Chuong 3

OQNG HOC CAC PHAN ONG OIEN H6a

MUC TIEU

Hoc xong chuong nay, sinh vidn c6 kha nang :

1. Phan bidt cac dac tnmg co b&n cua qua trinh didn cue khdng can bang so vdi cac qui
trinh can bang trdn didn cue.
2.MA ta dupe hidn tupng phan cue, nguydn nhan phan cue.

3. Phan bidt duoc su phan cue hda hoc vdi su phan cue n6ng dd.
4. Nam duoc m6i lidn ha giiia t6c dd qui trinh didn cue vdi thd dian cue va vdi ha s<5
chuyd'n.
5. Trnh dupe mat dd dong an6t va catdt.

6. Dinh nghla dupe qua thd tran dian cue, mat dd ddng trao ddi.
7. Thidt lap dupe phuong trinh Volmer - Butler ddi voi mat dp ddng.
8. Thidt lap cic phuong trinh gidi han cua phuong tiinh Volmer-Butler dPi vdi cic
truong hop ridng khi qua thd nho hon 10 mV va khi qud tha' ldn hon 100 mV.

9. Phan bidt dian cue phan cue H tudng vdi dian cue khdng phain cue It tudng.
10. Md ta dupe su phan cue khudch tan va ldp khudch tan Nernst, thidt lap dupe bidu
thuc mat dp dong khudch tan va mat dp dong khuech tan gidi han.
11. Ndu dupe co so cua phuong php cue phd trong hda hoc phan tich.
12. Ndu dupe co sd cua cac phuong phap nghifin cuu thuc nghidm cac qua trinh dian
cue.
13. Ndu dupe co sd cua thuydt lupng tu vd cac phan ung dian h6a.

94
 3.1. NHONG OAC

TRLfNG CUA QUA TR1NH DIEN

CUC KHONG CAN BANG

Khac vdi trang thai can bang tren didn cue cung nhu trdn toan mach dien hoa, d do
khong co dong dien luu thong (I = 0), ddi vdi he didn hoa khong can bang luon luon co
mot dong dien luu thong (I 0). Ndu he dien hoa la mdt nguon didn nang dupe noi vdi mdt
*
thid't bi tidu thu dien thi dien ip cua hd bao gid cung nho hon siic dien ddng cua hd (V < E);
con nd'u hd dien hoa lam vide theo chd dd didn phan tire la dung nguon didn nang tu ben
ngoai dd gay ra six bid'n doi chat trdn didn cue thi V > E. Nhu vay, cdng suat cua nguon tidu
thu dien nang se nho hon cong sua't cue dai tinh theo II thuyd't (l.V < I.E). Trong su didn
phan, trai lai, cdng suat tieu thu l.V lai ldn hon cdng sua't II thuyd't I.E (l.V > I.E). Ndu he
dien hoa can bang la mot didn cue thi td'c dd oxi hoa andt theo mot chidu nao do se bang
tdc dd khir catdt theo chidu nguoc lai va bang dong trao d6i
u : i, = ir\ =1,

(mat dd dong i bang cudng do dong didn Iluu thdng quy ve mdt don vi be mat phan chia
pha). Trang thai khdng can bang trdn dien cue duqc dc trung bang su khac nhau vd mat do
dong anot va catot: ia | ic |*i0.
*
Dd'i vdi mdt didn cue da cho khi tdc dd oxi hoa andt Idn hon tdc dd khir catdt theo
I
chieu nguoc lai thi hidu ia - 1 ic = i+ (i+ > 0) vdi i+ la tdc dd thuc, do dupe trdn andt. Ngupc
1 I
lai neu tdc dd oxi hoa andt nho hon td'c dd khu catdt thi hieu ia - ic = i_ (i_ < 0) vdi i.. Ia
tdc dd thuc do dupe tren catdt. Hinh (3.1) minh hoa tdc dd thanh phan va tdc dd thuc cua
didn cue d hai trang thai can blng va khdng can blng:

a) / b) c) /

'a
I'cl 'a > 'c
khong co sV d6ng <Ji$n thyc i_ d6ng di$n thuc i+
luu thong luu thdng trdn luu thdno trdn andt
dongdin
i = i, - I i, = 0
catdt
ig
U-1.- 'U
i >0
i_ < 0

Hinh 3.1. Mat do dong ihitc va mdt dd ddng thdnh phdn d trang thdi
can bang (a) vd khdng cdn bang;(b) ddng catdt; (c) ddng andt

Do trang thai khdng can bang cua hd didn hoa ( didn cue hoac pin didn) ma phan
ung hoa hoc trong trong hd didn ra theo mdt chidu uu tidn, didu nay da lam cho lupng chat
cua didn cue va thanh phan cua lap dung djch sdt didn cue thay ddi so vdi trang thai can
bang.

95
 The' cua didn cue khi c6 d6ng didn luu th6ng tp{ khdng bang thd didn cue can bang
<pi=0 tfnh theo phucmg trinh Nernst. Dd Ion cua dien thd <px khdng ti'nh duoc bang cac
phuefng trinh rut ra tir nhidt ddng luc hoc va noi chung ngoai cac ye'u t<5 phu thudc nhu ban
chat cua he dien hoa, nhiet dd, ap suet, <pt con phu thudc cudng dd dong didn luu thdng.

Tai trang thai dung cua qud trinh dien cue khdng can bang, dd ldm cua dien the
khdng cdn bang <ps khdng d6i theo thdi gian do d6 dien the cung duoc goi la the diifng.

Ddi vdi he didn hod khdng cdn bang, giua cucmg dd( (hay mat dd) ddng didn luu
thdng va td'c dd cac qua trinh hoa hoc xay ra trong he; gifta cudng dd (mat dd) ddng didn
luu thdng vd dd ldn cua s.d.d hay the didn cue ludn ludn co mdi quan he ham sd'.

3.2. DAC TRONG PHAN Cl/C CClA HEDIEN HOA KHONG CAN BANG

3.2.1. Syphan cyt cua he dien hod va s.d.d phan cut:

Tu phdn trucrc ta da bid't rang mdt hd didn hoa du dong vai trd mdt ngu6n didn ndng
hodc mdt binh didn phan thi khi c6 ddng didn luu thdng, didn ap V va s.d.d E khdng bang
nhau (V la hidu didn thd' do duoc b hai didn cue cua hd didn hoa khi co ddng didn luu
thdng; E la hidu didn the cua hd b trang thai can bang tai do khdng co dong didn luu thdng,
I= 0). Thuc nghidm cho they ndu hd didn hod khdng cdn bang lam vide theo chd dd didn
phan thi:
V = E+RI+Ep (3.1)

Ndu hd didn hda cung cdp didn ndng cho bdn ngoai thi :
V = E+rI-Ep (3.2)

vdi RI la tdng dd sut thd ohm cua dung dich va didn cue ;EP la sure didn ddng phan cue.
Nd'u goi A<pa vd A <pc la dd bien thidn cua ede thd didn cue uug vdi andt va catdt khi co dong
dien luu thdng thi tdng dai s6 hai dai luong ndy la sdd phan cue cua EP :

EP = A <pa + A <pc (3.3)

Tir (3 - 1) va (3 - 2), mdt each khdi qudt, ta c6 :
|V-E| = RI + Ep (3.4)
= ZRI+Pa+c

Nhu thd tri tuydt ddi cua hidu didn ap va sdd gdm ba hyp phn : tdng dd sut thd ohm
RI va dd bidn thidn cua ede thd didn cue urng vdi qud trinh andt vd catdt khi cd ddng
.
didn luu thdng Aa va A <pc Nguydn nhan cua su xud't hidn s.d.d phdn cue Ep la su luu

96
thdng cua mdt d6ng dien mil dd i qua cac dien cue. Dd ldn cua EP phu thudc vao dd Ion
cua mat dd ddng i. Hay khao sat dnh hudng cua mat dd dong i tdi EP, tut la tdi timg dd bin
thien the' dien cue A <p .

3.2.2. St/ phan cut dien cut

Khi co dong dien mat dd i luu thdng trSn dien cue thi he dien hoa (dien cue) chuyn tir
trang thai can bang (duqc dac trung bang the dien cue tmh theo Nemst) sang trang thai
khong can bang ductc dac trung bang the dien cue . Ngucri ta goi su ch6ch cua the' dien
cue can bang (pi=0doi vdi mdt dien cue qua d6 c6 dong dien luu thdng la su phan cue dien
cue, va dd ldn cua su chech nay la dd phan cue dien cue Tt
n = <Pi~ <Pt=o

Dd phan cue dien cue (tren d6 chi xiy ra mdt phan ung) c6n duqc goi la qua the do d6
(3.5) duqc viet 6 dang

r\ = <Pi~<Pi=o (3-6)

a day <pi=0 hoan toan duqc tmh dua vao phuefng trinh Nernst duqc rut ra tir nhiet ddng
luc dien hoa. Qua the q va q>x la ham cua mat dd dien i. Dudng cong m6 ta mdi quan he
ham s6 giua dien the <p{ hoac qua the q vao mat dd dong i duqc goi la dudng cong phan
cue. Su ghi lai ducmg cong phan cue, cho de'n nay v&n duqc xem la mdt trong nhung
phucmg phap nghien cuu ddng hoc cac qua trinh dien cue khdng thi thieu ne'u mudn di sau
vao ITnh vuc ddng hoc dien hoa.
Tir (3.6) they rang khi the can bang <pi=0chuyen dich vd phia ducmg hctn tiJc la
cpx > <ci=0thi qua the' co da'u duefng (q >0), do la qua the' andt, khi the' can bang i=0
chuye'n dich sang phia am hem tile la <pt < j=0 , thi qua the se mang da'u am ( q < 0), do la
qua the' catdt.
Trudng hqp he dien hod ia mdt pin dien cung cap dien nang cho ben ngoai thi tai catdt
xay ra phan ung khrr: Ox + ne -> Red voi td'c dd i_
Trong khi dd tai andt cd qua trinh oxi hoa: Red - ne ->Ox vcri tdc dd i+
Ne'u pin lam vide theo chd dd dien phan bang ngudn dien bdn ngoai thi cic qua trinh se
nguqc lai tuc ia

Red - ne > Ox

Ox + ne Red

Nhu the, andt cua pin dien se la catdt cua binh dien phan va catdt cua pin dien se ia
andt cua binh dien phan; Tom lai co su ddi da'u is ede dien cue cua he dien hoa. Hinh 3.2

-
7 ' PirOH&UD k 97
md ta sir bidn thidn cua thd" didn cue phu thudc mat dd ddng ddi voi hd didn hoi lim vide
nhu mOt ngudn didn ning vi 1km vide theo chd dd didn phin.
-q>

o
V
o

<p> (Ox1 + ne Red')

Ina=* 0 1

&
II
r)c<0 UJ
o
A V'i-o (Ox' + ne Red)
a
C

Khi din phSn 0 Pin dipn l&m vic

Hinh 3.2 Subien thien thd'didn cue phu thudc mat do ddng
theo hai che do lam viec (ngudn di$n ndng-ben phdi vd didn phdn.bdn trai) cua he didn h6a.

3.3. toc o0 cGa phAn Ong dien h6a

Hay xdt mdt phan umg xay ra trdn bd mat didn cue :
Ox + ne Red

Phan img trdn Ik mdt phan umg didn hod vi dd co thd thuc hidn duoc phan ung thl phai
co su chuydn n electron tir pha din didn electron (kim loai, ban din) sang pha din didn ion
(dung dich 16ng chit didn phin) hoic ngircrc lai. VI sir chuydn didn tfch xiy ra trdn ranh
gidri phin chia pha co ban chit khic nhau ndn phan ung didn hoi thudc hd phan ung dj thd.
Gii str phan ting didn hoi duoc bidu thi bing mdt phucmg trinh phan umg khii quat:
v(Mj+ne * O

6 diy hd sd hop thuc Vj duoc tlnh la duong ddi vcri chit tham gia phan umg vi im ddi vcri
san phim phan umg. Gidng nhu ddng hoi hoc c6 didn, tdc dd phan umg da cho duoc xic

dinh bing hd thtic: v =

Vj dt

6 diy libid'n thidn sd mol chit Mj quy vd don vi thtii gian vi don vi didn tich bd
dt
mit didn cue. Do su chuydn n electron khi thuc hidn phan umg didn hoi ndn tdc dd v cung ti
Id vcri sd mol electron, do do:

n dt

98 -
7 PITDH&UU - 8
 dN
vdi - la sd mol electron tham gia phan iftig didn hod trong khoang thdi gian dt vk quy
dt
dN
...
vd don vi didn tfch b& mat didn cue. Vi dt
- ti 16 vdi mat. d6. d6ng in6n biu thirc v trd thknh:
&

v =
--
1 .
nF
.1

Theo quy udc cua Li6n doan qudc td v Hoa hoc H thuydt va umg dung thi mat dd dong
i duoc tfnh Id duong n6u phan tfng didn hoa Id mdt su oxi hoa va dm ndu la phan urng khur,
do do :

'a=nFvOx
ic = -nFvRed
VI ca hai qua trinh oxi hoa va khii diSn ra nguoc chiu nhau va tr6n chng mdt didn cue
n6n mdt dd dong tdng hop ise bang:

i= ia + ic = nF(v0x-vRcd).
Tur mdi quan hd mdt dd dong iva tdc dd phan umg v da thidt lap, ta thd'y ring mdt dd i ti
16 thudn vdi tdc dd v, do d6 hoan toan c6 th dung mdt dd ddng i dibiu thi tdc dd cua
phan ung didn hod.
Khac vdi ddng hoa hoc b d6 tdc dd ti 16 vdi ndng dd chit tham gia phan ling thdng qua
hing sd tdc dd k la ham cua nhidt dd, dp suit; d ddng hoc didn hod, tdc dd phan umg cdn
phu thudc mdt tham sd phu trd, do Id thd didn cue. Mdt edeh khdi qudt tdc dd v cua phdn
ung didn hod duqc biu thi bang phuong trinh.
v = (T. p. <p y f (Q)
6 ddy f(Cj) Id mdt hkm cua ndng dd chd't phan umg M;, va thudng duoc vid't dudi dang
tfch cua nong dd C; cua cac chit tham gia phkn umg vdi luy thita to; Id bkc ri6ng cua mdi
chdt M; f(Cj) v. P (p ) Id hang sd tdc dd phan umg didn hod.

Cac qud trinh didn cue bao gid cung la nhung qua trinh ddng vi ede electron khdng
ngiimg duoc tai di theo hai hudng. Khi didn cue d trang thai cdn bang, su tai electron vin
tidp didn vdi tdc dd bang nhau theo hai hudng nguoc nhau n6n kdt cue khdng cd su tai thuc
ndo xay ra. Khi qua trinh didn cue Ik khdng ckn bang thi su tai electron theo mdt hudng la
uu ti6n vk k6't qua lk se co mdt dong thuc cua electron luu thdng tr6n didn cue. Dong
electron nay ho3c se hudng ttr bd mat didn cue tdi dung dich (kdm theo su khir tr6n catdt),
hokc tir dung dich tdi didn cue (kdm theo su oxi hoa trdn andt). Dd mdt ion cd thd tham gia
vao su tai didn tfch trdn didn cue thi sau khi tdi duoc ban Helmholz ngoki cua lap kdp phai
cd su khir hidrat hay sonvat dd trd thanh mdt ion trkn trui r6i ion nky mdi vuqt qua Idp kep
dd tdi ban Helmholtz trong rkt gkn bd mat didn cue, tai day dang oxi hod se tid'p nhkn
99
electron tit dipn cue d thuc hipn phan ting khir. Cung tuefng ttr, mpt chit khur da cP sin b
ban Helmholtz trong cua lPp kPp phai rcri bo ban nay dP din chuyPn vao 16ng dung dich. 6
ca hai qua trinh khu va oxi hod niy( cac ion phai vupt qua hing rio dipn ning cua lPp dipn
kep; muPn viy chung phai dupe hoat hod.
DPi vPi phan ting dipn cue dupe viPt dudri dang khai quit:
Ox + ne Red

tPc d6 v cua qua trinh cP dang phu hpp vPi quy luit dpng hoc dj thP hie mPt: v = k'. CQx

0 ddy biPu thi lupng chit hinh thanh trong dcm vi thcri gian vi don vi dipn tich bP
v
3
mat (mol.m- 2. s~ hope mol.cm 2. s"1); Cox li nPng dp chit oxi hoa biPu thi ra mol.dm"
1

hoic mol.cm-3 ... k' la hang sP tPc dp cua phan ting hoi hoc dupe cho bang phuong trinh
arhenius quen thuPc:

k' = A.exp.
RT

VI phan ting dipn hoa co liPn quan dPn sir chuyPn dipn tich qua lop dipn kep nin ngoii
hang rao ning lupng biPu thi qua Ea c6n phai c6 th6m hang rio dipn ning do su co mat cua
dipn thP <p gitia dipn cue va dung djch; do do hing sP tPc dp chuyPn dipn tich bay giP cP
dang

k = A.exp (37)

Phan ting dipn cue la mPt phin ting hai chiPu trong dp cP mpt chiPu uu tifin, dP la chiPu
khu hoic chiu oxi hoi. Phin dipn ning nF tp se khic nhau dPi vPi qui trinh khur vi oxi
hoi. Hay xet qui trinh khir trPn catPt dPi vPi chit oxi hoi Ox. DP qua trinh xiy ra dP dang
thi phin diPn nang giy boi dipn tnrdng Ipp kPp tao thuin lpi cho chit oxi hoi tiPp nhin
electron tir dipn cue se li anF<p , khi dp tir 3.7 hing sP tPc dP khir co dang

k= k_
p(ffi (3.8)

a lihP sP chuyPn cP gii tri gitia 0 vi 1 va thupng bing dp tinh dPi xting cua hang
rao ning lupng, chinh vi le nay mi a con goi lihp sP dPi xting.

MPt cich tuong tu dpi vPi su oxi hoi cua chit khir Red, theo chiPu ngupc lai, hing sP
tPc dP co dang

M >c'-exp<lp (3.9)

100
 Hinh 3.3 minh hoa gian d6 thd ndng trong sir khur cat6t vcfi didn th Am (tao thudn lori
cho qua trinh chuyn di6n ti'ch qua ldp kep),

Ea+anF<f> <J>S Khoing cich

0

cua loan bo ip
tao thu$n lg
cho ion vuprt
hftng rSo
nSng lupng

,x o Ban Helmnoltz
/
/ ngocii
Kholng cch

Hinh 3.3. Gian dd the ndng cua qua trinh khif

(dirfrng chain chain khdng c6 di6n tnrfrng do <p = 0) . Khdng phai tohn bd difin th <p mi chi c6 apgiup
cho chit Ox dat t6i dinh hang rao th n3ng.)

Vtii cac gid tri cua hang s6 t6'c d6 phan ting didn hod duoc cho bang cac phuong trinh
(3.8) hodc (3.9), t6'c d6 phan ting khir catfit va phan ting oxi hod andt se co dang

vox = k+ CRed (tdc dd oxi hod andt)

a"F
vRed = k- exP .C0x (tdc dd khir catOt)

3.4. co ch cCia phAn ltngdi$n hoa

3,4.1. Cac giai doan phan umg

Qua trinh difin bife'n cua phan ting didn hoa bao g6m nhiu giai doan. Mdt each t6ng
qudt, cac giai doanndy duoc tap hop trdn so d6 sau (hinh 3.4),
Cung nhu phan ting hoa hoc, ede phan ting didn hod la su nd'i tid'p cac giai doan so cd'p,
d6 Id giai doan:

Tai khdi: su tai khdi la sir chuyn chd't gitia I6ng dung djch va bi mat didn cue (su
tai chdt tori b mdt didn cue, ede san phdm thoat khdi bi mdt didn cue).
Ngudi ta phdn bidt ba edeh chuyln chdt trong dung djch:

101
 - Su dien chuyPn: su di chuyn cic ion dudi tic dung cua dien truong khi co mPt
gradien dien thP

DiSn eye m$t di$n eye Dung djch

OX i ~ OX

Tai dien tich Phan i>ng

bfe m$t
Phan Ling
h6a hpc
J khoi

H\nh 3.4. Cdc giai doan cua phan ting dien hod

- Su khuPch tin: su di chuyln chit tit ncri cd nPng dp cao tdi ncri c6 n6ng dp thip hem.
Su khuech tin chit dupe thuc hien dudi tic dung cua mPt gradien hoa thP. Do thuc hien
phan ting dien hoi ma n6ng d6 cic chit khdng nhu nhau d be mit dien cue vi dung dich.
- Su dPi luu: su di chuyPn chit giy bdi cic hien tupng ngoai su dien chuyn vi su
khuPch tin, dupe gpp chung dudi cii ten ddi litu. Su dPi luu co th c6 nguyfin nhin li
gradien nhiet dp, ip suit ... Su khuiy co hoc dung dich liquan trpng nhit.
/

Su tai dien tich : su tai electron, ion qua ldp kep tofi bP mit din cue.

Cic phan ting hoa hoc nhu su khir hidrat, su tao phtic, su trao d6i proton ... co thP
xay ra trudc hoic sau su tai electron.

Cic phan ting b mit nhu su hip phu, su khir hip phu hoic su ting trudng cic tinh
thP.
Nhu viy nhting hin tupng co ban chit khic nhau co thP can trd su tin triPn cua h
dudi tac dung cua mPt su phin cue dien cue, vi han ch tPc dd cua phan ting dien hoi trong
toin bd. D6 lisu phin cue nPng dd khi su gidi han la do su tii khPi; su phin cue hoat hoi
khi su gidi han lido su phdng din - ion hoi. Trong mPt sP truefng hpp cPn co su phin cue
didn trcr gin liPn vdi su sut the' ohm trong dung dich.

3.4.2. Cd che
Cung nhu ddng hoi hoc, tPc dp phan ting toin bp phai dupe tinh tir cac quy luit tPc dp
cua cic giai doan so cip. Nhting giai doan niy phai dupe phep vP mit nhiet ddng luc va dip
ting cic tieu chi sau:
- M6i giai doan so cip chi co mPt sP it cic lien kit hoi hoc bi phi vd hay hinh thinh,
hoic chi cd su tai cua mPt sP ft electron.
102
 - C6 th van dung nguydn litrang thdi dimg nhu ddi vdi ddng hod hoc.

- Ddi vdi phan tfng phuc tap Id kd't qua cua cac phan trng nd'i tidp, giai doan quydt dinh
tdc dd phan ting trong toan bd duqc goi la giai doan quydt djnh ve mat ddng hoc, hodc mdt
cdch ngan gon la giai doan gidi han.

3.5. DONG HOC CCJA Stf CHUyIn DIEN TiCH. QUA TH' HOAT HOA. PHUCJNG
TRINH VOLMER-BLTTLER

C3 day chung ta quan tarn t6i tdc dd chuyn didn tich (electron hoac ion) qua ranh gidi
pha didn cue / dung djch. Giai doan chuydn didn tich mang dac trung didn hod thuc thu.
Ngtiy nay nguoi ta da chting to duqc rang giai doan phong didn - ion hoa cua bat ki
qud trinh didn cue ndo cung din bidn vdi mdt tdc dd huu han. Vd mat thuc nghidm, dd dat
duqc didu ndy ngudi ta phai tao ra cac didu kidn sao cho cac giai doan khac, ngodi giai
doan chuydn didn tich, khdng phai la giai doan gidi han, do dd thuyd't vd su chuydn didn
tich qua ranh gidi pha con duqc goi la thuyd't phong didn cham.

3.5.1. Mota hien tilting

Tti dang didu cua dudng cong phan cue (dudng cong trong he toa dd mat dd dong -
didn the' ) he dien hod duqc chia thanh he nhanh va he cham.
A ,
He nhanh. Xdt he didn hod gdm mdt didn cue platin nhung vao dung dich Fe ,
Fe3+. Khi khdng cd dong didn luu thdng, didn cue co didn thd can bang FeJ+/Fe2* duqc tinh
bang phucrng trinh Nernst. Ndu dat mdt didn thd <p> <p&i, /? , trdn didn cue cd mdt ddng
didn (ddng andt) tuong ddi manh luu thdng, ngay ca khi {<p-q> /Fe2, )nho. Hoan toan
tuctng tu, khi <p < <pfj, , mdt ddng didn (catdt) cudng dd tuong ddi ldn luu thdng, ngay
ca khi qua thd nho. 6 ca hai trudng hop , trdn didn cue platin cd mdt ddng didn manh luu
thdng ngay ca khi didn thd <p ft khac vdi didn thd can bang PFeJ+/FeJ* , didu nay cho thtiy tdc
dd chuydn electron trdn platin Ik cao. Hd didn hod dang xdt thudc hd nhanh. Hidn tuqng
cucmg dd dong luu thdng trdn didn cue la cao cd thd duqc phan tich nhu sau. Trong dung
dich chi chtia hdu hdt la Fe2+, didn thd can bang se la <p3 nho hon didn thd can bang
/Ft2*
X1 trdn. Khi dat vao didn cue mdt didn thd <p><pa thi chi gay ra duqc su oxi
hod Fe2+ (dudng cong chtim cha'm andt trdn hinh ve 3.5),
Trudng hop dung dich chi chtia hdu hdt la Fe3+, didn thd se la <pc > tp /+ Khi dat
mdt didn thd <p<(pc vao didn cue thl da gdy ra su khir Fe3+ (dudng cong chtim chdm catdt).

