pH AND ALKALINITY CONTROL Introduction The importance of obtaining correct pH measurements has greater emphasis today than at any

other time. Its measurement is necessary both in the field and the laboratory as pH directly affects the functioning of drilling fluid additives. pH pH is the measurement of the relative degree of acidity or alkalinity of an aqueous solution. The numerical reading of the pH scale ranges from 1 (acid) to 14 (base), with 7 being the neutral point. It is known that the value of pH in the ranges stated are directly related to the effective or active acid concentration of a solution by the negative logarithm of the hydrogen ion concentration. The equation may be written as follows: pH = - log [H+] The [H+] in the equation represents the hydrogen ions in the solution, and can be referred to as the strength of the hydrogen ion in solution. If we have a strong acid of 0.01 molar, the pH is equal to 2 because the hydrogen ion concentration is as follows: H+ is 10-2 molar pH = - log [10 -2] pH = 2 The pH scale is based on the dissociation constant of water. In distilled water, there are a + few molecules that react with one another to form hydronium ions (H3O ). This accounts for the acidic properties. The base properties are given by hydroxyl (OH-) ions of the solution. The following reaction is how they focus:

2H2O = H3O+ + OH-

or

H2O = H+ + OH-

Distilled water, at 25 C, will dissociate until the acid (H+) and the base (OH-) concentrations are equal. So the neutral pH value is as follows: 1 x 107 molar The product of both concentrations is the equilibrium constant for water. It is referred to as the dissociation constant Kw: KW = (H+) (OH-) Kw = [1 x 107] [1 x10-7] 14 Kw = [1 x 10 ] In this equation, the hydrogen (H+) ion concentration equals 1 x 10-7, thus the pH is 7. This is referred to as the neutral point. In the continuous phase of drilling fluids, water is the primary aqueous solution. Drilling fluids allow us the flexibility of an increase in either the acid or base concentration, and

an increase in either concentration always results in a decrease in the other concentration. To demonstrate how a strong base material will effect the hydroxyl ion concentration, a solution of strong caustic soda (0.01 NaOH) will be used in the example below:

Kw 10 -14 = = 10 -12 -2 [OH] 10 12 pH = -Log [10 ] pH = 12 H+ = The pH chart in Figure No. 1 clearly shows the relationship of pH value to the activity of base/acid solutions. It must also be remembered that: All concentrations are expressed in moles/liter (H+) x (OH-) = Kw = 1 x 10-14 moles/liter Kw = Equilibrium constant for water As (H+) decreases, (OH-) must increase if the product is to remain constant (1 x 10-14 moles/liter) = Kw (H+) moles/liter 1 x 10-0 1 x 10-1 1 x 10-2 1 x 10-3 1 x 10-4 1 x 10-5 1 x 10-6 1 x 10-7 1 x 10-8 1 x 10-9 1 x 10-10 1 x 10-11 1 x 10-12 1 x 10-13 1 x 10-14 Figure 1 API recommends two methods for measuring the pH of drilling fluids. They are: Colorimetric method - paper strips impregnated with indicator dye. accurate to only 0.5 pH unit improper field storage, temperature and humidity affects dye high salt concentrations affect readings (10,000 mg/L or more) dark filtrates affect recognition pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 (OH-) moles/liter 1 x 10-14 1 x 10-13 1 x 10-12 1 x 10-11 1 x 10-10 1 x 10-9 1 x 10-8 1 x 10-7 1 x 10-6 1 x 10-5 1 x 10-4 1 x 10-3 1 x 10-2 1 x 10-1 1 x 10-0

Very High concentrati on ACID

Very Low Concentrati on ACID

Very Low Concentrati on BASIC

Very High Concentrat ion BASIC

Electrometric method - pH meter with a glass electrode accurate to within 0.02 pH unit can be standardized by calibrating with buffer solutions temperature compensated pH predicted by low voltage, which is very accurate poor accuracy with saturated NaCl and KCl solutions
E = Eo 2.303 (RT) pH F

where: E = measured voltage Eo = total constant voltage in the measuring system R = gas law constant T = temperature in OKG F = Faraday's constant Denotes for use in salt solutions (not saturated Cl- solutions)

pH is related to alkalinity, but it is not the same as alkalinity.

