Gibbs Free Energy Research Articles

Heat capacities and thermodynamic functions of three 1-benzyl-4-aryl-1H-1,2,3-triazoles in the temperature range of (0 – Tm) K

In this paper, we present the results of comprehensive thermodynamic study of some functionally substituted triazoles such as 1-benzyl-4-phenyl-1H-1,2,3-triazole, 1-benzyl-4-(m-tolyl)-1H-1,2,3-triazole and 1-benzyl-4-(4‑tert-butylphenyl)-1H-1,2,3-triazole. The temperature dependences of heat capacities of 1-benzyl-4-(m-tolyl)-1H-1,2,3-triazole and 1-benzyl-4-(4‑tert-butylphenyl)-1H-1,2,3-triazole were measured in a wide temperature range of ∼(5 – 370) K using the adiabatic calorimetry. Those of 1-benzyl-4-phenyl-1H-1,2,3-triazole were determined at the range of ∼(5 – 80) K, supplementing the previous measurements at the more elevated temperatures. The melting parameters and thermal stability (melting temperature, enthalpy of fusion, temperature of thermal destruction) of the compounds were determined using the differential scanning calorimetry. Also, the standard thermodynamic functions (absolute entropies, reduced enthalpies and Gibbs energies) were calculated in the temperature range of (0 – Tm) K.

In Silico Modeling of Myelin Oligodendrocyte Glycoprotein Disulfide Bond Reduction by Phosphine-Borane Complexes

Background: Neurodegenerative diseases can cause vision loss by damaging retinal ganglion cells in the optic nerve. Novel phosphine-borane compounds (PBs) can protect these cells from oxidative stress via the reduction of disulfide bonds. However, the specific targets of these compounds are unknown. Proteomic evidence suggests that myelin oligodendrocyte glycoprotein (MOG) is a potential target. MOG is of significant interest due to its role in anti-MOG optic neuritis syndrome. Methods: We used in silico modeling to explore the structural consequences of cleaving the extracellular domain MOG disulfide bond, both in isolation and in complex with anti-MOG antibodies. The potential binding of PBs to this bond was examined using molecular docking. Results: Cleaving the disulfide bond of MOG altered the structure of MOG dimers and reduced their energetic favorability by 46.13 kcal/mol. The energy profiles of anti-MOG antibody complexes were less favorable when the disulfide bond of MOG was reduced in the monomeric state by 55.21 kcal/mol, but the reverse was true in the dimeric state. PBs exhibited reducing capabilities with the MOG extracellular disulfide bond, with this best-scoring compound binding with an energy of −28.54 kcal/mol to the MOG monomer and −24.97 kcal/mol to the MOG dimer. Conclusions: These findings suggest that PBs can affect the structure of MOG dimers and the formation of antibody complexes by reducing the MOG disulfide bond. Structural changes in MOG could have implications for neurodegenerative diseases and anti-MOG syndrome.

Hierarchical equations of motion for multiple baths (HEOM-MB) and their application to Carnot cycle.

We have developed a computer code for the thermodynamic hierarchical equations of motion derived from a spin subsystem coupled to multiple Drude baths at different temperatures, which are connected to or disconnected from the subsystem as a function of time. The code can simulate the reduced dynamics of the subsystem under isothermal, isentropic, thermostatic, and entropic conditions. The extensive and intensive thermodynamic variables are calculated as physical observables, and Gibbs and Helmholtz energies are evaluated as intensive and extensive work. The energy contribution of the system-bath interaction is evaluated separately from the subsystem using the hierarchical elements of the hierarchical equations of motion. The accuracy of the calculated results for the equilibrium distribution and the two-body correlation functions is assessed by contrasting the results with those obtained from the time-convolution-less Redfield equation. It is shown that the Lindblad master equation is inappropriate for the thermodynamic description of a spin-boson system. Non-Markovian effects in thermostatic processes are investigated by sequentially turning on and off the baths at different temperatures with different switching times and system-bath coupling. In addition, the Carnot cycle is simulated under quasi-static conditions. To analyze the work performed for the subsystem in the cycle, thermodynamic work diagrams are plotted as functions of intensive and extensive variables. The C++ source codes are provided as supplementary material.

