A binary mixture proportioning optimization method based on excess viscous flow activation Gibbs free energy and application thereof

Abstract

The application provides a binary mixture ratio optimization method based on excess viscous flow activation Gibbs free energy and application thereof. Based on Eyring theory, the concept of excess viscous flow activation Gibbs free energy (Delta G ≠E ) is proposed, and according to the first law of thermodynamics, the key thermodynamic functions of excess viscous flow activation entropy (Delta S ≠E ) and excess viscous flow activation enthalpy (Delta H ≠E ) are further obtained. Delta G ≠E is obtained by measuring the density and viscosity of the binary mixture system, and the best ratio of the system is screened through the relationship between Delta G ≠E and the mole fraction of the components. The method breaks through the limitations of traditional ratio screening relying on single property, experience trial and error or statistical optimization, and realizes scientific, accurate and universal ratio optimization. The application is suitable for ratio optimization of various binary mixtures (such as solvent-solvent, ionic liquid-water, DES-water, etc.), and has wide application prospect and important guiding value in many fields such as drug delivery, biomass treatment, extraction separation, catalytic reaction, etc.

Description

Technical Field

[0001] This invention belongs to the fields of thermodynamic analysis technology and functional application technology, specifically relating to a method for screening the proportions of binary mixtures based on thermodynamic theory, and particularly to a method for activating Gibbs free energy (ΔG) using excess viscous flow. G ≠E Using density and viscosity data as the core criterion, a thermodynamic method for screening the optimal ratio of various binary mixtures is achieved by combining systematic measurement of density and viscosity data with RK equation fitting, and its application in the field of surfactant solubilization is also discussed. Background Technology

[0002] Eutectic solvents (DES), as an emerging class of green solvents, have shown great application potential in various fields such as extraction and separation, catalysis, and electrochemistry. However, their high viscosity often limits practical flow and mass transfer processes, and their performance is usually adjusted by compounding with water. The performance of the compounded system is strongly dependent on the ratio of its components; improper ratio selection may lead to microstructural imbalance, unstable phase behavior, or functional failure. Therefore, developing a scientific, universal, and mechanistically sound ratio selection method is crucial for optimizing the performance and engineering applications of compounded solvent systems.

[0003] Currently, common formulation screening methods are mostly based on determining the maximum or minimum value of a single physical property (such as viscosity), or using statistical methods such as orthogonal experiments and response surface methodology for optimization. While these methods have some practicality, they have significant shortcomings: on the one hand, they rely on a large number of gradient experiments, which are cumbersome, time-consuming, and labor-intensive, resulting in long screening cycles and low efficiency; on the other hand, they lack a thermodynamic understanding of the microscopic interactions and structural evolution of the system, and the screening results are often limited to specific systems or conditions, making it difficult to reveal the essential relationship between formulation, structure, and performance, let alone extend to multi-component systems composed of different components.

[0004] Excess viscous flow activation Gibbs free energy (Δ) G ≠E Δ is an important thermodynamic function characterizing intermolecular interactions and structural rearrangements during liquid flow. Its value directly reflects the degree to which the mixed system deviates from ideal flow behavior and can sensitively capture the microenvironment and structural transformations caused by changes in component ratios. However, to date, no systematic research has established a method based on Δ... G ≠E A generalized, mechanism-driven ratio screening method was developed and extended to the optimization design of different types of binary mixture systems.

[0005] To address the aforementioned problems, this invention proposes for the first time to use Δ G ≠EA universal thermodynamic screening strategy with the core criterion. This method only requires measuring the density and viscosity of the binary mixture at different temperatures and calculating the excess viscous flow activation Gibbs free energy (ΔG). G ≠E The minimum value corresponds to the optimal ratio. This minimum value signifies that the intermolecular interactions within the system have reached a thermodynamically favorable equilibrium state, the original structure is moderately modulated, and a new interaction network is established, thereby optimizing the overall performance at the microscopic level, rather than merely improving macroscopic fluidity. Furthermore, based on the first law of thermodynamics, the activation excess entropy (Δ) of viscous flow is obtained. S ≠E ) and viscous flow activation excess enthalpy (Δ H ≠E Key thermodynamic functions. This invention not only provides a precise and efficient ratio screening scheme for DES-water systems, but more importantly, it constructs a universal thermodynamic screening method applicable to ratio optimization of various binary mixture systems, which has significant theoretical foresight and broad industrial application value. Summary of the Invention

