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CHNG 8
PHNG PHP HP THU PHN T UV VIS
8.1 Tng quan
u th k 19, hu ht phn tch ho hc nh lng u s dng phng php trng lng
(gravimetry method) hoc phng php chun (titrimetry method). Vi nhng phng
php ny u t c ng (accuracy) cao, nhng kh c th xc nh c nhng thnh
phn hp cht c nng thp trong nc. Trong sut thi gian ny nhiu nghin cu c
bt u m rng kh nng phn tch nh lng c bit cc cc yu t vt trong mi
trng. Mt trong s nhng pht minh l phng php so mu quang ph.
Phng php so mu u tin l phng php Nessler phn tch hm lng ammonia trong
nc vo nm 1856. Nessler khm ph ra rng khi thm HgI
2
v KI vo trong mi trng c
cha NH
4
+
s to thnh dung dch mu t mu vng n mu nu tu theo nng ca
NH
4
+
. Mu ca mu s c so snh vi mu ca mu chun xc inh nng tng ng
trong mu. Cho n ngy nay phng php ny c nghin cu b sung phn tch
nc mt v nc thi trong Standard Methods. Cui th k 19, mt s phng php mi bt
u c khm ph nh phng php hp thu, pht x, tn x, tia cc tm, in t hng ngoi
pht x. Th k 20 l giai on pht trin ca tia X, microwave, v sng radio, cc ht nng
lng bao gm ht electron v ion.
8.2 Lch s nghin cu quang ph hc
Quang ph hc l mt mn hc chnh yu trong thin vn hc, n c ng dng thnh
cng nghin cu v kh quyn trong hnh tinh chng ta. Cch y 200 nm, Joseph von
Fraunhofer (1787-1826) ln u tin sn xut loi my o quang ph m tnh nng khng c
g snh kp lc by gi. ng y khm ph ra rt nhiu cc ng ti trong quang ph ca
nh sng mt tri. ng y c th xc nh chnh xc di bc sng ca nhiu Fraunhofer
lines (vch) v thut ng ny ngy nay vn c dng. Tuy nhin, trong thi gian ny ng y
khng hiu c nhng c s vt l v ngha v nhng vn m ng y khm ph ra.
Hnh 8.1. Thit b Spektralapparat thit k bi Kirchhoff v Bunsen (1833)
50
Thnh tu quan trng k tip v Fraunhofer lines l qu trnh tm ra nguyn l vt l ca s
hp thu v pht x vo nm 1859 vi s cng tc ca nhiu nh vt l ni ting nh Gustav R.
Kirchhoff v Robert W. Bunsen ti Heidelberg. Thit b m h s dng l Spektralapparat,
h ghi nhn c qu trnh pht x rt c bit ca nhiu nguyn t khc nhau. Vi phng
php ny h tip tc khm ph ra 2 nguyn t mi l Csium v Rubidium, h chit c
mt lng rt nh (7g) t 44.000 lt nc khong gn ni Bad Nauheim, c. S khm ph
ny l nn tng cho s khm ph tip theo v s hp thu v pht x ca hp thu phn t.
Nm 1879 Marie Alfred Cornu thy rng, nhng tia c bc sng ngn ca bc x mt tri
trn b mt tri t b hp th bi kh quyn. Mt nm sau , Walther Noel Hartley m t rt
t m v s hp th UV ca O
3
vi di bc sng 200 v 300 nm v n tr nn r rng hn
khi h pht hin ra rng O
3
cha y trong bu kh quyn. Nm 1880, Chappuis khm ph ra
s hp thu trong vng kh kin (400 840nm). Nm 1925 Dobson pht trin mt my quang
ph mi rt n nh s dng lng knh bng thch anh.
8.3 i cng v quang ph
Trong quang ph hc, nh sng nhn thy (nh sng kh kin), tia hng ngoi, tia t ngoi, tia
Rnghen, sng radio... u c gi chung mt thut ng l bc x.
Theo thuyt sng, cc dng bc x ny l dao ng sng ca cng in trng v cng
t trng, nn bc x cn c gi l bc x in t.
Sau thuyt sng, thuyt ht cho thy bc x gm cc ht nng lng gi l photon chuyn
ng vi tc nh sng (c = 3.10
8
m/s). Cc dng bc x khc nhau th khc nhau v nng
lng v h ca cc photon. y, nng lng ca bc x c lng t ha, ngha l nng
lng ca bc x khng phi lin tc m cc lng t nng lng t l vi tn s v ca dao
ng in t theo h thc Planck.
v c h =
h = 6,625.10
34
J.s: hng s Planck.
