B CNG THNG

TRNG CAO NG CNG NGHIP TUY HA

..H I

BI TIU LUN :

SV : Hunh Th Phi Dim

Lp : C Ho 31

Tuy Ho, ngy 15 thng 12 nm 2009

..H I

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LI M U
Vn n v luyn, hc phi i i vi hnh l chn l ca cha ng ta c kt t ngn
i nay. V t chn l , trong qu trnh s phm cc thy c lun cho cc hc sinh ca
mnh nhng bi tp thc hnh va p dng c nhng kin thc hc vo vic gii
cc bi tp va cng c v gip cc em ghi nh lu hn cc kin thc. Mn hc Ho
L ny cng khng xa ri chn l . Vic gii cc bi tp,lm cc bi thc hnh v cc
bi tiu lun gip cho cc em va cng c cc kin thc hc va c th tm hiu
c nhiu hn cc kin thc chuyn mn. V trong bi tiu lun ny em d i su vo
nghin cu v pin in, mt trong nhng vt dng khng th thiu trong mi gia nh v
trong cc nghin cu khoa hc, cc bi tp trong bi tiu lun ny cng xoay quanh vn
v pin in. c bit ,vic o sc in ng ca pin c th ng dng tnh h s
hot , s ti , tch s tan ca cc mui kh tando cc bi tp v pin in cng c
ngha thc t kh ln.
Bi tiu lun ny c vit da trn nhng thng k cha y t mt s sch tham
kho, c th cn nhiu thiu st v c ch cha chnh xc nn rt mong c cc bn
gp .
Bi vit bao gm nhng tm tt l thuyt v pin in, a ra mt s dng bi tp, cch
gii v v d tham kho.
Cc phn c trnh by:
Tm hiu v pin in
- in cc
- Pin in
- Th khuch tn
Cc dng bi tp v pin in
- S ca pin
- Cc ng dng ca phng php o sc in ng
- Xc nh hiu ng nhit ca pin

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1. Tm hiu v pin in
1.1.in cc (na pin):
1.1.1 Cc loi in cc:
a) in cc loi 1:
-KN : l in cc gm 2 thanh kim loi(KL) hay kim tip xc vi dung dch cha ion
ca KL hay kim .
-K hiu :
MeMen+
: Men+ + n e ' Me
x:A
+x e ' Ax(Pt) AA
n+
n+
(Pt) Hg[Me] Me
: Me + n e ' Me
b) in cc loi 2 :
-KN : gm 1 thanh KL c ph bi hoc tip xc vi mui kh tan ca KL ri
nhng vo dung dch cha anion ca mui kh tan .
: n MeA + (x n)e ' n Me + n Ax-K hiu : Ax- MeA,Me
c) in cc loi 3:
L loi in cc 3 lp c dng :
Me,MeA,MeAMeA
MeA + Men+ + n e ' Me + MeA
d) in cc oxi ho - kh: (oxh-Red)
-KN : gm 1 thanh Kl tr (Au,Pt) v mt ho hc nhng vo dung dch cha ng thi
dng oxh v dng kh ca cng mt nguyn t.
-K hiu :
oxh,Red (Pt)
: oxh + ne ' Red
1.1.2 in th ca in cc :
Trn ranh gii phn chia 2 pha gm 1 tm Kl c dng lm in cc ( vt dn loi 1 )
v dung dch in phn ( vt dn loi 2 ) xut hin mt hiu th c gi l th in cc
c ln c xc nh bng phng trnh Nernst :
i
RT a oxh
0
oxh/ Red = oxh
+
ln
/ Re d
nF a Rej d
a) in cc loi 1 :
0
oxh / Re d = oxh
/ Re d +

-KL :

VD : CuCu2+
Cu2+ + 2e ' Cu

-Cht kh :

Cu 2+ / Cu

oxh/ Red
oxh/ Red

RT
i
ln a cation
nF

RT
ln a Cu 2 +
2F
i
Poxh
RT
0
= oxh / Re d +
ln
nF a Rej d

= 0 Cu 2+ / Cu +

0
oxh / Re d

i
RT a oxh
+
ln
nF PRej d

VD :* ( Pt) Cl2Cl
Cl2 + 2e ' 2Cl

Cl

2 / Cl

= Cl0

/ Cl

RT PCl2
ln
2 F aCl2

* (Pt) H2 H +
2H + + 2e ' H2

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H
-Hn hng :

