polymer si
n, chui c th sp xp thnh cc min c trt t. Cc min trt t ny
c gi l cc tinh th nh hay vi tinh th.
Zeolit
Zeolit t nhin v tng hp l alumosilicat c cu trc tinh th xc nh
vi cc l xp c kch thc u n. Cc l ny c ni thng vi nhau
bng nhng ng rnh cng c kch thc n nh to thnh mt h thng
l v ng rnh pht trin c kh nng hp ph cc phn t c kch thc
nh hn.
Zeolit cn c gi l "ry phn t".
Cng thc thc nhim ca zeolit nh sau:
M2/mO.Al2O3.nSiO2.pH2O
Trong : M cation kim loi ha tr m.
P s phn t H2O kt tinh.
to thnh tinh th zeolit cc t din SiO4/2 v AlO4/2 lin kt vi nhau
qua nguyn t Oxy. T s gia Si v Al l i lng quan trng.
Thng thng t l SiO4/2 v AlO4/2 = n.
Trong n s nguyn dng, n = 1, 2, 3...
Khi tng n bn ca cu trc zeolit tng. Nhng t din SiO4/2 v AlO4/2
l n v cu trc s cp. Nhng n v ny lin kt vi nhau to thnh n v
th cp. Hin nay tng hp v pht hin ra khong 7100 lai zeolit khc
nhau nhung trong thc t ch c khong 710 loi c ng dng tch cc, trong
cc loi quan trng nht l zeolit Y, X, v ZSM-5.
Cc zeolit X, Y c cu trc tng t vi cu trc ca fausasit l mt loi
zeolit t nhin. Zeolit X, Y c ng knh hc ln l 13Ao, th tch 811 A03,
ng knh ca s thng vi hc ln l 8-9 A0.
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157

n v cu trc th cp ca zeolit X, Y l nhng sodalit c to thnh


t 24 t din SiO2 v Al2O3.

nh 3.17: S cu trc mng tinh th zeolit Y:


Zeolit ZSM-5 tng hp khng c trong t nhin. T s SiO2 /Al2O3 rt ln,
thng l 90-100.
Thnh phn ha hc ca SZM-5 dng Na
NanAlnSi96-nO192.16H2O
Trong n < 27 (thng khong 3)
Hng s mang cc gi tr sau: a = 20.1, b = 19.9, c = 13.4 A0
Mng li khng gian ca ZSM-5 gm nhng h thng ng ct nhau to
thnh mng khng gian 3 chiu.

Hnh 3.18: Zeolit ZSM 5


Zeolit ZSM-5 hp ph c cc phn t n-parafin, o,p-xylen, 1,2,3trimetylbenzen, khng hp ph cc phn t ln, cng knh nh penta metyl
benzen, 1,2,3- trimetylbenzen.
Trong thc t ch c mt s lai zeolit t nhin v tng hp c s
dng rng ri trong cng nghip c bit l cng nghip ch bin du m v
158

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ha du nh zeolit X, zeolit Y, zeolit ZSM5,... mt s cc vt liu polymer cng


c cu trc rt c bit nh lai polymer tinh th lng.
Tn ti mt s loi polymer bao gm cc phn ht vi tinh th phn tn
trong nn v nh hnh.
V d: Cc chui PE (CH2 CH2)n hoc poly tetra fluoroetylen (CF2
CF2)n u c phn trm khi lng ln vi tinh th.
Kch thc ca cc vi tinh th ny c th xc nh bng s m rng ca
pic nhiu x.

Hnh 3.19: Vi tinh th trong polymer


Vt liu tinh th cho mt loi pic nt do tia nhiu x pht sinh t cc mt
phng mng khc nhau.
Vt liu v nh hnh cho pic m rng m v tr nh pic trng vi v tr pic
mnh quan st thy trong nh nhiu x ca vt liu tinh th ca cht .
V d: nh nhiu x ca SiO2 v nh hnh (thy tinh) v SiO2 tinh th
(cristo latite) c a ra trong hnh sau:

Hnh 3.20: Nhiu x tia X ca SiO2 tinh th (a) v SiO2 v nh hnh (b).

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159

Trong vt liu v nh hnh khng c trt t xa nh trong tinh th. Vt liu v


nh hnh ch c trt t gn.

Hnh 3.21: Trt t mng dng tinh th v dng v nh hnh.


