FORMATE MAN A6 PH and Buffering

C ABOT SP E C I A LT Y F L U I D S F O RM ATE TECH N ICAL M AN UAL
CH EMIC AL AND PH Y S ICAL PR OPE R T IE S
Section A6
pH and Buffering
A6.1 pH of formate brines ..............................................................................2

A6.1.1 Controlling pH in formate brines . ....................................................3
A6.1.2 Measuring pH in formate brines . ....................................................3
A6.2 pH buffering of formate brines ..............................................................5

A6.2.1 How the carbonate / bicarbonate buffer works ..............................5
A6.2.2 Buffer protection against CO2 influx ................................................6
A6.2.3 Buffer protection against H2S influx .................................................6
A6.3 Buffering requirement and buffer capacity ........................................... 7

A6.3.1 Buffer capacity ................................................................................ 7
A6.3.2 Buffer concentration . ...................................................................... 7
A6.3.3 Buffer requirement for field use ......................................................8
A6.3.4 Determining buffer concentration and capacity ................................. 8
A6.3.5 Maintaining buffer concentration and capacity .................................10

References ..................................................................................................... 10
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V ER S IO N 1 – 1 2/ 07 SSEECCTTI IOON
N A
A66 PAGE 1
C ABO T S PE C I A LT Y F L U I D S 1 pH = − log [H + ] FORMAT E T EC HNI C AL MANUA L
2 pH = − log(a H + ) aH +
A6.1 pH of formate brines 3 Ka

HCOO− + H3 O +←⎯→ HCOOH + H2 O pKa (3)
pH is a measure of the acidity or alkalinity of a pKa2=

− 3.75 pKa − 2− −
4 CO3 + H + ←⎯ → HCO3 2
pKa2 CO3 HCO3
solution, numerically equal to 7 for neutral solutions,
increasing with increasing alkalinity and decreasing 5 The
HCO3pH
−
of+ formate
+H ←⎯⎯
pKa1
→ Hbrine
2 CO3
can be decreased
pKa1 toHCO3
−
H2 CO3
with increasing acidity. For dilute solutions, pH can 3.75 by adding a strong acid, but the brine will
be defined as the negative logarithm base 10 of the resist further pH change until all the formate ions
hydrogen concentration in the solution [H +]: 6 CO 2 ( g )been
have ←⎯→ CO 2 ( aq )
converted to formic acid ions.
1 pH = − log [H + ] (1) At a pH of 3.75, the formic acid and formate anions

will exist in a 1:1 molar ratio. When the pH of a
2 pHmore (a H + )
= − logconcentrated aH + CO2 ( aq) + H H 2CO3 ( aq
or) lowered one unit from this
In solutions, the behavior 7 formate 2O ←
brine ⎯→
is raised
3
of the −ions in +the K a solution depends not on their
pKa
value the ratio of formate to formic acid will change
HCOO + H3 O ←⎯→ HCOOH + H2 O
concentrations, but on activities. Thus, in reality, by a factor of
H2 CO3 ( aq) ←⎯
K a approximately
− ten, as shown in Table
⎯→ HCO3 ( aq) + H + ( aq)
8 1
apHmore precise
+
] a definition is: 1. Figure 1 shows how the pH of unbuffered formate
1 2=− − log [ H pK − 2− −
4 CO3 + H + ←⎯ → HCO3
2
pKa2 CO3 9 HCObrine
CO
3 3
2−
+changes
H + ←⎯ ⎯→with
Ka
HCOthe
3
−2
addition of a strong acid.
2 pH = −− log(a+H + ) pK a + (2)
H = − log [H5+ ] HCO3 + H ←⎯⎯ a1
→ H2 CO3 H pKa1 HCO3
−
H2 CO3
Table−1 ‘Theoretical’ formate
2− / formic acid molar ratio
3 HCOO −
+ H O +
← Ka
⎯→ HCOOH + H O pK 10 HCO3 + OH − ← ⎯→ CO3 + H 2O
H = − log(a H + ) where a H + 3is the activity. 2 a as a function of pH
6 CO2 ( g ) ←
Ka
⎯→ CO2 ( aq )
HCOO− + H3 O +←⎯→ 2HCOOH
Commonly +pKHa22 O high-density − pKa − 2 − pH Approx. formate / formic acid molar ratio
CO3 + H + ←used oilfield brines pKa2 (CaCl CO32, 11 HCOCO
−
3 + CO2 + H 2O ⎯ ⎯→ 2HCO
− 2−
4 ⎯→ HCO3 3 3
CaBr2, and ZnBr2) have a naturally acidic pH. 6.75 1 000
2− 2+
2− HCO
+ 5 pKa 2 Attempts
−
− + H to
+
← ⎯
pKa1
⎯
raise → H
the CO pH to alkaline 2 − levels pK in HCO
−these
−
12 H2 CO CO 3 ( aq) + Ca ( aq) ⎯ ⎯→ ↓ CaCO3 ( s)
CO3 + H ←⎯→ HCO3 3 2 pKa2
3 CO3 HCO3
a1 3 3
5.75 100
[ CO32− ]
7 pKa halide-based
CO2 ( aq) + H 2O ← brines
⎯→ H 2CO can
3 ( aq)
result in precipitation
13 CO ( g )
4.75 + H O ← ⎯→K
HCO
−
+ H +
( aq) s
= A exp( B × pH )
−
HCO3 + H ←⎯⎯1of +
H CO3
→ insoluble calcium or pK zinc HCO
−
H2 CO3 2, 2 2 3 10 [ HCO− ]
a1 salts. (e.g.
3 Ca(OH)
CO2 (2g ) ←
3
6 ⎯→ CO2 ( aq )
Zn(OH)2). 3.75 1
H2 CO3 ( aq) ←⎯
K a1 −
⎯→ HCO3 ( aq) + H + ( aq) [H + ] × [HCO3 − ]
8 14 K = 2.75
CO2 ( g ) ←⎯→ CO2 ( aq ) PCO2 0.1
Formate
2− salts K a2 dissolved − in water exhibit a naturally
9 CO3 + H + ←⎯ ⎯→ HCO3 15 pH = 1.75 − log K − log PCO2 + log[HCO3 ] 0.01
− 2−
OH − CO32 − HCO3 − [CO3 ] [HCO3 ] H 2 SO4
−
alkaline pH (8 – 10). The pH of the formate brines
7 CO ( aq) + H 2O ← ⎯→ H 2CO3 ( aq) 0.75 0.001
can2 be adjusted to almost any level with common
− − 2−
10 HCO3 and
acids + OHbases ← ⎯→ CO without
3 + H 2causing
O the precipitation 16 0.02× Pf
CO2 ( aq) + H 2O ← ⎯→ H 2CO3 ( aq) K a 1
8 of
H2insoluble
CO3 ( aq) ←⎯ salts.
⎯→ HCO The −
pH of fluids
3 ( aq) + H ( aq)
+
based on formate The pKa value in formate brines has been shown to
brines can therefore be safely adjusted to the level 17 [CO32 − ] + [OHwith
increase
−
] = 0temperature
.02× Pf ( mol / L ) [1]. In very concentrated [ CO32 − ]( mg / L) = 1200 × Pf
2− −
119⎯ CO 2 −+ CO ++ HK aO
CO3 delivers
3 −+ H ←⎯2 ⎯2 2 ⎯ ⎯→
+ → HCO3
2HCO−
3
→that the optimal performance. brines,
[HCO3− ] =pH (and thereby pKa) are poorly defined.
K
H2 CO3 ( aq) ← ⎯ a1
HCO 3 ( aq) + H ( aq) 0 [CO32 − ]( kg / m3 ) = 1.2 × Pf
2−
18
2+
2−
12 K a2
CO 3 ( aq
−
) + Ca ( aq ) ⎯ ⎯→ ↓ CaCO 3 ( s )
CO3 + H + ←⎯ ⎯→The HCO3−
HCOformate − ion is a2 buffer
CO3 +− H 2O+in itself, and [ COformate
− 2−
10 3 + OH ← ⎯→ ]
13 CO2 ( g) therefore
brines + H 2O ←⎯→have K
HCO3a +natural H ( aq) buffering −capacity s
3
= A exp( B at× pH
19 ) [OH − ] = 0 [CO3 2− ] (ppb) = 0.42× Pf [C
[ HCO3 ]
−
HCO3 + OH ← − low pH:
2−
⎯→ CO23− ++ H 2O
11 CO3 [H + CO + H 2O
] ×2[HCO − ⎯→ 2HCO −
] 20 [CO32 − ] = 0.02× Pf ( mol / L)
3 ⎯ 3
14 K=
2− PCO2 2+
CO3 + CO2 12
2−
+ H 2O ⎯ CO3 2HCO
⎯→ ( aq) + −Ca ( aq) ⎯ ⎯→ ↓ CaCO − 3
( s) 2− −−
HCO3 of[CO 213 ] [HCO
2− −
15 pH = − log K 3 − log P
CO2 + log[HCO3 ] OH − CO [HCO ] H SO [ OH − ] [CO
pH23−behavior
[ CO ] unbuffered 3 ] = 02
3formate brines
4
K − 3
= A exp( B × pH )
CO3 ( aq) +13
+
Ca 2+ ( aqCO 2 ( g) ↓ + H 2O ←⎯→ HCO3 + H ( aq) s
2−
)⎯
⎯→ 14CaCO 3 ( s) [ HCO3− ] [OH − ] = 0
22
16 K 0.02× Pf− [ CO3
2−
]
CO2 ( g) + H 2O ←⎯→ HCO [H ] ×+
+ [H +
HCO ( aq3 )]
− s = A exp( B × pH )
14 K = 2 − 312 − [ HCO3− ] 23 [CO32 − ] = 0.02× Pf ( mol / L)
17 [CO3 ] + [OH PCO2 ] = 0.02× Pf ( mol / L ) [ CO32 − ]( mg / L) = 1200 × Pf
[H + ] × [HCO
15 3 ] pH = −− log
−
10 K − log PCO + log[HCO3 − ] OH − CO32 − HCO3 − [CO
2−
2 −3 ] [HCO
−
[ CO []OH ] [CO
−
K= 3 3 ]− H SO
18 [HCO3 ] = 0 No formic acid
2
[CO324 ]( kg / m
[ HCO ) = 1.]2=× P2f 4 32− ( mol/ L)
PCO2
A . exp ( B . pH )
3
pH = − log K − log PCO2 + log[HCO3 ] 8 − −

OH Traces 2−
CO3 of HCO3
−
[ CO3
2−
] −
[HCO3 ] H 2 SO4 [ OH ] [CO −11 −
16 0.02× Pf 25 A = 9.69164 10
19 [OH −pH ]= 0 formic acid [CO3 2− ] (ppb) = 0.42× Pf [CO3 2− ]
6 BL=
[ CO26 ]( mg /pK )a=2=.1200
29762135
3.75× P
2−
[CO 2 − ] + [OH − ] = 0.02× P ( mol / L )
.02× Pf 17 20 [CO332 − ] = 0.02× Pf ( mol / fL) 3
50%−formate f
27 [ OH formic
50% ] = 0 acid
[HCO − ] =40 [CO32 − ]( kg / m3 ) = 1.2 × Pf
CO3 ] + [OH18− ] = 0.02× Pf 3( mol / L ) [ CO32 − ]( mg / L) = 1200
2−
× Pf [ 2−
]=0
28 CO 3
21 [HCO3− ] =20
−
HCO3 = 0 ] 2−
[CO3 ]( kg / m ) = 1.2 × P2f−
3 − 2− −
pKa
19 [OH −− ] = 0 [CO3 ] (ppb)OH = 0.42× Pf
CO3 [
CO3 ]
2− HCO3
22 [OH ] = 00
[OH ] −
[CO3 ] 2−
[ HCO3 ] −
Pf H 2 SO4
[CO322 −− ] = 0.02× Pf ( mol / L)
OH − ] = 0 20 [CO3 2− ] (ppb) = 0.42Addition 2−
23 [CO ] = 0.02× P ( mol / L) × Pf of[CO
strong
3
] acid
3 f
2−
CO3 ] = 0.02× Pf ( mol / L)
Figure
21 [HCO3−1] =Graph shows
0 [ CO 32 −
] how the pH of unbuffered formate brine changes with the addition of a strong acid.
24 [ HCO3− ] = . . ( mol/ L)
A exp ( B pH )
− 22 [OH − ] = 0
HCO3 ] = 025 A = 9.69164 10−11
PAGE 2 SECTION A6 VE R SION 1 – 1 2 / 0 7
OH − ] = 0 23 [CO32 − ] = 0.02× Pf ( mol / L)
26 B = 2.29762135
2−
CO3 ] = 0.02 [OH/ −L])= 0
27× P ( mol [ CO32− ]
f
24 [ HCO − ] = ( mol/ L)
28 [CO32 3− ] = 0A . exp ( B . pH )
SECTION A: CHEMICAL AND PHYSICAL PROPERTIES CABO T S P ECIALTY FLUIDS
A6.1.1 Controlling pH in formate brines method is not recommended in concentrated

There are two means of controlling pH in formate halide brines because interference with the divalent
brines: cations (Ca2+ and Zn2+) causes unpredictable pH
changes with dilution [2][3].
• Addition of hydroxide, in the form of NaOH or
KOH. This method can be used to increase pH Some examples of pH measurements with
in unbuffered brines or increase buffer capacity glass electrode and pH papers in buffered and
in buffered brines. However, the OH- ion is not a unbuffered formate brines as a function of dilution
buffer and in unbuffered formate brines, pH will are shown in Figure 2 and Figure 3. The pH papers
drop immediately when the brine is contacted by were BDF pH indicator sticks. These sticks
acid gases. Relying on OH- addition to maintain indicated a pH of 14 in all of the undiluted buffered
pH of a formate fluid is therefore not advised in formate brines. As these brines were all buffered
applications where the formate will be exposed with both carbonate and bicarbonate (6.25 ppb
to influxes of acid gases from the reservoir. K2CO3 and 3.75 ppb KHCO3), we know that the real
pH in these systems should be close to the pKa2 of
• Buffering the formate brine with carbonate / this buffer system (i.e. 10.2). This is very much in
bicarbonate. Unlike the heavy bromide brines agreement with the pH levels that are measured in
based on the divalent calcium and zinc ions, the diluted brines. It is evident that measuring pH
formate brines are fully compatible with a directly in undiluted formate brine with pH paper
carbonate / bicarbonate buffer. Buffers are can result in errors of up to four pH units. The data
designed to resist changes in fluid pH and can also shows that measuring pH in undiluted formate
cope with large influxes of acid gas. brines with a glass pH electrode can lead to errors
of up to one pH unit in the alkaline direction.
A6.1.2 Measuring pH in formate brines
pH is a measure of the hydrogen ion activity of a
solution. Because pH is dependent on activity, a
property that cannot be measured easily or
predicted theoretically, it is difficult to determine an
accurate value for the pH of very concentrated
solutions, such as high-density brines. Consequently,
any pH values that are measured in neat formate
brines are not a true measure of hydrogen ion
activity and should only be used in a relative sense.
pH can be measured in formate brines by potentio

metric measurements or with pH paper. In both
cases, dilution of the fluid with nine parts (vol/vol)
deionized water is recommended in order to get
more accurate readings. Please notice that this
V ER S IO N 1 – 1 2/ 07 SECTION A6 PAGE 3
C ABO T S PE C I A LT Y F L U I D S FORMAT E T EC HNI C AL MANUA L
pH measurements in buffered and unbuffered potassium formate brine
15.0
KFo 1.56 s.g.unbuffered (glass electrode)
14.0
KFo 1.56 s.g. unbuffered (pH paper)
13.0 KFo 1.561 s.g. buffered (glass electrode)

KFo 1.561 s.g. buffered (pH paper)
12.0
11.0
pH
10.0
9.0
8.0
7.0
6.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Dilution factor
Figure 2 Effect of dilution when measuring pH in buffered 2.0 s.g. / 16.7 ppg CsKFo brine and buffered 2.2 s.g. / 18.3 ppg CsFo brine.
pH measurement in buffered CsFo and CsKFo brines
15.0
CsFo 2.199 s.g. buffered (glass electrode)

CsFo 2.199 s.g. buffered (pH paper)
14.0 CsKFo 2.0 s.g. buffered (glass electrode)
CsKFo 2.0 s.g. buffered (pH paper)
13.0
pH
12.0
11.0
10.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Dilution factor
Figure 3 Effect of dilution when measuring pH in buffered 2.0 s.g. / 16.7 ppg CsKFo brine and buffered 2.2 s.g. / 18.3 ppg CsFo brine.