= H0
+
/ H2

oxh/ Red

/ H2

2
RT a H +
ln
2 F PH 2

0
= oxh
+
/ Re d

a i n+
RT
ln jMe
nF a Me( Hg )

VD : (Pt) Hg [Cd] ( 2,5 %)Cd2+

Cd2+ + 2e ' Cd (Hg)

Cd

2+

0
= Cd

/ Cd(Hg)

2+

/ Cd ( Hg )

a 2+
RT
ln Cd
2 F aCd ( Hg )

b) in cc loi 2 :
RT
j
ln a anion
nF
VD : (Pt) Hg,Hg2Cl2Cl
Hg2Cl2 +2e ' 2Hg + 2Cl

oxh/ Red

0
= oxh
/ Re d -

Hg Cl / Hg,Cl
2

0
= Hg

2 Cl 2 / Hg , Cl

RT
ln aCl2
2F

c) in cc loi 3 :
RT
i
0
oxh/ Red = oxh
ln a Me
/ Re d +

n+

nF
VD : Pb,PbC2O4,CaC2O4CaCl2
PbC2O4 + Ca2+ + 2e' Pb + CaC2O4

PbCO ,Ca
2 4

2+

/ Pb,CaC2O4

0
= PbC
+
O ,Cd 2 + / Pb ,CaC O
2

RT
ln aCa 2 +
2F

d) in cc oxh- kh :
i
RT aoxh
0
oxh/ Red = oxh
ln
/ Re d +
nF a Rej d
VD : (Pt)Fe3+,Fe2+
Fe3+ + e ' Fe2+

Fe

3+

/ Fe2+

0
= Fe

3+

/ Fe 2 +

RT aFe3+
ln
F
aFe2+

0 c tnh so vi in cc hiro chun khi PH 2 = 1atm ,nn khi tnh th in cc kh

p sut tnh theo n v atm.

1.2 PIN IN :
-KN : l dng c dng bin ho nng thnh in nng, dng in pht sinh trong pin
l do kt qu ca cc phn ng xy ra in cc.
-Cu to : pin in c cu to t 2 in cc, mi in cc c nhng vo trong mt
dung dch in ly thch hp.
-K hiu : Cc (-) ghi bn tri
Cc (+) ghi bn phi
Gia cht lm in cc vi dung dch ghi mt gch ()
Gia 2 dung dch ta gch hai gch song song ( )
1.2.1 Cc loi pin in :
a)Pin thun nghch Jacobi Daniel
b) Pin khng thun nghch Vonta
c) Pin nng

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L pin gm hai in cc ging nhau c nhng vo hai dung dch ca cng mt cht
in ly c nng khc nhau.
- Pin nng loi I : hai in cc l hn hng hoc kh
- Pin nng loi II : + pin nng thun nghch vi cation
+ pin nng thun nghch vi anion
1.2.2 Sc in ng(S) ca pin :
L hiu th o c i vi pin in khi khng c dng in lu thng trong mch gi l
sc in ng ca pin.
E = + > 0
1.2.3 Nhit ng lc hc v pin in :
RT
G 0 = nFE p0
E p0 =
ln K CB
nF
G = nFE p
1.2.4 Mi lin h gia S ca pin v cc hm nhit ng :
dE p

S = nF
dT P
H = G + T .S
dE
H = nFE P + T .nF P
dT P
d 2 EP
dH
C P =
= nFT
2
dT P
dT
E=

H
dE
+ T . P
nF
dT P

1.3 TH KHUCH TN
Khi hai dung dch cht in ly tip xc nhau, ch tip xc xut hin mt hiu
in th do qu trnh chuyn ion qua ranh gii tip xc gy nn. Hiu th ny c gi l
th khuch tn. K hiu : kt
Do : Echung = E + kt
Ta ch kho st th khuch tn 3 loi pin sau :
a)Pin nng thun nghch vi cation :
VD : Ag AgNO3AgNO3Ag
<
C2
C1
RT C2
kt = (t + t )
ln
nF C1
b) Pin nng thun nghch vi anion :
VD : Ag , AgCl Cl Cl AgCl , Ag

>
C2
RT C1
kt = (t t + )
ln
nF C 2
c) Pin vi hai dung dch c nng ging nhau v c mt ion trong chung :
VD : Zn Zn( NO3 )2 Cu ( NO3 )2 Cu
C1

0,1N

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0,1N

RT 1
ln
nF 2
1 , 2 l dn in ca 2 dung dch
(*) Cch trnh th khuch tn :
- Dng cu mui ( dung dch lm cu mui c linh cation, anion gn bng nhau )
- Cho vo c hai dung dch cht in ly l c nng cao hn nng cc cht in ly
ca pin nng , lc ny ton b dng in l do cc ion cht in ly l ny chuyn i.
- Dng mch ho hc kp : mc xung i 2 pin ho hc.
VD : Ag , AgCl HCl (a1 ) H 2 ( Pt ) LL ( Pt ) H 2 HCl (a 2 ) AgCl , Ag

kt =

E = E1 E2
2.CC DNG BI TP V PIN IN :
2.1. S ca pin :
-Bi ton tng qut : T pin in ( phn ng trong pin ) + nng + th cc chun
Tnh : th in cc, S , nng cc ion khi pin dng ht.
-Cc dng bi tp :
Cho phn ng vit s pin in.
Cho s pin vit phn ng xy ra trong pin.
Cho in cc , th in cc chun lp pin.
Pin in c th khuch tn.
-Cch gii : Thit lp phn ng in cc, th in cc.
E p = (+) () > 0
Pin ngng hot ng E=0
Lu : dung dch v cng long
+ = =+

hay lg + = AZ + Z I

I = 1 C i Z i2
2
-V d :

Zn + 2Ag+ Zn2+ + 2Ag l phn ng tng qut khi pin lm vic.Cho

0
0
Zn
= 0,76V ; Ag
= 0,80V . 250C ,
2+
+
/ Zn
/ Ag

[Zn2+]=0,1M;[Ag+]=0,1M.Hy
a) Thit lp s pin in
b) Tnh Ep
c) Nng ion khi pin khng cn kh nng pht in
Gii:
Ta thy:
Zn 2e Zn2+ cc (-)
2Ag+ +2e Ag cc (+)
Vy s pin : Zn Zn 2+ Ag + Ag

0,059
lg Zn 2+ = -0,7895 (V)
2
0
,
059
0
(+ ) = Ag
+
lg Ag + = 0,741 (V)
+
/ Ag
1
E = ( + ) ( ) = 1,5305 (V)

0
+
b) ( ) = Zn
2+
/ Zn

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c)Khi pin ht in tc l E = 0 hay ( + ) = ( )

0
Ag
+
+
/ Ag

[Ag ] = (
lg
[Zn ]
+ 2
2+

0,059
0,059
0
lg Ag + = Zn
+
lg Zn 2+
2+
/ Zn
1
2
0
Zn 2 + / Zn

0
Ag
+
/ Ag

2
) 0,059
-53

[Ag ] = 10-53
[Zn ]
+ 2
2+

Gi x l lng km phn ng
2x l lng bc phn ng
[Ag+]=0,1-2x
[Zn2+]=0,1+x
Pin ngng hot ng [Ag+] 0 x 0,05 M
[Zn2+]= 0,1 + 0,05 = 0,15 M
[Ag+] 10 53 0,15 1,22.10-27
250C, mt pin in c to ra t 2 in cc : mt in cc gm 1 tm
Cu nhng trong dung dch CuSO4 0,5M .in cc th 2 l mt day Pt
nhng vo dung dch Fe3+,Fe2+ vi lng sao cho [Fe3+]=2[Fe2+]. Dng
mt dy dn c in tr Rni hai u Cu v Pt.
a)Vit s pin in v phn ng xy ra trong pin.
b)Tnh S ca pin.

c)Bit rng th tch dung dch CuSO4 kh ln, tm t s

ngng hot ng
0
0
Cho bit Cu
= 0,34V ; Fe
= 0,77V
2+
3+
/ Cu
/ Fe 2 +

[Fe ]
[Fe ]
3+

2+

khi pin

Gii:
Cu 2+ + 2e ' Cu
0,059
0
(1) = Cu
+
lg Cu 2 + =0,331 (V)
2+
/ Cu
2
Fe3+ + e ' Fe2+
0,059 Fe 3+
0
= 0,788 (V)
(2 ) = Fe3+ / Fe 2 + +
lg
1
Fe 2 +
Ta thy : 2 > 1 Cc Cu l cc (-)
Cc Pt l cc (+)
S pin in :
Cu CuSO 4 Fe 3+ , Fe 2+ ( Pt )

