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) !ith " being the neutral point. It is kno!n 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 !ritten as follo!s# 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 !e have a strong acid of ).)1 molar the pH is equal to * because the hydrogen ion concentration is as follo!s# H' is 1)%* molar pH $ % log &1) %*( pH $ * The pH scale is based on the dissociation constant of !ater. In distilled !ater there are a fe! molecules that react !ith one another to form hydronium ions (H+ ,'). This accounts for the acidic properties. The base properties are given by hydro-yl (,H %) ions of the solution. The follo!ing reaction is ho! they focus#

*H*, $ H+,' ' ,H%

or

H*, $ H' ' ,H%

.istilled !ater at */0 1 !ill dissociate until the acid (H ') and the base (,H%) concentrations are equal. 2o the neutral pH value is as follo!s# 1 - 1)%" molar The product of both concentrations is the equilibrium constant for !ater. It is referred to as the dissociation constant 3!# 34 $ (H') (,H%) 3! $ &1 - 1)%"( &1 -1)%"( 3! $ &1 - 1)%14( In this equation the hydrogen (H') ion concentration equals 1 - 1)%" thus the pH is ". This is referred to as the neutral point. In the continuous phase of drilling fluids !ater is the primary aqueous solution. .rilling fluids allo! us the fle-ibility of an increase in either the acid or base concentration and

an increase in either concentration al!ays results in a decrease in the other concentration. To demonstrate ho! a strong base material !ill effect the hydro-yl ion concentration a solution of strong caustic soda ().)1 5a,H) !ill be used in the e-ample belo!# 3! 1) %14 $ 1) %1* $ %* &,H( 1) pH $ %6og &1)%1*( pH $ 1* H' $ The pH chart in 7igure 5o. 1 clearly sho!s the relationship of pH value to the activity of base8acid solutions. It must also be remembered that# 9ll concentrations are e-pressed in moles8liter (H') - (,H%) $ 3! $ 1 - 1)%14 moles8liter 3! $ :quilibrium constant for !ater 9s (H') decreases (,H%) must increase if the product is to remain constant (1 - 1)%14 moles8liter) $ 3! (H') moles8liter ;ery High concentrati on 91I. 1 - 1) 1 - 1)%1 1 - 1)%* 1 - 1)%+ 1 - 1)%4 1 - 1)%/ 1 - 1)%= 1 - 1)%" 1 - 1)%> 1 - 1)%< 1 - 1)%1) 1 - 1)%11 1 - 1)%1* 1 - 1)%1+ 1 - 1)%14
%)

pH ) 1 * + 4 / = " > < 1) 11 1* 1+ 14

(,H%) moles8liter 1 - 1)%14 1 - 1)%1+ 1 - 1)%1* 1 - 1)%11 1 - 1)%1) 1 - 1)%< 1 - 1)%> 1 - 1)%" 1 - 1)%= 1 - 1)%/ 1 - 1)%4 1 - 1)%+ 1 - 1)%* 1 - 1)%1 1 - 1)%) ;ery 6o! 1oncentrati on 91I.

;ery 6o! 1oncentrati on ?92I1

;ery High 1oncentrat ion ?92I1

7igure 1 9@I recommends t!o methods for measuring the pH of drilling fluids. They are# A 1olorimetric method % paper strips impregnated !ith indicator dye. A accurate to only )./ pH unit A improper field storage temperature and humidity affects dye A high salt concentrations affect readings (1) ))) mg86 or more) A dark filtrates affect recognition

A :lectrometric method % pH meter !ith a glass electrode A accurate to !ithin B ).)* pH unit A can be standardiCed by calibrating !ith buffer solutions A temperature compensated A pH predicted by lo! voltage !hich is very accurate A poor accuracy !ith saturated 5a1l and 31l solutions
: $: o % *.+)+ (DT) pH 7

