CC PHNG PHP PHN TCH CNG C

PHN 1 CC PHNG PHP PHN TCH

QUANG HC
PHN 2 CC PHNG PHP PHN TCH IN
HA
PHN 3 CC PHNG PHP TCH
PHN 1 CC PHNG PHP
PHN TCH QUANG HC
CHNG 1
I CNG V PHNG PHP PHN TCH QUANG HC
CHNG 2
PHNG PHP QUANG PH HP TH PHN T UV-VIS
CHNG 3
PHNG PHP QUANG PH PHT X NGUYN T
CHNG 4
PHNG PHP PHN TCH PH HP TH NGUYN T

1.I CNG V PHNG PHP PHN TCH QUANG HC
Sng in t chnh l cc ht foton di chuyn v dao ng trong khng gian vi vn
tc ln.



di sng 10- 190 nm 190 -370 nm 370-800 800 - 2500 nm
Min ph T ngoi xa T ngoi gn Kh kin Hng ngoi gn
Tc dng
vi vt cht
Kch thch cc electron lm cho chng chuyn
ln mc nng lng cao hn
Kch thch dao
ng ca phn t
1.1 PH IN T V NNG LNG CC VNG PH KHC NHAU
1.1 PH IN T V NNG LNG CC VNG PH KHC NHAU
Nng lng ca sng in t : E = hv ; v = C/;vy

C
. h E = , h l hng s Plank
6,62.10
-27
erg.giy; v l tn s dao ng in t; C l tc nh sng 3.10
10

cm/giy. Sng in t c nng lng cao khi tn s cao hay bc sng ngn
- 0,005 -10 nm l vng tia X, nng lng rt cao
- 10- 200 nm l vng t ngoi xa b oxi, hi nc, polime, thu tinh hp th.
- 200-800 nm phng php quang ph nguyn t v phn t.
- 400 800 nm gi l vng kh kin v mt ngi ta cm nhn c.
- 800 2500 nm c gi l vng hng ngoi gn, t c dng trong phn
tch nh lng nhng c dng nhiu phn tch cu trc.
Trong quang ph hp th dng s sng v (cm
1
), n l s bc sng trong 1
cm. Nh vy v = 1(cm) hay v (nm) = 10
7
.
Suy ra: v (cm
1
) =
) nm (
10
7

