NOTICE: This standard has either been superseded and replaced by a new version or discontinued.

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Designation: E 516 – 95a

Standard Practice for

Testing Thermal Conductivity Detectors Used in Gas
Chromatography1
This standard is issued under the fixed designation E 516; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope CGA P-1 Safe Handling of Compressed Gases in Contain-

1.1 This practice is intended to serve as a guide for the ers5
testing of the performance of a thermal conductivity detector CGA G-5.4 Standard for Hydrogen Piping Systems at
(TCD) used as the detection component of a gas chromato- Consumer Locations5
graphic system. CGA P-9 The Inert Gases: Argon, Nitrogen and Helium5
1.2 This practice is directly applicable to thermal conduc- CGA V-7 Standard Method of Determining Cylinder Valve
tivity detectors which employ filament (hot wire) or thermistor Outlet Connections for Industrial Gas Mixtures5
sensing elements. CGA P-12 Safe Handling of Cryogenic Liquids5
1.3 This practice is intended to describe the performance of HB-3 Handbook of Compressed Gases5
the detector itself independently of the chromatographic col- 3. Significance and Use
umn, in terms which the analyst can use to predict overall
system performance when the detector is coupled to the 3.1 Although it is possible to observe and measure each of
column and other chromatography system components. the several characteristics of a detector under different and
1.4 For general gas chromatographic procedures, Practice unique conditions, it is the intent of this practice that a
E 260 should be followed except where specific changes are complete set of detector specifications should be obtained at
recommended herein for the use of a TCD. For definitions of the same operating conditions. It should be noted also that to
gas chromatography and its various terms see Practice E 355. specify a detector’s capability completely, its performance
1.5 For general information concerning the principles, con- should be measured at several sets of conditions within the
struction, and operation of TCD see Refs. (1-4).2 useful range of the detector. The terms and tests described in
1.6 This standard does not purport to address all of the this practice are sufficiently general so that they may be used at
safety concerns, if any, associated with its use. It is the whatever conditions may be chosen for other reasons.
responsibility of the user of this standard to establish appro- 3.2 Linearity and speed of response of the recorder used
priate safety and health practices and determine the applica- should be such that it does not distort or otherwise interfere
bility of regulatory limitations prior to use. For specific safety with the performance of the detector. Effective recorder re-
information, see Section 4.3 sponse, Refs. (5, 6) in particular, should be sufficiently fast that
it can be neglected in sensitivity of measurements. If additional
2. Referenced Documents amplifiers are used between the detector and the final readout
2.1 ASTM Standards: device, their characteristics should also first be established.
E 260 Practice for Packed Column Gas Chromatography4
4. Hazards
E 355 Practice for Gas Chromatography Terms and Rela-
tionships4 4.1 Gas Handling Safety—The safe handling of compressed
2.2 CGA Standards: gases and cryogenic liquids for use in chromatography is the
responsibility of every laboratory. The Compressed Gas Asso-
ciation, (CGA), a member group of specialty and bulk gas
suppliers, publishes the following guidelines to assist the
laboratory chemist to establish a safe work environment.
Applicable CGA publications include: CGA P-1, CGA G-5.4,
1
This practice is under the jurisdiction of ASTM Committee E13 on Molecular CGA P-9, CGA V-7, CGA P-12, and HB-3.
Spectroscopy and is the direct responsibility of Subcommittee E13.19 on Chroma-
tography. 5. Sensitivity (Response)
Current edition approved Sept. 10, 1995. Published November 1995. Originally
published as E 516 – 74. Last previous edition E 516 – 95. 5.1 Definition:
2
The boldface numbers in parentheses refer to the list of references at the end of
this practice.
3 5
See Appendix X1. Available from Compressed Gas Association, Inc., 1725 Jefferson Davis
4
Annual Book of ASTM Standards, Vol 14.01 Highway, Arlington, VA 22202-4100.

