Designation 1P 226/76

(Reapproved 11989)

COPPER IN AVIATION TURBINE FUELS

AND LBGHT PETROLEUM DISTILLATES
\
Attention is drawn to the SAFETY PRECAUTIONS-NOTICE TO USERSpublished in the I ~ ~ ~ ~ ~ I I C II,,I C III:,
II,,~.,,. /
of l p Standard Methods for Analysis and Testing of Petroleum and Related Products (see Con~~:lit:, ,:,,,,,:,,,,,,,,,,
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-
need for ensuring that the methods of test are carried out with suitable attentiot~10 :..,l,:ly
___i

1. SCOPE
1.1. The method is suitable for the determination of coppcr I ' I x ) ~ ~250
~
down to about 10 pg/kg [Note I] in aviation turbine fuels and ~xlrolcumcjijlill;llr\
of similar boiling range.
NOTE 1: This lower limit may not be achieved in a contaminated a 1 1 i i o s l ~ l l ~ 1lllllcj,
.c jp,,,,
precautions are taken.

2. S U M M A R Y OF METHOD
2.1. The sample is treated with sodium hypochlorite solutio~i:111d1 1 1 ~COPpc,
extracted by washing with hydrochloric acid. Ammonium ci(l-:~tc:lntj t;[).l.,,j
(disodium salt of ethylene diaminetetra-acetic acid) are used Lo climinatc illtcrl.cr
ences and the copper is complexed with sodium diethylditliioc:~~.lj:~nl:~(c. -ill,
coloured complex is extracted with chloroform and the col7ljc1.cslini;~rcdb,
measuring the colour intensity on a spectrophotometer.

3. APPARATUS
3.1. Spectrophotometer - capable of measuring light absorpliori ; I I 435 11111
3.2. Separating Funnels - 100, 250, and 500 ml.
3.3. Graduated Qlinders - 10, 25, and 250 ml.
3.4. Pipettes - 10ml.
3.5. Glass Funnels.
3.6. Glass stoppered Flasks - 10 ml.
3.7. Sample Container - a suitable, clear glass bottle, appl-oxi~lli~rcl> 200 m!
capacity, fitted with a glass stopper. Preferably new bottles shoultl he tlsccl.
NOTE 2: It- has been found that some samples deteriorate on standing, p ~ . c ~ . i p i l ; ~c,oppcr ~ i ~ ~ 0::
g
the walls of the container. T o account for this, steps are taken in the procccl~~~.c 10 ;~c.itlc s l r ; l d ~ h (
bottles and to add the extract to the solution for analysis. For this reason, i t is i ~ ~ ~ l ~ o ~10' l u; qi ~ l l
bottles of the right size for sampling to bring the total quantity of copper w i l l l i ~ lI l l c clcjircd r.lri$c
for determination.
All sampling bottles should be clean and dry. If necessary they can be rinsed ii.11I1 1 1 1 ~1 ~ 1 1 ~ l ~ I 1 1 ~ ~ r ~ ~ ~
solution and the hvdrochloric acid stipulated in paras 4.2 and 4.3. Used bottles ~110111t11101 h~ 1 1 ~
when samples of low copper content a r e expected.

4. REAGENTS
4.1. Distilled Water - copper content not to exceed 20 pg/lit IT.
This is required. for the preparation of the reagent solutions : ~ n dlor Llsc ill
test procedure.
 COPPER IN AVIATION TURBINE FUELS, IP 226

4.2. Sodium Hypochlorite - approximately 5% weight available chlorine solu-

tion. This should be checked by the classical iodinelstarch titration procedure.
4.3. Hydrochloric Acid - BDH foodstuffs grade 4W approx.
4.4. EDTA (disodium salt) - 5 g per 100 ml of aqueous solution.
4.5. Ammonium Citrate - 10 g per 100 ml of aqueous solution.
4.6. Ammonium Hydroxide - re1 d 0.88.
4.7. Chloroform.
4.8. Sodium Diethyldithiocarbamate - 1 g per 100 ml solution prepared daily
and filtered.
4.9. Sodium Sulphate - anhydrous powder.
4.10. Copper Sulphate - standard solution of 5 pg Cu per ml prepared from
clear crystals (i.e. showing no efflorescence) of copper sulphate CuS04.5H20 as
follows:
,g/kg Dissolve 0.393 g of CuS04.5H20in the distilled water. Add 5 ml of concen-
lates trated hydrochloric acid and dilute to 1 litre with the distilled water. Take 5 ml of
this solution and dilute to 100 ml with the distilled water. This gives a standard
solution containing 5 pg Culml.
4.1 1. Acetone.
5. PREPARATIOI!I O F APPARATUS
5.1. It is desirable to have a set of glassware which is used only for these
analyses [Note 31.
5.2. New glassware should be cleaned with concentrated hydrochloric acid and
rfer- washed with very pure water. When necessary use a small quantity of acetone and
The a vacuum line for drying glassware.
1 by NOTE 3: Stopcock grease is often a source of contamination. Lubricate separating funnel taps
with a polytetrafluoroethylene (PTFE) aerosol spray or employ PTFE taps.