(nm) =
10
7
v( ) cm
1

1.I CNG V PHNG PHP PHN TCH QUANG HC
1.2 S BIN I NNG LNG KHI SNG IN T TC DNG VI VT CHT
1.2.1 Cc kiu bin i nng lng
Khi photon ca tia sng i qua ht nguyn t c kh nng hp th (ph hp v nng
lng), nng lng ca photon truyn cho ht c bn lm cho chng tr thnh trng
thi kch thch. Tuy nhin trng thi ny khng bn, khong 10
-6
- 10
-9
giy, n nhanh
chng tr v trng thi c mc nng lng thp hn hoc mc c bn v gii to nng
lng di 3 dng ch yu sau:
1. Bin i ha hc ca cht ( th d chuyn ho Fe
3+
thnh Fe
2+
).
2. Gii phng nng lng di dng nh sng (hunh quang)
3. Bin i nng lng thnh chuyn ng quay, dao ng ca nguyn t, chuyn
dch electron ln mc nng lng mi v cui cng l gii phng nhit.
Cc bin i trn tu thuc cht hp th v nng lng nh sng kch thch, tuy
nhin hai dng bin i sau c s dng nhiu trong phn tch.
1.I CNG V PHNG PHP PHN TCH QUANG HC
1.2 S BIN I NNG LNG KHI SNG IN T TC DNG VI VT CHT
Trng hp th nht, s bin i ho hc xy ra c th
lm tng hoc gim s oxi ho ca cht b tc ng.
Trng hp th hai khi b kch thch, electron nhy ln
mc nng lng cao hn v trng thi ny vi thi gian
rt ngn, khi tr li trng thi mc nng lng thp hn,
nng lng gii to di dng nh sng, cn gi l nh ng
th cp. Do nng lng b mt mt phn do bin thnh
nhit nn nh sng th cp c bc sng di hn so vi
nh sng kch thch.
1.I CNG V PHNG PHP PHN TCH QUANG HC
1.2 S BIN I NNG LNG KHI SNG IN T TC DNG VI VT CHT
Nng lng bin i thnh nhit nng
Khi cc phn t nhn nng lng t sng in t, phn t chuyn ln mc nng
lng mi, trng thi ny khng bn, nng lng c chuyn ha vi ba dng nng:
- Phn t quay xung quanh cc trc khc nhau.
- Nguyn t hoc nhm nguyn t trong phn t dao ng tng i vi nhau.
- Cc electron trong h chuyn dch ln cc orbital khng lin kt.
C ba trng hp ny nng lng nhn c nh ch yu l cc sng UV-VIS. Cc
electron trong phn t c chia lm 4 loi:
- Electron cc qu o bn, khng tham gia lin kt, khng hp th UV.
- Cc electron ha tr tham gia lin kt, loi ny cn nng lng cao mi kch thch
c, thng l vng t ngoi nn c kh nng hp th UV.
- Cc electron t do khng tham gia lin kt, th d cc cp e ca N, O, S. cc
electron ny rt d kch thch.
Loi cui cng l cc electron tham gia lin kt t, loi ny cng rt d b kch thch n
t*.Cc th d v chuyn dch electron trong phn t foocmadehit: HCHO:
= C = O = C
+
O
-
y l kiu chuyn dch t t* v e
-
t do t*.
1.I CNG V PHNG PHP PHN TCH QUANG HC
S bin i nng lng to ph hp th phn t UV-VIS.
Khi chm sng (photon) c nng lng thch hp nm trong vng sng 190 - 800 nm
chiu vo, phn t nhn nng lng, tr thnh trng thi kch thch. Nng lng tng E(ts) ca
chm sng m phn t nhn c cui cng bin thnh nhit nng nhng c 3 dng
chuyn ha:
E(ts) = E(e) + E(d) + E(q)
E(e) l dng chuyn mc cc electron: Trong phn t, cc in t tham gia vo lin kt
trong cc lin kt o, t, ngoi ra cn c cc i in t khng lin kt (n), s hp th nng lng
ca chm sng v n chuyn ln trng thi nng lng cao Em. Khi phn t cht b kch thch
nh th, n c s chuyn mc nng lng: o o* ; t t* ; n o * hay n t *
Ed v Eq: l nng lng quay v dao ng ca nguyn t trong phn t. N c hnh
thnh khi phn t ca cht nhn nng lng bi chm sng kch thch, tuy nhin do nng lng
thp nn tc ng ca n ch lm quay hoc dao ng cc nguyn t quanh v tr cn bng.
Sau khi cht hp th, ta o phn cn li ca chm sng chiu vo ban u to ra ph
hp th quang phn t ca cht. V th ph loi ny c gi l quang ph hp th phn t UV-
VIS.
1.I CNG V PHNG PHP PHN TCH QUANG HC
1.2 S BIN I NNG LNG KHI SNG IN T TC DNG VI VT CHT
a nguyn t sang trng thi kch thch, mt yu cu bt buc l n phi
dng kh hay th kh.
Mu ban u c th rn hay lng, tuy nhin sau khi chun b mu, chng dng
lng. Qu trnh ha hi lm n chuyn sang rn ri kh, do : M(r) + E M(k).
Khi kch thch M(k) bng ngun nng lng Em, c hai kh nng:
1. Nng lng Em khng ph hp, nguyn t khng hp th Em, tng tc n hi
v khng sinh ph.
2. Nng lng Em ph hp, nguyn t s hp th nng lng Em v nhy ln mc
nng lng cao, va chm khng n hi. C s trao i nng lng (cho- nhn),
nguyn t b kch thch ln trng thi M(k)* v sau pht ra cc tia pht x, di
dng hv, l ph pht x ca nguyn t.
Mu (M) M(k)
Em + M(k) M(k)*
M(k)* M(k)o + E(hv) Ph AES ca M
1.I CNG V PHNG PHP PHN TCH QUANG HC
S bin i nng lng to ph pht x nguyn t.
1.2 S BIN I NNG LNG KHI SNG IN T TC DNG VI VT CHT
a nguyn t t trng thi c bn th rn v th kh, M(r) + E M(k)
ri chiu vo m hi 1 chm sng kch thch c xc nh, c hai trng
hp:
1. Nng lng E ca chm sng khng ph hp, nguyn t khng hp th E,
tng tc n hi, khng c ph.
2. Nng lng E ca chm sng ph hp, nguyn t hp th nng lng E ca
tia v nhy ln mc nng lng cao. Va chm khng n hi xy ra v c s
trao i nng lng, E(hv) + Mo(k) M(k)*. l qu trnh hp th nng
lng E ca nguyn t, v n t mc Ecb Em. Khi o phn cn li ca chm
sng kch thch, thu c ph gi l Ph hp th nguyn t. Ph hp th
nguyn t c tnh cht sau:
+ S tng tc ca nng lng ca chm sng n sc nht nh vi vt cht
th kh, l cc nguyn t t do ca kim loi mc nng lng c bn Eo.
+ Xy ra i vi cc vch ph c trng v nhy ca cc nguyn t.
1.I CNG V PHNG PHP PHN TCH QUANG HC
1.2 S BIN I NNG LNG KHI SNG IN T TC DNG VI VT CHT
S bin i nng lng to ph hp th nguyn t.
Cc phng php phn tch quang hc

















CC PHNG PHP PHN TCH
QUANG HC

CC PHNG PHP PHN TCH
QUANG PH NGUYN T

CC PHNG PHP PHN TCH
QUANG PH PHN T
PP HP TH
PHNNT
UV-VIS

PP
HUNH
QUANG

CC PP KHC
(HNG NGOI,
PHN CC,
KHC X,
C,
PP QUANG PH
PHT X NT

PP QUANG PH
HP TH NT


1.I CNG V PHNG PHP PHN TCH QUANG HC
Cc phng php khc
1. Phng php khc x, da trn php o chit xut ca cht nghin cu;
2. Phng php phn cc, da trn s nghin cu gc quay ca mt phng nh sng
phn cc;
3. Phng php ph hng ngoi, nghin cu s hp th bc x hng ngoi ca cht
phn tch nh lng v nh tnh.
4. Phng php ph tia X, nghin cu s nhiu x (ch yu) ca tia X khi chiu vo
mu nhm nh tnh v nh lng.
5. Phng php ph Raman, nghin cu ph tn x ca chm sng ti c bc sng
xc nh trong vng nhn thy khi chiu vo cht phn tch dung dch, thng
gc 90
o
so vi tia ti sau khi loi chm sng hunh quang ...
Nhng phng php ny c s dng khng nhng nh tnh v nh lng
m cn nghin cu cu trc ca cht.
1.I CNG V PHNG PHP PHN TCH QUANG HC
1.4 I CNG V CC THIT B PHN TCH QUANG
HC
- Nhm cc thit b quang phn t, l cc thit b phn tch cht trng thi
phn t. Nhm ny gm cc my o: + My quang ph hp th phn t UV-
VIS; + My o hunh quang phn t; + My hng ngoi; + My o khc x

