CHNG 14 CHNG 14

PIN & IEN CC PIN & IEN CC Chng 14 PIN & IEN CC

2006 Brooks/Cole - Thomson

Pin ien hoa la 1 he thong bien oi hoa nang thanh ien nang nh phan ng oxy hoa kh xay ra 2 ien cc
NGUYEN TAC TAO THANH PIN IEN HOA

cho 2 qua trnh oxy hoa va kh xay ra 2 ni rieng biet (c goi la 2 ien cc) roi noi 2 ien cc nay bang 1 day dan loai 1 th dong electron se c chuyen nh hng t cc am sang cc dng.

2006 Brooks/Cole - Thomson

Cac thuat ng cua PIN

2006 Brooks/Cole - Thomson

KY HIEU PIN
Cr(s) || Cr3+(1M) || Ag++ (1M) || Ag(s) Cr(s) Cr3+(1M) || Ag (1M) Ag(s)

ien cc CATOD ien cc ANOD ban p/ kh ban p/ oxy hoa la ien cc dng (+) la ien cc am (-) Anion b hut ve anod Cation b hut ve catod Dong electron luon chuyen di ve pha catod. - Pin c viet t TRAI sang PHAI [t (-) sang (+)] - Ranh gii gia ien cc va dd: - Ranh gii gia 2 dung dch:

| ||

2006 Brooks/Cole - Thomson

- Ranh gii gia 2 dd co the khuech tan: - Gia cac thanh phan trong dd hay ien cc: dau phay

S hnh thanh lp ien tch kep:

Khi nhung kim loai vao trong dd muoi cua no, do chenh lech ve hoa the cua ion kim loai tren ien cc va trong dd ma xay ra qt hoa tan hay ket tua.

THE IEN CC

2006 Brooks/Cole - Thomson

The ien cc
- S hnh thanh lp ien tch kep gay nen mot bc nhay ien the ien cc.

Khong the xac nh c gia tr tuyet oi cua cac bc nhay the nay, nen dung mot ien cc lam chuan e so sanh: ien cc chuan Hydro Qui c 0H+/H2 = 0 2H+ + 2e- H2

2006 Brooks/Cole - Thomson

 Khi ghep ien cc khao sat vi ien cc 7 chuan th sc ien ong E cua pin tao thanh chnh la o ln cua cua ien cc o. iu kien chuan (25oC, hoat o cac chat =1) ---> the ien cc chuan 0298 QUY C: Neu qua trnh la kh >0 chat Oxy hoa co tnh Oxy hoa > H+ Neu qua trnh la oxy hoa < 0 chat Kh co tnh Kh > H2
2006 Brooks/Cole - Thomson

SC IEN ONG CUA PIN

Pin Zn-Cu: (-) Cu|Zn | ZnSO4 || CuSO4 | Cu (+) K hieu pha: 1 2 3 4 1' Sc ien ong cua pin la hieu the pha 1 va 1'. E= 1' - 1

Khi xet chi tiet cac bc nhay the cac ranh gii phan chia pha ta co: E= (1' -4) + (4 - 3) + (3 - 2) + (2 -1) Khi bo qua the khuech tan th: 4 - 3 =0 E= 1',4 + 3,2 + 2,1 Vi i,j la hieu the gia hai iem nam sau trong long hai pha i,j. Do i,j khong o c bang thc nghiem nen phai s dung ien cc so sanh.

2006 Brooks/Cole - Thomson

9 e xac nh S cua pin: (-) M2| M1 | L1 || L2 | M2 (+) (mach A) ta tao hai mach:(-) M0 | L0 || L1 | M1| M0 (+) (mach B) (-) M0 | L0 || L2 | M2 | M0 (+) (mach C)

Ta co:

EC

EA= M2,L2 + L1,M1 + M1,M2 EB= M0,M1 + M1,L1 + L0,M0 EC= M0,M2 + M2,L2 + L0,M0 - EB = (M0,M2 - M0,M1) + M2,L2 - M1,L1 = M1,M2 +M2,L2 + L1,M1 EA= EC - EB

Nen:

2006 Brooks/Cole - Thomson

Neu ien cc so sanh la ien cc tieu chuan Hydro th EC , EB la the ien cc C , B cua cc (+) & cc (-)

10

Sc ien ong cua mot mach ien hoa bang hieu the gia the ien cc dng va the ien cc am (khi khong co the khuech tan).

