Accepted Manuscript

A chemical equilibrium modelling strategy for tuning the apparent equilibrium

constants of the chemical systems

Somaiyeh Khodadadi Karimvand, Marcel Maeder, Hamid Abdollahi

PII: S0003-2670(18)31277-7
DOI: https://doi.org/10.1016/j.aca.2018.10.047
Reference: ACA 236353

To appear in: Analytica Chimica Acta

Received Date: 21 August 2018

Revised Date: 21 October 2018
Accepted Date: 22 October 2018

Please cite this article as: S. Khodadadi Karimvand, M. Maeder, H. Abdollahi, A chemical equilibrium
modelling strategy for tuning the apparent equilibrium constants of the chemical systems, Analytica
Chimica Acta, https://doi.org/10.1016/j.aca.2018.10.047.

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

A chemical equilibrium modelling strategy for tuning the apparent equilibrium

constants of the chemical systems

Somaiyeh Khodadadi Karimvand a, Marcel Maeder b, Hamid Abdollahi *a

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a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences,

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P.O. Box 45195-1159, Zanjan, Iran

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b
Department of Chemistry, University of Newcastle, NSW 2308, Australia

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*
To whom correspondence should be addressed. E-mail: abd@iasbs.ac.ir,
Tel.: (+98 24) 33153122, Fax:(+9824) 33153232.

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 ACCEPTED MANUSCRIPT
Abstract:

In many equilibrium systems, it is customary to use a simplified, apparent equilibrium

reaction instead of the complete reaction model. The resulting apparent equilibrium constants
are altered or controlled by changes of the chemical system, usually modifying the total
concentration of auxiliary reagents, but the variation of other parameters such the intensity of
light in photo-controlled reactions, types and concentration of solvents or composition of

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mixed solvents, the ionic strength of the chemical media, etc. is also possible. The main goal
of this work is to propose a chemical equilibrium modelling based strategy to control the

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conditions governing equilibrium systems in order to tune the apparent constants. Indeed, by
extracting the analytic relationship between the parameters of the complete model and

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apparent model, the magnitude of the apparent constant(s) can be predicted.

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At first, a basic strategy for calculating the tunable range of apparent constants of chemical
equilibria is proposed. Next, three case studies for tuning the apparent constants are
investigated in detail: inclusion complexes with cyclodextrin, aqueous micellar solutions for
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investigating the solvent effects and the boric acid/Mannitol system that allows the tuning of
the apparent protonation constant. In all examples tuning the apparent constant is possible by
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regulating the chemical composition.

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Keywords: Chemical equilibria modelling, Apparent equilibrium constant, Cyclodextrin,

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Micelle, Boric Acid

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Introduction:

For many important equilibrium systems, it is customary to use a simplified apparent, instead
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of a complete but rather complex equilibrium system. The following equilibria exhaustively
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describe all interactions between Ni2+ and protons with EDTA (Y) in aqueous solution [1]:

Scheme 1. The equilibrium reactions between Ni2+ ions, protons and EDTA in aqueous solution.

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The collection of 9 equilibrium constants (K1, K2….K9) together with the total concentrations
for the components quantitatively defines the speciation in any solution of the three
components.

For most relevant applications, i.e. complexometric titrations, this complex equilibrium
system is reduced to an apparent simple equilibrium under condition of constant pH. Most
titrations are conducted at a certain pH in buffered solutions.

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Ni + Y ⇌ NiY K = (1)

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K' is the conditional formation constant which describes the action quantitatively as long as
the pH is constant [1], it’s value is pH-dependent. In other words, there is a range of the

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apparent equilibrium constant, K’, can be tuned by the adjusting the pH in a predefined value.
The simple form is appropriate for the application of EDTA in complexometric titrations.

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Note, K’ is not the same as K7 (K = ), in this notation [NiY’] represents all
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complex species, [NiY’] =[ NiY2-]+[NiYH-]+[NiYH2], similarly [Y’] = [Y4-]+[YH3-
]+…+[YH62+].
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While the application of the above ideas for the EDTA metal interactions are well-known,
there are other applications where the simplification of using apparent constants have been
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utilized. The effect of different pH on chelating agents for complexing metal ions
have been investigated by several groups [2-4]. For such cases the pH can be used as a
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controllable variable for adjusting or tuning the apparent equilibrium constants.

