Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a
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Model-based analysis for kinetic complexation study of Pizda and Cu(II) Spectrochimica Acta Part A M. Vosough , M. Maeder , M. Jalali-Heravi , S.E. Norman. Introduction. Chemical kinetic reactions : Model-based analysis kinetic model.

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Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Model-based analysis for kinetic complexation study of Pizda and Cu(II)

Spectrochimica Acta Part A

M. Vosough , M. Maeder , M. Jalali-Heravi , S.E. Norman


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Introduction and Cu(II)

Chemical kinetic reactions :

Model-based analysis

kinetic model

  • The main goals for model-based analysis of kinetic reactions :

  • rate constants

  • molar absorption spectra

  • pure kinetic profiles of all reacting species


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Introduction and Cu(II)

Many kinetic reactions in aqueous solutions are strongly pH-dependent and coupled to one or more protonation equilibria.

The kinetic reactions have to be studied at feasible pH ranges.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Complications due to addition of buffers: and Cu(II)

Introduction

  • The conjugate bases of the buffers can coordinate to the metal ions.

  • Buffer anions can form outer-sphere complexes with highly charged polyprotonated ligand cations.

  • Buffer components can absorb in the wavelength region where the complexation is observed.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Introduction and Cu(II)

Recent developments in model-based methods :

incorporation of the effects of non-ideal experimental conditions into the fitting algorithm

The quantitative analysis of kinetic measurements that are not buffered is possible.

The complications due to addition of the buffers can be removed.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Introduction and Cu(II)

  • The concentration profiles in kinetic studies are defined by:

  • Model

  • rate constants

  • initial concentration of the reacting components


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Y and Cu(II)= CA + R

A_hat= C+Y

(C+ = (CtC)−1Ct)

R = Y − Ycalc = Y − CA

ssq =ΣR2i,j= f (Y, model,parameters)


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Δ and Cu(II)k = −J+R = −(JtJ)−1JtR

knew = k +Δk


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

The complexation is between: and Cu(II)

copper(II) and 1-(2-hydroxyl cyclohexyl)-3-[aminopropyl]-4-[3-aminopropyl]piperazine (Pizda)

in 50% ethanol–water

Pizda is a five-dentate ligand.

1:1 complex forms in a very fast second order reaction and strongly dependent on the initial pH.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Scheme 2. and Cu(II) Cu(II)–Pizda complex in all possible complexation sites


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

k and Cu(II)L

Cu2+ + L (CuL’)2+

k (CuL’)2+

(CuL’)2+ CuL2+

k-1 (CuL’)2+

K4

(CuL’)2+ + H+ CuLH3+

k LH

Cu2+ + LH+ CuLH3+

k-1 LH

kLH2

Cu2+ + LH22+ CuLH+ + H+

Mechanism:


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

K and Cu(II)1

K2

K3

L + H+ LH+

LH+ + H+ LH22+

LH22+ + H+ LH33+

Protonation equilibria:


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Forward and Cu(II)reaction (F):

the kinetics of complex formation

Proton releases and therefore the pH decreases and finally would reach to its equilibrium value.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Backward and Cu(II) reaction (B):

the kinetics of complex dissociation

The complex decomposes and therefore pH increases and finally would reach to its equilibrium value.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Globalization of second-order data and Cu(II)

  • Elimination of linear dependencies of concentration profiles

  • Combination of all information gathered in the individual measurements

  • More robust determination of the fitted parameters


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Scheme 1. and Cu(II) Representation of global analysis

Ytot = CtotA + Rtot


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 1. and Cu(II) Concentration distribution diagram obtained for all chemical species in

complexation of Cu(II) by Pizda in equilibrium state as a function of pH


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Table 1 and Cu(II)

Protonation and complexation constants obtained from potentiometric study of

complex formation equilibria between Pizda and Cu2+ in 50% ethanol–water

solution and 25±0.5 ◦C and ionic strength of 0.1M (NaClO4)


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 2. and Cu(II) pH trends calculated by Newton–Raphson method in:

forward pre-kinetic, backward pre-kinetic and equilibrium states.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 3. and Cu(II) Two kinetic series in 21 wavelengths with stopped-flow measurements:

(a) in forward case withinitial concentration of acid 2.97×10−2 M

(b) in backward case with initial concentration of acid 4.70×10−2 M


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 4. and Cu(II) Some results obtained using global analysis. The results depicted for two kinetics traces in Fig. 3 in some selected wavelengths (520,565 and 655 nm) contains the calculated absorbance measurements and residual plots :

(a) forward and (b) backward reactions.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

The main advantage: and Cu(II)

The possibility of working in unbuffered solutions.

The tedious measurements and analysis of buffer dependences is replaced by few reactions.

All pH ranges can be covered.

The main disadvantage :

The time consuming of the fitting process relative to the other methods which use the buffer solutions.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

  • This procedure delivers : and Cu(II)

  • Nonlinear parameters which are rate constants and define the matrix C.

  • The fitted equilibria constants involved in kinetics.

  • The matrix of molar absorptivity spectra A for all absorbing species.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Table 2 and Cu(II)

Rate constants and the protonation constants for complexation reaction between

Pizda andCu2+ in50%ethanol–water solution and 25±0.5 ◦C and ionic strength

of 0.1M (NaClO4)


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 5. and Cu(II) The calculated concentration profiles for the measurement series in Fig. 3: (a) forward and (b) backward reactions.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 6. and Cu(II) pH profiles calculated with global analysis in the selected kinetic measurements (Fig. 3).


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Fig. 7. and Cu(II) Calculated absorption spectra in kinetic measurements for four absorbing species of Cu, CuL, CuL’ and CuLH in a global way.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Reference: and Cu(II)

M. Maeder, Y.M. Neuhold, G. Puxty, P. King, Phys. Chem. Chem. Phys. 5(2003) 2836.


Model based analysis for kinetic complexation study of pizda and cu ii spectrochimica acta part a

Thanks and Cu(II)