L&I

Wall Wash Sampling & Analysis Procedures.

Contents.

1. Introduction.

2. Visual Inspection of Tanks.

3. Wall Wash Equipment List.

4. Wall Wash Sampling.

5. Analysis, Sample Appearance.

6. Analysis, Sample Odour.

7. Analysis for Hydrocarbon.

8. Analysis for Colour.

9. Analysis for Permanganate Fade Time.

10. Analysis for Chloride.

11. Analysis for Acid Wash Colour.

12. Laboratory Organization and Maintenance.

13. L&I Lightwave II UV/Vis Spectrophotometer.

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1. Introduction.

Whilst the chemical analysis of a wall wash sample, performed correctly (in
accordance with ASTM test methods) will accurately define a result which can be
both repeated and/or reproduced, the same cannot be said for the process of
wall wash sampling.

Wall wash samples can and will differ between two separate samples taken
independently, from the same cargo tank. Therefore, results can be different and
whilst one sample may pass, the other may fail and there is no way of knowing
which sample is right and which is wrong.

The reason for this is more clearly understood when a surveyor/crew member,
takes samples from areas blind to the full effect of the tank cleaning machines
or perhaps from sloping bulkheads, as opposed to samples taken from the
vertical bulkheads or areas where there are no shadows from the tank cleaning
machines.

At best, the process of wall wash sampling is random and only reflects the areas
where the samples are drawn from, normally the bottom 2.5 meters of the tank
bulkheads. It follows that it is just not possible to say that this sample is
representative of the condition of the whole tank, yet in many cases, this sample
directly determines whether a vessel should load or stay idle.

When cleaning to a Methanol (High Purity) Standard, great care has to be taken
to ensure the wall wash results obtained after the completion of a tank cleaning
process, give the best reflection of the condition of the entire cargo tank, rather
than trying to match where the inspector might choose to sample the cargo
tanks upon arrival at load port. There are absolutely no guarantees that wall
wash samples taken on board will be the same as the samples drawn by the load
port inspectors, so real care needs to be taken when selecting the ‘spots’ from
which the sample will be taken, in order to provide as good an ‘average’ of the
condition of the cargo tanks as possible.

This document has been designed to provide some considerations and

background to help users achieve the best possible, most representative and
accurate wall wash sample results.

It is also aimed at assisting the reporting process, so when results are

communicated from vessels to operators or supercargoes, there is a more in-
depth and precise understanding of the condition of the cargo tanks, which will
help to quickly identify and execute the most appropriate corrective action.

For this reason, it is extremely important to follow the suggested Wall Wash
Sampling Procedure (4) below, in order to standardise the technique for all
users.

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2. Visual Inspection.

When preparing for ‘Methanol Standard’, there should be no visible evidence of

previous cargo, loose residues from cleaning materials, cargo tank coatings or
inert gas systems.

If previous cargo(s) were viscous or high melting, check machine blind areas, the
underside of angle brackets and underneath the heating coils.

Take a clean white rag and wipe reachable surfaces. Nothing should come off
onto the rag. There should be no grease and / or any loose dust and rust
spotting must be removed.

The cargo tank surfaces and suction areas should be completely dry.

The following pictures are perhaps an overstatement of visual surface matter,

but make the point; the cargo tanks clearly need further appropriate washing.

Rust stains / discolouration

on zinc silicate cargo tank
coatings may be improved by
washing with a controlled
acidic cleaner (bufferclean).
Rusting should not be loose
so it rubs off as powder.

Organic cargo tank coatings should be sound. Loose or flaking surfaces should
also be made sound. In general, coating breakdown should not be greater than
2% of the total tank surface area.

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Rust spots on organic

cargo tank coatings
should be sound with no
loose matter or staining
coming off when wiped
with a clean rag.

Odour, during the visual inspection can also be a problem. Tanks should not
retain the smell of previous cargo(s) or washing chemicals. (Always be aware
that the packing material around the top lip of the man entry very often retains
previous cargo residues and is a common source of odour problems because an
inspector will pass through this region at the start of the internal inspection and
will assume that the cargo tank smells the same way as the packing material).

Never forget the

inspection of the
cargo / drop lines

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3. Wall Wash Equipment List.