!here# : $ measured voltage :o $ total constant voltage in the measuring system D $ gas la! constant T $ temperature in ,3 E 7 $ 7aradayFs constant A .enotes for use in salt solutions (not saturated 1l% solutions) pH is related to alkalinity but it is not the same as alkalinity. Alkalinity 9lkalinity may be defined as !ater soluble ions that neutraliCe acid. In other !ords any ion that places a proton (H') in the mud acts as an acid. ,n the other hand any ion !hich combines !ith a proton (H') is a proton acceptor and contributes to alkalinity. The follo!ing are some e-amples# 1. 2, The acid places * protons * 4 4 2ulfuric 9cid Hydrogen 2ulfate (H') in the !ater *. 5a,H 5a' ' ,H% The hydor-ide (,H%) 2odium hydro-ide 2odium Hydro-ide combines !ith the proton % ' ,H ' H H,H (,H%)contributes to Hydro-ide Hydrogen 4ater alkalinity There are basically three ions in !ater base muds that contribute to alkalinity# Hydro-yl ions 1arbonate ions ?icarbonate ions ,H% ' H' H,H (!ater) 1,+*% ' H' H1,+% (bicarbonate) H1, ' H' 1, ' H,H (!ater)
+ *

H 2,

* H'

*%

'

In the above reactions a proton (H') combined !ith each ion. Therefore each ion contributes to the alkalinity of a drilling fluid. 9lkalinity and pH are related but they are not the same. Sources of Alkalinity

1austic soda (5a,H) potassium hydro-ide (3,H) and lime &1a(,H)* drilling fluids at times to increase the pH of the fluid.

( are added to

1ement is a common source of hydro-yl (,H%) ions. The chemical reaction is as follo!s# 1a(,H) 6ime G 1a*' 1alcium *,H% Hydro-yl

9nything added to the drilling fluid that places an ,H% ion in solution !ill increase the pH. The carbonate (1,+ *%) ion has several interesting sources in nature. It is sometimes found in the form of potash (3 1, ). It may also be the product of a chemical reaction taking * + place as a result of a gas kick. 4hen 1,* enters the drilling fluid the follo!ing reaction occurs# 1. 1,* *. H 1,
*

' '

H*, ,H%

G G

H*1,+ 1arbonic 9cid H1, %

+

'H, * ?icarbonate +. H1, ' ,H% G 1, *% ' H , + + * 1arbonate 9 third source of 1,* comes as a byproduct of bacterial action on certain types of organic matter. 7luids that contain mi-tures of vegetable fibers (loss circulation materials) or polymers are subHect to bacterial action. This is also true of fluids that contain certain types of organic filtration control additives. 9 prime e-ample is corn or potato starch. 9 chemical biocide should be added in conHunction !ith the starch to control bacterial activity or !hen the fluids contain biodegradable organic substances.
+

9 fourth source of the carbonate8bicarbonate ion is make%up !ater. 9ny !ater used to mi- or build drilling fluids should be checked for the presence of both ions prior to actual mi-ing of the fluid. The bicarbonate (H1, %) ion generally occurs as the result of 1, gas in the drilling + * fluid# The presence of the H1,+ % ion is dependent upon the pH or ,H% concentration (2ee 7igure 1.) 9lso note the reaction belo! !hich occurs at pH of 1).+ and above. H1,+% ?icarbonate ' ,H% Hydro-yl G H,H ' 4ater 1, + 1arbonate
*%

The reaction sho!s that the bicarbonate ion cannot co%e-ist in a fluid of relative high pH. The hydro-yl ion reacts to produce carbonate and !ater. This concept is used to counteract bicarbonate contamination. The pH range in !hich the ma-imum amount of bicarbonate ions can be found is ".) % 1)./ as seen in 7igure *.

