*

A combination of acids, bases, and pH

 The amount of acid or base that a water can
tolerate before the pH changes significantly.

a.k.a.
Buffer capacity,
Carbonate buffering,
Carbonate alkalinity,
Acid absorption capacity

In Produced water, Alkalinity is usually bicarbonate

*
Buffer Titration product Buffer Titration producct

*
* It keeps the water pH stable – pH will not
change significantly if acids are added (like
stimulation fluids)
* It protects against corrosion because it reduces
the amount of free acid (H+)

*
 pH buffer zone
(~5.3-7.3pH)

HCO3- + H+ = H2CO3

The acid volume needed to consume the buffer pH

inflection
point

Acid consumed at
inflection point

*
A buffer against Acid
Any chemical that will absorb H+ ions in the pH region where the buffer is active
 HCO3- + H+ = H2CO3
Available Buffer Consumed Buffer

Excess Acid

*
 HCO3- + H+ = H2CO3
Available Buffer Consumed Buffer

Excess Acid

*
*
 Buffer Buffering reaction Buffering pH Titration Conc. range in
Region (pH)1 End Point reservoir water

Carbonate CO3-2 + H+ = HCO3- 11.3 to 9.3 8.3 <1

Bicarbonate HCO3- + H+ = H2CO3 7.3 to 5.3 4.32 100-1000

Formate HCOO-+H+=HCOOH 4.8 to 2.8 1.8 1-100

Acetate CH3COO- + H+ = 5.7 to 3.7 2.7 20-2000

CH3COOH
Propanate C2H5COO- + H+ = 5.9 to 3.9 2.9 1-100
C2H5COOH
Borate H4BO4- + H+ = H3BO3+ ~10 to 8 6.5 10-300
H2O
Ammonia NH3 + H+ = NH4+
* 10.2 to 8.2 7.2 <10

Sulfide S-2 + H+ = HS- 12 to 10 9 <1

Bisulfide HS- + H+ = H2S 8 to 6 5 1-100

1 – This represents about 90% of the buffering region

2 – Recognize this endpoint? This is the Total alkalinity endpoint we use in produced water analyses
* Acid consumes the
buffer
* Converting to an
equilibrium equation

* The value of the

K .

determines the pH
buffer range

*
 pH region where the HCO3-1
buffer is active

HCO3- + H+ = H2CO3

*
HCO3-1 buffers between pH=7.3 and pH=5.3 (at zero salinity)
 pH region where the Acetate-1
buffer is active

CH3COO- + H+ = CH3COOH

*
Acetate-1 buffers between pH=5.7 and pH=3.7 (at zero salinity)
 pH region where the HS-1
buffer is active

HS- + H+ = H2S

HS-1 buffers between pH=8 and pH=6 (at zero salinity)

 pH region where the B(OH)4-1
buffer is active

B(OH)4- + H+ = H3BO3+H2O

B(OH)4-1 buffers between pH=10 and pH=8 (at zero salinity)

Cations Mg/l Anions Mg/l Neutrals Mg/l
Na+1 10561 Cl-1 18980 SiO2 5
K+1 380 SO4-2 2648
Ca+2 400 Br-1 65
Mg+2 1272 B(OH)4-1 33.6
Sr+2 13 F-1 1.4
Ba+2 0.05 I-1 0.05
Li+1 0.1 HCO3-1 144

A seawater analysis
 0.1L sample titrated using 0.1M HCl

Two inflection points

Inflection point

Titration endpoint

*
 First inflection Point Second Inflection Point
Acid volume (L) pH Acid volume (L) pH
0.00044 7.38 0.00245 5.12
0.00053 7.09 0.00254 5.00
0.00061 6.87 0.00263 4.85
0.00070 6.71 0.00271 4.66
0.00079 6.58 0.00280 4.42
0.00088 6.47 0.00289 4.18
0.00096 6.37 0.00298 3.98

*
* Calculate Total Alkalinity from total volume
acid used
* Calculate Alkalinity using acid volume from
first titration point
* Calculate Alkalinity using acid volume from
first to second titration point
* Compare all three results to seawater
concentrations

*
Additional experimental data
Acid Concentration 0.1 moles/l
Sample volume 0.1 L