103
 Hinh 3.5. Duimg cong phdn ci/c trong hi nhanh

Khi tr6n hai ion Fe2+ va Fe3+ vao nhau thi duPng cong ph&n cue t6ng hop nh&n dupe
(dupng lidn ndt trdn hinh 3.5) se la su td hpp cua hai dudng cong rhanh phn (cic ducmg
chm cha'm).

i= ia + ic
Ddi vdi cic hd nhanh se t6n tai mdt min didn thd theo do hai phan ting didn hoa ngupc
chidu nhau xay ra d6ng thai vdri tdc d6 ngang nhau
Ox + ne Red
*
Tai didn thd c4n bang <p0x/Red
6 dong bang khdng (i = 0) do do

'a. o 'c, o 'o

D6i vdi hd nhanh, ddng trao ddi i0 bidn thidn tti 10 3 ddn 1A/ dm2

Hd ch4m

As(lll)

Hinh 3.6. Dudng cong

phdn cue cua he chdm

As(lll)

0i$n thg

Xet cap oxi hoi - khu As(V) / As (III) trong m6i tructng axit. D<5i vdi cap nay didn thd'
can bang ia ipQ, . Ndu dat vao didn cue platin nhung vao dung dich mdt didn thd' <p cao hon

104
<pcb (<p > q, ); cirdng dd dong luu th6ng vin gin nhir bang kh6ng chirng nao chua dat mdt
dien the' rd't khac vdi dien th can bang ( xem hinh 3.6).
Tuung tir, d quan sat duuc cirdng dd ddng dien cua su khir As (V) thi dien thd catdt
phai khac xa dien th can bang. Mdt he dien hoa nhir viy la he cham. Scr dl phai dat vao
dien cue mot dien the' khac xa dien the can bang vi cac phan umg dien hoa xay ra cham.
Trai vdi he nhanh, cr he cham khdng t6n tai min di6n the dihai phan ung dien hod nguuc
nhau xay ra ddng thai. Dong trao ddi i0 r#t nho (iG < 10"6 A / dm2). Tir day suy ra, dien cue
platin nhung vao dung dich As (V) / As (III) khdng co dien the xdc djnh. <pCb duuc xac djnh
tir su tinh nhiet ddng luc va khdng do duuc.
Cdn luu y rang mdt cap oxi hoa - khir co thd la he nhanh ddi vdi mdt dien cue song la
he chdm ddi vdi dien cue khac. Thi du ddi vdi cdp H+ / H2. Vdi dien cue platin, i0 = 10" 3
A / cm2; vdi dien cue thuy ngdn i= 1(T12'3 A / cm2. Vdi ba giai doan su cdp va bdn cu che
co the co, thuc nghidm cho thdy:
- Vdi platin va rddi (M): giai doan gidi han la su khuech tan khi hidrd vdo dung djch

h3o+,mh -> H2
- Vdi thuy ngdn vd chi (M): giai doan gidi han la su phong dien cua proton

H30+ - MH H2

Cac. dien cue loai mdt va loai hai la cac he nhanh. Cac cap oxi hoa - khir thudc he
chdm thi cd nhidu hun. Dien hinh la cdp oxi hoa - khir co chua oxi, thi du cdp As04 /
~

As03 ; cdp 02 / H20, khdng phu thudc ban chdt kim loai lam dien cue.
3.5.2. Phuurig trinh Volmer-Butler doi vdi st/phdrig dien - ion hod
Ne'u qud trinh dien cue ducrc gidi han bdi giai doan phong dien - ion hoa thi ddi vdi
dang khai quat cua phan ting dien cue.
Ox + ne Red
ta cd bidu thtic td'c dd i :
1 = a - 1 U v6i :

i. = nFv,Ox
(1- a)nFtp
= nFk+exp .CRed (3.10)
RT

va licl= nFvRed
-anFip
= nFk exp C,Ox (3.11)
RT

105
 Khi ia = I icl = ic thi difin th strong cdc phucmg trinh (3.10) va (3.1 1) trd thanh didn
th can bang <pcb diroc tmh theo phucmg trinh Nernst (cplk didn th khi co sir liru thdng dong
didn trfen didn cue). Do d6 tur (3.10) vk (3.11) ta c6

_
(1-ct)nFff>eb -qnF<Pcb
i0= nFk+exp RT
CRed = nFk_exp RT
"ox

VI rcp-cpnentCrlS.lO) vkG.ll)rut ra
(1- a)nFq
la = 1q exP
RT

vk ILI = iQ exp -anFri

RT

T6'c dd cua qud trinh chuyn difen tfch i, bky gid se bang

!(1-a)nFr|"
e
(l-a)nFii
RT
-exp
[-anFr) (3.12)

Phucmg trinh (3. 12) m6 ta su phu thudc cua mat dd d6ng ivko qud th hoat hod q vk la
phucmg trinh co ban ddng hoc cua su chuyn didn tlch. Phucmg trinh (3.12) duofc goi lk
phucmg trinh Volmer -Butler. Su bilu difen d6 thi cua phucmg trinh Volmer - Butler cho ta
cdc ducrng cong phkn cue ting vdi cdc thanh phdn andt, catdt cung nhu dudng cong phan
cue tdng hop (hinh 3.7).

Hinh 3.7. Cdc du&ng cong phdn cifc andt

vd catdt (du&ng chd'm chd'm). Du&ng cong
phdn cue t&ng hap i(dudng lien net)

Mdt s6 he qua cua phucmg trinh Volmer-Butler.

Khi qud th hoat hod r| bangkhdng (trang thdi cdn bang cua didn cue) thi khdng c6
dong dien luu thdng (i = 0), tir phucmg trinh Volmer-Butler, ta tha'y lai phuomg trinh
Nernst ddi vdi the dien cue cdn bang

RT, [Ox]
ch =cb+ 1"
nF [Red]

106
 - Tir phucfng trinh Volmer - Butler c6 th xdy dung cac duong cong ph&n cue img vdi
cdc gia tri khdc nhau cua ddng trao d6i vd tir day se thdy lai mdt cdch dinh lucmg nhflng
khai nidm da duoc dua ra mdt cdch djnh tfnh trong phdn m6 ta hidn tucmg 6 muc 3.5.1.

0.05

l/A.cm"2
Hinh 3.8. Cdc dating cong phdn cue
Volmer - Butler tai cac gia tri i0 khdc Q
nhau (1).J0~3 ;(2) 10~5 ;(3) 10~7; (4)
10~"

Hinh 3.8 bidu thi cdc dudng cong dbng - th cua mOt c3p Ox / Red theo phucfng trinh
Volmer - Butler vori cdc tham sd n = I; a = 0,5; T = 298 vd i0 /A.cm-2 la 10~3; 10~5 ; 10~7;
10~9 tfng vcti cac ducmg cong 1-2-3-4. Ttir hinh ve suy ra nffu d6ng trao d6i c6 gia tri rift 1cm
thi qua th r) thuc t Id bang khdng, kh6ng phu thu6c d6 1dm cua d6ng didn luu th6ng, day
la trucmg hop cua didn cue khdng phan cue. Trai lai nu dong trao d6i cd gid tri nho thi
didn cue se bi phdn cue: phai dat m6t qud thd' kha ldrn vao didn cue thi mdfi cd duoc mdt
dong didn cd cucmg dd dang kd. Bang 3.1, ghi lai ede gid tri cua dong trao d8i i0 ddi vofi cap
H+ / H2 va m6t s6 cap oxi hod-khir khdc theo thir tu giam din.
2
Bdng 3.1. Dong trao dl l0 / A.cm

Nhttng cap Redox khac

C*pH+/H2
Kim loai Kim loai Kim loai Ox / Red
"'E'o "Igio -'8o
Pd 3 Fe 7 Pd c 3+ 2+ 2.2
Fe /Fe
Pt 3,1 Sn 9 Pt
Fe3+/Fe2+ 2.6

Rh 3.6 Cd 10,8 Pi
Ce44/ Ce3+ 4,4

Ni 5.2 Mn 10,9 Cu
Cu2+/Cu 4,7

Au 5.4 Pb 12 Zn
Zn2+/Zn 4.7
Cu 6 Hg 12,3 Fe
Fe2+/Fe 8

Pt 11
o2/h2o

107
 Mdt sd trudng hap gidi han khi vln dung phuang trinh Volmer - Butler.
Nhu vha dd cap a trdn, phuang trinh ca bin cua su phdng didn - ion h6a bidu thi su
phu thudc lln nhau cua hai dai luqng mat dd ddng va qui thd hoat hda. Mat dd d6ng nly cd
do 1cm phu thudc vao hai yd'u td, do la ddng trao ddi va clu true lap kep. Dong trao ddi lai
thay ddi kha nhidu tuy theo timg loai didn cue, chlng han, i0 cua N3,N2/Ptblng 10~76
A.cm2 trong khi do ddi vcri Hg2+, Hg / Pt thi i0 bang 1010 A.cm"2 tuc 1dm han 86 lln. Dd
lam sang to phuang trinh Volmer - Butler hay xdt hai trudng hap gidi han :

RT
- Trucrng hop khi qui thd' hoat hoa co gia tri kha nho (q ) khoang 10 mV.
nF
Phuang trinh Volmer-Butler se cd dang don gian han khi khai tridn ham mu (ex 1 + x):

(1- a)nFq anFr|

1 SSI
,|[u RT
1-
RT

nFq
1 Ss I (3.13)
~RT

hole ti= . (3.14)

nF i0
Cac phuang trinh (3.13) va (3.14) cho thly khi qua thd' co gia tri nho thi mat dd ddng
RT
ti 16 thuan vdri qui thd. Ndu goi dai luctng - = Rp thi (3.14) cd dang
nFi0
q = RP.i (3.15)

(3.15) bidu thi mdi quan hd tuydn tinh cua qua thd vao ddng, tuang tu nhu ndi dung cua
dinh lult Ohm ddi vdi vat din loai mdt, do dd RP duqc goi la didn tra phln cue vl nhu vdy
ranh gicri pha didn cue / dung djch duqc xem nhu la mdt thd vat din loai mdt.

Til (3. 14) , tha'y ring tai mdt mat dd dong i da cho, dong trao ddi i0 cang ldn thi dd
phln cue didn cue cang nho. Tai gidi han khi iQ oo thi q -> 0 , didn cue nlo dap dng didu
kidn nay duqc goi la didn cue khdng phln cue K tudng. Nhflng didn cue so slnh duqc chd'
tao dua trdn ca sd cua nhflng hd co dong trao ddi ldn.

Thi du: - Ddi vdi didn cue IT1" / H2, Pt, ddng trao ddi bang 0,79 mA /cm2. Tinh cudng
dd dong trdn didn cue chuln co didn tich 5 cm2 khi didn thd dat vlo didn cue II5 mV; cho
tC = 25va aH,= l.

108
 Giai: 6 didu kifen da cho v6 nhiet d6 va hoat d6 proton didn the can bang Nernst bling
khdng, do do 5 mV Ik qua the. Dua gia tri nay vao phuong trinh (3.13) va luu y rang
RT 1
-= 25,68 mV; n = 1 ung v6i phuong trinh phan ung khir proton H* + e H2

i= - 0,79 mA.cm 2 x (
25,68mV
) = - 0,154 mA.cm 2

1= lil x s = 0,154 x 5 = 0,77 mA.

Chuy.

Gia tri &m cua i chutng to d6ng electron xua't phdt til didn cue, hudng vt phia dung
dich chtia H+ .
aT
RT
= 0,097 1 churng to gia thiet su gin dung tuyn tmh la dung.

Nhung dien cue co i0 > 0 dupe goi la dien cue phan cue If tuong. Dien cue giot thuy
ngan trong phuong phap do dien mao quan thuoc loai difin cue nay.
RT
- Trucmg hop qua the' hoat hoa co gia tri 1dm (
nF
r\ ) khoang 100 mV trb Idn (qua
the duong va am), mpt trong hai s6 hang mu cd the dupe bo qua:
+ Neu rj = r|a > 0 thi
"(l-a)nFtia
* i exp hoSc

--
l= ia
RT

RT RT ,
(3.16)
ha = lni In i
(l-a)nF (l-a)nF

+ Ndu ti = r|c < 0 thi

-anFric hoac
1
* !c = "i0 exp RT

RT , . RT, .
rie = -lni +
-anF anF
-
lni.. (3.17)

Tir hai phuong trinh qua the an6t (r|a ) vi qua the cat6t ( t]c ) o trdn ta co hai phuong
trinh tuyen tinh cua Tafel:

ha=a + blgi (3.18)

2,303RT 0,059
VOl b=
(l-a)nF (l-a)n

109
va a = - bigi0

r|c = a' + b Igi (3.19)

RT 0,059
vcn b'=- 2,303
anF an

va a = - b lgi0

Nhu v4y khi qu4 the khd Ion du

Hinh 3.9. Dircmg cong phin cue
cua su chuyen difin tfch khi a = 0,5
ho4nh tai diem lg ie. Tir d6 ddc cua hai nh4nh andt v4 catdt
chuydn a .
mang d4u duong hay 4m thi qua the'
se phu thubc tuyen ti'nh vao logarit
cua mat d6 dbng. Phirang trinh tuyen
tfnh n4y mang ten Tafel khi dng
jighien cull thuc nghiem su phong
dien cua H30+ tirdung dich H2S04
loang tren dien cue platin.
Hinh (3.9) biiu thi duemg ph4n
cue Tafel dtfi vdi a = ~ . Dudng biu
din lam xu4t hien hai nhinh ph4n cue
an6t va catdt. C4c nh4nh nky se trd
th4nh nhung doan thang khi qua the
c6 gi4 tri du lefn. Bang ngoai suy d6
thi cc doan Tafel d6i vdj qu4 trinh
andt v4 catdt ta nh4n duoc d6ng trao
ddi hai doan thang se cat nhau tai true
ta c6n xac dinh duqc he sd

Thi du: - Nhung du kidn thuc nghiem dudi d4y, thu ducrc dd'i vdi dien cue Fe3+, Fe2+ /
Pt cr 25C:
r|/mV 50 100 150 200 250

I/mA 8,8 25 58 131 298

Xac dinh mat dd dong trao d6i va he s6 chuyen ddi vdi qua trinh dien cue (cho bie't
dien rich dien cue Pt bang 2 cm2).
Gidi. Sif dung phucmg trinh Tafel. Ve d6 thi lni phu thudc x\ . Su phong dien
2+
Fe3+ + e -> Fe2+ doi hoi mdt electron chuyen qua ldp kep, se 14 giai doan gidi han.
L4p bang:
110
 q/mV 50 100 150 200 250

I/ mA.cm2 4,4 12,5 29 65,6 149

lni 1,5 2,53 3,37 4,18 5
Ini

4.1:

3.37

2,53

0 50 100 150 200 250 300 r|/mV

Hlnh 3. 10. Dtfimg thing Tafel ddi vdi h Fe3* / Fe2*

Hinh 3.10 cho th&'y or midn qua th cao, dirong biu di6n lni phu thuOc r\ lk mdt dudng
thing. (!) midn q < 150 mV, dirang Tafel khdng thing. Sir ngoai suy dufrng thing tdi gdc
toa do cho gia tri true tung bang 0,916, d6 la gia tri cua lniQ, suy ra iQ = 2,5 mA / cm2.
Duimg thing co d6 dOc bang 0,0163; d6 la gik tri cua = 0,063 raV, suy ra a =
RT
0,58.
D xky dung gian d6 Tafel cin bit hai tham sO qua th va mat d6 dOng. Dl xic djnh
thuc nghiOm hai dai luong nky ngufri ta sir dung mOt thidTl bi ba diOn cue nhu hlnh ve 3-11.

i 5 2 3
Hinh 3.11. Thii't bi do quA th/
t.Difin cue so s4nh; 2. Difen cue liim vi$c; 3. D6i cue; 4. Difin th k; 5. Mao quin Luggin.

Ill
 Trfen so d6 thid't bi, di6n cue lam vide lididn cue trfen do ngudi ta nghi6n ctiu qua trinh
difen hoi. Dong didn t6i hoic di kh6i di6n cue lim vide, dupe kiem tra qua ngu6n diftn
ngoai. Nu S li di6n tich difen cue va Ili cucrng d6 ddng thi mit dd dong i = Th cua
S
.
din cue lam vide dupe do so v6i m6t didn cue so sinh, thudng la din cue calomel. NhP
difen th k, din cue lam vide vi di6n cue so sinh dupe dit vio txang thai cin bang, nhu th
se kh6ng co dong difin t6ng hop nao luu th6ng qua ph&n niy cua mach. Khi cuPng d6 dong
thay d6i thi lim cho didn th cua dien cue lam vifec thay d6i theo. Bang di6n th k xac
dinh dupe gii tri mdi cua difin the so vaii di6n cue so sanh.
De do qui th bang h6 ba din cue, nguoi ta ntfi di6n cue so sinh vdri didn cue lam vific
bang mao quan Luggin d tifeu giam dA sut th ohmic. Hinh 3.10 cho thSy co su phi hop
tuyn tinh tdt giua r\ va lni, tit day hai dai lupng quan trpng li i0 vi a dupe xac dinh, cho
phdp nhin nhin dung dan v ci'u true lop kep. Bang 3.2 ghi lai m6t vai tri s6 cua hai dai
lupng a va i ddi vPi cic phan urng didn hoi khic nhau trn m6t s6 kirn loai khac nhau
dupe diing lim di6n cue.

Bang 3J. Cac gii tri cua m&t dd d6ng iQvi hfc s6 chuydn a 6 25C

a
Phan urng Dien cue
A-cm 2/la
Pi 7.9.10"4

t
H+ +e -H2
. Ni 6.3. 10"6 0,58

, 2

Pb 5,01. 10"12 0,5

Hg 0,79. 10"12
Pe3+ + e Fe2+ 2.5. 10"3
Pt 0,58

Ce4* +e Pt
4.I0"5 0,75

3.5.3. Anh huting cua cau true ldp kep tdi dong hpc cua spchuyen dien tich
Khi thit lip phucrng trinh co ban cua ddng hpc qua tiinh chuyn difin tich, ta da c6 hai
don gian hoi sau:
a) N6ng dd chit tham gia phin ting didn hoi dupe liy la n6ng dd <r trong 16ng dung
dich.
b) Th didn cue cp dupe xem lihidu didn th cua didn cue va dung dich

p = A<J> = (j>M 4>s .

112
 Vdi hai don gian hoa trdn, phacmg trinh Volmer-Butler dupe thiPt lap trdn cd sd bo qua
qua cu true ldp kep. Sir bo qua nay se khdng c6 nghla khi trdn didn cue cd su ha'p phu die
bidt (su ha'p phu khdng co ban chat tinh didn) cac ion. VI ldp kep bao gid cung cd mat d
ranh gidi didn cue / dung dich ndn su chuyn didn tfch bi cdn trd ddng hoc or phn cufng cua
ldp kep tai do cd didn thP <j\ , nhu thP khdng phii toan bd didn thd (p tham gia vao su chuy&i
dipn tfch ma chi mdt hop phn cua <p turc la (-<J2) khu tru d ldp cumg cua ldp didn kdp
true tid'p ddng gdp vao giai doan sd c&p cua su chuyn didn tfch. Hop phn cua didn thd
<p la dien thd cua ldp khuech tan Gouy. Day la su hidu chinh thu nha't ddi vdi didn thd. Su
hidu chinh thur hai dupe tid'n hAnh ddi vdi ndng dd cha't oxi hod hay khit. Ndng dd cua
chung d bd mat ldp kep tuan theo dinh luat phan bd Bolzmann, turc la su lidn hp giua ndng
do bd mat va ndng dd trong ldng dung dich tuan theo phuong trinh

C,-C?exp|- (3.20)

6 day Zj la dipn tfch (kd ca du) cua chat phan dng, didn cue. Difin thd ldp khudch tan
<jh cd dau trung vdi da'u cua didn cue va ngupc vdi dau cua cha't phan ung. Phucrng trinh
(3.20) cho thay ddi vdi su khu catdt ndng dd cation d ban Gouy cao hon so vdi trong long
dung dich, trong khi dd ndng dd anion Lai tha'p hon. Vdi hai hidu chinh nay do su cd mat
cua ldp kdp, cac dong thanh phin andt va catdt cd dang

ia
;
- nFk C
nrk+CRed L::n-ZRedF<t>2 .exp U-aWy-fc)
exp

~ZQ"F< n-anF()
li|ic|I - nFk' C .::n
nrK_u0x exp .exp

Trudng hop cha't khur Red khdng mang dipn tfch (ZRed = 0 va Zqx = n ) thi hai phucmg
trinh ddng thanh phn 6 tren trd thanh:

a = nPk+CRed exp(1 "F<Z>.exp (1

(3:21)

-(l-a)nF<
jic|| = nFk_C0x exp -anF<?
j.

.exp-
rt RT

So sanh (3.21) vdi (3.10) va (3.11) thay rang cd thdm sd' hang expo)nF s<5
RT
hang nay phan anh anh hudng cua ldp kdp tdi td'c dd qua trinh dipn cue theo dd dac trung
cua anh hudng nay phu thudc vao didn thd' <k cua ldp khud'ch tin.

0 - PLT0H4L/O - A 113
 3.6. Li thuy't quA th hidro

Nhir da dd cap or phdn trudc, qua thd cua sir thoat kim loai trdn cat6t nho, khdng dang
k trong khi do su thoat khi doi hoi qua thd' ldn. Qua the cua su thoat khi hidro phu thudc
nhieu vao ban chat vat lieu kim loai lam catht vh. c 6 gia tri bidn thidn trong mdt dai rdng tir
khdng ddri 0,78 V tuy thudc tung kim loai. Vide khao sat vd mat ddng hoc cua su thoat
hidro chang nhtfng gop phn lam sdng to ccr chd cua qua trinh didn cue ndi chung ma cdn
co y nghia cdng nghd cua cac qua trinh didn hoa nhu an mon kim loai, ma didn, tdng hop
dien hoa... Ngay tCr 1905 Tafel da la nguai du tidn nghidn cuu thuc nghidm su thoat hidro
trdn cac kim loai catdt khac nhau da thidt lap duqc phuong trinh kinh nghidm cua su phu
thudc tuyd'n tmh qua thd vao logarit cua mat dd dong. Do la phucrng trinh mang tdn dng cd
dang khai quat:
f| = a blg| i]
Cac gia tri 'hue nghidm cua b dtfi vori mdt s<5 kim loai 1km catdt duqc ghi lai or bang 3.3
dudi day.
Bang 3.3. Cac gia trj cua b (V) dot \6i sir phdng din ion hidro a 25C

Kim loai b Kim loai b

Ag 0,12 Hg 0.12-0.15
Al 0,12 Ni 0.11
Au 0,08-0,12 Pb 0,23-0,3
Bi 0,10 Pi nhSn 0,19-0,3
C 0.84 Pi phu den Pt 0.02 - 0,08
Cd 0,25 Rh 0.14
Cu 0,12-0,16 Ta 0,34
Fe 0,12 T1 0,08

Bang trdn cho tha'y tham sd Tafel b thay d6i vdri ban chat didn cue; song dtfi vdi nhidu
2RT
kim loai, b cd gia tri gan vdi 0,12, didu nity co nghia la b bang - khi dung logarit tu
F
nhidn thay cho logarit thap phan, va nhu
vay phuong trinh Tafel se c6 dang
0,8-- 2RT ,
n = a- ln|i|
0,6--
D6 thi (3.12) minh hoa quy luat tuyn
0.4-- tinh cua Tafel ddi voi mdt s6 kim loai
catdt trdn do cd su phong didn cua ion
0,2 hidro tor dung dich axit sunfuric loang vdi
mat dd d6ng catdt bidn thidn tir 1CT6 ddn
- 6,5 -5.5 -4,5 -3,5 lg|i| lO'A/cm2.
Dd thi 3.12. Bie'n Ihien qu6 the vcri mat dd ddng.
114 B-PirGH&VD-B
 D6 thi cho thd'y cric dudng thang hdu nhu song song chdng to tham sd b la nhu nhau
ddi vdi mdt s6' catdt duqc xet. Nham c6 gang giai thlch If thuydt quy lu&t tuydn tfnh cua qua
thd' hidro, nhidu nha didn hoa tir thcri Tafel da dua ra c&c thuydt khac nhau song dang liru y
co hai thuydt,dd la thuydt xuc tac cua Tafel vh thuydt phdng didn cham cua Frumkin.

