Corresponding author. Tel.: +34 926 295 212; fax: +34 926 295 361.
Email addresses: L.RodriguezAragon@uclm.es (L.J. RodrguezAragn),
Jesus.LopezFidalgo@uclm.es (J. LpezFidalgo).
URL: http://areaestadistica.uclm.es (J. LpezFidalgo).
01697439/$  see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemolab.2007.05.004
water per amount of adsorbent. Water activity, a
w
=p/p
0
, where p
is the water vapour pressure exerted by the food material, and p
0
is
the vapour pressure of pure water at the experiment temperature.
Water activity can vary within [0,1].
BET gas adsorption isotherm is one of the classical models
of multilayer adsorption. It expresses the amount of gas or water
adsorbed, w
e
, in terms of water activity a
w
, following a normal
distribution of mean and variance,
E w
e
w
mB
c
B
a
w
1 a
w
1 c
B
1 a
w
; var w
e
r
2
: 1
The parameter w
mB
is the monolayer capacity and c
B
is related
exponentially to the enthalpy of adsorption in the first adsorbed
layer. Monolayer capacity is used to measure the surface area of
the adsorbent. Areport of 1985 of the Commission on Colloid and
Surface Chemistry [6] recommends the BET model for a standard
evaluation of monolayer values in adsorbate activity values not
higher than 0.3. Meanwhile in water adsorption by foodstuff this
limit is usually increased up to 0.5 [7].
In recent years GAB gas adsorption isotherm has been
widely used to especially describe the sorption behaviour of
foods and it has been recommended by the European Project
Group COST90 [8]. This model introduces the idea that the
sorption state of the sorbate molecules beyond the first layers is
the same, but different from the pure liquid state. This difference
demands the introduction of a new parameter. Then, the amount
of water adsorbed w
e
is normally distributed with the following
mean and variance,
E w
e
w
mG
c
G
ka
w
1 ka
w
1 c
G
1 ka
w
; var w
e
r
2
: 2
The parameters w
mG
and c
G
are the analog to those in BET
model, i. e., monolayer capacity and energy constant. The
additional parameter introduced, k, is a measure of the free
enthalpy of the sorbate molecules in these two states: the liquid
and the second sorption state. Measurement are then carried out
for upper limits of water activity up to 0.8 or even 0.9 [7].
1.2. Optimum design background and approach
An experimental design consists of a planned collection of
points a
w1
, a
w2
,, a
wN
, in a given space X. Some of these N
points may be repeated, meaning that several observations are
taken at the same value of a
w
. The total number of observations
is N and this number is usually predetermined by experimental
cost constraints. A convenient way to understand designs is to
treat them as a collection of different points of X, together with
the proportion of the N observations allocated at the different
points. This suggests the idea of the socalled approximate
design as a probability measure on X. Then (a
w
) is the
proportion of observations to be taken at the point a
w
. Kiefer [9]
pioneered this approach. Its many advantages are well docu
mented in design monographs [10]. This approach has been
recently applied to find optimum estimation of the parameters of
the MichaelisMenten model [11] and the Arrhenius equation
[12]. In what follows, the approximate design approach will be
adopted restricting the attention to designs with a finite set of
support points. For convenience, the design will be described
using a two row matrix with the support points displayed in the
first row and their corresponding proportion of observations in
the second row.
The paper is organized as follows. The aim of Section 2 is to
introduce and solve the problem of discriminating between both
adsorption isotherms using Toptimality. Once the adequate
model has been selected, D and coptimality criteria are intro
duced in Section 3. D and coptimum designs are computed in
Sections 4 and 5 for each adsorption isotherms respectively.
Advice on designing adsorption experiments can be obtained
from the efficiency plots. Comparisons between the optimum
designs and conclusions are finally presented in Section 6.
2. Designing to discriminate between rival models,
Toptimality
The first objective to characterize adsorption phenomena is
to choose which of the models will best fit the data. The main
difference is the water activity range in which the measurements
are taken, for BET model the water range is recommended to be
X
B
=[0.05, 0.30.5] while GAB model can be used in a wider
range X
G
=[0.05, 0.80.9]. BET model is supposed to be ex
posed to lack of fit beyond 0.5 [7], which according to literature
is said to be caused by the linearization of the model. The
simplicity of BET model is preferred to the extension made in
GAB model while performing a direct non linear regression
[13,14].
