Ion Chromatography

17
1 Ion Exchange Chromatography

description

kromatografi

Transcript of Ion Chromatography

Page 1: Ion Chromatography

1

Ion Exchange Chromatography

Page 2: Ion Chromatography

2

ComponentsSame as any HPLC Instrument

ReservoirsPumpInjectorColumnDetectorChromatography Software

Specific Components

Membrane Suppressor

Page 3: Ion Chromatography

3

Ion Exchange Chromatography

Basic Separation Principle: Exchange equilibria between ions in solution and ions (of the same charge) held by surface bonded functional groups

Page 4: Ion Chromatography

4

Ion Exchange Functional Groups

Cation ExchangeSulfonic acid – SO3

- (H+)

Carboxylic Acid

Anion ExchangePrimary Amine – NH3

+(OH-)

Tertiary Amine

– C – O-(H+) =O

– N – CH3

CH3

CH3

+

(OH-)

Page 5: Ion Chromatography

5

Mobil Phase

Cation Exchange – H+

Anion Exchange - OH-

pH is controlled with a Buffer Solutione.g. HCO3

-/CO3--

Page 6: Ion Chromatography

6

Stationary Phase – Ion Exchange Resin

Page 7: Ion Chromatography

7

Stationary Phase – Solid Support “Backbone”

CH CH2 CH CH2

CH CH2

styrene Divinylbenzene (DVB)

Page 8: Ion Chromatography

8

Polystyrene Divinylbenzene

R R

RR R

CH CH2 CH CH2CH CH2

CH CH2 CH CH2CH CH2 CH CH2

Page 9: Ion Chromatography

9

1. Cellulose (the cellulose, derived from wood or cotton, is lightly derivatized with ionic groups to form the ion exchanger).

Anion exchange

Cation exchange

2. Gel-type ion exchangers: combine the separation properties of gel filtration with those of ion exchange. Because of their high degree of substitution of charged groups, which results from their porous structures, these gels have a higher loading capacity than do cellulosic ion exchangers.

Stationary Phase – Ion Exchange Resin

Page 10: Ion Chromatography

10

Separation of Ca2+ Mg2+ Sr2+ and Ba2+

Exchange equilibrium at the head of the column:2(R-SO3-H) + M2+ = (R-SO3)2-M + 2H+

solid solution solid solution

Separtion/Elution begins when acid solution is added

Equilibrium shifts to the leftCation goes into the mobil phase (momentarily)Cation desorbs/re-adsorbs many times

Page 11: Ion Chromatography

11

The time the cation spends in each phase is governed by its unique value of Kexchange

Rearranging gives:

Separation of Ca2+ Mg2+ Sr2+ and Ba2+

aq2

solid2-

3

aq2

solid2

2-

3reaction exchange

][M ]H[RSO][H M)[(RSOK

++

++

=]

aq2

solid2-

3ex

aq2

solid2

2-

3

][H]H[RSO K

][MM)[(RSO

+

+

+

+

=]

Page 12: Ion Chromatography

12

Separation of Ca2+ Mg2+ Sr2+ and Ba2+

The terms on the r.h.s. are constant when:

[H+]aq > [M+2]aq

[RSO3-H]s > [(RSO3

-)2M2+]s

i.e. [acid] > [cation] and binding sites are not saturated

aq2

solid2-

3ex

aq2

solid2

2-

3

][H]H[RSO K

][MM)[(RSO

+

+

+

+

=]

Page 13: Ion Chromatography

13

Separation of Ca2+ Mg2+ Sr2+ and Ba2+

Normal Chromatography Separation Principles Apply:

M

SD

aq2

solid2

2-

3

CC K

][MM)[(RSO

==+

+ ]

Page 14: Ion Chromatography

14

Ion Exchange Chromatography –General Characteristics

In general, ion exchangers favor binding of ions with:

↑ charge3+ > 2+ > 1+

↓ hydrated radiusH+ > Li+ > Na+ > K+ (p. 174)H+ bound least strongly b/c hydrated radius is highest

↑ polarizability

Page 15: Ion Chromatography

15

ExampleChromatograms

Cation ExchangeAnion Enchange

Page 16: Ion Chromatography

16

Example Chromatograms

Page 17: Ion Chromatography

17

Illustration of Ion Exchange Chromatography