Cromatografía Iónica - Metrohm

Ion Chromatography
Dr. Helwig Schfer Dr. Markus Lubli Dr. Roland Drig
Metrohm Ltd. CH-9101 Herisau Switzerland
Helwig Schfer Markus Lubli Roland Drig
Ion Chromatography
Theory Columns and Eluents
Metrohm Monograph 8.014.5003 8.732.2003
All Rights Reserved. Printed in Switzerland by Metrohm AG, CH-9101 Herisau 11.96
Table of Contents
Table of Contents
1 Theory of Ion Chromatography ............................................. 1
1.1 Introduction ......................................................................................... 1 1.2 Ion exchange as a separation mechanism ..................................... 2 1.3 Chromatographic characteristics .................................................... 4 1.3.1 Retention time and peak width ................................................. 4 1.3.2 Capacity factor k' ..................................................................... 5 1.3.3 Selectivity .............................................................................. 5 1.3.4 Plate number N ........................................................................ 5 1.3.5 Resolution R ............................................................................. 6 1.3.6 Asymmetry factor T .................................................................. 7 1.4 Ion chromatographic separations.................................................... 8 1.4.1 Dependence of the separation on the column material ........... 8 1.4.2 Influence of the eluent composition on the separation ............ 9 1.4.3 Interferences in the chromatogram: system peak.................. 11 1.5 Conductivity detection..................................................................... 12 1.5.1 General................................................................................... 12 1.5.2 Direct ion chromatography..................................................... 14 1.5.3 Ion chromatography with chemical suppression.................... 15 1.5.4 Comparison in the sensitivities of conductivity detection with and without chemical suppression.................. 15 1.5.5 Linearity of the calibration curve............................................. 17 1.6 Optical detection .............................................................................. 18 1.6.1 General................................................................................... 18 1.6.2 Direct UV-VIS detection .......................................................... 18 1.6.3 Indirect UV-VIS detection........................................................ 19 1.6.4 UV-VIS detection with post-column derivation ....................... 20 1.6.5 Fluorescence detection .......................................................... 20 1.6.6 UV-VIS multiwavelength detection.......................................... 20 1.7 Electrochemical detection............................................................... 21 1.8 Multiple detection ............................................................................. 23 1.9 Suppressors...................................................................................... 24 1.8.1 Suppressor reactions ............................................................. 24 1.8.2 Construction of suppressors .................................................. 25 1.10 Evaluation and calibration .............................................................. 26 1.10.1 Evaluation of peak area.......................................................... 26 1.10.2 Evaluation of peak height ....................................................... 26 1.10.3 Calibration with external standard .......................................... 26 1.10.4 Calibration with internal standard ........................................... 27 1.10.5 Calibration by standard addition ............................................ 29 1.11 References......................................................................................... 29
8.732.2003 Monograph Ion chromatography
Table of Contents
Columns and eluents .................................................................. 31

2.1 General hints..................................................................................... 31 2.1.1 Eluents ....................................................................................31 2.1.2 Protection of separating columns ...........................................31 2.1.3 Regeneration of columns ........................................................32 2.2 IC Anion Column Hamilton PRP-X100 (6.1005.000)..................... 33 2.2.1 Column specifications.............................................................33 2.2.2 General remarks......................................................................33 2.2.3 Phthalic acid eluent .................................................................34 2.3 IC Anion Column SUPER-SEP (6.1009.000).................................. 35 2.3.1 Column specifications.............................................................35 2.3.2 General remarks......................................................................35 2.3.3 Phthalic acid eluent .................................................................36 2.3.4 Benzoic acid eluent.................................................................37 2.4 IC Glass Cartridge Metrosep Anion Dual 1 (6.1006.020)............. 38 2.4.1 Column specifications.............................................................38 2.4.2 General remarks......................................................................38 2.4.3 Phthalic acid eluent (without chemical suppression) ..............39 2.4.4 HCO3/CO32 eluent (with chemical suppression)....................40 2.5 IC Anion Column Metrosep Anion Dual 2 (6.1006.100)............... 41 2.5.1 Column specifications.............................................................41 2.5.2 General remarks......................................................................41 2.5.3 Phthalic acid eluent (without chemical suppression) ..............42 2.5.4 HCO3/CO32 eluent (with chemical suppression)....................43 2.6 IC Anion Column Phenomenex STAR ION A300 (6.1005.100) ... 44 2.6.1 Column specifications.............................................................44 2.6.2 General remarks......................................................................44 2.6.3 HCO3/CO32 eluent (with chemical suppression)....................45 2.7 IC Exclusion Column Hamilton PRP-X300 (6.1005.030).............. 46 2.7.1 Column specifications.............................................................46 2.7.2 General remarks......................................................................46 2.7.3 HClO4 eluent............................................................................47 2.8 IC Cation Column Nucleosil 5SA (6.1007.000) ............................. 48 2.8.1 Column specifications.............................................................48 2.8.2 General remarks......................................................................48 2.8.3 Tartaric acid/citric acid eluent .................................................49 2.9 IC Cation Column Metrosep Cation 1-2 (6.1010.000)................... 50 2.9.1 Column specifications.............................................................50 2.9.2 General remarks......................................................................50 2.9.3 Tartaric acid/dipicolinic acid eluent.........................................51 Index................................................................................................... 53
II
1.1 Introduction
Theory of Ion Chromatography

Introduction
The term "chromatography" is the general name for a wide range of physicochemical separation processes in which the components to be separated are distributed between a stationary and a mobile phase. The classification of the various types of chromatography depends on the state of aggregation of these two phases:
Mobil phase Stationary phase
1.1
liquid gaseous liquid

GLC LLC
solid
GSC LSC (HPLC) gas chromatography liquid chromatography
Since the introduction of high pressure or high performance liquid chromatography (HPLC) at the end of the sixties, liquid chromatography has developed into one of the most comprehensive and important methods of modern instrumental analysis. Based on the polarity of the stationary and mobile phases, a distinction is made between the following methods:
Polarity of the stationary phase
ionic polar
4 1 2 3
1 Normal phase chromatography 2 Reversed phase chromatography 3 Ion pair chromatography 4 Ion chromatography
non-polar
non-polar
polar
ionic
Polarity of the mobile phase
8.732.2003 Monograph Ion Chromatography
1 IC Theory Ion chromatography was first introduced in 1975 and within a short space of time has developed into an independent analytical technique which today encompasses all HPLC methods to determine inorganic or organic ions. The combination of ion exchange columns and conductivity detection continues to represent the most important type of ion chromatography, and two different techniques are used in practice. In the technique with chemical suppression, the background conductivity is suppressed both chemically and electronically. In contrast, the direct chromatographic technique (ion chromatography with electronic background suppression) employs eluents with salts of organic acids in low concentration on ion exchangers of very low capacity to achieve a relatively low background conductivity, which can be suppressed directly by electronic means. The following sections deal with both techniques which have also been implemented in the 732/733 Metrohm IC system.
1.2
Ion exchange as a separation mechanism

The vast majority of ion chromatographic separations occur by ion exchange on stationary phases with charged functional groups. The corresponding counter ions are located in the vicinity of the functional groups and can be exchanged with other ions of the same charge in the mobile phase. For every ion, the exchange process is characterized by a corresponding ion exchange equilibrium, which determines the distribution between the mobile and stationary phase, for example in the case of an anion A : E stat + Amob KA = Astat + Emob
A: sample anion E: eluent anion (counter ion)
[ A ] stat [ E ]mob [ A ]mob [ E ] stat
The various ionic components of a sample can thus be separated on the basis of their different affinities for the stationary phase of the ion exchanger (different equilibrium constants K). The most important group of ion exchangers is that of the organic materials based on synthetic resins. A copolymer of styrene and divinylbenzene is frequently employed as the support.
1.2 Ion exchange as a separation mechanism
(
+
Styrene Divinylbenzene
) )
Styrene-divinylbenzene resin
Cation exchangers are obtained by subsequent sulphonation of this styrenedivinylbenzene resin, anion exchangers by chloromethylation followed by amination.
SO3Cation exchanger
NR3+
Anion exchanger
In addition to these resins, other polymers and silica gels with chemically bound phases are also employed. Whereas the classical ion exchange is performed on macroporous particles of a high exchange capacity with a size of 75 - 250 m in the batch or column process, in modern ion chromatography, ion exchange materials of low capacity with particle sizes of 5 - 10 m are employed. This makes it possible to separate and detect anions and cations efficiently and rapidly with eluents of low concentration.
1 IC Theory
1.3
1.3.1
Chromatographic characteristics
Retention time and peak width
The elution curve (signal vs time) following a chromatographic separation is called a chromatogram. It generally has the following appearance:
Signal
Component 1 Component 2
tR,2 tR,1
Injection peak
2 t,1 t0 w0.5,1 w0.5,2 2 t,2
wb,1 t'R,1 t'R,2
wb,2
Time
The time parameters of the resulting bands (peaks) characterize the chromatogram and are illustrated in the Figure:
t0 tR
Dead time Retention time
time needed by the mobile phase to flow through the separation system time needed by an injected substance until its concentration maximum appears at the end of the separation system = retention time tR dead time t0 half peak width at the inflection points
t'R
Net retention time Standard deviation
t
wb
w0.5 Peak width at half height = 2.354 t

Peak base width = 4 t
The time parameters t0, tR and t'R can be converted into the dead volume V0, retention volume VR and net retention volume V'R using the constant flow rate. If symmetric elution profiles are found, the shape of the chromatographic peaks can be described with sufficient accuracy by a Gaussian curve. The width of such a Gaussian-shaped peak is determined from the chromatogram as standard deviation t, width at half height w0.5 or base width wb.
1.3 Chromatographic characteristics
1.3.2
Capacity factor k'

