Journal of Chromatography A, 1216 (2009) 1607–1623

Contents lists available at ScienceDirect

Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Review

Retention models for programmed gas chromatography

G. Castello ∗ , P. Moretti, S. Vezzani
University of Genova, Dipartimento di Chimica e Chimica Industriale, Via Dodecaneso 31, Genova I-16146, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The models proposed by many authors for the prediction of retention times and temperatures, peak
Available online 25 November 2008 widths, retention indices and separation numbers in programmed temperature and pressure gas
chromatography by starting from preliminary measurements of the retention in isothermal and isobaric
Keywords: conditions are reviewed. Several articles showing the correlation between retention data and thermody-
Reviews namic parameters and the determination of the optimum programming rate are reported. The columns
Programmed temperature
of different polarity used for the experimental measurement and the main equations, mathematical
Programmed pressure
models and calculation procedures are listed. An empirical approach was used in the early models,
Mathematical models
Retention indices
followed by the application of thermodynamic considerations, iterative calculation procedures and
Retention times statistical methods, based on increased computing power now available. Multiple column arrangements,
Retention temperature simultaneous temperature and pressure programming, applications of two-dimensional and fast
Peak width chromatography are summarised.
Separation number © 2008 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1607
2. Prediction of programmed temperature retention times or retention temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1609
3. Prediction of programmed temperature retention indices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1613
4. Prediction of retention in multiple columns systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
4.1. Two-dimensional gas chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
5. Prediction of separation number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
6. Pressure and temperature programming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1618
6.1. Fast gas chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1620
7. Comments and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1620
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1621

1. Introduction chromothermography, which modifies temperature during the

analysis, a fixed temperature gradient is moved along the column,
Programmed temperature gas chromatography (PTGC) permits so that various points are at different temperatures and the motion
a faster elution of solutes than isothermal technique. When sepa- of the gradient furnace produces a motion of the solute bands. This
ration and identification of the components of a complex mixture technique is correlated with the work of Tumer [8] who described
cannot be obtained in isothermal conditions due to their extended the displacement of hydrocarbons from adsorption columns, which
boiling point range, temperature-programming is necessary, which was applied to chromatography [9,10] but remained a minor tech-
decreases the analysis time. In PTGC the temperature of the entire nique with respect of PTGC, which controls the change of the entire
column is changed with time in a manner according to the sep- column temperature during the analysis. PTGC improves, simpli-
aration to be effected. Griffiths et al. [1] first applied PTGC to fies or accelerates the separation of the components of the sample,
the elution of organic halides. Other workers reported apparatus as isothermal operation limits gas chromatographic analysis to
requirements and some applications [2–7]. In another technique, a narrow range of boiling points, because the early peaks may
emerge rapidly and can overlap while higher boiling compounds
emerge as flat and often immeasurable peaks. With temperature
programming, if a low initial temperature is used, the early peaks
are well resolved and the high boiling compounds eluted in a
∗ Corresponding author. Tel.: +39 010 353 6176; fax: +39 010 353 6190. shorter time as sharp peaks. The total analysis time is considerably
E-mail address: castello@chimica.unige.it (G. Castello). reduced.