GAB model is an extension of BET model in which a new
parameter k is introduced, being both models identical for k=1. It
is frequently observed that GAB model is treated as a purely
empirical one with values of k unwarranted by the physics behind
the equations, with kN1, as remarked in [15]. This fact leads to
prefer BET model being the water range extended up to 0.8 or
even 0.9 in some works, while in others it is kept up to 0.5 [16].
The most popular design criterion for model discrimination is
Toptimality which was proposed by Atkinson and Fedorov [17].
It has lately been extended to nonnormal models [18]. A design
for model discrimination should provide a large lack of fit sumof
squares for an incorrect model [19]. Given two competing
models there may be two Tcriteria functions, depending on the
model considered true. The aim of this work is to obtain a good
design to discriminate between GAB and BET models for the
wide range of water content X
G
.
It will be used to say whether it is adequate to apply the
simpler BET model to adsorption phenomena in X
G
or not. The
Toptimum design provides the most powerful Ftest for lack of
fit of the second model when the first is true [19].
Consider the general non linear regression model
w
e
g a
w
; a
w
aX; 3
where the random variable is independent and normally
distributed with zero mean and constant variance
2
. The
function (a
w
) is either GAB model,
G
(a
w
,
G
), or BET
37 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644
model,
B
(a
w
,
B
), where h
t
G
w
mG
; c
G
; k aX
G
o
3
and
h
t
B
w
mB
; c
B
aX
B
o
2
are parameter vectors. Henceforth,
(a
w
) =
G
(a
w
,
G
) will be assumed the true model with the
corresponding known parameters
G
.
The T criterion function is then
T
BG
n min
h
B
aX
B
i
n a
wi
g a
wi
g
B
a
wi
; h
B
2
: 4
A design
T
that maximizes T
BG
() is called Toptimum. For
regular designs the Equivalence Theorem [17] is applied in such
a way that a design
T
T
_ _
g a
w
g
B
a
w
;
h
B
_ _ _ _
2
i
n a
wi
g a
wi
g
B
a
wi
;
h
B
_ _ _ _
2
V 0; a
w
aX;
5
with equality at the support points of
T
) is a measure of the
efficiency of with respect to the Toptimum design
T
. This
efficiency will be considered as a measure of the design
goodness with respect to this criterion.
The construction of Toptimum designs is numerically de
manding due to the need of estimating
B
for the competing
model (6). The criterion function T
BG
() has
B
as argument
and its value will change at each step the algorithm.
In practice, a first order algorithm is used to find the
Toptimum design [17].
The iterative procedure is as follows.
Step 1: For a given design
s
supported at points a
w1
, a
w2
,...,
a
ws
, take
h
B;s
n
s
arg min
h
B
a X
B
i
n
s
a
wi
g a
wi
g
B
a
wi
; h
B
2
:
6
Step 2: Find the point a
ws + 1
=arg max
a
w
X
((a
w
)
B
(a
w
,
B,s
))
2
.
Step 3: Let
a
ws + 1
be a design with measure concentrated at
the single point a
ws +1
. A new design is constructed in the
following way:
s +1
=(1
s +1
)
s
+a
s +1
a
ws + 1
, where typ
ical conditions for the sequence {
s
} are lim
sYl
a
s
0;
l
s0
a
s
l;
l
s0
a
2
s
bl:
Step 4: A lower bound for the Eff
BG
() has been proposed,
so that the iterative procedure will stop when
1
max
a
w
aX
w a
w
; n
s
T
BG
n
s
_ _
1
N d; 7
where 0bb1 is a suitably chosen value, e.g. =0.998 [18].
To ilustraste the Toptimum design calculation process two
examples are presented. The range of water content (design space)
considered will be X
G
=[0.05, 0.8]. To calculate the Toptimum
design initial estimates for
G
obtained from real experimental
works are used.
Example 1. In [20] water sorption behaviour of coffee was
studied for predicting hygroscopic properties as well as de
signing units for its optimum preservation, storage, etc. The case
of coffee roasted with sugar was considered in that work. The
results at 25 C for the GAB isotherm were w
mG
=0.03445 g of
H
2
O adsorbed/g of coffee, c
G
=11.70 and k=0.994. Notice that
for k=1 GAB and BET models are identical. To compare both
models the Toptimum design will provide the Ftest for lack of
fit of BET model.