There are several examples in the chemistry literature where the apparent equilibrium
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constants have been adjusted by different controllable variable such as solvent, micelle
concentration or some interfering chemical species. One application of micells in analytical
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chemistry is to study the pH indicators in order to shift the chemical equilibrium and
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therefore the pKa [5-8]. Garcia and Medel studied the mechanism of dye-surfactant
interactions in micelles solutions in detailed [9]. Safavi and Abdollahi have observed
significant shift in equilibrium and kinetic constants in micelle solutions [10]. The effect of
ionic liquids on the apparent acidy constants of acid-base equilibria of indicators were
reported by several works [11-13]. Also it has been shown that investigation of some
chemical equilibria have been possible by adjusting the apparent equilibrium constants under
certain chemical-physical conditions [14, 15].

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The objective of this study is first to quantitatively investigate the effects of side equilibria in
order to find the tunable range of the apparent or conditional constants of different chemical
equilibrium systems. In the second part we investigate and analyze the theoretical results for
a few practically relevant systems. Three case studies were investigated. In the first example
the effect of micelle concentration on apparent protonated constant was investigated. In the
second case study, the effect of presence of Cyclodextrins (CD) on the acid-base equilibrium

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of Neutral Red (NR) was studied. Finally, in an experimental investigation, the apparent
protonation constant of the weak boric acid was tuned by the addition of different amounts of
Mannitol.

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The concept of equilibrium reactions is extremely important in chemistry as many main

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applications of chemistry processes are based on the laws which govern the equilibrium
reactions. In a typical equilibrium reaction, the amount of activities of involved components

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is determined by the relevant thermodynamic constant. As the activities of equilibrium
involved components are controlled by the thermodynamic parameters then tuning the
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relevant equilibrium constants can control the efficiency of the equilibria based process such
as chemical sensing. The efficiency of the most biosensors and chemosensors is governed by
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the amount of equilibrium constants which define the sensitivity and selectivity of sensing
processes. The difference in the affinity constants of different analytes with receptor makes it
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possible to qualitative and/or quantitative analysis of them in competitive reactions. Usually,

for improving the sensitivity or selectivity of sensors, the equilibrium constant has been tuned
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by optimizing the temperature of the reactions. Indeed, by tuning the equilibrium constant,
the affinity of analytes to the receptors can be controlled and placed under optimum
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conditions. The purpose of this study is to provide a general strategy for tuning the apparent
equilibrium constants using other controllable variables which can have many applications in
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designing efficient sensors for determination and quantification of analytes. It is clear that the
ability for tuning the equilibrium constants can be effective in the application of many of
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equilibrium-based chemical processes.

General strategy for tuning the apparent constant:

To further investigate the issues of using apparent equilibrium constants, we quantitatively

analyze a simpler equilibrium system.

A + B ⇌ C K = (2)
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Consider a situation where both a reactant and the product are involved in competitive
equilibrium reactions with an interferent I, this is represented in scheme 2.

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Scheme 2. The basic equilibrium A+B = C, with two auxiliary equilibrium interaction between the interferent I
and the equilibrium species A and C.

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In addition to the initial equilibrium there are now two additional interactions of I with A and

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with C:

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.$
K .$ = (3)
$

.$
K = (4)
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.$ $

The apparent equilibrium reaction and its constant K is defined as:

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A′ + B ⇌ C′

K = (5)
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The hypothetical components A' and C' are defined as the sum over all species containing
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component A or C.

A = A + A. I (6)
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And:
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C = C + C. I (7)
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Thus, in the presence of the side reaction(s), the relationship between the hypothetical
components A' and C' and the real species of the system can be defined by combining
equations 5, 6 and 7:
.$
K =( .$ ) !

Next equations (3) and (4) are used to replace [A.I] and [C.I]

,-.. $
K =(
,/.. $)!

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Rewriting results in
1 ,-.. $
K = !
× 1 ,/.. $

Therefore,
1 ,-.. $
K =K 1 ,/.. $
(8)

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In this system of complete and apparent reaction schemes, an analytical relationship between
the real and the apparent constants can be established. According to Eq. 8, the value of the

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apparent constant is defined by the constants of the complete model KC, KA.I and KC.I as well
as the free [I] concentration of the interferent I. Equation (8) also shows that the influence of

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[I] on K is more prominent if the equilibrium constants KA.I and KC.I are dissimilar. If the
interferent is added in large excess, it’s free concentration is approximately constant and thus

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also the value for the apparent equilibrium constant K . If just the reactant A gets involved
in the side reaction KC.I would be zero, and in the situation where only the product (C) is
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involved in the side reaction KA.I is zero.