3.6.1. Thuyet Tafel ve qud the hicfro

Nghidn cuu anh hucmg cua ban chat catdt tdi sir phdng didn hidro tit dung dich axit
sunfuric loang, Tafel di tdi ket luan: co nhung kim loai xuc trie tdt cho sir hinh thanh phan
tir hidro nhu Pt, Pd, Ni, Cu...song cung c6 kim loai xuc tac am, can trd su tao khi hidro,
chang han nhu Hg, Sn, Cd...Dd' li giai tac dung xuc tac cua kim loai lam catdt trong su thorit
hidro, Tafel cho rang su khir ion hidro g6m hai giai doan so ca'p lidn tid'p:

Giai doan didn hoa hoc: H+ + e H (1)

Giai doan hoa hoc : 2H > H2 (2)

Mdi giai doan so ca'p c6 mdt tdc dd ridng vri trong trudng hop chung ca hai tdc dd ddu
co mat trong phuong trinh tdc dd tdng quat cua torin bd qua trinh didn cue, vi vriy ddng hoc
dien hoa tuan theo che dd ddng hoc h6n hop. Trong trudng hcrp nay, tir ddng hoc khrii quat
ngufri ta da chumg minh duqc ring qua trinh trong toan bd tid'n tdi trang thai dimg d do tdc
dd cua hai giai doan se bang nhau, tire la n6ng dd nguydn tir hidro trdn b6 mat didn cue
khdng thay ddi nua. Vd mat If thuydt trang thai dimg chi dat tdi trong thori gip lau vd cung.
Tuy nhidn nd'u mdt trong cac giai doan xriy ra cue nhanh thi qua trinh tuong ting se tdc khac
dat tdi trang thai can bang va do do giai doan kia se quyd't dinh tdc dd cua qua trinh trong
toin bd (giai doan gidi han). Chd dd ddng hoc luc nay duqc goi la ddng hoc thurin khidt va
trang thai ddng xay ra ngay tir luc bat ddu phan ting didn hoa. Ddi vdi trudng hqp hidro vdi
hai giai doan didn hoa va hod hoc thi tu thcri Arrhenius cho ddn nhflng nam 20 horic cham
hon cua thd' ki hai muoi, y kid'n chu dao vin cho rang giai doan didn hod xiy ra nhanh hon
nhidu giai doan hod hoc. Chfnh vi le dd ma Tafel cho ring giai doan kd't hop hai nguydn tir
thanh phan tir hidro la giai doan gidi han, va tac dung xdc trie cua kim loai lam didn cue co
anh hudng quan trong tdi giai doan gidi han nay. Vi trang thai dung dat tdi ngay tir dau ndn

d[H]_ (m)
dt V
dt / 1
{ dt
J2
Theo giai doan ( 1) tdc dd tao thanh nguydn tir H ti Id vdi mat dd ddng i:

MhII _|i| (b)

dt

Theo giai doan (2), tdc dd mat di cua cric nguydn tir H duqc bidu thi bang bidu thtic:

115
 (m) = k[Hf (c)
dt n
Mat khac, do giai doan 1 dat trang thai can bang, th didn cue duqc ti'nh theo phuong
trinh Nernst:

<p =
RT
-
[H+
InV-r (d)
F [H]

Tir (a), (b), (c) rut ra [H] = j rdi thay vao (d)
*'kF

dt |~H+ ~1
Ta duoc <p - -In , -
hoac
F

RT . r +~i
Kl
a- -In H
F

RT
L
-- J
RT,In l RT
2F
Kl
11 + -
InkF
2F

u
hay * ri=

rj = a
RT,InkF
-
2F
.-
--
c RT, I I
In i

b In|if
2F
Phuong trinh nay co dang cua phuong trinh da duoc Tafel tidn doan

0,059
song hd stf b c6 gia tri thay vi gia tri thuc nghidm bang 2 x 0,059. Nhu th thuydt

xuc tac cua Tafel khOng cho duoc kdt qua phu hop vdi thuc nghidm. Tuy nhidn o thdi dim
dd If thuyet cua Tafel da giai thfch duoc tac dung xuc tac cua kim loai toti su kt hop hai
nguydn tu H thanh phkn tvr H2 va dilu nay da dua tdi nhihig gid tri rdt khac nhau vi qua thd
hidro trdn cdc kim loai khac nhau.

3.6.2, Thuyet hien dai ve qua the hidro (thuyet phong dieri cham cua Frumkin)

Thuyd't Tafel vd qua thd hidro da dua tdi gia tri b bang mdt phdn tu tri sd thuc nghidm
ia didu khdng thd chdp nhdn duoc. Hon ntfa anh chup trdn dao ddng ki cho thdy thoat ddu
khi vijra n6i didn qua thd tang tuydn tfnh vdi thdi gian va nhu vdy qua thd ti id vdi didn tich
luu thdng r6i mdi ti 16 vdi luqng nguydn tu H. Didu nay cho phep gia dinh rang giai doan
didn hoa ia giai doan gidi han tdc dd qua trinh didn cue. Ngudi ddu tidn (1930) dat ndn
mong cho co chd didn hod nay la Erdey Gruz va Volmer vd duqc Frumkin hodn thidn vao
nam 1933.
116
gradien
' dr)
=
d Ini

ndu a = .
2
RT
aF
=
--
2RT
F

Nhu thd ndu su phdng didn

-
Ndu giai doan dien hoa cua sir phdng didn ion hidro trd thnh giai doan gidi han thi ap
dung phucmg trinh Volmer - Butler ddi vdi qua trinh catdt ta co

proton la giai doan gidi han thi

dd dd'c cua dudng thing thuc
nghidm se la

F
9RT
-2,303. =-0,120 V
.

Mdt ln nura ta tha'y lai dang

cua phuong trinh Tafel vdi
-aFr|
=1<>exp-
RT

-
180

120

-60
hay

r|/mV

-
rj =

Sy phOng
RT . .
RT Ini0 --

di6n chm

2.303.RT

Hinh (3.13) bidu thi qui thd hidro theo hai thuydt Tafel va Frumkin,

3.7. DQNG HOC KHUECH TAN VA QUA TH NONG Dp

-In

cua proton
i

120mv

2,303.2 RT/F

30mV

Mdt trong nhung gia thid't duqc sir dung dd thidt lap phuong trinh ddng hoc cua qui
trinh phong dien ion hoi - phucmg trinh Volmer-Butler - dd la su ddng nha't vd ndng dd
dung dich d khu vuc gin dien cue va didu nky cung duqc van dung cho ca trucmg hop khi
hd chua can bang. Gia thiet nay se khdng con ddng nQa khi mat dd ddng cd gia tri ldn
khidn cho qua trinh khudch tan chat v6 didn cue trd ndn rdt cham, khi dd su khudch tin cd
thd trd thanh giai doan quyd't dinh tdc dd qua trinh didn cue. Hidu ung nhy goi la su phan
Thuyfet xuc tAc
Tafe!

Hinh 3. 13. Do thi qud th?hidro phu thudc mat do

ddrtg theo hat ihuyet phong dien cham vd xuc tdc.

Kdt qua nay cho thdy mdi khi mat dd dong catdt tang mircri lin thi qua thd trd ndn am
hcfn 0,120 V.

cue ndng dd, va de qua trinh didn hoa cd the didn ra vdi tdc dd dang kd thi phai dat mdt qua
the kha ldn: qua thd phu nay la qui thd ndng dd (cung duqc goi la qui thd khudch tin),

3.7.1. Si/thiet lap phuong trinh dong hoc khuech tan

Khi mat dd dong tdng quat trdn hd didn hoi bang khdng thi can bang duqc thidt lap, khi dd
ap dung phuong trinh Nernst cho chat phan utng cd hoat dd aM+ trong long dung dich, ta

co: ?=?
o RT,
~~p" 3m

117
 Ddi vdi hd didn hoa khdng can bang (mat dd d6ng tdng qut khic kh6ng), ndng dd ldp
dung dich sat didn cue thay ddi. Khi do hoat dd aM. trd thanh aM, va the' didn cue c6 ddng
didn luu thdng co dang:

o RT.
o>' = <p + In a
nF Mn+

Qua the n6ng dd qD gay bcri su thay ddi n6ng dd se bang:

RT , aM,w
tId =<P'-<P =\n-y
nF aM-

Nd'u dung djch la du loang dd co the thay hoat dd bang n6ng dd, phudng trinh qua the
n6ng dd tret thanh:

RT, C (3.22)

vdi C va C la n6ng dd chat Mn+ & dung dich va trdn hd mat didn cue.

Dd Ion cua qua the ndng dd se duqc xdc dinh khi biet n6ng dd C cua chat phan ting
trdn be mat dicn cue. Su khdc nhau giua C' va C phu thudc va dd ldn cua he sd khudch tin
ion trong dung dich: nd'u linh dd cac ion ia kha ldn va he sd' khud'ch tin D co gia trj ldn thi
su kh4c nhau giua C' va C kh6ng dang ke, ngay ca khi mat dd ddng ldn.

Cach don gian nhat de xac dinh ndng dd bd mat C' la xua't phat tur dinh luat Fick vd
khudch tan. Dinh luat nay lien he thdng luefng khud'ch tan chat (ludng chat khudch tan
thang goc vdi be mat didn cue quy vd don vi didn rich bd mat phang, trong don vj thdi gian)
vdi gradien cua ndng dd:

a) b)

Hinh 3.14. Su bien thien ndng dd Iheo khoang edeh tdi didn cifc

118
 6 day D la he sb khudch tan c6 thti nguydn trong hd SI la m2. s 1 (don vi thbng dung
cua D la cm2.s_1). D co dp lbn khoang 10~5 m2.s_1 dPi vcri cic chat trong dung dich. x la
dC
khoang cich toi bd mat didn cue va la gradien cua nbng db.
dx
Dinh ludt Fick dupe dp dung cho ch db khudch tan dung, khbng tinh dd'n su didn
chuydn vd su dPi luu. Su bien thidn n6ng dp chat do khudch tdn, theo khoang each x tbi be
mat didn cue dupe bid'u thi trdn hinh (3.14),

Trdn hinh 3.14 a, ducmg cong C'LM mb gradien n6ng db H thuydt theo do su bidn
ta
thidn n6ng dp co thd trien khai tir bd mat didn cue tai day n6ng dd la C\ tbi sdu vao long
dung djch co n6ng dp C. Day la trubng hop dung dich tinh khbng bi khudy trpn . Khi co su
khuay dung dich, ndng dp co thd xem gdn dung la khbng dPi tai mpt didm nao do cua lop
bd mat each didn cue mbt khoang edeh bang 5 , dp Id bd day lop khudch tan Nernst, tai day
nPng dp bid'n thidn tuydn tinh theo khoang each x (hinh 3-14 b) vd nhu vdy d6 thi gradien
nPng dp C'LM dupe thay bang C'NM.
Phuong trinh Fick bay gib dupe viet:

J= -D*
dx

C -C
J a -D-
5
ThOng lupng khudch tan cua chat mang didn tich ne se ung vbi mat dp dong i theo
phuong trinh:
i = nFj

i= -nFD (3.23)
S
Bd day 5 cua lbp khudch tdn se giam ndu tang tPc dp chuydn dbng cua dung dich so vbi
didn cue. Tai gid tri hang dinh cua 8 , mat dd dPng se tang khi C giam. Khi nPng dp bd mat
C giam tPi khbng thi mat dd dbng dat tbi gid tri gibi han iL.

nFDC
L (3.24)
5
Chia phuong trinh (3.23) cho (3.24), ta dupe:

i -C'-C
= -uhay =1,
i C'
i. C i, C

Tir day
C

C
=1
--
i
i.
C
. Thay tir phuong trinh nay vao (3.22) ta duoc:
C

119
 / \,
RT,

nF
In (3.25)
L >
Phuong trinh (3.25) con dnac vid't dudi dang ddi vdi dong khuech tan

i= ii 1-exp-nFrio (3.26)
RT

Thi du. Xac djnh mat dd dong gidi han trdn didn cue nhung vao dung djch chura Cu2+
c6 ndng do 0,01 mol/1. Cho bid't 5 = 0,5 mm va D+= 7, 1.10" 6cm2/s.
Giai: Sir dung phuong trinh (3.24) tinh mat dd d6ng gidi han iL vdi n = 2;
F = 96500; D = 7, 1.10 6; C = 10"5 mol / cm3; 8=5. I0~2cm
nFDC

2x96500x7, 1.10" 6 x I0"5

-2
5.10

= 2,74.10"4A /cm2 hay 0,274 mA/ cm2.

Gia tri 0,274 mA / cm2 cho thy ddng didn hudng tdi didn cue 1 cm2 khdng thd' vum
qua 0,274 mA trong dung dich. Trucrng hop dung dich duoc khua'y trdn va co sir thay ddi bd
mat didn cue (nhu trong cue phd), su tinh dong gidi han se phdc tap hon.

Cac phucmg trinh (3.23), (3.25) va (3.26) la nhung phuong trinh co ban cua ddng hoc
khud'ch tan dung.
Tir phuong trinh (3.26) co thd' nit ra ma'y nhan xet sau day:

Khi r)D = 0 thi i = 0 ( hd didn hoa can bang).

Khi -qD co gia tri dm , Idn thi i iL .

( RTl
Khi r]Dco gia tri rat nhd ( |riD| , su khai tridn ham mu ddi vdi r|D iam cho
V nF )
phuong trinh (3.26) trd thanh:

nFqD
1-1-
RT

nFqD
i= -ii
RT

i phu thudc tuydn tinh vao r)D

120
 Co th torn tit cic trudng hop khac nhau cua sir phu thudc d6ng khuich tin vao qua
thd ndng dd bang dd thi trong toa d6 phu thu6c r|D (hinh 3. 15).
'l

-7 -5 -3
0,5

-- 1

Hinh 3.15. Dudng cong phan cue dd? vdi su khuech

Di qui trinh dien hoi duqc thuin lqi, phai giam qua thd. Qui th n6ng dd t|D tai mdt
gia tri da cho cua mat dd d6ng, se giam khi ting ndng dd C cua dung dich. Mat khac qua
th ndng dd cung c6n c6 thi b| giam khi giam bdt bi day lop khudch tin 5 bang cich
khuiy trdn hoac tang hd s6' khudch tin ion bang su ting nhidt dd.
Ddng hoc khudch tin cung vdi cic phuong trlnh dinh luqng co ban d6 cip d trfin, dng
vdi trang thai dung, khdng c6 su khuiy trdn dung dich. Didu nay ft c6 y nghla thuc tidn d6
la vi di dat tdi chd dd khud'ch tin niy cin nhidu thdi gian (hing gift ddng h6). VI viy trong
thuc t, qua trinh dien cue duqc thuc hidn hoac theo ch dd diirng c6 su khuiy trdn dung
dich hoac theo chd dd khdng dimg. Theo hudng
thCr nhi't cua ddng hoc didn hoi, qui trinh didn cue
duqc tid'n hinh vdi mdt didn cue dia quay; C6n cr
hudng thd hai ngudi ta sir dung phuong phip cue
phd hoic cic phuong phip hdi phuc.

3.7.2. Dong hoc khuech tan ddng vdi dien cue

dia quay
4

Dd thiit lip chi dd ddng vdi su khuiy dung

dich ngudi ta sd dung mdt loai didn cue duqc goi
la didn cue dia quay (hinh 3.16).
Dd li mdt dia kim loai (thudng la platin) kich
thudc nho duqc gin vao mdt vat cich didn. Hinh 3.16. Dien cUc dia quay

Vit cich didn cung didn cue dia duqc gin vdi
mdt true quay ndi vdi mdto didn. Trong khi quay,
didn cue dia duqc phin cue bang mdt ddng didn
ngoai. Khi didn cue quay, dung dich chuydn ddng
theo hudng tir tam didn cue sang hai phi'a goc, tir
1.Dia platin; 2. Nhua Teffon
cich difin; 3. Day din di6n; 4.
Hirdng chuyn dftng cua chit long:
5. Dung djch.

121
phfa dudri ldn phfa trdn hudng tori tim didn cue. Theo If thuydt thuy ddng lire hoc, tai tdc dd
khdng ddi cua d6ng chay ting cua dung dich gin didn cue, bd day ldp khudch tan dat gii tri
gidri han khdng ddi, duqc xic dinh bang phuong trinh:

fvx

6 diy Id d6 nhdt ddng luc hoc; x Iikhoang edeh tcfi bd mat didn cue; u Id tdc dd
v
dong chay ting giafi han.
Mat khac vdi didn cue dia quay, thuydt thuy ddng luc hoc con thidt lip mdi quan hd
gitfa bd day ldp khudch tin vd vin tdc gdc cua didn cue:
8 = 1.62D1'V/6or"2 (3.27)

vdi co la vin tdc goc cua didn cue dia quay.

Thay 5 tir (3.27) vdo phuong trinh (3.23) ta duqc phuefng trlnh dong khudch tan
i= -0,062nFD2/3v~1/6oj1/2(C -C) (3. 28)

Cic hd sd 1,62 vd 0,62 trong hai phuong trinh (3.27) vd (3.28) Id do thtf nguydn duoc
chon d5i vdi i la A/ cm2, ddi vdi D va v Id cm2/ s ; ddi vdi C Id mol/cm3 va co Id rad/s.
Phuong trinh (3-28) duqc nghidm dung trong trudng hop chit ndn phai du va nhd viy md
c6 thd loai trCr su didn chuydn. Phuong trlnh d6ng khudch tin dOrng vdi didn cue dTa quay
duqc thidt lip bang U thuydt cho kit qua phu hop khd tdt vdi thuc nghidm (sai sd 1%). 6
nhung dd phin cue ldn, khi d6 C' -> 0 ,dong khudch tin itrd thanh :

iL = 0,62nFDv~<oC (3. 29)

Khi liy phuong trinh (3-28) chia cho phuong trinh (3-29) se thiy lai cic phuong trinh
da thidt lip 6 phin trdn :
(C-C) .
-vd i = iL 1-exp fnFhol
RT
Didu nay chung to su khuiy dung dich khdng lam bid'n ddi dang cua dudng cong phin
cue, ma cdn rut ngin rit nhidu thdi gian thidt lip trang thii dilrng tir vai gid xudng cdn chua
diy mdt giiy.

3.7.3. Phuong phip cue pho

Tir (3 - 29) thiy ring tai 8 = const, dong gidi han ti Id vdi ndng dd C cua chit trong
dung dich. Su phu thudc nay Id co so d! nha didn hda hoc Tidp khdc Heyrovsky xiy dung
ndn mdt phuong phip phin rich, dd Id phuong phip cue phd (1923) trong phin tich d|nh
tfnh va dinh luqng cic chit c6 kha ning bi khu trdn catdt thuy ngin. Hlnh (3-17) trinh bdy so dd
nguydn If cua phuong phip cue phd vdi didn cue giot thuy ngin. Thidt bi do cue phd gdm mdt

122
binh cue pho A chua dung dich nghidn curu. MPt d6ng hidro dupe thPi qua Png dan B vao
dung dich dP duPi oxi. Tir bdu chufa thuy ngan C, thuy ngan chay vko dung djch qua mpt
mao quan D c6 dudng kfnh khoang 1- 2mm cho phep tpc dp nho giot tir 20 - 30 giot trong
mpt phut. NhiJng giot thuy ngan se dong vai tro catPt thuefng xuydn dupe dPi mdi va tinh
khiPt. Mpt IPp thuy ngan dupe trai 6 day binh A se d6ng vai tro anPt E. Catdt C va anot E
dupe dPu vao cue am va cue duefng cua ngu6n didn F. Hidu thP giua anPt va catPt dupe biPn
dPi nho con chay J chuydn dich doe theo dipn tro HI. Cucmg dP d6ng dipn trong mach dupe
chi trdn dipn ke G. Vi didn tich cua anPt E ra't 1dm so vdi dipn tfch giot thuy ngan, hon nura
cucmg dp d6ng dien thudng lai nho, khoang lOA, ndn co thd xem anPt khPng bi phan cue
va su phln cue catPt dupe thuc hipn nho hidu thP bid'n dPi tir bdn ngoki. ThP cua catPt bi
phan cue, dupe do so vdi mPt dipn cue so Siinh nao do. Do dPng dipn luu thPng tren difin
cue giot thuy ngan la mpt ham cua thdi gian nPn trong khi do, giitri cua dong dupe lPy
trung binh theo chu ki nho giot cua didn cue. DP thj cua dong trung binh Iphu thuPc the <p
dupe goi la phP d6. Dong trung binh Idupe Ilkovic tinh todn dPi vdi dipn cue giot thuy
ngan, cd dang :

T = 607nDmt(C-C') (3.30)

vori m la khPi lupng (mg) giot thuy ngan rcri xuPng trong mOt giay ;t la thPi gian trung binh
(s) sPng cua mot giot thuy ngan; C la nPng dP chPt (niol / cm3); D la hp s6 khuPch tdn
(cm2 / s).
Tai gicri han khi C' > 0, phuong trinh dong trung binh gidri han co dang:

IL =607nDmtC (3.31)

Khi giai phuong trinh thP dipn cue cua dipn cue giot thuy ngan dPi vdri dong trung binh
umg vdi cac phan Ung va san phdm cua su khir catPt, va dPi vdi dong gidri han, thu dupe biPu
thurc dPi vdi thP:

<P = <P\/2+
nF ln"kr-
I
(3.32)

vdi <pm dupe goi D thP nira sPng, chi phu thupc ban chPt hp oxi hod - khir.

Tir (3.32) suy ra phuong trinh dPi vdi } :

1= -- - (3.33)
nF
1+ exp

Pho d6 umg vdi phuong trinh (3.33) co dang dipu cua mPt sdng, dd la song cue phP
(hinh 3.18)

123
 G

*L

-q>

Hinh 3.17. So dd thi&t bi Hlnh 3.18. Sdng ci/c phd

don gian nha't ve arc phd'

Trucmg hop dung dich chura nhidu chat phan img trfin catdt thi cung vdi su tang dan cua
hi6u th6' gitfa C va E (con chay se di chuyfcn tir Itori H), cuomg d6 dong tang theo hinh
"song", do la song cue ph6. M6i s6ng se ting voi sir khu dien cua m6t chat. Hinh (3.19)
biu thi s6ng cue ph6 trong dung dich CaCl2 0,1 N chtia cac ion d6ng, chi, cadimi, kem,
mangan va bari n6ng d6 10" 4M. N6'u dong gidri han IL duoc su dung d xac dinh dinh
luong chat trong dung dich thi th nira song <p1/2 duoc dung d xac dinh tinh chat. The' nua
song la the' ting vdri dim u6n cua ducmg cong cubng d6 th (xem hinh (3.18)).

Bang 3.4 dudi day ghi lai the' nua song dd'i vdi mdt s6 ion.
Bang 3.4. Th nua s6ng so vdi dien cue so snh calomel IN

Cation Dung djch nen rpml\on

Cu2+ O.INKNO3
-0,02

Sb IN KQ -0,19

Ag+ -0,34
KCN + KNO3

Pb2+ IN KQ -0,47

Cd2+ IN KQ -0,68

Zn2+ INKCl - 1.06

Ni2+ IN KQ -1.14

Mn2+ IN KQ -1,55

124
 Cation Dung djch nn <pin/\on
I
ai3+ 0.05NKCI -1,75

TCli**

Hlnh 3.19. Song cite phS

LTu dim ndi bat cua phuong phap phan ttch cue ph6 la cho phep phan tich lupng nho
(10~ 4 -10~3 mol/1) cua mdt s6 ldn cac chat trong dung dich. Han chd cua phirong phap la d
chd b6n canh d6ng Faraday con c6 d6ng d tich didn ldp kep, do d6 khdng phai toan bd
chidu cao song cue phd ti 16 vdi ndng dd chat trong dung djch ma chi mdt phan nao do cua
s6ng la ling vdi dong Faraday. Nu ddng Faraday nho hem dong tich di6n ldp kdp thi dd
chinh xic cua phutmg phap cue ph<5 giim nhanh.

3.8. CO s6 THUYt LtfONG tCTv PhAn tfNG DlfiN Cl/C

3.8.1. Cau true electron cua kim loai

6 day chi gidi han xdt ede electron linh ddng trong mang tinh th kim loai. D6 la
nhiing electron hoa tri se tham gia vao su trao ddi giua didn cue va dung dich. Trong su gdn
dung bac nhat, nhiing electron hoa tri nay dupe xem ia chuyin d0ng tu do trong mang tinh
th, tao ra mdt ldp khi electron. Nang lupng cac electron nay c6 ngudn g6c la ddng nang,
do dd v6 nguydn tac c6 th bidn thidn tir khdng dn vd cung.
Cac electron dupe phan bd theo cac miic nang lupng khac nhau, theo Iu0t thdng kd
Fermi - Dirac, theo dd xac su#t P (E) d mdt mute nang lupng E bi chidm dupe xac dinh
bng bidu thiic:

P(E) = (3.34)
1+ exp
(E-Ef)
kT

125
vdi Ef Ik nkng lucmg Fermi cua kim loai, c6 gid tri khdng dli 6 nhilt dd thudrng.

TCr (3.34) thly rang dl E = Ep thi ham Fermi P(E) bang - . Tai OK, P(E) bdng 1 nlu
2
E < EF vk P (E) = 0. Khi E > Ep. Su phu thuftc cua P (E) vko ning iircmg E dude biu thi
trdn hinh (3.20). 6
nhung
nhilt dd cao hon, ducmg cong
c6 mdt dilm uln tai E = Ep.

