The Lost Work in Dissipative Self-Assembly Koper, G. J. M.; Boekhoven, J.; Hendriksen, W. E. ...
International journal of thermophysics,
07/2013, Volume:
34, Issue:
7
Journal Article
Peer reviewed
A general thermodynamic analysis is given of dissipative self-assembly (DSA). Subsequently, the analysis is used to quantify the lost work in a recently published chemical realization of DSA ...(Boekhoven et al., Angew Chem Int Ed 49:4825,
2010
) where a formation reaction produces the monomers that subsequently self-assemble and are finally annihilated by means of a destruction reaction. For this example, the work lost in self-assembly itself is found to be negligibly small compared to the work lost in the reactions driving the non-spontaneous formation reaction and the kinetically hindered destruction reaction.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
An analysis of the recent experimental results by Fang and Ward is given. They found a temperature jump almost upto 10 K across the evaporating surface of water, octane and methylcyclohexane. We use ...nonequilibrium thermodynamics to obtain the appropriate boundary conditions at the surface. Interfacial transfer coefficients, appearing in these boundary conditions, can then be determined from the experiments. We present them in a form useful for engineering calculations. A comparison is made with the predictions for the transfer coefficients from kinetic theory. For the three materials the kinetic theory values were found to be 30 to 100 times larger than those found from the experiment. It is explained why this gives a liquid surface, which is colder than the adjacent vapor, contrary to the prediction by the kinetic theory. The relative magnitude that we find for the interfacial transfer coefficients, suggests that the condensation coefficient of the kinetic theory decreases with increasing internal degrees of freedom in a molecule. However, a lower value of this coefficient is not sufficient to explain the small value of the transfer coefficients. As a possible explanation for this, we forward the hypothesis that the single-particle collision model used in the kinetic theory for this phenomenon, should be modified to account for multiparticle events.
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IJS, IMTLJ, KILJ, KISLJ, NUK, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Non-equilibrium molecular dynamic (NEMD) simulations have been used to study the kinetics of adsorption of
n-butane molecules in a silicalite membrane. We have chosen this simple well-known process ...to demonstrate that the process is characterized by two stages, both non-isothermal. In the first stage the large chemical driving force leads to a rapid uptake of
n-butane in all the membrane and a simultaneous increase in the membrane temperature, explained by the large enthalpy of adsorption,
Δ
H
=
−
61.6
kJ
/
mol
butane. A diffusion coefficient for transport across the external surface layer is calculated from the relaxation time; a value of
3.4
×
10
−9
m
2
/
s
is found. During the adsorption, a significant thermal driving force develops across the external surface of the membrane, which leads to an energy flux out of the membrane during the second stage. In this stage a thermal conductivity of
3.4
×
10
−4
W
/
K
m
is calculated from the corresponding relaxation time for the surface, confirming that the thermal conduction is the rate-limiting step. The aim of this paper is to demonstrate that a thermal driving force must be taken into account in addition to a chemical driving force in the description of transport in nano-porous materials.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
We present evidence for the hypothesis of local equilibrium for a liquid–vapor interface in a one-component fluid, using molecular dynamics simulations. Lennard-Jones/spline particles are studied in ...a two-phase system that is out of global equilibrium. Equilibrium simulations are first used to establish the equation of state for the vapor and interface. A procedure is developed to define the boundaries of the interface. Finally it is shown that the equation of state for the interface applies also when there is heat and mass transport through the interface. The temperature gradient in the vapor was 108 K/m in these studies.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Some eutectic stripes have been generated in a hexagonal (Zn) - single crystal. The stripes are situated periodically with the constant interstripes spacing. The eutectic structure in the stripes ...consists of strengthening inter-metallic compound, Zn16Ti, and (Zn) - solid solution. The rod-like irregular eutectic structure (with branches) appears at low growth rates. The regular lamellar eutectic structure is observed at middle growth rates. The regular rod-like eutectic structure exists exclusively in the stripes at some elevated growth rates. A new thermodynamic criterion is recommended. It suggests that this eutectic regular structure is the winner in a morphological competition for which the minimum entropy production is lower. A competition between the regular rod-like and the regular lamellar eutectic growth is described by means of the proposed criterion. The formation of branches within irregular eutectic structure is referred to the state of marginal stability. A continuous transitions from the marginal stability to the stationary state are confirmed by the continuous transformations of the irregular eutectic structure into the regular one.
An extension of the scheme of non-equilibrium thermodynamics developed previously is given for quantum mechanical systems. A master equation for the density matrix of the system follows from this ...scheme. Onsager relations are given and derived. Application to a spin system gives the Bloch equations. The application to a one-dimensional damped harmonic oscillator results in equations, which enable us to calculate the usual Green functions. For the last case we derive, as a new alternative, quantum mechanical Langevin equations. A new element, compared to the classical Langevin equations, is a random velocity. The correlation of the random velocity with the random force then results from the zero point motion of the oscillator. The application of mesoscopic non-equilibrium thermodynamics to these wellknown problems illustrates the usefullness of this method.
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IJS, IMTLJ, KILJ, KISLJ, NUK, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
We present a systematic procedure to describe fluid-fluid interfaces of multi-component systems out of equilibrium in a clear macroscopic context on a basis of non-equilibrium thermodynamics. The ...macroscopic description uses, as Gibbs did for equilibrium interfaces, excess densities. Comparing it with the local description which is based on the non-equilibrium square gradient theory, we show that two descriptions are consistent. This implies that out of equilibrium one can still use interfacial excess densities as if they are functions only of the local temperature and chemical potentials. This justifies that the surface is a separate thermodynamic system and is in local equilibrium.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
In this paper we apply the general analysis described in our first paper to a binary mixture of cyclohexane and n -hexane. We use the square gradient model for the continuous description of a ...nonequilibrium surface and obtain numerical profiles of various thermodynamic quantities in various stationary state conditions. Details of the numerical procedure are given and discussed. In the second part of this paper we focus on the verification of local equilibrium of the surface as described with excess densities. We give a definition of the temperature and chemical potentials of the surface and verify that these quantities are independent of the choice of the dividing surface. We verify numerically that the surface in a stationary state of the mixture can be described in terms of Gibbs excess densities, which are found to be in good approximation equal to their equilibrium values at the stationary state temperature and chemical potentials of the surface.
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CMK, CTK, FMFMET, IJS, NUK, PNG, UM
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