Designation: E355 – 96 (Reapproved 2007)

Standard Practice for

Gas Chromatography Terms and Relationships1
This standard is issued under the fixed designation E355; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope 2.6 Gas-Displacement Chromatography employs a desor-

1.1 This practice covers primarily the terms and relation- bent as the carrier gas or in the carrier gas to displace a less
ships used in gas elution chromatography. However, most of strongly held solute from the stationary phase which in turn
the terms should also apply to other kinds of gas chromatog- displaces the next less strongly held one etc., causing the
raphy and are also valid in the various liquid column chro- components to emerge in the normal order, that is, least-to-
matographic techniques, although at this time they are not most strongly absorbed.
standardized for the latter usage. 2.7 Isothermal Gas Chromatography is the version of the
technique in which the column temperature is held constant
2. Names of Techniques during the passage of the sample components through the
2.1 Gas Chromatography, abbreviated as GC, comprises all separation column.
chromatographic methods in which the moving phase is 2.8 Programmed Temperature Gas Chromatograp-
gaseous. The stationary phase may be either a dry granular hy (PTGC), is the version of the technique in which the
solid or a liquid supported by the granules or by the wall of the column temperature is changed with time during the passage of
column, or both. Separation is achieved by differences in the the sample components through the separation column. In
distribution of the components of a sample between the mobile linear PTGC the program rate is constant during analysis.
and stationary phases, causing them to move through the Isothermal intervals may be included in the temperature
column at different rates and from it at different times. In this program.
recommended practice gas elution chromatography is implied. 2.9 Programmed Flow, Pressure, or Velocity Gas Chroma-
2.2 Gas-Liquid Chromatography, abbreviated as GLC, uti- tography is the version of the technique in which the carrier
lizes a liquid as the stationary phase, which acts as a solvent for gas flow, pressure, or velocity is changed during analysis.
the sample components. 2.10 Reaction Gas Chromatography is the version of the
2.3 Gas-Solid Chromatography, abbreviated as GSC, uti- technique in which the composition of the sample is changed
lizes an active solid (adsorbent) as the stationary phase. between sample introduction and the detector. The reaction can
2.4 Gas Elution Chromatography utilizes a continuous in- take place upstream of the column when the chemical compo-
ert gas flow as the carrier gas and the sample is introduced as sition of the individual components passing through the col-
a gas or a liquid with a finite volume into the carrier gas stream. umn differs from that of the original sample, or between the
If the sample is introduced as a liquid, it is vaporized in the column and the detector when the original sample components
system prior to or during passage through the separation are separated in the column but their chemical composition is
column. changed prior to entering the detection device.
2.5 Gas-Frontal Chromatography is a technique in which a 2.11 Pyrolysis Gas Chromatography is the version of reac-
continuous stream of carrier gas mixed with sample vapor is tion gas chromatography in which the original sample is
instantaneously replaced by a continuous stream of carrier gas decomposed by heat to more volatile components prior to
containing sample vapor at a different concentration. The passage through the separation column.
concentration profile is therefore step-shaped at the column
3. Apparatus
inlet.
3.1 Sample Inlet Systems, represent the means for introduc-
ing samples into the separation column, including the heated
1
This practice is under the jurisdiction of ASTM Committee E13 on Molecular zones permitting the vaporization of the introduced liquid
Spectroscopy and Separation Science and is the direct responsibility of Subcom- samples prior to their passage through the column. Sample
mittee E13.19 on Separation Science.
Current edition approved March 1, 2007. Published March 2007. Originally
introduction can be carried out by introduction of a liquid,
approved in 1968. Last previous edition approved in 2001 as E355 - 96 (2001). solid, or gas into the carrier-gas stream. The sample may be
DOI: 10.1520/E0355-96R07. vaporized before or after introduction into the column.

