simulation of gel permeation (size exclusion) chromatography

Jetse Reijenga1, Wieb Kingma1, Dušan Berek2, Milan Hutta3

1Eindhoven University of Technology2Slovak Academy of Science, Bratislava

3Comenius University Bratislava

ISSS-2006 Lipica 27-29 september 2006

Demonstrate and visualize the influence of following parameters on chromatographic results and interpretation:• Choice sample: polymer, molar mass, distribution• Choice of column parameters• Choice of instrument parameters

target audience

• Polymer scientists• Chromatographers• Teachers of separation science• Students

purpose of the simulator

• flow rate (0.1-10 ml/min, default 1 ml/min)• injection volume (1-1000 l, default 10 l)• temperature (25-220 ºC, default 40 ºC)• column length (50-1200 mm, default 300 mm)• column ID (2-20 mm, default 7.5 mm)• connection (dead) volume (0-1000 µl)• detector type (Refractive Index, Viscosity, Density, Lightscatter• detector volume (1-1000 µl)• detector path length (1-25 mm)• detector time constant (0.01-5 s)

instrument parameters that can be manipulated and trained

PS calibration typical for commercially available columns

broad range columns

4

5

6

7

8

9

10

2 3 4 5 6 7

log(molar mass)

elu

tion

volu

me [

ml]

narrow range columns

4

5

6

7

8

9

10

2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7

log(molar mass)

elu

tion v

olu

me [

ml]

column types (default size 300x7.5 mm)

• type of polymer• molar mass (1,000 - 10,000,000 g/mol)• sample: either single polymer of variable distribution or mix of

infinitely narrow distributions of several different polymers• distribution function (Poisson, Lognormal or Flory)• sample concentration (0-1000 mg/ml)

PS (as calibration reference), PMMA, PEMA, PBMA, PiBMA, P2EHMA, PC10MA, PMA, PEA, PBA, P2EHA, PiBoMA, PVA, PCL, PC etc

sample parameters

• calibration through PS as a reference using polynomal fit to the

calibration curves from the manufacturer:

Ve = A + B.LogM + C.LogM2 + D.LogM3 + E.LogM4 + F.LogM5

• other polymers i modeled using K and a coefficients:

log(MPS) = (1/(aPS + 1))log(Ki/KPS) + ((ai + 1)/(aPS + 1))log(Mi)

• K and a coefficients (THF, 25ºC) were taken from literature

• detailed modeling of chromatographic peak broadening

• simulation of influence of extra-column broadening (injection,

connections, detection)

modeling retention & dispersion

universal calibration

choose column….

choose detector

bandbroadening details

conclusions

Using one can:

• Visualize all retention and dispersion effects• Validate experimental setup• Check sensitivity of results for many operating parameters• Extrapolate current instrument specifications• Perform hypothetical experiments

http://chem.tue.nl/ce

Thank you

Thank you