0021-9673/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2008.11.049
1608 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
Some requirements must be met for programmed temperature
(PT) operation. The heated zones (injectors, columns, detectors)
should be well insulated and controlled by separate heaters,
because the detector temperature should remain as constant as
possible to avoid response changes and baseline drift. Reproducible
programming rates are essential for identification and quantitation.
All the available gas chromatographs offer now a wide choice
of temperature programming options: linear with many different
heating rates, linear initial and final isothermal tracts, multi-
linear programming with different heating slopes and intermediate
isothermal tracts. The programmer should offer a high degree of
precision and accuracy. The main problems are the uniformity of
temperature in the column oven, the reproducibility of the tem-
perature profile in repeated runs and the correct measurement of
the true temperature of the column. In the early applications of
temperature programming with packed columns, the vaporisation
of the liquid phase (column bleeding) caused noise and a shifting
baseline. Therefore, dual column gas chromatographs were used in
order to compensate the bleeding of a single column, because the
signal from the reference column was subtracted from that of the
matched analytical column and this procedure maintained a stable
baseline to high temperature. The introduction of thin-walled stain-
less steel capillary tubing with low heat capacity and high thermal
conductance enabled satisfactory applications of temperature pro-
gramming to very efficient columns [11] and the reduced amount
of stationary phase with respect of packed columns decreased the
baseline shift. The first metal capillary columns commercially avail-
able were unsuitable for temperature programming because of the
slow heat transfer to the inner layers of strict1y coiled tubing, which
was rewound with space between the layers for rapid air circulation
[12]. The fused silica columns now available, with low thermal mass
and spaced coils, easily follow the temperature change of the oven
atmosphere; the bonding of the liquid phase to the inner surface
of the silica column and the production of stationary phases with
very low bleeding avoid the necessity of dual column operation;
programmed runs with fast heating rate and to very high temper-
ature can be now carried out with single column instruments. The
residual baseline shift at high temperature can be compensated by
recording the baseline of a blank programmed temperature run and
subtracting it from the chromatogram of the sample analysed with
the same program.
When compounds of different polarities are present, whose par-
tition coefficients depend in a different way on temperature, any
change of temperature program rate may modify the elution order
and require a new identification. Many preliminary runs are there-
fore necessary in order to find the conditions that offer the best
resolution of closely eluting peaks. If some couples of peaks cannot
be resolved, another column of different polarity or greater length
has to be selected and the entire procedure repeated. Therefore,
calculation methods that can predict the retention times and the
resolution in different analytical conditions decrease the number
of preliminary runs. Many authors investigated this possibility and
proposed different procedures for the calculation and prediction of
retention data and optimisation of the column efficiency.
Dal Nogare and co-workers [4,6,13], McFadden [14], Stewart
[15], Habgood and co-workers [16–20] published the first the-
oretical investigations on the mechanism of PTGC, taking into
account the parameters that influence the resolution in packed
and capillary columns. A discussion of the plate height theory of
PTGC was made by Giddings [21] and a detailed survey of the
technique until 1966 was published in the book of Harris and Hab-
good [22]. From the early development of PTGC, many attempts
were made in order to correlate the retention times obtained in
isothermal runs with those found in programmed temperature
analysis and to predict retention times and retention tempera-
tures in any programmed run by starting from isothermal data. The
effect of inlet pressure on the reproducibility of retention times
and temperature which influence the accuracy of the prediction,
was also investigated [23–27]. Some authors studied the relation
between isothermal retention times, tR , and programmed temper-
ature retention times, tRT , and the possibility of predicting times,
peak widths and peak shape, and as a consequence to optimise the
resolution. Other researchers investigated the methods for the mea-
surement and prediction of the elution or retention temperature,
TR, under linear temperature programming [18,19,24–27], whereas
retention volumes were less used [19]. Works were published on
the correlation between retention index values in isothermal and
programmed temperature conditions. Also the prediction of sep-
aration numbers (Trennzahl, TZ) was investigated. Some books
on gas chromatography presented and discussed the programmed
temperature procedures or reported the various equations and rela-
tionships [28–32].
The control of the flow rate is also important for efficiency
and reproducibility of the analysis. At high temperature, gas vis-
cosity increases and under constant inlet pressure conditions the
flow rate decreases. If the carrier gas velocity falls below the min-
imum of the plot of height equivalent to theoretical plate (HEPT)
against velocity [33,34] a sharp decrease of the resolving power of
the column may be observed. Therefore, when constant flow con-
ditions are required, controllers must be used to compensate the
increased viscosity of the carrier gas by increasing the inlet pres-
sure. A detailed description of the effects of different flow control
systems (needle valves, constant head pressure, constant mass flow,
programmable head pressure, linear and multi-step pressure pro-
gramming) on the performance of packed and capillary columns
was published by Gonzalez et al. [35,36] and the influence of tem-
perature on gas hold-up time, on the thermal expansion of the
solid support and on retention times of polar and non-polar com-
pounds was examined. Different initial temperatures and linear
or multi-ramp programming rate were evaluated. The prediction
of an optimal heating rate was investigated by Giddings [37] and
by Snijders et al. [38,39] which examined the effect of single-
and multi-ramp temperature programming on the retention and
resolution of several compounds of different functionality on non-
polar polydimethylsiloxane columns with phase ratio, ˇ, ranging
between 153 and 470. Blumberg and co-workers [40–42] evalu-
ated the optimal heating rate at high pressure drop and compared
the performance of low-polarity columns with different phase
thickness (0.25 and 0.32 ␮m) in isothermal and programmed tem-
perature analysis of n-alkanes and pesticides with constant flow
and constant inlet pressure. They found that there is no signif-
icant difference between the speed-separation capability of the
column in either of the two pneumatic modes. In further theoretical
papers [43,44] Blumberg and Klee evaluated the effect of various
parameters on the resolution of solutes in static and dynamic gas
chromatography and defined some metrics describing√ the separa-
tion process in PTGC: separation power, P = N, where N is the
column plate number, separability, g, a measure of the solute
thermodynamic different with respect to a given column, specific
separation measure, s = S/P, the separation measure per unit of
separation power.
In this review on the calculation and prediction of data in
programmed gas chromatography, retention times and retention
temperatures, retention indices and separation numbers are
treated. A chronological approach is followed, except when the
same authors or research group published many papers in different
years on the same subject or when other authors applied a similar
procedure. When different retention parameters are investigated
in the same work, the discussion is included into one of the
sections according to the title or to the importance given by the
authors to each argument. In order to compare the equations taken
from various papers, some of the symbols used by the authors,
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
sometimes different for the same parameter, are replaced with
the IUPAC recommended symbols [31,45,46]. A description of the
procedures used for the prediction of retention data in pressure
programmed gas chromatography (PPGC) and temperature and
pressure programmed gas chromatography (PPTGC) is also made.
2. Prediction of programmed temperature retention times
or retention temperatures
The retention time of a substance in isothermal condition, tR , or
in PTGC, tRT , depends on the composition and polarity of the station-
ary phase, on its concentration in packed columns or layer thickness
in capillary columns and therefore on the phase ratio, on the col-
umn diameter and length, on the type, temperature, pressure and
flow rate of the carrier gas. The adjusted retention time, tR or t  TR ,
obtained by subtracting from tR or tRT the gas hold-up or void time,
tM , is better correlated with the solute-solvent interaction and with
the partition coefficient, but still depends on the parameters used
for the analysis. The determination or prediction of the retention
or elution temperature, TR , at which a given analyte emerges from
the column, is also a procedure that permits to investigate the PTGC
retention behaviour of a substance. The starting data for computer
calculation of tRT , t  TR or TR can be a set of isothermal analyses carried
out within the temperature range of expected programmed run, or
some PT separations are used to predict retention times for other
programming rates. In the first instance, the tRT are predicted by
summation of the data calculated for each compound from ther-
modynamic data, in the other, the analysis is divided into many
short time intervals within which the carrier gas velocity and the
retention factor are taken as constants, and the experimental data
of the preliminary analyses are used through iterative computation
procedure to obtain the sum of the distance travelled by the ana-
lyte in each segment. The total retention is equivalent to the sum
of the individual time segments corresponding to a migration dis-
tance equal to the column length. Both procedures were followed
by different authors.
Grant and Hollis [47] suggested a simplified method for the
prediction of linear tRT on non-polar packed, capillary and porous
layer open tubular (PLOT) columns, based on the observation that
aromatic hydrocarbons (naphtalene and some polyaromatic com-
pounds) show a linear relationship between PTGC retention time
and boiling point. They made some simplifying assumptions: the
hold-up time can be neglected, the mean carrier gas velocity u
remains constant during temperature program, no effect of tem-
perature on the entropy and entalpy terms, Hs /TB values constant
within the members of homologous series. With this simplified
treatment, it was found that for aromatic hydrocarbons the reten-
tion temperature TR in linear PTGC depends on the boiling point
TB , on the temperature gradient and on the ratio aL/ˇū, where a
is a constant for a given solute, L the column length, ˇ the col-
umn phase ratio, u the mean carrier gas velocity. Therefore the
molar entropy of solution and other data required to apply their
equation can be derived from plots of log tR vs 1/Tc measured at
two column temperatures Tc . The effect of the initial tempera-
ture is important and its optimum value is found when a linear
correlation exists between TR and TB . For this reason this proce-
dure was useful for simulated distillation of petroleum fractions.
Anders et al. [48] predicted on a capillary OV-1 column with dif-
ferent programming rates the tRT of the components of a gasoline
sample by using isothermally determined retention indices and the
temperature profile of the PT run. Bártů and co-workers [49–52]
proposed strategies for the prediction of tRT and the optimisation of
linear and multiple PTGC in order to separate pairs whose retention
time plots show intersecting elution functions. They used packed
columns filled with 10% Apiezon L and QF-1 and analysed mixtures
of chloroform, benzene, toluene and orto-xilene with programming
1609
rates from 2 to 20 ◦ C/min. The retention time of the nth compo-
nent can be determined from the sum of many short tracts through
an iterative procedure to obtain the distance travelled by the ana-
lyte. The peak width at the end of the column is correlated to the
actual width of the zone of the nth component; in isothermal con-
ditions, if the plate height is constant along the column, the actual
width is approximately proportional to the square root of the length
of the migration path; in PTGC, a zone width increment for the
nth component depending on time can be calculated. The differ-
ences between calculated and measured values are of the order of
few percent. The following equation, similar to that suggested by
Bártů [50] and consistent with that derived by Habgood and Harris
[16,20]:
 Tt  Tt
dT
r= = y(T ) dT (1)
T0
A + a exp [b/ (273 + T )] T0
where r is the temperature programming rate, T0 is the initial
temperature, A is the gas hold-time under isothermal conditions,
must be solved in order to obtain the Tt value. This integral
has no analytical solution and therefore some approximate inte-
gration methods must be applied. Said [53–55], in a theoretical
work on capillary PTGC, used curve-fitting techniques to replace
the inverse retention time function, y(T), by a function that can
be integrated. In the first method, a temperature T, lower than
the temperature Ti of the inflection point of the function y(T)
so that T = Ti − x, is considered. Another method iteratively cal-
culates the intermediate constant values. These procedures were
used and sometimes modified by other authors. Said’s equations
were used by Gerbino et al. [56–59] for the prediction of PTGC
retention times of all the chlorobenzenes and some bromoben-
zenes on mega- and narrow-bore capillary columns coated with
DB-5 and DB-WAX, separated or connected in series. The same
authors applied Said’s method to the prediction of the elution tem-
perature of fifteen polyciclic aromatic hydrocarbons on a narrow
bore DB-5 column [60]. A comparison of the two Said’s methods
with the trapezoid method, linear, step and quadratic interpo-
lation and with the Simpson method [61–64] was published by
Castello et al. [65,66] and the minimum number of preliminary
isothermal runs necessary for the prediction of the tRT values of
n-alkanes, chloro- and nitro-benzenes on SPB-1, DB-1, Supelcowax-
10, DB-WAX and on a carbon layer open tubular (CLOT) column
partially deactivated with polyethylene glycol was evaluated. In
the majority of cases only three isothermal runs must be car-
ried out. A substantial equivalence of the tested methods was
found, notwithstanding the differences in retention and the inver-
sion of the elution order when columns of different polarity were
used. Multi-linear temperature programming was also investigated
[67] and the tRT of chlorobenzenes, chloroanilines, naphtalene and
chloronitrobenzenes predicted on SPB-1 and SPB-octyl capillary
columns. The total tRT is the sum of the retention times of the
compound during the initial isothermal tract, in the PT tracts at
one or more temperature gradients and in the final upper isother-
mal tract, and it is therefore necessary to calculate the position of
every compound in the column and the pressure existing at that
point when the programming mode changes. The influence of the
uncertainty of the various analytical parameters (column length
and diameter, inlet and outlet pressure, initial and final temper-
ature, gradient of the run) on the accuracy of the prediction was
investigated.
Dose [68] estimated on DB-17 and DB-210 columns of different
diameter and phase thickness the tRT of organochlorine pesticides
and nitroaromatic compounds in any temperature program applied
to the same analytical conditions (stationary phase and carrier gas)
at which were determined for the ith analyte the partition ratio ˇi ,
the hold-up time tM , the entropy and entalpy of vaporisation Sv,i
1610 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
and Hv,i . The thermodynamic parameters were assumed to be
temperature independent for relatively narrow temperature ranges
and the agreement between estimated and experimental reten-
tion times was generally within 1%. A more complicated procedure
was used for the estimation of the peak widths, and the agree-
ment obtained was 10–15%. The same author proposed to use Sv,i
and Hv,i as thermodynamic retention indices representing each
of the analysed compound in an abstract planar coordinate system
where Sv,i values lie along one axis and Hv,i along the other. The
position of an analyte in the thermodynamic abstract plane yields
structural information, which can be improved by measuring the
thermodynamic constants on stationary phases of different polarity
and setting the analyte’s position in a multi-dimensional abstract
hyperspace. In a further paper [69], a simplex boundary-handling
algorithm was described, which correlates the initial temperature
and the heating rate and can compare the possibility of different
phases to effect a given separation at the optimum temperature
program and optimise the column geometry and carrier flow rate,
systematically searching for the best compromise between reso-
lution and run time. A chromatographic response function (CRF)
and its subclass time/resolution response function (TRRF) are intro-
duced:
 transfer effects avoiding the theoretical plates theory. The pas-
TRRF = tR,n /tR,crit + e−Rij /Rcrit
i=
/ j
where tR,n is the retention time of the last peak, tR,crit is a user-
selected time-cost weighting or compromise factor, Rcrit is a user-
selected resolution target value, Rij is the resolution between peaks
i and j having widths at half height whi and whj respectively:
tR,ij
Rij =
2(whi + whj )
Both analysis time and resolution are incorporated in the CRF
and all the possible peak-to-peak interactions are included. Sanz
et al. [70] predicted and optimised the separation of mixtures
of common components of alcoholic beverages flavours (alco-
hols, aldehydes, lactones, esters) on micropacked columns filled
with OV-1, Superox-20 M, SP-2310 and with mixtures of OV-1 and
Superox 20 M. They, assuming that the carrier gas behaves in the
column as an ideal gas and for columns having the same perme-
ability and length, used simple equations to correlate the hold-up
time tM , the retention time tR , the capacity factor k and the peak
width ah half height wh :
ln tM = ln At + Bt ln T
k = Ak T exp(Bk /T )
wh = atR + b
In PTGC, both gas velocity and capacity factor are continuously
changing when temperature is varied, but in a short enough time
interval the models used in isothermal conditions are valid and the
velocity of a band after travelling a short length z of the column can
be deducted from Darcy’s law. The following equation
−1
(Jp /L)dz = [tM (1 + k)] dt
where
1/2
Jp = j[1 + ((Pi /Po )2 − 1)(1 − z/L)]
can be integrated between column inlet and outlet:
 L  tR
−1
(Jp /L)dz = [tM (1 + k)] dt
0 0
and solved by a numerical procedure. It was confirmed with
approximation good enough that, according to Habgood and co-
workers [16,22] the wh of a compound in PTGC is similar to the
value obtained in isothermal runs carried out at the retention tem-
perature. The values of the constants At , Bt , Ak , Bk , a and b were
obtained for eight selected solutes on three stationary phases and
the experimental and calculated retention times and peak width
values were in good agreement for mixed phases too.
The problem mentioned in Section 1 about the correspondence
between the oven and the column temperature was examined by
Shrotri et al. [71], which applied a calculation method based on a
partial differential equation relating these two temperature, solved
with Bessel function, to the prediction of tRT of some alcohols in
four packed gas-solid (Porapak Q) and gas–liquid (Carbowax 20 M
and TEPA) columns. Two different methods were compared and
the average errors, ranging from 1.3 to 13%, estimated. Akporhonor
et al. [72] predicted on an HP-ultra 2 column the tRT and TR of
18 compounds (n-alkanes, phenones and 1-phenyl-alkanes) at all
combinations of four initial temperatures and eight programming
rates. The errors of tRT ranged between 1 and 52 s, and those of
TR between 0.02 and 3 K. Wernekenschnieder et al. [73] applied
the Monte Carlo calculation procedure to the simulation of the
chromatographic process and the prediction of isothermal and
PTGC retention times and peak widths on the basis of the prob-
abilistic renewal theory of Scott and Fritz [74], focused on mass
(2)
sage of a single molecule through the column is considered as a
series of steps of random length and random time between the
mobile and the stationary phase. Each step is independent from
the previous ones and the process is therefore “renewed”. The total
retention time is the sum of the waiting time in the stationary
phase and of the travelling time in the carrier gas. A simple equa-
tion for calculating the temperature dependence of the capacity
factor:
(3)
k(T ) = exp(+HV /RT + c2 ) (10)
shows that when the vaporisation entalpy is known (e.g. tabulated
for many compounds) and the constant c2 is determined by an
isothermal calibration measurement at the initial temperature, the
method can be applied for any arbitrary temperature. Snyder and
co-workers [75–78] used the linear elution strength (LES) approx-
imation, similar to the linear solvent strength (LLS) procedure of
gradient liquid chromatography [79] for predicting with a computer
program the retention, peak width and resolution of many differ-
ent Supelco test mixtures, vegetal oil samples, gasolines and mixed
samples of alkanes, alcohols, esters and nitro- and chloro-benzenes
(4) in isothermal and linear or segmented PT runs on a non-polar
(5) (SPB-1), a slightly polar (DB-5) and a polar (Nukol) column. Only
two PTGC preliminary runs were used for the determination of the
(6) dependence of sample retention on temperature, avoiding many
time-consuming isothermal runs. An average plate number was
measured from one isothermal run, and this value was assumed
to be valid for all solutes and experimental conditions, isother-
mal or PT runs, in computer simulations. The band spacing change
as a function of temperature and the inversion of elution order
was investigated. Many applications of the computer procedure are
(7) illustrated, and resolution maps are applied to the optimisation of
the analysis of complex samples, which require multi-ramp tem-
perature programs. Snow et al. [80] applied the method proposed
(8) by Curvers et al. [81,82] to the numerical simulation of the tRT of
alkanes and aromatic hydrocarbons in multiple-segment tempera-
ture programming of a DB-1 column. The overall percent deviation
for all runs was 2.8%. Cavalli et al. [83] used a simple equation for
(9) the prediction of tRT from isothermal data: the column is divided
in a succession of short elements that can be considered under
isothermal conditions during a short time interval; the precision
of calculation depends on the gas hold-up time, on the number of
elements and on the logarithm of the temperature gradient. In a
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623 1611

