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Chng 17

Phng phap phan tch


da vao viec o the - PP
chuan o ien the

Do the va Chuan do dien the

Phng phap chuan o ien the


)
)
)
)
)

Nguyen tac
ac iem cua phng phap
ien cc
Can bang chuan o
Cach xac nh iem tng ng

Do the va Chuan do dien the

Nguyen tac
) Thc

hien s chuan o
) Nhung vao dd chuan
o ien cc co tham gia
phan ng ien hoa vi
mot trong nhng cau t
co trong can bang chuan
o.
) Khao sat s bien thien
the can bang cua ien
cc theo lng thuoc th
them vao
) T ng cong E =
f(V), xac nh iem tng
ng

Do the va Chuan do dien the

Buret, C
ien cc
so sanh
ien cc
ch th

dd phan
tch, X

ac iem cua phng phap


) Phng

phap vi ien phan vi cng o dong trong dd


that nho hay triet tieu. Lng cau t tham gia p ien
hoa rat nho so vi lng tham gia p chuan o
) Can chon ien cc thch hp vi loai can bang chuan
o
)u iem so vi pp hoa hoc
- o nhay cao, co the en 105 M
- Chuan o c dung dch co mau
- Chuan o khong can chat ch th

Do the va Chuan do dien the

Cac loai ien cc thong dung


) ien cc ch th (indicator electrode)

ien cc co p ien hoa vi cau t cua can


bang chuan o
ien cc kim loai
ien cc thuy tinh (Glass pH electrode)

) ien cc so sanh (reference electrode)


ien cc Calomel
ien cc Ag/AgCl

Do the va Chuan do dien the

ien cc kim loai


- S o ien cc
- P ien cc
E cb =

E 0 n+
/M
M

0
E n+
/M
M

0
= E MA
/ M

M / M n+ hay M / An
n+
n+
n
M ne
M , M +A
MA

0,059
+
lg[ M n+ ] -Th du: /c Ag
n
+
Ag e
Ag
0,059 TMA
+
lg n
0,059
+
n
[ A ] Ecb = E 0 +
lg[ Ag ]
+
Ag / Ag
1
0,059
1
+
lg n
0,059
1
0
lg
n
[ A ] hay Ecb = E AgCl / Ag +
1
[Cl ]

Do the va Chuan do dien the

ien cc kim loai tr


ien cc kim loai tr ong vai tro trao oi
e- vi cau t oxy hoa hay kh trong dd

- S

o ien cc

- P ien cc

Pt / Ox , Kh

-Th du: /c

Pt / Fe 3+ / Fe 2+

Ox + ne
Kh

0,059 [Ox ]
0
Ecb = EOx / Kh +
lg
n
[ Kh]

Fe 3+ + e Fe 2+
Ecb = E 0

Fe 3+ / Fe 2 +

- /c tr thong dung: /c Pt, Au, C

Do the va Chuan do dien the

0,059 [ Fe 3+ ]
lg
+
1
[ Fe 2+ ]

ien cc thuy tinh (glass


pH electrode)
- Nhung ien cc vao dd khao
sat nong o H+
- Hai ben be mat mang thuy
tinh tiep xuc vi H+ co phan
ng trao oi
+
H dd

+
Natt

+
H tt

+
Nadd

- Hai mat lp thuy tinh tao hai


lp gel Acid silicic do s hien
dien cua H+ trong thuy tinh, lp
nay day khoang 104 10-5 mm
Do the va Chuan do dien the

Ag

H+
(a2
const)

Cau
truc
cua
ien
cc
thuy
tinh

AgCl

H+
(a1)
Glass membrane (64% SiO 2,
28% Na2O, 8% MgO) (0,06 0,10
mm)
8

ien cc thuy tinh


Lp thuy tinh kho (0,1 mm)