[
[

]
]

Cc (-) : Cu 2e Cu2+
Cc (+) : 2Fe3+ +2e 2Fe2+
Cu + 2Fe3+ Cu2+ +2Fe2+
b) E = ( + ) ( ) = 0,788-0,331 = 0,457 (V)
c)Pin ngng hot ng E = 0 hay ( + ) = ( )

V th tch dung dch CuSO4 kh ln nn [Cu2+] xem nh khng i.

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 0,77 +0,059 lg

[Fe ] = 0,331
[Fe ]
3+

2+

[Fe ] =4,8.10-8
[Fe ]
3+

2+

Tnh S 250C i vi pin Zn ZnSO4 (0,01m) KCl (bh) Hg 2 Cl 2 , Hg ;bit

th chun ca in cc km bng 0,387 v th ca in cc calomel bo

ho l 0,242 V.
Gii:
Cc (-) : Zn
-2e Zn2+
Cc (+) : Hg2Cl2 +2e 2Hg + 2ClZn + Hg2Cl2 2Hg + ZnCl2
0
( + ) = Hg
Cl
2

/ Hg ,Cl

0,059
lg aCl2 = 0,242(V )
2

0,059
lg a Zn 2 + = 0,763 + 0,0295 lg(0,387.0,01) = 0,834(V )
2
0
E p = ( + ) ( ) = cal
( ) = 1,076(V )

0
( ) = Zn

2+

/ Zn

S ca pin c khuch tn (Xem phn 1.3 )

t+ =

+ +

t =
+ +
Vi + ,- l dn in ng lng ca cation,anion.
Vd : Tnh S ca pin sau 180C
( Pt ) H 2 KOH (0,001N ) KCl (0,001N ) HCl (0,001N ) H 2 ( Pt )

Cho + ca HCl v KCl =1.Tch s ion ca nc =1,2.10-14

H + = 315cm 2 / , Cl = 65,5cm 2 / , K + = 64,9cm 2 / , OH = 174cm 2 / .

Gii:
S dng cng thc Lewis-Sergent ( 1.3.c)
-Trn ranh gii HCl(0,001N)KCl(0,001N)
RT HCl
8,314.291 315 + 65,5
kt' =
ln
=
ln
= 0,027
F
KCl
96500
64,9 + 65,5
-Trn ranh gii KOH(0,001N) KCl(0,001N)

kt" =

8,314.291 64,9 + 174

RT KOH
ln
=
ln
= 0,015
96500
64,9 + 65,5
F
KCl

M:

aH + =

K H 2O
aOH

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1,2.10 14
= 1,2.10 11
0,001

S ca h khng c khuch tn:

RT a H + (1)
E=
ln
F
a H + ( 2)
8,314.291
0,001
ln
0,457;
96500
1,2.10 11
a H _ (1) , a H + ( 2) l hot H+ dung dch c v long).
E=

S ca c mch E chung = E + kt' + kt" = 0,415 (V)

2.2.Cc ng dng ca phng php o sc in ng :
2.2.1.Tnh h s hot trung bnh :
-Bi ton : cho Ep , E p0 , nng dung dch .Tnh .
-Cch gii :Vit biu thc tnh Ep
Thay ai = i.C i
Xem + = =

Biu thc s c dng : E p = E p0 +

RT
ln( i .C j )
nF

-V d :
i vi pin Cu CuCl 2 (m) AgCl , Ag ,S 250C E=0,191 (V) khi m=10-4,

E=-0,074 (V) khi m=0,2.Tnh =?