4. nh lng thnh phn pha tinh th.
4.1.Cu to my nhiu x: gm 3 b phn chnh
-

Ngun to tia 10.

Detect tia 10.

B phn mu.

Hnh 3.23: Cc loi gi mu chp ph XRD

160

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Loi ng mao qun

Loi truyn qua


Loi phn x

Cc b phn ny nm trn chu vi ca vng trn tiu t (hnh 15). Gc


gia mt phng mu v gc tia ti l .
Gc gia phng chiu tia X v tia nhiu x l 2 .
Gin nhiu x theo hnh hc ny thng c gi l gin qut
0- 2 .
Trong ngun tia X c gia c nh cn detect chuyn ng sut
trong thang o gc.
Thang o 2 thng l t 0o 170o.
Thng thng ngi ta qut t 0o 140o.

Hnh 3.24: Hnh hc nhiu x k tia 10.


chp ph nhiu x tia X, mu thng c ch to dng bt vi
mc ch nhiu tinh th c nh hng ngu nhin v chc chn rng mt
s ln ht tha mn iu kin nhiu x Bragg n n
2d sin .
4.2. Phng php Rnghen dng bt phn tch cu trc vt liu
Mu vt liu dng rn
Mu c nghin nh c 1,0 3,0m v c to di dng lp mng
vi miligram trn phng. Kch thc bt c nh hng n sai s ca
cng peak. sai s ny nh hn1% i hi phi nghin vt liu n
kch thc ht c 0,5 1m. Trong thc t t kch thc ht ny rt kh
thc hin, cho nn thng th kch thc ht t khong 1 - 5m l kh thi v
sai s trong trng hp ny cho php l khong 5% c th chp nhn
dng phn tch nh lng.
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161

S ng u ca kch thc ht cng c ngha quan trng khi chm tia


X chiu vo mt phng cha mu, m bo s sp xp ngu nhin m phn
ln cc tinh th tun theo nh lut Bragg.
Tia X c chiu ti vi cng tia nhiu x c thu bng detector,
b chun trc c t trn ng tia to tia mnh v tch t. B lc n
sc thng l tinh th.
Mu c quay vi tc
Cng tia nhiu x 2

. Detector quay quanh vi vn tc 2 .

c ghi t ng trn giy v v tn hiu c x

l bng my vi tnh cho ngay kt qu.


Hnh hc v kch thc n v c th xc nh t v tr gc ca cc pic
nhiu x, cn s sp xp ca cc nguyn t trong n v lin quan n
cng tng i ca cc pc.
Trong ph nhiu x Rnghen bt c th xc nh thnh phn cc pha
ha hc ca mu phn tch v cc dng tn ti ca cng mt hp cht v nh
lng cc pha.
Mi pha gm mt mng nht nh v cho mt h vch nhiu x tng
ng trn gin nhiu x.
Nu mu gm nhiu pha th trn gin nhiu x s tn ti ng thi nhiu
h vch c lp vi nhau.
S c mt ca cc vch nhiu x c trng l c s xc nh nh
tnh pha c trong mu.
4.3. Phn tch nh lng bng ph nhiu x tia X
Da vo s ph thuc cng nhiu x v nng pha theo biu thc
sau:
I=K

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

Cc pha cha bit trong vt liu c th xc nh bng cch so snh s


liu nhn c t gin nhiu x thc nghim vi s liu chun trong ti
liu tham kho.
162

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Trong gin nhiu x, v tr pc ni ln cu trc v i xng ca pha,


cn cng pc phn nh tng ca cc pha nhiu x t mi mt phng
trong pha tinh th v ph thuc trc tip vo s phn b ca nguyn t trong
cu trc tinh th.
Nh vy cng pc khng nhng ch lin quan n thnh phn nh
lng pha m cn cu trc ca pha.
4.4. o cng vch ph
Vic o c cng vch ph trong phn tch nh lng rt quan
trng v ph thuc vo cc yu t sau:
nhy cu trc
nhy ca thit b
-

nhy ca mu o
nhy ca php o

Tt c cc yu t ny phn ln u cha trong tha s K hkl cu trc


mng.
Cng nhiu x lin quan n thnh phn pha, cu trc tinh th ca
pha v c biu din qua biu thc sau:
I

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

X - t s gia khi lng v th tch ca phn on.