Louis de Broglie a ra thuyt thng nht c khi nim sng v khi nim ht ca sng nh
sng. nh sng va c tnh cht sng va c tnh cht ht. Tng qut hn l bc x c bn
cht sng ht. Ni dung nh sau:
Ht c khi lng m chuyn ng vi vn tc v c bc sng i i vi n l
cho bi h
thc:
p
h
mv
h
= =
Trong : p = mv l ng lng ca ht
l bc sng (de Broglie)
h = 6,625.10
-34
J.s l hng s Planck.
51
8.3.1 Cc i lng o bc x in t
Bc sng : L qung ng m bc x i c sau mi dao ng y .
n v: m, cm, m , nm,
o
A . (1cm = 10
8
o
A = 10
7
qm =10
4
m)
Tn s v : L s dao ng trong mt n v thi gian (giy)
Trong 1 giy bc x i c c cm v bc sng cm, vy:
v
c
=
Lu : Bc x truyn trong chn khng vi vn tc c = 2,9979.10
8
m/s (thng ly trn 3.10
8
m/s)
n v: CPS ( VNG DY), Hz, KHz, MHz. (1CPS=1Hz; 1MHz=10
3
KHz=10
6
Hz)
Nng lng bc x: Cc dao ng t (phn t chng hn) ch c th pht ra hoc hp th
nng lng tng n v gin on, tng lng nh nguyn vn gi l lng t nng lng:
v
v c hc
hc
h = = =
n v: Jun (J), Calo (Cal), electron von (eV).
8.3.2 Cc dng bc x
Bc x in t bao gm 1 dy cc sng in t c bc sng bin i trong khong rt rng:
t c mt sng raio n c
o
A (10
10
m) tia Rnghen hoc nh hn na. Ton b dy
sng c chia thnh cc vng ph khc nhau.
Bc sng (nm)
Cam Vng Lc Tm Chm Lam
(Kh kin)
Vi sng Sng radio Tia hng ngoi Tia X Tia UV
Vng VIS
Hnh 8.2. Cc ph ca sng in t
52
Mt ngi ch cm nhn c mt vng ph in t rt nh gi l vng nhn thy (kh kin)
bao gm cc bc x c bc sng t 396 760 nm. Hai vng tip gip vi vng nhn thy l
vng hng ngoi v vng t ngoi UV.
8.3.3 S tng tc gia vt cht v bc x in t
iu kin bnh thng, in t ca phn t nm trng thi lin kt, nn phn t c mc
nng lng thp, gi l trng thi c bn E
o
(Hnh 8.3).
Khi chiu mt bc x in t vo mt mi trng vt cht, s xy ra hin tng cc phn t
vt cht hp th (absorption) hoc pht x (emission) nng lng, hay c gi l trng
thi kch thch (Hnh 8.3). Nng lng m phn t pht ra hay hp th vo l:
AE = E
2
E
1
= v h
Trong , E
1
v E
2
l mc nng lng ca phn t trng thi u v trng thi cui
v (hay cn gi l trng thi kch thch) l tn s ca bc x in t b hp th hay pht x ra.
Nu AE > 0 th xy ra s hp th bc x in t.
Nu AE < 0 th xy ra s pht x nng lng.
Hnh 8.3. S hp th (A) hoc pht x (B) nng lng ca mt photon
Theo thuyt lng t, cc phn t v cc bc x in t trao i nng lng vi nhau khng
phi bt k v lin tc m c tnh cht gin on. Phn t ch hp th hoc pht x 0, 1, 2,
3,n ln lng t v h m thi. Khi phn t hp th hoc pht x s lm thay i cng
ca bc x nhng khng lm thay i nng lng ca n, bi v cng bc x in t xc
nh bng mt cc ht phton c trong chm tia, cn nng lng bc x in t li ph
thuc tn s v ca bc x.
V th khi chiu mt chm bc x in t vi mt tn s duy nht i qua mi trng vt cht
th sau khi i qua nng lng ca bc x khng h thay i m ch c cng bc x thay
i. Cc phn t khi hp th nng lng ca bc x s dn n thay i cc qu trnh trong
phn t (quay, dao ng, kch thch electron) hoc trong nguyn t (cng hng spin
electron, cng hng t ht nhn)
Mi mt qu trnh nh vy i hi mt nng lng c trng cho n, ngha l i hi bc x
in t c tn s hay chiu di sng nht nh kch thch. Do s hp th chn lc ny m
khi chiu chm bc x in t vi mt di tn s khc nhau i qua mi trng vt cht th sau
A B
53
khi i qua chm bc x ny s b mt i mt s bc x c tn s xc nh, ngha l cc tia ny
b phn t hp th.