Alkalinity

Alkalinity may be defined as water soluble ions that neutralize acid. In other words, any ion that places a proton (H+) in the mud acts as an acid. On the other hand, any ion which combines with a proton (H+) is a proton acceptor and contributes to alkalinity. The following are some examples: 1. 2. H2SO4 Sulfuric Acid 2 H+ Hydrogen + + SO42Sulfate The acid places 2 protons (H+) in the water The hydorxide (OH-) combines with the proton (OH-)contributes to alkalinity

NaOH Na+ Sodium hydroxide Sodium + OHHydroxide

OHHydroxide H+ HOH Hydrogen Water

There are basically three ions in water base muds that contribute to alkalinity: Hydroxyl ions Carbonate ions Bicarbonate ions OH- + H+ CO32- + H+ HCO3 + H+ HOH (water) HCO3- (bicarbonate) CO2 + HOH (water)

In the above reactions, a proton (H+) combined with each ion. Therefore, each ion contributes to the alkalinity of a drilling fluid. Alkalinity and pH are related, but they are not the same.
Sources of Alkalinity

Caustic soda (NaOH), potassium hydroxide (KOH) and lime [Ca(OH)2] are added to drilling fluids at times to increase the pH of the fluid. Cement is a common source of hydroxyl (OH-) ions. The chemical reaction is as follows: Ca(OH) Lime Ca2+ Calcium 2OHHydroxyl

Anything added to the drilling fluid that places an OH- ion in solution will increase the pH. The carbonate (CO32-) ion has several interesting sources in nature. It is sometimes found in the form of potash (K2CO3). It may also be the product of a chemical reaction taking place as a result of a gas kick. When CO2 enters the drilling fluid, the following reaction occurs: 1. CO2 2. H2CO3 3. HCO3 + + + H2O OHOH H2CO3 Carbonic Acid HCO3- + H2O Bicarbonate CO32- + H2O Carbonate

A third source of CO2 comes as a byproduct of bacterial action on certain types of organic matter. Fluids that contain mixtures of vegetable fibers (loss circulation materials) or polymers are subject to bacterial action. This is also true of fluids that contain certain types of organic filtration control additives. A prime example is corn or potato starch. A chemical biocide should be added in conjunction with the starch to control bacterial activity, or when the fluids contain biodegradable organic substances. A fourth source of the carbonate/bicarbonate ion is make-up water. Any water used to mix or build drilling fluids should be checked for the presence of both ions prior to actual mixing of the fluid. The bicarbonate (HCO3-) ion generally occurs as the result of CO2 gas in the drilling fluid: The presence of the HCO3- ion is dependent upon the pH or OH- concentration (See Figure 1.) Also, note the reaction below which occurs at pH of 10.3 and above. HCO3Bicarbonate + OHHydroxyl HOH + Water CO32Carbonate

The reaction shows that the bicarbonate ion cannot co-exist in a fluid of relative high pH. The hydroxyl ion reacts to produce carbonate and water. This concept is used to counteract bicarbonate contamination. The pH range in which the maximum amount of bicarbonate ions can be found is 7.0 - 10.5, as seen in Figure 2.

At a pH of 10.5 and above the OH- concentration becomes large enough that the above reaction predominates leaving CO32- and water. Occasionaly bicarbonate of soda can be found in the earth's formations, however the primary source is CO2 gas. The following chart shows the predominate pH range for the alkalinity ions. p H 4.3 - 6.3 Carbon dioxide (CO2) gas mainly in solution pH 6.3 - 10.3 Bicarbonate (HCO3-) ion mainly in solution pH 10.3> Carbonate (CO32-) ion mainly in solution Knowledge of the relationship between pH and alkalinity can provide insight into which ion or ions are in solution and contributing to contamination problems. For example, it is virtually impossibe to have CO2 or HCO3- contamination if the pH is 11.5 - 12.0. On the other hand, it is also highly unlikely to experience CO32- contamination if the pH is 8.5 9.5.
Pf Alkalinity

The Pf titration is performed on the mud filtrate. Phenolphthalein is used as the indicator and N/50 (0.02N) sulfuric acid (H2SO4) is the titrating solution. The endpoint for the titration occurs when the color of the sample being titrated turns from reddish-pink back to the original color of the filtrate. The color change occurs at a pH of 8.3, and Pf is reported as the number of milliliters of N/50 sulfuric acid used to reach the endpoint. Noting the pH ranges listed above, it is readily seen that in the Pf titration the two ions that predominate are CO32- and OH-, with a small quantity of HCO3- ions present. Therefore the two reactions which occur in the Pf titration are: 1. CO32Carbonate 2. OHHydroxyl + + H2SO4 (N/50) Acid H2SO4 (N/50) Acid HCO3Bicarbonate HOH Water + + HSO4Bisulfate SO42Sulfate

