CH3320

PHN TCH BNG CNG C

Phn 1. Cc phng php phn tch quang hc ................................................................... 2

Chng 1. M u ............................................................................................................... 2
1.1. M u ....................................................................................................................... 2
1.2. Tnh cht c bn ca bc x in t .......................................................................... 2
1.2.1. Tnh cht sng ca bc x in t ....................................................................... 3
1.2.2. Tnh cht ht ca bc x in t.......................................................................... 5
1.3. Ph bc x in t ..................................................................................................... 5
Chng 2. Phng php quang ph hp th nguyn t ...................................................... 6
2.1. S hnh thnh ph phn t ......................................................................................... 6
2.1.1. S hp th bc x in t v s hnh thnh cc loi ph hp th phn t ......... 6
2.1.2. Ph hp th.......................................................................................................... 7
2.2. nh lut c bn v hp th bc x in t ................................................................ 9
2.2.1. nh lut Lambert-Beer ........................................................................................ 9
2.2.2. Tnh cht cng tnh ca hp th quang ......................................................... 10
2.2.3. Cc yu t lm sai lch nh lut Lambert-Beer ................................................. 11
2.2.4. chnh xc ca php o hp th v php o nng ................................ 12
2.2.5. iu kin nng tin hnh phn tch o quang ........................................... 13
2.3. Cc th tc thc nghim trong phn tch o quang .................................................. 13
2.3.1. Phng php ng chun ............................................................................... 13
2.3.2. Phng php tnh .............................................................................................. 14
2.3.3. Phng php thm tiu chun ........................................................................... 14
2.4. Phng php o quang vi sai ................................................................................... 15
2.5. S thit b quang ph hp th phn t................................................................. 16
2.6. Mt s ng dng phng php o quang ................................................................ 20
2.6.1. Xc nh thnh phn phc cht trong dung dch bng phng php dy ng
phn t gam (phng php bin thin lin tc_Continuous Variation) ......................... 20
2.6.2. Xc nh thnh phn phc cht trong dung dch bng phng php ng cong
bo ha ........................................................................................................................ 22

Phn 1. Cc phng php phn tch quang hc

Chng 1. M u
1.1. M u
Trc kia, thut ng quang ph cp ti mt nhnh ca khoa hc nh sng ( l
cc bc x nhn thy) c phn gii thnh cc bc sng ca n to thnh ph, c biu
din di dng hm ca cng bc x v bc sng hoc tn s. Ngy nay, ngha c a
quang ph c m rng bao gm vic nghin cu khng ch trong vng trng thy m cn
cc loi ph in t khc, chng hn nh ph tia X, ph t ngoi, hng ngoi, sng viba v
radio. Thc t, vic s dng hin nay m rng ngha ca quang ph ra hn c vic bao gm
cc k thut m khng bao gm bc x in t, v d nh ph m thanh, ph khi v ph
in t.
Quang ph ng mt vai tr quan trng trong s pht trin l thuyt nguyn t hin i.
Ngoi ra, cc phng php ph ha cung cp cng c s dng rng ri cho vic d on cu
trc ca cc phn t phn t cng nh vic xc nh nh tnh v nh lng cc hp cht v
c v hu c.
Chng m u ny gii thiu cc tnh cht ca bc x in t v s tng tc a dng trong
vn ny
1.2. Tnh cht c bn ca bc x in t
Bc x in t l mt dng nng lng tn ti rt nhiu dng hnh thc, dng c th d
dng nhn ra l nh sng vng trng thy v bc x nhit. Biu hin t r rng hn bao g m
tia gamma, tia X, t ngoi, viba, v bc x tn s radio. Nhiu tnh cht ca bc x in t l
thun tin c m t bi m hnh c in dng sng hnh sin, ci m c s dng cc tham
s nh bc sng, tn s, vn tc v bin . Ngc vi hin tng sng, chng hn m
thanh, bc x in t khng i hi mi trng khi truyn v n c th d dng truyn qua
mi trng chn khng.
M hnh sng b li khi tnh ti hin tng hp th v pht x bc x in t. hiu cc qu
trnh ny, cn thit s dng m hnh ht, trong bc x in t c xem nh l mt dng
ca cc ht ri rc hay cc gi sng ca nng lng c gi l photon vi nng lng ca
mt photon t l vi tn s ca bc x. M hnh kp bc x va c tnh cht sng va c tnh
2

cht ht khng loi tr ln nhau m cn b sung cho nhau. Thc t, m hnh kp c tm

thy ng dng cho tnh cht ca cc dng in t v cc ht th cp chng hn nh proton
v m hnh kp l hon ton hp l vi c ch sng.
1.2.1. Tnh cht sng ca bc x in t

Hnh 1-1: Thnh phn in trng v t trng

Theo m hnh sng, bc x in t l nhng dao ng c hai thnh phn in trng v t

trng lm truyn theo mt phng. Cc thnh phn in trng v t trng vung gc vi
nhau v c biu din bng cc sng phn cc phng (hnh 1-1).
Cc tham s sng:
U

Cng A ca sng hnh sin c ch trn hnh v (1-1) v biu din l di ca vect
cc i ca sng.
Tn s l s dao ng m bc x in t thc hin trong mt giy.
Bc sng l qung ng gia hai im cn bng bt k m bc x in t i qua (khong
cch gia hai cc i hay cc tiu).
Vn tc truyn bc x in t vi (m/s) l tch s gia tn s v bc sng (tnh bng m):
vi =

(1-1)

Vn tc ca bc x in t ph thuc vo thnh phn ca mi trng m bc x in t i

qua. Ch s di din t mi trng m n truyn qua.

Trong mi trng chn khng, vn tc ca bc x in t tr nn khng ph thuc vo bc

sng v n t cc i. Vn tc ny c k hiu l c, v c xc nh bng 2,99792.10-8
m/s. iu ng ch l v n tc ca bc x in t trong khng kh ch khc rt t (khong
0,03% nh hn) vn tc nh sng trong chn khng. Trong cc trng hp ny phng trnh
(1-1) c th vit di dng:
c = = 3.00.108 m/s = 3,00.1010 cm/s

(1-2)

Trong cc mi trng khc, vn tc ca bc x in t b chm li do s tng tc gia

trng in t ca bc x v cc electron xung quanh cc nguyn t hay phn t c mt trong
mi trng. Do tn s ca bc x l bt bin v c nh bi ngun, bc sng s phi gim
khi bc x t mi trng chn khng sang mi trng khc. Hiu ng ny c minh ha
hnh 1-2 cho tia bc x vng trng thy. Ch l b c sng b ngn li gn 200 nm (hn
30%) khi i qua thy tinh v ngc li n li di ra khi bc x i ti mi trng khng kh.

Hnh 1.2. S thay i bc sng khi bxt truyn t khng kh qua thy tnh v truyn tr li
khng kh

S sng, , c nh ngha l nghch o ca bc sng (tnh bng n v cm) l mt cch

khc m t bc x in t. n v ca s sng l cm-1.

S sng c s dng rng ri trong ph hng ngoi. S sng l mt n v thun tin, v

ngc vi bc sng, n t l thun vi tn s (do vy t l vi nng lng) ca bc x. Nh
vy, ta c th vit:
= k

(1-3)

y, k l h s t l, ph thuc vo mi trng v v gi tr l nghch o ca vn tc.

V d: Tnh s sng ca tia bc x hng ngoi vi bc sng l 5,00 m.

5 104

= 2000 cm-1

1.2.2. Tnh cht ht ca bc x in t

Nng lng ca photon ph thuc vo tn s ca bc x v c a ra di dng:
E = h

(1-4)

y h l hng s Planck (h = 6,63.10-34J.s).

C th biu din nng lng ca photon di dng bc sng v s sng:
E=

= hc

(1-5)

Ch l s sng ging nh tn s, t l thun vi nng lng.

V d: Tnh nng lng photon (J) ca bc x in t nu bit = 2000 cm-1

p dng phng trnh (1-5):

E = hc = 6,63.10-34 (J.s) 3,00.1010

1.3. Ph bc x in t

2000 cm-1 = 3,98.10-20 (J)

Ph bc x in t l quen thuc vi bn hn bn ngh. L vi sng, bn s dng lm nng

thc phm ca bn v in thoi di ng m bn s dng l mt phn ca ph bc x in t.
nh sng m i mt ca bn c th nhn thy cng l mt phn ca quang ph in t. Mt
phn c th nhn thy c ca ph bc x in t bao gm cc mu sc m chng ta thy
trong cu vng - t mu v cam, n lam, chm v tm (hnh 1-3).

Hnh 1-3. Mi mt mu sc tng ng vi mt bc sng nh sng khc nhau

Cc sng ca ph bc x in t thay i di trong mt phm vi v cng rng, t bc

sng di nh kch thc ca ta nh l sng radio, n v cng ngn nh ht nhn ca mt
nguyn t l tia (hnh 1-4).

Hnh 1-4.Thang o bc x in t

Chng 2. Phng php quang ph hp th nguyn t

2.1. S hnh thnh ph phn t
2.1.1. S hp th bc x in t v s hnh thnh cc loi ph hp th phn t

Mt trong nhng khi nim quan trng t c hc lng t cn thit cho s hiu bit v s hp
ph hay pht x phn t l nng lng phi c lng t ha. Ni cch khc, cc phn t c
th tn ti cc trng thi lng t c th v mi trng thi lng t c gn mt nng
lng. Nng lng phn t c lu gi c th coi l tng nng lng lu tr ca ba dng:
quay, dao ng v in t.
Trong iu kin bnh th ng, cc phn t tn ti trng thi nng lng thp nht (nng
lng c bn). Khi phn t nhn nng lng, v d khi phn t hp th bc x in t, phn
t c th chuyn sang mc nng lng cao hn ng vi trng thi kch thch ca phn t.
Phn t ch tn ti trng thi kch thch trong khong thi gian rt ngn (10-6-10-9s) v quay
tr li trng thi c bn.
Qu trnh pht x l qu trnh mt phn t chuyn trng thi lng t cao hn sang thp hn
v thot ra mt photon. Qu trnh hp th l mt qu trnh mt phn t chuyn t trng thi
lng t thp hn sang cao hn v hp th mt photon.
S thay i trng thi lng t ca phn t s dn n s bin thin nng lng E ca phn
t tun theo nh lut Planck.
E = Ecao E thp = h

(2-1)
6

Do nng lng phn t c lu gi di ba dng: quay, dao ng v in t nn:

E = Equay + Edao ng+ Ein t

(2-2)

Nh vy, do hin tng hp ph bc x in t ca phn t gy nn cc bc chuyn nng

lng quay, dao ng v in t ca phn t v l ngun gc ca cc loi ph hp th phn
t m chng ta s nghin cu cc chng tip theo.

Hnh 2-1. S dch chuyn in t trng thi nng lng lng t ca mt nguyn t to ra s pht x
ca mt photon.

2.1.2. Ph hp th

Ph hp th m t cc tnh cht hp th ca cc ht, n c biu din dng hm s gim

cng tia bc x in t v bc sng (hay tn s, hay s sng). Hai i lng thng
c s dng nh lng s gim cng tia bc x in t l truyn quang v
hp th.
truyn quang
U

nh sng n sc (bc sng thuc min t ngoi v trng thy) c cng Io chiu qua
cuvet ng mu dung dch c nng C, c b dy l b, khi nh sng i qua khi cuvet c
cng l I, mt phn nh sng b hp th bi mu bi vy IIo.
T s gia cng nh sng i qua mu v cng nh sng ban u c gi l
truyn quang T

T=

(2-3)

Bi vy, T thay i t 0-1. Phn trm truyn quang, n gin l 100T%, v n thay i tng
ng t 0-100%.
hp th A c nh ngha:

A = lg = -lgT

(2-4)

Nu nh sng khng b hp th, I = Io v A = 0

Nu 90% nh sng b hp th, 10% c truyn quang, khi

ny nhn c A = 1

= 10 v vi t s

Nu ch c 1% nh sng c truyn quang, A = 2

( hp th A i khi cn gi l mt quang optical density)

Gi s chng ta lin tc theo di vo hp th ca dung dch nghin cu c nng C

khi tng dn bc sng tia ti v pha sng di v xy dng nn th mi quan h A- th
ng cong A=f() c gi l ph hp th. th A=f() thng c dng hnh chung p
(hnh Gaux) (hnh 2-2).

Hnh 2-2. Ph hp th ca cht A dng dung dch

Cc i Amax ng vi gi tr max gi l cc i hp th, max ch ph thuc vo bn cht dung

dch, c th dng trong phn tch nh tnh.

Khi tin hnh phn tch theo phng php quang ph o quang ngi ta thng chn o
hp th A ca dung dch nghin cu ti max bi v vic o A max s cho ta kt qu phn
tch c nhy v chnh xc cao nht.

2.2. nh lut c bn v hp th bc x in t
2.2.1. nh lut Lambert-Beer
nh lut Lambert Beer

A = bC = lg = -lgT

(2-5)

hp th A l mt i lng khng th nguyn. Nng ca mu thng c s dng n v l

mol/l. Chiu dy ca cuvet ng mu b, thng c m t bng cm. i lng gi l hp th
mol (hay cn gi l h s tt phn t) v c n v l M-1cm-1, bi vy tch s bC l khng th
nguyn. Phng trnh (2-5) mang tn nh lut Bouger Lambert Beer.
Trong phn tch o quang, vi dung dch phn tch xc nh, bc sng tia ti l n sc th l xc
nh, ngi ta lun c th chn b xc nh nn nh lut hp th nh sng c th vit di dng:
A = KC vi K= b = const

(2-6)

Phng php phn tch o quang nh lng c t trn c s phng trnh (2-6)
Chng minh nh lut Lambert Beer
U

( tr li cho cu hi ti sao mi quan h gia truyn quang T v nng li tun theo mi quan
h logarit)
b
nh sng ti (Io, )

I-dI

nh sng l, I
C

x= 0

dx

x=b

Hnh 2-2. Chng minh nh lut Bouger Lambert Beer

Bng trc gic ta nhn thy rng, khi nh sng i qua dung dch, nh sng b hp th nhiu hay t ph
thuc vo s phn t m n gp, m s phn t li ph thuc qung ng v nng . By gi ta
s chng minh bng ton hc.

Chng ta hy t ng tng chiu mt chm nh sng n sc c cng I i qua mt lp

mng ca dung dch c b dy dx, nh sng b hp th v cng ca n gim i l dI.
dI = - ICdx

(2-7)

y l h s t l v du m ch s gim cng I khi x tng

Bin i phng trnh (2-7) v ly tch phn i vi I ta c:

= 0

(2-8)

Gii hn ca tch phn y l I = Io x=0

v I = I x=b
T (2-8) a ti:

-lnI (-lnIo) = bC = bC

Cui cng, bin i ln v lg, s dng mi quan h lnz = ln(10)(lgz), ta nhn c nh lut
Bouger Lambert Beer:

= 10bC = bC

hp th A

Hng s

y chnh l biu thc (2-5)

V d: Tm hp th v truyn quang ca dung dch 0,00240M ca mt dung dch c
hp th mol = 313 M-1cm-1, vi b dy cuvet l b = 1,00 cm
Gii: Theo (2-5) ta c:
hp th A = bC = 313 M-1cm-1 x 1,00 cm x 0,00240M = 0,751
truyn quang T = 10-A = 10-0,751 = 0,177
c 17,7% nh sng truyn qua dung dch (nh sng l)
2.2.2. Tnh cht cng tnh ca hp th quang
Gi s chng ta chiu lin tip mt chm tia sng n sc qua hai dung dch c nng ln lt l C1
v C2, hp th mol tng ng l 1 v 2.

dung dch 1 c hp th A1 = , dung dch 2 c hp th A2 = 1

Ta c: + 1 = 1 = A1 + A2 = A
1

10

Nh vy, chng ta nhn thy rng hp th c tnh cht cng tnh:

A = =1

(2-9)

Ni cch khc, nu c i cht trong cng mt dung dch hp th mt nh sng no , hp

th s l hp th ca i cht.
Chng ta hy xem xt tnh cht ny c ngha th no trong phn tch bng phng php
quang ph o quang.
Nu mt dung dch gm cht nghin cu v tp cht th hp th:
Adung dch = Anghin cu + Ann
Trong phn tch o quang chng ta chun b dung dch trng cha cc tp cht, c ngha l:
Atrng = Ann (do khng c mt ion cn xc nh)
V

Anghin cu = Adung dch - Atrng

Nh vy, trong phn tch o quang bng vic s dng dung dch trng, gi tr A o c s
phn nh ng nng cht nghin cu, ni cch khc phng tr
nh (2 -6) c tun theo
cht ch.
2.2.3. Cc yu t lm sai lch nh lut Lambert-Beer

nh lut Lambert-Beer c th b sai lch do nhiu nguyn nhn vt l v ha l, i u nh

hng n tnh ng n ca phng trnh (2-5), tc l nh hng trc tip n chnh xc
ca kt qu phn tch thu c theo phng php quang ph o quang.
- Tnh n sc ca nh sng ti: Nh ta bi t nh lut Lambert-Beer ch ng vi bc x
in t n sc xc nh. Nu ta o hp th ca dung dch bng mt chm tia a sc th
nh lut Lambert-Beer khng cn ng na, dn n ph v tnh ng n ca phng trnh
(2-5).
- nh lut c th b thay i vi mt s iu kin ha l ca dung dch nghin cu. V d, s
c mt ca ion l lm bin dng cc phn t hp th nh sng, lm thay i ph hp th ca
cht nghin cu.

11

Khi thay i nng cht nghin cu lm thay i kh nng hp th ca cc phn t. Khi

thay i nng H+ ca dung dch nghin cu c th lm thay i dng tn ti ca hp cht.
V d, vi ion CrO42- khi tng nng [H+] c th to thnh ion Cr2O72- theo phn ng:
2 CrO42- + 2H+ Cr2O72- + 2H2O
Lm thay i min bc x in t b hp th.
Mt v d khc, phc Fe3+ vi axit sunphosalysylic ty thuc pH m to phc c min ph hp th
khc nhau.
[Fe(Saly)]+ pH = 1,8-2,5

max = 510 nm

[Fe(Saly)2]- pH = 4-8

max = ... nm

[Fe(Saly)3]3- pH = 8-11

max = 420 nm

- Khi thay i dung mi c th lm thay i kh nng hp th ca cht nghin cu, do thay i

solvat, do c th lm thay i kh nng hp th nh sng ca cht nghin cu.
2.2.4. chnh xc ca php o hp th v php o nng

T h thc A =lg

= lg (vi T l truyn quang c gi tr t 0-100%), nn vi mi my

o no , vi mi php o truyn quang T gy nn sai s dT th s gy nn cc sai s dA

tng ng khc nhau ty thuc dA tng ng vi min no ca gi tr T o c. M A li

ph thuc tuyn tnh vi C nn kt qu l cng vi mt sai s dT ca my, ti cc min o

khc nhau c th gy sai s dC khc nhau v do sai s

Ta c: C = =

s khc nhau.
(2-10)

Ly vi phn: dC = 2,3

(2-11)

T (2-10) v (2-11) ta c:

= 2,3 =

Chuyn sang gia s hu hn ta c:

(2-12)

12

T (2-12) ta c th kho st s bin thin

T cho trc.

trong min gi tr ca T (T = 01) vi mt sai s

tm cc tr ta ly vi phn phng trnh (2-12) theo T vi T = const v cc tr xy ra khi:

()2

(+1)
()2

=0

V T 0, nn r rng (lnT+1) = 0. T lnT = 2,3lgT = -1 v lgT = A = 0,435.

Vy vi gi tr hp th A = 0,435 th php o s cho gi tr chnh xc nht trong php
xc nh nng C ca cht nghin cu.
2.2.5. iu kin nng tin hnh phn tch o quang

iu kin c th tin hnh phn tch o quang l phi to c cc hp cht c hiu ng

hp th bc x in t trong min t ngoi hoc trng thy. c hiu ng ph hp th trong
min trng thy, thng thng ngi ta to hp cht mu bng phn ng oxy ha kh hoc
phn ng to phc. i vi phn ng oxy ha kh trong phn tch o quang thng xy ra
thc t hon ton (v d nh phn ng oxy ha Mn2+ thnh MnO4-). i vi cc phn ng to
phc th tnh hnh phc tp hn nhiu. Phn ng to phc chu nh hng ca nhiu yu t:
qu trnh to phc nhiu cp, H+, hng s bn...

2.3. Cc th tc thc nghim trong phn tch o quang

Theo phng trnh (2 -6) mi quan h gia A v C l tuyn tnh. xc nh nng trong
phng php o quang chng ta phi xc nh hng s K trong phng trnh ny. C ba cch
xc nh hng s K: phng php ng chun, phng php tnh v phng php thm tiu
chun.
2.3.1. Phng php ng chun

Trc ht chng ta pha ch cc dung dch c nng chnh xc C1, C2, C3, ..., xc lp cc
iu kin to cc hp cht c hiu ng ph hp th bc x in t max chn trc. o
hp th tng ng A1, A2, A3, ... Mi quan h gia A v C tun theo nh lut LambertBeer, do vy ta c th hi qui cc s liu thc nghim ri rc ny v hm bc nht v h s
gc ca n chnh l hng s K.

13

0,700
0,600

0,500

y = 1,4963x
R = 1

0,400
0,300
0,200
0,100

C, mg/l

0,000
0,000

0,050

0,100

0,150

0,200

0,250

0,300

0,350

0,400

0,450

Hnh 2-3. Phng php ng chun

2.3.2. Phng php tnh

T phng trnh (2 -6) A= bC = KC, vi mt cht nghin cu xc nh v b chn trc

(thng s dng cuvet c b = 1,00 cm) v vi cht nghin cu bn th vic xc nh nng
c th ch cn mt mu chun c nng bit chnh xc l . V trong i u kin trn th
K s khng thay i t th nghim ny sang th nghim khc.
Chng ta o hp th ca dung dch mu nghin cu c nng Cx v dung dch chun Co.
Vit phng trnh ng thng i qua hai im v t tnh c Cx.
2.3.3. Phng php thm tiu chun

Tin hnh o hp th ca dung dch nghin cu c nng Cx, sau thm mt lng
dung dch chun vo dung dch nghin cu C1 v o hp th ca dung dch ny. Thng
ngi ta pha ch t nht l ba dung dch, v d Cx, Cx + C1 v Cx +2C1. Mi quan h gia cc
s liu ri rc l mi quan h tuyn tnh. Hi qui cc s liu ri rc v phng trnh bc nht,
t cho php chng ta tnh c h s gc K.
php o c tin cy cao, thng ngi ta chn nng C1 c nng gn bng Cx.

14

2.4. Phng php o quang vi sai

Nh trnh by phn 2.5, vic o hp th cc gi tr A ln c th mc phi sai s ln
trong vic xc nh nng . Vi cc dung dch c hp th ln ngi ta s dng phng
php o quang vi sai. Trong phng php ny hp th ca dung dch o khng phi so vi
dung mi hoc dung dch trng nh phng php o quang thng dng. Dung dch so snh
y thng l dung dch c nng bit trc Css , Css phi chn th no hp th ca
n so vi dung mi hoc dung dch trng kh ln nhng phi nh hn hp th ca dung
dch o mt t.
Chng ta c th xc nh nng ca cht nghin cu s dng cc th tc phn tch nh vi
o quang thng.
C s phng php:
U

Dung dch so snh c nng Css, o c Ass (qui v 0,000)

Dung dch phn tch c nng C, o c A
Khi dung dch so snh c nng khc khng, gi tr A o c s l hiu ca A-Ass, da
trn tnh cht cng tnh ca hp th
A = A-Ass = b(C-Css)
Khi dung dch phn tch c nng ln (gi tr A s rt ln), ngi ta s dng phng php
o quang vi sai nhm lm gim gi tr o A vi vic s dng dung dch trng cha cht cn
phn tch bit nng , v khi gi tr o c s nm trong khong tuyn tnh, tc l h
thc (2-5) lun ng.
Phng php tnh:
U

Chng ta cn chun b dung dch chun, dung dch so snh v dung dch phn tch
V d:
dung dch chun

dung dch so snh

dung dch phn tch

Cu2+

Cch

Css (Css <Cch, Cx)

Cx

hp th

Ach

0,000

Ax

Ta c: =

Cx

15

Phng php th:

U

Chng ta cn chun b mt dy dung dch chun, dung dch so snh v dung dch phn tch
Dy dung dch chun

dung dch so snh

dung dch phn tch

Cu2+

Cch1, Cch2, ...Cchi

Css (Css <Cchi, Cx)

Cx

hp th

Ach1, Ach2, ... Achi,

0,000

Ax

o hp th Achi ng vi cc dung dch chun th i, dung dch so snh c la chn sao

cho nng ca n nh hn Achi. Xy dng th mi quan h A-C.
Ta cng tin hnh o quang vi cng iu kin cho dung dch phn tch c nng Ax vi
dung dch so snh.

1,400
1,200

y = 1,4963x
R = 1

1,000
0,800
0,600

y = 1,449x - 0,2898
R = 1

0,400

o quang vi sai
0,200

C, mg/l
0,000
0,000

0,100

0,200

0,300

0,400

0,500

0,600

0,700

0,800

0,900

Hnh 2-4. Phng php o quang vi sai

T th ta c th tnh c nng ca dung dch nghin cu sau khi tin hnh o hp

th Ax

2.5. S thit b quang ph hp th phn t

S thit b quang ph hp th phn t c m t bng s khi hnh 2-5 di y:

16

Hnh 2-5. S thit b quang ph hp th phn t

Ngun sng:
Cc loi n H2 v D2 cho nh sng vi bc sng t 160-380 nm (hnh 2-6)
n si t vonfram cho nh sng t min 350-2200 nm (hnh 2-7)
Cc thit b UV-VIS hin i thng s dng c hai n D2 v n si t vonfram cho min nh n
nh t min t ngoi v min trng thy.

Hnh 2-6. n Deuteri (a) v ph pht x ca n (b)

Hnh 2-7. n si t vonfram (a) v ph pht x ca n (b)

B tn sc:

17

Cc thit b phn tch quang hc thng cn n b tn sc gip vic phn chia nh sng thnh nh
sng n sc, n c s dng cht phn tch hp th hay pht x. Do vy, b tn sc nng cao c
nhy v chn lc. Ngoi ra, tnh n sc ca nh sng ti lm tng tnh ng n ca phng
trnh ton hc ca nh lut Lambert-Beer.
u tin, cn hiu rng khng c c b tn sc no l c kh nng to ra bc x c bc sng n sc.
Mc d, u ra ca thit b l mt min nh sng lin tc c gi l m; Cc bc sng ny phn
b t nhiu i xng qua trung tm ca bc sng danh ngha 1 (nominal wavelength).

Hnh 2-8. u ra ca mt b tn sc
Nh c ch ra hnh 2-8, rng hiu qu ca m hay cn g i l n sc c nh ngha l
rng ca m ph chiu cao ca chiu cao pic. n sc ca b tn sc thay i rt ln i
vi cc b tn sc khc khau. V d, b tn sc c cht lng cao cho min trng thy c th cho
n sc nh hn 1/10 nm, trong khi cc b lc trong vng trng thy c th cho n sc ti 200
nm hay ln hn.
Cch t: Hu ht b tn sc trong cc thit b phn tch hin i l cc bn sao cch t, nhn c
bng cch c t cch t ch. Cch t ch l mt knh phng, c nh bng b mt v c chia
vch bng kim cng. Mt ct ng c phng i hnh 2-9 ch cho ta thy mt vi rnh. Mt cch
t s dng cho min t ngoi v trng thy thng cha t 300-2000 rnh/mm.

18

Hnh 2-9. C ch nhiu x t mt loi cch t

Cuvet ng mu:

Hnh 2-10. Cc loi cuvet ng mu

Cuvet ng mu thng lm bng thy tinh (lm vic trong vng trng thy) hoc bng thch
anh (lm vic trong min t ngoi v trng thy) nh c ch ra hnh v 2-10.
Detector:
Cc tnh cht ca b chuyn i tn hiu bc x in t:
-

Phn hi nhanh chng vi cc vi cc bc x mang nng lng thp trn mt min

bc sng rng.

To ra tn hiu in c th d dng khuch i v c nhiu thp.

Tn hiu c to ra bi u d t l thun vi cng ca tn hiu ca u vo.

Detector lm vic trong min UV-VIS thng dng l ng quang (phototubes) lm vic trong
min t 150-1000 nm (hnh 2-11).
19

Hnh 2-11. ng quang v cc ph kin

Mt lm ca b mt catot c ph mt lp vt liu quang in, chng hn nh mt kim loi

kim hay cc oxit kim loi. Cc vt liu quang in c xu hng pht x electron khi b kch
thch. Khi mt in p c t vo cc in cc, cc electron chy theo anot (dng dy), to
ra mt dng c th d dng c khuch i, hin th v ghi li.
S electron c y ra t b mt ca quang in t l thun vi bc x tia ti tn cng b
mt ny. Vi in p khong 90V, cc electron ny c th ti c anot v cho mt dng t l
thun vi cng tia ti.

2.6. Mt s ng dng phng php o quang

Vic ng dng phng php quang ph o quang khng ch phn tch nh lng m n
cn c ng dng nghin cu trng thi cn bng trong dung dch nh xc nh hng s
phn ly ca cc axit hu c, hng s cn bng ca phn ng to phc v thnh phn phc
cht.
2.6.1. Xc nh thnh phn phc cht trong dung dch bng phng php dy ng phn t
gam (phng php bin thin lin tc_Continuous Variation)

xc nh h s ha hc trong phn ng to phc cht ngi ta hay dng phng php dy

ng phn t gam. Phng php ny ch ng cho trng hp h thng to thnh mt phc,
khng c phn ng ph nh thy phn, trng hp hay phn ly.
Gi s c ion kim loi Me tc dng vi thuc th R cho phc MeRn theo phn ng:
Me + nR MeRn

(2-13)
20

Vi hng s cn bng:
[ ]

Kcb = [][]

(2-14)

T phng trnh (2-13) cho thy khi tng nng thuc th R th l ng phc to thnh s
tng ln. Nu pha mt dy dung dch trong lng tng i ca Me v R khc nhau,
nhng lng chung ca chng khng i, th s c mt dung dch c nng MeRn cc i.
Thnh phn ca dung dch ny s ph thuc vo nng ban u ca Me v R cng nh K cb.
Nu pha ch dy dung dch xut pht t dung dch Me v R c nng phn t gam (mol/l)
ging nhau, trong tng dung dch ca dy, tng nng phn t gam ca Me v R l khng
i, cn t l nng Me vi nng R thay i (dung dch ng phn t). Dung dch c
thnh phn phc cht cc i l dung dch m trong t l nng ca Me v R bng thnh
phn ca chng trong phc cht.
Cc iu lu khi s dng phng php bin thin lin tc:
- m bo tnh ng n ca nh lut Lambert-Beer.
- Gi lc ion khng i v pH n nh (c th s dng dung dch m).
- o nhiu hn mt bc sng tia ti; cc i hp th xy ra cng phn mol cho mi
bc sng.
- Lm th nghim vi tng nng Me + R khc nhau.

Hnh 2-12. Phng php dy ng phn t gam

21

T c s trn y ta c th tin hnh xc nh n bng thc nghim. Ta pha ch hai dung dch
u ca Me v R c nng mol chnh xc bng nhau. Pha ch mt lot dung dch dy ng
phn t bng cch trn hai dung dch Me v R vi th tch ca Me v T khc nhau nhng
tng th tch VMe + VR = const.
Trong mi dung dch ca dy ta phi chn v to iu kin to phc MeRn tt nht. Lc
trong mi dung dch s to thnh phc MeRn v nng MeRn to thnh ph thuc vo
phn mol ca ligan. Tin hnh o quang dy dung dch to thnh. Trong dy chng ta s tm
c mt thnh phn m xut hin Amax v ng vi t s ha hc phi tm.
2.6.2. Xc nh thnh phn phc cht trong dung dch bng phng php ng cong bo ha

y l phng php ph bin, c th ng dng trong trng hp phng php bin dy ng

phn t khng cho kt qu tt. i vi cc phn ng c hiu ng ph hp th, lun lun ta c
th xy dng c ng cong bo ha.
Khi xy dng ng cong bo ha th ng
i ta gi nng mt cu t khng thay i
(thng l cu t Me) cn thay i nng cu t kia. o hp th ca cc dung dch
trong dy. Xy dng th mi quan h A-CR/CMe. Nu phc bn th th thu c s c

im gy ng vi honh = n

Hnh 2-13. Phng php ng cong bo ha

22

Cu hi ca sinh vin:
U

1. n v ca cng nh sng?
n v ca nh sng l Candela (cd)
Candela hay cn c gi l nn (Candle), l n v o cng chiu sng, l cng chiu sng
theo mt hng cho trc ca mt ngun pht ra bc x n sc vi tn s 5401012 hc v cng
bc x theo hng l 1/683 ot trn mt Sterradian

2. Hm trc c dy chng em phn "phng php ph hp th phn t" c 1 mc l: nh

ngha v ph hp th phn t: l nhng ng cong th hin mi quan h gia mt quang
v bc sng. Nhng tha c, em c c ti liu quyn C s ha hc phn tch ca thy
Chu, trong sch ghi: Ph hp th l nhng ng cong th hin mi quan h gia hp
th phn t ( p xi non) vi bc sng .
Tha c, 2 nh ngha ny c khc nhau khng ? M sao em thy th ca chng nh
nhau.
Chng ta c nh lut Lambert-Beer, l nh lut c bn ca bc x in t:
A= bC
Trong :
hp th A (Absorbtion), i khi cn gi l mt quang D (Density)
b: l qung ng m nh sng i qua dung dch, cm
: l k hiu ca hp th mol phn t ( ngha vt l ca n l: n chnh l hp th khi
nh sng i qua dung dch 1M vi qung ng l 1cm
Ph hp th: Chng ta lin c
t thay i bc sng tia ti i qua dung dch nghin cu c
nng C v qung ng l b, ghi li cc gi tr A tng ng (da trn vic o s gim
cng bc x in t khi i qua dung dch). ng cong th hin mi quan h ny c
gi l ph hp th. A-
T phng trnh Lambert-Beer chng ta c th tnh c tng ng.
Nh vy chng ta c th thy l th mi quan h gia A v ging dng th -

23

Ni dung
Chng 3. Phng php quang ph pht x nguyn t ....................................................... 1
3.1. Nguyn tc phng php ph pht x nguyn t....................................................... 1
3.1.1. S to thnh ph pht x nguyn t .................................................................... 1
3.1.2. Tnh a dng ca ph pht x nguyn t ............................................................. 4
3.1.3. Cc loi vch ph c trng ca mt nguyn t................................................... 5
3.1.4. S thit b quang ph pht x nguyn t......................................................... 6
3.2. Phn tch bng phng php quang ph pht x nguyn t ................................... 11
3.3. Cc yu t nh hng n chnh xc .................................................................. 12
3.4. ng dng ca phng php trong phn tch ............................................................ 13
3.5. Cu hi n tp .......................................................................................................... 14

Chng 3. Phng php quang ph pht x nguyn t

Phng php ph pht x nguyn t (AES) c Bunsen v Kirchoff pht minh vo gia th
k 19. T khi c pht minh, phng php AES ng gp quan tr ng vo s pht minh
cc nguyn t ha hc mi vo cui th k 19, u th k 20. Phng php c ng dng
vo cc mc ch phn tch nh tnh, bn nh lng v nh lng hu ht cc kim loi v
nhiu nguyn t phi kim loi n h P, Si, As v B vi nhy thng ti cp hm lng
0,001% hoc hm lng thp hn. Mt nt ht sc c th ca phng php AES l c th
phn tch c nhiu nguyn t trong mt ln phn tch v c th phn tch cc nguyn t
trong cc i tng rt xa da vo nh sng pht x t i tng .

3.1. Nguyn tc phng php ph pht x nguyn t

3.1.1. S to thnh ph pht x nguyn t

Phng php AES da vo vic o bc sng, cng v cc c trng khc ca bc x

in t do cc nguyn t hay cc ion trng thi hi pht ra. Vic pht cc bc x in t do
cc nguyn t hay cc ion trng thi hi pht ra l do s thay i trng thi nng lng ca
nguyn t. Theo hc thuyt cu to nguyn t, cc nguyn t c th c mt s mc nng
lng gin on Eo, E1, E2, ... m khng c trng thi nng lng trung gian v d gia Eo v
E1, hoc gia E1 v E2... Trong iu kin bnh thng cc nguyn t trng thi nng lng
thp nht Eo hay cn gi l nguyn t trng thi c bn. Khi cp nng lng cho nguyn t
bng mt bin php no , v d do s va chm vi cc in t chuyn ng nhanh hoc
1

bng ngun nhit c nhit cao (ngn la, h quang, tia la in, ...) cc nguyn t c th
chuyn ng ln mc nng lng cao hn E1, E2, E3, ..., En,... ngi ta ni cc nguyn t
chuyn sang trng thi kch thch hay cn gi l b kch thch. Sau mt khong thi gian ngn
(10-7-10-8s) cc nguyn t trng thi kch thch s t quay v trng thi nng lng thp hn
(trng thi c bn hay trng thi kch thch no mc nng lng thp hn). Nng lng
E c gii phng di dng cc lng t nh sng h theo (3-1)
E = h

(3-1)

Tn s ca nh sng c xc nh theo h thc:

=

(3-2)

Trong : , EA- nng lng ca nguyn t trng thi kch thch v trng thi nng lng

thp hn;

Hoc nu c trng cho bc x nh sng pht ra di dng s sng theo h thc:

=

(3-3)

Hnh 3-1: Qu trnh hp th v pht x ca mt nguyn t

S hng quang ph:

U

T cng thc (3-2) v (3-3) cho thy mi bc x in t khi b kch thch lin quan n trng
thi nng lng ca nguyn t.
Trng thi nng lng ca nguyn t n gin nh nguyn t hydro c mt in t, khi c
th gii phng trnh Schodinger cho tr ng thi dng vi nguyn t hydro v tm c biu
thc sau y v trng thi nng lng in t ca nguyn t hydro:
=

22 4

(3-4)

2 2

Thay (3-4) vo (3-2) v (3-3) ta c:

=

2 2 4

2 2 = 2 2

2 2 4
3

(3-5)

2 2 = 2 2
1

(3-6)

n1 v n* l s lng t chnh ca in t trng thi c bn v kch thch

R- hng s Rydberg, mt hng s vt l c bn
R=

2 2 4
3

S sng ca cc vch ph xc nh theo phng trnh (3-6) c th biu din dng hiu hai
i lng:

= 2 - 2
1

(3-7)

Cc i lng c k hiu chung l T v:

T(ni) = 2
1

T(n*) = 2

(3-8)

Cc s hng quang ph ca nguyn t hydro c th c tnh trc tip theo (3-8), vi ni = 1,

ta tnh:

T(ni = 1) = R/1 = 109.687,76 cm-1

ng dng cc cng thc (3-6) ta c th tnh tn s v s sng ca cc dy vch ph pht x
ca nguyn t hydro.
V d: ni = 1 v n* 2 ta c dy Lyman
ni = 2 v n* 3 ta c dy Balmer
ni = 3 v n* 4 ta c dy Paschen
...
3.1.2. Tnh a dng ca ph pht x nguyn t

Khi c cung cp nng lng ha hi, nguyn t ha mu phn tch, khng phi ch c
nguyn t t do b kch thch, m c c ion, phn t, nhm phn t. Cc phn t ny cng b
kch thch v pht ra ph pht x ca n. Tt nhin l trong mc khc nhau ty thuc vo
kh nng kch thch ca ngun nng lng. Ph pht x ca vt mu lun bao gm ba thnh
phn:
- Nhm ph vch. l ph ca nguyn t v ion. Nhm ph vch ny ca cc nguyn t
ha hc hu nh thng nm trong vng ph t 190-1000nm (vng UV-VIS). Ch c mt vi
nguyn t kim hay kim loi kim mi c mt s vch ph nm ngoi vng ny.
- Nhm ph m. l ph pht x ca cc phn t v nhm phn t. V d ph ca phn
t MeO, CO v nhm phn t CN. Cc m ph ny xut hin thng c mt u m v
mt u nht. u m pha sng di v nht pha sng ngn. Trong vng t ngoi th
ph ny xut hin rt yu v nhiu khi khng thy. Nhng trong vng kh kin th xut hin
rt m, v lm kh khn cho php phn tch quang ph v nhiu vch phn tch ca cc
nguyn t khc b cc m ph ny che lp.
- Ph nn lin tc. y l ph ca vt rn b t nng pht ra, ph ca nh sng trng v ph
do s bc x ring ca in t. Ph ny to thnh mt nn m lin tc trn ton di ph ca
mu, nht sng ngn v m dn v pha sng di. Ph ny nu qu m th cng s cn tr
php phn tch.
Ba loi ph trn xut hin ng thi khi kch thch mu phn tch v trong phn tch quang
ph pht x nguyn t ngi ta phi tm cch loi bt ph m v ph lin tc. l hai yu
t nhiu.

3.1.3. Cc loi vch ph c trng ca mt nguyn t

Trong ba thnh phn: ph vch ca nguyn t v ion; ph m ca phn t v nhm phn t;

ph nn lin tc th ph vch l thnh phn chnh c trng cho nguyn t v ion trng thi
hi t do, khi chng b kch thch, ngha l trng thi hi. Khi b kch thch, cc nguyn t
v ion s pht ra mt chm bc x quang hc gm nhiu tia c bc sng khc nhau nm
trong di ph quang hc (190-1100nm). Nu thu, phn li v ghi chm sng li ta s c
mt di ph gm cc vch pht x ca nguyn t v ion ca cc nguyn t c trong mu.
Trong tp hp cc vch ph , th mi loi nguyn t hay ion li c mt s vch c trng
ring cho n. Cc vch ph c gi l cc vch ph pht x c trng ca loi nguyn
t y.
V d: Khi b kch thch:
-

nguyn t Al pht ra vch c trng trong vng UV: 308,215; 309,271nm.

nguyn t Cu pht ra vch c trng trong vng UV: 324,754; 327,396nm.

Chnh nh cc vch ph c trng ny ngi ta c th nhn bit c s c mt hay vng

mt ca mt nguyn t no trong mu phn tch qua vic quan st ph pht x ca mu
phn tch, v tm xem c cc vch ph c trng ca n hay khng, ngha l da vo cc vch
ph pht x c trng ca tng nguyn t nhn bit chng. l nguyn tc ca phng
php phn tch quang ph pht x nh tnh.
Mun xc nhn s c mt hay khng c mt ca mt nguyn t no trong mu phn tch,
ngi ta phi tm mt s vch ph c trng ca nguyn t trong ph ca mu phn tch
xem c hay khng, t m kt lun c n hay khng c n trong mu phn tch. Nhng
vch ph c trng c chn c gi l vch chng minh ca nguyn t y. Ni chung,
pht hin mt nguyn t t kt qu chnh xc v chc chn, ngi ta phi chn t nht
hai vch chng minh khi quan st ph ca mu phn tch. Cc vch ph ny phi tha mn
mt s iu kin sau y:
-

Nhng vch ph ny phi r rng v khng trng ln vi cc vch ca nguyn t

khc, nht l nguyn t nng ln.

N phi l nhng vch ph nhy, c th pht hin c cc nguyn t trong mu

vi nng nh (phn tch lng vt).

Vic chn cc vch ph chng minh cho mt nguyn t phi xut pht t ngun nng
lng dng kch thch ph ca mu phn tch, v trong ngun kch thch c nng
5

lng thp th ph ca nguyn t l ch yu v vch nguyn t ca n thng l

nhng vch nhy. Ngc li, trong ngun kch thch giu nng lng (ICP) th ph
ca Ion l ch yu. Cho nn phi ty thuc vo ngun nng lng dng kch
thch ph m chn vch chng minh l vch nguyn t hay vch ion cho ph hp.7
-

Phi cn c vo my quang ph c th thu, phn li v ghi c trong vng sng no

m chn vch chng minh cho mt nguyn t nht nh. V d chng minh Na,
nu ph mu c ghi trn my Q-24 (vng ph 200-400 no th ta phi chn hai
vch Na 330,30 v Na 330,27 nm. Ngc li, nu ghi trn my lng knh thy tinh
(vng ph 360-780 nm.), th li phi chn hai vch Na 589,60 v 589,00 nm. Nu
dng my cch t PGS-2 (vng ph 200- 1100 nm) th chn 4 vch trn u c.

3.1.4. S thit b quang ph pht x nguyn t

Hnh 3-2 m t s thit b quang ph pht x.

