ANNEXURE-1

DETERMINATION OF H2S CONCENTRATION BY IODOMETRIC

TITRATION

STANDARD SOLUTIONS & REAGENTS USED

0.1N iodine solution ,0.1N sodium thio sulphate solution,Conc.HCL,starch

indicator

STANDRDISATION OF IODINE SOLUTION

Titrate 25ml 0.1N iodine solution using starch indicator against 0.1N sodium
thiosulphate solution using starch indicator.

Factor = B [normality of sodium thio sulphate X volume used ]

A [normality of iodine solution X volume used]

If factor is within 0.95 – 1.05 solutions are acceptable & factor can be used
For calculation.

PROCEDURE

 Pipette 25 ml 0.1N iodine solution in conical flask , acidify with approximate 5 ml

HCL .
 Transfer approx. 50 ml of the test solution in the beaker pipette 10 ml test
solution in 250 ml conical flask containing 25 ml iodine soln.& 5ml HCL
Titrate with 0.1N sodium thio sulphate solution using starch indicator
End point would be dark blue to pale straw.

H2S conc. Ppm = [A-B] x [factor] x 17030

C
Where A = [normality of iodine solution X volume used]

B = [normality of sodium thio sulphate X volume used ]

C = volume of the test solution .

Factor = standardization factor for standard iodine solution.

 ANNEXURE-2

PREPARATION OF TEST SOLUTION AS PER TM-0284

 Solution A shall consist of 50 % by weight NaCl & 0.5% by weight glacial acetic
acid in distilled water i.e . 50gm NaCl & 5gm glacial acetic acid in 945 gms of
distilled water .
Initial PH of the solution shall be 2.7 + 0.1
 The PH at the start of the start of test shall be measured immediately after H 2S
saturation shall not exceed 3.3
PH at end of the test shall not exceed 4.0 for the test to be valid.

Solution B shall be prepared in accordance with ASTM D 1141,synthetic sea

Water , the initial PH of the solution shall be 8.2 + 0.1
PH after H2S saturation shall be within range of 4.8 – 5.4 & PH at the end of the
Test shall be within the range of 4.8 -5.4 for the test to be valid .

PREPARATION OF TEST SOLUTION AS PER TM-0177

 Solution A shall consist of 50gms of NaCl & 5gms of glacial acetic acid
dissolved 945 gms of deionised or distilled water. The initial PH of the solution
Before contact with the specimen & after H2S saturation expected to range betwn
2.6 -2.8. & at the end of the test shall not exceed 4.0.

 Solution B shall consist of 50gms + 4gms sod. Acetate + 2.3 gms Glacial
Acetic acid + 953.7 gms of deionised or distilled water , PH of the solutiton
Before contact with specimen & after H2S saturation shall be betwn 3.4&3.6
PH at the end shall not exceed 4.0.
 Work instruction for hydrogen induced
cracking [ H.I.C ]
1. GENERAL

This procedure establishes a test method for evaluating the resistance of pipe line &
pressure plate steel to HIC caused by hydrogen absorption from aqueous sulfide
corrosion.
The test method consists of exposing unstressed test specimens with to one of the test
solutions as per annexure-2, saturated with H2S gas at ambient temperature & pressure.
After a specified time the test specimen shall be removed and evaluated.
This test method is not intended to duplicate service conditions. It is intended to provide
reproducible test environment capable of distinguishing the susceptibility of different
steel samples to HIC in relatively short time.

2. PRECAUTIONS

H2S is highly toxic and must be handled with caution & any experiment using it must be
planned carefully.
Sufficient coolant must be used during cutting so that excessive heating of test
component does not occur.

3 TEST SPECIMEN

Each test specimen shall be 100 + 1mm long by 20+1mm wide, for pipe & plates three
test specimen shall be taken from each test blank.

The test specimen shall be full thickness or limited to maximum thickness of 30mm. a
maximum of 1mm may be removed from each surface. The test blank shall not be
flattened.

The test specimen shall be parallel to rolling direction.

Perpendicular to the weld for weld area of the welded pipe or plate.

Small diameter ,thin wall ERW & seamless line pipe test specimens shall have all mill
scale removed from inner & outer surface such that maximum of 0.05mm of material is
removed by machining or grinding resulting in finish equivalent to 320& grit , curved
test specimen shall be tested ,specimen shall not be flattened .
For plates over 30mm thk. To 88 mm inclusive, three test specimen shall be prepared
each 30mm thk. Located near both surfaces & at the centre line shall be taken to provide
for testing of total plate thickness.

For plates over 88mm thk. Five or more test specimen [uneven numbers ] each 30mm
thk. Minimum overlap shall be 1mm between adjacent test specimen.

For welded pipe the test specimen shall be taken from the weld ,90o from the
weld & 180o from the weld.for seamless pipe ,the test specimen shall be taken
120o apart around the circumference .for plates the specimen shall at one
end ,mid width of the plate.

4 SPECIMEN PREPARATION

The four cut edges surface shall be polished 320 grit paper .

Before exposing the specimen to the test solution the tset specimen shall be degreased
using acetone , the adequacy of degreasing shall be tested by the atomizer test in
accordance with ASTM F21, the method shall be reported.

The specimen shall be stored in desicator for not more than 24 hrs. after degreasing

5 TEST PROCEDURE

Test vessel shall be air tight & fabricated from glass or any other material
Non reactive with the test environment the test assembly schematic diagram as
per figure 1.

test specimen shall be placed in the test vessel with wide faces vertical &
separated from the vessel & other specimen by 6 mm dia. Glass rod.

5.3 the minimum quantity of the test solution shall be 3ml per cm2 of the total
Surface area of the specimens and fully submerged in the solution .
5.4 preparation of test solution & initial PH, PH after H2S saturation , PH at the end of
The test shall be as per ANNEXURE-2 attached.

5.5 purging of oxygen free nitrogen shall begin immediately after the test vessel is
Filled with test solution for removal of air & flow rate shall be maintained at
100 ml/minute/ litre of test solution for 1 hour minimum.

5.6 after nitrogen purging H2S shall be bubbled at the rate of 200ml/minute for 1hour
The test solution, thereafter a positive pressure of H2S gas shall be maintained.
The concentration of H2S in the test solution shall be measured by iodometric
titration shall be minimum 2300ppm . an accepted iodometric titration procedure
is detailed in APPENDIX-1 attached.

5.7 PH after H2S saturation and at the end of the test is recorded , shall be as per
APPENDIX-2.

6. TEST DURATION

Test duration shall be 96 hours . the test time shall begin immediately after
completion of the 60minutes H2S introduction period.

7 TEST TEMPERATURE

Test temperature shall be 250C + 3 0C .

8 EVALUATION

8.1 after exposure each specimen shall be cleaned to remove aal loose scale and
Corrosion products major surfaces shall be visually examined for evidence of any
Hydrogen blistering and recorded.

8.2 the specimen shall sectioned as per figure and shall be polished
metallographically

8.3 All identifiable cracks at magnification upto 100X shall be included in the
Calculation , except those lie entirely within 1mm of the internal & external
Surfaces of the test specimen , cracks separated by 0.5 mm shall be considered
As single crack.
8.4 the CLR , CTR , CSR shall be calculated as per equations 1, 2,3 given below
reported for each section & average for each test specimen

CLR = ∑ (a) x 100 % -------------------- equation (1)

W

CTR = ∑ (b) x 100 % -------------------- equation (2)

T

CSR = ∑ (a x b) x 100 % -------------------- equation (3)

WxT

Where , a = crack length, b= crack thickness , W=section width ,

T= test specimen thickness.