1. Clear glass sample bottles. 500ml. Best to use new, chemically clean
bottles. (Re-used bottles are acceptable, always making sure they have
been carefully flushed with D.I. water followed by two flushes with
laboratory grade methanol).
2. Cut plastic or stainless steel flat sided funnel. Approx. 10 – 14 cm in
diameter.
3. Polypropylene plastic “squeeze” wash bottle with spray nozzle. 500ml.
4. Laboratory Grade Methanol. 500ml per tank.
5. Eye Protection glasses.
6. Latex / Nylex gloves.
7. Shoe covers.
8. Marker pen. (Preferably ‘paint marker’. Methanol will wash away
labelling from most permanent markers).
9. Portable gas detector. (Leave this at the bottom of the stairwell or overall
back pocket. It will give an alarm from the methanol vapours if you have it
on your top pocket).

Keep all items as

clean as possible

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4. Wall Wash Sampling Procedure.

It is very important to ensure all equipment used is visually and chemically

clean. All items should be washed in the laboratory prior to use and again rinsed
with lab grade methanol before use in each cargo tank to ensure contamination
from one tank does not carry over to the next. Also take great care not to spoil
the sample by picking up contamination from hands, clothes or sweat. It really
does not take a lot of contamination to contaminate a wall wash sample.

Do not touch or lean against bulkheads that have not been inspected. If the wall
wash sample becomes contaminated because of surface contamination that has
not come from the previous cargo or cleaning process, this could directly lead to
unnecessary over-cleaning.

Never wall wash tanks that are wet. Water or moisture will directly affect the
ability of the methanol solvent to absorb contaminants from the surface of the
cargo tank / coating, which may give misleading colour, hydrocarbon and
chloride results. It is also advisable not to wall wash when the cargo tanks are
too hot, for example directly after hot washing or steaming, because the
methanol has a tendency to quickly evaporate, leading to a “concentrating” effect
of any contaminants in the sample.

The basic procedure is to spray 500ml of pure laboratory grade methanol

from the plastic squeeze wash bottle over approximately 1 square meter of
the cargo tank bulkheads for collection via the flat sided funnel into the
glass sample bottle. Some methanol will always run past the funnel and be lost
to evaporation, but a recovery rate of 50 – 60% of the 500ml is normal, leaving
250ml – 300ml of sample for analysis.

As noted, the primary objective of the wall wash inspection is to finish with a
sample that represents the chemical condition of the entire tank. However, in
practice it is accepted that “normally” the sample can only be taken from
random spots representing the lower 2.5 meters of the cargo tanks. This
“randomness” explains why no two wall wash samples will ever be exactly the
same and it is quite possible for one sample from a cargo tank to be considered
as acceptable whereas another sample from the same cargo tank may be
unacceptable. And of course, the upper areas of the cargo tanks are largely and
routinely not represented at all.

Suggested Standard Practice

Choose two places from each bulkhead to sample, meaning the completed wall
wash sample will be representative of a minimum of 8 spots (samplings) for each
cargo tank. Place the flat-sided funnel against the bulkhead at waist height with
one hand and in the other hand, extend the wash bottle as high as possible
directly above the funnel. Spray the wall wash solvent (usually methanol, but
not always) – and allow it to stream / flow down the surface of the bulkhead.
Collect as much of the solvent as possible in the sample bottle.
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Repeat as described above and when added together, the volume of collected
sample should be around 250ml and the total surface area sampled should be
approximately 1M2. Choose areas that represent the good, the typical and the
worst (cleaning machine blind spots) parts of the cargo tanks, rather than just
the best parts. It is better to know the worst, before the load port inspectors.

If through experience or visual observation there are a number of areas that

appear to be non-typical, take and analyse a separate wall wash sample just
from these spots, in order to identify the source of the contamination, if at all
possible.

At the top of the tank, put on

the shoe covers.

At the bottom of the tank,

put on the protective gloves.

Transfer the pure methanol to

the wash bottle.

Rinse the wall wash funnel

with pure methanol.

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With the flat side of the wall

wash funnel against the
bulkhead, extend the wash
bottle above the funnel and
spray the methanol so that it
runs down the bulkhead to
be collected in the sample
bottle, via the funnel.

