PPVon Ampe

S LC VE PHNG PHAP VON - AMPE
- PHNG PHAP VON AMPE C PHAT TRIEN T PHNG

PHAP CC PHO (POLAROGRAPHY).

- PHNG PHAP CC PHO C TM RA VA PHAT TRIEN BI
NHA HOA HOC NGI TIEP JAROSLAV HEYROVSKY VAO NAM
1922.

- NH VIEC PHAT TRIEN PHNG PHAP PHAN TCH CC PHO
VA VON AMPE ONG A C TRAO GIAI THNG NOBEL
HOA HOC VAO NAM 1959.
Jaroslav Heyrovsky as a
student at the University
College, London (1911).
Masuzo Shikata and Jaroslav Heyrovsky on the occasion of Faraday Discussion in London
(December, 1923).
Jaroslav Heyrovsky having received the Nobel Prize from the Swedish king.
- PHNG PHAP VON AMPE LA PHNG PHAP TRONG O MOI QUAN
HE GIA DONG VA THE CUA MOT HE PHAN NG IEN HOA
TAI MOT HE THONG IEN CC C THEO DOI VA GHI LAI .

- THONG THNG NGI TA S DUNG HE THONG HAI IEN
CC(HOAC 3 IEN CC) BAO GOM 1 IEN CC SO SANH (HAY QUI
CHIEU REFERENCE ELECTRODE); 1 IEN CC LAM VIEC (HAY
CH TH :WORKING HAY INDICATOR ELECTRODE) VA 1 IEN CC PHU
TR ( AUXILARY HAY COUNTER ELECTRODE NEU HE 3 IEN CC) .
- HE IEN CC C NHUNG VAO DUNG DCH CAN O.

- T MOT GIA TR THE BAN AU AP VAO HE IEN CC, THE
SE C THAY OI THEO NHNG QUA TRNH A NH SAN .
QUA TRNH NAY GOI LA QUET THE.

- CUNG LUC VI VIEC QUET THE, CNG O DONG IEN SINH
RA DO THE AP VAO CUNG C GHI LAI .
- DO AY LA PHNG PHAP GHI DONG BIEN THIEN THEO THE
AP VAO HE IEN CC NEN PHNG PHAP C GOI LA
PHNG PHAP VON AMPE HAY PHNG PHAP NG DONG -
THE.

- NG CONG BIEN THIEN CUA CNG O DONG THEO THE
AP VAO C GOI LA NG CONG VON AMPE .

- TRONG PHNG PHAP VON AMPE NGI TA CHIA THANH NHIEU
PHNG PHAP KHAC NHAU .
- MOT TRONG NHNG PHNG PHAP QUAN TRONG NHAT LA
PHNG PHAP CC PHO. PHNG PHAP CC PHO LA PHNG
PHAP VON AMPE KHI S DUNG IEN CC GIOT THUY NGAN
RI (DME : DROPPING MERCURY ELECTRODE)

- KHI S DUNG CAC IEN CC KHAC (IEN CC RAN, IEN
CC GIOT THUY NGAN TREO ) NGI TA GOI CHUNG LA
PHNG PHAP VON - AMPE.
- CAC PHNG PHAP QUAN TRONG KHAC TRONG HE THONG
CAC PHNG PHAP VON AMPE NH :

+ PHNG PHAP VON AMPE TUAN HOAN (CYCLIC VOLTAMMETRY
METHOD)

+ PHNG PHAP VON AMPE HOA TAN (STRIPPING VOLTAMMETRY
METHOD), NHOM NAY BAO GOM NHIEU KY THUAT KHAC
NHAU NH TCH GOP - HOA TAN; HAP PHU - HOA TAN .

+ CHUAN O AMPE
CAC LOAI IEN CC S DUNG TRONG PHNG
PHAP VON - AMPE
IEN CC SO SANH (REFERENCE ELECTRODE):

- LA IEN CC CO THE KHONG OI TRONG NHNG IEU
KIEN XAC NH.

- C S DUNG E XAC NH THE THC CUA IEN
CC LAM VIEC. THE AP LEN IEN CC LAM VIEC
LUON LA HIEU THE GIA IEN CC LAM VIEC VA
IEN CC SO SANH.
PHAP VON - AMPE
- IEN CC LOAI I VA LOAI II THNG C S DUNG LAM
IEN CC SO SANH, TRONG O IEN CC LOAI II THNG
C S DUNG NHAT.

- CAC IEN CC LOAI II : M/MX/X
THNG C S DUNG
DO CHUNG CO THE KHONG OI KHI DUY TR NONG O
ANION X LA HANG SO.

- MOT SO IEN CC LOAI II THNG S DUNG LA CALOMEL
, Ag/AgCl/Cl. TRONG NHNG TRNG HP DUNG PHAN TCH
HALOGENUA NGI TA S DUNG IEN CC Hg/Hg
2
SO
4
/SO
4
2-
.
PHAP VON - AMPE
- DO THE CUA CAC IEN CC NAY PHU THUOC VAO NONG
O ANION TRONG DUNG DCH NEN TUY THEO NONG O ANION
MA THE CUA IEN CC SE KHAC NHAU. KHI LAM THC
NGHIEM LUON CAN GHI LAI NONG O CUA ANION TRONG
IEN CC SO SANH

- MOT SO IEN CC LOAI I THNG C S DUNG LAM
IEN CC SO SANH NH IEN CC AY Hg, IEN CC Ag.

