“Aquamax

KF”

Coulometric

User Manual

Aquamax KF v.08.10

Aquamax KF Coulometric v08.10

CONTENTS

Introduction …………………………………………………….……… Page 3

Principle of Measurement ……………………………………………… Page 4

Specifications & Features ……………………………………………… Page 5

Unpacking & Parts List ……………………………………………… Page 6

Titration Cell Assembly Instructions …………………………………… Page 7-8

Filling & Changing Reagents ………………………………………….. Page 9

Front & Rear Panel Description ………..……………………………… Page 10

Setting Time & Date …………………………………………………… Page 11

Connection & Start Up Procedure ……………………………………… Page 12

Programming A Method ……………………………………………….. Page 13-19

Example Methods & Applications……………………………………… Page 20 - 23

How To Run A Test………………Examples V/SG & W/w…………… Page 24 - 25

Printer …………………………… Loading the paper…………………. Page 26

Example Print Out…………………. Page 27

Drift Compensation ……………………………….……………………. Page 28

Overtitration ……………………………………………………………. Page 28

Reagent Life ……………………………………………………………. Page 28

Cleaning the Glassware ………………………………………………… Page 29

Troubleshooting ……………………………………………………….. Page 30

Warranty ……………………………………………………………….. Page 30

Accessories ……………………………………………………………….. Page 31

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Aquamax KF Coulometric v08.10

G.R. Scientific Ltd.

Tel: +44 1525 404747 Fax: +44 1525 404848

E-mail: [email protected] Website: www.grscientific.com

Correspondence Address: Delivery Address:

P.O. Box 242

Ampthill

Bedfordshire

MK45 5AQ

United Kingdom

Building 69

Wrest Park

Silsoe

Bedfordshire

MK45 4HS

United Kingdom

INTRODUCTION

Key personnel at G.R. Scientific are recognised experts in coulometric Karl Fischer titration technology.

They have designed and manufactured coulometric titrators since the early 1980’s and are widely regarded as some of the leading specialists in this technique.

The Aquamax KF Coulometric has a small footprint, is easy to use, and supplied complete with a specifically designed low drift cell which is also suitable for outdoor use. The built-in battery and optional carry case, provide the versatility required by the laboratory and also the ease of use and portability required by the field engineer.

Cou-Lo Formula reagents have been specially formulated for use with Aquamax KF titrators. Formula

A anode reagent is suitable for most routine applications and is especially useful for water content determination of oil samples, e.g. transformer oils, crude oils, etc. This anode reagent is supplied in

“single shot” bottles of 100ml – No measuring of volumes required – No mixing of other solvents required. Cathode reagent Formula C is supplied in “single shot” 5ml vials which have “safety snappers” pre-fitted thereby reducing risk to the operator.

Where appropriate G.R. Scientific products include traceable calibration certificates and are backed up by a five year warranty. These titrators are used by many leading companies in the oil, petrochemical, gas, pharmaceutical, biotechnology, automotive and power generation industries.

For a list of users, typical applications or details of our network of international distributors, please visit our website, www.grscientific.com , or contact G.R. Scientific Ltd. on:-

Tel: +44 1525 404747. Fax: +44 1525 404848. E-mail: [email protected]

To obtain the full benefits that this instrument can offer it is recommended that you read this user manual before assembling the unit.

Cou-Lo and Aquamax KF are registered trade marks of G.R. Scientific Ltd. “ACE” control system is patented technique owned by G.R. Scientific Ltd.

(All Aquamax KF power supplies are double insulated units that do not need an earth (ground) connection. These units are sealed and conform to CSA(LR84459), UL listings and CE requirements. Aquamax KF titrators only require a low voltage 15V input to the electronic / control circuitry. The moulded plastic casing of the instrument also provides additional insulation.)

3

Aquamax KF Coulometric v08.10

PRINCIPLE OF MEASUREMENT

Karl Fischer titration is simply a means to measure water content of samples. Modern instruments, such as the Aquamax, use the coulometric principle, whereby the water present in the sample is coulometrically titrated to a predefined end point at which there is a minute excess of free iodine present.

Stoichiometrically, 1 mole of water will react with 1 mole of iodine, so that 1 milligram of water is equivalent to 10

×71 coulombs of electricity. Combining the coulometric technique with Karl Fischer titration, Aquamax KF titrators determine the water content of the sample by measuring the amount of electrolysis current necessary to produce the required iodine. This is an absolute technique which does not require calibration of the reagents. For further information, visit www.grscientific.com, and download the

PDF article titled “Recent Advances”.

SO

I

2

+SO

2

+3C

5

H

5

N+H

2

O

® 2C

5

H

5

N.HI+C

5

H

5

N

2

O

SO

2

SO

4

CH

3

C

5

H

5

N +CH

3

OH

® C

5

H

5

N

O H

2I

` - 2e ® I

2

Using the latest pulse current technology and our patented “ACE” control system, (Patent No.GB2370641), the Aquamax KF automatically selects the appropriate titration speed dependent upon the amount of water present in the sample. The titration speed is reduced as the end point is approached, and when the titration is completed the instrument prints out and displays the results. For a more detailed explanation of the technique, and a comparison with volumetric Karl Fischer titration, please visit our website, www.grscientific.com

4

Aquamax KF Coulometric v08.10

Titration method

Electrolysis control

End point detection

End point indication

Display

Measuring range

Moisture range

Max. sensitivity

Max. titration speed

Max. electrolysis current

Drift compensation

Start delay time

Min. titration time

Power supply

Precision

Calculation modes

Display format

Print format

Statistics

Method storage

Sample ID number

Printer

Stirrer speed

Battery life

Charging time

Battery low indication

Dimensions

Weight

Carry case

Calendar / clock

SPECIFICATIONS & FEATURES

Aquamax KF Coulometric

Coulometric Karl Fischer Titration

Patented “ACE” control system (GB2370641)

AC polarisation

Visual display / print out / acoustic beep

40 character alphanumeric backlit LCD

1μg – 10 mg water

1 ppm – 100 % water

0 • 1μg

2 mg per minute

400 ma

Automatically controlled

0 – 30 minutes user programmable

0 – 30 minutes user programmable

90-264 VAC, 47-63 Hz, 12V DC car adapter/internal battery

10 - 100μg ± 3μg, 100μg – 1 mg ± 5 μg, above 1 mg ± 0•5%

User programmable calculations:- Weight/weight,

Volume/density, Volume/volume, Weight/Dilution ratio.