c im chung ca cc thit b ny l s dng sng in t nghin cu mu
trng thi phn t dng lng hoc rn. Cc my o c ba phn chc nng c
bn: Ngun pht sng in t; Phn gii ph; X l tn hiu
- Nhm cc thit b quang nguyn t, l cc thit b nghin cu cc cht phn
tch trng thi nguyn t. Nhm ny gm cc my o:
+ My quang ph pht x nguyn t
+ My quang ph hp th nguyn t
+ My hunh quang nguyn t hay c th gi pht x hunh quang nguyn t.
1.I CNG V PHNG PHP PHN TCH QUANG HC
Thit b phn gii ph trong cc my o quang
a) Phn gii ph bng lng knh

Hnh 2.9 Phn gii ph bng lng knh
Lng knh ABC c chit sut n, khc vi chit sut ca mi trng. Khi chiu chm sng c bc
sng v gc ti o vo lng knh c chit sut n, tia l c gc lch | i qua lng knh. D l gc
lch gia tia ti v tia l ra khi lng knh.
Cng thc c trng cho lng knh l:
2
A
n.sin
2
D A
Sin =
+
v
(A/2) sin n 1
2sin(A/2)
.
d
dn
d
dD
2 2

=
Nu gc A l 60
o
th tn sc gc c
th tnh theo cng thc:
) n (1
2
.
d
dn
d
dD
2

=

1.I CNG V PHNG PHP PHN TCH QUANG HC
1.4 I CNG V CC THIT B PHN TCH QUANG HC
b) Phn gii ph bng cch t.
Cch t c hai loi l phn x v truyn qua. Cch t phn x c ch to bng
tm nhm phng hoc lm, khc rt nhiu cc rnh nh song song (650-3600 vch trn
1mm). bo v cch t sau khi to rnh, ngi ta ph mt lp mng SiO
2
.

Hnh 2.10 Cch t phn gii ph
Cch t c iu ch nh vy ging nhng khe hp c nm. Khi chiu chm
sng in t vo cch t, gp nhng khe hp c nm xy ra hin tng nhiu x. Ty
thuc vo rng ca khe hp v ty thuc vo bc sng ca tia ti, gc phn x r c
gi tr khc nhau theo biu thc:
d
m
Sinr = trong r l gc phn x, d l
rng khe hp trn cch t, l bc sng ti
(cm), m l bc nhiu x, l cc s nguyn.
Thit b phn gii ph
1.I CNG V PHNG PHP PHN TCH QUANG HC
Thit b khuch i, nhn quang in (photomultiplier tube)
Thit b dng ng, c chc nng chuyn tn hiu quang (h) thnh tn hiu
in, ng thi khuch i tn hiu ln c th t hng triu ln.

Tn hiu quang hc l nhng photon i
vo nhn quang in c chuyn
thnh electron. Cc cc 2,3,4,5,6
thng l cc kim loi kim, c th
cc sau cao hn cc trc tng tc
cho e. Nhng thit b hin nay c th
nhn 10
7
electron cho mi photon
Hnh 2.11 Thit b nhn quang in

1.I CNG V PHNG PHP PHN TCH QUANG HC
2.1 NH LUT BOUGHE - LAMBE BEER (nh lut Beer)
Chiu mt chm sng c bc sng xc nh i qua b lp dung dch. Do hp
th, sau mi lp dung dch, nh sng gim i n ln. Gi cng nh sng ban u l
I
o
, sau khi i qua lp th nht l I
1
ta c:
n
I
I
o
1
= . Khi i qua lp th hai, nh sng
gim i n
2
ln, ta c
2
o
2
n
I
I = , tip tc vi b lp ta c I
n
I
I
b
o
n
= = hay
b o
n
I
I
=

Ly logarit hai v, ta c: log
I
I
o
= b.log n = k b. i lng log
I
I
o
ta gi l hp th
quang A, k l h s, ta c: A= k.b (2.1)
Hnh 2.1
a)Cuvet cha dung dch hp th
quang
b) Hai cuvet cng cha mt lng
cht mu c quan st t trn xung
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
CHNG 2 PHNG PHP QUANG PH HP TH PHN T UV-VIS
- Ly hai lng cht mu bng nhau, cng loi, ha tan trong cuvet, c th quan st dung dch
t trn xung. cng loi, dung dch mt c chiu cao h1, dung dch 2 c chiu cao h2; h1>h2.
Nh vy, nng dung dch 1 nh hn dung dch 2, ta c: K C
1
b
1
= K C
2
b
2