1 pH = − log [H + ]
A6.2 pH buffering of formate The carbonate / bicarbonate buffer system
brines 1 pH = − log [H + ]
2 pH = − log(strong
provides aH + ) a H + at two different pH levels:
buffering
Ka
a H +3 HCOO− + H3 O +←⎯→ HCOOH + H2 O pK
Formate brines used in2oilfield pHapplications
1
= − log pH(a=H +−)log should
[H + ] • Upper buffering level at pH = 10.2 a
be buffered by the addition of potassium 1+or Ksodium pH = − log [H + ]
3 HCOO
+2
−
pH+ H= 3O − ←⎯→
log ( a
a
)HCOOH + H2aO 2 − pK a pKa − 2− −
carbonate and 1 potassium
pH = − log [H ] or sodium bicarbonate. H+ 4 H CO +
3 +H+ ← ⎯→ HCO3
2
pKa2 CO3(4) HCO3
The main purpose of this buffer is to provide 2 an + K apH = − log ( a H+
) a H+
3 2 − HCOO −
pKa + H3 O ← −⎯→ HCOOH HCO +H −
O H + ←⎯ pKa1
pK→ −
3 2 +pK a H 2 − CO pKa1
2 to pH =− 4 logthe (a HCO + ) a H→ HCO3 − 5 ⎯ HCO3 H2 CO3
−
alkaline pH and prevent pH +from H + ←fluctuating ⎯ + 2
+where a 2+= 10.2 CO 2 3 HCO
3
3 HCOO 1+ H3 O pH ←⎯→ Ka
= − log HCOOH [H ] + H2 O3 pKa 3
as a consequence of acid − or base K influxespKinto
3 HCOO 5 + H3HCO O +←⎯→ −a
HHCOOH + a1 + H O pK −
4 3 +CO +→ H 22aCO3 pK HCO H2 − CO solution
2 −←⎯ ⎯ pK − a −
the brine. 3 + + H ←⎯→ HCO 26 3 At
2
pH
CO pH=( g − ) =⎯→
log
← 10.2
( a a1
CO+ )
( (pK aq a)2) the CO
3 buffered
a H 3+ 2 3 HCO contains
1 pH = − log [H ] 2− + pKa 2
−
H 2 3
2− −
−
4 CO 3
pKa1
+ H ← ⎯ the → same
HCO
2
3 amount of carbonate pK
− 2 a ( CO 3 ) and HCO3
+
Maintaining an 4 alkaline
CO3 2pH
2− + 5pKa HCO − + H ←⎯ ⎯ → H 3 CO HCOO − 2−
+ H O +
← pK Ka
⎯→ −HCOOH HCO + H O H CO pK
6+ H environment
←pH ⎯(→
1 = − log HCO (a = 3+in
3
−) 5log
formate a−H + +pKabicarbonate
2 3 CO3 3 ( HCO a
3 ).
3
2 2 3
CO 2 g) ← H CO 2 ( aq [H) +HCO
2 a
⎯→
pH ] 2pKa
1
−
brines is important for the following reasons: 3 + H ←⎯ ⎯1 → H2 CO3 pKa1 HCO3 H2 CO3
− + pKa1 −
5 HCO33 + H HCOO ←⎯⎯→ − H CO
+ H 23 O ←
+ Ka
3 ⎯→ HCOOH + H pK O a• 1 Lower
HCO pK pKa H 2 CO3 level
3buffering at pH = 6.35
26+ pH
CO2=( g−) log ← ⎯→ (a HCO + )
2 ( aq ) 4
2 a HCO 2 −
+ H ←⎯ + a
→ HCO
−
pKa2 CO3
2−
HCO3
−
1 pH = − log [H ] 7 CO 2 ( aq) + H 2O ← ⎯→ H 2CO 3 3 ( aq)
+ 2
3
- Many polymeric additives are prone 1 topH degradation
6− = − logCO [+H2 +(Kg] ) ← ⎯→ CO2 ( aq )
under acidic 3chapter HCOO + H3 O ← − ⎯→ HCOOH + H−2 O H + ←⎯⎯
pK pK −
62 conditions (see on pKa polymers) HCO(5)
a
pH2 (=g 47− )← log (aCO )2 − aq a→ + 5 HCO 3 +pK
a1
→ a H 2 − CO pKa1 H2 CO3
CO H + 322((aq
CO )1++H← −
⎯→ CO + )H HCO ( aq ) CO 3 HCO
2O ← H−2log CO
⎯ pH
⎯→ H +=
2
3 [3H ] 2 3
- Alkaline pH control is a critical factor in limiting H 2 pH = − log ( a + ) 8 H a CO

2 H 3 + ( aq )
a2 K a
← ⎯ ⎯
1
→ HCO
3
3
−
( aq ) + H
3+
( aq )
+ − Ka
gas diffusion 3 in formate
HCOO 5 +
−
HHCO
brines 3O ← ⎯→+2H +HCOOH
pKa1
→+−H H 2O −pK
−
47 3(see chapter on where
a + ] 2 −a pK = 6.35
2← − ⎯ ⎯+1 pKaCO HCO3 − COH22−CO3 HCO −
3 CO + pH + H=−← log (a H
pH += ) KCO
− log [H K a pK
CO32 (HCOO aq K a) H 2O +⎯ O3+HHCO
→ 9a 3 3+(HCOOH aq ) 23( g )+
2 ⎯→
H2+aO a)2pKa
2
←
H − ← 26⎯→ CO CO H++⎯→
← H 1
←CO ⎯ ⎯ 2
(→ aqHCO 3 3
well control) 8 H2 CO3 ( aq) ←⎯ ⎯→ HCO3 ( aq) + H ( aq) 1 3 2 3
− 7 2 + − pK
CO2a( aq) ++ H 2KO ← ⎯→ H 2CO3 ( aq)
- Formic acid4decomposes + at a2a lower 3 HCOO
temperature + pH
H O = −← log
⎯→ ( a HCOOH ) + H O a pK −
HCO 3 At H pH = 6.35
CO3 2 (HpK a1) theHCO abuffered Hsolution contains
5⎯ − + H ←⎯ → H2 CO
a
⎯ 2 CO3
2− pK 1 + 2− + −
CO23( aq − 3 pK HCO
7 CO 69+) +HHCO 2O
← ← ( g−→
⎯→ HHCO
H2CO + 3 (K aqa ) 3
2
CO )← +⎯→ CO
← 33 ⎯ ⎯ 22(−aq→) )← HCO K 2
+a 3 pKa − a−2 +− 32−
4 H2 CO 3 (3aq+ HCO ( aqthe ) + +Hsame ( aqOH ) amount 2−
than formate (see chapter on 82 3 thermal CO stability) H⎯ ⎯ ← →⎯ 10HCO
1
→ 3
2
3HCO 3 K+
−
← ⎯→ CO pK of bicarbonate
3 a 2 + H 2O 3
CO (HCO3− ) and
3 HCOO + H −
K a O ←⎯→
3 → HCO − (HCOOH
a
+ + H2 O pKa
H2 CO + 3 (pK aq a )← aq )+H (H2(CO aq)3 ).
pKa1
- Formic acid5is corrosive
HCO3 + whereas
−
H + ←⎯⎯ →4formates
H22CO 83 2 −are pK⎯ ⎯ carbonic
1
− HCO 3 acid
−
2− −
69K a 5− CO CO ( − CO
−g )+ ← ⎯→ H − + +KH
CO a+
( aq ← )
pK
HCO⎯ a1 → HCO
− a1
2 3 pKa2 CO−3 HCO
HCO 3 + ← H+⎯ ⎯ →← ⎯ ⎯ 7
2
→ H CO CO 3 ( aq) + H O ← ⎯→ H pK CO ( aq ) HCO H2 CO3 3
8
not (see chapter Hon 2 CO 3 ( aq) ←
corrosion) ⎯⎯→ HCO (← aq )3+ H ( aq2+ )− H O+ 2K 322 −
2 3 − 1 22 − 3
10 HCO + OH 3 ⎯→ CO −
2 2 a1 3
−
3
3
9 −CO3 + +
3
211−H
2
pKa1←+⎯ ⎯ a
CO → pK3aHCO
2
+ CO 32 +H − 2O ⎯ ⎯→ 2HCO3 − 2− −
2− 5 − HCO 43 +H CO← 3 ⎯ +⎯H→ ← HThe 2⎯ COexact →3 HCOlevels
2
3 of pKa1 and HCO pKa2 3will vary
CO H23CO somewhat
3 HCO3
96 CO CO32 (7g+) ← H
⎯→ +
←
CO CO Ka
⎯⎯ ( → ( aq HCO
2 ) + H 2O
aq ) 3 ←
2
−⎯→ H−2CO3 ( aq)
The buffer also plays a very important 10 2 −6 HCO
2 part
CO+( OH gin) ← ← ⎯→ COCO 8−−3 ) + H+with
2−
2O
2 −brine ( aq) ← concentration,
K −
)temperature, + and pressure.
3 (↓ + H 3 ((saq ) )
a
⎯→ 2 (12 aq H
CO 2 CO 3pKa(13aq) + Ca ( aq) ⎯
⎯ ⎯→ HCO
2
1 +
⎯→ aqCaCO
11 CO3 + CO2 + 3H 22O ⎯ ⎯→ 2HCO HCO − 33 + −H ←⎯ 2 −H CO pKa1
−
encouraging the formation of the high quality 10 5 HCO 3 + OH ← ⎯→ CO3 +2 H 2O3
⎯→ HCO23−
[ CO ]
H2 CO3
−7 2 −
6 22 (−aq
CO CO
) + H ( gO ) ←
← ⎯→
⎯→ CO
H CO ( aq ( )
aq ) 2− + Ka K − − 3
=buffer
A exp( B × pH )
+9H +3((aq
) 13 CO )− 32 ( g+) + HHdemonstrates → HCO +
protective film10 on steel 8surfaces. (See chapter )CO 2O ← HCO 3 3 + H ( aq ) carbonate
2 on
sFigure 4 how the
HCO12
−
+ OHHCO CO +a +H 2 2 ←⎯ 2
⎯⎯→
2O
K2 − 2 3 s
←
2 CO
⎯→ ( aq ) 3← HCO 3 ( aq
3 (3aq )+ Ca ( aq )⎯ CaCO
2 −⎯ ⎯ → 1
3
11 CO ⎯→ ↓⎯→ [ HCO3− ]
3 + CO2 + H 2O ⎯ 2HCO
corrosion.) 6 2 − 2 ( g) ←
CO ⎯→ works3
CO ( aq when
[ CO) 2−
]
a
−
strong acid is added. The carbonate
7 CO2 (13 9aq) + HCO O← 2⎯→− HH +COK 11 (aaq K) CO − + − CO2+ + H 2O ⎯ ⎯→
2
+2HCO 3 3= A− exp( B × pH )
2CO
8 3 2 ( g+) H + 2 ←
2O
2 −⎯ 3⎯ → HCO HCO )+⎯ H −( aq )reacts H[)3+H ] ×) [HCO
with − − added 3 ] acid until all the carbonate is
← ⎯→ 2
K2a+ 3 s
HCO 2 CO (3aq ( aq )+ −) )← Ca+⎯ ⎯H32→ (O aq 3 HCO
3H (2↓ aq CaCO)K+( aq −( aq
([sHCO
+) OH
CO3 + CO2 +12
1 2−
11
2−
H 2O 7 ⎯ ⎯→ 3 CO
2HCO 2 ( aq ← ⎯→ 10⎯→
14 CO HCO 3 = 3 3
]← ⎯→ CO3 + H 2O
The main reason for loss of pH control in12oilfield 3
CO
2−
( aq ) + Ca 2 +consumed.
( aq ) ⎯ ⎯→ P ↓COCaCO As
[
long
2(−s )
]
as there is still carbonate left in
2 CO
] (and
+ aq)K+
CO H +3=((solution,
aq))
a H 3
K O← H 2CO 3
13 92K⎯ [aq 7
CO
]×
CO [HCO
2−
32−(−g +)aq +3H−)H ← O⎯ ⎯ → 2HCO ⎯→ − − 3
= remains
A exp( B2×−−]pH ) OHaround
fluids is the influx ofCOHacid gases +asuch H )+HCO as CO )a HCO 15 3 3 +the aq the PCO−pH high CO3 theHCO ‘higher [CO32 − ] [HCO3− ]
2 2− −
←
2 (−⎯→
−
pH − log K − [log ] + log[HCO
2− 2 + s
2 3CO 3 ( aq
) +)Ca ↓(⎯→ 2+
128 ( aq 2H aq
← K⎯ =(3→ CaCO 33( s ) +K H
− 1
1014 HCO + OH ⎯ ⎯→ 3← CO 2O − K 2− HCO 2 [ CO − 3
3 ] 3
H 2S. These are both weak acids withPCO 8 H
a 2pK 13 CO
2 a higher ( aq )
CO2 ( g) + H 2O2←
← ⎯⎯ → 11 HCO 1
CO
buffer
⎯→( aq )
3 HCO++ H
COlevel’
+ −
( aq
+ +HH ) O +
(10.2±1).( aq)
⎯ ⎯→3
2HCO As[ soon −
s = A exp(
as the carbonate is B × pH )
2− Ka K −−
3
7+ CO2 ( aq[ CO ) + 3H−32]O ← ⎯→ H 223CO3 (2aq) HCO3
]
than the pKa13 9 formic
of CO CO23(acid.15g)++HH 2O
+
←pH ←⎯ ⎯ ⎯→
= → − HCO
log HCO K [−H 2
− log +2] ×
+
HP [COHCO ( aq + )3 −)]←
log [ HCO K a 2 −−
] −consumed,
OH =− A− exp( CO B2×+− pH
s
pH HCO) drops −
[ CO down 2−
]
3
[ to the
HCO
−
] ‘lower H 2 SO4 buffer [ OH − ] [CO
10142 − 9 HCO 8
K = 3 +3 2OH
3 H CO − ( aq CO ⎯ ⎯ [→ HCO
+H
1
] ( aq ) + H ( aq )
02O
3
+ H3← ⎯→ − 3HCO
− + K − 2 − 2 +
CO3 + CO2 + CO 12 HCO 33CO 3 ×( aq Pf ) + Ca ( aq) ⎯ ⎯→ ↓ CaCO3 ( s) 3
a 3 3
11 H 2O ⎯ 2HCO←⎯
[
⎯ 2
+→ 16
] [
2
.−302
]
3 3
P⎯→ H 3 × HCO level’
3 where it remains as long as bicarbonate is
14 2CO−2 K = + K a [ CO−32− ]
A6.2.1 How the carbonate [H−+ ] × [HCO − 23− ] 9
15
− / bicarbonate
2=− −CO 8 +log HHP2← CO ⎯ ⎯ P → ( aq HCO
[ )2
← available⎯
K a−
⎯ −→2] − HCO
1
OH to
−
− ( aq
react K) +2H −with
+
( aq )
the − added +[CO 2 − ] acid [ HCO for ] conversion
H
= A SO exp( [×OH 2− −] [CO
pH log CO HCO 4 [B pH )]( mg
3K − + log HCO [CO −
CO 13 17 CO2( s) CO 3 ( g]) + +[OH H 2O]← HCO 3 + 3/ HL ) ( aq)3 CO / L) = 120
−
10
14 KHCO = 12 3 + OH CO ← ⎯→ ( aq CO
) + Ca 32 − +(H
2+
aq−2O )⎯ CaCO
3 3 3
=⎯→ 0.02 3 × Pf ( mol 3 −
s
2
buffer works 16 0.02 3 × PfCO ⎯→ −↓
2 − 23
−[ HCO3 ]2 −
3
PCO11 10 3 HCO +15 CO
3 2 + + H
OH pH 2O= ⎯← ⎯→
−
⎯→ log
2 −
2HCO
CO
K
3 2−
− 3 +logto 3 +P K
carbonic
H 2 O + log [HCO −
acid. −
] In OH order −
CO for 2−
the HCO pH to [ drop
CO ] down
[HCO
−
] H SO [ OH − ]
2
9− CO3 − + H 2 ← −[HCO [ CO
⎯ ⎯CO
a
→ −
]HCO
2 2 2−
− 30 ]3
3 3 3 3
[
3
2 −
]
2 4
3
A buffered solution is = defined as a solution = CO ( kg / m ) = 1.2 ×
0) that 18 below 3 + this second B[buffer level, / L4) an acid ×] Pneeds[CO to
2− −2 −
15 pH 13 − log KCO −
[CO log P]+ [H+ 2log − [HCO
] =HCO K
×−] P OH−
) CO
+ 2 −HCO
+[3H
[CO =A −]
3 ]exp( [HCO × pH 33 ] ) ]( mg H 2 SO [ OH −
s)23]O × [HCO
2 −
2 (3g )CO
2O 3 HCO
17
0OH .+02 3 + /← H ( aq )3CaCO CO = 1200
10 ← ⎯→ 2 + ( mol −
L⎯→ 3
3 +f OH ↓CO [(H
s
−
11 in CO
2−
+ CO 1216 CO .02 ×( aqPf ions −Ca
2
( aq
+ )⎯ ⎯→
14 K3 =added HCO
−
] 3 f
2 + H 2O
32HCO
resists a change its3 pH when hydrogen
⎯ ⎯→ 2− 3 (H ) be −
3 that is stronger than the carbonic acid,
PCO2 [
[HCO 11− ] CO 163 + CO02.02 + H×2P Of ⎯ −⎯→ 2HCO 2 − CO3 ] [
2−
2−
](CO 3
or hydroxide ions (OH2-18 )− are added. =[The 0 2 −ability − 10 −to KHCO − which
−aq)is COformed. + H 2O− As =CO Aany kg ×−/ 2pH
m2gas−)) = 1influx
.2 × Pf into the
− 3
1317 2 +[H 3 + ]CO × CO[ HCO ( g ]
) + + [ H
]
OH O ]← = ⎯→0 . 02 × HCO P +( molOH + / [ HL ←
)
+⎯→
( ] 3exp( [BCO ](OHmg−/ L)CO = 12002−
× Pf 3 −[CO [CO 2− 2 −
] ] [HCO −
15 pH OH = − = 0
log K − log P CO ] + log[HCO3 ] 3 HCO 3 3 (ppb ) = 0.342] × P
s
12
16 0 CO.02 ×
314 (Paq ) +K Ca= ( aq11 )⎯ ⎯→ ↓CO
2 3 3 CaCO 2− 2
3 ( s ) 2+
193
f 3 −
3
[ HCO
resist changes in pH comes about f by the 2buffer’s
− + CO
[ 2−+ H
] [O ⎯ − buffered
⎯→ ] 2HCO solution 32
dissolves and converts [
3
2to
− carbonic
]
12 PCO2 17 CO (3aq ) + Ca ( aq )
CO3 + OH 2=− 0.02× Pf (3mol / L )
2 2 ⎯ ⎯→ ↓ CaCO 3 ( s ) CO3 ( mg / L) = 1200 × Pf
[ +) and − 3
] ] /0[2or [ CO3 ] 2 − 2−
ability to consume [hydrogen ions
18 K(H
×HCO 3 += 2220
acid,
[CO = −A a =CO
]exp( 0[.CO02 2×pH
influx
Pf]()(mg mol − is
/[/COL2L−[therefore −2 − [ CO 3 not
]( kg / m3 ) = 1.2 ×ofPfpulling
− capable
2B −×
])=3 21200
− 2−
13
17 CO
CO315 ( g] +
2−
219 ) +[OHHpH 2[O
−
OH ] =← = 0⎯→
−.02
− ] =log
120 PKf (−[mol
HCO H log
3 CO +/×P LH
11 )HCO +
− ( aq3) ]
( +
aq log)
−
+CO[HCO
Ca
−+ −
+ ( aq
CO ] ) ⎯ +
⎯→−OH 3
H O↓ CO
CaCO
⎯ ⎯→
s
2HCO( s3 )HCO
− [ CO )CO ] ]
(ppb ×[HCOP
) =f 03.42 ] × H
P SO42 −[CO [ OH 2− −
] ] [CO
14 13 K = CO 182 ( g 3) + [H
CO
HCO
− 3] = 0HCO
K 3 [ 03.02 ] −
× +
HPf (much 3 3 3
= A exp( B × pH ) [COlevel.
3 f 2
]( kg3/ m3 ) = 1.2 × Pf
hydroxide ions (OH -). 2O ← 3 ⎯→ 16 HCO the + pH aq)3 below −this second buffer
2 2 3 2 3 s
P [ HCO [ ]2 −
]
3
[HCO20 −
] 0 [CO − ] = 0.02− × P ( mol / L) 2 − K CO2
[CO 2− CO
]( kg2 −/ m ) 3= 1.2−=×APfexp(
33
18 [3H +=] ×
2 − 2 +− − 2− 2 −B × pH )
19 33 ] 13 CO +(⎯→ aq
log)[+ Ca ( aq − )H
+ − 3)↓ CaCO
[HCO [OH= ]−=CO 0f 12 2(g −)log +H 2O HCO −+
[⎯ ⎯→ ( aq 3 (HCOs) − [CO ] ] [HCO − ] H SO4 [CO
]3/ L ) [CO
15 pH log K PCO ← HCO 3 33] ] + OH
OH − ] =CO [ OH ] ] [CO
2−2 −−
3 3 (ppb) = 0.342× Pf 2
s
14 K =16 3 17
−21 [[COHCO
2
3 ]=0
0.02 3 ×[ P HCO f ( mol
[ CO 3 3 ]( mg / L ) = 120
0.02× Pf [H + ] × [HCO 3 ]
2
3
PCO2 14 K19 = [OH ] = 0 − [ CO
2−
] [ CO
2−
] (ppb ) = 0 .42 × P [CO3 2− ]
[ 2−
] 13 P CO (−/gL)−)+] H 2[O − ←
K
− − ] HCO
⎯→
−
32− +2 − H + ( aq) 2 −−
3 s
= A2− exp( 3B × pH )
2−
f
[OH ]= 20 CO = 0 . 02[ H −× +CO P
] × (
[ mol
HCO 218 22 [
HCO
OH ] = =
0 −0
[CO[CO ]3 (ppb ] [)[HCO [ −
] [ OH] ] [CO [ CO ] ( kg / m 3
) = 1.2 ×
L) 34=[CO
−
15
19 pH 17 −
=21 −0 log K[CO [−HCO log]P+CO
2 −
3 3 14
−
] [0=OH +
0 log 3 ] [HCO ]
−
= Kf0.02 = ×3 P[ f ( mol
f OH 3 CO
2
2 − / L) 3 HCO 3
−3 3 =
CO 0.42]× PfH
2 − 3 3 ( mg
HCO/−2 SO 1200 23− × Pf
3
16 15 . 02 ×
pH P
20= − logCO
2
KP −3 log ] =P0CO.02+×log Pf [(HCO mol /3 L]) OH CO3
−
HCO3 [ CO3 ] [HCO3 ] H 2 SO4
−
[ OH −
] [CO
CO2 2
20 [CO318 2−
22] = 0.02 [HCO[× Pf−3(−]mol ]=15 0/ L2) − ]−+pH [H + ] × [HCO
23 [CO332−−]] = 0.−02× Pf ( mol / L) 22−−]( kg / m23−)− = 1.2 ×2P−
=0[CO OH − [CO
−
1721OH [ HCO ] =[OH140 = −−]log = 0 K
.K02 =−×log P ( P
molCO /+ [ Llog ) −[HCO ]= 0 3 ] CO33 [HCO
CO3 3 ]( mg [CO /L ] [HCO
3 ) f= 1200 ×3P]f H [CO 2 SO4 ] (ppb
2− [ OH − ] [CO
16 0.02× Pf 3 3 19 f
P OH 2
3 ) = 0.42× P
CO
216 − 0.21 02× Pf [HCO3− ] = 0 2
[ CO ]
23 [22
18 CO ] =[[HCO 0.02× P0f 15
OH −3] =] =
− ( mol / L)pH = − log K − log
0 2 −P −CO + log[HCO 2−3 3 ]
−
OH [CO − 2−
CO3]( kgHCO
2 −
/ m ) 3= 1.2[CO
3 − 2−
× P3 ] [HCO3 ] H 2 SO4 [ O
−
[[CO ] ] =0.[02
2−
17
21 [HCO
[CO19 2 −−
33 +
] =[OH0 [OH − −3
] = 0] =.02 0 × Pf ( mol /−L )× P 20
24 HCO 3 3 = CO ×3P f ]((molmg[CO // L L( )mol
) 2=− 1200/ L) ×3P0 [CO3 f2− ]
) 3 ] (ppb) =[ CO f .42 2× − Pf
2
17 16 [CO 22
0.202 ] + [OH [ f − −] =
OH ] = 0 .
0 02 × P ( mol / L ) A . exp ( B . pH ] ( mg / L ) = 1200 × Pf
2− 3 f 3
[[OH
HCO − −]
]24 23 2 − − [CO3 [ CO ] = 30.02 ] × Pf ( mol25 / L) A = 9 . 69164 [ CO 10 2−−11
] ( kg / m 3
) = 1 . 2 × P
18
22 3= 0= 0 [CO ]
2−
20 [ HCO 3 3 17 = 0 . 02
] = .[ ] =[f0CO × P ( mol 2−
/ L
] + [(OH ) mol
02.−02 /]L× =) P [ CO 2−
=]0(/mg m3×/) LP =)f1= .21200 × P3 2f− ]
−
19 18 [OH
− 16 3.] = [0 0.f02× Pf ( mol−/ L ) 3
[CO3 [CO f2 −
] (ppb ]3()kg .42 × P[fCO
× P[HCO
− 2−
A exp HCO
23 ( B 3 pH CO) 3 ] =210.02 f ( mol 3 /] L =) 0 3
23 [CO3225 −
] = 0.02A×=Pf9(.mol / L2)10 −[ CO ] 226
B = 2.29762135
− − [−HCO
.023 ×] P [CO32 2−−]( kg[/CO
11
2024 − 18
69164 [[CO ] ] =017 = 03([CO / L](+)mol
− 2−
[OH/ L−)] = −0.02× Pf ( mol
[OH] −] = 0 [CO3 2− ]/ (ppb L) m33)2 −=]1( mg .2 ×/PLf ) = 1200 × Pf
19 [OH21 −
] = 0 [HCO HCO 3 3 = f mol 322
) = 0 .42 × P [CO3 ]
] = 0 − A exp B pH
. ( . − 27 ) [ CO [ OH ] = 0 f 2−
[ ] [ ] [CO 2− ]
2−
26 B[ CO = 219
3
.29762135 OH24 = 0 [ HCO 3 ] =− ] .
3
( mol/ L) CO3 (ppb) = 0.42 × Pf
25 ] A = 9.69164 18 10−11[HCO 23 3 A=exp 0 ( B . 2pH
[ [
CO 2−− )
] ]= 0 .02 × P ( mol / L )
[CO32 − ]( kg / m3 ) = 1.32 × Pf
[ 2 −−
] 28 CO = 0
2−
20
24 CO
[ HCO 22 = 0 . 02 ×
[OH −f] =.019P− 3
( mol / L
( mol) − [OH / L) 2 −
[CO3 2− ]
] =2 −0] =] =0A.002 [CO3 ] (ppb) = 0.42× Pf
− 3 f
0[HCO
3
27 A .21
33
[exp
OH (20 B] =pH ) [CO 325 3 =× 9.P f ( mol10
69164 / L−)11 − 2− −
26−11 B = 2.29762135 OH CO3 HCO3 pKa
25 A = 23 928 .69164[CO 10
[CO
2−
3 3 ]=
2−
]20=[0OH .002−×] =P[CO f0(19 mol 2−
]/B=L=)0[.OH 02 ×−P] =f (0mol / L) − [ CO3 ] [CO3 2− ] (ppb) = 0.42× Pf [CO3 2
[HCO3− ] = 0 22 − 26 2 .29762135 2−
21 27 − [ OH =2 0− − ]
3
24 [ [ HCO
OH −3 ] =
] [.CO
2−
] . [( mol
HCO / L −)
]
[HCO A exp 3 ( B pH ) 3 P H SO
26 B = 2.29762135 OH 21 CO 3 ] =[HCO 0 − ]3 − 2 − pKa f 2 4
OH mol =3 0/ L] =
27]3]==3020 0.]02−× Pf [(CO ) 0.02A×=P9f .(69164 mol / L) −11
22−−
22 [OH24 − ]= 0
− 2328 − [[CO CO33[ CO 2−
25 10
[OH ] = 0 [ HCO ]
3 ] 21 .[CO[HCO
= ( mol
] =[ HCO02 − ] ]/ L )
27 283( −B]].=pH
2 − −
[OH22 −
A exp −[OH 03 [)CO 2− 3= 0 P
− f H 2 SO4
23 [ [CO 22 −−
] = 0 . 02 × P ( mol
OH
/ L )
CO3 3 26
[ CO ]
HCO3 B = pK 2.29762135
a
28 25 A = 9 .
f 69164 22 10 −
− [OH
11
21 −
] = OH 0 3[−HCO
−2−
] = 0 2− −
pKa S E C T I O N A 6
V ER S IO N 1 – 1 2/ 07 33
24 23 [[HCO [ −3 ] = ] = 0
CO
2 −
. 022 − × P ( mol 3 ( mol CO / L / L
) −)
] ] =HCO PAGE 5
− 2− OH ] −3 A[.CO exp3 ( B] . pH f ) [ HCO3[OH
27
3 −
P0f H 2 SO4
3
OH 26 COB= 3 2.29762135 HCO pK
2− [a [ 2 −
] [ −
]
3
] =OH
−
] CO3/ L) 2 − HCO3
25[ CO 3 23
] A = 9.69164 [CO 22 0.[02OH× P] =f (0mol Pf H 2 SO4
−11 −
( mol/−L]−) 10 [ CO28 [CO3 ] = 0