6 dilu kiln nhilt dd

thucrng (25C) do nang lu<mg
kT qua nh6 so v6i nkng luong
Fermi (0,025 eV so vdi 2-10 11 E/eV
eV) , mk P(E) c6 nhiing gid tri
rkt khac 0 hokc 1 tai vung Hlnh 3.20. Hdm Fermi - Dirac
tuong d(5i hep cua nkng luong 6
hai phia cua mure Fermi.
Nhu vky mkc du duoc xem lk hokn tokn tu do, ede electron c6 nang lu<mg thk'p hon
muc gicri han nao dd (muc Fermi chkng ham) thi thuc tl khdng tham gia vko su dan diln vi
nlu P(E) = 1 thi tat ca cac miic nkng lucmg c6 thi cd da bi chilm, electron mat kha nkng di
chuyln do khdng c6n ch6 trdng. Trdi lai nlu P(E) = 0, c6 nhilu miic trdng dl c6 thi tdfi
song lai khdng c6 electron.
Tom lai mdt each gkn dung c6 thi xem ckc electron hod tri cua kim loai cd miic nkng
luong trung blnh bdng miic Fermi.
Tu phuong trinh (3.34) ta tinh duqc xac suit chilm ciia mdt electron (quy vl mdt don
vj thi tich) co nkng lucmg nkm giiia E va E + dE, phai nhkn xac suk't nay vdi mat dd trang
thai nkng lUong (bi chilm hay khdng bi chilm) pdE. Hkm mkt dd trang thdi nkng luong c6
phuong trinh:
13/2
2m jl/2
p(E) = 4n (3.35)

d dky h lk hang s6 Planck, m lk khli luong electron. SI electron trong don vi thi tich
c6 nkng luong nkm givta E va E +dE, se bang:
1
n(E).d(E) = p(E).P(E)dE = p(E) (3.36)
(E-Ep)
1+ exp
kT

126
 TCr day tdng s<5 electron trong kirn loai duoc xac dinh bang each lay tich phan phuong
trinh (3.36) tiit 0 den <x> .Trong sd electron nay, nhflng electron nao dupe xem la linh ddng
thi phai co ning lupng Ion hon m6t gia tri gidi han nao do.
Mdt each tirong tu, mat dd trang thii khdng bi chiem (16 h6ng electron) duoc cho bang
cong thuc
1
n(E).d(E) = p(E).[l - P(E)]dE = p(E)- dE (3.37)
1+ exp
(e-ef)
kT

Cho ddn nay electron hod tri vin dupe xem la khi electron di chuydn tu do trong kim
loai va kh6ng tuong tac voi mang tinh thd. Su thuc nhflng tuefng tac nay t6n tai va khdng thd
bo qua dupe. Nhung muc ning lupng co thd co cua electron dang le bidn thidn tir 0 ddn
co thi lai chi bidn thidn trong mpt khoang gidi han nao do, dupe goi la nhung dai. D6i vdi
don chat m6i dai se ung vdi m6t trong s6 cac muc ning lupng electron trong mpt nguydn tur
c6 lap tuc la ung vdi m6t obitan nguydn tur. Tnrcrng hop cic hop chat, mdt dai se irng vdi
mdt obitan phan tur.
Trong kim loai, mdt electron dupe xem lilinh d6ng ndu dai ning lupng cua n6 phai co
nhflng ch6 trO'ng. Tir day phat sinh hai khai
1 r nidm d6 la dai hoa tri va dai din.
4,3eV:
;7,7eV Dai hoa tri la dai nang lupng tha'p trong
Dili 4s do cic muc electron ddu da bi chidm. Dii
i 4s. -" ' ' Oil 3d din se ling vdi mtfc nang lupng cao b do cac
10 .
-3d - v\\W
muc hay c6n trdng hoic bi chidm ptdt phin.
>o
Trong thuc td nguPi ta chi co vin dd vdi
3P nhflng dai hoa tri vi dai din co mure nang
c - 100
z
KO
3s
lupng rit gin nhau. Trong trucrng hop nay
ngucri ta goi dai hoa tri la dai cudi cung
hoan toan bi chidm theo truth Jru tang din
2p
1000 cua nang lupng. Dai b ngay phfa trdn dai
2s hoa tri li dai din. Nhq viy d6i vdi kim loai
d6ng (Is2 2s2 2p6 3s2 3p6 3d10 4s1) chi
- 10000
1s nhflng muc 3d va 4s lico ci'u true dai. Mtfc
Nguydn tCr Tinh thi 3d hoan toan bi chidm se ung vpi dai hoa tri
c6 l$p
con mure 4s con trtfng se li dii din. Hai dai
niy mdt phin xen phA vao nhau, didu niy
Hlnh 3.21. Cau true dai cua dSng lam ting kha ning didn chuydn cua
electron. Hlnh (3.21) m6 ta su sip xdp cac
dai. Trdn hinh ve, nang lupng ion hoa cua
nguydn tir c6 lap la 7,7 eV, con ning lupng thoat electron la 4,3 eV.

127
 Ddi vdi kim loai nhe hem nhir natri thi dai din Ik mite 3s. Dai niy xen phu mdt phin
vio dai 3p cdn trdng.

3.8.2. Hieu ling hm cua electron

Chan khong
Muc trdn da dd cip tori sir phin bd mure
ning luqng electron trong kim loai qua him
phin bd Fermi - Dirac P(E).
Vi'n dd dat ra cf day \h trong phan urng
chuydn didn tfch cr ranh gidi kim loai - dung
djch, electron se vuqt qua hing rio nang luqng
x =0
nay nhu thd nao dd co thd tori duqc chit nhin
electron trong dung djch. Dd co thd giai dap
duqc vin dd khdng dem gian niy, trudc hdt hay
Hlnh 3.22. Thi'ndng cua electron trong
kim loai vd trong chan khdng (Vt # V2)
xet su chuydn electron qua ranh gidi kim loai -
chan khdng bang gian dd thd nang electron, V
theo khoang cich x trong kim loai vi trong chan khdng (Hinh 3.22).

Gia thiS't trong kim loai, thd nang electron tai x < 0 li V,, cdn a bdn ngoii kim loai
(chin khdng) tai x > 0, thd nang tuomg dng liV2.

Hang rao nang luqng duqc dung Idn tai ranh gidi x = 0 giua 2 pha. Electron se vuqt
hang rao nang luqng nhu thd nao dd chuydn tu kim loai vio chin khdng?

Trong kim loai, nang luqng toin phin cua electron Ej duqc xac djnh Wang bidu thuc :

Ej1 = + Vj1 (3.38)

2m
Nang luqng toin phin cua electron trong chin khdng Ej bang

EJi+v,
2m 2 (3.39)

Chung nao khdng cd su phit vi thu btfc xa (su chuydn electron duqc xem la khdng burc
xa), nang luqng toan phin cua electron b hai phi'a cua hing rao nang luqng la nhu nhau, tiic
la Ej= E2 hoac

(3.40)

128
 2
Gia thiet dbng n&ng electron trong kim loai,
2m
, tha'p hem chiPu cao hang rko nang
2
lucrng ( V2 -V,) tire la < (V, -V.) thi theo quan nibm c6 diPn electron khbng thP nhay
2m
tir kim loai vao chan khbng.
2
Tir (3.40) < 0. Mat khac dai lupng m6men dbng binh phuong (p2 ) khbng the am,
2m
khPi lupng m cua electron la dai lupng ducmg, nhir v$y dbng nang cua electron trong chan
khbng khong thP am. KPt qua am cua dbng nSng khdng thP dupe chap nhan theo quan diPm
c6 diPn cua ccf hoc Newton dp dung cho cac vat thP vT m6 dtfi voi trirdng horp xet trfin hinh
(3.22).

DP giai quyPt bki toan dtfi vdri vat thP vi mb nhu electron phai van dung quy luat lucrng
tir theo do xac suat tim tha'y electron tai mbt diPm trong chan khbng dupe tfnh bang binh
phuong bidn dp xac sua't trong chan khbng. Dai lupng 2 phu thubc vao dpng nSng va
thP nang electron trong chan khbng nhu sau (su tfnh todn dua vao cac hp thurc Planck va
de Broglie):

/ 2
H-exp-j-- P2 V, t-p2x (3.41)
+
2m

vori i= 4~\ ; h =
2tc
; t la then gian.

- 2 2
Tir su phan tich b trbn vP dai lucmg
2m
< (V2 -V<), da tha'y < 0 tire la
2m
p2 < 0. VP
mat loin hoc p2 la dai lupng ao, se bang dai lupng thuc p2 nhan vdi sP ao i:

p2 = ip2 (3.42)

Dua p2 tir (3.42) vao (3.41) ta dupe

~ exp W+ 2m
V, t-ip'2x (3.43)

NPu bo qua yPu to thai gian, chi xet ypu tP khoang each x tir kim loai dPn chan khPng,
(3.43) trcf thanh:

i ip2x p2x
2 ~ exp Arexp (3.44)

9 * PUOHAUD - A 129
 (3.44) cho thdy khi xem electron la tiu phan mang tfnh chdt s6ng thi sit cd mat cua
electron trong chan kh6ng duoc xlc dinh bang binh phuong bidn dd xdc sud't 2 ; 2 bay
gid chi g6m cac dai luong thuc p'2 , x, A . Nhu vay su nhay electron tir kim loai vao chan
kh6ng bi ngan cam bdi co hoc Newton thi lai duoc ph6p bang co hoc luong tir.
Su co mat cua electron trong chan khdng mac du ddng nang electron trong kim loai
thap hon trong chan kh6ng duoc giai thich bang hifcu ung hdm theo d6 thay vi phai leo qua
hang nang luong, electron da xuydn qua dudng hfim cua hang rho nang luong Ai chuyn
vao chan khdng, dieu tudng chimg khdng th xiy ra d<5i vdi electron trfin ranh gidi pha kim
loai - chan khdng.
Xac suat tim thay electron trong chan khdng cung co co nghia 1& xdc suat ham PT duoc
xac dinh bang phucmg trinh

PT=|4f =exp (3.45)

(3.45) cho thay xdc suat co mat electron trong chan khdng se giam theo ham mu vdi
khoang cdch x tfnh tir bd mat kim loai. Nhtfng dim trong chan khdng cng xa b6 mat kim
loai cang it kha nang tim thay electron.
Hinh (3.23) minh hoa hidu ung hdm cua electron trdn ranh gidi kim loai - chan khdng.

electron xuy6n
dirimg hAm
NSng luong
electron ~
trong kim loi

x
Hinh 3.23. Hieu ting hdm cua electron

3.8.3. Hieu ung hdm cua electron giua V]

/
dien cue va ion trong dung dich / Dung djch
Kim loai /
Nhu* da bidt, co sd cua thuydt luong tu /
v hidu umg hdm cua electron khdng burc /
/
/
xa la: nang luong toan phdn cua electron
la nhu nhau d phia bdn ndy vd phia bdn kia
cua hang rao nang luong. Trucrng hop didn
A
cue - dung dich, electron xuydn hdm co
ciing nang lucmg tren didn cue cung nhu Hinh 3.24. Hiiu ting hdm cua electron
trong dung dich. Didu ndy duoc th hidn gitia didn cue va dung dich
trdn hinh (3.24).

130 9 pjeH&iro

-e
 Didu kidn dd electron xuydn him chuydn tir kirn loai vo dung dich linang luong trdn
kim loai Ey phai bang nang luong trong dung dich EP.
Tu muc trudc ta da thay ring n&ng lupng trung binh cua electron trong dai din kim loai
bang nang lupng Fermi EF . Dd bat electron khoi mure Fermi, chuydn vao chan kh6ng b xa
v6 cue thi phai tieu ton c6ng 0> . M6t each tuong tu, tu xa v6 cung trong chan kh6ng (ung
v<jti mure nang luong kh6ng cua electron) khi chuydn vd muc Fermi, electron phai sinh c6ng
(J) ; Nhu vay O dupe xem la nang luong trung binh cua electron trong kim loai (so vdi nang

luong khdng trong chan khdng), do do

Ep=
Tir didu kidn xuydn him (Eq- = EP) suy ra

EP= O
Dd electron co the xuydn him chuydn tir kim loai vao dung dich c6 chua chit oxi hoi
thi trang thai nang luong electron cua chit oxi hoi trong dung dich phai phu hop vdi
nguydn If ngoai trir Pauli. Gia sir EP < <t> , hidu bng him cua electron khdng xay ra do
nguydn If Pauli bi vi pham (hinh 3.25).

loai Dung
dich

| Nang luong
NSng luong/
! chit oxi h6a
Fermi y. i( cua IOp dung dich
i gin kim loai

x =0 8 x

Hinh 3.25. Hiu ung ham hi can trirdo chat oxi hod
(nhan electron) khdng cdn obitan trong

Dd electron co thd xuydn him va thuc hidn phan irng khur thi O < EP.
Didu nay dupe minh hoa trdn hinh (3.26) vdi O < EP.
Nghidn curu hidu ung him ddi vdi su chuydn electron giura kim loai didn cue va proton
hidrat hoa H30+ trong dung dich theo phan dng
M (e) + H+ - H20 M-H + H20
Ngucri ta thidt lip dupe md'i quan hd giOa nang lupng EP va cac dai luong

131
 - nang lucmg hp phu A cua nguy&n tir H vcfi kim loai M

- nang luong cua tuong tac dy R giira nguySn tu H va nguyfin tCr O cua H20 0 khoang
each gan.

- nang lirong ion hoa hidro d thu duoc m6t electron 0 xa v6 tin trong chan khdng , I

- nang Iirong hidrat hoa ion H+, L

Ep = A R + 1+ L
= (I + L) - (A + R)
Di6u kidn d electron xuyfen h&m, chuyln til kim loai tdi H30+ trong phan ufng khfr
proton hidrat hoa la

a> <EP
d> (I + L) - (A + R)
hoac (A + R) < (I + L) - d>
e~ 60c
trong
trong
chin
khong chan
Dung khbng
Kim dich
loai

Dung Nang luang chat

dich nhn electron trong lop
dung dich gan kim logi

X=0 5 x

Hinh 3.26. Electron duoc phep xuytn ham do Ef > d> , tai do trang thdi
trd'ng ndng lucmg tao thuan loi cho electron chttyen vao.

Cac s6' hang nang luong trong phuong trinh (3.46) duoc cho trong bang (3.5) doi voi sir
khuhidro trdn platin.

Bang 3.5. CAc gia tri cua so hang nang luong doi vdi sir khu hidro tren platin

S6 hang Nang lucmg ,kj 1 mot

R 96,14

A - 209,00

I 1308,34

L - 1124,42

132
 So hang Nang luong ,kj / mol

O 501.60

R+A - 112,86
I+ L- Cp - 250,80

Cac trj so vd nang Iirong ghi trong bang trdn ddu ung vdi khoang each c6 dinh giffa
nh&n hidro va be mat kim loai , va do do R + A >I + L-<t>; Vdi kdt qua nay electron
khOng tdi dupe H30+ bang hipu ung ham de thuc hidn phan ting khir hidro. Mau thuin nay
duqc If giai bang su khdng hang djnh ciia R, A, va L theo khoang each giufa H - H20 (ddi
vdi R), giiraM - H (dd'i vdi A) va H+ - H20 (ddi vdi L).
Ndu bieu didn su phu thudc ciia thd nang theo khoang each tdi bd mat dien cue ddi vdi
hai he M(e) + H+ - H20 va M - H + H20 ta thu dupe 2 dudng cong thd nang tuong ting
(hinh 3.27).

Kim

oai s
Dgrig electron hoa cua he

R +A

Trang thai co
Trang thai ca
b; ban ciia he
M M(e) + H4 - H20
x x
KhoAng each tdi kim loai

Kim
ioei /
He truwc luc khir

Hinh 3.27. Sukhu ion hidro chixdy ra khi lien ket

H* - H20 dMc keo edng de nang luong AE bi thu hep t&i khdng

Gia thidt trudc khi thuc hidn phan ung khir, ion hidro chidm vi trf x gitia bd mat kim
loai va phan tir nude, thd nang cua hd M(e) + H+ - H20 duoc bidu thi bang didm Y tren
.
dudng cong thd nang I+ L - <I> Neu tai x su chuydn electron tir kim loai tdi H+ dupe thuc
hidn thi xay ra su bidn ddi:

M(e) + H+ - H20 - M - H + H20

va hp se d vao trang thai bi electron hod, M - H + H20, vdi nang lupng dupe bidu didn bang
diem Z tr6n dudng cong the nang R + A ung vdi didm x.
133
 Khi H+ 6 vi tri x thi R + A > I+ L - O tire la
(R + A) - (I + L - <t> ) = AE , nhir vay hieu ung hm cua su chuydn electron tit kim loai
hudmg tdi H+ trong dung dich bi ngSn cdm.

Hinh 3.27 cho thdy chirng nao H+ cdn each xa bd mat kim loai mdt khoang Ion hem
khoang each tori han x' thi electron khdng thd xuyen ham. Ndu ion hidro hidrat hoa cr vao
trang thai nSng lupng co ban thi khoang each giua n6 va kim loai la cue dai ting vdi gia tri
cue dai ciia AE, didu nay lam electron khong thd xuydn ham tori H+. Din theo su keo cang
lidn kdt H+ - H20, AE giam dan va su keo cang dat cue dai ting vdi vi tri x1 cua H+ thi
AE = 0 khi do
R + A = 1+ L- d>
Dieu kien xuydn ham dupe thoa man va electron co thd ten dupe proton dd thuc hidn su
khir. Mpt khi nguyen tur H duoc hinh thanh thi su ph<5i hop cua hai hidu urng day giua H va
H20 va hut giua H va kim loai lam nguydn tir H bi hap phu ldn kim loai.
Tdi day co che cua su chuydn electron trdn ranh gicri pha didn cue - dung dich da duoc
sang to.

3.9. PHUONG PHAP THUC NGHIEM vi OQNG HOC

CAC PHAN CfNG D1EN HOA

Trong nghidn cuu thuc nghiem vd ddng hoc didn hoa, ngupi ta chia cac phuong phap
nghidn cuu lam hai loai. Loai phuong phap c6 didn va loai phuong phap h6i phuc
(relaxation method).

Trong phuong phap cd didn, dudng cong phan cue thu duoc bang su do ddng mdt chidu
luu thdng trong he dien hoa phu thupc vao thd dat vao hfi; day la phuong phap thd tTnh
(potentiostatic method). Ndu duong cong phan cue thu duoc nhcr su do thd phu thudc vao
mat dd ddng dat vao he thi ta co phuong phap dong tTnh (galvanostatic method). Phuong
phap ghi during cong phan cue cd didn duoc ap dung cho hd didn hoa khdng can bang cr do
tdc dd phan ring didn hoa la nho bd, do do d6ng trao ddi ie nho, qua thd hoat hoa 1dm hem
nhidu qua thd ndng dd , c&c thdng sd didn hoa co ban nhu hd sd chuydn a, dong trao ddi i0,
...
cung nhu cac hd sd Tafel ba, bc dupe xac dinh dd ding tu cac doan Tafel cua dudng cong
phan cue. Trong trucmg hop n&y khi cho di qua hd didn hoa mdt ddng didn co mat dd ddng
dang kd trong mdt thdi gian kha dai thi ndng dd chat trdn ranh girii didn cue - dung dich
cung khdng bi thay ddi dang kd.

Trudng hop khi toe dd phan ung didn hoa la dang kd (ddng trao ddi iD kha lorn) thi qua
trinh didn cue dupe xem la can bang (tdc dd phan ring thurin khdng khac may so vdi tdc dd
phan umg nghjch khi cd dong didn luu thdng). Khi do bang phucmg phap ddng tTnh hay thd
134
tlnh co dien, ta kh6ng do dupe ckc thdng sd dienhok cua qui trinh. Trong truPng hop nky
ta phai dung phuong phap hPi phuc (c6n dupe goi la phuong phap rich thoat). Thuc chit cua
phuong phap h<5i phuc la trong m6t thfti gian cue ngkn (105 - 10-4 giky) nhP m6t xung
dien vuOng ta (km chuyen dich the ckn bang r6i giu c6 djnh the nky, do biPn thien mkt dp
dong theo ihPi gian (hinh 3.28).

o t

Hinh 3.28. Su phu thupc thi' vd ddng theo

thtii gian theo phucmg phap thi'tlnh xung

Phuong phap do nay dupe goi lk phuong phap the' tlnh xung. Su do dupe thuc hien nhP
mOt thie't bj chuyen dung, dupe goi Ik potentiostat. NPu trong phuong phkp the tlnh xung
nguPi ta do d6ng theo thPi gian, thi ngupc lai trong phuong phkp dong tlnh xung nguoi ta
do the theo thefi gian nho thiPt bi galvanostat, khi dat vao dien cue ckn bkng (i = 0) m6t
xung dong trong thfti gian rk't ngkn (hinh 3.29).

o , t o
Hinh 3.29. Suphu thudc ddng ivd thi' cp theo thai gian t

Kit qua cua tac d6ng xung d6ng la thP dien cue bi chuyen dich khoi trang thai can
bang. Su chuyfin djch the la do: (1) su giam the' ohm iR, (2) Qui the hoat hoa , (3) Qua the'
nPng dp, (4) sir rich dien lPp kdp.
Phuong phkp ghi duong cong phkn cue trong che dp dong xurig dupe goi Ik phuong
phap dbng tlnh xung. Duong cong phkn cue con c6 the dupe ghi theo chP dp the' dpng
(potentiodynamic) hokc dong dong (galvanodynamic). Trong chP dp the' dOng, the dupe
tang tuye'n trnh theo thoi gian ( ) va ghi lai dbng nho mOt thiPt bi dupe goi potentiomet
dt
dipn tr. Cung bkng thie't bi nay nguPi ta ghi the' khi dbng dupe tkng tuyPn tinh theo thoi
/ dj \
gian
vdi,
. Toe dp quet thi hay qupt dong dupe chon thy thudc vao muc dich cua phdp do
va co the thay dPi trong m6t gidi han rpng.

135
3.9.1. PhUttig phap the tlhh xung (Pulse potentiostatic method)

Bang potentiostat, trong khoang 10~7 giay, thP didn cue dupe dich khoi gia tri can bang
khoang vai mV va dupe giO khPng dPi; khi d6 dipn dung 16p kep la mPt hang sP, con su
phu thupc cua dong i vao thoi gian t dupe xac dinh chi bang bien thien n6ng dp cha't cua
lPp dung dich gan kP dien cue. VPi t < 10 s su phu thuPc ivao t c6 dang phuong trinh

(3.47)

RT
VPi t| la dp phan cue dipn cue; 0 = la diPn tro phan cue, k la mPt hd sP, co gia tri
nFi
bang

2L
k= (3.48)
v/nnF C0qJ0Ox CRedVReT
Khi ngoai suy d6 thi cua dong i
phu thuPc thfti gian 7t tPi t = 0, se
xac djnh dupe diPn tro phan cue 0 , tiir
day suy ra dong trao dPi iG.

3.9.2. PhUtihg phPp dong trih xung

Hinh 3.30. Set do do theo phitcrng phap dong ttnh
(G.may phat xung; C binh do difn hod;
O: dao dong ki, R,: dien trd)
Hinh 3.3 1. Scf do do theo phtfemg phdp ddng
tinh co sit bu trd do giam the dm
(G - may phSt xung; C - binh do di$n hod; O: dao
d6ng ki; V: Von kfi'; R, va R3; cac din tro c6 dinh; R2:
dien trd bin ddi de bi) trir d6 gidm tb 6m)
Phuctng php nay cho phep xac
djnh cac thdng sP dpng hoc diPn cue
khi lam biPn dPi dpt ngPt mat dp dong
tu gia tri i = 0 (can bang) tPi mpt gia
tri xac djnh nao do rPi ghi lai su biPn
thibn difin thP theo thPi gian. So d6
nguyPn tdc cua phuemg phap dPng tinh
dupe thP hidn trPn hinh 3.30.
Trong so dp do trPn, dipn cue phu
trp dPng thoi la difin cue so sanh. Dien
tro R, dupe chon sao cho R( Rdd .
Trong truPng hop nay khi diPn ap cua
mdy G cP dinh thi I= const. Voi so dP
do nay, dp giam thP 6m khPng bi loai
trCr va bang Rdd.I. DP tript tiPu n6 can
sir dung so dP do thich hop (hinh 3.31)

136
 R R
Khi = thi d6 giam th 6m trong binh do se bang d6 giam th6 6m trfen R2 va
Rdd
, v
.
dao d6ng ki chi ghi lai q D6ng di6n luu th6ng trong binh do difin hod se bang Sir phu
R,
.
thu6c qua th6 ti vao thdi gian t duoc cho bang phircmg trinh:

RT. 2N r 1
n = 1 -7=vt +
nF
(3.49)
0 /

1 1
vdi N = _1_
nF Cqx n/ Ox 'RedV Red 7

Phuong trinh (3.49) duoc su dung d xic dinh ic tir su phu thu6c thuc nghiem cua r|

vo t. Song, (3.49) kh6ng cho k6t qua phu hop thuc nghidm. Thuc vy khi t = 0 thi r\ =0
vi
RT i RT i
i = 0. Khi t = 0 thi tir (3.49), rt as , nhu th khi t = 0, qua th chuyn tr 0 tdi ,
nF ic nF L
r6i lai tang ti 16 vdi Vt . (xem hinh 3.32)
Nguy6n nhin cua su khac bi6t vdi
thuc nghiem cua (3.49) la d ch6 khdng
tinh dn dong tich di6n Idp kep.
Bli
N6u chu tdi y6'u t6 nay, (3.49) se co nF L
dang khac:

RT. _/t
2N r RTKr2r, 1
~N CH + (3.50)
nF ' V7t nF o /<
Hinh 3.32. Suphu thudc qua the T] vdo thdi
gian t trong phuong phdp do dong tinh
vdi Cd la di6n dung ldp kep. dudng 1(phuong trinh 3 .49)
dudng 2 thytc nghiem.

cAu h6i va bai tap

3.1. Neu nhufng dSc trUng ciia qua trinh dien cite khong cdn blng doi v6i pin dien v6 dtfi v6i
binh di6n phan.
3.2. Phan biSt su phan cite hoa hoc vdi su phan cite n6ng d6.

