STIMULATION LABORATORY

PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

QUALITY CONTROL OF ACIDS

INTRODUCTION

In order to obtain the optimum response from any acid stimulation treatment
it is important that the strength and type of acid used are the same as in the
original design. Variations in acid concentration can lead to an
unsubstantiated evaluation of the treatment as well as a poor or damaging
formation response.

SAFETY

When handling HCl, HF and sodium hydroxide, rubber gloves, apron and
goggles must be worn as these chemicals cause severe burns. A face
shield should be worn when handling HF, sodium hydroxide and
concentrated HCl.

NOTE: Never add water to concentrated acid when preparing dilute

acid solutions.

1.0 TESTING ACID CONCENTRATION

1.1 Specific Gravity Method

1.1.1 Equipment

• Graduated Cylinder (500 mL)

• Hydrometer (specific gravity scale)
• Thermometer (0° to 250°F or -17 to 120°C with an accuracy of
±1.0°F,0.1°C ).

1.1.2 Procedure

1. Obtain 350 to 400 mL of an acid sample and pour it into the graduated
cylinder (500 mL).

2. Place a clean and dry hydrometer, corresponding to the expected

density range, in the acid column so that it floats freely.

3. Read the point on the hydrometer scale from the bottom of the fluid
meniscus.

4. Record the temperature of the acid immediately after the hydrometer’s

specific gravity reading is taken. Use Table 1 to correct the temperature
dependence of the specific gravity reading.

5. Convert the corrected SG to concentration of HCl as a percent by using

the following equation

%HCL = [(Corrected SG x 2) - 2] x 100

ECA Stimulation Page 1 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

NOTE: For a sample reading above 60°F (15.6°C), the correction should be
added to the specific gravity reading. Conversely, for a temperature below
60°F (15.6°C), the correction should be subtracted from the specific gravity
reading.

For example, if the acid sample has a specific gravity of 1.085 at 40°F
(4.4°C), the temperature correction factor is 0.004 (Table 1). Since the
temperature is below 60°F (15.6°C), the correction factor should be
subtracted from the observed reading to give 1.081. The concentration of
HCl is 16.2%.

NOTE: PERIODICALLY CONFIRM SG = 1.0 FOR WATER.

1.1.3 Results

Based on the final value obtained for the HCl concentration (%) adjustments
must be made to the acid concentration using the dilution/mixing schedules
found in the Engineers’Handbook.

NOTE: The Dowell Schlumberger specification for delivered acid is as

follows:

Acid Strength (%) Concentration

Variation (%)
0 to 5 ± 0.5
6 to 14 ± 1.5
>15 ± 2.0

The above procedure and equipment are for determining HCl acid
concentration only. If a QA/QC procedure is required for Mud Acid or Acetic
Acid, then a titrimetric analysis must be done.

ECA Stimulation Page 2 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

TABLE 1
TEMPERATURE CORRECTIONS FOR SPECIFIC GRAVITY HYDROMETER
Correction for 1.000 to 1.075 1.075 to 1.120 1.120 to 1.180 1.180 to 1.210
Specific Gravity SG Acid SG Acid SG Acid SG Acid
Temp. °F (°C) Temp. °F (°C) Temp. °F (°C) Temp. °F (°C)
Subtract 0.009 - - 30 (-1.1) 34 (1.1)
Subtract 0.008 - 20 (-6.7) 33 (0.6) 37 (2.8)
Subtract 0.007 - 25 (-3.9) 37 (2.8) 40 (4.4)
Subtract 0.006 20 (-6.7) 30 (-1.1) 40 (4.4) 43 (6.1)
Subtract 0.005 27 (-2.8) 35 (1.7) 43 (6.1) 46 (7.8)
Subtract 0.004 33 (0.6) 40 (4.4) 47 (8.3) 49 (9.5)
Subtract 0.003 40 (4.4) 45 (7.2) 50 (10.0) 51 (10.6)
Subtract 0.002 47 8.3) 50 (10.0) 53 (11.7) 54 (12.2)
Subtract 0.001 53 (11.7) 55 (12.8) 57 (13.9) 57 (13.9)
0 60 (15.6) 60 (15.6) 60 (15.6) 60 (15.6)
Add 0.001 67 (19.5) 65 (18.3) 63 (17.2) 63 (17.2)
Add 0.002 73 (22.8) 70 (21.1) 67 (19.5) 66 (18.9)
Add 0.003 80 (26.7) 75 (23.9) 70 (21.1) 69 (20.6)
Add 0.004 87 (30.6) 80 (26.7) 73 (22.8) 71 (21.7)
Add 0.005 93 (33.9) 85 (29.5) 77 (25.0) 74 (23.4)
Add 0.006 100 (37.8) 90 (32.2) 80 (26.7) 77 (25.0)
Add 0.007 107 (41.7) 95 (35.0) 83 (28.4) 80 (26.7)
Add 0.008 113 (45.0) 100 (37.8) 87 (30.6) 83 (28.4)
Add 0.009 120 (48.9) 105 (40.6) 90 (32.2) 86 (30.0)
Add 0.010 - 110 (43.4) 93 (33.9) 89 (31.7)
Add 0.011 - 115 (46.1) 97 (36.1) 91 (32.8)
Add 0.012 - 120 (48.9) 100 (37.8) 94 (34.5)
Add 0.013 - - 103 (39.5) 97 (36.1)
Add 0.014 - - 107 (41.7) 100 (37.8)
Add 0.015 - - 110 (43.4) 103 (39.5)
Add 0.016 - - 113 (45.0) 106 (41.1)
Add 0.017 - - 117 (47.3) 109 (42.8)
Add 0.018 - - 120 (48.9) 111 (43.9)
Add 0.019 - - - 114 (45.6)
Add 0.020 - - - 117 (47.3)