Gii:
Cc (-) : Cu 2e Cu 2+
Cc (+) : 2 AgCl + 2e 2 Ag + 2Cl
Cu + 2 AgCl 2 Ag + CuCl 2
0,059
E p = E p0
lg(aCu 2 + .aCl2 )
2

([ ][ ] )

E p = E p0 0,0295.3 lg 0,0295 lg Cu 2+ . Cl
Vi m=10-4 c th xem =1, do :

0,191 = E p0 0,0295 lg 10 4. 2.10 4

) ]= E
2

0
p

+ 0,036

E p0 = 0,145(V )

Vi m=0,2 :
2
0,074 = E p0 0,0295.3. lg 0,0295 lg 0,2.(0,4)

ThayE p0 = 0,145(V )
lg 0,3 0,5
S ca pin 250C ( Pt ) H 2 HCl AgCl , Ag bng 0,3524(V) . Cho bit th

chun ca in cc phi l 0,2224(V) .Xc nh trong dung dch HCl

0,1 m ,bit PH 2 = 1atm .
Gii:
0
( + ) = AgCl
0,059 lg aCl
/ Ag ,Cl

( ) = H0

/ H2

+ 0,059 lg a H + = 0,059 lg a H +

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E = ( + ) ( ) = E p0 0,059 lg(a H + .aCl )

Ta c :

a H + .aCl = a 2

1 1 2
C = 1 .1 .C dd = C dd
a = .C

dd

Hay:
E = E p0 0,059.2. lg( .C dd )
E = 0,2224 0,059.2. lg( . .0,1)
lg( .0,1) = 1,10169

.0,1 = 0,079
Vy =0,79
S ca pin 250C

Hg , Hg 2 Cl 2 KCl bh KCl (0,1m) AgCl , Ag bng

0,047 V.Cho bit th chun ca in cc phi l 0,2225 v cal =

0,2415.Xc nh h s hot ca ion trong dung dch KCl 0,1m.
Gii:
Ta c:
2 Hg + 2Cl 2e Hg 2 Cl 2
2 AgCl + 2e 2 Ag + 2Cl
2 Hg + 2 AgCl Hg 2 Cl 2 + 2 Ag
0,059
0
( + ) = AgCl

lg aCl
/ Ag ,Cl
1
0
E p = ( + ) Cal = AgCl
0,059 lg( Cl ) Cal
/ Ag ,Cl

[ ]

0,047 = 0,2225 0,059 lg( 0,1) 0,2415

lg( .0,1) = 1,12 0,77

673K, pin Ag AgCl nongchay Ag ( hp kim Ag-Au,NAg=0,5)

a1
a2
c S E=0,072V .Tnh hot v h s hot ca Ag trong hp kim
Gii:
Pin nng a1>a2 v a1=1 (cht rn ).
RT
E=
ln a 2
nF
8,314.673
0,072 =
ln a 2
96500
ln a 2 = 1,24
a 2 = 0,289
a 2 = N =

0,289
= 0,578
0,5

Vy =0,578
2.2.2. Xc nh tch s tan ca mui kh tan:
-Bi ton : Cho th chun ca mui kh tan,th chun ca cation mui kh tan (hoc t
hot v S tnh c th chun ).Xc nh tch s tan .
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10

-Cch gii : da vo cng thc

0
0
MeA
= Me
/ Me , A

-V d :

n+

RT
ln TMeA
nF

/ Me

250C, sut in ng ca pin:

+
Ag , AgCl Cl (a = 0,0769) Ag (a = 0,072) Ag
bng 0,4455V. Tm tan (ra mol/l) ca AgCl 250C.
Gii:

Cc (-): Ag + Cl e AgCl
Cc (+): Ag + + e Ag

Ag + + Cl AgCl
0
( + ) = Ag

/ Ag

+ 0,059 lg a Ag +

0
( ) = AgC
0,059 lg aC1
1 / Ag ,C1

0
0
m AgC
= Ag
= 0,059 lg T AgC1
+
/ Ag
1 / Ag ,C1

E = ( + ) ( ) = 0,059 lg
0,4455 = 0,059 lg

a Ag + .aC1
T AgC1

0,0769.0,072
T AgC1

T AgC1 = 1,557.10 10

][ ]

M T AgC1 = Ag + . Cl

] [ ]

Ag + = Cl = T AgC1 = 1,248.10 5 (mol / l )

S ( Pt ) H 2 ( P = 1atm) H 2 SO4 (m) Ag 2 SO 4 , Ag . 250C E0 = 0,627 V .
0
= 0,799V .
Tnh tch s tan ca mui kh tan Ag2SO4, bit Ag
+
/ Ag

(+)
()