3.3. d 25C tdc do tan cua Ag trong dung dich AgN03 0,1 M b&ng 100 A / m2 tai didn thd
0,74 V. Tfnh toe d6 tan cCia Ag khi dien th6 diteng hdn 0,24 V nOa.

137
 Khi dien thd giam di 0,24 V thi tdc dd tan cua Ag thay ddi thd ndo ? Cho he s6 chuyen a =
0,5; F = 96500

0S:iOi98 = 104A/m2
io,5o = 1 A / m2 .
3.4. 6 25C ddi vdi su phdng di|n ion H30+ trdn Pt
H30* + e H2, Pt + H20
o
tt/ dung dich axit, i0 = 0,79 mV / cm .
Xdc dinh cudng dd ddng dien li/u thdng tren 5 cm2 dien cut khi d|t vao dien cut mot dien the

5 mV.
BS:0,77 mA.

3.5. Bd'i vdi dien cue Pt dien tich 2 cm2

tidp xuc v6i dung djch Fe3+, Fe2+ d 25C, kd't qua do
qua thd phu thudc ddng duoc ghi lai nhu sau;
r|(mV) 50 100 150 200 250

I(mA) 8,8 25 58 131 298

Blng do thj hay xac dinh ddng trao ddi iD vd hd s6 chuyln a.

0S:2,5mA/cm2; a =0,58

3.6. Tinh hd s6' Tafel cCia qud trinh andt (ba) d 25C ddi vdi si/ chuyln dien tich d dd cd mot
electron, 2 electron tham gia phln ting. Cho hd sd chuydn a = 0,5 ,

0S:O,12 V; 0,06V.

3.7. Xac dinh ddng khudch tdn gidi han doi vdi si/ khti catdt tti dung djch CuS04 1 m d 25C
bidt ring he sd khudch tdn O ddi vdi Cu2+ blng 2.10-10 m2 / s vd bd ddy Idp khudch tdn blng 100
(im .
OS: 386 A / m2

3.8. Cho bidt thd chudn cua Cd2+/ Cd blng - 0,403 V; ddng trao ddi ddi vdi hd
didn cut
H+ / H2, Pt blng 0,79 mA / cm2. Lidu cd thd phO Cd Idn R tU dung dich Cd2+ v| H+ c6 hoat dd
blng nhau vd blng ddn vj ?
3.9. Cho bidt trong nhting dilu kidn n&o mdt kirn loai cd thd di/dc thoat ra tU dung djch axit md
khong cd sU thodt ddng ke hidro? Tai sao bac lai thodt ra dd ddng tUdung dich bac nitrat? Tai sao
Cd cd thd thodt ra tCr dung djch CdS04? (Qud thd cCia si/ tholt hidro tren Cd gin blng 1 V khi mdt
do ddng kholng 1 mA / cm2).

138
 3.10. Boi v6i stf phong didn cua H Iren kem, d6ng trao ddi vdo khoang 5.10
-1 1 2
A/ cm . Hoi
*

kem c6 thi thoat ra ti/ dung dich co hoat d6 kem b&ng ddn vj?

3.11. Hoi dien the toi thiiu nhiet d6ng hoc dl tir do kem, ding c6 thi thoat ra tCf dung djch
1M? Tinh dien the ttfang ting dfii vfii nong d6 0,01 M.
OS:- 0,76; 0,34; - 0,82; 0,28 V.
3.12. The chuln cCia <Jiin cue bac, dong, kem bang 799 mV, 337 mV va - 763 mV, Trong
dung dich xianua, ba kirn loai trdn thoat ra d6ng thdi. Gilii thich kit qua ndy.

3.13. Bang thiet bj do potentiostat ngifdi ta ghi dude duting cong phan ctic catit cCia cSp H+/
H2 ttidung dich H2S04 c6 pH = 1 6 25C. Oiin ci/c so sdnh la dien cut calomel bao hoa; diin ctic
lam vide la Pt c6 dien ti'ch 0,5 cm . Ket qua do nhif sau:

te(mV) "550 -600 -650 -700 -750

lc (mA) -2.2 "M -5'2 -7." " ,2

Tinh he so chuyen a doi v6i qua trinh catot vd dong trao doi cua cap H+ / H2 trong dieu kien
thi nghiem. The cua dien cut calomel bio hoa being 241 mV,
0S:O,23; 0,59 mA / cm2.

3.14. D6ng trao doi cua he H+/ H2 tren dien ctic kirn loai nhung vdo dung dich axit
pH = 2, bang 10~5 A / cm2. Bat vao diin ctit m6t thi b&ng - 0,70 V so vdi the cCia dien ctic
calomel bao hod.Tinh d6ng catot ic. Cho biit T = 298 K; thi cua dien cut calomel bao hoa bang
0,24 V; he s6 Tafel catot bc = - 0,13 V.
BS:41,2 A/m2

139
 Chuong 4
MQT S6 LTNH VUC Ong DyNG cOa oqng hoc oien hoa

MUCTIEU

Hoc xong chuong nay, sinh vidn co kha nang:

1. Nam duoc nguyen nhin gay ra an mbn dien hoa kim loai
2. Ti'nh toin duoc trong didu kidn da cho, kim loai bi phd buy theo cor che nao.
3. Tmh duoc didn thd an mbn, tdc do an mon.
4. Nam vflng va van dung cac bidn phap thuc td chdng lai su an mon .
5. Hieu duoc su chd tao cung nhu hoat d6ng cua cac loai ngudn didn nang nhu pin,
acquy, pin nhidn lidu.
6. Nam duoc mOt sd ting dung cua su didn phan (ma didn, tinh che kim loai).
7. Nam duoc nguydn If cua qui trinh san xudt didn hoa hoc mdt so san phdm hoa hoc.
8. Nam duoc nguydn If cua su van dung ddng hoc didn hoa vao mdt sd ITnh vuc cua hoa
hoc phan tlch.

4.1. An mon kim loai

4.1.1.Dai cuong ve an mon kim loai

An mon kim loai la mdt ITnh vuc ma khdng mdt nuoc nao trdn thd gibi khdng quan
tarn, nha't la cac qudc gia co ndn kinh td phat tridn bcri vi theo danh gia hang nam cua cO
quan phat tridn Lidn hop qudc (UNDP), an mon kim loai lam ton that kha ldn ndn kinh td
qudc dan, va chidm tbi 3% tdng san phdm qudc gia (GNP). Bcri vay, nghidn ctiu v an mon
va bao vd kim loai da duoc quan tarn tir lau. Ngay nay, ITnh vuc an mbn kim loai vin con
duoc nghien ctiu ra't manh vbi nhting phuong phap va thidt bi ngay ding duoc cai tidn va da
dem lai hidu qua ngay cang lbn. Hang nam trdn toan thd gibi hang ngan cdng trinh trong
V

ITnh vuc nay duoc cdng bd. O nubc ta, an mbn va bao vd kim loai duoc quan tarn nghidn

140
cutunhieu hem trong may chuc nam qua 6 mdt s6 vien nghien cuu va cac truing dad hoc
nhu Vien KI thuat nhiet ddi thudc TTKHTN va CNQG chuydn vfi an mon bin, Trung tam
An m6n kirn loai thudc DHBKHN chuydn vi nghidn cuu bao v6 protector.
Ngirdi ta goi an mon kim loai la mdt qua tiinh tir pha huy kim loai do tac ddng hoa
hoc, dien hoa hoc cua mdi trucmg xung quanh (m6i tnrcfng xim thuc) d chuyn sang dang
bn nhiet ddng lire cua cac hop cht nhu oxit, hidroxit, mudi.
Dua vao co chd pha huy kim loai, ngudi ta phan bidt in mon hoa hoc vdi an mon didn
hoa hoc.
An mon hoa hoc xay ra khi phan ung hoa hoc di the didn ra giua cac nguyen tvr kim
loai vdi phi kim, thi du phan ung d nhiet dd cao giffa kim loai va oxi, su oxi hoa be mat cua
nh6m trong khdng khi... Su an mon didn hoa chi xay ra trong dung dich dien phan va qua
.
trinh oxi hoa - khir xay ra bang con ducmg dien hod hoc.. Tdc dd an mon dien hoa phu
thudc vao dien the cua kim loai bi an m6n.

4.1.2. Phan loaidn

mdn dien hoa

Can cur v&o dac trung cua mdi trucmg an mdn, an m6n kim loai duoc phan th&nh:

An mon khi quydn khi be mat kim loai c6 hoi nude ngung tu.
An mon bidn.
An mdn trong mdi trudng axit, trung tinh hoac kidm.
An m6n dong do gay bdi su d6 dien khien cac cu kidn kim loai d trong dt bi phan
cue thanh an6t va catdt.
Ngudi ta cdn phan loai an mon theo dac trtmg pha huy kim loai, dua vao day ta cd:
An mon deu: su an mon xay ra d6ng du tren toan bd be mat, c6 the kem theo su
thay ddi thanh phan be mat do su hoa tan.chon loc cua cic c&u tut hoat ddng nhat cua dung
dich ran, thi du d6ng thau bi an mon trong nhieu dung dich nude do ca'u tir kem bi hoa tan..

An mon khu tru: dang an mon nay du or tim vi md hay vl m6 ddu gin lien vdi hinh
hoc cua ranh gidi kim loai / dung dich dan tdi su thdng khi vi phan cua dung dich. Dac
trung khai qudt cua dang an mon khu tni la su tdn tai cua v6 van c&c pin an mon khu tru;
chung khdng khac may so vdi dang an mon Galvani do su ghep ndi hai kim loai ban chat
khac nhau. 6 dang an m6n khu tni (an m6n hang) su thdng khi vi phan gay ra su thay ddi
tai chd ham luong oxi. Vung nao giau oxi trd thanh catdt, vimg ngheo oxi dong vai trd andt
tai day su hoa tan (an mdn) kim loai xay ra.
Su an mdn khu tru xay ra ciing manh nd'u ti sd dien tich catdt va andt cang Idn. Tit li
thuydt v6 an mdn, su an mdn xay ra khi tdng tdc dd phan ung catdt phai bang t6ng td'c dd
andt:

141
Trubng hop an mdn dbu, dibn tfch an6t va catbt bang nhau (SA = Sc), do d6

Z = Z hay
Lj q q j

Z'.=Z'c
Trubng hop an mon khu tru SA Sc do do ia 1
An mon khu tru lai dupe phan thanh cac dang :

+ an m6n hang
+ an mbn 16
+ 3n mbn nth
An mbn galvani xay ra khi hai kim loai kh4c nhau tififp xuc nhau trong cung mbt
mbi trubng xim thuc. Hai kim loai n4y tao vdi nhau mbt cap galvani v4 dupe xem nhu mbt
dien cue duy nha't trbn do xay ra nhibu phan ung anbt va catbt.

An mbn nut: Dang an mbn nay thucmg gap khi vat Iibu bi tac dbng cua ung sub't
nbi hoac ngoai cua mbi trubng xam thuc va kbt qua 14 vat Iibu bi giy hay bj nut.

4.1.3. Die tntig den hoa cua an mon kim loai

Mbt kim loai bj an mbn trong mbi trubng nubc (su ph huy mang tinh thd kim loai)
dupe xem la mbt dibn cue kbp trbn db xay ra cac phan ung:
- Hoa tan anbt M = Mn+ + ne ( 1)
- Khir catbt cua ch4t khir phan cue D
D + ne = Dne (2)
Phan ting catbt la c4n thibt db su hoa tan anbt cb thb tibp tuc xay ra vi phan ung nay
"tibu thu" cac electron sinh ra tif phan ung anbt. Nb'u goi ia va ic ia mat db dbng anbt va
catbt tucrng ting vdi hai phan ung anbt va catbt cua su 4n mbn kim loai thi khi khbng co
dbng dibn ngo4i, ia + ic = 0, tti day suy ra ia = I ici = i 14 mat db dbng an mbn.

Nhibt dbng luc hoc vi an mbn kim loai

Dibu kibn nhibt dbng luc db mbt kim loai bi an mbn trong dibu kibn da cho cua mbi
trubng xam thuc 14 dibn thb c4n bang (dibn thb Nernst) cua phan ting ho4 tan anbt phai 4m
hon dibn thb Nemst cua phan ung khir catbt, ttic 14

<,8 < Pn.C

n.s v3 "Pn.c la thb Nernst cua qu4 trinh anbt v4 catbt trong an mbn kim loai.
Dbi vdi phan ung anbt (1), dibn thb c4n bang a dupe xac djnh bang phuong trinh :

142
 RT
<Pn,* =<!>N,a +"pr'naMn
Di phan ung (1) co thd difin ra theo chidu ttr trfi sang phai, phan urng (2) duoc ghep v6i
phan ting ( 1) dd su tidu thu electron c6 thd xay ra. Cht D trong an mbn thircmg ik proton
hokc oxi:
(*) Trong dung dich axit, sit khir proton hokc oxi theo phan ting:

a) H*+e -H2 h*/h2o =

b) H*+io2+eiHiO <.,Hi0 = U3V

(*) Trong dung dich kidm chi xiy ra su khir oxi

io2+lH!0+e=iOH- Oj/OH" = 0,401V

Nhu vky a didu kidn chukn, ba didn th ring vtii ba phan ting khir H+ vk 02 trong ba
m6i tnrcrng axit, bazcr, trung ti'nh ddu ducmg do do cic kim loai dting trudc hidro trong day
didn hoa ddu c6 thd bi an m6n. Nhkn xet nay chi dung 6 didu kidn chuin. & ngoai didu kidn
chukn, didn thS' co thd ch6ch nhidu so vcri gik tri chukn vk su an m6n nhidt ddng co thd xay
ra ngay ca ddi voi kim loai dting sau hidro trong day didn hoa.. Thuc vky, ddi vdi su khir
H+ va oxi trong m6i truong axit, din thd Nernst cua hidro vk oxi phu thudc vko pH cua m6i
truimg:.
RT
<PH'/h1 ="VlnV
F
="0.059pH 625C

PD2HVHj0= 1,23- 0,059 PHd25C

Thi du: Lifiu ddng c6 thd bi pha huy trong mdi truimg c6 pH = 3?
Ung vtii phan ring didn cue Cu2+ + 2e =Cu,

RT,
didn thd' ckn bang (pCyj2+
= 0, 34 + - InT Cu2+ 1
2F *-

Didn hoa hoc vd an m6n kim loai da chkp nhan m0t nguong chung cho n6ng dd ion
kim loai bang 10" 6 mol/1, dudi nguong nay su an m6n khdng xky ra. Nhu vky 6 25C
PCu2+ /Cu = 0,34 + 0,0295 lg 10"6 = 0,163 V

Oj.rr /HjO = 1-23-0,059x3 = 1,053 V(P0j = latm).

Dieu kifin nhidt dOng lire vd an m5n d6ng duoc thoa man:

143
 ( (pQi* < <p() ) va do do d6ng bi an mdn vdi su khu phan cue oxi theo phan
/Cu /H o

ting

Cu = Cu2+ +2e
Cu + io,+2H+ = Cu2++H20
2 2
On2 + 2H+ +2e = H20 2
2

Chu y: Kdt lutin v an mon ddng trdn day duoc ti'nh khi dd tan cua oxi trong nude
P0j = ] . Binh thudmg 6 25C, oxi t6n tai trong nude dudi tip sua't ridng PQi = 0,21atm, khi
do th6' cua oxi bang H. /HO= 1.23+ 0,0295 lg - 0,059 pH
.= 1,23 + 0,02951gV(Ui -0,059x3= 1,043 V

Ddng hoc cua an mon didn hoa

Nghidn ctiu an mon dudi g6c dd nhidt ddng luc hoc cho bidt kha nang va diu ki6n xay
ra an m6n song vdn dd co tim quan trong hang ddu cua an m6n lai la.vtfn dd ddng hoc ttic
la tdc dd va nhung ydu to anh hudng tdi tdc dd an mon .
Xet mdt hd an mon g6m mdt kim loai tidp xuc vdi dung dich didn phan. Qua trinh an
mon d day bao g6m phan ting oxi hoa kim loai xay ra or khu vuc andt cua kim loai vk phan
ting khir tai khu vuc catdt. H6 an mon nay tucmg duong vdi mdt pin didn doan mach do do
rnoi dong didn xuift phat tir khu vuc andt Ia (Cudng dd ddng chti khdng phai mat dd ddng)
phai tdi khu vuc catdt. Day ia cudng dd dong an mdn Ia/m.

/m
Ngoai dac trung nay, cdn mdt dac thu nua gan lidn vdi didu kidn doan mach cua pin an
mon, do Id su tridt tidu cua hidu thd V cua pin:

V = 0 = <pc -<p +IR.

Vdi <pc va <p.A la didn thd catdt va andt cua pin an mdn, I.R ia dd gidm thd dm .Trudng
hop chung cua pin an mon d dd khoang each khu vuc andt va catdt vao khoang vai micron
thi cd thd coi IR = 0 khi a'y

Vcaa/m (4-1)

Xet mat ddng hoc cua an mon kim loai, hai thdng sd dac trung cin tridn khai ia tdc dd
va thd an mon.
*
a) Tdc do an mdn

Ndu S la didn tich khu vuc andt thi

I
AaM i s
= Ta = *a

144
 Trong trudng hop an mon kh6ng kem sir tao lbp oxit va an mon bi khb'ng che bcri
qua trinh chuyen dibn tich, co th van dung phucfng trinh Volmer-Butler db'i voi mat
do dong iu, ic

Ia / m ~ Ia ~ a-ia ~ Sa . eXP
RT
(4.2)

6 day iQ M la dong trao ddi cua phan ting Mn+ + ne M. aM la h6 sb chuyen cua

phan ting oxi hoa anot kim loai M. r|M la qua thti hoat hoa cua su hoa tan kim loai
(Pm -"Pa-N,M)va co gia triduong.

Mot each tucfng tu, db'i vbi phan ting khu catbt tren kim loai an mon, ta co:

la / m = - = Sc- ic
'-qpnFrip (4.3)
Sc.i0 D.exp
RT

V6i aD la he sb chuyen cua qua trinh khir catbt db'i vdri chat khti phan cue D. io n la
dong trao dbi dbi vdi phan ting D + ne Dnc.
r|D la qua the hoat hoa cua phan ting khu catbt

Pd = *Pc ~~ "n,D ' (Pd**0)

De' don gian hoa va'n dl ma khong lam mat y nghla cua an mon, gia thiet rang
aM = aD = '5 c 1 electron trao doi trong phan ting anot va catbt. Khi do:
/ p\ /
|!).rap{
p\

(4.4)
= k>.M exP
Urtj= o.m exp 2RT ) 2RT
/ /
a/mF \I
p p

F% Pn,dF (4.5)
!c = lo.D exp = -lo.D exp exp
2RT v 2RT ) 2RT

VI Im ~ a~ 'c'
- ia- - 'Ic' Sc

--\/'a|'c|-Sa-Sc (4-6)

Thay ia va licl tit (4.4) va (4.5) vao (4.6) ta duoc cudng db dong an mon Ia t m:
la/m- A/Stt.Sc.i0 M.i0,DexP |p[Vn,D (4.7)

-
tO- PLTDH4LTD A 145
 Phircmg trinh (4.7) cho tha'y <36 Ion cua cuing dd ddng an mon phu thudc vao dien tich
va cac yeu to can bang nhu dong trao d6i va cac thd Nernst.
t
g
V6 ydu t6' dien tich, ti s6 cang Ion thi t6c dd an mon cang ldn. Thuc vay, tic dd an
Sa
mon va/m=-
nF

Sa.nF Sa.nF nFSa nF Sa

Vi ydu t6 dien the' can bang Nemst, khi i0 M i0 D, sir an mon cang nhanh neu hieu the
Nemst cua phan urng catdt va an6t cang Ion.
tha'y ro vai tro cua dong trao d6i cua phan ting an6t va catdt toi t6c dd an mon hay
xet truing hop cua sat. Sat co the bi an mon nhiet ddng luc tir hai phan tfng catdt

(1) ST+eiH,

(2) io!+2e+2H*
2
= H,0 <.h*/h,o =>'23v
song kha nang bi an mon tir (2) nhidu hon vi {(pQ H+/H Q - <pf j Fc ) ldn. Dong trao ddi cua

(2) bang 1CT14 A / cm2 trong khi do dong trao ddi cua (1) la 10-6 A / cm2 do do phan ling
(1) xay ra nhanh hon va sat bi an mon vdi su khi phan cue hidro trong axit

b)Thedn mdn

Khi Ia = -Ic = Ia im ta co dien the tucrng urng la the' an mon <pa/m .

Sa.iG M exp.exp-
2RT 2RT
= Sc.iQ D exp-.expl
' 2RT 2RT

suy ra exp >a/mF x Sc-io.D expi77(N.M+,D)r

f F <4-8)
RT ) Sa-'o,M [2RT

hac /m-ln|-]
F[Sa.i0jMJ
+ |(NiM+iD)
2v
(4.9)

Ding qudn rang cac phuong trinh cucmg dd dong an mon (4 - 7) vi the an m6n (4.9)
ducrc thiet lap trong truing rieng a do cac he chuydn cua qua trinh andt va catdt la bang
nhau va bang 0,5; su chuyn didn tich umg vdi mdt electron.

Trong truing hop ting quat n6u aM va aD la he sd chuydn cua su oxi hoa kim loai va
su khuchdt D thi
146
 i , _ rac /au+aM TaM/aM+"D rxn aM ap F (rj. (4.10)
'a/m-U Aq.D exP , dtIPn,D yV.M)
aM +aD K1

va

9a /m
RT lnifii aM
"9n,m +
ar
Pn.d (4.11)
(aM+aD)F IOM aM+aD "M + Cr

4.1.4. Dudng cong phan cut va giSn do Evans ve 3n mdn

Cung nhu moi phan ting
didn hoa khac, trong an mon (p,

kim loai, cac phan ting an6t va <Pn,o- M=M

catdt co th duoc biu difen
bang ducmg cong phan cue <p =
f (I). <(> la dien th cua
kim loai / dung dich so vtii the

D + ne = Dne"
*2
.....
N.M
X/
cua mtit difin cue so sanh nao -1 o +1
do ((p = cpN +r\ ). Nu chi tinh Hinh 4.1. Cdc duifng cong phdn arc andt (J) vd catdt (2)
tdfi qua the hoat hoa, ducmg
cong phan cue c6 dang nhu hlnh ve (4.1).

Cucmg dd dong tai d6 Ia = ly la cuting d6 dong an mon 1 ting vtii th an mon <p,!m

Gian d6 Evans (4.1) cung ducrc xiy dung trong h toa d6 rp - f (III) hoac rp = f (lglll).
Xem hinh 4.2.
a/m

M - Mn* + ne

Tfl/lH

D + ne = D

Hinh 4.2. Gian d6 &n mdn Evans d6\ vdi dn mdn bi khd'ng chebdi suchuy/n dien rich.

4.1.5. NhQhg yeu to dong h$c quyet djnh toe do 3n mdn

Phan ting an m6n g6m nhi6u giai doan so cp. Giai doan nio c6 ttfc dd nh6 nhat se
quyd't dinh t6c d6 an mon.

147
 Truring hop tdc dd chuyfen electron trdn ranh gicfi kim loai - dung dich didn phan la
giai doan quydt dinh in mon (sat bi in mon trong mdi truring axit) thi the' an mon va tdc dd
an mon dupe x&c dinh tCr phucfng trinh Tafel suy ra tu dinh lu|t Volmer-Butler 6 nhiing gia
tri ldn cua qua the an mon
Truring hop sir tai chat khir phan cue D la giai doan quydt dinh tdc dd an mon (su an
m6n thep trong m6i truring trung tinh c6 oxi hoa tan) do dd tan nho cua oxi trong mdi
truring xAm thuc gay ra thi tdc dd an mdn trong toan bd se duqc quydt dinh bdi tdc dd khir
cua oxi trdn kim loai. Hinh 4.3 se the hidn didu niky.

iOg + 2e + 2H* = HjO

Iglil
a)

Hinh 4.3. Giart dd Evans trong trudng hop in mdn khdng bi khdng chi
bod sit tqi oxi (a) vd c6 sukhd'ng chi'bdi sit tai oxi (b) ia/m < iaJm ia/m =
Trong an mon kim loai, hai phan ting andt hoi tan kim loai va phin ring khir catdt xly
ra ddng thrii. Tuy nhidn mdt vdh dd dat ra la phan ting nao se co vai trd quydt dinh trong
qua trinh phti huy kim loai. De tra lrii vdn dd n&y hay xdt dd ldn cua ddng trao ddi ddi vdi
qua trinh andt va catdt.
Ndu io M iQ D thi hidn nhidn rang dd ldn cua ddng an mon, tdc la vi tri cua giao
didm hai dudng cong phan cue, se chu ydu phu thudc vao during cong phan cue catdt; didu
nky co nghia la tdc dd an mon bi khdng chd bdi phan ung khir catdt (an mon do qua trinh
catdt khdng chd)

ig 1 11 ifl
a) b) c)
Hinh 4.4. Gian d6 Evans trong su khdng chi' catdt (a) (dd dd'c cua dudng phdn cue catdt nho);
khdng chi andt (dd dd'c dudng phdn cue andt nho) (b) va khd'ng chi'hdn hop (c ) (dd dd'c 2 dudng phdn cite
gdnbdngnhau).

