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Thermodynamic analysis of aqueous solution of KCl by electric characterization.

F. C. M. Freire∗ and A. R. Duarte, T. M. Andrade, and A. J. Santana


Departamento de Física, Universidade Estadual de Maringá,
Avenida Colombo, 5790, 87020-900, Maringá, Paraná, Brazil.
(Dated: 30 de maio de 2018)
texto

I. INTRODUCTION evolutions of the SBF. Theories and experiments have


shown that the electrodes play a fundamental role in the
O estudo da dispersao de solucoes ionicas tem desper- impedance measurements, and this will also be taken in
tado muito interesse ao longo do tempo. Muitos pes- consideration [10].
quisadores desde o final do seculo XIX tem procurado modificar Materials and methods used are shown in
compreender o mecanismo de difusao de ions em uma so- Sec. II. The dielectric properties of the SBF have been
lucao eletrolitica. Diversas areas do conhecimento tem determined by means of the impedance spectroscopy te-
interesse nos estudos de liquidos ionicos, como indus- chnique, as described in Sec. III. The admittance models
trias quimicas, farmaceuticas, engenharia, biologicas, etc. are explored in Sec. IV, where we propose a single mo-
Com a existencia de uma grande variedade de liquidos del describing the frequency dependencies of the real and
ionicos, ha uma enorme possibilidade para ser explo- imaginary parts of the electrical admittance in the time.
rada. Um dos primeiros experimentos realizados para Our results are discussed in Sec. V. Section VI is devoted
o estudo do coeficiente de difusao foi feito por Herbert e to the conclusions.
colaboradores. Neste trabalho eles afirmaram que o co-
eficiente de difusao dos ions de cloreto de potassio em
solucao se mantem constante em relacao a variacao da II. METHODS AND MATERIALS
concentracao[1]. Outro possivel estudo era entender os
fenomenos de polarizacao sobre um cristal de KCl em The dielectric properties have been acquired by means
uma solucao ionica quando submetido a um campo ele-
of the dielectric spectroscopy technique [6] using a So-
trico estatico. Este campo produziria uma polarizacao do
lartron 1260 Impedance/Gain-Phase Analyzer. Usamos
espaco de carga que afetaria o decaimento da corrente em
o analisador de impedancia Solartron SI 1296A com um
funcao do tempo e a condutividade eletrica devido a ori-
porta-amostra modelo 12962A, equipado com um micro-
entacao dipolar[2]. Atualmente o interesse nos estudos de
metro com uma precisao de centesimo de milimetro. O
solucoes eletroliticas, principalmente com KCl, e devido
eletrodo utilizado em formato de disco feito de aco inox,
que as mobilidades dos ions K+ e Cl− serem aproxima-
com uma area superficial de S=3.14 cm2 . As medidas efe-
damente iguais. Muitos trabalhos foram feitos com dife-
tuadas foram realizadas com uma distancia de d=0.5 mm
rentes concentracoes em temperatura ambiente[3]. Neste
entre os eletrodos. As solucoes eletroliticas investigadas
trabalho apresentamos um estudo realizado com solucoes
foram solucoes aquosas de KCl, com concentracoes de sal
aquosas de KCl com diferentes concentracoes, variando
de 10−1 M, 10−2 M, 10−3 M, 10−4 M e 10−5 M. A solucao
a temperatura. Utilizamos a tecnica de espectroscopia
base de KCl com concentracao de 10−1 M, foi feita a par-
de impedancia com intervalo de frequencias de 10mHz a
tir do cloreto de potassio P.A. (marca???) em po. A
10MHz.
partir desta, foram diluidas em agua Milli-Q as outras
modificar Electrical conduction in electrolytic cells
solucoes de concentracoes diferentes, ja mencionadas.
has been widely used to investigate the role of the ions.
Uma tensao senoidal de amplitude V0 =20 mV foi apli-
In general, the aim is to investigate the frequency depen-
cado nos eletrodos. The frequency range used was from
dencies of the real and imaginary parts of the impedance
10 mHz to 1 MHz. The data was acquired with an ap-
of a sample in the shape of a slab, of ionic solutions. Par-
propriated software modified by us. A variacao de tem-
ticular attention is devoted to the SBF when is evolving
peratura da amostra foi feita pelo banho termostatico,
in the time [4, 5].
modelo ????. As medidas foram realizadas entre as tem-
modificar The objective of this work is to explore,
peraturas de 20o C a 50o C. O procedimento de limpeza
from the dielectric point of view, the aqueous soluti-
dos eletrodos consiste, primeiramente em lavar o eletrodo
ons using Impedance Spectroscopy (IS) Technique. Some
com um detergente neutro, lavar com agua milli-Q em se-
models have been used to understand the basic mecha-
guida, um banho ultrasonico por 5 min. Depois disso, os
nisms in simulated body fluids [5–9]. Equivalent circuit
eletrodos foram secos em um forno por 10 min a 65o C.
models have long been used to model the interface im-
Este procedimento foi repetido antes de cada medicao.
pedance; and, here our focus is to study the temporal
Deixar ou não? From the analysis of the real, R, and
imaginary, X, parts of Z, versus the frequency of the ap-
plied voltage, f = ω/(2π), it is possible to find an equi-
∗ fcmfreire@gmail.com; Corresponding author valent representation in form of RLC circuits. We have
2