Gii:
Cc (-) : H2 -2e
2H+
Cc (+) : Ag2SO4 +2e 2Ag + SO42H2 + Ag2SO4 2Ag + H2SO4
Hay
H2 +2Ag+ 2Ag + 2H+
Xem h s hot ca cc ion l1,
0,059
2
0
= Ag
lg SO4
2
2 SO4 / Ag , SO4
2
+ 2
0,059 H
=
lg
2
PH 2

E p = E p0

[ ]

[ ] [SO ] ) (1)
0,059 [Ag (tan)]
+
lg
2
[H ]

0,059
lg( H +
2

0
E p = ( + ) ( ) = Ag
+
/ Ag

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+ 2

11

0
= Ag
+ 0,0295 lg
+
/ Ag

0
= Ag
+ 0,0295 lg
+
/ Ag

[ ][
2

[Ag ] [SO ]
[H ] [SO ]
+ 2

+ 2

T Ag 2SO 4

[H ] [SO ]
+ 2

Khi H + SO4 = 1 , t (1)

Ep = E0p = 0,627 (V)
Hay :
0
0,627 = Ag
+ 0,0295 lg
+
/ Ag

T Ag 2SO 4
1

0,627 = 0,799 + 0,0295 lg T Ag 2 SO4

T Ag 2 SO4 1,48.10 6
2.2.3.Xc nh s vn ti:
-Bi ton: Cho : + Echung/Eti. + hot /(nng ,h s hot ).
Tnh s ti.
-Cch gii: Xc nh a1(-); a2 (+) ( l hot cc m v dng)
RT a 2
N u a1< a2: E chung = 2t + .
ln
nF a1
RT a 2
ln
Et = 2t .
nF a1
RT a1
ln
E chung = 2t.
nF a 2
N u a1>a2 :
RT a1
ln
Et = 2t.
nF a 2
E chung = E + kt .
Lu :
Et = E kt
-V d :
Xc nh s ti ca ion Cu+ trong dung dch CuSO4 long , bit 250C
sut in ng ca pin nng c ti:
Cu CuSO4 (0,001m) CuSO4 (0,01m) Cu

bng 0,0268V. + ca CuSO4 trong dung dch CuSO4 0,001m l 0,74, ca

dung dch CuSO4 0,01m l 0,44.
Gii :
a = C1 . 1 = 0,001.0,74 = 7,4.10 4
Ta c: 1
a 2 = C 2 . 2 = 0,01.0,44 = 4,4.10 3
a1 < a 2 pin nng thun nghch vi cation.

kt = (t + t )
E=

RT a1
ln
2F a2

RT a1
ln
2F a2

E t = E kt =
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RT a 2
ln (1 t + + t )
2 F a1
12

t+ =

+ +

t =
;
+ +

1 t+ + t =

2
+ + + +
=
= 2t
+ +
+ +

Et = 2t .
0,0268 = t .2.

RT a 2
ln
2 F a1

0,059 4,4.10 3
lg
2
7,4.10 4

t = 0,587
t + = 1 t = 0,413
Vy s ti ca Cu2+ trong dung dch l 0,413
2.3.4.Xc nh hng s cn bng:
-Bi ton : Cho pin in, th chun ca ion .Xc nh KCB.
j
a sau
-Cch gii : K CB = i
atruoc
G = nFE = 0 E = 0

Khi CB :
RT
0
E p = nF ln K CB
Hoc dng cng thc :
0

KCB =10G / 2,303RT

-V d :

Tnh KCB ca phn ng ZnSO4+Cd'CdSO4+Zn 250C vi

0
0
Zn
= 0,763(V ) ; Zn
= 0 , 076 (V )
2+
2+
/ Zn
/ Zn

Ta c

0
Zn 2 + / Zn

0
Cd 2 + / Cd

Gii:
<0 phn ng xy ra theo chiu nghch

Phn ng c th vit
Zn + Cd2+ 'Zn2+ +Cd
a 2+
(xem hot ca kim loi l 1)
K Cb = Zn
aCd 2 +
Nu to pin t cc in cc trong hot ca cc ion bng hot cn bng
th phn ng khng xy ra v E = 0 hay:

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0,059 aCd 2 +
lg
=0
2
a Zn 2 +

0
0
Zn
+
E = Cd
2+
2+
/ Cd
/ Zn

0,402 + 0,763 +

0,059
1
lg
=0
2
K CB

K CB 1,73.1012
2.3.5.Tnh hng s phn ly:
a)Tnh hng s khng bn ca ion phc:
0
-Bi ton : Cho ion phc R c ion trung tm Men+ c R0 / Me ; Me
.Tnh hng s
n+
/ Me

khng bn ca ion phc.