After 182 iterations of the algorithm, with
s
=1/(s +1), a
design supported at three experimental points was obtained with
a lower efficiency bound of =0.998.
n
T
0:056 0:62 0:8
27
182
4
7
51
182
_
_
_
_
T
0:099 0:64 0:8
47
270
74
135
5
18
_
_
_
_
a
w
aX
f a
w
f
t
a
w
n a
w
; 10
apart from an unimportant multiplicative constant. When the
number of observations N is large, the covariance matrix of the
estimates of is known to be approximately
2
/N times the
inverse of this matrix [10].
The design criteria used in this work for estimating the model
parameters are given by two criteria functions. Doptimality is
given by
D
[M (, )] =det M (, )
1/m
, where m is the
number of parameters in the model, while coptimality is defined
by
c
[M (, )] =c
t
M (, )
1
c, being c
t
the linear combination
of the parameters to be estimated. A design that minimizes one
of these two functions among all the designs on X is called a D or
coptimum design respectively. An advantage of working with
approximate designs is that their optimality can be easily checked
using the Equivalence Theorem. In addition this result provides
methods for the construction of optimum designs [21,22]. For a
general criterion function non decreasing, convex and
differentiable, defined on the information matrices, a design
U
_ _
f
t
a
w
jU n
U
_ _
f a
w
trM n; h jU n
U
_ _
z0; a
w
aX;
11
with equality at the support points of
. Here () is [M (, )]
for simplicity of notation and () denotes the gradient of
().
The goodness of a design is measured by its efficiency,
defined by Eff
() =(
.
It is important to remark that both BET and GAB models
are partially nonlinear in terms that the models are linear for
the monolayer capacity, w
m
, and nonlinear for the other param
eters [23]. Therefore, the D and coptimum designs obtained
will be independent of the initial best guesses of the mono
layer capacity and will only depend on the truly nonlinear
parameters.
4. Optimum designs to estimate the BET model
For BET model, being
B
t
=(w
mB
, c
B
) the unknown param
eter vector let f (a
w
) =E(w
e
)/
B
be evaluated at the best guess
of the parameters
B
,
f a
w
c
B
a
w
1 a
w
1 c
B
1 a
w
;
w
mB
a
w
1 c
B
1 a
w
2
_ _
t
;
a
w
aX
B
a
w0
; a
wF
:
12
4.1. Doptimum designs
To estimate both parameters of BET model simultaneously,
Doptimality criterion has been used. A 2point design maxi
mizing the determinant of the information matrix is computed.
It is well known that the weights of a Doptimum design with m
points in its support have to be equal. Then the equivalence
theorem is used to check whether this is actually the Doptimum
design or not. A Doptimum design
D
is equally weighted at
two points in X
B
: (a
wD
, a
wF
) if a
wD
X
B
or (a
w0
, a
wF
) other
wise. The point a
wD
is the unique solution on X
B
of the fol
lowing equation (Sturm Theorem):
a
3
wD
a
2
wD
2a
wF
1
c
B
1
_ _
a
wD
a
wF
2
c
B
1
_ _
a
wF
c
B
1
0:
13
Fig. 2. Values of a
wD
as c
B
varies in the design space X
B
and for the extended
X
G
. In both cases for values c
B
N20, a
wD
=a
w0
=0.05.
39 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644
Note that equally weighted means that half of the obser
vations are taken at one of the support points and the other half
at the other.
The Equivalence Theorem (11) provides a condition to check
the Doptimality of
D
is Doptimum if
and only if
f
t
a
w
M n
D
_ _
1
f a
w
V m; a
w
a X
B
; 14
where m=2 is the number of parameters. The equality is
satisfied at the support points. The values of a
wD
for c
B
[1,30]
and for two different water ranges are plotted in Fig. 2.
Example 3. Most of the times a Doptimum design will not
satisfy an experimenter due to its radical form, only supported at
two points. In real experiments the need of a larger group of
support points is mostly required. The experimental points are
usually settled along the design space without any kind of special
distribution. Any design is compared to the Doptimum by
computing its criterion value
D
() =det M(,
B
)
1/2
and
the efficiency respect to the Doptimum, Eff
D
() =
D
(
D
)/
D
().
