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25

3. TAYLOR DISPERSION THEORY

In chapter 1 the important role of diffusion in liquid-liquid extraction has been pointed out. For

a quantitative description of a ternary extraction, we need the diffusion coefficients of the

system. Measuring diffusion coefficients used to be, and still is, a rather time-consuming

occupation. There are two methods in common use: the diaphragm cell method [13] and the

Taylor dispersion method. This chapter deals with the latter, which is named after G.I.Taylor,

who, in the 1950’s, published a number of articles on the dispersion in fluid media flowing

through a tube [15, 16]. Although it has taken a while before the principles he discussed were

actually applied, the method is now recognised as a fast and reliable way to measure

diffusivities in homogeneous fluids.

This chapter consists of two parts. To start with, we look at the theory of the dispersive

process, but not in too great a detail, because this has been done by others. Instead, we will pay

special attention to the design of the dispersion tube. In the second part, we will see how to

obtain multicomponent diffusivities from dispersion measurements.

3.1 THE TAYLOR DISPERSION EXPERIMENT

To decide what equipment exactly is needed, and how it must be designed, we must be

acquainted with the theory behind the processes on which the measurements are based. Thus

we will briefly discuss this theory, and then some design rules.

3.1.1 Theory of the dispersive process

When a fluid flows through a tube, a velocity profile develops. This profile is not uniform over

the cross-section of the tube: at some radial positions, the fluid flows faster than at others. The

laminar profile for Newtonian fluids has a parabolic velocity distribution. Matter present in the

fluid moves along with it and is therefore dispersed along the tube axis. Apart from this purely

convective dispersion, diffusion can also be of influence.

Suppose that somewhere in the tube we have a small ‘plug’ of fluid with a composition

different from an otherwise similar bulk of fluid. The flow of the fluid causes this plug to

disperse, but it also induces radial composition gradients. This leads to diffusive fluxes at the

front and back sides of the plug. These fluxes become important if the radial diffusive fluxes

are roughly of the same order of magnitude as the convective axial fluxes. This is the case

when either the axial velocity is very low, or when the radial distances are very small. When

either condition is satisfied, diffusion tends to keep the plug together, in contrast to what one

might intuitively expect. So, through the combined action of convection and diffusion, the plug

will leave the tube as a broadened, but still more or less compact plug. To achieve this

situation, Taylor dispersion experiments are usually carried out in tubes with small diameters,

also called capillaries.

Chapter 3

26

Taylor considers the dispersion of a Dirac-pulse of a tracer fluid in a laminar flow. The tube is

circular with a diameter d, and the bulk fluid has a superficial velocity u

sup

. The distribution

after t seconds is given by

∆c z t

n

d t

z u t

t

1

1

2

2

2

4

, b g

d i

= −

−

F

H

G

G

I

K

J

J

E

sup

exp

π πκ

κ

(1)

Here, ∆c

1

is the concentration of component 1 (the ‘tracer’

†

) minus its concentration in the

eluent, n

1

E

is the excess number of tracer moles in the pulse, κ is the dispersion coefficient, and

z is the down-stream distance from the initial location of the Dirac-pulse. The approximate

expression for κ given by Taylor [15] is

κ =

u d

D

sup

2 2

192

(2)

where D is the molecular Fick diffusivity of the tracer with respect to the eluent. Aris [2] showed

that the exact solution is

κ = +

u d

D

D

sup

2 2

192

(3)

Later, Price [12] derived expressions for the concentration distributions for three components

in a way analogous to Taylor, and which are therefore not exact.

∆

∆

c z t

K

d t

z u t

t

K

d t

z u t

t

c z t

K

d t

z u t

t

K

d t

z u t

t

1

1

2

1

2

1

2

2

2

2

2

2

3

2

1

2

1

4

2

2

2

2

2

4

2

4

2

4

2

4

,

,

b g

d i d i

b g

d i d i

= −

−

F

H

G

G

I

K

J

J

+ −

−

F

H

G

G

I

K

J

J

= −

−

F

H

G

G

I

K

J

J

+ −

−

F

H

G

G

I

K

J

J

π πκ

κ

π πκ

κ

π πκ

κ

π πκ

κ

exp exp

exp exp

sup sup

sup sup

(4)

with

κ κ κ κ κ

κ κ

κ κ

i i i

i

u d

D

D D

K

D n D n

D

K

D n D n

D

K

D n D n

D

K

D n D n

D

= = = + −

=

− −

= −

− −

=

− −

= −

− −

+

0 0

2 2

1

2

1

1

2 2 2 1 1 2 2

2

2 2 1 1 1 2 2

3

1 1 2 2 2 1 1

4

1 1 1 2 2 1 1

192

1

* *

,

*

, ,

*

,

,

*

, ,

*

,

,

,

,

where tr disc

disc disc

disc disc

sup

E E E E

E E E E

b g

e j

d i d i

d i d i

(5)

†

Strictly speaking, components 1 and 2 are not interchangeable except when the total number of excess

moles in the pulse is zero, that is, when the partial molar volumes are equal and constant. But this is a

prerequisite for the derivation of eq. (1) anyway.

TAYLOR DISPERSION THEORY

27

So, by monitoring the concentration distribution we are able to determine the dispersion

coefficient(s).

