Chromatogmzfihic

Reviews

Elsevier Publishing Company, Amsterdam Printed in The Netherlands

SELECTIVE

DETECTORS

IN GAS CHROMATOGRAPHY

M. KREJCI

AND M. DRESSLER

Institute of Instrumental Brno (Czechoslovakia) (Received February

1201,

Analytical

Chemistry, Czechoslovak Academy

of Sciences, Leninova

82,

1970)

CONTENTS 1. Theoretical .................................. A. Trends in the development of chromatographic detectors and basic terms. ..... .................... B. Qualitative chromatographic analysis a. Identification of substances from information derived from the chromatogram b. Reaction chromatography and chemical multipliers : : : : : : : : : .. .... ......... C. Selective detectors. .... a. Definition of selective detectors ....................... b. Requirements following from the definition of a selective detector ........ D. Quantitative characteristics of detector selectivity ................ a. Detector characteristics .......................... b. Selectivity as the ratio of the time integrals of the responses of two detectors ................. c. Classification of selective detection systems d. Detector selectivity as relative response ................... ................... E. Forecast of selectivity for some detectors a. Electron capture detector ......................... b. Alkali flame ionisation detector ....................... ................... F. Methods of connecting selective detectors. a. Parallel coupling of detectors ........................ b. Series coupling of detectors ........................ c. Carrier gas separators ........................... , ................... z. Analytical part. ............. A. The electron capture detector ........................ B. The alkali flame ionisation detector ...................... C. The surface ionisation detector ........................ D. The flame photometric detector ........................ E. Emission spectrometry ........................... F. Spectrofluorometric detection ......................... G. The ultraviolet spectrophotometer detector ................... H. The infrared spectrophotometer detector .................... I. Mass spectrometry. . . . . . . . . . . . . . . . . . . . . J. Galvano-coulometric detectors . . . . . . . . . . . . . . . . . K. The electrolytic conductivity detector . . . . . . . . . . . . . L. The polarographic detector . . . . . . . . . . . . . . M. The piezoelectric sorption detector . . . . . . . . . . . . . . . 3. Conclusions . . . . . . . . . . . . . . . . . . . _ . _ . . . . References. . . . . . . . . . . . . . . . . . . . . . .
I I 2 2

_ . : : :

4 5 5 6 7 s7
IO

13 13 13 14 15
16 16 17

17 17 24 29 31 35 38 39 39

. . . . . .

. . . . . . . . _ . . .

41

45 48 51 53

50 50

I. THEORETICAL

A. Trends in the develo$ment

of chromatogra$hic

detectors

and basic terms systems that are

13 (1970) I-59

In the present review we propose to deal only with detection

Chromatog.

Rev.,

M. KREJti,

M. DRESSLER

directly connected to a chromatographic column. We regard gas chromatography as an analytical method which includes the separation, identification, and quantitative determination of the individual components in the mixture analysed. We shall not discuss analytical procedures which involve further independent processing of the mixture of substances under analysis either before or after the chromatographic separation. We shall, however, discuss analytical methods often used as independent analytical methods (e.g. mass spectrometry) when they are used in direct conjunction with chromatographic columns for detection purposes. A detection system is considered selective to substance i when the analytical property of substance i, ai, induces a signal and/or response sufficiently quantitatively different to distinguish it from the response induced by the analytical property of substance j, ai. An analytical property is called such property of mass that is in exactly defined relation to the quantity and quality of the mass analysed72. Signal and response are (cf. ref. 222) defined as the immediate effect of the mass on the detecting element and the response of the detecting element to the signal. The application of gas chromatography has reached the stage where information on the character of the individual components cannot be based on the interpretation of retention characteristics alone. This is why a considerable changeover to the use of more selective rather than non-selective 271detectors can be seen. This phenomenon can be explained without difficulty. While pioneer work dealt with simple mixtures of substances, the identification of which did not usually present any serious problem, today the main task in research applications of gas chromatography is the analysis of complex natural materials (e.g. biological materials, crude oil etc.) where the identification of individual components by means of retention characteristics interpretation alone is practically impossible. From todays point of view the not very high precision of the early quantitative work in gas chromatography led further to considering many detectors as completely non-selective, even though more recent precise studies have shown their responses to be dependent on the properties of the component analysed. The processing have been stances205 increasing tendency of manufacturers and analysts to use automatic data will probably also allow the use, in future, of those detectors where ways found to record small differences in detector response to individual subas selective detectors. analysis

B. Qualitative chromatographic

(a) IdentiJication of substances from information derived from the chromatogram Retention characteristics are the values most often used in chromatographic qualitative analysis. Both absolute values of the retention characteristics such as e.g. retention times, retention volumes, or specific retention volumes4,233, and relative values of these quantities such as e.g. relative retention times (volumes)233, or Kovats retention indices* are used. Characteristic parameters of a chromatographic curve, such as e.g. the height of the curve, the width of the curve, are reflections of the analytical characteristics of the substance analysed. A chromatographic curve is in definable relation to the character and quantity of the substance analysed. In general practise, however, i.e. when common stationary phases and non-selective detectors are used, this curve is
ChtOWXZtOg. Rev.,

13 (1970)

I-59

SELECTIVE

DETECTORS

IN

GC

neither selective nor specific for the substance analysed. The retention volume VR is partly due to the values characterising the chromatographic system (dead volume of the column V,, and volume of stationary phase V, or surface area of adsorbent for a gas-solid system) and partly due to the partition coefficient K, whose value depends on the substance analysed and the stationary phase, i.e. vn = v, + KV, As the partition coefficient, generally speaking, is a function of the intensive thermodynamic value-chemical potential-(+ refs. 108 and 232), the retention volume for a given system of solute and stationary phase, at constant temperature and pressure, is constant, however it is not selective or even specific. From the theoretical point of view a negative result only can be considered as conclusive in a chromatographic experiment, i.e. substance A is not identical with substance B in case that IRA # VRB. If we carry out a qualitative identification from the values of retention characteristics only, we must be aware of the risk that the chromatographic curve may not pertain to the substance selected for calibration although the latter has the same characteristics, and even that the curve may not be induced by a single substance but by two251 or even more substances that have the same partition coefficients in the given system. Similarly with the retention volume, the shape of a chromatographic curve is again a function of the partition coefficient and of a series of further values characteristic of the chromatographic column being used (e.g. the particle size of the packing, the thickness of the liquid film etc.) and of the system used, viz., solute-stationary phase (e.g. the diffusion coefficient of the solute in the liquid phase) or solute-mobile phase (e.g. the diffusion coefficient of the solute in mobile phase). It is obvious that the width (shape) of a chromatographic curve is influenced by further non-selective values so that the probability of the existence of two substances which would, in the given system, have not only the same partition coefficients but also all other identical parameters, considerably decrease. A procedure 233has been suggested for verifying the identity of a substance by comparing the chromatographic zone widths (or by comparing the heights of theoretical plate) of different substances. Because of the complexity of the dependence of above-mentioned values on carrier gas flow, temperature, and comparatively small differences in zone widths, this identification procedure has not been used very much. We only mention it here as it is a procedure characteristic of the efforts to obtain from chromatographic experiments further information that would decrease the probability of confusion among the substances being analysed. Methods by which identifications have been made by taking advantage of the change in the partition coefficients in an homologous series, which are known or can be forecasted from several experimental data, have been used extensively in chromatoretention characteristics-retengraphy; it being possible to correlate74~144~2s4~250~305 tion volumes, specific retention volumes, relative retention volumes, Kovats indices (retention indices) etc.-with the values characterizing the homologous series. Such values are either those which cannot be in any way determined from the chromatogram (e.g. molecular weight, number of carbon atoms, boiling point, the ratio of critical and experimental temperatures etc.), or those found by one or several chromatographic experiments (e.g. the above-mentioned shape of curve, the ratio of the retention characteristics on two stationary phases mostly differing in polarity, retention characChronzatog. Rev.,
13 (1970) I-59

M.

KREJti,

M.

DRESSLER

teristics measured at different temperatures, etc.). By interpolation of these dependences, the retention characteristic of a particular member of an homologous series can be obtained and compared with retention characteristics determined experimentally. Agreement between the two sets of data increases the probability of the identity of the substance being predicted and the substance being analysed. This identfication procedure is, of course experimentally exacting and timeconsuming. That is why procedures have been suggested to speed up the identification procesP4. The simultaneous determination of the retention characteristics of a substance on a system of several columns connected in parallel and having packings of different polarity enables one to obtain a set of retention characteristics in one single experiment. These data can then be correlated in any of the above-mentioned ways. If known reference substances are used as standards in the system, the probability of error in the qualitative analysis is essentially decreased, since the deductions are made from several sorption characteristics independent of each other, i.e. from several pieces of information independent of each other. All the identification procedures which have been indicated employ non-selective detectors. Detector data, therefore, cannot be used in any way as an independent source of information about the identity of the substance being analysed.
(b) Reaction chromatography and chemical multipliers Reaction gas chromatography 23v24 has been used by a number of workers for facilitating the identification of individual components of a chromatogram. In a nonof selective cycle, for example, the conversion 121y200 the analysed substances into carbon dioxide and water has been used. A hydrocarbon with n C atoms, e.g., provides n moles of carbon dioxide. The sensitivity of detection is considerably increased in this way. In a selective detection cycle, group or selective (mostly catalytic) reactions, can be used, whereby selected types of substance or one substance can be removed from the chromatographic spectrum174,or converted into different substances261.The chromatograms of the unchanged substances are then compared with those obtained after the chemical changes of the substances. This type of reaction gas chromatography can be considered as the predecessor of selective detectors. In Fig. I the reactor
kl)
3 1 4

(bl
H
of compounds.

Fig.
I =

I. Exploitation of reaction gas chromatography for selective determination Sample chamber; 2 = column; 3 = reactor; 4 = detector.

is positioned in front of one of two non-selective detectors connected in parallel (a) or between two non-selective detectors connected in series (b) behind the column145. This identification method should have a revival when chemical (molecular) multipliers are introduced into chromatographic methods201. It is obvious that the sensitivity of detection can be controlled to a considerable extent by connecting n multiplier reaction units in a series, as the amplification factor is an exponential function of n. Even though chemical multipliers can be used in a Chromatog.Rev., 13 (1970) I-59

SELECTIVE DETECTORS GC IN non-selective cycle as e.g. (see ref. 252) -+2co CO2 C 2co -+ cue 2 CO, etc.

1st step co, --(% = q. 2 CO2 the multipliers employing selective reactions will remain especially significant for selective detection systems. E.g. for hydrogen sulphide in a mixture with hydrocarbons (see ref. 22) I, + H,S = 2 HI + S 5 HI + HIO, = 3 I, + 3 Hz0 i.e. 5 I, -+ 5
I2 -+ H2S

HI0 IO HI 36

I,

1st

step 6 I,.

The use of reactive organo-metallic compounds permits extraordinarily high sensitivities to be reached. The combination of these sensitivities with group or selective reactions gives rise to new possibilities of selective detection. By introducing chemical reactions into the detection system, further information about the identity of the substances analysed is obtained from a chromatogram and the possibility of confusing the identity of the substances in the chromatogram is again reduced. In practice, the use of selective detectors combines the function of reactor and non-selective detector in a number of cases. C. Selective
detectors

Katharometers and emissive detectorP were first used for direct comparison of the responses of two different detectors. The ratio of the responses of both detectors was assumed to be constant for individual groups of substances. Thus e.g. the ratio of the response of the emissive detector to that of the katharometer233was found 0.14 for a-paraffins, 1.25 for aromatic compounds and 0.44 for naphthenes. AS will be shown later, the assumption of constant response ratios for individual groups of substances was too optimistic. It only holds for a limited number of members of individual groups of homologous series. GRANTSworkll* can, today, be considered as the first significant step in the utilisation of detector responses for the identification of substances. The significance of this procedure was demonstrated later when the electron capture detector was used for identification purposesrg4. (a) Definition of selective detectors The definition of detector selectivity is far from uniform. Two aspects can be considered as basic according to which the selectivity of the detection system can be evaluated250. Firstly, we take the case where the response of two detectors to a signal from one substance only is compared; and in the second case we compare the response of one detector only to the signal of two different substances. Chromatog.Rev., 13 (1970) I-59

6 I. A detection system is considered selective

M. KREJCf, M. DRESSLER if the molecular response of a

detector S to a signal (or response to a unit of mass) from a substance (A) (or the group of substances A) differs from the response of a detector A to a signal from the same substance and if the ratio of responses of both detectors is sufficiently (see Section r.D.a.) different from the ratio of both detectors to a signal from substance B. 2. Detector response can be considered selective if the molar response (or relative molar response, or response to unit mass) of the detector to a signal from substance A (or the group of substances A) differs sufficiently (see Section 1.D.c.) from the molecular response of substance B. The suitability of the individual definitions depends considerably on the purpose for which the detector is to be used. The application of a detection system according to the first definition is obviously more suitable for practical qualitative analysis, especially for selective differentiation of groups of substances in mixtures to be analysed. This system permits the quantitative determination of individual components in the mixture or, at least, the determination of their interrelationships. It is therefore suitable to use as a reference such detector that is the least selective. The interpretation of the information then consists of merely comparing the detectors response to the individual components of the mixture being separated in the column. The characteristics derived from the second definition are mostly used for the determination of detector properties. Experimentally, less exacting attitude to detector characteristics acquires, of course, a knowledge of the proportions of the components in a mixture. It is necessary to note that, in accord with the second definition, it is necessary to set the limit between selective and non-selective detectors by means of the determination of the value of the response ratio only. From todays point of view, the value of the relative molar response for different substances also differs in the case of detectors which are generally considered to be representatives of the category of non-selective detectors (as e.g. the FID12*,205,264). (b) Requirements following from the dejkition of a selective detector From the above definitions of detector selectivity it follows that the mere determination of the detector response is not, alone, sufficient for qualitative analysis. (The term selectivity should in this case be substituted by the term sensitivity.) In the simplest case it is essential to determine the response of a reference (non-selective) detector. These requirements can be met, essentially, in three different ways: I. Both responses are determined in the course of one analysis, two detectors being coupled with a column outlet, in parallel or in series. Two chromatograms are thus obtained, the peaks of which can be compared. This solution entirely satisfies the conditions mentioned in the introduction to this work. The results of only one analysis provide information concerning three things, viz., the retention characteristics, the response of the selective detector, and the response of the reference detector. The particular advantage of this method is that the responses of both detectors are recorded under the standard quantitative conditions, i.e. either the same amount of substance enters both detectors (in the case of connection in series), or a known proportion of the total amount passes through (in the case of parallel detector). Furthermore, any column effects (ratio of area and height of curve, shape of curve) are almost entirely eliminated. 2. The responses of selective and non-selective detectors can be determined in Chronzato,o. Rev., 13 (1970)
I-59

SELECTIVE

DETECTORS

IN

GC

two analyses in one chromatographic column. This is possible with most commercial apparatus. One analysis is usually not sufficient. The calibration curve must be used, as far as possible, over only a small range to eliminate the errors caused by inaccuracies in sampling. However, this method of determining the response does not agree, in the main, with the concept of selectivity for a detection system, as defined in Section I.A. 3. An entirely independent chromatographic system is used for the determination of the response of a standard system. In this case, a qualitative analysis to determine the ratio of individual responses is not, in general, sufficient but a complete quantitative analysis must be carried out. If the column selected is such that the chromatographic spectrum (the sequence of eluted substances) is changed, then apart from the quantitative analysis, the qualitative composition of the mixture must also be determined. The selective detector is then used only for verification of our assumptions. This solution does not agree with the assumption in Section I.A, either. From the procedures introduced for taking advantage of detector selectivity it follows that only in the last case can the detector selectivity be characterised according to the second definition in Section 1.C.a. In all the other cases, i.e. when a really selective detection system is of interest, it is advantageous to use the first definition.
D. Quantitative characteristics (a) of detector selectivity (ref.
222)

Detector characteristics

The value of the detector response Ra to a component i must inevitably be determined mathematically for the quantitative characterization of detector selectivity. It will be derived from relationships for detectors mostly in use in chromatography and form the basis of a classification222 of them. Instantaneous detector response is generally described as
Rc /=

$,

P, K ,

$,

a, a,, aa,yip T /

where K = construction parameter, a = the analytical property, y = the molar fraction of the solute in the gaseous phase, T = temperature; indices: i = solute, o = carrier gas, a = scavenger gas. The dependence of the response on the first two values, viz., carrier gas flow rate dV/dt and pressure P, can be used with advantage for the classification of the detectors into the following groups: destructive D, nondestructive N, mass M, concentration C; at the same time, each of the detectors used can be included into one of the groups: MD, DC, NM, NC for certain concentration ranges and working regimes of the detector. For a selective detection system it is inevitably so that at least one of the values of a, for a selective detector ai, will be different from the a value of a standard detector at. All the values in eqn. I are, of course, assumed to be constant during the elution, except yr, which will change in both detectors in the same way or in a known way (see eqn. 8). For analytical purposes it is more important to know the quantitative relationship between the detector response and the total quantity i?i than merely the response under given conditions. The relation222then holds
Chromatog. Rev., 13 (1970)
I-59

M.