Design of some phthalazine molecules as novel VEGFR-2 target inhibitors through 3D-QSAR modeling, molecular docking and dynamic simulation and pharmacokinetics profiling

AbstractBreast cancer is one of the dominant cause of cancer-related mortality in females, with an incidence of approximately 1.3 million cases annually, necessitating the development of effective therapeutic strategies. In this study, 3D-QSAR models were reported based on Phthalazine derivatives as VEGFR-2 inhibitors. The activities of these derivatives were correlated with the steric (S), electrostatic (E), hydrogen bond acceptor (A), and donor (D), and hydrophobic (H) fields, which served as critical parameters in model development. Statistical studies of these models showed that the best models are; CoMFA_S (Q2 = 0.623, R2 = 0.941), and CoMSIA_E + D (Q2 = 0.615, R2 = 0.977). Based on the insights from the model fields and docking simulation of the template (compound 17), twelve molecules were designed. These novel molecules exhibited stronger potency compared to the template and the standard, Sorafenib. Compound 17A emerged as the most potent, with pIC50 = 5.98, for CoMFA_S and 5.85, for CoMSIA_E + D, and a strong docking affinity of − 97.271 kcal/mol, therefore subjected to a 100-ns MD simulation. Results indicate better interaction and stabilizing potential over Sorafenib, due to the lower RMSD, RMSF, Rg, values and favorable hydrogen bond analyses. These conclusions were validated by Gibbs free energy analysis and MM-GBSA calculations, revealing a more favorable interaction free energy of − 18.48 kcal/mol related to Sorafenib. Furthermore, these designed compounds demonstrated promising pharmacokinetic profiles.

Chemically Stable Group IV-V Transition Metal Carbide Thin Films in Hydrogen Radical Environments.

Hydrogen is a crucial element in the green energy transition. However, its tendency to react with and diffuse into surrounding materials poses a significant challenge. Therefore, developing coatings to protect system components in hydrogen environments (molecular, radicals (H*), and plasma) is essential. In this work, we report group IV-V transition metal carbide (TMC) thin films as potential candidates for protective coatings in H* environments at elevated temperatures. We expose TiC, ZrC, HfC, VC, NbC, TaC, and Co2C thin films, with native surface oxycarbides/oxides (TMO x C y /TMO x ), to H* at elevated temperatures. Based on X-ray photoelectron spectroscopy performed on the samples before and after H*-exposure, we identify three classes of TMCs. HfC, ZrC, TiC, TaC, NbC, and VC (class A) are found to have a stable carbidic-C (TM-C) content, with a further subdivision into partial (class A1: HfC, ZrC, and TiC) and strong (class A2: TaC, NbC, and VC) surface deoxidation. In contrast to class A, a strong carbide reduction is observed in Co2C (class B), along with a strong surface deoxidation. The H* interaction with TMC/TMO x C y /TMO x is hypothesized to entail three processes: (i) hydrogenation of surface C/O atoms, (ii) formation of CH x /OH x species, and (iii) subsurface C/O atom diffusion to the surface vacancies. The number of adsorbed H atoms required to form CH x /OH x species (i) and the corresponding thermodynamic energy barriers (ii) are estimated based on the change in the Gibbs free energy (ΔG) for the reduction reactions of TMCs and TMO x . Hydrogenation of surface carbidic-C atoms is proposed to limit the reduction of TMCs, whereas the deoxidation of TMC surfaces is governed by the thermodynamic energy barrier for forming H2O.

First-Principles Calculations on Relative Energetic Stability, Mechanical, and Thermal Properties of B2-AlRE (RE = Sc, Y, La-Lu) Phases

The relative energetic stability, mechanical properties, and thermodynamic behavior of B2-AlRE (RE = Sc, Y, La-Lu) second phases in Al alloys have been investigated through the integration of first-principles calculations with the quasi-harmonic approximation (QHA) model. The results demonstrate a linear increase in the calculated equilibrium lattice constant a0 with the ascending atomic number of RE, while the enthalpy of formation ΔHf exhibits more fluctuating variations. The lattice mismatch δ between B2-AlRE and Al matrix is closely correlated with the transferred electron et occurring between Al and RE atoms. Furthermore, the mechanical properties of the B2-AlRE phases are determined. It is observed that the calculated elastic constants Cij, bulk modulus BH, shear modulus GH, and Young’s modulus EH initially decrease with increasing atomic number from Sc to Ce and then increase up to Lu. The calculated Cauchy pressure C12-C44, Pugh’s ratio B/G, and Poisson’s ratio ν for all AlRE particles exhibit a pronounced directional covalent characteristic as well as uniform deformation and ductility. With the rise in temperature, the calculated vibrational entropy (Svib) and heat capacity (CV) of AlRE compounds exhibit a consistent increasing trend, while the Gibbs free energy (F) shows a linear decrease across all temperature ranges. The expansion coefficient (αT) sharply increases within the temperature range of 0~300 K, followed by a slight change, except for Al, AlHo, AlCe, and AlLu, which show a linear increase after 300 K. As the atomic number increases, both Svib and CV increase from Sc to La before stabilizing; however, F initially decreases from Sc to Y before increasing up to La with subsequent stability. All thermodynamic parameters demonstrate similar trends at lower and higher temperatures. This study provides valuable insights for evaluating high-performance aluminum alloys.