In other words, at the 8.3 pH endpoint the following is true: Most of the CO32- has been converted to HCO3- as seen in Reaction No. 1, and most of the OH- has been converted to HOH as seen in Reaction No. 2. Therefore, it is possible to conclude that when there is a high concentration of either OH- or CO32- ions, the Pf will be rather large. The question is then how does one tell which ion is present? In order to determine which of the two ions is present in the Pf titration, the Mf titration must be conducted. Of the two ions (OH- and CO32-), only CO32- will affect the Mf titration. This is readily seen in Reaction No. 1, as the product produced is HCO3- The bicarbonate ion will then manifest itself in the Mf titration. The following reaction occurs when conducting the second titration to determine Mf: + 3. HCO3Bicarbonate H2SO4 Acid CO2 Carbon Dioxide + H2O + Water HSO4Bisulfate

In Reaction No. 3, most of the HCO3- is converted to CO2 at the 4.3 pH endpoint. The HCO3- ion determined in this titration may have come from the titration in Reaction No. 1 or the HCO3- ion may have been present in the filtrate prior to conducting any of the titrations. In other words, high concentrations of CO32- ions in the Pf titration will produce high concentrations of HCO3- ions in the Mf titration as seen below: Pf titration converts CO32- to HCO3Mf titration converts HCO3- to CO2
Mf Alkalinity

After performing the the Pf titration, add methyl orange or bromo-cresol green/methyl orange and continue to titrate with N/50 sulfuric acid. If methyl orange is used as the indicator, the sample will change from orange to salmon-pink when the endpoint is reached. If bromo-cresol green is used as the indicator, the sample will change from blue-green to yellow. The pH of the sample should be approximately 4.3 when the endpoint is reached. This is the second titration, and the milliliters of acid used in the titration are added to the milliliters of acid required to reach the Pf endpoint and the total amount of acid used is recorded as Mf alkalinity. The following is an example titration of a filtrate with a pH of 10.4. pH = 10.4 Pf = 3.2 ml N/50 H2SO4 to original color pH = 8.3 Color change: pink

Mf = 5.3 ml N/50 H2SO4 (3.2 ml + 2.1 ml to reduce pH from 8.3 to 4.3)

pH = 4.3

Color changes from orange to pink or blue to yellow

In the example above, a total of 5.3 ml of N/50 sulfuric acid was required to reduce the pH from 10.4 to 4.3. The Pf alkalinity is reported as 2.1 and the Mf alkalinity is reported as 5.3 (3.2 + 2.1 = 5.3). Using the following diagram it is possible to examine Pf and Mf in terms of the ions present in a given titration: pH OH- ions, OH- + CO32- ions, or CO32- ions 11.4 8.3 OH- ions, OH- + CO32- ions, or CO32- ions + HCO3- ions 4.3 HCO3- ions and CO2 gas Interferring ions Filtrate pH Pf Filtrate pH Mf Filtrate pH

Knowing that CO32- effects both the Pf and the Mf, it is easy to distinguish which ion is present in the Pf. OH- will not be present in the Mf titration High concentrations of OH- and HCO3- cannot exist simultaneously. This is due to the following reaction: HCO3- + OH- HOH + CO32If the Pf and Mf values are both high, the main contaminant has to be CO32- If the Pf is high and the Mf is relatively unchanged, the predominate ions are OH- ions. If the Pf value is relatively small and the Mf value is large, the predominate ions are HCO3- ions. Relating these values to pH can be easy. When the pH is greater than 10.5 and the Pf and Mf values are relatively high, the predominating ions will be CO32- ions. If the pH is less than 10.0 and the Mf value is large, the predominate ions will be HCO3- ions. If the pH is greater than 10.0, Pf is high and Mf is virtually unchanged, the predominate ions are most likely OH- ions. HCO3- and CO32- ions can co-exist in certain pH ranges, therefore, knowledge of the pH can aid in determining which of the two ions is causing the problem.

