Tank wall wash test

Permanganate Time Test

The Permanganate time is used to judge the presence of oxidizable materials that may be
associated with contamination during distribution and to access compliance with a
specification. The test is based on the ability of potassium permanganate (KMnO4) to
oxidise hydrocarbon impurities that could be present in the wall wash liquid. If there is a
reaction in a neutral solution, the potassium permanganate is reduced and changes its
colour from pink-orange to yellow-orange. The more impurities the faster a change in colour
occurs.
Water Miscibility (hydrocarbon test) The purpose of this test is the qualitative detection
of non-water-soluble contaminants. It works on the basis that many impurities are soluble in
the wall wash liquid (Methanol, Acetone) but not in water. Sometimes this test is also called
Hydrocarbon test.
Chloride Test The Chloride test is used the judge the presence of chlorides on bulkheads
etc. Chloride levels vary from 0.1 ppm to 5 ppm depending on the requirement of the
charterer. Chlorides will react with Silver nitrate/nitric acid solution forming Silver chloride
(AgCl) which makes the solution turbid. By comparing the sample solution with the various
prepared standard solutions one can establish the ppm chlorides in the wall wash.
Colour Test Certain impurities result in discoloration of the wall wash sample. The colour of
the wall wash liquid is compared with unused wall wash solvent. Mostly the so-called Apha
colour is measured.
UV Test The UV-Test is used to identify certain hydrocarbons and chemicals. Many
hydrocarbons and chemicals have the ability to absorb UV-light when they are exposed to
such light. Certain molecular electrons will get exited if exposed to light. This exitation
results in absorbance of light which can be measured. Absorbance at a specific wavelength
is a measure for concentration of specific compounds. In a special apparatus called
Spectrometer a sample (containing hydrocarbons) and a reference sample (containing just
a solvent such as methanol) are exposed to a UV light source.
Acid Wash The Acid Wash Test Method is used to determine the presence of Benzene,
Toluene, Xylenes, refined Solvent Naphthas, and similar industrial aromatic hydrocarbons.
This test is also used for detecting of impurities in methanol. Compounds which cause
darkening in the presence of concentrated sulphuric acid due to carbonization can be
detected with this test. In Methanol analysis this is often referred to as Carbonizables
NVM Test Used to determine if there are non-volatile impurities on the tank surface. A
defined quantity of the wall wash liquid is evaporated. The weight of the residue, the socalled NVM (Non Volatile Matter), is detected by weighing. This is then divided by the
original weight of the sample. The NVM content must not exceed the value specified by the
loader.

Wall-Wash tests procedures on Chemical Tankers

Preparation
-ReagentPure Methanol (500 ml/bottle)
Pure Water (DI Water)
2% Silver Nitrate Solution (500 ml / bottle)
20% Nitric Acid Solution (500 ml / bottle)
10 ppm (0.01 mg/ml) Chloride Standard Solution (500 ml / bottle)
0.02% Potassium Permanganate solution (100 mg in 500 ml of DI Water) to be stored in a dark
bottle in a dark bottle and cool temperature.
Concentrated Hydrochloric Acid (500 ml / bottle)

-InstrumentFunnel x 1
Plastic Bottles (500 ml x 2 bottles for collecting wall wash samples)
Nessler Tube (100 ml x 6 nos.)
Pipette (5 ml x 4 nos. for Nitric Acid / Silver Nitrate/Chloride Solution / KmnO 4
A petridish or Shalle x 2 nos. (for testing Non-volatile matters)
Disposable Vinyl gloves (200 sheets / case)
Disposable Shoe covers
A.P.H.A. Color Standard (No. 3, 5, 8 & 10) for color test.
Black colored plate (for testing turbidity of Hydrocarbon / Chloride)
White colored Plate (for testing of turbidity of color)
Flash Light.

Wall Wash Sample Collection

Before entering into the tank for sampling, ensure that the tank has dried up completely and has
no humidity on the wall and gas freed.
Check for toxic gas /combustible gas / oxygen prior entry.
One man standby in attendance
Carry the test kit for WWT in a closed bag or wooden box and keeping in mind not to drop the
same in the tank while going into and coming out of tank.
Put the shoe covers and wear the vinyl gloves.
Wash the equipment to be used for WW sample collection by methanol.
A sample of test methanol is sprayed on the bulkhead and collected in a sample bottle by using
half cut funnel.
Take sample from four parts of forward / aft / port / Stbd bulkheads and in the area of 1 meter in
height x 30 cm in width at the position of 1.5 m from the bottom by methanol wash on the wall.
The necessary quantity of sample from each tank is about 200 to 250 ml (50 ml for color, 50 ml
for Hydrocarbon, 50 ml for Chlorides & 50 ml for PTT).
Sample Analysis
Colour
This is represented by APHA from 1 to 30 where >APHA5 is the most stringent. The number is
determined in the lab by passing light through the sample. Most ships do not have this
equipment but if you hold the sample against a white sheet of paper and it appears absolutely
colorless you can be quite sure that the number is less than 5. For this fill up sample about 50
ml and add 50 ml methanol into a 100 ml Nessler Tube.

Suspended matter
Switch of all light and hold torchlight at the bottom of the tube containing the sample. Any
suspended matter will be clearly visible.
Hydrocarbon Test
Hydrocarbons together with water will form a milky solution. To 50 ml of wall wash methanol
add 50 ml of DI water. The mixture is shaken and allowed to stand for 20 minutes. Initially
turbidity will appear and the same will reduce in a few seconds. Compare this to a nessler tube
containing 50 ml of pure distilled water and 50 ml of pure methanol (as a standard solution for
comparison) on the black plate or background. Switch off the lights and using a flashlight shine
the beam first from one side and then from other. Look into the tubes from the top for turbidity.
If the sample appears cloudy or not completely clear then hydrocarbons are too high and the
tank needs to be washed with methanol.
NOTE :- The proportion of methanol to distilled water for testing will depend on the terminal
where the product is to be loaded. Includes, where available, the required wall wash
specifications of terminals. If a terminal's required specification reads "hydrocarbons pass
(10/90)" this means that the surveyor conducting the wall-wash test will use a mixture of 10ml
of methanol to 90ml of distilled water. The responsible officer conducting the test onboard his
vessel may then use the same proportion of methanol to distilled water, however the
proportions of 30/70 will provide a more accurate picture of the tank wall.
Chloride Test
Normally 10ppm standard chloride solutions are available on board:
To make a 2 ppm standard solution add the following:
Pure methanol
50 cc
10ppm standard chloride solution 8 cc
Distilled water
38 cc
20% nitric acid solution
2 cc
2% silver nitrate solution
2 cc
To make a 0.5 ppm standard solution add the following:
Pure methanol
50 cc
10ppm standard chloride solution 2 cc
Distilled water
44 cc
20% nitric acid solution
2 cc
2% silver nitrate solution
2 cc
The principle of the test is that chloride together with a silver-nitrate solution gives a milky,
cloudy solution.
In a clean, graduated Nessler-tube transfer 30ml of the methanol and top up to 100ml with
certified distilled water, add 5 drops of nitric acid * and then 5 drops of silver-nitrate solution
and mix the contents thoroughly.
* Before adding the silver nitrate, take a reading as well. If there is a reaction between the nitric
acid and wallwash sample there is something else left on the coating which are not chlorides
and will reject the tank also. Then add the silver nitrate and take a reading again. The
difference in readings before and after is due to the actual chlorides. Prepare a standard solution
of 30ml certified methanol and 70ml certified distilled water with 5 drops of silver-nitrate
solution. In a dark room, and preferably against a dark background shine a penlight through the
contents and compare against the standard solution. If turbidity in the test Nessler-tube is
observed then chlorides are present.

1
2

3
4
5

Permanganate time test(PTT)

Make a standard solution with 0.1 gm of potassium permanganate in 500 ml of water.
This method serves as a means of detecting the presence of impurities in alcohols or ketones
that reduce potassium permanganate and is applicable to Methanol, Propanol, Butanol, Methyl
Ethyl Ketone and Methyl Isobutyl Ketone.
Substances reacting with potassium permanganate in neutral solutions reduce it to manganese
dioxide, which colours the solution yellow. In the PTT the time required for the colour of the test
solution to change to that of a standard solution is measured. The colour of the test solution
changes from pink-orange to yellow-orange. For shipboard testing the time for the colour to
differ from a test solution measured against a standard solution of certified methanol is
sufficient.
The equipment required for PTT are as follows:Cylinders, glass-stoppered, 50ml.
Constant temperature bath, capable of maintaining a temperature of 15.0 +/- 0.5 degrees C or
25.0 +/- 0.5 degrees C. If a constant temperature bath is not available then a bucket of water
cooled with ice is an acceptable shipboard substitute.
Pipette, capable of delivering 2ml of solution.
Clock or stopwatch.
Potassium Permanganate Solution (0.100 g of KMnO4 per 500ml of water).
Fill a 50ml glass-stoppered cylinder beyond the mark with certified methanol and place it in the
same bath.
When the samples have reached the bath temperature (about 5 minutes) add 2ml of potassium
permanganate solution with a pipette, invert once to mix the contents and return to the bath.
Keep the samples in the dark, and check about every 10 minutes.
Determine the time from the addition of the KMnO4 until the colour differs (fades) from the
standard of certified methanol.
Violet Light Violet Orange Color Light Yellow
When the test is finished wash the tubes with tap water and fill with concentrated hydrochloric
acid. Use protective gloves and goggles for this and preferably do it in the open.
Non-Volatile Matter
NVM can only be checked in a lab. A small portion of the test sample is placed in a petridish or
shalle and allowed to evaporate by applying heat to it. The weight of the dish when the entire
methanol has evaporated will determine the quantity of NVM in sample. It is preferable to carry
out this test with Acetone rather then methanol i.e. the sample should be taken using Acetone.
Acid Wash Test
Pour 7ml concentrated laboratory grade Sulphuric acid into a test tube. Add 21ml of the
wallwash sample (toluene). Shake vigorously for 30 seconds. Place in the dark for 15 minutes.
Look for colour (haze) in the Sulphuric acid layer. Compare with colour standard if one is
available on board. When toluene is used as a test medium, acceptable haze/colour of the acid
is 2 on the standard scale.

Wallwash test precautions and some causes of failure

Always use disposable plastic gloves when wall washing - the human hand contains
more salt than normal requirements and is a common cause of chloride
contamination.
Wear clean clothes and do not allow working gloves in the tank, avoid all contact of
clothing with the tank, wear protective disposable shoe covers.

15

Use a clean bucket on a clean line for transferring test equipment into the tank.
Wash the funnel and sample bottles with certified methanol prior to collecting the
sample.
Always test the distilled water and certified methanol prior to use for testing and
always run a standard against the test sample.
The glue used for the seals on some types of sample bottles have been known to
cause sample contamination.
When using acids for washing wear the proper protective equipment.
Take your time, sampling in a hurry or rushing through the test procedures cause
failure.
If the sample passes all tests, be suspicious, and test again.
Never test a wet tank, the tank wall must be dry.
Allowing a tank to "rest" after prolonged washing (especially hot washing) can often
turn a failed tank into a passed tank.
Keep a record of your wallwash results, especially if testing multiple
tanks. Consulting this record over days of tank cleaning may provide a useful
indication of which washing procedure is working best.
Removal of Hydrocarbon
If HC < 2 ppm
If 2 ppm < HC < 3 ppm
Methanol Spray
If 3 ppm < HC <
LEL) Methanol spray
If HC > 5 ppm
tank coating
Removal of Chloride
If Cl < 2 ppm
tank
If 2 ppm < Cl < 5 ppm
If Cl > 5 ppm
Spray

Spray Methanol in the tank

Toluene Steaming (Only in inert atmosphere) for 3 hours &
5

ppm

Toluene

Wash Steaming

(within

Re-cleaning with detergent or solvent depending upon

Steaming or Spray DI Water and then Methanol in the

Methanol Steaming (Within LEL)
Hand wash by Fresh Water Steaming Methanol

Removal of Oxide Residue (PTT)

If 30 min < PPT < 50 min
Methanol Spray
If 15 min < PPT < 30 min
Methanol Steaming Methanol Spray
If PPT < 15 min
Re-tank cleaning with detergent or solvent
Removal of Color
No. 5 < APHA < No. 10
Treatment with Rust Remover in case of rust & Methanol
spray
No. 10 < APHA < No. 15
Treatment with Rust Remover in case of rust
&Steaming & Methanol Spray
Treatment with Rust Remover in case of rust &Hot water butterworth Methanol
Spray
Removal of NVM Residue
Almost Nil NVM
Normal

Methanol Spray
Toluene wash Methanol wash

Too much

Re-tank cleaning by detergent or solvent