- Tin hnh vi nng dung dch C
1
nh hn C
2
n ln, tuy nhin s lp cht mu li tng n ln
nn tch s K.C.b khng i.
- Khi thay dung dch th hai bng cht mu khc, sao cho hai dung dch 1 v 2 c cng nng ,
v s lp cht mu, C
1
= C
2
v b
1
= b
2
. Tuy nhin, lc ny K
1
khc K
2
cho nn hp th
quang khc nhau, ta c phng trnh:
K
1
C b = K
2
C b (2.2)
Nh vy hp th quang ca mt cht mu ph thuc vo:
- Bn cht ca cht mu vi h s K tng ng
- Nng cht mu, C
- Chiu dy lp hp th, b
Kt hp c (2.1) v (2.2), h s k trong 2.1 l hng s ph thuc c hai yu t: nng v bn cht
ca cht, ta c phng trnh: A=bC
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.2 TNH CHT CA H S HP TH PHN T, c
Trong biu thc A = cbC, nu C c biu din bng mol/l v b tnh bng
cm th c l h s hp th phn t gam. Biu thc trn cho thy c c gi tr bng A
khi dung dch c nng bng 1M o vi cuvt c b dy b = 1cm.
- H s hp th phn t gam c c trng cho bn cht hp th nh sng v
khng ph thuc vo th tch dung dch, b dy lp dung dch v ch ph thuc vo
ca dng sng ti (I
0
). Do i lng c thng c coi l tiu chun khch
quan quan trng nht nh gi nhy ca php nh lng trc quang, c =f().
- Th nguyn ca c:
Ta c: c =
A
bC
(2.4)
c =
l) b(cm).C(M/
A
= l /cm
-1
M
1
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.3 TNH CHT CA HP TH QUNG A V H QU
2.3.1 Cc tnh cht
a) Ph hp th quang A ph thuc bc sng ca nh sng ti.
Chiu chm sng c bc sng khc nhau i qua dung dch hp th, hp th
ca dung dch ph thuc nhiu vo bc sng (thay i bc sng).






Chiu cc chm sng c bc sng thay i mt cch lin tc t bc sng di n
bc sng ngn hn (hoc ngc li), cn gi l qut ph, ta thu c ph hp th l
nhng di lin tc, c nhng cc i hp th, cc v tr
max
khc nhau tu thuc
cht phn tch (hnh 2.1).
Hnh 2.1
Ph hp th quang ph
thuc bc sng
e
l
(nm)
l max
e max
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
b) hp th quang A ph thuc nng cht
Lp dy chun cht hp th quang c nng khc nhau trong iu kin
ph hp v chiu chm sng c bc sng c nh ng vi cc i ca ph hp
th cht mu qua dung dch, ta thu c mt dy s liu v hp th quang ca
cc dung dch, v vo th, ta thu c ng chun biu din s ph thuc
hp th quang vo nng cht, A=f(C).






Hinh2.2. ng chun biu din s ph thuc A vo nng C.
C Cx
Ax
A
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.3 TNH CHT CA HP TH QUNG A V H QU
d) hp th quang A c tnh cht cng tnh
Nu dung dch c nhiu cht hp th, hp th quang ca dung dch mt
bc sng nht nh l tng cc hp th quang thnh phn (hnh 2.3):
A= c
1
C
1
b + c
2
C
2
b ++ c
n
C
n
b

2.3.2 Bit c v A
max
ring c th xc nh ng thi nng hai cht trong dd
Hai cht P v Q c hai cc i hp th ti hai bc sng
1max
v
2max

o hp th quang ti hai bc sng trn, thu c hai i lng hp th A
1
v A
2
,
trong A
1
v A
2
u l tng ca cc i lng hp th thnh phn ti mi bc sng
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.3 TNH CHT CA HP TH QUANG A V H QU
Th d 1.2: P v Q to phc vi thuc th X, to thnh PX v QX c hai cc i hp
th 400nm v 500 nm, c tng ng vi mi nguyn t nh sau:
400 nm 500 nm
c ca phc PX 1.10
4
l /cm
-1
M
1
1.10
3
l /cm
-1
M
1

c ca phc QX 1.10
3
l /cm
-1
M
1
1.10
4
l /cm
-1
M
1

Ho tan hon ton 0,10g mu, thm cht che v thuc th ri nh mc n 100
ml. o hp th quang (A) hai bc sng 400 nm v 500 nm, c cc s liu sau:
A
400
= 1.10
4
C
P
+ 1.10
3
C
Q
= 0,500 (2.5)
A
500
= 1.10
3
C
P
+ 1.10
4
C
Q
= 0,300 (2.6)
Tnh hm lng P, Q trong mu bit M
P
= 65, M
Q
= 60.
Gii: Nhn hai v ca phng trnh (2.6) vi 10 ta c
1.10
4
C
P
+ 1.10
3
C
Q
= 0,500
1.10
4
C
P
+ 10.10
4
C
Q
= 3,00
Ly 2 tr 1 ta c 9,9.10
4
C
Q
= 2.50
Tnh c C
Q
=
4
10 . 9 , 9
50 , 2
=2,525.10
-5
M %Q = % 00152 , 0
1 , 0 1000
. 100 . 60 . 10 . 525 , 2
5
=

x

C
P
= 4,75.10
-5
M/l %P = % 00308 , 0
1 , 0 1000
. 100 . 65 . 10 . 75 , 4
5
=

x

2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
MI LIN H
GIA TRUYN QUA T V HP TH A
truyn qua c nh ngha,
o
I
I
T = ;
T
1
log A =
-logT =
0
I
log .C.b
I
= hay
Cb
10 T