Hnh 3-2: S thit b pht x nguyn t

Ngun
Ngn la: Ngn la n kh c nhit khng cao (1700 3200 C), c cu to n gin,
U

nhng n nh v d lp li c cc iu kin lm vic. Do c nhit thp, nn ngn la

n kh ch kch thch c cc kim loi kim v kim th. V ng vi loi ngun sng ny
ngi ta c mt phng php phn tch ring. l phng php phn tch quang ph ngn
la (Flame Spectrophotometry). Song v bn cht n vn l ph pht x ca nguyn t trong
ngn la. Cc cht kh t to ra ngn la ca n kh thng l mt hn hp ca hai kh
(1 kh oxy ha v 1 kh nhin liu) c trn vi nhau theo mt t l nht nh. Bn cht v
6

thnh phn ca hn hp kh quyt nh nhit ca ngn la v hnh dng cu to ca ngn

la.

Hnh 3-3: To ngn la v bm mu trong AES

H quang in:
U

c im v tnh cht
H quang l ngun kch thch c nng lng trung bnh v cng l ngu n kch thch
vn nng. N c kh nng kch thch c c mu dn in v khng dn in. Ty thuc vo
cc thng s ca my pht h quang v loi in cc ta chn m h quang c nhit t
3500 6000C. Vi nhit ny nhiu nguyn t t cc nguyn liu mu khc nhau c th
c ha hi, nguyn t ha v kch thch ph pht x. Nhit ca h quang ph thuc rt
nhiu vo bn cht ca nguyn liu lm in cc. V th trong mt iu kin nh nhau, h
quang in cc than (graphite) c nhit cao nht. Cng dng i n trong mch h
quang l yu t quyt nh nhit ca h quang.
H quang l ngun kch thch cho nhy tng i cao, v trong h quang mu phn
tch c ha hi tng i d dng hn trong cc loi ngun nng lng khc, c bit l h
quang dng mt chiu. Nhng cng do tnh cht ny m php phn tch dng h quang c
n nh v lp li km ngn la v tia in. y h quang dng xoay chiu cho kt qu
n nh hn h quang dng mt chiu, v th h quang dng xoay chiu c s dng nhiu
hn.

Cu to v nguyn tc hot ng ca my pht h quang

Tuy c nhiu loi my pht h quang khc nhau, nhng v nguyn tc cu to, tt c cc my
pht h quang u gm hai phn chnh.
- Phn 1 l mch pht h quang (mch chnh), n c nhim v cung cp nng lng ha
hi, nguyn t ha mu v kch thch m hi i n pht x. Nu h quang mt chiu th
l mch ca dng i n mt chiu (hnh 3.4). Nu l h quang xoay chiu, th l dng
in xoay chiu.

Hnh 3-4: S nguyn tc cu to ca my pht h quang

- Phn 2 l mch ch huy (mch iu khin), c nhim v ch huy phn mch chnh hot ng
theo nhng thng s c chn cho mt mc ch phn tch nht nh. Theo s hnh
3-4, nu cng tc K c ng v tr AA, ta c h quang dng xoay chiu. Cn khi v tr
BB' ta c h quang dng mt chiu. S hot ng ca h quang din ra nh s hnh 3-4:
Khi ng cng tc K', ngha l a i n vo my, qua h thng bin tr R1 ta chn c th
lm vic ph hp a vo bin th Tr1 tng th. Khi th hai u cun th cp ca
bin th ny t n hng ngn vn (2000-7000V). Hai u cun ny c ni vi cun cm
Ll, t in C1 v khong n ph E. Lc t C1 c tch in v khi t n th Vf chn
th c mt tia in c nh qua khong E, nh th lp tc trn mch dao ng L1C1 xut
hin mt dao ng cao tn. Do mch dao ng L2C2 cng ghp vi mch dao ng L1C1, nn
trn mch L2C2 cng xut hin mt dao ng cao tn cm ng nh th. Nhng s vng ca
L2 l ln hn nhiu L1, nn th trn hai ct ca t C2 cng s ln hn C1. Th ny li xut
hin tc khc khi c tia in nh E v iu khin s phng in qua khong F ca hai in
cc h quang. Nh th mt chu k phng in th nht c thc hin v kt thc, ri li tip

din n chu k phng in th hai, th ba,... v c th din ra cho n khi no ta ngt cng
tc K', tc l ngng s phng in ca h quang.
Khi h quang lm vic, in cc F s c t nng v di tc dng ca in trng cc
in t bt ra khi b mt in cc m, chng c gia tc v chuyn ng v cc dng.
Nhng in t ny c ng nng rt ln, v khi chuyn ng trong plasma gia hai in cc,
cc in t va chm vo cc phn t khc (nguyn t, ion, phn t...) trong plasma F, n
truyn nng lng cho nhng phn t . Khi trong plasma c phn t b ion ha, b phn
li v b kch thch. Kt qu li c thm in t t do na cng vi mt s nguyn t, ion, phn
t b kch thch. Nh vy chnh cc phn t mang in tch dng v m duy tr dngi n
qua ct kh ca plasma. Gia hai in cc F cc phn t b kch thch s sinh ra ph pht
x ca n. Trong h quang mt chiu in t lun lun p vo in cc dng, nn in cc
dng nng hn in cc m. Cn ng c li, trong h quang dng xoay chiu, hai in
cc li c t nng nh nhau. H quang dng mt chiu thng xut hin s st th
hai u ca in cc. Hiu ng ny xut hin rt r rng trong thi gian u ca s phng
in v h quang c dng thp (di 5A). Nhng sau c nng lng ca ngun kch
thch b vo th s st th s gim i. Nguyn nhn ca s st th ny l do s xut hin
lp in kp hai u ca in cc v lp in kp ny c t trng ngc vi t trng
chnh ca h quang. Vi h quang xoay chiu, do dng i n lun lun i chiu, nn s st
th xut hin khng r rng v rt t c tc dng. chnh l l do gii thch ti sao s
kch thch ph pht x bng h quang dng i n xoay chiu lun lun n nh hn s kch
ph trong h quang dng in mt chiu.
Tia la in
U

c im v tnh cht ca tia la in

Tia la in l ngun kch thch ph c nng lng tng i cao. Ty theo cc thng
s ca my pht tia la in chn, ta c th t c nhit trong plasma tia la in
t 4000 6000C. Tia la in l ngun kch thch tng i n nh v c lp li cao
nhng v nhy li km h quang in. Do thi gian ghi ph cn phi di hn h quang.
V bn cht ca s phng in, tia in l s phng in gia hai in cc c th hiu
rt cao (10.000 - 20.000kV) v dng in rt thp (<1A). N l s phng in gin on t
50 - 300 chu k trong mt giy, ty thuc vo cc thng s ca my pht tia la in c
chn. Do in cc khng b t nng . Do c im ny m tia la in l ngun kch
9

thch ph hp i vi php phn tch cc mu thp, hp kim v dung dch, nhng li khng
ph hp cho vic phn tch cc mu qung, t v bt v khng ha hi t t cc mu loi
ny.
Trong tia la in qu trnh chuyn vt cht mu t in cc vo plasma l gin on
theo tng chu k phng in gia hai in cc.
Nguyn tc lm vic ca tia la in
Trong my ny c mt tia in chnh v mt tia in ch huy. Theo s hnh 3-5, khi
ng mch in K, bin th Tr c np in v tng th ln hng ngn vn. Lc h t
in C c tch in v th hai ct ca t C l th ca khong n gia hai qu cu E. Lc
ny trn mch in LC khng c dng i n, t C c tch in cho n khi t c th Vf
(th phng in gia hai qu cu E) th tia i n s nh qua hai qu cu E, t C phng in
qua E lm cho trn mch dao ng LC xut hin tc khc mt dao ng cao tn, dao ng
ny khng qua c L2 (hay R1); do bt buc phi nh qua khong n F (khong cch
gia hai in cc chnh). Nh vy, h c mt dao ng v mt tia in nh E, th cng c
mt tia in phng qua F, ngha l tia in E iu khin tia in F. Sau qu trnh c
th tip din cho n khi ta ngt cng tc K. Mun cho qu trnh phng in c n nh th
hai qu cu E phi c kch thc xc nh, khong cch khng i v b mt phi nhn. C
nh th in th Vf mi c nhng gi tr xc nh ng vi tng cp thng s ca my pht tia
in c chn, m bo cho qu trnh phng i n F n nh V mt nng lng, v
c hai tia in xy ra ng thi, nn nng lng phi chia i hai khong n E v F. V th
mun c nng lng ln (nhit cao) th th Vf phi rt ln.

Hnh 3-5: S my pht tia in dng hai tia in

Cc b phn khc ca thit b AES xem chng 2.
10

3.2. Phn tch bng phng php quang ph pht x nguyn t

Cng vch ph c trng bng chi sng ca vch ph v ngi ta thng k hiu
cng vch ph l I. Cng I ca vch ph ph thuc vo iu kin kch thch ph,
trng thi vt l ca mu nghin cu v quan trng nht l ph thuc nng nguyn t
nghin cu trong mu. S ph thuc ca cng vch ph vi nng c biu din
bng phng trnh Lomakin-Schaibe.
I = aCb

(3-9)

Trong a, b l cc hng s ph thuc iu kin kch thch v trng thi vt l ca mu

nghin cu.
T (3-9) ta d dng thu c:
lgI = lga + blgC

(3-10)

Phng trnh (3-10) cho thy s tuyn tnh gia lgI v lgC. y l biu thc t c s cho
phng php phn tch nh lng bng quang ph pht x.
Theo phng trnh ny, nu c mt s mu u (mu chun) c nng C bit chnh xc,
v d C1, C2, Cn v xc nh c cng ca 1 vch ph pht x I tng ng ca
chng, th ta c th dng c ng chun I - C, ri t c th d dng tm c nng
Cx cha bit.
Nhng trc y (trc 1965), do khng xc nh trc tip c gi tr cng pht x I
ca mt vch ph, m ngi ta phi chiu chm sng pht x cng I ln knh nh. Sau
xc nh cng hay en ca chng trn knh nh ti ch b chm sng I tc dng
ln. en S ny c tnh theo cng thc:
S = lgI

(3-11)

trong l h s nh tng ca knh nh. Nh vy, ta c phng trnh h qu nh sau, vi

k = lg a:
S = blgC + k

(3-12)

T thc t , hin nay chng ta c hai phng trnh c b n ca php phn tchnh lng
theo ph pht x ca nguyn t. Nu cc my cho php xc nh trc tip c gi tr cng
11

 I th chng ta tnh ton theo phng trnh ( 3-9). Nu cc my quang ph phi xc nh

gin tip cng I qua vic xc nh en S, th phi tnh ton theo phng trnh (3-12),
ngha l phng trnh th nht c dng y = ax, cn phng trnh th hai th c dng y = ax +
b, song chng u l phng trnh ca mt ng thng. Nhng nu o theo phng trnh
en S, chng ta phi loi en ca ph nn. V th trong trng hp ny phng trnh th c
nghim s phi l:
S = .b.logC + ko

(3-13)

Do , phng trnh ( 3-12) v phng trnh ( 3-13) c gi l phng trnh c b n ca

phng php phn tch quang ph pht x nguyn t nh lng. ng biu din cc
phng trnh ny c m t trong hnh 3-6.

Hnh 3-6: Mi quan h gia vch ph v nng cht: (A) I-Cx; (B): S-lgC

3.3. Cc yu t nh hng n chnh xc

Yu t ph
U

- S pht x ph nn
- S chen ln ca cc vch ph gn nhau
12

- S bc x ca cc ht rn
Yu t vt l
U

- nht v sc cng b mt ca dung dch mu

- S ion ha cht phn tch
- Hin tng t o (t hp th)
Hin tng ny thng xut hin trong vng ngoi ca plasma l r rt nht hay khi nng
cht phn tch ln. V vng ny c nhit thp, nn cc nguyn t ca cht phn tch li hp
th chnh tia pht x m cc nguyn t trong li ca ngn la sinh ra, v th lm mt bt i
mt phn cng pht x ca cht phn tch. iu ny cng gp phn gii thch ti sao
nng ln th mi quan h gia cng vch ph pht x Iv nng Cx ca cht l
khng cn tuyn tnh na.
Yu t ha hc
U

- Nng axit v cc loi axit trong dung dch mu

- nh hng ca cc cation
- nh hng ca cc anion
- Thnh phn nn ca mu

3.4. ng dng ca phng php trong phn tch

Phng php phn tch quang ph pht x nguyn t ngy nay gi vai tr quan trng trong
ha hc phn tch. Cng vi s pht trin mnh m ca cc ngnh khoa hc k thut, c bit
l vt l v ha hc, s pht trin ca k thut o v ghi tn hiu, lm tng kh nng ng
dng to ln ca n. Bng phng php ny ngi ta c th xc nh nh tnh, bn nh lng
v nh lng c hn nm chc kim loi v gn mt chc nguyn t kim trong cc i
tng mu khc nhau (v c v hu c).
Phng php phn tch ny tr thnh cng c phn tch nguyn t c lc cho nhiu lnh
vc, nht l sau khi c ngun kch thch ICP.
Phn tch quang ph pht x trong ngnh ha v cng nghip ha hc. N l cng c cc
nh ha hc xc nh thnh phn nh tnh v nh lng ca nhiu cht, kim tra tinh
khit ca cc ha phm, nguyn liu v nh gi cht lng ca chng. N cng l mt
phng php xc nh cc ng v phng x v nghin cu cu trc nguyn t.
Phn tch quang ph pht x nguyn t trong a cht. Ngay t khi mi ra i, phng php
ny c cc nh a cht s dng phn tch cc mu qung phc v cho cng vic thm
13

d a cht v tm ti nguyn khong sn. V th ngnh a cht ca tt c cc nc u c

phng phn tch quang ph pht x rt hin i v hon chnh.
Phn tch quang ph pht x trong luyn kim. Luyn kim cng l mt ngnh s dng phng
php phn tch quang ph pht x u tin vo mc ch ca mnh trc c ngnh ha. Chnh
tnh cht nhanh chng v nhy ca phng php ny l mt iu rt cn thit i vi
ngnh luyn kim. N c th l cng c gip cc nh luyn k im xc nh ngay c thnh
phn ca cc cht ang nng chy trong l luyn kim; qua m h c th iu chnh nguyn
liu a vo ch to c nhng hp kim c thnh phn mong mun, kim tra thnh phn,
kim tra nguyn liu.
Phn tch quang ph pht x trong tiu chun hc. Trc y con ngi tng rng kh c
th hiu bit c thnh phn ha hc ca cc hnh tinh xung quanh tri t chng ta. Nhng
phng php phn tch quang ph pht x ra i m rng tm vi cho con ngi. Bng
phng php ph pht x v kt hp vi mt s knh thin vn, cc nh thin vn c th quan
st c thnh phn ca cc nguyn t ha hc ca cc hnh tinh khc nh mt trng, cc v
sao. Chnh nhng kt qu phn tch thnh phn ca cc mu t do v tinh ly t mt trng v
ni ln ngha ca php o ph pht x trong lnh vc nghin cu thin vn. V nhng kt
qu phn tch thc t cc mu l rt ph hp vi nhng s liu thu c trc y qua phn
tch tia sng t mt trng bng h thng my quang ph v knh thin vn.
Phn tch quang ph pht x trong nng nghip, y v sinh hc. y l nhng ngnh khoa hc
s dng phng php ny em li nhiu kt qu rc r, c bit l trong vic nghin cu th
nhng, nghin cu cc nguyn t vi lng trong t trng, trong cy trng, trong phn bn
ca nng nghip, hay nghin cu thnh phn thc n phc v chn nui, phn tch nguyn t
vi lng trong mu, serum, nc tiu, phc v cha bnh.

3.5. Cu hi n tp
1. Trnh by s xut hin ca ph pht x nguyn t AES.
2. Trnh by c ch hot ng ca ngun h quang in v tia la in.
3. Trnh by phng trnh Schaibe-Lomakin pht biu mi lin h gia cng vch ph
pht x nguyn t vi nng cht c trong plasma.
4. Trnh by cc phng php phn tch nh lng trong phng php quang ph pht x
nguyn t.

14

Ni dung
Chng 4. Phng php quang ph hp th nguyn t ...................................................... 1
4.1. Nguyn tc phng php ph pht x nguyn t (AAS) ............................................ 1
4.2. iu kin to thnh ph hp th nguyn t ................................................................ 3
4.2.1. Qu trnh nguyn t ha ...................................................................................... 3
4.2.2. S hp th bc x cng hng ........................................................................... 5
4.3. S thit b quang ph hp th nguyn t ............................................................... 7
4.3.1. Ngun pht bc x cng hng .......................................................................... 7
4.3.2. iu bin ngun bng gng xoay ...................................................................... 9
4.3.3. Thit b nguyn t ha ......................................................................................... 9
4.4. Phng php phn tch ph hp th nguyn t ....................................................... 10
4.5. ng dng ca phng php ph hp th nguyn t ................................................ 11
4.6. Cu hi n tp .......................................................................................................... 11

Chng 4. Phng php quang ph hp th nguyn t

(Atomic Apsorption Spectroscopy)

4.1. Nguyn tc phng php ph pht x nguyn t (AAS)

Phng php AAS da vo kh nng hp th chn lc cc bc x cng hng ca nguyn
t trng thi t do. (i vi mi nguyn t vch cng hng l vch quang ph nhy nht
ca ph pht x nguyn t ca chnh nguyn t ).
Thng thng th khi hp th bc x cng hng, nguyn t s chuyn t trng thi ng vi
mc nng lng c bn sang mc nng lng cao hn mc gn mc nng lng c bn
nht, ngi ta gi l bc chuyn cng hng (hnh 4-1).

NNG LNG

NGUYN T TRNG

NGUYN T

THI C BN

TRNG THI KCH THCH

Hnh 4-1. Qu trnh hp th nguyn t

Trong phng php ny, cc nguyn t t do ( trng thi hi) c to ra do tc dng ca

ngun nhit bin cc cht t tp hp bt k thnh trng thi nguyn t, l qu trnh
nguyn t ha.

Qu trnh nguyn t ha c th thc hin bng phng php ngn la: bng cch phun m
dung dch phn tch trng thi sol kh vo ngn n kh, hoc bng phng php khng
ngn la: nh tc dng nhit ca l graphit.
Aerosol (sol kh) l trng thi huyn ph ca cc ht rn hay lng (cc ht kch thc siu
hin vi) c phn chia rt tt trong pha kh.
Trong ngn la hoc trong l graphit cht nghin cu b nhit phn v to thnh cc nguyn
t t do. Trong iu kin nhit khng qu cao (15003000C) a s cc nguyn t c
to thnh trng thi c bn. By gi nu ta hng vo lung hi mt chm bc x in t
c tn s bng tn s cng hng, mt phn bc x in t s b hp th bi cc nguyn t,
bi vy,
I Io
Nghin cu s ph thuc ca cng mt vch ph hp th ca mt nguyn t vo nng
C ca nguyn t trong mu phn tch, l thuyt v thc nghim cho thy rng, trong mt
vng nng C nh ca cht phn tch, mi quan h gia cng vch ph hp th v
nng N ca nguyn t trong m hi cng tun theo nh lut Lambert-Beer, ngha l
nu chiu mt chm sng cng ban u l Io qua m hi nguyn t t do ca nguyn t
phn tch nng l N v b dy l L cm, th chng ta c:
I = Io .
A = lg

= KLC

(4-1)

A: hp th l mt i lng khng th nguyn

Io, I: cng nh sng trc v sau khi b cc nguyn t hp th
K: h s ph thuc vo bc sng , M-1cm-1
L: dy lp hi nguyn t, cm
C: nng cht nghin cu trong lp hi, M
Vy, nu trong phng php ph pht x nguyn t, nng cht nghin cu c xc nh
da vo cng vch pht x m cng vch ny li t l vi nng cht b kch thch
2

th phng php AAS c c s khc hn. y tn hiu phn tch li lin quan n cc
nguyn t khng b kch thch.
Ngi ta chng minh c rng thng thng s nguyn t trng thi kch thch khng
qu 12% s nguyn t chung. l l do phng php AAS c nhy cao (c th xc
nh nng trong phm vi ppm-ppb) vi chnh xc cao.

4.2. iu kin to thnh ph hp th nguyn t

4.2.1. Qu trnh nguyn t ha

c th phn tch cc cht theo phng php AAS, ngi ta phi bin cht nghin cu t
trng thi tp hp no thnh trng thi nguyn t t do, l qu trnh nguyn t ha
trong phng php AAS. Qu trnh nguyn t ha thng c thc hin vi tc dng ca
cc ngun nhit theo phng php ngn la hay khng ngn la.
Qu trnh nguyn t ha l qu trnh m trong m u thng dng dung dch b bay hi

v phn hy thnh cc nguyn t.

Gi s kim loi nghin cu Me trong dung dch hp cht MeX, dung dch MeX c phun
vo ngn la n kh dng sol kh. Trong ngn la n kh s xy ra qu trnh nhit phn ca
phn t MeX.
MeX = Me + X

(4-2)

Bn cnh qu trnh (3-2) cng c xy ra qu trnh khc nh qu trnh t o hp cht nh MeO,

MeOH, MeH lm gim nng nguyn t Me.
gim qu trnh to hp cht cha oxy ca kim loi, ngi ta phi to iu kin bu kh
ngn la c tnh kh mnh.
Trong ngn la cng c th xy ra qu trnh ion ha nguyn t lm gim nhy ca php
phn tch. hn ch s ion ha ny, ngi ta phi a vo dung dch phn tch cc cht d
b ion ha tng nn electron trong bu kh.
C hai loi nhiu c k n trong phng php AAS
Th nht, s nhiu ph (spectral interferences), xy ra khi cc ht vt cht t qu trnh nguyn t
ha tn x bc x tia ti, hay khi cc ht (phn t, ion, nguyn t) hp th bc sng rt gn vi
bc sng cng hng ca cht phn tch gy ra nhiu.

