1.

CATION EXCHANGE CAPACITY

The Methylene Blue Dye Test, (MBT), is used to determine the Cation Exchange Capacity of the solids present in a water base drilling mud. Only the reactive portions of the clays present are involved in the test and materials such as Barite, Carbonates, and Evaporites do not affect the results of the test, since these materials do not adsorb the Methylene Blue.

The Cation Exchanged Capacity of some typical clays is:

Clay Wyoming Bentonite Soft Shale Kaolinite Drilled Cuttings

CEC (milliequiv. / 100 gm moisture free) 75 45 10 8-12

For Bentonite based mud systems, the MBT provides an indication of the amount of reactive clays which are present in the drilling mud solids and for Bentonite free, water based mud systems, the MBT reflects the reactivity of the drilled solids. The test cannot distinguish between the type of clays but, if a reactivity for the drilled solids is known or assumed, it can be used to determine the amount of Bentonite present in the Bentonite based systems. Equipment: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Erlenmeyer flask Hot plate or bottle warmer Stirrer Rod Hydrogen Peroxide Solution (3%) Sulfuric Acid 5N Methylene Blue Solution 10 ml pipette 3 ml syringe No. 4 Whatman Filter Paper 25 ml Graduated Cylinder

Test Procedure: 1. Using the completely filled, 3 ml syringe, measure 2.0 ml of mud sample to be tested into the Erlenmeyer flask containing 10-15 ml of distilled water. 2. Add 15 ml Hydrogen Peroxide and 1 ml of 5N Sulfuric Acid. Swirl or stir as required to mixed the solution 3. Boil gently for approximately 10 minutes, and dilute with 20 ml fresh water. 4. Add Methylene Blue Dye in 1.0 ml increments. After each dilution, swirl the flask and stir vigorously for at least 20 seconds, and remove a drop of sample on the end of the stirring rod. 5. Apply the drop to a piece of filter paper making the drop with the amount of Methylene Blue added between each increment. The approximate end point is reached when a blue ring spreads out from the blue spot on the filter paper. At this point, without further addition of Methylene Blue, swirl the flask an additional 2 minutes, and place another drop on the filter paper. If the blue ring is again apparent, the end point has been reached.

If the ring did not appear, continue with the Methylene Blue increments until a blue ring permanently forms after two additional minutes of swirling. Note: For increased accuracy, 0.5 ml increments may be used as the end point is approached. The blue ring is more apparent on the reverse side of the filter paper from which the drop is placed. Calculations: Note: There are 2 different strengths of Methylene Blue dye that is used to determine the Equivalent Bentonite Content. One will have to determine which strength of dye the chemical testing company is supplying. 1. Stronger Strength of Methylene Blue: kg/m Reactive Clay ( Equivalent Bentonite Content) = 14.25 X ml Methylene Blue ml of Mud Sample Care of Reagents: The Methylene Blue Dye and Hydrogen Peroxide should be stored in a cool, dark place to extend the life. These solutions should be replaced every 4 months.
3

1.3

pH DETERMINATION

The acidity or alkalinity of a drilling mud is indicated by the Hydrogen ion concentration, which is commonly expressed in terms of pH. A perfectly neutral solution has a pH of 7.0, whereas alkaline (basic) solutions have a pH range between 7.0-14.0, and acidic solutions have a pH less than 7.0. The pH measurement is used as well to indicate the presence of contaminants such as cement or anhydrite. The two most common field methods for determining pH are described as follows: pHydion Paper: 1. This method may be used on the mud filtrate, or whole mud directly. 2. Place a 25 mm (1 inch) strip of indicator paper on the surface of the mud to be tested and allow it to remain until the liquid has wet the surface and the color has stabilized. This takes approximately 1 minute. 3. Compare the color standards provided with the test paper (which was not in contact with the mud solids) to the color standards provided with the test paper, and estimate the pH of the mud accordingly. Color pH Strips: 1. This method applies only to the mud filtrate. 2. After obtaining a sample of mud filtrate, totally immerse the colored portion of the color pH strip into the filtrate, and remove immediately. 3. After a short period of color stabilization (10-15 seconds), compare the color of the wetted strip with the color standards provided in the color pH plastic container. An estimate may be necessary if a color does not exactly match a particular pH value.