Cung tuong tu nhu vay, ndu Iq d iQ M thi su in mon do qua trinh andt khdng chd.
Cung cd th xiy ra su khdng chdhdn hop theo d6 tdc dd an mdn duqc quydt dinh bdi ca hai

148
td'c do qua trlnh andt va catdt. Hinh 4.4 minh hoa su khdng chd catdt, khdng chd' andt va
khdng che hdn hop.

4.1.6. Bao ve kim loai chong an m6n

De ngan chan hoac han che an mon, da co nhidu phuong phap khac nhau. NhOng
phuong phap nay ddu bat ngu6n tir dac trirng pha huy kim loai hoac tir nhflng dieu kien sir
dung khai thac vat lieu kim loai.

Phuong phap che phu. Phuong phap nay nham cd lap bd mat kim loai khoi mdi
trudng xam thuc. Ldp phu co the la mdt Idp son khdng tham nude. Ldp phu se mat tac dung
bao ve mot khi nhung khuyet tat cua ldp phu tao dieu kidn cho khdng khi m co thd tdi
dupe kim loai. khi do oxi hoa tan se cung ca'p electron, d rdi cac electron nay se dupe tieu
thu tai nhung diem trdn bo cua khuyet tat la noi ngheo oxi hon. Nhu vay an mon se xay ra d
dudi ldp son phu va se lan truydn lam tang dien an mon.
Ngoai son, ngudi ta con co thd phu len kim loai can bao vd (con goi la kim loai ndn)
mot kim loai khac. Co hai loai phu kim loai: phu catot va phu anot. Trong su phu catdt, kim
loai phu co the ducrng hon thd' cua kim loai nen, thi du phu thid'c ldn s&t | j, /Sn > /Fc j.
Vi mot ll do kl thu&t nao do, ldp phu co khuyet tat dd 16 ra mot didm cua kim loai nen thi
kim loai cdn bao vd bi an mon rat nhanh. Ngupc vdi su che phu catdt trong su phu andt,
kim loai ndn co dien thd duong hon kim loai phu. Thi du phu kern len sat
{Pzn/zn < fc-+/fc) ' co khuydt tat thi ldp kim loai phu bi pha huy va chira ra

kim loai nen.

Phuong phap didn hoa hoc. Thuc chat cua phuong phap nay la lam cho the cua kim
loai can bao vd thay d6i theo hudng dua kim loai vao vung duoc bao vd (phuong phap bao
vd catdt) hoac vao vimg thu ddng (phuong phdp bao vd andt).

a) Phitcfng phap bao ve catdt bang dien cue "hi sinh". Trong phuong phap nay, kim
loai can bao ve dupe ghep nd'i vdi mdt kim loai khac co thd' thdp hon nhidu, kim loai magie
ching han {(/>* /Mg= - 2,363 V). Magie ddng vai tro " andt hi sinh " trong qua trinh cung
cap electron cho kim loai cn bao vd va bang each nay magie tu huy hoai dd bao ve kim
loai khoi an mon.
b) Phucmg phap bao ve catdt bang ddng dien catdt

Trong phuong phap nay nguon cung cdp electron cho kim loai cln bao vd la ngudn
dien mdt chidu tir bdn ngoai. Kim loai can bao vd dupe nd'i vdi cue dm cua ngudn dien; cue
duong cua ngudn dupe noi vdi mot kim loai bat ki cung dupe dat vao ciing mdt mdi trucmg
xam thuc. Dien ap ngudn dupe dat sao cho thd cua kim loai can bao vd phai ling vdi viing
dien the bao ve (xem hinh ve d).

149
 Phucmg phip bao v6 catdt duoc torn tit bing hinh ve (4.5)

<p
FeFe + 2e

Zn -/> Zn2* + 2e
Fe + 2e
Zn - Zn2* + 2e

a) b)

Fe Fe2* + 2e
Anftt

Red

c)

Hinh 4.5. Phircmg phdp bao vi catdt (a,b) bdng diin cite hi sinh,(c, d) bdng ngudn mdt chieu.

c) Phucrng phdp bao ve andt. Trong phircmg phap nay kirn loai cin bao v6 dirpc phin cue

Bang 4J. The thu ddng cua kim loai pH = 0 vd 25C

Ktm loai Thd thu ddng (V)

,Au 1,36
Pt 0,91
Fe 0,58
Ag 0,40
Ni 0,36
Cr -0,22
Ti -0,24

bing dong didn andt, khi do thd cua kim loai se bi chuyn dich vio vung thd cua trang thai
thu ddng. Ducmg cong phin cue trong su thu ddng hoi kim loai duoc thd hidn a hinh ve 4.6.

150
Hinh (4.6) cho tha'y khi the chuydn dich sang phi'a duomg hem thi thoat tien dong an mon
tang; tai mdt gia tri nao do cua thd, dudng
Vung
phan cue bat du ddi hudng Sn m6n
Dbng
thy d$ng
va giam nhanh vdi thd. Didn the tai do co
su giam nhanh cua mat dd dong la the thu
dong. Cac kim loai khac nhau thd hien thd
Dong
thu ddng khac nhau nhu trong bang (4.1). Sn m6n
nh6
Mot khi kim loai duoc dua vao trang
Hlnh 4.6. Ducmg cong phdn cue
thai thu ddng thi dong didn luu thdng trong phuong phap bao ve andt
khong dang ke, thuong nho hon d6ng hoa
tan tai cue dai cua ducmg phan cue, 100 tori 1000 lan. Va nhu thd, su an m6n dCrng lai do
kim loai duoc bao ve andt bang each bom electron ra khoi kim loai thay vi bom electron tdi
kim loai nhu trong phuong phap bao vd catdt.
Kim loai cung co thd chuydn vao trang thai thu ddng khi duoc xir li bang dung dich co
chua cac chat oxi hoa. Thuc vay, sat se bi thu ddng hoa bang axit sunfuric dac, axit nitric
dac. Hien tuong thu dong gin lidn vdi su hinh thanh tren bd mat kim loai mot mang ha'p
phu oxit hoac mang mudi. Su hinh thanh nhQng mang nay chang nhOng anh hudng nhidu
tdi su hoa tan andt kim loai ma con kim ham nhidu qua trinh dien cue khac. Chxnh vi vay
viec nghien ciiu co chd cua sir thu ddng, su hinh thanh va cac thuoc tfnh cua mang thu ddng
van con la vdn dd thdi sir cua didn hoa hoc.
d) Bien doi mdi trudng xam thitc

De lam giam tinh xam thuc cua mdi trucmg, ngudi ta su dung chat lie chd' an mon; dd
chat hoa hoc vdi lieu sir dung nho dua vao mdi trudng co thd kim ham cac qua trinh dien
cue. Tac dung lie che la do;
- Hap phu phan tu chat uc chdhiiu co ldn bd mat.
- Thu ddng hoa kim loai.

- Tao lop ke't tua mud'i ldn bd mat,ngan oxi cd thd tiep can kim loai.

- Loai bo tac nhan an mon (oxi hoa tan)...

Nhung tac ddng tren, tuuchung hoac lam giam Iq m. IqD hoac lam giam i0 MSa .
I0 DSc trong phuong trinh ddng an mon (4.7).
Tuy theo su kim ham xdy ra d catdt hoac andt ma chat urc chd in mon duoc phan loai
thanh chat lie che catdt hay chat lie chd andt. Chat lie chd catdt lam tang su phan cue catdt,
thi du nhu cac hop cha't cua photpho, asen, antimon lam giam dong trao ddi i0 H cua sir
thoat hidro ddi vdi an mon vdi su khu phan cue hidro (hinh 4.7a). Ddi vdi in mon vdi su

151
khir phan cue oxi, hidrazin cd the duoc dung de lam giam ham lutmg oxi hoa tan do do lam
giam dong trao doi j ddi vdi su khir oxi

2 N2H4 + 7 02 = 4 N03" + 4 H+ + 2 H20

Chat tire che' anOt kim ham qua trinh hoa tan andt kim loai (hinh 4.7b). Nhutig chat nay
thubng la cac hop chat hum co co chtita nito (cac amin thang hoac amin vong thorn), chua
liru huynh (tioure va cac din sua't) hoac chua oxi (cac aldehit). Chung bi ha'p phu ldn phan
be mat anot kim loai va lam giam toe dd hoa tan do su giam cua dong trao doi i0 M.

1121 - C6
- Khflng utche
M = M + ne 1 - Kh6ng ut ch6
2H + 2e = H, lie che 2 - Co tic ch6
2

D + ne = One

a) b)
Hinh 4.7. Gian dd dn mon ire chi'. (a) ire che catot ,(b) ire chi'andt

Can luu y rang su ha'p phu chat tire che khdng chi phu thuoc ban cha't hoa hoc cua
chung ma con phu thudc vao dien tich cua dien cue, do do dd che phu 0 be mat phu thudc
vao kim loai bi phan cue catot hoac anot so vdi the an mon.

Tren day de cap ton anh huong cua chat uc che tdi dong trao ddi catot i0 D hoic anot
'O.M-
.
De lam giam tich so (Sa . i0,M)(Sc i0,D lhi phai thu hep phan dien tich anot hoac
catot.Phan dien tich andt duoc thu hep bang each tao ra san pham ran trong qua trinh hoa
tan kim loai. De thu hep phan dien tich catdt, ngudi ta su dung mdt chat uc che' cd kha nang
tao mang ran tren catdt cua kim loai bi an mon. Mdt thi du chat uc chd tao mang la HCOj .

Ion nay tac dung vdi OH" tao bdi su khir oxi, de cho mot cMt kdt tua la mang cacbonat bao
phu phan dien tich catdt. Ion P04~ cung cd tac dung tuong tu, tao mang photphat sat (II) va
sat (III) tren be mat thep. Tieu chi de phan biet su tao mang andt vdi su tao mang catdt do
lie che' la su chuyen dich the' an mon ve phia duefng hem ddi vdi urc che andt; the' an mon
chuyen dich ve phia am hem neu la su tao mang catdt.
Trong urc che an mon, su phan loai chat ire che con dua vao tac dung cua chung trong
timg loai mdi truong, theo do ngucri ta phan biet tic che' trong mdi trudng axit, trung tinh va
kidm. Bang 4 - 2 ghi lai mdt sd' cha't tic che dung trong cac mdi trucmg khc nhau.

152
 Bang 4.2. Mot so chdt ire ch" vO ca vh hilru co trong moi truimg axit, trung tinh va kiem

Kim loai Moi trirtmg Chat tire ch

hOru co vo co

s&l axit anilin ; etyl vii dietylamin; piridin, quinolin ;

AsO ; NaAs02 i K2Cr207
P-naphtoquinolin ;aldehit fomic ; thiodiglicol

trung tinh natribenzoat, hidrazin

Na2S03
thep axit (nhtr ddi vdi sat)

trung tinh natri benzoat

d6ng axit thioure

K2Cr207 ; KMn04
trung tinh
Ca(HC03)2; Cr042"
trung tinh - Ca(HC03)2; natri va
nh6m va canxi hex ametaphotphat
kem

kiem glucozo 2- 2-
S vaSiOj

4.2. NGUON Dl|N NANG

Nguoi ta goi may phat diSn hod. mdt thit bj cho phep bin d6i hoa nang thanh din
ndng trdn ccr so cac qua trinh oxi hoa - khur di6n ra trong do. Neu chi don thudn dua vao
tieu chi nay thi co the chd' tao mot so rd't ldn cac may phat di6n hoa. Thuc ra sd luong cac
nguon didn nang duoc dem vdo khai'lhac kh6ng nhiu, do Id vi dl co gia tri su dung thi cac
nguon difin nang phai dat duoc cac ydu cau sau ddy:
Sure dien d6ng phai 1cm.
Su ph&n cue phai nho, tire la di6n ap cua ngu6n dien lam vide phai co gia tri it khac voi
sure din dong. Sit giam cua s.d.d khi co dong
dien luu thdng la do su phdn cue din cue va d6 u
giam th ohm gdy ra:
U = (9t-%)-LRdd

= (AC. cb + Tic) "

(%. cb + T1a) "
IRdd
U = E + Tie - r)a - I.Rdd

6 d&y U la di6n ap, E - s.d.d, qc va T|a la Hlnh 4.8. Ditcmg cong phdng dien lai
d6 phan cue catbt (r[c < 0) va anot.

153
 DP'i voi mpt ngudn dien nang thi dien ap U va cucrng do dong difin Ila hai dai lupng co
y nghla quan trong . Thuc vly dico dien ap cao thi phai giam dp phln cue catdt va anot,
giam td'i da dien trdi R cua dung dich bang each su dung chat dien phan co dp din dien cao.

Dung luqng rieng (du tru dien quy v6 don vi thi tfch hay khoi luong co don vi tfnh
-o
bang Wh/cm hoac Wh/kg) 1cm. Die trung nay dupe xac dinh tit ducmg cong phong dien
bieu thi sir phu thuoc U theo thdi gian phong dien tai I= const. (Hinh 4.8). Thai gian sur
dung cue dai cua may phat dien hoa dupe xac dinh tir su giam dot ng6t va nhanh cua dong
dien phat ra.

Cong suat rieng (dien nang quy vi don vi thai gian va don vi kh<5i lupng hay the
tich, co don vi tinh blng W/kg hoac W/m3) 16n cue dai. De dat ducfc dieu nay phai dung
nhung dien cue xop co dien tfch tiip xuc lem giua dien cue va dung dich.

Kha nang tu phong dien nho nhl't. Nguyen nhln cua hien tupng tu phong dien la su
hinh thanh cac pin an mon co xult xur tir su khPng d6ng nhl't cua vlt lieu lam dien cue hoac
cac chat nhiem co trong chit dien phln. Cho den nay cac ngu6n dien nlng dupe che tao
dua tren nam tieu chi tren. Chung dupe phln chia llm ba loai: ngu6n dien so clp (pin),
ngubn dien thur cap (acquy) va pin nhien lieu.
1. Nguon dien so cap dupe che' tao trln co set cac phan ung khong thuln nghich;
cac san pham hinh thanh trong qua trinh lam viec cua pin khPng the chuyen hoa tro lai
thanh cac chit dlu va khi hit kha nlng phat dien pin dupe bo di.

Pin dlu tien la pin Volta co so do (-)Znl H2S04l Cu(+)

4 0
Tai cue Im, kem bi oxi hoa vl giai phong electron

Zn = Zn2+ + 2e
tai cue duong, K1" bi khir de giai phong H2

2H+ + 2e = H2
Su tfch tu H2 xung quanh cue duong da tao ra m6t su phln
cue ldn tren dien cue. De khlc phuc tinh trang nay cue duong la
3 0 m6t cap oxi hoa - khir co the' cao hon the cua clp 2H+/H2. Din
Ifinh 4.9. Pin khd Ie clanche hinh cho loai pin nay la pin Leclanche' (con goi la pin kh6) co
1. MnOj + C + sod6
+ nh4ci + h2o
2. Keo nhao NH4CI
(-) Zn I NH4Cl I Mn02 + C I C (+)
3. Vo kem
4. Oau dong thau
Clp oxi hoi - khir cua pin Leclanche' la Zn2+ / Zn va

Mn02/ Mn203.
154
 Cac phan ting chfnh nhu sau:
(-) Zn = Zn2+ + 2e
(+) 2Mn02 + 2H+ + 2e = Mn203. H20
(Mn203 ngim nude cung dupe vidt D MnO(OH)).
Bdn canh phan umg chinh con c6 phan umg phu g4y ra sir phan cue didn cue do su co
mat cua NH3, NH4+ va CP ; chung se phan umg vdi Zn2+ dl tao ra cac san pham phu nhu
ZnMn204; ZnCl2, Zn(OH)2; Zn(NH3)2Cl2. Pin Leclanche dupe cai tid'n nhieu ian chu yd'u
nham vao ban chat hoa hoc va vat IIcua chat didn phan nhu ZnQ2, NH4C1 o dang keo nhao
dupe thay bang KOH, do do pin mang mdt cai tdn mdi D pin kidm. Pin kidm co uru the so
vcfi cac pin mudi khac la dung lupng rieng rat ldn (Xem bang 4.3), mac du s.d.d khdng
khac bao nhidu do khong co su khac biet ve cac dien thd cua hai cap oxi hoa - khti trong
hai trudng hop. Dung lupng quy vi dcrn vi th tich cua pin kidm cd su cai tidn ro net do
Mn02 dupe thay bang HgO hoac Ag20. khidn cho pin co ki'ch thudc kha nho be (pin cue
ao). So do cua pin kiem, loai HgO dupe vidt :
Znl KOH I HgOl C
Phan umg didn cue:
(- ) Zn + 40H~ = Zn(OH~)42~ + 2e
(+) HgO + 2e + H20 = Hg + 20FT
Vi thuy ngan thoat ra, gay 6 nhifim nen loai pin kidm nay cd xu hudng it dupe chd tao
va sir dung.
Bang 4.3. C&c loai pin thvfnig dung

Pin mudi Pin kilm Pin Liti

An6t Zn Zn Li

Cht dien ph4n KOH LiBr

ZnCt2+NH4a
(keo nhao)

Cat6t C, Mn02 C, Mn02 C. Hg C. AgjO C, S02 long

s.d.d (V) 1,5 1.5 1,35 1,4 3

Dung lirong rifing 84 100 123 J36 330
[Wh/kg]

Ngay nay loai pin dupe dung kha pho bid'n la pin Liti. Goi la pin Liti vi andt cua pin la
kim loai kiem Liti rt hoat ddng. Sue dien ddng cua pin Liti rat ldn (3V). Dien nang quy ve
dom vi khdi lupng cung cao. Kim loai Liti cd khoi lupng rieng nho. Vdi uu thd nay, pin Liti
rt nhe, ra't thuSn lpi cho sir dung, di chuydn. Mot van dd dat ra cho pin Liti la Liti khii nude
rat manh do do dung mdi dupe dung budc phai khan nhu tetrahidrofuran (THF), cac ete
huu co ... Cac hop chat dung chd tao loai pin nay thudng la S02 long, tionyl clorua SOCl2
hoac sunfuryl clorua S02C12. Pin Liti cung cd nhidu loai tuy thudc vao trang thai vat IIcua
chat oxi hoa. Vdi chat oxi hoa ran nhu CuO hoac mangan oxit ta cd so do pin Liti:

155
 (-) Li / LiC104 / THF / CuO / C (+)
Vdfi chit oxi hoa long nhu S02 dong vai tro dung m6i ta co
(-) Li I LiBr I S02 I A1 I thep (+)

D6'i vdi pin S02 , cac phan ung scr cip nhu sau:
(-) Li = Li+ + e
(+) S02 + e S02
2S02" = S2042~
Dong hoc dien hoa dong vai tro ri't 1cm trong nghidn ciru ch tao loai pin Liti nay vl su
khir cua dung m6i khong duoc ph6p xiy ra trdn be mat Liti mi x&y ra khi tidp xuc vcri didn
cue kia cua pin.
2. Nguon dien thu cap la nhung he didn hoi c6 th sir dung duoc nhiu lin do kha ning
tai tfch didn cua he sau qua trinh phong didn. Dieu nay doi hoi hai hd dien cue phai thuin
nghich tutc la phan ung thuin trong qua trinh phong didn co thd dao ngupc trong qua trinh
tfch didn.
Ngu6n dien thii cip la nhung acquy ma didn hinh vi c6 din nha't la acquy chi (con
goi l& acquy axit).
Sir hoat dong cua m6t acquy g6m hai giai doan: Giai doan tfch didn va giai doan phong
didn.
6 giai doan tfch dien, dat m6t dien ap U cao hem sire dien d6ng E (Xem hinh 4.10)
U = E + r|a - ric + RI
6 giai doan phong didn, acquy cung c&'p didn ning cho bdn ngoai. Hoat d6ng cua
acquy 6 giai doan nay duorc minh hoa trdn hinh (4.10).

Red, V- Ox,
I

Oxf- Redg
' Red

Tich dien Phdng <Ji$n

ut = E + tia + Ri (Tic < > = E - na + ric - Ri (nc < 0)

Hinh 4. 10. Dicdmg cong phdn cue trong sit tich vd phdng diin

Bang 4.4. ghi lai cic loai acquy chfnh da thucrng mai hoa.

156
 Bang 4.4. C6c loai acquy

Axil Ki6m
Chi Niken - s5t Bac kSm Niken-Cadimi

Anfit Pb Fe Zn Cd

Catbt C,NiOOH C, NiOOH

Pb. PbO2 Ag. Ag202

s.d.d [V ] 2 1.36 1.6 1.3

Acquy chi. Loai acquy nay rd't hay dugrc su dung trong dbi s6'ng. So d6 nhu sau:
(-) Pb t PbS04 I H2S04 (30%)l PbS04l Pb02l Pb (+)
An6t cua acquy la cue am, tai d6 xy ra su oxi hod khi phong di6n vd la cue ducmg khi
tich dien.
Phan ting didn cue nhu sau:
Pb + PbO,2 + 2H+ + 2HS04"
4 , phdngdidn - 2PbS04 + 2H20
4 2

Nhuqc didm chinh cua acquy chi la dung luqng din quy v don vi khoi luqng nho,
thdi gian sir dung khbng dai do su sunfat hoa dan ede difen cue (su chuyn hoa kh6ng hoan
toan cua PbS04 thanh Pb vd Pb02 trong qua trinh tich di6n).

Ngoai phan urng chinh cua qua trinh phong va tich di6n cr trdn con co nhung phan utng
phu do su tu phong didn cua acquy gay ra. Do la su khir proton 6 cue dm
Pb + 2H+ + S042- = PbS04 + H2
va su thoat oxi b cue duong

Pb02 + SO + 2H* = PbS04 + H20 + |o2

Acquy kidm, duqc goi do kidm Id chd't didn phdn. Acquy kidm phd bid'n nhd't Id
acquy Niken-Cadimi co scf d6:
(-) Cd I Cd(OH)2 1 KOHaq I NiOOH I Ni(OH)2 I Ni (+)
Tai cue duong, niken b hai muc oxi hoa Ni(II) va Ni(III),kim loai niken chi lam nhidm
vu thu nap dong didn:

NiOOH + e + H20 , Ph"g

Ni(OH)2 + OH"
Tai cue dm:
Cd + 20H" , Phrt"6
Cd(OH)2 + 2e

157
 Phan ting t6ng quat:

2NiOOH + Cd + 2H,0 ; Ph6"fi

tfch
> 2Ni(OH)2 + Cd(OH)2.

3. Pin nhien lieu. Do la mdt may phat didn hoa bidn d6i nSng ltfdng cua phan ting ddt
chay thanh didn nang. Khac vdi ngu6n didn so c&p va thti cp da xet, b do nng luong didn
duoc ti'ch lai, b pin nhien lidu khdng co vn d6 tfch tu didn nang ma didn nang lidn tuc duoc
sinh ra nho khdng ngting cung chat nhidn lidu va chat oxi hoa.
Mot thi du dfcn hinh cho pin nhidn lidu la pin hidro-oxi g6m mdt chat didn phan la
dung dich dam dac cua KOH trong nude va hai didn cue iam tir vat lidu kim loai mang hoat
tfnh xuc tac cao nhu Pt chang han. Kht hidro va oxi duoc bom vao khu vuc andt va catdt, tai
day xdy ra phan ting:
Andt 2H2 + 40H"aq = 4H20 (1) + 4e
Catdt 02 + 2H20 (1) + 4e = 40H~aq
aq

Tdng qudt 2H2 + 02 = 2H20(1)

S.d.d chun cua pin E = +<pRed = 0,83 +0,40 = 1,23 V
Cac didn cue platin co hai chtic nang, din didn va didn xtic tic cho su phan tfch ban
ddu cac phan tu thanh nguydn tti trutic khi xay ra phan ting chuyln electron. Ngoai platin,
con co th dung niken, rodi v.v...

Hinh ve 4. 11 minh hoa pin nhidn lidu hidro-oxi

Hinh 4. 11. Sa do pin hidro - oxi.

158
 4.3. 0IEN TONG HOP VA DIEN XUC TAC

Diy la mdt lanh vac r&'t to ldn cua didn hoa hoc ung dung vao san xudt. Thuc v$y, c6ng
nghd san xudt xut clo co co sd la su didn phan dung dich mudi NaCl trong nude. Su didn
phan nadc d thu daoc hidro, oxi cung nha nadc n3ng ddu dua trdn co sd cac phan dng didn
cue. San ph&n hidro, oxi la ngudn nguydn lidu cho cac pin nhidn lieu khdng gay 6 nhidm
mdi tradng. Nhidu hoa pham v6 co daoc san xudt bang con dudng didn hoa va mang lai y
nghia kinh td to ldn nha cdng nghd san xudt hipoclorit, clorat, perclorat, hidroperoxit,
persunfat, permanganat, mangan dioxit v. v...