μg, mg/kg, ppm, %

μg count plus calculated mg/kg, ppm, % water

Upto 99 runs, user programmable

10 programmable methods

User programmable

42 character high speed thermal printer

Microprocessor controlled

8 hours running time from fully charged

Fully charged 14 hours

Display & print out indication

10 x 9½ x 5 inches (250 x 245 x 120 mm)

6 pounds (3 kg)

Optional

Analysis time & date print out

5

Aquamax KF Coulometric v08.10

UNPACKING & PARTS LIST

Inside the shipping carton you will find a plastic case which contains the glassware and accessories pack and the user manual. The Aquamax KF titrator is located underneath the glassware case (or inside the optional carry case if ordered). The mains power lead, power pack and in-car adapter are inside the carry case lid compartment.

Remove all of these items and check that they have arrived undamaged.

After unpacking your Aquamax KF check that the glassware/accessories pack contains:-

Item Description Low Drift Cell

1 pce

1 pce

1 pce

1 pce

1 pack

1 pce

1 pce

1 bottle

1 pce

1 pce

1 pce

Titration Vessel

Detector electrode

Generator electrode

Desiccant tube & cap

Injection septa (10)

1ml Gas Tight syringe

Luer needle

Molecular sieve

Stirrer bar

Funnel

Thermal paper roll

71- 0102

71- 0103

71- 0104

71- 0106

71- 9507

71- 9508-GT

71- 9509

71- 9512

71- 9514

71- 9515

71- 0119

1 pce

1 pce

1 pce

1 pce

1 pce

1 pce

Mains lead

Mains power pack

In Car Adapter

User Manual

Dust cover

Carry case (optional)

ACCESSORIES

71- 4014 /18 /19/20 UK/EU/US

71- 401607

71- 401421

71- 9517

71- 301301

71- 201109

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Aquamax KF Coulometric v08.10

AQUAMAX KF TITRATION CELL

STEP BY STEP ASSEMBLY INSTRUCTIONS

Position titration vessel on Aquamax KF titrator

The glass joints do not require Teflon sleeves or grease. The special screw fittings seal the vessel from ingress of moisture from the atmosphere and are easily released, even after several weeks.

Position electrodes on titration vessel. It is not necessary to overtighten these screw joints.

Connect leads to generator and detector electrodes then connect the leads to the titrator. Generator electrode lead connects to socket marked

“GENERATOR”

– detector electrode lead connects to socket marked

“DETECTOR”

Place stirrer bar inside titration vessel

Fit injection septa into plastic screw cap connectors and locate onto injection ports of titration vessel.

Fill drying tube with molecular sieve and locate on top of generator electrode

The assembled titration cell is now ready to be charged with reagents prior to use. Please be sure to assemble correctly every time the cell is cleaned or re-filled. It is recommended that the titrator is NOT switched on until after the titration vessel has been charged with reagents. This will avoid damage being caused to the electrodes by the stirrer bar. Avoid twisting the electrode leads otherwise they may become damaged.

7

AQUAMAX KF TITRATION CELL

Aquamax KF Coulometric v08.10

8

Aquamax KF Coulometric v08.10

FILLING & CHANGING REAGENTS

The Aquamax KF has been designed to operate with all major coulometric Karl Fischer reagents, however optimum performance can be obtained by using Cou-Lo Formula reagents which have been specifically formulated for use with these instruments. For most routine applications 100ml of

Formula “A” (anode reagent) and 5ml of Formula “C” (cathode reagent) are used. When analysing

Transformer oils, Crude oils and other petroleum products Formula “A” is especially suited as it contains other solvents to improve sample miscibility and solubility.

(When analysing samples of Ketones, amines or others which may interfere with the reaction it is advisable to use specialised reagents which can be obtained from various suppliers).

Although reagents can be poured into the titration vessel whilst it is located on the titrator, we recommend that the vessel and electrodes are removed from the instrument whilst this procedure is performed to avoid reagent spillage onto the instrument casing.

(Any spillage onto the instrument casing should be wiped off immediately to avoid damage or staining).

Remove the drying tube and injection septa. Using the funnel supplied, charge the titration vessel upto the lower line with

Formula “A” reagent. For your convenience these reagents are supplied in “single shot” bottles which contain 100ml so it is not necessary to measure any volumes – simply pour in the complete bottle

Also using the funnel, charge the inner chamber of the generator electrode with Formula “C” reagent which are supplied in “single shot” 5 ml vials which havce “safet y snappers” pre-fitted thereby reducing risk to the operator.

(It is not necessary to clean the funnel between reagents.)

Reconnect the drying tube and injection septa so that the titration vessel is sealed from ingress of atmospheric moisture.

Locate the complete titration vessel onto the titrator and connect the electrode leads onto the appropriate sockets

The colours of anode and cathode reagent are only an illustration to show that there are two different liquids. These are not necessarily the exact colours of the reagents being used.

The Aquamax KF titrator is now ready to be switched on.