The retention time tR is the qualitative information of a chromatogram. It is constant for a given component provided the chromatographic conditions remain unchanged (column, mobile phase, temperature, etc.). For the characterization of a substance, it is more convenient to quote the capacity factor k' since, in contrast to the retention times, this is dependent neither on the flow of the eluent nor on the column length: k' = t 'R t0 = t R t0 t0 = tR 1 t0
Low values of k' signify that the corresponding ions are eluted in the vicinity of the injection peak and the separation is consequently very poor. Capacity factors between 1 and 5 are optimum in practice; larger k' values lead only to peak broadening, lower detection sensitivity and long analysis times.
1.3.3
Selectivity
Two substances are separated only if they have different k' values. A measure of the separation efficiency of a chromatographic system is the selectivity (also known as relative retention): =
' k2 ' k1
t R ,2 t 0 t R ,1 t 0
(k
' 2
' > k1
1.3.4
Plate number N
An additional useful quantity to characterize a separation system is the plate number N (number of theoretical plates). A theoretical plate is defined as that zone of a separation system within which a thermodynamic equilibrium is established between the mean concentration of a component in the stationary phase and its mean concentration in the mobile phase. If a Gaussian peak shape can be assumed, the plate number N for peaks with a relatively large retention time can be calculated as follows with the aid of the parameters retention time and peak width read off from the chromatogram: N tR = t
2
tR = 5.54 w0.5
tR = 16 wb
1 IC Theory
1.3.5
Resolution R
A measure of the quality of the separation actually found in practice is the resolution R between neighboring peaks: R = 2 ( t R ,2 t R ,1 ) wb ,1 + wb ,2 = 1177 ( t R ,2 t R ,1 ) . w0.5,1 + w0.5,2
If the peak base widths wb,1 and wb,2 are approximately the same, the resolution R signifies the number of times the peak width wb can be fitted into the distance between the peak maxima. At a resolution of R = 0.5, two maxima can still be perceived separately. For quantitative analysis, a resolution of up to R = 1.5 is desirable; greater values of the resolution lead only to unnecessarily long analysis times. The resolution R is dependent on the parameters k2' (capacity factor of the later eluted substance), selectivity and plate number N of the column:
' 1 k2 N ' 4 1 + k2
R =
There are thus three possibilities to improve the resolution of two peaks: Altering the k' values: The capacity factors of the individual components are dependent essentially on the elution strength of the mobile phase, i.e. changing the concentration and ionic strength of the eluent gives rise to other k' values. Here, however, the capacity of the column and frequently also the detector are limiting factors. Increasing the plate number N: The more plates a column possesses, the greater the resolution, but the retention times are also longer thereby increasing the analysis time. The plate number increases with increasing efficiency and length of the column. With packing materials of particle size 10 m or greater, the plate number increases with decreasing flow. Increasing the selectivity : The most effective possibility to improve the resolution involves increasing the relative retention by using a different column better suited to the separation problem or by changing the composition of the eluent. However, this is sometimes extremely difficult or very time intensive. If a given column and one particular eluent have to be used, the plate number N is the controlling influence with regard to the resolution and hence the quality of the chromatogram. For a given column length, the plate number N depends only on the quality of the packing material and the packing itself.
1.3 Chromatographic characteristics
1.3.6
Asymmetry factor T
The elution of chromatographic signals as Gaussian peaks is often not achieved in practice. An asymmetric peak shape, known as tailing, is often found.
h a c = 0.1 h c
The peak asymmetry is quantified by the asymmetry factor (tailing factor) T with a and b being determined at 10% peak height: T = b a
For trouble-free evaluation of the area of a peak, T must be < 2.5, above this, the end of the peak can be recognized only with difficulty. Tailing can have many causes: Dead volume Dead volumes between injector and detector lead to peak broadening and tailing. The asymmetry is more pronounced with peaks eluted earlier than with those eluted later, and the tailing increases with the flow. Column overloading If too much substance has been injected, i.e. the maximum loading of the column has been exceeded, broadened peaks with severe tailing are obtained. Overloading is recognized by a lowering of the capacity factor by more than 10%. Chemical effects The dominant separation mechanism is adversely influenced by another mechanism, e.g. adsorption phenomena in ion exchange chromatography. The lower the flow, the more evident this tailing.
1 IC Theory
1.4
Ion chromatographic separations

The chromatographic parameters retention time, peak shape, dead time and selectivity are the results of the whole chromatographic system, i.e. alterations to the column, the eluent or the flow rate inevitably lead to alterations of the chromatographic parameters. This is why test chromatograms are normally included with the separation columns to demonstrate that the separation behavior described can be achieved under exactly defined conditions. The following sections contain several useful items of information about the optimization of the column, eluent and flow rate parameters with reference to analytical problems which may be encountered.
1.4.1
Dependence of the separation on the column material

The separatory behavior of an ion exchange column is basically determined by the ion exchanger groups bound to the support material (under otherwise identical chromatographic conditions). However, interactions of the analytes with the support material also occur: these are considerably stronger for organic ions than for inorganic ions. For this reason it is a good idea to use columns with different support materials to solve an analytical problem. The following are the main support materials used today for separatory columns: polystyrene/divinylbenzene copolymers polymethacrylate, polyhydroxy alkylmethacrylate coated silica gels The use of suitable combinations of support materials and ion exchanger groups allows optimal conditions to be provided for special separation problems. Even interferences such as those caused by the eluent or, for example, by the carbonate content in water samples can be avoided by the selection of a suitable column as is shown in the following illustrations on page 9. Whereas with the first column the carbonate peak and the chloride peak overlap, on column 2 a separation of carbonate and chloride is obtained. This differing behavior can be traced to the column support material (column 1: polystyrene/divinylbenzene copolymer; column 2: hydroxyethyl methacrylate). These effects are far stronger in the separation of organic anions. In such cases it is also a good idea to test separatory columns with different combinations of support materials and ion exchanger groups.
1.4 Ion chromatographic separations

Cl
1 S/cm
Sample: Drinking water Column: STAR ION A300 (Polystyrene/Divinylbenzene Copolymer) Chloride found: 6.7 mg/L NO3
SO4
2 CO3
1 S/cm
Cl
Sample: Drinking water Column: Metrosep Anion Dual 1 (Hydroxyethyl methacrylate) Chloride found: 5.7 mg/L NO3
SO4
CO3
1.4.2
Influence of the eluent composition on the separation

During the separation of ions by means of ion exchanger columns small ions are eluted before larger ions and monovalent ions before di- and trivalent ions; i.e. for anions the following sequence is obtained: fluoride, chloride, nitrite, bromide, nitrate, phosphate, sulfate, arsenate, selenate, etc. When carbonate eluents are used (pH 910; mixture of Na2CO3 and NaHCO3) the ions are eluted in the same sequence. If the pH is shifted towards higher values then dissociation of phosphate and arsenate occurs: HPO42 to PO43 and HAsO42 to AsO43. There is thus an increase in the retention time which means that by increasing the Na2CO3 share of the eluent both phosphate and arsenate can be shifted in ion chromatograms so that, for example, phosphate is only eluted when sulfate has already been eluted.
1 IC Theory In principle retention times can be shifted by the addition of ligands to the eluent for the determination of cations. The more selective the ligand, the less the retention times of the other cations are influenced. This effect is used in particular for the separation of the complex-forming metals, the transition metals. However, ligands can also be used to obtain better separation of alkali metal ions. The addition of crown ether, for example, leads to a better separation of sodium, ammonium and potassium, as can be seen in the following illustrations.
+
Na Li
+
Column: Metrosep Cation 1-2 Eluent: 4 mmol/L Tartaric acid 1 mmol/L Dipicolinic acid
+
NH4
Mg Ca K
+ 2+
2+
1 S/cm
Na Li
+
Column: Metrosep Cation 1-2 Eluent: 4 mmol/L Tartaric acid 1 mmol/L Dipicolinic acid 1 mmol/L 18 Crown-6 Ca NH4
+ 2+
Mg
2+
1 S/cm
10
1.4 Ion chromatographic separations
1.4.3
Interferences in the chromatogram: system peak

Ionic eluents are normally used in ion chromatography (see section 1.2); these compete with the analyte ions at the ion exchanger. For these eluent anions, e.g. carbonate, phthalate or benzoate, the same chromatographic conditions apply as for all other ions, i.e. there is also a defined retention time for the eluent anions in each chromatographic system. When the sample is injected into the chromatographic system the eluent flow is interrupted by the sample (water with low analyte contents), i.e. there will be a negative amount of eluent ions compared with the eluent concentration injected. This must lead to a negative peak in the ion chromatogram with the retention time of the eluent anion. This peak must not be confused with the water peak, which is obtained at the start of the chromatogram (dead time). Such peaks which can be allocated to the eluent anions are actually obtained; these are generally known as system peaks. These system peaks not only appear when the eluent is diluted, but also for each chemical reaction of the eluent ions with the sample. Examples of this are alterations to the pH and thus the shift in the dissociation equilibrium or reactions of metal ions with the eluent ion (e.g. Ca2+ with CO32). The system peaks are most apparent in direct ion chromatography as here measurements are made at a high conductivity level and small differences in the ionic strength of the eluent are extremely noticeable. In contrast, in ion chromatography with chemical suppression measurements are carried out at a low conductivity level and the system peak is thus considerably smaller. Previously the carbonate system peak has been deliberately ignored as it lies in the area of the chloride peak on the polystyrene/divinylbenzene columns which were normally used and almost all samples contain sufficient chloride to obscure the carbonate peak. Only since acrylate columns have been used has it been clearly seen that the carbonate system peak is present and that this presence can lead to false results (see Fig. page 9). In particular, in the analysis of natural waters with varying carbonate contents the total of carbonate + chloride has usually been determined as chloride.
11
1 IC Theory
1.5
1.5.1
Conductivity detection
General
As a universal method to determine ionic components, conductivity measurement (conductometry) occupies a central position in ion chromatography. Conductometry is defined as the ability of electrolyte solutions in an electric field applied between two electrodes to transport current by ion migration. The relationship between the applied voltage U and the current I is given by Ohm's law: R =
U: I:
U I
voltage [ V ] current [ A ]
The reciprocal of the ohmic resistance R is the conductance G, which has the unit Siemens: G = 1 R
[S]
The conductance of an electrolyte solution depends on the electrode surface A and the interelectrode distance l. The usual measured variable in conductometry is thus the conductivity : = G Kc Kc = l A
[ S cm1 ] [ cm1 ]
The quotient l/A is known as the cell constant Kc, this can usually not be calculated directly but is determined with calibration solutions. The dependence of the electrical conductivity on the type and concentration of the dissolved components can be described as follows: = : c(eq ) 1000
equivalent conductivity [ S cm2 mol1 ] equivalent amount-of-substance concentration [ mol/1000 cm3 ]; c(eq) = c z amount-of-substance concentration [ mol/1000 cm3 ] valency
c (eq): c: z:
The conductivity thus increases with increasing electrolyte concentration. This linear relation holds only for dilute solutions, however, since the equivalent conductivity is itself dependent on concentration in accordance with Kohlrausch's law:
12
1.5 Conductivity detection = A c(eq ) : A: equivalent conductivity in an infinitely dilute solution constant
The equivalent conductivity is given by the sum of the ionic conductivi+ ties and : = +
The ionic conductivities of anions and cations are usually between 35 and 80 S cm2 mol1, the only exceptions being H+ and OH ions on account of their very high mobilities of 350 and 198 S cm2 mol1, respectively. With the aid of the tabulated ionic conductivities, the conductivity of a pure solution for dilute, aqueous electrolyte solutions can be calculated in advance with considerable accuracy. In addition to the ionic species and ionic concentration, the temperature and polarity of the solvent also influence the electrical conductivity. The temperature dependence of 2 10 %/C is very pronounced.
Equivalent ionic conductivities for infinite dilution in aqueous solutions at 25C

