Phn I: C S L THUYT

Trong cc phng php in ha nghin cu v s n mn kim loi, c s dng ph

bin nht l cc php o sau:
- Xc nh th n mn trng thi tnh (Eam)
- o ng cong phn cc (i-E)
- Xc nh s bin thin ca Eam theo thi gian
- Xc nh mi quan h i-t trong qu trnh phn cc th khng i (Potentiostatic)
- Xc nh mi quan h E-t trong qu trnh phn cc mt dng khng i
(Galvanostatic)
- Phng php o tng tr
Phn II: THC HNH
Nghin cu kh nng n mn ca in cc Cu trong dung dch axit
1. H in cc:
in cc lm vic (WE): Cu
in cc so snh (RE): AgCl/Ag
in cc i (CE): Thp khng g.
2. Dung dch in ly: hn hp dung dch NaCl + H2SO4 ;
3. My o: CPA-HH5M
4. Phn mm: PGSDynamic v PGSStatic.
Phn III: KT QU V THO LUN
1. Th ng: Xc nh tc n mn
a) ng cong phn cc: o in tr phn cc
+ ng dng th (hnh 1) l kt qu tng hp ca cc dng anod (i a) v dng cathod
(ic) xy ra trn b mt in cc. Theo l thuyt ng cong phn cc ny tun theo
phng trnh Butler-Volmer. Dng cng thp, ng hc cng kh khn th cng cn c
qu th hot ha ln t ti mt gi tr dng no .
+ T ng cong phn cc cho php xc nh c dng n mn im v tc n mn
(g/S.t):
A.i am .t
m
=
m =
S.t
n.F
Trong :
A = nguyn t lng ca kim loi (gam)
iam = dng n mn (A)
t = thi gian din ra qu trnh n mn (gi, ngy m, thng, nm)
n = s electron trao i trong qu trnh oxy ha kh
F = hng s Faraday (C.mol1)
S = din tch mu (cm2)

Hnh 1. ng cong phn cc ca in cc Cu

trong dung dch hn hp NaCl + H2SO4
* S liu thu c t phn mm:
V ==> U = -0.1229 + 0.1847* I
Corr. Potential : -0.1229 vol, Pol. resistance : 184.6553 Ohm
Corr. density
: 3.5323E-0002mA
Equal to 1.0250E-0005mg.S or 3.6321E-0001mm/year
* T cc d liu thu c trn ta c:
- Th n mn Eam = -0.1229 V
- in tr phn cc l: 184.6553
- Mt dng n mn l : 3.5323.10-2mA/cm2
- Tc n mn l : 3.6321.10-1 mm/nm
Lu :
Php o in tr phn cc tin hnh qu th rt nh do dng quan h cng rt
nh. iu ny c ngha l dng trao i (dng t) c th ng gp mt cch ng k
vo to tn hiu nhiu. Cn ch loi tr sai s ny nu c.
C th s dng mt thit b s dng tn hiu tn s ln trc khi o in tr xc
nh in tr nn v dung dch. iu ny cn ch vi nhng h m in tr RP khng
ln v in tr dung dch cao ( dn thp), ng gp ng k vo gi tr o c. V
vy tc n mn tnh c s nh hn gi tr thc t. Nu thc hin php o xc nh
in tr dung dch v nn trc th in tr o c s phi tr i cc gi tr ny c
gi tr thc. Hoc ci thin tnh dn in ca dung dch in ly. Thun li ca k thut
ny l o dng o ti th gn nh khng i nn dng thay i gn nh l bng 0, do
in tr Ohm hu nh khng c ngha.
Nn s dng tc qut chm.
Nu ng i-E l mt ng cong (khng thng khi i qua i=0), in tr phn cc c
th tnh bng cch v mt on thng tip tuyn vi ng cong ti Eam v i = 0.
o in tr phn cc l qu trnh o nhanh nh gi tc n mn. tc qut
th 0,1mV/s, vi khong th 50mV cn cha n 10 pht. Vic o nhanh cng lm cho
php o in tr phn cc rt hu ch cho cc thc nghim nh nh gi nh tnh cc
cht c ch. V in th p vo khng xa khi th n mn nn mu khng b ph hy
trong qu trnh o, do mu c th s dng cho cc nghin cu khc.
Vic qut nghch c th dung cp mt ng cong i-E ghi li nhng du vt ng
thun b qua khng ghi c.
b) ng ngoi suy Tafel:

ng ngoi suy Tafel catot v anot chnh l phng trnh:

i
= log
icorr
Hay ng -logi l ng thng c dc .
Khi = 0 (ti Eam), logi/iam = 0 hay i = iam.