10 -4 M Subida
performed the measurements of impedance spectroscopy 5.5

on several concentrations; but only the most significant 5


Real-Experimental
Imaginario-Experimental
Real-Teorico
ones are presented. Imaginario-Teorico

The sample holder has circular shape (of radius r = 4.5

10 mm) of parallel plates, separated by fixed thickness. 4

The electrodes were made with stainless steel. The thick- 3.5

Log(R), Log(X)
ness of the sample, d, considered in our measurements
was fixed in 0.50 mm. 3

2.5

2
III. STANDARD IMPEDANCE BEHAVIOR OF
THE KCL SOLUTIONS 1.5

The behavior of the resistivity spectrum derived by 0.5


R = R(Z) and X = I(Z), reported in Fig. 1, are res- -2 -1 0 1 2
log(freq)
3 4 5 6 7

pectively the resistance and the reatance. This figure in-


dicates the presence of one more sensible region (around Figura 2. Frequency dependence of the real, R, and imagi-
103 Hz). Fig. 2 shows the amount of ... , ranging form nary, X, parts of the electrical impedance of cells filled with
blue until red color curves. The figure shows the behavi- Milli-Q water. Differents colors means the temperature incre-
our of the pure water without introduce the KCl. asing (blu to red).Mudar a figura, colocar sem os fits e
colorindo as curvas conforme a temperatura vai su-
10 0 M Subida bindo. Colocar corretamente as unidades e as legen-
5.5
Real-Experimental
das
Imaginario-Experimental
5
Real-Teorico
Imaginario-Teorico
4.5
the differential equation [9, 11]:
4
d2 x c dx k q
+ + x = E(t), (1)
3.5
dt2 m dt m m
Log(R), Log(X)

3 The solution for the complex impedance Z = R+iX may


2.5
be written as
 
d V k
2
Zosc = iωm + c + , (2)
S N q2 iω
1.5

1
where the amount
k
0.5 O = iωm + c + (3)
-2 -1 0 1 2
log(freq)
3 4 5 6 7

has a mechanical response (say, an “amortance”) form,
Figura 1. Frequency dependence of the real, R, and imagi- and is related with the impedance in the form Zosc =
nary, X, parts of the electrical impedance of cells filled with ϕN O, where ϕN = dV /SN q 2 .
Milli-Q water. Differents colors means the temperature incre- In the sequence, a modification was proposed in the
asing (blu to red).Mudar a figura, colocar sem os fits e model, introducing a term of complex viscosity. This
colorindo as curvas conforme a temperatura vai su-
redefinition of the viscosity changes the equation Eq. (3)
bindo. Colocar corretamente as unidades e as legen-
das in such a way that
k
O = iωm + c1 (iω)γ−1 + c2 +
. (4)
As medidas para concentraçõe de KCl apresentam iω
comportamentos semelhantes, variando somente os valo- Leading us to a new expression for impedance
res e as posições dos máximos e mínimos, como podemos  
ver, por exemplo, para a concentração de 10−4 M, Fig. 2. γ−1 k
Zosc = ϕN iωm + c1 (iω) + c2 + . (5)

These equations constitute a model which is equivalent to
IV. DIELECTRIC CHARACTERIZATION the electrical circuit model containing a CPE component,
USING TWO EQUIVALENT MODELS i.e.,
1 1
Recently, we have proposed a model where the motion Z = iωL + α
+R+ , (6)
A(iω) iωC
of an ion, with mass m and charge q, in the presence of
an external electric field E(t) = E0 eiωt , is governed by where γ = 1 − α and both vary between 0 and 1.
3