1.2 Acid Titration Method

1.2.1 Equipment

• Hach Digital Titrator (16900-01)

• Distilled Water (200 mL)
• Hydrometer (1.0 to 1.2 SG)
• Phenolphthalein Indicator (0.005N)
• Sodium hydroxide Solution (1.6N)
• Sodium bicarbonate
• Potassium chromate Solution (0.05N)
• Silver nitrate Solution (1.128N)
• Dropper Bottle (single-drop dispenser)
• Mixer
• Titration Cartridges and Delivery Tubes
• Graduated Cylinder (500 mL)

ECA Stimulation Page 3 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

1.2.2 Single Acid Titration

1. Obtain the acid specific gravity (SG) using the hydrometer in 350 to 400 mL
of acid placed in a 500 mL graduated cylinder.

2. Pour the acid into an empty cartridge and attach a dispenser. Evacuate the
air by pushing the plunger against the seal and rotating the dial (refer to
procedure on page 14 of the Hach Titrator Instructions Manual in Appendix
D).

3. Reset the dial to zero.

4. Add 0.25 mL (200 digits) of acid to 75 to 100 mL of DISTILLED WATER

while stirring at a slow RPM and ensuring the dispenser tip is below the level
of the acid.

Note: Distilled water must be used to eliminate any inaccuracies that would
be caused from the salts that occur in potable and/or rig water.

5. Add two or three drops of phenolphthalein indicator to the acid solution.

6. Load the sodium hydroxide cartridge into the titration and attach a new
delivery tube. Evacuate the air and reset the dial to zero.

7. Dispense NaOH (1.6M Molarity) into the acid while stirring until a pink end
point (pH > 7) is reached; record the amount of digits dispensed.

Results

1. Calculate the percentage acid strength using one of the following formulas
and report the results on the worksheet provided in Appendix C-9.

% HCl = _ D1___
SG x 34.25

% HF = _ D1___
SG x 62.51

% Acetic = _ D1___
SG x 20.84

1.2.3 Mud Acid Titration

Note: Before taking an acid sample, ensure the acid has been “rolled”,
because he may “layer out”in a static tank.

1. Repeat the above procedure, using a sample of Mud Acid.

2. Add 0.5 to 1.0g of sodium bicarbonate to the solution and stir.
3. Add four to five drops of potassium chromate.
4. Load the silver nitrate (1.128M Molarity) cartridge into the titrator and attach
a new delivery tube. Evacuate the air and reset the dial to zero. Note: The

ECA Stimulation Page 4 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

delivery tube must be labelled as the same or a new delivery tube must be
used with each respective reagent cartridge.
5. Stir the acid solution continuously, dispense AgNO3 until the solution turns a
red tinge and records the digits dispensed.