Hieu the mang qua lp thuy


tinh
E = e e
1

a1

a1

Lp gel tren mat


ngoai thuy tinh

a2

a2

Lp gel tren
mat trong
thuy tinh

Goi e1 va e2 la ien the lp


gel mat ngoai va ien the
lp gel mat trong

0,059 a1
e1 = K1 +
lg '
1
a1
0,059 a2
lg '
e2 = K 2 +
1
a2

Do the va Chuan do dien the

Gia s hien tng trao oi


xay ra hai mat thuy tinh
gan giong nhau

K1 K 2 ; a '1 a '2

0,059 a1
E = e1 e2 =
lg
1
a2
Vi a2 la hang so

E = K + 0,059 lg a1 = K 0,059 pH
9

ien cc mang (Ion selective electrode)


) ien cc mang ran
) ien cc mang long

Do the va Chuan do dien the

10

ien cc so sanh (reference Electrode)


Cau tao chung Kim loai c phu mot
hp chat kho tan cua kim loai, nhung vao
trong dd cha anion cua hp chat kho tan
co nong o xac nh
n
M
,
MA
/[
A
]
- S o ien cc
n
MA

+
ne

M
+
A

- P ien cc

E cb =

0
E MA
/ M

Do the va Chuan do dien the

0,059
1
+
lg n
n
[A ]

Cau
truc
cua
ien
cc
so
sanh
11

Silver/Silver Chloride Electrodes


Ag, AgCl/KCl (xM)//
Ag , AgCl /[ Cl ]
[ Cl ] = 1 M E = 0 , 237 v
[ Cl ] = 0 ,1 M E = 0 , 290 v

S o ien cc Ag/AgCl
Do the va Chuan do dien the

12

ien cc Calomel
/c Calomel Kim loai Hg c phu muoi Hg2Cl2
nhung vao dd Cl- co nong o xac nh
- S o ien cc Hg , Hg 2Cl 2 /[Cl ]
- P ien cc
E cb =

Hg2Cl 2 +2e
2 Hg +2Cl

0
E Hg
2Cl 2 / 2 Hg

0
= E Hg

2Cl 2

Do the va Chuan do dien the

1
0,059
+
lg 2
2
[Cl ]

0
,
059
lg[
Cl
]
/ 2 Hg

13

Saturated Calomel
Electrode
Calomel bao hoa (S.C.E
Satured Calomel
Electrode) vi dd KCl bao
hoa, E = 0,244 v 250C
Calomel nguyen chuan
(N.C.E Normal Calomel
Electrode) vi dd [KCl] =
1M, E = 0,284 v 25 0C

Do the va Chuan do dien the

14

ien cc kh
Cau tao Kim loai tr nh Pt, Au, tiep xuc ong

thi vi kh va dd cha ion cua kh nay

Th du: ien cc Hydro (Standard hydrogen electrode


SHE)
- S o ien cc

Pt , H 2 / H +

- P ien cc

H 2 2e
2H +

Ecb = E 0

0,059 [ H + ]2
+
lg
2
pH 2

2H + / H2

= o + 0,059 lg[ H + ] = 0,059 pH


Do the va Chuan do dien the

ien cc
Hydro khong
tien dung,
c dung
lam ien cc
chuan e
nh nhng
the khac
15

Standard hydrogen electrode SHE

S o ien cc Hydro chuan


Do the va Chuan do dien the

16

ien cc ghep (combination electrode)


ien cc so sanh
ien cc ch th
/c Clorua Bac
Ag , AgCl /[Cl ]

E=

0
E AgCl
/ Ag

0,059
1
lg
+
1
[Cl ]

/c thuy tinh
E = K + 0,059 lg a1 = K 0,059 pH

Do the va Chuan do dien the

ien cc so sanh

ien cc ghep
ien cc thuy tinh

17

ien cc ghep

S o
ien
cc
ghep
(ien
cc
thuy
tinh)

Do the va Chuan do dien the

18

Cac loai can bang trong chuan o ien the


)
)
)
)

Can bang Acid Baz


Can bang tao tua
Can bang Oxy hoa kh
Can bang tao phc

Do the va Chuan do dien the

19

Can bang Acid-Baz


- Chon ien cc
thch hp
- Phan ng chuan
o

H + + OH
H 2O
-Ve ng cong
chuan o thc
nghiem pH = f (V).
T o nh iem
tng ng
Do the va Chuan do dien the