2−
− 3
24 [[OH HCO − 3 ]=
27] A[[CO. exp
OH − ] .
2−
3 (]B = 0pH )[ HCO Pf H232−SO4 ( mol/ L)
] 2−
24 [ HCO 3 ] =
A . exp [CO[(3CO B .]pH L) 32 −
3
26 −211− B = 2.29762135 23 = ]0).02 OH × P−f ( mol / CO HCO3
−
pKa
25 A =28 9.69164[CO 10 ] = 0 − 3 2−
pH behavior of carbonate / bicarbonate buffer when adding strong acid

12
11
pKa 2
10
9
8
pH
7
pKa 1
6
5
4
3
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Fraction of buffer consumed
Addition of strong acid
1 Figure
pH = − 4 logThe [H ++pH ] in water buffered with carbonate as a function of added acid (H ). The x-axis shows the fraction of the buffer that
+
1 pH = − log [ H ]
is consumed by the added acid. As can be seen, carbonate buffers twice, first at pH = pKa2 = 10.2 (upper buffer level) and then at
2 pH
pH ==pK − loga 1 ((=a
a H6.35
+ ) (lower buffer a +level). In the case that the added acid is carbonic acid (from CO2 influx), the pH can never drop much
2 pH = − log + ) a HH +
1 lower
pH = than − logpK [HH +a]1 = 6.35.
Ka
3 HCOO− + H O +←⎯→ Ka HCOOH + H O pK
3 HCOO− + H33 O +←⎯→ HCOOH + H22 O pKaa
2 pH = − log(a H + ) aH +
• Buffered formate brines are capable of
4 A6.2.2
CO
2− + Buffer pKa protection
− against pKaa2
2−
CO32 − HCObuffering
−
large amounts of CO2. Unless the influx is
32 − + H
K aHCO
+H← ⎯pK+a← →
43
−
HCOO + O HCOOH + H O pK
2
CO3 + H CO ←3 ⎯→ HCO ⎯→ 3−
pKa2 CO3 HCO33
−
influx
2 2
2
3
unusually large, the brine maintains a pH around the
− + pK −
5 HCOmajor
The 3− + H + cause ←⎯ pK ⎯ a1
→ofH2acidification
CO3 pK
of conventional HCO3− H COupper buffer level (pH = 10.2), which is high enough
5 HCO 2 −3 + H + ← pK ⎯ a ⎯→ H 2 CO
a1
− 3 pKaa11 HCO 23− H22CO 3
−3
4 CO
completion
3 + H ← 2
⎯ → HCO
brines is influx 3 or diffusion of carbon pK a2 CO 3 HCO to
3 prevent carbonic acid being present in the brine.
6 dioxide gas (CO pKa1 2) into the wellbore from the With a large influx of CO2, the pH drops down to the
CO 2(g )← CO ( aq →) H2 CO3
− −
65 HCO 3 +
⎯→H + CO ←⎯ 2⎯ pKa1 HCO3 H2 CO3
CO 2 ( g) ←
surrounding ⎯→ 2 ( aq ) formations:
rock lower buffering level (pH = 6.35) where it stabilizes.
Measurements of pH in formate brines exposed to
aH + 6 CO2 ( g ) ← ⎯→ CO2 ( aq ) (6) various amounts of CO2 have confirmed that the pH
never drops below 6 – 6.5. This pH is still close to
OH + H2 O 77 CO2 ( aq) + H 2O ←
pK ⎯→ H CO ( aq)
CO a ( aq) + H O ←
2 2 ⎯→ H 22CO33( aq) (7) neutral, meaning that this brine system cannot be
‘acidified’ to any great extent by exposure to CO2.
Ka −
8 H
CO CO ( aq (
) aq
+ H )
1
← O2⎯⎯− → HCO (−aq) + H + ( aq)
H CO ( aq ) (8)
87 pKCO CO ← ⎯→ HCO
K − +
2 2 3 ( aq) ←⎯ 3 ( aq) + H ( aq)
a
H 2
a2
3 1 2 3 ⎯→ HCO 2 3
33
2− Ka −
• Unbuffered formate brines: The pH of these
+
9 CO
pKa321=− 6.35 + H 2
← ⎯ ⎯ − → HCO brine systems responds in a similar fashion to
3 9 CO 3 + HHCO +2
←⎯ Ka
3 → HCO
K⎯
H2 CO3−
3− 3 +
8 H2 CO3 ( aq) ←⎯ 1
⎯→ HCO3 ( aq) + H ( aq)
a
halide brines when exposed to CO2 gas. However,
10
9 Depending
HCO 2 −−
+ OH + −on ←K⎯→a the COoriginal
2 −−
+ H O pH of the receiving brine they do have a higher initial pH, and the pH drop
10 CO3 3− ++H
HCO OH
2
←− ⎯ ⎯ → HCO 2−
CO33 3 +CO H 22Oremains in the brine as
system, 3 the ← ⎯→
dissolved 2
will be limited as the formate brine is a buffer in
either carbonic acid (H2CO ) or bicarbonate
+ (HCO3-), itself (pKa = 3.75). If there is any chance of an acid
1⎯→ 22HCO− pH = − log [ H ]
2−− − 3
11
10 CO
HCO 32 −3+ CO
according + OH 2 +to
−H O ⎯
← reaction
⎯→ CO32HCO + HThis
8. 32−O is demonstrated in gas influx, the use of unbuffered formate brines is
11 CO 3 + CO 2 + H 2
2
O ⎯ ⎯→ 3
Figure 2− 5. As 2more + 2 COpH gas
= − enters
log ( a + )
into the brine, a not recommended.
q) 12 CO 2 −( aq) + Ca2+ ( aq) ⎯ ⎯→ ↓ CaCO3 ( s) H
2 H +
12 CO332carbonic
the −( aq) + Ca acid ( aq) ⎯ ⎯→ ↓ CaCO
concentration − 3 ( s ) builds up and the
11 CO3 + CO2 + H 2O ⎯ ⎯→ 2HCO3 − [KCO 2 −
−]
pH
CO drops ( g) + H and K 3
allows HCOO
HCOunbuffered + + H O ←⎯→
+
3 brines [ CO 32HCOOH
3to
] = A exp( + HB ×OpH ) A6.2.3
pK Buffer protection against
− acidify. 2
− a
13 O ←⎯→ 3− + H + ( aq)
s
a
13 CO222(−g) + H 22O 2← K
+ ⎯→ HCO3 + H ( aq)
s
[ HCO ] = A exp( B × pH ) H2S influx
q) + H + ( aq12
) CO ( aq) + Ca ( aq) ⎯
3 ⎯→ ↓ CaCO ( s)
3 3
[ HCO−3 ]
The [three H ++ ] × [HCO different
3 − ]4
− brine
CO
2systems
−
++ H + ←⎯
2
pKina Figure
→[ CO
HCO
2 − − 5 will
] Influx
pKa2 of CO CO22− into HCO a wellbore
− is often accompanied
14
13 K
CO = [(H g ) +] ×H[HCO
O ← ⎯→
3
K]
HCO
− 3
+ H ( aq)
3 3
s
= A exp( B × pH ) 3 3
14 react
K = in the
2
PCO2 following ways to a CO2 [influx:
2 3
HCO3 ]
− by hydrogen sulfide (H2S). H2S is a weak acid with a
PCO2 − + pKa1 −
pH = − +log K − log−P5CO + log HCO 3 −+] H OH
− ←⎯ −⎯→ H2 −CO −
[CO322 −− ] [HCO pKa1 of − around
HCO 3 7. [ OHUnless
H2−CO] 3[CO the buffer is overwhelmed
15 [HCO CO322− HCO 3− ] H 2 SO4
3
15 pH = [ H−
•KConventional log] × [
K −
HCO log 2
P] + log
3 COdivalent 3 [ HCO 3
]
halide OH −
brines CO 3 can not HCO 3−
3
[ CO 3
] [HCO
by large
3 ] H SO
influxes
2 4
[ OHof
−
] [CO
CO , the carbonate buffer traps
H 2O 14 = 2
2
be buffered PCO2 with carbonate / bicarbonate because and retains this toxic gas in its less harmful form,
16
15 × Pf K − log P6CO +
0.02=corresponding CO2 ( g ) ←
log[HCO
− ⎯→ CO2−( aq )
3 ] OH (CaCO 2−
CO3 3, HCO
−
3 3) CO3
[ 2−
] [HCO −
3 ] H 2 SO4
[ OHHS] -. [CO
−
−
16 0pH
the.02×−Plog f 2
metal carbonate ZnCO namely bisulfide,
O3 precipitates out of solution resulting in the formation of 2 −
17 [CO 2 − ] + [OH −− ] = 0.02× Pf ( mol / L ) [ CO 2 − ]( mg / L) = 1200 × Pf
17 [CO332 − ] +in[OH
solids the] clear Pf ( mol / L/) completion fluid. These[ CO33 ]( mg /The
= 0.02×packer L) = 1200 fact ×that Pf any H2S is converted to HS - in a
CaCO3 ( s) 16 0.02× −Pf
18 [HCO
divalent ] = brines
0 have a naturally low pH (2 – 6), and[CO32 − ]( kg / m 2−
buffered
3
) = 1.2 × Pformate brine does not mean that the gas
18 [ CO[HCO
2 − 3− ]
]2 3− = 0 − CO ( aq) + H O ← [CO3 2 −]( kg / m3 ) = 1.2 × Pff
the 3 influx of ]CO 7
, dependent ⎯→ H 2CO 3 ( aq)
+ H + ( aq) 17 [CO −3
=] +A[OH
s exp( B=×0pH.202 )× Pf ( mol2/ L ) on 2the partial pressure [ CO3 ]( mg /isL)scavenged= 1200 × Pf and made permanently safe. If the
[ HCO3 ]
of CO − −2
, further lowers the pH. The CO2 largely 22−−
buffer was to be 2overwhelmed by an excessive
19 [OH ]
− 3 =] 0
[[CO ] kg / m
332− ]((ppb ) = 0) .=
3 42 × P×f Pf [CO32−− ]
18
19 HCO
converts
[OH ] = 0= 0to carbonic acid, which is
K a very corrosive.− [ +CO
CO ] (ppb )influx
= 0 . 42 1× .of
2P CO /
[ H
CO S,
] then H S gas would come back
8 2 3H CO ( aq) ←⎯1
⎯→ HCO ( aq) + H ( aq
3 3 ) f 2 2
3 2
20 [CO 2 − ] = 0.02× P ( mol / L)

20 − [CO332− − ] = 0.02× Pff ( mol
9 / L) CO32 −− + H + ←⎯ K a2
⎯→ HCO3
−
−
19 [OH2 − ] =HCO
0 3 − [CO32 − ] [HCO H 2 SO4 [ OH − ] [CO [CO3 2− ] (ppb) = 0.42× Pf [CO3 2− ]
HCO3 ] OH CO 3 3 ]
[[CO 2− ]−
21
20 HCO −] = 0
3 3 ]==00 .02× Pf ( mol / L)
21 [HCO 3 10 −
HCO3 + OH − ←
2−
⎯→ CO3 + H 2O
22 [OH ] = 0
−
22 [OH − ] =− 0
l / L) 21 [HCO 2 −3
] = 0 [ CO32 − ]( mg / L) 2=−1200 × Pf −
pH in various brine systems as a function of CO2 influx volume

12
11
Buffered formate brine pH>6.35:
10
CO2 mainly converted to
9 bicarbonate (HCO3-),
which does not promote corrosion
pH 8
Unbuffered formate brine
7
6 pH<6.35:
CO2 mainly converted to
5 carbonic acid (H2CO3),
Calcium bromide brine which promotes corrosion
4
0 50 100 150 200 250 3 00 3 50 40 0 450 500
BBL gas i nflux / BB L bu ffer ed fo r m ate br i n e ( 2% CO 2, 21°C / 70° F , 1 atm )
Increasing time of CO2 influx
Figure 5 pH as a function of CO2 influx in a typical halide brine, an unbuffered formate brine, and a buffered formate brine.
1 pH = − log [H + ]
2 pH = − log(a H + ) aH +
out of solution when pH dropped to below around to influx of acid Ka
gas. As acid gas initially enters the
3 HCOO− + H3 O +←⎯→ HCOOH + H O pK
7.0. CO2 gas would first be present in equilibrium brine, the carbonate (CO32-) 2is graduallya converted
with the bicarbonate in the brine at a lower pH topHbicarbonate
= − log [H + ] (HCO3-), whilst the pH remains at
1 1 pH = 2−− log [H+ + ] pKa − 2− −
(6.35). It is therefore important to remove any HS - 4 CO around
3 + H the ←⎯ upper
→ HCObuffer 3
2
level (pH = pKa2= 10.2). CO3 HCO3
contamination from used field muds, and never 2 2 pH = − log (a + ) a
pH When= − log −
(aall + )
the H
pKa1
carbonate a H + His converted, the buffer −
+
lower the pH or let the buffer deplete in a formate 5 HCO loses 3 +its HH +ability
←⎯⎯ → to H2 CO3 pKa1 HCO3 H2 CO3
+ K a maintain pH. The carbonate
3 3 HCOO
−
HCOO pKa
mud or brine that has been exposed to H2S without component
−
+ H3+OH+3← O⎯→ K a←⎯→ HCOOH + H2 O
of the HCOOH buffer +H 2O
system, ispK nowa referred
first checking if it is contaminated with HS -. If there 6 to( gas ‘overwhelmed’ or ‘swamped’ and the buffer
CO 2 2)−← ⎯→
+
CO2pK( aq ) − 2− −
pKisa2pK
2CO
a
is any concern about H2S-related corrosion then 4 4 CO 2capacity CO − 3 ++ H pK
+ H ←⎯→ HCO3 at←a ⎯ the → HCO
upper −
2 3 buffering level
2
zero.
a 2 CO Any − 3
HCO HCO− 3
3 3 3
H2S scavenger should be added (see Section B6 further −
influx +
of
pKa1
acid gas can now easily lower the −
5 5 HCO HCO − 3H + + H pK ← a1 ⎯ ⎯H→CO H2 CO3 pK 1 HCO − H2 CO3
‘Compatibility with metals’ and Section B5 pH 3 + down to the 2lower buffer level ( pKa1 = a6.35) HCO
←⎯ ⎯ → 3 H CO
3 3 2 3
‘Compatibility with additives’). provided by the bicarbonate. (See Figure 5.)

7 CO2 ( aq) + H 2O ← ⎯→ H 2CO3 ( aq)
1 pH = − log [H + ] 6 6 CO2CO ( g )2← (⎯→
g) ← ⎯→CO2CO ( aq2)( aq )
It is important to notice that whilst the pH of a
2 A6.3 Buffering
pH = − log(a H + ) a Hrequirement
+
and 8 CO3 ( aq) ←formate
H2buffered ⎯
Ka
⎯→ HCObrine
−
3 ( aq) is
1
+ Ha +function
( aq) of the ratio of
buffer capacity concentrations
2− Ka
of carbonate
−
and bicarbonate, the
3 HCOO− + H3 O +←⎯→ Ka
HCOOH + H2 O pKa 9 CO3 + H + ←⎯ ⎯→ HCO3 2
buffer capacity depends upon the actual carbonate

Whenever formate brine is used in the field, it is 7
7 CO CO ( aq2)(+aqH) 2+OH←
2concentration.
2O ←
⎯→ ⎯→ H 2CO H 2CO
3 ( aq)
3 ( aq)
important topKmaintain − the ability of the buffer to

− − 2−
CO3 10 HCO HCO 3 + OH ← ⎯→ CO3 + H 2O
2− 2− −
4 CO3 + H + ←⎯ a
→ HCO3
2
pKa2 Ka −
resist acid influxes. In order to do this, both the 8 3
H2 CO
Whenever ( )(←aq⎯ K) a←⎯ ⎯
the HCO
→buffer − ( aq) ++ H + ( aq
1
3 capacity in) the field is getting
8 H CO aq ⎯ → HCO 3 ( aq) + H ( aq)
3 1
2 3
5 buffer
HCO3 +
−
capacity
H ←⎯⎯and
+ pKa1
→ H2theCO3 total buffer concentration
pKa1 HCO3
−
H2 CO low, 2 − it can + be K increased − by a simple addition of OH-
11 9 CO 2CO ++ 2←
H+⎯ HCO
3−2 − a −
CO + CO KH a←O ⎯ ⎯⎯ → 2HCO
2
9 3 + 3 H ⎯ →2 HCO ⎯→ − 3
need to be monitored and maintained. 3(NaOH or KOH): 3
2
3
CO
2−
) + Ca 2+ ( aq) ⎯
6 CO2 ( g ) ← ⎯→ CO2 ( aq ) capacity 12 3 ( aq ⎯→2 ↓ CaCO3 ( s)
A6.3.1 Buffer 10 HCO −
−
+ OH
−
−
← ⎯→ 2CO−
−
+ H O (10)
10 HCO3 + 3OH ← ⎯→KCO3 +3 H− 2O 2+ [ CO3 ] 2 −
Buffer capacity is defined as the moles of acid or 13 CO2 ( g) + H 2O ←⎯→ HCO3 + H ( aq) −
= A exp( B × pH )
s
[ HCO3 ]
base necessary to change the pH of one liter of In other 2− words, it is unnecessary − to add new
11 11 2CO − 3 + CO2 + H 2O ⎯
CO3carbonate
+[CO
⎯→ 2HCO −
solution by one unit. H + 2] ×+[HCO H 2Obuffer ⎯
3 ]
⎯→ 2HCO
in order to regain buffer capacity.
− 3
3
CO2 ( aq) + H 2O ← ⎯→ H 2CO3 ( aq) 14 K = 2−
7 2CO − 3 ( aq)CO P 2+
12 12 CO3A6.3.2 ( aq) + Ca+22Buffer Ca
+
( aq)( ⎯ aq
⎯→ )⎯ ⎯→↓ CaCO ↓ CaCO
concentration 3−( s )
3 ( s)
In alkaline brines that are buffered with a carbonate /15 pH = − log K − log PCO + log[HCO3 ] OH − CO [ − 3 32− ] HCO3 [CO3 ] [HCO3 ] H
2− − 2− −
aH + 13 CO ( g ) + H O K
HCO
−
+ H
2 +
( aq ) [ CO32CO ] = A exp( B × pH )
bicarbonate K buffer,
→ HCOthe following equilibrium exists: 13 CO2The ( g)2+total H 2O ← buffer
K
2⎯→ HCO← ⎯→ concentration
− + in a brine [ − =that is B
A] exp(
s
buff-
× pH )
3 + H ( aq)
− + −
8 H2 CO3 ( aq) ←⎯ ⎯ a 1
3 ( aq) + H ( aq)
3
[ HCOHCO ] 3
s
ered with carbonate / bicarbonate is 3defined as the

⎯→ HCOOH + H2 O pKa 2 − 0.combined
02×+ P
(9)16 [Hf + ] × [HCO 3 ]
Ka − −
9 CO3 + H + ←⎯ ⎯→ HCO3
2
concentration of carbonate (CO32-),
K[H= ] × [HCO3 ]
−
14 14 K =bicarbonate PCO ] = 0(HCO ), and carbonic acid (H2CO3).
-
2−
17 [CO32 − ] +P[CO OH − 2
.02× Pf 3( mol / L ) [ CO32 − ]( mg / L) = 1200 ×
− −
pKa2 =− 10.2 IfpHthe = −total buffer
log PCOconcentration −has been − 3 removed
2−
2 −
HCO3 CO−3 HCO 15 log K − +[ log[HCO
−
] OH −
2CO
2−
HCO
−
[2CO
− ] [HCO − ]
HCO3 [CO32 −] 3 [HCO33 ] 3 H 2 S
− −
10 HCO3 + OH ←
2 −3
⎯→ CO3 + H 2O 15 pH = − log − K − log PCO + log HCO3
] 3
2 OH CO3 3
18 [HCOfrom 3
] =the0 fluid in other reactions,
2
new buffer will [ CO 3
] ( kg / m ) = 1.2× P
−
→ H2 CO3 pKthe
In a1 HCO
field, buffer
3 H2 CO3 is typically lost by exposure
capacity need to be added to the fluid.
11
2−
CO3 + CO2 + H 2O ⎯ ⎯→ 2HCO3
−
16 16 0.020×.02 P × Pf
19 [OH − ]f= 0 [CO3 2− ] (ppb) = 0.42× Pf
2−
) 17 [ 2−
] [ ] [ 7 [3CO ](3mg](/mg L) /=L1200
) = 120
−
17 [CO3 2] +CO
2 − + OH
3 [OH ] = 0.02× P ( mol = 0 . 02 × P ( mol / L ) 2−
P A G E CO ×P
2− − f / L)
12 CO
V E 3R (Saq Ca 21+ ( aq
I )O+ N – ) 1⎯2 / 0↓7CaCO3 ( s)
⎯→ − f SE CTION A6
2−
20 [CO 3
] = 0 .02 × P f ( mol / L )
[ CO3 ] 18) [HCO [HCO −
] 3 ]=0
−
[CO[32CO
2−
− 3 ]( kg3 / m ) = 1.2 ×
3
]( kg / m ) = 1.2 × Pf
18
= A exp( B × pH 3 =0
K −
13 CO2 ( g) + H 2O ←⎯→ HCO3 + H + ( aq) −
s
[ HCO3 ]
21 [HCO3− ] = 0 −
2−
H 2CO3 ( aq) [H + ] × [HCO3 − ] [OH ] = 0 [CO[CO
2− 3 ] (ppb) = 0.42× P
14 19 19 [OH − ] = 0 ] (ppb) = 0.42× P
11
10
Carbonate / bicarbonate molar ratio
8
+
+
1 pH = − log [H ]
1 7 [H ]
pH = − log [ CO32− ] −111 pH = − log [H ] +
−
= 9.69164 10 · exp( 2.29762135 × pH )
2 6 (a + )
pH = − log H
aH + [ HCO3 ] 2
2
pH = − log(a )
pH = − log(a )
a
a H+
H+
H+
H+
5 Ka
3 Ka
HCOO− + H3 O +←⎯→ HCOOH + H2 O pKa 3 HCOO−− + H3 O ++←⎯→
Ka HCOOH + H2 O pKa
3 HCOO + H3 O ←⎯→ HCOOH + H2 O pKa
4
3+
2− a2 pK −
pKa2
2−
CO3 4 3−
2−
CO32 − + H ++ ←⎯ a2 pK
pKa → HCO3 −
−
pKa2
2−
CO32 − HCO3−
−
4 CO3 + H ←⎯ → HCO3 HCO
pKa2 CO3
4 CO3 + H ←⎯ 2
→ HCO3 HCO3
2 − pK −
5 HCO3 + H + ←⎯⎯
a1
→ H2 CO3
− pK
pKa1 HCO3
−
H25CO3 HCO3− + H ++ ←⎯⎯
pK
a1
→ H2 CO3 pKa1 HCO3− H2 CO3
1 5 HCO3 + H ←⎯⎯ a1
→ H2 CO3 pKa1 HCO3 H2 CO3
+
1 pH = − log 0 [H ]
6 CO2 ( g ) ←
⎯→7CO2 ( aq ) 7.5 8 8.5 69 CO2 ( g ) ←⎯→ CO2 ( aq ) 10
9.5 10.5 11
6 CO2 ( g ) ←⎯→ CO2 ( aq )
2 pH = − log(a H + ) aH + pH
Ka
3 Figure H3 O +←⎯→
HCOO−6+Relationship HCOOH the
between + H2carbonate
O pK
to abicarbonate ratio and the pH in a formate brine. The pH is measured with a calibrated
glass electrode in a variety of laboratory and field brines, diluted with nine parts
COwater.
( aq) + H O ←⎯→ H 2CO3 ( aq)
7 CO2 ( aq) + H 2O ←⎯→ H 2CO3 ( aq) 7
2− pKa − 2− 7 − CO22 ( aq) + H 22O ←
⎯→ H 2CO3 ( aq)
4 CO3 + H + ←⎯ → HCO3 pKa2 2
CO3 HCO3
K Ka − +
8
5 H2 CO
HCO
−
( aq) ←
3 3 + H ←⎯
+
⎯
⎯a pKa
→ HCO
−
H23CO ( aq ) + H + ( aq) pKa1 HCO3
−
H2 8 H2 CO3 ( aq) ←⎯ ⎯ a 1→ HCO3 − ( aq) + H + ( aq)
1
8COFormate
1
⎯1 → 3 3 ( aq) ←⎯
H2 CO3brines
K
⎯ → HCO ( aq) + H buffered
( aq)
There are three ways in which the buffer concentration that are3 heavily with
2− K a2 −
9 in
2−
+ H + ←⎯
COa3 formate Ka
⎯brine
→ HCOcan
−
3 be altered during field use:
2
CO32 − + H/ ++bicarbonate
9 carbonate ←⎯ ⎯
K a2 → HCO − equilibrate faster and
9 CO3 + H ←⎯ ⎯→ HCO33
6 CO2 ( g ) ← ⎯→ CO2 ( aq ) decompose less.
1. Influx of acid gas (CO ) increases buffer − 2−
10 −
HCO3 + OH − ←
2−
⎯→ CO3 + H 2O 2 10 HCO3 − + OH −− ←
⎯→ CO32 − + H 2O
concentration: 10 A6.3.3
HCO3 Buffer
+ OH ← ⎯→requirement
CO3 + H 2O for field use
1 pH = − log [H + ]
The recommended buffer concentration required
2− −
11
7
2−
CO23 ( aq
+ CO
) + 2H+2OH←O⎯
2⎯→ H2
⎯→ 2HCOpH ) = − log(a H + )
2CO3 ( aq3
−
a H +(11) 11 in formate
CO32 −+ CO + H Odepends
brines ⎯ ⎯→ 2HCO on − the application. The
11 CO3 + CO22 + H 22O ⎯ ⎯→ 2HCO33
amount 2−
of time the brine will be in contact with the
2−
CO3 ( aq Ca 2+converts3 ↓carbonate − + Ka
HCOOHto+ H2 O 12 reservoir pKCO ( aq) + Ca 2++ ( aq) ⎯ ⎯→ ↓ CaCO3 ( s)
12 Influx of) +CO K
2a1
( aq) ⎯
⎯→
−
CaCO
HCOO 3 ( s )+ Hfrom
3 O ←⎯→ the buffer 12 CO a 32 − fluids, 2and
3 ( aq ) + Ca ( aq ) the
⎯ ⎯→ expected
↓ CaCO 3 ( s)
level of acid gas
8 H2 CO3 ( aq) ←⎯ ⎯→ HCO3 ( aq) + H + ( aq) [ CO32− ] drops [ CO322−− ]
13 bicarbonate. The
K buffer − capacity
+ therefore = A exp( B × pH ) 13 influx,
CO are
( g ) important
+ H O K factors.
HCO
−
+ HIn+ (well
aq ) suspension
[ CO3 −] = A exp( B × pH )
CO2 ( g) + H 2O ←⎯→ HCO3 + H ( aq) s
←⎯→ s
whilst HCO
−
[(carbonate ] 13 CO2 ( g) + Happlications
2
2O
2
− ←
K
⎯→ HCO 3− +
− 3 + H ( aq [
) formate HCO ] = A exp( B × pH )
s
CO3 +the total