3.1.2 The capillary: coiled or straight?

To obtain a concentration distribution at the end of the capillary which has spread enough to

allow us to extract the value of the diffusivity with a reasonable accuracy, the dispersive

process must have had enough time to do its work. For several reasons outlined in this section,

we cannot decrease the fluid flow at will, and therefore the capillary must have a definite

length, which turns out to be about 20 m. This makes it desirable to coil the capillary: this

configuration saves space, makes the capillary less vulnerable, shortens data communication

lines, and enables better temperature control. But can we do it without any repercussions?

Arguments for a straight capillary are of a theoretical nature: the solutions of the mathematical

equations governing the Taylor dispersion dynamics are simpler and require fewer

simplifications in the case of a straight capillary. These solutions may therefore be assumed to

be more accurate, and also fitting these solutions to measured RTD curves favours simple

equations.

Usually, the best of two worlds is taken: the capillary is coiled but at the same time it is

assumed to be mathematically straight. Under what circumstances are we allowed to do this?

Taylor dispersion is usually carried out in a coiled capillary, the coil diameter δ being of the

order of several decimetres, about 4 dm

†

say. Although the measured diffusivities are probably

accurate enough, literature does not provide a firm theoretical basis for neglecting the curvature

of the capillary. At least, it is impossible to satisfy all criteria for a Taylor dispersion capillary

for all possible system parameters without falling out of the range of reasonable dimensions

and experimental conditions. These criteria are:

1. The flow within the capillary should be laminar, so

Re = <

4

2000

Φ

V

ρ

π η d

(6)

2. The volume of the injected sample V

inj

must be very small compared with the capillary volume

V

cap

[13]. This gives the sample enough volume to disperse in, and allows us to ignore the initial

shape of the pulse.

V

V

cap

inj

> 100 (7)

3. This criterion originates from the theory of Taylor dispersion [1, 2, 15, 16]. The cross-section

averaged second moment of the concentration distribution in the capillary, m

2

, is given by

†

Rutten [13] used a capillary with an inner diameter of 0.53 mm and a coil diameter of 0.40 m, for Snijder's

[14] capillary these measures were 0.56 mm and 0.1 m, and v.d. Ven [21] uses a capillary of similar

dimensions.

Chapter 3

28

m D

u d

D

t

u d

D

Dt

d

i

i

i

2

2 2 2 4

2

8

2

2

1

2

192

8 1

4

= +

F

H

G

I

K

J

− −

F

H

G

I

K

J

L

N

M

M

O

Q

P

P

−

=

∞

∑

sup sup

exp α

α

(8)

In this expression, α

i

represents the ith zero of the derivative of J

0

, the zeroth-order Bessel

function of the first kind. Although not strictly necessary, it is convenient to simplify the first term

on the right-hand side: in most cases the diffusivity D will be much smaller than u

sup

2

d

2

/ 192 D,

and when it is negligibly small, it can be omitted. However, under what conditions do we say that

one term is negligibly small compared to another term? Let us say that a positive number a is

negligible compared to another positive number b if a < ε b, ε being some small number between 0

and 1, 0.01 for instance.

With the definition of the radial Péclet number Pe (= u

sup

d / D) and with u

sup

= 4 Φ

V

/ π d

2

, we find

D

u d

D

u d

D

Pe + = >

sup sup

if

2 2 2 2

2

192 192 192

1

ε

(9)

4. This condition also follows from equation (8). Note that the summation function is quite

impractical for curve-fitting, and it would be convenient if it could be eliminated. First the

exponential terms get in our way, but it turns out that all of them are usually much smaller than 1.

Of all α

i

, α

1

has the smallest value: α

1

≈ 3.83, α

2

≈ 7.01 etc. Hence, we only have to consider

whether the term containing this first root is negligible, because if it is, so are all the other terms.

This means according to our negligibility definition:

Dt

d

2

1

2

4

> −

lnε

α

(10)

Now, equation (8) reduces to

m

u d t

D

u d

D

A

2

2 2 2 4

2

96

8 = −

sup sup

(11)

where A represents the sum Σ α

i

−8

, which has a value of 2.1701...⋅10

−5

. The second term of this

expression can be ignored if

ε

ε ε

u d t

D

u d

D

A

Dt

d

A

sup sup

or

2 2 2 4

2 2

2

96

8

768 167 10

> > ≈

⋅

−

.

(12)

Both conditions (10) and (12) concern the same quantity D t /d

2

, called the Fourier number Fo. It

turns out that whenever (12) is satisfied, so is (10), which is therefore a redundant criterion.

What is the meaning of t in eq. (12)? Strictly speaking, t is the time after injection of the sample. A

representative value of t is the mean residence time τ of the sample:

τ

π

=

L d

2

4Φ

V

(13)

TAYLOR DISPERSION THEORY

29

If this expression is inserted in (12) for t, then this equivalent to the statement that this criterion

holds at t = τ, and it will be assumed that it still holds when the last traces of the sample leave the

capillary. The resulting inequality is

D L A π

ε Φ

V

>

3072

(14)

5. This condition is a rather prosaic one, for it is imposed by the limitations of the HPLC-pump

used for pumping the fluid through the capillary. The maximum pressure drop ∆ P

max

such pumps

usually can generate is about 400 bar, and according to Poiseuille's law, the parameters must be

chosen to satisfy the inequality

∆

Φ

∆ P

L

d

P = <

128

4

V

max

η

π

(15)

6. The criteria discussed so far concern straight capillaries, and, apart from numbers 3 and 4, are

not likely to cause too many problems. The next criterion should take care that coiling does not

lead to significant deviations of the measured diffusivities. Intuitively, one might argue that coiling

the capillary leads to a secondary flow perpendicular to the tube axis. The extra radial mixing

diminishes radial concentration gradients. Radial transfer in straight capillaries is a diffusive

process only, and therefore we would expect convection due to coiling to increase the radial

transport. However, it will be seen that coiling also influences the axial profile, and can even

reduce the dispersion coefficient.