=


2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.3.3 Mi lin h gia hp th quang (A) v truyn qua (T)
Th d 1.4 Mt mu dung dch cha trong cuvet 1cm o truyn
qua t 80% nh sng mt bc sng nht nh. Nu hp th
quang ca cht ny cng bc sng l 2,0 th nng cht l
bao nhiu.
Gii: truyn qua l 0,8 hay phn trm truyn qua t 80% nn
T=0,8. Theo nh ngha: log T = - .b.C hay log 1/T = .b.C, vy
theo u bi ta c
Log 1/T = 2,0 cm
-1
mol
-1
.l .1 cm.C
Log 1/0,8 = log 1,25 = 2 mol
-1
l.C
C = 0,10/2,0 = 0,05M/l
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.4 NHNG SAI LCH CA NH LUT BEER
2.4.1 Nhng du hiu
hp th quang A l hm bc nht ca bc sng, nng C v chiu
dy lp dung dch o b: A = f(, C, b). Khi c nh iu kin o v bc sng, v
chiu dy lp dung dch (thng o vi cuvet 1cm) th A=f(C), y l s ph
thuc tuyn tnh (hnh 2.2). Khi s ph thuc ny khng tuyn tnh iu c
ngha l c s sai lch. y l du hiu th nht v s sai lch khi nh lut
Beer.
Du hiu th hai l ph hp th ca dung dch cht hp th quang nhng
nng khc nhau phi c cc i cng mt bc sng (cc iu kin khc
nh pH, thnh phn dung ging nhau). Cc dung dch c thnh phn ging nhau
tr cht hp th quang c thnh phn khc nhau nhng cc i hp th lch nhau
th y cng l du hiu ca s khng tun theo nh lut Beer.
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
a) Do nh sng khng n sc
Khi nh sng khng n sc chiu qua cht hp th quang,
c ngha dng sng ti c nhiu tia sng vi cc bc sng khc
nhau, cht phn tch ch hp th mt s tia sng nht nh, t l
hp th khng ng u. Khi tng nng cht phn tch, mt s
tia sng c th b hp th hon ton trong khi mt s tia sng
vn b hp th t, thm ch khng hp th. Kt qu l thu c
ng biu din khng tng tuyn tnh v hp th quang theo
nng (do cc tia sng khng b hp th c cng i ra (I)
khng gim khi tng nng )
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.4.2 NHNG NGUYN NHN SAI LCH CA NH LUT BEER
2.4.2 NHNG NGUYN NHN SAI LCH CA NH LUT BEER
b) Cht hp th quang c thnh phn thay i
1. Cht hp th quang khng bn, thnh phn thay i khi pha long dung dch
Gi o l phn ly ca phc mu MX, phng trnh phn ly nh sau:
MX M + X
(1-o)C oC oC Hng s phn ly K l
K =
[MX]
[M][X]
= o
2
C
o 1
1
K = o
2
C o =
C
K
(cha pha long) (2.7)
Pha long n ln o
n
=
n / C
K
=
C
nK
; S = o
n
o
1
= 1) n .(
C
K





C
K

sai lch S t l thun vi K v n , t l nghch vi C .(hnh 2.4).
trnh s phn ly ca phc MX, nng thuc th X cao, o
n
= o
1
, S =0.
S
Hnh2.4
S ph thuc ca sai lch S
vo t l
C
K


2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
nh hng ca ion H
+
(pH) ti s hnh thnh phc mu.
a s cc thuc th dng trong phn tch ph hp th phn t l nhng
mui ca axit hay baz:
M + HX MX + H
+

Khi tng hoc gim nng H
+
, u lm cn bng to MX thay i.
Trng hp pH cao, kim loi M c th b thu phn v kt ta, mt khc X
trng thi X
-
, nh vy, phc c th trang thi a phi t (th d phc Fe(III)-
salixilic pH 1-3 hnh thnh phc 1:1 FeSal
+
c mu tm, khi tng pH ln 4, mt
na phc c 2 phi t, FeSal
2
-
c mu ; n pH 9, phc chuyn sang dng 3
phi t, FeSal
3
c mu vng).
Trng hp nng H
+
cao, pH thp, HX tn ti nhiu, MX cng hnh thnh t.
Ngi phn tch cn chn ra pH ph hp cho vic hnh thnh phc mu va m
bo phc MX hnh thnh tt, chnh xc v lp li cao.
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.4.2 NHNG NGUYN NHN SAI LCH CA NH LUT BEER
3 nh hng ca cc cu t l
a) Cc cu t l l cation
K hiu cu t l l ion kim loi M, n cng tc dng vi
thuc th X to hp cht mu MX tng t MX. Nh vy, hp
cht ny cng hp th quang, lm sai lch kt qu o v pha
dng. trnh hin tng ny, phi chn thuc th X c hng
s bn vi M cao hn vi M (hng s bn ln hn 10
4
ln th
khng nh hng). Trng hp thuc th l anion ca axit yu,
cn s dng nng H
+
lm phng tin che.
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.4.2 NHNG NGUYN NHN SAI LCH CA NH LUT BEER
Th d 1.6 Tnh pH cn thit xc nh Fe
3+
bng phng php quang ph hp th
phn t UV-VIS vi thuc th axit salixilic (H
2
Sal) 10
-2
M khi c mt Cu
2+
. Cho hng
s phn ly H
2
Sal l 10
-16
, hng s phn ly ca Fe(Sal)
2+
l 10
-16
, ca Cu(Sal) l 1.10
-12
.
Gii: Phn ly ca Fe(Sal)
2+
l Fe(Sal)
+
=Fe
3+
+Sal
2-
; K
PL
=
] [Fe(Sal)
] ][Sal [Fe
2
2 3
+
+
=10
-16

Cu(Sal)=Cu
2+
+Sal
2-
; K
PL
=
[Cu(Sal)]
] ][Sal [Cu
2 2 +
=10
-12
Khi 99% Fe
3+
to phc tc l

