Significance and Use
pH measurements are typically made in solutions that contain relatively large amounts of acid, base, or dissolved salts. Under these conditions, pH determinations may be made quickly and precisely. Continuous on-line pH measurements in water samples of low conductivity are more difficult (4, 5). These low ionic strength solutions are susceptible to contamination from the atmosphere, sample stream hardware, and the pH electrodes. Variations in the constituent concentration of low conductivity waters cause liquid junction potential shifts (see 3.1.1) resulting in pH measurement errors. The aggressive nature and the high electrical resistance of pure and ultra-pure, low conductivity waters may degrade the pH measurement electrodes resulting in unstable and drifting pH output signals.
It is essential to make on-line pH measurements of low conductivity water as accurately as possible to determine the proper control of pH adjustment chemicals, the effectiveness of demineralizer equipment, the event and nature of impurity contamination of the water, and information pertaining to the overall status of the pure water system.
Scope
1.1 This test method covers the precise on-line determination of pH in water samples of conductivity lower than 100 μS/cm (see Table 1 and Table 2) over the pH range of 3 to 11 (see Fig. 1), under field operating conditions, utilizing a sealed, non-refillable, reference electrode. pH measurements of water of low conductivity are problematical for conventional pH electrodes, methods, and related measurement apparatus.
1.2 This test method includes the procedures and equipment required for the continuous pH measurement of low conductivity water sample streams including the requirements for the control of sample stream pressure, flow rate, and temperature. For off-line pH measurements in low conductivity samples, refer to Test Method D 5464
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
TABLE 1 Calculated Conductivity and pH Values at 25°C of Low Concentrations of NaOH in Pure Water A
Note 1—This table tabulates the theoretical conductivity and pH values of low levels of NaOH in pure water as calculated from available thermodynamic data.
Note 2—To illustrate the high sensitivity of the sample pH at these low concentrations to contaminants, the last column lists errors that would result if the sample were contaminated with an additional 1 mg/L through sample or equipment handling errors.
| Sample Concentration, mg/L | Sample Conductivity, μS/cm | Sample pH | Δ pH Error from Additional 1 mg/L NaOH Contaminate |
|---|---|---|---|
| 0.001 | 0.055 | 7.05 | Δ 2.35 |
| 0.010 | 0.082 | 7.45 | Δ 1.95 |
| 0.100 | 0.625 | 8.40 | Δ 1.03 |
| 1.0 | 6.229 | 9.40 | Δ 0.30 |
| 8.0 | 49.830 | 10.30 | Δ 0.05 |
A Data courtesy of Ref (13). This data developed from algorithms originally published in Ref (14).
TABLE 2 Calculated Conductivity and pH Values at 25°C of Low Concentrations of HCl in Pure Water A
Note 1—This table tabulates the theoretical conductivity and pH values of low levels of HCl in pure water as calculated from available thermodynamic data
Note 2—To illustrate the high sensitivity of the sample pH at these low concentrations to contaminants, the last column lists errors that would result if the sample were contaminated with an additional 1 mg/L through sample or equipment handling errors.
| Sample Concentration, mg/L | Sample Conductivity, μS/cm | Sample pH | Δ pH Error from Additional 1 mg/L HCl Contaminate |
|---|---|---|---|
| 0.001 | 0.060 | 6.94 | Δ2.38 |
| 0.010 | 0.134 | 6.51 | Δ 1.95 |
| 0.100 | 1.166 | 5.56 | Δ 1.03 |
| 1.0 | 11.645 | 4.56 | Δ 0.30 |
| 8.0 | 93.163 | 3.66 | Δ 0.05 |
A Data courtesy of Ref (13). This data developed from algorithms originally published in Ref (14).
FIG. 1 Restrictions Imposed by the Conductivity pH Relationship