-Cch gii : p dng cng thc
RT
ln K kb
nF
Vi R l ion phc ,Men+ l ion trung tm.
0
R0 / Me = Me

n+

/ Me

-V d :
0
Au
= 1,7V
+
/ Au

25 C , 0
.Tnh Kkb ca ion phc Au (uCN)2 .
Au (uCN )2 / Au , SCN = 0,69V
Gii :

Au + 2SCN e Au (SCN )2

Au + + e Au
Au + + 2 SCN Au (SCN )2

0
Au
( SCN )

/ Au , SCN

lg K kb =

0
= Au
+ 0,059 lg K kb
+
/ Au

1,7 + 0,69
17,12
0,059

K kb 7,6.10 18
b)Tnh hng s phn ly ca ion:
-Bi ton :Cho pin in,Ep ,th in cc,hot ( nng dung dch + h s hot ),Kpl
ca cht trong nc. Xc nh Kpl ca cht trong pin.
-Cch gii : Thit lp S ca pin

K pl =

aMen+ .a Ax
aMeA

Nng cc cht v ion trong dung dch b nh hng bi s phn ly nn cn

thit lp li da vo phng trnh phn ly v Kpl cho.Thay cc d kin vo biu thc
E gii bi ton.
-V d :
( Pt ) H 2 ( P = 1) HAc(0,01m), NaAc(0,01m), NaCl 0,01m AgCl , Ag.
0
250C c E =0,6220, AgC
= 0,2225V. Xc nh Kpl.
1 / Ag ,C1

Gii:
+

Cc (-): H 2 2e 2 H
Cc (+): 2 AgCl + 2e 2 Ag + 2Cl
H 2 + 2 AgCl 2 Ag + 2 HCl.

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14

 ( ) = 0,059 lg a H

0
( + ) = AgC
0,059 lg aCl
1 / Ag ,C 1

E P = E P0 0,059 lg(a H + aC1 )

Ka l hng s phn li ca HAc trong dung dch, ta c:

Ka =

a H + a Ac
a HAc

aH + =

a HAc .K a
a Ac

a a HAc .K a
E P = E P0 0,059 lg C1

a Ac

a .a HAc
E P0 E P
= lg C1
lg K a .
0,059
a Ac

B qua h s hot , ta c:

[ ]
[ ]

E P0 E P
Cl .[HAc ]
= lg
0,059
Ac
HAc H + + Ac
NaCl Na + + Cl
H 2 O H + + OH

[Cl ]

NaCl Na + + Cl
= [NaCl ] = 0,01m

[HAc] = 0,01 [H + ] + [OH ]

[Ac-] = 0,01+ [H+]-[OH-]

[HAc]= [HAc] ban u tr lng b phn ly + lng H+ do nc phn ly ( s kt
hp Ac- thnh Hac )
[NaAc] = [NaAc] ban u tr lng b phn ly +NaAc mi to thnh (Na+ phn
ly s kt hp ion Ac- do Hac phn ly to li NaAc, nhng lng H+ do H2O phn
ly cng c kh nng kt hp Ac- to HAc )
S phn ly nc l khng ng k hay [OH-] 0
S phn ly ca Hac trong nc l 1,8.10-5- ,ta c :
H + . Ac
'
Ka =
1,8.10 5
[HAc]

V Ac [HAc ] H + 1,8.10 5

[ ][ ]

[ ]

[HAc] = 0,01 1,8.10 5 9,982.10 3 (m)

Ac = 0,01 + 1,8.10 5 0,010018(m)
Ta c biu thc :

[ ]

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 0,01.9,982.10 3
0,6220 + 0,2225
+ lg K a
= lg
0,059
0,010018
K a 1,7.10 5
2.3.6. Xc nh pH ca dung dch:
-Bi ton:Cho pin in, th tiu chun,S, hot ( nng ,h s hot ).Xc nh
pH ca dung dch.
-Cch gii: Da vo cng thc tnh th in cc
-V d :
Cho pin in ( Pt ) H 2 ( P = 1) H + (a = x) KCl (0,1M ) Hg 2 Cl 2 , Hg . 250C,
0
Hg
Cl
2

/ Hg ,Cl

= 0,268V v E=0,5000V .Xc nh pH.