[0006] The purpose of this invention is to provide a scientifically accurate and easy-to-operate method for screening the optimal ratio of binary mixtures, and to apply it in the field of solubilization. This addresses the problems of existing DES aqueous solution ratio screening methods lacking thermodynamic theoretical support and exhibiting insufficient performance stability.

[0007] The technical solution adopted in this invention is:

[0008] A method for optimizing the sizing of a binary mixture system based on the activation Gibbs free energy of excess viscous flow includes the following steps:

[0009] S1) Prepare a binary mixture system covering the entire mole fraction range, wherein the binary mixture system is a component-solvent binary mixture system;

[0010] S2) Under a pressure of 0.1 MPa, the density and viscosity of the binary mixture at different temperatures were measured in the temperature range of 298.15 K to 318.15 K.

[0011] S3) Calculate the excess viscous flow activation Gibbs free energy Δ based on the density and viscosity measured in step S2). G ≠E , through Δ G ≠E Fitting the RK equation to the mole fraction of the components, plotting Δ at different temperatures. G ≠E The relationship curve between the component mole fraction and the stoichiometric ratio is used to determine the optimal ratio of the binary mixture system, expressed as Δ. G ≠EThe minimum value corresponds to the optimal ratio;

[0012] Among them, the excess viscous flow activation Gibbs free energy Δ G ≠E Calculated using formula (6):

[0013] (6);

[0014] In the formula: Δ G ≠E The activation Gibbs free energy for excess viscous flow is kJ·mol⁻¹. -1 ; R =8.314 J·K -1 ·mol -1 , where is the gas constant; T K represents absolute temperature. or r ρ represents the relative viscosity of the binary mixture, in mPa·s; V The average molar volume of the binary mixture is given in cm³. 3 ·mol -1 ; x 1. x 2 represents the mole fraction of the component and the solvent, respectively; V 1 0 , V 2 0 The average molar volumes of the components and solvent are shown in cm. 3 ·mol -1 ;

[0015] The average molar volume of the binary mixture system V Calculated using formula (1):

[0016] (1);

[0017] In the formula: M1 and M2 are the molar masses of the component and solvent, respectively, in g·mol⁻¹. -1 ; r The density of the binary mixture is given in g·cm³. -3 ;

[0018] The relative viscosity of the binary mixture system or r Calculate using formula (2):

[0019] (2);

[0020] In the formula: or The viscosity of the binary mixture is given in mPa·s. or 1. or2 represents the viscosity of the component and the solvent, respectively, in mPa·s.

[0021] Furthermore, in the above-mentioned method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow, in step S1), the total mole fraction range is the component... x 1 = 0.0000~1.0000.

[0022] Furthermore, in the above-mentioned method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow, the binary mixture system is selected from one of the following: solvent 1-solvent 2, ionic liquid-water, or eutectic solvent DES-water binary mixture system.

[0023] Preferably, the binary mixture system is a eutectic solvent DES-water binary mixture system.

[0024] Furthermore, the synthesis method of the DES is as follows: choline chloride, a hydrogen bond acceptor, is mixed with a hydrogen bond donor in a 1:1 molar ratio and refluxed in an oil bath at 69–71°C for 11.5–12.5 hours.

[0025] Preferably, the hydrogen bond donor is selected from ethylene glycol, propylene glycol, and glycerol, all with a purity of 99.9% or higher; and the choline chloride has a purity of 99.5% or higher.