Estimating the Concentration of OH-, HCO3- and CO32- Ions in Water Base Drilling Fluids

If a red color does not develop upon the addition of phenolphthalein to a sample of filtrate, the Pf is recorded as zero (0). (See Figure No. 3.) If Pf = 0, the pH is <8.3, and the ions contributing to alkalinity are HCO3- ions which will be revealed by the Mf titration and reported as follows: OHCO32HCO3-, meq/L = 0 = 0 = Mf x 20

If a pink or yellow color does not develop when methyl orange or bromo-cresol green is added to a sample of filtrate following the titration for Pf, additional titration with acid is not required as the pH is already at 4.3. When this occurs the ions contributing to alkalinity are OH- ions only. (If CO32- ions were present, titration for Mf would have been required, and its not.) The ions are reported as follows: OH-, meq/L = Pf x 20 = 0 CO32= 0 HCO3 (When a second titration is not required, Pf = Mf.) The following expressions are used to determine the ions contributing to alkalinities. Pf = 0 Pf = Mf 2 x Pf > Mf 2 x Pf = Mf 2 x Pf < Mf The alkalinity is all HCO3- ions The alkalinity is all OH- ions The alkalinity is a mixture of CO32- and OH- ions The alkalinity is all CO32- ions The alkalinity is a mixture of HCO3- and CO32- ions

The following explains the reasoning behind the statements above: Pf = O Pf = O

no (OH ) 2 no (CO 3 )

8.3 pH

HCO 3 2nd = 3 ml 4.3 pH

Upon adding the phenolphthalein, there was no color change. This means the pH is already at 8.3 or less. Therefore, there cannot be any OH- or CO32- ions in the filtrate. The only ions that can be in the second titration will be HCO3-. 0 ml + 3ml 3 ml (OH-) me/L (CO32-) me/L (HCO3-) me/L Pf = Mf
Pf = 2 ml 2nd = 0 (OH - ) only no (CO32-) no (HCO 3 - ) 4.3 pH

= = = = = =

Pf 2nd titration Mf 0 0 20 x Mf

8.3 pH

Upon adding phenolphthalein, a red color develops indicating possible OH- or CO32ions. After titrating to the 8.3 pH endpoint, methyl orange is added and immediately a salmon pink color results. This simply means that the 8.3 pH endpoint is the same as the 4.3 pH endpoint. In other words, there is no second titration. Therefore, there can be no HCO3- ions. Also, there can not be any CO32- ions. CO32- ions would have been converted to HCO3- in the Pf titration, and a Mf titration would have followed. (OH-) me/L (CO32-) me/L (HCO3-) me/L 2 x Pf > Mf
Pf = 2 ml
OH H 2 O 2 CO 3 HCO 3

= = =

Pf x 20 0 0

8.3 pH HCO3 CO2

-

Since most of the acid was used in the Pf, it is likely that OH- and CO32- were present. Since CO32- shows up in the 2nd titration, it is likely there is some CO32- because there was a small titration. With HCO3- present, the 2nd titration would have been much larger.

2nd = 1 ml 4.3 pH Pf 2nd Mf (OH ) me/L (CO32-) me/L HCO3- me/L = = = = = = 2 ml 1 ml 3 ml (40 x Pf) (20 x Mf) 40 (Mf Pf) 0

2 x Pf > Mf
Pf = 1 ml 2nd = 3 ml CO 3
2-

HCO 3
-

HCO 3

CO 2 from Pf

HCO 3

CO 2

(present before Pf )

Since the second titration was large, it is sure that HCO3- is present. The Pf has to be 22mostly CO3 because the OH would have reacted with the HCO3 to form CO3 + H2O. The HCO3 produced in the Pf shows up in the Mf. Pf 2nd Mf = = = 1 ml 3 ml 4 ml

Remember: HCO3- that shows up in the Mf titration can come from two sources: The titration of the CO32- ion in the Pf yields HCO3- ion. There may be some HCO3- ions in the filtrate prior to running the Pf or Mf test. (OH-) = 0 (CO32-) me/L = 40 x Pf (HCO3-) = (20 x Mf) - (40 x Pf) 2 x Pf = Mf