Bng 8.1. ng dng quang ph in hnh do s thay i nng lng
Kiu chuyn i nng lng Vng bc sng Thit b quang ph
Hp th (absorption)
Tia
My quang ph Mossbauer
Tia X My hp th quang ph tia X
UV/Vis
My so mu quang ph UV/Vis
My hp thu nguyn t AAS
Hng ngoi
My so quang ph hng ngoi
My so mu hiu ng Raman
Microwave My quang ph vi sng
Sng radio My quang ph t ht nhn
Pht x (emission)
UV/Vis My pht x nguyn t
Tia X My pht x hunh quang tia X
UV/Vis
My quang ph hunh quang
My pht ln quang
My quang ph pht x hunh quang
nguyn t
Bng 8.2. Quang ph in hnh khng do s thay i nng lng
Vng bc sng Kiu tng tc Thit b
Tia X Nhiu x My nhiu x tia X
UV/Vis Khc x My khc x
Tn x My o c
8.3.4 S hp th bc x v mu sc ca cc cht
nh sng nhn thy bao gm tt c di bc x c bc sng t 396 760 nm c mu trng
(nh sng tng hp). Khi cho nh sng trng (nh sng mt tri) chiu qua mt lng knh, n
s b phn tch thnh mt s tia mu (, da cam, vng, lc, lam, chm, tm). Mi tia mu
ng vi mt khong bc sng hp hn (xem Bng 8.3). Cm gic cc mu sc l mt chui
cc qu trnh sinh l v tm l phc tp khi bc x trong vng kh kin chiu vo vng mc
ca mt. Mt tia mu vi mt khong bc sng xc nh. Chng hn bc x vi bc sng
54
400430 nm gy cho ta cm gic mu tm, tia sng vi bc sng 560 nm cho ta cm gic
mu lc vng.
nh sng chiu vo mt cht no n i qua hon ton th i vi mt ta cht khng
mu.
Th d, thy tinh thng hp th cc bc x vi bc sng nh hn 360 nm nn n trong sut
vi cc bc x kh kin. Thy tinh thch anh hp th bc x vi bc sng nh hn 160 nm,
n trong sut i vi bc x kh kin v c bc x t ngoi gn.
Mt cht hp th hon ton tt c cc tia nh sng th ta thy cht c mu en. Nu s hp
th ch xy ra mt khong no ca vng kh kin th cc bc x khong cn li khi n
mt ta s gy cho ta cm gic v mt mu no . Chng hn mt cht hp th tia mu
( = 610730 nm) th nh sng cn li gy cho ta cm gic mu lc (ta thy cht c mu
lc). Ngc li, nu cht hp th tia mu lc th i vi mt ta n s c mu . Ngi ta
gi mu v mu lc l hai mu ph nhau. Trn hai mu ph nhau li ta s c mu trng.
Ni cch khc, hai tia ph nhau khi trn vo nhau s to ra nh sng trng. Quan h gia mu
ca tia b hp th v mu ca cht hp th (cc mu ph nhau) c ghi bng sau:
Bng 8.3. Quan h gia mu ca tia b hp th v mu cht hp th
Tia b hp th Mu ca cht hp th
(mu ca tia cn li)
(nm) Mu
400 430
430 490
490 510
510 530
530 560
560 590
590 610
610 750
Tm
Xanh
Lc xanh
Lc
Lc vng
Vng
Da cam
Vng lc
Vng da cam
ta
Tm
Xanh
Xanh lc
Lc
Lu : Gia cc tia mu cnh nhau khng c mt ranh gii tht r rt.
Vic phn chia nh sng trng thnh 7, 8 hay 9 tia mu cn ty thuc vo lng knh v s
tinh t ca mt ngi quan st.
Mt cht c mu, th d nh mu chng hn l do n hp th chn lc trong vng kh
kin theo mt trong cc kiu sau:
- Cht hp th tia ph ca tia (tc l hp th tia mu lc)
- Cht hp th cc tia tr tia mu .
- Cht hp th hai vng khc nhau ca nh sng trng sao cho cc tia cn li cho
mt ta cm gic mu .
55
mt hp cht c mu, khng nht thit
max
ca n phi nm vng kh kin m ch cn
cng hp th vng kh kin ln. Ni mt cch khc tuy gi tr cc i ca vn hp
th nm ngoi vng kh kin nhng do vn hp th tri rng sang vng kh kin nn hp cht
vn c mu. Tt nhin c c s hp th thy c vng kh kin th
max
ca cht
cng phi gn vi ranh gii ca vng kh kin.
Tng ng vi mt bc chuyn in t, ta thu c ph hp thu c dng:
Hai i lng c trng ca ph hp thu l v tr v cng
- V tr cc i hp thu, gi tr
max
ty thuc vo E A m hp cht ny hp thu cc
vng ph khc nhau. Bn chiu rng ca vn ph in t dao ng kh rng khong
50 60 nm.