PHAP VON - AMPE
- CAC IEN CC NAY PHAI CO DIEN TCH BE MAT LN HN
NHIEU DIEN TCH IEN CC LAM VIEC. KHI NAY QUA TRNH
PHAN CC TREN IEN CC SO SANH SE CHAM HN IEN
CC LAM VIEC RAT NHIEU NEN THE THAY OI KHONG
ANG KE.

- PHNG PHAP VON AMPE CHO PHEP THAY OI THE TRONG
KHOANG VAI CHUC MV NEN IEU NAY KHONG ANH
HNG NHIEU EN KET QUA THU C.

PHAP VON - AMPE
- CAC IEN CC LOAI NAY THNG CO IEN TR THAP
HN IEN CC LOAI II NHIEU NEN C DUNG NHIEU VI
CAC DUNG DCH CO IEN TR LN.
PHAP VON - AMPE
THE MOT SO IEN CC SO SANH TAI 25
O
C TRONG MOI TRNG
NC
IEN CC THE (VOLT)
CALOMEL / 0.1M KCl 0.3356
CALOMEL / BAO HOA KCl 0.24453
Ag/AgCl / 0.1M KCl 0.288
Ag/AgCl / 1.0M KCl 0.22234
Ag/AgCl / BAO HOA KCl 0.198
PHAP VON - AMPE
PHAP VON - AMPE
IEN CC LAM VIEC (IEN CC CH TH WORKING
ELECTRODE)

- IEN CC AU TIEN C S DUNG LA IEN CC GIOT Hg
RI, SAU NAY NHIEU LOAI IEN CC KHAC A C S
DUNG NH BACH KIM, VANG, BAC, CARBON.

- DO Hg LA CHAT LONG NEN NGI TA CHIA LAM 3 NHOM :
IEN CC GIOT Hg, IEN CC RAN VA IEN CC A QUAY.
NGOAI RA HIEN NAY NGI TA CON S DUNG IEN CC RAN
TRANG THUY NGAN.
PHAP VON - AMPE
- CC GIOT Hg C CHIA LAM 3 LOAI KHAC NHAU : GIOT RI,
GIOT TNH VA GIOT TREO.

+ IEN CC GIOT RI : GIOT Hg C TAO THANH KHI CHAY
QUA MOT ONG MAO QUAN DI TAC DUNG CUA TRONG
LC HOAC DI AP LC CUA KH NEN AP SUAT
KHONG OI.

+ LNG Hg TRONG BAU Hg LUON PHAI RAT LN SO VI
GIOT Hg TAO THANH E LNG Hg MAT I KHONG ANH
HNG EN LNG CAC GIOT MI SE TAO THANH.
PHAP VON - AMPE
+ DO GIOT Hg TAO THANH DI TAC DUNG CUA TRONG
TRNG NEN CAC GIOT TAO THANH CO KCH THC,
TRONG LNG VA DIEN TCH BE MAT HOAN TOAN NH
NHAU.

+ IEN CC GIOT TREO (HMDE HANGING MERCURY DROP
ELECTRODE) : GIOT Hg SAU KHI C TAO THANH SE TON TAI
TRONG SUOT QUA TRNH AP THE VA GHI DONG. SAU MOI
LAN O, MOT GIOT Hg MI SE C TAO THANH CHO
LAN O KE TIEP.
PHAP VON - AMPE
CAC LOAI IEN CC
GIOT Hg
a. GIOT Hg TREO
b. GIOT Hg RI
c. GIOT Hg TNH
PHAP VON - AMPE

+ IEN CC NAY THCH HP CHO PHAN TCH CAC CHAT
NONG O NHO CAN LAM GIAU BANG CACH TCH GOP
TREN IEN CC TRONG MOT THI GIAN NHAT NH .

+ CO HAI LOAI IEN CC GIOT Hg TREO : THAO TAC BANG
TAY HOAC T ONG. LOAI THAO TAC BANG TAY GIOT Hg
C TAO THANH CO O LAP LAI KHOANG 5 10% TUY
THEO MAT NGI S DUNG. LOAI T ONG CO O LAP
LAI KHOANG 2%.
PHAP VON - AMPE
+ IEN CC GIOT Hg TNH (SMDE STATIC MERCURY DROP
ELECTRODE) : GIOT Hg C TAO THANH VA S DUNG E
GHI 1 IEM TN HIEU, SAU O SE C GO RI VA THAY
THE BANG GIOT KHAC. SE CO MOT SO LNG LN GIOT
TAO THANH TRONG MOT LAN QUET THE NH TRONG
TRNG HP GIOT Hg RI.

+ S KHAC NHAU GIA IEN CC GIOT TNH VA GIOT RI :
TRONG KHI O DIEN TCH CUA GIOT RI THAY OI LIEN TUC
NHNG VI GIOT TNH DIEN TCH BE MAT LA KHONG THAY
OI .
PHAP VON - AMPE
+ IEN CC GIOT Hg TNH CHO O NHAY CAO HN IEN
CC GIOT Hg RI.