A Rootless Duckweed-Inspired Flexible Artificial Leaf from Plasmonic Photocatalysts.

The naturally existing leaves are ubiquitous two-dimensional flexible solar-to-chemical conversion systems that can run continuously in a sustainable manner. However, the current artificial photocatalytic systems are unable to achieve this due to the grand challenge in integrating existing photocatalysts in a flexible layout with high conversion efficiency and the ability to function independently. Here, we report on a rootless duckweed-inspired artificial leaf based on a lightweight, flexible, Janus plasmonic nanosheet-integrated sponge. The Janus plasmonic catalytically active nanosheet was made from self-assembled gold nanocube nanoassemblies grown on the porous sponges, which were further coated with an ultrathin palladium layer on one side via a ligand symmetry-breaking method. This sponge-based photocatalytic system is lightweight yet able to float on a water surface and conducts the gas-liquid reaction without auxiliary pumping and mixing devices. In a model reaction of 4-nitrophenol reduction, this floating leaf could achieve 2.5-fold and 65-fold higher efficiency than the corresponding dispersion and precipitation systems, respectively. The film theory is used to explain the sponge-based lightweight solar-to-chemical conversion system in a detailed kinetic and thermodynamic analysis, including the reaction rate constant, activation energy, enthalpy, entropy, Gibbs energy, and equilibrium constant.

Modulation of d-Orbital Interactions in Dual-Atom Catalysts for Enhanced Polysulfide Anchoring and Kinetics in Lithium-Sulfur Batteries.

Modulating the electronic structure is essential for improving the anchoring and catalytic capabilities of catalysts in lithium-sulfur batteries (LSBs). This study delves into the modulation of d-orbitals in transition metal dual-atom catalysts (DACs) supported by boron nitride and graphene (BNC) hybrid sheets for LSBs. This study reveals that the d-band center of the DACs, a key determinant of material chemical properties, is primarily determined by the electronic configuration of the dyz and dx2-y2 orbitals. Furthermore, the interaction between dz2 of transition metals and S_3 p orbitals is critical for the binding strength of LiPSs. By understanding these interactions, the functionality of DACs can be customized for optimal performance in LSBs. For example, the MnCrBNC catalyst with 10 d-electrons exhibits the optimal d-band center and demonstrates exceptional LiPSs binding capability, the lowest Li2S decomposition energy barrier, and the lowest Gibbs free energy of reaction for the rate-determining step of sulfur reduction. This study elucidates the fundamental mechanisms for designing high-performance LSB catalysts through electronic structure modulation.

Design and Optimization of a Chemical Looping Hydrogen Production System Using Steam Reforming for Petrochemical Plants.

Industrial pollution is a significant environmental concern, and researchers are seeking solutions to minimize its impact. Chemical looping combustion is an efficient technique to decrease CO2 emissions. This study delves into its application within petrochemical plants for hydrogen production. In addition to its high efficiency in hydrogen production, this method yields pure CO2 and nitrogen. The design features four reactors utilizing iron and nickel metals as oxygen carriers. A model in Aspen Plus was developed to simulate this design and evaluate its performance. Aspen Plus uses RGIBBS submodel which works based on minimization of the Gibbs free energy. The research findings indicate that this design significantly boosted the hydrogen production rate from 3380 kmol/h in conventional steam reforming reactors and 4258 kmol/h in the three-reactor chemical looping combustion setup to 4408 kmol/h. Lowering the temperatures of the iron and nickel fuel reactors, as well as the iron steam reactor, reducing the airflow rate, and increasing the pressure of the iron steam reactor all led to increased hydrogen production. Conversely, changing the pressure of the nickel fuel reactor had minimal impact. The inlet steam flow rate exhibited a nonlinear effect, initially increasing and then decreasing the hydrogen production rate.

Electronic Effects in Cobalt Phthalocyanine Catalysts Towards Noble-Metal-Free, Photocatalytic CO2-to-CO Reduction.