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 E355 – 96 (2007)
3.1.1 Direct Inlets, rapidly vaporize the sample prior to 3.3.4 Spectrometric Detectors, measure and record spectra
entering the column. All of the sample vapor enters the column. of eluting components, such as the mass spectrum of the
3.1.2 On-Column Inlets, introduce a liquid sample into the infrared spectrum.
column. The sample vaporizes as the column section contain- 3.4 Traps, are devices for recovering sample components
ing the liquid heats up after injection. from the mobile phase eluting from GC columns.
3.1.3 Split Inlets, rapidly vaporize the sample prior to
entering the column. A defined fraction of the sample vapor 4. Reagents
enters the column; the remainder leaves the inlet through a vent 4.1 Carrier Gas is the Mobile Phase used to sweep or elute
at a flow rate Fv. The ratio of the total inlet flow (Fv + Fc) to the sample components through and from the column.
the column flow ( Fc) is called the split ratio (s): 4.2 The Stationary Phase is composed of the active immo-
Fv 1 F c bile materials within the column that selectively delay the
s5 (1)
Fc passage of sample components by dissolving or adsorbing
3.1.4 Splitless Injection, utilizes a split inlet wherein the them, or both. Inert materials that merely provide physical
split vent flow is blocked during the injection period such that support for the stationary phase or occupy space within the
most of the sample vapor enters the column. The injection column are not part of the stationary phase.
period is typically one minute. The split vent flow is reestab- 4.2.1 Liquid Stationary Phase is one type of stationary
lished afterward usually for the remainder of the run. phase which is dispersed on the solid support or the inner
3.1.5 Programmed-Temperature Vaporizers (PTV), accept a column wall and causes the separation of the sample compo-
liquid sample that vaporizes as the inlet system heats up after nents by differences in the partitioning of the sample compo-
injection. A PTV may operate in either a split, splitless, nents between the mobile and liquid phases.
on-column, or direct mode. 4.2.2 An Active Solid is one that has ab- or adsorptive
3.1.6 A Retention Gap, is a section of tubing inserted properties by means of which chromatographic separations
between the inlet and the analytical column proper. The may be achieved.
retention gap may have an inner diameter different than the 4.3 The Solid Support is the inert material that holds the
analytical column. The retention gap has significantly lower stationary (liquid) phase in intimate contact with the carrier gas
retaining power than the analytical column; in practice the flowing through it. It may consist of porous or impenetrable
retention gap is deactivated but not coated. particles or granules which hold the liquid phase and between
3.2 Columns, consist of tubes that contain the stationary which the carrier gas flows, or the interior wall of the column
phase and through which the gaseous mobile phase flows. itself, or a combination of these.
3.2.1 Packed Columns, are filled with granular packing that 4.4 The Column Packing consists of all the material used to
is kept in place by gas-permeable plugs at both ends. fill packed columns, including the solid support and the liquid
3.2.2 Open-Tubular Columns, have unobstructed central phase or the active solid.
gasflow channels. 4.4.1 The Liquid-Phase Loading describes the relative
amount of liquid phase present in a packed column when the
3.2.2.1 Wall-Coated Open-Tubular Columns, abbreviated
column packing consists only of the liquid phase plus the solid
WCOT columns, have the liquid phase coated directly on the
support. It is usually expressed as weight percent of liquid
inside, relatively smooth wall of the column tubing.
phase present in the column packing:
3.2.2.2 Porous-Layer Open-Tubular Columns, abbreviated
PLOT columns, have a solid porous layer present on the tube Liquid2phase loading, wt%
wall but still maintain the unobstructed central gas-flow ~amount of liquid phase! 3 100
5 ~amount of liquid phase 1 amount of solid support! (2)
channel. This porous solid layer can either act as an adsorbent
or a support which in turn is coated with a thin film of the 4.5 Solutes are the introduced sample components that are
liquid phase, or both. The solid layer can either be deposited on delayed by the column as they are eluted through it by the
the inside tube wall or formed by chemical means from the carrier gas.
wall. 4.6 Unretained Substances are not delayed by the column
3.2.2.3 Support-Coated Open-Tubular Columns, abbrevi- packing.
ated SCOT columns, refer to those PLOT Columns where the
solid layer consists of the particles of a solid support which 5. Gas Chromatographic Data
were deposited on the inside tube wall. 5.1 A Chromatogram is a plot of detector response against
3.3 Detectors, are devices that indicate the presence of time or effluent volume. Idealized chromatograms obtained
eluted components in the carrier gas emerging from the with differential and integral detectors for an unretained
column. substance and one other component are shown in Fig. 1.
3.3.1 Differential Concentration Detectors, measure the in- 5.2 The definitions in this paragraph apply to chromato-
stantaneous proportion of eluted sample components in the grams obtained directly by means of differential detectors or by
carrier gas passing through the detector. differentiating the records obtained by means of integral
3.3.2 Differential Mass Detectors, measure the instanta- detectors. The Baseline is the portion of the chromatogram
neous rate of arrival of sample components at the detector. recording the detector response in the absence of solute or
3.3.3 Integral Detectors, measure the accumulated quantity solvent emerging from the column. A Peak is the portion of the
of sample component(s) reaching the detector. chromatogram recording the detector response while a single

