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Buffer capacity,
Carbonate buffering,
Carbonate alkalinity,
Acid absorption capacity
*
* 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
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
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
B(OH)4- + H+ = H3BO3+H2O
A seawater analysis
0.1L sample titrated using 0.1M HCl
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
*
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
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
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
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
*
*
Bicarbonate buffer
Acetate buffer
*
0.003 mol (183ppm) bicarbonate-1
0.002 mol (120ppm) acetate-1
0.0002 mol (9 ppm) formate-1
Do Chapter 10 – Alkalinity
And we’ll discuss the results
H2CO3+OH-=HCO3- + H2O
*
A Buffer against base
Any chemical that will absorb a OH- ion in the pH region where the buffer is active