Now, this question can be asked that under what situation the apparent model and the related
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constant (K ) is applicable in an equilibrium system. By involving the side reaction(s), total

concentrations of all components can be applied as controllable variables for changing [I].
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Thus, the equation 5 is applicable where the [I] is independent to the total concentrations of
all involved components (A, B and I).
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The question is under what circumstances can the apparent model and the related constant
(K ) be applied to an equilibrium system. By involving the side reaction(s), the total
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concentrations of all components will influence [I]. Thus, the equations 5 and 8 are applicable
where the [I] is independent to the total concentrations of all involved components (A, B and
C

I). In this section we investigate situations where the apparent model is valid.
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Herein, the effect of total concentration of interferent I (which is introduced to the system and
can be used to tune the apparent constant) on the [I] and consequence the fixedness of
apparent constant during a typical titration is investigated. As an example, in Figure 1 the
value of [I] as a function of CI during the titration for KC = 106, KA.I = 104.5 and KC.I =101.2
has been shown. It is clearly manifested from the figure 1 that in the low total concentrations
of the interferent I, the free concentration of I, [I], and thus the apparent constant is not
independent to the equilibrium situation (Part A in Figure 1), while part B shows the region

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where the CI and [I] are independent. Therefore, since [I] in each titration is approximately
constant in a certain range of total concentrations of I, (the percent change of [I] during the
under studying system is <=1%) this range of CI can be applicable for applying the apparent
model. Notably, this range is practically limited in the higher concentrations of I. Thus, for
any equilibrium system, a limited range of interferent concentration can be achieved in which
the apparent model is applicable.

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As can be seen clearly from the figure 1, in the permissible range of the apparent model (part
B), by changing the total concentration of I (CI) the [I] is altered. Thus, in part B by changing

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CI the apparent constant will be changed. Obviously, this is the permissible range of tuning
the apparent constant. Figure 2 shows the dependency of apparent constant (K ) in its

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calculated tunable range as a function of the total concentration of interferent I. This tuned
range of apparent constant for any equilibrium reaction can be determined from the complete

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model of the related system. This is clear from the Figure 2 that under the mentioned
condition the apparent constant of the system could be tuned from 103.69 to 102.48.
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While for many practical applications, it is not crucially important to have a constant value
for K , or to maintain constant free [I], it is instructive to investigate the change in K
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during a typical titration.

The change in [I] is also depend on the initial concentrations of all involved components A, B
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and I. A complete picture can show the effect of all controllable parameters on the tunable
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range of apparent constant. The Figure (3) shows the effect of different total concentration of
reactants (CA and CB) for the mentioned equilibrium system with determined equilibrium
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constants. 28 samples with different CA (10-6 to 1M) and CB (10-6 to 1M) were simulated.
Each surface in Figure 3. displays the effect of changing the CI for each sample with
determining CA and CB on the tuned range of apparent constant. Indeed, for the equilibrium
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system of equation 2 with defined constants (KC, KA.I and KC.I) the tuned range of apparent
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constant is determined in all permissible range of total concentrations of all involved

components (Figure 3.). Thus, the apparent constant of this system can be tuned from 105.9 to
102.48.

It can be generalized that for any equilibrium system the tunable range of apparent constant is
achieved in permissible ranges of all externally controllable parameters.

Case studies:
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This work includes three case studies where the above ideas are applied for the tuning the
apparent model parameters of exemplary chemical equilibrium systems. Two systems are
simulated using equilibrium constants from published chemical systems. All simulations
were performed in MATLAB using the standard Newton–Raphson algorithm [16]. This
algorithm is generally applicable and solves chemical equilibrium problems of any degree of
complexity. It calculates the species concentrations for a solution for which the total

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component concentrations, the chemical model, and its formation constants are known.

The analysis of real experimental data sets for case study 3 was performed by the Reactlab-

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pH software [http://jplusconsulting.com].