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

1
 E 516
5.1.1 Sensitivity (response) of the TCD is the signal output 5.4 Exponential Decay Method:
per unit concentration of a test substance in the carrier gas, in 5.4.1 A mixing vessel of known volume fitted with a
accordance with the following relationship (7): magnetically driven stirrer is purged with the carrier gas at a
S 5 A Fc/W (1) known rate. The effluent from the flask is delivered directly to
the detector. A measured quantity of the test substance is
where: introduced into the flask, to give an initial concentration, Co, of
S = sensitivity (response), mV·mL/mg, the test substance in the carrier gas, and a timer is started
A = integrated peak area, mV·min, simultaneously.
Fc = carrier gas flow rate (corrected to detector tempera- 5.4.2 The concentration of the test substance in the carrier
ture5), mL/min, and gas at the outlet of the flask, at any time is given as follows:
W = mass of the test substance in the carrier gas, mg.
5.1.2 If the concentration of the test substance in the carrier Ct 5 Co exp @2 Fc t/Vf # (3)
gas, corresponding to a detector signal is known, the sensitivity where:
is given by the following relationship: Ct = concentration of the test substance at time t after
S 5 E/Cd (2) introduction into the flask, mg/mL,
C o = initial concentration of test compound introduced in
where: the flask, mg/mL,
E = peak height, mV, and Fc = carrier gas flow rate, corrected to flask temperature
Cd = concentration of the test substance in the carrier gas at 4 mL/min,
the detector, mg/mL. t = time, min, and
5.2 Test Conditions: Vf = volume of flask, mL.
5.2.1 Normal butane is the preferred standard test substance. 5.4.3 To determine the concentration of the test substance at
5.2.2 The measurement must be made within the linear the detector, Cd , it is necessary to apply the following
range of the detector. temperature correction:
5.2.3 The measurement must be made at a signal level at
Cd 5 Ct ~T f/Td ! (4)
least 100 times greater than the minimum detectability (200
times greater than the noise level) at the same conditions. where:
5.2.4 The rate of drift of the detector at the same conditions Cd = concentration of the test substance at the detector,
must be stated. d mg/mL,
5.2.5 The test substance and the conditions under which the Tf = flask temperature, K, and
detector sensitivity is measured must be stated. This will Td = detector temperature, K.
include but not necessarily be limited to the following: 5.4.4 The sensitivity of the detector at any concentration can
5.2.5.1 Type of detector (for example, platinum-tungsten be calculated by:
filament type), S 5 E/Cd (5)
5.2.5.2 Detector geometry (for example, flow-type,
diffusion-type), where:
5.2.5.3 Internal volume of the detector, S = sensitivity, mV·mL/mg,
5.2.5.4 Carrier gas, E = detector, signal, mV, and
5.2.5.5 Carrier gas flow rate (corrected to detector tempera- Cd = concentration of the test substance at the detector,
ture), mg/mL.
5.2.5.6 Detector temperature, NOTE 1—This method is subject to errors due to inaccuracies in
5.2.5.7 Detector current, measuring the flow rate and flask volume. An error of 1 % in the
5.2.5.8 Method of measurement, and measurement of either variable will propagate to 2 % over two decades in
5.2.5.9 Type of power supply (for example, constant volt- concentration and to 6 % over six decades. Therefore, this method should
not be used for concentration ranges of more than two decades over a
age, constant current). single run.
5.2.5.10 For capillary detectors, the make-up gas, carrier, NOTE 2—A temperature difference of 1°C between flask and flow
and reference flows should be stated. measuring apparatus will, if uncompensated, introduce an error of 1⁄3 %
5.3 Methods of Measurement: into the flow rate.
5.3.1 Sensitivity may be measured by any of three methods: NOTE 3—Extreme care should be taken to avoid unswept volumes
5.3.1.1 Experimental decay with exponential dilution flask between the flask and the detector, as these will introduce additional errors
(8, 9) (see 5.4), into the calculations.
5.3.1.2 Utilizing the permeation tube (10), under steady- NOTE 4—Flask volumes between 100 and 500 mL have been found the
state conditions (see 5.5), most convenient. Larger volumes should be avoided due to difficulties in
obtaining efficient mixing and likelihood of temperature gradients.
5.3.1.3 Utilizing Young’s apparatus (11), under dynamic
conditions (see 5.6). 5.5 Method Utilizing Permeation Tubes:
5.3.2 Calculation of TCD sensitivity by utilizing actual 5.5.1 Permeation tubes consist of a volatile liquid enclosed
chromatograms is not recommended because in such a case the in a section of plastic tubing. They provide low concentrations
amount of test substance corresponding to the peak cannot be of vapor by diffusion of the vapor through the walls of the
established with sufficient accuracy. tubing. The rate of diffusion for a given permeation tube is