V. EXPERIMENTAL RESULTS
Tabela I. Representative values of the constant parameters
versus the molar concetraction of KCl. Corrigir os valores
In order to fit the experimental curves a Genetic Al- da tabela.
gorithm (GA) program was used to fit the experimental Parameter Water 10−5 10−4 10−1
data. Details can be found in Scalerandi et. al. [14]. The
Ionic mass [m] 10−13
Kg 10−13
Kg 10−13
Kg 10−13 Kg
models used in this fit were mentioned above in equati-
ons 5. Conferir se usamos estas equacoes ou foi Viscosity potency [γ] 0.8 0.8 0.8 0.8
aquela como o termo de kp???
Figures 3 and 4 shows an example of the fit using the
electro-mechanical model. tivo, omitiremos apresentar todas as curvas e seus ajuste.
Apresentaremos a seguir os principais resultados obtidos
5
Impedância das Concentrações (Real)
a partir destes ajustes.
4.5
10 -1 Msub Dois dos parametros ajustados são praticamente cons-
10 -2 Msub
10 -3 Msub tantes ao variar da temperatura, tendo valores legeira-
4 10 -4 Msub
10 -5 Msub
mente diferentes somente quando mudamos a concentra-
3.5 10 0 Msub ção molar. São eles a massa m e a potencia do termo
viscoso γ, que podemos ver na tabela I.
Log(R), Log(X)

3
Using the single RLC model (Eq. ??) we have obtained,
2.5
for the three cases, the parameters as they can be seen in
2 the Table ??. The other parameters have presented softly
1.5
exponential behaviour. Figure ??, the bulk capacitance,
presents an exponential decay.
1
It is possible to see that the bulk contribution (Rb and
0.5
-2 -1 0 1 2 3 4 5 6 7
Cb ), despite the exponential capacitance decay, was the
Log(Frequência) same in all cases (channels), which leads us to believe
that the main differences are surface contributions, such
Figura 3. Frequency dependence of the real, R, parts of the us surface capacitance Cs , can be seem in Fig. [??].
electrical impedance for differents concentrations of KCl and On the other hand, using the RLC-CPE model
pure water. All to the temperature around 20 Celsius degrees. (Eq. ??) we have obtained, for the three cases, the fol-
Corrigir o grafico para tres curvas e colocar a legenda lowing constant parameters, as can be seen in the Ta-
corretamente.
ble ??. The value of LS can be identified with the elec-
trical inductance of the cables. The other parameters
Impedância das Concentrações (Imaginário)
have presented different exponential behaviour. Figure
6
10 -1 Msub
?? shows us an exponential decay for the A variable CPE
10 -2 Msub model.
5 10 -3 Msub
10 -4 Msub MODIFICAR In the same way, Alexe-Ionescu et.
10 -5 Msub
10 0 Msub al. [8] show that the conductivity equivalent of KCl and
4
NaCl is directly proportional to the ionic concentration.
Therefore, if the conductivity is proportional to the ions
Log(R), Log(X)

3
concentrations, the results show that, with the growth of
the apatite, the conductivity decreases in time.
2

1
VI. CONCLUSIONS
0

The impedance spectroscopy measurements have been


-1 performed on samples with different SBF activities, pure
-2 -1 0 1 2 3 4 5 6 7
Log(Frequência) SBF and SBF plus HA. The measurements have been
performed during approximately 600 hours, with an ad-
Figura 4. Frequency dependence of the imaginary, X, parts of mittance curve being collected every our for three diffe-
the electrical impedance for differents concentrations of KCl rent set-ups. Two models corresponding to the equivalent
and pure water. All to the temperature around 20 Celsius circuit models have been used to quantify the electrode-
degrees. Corrigir o grafico para tres curvas e colocar a electrolyte interface and separate the bulk from the sur-
legenda corretamente. face contribution. The time behaviour of the admittance
was presented and, using the integrated rate law was pos-
Estas duas figuras mostram exemplos que quão bom sible to find, that qualitatively, the half-life time.
foram os ajustes, que foram feitos para todas as curvas An other important aspect is that, despite the expo-
medidas e para as diversas concentrações. Por este mo- nential behaviour, the ranges of the conductivity was
4

small, showing the stability (or quality) of the SBF pro- is financially supported by Fundaćão Araucária. T.
duced in our labs. That control is very important be- M. de Andrade is supported by Conselho Nacional de
cause, right after the SBF synthesis, it can be checked Desenvolvimento Científico e Tecnológico (CNPQ).
with the impedance spectroscopy without having spend
days to verify the grown of the apatite in bones samples.
Further steps will be taken to further facilitate the ve-
rification and the quality of SBF. VII. BIBLIOGRAPHY
MODIFICAR Acknowledgments: F. C. M. Freire

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