Cathode Reagent Anode Reagent

9

Aquamax KF Coulometric v08.10

DESCRIPTION

Front Panel

Printer Display panel

Keypad Stirrer speed

Rear Panel

Power Jack:-

Fuse:-

RS232:-

USB-B:-

Nominal 15v DC 40w. Supply Input

3,15amp T type Time delay

Standard 4 wire RS232 Input / Output

Port.

Direct cable to PC / Results Manager

Port.

Removable Flash Memory Store Port. USB-A:-

RS232 Port. –

For updating titrator software, connecting to other equipment for remote controlling (software specific protocols to be provided).

USB-B Port. –

For connecting directly to PC to export data to Results Manager and enable results to be saved on files for future reference. (See Results Manager User Manual section)

USB-A Port. –

For exporting results data to a Removable Flash Drive (memory stick), when running sample tests in the field or remote locations, and subsequent transfer to PC at a later date for loading onto Results Manager files.

To use the memory store, insert Flash Drive into USB port A, titrator will see it and a symbol will appear on the display.

The symbol will appear blacked out while the drive is being written to and then as when idle.

The drive should only be removed when in the idle mode.

To read data saved on drive insert it into PC USB port. Start Results Manager, load selected file and then save in the format you require, see Results Manager user manual for full instructions.

There is a separate power ON/OFF switch on the rear panel. Whilst connected to mains power supply, a trickle charge is continuously applied to the battery. It is therefore recommended that the instrument is used from mains power supply whenever possible so that the battery is kept fully charged. Maximum battery operating time is 8 hours continuous use. This may be reduced if repeated high water contents are being determined or if the printer is being continually used.

10

SETTING THE DATE AND TIME

1. Switch on the Aquamax KF and wait for it to display the following :

Aquamax KF Coulometric v08.10

Aquamax KF

Press START

2. Hold down the

START

KF displays:-

Set Date / Time:

DD/MM/YYYY HH:MM:SS

3. Use the

•

decimal point key to move the cursor across the screen.

4. Use the numerical keys to set / alter the required number

START

key to save the changes and exit.

11

Aquamax KF Coulometric v08.10

CONNECTION & START UP PROCEDURE

1. Assemble glassware (see Assembly Instructions )

2. Charge vessel and generator electrode with reagents (see Filling & Changing Reagents )

3. Locate assembled titration vessel onto the Aquamax

4. Connect electrode leads

5. Connect mains lead / power cord

6. Switch ON (using switch on rear panel) and wait for display to show:-

Aquamax KF

Press START

(If required adjust the stirrer speed using the black toggle switch on the front of the instrument.)

microgram count

Aquamax xxxx mg

|||||||||| 4 detector signal titration speed

At the end of the precondition period the display will show:-

Precondition

Dft = xxxx mg

||| Drift Test

After the initial drift has been calculated, in micrograms of water per minute, the Aquamax KF is ready for operation.

Dft = xx xxxx mg

|| 1 Ready

The background drift value will usually slowly decrease with time as the titration vessel becomes drier and more stable. Although it is possible for the titrator to be used at high drift values, it is advisable to wait until the drift value is below 20 mg/minute, and stable, before commencing, especially for low water content samples in the ppm ranges. The lower, and more stable the drift – the more accurate the result.

12

Aquamax KF Coulometric v08.10

PROGRAM FUNCTIONS

When the Aquamax KF displays Ready you can enter titration parameters, recall or edit existing methods, enter new method files, etc., by using the

PROGRAM, ENTER, CLEAR

and

·

keys.

Key Functions:-

PROGRAM

ENTER

CLEAR

- press PROGRAM key to scroll through menus listed. allows parameter values for the displayed menu to be entered into memory. this key has two functions:

(1) If you have finished entering data, press CLEAR and the Aquamax KF will return to the Ready condition.

(2) If you have started to enter an incorrect value, press CLEAR and the

Aquamax KF will display the previously stored value, you can now select the correct value and press ENTER.

• ]

decimal point key allows scroll through of individual parameters in each menu.

When the required parameter is displayed, press ENTER to store it.

MENU LIST

Sample ID Number

Result Format

Calculation Mode

- upto 8 digits

- mg, ppm, mg/kg or % water

- V/SG, W/W, W/K or V/v

Printer Mode

Statistics Print

Print Drift

Start Delay Time

- off, every result or full report

- upto 99 runs, will print min., max., mean, SD & CV

- on or off

- upto 30 minutes

Min. Titration Time

End Sensitivity

Beep Mode

- upto 30 minutes

- 0 – 9 seconds

- off, keypress, end titration or both

Language

Generator Electrode

- select language

- with frit, without frit

Save Method - store upto 10 methods

See PROGRAMMING A METHOD for an explanation of each Menu List parameter

13

PROGRAMMING FLOW CHART

Aquamax KF Coulometric v08.10

14

Aquamax KF Coulometric v08.10

PROGRAMMING A METHOD

After the initial drift has been calculated, in micrograms ( mg) of water per minute, the Aquamax

KF is ready for operation. It is now possible to step through the PROGRAM parameters and enter the required calculation data.

Dft = xx xxxx mg

|| 1 Ready

The Flow Chart on the previous page may prove helpful. Press the PROGRAM key until the required option is displayed then simply follow the Flow Chart to enter the specific data values. Pressing

PROGRAM will move you on to the next prompt, pressing CLEAR will return to Ready condition. It is not necessary to step through all of the programme functions for every method, for example, if you only require to change the

Beep Mode from Off to Both – simple press PROGRAM until display shows Beep Mode, press the decimal point key

·

until display shows Both, then press ENTER and CLEAR to return to Ready.

SAMPLE ID NUMBER

Press PROGRAM → Display will show → Key upto 8 numbers → Press ENTER

PROGRAM

Sample ID No.