[0026] Furthermore, in the above-mentioned method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow, in step S2), the density is measured using a DMA4500M densitometer, calibrated with anhydrous ethanol of 99.7% purity or higher before measurement; the viscosity is measured using a Lovis 2000ME viscometer, with a capillary tube of 1.59 mm or 1.80 mm diameter selected according to the viscosity range of the system; all measurement data are the average of three parallel experiments, with a relative standard deviation ≤0.3%.

[0027] Furthermore, the aforementioned method for optimizing the sizing of a binary mixture system based on the activation Gibbs free energy of excess viscous flow further includes step S4): based on the calculated Δ... G ≠E The values ​​are further derived to identify the activation excess entropy and activation excess enthalpy of viscous flow. The calculation formulas are as follows:

[0028] (8);

[0029] (9);

[0030] In the formula: Δ S ≠E For viscous flow, the activation excess entropy is kJ·K-1 ·mol -1 ;Δ H ≠E The excess enthalpy for activation of viscous flow is kJ·mol⁻¹. -1 ; T The absolute temperature is (K).

[0031] By examining Δ simultaneously G ≠E Δ S ≠E With Δ H ≠E This study reveals the behavioral mechanism of the system's mixing process from two dimensions: energy and entropy effects.

[0032] Furthermore, the aforementioned method for optimizing the proportions of a binary mixture based on the activation Gibbs free energy of excess viscous flow results in a binary mixture system with a stable molecular interaction network and a suitable solution microenvironment within a temperature range of 298.15 K to 318.15 K.

[0033] The optimal binary mixture system selected by the binary mixture system ratio optimization method based on the excess viscous flow activation Gibbs free energy described above can be applied in surfactant solubilization, drug carrier, biomass treatment, extraction separation or catalytic reaction.

[0034] The beneficial effects of this invention are:

[0035] 1. This invention is the first to propose an activation Gibbs free energy (Δ) based on excess viscous flow. G ≠E This generalized thermodynamic screening method overcomes the limitations of traditional proportioning optimization, which relies on empirical trials or single property extrema. Further analysis of Δ... H ≠E With Δ S ≠E This study fully reveals the thermodynamic essence of the relationship between proportion, structure, and performance from the perspective of energy and entropy synergy, providing a solid theoretical foundation for the rational design of binary hybrid systems.

[0036] 2. This method only requires the systematic determination of the density and viscosity of the binary system at different temperatures. It can then achieve rapid and accurate proportioning screening using Eyring theory, and is applicable to various binary mixtures, including eutectic solvent-water and ionic liquid-organic solvent systems. The instruments used are conventional, the procedures are standardized, and it possesses good repeatability and scalability.

[0037] 3. With Δ G ≠EThe minimum value is used as a criterion, which can sensitively identify the optimal balance point between microscopic interactions and structural transformations in a system, avoiding misjudgments caused by fluctuations in macroscopic properties. The screening results have both thermodynamic rationality and structural stability, significantly improving the scientificity and reliability of ratio optimization.

[0038] 4. The optimal formulation system obtained using the optimization method of this invention exhibits excellent performance improvement potential in fields such as surfactant solubilization, drug delivery, biomass treatment, extraction and separation, and catalytic reactions. Taking the eutectic solvent (DES)-water system as an example, the optimal formulation screened using this method achieves structural reconstruction of the hydrogen bond network, which not only significantly reduces the system viscosity but also reduces the critical micelle concentration (CMC) by up to 88% in surfactant solubilization applications, greatly improving process efficiency and reducing costs. It has significant engineering guidance value and promising prospects for industrial application. Attached Figure Description

[0039] Figure 1 The graphs show the relationship between the excess viscous flow activation Gibbs free energy and mole fraction for different DES-water mixtures in the temperature range of 298.15 K to 318.15 K, where (A) DES1 (1ChCl:2EG) + water; (B) DES2 (1ChCl:2PG) + water; (C) DES3 (1ChCl:2Gly) + water.

