Ion Chromatography:

Separation of Polar and Ionic Compounds

Tracy Benson, Ph.D.
Typical LC System Operation
! Analytes adsorb onto solid
surface due to analyte/surface
intermolecular forces
! Good chromatography
occurs from proper selection
of adsorbent material and
mobile phase
! Changes in conc gradient
of mobile phase disturbs the
analyte/surface forces and
analyte migrates through bed
and onto the dectector
Mobile Phase Conc Gradient !
Packed Tubular Column
!"#$%&'($) &+,)$-,)$)
Adsorption is
" The attraction of molecules onto a
particle surface
" Driven by a concentration gradient
" Interacted by molecular forces
(short range and long range)
between the adsorbate and
adsorbent
" An exothermic process
C
A
,b
Porous
Pellet
Internal
Diffusion
C
A
,s
C
A

IC Solid Surface Chemistry
Retention is based on the affinity of different
ions for the site and on a number of other
solution parameters (pH, ionic strength,
counterion type, etc.).
Ion - Pair Chemistry
Ion: particle formed when a neutral atom or group of atoms gains or loses one or
more electrons. An atom that loses an electron forms a positively charged ion (cation);
an atom that gains an electron forms a negatively charged ion (anion).
In Solution
A
aq
m+
+ B
aq
n-
"! (nA
m+
! mB
n-
)
org
Ion pairs are oppositely charged
ions held together by coulombic
attractions, non-covalently, and
behave as a single unit
On a Solid Surface
A
m
+
+ B
m
-
"! Ab
m
A
m
+
+ Y
m
-
+ L
s
"! SYL
s
B
m
-
+ Z
m
+
+ L
s
" ! BZL
s
A
m
+
+ B
m
-
+ Ls " ! ABL
s
Ion pair formation in mobile phase
Adsorption of solute ion onto ligand
Adsorption of counter-ion onto ligand
Adsorption of ion pair onto ligand
EQUILIBRIUM DRIVEN BUT KINETICALLY CONTROLLED
LluenL
8oule
./$
0
1
+/$
0
2
ump
Cuard Column
Analyucal
Column
Suppressor
8egen ln
.+
3
#$
4
2
ConducuvlLy
Cell
ChromaLograph
Soware
lon
Lxchange
Separauon
osL-
Suppresslon
ConducuvlLy
uaLa
Pandllng and
lnsLrumenL
ConLrol
Sample
ln[ecuon
8egen CuL
.+
3
#$
4
2
Conventional Ion Chromatographic System
Anion Analysis
Pump Module
Pump Module
Specification Highlights
Flow
Range = 0.001 to 10 mL/min
Accuracy = 0.1% at 1 mL/min
Precision = 0.1% at 1 mL/min
Gradient reproducibility = +/- 0.5%
Gradient accuracy = 0.5%
Delay volume < 400 "L
Pressure range = 50 to 5000 psi
Pressure ripple typically < 1.0%
"& "567 &589
Eluent Generator Module
Eluent Generator Module
Same device supports single
or dual chemistry
OH, MSA, CO
3
,
CO
3
:HCO
3
eluents
Supports CR-TC technology
Supports CRD technology
Supports EPM
(Electrolytic pH Modifier)
Slide-out tray
Optical leak sensor
Status bar for basic operation
Same footprint for single or dual
,: ,75;<= :;<;>6=?>
%@(/ #AB=;8 !CD6<=6E;B
rovldes rellable and convenlenL eluenL sources
and ellmlnaLe Lhe convenuonal eluenL
preparauon errors
Slmplles and performs boLh lsocrauc and
gradlenL lon chromaLographlc separauons
!usL add waLer"-prolongs pump seals, reduces
malnLenance
8euer gradlenL performance
Lower cosL of ownershlp
Eluent Generator Module
Advantages of Using Eluent Generators
Use only deionized water
On-line high purity eluent
generation
Insure reproducible eluent
concentration
minimal gradient delay
Reduce pump maintenance
Gradient eluent
programming now practical
MSA Eluent Generation for Cation
Analysis
-#!F
,7;G=>?7A=;
%;B;>D?H>
,75:;<
I
-#!
/6>=>HCE;
Anlon-Lxchange
ConnecLor
MSA
Cenerauon
Chamber
venL
ump
P
2
C
L Anode
L CaLhode
(2 P
2
C + 2e
-
2CP
F
+ P
2
)
J-#!K !
/5>>;<=
@7?L %6=;
J F K
J M K
-#! M $
3
-#!
C
2