- IEN CC RAN THNG C LAM T VAT LIEU LA
CAC KIM LOAI TR NH BACH KIM, IRIDIUM, VANG HOAC
CARBON. NGOAI RA MOT SO KIM LOAI MA DU KEM TR VE
MAT IEN HOA HOAC HOA HOC NH BAC CUNG C
S DUNG TRONG MOT SO PHEP PHAN TCH.

PHAP VON - AMPE
- VI VAT LIEU LA CARBON CO NHIEU LOAI KHAC NHAU
NH GRAPHIT, GLASSY CARBON, CARBON NHAO (PASTE CARBON).
MOI LOAI SE C S DUNG TRONG NHNG PHEP PHAN
TCH KHAC NHAU.

- CAC IEN CC NAY THNG CO HNH A NEN CON
GOI LA IEN CC A. CAC IEN CC NAY THNG GAP
KHO KHAN NEU MUON TIEN HANH TCH GOP LAM GIAU
DO KHI NAY PHAI TIEN HANH KHUAY TRON LIEN TUC
TRONG QUA TRNH LAM GIAU.
PHAP VON - AMPE
- TRONG PHNG PHAP VON AMPE HOA TAN THNG VIEC
LAM GIAU CAC CHAT PHAN TCH TRONG IEN CC C
TIEN HANH TRONG DUNG DCH C KHUAY TRON EU
TOC O KHONG OI.

- VI IEN CC RAN VIEC KHUAY TRON THNG THC
HIEN BANG MAY KHUAY T, TOC O KHONG ON NH
VA CHAM NEN GAP NHIEU KHO KHAN TRONG VIEC PHAN
TCH.
PHAP VON - AMPE
- E KHAC PHUC NHNG NHC IEM TREN NGI TA
CHE TAO IEN CC A QUAY.

- TRONG O VAT LIEU IEN CC (Pt, Au, Carbon) C GAN
VAO TRUC QUAY CO THE IEU KHIEN TOC O CHNH
XAC. LOAI IEN CC NAY GOI LA IEN CC A QUAY.

PHAP VON - AMPE
Cc in cc c b tr :
Gm cc in cc c nh km mt s
hp cht gip cho vic tch gp xy ra khng
cn p th.
Cc in cc ny thng c s dng trong
cc phng php Von-Ampe ha tan catod
xc nh kim loi.
Cc in cc loi ny thng l cc in cc
cacbon c b tr bng cch gn thm cc
nhm to phc hoc kt ta vi kim loi
PHAP VON - AMPE
IEN CC PHU TR (AUXILARY ELECTRODE HAY COUNTER
ELECTRODE)

- C S DUNG TRONG HE THONG 3 IEN CC.

- DUNG CUNG CAP DONG IEN T CHO QUA TRNH PHAN
NG TAI IEN CC LAM VIEC CUA HE 3 IEN CC.

PHAP VON - AMPE

- THNG LAM BANG CAC VAT LIEU TR NH BACH KIM,
GLASSY CARBON HAY VANG

- TRONG CAC HE IEN CC CU NGI TA KHONG S
DUNG IEN CC NAY. VI HE THONG VI IEN CC
NGI TA CUNG CO KHUYNH HNG BO IEN CC NAY.
S PHN CC iN CC
Khi c dng in i trong mch, theo nh lut ohm
ta c:
E
v
= i.R
E
v
l th p vo hai in cc, R l in tr ca
mch.
Mt khc khi p th vo hai in cc, cathod xy
ra qu trnh phn cc v sinh ra mt th in ng P
Nh vy th thc p vo h s l E
v
- P
S PHN CC iN CC
Hay
E
v
P = i.R
Trong cc trng hp khi in tr ca dung dch
nh ( dung dch rt m c) v in tr ca in cc so
snh cng nh gi tr iR thng khng ng k.
V d vi cng dng I khong 10uA v in tr
dung dch + mch khong 100 ohm, gi tr iR ch khong
1mV
S PHN CC IN CC
Tuy nhin trong nhiu trng hp in tr ca dung
dch hoc in cc so snh kh ln gi tr ny tr ln ng
k, c th ln ti vi trm mV
Khi ny s st th tr nn nghim trng v khng
th b qua c v ngi ta gi hin tng ny l hiu
ng iR
gii quyt vn ny ngi ta thng s dng
nng nn ln v thit k thm b b tr hiu ng iR
Tuy nhin vic s dng h 3 in cc l ti u nht
S PHN CC iN CC
Do nh hng ca hiu ng iR nn vic chn in
cc so snh cng rt quan trng.
Khi cn c th chnh xc ngi ta thng s dng
cc in cc so snh nh Ag/AgCl hc Calomel
Tuy nhin in tr ca cc in cc ny khng nh
lm, mt khc trong phn tch von-ampe chnh xc th
khng i hi qu cao nn ngi ta c th s dng in
cc y Hg c din tch ln hoc in cc Ag c din tch
ln lm in cc so snh.
S PHN CC iN CC
S d chnh xc th khng i hi qu cao do ty
theo dung dch nn m th bn sng ca mi phn ng c
th khc nhau.
Ci chng ta cn l th bn sng phi n nh trong
khong cho php v hn ch ti a s lch th p vo h
in cc cc nng khc nhau.
Cc in cc Hg hay Ag l anod v s tham gia
phn ng (v d nn Cl
-
)
2Hg 2e Hg
2
Cl
2

