PHNG PHP KARL FISCHER

XC NH HM LNG NC
Coulometric KF Volumetric KF
Chun Karl Fischer (KF)
Nhanh (1...2 pht)
Chn lc i vi nc
chnh xc cao (0.3% srel) chnh xc cao (0.3% srel)
Khong o rng: ppm to %
Phn ng KF
SO
2
+ RN + ROH (RNH)SO
3
R
Hp cht sulfite
Chun Karl Fischer (KF)
Hp cht sulfite
(RNH)SO
3
R + H
2
O + I
2
+ 2RN (RNH)SO
4
R + 2(RNH)I
Hp cht sulfate
Tm tt:
H
2
O + I
2
+ SO
2
+ 3RN + ROH ----->(RNH)SO
4
R + 2(RNH)I
Dung mi (thng l methanol) tham gia phn ng
S c mt ca mt ba-z hu c gi pH 5 7
RN: pyridine, imidazole
Khong pH
log K
Cn b sung dung dch m
ti u 5 - 7
Chun Karl Fischer (KF)
Ti u
Phn ng ph
2
4
Cn b sung dung dch m
Chm
pH
2 4 6 8 10
0
Chun th tich/Chun in lng (in th)
Volumetric / Coulometric Titration
Chun th tch Karl Fischer
Iode c thm vo t burette trong qu Iode c thm vo t burette trong qu
trnh chun
p dng i vi mu c hm lng nc cao
100 ppm - 100 %
Chun in lng (in th) Karl Fischer
+
-
Chun in lng (in th) Karl Fischer
Iode c sinh ra bng phn ng in ha
trong qu trnh chun
p dng i vi mu c nc dng vt
1 ppm - 5 %
Chun in lng (in th) KF
-
+
Double platinum
pin electrode
Generator
electrode
Anode Cathode
+
Bnh chun v ha cht
Chun in lng (in th) KF
Anolyte
(sulfur dioxide, imidazole,
iodide, different solvent for
pin electrode
Catholyte
(similar or
+
iodide, different solvent for
different application -
methanol, ethanol with
chloroform, octanol,
ethyleneglycol )
(similar or
modified
solution)
Diaphragm
Iode (I
2
) to ra bng phn ng trn anode t I
-
+

Cathode
Chun in lng (in th) KF
+

Phn ng ph:
Kh cc hp cht cha S.
Sau 1 - 2 tun, mi mercaptans
Thay i cht in ly cathode hng tun
H
2
2 H
+
+ 2 e
-
Cathode
H
+
-
H
I
-
-
I
2 I
-
I
2
+ 2 e
-
Anode
I
2
to thnh t phn ng o_xy ha in ha
Thay i cht in ly cathode hng tun
L thuyt in lng Coulometry Theory
in lng (C: Coulomb)
1 C = 1 A .1 s
Phng php tuyt i Khng cn
chun ha!
sn xut 1 mol cht, tiu th 1/phn t
cn 96484 C.
2 ion I
-
phn ng to ra I
2
v tip tc phn
Charles Augustin de Coulomb
14.6.1736 - 23.8.1806
2 ion I
-
phn ng to ra I
2
v tip tc phn
ng vi 1 phn t H2O
1 mol H
2
O (18g) phn ng s tng ng
mt in lng 2 x 96484 C hoc l
10.72C/mg H
2
O.
Mc dung dch Anode v Cathode
Dung dch Anode (anolyte)
~ 100 mL
Dung dch Cathode (catholyte)
5 mL catholyte.
Anode
+
Cathode
~ 100 mL
Mc dung dch anode 3 - 5 mm cao hn
mc cathode to dng chy t
vng anode sang vng cathode
Gim s nhim m
(Low drift value)
Catholyte
Anolyte
(Low drift value)
Mc dung dch Anode v Cathode
Dung dch Anode (anolyte)
Dung dch Cathode (catholyte)
5 mL catholyte.
Anode
+
Cathode
Dung dch Anode (anolyte)
~ 100 mL
Lng mu s dng
Catholyte
Anolyte
Anode
+
Cathode
Mc dung dch Anode v Cathode
+
Vng cathode lun b nhim nc!
Nu mc cathode bng cao
hn mc anode
S c mt dng m i vo vng anode
Catholyte
Anolyte
S c mt dng m i vo vng anode
Tng s nhim m
(High drift value)
ng Cathode c v khng c mng ngn
C mng ngn
+

