Fluoride

INSTRUCTION
INTERNAL
CEMENT DIVISION LABORATORIES

1 Theory....................................................................... 2
2 Experimental..............................................................3
3 Data processing.........................................................7
4 References.................................................................8

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Fluoride

1 Theory
Purpose
The purpose of the test is to determine the content of fluoride in cement, clinkers, raw
meal, and similar materials.

Description of method
To open the sample it is melted with KNaCO3. Citrate buffer is added to a portion of the
sample; this will partly complex bind Al and Fe and partly adjust the pH value and the
ionic strength to values that are optimal for the measurement. The fluoride content in
the compound is then measured using an ion-selective electrode.

Measuring principle
The concentration of fluoride is measured using an ion-selective electrode.

Formulae and units

The apparatus states the measuring solution, the F- concentration, in mmol/l (C), and
the percentage content of fluoride in the sample is calculated using the formula below:

C∗V ∗f∗18 , 9984 gF− /mol∗100 %

%F-= m∗1000 ml /l

C = concentration of the measuring solution, in mmol/l

V = volume of the measuring solution, in l (usually 0.04 l)

f = conversion factor (final volume extracted for analysis in relation to the volume after
opening). The number of mmol in the volume extracted for the measuring solution is
converted to the total number of mmol in the original test solution by using
f: f = 250/20 = 12.5

m = initial weight, in g (normally approx. 0.3 g)

18.9984 = molar weight of F-

SCOPE OF APPLICATION VALUES

Detection Limit 0,05 %
Quantification Limit: 0,05 %
Normal values: 0,05 % – 6 %
Uncertainty of the method 3-5 %

2 Experimental
Test arrangement
-

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Fluoride

List of equipment
Ion-selective electrode: Metrohm 6.0502.150, F- 0-80°C
pH/ion meter: Metrohm 781 pH/ION Meter inkl. 801 Metrohm Stirrer
Reference electrode: Metrohm 6.0750.100, AgCl/3M KCl
Or equivalent.

Other equipment needed: 500 ml and 1000 ml plastic bottles for storage of various
standards and stock solutions, 100 ml plastic beakers for test and standard samples,
various other plastic- and glassware, spatulas, and platinum crucibles are mentioned in
the procedure.

List of chemicals
1:1 HCl 500 ml of concentrated hydrochloric acid (HCl – Merck 1.00317)
are carefully transferred into a bottle with 500 ml of
demineralised water.
No requirement for durability.

0.8% alun 8,000 g of alun [KAl (SO4)2,12 H2O – Merck 1047] are transferred
into a 1000 ml volumetric flask. 800 ml of hydrochloric acid
(1:1)1 are added, and the solution is diluted up to 1000 ml with
demineralised water. Store in plastic bottles. No requirement for
durability.

Citrate buffer 500.0 g of sodium-citrate dihydrate (Na3C6H5O7,2H2O – Merck

1.06448) and 20.0 g of potassium nitrate (KNO3 – Merck 5063)
are dissolved in demineralised water and diluted up to 1000 ml.
Store in plastic bottles.
No requirement for durability.

Potassium-sodium
carbonate KNaCO3 (Merck 1.06683)

Fluoride stock
Solution 0.1000 mol/L NaF, Ion standard, (Metrohm 6.2301.030)
Durable 6 month after opening.

Fluoride 0.01mol/L
for std. addition 5.00 ml Fluoride stock solution 0.1 mol NaF/L are transferred into
a 50 ml volumetric flask and the solution is diluted up to 50 ml
with demineralised water.
Store in a plastic bottle. Durable for 3 months.

Standards are made according to the specifications in table 1 below. Fluoride stock
solutions, alun and citrate are measured out using a pipette.

Standard F- conc. Vol. ml ml citrate To be diluted up

no. mmol/l 0.1000 0.8% Alun solution to ml
mol/L solution
1
Or 400 ml of water and 400 ml of concentrated hydrochloric acid (caution)

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Fluoride

F- solution
1 0.010 20 µl 5.00 100.00 200
2 0.100 200 µl 5.00 100.00 200
3 0.300 600µl 5.00 100.00 200
Table 1
The final concentrations of both alun and citrate buffer are identical as standard and
test solutions.

All standards are to be transferred into plastic bottles with date stamp immediately
after production and must be renewed every 2 weeks.

As an alternative std 2 and 3 can be made by adding standard to the measured std 1

Standar
d no.
1 40.00ml of the above Std. 1 solution is measured as described in
calibration
2 Add 36µl fluoride stock solution, 0.1mol/l to the measured std 1, stir for 2
min measure again.
3 Add 80µl fluoride stock solution, 0.1mol/l to the measured std 2, stir for 2
min measure again.

Safety
Be cautious and use safety goggles and protective gloves during work with strong acids
and bases.

