02-kf-theory
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02-kf-theoryTRANSCRIPT
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KF TitrationKF Titration
Karl Fischer TitrationKarl Fischer Titration
Regina Schlink Regina Schlink Metrohm Ltd, HerisauMetrohm Ltd, Herisau
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF Titration• Coulometric KF Titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF Instruments
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
Method for water determinationMethod for water determination
• in technical products
(oil, plastics and gases)
• in cosmetic products
• in pharmaceutical products
• in food industry
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KF TitrationKF Titration
The KF reactionThe KF reaction
I.
CH3OH + SO2 + RN [RNH]SO3CH3
II.
H2O + I2 + [RNH]SO3CH3 + 2RN [RNH]SO4CH3 + 2[RNH]I
(RN = Base)
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KF TitrationKF Titration
Basic ingredients of KF reagentsBasic ingredients of KF reagents
I2
SO2
Imidazole
Methanol
Iodine
Sulphur dioxide
Buffer
Solvent
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KF TitrationKF Titration
pH dependencypH dependency
0
2
4
6
0 2 4 6 8 10 12
log K
pH
Optimum: pH range between 5 and 7
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
KF titration methodsKF titration methods
Volumetric KF titration Coulometric KF titration
Working medium & titrant Iodine is generated in titration cell (anodic oxidation)
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KF TitrationKF Titration
Volumetric KF titration step by stepVolumetric KF titration step by step
• Fill titration vessel with solvent
• Pretitration with KF reagent• Add the sample• Titrate with KF reagent
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KF TitrationKF Titration
Volumetric KF reagentsVolumetric KF reagents
One component reagents
– Titrant contains iodine, sulphur dioxide, buffer and methanol/ethanol
– Working medium contains only the methanol/ethanol
– Disadvantage: the titre decreases 5% per year in the closed bottle!
Two component reagents
– Titrant contains iodine
– Solvent contains buffer and sulphur dioxide
– Advantages: pH optimum in the solvent / fast reaction / titre is very stable
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
Coulometric KF titration step by stepCoulometric KF titration step by step
• current is our burette• iodine is produced from a iodide
containing solvent by anodic oxidation
• generating current is switched off as soon as a slight excess of free iodine is present
• free iodine is indicated by a double platinum electrode
H+ H
II-
-
-
+-
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KF TitrationKF Titration
Coulometric KF titrationCoulometric KF titration
Cell with diaphragm Cell without diaphragm
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KF TitrationKF Titration
How to fill coulometric cell with diaphragm?How to fill coulometric cell with diaphragm?
• Catholyte Catholyte 5 mL5 mL
Reduction: 2 HReduction: 2 H+ + +2 e+2 e- - = H = H22
change catholyte weekly!change catholyte weekly!
• Anolyte: Anolyte: about 100 mLabout 100 mL
2 I2 I- - = I= I2 2 + 2 e+ 2 e--
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KF TitrationKF Titration
Comparison with and without diaphragmComparison with and without diaphragm
Without diaphragm With diaphragm
Recommendable for most applications, sample should have a good solubility in alcohol
Reagents with low conductivity (the addition of chloroform or xylene > 10%),
with ketone reagents
absolute water content < 50 ppm
Generator I: 400 mA Generator I: auto
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KF TitrationKF Titration
Coulometric KF reagentsCoulometric KF reagents
• Capacity of more than 1000 mg of water (100 mL KF reagent)
• Anodic and cathodic reagents• Combined reagents• Special reagents for ketones
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KF TitrationKF Titration
• Volumetric titrationrange of application 0.1 % - 100 % depends on sample size
• Coulometricrange of application 0.001 % - 1 % (10 µg - 200 mg absolute water content), mainly liquids and gases
Which is the right method for my Which is the right method for my application?application?
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
Endpoint indicationEndpoint indication
Bivoltametry Ipol = 50 uAConstant current applied to double Pt electrode
During titration: Excess H2O High voltage between Pt wires
At end of titration: Small excess of free iodine Voltage decreases sharply
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KF TitrationKF Titration
Endpoint indicationEndpoint indication
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
permanent consumption of KF reagentpermanent consumption of KF reagent
DriftDrift
Aim: constant and low drift
Optimal: Volumetry <10 L/min
Coulometry 2...10 g/min
• Influence on the results drift correction
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KF TitrationKF Titration
DriftDrift
• Start drift – acceptable drift value for start of determination (cond. OK)
• Stop criteria drift – absolute or relative drift value- Absolute drift– the entered value is the stop drift- Relative drift – the stop drift is calculated from the
measured drift value (start) and the entered value
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
Titration parameterTitration parameter
VolumetryVolumetry
EP at U 250 mV
Dynamics 100 mV
Stop criteria drift/time
Stop drift 20 uL/min
Delay time 10 s
I(pol): 50 uA
CoulometryCoulometry
EP at U 50 mV
Dynamics 70 mV
Stop criteria drift/rel drift
Stop drift 5 ug/min
Rel. Drift 5 ug/min
Start drift 20 ug/min
I(pol) : 10 uA
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KF TitrationKF Titration
TopicsTopics
• KF reaction• Volumetric KF titration• Coulometric KF titration• Endpoint indication • Drift as second endpoint indication• Parameters• KF instruments
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KF TitrationKF Titration
Volumetric KF Titration
Titrinos:
787 KF Titrino795 KFP Titrino
Titrandos:
841 TitrandoPC Control / tiamo
Touch Control
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KF TitrationKF Titration
Volumetric KF TitrationVolumetric KF Titration
Modi 841 Titrando
KFT X
SET X
Meas X
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KF TitrationKF Titration
Only a version with dosing units ?
• Advantages:
The dosing unit can be totally emptied that means:
– No crystallisation in cock and tubings
– Rinsing the buret several times after changing the titrant is no longer necessary
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KF TitrationKF Titration
Coulometric KF titrationCoulometric KF titration
756 Coulometer– with internal printer
831 Coulometer
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KF TitrationKF Titration
Coulometric cell Vial placed in the oven
Principle of the oven techniquePrinciple of the oven technique
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KF TitrationKF Titration
832 Thermoprep832 Thermoprep 774 Oven Sample 774 Oven Sample ProcessorProcessor