PT Dien Hoa

Trn Mai Lin Phn tch in ha 1
PHN TCH iN HA
Electroanalytical methods
Trng i hc Cng nghip TP HCM
Gii thiu mn hc
S n v hc trnh: 3
Phn b thi gian: 75% l thuyt 25% tho lun
v kim tra
Ti liu hc tp:
Cc phng php phn tch in ha hin i T
Vng Nghi, Trn Chng Huyn, Phm Lun
Phn tch ha l H Vit Qu
Bi ging
Chng 1: C s l thuyt chung v phn loi cc
phng php phn tch in ha
Chng 2: Phng php in th dng cc cc
chn lc ion
Chng 3: Phng php cc ph xung
Chng 4: Cc phng php phn tch in ha ha
tan
Chng 5: K thut in ha trong phn tch HPLC
v FIA
Chng 1: C s l thuyt chung v phn loi
cc phng php PTH
1.1 S in phn
1.2 Qu trnh in cc
1.3 Phn loi cc
phng php PTH
M u
Ha hc phn tch: Cc phng php ha hc v
Cc phng php pt cng c
Cc pp phn tch cng c (ha l):
Cc phng php tch (sc k)
Cc phng php quang hc
Cc phng php in ha
Cc pp in ha: ng dng cc qui lut lin quan ti
phn ng in ha xy ra trn ranh gii tip xc gia
cc cc v dung dch phn tch
M u
H thng phn tch in ha:
Dung dch cht
in li cha trong
bnh in ha

Cc in cc

My o

1.1 in cc Th in cc cn bng
Nguyn t in ha
in cc: h ni tip nhau ca cc tng dn in
(kim loi, dung dch cht in li)
in cc kim loi ion kim loi (in cc tan)
Me / Me
n+
//
in cc
Pt / Ox / Kh //
in cc kh
Pt(H
2
) / H
2
/ H
+
//
in cc
in cc bc clorua
Ag / AgCl ; Cl
-

in cc calomel
(Pt) Hg / Hg
2
Cl
2
; Cl
-

Th in cc cn bng
Ranh gii tip xc gia kim loi v dung dch cht in
li lun xut hin mt th - Th in cc cn bng
Nguyn nhn: do xut hin lp in kp ranh gii
gia kim loi v dd cht in li
Cc kim loi c tnh m in cao (Zn, Fe ) tch in
m trn b mt
Cc kim loi km hot ng (Cu, Ag, Hg) tch in
dng trn b mt
Hnh nh lp in kp
+
+
+
+
+
-
-
in cc dung dch cht in li
+
+
+
+
Hnh nh lp in kp
Hnh nh lp in kp
V d
Xt in cc Zn / ZnSO
4
//
B mt in cc tch in m
Tc qu trnh Zn nhng e ln hn tc
Zn
2+
dung dch nhn e
Lp kp hnh thnh khi tc hai qu trnh ny
bng nhau
Zn Zn
2+
+ 2e

Xt in cc Pt / Fe
3+
/ Fe
2+
//
Mng li tinh th Pt bn vng, khng b ha
tan, ng vai tr vn chuyn e
Fe
3+
+ e = Fe
2+

V d
Pt

+
O
O
O

+
+
+

+

O
O
Lp in kp
Xc nh th cn bng ca mt in cc
Khng th o trc tip th cn bng ca mt in cc
Da vo hiu th cn bng ca 2 cc
Chn cc tiu chun c th = 0
Pt (H
2
) / H
2
p = 1at / H
3
O
+
a = 1
Th in cc
Nguyn t in ha
Nguyn t in ha (nguyn t Gavanic)
M
1
| M
1
n+
|| M
2
m+
| M
2
Ni 2 cc vi nhau bng mt dy dn
S in phn
Ni 2 cc vi ngun in mt chiu
Trn 2 cc xy ra qu trnh in cc nhng ngc vi
qu trnh trong nguyn t Gavanic
Cc ion Zn
2+
i v catot, nhn e to thnh Zn
cc Cu, Cu b tan ra, Cu
2+
khuch tn vo trong
dung dch
S in phn ch xy ra khi th t vo ln hn hiu
th cn bng ca 2 in cc
U = E
a
E
c
+ IR
IR: gim th ca bnh in phn
Nu trong dung
dch cha
lng ln cht
in li tr
U = E
a
E
c

Nu s dng
mt cc c th
khng i
E = U + E
ss

S in phn
S in phn
1.2 Qu trnh in cc
Qu trnh in cc gm cc giai on:
a cc cht in hot ti b mt in cc
Phn ng in cc
Qt chuyn sn phm t in cc ra dd, s to
thnh kim loi hoc hn hng (nu l cc Hg)
Tc ca qt in cc c biu th qua i lng
cng dng
Nghin cu qt in cc: v ng biu din s ph
thuc gia cng dng v th in cc ng
dng th (ng von ampe)
Phn ng in cc

c
a
K
K
Ox + ne Kh
Ox Kh
c Ox a Kh
dn dn
v = - = = K C - K C
dt dt
0
a a
(1 )nF
K = K exp E
RT
o
(
(