In this example the performance of different types of designs
for estimating the parameters will be compared to the Dop
timum design. All the designs compared are supported at 6
different points and all of them are supposed to be equally
weighted. Therefore, N/6 observations will be taken at each
point. The total number of observations taken, N, remains con
stant in all the designs. This number is usually established by
experimental cost constrains. The designs to be compared are:
A uniform design, where the support points are uniformly
distributed along the design space with a constant spacing
parameter, d, which is the distance between every pair of
consecutive support points.
An arithmetic design, where the spacing parameter grows in
an arithmetical progression (id) from left to right of the
design space, where i =0, , 5.
A geometric design (left), where the spacing parameter
grows in a geometrical progression d
i
from left to right of the
design space.
A geometric design (right), where the geometrical progres
sion goes from right to left of the design space.
A linear inverse design where the interval [
B
(a
w0
),
B
(a
wF
)] is uniformly divided. Then the corresponding points
in the design space X
B
through the inverse regression function
are taken as support points.
In all these cases the rates d are setup in such a way that the
extremes are the first and the last design points.
Efficiencies of these five different experimental designs have
been plotted in Fig. 3 for different values of c
B
and for the two
different design spaces. The experimenter may use this graphs
as a reference to choose one of the five designs according to the
foreseen.
4.2. coptimum designs
In order to estimate a linear combination of the parameters,
say c
t
B
, the coptimum criterion should be used, being this
method useful when single estimations of the parameters are
required.
Fig. 4. Elfving set for BET model. Points f (a
w0
) =(x
0
, y
0
)
t
and f (a
wF
) =(x
F
, y
F
)
t
are the values of f for the extremes of the design space X
B
. In this particular case
the coptimum designs are both defined by f (a
wt
) =(x
t
, y
t
)
t
and f (a
wF
) =(x
F
, y
F
)
t
.
The points (x
, 0)
t
and (0, y
)
t
are convex combinations of these two points f (a
wt
),
f (a
wF
) and the corresponding coefficients give the weights of the optimum
designs.
Fig. 3. Efficiencies of the five different experimental designs in comparison to the Doptimum design. The efficiency will provide the experimenter with important
information to choose an appropriate distribution of the observations.
40 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644
Elfving [24] proposed a nice graphical method of obtaining
optimum designs to estimate linear combinations of the param
eters. Elfving's set is defined as =Hull{ f (X
B
) f (X
B
)}.
Hull means that is the smallest convex set containing
{ f (X
B
) f (X
B
)}. Then the coptimum design
c
is determined
by c
c
(
c
) =( c/c
 )
2
.
Elfving's set for BET model is shown in Fig. 4. For
example in order to estimate w
mB
, the monolayer capacity, the
linear combination of the parameters should be set to c
t
=(1, 0)
and the resulting optimum design is called w
mB
optimum. This
method provides analytical designs in this case. The vertices of
are the following points and their symmetric ones,
(1) The end point of the curve f (X
B
), f (a
wF
) =(x
F
, y
F
).
(2) The tangential point f (a
ws
) =(x
s
, y
s
) of the line starting at
f a
wF
; a
ws
1=
a
wF
1 c
B
_
.
(3) Either the starting point of the curve f (X
B
), f (a
w0
) =(x
0
, y
0
),
or the tangential point f (a
wt
) =(x
t
, y
t
) of the line starting
at f (a
wF
). Where a
wt
is the real solution in X
B
of the
equation,
a
4
wt
a
wF
1 c
B
2
2a
3
wt
a
2
wF
1c
B
2
a
2
wt
a
3
wF
c
B
1
2
2c
B
a
2
wF
c
B
1 6a
2
wF
c
B
1 a
wF
4c
B
6 1
2a
wt
a
wF
a
2
wF
0:
15
(4) The points of the curve f (X
B
) between points 2) and 3).
Fig. 6. Efficiencies for the five experimental designs. Left, efficiencies to estimate w
mB
for the two design spaces. Right, efficiencies to estimate c
B
.
Fig. 5. Left, variation of a
wc
against c
B
for the two different design spaces. Right, variation of the proportion of observations to be taken at a
wc
to obtain the w
mB
 and
the c
B
optimum designs. Squares represent the evolution for the space design X
B=
[0.05, 0.5] and triangles for X
B
=[0.05, 0.8].