further paper [84], the validity of the procedure used by dividing conditions. The following equation of peak motion in programmed
theoretically the column into short slices was experimentally con- pressure and temperature GC (PPTGC) was used:
firmed by shortening the used column (Spirawax 50 m × 0.32 mm)
cutting off lengths of 1–2 m at a time and repeating the initial pro- dz L
=  (13)
grammed run. It was necessary to adjust the gas-hold time that was dT f (T )Q (z, t)tM (T )[1 + k(T )]
found to depend linearly on the column length, and a linear corre-
where z is the axial position of the peak in the column, T is the
lation was also found between calculated and observed retention
absolute temperature, L the length of the column, f  (T) is the
times.
first derivative of the relationship between time and temperature,
Snijders et al. [38] predicted the retention times and peak widths
T = f(t), that describes the used temperature program. Taking into
in isothermal, linear and multi-linear PT analyses on a non-polar
account the previous works of Dal Nogare and Langlois [13] and of
HP-1 column, extracting entalpy and entropy terms from isother-
Snijders et al. [38] the validity of the following equation in PPTGC
mal retention indices at two temperatures, when the adjusted
was investigated.
retention times of two n-alkanes at the same temperatures are
known. The process is divided in segments corresponding to very  TR
dT
small time intervals, within which the retention factor and the gas 1= (14)
f (T )tM (T )[1 + k(T )]
velocity can be assumed to be constant; if the temperature of a T0
given segment is known on the basis of the selected programming
rate, the tRT is calculated with a numerical iterative method. The vis- It was found that the equation of peak motion Eq. (13) becomes
cosity and the compressibility of the mobile phase had to be taken an exact equation when z = L and that Eq. (14) is applicable only if the
into account and were calculated according to Hawkes [85] and integration is performed along the whole domain of z. In a further
James and Martin [86] respectively. The peak widths are calculated paper [91], the inversion phenomena in PTGC were examined. The
dividing again the process into short time segments and using the coelution temperature TCe of a couple of solutes x and y is expressed
Golay equation [14] which correlates the theoretical plate height, in terms of thermodynamic constants and calculated with
H, to the diffusion of the solutes in the gas and stationary phase,
(Hy − Hx )
being the corresponding coefficients indicated with Dg and Ds TCe = 

(15)
respectively:
 2

2Dg (1 + 6k + 11k2 )r 2 2kdf
H= + 2
+ 2
ū
ū 24Dg (1 + k) 3Ds (1 + k)
where k is the retention factor, r is the internal radius of the column,
u is the mean velocity of the carrier gas in the column, df is the thick-
ness of the stationary phase layer and Dg is the average value of the
diffusion coefficient in the gas phase along the column. A simpli-
fication is made by estimating that the Ds is directly proportional
to Dg . By taking into account the mobile phase compressibility and
the expansion of the solute band due to pressure decrease along the
column, the chromatographic band broadening is given by

n 2
 2 (1 + kn )
t =
x=1 L,x
u2n
where kn and un are the retention factor and the mobile phase veloc-
ity in the last segment. The peak width at half height or at the base
can be obtained from the relationships wh = 2.354  t and wb = 4  t
respectively. In a further paper [39] the same authors described
the off-line optimisation of PTGC analyses, adopting the CRF used
by Dose [69] and shown in Eqs. (2) and (3). The modified simplex
method (MSM) by Nelder and Mead [87] was used for computa-
tion and the optimum resolution between sixteen compounds of
different functionality was found. Comparison of simulated and
experimental chromatograms shows that linear and multi-ramp
PTGC separation can be optimised off-line with a minimum of pre-
liminary experimental work.
Hawkes [88] published a method for extrapolating tRT and TR val-
ues in a given PTGC analysis starting from tabulated data obtained
in different programming conditions when the temperature gra-
dient, the mass of the stationary phase and the flow-rate of the
carrier gas are known; the calculation of IT from I values was also
described [89]. Gonzalez and Nardillo [35,36,90,91] in their papers
on the aspects of flow control in PTGC and PPGC, evaluated the effect
of different settings of the pressure control devices on the gas hold-
up time tM and on the methods for the prediction of retention times
in packed and capillary columns of different polarity (AT-1 and Car-
bowax 20 M). They used the Curvers equation [81,82] and discussed
other equations for the determination of tM in the various analytical
Sy Sx
R R
− ln ˇ − R
− ln ˇ
(11) As the TCe is unique for each pair of crossing analytes, the separa-
tion of all crossing couples of a mixture will evolve differently when
a pressure–temperature program is applied and no simple solution
can be found to the problem of peaks coelution and inversion in
programmed GC.
Krupčik and co-workers [92–96] predicted from Kováts reten-
tion indices the TR of hydrocarbons and substituted phenols on
OV-1 and OV-1701 columns. A sequential simplex optimisation of
initial temperature, hold-up time and temperature programming
rate permits to obtain the retention times and the areas of partially
overlapping gaussian peaks. The dependence of carrier gas pres-
sure on the column under PTGC conditions with a second-order
(12) non-linear partial differential equation was calculated and this pro-
cedure was used for the prediction of retention times, comparing
the results with those obtained assuming a constant pressure pro-
file along the column. Significant differences between the values
obtained with the two methods were found when very long cap-
illary columns (more than 50 m) of small internal diameter (less
than 0.3 mm) are used at high temperature programming rate. Guil-
laume and Guinchard [97] used a simplex process for optimising
the separation of four psoralenes on a DB-1 column both in isother-
mal and PTGC conditions. They found that many initial data were
necessary in order to obtain acceptable correlation between experi-
mental and calculated values of tRT . Chen et al. [98] proposed for the
prediction of tRT of n-alkanes, ketones, alcohols, substituted ben-
zenes and ethers in temperature and inlet pressure programmed
GC a method differing from the previous systems based on Curvers’
approach. In this instance the columns, OV-101 and Carbowax 20 M,
are divided in many segments of equal length and the velocity of a
solute moving in the column under temperature or pressure pro-
grammed conditions is evaluated. According to Darcy equation, it
is given by
dc2 ∂p (x, t)
u(x, t) = − (16)
32(T (t)) ∂x
where dc is the diameter of the column, (T(t)) is the viscosity of
the carrier gas at temperature T(t) and p (x, t) is the carrier pressure
at position x along the column at the time t. The following equation
1612 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
is obtained:
dt
Hi S d
− + Ri
= (1 + e RT (t) /ˇ) = ti∗ (, t)
d i dt
where  = L/x, i.e. the fraction of x found in the length of the
column L (its values always varies from zero to one), ti∗ (, t) is the
retention time of solute i when it moves through the whole col-
umn with its velocity at time t and position . As the variables 
and t cannot be separated in Eq. (17), it cannot be transformed to
an equation expressed with a simple definite integral. In order to
solve the equation, the range of  (and therefore the column) is
divided into n segments and the relative distance of a segment h to
whole column length is computed with h = 1/n for all solutes. The
tk,i of solute i when the band moves through the kth segment of the
column is given by