Pf = 2 ml 2nd titration = 2 ml

{ CO

23

HCO 3
-

{HCO

CO 2

In the case where 2 x Pf = Mf,it is easy to see that the only ion present is CO32- If the alkalinity was solely from HCO3- then the Pf would have been small because HCO3- does not effect the Pf. The Pf could not have been from OH- and HCO3-, as they cannot coexist in high concentrations at the same time. 2 Mf + 2 ml 4 ml
= Pf = 2nd = Mf

In other words, all CO32- in the Pf was converted to HCO3- in the Pf titration. The HCO3was then converted to CO2 in the Mf titration. (OH-) = 0 2= 40 x pf (CO3 ) (HCO3-) me/L = 0 The alkalinity titrations discussed here are normally recorded on the daily drilling muil report. It is necessary to keep these values in line for the type system that is run, or a great number of problems may occur.
P1 P2 Alkalinity

In determining P1, 2 ml of N/10 (0.1 N) NaOH is added to the mud filtrate. The NaOH is required to raise the pH above 11.4. Above 11.4 pH, any HCO3- will be converted to CO32- via the following reaction: HCO3Bicarbonate + OH- NaOH 2 mls N/10 CO32- + Carbonate HOH Water

The next step is to add Barium Chloride (BaCl2). Remember, never pipette barium chloride as it is toxic. The barium (Ba) reacts with CO32- to form insoluble BaCO3 (barium carbonate): BaCl2 CO32- + Carbonate Barium Chloride Chloride BaCO3 + Barium carbonate Cl-

This leaves only OH- in solution. The concentration of OH- will equal the original concentration of OH- in the filtrate plus that added via N/10 NaOH. From the total (OH-) concentration, one must now subtract the OH- ions used in the conversion of HCO3- to CO32-. Emperically it looks like this: Hydroxyl Concentration (OH-) + Original In Filtrate (OH-) From N/10 NaOH added (OH-) + Used in conversion of HCO3- to CO32(OH-) After adding BaCl2

The OH- concentration remaining after the addition of BaCl2 in step 2, is then titrated with (N/50) hydrochloric acid. OHHydroxyl After BaCl2 is added + HCl HOH + N/50 Water hydrochloric acid ClChloride

In determining P2, the exact same procedure for determining P1 is followed, except that the mud filtrate is left out. P2 measures the total OH- which was added in P1. If P1 > P2, this indicates that none of the OH- ions in P1 were consumed in the conversion of HCO3- to CO32-. Therefore the only ions in the filtrate are CO32- + OH-. Since the CO32was removed by the BaC12, the OH- concentration is equal to the difference in the amount of acid used in P1 and in P2. So, me/L (OH-) = 20 x (P1 P2) or mg/L(OH) = 340 (P1 - P2)

Since the Pf gives a total amount of HCl to neutralize both the CO32- and the OH-, then ME/L CO32- = Pf (P1 P2) x 40 or mb/L CO32- = 1200 [Pf - (P1 P2)}

The me/L of acid used in neutralizing the CO32- must be multiplied by 2 since the carbonate ion has a -2 charge. Therefore, the multiplying factor of Mg/L for CO32becomes 40 instead of 20. To covert to mg/L of CO32- multiply the me/L x 60/2 (Eqwt of CO32-. If P1 < P2, this indicates that some of the N/10 NaOH added in P1 was consumed in the following reaction: NaHCO3 Sodium Bicarbonate + + NaOH Sodium hydroxide Na2CO3 Sodium carbonate + HOH Water

Since P2 = total OH- concentration added in P1, the P2 - P1 = the amount of acid (ml) used in converting the HCO3- to CO32-. Therefore, me/L HCO3- = 20 x (P2 - Pl) or mg/L HCO32- = 1200 Pf

It has been established that 40 x Pf - (Pf - P2) = me/L CO32-. However, one cannot ave HCO3- and OH- ions simultaneously in the mud filtrate, only HCO3- and CO32-. If OH- = 0, then P1 - P2 = 0, and the equation for determining the me/L CO32- becomes; CO32- = 40 x Pf - (0), since P1 - P2 = 0. This simplifies to 40 x Pf. So, me/L CO32- = 40 x Pf when P1 < P2. Or mg/L CaCO32- = 1200 Pf

The P1 - P2 is a alternate test but it has a standard place on the daily drilling mud report. It is not normally run unless an alkalinity problem may exist. (BARIUM CHLORIDE TITRATING SOLUTION, IF INGESTED, CAN KILL YOU).