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IC IC ICIC
Theory of IC
An introduction to Ion Chromatography
K. H. Viehweger
Metrohm AG, Herisau, Switzerland
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Theory of IC
Content
What is chromatography?
Chromatography
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Theory of IC
History
Definition
Greek
chroma = colour
graphein = to write
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Theory of IC
History
topsoils as ion exchanger for Mg2+, Ca2+ and NH4+
sulfonated and aminated polymers
sulfonated polystyrene/divenylbenzene resins
(Manhattan project)
LC
1947 aminated PS/DVB resins as ion exchanger
1953 ion exclusion chromatography
1957 macro pore ion exchanger
1959 theoretical background
1967-70 pelicular ion exchange materials
1975 ion exchange chromatography with conductivity
detection and stripper (suppressor)
HPLC
1979 conductivity detection with electronic
suppression
1976-80 ion pair chromatography
1850
1935
1942
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Thomson, Way
Adams, Holms
dAlelio
McBurney
Wheaton, Baumann
Corte, Meyer et al.
Helfferich
Horvath, Kirkland
Small, Stevens, Baumann
Gjerde, Fritz, Schmuckler
Waters, Bidlingmeier, et. al
IC
IC IC ICIC
Chromatography
Going back to school
A simple experiment from school
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Chromatography
Physico chemical
Definition
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.
mobile phase
stationary phase
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gaseous
liquid
liquid GLC, LLC
solid GSC, LSC
(HPLC - IC)
IC
IC IC ICIC
Chromatography
Column interactions
Types of chromatography
Mobile phase dissolves and transports the analyte
Stationary phase retains the analyte
adsorbing adsorption
chromatography
dissolving distribution
chromatography
reacting ion exchange
chromatography
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Chromatography
Polarities
Methods of chromatography
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Chromatography
Traditional methods
Group 1 traditional TLC + HPLC
1. Normal phase chromatography
Stationary p. = polar (e.g. SiO2)
mobile p. = non polar (e.g. n-hexane)
2. Reversed phase
chromatography
Stationary p. = non-polar (e.g. C18)
mobile p. = polar
(e.g. acetonitrile or methanol/water)
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IC
IC IC ICIC
Chromatography
IC methods
Group 2 IC
4. Ion exchange chromatography
Cations and anions form a weak ionic binding with the stationary phase.
C: Stationary p. = polar (e.g. R-SO3) mobile p. = polar (e.g. HNO3 aq.) or
A: Stationary p. = polar (e.g. R-NR3+) mobile p. = polar (e.g. Na2CO3 aq.)
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IC
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Chromatography
IC methods
Group 2 IC
3. Ion pair chromatography
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IC
IC IC ICIC
Chromatography
IC methods
Group 2 IC
5. Ion exclusion chromatography
By adding H+-ions the stationary phase is transformed into a non ionic but polar
Donan membrane. Only non dissociated molecules can enter this membrane. If
they dissociate they are excluded from the stationary phase. The separation is
though depending on the dissociation constant of the respective molecules.
mobile p. = polar (e.g. H2SO4 aq.)
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Chromatography
Resume
Definition
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IC
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Chromatography
HPLC and IC
Liquid-solid-chromatography
Since the introduction of high pressure or high performance
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. Ion chromatography is an aliquot
of the HPLC-family.
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IC
IC IC ICIC
Chromatography
Most popular set up
Eluent
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IC
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Chromatography
Where does it actually happen?
Eluent
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Detector
IC
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Chromatography
Ion exchange
The stationary phase
Styrene
Divinylbenzene
Styrene-divinylbenzene resin
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Anion
exchanger
IC
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Chromatography
Anion exchanger
Ion exchange
Composition of the
stationary phase
quaternary
ammonium groups
alkyl amines
hydroxyalkylamines
alkyl amines with
acrylate type
crosslinking
Substrates
Cation exchanger
Polystyrene/divinylbenzene
Polymethacrylate
Polyalcohol
Hydroxyethylmethacrylate (HEMA)
Silicate
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sulfonates
carboxylates
Spacer
alkyl chain
IC
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Chromatography
Ion exchange
Mobile Phase
anions (I)
...
Phthalic acid
Salicylic acid
p-Hydroxybenzoic acid
Benzoic acid
Borate
Borate/Gluconate
Potassium hydroxide
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anions (II)
cations (I)
...