2
 E 516
dependent only on the temperature. As the weight loss over a signal equal to twice the noise level and is calculated from the
period of time can be easily and accurately measured gravi- measured sensitivity and noise level values as follows:
metrically, the rate of diffusion can be accurately determined. D 5 2N/S (8)
Hence, these devices have been proposed as primary standards.
5.5.2 Accurately known concentrations can be prepared by where:
passing a gas over the previously calibrated permeation tube at D = minimum detectability, mg/mL,
constant temperature. The concentration of the test substance N = noise level, mV, and
in the gas can then be easily calculated according to the S = sensitivity of the detector, mV·mL/mg.
following relationship: 6.2 Test Conditions—Measure sensitivity in accordance
with the specifications given in Section 5. Measure noise level
C 5 RT/Fc (6)
in accordance with the specifications given in Section 9. Both
where: measurements have to be carried out at the same conditions
C = concentration of the test substance in the gas, mg/ (for example, carrier gas identity and flow rate, detector
mL, temperature, and current) and preferably at the same time.
RT = permeation rate of the test substance at the tempera- When giving minimum detectability, state the noise level on
ture of the permeation tube, mg/min, and which the calculation was based.
Fc = flow rate of the gas over the tube at the temperature
of the tube, mL/min. 7. Linear Range
NOTE 5—If the flow rate of the gas is measured at a temperature 7.1 Definition—The linear range of a TCD is the range of
different from the tube temperature, correction must be made, as described concentrations of the test substance in the carrier gas, over
in Appendix X1. which the sensitivity of the detector is constant to within 5 %
5.5.3 When using a permeation tube for the testing of a as determined from the linearity plot specified in 7.2.2.
TCD, the carrier gas is passing over a previously calibrated 7.1.1 The linear range may be expressed in three different
permeation tube containing the test substance at constant ways:
temperature and introduced immediately into the detector, kept 7.1.1.1 As the ratio of the upper limit of linearity obtained
at the desired temperature. Knowing the concentration of the from the linearity plot, and the minimum detectability, both
test substance in the carrier gas leaving the permeation tube at measured for the same test substance as follows:
the temperature of the tube, the concentration at detector L.R. 5 ~Cd! max/D (9)
temperature can be calculated directly, by applying the correc-
tion specified in 5.4.2. Knowing this value and the detector where:
signal, the sensitivity of the detector can be obtained according L.R. = linear range of the detector,
to the equation given in 5.4.4. (Cd)max = upper limit of linearity obtained from the
linearity plot, mg/mL, and
NOTE 6—Permeation tubes are suitable only for preparing relatively D = minimum detectability, mg/mL.
low concentrations in the part-per-million range. Hence for detectors of If the linear range is expressed by this ratio, the minimum
relatively low sensitivity or of higher noise levels, this method may not
detectability must also be stated.
satisfy the criteria given in 5.2.3, which requires that the signal be at least
100 times greater than the noise level. 7.1.1.2 By giving the minimum detectability and the upper
limit of linearity (for example, from 1 3 10−6 mg/mL to
5.6 Dynamic Method:
2 3 10−1 mg/mL).
5.6.1 In this method a known quantity of test substance is
7.1.1.3 By giving the linearity plot itself, with the minimum
injected into the flowing carrier gas stream. A length of empty
detectability indicated on the plot.
tubing between the sample injection point and the detector
7.2 Method of Measurement:
permits the band to spread and be detected as a Gaussian band.
7.2.1 For the determination of the linear range of a TCD,
The detector signal is then integrated by any suitable method.
either the exponential decay or the dynamic methods described
This method has the advantage that no special equipment or
in 5.4 and 5.6 respectively may be used. The permeation tube
devices are required other than conventional chromatographic
method (5.5) will not be suitable except for detectors of
hardware. For detectors optimized for capillary column flow
extremely unusual characteristics because of the limited range
rates, uncoated, deactivated, fused silica tubing should be used.
of concentrations obtainable with that method.
5.6.2 The sensitivity of the detector is calculated from the
7.2.2 Measure the sensitivity at various concentrations of
peak area according to 5.1.1.
the test substance in the carrier gas in accordance with the
NOTE 7—Care should be taken that the peak obtained is sufficiently methods described above. Plot the sensitivity versus log
wide so the accuracy of the integration is not limited by the response time concentration on a semilog paper as shown in Fig. 1. Draw a
of the detector or of the recording device. smooth line through the data points. The upper limit of
NOTE 8—Peak areas obtained by integration (Ai) or by multiplying peak
height by peak width at half height (Ac ) differ by 6 % for a Gaussian peak:
linearity is given by the intersection of the line with a value
0.95 3 Smax where Smax is the highest value of sensitivity on
A c 5 0.94 Ai (7)
the fitted curve.
6. Minimum Detectability
NOTE 9—The dynamic method will give somewhat larger values for the
6.1 Definition—Minimum detectability is the concentration upper limit of linearity as compared to the exponential decay method,
of the test substance in the carrier gas which gives a detector because the integrated signal will average increments of signal obtained