Buret, H+
ien cc ch
th (ien cc
thuy tinh)

ien cc so
sanh
(Ag, AgCl/Cl-)

dd phan
tch, OH-

Edo = E chithi E sosanh


= K 0,059 pH E sosanh
= 0,059 pH
hay pH =

Edo
0,059
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Can bang tao tua


- Chon

ien cc thch hp

- Phan ng chuan o
Ag + + Cl
AgCl

- Phan ng ien cc
Ag e
Ag +

ien cc so
sanh
(Ag, AgCl/Cl-)

Buret,
Ag+
ien cc ch th
(/c Ag kim
loai)
dd phan tch,
Cl-

- Ve ng cong chuan o thc nghiem E


= f (V). T o nh iem tng ng

Do the va Chuan do dien the

21

Can bang tao tua

Buret,
Ag+
ien cc ch th
(/c Ag kim
loai)

ien cc so
sanh
(Ag, AgCl/Cl-)

dd phan tch,
Cl-

E do = E chithi E sosanh

E chithi =
=

0
E +
Ag / Ag

E0 +
Ag / Ag

+ 0,059 lg[ Ag ]
+ 0,059 lg

Tai iem tng ng

E chithi = E 0

Ag + / Ag

Do the va Chuan do dien the

TAgCl

[Cl ]

+ 0,059 lg TAgCl
22

Can bang tao tua Th du


- Th du: Chuan o Cl- va Br- Phan ng chuan o
Ag + + Br
AgBr
Ag + + Cl
AgCl

- Phan ng ien cc
Ag e
Ag

ien cc so sanh
(Ag, AgCl/Cl-)

TAgBr = 5,3 10 13
TAgCl = 1,8 10 10

TAgI = 8,3 10 17
Buret, Ag+

ien cc ch th
(ien cc Ag kim loai)

dd phan tch, Cl-, BrDo the va Chuan do dien the

23

Can bang tao tua Th du


Tai iem tng ng (1)

E chithi =

0
E +
Ag / Ag

E do = E chithi E sosanh

+ 0,059 lg TAgBr

Tai iem tng ng (2)

E chithi = E

Ag + / Ag

+ 0,059 lg TAgCl

E = E 2 E 1

Muon nh chnh xac tng


iem tng ng E 0,2

= 0,059(lg TAgCl lg TAgBr )


0,059 TAgCl
=
lg(
) = 0,077 v
2
TAgBr
Do the va Chuan do dien the

0,059 T2
T2
lg( ) 0,2 hay
10 6,8
2
T1
T1
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Can bang oxy hoa kh


- Th

du: Chuan o Ox2 bang Kh1

- Phan ng chuan o

Ox 2 + Kh1
Kh2 + Ox1

ien cc so
sanh
(Ag, AgCl/Cl-)

- Phan ng ien cc

E do = E chithi E sosanh

Do the va Chuan do dien the

Buret,
Ox2
ien cc ch
th
(ien cc Pt)
dd phan tch,
Kh1

25

Can bang oxy hoa kh


Trc iem tng ng: Ox1/Kh1; Kh2

E chithi =

0
EOx1 / Kh1

0,059 [Ox1 ]
lg
+
n1
[ Kh1 ]

Tai iem tng ng

E chithi

n1 E10 + n2 E 20
=
n1 + n2

Sau iem tng ng: Ox2/Kh2; Ox1

E chithi =

0
EOx2 / Kh2

Do the va Chuan do dien the

0,059 [Ox 2 ]
lg
+
n2
[ Kh2 ]
26

Can bang tao phc


- Th

du: Chuan o kim loai M bang EDTA

- ien cc: Ch th : Hg; So sanh: Calomel


- Phan ng chuan o
(1) M + Y
MY , MY

- Phan ng ien cc

Hg 2e
Hg

2+

[ MY ]
=
[ M ][Y ]