K a2 buffer− concentration + and pKpacker HCO3 where the [ HCO33−brine
2− pK −
9 2−
H+← ⎯⎯→ HCO 4 3 CO3 + H + ←⎯ a2
→ HCO
3
3 a2 CO32 ]
bicarbonate + carbonic acid) increases by the may be[Hexposed to] well conditions for a long time,
+ ] × [HCO
+ −
[H + ] × [HCO3 − ] − 3−
14 K=
amount of CO2 entering5 HCO
−
the 3brine.
+
+ H ←⎯⎯→ H2 CO3
pKa1
14 a high K a1=level
pK [H ]HCO [HCO
×of 3 ] H 2 CO
buffering would be appropriate. In
− PCO2− ← 2− 14 K= PCO23 3
10 HCO3 + OH ⎯→ CO3 + H 2O applications P where
CO well exposure times are short, 2− −
2− 2−
HCO3 [CO3 ] 15[HCO3pH
− −
log K −[log OHP] 2 +[CO log[HCO3 − ]
−
OH −− CO322 −− HCO3 −− [CO32 − ] [HCO3− ] H 2 S
− 2
15 pH = − log K − log PCO2 + log[HCO3 ] OH CO3 −
] =H−2 SO −
2. Influx of multivalent cations decreases 15 andpH in = − log4K − log PCO
applications where + log[HCO 3 ]
no acid OH is CO
gas expected, HCO3 [CO3 ] [HCO3 ] H 2 S
6 CO2 ( g ) ← ⎯→ CO2 ( aq ) CO 2 3
11 buffer
CO3 + COconcentration:
2− − a smaller buffer concentration will do.
2 + H 2O ⎯ ⎯→ 2HCO3
16 0.02× Pf 16 0.02× Pf
2− 16 0.02× Pf
12 CO3 ( aq) + Ca 2+ ( aq) ⎯ ⎯→ ↓ CaCO3 ( s) (12) 2 − Adding2 only soluble carbonate to the brine provides
17 [CO32 − ] + [OH − ] = 0.02× Pf ( mol / L ) [ ]
CO3 ( mg 17 = [[1200
CO3level
−
] +P[OH −− ] = 0.02× Pf ( mol / L ) [ CO322 −− ]( mg / L) = 1200 × P
[ CO32− ] 17 /aL)high 2 −×
CO3 ] + [fOH of buffer
] = 0.02×capacity,
Pf ( mol / L ) but the pH might [ CO3 ]( mg / L) = 1200 × P
7 3 +CO H 2 ((aq
aq))+consumes
H 2O ← ⎯→ H = A3 (exp(
CO aq) B × pH )
K −
13 CO2influx
( g−) + Hof 2O multivalent
←⎯→ HCO + s
An cations [ HCO
− 2
] the buffer become
18/ m ) =[[1
−higher than wanted. This problem can be
[HCO3 ] = 0 .2 ×3P− ]]f = 0 [CO322 −− ]( kg / m33 ) = 1.2 × Pf
2−
18 3 [CO3 ]( kg 3
HCO
by precipitating out insoluble calcium carbonate. 18 solved HCO by3 = 0
including some bicarbonate. Although the [CO3 ]( kg / m ) = 1.2 × Pf
The [H + ] × [HCO3 − ]
K = total amount of 8 carbonate / )bicarbonate
K a1
⎯→ HCO3 (buffer addition of bicarbonate does not contribute to the
−
14 H2 CO3 ( aq ←⎯ aq) + H + ( aq)
19 [OH ] = 0 PCO
−
available decreases by the amount of carbonate[CO3 ] (ppb
2−
[OH
19 )initial
= 0.42 P−f]] = 0 capacity
−
×buffer [CO3 2− ] it will contribute positively to [CO3 22−− ] (ppb) = 0.42× Pf
2
2 − + K − 19 [−OH =0 [CO3 ] (ppb) = 0.42× Pf
15 pH = is
that − log 9
K − log PCO2 + log
precipitated, and[HCOCO
new
−
+
33 ] buffer
H ← −
OH should ⎯⎯ a 2
→
CO3 HCO
2−
HCO
be
3 3
−
[ CO3
2−
] [HCO ] HpH
the3 final 2 SO4of the
[ −
OH brine] [ COif the buffer is overwhelmed
20 [CO32 − ] = 0.02× Pf ( mol / L) 20 [CO322 −− ] = 0.02× Pf ( mol / L)
added to the fluid. 20 by acid[CO3 gas ] = 0.influx,
02× Pf ( and mol / Lit) will contribute positively to
16 0.02× Pf 10 −
HCO3 + OH − ←
2−
⎯→ CO3 + H 2O the fluid’s thermal stability.
21 [HCO3 ] = 0
3. Formate
−
decomposition increases buffer 21 [HCO3−− ] = 0
2− 21 [HCO3 ] = 0
17 [CO3 ] + [OH ] = 0.02× Pf ( mol / L )
concentration
2− −
[ CO3 ]( mg /ItL)has= 1200been × Pf shown that the pH of buffered formate
22 [Small
OH − ] =amounts
0 of 11
soluble CO
2−
+
carbonate CO + H O
and ⎯
⎯→ 2HCO
bicarbonate
−
22 brine [OHis
−
]= 0
− dependent on the ratio between carbonate
3 2 2 3
22 [OH ] =0
[HCO3− ] = 0 [ 2−
] 3
18 can 2 form
− as a result of formate 2− decomposition if CO3 ( kg / m and ) = 1bicarbonate
[
.2 ×2 −Pf
] according to the following equation:
23 [CO3 ] = 0.02× Pf ( mol12
/ L) CO3 ( aq) + Ca ( aq) ⎯ 2+
⎯→ ↓ CaCO3 ( s) 23 CO = 0.02× P ( mol / L)
the brine is exposed to high temperature for an 23 [CO332 − ] = 0.02× Pff ( mol / L)
[ CO 2− ]
extended
[OH − ] = 0 period of timeCO (See Section⎯→ KA13 Thermal
− 2−
)] (ppb) = 0.42−× P=f A exp(
3
B[ × 2pH
− ) (13)
[ CO3 ] 13 [CO
+
19 2 ( g ) + H 2O ← HCO3 + H ( aq [CO CO ]
3 3 ]
s
2− 3 [ HCO3 ] − [ CO ]
2−
24
−
[ HCO3 ] = The
stability). reaction ( molis
/ L reversible
) and the 24 [ HCO3− = .] 3
. ( mol/ L) 2−
. exp ( B . pH ) 24 [ HCO3 ] = A . exp ( B . pH ) ( mol/ L)
20 [CO32 − ] = 0.A02
establish × Pf (of
ment molequilibrium
/ L) [Hin + closed− HPHT well
] × [HCO3 ] where A exp ( B pH )
25 A = 9 .69164 10 −11
14 K= 25 A = 9.69164 10−−11
systems usually limits formate decomposition PCO2 to a 25 A = 9 .69164 10 11
26 few
B = 2 percent
.29762135 in typical formate brine formulations. 26 B 2=
− 2.29762135 2− −
[CO3 ] [HCO3 ] H 2 SO4 [ OH ] [CO
[HCO3 ] = 0 −
− − −
21
−
15 pH = − log K − log PCO + log[HCO3 ] 2
OH26 COB3 = 2HCO .29762135
3
27 [OH −− ] = 0 27 [OH −− ] = 0
22 [OH ] = 0 27 [OH ] = 0
28 [CO32P− ]A=G 0E 8 16S E C T 0.I02 O×NPf A 6 28 [CO322 −− ] = 0 VE R SION 1 – 1 2 / 0 7
28 [CO3 ] = 0
23 [CO3−2 − ] = 0.02× P ( mol / L ) − 2− −
OH CO3
2 −f
17
−
pK
HCO3 [CO ]a+ [OH − ] = 0.02× P ( mol / L )
2 − OH CO [ CO 2 − HCO
32 − ]( mg / L ) 3=
pKa
OH − HCO3 1200 pK×a Pf
−
3 f CO 3 3
[OH − ]− [CO [ CO
2 −
]
3 3 ]
[ HCO
−
] −P H SO [ OH −
] [CO
2 −
] [ HCO
−
] Pf H 2 SO4
[ HCO3 ] = . 18 ( mol/[LHCO
3
) 3 ] =f 0 2 4
2−
[OH − ] [CO
[CO332 −] ]( kg /[m
2
3 −
HCO
3
) =31].2 × PP
3 −
H 2 SO4
24 f f
A exp ( B . pH )
27−7 COCO 2 (2aq( aq ) +) +HH2O2O← ⎯→
← ⎯→HH2CO 2CO
( aq ))
( aq
+
1 1 pH = −
pHlog=[H− log] [H + ] 2− 2− + + pKapK [ CO− − ] 23−23 − − −
4 4 K CO 3 3+ − H HCO = A exp( B × pH )pKpK CO CO HCO
2 a2
CO2 ( g) + H 2O ← 13 ⎯→ HCO CO + H← + ← ⎯ ⎯ →→ HCO 3 33 HCO

3 + H ( aq)
+ a2 a2 3 3 3 3
1 pH = − log [H ]
s
−
[ HCO3 ]
2 2 pH = −
aH + aH +
pHlog=(a−Hlog
+ ) (a + ) − − + + pKapK − −− −
H 55 HCO HCO 3 3+ + HH ←← ⎯⎯ ⎯ ⎯→→
1 a1
H2HCO 2 CO
pK pK
K aK1 a 1 HCO HCO HH2H+CO
(CO
2 pH = − log(a H + ) aH + 8
3 83 HH 2 CO2 CO 3 (3aq( aq )← )← ⎯
⎯ a⎯
1⎯ →
a1→ HCOHCO 3 33( aq
(3aq) +) +H (+2aq 3) 3
aq )
S E C T I O N A : C H E M I C A L A N−D P H − Y+ S I K Ca14
A+ L KP 7 [ H
a R O P E R T I E S
+
]
CO × [2 (
HCOaq ) +
3
−
H] 2O ← ⎯→ H 2CO ( aq )
CABO T S P ECIALTY FLUIDS
3
3 3HCOO HCOO+ H3 O+ ← H3⎯→ O ←HCOOH⎯→ HCOOHK = + H2 O+ H2 O pK a pK a
Ka PCO2 99 COCO
2 −2 −
3 3 ++ HH ←← + + K aK2 a2
⎯ ⎯ ⎯⎯ →→HCO HCO
−−
3 HCOO− + H3 O +←⎯→ HCOOH + H2 O pKa 66 ( g2 ([)HCO
3 3
CO CO g← )←
⎯→ ⎯→ −CO CO 2 (OH
aq )−
2 ( aq+) CO
2− −
15 pH = − log K − log P +
K a2log −]
2−
HCO
−
[ CO ] [HCO ] H 2 SO4 [ OH − ]
2− 2+− pKa+ pKa − 8 − H 2 CO 3 ( aq ) ←
CO 2 ⎯⎯ 1
→ HCO 3
2
3 − ( aq )
2 +− H ( aq
− ) 3
−
3 3 3
4 4CO3 CO + H3 ← +⎯ H 2← →⎯ HCO 2
→3HCO3 pKa2 pKa2CO3 CO3 HCO3HCO3 −− − 2 −2 −
4
2−
CO3 + H + ←⎯
pKa
→ HCO3
−
pKa2 CO3 pK
2−
HCO
− 2− + K a2 − 1010 HCO
HCO 3 3 ++ OH OH −← ⎯→
← ⎯→CO CO 3 3 ++ HH2O 2O
9
2
− − pKa1 3 CO
Titration 3 + H
curves ←⎯ ⎯→ HCO3 − −
5 5HCO3HCO + H3 ←+
+H ⎯⎯← +a1
→16⎯H⎯ 2 CO
→ H0
3 2
.02CO × 3
P f pK a1
pK a 1
HCO 3 HCO 3H 2 CO H
3 2 CO 3
− pKa1 −
5 HCO3 + H + ←⎯⎯ → H13
2 CO3 pKa1 HCO3 H2 CO3 2 − ( aq ) +/)LH
[CO3 ] + [OH − 7 7 CO CO 2 ( aq +)2 2HO← O⎯→ H 2HCO 2CO3 (11
aq ) ) CO
( aq 2 −2 − − −
17 −] = 0.02×
← ⎯→ 311 CO 3 3[+ CO +CO CO 2−+ H O ⎯
] + H2 /2O L)⎯→ 2HCO
2HCO
3 2 2( mg = 1200 × P3f 3
− Pf2( mol − 2 ⎯ ⎯→
12 10 HCO3 + OH ← ⎯→ CO3 + H 2O
6 6CO2 ( gCO
)← Phenolphthalein endpoint
2 ( g) ←
⎯→ CO⎯→ 2 ( aqCO ) 2 ( aq )
Methyl orange12 endpoint CO
2 −2 −
( aq )2+)− +
]Ca
2+ + 3
Ca/2(m aq
6 CO2 ( g ) ←
⎯→ CO2 ( aq )
11 18 [HCO3− ] = 0 12 CO[CO
+ + 3 3
( aq ( kg )) =⎯
( aq )⎯→
1⎯.2 ×↓P↓CaCO
⎯→ CaCO 3 (3s()s )
) ←Water
K a 1K a 1 + standard
10 88 H2HCO 2 CO 3 ( aq3 ( aq) ←⎯
⎯ ⎯⎯ →−→ HCO HCO
− −
3 3( aq ) buffer
( aq +) H+H ( aq ) ) 3
( aq
f
11
2−
CO3 + CO2 + H 2O ⎯ ⎯→ 2HCO KFo + standard buffer K −
9 2 −2 − + + K a2K a2
3
− −
1313 COCO 2 (2g (g)+ ) +HH2O 2O ←
←⎯→ ⎯→K
HCOHCO 3 3++
− +
HH (+aq ( aq ))
[ OH −
] = 0 99 CO CO +H + H← ⎯
← ⎯⎯ ⎯→→ HCO HCO [ CO
2−
] (ppb ) = 0 .42 × P [ 2−
]
8 19 2−
CO3 ( aq) + Ca ( aq) ⎯ 2+ 3
3
⎯→ ↓ CaCO3 ( s)
3 3 CO
12 3 f 3
pH 7 CO
7 2 ( aq
CO) +
2 (Haq
2 )
O +← H
⎯→ 2O H
← ⎯→2 CO H (
3 2 aq CO ) 3 ( aq ) [ H[ H
+
]+
× ] [
× [
HCO HCO
−
]−
]
7 [CO32 − ] = 0.02× Pf ( mol / L)K − − 1414 [ COK3 K=
2 −
]= 3 3
7 CO2 ( aq) + H 2O ← ⎯→ H 2CO3 ( aq) 20 13 − −− + H + ( aq2) −2 − = A exp( B × pH )
6 CO2 (10 g10
) + H 2O HCO ←⎯→
HCO 3 3+ OH
HCO
+ OH3← ⎯→← ⎯→ CO 3 3+H
CO + 2HO 2O
− PCO PCO
s
[ HCO 3
] 2 2
− −
5 8H2 COH3 (2aq )←
K a1 K a1 − − + + 1515 pHpH==−−log logKK−−log logPCO PCO ++log log[HCO
[HCO 3 3] ] OH OH
8 CO 3 (⎯⎯)→
aq ←HCO⎯⎯→3HCO ( aq)3+ (H aq)(+aqH) ( aq) 2 2
8 H2 CO3 ( aq) ←⎯
K a1 −
⎯→ HCO34 ( aq) + H ( aq)+ 21 [HCO3 K
−
] = 0= [ H +
] × [ HCO 3
−
]
14 1111 CO
2 −2 −
CO+ CO + CO 2 + H HO2O
2 +2
⎯ ⎯→ ⎯⎯→ 2HCO2HCO
− −
3 9 9CO32 −CO 2−
+ H3 + ← +⎯ HK a2+
⎯→ ←HCOK a2
⎯⎯→3HCO3
− −
PCO2 3 3 3 3
9 2−
CO3 + H ←⎯ + K a2
⎯→ HCO32
− 22 [OH −
] = 0 1616 0.0
202.−02 ××PP
15 pH =12 −12 log K CO − COlog P
2 −
(2aq −
CO ) ++)log
( 2aq Ca
+ Ca [2HCO
+ 2+
( aq
−
3) ⎯
( aq ])⎯→
⎯⎯→ OH↓ CaCO
−
↓ CaCO CO(3s)( s) HCO f f −
3
[CO32 − ] [HCO3− ] H 2 SO4
3 3 3 3
-0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.42 −2 − 0.5
10HCO3HCO −
10 + OH
−−
3 +← OH⎯→ −
23
CO
←⎯→
2−
3 CO + [H
CO 2− 2−
3 2O 3+ H ] =2O 0.02× Pf ( mol / L) 1717 + [CO [CO 3 3 +
] ] +[OH[ [CO
OH
[ CO
− 2]− 2 −
=] =0].002 .02 ××PP f ( mol
( mol / L/ )L )
1313 CO CO 2(g ) + H 2O2O K K
HCO
− −
+H + H( aq +
) )
3 3
= A exp(f B × pH )
− − = A exp( B × pH )
2 ( g) + H HCO ( aq
− 2− ←⎯→ ← ⎯→ s s
10 HCO3 + OH − ← ⎯→ CO3 + H 2O 16 0.02× Pf

3 3
[ HCO[ HCO ] ]
Added OH- [mol/L] + 1818 [HCO[HCO − −
3 3 =
] ] =0 0 3 3
2− 2− − − −
[ CO32− ]Added H+ [mol/L]−
11 11CO3 +CO CO 3 2+ +CO H 22O+⎯ H24
⎯→ 2O 2HCO ⎯ ⎯→ [ HCO
2HCO 3 ]3= [CO ]14
+ ([OH
[H[H/]L×)][×HCO
( mol +
[HCO ] ]−
[ CO32 − ]( mg / L) = 1200 × Pf
K] K
2−
2− −
17 3
A3.14 exp B . pH
−
=
)=0=.02× Pf ( mol / L )
3 3
11 CO3 + CO2 + H 2O ⎯ ⎯→ 2HCO3 PCOPCO

Figure 7 Titration curves 12 for 12CO buffered
2−
aq)3water
2−
aq) +and
2+
Ca)25 buffered
2+
A potassium
= 9↓.69164 ) formate.
10 −11
Both fluids contain the same 1919amount [OH [OH of]added
− −
=]−=0 0 carbonate /
3 (CO +(Ca ( aq ( aq) ↓ CaCO CaCO
3 ([s 3 ( s]) = 0
2 2
⎯ ⎯→ ⎯ ⎯→
18 HCO
−
[CO 2−
2 −2 − ]( kg /−m−3 ) = 1.22−× 2 −P
15
3 15 pH pH = 2− =− log− log KK − log
− log PCOP2CO+2 log + log [HCO[HCO
− −
3 ]3 ] OH OH −
CO CO 3 3 HCO
3 HCO 3 3 CO
[ [CO ] ] [fHCO
[HC3
CO3 ( aq) + Ca 2+ (bicarbonate buffer3 ((17.8 kg/m3 / 6.25 ppb K2CO3 and 10.7 kg/m3 / 3.75 ppb 2KHCO ).] The phenolphthalein and methyl orange endpoints
2− 3 3
12 aq) ⎯ ⎯→ ↓ CaCO s) [ CO
−
[
] CO 2 −
13 13 CO ( g CO ) + H( g O
) + ← H⎯→K 26 K
O ← HCO
⎯→
−B = 2
HCO
+ H +−.29762135
(+aq H ) +
( aq )
3
= 3
A
3
exp(
= A B exp(
× pH B ) × pH ) 2020 [CO [CO
2−
] =] =0 .002
. 02 × ×P P ( mol
f f ( mol / L ) / L )
from the standard API RP 13B-1 [ CO3 2 alkalinity 2 2 titrations are 3shown. 3 No methyl orange endpoint can be detected in the buffered formate brine
s s
2 − 3 3
] 2
[ HCO3[ HCO−
] −
]
13 CO2 ( g) + H 2O ←⎯→ K −
+ H + ( aq) = A exp( B × pH ) 3
due HCO at[19 ] = [0OH ] =16 [CO3 2− ] (ppb) = 0.42× Pf [C
−
27 OH −
0
s
to the3 formate/formic acid