Approximate solutions of the equations describing simultaneous convection and diffusion in

curved pipes have been found by Erdogan and Chatwin [8], and Nunge, Lin and Gill [10]. In both

papers power series expansions in the coil-capillary diameter ratio λ are used. In the first paper the

authors find the following expression for the dispersion coefficient κ, which is based on the

velocity profiles derived by Dean [6, 7]

κ λ

EC

= + − +

−

Pe D a a a Sc a

2

1 2

2 4

3

2

4

Re

d i

(16)

Here the constants a

1

to a

4

have the following values

a a a a

1 2

2

3 4

1

192

1

576 40

2569

15840

1109

43200

= = = = ; ; ; (17)

In the straight capillary case, that is, as λ → ∞, κ

EC

→ D Pe

2

a

1

, which is the approximation found

by Taylor [15]. This indicates that the approximation is not accurate, since the limit should yield

the Aris solution for straight tubes.

In the article of Nunge, Lin and Gill, equation (16) was extended to

κ κ λ κ

NLG

= +

−

Pe D

2

20

2

22

d i

(18)

with

Chapter 3

30

κ

κ κ

20

2

1

22 2

4

3

2

4 5

2

6 7 8 9 20

1

= +

= − + + − + +

Pe

a

a a Sc a a a Sc a a a

r

Re Re

d i b g

(19)

The constants a

1

,..., a

4

have the same values as before, and

a a a a a

5 6 7 8 9

1

41472

31

60

8499

4480

419

11520

1

4

= = = = = ; ; ; ; (20)

Figure 1 shows a plot of the deviation of κ

NLG

relative to the Aris solution,

∆

NLG

NLG A

A

=

−

=

+

−

κ κ

κ

λ κ

2 2

22

2

1

1

Pe

Pe a

(21)

We see that

• The straight-tube limit of equation (18) is the Aris solution, as expected.

• For high Re-numbers both dispersion coefficients κ

EC

and κ

NLG

tend to the same limit.

• For normal liquids (Sc ≈ 10

3

), an increase of the dispersion coefficient due to coiling is found

only at very low Re-numbers.

• For higher Sc-values very large deviations may be found, even at moderate Re-numbers. To

keep the relative error smaller than 1% may require an extremely high λ.

Although both equations predict that the dispersion coefficient increases only for Re-, Sc- and λ-

values within definite ranges, there are notable differences, and equation (18) is probably the better

approximation. The criterion for coiling then becomes

ε λ κ

κ

2

20

22

1 ≥ (22)

Re (-)

0.0 2.5 5.0 7.5 10.0

λ

2

∆

NLG

(-)

-10

0

10

10

100

1000

Sc (-)

Figure 1. The deviation of the dispersion coefficient according to Nunge, Lin and Gill for several Sc-

numbers.

TAYLOR DISPERSION THEORY

31

7. A last criterion is that the sampling time must be long enough for accurate measurements. We

will choose the minimum sampling time (t

m

) as 120 s. After having injected a Dirac-pulse in the

fluid stream at the beginning of our capillary at t = 0, we stroll over to the other end of it and wait

for the pulse to come out. So, our position is fixed (z = L), and the remaining variable is the time t.

The response of the system is given by equation (1), which is a Gauss function with respect to t.

The ‘standard deviation’ σ of this function equals (2 κ t)

½

. Since the peak width interval is chosen

arbitrarily, there is no need for excessively scrutinous consideration of which κ should be used, and

here it is taken to be the Aris approximation. The peak width of a response curve is usually defined

as 4 σ [3], and the seventh criterion then becomes

t

t

u

m

= >

4 2

120

κ

sup

(23)

As stated above, the criteria 1, 2, and 5, which concern straight tubes and are not related to ε, are

usually easily satisfied. The additional peak width criterion may not be met in all practical cases,

but this is a problem we can live with. The most severe troubles can be caused by the criteria 3, 4

and 6. For a given configuration these criteria can be written in the form ε > f (Φ

V

). In figure 2

these three functions are plotted for a capillary with dimensions L = 20 m, d = 0.53 mm, and

δ = 0.80 m. The relevant physical fluid parameters were taken as D = 5·10

-9

m

2

s

−1

, ρ = 1.5·10

3

kg m

−3

and η = 2·10

−4

Pa s. It is clear that the highest accuracy is obtained at a flow rate of

about 1.5·10

−9

m

3

s

−1

.

10

9

Φ

V

(m

3

s

-1

)

0.0 0.5 1.0 1.5 2.0

10

3

ε (-)

0.0

0.2

0.4

0.6

0.8

1.0

3

4

6

criterion #

best

accuracy

Figure 2. The accuracy ε derived from the criteria 3, 4 and 6 as a function of the volume flow. The

equipment parameters are: L = 20 m, d = 0.53 mm, and δ = 0.80 m, and the physical fluid properties are

D = 5·10

−9

m

2

s

−1

, ρ = 10

3

kg m

−3

and η = 2⋅10

−4

Pa s.