k−1
1
tk,j = ti∗ (j , tj,i )
n
j=0
being i = j/n + 1/n with k = 1, 2, . . ., n − 1 [83]. The method
can be accurately applied to linear and multi-ramp temperature-
programmed runs, but its application to pressure programming
leads to large errors, because column efficiency is seriously affected
by the carrier gas velocity.
Kittiratanapiboon et al. [99] used a modification of the method
based on the division of the column in many short tracts [84] and the
Krisnangkura equation [100] for the calculation of equivalent chain
length (ECL) of fatty acid methyl esters (FAMEs) for the prediction
of tRT and as an aid in the identification of natural fatty acids, as pre-
viously done by Krupčic and Bohov on SP-2340 [101]. An empirical
approach for the estimation of ECL of natural FAMEs in multi-step
PTGC analysis on an SA-WAX column was reported by Lomsugarit et
al. [102]. Kavanagh et al. [103] estimated the tRT on a HPU-1 capillary
column of the members of homologous series (C4 -C15 n-alkanes
and C11-C20 saturated methyl esters) by taking into account the
slight curvature of the plot of tR as a function of z. Blumberg and
co-workers [40,41] compared the peak capacity in constant flow
(isorheic) and constant inlet pressure (isobaric) PTGC runs of HP-5
columns with different phase layer thickness (0.25 and 0.32 ␮m).
Starting from the Darcy’s and Golay’s equations the authors found
that the optimum flow rate is given by
3Dm dc po
T
−1 basicity; a and b, hydrogen-bond acidity. The capital letters are
Fopt =  c
8pr Tr
where dc is the internal diameter of the column, po the outlet pres-
sure, pr and Tr the reference pressure (1 atm) and temperature of
the flow rate measurement, Tc the column temperature, Dm the dif-
fusion coefficient of a solute in the carrier gas. The optimal pressure
for isobaric mode was higher than the initial pressure in constant
flow mode, but no appreciable difference was found in the perfor-
mance of the capillary column. The choice of the preferred mode
may depend on other considerations, e.g. the preference of some
detectors for constant flow-rate. In a further work [42], it was found
that the optimum normalised heating rate that leads to an adequate
separation of a required number of solutes in the shortest time,
r = tM RT , where tM is the hold-up time or void time in min and RT
is the programming rate in ◦ C min−1 , is about 10 ◦ C per void time
when the pressure drop is high. The same authors [43] studied the
elution parameters in PTGC comparing different ways to express
the relationship between the velocity of migration of a solute and
that of the carrier gas (retention factor, solute mobility factor, solute
interaction level) and [44] compared the performance of isothermal
and PT analysis by using the separation measure, S, that repre-
sents the number of non-overlapping ␴-wide subintervals within
an arbitrary ta − tb interval of the chromatogram and evaluates the
separation of two peaks regardless of their shape and distance:
 tb
(17) S= dt/ (20)
ta
They concluded that an isothermal analysis can separate in a
complex sample more peaks than a single-ramp PT run carried out
on the same column, but with a prohibitive increase of the analysis
time; if a longer column is used for PTGC, the separation of isother-
mal run can be recovered and the analysis speed greatly increased.
Zhang and co-workers [104] proposed the use of a wavelet neural
network (WNN) to predict from density and isothermal retention
indices the programmed temperature retention values of branched
chain hydrocarbons in naphthas on a HP-PONA column designed
for the analysis of petroleum products. As the results obtained by
application of the integral Curvers formula [81,82] improved by
Guan et al. [105] by studying the separation of many hydrocar-
(18) bons on capillary columns (Squalane, OV-1, SE-54) with different
lengths, diameters and film thickness were not good enough for
the identification of hydrocarbons in the petrochemical industry,
the authors tried to apply the WNN to predict the tRT values. Other
calculation procedures, the artificial neural network (ANN) and
the Simpson integral method, were tested. The best results from
the points of view of the accuracy and of the convergence speed
were obtained with the WNN procedure. No previous application
of this method to the prediction of PTGC retention values was
found.
Nawas et al. [106] applied to PTGC the solvation parameter
model (SPM) previously used by Poole and co-workers [107–110]
for investigating in isothermal conditions the retention mechanism
and the selectivity in the separation of many compounds on packed
and capillary columns with stationary phases of different polarity:
DB-1701, DB-210, DB-225, EC-Wax, Carbowax 20 M and DB-FFAP.
The retention factor k describes the retention with the sum of dif-
ferent contributions:
log k = c + lL + eE + sS + aA + bB (21)
where c is the model constant depending on phase ratio, and the
other lower case letters are constants representing the station-
ary phase contributions to intermolecular interaction and cavity
formation: l, interaction with n- or ␲-electrons of the solute;
e, contribution from dipole-type interactions; s, hydrogen-bond
(19)
solute descriptors for the interactions with the stationary phases:
L, gas-liquid distribution constant of hexadecane at 298 K; E, excess
molar refraction; S, capacity of the solute to stabilise a neighbour-
ing dipole; A, solute’s effective hydrogen-bond acidity; B, solute’s
effective hydrogen-bond basicity. By studying the behaviour of 52
compounds on DB-1701, DB-210 and EC-WAX capillary columns,
the values of the system constants were obtained and used for pre-
dicting the tRT of compounds not included within those used for
the construction of the model, with errors ranging from 0.15 to
0.89 min. It was concluded that for isothermal analysis the SPM
is consistent with the thermodynamic theory of solute gas-liquid
transfer, and that its application in PTGC for predicting tRT from
structure is possible for compounds whose descriptors are known
or can be generated by computer procedures, but it was also found
that the method was not sufficiently accurate for selectivity opti-
misation of difficult mixtures, probably due to descriptors quality
and mixed retention mechanisms. The behaviour of mixed-phase
columns was also investigated [111]. Aldaeus et al. [112] applied
computer simulation to the prediction of tRT of n-alkanes and pol-
yaromatic hydrocarbons on DB-1, DB-5 and DB-17 columns in
programmed runs by starting from isothermal analyses. As pre-
viously considered by other authors, the method is based on the
hypothesis that in a short time interval t an analyte moves along
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
the column for a tract z; when the sum of the z is equal to the
column length, the tRT is found. The G is considered to depend
on temperature as a function of the heat capacity difference, Cp ,
which is assumed to be constant across the temperature range used.
3. Prediction of programmed temperature retention indices
In isothermal analysis the use of retention times relative to a
reference compound permits to compare chromatograms carried
out with different column length and carrier gas flow-rate, but this
method cannot be applied when programmed temperature anal-
yses are compared. The use of the retention volumes, VR and VR ,
and of their ratio does not solve the problem as the influence of the
variation of carrier gas flow-rate is eliminated, but the other param-
eters still influence the results. Again, only isothermal analyses can
be used as the source of data. The retention index with respect of the
homologous series of n-alkanes, I, proposed by Kováts in 1958 [113],
is an useful tool for the comparison of retention data obtained by
various authors in different conditions as it is nearly independent
on many of the parameters of the gas chromatographic analysis. It
is an aid for the preliminary identification or confirmation of sub-
stances and is also used for the characterisation of liquid phases
[114–116]. As the components of an homologous series are eluted
in isothermal conditions with retention times increasing exponen-
tially, the plot of the logarithm of the retention values follows a
straight line as a function of the number of carbon atoms, z. Accurate
measurements have shown that this linearity is not rigorously fol-
lowed and a slight curvature is observed [117–119]. However, when
the range of z values is small, the straight line correlation can be
accepted. The fundamental Kováts equation for the retention index
of a solute i is
st.ph. log Xi − log Xz
Ii (T ) = 100 + 100z
log X(z+1) − log Xz
where I is the isothermal retention index at temperature T; i the
compound of interest; st.ph. the stationary phase; z and z + 1 are n-
alkanes with consecutive carbon atoms numbers; X the retention
value (adjusted retention time t R or volume V R ) used in the calcu-
lation. The thermodynamic meaning of I, i.e. its correlation with the
partial molar free energy of solution is expressed by the equation
[120,121]:
Gi − Gz ı Gi−z
Ii = 100 + 100z = 100 + 100z
Gz+1 − Gz G(CH2 )
where G are the Gibbs energy differences in the solvation of solute
i and of reference n-alkanes z and z + 1, the subscripts have the same
significance as in Eq. (22) and ı denotes the difference between the
given properties of two substances.
The retention indices of the n-alkanes used as reference com-
pounds are by definition taken as equal to 100 z for any stationary
phase and at any column temperature. Mathematical interpola-
tion of the straight line whose slope and intercept are obtained
by applying least-squares procedures to the retention values or to
the G of the n-alkanes is also used for calculation of I, but the
strict application of Eq. (22) decreases the effect of the curvature
of these values as a function of z, that can be considered negligi-
ble within two or three contiguous terms of the homologous series.
In order to solve the problem of the non-linearity of the n-alkanes
retention with respect of the number of carbon atoms, Zenkevich et
al. [122–125] performed a linear logaritmic interpolation between
n-alkanes with z and z + k carbon atoms and proposed the “gen-
eralized retention index”, GIx that, for a solute x with an adjusted
retention time t Rx is:
  ) − (t  + q log t  )
(tRx + q log tRx Rz Rz
GIx = 100z + 100k    + q log t  )
(tRz+k + q log tRz+k ) − (tRz Rz
1613
where q is
 + (n − n )t  − (n − n )t 
(n2 − n1 )tR1 3 2 R3 3 1 R2
q= (25)
 t )
log(t  2R2 /tR1
R3
being n1 , n2 and n3 the number of carbon atoms of three n-alkanes
1,2 and 3 eluting under the same experimental conditions. Wang
and Sun [126,127] proposed a regression equation
I = a0 + a1 ln Y + a2 Y B (26)
where a0 , a1 , a2 and B are constants and Y is the retention parameter
used (t R or Vg ), and modified the expression for GIx :
(q ln Yx + YxB ) − (q ln Yz + YzB )
GIx = 100n + 100 B ) − (q ln Y + Y B )
(27)
(q ln Yz+1 + Yz+1 z z
where B has a value greater than unity and q is calculated with Eq.
(25).
Korány et al. [128,129] analysed many compounds (alkanes, ter-
penes, spices and fragrance constituents) on a polar Supelcowax-10
column and, by substituting the saturated vapour phase tension
of n-alkanes in the expression of the specific retention volume,
Vg , found that the retention of the members of the homologous
series follows an exponential dependence on z in isothermal, and
a near linear dependence in linear PTGC runs. An accurate cali-
bration procedure was followed, by injecting reference mixtures
daily, at the beginning and at the end of work, and checking the
repeatability of the obtained retention indices. An extremely high
day-to-day stability of the results was observed, and the gradual
change of retention indices values during a long period of time
(10–12 months) depending on the ageing of the column evalu-
ated. Homologous reference series different from n-alkanes were
proposed for the determination of the retention indices of some
(22)
types of compounds or when specific detectors as the electron cap-
ture detector are used. A review on the alternative to n-alkanes as
calibration standards was published by Castello [130]. In order to
avoid the reference to standard homologous series, Harangi [131]
and Ettre [132] introduced and investigated the concept of virtual
carbon number: when the retention indices of some well identified
compounds enclosed in the sample are known, they can be used
as reference instead of the n-alkanes, without adding them to the
sample. The system works very well in isothermal analysis carried
out at the same temperature at which the I values of the reference
(23)
compounds were measured, but shows some disadvantages when
in other isothermal or PT runs the indices change.
A drawback of the Kováts isothermal retention index is related to
its dependence on the temperature of the column, as the adjusted
retention times (or volumes) are related to temperature T by the
equation:
log t  R(T ) = a + b/T (28)
It was found that he retention index values change with chang-
ing temperature following an Antoine-type equation [115] and
therefore in an hyperbolic way, but it has been demonstrated
[133–135] that in the temperature interval used in practice the
index values follow a near linear relationship and therefore can be
obtained by extrapolation [136,137] or with the application of more
complex empirical calibration and comparison methods [138,139]
to the values that can be found in many published tables of retention
values [140–152]. The knowledge of the temperature dependence of
the net retention volume [153] and the calculation of a temperature
coefficient permit to apply the values obtained at one temperature
to analyses carried out at another but, as the temperature depen-
dence of the index is hyperbolic, the error in values obtained by
(24) linear extrapolations may be high. Grigor’eva et al. [154,155] dis-
cussed the inequality of temperature increments of n-alkanes as the
1614 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623