1.4

CHLORIDE DETERMINATION

Chloride ions exist in a mud system as Salts of Sodium, Magnesium, Calcium, or Potassium. The determination of the Chloride ion present in the mud filtrate may give an indication of a Salt water flow, or the presence of a Salt formation or stringer. In mud systems to which Salt has been added, the Chloride measurements show the amount of salinity present in the mud. Equipment: 1. Silver Nitrate solution: - 0.0282 N for low Chloride concentrations - 0.282 N for high Chloride concentrations 2. Potassium Chromate indicator 3. Sulfuric Acid (N/50) 4. Phenolphthalein indicator 5. Pipettes (1 ml) 6. White titration dish 7. Stirring rod Test Procedure: 1. Measure 1.0 ml of filtrate into a white titration dish and dilute to a convenient volume with distilled water. 2. Add a few drops of Phenolphthalein indication solution. If a pink color develops, add N/50 Sulfuric Acid until the pink color completely disappears.

3. Add 4-5 drops of Potassium Chromate indicator to obtain a yellow color. 4. Add Silver Nitrate while swirling or stirring until the color changes from yellow to orange-red (brick red), and persists for 30 seconds. Calculations: 1. If 0.0282 N Silver Nitrate is used: mg/L Chlorides = 1000 X ml of Silver Nitrate added If 0.282 N Silver Nitrate is used: mg/L Chlorides = 10000 X ml of Silver Nitrate added

2.

Remarks: 1. mg/L Salt (NaCl) = 1.65 X mg/L Chlorides 2. The Chloride test may be run on the same sample used in the Pf determination, if the Mf test was not performed. 3. Avoid contact with the Silver Nitrate solution. Wash immediately with water if Silver Nitrate gets on the skin or clothing. 4. The end point of the reaction is when the Silver Chromate is when the first detectable permanent color change from yellow to a light brick red occurs. When using the weak Silver Nitrate solution, the end point is approached very gradually. Therefore, the formation of the Silver Chromate can be seen by a color change for yellow to brick red. If the strong Silver Nitrate is used, the end point is approached much more rapidly. Hence the early formation of the Silver Chromate, and is brick red color may be missed due to the larger amounts of Silver Nitrate being added. The color change will go from yellow to red. As soon as the red color is seen, the titration is complete. 5. White lumps of Silver Chloride form when titrating high concentrations of Salt. This should not be mistaken for the end point. 6. A high pH will precipitate Silver Oxide.

1.5

FILTRATE HARDNESS (Total Hardness, Calcium & Magnesium)

Water containing large amounts of Calcium or Magnesium Salts is commonly referred to as hard water. Make up waters that are hard make it difficult to obtain the maximum yield from Bentonite , so it becomes necessary to treat out excess Calcium. As a general rule, the total hardness as Calcium should be brought to less tan 40 mg/L. The presence of Calcium in the mud filtrate may also indicate the presence of contaminants, such as anhydrite or cement. Equipment: 1. 2. 3. 4. 5. 6. 7. 8. Titraver Solution, 1 ml = 1 mg CaCO3 Strong Buffer Solution Manver Indicator 1 ml Pipettes Distilled Water Stirring Rod Calver II Indicator (to distinguish Calcium form Magnesium) Potassium Hydroxide (8N) solution to distinguish Calcium from Magnesium)

Test Procedures: Total Hardness (as Calcium): 1. Using a pipette, measure 1.0 ml of filtrate into a white titration dish, and dilute to a convenient volume with distilled water. 2. Add 4-5 drops of strong Buffer solution, and 2-3 drops of Manver Indicator. A red or wine color will develop if Calcium is present. 3. While swirling or stirring continuously, add Titraver with a pipette until the color changes from red to blue. At this end point, record the number of milliliters of Titraver added. Calculations: mg/L Hardness (as Calcium) = 400 X ml Titraver added