KREJti,

M. DRESSLER

(2)
where t, to t, is the time interval during which yi increases above, or decreases below, the limit of detectorla sensitivity. The area under the chromatographic curve S is given by:

SC =

$- f,
tl

dt

(3)

where dbldt is the chart speed. For individual types of detector

then holds222 (4) . N

Si

CN

=-&

.$..$..?!%.Ni
db .-.-.-.dt RT P I

dV/dt I dV/dt da,

dYC da, dyf . Aii

StCD =KbD

S,

MN

db . v .-. MN *dt . $ . e da Y,

dV/dt * Ni

dYt

srD

= KdD

If an additional gas is used in the detectors, which often occurs with selective detectors, the constants K acquire different values Kf and the sum of the flow rates of carrier and the additional gases dV/dt + dV,/dt must be substituted for the carrier gas flow rate. (b) Selectivity as the ratio of the time integrals of the responses of two detectors If linearity of response is assumed, the ratio of the time integrals of the responses of detectors used will be identical with the ratio of the instantaneous responses of the two detectors [%(t)lS The term response. =
kbi(t)lA (8)

response

will from now on be substituted of detection system selectivity

for the term time integral

of

The concept detectors

as a ratio of the responses

of two

(9) is very suitable for qualitative analysis, as it implies both the element of selective response and the element of quantitative analysis of the mixture of compounds investigated. It is assumed that SA # o. Although the responses of both detectors can be either positive or negative, both values are always considered positive in connection with selectivity; therefore o < s < 00. Chromatog. Rev.,
13 (1970) 1-59

SELECTIVE TABLE
A FLAME

DETECTORS IN

GC

1
AS THE RATIO OF THE RESPONSES OF A THERMAL CONDUCTIVITY DETECTORala AND IONISATION DETECTOR

SELECTIVITY

Compound Pentane Hexane Heptane 2,sDimethylbutane Cyclohexane Benzene

RG(TC)&

RG(FI$

1.023 I.000 0.953 1.040 0.905

1.020

0.982 0.996 I.000 1.021 1.028 I.093

I.042

1.024 I.000 0.933 1.012 0.828

I.

a RG is a response of a weight unit compared to the heptane response RG =

Only in cases where a change in selectivity is investigated with respect to some parameters of the system, is it necessary to use negative values of s for the calculations. The requirement that S # o holds, of course, even in this case. From the theoretical point of view, a system whose s = I + 6, where 6 is the error in the determination31 of the ratio Ss/S*, can be considered as non-selective. The increasing demands on the accuracy of the quantitative determination of the substances lead to the situation that when 6 = 2%, such systems of detectors will also satisfy the criteria of selectivity that are considered to be typical of representatives of non-selective detectors, see e.g. the system of thermal conductivity-flame ionisation detectors for hydrocarbons. The values of s according to eqn. 9 for hydrocarbons, relative to heptane = I, are given in Table I. It is obvious that under these conditions s differs by more than 2% even for the simplest type of homologuos series: pentane, hexane, heptane. However, with the present state of instrumentation 6 can be made lower by an order of magnitude235. Equally significant deviations of s values from I can be obtained in case of a single flame ionisation detector using different ratios of nitrogen to hydrogen in the burneG*. The ratios of the maximum and minimum relative molar responses which can be attained for different substances are shown in Table 2. The RMR value in this case is influenced by the working conditions of the detector. It could be expected, in future, that these very small changes in the values of the selectivity s might be used for quantitative interpretation. The increasing accuracy of interpretation of quantitative chromatographic data and the wider and more universal application of automatic integrators and computers, which can process the resulting data further235,indicate this development.
TABLE RMR 2
RATIOS FOR ONE

FID USING DIFFERENT NITROGEN AND HYDROGEN RATIOS

Compound

Benzene Acetone Butyl acetate Tetrachloromethane Pyridine

I.079 1.278 1.194 1.110 1.116

Chromatog.

Rev., 13 (1970) 1-59

IO

M. KREJei,

M. DRESSLER

At present,

detection

systems

are usually

considered

as selective

when they

have s > IO. With regard to the quantitative values as a criterion of the selectivity of a chromatographic detection system it must be emphasised once again that the substance or group of substances to which the selectivity is related and the operating conditions of the detection system (for each of the detectors) must always be considered. For example, let us consider the system of two of the detectors already mentioned, viz. the thermal conductivity and flame ionisation detectors, they were rightly considered as non-selective; but to the group of permanent and noble gases, carbon disulphide etc., this system will show high selectivity regarding the imperceptible response of the flame ionisation detector to the substances mentioned above. This property of the flame ionisation detector is often made use of when either the vapours analysed are diluted with permanent gases or carbon disulphide is used as soIvent23g. Under certain conditionsa a mere change in the flow rate of the hydrogen introduced into the flame ionisation detector can change the value of s considerably. In Table 3 this value changes more than twelve times. At a hydrogen flow rate of 95 ml/min there is a molar response of the detector to octane and the response to tetrachloromethane nearly equal, however, at a flow rate of 55 ml/min the molar response of tetrachloromethane is fifteen times smaller than that of octane. In the latter case the detection system can be considered as selective for octane.
TABLE RM RATIO 3
FOR ONE

FID WlTH DIFFERENT

HYDROGEN

FLOW

RATES

H, velocity (ml/min)

RM(C,HI,) / RM(ccl,)
15.0

16.4

(c) Classification of selective detection systems As the basis for the classification of selective detection systems the general eqn. I has been used and a classification of detectors followed from it. The basis of our classification of detectors depends on three variable elements: the analytical property of the substance, the detector type and the working parameters of the detector. The analytical property of the substances employed in the detector usually allows one to categorise the selectivity of the detection system according to a group of substances and/or an homologous series. Detector type shows the dependence of the detection system on the flow rate of the carrier or carrier and additional gases, temperature and pressure. A change in detector working parameters can cause a transference in the significance of the individual elements of the analytical property, a change in signal, response, and thus even in the selectivity of the system. Diferent analytical property, the same detector type. The basic characteristics of a detection system of this type are given by eqn. 9. From eqn. 9, the selectivity is proportional to the ratio of the analytical properties of selective (index S) and nonChromatog. Rev.,
13 (1970)

r-59

SELECTIVE

DETECTORS

IN GC

II

selective (index A) detectors. A linear range for both detectors is assumed and that when y = o, ato = o also. If the above-mentioned dependence does not pass through the origin (the latter part of the assumption), then the value of s = f(y) and the coefficient of selectivity have a limited significance. The constant k includes an apparatus constant. In the case when the values T and P (see eqns. 4 to 6) are not identical in both detectors, then this constant also includes the terms characteristic of the ratio of these values. The MD type detector (eqn. 7), being independent of pressure and temperature, is the exception. The basic advantage of the detection system consisting of two detectors of the same type is the fact that value s is independent of the gas flow through both detectors and thus, in case of connection in parallel, is even independent of the splitting ratio of carrier gas flow. If the carrier gas flow at the column outlet is split in a certain ratio between two detectors (&A), then

(dV/dt)s
(dV/dt)*

lNak
= - (N~)A =

k+

(10)

After substitution from selected eqns. (4 to 7) with respect to eqn. 9 it can clearly be seen that s is independent of the ratio of gas flow through both detectors. The validity of the basic eqns. 4 to 7 is assumed. Diffeerent agzalytical property, diffeerent detector type. The basic characteristic of the detection system, similarly to the previous case, is given by the ratio of analytical properties of a selective and a non-selective detector (eqn. 9). In addition it is also necessary to consider the parameters (pressure, temperature, volume), thus follows from the requirements of the quantitative characteristics of detectorszz2 (eqns. 4 to 7). If equal temperature and pressure are assumed for both detectors, TA = Ts, PA = Ps, a condition which is often satisfied, then use of the expressions 4 to 7 leads to the relations:
CN St yiiKCN = z daijdyt da,ldyt

s1 =

(11)
da,b da,ldyc

CN St .Sg=-=-

KCN KMN

RTCN PCNVMN

SF

w
dalldys _da,ldyc
(13)

Sic* S3==T=-

KCN KMD

RTCN PMD

k+
(dl/'/dt)cN

St
s4 = "FD

MN KNIN = KMD '+ VMN

(dV/dt)Mx
k+

da,ldyt -da,/dyt

(14)

.SfD
S5=F=CD St

KCD KMD

RTCD PCD

(15) (16)
Chromatog. Rev., 13 (1970) I-59

(dv/dt)cD

KCD

RTCD

da,/dyi
da,/dyi

s, = F

= G

PCDVMN

12

M.KREJCi,M.DRESSLER

In contrast to selective systems consisting of pairs of detectors of the same type, selective systems consisting of pairs of detectors of different types are usually dependent on the flow rate or on ratio of carrier gas flow rates. In our case only sl, s2, and s6 are independent of the carrier gas flow rate. Detectors of the CD type are relatively rare. Thus only the value s2, independent of the ratio of the carrier gas flow through the detectors, has practical significance. The same detectors under d#eerent working parameters. Detection systems con-

sisting of the same detectors working in different working parameters in such a way that one of the processes provides the selectivity of the system fall into the third category. The selective determination of carbon monoxide240 by a catalytic combustion detector is an example of this. By suitable temperature contro1171J72 of the detector wire, the combustion of carbon monoxide, specifically, in a mixture of other gaseous hydrocarbons, can be achieved and thus a detector signal specific to carbon monoxide also. Different detector characteristics can often be imparted by reaction chromatography or chemical multipliers (see section 1.B.b.). Detector sensitivity can often be changed selectively by conversion of the effluent before its entry into the detector23!24. A substance or a group of substances are converted in a reactor into compounds to which the detector is sufficiently sensitive. In some cases (e.g. conversion275 CO -+ CH, or hydrogenation of sulphur compounds261), selectivity can be increased by several orders of magnitude and thus the value of s is also proportionally increased. In the future, use of chemical multipliers201 may supersede a number of these reactions and expand the use of this type of selective system. Use of another analytical method. The three groups of detection systems that have been described up to now are all detectors of binary mixtures. That means that a qualitative change in the effluent composition in a chromatographic zone cannot be registered by the detector. This fact, among others, has led to the use of a complete analytical method as the detection system. When gas chromatography is used in combination with another analytical method several basic demands must be met : I. The analyser being used must have a sufficiently low time constant so that only a fraction or part of a fraction leaving the chromatographic column is analysed. 2. The analyser being used must be sensitive enough so that the efficiency of separation on the chromatographic column need not be decreased by increasing volume of the mixture being led in. 3. The effective volume of analyser must be sufficiently small otherwise it could cause a decrease in the efficiency 236of the chromatographic column. The price of these detection systems is such that it often leads to the use of simplified versions of these analysers. Thus, e.g. a mass spectrometer with an adjustable value of the mass being detected permits the selective detection of substances having selected groups or elements 251. Even so, although this simplified and cheaper method can solve some interesting analytical problems, an increasing number of producers and users incline to equipment which gives a complete and more or less concIusive analysis of the chromatographic fractions. But under neither of these circumstances chromatography can be considered as a separation method only. The conclusive analysis, without previous orientational identification resulting from retention characteristics of individual fractions, is very difficult in most complicated Chro~2atog. Rev., 13 (1970) 1-59

SELECTIVE

DETECTORS

IN

GC

I3

analyses (natural mixtures of substances) and, in many cases, even questionable. The use of complete analysers as detection systems in gas chromatography is a typical example of systems combining a selective analyser (e.g. a mass spectrometer) and a non-selective chromatographic detector (a flame ionisation detector connected in parallel or a record of the response of the ion source of the mass spectrometer). This illustrates that chromatography can be used here as an analytical (not only separation) method permitting quantitative analysis of the mixture and also makes qualitative analysis easier. (In many cases a selective analytical method is used as a conclusive method for the identification of substances the composition of which was forecast from the elution characteristics.)
(d) Detector selectivity as relative response

While for qualitative analysis it is necessary to use a two-detector system, which gives some information on the quantitative composition of the mixture being analysed, the use of one detector only is sufficient to determine the detector selectivity characteristics-and generally experimentally easier. Under these conditions, the detector response to the signal of the substances being studied is then compared with that of the standard substance. The result is then expressed either in the form of relative molar response222~250~303 (RMR)s, of the substance relative to the standard Y
RMRz, =

darddyr
da&b+-

(17)

or in the form of relative weight response66r250 (RWR)t,)

RWRz, =

daddct
dadb

(1s)

where c is weight concentration of the solute in the carrier gas. Hydrocarbon is usually selected as the reference substance. Detector response to it is considered as non-selective. Under these conditions, as in the case of the two-detector system, it is suggested66 that a detector is considered as selective to a substance if the RWR or RMR is higher than IO. In certain special cases of the study of the characteristics of detector selectivity303 even the substances to which the detector was just selective were used as standards. In this case, unlike that above, such a detector can be considered selective when RMR -+ 1.0. This way of expressing detector selectivity accords better with physicochemical studies of detector performance than with analytical practice.
E. Forecast of selectivity for some detectors

Regarding the complexity of the processes taking place in some detectors, it is very difficult to apply the general relations from Section I.D. to concrete cases. The import of selective detector information, however, frequently leads one to try to forecast the response or relative response of the detector.
(a) Electron capture detector

The electron capture detector is considered to be mass non-destructive. response222to a substance i can be expressed as follows:

Its

Chromatog. Rev., 13 (1970) I-59

I4

M.KREJti,M.DRESSLER

Ri = KMN g

(-3-0) yi

(18)

where KMN is a constant of the detector, and ei and cc, are the molar extinction coefficients of effluent and carrier gas, respectively. The molar extinction coefficient is an analytical property of the substance i and, therefore, according to eqn. 17 in the preceding section, we can write for the relative molar response :

RMRi =

(&a 80) (Br_-80)

(19)

Over a small range, the contributions of the individual substituents in a molecule to the molar extinction coefficient are additive (for the relative molar response related to the substance to which the detector is selective301y303, this range is estimated30a as having a value of RWR = I to 2). Then &=ZI&s (20)

where es is the contribution of a substituent to the molar extinction coefficient. The values for the individual substituents have been tabulated301-303 in the range of additivity, and the value of the relative response can be estimated from these. The estimations, of course, suffer from a considerable error (usually up to 30%). (b) Alkali jame ionisation detector The response of the flame ionisation detectoP2 is proportional of effective carbon atoms C,r and to the ionisation efficiency a. Ri = Km .a (Z Cer) . (dN/dt) One can also write for the alkali flame ionisation

to the number

(21) detector

where KI\ID is a constant. (AFID) RP =

[KM~* (Z&f)

KMD

a (ZCef)l (dN/dt)

(22)

where KM is a constant and a* is the ionisation efficiency. In addition to the ionisation in the flame ionisation also occurs which is caused by the presence of alkali metals and effective elements E,f (e.g. halogens, phosphorus) in the molecules of the effluent. If a hydrocarbon is taken as a reference substance (i.e. the substance for which E,r = 0), then the relative molar response for an alkali flame ionisation detector can be written as RMRi =
KMD a (ZC& KMD + KM a* (ATE&

(23)

a (2:Cef)r

Eqn. 23 will have the same form for the selectivity s as that according to eqn. 9 if the value s is taken as the ratio of the response of a flame ionisation detector to that ofan alkali flame ionisation detector. Of course, the assumption (dN(dt)Frn = (dN/dt)AFrn must be fulfilled otherwise eqn. IO would have to be included in eqn. 23. If the ionisation efficiency of both detectors is compared, it is found that
KMD a < KM a*

(24)

Chronzatog. Reu., 13 (1970) 1-59

SELECTIVE

DETECTORS

IN

GC

15

If a substance containing substance, the expression in the form

effective elements E,f in its molecule is used as reference for relative molar response can be written approximately

RMRt = (Z EeM(Z Eef)r

In the cases where Cer is a constant the response (relative molar response) increases relative to the number of effective elements in the molecule E,f in accordance with eqn. 22, 23 or 25. An example g2 is shown in the first part of Table 4 in the case of the first four substances. On the other hand, the second part of Table 4 (substances 5 to 9) shows the cases when E,f is constant while the number of effective carbon atoms is different. Taking condition 24 into account, the ionisation efficiency calculated for a mole of effluent is constant.

