PHNG PHP KARL FISCHER XC NH HM L NG N C

Coulometric KF Volumetric KF

Chu n Karl Fischer (KF)

Nhanh (1...2 pht) Ch n l c i v i n c chnh xc cao (0.3% srel) Kho ng o r ng: ppm to %

Chu n Karl Fischer (KF)

Ph n ng KF SO2 + RN + ROH (RNH)SO3R H p ch t sulfite (RNH)SO3R + H2O + I2 + 2RN (RNH)SO4R + 2(RNH)I H p ch t sulfate

Tm t t: H2O + I2 + SO2 + 3RN + ROH ----->(RNH)SO4R + 2(RNH)I Dung mi (th ng l methanol) tham gia ph n ng S c m t c a m t ba-z h u c gi pH 5 7 RN: pyridine, imidazole

Chu n Karl Fischer (KF)

Kho ng pH t i u 5 - 7
log K

C n b sung dung d ch m Ph n ng ph T i u

Ch m
pH
2 4 6 8 10

Chu n th tich/Chu n i n l ng (i n th) Volumetric / Coulometric Titration

Chu n th tch Karl Fischer Iode c thm vo t burette trong qu trnh chu n p d ng i v i m u c hm l ng n c cao 100 ppm - 100 %
+

Chu n i n l ng (i n th ) Karl Fischer Iode c sinh ra b ng ph n ng i n ha trong qu trnh chu n p d ng i v i m u c n c d ng v t 1 ppm - 5 %

Chu n i n l ng (i n th ) KF

Chu n i n l ng (i n th ) KF
Bnh chu n v ha ch t
Cathode Anode

Double platinum pin electrode

Generator electrode

Anolyte
(sulfur dioxide, imidazole, iodide, different solvent for different application methanol, ethanol with chloroform, octanol, ethyleneglycol )

Catholyte
(similar or modified solution)

Diaphragm

Chu n i n l ng (i n th ) KF
Iode (I2) t o ra b ng ph n ng trn anode t I+

Cathode

2 H+ + 2 e-

H2

Ph n ng ph : Kh cc h p ch t ch a S. Sau 1 - 2 tu n, mi mercaptans Thay i ch t i n ly cathode h ng tu n

H+
-

Anode
I2 t o thnh t ph n ng o_xy ha i n ha

2 I

I2 + 2 e-

L thuy t i n l ng Coulometry Theory

i n l ng (C: Coulomb) 1 C = 1 A .1 s Phng php tuy t i Khng c n chu n ha! s n xu t 1 mol ch t, tiu th 1/phn t c n 96484 C. 2 ion I- ph n ng t o ra I2 v ti p t c ph n ng v i 1 phn t H2O 1 mol H2O (18g) ph n ng s tng ng m t i n l ng 2 x 96484 C ho c l 10.72C/mg H2O.

Charles Augustin de Coulomb 14.6.1736 - 23.8.1806

M c dung d ch Anode v Cathode

Cathode Anode

Dung d ch Cathode (catholyte) 5 mL catholyte. Dung d ch Anode (anolyte) ~ 100 mL

M c dung d ch anode 3 - 5 mm cao hn m c cathode t o dng ch y t vng anode sang vng cathode

Gi m s nhi m m (Low drift value)

Catholyte

Anolyte

M c dung d ch Anode v Cathode

Cathode Anode

Dung d ch Cathode (catholyte) 5 mL catholyte. Dung d ch Anode (anolyte) ~ 100 mL L ng m u s d ng

Catholyte

Anolyte

M c dung d ch Anode v Cathode

Cathode

Anode

Vng cathode lun b nhi m n c!

N u m c cathode b ng cao hn m c anode S c m t dng m i vo vng anode

Catholyte

Anolyte

Tng s nhi m m (High drift value)

ng Cathode c v khng c mng ngn

ng Cathode c v khng c mng ngn C mng ngn Khng mng ngn

+
-

I I-

I2 ch vng anode v ph n ng v i H2O

I2 c th di chuy n v vng cathode v b kh thnh I-

Khng mng ngn

H+ IH

I2 c th b kh trn cathode thnh ICc phng php h n ch sai s : Di n tch Cathode nh

Tng t c khu y

I
Tng t c s n sinh I2 H2 sinh ra b o v cathode L ng m u s d ng l n

Gy nn m t sai s nh i v i cc m u c n ng H2O nh .

Khng mng ngn

R-NO2

+
R-NH2 + H2O

H2 sinh ra cathode l tc nhn kh t t.

H+ I
-

H
D dng kh cc h p ch t ch a Nit (nitro compounds) v sinh ra n c. K t qu hm l ng n c r t l n

Khng s d ng phng php ny cho cc h p ch t d b kh VD: nitrobenzene, Axit bo khng no...

Khng mng ngn

U I M C A H KHNG MNG NGN

+ Bnh chu n d lm v sinh. + Gi tr nhi m n c n nh hn trong th i gian di. + Ch s d ng m t lo idung d ch.

p d ng:
Hydrocarbons, hydrocarbons halogen ha, R u, esters, ethers, D u khong, d u n - C m t t sai s khi l ng H2O th p trong m u(< 50 g/sample).

PHN GI I V GI I H N PHT HI N
Chu n i n l ng Karl Fischer

Coulometric Karl Fischer Titration

phn gi i: 0.1 g water Gi i h n pht hi n: 5 g H2O

M u 5g 1 ppm

Kho ng o: 10 g - 100 mg H2O/m u 1 ppm - 5 % H2O

NGUYN L CH TH KARL FISCHER

(Xc nh i m k t thc qu trnh chu n - i m tng ng)

Ch th hai i n th - Bivoltametric indication p t dng i n khng i gi a hai i n c c b ng Pt

Dng phn c c (polarization current) (Ipol)

Trong qu trnh chu n

I2 ph n ng v i H2O

Ipol = 20 A U = 650mV

Khng c I2 t do trong dung d ch high potential (650 mV)

NGUYN L CH TH KARL FISCHER

(Xc nh i m k t thc qu trnh chu n
Ipol = 20 A U = 84mV

- i m tng ng)

T i i m k t thc (endpoint)
T t c n c ph n ng v i I2
2

Sau i m k t thc chu n

I2 t do trong dung d ch
e e

I2 b kh v I- t i cathode
I2
I2 + 2e2 I-

+ I2
2 II2 + 2e-

2I-

d n i n tng ln, i n th o c s gi m nhanh S thay i i n th = i m k t thc

Chu n Karl Fischer : Ki m tra

Cc i m lin quan c n c ki m tra
Ki m tra c n th n Xc nh s nhi m m t khng kh (Drift determination) S n nh c a ch t chu n: M u tiu chu n Ph n ng ph : Ki m tra ti li u L y m u: chnh xc kn c a h th ng: m mi tr ng: