Solved with COMSOL Multiphysics 5.

L iq ui d C hr o m a t o grap h y
Introduction
Chromatography is an important group of methods to separate closely related
components of complex mixtures. The following example simulates the separation in
High Performance Liquid Chromatography (HPLC). In this technique an injector
introduces a sample as a zone in a liquid mobile phase. The mobile phase containing
the sample zone is pumped through a column containing a solid stationary phase;
Figure 1 shows a diagram of such an instrument.

Mobile phase
reservoir

Pump

Injector

Column

Detector

Figure 1: Diagram of an HPLC system.

The mobile and stationary phases are chosen so that the sample components are
distributed to varying degrees between the two phases. Those components that
strongly adsorb to the stationary phase move only slowly with the flow of the mobile
phase, and those that are weakly adsorbed move more rapidly. As the sample zones
migrate through the column, the components are separated into discrete zones that
are recognized in a detector, situated after the outlet of the column.

Model Definition
This model studies the separation of two species under conditions of nonlinear
chromatography, where the analyte concentration is high, and in a 1D geometry.
The governing equation for analyte transport through a chromatographic column,
with constant porosity, is
( + b k P, i )

c i
+ u c i = [ ( D D, i + F, i D F, i ) c i ] + R i + S i
t

(1)

Here, ci is the concentration of component i (SI unit: mol/m3), is the porosity, b

is the bulk density of the column solid phase (SI unit: kg/m3), kP,i is an adsorption
isotherm, and u is the volume average velocity of the fluid phase (SI unit: m/s). The

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second term on the right-hand side describes the mixing of the solutes, including
mechanical mixing (dispersion) and molecular diffusion. The two last terms on the
right-hand side are a reaction rate term and a fluid source term.
If you neglect the dispersion of the chromatographic zone during the migration, the
mass transport equation takes the form
( 1 ) n i c i
v c i
S -------------------- -------- + ------- = ------- ------
A x
t
t
where S denotes the specific surface area of the particles in the column (SI unit: m2/
kg), denotes the density of the solid particles (SI unit: kg/m3), equals the column
porosity, A gives the inner area of the column tube, ni equals the analyte concentration
in the stationary phase of component i (SI unit: mol/m2), v is the mobile phase flow
(SI unit: m3/s), and ci equals the analyte concentration in the mobile phase of
component i (SI unit: mol/m3).
The ideal model for chromatography, which have been applied in Equation 1, assumes
that the equilibrium for the analyte between the mobile and stationary phases is
immediate, that is:
c P, i
c P, i c i
------------ = ----------- ------- = k P, i
c i t
t
where cP,i is the concentration of component adsorbed to the solid (moles per dry
unit)
The mass transport equation for the ideal chromatography model therefore becomes
c i
( 1 -) dn
v c i
1 + S
------------------ ------- ------- = ------- ------

dc t
A x
The dispersion or band broadening of the analyte zone that is obtained during the
migration through the column is a result of a great number of random processes that
the analyte experiences (for example, inhomogeneous flow and diffusion in pores and
the mobile phase). It is therefore possible to formally express the band broadening as
a diffusion process with an effective diffusion constant, Deff. Thus, Deff is a measure of
the chromatographic systems efficiency for a particular analyte. This constant is closely
related to the concept of the height equivalent of a theoretical plate, H, that is
customarily used in chromatographic practice. It can be shown that

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Hv zi
D eff = -----------2
where vzi is the migration velocity of the analyte zone through the column. A mass
balance that includes the zone-dispersion term gives the following equation:
2

c
c
c
1 + dn
------- -------i = v l -------i + D eff ----------i
2

dc t
x
x
Here = S( 1 )/ denotes the phase ratio of the column (SI unit: m2/m3), vl = v/
(A) gives the linear velocity of the mobile phase in the column (SI unit: m/s), and
Deff is the effective diffusion constant (SI unit: m2/s).
This first example covers the migration within the column of two components. The
adsorption isotherm for both components is assumed to follow a Langmuir adsorption
isotherm, that is,
n 0i K i c i
n i = -------------------1 + Ki ci
and
n 0i K i
dn i
--------- = --------------------------2
dc i
( 1 + Ki ci )
where Ki is the adsorption constant for component i (SI unit: m3/mol), and n0i is the
monolayer capacity of the stationary phase for component i (SI unit: mol/m2).
Using an effective zone-dispersion term gives the following 1D equation:
c i
c i
c i

( + b k P, i ) ------- + u ------- = ------ D eff, i -------

t
x
x
x
INPUT DATA

This example looks at the migration of a chromatographic zone migrating only within
the column. The physical data for the column correspond to a 12 cm-by-4 mm inner
diameter column filled with 5 m porous particles (column= 0.6) with a specific
surface area of 100 m2/g, which gives a column phase ratio, , of 1.533108 m1.

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Additional input data appear in Table 1.

