Kinetic Study of the Low Temperature Transformation of Co(HCOO)3[(CH3)2NH2]

López-Beceiro, Jorge; Gracia-Fernández, Carlos; Gómez-Barreiro, S.; Castro‐García, Socorro; Andújar, Manuel; Artiaga, Ramón

doi:10.1021/jp208070d

Cited by 23 publications

(17 citation statements)

References 33 publications

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“…A value of 22 kJ mol −1 was obtained for the P1 process. This value is very different from others obtained in solid–solid and melting transformations …”

Section: Methodscontrasting

confidence: 98%

“…While the generalized logistic function was proposed in 1959 as a flexible growth function for empirical use, it was not until our recent work that a true kinetic approach was used to interpret the processes that can be described by that function . A complete kinetic description should consider both isothermal and nonisothermal situations.…”

Section: Methodsmentioning

confidence: 99%

“…A complete kinetic description should consider both isothermal and nonisothermal situations. The nonisothermal caseEquation can be expressed as functions of the conversion of the process, α:

y_{r a m p} true(t, α true) = c_{r a m p} \cdot b_{r a m p} \cdot exp true(- b_{r a m p} \cdot true(m_{r a m p} - t true) true) \cdot {true(1 - α true)}^{1 + τ}

Based on this expression the model can be understood as a reaction order model, being the reaction order represented by 1 + τ

b_{r a m p} = \frac{E_{r a m p}}{R \cdot t_{p r a m p} \cdot T_{c}}

where T c is the critical temperature for the process to occur, t pramp represents the time elapsed from the instant where temperature reached a critical value, T c , to the instant where the maximum rate of change is observed, m ramp .…”

Section: Methodsmentioning

confidence: 99%

“…Equation can be expressed as functions of the conversion of the process, α:

y_{r a m p} true(t, α true) = c_{r a m p} \cdot b_{r a m p} \cdot exp true(- b_{r a m p} \cdot true(m_{r a m p} - t true) true) \cdot {true(1 - α true)}^{1 + τ}

Based on this expression the model can be understood as a reaction order model, being the reaction order represented by 1 + τ …”

Section: Methodsmentioning

confidence: 99%

“…This new model will be applied to the thermogravimetric thermal degradation data of PEI with the aim of checking if it can accurately reproduce its kinetics and, if so, to obtain insightful kinetic parameters (critical temperature, energy barrier and reaction‐order) which allow to make predictions in both isothermal and nonisothermal contexts. The approach used for this model is based on other developments of the authors and consists of fitting thermogravimetric curves to mixtures of generalized logistic functions. Some simplifications of the model can be done when working with TG data: there is no need of baseline subtraction; the first derivative of a generalized logistic function can fit DTG curves.…”

Section: Introductionmentioning

confidence: 99%

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Thermogravimetric study of thermal degradation of polyetherimide

Zaragoza

Álvarez

Lasa-Alvarez

et al. 2015

J of Applied Polymer Sci

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Thermal stability in nonoxidizing atmosphere of a polyetherimide (PEI) is investigated by thermogravimetry (TG). It is observed that thermal degradation of this product consists of two overlapping processes, which are conveniently separated by fitting the TG curves to mixtures of generalized logistic functions. Thus, each process is represented by a single function. The analysis of the fitting parameter values obtained for the main degradation process in different isothermal and heating ramp conditions allows to obtain insightful kinetic parameters (critical temperature, energy barrier, and reaction-order) which allow to make predictions in both isothermal and nonisothermal contexts. There is a minimum temperature for each process to occur and a ramp-energy barrier related to the process rate. In the ramp context, the values of these two parameters explain that, although one process starts at lower temperature, it proceeds at a very low rate until reaching temperatures at which the other process goes much faster. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42329.

