Storage of energy in constrained non-equilibrium systems

We study a quantity $\mathcal{T}$ defined as the energy U, stored in non-equilibrium steady states (NESS) over its value in equilibrium $U_0$, $\Delta U=U-U_0$ divided by the heat flow $J_{U}$ going out of the system. A recent study suggests that $\mathcal{T}$ is minimized in steady states (Phys.Rev.E.99, 042118 (2019)). We evaluate this hypothesis using an ideal gas system with three methods of energy delivery: from a uniformly distributed energy source, from an external heat flow through the surface, and from an external matter flow. By introducing internal constraints into the system, we determine $\mathcal{T}$ with and without constraints and find that $\mathcal{T}$ is the smallest for unconstrained NESS. We find that the form of the internal energy in the studied NESS follows $U=U_0*f(J_U)$. In this context, we discuss natural variables for NESS, define the embedded energy (an analog of Helmholtz free energy for NESS), and provide its interpretation.Comment: 16 pages, 5 figure

Thermodynamics of stationary states of the ideal gas in a heat flow

There is a long-standing question as to whether and to what extent it is possible to describe nonequilibrium systems in stationary states in terms of global thermodynamic functions. The positive answers have been obtained only for isothermal systems or systems with small temperature differences. We formulate thermodynamics of the stationary states of the ideal gas subjected to heat flow in the form of the zeroth, first, and second law. Surprisingly, the formal structure of steady state thermodynamics is the same as in equilibrium thermodynamics. We rigorously show that $U$ satisfies the following equation $dU=T^{*}dS^{*}-pdV$ for a constant number of particles, irrespective of the shape of the container, boundary conditions, size of the system, or mode of heat transfer into the system. We calculate $S^{*}$ and $T^{*}$ explicitly. The theory selects stable nonequilibrium steady states in a multistable system of ideal gas subjected to volumetric heating. It reduces to equilibrium thermodynamics when heat flux goes to zero

Formation of net-like patterns of gold nanoparticles in liquid crystal matrix at the air–water interface

Controlled patterning and formation of nanostructures on surfaces based on self-assembly is a promising area in the field of “bottom-up” nanomaterial engineering. We report formation of net-like structures of gold nanoparticles (Au NPs) in a matrix of liquid crystalline amphiphile 4′-n-octyl-4-cyanobiphenyl at the air–water interface. After initial compression to at least 18 mN m(−1), decompression of a Langmuir film of a mixture containing both components results in formation of net-like structures. The average size of a unit cell of the net is easily adjustable by changing the surface pressure during the decompression of the film. The net-like patterns of different, desired average unit cell areas were transferred onto solid substrates (Langmuir–Blodgett method) and investigated with scanning electron microscopy and X-ray reflectivity (XRR). Uniform coverage over large areas was proved. XRR data revealed lifting of the Au NPs from the surface during the formation of the film. A molecular mechanism of formation of the net-like structures is discussed. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s11051-012-0826-4) contains supplementary material, which is available to authorized users

Steady state thermodynamics of ideal gas in shear flow

Equilibrium thermodynamics describes the energy exchange of a body with its environment. Here, we describe the global energy exchange of an ideal gas in the Coutte flow in a thermodynamic-like manner. We derive a fundamental relation between internal energy as a function of parameters of state. We analyze a non-equilibrium transition in the system and postulate the extremum principle, which determines stable stationary states in the system. The steady-state thermodynamic framework resembles equilibrium thermodynamics

Accurate Genetic Switch in Escherichia coli: Novel Mechanism of Regulation by Co-repressor

Understanding a biological module involves recognition of its structure and the dynamics of its principal components. In this report we present an analysis of the dynamics of the repression module within the regulation of the trp operon in Escherichia coli. We combine biochemical data for reaction rate constants for the trp repressor binding to trp operator and in vivo data of a number of tryptophan repressors (TrpRs) that bind to the operator. The model of repression presented in this report greatly differs from previous mathematical models. One, two or three TrpRs can bind to the operator and repress the transcription. Moreover, reaction rates for detachment of TrpRs from the operator strongly depend on tryptophan (Trp) concentration, since Trp can also bind to the repressor-operator complex and stabilize it. From the mathematical modeling and analysis of reaction rates and equilibrium constants emerges a high-quality, accurate and effective module of trp repression. This genetic switch responds accurately to fast consumption of Trp from the interior of a cell. It switches with minimal dispersion when the concentration of Trp drops below a thousand molecules per cell

The first law of thermodynamics in hydrodynamic steady and unsteady flows

We studied planar compressible flows of ideal gas as models of a non-equilibrium thermodynamic system. We demonstrate that internal energy $U(S^{*},V,N)$ of such systems in stationary and non-stationary states is the function of only three parameters of state, i.e. non-equilibrium entropy $S^{*}$, volume $V$ and number of particles $N$ in the system. Upon transition between different states, the system obeys the first thermodynamic law, i.e. $dU=T^{*}dS^{*}-p^{*}dV+{\mu}^{*}dN$, where $U=3/2 NRT^{*}$ and $p^{*}V=NRT^{*}$. Placing a cylinder inside the channel, we find that U depends on the location of the cylinder $y_{c}$ only via the parameters of state, i.e. $U(S^{*}(y_{c}),V,N(y_{c}))$ at V=const. Moreover, when the flow around the cylinder becomes unstable, and velocity, pressure, and density start to oscillate as a function of time, t, U depends on t only via the parameters of state, i.e. $U(S^{*}(t),V,N(t))$ for V=const. These examples show that such a form of internal energy is robust and does not depend on the particular boundary conditions even in the unsteady flow.Comment: 17 pages, 9 figure