Case study1:

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Cyclodextrins, CD, in aqueous solution form inclusion complexes with many molecules. The

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resulting increased aqueous solubility, bioavailability and stability of compounds (drugs)
make these interactions attractive in many fields [17-20]. Amongst other effects, shifts in
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apparent equilibrium constants of different compounds in the presence of CD have been
investigated in several works [21, 22].
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In this first case study, we explore the protonation equilibrium of the pH indicator Neutral
Red (NR) in the presence of β-cyclodextrin which was reported in a spectrophotometric study
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[23]. The authors have observed that the apparent protonation constant of NR is altered in
the presence of different total concentrations of CD. Thus, based on the proposed strategy,
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the main goal of this case study is to find the tunable range of apparent constant of indicator
NR in the presence of β_CD. It was established that both acidic and basic forms of NR (with
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pKa = 6.8) form inclusion complexes with β-cyclodextrin with interaction constants of 174
(M-1) for protonated and of 655 (M-1) for deprotonated NR [23]. The complexation of neutral
form (NR) with β-CD is stronger than protonated form (NRH+) because of the stronger
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hydrophilicity of the protonated form. For the same reason, the proton is not interacting
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measurably with CD.

The protonation equilibrium of NR in the presence of β-CD and the related equilibrium
constants can be written as in scheme 3:

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Scheme 3. The equilibrium model for acid–base equilibrium of Neutral Red (NR) in the presence of β-CD.

With,

34
K 34 =
3 4

(9)

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3. 5
K 3. 5 = 3 5

(10)

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34 . 5
K 34. 5 =
34 5

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(11)

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As demonstrated earlier, such a system may be represented as a single protonation
equilibrium with the apparent constant K 34
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NRH
H + NR ⇌ NRH K 34 = (12)
H NR′
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Where the relationship between K 34 and the actual value KNRH is equivalent to equation
13:
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1 ,89:.-; 5
K 34 =K 34 1 ,
89.-; 5
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(13)

As it is obvious from the above equation, the apparent acidity constant is affected by the
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concentration of β-CD and thus the observed value K 34 can be tuned by choosing
appropriate concentrations of β-CD. Due to the higher formation constant of the inclusion
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complex for deprotonated NR (KNR.CD > KNRH.CD) the apparent constant K 34 is shifted to
lower values with increasing CD. Indeed, by adding CD, Neutral Red appears to be a stronger
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acid.

The effect of addition of different total concentration of β-CD on the apparent protonation
constant of acid-base equilibrium of NR is investigated and the results are displayed in Fig. 4.
As mentioned in the theory section, the apparent model is acceptable as long the equilibrium
concentration of β-CD and thus the apparent constant K 34 is sufficiently constant during
the process. As the passable amount for percent change of equilibrium concentration of β-
CD, [β-CD], and consequence the apparent constant during the studding system is considered

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(<= 1%), the permissible range of apparent constant, indeed the tuned ranged of observed
constant against the various of total concentration of β-CD is displays in Figure. 4. a. Also,
the acid-base titration curves of these permissible range for different concentrations of
additive component (β-CD) as well the titration curve in the absence of β-CD is shown in
Figure. 4. b. It demonstrates that NR act as stronger acid with increasing addition of β-CD.
Indeed, the pH of equivalence point of NR could be tunable over the permissible range of β-

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CD.

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Case study 2:

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According to the IUPAC definition, the transition interval of an acid-base (pH) indicator is

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the concentration range of a chemical species that can be easily detected using the change of
color of two forms of an indicator. The capability of indicators in changing their color near
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the equivalent point in acid-base titrations is dependent on their acidity dissociation constant
(pKa). The conditional dependence of the apparent constant of some pH indicators have been
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reported previously [13]. It has been shown that the transition point and transition interval as
well as the apparent constant of pH indicators has been altered under the influence of the
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different types of ionic liquids and even the concentrations of them. Also, the effect of
different concentrations of micellar pseudo-phase on the apparent acidity constant of a pH
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indicator have been investigated [24].