Anions OH F

[ S cm2 mol-1 ] 198 54 76 78 77
Cations H
+ + +
+ [ S cm2 mol-1 ] 350 39 50 74 73
Li K
Cl I
Na
+
Br
NO2 NO3
NH4
+ 2+
72 71 45 72 33
2
Mg Ca Sr Ba Zn
53 60 59 64 53 53 55 71 53 70 33
2+
HCO3
2+ 2+
CO3 H2PO4
13
2+ 2+
HPO4 / PO4
57 69 80 66 41 38 36 32 30
Hg Cu Pb
13
2+
SO4 SCN
2+ 2+
Co / Fe
Acetate Phthalate Propionate Benzoate Salicylate
3+ +
N(Et)4
13
1 IC Theory
1.5.2
Direct ion chromatography

In ion chromatography without chemical suppression (direct ion chromatography), very high demands are made on the conductivity detector since the background conductivity which must be compensated is relatively large in comparison with the measuring signal. Of prime importance for the electronic suppression is the constancy of the background. Since the conductivity is, as mentioned above, greatly dependent on the temperature, an extremely good temperature constancy of the eluent in the conductivity measuring cell is required ( 0.01C). The sensitivity of the conductivity measurement depends on the difference between the equivalent ionic conductivities of sample ion (a) and eluent ion (e): c(eq ) ( a e )
a > e: a = e : a < e:
positive peak no peak negative peak
In anion determinations, salts of phthalic, salicylic or benzoic acid are usually employed since these possess a low equivalent ionic conductivity (see Table on page 13). If now an anion with a higher equivalent ionic conductivity appears in the detector cell, the conductivity increases and a positive peak is obtained. On the other hand, negative peaks appear if the equivalent ionic conductivity of the sample ion is lower than that of the eluent ion. An example of this is phosphate that, for example, in 2 mmol/L phthalic acid pH = 5.0 is present as H2PO4. Since (H2PO4) = 33 is lower than (phthalate) = 38, an insensitive negative peak is obtained under these con ditions (corrective measure: higher pH since (HPO42) = 57). The sensitivity for anions is in general 0.1 0.5 S/cm per 1 mg/L (= 1 ppm). With alkali and alkaline earth cations, chromatography is generally performed with dilute acids such as 2 mmol/L HNO3 as eluent. Since the proton has an exceptionally high equivalent ionic conductivity as a result of its special migration mechanism, the conductivity sinks drastically as soon as other cations replace the H+ ions. Generally, negative peaks are obtained which are very sensitive owing to the high value (in general 1 10 S/cm per 1 mg/L). The lower limit of the sensitivity depends on the detector noise, which lies between 0.1 10 nS/cm. This noise is determined essentially by the quality of the high pressure pump and the background conductivity. If the detection limit is defined as the signal height at a signal/noise ratio S/N = 3, it has the value 2 50 g/L for anions and 1 10 g/L for cations.
14
1.5 Conductivity detection
1.5.3
Ion chromatography with chemical suppression

Chemical suppression is based on the use of the salts of weakly dissociating acids (e.g. NaHCO3) as eluents. These eluents can be eliminated to a large extent by cation exchange in a post-column reaction according to the following equation. Na + + HCO3
+H+ Na +
H2 CO3
The carbonic acid formed as a result of cation exchange is very weakly dissociated and thus exhibits a very low residual conductivity. The sample anions undergo a corresponding reaction, shown here with the chloride anion as an example: Na + + Cl
+H+ Na +
HCl
The NaCl is converted to the corresponding free acid by the suppression; this has a considerably higher conductivity than the original salt. Of course this only applies for stronger acids; for medium-strong and weak acids the increase in sensitivity is correspondingly lower. The signal to be measured is + thus the sum of (Cl) and (H+) against a low background conductivity. For reasons which up to now are not completely clear the calibration function of this system is not linear with the concentration. This means that for calibration a considerably higher expenditure is required.
1.5.4
Comparison in the sensitivities of conductivity detection with and without chemical suppression
For anions the relationships mentioned above can be used to determine the following sensitivities for conductivity detection with electronic and chemical suppression:
Anion Sensitivity with electronic background suppression Sensitivity with chemical suppression
(
Fluoride Chloride Nitrate Sulfate Acetate
sample
phthalate
16 38 33 42 3
sample
+ +H
404 426 421 430 391
15
1 IC Theory According to these calculations the sensitivity of conductivity detection with chemical suppression should be higher for anions by a factor of 10 or more. However, when measurements made with the same instrument configuration are compared directly then chemical suppression normally only produces sensitivities which are higher by a factor of 2 to 4, as can be seen from the following table.
Detection limit with electronic background suppression Detection limit with chemical suppression
Anion
g/L
Chloride Nitrite Bromide Nitrate Sulfate 5 11 16 16 7
g/L
2 4 4 4 4
For cations the sensitivity with direct conductivity detection is already higher than with chemical suppression. The hydroxides of ammonium and the doubly charged cations also show a lower dissociation. Thus chemical suppression has no advantages for cation chromatography.
Sensitivity with electronic background suppression Sensitivity with chemical suppression
Cation
(
Lithium Sodium Potassium Ammonium Magnesium Calcium
+ sample
+H
+ sample
+ OH
311 300 276 277 397 290
237 248 272 271 251 258
16
1.5 Conductivity detection
1.5.5
Linearity of the calibration curve

An important parameter for analytical determination methods is the linearity of the calibration. If chemical suppression is used slightly curved calibration curves are usually obtained. In such cases the calibration values must be located as close as possible to the contents of the sample in order to obtain the most accurate results. In contrast, calibration curves obtained without chemical suppression remain linear for several decimal powers. An example of the differing linearity is shown in the following illustration. Calibration curves for nitrate with and without chemical suppression
100
area %
75 50
25
non suppressed suppressed (MSM)
0 0 5 10 15
ppm
20
Apart from this curve, which only shows a slight variation from linearity, the linear working ranges with and without the use of a suppressor differ considerably:
Anion Linear working range in g/L without suppressor Chloride Nitrate Sulfate 5 25000 15 10000 20 10000 with suppressor 5 500 5 500 5 200
17
1 IC Theory
1.6
1.6.1
Optical detection
General
In ion chromatography four different types of optical detection have been used up to now: Direct UV-VIS detection Direct UV-VIS detection is used as an addition to conductivity detection, e.g. for the determination of ions which absorb strongly in the UV range (nitrite, nitrate, organic anions) in the presence of high concentrations of inorganic ions (chloride, phosphate, sulfate), which either have no UV absorption or very little. Indirect UV-VIS detection Indirect UV-VIS detection finds universal application in direct ion chromatography for use with eluents with high UV absorption (e.g. phthalate buffers). Ions with no or very low UV activity show negative peaks and ions with a larger UV activity than the eluent show positive peaks. UV-VIS detection with post-column derivation UV-VIS detection is partly used coupled with post-column derivation for the detection of transitional metals (iron, nickel, copper, manganese, zinc...). Fluorescence detection In some special applications fluorescence detection is used for the highly sensitive detection of fluorescent compounds.
1.6.2
Direct UV-VIS detection

In direct UV-VIS detection the advantage of having different chromophore groups and thus very different detection sensitivities for the ions is used. The main area of application lies in the UV range, in which almost all organic ions absorb. The more chromophore groups (NO2, NO3, double bonds, phenyl, ketone, ...) which a molecule contains, the better the detection sensitivity. The maximum absorption of the most important functional groups is as follows:
18
1.6 Optical detection

Functional group Amino Aldehyde Carboxyl Ester Ethylene Ketone Nitro Phenyl
max. in nm
195 210 200 205 190 195 310 200
The very different detection sensitivity of the inorganic ions can be used with advantage for matrix reduction, particularly if the analytical samples have a high salt content. Chloride, sulfate and phosphate exhibit only very low UV absorption so that, for example, very low nitrite concentrations can be determined in the presence of large amounts of chloride. In addition the use of a UV detector allows the determination of organic acids which coeluate with sulfate as in this case only the organic acids, and not however the sulfate, are detected.
1.6.3
Indirect UV-VIS detection

In indirect UV-VIS detection an eluent with as high an absorption as possible is used so that the analytes reduce the detector signal. As already shown in section 1.5.2, the eluent concentration in the region of a peak is reduced by the amount of the analyte concentration. This means that at the same UV absorption of analyte and eluent no detector signal will be received while lower analyte absorption will result in a negative signal and higher analyte absorption a positive signal. Typical eluents for indirect UV-VIS detection are phthalate, benzoate, salicylate, various sulfonates and many others. The following table gives the optimum wavelengths and some detection limits for this type of detection:
Eluent Phthalate Benzoate Citrate
max. in nm
300 254 290
Detection limit (mg/L) 0.1 1 0.1 1 0.2 2
19
1 IC Theory
1.6.4
UV-VIS detection with post-column derivation

