At ambient pressure ( Π = 0), contours showing how voltage and temperature affect the reaction equilibrium are visualized (B).
When no voltage is applied ( Ψ = 0), contours showing how pressure and temperature affect reaction equilibrium are visualized (A). (A and B) Every chemical reaction can be mapped onto these universal plots. Results and Discussion Non-dimensionalization of Reaction Equilibrium Our approach provides a simple, universal framework with a thermodynamic basis to compare and justify using temperature, pressure, or voltage as a driving force for a chemical reaction, and our analysis can be leveraged by researchers in a broad range of fields to help determine the important systems-level choice of thermodynamic driving force. After constructing a universal equation, we then introduce a facile visualization method for comparing chemical reactions, with a focus on redox reactions (voltage is generally not an option for non-redox reactions) and show a clear divide between chemical reactions traditionally driven by elevated temperatures and pressures in industry and reactions that rely on electrical voltage. We compare heat, mechanical work, and electrical work as energy inputs to a chemical system and find that an ideal, lossless model of energy comparison provides a physical basis for our non-dimensional thermodynamic parameter analysis. We have focused on these driving forces due to their prevalence in chemical synthesis, although the analysis can be extended to the direct use of photons or mechanochemical methods. In this work, we construct a universal equation to describe and analyze the thermodynamics of chemical reactions driven by temperature, pressure, and voltage. Overall, this universal equation and facile visualization of chemical reactions provides a consistent thermodynamic framework for comparing electrochemical versus thermochemical energy sources without knowledge of detailed process parameters. Additionally, we show that our expression has a strong physical basis in work and energy fluxes to the system, although specific data about operating conditions are necessary to provide a quantitative energy analysis.
With a specific set of axes, all reactions are represented by a single ( x, y ) point, and a quantitative divide between electrochemically and thermochemically driven reactions is visually evident. In this work, we present a reaction-independent expression for the equilibrium constant as a function of temperature, pressure, and voltage. Chemical transformations traverse large energy differences, yet the comparison of energy sources to drive a reaction is often done on a case-by-case basis there is no fundamentally driven, universal framework with which to analyze and compare driving forces for chemical reactions.
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