IP 30/07 (2014)

Detection of mercaptans, hydrogen sulfide, elemental sulfur

and peroxides — Doctor test method

This standard does not purport to address all of the safety problems associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability
of regulatory limitations prior to use.

1 Scope possibility of applying the most recent editions of

the standards indicated below.
The Standard describes the 'Doctor' test for
detecting the presence of mercaptans (thiols), IP 475, Petroleum liquids — Manual sampling.
hydrogen sulfide, elemental sulfur and traces of
peroxides, see note 1, in automotive fuels, ISO 3696, Water for analytical laboratory use —
kerosines, and other middle distillate petroleum Specification and test methods.
products.
3 Principle
NOTE 1 - The presence of a number of substances in the
test sample can affect the result of the test. A test portion is shaken with sodium plumbite
solution and the mixture observed. From its
Peroxides appearance, the presence or absence of mercaptans
(thiols), hydrogen sulfide, peroxides or elemental
This method cannot be used if there are more than sulfur may be deduced. Mercaptans may be
trace amounts of peroxides in the test sample. confirmed by the addition of sulfur, shaking and
observation of the appearance of the final mixture.
Carbon disulfide
4 Reagents and materials
If the test sample contains more than 0,4% (m/m)
of sulfur as carbon disulfide it causes a darkening of For the analysis described in this method, use only
the aqueous layer on standing and caution is reagents of recognised analytical grade and water
necessary to avoid confusing this darkening with complying with the requirements of Grade 3 of
the immediate blackening due to hydrogen sulfide or ISO 3696.
that produced by mercaptans.
4.1 Sulfur powder, sublimed ('flowers of sulfur'),
Phenolic substances dry.
Certain phenolic substances (which may have been 4.2 Acetic acid glacial
introduced as inhibitors) cause colouration of the
aqueous layer and if their presence is suspected, a 4.3 Sodium hydroxide
blank test with sodium hydroxide solution in place
of the sodium plumbite solution should be carried 4.4 Sodium hydroxide solution.
out first for the purpose of comparison, see 6.1.
Dissolve approximately 120 g of sodium hydroxide
2 Normative references (4.3) in approximately 200 ml of water.

The following standards contain provisions, which 4.5 Lead acetate trihydrate
through reference in this text, constitute provisions
of this Standard. At the time of publication, the 4.6 Sodium plumbite solution, (Doctor solution)
editions indicated were valid. All standards are
subject to revision, and parties to agreements based Place 25g ± 0,5 g of lead acetate trihydrate (4.5)
on this Standard are encouraged to investigate the crystals in a 400 ml beaker add approximately

30.1

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 DOCTOR TEST, IP 30

200 ml of water. Stir until dissolved. Add 5 Apparatus

approximately 100 ml of sodium hydroxide solution
(4.4). Heat the mixture on a boiling water bath for 5.1 Stoppered cylinder, made of glass, of
approximately 30 min. Allow the solution to cool approximately 50 ml capacity.
then pour into a 1l volumetric flask (5.5) and make
up to 1l with water. If the solution is cloudy filter 5.2 Measuring cylinders, 100 ml, 10 ml and
using a filter funnel (5.6) and a general purpose 5 ml capacity.
rapid filter paper (4.13). Store the solution in a
tightly closed, stoppered bottle and filter before use 5.3 Stoppered separating funnel, glass
if it is not clear. approximate capacity 50 ml.

4.7 Zinc acetate dihydrate 5.4 Beaker, glass, approximately 400 ml

capacity.
4.8 Zinc acetate solution
5.5 Volumetric flask, 1l capacity.
Dissolve approximately 15 g of zinc acetate
dihydrate (4.7) in approximately 100 ml of water. 5.6 Filter funnel
Add glacial acetic acid (4.2) in drops until the
solution is clear then add a further 1 ml 6 Sampling
(approximate) of glacial acetic acid.
Unless otherwise specified, obtain samples for
4.9 Potassium iodide
analysis in accordance with IP 475.
4.10 Potassium iodide solution, approximately
100 g/l solution
7 Procedure

Dissolve approximately 1 g of potassium iodide (4.9) 7.1 Check for the presence of phenolic
in approximately 10 ml of water. This shall be substances
freshly prepared for each test.
Place 10 ml ± 0,5 ml of the sample in a stoppered
4.11 Acetic acid, approximately 100 g/l solution cylinder (5.1) and add 5 ml ± 0,5 ml of sodium
hydroxide solution (4.4) and shake the mixture
Add approximately 10 ml of glacial acetic acid (4.2) vigorously for 15 s. If the sodium hydroxide solution
to approximately 100 ml of water. becomes coloured use this as a blank when
observing the colour of the aqueous layers in 7.2,
4.12 Starch solution, approximately 5 g/l 7.4 and 7.5.

This solution shall be freshly prepared. 7.2 Preliminary test

4.13 Filter paper, rapid general purpose grade Place 10 ml ± 0,5 ml of the sample in a stoppered
cylinder (5.1) add 5 ml ± 0,5 ml of the sodium
NOTE 2 - A Whatman number 4 grade has been found to plumbite solution (4.6) and shake the mixture
be suitable. vigorously for 15 s. Observe the appearance of the
mixture and continue the procedure as instructed in
Table 1.