9t a pH of 1)./ and above the ,H% concentration becomes large enough that the above reaction predominates leaving 1,+ *% and !ater. ,ccasionaly bicarbonate of soda can be found in the earthFs formations ho!ever the primary source is 1,* gas. The follo!ing chart sho!s the predominate pH range for the alkalinity ions. p H 4.+ % =.+ 1arbon dio-ide (1,* ) gas mainly in solution pH =.+ % 1).+ ?icarbonate (H1,+%) ion mainly in solution pH 1).+I 1arbonate (1,+ *%) ion mainly in solution 3no!ledge of the relationship bet!een pH and alkalinity can provide insight into !hich ion or ions are in solution and contributing to contamination problems. 7or e-ample it is virtually impossibe to have 1, or H1, % contamination if the pH is 11./ % 1*.). ,n the * + other hand it is also highly unlikely to e-perience 1,+ *% contamination if the pH is >./ % <./. Pf Alkalinity The @f titration is performed on the mud filtrate. @henolphthalein is used as the indicator and 58/) ().)*5) sulfuric acid (H 2, ) is the titrating solution. The endpoint for the * 4 titration occurs !hen 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 >.+ and @f is reported as the number of milliliters of 58/) sulfuric acid used to reach the endpoint. 5oting the pH ranges listed above it is readily seen that in the @f titration the t!o ions that predominate are 1, *% and ,H% !ith a small quantity of H1, % ions present. + + Therefore the t!o reactions !hich occur in the @f titration are# 1. 1, *% + 1arbonate *. ,H% Hydro-yl ' ' H 2, (58/)) * 4 9cid H*2, 4 (58/)) 9cid G G H1, +% ?icarbonate H,H 4ater ' ' H2,4% ?isulfate 2, *% 4 2ulfate

3 d $ K
!

J 9 4
;

'

,
L 16JL

9
11=

)
5
'
4> 4

19 14@

4 1 o ,v
O O

(H

44

I6

4 'M

I1=

L .H
P%Q

6L
-

1.

d ,;

% 1

4 J dR

7igure I

4)

7igure *

In other !ords at the >.+ pH endpoint the follo!ing is true# Sost of the 1, *% has been converted to H1, % as seen in Deaction 5o. 1 and most of + + the ,H% has been converted to H,H as seen in Deaction 5o. *. Therefore it is possible to conclude that !hen there is a high concentration of either ,H% or 1,+ *% ions the @f !ill be rather large. The question is then ho! does one tell !hich ion is presentR In order to determine !hich of the t!o ions is present in the @ titration the S titration must be conducted.
f f

,f the t!o ions (,H and 1, ) only 1, !ill affect the S titration. This is readily + + f seen in Deaction 5o. 1 as the product produced is H1,+ % The bicarbonate ion !ill then manifest itself in the Sf titration.
% *% *%

The follo!ing reaction occurs !hen conducting the second titration to determine Sf# +. H1, %
+

' ?icarbonate

H* 2,4 9cid

1, * 1arbon .io-ide

'

H* , 4ater

'

H2,4% ?isulfate

In Deaction 5o. + most of the H1, % is converted to 1, at the 4.+ pH endpoint. The + * H1,+ % ion determined in this titration may have come from the titration in Deaction 5o. 1 or the H1,+ % ion may have been present in the filtrate prior to conducting any of the titrations. In other !ords high concentrations of 1, *% ions in the @ titration !ill + f produce high concentrations of H1, % ions in the S titration as seen belo!# + f % @ titration converts 1, *% to H1, f + + S titration converts H1, % to 1,
f + *

Alkalinity

9fter performing the the @f titration add methyl orange or bromo%cresol green8methyl orange and continue to titrate !ith 58/) sulfuric acid. If methyl orange is used as the indicator the sample !ill change from orange to salmon%pink !hen the endpoint is reached. If bromo%cresol green is used as the indicator the sample !ill change from blue%green to yello!. The pH of the sample should be appro-imately 4.+ !hen 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 @f endpoint and the total amount of acid used is recorded as Sf alkalinity. The follo!ing is an e-ample titration of a filtrate !ith a pH of 1).4. pH $ 1).4 @f $ +.* ml 58/) H*2,4 to original color pH $ >.+ 1olor change# pink

S $ /.+ ml 58/) H 2,4 f * (+.* ml ' *.1 ml to reduce pH from >.+ to 4.+)

pH $ 4.+

1olor changes from orange to pink or blue to yello!

