1

TH IN CC
V PIN IN HA
Chng 5
2
1. Khi nim Th in ha
2. Hiu th trn ranh gii pha
3. Th in cc
4. Nhit ng hc pin in ha

CHNG 5
3
animal electricity Luigi Galvani (1737-1798)
4
1. Khi nim th in ha
Ha th (chemical potential): phn ng gp ca mi cht vo
nng lng chung ca h ha hc (xc nh bng cng a cu
t I khng mang in t trng thi kh i vo pha o)


Th in ha: Khi cht l ht tch in (ion hoc in t) th cn
phi tnh thm c tng tc ca ht tch in vi in trng.
Phn ng gp ca ht tch in vo nng lng chung ca h
th in ha (electrochemical potential).
o

i
5
Ha th (hay th in ha nu l ht tch in) l i lng cho bit
cc tnh cht nhit ng s bin i nh th no khi thay i
lng cht trong h Cng a 1 mol ht t chn khng vo
h.
Th in ha v Ha th
Mt cch hnh thc c th vit:
i j
i
i
N T P
N
G
=
|
|
.
|

\
|
c
c
=
, ,

cF
i j
i
i
N T P
N
G
=
|
|
.
|

\
|
c
c
=
, ,

6
Th in ha l cng chuyn mt mol ht tch in t chn
khng vo bn trong mt pha no .
i i
Z F
o o o
= +

o
- Ni th (Inner electrical potential): bin i nng lng do
chuyn ht i qua lp in kp trn b mt pha + nng
lng tng tc ca i vi cc in tch t do trong pha .

Th in ha, ni th, ngoi th,
(E.A.Guggenheim 1929)
7
Phn b th ca qu cu KL bn knh R, tch in Q
Ni th, ngoi th, th b mt
o o o
_ = +
+
o
- Ngoi th (Outer electrical
potential): cng cc i chuyn i tch in q
t chn khng n b mt ca pha .
_
o
- Th b mt (Surface potential)
cng cc i chuyn i tch in q t b
mt vo pha o

8
o o
o
| F Z
i i i
+ =
o
| F Z
i
o

i
o o
o
| F Z
i i i
+ =
Gi thit: pha hnh cu, tch in;
in tch phn b u thnh lp mng trn b mt cu
i (Z
i
e
o
) trong chn khng.
i
i
i
Hp phn ha hc
i

: cng chuyn i t xa v
cng ti mt im bn trong ca qu cu (pha )
tc b in tch b mt
Hp phn in Z
i
F

: cng cn chuyn 1 mol

cu t i n mt im bn trong qu cu rng
c b mt tch in
Th in ha : cng phi tiu tn chuyn
cu t i n mt im bn trong pha tch in .
o

i
9
Ht khng tch in (Z
i
= 0):
o
o

i i
=
Ht bt k :
i
o
i i
a RT ln
,
+ =
o o

,
ln
o
i i i i
RT a z F
o
o o
= + +
Pha nguyn cht (Z
i
= 0; a
i
= 1):
o
o

, o
i i
=
i i i
z F
o
o o
= +
Th in ha v Ha th
in t trong kim loi
kl kl
e
kl
e
F| ) 1 ( + =
10
2. Hiu th trn ranh gii pha
11
iu kin cn bng gia hai pha o v | :
| o

i i
=
Th in ha v Cn bng pha
1) CB trn ranh gii 2 KL tip xc
2 1
2 1
2 1


F F
M
e
M
e
M
e
M
e
=
=
Th Galvani :
F
M
e
M
e
M M M
M
1 2
1 2 2
1



= = A
Trong cht rn nh kim loi, bn dn th in ha tng ng nng
lng mc Fermi
e
M
=N
a
E
F
)
12 12
Cc mc nng lng
a
Nguyn t
N
L

