CC PHNG PHP

PHN TCH IN HA

NGUYN TC CA PHNG PHP PHN TCH IN HA

Ngun kch thch
Dng in

u im:

Nhanh

Chnh xc

nhy cao

chn lc cao

Cht phn tch

Tn hiu
(dng in)

PHN LOI CC PHNG PHP PHN TCH IN HA

Cc phng php o cc tnh cht ca ton b dung dch
V d: o dn, chun dn

Cc phng php o cc tn hiu lin quan n b mt tip xc

gia in cc v dung dch
V d: o pH

CC PHNG PHP LIN QUAN N B MT TIP XC

Cc PP lin quan
b mt tip xc
Cc PP ng (c dng), I 0
C phn ng in cc

Cc PP tnh (khng c dng), I = 0

Khng c phn ng in cc

PP in th k

PP chun in th

PP th kim sot

PP th thay i

PP qut th

C s khuy dd

PP qut th thy ng lc

PP vn ampe

PP cc ph v qut th
vi in cc tnh

PP th c nh

PP ampe k

PP dng kim sot

PP in phn dng kim sot

PP in phn th kim sot

Khng c s khuy dd

PP cc ph xung
v qut th

PP qut th chu k

PHNG PHP IN TH K
Nguyn tc:
o th ca mt h in cc (t bo in ha, t bo Galvanic) nhng
trong dung dch trong iu kin khng c dng hoc dng rt nh.
Th ca t bo in ha t l vi nng (hot ) ca cht phn
tch trong dung dch o
xc nh c nng ca cht phn tch.
iu kin:
Cht phn tch phi c hot tnh in cc

PHNG PHP IN TH K
c im ca phng php:
o th trong iu kin khng c dng hoc dng rt nh
khng c phn ng in ha xy ra b mt in cc
nng ca cc cht trong dung dch o khng b nh hng bi
t bo in ha
th o c phn nh chnh xc nng ca cht phn tch

CU TO CA T BO IN HA

Lm th no phn ng trn xy ra m khng c s tip xc

trc tip gia thanh Zn v dd CuSO4?

CU TO CA T BO IN HA
Cu

Cu mui

Zn

dd CuSO4

dd ZnSO4

in th k

CU TO CA T BO IN HA

Porous frit

CU TO CA T BO IN HA
Cathode (qu trnh kh):
Cu2+ (aq) + 2e Cu (s)
Anode (qu trnh oxy ha):
Zn (s) Zn2+ (aq) + 2e
Phn ng:
Cu2+ (aq) + Zn (s) Cu (s) + Zn2+ (aq)
K hiu ca mt t bo in ha:
Zn (s) ZnSO4 (aq, 0,1 M) || CuSO4 (aq, 0,1 M) Cu (s)

CU TO CA H O TH

vn k
84.2 mV

Vn k c in tr ln cng dng trong

cell rt nh
Cu mui c tch hp vo in cc qui chiu

in cc qui chiu, Eref

in cc ch th, Eind
Cu mui, Ej

MI QUAN H GIA TH O V NNG

Th o ca cell l hiu th ca in cc ch th v in cc qui chiu
Ecell = Ec Ea = Eind Eref
Ec, Ea: th kh ca cc phn ng xy ra cathode v anode tng ng

Th cn bng, c biu din theo phng trnh Nernst

Eind

RT aox
=E +
ln
nF ared
o

Eref = const
Ecell

RT aox
ln
=E +
nF ared
o'

E: th oxy ha kh tiu chun (V)

R: hng s kh = 8,314 J/mol.K
T: nhit Kelvins (K)
n: s electron tham gia phn ng
F: hng s Faraday = 96485 C/mol
aOx, aRed: hot cc cht oxy ha v kh,
cht no dng rn hay kh th a = 1

MI QUAN H GIA TH O V NNG

iu kin 25C hay 298K v dung d ch long:
Ecell

aox
0.05916
=E +
log
n
ared
o'

Khi cht kh dng rn hay kh:

Ecell = E o ' +

0.05916
log Cox
n

V d: Tnh Ecell ca h in ha sau 25C

Zn (s) ZnCl2 (aq, 0,0167 M) AgNO3 (aq, 0,1 M) Ag (s)
EAg+/Ag = 0,7996 V; EZn2+/Zn = -0,7618 V