Calcium Hardness: 1. Using a pipette, measure 1.0 ml of filtrate into a white titration dish, and dilute with a small amount of distilled water. 2. Add 2-3 drops of 8N KOH (Potassium Hydroxide) solution. 3. Add several grains of Calver II, and swirl or stir to mix. 4. Using a pipette. Titrate with Titraver solution to a color change from red to blue. Calculations: mg/L Calcium Ion = 400 X ml Titraver added

Magnesium Hardness: The Magnesium hardness is calculated as follows: mg/L Magnesium = mg/L Total Hardness (as Calcium) mg/L Calcium 1.6 MUD FILTRATE ALKALINITY

Acidity is one measure of alkalinity that is indicated by the pH. However, the nature and amount of other ions such as Carbonates or Bicarbonates can also effect mud filtrates alkalinity. For fresh water mud systems, these ions can be indicative of the rheological stability of such mud systems. Concentrations of either ion can result in high, low shear rate viscosity (Yield Point) and high, progressive Gel Strengths. Three methods can be employed for the determination of Carbonate and Bicarbonate concentration. The very common Pf / Mf method is restricted to mud systems having a low organic content, whereas the P1 / P2 method or Garret Gas Train may be used for better, more quantitative method, especially in the systems with high organic content. 1.6.1 Pf / Mf Method

Equipment: 1. 2. 3. 4. 5. 6. 7. Phenolphthalein Indicator Solution Bromo Cresol Green Indicator Solution Distilled Water N/50 Sulfuric Acid White Titration Dish Stirring Rod 1 ml Pipette

Test Procedure: 1. Using a 1 ml pipette, measure 1 ml of filtrate into a white titration dish. Dilute with distilled water. 2. Add 2-3 drops of Phenolphthalein Indicator. - if no color change occurs, then the Pf = 0; continue to step 4 - if a pink or red color develops, the Pf > 0; continue to step 3 3. Using a pipette, add N/50 Sulfuric Acid continuously while swirling or stirring until the sample changes from pink to colorless (or original filtrate tint). 4. The number of ml of N/50 Sulfuric Acid to reach this point is recorded as the Pf value. 5. To the sample, which has been titrated to the Pf end point, add 2-3 drops of Bromo Creosol indicator solution to obtain a light blue color. Continue titrating with swirling (or stirring) until the color changes from light blue to apple green (pH 4.0-4.5). This end point is recorded as the Mf end point. Calculations: Use the following table to estimate the Carbonate (CO 3 ), Bicarbonate (HCO3 ), or Hydroxyl (OH ) alkalinity present in the mud system. Pf / Mf Relation Pf = 0 Pf = Mf 2Pf = Mf 2Pf > Mf 2Pf < Mf Bicarbonate -2 (mg/L HCO3 ) 1220 X Mf 0 0 0 1200 (Mf 2Pf) Carbonate (mg/L CO3 ) 0 0 1200 X Pf 1200 (Mf Pf) 1200 X Pf Hydroxyl (mg/L OH ) 0 340 X Mf 0 340 (2Pf Mf) 0
-2 -

1.6.2

P1 / P2 Method

Inorganic ions such as Borate, Silicate, Sulfide, and Phosphate ions can have a real effect on mud alkalinity. Additionally, organic compounds (ex: anionic organic thinners, fluid loss additives, or other Polymers) and their degradation by-products, may also affect the determination of the relative amounts of Carbonate, Bicarbonate, or Hydroxyl ion in solution. The P1 / P2 method eliminates these effects. Equipment: 1. 2. 3. 4. 5. 6. 7. 8. Sodium Hydroxide Solution (0.1 N) Barium Chloride Solution Phenolphthalein Indicator Solution N/50 Sulfuric Acid White Titration Dish Stirring Rod Distilled Water Pipettes (1 ml)

Test Procedure:

1. Determine the Pf end point as outlined in steps 1-3 of the Pf/Mf method. If the Pf = 0, there are no carbonates present. 2. Place 1 ml of filtrate into a white titration dish, and dilute with distilled water. 3. Add a measured 2 ml of 0.1 N Sodium Hydroxide solutions to convert all Bicarbonate to Carbonates. Check the pH if it is less than 11.5, continue to add 0.1N Sodium Hydroxide in 1 2 ml increments, until the pH exceeds 11.5. Make a record of the total amount of Sodium Hydroxide added in this step.