S nhiu ph do xem ph vch (chng vch ph) l rt him v cc vch pht x ca ngun catot
rng l rt hp. Tuy nhin, s nhiu c th xy ra nu khong cch gia hai vch ph l 0,01 nm. V
d, vch Vanadi 308,211 nm gy nhiu khi phn tch Al vch 308,215 nm. S nhiu ny c th
bit v trnh c, v d nh ta c th chn vch Al khc, v d, vch 309,270 nm.
S nhiu ph cng do bi s c mt ca cc sn phm chy dng phn t, th hin m ph hp
th b gin n hay cc sn phm dng ht gy tn x nh sng. Trong cc loi nhiu ny, cng
tia l b lm yu i do cc cu t nn, cng tia ti gi nguyn, vic o A mc sai s dng, do
nh hng ti kt qu xc nh nng C. V d, xc nh Ba trong hn hp cha cc kim loi
kim. Bc sng ca vch Ba s dng trong phn tch AAS xut hin gia cc m ph ca CaOH ,

nh vy Ca gy nhiu khi phn tch Ba. Ta c th loi tr nhiu ny bng cch thay th KNO3 trong
khng kh nh mt cht oxy ha, nhit ngn la nh cao hn phn hy v loi tr m ph

CaOH hp th ny.
S nhiu ph do s tn x bi cc sn phm nguyn t ha thng xy ra khi dung dch cha cc
nguyn t nh Ti, Zr (Ziconium) v Vonfram - dng oxit bn c to ra trong ngn la.
May thay, s nhiu ph do sn phm nn khng ph vi qu trnh nguyn t ha bng ngn la v
thng trnh c bng nhiu cch nh iu chnh cc tham s ca qu trnh phn tch nh nhit
v t l nhin liu/cht oxy ha.
Ngi ta c th thm vo cht m bc x in t (radiation buffer) l cht c thm vo vi mt
lng ln vo c dung dch chun v mu nghin cu m s c mt ca cc cht ny ngn cn
c s nhiu ph.
Th hai, s nhiu ha hc (chemical interferences), kt qu ca rt nhiu qu trnh ha hc xy ra
trong qu trnh nguyn t ha v lm thay i tnh cht hp th ca cht phn tch.
S nhiu ha hc c th c gim ti mc nh nht bng vic la chn cc iu kin thch hp.
Hu ht cc loi nhiu ha hc l do cc anion, cc anion ny to hp cht c bay hi thp vi
cht cn phn tch, do lm gim tc nguyn t ha. Kt qu thu c s mc sai s m. V d,
khi xc nh Ca, hp th ca n s gim khi tng nng cc anion gy nhiu nh SO4 , PO4 do
2-

3-

to hp cht kh bay hi vi ion canxi.

S nhiu do to cc ht c bay hi thp c th c loi tr hoc gim thiu bng cch s dng
nhit cao hn.
Cc tc nhn gii phng (releasing agents) l cc cation m u tin phn ng vi cht gy nhiu,
ngn cn cht gy nhiu phn ng vi cht phn tch, c th c a vo. V d, chng ta thm ion
Sr (Strontium) hay La lm gim nhiu do ion PO4 khi xc nh Ca. y, ion Sr hay La thay th cht
3-

phn tch to hp cht kh bay hi.

Cc tc nhn bo v (protective agents) ngn cn nhiu bng cch u tin to hp cht n nh

nhng d bay hi vi cht phn tch. C ba thuc th ph bin dng cho mc ch ny l EDTA, 8hydroxyquinolin v APDC (mui amoni ca 1-pyrolidin-cacbodithioic axit). V d, s c mt ca
EDTA loi tr nhiu do Si, ion PO4 , SO4 khi xc nh Ca.
3-

2-

Hiu ng ion ha:

Qu trnh ion ha cc nguyn t v phn t thng khng ng k trong hn hp chy m khng kh
l cht oxy ha. Tuy nhin, khi oxy hay KNO3 l cht oxy ha, nhit ca ngn la cao, s ion ha
trong ngn la l ng k. Ta c cn bng:

M M+ + e y, M l nguyn t trung ha, M l ion. Thng thng ph ca M hon ton khc ph ca M,

+

bi th qu trnh ion ha cht phn tch lm kt qu nhn c thp hn thc t.

Nu ta a thm vo mi trng ny ht B, n cng b ion ha theo phng trnh:

B B+ + eTh mc ion ha ion M s gim do hiu ng khi lng hot ng (mass action effect) ca cc
electron dng B.
Nh vy, sai lch do qu trnh ion ha th ng c loi tr bng cch thm cc cht d b ion ha
(ionization suppressor) vi nng ln. Mui ca kali thng c s dng nh mt ionization
suppressor bi nng lng ion ha ca nguyn t ny rt thp.

4.2.2. S hp th bc x cng hng

Khi ta hng vo lp hi nguyn t kim loi Me chm bc x in t c tn s ng bng

tn s cng hng ca nguyn t kim loi Me, s xy ra hin tng hp th cng hng
chuyn ln mc nng lng kch thch gn nht.
Me + h Me*

(4-3)

Qu trnh hp th (4-3) tun theo nh lut hp th (4-1). Nh cp phn trc,

ngun nhit khng cao qu (T3000C), i vi nhiu nguyn t, nng cc nguyn t b
kch thch l khng ng k (1-2% so vi nng chung ca cc nguyn t) v t b thay i
theo nhit . Do , trong ph hp th nguyn t, s nguyn t c kh nng hp th bc x
cng hng thc t bng s nguyn t chung ca nguyn t cn xc nh v t b nh hng
ca nhit ngun nhit. l l do ti sao phng php ph hp th nguyn t thng cho
kt qu phn tch chnh xc hn v nhy cao hn phng php ph pht x nguyn t.
5

, nm
200

300

400

500

600

E, eV

5p

4,0

4p

3,0
3p
2,0
1,0
0,0

285nm

330nm

590nm

3s

Hnh 4-2. (a) Ph hp th ca Na, (b) s bc chuyn nng lng Na

Vch cng hng =590nm; =330nm; =285nm;

Cu hi: Ti sao phng php AES li c nhy cao hn khi thay i nhit ca ngn
la so vi phng php AAS?
Tr li: Trong AES, tn hiu phn tch c quyt nh bi s nguyn t hay ion b kch
U

thch, trong khi trong AAS, tn hiu phn tch li lin quan n s nguyn t khng b kch
thch. Thng thng, s nguyn t khng b kch thch vt qu s nguyn t b kch thch
nhiu ln. T s gia cc nguyn t khng b kch thch v s nguyn t b kch thch trong
mi trng nhit cao bin thin theo hm s m vi nhit . Bi vy, mt s thay i
nh v nhit cng s a ti mt s thay i ln v s nguyn t b kch thch. S nguyn
t khng b kch thch thay i rt nh bi chng c mt vi mt lng rt ln. Nh vy,
phng php AES c nhy ln hn theo s thay i ca nhit so vi AAS.

4.3. S thit b quang ph hp th nguyn t

gng xoay
Ngun
Mu

Ngn la

B tn sc

Detector

My tnh

Hnh 4-3. S ph hp th nguyn t

Hnh 4-4. Thit b ph hp th nguyn t

4.3.1. Ngun pht bc x cng hng

C hai loi n c s dng trong AAS: n catot rng (HCL-hollow cathode lamp) v n
phng in khng cc cao tn (EDL-electrodeless discharge lamp).
HCL c dng ph bin, l loi n pht bc x tt, c chi sng cao, vch ph hp v
cng n nh.
Cu to: gm anot bng vonfram, catot c ch to bng kim loi cn phn tch c dng
hnh tr hay ci cc nh, i khi ngi ta s dng loi vt liu bn lm cht mng ph lp
kim loi cn phn tch.
Anot v catot c bt kn trong mt bng thy tinh hnh tr (hnh 4-5) trong cha kh tr
Ar hoc Nr vi p sut 1-5 at.

Hnh 4-5. S v n catot rng

S bt x (sputtering): Khi t in p khong 300V gia hai in cc s xy ra s ion ha

Ar, cc cation Ar v cc in t di chuyn n hai cc (dng i n phng khong 5-10 mA).
Nu in p ln, cc cation Ar s tn cng catot vi nng lng nh bt mt s
nguyn t kim loi v to m my nguyn t.
Nh vy, s bt x l qu trnh m trong cc nguyn t hay cc ion c pht ra t b mt
kim loi bi chm tia ca cc ht tch in.
Ar+
(-)

M*
(-)

S bt x

M*

Ar

(-)

S kch thch

S pht x

Hnh 4-6. Qu trnh trong n catot rng

Mt s nguyn t kim loi b bt x v chuyn ln trng thi kch thch v pht x bc sng
c trng (bc sng cng hng) v tr v trng thi c bn.
Cc nguyn t kim loi bt x trong n tch in khuch tn ti b mt catot v lng kt.

HCL ng dng cho khong 62 nguyn t v c kha cnh thng mi. Mt vi loi HCL c
th cha a nguyn t (c th ln ti 17 nguyn t). Nhng nghin cu v HCL c quan
tm rng ri v n gn lin vi s pht trin ca phng php AAS.
n phng in cao tn EDL:
i khi EDL cung cp ngun bc x cng hng c cng ln hn v thi gian sng di
hn so vi HCL. S dng EDL s nng cao c nhy khi xc nh mt s nguyn t so
vi HCL, v d As, Se, P. EDL ng dng cho 18 nguyn t v c kha cnh thng mi.
Cu to: mt lng nh nguyn t cn phn tch hay mui ca n c bt kn trong mt
bng n thch anh vi mt lng nh kh tr trong (mt vi at). Bng n c t trong
mt xylanh bng gm, trn l hp cng hng c dng hnh xoy c.
Trong trng tn s radio hay vi sng, Ar b ion ha v cc ion ny c gia tc bi dng cao
tn n khi t nng lng kch thch cc nguyn t kim loi pht x c bc x
cng hng.
4.3.2. iu bin ngun bng gng xoay

Qu trnh iu bin c nh ngha l s thay i mt vi tnh cht ca tn hiu nh tn s,

khuch i, hay bc sng trong AAS, tn s ca ngun c iu bin t lin tc n
gin on.
Gia ngun v ngn la ngi ta t mt gng xoay (quay bng m t) (hnh 4-3). Phn
kim loi ca gng c chuyn ng bc x i qua mt na gng, v na kia phn x.
Gng c quay vi tc khng i lm cho tia ti ca ngn la bin i nh k t
cng bng 0 n cc i v sau quay tr li bng 0.
4.3.3. Thit b nguyn t ha

Trong phng php ph hp th nguyn t ngi ta hay dng ngn la lm phng tin
nguyn t ha. Ngn la dng trong phng php ny cng gi ng vi ngn la trong phng
php quang ph pht x nguyn t. Ngoi ra, trong phng php cn dng cc lo i l graphit
lm thit b nguyn t ha. Mt trong cc kiu l ny c trnh by hnh 4-7.

Hnh 4-7. L graphit

y l loi l ng bng graphit c thnh mng di t 930 mm, ng knh trong 45 mm.
Hai u l c kp cht vo hai tip im graphit dy, chc. l khi b chy ngi ta
lun thi qua l mt dng argon, dng kh ny cng ngn b t s tht thot ca lng mu
bay hi khi bung nguyn t ha. Ton b l c t trong bao lnh, lm lnh bng nc.
Dung dch mu c a vo l bng pipet vi lng 50100 l qua l m gia l. Sau khi
sy mu, l c t nng n nhit khng cao qu 3000C. Khi b kh c a mu c
bay hi, hi mu chim y ton b ng l. Nhit ca l graphit c iu khin bng
thit b in t theo chng trnh chn trc.
Thng th nhit ca l c iu khin theo thi gian c chia lm 3 giai on:
-

Giai on sy mu ( lm bay hi dung mi);

Giai on tro ha (tro ha phn t hp cht hu cwo v ui bt nguyn t nn);

Giai on nguyn t ha (cho bay hi ring nguyn t cn xc nh v chuyn nguyn

t xc nh v trng thi nguyn t);

4.4. Phng php phn tch ph hp th nguyn t

Vic gim cng bc x cng hng do hin tng hp th cng hng ca cc nguyn
t nguyn t tun theo nh lut Lambert-Beer (phng trnh 4-1).
i vi bc sng tia ti l n sc v vi mt cht nghin cu c th th K = const, vi
mt iu kin thc nghim c th th chiu di ngn la L = const. Nh vy phng trnh (41) c th vit di dng:
10

A = lg

= KC

(4-4)

Da vo s ph thuc tuyn tnh gia hp th A v nng nguyn t nghin cu ngi

ta c th xy dng phng php xc nh nng theo cc th tc ca phng php ng
chun, nhng thng thng ngi ta thc hin theo phng php thm tiu chun.
Ni dung ca cc th tc ny tng t nh trnh by chng 2.

4.5. ng dng ca phng php ph hp th nguyn t

Phng php AAS c th c ng dng phn tch cc cht trong nhiu i tng phn
tch khc nhau, c bit vi cc mu c nng cht nghin cu thp. Vi phng php ph
AAS, ngi ta c th xc nh hn 70 nguyn t (Mg, Zn, Cu, Ca, Pb, Fe, Ag, Ni, Hg, Cd,
Au, As..) trong cc i tng thc t khc nhau.

4.6. Cu hi n tp
1. Trnh by phng trnh Lambert-Beer pht biu cng vch ph hp th nguyn t ph
thuc vo nng cht phn tch.
2. Trnh by cu to v c ch hot ng ca n catot rng HCL khi ng vai tr b c x
n sc ca ph hp th nguyn t.
3. Ti sao phng php AES li c nhy cao hn khi thay i nhit ca ngn la so vi
phng php AAS?

11

Ni dung
Chng 5. in cc v o in th............................................................................................ 1
5.1. Cc in cc so snh ....................................................................................................... 1
5.1.1. in cc so snh bc-bc clorua .............................................................................. 2
5.1.2. in cc calomen .................................................................................................... 2
5.2. in th tip xc (liquid-junction potentials) ................................................................. 3
5.3. Cc in cc ch th......................................................................................................... 4
5.3.1. Cc in cc kim loi .............................................................................................. 5
5.3.2. Cc in cc mng ................................................................................................... 6
5.3.3. Cc sensor ha hc dng rn .................................................................................. 12
5.4. Cu hi n tp ............................................................................................................... 12

Chng 5. in cc v o in th
Cc nh ha hc thng minh thit k ra cc in cc. Cc in cc ny phn hi chn lc
vi cht cn phn tch trong dung dch (pha lng) hay trong pha kh. Kch thc ca cc in
cc chn lc ion ch c kch thc ca ci bt vit. Cc nh ha hc thc s rt thng minh
khi to ra cc in cc bn dn cm bin ion kch thc siu nh c vi trm micromet v c
th a vo cc mch mu. Vic s dng cc in cc o in th t cho ta thng tin
v ha hc c gi l o in th.
Trong trng hp n gin nht, cht phn tch l cc ht c hot tnh in (electroactive) v
l mt phn ca pin galvanic. Mt in cc, ch hn nh thanh Pt c th nhng vo mt dung
dch cha bit nng , in cc ny c th truyn electron ti hoc t cht phn tch. Do
in cc ny phn hi vi cht phn tch nn n c gi l in cc ch th. Chng ta ni
na pin ny vi na pin cn li qua 1 cu mui. Na th hai ca pin c thnh phn c nh,
n c in th l khng i. Bi v in th ca n khng i nn na th hai ca pin c
gi l in cc so snh. in th ca pin l s khc nhau gia th ca in cc ch th v
in cc so snh.

5.1. Cc in cc so snh
Mt in cc so snh l tng l in cc c in th c bit trc chnh xc,
khng i v hon ton khng nhy cm vi cht phn tch. Ngoi ra, in cc ny phi

chc chn, d dng lp rp v duy tr c th khng i khi c cc dng in nh chy

qua.
5.1.1. in cc so snh bc-bc clorua

in cc bc-bc clorua trn hnh 5-1 da trn phng trnh

Ag(r) + Cl

AgCl(r) + e

Ess (KCl bo ha) = + 0,222 +

E = +0,222V
= + 0,197V

Th kh tiu chun E cho phn ng ny l +0,222V. Nu pin c bo ha vi KCl

25C, th ny l +0,197V.

Hnh 5-1. in cc so snh bc-bc clorua

5.1.2. in cc calomen

in cc calomen trn hnh 5-2 da trn phn ng in cc

Hg2Cl2(r) + e

Hg(l) + Cl

E = +0,268V

Thy ngn (I) clorua (calomen)

Ess. (KCl bo ha) = + 0,268 +

= + 0,241V

Th kh tiu chun E cho phn ng ny l +0,068V. Nu pin c bo ha vi KCl

25C, th ny l +0,241V. in cc calomen bo ha c vit tt l S.C.E (saturated

calomel electrode). S thun tin trong vic s dng KCl l [Cl] l khng thay i khi
cht lng bay hi.

Hnh 5-2. in cc calomen bo ha

5.2. in th tip xc (liquid-junction potentials)

in th tip xc xut hin dc theo lp bin gia cc dung dch in ly c thnh phn khc
nhau.

HCl 1M

HCl 0,01M

Cl

H+

+
Ej

Hnh 5-3. S ch ra th tip xc Ej. di ca mi tn t l vi linh ng ca hai ion

Hnh 5-3 ch ra mt v d n gin v tip xc gia dung dch HCl 1M v dung dch HCl
0,01M. Mt mng xp, ngn cn hai dung dch ny khi s trn ln. C ion H+ v Cl c xu
3

hng khuch tn t pha c nng cao n pha c nng thp. Lc iu khin cc ion t
l vi hot gia hai dung dch.
v d ang xt, cc ion hydro chuyn ng nhanh hn cc ion Cl, nh c ch ra trn
hnh v v kt qu l c mt s phn cc v in tch. Pha bn nng thp in tch lp
bin s tr ln dng hn. Pha bn nng cao c in tch lp bin m hn do s chuyn
ng chm hn ca cc ion Cl. S tng in tch lp bin c xu hng chng li s khc
nhau gia tc khuch tn gia hai ion v cn bng t c nhanh chng. S khc nhau v
in th c to ra do s phn cc in tch c th mt vi phn trm ca vn.
Cng ca th tip xc c th gim i ti a bng cch s dng cu mui gia hai dung
dch. Cu mui s hiu qu nht nu linh ng ca ion m v ion dng trong cu mui l
xp x nhau v nu nng ca chng ln. Dung dch KCl bo ha tha mn c hai yu cu
trn (bng 5-1). Th tip xc ca mt cu mui nh vy l vi milli vn.
Bng 5-1. linh ng ca cc ion trong nc 25C
Ion
+

H
+
Rb
+
K
+
NH4
3+
La
2+
Ba
+
Ag
2+
Ca
2+
Cu
+
Na
+
Li
OH

linh ng, m /V.s

8

36,3010
8
7,9210
8
7,6210
8
7,6110
8
7,2110
8
6,5910
8
6,4210
8
6,1210
8
5,5610
8
5,1910
8
4,0110
8
20,5010

linh ng, m /V.s

Ion
4

Fe(CN)6
3
Fe(CN)6

2
SO4

Br

Cl

NO3

ClO4

HCO3

CH3CO2

11,4510
8
10,4710
8
8,2710
8
8,1310
8
7,9610
8
7,9110
8
7,4010
8
7,0510
8
5,7010
8
4,6110
8
4,2410

Lu rng khng m bo v cng ca th tip xc dc theo cu mui l nguyn

nhn hn ch chnh xc ca phng php phn tch bng o in th.

5.3. Cc in cc ch th
Mt in cc ch th l tng phn hi nhanh chng v lp li vi s thay i nng
ca mt ion cht phn tch. Cc in cc ch th c chia lm ba loi: kim loi, mng v
cc bng bn dn chn lc ion.

5.3.1. Cc in cc kim loi

in cc kim loi ph bin nht l in cc platin, l loi in cc tr n khng tham

gia vo phn ng. in cc ny c nhim v n gin l chuyn cc electron vo hay t
cc phn t trong dung dch. Cc in cc vng c phn tr hn Pt. C nhiu loi cacbon
c s dng lm in cc ch th v tc ca nhiu phn ng oxy ha kh trn b mt
in cc cacbon rt nhanh. in cc kim loi lm vic tt khi c b mt sch v rng.
lm sch in cc, nhng in cc trong dung dch HNO3 nng v sau ra li bng
nc ct.
Hnh 5-4 ch ra phng thc lm vic ca in cc Ag khi n kt hp vi in cc so
snh o nng Ag+. Phn ng in cc Ag l:
Ag+ + e

Ag(r)

E = +0,799V

Phn ng in cc so snh l:
Hg2Cl2(r) + e

Hg(l) + Cl

E = +0,268V

Hnh 5-4. S dng in cc Ag v in cc so snh calomen xc nh nng [Ag+]

Th ca in cc so snh c c nh 0,241V bi v pin in cc c bo ha vi

KCl. Phng trnh Nernst cho ton b pin bi vy s l:

E = 0,558 + 0,05916log[Ag+]

(5-1)

iu ny c ngha l th ca pin trn hnh 5-4 cho php xc nh nng [Ag+]. L tng
nht l th ny thay i 59,16 mV ( 25C) cho mi s thay i phn 10 ca nng
[Ag+].
V d
100,0 ml dung dch NaCl 0,1000M c chun vi AgNO3 0,1000M v th ca pin
trn hnh 5-4 c iu khin. Tnh in p sau khi thm c 65,0 ml AgNO3.
Gii
Phn ng chun l
Ag+ + Cl = AgCl(r)
Th tch ti im tng ng l 100,0 ml. 65.0% ca Cl c kt ta v 35.0% d:

xc nh th ca pin theo phng trnh 5-1, chng ta cn bit nng [Ag+]

[Ag+][Cl] =

[Ag+]=

= 8,5109M

Bi vy in th ca pin s l:
E = 0,558 + 0,05916log(8,5109) = 0,081V
5.3.2. Cc in cc mng

Cc in cc mng i khi cn c gi l in cc pIon bi v cc s liu nhn c

thng c biu din di dng hm p- chng hn pH, pCa hay pNO3.
5.3.2.1. in cc thy tinh o pH
in cc thy tinh c s dng o pH l loi in cc ph bin nht trong cc loi
in cc ion.
Mt loi in cc t hp thy tinh pH kt hp c thy tinh v in cc so snh trong
cng mt thn, c ch ra trn hnh 5-5. S ca pin c th vit nh sau:
Ag(rn)|AgCl(rn) |Cl (dung dch) ||H+(dung dch, ngoi)
in cc so snh ngoi

(dd. phn tch)

H+(dung dch, trong), Cl (dung dch) | AgCl(rn) | Ag(rn)

H+bn trong in cc

in cc so snh trong

(mng thy tinh)

Phn hi ca in cc thy tinh:

Ein cc = constant + 0,05916 log (

25C

(5-2)

Ein cc = constant 0,05916 pH(bn ngoi)

25C

(5-3)

: hiu sut in ng (xp x bng 1, thng th >0,98), phn khng i gi l th bt i

(bi v hai pha ca mt i tng thc l khng ging ht nhau v mt in th nh vn tn
ti ngay c hot ca H+ l nh nhau hai pha ca mng. Chng ta c th xc nh n
bng cch chun ha in cc vi dng dch c pH bit trc.