Tc ca phn ng:
0
c C
nF
K = K exp( E)
RT
o

Ta phn ng
G
ox
G
ox
-nEF
G
kh
G
ox
+(1-)nEF
Nng
lng
Dng kh
Dng oxi ha
Phc hot ng
S ph thuc ca nng lng hot ha
ca phn ng in cc vo in th
Thay cc gi tr K
a
v K
c
vo biu thc v:
0 o
ox kh
c ox a kh
dn dn nEF (1- )nEF
v = - = =K C exp(- ) -K C exp( )
dt dt RT RT
Phn ng in cc
Cng dng in = v * din tch b mt (S) * in
tch tiu tn bin i 1 mol cht in hot (nF)
Mt dng (j): l gi tr cng dng khi S = 1
0 o
c ox a kh
nEF (1- )nEF
j =nF k C exp(- ) - k C exp( )
RT RT

`
)
Mt dng j o c l tng j
c
v j
a
:
0
c c ox
nEF
j =nFk C exp -
RT
(
(

Phn ng in cc
o
a a kh
(1- )nEF
j =-nFk C exp
RT
(
(

Nh vy: j = j
c
+ j
a
H t cn bng khi j = 0, tc j
c
= j
a

0 o
c ox a kh
nEF (1- )nEF
nFk C exp - =nFk C exp
RT RT
( (
( (

Phn ng in cc
0
0
c ox ox
cb
o
a kh kh
k C C RT RT RT
E = ln + ln =E + ln
nF k nF C nF C
E
0
ch ph thuc vo cc hng s
0 o '
c a
nEF (1- )nEF
k exp - =k exp =k
RT RT
( (
( (

0 0
ox kh
nF (1- )nF
j =nFk' C exp - (E-E ) - C exp (E-E )
RT RT

( (
`
( (

)
Biu din phng trnh trn th
Phn ng in cc
i
c

i
E
i
c
= i
o

i
a
= i
o

E
CB

i
a

Phn ng in cc
ng phn cc ca h nhanh (a); h chm (b)
j
a

j
c

E
CB

E
CB

a
b
Cc qu trnh vn chuyn cht in hot ti in cc
Cht c th c chuyn trong dung dch do:
S khuch tn: do chnh lch nng
S i lu: bng cch khuy trn dung dch, quay cc
S di chuyn cc phn t tch in: do lc ht tnh in
gim s in di: thm mt lng ln cc cht in li tr
Qu trnh in cc chia lm 2 trng hp:
Qu trnh n nh: gradien nng khng i, I v E
khng i, c th o trc tip
Qu trnh khng n nh: gradien nng thay i theo
thi gian, I v E l hm ca thi gian
Qu trnh n nh
iu kin: gradien nng = 0:
C
= 0
t
c
c
S ph thuc nng cht in hot vo khong cch n
b mt in cc (dd ban u ch c cht Ox)
x
0
C
C
*
kh

C
*
ox

C
0
ox

ox

kh

nh lut Fick 1:
B
dn c
DS
dt x
c
| |
=
|
c
\ .
Qu trnh n nh
Gradien nng dng oxy ha v dng kh:
0 * *
ox ox ox kh kh
ox kh
C C C C C
;
x x
c c
| | | |
= =
| |
c c
\ . \ .
Mt dng
B
dn dQ
j ( )nF
dt dt
= =
Qu trnh n nh
0 *
ox ox ox
ox ox
ox
*
kh kh
kh kh
kh
C C C
j nFD nFD
x
C C
nFD ( ) nFD
x
c
| |
= =
|
c
\ .
c
= =
c
0 * *
ox ox ox kh kh
j (C C ) C = =
Mt dng t gi tr cc i khi C
*
Ox
= 0
Dng in phn khi gi l dng gii hn khuch tn
0
gh ox ox
j C =
(1)
Dng gii hn khuch tn:
Khng ph thuc vo th in cc
Pt (1) l c s ca cc phng php phn tch nh
lng trong phn tch in ha
Ph thuc vo tc khuch tn i lu (khuy dd,
quay cc), nhit
Nh vy dng gii hn khuch tn ch ph thuc
vo nng th phi gi cc iu kin trn khng
i
Qu trnh n nh
Chia v vi v ca 2 pt trn:
0
gh
* *
ox ox
ox kh
ox ox kh
j j
C j j
C ; C

= = =
Qu trnh n nh
Phng trnh ng phn cc catot:
*
gh
Ox kh
*
ox Kh
j j
C
.( )
j C
=
Theo Nernst:
*
0
Ox
*
Kh
C RT
E E ln
nF C
= +
Suy ra:
gh
0
Ox
Kh
j j
RT RT
E E ln ln
nF nF j
= + +
gh
0
kh
ox
j j
nF
.( ) exp (E E )
j RT
(
=
(