[ HCO equilibrium
−
] establishing a higher pH.16 0.02 0.02 ×P ×f Pf
3
[H + ] ×[[H HCO +
] [ −
× 3HCO3] −
] 2121 [ [
HCO
−
]−
=
] 0
14 14K = K = 28 [CO3 ] = 2−
0 2 − ] = 0.02× P 2(−mol HCO = 0
20 [CO 3 1717 [CO [CO 2 − / L )− −
] ][OH [OH] =] 0=.02
3 3
[ CO [ CO 2 −2 −
] ]( mg
[H + ] × [HCO3 − ] PCO2 PCO2 3f 3 + + 0.02 × P×f P( mol f ( mol / L/) L ) 3 3 ( mg / L/)L=)
14 K= − 2− −
pK
PCO2 This relationship is shown in Figure 6, and is valid [ OH [ −
] −CO−3 at pH
OH ] OH −2 − HCO = 3.75 23− −(
[ CO −formic acid).
2 −
[]CO [
2 −
] 2222
−
[ ] This
H
− [
]OH
SO [OH is
−
H ]− illustrated
=]
SO =
[0OH0 −
][ OH [ − in
] [
15 15pH = − pH log=K−− log log KP−COlog +P log
CO2 HCO
+ log3 HCO3 CO3[ [CO HCO3− ] − ] 3HCO3 3 3HCO3 HCO3 2 CO CO
a
2 −2 −
18−18 HCO HCO 3 =−0 =can 0 be seen, 4 2 4 [CO [CO ] ]( kg
3 3 ( kg / m/ 3m) 3=)
pH = − log K − logfor PCO2pH measured with− a calibrated
HCO3 glass [CO32electrode 2Figure 7.3[CO As the formic / formic acid
2
− −−
15 + log [HCO3 − ] OH CO3
2− −
] [HCO [OH 3 ] ] H [HCO 2 SO
[CO −
[]OH − ] [ HCO ]
21 34 ]3= 0 Pf H 2 SO4 23 2 −2 −
in formate brine that is diluted 1:10 with water. From equilibrium starts to establish
3
23 at a[CO [CO pH ] = 0 . 02
] = 0.02× P
3 3 significantly × P ( mol
f f ( mol / L ) / L )
this figure it can be 16 seen160.02 that ×0P.02 × Pf
fbuffering the brine 0higher than
22 [OH −19 ] =19 [OH [OH ] =]0= 0the methyl orange endpoint.
− −
[CO [CO 2− 2−
] ] (ppb
3 3 (ppb ) =)0=.40
16 0.02× Pf with carbonate and bicarbonate [ CO
[ CO 2 − 2]− ]
2 −in a ratio of about − 3 3
17 17[CO3 []CO 2−
+ [OH ] +][=
−
OH 0.02] =
−
×P 0.f02 ( mol
×P / L
( mol
) / L ) 2− [ CO
2−
[ ]
CO ( mg
2−
/ ]L( mg
) 24
= 241200
/ L ) = × [ HCO
1200
P[ HCO ×3P ]−
=
3 f] = . . . ( mol
( mol / L/ )
L )
5:3 (1.67) will yield an ideal pH of about210 – 10.5. 23 [CO3 20]20 =The0.02[CO × P3f ( mol
[CO
fact
2 − 2
] =] 0=/.02
− L0only
.)02 AAexp exp( B( BpH . pH ))
3that ×P ×f P(one mol /ofL/)Lthe two standard titration
3 f 3 3 f
f ( mol )
17 [CO32 − ] + [OH − ] = 0.02× Pf ( mol / L ) [ CO3 − ]( mg / L) = 1200 × Pf
[
18 18 HCO3 HCO [
−
] = 03 = 0
−
] endpoints can [ CObe 3
2 −determined
[ ]
CO( kg 3
2− 3
/ m] ( kg) 25
=25
/ 1
m .23 in A
)× =P 1 a
f.A2= formate
×=9 .
9
P 69164
f
. 69164 10brine,
10
−11−11
[ CO3that 2− ]
18 [HCO3− ] = 0 [CO32 − ]( kg / m24 3
) = 1.2 ×[ HCO Pf 21− ] means = . [HCO − − the standard API alkalinity test method
3 21 [ HCO
exp ( B3 . pH
]
3 ) = ] 0
= ( mol
0 / L ) 2626 B B = =2 .229762135
.29762135
A buffer level of at least 17 to 34 kg/m3 / is Aunsuitable for determining
2− 2−
buffer and 2buffer − 2−
19 19 [OH −
] [=
OH 0 −
] = 0 [ CO [ ]
CO (ppb ]
) =(ppb0 .42
27 ) =×
27 f [OH 0
P .42 ×[OHf ] =] =030[]CO3 ]
P −[ CO
−
22capacity − −in this brine 3system.
− 11
6 to 12 ppb of sodium and / or potassium
2−
25 A = 922 .69164 10[OH
2− [OH ] =]0= 0 3
19 [OH ] = 0
−
[CO3 ] (ppb) = 0.42× Pf [CO3 ] 2 −2 −
carbonate / bicarbonate 20 20[CO3 [CO
2−
] = is 2−
03 .02 ]recommended
=× 0P.f02( mol
× Pf/ (Lmol ) 26 / L) B = 223 .29762135 2 −2 −
2828 [CO [CO 3 3 =
] ] =00
23 The [CO [CO 3 3 ] =] 0
consequences =.02 0.02 ×P ×f P( mol
f (ofmol /this
L/)L) are:
20
2−
[CO3 ] = 0.02× Pf ( mol / L) for most applications of formate brines. − 2 −2 − −−
pKpK
27 [OH − ] = 0- The phenolphthalein endpoint OH OH −
can be used
CO CO 3 3
to
HCOHCO 3 3 a a
A 5:3 molar ratio of carbonate to
21 21[HCO3[HCO [ CO 2 − ]2 − ]
[ buffer
CO
− −
] = 03 ] = 0 [CO32424 2− determine
] = 0 [ HCO the capacity [
( OH[ OH
−
]
−
] + [CO[ CO
2 −2
]−
]
). [ [
HCOHCO
−
]−
] PP
bicarbonate provides an ideal pH in the 28 f f H
− − 3
3 ]3=] = . .
3
[ HCO ( mol ( mol/ L/) L) 3 3 3 3
21 [HCO3− ] = 0 - The2 methyl AA expexp
orange ( B(.BpH . pH) )
endpoint cannot be used to
range of 1022– 10.5. [
22 OH =OH The
−
] [ 0 =0use
−
] of cesium OH −
CO3
−
HCO3−11−11 pKa
−
carbonate / bicarbonate might be beneficial 2525 determine AA =9 =.69164

9.69164 the 1010total buffer concentration
22 [OH − ] = 0
in certain high-density 23 23[CO3 [CO
2− 2−
] =cesium
03 .02 ] =× 0P.f02 ×formate
( mol Pf/ (Lmol ) / L) [ OH −
] [CO
(including
2−
3
] [ HCO3− ] ). P H SO
2626 B B =2 =.29762135
2.29762135 f 2 4
23 [CO32 − ] = 0.02× Pf ( mol single/ L) salt formulations to increase density.

[ CO32− []CO32− ] 2727Another [OH [OH ]method
− −
=]0= 0 is therefore required for measuring
− −
[ CO 24 24 [ HCO [ ]
HCO = 3. ] = . . ( mol
. / L( mol
) / L ) the bicarbonate 2 −2 − concentration. One standard
2− ]
3
A expA( Bexp pH()B pH ) 28 28 [ CO [ CO ] = ] 0= 0
24 [ HCO3− ] = . 3
( mol/ L) method− of
3 3
doing2 −this is by −the use of a Garrett Gas
A exp ( B . pH ) 25 25A = 9.69164
A = 9.69164 10 10 −11 −11
OH OH −
CO CO
2−
HCO HCO
−
pKpK
A6.3.4 Determining buffer concentration Train (GGT). The 3 3
GGT determines 3 3 a a
the total amount
25 A = 9.69164 10−11
and capacity 26 26B = 2.B 29762135
= 2.29762135 [OH
of carbonate [OH] ] [CO
− −
( [CO
2 −
] ] + [ HCO
2 −
[ HCO −
] ] P Pmethod
−
3 3). The is time
3 3 f f H2 HSO 2 SO 4 4
26 B = 2.29762135 For standard water-based −mud− filtrates, API RP consuming, and therefore not very popular on
27 27 OH = [ ][ OH 0 =0 ]
27 [OH − ] = 0 13B-1 [5] recommends that2 −carbonate and the rig.
28 28 [CO3 [CO ] = 032 − ] = 0
2−
bicarbonate content are measured by pH titrations.
28 [CO3 ] = 0
Alkalinity in the form of OH − content, OH − CO32 −CO32 −HCO content, −
3HCO3 a
pK−
pKa A precise method for accurate
OH − 2−
CO3 and HCO3 content −
pKa is determined − by the combination determination of buffer concentration
[OH ][OH []CO3 [CO
− 2−
] 3 ][ HCO3[ HCO
2− −
] 3P −
] HP2fSO and 4H 2 SO capacity
[CO32 −of ] a phenolphthalein titration with an endpoint f 4
[OH − ] [ HCO3− ] Pf H 2 SO4
of pH = 8.2, and a methyl orange titration to an Cabot Specialty Fluids has found that bicarbonate
endpoint of pH = 3.1. can be determined with a fairly good accuracy by
conducting an upwards titration with OH-. This is
In formate brines, the determination of the methyl shown in Figure 8. As can be seen, there is an unclear
orange titration endpoint is complicated by the inflection point, and with increased bicarbonate
formate / formic acid equilibrium that is present concentration, the inflection point is even more
2 pH pH = == −−log log(([a [aHHH++++ )])] a +
99 CO
CO
2 2− −
H+ +← KK −− 211 pH pH =− −log log a HH +
3 3 ++H →HCO
HCO [aH H ++ ]
a 2a 2
←⎯⎯⎯
⎯ → pH = − log [H + ] 2 1 1 pH
pH =
= −
− log
log ( ) a
33
2
3 pH = −−log
HCOO +H (aHHO ++ )+ Ka
HCOOH aHH++ 11 CO3 +pK
2−
CO2 + H 2O ⎯ ⎯→ 2HCO3
−
7 CO2 ( aq) + H 2O ←
⎯→ H 2CO3 ( aq) a H + + H2 O
+
3
12
2
pH
pH pH = ==− −−−log log
log (([aaH3H + ])+) ←⎯→ Ka
a pK
a
HCOO + H O ← ⎯→ HCOOH + +H O
2 pH = − log(a H + ) 2 pH = =a− −−+log ([aH )++ KKaa a HH ++ a
3H+ + 2
13 pH log ++ ]
−− −− 2 2− − 31 HCOO
pH HCOO = − log
H −
log ++H H [aH 33HO
H+
O ])+← ←⎯→ ⎯→ HCOOH
HCOOH H + +H
12 H22O O CO32 −(pK pK)aa+ Ca 2+ ( aq) ⎯
aq ⎯→ ↓ + CaCO ( s )
C AB 10 10O T S HCOHCOP E3 3C++IOH OH
A LT ← ←⎯→⎯→FCO
Y CO L 3U 3 I++ DHH 2O
S 2O 2 3 pH HCOO =− − + (H
−
O
F+pK O
+← R⎯→ Ka
KM A HCOOHT E aT +E + CH HO N I C A L1 pK Ma A NpH U A= L− log [H ] 3
8 H2 CO3 ( aq) ←⎯
K a1
⎯→ HCO3 ( aq) + H + ( aq) 3
−
+4
33 K a CO HCOO+−−H+ 2 − ++H H← 3H
O ⎯ ++a← 2 ⎯→
→
a
KaaHCO
K HCOOH + − H
+H H2 O 2 O pK
pKaaa2 CO32 −
2−
HCO
−
[C
HCOO −
+ H O ← 2 ⎯→ HCOO
HCOOH
pH 32= − − log + + (H a 3
3O
O pK ) ← ⎯→ HCOOH
pK 3−a a + 2 pK 3−
pH = − log [H + ] 3
423 CO pH 32= −+−log H +(a← 32H⎯ a
)+ 2 →⎯→ K aHCO3 a HH + 13 pK a
O ←CO K
HCO HCO
−
+ H3+−−( aq)
= − log [H + ] + H2 O CO2 ( g2 ) +aH
2
1
+
HCOO + +H← pK ⎯→ a H +[ H
3O HCOOH 2 −− (a 3+ )
H +pK pKaa← 2 2 pH = − 32 log
2−− −−
2− + K a22 2− − − −− 44 CO CO 332 − − ++ H H ←
+ ⎯⎯ pK
22
→ → HCO
HCO pK
pK a CO
CO − H HCOHCO
9 CO3 11 +H ←
11 CO CO
⎯ ⎯3→ 3 ++CO
HCO CO 2 2+3 +H H2O 2O⎯ ⎯
⎯→ ⎯→2HCO 2HCO 534 HCO CO322−−3−+
HCOO +−−+H +HH++H+←← O⎯
pK ⎯
+a⎯ 2 K
a 1
→
K a HCO
H2 CO 33− pK
pKaaa122
pK
aa2 HCO 3
CO322 −3−−
32 − HHCO 2 CO−3
33−
⎯ 2 a→
HHCOOH + H22O−
33 pK +pKa← 1⎯→
a 3
4 HCO 3− CO
2 a H pH pKa5 3 CO
HCOO − 32 −3 +H +++H← ← OpK → →HCO 2 CO
HCOOH +CO H2 O pK HCO HCO
H+2 CO
aH + 3← ⎯ ⎯
= − log(a H + ) = − log(a H + ) 4 CO
2−
+ H +
4 HCO CO + H ++3 ⎯
pK aa←
2→
⎯→
aa1 HCO pK 3−− 3
HCO[ pK
3 + a−
] a12
[ HCOO CO − 32−3−−
] +
− H3 O HCO
3
K3−−
HCOOH
H × HCO ← ⎯→ a3
2
+
← ⎯ 2
→ HCO
−− pK
2 −33 − + H H CO pK
pK
2 2− − 2 +2 +
3 55 HCO 3 3 3 + H + +← ← pK ⎯ ⎯ ⎯⎯ 1 →→ H CO
3
3 a
− 2 33 14 3
K = pK 3 aa 2 HCO
HCO
3 3
32 3−3 − HH CO
CO 3
3 −33
CO CO3 3 ( aq ( aq )+ )++Ca Ca ( aq
( aq ) ) CaCO
CaCO ( s
( s
) ) 2 a 2
12 12 ⎯ ⎯→
⎯ ⎯→ ↓ ↓ OH -
- titration 45 curves CO HCO + + H H ← ← ⎯ ⎯
apK 2
⎯ → a1 HCO
→ H 2
CO pK
pK
a 11 CO
HCO HCO
H
22
CO
aP
3 3 3 − + pK 3 a 3 − 3
−
OO + H3 O ← + Ka
10⎯→ HCOOH 3HCO3 HCOO −
++OH H2 O← − −
+⎯→ H3 OCO pK
← 2K
⎯→ HCOOH + H2 O
−a
pKa− + H2+−2−←⎯ 65 HCO 3− + H + ←⎯ pK ⎯ a1
→ H 2 CO3 pK 2
HCO 3− H 2 CO3
22(3 )← pKa ( aq ) HpK
3 a + H 2O
CO
→ HCO 2 −g + CO
pK
HCO −33 ++ HH++ ←
pK 2CO
H pK
1
5 HCO 3 [ CO [ CO3 3 ] ] 6 54⎯ a1
2 CO
CO
3− ⎯→ ← ⎯ pK ⎯ ⎯
2 a1 →
a 2 → HCO
2
a 1 − 3
HCO
−
COaaaa3111
pK
2
HCO
CO
2−
32 3−
3− H222CO−−333
HCO
1313 13 CO CO2 2( g ( g) )++HH2O KK −−
HCO3 3 ++HH+ +( aq ==4 AAexp( exp( COB CO B××233pH (pH g )−+ )← )+⎯→ HH ← +CO ⎯ pK (→ aq
a1 HCO ) H22 CO 3 −a1 33
15 3 pH = 2−4pK loga22K −CO log CO 2−PCO 3−
++log HCO
[⎯pK 3
] OH −
−
2O← HCO ( aq) ) 5 HCO pK HCO + Ha22CO
← ⎯→ ⎯→ s s
← ⎯2⎯ → 3 3 2H ← →3 HCO
[ HCO −−
[ HCO3 3] ] 6 6 CO CO22((gg−))← 3
← ⎯→+CO
⎯→ CO2pK ((aq
2Water aq )) + standard buffer
2 3 a 1 3 3
−
3 3
25
66− CO2(( g
HCO g3−−) ← +⎯→ ⎯→ H + CO CO
←⎯ 2⎯ ((aaq
aq →)) H2 CO3 pKa1 HCO H2 CO3
a1
pKa pKa pK −
CO 2 33 ) ←
2− − 2− 2− −− 2− −
+ H + ←⎯ +
5 HCO +⎯→ H CO →+Hstandard 2 CO3 5pKa1 HCO HCO + HpK CO
→ HCO 4CO 3 3 +CO CO32 ++HH2O ← pK a 2HCO CO3 6 3 COpK
HCO a 2 ⎯→CO CO326( aq ) HCO
11
2
⎯ ⎯→ ⎯ 2
→2HCO ←⎯ 2KFo⎯ 1
buffer − 3
3 + H ←⎯
3 H CO
CO 22( g ) ← 22 ( aq )
2⎯ →
2 ( g) ←
a1
3 3−3− 3
[H[H+ +] ×] ×[HCO [HCO 33 ] ] 16 0 .02 × P
2 3
pKa1 1214 14 K K = = pK
6 CO2 ( g ) ← ⎯→ CO2 ( aq ) f
−
O3 + H ←⎯ +
⎯ → H 5 CO 2−
HCO
−
+ 2 +H ←⎯ +
P
pK
⎯ P
a
→ H CO HCO
−
H CO pK HCO
−
H CO
2 2 ( aq
12 2CO33 ( aq) + 3 Ca ( aq) ⎯ 2 CaCO 33 ( s3) 763 CO g23)2−))← + H 2O H CO3 ( aq)
1
⎯→a21↓CO CO ← ⎯→
CO 2(((aq OCO 2−((−aq ) 2CO
2 2 3 a1
⎯→ [CO32 − ] + [OH − ] = 0.02× Pf ( mol / L )
6HCO− −CO ]−+⎯→] H[HCO H 3 ( aq) [ OH [ 17− ]− ] [CO
2 2− − 7
2 g) ← CO 2 aq )H
−−
OH− − CO [CO
[2CO [2HCO ← ⎯→ [CO
15 15 pH pH==−−log logKK−−log logPP ++log log [HCO
[HCO 3 3 ] ] ] OH CO HCO 3 3] ] H H2 SO 2 SO 4 ) OH 6 CO2 ( g ) ← ⎯→ CO2 ( aq )
2− 2
CO CO [ CO 33
7 3 3 CO
CO ( ( aq
aq 3 3) + H
) + H O O ← ⎯→ H CO
CO 4( aq
( aq )
13 CO211 ( g) + H 2O ←⎯→ HCO3 + H ( aq) K − +
2 2 3
= A exp( B × pH ) 7 s 2 2 22 ← ⎯→ 2 2 33
[ HCO
−
] 7 CO ( aq ) + H O ← ⎯→ H CO ( aq )
H + ( aq) [HCO3 ] = 0
−
COCO 2((aq aq) + +H H 2O H 2CO CO3((aq aq))+ 18
77 H 2CO
2 ( g) ← ⎯→ CO2 ( aq ) 6 CO2 ( g ) ← ⎯→ CO2 ( aq ) 2 2 K ← ⎯→ 2 − 3
( aq3) )( aq )← a
7
3
CO2 ( aq) + H 2O ← ⎯→ 8 H
CO 2322 22OK←
⎯ ⎯ a⎯→
1
→ HCO H 22 3 −33( aq )
pH 16 16 0 0. 02
. 02 −××PP
8 H CO 2 CO ( aq 3 ()aq + )←
H O ⎯⎯ 1
→ HCO H CO 3 − ((aq aq ))+ H + ( aq)
[H ] × [HCO3 ]
+ 7 2 − 3 ((aq )+)←
KK← aa⎯→ +
88 H H22 CO → HCO HCO33 −−((aq aq))++H H ++((aq aq))
f f −
CO ⎯ K a2→
11
+)(aq
2 2 2 3
14 K= 98 CO 3 HH ←← ⎯⎯ ⎯
K⎯ a 1 → HCO
7 CO H CO
3 2(− aq aq
+ +) ← O ⎯ K⎯← a⎯→2 → HCO H CO 3− ( aq) + H + ( aq)
K a 19 H − CO ( aq ) 11 → HCO −− ((aq ) + H ++ ( aq) [OH ] = 0
17 PCO2 [CO 8 CO + H −
1017 [CO3 3 ] +] +[OH
2 2
− −
[OH− −] ]==00.02 .02××PPf f( mol ( mol/ /L L) ) 7 [ CO CO[ CO
2 2 (
2 aq2− −
]
3
( )
] mg
(
( aq + mg H / ←2
/LO L ⎯
K
) ⎯⎯
←
) aa⎯→
=
1
= 12001200 H 2
× CO
× P
3
P
3 aq 19
8 H CO3 ( aq ) ←⎯ ⎯29 8
→ HCOCO H322 CO 2
(−3aq
3 2 2 − )3+
3
H+)+← + 2 ( aq ⎯ ⎯K
KKaa)2→ HCO3 f−f( aq) + H ( aq) 2 3 − 3 7 CO2 ( aq) + H 2O ← ⎯→ H 2CO3 ( aq)
332 − + H
23− 3
← ⎯ ⎯ 2→ HCO3
pH = − log K − log PCO2 + log[HCO3 ]
−
OH CO3 − 2− 2 −
[ CO3 89 [HCO 9 −
] CO ]− 3+(H + H ← K⎯ ⎯ a 1 → HCO
[ OH −
] 3 −[CO
15 H2 SO
33−−
HCO3 H CO 2 3CO aq )+ ←
+
← 4⎯ ⎯
⎯ K
K⎯
a 2→
a 2 → HCO
HCO ( aq) + H ( aq) +
9 CO 322 −−−+ H + ← HCO [ 2−
]
2 ( aq) + H 2O ← ⎯→ H 2CO 7 3 ( aq18 CO2 ( aq[)HCO
)18 [+HCOH 23O −−
]← ]⎯→ H 2CO3 ( aq) K10 [HCO [CO 3 ]+
2− 2−
](kg − 3 3 ⎯ ⎯ → 2 −3− 20 CO = 0 . 02 × P ( mol / L )
3 33− (+ OH 2CO
CO (aq kg /)+/m m )KK⎯ )⎯→
a=
a122= 11.2.HCO ××PP 3− + H O
3 ==00
a 29 K
9 2 −
CO3 + H + ←⎯ 8→ HCO CO − 2
H ← ←
⎯ K
⎯ a
→ −
2+ H +
33−− (( aq H ))2O ( aq)
⎯ H 32 CO 33 ← −⎯ a 1→ HCO 32f f3
−
3 f
10 8
9 HCO HCO 2 CO
2 − 3+
3 − 3 ( aq OH )+ ← ←
⎯ ⎯K⎯→ a 2→ HCO
→ CO 32 3− + aq + H + ( aq) K a1 −
9
10 HCO 3 −+ + HOH ← −− ⎯
← ⎯
⎯→ HCO
CO 2 3−
+ H O 8 H2 CO3 ( aq) ←⎯ ⎯→ HCO3 ( aq) +
16 0−.02×-0.40 Pf -0.35 -0.30 -0.25 10
-0.20 HCO 2 3− 3− -0.15 + OH + − K a2
← ⎯→ CO -0.10 332 −− + H22O -0.05 0.00
10 9 CO HCO − + + H OH ← ←
⎯ ⎯ ⎯→ → CO
HCO 2 − + H O
CO3 ( aq) ←⎯
K a1
⎯→ HCO83 ( aq19 )19H+2HCO +
( 3aq[(OH
[aq) )−←
OH ]=
− ⎯
K
] =⎯ 00→ HCO3 ( aq) + H (10
a1 − +
aq) 10
11
10 9
CO[ CO [HCO
HCO CO
2− 3
CO+
2
22−23−− + −
+]−](ppb CO +(ppb H OH
2 +
+
)= ←
−
)−−=H0← ←
⎯K
0⎯ ⎯→
.2⎯→
a2
O
42.42 → ×⎯→
⎯ PCO
×HCO
3−
Pf f 322HCO
3 −
2 3− +[CO H
[CO 2O21
2− 2−2−
]] [HCO39] = 0 CO 2 − + H + ←⎯
−
K a2 −
33 2+ OOH CO +H 32−O
−
HCO3 + OH − ← ⎯→ 3323−H
3 3
2 33
⎯→ HCO3
17 [CO32 − ] + [OH − ] = 0.02× Pf ( mol / L ) [ CO3211 −
10 ]-( mg / LCO
3
) = 321200 +−CO×2 P+ −H 2O ⎯ ⎯→332HCO 2−
3
11 HCO − + OH ← ⎯→ CO + H 3 −O
11/ Liter]CO CO3322 −−+ CO 22 + +f −H H22+2O 32HCO 2−
2 −3
2−
+ H + ←⎯ K a2
⎯→ HCO 93 − 20 CO3 +[CO
2−
H +2 2← −− ⎯ Ka
HCO
− [mol OH + CO O ⎯ ⎯ ⎯→
⎯→ 2HCO33 − 22 ( s) [OH − ] = 0
20 [CO ] ]⎯2 →
3 3 ==00 .02
.02 ××PPf f(3mol ( mol/ /LL) ) 12
11 CO CO3322 −−3+ (+−−aq +))OH
CO + Ca+−H H2← ( aq
O )CO ⎯ ⎯→ 2 − ↓ CaCO
2HCO
−10 HCO − + H 32−O 3
3 ⎯ ⎯→
+⎯→ 32
[ −
] 2 1211
10 CO CO
HCO ( aq CO
+ OH+ 2 Ca + ← 2O
⎯→ ( aq ⎯ )
⎯→ CO⎯ ⎯→ 2HCO ↓+ CaCO H32−−O 3 ( s)
CO3 + CO[2CO ]( kg 3
18 HCO3 = 0 11
2 −
+H 3 211 O / mCO CO ) =333221−3−+
2HCO 2 − .2CO × P22f +
−
HH22+222+O ⎯ ⎯→ 32HCO 10 HCO3 + OH − ←
−
⎯→ CO3 + H 2O
2−
3 (+ CO + O 2HCO 2−
s))) [CO3[[2CO − 3 ]
⎯ ⎯→ CO aq ))++ 2 Ca ((aq ⎯ ⎯→ CO
12 CO ( aq Ca Kaq)) ⎯ ⎯→ ↓↓− CaCOCaCO 33((s
33
12
13 CO 3322 −−
( g
3
) + H O ⎯⎯→
HCO + H − + 23( aq ] =2−−0].02 = ×APexp(f ( mol B × / LpH ) )
Figure 8 HCO OH titration 11
12 CO 22 −( aq + CO )+ + +Ca H ←2 +O ⎯→
2 (Kaq)the ⎯ ⎯→ 2HCO − CaCO 3 (s )
s
OH curves ⎯→for CObuffered water and buffered potassium formate. Both )fluids contain same 3amount
) ) of added carbonate / B × pH )
- 3 2 2 2+ ⎯ ⎯→ 3↓
[[HCO 32 − ]
2 − = A exp(
2 +13
12 CO ((aq aq +))H Ca ((Kaq aq)) ⎯ +CaCOH− ++ ( aq 3 (s
32 −g
2322(−− 2O 2← HCO
− 2− − 2−
O3 + OH − ← ⎯→ CO10 + H21 O 3 [+HCO [HCO
−− −
← + H 2O 2++⎯→ ⎯⎯→ ↓ CO3323−−]]] = A exp( B × pH )
[CO
s
221 3 3] ]==00 3 3 12 CO +3Ca −− CaCO 33 ( s) )