3
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FIG. 1 Example for a Linearity Plot of a Thermal Conductivity Detector

over the linear range of the detector with those obtained in the nonlinear 8.2.2 Express the dynamic range according to 8.1.1.
range. 8.2.3 In giving the dynamic range or the dynamic range
7.2.3 Express the linear range in accordance with 7.1.1. plot, specify the test conditions in accordance with 5.2.5.
7.2.4 In giving the linear range of the linearity plot, specify
the test conditions in accordance with 5.2.5. 9. Noise and Drift
9.1 Definitions:
8. Dynamic Range
9.1.1 noise—the amplitude expressed in microvolts of the
8.1 Definition—The dynamic range of the detector is that peak-to-peak envelope of the baseline which includes all
range of concentrations of the test substance, over which a observed random variations of the detector signal of a fre-
change in concentration produces a change in detector signal. quency on the order of one or more cycles per minute (see Fig.
The lower limit is given by the minimum detectability. The 3). This noise corresponds to the observed noise only. The
upper limit is the highest concentration at which a slight further actual noise of the system may be larger or smaller than the
increase in concentration will give an observable increase in observed value depending upon the method of data collection
detector signal, and the dynamic range is the ratio of the upper or signal monitoring from the detector, since observed noise is
and lower limits. The dynamic range can be greater than the a function of the frequency, speed of response, and the
linear range, but obviously cannot be smaller. bandwidth of the electronic circuit measuring the detector
8.1.1 The dynamic range may be expressed in three different signal.
ways: 9.1.2 drift—the average slope of the noise envelope ex-
8.1.1.1 As the ratio of the upper limit of dynamic range and pressed in microvolts per hour as measured over 1⁄2 h.
the minimum detectability by simultaneously stating the mini-
9.2 Methods of Measurement:
mum detectability (for example, 2 3 106 with a minimum
detectability of 1 3 10−6 mg/mL). 9.2.1 With the attenuator set at maximum sensitivity (mini-
8.1.1.2 By giving the minimum detectability and the upper mum attenuation) adjust the detector output with the “zero’’
limit of dynamic range (for example, from 1 3 10 −6 mg/mL to control to read near mid-scale on the recorder. Allow at least 1⁄2
2 mg/mL). h of baseline to be recorded.
8.1.1.3 By giving the dynamic plot itself with the minimum 9.2.2 Draw two parallel lines to form an envelope which
detectability indicated on the plot. encloses the random excursions of a frequency of approxi-
8.2 Methods of Measurement: mately 0.0167 Hz (1 cycle per minute) or more. Measure the
8.2.1 Using the exponential decay method (see 5.4), mea- distance between the parallel lines at right angles to the edge of
sure the detector output signal (E) at various concentrations (Cd the chart paper. Express the value as microvolts of noise.
) of the test substance in the carrier gas. Plot E versus Cd on 9.2.3 Measure the net change in microvolts of the lower line
rectilinear graph paper, and draw a smooth curve through the of the envelope over 1⁄2 h and multiply by two. Express as
data points as shown in Fig. 2. The upper limit of the dynamic microvolts per hour drift.
range is the concentration at which the slope is zero. 9.2.4 In specifications giving the measured noise and drift