S PHN CC iN CC
Do nng Cl
-
trong dung dch ln nn coi nh
khng i, khi ny anod tr thnh in cc Calomel nhng
c in tr thp hn in cc Calomel thng thng rt
nhiu.
Tng t vi in cc Ag.
Cc in cc so snh loi ny thng c s
dng vi h 2 in cc v ng dng ch yu trong phn
tch.
Vi cc nghin cu l thuyt cn chnh xc th
cao ngi ta vn s dng in cc so snh thng thng.
CNG DNG TI iN CC
GiT Hg RI DME
in cc git Hg ri l in cc c s dng
nhiu nht trong phng php Von-ampe. Din tch ca
n thay i trong sut qu trnh sng ca git.
Din tch ca git Hg s t i 0 v tng n cc i
thi im git ri.
Nu gi :
Khi lng Hg chy trong 1 giy (g/giy) l m;
t l thi gian to git (giy) (tc thi gian sng ca
1 git)
CNG DNG TI iN CC
GiT Hg RI DME
T trng ca Hg l d
Hg

Ta s c khi lng ca 1 git s l :
Bn knh r
0
v din tch A ca git s c tnh nh
sau:
CNG DNG TI iN CC
GiT Hg RI DME
Cng dng tc thi ghi c chnh l cng
dng tc thi ca ion in hot n b mc in cc trong
thi gian. Tuy nhin trn thc t khng th ghi c cng
dng tc thi nn ngi ta tnh dng trung bnh ti thi
im o.
Gi tr dng trung bnh ti din tch cc i (cui chu
k sng ca git) c In-co-vit (Ilkovic) tnh nh sau:
CNG DNG TI iN CC
GiT Hg RI DME
Hay ti thi im dng cc i ta c:
Tuy nhin cng cn nh l trn thc t do din tch
ca git Hg thay i lin tc nn gi tr cc i ti mi din
tch khc nhau cng s khc nhau. Chnh v vy Incovit
cng tnh ton gi tr cng dng khuch tn cc i
trung bnh cho c i sng git.
CNG DNG TI iN CC
GiT Hg RI DME
V phng trnh l :
CNG DNG TI iN CC
GiT Hg RI DME
DNG D
Bn cnh dng khuch tn, mt s dng
khc chng ta lun thu c khi ghi sng cc
ph ngay c khi khng c cht phn tch. Dng
ny c gi l dng d.
DNG D
DNG D
Hai thnh phn chnh ca dng d l dng
faraday v dng non-faraday.
Dng faraday sinh ra do tp cht nhim bn
trong dung dch, trn b mt in cc (nh cc kim
loi, cht hu c, oxi ha tan ). Dng ny c th
gim thiu hoc loi tr nu dung dch v in cc rt
sch v tinh khit.
Dng non-faraday thng gi l dng t in,
y l dng quan trng trong phng php von-ampe
DNG T IN
Dng t in xut hin ngay c trong nhng
dung dch c tinh khit rt cao.
Khi nng cht phn tch cao, cng
dng t in khng nh hng ng k, tuy nhin
khi nng cht phn tch nh n nh hng
nghim trng n phng php cc ph c in.
Ngi ta tnh c rng khi nng cht
phn tch khong 10
-5
M cng dng t s bng
hoc ln hn cng dng khuch tn.
DNG T IN
iu ny dn n phng php phn tch
cc ph c in vic nh lng b gii hn nng
khong 10
-5
n 10
-6
M
Vic ny lm gii hn ng dng ca phng
php cc ph trong mt s lnh vc phn tch i
hi nhy cao.
Ngi ta phi nghin cu v pht trin rt
nhiu k thut ci thin nhy thng qua vic
gim thiu nh hng ca dng t in
DNG T IN
Khi p th vo in cc lm vic, ty theo th
m hay dng m n s to ra mt lp in tch
tri du trong dung dch ngay st b mt in cc
DNG T IN
Nu nh ch to thnh bn t in vi 1 gi
tr nht nh th s khng to thnh dng, do dng
in 1 chiu khng i qua c bn t. Tuy nhin
do :
- in cc git Hg ri c b mt thay i lin
tc dn n ln lp t in b bin i lin tc
- Qu trnh qut th lm in tch trn b mt
in cc thay i lin tc.
DNG T IN
Cc nguyn nhn trn dn n vic to
thnh mt sc in ng lm pht sinh dng t
in i
c
.
DNG T IN
Ngi ta tnh i
c
theo cc cng thc :
U V KHUYT IM CA IN
CC GIT Hg
u im :
- Qu th hydro ln : trong dung dch axit (HCl
1M) qu th hydro khong 1,1V. iu ny cho php
khong th s dng ca in cc git Hg trong mi
trng axit n -1,1V vs. SHE
- Tng ng trong mi trng trung tnh th
ph nn s khong -1,5/-1,6V vs. SHE
- Trong mi trng kim th ph nn khong
-1,8/-1,9V vs. SHE
U V KHUYT IM CA IN
CC GIT Hg
- Do git lun c to mi nn b mt git
lun i mi, khng nhim bn. Lp dung dch tip
xc vi git cng lun c i mi.
- Din tch git ti cng thi im rt ging
nhau nn lp li ca cng dng cao.
- Vi 1 git : rt nhiu sn phm in ha tan
trong git Hg to hn hng nn b mt git Hg vn
sch trong qu trnh phn tch
U V KHUYT IM CA IN
CC GIT Hg
Nhc im :
- Ch c th lm vic c vi cc kim loi c
th m hn +0,43V do khi dng hn th ny Hg
s b ha tan.
- Hg rt c hi nn iu kin phng th
nghim i hi rt nghim ngt. Hin nay ti chu
u ch nhng phng th nghim c bit mi c
php s dng in cc ny.
U V KHUYT IM CA IN
CC RN
Cc in cc rn thng l cc in cc lm t cc
kim loi tr nh Pt, Au, Ir hay cc loi cacbon nh
Glassy cacbon (cacbon thy tinh), cacbon graphit,
cacbon nho (cacbon paste)
u im :
- C th lm vic cc th dng hn in
cc git Hg
- Khng c hi
U V KHUYT IM CA IN
CC RN
Nhc im :
- Qu th hydro nh nn hn ch v pha m
- in cc b bn nu sn phm ca qu trnh
in ha bm ln trn b mt in cc. Khi ny tnh
cht ca b mt in cc b thay i mt phn.
- Din tch in cc thng khng ng nht
sau mi ln x l sau khi o nn lp li km hn
git Hg
Cu to ca in cc rn dng a
U V KHUYT IM CA IN
CC RN
in cc rn c mt s dng cu to khc
nhau nhng dng a l ph bin nht.
Trong trng hp s dng in cc tnh do
ch c s khuch tn y nn cng dng tng
dn n dng khuch tn gii hn, tuy nhin dng
ny s gim dn do s ngho i nhanh chng ca
cht in hot cc cnh ca in cc.
V vy ng cong von-ampe trong trng
hp ny c dng cc i dn n kh xc nh
dng khuch tn gii hn.
U V KHUYT IM CA IN
CC RN
trnh nh hng ny ngi ta s dng
in cc dng a quay, khi ny s c s i lu
dn n nng cht in hot trong dung dch u
nhau hn.
Tuy nhin khi ny kh khn khc li xut hin,
l qu trnh khuch tn ca cht trong dung dch
tnh khc vi qu trnh khuch tn trong cht lng
chuyn ng.
Trong thc t in cc rn thng s dng
trong phng php von-ampe ha tan.
CC PHNG PHP VON-AMPE
KHC
Do gii hn ca dng t in nn phng
php cc ph c in b gii hn nng 10
-5
M.
Nng ny kh ln nn gii hn ng dng
ca phng php cc ph c in trong cc lnh
vc phn tch i hi nhy cao.
nng cao nhy ngi ta s dng k
thut mi ci tin
PHNG PHP XUNG THNG NPP
Trong phng php NPP, in cc lm vic c
phn cc bng in p mt chiu chn trc v gi
khng i trong sut qu trnh o.
in p ny gi l in p khi im, tng ng vi
chn sng trong phng php c in.
Trong mi chu k git, in cc c b sung bng
mt xung vung gc c khong tn ti rt ngn (40
n 100 ms) c a vo ngay trc khi git ri