cause for the non linear behaviour of retention values and proposed Kováts Eq. (22) and its modifications cannot be used in PTGC
an equation: analysis, as reported and discussed by Sun et al. in their review
[167], notwithstanding some attempts were made to extend its use
T
Ipr = a + btR + c ln tR + d/tR (29)
by Chen et al. [168] and Jennings et al. [142]. Guiochon [169] sug-
derived from Wang and Sun’s Eq. (26) [126,127,156] where Ipr T = gested an equation based on the elution temperature, as it exists
100z is the retention index of an n-alkanes in PTGC and tR is its an approximate linear relationship between elution temperature
adjusted retention time. To determine the IT of any compound, the of n-alkanes and their carbon number. According to Van den Dool
four parameters a, b, c, d, are calculated by the least-squares method and Kratz [170,171] the PTGC retention index of a compound s, Is T ,
T and the experimental t  of n-alkanes on a SE-30 col-
using the Ipr is calculated with the formula:
R
umn. This procedure permits to calculate the retention indices by tRT (s) − tRT (z) TR (s) − TR (z)
taking into account the non-linear variation of the retention param- IsT = 100 + 100z = + 100z (39)
tR (z + n) − tRT (z)
T TR (z + n) − TR (z)
eters of the n-alkanes. Golovnya et al. [157] used a modification of
Eq. (29) for the calculation of IT of alkanols on SE-30 and on a polar where n is the difference in carbon number of the two n-alkanes
PEG-40M+ Na3 PO4 . In the equation, the adjusted retention times taken as references, tRT are the PTGC retention times of compound
were replaced with the retention factors k and the coefficients cal- s and of the alkanes and TR denotes retention temperatures. This
culated with the least-squares method using the t and k values formula is used when linear temperature programs are carried out,
found experimentally. as for single ramp PTGC the TR values can be replaced by the cor-
Tudor et al. [158–164] analysed C6-C26 n-alkanes and 345 com- responding programmed temperature retention times. In theory,
pounds of various polarities on SE-30 and Carbowax 20 M columns, the formula is strictly valid when and “ideal” temperature program
evaluated many equations for the temperature dependence of I and is selected, i.e. when the retention times of the n-alkanes (and not
considered the thermodynamic meaning of the hyperbolic Antoine their logarithms) behave linearly as a function of the carbon number
equation and of two linear approximates: z, and the difference between the retention times of two adjacent
B B homologues is the same in the whole programmed analysis. The
I =A+ =A+ (30) retention times tRT and not the adjusted t  TR are used in the formula:
t+C T + C
this may be an advantage because the measurement or calcula-
I = a + bt = a + bT (31) tion of the dead time is not necessary; however, when capillary
I = ˛ + ˇ/T (32) columns with carrier gas hold-up times great with respect of the
retention of the first eluted peaks are used or multi-linear tem-
whose parameters depend on the entalpy and entropy of solution perature programming is set, this simplified approach may lead to
at the transfer of a mole of solute between its standard states in the large errors. Golovnya and Uraletz [172] demonstrated that the non-
mobile and in the stationary phase: linear behaviour of the retention of n-alkanes in PTGC depends on
100 the considerable differences in temperature increments of sorp-
A= S
(SiS − SzS ) + 100z (33) tion parameters and investigated the influence of the gas hold-up
SCH
2 time on the initial temperature and programmed rate [173,174].
S
HCH They suggested the use of a non linear equation for extrapolation
100
B = 100 2
2
(SiS − SzS ) − S
(HiS − HzS ) (34) and interpolation calculations of retention indices, which shows
S )
(SCH SCH
2 2 some advantages in comparison with the Van den Dool and Kratz’s
S S method, mainly when some members of the n-alkanes series are
HCH HCH
C = 2
C = 273.15 − 2
(35) missing. Janssens [175] determined the retention indices in PTGC by
S
SCH S
SCH linear interpolation with respect of even carbon number n-alkanes.
2 2
Halang et al. [176] compared a method based on natural cubic spline
The thermodynamic meaning of the parameters, the contribu- interpolation with the polygonal technique and calculated the IT
tion of the methylene group to the standard free energy, entalpy by starting from tR values. They found that the cubic spline pro-
and entropy of solution were evaluated, and the correlation of the cedure yields values more accurate than the polygonal method.
retention indices with the partial molar free energy of solution Eq. Erdey et al. [177] suggested a modified Antoine-type equation for
(23) and the energetic equivalence of the index unit: the calculation of retention indices in linear PTGC:
S
GCH 2.3B log[(TR + C)/(T0 + C)]
S
Gi.u = 2
(36) IT = A + (40)
100 TR − T0
according to the definition of other authors [165,166] were exam- where TR and is T0 are the retention temperature and the initial
ined. A series of equation was developed which describes from temperature in K, respectively, and the constants A, B and C can be
a thermodynamic point of view the parameters of Eqs. (30)–(32) determined from experimental retention index of benzene mea-
in relation to the stationary phase dependent factors. Görgényi sured on many packed columns of various polarities. Robinson et al.
et al. [121] correlated the temperature dependence of the Kováts [178] compared the retention indices calculated in isothermal runs
retention index to a entropy index, I(S), based on solvation entropy and in non-linear PTGC and proposed the concept of “average tem-
instead of the free energy of solvation of a given compound s com- perature of elution” to correlate the IT values obtained in non-linear
pared with that of two n-alkanes with z and z + 1 carbon atoms: PTGC and those found from plots of I against temperature. Majlát et
Ss − Sz al. [179] described how to calculate retention indices when the tem-
Is (S) = 100 + 100z (37) perature program consists of isothermal and linearly programmed
Sz+1 − Sz
tracts and a constant mass flow-rate of the carrier gas is maintained.
where the temperature dependence of the standard free energy Lee and Taylor [180] found a relationship between isothermal and
difference at a given temperature is PTGC retention indices which indicates that on non-polar stationary
  phases the IT of non-polar compounds will correspond to an isother-
∂ G/∂T = −S (38)
P mal I measured with the column temperature at the harmonic mean
The temperature dependence of the retention index will be pos- of injection and elution temperatures. Zhu [181] proposed a method
itive if I > I(S), negative if I < I(S), zero if I = I(S). suitable for constant inlet pressure analyses on capillary columns
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623 1615

operated with complex temperature programmes. Podmaniczky
et al. [182–185] measured retention data in isothermal conditions
and, by using the capacity ratio obtained at various temperatures
and those calculated under programmed temperature conditions,
established linear relationships between the carbon number of
homologous series and thermodynamic characteristics, that were
used for the calculation of retention indices in linear PTGC.
Curvers et al. [81,82] calculated the IT from isothermal data and
proposed the following equation:
 polation correlating the retention temperatures of n-alkanes and
TR
n-alkanes, characteristics of each column. It was found that the
entropy and entalpy terms depend on the film thickness or phase
ratio, and the IT values were calculated from those of S, H, ˛
and ˇ. Further application of the same procedure [192] permitted
to calculate retention times and indices in multi-step PTGC runs
with an accuracy better than 1%.
Messadi et al. [193] compared the PTGC retention indices of
some plasticisers on a packed OV-17 column calculated with
Kováts equation with those predicted with a cubic spline inter-
   
r= dT /tM (T ) 1 + a/ˇ exp(H/RT )
T0
where a = exp(S/R) and H/R are the entropic end entalpic param-
eters, r is the programming rate, tM (T) is the hold-up time function.
This equation was further used by several authors for the prediction
of programmed retention values. Chen and co-workers [168,186]
calculated the PTGC retention indices of 31 compounds on an HP-1
column with the Kováts equation for isothermal analyses, by replac-
ing the isothermal adjusted retention times of the formula with
corrected values which take into account the average retention
temperatures in PTGC. In a further paper [187], a linear correlation
between temperature and retention index was described:
T − T1
I T = I1T +
A + BT
which permits to calculate the IT at any temperature T if its value I1T
at a reference temperature T1 is known, and if the two constants A
and B are determined from experimental data and from the linear
dependence of the tR on temperature. With the proposed method
the retention indices at any temperature can be calculated from
retention data measured at two temperature-programming rates.
Krupčik et al. [92] calculated the IT from I, through the prediction
of the retention temperatures of n-alkanes and other compounds
and their temperature coefficients. This procedure allows to use
published Kováts retention indices or values at other temperatures
deducted from tabulated data for a preliminary indication of the
nature of an analyte, whose identity must be confirmed by the
simultaneous use of different specific detectors or by GC-MS tech-
nique and comparison with authentic samples. The indices were
also used for the calculation of TR in PTGC [93,94] and for the opti-
misation of the separation of hydrocarbons on a system of three
columns by using chemometric multivariate analysis [95].
Akporhonor et al. [72,188,189] and Al Bajjari et al. [190,191] used
the following equation, obtained by modifying the Curvers equation
Eq. (41),
 TR
 