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FIG. 2 Example for a Plot to Determine the Dynamic Range of a Thermal Conductivity Detector

constant may also be separately specified in addition to the

response time.
NOTE 10—For diffusion geometry detectors, the time required for the
composition to come to equilibrium in the measuring region depends
primarily on the volume, length, and diameter of the measuring region and
diffusion channels, and of the diffusion constant of the carrier gas-test
substance pair. For flow-geometry detectors, the response time is depen-
dent primarily on the volume of the measuring region and the carrier gas
flow rate. Hence a statement of the internal volume and geometry of the
detector and of the flow rate is necessary for the specification to be
complete.
10.2 Method of Measurement:
10.2.1 The composition of the gas entering the detector is
changed in a stepwise manner and the output signal recorded.
The time required for the signal to reach 63.2 % of the new
FIG. 3 Example for the Measurement of the Noise Level and Drift equilibrium value is determined from the recorder chart (see
of a Thermal Conductivity Detector Fig. 4). The test may be repeated at various flow rates.
10.2.2 Flow rates for the measurement should be chosen
of the TCD, specify the test conditions in accordance with with due regard for the types (diameter) of columns for which
5.2.5. the detector is designed. Table 1 lists typical flow rates used
with various column types. The flow rates should be corrected
10. Response Time to detector temperatures.6
10.1 Definition—The response time (speed of response) of 10.2.3 A stepwise change in composition may be obtained
the detector at a given flow rate is the time required for the by means of high-speed valves which rapidly substitute carrier
output signal to reach 63 % of the new equilibrium value when gas with added test substance for pure carrier gas or for gas
the composition of the gas entering the detector is changed in containing a different amount. The test substance may be added
a stepwise manner, within the linear range of the detector. by means of a saturator which saturates the carrier gas with the
Internal volume and geometry of the detector must also be vapor of a volatile liquid in the manner of Schmauch (12).
stated as part of this specification. Response time may be NOTE 11—Design of the apparatus should be such as to prevent
determined and specified at various flow rates. backmixing of the two gases ahead of the detector, which would result in
10.1.1 The response time of the detector is determined by a a diffuse composition change.
combination of effective volume and time constant of the 10.2.4 Alternatively, a mixture of the carrier gas containing
sensing elements. Effective volume determines the time re- a known amount of the test substance may be used.
quired to introduce a compositional change into the measuring
region. Time constant is the time required for the elements to
respond to concentration changes. Effective volume and time 6
For correlation, see Appendix X1.

5
 E 516
microlitres) of the detector must be stated.
10.3.2 The effective volume of the detector and the time
constant of the sensing element may be established from the
same data in the following way:
10.3.2.1 Plot the response time in seconds versus the recip-
rocal of the flow rate (that is, seconds per millilitre), draw a
straight line through the data points, and extrapolate back to
zero reciprocal flow rate (for example, infinite flow rate), as
shown in Fig. 6.
10.3.2.2 The effective volume of the TCD is given by the
slope of the straight line:
Ve 5 @Dt/D ~1/Fc!60#103 (10)