E = +

2006 Brooks/Cole - Thomson

NHIET ONG HOC CUA PIN VA IEN CC:

1. Phng trnh nhiet ong c ban cua pin:

11

G = nFE G = nFE
J so ien t trao oi V so Faraday

2006 Brooks/Cole - Thomson

12 2. Anh hng cua nong o en S (E) va the ien cc () - Phng trnh Nernst:

Xet phan ng tong quat xay ra trong pin: aA + bB dD + eE Theo phng trnh ang nhiet Vant Hoff, ta co: G = - RT ln(Ka / a ) nFE = RT ln(Ka / a )= RT lnKa - RTlna d e RT R.T aD .aE E= ln Ka ln a b nF n.F aA .aB PT Nernst:
d e aD .aE 0 RT R.T 0 E=E ln a b E = ln Ka nF n.F aA .aB

2006 Brooks/Cole - Thomson

 Ap dung PT Nernst cho phan ng ien cc: Ox + ne = Kh

13

R.T a Kh ln = n.F a Ox
0

250C, T=298 K , R= 8,314, F=96500, ln10 = 2,303 th:

0,059 aKh lg = n aOx

0

0 : the ien cc chuan (la the ien cc khi hoat o cac cau t bang 1).
2006 Brooks/Cole - Thomson

3. Anh hng cua nhiet o:

H dE E= +T n.F dT
He so nhiet o cua S He so nhiet o cua the ien cc: Trong khoang T hep gan 298K:

14

dE S = dT nF d S = dT nF

=
o T
2006 Brooks/Cole - Thomson

o 298

d + ( T 298) dt

4. He thc Luther

15

Kim loai M co hai cation la Mh+ va Mn+. He nay se co ba qua trnh ien cc: Mh+ + he M (1) G1 = -hFh Mn+ + ne M (2) G2 = -hFn Mh+ + (h-n)e Mn+ (3) G3 = -(h-n)Fh/n V (3) = (1) (2) nen: G3 = G1 - G2 (h-n)h/n = hh -- nn (h-n)h/n = hh nn
2006 Brooks/Cole - Thomson

PHAN LOAI IEN CC

(a) ien cc loai 1 (b) ien cc loai 2 (c) ien cc loai 3 (d) ien cc kh (e) ien cc oxy hoa kh

16

2006 Brooks/Cole - Thomson

ien cc loai 1: ien cc thuan nghch cation/anion

M || Mnn++ :: Mn+ + ne M M M Mn+ + ne M A || An- :: A + ne AnA AnA + ne AnPt Nernst: Pt Nernst:

17

Kim loai hoac phi kim nhung vao dd cha ion cua no.

aM R.T R.T 0 ln ln aM n+ = = + n.F aM n+ n.F

0

R.T aAn R.T 0 = = ln ln aAn n.F aA n.F

0
2006 Brooks/Cole - Thomson

Kim loai c phu chat kho tan cua chnh no (muoi, oxit, hydroxyt) nhung vao dd cha anion cua hp chat kho tan.

ien cc loai 2:

18

M || MA || An- :: MA + ne M + AnM MA An- MA + ne M + AnR.T = ln aAn n.F

0

ien cc calomel: Cl- | Hg2Cl2 | Hg, Pt ien cc bac clorua bac: Cl- | AgCl | Ag

2006 Brooks/Cole - Thomson

kim loai tiep xuc vi hai muoi kho tan co chung anion Mn+ | MA, MA | M : MA + Mn+ = MA + M

ien cc loai 3:

19

MA co o tan nho hn MA : TMA < TMA

=
0 M n+ / M

R.T aM ' A .aM R.T 0 ln ln aAn = M n+ / M + n.F aMA .aAn n.F

2006 Brooks/Cole - Thomson

ien cc kh: kim loai tr tiep xuc vi kh va ion kh.

H++ || H22,, Pt :: 2H++ + 2e H22 H H Pt 2H + 2e H OH || O22,, Pt :: O22 + 2H22O + 4e 4OH OH O Pt O + 2H O + 4e 4OH Cl || Cl22,, Pt :: Cl22 + 2e 2Cl Cl Cl Pt Cl + 2e 2Cl

20

Kim loai tr : truyen dan ien t xuc tac cho p/ ien cc

2006 Brooks/Cole - Thomson

ien cc oxy hoa kh: gom mot kim loai tr nhung vao mot dd co ca hai dang oxy hoa va kh.
V du: Fe3+ | Fe2+, Pt
Ox || Kh, Pt :: Ox + ne Kh Ox Kh, Pt Ox + ne Kh

21

ien cc hon hong ien cc thuy tinh

2006 Brooks/Cole - Thomson

22

Cac loai mach ien hoa

a. Mach hoa hoc mach nong o: Mach hoa hoc: hai ien cc khac nhau ve ban chat hoa hoc hnh thanh mot pin. Mach nong o: hai ien cc giong nhau ve ban chat hoa hoc nhng khac nhau ve hoat o cua dung dch ien cc.

2006 Brooks/Cole - Thomson

23

b. Mach co tai va mach khong tai:

Mach co tai: khi hai ien cc co hai dung dch, giong hoac khac nhau ve ban chat, tiep xuc nhau qua mang xop ton tai the khuech tan. Mach khong tai: 2 dung dch ien cc khong tiep xuc trc tiep nhau. Co the s dung mach kep e loai bo hoan toan the khuech tan.