E do = E chithi E sosanh
E chithi =

E chithi =

E 0 2+
Hg / Hg

Do the va Chuan do dien the

E 0 2+
Hg / Hg

0,059
+
lg[ Hg 2+ ]
2

0,059
[M ]
0,059
[M ]
+
lg( K
) = A+
lg(
)
2
[ MY ]
2
[ MY ]
27

Can bang tao phc


Ngay t au chuan o, them mot lng xac nh dd [HgY2- ]
vao dd khao sat

( 2) HgY

HgY

Hg

2+

+Y

[ HgY ]
21,8
=
= 10
2+
4
[ Hg ][Y ]

Khi them Y vao, Y tham gia ong thi 2 can bang (1) va (2)
2

[ HgY ] [ HgY ] [ M ] MY
[ Hg ] =
=

4
[ MY ]
HgY
HgY [Y ]
2+

=
Do the va Chuan do dien the

[ HgY 2 ]

HgY

MY

[M ]

[ MY ]
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Cach xac nh iem tng ng


Th du:

Do the va Chuan do dien the

29

Cach xac nh iem tng ng

Do the va Chuan do dien the

30

Cach xac nh iem tng ng

Do the va Chuan do dien the

31

Cach xac nh iem tng ng

440
= 24,34 ml
440 + 590
590
= 24,34 ml
Vtd = 24,40 0,10
440 + 590
E td = 233 + 83
Vtd = 24,30 + 0,10

Do the va Chuan do dien the

440
= 268 mV
440 + 590

32

Cach xac nh iem tng ng

440
= 24,34 ml
Vtd = 24,30 + 0,10
440 + 590
590
= 24,34 ml
Vtd = 24,40 0,10
440 + 590
E td = 233 + 83

Do the va Chuan do dien the

440
= 268 mV
440 + 590

33

Cach xac nh iem tng ng


Th du: nh o kiem cua mau nc
Phan ng chuan o
+

H + OH
H 2O

-Ve ng cong
chuan o thc
nghiem pH = f (V).
T o nh iem
tng ng

ien cc so
sanh
(Ag, AgCl/Cl-)

ien cc ch th
(/c thuy tinh)

E do = E chithi E sosanh

dd phan
tch, OH-

= K 0,059 pH E sosanh
= 0,059 pH
hay pH =

Do the va Chuan do dien the

Buret, H+

Edo
0,059
34

Cach xac nh iem tng ng


Th du: 40 mL nc kiem c chuan o bang dd HCl 0,100 N theo pp ct
pH/ V 2pH/ 2 V

V HCl

pH

0,00
5,00
10,00

10,669
10,172
8,520

12,30
12,40
12,50
12,60
12,70

8,487 - 0,117
- 0,003
8,370
- 0,120 + 0,005
8,250
8,135 - 0,115 + 0,012
- 0,103
8,032

20,00

6,478

30,00
30,10
30,20
30,30
30,40

4,382
- 0,236 - 0,051
4,146
- 0,287
+ 0,039
3,859
- 0,248
3,611
+ 0,076
- 0,181
3,430

35,00
40,00

2,190
1,910

Do the va Chuan do dien the

Phng phap noi suy


Vtd 1 = 12,40 + 0.10

Vtd 2

0,003
= 12,44 mL
0,008

0,051
= 30,10 + 0.10
= 30,16 mL
0,090

35

ng dung cua pp o the


) o trc tiep pH hay E
cua dd
) Chuan o ien the
) nh nhng hang so can
bang

Do the va Chuan do dien the

36

ng dung Xac nh hang so can bang


) Hang so phan ly cua acid yeu
Pt ,H2/[HA]0 = 0,1 M, [NaA]0 = 0,1 M // S.C.E
[ H + ][ A ]
C A
K HA =
pH = pK HA + lg
[ HA]
C HA
) Hang so ben cua phc
Cu/[Cu2+ ]0 = 10-4 M, [Y4-]0 = 10-2 M // S.C.E

CuY

[CuY ]
=
[Cu 2+ ][Y 4 ]

) Tch so tan cua tua


Cu/[Na 2 S]0 = 0,1 M // S.C.E

T = [Cu+ ]2[S2-]
Do the va Chuan do dien the

37

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