where:
Ve = effective volume of the detector, µL,
t = response time of the detector, s, and
Fc = carrier gas flow rate corrected to detector tempera-
ture,4 mL/min.
10.3.2.3 The time constant of the sensing element is equal to
the value of the ordinate at the intersection of the straight line
at zero reciprocal flow rate.
10.3.3 The effective volume of the detector and the time
constant of the sensing element may also be determined by the
method of Kieselbach (13), in the following way:
10.3.3.1 Use a high-speed sampling valve to inject a plug
FIG. 4 Example for the Measurement of Response Time of a sample of air into the detector. Determine the response time at
Thermal Conductivity Detector (12) various flow rates from the shape of the recorded peak, by
drawing tangents through the inflection points. The response
TABLE 1 Typical Carrier Gas Flow Rates for Various Column time is equal to the time interval from the intersection of the
Types tangents to the point at which the signal has returned to 37 %
Column Outside Column Inside of the value of the height of the intersection of the tangents (see
Flow Rate,
Diameter, Diameter,A Fig. 7).
mL/min
in. (mm) in. (mm)
10.3.3.2 Plot the data as described in 10.3.2.1 and calculate
0.02 ~0.5! Open tubular 0.01 (0.25–0.32) 1 to 3 effective volume and time constant as described in 10.3.2.2 and
0.03 ~0.75!% Columns 0.2 (0.53) 5 to 25
1⁄16 (1.6) 0.01 to 0.04 (0.25–1.02) 1 to 10 10.3.2.3.
1⁄8(3.2) 0.085 (2.16) 10 to 30
1⁄4(6.4) 0.180 (4.57) 50 to 100 11. Standard Values
A
Typical values. 11.1 Detector characteristics measured at optimum condi-
tions and at the current recommended by the manufacturer may
10.2.5 The concentration of the test substance must be be expected to fall within the typical range of values listed in
within the linear range of the detector. Table 2 which also indicates the way these values should be
expressed. All data refer to n-butane as the test substance.
NOTE 12—Extreme care must be exercised to adjust the flow rates so
that a change in flow rate does not occur when compositions are switched;
12. Data Handling
otherwise errors due to flow sensitivity of the detector are introduced.
12.1 All manufacturers supply an integral electrometer to
10.3 Calculation:
allow the small electrical current changes to be coupled to
10.3.1 The response time of TCD may be expressed in two
recorders/integrators/computers. The preferred system will in-
ways:
corporate one of the newer integrators or computers that
10.3.1.1 As the time, in seconds, obtained from a plot
converts an electrical signal into clearly defined peak area
similar to Fig. 4 and the flow rate in millilitres per minute at
counts in units such as microvolt-seconds. These data can then
which the test was made.
be readily used to calculate the linear range.
10.3.1.2 As a rectilinear plot of response time, in seconds,
12.1.1 Another method uses peak height measurements.
versus carrier gas flow rate, in millilitres per minute (see Fig.
This method yields data that are very dependent on column
5).
performance and therefore not recommended.
NOTE 13—Use of the plot of response time versus carrier gas flow rate 12.1.2 Regardless of which method is used to calculate
is strongly recommended because it provides a better picture of the linear range, peak height is the only acceptable method for
contributions of effective volume and sensing element time constant. determining minimum detectability.
10.3.1.3 In either case, the internal geometry (for example, 12.2 Calibration— It is essential to calibrate the measuring
diffusion- or flow-through type) and the internal volume (in system to ensure that the nominal specifications are acceptable

6
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FIG. 5 Example for a Response Time versus Flow Rate Plot of a Thermal Conductivity Detector (12)

FIG. 6 Example for the Measurement of the Effective Volume and the Time Constant of a Thermal Conductivity Detector

and particularly to verify the range over which the output of the peak area or peak height measurements.
device, whether peak area or peak height, is linear with respect
to input signal. Failure to perform this calibration may intro- 13. Keywords
duce substantial errors into the results. Methods for calibration
13.1 flame ionization detector (FID); flame photometric
will vary for different manufacturers’ devices but may include
accurate constant voltage supplies or pulse generating equip- detectors (FPD); gas chromatography (GC); packed columns;
ment. The instruction manual should be studied and thoroughly supercritical fluid chromatography; thermal conductivity de-
understood before attempting to use electronic integration for tectors

7
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FIG. 7 Example for the Calculation of the Response Time of a Thermal Conductivity Detector from the Air Peak (13)