Ecell = {EAg+/Ag + 0,059 log[Ag+]} {EZn2+/Zn + 0,02958 log[Zn2+]} = 1,555V

IN CC QUI CHIU

in cc so snh hay in cc qui chiu tng ng vi bn cell
in ha c th gn nh khng thay i v bit trc.

in cc so snh dng xc nh gin tip th ca in cc ch th

Khi cell in ha c k hiu: Reference || Indicator

Th ca in cc so snh ch ph thuc vo nhit

Cc loi in cc so snh thng dng:
-in cc hydro tiu chun
-in cc Calomel
-in cc bc / bc clorua

IN CC QUI CHIU

in cc so snh hay in cc qui chiu tng ng vi bn cell

in ha c th gn nh khng thay i v bit trc.

in cc so snh dng xc nh gin tip th ca in cc ch th

Khi cell in ha c k hiu: Reference || Indicator

Th ca in cc so snh ch ph thuc vo nhit

IN CC HYDRO TIU CHUN

in cc hydro tiu chun (standard hydrogen electrode SHE) c
th rt n nh mi nhit nn c chn lm th chun = 0 V.

Biu din bn cell: Pt (s), H2 (g, 1atm) H+ (aq, a = 1M)

Phn ng ca bn cell: 2H+ + 2e H2 (g)

IN CC HYDRO TIU CHUN

ECu2+/Cu = 0,337 V

IN CC CALOMEL

in cc Calomel da trn phn ng oxy ha kh gia Hg v Hg2Cl2 (calomel)
Biu din bn cell: Pt (s), Hg (l) Hg2Cl2 (s), KCl (aq, sat)
Phn ng ca bn cell: Hg2Cl2 (s) + 2e 2Hg (l) + 2Cl- (aq)
25C: Ecal = EHg2Cl2/Hg 0,05916 log [Cl-]2
2
= 0,2682 0,05916 log [Cl-]2
2

Th in cc Calomel bo ha t ph thuc vo nhit

nn in cc ny c s dng nhiu lm in cc so
snh.

Ecal (KCl sat., 25C) = 0,241 V

IN CC BC/BC CLORUA

in cc bc/bc clorua da trn phn ng oxy ha kh gia Ag v AgCl
Biu din bn cell: Pt (s), Ag (s) AgCl (s), KCl (aq, sat)
Phn ng ca bn cell: AgCl (s) + e Ag (s) + Cl- (aq)
25C: EAgCl/Agl = EAgCl/Ag 0,05916 log [Cl-]
= 0,2223 0,05916 log [Cl-]
Th in cc ph thuc nng Cl-

Porous plug

in cc bc/bc clorua c dng nhiu nht lm in cc so snh

EAgCl/Ag (KCl sat., 25C) = 0,197 V

MT S IN CC QUI CHIU KHC

in cc thy ngn sulphate Hg/Hg2SO4

in cc Cu/CuSO4

in cc Hg/HgO

in cc Ag/Ag+

in cc gn qui chiu (hay gi qui chiu): dy Pt, dy Ag

IN CC CH TH

Th in ha thay i theo hot ca ion cn phn tch

Cc loi in cc ch th
 in cc loi 1
 in cc loi 2
 in cc loi 3
 in cc oxy ha kh
 in cc mng chn lc ion

IN CC LOI 1

Cu to t mt cp oxy ha - kh gm n cht (kim loi / khng kim loi) v ion (cation / anion)
xut pht t n cht : Mn+/M, Xn+/X, X/Xn-.

in cc loi 1 thng dng nht l in cc gm mt thanh kim loi M nhng trong dung dch cha
ion Mn+: Mn+/M. mt nhit xc nh, th ca in cc ny ch ph thuc vo hot ion Mn+.
Mn+ (aq) + ne- M (s)
25C: E = EMn+/M +

0,05916

log [Mn+]

Thng c nh lc ion (c nh h s hot ) bng cch thm mt mui tr (vd: KCl), khi E t l vi
nng Mn+.

Vd:
in cc Cu trong dd CuSO4

Cu

Ag

in cc Ag trong dd AgNO3

CuSO4

AgNO3

IN CC LOI 1

Cc in cc loi 1 khc: in cc Pt, H+/H2 (SHE); in cc Pt, I3-/I-

in cc SHE

Cc kim loi hay c s dng lm in cc: Ag, Bi, Cd, Cu, Hg, Pb,
Sn, Tl v Zn.