Sample ID No

ENTER

12345678

If you do not want to enter any further parameters simply press CLEAR to go back to the Ready condition.

Press PROGRAM if you want to continue entering other parameters

RESULT FORMAT

→

Display will show Press PROGRAM

PROGRAM

Result Format mg

Results can be selected in mg, ppm, mg/kg or % water.

If you want to select the format already stored in memory (and shown on display), press PROGRAM and the instrument will go to the next prompt. If you want to change format to give results in ppm, mg/kg or % you can scroll through these options by pressing decimal point key

·

until the required format is displayed, then press ENTER to store this in memory and PROGRAM to move onto the next prompt. If you have selected a result format in ppm, mg/kg or % the instrument will prompt you for the necessary calculation mode and data values.

Result Format

%

ENTER PROGRAM

Calculation Mode

V / SG

The display shows the calculated water content according to the programmed Result Format and

Calculation Mode program settings, ie. whatever has been chosen to be shown/printed at the end of the titration. The only exception to this is in the W/w mode when the Tare Weight has not yet been entered. In this case the display will show the mg count. The PROGRAM key can be used to enter the Tare Weight at any time during the titration, once this has been done the display will start to show the calculated result in ppm, mg/kg or % water.

15

Aquamax KF Coulometric v08.10

CALCULAT ION MODE

The Aquamax KF has four standard calculation modes in memory. Each of these allow the instrument to divide the microgram count by the gram weight of sample introduced so that the calculated result can be printed out in either ppm or percentage of water.

Press the decimal point key

·

to scroll through the options available.

Select the calculation mode required and press ENTER.

The display will prompt you with the appropriate parameters.

Enter the numerical value for each parameter and press ENTER.

The four standard calculations are:-

1. Weight difference W/w

(This is the most accurate calculation and is suitable for almost all types of samples, powders,

liquids, gases, etc.)

Result (ppm or %) = microgram count

W - w

Where W = total weight of sampler + sample (gm)

w = tare weight of empty sampler (gm)

After entering the total weight (W) the instrument will return to the Ready condition. The Tare weight

(w) can be entered at any time during the titration by pressing PROGRAM, or at the end of titration. For ease of operation it is possible to enter the Total weight (W) as 0.0000gm, then place the full sampler on the balance and tare to zero. Thereafter it is only necessary to enter the weight difference (tare weight w) for each titration. This procedure reduces potential data entry errors.

2. Weight/Dilution ratio W/K

(Use this method if you need to dissolve a sample in another solvent. Suitable for samples which will not dissolve in the anode reagent or which might interfere with the KF reaction)

Result (ppm or %) = microgram count - bl where:

W

W = weight of sample dissolved (gm) x K

K = total volume of diluent + sample volume injected into Cou-Lo Aquamax bl = micrograms of water for same injected volume of diluent ( mg) e.g.

Accurately weigh approximately 2 gm of sample into a 20ml stoppered graduated flask. Make upto the volume line with suitable solvent / diluent. Using appropriate syringe inject 100 ml of diluted sample into the titration cell. Calculation parameters for this example would be:-

W

K bl

=

=

=

2 gm

20ml =

100 ml

200 microgram count of 100 ml injected volume diluent

16

Aquamax KF Coulometric v08.10

3. Volume / Specific Gravity V/SG

(The most widely used technique for liquid samples. However, care must be taken to ensure

removal of all air bubbles from the syringe)

Result (ppm or % ) = microgram count

4.

V x SG where V = volume of sample (ml)

SG = specific gravity

Volume V/v

Result % volume = microgram count

V x 1

×0 where V = volume of sample (ml)

This is essentially the same as V / SG mode, except that the sample S.G. is fixed at 1

×0

PRINTER MODES

Selecting this program allows the printer to be turned ON or OFF. It also enables you to print out the titration parameters being used at that time. Simply scroll through the options using the decimal point key

·

until the required mode is displayed, then press ENTER.

Options available:

Off - no result print out

Every result - will print result after every titration, first result also prints all calculation input data.

Full Report - will print results after every titration and then print out statistical data after a selected number of titrations.

STATISTICS PRINT

The Aquamax KF can be programmed to print out the statistical data from a series of results when using

“Full Report” print mode. If no number has been selected, the Aquamax will automatically clear after 99 runs. If 3 or more runs have been selected the Aquamax will print out the minimum, maximum, mean, SD

& CV values.

PRINT DRIFT

The Aquamax KF can be programmed to print out the drift value for each titration. This is a useful indicator of titration cell stability. If drift is above 25 μg / minute print will show **XX**. This is a warning that a high drift value was present at start of the titration.

17

Aquamax KF Coulometric v08.10

DELAY TIMES

The Aquamax KF has been programmed to accept two different types of delay times, one at the start of titration and one at the end as a minimum titration time.

START DELAY TIME

The Aquamax KF has a preset delay of five seconds which allows samples to be dispersed into the reagents before the titration starts. Some samples, particularly powders and viscous samples, may need additional time to fully dissolve. By selecting the start delay program, you can increase this time by upto 30 minutes.

Display shows: Start Delay Time

00 mins 00 secs

Select required time delay and press ENTER.

Whilst a delay time is in operation, the display will show “add sample” and the clock counter will show the time remaining before the start of titration. A start delay can be overridden by simply pressing START

MINIMUM TITRATION TIME

For some applications, such as certain gas samples or when using the Aquamax KF combined with a solid sample vaporiser unit, such as the ADP 511, it can prove useful to delay the end point of the titration. By selecting this parameter you can increase the minimum titration time by upto 30 minutes.

Display shows:

Min. Titration Time

00 mins 15 secs

Select required minimum time and press ENTER.