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 E355 – 96 (2007)

FIG. 1 Typical Chromatogram.

component is eluted from the column. If two or more sample Gas holdup time = OA
components emerge together, they appear as a single peak. The Retention time = OB
Adjusted retention time = AB
Peak Base, CD in Fig. 1, is an interpolation of the baseline Partition (capacity) ratio = AB/OA
between the extremities of the peak. The area enclosed between Peak width at half height = HJ
the peak and the peak base, CHFEGJD in Fig. 1, is the Peak Peak width at base = KL
Number of theoretical plates = 16 (OB/KL)2 = v 5.54 (OB/HJ)2
Area. The dimension BE from the peak maximum to the peak Relative retention = (AB)j/(AB)i or (AB)i/(AB)s
base measured in the direction of detector response is the Peak Peak resolution = 2[~OB!j – ~OB!1 ]
=
Height. Retention dimensions parallel to the baseline are ~KL!i 1 ~KL!j

termed as the peak widths. The retention dimension of a line ~OB!j – ~OB!i
parallel to the peak base bisecting the peak height and ~KL!j

terminating at the inflexion points FG of the tangents drawn to

the inflection points (= 60.7 % of peak height) is the Peak Subscripts i, j, and s refer to any earlier peak, any later peak,
Width at Inflection Points, wi. The retention dimension of a line and a reference peak, respectively.
parallel to the peak base drawn to 50 % of the peak height and
terminating at the sides HJ of the peak is the Peak Width at 7. Presentation of Isothermal Retention Data
Half Height, wh. The retention dimension of the segment of the 7.1 Retention values should be reported in a form that can
peak base KL intercepted by the tangents drawn to the be applied for a specific stationary phase composition in
inflection points on both sides of the peak is the Peak Width at different apparatus and for different conditions of column
Base or Base Width, wb. length, diameter, and inlet and outlet pressures, and for
5.3 The following definitions apply to chromatograms ob- different carrier gases and flow rate. When the solid support is
tained with integral detectors, or by integration of the records inert, its particle-size range and distribution, and (within limits)
obtained by means of differential detectors. As sample compo- the amount and mode of deposition of the liquid phase, may be
nents pass through the detector the baseline is displaced varied also. While the solid support is commonly assumed to
cumulatively. The change in baseline position as a single be inert, often this is not so. The physical disposition of the
sample component is eluted is a Step. The difference between liquid phase may also affect retention values (1).2 Conse-
straight line extensions of the baselines on both sides of the quently, all components of the column packing and the
step, measured in the direction of detector response, is the Step procedure for combining them must be fully specified to enable
Height, NM. other workers to prepare identical compositions.
7.2 Retention in gas-liquid chromatography can be ex-
6. Retention Parameters pressed on an absolute basis in terms of the partition coefficient
6.1 Retention parameters are listed in Table 1. The interre- or specific retention volume of a substance (tacitly assuming an
lations shown apply only to gas elution chromatography
columns operated under constant conditions and for which the
partition coefficients are independent of concentration. Fig. 1 2
The boldface numbers in parentheses refer to the list of references at the end of
can be used to illustrate some of these parameters: this practice.