Observe the methanol as it flows down the bulkhead surface. If there are
excessive hydrocarbon residues or perhaps a “film” of solidified vegetable oil on
the surface of the tank, the methanol may not be able to fully dissolve this and
may pass over the residues in “small ripples”.

Also closely observe the washed area after the methanol evaporates. The
presence of brown “burn marks” around the edges very often indicates the
presence of non-volatile matter (NVM), which will usually result in a positive
hydrocarbon identification or a depressed permanganate time.

Visible signs that the wall wash

methanol has extracted surface
contaminants. “Burn” marks
around the outer edge of the
wall wash area.

When the sampling process has been completed, rinse the sample bottle cap
with clean methanol and close securely. Mark the bottle with the relevant tank
number. Good sample identification is important. Be aware that most marker
pen inks will dissolve in methanol.
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Wall Wash Analysis Procedures

It is very important to have a designated laboratory area, preferably dedicated, to

perform the wall wash analysis. The location of this laboratory area should have
a good supply of fresh water (sink), ventilation and air conditioning. Personal
safety equipment such as latex gloves and eye glasses should always be worn
and a fire extinguisher should be near-by because methanol is highly
flammable. A well organized and maintained laboratory space greatly assists to
ensure results are correctly determined and reported.

As with the wall wash sampling procedures, cleanliness in the laboratory area is
vital. If a sample is contaminated for reasons other than the cleanliness of the
bulkheads, a test may fail, directly resulting in the cargo tank being un-
necessarily re-washed.

Ensure all equipment and glass tubes are clean. Do not assume because
something looks clean, it is actually clean. Before using any glassware, as an
absolute minimum, flush twice with laboratory grade methanol.

Newly delivered supplies of laboratory chemicals / solvents should be in sealed

containers and checked for purity before use. Laboratory grade methanol is
typically in sealed 2.5 or 4L amber glass bottles. Laboratory grade D.I. water
should also be in sealed bottles, but plastic bottles are acceptable.

Laboratory reagents should be clearly labelled and indicate an expiry date.

Results from each test should be recorded immediately. Work in an organized

and logical manner.

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5. Analysis – Sample Appearance.

Equipment Required

1. Sample bottle of pure methanol – for comparison as a reference.

2. Cargo tank wall wash samples.

Procedure

Compare the appearance of each cargo tank wall wash / cargo sample with a
blank sample of pure methanol.

Reporting – Sample Appearance

The individual wall wash / cargo samples should have the same clear and
bright appearance as the pure methanol.

Note any sediment in the bottom of the bottle and report.

Note any matter still suspended in the sample (fibres etc) and report.

For a sample to pass on appearance it should be “clear and bright” and be

substantially free from sediments and/or suspended matter.

1 2 3 4 5 6
. . . . . .

Sample 1 – Pure laboratory grade methanol. “Clear & Bright” without any
suspended matter or particles/sediments. Wall wash sample equivalent is “pass”

Sample 2 – Clear & Bright with only very slight suspended matter and / or
particles that settle out to the bottom of the sample bottle. This sample should
be acceptable. Wall wash sample equivalent is “borderline”.

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Sample 3 – Clear & Bright with more obvious sediment which settles out to the
bottom of the sample bottle. This sample will most likely fail the appearance
test. Wall wash sample equivalent is “fail”. (The cargo tank may need spot
sweeping or flushing with D.I water to improve the appearance of the sample).

Sample 4 – Clear & Bright with heavy sediment settling out to the bottom of the
sample bottle. Wall wash sample equivalent is “fail”. (The cargo tank will need
flushing with high pressure D.I. water over the lower sloping sides and tank top
in order to improve the appearance of the sample).

Sample 5 – Hazy appearance with (or without) sediment and / or suspended

matter. Wall wash sample equivalent is “fail”. (This cargo tank will likely need
re-washing).

Sample 6 – Sample appearance is coloured and will therefore fail the test. If the
discolouration is yellow, the colour can be measured on the APHA colour scale.
But any visible discolouration of the wall wash sample, which could be the
result of a dyed or naturally coloured previous cargo, or chemical reaction, will
result in the wall wash sample being rejected on appearance.