41 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644
From the geometry of Fig. 4 and Elfving's argument,
the w
mB
 and c
B
optimum designs are:
n
cB
a
wc
a
wF
p
wmB
1 p
wmB
_ _
;
p
wmB
a
wF
1 a
wc
c
B
1
2
a
wc
a
wF
1 a
wc
c
B
1 4 a
wc
c
B
1 a
wF
c
B
1
:
16
n
cB
a
wc
a
wF
p
cB
1 p
cB
_ _
;
p
cB
a
wF
a
wc
1 1 a
wc
c
B
1
a
wc
a
wF
1 a
wc
a
wc
a
wF
4 c a
wc
a
wF
2 a
wF
c
B
2
:
17
where a
wc
=a
wt
if a
wt
X
B
and a
wc
=a
w0
otherwise.
As for the Doptimum design, the values for a
wc
versus c
B
are plotted in Fig. 5 for the two different water ranges. The
proportion of observations to be taken at this point to obtain the
w
mB
and the c
B
optimum designs are also plotted.
Example 4. The w
mB
 and c
B
optimum designs,
w
mB
and
c
B
,
provide a tool for the experimenter to measure the efficiency of
any experimental design, , when only the estimation of one of
the parameters is required. Any design is compared to the cor
responding coptimum by obtaining its criterion value
c
() =
c
t
M (,
B
)
1
c, then the efficiency Eff
c
() =
c
(
c
)/
c
().
As in Example 3 the previous five experimental designs are
compared with both coptimum designs. Efficiencies for both
design spaces have been plotted and shown in Fig. 6 for
different values of c
B
.
The differences between the efficiencies to estimate either
w
mB
or c
B
should be remarked. For example, in order to esti
mate w
mB
with initial nominal values of c
B
N10, the best ex
perimental design from the five proposed is the geometric
design (right), being the geometric design (left) the one with
lowest efficiency. However, in order to estimate c
B
for the same
conditions the situation turns out to be the opposite.
5. Optimum designs to estimate the GAB model
For GAB model, being
G
t
=(w
mG
, c
G
, k) the unknown
parameter vector, let f (a
w
) =E(w
e
)/
G
be evaluated at the
best guesses for parameters
G
,
f a
w
c
G
ka
w
1 ka
w
1 c
G
1 ka
w
;
w
mG
ka
w
1 c
G
1 ka
w
2
;
w
mG
c
G
a
w
1 c
G
1 k
2
a
2
w
_ _
1 ka
w
2
1 c
G
1 ka
w
2
t
; a
w
aX
G
a
w0
; a
wF
:
18
5.1. Doptimum designs
To estimate the three parameters of GAB model simulta
neously Doptimum designs have been calculated. An analy
tical expression of the designs is not available now. The aim
is to find a design minimizing the expression
D
[M (,
G
)] =
det M (,
G
)
1/m
, m=3.
The Doptimum designs are equally weighted at three
points: a
w1
, a
w2
and a
wF
; where a
wF
is the upper extreme of
X
G
, a
w2
X
G
and a
w1
is either in X
G
or it is the lower extreme
of X
G
, a
w0
.
For GAB model, Doptimum designs in the design space
X
G
=[0.05, 0.8] have been numerically calculated for different
nominal values of the parameters. The support points a
w1
and
a
w2
are plotted in Fig. 7. As the model is partially nonlinear, D
optimum designs depend only on the parameters c
G
, k, and the
design space. A design will be Doptimum if and only if the
condition in [14] is fulfilled.
Example 5. As done for BET model in Example 3, the ef
ficiencies of different experimental designs with 6 support
points and with the same proportion of observations at each
Fig. 8. Efficiencies of the five experimental designs in comparison to the Doptimum design.
Fig. 7. Values of a
w1
and a
w2
as c
G
varies and for values of k=0.5, 0.8.
42 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644
support point, N/6, have been calculated and shown in Fig. 8.
The design space for GAB model is X
G
=[0.05, 0.8] and the
efficiencies have been obtained for two different values of the
parameter k=0.5, 0.8.
In this case, the arithmetic design gives the highest
efficiencies for high values of c
G
, while the uniform design
should be preferred for low values. Optimum designs give the
chance to measure the efficiency of any design that want to be
performed.
5.2. coptimum designs
Since the dimension of the parameter vector
G
is three, the
resulting Elfving set for GAB model in
3
makes the task of
obtaining the convex combinations much more difficult than for
BET model. Although Elfving's method [24] is valid for any
dimension, it is rarely used geometrically for more than two
parameters. A computational procedure, proposed for more than
two parameters [25], has been followed in this work. When a
single parameter is of particular interest coptimality becomes
D
s
optimality and the procedures to compute D
s
optimal
designs may be used here as well.