Results

1. Calculate the total acidity using the formula and report the results on the
worksheet provided in Appendix C-9.

TA = _ D1__
SG x 125

2. Calculate the total chlorides as follows:

TC = _ D2__
SG x 177

3. Calculate the percentage of HF and HCl, if using 20% HF to formulate the

Mud Acid, as follows:

% HCl = TC x 3.65 and

% HF = (TA - TC) x 2

If using Intensifier Y1 to make the Mud Acid, then

% HCl = [(2 x TC) - TA] a 1.65 and

% HF = (TA - TC) x 4

For Mud Acid strength corrections, refer to Appendix C-11 through C-14
where anumber of tables give some contingency correction values for
various under-strength and overstrength Mud Acid concentrations using 20%
HF or Y1 with 35% HCl.

ECA Stimulation Page 5 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

2. DETERMINATION OF IRON IN ACID

Large amounts of iron in acid mixtures can affect the efficiency of treatment,
or can provide problems of precipitation, emulsion or incompatibility with
some additive. The control of iron content in acid mixtures before injection is
then required to prevent such problems.

The Dowell recommendation for total iron in acid is 100 ppm.

2.1 Method 1: Determination of Iron using a HACH DR/2000

Spectrophotometer

2.1.1 Equipment

• HACH DR 2000 Spectrophotometer

• Volumetric flasks (100 mL)
• Pipettes (1 mL graduated, 5 mL, 10 mL
• Deionised water
• Ferrover Iron Reagent Powder Pillows
• Ferrous Iron Reagent Powder Pillows
• Two matching sample cells (25 mL)
• pH indicator strips

2.1.2 Sample Preparation

1. Take a sample of acid to be analysed.

2. Take a clean 100 mL volumetric flask and to this pipette 0.2 mL of the
sample.
3. Dilute to the mark with deionised water, stopper and shake.

2.1.3 Determination of Total Iron

1. Press the power key of the HACH spectrophotometer and wait until the end
of the automatic self-test.
2. Press”2 READ/ENTER”. The display will show “Dial nm to 510”.
3. Rotate the wavelength dial to display “510 nm”. Press “READ/ENTER”. The
display will show “mg/L Fe FV”.
4. Fill a sample cell with 25 mL of the prepared sample. Add the contents of
one Ferrover Iron Reagent Powder Pillow to the sample cell. SWIM to mix.
Press “SHIFT + TIMER”. A 3 minute reaction period will begin. When the
timer beeps, the reaction is complete. The display will show “mg/L Fe FV”
and measurements can be made.
5. Fill a second sample cell (the blank) with 25 mL of prepared sample. Place
in the cell holder, close the light shield and press “zero”.
6. The display will show “WAIT” then “0.0 mg/L Fe FV”. Remove the blank
sample and replace with prepared sample. If the solution is (or becomes
cloudy) then see note 1 below. Press “READ/ENTER”.
7. The display will show “WAIT”, then the result in mg/L Fe will be displayed.
8. Calculate as follows: Reading* 500 = Fe (mg/L).
9. If the reading on the spectrophotometer is really low, this suggests that the
1/500 dilution is too great. Repeat the test with a lower dilution.

ECA Stimulation Page 6 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

Note 1: All analytical procedures require a dilution stage before analysis.

The measurements can be affected by the pH of the solution. This
colourimetric method does not work at low pH (<5), so the dilution factor and
acid strength must be considered for such an analysis.

This problem can be identified from:

- The reading on the HACH Spectrophotometer is not stable and increases

slowly
- The solution appears cloudy before analysis.

This problem can be eliminated by:

- Having a larger dilution factor when possible, if high amounts of iron are
present (>100 ppm).

- When a low level of iron does not permit the increase in dilution factor, a
pH increase is possible with sodium hydroxide until a neutral pH is reached.
This pH can be checked with pH paper with sufficient accuracy.

2.1.4 Determination of Ferrous Iron

1. Repeat the procedure for Total Iron with the following alterations:

Select method 255 for Fe (II)

Add Ferrous Iron Reagent Pillows to the sample.

2. Calculate: Reading* 500 = Fe (II) (mg/L).

2.1.5 Determination of Ferric Iron by Calculation

Total Fe (mg/L) - Fe (II) (mg/L) = (mg/l)

2.2 Method 2: Determination of Iron by Titration

If a HACH Spectrophotometer is not available, a straight forward titration

may be employed. This procedure however is very sensitive.