In the e-ample above a total of /.+ ml of 58/) sulfuric acid !as required to reduce the pH from 1).4 to 4.+. The @ alkalinity is reported as *.1 and the S alkalinity is reported
f f

as /.+ (+.* ' *.1 $ /.+). Lsing the follo!ing diagram it is possible to e-amine @ present in a given titration# and S in terms of the ions
f f

pH ,H% ions ,H% ' 1, *% ions or 1, *% ions + + 11.4 >.+ ,H% ions ,H% ' 1, *% ions or 1, *% ions ' H1,
+ +

7iltrate pH
%

ions

4.+ H1, % ions and 1,* gas + Interferring ions 3no!ing that 1, present in the @f. ,H% !ill not be present in the S f titration High concentrations of ,H% and H1,+ follo!ing reaction# H1, % ' ,H% G H,H ' 1,
+ *% + %
*%

@ f 7iltrate pH S f 7iltrate pH

effects both the @f and the S it is easy to distinguish !hich ion is

f

cannot e-ist simultaneously. This is due to the

If the @ and S values are both high the main contaminant has to be 1, *% If the @ is f f + f high and the S is relatively unchanged the predominate ions are ,H% ions. If the @ f f value is relatively small and the S value is large the predominate ions are H1, % ions.
f +

Delating these values to pH can be easy. 4hen the pH is greater than 1)./ and the @f and *% S values are relatively high the predominating ions !ill be 1, ions. If the pH is less f + than 1).) and the S value is large the predominate ions !ill be H1, % ions. If the pH is f + greater than 1).) @ is high and S is virtually unchanged the predominate ions are f f most likely ,H% ions. H1, % and 1, *% ions can co%e-ist in certain pH ranges therefore + + kno!ledge of the pH can aid in determining !hich of the t!o ions is causing the problem.

!sti"atin# t$e Concentration of OH %& HCO'% and CO'(% Ions in )ater *ase Drillin# +luids If a red color does not develop upon the addition of phenolphthalein to a sample of filtrate the @ is recorded as Cero ()). (2ee 7igure 5o. +.) If @ $ ) the pH is T>.+ and f f the ions contributing to alkalinity are H1, % ions !hich !ill be revealed by the S + f titration and reported as follo!s# ,H% 1,+*% H1, % meq86
+

$ ) $ ) $ S - *)
f

If a pink or yello! color does not develop !hen methyl orange or bromo%cresol green is added to a sample of filtrate follo!ing the titration for @f additional titration !ith acid is not required as the pH is already at 4.+. 4hen this occurs the ions contributing to alkalinity are ,H% ions only. (If 1, *% ions !ere present titration for S !ould have been + f required and its not.) The ions are reported as follo!s# ,H% meq86 $ @f - *) 1,+*% $ ) H1,+% $ ) (4hen a second titration is not required @

$ S.)
f

The follo!ing e-pressions are used to determine the ions contributing to alkalinities. @ $) The alkalinity is all H1, % ions f + @ $S The alkalinity is all ,H% ions f f * - @fI S The alkalinity is a mi-ture of 1, *% and ,H% ions f + *-@ $S The alkalinity is all 1, *% ions f f + *-@ TS The alkalinity is a mi-ture of H1, % and 1, *% ions f f + + The follo!ing e-plains the reasoning behind the statements above# @f $ , @ $, f no (,H%) no (1,+ *% ) >.+ pH *nd $+ ml % H1, + 4.+ pH