Gii:
Cc (-) : H2 -2e
2H+
Cc (+): Hg2Cl2 +2e 2Hg + ClH2 + Hg2Cl2 2Hg + 2HCl
0
( + ) = Hg Cl / Hg ,Cl 0,059 lg aCl
2

( ) = 0,059 lg

aH +

PH 2
Xem h s hot l 1,
0
0,059 lg
E = ( + ) ( ) = cal

[ ]

[H ][. Cl ]
+

PH 2

0
E = cal
0,059 lg Cl + 0,059 pH

pH 2,393
2.4.Xc nh hiu ng nhit ca pin:
dE p
; cho Ep hoc E p0 .Xc nh hiu ng nhit
-Bi ton: Cho h s nhit ca S
dT p
ca phn ng trong pin.
-Cch gii :Vit phn ng trong pin xc nh n , p dng cc cng thc
G = nFE
dE p
S = nF
dT

H = G + T .S
d 2Ep
C p =
dT 2

-V d :
Cho phn ng trong pin
8
8
Cd + Hg 2 SO4 (r ) + H 2 O 2 Hg (l ) + CdSO4 . H 2 O(r ) .Nhit dung
3
3
SO
,H
O
ln
lt
l
27,82
/ 25,90 / 131,8
ring ca Hg(l),Cd,Hg2 4 2
-3
/75,31(J/kmol.K). E = 1,018 - 0,041.10 ( t -20) 9,5.10-7 ( t -20)2 +10-8 ( t
-20)3 .

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a) Tnh Cp ca caimi sunfat ngm nc 298K.

b) Xc nh G , S , H .
Gii:
2
d E
a) Ta c C p = 2 ,ly o hm cp hai ca E ta c :
dT p

C p = -9,5.10-7.2+10-8.3.2.(25-20)= -16.10-7(V/K)
M theo phng trnh phn ng
C p = C p ( Hg ) + C
C p ( H 2O ) C p ( Hg 2 SO4 ) C p ( Cd ) = 16.10 7
8
p ( CdSO4 . H 2O )
3

8
p ( CdSO4 . H 2O )
3

= 210,8.10 3 ( J

kmolK

b) Ly o hm cp mt ca E ta c
dE p

= 0,041.10 3 19.10 7 (t 20) + 3.10 8 (t 20)2

dT

p
dE p
= 4,975(V / K )
298 K
dT p
E = -1,018 (V)
G = nFE p 196518( J / molK )

dE p
S = nF
dT

9,6( J / molK )
p

H = G + T .S = 193657,2( J / mol )
Tnh bin thin enthapi v nhit lng Q thot ra trong pin c phn ng
CuSO4 + Zn Cu + ZnSO4 .bit Ep hai nhit :
T0K
273
276
E(V) 1,0960 1,0961
Gii:
dE p E p 0,001
Ta c :
=
=
dT
3
T
H = G + T .S
dE p
H = nF T
dT

p
0,001

H = 2.96500. 273.
1,0960
3

Nn H =-209772 ( J/mol)
Q = T. S =1756,3 (J/mol)

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KT LUN
Bi vit c mt s lng rt t bi tp, c nhiu dng bi cha c a ra gii quyt.
c bit mt bi ton tng qut v pin in bao gm rt nhiu d liu cn tnh ton,
trong cc bi gii, thng b qua h s hot , rt nhiu php tnh ch c th cho kt
qu gn ng .Trong mi dng bi tp li bao gm nhng dng khc, kh c th phn
chia trit ,chia dng bi tp ch c tnh tng i.
Ti liu tham kho
1. Ho l II (Trn Vn thm ) (trang 121-180)
2. Ho l IV (Nguyn Vn Tu) NXB GD ( trang 80-127)
3. Bi tp ho l
( dch t ting Nga) NXB H v trung hc chuyn nghip
(trang 214-265)
4. Bi tp ho hc i cng (Lm Ngc Thm) NXB H Quc gia HN (trang 141157)
5. Bi tp Ho l c s (Lm Ngc Thm) NXB khoa hc-k thut (trang 243-263)
6. in ho hc (Trnh Xun Sn) NXB H Quc gia HN (trang 114-182)

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