Inspiring the strategy of tuning the apparent constants, the goal of this case study is to tuning
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the pKa of acid-base indicator Neutral Red (NR) in micellar pseudo-phase for improving the
range of its transition points and transition interval for more application.
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Aqueous micellar solutions have several applications in analytical chemistry, they can
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increase the solubility of solutes, they can also shift observed equilibrium constants, in
particular the protonation constants of weak acids, e.g. pH indicators. Further, shifts in
absorption spectra and changing apparent equilibrium and kinetic constants have been
observed due to change the chemical/ physical properties of the solutions. These effects are
due to interactions of solutes with micelles, i.e. the solutes can either remain in the aqueous
phase or the can be dissolved in the micellar phase. Naturally, these different solvents will
affect many properties of dissolved chemicals [25-29].

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A complete model which describes the behavior of aqueous micellar systems is the partition
model in which the solutes distributes between the aqueous phase and the micellar pseudo-
phase [30]. The acid–base equilibrium of Neutral Red (NR) in aqueous micellar solutions of
Brij-35 (polyoxyethylene (23) lauryl ether) is considered in the present case [24]. Scheme 4.
displays the partition model for distributions of NR in aqueous micellar solution.

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Scheme 4. The partition model for acid–base equilibrium of Neutral Red (NR) in an aqueous micellar solution

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of Brij-35.

Based on above model, both forms of NR are distributed between the aqueous phase and

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micellar pseudo-phase. The corresponding distribution cofficients, Kd1 and Kd2, are defined as
follow:
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3=
K <1 =
3>

(14)
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34 =
K< =
34 >
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(15)
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In which the [NRH+]w and [NRH+]m are local concentrations of NRH+ in aqueous and
micellar phase and [NR]w and [NR]m represent the local concentrations of deprotonated form
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of NR in both phases.

By ignoring the distribution of protonation and deprotonation forms of acid between aqueous
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and micellar phase in the complete model, the simple apparent model of system can be
defined same as equation 12.
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As before, we define NRH+' as the sum of the species NRH in both aqueous and micellar
phase (NRH+' = [NRH+w] + [NRH+m]) and NR' is the sum of the species NR in both phases
(NR' = [NRw] + [NRm]). Thus, as the total concentrations of species NRH and NR in
different concentration of surfactant is constant we can consider:

NRH = NRH > (1 ? R) + NRH = (R)

(16)

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NR = NR > (1 ? R) + NR = (R)

(17)

In these equations R is the ratio of micellar volume (V= ) to the total volume of solution (V),
which is defined as:
AB
R = = (C= ? cmc)VE
A

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(18)

Where Cm is the total concentration of surfactant, cmc is the critical micelle concentration

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(cmc Brij-35 = 0.09mM) and VΦ is the partial molar volume of micellized surfactant.

Then, by replacing the equations 16 and 17 in equation 12 and applying equations 14 and 15,

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the relationship between apparent constant (K 34 ) and the constant of complete model can

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be extracted as:
1F3(1 ,G )
K 34 = K 34 1F3(1 , )
GH
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(19)

As it is expected, the apparent constant (K 34 ) can be controlled by the surfactant

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concentration. Of course, different surfactants have different distribution constants

(K <1 andK < ) as well as different cmc values.
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In what follows, the effect of different total concentration of Brij-35 on the apparent acidity
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constant of Neutral Red (NR) is investigated and the results are shown in Figure. 5. The
permissible range of total concentration of Brij-35 in which the apparent constant is correct
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has been shown in Figure 5.a. Also, the potentiometric titration curves for NR in the absence
and presence of Micell for the permissible concentration range of Brij-35 is display in Figure
5. b.
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It is notable that these tuned range of apparent constant of NR in the present of Brij-35 is
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different for another kind of Micell.

Since the pH indicators are versatile for the detection of the pH of a solution, a great number
of sensors utilize indicators. The color change of pH indicators is dependent on their
protonation constant (logK). Thus, by tuning the apparent constants of indicators in different
chemical environmental conditions, the apparent constant of pH indicators can be shifted to
desired value and thus also the transition pH. It means that the range of transition interval of
an indicator can be tuned.

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There are several reports which pH indicators have been used as the probe in designed sensor
arrays to identification of different targets [31- 34]. In such sensors, the identification of an
analyte is dependent to the pH of the chemical environment. Interaction of different targets
by the appropriate receptors change the solution pH, in the transition interval of the probe
indicator, which produces the signal for identification of the target analytes. Since the
detection method in such sensors is dependent on the changing pH, by tuning the apparent

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constant of pH indicators, efficient identification a range of target analytes will be possible.