Carbonat/bicarbonate
Potassium hydroxide
Borate
Nitric acid
Tartaric acid
Tartaric acid/dipicolinic acid
Tartaric acid/citric acid
Sodium dihydrogene phosphate
oxalic acid/ethylene diamine/acetone
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Chromatography
Ion exchange
Cation separation mechanism
Stationary phase and mobile phase compete for the analyte
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IC
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Chromatography
Ion exchange
Cations
C2 250
Tartaric-/dipicolinic acid/crown
ether; 4/0.45/0.05 mmol/L
0.5
1 Lithium
2 Sodium
1.0
3 NH4+
1.0
4 MEA
1.0
5 DEA
1.0
6 Potassium
4.8
7
TEA
5.0
MDEA
4.8
9
10
Calcium
Magnesium
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5.0
4.0
ppm
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IC
IC IC ICIC
Chromatography
Ion exchange
Cations (selected)
I
II
III IV
VI VII
VIII
II
III
IV
VI VII VIII
H
Li
He
Be
Ne
Na Mg
Al
Si
Cl
Ar
Cu Zn Ga Ge As Se
Br
Kr
Xe
At
Rn
Ca Sc
Ti
Sr
Zr
Nb Mo Tc Ru Rh Pd Ag Cd
In
Sn Sb Te
Cs Ba
La
Hf
Ta
Tl
Pb
Rb
Fr
Cr Mn Fe Co
Re Os
Ir
Ni
Pt
Ra Ac Ku
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Au Hg
Bi
Po
IC
IC IC ICIC
Chromatography
Ion exchange
Anion separation mechanism
Stationary phase and mobile phase compete for the analyte
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IC
IC IC ICIC
Chromatography
Ion exchange
Anions
A Supp 5 250
NaHCO3/Na2CO3; 1/3.2 mmol/L
1
Fluoride
5.0
Chlorite
5.0
Bromate
5.0
Chloride
5.0
Nitrite
5.0
Chlorate
5.0
Bromide
5.0
Nitrate
5.0
10
Phosphate
5.0
11
Sulfate
5.0 ppm
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IC
IC IC ICIC
Chromatography
Ion exchange
Anions (selected)
I
II
III IV
VI VII
VIII
II
III
IV
VI VII VIII
H
Li
He
Be
Ne
Na Mg
Al
Si
Cl
Ar
Cu Zn Ga Ge As Se
Br
Kr
Xe
At
Rn
Ca Sc
Ti
Sr
Zr
Nb Mo Tc Ru Rh Pd Ag Cd
In
Sn Sb Te
Cs Ba
La
Hf
Ta
Tl
Pb
Rb
Fr
Cr Mn Fe Co
Re Os
Ir
Ni
Pt
Ra Ac Ku
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Au Hg
Bi
Po
IC
IC IC ICIC
Chromatography
Ion exchange
Cations
Anions
Separation
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IC
IC IC ICIC
Chromatography
Ion exclusion
Anion separation mechanism
Lipophilic interaction between analyte and stationary phase
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IC
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Chromatography
Ion exclusion
Organic acids
Metrosep Organic Acids
Perchloric acid; 0.5 mmol/L
1
Lactate
1.0
Formate
1.0
Acetate
1.0
Propionate
1.0
Butyrate
1.0
iso-Butyrate
1.0
Valerate
1.0
iso-Valerate
1.0
ppm
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IC
IC IC ICIC
Chromatography
Ion exclusion
Mobile Phase
Anions are excluded and elute with the void volume in the solvent front.
Anions of organic acids form with protons weak organic acids. These
acids are only to a small degree dissociated and have a low polarity.
Stationary phase
Interaction
As long as the organic acids are not dissociated they can stay in the
Donan membrane. If they are dissociated they become ionic. In this
case they are excluded from membrane.
Attention!
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IC
IC IC ICIC
Chromatography
Ion pair
Cation and anion separation mechanism
RP reversed phase mechanism
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IC
IC IC ICIC
Chromatography
Ion pair
Mobile Phase
Stationary phase
Cations
Analyte cation (e.g. Na+) plus lipophilic anion (e.g. alkyl sulphonic acid)
form a non polar molecule
Anions
Analyte anion (e.g. Cl) plus lipophilic cation (e.g. tetra butyl ammonium)
form a non polar molecule
The lipophilic end of the modified anion or cation molecule interact with the
stationary phase in the RP-mode. This interaction leads to different
retention times and that means separation of substances which are
chemically quite similar.
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IC
IC IC ICIC
Chromatography
Detection
Eluent
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Detector
IC
IC IC ICIC
Chromatography
Detection
Types of detection
Conductivity detector
Amperometric detector
UV/VIS detector (optical)
RI detector (optical)
IC/MS
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IC
IC IC ICIC
Detection
Electrochemical
Measuring principle
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IC
IC IC ICIC
Detection
UV/VIS
Characteristics
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IC
IC IC ICIC
Detection
UV/VIS indirect
Characteristics
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IC
IC IC ICIC
Detection
UV/VIS with pcr
Characteristics
Selective determinations
Time consuming (wet chemistry is needed)
More complex system
Additional peak broadening
Last possibility if all other approaches fail
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IC
IC IC ICIC
Detection
IC/MS
Characteristics
+
+++
++++
Skimm
Capilla ers Octopo
le
ry
Fragme
ntation
zone
(CID)
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+ +
Lenses
Detect
or
Quadru
pole
IC
IC IC ICIC
Detection
Conductivity
What is conductometry?
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1
* Kc
R
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IC
IC IC ICIC
Detection
Conductivity
What is specific conductivity?