- 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

4.5. Phng php inh lng da trn t l cng nhiu x


Phng php hp th nhiu x
Da trn t s cng ca pha trong mu phn tch v trong mu tinh
khit chun theo biu thc sau:
I ( hkl )
I

( / )
( / )s

o
( hkl )

(3.20)

Trong :
I o - cng ca pc trong pha tinh khit.

I - cng ca pc trong mu phn tch.


( / ) - h s hp ph khi trong hn hp.

Trong nhiu trng hp h s ny thng kh xc nh nn n gin,


h s ny c coi nh trong pha cn xc nh. Khi biu thc trn c th
vit n gin nh sau:
X

I ( hkl )
I o ( hkl )

(3.21)

Trng hp vi hn hp 2 pha h s hp ph khi (/) cho mi


pha tinh khit c bit trc, cho php tnh ton hm lng mi pha m
khng cn h s (/)s bi biu thc sau:

164

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( I ( hkl ) / I o ( hkl ) )( / )
( / ) ( I ( hkl ) / I o ( hkl ) ) ( / )

( / )

(3.22)

Biu thc ny c gi l biu thc Klug. Ni chung phng php ny


i hi h s hp ph khi ca mu phi c bit trc. Do vy, nu dng
phng php ny nh lng pha s c sai s ng k.
Trong ti liu c th tra cu h s ny theo tha s tn x nu ha hc
ca mu phn tch c bit r.
4.6. Phng php chun ni
Phng php chun ni l phng php ph bin nht nh lng
pha trong phn tch bng XRD. Phng php ny s loi tr c vn v
h s hp ph khi bng cch chia cng ca mi pha cho nhau ( v )
I ( hkl )
I ( hkl )

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 .

Hnh 3.25. th chun ni


Phng php ny i hi dng ng chun mt cch cn thn v c
th nh lng mt pha no khng ph thuc vo nhng pha khc c trong
mu.
Cn phi chn cc pic chun r rng, khng b chng ln v kch thc
ht ca mu phn tch phi ging nhau i vi mu chun v mu phn tch,
thch hp nht l khong 1m.
4.7. Phng php so snh cng nhiu x vi cht chun l
Corundum (Al2O3). (Saphia hng ngc) I/Icorundum
Phng php ny i hi dng Corundum l pha t l 50/50 so vi mu
phn tch v dng th ca biu thc

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165

X (

I ( hkl )
I ( hkl )

) theo X s thu c mt ng thng vi h s gc l K

Hnh 3.26. th ng chun theo cht chun Corundum Al2O3.


Kch thc ca corundum ti u l 1m.
Trong thc t c th dng cng thc tng qut xc nh pha trong
vt liu so vi pha chun theo cng thc sau
I ( hkl )

RIR

I ( hkl )

I rel ( hkl )
I

rel
( hkl )

X
X

(3.24)

Trong Irel - t l ca pic no s dng trong ph XRD.Nu 100%


peak trong ph XRD c s dng th gi tr ca t l ny l 1.
i lng RIR c th xc nh bng thc nghim cho bt k pha no khi
s dng bt k vt liu no lm cht chun:
Al2O3 (corundum), SiO2 (thch anh) thng s dng lm cht chun n1.
ZnO l cht chun ph bin vi nhng pc r rng.
chun ha phng php RIR, Chung(1974) nhn thy rng nu tt
c cc pha trong hn hp c bit v nu RIRs cng c xc nh, c th
dng biu thc sau tnh ton khi lng ca pha cn bit

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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trong. Vch so snh cn c th kch thch gn vi vch nghin cu,ngha l


chng c di sng bng nhau.
T l cng vch nguyn t cn xc nh v vch cht chun theo
biu thc sau:
I nc
I ch

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.

Phng php Rnghen c th p dng xc nh cc nguyn t c


nng ln (hng chc phn trm > 10%) hoc nng nh (2 10%), sai s
trung bnh ca phng php l 2 5%.
5. Phn tch cu trc pha
Phng trnh nhiu x tia X c th xc nh c cu trc vt rn tinh
th. Vic phn tch cc s liu nhiu x thng rt phc tp v tnh a dng
ca vt liu. V vy vic phn tch cu trc ch kho st trong trng hp vt
liu tinh th c cu trc n gin da trn tinh th lp phng.
S sp xp cc nguyn t hay n v quyt nh cng ca pic, cn
kch thc v hnh dng ca n v quyt nh v tr gc ca pic.
Vic xc nh cu trc tinh th cha bit gm cc bc sau:
Tnh kch thc v hnh dng n v t v tr ca pic nhiu x.
-