- Cng th hin qua din tch hoc chiu cao ca nh biu (peak). Cng
vn ph ph thuc vo xc xut chuyn mc nng lng ca in t. Xc sut ln cho
cng vn ph ln.
Mt hp cht mu c ph hp thu tt khi nh biu (peak) cao v bn chiu rng vn ph
hp.
Peak
rng
Bn vn ph
max
56
Hnh 8.4. nh (peak) v bn chiu rng vn ph
Khi bn chiu rng vn ph hp, khi thay i nh th hp thu A thay i ln. iu ny
rt c ngha trong phn tch nh lng. Gi s hp cht X c A
max
500 nm. Khi chng ta
o bc sng 510 nm... th hp thu o c s khc rt xa i vi bc sng 500 nm.
T ta thy rng mi hp cht mu c mt gi tr
max
nht nh v n phn nh nhy
ca phng php. Mt khc, mt hp cht i hi nh biu cao ngha l khi ta o bc
sng
max
th ta c hp th quang cc i, khong lm vic rng.
8.3.5 nh lut Lambert Beer
Khi chiu mt chm tia sng n sc i qua mt mi trng vt cht th cng ca tia sng
ban u (I
o
) s b gim i ch cn l I
T s T
I
I
o
=
0
0
100 c gi l truyn qua.
T s A
I
I I
o
=
0
0
100 c gi l hp th.
Nguyn tc ca phng php biu din theo s :
Mu
Cuvette
I
o I
A
I
I
R
I
o
= I
A
+ I
R
+ I
Hnh 8.5. S m t s hp th nh sng ca mt dung dch
Trong :
I
o
: Cng ban u ca ngun sng
I
A
: Cng nh sng b hp thu bi dung dch
I: Cng nh sng sau khi qua dung dch.
I
R
: Cng nh sng phn x bi thnh cuvette v dung dch, gi tr ny c loi
b bng cch lp li 2 ln o.
Gia I
A
, I, dy truyn nh sng (l) v nng (C) lin h qua quy lut Lambert Beer l
nh lut hp nht ca Bouguer:
57
Lambert (1766) l K
I
Io
1
lg =
Beer (1852): C K
I
Io
1
lg =
truyn quang (T) hay hp th (A) ph thuc vo bn cht ca vt cht, dy truyn
nh sng l v nng C ca dung dch. C th vit:
nh lut Lambert Beer : l C
I
I
A = =
c ) lg(
0
Trong : c l h s hp thu phn t, C nng dung dch (mol/L), l dy truyn nh sng
(cm), A l hp th quang. (Lu phng trnh trn ch ng i vi tia sng n sc).
Trong phn tch nh lng bng phng php trc quang ngi ta chn mt bc sng
nht nh, chiu dy cuvet l nht nh v lp phng trnh ph thuc ca hp th quang A
vo nng C.
Kho st khong tun theo nh lut Lambert Beer:
Khi biu din nh lut Lambert Beer trn th ty theo cch thc hin php o, ta thng
gp ng biu din s ph thuc hp thu A vo cng C ca dung dch c dng: y =
ax + b
H s gc a cho bit nhy ca phng php, trong phng php trc quang ngi ta ch o
dung dch trong khong tun theo nh lut Lambert Beer tc l khong nng m
gi tr c khng thay i. H s gc a cng ln v khong tun theo nh lut Beer cng rng
l iu kin thun li cho php xc nh.
S lch khi nh lut Beer:
S lch khi nh lut Beer c biu din bng s sau:
Hnh 8.6. Gii hn ca nh lut Beer v s hp th quang
Khong tuyn tnh LOL (Limit of Linear Response) l khong nng tun theo nh lut
Beer ) ( C l A = c ngha l khi nng tng th hp th quang A tng. Ngoi gii hn
LOL l s lch khi nh lut Beer, ngha l khi nng tng th hp th quang A hu nh
58
khng tng na. Nguyn nhn ca qu trnh ny l do nng dung dch qu ln. Ngoi ra,
khong tuyn tnh LOL cn b nh hng ca mc n sc ca nh sng s dng, pH ca
dung dch, lc ion, s pha long...
ngha ca cc i lng:
- H s hp thu mol c: ph thuc bn cht mi cht, bc sng , nhit , chit sut
(theo nng ). Gi tr tnh l thuyt ca mt bc chuyn c php cho 1 electron l
c = 10
5
mol
-1
.cm
-1
.
lC
A
= c (l. mol
-1
cm
-1
)
c cao cho ta bit c nhy ca phn ng, l thc o nhy ca phng php.