";E6
B
N<H=
(P
2
C 2P
+
+
1
/
2
C
2
+ 2e
F
)
-#! O -;=P6<;B57Q?<HG !GHC
C8-C1C
Cauon 1rap
-#!
F
lmproved erformance for 1race Anlon
Analysls uslng a kCP LluenL CeneraLor
Column: IonPac

AG11, AS11, 2 mm
Eluent: (A) NaOH
(B) KOH (EGC-KOH cartridge)
0.5 mM to 2.5 min, to 5.0 mM at 6 min,
to 26 mM at 20 min
Flow Rate: 0.5 mL/min
Inj. Volume: 1.0 mL
Suppressor: ASRS

, external water mode

Detection: Suppressed conductivity
Peaks: 1. Fluoride 0.37 "g/L (ppb)
2. Acetate 1.0
3. Formate 0.93
4. Chloride 0.44
5. Nitrite 0.27
6. Bromide 1.0
7. Nitrate 0.33
8. Carbonate
9. Sulfate 0.64
10. Oxalate 0.39
11. Phosphate 1.1
S
1.20
0
.!2 /?<D;<R?<67
:>6CH;<=
11
10
9
8
7
6
3
4
3
2
1
MlnuLes
0 3 10 13 20
0
S
1.20
.S2 ,: :>6CH;<=
11
10
9
8
1
2
3 4
3
6
7
Column: lonac

AC11, AS11, 4 mm
LluenL: 0.3 Lo 23 mmol/L kCP
lrom: LC40 or 0.1 mol/L kCP
llow 8aLe: 2 mL/mln
ln[ecuon: 23 L
ueLecuon: ConducuvlLy aer AS8S

suppresslon, recycle mode
eaks: 1. lluorlde 0.2 mg/L
2. Chlorlde 0.3
3. nlLraLe
1.0
4. SulfaLe
1.3
3. hosphaLe 1.3
S
0 2 4 6 8 10
0
1
2
3
4
.!2 :>6CH;<= ,:4T
3
4
3
2
1
MlnuLes
0 2 4 6 8 10
0
1
2
3
4
S
.S2 /?<D;<R?<67 :>6CH;<=
1
2
3
4
3
Detector Module
1hree dlsuncL secuons for separauon, deLecuon and auLomauon
SeparaLe LemperaLure conLrol for columns and deLecLors
AuLomauo
n
ueLecuon
Separauon
10 Lo 70 C
13 Lo 40 C
uual 1hermal
ComparLmenLs
Secuon uC Module
Detector Module
Role of Suppression in Conductivity
Detection
Neutralize eluent and reduce background
conductance to a low or negligible level
Increase sensitivity by converting the analyte
ions to highly conductive form
Removes sample counter ions (cations or
anions)
# = #
$a+
+ #
Cl-
%
# = #
&+
+ #
Cl-
LqulvalenL Conducuvlues
Anions #
OH

198
F

54
Cl

76
NO
3

71
Acetate

41
Benzoate

32
20383
Cations #
H
+
350
Li
+
39
Na
+
50
K
+
74
CH
3
NH
3
+
58
N(CH
3
CH
2
)
4
+
33
Range of IC Autosamplers
5 mL
AS40 AS AS-HV
10 mL
250 mL