Post-column derivation should only be used if no other possibility exists; in principle all chemical or mechanical manipulations of any sort should be avoided after the separation as such reactions always result in a deterioration in the separation efficiency and in particular of the peak shape. One of the main uses of post-column derivation is the determination of transition metals in ion chromatography. If direct conductivity detection is no longer possible (electrical baseline compensation too low, sample with high salt content) then a photochemical reagent and auxiliary solutions are added to the eluent stream after the separation column. After passing through a reaction spiral the optical absorption of the metal complex is measured. Because of the different locations of the maximum absorption and the intensity of the color complexes of the individual metals the detection limits are very variable. However in some cases any matrix problems present can be reduced by selection of a suitable wavelength.
1.6.5
Fluorescence detection
Direct fluorescence detection has virtually no applications in ion chromatography as the analytes are inactive with the exception of a few metal complexes with fluorescent ligands. On the other hand there are several eluents used in IC which are suitable for use in indirect fluorescence detection (e.g. salicylate).
1.6.6
UV-VIS multiwavelength detection

The use of multiwavelength detectors such as diode arrays or "fast scanning" detectors requires a considerably larger expenditure for the necessary calculations (PC programs) but produces far better interpretations for problematical analyses. In particular for samples with peaks whose allocation is unknown certain statements about the structure of the ions under investigation can be made from the UV or VIS spectra obtained.
20
1.7 Electrochemical detection
1.7
Electrochemical detection
Electrochemical detection has occasionally been used with a lot of success. A pre-requirement is that the ions to be determined must be able to be either reduced or oxidized. This includes many organic compounds, the transitional metals and anions such as nitrite, nitrate, halides, oxohalides, pseudohalides, sulfide, sulfite, etc. There are four different techniques: Amperometry Coulometry Measurement of the current at a constant potential Measurement of the current at a constant potential but with 100% conversion of the analyte Measurement of the current against potential in a defined range of potential Measurement of the current at constant potential pulses
Voltammetry Pulsed amperometry
Amperometric (including pulsed) and coulometric detectors are most frequently used. The cells normally contain three electrodes: the working electrode, where the electrochemical reaction occurs, the reference electrode for currentless potential measurement and the auxiliary electrode as opposite pole to the working electrode. There are two different types of cell, the thin-layer cell and the wall-jet cell, which are shown schematically in the following illustration.
Thin-layer cell Wall-jet cell
1 Working electrode (WE) 2 Reference electrode (RE) 3 Auxiliary electrode (AE)

21
1 IC Theory The three electrodes are located in very different positions in various types of thin-layer cell. In the sequence in the direction of eluent flow all possible combinations can be found, e.g. WE first, then RE and finally AE or RE first, then WE followed by AE. The arrangement with WE and AE opposite each other followed by RE seems to be the best. In the wall-jet cell the WE is always the first electrode with the flow directed vertically onto it. The RE and AE follow in different sequences. The wall-jet cells are to be preferred to the thin-layer cells because of their greater sensitivity; however, after the WE there is a stronger mixing effect and turbulence in the eluent which is a disadvantage if a second detector has to be included. For the working electrodes mainly carbon (graphite or glassy carbon), gold, platinum, silver and very occasionally mercury (voltammetric detector cells) are used as electrode materials. When selecting the electrode material it must be remembered that every material is also electrochemically reduced and oxidized, i.e. each material provides a different potential window. These application ranges depend to a great extent on pH, solvent, type of ion and ionic concentration of the electrolyte. In the negative potential range the measuring range is limited by the electrolytic production of hydrogen from the protons of the solution and in the positive potential range by the electrochemical dissolution of the electrode material. The dissolution potential of the electrode depends very strongly on the anion of the electrolyte and on complex formers in particular. Approximate ranges for the various materials are given below:
Electrode material Potential range( V vs SCE) 1 mol/L NaOH Glassy carbon Platinum Gold Silver Mercury 1.4 1.0 1.2 0.5 1.2 0.8 1.2 0.2 2.6 0.0 1 mol/L HClO4 0.9 1.4 0.3 1.3 0.4 1.0 0.5 0.4 1.1 0.4
Voltammetric detector cells are usually constructed by the users themselves or voltammetric flow-through cells are integrated in the existing IC system.
22
1.8 Multiple detection
1.8
Multiple detection
The use of several detectors during a chromatographic analysis may be appropriate for complicated analytical problems. For example, it is a good idea to use a UV detector or ELCD together with the conductivity detector for the determination of very small amounts of nitrite in the presence of large amounts of chloride, as can be seen from the following example of its determination in surface water.
NO2 : 3.6 g/L
ELCD detection
Cl : 5528 g/L
Conductivity detection
NO3 F
SO4
For the safe identification of organic anions (e.g. hydroxy, di or tricarboxylic acids) in the presence of inorganic anions the coupling together of a conductivity detector with a UV or even a diode array detector is in many cases important.
23
1 IC Theory
1.9
Suppressors
All suppressors have basically the task of improving the detection of the analyte. In this respect a differentiation must be made between two effects or criteria in the suppression reaction: The high conductivity of the eluent is to be reduced to as low a level as possible. In addition the various counter ions of the analyte ions should be converted to a single ionic species with a higher equivalent conductivity.
1.9.1
Suppressor reactions
The basic reaction of such a suppressor in the anionic range has already been described in section 1.5.3. In the anion analysis sector when the normal sodium carbonate/hydrogen carbonate electrolytes are used the suppressor exchanges the sodium ions against protons and this carbonate ion leads to the formation of poorly dissociated carbonic acid. This reaction leads to a reduction in the conductivity of the electrolyte (first criterion). Na + + HCO3
+H+ Na +
H2 CO3
In addition all cations in the sample are converted to protons. As the proton has the largest equivalent conductivity of all cations this reaction provides a better detection sensitivity (second criterion). Na + + Cl
+H+ Na +
HCl
Careful attention must be given to both criteria when assessing whether the use of a suppressor makes sense. Such considerations lead to the result that in the anionic range the use of suppressors is indicated if carbonate eluents can be used. On the other hand only the first criterion is fulfilled for the use of suppressors in cationic analysis (reduction of the eluent conductivity), but not the second. Then in this case, for example, the suppressor reactions are as follows if nitric acid is used as the eluent and sodium chloride is present as analyte: Eluent: Analyte: H+ Na + + NO3
+OH NO3 +OH Cl
H2 O Na + + OH
+ Cl
24
1.9 Suppressors It follows that in direct ion chromatography the analyte ion Na+ is measured against H+, i.e. a negative peak will be obtained (difference {Na+} {H+} = 300 S). In contrast in the suppressor reaction the sodium ion is measured against water and all analyte anions will be converted to hydroxide ions (sum of {Na+} + {OH} = 248 S). From these figures it can be seen that normally the use of suppressors is only required when the detector of the IC system does not permit accurate measurements at higher basic conductivities.
1.9.2
Construction of suppressors
In the initial phases of ion chromatography ion exchanger columns were used as suppressors. After several hours of operation the columns were exhausted and had to be regenerated. A disadvantage of these columns was, apart from the necessary regeneration, a shift in the water peak which depended on the degree to which the column was exhausted and the oxidation of nitrite in the suppressor columns. At the moment both continuously and discontinuously regenerable suppressors are in use. All the continuously regenerable suppressors contain ion exchanger membranes or fibers and work on the counter-current principle. The fibers are immersed in the regeneration agent, e.g. diluted sulfuric acid. The eluent and the analyte flow through the fibers. The exchange of the sodium ions of the eluent against protons takes place through the ion exchanger membrane of the fibers. The membrane suppressors are constructed according to the sandwich principle. The eluent and analyte ions flow through a film between two membranes and the regeneration solution in spaces above and below these membranes. The advantage of these membrane and fiber suppressors is their continuous regeneration, however their pressure sensitivity and the diffusion of regenerator ions into the eluent are disadvantages. In the discontinuously regenerable suppressors, which can also be operated completely automatically, small ion exchanger columns with or without microchannels packed with ion exchangers are used. In this procedure the suppressor compartments are exchanged automatically after one or a few chromatograms. The advantages of these suppressors are their high pressure stability and their purity. The self-regenerable suppressors are basically membrane or discontinuously regenerable suppressors in which the protons for regeneration are obtained electrochemically by the electrolysis of water.
25
1 IC Theory
1.10
1.10.1
Evaluation and calibration

Evaluation of peak area
For a chromatogram recorded using a conductivity detector, the area under a substance peak is directly proportional to the amount of substance. To determine the peak areas, today electronic integrators or evaluation programs incorporating special algorithms for peak smoothing, peak recording and consideration of baseline drift are used almost without exception. Provided the start and end of the peak can be identified reasonably accurately, the peak area evaluation provides very good results for medium to high concentrations. The peak area determination must particularly be employed in cases where the capacity factors k change (e.g. through matrix effects). The area calculation can be problematic when the peak overlap is extensive, with peaks exhibiting severe tailing and with perceptible detector noise.
1.10.2
Evaluation of peak height

When the peak shape is constant, the peak height (the distance between the baseline and the peak maximum) is a quantity which is proportional to the peak area and which can also be used to evaluate chromatograms. The peak height determination is easily performed manually and is thus the method of choice if the chromatograms are only plotted on a recorder. A condition for the applicability of the height evaluation is constant k values. For reasons of linearity, it is suitable only for low to medium sample concentrations. The linear range is larger for components eluted later than for those eluted rapidly. With excessive peak overlap or a noisy baseline, the peak height evaluation can be superior to that of the peak area.
1.10.3
Calibration with external standard

The direct comparison of the signal magnitude (peak area or peak height) in an unknown sample with that of a standard solution of the same substance is by far the most frequently employed method of calibration in ion chromatography. It requires the injection of constant volumes under invariable chromatographic conditions. The substance to be analyzed is injected as a standard solution of about the same concentration as that in the sample. This can also be carried out repeatedly at different concentrations (onepoint, two-point, multipoint calibration). In a one-point calibration, the sample concentration sought is calculated as follows:
26
1.10 Evaluation and calibration ca

ca : cst : Sa : Sst :
= Sa
cst S st
concentraion in analysis sample concentration of standard solution signal of sample signal of standard
With two-point and multipoint calibrations, the calibration function specific to the substance is first plotted. Frequently, this function can be described by a calibration line obtained from the measured points with the aid of a linear regression analysis: S st
S0 : m:
S0 + m cst
intercept of the calibration line slope of the calibration line
In this case, the concentration in the analysis sample is calculated from the formula ca = Sa S0 m
The signal magnitude of the sample under investigation should lie between that of the lowest and the highest calibration standard since the calibration line is defined only within the concentration range investigated.
1.10.4
Calibration with internal standard