TABLE

4
OF THE

NUMBER OF EFFECTIVE ATOMS E AND IONISATION EFFICIENCY

AFID=

No.

Compound

Zonisation eficienc?, (C/mole)

1.38

3 4 2 ; 9

Chlorobenzene I, q-Dlchlorobenzene r,3,5-Trichlorobenzene r,z,4,5-Tetrachlorobenzene Bromocyclohexane q-Bromotoluene /7-Bromostyrene Bromobenzene 2-Bromocymene

I 2 3 4 I I I I

2.79 4.10 5.53 2.4 2.5 2.4 2.4 2.5 -

In the. case shown in Table 4, a simple dependence of the retention characteristics (relative elution volumes) on the ionisation efficiency of the detector can be found. The dependence of the relative elution volumes on ionisation efficiency of alkali flame ionisation detector for the substances, marked in the same way as in Table 4, is shown in Fig. 2. The apparent linearity of log Y with respect to ionisation efficiency is in this case caused essentially by the lower ionisation efficiency of the flame ionisation detector in comparison with the alkali flame ionisation detector (condition 24). F. Methods of connecting selective detectors From the requirements following from the characteristics of detection systems it is obvious that there are three basic possibilities with respect to the pneumatic coupling of detectors. The coupling whereby a change in the ratio of effluent to carrier gas does not occur (resulting molar fraction remains constant) is realised by either in parallel or in series connections. In some special cases (mass spectrometry) the Chromatog. Rev.,
13 (1970) I-59

16
1 Cl IBr 20 30 4CI

hl. KREJCf, M. DRESSLER

Fig. 2. Relation between relative retention volumes v and ionisation efficiency or the number of halogen atoms in solute molecule using an AFIJ).

concentration of effluent in the carrier gas beyond the column outlet must be increased. In this case so-called carrier gas separators are used. (a) Parallel coupling of detectors A series of separators used in preparative chromatography behind the column outlet for separating the effluent into two unequal portions had already been described in chromatography. At the same time, approximately, carrier gas splitters were also used in front of a column. These devices both have the same aim: to permit the sampling of accurately measured-and thus also bigger-amounts of the mixture of substances being analysed, as well as maintaining optimum performance (i.e. small loading) in the former case of the detector, and in latter case of the capillary column. In both these cases, carrier gas flow is usually split in ratios I/IO to I/IO. The carrier gas flow is usually only split into two equal or only slightly differing portions in a system where the columns are connected in parallel, i.e. in equipment for temperature programming with a compensating column connection. It is evident that the instrumental introduction of selective detectors in parallel does not involve many complicated problems. The detectors can be connected in parallel regardless of their type and sensitivity. Even when detector systems, the sensitivity of which does not differ much one from another, are preferred, the differences in detection sensitivity can be compensated by the splitting ratio of the carrier gas flow. At present, the most frequently used reference detector is the flame ionisation detector which is used in parellel with selective detectors, usually an electron capture or alkali flame ionisation detector. The dependence of the detector signal on the ratio of the gas flow rate is discussed in Chapter I.D. (b) Series cou$ing of detectors Series connection of detectors Chromatog. Rev., 13 (1970) r-59

poses, much

oftener

than

the case of parallel

SELECTIVE

DETECTORS

IN

GC

I7

coupling, problems concerning the separation of the components and the maintenance of column efficiency. Although detectors with very small working volumes are used at present, spreading of the chromatographic zones always occurs in the first detector and with a consequent decrease in the separation quality of individual components in the second detector. Furthermore, a destructive detector cannot be used as the first one in the series. The only exception to this is in the use of flame ionisation and alkali flame ionisation detectors in series. This exceptional case follows from the properties of the alkali flame ionisation detector, the effective component of which is not subjected to a change on passing through the ionisation detector. In addition the selectivity of this system is increased still further on account of the removal of the carbon skeleton of the substances. In general, however, the use of a non-destructive type detector is an essential requirement.
(c) Carrier gas separators

The combination of high separation efficiency, especially in the case of capillary columns coupled with the high selectivity of spectral methods, particularly mass spectrometry, has been shown to be extraordinarily efficientzg6. Direct instrumental coupling brings about advantages in the form of time and labour saving, and also permits the transfer of extremely small amounts (approximately IO-* g) of the substances, without any danger of their decomposition by moisture or air, from the chromatograph into the spectrometer. To maintain the optimum conditions of chromatographic separation and the function of mass spectrometer, carrier gas separators (see Section 2.1) must be used so that the carrier gas is enriched by solute. A maximum amount of 0.1 to 0.3 ml/min of carrier gas may enter the ion source of the spectrometer. This carrier gas flow is, of course, too low to maintain good efficiency of the chromatographic column. Gas chromatography coupled with mass spectrometry is the most efficient system.of qualitative analysis of complex natural mixtures known at present. Flame ionisation detectors in parallel are used as non-selective reference detectors or the ionisation current from the source of ions is directly measured on the entry of the solute into the mass spectrometer from the chromatographic column.

2. ANALYTICAL

PART

A. The electron capture

detector

The physical basis of detection is the reaction of free electrons with molecules of gases which results in the formation of stable negative ions1g011g3. AB + e- = AB- f energy (1) (II)

AB + e- = A + B- A energy

In the case of ionisation of an inert gas-nitrogen-only electrons are present as far as negative particles are concerned. The probability of the recombination of
Chromatog. Rev., 13 (1970) I-59

18

M.KREJCi,M.DRESSLER

these electrons with positive ions is low because of their very different velocity (the velocity of an electron is approximately 10~ times higher than that of positive ions)288. In this case, only a low potential is necessary for the collection of the electrons i.e. to attain the saturation current lg3,194.If an ionised inert gas contains compounds having high electron affinities, some free electrons may be captured by the molecules of these compounds with the formation of negative ions proceeding according to reaction (I) or (II). The velocity of these anions is much lower than that of the free electrons, and the probability of recombination between negative and positive ions is, therefore, IO~--IO~ times higherlag than that between electrons and positive ions. The presence of a compound able to capture electrons will be indicated by a decrease in the ionisation current in the detector. In this case, the potential, necessary for the collection of the negative particles and attaining saturation current, is higher and proportional to the electron affinity of the compound present in the detector. For a given compound, however, this potential does not depend on electron affinity alone but also depends on the pressure, construction, and detector temperatureXg4. According to the type of potential applied, two detection methods are recognised, i.e. the so-called d.c. methodls4 and the pulse method lge. In the former case, a constant d.c. potential is applied to the detector electrodes and the detector is exposed to this potential for the whole course of the working operation. With the pulse method, a potential is applied to the electrodes in short time intervals (approximately xoo,usec) for a short period (approximately 0.5 psec). Thus for most of the working period the detector is not subjected to the potential. The scheme of the circuit connections for both methods is shown in Fig. 3.

Fig. 3. Circuit connections for the electron capture detector193. (A) d.c. mode of operation: S = source of potential zoo V; R, = I ML?; D = detector; A = amplifier and recorder; V = voltmeter. (B) Pulse method of operation : P = pulse generator, source impedance 1000 f2 or less;D = detector; C, = IOOO ,u,uF; R, = IO MSZ; A = amplifier and recorder.

The probability of electron capture by different types of molecules spreads over a range of ro6 and depends on the presence of the so-called electrophores in the molecules. Electron affinities of some compounds expressed relative to chlorobenzene are shown in Table 5. In addition to the type of electrophore, the number of bonds and eIectrophores and structure of the molecular fragment also affect the detection sensitivity. In the case of halogen compounds the detection sensitivity increases in the
Chromatog. Rev., 13 (1970) I-59

SELECTIVE DETECTORS IN TABLE

RELATIVE COMPOUNDS

GC

5
ELECTRON FOR ABSORPTION COEFFICIENTS OF VARIOUS COMPOUNDS AND OF CLASSES OF

THERMAL

ELECTRON+

Electron absorption coejicient

0.01

Compounds and classes

Electrophores

O.OI--0.x O.I--I.0 r.o--IO IO--IO0 IOO--IO00

1000-10~

Aliphatic saturated, ethenoid, ethinoid and diene hydrocarbons, benzene and cyclopentadiene Aliphatic ethers and esters and naphthalene Aliphatic alcohols, ketones, amines, aldehydes, nitriles, monofluoro and chloro-compounds Enols, oxalate esters, stilbene, azobenzene, acetophenone, dichloro, hexafluoro and monobromocompounds Anthracene, anhydrides, benzaldehyde, trichlorocompounds, acyl chlorides Azulene, cyclooctatetrene, benzophenone, cinnamaldehyde, monoiodo, dibromo, tri- and tetrachlorocompounds, mononitro-compounds Quinones, r,e-diketones, fumarate esters, pyruvate esters, diodo, tribromo, polychloro, and polyfluorocompounds, dinitro-compounds

None None .OH, .NH,, halogens .CH:C.OH, halogens .CO.O.CO

phenyl . CO.

.CO.,

.CN,

.CO.CO., ., halogens,

halogens, NO,, phenyl.CH:CH.CO* .co.co., .CO.CH:CH.CO., quinone structure, NO,, halogens

sequence Cl < Br < I; for the butylhalides, e.g., the corresponding values for minimum detectable amounts are I x ~o-ll, 8 x 10-14, 2 x 10-1~ moles/set. In addition the response is not proportional to the number of halogen atoms in the molecule, but With sterol-halogenoit increases rapidly with an increasing number of atoms 7*-80,1g3. acetates, however, the response was found 17 to increase in the inverted sequence, i.e. trichloro- < dichloro- < monochloro-compounds or Br < Cl. This anomaly is explained by the increase in induced polarity of the double bond C=O and by addition of an electron to the carbon atom of the CO group instead of to the carbon atom binding a halogen atom.
TABLE
EFFECT

6
OF THE POSITION AND THE MULTIPLE SUBSTITUTION OF ELECTROPHORES ON ELECTROW

ABSORPTIONQS

Electrophore

Compound or class

Absorption coeffccient
0.2 I

Cl

Cl*

Cl,

Cl.3

Vinylic Aromatic Aliphatic Allylic Benzylic Benzene, o Benzene, m Benzene, p . CHCl, Benzene, 1,2,3 Benzene, 1,2,4 Benzene, 1.3,; . ccl, Hexachlorobenzene

0.3 55
110

42 30 II I 113 75 60 500 1100

ChtOmUtOg.

Rev.,

13

(1970)

I-59

20

M.KREJCi,M.DRESSLER

In the d.c. method

the effect of the molecular

fragment

on the response

to

chlorobutane can be seen as an increase resulting from velocities of the electron additions. The sequence is n < bromo and iodobutane the sequence is vz < iso < sec. < In case of the pulse method the highest response is

the different stabilities and iso < ted. < sec., while for
ted.

always given by the tertiary

halogenobutane176. The responses to acetyl and alkylchlorides are considerably higher than those to arylchlorides2s8, the response to halogen bound to a double bond of ethylene or benzene is low in comparison with halogen in an allylic or benzylic position18s~1s3. Likewise herbicides, such as Diuron, Linuron etc., containing chlorine, do not show very high sensitivities126, probably due to the influence of the chlorine bond on the aromatic ring. A survey of the effect of the number and position of electrophores in a compound on electron absorption is shown in Table 6. With phosphorus pesticides, electron affinity is also dependent on the molecular structure, and increases in the systox group in the sequence

0 II

S
< P-O

P-O

II

< P-S

II

< P-S

II

ZIELINSKI et a1.301-303 tried to determine the mean relative response due to individual structural groups, and from these individual contributions to calculate the total relative response of a molecule. Their theoretical calculations are in very good accordance with experimental results. It is interesting that the detector is sensitive not only to the compounds containing halogens1ss~1s0~1s3~1s4~2ss, phosphorus and sulphur 56,106,116,223, lead75,120,1S3,195, nitrogen dioxide218s21Qand nitrates4Q+, oxygen compounds, ozone and oxygen101J8Q, but also to certain hydrocarbons such as e.g. azulene and stilbene18sJs3, cyclooctatetraene, anthracene and other aromatic compounds lss. Some examples of the sensitivity to some compounds are as follows : Parathion -I x 10-l~ moles/sec5s, tetraethyllead -3.7 x 10-l~ moles/sec75, tetrachloromethane -I x 10-l~ g/seclQO, and chloroform -3 X IO-l3 g/seclQ3. Detector response depends on detector temperature, the higher the temperature the higher the response. This increase in response is higher, however, with the d.c. method176 than with the pulse method 176,218. The higher the detector temperature, the lower is the potential necessary to attain the value of the saturation background current7sps0. This effect may be caused by changes in gas density; at higher temperatures electron collection is easier as the number of collisions with gas molecules is smaller. The maximum value of the background current, however, does not change. Maximum response does not change either; with increasing temperature, however, the potential necessary for it to be attained again decreases78,80. In the case of reaction (I), in which a molecular negative ion is formed, the energy ofelectron capture (electron affinity) is released either as radiation or is divided among other molecules during subsequent collisions. With this type of capture, the crosssection for electron capture decreases with temperature or with increasing electron energy. Dissociation with the formation of a radical and atomic or molecular negative Chromatog. Rev., 13 (1970) 1-59