Tnh s nguyn t thuc n v v hnh dng ca n v, thnh


phn ha hc ca mu v mt o c ca n.
Suy ra cc v tr nguyn t thuc n v t cng ca pic.
5.1. Xc nh ch s Miller
Khong cch gia cc mt phng d, khang cch gia cc mt ln cn
trong mt phng hkl vi cc thng s mng a ca vt liu c cu trc lp
phng c th c xc nh t phng trrnh:
1
d2

h2

k2
a2

l2

(3.27)

Kt hp phng trnh Bragg vi phng trnh trn ta c:


h2

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

K l mt hng s cho bt k nh nhiu x no.

4a 2

Khi gc

tng, mt phng vi ch s Miller ln hn s tham gia nhiu x

c th vit theo phng trnh sau:


sin 2 Q1
sin 2 Q2

h12
h2 2

k12 l12
k2 2 l2 2

(3.30)

Trong h lp phng i vi mng lp phng, phn x bc nht do


phn x t cc mt vi ch s Miller kiu:
-

(100) cho lp phng n gin

(110) cho lp phng tm khi


(111) cho lp phng tm mt

Tng ng vi tng h 2

l 2 = 1, 2, hoc 3.

Bng cch chia cc gi tr sin2

ca cc phn x khc nhau cho sin2

ca cc phn x bc nht v nhn cc t s thu c vi s nguyn thch hp


thng l 2 hoc 3 s thu c cc gi tr ca hkl tng ng.
Bng 3.7: Dng tng bnh phng ca mt s ch s Miller cho h lp
phng.
h2

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

5.2. Nhn bit mng Bravais


Theo qui tc chn la gi tr h 2

l 2 cho mng lp phng tun theo

qui lut sau.


n gin: 1, 2, 3, 4, 5, 6, 8, 9,
Tm khi: 2, 4, 6, 8,10, 12,
Tm mt: 2, 4, 8, 11, 12, 16, 19, 20,
Mng Bravais v cu trc tinh th c th nhn bit c t trnh t cc
gi tr h 2

l 2 trong nh nhiu x.

Bng 3.8: Qui tc chn la cho phn x.


Mng Bravais

C phn x

n gin
Tm khi

Tt c cc mt

Tm mt

Khng c phn x
Khng

l - chn
2

h, k, l cng chn hoc cng

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

V d: tnh ton thng s mng ca nguyn t Al

Hnh 3.27.Ph nhiu x ca Al


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169

Ta c th t

4a 2

= A v y l hng s cho bt k nh nhiu x no.

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

Nh bng trn tnh ton cho thy ch c cc phn x vi cc gi tr hkl


chn c hoc l c l hin din. Theo quy tc chn lc c th kt lun rng
mng Bravais l LPTM v cu trc tinh th l cu trc LPTM.
5.3. Kch thc tinh th
i vi nhng tinh th kch thc ln (khong 1000 n v c s), ph
nhiu x th hin bng nhng pc nhiu x v tr gn gc Bragg. Cn nhng
pc khc b trit tiu khng th hin trn ph nhiu x.
i vi nhng tinh th c kch thc nh (khong 1 m) c th dng cng
thc Sherrer tnh ton kch thc tht t ph nhiu x nh sau
D

Trong :

K
D cos

- chiu rng na pc

K - h s hnh th (thng khong 0,9)


- bc sng pht x

170

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(3.31)

Quan h gia b rng pc nhiu x thu c trn ph v kch thc ht


nh sau

Hnh 3.28. th ph thuc dong pc v cng nhiu x


6. c trng ph XRD ca mt s vt liu
C th ni khong 90% vt liu rn v c nhn to hoc t nhin c cu
trc tinh th.Trong s cc nhm vt liu khong v vt liu xc tc cho ngnh
cng nghip du kh v cc ngnh khc thung c s dng l cc nhm
sau.
Vt liu khong st
Vt liu zeolit
Vt liu kim loi v oxit kim loi
Sau dy l mt s th d v cc ph c trng ca chng.
6.1. Nhm vt liu khong st

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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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Hnh 3.28: Ph XRD ca vt liu canxit, ngun pht CuK

Hnh 3.29: Ph XRD ca vt liu khong Ilit

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173

Hnh 3.30: Ph XRD ca vt liu thch anh

Hnh 3.31: Ph XRD ca vt liu Analcim


6.2. Nhm vt liu zeolit

174

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Hnh 3.32: Ph XRD ca vt liu zeolit Li-ABW