E = 0
a
Mt phn t
nh
a
Mt phn t
ln
Mc lp
y
Mc
trng
HOMO
LUMO
Mc
Fermi
Mc chn
khng
Tnh cht ha hc c quyt nh bi trao i in t
chuyn di t mc y trng.
Vt liu khi
Mc Fermi trong KL ging nh mc HOMO trong 1 phn t
13
Cu trc di nng lng
Kim loi
Cc di
ct li
Di ha tr
Khong cch
v cng nh
gia trng
thi y v
trng
Khong cch
nh (nhng
khc 0) gia
trng thi y
v trng
Khong
cch ln
gia trng
thi y v
trng
Band Gap
Chng ta tp trung vo kim loi.
Bn dn Cht cch in
14
Mc Fermi
Tp trung vo in t gn ranh gii y/trng.
E=0 (mc chn khng)
E
F
(mc Fermi)
Nng
lng ti
thiu
tch ra
khi mu
Phn b cc trng thi nng lng ca mi vt liu l duy nht.
KL 1 KL 2
E
F
(mc Fermi)
in t cng gn mc chn khng th cng lin kt yu vi khi rn
hay, nng lng ca in t cng cao
Mi vt liu c mt mc nng lng Fermi khc nhau.
Trong p.t, cc mc LUMO va HOMO xc nh, nhng trong KLc
rt nhiu trng thi xung quanh mc Fermi
15
Hai vt dn tip xc nhau
dng in t
+
+
+
+
+
Dn ti cch bit in tch
Hiu th tip xc
Mc Fermi nh nhau trong ton h
16
Ion trong dung dch
cu trc in t ca ion: HOMO, LUMO, HOMO-LUMO gap.
Lowest Unoccupied Molecular Orbital
Highest Occupied Molecular Orbital
HOMO-LUMO Gap
Mc Fermi
- Trng thi ni phn t (quay, dao ng, ) v tng tc ca ion
vi dung mi.
- Mc Fermi!
17
Kim loi trong dung dch in ly
Cc mc Fermi c
xp thng hng
in tch chuyn di
cn bng cc mc
Fermi,
Gy ra cch bit in
tch v hiu th tip
xc.
+
+
+
18
Hai dung dch in ly
+
+
+
Mc Fermi
Xut hin cch bit
in tch lm
bng mc Fermi
v gy ra hiu th
trn ranh gii
19
Th tip xc
Trong mi mch u c th tip xc khi c hai
vt liu khc nhau tip xc vi nhau.

Trong chng trnh mn hc chng ta quan
tm nht n giao din kim loi dung dch.
20
(Hiu) Th Volta : chnh lch in th gia hai im trong chn khng; mt
im gn b mt ca pha th nht, cn im kia th gn b mt ca pha th
hai. Th Volta l hiu ngoi th ca hai pha.
Th Volta c th o c.
o o |
|
A =
o o |
|
A =
(Hiu) th Galvani : hiu th gia hai im nm trong lng hai pha (gi s
l 2 pha v ) hay chnh l hiu ni th ca 2 pha v .
Hai pha ny c th l hai kim loi khc nhau hay mt kim loi v mt cht
lng, hay gia hai pha lng, .
Th Gavani khng th o c
Th Galvani v th Volta
21
Th b mt, th Galvani v th Volta
Chn khng
pha pha
Hiu th volta
Hiu th galvani
22
3. Cn bng trong mch in ha
23
Sc in ng (the electromotive force)
A
ij
=
i

j

A
ij
bc nhy th trn ranh gii gia vt dn i v j;
i
th ca vt dn i.
Sc in ng (s..) E ca mch (1|2|3||N|M) :
E = A
12
+ A
23
+ ... + A
NM
E =
M

1

S.. ca mch ch gm cc kim loi s bng hiu in th gia vt dn cui
cng v vt dn u tin.
Mch h ng : vt dn u tin v cui cng hon ton ging nhau.
Nu mch h ng ch gm ton kim loi E = 0
S.. ca mch h ng c t nht 1 cu thnh l cht in ly s khc 0.
pin in ha hay nguyn t galvani
Pin in ha nguyn t Galvani
24
Fig 18-14 Pg 877
The copper/zinc electrochemical cell. The voltmeter measures the
difference in electrical potentials between the two electrodes.
25
Hm Gibbs v Cng
dG
T
= dH
T
- TdS
dH
P
= dU
P
+ PdV
dG
T,P
= dU
T,P
+ PdV - TdS
dG
T,P
= TdS PdV + W
in
+ PdV - TdS
dU = oq + W
oq = TdS
W = PdV + W
in

dU
T,P
= TdS PdV + W
in

dG
T,P
= W
in

Nh vy, hm Gibss l tm im ca in ha hc, v n xc nh
lng cng in ti a c th nhn c t mt h ha hc.
26
Hm Gibbs v Sc in ng (Hiu th pin)
dG
T,P
= W
in

dG
T,P
= W
in

ngoi

W
in ngoi
= V.Q
V: hiu th gia 2 u mch
Q: in lng di chuyn
H in ha
V = E
pin
(sc in ng)
(nu h thun nghch)
Q = n.F
(khi 1 mol cht phn ng)
/l Faraday
dG
T,P
= W
in

ngoi, max
= nFE
pin

W
n
s AG
T,P
Thc t:
27
Mi lin h gia sc in ng v cc hm s nhit ng
nF
G
E
A
=
P
|
.
|

\
|
A
+ A = A
T
G
T H G
c
c
(

+
A
=
dT
dE
T
nF
H
E
H s nhit ca s...:
2 1
2 1
T T T T
E E E
d
dE

=
A
A
~
(E
1
v E
2
s.. ca
nguyn t ti nhit
T
1
v T
2
)
T T d
dE
nF
G
S =
|
.
|

\
|
A
= A
c
T d
dE
nFT nFE H + = A
AG = nFE
Cn bng, ng
nhit, ng p
28
S v hng s cn bng ca phn ng
v
a
A + v
b
B v
c
C + v
d
D
v v
v v

v
b a
B A
D C o
i
i
a a
a a
RT G
d C
.
.
ln + = A

AG
T,P
= E v
i
.
i

i
o
i i
a RT ln + =
1 = = H
v v
v v
b a
B A
D C
i
a . a
a . a
a
d C
AG
o
= E v
i

o
i

v v
v v
b
B
a
A
d
D
c
C
a a
a a
RT G G
.
.
ln
0
+ A = A
v v
v v
b a
B A
D C
o
P T
a a
a a
nF
RT
nF
G
E
d C
.
.
ln
,

A
=
(sp)
) (
ln
.
.
ln
o
o
j
j
i
i
d
D
c
C
b
B
a
A
a
tc a
nF
RT
E E
a a
a a
nF
RT
E E
v
v
v v
v v
[
[
+ =
+ =
phng trnh Nernst
29
trng thi cn bng AG = 0 nn
0
0
= + A =
|
|
.
|

\
|
+ A = A
v v
v v
K ln RT G
cb
a . a
a . a
ln RT G G
P , T
B A
D C o
P , T P , T
b a
d C
AG
o
= nFE
o
= RT ln K
cb
b a
B A
D C
a a
a a
K
d C
|
|
.
|

\
|
=
v v
v v
.
.
cb
K
nF
RT
E ln
o
+ =
30
Trng thi tiu chun (i chng)
Trng thi tiu chun thng c chn l:
p sut = 1 bar (10
5
Pa)
Nng = 1 molal (mol cht tan/kg dung mi)

Nhit = 298 K (25C = 298,15 K)
NHNG
Tt c cc hm nhit ng u ph thuc vo trng thi; khng c
gi tr tuyt i (tr ENTROPY: c tr tuyt i theo l thuyt).
nh lng cc hm nhit ng, quy c chn trng thi tiu
chun.
31
n v ca p sut thng dng l atmosphere.
1 atm = 1,0134 bar
Trng thi tiu chun i vi p sut thng l 1 atm
Trng thi tiu chun v nng hay dng nht : 1 M (mol/lit).
Trng thi tiu chun (i chng)
32
Trng thi tiu chun ca cht tinh khit
Cht rn tinh khit: l chnh n
Lng tinh khit: l chnh n
Dung mi (thng dng vi lng d): l chnh n