Phng trnh ng phn cc catot
Biu din trn th ng phn cc
j
c

j
a

0
j
c gh

j
agh

E
E
a
1/2

E
c
1/2

E
1/2

E
1/2

1
2
3
5
4
Th bn sng: th khi mt dng bng na dng
gii hn
Qu trnh n nh
0
Ox
1/ 2
Kh
RT
E E ln
nF
= +
Qu trnh khng n nh
C
0
t
c
=
c
2 2 2
ox ox kh kh
ox kh
2 2
C C C C
D ; D
t x t x
c c c c
= =
c c c c
0 0
ox ox kh kh
ox kh ox kh
C C nF (1 )nF
D D k' C exp (E E ) C exp (E E )
x x RT RT
c c
( (
= =
`
( (
c c

)
Chng 2: Phng php in th dng
cc cc chn lc ion
2.1 Gii thiu
2.2 L thuyt v cc th mng ca cc cc chn lc
2.3 Nguyn tc cu trc cc cc chn lc ion
2.4 K thut thc nghim
2.5 Mt s phng hng ng dng cc cc chn
lc ion
2.1 Gii thiu
Phng php phn tch in th
Cc so snh
Cc ch th
in cc chn lc ion (ISE): c kh nng o chn lc
hot ca mt phn t ion c bit no
in cc thy tinh: H
+

in cc florua: F
-
in cc chn lc ion (ISE)
Picture of a commercial fluoride ISE
2.2 L thuyt v cc th mng ca cc cc chn lc ion
Cu to cc chn lc (ISE: ion
selective electrode):
Cc so snh trong 1
Dung dch trong 1: c thnh
phn, nng xc nh
Mng: rn, lng, thy tinh
Cc ss
trong 1
Dd trong 1
Mng
H in ha khi
s dng ISE:
ISE
Cc so snh 2
Dung dch
phn tch
Khuy t
Mng thy
tinh
Dy Ag
Dd cha bit
gt pH
in cc calomel
bo ha
in cc
thy tinh
S in ha:
Cc so snh 1/ Dd trong 1/ Mng//Dd phn tch/ cc so snh 2
Th ca nguyn t in ha:
E = E
2
+
M
E
1

Khi dd 1 v dd phn tch cha cng loi ion (J),khng c
ion no gy cn tr:

Th ca ISE l:

A
J
M
J
a (1) RT
= ln
zF a (2)
ISE J
RT
E = Const + lna (1)
zF
Nu trong dung dch c ion K gy cn tr:

Th ca ISE s thay i:

K
J/K
: h s chn lc cho ion K i vi ion cn xc nh J (K
gip nh hng c s nh hng ca cc ion khc ti
vic x ion cn phn tch)
+
A
J JK K
M
J
a (1) K a RT
= ln
zF a (2)
ISE J J,K K
RT
E =Const + ln a (1) k a (1)
zF
( +

Cu trc mng mt s loi mng chn lc
Mng cha ion tan c kh nng trao i ion
Tnh cht ca mng ph thuc:
H s phn b ca mui cha ion trao i v ion cn
xc nh
S to cc cp ion trong mng
Gi s mng cha mt loi mui JA: J
+
l ion cn
xc nh; A
-
l ion trao i
Hiu th ranh gii gia mng v dung dch:

J
1
J
J
2
J
a (m) RT
ln
F a (1)
a (m) RT
ln
F a (2)
=
=
Mng dd 1

Mng dd2
Cu trc mng
Th chung ca mng:

Tng qut:

Nu trong dung dch c ion K gy cn tr - Phng trnh th s
thay i:
J
2 1
J
a (1) RT
ln
F a (2)
A = =
+
+
A =
n
n
J
J
a (1)
RT
ln
zF a (2)
ISE J J,K K
RT
E =Const + ln a (1) k a (1)
zF
( +

Khi in tch ca ion nh hng l +2 th:

Mng cha cht mang ion trung tnh
Cc mng rn v vt liu thy tinh

2 2
1/ 2
ISE
J J ,K K
RT
E =Const + ln a (1) k a (1) (2.20)
zF
+ + + +
(
+

2.3 Nguyn tc cu trc cc cc chn lc ion
V cc
Dung dch trong cc
Cc so snh
Mng (rn hoc lng)
Cc so snh trong
Dung dch trong
Mng
Dung dch
trao i ion
Mng
V cc
Yu cu: ngn cch hon ton dung dch trong cc
dung dch phn tch
Cc mng rn: PVC, Teflon, nha
in cc Florua: in cc mng rn
c cu to bi cc tinh th v c
Mng l tinh th LaF
3
trn vi ph
gia EuF
2
C nhng khong trng trong mng
lm cho cc anion c th khuch tn
qua (F
-
)
Th ca ISE F
-
:
E = const 0,059lg[F
-
] = K + 0,059pF
Cc so snh trong:
Ag/AgCl
Dung dch trong: 0,1M KCl; 0,1M NaF
in cc nhy vi ion F
-
gp 10 ln OH
-
; nh vy tng
qut:
E = K 0,059lg([F
-
] + 0,1[OH
-
])
(Nu dng F
-
trong mi trng kim s mc sai s)
Mt s in cc mng rn
Dy Ag
Dung dch
Cl
-
c
nng
xc nh
v cation
cn phn
tch
Ag/AgCl
mng rn)
Mng Ion cn xc nh
LaF
3
F
-
, La
3+
AgCl Ag
+
, Cl
-
AgBr Ag
+
, Br
-
AgI Ag
+
, I
-
Ag
2
S Ag
+
, S
2-
Ag
2
S + CuS Cu
2+
Ag
2
S + CdS Cd
2+
Ag
2
S + PbS Pb
2+
Solid-State Electrode Analytes
in cc mng rn
V d v in cc mng lng
Trao i ion qua mng
V d: mng hydrophobic trao
i Ca
2+
Khi cn bng th, s trao i kt
thc
Phng trnh trao i ion Ca
2+
:
[(RO)
2
POO]
2
Ca 2(RO)
2
POO
-
+ Ca
2+
Th ca in cc:

E khng ph thuc vo pH trong khong t 5,5 11
nhy ca in cc vi Ca
2+
gp 50 ln Mg
2+
; gp 1000
ln K
+
v Na
+

2
0, 059
lg
2
ISE
Ca
E K a
+
= +
in cc mng lng
Liquid-Based ISE Analytes
V d v in cc nhy vi cht kh
Nguyn tc: da trn hot ng ca mt mng thm
kh
V d: in cc nhy vi kh SO
2
(tan trong dung dch)
SO
2
khuch tn qua mng ti khi t trng thi cn
bng:

Cc l nh ca mng tip xc vi dung dch bn
trong v xy ra cn bng th 2
SO
2
SO
2

Dung dch phn tch
Cc l nh ca mng
V d v in cc nhy vi cht kh
SO
2
+ 2H
2
O HSO
3
-
+ H
3
O
+

Nng H
+
s c o vi mt in cc thy tinh
(sensor) c t ngay sau mng bn thm
V H
+
t l vi SO
2
nn:

SO
2
SO
2

Cc l mng cha kh
Dung dch trong
2
0, 059
lg[ ]
1
ISE
E K SO = +
ng dng ca ISE
in cc thy tinh
Mng u tin c khai thc lm in
cc l mng thy tinh, rt chn lc vi H
+

S :
c Calomel // [H
+
] = a
1
/ mng thy tinh / [H
+
] = a
2
, [Cl
-
] = 1M, AgCl/Ag
V
1

V
2

c so snh 1 Dd phn tch c thy tinh
in cc thy tinh
Thnh phn ca thy tinh nhy vi H
+

Khng phi mi loi thy tinh u nhy vi s thay
i pH (v d: thch anh v pyrex)
Thnh phn gn ng: 22% Na
2
O; 6% CaO; 72%
SiO
2

Mng ny nhy vi hiro c pH ~ 9. Khi pH cao
hn, mng tr nn nhy vi Na
+
v kim loi kim
khc

in cc thy tinh
Tnh ht nc ca mng thy tinh
Mng thy tinh cn phi cha nc
nhy ca mng c th c phc hi
khi ngm in cc trong nc mt vi
gi
S ht nc ca mng c km theo s
trao i gia cc cation (ca mng) v
H
+
(hu nh ch cc cation +1 tham gia)
in cc thy tinh
Phn ng trao i:

H
+
dung dch
+ Na
+
- Glass Na
+
dung dch
+ H
+
- Glass

Dung dch
trong
H
+
chim v tr
cc l trng
[H
+
] = a
2

Lp gel
hirat
ha
~ 10
-4
mm
H
+
, Na
+

Lp thy
tinh
kh
0,1mm
Na
+

Lp gel
hirat
ha
~ 10
-4
mm
H
+
, Na
+

Dung dch
ngoi
H
+
chim v tr
cc l trng
[H
+
] = a
1

V
1
V
2

in cc thy tinh
L thuyt th ca in cc thy tinh
Th tip xc ca mng
E = V
1
V
2

Trong :

1
1 1
'
1
ln
a RT
V k
F a
= +
2
2 2
'
2
ln
a RT
V k
F a
= +
a
1
v a
2
hot ca H
+
trong 2 lp gel
in cc thy tinh
1
1 2
2
ln
a RT
E V V
F a
= =
a
2
l hng s, nn:
1
ln
RT
E const a
F
= +
Sai s ca in cc thy tinh
Th bt i: loi tr bng cch chun ha in cc
trc khi o (pH = 4, 7, 10)
Sai s kim sai s axit

0
0,5
-0,5
0
-2
2 4 6 8 9 10 12 14
pH

s
a
i

s
p
H

in cc thy tinh
2.4 K thut thc nghim
Chun b mu
Phn hy, ph mu
Bo qun mu
Chn cc iu kin thc nghim: nhit , pH, lc ion,
cc ion cn tr.
Xc nh bng phng php ng chun
Xc nh bng phng php thm chun
K thut o in th trc tip
So snh th ca in cc ch th nhng trong dung
dch phn tch vi th ca in cc nhng trong dung
dch chun
Cc yu t cn ch :
Th tip xc lng: hn ch chnh xc ca php
o
Do s phn b khng ng u ca cc cation v
anion, tc di chuyn khc nhau
PP loi tr: dng cht in gii: KCl, KNO
3
, NH
4
NO
3