Trong phn tch trc quang, c = 10
3
10
5
mol
-1
. cm
-1
l nhy dng cho phng
php trc quang, c ph thuc vo chit sut m chit sut li ph thuc vo nng .
Khi chit sut tng ln th c gim v c khng thay i th phi thc hin C s 10
-2
mol/L.
- hp th quang A: L i lng khng c n v, c tnh cht quan trng l tnh
cng hp th quang.
Gi s 2 cht A v B c nng C
A
v C
B
, hp thu ti bc sng l:
A = A
A
+ A
B
= l (c
A
C
A
+ c
B
C
B
)
Nu mt cht tan X no c hp th quang l A
X
, dung mi c hp th quang l A
dm
,
ta c:
A = A
x
+ A
dm
o c chnh xc A
x
th A
dm
= 0, c ngha l phi chn
max
ca dung mi khc xa vi
max
cht tan. Nhng cht c chn lm dung mi thng c hp thu min ranh gii t
ngoi chn khng.
Bng 8.4. Cc dung mi thng s dng trong vng UV VIS
Dung mi Bc sng (nm) Dung mi Bc sng (nm)
Nc ct 190 Benzen 280
HCl 190 Cloroform 245
Etanol, metanol 210 Tetra Clorocarbon 265
n- Butanol 210 Dietyl Eter 218
n- Hexan 210 Aceton 330
Cyclohexan 210 1,4 Dioxan 215
Trong hn hp c nhiu cu t khng lm thay i tng tc, khng phn ng ha hc, khng
dch chuyn cn bng, th c th xc nh hn hp cc cu t theo h thc sau:
59
n n i i
lC lC lC lC A
c c c c + + + + + = ...... .......
2 2 1 1
- truyn quang T:
o
I
I
T = m ) lg(
0
I
I
A = do T A lg =
V T tnh theo % nn: T A lg 2 =
Nu T = 100% th A = 0 (ngha l khng hp th nh sng (I = I
o
)
Nu T = 1% th A = 2
Nu T = 0 % th = A (hp thu hon ton nh sng)
0.0
0.5
1.0
1.5
2.0
0 10 20 30 40 50 60 70 80 90 100
p
t
h
A
truyn quang T (%)
Hnh 8.7. Mi quan h gia truyn quang (T) v hp th (A)
V d 8.1:
Mt mu c truyn quang l 50%, tnh hp thu A ca mu?
Gii quyt vn :
Ta c : A = -lg T = -lg(0,5) = 0,301
V d 8.2:
Mt dung dch c nng 5 10
-4
M c phn tch v o bng cuvette 1 cm bc sng
490 nm c hp thu l 0,338. Hy tnh hp thu phn t ca cht bc sng ny ?
Gii quyt vn :
lC
A
= c =
M cm
4
10 . 5 1
338 , 0
= 676 cm
-1
M
-1
8.3.6 Nguyn l cu to ca my quang ph
Ngun sng
Ngun sng cho my quang ph l chm bc x pht ra r n. My quang ph dng n
hydro hay n Deuterium cho ph pht x lin tc trong vng UV t 160 380nm (nhng
thng s dng 200 - 340 nm) v n tungsten halogen o vng 380 1000 nm. lm vic
60
cho c hai vng th phi c 2 loi n trn. Mt yu cu i vi ngun sng l phi n
nh, tui th cao v pht bc x lin tc trong vng ph cn o.
n Deuterium: cu to sm mt si t ph xit v mt cc kim loi t trong mt bng
thu tinh cha kh Deuteri hoc hydro c ca s bng thch anh bc x t ngoi i ra v n
khng truyn qua c thy tinh. Khi si t c t nng, electron sinh ra kch thch cc
phn t kh Deuteri (hoc hidro) bin thnh nguyn t v pht ra phton theo phn ng:
D
2
+ E
e
*
2
D D + D' ' + v h
E
e
=
*
2
D
E = E
D
+
E
D
+ v h
y l nng lng electron kch thch, bc x pht ra l mt ph c bc sng t 160 nm
n vng kh kin.
Bng 8.5. Ngun pht nng lng trong cc thit b quang ph
Ngun Vng bc sng S dng cho
n H
2
v D
2
160 380 nm Hp th phn t t ngoi
nTungsten 320 2400 nm Hp thu phn t kh kin
n h quang Xe 200 1000 nm Pht x hunh quang phn t
n Nernst 0,4 20 m Hp th phn t hng ngoi
n cc m hallow UV/Vis Hp th nguyn t
n hi nc Hg UV/Vis Pht x hunh quang phn t
Laser UV/Vis Hp th phn t, nguyn t, hunh
quang, tn x
B n sc
B n sc c chc nng tch bc x a sc thnh bc x n sc, bao gm knh lc, lng
knh hay cch t.