SELECTIVE DETECTORS IN GC

21

ion occurs with reaction (II) after electron absorption. The increase in temperature or energylgl of the electrons may increase the probability of electron absorption. The change in response with detector temperature thus depends on the reaction mechanism. In reaction (I) the response decreases, e.g. as for azulene; in reaction (II) it increases, e.g. as for dodecylbromide 25g. A detailed analysis of the influence of the reaction mechanism on the temperature dependences has been given by WENTWORTH AND CHEN~$~,and shown in examples by ZLATKIS et al.22%304a. The maximum working temperature of the detector is, however, limited by the material of the radiation source. The most frequently used material, 3H, looses 4 ,uCi daily, but on heating above 188 almost five times as much76 3H is lost. In practice it is not recommended to use a temperature above 2oo15Q57,25* with a 3H detector. Above this temperature 226Ra, 241Am or 63Ni are used 257,259@*. The decrease in background current is very small with 6aNi; in the course of four months running at a temperature of 3oo-400 it decreased from a value 9.65 x IO-~ A by 0.8 x 10-l~ A (ref. 259). A comparison of 3H and 63Ni detectors was carried out by HARTMANN et a1.133, who found that the response of the 3H detector (detector is higher than that of the 63Ni one (detector temperature 240~) ; the response of the 3H detector was approximately higher by an order Changes in response due to carrier gas flow rate depend on tection being used. With the d.c. method response increases with rate84~85J76~253.Below a certain flow rate, however, the response temperature 20.5~) linear range of the of magnitude. the method of dea decrease in flow decreases78-80~84,85

very rapidly. The carrier gas flow rate through the detector should be higher than 100 ml/min1g3. In order to reach these velocities, a so-called scavenger gas is sometimes used; it is added to the carrier gas after the chromatographic co1umn7a--80~1g3. this In case, the chromatographic peak height is inversely proportional to total flow rate78-80. WASHBROOKE~~~showed, however, that the response increases with increasing carrier gas tlow rate. With the pulse method the tlow rate dependence is negligible54 and above a certain value the flow rate has no effect at allr76. Detector response is also dependent on detector construction58. It depends very much on the distance between the electrodes. For 8 mm and greater distances the response is constant, below 8 mm it decreases rapidly229. An inverse dependence was also found by WASHBROOKE~~~, who, in addition, found that the response disappears at a distance of 0.45 mm. With the pulse method, the response is dependent on the pulse duration and on the interval between individual pulses. With increasing pulse duration time the response increases up to a certain level and then remains constant78~80,254*25g. The same dependence holds also for the pulse period78~80~1s1,25D. The background current is within the range of 2 x IO-~ to 2 x IO-~ A54,18g~218*21g, detector noise in the range of I x IO-i2 to 7 x IO -12 A5%75,218?9. Detector response and it is the same for is linear over a range of three orders of magnitude 54,84,85,17%191 both the pulse and d.c. methods54. The cross-section for the capture of free electrons is rather small (approx. IO-l6 cm2)lBg even with highly absorbing gases. However, in the course of electron transfer through a layer of gas of I cm thickness at atmospheric pressure up to IO5 COlliSiOns with gas molecules occur. Capture probability thus very high for strongly absorbing gases, The ionisation efficiency for Parathion and effective ionisation efficiency are

is approximately

ro3 C/mole58; for

Chromatog. Rev., 13 (1970) r-59

22

M. KREJCi, M.DRESSLER

compounds containing more halogen atoms it is still higher. This high molar response means that minimum detectable amounts are very low even at high noise levels (approx. 5-10-l~ A), e.g. for butyliodide 176the level is 2 x 10-l~ moles/set. This optimum The response attains a maximum at certain voltages 8%190,218,299_ voltage is different for different types of compounds and is thus characteristic of a given compound and can serve as qualitative characteristic. With the pulse method, this means of identifying the compounds cannot be used unless the concentration of the vapours is known. Electron absorption is, in this case, determined by comparison of signals of an electron capture detector and of a quantitative detectoP3. Another method for the differentiation of compounds, which is a modification of the pulse method, was used by LOVELOCK et al. lg2. It consists in changing the energy of the electrons by applying a high frequency electric field during the time interval between individual pulses; electron energy influences the velocity of electron capture. With compounds where capture proceeds according to reaction (I), capture velocity decreases with increasing electron energy. In case of reaction (II), the velocity increases to a maximum and then decreases again. Application of such a field may heighten the response to compounds in reaction (II), e.g. to chlorobenzene, while the response to compounds absorbing electrons according to reaction (I) decreases, e.g. to benzaldehyde. A simple ionisation cell with a low potential does not work as absorption deTABLE7 FALSE RESPONSE OF THE D.C. ION CHAMBER
VARIOUS a CARRIER GASES AND TEST SAMPLES-l

ELECTRON

ABSORPTION DETECTOR

WHEN

USED

WITH

= Low concentration of a strong electron absorber; b = high concentration of a weakly absorbing compound or a low concentration of a strong absorber mixed with a high concentration of non-absorber; c = high concentration of a non-absorber.

Unwanted detection

mode

of

Carrier gas

test sanzples
a

Extent

and

nature

of CYYOYfalse wsponse z&h OY

Cross-section

Helium Hydrogen Nitrogen Argon Argon-methane

Very slight reduction None

Signal reduced Signal reduced Signal reduced greatly None Signal increased Signal increased None

Negative response Slight negative response Large negative response None Large false response False response None

Metastable atom processes (argon detector)

Helium Argon Nitrogen Argon-methane

Slight reduction None Slight reduction None None

Electron mobility effects

Argon Helium Nitrogen Argon-methane .____ 13 (1970) I-59

.._____
&O?lZUtOg. Rev.,

SELECTIVE

DETECTORS

IN

GC

23

tector onlylgl; it can also work as a cross-section detector, an argon detector, or a detector of electron mobility. The range of these detection processes depends on the gas composition, intensity of the radiation source, potential, and detector geometry, as is shown in Table 7. Traces of eluted components absorbed on the surfaces of electrodes may, under certain circumstances, be the cause of a potential which is either complementary or inverse to the potential applied lgl. This constant potential is usually of the order of several volts. If it is inverse, the chromatographic peak has an anomalously large area and often tails; if it is complementary, the response decreases and the baseline, after passing the substance through the detector, can be depressed. Electron energy, in noble gases and to lesser extent also in nitrogen, is considerably higher than the energy at thermal equilibrium for gas molecules, as the electron energy obtained from the applied field only weakens slowly due to the elastic collisions. Polyatomic gases, however, reduce electron energy by non-elastic collisions. The cross-section for electron capture changes considerably with electron energy in the case of some compounds, especially if they contain halogen atoms. If more than one compound is present in the detector, distortion of the results may occur as a result of changes in molar response. The differences in mobilities of positive ions and electrons can result in a space charge being formed in the vicinity of the cathode in the detector, the potential of this charge being inverse to the potential applied. This charge changes the mobility of the free electrons and as the probability of absorption depends on the length of time the electron spends in the detector, the response also changes. At the same time the linearity of response may change as well. By use of a carrier gas with the addition of non-absorbing material, the energy of the free electronslgl can be reduced due to non-elastic collisions. A suitable mixture is argon with 5% of methane. The addition of methane also serves as a means of removing metastable argon atoms by deactivating collisions. Thus, under these conditions the detector can neither work as an argon detector nor as a detector of electron mobility. Electron energy (and thus also the absorption cross-section of the solute) can no longer change in the presence of other vapours as it is already sufficiently low. Contact potential and space charge will, however, have a still greater effect under these conditions as electron velocity in the mixture is higher, and the potential used must thus be lower. It is obvious that the use of the d.c. method cannot remove all the detector troubles. However, they can be removed by use of a method in which recombination is more effective as a result of shortlasting application of potential. The detection sensitivity is dependent on the background current. Every stationary phase has a certain vapour pressure at a given column temperature. As even a small vapour pressure may cause change in the background current, and thus also in sensitivity, the temperature limit for use of the phases in the case of an electron capture detector is far lower than that for other detectors78~80 (Table 8). For some phases, especially non-polar ones, such as Apiezon L and methylsilicones, this effect of column temperature may be decreased by increasing the detector temperature25g. A further disadvantage of the detector is the relatively high number of parameters affecting the sensitivity of detection. The fact that the change in sensitivity
Chromatog. Rev.,
13 (1970) I-59

94 TABLE 8 INFLUENCEOF PHASE BLEI?,,INGON

.__ DETECTOR RESPONSE _~__

M. KREJCi, M. DRESSLER

__.
Maximum working
tewzperatuve (Cl

Phase

Preconditioning

.._~

._~~_~

___

-~-

With an EC detector IO0

With a conventional detector

100

Squalane Apiezon L Silicone SE-30 Silicone SE-52 Polyethylene glycol succinate Carbowax 20 M Di-n-decylphthalate Tri-z,+xylenylphosphate P,fi-Oxydipropionitrile
~~ ~~__ .__-

105
200

280 280 200 200 50 115 7o

~_._~_

16 16 16 16
20

=5o
210

16
16

170 150
II0

250 350 350 225

200

16 16

65
80

< ambient

I75 150 65

can differ for different compounds, depending on the conditions, is especially significant since changes in relative response may occur on account of this. Relative responses were found to change with potential, temperature, and pulse period, but the effect of a change in pulse time on the response was negligible. The response is approximately the same with the pulse method as with the d.c. method54,2g9, however, it is relatively independent of voltage81~218J5g and has better reproducibility i6*. Hence the pulse method obviously has advantages over the d.c. method. The sensitivity of a miniaturised detector coupled with capillary columns is somewhat higher82 than that of an ordinary detector for work with packed columns. Scavenger gas is used with a detector of this type; its minimum tlow rate is given as IO ml/min as at lower flow rates an increase in HETP82a occurs. The flow rate influences the dependence of the response on the potentialsza and on the distance between the electrodes231a. For qualitative determinations, an electron capture detector in parallel with a flame ionisation detectorgg,225,304 is often used. B. The alkali flame ionisation detector The alkali flame ionisation detector, also called a thermionic detector, sodium detector or phosphorus detector, is a modification of the flame ionisation detector. It makes use of differing ionisation processes in the flame in the presence of an alkali metal. It was found that the response of this detector to some compounds containing certain heteroatoms is many times higher than that of the flame ionisation detector ; e.g. for phosphorus compounds this increase is about 1,000 times. KARMEN~~, in one of the first papers on this detector, ascribes the enhancement of the response to augmentation of alkali metal salt concentration in the flame as a result of the increased volatility of the salt in the presence of phosphorus. Later, it was, however, found that response is also enhanced if the alkali metal is introduced into the flame in a stream of helium@?.
Chronzatog. Rev.,
13 (1970) x-59

SELECTIVE DETECTORS GC IN

25

PAGEANDWOOLLEY~~~ ascribe this effect to reactions in the flame. Alkali metal ionisation proceeds in the flame according to the reaction A+X +A++e-+X (111)

where A and X are molecules of the alkali metal and the gas, respectively. According to the above-mentioned authors the ionisation proceeds as a result of the catalytic action of certain substances (phosphorus, chlorine) according to the reaction A + zH + A+ + e- + H, (IV)

which as a result of the non-equilibrium concentration of H in the flamea leads to an increase in the ionisation of the alkali metal already present. The mechanism of this enhanced response has not, however, been solved explicitly; KARMEN~~@, in this e.g. last paper explains the response to halogen compounds as resulting from reactions on the source of alkali metal, while that to phosphorus compounds is thought to be due to reactions in the flame. Detector construction differs mainly in the manner of mounting the alkali metal salts, in heating, and in detector geometry, which all affect the detector response. The salt is usually coated on to a suitable carrier coi110g-111~248~2g5, screen157y15s or loop14s~270 on to porous metal150and is heated either by a flame (see refs. 109or III), or electronicallyl. COAHRAN~~I~~ placed a tip filled with crystals of sodium bromide on the jet of the burner of a flame ionisation detector. The stability of this detector was significantly better than that of other detectors. Further improvement in stability was achieved by HARTMANNet a3.130,131,22*, used a tip of pressed who cesium bromide. Depending on their construction the detectors can be divided into two groups. The first group contains the so-called double-flame detector (refs. I, 53,157,226,270), where two flame ionisation detectors are placed one above the other and the alkali metal salt is placed between them. The lower system works as a flame ionisation detector, and the upper one as an alkali flame ionisation detector. So-called singleflame detectors (refs. 5, 32, 97, IIO, 124, 151, 214, 215, 238, 241, 291) belong to the second group, where the salt is placed in the flame of an ordinary flame ionisation detector. Diagrams of basic types of this detector are shown in Fig. 4.

Air-

Fig. 4. Diagrams of basic types of the AFID. A = A double-flame detector15; B = a single-flame detector15 with the alkali salt fused on a loop; C = a single-flame detectorez4 with a pressed alkali salt tip.

The response value for a given compound depends on a series of parameters. In addition to those mentioned above there are the following: air and carrier gas flow rates88*109, electrode distance from the flame81277, polarity of the electrodes17,
Chromatog. Rev., 13 (1970) r-59

26 TABLE 9
OF

M. KREJCi, M. DRESSLER

DEPENDENCE

AFID

RESPONSE

ON

THE

ALKALI

METAL

Compound

Ratio40 K

A FIDIFID Rb CS

A FID NlZ

responses K
10-I 102 5.9

(Clmole)88
Rb
x 100

cs

N compound P compound As compound

30 10 000 5

60 II 000
IO

150 12 000 30
A.

3.5 x 2.1 x

6.4 x 10~

1.3 x 101 8.1 x 102

1.7 x 101
I.2 x 103

a Background current = 6.10-f

148369,270, jet diam&+@J46, car&r gaslOO,l46, and the effect of the anion of the salt being used179as. The alkali metal8,89,96,100,112,146,148,158 the hydrogen flow rate8J7J0gJ57~177J77 and

have the greatest influence on the response value. The response increases on increasing the atomic number of cation89*146 (Table 9). Small changes in the hydrogen flow rate affect the response value considerably. The amount of hydrogen determines the flame temperature and, therefore, also the temperature of the alkali metal salt. This means that on increasing the hydrogen flow, the background current increases as a result of stronger emission and higher ionisation of the alkali metal salt. It was founds8 that under constant conditions (air

Fig. 5. Plot of AFID ionisation efficiency against background currenta8. N compound; 3 = C compound; 4 = Cl compound; 5 = S compound.
Chromatog. Rev., 13 (1970) I-59

P compound;

z =

SELECTIVE

DETECTORS

IN

GC

27

and carrier gas flow rates, jet diameter and detector geometry) and if the background current is maintained at a constant value, the detector response is not dependent on small changes in the hydrogen flow rate which compensate the changes in background current caused by the leak of alkali metal salts with time and on the distance of the collector electrode from the flame. The increase in response with increasing hydrogen ilow rate, therefore, may be connected with the increase in background current, Changes in direction (polarity) of the responses9 are also connected with an increasing value of the background current. Such changes for compounds containing phosphorus, nitrogen, chlorine, sulphur and hydrocarbons, and a potassium salt are shown in Fig. 5. The response to all these compounds at first increases, but that to compounds containing chlorine and sulphur and to hydrocarbons first reaches a maximum and then acquires negative valueP at a certain value of background current depending on the heteroatom of the solute and on the cation of the salt used. The response curves for other cations are similar, only with chlorine-containing compounds and sodium as the alkali salt the response increases continuously. Table IO shows the ionisation efficiencies for compounds with different heteroatoms, obtained under optimum operating conditions. The alkali flame ionisation detector is selective to phosphorus compoundslos, 111~157J60,267~276, halogen compounds74J0sJ57~267 (with the exception of fluorine), arsenic146J4s, nitrogen~~66~88~s8~132~146~2s2, tin14s, and sulphur compoundsso~91. The selectivity s (9) for phosphorus compounds, in the case of a flame ionisation detector, increases up to a value of 103-104 if salts of any of the alkali metals (Na, K, Rb, Cs) are used. There is a selective increase in the response in the case of nitrogen compounds with all alkali metals except sodium 89,146. Molar response is essentially independent

TABLE

10
ALKALI FLAME IONISATION DETECTOR

SENSITIVITY OF AN

Compound

Ionisation efficiency (Clmole) Double-jlame detector@ Single-flame detector

Reference for shgle&me detector

O,O-Diisopropyl methylphosphonate DDVP Disyston Triethylarsine Tetrapropyltin Thiophene Thiophane Hexyl hydrosulphide Pyridine a-Methylpyridine Acrylonitrile Chlorobenzene Bromobenzene 4-Bromotoluene /3-Bromostyrene

1.3 x
I.5 x I.9 x

IO* 108 IO=

2.2 -

102

88

2.3 x 10-l -7.0 x 100 4.5 x 10-z -

2.3 x 10-l
-

-6.0 -5.7 -6.1 4.6 4.8 4.8

2.4

x IOO x 100 x 10~ x IO x 100

x 10~ Id IO0 10~ IO0

91 91 91

*7a
87 87 92 92 92 92 13 (1970) r-59

I.6

100 100 10~ 10-l

I.4 x x

3.4 x 2.3 x 7.0 x

2.5 x
2.2 x

Chrwnatog.