Sau thi gian , xung b ngt v th in cc
tr v in p khi im.
Bin xung tng dn u theo thi gian ging
nh tc qut th tuyn tnh trong cc ph c
in.
Cng dng c ghi theo mt trong hai
cch sau:
Cch 1:
Xung c p vo cng thi gian ng vi mi
chu k git nn din tch ca cc git l hon
ton nh nhau.
Dng c ghi ti mt thi im nht nh sau
khi t xung, thng l 17 ms trc khi xung
ngt.
Cch 2:
Cng dng cc ph c ghi hai ln.
Ln th nht 17 ms trc khi t xung.
Ln th hai 17 ms trc khi ngt xung.
Cch ny cho hiu qu tt hn nhng thit b
phc tp.
Phng php xung vi phn
(Differential Pulse Polarography-
DPP)
Trong phng php cc ph xung vi phn in cc
c phn cc bng mt dng in p mt chiu
bin thin tuyn tnh vi tc chm.
Vo cui mi chu k git (git ri cng bc nh
mt b g) trn khung in p bin i mt chiu
ngi ta t thm mt xung vi bin thay i
trong khong 5 100 mV, thi gian t xung t 40
100 ms.
Phng php xung vi phn DPP
Trong phng php cc ph xung vi phn in cc
c phn cc bng mt dng in p mt chiu
bin thin tuyn tnh vi tc chm.
Vo cui mi chu k git (git ri cng bc nh
mt b g) trn khung in p bin i mt chiu
ngi ta t thm mt xung vi bin thay i
trong khong 5 100 mV, thi gian t xung t 40
100 ms.
Cng dng cc ph c ghi 2 ln.
Mt ln ti thi im t
1
, thng l 17 ms trc khi
np xung, ghi dng i
1
.
Ln th hai o ti thi im t
2
, thng l 17 ms
trc khi ngt xung, ghi dng i
2
.
Hai gi tr o ny cha cng gi tr bin thin ca
dng t do qut tuyn tnh nn khi ly hiu cng
dng sau hai ln ghi th gi tr A i = i
2
i
1
hu nh
khng ph thuc vo dng t.
ng cc ph biu din A i theo E c dng
nh.
Chiu cao ca nh t l vi nng cht in
hot c trong dung dch.
Th ca nh c gi tr c trng ging nh th
bn sng trong cc ph c in
Phng php DPP cho php xc nh tng cht
trong dung dch khi th bn sng ca chng ch
cch nhau 0.05 V.
y chnh l u im ca phng php cc ph
xung vi phn so vi phng php cc ph c
in v phng php xung thng thng.
nhy cao ca phng php DPP nh vo s
tng dng Faraday cng vi s trit tiu ca dng t.
Gii hn pht hin ca phng php ny trong
khong t 10
7
10
8
M.
Hin nay cng vi s pht trin ca cc k thut c
chnh xc cao, ngi ta c th t n nhng tc
qut rt ln, do c th rt ngn thi gian phn
tch v thm ch c th o nhiu ln trn cng mt
git thy ngn trong thi gian rt ngn, do lm
tng chnh xc.
C s l thuyt ca phng php
xung thng
Trong phng php cc ph xung thng ng
biu din i E c dng tng t cc ph c in,
nhng c nhy cao hn.
Nu chn in p khi im tng ng vi chn
sng cc ph c in, ti y dng Faraday thc
t bng khng. Vi qu trnh in cc thun
nghch
A + ne B
xung thng
Gi tr dng Faraday c th c biu din bng
phng trnh:
)
1
1
( *
*
* * * *
P t
D
A C F n I
m
+
=
t
Trong :
A : din tch b mt in cc ti thi im o.
C : nng cht in hot.
D : h s khuych tn.
t
m
: khong thi gian tnh t khi cng xung n khi
o dng.
xung thng
P c tnh theo cng thc :
) ( * )
*
*
exp(
2 / 1
r
E E
T R
F n
P =
Vi E l th ca xung c gi tr bng bin ca
xung cng vi in p khi im
E
r
l th bn sng trong phng php cc ph c