6. PROCEQURE
6.1. Preparation of calibration graph.
Add 0, 1.0, 2.0, 4.0, 6.0, and 8.0 ml portions of the 5 pglml standard copper
sulphate solution to a series of separating funnels and then add 8 ml of the
hydrochloric acid and 15 ml of the ammonium hydroxide mixing well with
frequent venting after each addition. Add 2 ml of the sodium diethyldithiocarba-
mate solution to each separating funnel, mix, and allow 3 min for the yellow
coloured complex to develop. Add exactly 10 ml of the chloroform to each
separating funnel and extract by shaking vigorously for 2 min. Collect each
chloroform extract in a glass-stoppered flask containing a little sodium sulphate
:r on
t the (approximately 25 mg).
I use Measure the absorbance at 435 nm of each chloroform extract in a 1 cm cell
mge using chloroform as the reference solution (also determine the correction values
]rite for each cell used if matched cells are not available). Plot the corrected absorbance
used values against pg copper (per 10 ml of chloroform solution).
6.2. Analysis of sample.
6.2.1. Take samples for analysis in the special bottles defined in para 3.7.
6.2.2. Run a blank omitting the sample.
6.2.3. Weigh the bottle and sample to the nearest 1.O g. Pour the sample into
the a 250 ml separating funnel and allow the sample bottle to drain. Reweigh the
bottle and determine the weight of the sample. Add lOml of the sodium
COPPER I N AVIATION TURBINE FUELS. IP 225

hypochlorite solution to the bottle and swirl for 1 min so that it washes
interior surface. Pour the hypochlorite solution from the bottle into the separating
funnel. Shake the separating funnel vigorously for 2 min with frequentvent.
Add 10 ml of the hydrochloric acid to the bottle and swirl as before, pour"', the
hydrochloric acid from the bottle into the separating funnel and shake for a
further 2 min. Run the aqueous extract into a 100 ml separating funnel, R~~~~~
washing procedure with 5 ml hydrochloric acid, and then 10 ml of the water,
the washings to the 100 ml separating funnel.
6.2.4. Add 5 ml of the ammonium citrate solution and 5 ml of the EDTA
solution to the aqueous phase and mix. Finally add 15 ml of the ammonium
hydroxide and mix again. (CAUTION: add ammonium hydroxide slowly,par-
ticularly to the blanks.)
6.2.5. Wash the ammoniacal extract with 20 ml aliquots of chloroformuntil
the chloroform has a very low optical density at 435 nm. Three washings are
normally adequate. Finally allow layers to separate completely and drain 08as
much chloroform as possible. Discard washings.
6.2.6. Pipette 10 ml of the sodium diethyldithiocarbamate solution into the
ammoniacal extract, shake and allow to stand for 3 min to enable the yellow
coloured complex to develop. Add exactly 10 ml of chloroform, shake vigorously
for 2 min, and allow the layers to separate.
6.2.7. Run the chloroform layer into a glass-stoppered flask containing a
small quantity of sodium sulphate.
6.2.8. Shake the flask and allow the phases to separate. Within 20min
measure the absorbance of the chloroform extract at 435 nm in a 1 cm cell, using
chloroform as a reference.
NOTE 4: If preferred 300 ml of the sample may be used. In this case use 25 ml of chloroform [or
the final extraction of the coloured complex. This would permit the use of 40 mm cells for mcasurine
the absorbance. A calibration graph representing pg copper in 25 ml chloroform against rhc
absorbance measured in 40 mm cells should be plotted.

7. CALCULATION
7.1. Calculate .the copper content pg/kg by the following formula:
A x 1000
Copper content, pglkg = W
where A = pg copper in sample - pg copper in blank;
W = weight of sample in g.
8. REPORT
8.1. Report the result as Copper Content, IP 225.
9. PREClSlOlU
9.1. The following criteria should be used for judging the acceptability of
results (95% confidence) [Note 51.
9.1.1. Repeatability - Duplicate results by the same operator should be
considered suspect if they differ by more than 20 micrograms per kg.
9.1.2. Reproducibility - The reproducibility of the method has not yet been
established.
NOTE 5: These precision values have been obtained by statistical examination or interlaborator!'
test results (see Appendix E) and were first published in 1976.