Hnh 5-5. S in cc t hp thy tinh

Hnh 5-6. S mt ct ngang ca lp mng thy tinh ca in cc pH

Chun ha in cc thy tinh:

in cc thy tinh phi c chun ha vi hai (hay nhiu hn) dung dch m chun pH
ca dung dch phn tch nm trong phm vi ca dung dch m chun ny.
Hi qui cc s liu ri rc (pH1, E1), (pH2, E2)... v phng trnh bc nht, h s gc ca
ng chun ny l 0,05916 mV/pH 25C cho mt in cc. Da vo phng trnh ta
c th tnh c pH ca dung dch phn tch khi o c th ca dung dch.
Thc t chun ha in cc thy tinh l xy dng mi quan h gia tn hiu o c v pH
bng cch thc hin cc php o vi cc dung dch bit pH (hnh 5-7).

Hnh 5-7. Chun ha in cc thy tinh vi cc dung dch m chun

Cc sai s trong php o pH bng in cc thy tinh:

-

Dung dch chun: Mt php o pH khng th chnh xc hn dung dch pH chun,

thng thng cc dung dch pH chun c sai s 0,01 (v d pH = 4,01; pH=7,01, pH
= 10,01).

in th tip xc: in th tip xc tn ti trong cc nt xp gn y ca in cc

trn hnh 5-5. Nu thnh phn cc ion ca cht phn tch l khc vi cc dung dch
m chun, th tip xc s thay i mc d pH ca hai dung dch l ging nhau.
Hiu ng ny gy nn mt khng m bo t nht l ~0,01 n v pH.

S tri th tip xc: Hu ht cc in cc t hp c in cc so snh Ag/AgCl cha

KCl bo ha. Hn 350mg Ag /lit c ha tan trong KCl ch yu di dng
v

. Trong cc nt xp, KCl b pha long v AgCl c th kt ta. Nu dung

dch cht phn tch cha cht kh, Ag c th kt ta trn nt xp. C hai hiu ng

ny u gy ra s thay i th tip xc v l nguyn nhn tri nh ca gi tr pH c

c. C th hiu chnh (b) li ny bng cch chun ha li in cc sau mi
khong thi gian l 2h.
-

Li kim: khi nng [H+] rt thp v [Na+] l cao, in cc phn hi vi Na+ v pH

c l thp hn gi tr pH thc. Li ny c gi l li kim.

Li axit: Trong axit mnh, gi tr pH o c s cao hn gi tr pH thc t c th do

thy tinh bo ha bi H+ v khng th tip tc proton ha.

Thi gian cn bng: cn thi gian nht nh in cc cn bng vi dung dch. Mt

dung dch m tt i hi khong 30s vi s khuy trn . Mt dung dch m ti
(gn im tng ng ca mt qu trnh chun ) cn nhiu pht in cc cn
bng vi dung dch.

Hydrat ha thy tinh: in cc i hi vi gi ngm trong dung dch phn hi vi

H+ chnh xc.

Khng c php ngm in cc trong nc ct hay kh (qu trnh dehydrat

ha)

Nhit : Thang o pH phi c chun ha cng nhit vi nhit m php

o s c thc hin.

Lm sch: Nu mt in cc va mi tip xc vi cc cht lng k nc, chng hn

nh du, n phi c lm sch vi mt dung mi m c th ha tan c cht
lng k nc ny v sau ngm li vo trong dung dch nc.

5.3.2.2. in cc chn lc ion mng rn

Hnh 5-8. S in cc chn lc ion rn

s dng mui v c dng tinh th lm mng chn lc ion

in cc chn lc ion mng rn (solid-state ion selective electrode) da trn tinh th v

c c ch ra trn hnh 5-8. Mt loi in cc ph bin l in cc Florua, s dng tinh
th LaF3 thm Eu2+ (droped). Thm (doping) y ngha l thm mt lng nh Eu2+
thay th La3+. Dung dch thm cha NaF 0,1M v NaCl 0,1M. Cc in cc Florua c s
dng iu khin v iu chnh s Flo ha cc ngun cung cp nc ca thnh ph.
thc hin mt dng in nh, F di chuyn dc theo tinh th LaF3 nh c ch ra
trn hnh 5-9. Cc ch trng anion c to ra trong tinh th khi chng ta thm mt
lng nh EuF2 vo LaF3. Cc ion F lin k c th nhy vo cc ch trng, li mt ch
trng mi sau n. Trong cch ny, F khuch tn t pha ny sang pha khc.

Hnh 5-9. S di chuyn ca F- qua mng LaF3 b sung EuF2.

Bi v Eu c in tch nh hn La3+, cc cc v tr trng xy ra vi tt c Eu2+. Cc anion F lin k c th
nhy vo cc ch trng ny, do c s di chuyn trng t ni ny sang ni khc. S lp li ca qu trnh ny
s gip F di chuyn qua mng tinh th.
2+

Tng t nh vi in cc mng thy tinh o pH, s phn hi ca in cc F l:

Ein cc = constant 0,05916 log(

25C

(5-4)

y xp x bng 1,00. Vi phm vi nng ca F t 106M n 1M, in cc F phn hi

tun theo h thc Nernst.
Ion nhiu cho php o nng F l OH. pH thp, F b chuyn thnh HF (pKa = 3,17)
lm mt nhy ca in cc.
Qui trnh phn tch F ph bin l pha long dung dch cn phn tch trong dung dch m c
lc ion ln cha axetic axit, natri citrat, NaCl v NaOH v iu chnh pH n 5,5. Dung dch

10

m c tc dng gi cc cht chun v dung dch phn tch lc ion khng i, do vy h s

hot ca F l khng i cho tt c cc dung dch.
0,05916 log [F]

Ein cc =
Phn ny l khng i bi v

(5-5)

= cosnt khi lc ion l khng i

pH = 5,5, khng c s nhiu do OH v ch c mt phn v cng nh s chuyn ha t F

sang HF. Ligan citrat trong thnh phn m li to phc vi Al3+ v Fe3+, nhng ion c th
lin kt vi F v gy nhiu cho qu trnh phn tch.

Hnh 5-10. Chun ha in cc mng rn F

V d: Ngi ta s dng in cc F nhng vo cc dung dch chun (gi lc ion khng i

vi dung dch NaNO3 0,1M, cc in th o c ng vi cc nng dung dch chun nh
sau:
[F-], M

E (mV)

1,00105

100,0

1,00104

41,5

1,00103

17,0

Bi v lc ion l khng i, s phn hi ph thuc vo logarit ca nng F. Hy tnh nng

F trong mu nu in th o c l 0,0 mV.
Gii
T s liu thc nghim chng ta thu c hm hi qui
E (mV) = 58,5log[F] 192,5

11

Do E = 0,0 mV [F] = 5,1104M

5.3.3. Cc sensor ha hc dng rn

Cc sensor (cm bin) ha hc c ch to vi k thut tng t nh ch to cc

chip vi in t. Cc bng bn dn (field effect transistor-FET) l sn phm thng mi
sn c, chng hn nh in cc pH c ch ra hnh 5-11.

Hnh 5-11. in cc t hp pH da trn hiu ng bn dn. in tr nhit (thermistor) cm ng

nhit v vic ng dng trong vic t ng b nhit.

Cc bng bn dn cm bin ha hc c thit k phn tch cc ion nh H+, NH4+, NO3,

CO2...

5.4. Cu hi n tp
1. Ti sao khi xc nh nng ion F bng phng php o in th s dng in cc mng
rn chn lc ion, ngi ta thng dng dung dch m c lc ion ln cha axetic axit, natri
citrat, NaCl v NaOH pha long v iu chnh pH n 5,5?
2. Nguyn nhn no lm xut hin th tip xc trong phng php o in th? Gi tr in
th tip xc nh hng nh th no n vic phn tch? Lm th no lm gim in th
tip xc?
3. Vit h thc Nernst cho in cc mng thy tinh? Ti sao phi chun ha in cc thy
tinh trc khi o pH. Hy gii thch cc sai s gy ra khi s dng in cc thy tinh trong
mi trng pH qu cao v qu thp.
4. ngha khi s phn hi in cc ch th tun theo h thc Nernst l g?
12

5. Nu nh ngha in cc ch th, in cc so snh, in cc kim loi. Ly v d cho mi

loi in cc v nu yu cu i hi vi cc in cc ny.
6. Vi in cc bc-bc clorua, chng ta c E = 0,222V, E(KCl bo ha) = 0,197V. Hy d
on gi tr E ca in cc calomen nu E ca n l E = 0,268V.
7. S dng cc gi tr in th cho di y tnh hot ca Cl trong KCl 1M
E (in cc calomen) = 0,268 V, E (in cc calomen, KCl 1M) = 0,280V

13

Ni dung
Chng 6. Phng php in phn........................................................................................................ 1
6.1. S in phn v qu trnh ha hc xy ra khi in phn............................................................. 2
6.2. Th Ohm, s phn cc nng v qu th ................................................................................. 4
6.2.1. Th Ohm................................................................................................................................ 4
6.2.2. S phn cc nng (concentration polarization) .............................................................. 5
6.2.3. Qu th (Overpotential) ........................................................................................................ 5
6.3. Phn tch bng phng php in phn ..................................................................................... 6
6.3.1. in phn vi hai in cc ................................................................................................... 8
6.3.2. iu chnh in p in phn vi in cc th ba ............................................................... 9
6.4. Cu hi n tp ............................................................................................................................ 10

Chng 6. Phng php in phn

(Electrogravimetric)

Trong phn tch bng phng php in phn, cht phn tch c nh lng da trn
khi lng cht kt ta rn bm trn anot hay catot khi in phn dung dch ti hon
ton. S tng v mt khi lng ca in cc ch r cho chng ta lng cht phn tch c
mt l bao nhiu.
Trong h hp v quang ha, cc electron c dch chuyn trong mt chui cc bc t
mt trung tm oxy-ha kh ny sang mt trung tm oxy-ha kh khc, trong nng
lng c lu gi bi cc phn t chung chng hn nh adenosin triphotphat (ATPcoenzim c to bi adenosin triphotphat vi cc nhm photphat ph, l hp cht
quan trng trong qu trnh trao i cht). S h hp l t pht c iu khin bi s
dch chuyn e- t phn t thc n (dng kh) n phn t oxy (dng oxy ha). Quang
ha l qu trnh khng t pht, n i hi nng lng t nh sng mt tri chuyn
ha CO2 v H2O thnh cacbohydrat v O2.
Trong phng php o in th, chng ta thy rng cc phn ng in ha t pht vi
dng khng ng k c iu chnh cho mc ch phn tch. By gi, chng ta s xem
xt cc phn ng oxy-ha kh khng t pht, c iu khin bi dng bn ngoi t
vo, c s dng cho mc ch phn tch.
1

6.1. S in phn v qu trnh ha hc xy ra khi in phn

Xt phn ng:
Catot

Cu2+ + 2e

Cu

Anot

H2O

O2(k) + 2H+ + 2e

2H2O + 2Cu2+ Cu + O2(k) + 4H+

E = (1,2290,337) = 0,892V
Phn ng xy ra theo chiu t phi qua tri (t pht) v th tiu chun E<0.
Gi s chng ta mun iu chnh phn ng ny sang phi trong mt dung dch CuSO4
0,200M v [H+] = 1M, coi p sut oxy

= 1at. Th ca pin l:

Epin = Ecatot Eanot

Nh vy, ta phi t th ln hn 0,913V th chiu phn ng mi din ra t tri sang

phi.
Mt khc trong qu trnh in phn, nng Cu2+ gim, in phn ht Cu2+
([Cu2+]=106M) ta phi t th ln hn 1,069V

Ein phn = Epin = 1,069V

Hnh 6-1. S thit b in phn

Hnh 6-1 ch ra mt cp in cc Pt c nhng vo dung dch, th ln hn 0,913V c

t vo. catot ( din ra s kh) phn ng l:
Cu2+ + 2e Cu
V anot (s oxy ha din ra), phn ng l:
H2O 2e O2(k) + 2H+
Nu dng in I chy trong mch vi thi gian t, in lng i qua bt k im no
trong mch s l:
=
S mol e l:
Mol e =

Nu mi ht (ion, phn t, nguyn t) trao i n electron th s mol phn ng =

S gam phn ng:
m=

, (g)

(6-1)

(6-1) l biu thc ca nh lut in phn Faraday

3

V d: dng I = 0,17A, t = 16 pht, c bao nhiu gam PbO2 s kt ta?

Pb2+ + H2O PbO2 + 4H+ + 2 e

anot

2H+ + 2 e H2(k)

catot

S mol e =

= 1,6103 mol

2 mol e- cho mi mol PbO2 kt ta, bi vy

S mol PbO2 = mol e = 8,4103 mol
= 8,4103 (mol)239,2 (g/mol) = 0,20g

6.2. Th Ohm, s phn cc nng v qu th

phn trc, chng ta xem xt pin in ha di iu kin l b qua s thay i ca
dng. i vi mt pin hot ng tt, hay qu trnh in phn xy ra, dng in nht
thit phi thay i. Khi dng thay i, c ba yu t lm gim cng ca in p t
vo pin galvanic v do lm tng cng in p cn thit t vo cho qu trnh in
phn. Ba yu t l th Ohm, s phn cc nng v qu th.
6.2.1. Th Ohm

Bt k 1 pin no cng c in tr dng in. in p cn thit ion c th chy trong

pin gi l th Ohm, c a ra bi nh lut Ohm.
EOhm = IR

(6-2)

Trong I l cng dng in, ampe v R l in tr ca pin, Ohm.

Nu khng c dng chy trong pin, s khng c th Ohm v I = 0. Nu c dng chy trong
pin, in p t bn ngoi gim bi v mt phn nng lng gii phng bi phn ng
ha hc c dng thng in tr trong pin. in p t vo trong pin in phn
nht thit phi ln thng in tr ca pin v iu khin phn ng ha hc.
Gi s khi vng mt ca cc nh hng khc nh phn cc nng , qu th, in p ca
pin galvanic b gim bi IR v cng ca in p t vo pin b tng bi IR.
Th t vo bn trong pin in phn: Ein phn = ENernst IR

6.2.2. S phn cc nng (concentration polarization)

S phn cc nng xy ra khi nng ca ht to ra hay tiu th mt in cc

khng ging nhau b mt in cc v trong dung dch.
S phn cc nng lm gim cng in p ca pin galvanic v lm tng in p
cn thit cho qu trnh in phn.
Catot

Cu2+ + 2e

Cu

Trong qu trnh in phn, nu ion Cu2+ chuyn ng nhanh n b mt in cc bi s

khuch tn v i lu, nng Cu2+ s nh nhau trong ton b dung dch. Gi nng
ca Cu2+ trong dung dch l [Cu2+]o v nng gn b mt in cc l [Cu2+]s. Th
ca phng trnh Cu2+ + 2e Cu ph thuc [Cu2+]s ch khng phi l [Cu2+]o. Chng ta
vit:
Ecatot = 0,339 +

log[Cu2+]s

(6-3)

Nu [Cu2+]s = [Cu2+]o, th ca catot s ph hp vi nng ca Cu2+ trong dung dch.

Nu dng thay i nhanh ti mc m Cu2+ khng kp tin n ln cn ca in cc v
[Cu2+]o s ln hn [Cd2+]s. chnh l s phn cc nng . Kt qu l, th ca phng
trnh (6-3) s tr nn m hn v th pin = (Ecatot Eanot) tr nn m hn.
S phn cc nng lm gim cng in p pin galvanic v lm tng in p i
hi cho qu trnh in phn.
Th t vo trong pin in phn Ein phn = ENernst IR Ephn cc nng
Cc ion c th chuyn ng bi s khuch tn, i lu v lc tnh in. Tng nhit s
dn ti tng tc khuch tn v bi vy lm gim s phn cc nng . Tng lc ion,
lm gim lc tnh in gia ion v in cc. Cc yu t ny u c nh hng ti mc
phn cc. Cng tng t, in cc c b mt ln hn, dng c th ln hn i qua m
cha c s phn cc.
6.2.3. Qu th (Overpotential)

Hnh (6-2) ch ra tnh cht ca catot Pt v Ag phn ng kh H+

H+ + 1e H2(k) + H2O
Pt

Ag

I, A
2,0
1,5
1,0
0,5
0
0,2

0,3

0,4

0,5

0,6 0,7 0,8

0,9 Ein phn, V

Hnh 6-2. Mi quan h dng-th ca in cc Pt v Ag trong mi trng dung dch H2SO4

c pH = 3,2, khng c O2. Trong c hai trng hp, in cc calomen bo ha c s dng.

Phn ng ny bt u 0,35V in cc Pt v 0,8V in cc Ag. iu g din ra

y? Nu qu trnh ha hc l nh nhau, ti sao li khng i hi th nh nhau in
cc khc nhau. Khi in cc Hg c s dng vi thc nghim ny, th kh bt u
tn 1,3V.
D s phn cc nng v th Ohm c tnh vo, vn cn mt hiu in th ln
hn qu trnh in phn xy ra. S khc nhau gia th tnh (sau khi tnh ti s phn
cc nng v th Ohm) v th qu trnh in phn xy ra c gi l qu th.
Th t vo pin in phn Ein phn = ENernst IR Ephn cc nng Equ th
Qu th ph thuc vo:
-

Bn cht ca in cc, cc in cc khc nhau, qu th l khc nhau;

Mt dng cng ln, qu trnh in phn xy ra cng nhanh, qu th s cng

ln. Qu th trn b mt in cc c din tch ln nh hn qu th trn in cc
c b mt nh (lin quan n mt dng);

Nhit tng, qu th gim;

6.3. Phn tch bng phng php in phn

Trong phng php in phn, cht phn tch c kt ta trn b mt in cc. S
tng v mt khi lng trc v sau in phn dung dch n hon ton ch cho chng
ta bit lng cht phn tch c mt l bao nhiu.
6

V d
Mt dung dch cha 0,40249g CoCl2.xH2O c in phn xc nh lng nc kt
tinh trong phn t. Sau khi tin hnh phn tch ngi ta xc nh c khi lng
Coban bm trn in cc Pt l 0,09937g. Hy xc nh x?
Gii
Co2+ + 2e Co
Hp cht ch cha CoCl2 v H2O, chng ta c th vit:
=

x=6

Vy hp cht c thnh phn l CoCl2.6H2O

Thit b in phn c minh ha trn hnh 6-1. Cc cht phn tch thng c kt ta
trn in cc sch, tr v c din tch b mt ln.
Cc du hiu nhn bit qu trnh in phn hon ton hay cha bao gm: mt mu dung
dch, khng c du hiu ca cht kt ta trn b mt in cc mi ngp, hoc nh tnh
s c mt ca ion trong dung dch.
V d nh khi in phn Cu2+ hoc Co2+, mu ca dung dch mt dn i trong qu trnh
in phn. Mt cch khc l khi in phn, ngi ta khng nhng ton b in cc vo
dung dch. bit phn ng in phn din ra hon ton hay cha, ngi ta c th
nhc cao v tr cc in phn ln, hoc thm nc c thm phn in cc mi ngp.
Sau khi in phn thm 15 pht, nu khng thy lp sn phm in phn phn in
cc mi ngp th c th coi qu trnh in phn l hon ton. Cch th ba l ly mt t
dung dch ang in phn v kim tra nh tnh xem c cn ion kim loi ang in phn
khng.
Phng php in phn c th coi l mt phng php phn tch n gin nu chng ta
ch phn tch mt ion kim loi trong mt dung dch tr (khng c ion gy nhiu). Trong
thc t, c th c cc yu t nhiu cng kt ta trong qu trnh in phn. Nc c th b
7

in phn, n phn hy thnh H2 v O2 in p t vo bnh in phn cao. Bt kh

thot ra in cc c th gy nhiu qu trnh kt ta cht rn. Bi nhng yu t phc
tp ny, iu chnh in p t vo in cc l rt quan trng cho vic phn tch thnh
cng.
6.3.1. in phn vi hai in cc

Khi khng c s phn cc nng , in p cn thit qu trnh in phn xy ra bao

gm:
Ein phn

= ENernst IR Equ th
= (Eanot Ecatot) IR Equ th

(6-4)

Gi s rng chng ta gi in p cho qu trnh in phn dung dch Cu2+ 0,10M trong
mi trng HNO3 1M l 2,0V. Do ng c in phn, nng Cu2+ gim. Cui cng, s
phn cc nng c thit lp v Cu2+ khng th vn chuyn ti catot duy tr dng
ban u. Khi dng gim, cng ca th Ohm v qu th phng trnh (6-4) gim.
C th coi Eanot = cosnt v kt qu lm nng ca dung mi ln v b oxy ha anot.
Phn ng oxy ha anot l:
H2O O2 + 2H+ + 2e
Nu Ein phn (l in p thc t t vo bnh in phn) v Eanot l khng i trong
phng trnh (6-4) v nu IR v qu th gim trong qu trnh in phn, th Ecatot phi
tr nn m hn gi gi tr i s cn bng. Trn hnh (6-3) th catot gim ti 0,4V,
vi gi tr ny H+ b kh ti H2. Do th catot gim t +0,3 n 0,4V, cc ion khc nh
Co2+, Sn2+ v Ni2+ c th b kh. Tm li, khi in p t vo bnh in phn l khng i,
th catot tri ti gi tr m hn v bt k cht tan c th d dng b kh hn H+ c th b
in phn.
ngn cn th catot tr nn m hn v cc ion nhiu c th b kh, cht kh cc catot
chng hn nh NO3 c thm vo dung dch. Cht kh cc catot l cht c th d dng
b kh hn H+
NO3 + 10H+ + 8e NH4+ + 3H2O

Ecatot,V

Th kh ca Cu2+

0,3

Bt u s phn cc nng

Bt k ht gy nhiu

0,2

no c th b kh

0,1

trong min in th
ny u c th gy

nhiu cho qu trnh

0,2

phn tch

0,3
0,4

Th kh ca H+
Thi gian

Hnh 6-3. Ecatot thay i theo thi gian khi in phn vi hai in cc khi in p t vo
in cc l khng i

6.3.2. iu chnh in p in phn vi in cc th ba

Qu trnh in phn vi ba in cc duy tr c th catot khng i v do vy s lm

tng chn lc ca phng php in phn ln rt nhiu. in cc m phn ng
nghin cu xy ra c gi l in cc lm vic. in cc calomen c s dng lm
in cc so snh cho in cc lm vic. in cc ph tr (cn gi l in cc truy cp)
l in cc cp dng ph tr cho in cc lm vic. C mt dng ng k gia in cc
lm vic v in cc so snh. Dng chy qua in cc so snh c th b qua, bi vy in
th ca n s khng b nh hng bi th Ohm, s phn cc nng v qu th. N thc
s c duy tr bng in cc so snh. Trong qu trnh in phn kim tra th (hnh 64), in p gia in cc lm vic v in cc so snh c gi khng i bng mt thit
b c gi l iu p (potentiostat).

e-

e-

Catot
(in

Anot (tr
in cc)

cc lm
vic)

A
in cc so
snh
calomen

V
iu bin

Hnh 6-4. Mch in s dng cho qu trnh in phn vi mt in cc th ba

 hiu ti sao khi th catot l khng i c th tng chn lc cho qu trnh phn tch,
chng ta hy xem xt v d khi in phn dung dch cha Cu2+ 0,1M v Sn2+ 0,1M. T th
kh tiu chun chng ta c th ni Cu2+ s c in phn trc Sn2+.
Cu2+ + 2e Cu

E = 0,339V

Sn2+ + 2e Sn

E = 0,141V

Th catot ti Cu2+ c th b kh l:
Ecatot = 0,339 +

log (0,1) = 0,31V

Nu 99,99% Cu2+ c in phn, nng ca Cu2+ cn li l 105M v in p catot i

hi qu trnh kh tip tc l
Ecatot = 0,339 +

log (105) = 0,19V

Khi th catot l 0,19V, c th coi qu trnh in phn Cu2+ l hon ton. Cu hi y l

liu Sn2+ c b kh hay khng? kt ta Sn t dung dch cha Sn2+ 0,1M, in p catot
cn t vo bnh in phn l:
Ecatot, kh ion thic) = 0,141 +

log (0,1) = 0,17V

Do vy, qu trnh kh Sn2+ l khng xy ra.