TABLE 1: INPUT DATA
NAME

VALUE

vl

2.22 mm/s

Deff1

110-8 m2/s

Deff2

310-8 m2/s

K1

0.04 m3/mol

n01

110-6 mol/m2

K2

0.05 m3/mol

n02

510-7 mol/m2

The initial concentrations for the two components are described by the normal
distribution
c 0i ( x ) = c 0i e

a ( x 0.01 )

where a equals 1105 m2, and the starting point at t = 0 is at x = 0.01 m. You first
solve the model for the initial injector concentrations c01 = c02 = 0.1 mol/m3, which
corresponds to the linear regime for the adsorption isotherm. In a second stage, you
increase the injector concentrations to c01 = 1 mol/m3 and c02 = 10 mol/m3.

Results and Discussion

Figure 2 shows the zones of the two components at various times (0 s, 80 s, and 160 s)
as they migrate within the column. In this example, the analyte concentration at t = 0
is low for both components (c0i = 0.1 mol/m3); the solution is in the linear domain

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of the adsorption isotherm. This implies that the zones are symmetrical and normally
distributed.

Figure 2: The concentrations of components 1 (solid) and 2 (dashed) in the mobile phase
during the migration through the column at times 0, 80, and 160 s for initial injector
concentrations c01 = c02 = 0.1 mol/m3.
When the initial concentrations increase, c01= 1 mol/m3 and c02 = 10 mol/m3, the
solution enters into the nonlinear domain of the adsorption isotherm, changing the
behavior radically (see Figure 3). A comparison of the zone for component 2 between

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the two simulations clearly shows that both the zone width and form is strongly
influenced by migrating into the adsorption isotherms nonlinear domain.

Figure 3: The concentrations of components 1 (solid) and 2 (dashed) in the mobile phase
during migration through the column at times 0 s, 80 s, and 160 s for initial injector
concentrations c01 = 1 mol/m3 and c02 = 10 mol/m3.

References
1. D. DeVault, The Theory of Chromatography, J. Am. Chemical Soc., vol. 65, pp.
532540, 1943.
2. S. Golshan-Shirazi and G. Guiochon, Analytical solution for the ideal model of
chromatography in the case of a Langmuir isotherm, Analytical Chemistry, vol. 60,
no. 21, pp. 23642374, 1988.
3. B. Lin and G. Guiochon, Modeling for Preparative Chromatography, Elsevier
Publishing, Amsterdam, 2003.

Application Library path: Chemical_Reaction_Engineering_Module/

Mixing_and_Separation/liquid_chromatography_1

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Modeling Instructions
From the File menu, choose New.
NEW

1 In the New window, click Model Wizard.

MODEL WIZARD

1 In the Model Wizard window, click 1D.

2 In the Select physics tree, select Chemical Species Transport>Transport of Diluted
Species in Porous Media (tds).
3 Click Add.
4 In the Number of species text field, type 2.
5 Click Study.
6 In the Select study tree, select Preset Studies>Time Dependent.
7 Click Done.
GLOBAL DEFINITIONS

Parameters
1 On the Home toolbar, click Parameters.
2 In the Settings window for Parameters, locate the Parameters section.
3 In the table, enter the following settings:
Name

Expression

Value

Description

Phi

1.533e8[1/m]

1.533E8 1/m

Phase ratio

v_l

2.22[mm/s]

0.00222 m/s

Linear velocity, mobile

phase

D_eff1

1e-8[m^2/s]

1E-8 m/s

Effective diffusion
constant, component 1

D_eff2

1e-8[m^2/s]

1E-8 m/s

Effective diffusion
constant, component 2

c01

0.1[mol/m^3]

0.1 mol/m

Initial injector
concentration,
component 1

c02

0.1[mol/m^3]

0.1 mol/m

Initial injector
concentration,
component 2

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Name

Expression

Value

Description

K1

0.04[m^3/mol]

0.04 m/mol

Adsorption constant,
component 1

K2

0.05[m^3/mol]

0.05 m/mol

Adsorption constant,
component 2

n01

1e-6[mol/m^2]

1E-6 mol/m

Monolayer capacity,
component 1

n02

5e-7[mol/m^2]

5E-7 mol/m

Monolayer capacity,
component 2

1e5[1/m^2]

1E5 1/m

Normal-distribution
parameter

x0

10[mm]

0.01 m

Starting point

epsp

0.6

0.6

Porosity

rho

2300[kg/m^3]

2300 kg/m

Solid material density

1e5[m^2/kg]

1E5 m/kg

Particle specific
surface area

v_in

1.332[mm/s]

0.001332 m/s

Linear velocity, mobile

phase

GEOMETRY 1

Interval 1 (i1)
1 On the Geometry toolbar, click Interval.
2 In the Settings window for Interval, locate the Interval section.
3 In the Right endpoint text field, type 0.12.
4 Click the Build All Objects button.
5 Click the Zoom Extents button on the Graphics toolbar.
TR A N S P O R T O F D I L U T E D S P E C I E S I N PO RO U S M E D I A ( T D S )

To obtain a properly resolved solution, use quadratic elements.