1= dt/tM (T ) 1 + k1 exp [k2 /(T0 + k3 t)]
0
where tM (T) is the hold-up time function, T0 is the column tem-
perature at injection, and k1 = ˇ exp(S/R) is the entropic term,
k2 = −H/R is the entalpic term, k3 is the programming heating
rate, ˇ = VL /VM is the phase volume ratio for the calculation of PTGC
characteristics (retention times, retention temperatures, retention
indices, peak widths [190], peak asymmetries, resolution [191] and
two kinds of equivalent temperatures, that are the temperatures of
the isothermal run for which retention times and indices are the
same as calculated PTGC values. Different procedures were tested
and the accuracy of the results evaluated. Guan et al. [105] proposed
an interactive retention index database for preliminary identifica-
tion or confirmation of compounds in PTGC and calculated the IT
from Kováts isothermal I values on capillary columns of low or
medium polarity by using Curvers equation for the prediction of
the PTGC retention times or temperatures. The procedure employs
Kováts indices which represent the properties of a given station-
ary phase for each component, and the tR or the capacity ratio of
(41) their carbon number; this method does not require the presence of
consecutive normal alkanes and yields constant values for different
programming rates. Also the values of the solution thermodynamic
constants, Hv0 and A, were quite constant throughout the temper-
ature range between 100 and 300 ◦ C. In further papers [194,195]
the retention indices on a capillary OV-101 column have been
determined by linear and polynomial interpolations by taking into
account the temperature dependence of carrier gas viscosity. It was
found that retention indices may differ by as much as 26 units
depending on the method of calculation. Other mathematical mod-
els (Bezier functions and from 2 to 6 order B-splines) were used by
Lourici et al. [196,197] for the calculation of IT of phtalates on a SE-30
packed column.
A comparison of various calculation methods of PTGC reten-
(42)
tion indices was published by García Domínguez et al. [198,199],
which measured the retention of C6 –C12 n-alkanes and of the ten
Mc Reynolds’ probes on packed OV-105, PS-255; di-n-decil phtalate
and OV-275 columns and compared the equations of Giddings [37],
Habgood et al. [16], Grant et al. [47], Curvers et al. [81], Guiochon
[169], Lee et al. [180]. Golovnya et al. [172], Erdey et al. [177], Halang
et al. [201]. Zenkevich et al. [122,123], Podmaniczky et al. [182],
Wang et al. [126] and Chen et al. [168,186]. They concluded that
Kováts method is incorrect if applied to PTGC data, whereas the Van
den Dool and Kratz equation is the surest method but is influenced
by the curvature of the plot with high TR solutes. The most reliable
of the tested methods was found to be the cubic interpolation. Fur-
ther, García Domínguez et al. [200] calculated the IT values on the
same columns used previously of McReynolds’ probes and acetone,
cyclopentanone, toluene, ethyl acetate, n-octanol and dimethylani-
line with a cubic spline interpolation. Seven different equations
were examined: Giddings [37], Said [54], Akporhonor et al. [72],
Curvers et al. [81], Guiochon [169], Lee and Taylor [180], Halang
et al. [176] and Krupčik et al. [201]. The interpolation was carried
out by using retention temperatures, TR , experimentally measured
or calculated by using three of the above mentioned equations:
Curvers and Akporhonor (direct equations) or Krupčik (through the
dependence of I on T). Twelve isothermal runs and seventeen dif-
(43) ferent programmed runs were used, and it was found that the best
methods for the prediction of retention temperatures in PTGC are
the Curvers and Krupčik equations; the Akporhonor and Said equa-
tions follow with larger errors, but the largest errors result with
the empirical equations of Giddings, Guiochon and Lee and Tay-
lor. When cubic spline retention indices are compared, the Curvers
equation is better that the other two compared.
Baaliouamer et al. [202] used a local Lagrange interpolation for
the calculation of IT values on an OV-101 column and compared
the results with those obtained with Kováts and Van den Dool
equations. Bemgård et al. [203] related the PTGC retention indices
of polynuclear aromatic hydrocarbons with calculated molecular
properties. They used five descriptors (first-order valence molecu-
lar connectivity, ionisation potential, length, height and quadrupole
moment); 70 compounds were analysed on a XTI-5 capillary col-
umn, and an average error smaller than 6 index units was found
between experimental and calculated indices. Gerbino and Castello
[56,58,204] used the method of Said [53–55] for the prediction of
the tRT and the IT of chlorobenzenes and substituted phenols on
1616 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
narrow and wide bore capillary columns DB-1 and DB-WAX. Errors
ranging from 0.05% and 0.15% between experimental and predicted
values were observed. Girard [205], for the calculation of PTGC
retention indices suggested modelling Kováts proportionality con-
stants (or slopes), K, of the plots of isothermal retention index as a
function of log t’R . He analysed on a SPB-1 and on a Supelcowax-10
column mixtures of C7 –C22 n-alkanes and found that K values were
related in a curvilinear fashion with temperature. The following
correlation between IT and K was tested:
I T = a1 + K ln(tR − a2 )
with the substitution forms
logarithmic-linear (LTKC) ln K = b0 + b2 T, K = b1 + eb2 /T
logarithmic-inverse (ATKC) ln K = b0 + b2 /T, K = b1 eb2 /T
linear-quadratic (QTKC) K = b1 + b2 T + b3 T 2
b3
linear-exponential (ETKC) K = b1 + b2 T
where a1 , a2 , b0 , b1 , b2 and b3 are constants. Eq. (46) corresponds
to the Arrhenius equation with
b2 = −Ea /R
being Ea the energy of activation, R the gas constant and b1 the
Arrhenius factor. Also the model developed by Wang and Sun
[126] and the cubic spline functions were tested on retention data
obtained with three column headpressures and three flow-rates on
the polar and on the non-polar column. It was found that the QTKC
model and the cubic spline functions are comparable and provide
the most accurate results, being the QTKC model simpler to apply
than splines. Eveleigh et al. [206] used Curvers equation for the pre-
diction of retention indices of monoterpenes analysed on capillary
columns of different length, diameter and phase thickness coated
with polydimethylsiloxane phases BP-1 and HP-1. The differences
between experimental and predicted values ranged from 0.06 to 4
units of Van den Dool and Kratz index. Didauoni et al. [207] tested
a multiparametric least-squares regression iterative method using
the adjusted retention times and a cubic interpolation using the
uncorrected retention times for the calculation of retention indices
at high temperature (200–260 ◦ C). Tóth et al. [208] described a
correction for the retention times on a DB-1 column of reference
alkanes which improves the reproducibility of the retention indices
in PTGC when the n-alkanes cannot be mixed with the sample due
to interference with the analytes and their retention times must
be determined with separate injections.
Takács [209] proposed an unified system for the prediction of
retention data in GC, that can be used for the calculation of retention
values at any column temperature by starting from data measured
at another temperature on the same stationary phase, or can con-
vert the data at standard column temperature from one phase to
another. A computer program was described that allows to cal-
culate retention times and indices in the range 60–130 ◦ C for 400
stationary phases, non-polar columns as the hypothetical Zerolane,
Squalane and OV-101 being used as fundamental phases for precal-
culation, using quantities as the retention polarity (RP), the relative
volatility (Q), the Kováts coefficient (K), the retention volume (Vg ) of
selected alkanes, the molecular structural coefficient (Sc ). The aver-
age standard specific polarity factor (APF) obtained by the sum of
the first five McReynolds constants, and the effective polarity of the
stationary phase (Pc ) can also be calculated. Except for few phases,
the difference between calculated and measured retention indices
is smaller than 0.2%. Hennig et al. [210], Héberger et al. [211,212],
Kovalska et al. [213,214] reported that in some chromatographic
systems, when polar analytes are chromatographed on non polar
stationary phases, the dependence of I on temperature is no more
linear but show a minimum, that can be calculated by the use of
the equation
I = A + B/Tc + C ln Tc (50)
that also permits to evaluate the activation enthalpy and the chem-
ical potential of partitioning of one methylene group between the
two phases of the gas chromatographic system.
Whereas the majority of workers investigated the possibility of
predicting PTGC retention indices from isothermal retention data,
(44)
Chen et al. [168,187] calculated isothermal I values at various tem-
peratures and their temperature coefficients from the results of
PTGC retention data, investigating the relationship between the
(45)
average retention temperature of the solute and its adjusted PTGC
retention time, taking into account the flow velocity and evaluat-
ing how the solute moves through the column by the sum of its
(46) behaviour at various times and positions. Linear and step tem-
perature programs were used. Also the retention times in PTGC
(47) conditions were predicted. Chen et al. [98,215] described an inte-
gration procedure for the prediction of retention values of alcohols,
(48)
ketones and substituted benzenes from data determined under
PTGC conditions on OV-1, OV-101 and PEG 20 M columns. Also
Bautz et al. [75,76] used the data of two PT runs for the predic-
tion of isothermal runs. Santiuste [216] obtained the IT values from
(49)
isothermal data measured on packed columns of different polarity
(OV-105, PS-255 and OV-275) by interpolating the retention tem-
peratures calculated with Curvers method and obtained deviations
of about 2%. Again, Santiuste et al. [217] proposed a procedure for
the calculation of isotherm I values from the results of a linear PTGC
analysis on OV-1, OV-101, HP-5, SE-30 and SE-54 columns, with a
deviation between experimental and predicted values lower than
1.5 index units. They also expressed Van den Dool-Kratz’s IT as a
function of the volatility of the solute and of reference n-alkanes,
defined a PTGC “volatility” retention index based on the ratio of the
retention times or specific retention volumes between the solute
and a n-alkane or between two consecutive n-alkanes, compared
the results of this new index with the equations of Van den Dool
and Kratz, Golovnya and Uraletz [172] and with the Antoine’s inte-
grated equation of Erdey [177] and proposed a calculation program
based on an “equivalent temperature” method that facilitates the
use of the Sadtler retention index library [144]. Zhao et al. [218] used
topological descriptors for the conversion of IT in different sets of
conditions on the same column, between columns with different
polarities (DB-5, HP-5, DB-35) and between different initial tem-
peratures of the programmed runs. The errors were of few retention
index units.
Some reviews of papers on the retention indices in temperature-
programmed gas chromatography were published previously. In
1993 Sun et al. [167] reviewed previous articles on the Van den
Dool and Kratz equation, the generalised retention index (GIx ) by
Zenkevich and Ioffe [123] and the methods of Wang and Sun [126],
Messadi et al. [194], Podmaniczy et al. [182], Halang et al. [176].
In the discussion of the extended Kováts retention index methods,
so-called because their equations are similar to that of the isother-
mal I, they reported the methods of Chen et al. [168], Jennings et al.
[142] and the equations of Majlat et al. [179] and Zhu [181] for the
calculation of the net retention volume VN when this parameter is
used in the Kováts equation. Also the methods of Janssen [175] and
the relative elution temperature of Watts and Kekwick [219] were
cited. The comparison of retention index definitions and the meth-
ods suggested for converting retention values from isothermal data
to PTGC and from a set of PT conditions to another were reviewed.
A list of existing databases on retention data was given. Examining
the reproducibility and transferability of IT values and the studies
of Weber [220], Knoeppel et al. [221], Wang et al. [156] and Yin et
al. [222]. The authors concluded that they can be reproduced only
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
if all the numerous parameters involved are rigorously reproduced
or are clearly specified in the databases.
In 1999 Gonzalez and Nardillo [120], in their review, discussed
the “retention index approach” of those works based on empirical or
semi-empirical parameters that permits to compare experimental
results obtained by various researchers, as the formulas of Kováts,
Van den Dool and Kratz, and the non linear index expressions, with
the “thermodynamic approach” of works which intend to apply
basic thermodynamic data for predicting the IT in various analyt-
ical conditions. In the first approach, they compared the different
equations proposed for the calculation of IT , investigated the fac-
tors that influence its accuracy, reproducibility and elution order
and stated, according to Curvers et al. [81], that the direct con-
version from isothermal to programmed temperature indices is
not feasible due to the influence of the gas hold-up time function.
The thermodynamic approach was widely discussed and various
aspects were considered: peak motion equation and its solution,
fluid dynamic functions, thermodynamic functions. The authors
observed, according to Vezzani et al. [67], that the main source of
errors in the prediction of tRT is not the used theoretical approach
but the discrepancy between the values of the analytical parame-
ters used for the calculations and the true experimental conditions
(pressure, flow rate, temperature, programming rate, length and
diameter of the capillary and thickness of the phase layer). They
found that some method proposed for the prediction of reten-
tion from thermodynamic data yield an excellent agreement to the
experimental values but, considering the physical and thermody-
namic meaning of isothermal and programmed retention indices,
concluded that any empirical correlation of IT as a function of ther-
modynamic parameters or structural factors is only valid in the
specific conditions in which it is determined. The problem of the
correct calculation and prediction of PTGC retention indices is still
matter of study. because of its importance for the prediction of
retention in different temperature programmed analysis.
4. Prediction of retention in multiple columns systems
The majority of authors investigated the possibility of predict-
ing the retention times, retention temperatures, retention indices
in PTGC using single columns, and many of them compared
the behaviour of stationary phases of different polarity. In some
instances, mixed liquid phase or serially connected columns were
used and this solution, with the control of the inlet pressure and
of the temperature programming rate, increased the possibility of
optimising the resolution of closely eluting compounds. Sanz et
al. [70] and Molera et al. [223] investigated the performance of
mixed stationary phases in PTGC. Krupčik, Hevesi et al. [224–227]
described computer procedures for the optimisation of the separa-
tion of multi-component samples on two or three coupled columns
of different polarity (SE-30, SE-52, Nukol). Multivariate analysis
was used for optimising the separation of many linear, branched
and aromatic hydrocarbons. Gerbino et al. [58,59] used mega- and
narrow-bore capillary columns of polydimethylsiloxane and 20 M
polyglycol, separated or connected in series. Wright et al. [228]
using an equation similar to that proposed by Curvers in his thermo-
dynamic approach to the prediction of retention indices, calculated
the tRT obtained with temperature-programmed serially linked cap-
illary columns coated with DB-1 and DB-524. The procedure is valid
in conditions of constant inlet and outlet pressure and linear pro-
grams initiated upon injection. Bakeas et al. [229] used a BP-1and
a Al2 O3 /Na2 SO4 PLOT column connected in series for the determi-
nation of TZ and HETP.
4.1. Two-dimensional gas chromatography
A special application of multiple column systems is the com-
prehensive two-dimensional gas chromatography (GC × GC), a
1617
powerful analytical technique for very complex samples. In con-
ventional or one-dimensional capillary GC, one hundred or more
peaks can be separated in one run. When much more analytes
have to be separated, one way to improve the separation is to
couple two independent columns through an interface. The first
applications of multidimensional GC (MDGC) used the hearth cut-
ting procedure [230,231] but a limitation of this technique is that
few fractions eluting from the first column are sent for further
separation to the second column, in order to resolve some impor-
tant tracts of the first chromatogram where interfering peaks are
present. As the complete screening of the entire sample with MDGC
is time-consuming, the comprehensive approach of GC × GC has to
be used, and all the eluate of the first column (first-dimension) is
cut in small fractions subjected to further analysis on the second-
dimension (2D) column. If the second column is much shorter and
narrower than the first one, the total 2D separation can be com-
pleted within the total time of the first-dimension run and the
resolution is improved with respect of the MDGC technique in a
shorter time. Different combinations of columns were tested, with
the same (one oven) or different temperature programming (two
ovens configuration). The first column used in many works is a non-
polar one, a boiling-point separation is obtained in the temperature
programmed first-dimension, and the second-dimension separa-
tion, which is fast and essentially isothermal, depends on specific
interactions and on the choice of the polar phase selected. Reversed
(polar-non polar) configurations also yielded good resolution of
very complex samples. The interface between the two columns
(modulator) traps, focalises and releases the fractions eluted from
the first column, and this is generally accomplished by cooling with
cryogenic gases (CO2 or N2 ). A detailed description of the GC × GC
technique is out of the scope of the present review, but many excel-
lent reviews with hundreds of literature references were published
on instrumental set-up, modulation and detection methods, data
processing, software and chemometric procedures, application to
many samples as petrochemicals, halogenated compounds, fats
and oils, flavours and essential oils, beverages and other complex
mixtures [232–239]. Comparison of one-dimensional and GC × GC
separations [240] and description of computer models to predict
and optimise separation [241] were published recently. An article
on solvation parameter model of GC × GC separation is enclosed
in the special issue of Journal of Chromatography A on retention
mechanisms in gas chromatography [242].
5. Prediction of separation number
As seen above, the prediction of retention values in PTGC can
be carried out by using as the input data the retention measured
in isothermal runs. However, information on the efficiency of the
column can only be obtained by predicting if the widths of closely
eluting peaks is small enough to permit complete or almost suffi-
cient resolution and establish if the column is operated in a region
of reasonably good efficiency. In isothermal conditions, the vari-
ation of separation efficiency due to modified carrier gas velocity
[201,243–246] is indicated by the change of plate height, H. In order
to optimise the column performance in isothermal analysis, the
plate height should be measured at different values of tempera-
tures and carrier gas velocity; the conditions corresponding to the
lowest value of the minimum of the Van Deemter plot [33] should
be selected. In PTGC, the theoretical plates measurement or predic-
tion cannot describe the separation efficiency. If the determination
of the plate height is done applying classical methods [15,31,247] to
the retention time and to the peak width obtained in PTGC, unrea-
sonably high plate number is found because these values are no
more strictly correlated as in isothermal conditions. Habgood and
Harris [17] suggested to employ for the calculation of the plate num-
ber in programmed temperature analysis the gas volume equivalent
1618 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
to the base line intercept of the peaks obtained in the programmed
run and the retention volume that would be found in isothermal
elution at the retention temperature of every compound. The exper-
imental determination of these data increases the time necessary
to know the column efficiency and the results are questionable as,
by definition, the theoretical plate concept is valid for isothermal
operation only [31].
The column separation efficiency in PTGC can be evaluated by
using instead of the plate number the peak capacity, that is the
number of peaks that can be separated in a given segment of the
chromatogram between two main peaks selected as reference. The
separation number SN (or TZ “Trennzahl” in its original German
name) first introduced by Turkeltaub and Zuchowitsky in 1954
[248] and subsequently endorsed by Kaiser [249], is obtained by
using as the reference the retention time and the peak width at
half height of two consecutive members of the n-alkanes homol-
ogous series, and gives the number of peaks that can be resolved
between the reference peaks, with a 4.7 resolution between two
consecutive peaks:
tRb − tRa
TZ = −1
wha + whb
where tR are the retention times of two consecutive homologues
and wh the corresponding peak width at half height. This method
of evaluating the column efficiency is valid in programmed tem-
perature conditions too and more replicable than the plate number
[250], Rooney et al. related TZ to the relative retention ˛ and to the
effective plate number Neff [251]:
˛ − 1 1/2
TZ = 0.452 N −1
˛ + 1 eff
Jones et al. [252–255] studied the effect of the starting tem-
perature and of laminar and turbulent flow in PTGC on resolution
and column efficiency and found an inverse relationship between
H and TZ. They also found that isobaric flow rate, that decreases
with increasing column temperature [256,257], provides higher
efficiency than constant flow. The optimum flow rate can be deter-
mined by calculating the TZ slope as a function of the flow and
temperature programming rate, by finding the maximum value on
the inverse Van Deemter plot or by interpolating the TZ values
obtained at various flow-rates for two pairs of homologues, one
of low molecular weight and one of high molecular weight. The
correlation between TZ and the plate height was studied by Bakeas
et al. [229] in a system of two capillary columns, a polydimethyl-
siloxane and a gas solid PLOT Al2 O3 /Na2 SO4 , connected in series
under PTGC in isobaric conditions. The inverse TZ/H relationship
was confirmed and it was found that the TZ depends on the pressure
at the connection between the columns and on the initial tempera-
ture, whereas the plate height depends on the temperature program
rate. The prediction of the TZ in isothermal and programmed tem-
perature analysis on polar (CP-Wax 52), medium polarity (Zebron
50) and non-polar (CP-Sil 5) columns with various initial temper-
atures, carrier gas pressure and heating rate was made by Vezzani
et al. starting from the retention times and peak width measured
in preliminary isothermal and isobaric runs [258]. The following
equation was used in order to predict the peak width at half height,
wh(pr,cal) :
t
2  T 
∗ R(pr,cal) R(pr,cal)
wh(pr,cal) = w
t∗ Ti
where t* R(iso,cal) and w* h(iso,cal) are the retention time and peak
width at half height predicted in isothermal conditions at the initial
temperature, Ti , of the programmed-temperature run [38]; tR(pr,cal)
and TR(pr,cal) are the predicted retention time and retention tem-
perature of the given compound. This procedure is valid only if the
initial temperature of the programmed runs and the elution tem-
perature of the heaviest compounds are within the temperature
range of the preliminary isothermal calibration runs. The values
obtained can be used for the calculation of the separation number
in different tracts of the chromatogram and permit to select the car-
rier gas inlet pressure and the temperature programming rate that
offer the best resolution of the analysed mixture.
6. Pressure and temperature programming
In many cases, almost the same effects of the PTGC can be
achieved by programming the flow-rate of the carrier gas increas-
ing the inlet pressure of the column stepwise or linearly. During
this operation, the temperature of the column may either be kept
constant or the two methods can be combined and both the temper-
ature and the flow-rate programmed during the analysis (PPTGC).
Advantages and disadvantages of this technique were discussed
[259–261]. Pressure programming shortens the analysis time for
wide molecular mass range mixtures while permitting the opera-
tions of the column at a lower temperature. The stationary phase
(51) bleeding is significantly less, as it increases exponentially with tem-
perature while only linearly with flow rate, and the low temperature
decreases the possibility of decomposition of thermally unstable
samples. Since the height of a peak is related to the flow rate, broad
peaks which would emerge later will be much sharper allowing
for better detection of small concentration. In practical analysis
the flow rates are almost always higher than the optimum value
corresponding to the minimum of the Van Deemter plot but the
conditions can be adjusted so that the flow rate at the critical sep-
arations (usually in the earlier part of the chromatogram) is low,
(52)
close to the optimum; it is increased successively and thus the over-
all analysis time will still be equal to or shorter than that of the run
with constant flow rate.
The first application of PPGC was proposed in the 1959 when
Lipsky et al. [262], and at the same time Wolff [263,264] applied a
step programming of the carrier gas inlet pressure to reduce separa-
tion time in the analysis of fatty acid esters. Valussi et al. [265,266]
demonstrated the advantage of increasing the carrier gas inlet pres-
sure during the analysis of natural fatty acid samples and reported
results obtained by using linearly programmed carrier gas flow
rate. Morgantini [267] described a device which permitted the lin-
ear programming of the carrier gas flow rate and discussed some
theoretical aspects of the technique. In 1962 Purnell published a
survey on the advancement of this technique [268], stated that
results equivalent in many respects to those of temperature pro-
gramming could be obtained and observed that, if a reasonably
efficient column having a broad minimum of plots of HETP vs. car-
rier gas velocity were employed, flow changes of up to an order
of magnitude might be employed without much loss of efficiency.
Scott [269,270], Vergnaud [271,272], Costa Neto et al. [273,274],
Clarke [275], Mázor et al. [276–281] reported various theoretical
and practical aspects of the technique.
In 1964–1965 some commercial pressure programming units
became available, but this technique was partly abandoned because
of the impossibility of monitoring exactly the flow-rate change. A
review of the papers available up to the year 1968 was published by
Ettre et al. [259]. The influence of the James and Martin compress-
ibility factor [282] was investigated by Takács et al. [283] in PTGC,
in PPGC and in PPTGC; whereas the values of j in this instance is
(53) sometimes taken as the arithmetical mean of its values at the begin-
ning and at the end of the analysis, this procedure is not correct
theoretically and the authors described the method for the exact
determination of j in programmed runs. A method to calculate the
retention times of the solute in linear PPGC by evaluating the time
necessary to travel every small tract of the column in stationary flow
by using the time obtained in the previous tract was suggested by
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623 1619

