CL-610 Experimental Methods Experiment -2

Measurement of moisture content using Karl Fischer Volumetric Titration

Instructors Prof. Rajdip Bandyopadhyaya Prof. Y S Mayya

Group: M1 Shashwat Omar(133020005) Manish Rathi(133020013)

T A : Pushkar Ballal

Experiment Date: 27/01/2014

Submission Date: 3/01/2014

Department of Chemical Engineering I.I.T. Bombay

Aim: To determine the moisture content of given samples by Karl Fischer volumetric titration
technique.

Motivation: Amount of moisture in a sample plays an important role in governing its physical
and chemical properties, hence, it is required to be reported. Karl Fischer technique is widely used chemical method today for measuring the moisture content of sample.

Introduction: Described in 1935 by Karl Fischer, a chemist, the reagent that now bears his
name was composed of iodine, sulfur dioxide, pyridine and methanol. Its effectiveness, particularly for the determination of water in sulfur dioxide, was quite remarkable. The measurement of moisture content using Karl Fischer reagents is superior to other methods such as loss-on-drying, distillation and infrared absorption, or to electrolysis and other electrical methods, for the following reasons: (1) The absolute amount of moisture can be determined without a working curve (in the case of coulometric titration). Moisture content can be determined accurately, even where moisture is present at levels of only a few ppm. (2) Measurements can be taken over short periods of time. (3) Measurements can be taken using small samples (from a few mg to a few gm). (4) The method can be used with liquid, solid and gaseous samples. (5) The method is suitable for unstable substances that can alter when heated.

Principle: Volumetric Karl Fischer titration requires the determination of the titer of the Karl
Fischer reagent. It is usually quoted in mg of water per ml (mgH2O/ml of KF reagent) of Karl Fischer reagent. In volumetric Karl Fischer, iodine is added mechanically (directly as a component of KF reagent) to a solvent containing the sample by means of a burette during the titration. Water is quantified on the basis of the volume of Karl Fischer reagent consumed. Karl Fischer reagent comprises of pyridine (base) as buffer, sulfur dioxide, iodine and anhydrous methanol as solvent. As pyridine is toxic we use pyridine-free KF reagent which contain imidazole or primary amines as buffering agent. The fundamental principle behind the titration is Bunsen reaction. I2+ SO2+ 2H2O 2HI + H2SO4

Karl Fischer discovered that this reaction could be modified to be used for the determination of water in a non-aqueous system containing an excess of sulfur dioxide. The following reaction takes place during volumetric titration. I2+ SO2 + H2O + 3Base + CH3OH 2Base HI + Base HSO4CH3 Water and iodine are consumed in 1:1 ratio in the above reaction. This is utilized in quantitative determination of moisture content in the sample. Once all of the water present is consumed, the presence of excess iodine is detected voltametrically.

Detection of end point: A constant current of 1-30uA is applied to two platinum electrodes,
and the end-point is detected by measuring the voltage (polarization voltage) between the electrodes. If the titration solution has a relatively high water content, a polarization voltage of 300-500mV will be produced. The voltage varies according to the type of solvent used and the sample. In general, high voltages are produced in the case of substances with low conductivity, such as hydrocarbons. As the Karl Fischer titration continues and the end-point approaches, the voltage suddenly drops to 10-50 mV. With volumetric analysis, the endpoint is deemed to have been reached after the voltage has remains at this level for a specific period of time. With commercially available titration systems, the period is 30-60 seconds. The amount of water present in the sample is then calculated based on the concentration of iodine in the Karl Fisher titrating reagent (i.e., titer) and the amount of Karl Fisher Reagent consumed in the titration.

Materials and Set-up:

Glassware Beakers, Titration flask with magnetic stirrer, Karl Fischer Titrator, Weighing balance

Chemicals: Karl Fischer reagent, Karl Fischer grade dry methanol, Di-sodium tartrate
dihydrate (purified), Samples (KCl and Glycerol).

