CHNG 6

NGUN IN NG HC
CC QU TRNH iN HA
Ni dung
6.1. Ngun in ha hc
6.2. Qu trnh in phn
6.3. Qu th
6.4. ng dng php in phn
6.5. Bi tp
Phn ng oxy ha kh
6.1. Ngun in ha hc
6.1.1. M u
in nng
Ngun in
Mch in ha
Thc t
6.1. Ngun in ha hc
6.1.1. M u
Yu cu
Ngun in Thc t
Sc in ng ln, n nh
Dung lng ring ln: d tr nng lng ln.
Cng sut ring cao nht: ngun cung cp NL ln nht trong
mt n vi thi gian.
Kh nng t phng in nh
6.1. Ngun in ha hc
6.1.1. M u
Phn loi
Ngun in s cp
(Pin)
Ngun in th cp
(Acquy)
Ngun in lin tc
(Pin nhin liu)
c im
Lm vic 1 ln Lm vic nhiu ln Lm vic lin tc
Pin l loi nguyn t gavanic hot ng ch mt vng, ngha l khi
n phng ht in chng ta khng th khi phc li kh nng
phng in ca n.
6.1. Ngun in ha hc
6.1.2. Ngun in s cp Pin
Kho st pin KM - MANGAN
M hnh Pin kh Le Clanch
6.1. Ngun in ha hc
6.1.2. Ngun in s cp Pin
C (+)
MnO
2
+ ZnCl
2
NH
4
Cl
(20%)
Np nha
V
Zn (-)
Cc m (v km):
Zn - 2e = Zn
2+
Cc dng:
2MnO
2
+ H
2
O + 2e = Mn
2
O
3
+ 2OH
-
OH
-
sinh ra to phn ng khng thun nghch:
OH
-
+ NH
4
+
NH
3
+ H
2
O
V: 2NH
3
+ Zn
2+
+ 2Cl
-
[Zn(NH
3
)
2
]Cl
2
Phn ng PIN:
Zn + 2NH
4
Cl + 2MnO
2
= [Zn(NH
3
)
2
]Cl
2
+ Mn
2
O
3
+ H
2
O
(-) Zn / NH
4
Cl,ZnCl
2
/ MnO
2
, C(+)
6.1. Ngun in ha hc
6.1.2. Ngun in s cp Pin
E
pin
=1,6V
Mt s pin khc
Pin Km khng kh: (-) Zn / NaOH / O
2
/ C (+) c E
pin
= 1,4V
Zn + NaOH + O
2
NaHZnO
2
Pin oxt thu ngn: (-) Zn / KOH / HgO, C (+)
HgO + Zn + 2KOH = Hg + K
2
ZnO
2
+ H
2
O
Pin magi bc: (-) Mg / MgCl
2
/ AgCl, Ag (+)
2AgCl + Mg = 2Ag + MgCl
2
6.1. Ngun in ha hc
6.1.2. Ngun in s cp Pin
c quy l loi nguyn t gavanic hot ng thun nghch v
nhiu vng, c th phc hi kh nng phng in bng cch
cho dng in bn ngoi chy qua (np in)
V d
+ Acquy axt: acquy ch
+ Acquy kim: acquy niken - cadimi
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
ACQUY AXT (hay acquy ch)
Khi dung dch in ly vo c quy th xy ra phn ng gia cc
in cc v dung dch in ly lm cho in cc ph mt lp
PbSO
4
:
Pb + H
2
SO
4
= PbSO
4
+ H
2
O
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
(-) Pb, PbSO
4
/ H
2
SO
4
(25-30%) / PbO
2
, Pb (+)
Hot ng c quy ch
in cc m: PbSO
4
+ 2e Pb + SO
4
-2

in cc dng:
PbSO
4
- 2e + 2H
2
O PbO
2
+ SO
4
-2
+ 4H
+
Ton b h thng:
2PbSO
4
+ 2H
2
O = Pb + PbO
2
+ 2H
2
SO
4

Kt qu: Cc m: PbSO
4
Ch xp (hot ng)
Cc dng: PbO
2
Np in
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
Hot ng c quy ch
in cc m: Pb + SO
4
-2
2e PbSO
4

in cc dng:
PbO
2
+ 4H
+
+ SO
4
-2
+ 2e PbSO
4
+ 2H
2
O

Ton b h thng:
Pb + PbO
2
+ 2H
2
SO
4
= 2PbSO
4
+ 2H
2
O
Phng in
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
Sc in ng c quy ch
Trong acquy ch, ngi ta dng axt rt c nn hot ca nc
khng phi l hng s m l: a
H2O
= P/P
0;
cn i vi axt:
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
2
O H
3 3
0
2
O H
2
SO H
0
2 2
4 2
a
m 4 .
ln
F
RT
E
a
a
ln
nF
RT
E E

25
0
C: E
0
=
0
+
-
0
-
= 1,685 (-0,352) = 2,037V

3 2 3
SO
2
H
SO H
m 4 . a a . a a
2
4
4 2



Nu dng H
2
SO
4
27,3% (m = 3,83) th

= 0,165 v a
H2O
= 0,7 th E = 2,047V

ACQUY KIM (hay acquy niken cadimi)
Phn ng in cc:
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
(-) Cd/ Cd(OH)
2
, KOH (20%) // KOH (20%), Ni(OH)
2
, Ni(OH)
3
/ Ni (+)
Phn ng tng trong mch:
Cd + 2OH
-
- 2e Cd(OH)
2
Phng
Np
2Ni(OH)
3
+ 2e Ni(OH)
2
+ 2OH
-
Phng
Np
Cd + 2Ni(OH)
3
Cd(OH)
2
+ Ni(OH)
2

Phng
Np
E
pin
= 1,36V
Mt s acquy kim khc
(-) Zn / Zn(OK)
2
, KOH (40%) / AgO, Ag (+)
6.1. Ngun in ha hc
6.1.3. Ngun in thc cp c quy
Ngi ta thay Cd bng Fe ca acquy trn c acquy kim stniken
Mt loi acquy mi v rt tt l acquy bc km nh sau:
Phn ng tng trong mch:
Zn + AgO + 2KOH Ag + Zn(OK)
2
+ H
2
O

Phng
Np
E
pin
= 1,85V r thay Ag bng Ni E
pin
= 1,7V
S bin i nng lng
Ho nng
6.1. Ngun in ha hc
6.1.4. Ngun in lin tc Pin nhin liu
Pin nhin liu (my pht in ha)
(I) l phn ng
(II) My nhit
(III) My in
Nhit nng in nng C nng
(I)
(II)
(III)
6.1. Ngun in ha hc
6.1.4. Ngun in lin tc Pin nhin liu
Pin HYDRO OXY
(-) Ni/ H
2
/ KOH (30 - 40%) / O
2
, Ni (+)
in cc m: 2H
2
+ 4OH

4e 4H
2
O
in cc dng: O
2
+ 2H
2
O + 4e 4OH

Phn ng tng:
2H
2
+ O
2
= 2H
2
O
Sc in ng 25
0
C:
(thc t t 1 1,1V)
V 23 , 1
23060 . 4
) 690 , 55 ( 2
nF
G
E

M hnh Pin HYDRO - OXY
6.1. Ngun in ha hc
6.1.4. Ngun in lin tc Pin nhin liu
+ -
O
2
H
2
+
ti
Bung kh
in cc dng
(kim loi xp)
H
2
O
H
2
O
H
2
O
OH

OH

Dung dch in ly
KOH
in cc m
(kim loi xp)
Lp ph
xc tc
OH

OH

H
2
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
in phn l mt qu trnh trong c cc
phn ng ha hc xy ra trn b mt in cc
di tc dng ca dng in mt chiu i qua
dung dch in ly hay cht in ly nng chy.
nh ngha
BNH iN PHN dd ZnCl
2
Anod
(+)
Catod
(-)
Cl
-
Zn
2+
Pt
Dung dch ZnCl
2
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Hai in cc nhng vo dung dch in ly v hai in cc ni vi
ngun in mt chiu bn ngoi.
Cc m gi l Catod (-):
Dng oxy ho kh
Zn
2+
+ 2e = Zn
Qu trnh kh.
Cc dng gi l Anod (+):
Dng kh dng oxy ha
2Cl
-
= Cl
2
+ 2e
Qu trnh oxy ha.
QU TRNH iN PHN
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Qu trnh kh dng oxy ha ca cp oxy ha kh.
Khi c nhiu dng oxy ha th s kh dng oxy ha ca cp
no c kh nng oxy ha mnh nht tc l c th in cc
ln nht.
Dng oxy ha chnh l cation KIM LOI hay HYDRO trong
dung dch ION NO PHNG iN???
QU TRNH iN PHN
Ti cc m (Catod)
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Nguyn tc chung
Th hydro:
H2
= -0,059.pH
Trung tnh pH = 7
H2
= -0,059.7 = -0,41V
V vy:
+ Kim loi c > -0,41V s phng in
M
+n
+ ne = M
+ Kim loi c < -0,41V th H
+
/H
2
O phng in:
2H
+
+ 2e = H
2
(pH < 7)
2H
2
O + 2e = H
2
+ 2OH- (pH > 7)