To take into account errors in the sample pretreatment (e.g. dispensing errors) or to determine recovery yields, the calibration with a second substance added to both the external standard and the sample can be used. This component, called an internal standard, should be eluted as near as possible to the substance to be analyzed yet be completely resolved and have a similar concentration, response and chemical structure. Since the sensitivities of the internal standard and the substance under investigation are usually not the same, the correction factor Fx must first be determined with ultrapure calibration solutions. Here, a solution of known concentration of the substance of interest (cx) and the internal standard (cis) is chromatographed. Fx is obtained from the measured signal heights Sis and Sx:
27
1 IC Theory Fx = Sis c x S x cis
If the correction factor Fx can be assumed constant in the concentration range of interest, the concentration ca of a sample, to which the internal standard has also been added, can be calculated as follows: ca = Sa cis Fx Sis
1.10.5
Calibration by standard addition

The standard addition method is used in ion chromatography primarily when matrix problems occur. The sample solution is spiked with a known quantity of the substance to be determined. The signals of the untreated sample and the spiked sample solution are measured; the chromatographic conditions must be identical. The standard addition can be performed once, twice or several times. In the simplest case with one standard addition, the unknown sample concentration ca is calculated with the aid of the known, added concentration difference c and the measured signal increase S: ca = Sa c S
With several standard additions, the sample concentration is calculated by linear regression analysis. The advantage of the standard addition method lies in its greater reliability since calibration in the sample is performed under actual matrix conditions. Problems are recognized rapidly by non-linear standard addition or shifts in peak height. Long-term changes in temperature, pressure, etc. are taken into account by the continual updating of the calibration and have no influence on the measurement results. However, this reliability costs analysis time as calibration must be performed with every sample and not just periodically as with the external standard method.
28
1.11 References
1.11
References
Heinz Engelhardt Hochdruck-Flssigkeits-Chromatographie Springer-Verlag, Berlin, 1977 Frank C. Smith, Richard C. Chang The Practice of Ion Chromatography John Wiley & Sons, New York, 1983 Veronika Meyer Praxis der Hochleistungs-Flssigchromatographie Diesterweg Salle Sauerlnder, Frankfurt a.M., 1985 Georg Schwedt Chromatographische Trennmethoden Thieme Verlag, Stuttgart, 2. Aufl., 1986 D. Frahne, M. Lubli, G. Zimmermann Konduktometrische Detektion zweiwertiger Kationen mit Einsulen-IC GIT Fachz. Lab. 31, 1167-1169 (1987) Douglas T. Gjerde, James S. Fritz Ion Chromatography Dr. Alfred Hthig Verlag, Heidelberg, 2nd ed., 1987 James G. Tarter (ed.) Ion Chromatography (Chromatographic science; v. 37) Marcel Dekker, Inc., New York, 1987 Georg Schwedt Ionen-Chromatographie anorganischer Anionen und Kationen in: Analytiker-Taschenbuch, Band 7, Springer-Verlag, Berlin, 1988 Paul R. Haddad, Peter E. Jackson Ion Chromatography, Principles and Applications (Journal of Chromatography Library, volume 46) Elsevier, Amsterdam, 1990
29
1 IC Theory
Joachim Weiss Ionenchromatographie VCH, Weinheim, 2. Aufl., 1991 German Bogenschtz, Andreas Wild, Jochen Schfer Fortschritte in der Ionenanalytik mit IC LaborPraxis 20, 38-46 (1996) (available as offprint from Metrohm) Claudia Dengler, Maximilian Kolb, Markus Lubli Ionenchromatographische Applikationen mit Einsulen- und Suppressortechnik GIT Fachz. Lab. 40, 1104-1109 (1996) (available as offprint from Metrohm) Claudia Dengler, Maximilian Kolb, Markus Lubli Methodenvergleich der Ionenchromatographie mit und ohne chemische Suppression GIT Fachz. Lab. 40, 609-614 (1996) (available as offprint from Metrohm)
30
2.1 General hints
Columns and eluents
2.1
2.1.1
General hints
Eluents
For the preparation of the eluents one should use chemicals of a purity degree of at least "p.a.". For diluting please use high purity water. Fresh eluents should always be microfiltered (0.45 m filter) and degassed (with N2, He or vacuum). The eluent should be continuously stirred with a magnetic stirrer, particularly when the recycling procedure is employed or when alkaline eluents are used. For alkaline eluents and eluents with low buffering capacity one should preferably use CO2 absorbers. The supply vessel containing the eluent must be closed as tightly as possible to avoid excessive evaporation. This is primarily important with eluents containing organic solvents (e.g. acetone), the evaporation of which can lead to drifts in the long term. If work is performed in a very sensitive range, even if one drop of condensate falls back in the eluent this can cause a noticeable change in the background conductivity. Influence of various parameters on anion columns Concentration: pH: Organic modifiers: An increase in the concentration usually leads to shorter retention times and quicker separation, but also to a higher background conductivity. pH alterations lead to shifts in the dissociation equilibrium and thus to changes in the retention times. Addition of an organic solvent (e.g. methanol, acetone, acetonitrile) to aqueous eluents generally increases the retention times. The influence is usually greater on divalent anions than on monovalent anions.
31
2 Columns and eluents Eluent change When the eluent is changed, it must be ensured that no precipitates can be formed. Solutions used in direct succession must therefore be miscible. If the system has to be rinsed with an organic solution, several solvents with increasing or decreasing lipophilic character may possibly have to be used (e.g. water acetone chloroform).
2.1.2
Protection of separating columns

To protect the column against foreign bodies which could have an adverse influence on the separation efficiency, we advise you to subject both the eluents and all samples to microfiltration (0.45 m filter) and to siphon the eluent through the 6.2821.090 Suction Filter. To avoid contamination by abrasive particles arising from piston seals of the 709 IC Pump, it is advantageous to install an in-line filter between the pump and the 733 IC Separation Center. The optional 6.2821.000 Manufit Filter Unit is eminently suitable for this purpose. The use of readily interchangeable precolumns serves to protect the actual separating columns and increase their service life appreciably. The precolumns available from Metrohm are either actual precolumns or so-called precolumn cartridges which are used together with the 6.2821.050 Twin Cartridge Holder, the 6.2821.040 Cartridge Head, or the 6.2828.010 Precolumn Cartridge Holder. For preserving the column material from pressure drops caused by the injector it is recommended to use the optional 6.2620.050 Portmann Pulsation dampener between the 709 IC Pump and the 733 IC Separation Center 733. Always store the separating columns closed when not in use and filled with an eluent in accordance with the manufacturers specifications.
2.1.3
Regeneration of columns
If the separation properties of the column have deteriorated, it can be regenerated in accordance with the column manufacturers specifications. With the separating columns available from Metrohm, the instructions for regeneration can be found on the leaflet enclosed with every column.
In the case of separating columns with carrier material based on silica, no alkaline solutions may be used for regeneration, otherwise the columns could be damaged.
Dead volume at the end of a column can be the cause of extreme peak broadening or splitting (appearance of double peaks). Filling the column with glass beads ( 100 m) frequently improves the separation efficiency. 32
2.2 IC Anion Column Hamilton PRP-X100 (6.1005.000)
2.2
2.2.1
IC Anion Column Hamilton PRP-X100 (6.1005.000)

Column specifications
Column packing Polystyrene/divinylbenzene copolymer with quaternary ammonium groups Dimensions Precolumn 125 4.0 mm 6.1005.020 IC Precolumn cartridge PRP-X100 (use together with 6.2821.040 Cartridge head or 6.2821.050 Twin cartridge holder) 1 ... 13 (above 30C max. pH = 8) 8.0 mL/min 34 MPa (340 bar) The column is filled with phthalic acid eluent pH = 5.0. The column is stored in eluent for short periods (weeks) and in methanol/water (1:4) for longer periods (months). Wash the column by passing through 0.5 mol/L tartaric acid or nitric acid (10 mL nitric acid 6 mol/L in 1L methanol); flow rate 0.5 mL/min ca. 2 h.
pH range Max. flow Max. pressure Preparation Storage
Regeneration
2.2.2
General remarks
The column can only be used in systems without chemical suppression. Sample solutions must always be filtered through a 0.45 m membrane filter. Possibly dilute samples with eluent or use H+ ion exchanger cartridges (6.1012.110) for injection. For preserving the column it is recommended to use the 6.1005.020 Precolumn cartridge and the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector. For more information on this column, see Application Bulletin No. 265.
33
2 Columns and eluents
2.2.3
Phthalic acid eluent

Composition Preparation 2 mmol/L phthalic acid, 7.6 % acetone, pH 5.0 (NaOH); conductivity approx. 160 S/cm
Concentrate solution Add 3.323 g phthalic acid, 2 mL NaOH 30 % and 10 mL acetone to 950 mL of high purity water. After dilution (ev. with warming up), set the pH value to 4.5 with NaOH 1 mol/L and fill up to 1 L with high purity water. Ready-to-use eluent Mix 100 mL concentrate solution with 75 mL acetone and fill up to 1 L with high purity water. The pH value of this solution is now exactly 5.0.
Flow: Injection volume: Full Scale: Polarity: 2.0 mL/min 100 L 4 S/cm +
Standard chromatogram
2 1 3 4 5 6
1 S/cm
Peak 1 2 3 4 5 6
Component Fluoride Chloride Nitrite Bromide Nitrate Sulfate System peak
Conc. [mg/L] 5 5 5 10 10 10
tR [min] 1.2 1.8 2.0 2.7 3.2 9.9 14
34
2.3 IC Anion Column SUPER-SEP (6.1009.000)
2.3
2.3.1
IC Anion Column SUPER-SEP (6.1009.000)