In case studies one and two, the apparent constant of pH indicator Neutral Red (NR) is tuned,

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at first case by involving the NR in the inclusion complex reactions with β-cyclodextrin and
in the second one by changing the kind or concentrations of solutions (aqueous micellar

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solutions). It is notable that, these two conditions have changed the tunable range of apparent
constant of NR.

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Case study 3, experimental titrations for the boric acid-Mannitol system:
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Investigations of equilibrium reactions with very low or very large thermodynamic constants
can be difficult [35-37]. For example, aqueous potentiometric titration of a very weak acid,
results in a poorly defined end point, rendering the quantitative analysis difficult. In such
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cases, it is sometimes possible to add an auxiliary reagent to the solution which reacts with
the product and thus shift the equilibrium to the right–hand side, apparently increasing the
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acidity of the weak acid. The same principle can be applied for the improved analysis of
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weak bases. Now the end point of the potentiometric titration curve is more prominent and
the quantitative analysis of the titration is more robust.
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As discusses before, with the addition of auxiliary reagents interacting with either the
reactants or the products the apparent thermodynamic constant shifted to the lower or higher
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amounts respectively. By adjusting the concentration of auxiliary reagent, the apparent

constants could be tuned in the desired value.
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Orthoboric acid or boric acid is a rather weak Brønstedt acid with log K ≈ 9.24 resulting in a
poorly defined endpoint in potentiometric pH titrations. For this reason, it is common in
quantitative analyses of boric acid by potentiometric pH titration to add Mannitol or other
similar reagents such as glycerol. The interactions between boric acid and Mannitol was
investigated by several works [38-40]. Also changing the apparent constant of Boric acid in
different concentration of Mannitol were reported [41]. Borate forms 1:1 and 1:2 complexes
with Mannitol. The system of equilibrium reactions of the Boric Acid-Borate-Mannitol

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system is given in scheme 5 (M stands for Mannitol, B- stands for the borate ion, B(OH)4- and
BH for boric acid B(OH)3):

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Scheme 5. The equilibrium model for acid–base equilibrium of Boric acid in the presence of Mannitol.

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H + BF ⇌ HB
4!

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K !4 = 4 !
(20)

BF + M ⇌ B. M F
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!K
K !.K = (21)
K !

F
BF + 2M ⇌ B. M
M

!.K
K !.K = (22)
!.K K
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An apparent equilibrium reaction can be defined as:

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H + B F ⇌ HB
4!
K 4! = (23)
4 !
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The relation between hypothetical component B F and real components of the system are:
F
B F = BF + B. M F + B. M
C

(24)
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Combining equations 20 to 24 results in the relationship between the apparent constant

K 4! and the real constants of the complete model as below:

K 4! = K !4 (1 + K !.K M + K !.K M )
(25)

The apparent constant is dependent on the equilibrium concentration of auxiliary component

([M]) which is introduced to the system in order to increase the apparent constant.

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The titration of boric acid in the presence of different concentration of Mannitol with sodium
hydroxide was used for tuning the apparent acidity of boric acid.

Figure 6. displays the potentiometric titration curves of Boric acid solutions with
concentration 10-3M with sodium hydroxide (0.094M) as a function of different concentration
of Mannitol (0M, 0.01 M, 0.02 M, 0.0375 M, 0.05M, 0.10 M, 0.15 M, 0.20 M).

As it is clear from the Figure. 6, the titration curve of Boric acid in the absence of Mannitol

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does not result in a clear endpoint. By adding different amounts of excess Mannitol as an
auxiliary reagent in order to increase the apparent acidity, the potentiometric pH titration

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curves of this weak acid becoming increasingly better defined. As before, the analysis based
on an apparent acidity is possible.

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Different modes of analysis were employed. At first, the complete measured data set,

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including all titrations, was fitted globally, based on the complete model (scheme 5), allowing
the determination of all constants of complete model. Table 1 reports the log KBM, log KBM2
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and log KBH and the related standard deviations and compare them with the published values.
Next, each titration was analyzed individually, based on the apparent model of a simple
mono- protic acid resulting in values for K’. The apparent constants and their standard
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deviations of each titration and also the expected amount of apparent constant based on the
relationship between complete and apparent model (Eq. 25) (theory section) are listed in table
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2. The percent different between K’ as determined from the analysis of the titrations and the
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theoretical calculation using equation (25) is reported.