QU TRNH iN PHN
Ti cc m (Catod)
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Nguyn tc chung
Qu trnh oxy ha dng kh ca cp oxy ha kh, thng l
anion ca AXT hay HYDROXT
Khi c nhiu dng kh th s oxy ha dng kh ca cp no
c kh nng kh mnh nht tc l c th in cc nh nht.
QU TRNH iN PHN
Ti cc dng (Anod)
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Nguyn tc chung
ANOD tr: th t oxy ho nh sau:
anion khng cha oxy (I
-
, Cl
-
, S
-2
) OH

anion cha oxy

2OH
-
- 4e = O
2
+ 2H
2
O (pH > 7)
2H
2
O - 4e = O
2
+ 4H
+
(pH <= 7)
QU TRNH iN PHN
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Nguyn tc chung
Ti cc dng (Anod)
ANOD tan: anion phng in hay anod tan tu th.
+
anod
<
oxh/kh
anod s tan
M - ne = M
+n
+
anod
>
oxh/kh
anion s b oxy ha
QU TRNH iN PHN
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Nguyn tc chung
Ti cc dng (Anod)
Nh
vy
PIN: Ho nng in nng
Bnh in phn: in nng ha nng
S in phn l qu trnh ngc vi qu trnh xy ra trong pin
PIN
(-) Zn/Zn
2+
//2Cl
-
/Cl
2
,Pt (+)
IN PHN
Dung dch ZnCl
2
in cc Pt
Cc m Zn = Zn
2+
+ 2e
Qu trnh oxy ha
Catod Zn
2+
+ 2e = Zn
Qu trnh kh
Cc dng Cl
2
+ 2e = 2Cl
-
Qa trnh kh
Anod 2Cl
-
= Cl
2
+ 2e
Qu trnh oxy ha
C qu trnh Zn + Cl
2
= ZnCl
2
C qu trnh ZnCl
2
= Zn + Cl
2

6.2. Qu trnh in phn
6.2.1. Hin tng in phn
PIN IN PHN
Dng in
(in nng)
Phn ng ha hc
(ho nng)
in phn
Pin
Vy hin tng in phn l hin tng cc cht s
hnh thnh hay phn hu di tc dng ca dng in.
S in phn l qu trnh ngc vi qu trnh xy ra trong pin
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
in phn nng chy
IN PHN NaCl
- Qu trnh n gin hn
- Na
+
i v catod nhn electron t ngun thnh Na
- Cl
-
i v anod nhng electron cho ngun to Cl
2
.
Catod (cc m) Na
+
+ 1e = Na
Anod (cc dng) 2Cl
-
- 2e = Cl
2

6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Mt s v d v in phn qu trnh dung dch
IN PHN dd CuCl
2
vi anod tr (Pt)
- Catod xut hin kt ta Cu v th 0,337V > -0,41V
- Anod Cl
-
phng in cho kh Cl
2
bay ra.
Catod (cc m) Cu
2+
+ 2e = Cu
Anod (cc dng) 2Cl
-
- 2e = Cl
2

6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Mt s v d v in phn qu trnh dung dch
IN PHN dd K
2
SO
4
vi anod tr (Pt)
- Catod: K c th -2,924V < -0,41V nn H
+
/H
2
O b kh cho H
2

bay ra v to OH
-
KOH
- Anod: OH
-
/H
2
O b oxy ha to oxy bay ra v H
+
H
2
SO
4
Catod (cc m) 4H
2
O + 4e = 4OH
-
+ H
2
Anod (cc dng) 2H
2
O - 4e = 4H
+
+ O
2

6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Mt s v d v in phn qu trnh dung dch
IN PHN dd NiSO
4
vi anod tan Niken (Ni)
- Catod: Ni c th -0,25V > -0,41V nhng km thua th oxy
ha nc nhiu 1,228V nn to ta Ni
- Anod: in cc Ni ha tan to Ni
2+
Catod (cc m) Ni
2+
+ 2e = Ni
Anod (cc dng) Ni - 2e = Ni
2+
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
Mt s v d v in phn qu trnh dung dch
IN PHN dd H
2
SO
4
vi anod tr (Pt)
- Catod: H
+
b kh to H
2
- Anod: H
2
O b oxy ha cho Oxy bay ra v H
+
ti sinh

Catod (cc m) 4H
3
O
+
+ 4e = 4H
2
O + 2H
2
Anod (cc dng) 6H
2
O - 4e = 4H
3
O
+
+ O
2

Phn ng tng 2H
2
O = 2H
2
+ O
2
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
M hnh in phn dung dch H
2
SO
4
vi anod tr (Pt)
6.2. Qu trnh in phn
6.2.1. Hin tng in phn
V
mA
Pt Pt
H
2
SO
4
K
B
A
C
6.2. Qu trnh in phn
6.2.2. Th phn hu
IN PHN dd H
2
SO
4
vi anod tr (Pt)
V
mA
Pt Pt
H
2
SO
4
K
B
A
C
Khi tng in th bn ngoi E (bng con chy C), khi E cn nh
ng kha K th kim in k lch (c dng in) ri tr v 0 v ti
in cc cha c H
2
v O
2
thot ra.
Khi E t c gi tr 1,7V th kh H
2
v O
2
thot ra, I tng theo E.
Gi tr E
f
= 1,7V c gi l in th phn hy ca phn ng .
IN PHN dd H
2
SO
4
vi anod tr (Pt)
6.2. Qu trnh in phn
6.2.2. Th phn hu
Kho st tip h thng bnh in phn trn
6.2. Qu trnh in phn
6.2.2. Th phn hu
IN PHN dd H
2
SO
4
vi anod tr (Pt)
V
mA
Pt Pt
H
2
SO
4
K
B
A
C I
E
E
f
6.2. Qu trnh in phn
6.2.2. Th phn hu
S khc bit nh nht ca cc in th cn
thit to ra gia hai in cc s in phn
bt u c gi l in th phn hu!!!
Pht biu v th phn
hu
Th phn hy ny khng phi l mt hng s m n ph thuc
vo cc yu t nh:
+ Nhit
+ Kch thc v bn cht kim loi lm in cc
+ Ngay c cu trc b mt in cc.
Yu t nh hng th in cc
6.2. Qu trnh in phn
6.2.2. Th phn hu
Th phn hu khng nh nhau i vi 1 cht
in ly trong cc iu kin khc nhau
Kho st bnh in phn
6.2.3. S phn cc ha hc
Anod
(+)
Catod
(-)
O
2
H
2
Pt
Dung dch H
2
SO
4
K
6.2. Qu trnh in phn
Khi cha ng kha K th hai in cc nh nhau I = 0
Khi ng kho K, d t nhiu vn c phn ng sinh ra H
2
v O
2

nn trong mch hnh thnh pin:
(-) Pt, H
2
/ H
2
SO
4
/ O
2
, Pt (+)
chng li in th E bn ngoi
Hin tng ny gi l s phn cc
6.2.3. S phn cc ha hc
6.2. Qu trnh in phn
Kho st bnh in phn khi E
ngoi
< E
f
Sc in ng ca pin gi l sc in ng phn cc E
p
in th tng in cc gi l th phn cc
p
(
pc
-
pa
)
Ti anod:
E
p
=
oxy
-
hydro
6.2.3. S phn cc ha hc
6.2. Qu trnh in phn
Xc nh th
p
v E
p
Ti catod:

OH
O H
2 / 1
O
0
oxy oxy pa
a
a . P
ln
F 2
RT

2 2
2
H
2
H
0
hydro hydro pc
P
a
ln
F 2
RT



Khi E tng, H
2
va O
2
thot ra nhiu P
H2
v P
O2
tng, H
+
khu
catod gim nhng khu anod tng
oxy
tng v
hydro
gim. Kt
qu E
p
tng.