Column packing Polymethacrylate with quaternary ammonium groups Dimensions 100 4.6 mm Precolumn 6.1009.010 IC Anion precolumn SUPER-SEP or 6.1005.050 IC Precolumn cartridge PRP-1 (use together with 6.2821.040 Cartridge head or 6.2821.050 Twin cartridge holder) Whether or not this precolumn can be used, depends on the sample matrix and has to be tested in any case. 1 ... 13 2.0 mL/min 2.5 MPa (25 bar) The column is filled with phthalic acid eluent. The column is stored in eluent. Rinse with 0.1 mol/L HNO3/20 % acetonitrile; flow 0.3 mL/min ca. 24 h. If this is not sufficient, rinse with the following solutions: Metal impurities: 0.1 mol/L sodium tartrate Protein impurities: 0.1 mol/L NaOH or 20% acetic acid Organic impurities: 20 % acetonitrile in high purity water
pH range Max. flow Max. pressure Preparation Storage Regeneration
2.3.2
General remarks
The column can only be used in systems without chemical suppression. Sample solutions must always be filtered through a 0.45 m membrane filter. Eluents should not contain more than 20% of organic solvents. Large concentrations of divalent cations can perturb the base line. Especially for sensitive analyses, they should be removed with a 6.1012.110 H+ ion exchanger cartridge. The column must be used together with the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector.
35
2.3.3
Phthalic acid eluent

Composition Preparation 2.5 mmol/L phthalic acid, 5 % acetonitrile, pH 4.2 (TRIS); conductivity approx. 130 S/cm
Concentrate solution Dissolve 4.15 g phthalic acid in 950 mL high purity water with warming up. Add 10 mL acetonitrile and adjust the pH value to 3.8 with TRIS (solid). After this fill up to 1 L with high purity water. Ready-to-use eluent Mix 100 mL concentrate with 50 mL acetonitrile and fill up to 1 L with high purity water.
1 S/cm
4 5 6
Peak 1 2 3 4 5 6
Conc. [mg/L] 5 5 5 10 10 10
tR [min] 1.7 2.4 2.9 3.5 4.2 5.8 10
36
2.3 IC Anion Column SUPER-SEP (6.1009.000)
2.3.4
Benzoic acid eluent

Composition Preparation 3 mmol/L benzoic acid, 2 % acetonitrile, pH 4.65 (TRIS); conductivity approx. 120 S/cm Dissolve 366 mg benzoic acid in 20 mL acetonitrile and make up to 1 L with high purity water. Set the pH value of the degassed solution to 4.65 with TRIS. Flow: Injection volume: Full Scale: Polarity: 1.5 mL/min 100 L 4 S/cm +
1 S/cm
2 4
3 1
7 8
12
16
Peak 1 2 3 4 5 6 7 8
Component Acetate Fluoride Formiate Chloride Nitrite Bromide Nitrate System peak Sulfate
Conc. [mg/L] 10 5 5 5 5 10 10 10
tR [min] 1.7 2.2 2.6 3.4 4.4 5.4 6.7 10 14.3
37
2.4
2.4.1
IC Glass Cartridge Metrosep Anion Dual 1 (6.1006.020)

Column packing Spheric hydroxyethyl methacrylate with quaternary ammonium groups Dimensions Precolumn Glass cartridge 150 3.0 mm (installation in 6.2828.000 Glass Cartridge Holder) 6.1006.030 Precolumn Cartridge METROSEP Anion Dual 1 (installation in 6.2828.010 Precolumn Cartridge Holder) 2 ... 12 (>12 only briefly) 0.7 mL/min (recommended flow 0.5 mL/min) 9 MPa (90 bar) Column and precolumn cartridge are stored in phthalate eluent and can be used directly for ion chromatography without suppression. For ion chromatography with suppression, the system must be rinsed during ca. 4 h with the carbonate eluent at a flow rate of 0.5 mL/min. The column cartridge is stored for a short period (days) in the closed holder. For long-term storage (weeks) the cartridge is stored in the supplied storage vessel in acetone/water (1:9) in the dark. Rinse with 0.1 mol/L HNO3 for ca. 2 h at 0.3 mL/min, then switch to rinsing with standard eluent.
pH range Max. flow Max. pressure Preparation
Storage
Regeneration
2.4.2
General remarks
Sample solutions must always be filtered through a 0.45 m membrane filter. The orthophosphate determination requires an IC system with chemical suppression. The column is not suited for the determination of low fluoride concentrations with acidic eluents. The column is not suited for the determination of low nitrite concentrations with chemical suppression. Eluents may contain maximum 10% organic solvents. The column cartridge must not be rinsed with high purity water. The column cartridge must be used together with the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector. For more information on this column, see Application Bulletin No. 260.
38
2.4 IC Glass Cartridge Metrosep Anion Dual 1 (6.1006.020)
2.4.3
Phthalic acid eluent (without chemical suppression)

Composition Preparation 8 mmol/L phthalic acid, 2 % acetonitrile; pH = 4.1 (TRIS); conductivity approx. 400 S/cm
Concentrate solution Dissolve 13.3 g phthalic acid in 950 mL high purity water with warming up. Add 10 mL acetonitrile, let the solution cool down and adjust the pH value to 4.0 with TRIS (solid). Then fill up to 1 L with high purity water. Ready-to-use eluent Mix 100 mL concentrate with 20 mL acetonitrile and fill up to 1 L with high purity water.
Flow: Injection volume: Full Scale: Polarity : 0.5 mL/min 100 L 10 S/cm +
2 1
1 S/cm
4 5 6 3
Peak 1 2 3 4 5 6
Conc. [mg/L] 5 5 5 10 10 10
tR [min] 3.2 4.5 5.3 6.2 7.2 10.2 17
39
2.4.4
HCO3/CO32 eluent (with chemical suppression)

Composition 2.5 mmol/L sodium carbonate, 2.4 mmol/L sodium hydrogen carbonate; conductivity after chemical suppression ca. 16 S/cm Dissolve 265 mg sodium carbonate (water-free) and 201.5 mg sodium hydrogen carbonate in high purity water, then fill up to 1 L with high purity water. Depending on the sample organic acids may cause interferences with fluorides (lactate, glycolate) and with sulfates (tartrate, malate, malonate). Flow: Injection volume: Full Scale: Polarity:
2
1 S/cm
Preparation
Remarks
Standard chromatogram 0.5 mL/min 20 L 10 S/cm +
1 4 3 6 5 7
Peak 1 2 3 4 5 6 7
Component Fluoride Chloride System peak Nitrite Bromide Nitrate Orthophosphate Sulfate
Conc. [mg/L] 2 5 5 10 10 10 10
tR [min] 3.6 5.5 6.5 7.1 8.3 10.0 11.8 14.6
40
2.5 IC Anion Column Metrosep Anion Dual 2 (6.1006.100)
2.5
2.5.1
IC Anion Column Metrosep Anion Dual 2 (6.1006.100)

Column packing Polymethacrylate with quaternary ammonium groups Dimensions Precolumn 75 4.6 mm 6.1005.050 Precolumn cartridge PRP-1 (4 x 20 mm RP phase on polystyrene/divinyl benzene, use together with 6.2821.050 Twin cartridge holder) 1 ... 12 1.2 mL/min (recommended flow 0.8 mL/min) 7 MPa (70 bar) Columns are filled with borate/gluconate eluent. Columns are stored in the used eluent at room temperature. Rinse with 0.1 mol/L HNO3 at 0.3 mL/min during ca. 2 h, then rinse with standard eluent; or rinse with eluent containing 100 mmol/L of the buffer salt. Organic impurities: Rinse with eluent containing an organic solvent (<20 % vol.).
pH range Max. flow Max. pressure Preparation Storage Regeneration
2.5.2
General remarks
Sample solutions must always be filtered through a 0.45 m membrane filter. The orthophosphate determination requires an IC system with an alkaline eluent. Suitable for determination of anions in trace range. Eluents may contain maximum 20% organic solvents. No tris-(hydroxymetyl)-aminomethane (TRIS) must be used for setting the pH value of the phthalic acid eluent. For preserving the column it is recommended to use the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector. For more information on this column, see Application Bulletin No. 261.
41
2.5.3
Phthalic acid eluent (without chemical suppression)

Composition Preparation 5 mmol/L phthalic acid, 2 % acetonitrile; pH = 4.5 (NaOH); conductivity approx. 400 S/cm
Concentrate solution Add 5 mL NaOH 10 mol/L to 950 mL high purity water and dissolve 8.31 g phthalic acid in this solution with warming up. Add 10 mL acetonitrile, let the solution cool down and adjust the pH value to 4.3 with NaOH. Then fill up to 1 L with high purity water. Ready-to-use eluent Mix 100 mL concentrate with 20 mL acetonitrile and fill up to 1 L with high purity water.
2 1 4 5 3 6
1 S/cm
Peak 1 2 3 4 5 6
Conc. [mg/L] 5 5 5 10 10 10
tR [min] 2.3 3.4 4.1 5.0 5.9 9.5 15
42
2.5 IC Anion Column Metrosep Anion Dual 2 (6.1006.100)
2.5.4

Composition 1.3 mmol/L sodium carbonate, 2.0 mmol/L sodium hydrogen carbonate; conductivity after chemical suppression ca. 14 S/cm Dissolve 137.5 mg sodium carbonate (waterfree) and 168 mg sodium hydrogen carbonate in high purity water, then fill up to 1 L with high purity water. Depending on the sample organic acids may cause interferences with fluorides (lactate, glycolate) and with sulfates (tartrate, malate, malonate). Flow: Injection volume: Full Scale: Polarity: 0.8 mL/min 20 L 5 S/cm +
Preparation
Remarks
4 1
1 S/cm
6 3 5
9 8
Peak 1 2 3 4 5 6 7 8 9
Component Fluoride Acetate Formiate Chloride Nitrite Bromide Nitrate Orthophosphate Sulfate
Conc. [mg/L] 2 2 2 5 5 10 10 10 10
tR [min] 3.2 3.6 4.1 5.8 8.3 10.5 13.6 15.6 19.4
43
2.6
2.6.1
IC Anion Column Phenomenex STAR ION A300 (6.1005.100)