Cng thc ho hc: [Li4(H2O)4][Si4Al4O16]
Thng s mng c s:
a =10,313 Ao
b=8,914 Ao
c= 4,993 Ao
Gc alpha =90o, beta =90,o gama =90 o

Hnh 3.33:Ph XRD ca vt liu Zeolit AlPO-18


Cng thc ho hc: Al24P24O96
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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

Hnh 3.34:Ph XRD ca vt liu AFG


Cng thc ho hc: [ Na 17K4.7 Ca 10](SO4)6 [Si24Al24O96]
Thng s mng c s:
a = 12.76 Ao
b= 12.76 Ao
c= 21.41 Ao
Gc alpha =90o, beta =90,o gama =120 o
Cng thc ho hc: [C2H8N2)(H2O)16[Al24P24O96]
Thng s mng c s:
a = 10.321 Ao
b= 13.631 Ao
c= 17.454 Ao
Gc alpha =90o, beta =90,o gama =90 o

176

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Hnh 3.35:. Ph XRD ca vt liu ALPO-EN3

Hnh 3.36: Ph XRD ca vt liu euo


Cng thc ho hc: [H2O]36[Si112O224]
Thng s mng c s:
a = 13.695 Ao
b= 22.326 Ao
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177

c= 20.178 Ao
Gc alpha =90o, beta =90,o gama =90 o

Hnh 3.37: Ph XRD ca vt liu MON


Cng thc ho hc: [ Na 0.1K4.3 (H2O)5[Si11Al4.7O32]
Thng s mng c s:
a = 7.41 Ao
b= 7.41 Ao
c= 17.307Ao
Gc alpha =90o, beta =90,o gama =90 o
6.3. Nhm vt liu kim loi v oxit kim loi.

Hnh 3.38: Ph XRD ca kim loi Zn vi bc x CuK


178

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Hnh 3.39: Ph XRD ca vt liu TiO2 bc x CuK


7. Thc hnh chp ph XRD ca vt liu xc tc phng php rnghen
bt
Mc ch: Gip hc vin nm vng cch chun b mu o, cch thao tc
vn hnh trn my XRD v gii c cc ph , tnh ton thnh phn pha v
xc nh cu trc pha.
nh gi kt qu phn tch, vit bo co th nghim.
7.1. Cc cng vic chun b
7.1.1. Thit b o ph vi cc cu hnh gm
-

ng pht tia X, b lc sng.

Gi mu, thu tinh mu.


B nhn tn hiu v khuch i tn hiu.
B phn x l s liu.
7.1.2. Dng c, ho cht, ti liu tra cu
Kh N2, H2.
Ci nghin mu (ci m no).
Bnh ht m.
Cc mu vt liu chun v cc mu phn tch.
B ti liu tra cu thng s (ATLAS XRD ASTM).
7.2. Tin hnh th nghim
7.2.1. Chun b mu bt phn tch
-

Nghin nh mu phn tch sao cho t mn khong 1 - 5 m.

Cho mt lp mng mu bt v dn tht u trn mt knh lm gi

, sau t vo hp mu phn tch trn my.


7.2.2. Tin hnh chp ph XRD

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179

Trc tin phi kim tra an ton v tnh trng hot ng ca my,

kim tra in v kh.


Kim tra ng pht tia X, dng ngun pht t kim loi no bit r
bc sng ti ( ). Thng thng dng ngun l CuK vi

= 1,54

M my chy vo ch lm vic v ci t cc thng s theo


hng dn thao tc vn hnh ca tng loi my (ch c k

hng dn trc khi thao tc).


my n nh.

Tin hnh chp ph XRD ca cc mu phn tch theo gc 2 t 0

60 (hoc hn tu theo mc ch).


Chp ph XRD ca cc mu chun theo trnh t trn trong cng
iu kin nh nhau.
Kt thc php o v thu nhn cc ph .

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

liu gio trnh


Kch thc ht tinh th theo cng thc Sherrer.
Xc nh cu trc pha tinh th.
Tnh ton thng s mng t cc s liu ca ph theo cng thc
nh trnh by trn khi bit v tr ca cc peak (gc 2 ). T

tnh c cc thng s mng hkl (ch s Miller) v xc nh cu trc


tinh th ca vt liu.
Xc nh cng tng i ca cc peak trong ph v nh tnh,

nh lng cc pha trong mu.