2−
12 andCO 3 (kg/m aq) +3Ca 11( aqppb )⎯ ⎯→ CO ↓ CaCO +(O s=H )← ⎯→ 3↓
[ HCO
g+ )3)CO O 2HCO
3 K⎯
bicarbonate buffer (17.8 kg/m / 6.25 ppb K CO 10.7 / 2−13
3.75 13
11 CO
KHCOCO 3 322((−− g ++pH
). HH O 11.52⎯→ 2⎯→−hasHCO
HCO been ++ H − +( aq
found
H ( aq to) be a suitable
[ CO 23−− ] = A exp(
titration 2 − B × pH )
s
19 [ OH = 0 −
] [ CO3 12 ] (ppb) =CO CO 0.42 23 × + P CO 2 2
2 Ca CO + H [
2← + O ⎯→ ⎯ ⎯→ ] 2HCO 3 3
[[[[HCO
CO 2 − ] =CO
s
[ACO −
( aq )+ 2 (− aq
K )⎯ CaCO 3 ( s)) 11 − 323−3−]]] = 3exp( +] CO B× ×2pH pH+H O⎯ ⎯→ 2HCO3
)) /2 L)
3
2 3
13 CO 2
32[(H g ++ H 2
O← ⎯→
HCO 2− ↓ +
3 − 3 +
H + ((aq aq HCO
))++ ]f × [HCO ← ⎯→ ]3 [HCO CO3 33]−−− + CO
s
[[HCO
CO A exp(
exp(32 − B
K
endpoint22 for determining
22 [OH[OH −−
] ]
= = 0 bicarbonate content 13
0 [HCO3-].CO ( g) + H O ← 13
14
13 K CO = 2−2[((H g + +H
2O 3⎯→ K H 24
+ )B × [pH HCO ]33= ] == A s
B × (pH
pH mol )
12
K
⎯→ HCO CO
CO + −g
−( aq )H ] ×
)+ H [
( aq HCO 2O
22 ) 2 +3( aq) ⎯
Ca ←
2 +⎯→ −K] HCO
⎯→−33↓−] CaCO3 ( s) += H A ( aq
+exp( ) ) [ HCO
3 2 −−
] . s
A exp(
exp (2B− pH ) . B × )
[[[HCO
CO3 −3− ]]A
s 3 s
2− − 2− −
14 K CO =333222[([H ( aq + )P +[CO Ca (3−Kaq−] )[ ⎯ CaCO 3 ( s))
12 12 23−3− ] =CO
2 2
3 + CO2 + H 2O 20⎯ ⎯→11 [CO32 −3CO
2HCO ] = 03 .02 + CO × P2f (+mol H 2O / L⎯ )⎯→ 2HCO3 13 )+++ ]]××H [HCO ] HCO ⎯→3 ↓ + H + ( aq HCO A exp( B × pH ) 2+ ( aq) ⎯
CO ==2 [H g HCO
2O ← HCO 3 (−aq) + Ca ⎯→ ↓ CaC
3⎯→ s
14
14 K K H ] ×PCO [ HCO
2
−
] 3
25 A −= [9 [ HCO
CO
.69164 22−3 −]] 10
−11 2−
23 23 [CO[CO
2 2− −
] ]
= = 0 0. 02
.02 × × P P ( mol
( mol / /L L) ) 15
14
13 pH K = = [ H − log
+
] × P K[ HCO
2
− log 3 KP
−
] + log [ −HCO
−
+ ] OH [ CO
CO 3 ] = HCOA exp( B [×CO pH 32 )−
] [HCO3−− ] H 2 S
3 3 f f
[ H +
] × [ HCO 14 −
] CO
K = 2=[(H ( g ) + +] × P
H [ HCO O ← ⎯→
3 −K] CO HCO + H 3 − ( aq ) − 332 s
− = A exp( B[× pH
− 3 −
) ] [ 3 − ] −H
+ −
2− 2+
3 ( aq) + Ca ( aq) ⎯ ⎯→12 ↓ CaCO
2−
CO3 3 ((saq ) ) + Ca ( aq) ⎯ 2+
⎯→ ↓ CaCO3 ( s14 ) 15
13
14 3 pH CO
K =2=[ − log g− ) log + H K
PCO
CO CO 22O − 2 log
← 3⎯→
3 P 2
+
HCO log 3[HCO
−
+ H +
]
( aq ) OH CO
[ 13 3223−−−] CO (3g
− [ HCO
HCOs
CO K HCO S
K= 2 − ) +[[CO H 3O ⎯→ HCO + 2H
2 CO2 3 3−
] HCO 22−−←
+ P
2HCO CO2332 −]] [[HCO
−
15 pH ] ×PK [K − log3 −PP]CO + log[HCO 26 ] OH CO HCO33 −]] 3 H H22S
−
15 pH =H− log HCO 2− log
2
CO22 + log[HCO33 − ]
−
OH B −= .29762135
CO HCO S
21 difficult [ −
HCO3to] =determine. 0 [ CO From 2−
] [ CO
[=CO a2−2series
]−−] B ×+ pH of calibration [ CO3
2−
] P CO 14
15 Depending K pH = = =− −+log logon CO
CO
K 2−
CO 2
−pH, log−P Pfour + log situations
log HCO3−− ]] exist:
[HCO OH−− CO322 −− HCO3−− [[CO
− 3323
− 33 −
CO322 −− ]] [[HCO HCO3−− ]] H H 2S S
[ OH
2
( g ) + H O ← ⎯→K
HCO13 −
+ HCO +
( aq
24 2 [ HCO ( g )) + H
[ HCO O − −←
23 3]= ⎯→K3
]==11.5 HCO A 3 3 exp( + H ( mol
( mol( aq/15 )
/LL) ) to[pH = A exp( 15
16 B × pH ) 0 pH . 02 ×[ H P ] × −P [K HCO log ] CO2 + CO HCO [CO ] −[HCO ] H 22S
24 2 + log[HCO
27] 3 OH [OH ] =[0HCO
s
15 2 − −
s
2 2 tests, 3 however, pH [ HCO −
.]exp has .been
.3pH found be=3a−] log K − log
HCO
−
14PCO2 +0pH K pH log=[= =[H
HCO −−log +
f ]3× K
log ][K HCO
CO −2− log OH
log 3 P
3 − −
P]COCO22 CO
CO
+ log
2
3 HCO
−
HCO 3 − −
[CO − −
]CO 32 −
HCO[3H
3 ]
3 −
2+SO 33 [ OH
3 2 − −
] [33CO 3 − 2
3. exp ( ( 3H ] × 4[HCO
2− 3 ]
33
22 [OH ] = 0− A A B B pH ) ) 16
14 K . 02= × P f PK − log P
3 33
−
K = 3 [CO ] [HCO3 ] H 2 S
− − 2 − −
15 1. 0 pH =>−P11.5 log CO2 + log[HCO3 ] OH 2CO 14 HCO
suitable titration endpoint. Unfortunately, no suitable 16 pH ..02
022×× − Pf PCO−
CO2
16 [0 2 −3
− 3
25 25 [H +AA ==[9HCO
9.69164
.69164 − 10 10−11 −11
17 CO ] +f [OH 2 ] = 0.02× Pf ( mol / L ) 28 [CO ] =20− − [ CO P3CO 2](−mg / L ) = − 1200H× P
[H + ] × [HCO3 − ] ]× 3 ] 16 0 . 02 2× −−P
− − 3
[ 2 −22 − ]
15 pH −− log PCO + log[HCO3 − ] OH CO HCO CO ] [[/HCO −] S
3= log K
= 23 pH 14[CO indicator
2 −
K] ==0.02has × Pf been ( mol / Lidentified ) for this titration. 17
16 0
15 [0 pH CO .02
023= ×−−P ]P+log f OH
f [ K −] = log 0.02 PCO×22 P+f log ( mol [HCO / L ) 3 ] OH − CO − 32−
HCO (14) 3 −
[ CO [CO 3 ]( mg HCOL) = 31200 ] [HCO H×22P S
16 0 . 02 × P 16
17 [ . 22 × −] f [ ] OH 15 3
CO pH 2 −=3 − log
[ CO HCO K
3 22−−3− log
]
2 − ](3(mg
− P/ L pK +3log
32)) =a=1200 × P
−−
BB=P CO −]+ OH = 0 . 02 × P ( mol / L )
3
PCO2 26 26 =CO22.229762135
.29762135 f 17 0[HCO [ [CO ] + f [OH ] =
0 −− ] = 0.02× P ( mol / L ) 0 . 02 × P ( mol / L ) (15) [CO [[ CO ] mg /CO
L 1200.2 × P×f P ×
18 =[OH 322−− ]((kg /m )= 11200
3 f 3 3
16
17 − 2 [−[HCO
.
CO 02 3 2
× 3−−P
−
] +
f
CO
3 2 −
mg / L ) = P
SO4− ]3=18
−17
CO
2
23−−−] +
]] =[[OH
f
0− ] −− ]]H=20SO ] ×[[[[COCO[3323HCO 22 −−]]((kg mg −/ m
3
] // LL33))) = 11200
=1200 .2 × P×f P
== 00...02 02 ×P P[ffOH ( mol − / L)
= − log K − log PCO2The +15 [HCO
logrecommended pH
−
3 ]= − log OHK−−−− log COP3CO2 +HCO
2−
log [HCO−
[3CO
−
] 3217 −
]OH[HCO −
CO
− 2−
3 ] of
2 − H HCO
17 [ OH [CO
×]3P[Assuming
[CO ] [CO [332HCO ]/ L )[CO [of [OH ] have [CO 2−
− ] mg
OH32]− ]==0method therefore consists that large amounts not
2− −
27 27 [[OH
[CO 0 3 [CO 3 ] + [2OH
16
18 0.02 0 [ (.mol
CO
HCO 02 33×/−P L] ++=) 3OH
] OH
0 02 4× × P ff (( mol
mol / L ) CO ]( mg / L ) = 1200 [CO
P
CO 332 −]]((kg 3 /m P
= 1 . 2 H
× ×2 SO
P P
− 3 18
16 f
0[CO HCO
.022×3−3−−P f = 0 3 3
CO f ( kg / m ) = 1
f . 2 × P
24 the[ HCO 3 ]=
following . steps: ( mol/ L) 17
18 been HCO 3 3 added
]]+f=[OH 0 ] =to
−
0.02 this × Pf fluid, ( mol / Lone ) can 2assume 16 0.02× P[ CO
that
332 2− −
2 − ]( kg mg/ /mL33)) ==1200 1.2 × × PP
ff
2 2−.−
(B ] ]==0) 0 [[[OH HCO − −− ] = 0 [CO 2−− ]( kg / m3 ) = 1.2 × P f
f 3
28 A exp pH 18 3
28 [CO [CO [HCO3− ] = 0 19
18 HCO 2 ]3 −=] 0 = 0 [ −
] 3 [[COCO 322 −−]]]((ppb
kg / )/=L30)) .=
m 42
= 1 ×
. 2 P×f P
18 17 ] [ ] CO ( kg / m ) = 1 .2 × P [ CO ( mg 1200 ×
f
×LfP
−
[most CO −]of
+ OH this =
− alkalinity 0 . 02 × P ( mol
is from / L )
/ L ) carbonate.
3 2 −
CO33− ]3= 2 −[ CO
332 −]
33 − 3 3 2 − f
2× Pf 25 16A = 9.69164 0.02× P 10 −11 19
17 [ [HCO
OH 2 −
]+0=[OH 0 ] = 0.02× Pff ( mol 3
17 [ ] [CO
[
f
CO [ 3 23− −]](ppb ]
((kg
mg / )/m=L30)).= 42
= 1200
1 ×.2P×f P P)
18 [[OH CO + OH = 0 . 02 × P ( mol /
OH 2−−]−3]= 3 [[CO 3 ]] (ppb) = 0.42
f 2 2− − 19 00 2 − f ×P
1. Determine OH OH− − andCO CO3 3 buffer HCO
HCO
−−
capacity pKpKa a by use 19
20 [ CO −=] = 0 . 02 × P ( mol / L ) CO33 2−− (ppb) =3 0.42 × Pff f
33
19 2 − [[[CO
18 OH
HCO 32− −]−= ]= 00 f [[COCO3322−−−]]]]((ppb (ppb
kg / m ))==300) ..=42 1× .×2P P
×P
]3]−L=]= −[[CO
OH 3 ]=0 42
] 0× Pf 20 19 =00 .02× P×f P( mol / L) ]CO ( kg 2− / m
] ) = 0) .42 = 1× .2P×ff Pff
2−
O3 ] + [OH − ] = 26
2−
0.02× P17 B
f of L[CO
=a2/.standard) 3 ] + [OH
29762135 2−
−− ] = 0
−
/[LCO ]−8.
(−]mg / L)[OH = 1200 [ CO2.
18 ]pH(OH HCO
mg32−−/2= )11.5 1200
[OHacid ] ] titration [CO3 3 ] ] to pH
) 3 =19
] Although
( mol .02× P2f−2(−mol [HCO
[[[CO × Pf3 [CO ] (ppb
19 ] =000..02 [CO3 2− ] (ppb 18 ) = 0.42 = 033332[−CO
−
[OH [CO [ HCO
[ HCO PPf f HH2=SO
3 − f
33 2 SO
20
20 CO 33−2 − ]= 02 ××PPff ((mol mol // LL)) 2− 3 ff
less − accurate, this can also be done by use of 20 2 − [[[CO
19 CO322 −−] −3=]] =
OH =0 00..02 (16)[CO3 ] (ppb) = 0.42× Pf
44
27 [ OH ] =
[ 0 ] 20 02× ×P Pf (( mol mol// LL))
CO3 ] = 0
− − 2−
[CO3 ]( kg / m [) = 12.2− × 3
[CO3 ]([[CO kg
18Phenolphthalein HCO3 = 0
pH indicator. 20 CO3 ] =P0f .02× P21 20
19 f ( mol / [L [OH ) /33−2m−]3−=
HCO ] ])=0==00 1.02 .2 × P ff ( mol / L)
f (17)[[CO3 22−− ]] (ppb) = 0.42× Pf
[CO32 − ] = 0 21
19 OH3−2 3−]−=]]=0=00.02× Pf ( mol / L)
HCO [ CO3 (ppb) = 0.42× Pf
(18)] = 0
28 20 [CO 19 OH −
2. Determine bicarbonate concentration by use of a 21 [[[HCO
21 − 33 −]] = = 00
−
22 HCO
OH
3
2 ]−= 0
f
− 2 − −
pK[aCO3 2− ] (ppb) = 0.42× P 21
20 [
[[[CO [ HCO 3− ]3=
−] ] = 0
==00.02× Pf ( mol / L)2− ]
19OH titration [OH − CO ] = 03 to pHHCO = 11.5. 2 −
21 − ]=
22 HCO 3−]0
2− 2−
]= 0 [20 ] ] (ppb [CO
[HCO3− ]f = 0 [CO OH
CO ]00.= 00.02 × P×f Pf ( mol / L3)
−
3
21 21CO 3 3 HCO 3−) = 42 20 [CO32 − ] = 0.02× Pf ( mol / L)
22
22 3. [8.5 [[OH OH 2−−]−3]< 3= = pH00.02<× 11.5
[OH ] −
[CO3 ] 2−
[ HCO ] − 23
21
22 [[HCO
CO OH32−−]]3]=== ]
−
=
] 0= 0 P f ( mol / L )
[CO32field × Pf ( mol /3 L)for P H 2 SO4 22
23 [[CO [[[OH
OH 00.02× Pf ( mol / L)
−
2−
O3 ] = 0.02× Pf ( mol A/20Lsimple
) ] = 0.02 method determining
f
[OH − ] = 0 22 32−− −] = − 0 (19)
22 21
23 CO OH
HCO 3]]=
=]=0=00.0.02 ××PPff ((mol mol// LL))
2 −−
buffer concentration and capacity 23
21
22 [[[CO
[ [ CO
HCO
OH32 −]3=] =0 0.02[×CO
33−2 − ] = 0 02
21 [HCO
(20)3 ] = 0
−
23
23 CO − ] ==00..02 02[× ×CO P
Pf ((2−mol
f3
(
2 −mol
]
mol /
/ LL L )
) / L)
32− − ] ]=
2 −
23 between
2−
[CO3 ] = 0.02× P22 24
23 f ( mol / L
[ HCO
CO
[OH) 3 3]−= 0 . P ff3 .
] / ( mol
)
As 21there[HCO is a −reasonably good correlation [[[CO OH32− 3−]−=]]== 0 A exp ( 2− ]]pH ) ( mol/ L)
22 HCO P(f3B
−
CO3 ] = 0 3 ]=0
24
23 [×[CO CO [OH − ] = 0
3 −] =0A .02 . exp 3(2mol / L) 22
−.
the carbonate-to-bicarbonate ratio and brine pH 24
24 [[HCO HCO ] = . [[ CO
CO −11B2 − pH
32 −..]
] ) ((mol mol//LL)) (21)
25 A
[[[CO = 9 2 .−369164
3 −
A . 10
exp ( (B pH )
3−]] ]]==
HCO =0.A02 )
[ CO 23
242− ] A [×
exp
×CO
−P 11 3B (22−mol
]pH// L ((mol
mol
) // LL))
−
H − ]= 0 (Equation
22 [OH13 −
] =and 0 Figure 6), this can be used[ HCO to − ] = 25
24
23
24 3
[ COHCO
HCO = 3392.−369164 − = 0.A
] = 02 . .10 exp P11ff(33B −.
( mol . pH ) L
( mol
) / L) 23 [ CO
2−
] = 0.02× Pf ( mol / L)
24 . 25 . A ( mol= 929/..3369164 L) A.10 exp[ CO − −11 ( B2−.]pH))
determine buffer concentration and buffer capacity
3
A exp 25
26 ( B pH
where) B A == 69164
29762135
− A 10
exp ( B3 pH
3
24
25 B [ A HCO = 9 . 69164 ] = 10 − 11 ( mol / L )
2−
O3 ] = 0.02× Pf ( mol
2−
[CO3 formate ] = 0.02× brine 26
25 A= =2 99
..29762135
3
69164 A . 10 exp[ CO − 11
(3B2−.]]pH )
of/23
Lbuffered
) Pf ( molin / Lthe ) [ CO −−11
field. This 25 means A = 9.69164 10−26 25
26 B [A = − .69164
= .10 ( mol/ L)
11 − 11
24
27 [[B OHHCO=
=2 2.].29762135 =− ]0
29762135 32 − [ CO32− ]
24 HCO − 3 ]= ( B .. pH ) ( mol/ L)
rough levels of both carbonate and bicarbonate 26
25
27 [ B B
AOH =
= 9 2 ]. 29762135
=
369164 0 A
A . exp
10
exp
−11
( B pH ) 24 [ HCO3− ] = . ( mol/ L)
26 −2 . 29762135 ( B . pH )
[ CO32− ] [ CO32− ] 26 B = 2 .29762135 26
27
28
27 [B[ OH
CO
OH = 2 −.]29762135
2 −
] = ] 0
=
= 0 10−11 0 − 11 A exp
concentrations 25 A = 39 2−.−69164
( mol/ L[)HCO3 ] =can be determined ( mol/ L) just by measuring 28
27 [[B [A OH
CO 22−2.−]]−69164 ]
===000
− −
CO3 ] = . 24 25
26
27 OH = 3−9 29762135 102 − 25 A = 9.69164 10−11
A exp ( B . pH pH ) and performing A . exp the ( B .standard
pH ) 27
phenolphthalein [OH − ] = 0 28 4. [pH
28
27 OH CO3−3−2<]−=]]==0=8.5
CO
[OH 00 CO32(i.e. no HCO titration
−
pKa endpoint
26
28 OH B
[B [OH
CO = 2 . 29762135
2 − ] = 0CO
32 .]−29762135
−
== 0 0 3222−−−
−
HCO3 −
3−
pKa
27
26 = −2
9.69164 10−11 titration. 25 AThe= 9.69164 method 10−11is as follows: 28 [CO32 − ] = 0
28
28 [[[OH
can
OH CO
OH333−−−2−]−]be
CO −2 − ]] = 0determined)
CO
[COCO33232 − ] HCO
HCO[ HCO 33 −3− ]
−− pK
pKaaP H SO 26 B = 2.29762135
27 [[OH OH − =
] ] 0 [ CO
CO ] HCO[ HCO ] pKaPf H 2SO4
28
27 OH CO
OH −
= =0 0 CO
2
3232−−
−
HCO
−
3−3− pK [OH(22) −
]= 0
2.29762135 26 B = 2.29762135 OH − CO3
2−
HCO OH
[[OH −3
OH3−22−−]−−] ] = 0
−−
pKCO [[CO 33332 −]]
322−− HCO [[HCO 33 33 −]]
3− − pKaaaPf H 2 SO 274
aCO HCO Pff H22 SO44
1. Determine pH in a fluid sample diluted 1:10 with 28 [[OH [COOH ] ] = 0 CO [ CO 2− ] [ HCO − −] (23)
28 CO [ 3− ] HCO [ 3− ] pK a Pf H SO
3 2 −
H ]= 0
−
27deionized [OH ] =water.
−
0 [ OH −
] [CO CO 3 3 ]
2 HCO
[ HCO−33 ] Pf H H 2SO SO 28 [ CO3 ] = 0
2−
OH−−3] ] cannot 3 − 3 2 4
[OH − ] [CO3 ] [[HCO
2 − −
Pf 22332−−−H
2 −
be determined.
−
P
2 SO
4
OH [ −−
] CO
[ ] HCO
4
[ − 3−
] pK
pK a f
f 22 44
2−
[CO3 ] = 0 2−
pH OH OHneedsCO CO 3
to3 3be adjusted HCO HCO 3
3 3 to above aPf H 28.5 SO4 with OH − 2− −
O3 ] = 0 28 CO3 HCO3
[ OH −
] [ CO
2−
] [ HCO
−
] Pf be
2. Perform −a phenolphthalein titration according to before [OH ] the [CO bicarbonate 3 ] [ HCO33level ] Pf H
can SO determined.
− 2 − −
−
CO3
2−
HCO3 OHpKa
−
CO3
2−
HCO3
−
pKa 3 H 22 SO 4
4 [OH − ] [CO32 − ] [ HCO3− ]
API RP 13B-1 [5]. Report the phenolphthalein
[CO32 − ] H[CO ] [ HCOof ]
2−
H−] [ alkalinity,
HCO3 ][OH − P
−
] , as the 34 amount
−
3 0.02 PfN H 2 SO4 (mL) More detailed field procedures for buffer determi-
f 2 SO
required per mL of brine (or mud filtrate). nation are given in Section C2 ‘Procedures’.