Cch t l mt bng nhm hay cc kim loi Cu, Ag, Au... c vch thnh nhng rnh hnh
tam gic song song. Khi chiu nh sng qua cch t, phn cn li c tc dng to nn vn
nhiu x c bc sng khc nhau, khi quay cch t s to ra ph nhiu x ging nh trng
hp nh sng qua lng knh. u im l cho phn gii tt, tn sc tuyn tnh, rng ca
di n nh, chn bc sng n gin, gn nh, d ch to nn hin nay s dng cch t to
nh sng n sc c a chung. Cch t dng cho UV/Vis c 1200 vch/ mm (thng dao
ng t 300 3600 vch/mm, s vch cng nhiu th nng sut phn gii cng cao.
61
Hnh 8.8 S m phng cu to ca my quang ph
Lng knh ca my quang ph dng lng knh littrow (lng knh 30
o
) bng thch anh, c c
im nh sng i qua lng knh hai ln do phn x mt sau. Khi phn tch, hn ch mc
nhiu ca vn ph, tt nht nn chn bc nhy ca bc sng (bandwidth) mc thch
hp tu vo hp cht (Hnh 8.9)
Bandwidth 0,25 nm Bandwidth 1,0 nm
Bandwidth 2,0 nm Bandwidth 4,0 nm
Hnh 8.9. Mc nhiu cc di Bandwidth khc nhau
Cuvet ng mu
Cuvet phi lm bng cht liu cho bc x vng cn o i qua. Cuvet thy tinh khng thch
hp cho vng UV. Cuvet thch anh cho bc x i qua t 190 1000 nm. Cuvet nha ch dng
trong vng Vis v ch s dng c 1 vi ln.
62
Detector
Detector l b phn o tn hiu nh sng trc v sau khi i qua dung dnh (ng trong cuvet).
Cc tn hiu sau khi i ra Detector s c s c khuch i bng processor tn hiu (signal
processor), lu gi v x l trn my tnh. C 2 loi detector l: b cm bin photon
(photon transducer) v b cm bin nhit (thermal transducer) Bng 8.6.
Bng 8.6. c tnh ca mt s b chuyn i tn hiu (transducer)
Detector Lp Vng bc sng
n quang in (phototube) Photon 200 1000 nm
in k nhn (Photomultiplier) Photon 110 1000 nm
Quang diot Silic (Si photodiode) Photon 250 1100 nm
Quang dn (photoconductor) Photon 750 6000 nm
Pin quang voltaic (photovoltaic cell) Photon 400 5000 nm
Cp nhit in (thermocouple) Nhit 0,8 40 m
Nhit in tr (thermistor) Nhit 0,8 40 m
Ho in (pyroelectri) Nhit 0,3 1000 m
8.4 S dng phng php trc quang trong nh lng ha hc
Yu cu v cc hp cht cn xc nh l phi bn, t phn ly, n nh, khng thay i thnh
phn trong khong thi gian nht nh thc hin php o (1020 pht).
H s c ln c gi tr t 10
3
5.10
4
L. mol
-1
cm
-1
, c th thc hin phn ng to mu vi cc
thuc th v c v hu c.
Nng cc cht xc nh theo nh lut Lambert Beer. Khong xc nh nng theo
phng php l 10
-2
10
-6
mole. Gii hn pht hin ca phng php 10
-7
mole.
Cc hp cht l phc cn o phi c
max
khc xa vi
max
ca thuc th trong cng iu kin
tc l A > 2 ln na bn chiu rng ca vn ph (khong 80 100 nm). Th d, khi phn
tch Fe
2+
bng phng php O-phenanthroline. Sau khi thm thuc th ta c phc mu
vng cam (
max
= 510 nm), trong khi thuc th 1,10- Orthophenanthroline c
max
= 250
nm.
Bng 8.7 Mt s ng dng phng php trc quang trong phn mt s yu t thng
thng trong ao nui thu sn
Ch tiu Phng php Phc mu
max
(nm)
Al Phn ng vi Eriochrome cyanide R pH 6,0 Hng 535
Cu Phn ng vi Neocuprine, ly trch bng CHCl
3
Vng 457
63
Fe
2+
Phn ng vi O-phenanthroline, pH = 5 Cam 510
NH
3
Phenate, to phc Indophenol Xanh 630
NO
2
-
To mui diazonium, pH = 2 3 Hng ta 543
NO
3
-
To mui salicylate, pH > 9 Vng 410
PO
4
3-
To phc moybden Xanh 690
SO
4
2-
To phc vi sodium rhodizonate 520
SiO
2
To phc heteropoly Xanh 815
8.4.1 Phng php so snh
So snh cng mu ca dung dch cn xc nh vi cng mu ca dung dch chun
bit nng .
iu kin: c hai dung dch trn phi c nng nm trong khong tun theo nh lut Beer.