Devallez et al. [284]. Nygren [285] reported a method for exponen- tions of isothermal, isobaric, linear and step increase of temperature
tially programming the flow rate and found that with this method and pressure, by using only few isobaric and isothermal reference
the chromatograms were very similar to those obtained with linear runs. The calculation of peak width also permitted the number of
temperature programming. In 1984 Wičar [286,287] used a digital theoretical plates, the separation efficiency and the chromatogram
controller suitable for flow-rate programming and studied the flow profile very close to experimental ones to be predicted [297,302].
continuity equation and its consequence in PTGC. Dodo et al. [288] The effect of variations of the experimental parameters (inlet and
described a flow rate optimisation system for use with temperature outlet pressure, initial temperature and programming rate, column
programming. Today many instruments equipped with electronic diameter) with respect of the preset values on the accuracy of the
pressure controller are able to control and measure with precision retention times and peak widths prediction was evaluated [299]. It
the change of pressure in the column during the analysis and permit was found that uncertainty of inlet pressure and of programming
to obtain good reproducibility [289]. rate has the main effect on the accuracy of the predicted retention
The prediction of retention data in order to optimise the flow- times (up to 1,6%), whereas the effect of all the tested parameters
rate and the pressure-temperature programming in PPGC using on the peak width at half height ranged between 0.03 and 0.05 s.
separation numbers (TZ) was described by Jones et al. [252–255] A modification of the Golay equation [34] permits to calculate the
which proposed a Van Deemter-type relationship for determin- plate height Hj in a short tract of the column of length Lj :
ing the optimum set of conditions. They found that under PTGC
2
at constant flow-rate, the retention temperature of each solute 2Dg (1 + 6k (Pj ) + 11k (Pj )2 )r 2 2k (Pj )df
is obtained by multiplying its retention time by the temperature Hj = + 2
ucg,j + u
2 cg,j
ucg,j 24Dg (1 + k (Pj )) 3Ds (1 + k (Pj ))
programming rate and adding the result to the starting tempera- (54)
ture. A similar approach can be applied to pressure programming
in isothermal conditions: the existing head pressure at the time where Dg and Ds are terms correlated to the diffusion coefficients
the solute elutes can be calculated from the sum of the initial in the gas and stationary phases respectively; df is the thickness of
pressure and the product of retention time and of the pressure the stationary phase layer and r is the internal radius of the column;
programming rate. Relationships between TZ and the pressure and ucg,j is the carrier gas linear velocity, k the capacity factor and Pj the
temperature programming rates were found for laminar and tur- pressure in the Lj interval. It was found [303] that the simplifying
bulent flow and the optimum initial flow-rate calculated. Wu [290] hypothesis made by Snjiders et al. [38] and further accepted by
compared a differential equation for GC simulation in any pres- other authors by estimating that the Ds is directly proportional to
sure and temperature programming condition with an integration Dg must be modified. In fact, whereas Dg correctly represents the
equation valid in constant pressure mode and concluded that under diffusion coefficient in the gas phase, Ds seems to be a complex
the usual GC conditions the difference between the two models parameters, that depends on diffusion coefficient in the stationary
is very small, whereas appreciable difference could be obtained in phase and on other phenomena as partition and mass transfer and
low temperature and rapid pressure changes. Gonzalez and Nardillo changes as a function of pressure and temperature. When the Dg
[35,36,90,91] studied the effect of different systems of flow control and Ds values have been obtained, the following sum permits to
in linear and multi-step PTGC with linear pressure programming calculate the plate number:
and the inversions of the elution order due to pressure changes. The
equation of peak motion in PPTGC is shown above, Eq. (13), and the 
n

