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D 1129 Terminology Relating to Water 3.1.2 electrical resistivitythe a-c resistance in ohms mea-
D 1192 Specification for Equipment for Sampling Water sured between opposite faces of a centimetre cube of an
and Steam in Closed Conduits3 aqueous solution at a specified temperature.
D 1193 Specification for Reagent Water NOTE 2The unit of electrical resistivity is ohm-centimetre. The actual
D 2186 Test Method for Deposit-Forming Impurities in resistance of the cell, Rx, is measured in ohms, and is directly proportional
Steam to the length of the path, L (in cm), and inversely proportional to the
D 2777 Practice for Determination of Precision and Bias of cross-sectional area, A (in cm 2):
Applicable Methods of Committee D19 on Water Rx 5 RL/A
D 3370 Practices for Sampling Water from Closed Conduits
The resistance measured between opposite faces of a centi-
metre cube, R, is called resistivity. Resistivity values are
usually expressed in ohmcentimetre, or in megohm centime-
1
These test methods are under the jurisdiction of Committee D19 on Water and tre, at a specified temperature, normally 25C.
are the direct responsibility of Subcommittee D19.03 on Sampling of Water and 3.1.3 For definitions of other terms used in these methods,
Water-Formed Deposits, Surveillance of Water, and Flow Measurement of Water.
Current edition approved April 1, 2005. Published April 2005. Originally refer to Terminology D 1129.
approved in 1950. Last previous edition approved in 1999 as D 1125 95 (1999). 3.2 Symbols:Symbols:
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 3.2.1 Symbols used in the equations in Sections 14 and 16
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
are defined as follows:
Standards volume information, refer to the standards Document Summary page on
the ASTM website. J = cell constant, cm 1,
3
Withdrawn. K = conductivity at 25C, S/cm,
Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
Kx = measured conductance, S, cell that may cause erroneous readings. For example, biofoul-
K1 = conductivity of the KCl in the reference solution at the ing of the cell or a build-up of filming amines may cause poor
temperature of measurement (Table 1), S/cm, cell response. In most cases these problems can be eliminated
K2 = conductivity of the water used to prepare the reference by washing the cells with appropriate solvents.
solution, at the same temperature of measurement, S/cm, 5.3 If an unshielded cell is used to measure the resistivity/
Q = temperature correction factor (see Section 11), conductivity of high resistivity water there is a possibility of
R = resistivity at 25C, ohm cm, electrical pickup causing erroneous reading. For this reason it
Rx = measured resistance, ohm. is recommended that conductivity cells for this application be
of coaxial shielded type or equivalent, and that the cables and
4. Significance and Use instrument also be shielded.
4.1 These test methods are applicable for such purposes as
impurity detection and, in some cases, the quantitative mea- 6. Apparatus
surement of ionic constituents dissolved in waters. These 6.1 Measuring CircuitThe instrument may be a manually
include dissolved electrolytes in natural and treated waters, operated wheatstone bridge or the equivalent, or a direct
such as boiler water, boiler feedwater, cooling water, and saline reading analog or digital meter. Instruments shall energize the
and brackish water. conductivity cell with alternating current and, together with the
4.1.1 Their concentration may range from trace levels in cell and any extension leadwire, shall be designed to reduce
pure waters (1)4 to significant levels in condensed steam (see errors from the following sources:
Test Methods D 2186 and D 4519, and Ref (2)), or pure salt 6.1.1 In highly conductive solutionsUncompensated elec-
solutions. trode polarization due to excessive current density at the
4.1.2 Where the principal interest in the use of conductivity electrode surfaces can cause negative conductivity errors.
methods is to determine steam purity, see Ref (3). These test Insufficient series capacitance at the electrode/solution inter-
methods may also be used for checking the correctness of face can allow charging effects to distort the a-c measurement
water analyses (4). and cause errors if not compensated. Leadwire resistance can
add significantly to the measured resistance.
