Download ppt - Ic_sampl_prep_26062003_e.ppt 1 IC Metrohm inline sample preparation Techniques for analytical success Metrohm Ion Chromatography Bart Cleeren, Metrohm

ic_sampl_prep_26062003_e.ppt 1

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Metrohm inline sample preparationMetrohm inline sample preparationTechniques for analytical successTechniques for analytical success

Metrohm Ion Chromatography

Bart Cleeren, Metrohm België


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Inline sample preparationInline sample preparation

Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration


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UltrafiltrationUltrafiltration


Ultrafiltration cell

E Mobile phase: eluent

P1 High pressure pump

Injection valve «A»

C Analytical column

»MSM» Suppressor

D Conductivity detector

S Sample

P2 Peristaltic pump

A position fill

C

P1

E D

2


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Ultrafiltration CellUltrafiltration Cell


No particles on the acceptor side

Big particles are flushed away

and do not clog the membrane

High flow on the sample side

Low flow on the acceptor side


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# 1 Sample filtration




C Analytical column

»MSM» Suppressor


S Sample

P2 Peristaltic pump

A position fill

C

P1

E D

2


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# 2 Sample injection




C Analytical column

»MSM» Suppressor


S Sample

P2 Peristaltic pump

A position inject

C

P1

E D

2


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Ultrafiltration: vegetable juiceUltrafiltration: vegetable juice


A Supp 4 – 250

1 Organics n.q.

2 Organics n.q.

3 Cl– 4141

4 NO3– 102

5 HPO42– 577

6 SO42– 842

7 Oxalate n.q.

ppt

NaHCO3/Na2CO3; 1.7/1.8 mmol/L; dilution 1:100; 0.15 µm rec. cellul.


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Dialysis cell, acceptor solution




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump

P3 Peristaltic pump (2 Ch.)

Dialysis cell

A Acceptor solution

DialysisDialysis

C

P1

E D

2

A E

P1P2

P3

A D

CX

X


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# 2 Stopped flow dialysis




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump

Injection Valve «B»

Dialysis cell

A Acceptor solution

DialysisDialysis

C

P1

E D

2

A

P3

P2

A

P1

C

DEX


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Dialysis cellDialysis cell


Continuous flow dialysis

Exclusion diameter 0.2 µm

Ions can pass

Oil droplets, fat micelles, particles are excluded

Strong concentration gradient

No equilibrium concentration

Cellulose acetate membrane


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Dialysis cellDialysis cell


Stopped flow dialysis

Dialysis time 2 ... 8 min

Sample volume 10 mL

No loss of concentration on the sample side

Equilibrium concentration

Dialysis rate > 99 %

No filtration, no pre concentration

Unique technique, that had significantly improves the field of application for IC


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Dialysis: milkDialysis: milk


Metrosep Dual 1 – 70

1 Chloride 938

2 Nitrate n.q.

3 Phosphate n.q

4 Sufate 103

ppm

NaHCO3/Na2CO3; 2.4/2.0 mmol/L; dilution 1:5; 0.2 µm cellul. acetat


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Dialysis: cutting oil emulsionDialysis: cutting oil emulsion


Metrosep Dual 2

1 Chloride 74.7

2 Nitrite 20.5.

3 Nitrate 23.9

4 n. det. -

5 Phosphate 25.2

6 Sulfate 192.7

7 n. det. -

NaHCO3/Na2CO3; 2.0/1.3 mmol/L; dilution 1:5; 0.2 µm cellul. acetat


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# 1 Sample preconcentration




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump

C

P1

D

P3 2

S

Inline pre concentrationInline pre concentration

E

C

P1P 2

D


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# 2 Sample analysis


P 1 High pressure pump


C Analytical column

»MSM» Suppressor


P 2 Peristaltic pump

C

P1

E D

P3 2

S

Inline preconcentrationInline preconcentration

E

C

D

P1P 2


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Inline preconcentration: ultra pure waterInline preconcentration: ultra pure water


Metrosep A Supp 5 – 150

1 Acetate 2.3

2 Formate 22.0

3 Chloride 13.0

4 Carbonate n.q.

5 Nitrate 4.5

6 Phosphate 16.0

7 Sulfate 8.5

8 Oxalate 12.0

ppt

NaHCO3/Na2CO3; 1.0/3.2 mmol/L; 20 mL preconc,


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Inline preconcentration: ultra pure waterInline preconcentration: ultra pure water


Metrosep Dual 2

1 Fluoride 45 – 150

2 Chloride 100 – 210

3 Bromide 0 – 100

4 Nitrate 10 – 112

5 Sulfate 40 – 145

ppt

NaHCO3/Na2CO3; 2.0/3.2 mmol/L; 10 mL preconc, spiked 100 ppt


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P3



Transfer solution «T»




