Chapter 9

pH Control Additives

The pH means potentia hydrogenii and is defined as the negative decadic

logarithm of the concentration of protons or hydrogenated protons, respectively.
For example, a concentration of protons of 10−12 mol l−1 means a pH of 12.
Similar considerations are valid for equilibrium constants K , that are
sometimes expressed in terms of pK values.
Water dissociates to a small extent into protons or more correctly into
hydrogenated protons and hydroxyl ions, i.e.,

H2 O → H+ + OH− . (9.1)
In the presence of water, the proton as such is not stable, but will be attached
to another molecule of water:

H+ + H2 O → H3 O+ . (9.2)
For simplicity we will deal often only with H+ . The equilibrium constant
of the dissociation reaction, Eq. (9.1), is

[H+ ][OH− ]
K H2 O = . (9.3)
[H2 O]

The equilibrium constant K H2 O has in general a physical dimension. Since

the concentration has the physical dimension of mol l−1 , K H2 O has the physical
dimension of mol l−1 .

THEORY OF BUFFERS
The theory of buffers is a common part of physical chemistry, e.g., in the book
of Chang (2000). A protic acid A = B−H decomposes in the first step into a
proton H+ and into a base B− .

BH → H+ + B− ,
(9.4)
B− + H2 O → BH + OH− .

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116 Hydraulic Fracturing Chemicals and Fluids Technology

For the two reactions in Eq. (9.4) we have two equilibrium constants, for
the acid
[H+ ][B− ]
KA = (9.5)
[BH]
and for the base
[OH− ][BH]
KB = . (9.6)
[B− ][H2 O]
Summing up the two individual equations of Eq. (9.4), yields again the
dissociation equation if water.

H2 O → H+ + OH− . (9.7)
Therefore,
K A K B = K H2 O . (9.8)
As a further equation we have the balance of water

[H2 O]0 = [H2 O] + [H+ ]. (9.9)

Here [H2 O]0 is the concentration of the undissociated water. From the
principle of electroneutrality it follows

[H+ ] = [OH− ]. (9.10)

The equilibrium constant for water is very small, therefore we may safely
approximate [H2 O]0 ≈ [H2 O].
The relation
[H2 O]0 K H2 O = [H+ ][OH− ] (9.11)
is addressed as the ionic product of water. It is close to 10−14 mol2 l−2 .
Inserting Eqs. (9.10) and (9.9) into Eq. (9.3) results in

[H+ ]2
K H2 O = . (9.12)
[H2 O]0 − [H+ ]
From the relations Eq. (9.11) or Eq. (9.9) the pH of pure water can be calculated.
An extension of the above equations to weak acids and bases, Eq. (9.4) will
allow to calculate the pH value in buffer systems, as well as titration curves.
Common aqueous buffer ingredients are shown in Table 9.1 and in Figures 9.1
and 9.2.
Buffers, necessary to adjust and maintain the pH, can be salts of a weak
acid and a weak base. Examples are carbonates, bicarbonates, and hydrogen
phosphates, such as formic acid, fumaric acid, and sulfamic acid (Nimerick,
1996).
Increased temperature stability of various gums can be achieved by adding
sodium bicarbonate to the fracturing fluid and thus raising its pH to 9.2–10.4.
CHAPTER | 9 pH Control Additives 117

' $
TABLE 9.1 Common Buffer Solutions (Kolditz, 1967)

Reaction pKA
HCl → H+ + Cl− −7
H2 SO4 → H+ + HSO−4 −3
HSO− 2−
4 → SO4 + H
+ 1.92
H2 SO3 → HSO−3 +H
+ 1.92
−
HF → F + H + 3.14
CH3 COOH → CH3 COO− + H+ 4.75
H2 S → HS− + H+ 6.92
NH+4 → NH3 + H
+ 9.25
H2 O → H+ + OH− 15.47
Oxalic acid/hydrogen oxalate 1.27
Maleic acid/hydrogen maleate 1.92
Fumaric acid/hydrogen fumarate 3.03
Citric acid/hydrogen citrate 3.13
Sulfamic acid/sulfamate 1.0
Formic acid/formate 3.8
Acetic acid/acetate 4.7
Dihydrogen phosphate/hydrogen phosphate 7.1
Ammonium/ammonia 9.3
Bicarbonate/carbonate 10.4
Fumaric acid/hydrogen fumarate 3.0
Benzoic acid/benzoate 4.2

& %

OH
O C H
H O
O C C
H C O N S O
H C H
O H
OH OH

Formic acid Fumaric acid Sulfamic acid

FIGURE 9.1 Weak organic acids.

pH CONTROL
The buffer to be used depends on the intended pH range. For fracturing flu-
ids, several buffer systems have been recommended that are summarized in
Table 9.2.
For applications with zirconium crosslinked guar gums, the use of a
combination of buffers together with the use of an α-hydroxycarboxylic acid
118 Hydraulic Fracturing Chemicals and Fluids Technology

O O O O
O
H3C C C C C CH2 C
OH HO OH HO OH

Acetic acid Oxalic acid Malonic acid

O O O O
C CH CH C C CH2 CH2 C
HO OH HO OH

Maleic acid Succinic acid

O O O
C CH2 CH2 CH2 CH2 C C
HO OH OH

Adipic acid Benzoic acid

O O

C C OH
CH3 HO

O O HO C OH
C C C
OH OH O O

Benzoic acid o-Toluic acid Benzene tetracarboxylic acid

FIGURE 9.2 Carbonic and dicarbonic acids.

or its salt offers an advantage in that the crosslink delay time of the newly
proposed fluid is controllable over a wider pH range (Moorhouse and Matthews,
2004).

' $
TABLE 9.2 Buffer Systems (Putzig, 2012)

pH Range Buffer System

5–7 Fumaric acid
5–7 Sodium diacetate
7–8.5 Sodium bicarbonate
9–12 Sodium carbonate
9–12 Sodium hydroxide

& %
CHAPTER | 9 pH Control Additives 119

REFERENCES
Chang, R., 2000. Physical chemistry for the chemical and biological sciences. University Science
Books, Sausalito, California (Chapter 11).
Kolditz, L. (Ed.), 1967. Anorganikum: Lehr- und Praktikumsbuch der anorganischen Chemie; mit
einer Einführung in die physikalische Chemie. Dt. Verl. der Wiss., Berlin, p. 413.
Moorhouse, R., Matthews, L.E., 2004. Aqueous based zirconium (iv) crosslinked guar fracturing
fluid and a method of making and use therefor. US Patent 6 737 386, assigned to Benchmark
Research and Technology Inc., Midland, TX, 18 May 2004. <http://www.freepatentsonline.
com/6737386.html>.
Nimerick, K., 1996. Fracturing fluid and method. GB Patent 2 291 907, assigned to Sofitech NV, 7
February 1996.
Putzig, D.E., 2012. Zirconium-based cross-linking composition for use with high pH polymer
solutions. US Patent 8 247 356, assigned to Dorf Ketal Speciality Catalysts, LLC, Stafford,
TX, 21 August 2012. <http://www.freepatentsonline.com/8247356.html>.