5. Interferences 6.1.2 In low conductivity solutionsExcessive parallel ca-
5.1 Exposure of a sample to the atmosphere may cause pacitance in the cell and extension leadwire can shunt the
changes in conductivity/resistivity, due to loss or gain of measurement and cause positive conductivity errors. Tempera-
dissolved gases. This is extremely important in the case of very ture compensation errors can be significant below 5 S/cm if
pure waters with low concentrations of dissolved ionized variable coefficient algorithms are not employed as described
materials. The carbon dioxide, normally present in the air, can in Test Method D 5391.
drastically increase the conductivity of pure waters by approxi- 6.1.3 These sources of error are minimized by an appropri-
mately 1 S/cm. Contact with air should be avoided by using ate combination of a-c drive voltage, wave shape, frequency,
flow-through or in-line cell where feasible. Chemically pure phase correction, wave sampling technique and temperature
inert gases, such as nitrogen or helium, may be used to blanket compensation designed in by the instrument manufacturer. The
the surface of samples. instrument manufacturers recommendations shall be followed
5.2 Undissolved or slowly precipitating materials in the in selecting the proper cell constant, leadwire size, and length
sample can form a coating on the electrodes of the conductivity and maintenance of the electrode surface condition for the
range of measurement. Calibration may be in either conduc-
tivity or resistivity units.
4
The boldface numbers in parentheses refer to the list of references at the end of 6.1.4 When an output signal is required from an on-line
these test methods. instrument, it shall be electrically isolated from the cell drive
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7. Reagents
circuit to prevent interaction between a solution ground at the
7.1 Purity of ReagentsReagent grade chemicals shall be
cell and an external circuit ground.
used in all tests. Unless otherwise indicated, it is intended that
6.2 Cells:
all reagents shall conform to the specifications of the Commit-
6.2.1 Flow-through or in-line cells shall be used for mea-
tee on Analytical Reagents of the American Chemical Society,
suring conductivities lower than 10 S/cm (resistivities higher
where such specifications are available.5 Other grades may be
than 100 000 ohm cm), to avoid contamination from the
used, provided it is first ascertained that the reagent is of
atmosphere. However, samples with conductivity greater than
sufficiently high purity to permit its use without lessening the
10 S/cm may also be measured. In all other cases, pipet-type
accuracy of the determination.
or dip cells can also be used. Pipet or dip cells may be used to
7.2 Purity of WaterUnless otherwise indicated, references
measure samples in the range of 1 to 10 S/cm if the sample is
to water shall be understood to mean reagent water conforming
protected by an inert gaseous layer of nitrogen or helium.
to Specification D 1193, Type I. In making up the potassium
6.2.2 A cell constant shall be chosen which will give a
chloride solutions for cell constant determinations, use water of
moderate cell resistance, matching the instrument manufactur-
conductivity not greater than 1.5 S/cm. If necessary, stabilize
ers requirements for the range of measurement. For laboratory
to the laboratory atmosphere by aspirating air through the
bridges, Table 2 provides conservative guidelines.
water from a fritted glass or stainless steel gas dispersion tube.
6.2.3 Flow-through and in-line cells shall be mounted so
The equilibrium point is reached when the conductivity re-
that continuous flow of the sample through or past it is
mains constant but not greater than 1.5 S/cm. The equilibrium
possible. Flow rate should be maintained at a constant rate
conductivity must be added to Table 1.
consistent with the manufacturers recommendations for the
7.3 Alcohol95 % ethyl alcohol. Alternatively, use isopro-
cell being used, particularly at conductivities below 10 S/cm.
pyl alcohol or methyl alcohol.
The cell shall retain calibration under conditions of pressure,
7.4 Aqua Regia (3 + 1)Mix 3 volumes of concentrated
flow, and temperature change, and shall exclude the atmo-
hydrochloric acid (HCl, sp gr 1.19) with 1 volume of concen-
sphere and be constructed of corrosion resistant, chemically
trated nitric acid (HNO3, sp gr 1.42). This reagent should be
inert materials. The chamber or cell shall be equipped with
used immediately after its preparation.
means for accurate measurement of the temperature.