Column packing Polystyrene/divinylbenzene copolymer with quaternary ammonium groups Dimensions pH range Max. flow Max. pressure Preparation Storage Regeneration 100 4.6 mm 1 ... 12 2.0 mL/min (recommended flow 1.5 mL/min) 7 MPa (70 bar) The column is filled with sodium bicarbonate/carbonate eluent and can be used directly. The column is stored in the used eluent at room temperature. Rinse 30 min with a solution containing 17 mmol/L sodium bicarbonate and 18 mmol/L sodium carbonate (flow rate 1 mL/min).
2.6.2
General remarks
The column can only be used in systems with chemical suppression. Limited suitability for the analysis of chloride as carbonates interfere with chloride. Sample solutions must always be filtered through a 0.45 m membrane filter. Eluents must not contain any organic solvents. For preserving the column it is recommended to use the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector. For more information on this column, see Application Bulletin No. 262.
44
2.6 IC Anion Column Phenomenex STAR ION A300 (6.1005.100)
2.6.3

Composition 1.8 mmol/L sodium carbonate, 1.7 mmol/L sodium hydrogen carbonate; conductivity after chemical suppression ca. 14 S/cm Dissolve 190.5 mg sodium carbonate (waterfree) and 142.5 mg sodium hydrogen carbonate in high purity water, then fill up to 1 L with high purity water. Flow: Injection volume: Full Scale: Polarity:
2 1 4 5 7 6
1 S/cm
Preparation
Standard chromatogram 1.5 mL/min 20 L 5 S/cm +
Peak 1 2 3 4 5 6 7
Component Fluoride System peak Chloride Nitrite Bromide Nitrate Orthophosphate Sulfate
Conc. [mg/L] 2 5 5 10 10 10 10
tR [min] 1.5 1.9 2.1 2.6 3.4 4.3 7.5 9.3
45
2.7
2.7.1
IC Exclusion Column Hamilton PRP-X300 (6.1005.030)

Column packing Polystyrene/divinylbenzene copolymer with sulphonic acid groups Dimensions Precolumn 250 4.0 mm 6.1005.040 IC Precolumn cartridge PRP-X300 (use together with 6.2821.040 Cartridge head or 6.2821.050 Twin cartridge holder) 1 ... 13 8.0 mL/min 34 MPa (340 bar) The column is filled with 0.5 mol/L H2SO4. The column is stored in eluent for short periods (weeks) and in methanol/water (1:4) for longer periods (months). Divalent cations remain on the column and form complexes with citrates which give an incorrect citrate peak. It is thus a good idea to inject 100 L 0.1 mol/L Na2EDTA from time to time. If necessary the column can be rinsed for 6 h with 0.01 mol/L H2SO4 + 20 % methanol at a flow rate of 0.5 mL/min.
pH range Max. flow Max. pressure Preparation Storage
Regeneration
2.7.2
General remarks
The column can only be used in systems without chemical suppression. Sample solutions must always be filtered through a 0.45 m membrane filter. As monovalent cations are only eluted very late and divalent cations are not eluted at all these should be removed by a cation exchanger before the injection. For preserving the column it is recommended to use the 6.1005.040 Precolumn cartridge and the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector.
46
2.7 IC Exclusion Column Hamilton PRP-X300 (6.1005.030)
2.7.3
HClO4 eluent
Composition Preparation 1.5 mmol/L perchloric acid; conductivity approx. 300 S/cm
Concentrate solution 0.1 mol/L perchloric acid (ready-to-use solution, available on the market). Ready-to-use eluent Add 15 mL concentrate to 900 mL high purity water and fill up to 1 L with high purity water.
UV detection at 190 nm can also be carried out with this eluent; this has advantages in the determination of tartrate compared with conductivity detection. Flow: Injection volume: Full Scale: Polarity: 1.0 mL/min 100 L 5 S/cm +
Remarks
2
1 S/cm
3 4
Peak 1 2 3 4 5 6
Component Tartrate Malate Citrate Lactate Acetate Succinate
Conc. [mg/L] 4 7.5 7.5 10 25 40
tR [min] 1.8 2.6 3.1 4.2 6.3 8.8
47
2.8
2.8.1
IC Cation Column Nucleosil 5SA (6.1007.000)

Column packing Spherical silica gel with sulphonic acid groups, = 5 m Dimensions Precolumn 125 4.0 mm 6.1007.010 IC Precolumn cartridge Nucleosil 5SA (use together with 6.2821.040 Cartridge head or 6.2821.050 Twin cartridge holder) 2 ... 7 The column can be used directly. The column is stored in eluent for short periods (weeks) and in methanol/water (1:4) for longer periods (months). Inject 100 L c(Na2EDTA) = 0.1 mol/L Note: Do not use any alkaline EDTA solutions! Rinse with 30 mL c(HNO3) = 0.1 mol/L at a flow rate of 0.5 mL/min.
pH range Preparation Storage
Regeneration
2.8.2
General remarks
Sample solutions must always be filtered through a 0.45 m membrane filter. The pH of the standard and sample solutions must lie between 2.5 and 3.5. To ensure this the solutions are either made up or diluted with eluent or adjusted to this value with nitric acid (HNO3). For preserving the column it is recommended to use the 6.1007.010 Precolumn cartridge and the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector.
48
2.8 IC Cation Column Nucleosil 5SA (6.1007.000)
2.8.3
Tartaric acid/citric acid eluent

Composition 4 mmol/L tartaric acid, 0.5 mmol/L citric acid, 3 mmol/L ethylene diamine, 5 % acetone; conductivity approx. 500 S/cm Dissolve 0.6 g tartaric acid and 105 g citric acid in high purity water. Add 3 mL of a 1 mol/L ethylene diamine solution (6.7 mL ethylene diamine per 100 mL) and 50 mL acetone and fill up to 1 L. Flow: Injection volume: Full Scale: Polarity:
2
1 S/cm
Preparation
Standard chromatogram 1.5 mL/min 100 L 5 S/cm
Peak 1 2 3 4
Component Nickel Zinc Cobalt Manganese
Conc. [mg/L] 5 5 5 10
tR [min] 2.7 3.4 4.3 7.5
49
2.9
2.9.1
IC Cation Column Metrosep Cation 1-2 (6.1010.000)

Column packing Spherical silica gel with polybutadiene maleic acid groups Dimensions Precolumn 125 4.0 mm 6.1010.010 IC Precolumn cartridge Metrosep Cation 1-2 (use together with 6.2821.040 Cartridge head or 6.2821.050 Twin cartridge holder) 2 ... 7 The column is filled with eluent and can be used directly. The column is stored in eluent (storage temperature +4C). Avoid drying up of the column packing! Organic impurities: Rinse the column with 40 mL high purity water, 40 mL acetone and 40 mL high purity water (flow rate 1 mL/min).
pH range Preparation Storage Regeneration
2.9.2
General remarks
Sample solutions must always be filtered through a 0.45 m membrane filter. The pH of the standard and sample solutions must lie between 2.5 and 3.5. To ensure this the solutions are either made up or diluted with eluent or adjusted to this value with nitric acid (HNO3). The eluent can be preserved by addition of 1 % acetonitrile. Higher concentrations of organic solvents deteriorate the sodium/ammonium separation. Alcohols alter the selectivity of the column material; they should therefore not be used in eluents. For preserving the column it is recommended to use the 6.1007.010 Precolumn cartridge and the 6.2620.050 Pulsation dampener, which minimizes the pressure shocks caused by the injector. All solutions must be stored in plastic containers. To obtain a correct sodium determination all contact with glass must be avoided. For more information on this column, see Application Bulletin No. 257.
50
2.9 IC Cation Column Metrosep Cation 1-2 (6.1010.000)
2.9.3
Tartaric acid/dipicolinic acid eluent

