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23 Cards in this Set

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Van Deemter model equation

H = A + B/u + u [CM + CS]


A= random movement through stationary phase


B= diffusion in mobile phase


C= interaction with stationary phase


H = plate height


u = average linear velocity

Van Deemter model

relates the variance per unit length of a separation column to the linear mobile phase velocity by considering physical, kinetic, and thermodynamic properties of a separation

The rate theory of chromatography

Describes the process of peak dispersion

What does a Van Deemter plot show?

Plate height vs average linear velocity of mobile phase- used to determine the optimum mobile phase flow rate

What is term A in VD model?

-Molecules may travel unequal distances


-independent of u


-depends on size of stationary particles or coating (TLC)

Eddy diffusion

Solute molecules take different paths through stationary phase at random, causing broadening of solute band because different paths are of different lengths.

Term B of VD model

Longitudinal diffusion


B=2γDM




γ= Resistance factor due to packing


DM = molecular diffusion coefficient

In what situation does the B term dominate?

at low u B term dominates and is more important in GC than LC as diffusion coefficient is much bigger in gas than liquid

DM

Molecular diffusion coefficient: Measures the ratio at which a substance moves randomly from a region of high conc to low conc

Term C of VD model

C=resistance to mass transfer


Cs: stationary phase mass transfer


CM: mobile phase - mass transfer

Cs equation

Cs= [df^2]/Ds


df = stationary phase film thickness


Ds= diffusion coefficient of analyte in SP

Cm equation

[dp]^2 /Dm


dp: particle diameter


DM: diffusion in MP

How does the rate theory compare to the plate model?

Takes account of time taken to equilibrate between stationary phase and mobile phase (plate model assumes eq to be infinitely fast)

Limitations of van Deemter

Assumes all columns and chromatographic techniques are the same.


Doesn't consider viscosity changes


Doesn't consider pressure changes

Paper chromatography liquid-liquid partition

The mobile phase is a solution that travels up the stationary phase, due to capillary action. The mobile phase is generally an alcohol solvent mixture, while the stationary phase is a strip of chromatography paper.

What is the SP and MP for paper chromatography?

SP = H2O bound to cellulose


MP = organic solvents

TLC (Thin layer chromatography)

After the sample has been applied on the plate, a solvent is drawn up the plate via capillary action, because different analytes ascend the TLC plate at different rates, separation is achieved.

What is the SP and MP for TLC?

SP = alumina or silica gel coated onto glass


MP = Solvents

What does varying the polarity of the mobile phase do in TLC?

varies the time polar solutes spend on SP resulting in separation.

Adsorption solvent strength parameter, ε0

measure of adsorption energy/ unit area of solvent

Rf

=distance of travel of substance/ distance of travel of solvent




Reports elution characteristics

Column chromatography

Preparative technique rather than analytical (i.e. used for seperation)


Usually silica used (range pH:2-8)


particle diameter 40-60 μm

How does increasing the polarity of functional group on silica effect speed?

Increased polarity is slower e.g. Carboxylic acid is slow, Alkanes are fast