4. Add a measured amount (2-4 ml) of Barium Chloride to precipitate all the possible Carbonates. Add 2-4 drops of Phenolphthalein solution and stir with a stirring rod. 5. Using a 1ml pipette, tritrate immediately to the end point with N/50 Sulfuric Acid. Record the number of mls N/50 Sulfuric Acid added as the P1 end point. 6. Place exactly the same amounts of 0.1N Sodium Hydroxide, Barium Chloride, and indicator into 25 ml of distilled water, and titrate to the end point using N/50 Sulfuric Acid, and record this as the P2 end point. Calculations: Pf = 0 There are no Carbonates present P1 > P2: mg/L Bicarbonates (HCO3) = 0 mg/L Carbonates (CO3) = 1200 [Pf (P1-P2)] mg/L Hydroxyls (OH) = 340 (P1-P2) P2 > P1: mg/L Hydroxyls (OH) = 0 mg/L Carbonates (C03) = 1200 x Pf mg/L Bicarbonates (HCO3) = 1220 (P2 P1) WARNING: The reagents may be hazardous to the health and safety of the user if inappropriately handled. ALKALINITY OF THE MUD (Pm) This test measures the alkalinity of the whole mud. When used in conjunction with the filtrate alkalinity determination, the amount of excess Lime present in the mud can be determined. Equipment 1. 2. 3. 4. 5. Titration dish Syringe, 3 ml Distilled water Phenolphthalein indicator solution N/50 (0.02 N) Sulfuric Acid

Test Procedure 1. 2. 3. 4. 5. Measure 1 ml of a freshly stirred sample of mud into a titration dish using a syringe. Dilute the mud in the dish with about 50 ml of distilled water. Add 4-5 drops of Phenolphthalein indicator solution. If the sample does not change color, record the Pm as 0. If the sample turns pink, titrate rapidly with N/50 Sulfuric Acid until the pink color disappears.

Calculations Report the alkalinity of the mud, Pm as the number of ml of N/50 Sulfuric Acid added until the pink color disappears. Note: If the mud sample is deeply colored and the color change is hard to see, use 0.5 ml of mud, and report the Pm as the volume of Sulfuric Acid added X 2.0. If N/10 (0.1N) Sulfuric Acid is used, the Pm is reported as the volume of acid added to 1 ml of mud X 5.0.

1.7

POTASSIUM ION CONCENTRATION

When a drilling mud containing Potassium Chloride or Potassium Sulfate is used, the primary purpose is to prevent, or at least minimize hydration of water sensitive formations. Inhibition of hydration is + provided by the Potassium ion (K ), which is attracted to negative charges appearing through the flat surface. Therefore, it is extremely important to know the Potassium ion concentration at all times in these mud systems. There are two different methods of determining the amount of Potassium in a mud system; one utilizing a hand cranks centrifuge, and the other utilizing Potassium test strips.

1.7.1

HAND CRANK CENTRIFUGE METHOD

Equipment 1. Hand cranking centrifuge with 18:1 gear ratio 2. Two graduated 15 ml centrifuge tubes 3. 750 gm/L Sodium Perchlorate precipitating solution