Composition Preparation 4 mmol/L tartaric acid, 1 mmol/L dipicolinic acid; conductivity approx. 700 S/cm Dissolve 167 mg dipicolinic acid and 0.6 g tartaric acid in 100 mL high purity water with warming up, then fill up to 1 L with high purity water. Heavy metal ions contained in the sample solution are complexed by the dipicolinic acid and are eluated in the front peak; as a result they do not interfere with the determination. Flow: Injection volume: Full Scale: Polarity:
2 1 3 5 4 7 6
1 S/cm
Remarks
Standard chromatogram 1.0 mL/min 10 L 5 S/cm
Peak 1 2 3 4 5 6 7 8
Component Lithium Sodium Ammonium Potassium Calcium Magnesium Strontium Barium
Conc. [mg/L] 1 5 5 10 10 10 20 20
tR [min] 2.9 3.4 3.8 4.7 7.2 10.6 12.7 19.0
51
52
Index
Index
A
Acetate .....................................37,47 Acetone .........................................31 Addition of ligands ........................10 Adsorption.......................................7 Alkali cations..................................14 Alkali metal ions.............................10 Alkaline earth cations ....................14 Alkaline eluents..............................31 Ammonium ....................................51 Amount-of-substance concentration .............................12 Amperometry.................................21 Anion exchanger .............................3 Anions............................................15 Asymmetry factor ............................7 Auxiliary electrode .........................21 Columns and eluents ................... 31 Conductance................................ 12 Conductometry............................. 12 Conductivity.................................. 12 Conductivity detection.................. 12 Constancy of the background...... 14 Construction of suppressors........ 25 Correction factor........................... 27 Coulometry ................................... 21 Counter-current principle ............. 25 Crown ether .................................. 10
H
HAMILTON PRP-X100 .................. 33 HAMILTON PRP-X300 .................. 46 HClO4 eluent................................. 47 2 HCO3 /CO3 eluent ........... 40,43,45 High purity water .......................... 31 Hydroxyethyl methacrylate ........... 38
I
IC Anion Column HAMILTON PRP-X100 .............. 33 IC Anion Column Metrosep Anion Dual 2 ............. 41 IC Anion Column Phenomenex STAR ION A300 .. 44 IC Anion Column SUPER-SEP .............................. 35 IC Cation Column Metrosep Cation 1-2 ................. 50 IC Cation Column Nucleosil 5SA............................ 48 IC Exclusion Column HAMILTON PRP-X300 .............. 46 IC Glass Cartridge Metrosep Anion Dual 1 ............. 38 IC Precolumn Cartridge Metrosep Anion Dual 1 ............. 38 IC Precolumn Cartridge Metrosep Cation 1-2 ................. 50 IC Precolumn Cartridge Nucleosil 5SA............................ 48 IC Precolumn Cartridge PRP-1 ................................... 35,41 IC Precolumn Cartridge PRP-X100.................................. 33 IC Precolumn Cartridge PRP-X300.................................. 46 IC Precolumn SUPER-SEP ........... 35 Indirect fluorescence detection ................................... 20 Indirect UV-VIS detection ........ 18,19 In-line filter .................................... 32 Integrators .................................... 26 Interelectrode distance................. 12 Interferences in the chromatogram .................... 11 Internal standard .......................... 27 Introduction .................................... 1 Ion chromatographic separations ................................. 8 Ion chromatography with chemical suppression ....... 15 Ion exchange .................................. 2 Ion exchanger columns ................ 25 Ion exchanger fibers..................... 25 Ion exchanger membranes .......... 25 Ionic conductivity.......................... 13
D
Dead time ....................................... 4 Dead volume .......................... 4,7,32 Degassing .................................... 31 Detection limit.......................... 14,19 Detection limit with chemical suppression .............................. 16 Detection limit with electronic background detection............... 16 Detector noise .............................. 14 Diode array detectors................... 20 Direct ion chromatography........... 14 Direct UV-VIS detection................ 18 Dispensing error ........................... 27 Dissociation equilibrium .......... 11,31 Double peaks ............................... 32
B
Background conductivity...............14 Barium ...........................................51 Base line drifts...............................26 Benzoic acid..................................14 Benzoic acid eluent .......................37 Bromide.........................34,36,37,39, ....................................40,42,43,45
C
Calcium .........................................51 Calibration .....................................26 Calibration by standard addition.......................28 Calibration curves..........................17 Calibration with external standard .......................26 Calibration with internal standard ........................27 Capacity factor .............................5,6 Carbonate......................................44 Carbonate eluents ......................9,24 Carbonate in water ..........................8 Carbonate system peak ................11 Cartridge head ..............................32 Cation exchanger ............................3 Cations ..........................................16 Cell constant..................................12 Characteristics.................................4 Chemical effects..............................7 Chemical suppression ..................15 Chloride .........................34,36,37,39, ...............................40,42,43,44,45 Chromatogram ................................4 Chromatographic characteristics....4 Chromophore groups ...................18 Citrate ............................................47 CO2 absorber ................................31 Coated silica gels ............................8 Cobalt ............................................49 Column material ..............................8 Column overloading ........................7
E
ELCD ............................................ 23 Electrochemical detection............ 21 Electrode material ........................ 22 Electrode surface ......................... 12 Eluent anions ................................ 11 Eluent change .............................. 31 Eluent composition......................... 9 Eluents.......................................... 31 Eluents with organic solvents ....... 31 Equivalent conductivity............ 12,13 Equivalent ionic conductivity ... 13,14 Errors in sample pretreatment...... 27 Evaluation ..................................... 26 Evaluation programs .................... 26 Evaporation .................................. 31 External standard ......................... 26
F
Fast scanning detectors............... 20 Filter unit Manufit .......................... 32 Fluorescence detection........... 18,20 Fluoride ..... 34,36,37,39,40,42,43,45 Formiate ....................................... 37
G
Gaussian curve .............................. 4 Glass beads ................................. 32 Glassy carbon .............................. 22
53
Index
K
Kohlrausch's law ...........................12
L
Lactate ..........................................47 Liquid chromatography...................1 Ligands .........................................10 Linear regression...........................27 Linear working range.....................17 Linearity of calibration curves........17 Lipophilic character.......................32 Lithium...........................................51
M
Magnesium ...................................51 Malate............................................47 Manganese ...................................49 Matrix problems ............................28 Matrix reduction.............................19 Maximum absorption ....................18 Membrane suppressors................25 Metrosep Anion Dual 1 .................38 Metrosep Anion Dual 2 .................41 Metrosep Cation 1-2 .....................50 Microfiltration............................31,32 Multi-point calibration....................27 Multiple detection..........................23 Multiwavelength detection ............20
Peak height evaluation ..................26 Peak smoothing ............................26 Peak width....................................4,5 Peak width at half height .................4 pH changes...................................31 Phenomenex STAR ION A300.......44 Phosphate .....................................14 Phthalic acid..................................14 Phthalic acid eluent ........34,36,39,42 Plate number ................................5,6 Polyhydroxy alkylmethacrylate .........................8 Polymers .........................................3 Polymethacrylate...................8,35,41 Polystyrene/divinylbenzene copolymer..........................8,44,46 Positive peaks ...............................14 Post-column derivation ............18,20 Potassium .....................................51 Precipitates....................................32 Precolumn cartridge holder ..........32 Precolumn cartridges....................32 Precolumns ...................................32 Pulsed amperometry.....................21 Protection of separating columns ...................32 PRP-1 .......................................35,41 PRP-X100 ......................................33 PRP-X300 ......................................46 Pulsation dampener ......................32
Signal/noise ration.........................14 Silica gels .................................48,50 Single point calibration..................26 Sodium ..........................................51 Splitting..........................................32 Standard addition..........................28 Standard deviation ..........................4 Standard solution ..........................26 STAR ION A300.............................44 Stirring ...........................................31 Strontium .......................................51 Styrene-divinylbenzene resin ..........3 Succinate.......................................47 Suction filter...................................32 Sulfate ........34,36,37,39,40,42,43,45 SUPER-SEP...................................35 Support material..............................8 Suppression ..................................15 Suppressor reactions ....................24 Suppressors..................................24 System peak .................................11
T
Tailing ..............................................7 Tartaric acid/citric acid eluent .................................49 Tartaric acid/dipicolinic acid eluent .................................50 Tartrate ..........................................47 Temperature dependence ............13 Test chromatogram.........................8 Theoretical plate..............................5 Theory .............................................1 Thin-layer cell ................................21 Transition metals ......................10,20 Twin cartridge holder.....................32
N
Negative peaks .............................14 Net retention time............................4 Net retention volume .......................4 Nickel ............................................49 Nitrate............................17,34,36,37, ...............................39,40,42,43,45 Nitrite ........................19,23,34,36,37, ...............................39,40,42,43,45 Noise .............................................14 Nucleosil 5SA ................................48 Number of theoretical plates...........5
Q
Quality of the IC Pump ..................14
R
Recovery rate ................................27 Recycling.......................................31 Reducibility....................................21 Reference electrode......................21 References ....................................29 Regeneration of columns ..............32 Relative retention.............................5 Resistance.....................................12 Resolution .......................................6 Retention time .........................4,5,31 Retention volume ............................4
U
UV-VIS detection ...........................18 UV-VIS detection with post-column derivation.........18,20 UV-VIS multiwavelength detection....................................20
O
Ohm's law......................................12 Optical detection...........................18 Optimum wavelength ....................19 Organic anions..............................23 Organic modifiers..........................31 Orthophosphate........38,40,41,43,45
V
Valency..........................................12 Voltammetric detector cells...........22 Voltammetry ..................................21
S
Salicylic acid..................................14 Selectivity .....................................5,6 Sensitivity of conductivity measurement.............................14 Sensitivity with chemical suppression...............................16 Sensitivity with electronic background suppression ..........16 Separating columns ......................32 Shift of dissociation equilibrium ....11
W
Wall-jet cell ....................................21 Water peak ...............................11,25 Working electrode .........................21
P
Particle size .....................................3 Peak area evaluation.....................26 Peak broadening.....................5,7,32 Peak detection ..............................26 Peak base width..............................4
Z
Zinc................................................49
54

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Ion Chromatography

Dr. Helwig Schfer Dr. Markus Lubli Dr. Roland Drig

Metrohm Ltd. CH-9101 Herisau Switzerland

Helwig Schfer Markus Lubli Roland Drig

Metrohm Monograph 8.014.5003 8.732.2003

8.732.2003 Monograph Ion chromatography

Columns and eluents .................................................................. 31

8.732.2003 Monograph Ion chromatography

Theory of Ion Chromatography

liquid gaseous liquid

Polarity of the mobile phase

8.732.2003 Monograph Ion Chromatography

Ion exchange as a separation mechanism

[ A ] stat [ E ]mob [ A ]mob [ E ] stat

8.732.2003 Monograph Ion Chromatography

1.2 Ion exchange as a separation mechanism

8.732.2003 Monograph Ion Chromatography

2 t,1 t0 w0.5,1 w0.5,2 2 t,2

wb,1 t'R,1 t'R,2

Dead time Retention time

Net retention time Standard deviation

w0.5 Peak width at half height = 2.354 t

8.732.2003 Monograph Ion Chromatography

1.3 Chromatographic characteristics

Capacity factor k'

8.732.2003 Monograph Ion Chromatography

8.732.2003 Monograph Ion Chromatography

1.3 Chromatographic characteristics

8.732.2003 Monograph Ion Chromatography

Ion chromatographic separations

Dependence of the separation on the column material

8.732.2003 Monograph Ion Chromatography

1.4 Ion chromatographic separations

Influence of the eluent composition on the separation

8.732.2003 Monograph Ion Chromatography

8.732.2003 Monograph Ion Chromatography

1.4 Ion chromatographic separations

Interferences in the chromatogram: system peak

8.732.2003 Monograph Ion Chromatography

8.732.2003 Monograph Ion Chromatography

Equivalent ionic conductivities for infinite dilution in aqueous solutions at 25C

[ S cm2 mol-1 ] 198 54 76 78 77

+ [ S cm2 mol-1 ] 350 39 50 74 73

Acetate Phthalate Propionate Benzoate Salicylate

8.732.2003 Monograph Ion Chromatography

Direct ion chromatography

8.732.2003 Monograph Ion Chromatography

1.5 Conductivity detection

Ion chromatography with chemical suppression

404 426 421 430 391

8.732.2003 Monograph Ion Chromatography

311 300 276 277 397 290

237 248 272 271 251 258

8.732.2003 Monograph Ion Chromatography

1.5 Conductivity detection

Linearity of the calibration curve

non suppressed suppressed (MSM)

8.732.2003 Monograph Ion Chromatography

Direct UV-VIS detection

8.732.2003 Monograph Ion Chromatography

1.6 Optical detection

Indirect UV-VIS detection

Detection limit (mg/L) 0.1 1 0.1 1 0.2 2