Thermodynamic properties of propanol using DFT in the gas phase

doi:10.21203/rs.3.rs-3408579/v1

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Thermodynamic properties of propanol using DFT in the gas phase

https://doi.org/10.21203/rs.3.rs-3408579/v1

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This study aims to assess the impact of thermodynamic properties of propanols (propan-1-ol, propan-2-ol) and their isomers (2-methylpropan-1-ol and 2-methylpropan-2-ol) on fuel mixtures with gasoline, diesel, and kerosene. The evaluation is conducted using the Functional Density Theory, which determines various thermodynamic properties like specific molar heat at constant pressure, entropy, Gibbs free energy, and variation of formation enthalpy for calculating the heat of combustion. The simulation is performed using the functional hybrid B3LYP structures with bases 6–311 + + g (d, p) and 6-31g (d) through the software Gaussian 09W and the semi-empirical method PM3. Notably, 2-methylpropan-1-ol and 2-methylpropan-2-ol show higher energy gains, generating 13.38 KJ/g and 13.88 KJ/g more energy per unit mass compared to ethanol (22.73 KJ/g) and methanol (12.70 KJ/g), respectively. As the fraction of propanols increases by 10%, propan-1-ol with 33.49 KJ/g and propan-2-ol with 33.53 KJ/g exhibit the highest energy losses when compared to gasoline, which recorded 13.81 KJ/g and 13.77 KJ/g, respectively, under similar pressure and temperature conditions. The combustion of propan-1-ol shows the lowest values in all scenarios, particularly with diesel fuel at 11.31 KJ/g and kerosene at 12.71 KJ/g.

Additionally, the study highlights the potential of these propanol-based mixtures as viable alternatives in the combustion phase, offering potential benefits in terms of energy efficiency and reduced emissions.

DFT

propanol’s

gasoline

diesel

kerosene

enthalpy

the heat of combustion

The oil instability, resulting from geopolitical uncertainties or financial sector influences since 1979 in Arab countries, disrupted the productive sector of crude oil-based goods in the East, leading to higher prices in the global market [1]. This situation has spurred the emergence of various renewable energy sources, including solid urban waste [2], straw [3], forest waste [4], and biogas [5, 6].

Brazil's remarkable biodiversity in biomass makes it a prominent producer of biofuels [7], with raw materials categorized into first, second, third, and fourth generations, derived from food crops, plant species, and microalgae [8, 9]. Biofuels originate from organic and non-fossil sources, such as alcohols [10], biomass [11], biodiesel [12], gaseous/aerated fuels (natural gas/synthesis gas) [13], and agricultural waste [14].

The long-standing and valuable practical impact of biofuels has led to their overvaluation in Brazil and globally, driving advancements in technology and their adoption as alternatives to fossil fuels [15, 16]. The environmental appeal of these organic materials lies in their sustainability and recyclability, with minimal harm to nature [18]. Transforming these raw materials into fuel, whether rigid [19, 20] or liquid [21], necessitates chemical processes to alter their physical state [22].

Green fuels [23] have a significant positive environmental impact as they interact effectively with fossil fuels, making their industrial conversion successful and establishing an almost linear relationship with reduced toxicity [24].

As an alternative to green fuels, low molecular weight alcohols such as ethanol [25], methanol [26], and propanol [27] are gaining attention as an alternative for use as engine fuels [28, 29]. The conformational structures for the propan-1-ol (nP) molecule and some of its isomers, such as propan-2-ol (iP), 2-methylpropan-1-ol (2M1P), and 2-methylpropan-2- ol (2M2P) (Fig. 1), are interesting for internal combustion engines due to their energy density and adequate volatility to act as fuel [30].

The commercial production of biofuels involves biomass fermentation, glucose conversion, and petrochemical processing [31–34]. Within the European Union, the obligation to use propanol and its isomers as mixtures with fossil fuels has been deferred, classifying them as combustible alcohols and applying this measure to all member states [35].

A major challenge in biofuel development is determining whether their miscible structures are suitable for specific temperatures. Achieving good stability at various temperatures is crucial, and the comparability of these combustible alcohols to fossil derivatives has shown promising results [37].

At elevated temperatures, ethanol, methanol, and propanol are more suitable choices [38]. Higher concentrations of ethanol and methanol increase the oxygen content, leading to improved combustion with reduced carbon monoxide (CO) and hydrocarbons (HC). In terms of carbon dioxide (CO₂) and nitrogen oxide (NOX), ethanol performs better than pure gasoline [39]. The oxygen content also relates to the number of octanes, directly influencing the resistance and detonation factor of these fuels. When ethanol and propanol are mixed with unleaded gasoline up to 20%, particulate materials like CO, HC, and sulfur (S) decrease, while the octane number increases, proportionally raising CO₂ and NOX levels, which are directly affected by the mixtures [40].

In addressing environmental concerns, exploring higher alcohols as a new metabolic pathway through microorganisms offers a promising biological approach, making them potential future solutions to the energy crisis [41]. Alcohol, ethanol, methanol, propanol, and butanol all share configurations with up to four carbon atoms, placing them within the same substance family according to the National Agency of Petroleum, Natural Gas, and Biofuels (ANP) in Brazil.

Pure alcohol or alcohol added to gasoline is used in light vehicles for automotive purposes [42]. With the advent of flex-fuel technology (VFF), or biofuel, motor vehicles can now run on pure or fractionated alcohol, which exhibits better engine performance while balancing high consumption. Brazilian manufactured vehicles stand out from other markets for their ability to use any amount of bioethanol-gasoline mixture [43–45].

Ethanol [46] and methanol [47] are the main alternative biofuels used in operation today in vehicles powered by gasoline, being described by the energy sector as ethyl and methyl alcohol, their operation occurs through the air-fuel mixture that is activated by a spark, from the spark plug, occurring inside the combustion chamber of the conventional or flex car engine [48, 49].

Propanol’s are combustible alcohols to define which one can obtain the best influence, which is determined by the position of the hydroxyl group in the fuel [50–52], has been investigated as their differences between fuel flames are detected through these isomers and are pronounced as oxygenated intermediates that can be formed directly from the fuel, this indicates that the carbons in both propanol’s are framed in the first steps of fuel consumption [53].

Table 1

Combustion temperature, auto-ignition, degree of concentration and molecular weight for different substances of Propanol and their isomers [54–57].
	propan-1-ol	propan-2-ol	2-methyl propan-1-ol	2methyl propan-2-ol
Molecular formula	C₃H₈O	C ₃H ₈O	C₄H₁₀O	C₄H₁₀O
Combustion Heat (kcal/mol)	482.71	474.35	637.67	631.93
Boiling point (K)	370.15	355.60	381.00	355.03
Density at 20 C (kg/m³)	805.30	786.00	802.00	781.00
Molecular weight (g/mol)	60.10	60.10	74.12	74.12

Propanol, an advanced alternative biofuel, offers higher heating value than ethanol, making it a promising option for widespread use [58]. Its chemical formula is C3H8O, and it exists in four isomers: n-Propanol, i-Propanol, 2-methylpropan-1-ol, and 2-methylpropan-2-ol [60–62]. These isomers have distinct physical and chemical properties based on the position of their hydroxyl groups attached to the carbon chain [63].

Propanol's advantages over other alcohols include a higher boiling point, energy density, and oxygen content, resembling fossil fuels [64]. It can be used as an additive or in pure form with gasoline, diesel, or kerosene [65–67]. While short-chain alcohols like methanol and ethanol have limitations, they are still used in biodiesel production [68].

Propanol's isomers have potential as long-chain alcohols, offering benefits as a common energy base, producing oxygen, and improving combustion performance, leading to reduced emissions [71]. They can be obtained from renewable resources, promoting cleaner fuel production [73]. Propanol and its isomers maintain their physical-chemical properties, making them superior fuels [74].

Understanding the structural properties of fuels is vital for optimizing engine combustion and minimizing environmental impact when combined with fossil fuels [76–79]. Different countries have legal limits on biofuel percentages based on state policies [80, 81].

Utilizing the Functional Density Theory (DFT), this study proposes exploring propan-1-ol and its isomers as biofuels, analyzing their thermodynamic properties and the impact of temperature changes [91–93]. Mixtures of propanol with gasoline, diesel, and kerosene have been studied, with results in the gas phase influencing combustion behavior [94–97].

This research will provide insights into how propanol's isomers, when added in varying proportions, affect mass and volatility, directly influencing combustion efficiency in fuel mixtures.

Materials

In this study, four propanol were used, being ordered according to their auto-ignition temperatures: propan-2-ol > propan-1-ol > 2-methylpropan-2-ol > 2-methylpropan-1-ol (Table 1).

2.2. Methods

Theoretical studies employing DFT and semi-empirical PM3 were conducted to investigate the properties of a well-defined thermodynamic system, specifically focusing on the gas phase free energies of ∆Hº (enthalpy), ∆Sº (entropy), ∆Gº (Gibbs free energy), and Cvº (specific heat) for propanol and its isomers [98–110]. Conformational analysis of the fuel molecules was initially performed using Gaussian 09W software based on the fundamental laws of quantum mechanics [101]. The molecular geometries were optimized using DFT with the continuous polarizable model (PCM) and the functional hybrid B3LYP, as well as the semi-empirical PM3 method [102–110].

The study determined the properties of the multielectron system using DFT with the functional hybrid B3LYP, providing accurate and sensitive modeling of electronic density distribution in each molecule [108–109]. The PM3 method, with experimental parameters for carbon, hydrogen, and oxygen, was also used for quick calculations, as these elements are the main constituents of fuels and biofuels [110].

The investigation focused on the gas phase of propanol and its isomers, considering their flash points, which determine the lowest temperature at which the fuels release enough steam to form a flammable mixture with an external heat source [110–111]. The enthalpy differentials of these gases were extracted to obtain the heat capacity at constant pressure (Cp), and the results were compared with experimental data from the NIST database [112].

In-depth analysis of the enthalpy revealed prolonged delay times, indicating more energetic and efficient combustion for mixtures of propanol’s (Propan-1-ol and Propan-2-ol, 2-Methylpropan-1-ol, and 2-Methylpropan-2-ol) in oxygen diluted with gasoline, diesel, and kerosene in the gas phase [111]. Different percentages of propanol and its isomers in the fuel concentrations (10%, 20%, and 30%) were proposed, and their equivalence was evaluated by comparing computational modeling data (IsP30GS, IsP30D, IsP30Q) with experimental values [111].

To validate the kinetic mechanism, the simulated results were compared with experimental data from the NIST gas-phase measurements [112]. This comprehensive approach aimed to provide valuable insights into the thermodynamic properties of propanol and its isomers when used as biofuels in various fuel mixtures.

3.1 Molecular Mechanics Simulations

$$\partial W=\partial ϴ-\partial U$$

$${\left.Cp=\left(\frac{\partial h}{\partial {\rm T}}\right.\right)}_{p}$$

In Fig. 2, we can see here that the exposed data achieved good compatibility between the theoretical and experimental Cp values available in the academic literature. The approximations with the DFT method by the functional B3LYP together with the bases 6–31 + + g (d) and 6–311 + + g (d, p) showed low deviations regarding the theoretical/experimental values, thus conferring reliability of the method used for this analysis.

These two sets of bases, mentioned previously, were the ones that most described the properties in the gas phase, showing themselves to be more suitable for the description of the nominal and experimental characteristics of each propanol isomer. Still, such an approach obtained satisfactory and accurate results for the nP and iP isomers up to a temperature of 600K, allowing us to obtain results equivalent to experimental values in the combustion temperature ranges.

The data obtained for the values of theoretical absolute deviations in the temperature range of 298.15K-600K, Fig. 3, showed that the B3LYP methods with the bases 6–311 + + g (d, p), 6–31 + g (d ) presented high degrees of the fidelity of theoretical and experimental values for the isomers of n-propanol and i-propanol with deviations below 1% and 2%, respectively. The results obtained for 2M1P and 2M2P showed absolute deviations that ranged from 6–20% for all methods used.

They also demonstrated that the methods used to obtain thermodynamic properties were less precise about the lower molecular chain isomers. In Fig. 3, it is also observed that the 2M1P molecule had the lowest absolute deviation with the PM3 method. Such a method allowed a satisfactory result in terms of its geometries for hydrogen bonding angles, however less exact for bonding energy such as hydrogens, thus forming weaker bonds.

The method employed considers optimized values and with great availability of algorithms using Gaussian functions since the beginning of its process [113]. When we compared the results of the PM3 base with our results with DFT, we obtained a lower result due to its high deviation when compared to the experimental results. The PM3 base is indicated only for a quick calculation, where there is a reduced computational cost.

Figure 4 shows the specific heat at constant pressure (Cp), showing the performance with which, each propanol isomer obtained in the gas phase for each temperature point. It is worth mentioning that for low temperatures of 0.5K, all presented the same value of Cp = 31.2 J / mol.K.

The temperature variation analysis revealed that nP and iP molecules had lower calorific powers compared to the other isomers. This behavior can be attributed to their linear chain structure, which limits their vibrational freedom and results in greater intermolecular van der Waals repulsions of the apolar areas of propan-1-ol and propan-2-ol. As a result, nP and iP have less capacity to store heat and tend to lose heat more easily.

On the other hand, 2M1P and 2M2P showed higher Cp values than nP and iP due to the presence of bulky radical groups (-CH₃) in their structures. These groups cause some vibrational limitation and intramolecular repulsions between -CH₃ substituents, influencing higher Cp values. Consequently, 2M1P and 2M2P exhibit a greater capacity to absorb and retain more heat compared to nP and iP.

Monitoring the thermodynamic properties within the temperature range of 298.15K to 600K is economically crucial for incorporating these fuels into mixtures in the gaseous state. Depending on their percentages, these mixtures directly affect cooling and heating processes. Among the studied isomers, obtaining n-propanol with the B3LYP/6–311 + + g(d,p) configuration was found to be more suitable.

The thermodynamic potentials of molecules in the gaseous phase were closely observed, directly relating to chemical thermodynamics. This is essential for the energetic study of these fuels, as it involves energy conversions and transformations between chemical and thermal energy. Parameters such as entropy, Gibbs free energy, specific heat, and enthalpy were named and characterized according to their temperatures for nP, iP, 2M1P, and 2M2P molecules [114]..

The entropy of the propanols and isomers studied in this work was compared with their respective experimental values at a temperature of 298.15K, and the results were found to be very close, as shown in Fig. 5. It was observed that the entropy of these fuels increases with the rise in temperature, within the range of 0.5-1500K, due to the volatility of each component in its thermal environment.

Among the studied molecules, 2M1P and 2M2P exhibited the highest entropy values, indicating a greater variation of internal energy and a higher degree of agitation with increasing temperature. This enhances their interactions in the gas phase as fuels, making them more likely to react spontaneously and release energy.

On the other hand, propan-1-ol and propan-2-ol had lower entropy values as they have fewer carbon and hydrogen atoms compared to the other molecules. Consequently, they are less capable of withstanding high compression rates, leading to increased energy losses during their interaction in an internal combustion engine compared to other branched chain propanols.

As a result, the lower thermal agitation of propan-1-ol and propan-2-ol directly impacts their energy dissipation when mixed with fuels with higher volatility, such as gasoline, diesel, and kerosene. This results in reduced interaction and suboptimal exploitation of the thermodynamic potential in such mixtures. The quantity related to Gibbs free energy is crucial in assessing the spontaneity of a chemical reaction and determining the work carried out within a specific thermodynamic system, as shown in Fig. 6.

Because it is a process that enhances the release of energy that tries to convert one energy into another as described by the first law of thermodynamics that involves associated kinetic energies in the direct sense to form more products described by (ΔG < 0), products less than the free energy of the reagents. Spontaneity was analyzed taking into account the energy released during the reaction, entropy, and the temperature rise for each propane molecule and its isomer. Both nP, iP, 2M2P, and 2M2P developed good energy spontaneity with the increase in temperature being vulnerable to a chemical reaction.

The molecules of nP, iP, and 2M1P were more likely to perform work in the internal combustion chamber of an engine in the temperature range of 298.15K-600K and could perform better in their energy interactions when associated with other fuel sources. It is important to note for the 650K temperature, it is also possible to verify that 2-methyl-propan-2-ol had the least tendency to influence among the four fuels analyzed.

The thermal capacity in a constant volume of any gas, including an ideal gas, treats the heat given or absorbed in the form of its gaseous state. This is shown in Fig. 7. This represents the thermal capacity over a strong influence of the internal energy variation carried out in the function of temperature in their interactions of intermolecular forces, demonstrating how such propane fuels and their isomers were influenced to express their specific heat (Cv).

It was observed that the intensive molar capacity involving the nature of propanil alcohols and their isomers, despite having the same calorific capacity, the four molecules had different energetic development through the physicochemical properties. The Cv for all molecules proved to be a positive amount to the isovolumetric increase in temperature, necessarily implying an increase in the internal energy of the system, both for 2M2P and 2M1P between 298.15K-600K expressed having a good amount of potential energy for intramolecular interaction and a high thermal capacity confirming that such molecules can exchange heat over a constant volume, for 200K < T < 600K the 2M1P molecule has a greater energy absorption capacity and consequently greater capacity to store energy. The nP and iP molecules showed less capacity to store energy, making it clear that the internal energy and the heat capacity at constant volume are also a function of temperature.

Figure 8 shows through the thermodynamic system how the enthalpies of the four propanol fuels can be obtained by making a relationship between their chemical reaction components linked to the heat of their system and their calorific content contained in a substance when undergoing a reaction.

Molar enthalpy (H) by the temperature at constant pressure described endothermic reaction processes that dealt with the energy transferred to the system in the form of heat from each component. The magnitude factor that is of interest for the analysis is the positive enthalpy variation (ΔH > 0) showing notoriety in temperature variations, where greater temperature variations have greater variations in their enthalpies. The 2M1P has a spatial arrangement in which there is a larger surface area than the other molecules, therefore having a greater energy absorption capacity (ΔH).

The nP and iP presented very similar values concerning each other and, still, presented intermediate enthalpy values about the other isomers. Such consensus maybe because they have an effective flat surface area greater than 2M2P and less than 2M1P. The latter, however much it has a higher molecular volume, presents lower values of (ΔH) due to the total substitution of central carbon by R-CH₃ groups, which reduces the flat surface area of contact.

${{\varDelta H}_{c}}_{\text{298,15}K}^{600K}$ = H(600K) – H(298,15K).

It was evident for all three methods, using the nP and iP molecules, they obtained the best conceptions of adjustment in their data and parameters, thus obtaining the best results concerning the 2M1P and 2M2P, which obtained a smaller deviation directly reflecting their performances. As the simulations took place at constant pressure, the heat exchanged is equivalent to the combustion enthalpy of the alcohols considered.

As theoretical results we find the following values for the combustion enthalpies of the studied alcohols, using the functional base B3LYP-6–311 + + g (d, p): ΔHc (propan-1-ol) = -2013.15KJ / mol; ΔHc (propan-2-ol) = -2015.07KJ / mol; ΔHc (2-methyl-propan-1-ol) = -2676.63KJ / mol and ΔHc (2-methyl-propan-2-ol) = -2714.01KJ / mol. These results do not differ much from the values of the combustion enthalpies described in the literature as shown in Table 2.

Table 2

Experimental values in the literature for combustion and entropy enthalpy.
Fuel	ΔH_c (kJ/mol)	References	S (J/mol.K)	References
Propan-1-ol	-2023.14	[116]	322.49	[120]
Propan-2-ol	-1984.70	[117]	309.91	[121]
2-Methylpropan-1-ol	-2668.00	[118]	350.00	[122]
2-Methylpropan-2-ol	-2644.00	[119]	326.00	[112]

The described methods used to determine its combustion enthalpies As can be seen in Fig. 10 at a temperature of 298.15K first need to be analyzed from its formation enthalpy using data extracted from the DFT itself, appropriating its electronic energies (zero-point energy and thermal corrections, with its coefficients for their atomic corrections as described by Osmont (2007) and others.

$${\varDelta }_{c}H=\sum \varDelta {H}_{\left(Produto\right)-}\sum \varDelta {H}_{\left(reagente\right)}$$

For the reactions to occur and the combustion to be acquired, both the reagent and the product needed to acquire their equilibrium, the coefficients (a, b, c) were necessary so that these molecules provided the number of equal elements that was only possible through their balances.

In general, the values of the methods used had deviations below 3% as shown in Table 3. It is objective to note that 2-methylpropan-1-ol using the bases B3LYP-6–311 + + g (d, p) and B3LYP / 6 − 31 + + g (d) and PM3 obtained the best results with a deviation of less than 0.6%, which label such fuel with a better choice to be used in the combustion chamber of the engine, whether by ignition or compression.

In terms of delay, there was a better process of prolonged combustion frequency, it was observed that the ramifications of its isomers had a preponderant factor, making combustion more extensive due to the greater energy employed for its rupture to occur, directly reflecting a better combustion efficiency.

Table 3

Percentage deviation of the combustion enthalpy with the experimental values of the propanol isomers.
propan-1-ol			propan-2-ol		2-methylpropan-1-ol		2-methylpropan-2-ol
Functional	Deviation (%)		Functional	Deviation (%)	Functional	Deviation (%)	Functional	Deviation (%)
B3LYP/6-311 + + g(d,p)		0.493	B3LYP /6-311 + + g(d,p)	1.530	B3LYP / 6-311 + g(d)	0.322	B3LYP /6-311 + + g(d,p)	2.648
B3LYP/6-311 + g(d)		0.611	B3LYP /6-311 + g(d)	1.397	B3LYP /6-311 + g(d)	0.203	B3LYP /6-311 + g(d)	2.553
PM3		1.566	PM3	1.552	PM3	0.590	PM3	0.8977

The burning of fuels requires a good relationship between these fuels and the enthalpy developed in the interaction that occurs in the engine, influencing its pistons and consequently their intake, compression, explosion, and exhaust. The values of their combustion described in the literature are shown in Table 4.

Previous understandings on this subject reported that the length of a carbon chain involving all functional groups as described here also obtained a decrease in the delays in their ignitions, which is a positive impact factor for the understanding of their compositions. Evaluate the individual effects of linear isomers: propan-1-ol, propan-2-ol, and branched: 2-methyl-propan-1-ol, 2-methyl-propan-2-ol on the properties of mixtures in gasoline, diesel, and kerosene, in proportions of up to 100%.

Table 4

Enthalpy of combustion with the experimental values arranged for gasoline, diesel, and kerosene fuels.
Fuel	H_c (kj/g)	References	Calorific Value (MJ/kg)	References
Gasoline	47.30	[112]	43.92–46.50	[125]
Kerosene	46.20	[123]	43,11	[126]
Diesel	44.80	[124]	43.70	[127]

The results of the combustion characteristics developed theoretically are shown in Table 4. They are presented and discussed for mixtures (0–100%) of alcohol / Gasoline, Diesel, and Kerosene. These results were analyzed under conditions of low and high proportions of propanols at the temperature of 298.15K because they have a good mixture, thus involving a better absorption taking into account the polarity with these fuels.

We obtained a direct influence on the mixture, air/fuel, we can thus observe that all propanol molecules and their isomers had a performance of reduction at the rate of additions on average of 10% over the analysis of their Hc of propanols added to gasoline, diesel, and kerosene. Thus, through a longer interaction time, it is possible to differentiate the performance that each molecule exerted on fossil fuels in conditions of low and high load, Fig. 9.

The longer chain propanols, such as 2M1P and 2M2P, have a higher number of hydrogens and can improve the quality and premixed combustion phase. They cause a delay in the ignition temperature, allowing for better air/fuel mixture and improved gas combustion phase when mixed with traditional fuels.

In Fig. 9, the order of ignition delay and reactivity throughout the combustion process is as follows (from smallest to largest): iP, nP, 2M1P, and 2M2P. This order is correlated with their ignition properties, taking into account the number of ketones, octane, and methyl groups present in these alcohols when added to fossil fuels, affecting the spread of laminar flames, ignition, and formed species.

When propanols and their isomers are added to gasoline, diesel, and kerosene in proportions ranging from 0 to 100%, all combustible alcohols show a reduction in their enthalpies. However, they still have lower energy values than pure fossil fuels. The reduction in fossil fuel usage increases the number of octanes and reduces emissions, leading to better commercial acceptability.

Experiments involving n-Propanol and 2M1P/2M2P molecules mixed with gasoline and diesel were carried out, and theoretical chemical kinetic models were proposed to promote combustion chemistry in these mixtures. The use of propanol and its isomers in mixtures of up to 30% with fossil fuels was considered viable for commercial use, comparable to ethanol and methanol proportions in fossil fuels. Comparing the fuels' energy release after complete combustion, it was observed that 2M2P had the highest ignition temperature and delay due to its branching structure, resulting in slow isomerization. 2M2P also had the highest energy per unit weight when added to gasoline, followed by kerosene and diesel.

The use of G2M2P30, a mixture with 30% 2M2P, showed a reduction in energy variation per unit mass compared to pure hydrocarbons in gasoline, diesel, and kerosene. However, diesel with 30% 2M2P had the lowest energy variation when compared to other mixtures. The partial substitution of fossil fuels with propanol alcohols directly affects gas emissions and the environment. In conclusion, the study suggests that propanol alcohols, particularly 2M2P, have potential as additives in gasoline, diesel, and kerosene, providing better combustion properties and reducing the dependence on fossil fuels.

Propanol alcohols and their isomers, after being added in mixtures to petroleum derivatives (such as gasoline, diesel, and kerosene) [132, 133], were proposed and combined for analysis on their thermodynamic perspective by evaluating their combustion enthalpies with commercial alcohols ethyl (ethanol) and methyl (methanol) also added to fossils, with the same proportions of mixtures as shown in Fig. 11.

We can see how the alcohol family affected the combustion enthalpy in both gasoline, diesel, and kerosene, with the difference being the smallest to the largest mixed alcohol, expressed in methanol, ethanol, propan-1-ol, and propan-2-ol with the same values followed by 2-methyl-propan-1-ol and 2-methyl-propan-2-ol.

Regarding their delays in ignition temperatures, methanol obtained the lowest value and 2M2P the highest, it is plausible to better understand the enthalpy of combustion when analyzing the length of the carbon chain in these variations of alcohols was of fundamental importance, thus paying attention to the greater carbon number and its ramifications had a better energetic performance reflecting in better combustion.

The gaseous propellant formulated from the alcohol family demonstrated how ethanol obtained better use of energy in its gaseous combustion phases than methanol, which is why it is preferred by the market in addition to being an organic molecule with its production being on a large scale, with the same percentage by weight added up to 100% as fuel agents.

It was observed that the combustion enthalpy using 2M2P alcohol contained a very sharp loss when compared to the other alcohols when it comes to their energies while their fractions increased over pure fossil fuels. The methyl radical as well as its carbonic properties and structures in greater quantity present in these branched molecules demonstrated to be an association with more robust characteristics, formed a structural compound that makes them a more efficient thermal beat agent involving their kinetic and thermal energies for heat production.

This study focused on the theoretical investigation of propanol compounds and their isomers mixed with gasoline, diesel, and kerosene, aiming to assess their quality and efficiency as alternative fuels using quantum chemistry-based computational methods. The results showed reasonable agreement between theoretical and experimental values for all test conditions, with propanol isomers exhibiting promising reactions for combustion. The B3LYP 6-311 + + g (d, p) base was found to be the most suitable for accurately predicting the thermodynamic properties of linear propanols, while branched propanol isomers acted as retardants in combustion, with higher heat capacity and energy absorption capacities.

The Gibbs and enthalpy free energy properties indicated a lower tendency for energetic spontaneity and delayed work within an engine, but also demonstrated higher energy absorption capacities, making the isomers more efficient when combined with other fuel sources. Computational techniques proved effective in providing a close and detailed analysis of thermodynamic data, validating the theoretical findings against experimental results.

Given the efficient combustion energy and potential of propanol and its isomers, they could serve as probable substitutes, similar to ethanol, with potential incentives and government support for sustainable biofuels driving their adoption in the energy sector. These findings highlight the significance of computational methods in facilitating theoretical analyses that align closely with experimental observations, paving the way for the future use of propanol-based mixtures as a viable alternative in the fuel industry.The present study also clarified how the potential and use of computational techniques shortened the entire process to arrive at a theoretical analysis that lives up to the experimental one, showing very close and detailed deviations involving its thermodynamic data.

It is for these and other reasons that propanol and its isomers may be a probable substitute, just as ethanol has been in the past, due to obtaining intensive incentives, subsidized by the government through programs that encourage the use of sustainable biofuels and may also gain a prominent space in the energy sector.

Conflict of interests

The authors of the article entitled "Thermodynamic properties of propanol using DFT in the gas phase", submitted to the Journal of Molecular Modeling, declare that they have no conflict of interest that could influence or bias the research, analyzes or results presented in this work. There are no financial, personal, or professional ties with third parties, institutions or organizations that could create a conflict of interest in relation to the content of this article.

We reiterate that all aspects of this research were conducted ethically and impartially, in accordance with the standards and guidelines established by the scientific community.

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Thermodynamic properties of propanol using DFT in the gas phase

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1. Introduction

2. Materials and Methods

Materials

2.2. Methods

3. Results and discussion

3.1 Molecular Mechanics Simulations

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