Rev.,

28

M. KREJCf, M. DRESSLER

40-100 times higher than with an of compound structure146 and it is approximately FID. Data up to the present time show that the AFID response to halogen compounds appears to be very much dependent on the detector construction. JANAK AND SVOJANOVSK.';'~~* and KARMEN~~~found that the detector is selectively sensitive to these compounds when salts of all alkali metals are used, while GIUFFRIDA et ~1.l~~found that with the use of KC1 or KBr the response to halogen compounds can be depressed. The response of an alkali flame ionisation detector with a jet tip of pressed salt can be even negative92,130,75,15a to halogen compounds under certain conditions. Increase in the selective response, compared with the FID, for chloro- and bromo-compounds it only occurs with only occurs in the case of sodium saltss2, with iodo-compounds
a potassium salt. Selectivity to sulphur compounds is manifested, not only in the increase in the response (s = IO to 20) but also in the direction (polarity) of the response. In the case of potassium, rubidium and cesium salts, the response is negative, i.e. a decrease in ionisation current occursoolsl in the detector. The upper system of a double-flame detector is highly selective to compounds containing phosphorus and halogens (except for fluorine). It is not possible to say, however often it may be the case, that it is sensitive to the above-mentioned compounds only. Sensitivity to other compounds depends on the function of lower system The solvent for example always gives a and on the type of the cation used 14*1l~~. response. Each of the systems of the double-flame detector has its own electric field. Experimental work has shown that these two fields influence one another and that they can distort the performance of both detectors148~26g~270. The effect of column temperature on detector sensitivity was studied and it was found that : (I) with decreasing temperature (and therefore with increasing time of solute passage through the jet of the flame ionisation detector) the response value decreases, (2) the curves of the upper system are always narrower than those of the lower one, and (3) that narrowing of the elution curve and loss of sensitivity are caused by the action controlled by the relation holding for diffusion of the gases. This finding explains the different ionisation efficiencies of monobromo-compounds and the different contributions of individual chlorine atoms in mono-, di-, tri-, and tetrachlorobenzene, when ionisation efficiency always decreases in the sequence of increasing elution volumes140. Ionisation efficiencies of monobromo-compounds and chlorobenzenes are equal or are a multiple of the number of heteroatomsg2 in the case of a single-flame detector. This detector is, however, sensitive to all compounds which can be detected in an ordinary flame ionisation detector though the sensitivity in this is always lower. Selective enhancement of the response, however, occurs not only with halogen and phosphorus compounds but also with compounds containing nitrogen and sulphur. With a single-flame detector with a jet tip of pressed alkali metal salt, the noise is considerably lower than with a double-flame detector and the minimum detectable amount is, therefore, also lower at approximately the same ionisation efficiency. With this detector type the value and direction (polarity) of the response are strongly dependent on the type of alkali metal cation and on the background current. By suitable selection of the experimental conditions, it is possible to achieve a selectivity
Chromatog. Rev., 13 (1970) I-59

SELECTIVE DETECTORS IN GC.

29

of response to a given heteroatom not only by an increase in the selectivity s (9) but also by a change in the direction (polarity) of responsess~g1J2J75J75a. The ionisation efficiency of this detector is considerably higher than that of other ionisation detectors. When a cesium salt is used, it reachesa a value of approximately 2 x 10~ C/mole (2 %) for phosphorus compounds. This means that the absolute response is 2-3 orders of magnitude higher than that with the flame ionisation detector. However, detector noise is also higher by 2-3 orders of magnitude. The minimum detectable amount is, therefore, comparable with that of the flame ionisation detector. The disadvantage of both types of alkali flame ionisation detector is the decrease in sensitivity with time resulting from loss of the alkali metal in flame. The velocity and value of this decrease depend considerably on the geometry and the way in which the salt is placed in the flame. The rate of this decrease can be considerably lowered with some types of detector130,131,224, if at the same time the decrease in backand ground current is compensated by a change in hydrogen flow, it can, for a certain period of time, have a zero value*.
C. The surface ionisation detector

The surface ionisation detector (thermionic) makes use of an effect described by KINGDON AND LANGMUI@~P~~~ and was used as a leak detector by RICERS. The effect consists of emission of positive ions of an alkali metal from a heated electrode, the material of which has a higher electron affinity than is the value of the ionisation potential of the alkali metal. In the presence of halogens and in oxygen media, the emission of positive ions increases. According to MOESTA AND SCHUFF~~~ the increase in positive ion emission is caused by the fact that a complex, Cl-K+-0, is formed on the surface which changes considerably the work function. This detector was first used in gas chromatography by CREMER et a1.6g (Fig. 6) and it is usually called the thermionic detector6Q7.
3

Fromcolumn
Fig. 6. Diagram of a surface ionisation detector.
I=

Cathode;

anode; 3 = heater.
13 (1970) I-59

Chromatog. Rev.,

30

M.

KREJCf, M. DRESSLER

and to some It has been found sensitive to halogen compounds 66,67,69,70,74,179,210 210. Sensitivity to chlorine is giverPg organophosphorus pesticides containing sulphur as 3 x 10-10 g/set; the minimum detectable amount of tetrachloromethane is 1.5 x to mercaptans and hydrogen disulphide is approximately IO-lo g/secB3, sensitivity IO p.p.m.l*_ The response is independent of the type of chlorine atom bond and molecular structurejg. It was foundjhowever, that the solvents used in a large excess with respect to the halogen compound- s caused changes in the baseline70 after having passed through the detector. CREMER et al. 70 introduced a so-called pre-combustion removing all these effects and also improving the reproducibility of the response. At the same time this pre-combustion decreases sensitivity and increases noise. Molar responses of mono-, di-, tri-, and tetrachloromethane are in the ratio I :z:3:4 (ref. 18). Ratios from I :z up to I :2.2 were found for mono- and trichlorobenzene70, but after pre-combustion, the theoretical value of I :3 was reached. Detection sensitivity depends on the temperature to which the wire is heated (Table II) and is thus connected with the background current210.
TABLE
CHANGE WITH

11
IN THE RESPONSE OF A PLATINUM OF FILAMENT THERMIONIC HEATER DIODE TO SOME PESTICIDE COMPOUNDS

INCREASING

INCREMENTS

CURRENT=l

Pesticide

Injected CM?)

Filament measured 1.7 A

current and re.sponse as by peak height in mm 1.8 A

30 32 '7 26

1.9 A
91 116 72 97

Lindane Heptachlor Aldrin Telodrin Kelthane Heptachlor epoxide +,fi-DDT Dieldrin Methoxychlor Parathion Malathion Trithion

1.8 3.8 3.6 3.6 1.1 3.6 3.6 9.0 4.0 8.0 8.0 1.6 4.0 8.0

x x x x x x x x x x x x x x

10-4 IO-~ IO-~ IO-~ 10-4 10-4 IO-~ IO-~ 10-s 10-S 10-a 10-3 IO-~ 10-3 IO-~

IO '5 7 II

3.6 x

7
II 4 4 13 0 0 -a

I4
22 9 9 30 0 0 4

75
95 40 39 90 0 0 8 13

7 -

'7 -

::

a Dash indicates that no observations

were made under these conditions.

With increasing background current (higher temperature) the response increases but at the same time the detector noise also increases so that there is no sense in increasing the current above a certain value (differing with the age of anode)*. As a result of strong dependence of the sensitivity on temperature, the detector must be thermostated with accuracy i 0.5%r*@. The response depends on the type of carrier gaP, probably on account of the different thermal conductivities, on carrier gas flow rates3, and on pressure18*6g. At low pressures, the sensitivity is 5-10 times higher. Detector response is linear over a range of 4-5 orders of magnitude70~s3. ChVOWLatOg. &TV.,
I3 (1970) I-59

SELECTIVE

DETECTORS

IN

GC

31

As the molar response of this detector is independent of the type of halogen atom bond and molecular structure, and as it is a multiple of the number of atoms in a molecule, the response of more compounds can be forecast from one calibration. Relatively high selectivity is a further advantage of the detector. The essential disadvantage is the time instability of the detectorll. Sensitivity depends very much on the age of the anode 18.The molar response ratios for compounds containing fluorine, chlorine, bromine, and iodine is 0.9:1 :o.8:0.1. These ratios, however, also change with time. It is true that chlorine always has the highest value but the response can decrease to zero for fluorine, and can be nearly equal to that for bromine in the case of iodine. New anodes show non-linearity in response for a certain period of timen. The detector also has a relatively high time constantl reaching values of 10-20 seci8,69.
D. The flame photometric detector

The principle on which the flame ionisation detector is based consists in the photometric detection of the flame emission. Any flame photometer adapted to a given chromatograph and placed behind the chromatographic column can serve as a detector. The coupling of a chromatograph with a photometer has been described in detail by BRODY AND CHANEY~~ and JUVET AND DURBIN~~.An oxygen-hydrogen flame is used for excitement, and nitrogen or helium as carrier gas. The first use of flame photometry as a means of detection was the application of Beilsteins test for halogen determination125~g3~217 (with the exception of fluorine). A copper wire is placed in the flame and in the presence of halogenides the flame turns green. The sensitivity of this method was in the order of micrograms. Later, this method of detection was used in gas chromatography for the determination of metal chelatesg4~154~300. e sensitivities to individual elements are Th shown in Table 12, together with the appropriate wavelengths. Sensitivities are
TABLE
LIMITS

12
OF DETECTION FOR THE FLAME PHOTOMETRIC DETECTOR156,300

Emission wavelen$h ImpI MOF~ WF.9 SnCl*

Al(tfa),
C&b

Limit of detection (moles) j ; ::I::

520.0
520.0

358.0
486.0

7 x IO-*
5 x 10-9

CH,COCH, TiC14 AsCl,

ZrCll Rh(hfa), Cr(hfa), CO,

431.0

431.9 544.9 500.0

564.0
369.2 425.4 431.5

2 x 10-6 4 x 10-n 2 x 10-o

2 x
10-S

I x 10-B

1 x 10-11 I x 10-10 7 x IO-

Chromatog.

Rev.,

13 (1970)

I-59

32

M.KREJCi,M.

DRESSLER

expressed as the number of moles giving a signal double that of the noise level on passage of the compound through the detector. It can be increased by up to two orders of magnitude by improvement of the optical system300. By suitable selection of the slit width and the wavelength, the detection of emission of the element only may be obtainedi55. For example, in the case of volatile chromium chelates at 425.4 m,u even a ten-fold excess of iron chelates having the same elution volume is not detected. Likewise, chromium compounds have no effect on the detection of iron compounds at 372.0 rnp. As this detector is often 102-104 times more sensitive to metallic compounds than to organic ones, it is relatively insensitive to organic impurities and to bleeding of the stationary phase. Phosphorus and sulphur compounds (mainly insecticides and pesticides26,36,37,107,129,140,260) from organic compounds have been determined by means of a flame photometric detector. In this case 39 the flame is screened from direct view of the optical system and emission from compounds, which do not contain the heteroatoms mentioned, occurs inside the screened space of the flame on their combustion. If a compound contains phosphorus or sulphur atoms, the emission appears above the flame screen and this light is detected. This arrangement leads to high detector selectivity in spite of the fact that carbon monoxide and hydrocarbons also show an emission at the wavelength used for phosphorus. The sensitivity to phosphorus compounds, e.g. Parathion, is 5 x ~o-~~g/sec, which is 5 x IO-r3 g/set of phosphorus at 526 m,u, using an interference filter. The sensitivity to the same compounds is 0.6 p.p.m. at the wavelength specific to sulphur, 394 m,u. Sulphur compounds also give a response at 526 m,u. The response under these conditions is 5510% of the sulphur response at 394 m,u. The phosphorus compounds response26 is 10~ to 10~ times higher than that of compounds which do not contain phosphorus. In the case of compounds containing both phosphorus and sulphur atoms, the simultaneous detection of both the elements can be carried out by using two different interference filters and two optical pathways 36+22. Sensitivity to phosphorus is 800 times higher at 526 rnp than at 394 m,u; sensitivity to sulphur is 22 times higher at 394 rnp than at 526 m,u. It was found that the ratio Rp/dRs, where Rp is response to phosphorus and Rs response to sulphur, is with use of a dual system of FPD proportional to the contents of phosphorus and sulphur in a molecule 36. Thus amounts of the heteroatoms in a molecule can be directly estimated from the ratio of the response values. In connection with this it was found36 that for compounds having P = 0 or P = S groups in the molecule, the ratio R&IRS is essentially lower for all compounds having an SO group (sulphoxide) than that for those having SO, (sulphone) or S (sulphide) groups. It was also found36 that response of Imidoxone (with a P=O group) is lower than that of an equal amount of Imidane (P=S group). A carrier gas flow of up to 160 ml/mina$ has no effect on the detector sensitivity. Detector noise is approximately 2 x 10-10 A with the use of a P-filters9v265 at a background of 1.7 x 10-s A, and 1.5-4 x 1o-l0 A34,3gwith the use of an S-filter at a background of 2.2 x IO-* A. Experiments with non-stoichiometric ratios 0,/H, (1.22) in the flame showed that the noise is lower under these conditions and the minimum detectable amount is, therefore, also lower 3o0. Detector temperature can be as high as 250 (ref. 73). The detector ChtrO?MtOg. &V.,
13

response is linear to phosphorus

(1970) I-59

compounds

over a range of 3-4

SELECTIVE DETECTORSIN CG

33

orders of magnitude25133@, and to sulphur compounds the response is linear with respect to the square36,3gof the concentration. Beilsteins test has recently been applied to the determination of halogens in more sensitive manner3a; the emission of an oxygen-hydrogen flame burning above a copper screen at 526 m,u is picked up. The response to halogen compounds is one to two orders of magnitude higher than that to other compounds and the value of the response increases in the sequence I < Br < Cl. A detection systemz19 has been described for the selective determination of silicon compounds in which the emission of an oxygen-acetylene flame at 2516 k or the absorption of an acetylene-nitrogenous oxide flame at the same wavelength is measured. The emission from an oxygen-hydrogen flame was measured in all previous cases, AUE AND GEHRKE~ and later NOWAK AND MALMSTADT~~~measured flame emission in the presence of alkali metal salts. The detector is essentially an alkali flame ionisation detector with the only difference that instead of ionisation current the alkali metal emission at the appropriate wavelengths is measured. While AUE AND GEHRKE~ found a decrease in the emission for halogen and phosphorus compounds found both a decrease and an increase in the in all cases, NOWAK AND MALMSTADTa23 emission of sodium at 589 m,u depending on the hydrogen flow. Sensitivity and selectivity of this detector is obvious from Table 13. Response to halogen compounds (with the exception of fluorine) is approximately three orders of magnitude higher than that to compounds which do not contain halogens. Response to phosphorus compounds is only approximately an order of magnitude higher; the ratio is thus inverted to that for the AFID. TABLE
RESPONSE

13
OF THE FLAME PHOTOMETRIC DETECTOR IN THE PRESENCE OF AN ALKALI SALT-

Compound

Response (C/mole) 0.128 0.154 0.135 0.090 0.051

0.012

n-Pentane n-Hexane n-Heptane n-Octane Acetone Methanol Ethanol I -Propanol Ethyl bromide Ethyl iodide Methyl iodide Methylene chloride Chloroform Carbon tetrachloride 0.01 o/0 Carbon disulphide o.Io~/~ Carbon disulphide o.Io% Diethyl ether I .o% Diethyl ether o. I o 0/0 Methyl formate I .o oh Methyl formate IO o/0 Diethylamine o. I o o/o Trimethyl phosphate