7.5 Ethyl Ether.
6.2.4 Platinized cells shall not be used for measurement of
7.6 Hydrochloric Acid (sp gr 1.19)Concentrated HCl.
conductivities below 10 S/cm, except that a trace or flash of
7.7 Hydrochloric Acid (1 + 1)Mix 1 volume of concen-
platinum black may be used on cells for measurements in the
trated HCl (sp gr 1.19) with 1 volume of water.
range of 0.1 to 10 S/cm (see 9.4). Because of the cost and
7.8 Platinizing SolutionDissolve 1.5 g of chloroplatinic
fragility of platinum cells, it is common practice to use
acid (H2PtCl6 6H2O) in 50 mL of water containing 0.0125 g of
titanium, monel, and graphite electrodes for measurements
lead acetate (Pb(C2H3O2)2).
with accuracies on the order of 1 %. Note that these electrodes
7.9 Potassium Chloride (KCl)The assay of the potassium
may require special surface preparation. Titanium and monel
chloride must be 100.06 0.1 %. This standardization grade of
electrodes are especially suitable for high resistance solutions
KCl is available from NIST and from commercial sources. Dry
such as ultrapure water, but may introduce a small surface
at 150C for 2 h or until weight loss is less than 0.02 %; store
resistance which limits their accuracy when the measured
in desiccator.
resistance is less than a few thousand ohms (1).
7.10 Potassium Chloride Reference Solution ADissolve
6.2.5 It is recommended that cells intended for the measure-
74.2460 g of KCl (weighed in air) in water and dilute to 1 L at
ment of conductivities below 10 S/cm be reserved exclusively
20 6 2C in a Class A volumetric flask.
for such applications.
7.11 Potassium Chloride Reference Solution BDissolve
6.3 Temperature Probes:
7.4365 g of KCl (weighed in air) in water and dilute to 1 L at
6.3.1 For Temperature ControlThe measurement of tem-
20 6 2C in a Class A volumetric flask.
perature is necessary for control of a temperature bath, manual
temperature compensation, or automatic temperature compen-
sation, or all of these. Thermometers, thermistors, and resis-
tance temperature detectors with accuracies of 60.1C or 5
Reagent Chemicals, American Chemical Society Specifications, American
better are acceptable for this application. An ASTM precision Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
thermometer, Number 63C, as defined in Specification E 1, is
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
recommended. The calibration of temperature probes should be and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
checked periodically by comparison to a reference temperature MD.
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55 0.2095 3.6476
60 0.2514 3.9179
automatic temperature compensator, follow the manufacturers
65 0.2987 4.1882 instructions to calibrate the compensator or check its accuracy
70 0.3516 4.4773 and applicability to the sample being tested.
75 0.4102 4.7648
80 0.4744 5.0556
85 0.5444 5.3550 TEST METHOD AFIELD AND ROUTINE
90 0.6205 5.6527 LABORATORY MEASUREMENT OF STATIC (NON-
95 0.7030 5.9264 FLOWING) SAMPLES
100 0.7930 6.1933
A
From Thornton (1). 12. Scope
12.1 This test method is applicable to field and routine
be applied. Resistivity-reading instruments will indicate in laboratory measurements of the electrical conductivity of water
direct proportion to the cell constant, while conductivity using static samples.
reading instruments will indicate in inverse proportion to cell
constant. Conductivity cells may be calibrated with reference 13. Summary of Test Method
solutions in accordance with Section 14.
13.1 This test method utilizes dip-type or pipet-type con-
11. Temperature Coefficient of Conductivity/Resistivity ductivity cells for testing static samples having conductivities
greater than 10 S/cm. Temperature control and correction
11.1 The conductivity/resistivity of water and aqueous so-
methods are also provided.
lutions depends strongly upon the temperature. (See Table 3.)
The normal practice is to report conductivity and resistivity 14. Determination of Cell Constant
values referenced to 25.0C. The coefficient varies depending
upon the nature and composition of the dissolved electrolytes, 14.1 For the purposes of this test method, the cell constant
and upon the concentration. The dissociation of water contrib- of the conductivity cell used shall be known within 61 %. The
utes significantly to conductivities at 5 S/cm or less and manufacturers certification of the cell constant within this
increases the temperature coefficient from near 2 % per C at accuracy is generally considered satisfactory but the user is
above 5 S/cm to near 5 % per C at 0.055 S/cm. To avoid advised that damage could occur in shipment and it is best to
making a correction, it is necessary to hold the temperature of recheck the cell constant when received. If the conductivity
the sample to 25 6 0.1C. If this cannot be done, the cell has been in service for a period subsequent to this
temperature coefficient must be determined and a correction certification, it shall be rechecked by the manufacturer, or in
applied. This requires a series of conductivity and temperature the laboratory.
measurements on the sample over the required temperature 14.2 Rinse the conductivity cell several times with water,
range. Where automatic temperature compensation is used, the then at least twice with the KCl reference solution that has a
temperature compensation algorithm should be chosen that conductivity nearest to that of the sample under test (Table 1).
best simulates the composition of the samples to be tested. In Control the solution temperature to 25 6 0.1C. Measure the
high purity water, 5 S/cm or less, the variable coefficient shall resistance of the cell. Repeat the measurement on additional
be automatically determined and applied across the range of portions of the KCl reference solution until the value obtained
measurement for both the dissociation of water and its inter- remains constant to within the limits of precision in accordance
action with salt or other contaminations. (See Test Method with Section 18.