In table 1 the best obtainable accuracy of the Taylor dispersion method is listed for several sets of

physical properties of the fluid. The best accuracy is obtained at a specific flow rate, which may,

however, be too low for practical applications. Therefore, the accuracy is also computed for a more

convenient flow rate of 2.5⋅10

−9

m

3

s

−1

(= 0.15 ml min

−1

).

Chapter 3

32

Table 1. The best possible accuracy with the Taylor dispersion method for several sets of system

parameters, the corresponding flow rate, and the criteria by which this ε-minimum is determined.

Capillary dimensions: L = 20 m, d = 0.53 mm, and δ = 0.80 m.

We see that, although the minimum accuracy is quite good in all cases, it is not always obtained at

flow rates which allow quick measurements: τ is about 8 hours at a flow rate of 0.16⋅10

−9

m

3

s

−1

.

But it appears that the accuracy deteriorates dramatically in some cases if we choose a more

convenient flow. Thus, for mixtures with extreme properties, it is necessary to have a look at the

criteria before any measurements are carried out.

Extreme conditions as those of the last two rows of table 1 are not likely to occur, because low

viscosity is usually accompanied by high diffusivities, and only in the case of mixtures of large

entities such as macromolecules and low-viscous fluids, are problems to be expected.

With the above set of rules, it is no longer necessary to work with rules-of-thumb, as most

experimenters seem to do. Rutten [13] does not explicitly derive his coiling criteria (λ > 100,

Re < 50), although he claims them to be based on work done by Tijssen [17, 18, 20], Nunge et al.

[10], and Erdogan and Chatwin [8]. Snijder [14] uses the results of Janssen [9] to justify his choice

of capillary dimensions. Janssen found – on the basis of numerical simulations – that ’for values of

De

2

Sc < 100 there will be no significant difference with the straight tube’, whenever λ > 20. What

is meant exactly with significant is not completely clear, but it probably refers to relative errors of

up to about 3%, which is much more than the minimum allowable deviation of 0.1% used here. If

the more restrictive condition De

2

Sc < 50 is used, the relative deviation shrinks to less than 0.5 %,

which is in better accordance with the criterion given by Alizadeh et al. [1]: De

2

Sc < 20 and

λ > 100.

Evidence supporting the notion that coiling effects cannot always be ignored was found by Chen

and Blanchard [4, 5], who measured diffusivities of macromolecular substances (PS) in an organic

solvent (THF), and who found significant deviations from Taylor dispersion theory. Tijssen [19]

showed that these deviations can probably be ascribed to the small curvature of the tube used in the

experiments.

physical fluid properties best accuracy Φ

V

= 2.5·10

−9

m

3

s

−1

10

−3

ρ

(kg m

−3

)

10

3

η

(Pa s)

10

9

D

(m

2

s

−1

)

10

4

ε

(–)

10

9

Φ

V

(m

3

⋅s

−1

)

criteria

10

4

ε

(–)

criterion

1.5 200 5 3.3 1.6 3, 4 5.3 4

0.6 200 5 3.3 1.6 3, 4 5.3 4

1.5 0.2 5 3.7 1.5 3, 6 30 6

0.6 0.2 5 3.3 1.6 3, 4 5.3 4

1.5 200 0.5 3.3 0.16 3, 4 53 4

0.6 200 0.5 3.3 0.16 3, 4 53 4

1.5 0.2 0.5 3.3 0.16 3, 4 3.0·10

3

6

0.6 0.2 0.5 3.3 0.16 3, 4 4.8·10

2

6

TAYLOR DISPERSION THEORY

33

3.2 RETRIEVAL OF DIFFUSIVITIES FROM EXPERIMENTAL DATA

We now know how to conduct an experiment, and what to expect from the data it produces.

The final step is to extract diffusivities from the data. To this aim, eqs. (1) or (4) are fitted to

the experimental data. The following section treats the problems connected with this retrieval

of the diffusivities from the experimental data.

The extraction of the diffusivities from set of measured composition profiles is not always as easily

done as it is said. Problems can arise due to unruliness of the model functions as well as of the

detection method. First, the functions. We wish to fit the functions (1) and (4) to signals measured

at the end of the capillary, that is, at z = L. We will use the functions in the mole fraction form: the

mole fraction is simpler to determine than the concentration, especially at the moment that the

solution is prepared. The equations then become

∆ y t

b

t

k

t

t

b

n

c d

k L

1

2

1

3 2 2

1

2

2

1

2

b g

b g

c h

= −

−

F

H

G

I

K

J

= =

κ

τ

κ π

exp with and

E

(24)

or

∆

∆

y t

b

t

k

t

t

b

t

k

t

t

y t

b

t

k

t

t

b

t

k

t

t

b

K

c d

b

K

c d

b

K

c d

b

K

c d

1

1

1

2

1

2

2

2

2

2

3

1

2

1

4

2

2

2

1

1

3 2 2

2

2

3 2 2

3

3

3 2 2

4

4

3 2 2

1 1

1 1

2 2 2 2

b g

b g b g

b g

b g b g

= −

−

F

H

G

I

K

J

+ −

−

F

H

G

I

K

J

= −

−

F

H

G

I

K

J

+ −

−

F

H

G

I

K

J

= = = =

κ

τ

κ

κ

τ

κ

κ

τ

κ

κ

τ

κ

π π π π

exp exp

exp exp

, , ,

(25)

It will be shown below that there is little wrong with the first equation from a fitting point of view,

but the similarity of the two component profiles in the second one will cause trouble. The right-

hand members of these eqs. require the total concentration c, but because n

E

/ c = y

E

V

inj

everything can be defined in terms of mole fractions. V

inj

is a quantity that must be determined

anyway for the evaluation of the injected excess amounts of the independent components.