0.032 0.037 460 681 606 172 339 492 0.542 0.383 0.173 0.032 0.362 0.133 0.031 5.390

Chvomatog. Rev.,

13 (1970) I-59

34

M. KREJCi, M. DRESSLER

The detection is based on the energy emitted from the products of processes which occur in the flame in the presence of different materials. Selective detection of this detector response depends on the wave dependence of the emission of atoms, molecules, ions, or groups of atoms. If it were possible to find an emission line or a band selective for every functional group or heteroatom, this detector would have a high degree of selectivity. In practice, this selectivity is somewhat limited by the flame background and by the fact that emission spectra overlap. It can so happen that at a wavelength optimum for a certain element another element or group is also detected. This occurs particularly when interference filters with a broad width of spectral bands or slits with large widths are used. JUVET AND DURBIN~~~list certain interfering materials for a slit width of 0.3 mm and at the wavelengths 425.4 and 372.0 rnp in the determination of chelates of Cr and Fe. These difficulties, however, can be removed by use of narrower slits and monochromators. As the response to sulphur compounds is exponential with respect to concentration, the response can be increased by introducing a certain amount of sulphur dioxide into the flamel and the detector can thus be made to work in more sensitive parts of the curve. Under these conditions the detector has a certain background emission the value of which depends on the amount of sulphur dioxide being introduced. The value and sense (polarity) of detector response depend on the value of background emission (Fig. 7). By suitable choice of the background emission, as with the AFID, a positive

c,.,

40

80
I

I.,

120 160 [A
,,

Fig. 7. FPD response as a function of background luminescence intensityl. h = The peak height. I = zoo p,p.m. CH,Cl,; 2 = I p.p.m. CS,; 3 = I p.p.m. CS,(with a glass shield) ; 4 = 1300 p.p.m. n&H,, (with a glass shield); 5 = 2000 p.p.m. iso-PrOH; 6 = 1300 p.p.m. n-C,H1p; 7 = zooo p.p.m. EtAc. Chromatog. Rev.,
13

(1970)

r-59

SELECTIVE DETECTORS IN GC response to some types of compounds compounds is negative. can be obtained while the response

35 to other

A great advantage of this detector is the possibility of the simultaneous detection of more than one element by using several sensing elements, for example the determination of phosphorus and sulphur in a molecule of one compound36,122. In this case a separator, which can be a source of error, need not be used. Two electrodes may be placed in the detector at the same time and they can pick up the change in electric conductivity of the flame with respect to the individual elements without any mutual influence122. Since by selection of the appropriate slit width and wavelength high specifity may be reached, it is not necessary to purify solutions in advance in pesticides analysis. E.g., when determining nanograms of organophosphorus pesticides, chloro-compounds, even in microgram amounts, do not interfere. For the same reason, a serious increase in base-line does not occur3g in temperature-programmed chromatographic analysis. This detector is also suitable for the determination of inorganic compounds on account of its corrosion resistance. In the course of many years of operation300 no detector corrosion was noticed even when the burner was maintained at a temperature above the boiling point of metal halogenides under analysis. The disadvantage of the detector is the very expensive monochromator equipment required for the high resolution of wavelengths to give a high detection selectivity.

E. Emission qbectrometry
Detection by means of emission spectrometry is based on the same principle as that by flame photometric detection (FPD), only as emission source in this case serves plasma of the electric discharge. The most frequently used type of electric discharge is a 2450-MC (ref. 204) electrodeless discharge. The intensity of emitted spectra with this discharge is higher than with high voltage alternating and direct current glow discharges, direct current discharge with a hollow cathode, and S-MC electrodeless discharge. Sensitivities to individual elements expressed as minimum detectable amount and as wavelengths at which the detection of a given element is selective and the socalled selective ratio (ratio of responses to a given element and a hydrocarbon) are shown in Table 14. The differences in sensitivity to phosphorus compounds (first of Table 14) are caused by the type of bonds and by the different properties of the groups bound to the phosphorus atom lo. In the second part of the table the sensitivities to other elements, with the use of a monochromator and a slit width of 25 p and with argon as carrier gas, are shown. Under these conditions, sulphur, chlorine and bromine show band spectra at the given wavelengths; line spectra have not been noticed204. BACHE AND LISK~~ used helium instead of argon and found emission lines at which sensitivity and selectivity are higher than in the case of argon for the above-mentioned elements (part 3 of Table 14). These differences are explained by the higher metastable energy of helium and by a more intensive plasma source 14. MoYE~~~, however, found that the optimum composition of the gas, regarding the ratio of signal to noise and detector selectivity, is 15% argon in helium in the case of phosphorus compounds. Chromatog. Rev., 13 (1970)
I-59

36
TABLE 14

M. KREJ%, M. DRESSLER

.sENWrIITY OF *MIssIoN SPEcTRoMETRY Element Conzpound Wavelength (A) Detection limit (&?l=cl 6.1 4.4 1.1 1.5 3.7 I.3 1.5 I.3 I.7 5.7 9.4 3.0 2.2 1.0 I.3 4.3
2.4

Reference

Selectivity ratio

P P P P P P P P P P P P P P P P P F Cl Br I P S Br Cl I P S

Ciodrin Diazinon Dibrom Dimethoate Disyston Disyston sulphoxide Disyston sulphone Ethion Malathion Methyl parathion Parathion Phosdrin Phosphamidon Ronnel Systox Thimet Trithion Hexafluorobenzene Trichloromethane Tribromomethane Iodomethane Triethyl phosphate Carbon disulphide Various compounds Various Various Various Various compounds compounds compounds compounds

2535.65

x x x x x x x x x x x x x x x x
x

IO-*~

IO IO IO IO IO IO IO IO IO

IO-la 10-11
IO-la

10-12 10-11 10-11

10-12

IO-la
10-12

IO IO IO TO IO IO IO IO

10-13

10-12 ro-11
10-12
10-11

10-12 Io-'a

2516 2788 2985 2062 2555 2575 4785.3 4794.5 5338.2 2535.7 5453.8

5.0 x 8.0 x
2.0 7.0 1.0 I.0 x x x x

10-10 10-l" IO-' 10-14 10-11 10-9

204 204 204 204 204 204 13 r3 13 13 13

20 ZIS.n-hexane 20 IO 104-10' IO0 IO0

I.3 x 4.0 3.4 6.0 3.4

10-11

x 10-11 x IO-r1 x 10-l~ x 10-11

38 US.phenanthrene 44 38 1000
22

Detector response is significantly dependent on the microwave output power. The course is again dependent on the wavelength at which the element is measured (Fig. 8) and it is of fairly different kind. Some of the differing values of detector sensitivity could be explained by these dependences ; e.g. in the case of ioxynilll the sensitivity to iodine is given as 4.1 x 10-l~ g/set while for methyliodidezo4 it is 7 x IO-r4 g/set. The dependence of the response on pressure for phosphorus compounds is shown in Fig. g. response appears to be in the range of pressure of approximately with atmospheric pressure, by approximately an order of magnitude. The effect of pressure on the response to iodocompounds is much less even though the response maximum occurs in the same range12. MCCORMACK et aLzo4 showed that the response is dependent on the carrier gas flow and on column temperature. MOYE 220, however, found that when a mixture of 85% He and 15% Ar was used the detector was nearly insensitive to these parameters.
ZOO mm Hg and the response is higher, on comparison

The maximum

For each column temperature Chronzatog. Rev., 13 (x970) r-59

and flow rate used an optimum

power setting at

SELECTIVE DETECTORS IN

GC

37

50

100

(Watts)

Fig. 8. Effect of microwave power output on response *ad. R = Response (arbitrary unit). I = 2788 A; 3 = r,6dimethylnaphthalene, r-Chloropropane, 2788 A; 2 = carbon tetrachloride, 3883 A; 4 = n-heptane, 3883 A; 5 = r-chloropropane. 3883 A; 6 = chloroform, 2788 A; 7 = r,2-dichlorohexafluoropentene-r, 3883 A; 8 = ethyl iodide, 2062 A.

which the signal to noise ratio is maximum 10 for a given compound exists. This optimum power setting changes with the discharge tube geometry. Higher temperatures and higher flow rates usually demand a higher power setting. At a given power setting the response decreases sharply on increasing the inner diameter or thickness of the tube wall. Thick walls probably absorb more emitted radiationlO. Detector response linearity is approximately 4 orders of magnitudeg*2M. BRAMAN AND DYNAKO~~ studied an emission detector in which the discharge

16

Fig. Q. Effect of pressure on the response and base line of emission spectrometeris. h = The peak height; x = base line shift; p = pressure. I = Dimethoate; 2 = Thimet; 3 = base line. Chromatog.

Rev., 13

(1970)

I-59

38

M. KREJci,

M. DRESSLER

was caused by a direct current in helium. Sensitivity for compounds containing chlorine, bromine, and iodine is in the range of I x m-10~ C/mole depending on the type of compound and on the wavelength being used. What has already been said on selectivity in case of a flame photometric de-

tector essentially holds for emission spectroscopy. The selectivity is again influencedzo4 by overlapping of the spectra, by source background, monochromator dispersion and the slit width. The narrower the width of the slit, the higher the selectivity, however, the lower the sensitivity. E.g., with a slit width of 6 p the selectivity to the iodine line at 2062 A is approximately 3 orders of magnitude higher than that with a slit width of 50 ,H (ref. 204). The effect of slit width on the signal to noise ratio and on the selectivity to phosphorus (expressed by the ratios of responses to Parathion and Lindane) is shown in Fig. IO. When investigating optimum wavelength for the de-

400-

350-

300-

250-

zoo-

150-

IOO-

50xhJ:

20

40

60

00

,oo:,o-

Fig. IO. Effect of slit width on Parathion/Lindane selectivity ratiozaO.s = Selectivity ratio; x = slit width.

termination of sulphur compounds, it has been found that for different sulphur compounds the optimum wavelengths72& are also different. The sensitivity of this detector in comparison with an FPD is, however, higherzo4. Repeated passage of solvent through the detector; often causes deposition of carbonzo4. This difficulty may be resolved by igniting the discharge after the solvent has passed throughlO. This procedure, however, excludes compounds from chromatographic analysis having small elution volumes, especially when the discharge delay is up to 2 min and the solvent still tails after this time.

F. S$ectrojhorometric

detection

In this case, the compounds leaving the chromatographic column are absorbed by a stream of ethanol; the carrier gas escapes into the air and ethanolic solution is passed through the flow cell of the spectrofluorometer35.
Chromatog. Rev.,
13 (1970) 1-59

SELECTIVE DETECTORS IN GC

39

It is obvious that such a detector is only suitable for fluorescing compounds. By the suitable selection of the wavelength, the maximum response to a given compound, and virtually none to other compounds in the mixture, can be achieved. The response depends very much on the flow rate of the solvent--ethanol. With an increasing flow rate the response decreases, however, the chromatographic band broadening also diminishes. A suitable flow rate for solvent, which is a comprise, must therefore be selected. The minimum detectable amount for $-terphenyl is 4 x 10-l~ g. The imperfection of the detector is incomplete quantitativeness of sample transfer into the cell. In case of substances with low boiling points or substances poorly soluble in alcohol, considerable losses must occur. G. The ultraviolet s$ectrophotometer detector

Separated components are transferred in the stream of carrier gas through a heated tube to the cell of an ultraviolet spectrophotometer. The carrier gas used may be hydrogen, helium, nitrogen, or one of the noble gases, all of which have negligible absorption at wavelengths higher than 1400 Alal. If the wavelength of an ultraviolet spectrophotometer is constant and if the transmittance is measured as a function of time, the spectrophotometer works as an ordinary detector, i.e. it records ordinary elution curves. Detection selectivity is given by the selection of wavelength and by the ability of the substances to absorb at the selected wavelengths. E.g. MERRITT et al. 213 determined aromatic substances at a wavelength of 2537 A; paraffins and naphthenes do not interfere at this wavelength.
FRANC AND JoKL~O~P~ used this detection rated mixture of m- and P-xylenes. a record can be taken as a function spectra of individual spectra of the compounds. components of the wavelength. It is obvious eluted In this case is obtained for a given range of wavelengths and selectivity that in order to In addition method for the determination of an unsepa-

the spectrum of a compound is given by different determine the complete

in a chromatographic in such a way

analysis the spectrophotometer that the scanning

must have a scanning time which is as short as possible. DU spectrophotometer 1600-2100 A lasts 6 sec. Another

KAYE AND WASKA~~~~~~~ modified the Beckman possibility is the adjustment

over the range of wavelengths

of the carrier gas flow to the time necessary for spectral spectrophotometer and one of the main

analysis102p103. The disadvantage gas chromatographls2. of the ultraviolet reasons for its rare use is the high price, which is 5-20 times higher than is that of a

H. The infrared spectrophotometer detector For the characterisation of organic molecules the infrared range of the spectrum is of greater importance than the ultraviolet. Direct coupling of gas chromatography with IR spectrophotometry is, however, a relatively new technique. It was first used
by HAAHTI AND FALES~~. As in UV spectrophotometry, one can also work either at a constant wavelength

or determine the whole spectrum of a compound in IR spectrophotometry. Considerable selectivity can be achieved by the suitable selection of the wavelength. In the determinatiorP6 of o-, m-, and p-xylenes at the wavelengths 13.70 p, 13.20 p, and
Chromatog. Rev., 13 (1970) I-59

12.55 p the ratio of sensitivity to the component being determined and to that not being determined is ZO:I. When determining 266the carbonyl group content at 1739 cm-i this ratio is IO,OOO:I for acetone and o-xylene. With standard IR spectrophotometers there is a significant difference between the speed of scanning the whole spectrum and that of the chromatographic peak record. If during the passage of the peak through an IR cell the spectrum of a given compound is recorded, the vapour concentration of the spectrum changes so significantly during the recording that the transmittance of one end of the spectrum is distorted relative to the other. This distortion can be removed by different techniques of analysis.
SENN AND DRUSHEL~~~ always analyse only one component of the mixture with the IR spectrophotometer. By use of spectrophotometers with a short scanning time, the distortion can be practically eliminated and all the components of the mixture can be analysed. Times of spectrum scanning in the range of 2.5-15 ,u have been given as 45 sec2g7 or 5 sec30 in the range 2.7-9 p, 0.5 seclO, and in the range of 4-40 p even I seclg6~lg7, Another possibility is the use of two spectrophotometers in parallel, one covering the range 2.5-7 ,u and the other the range 6.5-16 ,u. The complete spectrum can then be obtained in 16 set 16.Another way is the interruption of the chromatographic

elution for the analysis of each component of the mixture by the IR analyser25512g3. This method of detection is not applicable to capillary columns as the necessary detector volume is too large and detection sensitivity low. From this reason BEHRENDT~O and BEHRENDT AND RICHTERING~~suggested another method of detection for capillary columns. The sample is converted into a beam of molecules which is irradiated. When the molecules absorb the radiation their rotational quantum number changes and this causes their deflection from the main beam which is detected by the detector. In this case the absorption cross-section of molecules for the radiation is measured and not the absorption of radiation by the molecules, that is, the effect of radiation on the sample is measured and not the effect of the sample on the radiation. A detailed description of individual methods for the use of infrared spectrophotometry in the analysis of compounds eluted from a chromatographic column, including absorption methods, has been given by LITTLEWOOD~~. The disadvantage of this detector is the relatively high price of the IR spectrophotometer and the low detection sensitivity. The least amount usable for detection at constant wavelength is 0.01 ,ul266. Further difficulties occur in the determination of the whole spectrum. Detection sensitivity is at least an order of magnitude lower. The spectra of gases differ somewhat from those of liquidsls7. With hydrocarbons and other substances of low polarity these differences are small. Generally, however, the spectral lines of gases are broader than those of liquids and the extinction coefficient of gases is in consequence of this broadening lower. Furthermore, a small shift in the frequencies can sometimes occur between the spectra of these two phases. With polar substances and especially with the substances with hydrogen bonds the differences are higher; e.g. the spectra of alcohols in the liquid and gas phases differ considerably. The spectra of the liquids are, in the main, the spectra of polymers while the gases give spectra of monomers or polymers of a lower degree. The distortion of the spectrum, resulting from concentration changes during the passage of a compound through the cell, can be removed by the use of high-speed scanning spectrophotometers. The time of 5 set is sufficiently short for the concenChromatog. Rev., 13 (1970) 1-59

SELECTIVE DETECTORS IN

GC

41

tration changes24gto be neglected. However, with a shorter time of scanning, spectrum resolution is worse and there is the danger of spectrum distortion resulting from omitting a certain part of the spectrum. Further difficulties follow from the cell volumels7 size. If the cell volume is smaller than the volume of gas in which the component under determination occurs in the chromatographic peak, only a part of the peak is analysed. If the volume is larger, two components may overlap and the separation of the two peaks is worsened. I. Mass spectrometry The combination of mass spectrometry with gas chromatography is a technique in which a part of the effluent is continually transferred from the chromatographic column to a mass spectrometer. The amount of effluent which can be introduced into a mass spectrometer is determined by the highest acceptable pressure of the analyser and of the ion chamber. This pressure should not exceed IO-~ torrP.
Capillary column

Mass

spectrometer

Packed capillary

or Mass column spectrometer

Molecular Packed or

separator

Fig. I I. Diagram of gas chromatographic

connections

to the mass spectrometePB.