Cc yu t gii hn ca cc kim loi khc:
 tc cn bng chm
d to thnh lp oxit trn b mt in cc
nhiu phn ng cn tr c th xy ra

IN CC LOI 2

Cu to gm mt in cc kim loi M ph mt lp mui t tan ca M v dung dch cha anion ca
mui : M/MXn/X-. mt nhit xc nh, th ca in cc loi 2 ph thuc vo hot ca anion.
Vd: Ag/AgCl/Cl-; Hg/Hg2Cl2/ClAg+ (aq) + e- Ag (s)
25C: E = EAg+/Ag + 0,05916 log [Ag+]
Khi cn bng: AgCl (s)
[Ag+] =

Ag+ (aq) + Cl- (aq)

TAgCl
[Cl-]

E = EAg+/Ag + 0,05916 log

TAgCl
[Cl-]

E = K - 0,05916 log [Cl-]

Khi c nh nng ion X-, E ch ph thuc nhit , in cc loi 2 c dng lm in cc qui chiu.

IN CC MNG CHN LC ION

Th ca in cc ny do phn ng oxy ha kh v s trao i ion
trn b mt mng

Th ca in cc ny ch ph thuc hot ca mt hoc mt nhm
ion nht nh

Ion cn tr phi c nng khc nhiu so vi ion phn tch
Phn loi in cc mng chn lc ion:

Gm hai nhm chnh: in cc mng rn v in cc mng lng

in cc mng rn gm ba nhm: mng thy tinh, mng n tinh th
v mng a tinh th (mng ng th v mng d th)

CU TO IN CC MNG CHN LC ION

Internal reference electrode (Vd: Ag/AgCl)

Internal reference solution (Vd: dd KCl)

Active membrane

S HNH THNH TH IN CC MNG

K , Cl

Cn bng v in tch
Khng cn bng v nng

Khuch tn ion

K , Cl

Mt cn bng v in tch

Cn bng

K+, Cl-

Th mng hnh thnh

trng thi cn bng

IN CC THY TINH

Chn lc cho cc ion: H+, Na+, K+, Li+, NH4+, Ca2+, Ba2+, thng dng
nht l ion H+ (in cc ch th pH)

Tnh chn lc ca cc in cc thy tinh ty thuc vo thnh phn
thy tinh s dng ch to mng

CU TO IN CC CH TH pH

in cc Ag/AgCl
in cc pH

TH IN CC CA IN CC CH TH pH

S ph thuc ca th in cc vo pH tun theo pt Nernst:

Ecell = E + 0,05916 log [H+]
Ecell = E - 0,05916 pH

XC NH pH BNG IN CC CH TH pH

o hiu th gia in cc pH v in cc qui chiu trong dd pH
chun (m pH)
Ecell, standard = E - 0,05916 pHstandard

o hiu th gia in cc pH v in cc qui chiu trong dd cn
xc nh pH.
Ecell, unknown = E - 0,05916 pHunknown

Gi tr pH o c l kt qu ca phng trnh:
pH unkown = pH s tan dard

1
+
( Ecell , s tan dard Ecell ,unknown )
0.05916

C IM CA IN CC CH TH pH

S dng cho nhiu mi trng khc nhau.

chn lc cao, t b nh hng bi cc ion khc.

chnh xc: 1; 0,1; 0,01 n v pH

Thi gian t cn bng c th n 30s.

Sai s kim (pH > 10)
Ecell = E + 0,05916 log (aH+ + KH, Na aNa+)

Sai s axit (pH < 0)

SAI S CA IN CC CH TH pH

CHUN MY O pH
V sao phi chun my o pH?
Chun my o pH:

Chun m 1: dng m pH 7 (6.86, 7.00, 7.01) loi b
nh hng ca E.

Chun m 2: dng m axit (4.00, 4.01) hay m baz (9.21)
to khong tuyn tnh cho khong pH s dng.

TNH CHN LC CA IN CC MNG CHN LC ION

Gi A l ion cn phn tch, I l ion cn tr, khi th in cc l:

Ecell = E o ' +

0.05916
log(a A + K A, I a Iz A / z I )
zA

zA, zI : in tch ca ion A v ion I tng ng.

KA, I : h s chn lc i vi ion A
KA, I << 1: in cc chn lc tt cho ion A.
KA, I = 1: in cc cho tn hiu nh nhau i vi ion A v ion I
KA, I > 1: in cc chn lc cho ion I hn ion A.