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6. Analysis – Sample Odour

In section 2, “Visual Inspection”, it was noted that any noticeable odour inside
the cargo tanks should be reported. This can be particularly relevant when the
previous cargo was styrene monomer, pygas, acrylates etc. Great effort should
be taken to remove any such odours, always bearing in mind all odours are
derived from volatile organic compounds and in the case of coated cargo tanks,
such compounds are often absorbed into the coatings, making removal more
challenging.

For methanol wall wash / cargo samples, there is a test for ‘Odour of Volatile
Solvents and Diluents’ with ASTM reference D1296 that essentially looks for
“Characteristic” or “Non-characteristic” odour and “Residual” or “Non Residual”
odour.

Most solvents used for wall wash sampling (typically methanol), are both
hazardous and mildly toxic, meaning they should not be inhaled. The ASTM test
method is based on immersing strips of absorbent paper into both laboratory
grade methanol and the wall wash samples in a well-ventilated space and
making a comparison to detect any difference in odour.

Many vessels have a box of ‘filter paper’ (circles) on board, which can be utilised
by cutting into strips of around 25mm x 75mm. (Always make sure the filter
papers are clean and odour free before use).

For “Characteristic” or “Non-characteristic” odour test

Immerse separate strips of the absorbent (filter) paper into the laboratory grade
methanol and wall wash / cargo sample(s) to a depth of around 50mm.

Whilst the filter paper is still wet, carefully smell them both and compare the
odours. If the odours are the same, report the odour result as “Characteristic” or
MCO – Methanol Characteristic Odour. If there is a difference in the odours,
report the result of the wall wash / cargo sample as having a “Non-
Characteristic” odour or NC.

For “Residual” or “Non Residual” odour test

Immerse separate strips of the absorbent (filter) paper into the laboratory grade
methanol and wall wash / cargo sample(s) to a depth of around 50mm.

Allow the filter papers to dry, before carefully smelling both and comparing the
odours. The laboratory grade methanol should not have any residual odour, and
should be reported as having a “Non-Residual” odour. If the wall wash / cargo
sample is different and has a persistent / lingering odour, report the sample as
having a “Residual” odour.

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7. Analysis – Water Miscibility / Hydrocarbon.

This test serves to determine water immiscible contaminants in wall wash or

cargo samples. The level of detection will vary widely dependent on the solvent
and the type of impurity. The test is qualitative, not quantitative and the results
can only ever be reported as either “Pass” or “Fail”.

The mechanism of this procedure for wall wash analysis is as follows. The wall
wash solvent for the hydrocarbon test is usually methanol or acetone and both
are completely soluble in water. As organic solvents, they also have the ability to
dissolve / extract hydrocarbon residues from the surface of the cargo tank,
(always bearing in mind the solubility of the hydrocarbon in the wall wash
solvent directly impacts how much of the hydrocarbon will be extracted).

When the wall wash sample is mixed with water, any hydrocarbon contaminant
that is soluble in the wall wash solvent, but insoluble in water, is forced out of
the wall wash solvent and shows up as a hazy / turbid emulsion in the solvent-
DI water solution. If the wall wash sample shows any sign of haziness, it is said
to contain water immiscible (hydrocarbon) contaminants and will fail the test.

The relevant test method for hydrocarbon/water miscibility is ASTM D1722,

which states that the wall wash sample must be diluted in a ratio of 1:9 with DI
water (10ml of wall wash sample to 90ml of DI water).

However, it is not uncommon for the hydrocarbon test to be run at dilutions of

1:3 (25ml of wall wash sample to 75ml of DI water) or 1:1 (50ml of wall wash
sample to 50ml of DI water), both of which will have a significant impact on the
final test result. If the hydrocarbon test is part of a wall wash inspection prior to
loading a sensitive chemical cargo, it is essential to know which dilution ratio
will be employed at the load port, otherwise there is an increased risk of failing
the test / inspection.

Equipment Required

1. 100ml graduated glass measuring cylinders with stoppers – (Avoid cylinders

with blue graduation markings where possible because these can interfere
with the interpretation of the results, particularly at low levels of
contamination)
2. Laboratory grade methanol
3. Laboratory grade DI water

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Procedure

1. For each cargo tank sampled, mix 10ml of wall wash / cargo sample with
90ml of lab grade DI Water in the 100ml measuring cylinder. Insert the
stopper and invert the cylinder two or three times, without shaking.

