VIT QU

II II II IINI III III III III II

.0000022498

CAGPHUONGPHAP
PHNTCHCNGcu

N H X U T BN I H C s P H A M

GS.TS H VIT QU

CC PHNG PHP
PHN TCH CNG c

TRONG HO HC HIN I

NH XUT BN I HC s PHM

MC LC
Li ni u ................................................................................................................................. 7
Chng 1. K hoa hc phn tch v h th ng cc phng p hp nghin cu . 11
1. Khoa hc phn tch (ngnh phn tch hin i)
v phng hng pht tri n .........................................................................................11
2. H thng cc phng php phn tch....................................................................... 12
3. Ho hc phn tch v vai tr ca n
trong ngnh Phn tc h ................................................................................................. 17

Chng 2. i cng v p h v cc phng p hp p h ....................................... 51

1. Bc x in t................................................................................................................ 51
2. Cc phng php quang ph..................................................................................... 53
3. Cc phng php t hp gia phn chia v xc nh c h t................................. 67

Chng 3. Phn tch l h o ................................................................................................ 69

1. Cc phng php phn tch cng cu v tn hiu phn tch.................................. 69
2. Phn tch o quang phn t ....................................................................................... 70
3. Cc phng php phn tch in ho....................................................................... 92
4. Mt s phng php phn tch, phn chia, lm giu..........................................136

Chng 4. C c phng php o quang nguyn t

vng p h U V - V IS ......................................................................................... 187
1. c im chung ca nhm phng php o quang
nguyn t vng U V -V IS ........................................................................................... 187
2. Phng php o ph pht xa nguyn t................................................................192
3. Phng php o ph hp th nguyn t .............................................................. 203
4. So snh php o ph hp thu nguyn t
v php o ph pht xa nguyn t ........................................................................ 216
5. Php o ph hunh quang nguyn t ................................................................... 218
6. Cc phng php o ph nguyn t khng dng ngon l a................................... 223

Chng 5. Phng p hp o p h hng ngoi ( IR ) .................................................229

1. c im ca phng php o ph hng n g o i..................................................229
2 C s l thuyt ca phng php.............................................................................229
3. K thut thc n g h i m .................................................................................................. 248
4 Cc yu t nh hng lm dich chuyn tn s c tr n g ................................. 250
5. Mt s v du c th v cc dao ng cd bn ca mt s phn t,
mt s nhm trong ph IR ....................................................................................... 254

6. Phn tch nh tnh v phn tch nh lng bng cch o ph I R ..................258

7. ng dng ca php o ph hng n g o a i.................................................................261

Chng 6. Phng p hp o p h tn x t hp (p h R a m a n ).......................... 263

1. Hin tng tn xa t h p ........................................................................................... 263
2 Ph k R am an.............................................................................................................. 271
3. Phn tch nh tnh v nh lng trong php o ph R a m a n ...........................271
4. ng dng ca php o ph R am an......................................................................... 272

Chng 7. Phng php o p h hp th electro n

(ph kch thch electron vng U V -V IS ).................................................... 275
1 C s l thuyt ca phng php o ph U V -V IS ............................................... 276
2. K thut thc nghim .................................................................................................. 290
3. ng dung ca php o ph hp th e le c tro n ....................................................... 295

Chng 8. Phng php o p h hunh quan g

v ln quan g phn t ................................................................................... 309
1. C s li thuyt ca phng p h p ............................................................................. 309
2. KT thut thc nghim .................................................................................................. 320
3. Tiu chun nh gi nhy ca phn ng hunh quang..................................... 323
4. ng dung ca php o ph hunh quan g...............................................................324
5. Gii thiu v s pht quang ho h c.........................................................................329

Chng 9. Phng p h p o p h c ng hng t h t n h n ................................ 331

1. Phn loi cc phng php vt l ng dng trong ho h o c ..................................... 331
2. Nhng u vit ca cc phng php phn tch vt l
dng trong ho h c ....................................................................................................332
3. C s l thuyt ca php o ph N M R ................................................................... 333
4. KT thut thc nghim ca php o ph N M R ....................................................... 345
5. dich chuyn ho h c ............................................................................................ 351
6. Tng tc spin - s p in ................................................................................................. 365
7. ng cong tch phn tn h i u ................................................................................. 372
8. Phn tch ph NMR phn gii c a o .......................................................................... 374
9. Ph NMR ca cc hat nhn khc ht nhn hiro (1H ) ....................................... 379
10. Cc loai ph NMR 2 chiu (2D -N M R ), ph NDE (1D),
ph NOESY (2D), 3 chiu (3D -N M R ) v 4 chiu (4 D -N M R )..................