Noble-metal-free CO2 reduction systems based on cobalt phthalocyanine (CoPc) and its derivatives have demonstrated remarkable photocatalytic performances; however, their structure-activity relationship with electronic tuning remains unexplored. Herein, we now provide a systematic study to investigate the electron effects of substituents on the CoPc family in photocatalytic CO2 reduction, where a Cu(I) heteroleptic photosensitizer is utilized. The highest performance can be achieved using cobalt tetracarboxylphthalocyanine in light-driven CO2-to-CO reduction, with a maximum turnover number of 2950 at 450 nm and an outstanding apparent quantum yield of 63.5% at 425 nm, over ten times the activity with the tetra-dimethylamino-substituted CoPc derivative. The favorable electron-withdrawing effects have been further verified by DFT calculations and cyclic voltammetry, which reduces the overpotential required for CO2 reduction and decreases the Gibbs free energy of the catalyst active intermediates, particularly the CO-desorption energetics.

Electrode Materials for NO Electroreduction Based on Dithiolene Metal–Organic Frameworks: A Theoretical Study

To quickly and efficiently screen catalytic materials with both activity and selectivity for the nitric oxide reduction reaction (NORR), we adopted a strategy that considers the activity of the side reaction hydrogen evolution reaction (HER) first. It can be seen that Fe3(THT)2 (THT = triphenylene-2,3,6,7,10,11-hexathiol) has extremely excellent HER activity, with a Gibbs free energy change (ΔG) of 0.007 eV. Based on the relationship between ΔG and theoretical exchange current density, all TM3(THT)2 can be divided into two regions: one is the absolute values of ΔG greater than 1 eV, the other is the absolute values of ΔG greater than 0 eV and less than 1eV. Obviously, the candidates with the absolute values of ΔG greater than 1 eV have poor HER performance, but this precisely provides the possibility of obtaining NORR catalytic materials with both excellent selectivity and activity. Subsequent calculation results show that the maximum ΔG change of the rate-determining step of Ta3(THT)2 is unexpectedly only 0.05 eV. Therefore, Ta3(THT)2 may be regarded as the NORR catalytic material with both excellent performance and selectivity. Based on the electron transfer and partial density of states (PDOS) analysis, it can be seen that Ta plays a crucial role in the activation stage of NO. The approach that considers the activity of the side reaction HER first may provide a new idea for rapidly screening highly selective and active NORR catalysts.

A Novel Method for Combination of Ionic Conductivity and pH-metry Methods for the Determination of the Aqueous Solubility of a New Diisopropylammonium Hydrogenmaleate Crystalline Molecule

Dissociation constant, solubility, and thermodynamic data are very important physicochemical parameters for biological substances and their knowledge is of fundamental importance for the validation of drugs. In addition to their low cost and accessibility, Conductometric and pH-metric methods seem to be particularly suitable for the determination of these parameters given the often weak acidic or basic nature of drugs. These parameters were determined for a new synthesized diisopropylammonium hydrogenmaleate (iPr2NH2-MA) crystalline molecule. Conductometric and pH-metric methods were used for this characterization. The pH-metric method lead to pKa1 = 3.6, pKa2 = 6.7 and pKa3 = 7.5, while the conductometric method made it possible to determine two pKa values which are pKa1 = 3.5 and pKa3 = 7.8. The values of the thermodynamic parameters calculated for the enthalpy change (∆rH0) and the entropy change (∆S) of the iPr2NH2-MA acidic dissociation reaction are of the order of ∆H = 25. 36 ± 0.06 kJ.mol-1 and ∆S = 6.08 ± 0.18 kJ.mol-1.K-1. In addition, the Gibbs free energy change (ΔG) of the molecule decreased as a function of temperature. The solubility varied between 1 and 84 mg mL-1 for pH values comprised between 3.5 and 8.5 and reached its maximum Smax = 84 mg mL-1 at pH 5.6. The dissociation process was found to be is non-spontaneous, endothermic and entropically favorable. These results demonstrated on the one hand the reliability and effectiveness of the Conductometric and pH-metric methods for the characterization of molecules with acidic and/or basic sites, and on the other hand the excellent physical and chemical properties of diisopropylammonium hydrogenmaleate (iPr2NH2-MA) crystalline molecule.

Assessment of Nuclear Fusion Reaction Spontaneity via Engineering Thermodynamics.