The detection of the concentration-time functions may give problems as well. A good measuring

device is linear, and does not deform or delay the output signal. That is, if f ( t ) is the output of the

apparatus, we have

f t S y t s r t b g b g b g = + + (26)

Ideally, the matrix [S ] of the detector is independent of y, and in even more ideal equipment, it is

also diagonal. In this section we will assume [S ] is constant for the composition ranges considered.

The constant s is the offset of the detector, and it would be nice if it equals o but we shall see

below that it is no problem if it is not. The function r (t) is the (white) noise function of the

measuring apparatus. The number of independent outputs, the dimension of f, is bound to a

maximum of n − 1, for we cannot obtain more information from the n − 1 independent mole

fractions y

i

.

Chapter 3

34

Measuring equipment can exhibit baseline drift, and eq. (26) should also include a drift function. If

the drift is not too serious, it does not render an experiment useless. Any moderate, well-behaved

function can be accurately described with a polynomial, and so, assuming the drift function is a

polynomial, we get

f t S y t s r t a t

j

j

j

m

b g b g b g = + + +

=

∑

0

(27)

We can, of course, try to fit the baseline drift simultaneously with the other parameters. Because of

the increased number of parameters, this slows down the fitting process, but above all it may

shrink the domain of convergence. This is the set of all combinations of initial parameter

estimates for which the fitting routine

†

converges to a solution. Luckily, there is a simple and

often effective alternative, namely ‘manual’ pre-fit baseline correction. Given the functions (24)

and (25), we can see that ∆ y (t) → 0 as | t | → ∞, so

f t s r t a t t

j

j

j

m

b g b g → + + → ∞

=

∑

0

as (28)

We now make a selection of data points at both sides of the peak that clearly belong to the baseline

of the curve. They represent measurements of the eluent composition. To these selected data we fit

a polynomial of a certain degree. (A degree of three will do perfectly in most cases.) This

polynomial is then subtracted from all points in the data set. For moderate forms of baseline drift,

this method gives us a neatly zeroed baseline. Apart from this, it also frees us of the constants s

(offset) and [S ] y

e

‡

(the eluent signal). These are incorporated in the constants a

0

, but this also

happens when the baseline drift is fitted along with the signal, and that is why the offset of the

detector is not important. The resulting signal f ( t ), which can be used to fit the equations (24) and

(25), is

f t S y t r t b g b g b g = + ∆ (29)

This baseline correction method has one possible disadvantage. The drift function is only fitted to a

limited selection of the data set. Any irregularities in the baseline in the part of the signal that does

not belong to this selection are not ‘seen’ and remain present in the corrected data set. This is why

it would be better to fit the baseline along with the other parameters, had it not been for the

drawbacks mentioned above. Further, ‘manual’ baseline correction requires that the data contain

enough baseline points

††

, otherwise it is not possible to determine the correction polynomial with

sufficient accuracy.

Do we need to know the linearity matrix [S ] to be able to fit eqs. (24) and (25)? We do not,

although it may make things easier if we do. In the binary case, substitution of eq. (24) into (26)

yields

†

The Marquardt-Levenberg method [11] was used for all parameter optimisations.

‡

As was mentioned at the beginning of this chapter, ∆c = c – c

e

. Since c is assumed constant, this is

equivalent to ∆y = y – y

e

. Hence: [S ] y(t) = [S ] ∆y(t) + [S ] y

e

.

††

A good fit always requires a well-defined baseline, so normally this constraint should be fulfilled

anyway.

TAYLOR DISPERSION THEORY

35

f t

S b

t

k

t

t

b g

b g

= −

−

F

H

G

I

K

J

1 1

2

1

,

κ

τ

κ

exp (30)

So, in principle S

1,1

b, D and τ can be determined from a single output data set. In this case practice

follows theory, and usually, the lumped parameter S

1,1

b and the other two parameters can be

determined from just one set of data with reasonable accuracy. Only if S

1,1

is known, it is possible

to evaluate n

1

E

, but the injected excess amount of a substance is a less relevant parameter anyway.

Besides, it can be determined beforehand while preparing the samples. If one really wants to fit

n

1

E

, two experiments at different sample compositions are required, and eq. (24) must be fitted

simultaneously to the two resulting data sets.

In the ternary case things are more complicated, because of the similarity of ∆ y

1

( t ) and ∆ y

2

( t ).

With three components, f can have two independent elements at most, but many measurement

devices have only one output (e.g. refractive index at one wave length, or conductivity). The

constants S

2,1

and S

2,2

then are zero, and the output becomes

f t

S b S b

t

k

t

t

S b S b

t

k

t

t

1

1 1 1 1 2 3

1

2

1

1 1 2 1 2 4

2

2

2

1 1

b g

b g b g

=

+

−

−

F

H

G

I

K

J

+

+

−

−

F

H

G

I

K

J

, , , ,

κ

τ

κ

κ

τ

κ

exp exp (31)

The fit of a single data set gives values for (S

1,1

b

1

+ S

1,2

b

3

), (S

1,1

b

2

+ S

1,2

b

4

), κ

1

, κ

2

and τ. Only

under certain conditions is one data set sufficient to fit all parameters. In most cases however, we

will need more than one set of experimental data. How many more? This depends on

1. whether we know the excess number of moles n

E

for each experiment,

2. whether the linearity [S ] is known

3. the number of outputs of the detector.