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 E355 – 96 (2007)
inert solid support). Relative retentions are more conveniently 7.3 Retention index is another retention parameter. It is
determined, however, and they should be expressed relative to defined relative to the retention of n-alkanes, and represents the
a substance which is easily available and emerges relatively number of carbon atoms, multiplied by 100, in a hypothetical
close to the substance of interest. n-alkane that would have an identical retention.

TABLE 1 Summary of Parameters, Symbols, Units, and Useful Relationships in Gas Chromatography

GC Parameter Symbol Unit Definition or Relation to Other Parameters

Absolute temperature of carrier gas T K °C + 273.15 at point where gas flow rate is measured
Absolute temperature of column Tc K
Absolute ambient temperature Ta K
Column inlet pressure pi Pa
Column outlet pressure Po Pa
Pressure drop along the column Dp Pa Dp = pi − po
Relative column pressure P P = pi/po
Ambient (atmospheric) pressure pa Pa
Partial pressure of water at ambient temperature pw Pa a value used in correcting the flow rate to dry-gas conditions if
measured with a soap-bubble flowmeter
Reference pressure pref Pa pressure at which the reference column flow (Fref) is expressed. An
example of a reference pressure is 101.325 kPa (1.000 atm).
Reference temperature Tref K temperature at which the reference column flow (Fref) is expressed. An
example of a reference temperature is 293.15 K (20°C).
Detector pressure pd Pa pressure in the detector.
Detector temperature Td K temperature in the detector.
Mobile-phase compressibility correction factor j
j 5 F G
3 P2 – 1
2 P3 – 1
Factor relating pressure drop and column permeability j’
j’ 5 F G
3 P2 1 2P 1 1
4 P2 1 P 1 1
Lūh
Dpj’ 5
Bo
Column length L cm
Column inside diameter dc cm
Column inside radius rc cm
Average diameter of solid particles inside column dp cm
Average liquid film thickness in open-tubular columns df cm
Interparticle porosity ´ fraction of column cross-section available for the mobile phase. For
packed columns, ´ < 1. For open-tubular columns, ´ = 1.0.
Weight of stationary phase in column WS g equal to WL in gas-liquid chromatography.
Density of stationary phase in column rS g/cm3 equal to rL in gas-liquid chromatography.
Volume of stationary phase in column VS cm3 at column temperature; equal to VL in gas-liquid chromatography
VS = WS/rS
Gas holdup volume VM cm3 VM = FCtM
Corrected gas holdup volume V°M cm3 V°M = FCtMj = jVM
Volume of mobile phase in the column (interstitial volume) VG cm3 In ideal case, assuming no extracolumn volume in the system:
VG = V°M = jVM
For open-tubular columns: VG = pL(rc − df)2
In actual systems:
VG = j[VM − ViP − VD]
where P is the relative pressure and j the pressure gradient correction
factor as defined earlier; V is the volume between the effective
injection point and the column inlet; VD is the volume between the
column outlet and the effective detection point; VM and V°M are
defined above.
Geometric column volume Vc cm3 pd2c L
Vc 5
4
Specific permeability of column Bo cm3 For packed columns:
dp 2 ´3
Bo 5 ·
180 ~1 2 ´!2
Po
Bo 5 2h´L 2 u
Pi – P o 2 o
For open-tubular columns:
dc 2 rc 2
Bo 5 5
32 8
Phase ratio of column b b = VG/VL
For open-tubular columns:
dc
b 5
4df
Gas flow rate from column F cm3/min measured at ambient temperature and pressure (with a wet flowmeter).
Gas flow rate from column corrected to dry gas conditions Fa cm3/min the value of F corrected to dry gas conditions.
Fa 5 F 1 – S Pw
Pa D
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 E355 – 96 (2007)

TABLE 1 Continued
GC Parameter Symbol Unit Definition or Relation to Other Parameters

Gas flow rate from column corrected to column temperature Fc cm3/min

Fc 5 Fa S DTc
Ta
Gas flow rate from column corrected to reference Fref cm3/min pa Tref
Fref 5 Fa
temperature and pressure pref Ta
the values of Tref and pref must be specified.

Gas flow rate from column corrected to detector temperature Fd cm3/min pa T d

Fd 5 Fa
and pressure pd Ta
the values of Td and pd must be specified.