Lpon adding the phenolphthalein there !as no color change. This means the pH is already at >.+ or less. Therefore there cannot be any ,H% or 1,+ *% ions in the filtrate. The only ions that can be in the second titration !ill be H1,+ %. ) ml $ ' +ml $ + ml $ (,H%) me86 $ (1,+ *%) me86 $ (H1, %) me86 $
+

@f *nd titration S f ) ) *) - S
f

@ $S
f

@ f $ * ml *nd $)

(,H%) only no (1,+*%) no (H1, ) 4.+ pH

% +

>.+ pH

Lpon adding phenolphthalein a red color develops indicating possible ,H% or 1,+*% ions. 9fter titrating to the >.+ pH endpoint methyl orange is added and immediately a salmon pink color results. This simply means that the >.+ pH endpoint is the same as the 4.+ pH endpoint. In other !ords there is no second titration. Therefore there can be no H1, % ions. 9lso there can not be any 1, *% ions. 1, *% ions !ould have been converted + + + to H1, % in the @ titration and a S titration !ould have follo!ed.
+ f f

(,H%) me86 (1,+ *%) me86 (H1, + %) me86 * - @f I Sf

@f $ * ml

$ $ $

@f - *) ) )

,H % G H *, *% 1, G H1, +

% +

>.+ pH H1, % G 1,
+ *

2ince most of the acid !as used in the @ it is likely that ,H% and 1, *% !ere present. f + 2ince 1, *% sho!s up in the *nd titration it is likely there is some 1, *% because there + + !as a small titration. 4ith H1,+ % present the *nd titration !ould have been much larger.

*nd $ 1 ml 4.+ pH @f *nd S f (,H%) me86 $ * ml $ 1 ml

$ + ml $ (4) - @) % (*) - S) f *% (1, ) me86 $ 4) (S % @) + f f H1,+ % me86 $ ) *-@ IS

f f

@f $1 ml

1, +

*%

G H1,
%

+%

H1, + G 1, * from @ f H1, % G 1, + * *nd $+ ml (present before @f ) 2ince the second titration !as large it is sure that H1, % is present. The @ has to be + f mostly 1, *% because the ,H% !ould have reacted !ith the H1, % to form 1, *% ' H ,. + + + * The H1, % produced in the @ sho!s up in the S. + f f @ f $ 1 ml *nd $ + ml $ 4 ml Sf Demember# H1, % that sho!s up in the S
+ f
*%

titration can come from t!o sources#

+

The titration of the 1,

ion in the @ yields H1, % ion.

f + f

There may be some H1, % ions in the filtrate prior to running the @ (,H ) (1, *%) me86 + (H1, %)
%

or S test.
f

$ ) $ 4) - @ f $ (*) - S) % (4) - @)
f f

* - @f $ S

@ $ * ml
f

U1,
+

*%

G H1,
%

% +

*nd

UH1,
$ * ml

titration +

G 1,

In the case !here * - @ $ S it is easy to see that the only ion present is 1, *% If the f + alkalinity !as solely from H1, % then the @ !ould have been small because H1, % does + f + not effect the @f. The @f could not have been from ,H% and H1,+ % as they cannot co% e-ist in high concentrations at the same time.
f

* Sf ' * ml 4 ml

$ @f

$ *nd $ S f
%

In other !ords all 1, *% in the @

+

!as converted to H1, !as then converted to 1, in the S titration.

f * f

in the @ titration. The H1, %

f

$ 4) - pf (H1,+ %) me86 $ ) 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.
+ *%

(,H%) (1,

$ ) )

P, P( Alkalinity In determining @1 * ml of 581) ().1 5) 5a,H is added to the mud filtrate. The 5a,H is required to raise the pH above 11.4. 9bove 11.4 pH any H1,+ % !ill be converted to 1,+ *% via the follo!ing reaction# H1, % ?icarbonate
+

'

,H% G 5a,H * mls 581)

