Basics of Ion Chromatography

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

1
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

2
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]

3
General setup of an IC
Detector

Mobile phase
(Eluent)

Injection
valve
High pressure
pump

Separation
column
4
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.

5
weak interaction
fastest movement
shortest retention time

6
weak interaction
fastest movement
shortest retention time

medium interaction
faster movement
faster retention time

7
weak interaction
fastest movement
shortest retention time

medium interaction
faster movement
faster retention time

strong interaction
slow movement
long retention time

8
Analytical column material

Styrene

 

Divinylbenzene
Styrene-divinyl-
benzene resin Cation Anion
exchanger exchanger

for cations for anions

9
Eluent

Mobile phase
(Eluent)

10
Eluent

The analytes compete for places on the stationary phase

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

11
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.

12
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
…

13
Detection
Detector

14
Detection

Various types of detectors exist, but most commonly

a conductivity detector is used

 electrical field between two electrodes

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

15
Detection
Conductivity, measuring principle

16
Suppression

17
Suppression

18
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

19
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 !

20
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
21
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 !

22
Suppression

23
1st Suppressing step : Chemical Suppression (MSM)

24
 2nd Suppressing step : Physical Suppression (MCS)

H2CO3 H2O + CO2

From MSM

CO2 
Removal

H2O
Outlet

25
Degasser

26
Degasser

27
28
29
 Chromatogram

12
2
11
Retention 10
time conc.

Conductivity [µS/cm]
9
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

30
 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

31
 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

32
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]

33