100
1
] [Fe(Sal)
] [Fe
3
=
+
+
=
] [Sal
K
2
Pl

[Sal
2-
] = 100K
PL
Khi Cu
2+
to phc 1% tc l

1
100
[Cu(Sal)]
] [Cu
2
=
+
=
] [Sal
K'
2
PL

[Sal
2-
] =
100
K'
PL
T y rt ra K
PL
=
10
-4
K
PL
hay ni
cch khc l 2 hng s phn ly phi hn nhau 10
4
ln v [Sal
2-
] =
PL PL
.K' K = 10
-14
.
Mt khc: H
2
Sal = 2H
+
+ Sal
2-
; K
PL
=
16
2
2 2
10
Sal] [H
] [Sal ] [H

+
=
[H
+
]
2
= 10
-16

4
14
2
16
2
2
10
10
10
10
] [Sal
Sal] [H

= = pH = 2
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
b) Cu t l l anion,
Khi c cc anion (A) phn ng vi kim loi M cn phn tch, n
lm cho phc mu MX hnh thnh khng hon ton, i khi nu nng
anion l ln, bn th phc MX khng hnh thnh. loi tr nh hng
ca cc anion c 3 kh nng chnh:
+ Chn thuc th X to phc tt vi M (c th p dng c k thut
che, pH) phc MA khng hnh thnh.
+ Thm vo dung dch cht chun mt lng anion l tng ng.
Trng hp ny nh hng ca cu t l n cht phn tch v cht chun
l nh nhau, kt qu o c so snh vi nng cht c trong mu
chun, t tnh ra nng ca n.
+ Tch loi cc anion trc khi cho thuc th X vo mu.
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.4.2 NHNG NGUYN NHN SAI LCH CA NH LUT BEER
2.4 CC PHNG PHP NH LNG




x
st
st
x
st
st
x
x
.A
A
C
C
A
C
A
C
= =


x
st
st
x
.A
A
C
C =


tg
h
C
.tg C A
x
x
x x
=
=


C
x
x
x
x
C
A
.
A
A
C
C
A

= =

CHUN 1 IM CHUN NHIU IM ( CHUN) THM CHUN
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
2.5 THIT B QUANG PH HP TH PHN T UV-VIS
2.5.1 S my quang ph hp th phn t UV-VI S

Hnh 2.8 S my UV-VIS
1. Ngun sng 5. Cuvet mu
2. B phn n sc 6 Dung dch so snh
3, Bn gng 7,8 T bo Quang- in
4 Gng 9 X l tn hiu
2.PHNG PHP QUANG PH HP TH PHN T UV-VIS
3.1 NH LUT V QUANG PH PHT X NT, NGUYN NHN XUT HIN QUANG PH
3. PHNG PHP QUANG PH PHT X NGUYN T
- Bnh thng, NT trng thi c bn. C nng lng kch thch m
hi nguyn t th chng chuyn ln trng thi kch thch.
- Trng thi kch thch rt ngn c 10
8
giy chng tr v trng thi ban
u, gii to ra nng lng dng bc x gi l ph pht x nguyn t.
- Cng vch ph, I v s nguyn t N trong plasma lin h =ptr
Schaibe Lomakin: I = KN. Trong N l s nguyn t trong plasma
lin h vi nng C ca cht phn tch bng biu thc sau: N =
K
a
C
b
trong , K
a
l hng s thc nghim. C < C
o
l nng ngng
th b =1. Ta c Schaibe Lomakin
I = aC
b

trong : a hng s thc nghim, ph thuc vo cc iu kin nguyn
t ho mu. C nng cht phn tch. b hng s thc nghim.
3.2 QU TRNH TO PH PHT X NGUYN T
3. PHNG PHP QUANG PH PHT X NGUYN T
3. PHNG PHP QUANG PH PHT X NGUYN T
3.2.1 S my quang ph pht x nguyn t








Hnh 3.1 S my quang ph pht x nguyn t
1 Ngn la kch thch ph 2- Thu knh 3- Khe o
4- Cch t to tia n sc 5- X l tn hiu
Ngun kch
thch quang ph

Nguyn t ho v
kch thch quang ph

Ho hi
mu
Phn gii
ph
Khuch i
v ghi ph
3.3 THIT B QUANG PH PHT X NGUYN T


N NGUYN T HA NGN LA (Burner-Perkin-Elmer)
3.3 THIT B QUANG PH PHT X NGUYN T
3. PHNG PHP QUANG PH PHT X NGUYN T
NGUN
KCH
THCH
QUANG
PH
PHT
X - ICP
3. PHNG PHP QUANG PH PHT X NGUYN T
CC THIT B KHC
H quang hc
B phn cch t chn tia n sc c trng
cho nguyn t phn tch c cu to v tnh cht
hon ton tng t cc cch t trong cc my
quang khc (UV-VIS, AAS)
H in t
H iu khin, Nhn Quang - in, h tch phn,
x l s liu, np mu ... l cc b phn khng
th thiu i vi cc my o
3. PHNG PHP QUANG PH PHT X NGUYN T
3.3 THIT B QUANG PH PHT X NGUYN T
3.4 CC NGUN KHCH THCH QUANG PH PX NT
3. PHNG PHP QUANG PH PHT X NGUYN T
3.3.1 Ngn la n kh
TT Hn hp kh chy Nhit ti a Tnh cht
1
2
3
4
Hn hp kh H
2
+ O
2

