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Basics of Ion Chromatography

Thomas Hartmann
Product Manager IC – Online System
Competence Center Ion Chromatography
Metrohm International Headquarters

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The principle of chromatography
take a piece of paper

make a little drop with «black» ink

just add water to it’s center

see the colors that make up


the «black» ink

Greek: Chroma - Colour


Grafein - to write
«chromatography» = wide range of physical chemical separation processes

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Basics of Ion Chromatography

chloride
12
11
10

fluoride

sulphate
9

nitrate
bromide
8

Conductivity [µS/cm]
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nitrite
6

phophate
5
4
-
NO3 3
2

1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
time [min]

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General setup of an IC
Detector

Mobile phase
(Eluent)

Injection
valve
High pressure
pump

Separation
column
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Separation mechanism

The separation of a sample takes place in the column.


Every component of the sample needs a specific time to
pass the column.
This time is called retention time and is used for the
identification of the analyte.

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weak interaction
fastest movement
shortest retention time

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weak interaction
fastest movement
shortest retention time

medium interaction
faster movement
faster retention time

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weak interaction
fastest movement
shortest retention time

medium interaction
faster movement
faster retention time

strong interaction
slow movement
long retention time

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Analytical column material

Styrene

 

Divinylbenzene
Styrene-divinyl-
benzene resin Cation Anion
exchanger exchanger

for cations for anions


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Eluent

Mobile phase
(Eluent)

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Eluent

The analytes compete for places on the stationary phase


with the eluent. The stronger the eluent the shorter the
retention time.

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Eluent

The analytes compete for places on the stationary phase


with the eluent. The stronger the eluent the shorter the
retention time.
Eluent composition is an important factor in IC.
Eluent has similar chemical properties as the analytes.

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Eluent
cations (+) anions (-) non suppressed IC
 tartaric acid/dipicolinic acid  phthalic acid
 nitric acid  salicylic acid
 tartaric acid  p-hydroxybenzoic acid
 tartaric acid/citric acid  benzoic acid
 sodium dihydrogene phosphate  borate
 oxalic acid/ethylene diamine/acetone  borate/Gluconate
...

anions (-) suppressed IC


 carbonate/bicarbonate
 sodium or potassium hydroxide
 Borate

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Detection
Detector

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Detection

Various types of detectors exist, but most commonly


a conductivity detector is used

 electrical field between two electrodes


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  * Kc in a flow through cell
ability of the solution to transport
R 
electrical charge is measured
 conductivity is the reciprocal of the
R = resistance []
resistance
Kc = cell constant [1/cm]
 = specific conductivity  eluent and analytes contribute to total
[1/  or S] conductivity
 non-specific detector

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Detection
Conductivity, measuring principle

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Suppression

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Suppression

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Why we need Suppression?
Λ0+(S·cm2mol-
Kation 1) Anion Λ0-(S·cm2mol-1)

H+ 349,8 OH- 198,6


Li+ 38,7 F- 55,4
Na+ 50,1 Cl- 76,8
K+ 73,5 Br- 78,1
Rb+ 77,8 I- 76,8
Ag+ 61,9 NO3- 71,5
NH4+ 73,6 ClO3- 64,6
N(C2H5)4+ 32,4 ClO3- 67,4
1/2 Mg2+ 53,1 HCO3- 44,5
1/2 Ca2+ 59,5 HCOO- 54,6
1/2 Ba2+ 63,6 CH3COO- 40,9
1/2 Cu2+ 56,6 1/2 SO42- 80,0
1/3 La3+ 69,7 1/2 CO32- 69,3
1/3 Ce3+ 69,8 1/3 Fe(CN)63- 100,9

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Why we need Suppression?

Specific conductivity

3 mM Na2CO3 (Eluent) ~ 507000 nS·cm−1

10 ppb Chloride (Analyte ~ 21900 nS·cm−1

Background conductivity 23 times higher than analyte signal !

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Suppression
Reduction of the background conductivity and
increase of analyte conductivity.
CO2
MSM Suppressor
Eluent: - + H+
Na+ + HCO3 H2CO3 H2O + CO2
- Na+
high low lowest
conductivity conductivity conductivity
+ H+
Sample: Na+ + Cl- H+ + Cl-
- Na+
low high
conductivity conductivity
all cations are replaced by H+ CO2 is removed
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Why we need Suppression?

Specific conductivity

3 mM Na2CO3 (Eluent) ~ 507000 nS·cm−1

10 ppb Chloride (Analyte) ~ 21900 nS·cm−1

Background conductivity ~ 23 times higher than analyte signal !

With Suppression

Ultrapure water 54,9 nS·cm−1

Background conductivity ~ 400 times smaller than analyte signal !

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Suppression

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1st Suppressing step : Chemical Suppression (MSM)

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2nd Suppressing step : Physical Suppression (MCS)

H2CO3 H2O + CO2


From MSM

CO2 
Removal

H2O
Outlet

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Degasser

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Degasser

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Chromatogram

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2
11
Retention 10
time conc.

Conductivity [µS/cm]
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Peak [min] Analyte [ppm] 8 1
1 3.36 fluoride 10 5 7
7 4
2 5.39 chloride 10
6 3
3 6.64 nitrite 10
5
4 8.48 bromide 10
4
5 9.89 nitrate 10
3 6
6 12.53 phosphate 10
7 14.69 sulphate 10 2
1
0
Retention time  identification 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1
time [min]
Peak area  quantification

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The performance of IC
Cations

I II III IV V VI VII VIII I II III IV V VI VII VIII


H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac Ku

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The performance of IC
Anions

I II III IV V VI VII VIII I II III IV V VI VII VIII


H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac Ku

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Basics of Ion Chromatography

chloride
12
11
10

fluoride

sulphate
9

nitrate
bromide
8

Conductivity [µS/cm]
7

nitrite
6

phophate
5
4
-
NO3 3
2

1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
time [min]

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