Didn tdng hop con md ra mdt hadng san xudt mdi cac chdt hiJu co nha sa khir catdt cac
lidn kd't ddi trong cac phan dng dime hod dien hod de thu daoc cac hidrodime. Ben canh sa
khd catot ngadi ta con sd dung sa oxi hod andt trong didn tdng hop cic hop chat h(ru co, thi
du sa oxi hoi cac axit cacboxylic d didn thd' andt cao dd tao ra cic gdc ta do, nhffng gdc
nay se tham gia tid'p vao cac phan dng ddcacboxyl hoa, kdm theo sa dime hoa.

+X(CK*
X(CH2)nCOO~ - e ->X(CH2)nCOO" X(CH2)'n >X(CH2)2nX

vdi X la CnH2n+1, F, CI, CH3COO, CN ...

Mdt sd phan dng oxi hoa - khd daoc xuc tic bang kim loai. Nhung kim loai dong vai
tro xuc tac nay daoc goi la chdt xuc tac didn hod1. Sir oxi hoa cac mudi Mn2+ thanh Mn04"
bang S2082" co tdc dd dang ke khi dung mudi Ag+. Tdc dd khd catdt ion hidre co tdp dd
tang 1011 ldn khi chuydn td kim loai chi sang rddi. Tidu chi dd danh gid hoac so sanh kha
nang didn xuc tic cua cic kim loai hay hop kim la %\i tri ldn nha't cua mdt dd dong tai mdt
didn the da cho. Hinh (4.12) cho tha'y hop kim 80% Pt va 20% Ru xuc tac td't hon Pt ddi vdi
sa oxi hoa etylen d didn the tha'p hon 0,45 V, trong khi do d dien thd cao hon 0,45 V thi Pt
lai didn xuc tac tot hon hop kim Pt-Ru.

Ndu goi i va , i2 la mdt dd ddng trdn hai chdt didn xtic tac 1 va 2 thi tur phuong trinh
Volmer - Butler ta co:
-b,Fr|
l, = io l exp
RT

h = io.2 exp -b2Fn

RT
(b, va b2 la hd sd Tafel)
Ndu phan ung didn cac trdn ca hai chdt didn xuc tic co chng mdt co chd (ducrng phan
umg va giai doan quydt dinh tdc dd) thi cd thd xem b, = b2, khi dd cac sd hang mu cua hai
hd thurc tren bang nhau va ta cd :

159
 '2 ('0)2
Nhu v$y khi so sanh mat d6 dong tai m6t di6n thd da cho ddi vdi hai chat dien xuc tic,
ta so sanh hai gid tri tuong ting cua dong trao d6i.

80%PI 20%Ru
ip[v]
0.6

0.5

0,4

0,3-

0,2 -2 -1 i [A/cm
10 10 10

Hinh 4. 12. Duong phan cue dot vai su oxi hod etylen
trin hai chat diin xuc tac la Pt va hap kirn 80% Pt 20% Ru.
D& lam ncii bat vai tro xuc tac cua vat lieu di6n cue, phucfng trinh Volmer-Butler duoc
vit lai dudfi m6t dang khac nhu sau:

i = nFCkRexp -bF#>
RT
kT -AG*
VOl R = !Texp RT

Khi luu tdfi hop phn dien thd bd mat x dien thd Volta vy cua didn thd cp, phuong
trinh mat d6 dong i b trdn tr6 thanh:

1=
.
nrckRexp
~bF<|)
J exp-
-bF(-<t>pzc)
RT RT

<t>pic la the' dien ti'ch khdng.

Voi phuong trinh nay vai trb xuc tac cua dien cue da the' hien ro. Thuc vay tdc dd phn
ting didn cue phu thudc trutic ht vko hidu the' qua ranh gidi b mat ti'ch dien, sau do la vao
chat xuc tac (s6 hang kR). Nhu vay didn xuc tc c6 hai dac trung, dac trung didn va dac
trung hoa hoc.

Dd phan bidt hien tuqng xuc ttic hoa hoc voi didn xuc tac ngucri ta can cur vko bidu thuc
t<5c d6 phan ting. D6i voi xuc tic cua phan ting hoa hoc di thd, t<5c d6 c6 dang
kT -AG*
v = c exp
h RT

160
 T6'c d6 phan ung di6n xtic tac co dang:
i kT -AG* -bF<p
v= = c exp exp
nF h RT RT

D6i vdri dien xiic tac, khi thay d6i dien the, ttfc d6 phan urng tr6n mdt chaft difen xtic tic
da cho co th thay doi dang k; trong mfit s6 trudng hop, t6"c dq co th ting 10 ldn. Trong
trucrng hop xuc tac hoa hoc, su tang nhiet d6, khdng lam tang qui lbn t#c do theo hai chiu
thuan va nghich.
Bang (4.5) ghi lai m6t sd dac trimg cua hai dang xtic tac.
Bang 4.S. Dac trimg cua hai dang xuc tac, xuc tac hod hoc vh difin xuc tac

Xuc tic hoa hoc Din xfic tic

T6c do phu thudc
-AG" -AG* -bF<p
exp exp exp
RT RT RT

Phu thuflc di6n th Khdng c6

Phu thudc nhiet dp c6 c6

Khoang nhiit dft phan ung Thucrng trdn 150C Thirong (hip hon 150C

Nang lirpng hoal hoi [kJ / mol] 41,8-418 21 - 146

4.4. MOT S6 PHlTONG PHAP PHAN TfCH BIN HOA

ft a

Cac qua trinh didn cue da duqc van dung c6 k6't qua vao hoi hoc phan tich dinh luqng
cung nhu dinh tinh d6'i v<5i cac chat va mdi trubng khac nhau. Phuong phap phan tfch dien
hoa da duqc hinh thanh tir the' ki 19 va cho ddn nay van khdng ngiimg phdt triln va hoan
thien them. Uu dim 1cm cua phuong phap Ik 6 ch6 khi he do chiu tac ddng dien (d6ng, the)
thi dap tuyen nhdn duqc cung la tin hiu dien. Dac didm ndi bat cua phuong phip phan tfch
dien hoa \h do nhay va d6 chon loc cao, khdng doi hoi the tfch dung dich 16n (nho hon 1
ml). Phuong phap phan tich dien hoi duqc chia thanh ede phuong phdp:

Do dien din.

Do difin luqng (Coulometry), xic dinh dien luqng Q cdn cho su chuy&i hoa (oxi
hoa hoac khu) hoan toan chat nghidn cuu.

Do von - ampe (Voltamperometry), xac dinh nhutig die trung phan cue b trang
thai dimg, kh6ng dimg cua dien cue trong cic phan ung dien cue.

Do dien the (Potentiometry), xac dinh the cdn bang cua dien cue chi thi b do co
mat chit nghien ciru la chat co n6ng d6 phu thubc the.

-
11 - PLTOHHilfO A 161
4.4.1. Phuttng phap do dien luong

Ccr luong cua phuong phap la dinh luat Faraday theo do m6t luong didn Q can
sal dinh
de chuydn hoa chat nghien cuu thanh san phdm dupe xac djnh. Didu kidn can cho vide su
dung phuong phap do didn luong trong hoa hoc phan tich la chat nghidn curu phai phan urng
vpi hidu suat dbng 100% tutc la khdng co phan ung phu kem theo.

De tranh phan ung phu, phuong phap do didn luong dupe tidn hanh trong chd dp tTnh
(Potentiostatic) theo do ngucri ta dat mOt didn the cP dinh va do dong luu thdng qua hp do
theo thPi gian. Luc dau dong co gia tri cue dai sau do se gidm dan theo su chuyen hoa chat
nghidn curu. Didm kd't thuc qua trinh do didn luong se umg vPi su giam tPi khdng cua dong.
Su giam cua dong trong qud trinh phan tich didn luong kd' Id do hai nguyen nhan; m6t la su
giam nong dd chdt nghidn curu o trong long dung dich, thu hai la su giam nPng do bd mat
cua cha't nghidn cun gay boi gradien cua nPng dp.

4.4.2. Phuong phap do von - ampe

Cac phuong phap do von - ampe dua trdn su do cac thPng sP didn hoa nhu thd nira
song, dong gicfi han, thd hodc dong tai cac didm cue tri; su do cac ducmg cong phan cue
trong chd dp dimg (khdng phu thudc thbi gian), kh6ng dimg (co phu thupc thbi gian).

Mot trong cac phuong phap do von - ampe kha phd bid'n trong phuong phap phan tich
didn hoa hidn dai la phuong phhp do thd - thai (chronopotentiometry) dua trdn su phu thudc
cua didn thd theo thbi gian tai mdt gid tri cho trupe cua dbng. Dd tidn hanh phep do nay
ngucfi ta sir dung mpt thidt bi dupe goi la amperostat (mdy pht dbng khdng chd) dd dat
dong luu thdng giua didn cue chi thi va didn cue phu trp, r6i do hidu thd giura didn cue ch't
thi va didn cue so sanh. Phuong phap thd - thbi ddn gian nha't la phuong phap thd' - thbi b
dong hang dinh. Ndi dung phuong phap la dat mpt dbng catdt cp cubng dp Ic = const. Su
luu thOng cua dbng Ic keo theo su khu vpi tdc dp khdng ddi cac chat didn hoat o gn didn
cue, khi do dien cue cP didn thd ling vbi cap oxi hoa
1 <p
Oap tuyen
Tin hi#u v&o

/ i

o t i
Hinh 4. 13. Phep do thi - thcri tai cucmg dd dong khdng doi

khu cua cha't nghidn curu va dien thd nay bid'n thidn vPi ti sd ndng dd cha't oxi hoa va chdt
khu. Dubng cong the -thbi cp dang tucrng tu ducmg cong nhan dupe trong qua trinh chudn
dd dien thd c6 didn (hinh 4. 13).

162 - -
11 PI/6H&ITD B
 Sau m6t thcri gian n6ng dd chdt oxi hoa tai dien cue bi tridt tidu, v& su tai chdt oxi hoa
tir long dung dich ve dien cue kh6ng dap urng duoc sir tidu thu electron trdn dien cue do do
dien the thay d<Si rat nhanh va trcr ndn am hon lm cho su khir cua chat dien hoat tidp theo
c6 thd xdy ta. Thcri gian tfnh tir luc dat dong co cucfng d6 I= const tdfi luc co sir bidn thidn
d6t ng6t cua dien thd duoc goi Ik thri gian chuydn tid'p (transition time) x .
Thcri gian x lien hd vdfi ndng dd va hd s6' khudch tan cua chit dien hoat khao st duoc
H.J.S.Sand thidt lap liin ddu tidn vao nam 1901:

ix1/2 nFADl/27tl/2 =85500nD1/2A (he don vi S.I)

C 2

Phuong trinh Sand cho thay su phu thudc cua n6ng dd C cua cha't nghidn curu vao ixl/2,
do do co thd xac dinh C tir ducmg chudn trong he toa dd ix,/2 C. Ndng dd C se duoc xac
dinh chinh xac tir ducrng chudn ndu bo qua ddng dung dd tfch dien lcrp kdp. Phuong phap
phan tfch the' - thofi cho phep xdc dinh n6ng dd tcri 2. 10"4 dlg/1.
Thay v] giu c6' djnh dong trong phdp do the thcri ,ngucri ta lai dao ddng trong mdt thcri
gian nao do sau khi dong mach. Day la phuong php do the - thcri dao chidu (Inversion
chronopotentiometry). Thuc cha't cua phuong phap nay nhu sau: gia sir thoat tien dung dich
chi chira cha't dien hoat Q co ndng dd C. Dat mdt d6ng catdt i = const trong thcri gian tj
(t, < x,). Tai thcri diem tj, dao chieu dong dien , tufc la chuydn dong catdt thanh dong anot
sao cho dang khir R duoc tao ra 6 giai doan ddu bi oxi hod trcr lai thanh O. Ghi lai thcri gian
x2 (tfnh tir thcri diem tj) ting vdi n6ng dd bd mat CR tridt tidu. Tai thdi didm x2 didn thd' didn
cue tang ddt ngdt.

a)

Hinh 4.14. Phuefng phdp do the th&i dao chiu (a) vd chu ki (b)

Phuong phdp thd - thcri dao chieu c6 thd duoc cai tidn them mdt budc bang edeh dao
chieu 6 mdi giai doan chuydn tidp. Vdi each lam nay phep do thd- thcri duoc goi la phep do
thd' - thcri chu ki (Cyclic chronopotentiometry). Hinh 4.14 minh hoa phep do thd - thdi dao
chidu (a) va phep do thd - thcri chu ki.

163
 4.4.3. PhiftJng phap cut pho
Phan tich cue ph<5 la m6t truofng hefp ridng cua phan tich hoa hoc dua vao su do von
ampe . Phuong phap nay gin lien vdi vide sir dung didn cue giot thuy ngan lam dien cue
lam viec. Phuong phap cue ph6 dupe ap dung trpng phan tich dinh tinh (dua vao thd' nua
song) va dinh lupng (dira vao mPi quan he tuyd'n tinh giua dong khudch tan giori han va
nong dp chat nghien curu trong dung dich). Nhln chung phan tich cue ph6 cP nhidu uu
didm so vcri mot s6 phuong phap phan tich phi didn hoa 6 ch6 bd mat didn cue thudng
xuydn dupe doi mciri, dp lap lai cua giot thuy ngan cao; hai yeu tP n&y lam cho phep do co
dp chinh xac cao. Mpt uu didm khac cua cue pho la qua thd' hidro cao tren didn cue giot
thuy ng&n da han chd' dupe su nhidu trong qua trinh khir catdt cac chat nghien cuu. Nhupc
diem chinh cua phuong phap cue ph6 1k vdi didn cue giot thuy ngan nguPi ta khdng thd lam
vide 6 cac didn the cao hon 0,0 V/ SCE. Trong phan tich cue pho c6 dien, nguoi ta do
ducmg cong phan cue o che dp gdn dung khi dat vao dien cue giot thuy ngan mpt didn the
quet tuydn tinh du cham sao cho trong thoi gian sPng cua timg giot thuy ngan, dien thd thay
ddi khdng qua 3-5 mV. Phuong phap cue pho c6 dien co the dupe cai tidn de lam tang dp
nhay va dp chon loc bang each ghi song cue phd khong phai trong toa dp I- cp ma trong toa
*. dl
do
--
dp
(p .

V6i he toa do nay dong cue pho the' hidn cac pic (hinh ve 4.15) doi xung co chidu cao h
ti Id v6i dong khuech tan gioi han trung binh Id , va do do cung vao nong dp cha't trong
dung dich, con dien thd cua pic la the nua song. Cue phd dang nay got la cue phd vi phan.
1 V6i hd toa dp nay dong cue phd thd hidn cac pic
(hinh ve 4.15) dPi xung co chidu cao h ti Id vdi
dong khudch tan gicfi han trung binh Id , va do do
cung vao n6ng dp chat trong dung dich, con didn
thd cua pic la thd nira song. Cue phd dang nay goi
la cue phd vi phan.
Dd gia tang dp nhay cua phuong phap cue phd
dl
d<p
ldn mpt bac (tir 10" SM ldn 10" 6M) ngudi ta tim
each lam tang hop phan Faraday IF va d6ng thai
lam giam hop phdn dien dung Ic cua dong do. Dd
lam vide nay co ba phuong phap cue pho dupe sir
dung, dp la phuong phap cue pho do (Tast
Polarography), theo do dong dupe do bien thidn
khPng lidn tuc theo thdi gian sPng cua giot thuy
Hinh 4. J 5. Song cue phS ngin (tir 5 ddn 20 ms, trupc khi giot tach khoi mao
quan). Phuong phap nay co mpt hidu Png phu anh
hucmg tPi dp nhay do viing gdn sat didn cue ngheo cha't didn hoat, do do can trP su chuyen
cha't Vd didn cue tai dung thoi didm chinh xac cua phep do. Dd khac phuc nhupc diem nay
nguPi ta sir dung mpt phuong phap mPi - phuong phap cue pho xung co bien dp tang dan

164
(Normal Pulse Polarography) do G. C. Barker xay dung nam 1957; trong phucmg phap nay
dien cue dugc tac ddng bad mdt loat cic xung didn co bidn dd tang din ; trong khoang thai
gian giura cac xung dien cue co dien thdT dugc duy tri dc khdng xay ra didn phan trong phdn
Ion thai gian song cua giot. Sau m6i xung, ngucfi ta do dong trong thdi gian cue ngin (5-
15ms). Then gian nay, dong tich dien ldp didn kep Ic thuc te bi tridt tieu, do do d6ng do
mang dac trung cua dong Faraday IF. Vi thai gian tic ddng cua xung rat ngin ndn su
khud'eh tan la khuech tan khdng dimg do do dong khuech tan nay ldn hem dong khud'ch tan
dung rat nhifeu lin, di6u nay cho phep xdc dinh tap chit co ham lugng nho.
Dd nhay cua phan tich cdn co thd dugc tang them so vdi phucmg phap cue phb xung co
bidn do tang dan, bang each dat vao difen cue nhung xung co bidn do nho (10-30 mV) c6
dinh, trong khoang then gian 40 ms, (hinh 4.16b). Day la phucmg phdp cue ph6 xung vi
phin; song cue phd ghi dugc a dang cac pic ma vi tri cua chung xic dinh ban chit cua chat
nghien cuu, con chidu cao thi xac dinh ndng dd.

-<p
<P
<*>*, SHJasoww*
S~ l00mS| _
110-30
|-Gio
Giot rot

mV

0,5 - 4s

a) b)

Hinh 4. 16. AT thudi xung co bi(n dp tang dan (a) vd cd bien do c6dinh (b)

Vdi phuong phap cue phd xung vi phin (Differential Pulse Polarography) gidi han phin
tich cd thd dat tdi lOM, song didu nay con tuy thudc vide chon mdi trucmg.

4.4.4. PhUOng phap dien ho& ban mong

Trong phucmg phap nay ngudi ta sir dung nhung didu kien d su dien phan ducfc thuc
hien hoan toan ma khdng cln tdi su tai chit bang ddi luu. Mudn vay, dung dich didn phin
co th tich cue nho (vii pi) dugc bd tn thanh mdt ldp mong (2 - 100 pm) ddi didn vdi bd
mat dien cue. Chumg nao bd day cua td bao dien hoa nho hem bd day cua ldp khudch tan
trong khoang thdi gian do (tire la l (2Dt)1/2 thi cd the bd qua su tai chat ben trong te bao
didn hoa. Ndu su quet th trdn didn cue lam vide theo chidu giam d&n bat dau td didn the tai
do chua xay ra su dien phan thi dong cue dai (pic) dugc xac dinh bang bieu thuc:

iP = n2F2vVC/4RT
vdi v la td'c dd quet thd, V la thd tfch dung dich.

Phuong trinh nay cho thay pic cua dong ti le thuan vdi ndng dd C cua dung dich va vao
tdc d6 quet thd'.

165
 4.4.5. Phuttng phap phan ti'ch dien the ke (Potentiometry)
Phucmg phap didn thd kd duoc dung dd xac dinh didm tucrng duong trong qua trinh
chun d6. Co scr cua su xdc dinh nay dua trdn sir do the cua dien cue chi thi. Tuy thuoc vao
dieu kidn do ma co thd sur dung m6t didn cue chi thi hoac hai didn cue chi thi . Trucmg hop
mot didn cue chi thi thi can co thdm mdt didn cue so sanh. Trong phep chudn d6 didn thd
ngucri ta phan bidt cac trudng hop sau:
.
a) Cucmg d6 dong trdn didn cue chi thi bang kh6ng Day la phdp do dien thd c6 dien.
Thd cua didn cue chi thi la didn the can bang Nemst, phu thu6c vao hoat do hay nong do
cua ion chat xac dinh.
b) Dat mot dong didn co cucmg dd khOng ddi vao hd do mdt hoac hai didn cue chi thi.
Didn cue chi thi trong phep do dien the' co thd la didn cue giot thuy ngan, vi didn cue
platin co khudy dung dich, hoac didn cue dia quay. Didn cue so sdnh ducfc chon, thudng la
didn cue calomel bao hoa SCE.
Trong phuong phap do thd' mdt didn cue chi thi, ngucri ta do hidu thd gifla didn cue chi
thi va didn cue so sanh; dong didn luu thdng tren dien cue so sanh nho (co the duong, am
hoac bang khong ). Ducmg cong chuin dd Fe2+ bang Ce4+ theo phan ung:
Fe2+ + Ce4+ = Fe3+ + Ce3+
duoc thd hien tren hinh (4. 17).

/ A
j/
/ ;
- - -0
.>-rTTi
'
i
*
=0--- i = ic
a

'.Sr\

o, 1 1,5 f
/
/

Hinh 4.17. Chudn dd dien the voi Pt I .

dm diin cite chi thi SCE la dien cite so sanh ddi vesi hi
FeJ*l Fe2*; Ce'+ICe", khi i= o i= iu (- o -) vd i = ic <-A-).f= [Ce],kJ [FeuU,

Tren hinh (4.17) duong cong i = 0 la ducmg cong chuin do co didn, cho thdy su bid"n
thidn cua dien the can bang Nemst phu thuoc vao ti s6' luong (s6 mol) Ce4+ them vao tren
lucmg Fe2+ban diu. Ndu co mdt dong an6t cucmg do nho luu thdng trdn didn cue chi thi, thi
didn the cua didn cue nay chi 1cm hem didn thd' Nemst mdt chut. Cung nhu vdy, khi i = ic,
didn the se tha'p hem thd Nemst mdt chut. Trong ca ba trucmg hop (i = 0; i = ia; i = Iq) tai
didm tucmg ducmg (f = 1) ddu co buoc nhay the.
Trong phucmg phap dien thd kd hai didn cue co dong didn luu thdng, ngucri ta theo doi
hidu s6 hai thd didn cue cua hai didn cue chi thi phu thudc f. Hai didn cue chi thi thucmg
166
 A<p
duoc chd tao tur cung m6t vat lieu va co kich
thircrc xa'p xi nhau, dong anot va cat6t phai
bang nhau. Dim tucmg duong dugc the
hien bang pic cua ducrng cong chuin do
(hinh 4.18).

0 - 1
-
0.5 '-
1
-
1,5
*
(
1

Hinh 4.18. Chudn dd diin Ihdvi phdn dd'i vffi

he hai dien cue trong chudn dd Fe2* - Ce4*

CAU h6i va bai tap

4.1. Cho bid't nhung dac trung cua 3n m6n didn hoa.
4.2. Cho bid't nhufng dieu kifen nhiet ddng lire va dieu kidn ddng hoc ctia an mdn didn hoa.
4.3.Trong so cac kim loai sau day, kirn loai nao c6 xu hifdng bj an m6n trong kh6ng khf Im d
pH = 7: Fe, Cu, Pb, Al, Ag, Cr, Co? Chp nhan nong dd ion kim loai tdi thiu d 3n m6n xay ra la
10-6 M.
4.4. Khi dong va thdp non tip xiic nhau, kim loai nao se bi an mdn ?

4.5. Tai pH blng bao nhidu thi ede kim loai a bai tap 4.3 bj an mdn d 25C ?

4.6. Tfnh do I6n cua ddng 3n mdn trdn mdt ti'm kem 0,25 cm tip xtic vdi mdt tm st cung didn
tlch trong mdi trirdng mrdc d 25C. Ddng trao ddi cua kdm va sdt blng nhau va bSng 10
A/cm2, [Fe2+] = [Zn2+] = 10" 6 mol/l.
OS. 0,13 mA
4.7. Hai kim loai sSt va thidc tiep xuc nhau trong dung djch cd pH = 4. Di/a vdo bang cac thd
chuan cua kim loai va qua the hidro trdn sdt (0,08 V) va trdn thidc (0,53 V) hay tfnh hidu thd cua pin
an mdn khi khong cd khdng khf. Gia thidt trong dung djch chi cd sir hinh thdnh cac ion don cCia sat
vd thiec. Cho bid't anh htfdng cua khdng khf (ttfc oxi c6 ap sut rifeng 0,2 atm) tdi dd Idn cua hidu
the pin an mdn va ban cht cCia 3n mdn.

4.8. Vidt nhCrng phi/dng trinh t? li/qng ddi vdi cac phan dng sau:

a) An mdn sat trong dung djch H2S04 da dudi hdt oxi.

b) An mdn dong trong dung djch H2S04 c6 oxi hod tan.

c) An mdn dong trong dung djch HCI cd oxi hod tan.

d) An mdn kem trong dung djch HCI.
167
 4.9. Doi v6i phan Ceng 2H+ + 2e = H2 , dien ra trdn didn cGc kim loai nhung trong dung djch axit
pH = 3, ddng trao ddi io H = lOA/cm2 d 25C. He sd Tafel catdt pc = 55 mV.
Ti'nh mat <56 d6ng catdt khi <J3t vdo didn cUc mdt didn th <p = - 600 mV so vdi din cifc
calomel bao hod.
0S: 0,21 mA/cm2
4.10. Ve dudng cong phan cut ddi v6i cac phan Gng didn cue sau vd xac dinh thd an m6n, tdc
doan mon i vdi gia thidt ede qua trinh andt va catdt la do sif khdng che chuyn difen Uch (theo an
m6n va d6ng an mon phai dugc xac djnh blng do thj),

M = M+ + e <Pan6t=-0.7V i0iM = lOA/cm2 Pa = 0,1 V .