Cc phng trnh biu din th

quansat sosanh chithi j
E E E E = +
Th tip xc lng
0
1
0, 059
lg
chithi chithi
E E a
n
= +
0
1
0, 059
lg
quansat sosanh chithi j
E E E a E
n
= +
0
1
( )
lg
0, 059/
quansat sosanh j chithi
E E E E
a pM
n
+
= =
0, 059 /
quansat
E K
pM
n
=
T pt trn s a ra cc pp phn tch khc nhau
Phng php ng chun
Phng php thm chun
Phng php ng chun

Xc nh hng s K:
o E
quansat
vi mt s dung dch chun bit pM
Gi thit K khng i theo thi gian

0, 059 /
quansat
E K
pM
n
=
0, 059 0, 059 /
quansat
n K
pM E
n
=
0, 059
0, 059 /
quansat
K
E pM
n n
= +
dc l thuyt
E
pM
K
Sai s ca pp ng chun gy ra do sai s ca K
Phng php thm chun
Th ca in cc c o trc v sau khi thm l E
1
v
E
2
. Gi thit qu trnh thm khng lm thay i lc ion v do
khng lm thay i h s hot f
Gi tr o th u E
1

Thm Vml dung dch chun, th s l E
2
:

1
log .
0, 059 /
x
E K
C f
n
=
2
log .
0, 059 /
x x C C
x C
C V C V E K
f
V V n
+
=
+
Chun in th
Nguyn tc: xc nh im
tng ng thng qua vic
o th nh in cc ch th
u im: c th xc nh
chnh xc im tng ng
ca cc dung dch (c mu
hay khng)

Chun in th
Chun axit baz
in cc ch th l in cc thy tinh
in cc so snh: calomel hoc Ag/AgCl
Php chun ny c bit thun li khi phn tch
a axit hoc baz (tch c im cui ca qt
chun )
C th chun trong dm khc nc
Chun oxy ha kh:
c ch th l in cc tr (Pt)

Chun in th
Chun to ta
c ch th l ISE vi ion cn xc nh
VD: chun Cl
-
bng Ag
+

Chun to phc
Chng 3: PHNG PHP CC PH XUNG
3.1 M u
3.2 Phng php c in v nhng hn ch
3.3 Cc phng php trit tiu dng t in
3.4 Phng php cc ph xung
3.5 Nhng hng pht trin mi ca phng php DPP

History
Jaroslav Heyrovsk l ngi pht minh ra
pp cc ph v nhng nghin cu v in
ha, vi nhng thnh cng ny ng
c nhn gii Nobel. Tt c nhng pp
voltampe hin i ang c s dng c
ngun gc t pp cc ph
On February 10, 1922, the "polarograph" was born as Heyrovsk recorded the current-voltage curve for a
solution of 1 M NaOH. Heyrovsk correctly interpreted the current increase between -1.9 and -2.0 V as
being due to deposition of Na
+
ions, forming an amalgam.
3.1 M u
Gii thiu phng php cc ph dng c in (DC
Polarography):
o dng in nh mt hm ca th, I = f(E), biu din
s ph thuc ny trn th: ng cc ph
Cc ph :
a
b
Phng php cc ph

Cc ph c trng bng dng gii hn
Th bn sng c trng cho cht in hot
Phng php cc ph
Nu quan st dng mt th c nh th dng s gim
theo thi gian
3

t
1
t
2

t
3

in cc git thy ngn
Phn ln cc php o cc
ph c thc hin vi c
Hg
Hg c cho vo mt mao
qun, vn tc nh git ph
thuc vo chiu cao, kch
thc ca ct
Mi ln git ri xung h li
tr v trng thi ban u
in cc git thy ngn
in cc git thy ngn
u im:
C vi giy li c mt in cc mi khi phc cc
iu kin ban u
Ngn khng cho tp cht bm trn b mt in cc
Cc sn phm kim loi hu ht tan c trong Hg
Nhc im:
Hg d b oxy ha nn khng quan st c sng
cc ph dng hn so vi qu trnh oxy ha Hg (~
0V)
DME rt kh thit k
Vic nh lin tc Hg tn km
Hg rt c
PP phn tch nh lng da theo phng trnh ilkovic:

(i
d
)
max
= 706nD
1/2
m
2/3
t
1/6
C
(i
d
)
avg
= 607nD
1/2
m
2/3
t
1/6
C
i max
i avg
Cc yu t nh hng n dng khuch tn
Theo pt trn chng ta c th xc nh nng
C nu nh o c gi tr I
d
Thc t khng th xc nh c nng <
10
-6
M
Nguyn nhn: dng t in c hnh thnh
do lp kp
I
t in
~ E
in cc

Cc cc i v hin tng
rng ca
1: do chuyn ng ca b
mt git Hg khi ln
2: do Hg tch khi mao
qun ri xung
Hn ch: thm cht hot
ng b mt
1
2
Hin tng rng ca
Lin quan n vic to git Hg, xc nh chu k git
ri
i
kt