6.2.3. S phn cc ha hc
6.2. Qu trnh in phn
Bt u in phn

Khi E
p
tng n khi P
O2
v P
H2
bng p sut kh quyn th lc ny
ti cc in cc trong bnh in phn thy thot ra kh H
2
v O
2
.
Khi E
p
t gi tr ti hn, chnh l th phn hu E
f
.
Vy E
ngoi
> E
f
Hin tng in phn xy ra

S phn cc nh trn gi l s phn cc ho hc
hay phn cc in ha.

Tng t phn cc ha hc cn c phn cc nng .
PCN lm gim nng cc ion tham gia phn ng phng
in gn b mt in cc trong qu trnh in phn.
PCN lm tng in th qu trnh in phn, dn n lm tiu
hao in nng do thc t cn kh i lng ny.
gim thng dng cch khuy trn.
PCN lm gim sc in ng ca ngun in khi s dng.
6.2.3. S phn cc nng
6.2. Qu trnh in phn
6.3. Qu th
Kho st li qu trinh in phn H
2
SO
4
1N
PIN
(-) Pt, H
2
/ H
2
SO
4
/ O
2
, Pt (+)
IN PHN
Dung dch H
2
SO
4
1N Pt
Cc m 2H
2
+ 4OH
-
- 4e = 4H
2
O Catod 4H
2
O + 4e = 2H
2
+ 4OH
-
Cc dng 4H
+
+ O
2
+ 4e = 2H
2
O Anod 2H
2
O - 4e = 4H
+
+ O
2
G
298
0
= -nFE
p
= 2x56690 E
p
= E
tn
= 56690/(4.23060) = 1,23V
Th phn hu: E
f
= 1,7V
Suy ra: = E
f
- E
tn
= 1,7 1,23 = 0,47V: qu th
6.3.1. Khi nim qu th
6.3. Qu th
6.3.1. Khi nim qu th
Qu th l s khc bit gia in th phn hu
v tng cc in th cn bng trn cc in cc.
nh ngha
Nm 1905, bng thc nghim tnh qu th ca mt in cc,
Tafel a ra cng thc sau:
a, b : h s ph thuc vo bn cht ca in cc.
i : mt dng.
6.3. Qu th
6.3.1. Khi nim qu th
Trong :
i lg . b a
Qu th ph thuc vo:
Bn cht ca ib cc;
Hnh dng ca in cc;
B mt ca in cc;
Cu trc ca b mt in cc.
6.3. Qu th
6.3.1. Khi nim qu th
in nng cn thit in phn 1 mol H
2
O thu 1mol H
2
v mol O
2
:
W = nFE = 2FE
Khng c qu th th in th din phn E = 1,23V; khi c qu th th
E
f
= 1,7 cho nn in nng tiu hoa tng ln khong 40%.
6.3. Qu th
6.3.2. ngha qu th trong thc t
in phn nc
Do qu th hydro trn kim loi thng rt ln nn c th m kim
loi t dung dch m khng c hydro thot ra.
6.3. Qu th
6.3.2. ngha qu th trong thc t
M kim loi
V d
Xt s in phn Zn
2+
c mt H
+
vi a
Zn
2+ = 1 v a
H
+ = 1;
Ta c:
0
(Zn
2+
/Zn) = -0,763V;
0
(H
+
/H
2
) = 0
Nu khng c qu th hydro th H
+
phng in trc nhng do:

H
2
= 1V (i = 0,1A/cm
2
) nn Zn
2+
phng in.
Trc kia, dng Na kh hp cht NaCl.AlCl
3
:
NaCl.AlCl
3
+ 3Na 4NaCl + Al
in ha, in phn hn hp Al
2
O
3
vi cht tr dung cryolit
3NaF.AlF
3
950
0
C vi catod l than ph Al nng chy:
Al
3+
+ 3e Al
Phng php in phn nng chy ny c th sn xut Mg,
Li, Ca, Ba, Th
6.4. Mt s ng dng thc t ca in phn
6.4.1. in luyn kim
Sn xut Alumin
Khi in phn dung dch CuSO
4
th thu ng kim loi catod:
Cu
2+
+ 2e Cu
Ngy nay, phng php trn dng sn xut cc kim loi
nh Cu, Zn, Ca, Co, Fe tinh khit (99,95%), Mn (99,5%), Cr
(99,8%)
Tinh luyn kim loi nh: Cu, Ag, Au, Pb, Sn, Bi, Ni
6.4. Mt s ng dng thc t ca in phn
6.4.2. M in
Sn xut kim loi tinh khit