TABLE 2 Typical Values for Thermal Conductivity Detector

Performance Characteristics
Performance Unit Range of
Characteristics Typical
Values
Sensitivity mV·mL/mg 5000 to 15 000
Minimum detectability mg/mL 3 3 10−7 to
1 3 10−5
Linear range (upper mg/mL 0.2 to 2.0
limit)
Dynamic range (upper mg/mL 2.1 to 2.4
limit)
Noise µV 5 to 50
Drift µV/h 20 to 250
Response time s 0.5 to 5
Effective volume µL 5 to 500
Time constant s 0.05 to 0.5

APPENDIXES

(Nonmandatory Information)

X1. CORRECTION OF FLOW RATE TO DETECTOR TEMPERATURE

X1.1 Since the carrier gas flow rate is usually measured at Fa = carrier gas flow rate measured at column or detector
ambient (room) temperature, it has to be corrected to the outlet and ambient temperature, mL/min,
conditions at the detector. Td = detector temperature, K,
Ta = ambient temperature, K,
X1.2 The correction is made as follows: pw = partial pressure of water at ambient temperature, Pa,
Fc 5 F a ~Td/Ta!@1 2 ~pw/ pa!#~pa/Pd! (X1.1) pa = ambient pressure, Pa, and
Pd = detector pressure, Pa.
where:
Fc = corrected flow rate, mL/min, X1.3 The factor [1 − (pw/ pa)] is to be applied only if a wet

8
 E 516
(for example, soap bubble) flow meter is used for the measure- permeation tube method (see 5.5.2), the temperature of the
ment. exponential dilution flask or the permeation tube should be
substituted for T d.
X1.4 If correction to other than detector temperature is
necessary, as in the exponential decay method (see 5.4.2) or the

X2. LIST OF SYMBOLS AND ABBREVIATIONS

N = noise level, mV or µV
A = peak area, mV·min Pa = ambient pressure, Pa
Ai = peak area obtained by integration, mV·min
Ac = peak area obtained by calculation (multiplying Pw = partial pressure of water at ambient temperature,
peak height by the peak width at half height), Pa
mV·min
C = steady state concentration of a test substance in Pd = carrier gas pressure in the detector, torr
the carrier gas (flowing over a permeation tube), RT = permeation rate of a test substance at the tempera-
mg/mL ture of the permeation tube, mg/mL
Cd = concentration of a test substance in the carrier gas S = detector sensitivity mV·mL/mg
at the detector, mg/mL S max = highest value of sensitivity on the fitted curve
Ct = concentration of a test substance in the carrier gas when plotting sensitivity versus concentration on
at time t (minutes) after introduction into the a semilog paper, mV·mL/mg
dilution flask, mg/mL Ta = ambient temperature, K
Co = initial concentration of a test substance in the Tf = temperature of the dilution flask, K
dilution flask, mg/mL Td = temperature of the detector, K
D = minimum detectability, mg/mL TCD = thermal conductivity detector
E = detector signal, mV t = time, min
Fc = carrier gas flow rate corrected to the temperature Ve = effective volume of the detector, µL
of detector, dilution flask, or permeation tube Vf = volume of the dilution flask, mL
(whichever is applicable), mL/min W = mass of the test substance in the carrier gas
Fa = carrier gas flow rate measured at the outlet of the corresponding to a peak, mg
column or detector, at ambient temperature, mL/ t = response time of the detector, s
min

REFERENCES

(1) Lawson, A. E., and Miller, J. M., “Thermal Conductivity Detectors in (8) Lovelock, J. E., “Argon Detectors. Author’s Additional Comments,”
Gas Chromatography,” Journal of Gas Chromatography, JCHSB, Vol Gas Chromatography Abstracts, GCHAA, Butterworths, London,
4, 1966, pp. 273–284. 1960, pp. 26–27.
(2) Ettre, L. S. and Zlatkis, A., The Practice of Gas Chromatography, (9) Lovelock, J. E., “Ionization Methods for the Analysis of Gases and
Interscience Publishers, Div. of John Wiley & Sons, New York, N. Y., Vapors,” Analytical Chemistry, ANCHA, Vol 33, 1961, pp. 162–168.
1967.
(3) Guiochen, G. and Guillemin, C. L., “Quantitative Gas Chromatogra- (10) O’Keefe, A. E., and Ortman, G. C., “Primary Standards for Trace Gas
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