Khng mng ngn

+

ng Cathode c v khng c mng ngn

+

I
-
-
I
I ch vng anode v
+

I
-
-
I
-
I I
-
I c th di chuyn v vng I
2
ch vng anode v
phn ng vi H
2
O
I
2
c th di chuyn v vng
cathode v b kh thnh I
-
Khng mng ngn
Cc phng php hn ch sai s:
I
2
c th b kh trn cathode
thnh I
-
+

H
+
H
Cc phng php hn ch sai s:
Tng tc khuy
Din tch Cathode nh
I
-
-
I
-
H
+
H
Tng tc sn sinh I2
Lng mu s dng ln
Gy nn mt sai s nh i
vi cc mu c nng
H
2
O nh.
Tng tc sn sinh I2
H2 sinh ra bo v cathode
H2 sinh ra cathode l tc
nhn kh tt.

H
+
H
R-NO
2
R-NH
2
+ H
2
O
+
Khng mng ngn
D dng kh cc hp cht
cha Nit (nitro compounds) v
sinh ra nc.
Kt qu hm lng nc rt ln
I
-
-
I
-
H
+
H
Kt qu hm lng nc rt ln
Khng s dng phng php ny cho cc hp cht d b kh
VD: nitrobenzene, Axit bo khng no...
U IM CA H KHNG MNG NGN
+ Bnh chun d lm v sinh.
Khng mng ngn
+ Bnh chun d lm v sinh.
+ Gi tr nhim nc n nh hn trong thi gian di.
+ Ch s dng mt loidung dch.
p dng:
Hydrocarbons, hydrocarbons halogen ha, Ru, esters, ethers,
- C mt t sai s khi lng H
2
O thp trong mu(< 50 g/sample).
Hydrocarbons, hydrocarbons halogen ha, Ru, esters, ethers,
Du khong, du n
+
-
Chun in lng Karl Fischer
Coulometric Karl Fischer Titration
PHN GII V GII HN PHT HIN
phn gii: 0.1 g water
Gii hn pht hin: 5 g H
2
O
Mu 5g 1 ppm
Khong o: Khong o:
10 g - 100 mg H
2
O/mu
1 ppm - 5 % H
2
O
NGUYN L CH TH KARL FISCHER
(Xc nh im kt thc qu trnh chun - im tng ng)
Ch th hai in th - Bivoltametric indication
p t dng in khng i gia hai in cc bng Pt
Dng phn cc (polarization current) (I
pol
)
I
pol
= 20A
U = 650mV
2
Dng phn cc (polarization current) (I
pol
)
Trong qu trnh chun :
I
2
phn ng vi H
2
O
Khng c I2 t do trong dung dch Khng c I2 t do trong dung dch
high potential (650 mV)
I
pol
= 20A
U = 84mV
Ti im kt thc (endpoint)
Tt c nc phn ng vi
I
2
NGUYN L CH TH KARL FISCHER
(Xc nh im kt thc qu trnh chun - im tng ng)
2
e
2
Sau im kt thc chun
I
2
t do trong dung dch
I b kh v I
-
ti cathode
+ -
e
e
I
2
I
2
+ 2e
-
2 I
-
2 I
-
I
2
+ 2e
-
2I
-
I
2
I
2
b kh v I
-
ti cathode
dn in tng ln, in
th o c s gim nhanh
S thay i in th = im
kt thc
Chun Karl Fischer : Kim tra
Cc im lin quan cn c kim tra
kn ca h thng: Kim tra cn thn
m mi trng: Xc nh s nhim m t khng kh
(Drift determination) (Drift determination)
S n nh ca cht chun: Mu tiu chun
Phn ng ph : Kim tra ti liu
Ly mu: chnh xc