Hn hp kh C
2
H
2
+ khng kh
Hn hp kh C
2
H
2
+ O
2

Hn hp kh dixianogen + O
2

2500
o
C
2300
o
C
2900
o
C
3000
o
C
n nh
n nh
n nh
n nh
Dng ngun kch thch l ngn la n kh c u im l cho
php ta chn c nhit kch thch tu v nhit kh n nh;
song c nhc im l cng vch ph thay i rt nhiu khi thay
i thnh phn hn hp mu phn tch v nh hng ca nn
(matrix).
3. PHNG PHP QUANG PH PHT X NGUYN T
3.3.2 H quang in
- Hin tng phng in gia hai cc gn nhau (4mm), th 220V
- Nhit ti vng h quang ln rt cao (4000-6000
o
C). Ti y, mu phn
tch thng cha trong mt pha in cc, s chuyn thnh hi ri b kch
thch quang ph. Vng ny ngi ta gi l plasma gm cc nguyn t, cc
ion, cc electron v c phn t, y l mi trng pht x.
- H quang in mt chiu dng in p phn cc, mt chiu v H quang
in xoay chiu dng in p xoay chiu. H quang in mt chiu m
bo nhy tt; nhng do nhit cao nn cc lm bng than s b n
mn nhanh.
- H quang in xoay chiu c vch ph to ra ch yu l cc vch ph
nguyn t lp li tt, lun c dng trong phn tch nh lng.
3.4 CC NGUN KHCH THCH QUANG PH PX NT
3. PHNG PHP QUANG PH PHT X NGUYN T
3.3.3 Tia la in
- Tia la in l s phng in gin on (50-300 chu k trong mt giy),
gia hai in cc c th rt cao, 10000-20000KV nhng dng nh (<1A).
- Nhit tm plasma n 4000 - 7000
o
C nn ph pht x ion l ch yu
- Tia la in l ngun kch thch tng i n nh v c lp li cao,
song c nhy km h quang in, cho nn thi gian ghi ph phi di
hn h quang.
- Khi phn tch cc mu kim loi, hp kim v dung dch, tia la in l
ngun kch thch rt tt. Nhng khi phn tch cc mu qung, t, th
ngun kch thch ny khng ph hp v ho hi km v khng n nh.
- Nhc im ca ngun ny l nhit ca plasma cao to thnh cc hp
cht km bn nhit t gp hn trong h quang in.
3.4 CC NGUN KHCH THCH QUANG PH PX NT
3. PHNG PHP QUANG PH PHT X NGUYN T
3.3.4 Plasma cao tn cm ng (ICP- I nductively Coupled Plasma)
- Nng lng cao tn sinh ra t ngun pht cao tn cung cp cho cun cm cao
tn u ming n nguyn t ho mu, to ra plasma.
- Nhit tm plasma khi dng ngun cao tn ti 5000-10000
o
C ho hi
mu, nguyn t ho v kch thch ph
- Plasma cao tn cm ng nguyn t ho c hu ht cc mu phn tch mi
trng thi vi hiu sut cao, ph pht x ion l ch yu.
- Dng ngun kch thch ICP th php phn tch c nhy rt cao (10
-4
- 10
-6

%) v n nh tt, nn sai s ca php phn tch nh
- Dng ngun ny nh lng nhiu nguyn t cng mt lc vi tc phn
tch nhanh, hn na vng tuyn tnh kh rng, khng c nh hng ca nn
nn phng php c dng phn tch cc mu qung c bit cha dy
cc nguyn t c tnh cht ging nhau nh dy cc nguyn t t him rt
thch hp.
3.4 CC NGUN KHCH THCH QUANG PH PX NT
3.5 NH TNH V NH LNG
3. PHNG PHP QUANG PH PHT X NGUYN T
3.4.1 Nguyn tc phn tch nh tnh
- nh tnh s dng nhng vch ph c trng ca nguyn t., vi 2 k
thut l quan st trc tip v dng bng so snh chun gi l Atlat.
- Phng php quan st trc tip ph bng mt vi mt vi nguyn t c vch
ph c trng trong vng kh kin. Th d Li - 670,8 nm () v 610,3 nm
(da cam), Na - 589,3 nm (vng), K - 768,2 nm () v 704,4 nm (tm).
- Phng php dng bng chun (Atlat), bn bc:
+ Chp nh ca st, nh du cc vch c trng ca nguyn t khc.
+ Chp ph ca nguyn t phn tch ln cng mt tm ba vi st.
+ Ghp trng cc vch ca ph st ca hai ba
+ Tm nguyn t trng vch c trng nhn ra nguyn t trong mu
phn tch.
3.4.2 Phn tch nh lng
a) Phng php ng chun
- Cc mu u c trng thi vt l v thnh phn nh mu phn tch.
- Mu u v mu phn tch phi c x l trong cng mt iu kin.
- Cc mu u phi bn vng theo thi gian,
- Nng mu phn tch nm trong khong tuyn tnh nng dy chun
trong cng iu kin.
b) Phng php thm chun