2.2.1 Equipment/Reagents

• HACH digital titrator

• Disposable 1 mL syringe or 1 mL pipette
• Glass or plastic beaker
• Disposable 10 mL syringe or 10 mL pipette
• Distilled or deionised water
• 1% potassium permanganate solution (KMnO4)
• Saturated hydrazine sulphate solution (H204 H2SO4)
• Potassium Iodide
• Thyodene indicator (iodine indicator)
• 0.1NSodiumthiosulphate(Na3S2O35H20)

ECA Stimulation Page 7 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

2.2.2 Procedure: Total Iron

1. Using the 1 mL pipette (or syringe) accurately measure 1.0 mL of acid

sample into the glass or plastic beaker.
2. Add approximately 10 mL of distilled (or deionised water. Using the 10 mL
disposable syringe.
3. Add 1% potassium permanganate dropwise until a permanent pink colour is
obtained. The addition of excess will not interfere with the results.
4. Add saturated hydrazine sulphate until the sample solution is clear or light
yellow in colour. Do not add any excess as this will affect the accuracy of
the results.
5. Add one half teaspoon (~2g) of potassium iodide to the sample solution.
Swirl to mix. A darker yellow colour should develop.
6. Add one half teaspoon (~2g) of thyodine indicator to the sample solution.
Swirl to mix. A blackish-blue colour should develop.
7. Prepare a 0.1N sodium thiosulphate solution and fill an empty HACH
cartridge.
8. Using the HACH digital titrator, titrate the sample with 0.1N sodium
thiosulphate whilst swirling to mix. The endpoint is reached when the
solution turns colourless.

2.2.3 Ferric Iron (Fe3+)

Repeat the procedure for ‘Total Iron’omitting steps 3 and 4.

2.2.4 Calculations

1. When using the HACH digital titrator multiply the reading by 6.9813 to obtain
the result in ppm iron (or mg/L iron).
2. If titrating with a 1 mL syringe multiply the reading in mL by 5585 to convert
the value to ppm iron (or mg/L iron).

2.3 Method 3: Determination of Iron in Acid using an Aquamerck Test Kit

The Aquamerck test kit may be employed as an alternative to the HACH

DR/2000 spectrophotometer method. The kit offers a quicker procedure to
the titration described in method 2 above. However, like the HACH
spectrophotometer method, the use of this kit requires the test sample pH to
be increased to approximately 5 for the bipyridine reagent to complex with
the iron in solution.

2.3.1 Equipment/Reagents

• Aquamerck Iron Test Kit

• Deionised or distilled water
• Sodium hydroxide solution (2M prepared in deionised water
• pH indicator strips
• 1 mL pipette (graduated), Volumetric flask (100 mL, 50 mL)

2.3.2 Procedure: Total Iron

ECA Stimulation Page 8 of 9

 STIMULATION LABORATORY
PROCEDURES
Procedure A01: QUALITY CONTROL OF ACIDS

1. Using the 1 mL pipette transfer 1 mL of acid under test to a ? mL volumetric

flask.
2. Make up to the mark with deionised water.
3. Check the pH of the test solution with pH indicator strips. If the pH is less
than 5 add dropwise, the sodium hydroxide solution until pH 5-7 is achieved.
4. Rinse the testing vessel several times with the sample solution then fill to the
upper calibration mark (=10 mL).
5. Add 6 drops of reagent 1. Stopper the vessel and shake. Leave for 2-3
minutes to allow all of the Ferric ions to be reduced to ferrous ions. Failure
to do so will give a false reading.
6. Add 6 drops of reagent 2. Stopper the vessel and shake.
7. Add 6 drops of reagent 3. Stopper the vessel and shake.
8. Wait for 10 minutes. Ascertain the total iron content in mg/L (ppm) by
comparing the red colour of the reaction solution with the corresponding
section of the colour scale. When reading the value, hold the white plastic
card provided behind the testing vessel.
9. If the colour is too pale or strong to interpret, repeat the procedure using a
different dilution factor. Remember to multiply the reading by the dilution
factor to obtain ppm iron.

2.3.3 Procedure - Ferrous Iron (Fe2+)

1. The sample solution as described in steps 1-3 above.

2. Rinse the testing vessel several times with the sample solution and then fill
to the upper calibration mark (=10 mL).
3. Add 6 drops of reagent 2. Stopper the vessel and shake.
4. Add 6 drops of reagent 3. Stopper the vessel and shake.
5. Wait 10 minutes. Ascertain the content of Fe2+ as described above.

2.3.4 Procedure - Ferric Iron (Fe3+)

The content of Fe3+ is given by the difference between total iron and Fe2+.

ECA Stimulation Page 9 of 9