This work recalls the basic thermodynamics of chemical processes for introducing the evaluation of the nuclear reactions' spontaneity. The application and definition of the thermodynamic state functions of the nuclear processes have been described by focusing on their contribution to the chemical potential. The variation of the nuclear binding potentials involved in a nuclear reaction affects the chemical potential through a modification of the internal energy and of the other state functions. These energy changes are related to the mass defect between reactants and products of the nuclear reaction and are of the order of magnitude of 1 MeV per particle, about six orders of magnitude larger than those of the chemical reactions. In particular, this work assesses the Gibbs free energy change of the fusion reactions by assuming the Qvalue as the nuclear contribution to the chemical potential and by calculating the entropy through the Sackur-Tetrode expression. Then, the role of the entropy in fusion processes was re-examined by demonstrating the previous spontaneity analyses, which assume a perfect gas of DT atoms in the initial state of the fusion reactions, are conservative and lead to assessing more negative ΔG than in the real case (ionized gas). As a final point, this paper examines the thermodynamic spontaneity of exothermic processes with a negative change of entropy and discusses the different thermodynamic spontaneity exhibited by the DT fusion processes when conducted in a controlled or uncontrolled way.

Molecular interaction studies of Gamma-aminobutyric acid (GABA) in an aqueous medium at various temperatures: A comprehensive analysis using volumetric, thermoacoustic and DFT methods

The interaction of Gamma-aminobutyric acid (GABA) in an aqueous medium at various concentrations (0.101–1.086) mol·kg−1 as a function of temperature is being studied using volumetric, viscosity and acoustic analysis. The calculation of apparent molar volume (VΦ), partial molar volume (V∅o), apparent molar isentropic compression (Kϕ) and partial molar isentropic compression (Kϕ0) of GABA in an aqueous medium has been done by measuring the densities and speed of the sound in the temperature range of 298.15–323.15 K. The thermo-acoustic parameters like adiabatic compressibility (βs), acoustic impedance (Z), intermolecular free length (Lf), relative association (RA), relaxation time (τ), internal pressure (πi), enthalpy (ΔH), Gibbs free energy (ΔG), and change in entropy (ΔS) are also computed. The strength of the hydrogen bond interaction of GABA in an aqueous medium and its dipole moment are calculated using single-point energy calculations. These calculations employ IEFPCM and PCM solvation models using DFT/B3LYP and MP2 methods with the 6-311G++ (d, p) basis set. The outcomes are interpreted in terms of hydrogen bond interactions that exist in the mixture.

Lattice Match-Enabled Covalent Heterointerfaces with Built-in Electric Field for Efficient Hydrogen Peroxide Photosynthesis.

Crafting semiconducting heterojunctions represents an effective route to enhance photocatalysis by improving interfacial charge separation and transport. However, lattice mismatch (δ) between different semiconductors can significantly hinder charge dynamics. Here, meticulous lattice tailoring is reported to create a covalent heterointerface with a built-in electric field (BIEF), imparting markedly improved hydrogen peroxide (H2O2) photosynthesis. Specifically, an In2S3/CdS heterojunction with a coherent heterointerface, characterized by covalent In─S─Cd bridge and exceptionally low lattice mismatch of 0.27%, and a BIEF from In2S3 to CdS, is rationally designed. This heterojunction entails rapid charge separation and transfer, achieving an outstanding H2O2 production rate of 2.09 mmol g-1 h-1 without the need for scavengers and oxygen bubbling, and a high apparent quantum efficiency of 17.73% at 400 nm. Density functional theory (DFT) calculations further reveal that this Z-scheme heterojunction facilitates the adsorption of *O2 and the generation of *OOH intermediates during the 2e- oxygen reduction reaction, associated with a low Gibbs free energy. This study underscores the significance of fine-tuning interfacial lattices and integrating BIEF to accelerate photocatalysis. The simple yet robust strategy can be conveniently leveraged to enhance device performance in optoelectronics, electrocatalysis, photoelectrocatalysis, and sensing.