Hnh 2. ng ngoi suy Tafel ca in cc Cu

trong dung dch hn hp NaCl + H2SO4
* S liu thu c t phn mm:
V ==> Uanod = -0.0397 + 0.0759 * log j
V ==> Ucatod = -0.8977 + -0.8887 * log j
Stational Potential : -0.1072 vol
Stational density : 1.2896E-0001mA
Equal to 3.7423E-0005mg.S
or 1.3260E+0000mm/year
* T cc d liu thu c trn ta c:
- Th n mn Eam = -0.1072 V
- Mt dng n mn l : 1.2896.10-1mA/cm2
- Tc n mn l : 1.3260 mm/nm
u im:
- C th s dng cho vic o trc tip dng n mn, nhanh so vi phng php trng
lng, rt thun tin cho vic nghin cu cc cht c ch, cc cht oxy ha v so snh cc hp
kim khc nhau.
- Qu trnh c iu khin bng cng c v do c tnh ng lot gia cc phng th
nghim khc nhau.
Nhc im:
- Mu khng dng li c cho cc php o khc sau khi phn cc ngoi suy Tafel.
- Phn cc nng v st th Ohm c th lm gim vng tuyn tnh, do vic ngoi
suy n iam s kh hn. Nu iu ny xy ra, an ton nht l o Iam ti im ng ngoi
suy Tafel catt ct Eam. Ngi ta c th gim nh hng phn cc nng bng cch khuy
dung dch. Trnh st th Ohm bng vic thit k bnh in phn sao cho ph hp vi iu
kin thc nghim hoc dng k thut phn hi dng, k thut ngt dng.
- p dng tt cho h c mt phn ng oxy ha kh.
Yu cu:
- K thut th ng i hi th n mn phi n nh v khng thay i trong qu trnh
o.

- Vic qut th ng cn phi chm m bo thuc tnh trng thi bn

Nhn xt:
T s liu trn ta thy c s chnh lch gia hai phng php c th do cc nguyn
nhn sau :
- H o thc nghim cha iu kin tun theo phng trnh Tafel.
- Vic la chn im tip tuyn trn ng thc nghim cha chnh xc.
- Thng thng vic o ng phn cc thng c qut th mt khong 25mV
xung quanh th n mn E am. Thc t y do vic qut th tng i rng (-0,7V n
0,3V) nn c th dn n im tip tuyn cha c chn ng.
c) Qut th tun hon (CV)
Phng phap von-ampe vong la phng phap quen thuc trong cac nghin cu in
hoa. Ban cht cua chung la phng phap th ng (potentiodynamic), th c quet phn cc
vi tc khng i theo chiu m dn ti mt gia tri xac inh ri lp tc cho phn cc
ngc lai va quan sat ap ng dong. Mi bc quet tin c tip tuc bi mt bc quet lui
v phia ban u.
Phng trinh ng von-ampe trong trng hp kh thun nghich ion kim loai thanh
kim loai trn in cc rn ia tr a c Delahay thit lp, 200C co dang:

E = Constant +
Trong o: E

0,058
lg ( I gh I )
n

: in th

I gh : dong gii han

I : dong o c
n : s electron trao i trong phn ng oxi ha kh thun nghch
Phn tich ap ng dong co th cho thng tin v nhit ng hoc va ng hoc cua qu
trnh vn chuyn electron tai b mt dung dich - in cc, cung nh ng hoc va c ch cua
cac phan ng hoa hoc dung dich.