2H+ + 2e = H2 <Pcat6t = 0.1V i0,H = itf A/cm2 pc = -0,1 V
OS (Pan, - 0,3 VSHE
U= 10"3 A/cm2
4.11. xac djnh sGc didn ddng ctia acquy ken - cadimi va cdng sudt ede dai bidt r&ng acquy
cung cap mdt d6ng didn cudng dd 100 mA d 25C.
DS;1,299 V; 0,13 W

4.12. Diia vao bang dOf kidn dudi day ddi vdi phSn Grig thoat H2 hay t/nh hoat dd didn xyc tac
tuting dd'i cua didn cue sat so vdi didn cue niken.
Dien cue Qua thd tai mat do ddng xac djnh [V] dr|/d{lgi) [V]
Fe -0,427 -0,120
Ni -0,350 -0,112

4.13. Ooi vdi pin Leclanche, tai mdt didn cue Zn bj oxi hod tdi Zn(OH)2 (r);d dien cue kia
Mn02 (r) bj khCr tdi MnOOH (r) vdi sG c6 mat cua dung djch NH4CI tao ra NH3 (aq). Hay vit ede
phan Gng didn cue vd phan Gng tdng qudt trong pin. Hay xdc dinh khdi lUdng tdi thilu cua ede chdt
tham gia phan Gng tong quat trong pin ndu pin sdn ra mot ddng didn
0,01 A trong 10 gid.
OS:0,122 g Zn; 0,324 g Mn02; 0,2 g NH4CI; 0,0634 g OH"

4.14. Trong qua trinh tfch dien acquy chi, PbS04 (r) bj khG tdi Pb vd PbS04 (r) bj oxi hod tdi
Pb02 (r); ca hai qua trinh deu xdy ra trong dung djch H2S04. Hay vidt ede phdn Gng xy ra. N&j
trong qud trinh ttch didn cho acquy , ngUdi ta dung ddng didn 10 A cho di qua acquy trong mdt gid
rudi thi cd bao nhieu PbS04 bj phdn ti'ch ?

DS:170g PbSO<

168
 tAi liu tham khAo

1. TrSn Hi6p Hai, Trin Kim Thanh, Giao trinh hoa If tip III, NXBGD, 1983.

2. Truong Ngoc Lifcn, Di6n hoa 11 thuyd't , NXBKHKT 2000.

3. P. W.Atkins, Physical chemistry, Oxford University Press 1992.

4. J. OM.Bockris, Comprehensive Treatise of Electrochemistry, Vol 2, Plenum Press,

New York 1981.

5. A.J.Bard, L. R Faulkner, Electrochemical Methods, Fundamentals and Applications,

John Wiley & Sons, Inc. Publishem , 1980.

6. C. Rochaix, Electrochimie. Editions Nathan 1996.

7. J. Sarrazin, M. Verdaguer, Loxydoreduction - Concepts et expediences, Edition

Marketing 1991.

8. J. Besson, Precis de Thermodynamique & cinetiquc Electrochimiques Edition

Marketing 1984.

9. B.B. Damaskin, O. A. Petrii , Osnovy teoretitcheskoiielectrokhimii, Mockva,

vytchaya szkola 1978

10. V. S, Bagotszki, osnovy Electrokhimii, Moskva Khimia 1988.

-
12-PUDH&LT0 A 169
 PHU LUC 1. DON VI VA CAC THtfA s6 HOAN D6l

Bang 1. Cac dan vi ca sb

Dai ltrong vat if Don vi SI Don v{ CGS
Chidu dai 1 mt (m)
xangtimet (cm)
Kho'i luong m kilogam (kg) gam (g)
Thai gian t giay (s) gi&y (s)
Dong dien I Ampe (A) Ampe (A)
Nhiet d6 T Kenvin (K) Kenvin (K)

Circmg d6 sang Iv Candela (Cd) -

Luong chat n mol -

Bang 2. Cac dan vi din xuat (he SI)

Dai luong vat H Ten Kf hieu Don vi
Nang luong Jun J kg mV2
Luc Niuton N kgms"2
Cong sua't Oat W kgmV3
Di6n tfch Culdng C As
Dien tro 6m n kgm2s~3A~2
Difin th Von V kgm2s~3A_1
dien dung Fara F A2s4kg"1m 2
Tan so Hec Hz s-1
Ap sua't Patcan Pa kgm_1s"2

170 12- PITDH4UD-B

 Bang 3. Cac hang so vat If cd bin (he SI)
S6 Avogadro
Ntt = 6,0225. 1023
Hang s6 khi If tircrng R = 8,3 14 J. mol"1.K~'
H&ng s6 Boltzmann
k [,3805.1OJ.K"
Na

Hang s6 Plack h = 6,6256. 10"34 J.s

Didn tfch electron e0 = 1,602. 10~19C
31
Khd'i luong tlnh cua electron me = 9,1096.10 kg
Hang s6 Faraday F = 96486,7 Cmo!"1
Kh<5i lucmg proton mp = 1,6725.10~27kg
Hang s6'dien mOi trong chan khftng
= _i_=8.8541.10-|2Fara.m-'
m.c!
D6 thdm chin khdng po = 4n. 10"7 H.m"'

T6c d6 anh sang trong chin khfing c - 299 792 458 m.s-1

Bang 4. Cac thtia so hoan chuyen thong dung

1angstrom (A ) = 10~8 cm = 0,lnm = 10'm

latm = 760 mmHg = 760 torr = 1,01325.106 dyn.cnT2 = 101325 N.nT2

1 bar = 106 dyn cm-2 = 0,987 atm = 100 007,8 N.m2

leal = 4,184 J = 4,184. 107ec

, lculong = 2,9979. 109 don vi tlnh didn (esu)

1 dyn = 10~5 N

1 ec = 2,39.10"8cal= 10~7 J

1eV = 23,06 kcal.mor1 = 1, 602. 10"12 ec

= 1,602. 10"19 J = 8066 cm"1

IF = 96 487 culdng. mol

171
 = 23 062 cal.V'.mol"1
1 R = 8,314 J. mof'-K"1 = 1.987 cal.mol'.K-1

= 82,06 cm3 atm K"1 mol1

= 0,08206 l.atm K"1 mol"1

1 lit. atmotphe = 24,22 cal

= 101,34 J
Bang 5. Cac thua so nho va I6n
Pico (P) 10" 12

Nano (n) 10" 9

Micro (p) 10" 6

Milli (m) 10"3

Centi (c) 10" 2

Deci (d) 1
10

Deka (da) 10

Hecto (h) 102

Kilo (k) 103
Mega (M) 106
Giga (G) 109
Tera (T) 1012

PHy Lyc 2. THt DlfN ClfC CHuXn 6 25C 1BAR

Bang th dien cue chun 6 25C duciii d&y dupe ghi lai ddi vciri m6t sd dien cue quan
trong dua tr6n didn cue chun hidro 6 1 bar thay vi 1 atm truyCn thdng. Ddi vcri nhtfng din
cue kh6ng c6 khi tham gia phan ung, su khac bit vt the dupe th hidn bang phutmg trinh :

cp (bar) - (f> (atm) = In

_
= 0,169 mV.
2F latm

172
 Nhu vay chi nhung the didn cue chun co 4 s6' th&p ph&n mdi c6 su thay ddi ve tri s6' khi
chuyen tir 1 atm sang 1 bar.

Bang 6. Cdc the dif n cyt chuan 6 25C va 1 bar

Phan ung <p/V Phan umg 0 ,
<p /V

,Li+ +e - 3,045 0
Li
H++ e 1

K+ + e - 2,925 0,0711
K AgBr + e Ag + Br

Ba2+ + 2e~ Ba -2,90

CuCI + e -y Cu + CI" 0,137

Sr2+ + 2e~ -Sr -2,89

AgCI + e -y Ag + CI
0,2222

Ca2+ + 2e > Ca -2,87

Hg2CI2 + 2e" 2Hg + 2 cf
0,2674

Na+ +e -> Na
-2,714
Cu2+ + 2e" y Cu 0,137

Ce3+ + 3e~ -yCe -2,48

PlCI42" + 2e~ Pi + 4Q
y 0,73

Mg2+ + 2e -> Mg
-2,37
Fe3+ + e~ y. Fe
c 2+ 0,771

Al3+ + 3e~ -y Al - 1.66 . +

Ag +e - Ag 0,799

Ti2+ + 2e~ y Ti
- 1,63
2Hg2+ + 2e" Hg 2+ 0,920

Mn2+ + 2e -y Mn -1,18
AuCl 4 + 3e - Au + 4CI
1,00

Zn2+ + 2e -> Zn - 0,763 1

Br2 (1) + e y Br~
1,065

Cr3+ + 3e~ -yCr -0,74

ClO 4 + 2H+ +2e~ -yClOj +H20
1.19

Re2+ + 2e -> Fe
-0,44
Mn02 + 4H+ + 2e~ -y Mn2+ + 2HzO 1.23

-0,41
Cr20 7" + 14H+ + 6e
~
-y 2Cr3+ + 7H20 1,33

Cd2+ + 2e"~ y Cd
-0,402 1 1,36

2
CU 4 e y G

Pbl2 + 2e~ -y Pb + 21"

-0,365
Au3+ + 3e -y Au 1,50

- 0,356
PbS04 + 2e y Pb + SO 4 Mn04 + 8H+ + 5e~ -y Mn2+ + 4H20 1,51

Co2+ + 2e~ -y Co
- 0,277
Pb02 + SO 4~ + 4H+ +2e > PbSO + 2H2O 1,685

PbCI2 + 2e~ -v Pb + 2 CI"

- 0,268 - 3+
Co +e -y Co2+ 1,82

173
 Phan ling Phan ung p/V
vrv

-0,151 2,65
Agl +e Ag + 1
-F2(K) +e -> F
2

-0,136
Sn2+ + 2e~ v Sn
Pb2+ + 2e~ -> Pb -0,126

PHU Lyc 3. CAC THONG SO DONG HOC DI0N HOA

Bang 7. Mat do dong trao doi cua mot so phan i/hg dien cut
trong dung djch nude d nhiet do phong
Dien cue Dung dich Dong trao d

H+/H2) Hg H2S04 0,5M 6.10"12

Ni2+/Ni Nia2 1M + H3BO3 2% O
1
CO V O
1

H+/H2, Zn h2so4 1M 10-11

Fe2+/Fe FeS04 1.25M 10 s

H+/ H2, Ni H2S04 0,5M + NiS04 1M 10-7

Zn2+/Zn ZnS04 0,25M da axit hoa 1(T5

H+/H2,Pd h2so4 1M 2.10 s

Cu2+/Cu CuS04 2M + H2S04 0,5M 10'5

H7H2,Pt h2so4 1M 10-3
Na+/Na, Hg Na(CH3)4OH 103M + NaOH 1M 4.10-2
Hg2+/Hg Hg(N03)2 10"3M + HC104 2M 5.10"'
Pb++/Pb,Hg Pb(N03)2 10"3M + KN03 1M 10'1

174
 Bang 8. Mat do ddng trao doi i0 vdi sy thoat hidro
H dew
tCrdung djch H2S04 1M

Kim loai -lgi0[A/cm2] Kim loai -lgi0[A/cm2]

Pd 3 Nb 6,8
Pt 3,1 Ti 8,2
Rh 3,6 * Cd 10,8
Ir 3,7 Mn 10,9
Ni 5,2 Tl 11,0
Au 5,4 Pb 12,0
W 5,9 Hg 12,3

Bang 9. Cac trj soava b cua phUdng tcinh Tafel doi vdi sir khurion hidro
tren vat

lieu
*
catot khac nhau o 25C

Dien Dung djch a/V b/V Din Dung djch a/V b/V
eye cue
Pb 1.56 0,110 Ag 0,95 0,13
H2S04 0.5 M H2S04 2.5M
Tl 1.55 0,140 Fe HQ 1M 0,70 0,125
H2S04 0.85M
Hg 1.415 0,113 Fe NaOH 2M 0,76 0,112
H2S04 0.5M
Hg HCI 1M 1,406 0,116 Ni NaOH 0,1 1M 0,64 0,100

Hg KOH 1M 1,51 0,105 Co HCI 1M 0,62 0,140

Cd 1,40 0,120 Pd KOH 1,1M 0,53 0,130
H2S04 0.65M
Zn 1.24 0,118 W HQ 1M 0,23 0,040
H2S04 0,5 M
Sn HCI 1M 1.24 0,116 W HCI 5M 0,55 0,11

Cu 0,80 0,115 Pt HCI 1M 0,1 0,13

H2S04 0.5M (nhn)

Ag HCI 1M 0,95 0,116 Pi NaOH 1M + 0,31 0.097

(nh&i)
Na2S04 1.5 N

175
 Bang 10. Qua the thoat hidro (dung djch H2S04 0,5M) va qua the thoat oxi
(dung djch KOH 1M) d nhiet do phong tren cac dien eye khac nhau.

Dien cue Qua thd hidro/V Qu the oxi/V

Pt platin hoa -0,00 0,25
Pd -0,00 0,43
Au 0,02 0,53
Fe 0,08 0,25
Pt nhkn 0,09 0,45
Ag 0,15 0,41
Ni 0,21 0,06
Cu 0,23 -
Cd 0,48 0,43
Sn 0,53 -
Pb 0,64 0,31
Zn 0,70 -
Hg 0,78 -

PHU LUC


4. M6T
SO HE THCrC TOAN HOC CO BAN

So mu va luy thifa
Nhidu sd duoc bieu thi mot each Ihukn tien hem dudi dang luy thifa cua 10:
1 =10 100.000 = 105
1
0,1 = 10 3,1623 = 10-5
Mdt each tong quat ndu viet an thi a Ik co so,n la sd mu.
Mdt sd phep toan ve sd mu va luy thira
am x an = am+n
(a"1)" = amXn
am

a"
= am'n

Ckn liru y rkng a0 = 1 vdi moi gia tri cua a trir phi a = 0. Khai nidm logarit la su md rdng
tu nhidn cua sd mu logarit cd so a cua mdt sd x la luy thira y, mdt sd ma x phai duoc nkng
ldn de x = ay. Khi do :
176
 y = iogax
Thi du : 34 = 81, ta co 4 = log381
Neu co s6 a la 10 thi :
logarit sdf mu
lgio' = 0 10 = 1
lg102 = 0,3010 lO0,301 = 2

lg1010=l 10' = 10
lgio 100 = 2 102= 100
lgloO,l=-l io_1 = o,i

Theo quy u6c, dung ki hi6u la thay cho lg1010 d chi logarit cua a.
Vi logarit cua mdt s6 Ik s6 mu nfin n6 cung co chung tinh cht c&a s6 mu:
logarit s<5 mu
IgAB = IgA + lgB 10A x 10B = 10A+B
lgB = lgA-lgB 12 = ioAB
10B
lgAn = nlgA
Mot khi logarit duoc My cho co s<5 e thi ta co loga tu nhin. Dai luong e lk mdt s6 duqc
cho nhir sau
.111
e = 1+
+ + +
1! 2! 3!
...
~ 2,7183
Trong Hoa 11 ham mu y = e* c6 tarn quan trong Ion
lny = xlne= x
Nd'u My loga co s6 10 cua y = ex thi

lg y = xlge

= In y.lge
= lny. Ig2,7183
= In y .0,4343 hay

177
 lny = 2,303 lgy.

Cac phutfng trinh ddn gian

Phuong trinh tuyn tinh (bac nha't) co dang y = mx + b.

D6 thi cua y theo x la mdt dudng thang c6 d0 d6c m va cat true y (tai x = 0) tai b.

Phuong truth bac hai co dang

y = ax2 + bx + c

vdi a, b, c la cac hang s<5 va a

* 0. D6 thi cua y theo x la mdt parabol .
Cac tri trung binh
Khi lap lai mdt phep do, thuong gap trufrng hop gii tri sau sai khac vdi gia tri trudc do
do ket qua nhan duorc la trung binh cua hai gia tri. Co hai loai trung binh, trung binh cdng

thubng gap nha't, do la

Nu hai gia tri do a va b kh6ng bid'n thidn mdt each nglu nhifin thi sii dung phep trung
binh nhan sf&b ,
Chuoi va phep khai trien

...
Cap so cdng 1, 2, 3, 4 ... hoac a, 2a, 3a, 4a

Cap sd nhan 1, 2, 4, 8 ... hoac a, 2a, 4a, 8a ...

Khai tri(in nhi thuc
, n(n-l) n(n-lUn-2) ,
- x +-- -V+...
>

v(1+ x) =1+ nx h--

' 2! 3!

Khai trin ham mu

ex =1 ...
1! 2! 3!
\2
S=1W.(50....
1! 2! 3!

Khai trin luong giac

sinx = x
-- x? + x5 x7
3!
+ + ...
5! 7!

178
cosx =1
-----
. x2 + x4 x6 + ...
4! 6!
2!
 Khai tri&n loga

-----
,, + x). = x x2 + x3 x4 + ...
.In(l
2 3 4

Toan tiTla m6t phep toan cdn tac d6ng vao m6t s6 hay m6t ham
Toan tu Ilm hoSc s6 Dang cuoi cung
lg 24,1 lg24, 1 = 1,382
sT 974,2 974,2=31,21
sin 61,9 sin 61,9 = 0,882
cos X COS X

d ekx del" - ke1"

dx dx

Tfnh vi phan
Ham don bi'n
y = f(x) dy
dx
11-1
nx

ekx kekx
sinx cosx
sin(ax+b) - asin(ax + b)
lnx 1

ln(ax + b)
ax + b

Vi phan toan phn

Vi phan toan phln cua ham hai bid'n U = U(x,y) c6 dang

dU= |
dx
dx + dy =f|(x,y)dx + f2(x,y)dy

179
 ... d2U d2U
V -= - ndn tu phucng tnnh titn suy ra
1
A A

dxdy dydx

ly> (&)
Kdx,X

vol dang thufc nay, lj(x,y)dx + f2(x,y)dy la vi phan loan phan dung.
Noi chung, vcri ham U(x,y) thi d<E dang tha'y rang dU la vi phdn toan phin dung hoac
kh6ng dung. Thuc vay gia. sir c 6 ham U = U(x,y) vdi
dU = (y2 + 3x) dx + exdy

Ta co
d(y2 +3x)N = 2y
dy

'3ex
=e
dx 'y

vay 2y ex do do dU khong phai la vi phan toan phiin diing. Y nghTa cua vi phan toan
*
phSn dung va khdng dung la 6 ch6 nu dU la vi phan toan phan dung thi gia tri cua tich
u, u,
phan J dU chi phu thu6c vao gidi han cua tich phan, tup la: JdU = U2 - U] .
Trai lai nC'u dU khdng phai la vi phan toan phan dung thi
u,

u,
JdU *U2-U,.
Mdt s6 tich phan hay dung

fxndx = xn+1
J n+ 1
+c
Jcosxdx -sinx + c
J = lnx+c
1x Jin xdx = xlnx-x + c
f axdX = -ln(ax + b) + c Je"dx =e" +c
i
+b a
M
Jsinxdx = -cosx-t-c Jfekxdx = -k
+c

180
 Bang tuan hoan cSc nguyen 16
(Khdi lupng nguyen t& cJi/a Iren ,2C.
Cic khoi lupng nguyen tutrong ngoSc don thuQC ve ddng vt bSn nhAf)

C
1

12,011

Nh6m
--
Ky
-- Nguyen lir s6
ht$u
~ Khdi luprig nguySn tr

1 2
H He
1,0079 4.00260
3 4 5 6 7 8 9 10
Li
6,941
Be
9,01218
B
10.81
c
12,011
N
14,0067
o
15.9994
F
I8,996403j
Ne
20,179
11 12 13 14 15 16 17 18
Na
22,98977
Mg
24,306
Al
26,98154
Si
28,0855
P
30,97376
s
32,06
CI
35,453
Ar
39,946
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
99.0983 40,06 44,9559 47,90 50,9415 51,996 54,9360 55,847 58,9332 58,70 63,548 65,38 69,72 72,59 74,9216 78,96 79.904 83.80
37 38 39 40 41 42 43 44 45 48 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Cd In Sn Sb Te I Xe
85.4678 67,62 88,9059 91,22 22,9064 95,94 (&8) 101,07 102,9055 106,4 al
107,868 112.41 114,8? 118,69 121.75 127,60 126,9045 131,30
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs
132.9054
Ba
137,33
La
138.9055
Hf
178,49
Ta
180,9479
w
183,85
Re
186,207
Os Ir Pt
195,09
Au Hg Tl Pb Bi Po At Rn
190,2 192,22 196,9665 200,59 204.37 207.2 208,9804 (209) (210) (222)
67 86 69 104 105 106
Fr Ra Ac Rf Db Unh
(223) 226,0254 227.0278 (261) (262) (263)

D3y Lantanit
56 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140,9077 144,24 (145) 150,4 151,96 157,25 158,9254 162,50 164.9304 167.26 168,9342 173.04 174,967

Day Actinit
1* 90 91 92 93 94 95 96 97 96 99 100 101 102 103
Th
232,0381
Pa
231.0359
u
238,029
Np
237.0462
Pu
(244)
Am
(243)
Cm
(247)
Bk
(247)
Cf
(251)
Es
(252)
Km
(257)
Md
(258)
No
(258)
Lr
(260)
oo
 Chiu trcich nhiem xudt ban:
Chu tich HDQT kim Tdng Giam ddc NGO TRAN AI
Pho Tdng Giam ddc ki6m Tdng bi6n tap VU DUONG THUY

Bien tap ndi dung va sua ban in :

PHUNG PHUONG LlN
Bien tap tax ban ;
VUTHIXUYfiN
Trinh bdy bia va ve hinh :
PHAN HUONG
Chi'ban :
BAN HOA (NXB GlAO DUC)
PH6NG CH BAN (NXB GIAO DUC)

i,

183
 PHANl/NGBlN HOA VA UNG DUNG
Ma s6: 7K532T5 - TTS
In 1.500 bin (02TK), kh6 19x27cm, tai Cdng ty In C6ng Do&n Vit Nam, 167 TSy S<m, Dtfng Da,
Hi Npi. S<5 in: 260. Sd XB: 21/363-05. In xong vi n0p ltfu chiu thring 2 nflm 2005.
184
 TlM OOC SACH DAI HOC VA CAO DANG
BO MON HOA HOC CUA NHA XUAT BAN GIAO DUC

-
1. Hoa hoc Vo cd Tap 1, 2, 3 HOANG NHAM
-
2. Hoa hoc Dai ci/dng Tap 1, 2, 3 renEdidier (VODANGOO,.
djch tir ban tieng Phap)
3. Co so li thuyet Hoa hoc (Phan I:Cau tao chat ) NGUYEN DiNH CHI
4. Co so li thuyet Hoa hoc (Phan II :Nhiet dong hoa hoc, ...) NGUYEN HANH
5. Co so li thuyet cac qua trinh Hoa hoc VO DANG 00
6. Hoa hoc cac hop chat dj vong NGUYEN MINH THAO
7. Hoa li - Tap 1, 2, 3 TRAN VAN NHAN (ChCi bien)
8. Hoa li - Tap 4 nguyEn VAN TUE
9. Hoa hoc Dai cirong (khoi Nong - Lam - Ngu) - Tap 1, 2 NGUYEn VAN tAu (Chu bien)
10. An mon va bao ve kim loai nguyEn VAN tuE
11. Phan tfng dien hoa va lirng dung trAn hip hai
12. Hoa hoc Phan tich
( Phan II :Phan ling cua ion trong dung dich nude
Phan III :Cac phucfng phap djnh luong hoa hoc ) nguyEn tinh dung
13. Giao trinh Hoa li - Tap 1, 2 nguyEn DiNH HUE
14. Hoa hoc - Nam thiinhat, nam thirhai ANDRE DURUPHTHY (DAO QUY chieu,
(Giao trinh dao tao kisuchat luong cao ) TLf NGOC ANH dich tir ban tieng Phap)
15. Hoa hoc Dai CUOng (CDSP ) - Tap 1 . trAn thAnh huE
16. Thirc hanh Hoa hoc Dai cUdng (CDSP) HA TH! NGOC LOAN
-
17. Hoa hoc Vo cd (CDSP ) Tap 1, 2
18. Hoa hoc Phan tich (CDSP)
nguyEn thE ngOn, trAn TH! DA
nguyEn tinh dung
19. Co so Hoa hpc Huru cO (CDSP ) Tap 1, 2, 3 trAn quOc son, nguyEn van tOng,
dAng van liEu
20. Phu-dng phap day hoc hoa hoc (CDSP) - Tap 1, 2, 3 nguyEn cltong, nguyEn manh dung,
nguyEn thi siru
21. Hoa hoc Cong nghe va Moi trUdng (CDSP) PHUNG TlEN DAT (Chu bien)

-
Ban doc co the mua tai cac Cong ti Sach Thiet bj trud'ng hoc 6 dja phuong
hoac cac Cua hang cua Nha xuat ban Giao due :
81 Tran Hirng Dao hoac 57 Giang Vo - Ha Noi
15 Nguyen Chi Thanh - TP. Da Nlng
- -
231 Nguyen Van Cir Quan 5 TP. Ho Chi Minh