END SENSITIVITY

The sensitivity of detector signal as the end point is approached can be set from 0 – 9 seconds. The default value is 3 seconds and there are very few occasions when this may need to be altered. Decreasing this value can prove useful if samples cause interference, e.g. some Lube Oil samples.

BEEP MODE

Four options are available for the audible alarm (beeper) and they can be scrolled through using the decimal point key

·

until the required one is displayed. Then press ENTER.

The options are:

Off - beeper inactive

Keypress - beep once every time a key is pressed

End titration - beep three times at the end of a titration

Both - beep after every keypress and three times at the end of a titration

18

Aquamax KF Coulometric v08.10

LANGUAGE

The Aquamax KF can be programmed to show all display prompts and print outs in various languages. Use the decimal point key

·

to select language then press ENTER.

Choose from English, Francais, Espanol, Portugues, Deutsch & Magyar.

GENERATOR ELECTRODE

The Aquamax KF can be operated using generator electrodes with or without frit (diaphragm). Use the decimal point key

·

to select either with or without frit then press ENTER. The titration electrolysis current settings are automatically adjusted for each style of generator and appropriate reagents.

SAVE METHOD

If you want to save a method for future use, this can be done by pressing a numerical key, 0 - 9, and

ENTER. All titration parameters, printer mode, beeper mode, etc. are stored automatically.

Display then shows:

Save Method

Done

Then press CLEAR and the instrument will revert back to the Ready condition.

RECALL METHOD

If any methods have been saved to memory then the first prompt (before Sample ID number) will be

“Recall Method”

When this prompt is displayed, simply press the number of the method file you wish to recall and press

ENTER. There are 10 method files available numbered from 0 to 9. The titration parameters etc will all be automatically recalled. Press PROGRAM to view the recalled method parameters or press CLEAR and the instrument will go back to the Ready condition.

If you do not want to recall a method, press PROGRAM to view the next prompt.

19

EXAMPLE COULOMETRIC METHODS

Aquamax KF Coulometric v08.10

Water Determination of Electrical Insulating Oils by Coulometric Karl Fischer

Titration

ASTM D 1533

ASTM D 4928

ASTM D 6304

IP 386

IP 438

IEC 60814

BS EN 60814

ISO 10101-3

ISO 10337

ISO 12937

Water Determination of Crude Oils by Coulometric Karl Fischer Titration

Water Determination of Petroleum Products by Coulometric Karl Fischer Titration

Water Determination of Crude Oils by Coulometric Karl Fischer Titration

Water Determination of Petroleum Products by Coulometric Karl Fischer Titration

Water Determination of Insulating Liquids, Oil Impregnated Pressboard by

Coulometric Karl Fischer Titration

Water Determination of Natural gas by Coulometric Karl Fischer Titration

Water Determination of Crude Petroleum by Coulometric Karl Fischer Titration

Water Determination of Petroleum Products by Coulometric Karl Fischer Titration

20

Aquamax KF Coulometric v08.10

EXAMPLE APPLICATIONS

LIQUID SAMPLES

Liquid samples are usually introduced into the titration vessel by using a syringe. The greater the amount of water introduced into the titration cell will cause the titration to take longer and also consume the reagents more quickly. It is recommended that the smallest representative amount of sample be used to ensure fastest titration speed and maximum sample throughput before reagents have to be replenished. Supplied as standard with every Aquamax KF titrator is a 1ml syringe and luer needle. These are suitable for injection of oil samples and water standards. Other volume syringes are commercially available from various suppliers. Please ensure that the needle is long enough to reach into the anode reagent.

This guide may be of assistance when selecting injection volume of samples:-

Expected water content…………….Suggested sample size

1 - 10 ppm……………… 1 or 2 ml

10 - 100 ppm……………… 1 or 2 ml

100 - 500 ppm……………… 0

× 5 or 1 ml

500 - 1000 ppm……………… 0

× 5 or 1 ml

0

× 001 - 0 × 01 % ……………… 1 or 2 ml

0

× 01 - 0 × 1

% ………..…..… 1 or 2 ml

0

× 1 - 0 × 5

% ……………… 0

× 5 or 1 ml

0

× 5 - 1 × 0

% ……………… 0

× 5 or 1 ml

1

× 0 - 5 × 0

% ……………… 0

× 2 ml above 5

× 0 % ……………… 0 × 1 ml or less

Please note that these volumes are only a guide. You may wish to experiment with sample size to determine the optimum balance between repeatability, reagent depletion and speed of analysis.

CRUDE OILS

(IP 386 & 438, ASTM D1533, D4928, D6304, API MPMS Chapter 10.9, ISO 10337 & 12937)

Most coulometric reagents contain Methanol as the main solvent and as such it is possible that waxy deposits from crude oils can “drop out” and contaminate the electrodes, requiring more frequent and thorough cleaning of the glassware. This problem can be reduced by using Cou-Lo “Formula A” anode reagent which has been specially formulated for this application. The most common interference in crude oil samples is usually caused by mercaptans or sulphides. Samples containing alkyl groups will react stoichiometrically so that:

100 ppm Mercaptans would show as approximately 30 ppm water

100 ppm Sulphides would show as approximately 50 ppm water

In normal practice oils containing less than 500 ppm mercaptans or sulphides are regarded as having no appreciable effect. Repeatability problems are usually caused by sampling inaccuracies or improper homogenisation of the sample.