C
x
----------------------- A
x
C
tc
---------------------- A
tc
Ta cn xc nh C
x
:
tc
tc x
x
A
C A
C
=
Khi s dng 2 dung dch chun:
) (
1
1 2
1 2
1
A A
A A
C C
C C
x x
+ =
Vi A
1
, A
2
, C
1
, C
2
l hp thu v nng ca dung dch chun tng ng sao cho A
1
<
A
x
< A
2
c ngha C
1
< C
x
< C
2
8.4.2 Phng php thm chun
Phm vi ng dng l xc nh cc cht c hm lng vi lng hoc siu vi lng, loi b nh
hng ca cht l. C 2 phng php l phng php s dng cng thc v phng php
th.
- Phng php s dng cng thc
x a x
x
a x
A A
A
C C
=
+
Trong : A
x
: hp thu ca dung dch xc nh tng ng vi th tch V
x
.
A
x+ a
: hp thu ca dung dch c thm chun.
C
a
: Nng cht chun thm vo.
64
C
x
: Nng cht cn xc nh trong th tch V
x
Cng thc c thit lp t: A
x
= c l C
x
A
(x+a)
= c l (C
x
+ C
a
)
C
x
c biu din theo n v ca C
a
.
Cch thc hin:
Ly 3 ln ca dung dch cn xc nh nng cho vo 3 bnh nh mc c th tch VmL.
Bnh 1: Thm thuc th v cc cht to mi trng pH cho dung dch, dung dch gi l
dung dch xc nh C
x
, hp thu quang tng ng l A
x
.
Bnh 2: Thm mt lng chnh xc dung dch tiu chun bit chnh xc nng C
a
, tin
hnh phn ng to mu ging nh bnh 1. Dung dch c hp thu tng ng l A
(x+a)
.
Bnh 3: ch thm cc cht to pH cho dung dch, ly dung dch ny lm dung dch so snh.
p dng cng thc:
x a x
x
a x
A A
A
C C
=
+
. T C
x
c trong th tch V
x
(mL) c th qui v th tch
ban u ca mu V
o
(mL):
x
o x
o
V
V C
C = mg/L
- Phng php s dng th
C t nht 3 dung dch thm chun. Ly t nht 4 ln ca dung dch cn xc nh nng cho
vo 4 bnh nh mc V(mL). Sau thm chnh xc mt lng V
1
, V
2
, V
3
mL dung dch tiu
chun c nng tng ng C
a1
, C
a2
, C
a3
vo 3 bnh nh mc trn. Tin hnh phn ng to
mu. Bnh cn li lm dung dch so snh, cng chun b ging nh phng php cng
thc.
hp thu ca cc dung dch thm so vi dung dch so snh.
Hnh 8.10. Tng quan ca phng php thm chun s dng th.
C th c kt qu trn th hoc s dng phng trnh hi qui c dng:
A = aC + b (hi quy tuyn tnh y = ax + b)
A
x
= b
65
C
x
= b/a
8.4.3 Phng php ng chun
u im l chnh xc, thc hin c nhiu ln.
- Chun b t 6 dung dch chun (trong khong tun theo nh lut Beer).
- Thc hin phn ng mu vi thuc th.
- o hp th quang A ca dung dch
max
so vi cc dung dch so snh c chun b
ging nh dung dch tiu chun nhng khng cha ion cn xc nh.
- Biu din s ph thuc A theo C trn th hoc tnh theo phng trnh hi qui A= aC +
b (a v b l h s cn tm ca phng trnh hi quy tng quan) (xem Bng 8.8)
- Dung dch xc nh: chun b v phn ng to mu vi thuc th ging nh mu chun.
Bng 8.8. Dung dch chun dng xy dng ng chun
Dung dch chun C (mg/L) A
1 0,00 0,010
2 0,05 0,480
3 0,10 0,930
4 0,15 1,370
5 0,20 1,830
6 0,25 2,281
Sau khi o c gi tr hp th quang ca cc dung dch chun, chng ta c th tin hnh
xy dng ng chun v tm ra phng trnh hi quy tng quan:
y = 9.0543x + 0.0184
R
2
= 0.9999
0.000
0.500
1.000
1.500
2.000
2.500
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Nng
p
t
h
A
Hnh 8.11. Biu xc nh phng trnh hi quy ca phng php ng chun
Sau khi thit lp ng chun, ta c dng phng trnh y = ax + b vi y l hp th
quang, x l nng . i vi dung dch xc nh, ta tin hnh phn ng v o c h s hp
thu ca mu (A
mu
= y), ta c th tnh c nng ca mu cn xc nh theo phng trnh:
a
b y
x
=
66
S tng quan gia hp th quang A v nng C khi const l = l ni dung ca nh lut
Beer. Khong nng tha mn nh lut ny khi R > 0,999.