To determine a coptimum design, the intersection u
,
c
G
and
k
c
a
w1
a
w2
a
wF
p
c
q
c
r
c
_ _
; 20
where a
wF
is the upper bound of X
G
, a
w2
X
G
, and a
w1
is either
in X
G
or the lower bound of X
G
, a
w0
.
The support points for coptimum designs in the design
space X
G
=[0.05, 0.8] have been calculated with the method
given by [25]. As the model is partially nonlinear, the designs
only depend on the parameters c
G
, k, as well as on the design
space. The support points a
w1
and a
w2
are shown in Fig. 9 for
different values of c
G
(1, 30) and for two initial best guesses
of parameter k=0.5, 0.8. For the c
G
optimum designs and for
Fig. 10. Efficiencies of the five experimental designs in comparison with the w
mG
optimum design.
Fig. 9. For k=0.8, the three coptimum designs are supported at a
w1
, a
w2
, a
wF
. The evolution of a
w1
, a
w2
as c
G
varies are shown, . For k=0.5, w
mG
 and koptimum
designs are also supported at a
w1
, a
w2
, a
wF
. The evolution of a
w1
, a
w2
as c
G
varies are shown, . For k=0.5, c
G
optimum design is supported for c
G
b5 at the same
three support points, , but for c
G
5 the design becomes singular and it is supported only at a
w1
and a
w2
, .
43 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644
the initial best guess of the parameter k=0.5 the c
G
optimum
design changes from three support points to two (a
w1
, a
w2
),
becoming a singular design, as observed in Fig. 9.
Example 6. As in previous examples, the efficiencies for the five
experimental designs with 6 support points equally weighted have
been calculated. These efficiencies for the w
mG
optimal design
are shown in Fig. 10 for different values of c
G
and k. The highest
efficiencies are obtained, depending on the value of c
G
: the
uniform and arithmetic designs for k=0.5, while for k=0.8, the
one with the highest values of efficiency is the uniform design.
6. Conclusions
Optimum designs to discriminate between GAB and BET
models have been shown through this work. Once the model has
been selected, optimum designs for estimating the parameters
have been obtained. Optimum designs obtained may be used as
references for the experimenters to measure the efficiency of
their designs according to the criteria of T, D and coptimality.
The prior selection of the model is addressed with Toptimality
criterion, which allows the experimenter to choose between
the two models. The choice of one of these two models has been
widely studied and justified in adsorption problems [7]. The
need of nominal values for the parameters as initial guesses
becomes a minor problem here due to the amount of works in
literature which supply values for the parameters to be used as
initial estimations. In practice estimating the adsorption of water
on food stuff needs to take measurements periodically. Therefore,
estimates from retrospective studies can be used as nominal
values to obtain the optimum designs.
The choice of the optimality criterion becomes easier once
the efficiencies of each optimum design in comparison with
other criteria are obtained. As an illustrative example, D and
cefficiencies of the Toptimum designs obtained in Examples
1 and 2 have been calculated and shown in Table 1. A high
efficiency was obtained for the koptimum design in Example
1, k=0.994 while for the Example 2, k=0.94, the efficiency is
much lower. The Toptimality criterion considers the GAB
model as the true one, being both models identical for values of
k=1. For nominal values of k near 1 the Toptimum design is
very close to the koptimum design.
The optimum designs computed in this paper claim for
observations at 2 or 3 points, some of them are quite extreme.
This is frequently disliked by the practitioners, who want some
other observations to be more confident on the final results.
In this paper the efficiency of typical sequences of points
have been analyzed according to the reference given by the
actual optimum designs.
Acknowledgements
The Authors would like to thank the Referees for their
helpful comments. This work was sponsored by Junta de
Comunidades de CastillaLa Mancha PAI0700192036.
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Table 1
D and c efficiencies of Toptimum designs of Examples 1 and 2
Eff
(
T
) GAB BET
D w
mG
 c
G
 k D w
mB
 c
B

Example 1 0.84 0.88 0.25 0.99 0.52 0.44 0.19
Example 2 0.81 0.69 0.28 0.88 0.59 0.40 0.27
44 L.J. RodrguezAragn, J. LpezFidalgo / Chemometrics and Intelligent Laboratory Systems 89 (2007) 3644