381

11. ng dung ca php o ph N M R ......................................................................... 382

Chng 10. Phng p hp o p h cng hng spin e le c tro n .......................... 383

1. C s l thuyt ca phng p h p ...................................................................

383

2 ng dung ph E S R ............................................................................................

395

Chng 11. Phng php o p h khi l n g ........................................................ 397

1. c im ca phng p h p .....................................................................................397
2. Nguyn tc chung ca phng php
(phng php ion ho bng va chm electron)...................................................398
3. K thut thc nghim .................................................................................................. 400
4. Phn loi cc io n ........................................................................................................406
5. C ch phn m n h .................................................................................................... 413
6. Ph khi lng ca mt s hp c h t...................................................................... 417
7. Mt s v du v phng php phn tch ph khi lng............................................. 426
8. ng dng ca php o ph khi lng.................................................................. 438

Chng 12. Phng php o ph tia X (tia R n g h en )........................................ 441

1. c im ca phng p h p ..................................................................................... 441
2. C s l thuyt ca cc phng php o ph tia X .............................................. 442
3. Php o ph hp th tia X. S tng tc ca tia X vi vt c h t...................... 451
4. Tia X nghin cu cu to mang tinh th .......................................................... 453
5. Nguyn li cu to ph k R nghen........................................................................ 454
6. Phng php ph nhiu xa tia X .............................................................................458
7. Phng php o ph hunh quang tia X ...............................................................466
8. ng dung chung ca php o ph tia X ................................................................. 471

Chng 13. Phng p hp kch hot p hng x .......................................................473

1. Bn cht ca phng p h p ...................................................................................... 473
2. Phng php kch hot phng xa trc ti p ........................................................... 473
3. Phng php kch hoat phng xa gin t i p .......................................................... 473
4 Hot dng phng xa t n h i n ...................................................................................473
5. Bin i phng xa nhn t o ..................................................................................... 474
6 Chu k bn phn h y .................................................................................................. 474
7. Tia y .......................... ..................................................................................................... 475
8 Xc inh nh tinh v inh lng.............................................................................475
9 th c h u n ................................................................................................................ 476
10. Xc inh theo chu k bn phn h y ......................................................................477
11. Phng php pha long ng v phng x a .........................................................477
12. Phn tch da theo kh nng ca cc nguyn t pht x tia p ........................478
13. Chun hoat ng phng x a .............................................................................. 479
14. Bc xa hoat ho bng cc ngun c nng lng l n ....................................... 480
15. Phn tch cc nguyn t t him bng phng php
kch hoat ntron........................................................................................................484

Chng 14. Phng p hp phn tch nhit

(nhit khi lng, nhit vi phn, nhit qut vi phn,

nhit c hc, phn tch kh thot ra )................................................... 487
1 Phn tch nhit khi lng (Thermogravimetry T G )............................................487

2 Phn tch nhit vi phn (DTA) v php o nhit lng

qut VI phn ( D S C ) ................. ...................................................................................... *"'

3 Phn tch nhit c h o c ........................................................................... ..................... 503
4 Phn tch kh tch ra ................................................................................. ...................509

Chng 15. P hp o ph p ht x tia X .......................................................................515

1 Nguyn tc ca phng php o ph pht xa tia X ...............................

515

2 Thit b ............................................................................................................................516
3 ng dung........................................................................................................................ 516
4 Cc nguyn t c ............................................................................................................ 516
5 Ki thut thc nghim .................................................................................................... 519