21

Aquamax KF Coulometric v08.10

TRANSFORMER/INSULATING OILS

(ASTM D 1533, BS EN 60814, IEC 60814)

Due to the viscosity of these samples, and the fact that typical water content levels are in the range 5 – 40 ppm, it is usually necessary to inject sample volumes of 1 ml. This means that upto 50 samples would fill the titration cell. Provided that the other criteria governing reagent life, (total water titrated and reagent age), have not been reached, then it is possible to switch off the titrator and allow the oil to separate from the reagent. The oil can then be siphoned off and the instrument switched on again. After this operation it may take upto 30 minutes before the instrument settles down to a stable baseline. If it takes longer than 30 minutes then it is advisable to clean the cell and recharge with fresh reagents. For optimum performance use Cou-Lo “Formula A” reagent.

TURBINE / LUBRICATING OILS

For most Lube Oil applications a sample size of 1ml is sufficient. However, if it is suspected that the water content is above 1 %, then a sample size of 0

× 2 to 0× 5 ml is suggested.

Some lubricating oils contain additives which can coat the detector electrode or block the glass frit of the generator electrode. These problems can be reduced by modifying the Anode reagent with 20 – 40 % volume Chloroform. If difficulties continue, contact G. R. Scientific Ltd for further information.

KETONES AND AMINES

These can react with the Methanol present in most coulometric reagents resulting in inaccurate results and, in extreme conditions, titration end point being unattainable. For samples containing ketones, amines or aldehydes the use of specially formulated coulometric reagents for ketone samples is recommended.

POWDER SAMPLES

One of the main advantages of the coulometric technique is that reagents do not have to be replenished after every analysis, therefore the introduction into the titration cell of solid samples, which do not dissolve, is not recommended.

Three options available:-

· Powder samples which readily dissolve in the Anode reagent can be introduced using the optional powder sampler, part no. 2000-9511. Calculation mode W/w.

· Powder samples which cannot be dissolved in the Anode reagent should be extracted or dissolved in a suitable solvent and then an aliquot injected. Calculation mode W/K.

· If neither of above methods are suitable you may need to use a ADP 511 oven in conjunction with the

Aquamax KF titrator.

Powder sampler ADP 511 Evaporator

22

Aquamax KF Coulometric v08.10

GAS SAMPLES

Gas samples can be introduced by fitting a needle onto the gas sampling bomb and selecting Calculation mode W/w. Alternatively, gas samples can be bubbled through the titration vessel and the passed volume measured. For this method we suggest using the optional Low Drift Cell (LDC-0101) complete with gas analysis kit (LDC-0121).

1. Fit the gas inlet and outlet adapters in place of the injection septa.

2. Remove the drying tube and seal the top of electrode using the injection port septa and screw cap.

3. Connect outlet adapter to wet gas flow meter.

4. Flush the sample lines and allow instrument to stabilise.

5. Press START and allow gas sample to flow through the cell at an approximate flow rate of 0

× 5 litres/minute.

6. Turn off gas flow and allow titration to reach end point.

Calculation

G x (273 + t ) x 22

× 4

W=

V x 273 x 18

W = moisture content

G = microgram count

V = gas volume, litres

t = water temperature of wet gas flow meter (

°C)

Gas sample adapter Fitted to vessel

23

10.

11.

12.

6.

7.

8.

9.

1.

2.

3.

4.

5.

Aquamax KF Coulometric v08.10

HOW TO RUN A TEST

Please read the section PROGRAMMING A METHOD then use the PROGRAMMING FLOW CHART before running any samples,

Example: Transformer oil sample by V/SG

Program the Aquamax KF with parameters for the analysis. For Transformer Oil samples, these parameters are usually:-

Result Format

Calculation Mode

Sample Volume

Sample SG

= mg/kg or ppm

= V/SG

= 1.0 ml

= 0.875

Other parameters such as Sample ID number, Printer Mode etc are optional.

ANALYSIS METHOD

Confirm that Aquamax KF is in “Ready” mode

Flush 1.0ml syringe several times (minimum 6 times) with sample

Fit luer needle and flush through with sample

Draw sample into syringe beyond the 1.0ml marking

Invert syringe so that any air bubbles can be ejected through the needle and adjust syringe plunger to the 1.0 ml mark

Wipe off excess sample from outside of needle using a clean, dry tissue or paper towel

Pierce needle through injection septa of titration vessel (1 – 2 cm)

Press START

Push needle into anode reagent and inject sample

Withdraw needle from titration vessel

Read result, in mg/kg (ppm) water, on display and printout

Repeat steps 2 – 11 if duplicate result required

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Aquamax KF Coulometric v08.10

Example: Powder sample by W/w

Program the Aquamax KF with parameters for the analysis.

ANALYSIS METHOD (1)

1. Confirm that Aquamax KF is in “Ready” mode

2. Place a suitable amount of sample in the powder sampler (p.n. 2000-9511) and seal with stopper provided.

3. Weigh sampler

4. Press PROGRAM until Calculation Mode displayed then select W/w

5. Enter the sampler weight when prompted by display, then press ENTER / CLEAR

6. Remove the injection septa port, press START, and pour the sample inside the titration vessel ensuring that sample does not stick to the inside of the vessel wall.

7. Reweigh the sampler.

8. The net weight of sampler can be entered either during the titration by pressing PROGRAM or waiting until the end of titration when display will prompt TARE Weight. Enter the weight then press CLEAR.

ANALYSIS METHOD (2)

1. Confirm that Aquamax KF is in “Ready” mode

2. Place a suitable amount of sample in the powder sampler (p.n. 2000-9511) and seal with stopper provided.

3. Place sampler on balance and tare to zero

4. Press PROGRAM until Calc. Mode displayed then select W/w

5. Enter the sample weight as 0.0 gram, then press ENTER / CLEAR

6. Remove the injection septa port, press START, and pour the sample inside the titration vessel ensuring that sample does not stick to the inside of the vessel wall.