in.
xung thng
Nu E m so vi E
th P ~0. Cng dng

Faraday t n gii hn I
1
.
Khi phng trnh chuyn v dng phng
trnh Cottrell:
m
l
t
D
A C F n I
*
* * * *
t
=
xung thng
Tng t nh phng trnh HeyrovskyIlkovic
trong cc ph c in ta c :
I
I I
F n
T R
E E
l
r

+ = lg *
*
*
* 303 . 2
2 / 1
xung thng
Cng ging nh phng trnh Ilkovic trong phng
php c in, phng trnh Cottrell cng c p
dng cho cc qu trnh in cc thun nghch v
khng thun nghch trong phng php NPP.
Bng cch so snh phng trnh Ilkovic v phng
trnh Cottrell ta thu c kt qu sau:
2 / 1
2 / 1
* 3 / 7
) (
) (
m
l
d
l
t
t
dc I
NPP I
=
xung thng
Vi cc gi tr t
1
= 4s, t
m
= 40 ms ta c t l
trong khong 6 7
Nh vy c th ni phng php NPP nhy hn
phng php cc ph c in rt nhiu ln
xung vi phn
Xt mt h thun nghch. T phng trnh Cotrell
ta c th tnh c Ai cho 2 ln o trong phng
php xung vi phn theo phng trnh sau:
o o o
o
* *
*
*
2 2
2
P P P
P P
t
A A A
A A
m
D
C A F n i
+ + +
-
H
- - - - = A
xung vi phn
Vi:
(
+
=
E
E E
P
r
A
RT
nF
2 / 1
2 1
2
exp
(

=
2
exp
1 2 E E
RT
nF
o
E
2
E
1
= AE, cn gi l bin xung
E
1
l th ti im o cng dng i
1
(ngay trc khi
cng xung).
E
2
l th ti im o cng dng i
2
(sau khi cng
xung thi gian t
m
).
xung vi phn
xung vi phn
Trong trng hp AE nh phng trnh trn biu
bin nh sau:
( )
( ) P
t
F n
i
P D
C A
RT
m
+
A
H
AE =
1
2
2 2
*
* * *
Khi P
A
= 1 , Ai s t cc i v c biu din
bng biu thc:
( )
1
1
*
* * *
max
+
H
=
A
o
o
t
i
m
D
C A F n
xung vi phn
Trong trng hp -AE/2 nh hn (RT/nF) v bin
xung nh, gi tr (Ai)max c th biu din theo
biu thc :
( )
( )
t
F n
i
m
D
C A
RT *
* * *
4
2 2
max
H
AE =
A
xung vi phn
Khi -AE >> (RT/nF) gi tr (o - 1) / (o + 1) 1 v
(Ai)max tr thnh phng trnh Cottrell
m
l
t
D
A C F n I
*
* * * *
t
=
T cc phng trnh thy rng khi AE tng, (Ai)
max

cng tng, tuy nhin trn thc t ngi ta nhn thy
rng khi bin xung AE tng th bn chiu rng ca
ph cng tng theo dn n gim phn gii.
xung vi phn
Bn chiu rng vch ph W
1/2
c tnh theo cng
thc :
|
.
|
\
|