The calculated apparent constants (line) and the experimentally determined apparent constant
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of each measured data (star markers) are shown in Figure 7. As it is clear from the table 2 and
Figure 7, the calculated and measured apparent constant are in good agreement.
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Conclusion:

Many equilibrium systems are reasonably complex, in such cases it is often possible to
reduce the complexity to an apparent model without significant loss of accuracy.

We have developed the theory of reduction of complexity for a generalized situation where
the starting material and the product both interact with an auxiliary interferent. We have
applied the theory to two examples taken from the literature. We have also applied the theory

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to the analysis of the Boric acid/Mannitol system used in potentiometric titrations. This
experimental study confirms the validness and applicability of the theoretical derivations.

In this work, a general strategy for tuning the apparent equilibrium constant of equilibrium
reactions was developed. This strategy could be further developed for the design of optimized
sensors and other chemical processes. The future studies of designing sensor arrays based on
the proposed strategy are in progress in our research group.

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of weak complex formation, Journal of Chromatography A, 695 (1995) 309-317.

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Tables:

Table 1. Stability constants of complete model and comparison with the published value.

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Published value Calculated value

pKa-BH (M-1) 9.20 [41] 9.25 ± 0.02

log KB.M (M-1) 2.98 [41] 2.90 ± 0.05

log KB.M2 (M-1) 2.00 [41] 1.44 ± 0.06

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Table 2. Measured and calculated apparent constant in different total concentration of Mannitol.

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C_tot Mannitol Determined apparent Calculated log of % Difference
constant (log K’) apparent constant
(equation 25)

0M 9.25 ± 0.02 Published value: -------

9.24

0.0100M 8.18 ± 0.01 8.25 0.9 %

0.0200M 7.94 ± 0.01 7.87 0.9 %

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0.0375M 7.43 ± 0.02 7.47 0.5 %

0.0500M 7.28 ± 0.02 7.27 0.1 %

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0.100M 6.65 ± 0.04 6.76 1.5 %

0.1500M 6.49 ± 0.05 6.44 0.9 %

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0.200M 6.25 ± 0.06 6.20 0.8 %

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Figures:

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Figure 1. Plot for log of [I] against different concentration of entered component I for titration of 10 ml A (CA =
1×10-4) with 0.14ml B (CB = 1×10-2) when CI changes from 1×10-6 to 3×10-1.

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Figure. 2. Plot of log of apparent constant against different concentrations of entered component I, for titration
of 10ml CA = 1×10-4M and I, with 0.14 ml CB = 1×10-2M, when CI changes from 3.5×10-3M to 3×10-1M.

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Figure. 3. Plot for the impact of total concentration of CA, CB and CI on the tuned range of apparent
constant.

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Figure. 4. (a) Plot of log of apparent K (K 34 ) against different concentration of entered component β-CD. (b)
Potentiometric curves for titration of 10ml CNRH = 10-5 M with 0.1ml CNaOH 2×10-3 M in the presence of different
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concentration for Cβ-CD (0, 10-5: 6×10-2).
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Figure. 5. a) Plot of apparent K (K 34 ) as a function of different concentration of Brij-35 micelle. b)
Potentiometric titration curves for passive concentration range of Brij-35 in which the apparent constant is
established.
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Figure 6. Potentiometric titration of Boric acid solutions (10-3M) with sodium hydroxide (0.094M) in the
presence of different amount of Mannitol (0, 0.01M, 0.02M, 0.0375M, 0.05M, 0.10M, 0.15M, 0.20 M) at 298K.
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Figure 7. Comparison of measured (star markers) and calculated (line) (Eq. 25) of apparent constant in different
concentration of Mannitol.
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Highlights

• For many important equilibrium systems it is customary to use a simplified apparent,

instead of a complete but rather complex equilibrium system.

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• By the thermodynamic laws and equilibrium models, the exact analytic relationship

between complete and apparent models of equilibrium systems can be extracted.

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• The extracted relationship formula between complete and apparent models of

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equilibrium systems, determine the external parameter (s) for controlling the apparent

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models of equilibrium systems.

• By controlling the conditions governing equilibrium systems, the apparent model and
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consequences the apparent constant of equilibrium systems could be tuned in the

desired value.
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