2. Simultaneously, prepare a “reference” sample by mixing 10ml of lab grade

solvent with 90ml lab grade DI water in a 100ml measuring cylinder in the
same way described above. This reference sample is used for comparison
purposes against individual wall wash / cargo samples. It also demonstrates
that the lab grade solvent is pure and free from water immiscible
contaminants.

If there is any haziness or turbidity in the reference sample and this

was the same source of solvent used for the wall wash samples, it may
be necessary to dispose of the wall wash samples and re-take the
samples with on specification solvent.

3. Leave the wall-wash / cargo and reference samples to stand for 20 minutes
before assessing the result.

Reporting

In order to pass the test, the wall wash / cargo samples must be free from any
haziness or turbidity after the 20 minutes standing time, compared to the
reference.

If any hydrocarbons are present, there will be a visual difference between the
test sample(s) and the reference sample. The presence of low levels of
hydrocarbons will typically be identified by the presence of a transparent blue
coloured tinge, compared to the presence of higher levels of hydrocarbons which
will be identified by the presence of an opaque white “milky” emulsion.

Some laboratories shine the beam of a pen-light / torch horizontally through the
measuring cylinder against a black background, which will show up trace levels
of hydrocarbons quite clearly. Strictly speaking, this is not in accordance with
ASTM D1722, but as the test can only be reported as “pass” or “fail” it is difficult
to argue against a rejection on the grounds of subjectivity.

Note. If there is any evidence of foam or bubbles on the top of the liquid
inside the measuring cylinder, this is generally an indication that tank
cleaning chemicals have not been completely rinsed away. This is far more
common in coated cargo tanks compared to stainless steel.

The results of ASTM D 1722 are given as either “Pass” or “Fail” only. There is no
allowance for the degree of failure.

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1 2 3 4 5
. . . .

Pic 1. (Above)

Sample 1. Reference sample – 10/90 Lab methanol & DI water

Sample 2. Result is equal to 10 FTU on Spectrometer (see later) – “Fail” Result
Sample 3. Result is equal to 50 FTU on Spectrometer (see later) – “Fail” Result
Sample 4. Result is equal to 200 FTU on Spectrometer (see later) – “Fail” Result
Sample 5. Result is greater than 200 FTU on Spectrometer (see later) – “Fail”
Result

Pic 2 (Right)

Wall wash samples observed

under torch beam.

Sample 1. Reference of 10/90

Lab methanol & DI water

Sample 2. 20 FTU on
spectrometer.

Note that even in the reference

sample, a beam is highlighted
by torch-light.

1 2
. .
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8. Analysis – Colour. Platinum Cobalt Scale (also referred to as APHA
Colour).

The Platinum Cobalt scale colour test describes the visual determination of
essentially light coloured liquids (yellow scale) as specified in the ASTM test
method D1209.

For the most accurate visual determinations, Platinum Cobalt colour standards
as described in ASTM D1209 and ‘long stem’ clear glass tubes (Nessler Tubes)
should be used. As can be seen below, the colour variations between 0, 5, 10
and 20 on the Pt-Co scale are minimal and it is fair to say that this test is
actually one of the most difficult to achieve, particularly for coated vessels.

In order to achieve a typical “methanol” standard wall wash, it is usually

required that the colour is less than 10, but in a growing number of cases, the
specification is maximum 5 which is effectively no visible discolouration.

100ml measuring cylinders may be used in the absence of Nessler Tubes, but it
is better to use cylinders with white markings because this reduces interference.

Pt-Co 0 Pt-Co 5 Pt-Co 10 Pt-Co 15 Pt-Co 20

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Equipment Required

1. 100 ml Nessler tubes / glass measuring cylinders.

2. ASTM D 1209 Pt-Co colour standards. Typically 20 / 15 / 10 / 5.
3. Laboratory grade methanol

Procedure

Note. Always use the same length of tube for this test because the path
length of the liquid has a direct impact on the colour determination.