6.4. Cu hi n tp
1. Trnh by s in phn v cc qu trnh ha hc xy ra trong qu trnh in phn.
2. Trnh by cc yu t nh hng n in p cn thit t vo bnh in phn phn
ng in phn xy ra.
3. Trnh by phng php in phn vi hai in cc v nu cc u nhc im.
4. Trnh by phng php in phn vi vic kim tra th in cc.

10

Ni dung
Chng 7. Phng php phn tch vn-ampe............................................................................ 1
7.1. C s ca phng php .................................................................................................. 1
7.1.1. c im chung ....................................................................................................... 1
7.1.2. Qu trnh xy ra trn in cc thy ngn ................................................................. 3
7.1.3. in th na sng v phng trnh sng cc ph ................................................... 9
7.1.4. Cc cc i trn sng cc ph ............................................................................... 10
7.1.5. Phng trnh Inkovich ........................................................................................... 10
7.2. Cc phng php vn-ampe trc tip ........................................................................... 11
7.2.1. in th na sng E1/2 v phn tch cc ph nh tnh .......................................... 11
7.2.2. Phng php cc ph dng mt chiu ................................................................... 12
7.2.3. Phng php o vi phn ........................................................................................ 13
7.2.4. Cc ph xung ......................................................................................................... 14
7.2.5. Phng php vn-ampe ngc (vn-ampe ha tan- stripping analysis) .............. 16
7.3. Cu hi n tp ............................................................................................................... 18

Chng 7. Phng php phn tch vn-ampe

7.1. C s ca phng php
7.1.1. c im chung

Phng php phn tch vn-ampe l nhm cc phng php da vo ng cong vn-ampe,
hay cn gi l ng cong phn cc, l ng cong biu din mi quan h gia cng
dng in vi in th khi tin hnh in phn dung dch phn tch. Qu trnh in phn c
thc hin trong mt bnh in phn c bit, trong c mt in cc c din tch b hn
in tch ca in cc kia nhiu ln. in cc c din tch b c gi l vi in cc. Qu
trnh kh (hay oxy ha) ch yu xy ra trn vi in cc.
V d, ng cong vn-ampe trn hnh 7-1 l ng cong m t mi quan h dng v th ca
in cc lm vic trong qu trnh oxy ha hay kh ca hn hp Fe(CN)63/Fe(CN)64 xy ra
trn in cc a quay. Theo qui c, dng l dng khi cht phn tch b kh trn in cc
lm vic. Gii hn ca dng khuch tn cho qu trnh oxy ha Fe(CN)64 xy ra in th
ln hn 0,5V (in cc so snh l calomen bo ha).
1

Fe(CN)64

Fe(CN)63 + e

Ferroxyanide

Ferricyanide

(xyanua st II)

(xyanua st III)

vng ny, dng c iu khin bi tc khuch tn ca Fe(CN)64 ti in cc. Hnh 72 ch ra dng ny t l vi nng [Fe(CN)64] trong dung dch.

Hnh 7-1. ng cong vn-ampe cho hn hp 10 mM K3Fe(CN)6 v 20-60mM K4Fe(CN)6 trong dung dch
Na2SO4 0,1M trn in cc a quay cacbon thy tinh. Tc quay 2000 vng/pht, in th qut 5mV/s.

Hnh 7-2. S ph thuc dng gii hn vo nng K4Fe(CN)6

Vic ng dng ng cong in phn cc vo mc ch phn tch c nh bc hc ngi

Tip Khc Heyrovski tm ra vo nm 1922. Do pht minh v phng php phn tch da vo
2

ng cong in phn cc v nhng ng gp xy dng pht trin phng php phn tch,
nm 1959 Heyrovski c tng gii thng Nobel v ha hc. Dng phng php vn-ampe
ngi ta c th xc nh c nhiu ion v c, hp cht hu c. Qu trnh phn tch c th
c thc hin trong mi trng nc v c mi trng khng nc. Php phn tch c th
c thc hin vi nhy, chn lc v chnh xc rt cao.
7.1.2. Qu trnh xy ra trn in cc thy ngn

Phng php vn-ampe da trn qu trnh in phn vi in cc git thy ngn c gi l

phng php cc ph (hnh 7-3).

Hnh 7-3. Thit b vn-ampe vi in cc lm vic Hg

Mt s lng ln cc phn ng c nghin cu vi in cc thy ngn l cc phn ng kh.

b mt in cc Pt, s kh H+ xy ra vi nhiu cht phn tch.
2H+ + 2e H2(kh) E = 0,000V
Bng 7-1 ch ra rng qu th cho s thot H2 trn b mt in cc Hg l rt ln. Trong mi
trng trung tnh hay kim, thm ch cc cation kim loi kim (nhm I) b kh d dng hn
H+. Hn na, s kh ca mt ion kim loi trn in cc Hg dng hn hng l d dng hn
s kh trn b mt in cc rn.
K+ + e

K(rn)

K+ + e + Hg K(hn hng Hg)

E = 2,936 V
E = 1,975 V
3

in cc thy ngn khng thun li cho vic nghin cu phn ng oxy ha bi v Hg d b

oxy ha trong mi trng khng to phc th gn 0,25V (c so snh vi in cc
calomen bo ha). Nu nng Cl l 1M, Hg b oxy ha gn gi tr 0V bi v Hg(II) c
n nh bi Cl do to phc:
Hglng + 4Cl

+ 2e

nghin cu cc phn ng oxy ha bng phng php vn-ampe, cc in cc lm vic

nh Pt, Au, C hay kim cng trong dung dch nn thch hp c s dng.
Bng 7-1. Qu th (V) ca qu trnh thot kh cc mt dng khc nhau 25C
10 A/m2

in cc

100 A/m2

1000 A/m2

10 000 A/m2

H2

O2

H2

O2

H2

O2

H2

O2

Pt

0,0154

0,0398

0,0300

0,521

0,0405

0,638

0,0483

0,766

Pt trn

0,024

0,721

0,068

0,85

0,288

1,28

0,676

1,49

Cu

0,479

0,422

0,584

0,580

0,801

0,660

1,254

0,793

Ag

0,4751

0,580

0,7618

0,729

0,8749

0,984

1,0890

1,131

Au

0,241

0,673

0,390

0,963

0,588

1,244

0,798

1,63

Graphit

0,5995

0,7788

0,9774

1,2200

Pb

0,52

1,090

1,179

1,262

Zn

0,716

0,746

1,064

1,229

Hg

0,9

1,0

1,1

1,1

S hnh thnh sng cc ph ca mt ion kim loi:

Ta nghin cu qu trnh in phn trn catot l in cc thy ngn, cn anot l in cc c
din tch ln v d in cc calomen. V in cc calomen c din tch b mt ln hn din
tch in cc git Hg rt nhiu nn qu trnh in cc ch yu xy ra trn in cc git Hg.
V in cc Hg l catot nn ngi ta gi y l phn cc catot. Nu trong dung dch khng c
cc cht c kh nng b kh di tc dng ca dng in, cng dng in I s t l vi
in th t vo hai cc (nh lut Ohm).
I=

(7-1)

I l cng dng in chy qua bnh in phn;

E l in th ging vo hai cc;
R l in tr ca bnh in phn;
4

T (7-1) cho thy cng I ph thuc tuyn tnh vi in th t vo hai cc bnh in

phn.
Khi c cc cht tham gia phn ng kh trn catot Hg trong min in th nghin cu, dng
ng cong I-E s thay i. Khi in th ging vo hai cc ca bnh in phn t n gi tr
in th kh ca ion nghin cu, trn in cc git thy ngn c th to thnh hn hng:
Mn+ + ne + Hg M(Hg)

(7-2)

in th ca in cc git Hg khi xy ra qu trnh thun nghch 7-2 tnh theo phng trnh
Nernst:
E = E +

ln

(7-3)

Ca (Camalgam) l nng ca hn hng (M);

l h s hot ca hn hng;
CM l nng ca ion kim loi b kh ti lp dung dch st b mt ca in cc, M;
l h s hot ca ion kim loi M trong dung dch;
aHg l hot ca thy ngn trong hn hng
E l th in cc tiu chun ca in cc, V
Do kt qu ca phn ng (7-2), khi cng dng in bt u tng th nng ion kim loi
lp dung dch st b mt in cc gim. Tuy nhin, do hin tng khuch tn, cc ion kim
loi su bn trong dung dch s tin n lp dung dch st b mt in cc. V vy cng
dng in s ph thuc tc khuch tn, m tc khuch tn ion li ph thuc hiu s
nng

su bn trong dung dch v nng CM st b mt in cc.

I = KM(

CM )

(7-4)

Trong thnh phn dng in chy qua bnh in phn, ngoi dng in sinh ra do s khuch
tn ion kim loi n st b mt in cc v gy ra phn ng in cc, ngi ta gi l dng
khuch tn, cn c thnh phn dng in sinh ra do s dch chuyn cc ion n cc in cc
do tc dng ca in trng d cc ion ny khng tham gia phn ng in cc. Ngi ta gi
dng in sinh ra n thun do s dch chuyn cc ion khng tham gia qu trnh in cc l
dng dch chuyn. Dng dch chuyn cn tr vic o thnh phn dng khuch tn (c trng
cho ion nghin cu) nn ngi ta phi loi b dng khuch tn khi phn tch theo phng
5

php vn-ampe. gim v i n loi b dng dch chuyn, ngi ta c th a thm vo

dung dch phn tch mt cht in ly tr (khng tham gia phn ng in cc) c nng ln
hn nng ion nghin cu nhiu ln. Ngi ta gi y l cht in ly nn. Cation ca cht
in ly nn s chn tc dng ca in trng v lm dng dch chuyn thc t bng khng.
in th bt u xy ra qu trnh in phn trc ht ph thuc vo bn cht ion b kh cng
nh thnh phn dung dch cht nghin cu nh: nng cc ion c mt trong dung dch,
nng ion H+, s c mt ca cc cht to phc...
in th phn hy ca cht in ly thc t bng hiu i s ca in th anot v catot:
E = Ea Ek

(7-5)

Khi dng in cc calomen lm anot th th anot Ea thc t khng thay i khi c dng in
nh chy qua bnh in phn. Thc vy, qu trnh anot trn calomen chnh l s oxy ha thy
ngn kim loi thnh ion Hg+ v chuyn Hg+ vo dung dch:
2Hg 2Hg+ + 2e

(7-6)

Nhng dung dch ca in cc calomen li c ion Cl vi nng khng thay i (thng l

dung dch KCl bo ha hoc dung dch KCl 3M) nn lp tc s xut hin kt ta calomen.
2Hg+ + 2Cl Hg2Cl2

(7-7)

Nng ion Cl lun lun khng thay i v do nng Hg+ khng i v th in cc

Ea trong sut qu trnh in phn khng i, Ea = const. Nu trong trng hp ny ta chp
nhn Ea = 0 V v din tch b mt ca anot qu ln so vi din tch ca catot nn phn cc
catot khng ng k) th th bt u in phn l:
E = Ek hay Ek = E
in th ny gi l in th thot kim loi (hay th kh) ca ion kim loi trong iu kin
ang xt. in th thot kim loi ph thuc vo nng ion kim loi b kh. Nng ion
kim loi cng b cng kh b kh, th in p t vo bnh in phn c th bt u qu trnh
in phn phi cng ln.
Khi tng in th t vo catot (in th t vo bnh in phn) th nng CM phng
trnh 7-4 s gim dn, d rng trong qu trnh in phn lun c cc kim loi mi lp su
6

bn trong dung dch b sung n st b mt in cc do hin tng khuch tn. Nhng s n

lc ng vi in th E no , vn tc kh kim loi s bng vn tc khuch tn v nng
CM lp dung dch st b mt in cc bng khng, CM = 0. Qu trnh in phn y
thng xy ra vi cng dng b (thng b hn 105A) nn nng dung dch su bn
trong ca khi dung dch thc t khng i v bng

. Cng dng chy qua bnh in

phn lc by gi t gi tr khng i Id d cho c tip tc tng in th t vo bnh in

phn. ng dng phng trnh 7-4 vi CM = 0 ta c:
Id = KM

(7-8)

Dng Id theo (7-8) c gi l dng gii hn. Thay Id vo 7-4 ta c:

I = Id KM CM v
CM =

(7-9)

Tng t, nng kim loi hn hng c to thnh theo qu trnh (7-2) cng t l vi
cng dng:
Ca = KaI =

(7-10)

Thay 7-9, 7-10 vo 7-3 ta c:

E = E +

ln

(7-11)

Trong qu trnh in phn xy ra trong bnh phn tch cc ph, ngoi thnh phn Id (dng
khuch tn) lin quan n qu trnh kh ion kim loi, cn c cc thnh phn khc khng lin
quan n qu trnh in cc gi l dng khng Faraday.
Vic to thnh dng khng Faraday c th do my nguyn nhn:
Khi nhng in cc vo dung dch, trn b mt s xut hin lp in kp. Lp in kp c th
xem nh mt t in, khi t ny phng in s tiu th mt lng in no . Khi tng in
th t vo hai in cc, in dung ca t ny s tng ln. Dng phng in ca t li to nn
mt thnh phn ca dng khng Faraday gi l dng t in. Ngoi dng t in, dng dch
chuyn nh nu trn cng l thnh phn dng khng Faraday.

Trong thc t phn tch, dng dch chuyn c th c loi b nh tc dng ca nn cc ph

l dung dch cc cht in ly mnh, tr c nng ln.
Tt c cc vn va m t trn y gii thch dng c bit ca ng cong I-E.

Hnh 7-4. Qut th dng bc thang. Dng c o min c t m mu xanh.

Hnh 7-5. Cc ph (a) Cd2+ 5mM trong HCl 1M, (b) HCl 1M

thc hin c vic o dng bng phng php cc ph vi vic thay i th dng bc
thang (stair voltage ramp) trn hnh 7-4. Sau khi git Hg hnh thnh t mao qun, th c
to ra m hn 4 mV. Sau khi i khong 1s, dng c o trong khong 17 ms cui trc khi
git Hg ri. Dng sng cc ph c m t trn hnh 7-5 l kt qu ca qu trnh kh Cd2+
to thnh hn hng:
8

Cd2+ + 2e Cd(hn hng)

Trn hnh 7-5, phn u ca ng cong, cng dng ng vi phn ny tuy khng bng
khng nhng cng rt b. l do tc dng ca dng khng Faraday. Ngi ta gi l
dng d. Thng thng dng d c vo khong 107A. Dng d c gy ra do dung dch
phn tch khng sch to nn qu trnh kh cc tp cht. Tuy nhin trong thc t phn tch
ngi ta phi tm mi cch gim bt nh hng ca tp cht bng qu trnh lm sch thch
hp, bng cc bin php che vi cc cht to phc. Phn tip theo ca ng cong nng ln
t ngt ng vi qu trnh xy ra trn in cc (kh ion kim loi trn catot) v cng
dng s tng nhanh. Phn cui ca ng cong gn nh nm ngang ng vi lc t dng gii
hn Id. ng cong I-E c dng sng nn ngi ta gi l sng cc ph.
7.1.3. in th na sng v phng trnh sng cc ph

T phng trnh 7-11:

E = E +

ln

Ta thy c mt s i lng khng ph thuc cc iu kin th nghim tr nhit . Bi v

hn hng to thnh khi in phn trn in cc git Hg c nng b nn hot ca thy
ngn trong hn hng aHg thc t bng hot ca Hg tinh khit v l mt gi tr khng i.
Khi phn tch s dng dung dch nn c nng ln pha long nn h s hot
coi l khng thay i. Cc h s hot

, h s KM, Ka cng khng thay i vi l do

tng t. Vy (7-11) c th vit di dng:

E = E +

ln

ln

(7-12)

Hay

E = E1/2 +

ln

(7-13)

Vi

E1/2 = E +

ln

(7-14)

i lng E1/2 c gi l th na sng v chnh l in th ng vi cng dng o

c bng mt na dng gii hn v khi I=Id/2 th theo phng trnh (7-13) s cho ta E = E1/2.
Th ny c trng cho cht phn tch mt dung dch nn xc nh v l c s cho phn tch
nh tnh. Vi cc phn ng in cc m cht phn ng v sn phm phn ng u dng
dng dch, chng hn nh Fe3+ + 1e Fe2+ th E1/2 gn nh bng th kh tiu chun E.
9

7.1.4. Cc cc i trn sng cc ph

i khi dng ng cong cc ph b bin dng khc vi dng l tng hnh 7-1, 7-5. l
vic xut hin cc cc i. Ngi ta phn bit hai loi cc i: cc i loi mt v cc i
loi hai. Vic xut hin cc cc i lin quan n cc hin tng ng lc hc khi to git
thy ngn, do hin tng hp ph ca cc ion trn b mt in cc. gim cc cc i trn
sng cc ph, ngi ta thng a vo dung dch phn tch cc cht hot dng b mt nh
gielantin, aga-aga.
Oxy phi c loi b khi dung dch phn tch bi v n gy ra hai sng do s kh ti H2O2
v ti H2O (hnh (7-6). Thng th N2 (hay Ar) c thi vo dung dch phn tch khong 10
pht ui oxy. Sau N2 c thi gi cho khng c O2 trong dung dch.

Hnh 7-6. Cc ph ca dung dch KCl 0,1M bo ha khng kh v sau khi thi N2 ui O2

7.1.5. Phng trnh Inkovich

Phng php phn tch cc ph nh lng t trn c s mi quan h gia dng gii hn vi
nng ion kim loi CM v cc i lng khc qua phng trnh Inkovich:
Id = 607zD1/2m2/3t1/6CM

(7-15)

Trong
z l in tch ion kim loi
D l h s khuch tn, cm2/s
CM l nng cht phn tch mM/lit
m l khi lng thy ngn chy ra t mao qun mg/s
t l thi gian to git Hg, s
Trong cc i lng trong biu thc (7-15), h s khuch tn D kh xc nh bng thc
nghim v cng t khi tm thy trong cc s tay.
10

Trong phn tch cc ph, m v t c trng cho mao qun, c th xc nh bng thc nghim.
Trong thc t, v D, n, v t c th c duy tr khng thay i trong iu kin thc nghim
nn phng trnh (7-5) c th vit di dng:
Id = KCM

(7-16)

T phng trnh (7-16) cho thy cng dng gii hn Id ph thuc tuyn tnh vi nng
cht nghin cu v (7-16) l c s cho phn tch cc ph nh lng.

7.2. Cc phng php vn-ampe trc tip

7.2.1. in th na sng E1/2 v phn tch cc ph nh tnh

in th na sng E1/2 l c trng nh tnh ca cht nghin cu. Nu phn tch nh tnh
ngi ta cn xc nh in th na sng E1/2. Ngi ta c th xc nh in th na sng bng
phng php th.
Theo phng trnh 7-13, ta thy log

ph thuc tuyn tnh vi E. Do da vo s liu

ph thuc in th E, ta s c ng thng ct trc honh ti

thc nghim thit lp log

im E = E1/2, ngha l khi log

= 0 (hnh 7-7)

Da vo th na sng tm c, ngi ta c th da vo s tay th na sng (hoc theo cc

ph chun), phn on nguyn t hoc hp cht nghin cu. Thng th ngi ta dng kt
qu ny chn nn cc ph cho vic tin hnh phn tch nh lng, trnh c cc nguyn
t hp cht cn tr.

log

E
E1/2

Hnh 7-7. Xc nh in th na sng bng th

11

Trong cc my cc ph hin i, c phn mm dnh cho vic tnh ton th na sng E1/2 theo
cc s liu thc nghim ca cc ph ghi c, nh ngi phn tch trnh c cc thao
tc tnh ton nh va trnh by trn.
7.2.2. Phng php cc ph dng mt chiu

Phng php cc ph dng mt chiu hay cc ph c in c ng dng kh rng ri trong

thc t phn tch nh lng. C s ca phng php ny l phng trnh 7-16.
Phng php ng chun:

Xy dng ng chun mi quan h gia I v Cch. ng chun l mt hm bc nht c

dng nh hnh 7-8.
Id

I = KC

Id4
Id3
Idx
Id2
Id1
0

C
Cch1

Cch2 Cx Cch3

Cch4

Hnh 7-8. Phng php ng chun trong phn tch nh lng bng phng php cc ph

Vi dung dch nghin cu cha bit nng , chng ta tin hnh ghi ph ca mu nghin cu
vi iu kin nh khi tin hnh xy dng ng chun. Vi gi tr Ix nhn c t dung dch
phn tch ta c th tnh c nng cht nghin cu.
Phng php thm tiu chun:

u tin ghi ph ca cht nghin cu ta c gi tr Ix. Thm vo dung dch nghin cu dung
dch chun c nng Cch, ta ghi cc ph cng vi iu kin ghi vi dung dch phn tch,
c gi tr cng dng gii hn Ix+ch. Sau li thm mt lng dung dch chun vo
dung dch trn vi Cx+2ch, o c cng dng gii hn Ix+2ch... Xy dng th thm
chun. T suy ra c Cx t Ix.

