Beruflich Dokumente
Kultur Dokumente
1. Scope
2. Referenced Documents
1.2 This practice is directly applicable to thermal conductivity detectors which employ filament (hot wire) or thermistor
sensing elements.
1
This practice is under the jurisdiction of ASTM Committee E13 on Molecular
Spectroscopy and Separation Science and is the direct responsibility of Subcommittee E13.19 on Separation Science.
Current edition approved Jan. 1, 2013. Published January 2013. Originally
approved in 1974. Last previous edition approved in 2005 as E516 95a (2005).
DOI: 10.1520/E0516-95AR13.
2
The boldface numbers in parentheses refer to the list of references at the end of
this practice.
3
See Appendix X1.
4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standards Document Summary page on
the ASTM website.
5
Available from Compressed Gas Association (CGA), 4221 Walney Rd., 5th
Floor, Chantilly, VA 20151-2923, http://www.cganet.com.
Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
5. Sensitivity (Response)
5.1 Definition:
5.1.1 Sensitivity (response) of the TCD is the signal output
per unit concentration of a test substance in the carrier gas, in
accordance with the following relationship (7):
S 5 A F c /W
(1)
where:
S
= sensitivity (response), mVmL/mg,
A
= integrated peak area, mVmin,
= carrier gas flow rate (corrected to detector
Fc
temperature5), mL/min, and
W
= mass of the test substance in the carrier gas, mg.
5.1.2 If the concentration of the test substance in the carrier
gas, corresponding to a detector signal is known, the sensitivity
is given by the following relationship:
S 5 E/C d
C t 5 C o exp@ 2F c t/V f #
(3)
where:
Ct = concentration of the test substance at time t after
introduction into the flask, mg/mL,
Co = initial concentration of test compound introduced in the
flask, mg/mL,
Fc = carrier gas flow rate, corrected to flask temperature4
mL/min,
t
= time, min, and
Vf = volume of flask, mL.
(2)
where:
E = peak height, mV, and
Cd = concentration of the test substance in the carrier gas at
the detector, mg/mL.
5.2 Test Conditions:
5.2.1 Normal butane is the preferred standard test substance.
5.2.2 The measurement must be made within the linear
range of the detector.
5.2.3 The measurement must be made at a signal level at
least 100 times greater than the minimum detectability (200
times greater than the noise level) at the same conditions.
5.2.4 The rate of drift of the detector at the same conditions
must be stated.
5.2.5 The test substance and the conditions under which the
detector sensitivity is measured must be stated. This will
include but not necessarily be limited to the following:
5.2.5.1 Type of detector (for example, platinum-tungsten
filament type),
5.2.5.2 Detector geometry (for example, flow-type,
diffusion-type),
5.2.5.3 Internal volume of the detector,
5.2.5.4 Carrier gas,
5.2.5.5 Carrier gas flow rate (corrected to detector
temperature),
5.2.5.6 Detector temperature,
5.2.5.7 Detector current,
(4)
where:
d
where:
S = sensitivity, mVmL/mg,
E = detector, signal, mV, and
2
(5)
A c 5 0.94 A i
(7)
6. Minimum Detectability
6.1 DefinitionMinimum detectability is the concentration
of the test substance in the carrier gas which gives a detector
signal equal to twice the noise level and is calculated from the
measured sensitivity and noise level values as follows:
D 5 2N/S
(8)
where:
D = minimum detectability, mg/mL,
N = noise level, mV, and
S = sensitivity of the detector, mVmL/mg.
6.2 Test ConditionsMeasure sensitivity in accordance
with the specifications given in Section 5. Measure noise level
in accordance with the specifications given in Section 9. Both
measurements have to be carried out at the same conditions
(for example, carrier gas identity and flow rate, detector
temperature, and current) and preferably at the same time.
When giving minimum detectability, state the noise level on
which the calculation was based.
(6)
where:
C = concentration of the test substance in the gas, mg/mL,
RT = permeation rate of the test substance at the temperature
of the permeation tube, mg/min, and
Fc = flow rate of the gas over the tube at the temperature of
the tube, mL/min.
NOTE 5If the flow rate of the gas is measured at a temperature
different from the tube temperature, correction must be made, as described
in Appendix X1.
7. Linear Range
7.1 DefinitionThe linear range of a TCD is the range of
concentrations of the test substance in the carrier gas, over
which the sensitivity of the detector is constant to within 5 %
as determined from the linearity plot specified in 7.2.2.
7.1.1 The linear range may be expressed in three different
ways:
7.1.1.1 As the ratio of the upper limit of linearity obtained
from the linearity plot, and the minimum detectability, both
measured for the same test substance as follows:
L.R. 5 ~ C d ! max/D
where:
L.R.
(Cd)max
(9)
NOTE 9The dynamic method will give somewhat larger values for the
upper limit of linearity as compared to the exponential decay method,
because the integrated signal will average increments of signal obtained
over the linear range of the detector with those obtained in the nonlinear
range.
8. Dynamic Range
8.1 DefinitionThe dynamic range of the detector is that
range of concentrations of the test substance, over which a
change in concentration produces a change in detector signal.
The lower limit is given by the minimum detectability. The
FIG. 2 Example for a Plot to Determine the Dynamic Range of a Thermal Conductivity Detector
FIG. 3 Example for the Measurement of the Noise Level and Drift
of a Thermal Conductivity Detector
NOTE 10For 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 dependent 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.
Column Outside
Diameter,
in. (mm)
0.02 s 0.5d
0.03 s 0.75d
Open tubular
Columns
(1.6)
(3.2)
14 (6.4)
1 16
18
Flow Rate,
mL/min
0.01 (0.250.32)
0.2 (0.53)
1 to 3
5 to 25
1 to 10
10 to 30
50 to 100
Typical values.
10.3 Calculation:
6
Column Inside
Diameter,A
in. (mm)
Performance
Characteristics
Unit
Sensitivity
Minimum detectability
mVmL/mg
mg/mL
mg/mL
Range of
Typical
Values
5000 to 15 000
3 107 to
1 105
0.2 to 2.0
mg/mL
2.1 to 2.4
V
V/h
s
L
s
5 to 50
20 to 250
0.5 to 5
5 to 500
0.05 to 0.5
NOTE 13Use of the plot of response time versus carrier gas flow rate
is strongly recommended because it provides a better picture of the
contributions of effective volume and sensing element time constant.
(10)
where:
Ve = effective volume of the detector, L,
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
FIG. 7 Example for the Calculation of the Response Time of a Thermal Conductivity Detector from the Air Peak (13)
13. Keywords
13.1 flame ionization detector (FID); flame photometric
detectors (FPD); gas chromatography (GC); packed columns;
supercritical fluid chromatography; thermal conductivity detectors
pw
pa
Pd
(X1.1)
where:
Fc = corrected flow rate, mL/min,
Fa = carrier gas flow rate measured at column or detector
outlet and ambient temperature, mL/min,
Td = detector temperature, K,
Ta = ambient temperature, K,
A
Ai
Ac
C
Cd
Ct
Co
D
E
Fc
Fa
N
Pa
= ambient pressure, Pa
Pw
Pd
RT
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.
This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/
10