Table 1
Observation Inference Continue test in accordance
with
Black precipitate forms immediately Hydrogen sulfide present 7.3
Brown precipitate forms slowly Peroxides probably present 7.4
During the shaking period the solution Mercaptans and elemental Discontinue the test
becomes opalescent and then darkens in sulfur present
colour
No change occurs or yellow colour is
7.5
produced

30.2

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 DOCTOR TEST, IP 30

7.3 Hydrogen sulfide present the interface between the sample and the sodium
plumbite solution.
7.3.1 Before continuing the test it is necessary to
remove the hydrogen sulfide from the test portion 7.5.2 Shake the mixture for 15 s, and allow to
by washing with the zinc acetate solution (4.8). settle for one min.

7.3.2 Place 20 ml ± 0,5 ml of fresh sample into 7.5.3 Observe the contents of the cylinder. If a
a stoppered separating funnel (5.3) and add brown or black precipitate is formed on the addition
approximately 1 ml of the zinc acetate solution of sulfur, mercaptans are present.
(4.8). Shake the mixture vigorously for 15 s. Allow
the layers to settle then decant 10 ml ± 0,5 ml of 8 Expression of results
the test sample into a stoppered cylinder (5.1) and
carry out a further preliminary test in accordance 8.1 If after shaking the test portion with sodium
with 7.2. If this second test does not produce a plumbite an opalescent colour is produced in the
black precipitate, continue in accordance with 7.5. aqueous layer and a brown or black precipitate is
formed after adding sulfur (7.5), report the result of
7.3.3 If the second test produces a black the test as 'Doctor Positive mercaptans (thiols)
precipitate draw off the zinc acetate aqueous layer present'.
add an additional 10 ml ± 0,5 ml of fresh sample to
the separating funnel. Add approximately 3 ml of 8.2 If after shaking the test portion with sodium
zinc acetate solution and shake the mixture for plumbite the aqueous layer becomes opalescent and
15 s. Allow the layers to settle and decant 10 ml ± then darkens in colour (7.2) report the result as
0,5 ml test portion into a stoppered cylinder and 'Doctor Positive mercaptans (thiols) and elemental
conduct a preliminary test in accordance with 7.2. sulfur present'.
Providing that the preliminary test does not produce
a black precipitate continue in accordance with 7.5. 8.3 If after shaking the test portion with sodium
If a black precipitate still forms repeat the washing plumbite an immediate black precipitate is formed
process on a fresh 20 ml ± 0,5 ml of test sample (7.2) report the result as 'Doctor Positive hydrogen
increasing the volume of the zinc acetate used for sulfide present'.
washing until the preliminary test does not produce
a black precipitate. 8.4 If, after removal of hydrogen sulfide from
the test portion (7.3) and shaking with sodium
7.4 Peroxides present plumbite produces a brown or black precipitate after
adding sulfur (7.5), report the result of the test as
7.4.1 To check if peroxides are present in 'Doctor Positive mercaptans (thiols) present and
sufficient concentration to invalidate the test, shake hydrogen sulfide present'.
10 ml ± 0,5 ml of a fresh portion of the sample
with approximately 2 ml of the potassium iodide 8.5 If no precipitate is formed after the addition
solution (4.10), add two drops of the acetic acid of sulfur (7.5), report the result of the test as
solution (4.11) and two drops of the starch solution 'Doctor Negative mercaptans (thiols) absent'.
(4.12). If the aqueous layer turns a blue colour this
confirms the presence of peroxides in sufficient 8.6 If peroxides are present (7.4), report
quantity to invalidate the test and the test should be 'peroxides present' and the result of the test is
discontinued. invalid.

7.5 Final test 9 Precision

7.5.1 Provided neither hydrogen sulfide nor not The test method only detects the presence or
more than trace amounts of peroxides were found absence of active sulfur species and no generally
to be present in the test portion add to the mixture acceptable method for determining precision is
of the test portion and sodium plumbite solution, available.
from 7.2, sufficient sulfur powder (4.1) to just cover

30.3

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IMPORTANT: This document is subject to a licence agreement issued by the Energy Institute, London, UK. It may only be used in accordance with the licence terms and conditions. It must not be forwarded to, or stored, or accessed by, any unauthorised user. Enquiries: e:pubs@[Link] t:
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 DOCTOR TEST, IP 30

10 Test report

The test report shall include at least the following

information:

a) the type and identification of the product

tested;

b) a reference of this Standard;

c) any deviation, by agreement or otherwise,

from the procedure specified;

d) the result of the test;

e) the date of the test.

30.4

This document is issued with a single user licence to the EI registered subscriber: Intertek
IMPORTANT: This document is subject to a licence agreement issued by the Energy Institute, London, UK. It may only be used in accordance with the licence terms and conditions. It must not be forwarded to, or stored, or accessed by, any unauthorised user. Enquiries: e:pubs@[Link] t:
+44 (0)207 467 7100