C A
x 1

=
C A

C 1
x
A
.A
C =

Hnh 3.2. th chun xc nh bng phng php thm
3. PHNG PHP QUANG PH PHT X NGUYN T
3.5 NH TNH V NH LNG
4.1 S XUT HIN PH HP TH NGUYN T V NH LUT C BN
4. PHNG PHP QUANG PH HP TH NGUYN T
- Bnh thng, nguyn t trng thi c bn, bn vng
mc nng lng thp
- Khi cc nguyn t trng thi t do trong mt m hi,
- Nu chiu chm bc x c bc sng xc nh ng vi
bc sng m chng c th pht ra khi trng thi kch
thch vo m hi nguyn t t do ,
- Nguyn t hp th bc x chiu vo . l qu trnh hp
th nng lng ca nguyn t t do trng thi hi to
ra ph hp th nguyn t ca nguyn t.
- A ph thuc vo s nguyn t N trong mi trng hp th: A = k.N trong
k l h s thc nghim, ph thuc vo bn cht nguyn t, nhit ca
mi trng hp th v b dy ca lp hp th.
- Gia s nguyn t N vi nng C ca nguyn t trong mu phn tch
c biu th bng biu thc: N = k
i
C
b
trong k
i
, l hng s thc
nghim, b c gi l hng s bn cht, n ph thuc vo nguyn t v
bc sng ca dng sng, b c ga tr s 1; b = 1 khi nng C nh.
- Kt hp cc biu thc trn ta c: A = aC
b
trong a l hng s thc
nghim. ng vi mi bc sng, mi nguyn t c mt ga tr C = C
0
l
gii hn, khi nng C nh hn nng ngng C
0
th b = 1
- Phng trnh biu din mi lin quan gia hp th A v nng C l
nh lut c bn ca php o ph hp th nguyn t:
A = aC
4. PHNG PHP QUANG PH HP TH NGUYN T
4.1 S XUT HIN PH HP TH NGUYN T V NH LUT C BN
4.1 S XUT HIN PH HP TH NGUYN T V NH LUT C BN
HAI PHNG PHP NGUYN T HA PH BIN
S MY
QUANG
PH HP
TH
NGUYN
T MT
CHM TIA
V HAI
CHM TIA
NGUN PHT BC X N SC TRONG AAS
4.2 CC PHNG PHP NGUYN T HA MU PHN TCH
4.2.1 Nguyn t ha mu theo phng php ngn la
Nng lng nhit ca ngn la n kh ha hi v nguyn t ha mu phn
tch. Ngn la cn c 5 yu cu c bn sau:
1. Ngn la lm kh mu phn tch, ha hi v nguyn t ha vi hiu sut cao.
2. Nng lng nhit ngn la phi ln v iu chnh c theo tng nguyn t.
3. Ngn la tinh khit, khng gy ra cc ng sng ph nh hng ti php o.
4. B dy ngn la ln to ra mi trng hp th c tit din ln (2-10cm)
5. Tiu tn it mu phn tch. Bng sau a ra mt vi loi ngn la n kh

Loi kh T l l/pht Nhit
KK Propan 6/1,4 2200
KK Acetylen 4,2/1,2 2450
KK Hydro 4/3 2050
O
2
Acetylen 1/1 3000
N
2
O Acetylen 2/1,8 2900
4. PHNG PHP QUANG PH HP TH NGUYN T
4.2.2 Nguyn t ha mu theo phng php khng ngn la
- K thut nguyn t ha khng ngn la xy ra nh nng lng ca dng in
c cng sut ln, in p 12V, cng 50 500A trong mi trng kh tr.
- Qu trnh nguyn t ha xy ra trong cuvet grafit theo bn giai on k tip
nhau: sy kh, tro ha, nguyn t ha mu v cui cng l lm sch cuvet.
- Cc giai on ca qu trnh xy ra nhanh, t vi giy n vi chc giy.
- Nhit ca cc qu trnh sy, tro ho v nguyn t ho tng dn, cui cng
t khong 3000- 5000
o
C.
- Mi nguyn t c mt nhit sy, tro ho v nguyn t ho ring. Th d
nhit nguyn t ha ca Al: 2850
o
C, Ca: 2800
o
C, Mn 2750
o
C
- Mi trng thun li cho ha hi mu, nguyn t ha cht phn tch l cc
axit d bay hi: HCl v HNO
3
1-5%. Ngoi ra cc yu t cn tr l cc nguyn
t khc, anion cn c xt n loi tr sao cho php o chnh xc.
4. PHNG PHP QUANG PH HP TH NGUYN T
4.2 CC PHNG PHP NGUYN T HA MU PHN TCH
4.3 CC U NHC IM CA PHP O PH HP TH NGUYN T
4.3.1 Cc u im
- Php o ph hp th nguyn t c nhy v chn lc cao. Trn 60
nguyn t ha hc c th xc nh c bng phng php ny vi nhy
t 10
4
10
5
. c th t ti n.10
7
%. vi k thut khng ngn la, nhy
- iu kin thc nghim tng i d, c th cho tt c cc phng th nghim
nh v va.
- C th xc nh ng thi hay lin tip nhiu nguyn t trong cng mt
mu.
- Kt qu phn tch n nh, sai s nh.
4.3.2 Nhc im
- Ch cho ta bit thnh phn nguyn t ca cht phn tch c trong mu phn
tch, m khng ch ra c trng thi lin kt, cu trc ca nguyn t.
4. PHNG PHP QUANG PH HP TH NGUYN T
4.4 NG DNG PHNG PHP PHN TCH PH HP TH NGUYN T
- Phng php quang ph ph hp th nguyn t dung
phn tch vt cc kim loi trong cc loi mu khc nhau ca
cc cht v c v hu c (khong trn 60 nguyn t l
cc kim loi trong qung, t , nc khong, cc mu y
hc, sinh hc, cc sn phm nng nghip, rau qu, thc
phm, nc ung, cc nguyn t vi lng trong phn bn,
trong thc n gia sc).
- Phng php phn tch ph hp th nguyn t cng c
dng xc nh mt s phi kim nh Si, P, As, Te, Se. Mt
s phi kim c th phn tch gin tip qua kim loi.
4. PHNG PHP QUANG PH HP TH NGUYN T