D 5391 and Refs (10), (11), and (12) for more information.) 14.3 For instruments reading measured resistance in ohms,
11.2 In static systems, exercise care to avoid change of calculate the cell constant:
composition caused by loss of volatile constituents or by J 5 10 26 Rx ~K1 1 K2!
pick-up of contaminants from the air to the containing vessel 14.4 For instruments reading measured conductance in Si-
during the series of measurements. emens, calculate the cell constant:
11.3 In flowing systems, provide means for variable heating
or cooling so that the desired range of temperature will be J 5 10 26 ~K1 1 K2!/Kx
covered. Regulate the rate of flow through each cell so as to NOTE 5Since the conductivities of a mixture of two solutions are not
keep the cell adequately flushed. exactly additive, the use of K1 + K2 is only an approximation and requires
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Allow sufficient time for equalization of temperatures. Read
the conductance or resistance. Calculate conductivity or resis- 17.2 Alternatively, report the value of the resistivity at 25C
tivity according to Section 16 using Q = 1, since no tempera- in terms of ohm-centimetres to the nearest 1 % of the deter-
ture correction is required. mined resistivity if measurements were made at 25 6 0.1C,
15.2 Routine Method Using Temperature CorrectionUse otherwise report to the nearest 3 % of the determined resistiv-
a dip-type or pipet-type cell. Rinse the conductivity cell ity.
thoroughly several times with water and then two or more
18. Precision and Bias 6
times with the sample. Measure the resistance or the conduc-
tance, and the temperature (to the nearest 0.1C), on successive 18.1 This test method was tested by nine laboratories, at
portions of the sample until a constant value is obtained. If the four concentration levels, with each operator analyzing each
measuring instrument is provided with a manual temperature sample on three different days. These collaborative test data
compensator, adjust this to the sample temperature value were obtained on reagent water. For other matrices, these data
before reading the instrument. If an automatic temperature may not apply. These data were developed using the routine
compensator is provided, no adjustment is necessary, but method (temperature correction) described in 15.2. The actual
sufficient time must be allowed to permit equalization of temperature of samples tested by the participants ranged from
temperature. If the instrument has no means of temperature 18.5 to 26.0C.
compensation, determine a temperature correction factor in 18.1.1 PrecisionThe precision of this test method within
accordance with the instructions in Section 11 to convert its designated range appears in Table 4.
readings to 25C. If instrument temperature compensation is 18.1.2 BiasRecoveries of known amounts of conductivity
used, calculate conductivity or resistivity according to Section values in a series of prepared standards appears in Table 5.
16 using Q = 1, otherwise use Q as determined in Section 11. 18.2 This test method meets requirements for precision and
bias specified in Practice D 2777 86.
16. Calculation
TEST METHOD BCONTINUOUS, IN-LINE
16.1 For instruments reading measured resistance in ohms, MEASUREMENT
calculate the conductivity of the sample:
K 5 10 6 J/RxQ 19. Scope
16.2 For instruments reading measured resistance in ohms, 19.1 This test method is applicable to the continuous, in-line
calculate the resistivity of the sample: measurement of the electrical conductivity of water.
R 5 RxQ/J 20. Summary of Test Method
16.3 For instruments reading measured conductance in Si- 20.1 This test method utilizes a flow-type conductivity cell
emens, calculate the conductivity of the sample: to sample a continuous stream of the water under test.
K 5 10 6 JKx/Q Temperature control and correction methods are also provided.