H s tng quan r bin i trong khong -1s R s 1 (R
2
= 0 1)
- Khi R ~ 1 c s tng quan cht ch gia x v y theo t l thun.
- Khi R ~ -1 c s tng quan cht ch gia x v y theo t l nghch.
- Khi R ~ 0 hai i lng ny khng cn tng quan.
8.5 chnh xc trong phng php trc quang:
Trong phn tch trc quang cng nh bt k phng php no khc c th chia sai s thnh 2
nhm:
- Sai s do tin hnh phn ng ha hc (ha cht, thao tc, dng c...)
- Sai s ca tn hiu o hp thu ca dung dch (do h thng o).
chnh xc trong phng php ny ph thuc vo hng lot nguyn nhn khc nhau rt
phc tp bao gm sai s ngu nhin v sai s h thng, trong sai s quan trng nht l sai
s ca tn hiu trong qu trnh o hp thu quang hc.
8.6 Mt s v d p dng phng php nh lng trc quang
V d 8.3:
hp th quang A ca dung dch anilin 2 10
-4
M trong nc o bc sng = 280 nm
l 0,252. Chiu di nh sng i qua cuvet l 1cm. Tnh truyn quang ca anilin 1,03.10
-3
M
khi o cng di bc sng nhng dng cuvet 0,5cm.
Gii quyt vn :
p dng cng thc l C
I
I
A ) lg(
0
c = = vi dung dch 1 ta c:
c = 0.252/(2.10
-4
1) = 1,26.10
3
l. mol
-1
cm
-1
.
p dng cng thc l C
I
I
A ) lg(
0
c = = vi dung dch 2 ta c:
A = 1,26.10
3
0,5 1,03.10
-3
= 0.649
M: A = -lg T suy ra: lg T = -A = -0,649, do T = 0,224 = 22,4%
Vy truyn quang T = 22,4%
V d 8.4:
hp th quang A o c t cc mu chun v mu nc thu t ao nui c cha ion PO
4
3-
nh sau:
Nng mu chun (mg/L) 0,00 0,05 0,10 0,15 0,20 0,25
67
hp th quang A 0,010 0,480 0,930 1,370 1,830 2,281
hp th quang A ca mu nc ao ca 3 ln lp li l: 1,256; 1,245; 1,264. Tnh nng
PO
4
3-
trong mu nc ao.
Gii quyt vn :
T cc nng mu chun v hp th quang A. T kt qu thit lp phng trnh hi qui
ta c: 0184 , 0 0543 , 9 + = X Y (R
2
= 0,9999).
T kt qu ca 3 ln phn tch lp li ta c y A = = 1,255
T ta c 137 , 0
0543 , 9
0184 , 0 255 , 1
0543 , 9
0184 , 0
=
=
y
x mg/L
Vy nng PO
4
3-
trong mu nc ao l 0,137 mg/L.
V d 8.5:
xc nh hng s phn ly ca Methyl da cam (k hiu HIn), ngi ta o hp th quang
A ca 3 dung dch cng nng Methyl da cam cc pH khc nhau:
- Dung dch 1 trong HCl 0,1M; A
1
= 0,475.
- Dung dch 2 trong NaOH 0,1 M; A
2
= 0,130.
- Dung dch 3 c pH = 4,34; A
3
= 0,175
Cho bit o bc sng = 510 nm v chiu di nh sng i qua cuvet l 1cm. Tnh hng s
phn ly K ca Metyl da cam?
Gii quyt vn :
hp th quang ca dung dch 3:
| | | | l HIn l In A
HIn
In
+ =
c c
3
(8.1)
Vi [In
-
] = x; [HIn] = y ta c: x + y = C
HIn
= C (8.2)
l C
A
In
2
c v ton b cht ch th dng In
-
(8.3)
l C
A
Hin
=
1
c v ton b cht ch th dng HIn (8.4)
Thay (8.3) v (8.4) vo (8.1) ta c:
C
y
A
C
x
A A + =
1 2 3
(8.5)
Qui c: = = ) 1 ( ; o o
C
y
C
x
0,175 = 0,130o + 0,475 (1-o) o = 0,869
Hng s phn ly ca HIn:
68
HIn H
+
+ In
-
; K
a
o
o
= = =
+
1
lg lg
] ][ [
pH
HIn
In
pH pK
HIn
In H
K
pK = 4,34 -
689 , 0 1
869 , 0
lg