A6.3.5 Maintaining buffer concentration References

and capacity
In order to get the full benefit of the carbonate / [1] Leth-Olsen, H.: “CO2 Corrosion of Steels in
bicarbonate buffer in the formate brine, both the Formate Brines for Well Applications”, 2004 NACE,
buffer concentration and the buffer capacity should paper # 04357, New Orleans, USA, March 2004.
be maintained during field use.
[2] Prasek, B.B. et al: “A New Industry Standard for
Buffer capacity (carbonate + hydroxide) can easily Determining the pH in Oilfield Completion Brines,”
be determined by the standard API phenolphthalein Paper # SPE86502, Lafayette, LA, February 2004.
titration. Some rough level of bicarbonate (over-
whelmed buffer) can be determined by a correlation [3] Javora P.H. et al: “A New Technical Standard
between the phenolphthalein titration endpoint and for Testing of Heavy Brines”, paper # SPE 98398,
measured pH, as shown previously. Lafayette, LA, February 2006.
In most field applications, it has been found that [4] “Dilution factors for accurate measurement
the most practical way to control pH and maintain of formate brine pH”, Cabot laboratory report
buffer capacity is by adding carbonate. This # LR-050, April 2004.
method has the advantage that the consequences
of over-treatment are not as severe as with KOH. [5] API RP 13B-1: “Standard Procedures for Field
A potential disadvantage with this method, however, Testing Water-Based Drilling Fluids”.
is that it allows the concentration of bicarbonate to
build up. Excessive concentrations of bicarbonate [6] Berg, P.C., et al.: “Drilling, Completion, and
are known to cause rheology and fluid loss problems Openhole Formation Evaluation of High-Angle
in water-based muds [6].A good indication that the Wells in High-Density Cesium Formate Brine: The
buffer concentration is getting low and addition of Kvitebjørn Experience, 2004 – 2006,” SPE 105733,
carbonate is required is that pH drops quickly after Amsterdam, February 2007.
it has been adjusted upwards with KOH.

FORMATE MAN A6 PH and Buffering

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FORMATE MAN A6 PH and Buffering

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C ABOT SP E C I A LT Y F L U I D S F O RM ATE TECH N ICAL M AN UAL

CH EMIC AL AND PH Y S ICAL PR OPE R T IE S

A6.1 pH of formate brines ..............................................................................2

A6.2 pH buffering of formate brines ..............................................................5

A6.3 Buffering requirement and buffer capacity ........................................... 7

A6.1 pH of formate brines 3 Ka

pH is a measure of the acidity or alkalinity of a pKa2=

1 pH = − log [H + ] (1) At a pH of 3.75, the formic acid and formate anions

pH = − log K − log PCO2 + log[HCO3 ] 8 − −

A6.1.1 Controlling pH in formate brines method is not recommended in concentrated

pH can be measured in formate brines by potentio­

pH measurements in buffered and unbuffered potassium formate brine

13.0 KFo 1.561 s.g. buffered (glass electrode)

pH measurement in buffered CsFo and CsKFo brines

CsFo 2.199 s.g. buffered (glass electrode)

PAGE 4 SECTION A6 VE R SION 1 – 1 2 / 0 7

- Alkaline pH control is a critical factor in limiting H 2 pH = − log ( a + ) 8 H a CO

( mol/−L]−) 10 [ CO28 [CO3 ] = 0

pH behavior of carbonate / bicarbonate buffer when adding strong acid

Addition of strong acid

20 [CO 2 − ] = 0.02× P ( mol / L)

pH in various brine systems as a function of CO2 influx volume

Increasing time of CO2 influx

‘Compatibility with additives’). provided by the bicarbonate. (See Figure 5.)

buffer capacity depends upon the actual carbonate

important topKmaintain − the ability of the buffer to

ered with carbonate / bicarbonate is 3defined as the

CO3 +the total

CO2 ( g) + H 2O ← 13 ⎯→ HCO CO + H← + ← ⎯ ⎯ →→ HCO 3 33 HCO

10 HCO3 + OH − ← ⎯→ CO3 + H 2O 16 0.02× Pf

11 CO3 + CO2 + H 2O ⎯ ⎯→ 2HCO3 PCOPCO

to the3 formate/formic acid

carbonate / bicarbonate might be beneficial 2525 determine AA =9 =.69164

23 [CO32 − ] = 0.02× Pf ( mol single/ L) salt formulations to increase density.

221 3 3] ]==00 3 3 12 CO +3Ca −− CaCO 33 ( s) )

PAGE 10 SECTION A6 VE R SION 1 – 1 2 / 0 7

A6.3.5 Maintaining buffer concentration References

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pH can be measured in formate brines by potentio