12

Id

I = KC

Idx+3ch
Idx+2ch
Idx+ch
Idx
0

C
Cx

Cx+ch

Cx+2ch

Cx+3ch

Hnh 7-9. Phng php thm chun trong phn tch nh lng bng phng php cc ph

7.2.3. Phng php o vi phn

y l mt ci tin trong phng php o trong cc ph dng mt chiu nhm tng chn
lc ca phng php phn tch cc ph. Trong phng php ny, thay cho vic o theo
ng cong I-E ngi ta dng ng cong

- E.

E
E1/2

Hnh 7-10. Cc ph ca phng php cc ph vi phn v cc ph thng

Vi phng php cc ph vi phn, ta c th xc nh cc hp cht c th na sng kh gn

nhau trong cng mt dung dch m khng cn tch chng ra khi nhau. iu ny thc hin
c v phng php cc ph vi phn c nng sut phn gii cao hn hn phng php cc
ph thng. V d, hai ion Pb2+ v Tl+ trong nn KNO3 2N c cc th na sng khc nhau
0,06V. Trn cc ph thng hai sng cc ph chp nhau trn cng mt cc ph . Tuy
13

nhin, trn ng cong vi phn, ta thy hai sng cc ph nh c hai cc tr phn bit r rt.
Phng php cc ph vi phn cng cho kt qu chnh xc hn cc ph thng v trong
phng php ny ta c th xc nh chnh xc cc cc tr, cng nh o chiu cao cc cc i
chnh xc hn o gi tr Id trong cc ph thng.
7.2.4. Cc ph xung

Trong cc ph dng mt chiu, chnh thnh phn dng t che lp dng Faraday khi gi tr
dng Faraday b, v th chnh dng t in hn ch nhy ca phng php cc ph
dng mt chiu. Vic tch dng Faraday khi dng in chung chy qua bnh in phn l
bin php tng nhy ca phng php vn-ampe. Cc ph xung l bin php nhm tch
dng Faraday khi dng t in. c im ca phng php ny l s phn cc ha in
cc ch th (cc git thy ngn) bng cc xung in trong thi gian thch hp.

Hnh 7-11. Cc ph xung. Dng c o min c t m mu xanh khi dng Faraday cn ln cn dng
t in thc t bng 0.

Thc nghim chng minh dng in np v dng phng in ca t in bt k (k c in

dung to ra do cc lp in kp) tng gim dn theo hm ly tha vi thi gian, trong kh
s tng gim ca dng Faraday khi ging in th vo cc in cc gy phn ng in
cc li theo hm bc hai theo thi gian. Ni cch khc dng t tt nhanh hn dng Faraday.
iu cho php tch dng t in do lp in kp to ra khi dng Faraday nu chn thi
im ghi cng dng thch hp, lc cng dng Faraday cn ln cn dng t in
thc t bng 0. D nhin, cc qu trnh ny xy ra vi cng dng rt b, nhng vi cc s

14

 in t hin i, cho php khuch i cc dng in b n gi tr cn thit c th iu

khin c cc my ghi m khng gy mo tn hiu, c bit l khi c cc my tnh vi
tc tnh ton ln.
Cng dng in chy qua bnh in phn t l vi b mt in cc, m in tch b mt
in cc thay i tng lc trong qu trnh ln ln ca git thy ngn. V vy phi ging xung
in ch mt ln vo lc xc nh thi gian sng ca git thy ngn. Thun li nht l ging
xung in vo git thy ngn cui giai on tng trng ca git Hg, lc git Hg sp ri.
Ti chnh thi im ny din tch b mt ca git Hg thay i khng ng k. Thi gian o
cng dng cui xung in.

Hnh 7-12. Dng sng cho cc ph xung vung. Cc thng s c trng l chiu cao xung Ep = 25mV, bc
chiu cao Es = 10 mV, thi gian xung l 5 ms. Dng c o gia vng 1 v vng 2. Gi tr ti u l Ep = 50/n
(ms), Es = 10/n (mV) trong n l s e- trong na phn ng.

C hai phng php cc ph xung: phng php thng v phng php xung vi phn.
Trong phng php u, cui giai on tn ti ca mt git, ngi ta cc ha git thy
ngn bng xung in hnh ch nht, ko di t 40-60 ms. Vy trong phng php ny xung
in ging vo cc c dn vo v cng dng c o giai on cui ca mi xung.
Trng hp ny cc ph khng khc cc ph ca cc ph thng.
Trong trng hp sau, in cc b phn cc nh cc ph thng bng in p thay i
chm. Nhng cui thi gian tn ti ca git Hg, ngi ta ging mt xung in b sung c
bin khng ln lm ~50 mV v thi gian ~100 ms. Vic o hiu s cng dng in
15

chy qua bnh in phn trc v sau khi ging xung in, tc l o gia s ca cng
dng vi gia th in th ging xung in c bin xc nh. V vy, ng cong s c
dng pic vi cc i ng vi E = E1/2 v th ca

v E (theo nguyn tc ca phng

php cc ph vi phn).
Cng dng y t ph thuc vo ng hc ca qu trnh in cc, v vy phng php
c nhy khng ch vi qu trnh thun nghch m cn c vi qu trnh khng thun nghch.
l u im ni bt ca phng php cc ph xung so vi cc phng php cc ph khc.
Trong thc t phn tch ngi ta hay dng cc ph xung vi phn.

Hnh 7-12. So snh gia cc ph xung thng v xung vi phn. Xung thng: thi gian ca git Hg l 1s, chiu
cao xung l 4ms v thi gian o l 17 ms. Xung vung vi phn: thi gian ca git Hg l 1s, chiu cao xung Ep =
25mV, bc xung l Es = 4 mV, thi gian xung l 67 ms v thi gian o l 17 ms.
u im ca cc ph xung vi phn:

- nhy tn hiu tng

- c phn gii tt, c th tch nhiu
- php o nhanh
7.2.5. Phng php vn-ampe ngc (vn-ampe ha tan- stripping analysis)
c im ca phng php:

- cht phn tch c lm giu vo mng Hg bng phn ng kh

- cht phn tch b oxy ha tr li bng ging th dng hn (qu trnh ha tan)
- o tn hiu trong qu trnh oxy ha
Ta bit rng qu trnh ion kim loi b kh trn catot Hg theo phn ng:
Men+ + ne- Me(Hg)
16

Kim loi c ha tan vo catot Hg to thnh hn hng. S kh c xy ra trn in cc

git Hg treo (khng phi git Hg ri) khi hiu in cc tng ng vi dng gii hn. Khi
nng ca kim loi trong hn hng nhanh chng ln hn nng ion kim loi trong dung
dch chung quanh in cc. By gi nu cho phn cc tuyn tnh anot trn cc git Hg treo
in th in cc ng vi s xut hin dng oxy ha ha tan kim loi trong hn hng thy
ngn.
Nu khi tin hnh in phn, ta chn iu kin lng kim loi b kh t l vi nng ion
kim loi c trong dung dch th dng (dng pic) s ph thuc vo nng ion nghin cu ,
cn v tr s cng ca pic s ln hn dng gii hn khi kh ion loi.

Hnh 7-13. Phng php vn-ampe ha tan xc nh Fe(III) trong mu nc bin vi vic thm tiu chun mi
ln 50 pM Fe(III).

S tng hu ch ca tn hiu phn tch m ra kh nng ln trong vic xc nh vi lng v

siu vi lng cc ion kim loi trong dung dch.

17

Hnh 7-14. (a) Cc ph ha tan anot ca mu mt ong (mt ong c ha tan trong nc v axit ha ti pH =
1,2 bng HCl. Cd, Pb, v Cu b kh t dung dch ln mng Hg trong 5 pht in p 1,4V (vs. S.C.E.) (b) Cc
ph nhn c khi khng qua giai on kh 5 pht.Nng ca Cd v Pb trong mt ong tng ng l 7 v
27 ng/g (ppb). chnh xc nm trong khong 24%.

Bng 7-1. Gii hn pht hin i vi phng php von-ampe ha tan

7.3. Cu hi n tp
1. Trnh by s hnh thnh sng cc ph ca mt ion kim loi trn in cc git Hg

18

2. Trnh by phng trnh Inkovich biu din s ph thuc cng dng khuch tn vo
nng cht phn tch.
3. Ti sao phi ui oxy khi phn tch bng phng php cc ph?
4. Cht nn cc ph l g? Nu vai tr ca cht nn cc ph.
5. Trnh by c s phn tch nh tnh v nh lng bng phng php cc ph. Trnh by
th tc ng chun v thm tiu chun trong phn tch nh lng bng phng php cc
ph.
6. Trnh by nguyn tc hai phng php tng nhy ca cc ph xung thng v cc ph
xung vi phn. So snh hai phng php.
7. Trnh by nguyn tc ca phng php vn-ampe ha tan. Tnh u vit ca phng php
ny so vi phng php cc ph thng.

19

Ni dung
Chng 8. Phng php chit.................................................................................................... 1
8. 1. c im chung ca phng php ................................................................................. 1
8.2. Phn loi qu trnh chit ................................................................................................. 2
8.3 Cc c trng nh lng ca qu trnh chit .................................................................. 3
8.3.1 nh lut phn b Nernst .......................................................................................... 3
8.3.2 H s phn b............................................................................................................ 3
8.3.3 chit R ................................................................................................................. 4
8.3.4. H s tch v h s lm giu ................................................................................... 6
8.4 Cn bng trong h thng chit ......................................................................................... 7
8.4.1 Cn bng trong h thng chit 1 baz hu c .......................................................... 7
8.4.2 Cn bng trong h thng chit 1 axit hu c ............................................................ 8
8.4.3 Cn bng trong h thng chit hp cht ni phc .................................................... 8
8.5 Mt s vn trong k thut chit................................................................................. 11
8.5.1 Cc phng php chit ........................................................................................... 11
8.5.2 Chn dung mi ........................................................................................................ 11
8.5.3 Cht tr chit ........................................................................................................... 11
8.5.4. Ra phn chit ....................................................................................................... 12
8.5.5 Gii chit ................................................................................................................. 12
8.6 Bi tp ............................................................................................................................ 12

Chng 8. Phng php chit

Trong mt s ln cc vn phn tch thc t, chng ta phi xc nh v nh lng mt
hay mt vi cu t t mt hn hp phc tp. Vic tch cht cn xc nh ra khi hn hp
l nhim v u tin. Trong chng ny chng ta s tho lun cc nguyn l tch trong
phn tch.

8. 1. c im chung ca phng php

Chit l qu trnh chuyn cht tan t mt pha ny sang pha khc da trn tnh tan khc nhau
ca cht tan trong hai pha (hnh 8-1).

L do ph bin thc hin qu trnh chit trong phn tch ha hc l tch hay lm giu
cht phn tch, hay tch n ra khi nhng cht l c th gy nhiu trong phn tch. Ph bin
nht l qu trnh chit gia dung mi nc v dung mi hu c.

Hnh 8-1. S phn b ca mt cht tan gia hai pha lng

Cc dung mi hu c l nhng hp cht t phn cc nn thng khng tan trong nc, cht
c phn cc rt ln.
Dietyl ete, toluen, hexan l cc dung mi c t trng nh hn nc, chng ni trn pha
nc. Clorofoc CHCl3, CH2Cl2, CCl4 l cc dung mi ph bin c t trng ln hn nc.
Trong hn hp hai pha, mt pha nc chim u th, pha kia dung mi chim u th.
Qu trnh chit thng xy ra vi vn tc ln nn c th thc hin qu trnh chit tch, chit
lm giu mt cch nhanh chng, n gin. Sn phm chit thng kh sch. V cc l do ,
ngy nay phng php chit khng ch c ng dng trong phn tch m cn c s dng
vo qu trnh tch, lm giu, trong sn xut cng nghip.

8.2. Phn loi qu trnh chit

Da vo bn cht hp cht chit, Morison v Freizer chia hp cht chit thnh hai
nhm ln l:
+ Chit cc hp cht ni phc (hay cn gi l cc chelat)
+ Chit tp hp ion
Chelat l hp cht phc, trong hp cht ny, ion kim loi (axit Lewis) b mt ligan (baz
Lewis) tn cng nhiu hn mt nguyn t.

Tp hp ion l cc tp hp khng tch in do s trung ha in tch ca cc ion i

nhau. S to thnh tp hp ion ch yu do lc tnh in. Cc tc gi chia tp hp ion
thnh ba nhm c th chit c theo cc kiu sau:
-

Qu trnh chit xy ra do cc ion kim loi tham gia to ion c kch thc ln c
cha cc nhm hu c phc tp, hoc i khi ion kim loi lin kt vi mt ion c
kch thc ln

Qu trnh chit ion kim loi do to cc solvat: tham gia to cc solvat l cc anion
( v d nh cc halogenua..) v cc phn t dung mi cha oxy nh ru, ete thay
vo cc v tr ca phn t nc trong ion kim loi

Qu trnh chit bng amin v axit cacboxylic: y cc ion kim loi c chit
di dng mui c khi lng phn t ln. Chnh nh khi lng phn t ln m
cc mui ny d tan vo dung mi hu c

8.3 Cc c trng nh lng ca qu trnh chit

8.3.1 nh lut phn b Nernst

Gi s cht tan S c phn b gia pha 1 v pha 2. Hng s phn b (partition

coefficient), K, l hng s cn bng ca phn ng:
S(trong pha 1) S(trong pha 2)
Ks =

(8-1)

Gi s pha 2 l hu c, pha 1 l pha nc

[S]i: nng ca S trong pha i (i=1,2)
Vi mt hp cht chit xc nh th Ks ch ph thuc vo nhit v bn cht dung mi.
Gi tr Ks cng ln th kh nng hp cht S t pha nc vo pha hu c cng ln khi thc
hin qu trnh chit.
8.3.2 H s phn b

Trong thc t rt kh xc nh dng xc nh ca hp cht ha tan trong c hai pha.

V d 1: 1 amin B, axit lin hp BH+, khi thay i pH th nng hai dng thay i

V d 2: HgCl2 tan trong pha hu c di dng HgCl2, nhng tan pha nc di dng
HgCl2, HgCl+, .. Xc nh ring nng HgCl2 th rt kh khn. c th c lng kh
nng chit ca mt hp cht no bng dung mi hu c ngi ta dng h s phn b D
D=

(8-2)

Chu c: tng nng cc dng ca hp cht nghin cu trong pha hu c

Cnc: tng nng cc dng ca hp cht nghin cu trong pha nc
8.3.3 chit R

nh ngha: chit R (%) l phn trm lng cht chit i vo pha hu c vi lng
cht trong pha nc ban u ti thi im cn bng.
R=

(8-3)

Gi s rng cht tan S c th tch V1 (dung mi 1: nc) c chit vi V2 ml dung mi

hu c (v d toluen). Gi m l s mol ca S trong h thng v gi q l phn S vn cn
trong pha nc thi im cn bng. Nng mol trong pha nc bi vy l

. Phn

cht tan S chuyn sang pha 2 l (1-q) v nng trong pha hu c 2 l (1-q) . Do vy,

(8-4)

Gii phng trnh (8-4) i vi q suy ra phn cht tan S cn li trong pha nc sau ln
chit th nht
=

(8-5)

T (8-5) cho php ta ni rng phn cht tan trong pha nc ph thuc vo h s phn
b v th tch. Nu cc pha c tch ra v dung mi hu c mi c thm vo, phn
cht tan cn li trong nc s l:
q.q =

(8-6)

Sau n ln chit vi th tch dung mi V2 hu c, phn cht tan cn li trong nc s l:

qn =

(8-7)

V d: Mt hp cht A c h s phn b gia pha hu c v pha nc l D = 60. Trong

500 ml dung dch c 10 mg cht A.
a. Sau 1 ln chit vi 50 ml dung mi hu c, c bao nhiu phn trm cht A c
tch vo pha hu c
=

Sau ln chit 1, phn trm cht A c tch vo pha hu c l:

R(%) =

= 85,7%

b. Sau bao nhiu ln chit nh trn th chit t c 99%

Phn cht tan A cn li trong pha nc l 1% = 0,01
C phng trnh:
qn =

= 0,01 =

ly logarit hai v:
log0,01 = log

n = 2,37

do nN n = 3
Nh vy, sau 3 ln chit th chit t c 99%
c. Mi ln chit ch s dng 10,0 ml dung mi hu c th sau 5 ln chit phn trm
A c tch vo pha hu c bng bao nhiu?
q5 ==
R(%) =

= 0,019
=

= 98,1%

Bi tp: Cht tan A c h s phn b gia toluen v nc l 3 (D = 3). Tnh phn cht tan
A cn trong pha nc khi thc hin chit 100 ml dung dch cha cht tan A 0.010M
vi
(a) Mt ln vi 500 ml toluen
(b) Nm ln vi mi ln l 100 ml toluen

S. (a) 6%; (b) 0.1%

5

Qua v d v bi tp ta c nhn xt:

Chit nhiu ln vi mi ln mt lng nh dung mi th hiu qu hn so vi chit t
ln vi lng ln dung mi.
8.3.4. H s tch v h s lm giu

c lng kh nng tch hai cht A, B ra khi nhau bng qu trnh chit, ngi ta
dng h s tch
=

(8-8)

Nu = 1, ta khng th thc hin tch hai cht

ra khi nhau bng qu trnh chit. Gi tr cng khc 1 bao nhiu th vic tch cng
thc hin d dng.
Mt tham s c trng ton din hn cho kh nng tch l h s lm giu S.
Gi s ta cn tch cc cht A v B trong hn hp ra khi nhau bng mt qu trnh no .
Ngi ta gi h s lm giu SB/A l t s nng ca cht A so vi cht B trong pha hu
c ln hn t s nng ca cht A so vi cht B trong dung dch nc ban u. Gi s
l nng cc cht A v B trong nc ban u v [A]hc, [B]hc l nng cc cht A
v B trong pha hu c sau khi qu trnh chit t trng thi cn bng.

SB/A =

V ta bit rng RA =

; RB =

(8-9)

; thay vo (8-9)

SB/A =
V d, gi s DA = 104, DB = 0,1 th h s tch =

(8-10)
= 105, ngha l h s tch rt ln.

Tuy nhin, qu trnh chit ny khng hon ton thnh cng v khi dng qu trnh chit
ny tch A khi B th d rng ta tch c 99,99% . A ra khi nc, nhng trong sn
phm chit vn cn mt lng kh ln cht B (gn 10%) v theo (8-10) th h s lm
giu ca qu trnh l:
6

SB/A =

0,1

Cng vi h s tch = 105, nhng nu DA = 102, DB = 103 th:

SB/A =

103

Ngha l SB/A s nh hn hai bc. Trong trng hp ny cht A s chuyn vo pha hu c

99%, cn cht B ch chuyn vo pha hu c 0,1%. Vy h s lm giu S phn nh kh
nng tch hai cht ra khi nhau thc cht hn h s tch .

8.4 Cn bng trong h thng chit

Trong qu trnh chit c nhiu qu trnh xy ra trong pha nc, pha hu c, trong mi
pha li c nhiu cn bng rt khc nhau. Cn bng trong h thng chit rt phc tp, khi
n gin ha phi cn nhc.
8.4.1 Cn bng trong h thng chit 1 baz hu c

Gi s 1 amin (1 baz hu c) B, axit lin hp vi n l BH+

B + H2O

BH+ + OH

Kb

Bnc

Bhu c

Kphn b =

Gi s BH+ ch nm trong pha nc tc ch c B i vo pha hu c.

D=
C [BH+]=

D=

= Kphn bB

(8-11)

chit 1 baz vo nc, chng ta phi s dng pH thp chuyn n thnh BH+.
Ngc li mun chuyn mt axit HA vo nc, chng ta phi s dng pH ln
chuyn axit thnh A.
V d: gi s rng h s phn b ca mt amin Kphn b = 3,0
Bnc Bhu c

Kphn b =

= 3,0 v BH+ c Ka = 109

Nu 50 ml dung dch amin 0,010 M c chit vi 100 ml dung mi, nng ca amin
cn li trong pha nc bng bao nhiu?
a. pH = 10,00
b. pH = 8,00
pH = 10,00: D =

% amin cn trong nc =

= 2,73
=

100 = 15%

[B]nc = 0,15.0,010M = 0,0015M

pH = 8,00: D =

% amin cn trong nc =

= 0,273
=

100 = 65%

[B]nc = 0,65.0,010M = 0,0065M

pH = 10,00, baz ch yu dng B v n c chit vo pha hu c, pH = 8,00 baz
ch yu dng BH+ v n vn c gi li trong nc.
8.4.2 Cn bng trong h thng chit 1 axit hu c

Gi s rng mt axit HA (Ka) c phn b gia hai pha hu c v nc.

HA + H2O

H3O+ + A

Ka

HAnc

HAhu c

Kphn b =

Gi s A khng tan trong pha hu c.

D=

= Kphn bHA

(8-12)

8.4.3 Cn bng trong h thng chit hp cht ni phc

Hu ht cc phc chit vo dung mi hu c phi khng mang in. Cc phc mang in

tch, v d, Fe(EDTA)- hay

khng tan trong dung mi hu

c. Mt cch thc trong vic tch cc ion kim loi ra khi nhau l chn lc ca phc
8

ion kim loi vi mt ligan hu c v tch n vo dung mi hu c. C 3 ligan c s

dng cho mc ch ny c ch ra di y: Dithizone (diphenylthoocacbazone), 8hydroquinolino (oxine) v cupfemon.
Mi ligan c i din nh mt axit yu, HL, n s mt 1 proton khi lin kt vi ion kim
loi.
HL(nc)
n

+
MLn(nc)

Ka =

(8-13)

(8-14)

Mi ligan trong s ny c th to phc vi nhiu kim loi, nhng v chn lc c

iu chnh bi pH.
Chng ta hy bt u t phng trnh h s phn b ca ion kim loi gia hai pha khi tt
c ion kim loi trong pha nc l Mn+ v tt c cc ion kim loi pha hu c dng
MLn (hnh 8-2).

Hnh 8-2. Chit mt ion kim loi vi vic to phc. Phn cht tan ch yu trong pha nc l Mn+ v
phn cht tan ch yu trong pha hu c l MLn.