Hnh 3. ng CV ca in cc Cu trong dung dch hn hp NaCl + H2SO4

Nhn trn hnh 3 ta thy xut hin 1 pic chiu kh iu c ngha Cu 2+ tan trong qu
trnh n mn b kh tr li thnh Cu, nhng y khng thy xut hin pic oxi ha Cu c th
do khong th qut cha n vng th xut hin pic oxi ha ca Cu.
cyc
Q+
QQ
Qt(mC)
1
94.44 -99.18 -4.7398
193.62
2
98.91 -105.8 -6.8581
204.69
3
100.9 -108.3 -7.4392
209.19
4
101.1 -108.9 -7.7607
210.05

101.3

-108.4

-7.0929

209.73

Hnh 4. th bin i in lng Q ca in cc Cu

trong dung dch hn hp NaCl+H2SO4
T th v in lng Q qua 5 vng qut ta thy |Q+| v |Q-| u gim iu chng
t sau mi ln qut in lng trao i trn b mt in cc u gim, iu c th gii
thch l do s khuch tn cc nng ion kim loi n b mt in cc chm trong khi tc
qut nhanh lm cho in lng Qt gim.
- Tc qut

Hnh 5. ng CV ca in cc Cu trong dung dch hn hp [Fe(CN)6]3-/[Fe(CN)6]4-

cc tc qut th khc nhau.
Thng thng th chiu cao pic t l thun vi tc qut v tun theo phng trnh
Randles Sevcik:
3

I p = (2, 69.105 )n2 AC* D 2 v2

Trong : n : s in t tham gia phn ng.

v : tc qut th (mV/s)
A : din tch in cc (cm2)
C*: nng cht in hot (mol/l)
D : h s khuch tn (cm2/s)
Nhng y ta thy tc qut cng ln th ip cng gim iu c th gii thch nh
sau: Khi tc qut ln th thi gian p th th n mn ca Cu rt ngn do Cu b n mn
t nn ip nh khi tc qut cng chm th lng Cu b n mn cng nhiu nn ip cao hn.
2. Dng ng
p dng trong khong t -1mA n 1mA vi tc qut 0,5mA/s theo di s bin i
ca th, theo kt qu thu c t hnh 6 ta thy khi dng tng th th cng tng theo v ngc
li.

Hnh 6. S ph thuc ca th vo dng ca in cc Cu

trong dung dch hn hp [Fe(CN)6]3-/[Fe(CN)6]43. Th tnh
p th U1=-0,5V, U2=0,5V trong thi gian 1s qut 5 chu k kt qu thu c hnh 7.

Hnh 7. S ph thuc ca dng vo thi gian ti U1=-0,5V, U2=0,5V

* S liu thu c t phn mm:
(1) At -0.5 V, Q=-9.1488176mC/cm^2
(2) At 0.5 V, Q=14.426844mC/cm^2
(3) At -0.5 V, Q=-12.528857mC/cm^2
(4) At 0.5 V, Q=14.442243mC/cm^2
(5) At -0.5 V, Q=-12.660009mC/cm^2
(6) At 0.5 V, Q=14.46859mC/cm^2
(7) At -0.5 V, Q=-12.690492mC/cm^2
(8) At 0.5 V, Q=14.496227mC/cm^2
(9) At -0.5 V, Q=-12.741688mC/cm^2
(10) At 0.5 V, Q=19.695241mC/cm^2
Total Q= 17.75928mC/cm^2
U1= -0.5V Total Q1= -59.769864mC/cm^2
U2= 0.5V Total Q2= 7.529144mC/cm^2

Hnh 8. S ph thuc ca dng vo thi gian

ti U=-0.5V v 0,5V khi chuyn v 0
T ta c:
Tng in lng trao i trn b mt in cc qui v 1cm2 sau 5 chu k:
-0,5V l -59.769864 mC
0,5V l 7.529144 mC
Tng in lng trao i ca h l Q= 17.75928 mC
4. Dng tnh
p dng ti I1=-0,5mA v I2=0,5mA trong thi gian 5s v qut 5 chu k. Kt qu thu
c hnh 9

Hnh 9. S ph thuc ca th vo thi gian ti I1=-0,5mA, I2=0,5mA

Hnh 10. S ph thuc ca th vo thi gian

ti I1= -0,5mA, I2=0,5mA khi chuyn v 0