4Fc
Linear gas velocity at column outlet uo cm/s uo 5
´dc 2p60
L
ū 5 uo j 5
60tM
Average linear gas velocity ū cm/s
Optimum average linear gas velocity in column uopt cm/s the value of ū at the minimum of the HETP versus ū plot
Viscosity of carrier gas h Pa·s expressed at column temperature
Retention time (total retention time) tR min time from sample injection to maximum concentration (peak height) of
eluted compound.
Gas holdup time tM min observed elution time of an unretained substance.
Adjusted retention time t8R min t8R = tR − tM
Corrected retention time t°R min t°R = jtR
Net retention time tN min tN = jt8R
Retention volume (total retention volume) VR cm3 VR = FctR
Adjusted retention volume V8R cm3 V8R = Fct8R
Corrected retention volume V°R cm3 V°R = jFctR = jVR
Net retention volume VN cm3 VN = FctN = jV8R
Specific retention volume Vg cm3 (net retention volume)/(g stationary phase), corrected to 0°C at effective
column pressure:
VN 273.15
Vg 5 •
WS Tc
Peak width at inflection points wi min retention dimension between the inflection points (representing 60.7 %
of peak height) of any single-solute peak.
Peak width at half-height wh min retention dimension between the front and rear sides of any single-
solute peak at 50 % of its maximum height.
Peak width at base wb min retention dimension between intersections of baseline with tangents to
the points of inflection on the front and rear sides of any single-solute
peak
Distribution constant (partition coefficient) Kc solute concentration in liquid phase, g/ml
Kc 5
solute concentration in mobile phase, g/ml
Wi~S!/VS
Kc 5
Wi ~M!/VM
V°R = VG + KcVS
Retention factor (capacity or partition ratio capacity factor, k K = bk
mass distribution ratio) k = t8R/tM

weight of compound in liquid phase

5
weight of compound in mobile phase
= K/b

Plate number N n = 16 (tR/wb)2 = 5.54 (tR/wh)2

Effective plate number
Plate height (height equivalent to one theoretical plate)
Neff
H cm
Neff 5 16 ~t8R /wb!2 5 5.54 ~t8R/wh!2 5 N
H = L/N
k
k 11 S D 2

Effective plate height (height equivalent to one effective Heff cm Heff = L/Neff
plate)
Peak resolution Rs 2~tR 2 2 tR 1! tR 2 – tR 1
Rs 5 >
wb 2 1 w b 1 wb 1
where tR2> tR1

Relative retention r r = t8Ri/t8R(st) = Ki/K(st) = ki/k(st)

Separation factor a a = t8R2/t8R1K2/K1 = k2/k1

The symbol r designates the retention of a peak relative to the peak of a
standard while the symbol a designates the relative retention of two
consecutive peaks. By agreement, tR2> tR1 and thus, a is always
larger than unity while r can be either larger or smaller than unity,
depending on the relative position of the standard peak.
Number of theoretical plates required for a given
resolution of peaks 1 and 2
Nreq
Nreq 5 16 Rs 2 S
a
a11 DS
2 k 1 1
2
k2
2 D

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 E355 – 96 (2007)

TABLE 1 Continued
GC Parameter Symbol Unit Definition or Relation to Other Parameters

Retention index (linear programmed temperature GC) IT

IT 5 100 F z 1 T
tTRi 2 tTRz
tR~z11! 2 tTRz G
T
where tR refers to the total retention times measured under temperature-
programmed conditions.
For definition of z, see above
Designations of subscripts a Ambient
c Column
eff Effective
f Film of liquid phase
i any solute
o outlet of column
p particle
st a standard or reference solute
G gas phase
L liquid phase
M mobile phase
N net
R retention
S stationary phase
1,2 two solutes from which solute 2 elutes later than solute 1
Designation of superscripts T temperature-programmed
8 adjusted
° corrected

REFERENCES

(1) Ettre, L. S., Pure and Appl. Chem. 65(4), 819–872 (1993). and Applied Chemistry, Vol 37, No. 4, 1974, pp. 447–462.
(2) “Recommendations on Nomenclature for Chromatography,” Pure

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