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“…A value of 22 kJ mol −1 was obtained for the P1 process. This value is very different from others obtained in solid–solid and melting transformations …”

Section: Methodscontrasting

confidence: 98%

Section: Methodsmentioning

confidence: 99%

“…A complete kinetic description should consider both isothermal and nonisothermal situations. The nonisothermal caseEquation can be expressed as functions of the conversion of the process, α:

y_{r a m p} true(t, α true) = c_{r a m p} \cdot b_{r a m p} \cdot exp true(- b_{r a m p} \cdot true(m_{r a m p} - t true) true) \cdot {true(1 - α true)}^{1 + τ}

Based on this expression the model can be understood as a reaction order model, being the reaction order represented by 1 + τ

b_{r a m p} = \frac{E_{r a m p}}{R \cdot t_{p r a m p} \cdot T_{c}}

Section: Methodsmentioning

confidence: 99%

“…Equation can be expressed as functions of the conversion of the process, α:

y_{r a m p} true(t, α true) = c_{r a m p} \cdot b_{r a m p} \cdot exp true(- b_{r a m p} \cdot true(m_{r a m p} - t true) true) \cdot {true(1 - α true)}^{1 + τ}

Based on this expression the model can be understood as a reaction order model, being the reaction order represented by 1 + τ …”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermogravimetric study of thermal degradation of polyetherimide

Zaragoza

Álvarez

Lasa-Alvarez

et al. 2015

J of Applied Polymer Sci

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A logistic kinetic model for isothermal and nonisothermal cure reactions of thermosetting polymers

López-Beceiro

Fontenot

Gracia-Fernández³

et al. 2014

J of Applied Polymer Sci

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A model describing the low-temperature crystallization kinetics observed for thermoplastic polymers from the melt by differential scanning calorimetry (DSC) was shown to accurately predict the cooling curves as a function of time and temperature. The model was successful for treating data for several cooling rates as well as for isothermal DSC data. In this article, we extended the model to cure reactions of thermosetting polymers. The parameters representing lower and upper exotherm reference temperatures in crystallization events have a different meaning for curing events. Thus, the model was modified to account for this change of context. The new model was tested for exothermic reactions of a HysolV R FP4527 epoxy adhesive system using data from DSC ramp heating experiments at several heating rates and also from isothermal experiments. Good fits were obtained for all the varied experimental conditions. The model made use of three fitting parameters with physical significance: a lower critical temperature (T c ) an activation energy (E b ), and a reaction order (s 1 1). Additionally, to complete the kinetic fitting, the dependence of the time to reach the reaction peak maximum for isothermal cure was considered. That dependence was found to follow a more simple model which is formally equivalent to that observed in isothermal crystallization, and which makes use of two parameters related to the limits of the temperature range in which the polymerization may occur.

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Selective Separation of Hazardous Chemicals from Vapor Phase by an Easily Accessible Breathing Coordination Polymer Derived from Terpyridyl/terephthalate Mixed Ligands

Bera

Dastidar

2023

Chemistry A European J

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Coordination polymers are extensively studied materials because of their various potential applications. Amongst them, breathing coordination polymers that are capable of exchanging lattice occluded guest molecules with other guests via single‐crystal‐to‐single‐crystal (SC–SC) fashion are particularly intriguing. Herein, we disclose an easily accessible breathing coordination polymer namely DMF@Zn‐CP capable of exchanging as many as 23 guest molecules of various kinds in SC–SC fashion when the crystals of the coordination polymer were exposed to the corresponding vapor of the guests. Selectivity experiments revealed that it was also capable of separating selectively hazardous chemicals such as dichloro‐methane, benzene and fluorobenzene from the corresponding complex mixture of vapors of halomethanes, aromatic hydrocarbons and halobenzenes. The breathing coordination polymer could also be exploited as drug delivery vehicle; slow and sustained release of anti‐bacterial agents (benzyl alcohol/phenethyl amine) as guests against both gram positive and gram negative bacteria was evident in zone inhibition assays. A mixed ligand strategy wherein a nitrile containing terpyridyl ligand (L) and terephthalate (TA) co‐ligand were reacted with Co(II)/Ni(II)/Zn(II) nitrate salts was adopted herein. Three coordination polymers namely MeOH@Co‐CP, DMF/H2O@Ni‐CP and DMF@Zn‐CP were isolated and characterized by single crystal X‐ray diffraction. Studies revealed that only DMF@Zn‐CP possessed the ability to breath in response to the vapors of the guests as stimuli.

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Kinetic Study of the Low Temperature Transformation of Co(HCOO)₃[(CH₃)₂NH₂]

Cited by 23 publications

References 33 publications

Thermogravimetric study of thermal degradation of polyetherimide

Thermogravimetric study of thermal degradation of polyetherimide

A logistic kinetic model for isothermal and nonisothermal cure reactions of thermosetting polymers

Selective Separation of Hazardous Chemicals from Vapor Phase by an Easily Accessible Breathing Coordination Polymer Derived from Terpyridyl/terephthalate Mixed Ligands

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