1, *% ' + 1arbonate

H,H 4ater

The ne-t step is to add ?arium 1hloride (?a1l* ). Demember never pipette barium chloride as it is to-ic. The barium (?a) reacts !ith 1, *% to form insoluble ?a1, + + (barium carbonate)# 1, *%
+

' ?a1l* 1arbonate ?arium 1hloride 1hloride

?a1, + V ' ?arium carbonate

1l%

This leaves only ,H% in solution. The concentration of ,H% !ill equal the original concentration of ,H% in the filtrate plus that added via 581) 5a,H. 7rom the total (,H%) concentration one must no! subtract the ,H% ions used in the conversion of H1,+ % to 1,+ *%. :mperically it looks like this# Hydro-yl 1oncentration (,H%) ' ,riginal In 7iltrate (,H%) G 7rom 581) 5a,H added (,H%) ' Lsed in conversion of *% H1, % to 1,
+ +

(,H%) 9fter adding ?a1l *

The ,H% concentration remaining after the addition of ?a1l * in step * is then titrated !ith (58/)) hydrochloric acid. ,H% Hydro-yl 9fter ?a1l* is added ' H1l G H,H ' 58/) 4ater hydrochloric acid 1l% 1hloride

In determining @ the e-act same procedure for determining @ is follo!ed e-cept that * 1 the mud filtrate is left out. @ measures the total ,H% !hich !as added in @ .
* 1

If @ I @ this indicates that none of the ,H% ions in @ !ere consumed in the conversion 1 * 1 of H1, + % to 1, + *%. Therefore the only ions in the filtrate are 1, +*% ' ,H%. 2ince the 1, +*% !as removed by the ?a11* the ,H% concentration is equal to the difference in the amount of acid used in @ and in @ .
1 *

2o me86 (,H%) $ *) - (@ % @ )
1 * f

or

mg86(,H) $ +4) (@ % @ )
1

*
*%

2ince the @ gives a total amount of H1l to neutraliCe both the 1, S:86 1, *% $ @ % (@ % @ ) - 4)
+ f 1 *

and the ,H% then

1 *

or

mb86 1,

*% +

$ 1*)) &@f % (@ % @ )W

The me86 of acid used in neutraliCing the 1,+ *% must be multiplied by * since the carbonate ion has a %* charge. Therefore the multiplying factor of Sg86 for 1,+*% becomes 4) instead of *). To covert to mg86 of 1,+ *% multiply the me86 - =)8* (:q!t of 1,+ *%. If @1 T @ this indicates that some of the 581) 5a,H added in @
* 1

!as consumed in the ' H,H 4ater

follo!ing reaction# 5aH1, + 2odium ?icarbonate ' ' 5a,H 2odium hydro-ide G 5a 1, 2odium carbonate
* +

2ince @ $ total ,H% concentration added in @ * in converting the H1, % to 1, *%. Therefore
+ +

the @ % @ $ the amount of acid (ml) used

* 1

me86 H1,

mg86 H1, *% $ 1*)) @ + f It has been established that 4) - @ % (@ % @ ) $ me86 1, *%. Ho!ever one cannot ave f f * + H1, % and ,H% ions simultaneously in the mud filtrate only H1, % and 1, *%.
%

$ *) - (@ % @)
*

or

If ,H% $ ) then @ % @
+ f

$ ) and the equation for determining the me86 1, *% becomesX 1 * + 1, *% $ 4) - @ % ()) since @ % @ $ ). This simplifies to 4) - @.
1 * f

2o me86 1, $ 4) - @ !hen @ T @ .
*%

,r

mg86 1a1,

*%

$ 1*)) @

The @ % @ is a alternate test but it has a standard place on the daily drilling mud report. 1 * It is not normally run unless an alkalinity problem may e-ist. (?9DILS 1H6,DI.: TITD9TI5E 2,6LTI,5 I7 I5E:2T:. 195 3I66 M,L).