Test Procedure 1. In order to balance the centrifuge, measure 14 ml of fresh water in the other centrifuge tube, and place it into the centrifuge. 2. Add 4.0 ml Sodium Perchlorate to 10.0 ml of filtrate to be tested in the centrifuge tube. A white precipitate which forms immediately indicates the presence of Potassium. 3. Invert slowly for 1 minute and place in the centrifuge. 4. Centrifuge for 1 minute at a cranking speed of 120 RPM (10 revolutions every 5 seconds). 5. Remove the centrifuge tube, and not the amount of centrifuged precipitate as the FLOC VOLUME in milliliters. Do not discard the centrifuged filtrate at the this point. 6. Determine the Potassium ion concentration from the table below: Note: For Potassium ion concentrations above 55,000 mg/L, save the centrifuge filtrate, clean the tubes, split the centrifuged filtrate evenly into each tube, add 4 ml Sodium Perchlorate to each tube, and centrifuge again. Record the total floc volume as the sum of the original floc volume, plus any additional floc volume obtained by double centrifuging.

Potassium Ion Concentration

Floc Volume (milliliters) 0.00 0.25 0.50 0.80 1.10 1.30 1.50 1.70 1.90 2.10 2.30 2.50 2.70

Potassium Ion Concentration (mg/L) 0 5000 7500 10000 15000 19000 24500 31000 38000 45000 53000 59000 65000

2.90 3.10 3.30

+ 3

70000 75500 81000

NOTE: 5250 mg/L K is approximately 10 kg/m KCl

1.8

POLYACRYLAMIDE (PHPA) POLYMER CONCENTRATION

Mud systems may utilize a Partially Hydrolyzed Polyacrylamide (PHPA) Polymer to provide or enhance inhibition by encapsulation of the Polymer around the hydratable clays that are encountered while drilling. In order for this method of inhibition to be effective, a residual PHPA concentration must be present in the drilling mud filtrate. Equipment 1. 2. 3. 4. 5. 6. Hand Cranking Centrifuge, 18:1 gear ratio Two Graduated Centrifuge Tubes Floc Developer Solution Cresol Red Indicator Hydrochloric Acid, 0.2 N Sodium Hydroxide, 0.2 N

Test Procedure 1. Measure 12 ml of fresh water into test tube and place in centrifuge tube for balance. 2. Measure 10.0 ml filtrate in the graduated centrifuge tube. 3. Add 6 drops of Cresol Red indicator and with the tube covered, invert gently. A reddish purple color will develop to indicate a pH greater than 7.0. 4. Add 0.2 N Hydrochloric Acid drop by drop, inverting gently each time until the solution just turns an orange-yellow. 5. Add 2 ml floc developer solution. 6. Invert the tube gently to mix for 15-20 seconds, and allow the solution to stand for 3-4 minutes. 7. Invert the centrifuge tube a few times and place it in the centrifuge. 8. Centrifuge for 1 minute at a cranking speed of 120 RPM (same as 10 revolutions every 5 seconds). 9. Remove the centrifuge tubes and note the amount of centrifuged precipitate as milliliters of precipitate. Calculations kg/m of Polyacrylamide (PHPA) = 1.4 X ml of Precipitate 1.9 POLYGLYCOL CONCENTRATION
3

Polygylcols can be added to drilling fluids as a primary shale inhibitor. The Glycol will slowly deplete from the drilling fluid as it is absorbed into the shale formations as drilling progresses. Equipment 1. API standard retort kit, 50 ml is preferred for accuracy. It must be fitted with a temperature control, which will permit heating at 150 degrees C (302 degrees F) and 510 degrees C (950 degrees F). Test Procedure 1. Place a known volume of mud in the loser part of the retort cell, It is important that this sample contains as little entrained air as possible. Insert fine steel wool, as required into the upper part of the cell.

2. Assemble the cell and seal the threads with a silicone high temperature grease to reduce leakage through the threads. 3. Set the temperature controller to 150 degrees C. Heat the retort until all the water has been collected (approximately 90 minutes) 4. Note this volume as V1. 5. Re-adjust the temperature to 510 degrees C, and continue to distil over the remainder of the liquid phase. 6. Note the final volume as V2.

Calculations Volume Glycol % = (V2 V1) X 100 Sample Volume (ml)

Note: The presence of other liquids with high boiling points, such as lubricants, will interfere with the result of this test.