n
Lj
conclusions of the authors summarised in the section reporting the N= Nj = (55)
Hj
prediction of retention times. Chen et al. [98] divided the column in j=1 j=1
many equal segments and evaluated the velocity of the carrier gas
in the column under temperature or pressure programmed condi- where n is the number of the short tracts of length Lj in which
tions. Nahir et al. [291,292] investigated pressure and temperature the column has been divided and where the number of theoretical
programming when the column outlet is at ambient pressure and plates, Nj , and the corresponding plate height, Hj , have been cal-
when it is in near-vacuum conditions as in GC-mass spectrome- culated. Eq. (49) can be applied in any pressure and temperature
try coupling. By starting from classical Poiseuille’s equations for condition and it is possible to predict through an iterative calcu-
the flow rate, the dead time in near vacuum outlet condition was lation procedure the number of theoretical plates for any isobaric
obtained, It was found that the hold-up time, important param- run. Eq. (54) can be summarised as
eter for the calculation of capacity factors and retention indices,
A
can be maintained constant in PTGC by compensating for viscosity Hj = + Bucg,j (56)
effects through adjustment of the inlet pressure. Nahir [293,294] ucg,j
also studied the effect of nonsteady-state flow when the inlet pres-
Other equations proposed in the literature have been applied
sure is subjected to fast changes. The prediction of the equivalent
to the prediction of programmed pressure analyses [299]. The first
chain lengths (ECL) of fatty acids methyl esters in different temper-
(Golay–Guiochon equation) can be summarised as follows [304]:
ature and pressure programs was carried out by Mjøs [295], using
the data obtained on a BPX-70 column with three initial tempera- A
tures, temperature gradients and column flow rate. The ECL were Hj = + Bucg,j + Cucg,j 2 (57)
ucg,j
calculated from the experimental data using polynomial regression.
With principal component analysis score plots were obtained that The terms A and B are the same as in Eq. (56) and C is
permit to establish the position of the double bonds in the fatty
acids chain. Moretti et al. [296] and Vezzani et al. [261,297–301] t 2
C= 2
(58)
published a series of papers on the prediction of retention times, (1 + k (P)) L
peak width and resolution in PPGC with linear gradient and with
initial and/or final isobaric tract on DB-1, DB-17, CP-WAX 52 and where  t is the dispersion describing the extra-column band broad-
Supelcowax-10 columns whose true diameters were checked by ening. The second (Van Deemter equation) is [305]
scanning electron microscopy (SEM) and found to differ up to 9%
from the nominal values. The methods predicted retention times in A
Hj = + Bucg,j + E (59)
programmed pressure isothermal and in many different combina- ucg,j
1620 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
where E is the eddy diffusion term. A third equation, also derived
as a modification of the Golay equation, has been used:
 
A uo
Hj = + Bucg,j
ucg,j ucg,j
where uo is the velocity of the carrier gas in any point of the column
if the analysis is carried in isobaric conditions at a pressure identical
to the initial value of the gradient run. The prediction of retention
times in temperature and pressure programmed analysis was also
made [299,300].
6.1. Fast gas chromatography
As shown above, many of the proposed models tried to opti-
mise both temperature and pressure programming and decrease
the analysis time without loss of resolution. Typically, analyses
performed with long capillary columns with internal diameter
0.2–0.32 mm provide analysis time in the range of 10–60 min. When
short analysis time is an important factor, fast GC procedures can be
used. By decreasing the column length, inner diameter and phase
thickness, using less viscous carrier gas (hydrogen), increasing
carrier velocity or temperature in isothermal analyses and tem-
perature/pressure programming rate in PT, PP and PPTGC, using
detectors that operate at low pressure, a substantial time gain can
be achieved. For complex samples, the minimum separation time
will be in the minute range, but for simple mixtures analysis time
in the millisecond range can be achieved. Some applications of
fast GC can be therefore considered an implementation of con-
ventional programmed methods. The theory of fast GC was widely
described by Blumberg [306–309] which investigated the effects
of pressure drop, flow rate and phase thickness on the efficiency
and analysis speed. Klee et al. [310] and Korytár et al. [311] con-
sidered the most important parameters and their combination for
obtaining the optimum speed and resolution. Van Lieshout et al.
[312], Davis et al. [313] and Cramers et al. [314] compared differ-
ent approaches for fast heating GC. A review on the use of fast
GC in trace analysis was published by Matisova et al. [315] and
several applications to different samples are reported. The meth-
ods development for fast GC was often carried out by modifying
current conventional capillary GC methods with translation pro-
cedures [310] and retention-time locking [40,313,316] to narrow
bore columns by taking into account the effect of changing vari-
ous parameters to achieve faster analysis without too much loss of
efficiency. The parameters that can be translated (columns dimen-
sions, carrier gas, pressure and flow rate, temperature program rate)
and not translatable ones (stationary phase, phase ratio, initial tem-
perature and isothermal tracts in programmed analysis) and the
influence of the injected amount were discussed by Klee et al. [310].
The concept of speed-optimised flow (SOF) was introduced and the
modification of the Van Deemter–Golay equation at high column
pressure [306] and its effect on plate height were evaluated. The
optimal temperature-program rate for fast GC was found to depend
on the void time tM and a suitable translation from conventional and
fast procedures should maintain the same normalised temperature
program; a ramp rate 10 ◦ C/tM was recommended [42].
7. Comments and conclusions
Many of the proposed models and calculation methods permit
accurate prediction of retention data and optimisation of the effi-
ciency and analysis time in programmed temperature and pressure
conditions. The procedures described by some authors were widely
applied, implemented and modified by further researchers. The
results of the predictions were more satisfactory when stationary
phases and analysis parameters similar to those used in the original
work were selected and the programmed runs carried out within
the temperature and pressure range set for preliminary analyses.
The majority of the experimental data used for the calculation
models were obtained by using columns coated with non polar or
(60)
low-polarity stationary phases. About two thirds of the authors or
research groups cited above used non polar polydimethylsiloxane
columns (AT-1, DB-1, DC-200, HP-1, HP-PONA, OV-1, OV-101, SE-30,
SPB-1), Apiezon L, Squalane and SPB-octyl. About 20% of them used
low polar 5% phenyl, 95% methyl polysiloxane phase (DB-5, HP-5
SE-52, HP-Ultra 2). Polyethylene glycol was the most used polar
phase (DB-WAX, CP-WAX, SA-WAX, Carbowax 20 M, Supelcowax
10, Superox 20 M, Nukol) and about one third of the cited authors
used this type of highly polar column in parallel with non-polar
phases. Other medium-polarity or highly polar phases, with greater
amounts of phenyl groups or different percentages of cyanosilicone
polymer were used in about one fifth of the cited articles. Some
authors applied prediction procedures to the data obtained using
three or more column of different polarity [65,66,70,105,106–111,
192,199,200,216,217,227,271,298–300,302,316] and therefore
tested the proposed models under different conditions.
The samples analysed for studying and checking the validity of
the various prediction models proposed were often standard solu-
tions of compounds belonging to homologous series (n-alkanes,
1-alcohols, fatty acids methyl esters, ketones), branched alkanes,
phenols, aromatic and polycyclic hydrocarbons, halogenoalkanes,
terpenes, anilines, chloroanilines, chloro-, bromo- and nitro-
benzenes. Many of these test mixtures were simultaneously
analysed on non polar and polar stationary phases, and sometimes
the accuracy of the procedures increased when the polarity of the
columns and of the compounds was the same or very similar. The
optimisation of the resolution was also tested with complex natu-
ral or synthetic mixtures, as petroleum products, pesticides, vegetal
oils, beverages flavours, wines, spices and fragrances.
Many articles did not list all the analytical parameters used and
their accuracy, precision and repeatability, and the phase concen-
tration in packed columns or the layer thickness in capillary ones
and other column’s characteristics were often omitted [13,16,18,25,
26,27,47,48,73,98,167,180,181,186,187,193,199,200,209,215,252,283,
285,290]. The authors that reported the length, the diameter and
the layer thickness, cited the nominal values given by the pro-
ducers. It was found by SEM measurements [258,299,300,317]
that the true diameter of capillary columns may differ up to 12%
from the nominal value. This uncertainty leads to an error of about
2% in the determination of the void time with difficulties in the
application of translation methods and to a greater uncertainty
(up to 10%) of the calculated retention of the analytes [318] and
of the thermodynamic functions [319]. Differences between the
parameters set in the gas chromatograph’s control software and
those checked with independent measurements also influences the
accuracy of the prediction [299]. The phase thickness measured
by SEM sometimes agrees with the nominal one, but in some
instances it was found to differ up to 6% for 0.25 ␮m and to 25% for
thicker layers [320,321].
Notwithstanding the fair results in the prediction reported by
many authors which used the described models, a doubt still
remains on the possibility of applying some of the proposed proce-
dures in conditions differing from those of the original work, mainly
when columns or compounds of different polarity are used. Also
when the mathematical models are theoretically valid, it is diffi-
cult to predict the reproducibility of the results when a method is
applied in another laboratory if the analytical parameters set by
the authors of the original method, their correlation and the accu-
racy and repeatability of the experimental data are not well known.
Very few complete listing of the experimental conditions and of the
procedure used were found in the collected literature. As an exam-
ple, an accurate measurement process was described by Korány and
 G. Castello et al. / J. Chromatogr. A 1216 (2009) 1607–1623
Amtmann [128,129] that reported the procedures followed to check
the day-to-day repeatability of the results. The evaluations of the
methods reported by some authors often show the accuracy of the
predicted values with respect of the experimental ones, but few
data on the precision and fluctuations of the values used for the
calculation are given.
To be generalised, a retention model should record exactly all the
conditions used for measuring the retention values of the isother-
mal or isobaric preliminary runs and of the TP or PP analyses whose
chromatograms have been predicted. Repeatability in the same lab-
oratory of the retention data, peak widths and peak shape with
the same column or with other columns with the same station-
ary phase and different length and phase ratio and the influence
of small variation of temperature, flow rate and injected amount
should be reported. All the properties of the column must be accu-
rately listed and the values of initial temperature, inlet pressure,
programming rate indicated with their accuracy and precision. An
independent measurement of these parameters often shows that
the true values differ from those shown by the gas chromatograph’s
control software. The evaluation of the influence of small variations
of the experimental parameters increases the quality of the results
and permits to judge if the reported difference between experimen-
tal and predicted data depends on the repeatability of the various
experimental runs or on the robustness, accuracy and precision of
the calculation method. The possibility of using some of the pro-
posed models and procedures to accurately predict the optimum
conditions for a fast and efficient separation of complex mixtures
on the basis of published databases encourages the research of new
and more accurate calculation methods, whose performance will
depend on the exact knowledge of the analytical conditions and on
their reproducibility.
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