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump


P3 Peristaltic pump

T Transfer solution

A position fill, B position fill

C

P1

E D

2

T

Matrix eliminationMatrix elimination


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IC

P3



# 1 Preconcentrator column inline




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump


P3 Peristaltic pump

T Transfer solution


C

P1

E D

2

T



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P3



# 2 Sample transfer, matrix elim.




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump


P3 Peristaltic pump

T Transfer solution

A position fill, B position inject

C

P1

E D

2

T



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P3



# 3 Sample inject




C Analytical column

»MSM» Suppressor


P2 Peristaltic pump


P3 Peristaltic pump

T Transfer solution

A position inject, B position inject

C

P1

E D

2

T



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Matrix elimination: organic solventsMatrix elimination: organic solvents


50 µL iPrOH

B with matrix elimination

A without matrix elimination

ppt

F–Ac–

443 Cl–

30 NO3– 28 SO4

2–

425 Cl–

24 NO3– 17 SO4

2–


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Matrix elimination: 35 % HMatrix elimination: 35 % H22OO22


left:

without m.e.

Loop 20 µL

right:

with m.e.

Loop 20 µL

transfer vol . 2 mL


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IC

P3



833.0030 IC Sample Prep. Unit




C Analytical column

»MSM» Suppressor


P2, 3 Peristaltic pumps


T Transfer solution

833 IC Sample Prep

A position inject, B position fill

C

P1

E D

2

T

Matrix neutralizationMatrix neutralization


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IC

P3



# 1 Preconcentrator column inline




C Analytical column

»MSM» Suppressor




T Transfer solution

833 IC Sample Prep


C

P1

E D

2

T



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IC

P3



# 2 Sample transfer/neutralization




C Analytical column

»MSM» Suppressor




T Transfer solution

833 IC Sample Prep


C

P1

E D

2

T



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IC

P3



# 4 Sample inject




C Analytical column

»MSM» Suppressor




T Transfer solution

833 IC Sample Prep


C

P1

E D

2

T



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0.74 F–

3.6 Cl–

0.97 NO3–

0.98 HPO42–

1.1 SO42–


Matrix neutralization: caustic sodaMatrix neutralization: caustic soda


30 % NaOH, 20 µL loop

B with matrix elimination

A without matrix elimination

ppm


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Matrix neutralization: caustic sodaMatrix neutralization: caustic soda


Metrosep Dual 2

1 Chloride 25.08

2 Carbonate n.q.

3 Chlorate 4.76

4 Sulfate 10.43

ppm

NaHCO3/Na2CO3; 1.7/1.8 mmol/L; 50 % NaOH, 20 µL loop


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Matrix neutralization: ammoniaMatrix neutralization: ammonia


Metrosep A Supp 4 – 250

1 Formate n.q.

2 Chloride 0.03

3 Nitrite n.q.

4 Bromide 0.95

5 Nitrat 0.04

6 Carbonate n.q.

7 Sulfate 0.13

ppm

NaHCO3/Na2CO3; 1.7/1.8 mmol/L; 26 % NH3, 20 µL loop

23

4

5 67


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IC

P3



OH cartridge




C Analytical column

»MSM» Suppressor




T Transfer solution

Cartridge


C

P1

E D

2

T


Ctr


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Matrix neutralization: HClMatrix neutralization: HCl


10 µL

HCl direct injection

ppm

Metrosep C2 – 250


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Matrix neutralization: HClMatrix neutralization: HCl


Metrosep C2 – 250

1 Nickel n.q.

2 Sodium 5.4

3 Ammonium 1.3

4 Potassium 0.8

5 Magnesium 1.5

6 Calcium 0.8

ppm

Tartaric-/dipicolinic acid; 4.0/0.75 mmol/L; 7 mol HCl, 10 µL loop

1

2

3

4 5 6


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Standard S, flow path




C Analytical column

»MSM» Suppressor


P1,2,3 Peristaltic pumps


S Standard


Inline calibrationInline calibration

C

P1

E D

P3 2

S


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# 1 Measurement of standard




C Analytical column

»MSM» Suppressor




S Standard


C

P1

E D

P3 2

S



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# 2 Preconcentrator inline




C Analytical column

»MSM» Suppressor




S Standard


C

P1

E D

P3 2

S



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# 3 Transfer of standard




C Analytical column

»MSM» Suppressor




S Standard


C

P1

E D

P3 2

S



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# 4 Inject of standard




C Analytical column

»MSM» Suppressor




S Standard


C

P1

E D

P3 2

S



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# 1: Transfer of 2 mL ultrapure water to the preconcentrator

Blank value

# 2: Transfer of 2 mL ultrapure water to the preconcentrator. Valve B is thrown from fill to inject and back once

Calibration level 1

# 3: Transfer of 2 mL ultrapure water to the preconcentrator. Valve B is thrown from fill to inject and back twice

Calibration level 2

# 4: Transfer of 2 mL ultrapure water to the preconcentrator. Valve B is thrown from fill to inject and back three times

Calibration level 3, etc



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Inline sample preparationInline sample preparationInline calibrationInline calibration

100 ppt 100 ... 400 ppt


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inline sample preparation ?inline sample preparation ?Metrohm can do thatMetrohm can do that