1. Fill one Nessler tube with 100ml of lab grade methanol. (Reference sample).
2. Transfer 100ml of the appropriate colour standard(s) into separate Nessler
tubes.
3. Decant the same volume of each wall wash / cargo sample into similar
Nessler tubes.

Reporting

Looking down the length of each tube against a clean white background,
compare the reference sample against the colour standards to confirm the
laboratory grade methanol is colourless.

If the maximum colour specification of the wall wash / cargo sample is 10 Pt-Co,
simply compare the prepared 10 Pt-Co colour standard directly against each
wall wash sample in turn.

If the wall wash / cargo sample has less colour than the 10 Pt-Co standard, it
can be reported as having a colour of “less than 10 Pt-Co”.

If the wall wash / cargo sample has more colour than the 10 Pt-Co standard, it
will fail to meet the required specification and should be reported as having a
colour of “greater than 10 Pt-Co”.

In order to identify the precise colour of the wall wash / cargo sample, it will
need to be compared against increasingly higher colour standards until it is
found which colour standard the wall wash sample is less than.

Note. In the event that no colour standards or spectrometer are available on board,
compare the wall wash / cargo sample against pure methanol. If the test
specification is 5 or 10 Pt-Co, there should not be any visible discolouration of the
wall wash / cargo sample. If there is visible discolouration, the sample will most
likely fail to meet the required specification.

The Pt-Co colour scale is based on a yellow colour, but wall wash samples may
contain other colours, the presence of which will almost always cause the wall
wash sample to be rejected.

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9. Analysis – Permanganate Fade Time (PFT).

This procedure is a non-quantitative and non-specific spot test for the presence
of oxidisable contaminants found in methanol and acetone. When used as part
of the analysis of wall wash samples, the most likely source of contaminants is
from previous cargoes or even traces of cleaning chemicals used in the tank
washing process.

The most appropriate published test reference is ASTM D1363.

The chemical principle behind this test is as follows. Potassium permanganate

solution is a strong oxidising agent that has a deep pink colour. Any
contaminant in the wall wash / cargo sample that can be oxidised by the
potassium permanganate will cause the permanganate to be partially reduced
and this is observed visually by means of a colour change from deep pink to
brown. In the presence of acid, the permanganate is completely reduced and the
accompanying colour change is deep pink to colourless, (normally in a very
short period of time).

The rate of the reaction is dependent on the concentration of contamination in

the wall wash / cargo sample; the higher the concentration of contaminants in
the sample, the faster the colour change will proceed.

It is also extremely important to run the test at a constant temperature of 15oC

as the rate of reaction is very much temperature dependent. The higher the
temperature, the faster the colour change will proceed.

Light and extremes of pH will also catalyse the colour change, so it is important
to ensure that the samples are pH neutral and the test is run in darkness.

Equipment required

1. Laboratory grade methanol

2. Glass measuring cylinders with stoppers.
3. Cool box with lid. (Igloo Box).
4. 0.02% solution of potassium permanganate KMnO4 in water. (0.1gram in
500ml of laboratory grade DI water.)
5. Pipette capable of accurately transferring 2ml of liquid
6. Thermometer to read 15oC
7. Cylinder rack for glass cylinders (as required)

Prepare the cool box with water and ice at a temperature of 15oC, ensuring that
the water level in the bath will completely cover the level of liquid in the
measuring cylinders.

Prepare the permanganate solution by dissolving 0.1 gram of KMnO4 crystals in

500ml of distilled water and storing in an amber coloured glass bottle

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(alternatively cover a clear glass bottle with silver foil). Keep in cool dark place
when not in use – for example a fridge if possible.

Procedure

1. Prepare a reference sample by transferring 50ml of laboratory grade

methanol into one of the glass measuring cylinders
2. Pour 50 ml of each wall wash / cargo sample into clean** glass measuring
cylinders.
3. Place all of the samples, including the reference, in the cool box and leave
for 10 minutes to allow the sample temperature to stabilise at 15oC. (If using
a fridge, check the internal temperature is stable for 15oC. You may need to
leave the samples a bit longer to bring the temperature down to 15oC).
4. To each sample, pipette 2ml of the 0.02% potassium permanganate
solution, invert to mix and place back in the cool bath/fridge.
5. Place the lid on the cool box to maintain darkness and note the time.