Chng 16. P hp o ph p lasm a cm ng t h p ............................................... 523

1. Nguyn tc ca phng p h a p ................................................................................... 523
2 Plasma cm ng t h p.............................................................................................. 523
3. Php o ph plasma cm ng t hp - ph khi lng..................................... 523
4 Cc nguyn t c ............................................................................................................ 524
5. Thit b| plasma cm ng t hp................................................................................525
6. Php o ph plasma cm ng t hp - khi p h ................................................ 527
7 ng dung........................................................................................................................ 529

Chng 17. C c phng php t hp gia tch - xc nh hp c h t .......... 531

1 Gii php t h p ........................................................................................................... 531
2 Chin lc phn tch t h p .......................................................................................532
3 Cch gii quyt vn ............................................................................................... 532
4. Cc u vit ca cc phng php (k thut) t h p .............................................533
5 Bin php t h p .......................................................................................................... 533
6 Gii quyt vn .................................................................................

534

7. Cc u th ...................................................................................................................... 535
8 Sc k kh - ph hng ngoai (Gc - IR /S )....................................................

536

9 Sc k lng - ph khi lng (Lc - M S )..........................................

542

10. Php o ph plasma cm ng t hp - ph khi lng (ICP - MS)

545

11 Cc phng php t hp gia chit v cc phng php xc inh

546

Chng 18. Kt hp cc phng php ph nhn bit

v xc nh cu trc phn t .................................................................. 5 5 5
1. Nhn bit v xc inh cu true phn t
t vi c kt hp cc phng php p h .............................................

555

2 Mt s nguyn tc ca phng php gii p h ...............................

ec;5

3 PQ dung..................................................................................................

55 '

Ti liu tham k h o ................................................................................................................55C

LI NI U

Cc phng php phn tch cng c bao gm cc phng php

phn tch l - ho v cc phng php phn tch vt l ng dng trong
Ho hc hin i. Trong cc phng php phn tch cng c, Ton hc,
Tin hc ng vai tr cc k quan trng. Chng gip cho vic x l thng k
kt qu, m hnh ho, k hoch ho, ti u ho thc nghim, tnh kt qu ,
x l th, tnh sai s phn tch ...

Cc phng php phn tch cng c l gio trnh phc v cho cc

h o to C nhn (h chnh quy, ti nng, ti chc, chuyn tu), Thc s,
Tin s Ho hc trong nhiu trng i hc v Cao ng ca nhiu
ngnh o to khc nhau.
Gio trnh ny c a vo chng trnh o to Thc s v Tin s,
C nhn cc h t nm 1991. Nh xut bn i hc Quc gia H Ni
xut bn ln u nm 1998, gio trnh phc v kp thi vic o to
cc h o to ni trn.
T nm 1991 n nay, trong lnh vc cc phng php phn tch
cng c xu t hin nhiu phng php, cc k thut phn tch hin
i, c hiu qu cao trong phn tch nh tnh, nh lng, cu trc,
v d k thut bin i Fourier (Fourier Transform ation = FT) trong cc
phng php F T - IR/S; FT - Ram an/S ; FT - MS; FT - NMR/S, cc th
h p h k NM R t 500MHz n 800MHz, a xung , a chiu, kh tng
tc, 1, 2, 3, 4 chiu (1D - NMR, 2D - NMR, 3D - NMR, 4D - N M R ,...)
cho php tng tn hiu o, gim tn hiu nhiu, gim sai s, tng phn