Electrochemical kinetic energy harvesting mediated by ion solvation switching in two-immiscible liquid electrolyte

Kinetic energy harvesting has significant potential, but current methods, such as friction and deformation-based systems, require high-frequency inputs and highly durable materials. We report an electrochemical system using a two-phase immiscible liquid electrolyte and Prussian blue analogue electrodes for harvesting low-frequency kinetic energy. This system converts translational kinetic energy from the displacement of electrodes between electrolyte phases into electrical energy, achieving a peak power of 6.4 ± 0.08 μW cm−2, with a peak voltage of 96 mV and peak current density of 183 μA cm−2 using a 300 Ω load. This load is several thousand times smaller than those typically employed in conventional methods. The charge density reaches 2.73 mC cm−2, while the energy density is 116 μJ cm−2 during a harvesting cycle. Also, the system provides a continuous current flow of approximately 5 μA cm−2 at 0.005 Hz for 23 cycles without performance decay. The driving force behind voltage generation is the difference in solvation Gibbs free energy between the two electrolyte phases. Additionally, we demonstrate the system’s functionality in a microfluidic harvester, generating a maximum power density of 200 nW cm−2 by converting the kinetic energy to propel the electrolyte through the microfluidic channel into electricity.

Energetic Salts of Cubane-1,4-Dimethylnitrocarbamate.

Several salts of cubane-1,4-dimethylnitrocarbamate (CMNC) were synthesized. The divalent CMNC is deprotonated by alkaline, alkaline earth metal, and nonmetal bases to form the corresponding salts. The compounds were characterized and analyzed by multinuclear NMR and IR spectroscopy, mass spectrometry, elemental analysis, single crystal X-ray, and thermoanalytical techniques. The energies of formation for the salts were calculated using Gaussian. Detonation performances were calculated with the Explo5 (V6.03) computer code. The sensitivities toward impact and friction were determined and compared to the neutral CMNC.

Enthalpy increment of PbBi12O19(s) and ϕ-Pb5Bi8O17(s) by drop calorimetry

Enthalpy increments of PbBi12O19(s) and ϕ-Pb5Bi8O17(s) were measured by drop calorimetry in the temperature range 463–895 K and 475–757 K, respectively. A Python-based computer program implementing the Shomate method was coded to fit the experimental data. The expressions for enthalpy increment of PbBi12O19(s) and ϕ-Pb5Bi8O17(s) as a function of temperature are:HT0-H2980 < PbBi12O19> (J/mol) = 180.994×T+4939.217×10-4×T2-1746.59×104×T-1-39289 (T: 463 – 895 K)HT0-H2980 < ϕ-Pb5Bi8O17> (J/mol) = 792.256×T-65.626×10-4×T2+1638.68×104×T-1-290589 (T: 475 – 757 K)Entropies and Gibbs energy functions were also derived from the enthalpy increment data.

Deciphering the Entropy-Driven Host-Guest Interactions within Single Covalent Organic Frameworks for Trapping of 131I.

By combining dark-field optical microscopy with an in situ thermochemical aqueous solution system, we report a single-particle imaging strategy to investigate the host-guest interactions between covalent organic framework-300 (COF-300) as a representative COF host and a series of linear-chain fatty amines. The thermodynamic parameters, such as dissociation constant, Gibbs free energy changes, enthalpy changes, and entropy changes for the binding events within COF-300 are quantified. Correlation between the hydrophobicity of various amines and other data suggests that the mechanism of the host-guest bindings arises from the entropy-driven noncovalent interactions such as hydrogen bonds and van der Waals forces. These mechanistic insights allow for the rational design and preparation of COF-300-encapsulated n-octylamine with enhanced trapping performance of radioactive 131I-. This study not only provides thermodynamic insights into the host-guest interactions within the COF framework but also establishes a structure-property relationship between fatty amines and energetic magnitude information.

Theory of Space Quantization and the Quantum Level Understanding of the True Logics of the Principles of Thermodynamics and Heat Engines

The recently discovered Topological Theory of Quantum Gravity (TTQG) is basically a Theory of Space Quantization (TSQ) and in this article first of all it has been substantiated that though the laws of thermodynamics, the well-known thermodynamic principles, the operations of heat engines are very much intuitive but they, in their conventional representations, miserably lack the harmony to the quantized ‘space -time’ of the universe. The well-known thermodynamic parameters, e.g., pressure (P), volume (V), heat content (H), internal energy (U), entropy (S), Gibbs free energy (G),....etc. and the related physical variables like ‘time’ (t)and ‘mass’ (m) do exist in the form of ‘quantum’ or ‘packets’(referred as Gravitons in TTQG) and those are continuously being exchanged between the so called ‘thermodynamic systems’ and the ‘space-time’. It has been shown in this article that a ‘thermodynamic system’ and the above said ‘space quantums’ are very much complimentary and ‘part and parcel’ to each other and a quantum level ‘space-time’ rich understanding has been made through the TSQ of the true logic behind the standing of the thermodynamic laws and the operations of the heat engines.