** Sample tubes should be thoroughly cleaned prior to the commencement

of this test. If the same sample tubes are consistently used for the
permanganate time test, they can start to become stained after a period of
time. This staining will affect the test results and should be removed using
hydrochloric acid (as recorded in ASTM D1363). After acid washing, the
sample tubes must be copiously flushed with water to remove all of the acid,
otherwise this could result in a premature permanganate time failure.

Reporting

The reference and test samples should be visually checked every 10 minutes
from the time the potassium permanganate solution was added to the reference
and test samples. (When checking the samples, also check that the temperature
of the water bath / fridge is constant at 15 +/- 1oC.

Keep visually comparing the colour of the test samples against the colour of the
reference sample every 10 minutes until the duration of the test has been
completed. If the colour of the test samples starts to change before the end of
the test, to an orange / brown / yellow colour, or “no pink hue” remains, note
the time that the sample finally changed colour.

Reporting of the results will be based on the ten minute checking intervals. If
the test sample has lost its pink colour after say 30 minutes, then the
permanganate time is reported as less than 30 minutes (< 30). If the colour of
the test sample is still similar to the blank at the scheduled end of the test, say
50 minutes, the permanganate time is reported as greater than 50 minutes
(>50).

When the PFT is a wall wash specification prior to loading methanol, the wall
wash samples should maintain their pink colour for 50 – 60 minutes depending

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on different load ports. Prior to loading MEG FG, a permanganate time of 30
minutes is the normal specification.

Pure laboratory grade methanol should maintain the pink colour for well over 90
minutes.

The following pictures show the various stages of colour deterioration that can
occur as the permanganate fade time proceeds.

Reference Sample is Sample is Sample

sample acceptable borderline has no
should even after failure evidence of
maintain some with only any pink
a bright oxidation the colour and
pink has slightest has failed
colour for occurred “pink hue”
60 – 90 apparent
minutes

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Looking down the length of the measuring cylinder, the colour of the sample
becomes much clearer to observe:

In cases where the test sample fades to a clear and colourless solution without
appearing to pass through the orange / yellow / brown stages, this is still a
failure and can indicate that the contamination is acid based, as below image.

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10. Analysis – Inorganic Chloride.

This test determines trace levels of inorganic chloride in test samples, which in
the case of wall wash samples, will normally be present from earlier seawater or
freshwater washing. Typically the chloride content of seawater is around 15,000
to 20,000 ppm whereas normal freshwater will be around 100 to 500 ppm.
Technical grade DI water, used for tank cleaning should contain less than 1ppm
inorganic chloride.

The chemical principle behind this test is as follows. Inorganic chlorides react
with acidified silver nitrate to form silver chloride which can be seen in solution
as an insoluble white precipitate. The more inorganic chloride there is in the test
sample, the greater the intensity of the white precipitate.

The reaction of silver with chloride occurs at a ratio of 1:1, in other words, one
part of chloride will react with one part of silver. Silver nitrate is typically
supplied in concentrations of between 2% and 10%. A concentration of 2% silver
nitrate is equivalent to around 12,000 ppm of silver which is equal to a massive
excess of silver, far higher than the level of inorganic chlorides that are typically
expected in a wall wash or cargo sample.

The reaction between silver nitrate and inorganic chlorides can be quite slow,
particularly at very low levels of chloride. For this reason, it is quite common to
add nitric acid to the mixture which acts as a catalyst, speeding up the
formation of the white precipitate. The most widely used concentrations of nitric
acid are 10% or 20% and this can added separately or as a mixture with the
silver nitrate.

Equipment Required

1. Laboratory grade methanol

2. Graduated 50ml glass measuring cylinders with stoppers
3. Solution of 2% silver nitrate in water
4. Solution of 20% nitric acid in water
5. Alternatively a solution of acidified silver nitrate **
6. Dropper bottle or pipette.
7. Solution of 10ppm inorganic chloride in methanol

** Laboratory prepared reagent based on Nitric Acid 20% and Silver Nitrate 2%

Procedure

1. Transfer 25ml of the 10ppm inorganic chloride standard into one of the
50ml measuring cylinders
2. Transfer 25ml of laboratory grade methanol into another 50ml measuring
cylinder. This is the reference sample.
3. Transfer 25ml of each wall wash / cargo sample to separate, clean 50ml
measuring cylinders.
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4. Add 5 drops of 20% nitric acid and 5 drops of 2% silver nitrate (or
alternatively, 5 drops of the acidified silver nitrate solution) to each of the
above samples.
5. Leave all samples to develop for 15 minutes in a dark space.