XC NH H S CHN LC K

Nu dd ch c ion A:

Ecell

0.05916
=E +
log(a A )
zA
o'

Nu dd ch c ion I:

Ecell

0.05916
=E +
log( K A, I a Iz A / z I )
zA
o'

Khi Ecell (A) = Ecell (I):

K A, I

[ a A ]E
=
[aI ]Ez A / z I

[a A ]E , [aI ]E : hot ca ion A v ion I sinh cng mt th in cc E

XC NH H S CHN LC K
Cch 1: o th ca dd c cha c A v I

Cch 2: o th ca dd c cha ring A v I

A

Ecell
I

- ln (aA)

- ln (aI)
- ln (aA) hay - ln(aI)

IN CC MNG N TINH TH

chn lc rt cao, hu nh khng b nh hng bi cc ion khc

in cc mng LaF3 chn lc cho ion fluorua:
Ecell = E + 0,05916 log ([F-] + KF, OH [OH-])

KF, OH = 0,1

 Xc nh nng fluorua n khong 10-6 M

 Ion cn tr l OH nh hng bi s to phc bn ca F- vi Fe3+ v Al3+

IN CC MNG RN NG TH

Mng

Ion phn tch

Khong phn tch (M)

Ion nhiu

AgCl (hoc AgCl-Ag2S)

Cl-

1-10-4

Br-, I-, CN-, S2-

AgBr (hoc AgBr-Ag2S)

Br-

1-10-5

I-, CN-, S2-

I-

1-10-6

S2-

S2-

1-10-5

CdS-Ag2S

Cd2+

10-1-10-7

Fe2+, Pb2+, Hg2+, Ag+

CuS-Ag2S

Cu2+

10-1-10-8

Ag+, Hg2+, Cd2+

PbS-Ag2S

Pb2+

10-1-10-6

Ag+, Hg2+, Cu2+

AgI (hoc AgI-Ag2S)

Ag2S

CC LOI IN CC MNG CHN LC ION KHC

in cc mng rn d th:
Vt liu hot ng c mang bi cc cht mang hu c tr nh
cao su, silicon, PVC, parafin, Thng dng nht l cao su silicon.
in cc mng lng:

Vt liu hot ng l cc cht trao i ion (cation hay anion) dng
hu c (lng hay rn) c ha tan trong mt dung mi khng tan
trong nc.

Gii hn pht hin v chn lc thng km hn cc in cc
mng rn.

Thng dng nht l cc in cc chn lc cho cc ion Ca2+ v K+.

CC LOI IN CC MNG CHN LC ION KHC

in cc mng lng:

CC LOI IN CC MNG CHN LC ION KHC

in cc mng lng:

CC PHNG PHP NH LNG

Phng php ng chun:
Ecell = Ec Ea = Eind Eref + Ej
Ecell = E o ' +

0.05916
log[ A]
n

Chun b cc dung dch chun bit trc nng C1, 2C1, 3C1, 4C1, 5C1,

o E ca cc dung dch chun t nng thp n cao.

Dng ng chun E theo pC, lp phng trnh hi qui theo phng php bnh phng ti thiu

o E ca dung dch mu c nng Cx cn xc nh, t phng trnh hi qui tnh ra nng Cx.

Sai s ca phng php ny < 1%.
V d: xc nh nng ion fluorua trong kem nh rng bng in cc chn lc ion fluorua.

CC PHNG PHP NH LNG

Phng php ng chun:

CC PHNG PHP NH LNG

Xc nh ion fluorua trong kem nh rng:

CC PHNG PHP NH LNG

Xc nh ion fluorua trong kem nh rng:

CC PHNG PHP NH LNG

Phng php chun in th:

Thng gp nht l cc trng hp chun axit-baz hay chun kt ta trong im tng
ng c xc nh bng cch o th ca dung dch.

V hai ng cong chun E theo V v E/V theo Vtb (V trung bnh):
 th E theo V cho im tng ng ng vi im E tng nhanh nht (im bc nhy).
 th E/V cho im tng ng ng vi im cc i.

chnh xc cao hn phng php ng chun.

Gn ti im tng ng nng cht phn tch rt nh nn th rt lu n nh.
V d: chun dung dch I- bng dung dch AgNO3 chun, chun axit phosphoric bng in
cc pH.

CC PHNG PHP NH LNG

Phng php chun in th:

vn k
84.2 mV

cht chun
in cc qui chiu, Eref

in cc ch th, Eind

cht phn tch

CC PHNG PHP NH LNG

Phng php chun in th:

CC PHNG PHP NH LNG

Phng php chun in th: