Alkane Molecules Research Articles

Features of the behavior of nanosized catalytic dispersions in Fischer-Tropsch synthesis in slurry reactorsof the CSTR and SBCR types

BackgroundThis study investigates the behavior of nanosized iron-containing dispersions during Fischer–Tropsch synthesis (FTS) in three-phase reactors of different types: CSTR and SBCR. MethodsThe catalytic activity of nanosized dispersions was studied in three-phase reactors of different types: CSTR and SBCR. Calculations of the parameters of kinetic models for different reactors were carried out using Excel 2013 spreadsheets, the physical properties of gas mixtures and liquid hydrocarbon media were carried out using built-in models of ASPEN HYSYS v 10. Significant findingsFor the first time, the influence of the type of slurry reactor on the catalytic behavior of a nanosized particles during FTS was systematically studied.It has been established that at various temperatures, pressure and GHSV in the presence of a nanosized Fe catalysts, XCO for SBCR in most cases is close to XCO for CSTR, which is not consistent with the literature data for these reactors with micro-sized slurry catalysts.The results of kinetic estimates indicate the presence of inhibition in the liquid/nanoparticle edge, which is hypothetically related to the dynamics of molecules of long-chain alkanes of the dispersion on this edge and may depend on the nature of the mechanical action on such a medium.

Effect of gas type on properties of anionic surfactant foam system

The foam drainage technique is considered to be a promising measure for solving the problem of liquid accumulation in natural gas wells and gathering pipelines. However, differences in gases can greatly affect the performance of surfactant foam, thus limiting the application of this technology. To elucidate the mechanism of natural gas components influencing foam properties, the interfacial properties of hydrocarbon gas-surfactant-water system were analyzed thermodynamically and kinetically by combining molecular dynamics simulations and foaming experiments. The results show that with the increasing alkane chain length, the foaming volume and half-life of the foam are gradually rising, while the gas–liquid interfacial tension is decreasing, which is consistent with the results of molecular dynamics simulations. Compared with air, hydrocarbon gases are more beneficial for foam generation and stabilization. The interfacial adsorption of alkane molecules and the interaction between alkanes and surfactants are the main factors affecting the interfacial tension and film stability of different systems.

Molecular Insights into CO2 Diffusion Behavior in Crude Oil

CO2 flooding plays a significant part in enhancing oil recovery and is essential to achieving CCUS (Carbon Capture, Utilization, and Storage). This study aims to understand the fundamental theory of CO2 dissolving and diffusing into crude oil and how these processes vary under reasonable reservoir conditions. In this paper, we primarily use molecular dynamics simulation to construct a multi-component crude oil model with 17 hydrocarbons, which is on the basis of a component analysis of oil samples through laboratory experiments. Then, the CO2 dissolving capacity of the multi-component crude was quantitatively characterized and the impacts of external conditions—including temperature and pressure—on the motion of the CO2 dissolution and diffusion coefficients were systematically investigated. Finally, the swelling behavior of mixed CO2–crude oil was analyzed and the diffusion coefficients were predicted; furthermore, the levels of CO2 impacting the oil’s mobility were analyzed. Results showed that temperature stimulation intensified molecular thermal motion and increased the voids between the alkane molecules, promoting the rapid dissolution and diffusion of CO2. This caused the crude oil to swell and reduced its viscosity, further improving the mobility of the crude oil. As the pressure increased, the voids between the internal and external potential energy of the crude oil models became wider, facilitating the dissolution of CO2. However, when subjected to external compression, the CO2 molecules’ diffusing progress within the oil samples was significantly limited, even diverging to zero, which inhabited the improvement in oil mobility. This study provides some meaningful insights into the effect of CO2 on improving molecular-scale mobility, providing theoretical guidance for subsequent investigations into CO2–crude oil mixtures’ complicated and detailed behavior.

Temperature-induced desorption and decomposition of the organic molecule on the fused silica surface: Cleaning mechanism of laser heating

Understanding the structure–property relationships of the organic molecule-fused silica interface at the molecular level provides insights into the nature of their adhesion and desorption. In this study, molecular dynamic simulation and the ReaxFF force field are employed to investigate the adhesion properties of benzene, toluene, dodecane and dibutyl phthalate (DBP) on fused silica at different temperatures. The result shows that adhesion energy between benzene or toluene molecules and fused silica decreases gradually with the increased system temperature. The temperature affects Coulomb and van der Waals forces significantly. Environmental humidity affects the evaporation rate of alkane contaminants from fused silica. Besides, ambient humidity also affects the number of alkane molecules adsorbed to the fused silica surface and the chain configuration of adsorbed alkane molecules. Although the coverage of alkane molecules on fused silica is different, the relationship between temperature and the amount of adsorbed alkane molecules is not affected by the surface coverage of alkane molecules on the fused silica surface. These findings provide theoretical support for removing transparent organic contaminants from glass-like material surfaces using laser heating, laying the theoretical foundation for developing laser cleaning technologies.

Unraveling Molecular Diffusion Behaviors on the Acidic Sites of H‐ZSM‐5 Zeolite Using Time‐Resolved In Situ FT‐IR Technique

AbstractZeolites, renowned for their abundant crystalline structures and moderate acidities, have garnered significant attention in industrial chemical processes. Among them, the diffusion behaviors of various hydrocarbons within zeolite play a pivotal role due to their profound impact on product selectivity and separation efficiency. While acid sites are essential in determining the catalytic performance of zeolites, their effect on intra‐crystalline diffusivities has often been neglected in catalyst design. Herein, we employ a homemade time‐resolved in situ Fourier Transform Infrared (TR in situ FT‐IR) spectroscopy to investigate the intricate interplay between Brønsted acid sites and various probe molecules. Our study reveals that an augmentation in the density of Brønsted acid sites within H‐ZSM‐5 zeolites remarkably enhances the diffusivity of 1‐butene, in stark contrast to the behavior observed for iso‐butane. This contrasting effect in diffusivity is attributed to the distinct nature of interactions between alkenes and alkanes with Brønsted acid sites. Specifically, the π‐H interactions between alkenes and acid sites act as a driving force, propelling the alkene molecules forward through the zeolite pores. These findings offer valuable insights into designing tailored zeolites with specific acid site properties, controlling the transport behaviors of various probe molecules, and promising new avenues for catalysis and separation.

The reverse-DADI method: Computation of frequency-dependent atomic polarizabilities for carbon and hydrogen atoms in hydrocarbon structures

A specific method, combining some ingredients of the well-known DDA and PDI approaches, has been developed in our group since many years to calculate the absorption cross-sections of carbonaceous nanoparticles based on their atomistic details. This method, here named the Dynamic Atomic Dipole Interaction (DADI) model, requires the knowledge of the position and frequency-dependent polarizability of each atom constituting the nanoparticles. While the atomic positions can be quite easily obtained, for example as the results of molecular dynamics simulations, obtaining the frequency-dependent atomic polarizabilities is a trickier task. Here, a fitting procedure, named the reverse-DADI method, has been applied to calculate the frequency-dependent atomic polarizability values for carbon and hydrogen atoms involved in aromatic cycles or in aliphatic chains, on the basis of frequency-dependent molecular polarizabilities of various PAH and alkane molecules, calculated with the TD-DFT theory, in the UV–Visible range. Then, using these frequency-dependent atomic polarizabilities as input parameters in the DADI model has been shown to lead to an accurate representation of the absorption cross-sections of various PAH and alkane molecules with respect to the corresponding values obtained at the TD-DFT level, with however the great advantage of a much shorter time of calculations. Furthermore, these results are indications of a good transferability of the frequency-dependent atomic polarizability values obtained here to any C or H atom of any PAH or alkane molecule. This opens the way for building large databases of optical properties for carbonaceous species of atmospheric or astrophysical interests.

Photodimerization-Triggered Photopolymerization of Triene Coordination Polymers Enables Macroscopic Photomechanical Movements.

Controlling the packing of olefinic molecules in crystals is essential for triggering solid-state [2 + 2] photocycloaddition reactions and the synthesis of photocontrolled smart materials. Herein, we report the stepwise photodimerization-triggered photopolymerization of two triene coordination polymers (CPs), {[Zn(2-BBA)2(tpeb)]·0.5CH3CN}n (1, 2-HBBA = 2-bromobenzoic acid, tpeb = 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene) and {[Zn(3-BBA)2(tpeb)]·CH3CN)}n (2, 3-HBBA = 3-bromobenzoic acid). Upon irradiation with 420 nm light, each pair of closely packed and parallel olefinic bonds in 1 undergoes a [2 + 2] cycloaddition reaction, which connects two adjacent Z-shaped chains into a ladder-like coordination chain [Zn(2-BBA)2(bpbdpvpcb)0.5]n (1a, bpbdpvpcb = 1,3-bis(4-pyridyl)-2,4-bis(3,5-di(2-(4-pyridyl)vinyl)phenyl]cyclobutene) through single-crystal to single-crystal (SCSC) transformation. After photodimerization from 1 to 1a has occurred, the olefinic bonds that were initially distant are brought in close enough proximity to meet the requirements for a subsequent [2 + 2] cycloaddition reaction. Upon further light irradiation, the neighboring bpbdpvpcb ligands in 1a experience a SCSC photopolymerization based on [2 + 2] photocycloaddition and transform into poly-3b,4,5,5a,8b,9,10a-octahydro-4,5,9,10-tetrapyridyl-2,7-di(2-(4-pyridyl)vinyl)dicyclobuta[e,l]-pyren (poly-otpdpvdcbp). 2 showed similar structural changes under UV light illumination. Under light exposure, single crystals of 1 and 2 with different morphologies exhibit bending, cracking, and jumping photomechanical motions. The composite film (1-PVA) engineered by dispersing crystalline particles of 1 in poly(vinyl alcohol) (PVA) displays interesting light-wavelength-dependent photomechanical motions and can perform photodriven swimming on a liquid surface. This work provides a useful and promising approach to enable photodimerization of those photoinactive olefin pairs embedded in CPs and opens a new route to synthesize organic polymers by using olefinic CP platforms.

Breaking the stability limit of zeolite-based alkane dehydrogenation catalysts

Metal catalysts confined inside zeolite micropores or crystals are widely applied in the chemical industry because of their distinctive catalytic functions, especially with regard to the conversion of small and stable alkane molecules [1,2]. Silicalite-1 (S-1), a pure silica zeolite with an MFI topology, has a robust framework capable of withstanding harsh thermal and chemical conditions. Recently, S-1-based catalysts have demonstrated significant advantages in the construction and stabilization of various active metal centers and have attracted considerable attention for their potential in alkane dehydrogenation reactions. The absence of acidic sites prevents various acid-catalyzed side reactions, rendering S-1 a promising candidate for high-temperature reactions such as non-oxidative propane dehydrogenation (PDH). Sun et al. revealed that encapsulating subnanometer bimetallic PtZn clusters in S-1 resulted in a high propylene selectivity of 99%, with no catalyst deactivation even after 200h in the PDH reaction [3]. However, sustaining high stability at high conversion rates is still challenging for PDH reactions, and commercial processes are still based on Pt- and Cr-based catalysts, which need frequent regeneration.

A comparative study of shale oil transport behavior in graphene and kerogen nanopores with various roughness via molecular dynamics simulations

Understanding the transport behavior of molecules within nanopores is crucial in various fields, including nanofluidic, bioengineering and geophysics. To elucidate oil flow within shale organic nanopores, the simplified carbon nanopores (e.g., graphene and CNTs) and realistic kerogen nanopores have been extensively applied. The variation in pore structure models leads to divergent findings in oil flow behavior. This study employs molecular dynamics simulations to compare alkane flows within graphene and kerogen nano-slits with similar surface roughness. We observe that using graphene nanopores with ultra-smooth surfaces may introduce errors of several orders of magnitudes in flux calculations. Conversely, when accounting for similar roughness, the static characteristics and flow behaviors in graphene and kerogen slit pores are largely comparable. The relative error of flux and the flow velocity could be lower than 6% when using graphene to replace the realistic kerogen. Alkane molecules exhibit a parabolic velocity profile, with a no-slip condition adjacent to the rough surfaces. In addition, when applying the Hagen-Poiseullie equation for alkane flow in rough nanopores, Gibbs dividing surface is recommended for defining the pore radius, reducing the error of flux predicted to below 10%. Our work fulfills the gap in accessing the suitability of using graphene as a model for oil transport in shale organic nanopores, and provides valuable insights and guidance for future studies on nanofluidic in shale, including molecular simulations, nanofluidic experiment designs, and multi-scale modeling.

Structural Chemistry Simulation Experiments: A Case Study on Conjugated Alkene Molecules

As a core branch of chemistry, structural chemistry presents challenges in teaching due to its theoretical constructs and complex mathematical derivations. The application of quantum mechanics is particularly difficult for students. This paper analyzes the limitations of traditional experimental teaching and proposes simulation experiments as an effective supplementary method. Simulation experiments, by reducing costs, improving safety, and enhancing intuitiveness, help students deeply understand the theoretical knowledge of structural chemistry and cultivate their critical thinking and problem-solving skills. This study designs a series of simulation experiment teaching activities aimed at enhancing students' understanding of the structural characteristics of conjugated alkene molecules and their impact on molecular properties. Through case analysis, interactive discussions, and feedback evaluation, the study demonstrates the advantages of simulation experiments in improving student engagement, knowledge mastery, and practical abilities. Additionally, it points out the shortcomings of simulation experiments in terms of authenticity and technological dependence and proposes corresponding improvement suggestions. Finally, it emphasizes the importance of combining practical experimental operations with cultivating students' autonomous learning abilities, aiming to provide a more comprehensive strategy for structural chemistry teaching.

A Pillararene-Based Cavitand: Synthesis and Solid-State Capsular Assemblies Induced by Linear Alkanes with Specific Lengths.

Herein, a novel pillararene-based cavitand with fixed planar chirality was synthesized by the SuFEx reaction. As demonstrated by single crystal X-ray analysis, host-guest capsules involving this cavitand and linear alkanes with specific lengths are observed in the solid state. The formation of each capsule is driven by hydrogen bonding interactions between a linear alkane molecule and two cavitand molecules, as well as noncovalent interactions between the two cavitand molecules in this capsule.

Experimental Reactivity of (MoO3)NO- (N = 1-21) Cluster Anions with C1-C4 Alkanes: A Simple Model to Predict the Reactivity with Methane.

Metal oxide clusters with atomic oxygen radical anions are important model systems to study the mechanisms of activating and transforming very stable alkane molecules under ambient conditions. It is extremely challenging to characterize the activation and conversion of methane, the most stable alkane molecule, by metal oxide cluster anions due to the low reactivity of the anionic species. In this study, using a ship-lock type reactor that could be run at relatively high pressure conditions to provide a high number of collisions in ion-molecule reactions, the rate constants of the reactions between (MoO3)NO- (N = 1-21) cluster anions and the light alkanes (C1-C4) were measured under thermal collision conditions. The relationships among the reaction rates of different alkanes were obtained to establish a model to predict the low rate constants with methane from the high rate constants with C2-C4 alkanes. The model was tested by using available experimental results in literature. This study provides a new method to estimate the relatively low reactivity of atomic oxygen radical anions with methane on metal oxide clusters.

Chemical heterogeneity size effects at nanoscale on interface thermal resistance of solid–liquid polymer interface via molecular dynamics simulations

The shrinking size of integrated chips poses thermal management challenges. Understanding the size effect of chemical heterogeneity on solid–liquid interfacial thermal transfer is essential for heterogeneous chip design, yet the underlying mechanisms remain lacking. The present work used the liquid n-alkanes as the thermal interface material between solid platinum substrates. To characterize chemical heterogeneity, periodic solid surface patterns composed of patches with alternating solid–liquid affinities were constructed. By using non-equilibrium molecular dynamics simulations, we investigated the size effect of chemically heterogeneous patterns on interfacial thermal resistance (ITR) at the nanoscale. At larger heterogeneity sizes, i.e., larger patch sizes, most alkane molecules directly in contact weak interaction patches cannot interact with strong interaction patches due to long atomic distances. In the case of alkanes in contact a cold substrate, alkanes in contact weak interaction patches transferred thermal energy to the substrate at a lower rate than those in contact strong interaction patches. The different rates resulted in the higher temperature of alkanes in contact weak interaction patches than those in contact strong interaction patches and, therefore, a larger disparity between temperature jump at the strong interaction areas and that at the weak interaction areas. The non-uniformity of temperature jump distribution increased ITR when compared to the heterogeneous surface system characterized by a smaller patch size with a more uniform temperature distribution in the plane perpendicular to the heat flux direction. In addition, the classical parallel thermal resistance model predicted ITR accurately for the heterogeneous surface systems with small size patches but overestimated overall thermal resistance.

Quantum chemical modeling of alkane 2D monolayer formation on graphene

The paper presents a quantum chemical approach for assessment of the thermodynamic parameters of association for alkanes CnH2n+2 (n = 6–14) and polyaromatic hydrocarbons (PAH) of the coronene series as model structures of the graphene surface within the framework of semiempirical methods. The enthalpy, entropy and Gibbs energy of formation and binding for alkanes with PAH were calculated using the PM3 and PM6-DH2 methods. It is shown that an adequate description of the interactions in the regarded complexes requires the use of PM6-DH2 method, since it contains corrections for dispersion interactions and hydrogen bonds. The parallel orientation of the alkane molecule relative to the coronene plane is proved to be more energetically preferable than perpendicular one, which is consistent with experimental data.Intermolecular C–H/π interactions are revealed to be crucial in the 2D film formation of alkanes on graphene/graphite. While interactions between alkane molecules make a destabilizing contribution due to the implementation of energetically unfavorable types of intermolecular CH/HC interactions. This stipulates a threshold chain length of alkanes capable of film formation on the graphene/graphite surface at standard temperature: 14 and 19 carbon atoms for parallel and perpendicular oriented alkanes, respectively. The obtained threshold values of the alkane chain length, as well as the geometric parameters of their orientation in 2D monolayers on the graphene/graphite surface are consistent with available experimental data.

Hydrosilylation of Olefins Activated on Highly Lewis-Acidic Calcium Cation.

The report introduces simple yet highly reactive calcium salt, Ca[Al(ORF)4]2 (RF=C(CF3)3), 1, which effectively catalyses olefin hydrosilylation through an unusual mechanism involving the activation of the alkene molecule. Upon dissolution in o-difluorobenzene (oDFB), 1 forms a highly Lewis acidic [Ca(oDFB)6]2+ complex. Our DFT calculations reveal that fluoride ion affinity is comparable to SbF5. Reactivity tests show that it effectively catalyses the hydrosilylation of olefins with high regioselectivity, also in reactions involving sterically demanding substrates like (iPr)3SiH or tetrasubstituted olefins. Experimental and computational results point to the mechanism where the olefin molecule forms a complex with Ca2+, which significantly facilitates the attack of H-SiR3 on the C=C double bond.

MD simulations of diffusion of cyanobiphenyl molecules adsorbed on the graphene surface coated with alkane and alcohol molecules

AbstractMolecular dynamics simulations were carried out to study the structural and diffusion properties of a cyanobiphenyl monolayer composed of pentyl cyano biphenyl (5CB) and pentyloxy cyano biphenyl (5OCB) molecules on a graphene surface coated with alkane and alcohol molecules. To investigate the diffusion properties of 5CB and 5OCB molecules on the graphene surface, the molecules of pentane ( ) and dodecane ( ) from alkanes and dodecanol ( ) from alcohols with a polar hydroxyl ( ) terminal functional group were chosen as orienting surfactant molecules. It was found that the diffusion ability of cyanobiphenyl molecules in a graphene substrate coated with alkane and alcohol molecules depends on the chain length of these molecules and on the presence of polar hydroxyl –OH terminal groups. With an increase in the length of alkane molecules from to , the value of the diffusion coefficient (or ), it decreases slightly, while the presence of the polar hydroxyl terminal group leads to a significant decrease in this diffusion coefficient of cyanobiphenyl molecules.

Electron Dynamics in Alkane C-H Activation Mediated by Transition Metal Complexes.

Alkanes, ideal raw materials for industrial chemical production, typically exhibit limited reactivity due to their robust and weakly polarized C-H bonds. The challenge lies in selectively activating these C-H bonds under mild conditions. To address this challenge, various C-H activation mechanisms have been developed. Yet, classifying these mechanisms depends on the overall stoichiometry, which can be ambiguous and sometimes problematic. In this study, we utilized density functional theory calculations combined with intrinsic bond orbital (IBO) analysis to examine electron flow in the four primary alkane C-H activation mechanisms: oxidative addition, σ-bond metathesis, 1,2-addition, and electrophilic activation. Methane was selected as the representative alkane molecule to undergo C-H heterolytic cleavage in these reactions. Across all mechanisms studied, we find that the CH3 moiety in methane consistently uses an electron pair from the cleaved C-H bond to form a σ-bond with the metal. Yet, the electron pair that accepts the proton differs with each mechanism: in oxidative addition, it is derived from the d-orbitals; in σ-bond metathesis, it resulted from the metal-ligand σ-bonds; in 1,2-addition, it arose from the π-orbital of the metal-ligand multiple bonds; and in electrophilic activation, it came from the lone pairs on ligands. This detailed analysis not only provides a clear visual understanding of these reactions but also showcases the ability of the IBO method to differentiate between mechanisms. The electron flow discerned from IBO analysis is further corroborated by results from absolutely localized molecular orbital energy decomposition analysis, which also helps to quantify the two predominant interactions in each process. Our findings offer profound insights into the electron dynamics at play in alkane C-H activation, enhancing our understanding of these critical reactions.

Dispersive surface free energy of adsorbents modified by supramolecular structures of heterocyclic compounds

In the present work, the dispersive surface free energy was calculated by Dorris-Gray method for 30 samples of adsorbents modified with chiral supramolecular structures of uracil, 6-methyluracil, 5-hydroxy-6-methyluracil, 5-fluorouracil, thymine, melamine, cyanuric and barbirutic acids, and perylene-3,4,9,10-tetracarboxylic dianhydride. It was shown that the homologous series of n-alkanes is better suited for measuring dispersive surface free energy than the homologous series of alcohols. It was established that the classical Dorris-Gray method does not allow obtaining well interpretable data for the objects studied. This is due to a noticeable effect that inductive interactions of a polar surface as an inductor with nonpolar alkane molecules have on the calculated values. We suggested to modify the Dorris-Gray method, making it possible to obtain data on the dispersive component of the free energy of adsorption. It was shown that the changes in dispersive surface free energy as a result of the modification correlate well with data on the structure and properties of supramolecular ensembles of the modifiers used. The results obtained can be used to predict the enantioselectivity of chiral adsorbents.

Solution Structure and Dynamics of Hf-Al and Hf-Zn Heterobimetallic Adducts Mimicking Relevant Intermediates in Chain Transfer Reactions.

Cationic cyclometalated hafnocenes [CpPrCpCH2CH2CH2Hf][B(C6F5)4] (4Pr) and [CpiBuCpCH2CH(Me)CH2Hf][B(C6F5)4] (4aiBu and 4biBu) were synthesized from the corresponding [(CpPr)2HfMe][B(C6F5)4] (1Pr) and [(CpiBu)2HfMe][B(C6F5)4] (1iBu) complexes via C-H activation. 4aiBu, 4biBu, and 4Pr, mimicking a propagating M-polymeryl species (M = transition metal) with or without a β-methyl branch on the metalated chains, serve to investigate whether and how the nature of the last inserted olefin molecules changes the structure, stability, and reactivity of the corresponding heterobimetallic complexes, formed in the presence of aluminum- or zinc-alkyl chain transfer agents (CTAs), which are considered relevant intermediates in coordinative chain transfer polymerization (CCTP) and chain shuttling polymerization (CSP) technologies. NMR and DFT data indicate no major structural difference between the resulting heterobridged complexes, all characterized by the presence of multiple α-agostic interactions. On the contrary, thermodynamic and kinetic investigations, concerning the reversible formation and breaking of heterobimetallic adducts, demonstrate that isomer 4aiBu, in which the β-Me is oriented away from the reactive coordination site on Hf, but not 4biBu, having the β-Me pointing in the opposite direction, is capable of reacting with CTAs. Quantification of kinetic rate constants highlights that the formation process is rate limiting and that the nature of the last inserted α-olefin unit modulates transalkylation kinetics. The reaction of 4aiBu, 4biBu, and 4Pr with diisobutylaluminum hydride (DiBAlH) allows the interception and characterization of new heterobinuclear and heterotrinuclear species, featuring both hydride and alkyl bridging moieties, which represent structural models of elusive intermediates in CCTP and CSP processes, capturing the instant when an alkyl chain has just transferred from a transition metal to a main group metal, while the two metals remain engaged in a single heterobimetallic intermediate.

Efficiency of Volatile Corrosion Inhibitors in the Presence of n-Heptane: An Experimental and Molecular Simulation Study

Volatile corrosion inhibitors (VCIs), specifically formulations based on thiols and amines, can be used to mitigate top-of-the-line corrosion (TLC) that arises during the transportation of wet gas through transmission pipelines. Nevertheless, the VCI inhibition efficiency (IE) can be compromised by the presence of condensable hydrocarbon phases. In this research, the IE of two thiol compounds (decanethiol and hexanethiol) and three combinations of VCIs for TLC scenarios, both in the presence and absence of n-heptane, representing a condensing hydrocarbon phase were studied. The results proved the IE of thiols in a water-only condensing environment, with effectiveness increasing with the alkyl tail length. Conversely, in a water/n-heptane co-condensing environment, a reversed trend was observed, where hexanethiol exhibited higher corrosion IE compared to decanethiol. Molecular simulation results indicated a synergistic adsorption behavior when the alkane was of a similar length as the alkyl tails of the inhibitors, leading to the incorporation of alkane molecules with the inhibitor molecules. A mixture of thiols (decanethiol and hexanethiol) and two mixtures of thiol and amines (decanethiol and diethylamine/t-butylamine) were also considered in both water-only and water/n-heptane co-condensing environments. In the presence of n-heptane, only the thiol mixture, featuring molecules with different tail lengths, demonstrated high IE. This behavior was attributed to the superior IE provided by thiol-based molecules with a shorter alkyl tail (hexanethiol) in the presence of n-heptane. Additionally, the results revealed that the mixtures of decanethiol and amines did not enhance corrosion inhibition in the presence of n-heptane within the system.