|
.
|
\
|
+
=
o
o
2
2
2
2 / 1
* 4 4
* 4
ln *
y
y y
W
nF
RT
Vi y = o
2
+4o +1 v
2
2 / 1
AE
=
E E
r
peak
Nh vy cho qu trnh kh, th nh s di v pha
dng hn khi bin xung tng (AE <0)
PHNG PHP VON-AMPE HA TAN
Phng php gm 2 giai on chnh : tch
gp v ha tan.
Giai on tch gp:
Th m c p vo trong mt thi gian
xc nh, kim loi quan tm s b kh trn b mt
in cc.
M
n+
+ ne
-
M(Hg) (in cc thy ngn)
M
n+
+ ne
-
M (in cc rn)
Phng php gm 2 giai on chnh : tch
gp v ha tan.
Giai on tch gp:
Tch gp cht phn tch ln b mt in cc.
Giai on ha tan :
Ha tan cht phn tch vo dung dch v ghi
th.
Trng hp xc nh Cation
Ty theo loi in cc s dng, ty thuc ion xc
nh v th in phn m phn ng trn in cc
s khc nhau
Phn ng xy ra nh sau:
M
e
n+
+ me M
e
(n-m)+

Th tch gp thng m hn th bn sng ca kim
loi t nht khong 0,3V.
+ Khi m = n s to thnh kim loi M
e
0

+ Khi m < n s to thnh ion M
e
(n-m)+
, trong trng
hp ny c th kt ta trn b mt, ion M
e
(n-m)+

to thnh phi tip tc phn ng vi mt anion X
p-

trong dung dch to kt ta (M
e
)
p
X
(n-m)
theo phn
ng:
pM
e
+ (n-m)X
p-
(M
e
)
p
X
(n-m)
+
Trong trng hp ny cc in cc tr nh Pt,
Cacbon v in cc git Hg treo thng c s
dng.
Cc ion kim loi hoc cc kt ta to thnh s bm
ln b mt cc in cc.
Ring vi in cc git Hg treo cc kim loi s to
hn hng vi thy ngn:
M
e
n+
+ Hg + ne Me
0
(Hg)
Cc in cc rn b gii hn v pha th m do
dng hydro theo phn ng :
2H
+
+ 2e H
2

Do nhiu ion kim loi c th bn sng m hn
th ca hydro s khng th xc nh c
Thi gian duy tr vic p th tch gp ln trn
cathod ph thuc vo nng ca cht cn phn
tch trong dung dch.
Do in cc rn b gii hn v pha m nn
ngi ta thng s dng in cc mng Hg bng
cch cho mt lng nh Hg
2+
vo dung dch
(khong 10
-4
M). Khi ny:
Hg
2+
+ 2e
-
Hg (mng Hg ph trn in cc rn)
M
n+
+ ne
-
M(Hg)
y l trng hp c ng dng nhiu nht trong
thc t, v d nh xc nh hm lng Cu
2+
, Pb
2+
, Cd
2+
trn cc in cc git Hg treo, trn in cc Cacbon,
Cacbon trng Hg
Trng hp m < n t gp hn trong thc t, v d xc
nh Tungsten dng WO
2
2+
trn in cc Cacbon
Graphite siu tinh khit:
WO
2
2+
+ e WO
2
+

WO
2
+
+ 3SCN
-
+ nR + 2H
+
WO(SCN)
3
R
n
+ + H
2
O
Trong R l pyramidone hoc antipyrine
Trng hp xc nh cc anion
Nhiu anion c th oxi ha kh nm ngoi
khong th lm vic ca cc in cc nn vic xc
nh trc tip thng rt kh khn.
xc nh cc anion thng ngi ta s s
dng cc in cc khng tr.
Khi ny trong qu trnh tch gp cc kim loi s
dng lm in cc s tan ra do phn ng in
ha :
M
e
0
ne M
e
n+

Ngay lp tc, cc ion ny s phn ng vi cc
anion cn xc nh to thnh hp cht khng tan
bm trn b mt in cc.
mM
e
n+
+ nX
m-
(M
e
)
m
X
n
+
Tiu biu cho cc qu trnh ny c th k n vic
s dng cc in cc git Hg treo hoc in cc
a Ag
Xc nh hm lng halogenua (to Hg
2
X
2
, AgX)
Hoc Sunfua (to HgS hoc Ag
2
S)
Trng hp s dng phng php hp ph
Trc ht thm vo dung dch xc nh mt s thuc
th hu c c th to phc t tan vi ion cn xc nh.
Cc phc ny s tch gp bng cch hp ph ln b
mt in cc (thng l in cc git Hg treo) v
tham gia phn ng in ha trong giai on ha tan.
Phng php ny c ng dng trong xc nh rt
nhiu cht nh xc nh Fe vi thuc th Catechol, Ni
v Co vi Dimethylglyoxim, Al vi Alizarin S.
Trng hp s dng cc in cc b tr
y l loi in cc mi c nghin cu pht trin
trong khong 20 nm gn y.
B mt cc in cc ny c gn thm cc cht
c kh nng to phc t tan vi cc ion cn xc nh.
Cc cht ny c th l cc axit hu c, cc amin hoc
cc nha trao i ion .
Cc in cc c b tr thng l cc in cc
Cacbon, c bit l cacbon nho do kh nng d trn
vi cc cht b tr v d ch to.
Trng hp s dng cc in cc b tr
Trong giai on tch gp, cc cht b tr s to
phc vi ion cn xc nh trn b mt in cc v
lm giu lng ion, qua lm tng nhy.
Cc in cc tiu biu cho loi ny c th k n l
in cc cacbon nho c b tr vi cc nha
trao i ion xc nh Cd
2+
,in cc cacbon nho
c b tr bng Zinc Diethydithiocarbamate
xc nh Hg
2+