Vit phiu nh gi thc hnh (theo mu).
Bng tng kt thc hnh phn tch xc nh cu trc v thnh phn pha
Tn mu

A (nm)

h2 + k2 + l2

hkl

Vit bi thc hnh v cc ch thch trong qu trnh thao tc


Nhn xt v quan h gia cng pic v thng s mng
Nhn xt v phn gii ca cc pic
8. Cu hi bi tp gii ph nhiu x tia X

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.

Ph XRD ca kim loi Pb chp theo phng php bt vi bc x CuK


( =1.539 Ao). Tnh gi tr ca khong cch mt mng tinh th theo cc
ng bc 1 v gc l

2.

=67.1 o
l

Ph XRD ca vt liu c cc pc nhiu x tng ng vi gc

24.3;23.4;21;v 17.5. Dng ng pht tia l Cu c bc sng l ( =1.539


Ao) Hy tnh phong cch mt phng d cc gc nhiu x theo phng
trnh Bragg.
3.

Tnh chiu di cng tinh th dng LPTK ca Fe bit rng ph XRD vi


=2Ao. o khong cch mt cho tinh th (110) c gc =30o

4.

Tnh gc 2 ca gic k khi vch K ca cc nguyn t Fe (1.76 A0)


Se(0.992 A0) Ag (0.497 A0) vi cc tinh th phn tch l:
a. Topaz d= 1.356
b. LiF d=2.014

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/

= (6,63.10-34x3,0.1010) /5.109 = 4.10-15 Jun

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

Bi 2: Ph hp thu nguyn t (AAS)


Cu 6
Phng ca tia = 300 nm (m = 1) ng thi trng chp phng ca tia
= 150 nm (m = 2). Vy c tia 300 nm thun khit phi dng thm knh lc
thch hp gi li tia 150 nm.
Trong my n sc cch t u c thm knh lc gi li cc tia thuc
bc nhiu x khc.
Cu 7
Nhn xt: Gc nghing
ngoi, cn gc nghing

2=

= 12,30 thch hp khi phn gii ph vng t

32,50 thch hp khi phn gii ph vng kh kin.

Vic s dng cch t kp va nng cao hiu nng phn gii ph va


tn mt cch t na.
Cu 8
f= 347 mm
Bi 3: Ph nhiu x tia X (XRD)
Cu 1
d=0.8109Ao
Cu 2
o

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

Tinh th phn tch Topar


i vi Se: 2 = 42,90

184

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i vi Ag: 2 = 21,10
b.

Tnh tng t cho tinh th phn tch l LiF


Ta c kt qu sau
2 : Fe = 31,80
Se = 28,50
Ag = 14,20

c.

Tinh th phn tch NaCl


2

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

17714, 3V 17, 7143KV

12400
0, 7

17714, 3V 17, 7143KV

20, 9459 KV

25 KV

Cu 6

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185

CC THUT NG CHUYN MN V CC CH VIT TT


IR - InfraRed spectroscopy -Quang ph hng ngoi
XRD X-ray Diffraction spectroscopy Ph nhiu x tia X.
AAS Atomic Absorption Spectroscopy Ph hp thu nguyn t.
ASTM - The Americal Society for tesying and materials.
HSX h s xp.
LPG Lp phng n gin.
PLTK - Lp phng tm khi.
LPTM Lp phng tm mt
SPXC - su phng xp cht.
Bn knh
:
r, R
Bc sng

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

TI LIU THAM KHO


1.
2.

Nguyn nh Triu, Nguyn nh Thnh - Cc phng php phn tch


Vt l v Ho l, NXB KHKT, H ni 2001
T Vn Mc - Phn tch dng c - NXB KH&KT, H ni 1999.

3.

Nguyn Hu nh, Trn th - ng dng mt s phng php ph


nghin cu cu trc phn t - NXB Gio dc, H ni 1999.

4.

Analytical Method for Atomic absorption spectroscopy, The perkin Elmer


Coproration, 1996.

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.

Janusz Ryczkowski - IR spectroscopy in Catalysis - Catal. Today, 68,


263-381, 2001
Roeges - A guide to the Complete interpretation of IR of Organic

strucrure - Wiley Chichester, 1994.


9. http://Zeolites.ethz.ch.
10. James R. Connolly - Introduction to X-ray Powder diffraction - EPS 400 002 , 2005

188

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