7. Reweigh the sampler.

8. The weight difference of sampler can be entered either during the titration by pressing PROGRAM or waiting until the end of titration when display will prompt TARE Weight. Enter the weight then press

CLEAR.

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Aquamax KF Coulometric v08.10

LOADING THE PRINTER

To load the paper into the printer, first open the paper roll holder lid above the print head and remove the old roll and rollers. Now fit rollers to new paper roll (LDC-0119), load as shown and insert the paper into the slot at the rear of the print head. As soon as the printer sees the paper it will automatically load it. To avoid damage to the printer mechanism it is advisable to only use the correct part number (LDC-0119) thermal paper rolls.

Cut the end of the paper roll at a slight angle as shown. This will make it easier to feed into the printer mechanism

The mechanism has optical sensors which detect the paper and will auto feed.

Schematic of paper feed

Fit rollers onto both sides of paper roll

Locate paper roll in to compartment

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Aquamax KF Coulometric v08.10

PRINT-OUTS

The Aquamax KF allows you to select different print modes. If you choose to have the printer on, you will receive a hard copy of the result obtained, together with the selected parameters for that particular titration every time a titration is performed. Options available;

Off - no result print out

Every result - will print result after every titration, first result also prints all calculation input data.

Full Report - will print results after every titration and then print out statistical data after a selected number of titrations.

The Aquamax KF automatically increments the next run number every time you press the start button. The run counter is reset to zero when power is switched off and back on again. A duplicate set of results can be printed out simply by holding down the start button for 3 seconds. Results memory is cleared after duplicate print out or when power is switched off.

PRINT OUT EXPLANATION

Aquamax KF

V xxxx

Serial No. 71000

Calibrated DD/MM/YYYY

Run Date

Run: 1 Run Time

Nett Count

Drift

Volume

Density

Result Format

0.0 µg

F

00

1.0000 ml

1.0000

%

Calculation Mode V/SG

Res: 0.0000%

Run: 2 Run Time

Nett Count

Drift

0.0 µg

00

Res: 0.0000%

Aquamax KF

Serial No.

V xxxx

71000

Calibrated DD/MM/YYYY

Run Date

Run: 1 Run Time

Nett Count

N

0.0 µg

Drift

Result Format

00

%

Calculation Mode W/w

Total Weight

Tare Weight

0.0000 gm

0.0000 gm

Sample Weight 0.0000 gm

Res: 0.0000%

EXAMPLE OF V/SG CALCULATION

Titrator model

Software version

Titrator serial number

Date titrator calibrated

Date sample run

Run number & time of analysis (F = generator electrode with frit)

Nett microgram count (after drift correction)

Drift value at start of titration

Result format selected

Calculation mode selected

Sample volume

Sample density

Calculated result water content

Subsequent runs of the same sample and calculation parameters show run number, run time, nett count,

Drift value and calculated result.

EXAMPLE OF W/w CALCULATION

Run number & time of analysis (N = generator electrode without frit)

Nett microgram count (after drift correction)

Drift value at start of titration

Result format selected

Calculation mode selected

Weight of syringe plus sample

Weight of syringe after sample injected

Weight of sample analysed

Calculated result water content

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Aquamax KF Coulometric v08.10

DRIFT RATE COMPENSATION

At the start of any titration, the drift value in the top left corner of the screen (in micrograms per minute), is stored in memory. This ensures that the displayed result is corrected for any ingress of atmospheric moisture during the titration period.

Whilst in READY condition, the Aquamax KF continually compensates for any drift caused by atmospheric moisture ingress or reagent decomposition and displays this information, which is updated every 10 seconds. If the drift value is above 25 μg /minute the display will show High Drift **XX**. This is a warning that the value is high, however the instrument can still be used by simply pressing START to continue. Provided the drift rate is stable then it usually acceptable to continue operation. The Aquamax titration cell design can provide drift values down to less than 5 μg /minute but can also operate at much higher values. The maximum drift value is 60 μg /minute but we recommend operating upto a maximum of

25 whenever possible.

If the drift value is above 60 mg per minute the display will read

“EXCESS DRIFT - SEE INSTRUCTION MANUAL”

Most common causes of excess drift are:

Titration vessel not properly sealed (check septa & fittings).

Reagent almost depleted (clean & recharge the cell).

Sample introduced before pressing START key.

Trace moisture on cell walls.

If excess drift occurs, switch the instrument off, remove titration cell from clamp, gently swirl the anode reagent around the cell walls, replace cell in clamp, switch instrument on and allow to precondition.

OVERTITRATION

If the detector electrode senses too much Iodine in the titration cell, usually caused by instrument being left unoperated for a long period, the display will read :-

“OVERTITRATION - SEE INSTRUCTION MANUAL”

Simply add 3 - 5 microlitres of water, or a small amount of a known wet sample, until the detector signal bars on bottom left of display are activated. Then instrument will automatically carry out its precondition.

REAGENT LIFE

There are three main factors which govern the life of reagents, and therefore, the frequency of cleaning and recharging the titration cell:

1. The physical size of the titration cell allows for 50 – 60 mls of sample to be added. For the analysis of most liquid samples (e.g. solvents) the Aquamax KF normally only requires a few microlitres to be injected, therefore the maximum volume of 50 – 60 mls should not become a limiting factor.

2.

(Oil samples are an exception and are dealt with elsewhere in this manual).

The total amount of water that can be analysed before saturation of the reagents varies slightly from one reagent manufacturer to another. Typically a 100 ml charge of Anode reagent (Formula

“A”) will analyse upto 1 gm water, whilst a 5 ml charge of Cathode reagent (Formula “C”) will

3. analyse upto 250 mg water. Considering that the injected sample volume is normally small, and also that the analysis is usually for the determination of low levels of water, these water capacity values are not normally a limiting factor.