Giai on ha tan :
Xc nh cc cation
Nu dng tch gp l kim loi, phn ng ha
tan nh sau:
M
e
0
ne M
e
n+

Nu tch gp dng kt ta :
(M
e
)
p
X
(n-m)
me pM
e
n+
+ (n-m)X
p-

Chiu cao peak ha tan s t l vi lng cht
tch gp v t l vi nng ion cn xc nh trong
dung dch.
Xc nh cc anion
Ta xc nh gin tip qua lng kim loi phn
ng to kt ta trn b mt. Khi ny phn ng ha
tan nh sau :
(M
e
)
m
X
n
+ ne mM
e
0
+ nX
-

Cng dng t l vi lng kim loi to thnh,
ng thi cng t l vi lng anion to kt ta
vi kim loi.
Trng hp hp ph v in cc b tr
Trong trng hp ny, qu trnh qut th khng c g
khc vi phng php cc ph.
im khc nhau y l nh vic tch gp thng qua
cc phn ng ha hc gip lm tng nng ion
xc nh trn b mt ln nhiu ln, do lm tng
nhy ln nhiu ln, mt khc qu trnh khi ny khng
ph thuc vo s khuch tn na do phn ng ch
xy ra bi cc cht trn b mt in cc
V nguyn tc thi gian tch gp c th ko
di v hn v lm tng lng cht tch gp trn b
mt in cc nn c th xc nh cc nng rt
nh.
Tuy nhin do nhiu l do nh s tch gp c
cht bn trong nn, nh hng ca dng t nn
gii hn phn tch vi k thut c in ch t n
nng khong 10
-7
10
-8
M .
Mun t nhy cao hn phi s dng cc
k thut von-ampe xung vi phn, sng vung
Mt s yu t nh hng n phng php
Trong phng php ny cng dng ph thuc
vo lng cht kt t trn b mt in cc, hay
chnh l ph thuc vo lng in tch cn thit
ha tan cht kt t. Ta c th biu din di dng
chung:
Q = f(n,A,D,e,,C)*t
Trong n l s mol in t trao i ca mi mol
cht phn tch,
A l din tch b mt in cc (cm
2
),
D l h s khuch tn ca ion xc nh (cm
2
/s),
l nht ng hc (cm
2
/s),
e l vn tc gc ca qu trnh khuy trn,
C l nng cht cn xc nh trong dung dch
t l thi gian tch gp (s)
nh hng ca din tch b mt:
Theo biu thc din tch in cc nh hng n
cng v din tch ca peak thu c, din tch
in cc cng ln, cng dng ha tan cng
ln.
Nu gia cc ln o, din tch b mt thay i s
gy ra lp li km cng nh gy sai s trong
vic xc nh
nh hng ca tnh cht b mt:
Vi cng din tch nh nhau, tnh cht ca b mt in
cc c th hon ton khc nhau, iu ny ph thuc
vo tinh khit ca in cc, t trng, xp ca
kim loi.
c bit ng nht ca in cc nh hng ln n
hot tnh ca in cc.
Cc in cc git Hg thng cho lp li cao hn khi
c cng mt din tch do thng c cc tnh cht khc
ging nhau v c b mt dng hnh cu hon ho.
Cc in cc rn thng c b mt khc nhau
gia cc ln o do qu trnh x l sau mi ln
o khng th t ti iu kin hon ton nh
nhau, do c th dn n lp li km.
Sau mt thi gian s dng b mt in cc
thng b nhim bn do cc cht kt t khng
ha tan ht v c th dn n sai s nu khng
x l k b mt.
Cc nh hng khc:
Khi tc khuy trn tng, lng cht kt t cng
tng theo do t c lp li v chnh
xc tt, tc khuy gia cc ln tch gp phi nh
nhau.
Trong trng hp s dng in cc c b tr,
qu trnh trao i din ra nh qu trnh chit do
vic tng tc khuy trn lm tng kh nng tip
xc v do tng lng trao i
Cc nh hng khc:
Thi gian tch t cng di, lng cht c tch t
cng ln, cng v din tch pic cng tng;
Ngoi ra vi trng hp xc nh anion, lng
cht kt ta cn ph thuc vo tch s tan ca cht
to thnh, tch s tan cng nh, lng cht tch t
cng ln .
CHUN VON-AMPE
Bn cnh vic xc nh trc tip cc cht in
hot bng cch ghi cng dng theo th p vo,
chng ta c th xc nh gin tip cc cht khng
in hot.
V d xc nh SO
4
2-
ngi ta thm chnh
xc mt lng d Pb
2+
sau xc nh li lng
Pb
2+
d .
Ta cng c th xc nh Cl
-
vi in cc Ag.
Khi p th dng s c phn ng:
CHUN VON-AMPE
Ag e
-
+ Cl
-
AgCl
Sau qut th v pha m ta thu c dng
ha tan :
AgCl + e
-
Ag + Cl
-

Cng dng s t l vi nng Cl
-
trong
dung dch.
Phng php von-ampe cng c th xc nh
rt tt cc hp cht hu c c tnh in hot v do
c s dng lm u d in ha trong HPLC.

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l th bn sng trong phng php cc ph c

th P ~0. Cng dng

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