Suppose that we have a number of m experiments at constant eluent composition. The

parameters [D ] and [S ] are the same for all m data sets, while τ may differ, and n

E

certainly

will. The diffusivities are unknown by definition, whereas the mean residence time is a fit

parameter for the sake of accuracy

†

. Table 2 contains an inventory of the number of unknowns

for all possible situations that can be encountered.

Table 2. The number of unknowns and equations for all possible sets of experimental conditions. The

numbers in parentheses are the numbers of experiments needed for the determination of the parameters.

The numbers in this table are valid for ternary dispersion only.

†

Note that a varying τ implies that either L is not correct or u

sup

deviates. Since L can be measured

accurately, it must be u

sup

that potentially contains a significant error. Therefore, we should use

u

sup

= L / τ in eqs. (3) and (4), which makes κ a function of both D and τ.

detector # # unknowns #

calibrated outputs n

E

unknown n

E

known equations

Yes 1 4 + 3 m (–) 4 + m (1) 2 + 3 m

Yes 2 4 + 3 m (1) 4 + m (½)

*

2 + 5 m

No 1 6 + 3 m (–) 6 + m (2) 2 + 3 m

No 2 8 + 3 m (3) 8 + m (1½)

*

2 + 5 m

*

In the case of two outputs, half an experiment corresponds to one peak.

Chapter 3

36

The minimum number of unknowns is 4 + m: the four D’s and m τ’s. For an uncalibrated

detector this number must be increased by the number of unknown linearity factors, namely 2

(single output) or 4 (dual output). The n

E

make for 2 m extra variables if they are not known.

The simultaneous fit of the data set from a single-output detector yields a number of 2 + 3 m

equations: namely values for κ

1

and κ

2

, which are the same for all sets, and 3 m values for τ

and the composite parameters (S

1,1

b

1

+ S

1,2

b

3

) and (S

1,1

b

2

+ S

1,2

b

4

). Dual-output detectors

supply us with two peaks per experiment and therefore we have 5 m + 2 equations.

The table shows that with a single-output measurement apparatus it is impossible to find the

values of all parameters unless we know n

E

. This is because every data set introduces as many

new unknowns as extra equations. With a dual-output device it is possible to fit all possible

parameters, which is why two outputs are to be preferred to one output. Thus, one peak suffices

to determine all 5 parameters with such a measuring device if the n

E

are known and if it is

calibrated. If it is not calibrated, we need three peaks. This may seem a bit strange, but this

situation is not essentially different from the single-output case with known n

E

, and we need

two peaks from, say, the first output to determine all parameters except S

2,1

and S

2,2

. For the

determination of these two parameters, we need a third data set from the second output.

If, as has been said above, it is easy to determine the n

E

, then why would we like to fit them?

This is because possible experimental errors in n

E

– or in [S ] if we choose to calibrate our

detector – can then ‘move into’ the fitted parameters, of which the D’s are the ones that really

matter. This is also the reason why the mean residence time of a sample is taken as a fit

parameter, even though it can be determined experimentally with good accuracy. The fact that this

introduces extra parameters does not weigh heavily, since τ usually can be fitted very accurately,

because it is almost independent of other parameters. Moreover, it is possible to make good initial

guesses, either from the flow rate and the capillary volume, or from the output data

‡

.

It must be realised that the numbers of experiments listed in table 2 are an absolute minimum.

More data sets usually give better fits, and tend to increase the stability and enhance the domain of

convergence of the fitting routine. As an example consider the case of a calibrated detector with

one output. Suppose that we know n

E

, then according to the table only one experiment should do.

To verify this, we use constructed data sets instead of measured ones so as to be sure about what

the exact values of all parameters are. Let L = 19.0 m, d = 5.3·10

−4

m, u

sup

= 1.0·10

−2

m s

−1

,

c = 1.33·10

4

mol m

−3

, D

1,1

= 3.0·10

−9

, D

1,2

= 5.0·10

−10

, D

2,1

= 1.3·10

−9

, D

2,2

= 5.0·10

−9

m

2

s

−1

,

S

1,1

= 2.0, S

1,2

= −1.0 V and s = o V. Artificial peaks were constructed with eq. (31) for 250 points

on the time interval [1.6, 2.2] ks (i.e., every 2.4 s). Noise was added according to

r t x t x t

r

b g b g c h b g = − σ π cos ln 2 2 (32)

which is said to give normally distributed random numbers with a variance of σ

r

2

if x(t) is a

uniformly distributed random number on [0, 1〉. The responses to the following samples were

calculated

‡

τ is located approximately at the (middle) extremum of the signal, but not exactly: if t

0

is the position of

this extremum, then to a good approximation we have (for binary dispersion): τ – t

0

≈ κ / u

2

sup.

TAYLOR DISPERSION THEORY

37

I. (n

E

)

T

= (5.0 9.0)·10

−7

mol, and

II. (n

E

)

T

= (8.0 −2.0)·10

−7

mol.

The noiseless composition-time distributions of these two samples in the absence of baseline drift

are shown in the figure 3.

t (ks)

1.6 1.8 2.0 2.2

-6e-5

0e+0

6e-5

-6e-4

0e+0

6e-4

f (V)

II

I

Figure 3. The simulated ideal responses of the two samples. Notice that the response of pulse II has a

maximum amplitude about 13 times larger than that of pulse I.

Although these distributions contain the same information about [D ], they are different when it

comes to parameter fitting. This is best illustrated by the actual fit results.