Sample requirements
Ground into -90 µm

Testing
Print a worksheet from LIMS upon start of the test. The worksheet will contain samples
and the currently available QC-samples.

Preparation

Preparation of test solution:

a) Water-soluble fluoride:

Weigh 0.5 g (4 decimals) of sample into a 250 ml beaker. The sample is stirred into 100
ml of demineralised water; the solution is heated up to boiling temperature and boils for
15 minutes.

The suspension is then filtered into a 250 mm volumetric flask through an OOM medium
filter. Rinse filter and precipitate a couple of times with boiling demineralised water.

Add 10.00 ml of 0.8% alum solution before the flask is filled. Cool the flask and fill it
with demineralised water up to the mark. Continue as specified under “Procedure”.

b) Not water-soluble fluoride - opening:

An appropriate portion of the sample; usually approximately 0.3 g (4 decimals) is

transferred into a platinum crucible together with the tenfold amount of KNaCO3 and

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Fluoride

melted at 1000C for 5 minutes. Sample and KNaCO3 should be carefully mixed prior to
melting.
For Kaolin only use 0,15 g of material and 3 g KNaCO3 to avoid extra violent reaction
when the melt is transferred to the beaker.

The crucible is transferred into a 250 ml beaker containing approximately 50 ml of

demineralised water. This is to be done carefully, as the very hot crucible and its
contents may cause splashing and spattering. Hereafter, 10.00 ml of 0.8% alun and
water are added until the bottom of the crucible is covered.

A spatula is placed in the beaker, which is then covered with a watch glass and placed
on a hotplate (100-110C) for approximately 1 hour in order to leach the crucible (stir
during leaching). Concentrated HCl is added into the crucible until all solid particles are
pulverized. This must be done very carefully because the solution effervesces easily.

Any residue of the melt remaining in the beaker after leaching must be dissolved with a
few drops of concentrated HCl.

Subsequently the solution cools down to room temperature (in water bath at least one
hour or allow it to stand the night over). Transfer the solution quantitatively into a
suited volumetric flask (usually 250 ml). Fill the flask with demineralised water up to
the mark and mix the solution carefully.

Stability: The samples must be analysed not later than the day after they are opened,
otherwise they must be transferred to plastic beakers or plastic bottles and can be
stored up to 5 days.

Preparation of test
Standards and test samples must have the same temperature (room temperature).

Preparation of apparatus
The apparatus is to be calibrated prior to each test series.

Remark: The unit on the instrument is mol/l but the used standard are in mmol.

Method “Fluoride” is used for normal fluoride analysis.

The reference electrode should be checked and, if necessary, filled with KCl prior to
measurement.

During calibration of the apparatus, the standard-values (mV) are noted in the logbook,
together with the values for “Slope”, “E (0)” and “C (blank) mmol/l”.

Procedure
Pipette 20.00 ml of the test solution, which must have room temperature, and transfer
it into a plastic beaker. Add 20.00 ml of citrate solution with a pipette.

NB! It is very important that the opened sample is mixed thoroughly before it is
pipetted for analysis. Any precipitate must be brought to suspension. Likewise it is
important that the sample has been properly stirred before the measurement starts.

Immerse the clean and dry electrodes into the sample and switch on stirrer with
<STIRRER>. After 2 minutes’ stirring switch off again. Wait until the electrodes have
stabilized; i.e. until the drift signal in the display no longer blinks.

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Fluoride

Read off the F- concentration in mmol/l but do not remove the electrodes.
Add 40µl Fluoride 0,01mol/l solution for std addition (~0,01 mmol/l) to the measured
sample. Again, after 2 minutes’ stirring switch off. Wait until the electrodes
have stabilized; i.e. until the drift signal in the display no longer blinks. Read off the F-
concentration in mmol/l.

If more than one sample is measured, the electrodes are to be rinsed with
demineralised water and dried, and the aforementioned process is repeated.

Final activities
The platinum crucibles are rinsed overnight in HCl (1:1), subsequent rinsing in
demineralised water and drying on a hotplate. Then ignite them for 15 minutes at
1200°C and add a few drops of concentrated HCl while they are still red-hot. If the
hydrochloric acid turns yellow the crucibles are not sufficiently clean, and the
aforementioned process is repeated. Otherwise rinse again in demineralised water, dry
on a hotplate and cool.

Calibration/Control
Calibration
The electrodes are rinsed with demineralised water, and excess drops are removed
carefully with lens paper. 40 ml of standard 1 are transferred into a plastic beaker that
is placed on a magnetic stirrer.

Immerse electrodes in the standard 1 and start calibration with <CAL>. After 2
minutes’ stirring enter the temperature and press <ENTER>. Confirm standard
concentration (0,01mmol/l) with <ENTER> or – if necessary – correct it. Wait for
measurement of the potential.