Thus, the most important part of the combination is the connection of the separation column with the source of ions in the mass spectrometer, i.e. the transfer from atmospheric pressure into a vacuum. It can be practiced essentially in three ways (Fig. II): (I) Direct connection of the column outlet with the ion source11~~20~~20g~213~~272~ 2s7,2g6. this case the column outlet leads directly into the vacuum. As a result of In the limited entrance flow of the gas into the mass spectrometer this connection is limited, practically, to capillary columns. (2) Leak connection15~41~57*g5~1a5~183. Th e advantage of this connection is that the position of the column outlet is such that it is under atmospheric pressure. The disadvantage is its application to capillary columns. In the case where the connection concerns a capillary, the positioning of the end of the capillary towards the opening of the leak is very critical. Very often scavenger gas is used to avoid the entrance of extraneous gases, e.g. air. A further disadvantage is the fact that a mixture which is predominantly carrier gas enters the spectrometer. The carrier gas thus makes the largest contribution to the resulting pressure while the partial pressure of the sample is very low. Sample signal is thus lower than it could in fact be in the absence of carrier gas.
Chromatog. Rev., 13 (1970) I-59

42

M. KREJCI,

M. DRESSLER

;o,um+GfE++&ass spectrometer
Pump

c~,um++++~ass

spectrometer

MOSS 4 Column 7

spectrometer 1 Mass spectrometer

Pump

Fig. 12. Diagram

of molecular

separators286.

(3) The connection of column with the spectrometer by means of a separator. In addition to reduction of the pressure the separator carries out a so-called enrichment of the sample, i.e. it preferentially removes the carrier gas from the effluent. Molecular separators (Fig. 12) make use of the fact that the carrier gas molecules are lighter than those of the sample. With separator of RYHAGE type (2) the mixture streams at high speed through a series of jets242,262. Relatively light molecules of the carrier gas helium diffuse to sides of the separator from which they are pumped out while the heavier molecules of the sample stream to another jet. Only one separator is used for capillary columns246. makes use of the easier effusion A separator made of sintered glass (I) 11s~182~2*g~2so of carrier gas molecules through the pores of the separator. In addition to sintered glass, silver membranes2s+5 and membranes of silver and palladiumlg* which only let through hydrogen have also been used for separators of this type. Teflon separators (4)9*@r9,rS4Js5, and organic diaphragm separators (3)28J33aJ8s make use of the differing permeabilities of materials for the carrier gas and compounds under determination. Helium goes preferentially through the walls of a teflon tube, an organic diaphragm permits the passage of organic vapours, but it retains most of the inorganic carrier gaP6. Separator function is determined 11Q~180 the so-called separation yield and by by the so-called enrichment factor. Separation yield lrs is defined as the ratio of amount of the sample entering the spectrometer Ql\ls to the amount entering the separator QGC.

y=Enrichment N =

QMS
QGC
N is defined as Q&Hem Qcc/H%c

Chomatog. Rev.,

13

(1970)

I-59

SELECTIVE TABLE 15

DETECTORS

IN

GC

43

SEPARATION A FUNCTION

YIELD

(Y)

AND GAS

ENRICHMENT FLOW RATE,

(N) OBTAINED
TEMPERATURE,

WITH AND

A POROUS COMPOUND@

TEFLON

SEPARATOR

AS

OF CARRIER

Temperature

Flow rate
min) 5 IO 15

Ethane N

n-Hexane N -Y

Benzene N
(%I

Isononane

(C)

(ml1

280

69

I.4
2.0

89
68 61

1.8

78
63 51 84 64 51 84 66 54

1.6 2.4 3.5 I.7 2.5 3.5 1.7 2.6 3.8

90
70 62 94 77 65 95 86 70

1.8 2.8 4.3 I.9 3.1 4.6 1.9 3.4 4.9

46 72 61

3.5 1.4

2.7 4.3
1.8 3.3

300

5 10 15

g2
82

53 75 64 54

2.4 3.7 I.5 2.5 3.8

75 94 88
82

5.2 1.9 3.5

5.7

320

5
IO

15

where QMs/HeMs is the ratio of the sample to the carrier gas on the MS side of the separator and Qoo/Heoc is the ratio on the GC side of the separator. By substituting, a relation between both factors is obtained: N=YHeoc HeMs efficiency depends119Js4J85 on the working conditions and on the organic compounds such as molecular weight, polarity etc. Tables 15 dependences of N and Y for separators of porous glass and teflon on temperature and type of compound.

Separator character of the and 16 show the carrier gas flow,

TABLE 16
YIELD

SBPARATION A FUNCTION

(Y)

AND GAS

ENRICHMENT FLOW RATE,

(N) OBTAINED
TEMPERATURE,

WITH AND

A SINTERED COMPOUND@

GLASS

SEPARATOR

AS

OF CARRIER

Temperature

(C)

Flow rate (mtl mi,n)

5
IO I5

Ethane -N

n-Hexane N

Benzene

Isononane

75

I9 18 18

4 2

54 53 56 47 46 48
41 46 42 43 41 38

11 *5
18

36 38 39 34 34 36 33 35 35 3' 32 29

7 IO 13 7 10 IZ 6 10 12 6 9 10

64 60 65 52 52 53 45 49 48 46 42 42

12 17 21 IO 14 18 9 14 16 9 12 I4

150

5 IO 15

15 14 15 I5
16 14 14 14 I3

3 4 5 3
: 3 4 5

9 I3
16 8 13 I4 8 11 13

22.5

5
IO

I5 300 5
IO

I5

Ctiromatog.

Rev.,

13 (1970)

I-59

44

M. KREJCf, M. DRESSLER

Y for the sintered glass separator is essentially independent of flow rate while N increases by 60-80~~ over the range of flow rates, s-15 ml/min. Y decreases with the rise of temperature to 300 by 15-20%, while N is approximately constant. With teflon both Y and N are dependent on flow, however, both factors are independent of temperature. The efficiency of RYHAGE separator242 increases slightly with temperature245. A mass spectrometry detector may, like other spectroscopic detectors, carry out the detection of the whole spectrum or detect the compounds at a certain constant value of the spectrum only. In the former case it is necessary to scan the whole spectrum as quickly as possible207~249 and as near to the maximum of chromatographic peakj4 as possible. To this end, it is necessary to use high-speed scanning spectron-ieters114,184,278~27g. The mass spectrometry detector is often connected in parallel with In a commercial gas chromatographic detector 29,137~143~180. this case, however, the sample enters the detector rather earlier than the spectrometer. As the spectrum should be recorded at the moment when the chromatographic peak shows a maximum, is a portion (10%) of the signal from the ion source 42,52,86,211,243,284,285 used for the determination of the maximum of the curve. This total ionisation current is dependent on flow244 and is proportional to the concentration of a compound272. SCOTTS method2s5 avoids the necessity of the high-speed scanning of the spectrum during the elution of a compound by stopping the carrier gas flow through the column during the analysis of the compound in the spectrometer. In the latter case only one constant mass characteristic of a certain group of substances115p134p137,153 detected. Even in this case ionic current is proportional to is the concentration of the compound272. Detection sensitivity115*272 expressed in g/set is IO-~~-IO-~~. This amount can still be reliably identified. Smaller amounts, IO-~~-IO-~~ g/set, may be detected but the identification is not very conclusive. For identification as a rule it is necessary for the signal to be 30-150 times higher than that for detection206 alone. The coupling of gas chromatography with mass spectrometry is described by a series of authors2,40,136,138,247,273,286; th e most detailed discussion of the method is given by MCFADDEN~O~. High selectivity of detection can be obtained by suitable selection of the mass to be detected, e.g., mass 43 is characteristic ofmethyl ketones115, 91 of alkylbenzenes13, 208 of alkyIlead137@Q, etc. A spectrometer working as a selective detector at constant mass does not essentially worsen the separation of the compounds on the column. Column efficiency, expressed by the height of a theoretical plate, was found274, excepting for higher carrier gas flow rates, to be the same for a flame ionisation detector and a mass spectrometer. The width of the gas chromatographic peak is also practically the same with both a flame ionisation detector and a detector of total ionisation currentr35. The use of a separator does not present many difficulties resulting from dead volume, sorption, or the reaction of separator material with the compounds. With a separator of sintered glass, tailing does not occur, except in the case of small concentrations. Column efficiency, however, decreases by IO%ZSO with use of the separator. With a separator of this type, adsorption of polar compounds was noticed; for this reason silanisation of the separator which reduces the losses through adsorptionlQ8a was carried out. Use of a one-stage jet molecular separator did not appear to disturb Ckmatog. Rev., 13 (1970) 1-59

SELECTIVE DETECTORS GC IN

45

the column separation efficiency 222a. The use of a silver membrane with a small active surface (0.1 cm2)2gdoes remove the problems of distortion of chromatographic peaks and absorption losses. When this membrane was used, no reactions between the silver of the membrane and halogen and sulphur compounds were noticed. Preferential retention of olefinic compounds was not noticed either. Helium is usually used as carrier gas as this element5 has a low ionisation efficiency, low mass, high ionisation potential and gives minimum interference. The energy of the electrons used in the ionisation chamber is sometimes reduced to 20 eV in order to decrease the helium ionisation 52.At this energy certain differences exist in the spectrum of compounds when compared with the commonly used energy of 70 eV, but generally the spectra are the same202. One disadvantage of this method of detection is the effect of stationary phase bleeding on to the filament of the ionisation chamber. At higher column temperatures, small amounts of stationary phase can change the filament characteristics, especially when tungsten is used. Large amounts of chromatographed compounds can have the same effect206. At temperatures around 200 some columns can release considerable amounts of carbon dioxide, carbon monoxide, and water. As a result of the release of these compounds relatively high background current occurs 2J6. addition the stationary In phase also contributes, by means of its molecules or decomposition products, to the background current. This effect shows at temperatures over 200 especially. It can, however, be reduced by connecting a short column beyond the chromatographic onelE1a where the stationary can be adsorbed. Most of the compounds eluted at temperatures over 150 have molecular weights over 150 and the most important characteristic masses are usually found to have a molecular weight of about 70; 80% of the mass of the stationary phase, which contributes to the background current, is generally below mass 45 and thus does not matter much206in the identification. A further disadvantage of the identification of compounds from the whole spectrum is the fact that mass spectra obtained on different apparatus and under different conditions frequently show significant variations. Reference spectra have thus relatively limited significance and hold rather for a specific apparatus and conditions136. A significant disadvantage of the mass spectrometer is its high price in comparison with that of the gas chromatograph. For this reason VARADI~~~ and VARADI AND ETTRE~*~ developed a combination of a thermionic triode and mass analysing system, but it has, however, a low resolution capacity. Another technique, which avoids the high price of the mass spectrometer and is at the same time similar to mass spectrometers, is the coupling of a pyrolyser between The two chromatographic columns 77,ii3~r*i~2g*. substance separated in the first column is decomposed in the pyrolyser and the pyrolysis products are analysed in the second column.
J, Galvano-coulometric detectors

Coulometric detectors consist of three parts-the destructive unit, the titration cell and the coulometer. The compound leaving the chromatographic column passes through the destructive unit where it is either oxidised or reduced into simple inorChromatog. Rev., 13 (1970) I-59

46

M.KREJ'%,M.DRESSLER

ganic compounds. These compounds pass into the titration cell, where they are titrated automatically by appropriate ions. The concentration of titrant in the titration cell is kept at a constant value; the loss of titration agent, caused by passage and titration of the decomposition products of the substance analysed, is brought to the original concentration by a variable electric current 61@. The ions produced in the course of the titration are directly proportional to the amount of a given element in the sample, and if the current is integrated as a function of time, this integral is proportional to the total amount of the element. With oxidative decomposition carbon dioxide, water, hydrogen chloride, nitrogen dioxide, and sulphur dioxide are produced from organic compounds. If silver ions are used as the titration agent, halogen compounds may be determined44~47~48~51~63 selectively. The minimum detectable amount is 2 x IO-~ g of chloride50. Bromocompounds are converted into elemental bromine which gives only half the response as it hydrolyses268 to HOBr and HBr and only HBr is precipitated by silver ions50. There are some solvents which, although they do not contain halogens, contain materials giving low response4. The conversion of compounds into sulphur dioxide depends on temperature203. At high temperatures (800-IOOO), sulphur dioxide is formed rather than sulphur trioxide. Quantitative conversion is not necessary but constant equilibrium ratio SO,/SO,, i.e. constancy of temperatureleg, is conditional. Titration of sulphur dioxide or iodine44,62,203p221.For bromine titration, the is carried out by either bromine2+ minimum detectable amounts are IO p.p.b. for hydrogen sulphide, 50 p.p.b. for sulphur dioxide, and IO p.p.b. for methyl mercaptan2. Nitrogen compounds give a negative response as nitrogen dioxide is a stronger oxidising agent than brominenrs. For the titration with iodine, the minimum detectable amount of sulphur is IO-~ g (ref. 203). Large amounts of hydrocarbons and compounds producing strongly oxidative substances in the course of decomposition, i.e. those of bromine, chlorine, and nitrogen, however, also give a response 203. The response to hydrocarbon may be decreased by increased flow rates of oxygen and of carrier gas through the reaction tube but it cannot be eliminated. Decrease of this response, however, increases noise. Strong oxidative substances, on the other hand, oxidise iodine ions and give a negative response. The effect of chloro-compounds may be reduced and sometimes even eliminated by bubbling oxygen through water. The effect of nitrogen is relatively small. Detector response linearity covers 3 orders of magnitude2J3. Change in carrier gas flow has no effect on detection sensitivity62. Hydrogen sulphide, hydrogen chloride, and phosphine originate under reducing conditions. Absorption methods must be used for specific detection45T46. Aluminium oxide is used for the removal of hydrogen sulphide and hydrogen chloride. A silica gel column binds hydrogen chloride and at the same time it separates phosphine and hydrogen sulphide. Thus the amount of phosphorus and sulphur in one compound can be determined simultaneously. In a direct determination of phosphine, hydrogen sulphide, and hydrogen chloride, these are detected with a relative sensitivity of 2 :2:I (ref. 45). The stoichiometric ratio of PH, to Ag+ is I :z (refs. 45 and 46). At the decomposition temperature (700) the yield of PH, is zero, sulphur bound to a phosphorus atom gives a quantitative yield but sulphur bound to a carbon atom gives a low and variable yield45. Ckromatog. Rev., 13 (1970)
r-59