*
Total Alkalinity (total acid used)
𝑚𝑔 𝑚𝑜𝑙𝑒𝑠 𝑚𝑔 𝐻𝐶𝑂 1
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂 = 0.00289 𝑙 ∗ 0.1 ∗ 61020 ∗
𝑙 𝑙 𝑚𝑜𝑙𝑒 0.1 𝑙
𝑚𝑔
= 176.3
𝑙

Alkalinity to first inflection (0.00053 L acid used)

𝑚𝑔 𝑚𝑜𝑙𝑒𝑠 𝑚𝑔 𝐻𝐶𝑂 1
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂 = 0.00053 𝑙 ∗ 0.1 ∗ 61020 ∗
𝑙 𝑙 𝑚𝑜𝑙𝑒 0.1 𝑙
𝑚𝑔
= 32.3 𝑎𝑠 𝐻𝐶𝑂
𝑙

Alkalinity to second inflection (0.00289 L-0.00053 L = 0.00236 L acid used)

𝑚𝑔 𝑚𝑜𝑙𝑒𝑠 𝑚𝑔 𝐻𝐶𝑂 1
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂 = 0.00236 𝑙 ∗ 0.1 ∗ 61020 ∗
𝑙 𝑙 𝑚𝑜𝑙𝑒 0.1 𝑙
𝑚𝑔
= 144 𝑎𝑠 𝐻𝐶𝑂
𝑙

*
 Cations Mg/l Anions Mg/l
Na+1 10561 Cl-1 18980
K+1 380 SO4-2 2648
Ca+2 400 Br-1 65
Mg+2 1272 B(OH)4-1 33.6 𝐹𝑖𝑟𝑠𝑡 𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑒𝑛𝑑 𝑝𝑜𝑖𝑛𝑡
Sr+2 13 F-1 1.4 𝑚𝑔
= 32.3 𝑎𝑠 𝐻𝐶𝑂
Ba+2 0.05 I-1 0.05 𝑙
Li+1 0.1 HCO3-1 144
𝑆𝑒𝑐𝑜𝑛𝑑 𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑒𝑛𝑑 𝑝𝑜𝑖𝑛𝑡
𝑚𝑔
= 144 𝑎𝑠 𝐻𝐶𝑂
𝑙

If the total alkalinity value us used to calculate the bicarbonate concentration, then other
alkalinity contributing species should be removed. Otherwise the value will be incorrect. The
bicarbonate alkalinity is 144 mg/l and not 176.3 mg/l.
*
1 L sample titrated using 0.1M HCl

*
 dpH/dvol vs. volume acid
0
-0.1
-0.2
-0.3

dpH/dvol
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1
5 5.5 6 6.5 7 7.5 8
volume acid (ml)

6.8 ml

The infection point is between 3.9 and 4.8 pH

 𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂
𝑙
𝑚𝑜𝑙𝑒𝑠
= 𝐴𝑐𝑖𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑖𝑛𝑓𝑙𝑒𝑐𝑡𝑖𝑜𝑛 𝑝𝑜𝑖𝑛𝑡 𝑙 ∗ 𝐴𝑐𝑖𝑑 𝐶𝑜𝑛𝑐.
𝑙
𝑚𝑔 𝐻𝐶𝑂 1
∗ 61.02 ∗
𝑚𝑜𝑙𝑒 𝑆𝑎𝑚𝑝𝑙𝑒 𝑉𝑜𝑙 𝑙

𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂
𝑙
𝑚𝑜𝑙𝑒𝑠 𝑚𝑔 𝐻𝐶𝑂 1 𝑚𝑔
= 0.0068 𝑙 ∗ 1.0 ∗ 61020 ∗ = 415 𝑎𝑠 𝐻𝐶𝑂
𝑙 𝑚𝑜𝑙𝑒 1 𝑙 𝑙

*
Cations (mg/L) Anions (mg/L)
Na+1 1800 Cl-1 3090
K+1 60 SO4-2 55
Ca+2 220 HCO3-1 400
Mg+2 30
Sr+2 60
Ba+2 10
Fe+2 2

𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 = 415 𝑎𝑠 𝐻𝐶𝑂
𝑙

*
*
 1 L sample titrated using 0.1M HCl

*
 dpH/dvol vs. volume acid
0

-0.1

-0.2

dpH/dvol
-0.3

-0.4

-0.5

-0.6

-0.7
10 11 12 13 14 15
volume acid (ml)

13.5 ml

The infection point is between 3.6 and 4.2 pH

 𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂
𝑙
𝑚𝑜𝑙𝑒𝑠
= 𝐴𝑐𝑖𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑖𝑛𝑓𝑙𝑒𝑐𝑡𝑖𝑜𝑛 𝑝𝑜𝑖𝑛𝑡 𝑙 ∗ 𝐴𝑐𝑖𝑑 𝐶𝑜𝑛𝑐.
𝑙
𝑚𝑔 𝐻𝐶𝑂 1
∗ 61.02 ∗
𝑚𝑜𝑙𝑒 𝑆𝑎𝑚𝑝𝑙𝑒 𝑉𝑜𝑙 𝑙

𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂
𝑙
𝑚𝑜𝑙𝑒𝑠 𝑚𝑔 𝐻𝐶𝑂 1 𝑚𝑔
= 0.013 𝑙 ∗ 1.0 ∗ 61020 ∗ = 793 𝑎𝑠 𝐻𝐶𝑂
𝑙 𝑚𝑜𝑙𝑒 1 𝑙 𝑙

*
Cation Conc Anions Conc Neutrals Conc
(mg/l) (mg/l) (mg/l)
Na+1 11600 Cl-1 19000 CO2 110
K+1 140 HCO3-1 800 H2S 70
Mg+2 650 SO4-2 200
Ca+2 100
Sr+2 125
Ba+2 1
Fe+2 10

*
*
1 L sample titrated using 0.1M HCl

*
 dpH/dvol vs. volume acid
0

-0.05

-0.1

dpH/dvol
-0.15

-0.2

-0.25

-0.3
1 1.5 2 2.5 3
volume acid (ml)

13.5 ml

The infection point is between 3.5 and 3.9 pH

 𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂
𝑙
𝑚𝑜𝑙𝑒𝑠
= 𝐴𝑐𝑖𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑖𝑛𝑓𝑙𝑒𝑐𝑡𝑖𝑜𝑛 𝑝𝑜𝑖𝑛𝑡 𝑙 ∗ 𝐴𝑐𝑖𝑑 𝐶𝑜𝑛𝑐.
𝑙
𝑚𝑔 𝐻𝐶𝑂 1
∗ 61.02 ∗
𝑚𝑜𝑙𝑒 𝑆𝑎𝑚𝑝𝑙𝑒 𝑉𝑜𝑙 𝑙

𝑚𝑔
𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑎𝑠 𝐻𝐶𝑂
𝑙
𝑚𝑜𝑙𝑒𝑠 𝑚𝑔 𝐻𝐶𝑂 1 𝑚𝑔
= 0.002 𝑙 ∗ 1.0 ∗ 61020 ∗ = 122 𝑎𝑠 𝐻𝐶𝑂
𝑙 𝑚𝑜𝑙𝑒 1 𝑙 𝑙

*
Cation Conc Anions Conc
(mg/l) (mg/l)
Na+1 82000 Cl-1 145000
K+1 900 HCO3-1 120
Mg+2 2050 SO4-2 90
Ca+2 8000 Br-1 400
Sr+2 250
Ba+2 230

*
 *

The Alkalinity titration represents the total

alkalinity, not only bicarbonate
 Borate buffer

Bicarbonate buffer

Acetate buffer

Traditional Alkalinity Endpoint Formate buffer

0.001 mol (78 ppm) borate-1

*
0.003 mol (183ppm) bicarbonate-1
0.002 mol (120ppm) acetate-1
0.0002 mol (9 ppm) formate-1

Notice how the buffers overlap

Let’s test this out in ScaleChem

Do Chapter 10 – Alkalinity
And we’ll discuss the results
 H2CO3+OH-=HCO3- + H2O

The amount of base added to consume the acid buffer

*
A Buffer against base
Any chemical that will absorb a OH- ion in the pH region where the buffer is active