Similar to all other Karl Fischer reagents, coulometric reagents will deteriorate when exposed to sunlight and with increases in temperature. Placing the instrument in direct sunlight or near to a heat duct can decrease the reagent life. As reagents age, the titration speed will reduce and the drift value will increase.

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Aquamax KF Coulometric v08.10

CLEANING GLASSWARE

IMPORTANT

The platinum mesh and wires of the electrodes are fragile and can be easily bent or broken. Extreme care

MUST be taken when disassembling, cleaning and reassembling the titration cell. The generator electrode is the most expensive part of the Aquamax KF glassware. DO NOT USE BRUSH TO CLEAN INSIDE

ELECTRODE AS THIS COULD DAMAGE CONNECTIONS. Coulometric reagents are flammable and toxic, so care should always be taken when handling them and when cleaning the glassware. Whenever possible this should be done in a safe area, e.g. inside a fume cupboard. Reagents should not be recharged while the titration cell is still attached to the titrator. See page 11 on charging procedure.

Under normal circumstances the titration cell can be used for a large number of samples before having to replenish the reagents. Once the reagents have been exhausted, or when the titration cell maximum volume has been reached, it should simply be necessary to:-

1.

2.

DISASSEMBLE titration cell (disconnect leads from titrator)

EMPTY the titration cell and generator electrode

3.

4.

RINSE all parts with methanol. Do not use brush on electrodes.

DRY all parts

5.

6.

REASSEMBLE glassware

RECHARGE with fresh reagents

If the cell is heavily contaminated then it may be necessary to clean it more thoroughly. For oil samples, cleaning with chloroform or xylene is suggested, whilst for salt deposits a water wash may be required. Use whichever solvent is most suited for the sample type. The titration vessel can even be cleaned with hot soapy water and a bottle-brush. However, after cleaning with suitable solvent, all glassware parts, MUST be rinsed inside and out with methanol. They can then be dried with a warm air blower, such as a domestic hair dryer, placed in a low temperature oven at 40 – 50

° C, or left in a desiccator.

After being fully dried, reassemble the titration cell and charge with fresh reagents.

THE MORE THOROUGHLY THAT THE TITRATION CELL IS CLEANED AND DRIED, THE

FASTER THE INSTRUMENT WILL STABILISE READY FOR OPERATION AFTER

RECHARGING REAGENTS.

Under normal conditions, the Aquamax KF should be ready for operation within 5 – 10 minutes after reassembly, however it could take up to 20 minutes before to completely stabilise if the drying procedure has not been properly carried out.

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Aquamax KF Coulometric v08.10

TROUBLESHOOTING

OVERTITRATION

Detector senses too much Iodine. Usually caused by old reagents or stirrer switched off. Check stirrer speed. Add 3-5 microlitres of water until detector bars activate, and allow to precondition.

EXCESS DRIFT

Indicates excess moisture ingress or condensation on cell walls. Switch OFF. Remove titration cell from clamp and gently swirl anode reagent around the cell walls. Reconnect, switch ON, and allow to Precondition.

LONG PRECONDITIONING TIME

Normally caused by glassware not being sufficiently dried before assembly. Re-clean glassware and electrodes, dry thoroughly and charge with fresh reagents.

PROGRESSIVELY LOWER RESULTS FOR SAME SAMPLE

Moisture contamination of syringe. Flush syringe and needle with sample several times before beginning new test.

POOR REPEATABI LITY FOR SAME SAMPLE

Sample size probably too small or moisture contamination of syringe. Increase sample size and flush syringe and needle several times before beginning new test.

WARNING LETTERS ON PRINT OUT

Warning letters will be printed after time of each analysis to signify the following:-

U – Uncalibrated, E – Calibration expired, B – Battery level low, A – ACE system active

Call G.R. Scientific Ltd or your local dealer for suggestions on sampling technique for your application.

E-mail: [email protected]

TEL: +44 1525 404747 FAX: +44 1525 404848

INSTRUMENT CARE

Although the instrument casing is highly resistive to most solvents care should be taken to ensure that any spillage is wiped off immediately to avoid staining or possible damage to the paint surface.

WARRANTY

Under the conditions of our warranty, all faults which are proved to be due to material, construction or manufacturing defects, which occur within 60 months of the delivery date, will be repaired or replaced, (at our discretion), free of charge at our premises. Freight costs will be chargeable along with any inspection work which was not necessitated by manufacturing or material defects. Breakages of glassware or electrodes are not covered by this guarantee. In the event of instrument failure during the warranty period, written authorisation must be obtained from the manufacturer prior to shipping.

The Cou-Lo Safe Warranty Registration Form must be returned so that we can register your details.

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Aquamax KF Coulometric v08.10

ACCESSORIES

CARRY CASE

Optional Carry case provides the portability required by the field engineer. The Aquamax

KF can be transported, complete with glassware assembled, ready for immediate use on arrival at destination. Power cords, syringes, etc, can all be carried inside the carry case lid which has a special compartment for this purpose.

(Part no. 201109)

COU-LO FORMULA REAGENTS

Specially formulated to ensure optimum performance, our uniquely packaged reagents provide improved sample miscibility and solubility. Packaged in “single shot” 100ml bottles and 5ml “easy snap” vials, Cou-Lo

Formula reagents are safer to use and safer to store.

OTHER PRODUCTS IN THE AQUAMAX RANGE

AQUAMAX KF VOLUMETRIC AQUAMAX TAN TITRATOR GAS TIGHT OIL SYRINGE

water content determination total acidity number 1.0ml with white markings

For further information about any of our products, pricing or details about local representatives, just contact

Telephone: +44 (0) 1525 404747 Fax: +44 (0) 1525 404848

Email: [email protected] Web: www.grscientific.com

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