Table 3. One-peak fit results for both peaks I and II for varying σ

r

. Calibrated detector, sample

compositions known. The diffusivities D

ij

are given in 10

9

m

2

s

−1

, the estimated standard errors (ESE’s)

∆D

ij

are given as a percentage of the fitted value of D

ij

. The τ’s, which are not shown, fitted very well

under all circumstances – not only with respect to their magnitude, but also to their ESE –, a fact that has

already been mentioned above. The enormous ESE’s are no mistakes!

The first thing that meets the eye, is the inaccuracy of the fits, but we will come to discuss that in

the next paragraph. What is of importance here, is that peak I is less sensitive to noise, that is, it

retains the information about the diffusivities better than peak II if the noise gets worse. This is

especially so if it is realised that for a given σ

r

, the signal-to-noise ratio is much smaller for peak I

than for peak II. Not only do the fits of peak I give more accurate values of the D

ij

, but also are the

Sample # σ

r

(V) D

1,1

± ∆D

1,1

D

1,2

± ∆D

1,2

D

2,1

± ∆D

2,1

D

2,2

± ∆D

2,2

10

−10

2.91 ± 4% 0.494 ± 3% 0.932 ± 6·10

1

% 5.02 ± 2%

I

10

−6

2.83 ± 6·10

4

% 0.593 ± 2·10

4

% 0.835 ± 8·10

5

% 5.26 ± 3·10

4

%

10

−5

2.62 ± 3·10

5

% 1.45 ± 2·10

5

% 1.39 ± 2·10

6

% 6.50 ± 1·10

5

%

10

−10

2.78 ± 2·10

1

% 0.153 ± 7·10

2

% 1.09 ± 3·10

1

% 5.22 ± 9%

II

10

−6

2.77 ± 3·10

4

% 0.208 ± 1·10

7

% 1.28 ± 3·10

4

% 6.15 ± 1·10

4

%

10

−5

2.77 ± 1·10

6

% 0.485 ± 3·10

7

% 7.80 ± 4·10

4

% 31.5 ± 1·10

5

%

Chapter 3

38

estimated standard errors (ESE’s) smaller on average. Moreover, it appears that the binary

dispersion function (30) can also be fitted well to peak II, which indicates that the information on

the two superpositioned peaks is ‘weak’. Therefore, it is worthwhile to choose the sample

compositions such, that the recorder signal has a peak I appearance, but this may not always be

possible.

Of the diffusivities listed in the table, only those at σ

r

-values of 10

−10

V are usable. For the higher

noise levels, the ESE’s are so big that the values of the diffusivities are statistically insignificant.

That the fitted values of the D

ij

are not too far off, is a result of the ideal peaks: apart from the

(almost) perfectly white noise there are no disturbing influences. For the example peaks, the

maximum signal-to-noise ratios at a σ

r

of 10

−10

V are as high as 4·10

5

(peak I) and 5·10

6

(peak II).

Since such levels can not be expected in practice, the conclusion must be that one peak simply is

not enough to determine the diffusivities with low errors. Fits to two peaks simultaneously, on the

other hand, give perfect results with low ESE’s. This is illustrated in table 4. If the peaks are good,

a fit of more than two peaks gives only slight improvement.

Table 4. Two-peak fit results for both peaks I and II for varying σ

r

. Calibrated detector, sample

compositions known.

But there is more! From table 2, we see that we need two data sets to fit the diffusivities for an

uncalibrated detector. With the result for the calibrated detector in mind, we might expect that we

may need more than two sets, but this is not so. The linearity [S ] can be fitted together with [D ]

and the two τ’s without apparent loss of accuracy of the fitted value of [D ]. (In fact, it slightly

improves them.) Thus we kill two birds with one stone: we avoid the work of calibration, and we

keep errors in the experimentally determined values of [S ] out of our other parameters.

3.3 CONCLUSIONS

The first conclusion that can be drawn from the foregoing is that for normal substances, no special

precautions need to be taken for diffusivity measurements with the Taylor dispersion method. For

normal capillary dimensions, the coil diameter can be relatively small, and flows can be chosen

that result in acceptable residence times of the pulses. However, in extreme cases such as

macromolecular substances and unusual combinations of density, viscosity and diffusivity, it may

be necessary to decrease the flow rate through the capillary to obtain good accuracy.

The second conclusion is that it is possible to measure multicomponent diffusivities with a detector

which can produce only one independent signal. As more is known about the samples and the

detector linearity, fewer measurements are needed to produce reliable results.

σ

r

(V) D

1,1

± ∆D

1,1

D

1,2

± ∆D

1,2

D

2,1

± ∆D

2,1

D

2,2

± ∆D

2,2

10

−10

3.00 ± 5·10

−5

% 0.500 ± 4·10

−4

% 1.30 ± 3·10

−4

% 5.00 ± 8·10

−5

%

10

−6

3.00 ± 4·10

−1

% 0.520 ± 4% 1.29 ± 3% 5.05 ± 8·10

−1

%

10

−5

2.96 ± 5% 0.700 ± 3·10

1

% 1.17 ± 3·10

1

% 5.45 ± 8%

TAYLOR DISPERSION THEORY

39

NOTATION

a

1

,..., a

9

constants in coiled-capillary dispersion model, (–)

A constant, Σ α

i

−8

≈ 2.1701⋅10

−5

, (–)

b, b

1

,..., b

4

fitting parameters, (m)

c concentration, (mol m

−3

)