16.4 For instruments reading measured conductance in Si-
21. Procedure
emens, calculate the resistivity of the sample:
21.1 Precision Method Using Temperature ControlUse a
R 5 Q/JKx
flow-type conductivity cell. Adjust the sample stream, known
16.5 Automatic recorders and indicators provided with tem- to be free of corrosion products and other particulate contami-
perature compensators, when used with conductivity cells of nation, to a proper flow rate and bring the temperature to 25 6
the required cell constant, usually read directly in terms of 0.1C as indicated by a thermometer as described in 6.3. Allow
siemens per centimetre or S/cm referred to 25C. No calcu- sufficient time to reach equalization of temperatures. Read the
lations are necessary if the compensator is corrected for the conductance or resistance. Calculate the conductivity or resis-
solution in the cell. tivity according to Section 16 using Q = 1, since no tempera-
ture correction is required.
17. Report 21.2 Routine Method Using Temperature CorrectionUse
17.1 Report the value of the conductivity at 25C in terms of a flow-type conductivity cell. Adjust the sample stream, known
microsiemens per centimetre to the nearest 1 % of the deter-
mined conductivity if measurements were made at 25 6 0.1C,
otherwise report to the nearest 3 % of the determined conduc- 6
Supporting data are available from ASTM Headquarters. Request
tivity. RR:D191139.
--``,`,,``,`,,,,`,,,`,,`,```,``-`-`,,`,,`,`,,`---
a manual temperature compensator, adjust this to the sample
temperature value. If an automatic temperature compensator is 23.2 Experience has shown that errors of 1 to 30 % may be
provided, no adjustment is necessary but sufficient time must encountered, depending on the equipment and techniques used.
be allowed to permit equalization of temperatures. Read the Errors in temperature compensation are especially troublesome
conductance or resistance. If the instrument has no means of at conductivities below 10 S/cm. Additional errors may be
temperature compensation, determine a temperature correction encountered with low constant cells because of the difficulties
factor in accordance with Section 11 to convert readings to involved in verifying the cell constant at low conductivity
25C. If instrument temperature compensation is used, calcu- levels.
late conductivity or resistivity according to Section 16 using Q
= 1, otherwise use Q as determined in Section 11. 24. Keywords
REFERENCES
(1) Thornton, R. D., Light, T. S., A New Approach to Accurate Resis- Specific Conductance of Primary Standard KCl Solutions, Journal of
tivity Measurement of High Purity Water, Ultrapure Water, Vol 6, No. Solution Chemistry, Vol 18, No. 6, 1989, pp. 515528.
5, 1989, pp. 1426. (8) Shedlovsky, T., The Electrolytic Conductivity of Some Univalent
(2) Symposium on Power Plant Instrumentation for Measurement of Electrolytes in Water at 25C, Journal of American Chemical Society,
High-Purity Water Quality, ASTM STP 742, ASTM, 1981. Vol 54, 1932, p. 1411.
(3) Methods for Determination of Quality and Purity of Steam, ASME (9) International Critical Tables, Vol 3, 1928, p. 87.
Power Test Code, Supplement on Instruments and Apparatus, Part
(10) Light, T. S., Licht, L. L. Conductivity and Resistivity of Water from
19.11.
the Melting to Critical Points, Analytical Chemistry, Vol 59, 1987,
(4) Rossum, J. R., Conductance Method for Checking Accuracy of Water
pp. 23272330.
Analyses, Analytical Chemistry, Vol 21, 1949, p. 631.
(5) Jones, G., Bradshaw, B. C., The Measurement of the Conductance of (11) Harned, H. S., Owen, B. B., The Physical Chemistry of Electrolytic
Electrolytes, V. A. Redetermination of the Conductance of Standard Solutions, Third Ed., Reinhold Publishing Corp., New York, 1958, p.
KCl Solutions in Absolute Units, Journal of American Chemical 234.
Society, Vol 55, 1933, p. 1780. (12) Gray, D. M., Tenney, A. S., Improved Conductivity/Resistivity
(6) Wu, Y. C., Koch, W. F., Hamer, W. J., Kay, R. L., Review of Temperature Compensation for High Purity Water, Ultrapure Water,
Electrolytic Conductance Standards, Journal of Solution Chemistry, July/August, 1986.
Vol 16, No. 12, 1987, pp. 985997. (13) Glasstone, S., An Introduction to Electrochemistry, D. Van Nostrand,
(7) Wu, Y. C., Pratt, K. W., Koch, K. F., Determination of the Absolute New York, 1942, pp. 50, 56, 61.
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