a = 1 cho tt c cc cht ny

33
Dng chuyn in tch
in tch chuyn ng trong pin nh th no?
NO
3

Zn
NO
3

Cu
Zn
2+

Cu
2+

Cl

K
+

e

Nu nng 1 M:
pin k tiu
chun v hiu th
o c = + 1,10
V.
V +
34
Bnh in phn
NO
3

Zn
NO
3

Cu
Zn
2+

Cu
2+

Cl

K
+

e

t hiu th ngoi theo
chiu ngc li.
ln ca hiu th t
vo phi > +1,10 V
/c Cu s ha tan v Zn
s kt ta .
DC V
+
35
4.
QUY C v SC IN NG V
TH IN CC (I.U.P.A.C, 1953)
36
1) Nguyn t (pin) Galvani c biu din di dng s :
Zn | Zn
2+
(a
1
) Cu
2+
(a
2
) | Cu hay
Zn | Zn
2+
(a
1
) Cu
2+
(a
2
) | Cu (*)
Pin Daniel
Ranh gii phn pha: |

Tip xc dung dch :

Ranh gii khng c th tip xc dung dch :
37
(-) Zn (s )| ZnSO
4
(aq ) CuSO
4
(aq )| Cu (s ) (+)
Zn (s )| ZnSO
4
(aq ) CuSO
4
(aq )| Cu (s )
Hnh thnh th tip xc dung dch/dung dch gia 2 ngn
Trit tiu th tip xc dung dch/dung dch gia 2 ngn
38
S bng hiu ca th in cc bn
phi trong s (xy ra phn ng kh)
tr th in cc bn tri s (xy ra
phn ng oxyha); hay:
E
pin
= E
phi (catod)
- E
tri (anod)

2. Sc in ng ca nguyn t Galvani
cm
dd
A
cm
dd
A
Th tip xc gia dung dch
v cu mui, th tip xc s
trit tiu khi tnh S
39
3. Phn ng trong nguyn t
40
3) Phn ng trong nguyn t

Zn
(
s
)
anode
ZnSO
4
(
aq
)
CuSO
4
(
aq
)
Cu
(
s
)
cathode




Phn ng in cc vit dng kh




Cu
2+
(
aq
)
+ 2e

Cu
(
s
)



Bn phn ng

Zn
2+
(
aq
)
+ 2e

Zn
(
s
)




Phn ng pin: cathode anode (phi tri),


Cu
2+
(
aq
)
+ Zn
(
s
)
Cu
(
s
)
+ Zn
2+
(
aq
)
41
4) Th in cc ca bn pin, th d
Zn
2+
| Zn (a)
Cu
2+
| Cu (b)
5) in cc hydro:
Pt,H
2
(P
H2
) | H
+
(a
H+
)
Th ca in cc hydro vi p sut ring
phn ca kh hydro bng 1 bar v hot
ion H+ bng 1 c quy c bng 0
mi nhit .
in cc H tiu chun:
(k hiu: SHE hoc NHE)
0
o
2
/
=
+
H H
E
42
l sc in ng ca cc pin c in cc bn phi (trong
s ) l bn pin v in cc bn tri l in cc
hydro tiu chun :
(Pt) H
2
(1 bar)|H
+
(a = 1)Zn
2+
|Zn (a)
(Pt) H
2
(1 bar)|H
+
(a = 1)Cu
2+
|Cu (b)
vi phn ng trong pin xy ra theo chiu :
H
2
+ Zn
2+
H
+
+ Zn (a)
H
2
+ Cu
2+
H
+
+ Cu (b)
Th in cc
43
Ox + n Red
Th in cc l s... ca pin c cu to in cc ang xt bn phi s
(catod) v in cc hydro tiu chun bn tri s (anod):
(Cu) Pt, H
2
(p = 1 bar)| H
+
(a = 1) Ox, Red |M (Cu)
n
n
H
d
H Ox
a a
P a
nF
RT
E E
+
+ =
.
.
ln
Re
o
2 /
2
Ox + n/2 H
2
Red + n H
+
Bn tri Anod p oxyha:
n H
+
+ n
Bn phi Catod p kh:
Ox + n Red
Phn ng pin
bar p a
H
H
1 ; 1
2
= =
+
(SHE)
(SHE)
d
Ox
a
a
nF
RT
E E
Re
o
ln + =
n/2 H
2

o th in cc tiu chun
19.3
Zn (s) | Zn
2+
(1 M) || H
+
(1 M) | H
2
(1 atm) | Pt (s)
E
0
= E
0
cathode
E
0
anode

E
0
= 0.76 V E
0
= 0.34 V
45
E
0
l th kh chun ( phn ng
kh)
E
0
cng dng th cht oxy
ha c tnh oxy ha mnh
Bn phn ng thun nghch
Gi tr E
0

khng thay i khi
thay i h s t lng
46
Nguyn t galvani c to thnh t hai in cc (bn pin):
anod v catod; trn catod xy ra phn ng kh, cn trn anod
phn ng oxy ha.
Trong s , in cc anod c vit bn tri, in cc catod
c vit bn phi.
Nu loi tr th tip xc gia cc pha lng th sc in ng
ca nguyn t galvani bng hiu ca th in cc bn phi s
(catod) tr i th in cc bn tri s (anod).
Th in cc l sc in ng ca nguyn t c in cc bn
phi (trong s ) l bn pin v in cc bn tri l in cc
hydro tiu chun.
Th ca in cc hydro tiu chun c quy c bng 0 mi
nhit .
Tm tt
47
5.
PHN LOI IN CC
48
PHN LOI IN CC
49
2 1
o
H
2
ln E
H
H
H
P
a
F
RT
E
+
+ =
in cc hydro (SHE, NHE)
vi bn phn ng: H
+
+ H
2

MT VI IN CC SO SNH
pH a
H
059 , 0 lg 059 , 0 0 E
H
= + =
+
25
o
C v p
H
= 1 bar:
Yu cu: Th n nh
50
in cc Ag/AgCl
C) 25 ( 0.05916 .2,303
nF
RT
log 0.059 E E ; ln E E
(S.H.E) mV 197 ) ( E
(S.H.E) mV 222 E
Cl Ag e AgCl
o
o o
o
) (
-
) (
-
) (
-
Cl
-
Cl
=
= =
=
=
+ +
a a
nF
RT
KCl bh
aq
r r
51
in cc Calomel
2 - 0
o o
o
) (
-
) (
-
) (
2 2
] [Cl ln
2F
RT
E E
log 0.059 E E ; ln E E
(S.H.E) mV 268 E
Cl 2 Hg 2 e 2 Cl Hg
-
Cl
-
Cl
=
= =
=
+ +
a a
nF
RT
aq
l
r
52
.6
PHN LOI PIN IN HA
53
Pin vt l
- Pin th hnh
- Pin trng trng
Hiu th nh, ch c ngha gii thch mt s hin tng
trong t nhin
t c trng hp c ti ion
Pin ha hc
- C th khng ti ion hoc c ti ion.
- Hiu th ln, c ng dng thc t nh ngun in ha
hc
- Rt a dng: pin s cp, th cp, pin sc, pin nhin liu,
solar cell,
54
Pin Nng
- C th khng ti ion hoc c ti ion.
- Hiu th khong vi chc n vi trm mV, c ng dng thc
t.
- Hin din nhiu trong c th sng y sinh (Nobel HH 1997)
- Rt a dng trong ng dng phn tch ha hc, y sinh, mi
trng, (u d cc loi)
Nobel Ha hc 1997 : 1/2 cho Paul D. Boyer and John E.
Walker "enzymatic mechanism underlying the synthesis of
adenosine triphosphate (ATP)" ; cho Jens C. Skou "for
the first discovery of an ion-transporting enzyme, Na
+
, K
+
-
ATPase".
55
56
57
Mt s ngun in ph bin
Pin s cp (Primary Batteries) : phn ng pin l bt
thun nghch pin khng sc.


Pin th cp (Secondary Batteries): Phn ng pin l
thun nghch pin sc
Hai loi pin in ha c bn
58
Pin s cp

Pin kh (Leclanche)
Pin
Pin leclanche kim
59
Acquy ch
Catod:
Anod:
Pin th cp - secondary batteries
60
Pin Nickel-Cadmium
Anode: Cd(s) + 2OH-(aq) Cd(OH)
2
(s) + 2e-

Cathode: NiO(OH)(s) + H
2
O(l) + e- Ni(OH)
2
(s) + OH-(aq)
61
Pin liti
62
Pin nhin liu