D Fick diffusivity, (m

2

s

−1

)

d inner capillary diameter, (m)

De Dean number, Re / λ

½

, (–)

disc[D] discriminant of [D], tr

2

[D]− 4 | D |, (m

4

s

−2

)

f detector signal, (V)

J

0

zeroth order Bessel function of the first kind

K

1

,..., K

4

constants in Price’s formulas eqs. (4) and (5), (mol)

L length of the capillary, (m)

m

2

second moment of the cross-section averaged concentration profile, (m

2

)

n number of moles (mol)

P pressure, (Pa)

Pe radial Péclet number, u

sup

d / D = Re Sc, (–)

r noise function, (V)

Re Reynolds number, ρ u

sup

d / η, (–)

Sc Schmidt number, η / ρ D, (–)

S detector linearity, (V)

s detector offset, (V)

tr [D] trace of [D], ∑

i

D

ii

, (m

2

s

−1

)

t time, (s)

u velocity, (m s

−1

)

V volume, (m

3

)

z axial capillary co-ordinate, (m)

Greek symbols

α

i

ith root of the derivative of J

0

∆ difference, deviation

δ coil diameter, (m)

ε accuracy, (–)

η fluid dynamic viscosity, (Pa s)

κ dispersion coefficient, (m

2

s

−1

)

λ coil / capillary diameter ratio, δ / d, (–)

ρ fluid mass density, (kg m

−3

)

σ ‘standard deviation’ of the response peak, (m)

σ

r

standard deviation of the normally distributed noise function, (V)

τ mean residence time, L / u

sup

, (s)

Φ

V

volumetric flow rate, (m

3

s

−1

)

Chapter 3

40

Subscripts

A Aris

cap capillary

EC Erdogan & Chatwin

i several counters

inj injected

m measurement

max maximum

NLG Nunge, Lin & Gill

sup superficial

V volume

Superscripts

E excess

T transpose

REFERENCES

[1] Alizadeh A., Nieto de Castro C.A., Wakeham W.A.

’The theory of the Taylor dispersion technique for liquid diffusivity measurements.’

Int. J. Thermophys., 1(3), 1980, pp 243–284.

[2] Aris R.

’On the dispersion of a solute flowing through a tube.’

Proc. Roy. Soc. A, 235, 1956, pp 69–77.

[3] Braam W.G.M.

’Scheidingsmethoden: chromatografie.’

1985, Wolters–Noordhoff, Groningen, NL.

[4] Chen H.R., Blanchard L.P.

Can. J. Chem., 53, 1975, p 228.

[5] Chen H.R., Blanchard L.P.

Can. J. Chem., 53, 1975, p 476.

[6] Dean W.R.

’Note on the motion of fluid in a curved pipe.’

Phil. Mag., 4, 1927, pp 208–223.

[7] Dean W.R.

’The stream-line motion of a fluid in a curved pipe.’

Phil. Mag., 5, 1928, pp 673–695.

[8] Erdogan M.E., Chatwin P.C.

’The effects of curvature and buoyancy on the laminar dispersion of solute in a horizontal

tube.’

J. Fluid Mech., 29, pp 465–484.

[9] Janssen L.A.M.

’Axial dispersion in laminar flow through coiled tubes’

Chem. Eng. Sci., 31, 1976, pp 215–218.

[10] Nunge R.J., Lin T.-S., Gill W.N.

’Laminar dispersion in curved tubes and channels.’

J. Fluid Mech., 51, 1972, pp 363–383.

TAYLOR DISPERSION THEORY

41

[11] Press W.H. et. al.

’Numerical Recipes.’

1986, Cambridge University Press, Cambridge, UK.

[12] Price W.E.

’Theory of the Taylor dispersion technique for three-component-system diffusion

measurements.’

J. Chem. Soc. Faraday Trans. 1, 84(7), 1988, pp 2431–2439.

[13] Rutten Ph.W.M.

’Diffusion in liquids.’

1992, Delft University Press, Delft, NL.

[14] Snijder E.D.

’Metal hydrides as catalysts and hydrogen suppliers.’

1992, Enschede.

[15] Taylor G.I.

’Dispersion of soluble matter in solvent flowing slowly through a tube.’

Proc. Roy. Soc. A, 219, 1953, pp 186–203.

[16] Taylor G.I.

’Conditions under which dispersion of a solute in a stream of solvent can be used to

measure molecular diffusion.’

Proc. Roy. Soc. A, 225, 1954, pp 473–477.

[17] Tijssen R.

’Effect of column-coiling on the dispersion of solutes in gas chromatography. Part 1:

theory’

Chromatographia, 3, 1970, pp 525–531.

[18] Tijssen R.

’Effect of column-coiling on the dispersion of solutes in gas chromatography. Part 2:

generalized theory’

Chromatographia, 5, 1972, pp 286–295.

[19] Tijssen R.

’On the dispersion of macromolecules in dilute solutions measured with the band-

broadening technique.’

Can. J. Chem. Eng., 55, 1977, pp 225–226.

[20] Tijssen R.

’Axial dispersion and flow phenomena in helically coiled tubular reactors for flow analysis

and chromotography’

Anal. Chim. Acta, 114, 1980, pp 71–89.

[21] Ven-Lucassen I.M.J.J. van der, Kieviet F.G., Kerkhof P.J.A.M.

‘Fast and convenient implementation of the Taylor dispersion method.’

J. Chem. Eng. Data, 40, 1995, pp 407–411.

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