Chng ta nh ngha hng s phn b ca ligan v phc nh sau:

HLnc

HLhu c

Kphn b (ligan) =

(8-15)

MLn(nc)

HLn(hu c)

Kphn b (phc) =

(8-16)

H s phn b chng ta cn tm l:
D=

(8-17)

T (8-14) v (8-16), chng ta c th vit:

[MLn]hu c = Kphn b (phc).[MLn]nc = Kphn b (phc)..[Mn+]nc[L]nnc
S dng [L]nc phng trnh (8-13) a ti:
[MLn]hu c =

(8-18)

t gi tr [MLn]hu c ny vo phng trnh (8-17) a ti:

D
Bi v hu ht HL l trong pha hu c, chng ta thay [HL]nc =

vo m

t h s phn b cho hu ht cc trng hp:

D
T phng trnh (8-18), chng ta nhn thy rng h s phn b khi chit cc ion kim
loi ph thuc vo pH v nng ligan. Hon ton c kh nng la chn mt pH m
ti D l ln vi 1 kim loi ny v nh vi mt kim loi khc. V d trn hnh 8-3 ch ra
rng Cu2+ c th tch ra khi Pb2+ v Zn2+ bng vic chit vi dithizone pH = 5,00.

Hnh 8-3. Chit cc ion kim loi s dng dithizone vi dung mi l CCl4. pH = 5, Cu2+ c chit
hon ton vo CCl4 trong khi Pb2+ v Zn2+ vn cn trong pha nc.

10

Dithizone (diphenyl thiocacbazone) l hp cht mu xanh l cy, n tan trong dung mi

khng phn cc v khng tan trong nc pH<7.
Dithizone c s dng rng ri trong qu trnh chit phn tch, xc nh cc kim loi
bng phng php so mu, v loi b lng vt cc kim loi t dung dch m.
Trong ng dng di y, mt dung dch chit lp nhiu ln vi dung dch mu xanh
dithizone trong CHCl3. Min l pha hu c tr nn , ion kim loi c tch ra t
dung dch m di dng phc mu . Khi phn chit xanh, vt ion kim loi cui cng
c tch. Hnh 8-3 ch cho chng ta thy rng ch nhng ion kim loi nht nh c
th chit c mt pH nht nh.

8.5 Mt s vn trong k thut chit

8.5.1 Cc phng php chit

Chit gin on: l sau mt ln chit, tch ly pha hu c, ri li thm dung mi hu c

vo phn pha nc, lp i lp li thao tc nhiu ln cho ti khi t yu cu v tch (xem
phn 8.3.3)
Chit lin tc: khi h s phn b b th cch chit nh trn l kh khn v mt th gi
(phi chit nhiu ln). Trong trng hp ngi ta hay dng cch chit lin tc: cho
dung mi hu c tip xc vi dung dch nc, c th thc hin bng nhiu cch, mt
trong nhng cch c m t hnh di.
8.5.2 Chn dung mi

Cn chn dung mi sao cho h s phn b D ln. Ngoi ra cn cn ch n nht, t

trng, mc tan ln nhau gia hai pha v yu t ny c nh hng n qu trnh chit.
8.5.3 Cht tr chit

l cc cht in ly lm tng kh nng chit. Cc cht tr chit thng dng vi nng

cao, sau ny c tr ngi cho vic x l pha nc, do , phi chn loi mui c th d
dng loi b khi dung dch khi cn, v d mui amoni. Ngoi ra, khi chit cn ch n
hin tng to nh v cn tm cc bin php ngn nga hin tng .
Khi c nhiu ion cng b chit, trong nhiu trng hp, phi dng cc cht che loi
tr nh hng ca ion nhiu.
11

8.5.4. Ra phn chit

Sau khi tch, trong phn dung mi hu c c tch ra khng trnh khi c ln mt t
tp cht, do cn ra phn chit , thng l lc vi dung dch nc c cht tr chit,
pH, .. thch hp.
8.5.5 Gii chit

Chuyn cht tch t pha hu c sang pha nc. C th dng dung dch axit mnh hay
dung dch thuc th thch hp, hoc cho bay hi dung mi hu c.

8.6 Bi tp
1. Axit yu HA (Ka = 106) c hng s phn b gia pha nc v hexan l 4,0 (Kpb = 4,0).
Tnh nng ca axit ny trong hexan khi 30 ml dung dch axit HA 0,080M c chit
vi 5,0 ml hexan pH bng 2,00 v 10,00. Hiu qu chit ca HA vo dung mi hexan
pH = 2,00 hay 10,00?

12

Ni dung
Chng 9. Phng php sc k .............................................................................................................. 1
9.1. nh ngha .................................................................................................................................... 1
9.2. Phn loi sc k ............................................................................................................................ 2
9.3. Cc i lng c trng ca sc k ............................................................................................. 4
9.3.1. Sc k ............................................................................................................................... 4
9.3.2. Mi quan h gia thi gian lu v h s phn b ................................................................ 6
9.4. Hiu qu tch ............................................................................................................................... 6
9.4.1. phn gii .......................................................................................................................... 6
9.4.2. S khuch tn ....................................................................................................................... 8
9.4.3. Chiu cao a ....................................................................................................................... 10
9.4.4. Phng trnh chiu cao a ................................................................................................. 11
9.5. ng dng phng php sc k .................................................................................................. 12
9.5.1. Phn tch nh tnh .............................................................................................................. 12
9.5.2. Phn tch nh lng ........................................................................................................... 13
9.6. Cu hi n tp ............................................................................................................................ 14

Chng 9. Phng php sc k

9.1. nh ngha
Nguyn l hot ng ca sc k nh qu trnh chit nhng mt pha c gi c nh v
mt pha ng di chuyn qua pha c nh ny.
Dung mi ra gii

CT SC K

Dung mi gii hp

Cht lng i vo ct gi l dung mi ra gii. Cht lng i ra khi ct gi l dung mi

gii hp. Qu trnh m cht kh hay cht lng i qua ct sc k gi l qu trnh ra
gii. Ct sc k c nhi vi cc ht c kch thc nh nh c ch ra hnh v 9-1.

Hnh 9-1. tng ng sau sc k: cht tan A c hp ph ln hn i vi pha tnh so vi cht tan B,
lu li trn ct lu hn.

9.2. Phn loi sc k

Trn c s s tng tc gia cht tan v pha tnh ngi ta chia sc k ra lm cc loi sau
y:
- Sc k hp ph: Pha tnh l cht rn, pha ng l cht lng hay kh. Cht tan c hp
ph trn b mt ca cc ht rn. Cc cht tan c hp ph cng mnh th n cng di
chuyn chm trong ct (hnh 9-2).

Hnh 9-2. Sc k hp ph v sc k phn b

Hnh 9-3. Sc k trao i ion v sc k loi c phn t

Hnh 9-4. Sc k i lc

- Sc k phn b: Pha tnh l cht lng c lin kt vi b mt rn, thng l SiO2. Pha
tnh thng l cht kh. Cn bng ca cht tan gia vi pha tnh v pha lng c thit
lp trong sc k kh (hnh 9-2).
- Sc k trao i ion: Cc loi nha trao i ion, v d nha trao i anion nha trao i cation

hay

c lin kt vi pha tnh bng lin kt cng ha tr. Pha

ng l cc cht lng cha cc ion cht tan c in tch tri du c lin kt vi pha
tnh bi lc tnh in (hnh 9-3).
- Sc k loi c phn t: cn c gi l sc k lc gel hay sc k thm thu gel. K
thut sc k ny cho php tch cc phn t da trn kch thc ca n. Cc cht tan c
3

kch thc ln hn s i qua ct nhanh chng. Trong trng hp l tng ca sc k

loi c phn t, s khng c tng tc gia pha ng v cht tan. Pha ng l cht kh
hay lng s i qua gel xp. Cc l xp l nh loi cc phn t cht tan c kch thc
ln. Cc phn t ln khng cn thm nhp vo cc l xp. Do vy, cc phn t nh s cn
nhiu thi gian hn i qua ct (hnh 9-3).
- Sc k i lc: y l loi sc k c chn lc cao nht s dng s tng tc chn lc
gia phn t cht tan v mt phn t th hai, phn t gn vi pha tnh nh lin kt cng
ha tr. V d, cc phn t bt ng c th l mt khng th vi mt loi protein c th.
Khi c mt hn hp cha hng nghn protein i qua ct, ch c mt protein l phn ng
vi khng th lin kt ca ct. Tt c cc cht tan khc c ra sch t ct, protein cn
tch s c tch ra bng cch thay i pH hoc cng ion (hnh 9-4).

9.3. Cc i lng c trng ca sc k

9.3.1. Sc k
Sc k l th m t s phn hi ca detector vi thi gian ra gii. Hnh 9-5 ch ra sc k
khi hn hp cha octan, nonan v mt cht cha bit c tch bng phng php sc k.

Hnh 9-5. S sc k kh i lc theo thi gian lu.

Thi gian lu, tr , ca mi cu t l thi gian cn thit cu t tip cn c vi detector k

t lc n c bm vo ct. Th tch lu, Vr , l th tch ca pha ng cn thit ra gii mt
cht tan ra khi ct.
Pha ng chuyn ng dc theo ct khi khng c cht tan vi thi gian tm. Thi gian lu hiu
chnh,

, ca mt cht tan l thi gian cn thit cht tan di chuyn theo chiu di ct tr i

thi gian cn thit dung mi i qua ct.

4

Thi gian lu hiu chnh:

= tr t m

(9-1)

Trong sc k kh, tm thng c ly l thi gian cn thit CH4 chuyn ng qua ct (hnh 95).
Vi hai cu t bt k 1 v 2, s lu tng i, l t s gia thi gian lu hiu chnh ca chng:
S lu tng i:
y

(9-2)

, vy nn >1. S lu tng i cng ln, kh nng tch gia hai cu t ra khi

nhau cng ln. S lu tng i khng ph thuc vo tc chy v v vy c th c s dng

xc nh pic khi tc chy thay i.
i vi mi pic trn sc k , tha s dung tch, k, c nh ngha:
Tha s dung tch:

k =

(9-3)

Cc cu t c lu li trong ct lu hn nu tha s dung tch cng ln. theo di hiu sut

ca ct sc k, tt nht l kim tra v o tha s dung tch, s a v tnh i xng ca pic. Vic
thay i cc tham s ny ch ra s gim hiu sut ca ct.
V d v cc tham s lu:
Mt hn hp gm benzen, toluen v metan c bm vo ct sc k kh. Metan cho tn hiu
42s, benzen 251s v toluen b ra gii 333s. Hy xc nh thi gian lu hiu chnh v tha s
dung tch cho mi cht tan v s lu tng i.
Gii
Thi gian lu hiu chnh:
Benzen:

= tr tm = 251 42 = 209s

Toluen:

= tr tm = 333 42 = 291s

Tha s dung tch:

Benzen: k =

= 5.0

Toluen: k =

= 6.9

S lu tng i c din t di dng t s gia thi gian lu hiu chnh ca toluen v

benzen:

= 1.39

9.3.2. Mi quan h gia thi gian lu v h s phn b

Tha s dung tch phng trnh 9-3 l tng ng vi:

k =

(9-4)

y Cs l nng cht tan trong pha tnh, Vs l th tch ca pha tnh, Cm l nng ca
cht tan trong pha ng v Vm l th tch ca pha ng.
T s Cs/Cm l t s nng ca cht tan trong pha tnh v pha ng. Nu ct c chuyn
ng chm t cn bng, t s Cs/Cm l h s phn b, K, c gii thiu trong
chng chit. Do , chng ta c th biu din phng trnh 9-4 di dng:
k = K

(9-5)

lin quan n thi gian lu ti h s phn b v th tch ca pha tnh v pha ng. Do
, s lu tng i c th din t:
=

(9-6)

iu ny c ngha l s lu tng i ca hai cht tan t l vi t s ca h s phn b

ca chng. Mi lin h ny l c s vt l ca phng php sc k.
Th tch lu,Vr , l th tch ca pha ng cn thit ra gii mt cht tan c th ra khi
ct:
Th tch lu: Vr = truv

(9-7)

y uv l tc chy ca pha ng (th tch trn n v thi gian). Th tch lu ca

mt cht tan c th l khng i trong mt phm vi ca tc chy.

9.4. Hiu qu tch

9.4.1. phn gii
Cc cht tan chuyn ng qua ct sc k c xu hng phn b nh ng cong Gaux vi
lch chun (hnh 9-6). Thi gian s dng di qua ct cng di, th pic sc k cng t. Thng
6

thng ngi ta o rng cao bng mt na chiu cao pic w1/2. T phng trnh ng
cong Gaux
c th thy l w1/2 = 2.35 v w = 4.

Hnh 9-6. ng cong Gaux l tng o w v w1/2. Cc gi tr ca w l thu c bng cch ngoi suy
cc tip tuyn vi cc im un xung ng c s.

Hnh 9-7. phn gii ca cc pic Gaux c din tch v bin bng nhau. ng nt t cho thy cc
pic ring bit v cc dng lin l tng ca hai nh pic. Phn chng sc k l phn bng m.

Trong sc k, phn gii ca hai pic vi nhau c nh ngha l:

phn gii =

(9-8)

 y, tr hay Vr l s tch gia hai pics (n v thi gian hay th tch) v wav l rng
trung bnh ca hai pic. Ngoi ra, phn gii c th biu din qua vic s dng w1/2av
chiu rng ti na chiu cao ca nh ng cong Gaux. Hnh 9-7 cho thy s chng
cho ca hai nh vi mc khc nhau ca phn gii. i vi phn tch nh lng,
phn gii l > 1,5 l iu trong i.
9.4.2. S khuch tn

Hnh 9-8. S m rng ca pic khi di chuyn qua ct sc k

Khi chuyn ng qua ct, l tng nht l pic sc k c dng hnh Gaux, theo chiu di
ca ct th pic c rng cng ln (hnh 9-8). t l tng hn, pic sc k s c dng
khng i xng.

Hnh 9-9. Thng lng ca cc phn t khuch tn qua mt n v din tch l t l thun vi gradient
nng v h s khuch tn: J =- D (dc / dx).

Mt trong nhng nguyn nhn chnh ca s n pic l s khuch tn. H s khuch tn

o s di chuyn ngu nhin t ni c nng cao n ni c nng thp. Hnh 9-9 cho
thy s khuch tn t pht ca cht tan qua mt mt phng vi mt gradien nng

dc/dx. S mol cht tan i qua mt mt vung trong mt giy gi l thng lng, J, t l
thun vi gradien nng :
(9-9)

Bng 9-1 cho thy s khuch tn ca cht lng l chm hn 104 ln so vi s khuch tn
trong pha kh. Cc phn t c khi lng mol ln nh ribonuclease v albumin khuch
tn chm hn t 10 n 100 ln so vi cc phn t nh. Gi s cht tan di chuyn qua
ct vi m mol trn mt n v din tch ct ngang ca ct, th s n ca ng cong
Gaux c m t bng:
(9-10)
trong c l nng (mol/m3), t l thi gian, v x l khong cch dc theo ct nh ca
pic (nh ca pic x lun lun = 0). So snh phng trnh 9-10 v phng trnh
ch ra cho ta thy lch chun ca m l:
=

(9-11)
Bng 9-1. H s khuch tn 298 K

Cht tan

Dung mi

H s khuch tn (m2/s)

H2O

H2O

2,310-9

Sucrose

H2O

0,5210-9

Glycine

H2O

1,110-9

CH3OH

H2O

1,610-9

Ribonuclease (M = 13700g/mol)

H2O (293K)

0,1210-9

Serum albumin (M = 65000 g/mol)

H2O (293K)

0,05910-9

I2

Hexane

4,010-9

CCl4

Heptane

3,210-9

N2

CCl4

3,410-9

CS2

Khng kh (293K)

1,010-5

O2 (g)

Khng kh (273K)

1,810-5

H+

H2O

9,310-9

OH-

H2O

5,310-9

Li+

H2O

1,010-9

Na+

H2O

1,310-9

K+

H2O

2,010-9

Cl-

H2O

2,010-9

I-

H2O

2,010-9

9.4.3. Chiu cao a

Phng trnh 9-11ch ra rng lch chun ca s n pic l

. Nu cht tan di

chuyn mt khong l x vi tc chy l ux (m/s) th thi gian cn thit di chuyn l

t = x/ux . Do vy,
2 = 2Dt = 2D

Chiu cao a:

= H.x

H=

(9-12)

(9-13)

Chiu cao a l hng s t l vi phng sai, 2, ca m v khong cch n va i qua,

x. Tn gi ny c ngun gc t l thuyt chng ct m s tch c th thc hin
c trong cc giai on ri rc gi l a. Chiu cao a cn c gi l chiu cao tng
ng vi mt a l thuyt. Chiu cao a l xp x vi di ca ct cn thit cho mt
cn bng ca cht tan gia pha ng v pha tnh. Chiu cao a cng nh, rng ca
pic sc k cng hp. Kh nng tch cc cu t trong hn hp ra khi nhau ca ct c
ci thin nu gim chiu cao a. Ct c hiu qu tch tt nu c nhiu a l thuyt. Cc
cht tan khc nhau i qua mt ct xc nh c chiu cao a khc nhau v chng c h s
khuch tn khc nhau. Chiu cao a l ~0,1 ti 1 mm trong sc k kh, ~10m trong sc
k lng hiu nng cao v trong mao mch in di.
Chiu cao a c gi tr l

, trong l lch chun ca pic hnh Gaux trn hnh 9-

7 v x l khong c di chuyn. Nu cht tan thot ra t ct c di L th s a N ca

ton ct s bng chiu di ca ct chia cho chiu cao ca mt a:
N= =

Bi v x = L v = w/4 . Trong m t ny, w c th nguyn l chiu di v s a l khng

th nguyn. Nu chng ta din ta L v w (hay ) di dng n v thi gian thay v chiu
di, s a N vn l khng th nguyn. Chng ta nhn c phng trnh:
S a trong ct: N =

(9-14a)

10

 y tr l thi gian lu ca pic v w l rng ca pic (xem hnh 9-7) vi n v l thi

gian. Nu chng ta s dng rng ng vi na chiu cao ca pic thay v rng ca
chn pic chng ta nhn c:
S a trong ct: N =

(9-14b)

V d: Tnh ton s a
Mt cht tan c thi gian lu l 407s v c rng chn pic l 13 s trn ct c chiu di
12,2 m. Tnh s a v chiu cao ca a.
Gii
N=

H= =

= 1,57.104
= 7,7710-4 m = 0,777mm

9.4.4. Phng trnh chiu cao a

Hnh 9-10. ng dng phng trnh Van Deemter vo sc k kh, A = 1,65mm, B = 25,8 mm.ml/pht; C =
0,0236 mm. Pht/ml

Chiu cao a, H, t l vi phng sai ca pic sc k (phng trnh 9-13): Chiu cao a cng nh
th pic cng hp. Phng trnh Van Deemter ch ra cho chng ta nh hng ca ct v lu lng
ti chiu cao ca a:

11

HA+

+ Cux

(9-15)

Trong A, B, C l cc hng s i vi mt ct v pha tnh c th, ux l tc chy (m/s).

Hng s A lin quan n tc dng ca khuch tn xoy, m khuch tn xoy li ph
thuc kch thc ht hp ph v mt nhi ct. B lin quan n h s khuch tn ca
phn t trong pha ng v c chu nh hng ca khuch tn dc ct. C c trng cho
qu trnh hp ph v gii hp, qu trnh chuyn khi v mt s yu t khc.
Thay i ct v pha tnh dn n s thay i A, B v C. i vi ct nhi (packed
columns) A, B, C 0 c ba yu t trn nh hng n s n ca pic. i vi ct ng m
(open tubular columns), A = 0 do vy rng pic gim v phn gii tng. Trong in
di mao qun (capillary electrophoresis) c A v C u bng 0, bi th chiu cao a gim
ti c micro do hiu qu tch tng cc k ln.

9.5. ng dng phng php sc k

9.5.1. Phn tch nh tnh
Sc k c s dng rng ri nhn din s c mt hay vng mt ca cc cu t trong hn
hp. V d, hn 30 amino axit trong protein hydrolysate c th c pht hin vi sc k .
Ngoi ra, da vo thi gian lu ngi ta c th phn tch nh tnh khi cc cht cn xc nh c
sc k chun.
Khi cc ct sc k c kt ni vi detector UV, hng ngoi hay khi ph, ngi ta c th d
dng hn hn khi phn tch nh tnh.

12

Hnh 9-... Sc k phn ch

Hnh 9-... Sc k phn ch

ph t ; tr ca

u
-

u mu khng c cht ma ty

u c th
chun MA, MDMA, MDA-d5 (tr ca
l 14 9 ph t ; tr ca
- 5
l 13 5 ph t).

l 9 99

9.5.2. Phn tch nh lng

1. Chun ho din tch pic: Coi t l % din tch pic hoc chiu cao pic tng ng vi t
l % khi lng cht. Ch yu p dng cho phn tch tinh du,
2. Ngoi chun: ng ngoi chun 1 im hoc nhiu im. Xy dng ng ngoi
chun da trn mi tng quan gia din tch pc hoc chiu cao pic vi nng cht.
3. Ni chun: ng chun ni c xy dng da vo mi tng quan gia nng
cht v t l din tch pic ca cht chun vi cht ni chun.
13

4. Thm chun: Cht chun c thm vo mu th

Hnh 9-... th tng quan tuy n tnh gia t l din tch pic v t l lng cht ca MA/MDA-d5
trong m u mu (phng php ni chun)

9.6. Cu hi n tp
1. Nu cc yu t nh hng n phn gii v chiu cao a l thuyt trong sc k.
2. Nu cc th tc trong phn tch nh lng bng phng php sc k. Hy gii thch
ti sao phng php ni chun c chnh xc cao nht.
3. Cho mt ct sc k c chiu di 120cm, tin hnh phn tch hai cht A v B thu c
kt qu sau:
Cht

Thi gian lu tr(s)

rng chn pic w(s)

trA = 250

wA =15 (s)

trB = 270

wA =17 (s)

Cho bit thi gian lu ca pha ng tm = 30s. Tnh

(a) S a l thuyt ca ct tch N =?
(b) Chiu cao a l thuyt H = ?
(c) phn gii ca ct tch R = ? Hai cht A v B c tch khi nhau khng?
(d) S lu tng i?
(e) tch hai cht hon ton ra khi nhau th ct sc k phi c chiu di ti thiu
bng bao nhiu?

14