gii, nhy, chn lc, chnh xc; hu nh trong nhiu trng hp

khng cn phi tch trc cc cu t cn tr trong mu phn tch, tit
kim c cng sc, gim thi gian phn tch... m t hiu qu phn
tch cao.
X u t hin nhiu k thut, nhiu phng php t hp (com bined
technigues, m ethods) gia cc phng php tch v phng p h p xc
nh hm lng cht nh: sc k kh (lng) - p h khi lng, p h hng
ngoi bin i F o urie r (G c - FT/M S; Gc - FT/IR; Lc - FT/M S ; Lc FT/IR), phng php tim mu vo trong dng chy (FIA = Flow
Injection A nalysis), chit - trc quang (hunh quang, cc ph), o
hot phng x, chun , p h plasm a cm ng t hp - p h khi
lng (ICP - MS = Ind u ctively Coupled plasma - Mass Spectrom etry)...
cho php va tch c cc cu phn t hn hp mu va xc nh c
hm lng ca chng. Ngy nay, trong Ho hc hin i, vic xc nh
hm lng ln v trung bnh l vn c gii quyt, cc phng php
phn tch cng c cho php xc nh c hm lng vt, siu vt (v d,
IC P -M S , AAS, A FS...).
Gio trnh Cc p h n g p h p p h n tch c n g c tro n g H o h c
h i n i gm 18 chng, cp m t cch ton din cc phng php
phn tch l - ho (phn tch quang hc, phn tch in ho. phn tch
phn t, phn tch nguyn t...), cc phng php phn tch vt l (cc
phng php phn tch quang p h , p h hp th electron vng U V -V IS
p h hunh quang, ln quang phn t, p h hp th. p h t xa. hunh
quang , tia X nguyn t, p h plasm a nguyn t, p h huynh quang, p h
Raman, p h khi lng, p h cng hng t ht nhn (NMR. PMR). p h
hp th, nhiu x, hunh quang tia X), cc phng php tch, phn
chia , lm giu.
Cc phng php phn tch sc k: sc k khi (rn, lng), sc ki lng
(rn, lng), sc ki bn mng, sc k giy, sc k gel (sc k ry phn t)
sc ki trao i ion , sc ki in di, sc ki mao qun...

Cc phng php chit bng dung m i hu c, chit pha rn..

Cc phng php tch bng in ho, kt ta, chng ct, thng h o a ..
Qua 28 nm o to h Sau i hc trc y v h Cao hc
(hin nay), tc gi thy cn p h i bin son gio trnh ny mc hin
i, cp nht c th c nhm phc v cc h o to C nhn (c
bit h C nhn cht lng cao), h o to Thc s v Tin s Ho hc
vi cht lng ngy cng tng.
Tc gi mong mun nhn c s gp , b sung ca bn c,
ng nghip ln xut bn sau cht lng gio trnh cng tt hn, phc
v c hiu qu hn s nghip o to, nghin cu khoa hc, bi dng
cn b...
Tc gi xin chn thnh cm n.

TC GI

Chng 1
KHOA HC PHN TCH V H TH N G
CC PHNG PHP NGHIN cu

1. Khoa hc phn tch (ngnh phn tch hin i)

v phng hng pht trin

Trong cng tc nghin cu khoa hc. ging dy t bc i

hc, trn i hc, n g n h Ho hc phi c tra n g b cc phng
php phn tch c hiu qu cao nhm phc v cho cc mc ch
nh: nh n bit cht, xc nh hm lng cht, c bit hm
lng vt. siu vt (c ppm. c ppb...). xc nh cu trc phn
t. tinh ch. iu ch cc hp cht siu tinh khit dng trong k
th u t cao nh bn dn. siu bn dn. cng nh tinh vi...
Ngy nay. trong Ho hc hin i v ang s dng nhiu
phng php phn tch ho hc, phn tch l ho, phn tch vt l
(thng i l phng php phn tch cng c), s dng ton
hc. tin hc x l s liu thc nghim (ton thng k), ti
u ho thc nghim, k hoch ho. m hnh ho thc nghim,
nghin cu co' ch ph n ng, xc nh cc tham s' nh lng
cc hp cht to th n h ...
Nh vy. do s kt hp hu c gia Ho hc. Vt l. Ton
hc. mt s khoa hc khc nh Sinh hc. Dc hc. Y hc. a l.
a cht. Mi trng. Kho c hc v.v... ra i Khoa hc
phn tch, tc ra i ngnh Phn tch hin i phc v c hiu
qu cho nghin cu khoa hc. ging dy Ho hc. khai thc, s
dng ti nguyn... phc v tt cho cng cuc hin i ho. cng
nghip ho t nc.

11