Set-up:

Procedure:
1. Fill around 50ml of methanol into an oven dried titration flask. 2. Place the tubes filled with silica gel and molecular sieves in flask and reagent bottle. These are used for adsorbing moisture present in air which flow across them and so as not to create vacuum in reagent bottle. 3. Attach the dispenser to the flask and start titration for neutralizing water present in the flask or solvent. 4. Standardize with di-sodium tartrate. Weigh a fixed amount of di-sodium tartrate in a balance using butter paper. Note the reading shown in the balance and add it to flask. Carry out the titration and determine the volume of KF reagent used. 5. Carry out similar experiment by taking samples, first KCl and then glycerol whose moisture content is unknown. Note the amount of sample added to the flask.

6. Repeat the titration thrice for both samples. The end point is detected by means of electrical detection circuit. Note down the corresponding readings and calculate the moisture content present in each sample. 7. Repeat the same procedure for tap water once.

Observations and sample calculation:

Standardization of Karl Fischer reagent using disodium tartrate dihydrate : Concentration factor = 4.0697 (mg/ml) Leak rate = 30 L/min = 30 10-3ml/min Weight of Disodium tartrate dihydrate used in standardization = 99.82 mg Blank volume = 0 ml The percentage of moisture can also be calculated from the given formulae

where S = Strength of KF reagent (mg/ml) or concentration factor W = Weight of Sample (mg) KF = Volume of KF consumed during titration (ml) B = Blank volume entered (ml) LV= Leak Volume (l) Considering 1st reading of KCl sample: S = 4.0697 mg/ml, KF = 0.348 ml, B = 0 ml, LR = 0 L/min, LV = 0 L, W = 82.12 mg

% moisture from experiment = 1.725 % error in calculation = 0

Similarly we find out % moisture for 3 readings of KCl and Glycerol sample. Calculated data are shown in Table 1 (KCl) & Table 2 (Glycerol).

Table 1 : Potassium chloride data:

Sl. No.

Weight of sample, W(mg)

1 2 3

82.12 94.55 115.86

Volume of Karl Fischer reagent dispersed, KF(ml) 0.348 0.324 0.335

Leak rate, LR( L/min) (for 1 min)

% moisture (from experiment)

% moisture (from calculation)

% error in calculation

Coefficient of variation of % moisture (/)

0 0 0

1.725 1.395 1.180

1.725 1.395 1.176

0.0 0 0.278

1.731

Table 2 : Glycerol data

Sl. No.

Weight of sample, W(mg)

1 2 3

71.30 93.40 122.50

Volume of Karl Fischer reagent dispersed, KF(ml) 1.133 1.565 2.197

Leak rate, LR( L/min) (for 1 min)

% moisture (from experiment)

% moisture (from calculation)

% error in calculation

Coefficient of variation of % moisture (/)

5 10 5

6.467 6.824 7.299

6.438 6.776 7.282

0.441 0.703 0.233

0.578

Results:
Average % moisture in sample 1 (KCl) = (1.725+ 1.395 + 1.176)/3 = 1.432 % Average % moisture in sample 2 (Glycerol) = (6.438 + 6.776 + 7.282)/3 = 6.832%

Discussions and Conclusions:

1. Percentage moisture in KCl and Glycerol sample is 1.432% and 6.832% respectively. 2. It is observed that coefficient of variation is more in sample 1 (KCl) than sample 2 (Glycerol) which might be due to better mixing of liquid in the solvent than a solid. 3. Percentage moisture obtained in tap water sample is 81.80%. We conclude that the remaining is amounts of salts, especially carbonates. 4. The method can detect moisture content as low which is usually difficult to obtain via oven drying. 5. The Karl Fischer method is used for compounds that contain volatile substances and for compounds that are amenable to thermal decomposition. 6. Karl Fischer method is widely used because of high accuracy and precision. The advantages are small sample quantity required, ease of sample preparation, short analysis duration, and can be used for analyzing solid, liquid and gases.

Sources of error:
1. More accurate results can be obtained by better stirring system (replacing the magnetic stirrer). 2. Sample must be charged precisely in the flask, none of it must remain on the surface. 3. Care must be taken such that sample doesnt contain large granules which settles down and hence gives erroneous results. 4. The location of anode also matters in the flask and hence, measurement of voltage depends upon the same.