E
nh hng ca oxy ha tan
O
2
+ 4 H
+
+ 4 e

2 H
2
O E ~ - 0,9 V
O
2
+ 2 H
+
+ 2 e

H
2
O
2
E ~ -0,1 V
Sc N
2
hoc Ar t 5 20 pht
Cc con ng tng nhy ca phng php
Lm giu cht phn tch trn b mt in cc bng
phn ng kh hoc oxy ha, sau ha tan sn
phm kt ta v ghi tn hiu ha tan (phng php
Von ampe ha tan)
Lm tng nng cht in hot trong lp phn
ng bng cc phn ng xc tc (phng php cc
ph dng xc tc
Tn dng nhng thnh tu ca k thut in t
loi tr dng t in
3.3 Cc con ng trit tiu dng t in
B tr tuyn tnh dng t in
Chn thi gian ghi:
I
F
~ t
1/6
; I
t
~ t
-1/3

Cui mi chu k: I
F
max, I
t
min
Ghi dng in phn trong thi gian ngn ngay
trc khi git ri
Phng php ny c th t nhy 10
-6
M
chn lc khng thay i
Phng php cc ph dng xoay chiu chnh lu pha
(pp xoay chiu chn pha)
t thm vo in p xoay chiu
Khi dng t in lch vi dng Faraday 90
0

Chn thi gian, chn pha ch ghi c dng
Faraday
Phng php ny chnh xc vi qu trnh thun
nghch ( nhy ~ 10
-7
M)
Phng php cc ph sng vung:
Thm mt in p dng xoay chiu sng vung gc
3.3 Cc con ng trit tiu dng t in
3.4 Phng php cc ph xung
Phng php cc ph xung bin i u (Normal
Pulse Polarography)

E
i

Normal Pulse Polarography
in cc git thy ngn c phn cc bng mt
in p mt chiu chn trc v gi khng i trong
qu trnh o
in cc c b xung bng mt xung vung gc
trong khong thi gian ngn trc khi git ri, sau
xung b ngt
Bin xung tng dn
Ghi cng dng: 2 cch
17s trc khi ngt xung
Ghi 2 ln: 17s trc khi t xung, 17s trc khi
ngt xung
Phng php cc ph xung vi phn (DPP)
drop time
voltage step
pulse
amplitude
time
U
U
I
in p c phn cc bng mt in p mt chiu
bin thin tuyn tnh
in cc c p thm mt xung vung gc
Chn thi gian ghi

So snh
So snh
(a) Differential pulse polarogram: 0.36 ppm tetracycline- HCI in 0.1 acetate buffer, pH 4, PAR Model
174 polarographic analyzer, dropping mercury electrode, 50-mV pulse amplitude, 1-s drop.
(b) DC polarogram: 180 ppm tetracycline HCI in 0.1 M acetate buffer, pH 4, similar conditions.
Differential pulse polarogram
The example above shows the simultaneous determination of Zn ,
Cd, Pb and Cu using standard addition
So snh
nh hng ca in tr h o
loi tr nh hng ca dn in thng s
dng h o 3 in cc
Khng dng nn in li c nng qu cao
nhy v chn lc ca cc ph xung
nhy c n.10
-8
M
phn gii cao, c th xc nh c nhiu cht
trong dd m khng cn tch
C th phn tch cc cht hu c: vitamin, cc thuc
khng sinh, cc cht c
C th kt hp s dd DPP vi Von-ampe ha tan cho
nhy cao
Chng 4: Cc phng php
phn tch in ha ha tan
4.1 M u
4.2 Nguyn tc ca phn tch in ha ha tan
4.3 Phng php Von-ampe ha tan
4.1 M u
Cc pp DPP, SWP loi tr c phn no dng t
in, tuy nhin nhy mi ch t ti 10
-7
M
in phn l phng php lm giu, c th tp trung
mt lng ln cht in hot trn b mt in cc
Kt hp s in phn v cc phng php o hin
i l nguyn tc ca pp in ha ha tan

4.2 Nguyn tc ca pp in ha ha tan
Qui trnh: gm 2 giai on:
in phn vi in cc git thy ngn
Ha tan kt ta v ghi ng ha tan bng mt
trong cc phng php: von-ampe, in th - thi
gian, dng thi gian

a
E
p

I
c
kC
Pb Pb
2+
Pb
2+

Hg
Hg
2+

Pb
2+

Pb(Hg)
I
c

I
a

E: (+ )(-)
b
4.2.1 Cc lm vic
Trong bnh in phn:
Cc lm vic: xy ra phn ng
Cc so snh: calomen hoc bc clorua, cc c th
khng i trong qu trnh o
Cc ph tr: Pt
Cc lm vic:
Kh nng xy ra phn ng oxy ha kh ca cht
in hot
Khong th ca in cc
Khong th tn ti ca mt s loi in cc
4.2.1 Cc lm vic
Cc git thy ngn :
C kch thc khng i, lp li cao (kh nng
lm mi)
Nu in cc t cht lng tt th vic phn tch
thun li do: khong th cho php rt rng, xc nh
c mt s ln kim loi
Mt s loi in cc ch to t Hg:
in cc git ri DME
in cc git treo HMDE
in cc mng Hg - MFE
4.2.1 Cc lm vic
4.2.1 Cc lm vic
in cc mng thy ngn:
Thm vo dung dch phn tch mt lng nh Hg
2+
,
khi in phn Hg
2+
Hg to thnh mng mng. Kim
loi khi in phn s to thnh hn hng vi lp thy
ngn ny
in cc rn:
in cc rn a quay
in cc rn n nh

4.2.1 Cc lm vic
in cc rn a quay:
The Levich equation
i
L
= (0.620) n F A D
2/3
w
1/2
v
1/6
C

4.2.2 Cc loi phn ng dng kt ta lm giu
Phn ng kh kim loi sau to hn hng vi Hg:

Qu trnh ny qu trnh catot, cn qu trnh ngc li - qu trnh
ha tan l qu trnh anot
Kh cc kim loi trn b mt in cc rn tr:

Phn ng lm giu di dng mt hp cht kh tan:
Xc nh anion A
n-
:

) (Hg Me ne Me
p
E
n
+
+
Me ne Me
p
E
n
+
+
+
+
+
+
+
A M nM A
ne nM nM
n
puhh n
E
c
p
4.2.2 Cc loi phn ng dng kt ta lm giu
Xc nh cation M
n+
:

ng dng hin tng hp ph in ha: thm vo dd mt cht
c kh nng b hp ph ln b mt in cc, sau to phc vi
cht cn xc nh:

Qt ha tan:

+
+
+ +
+ + +
+ + + +
+
H m n MeR RH m n Me
me Me Me
puhh m n
m n
E
n p
) ( ) (
) (
) (
hp
n puhh n
hp
hp
hp
RMe Me R
R R
) (
+ +
+

hp
puhh
hp
n
R Me ne RMe + +
+
) (
4.2.3 Cc pp theo di qu trnh ha tan
PP von-ampe: ng biu din xut hin pic ha tan
ca cht cn xc nh. Chiu cao ca pic trong cc
iu kin thch hp t l thun vi nng cht
PP in th - thi gian, dng - thi gian(T87-Gt)

4.3 Phng php von-ampe ha tan
4.3.1 Nguyn tc:
Thit b:
My cc ph t ghi
Bnh in phn gm 3 in cc
Bnh kh tr
Qt in phn:
Th c gi khng i
Dung dch c khuy trong sut qu trnh in
phn
Thi gian in phn ty thuc vo nng cht
phn tch v kch thc git thy ngn
4.3.1 Nguyn tc:
Sau khi in phn thng ngng khuy dung dch,
c mt khong thi gian ngh lng kim loi
phn b u trn in cc
Qt ha tan:
Phn cc ngc vi chiu in phn
Trn ng von-ampe ha tan xut hin pic ca
cht cn xc nh
E ti nh pic (E
c
) c trng cho cht cn xc nh
Chiu cao pic t l thun vi nng cht cn phn
tch
ng von-ampe ha tan ca mt s kim loi
PP Voltampe ha tan anot (ASV)
Differential-pulse anodic stripping voltammogram of 25 ppm zinc, cadmium,
lead, and copper.
PP Voltampe ha tan catot (CSV)
nh hng ca thi
gian in phn ti
chiu cao peak
V d
Voltampe ha tan hp ph
Mt s cht hp ph
PP Voltampe vng
Nghin cu c ch ca phn ng in ha (tnh thun
nghch, tnh cht in ha)

a ra nhng thng tin mang tnh cht nh tnh v
cht nghin cu

PP ny c tin hnh u tin trong cc php
nghin cu in ha

PP Voltampe vng
PP Voltampe vng
PP Voltampe vng
4.4 nhy, tnh chn lc v mt s iu cn ch
v k thut phn tch in ha ha tan
nhy, chnh xc, lp li cao
K thut phn tch n gin
Yu cu: dng c, ha cht s dng phi c tinh khit
cao, mi trng lm vic sch s
Tnh chn lc ca phng php:
Tnh chn lc tt, c th xc nh ng thi 4 5
nguyn t trong 1 dung dch
Tuy nhin vi cc kim loi c tnh in ha gn ging
nhau (Cu
2+
, Ag
+
,Sb
3+
, Bi
3+
) cn kt hp vi pp ha
hc (dng cht che, cht to phc chn lc) hn ch
s nh hng
Nhng iu cn ch (GT):
My mc, thit b
in cc
Ha cht
4.5 Cc hng ch yu ca PTH ha tan
Phn tch mi trng
Phn tch lm sng
Phn tch thc phm
Detection of cadmium (50 g/L) in NH
4
Ac (0.05 M) by differential pulse anodic stripping
voltammetry (DPASV). Scan from -775 mV to -550 mV. Pre-concentration step of 30 s at -
1100 mV. Scan rate was 15 mV/s and height of modulation pulse 65 mV. Low frequency
sound 40 Hz.
Differential pulse anodic stripping voltammetry (DPASV) scan from -1300 mV to -350
mV. Pre-concentration step of 120 s at - 1300 mV. Scan rate was 15 mV/s and height of
modulation pulse 50 mV. Concentration of zinc, cadmium and lead was 50 ppb.

Simultaneous detection of nickel, cobalt, and zinc in seawater
Differential pulse cathodic stripping voltammetry (DPCSV) scan from -400 mV to -1150mV in
seawater. HEPES buffer (0.01M, pH=7.3), oxine (0.00002M), and dimethyl glyoxime (0.0003M) added
directly into seawater sample. Pre-concentration step 120 s at -800 mV. Scan rate was 15 mV/s and
height of modulation pulse -50 mV.
Detection of zinc on silver with 4 % bismuth alloy electrode. Concentrations were 267, 534 and 800
mg l
-1
. All scan performed in DPASV mode in NH
4
Ac (0.05 M). Scan rate of 15 mV / s, pulse height
70 mV and a deposition time of two minutes. Current values corrected for offset.


Electrode system:
Working electrode DAM
Counter electrode Platinum
Reference electrode Ag/AgCl/KCl (sat')
Electrolyte NH4Ac (0.05 M)
Cadmium

Electrode system:
Elektrolyte NH4Ac (0.05 M)
Zinc
Electrode system:
Working electrode Gold/Bismuth
Counter electrode Glassy carbon
Reference electrode Ag/AgCl/KCl (3M)
Electrolyte 10mM HNO
3
+ 10mM HCl
Mercury
Copper
Electrode system
Working electrode Silver
Counter electrode Silver
Electrolyte NH4Ac
Thallium
Electrode system:
Electrolyte NH4Ac (0.05M)
Electrode system:
Elektrolyte HCl (0.01 M)
Lead
Lead in nickel plating solution
Electrode system:
Working electrode Silver
Counter electrode: Silver
Lead in process water.
80
130
180
230
280
330
380
-600 -500 -400 -300 -200 -100 0
E(mV)
I (
n
A
)
Schrder/Mikkelsen 2002
Zinc in nickel plating solution
Electrode system:
Reference electrode Ag/AgCl/KCl
70
90
110
130
150
170
190
210
-600 -500 -400 -300 -200 -100 0 100 200 300
Schrder/Mikkelsen 2002
Nickel and cobalt in seawater
Electrode system:
Working electrode Silver-Bismuth
Reference electrode Ag/AgCl/KCl
Electrolyte Ammonium buffer (pH9,6),
nioxim 0.01 nM)
Detection of Fe(II) with DPASV in tri-sodium citrat-5,5-hydrat (0.02 M) solution.
Freshly made Fe(II) solution added in sequences to solutions of 1,67 ppb, 3,34 ppb
and 5 ppb, 15 ppb, 25 ppb, 50 ppb. Scan parameters as follows: pre-deposition at -
1500 mV in 180 s, equilibrate time 10 s, scan rate 15 mV/s, modulation pulse 50 mV.
Sample (60 mL) purged with Nitrogen for 4 min.
Detection of iron in sea water (from Trondheim near Trondheim center). Sea water
sample (100mL) was added tri-sodium citrat-5,5-hydrat (to a conc. of 0.02 M) and then
scanned with DPASV. Scan parameters as follows: pre-deposition at - 1500 mV in 180
s, equilibrate time 10 s, scan rate 15 mV/s, modulation pulse 50 mV. Sample purged
with Nitrogen for 4 min. Concentration of Fe detected by standard addition method;
274 ppt.
Iron in sea water
Detection of zinc on silver with 4 % mercury alloy electrode. Concentration of zinc
was 100, 200, 300 and 400 g l
-1
. All scan performed in DPASV mode in NH
4
Ac (0.05
M). Scan rate of 15 mV / s, pulse height 70 mV and a deposition time of two minutes.
23
28
33
38
43
48
-1 200 -1 000 -800 -600 -400 -200
Chun in th

Chng V: K thut in ha trong HPLC v FIA
5.1 Nguyn tc
5.2 Cc loi detector in ha dng cho HPLC v FIA
5.3 ng dng ca detector in ha trong HPLC v FIA
5.1 Nguyn tc
i lng o c A (theo mt tnh cht in ha
ca cht phn tch v nng C ca cht phn tch t
l vi nhau:
A = kC
A c th l cng dng in, in th, in tr,
dn, in lng
K l hng s thc nghim
iu kin ca detector in ha:
Tnh chn lc i vi cht cn phn tch
nhy cao vi cht cn phn tch nhng khng
nhy vi cc cht khc
5.1 Nguyn tc
Bn v n nh theo thi gian, lp li ca php
o tt
Vng tuyn tnh ca php o khng qu hp
t b tc ng bi mi trng xung quanh
c trng ca cc detector:
nhiu t nhin ca detector: phi nh, t dao
ng
Gii hn pht hin: cng nh cng tt
rng pc: cng hp cng tt
Tn hiu o: lp li cao
5.1 Nguyn tc
Cu to ca cc detector: 2 b phn chnh
Flowcell (bung o) v h in cc
H in t (h o) nhn, khuch i, ghi kt qu
5.2 Cc loi detector in ha dng cho HPLC v FIA
5.2.1 Detector o dng
5.2.2. Detector o th vi in cc chn lc ion
5.2.3. Detector o dn
5.2.4. Detector o in dung
5.2.5. Detector in lng

5.3. ng dng EC detector trong HPLC v FIA

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Trn Mai Lin Phn tch in ha 1

Trng i hc Cng nghip TP HCM

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