When the request “Change std. <ENTER>” appears, do not remove the electrodes but
add 36µl fluoride stock solution, 0.1mol/L to the first standard and press ENTER. Wait
for 2 min before confirming standard 2 concentration (0,1mmol/l) with <ENTER> or –
if necessary – correct it. Wait for measurement of the potential.

When the request “Change std. <ENTER>” appears again, still do not remove the
electrodes but add 80µl fluoride stock solution, 0.1mol/L to the second standard and
press ENTER. Wait for 2 min before confirming standard 3 concentration (0,3mmol/l)
with <ENTER> or – if necessary – correct it. Wait for measurement of the potential.

When all 3 standards have been measured out, wait for potential measurement, result
will be displayed:

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Fluoride

Calibration
Slope-59.9 mV
E(0) 32.8 mV
C(blank)0.00 mmol/l
Temp. (Manuel) 25.0 °C
date 2010-03-29 13:31

cal
calibration ok

Note:
The calibration can also be performed using all 3 standards, see table 1. The standards
are measured out in numerical order – 1, 2 and 3, i.e. the standard with lowest
concentration is measured out first.

The electrodes are rinsed with demineralised water, and excess drops are removed
carefully with lens paper. 40 ml of standard 1 are transferred into a plastic beaker that
is placed on a magnetic stirrer.

Immerse electrodes in the standard with the lowest F- concentration and start
calibration with <CAL>. After 2 minutes’ stirring enter the temperature and press
<ENTER>. Confirm standard concentration with <ENTER> or – if necessary – correct
it. Wait for measurement of the potential.

When the request “Change std. <ENTER>” appears, remove the electrodes from the
first standard, rinse them with demineralised water and remove drops gently with lens
paper. Immerse electrodes in the next standard and continue the calibration sequence
with <ENTER>. Repeat procedure for each remaining standard.

When all 3 standards have been measured out, wait for potential measurement, result
will be displayed:

Calibration frequency: Before start of an analysis or daily.

Control
Control samples and acceptance criteria, see LIMS-worksheet and LIMS-QC.

Control frequency:

Monthly: Control samples are opened as described for samples.

These controls can be stored in a plastic bottles for one month.

Daily: Measure the monthly control mentioned above as described in procedure.

3 Data processing
Handling of results
Single determination is carried out.

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Fluoride

The worksheet are filled out where the calculation takes place. Entered the result in
LIMS

Check that the calculated mmol/l in relation to the measured mmol/L in the sample
without standard addition do not differ more than 0,003mmol/l - otherwise repeat the
measurement with 2 standard additions as described below.

Measuring with 2 standard additions:

After measuring sample and sample with 0,01mmol/l standard addition, add
furthermore 16 µl fluoride stock solution, 0.1mol/L (=0,05mmol added total) and
measure again as described in the procedure.
Enter all three results in worksheet. The Correlation Coeff. Should be above 0,999.

Measurement must always be within the calibration range. Otherwise the test sample
must either be diluted, or a lower initial weight must be used.

NB! In case of dilution remember to correct f in the calculation.

Export results to LIMS

The concentration is calculated by use of this formula:

C∗V ∗f∗18 . 9984 gF− /mole∗100 %

%F-= m∗1000 ml/l

Example:
−
0. 075 mmole/l∗0. 040 l∗12 .5∗18 .9984 gF /mole∗100 %
%F- = 0 .3000 g∗1000ml /l = 0.24 %

The result is expressed in % fluoride with 2 significant digits.

Handling of deviations
Contact the person responsible for the method, if deviations are observed.

Flow-sheet

Weigh KNaCO3 into platinum crucible

↓
Weigh sample into same platinum crucible
↓
Mix KNaCO3 and sample carefully
↓

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Fluoride

Melt the mass at 1000°C in an oven for 5 min

Place a glass beaker containing 50 ml of demineralised
water next to the oven
↓
Take the platinum crucible out and mix the melted mass by
carefully rotating the crucible
Place it in the glass beaker - be careful
↓
Add 10.00 ml of Alun and some additional water to the
beaker
Place on a hot plate app. 1 hour
↓
Add HCl into crucible until particles are pulverized
↓
Cool down solution to room temperature
↓
Renew standard-solutions; if they have expired
↓
Transfer the sample-solution to volumetric flask
↓
Pipette 20.00 ml of test solution to plastic-beaker
Add 20.00 ml of citrate solution to the same beaker
↓
Transfer 40 ml of standard-solution to plastic-beaker
↓
Calibrate the apparatus
↓
Measure the samples
↓
Platinum crucible are rinsed in HCl (1:1) overnight, and
ignited at 1200°C for 15 minutes

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