Reporting

In much the same way as the hydrocarbon test is reported, looking down the
length of the measuring cylinder compare the colour of the wall wash / cargo
samples firstly against the reference sample and secondly against the 10ppm
inorganic chloride standard.

If the test sample shows greater turbidity than the standard, the result should
be reported as greater than 10ppm inorganic chloride. Likewise if there is less
turbidity compared to the standard, the result should be reported as less than
10ppm inorganic chloride.

Diluting the inorganic chloride standard to lower concentrations may be done,

based on actual requirements or specifications. Always ensure that the dilution
is carried out with lab grade methanol and not DI water, because the degree of
turbidity in water is greater than it is in methanol, meaning that 1ppm inorganic
chloride in water will show a higher level of turbidity compared to 1ppm
inorganic chloride in methanol.

0 0.2 1 2 5 10
ppm ppm ppm ppm ppm ppm

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Samples under torchlight clearly show the degree of turbidity is intensified.

0 0 0.2 0.2 1 2 5 10
ppmppm ppm ppm ppm ppm ppm ppm

0 0.2
ppm ppm

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11. Analysis – Acid Wash Colour of Aromatic Hydrocarbons.

Scope

This method covers the determination of the acid wash colour of benzene,
toluene, xylene, refined solvent naphtha and similar hydrocarbons, in
accordance with ASTM D848.

Definition

Acid wash colour: The colour developed in the separated acid when a sample is
agitated with concentrated sulphuric acid under the conditions described in this
method.

Equipment Required

1. Acid wash colour standards, numbered 0 to 14 as described in ASTM

D848
2. Stoppered measuring cylinders, typically 30 or 50 ml.
3. Sulphuric Acid 96%. (For High Flash solvent or Heavy Solvent Naphtha,
use
4. Sulphuric Acid 78%. See below chart.)
5. Toluene (or Xylene) to be used as wall wash medium.

Procedure

1. Transfer 7ml of sulphuric acid with the strength as specified in Table 1

into a clean, dry glass stoppered measuring cylinder.

(Great care should be taken during this step, because concentrated sulphuric
acid is extremely corrosive and can cause serious injury even in the slightest
cases of exposure. Flush with copious amounts of water in the event of any
spillage or skin exposure.)

Table 1

Acid strengths and standing times

Sample Acid strengths Standing time

Group 1 Benzene, all ASTM grades 96% 15min

Toluene, all ASTM grades
Xylene, nitration grades
Xylene 5º
Xylene l0º

Group 2 Xylene industrial grade 96% 5min

Refined solvent naphtha
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Group 3 Hi-flash solvent 78% 5 min

Heavy solvent naphtha

2. Very carefully add sufficient of the toluene / xylene wall wash / cargo
sample to bring the total volume in the measuring cylinder up to 28ml.
3. Insert the stopper into the measuring cylinder and securely holding a
finger over the stopper, give vigorous shakes with a stroke of 10 to 25 cm,
shaking for a total of 150 cycles over a period of 40 to 50 seconds; that is
at a rate of 3 to 3.75 cycles per second.
4. Allow the cylinder to stand, protected from direct sunlight, for the period
of time shown in Table 1.
5. Without further delay invert the cylinder gently once or twice to obtain a
uniform colour in the acid layer and compare the colour of the acid layer
with those of the standards below. Make the comparison against a white
background.

Reporting

Designate the colour of the acid layer to the number of the nearest matching
colour standard, adding to the number a “plus” or “minus” sign if the sample is
respectively darker or lighter than the colour standard.

Acid Layer Colour Scale 0 to 4.

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Acid Layer Colour Scale 5 to 9.

Acid Layer Colour Scale 10 to 14.

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