1 In the Model Builder windows toolbar, click the Show button and select Discretization

in the menu.
2 In the Model Builder window, under Component 1 (comp1) click Transport of Diluted
Species in Porous Media (tds).
3 In the Settings window for Transport of Diluted Species in Porous Media, click to

expand the Discretization section.

4 From the Concentration list, choose Quadratic.

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5 Locate the Transport Mechanisms section. Select the Adsorption in porous media check

box.

Porous Media Transport Properties 1

1 In the Model Builder window, expand the Transport of Diluted Species in Porous Media
(tds) node, then click Porous Media Transport Properties 1.
2 In the Settings window for Porous Media Transport Properties, locate the Model
Inputs section.
3 Specify the u vector as
v_in

4 Locate the Matrix Properties section. From the p list, choose User defined. In the

associated text field, type epsp.

5 From the list, choose User defined. In the associated text field, type
rho*(1-epsp).

6 Locate the Diffusion section. In the DF,c1 text field, type D_eff1.
7 In the DF,c2 text field, type D_eff2.
8 Locate the Adsorption section. In the kL,c1 text field, type K1.
9 In the cP,max,c1 text field, type S*n01.
10 In the kL,c2 text field, type K2.
11 In the cP,max,c2 text field, type S*n02.

Initial Values 1
1 In the Model Builder window, under Component 1 (comp1)>Transport of Diluted
Species in Porous Media (tds) click Initial Values 1.
2 In the Settings window for Initial Values, locate the Initial Values section.
3 In the c1 text field, type c01*exp(-a*(x-x0)^2).
4 In the c2 text field, type c02*exp(-a*(x-x0)^2).

Inflow 1
1 On the Physics toolbar, click Boundaries and choose Inflow.
2 Select Boundary 1 only.

Outflow 1
1 On the Physics toolbar, click Boundaries and choose Outflow.
2 Select Boundary 2 only.

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MESH 1

Size
1 In the Model Builder window, under Component 1 (comp1) right-click Mesh 1 and

choose Edge.
2 In the Settings window for Size, locate the Element Size section.
3 Click the Custom button.
4 Locate the Element Size Parameters section. In the Maximum element size text field,

type 5e-5.
5 Click the Build All button.
STUDY 1

Step 1: Time Dependent

1 In the Model Builder window, expand the Study 1 node, then click Step 1: Time
Dependent.
2 In the Settings window for Time Dependent, locate the Study Settings section.
3 In the Times text field, type range(0,10,180).
4 Select the Relative tolerance check box.
5 In the associated text field, type 1e-4.

Solution 1
1 On the Study toolbar, click Show Default Solver.
2 In the Model Builder window, expand the Study 1>Solver Configurations node.
3 In the Model Builder window, expand the Solution 1 node, then click Time-Dependent
Solver 1.
4 In the Settings window for Time-Dependent Solver, click to expand the Absolute
tolerance section.
5 Locate the Absolute Tolerance section. In the Tolerance text field, type 1e-5.
6 On the Study toolbar, click Compute.
RESULTS

Concentration (tds)
Follow these steps to reproduce the plot in Figure 2:

1D Plot Group 2
1 On the Home toolbar, click Add Plot Group and choose 1D Plot Group.

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2 In the Settings window for 1D Plot Group, locate the Data section.
3 From the Time selection list, choose From list.
4 In the Times (s) list, choose 0, 80, and 160.
5 On the 1D Plot Group 2 toolbar, click Line Graph.
6 In the Settings window for Line Graph, locate the Selection section.
7 From the Selection list, choose All domains.
8 Click Replace Expression in the upper-right corner of the x-axis data section. From

the menu, choose Geometry>Coordinate>x - x-coordinate.

9 Click to expand the Coloring and style section. Locate the Coloring and Style section.

Find the Line style subsection. From the Color list, choose Black.
10 Right-click Results>1D Plot Group 2>Line Graph 1 and choose Duplicate.
11 In the Settings window for Line Graph, click Replace Expression in the upper-right

corner of the y-axis data section. From the menu, choose Component 1>Transport of
Diluted Species in Porous Media>c2 - Concentration.
12 Locate the Coloring and Style section. Find the Line style subsection. From the Line

list, choose Dashed.

13 On the 1D Plot Group 2 toolbar, click Plot.
GLOBAL DEFINITIONS

Parameters
1 In the Model Builder window, under Global Definitions click Parameters.
2 In the Settings window for Parameters, locate the Parameters section.
3 In the table, enter the following settings:
Name

Expression

Value

Description

c01

1[mol/m^3]

1 mol/m

Initial injector
concentration,
component 1

c02

10[mol/m^3]

10 mol/m

Initial injector
concentration,
component 2

STUDY 1

On the Home toolbar, click Compute.

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RESULTS

1D Plot Group 2
Compare the plot with that in Figure 3.

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