= ( i * zi * ci )
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IC
IC IC ICIC
Detection
Conductivity
Values for equivalent conductivity
Anions
OH
F
Cl
Br
I
NO2
NO3
HCO3
CO32
SO42
Phthalate
Cations
198
54
76
78
77
72
71
45
72
80
38
H+
Li+
Na+
K+
NH4+
Mg2+
Ca2+
Sr2+
Ba2+
Zn2+
Cu2+
350
39
50
74
73
53
60
59
64
53
55
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IC
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Detection
Conductivity
What influences the measured value?
the concentration
the temperature
1
= * Kc
R
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= ( i * zi * ci )
El . = c * El . + c * El .
+
El .
El .
42
T 2 %/C
Chemical suppression
IC IC ICIC
With or without?
Ion chromatography without suppression
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IC
IC
IC IC ICIC
Chemical suppression
Without
Characteristics
Det . = Peak El .
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Det . = cSmpl
*(
)
+
c
Smpl . El . Smpl . *( Smpl . El .)
.
+
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IC
IC IC ICIC
Chemical suppression
Without
Determination of cations and anions
+
Det . = cSmpl
. *( Smpl . El .) + cSmpl . *( Smpl . El .)
+
The counter ion of the sample is not retained and eluted in the void volume so
the counter ion is always that of the eluent
+
Det . = cSmpl
. *( Smpl . El .)
+
Det . = cSmpl
. *( Smpl . El .)
Keywords:
z one column technique non suppressed ion chromatography
z measurement of the difference between the conductivity of the
sample ion and the eluent ion
45
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IC
IC IC ICIC
Chemical suppression
With
Ion chromatography with chemical suppression
46
IC
IC IC ICIC
Chemical suppression
With
Characteristics
Det . = Peak El .
+
Det . = cSmpl
. *( Smpl . El .) + cSmpl . *( Smpl . El .)
+
47
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IC
IC IC ICIC
Chemical suppression
With
Determination of cations and anions
+
Det . = cSmpl
*(
)
+
c
.
Smpl . *( Smpl . El .)
Smpl .
El .
+
Keywords:
two column technique suppressed ion chromatography pcr
measurement of the sum of the sample ion and H+ or OH
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IC
IC IC ICIC
Chemical suppression
Comparison
IC without suppression
Cations
IC with suppression
Det . = c Smpl . * ( Na H )
Det . = cSmpl . * ( Na + OH )
D et . = c Sm pl . * (5 0 3 5 0 )
D e t . = c S m p l . * (5 0 + 1 9 8 )
= c
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Smpl
Det
* 300
49
D et.
= c
Sm pl.
* 248
IC
IC IC ICIC
Chemical suppression
Comparison
IC without suppression
Anions
IC with suppression
Det . = c Smpl . * ( Cl OH . )
Det . = cSmpl . * ( H + Cl )
D et . = c S m p l . * ( 3 5 0 + 7 6 )
Det
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Smpl
= c Smpl . * ( 76 198 )
= c
Det .
* 112
50
D et.
= c Sm pl. * 4 2 6
Chemical suppression
Comparison
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IC
IC IC ICIC
IC
IC IC ICIC
Chemical suppression
Comparison
IC without suppression
IC with suppression
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IC
IC IC ICIC
Suppressors
ASRS
H2O
Eluent/Sample
Eluent/Sample
H2 + O2
Anode
Na+ H+
Cl OH
OH OH
H+
OH
Na+ OH
OH Na+
OH
Na+
OH H+
Ion exchange
membranes
Auto self
regenerating
suppressor for
anions or cations
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Cathode
2 OH 4 e O2 + 2 H+
H2O H+ + OH
2 H+ + 2 e H2
53
H2O
Housing
[H2SO4]
IC
IC IC ICIC
Suppressors
Evaluation
Membrane Suppressor
Continuous regeneration
No additional solvents
Not solvent stable
Expensive
Limited lifetime
Noise 3-5 nS
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IC
IC IC ICIC
Suppressors
Metrohm Suppressor Module MSM
Packed bed suppressor
Na+ H+ / Na2CO3 H2CO3
Me+ H+ / MeCl H+ + Cl
Suppression
H2SO4
Regeneration
H 2O
Rinsing
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IC
IC IC ICIC
Suppressors
Evaluation
Metrohm Suppressor Module MSM
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IC
IC IC ICIC
Suppressors
Metrohm CO2 Suppressor MCS
Sequential suppression
H2CO3 H2O + CO2
From MSM
CO2
Removal
H2 O
Outlet
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IC
IC IC ICIC
Suppressors
Evaluation
Metrohm CO2 Suppresser MCM
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IC
IC IC ICIC
What is IC?
Resume
Ion Chromatography
Principles of chromatography
Chromatographic separation techniques
Ion chromatography separation techniques
Detection in ion chromatography
Conductivity measurements
Suppression reaction
Conductivity after suppression reaction
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