SELECTIVE

DETECTORS

IN

GC

47

Sensitivity to mercaptans is IOO times higher than with a katharometerios. Hydrocarbons and amines give no response46. Nitrogen compounds are converted into ammonia under reducing conditions and with use of catalyst (Ni or MgO) and again are automatically titrated by hydrogen ions to a constant pH31z02. Acid substances, i.e. H,S and HCl, adsorb irreversibly on MgO (below the temperature 4807, basic substances give a response. In quantitative analysis with a coulometric detector, no empirical calibration factors have to be determined. The amount of the substance analysed can be calculated from theoretical factors-Faradays constant and the percentage of an element in a compound. As the detector is practically insensitive to hydrocarbons and their oxidation products44 the background is also low. This fact permits the use of high doses of solvent without tailing of the corresponding chromatographic peak, programmed temperature, and more volatile or less stable stationary phases. However, hydrocarbons give a signal in iodine titrations if the large quantities of hydrocarbons are not entirely oxidised and some intermediate products can be further oxidised by iodine or, the other way round, reduced203. For absolute detection specificity it is necessary, as with the electrolytic conductivity detector, to use adsorbing material to remove unwanted elements. It was noticed45 that with the use of aluminium oxide for the specific detection of phosphine, the base line starts to increase as a result of packing saturation after a certain time. The detection of nitrogen compounds presents a whole series of difficultieszo2 due to the necessity of using a catalyst for the conversion of the compounds into ammonia. E.g., quantitativeness of the conversion decreases with time and the the catalyst must be changed after a certain time. The useful life of the catalyst depends on the concentration of the condensed aromatic and sulphur compounds. Even though the decomposition of the substances before the actual detection removes the necessity for individual calibration, the complicated nature of the whole analytical system has many disadvantages2. The decomposition, and also the titration, require a certain time and the time constant is thus higher203(2-5 sec50) than that for conventional detectors. The construction of a detector with a low time constant and high sensitivity1r4&(IO-i4 gequiv./sec) has recently been described. An electrochemical cell consisting of non-polarisable and polarisable electrodes can be used as the detector assuming that the compounds under detection react with the polarisable electrode. The electrode potential changes and if both electrodes are connected outside a current flows through the cell. BECHTOLD~~ used a cell consisting of Pt/Ag/AgI/Ag,S/Pt as a detector for sulphur and halogen compounds. The compounds are, prior to detection itself, oxidisedlB@$87into sulphur dioxide and trioxide and into elemental halogen or hydrogen halide. These substances react with silver and cause a change in the electrode potential and thus the initiation of an electric current. Minimum detectable amounts are 2 x 10-l~ moles/set for chlorine, 6 X 10~~~ moleslsec for bromine and iodine, and 1-5 x 10-l~ moIes/sec for sulphur. The sensitivity for the compounds containing only carbon, hydrogen and oxygen is three to five orders of magnitude lower. The detector background current is IO-~--IO-~ A, noise approximately rod9 A,
Chromatog. Reu., 13 (1970)
I-59

48

M. KREJCi, M. DRESSLER

and the range of the detector linearity for halogen compounds is approximately four orders of magnitude. CREMER et al.@ have described a detector with high selectivity to primary and secondary alcohols and aldehydes. The cell consists of porous platinum anode and a silver oxide cathode, the electrolyte is KOH. Under these conditions anodic oxidation of the compounds under detection occurs to give the corresponding acids and ketones. Detection sensitivity is approximately two orders of magnitude higher than with a katharometer. HERSCHS ce11141 a detector specific to oxygen. It consists of a silver cathode is and lead anode, the electrolyte contains hydroxyl ions. On passage of acids through the cell a reduction occurs on the cathode I/Z 0, + H,O + ze- --f 2. OHPb + 3 OH- - ze- + PbO,H-

+ H,O

and an electric current passes230. Detector response depends on the carrier gas flow rate. It increases with increasing flow; at a certain flow rate it reaches maximum and then again decreases230. HILLMAN AND LICHTWOOD~~~state, however, that the response decreases continuously from a flow rate of 20 ml/min and the sensitivity for optimum conditions is 1.8 x 10-l~ g of oxygen. Detection stability is dependent on moisture in the carrier gas. If its moisture content is too low or too high, sensitivity decreases230. The high selectivity of the detector renders it relatively easy to determine the oxygen in a mixture with argon. The compounds which could interfere have not been studied as yet, however, it has been found that hydrogen, nitrogen, carbon monoxide and dioxide, and methane give no response 142.Organic sulphur compounds, however, give an anomalous response; gives no response142. K. The electrolytic hydrogen sulphide in concentrations up to 50 p.p.m.

conductivity detector

The principle of detection consists in measuring the conductivity of water in which are dissolved the decomposition products of the compounds which have left a chromatographic column. The detector consists of two parts. In the first part-clecomposition-the compounds are decomposed catalytically, the other part-cellperforms the transfer of the decomposition products from the gaseous phase into water and the detection of the electrolytes in the liquid phase. The decomposition can be carried out under either oxidative or reducing conditions. In the former case50+o, the compounds containing carbon, sulphur and chlorine burn in a stream of oxygen or air, the decomposition products are carbon dioxide, sulphur dioxide, sulphur trioxide, and hydrogen chloride. Under these conditions the detector is sensitive to sulphur and halogen compounds. The response to carbon is practically nil due to the inability of the carbon dioxide to absorb quickly in water in the course of its passage through the detector which results in a negligible degree of ionisation for that part which is absorbed5s. The sensitivity is approximately 10~ times higher for sulphur and halogen compounds than it is for compounds of carbon, hyChromatog. Rev., 13 (1970) r-59

SELECTIVE DETECTORS IN GC

49

g/set,

drogen, oxygen, and nitrogen. The minimum detectable amount is for DDT ~%Io-~ which corresponds to z-IO-r g/set of chlorine rh2. With this detection method, it does not matter whether sulphur is oxidised into sulphur dioxide or trioxide. At solution in water both oxides form strong acids. As approx. 80% of the electrolytic conductivity is caused by H+ ions, the difference in conductivities of the acid ions can be neglected5D. Under reducing conditions5D+0, in addition to hydrogenated hydrocarbon fragments originating from organic compounds, ammonia is produced from nitrogen compounds, chloride from organic chlorides, hydrogen sulphide from sulphur compounds and water from oxygen-containing compounds. The detector gives a response to nitrogen and chloro-compounds while carbon, oxygen, and hydrogen are not detectable and such compounds give only a weak signal. During oxidative decomposition sulphur oxides or hydrogen chloride can be selectively removed by certain packings 60. Calcium oxide on quartz wool at 800 removes sulphur oxides and permits detection of hydrogen chloride; oxygen is presaturated by H,O vapour prior to entrance to the decomposition oven so that the calcium chloride which could originate is hydrolysed. Silver on quartz wool removes hydrogen chloride while sulphur oxides pass through the packing. Ammonia is the only base among the decomposition products resulting from the reduction of organic compounds. Strontium hydroxide on quartz wool removes any acidseO. Ascarit can be also used as the adsorbent5D. Gas flow rates through the detector in the range of IO-1000 ml/min have no effect on the response5g. Water flow rate must be in the range from I-Z ml/minss. At lower fiow rates the distortion of the chromatographic curve occursP. Detector response is linear over approximately z orders of magnitudesQ. A somewhat different decomposition method was used by STERNBERG et al.263, who used a flame ionisation detector for the decomposition. The combustion products are, in this case, trapped in a thin liquid stream which runs on a carrier above the detector. The sensitivity of detection is 3 x 10-l~ moles/set for chloro-compounds (dichloromethane) and z x 10-l~ moles/set for sulphur compounds (carbon disulphide). Methane gives a response approximately 4 orders of magnitude lower than carbon disuIphide. Background is 2 x IO- A, noise 1.3 x 10-l~ A. The advantage of the detector is the proportionality of the areas of chromate graphic curves to the chlorine content in every compound58. For Lindane, Aldrin and DDT the curves giving the response plotted against the amount of substance are identical. For quantitative purposes it is possible to work without preliminary calibration. There are a great number of factors which constitute disadvantages to this method of detection ; for instance, the decomposition of the solute and the transference of the gaseous products into water. These factors considerably affect the sensitivity
of STERNBERGS detector263. The electrolytic conductivity detector responds to all compounds which ionise when dissolved in water. The selectivity of detection must be increased by indirect methods, in this case by the suitable selection of substances which absorb all the compounds capable of ionisation in water excepting the one to be determined. Detector selectivity is thus relatively low. In the case of a long time for the passage of the decomposition products of the organic substances through the liquid, efficient

Chromatog. Rev., 13 (1970) I-59

50
absorption containing

M.KREJCi,M.DRESSLER

of carbon dioxide occurs and this detector is then sensitive to all compounds carbon atoms and the selectivity is lost entirely231.

L. The polarographic

detector

A polarographic method of detection was used first by JANAK et al.147 for the determination of halogens. At a constant voltage of +0.3 V, the process was followed by means of the increasing Ti(IV) wave resulting from the absorption of halogens in a solutionofTi(II1). MA~RANOVSKI~AND YANOTOVSKIPS proposed the simultaneous use of a polarograph and a thermal conductivity cell. A similar connection of two detectors has also been used for the determination of carbonyl compoundsss~. For the determination of basic nitrogen compounds the system Ni(II)-pyridine was investigatecP. Selectivity of polarographic detection is relatively high and it can be further increased by the use of catalysecl reactions281. The minimum detectable concentration is, however, low-7.1 x IO+ g/mleven though the response value is in comparison with that for a katharometer approximately 15times higher2s1. The essential disadvantage of this method is the broadening of the peaks resulting from the relatively large volume of the polarographic detector.

M. The $iezoelectric sorption detector

If material with sorption properties is deposited on the surface of a quartz crystal, the ability of that crystal to vibrate diminishes. In the case where this crystal is used as a detector for chromatographic analysis, the compounds leaving the column are absorbed in the material, and the frequency decreases further under the influence of an absorbed compouncPW66. The response value of this detector depends on the quantity absorbed in the film of material on the crystal. The signal-change thus given by the adsorption isotherm for a given materia1165J66 of the compound in frequency-is

AF=AF,--$
0

where AF,

of a compound A W = weight increase of adsorbed compound Detection selectivity is thus determined by the material constituting the film. Some examples of selectivity with the use of different materials are given in the literature, e.g. determination of water with the use of silica gel or molecular sieve165, of hydrogen sulphide with the use of lead acetate165, of organophosphates with the use of mercuric salts123 etc. It is obvious that this detector selectivity is rather low as it is given by the relative sorption properties of the system only. An interesting property of the detector is, however, the fact that response depends on the adsorption isotherm of the compounds. The relative sensitivity of the detection of two compounds is thus equal to the relative elution volumes of both substances on the same stationary phase165Js6.
ChvOWZfOg.

AW, AF

= change in frequency resulting from the film on crystal = weight of the film = change in frequency resulting from the adsorption of vapours

Rev.,

13

(1970)

1-59

SELECTIVE

DETECTORS

IN

GC

51

It is thus possible, with the use of one liquid as the stationary phase and another liquid as the detector film, to obtain elution data for both liquids from one analysis provided the quantitative composition of the mixture under analysis is known (see I.C.)

3.

CONCLUSIONS

Developments during recent years have shown the increasing significance of selective detectors in gas chromatography. The use of selective detectors opens the way to the solution of new complex tasks in analytical chemistry. The combination of the high resolution capacity of gas chromatography with selective detector response allows attempts at the analysis of complex natural mixtures. The relatively low purchase costs of detectors of binary mixtures (e.g. alkali flame ionisation or electron capture detectors) have resulted in these detectors becoming an integral part of modern chromatography. The combination of gas chromatography and mass spectrometry seems to be the most effective method of organic analysis at the present time. The purchase costs of the equipment for this method are, however, so high that cheap detectors of binary mixtures are used much more often in spite of their being essentially worse as far as analytical efficiency is concerned. A comparison of individual selective detectors on the basis of the data published as to their suitability of use for individual types of compounds is rather difficult, partly because of relatively few data on sensitivity, partly because of non-uniformity of expressing sensitivity (minimum detectable amount, ionisation efficiency, etc.). It is obvious that the question of the appropriate use of selective detectors is resolved by two factors: selectivity, which is discussed in detail in previous sections, and sensitivity. In Table 17 we have tried to summarise the sensitivity of individual detectors (with the exception of some spectral detectors) to different elements. The sensitivities are expressed by minimum detectable amounts. It must be mentioned that the sensitivity changes with the construction of the detectors, with working conditions, and with the type of compounds in the way which has been described for individual detectors, and that the comparisons given in Table 17 must only be taken as an indication of the sensitivity since optimum results only are shown.
Phosphorus compounds

Sensitivities of the electron capture detector (ECD), alkali flame ionisation detector (AFID), flame photometric detector (FPD), and emission spectrometer (ES) are comparable; from the sensitivity point of view all four detectors are equally suitable even though the response of the ECD is fairly strongly dependent on molecular structure. The sensitivity of the coulometric detector (CD) is rather low, with other detectors the sensitivity to phosphorus is not known.
Sul~hur compounds

The ES, FDP, AFID, and galvanic detector (GD) seem to be the most suitable
Chromatog. Rev., 13 (1970) I-59

TABLE

17

MINIMUM

DETECTABLE

AMOUNT

FOR

DETECTOR

comfiound f&c)
(glsec) 5.7 x
10-12 10-11 -

Type of
SID FPD ES (gb) CD

ECD

A FID

EC

(moles/set)
3.7 x
I.3 4.0 x x Icrll 10-11 10-14 I.5 x 10-l@ 1 2 x

(glsec)
x0-= 5 x -

(glsec except-Ti)

(moleslsec)
2 10-Q x 10-11

GC (molesjsec)

-P

I x x0-14

8.3 x

10-12

-S

1.1 x 10-10

Yx -

10-1s

2.5 x

10-10

3 x 10-12
-

-N -Br -Cl -1 Other elements

7.0 x

8 x 10-14 x 10-9 2.5 I x IO-l* 1.3 x 1o-9 2 x 10-16 -Pb 3.7 x IO-~* -As 7 x IO-* -Ti 4 x 10-l~ moles/ set and other metals

6 x IO-~* 2 x 10-13 6 x 10-l~

SELECTIVE

DETECTORS

IN

GC

53

ones. The sensitivity of the GD is again relatively lower. The response of the ECD to pesticides containing sulphur as well as phosphorus is usually described, and thus for these compounds the sensitivity described also applies to phosphorus compounds. The exception is sulphenon, which has no phosphorus atom but contains a chlorine atom in addition to sulphur. The response of the surface ionisation detector (SID) is only a little higher than that for hydrocarbons.
Nitrogen

compowads

The sensitivity of the AFID is 2.5 x 10-10 g/set for pyridine. The sensitivities of CD and electrolytic conductivity detector (EC) are lower. ECD is sensitive to nitrate; selective sensitivity has not been known with other detectors.
Chloro-,
bromo-, and

ioao-compounds

The sensitivity value depends on the number and kind of halogen atom. For monochloro-compounds the ES, EC, and GD seem to be the most sensitive ones. The sensitivities of the ECD, AFID, SID, and CD are somewhat lower. The response of the ECD, however, increases rapidly with an increasing number of halogen atoms while with other detectors this relation is linear. The ECD is by far the most sensitive detector to compounds with two and more chlorine atoms and to bromo- and iodocompounds. Compozlnds of other elements The ECD is sensitive to compounds of lead, the AFID to compounds of arsenic and tin, and the FPD to metallic compounds-e.g. to the compounds of MO, W, CO, Rh, etc.

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DETECTORS

IN GC

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Spectry,

Chromatog.

Rev.,

I3 (1970)

I-59

56

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