2006 Brooks/Cole - Thomson

c. Mach thuan nghch va khong thuan nghch:

Phan ng oxy hoa kh xay theo chieu nao con tuy hieu the tac ong: * Neu hieu the tac ong ln hn s cua mach V > E : mach lam viec nh ien phan (thu ien) * Neu V < E: mach lam viec nh pin ien (may phat ien)

24

2006 Brooks/Cole - Thomson

 Mach thuan nghch: Tuy vao ien the ap vao mach, p/ oxy hoa kh co the xay ra theo hai chieu ngc nhau che tao nguon ien lam viec nhieu lan Mach khong thuan nghch Khi thay oi ien the ap vao mach, th xay ra 2 p/ oxy hoa kh khac nhau khong co kha nang tai tao chat ban au

25

2006 Brooks/Cole - Thomson

 Khi 2 dd khac nhau ve dang chat ien ly hoac nong o ma tiep xuc nhau, tai be mat phan chia 2 dd se xuat hien 1 hieu ien the goi la the khuech tan. Nguyen nhan: linh o khac nhau cua cac cation va anion xuat hien lp ien tch kep xuat hien bc nhay the. S mach co tai co 3 bc nhay the:

ien the khuech tan

26

E tai = E + kt

2006 Brooks/Cole - Thomson

dng dng hay am hay am

27

Cach xac nh the khuech tan (t oc)

Neu t- > t+ tc - > + th kt > 0 Etai > E Neu t- < t+ tc - < + th kt < 0 Etai < E Neu t- = t+ tc - = + th kt = 0 Etai = E

2006 Brooks/Cole - Thomson

Bien phap loai tr the khuech tan Dung cau muoi: dung dch am ac cua mot muoi co linh o cation gan bang anion V du: KCl, KNO3, NH4Cl, NH4NO3, kt khong ang ke

28

Tao mach kep: loai bo hoan toan kt

(T OC)
2006 Brooks/Cole - Thomson

NG DUNG CUA PHEP O SC IEN ONG (t oc)

1. Phng phap o sc ien ong 2. o pH 3. Chuan o ien the 4. Xac nh mot so ai lng hoa ly: so tai, , tch so tan

29

2006 Brooks/Cole - Thomson

CAC NGUON IEN HOA Pin s cap Pin th cap Pin nhien lieu
30

Pin s cp lm vic 1 ln trn c s pin khng thun nghch ---> khng thu li cht ban u

Pin th cp (Acquy) lam viec nhieu lan da tren c s pin thuan nghch ---> np ien s dung lai

2006 Brooks/Cole - Thomson

Pin kho
( ) Zn NH 4Cl ( 20%) , ZnCl2
Anod (-)

31

MnO2 , C ( + )

Zn 2e = Zn2 +

Catod (+) 2 MnO2 + H 2O + 2e = Mn2O3 + 2OH

+ OH + NH 4 = H 2O + NH3

2 NH3 + Zn2 + + 2Cl = Zn ( NH3 )2 Cl2 (tinh the t tan) Zn+2NH 4Cl + 2 MnO2 = Zn ( NH 3 )2 Cl2 + Mn2O3 + H 2O
2006 Brooks/Cole - Thomson

Pin Alkaline

32

Anode (-): Zn + 2 OH- ---> ZnO + H2O + 2eCathode (+): 2 MnO2 + H2O + 2e- ---> Mn2O3 + 2 OH 2006 Brooks/Cole - Thomson

Pin Ch Acquy acid

33

Pb, PbSO4 H 2 SO4 ( 25 30%) PbO2 , Pb

Anod (-) Catod (+)
phong PbSO4 Pb + SO 2e nap 2 4 phong 2 PbSO4 + 2 H 2O PbO2 + 4 H + SO + 2e nap + 2 4 phong 2 PbSO4 Pb + PbO2 + H 2 SO4 nap

2006 Brooks/Cole - Thomson

Pin Ni-Cad - Aquy kiem

PHONG Cd ( OH ) Cd + 2OH 2e 2 NAP PHONG 2 Ni ( OH ) + 2OH 2 Ni ( OH )3 + 2e 2 NAP

34

Cd Cd ( OH )2 , KOH ( 20%) KOH ( 20%) , Ni ( OH )2 , Ni ( OH )3 Ni

PHONG Cd ( OH ) + 2 Ni ( OH ) Cd + 2 Ni ( OH )3 2 2 NAP

2006 Brooks/Cole - Thomson

PIN NHIEN LIEU

anode: 2H2(k) + 4OH-(dd) --> 4H2O(l) + 4ecathode: O2(g) + 2H2O(l) + 4e- --> 4OH-(dd) TONG: 2H2(g) + O2(g) --> 2H2O(l)

35

- Dong chat phan ng (nhien lieu + chat oxy hoa) c a vao lien tuc va ong eu cho cac ien cc - Pin nhien lieu lam viec lien tuc, khong tr lai hoa nang - Phan ng tong = phan ng ot chay
2006 Brooks/Cole - Thomson