[0040] Figure 2 Taking the binary mixture system of DES1 (1ChCl:2EG) + water as an example, the CMC values ​​of the surfactant [C6MOAmim][Br] under different ratios of DES and aqueous solution at temperatures ranging from 298.15K to 318.15K are analyzed. (A) x 1 = 0.00; (B) x 1 = 0.15; (C) x 1 = 0.40.

[0041] Figure 3 The linear relationship between absorbance and concentration (c) of cypermethrin in different DES-water systems with ionic liquid surfactants at a certain concentration was determined at 298.15 K. Detailed Implementation

[0042] To further understand the present invention, preferred embodiments of the present invention will be described below with reference to examples.

[0043] To address the shortcomings of existing binary mixture formulation screening methods, which rely on empirical trials, are cumbersome, and time-consuming, this invention proposes a novel screening method based on thermodynamic mechanisms: the activation Gibbs free energy (ΔGb) of excess viscous flow. G ≠EAs a core thermodynamic parameter characterizing the relationship between the strength of intermolecular interactions and flow behavior in a mixed system, Δ is able to accurately describe the structural features and intermolecular synergistic effects of the system at the microscopic scale. This method obtains Δ by measuring the density and viscosity data of a DES-water binary mixture across the entire molar concentration range. G ≠E and with Δ G ≠E The minimum value corresponds to the optimal ratio. This ratio system exhibits a stable microstructure, optimizes and reconstructs the solution microenvironment, and is more conducive to molecular mass transfer and interfacial activity regulation. In practical applications, it can significantly improve performance; for example, it can significantly reduce the critical micelle concentration (CMC) of surfactants in pesticide solubilization. The following detailed description of the technical solution of this invention, in conjunction with specific embodiments, further illustrates this invention.

[0044] Example 1

[0045] (I) Synthesis of DES

[0046] Three portions of hydrogen bond acceptor choline chloride (purity 99.5%) were mixed with hydrogen bond donors ethylene glycol, propylene glycol, and glycerol (purity 99.9%) in a 1:1 molar ratio. The mixtures were then added to three-necked flasks equipped with magnetic stirrups. The oil bath temperature was set at 70°C, and the mixtures were refluxed for 12 hours to obtain three transparent and homogeneous DES (DES1: choline chloride-ethylene glycol; DES2: choline chloride-propylene glycol; DES3: choline chloride-glycerol).

[0047] (II) Preparation of DES-water mixing system

[0048] For DES1, DES2, and DES3, molar fractions x A gradient of 1 = 0.0000, 0.1000, 0.2000, 0.3000, ..., 1.0000 was used. The DES and deionized water synthesized in Example 1 were accurately weighed and added to 50 mL wide-mouth plastic bottles respectively. After sealing, the bottles were placed on a magnetic stirrer and stirred for 2.5 hours to obtain a uniform DES-water mixture with a full molar concentration range. No stratification was observed after standing.

[0049] (III) Determination of physicochemical properties

[0050] Under a pressure of 0.1 MPa, the density and viscosity of three series of mixed systems were measured at different temperatures (298.15 K, 303.15 K, 308.15 K, 313.15 K, and 318.15 K) within the temperature range of 298.15 K to 318.15 K using a DMA 4500M densitometer and a Lovis 2000 MEI viscometer. The DMA4500M densitometer was calibrated with anhydrous ethanol (99.7% purity) before measurement; for the Lovis 2000ME viscometer, a capillary tube with a diameter of 1.59 mm or 1.80 mm was selected according to the viscosity range of the system. All measurement data are the average of three parallel experiments, with a relative standard deviation ≤0.3%. The results show that the relative deviation between the experimental data and the literature values ​​is less than 0.5%, indicating that the data are reliable.

[0051] Table 1. Taking a binary mixture of DES1 (1ChCl:2EG) and water as an example, at temperatures T = (298.15~318.15) K, the concentration range across the entire range... x Density of 1 r (g·cm) -3 Value and viscosity or (mPa·s) value

[0052]

[0053] (iv) Δ G ≠E Calculation and Optimal Formulation Screening

[0054] Based on the measurement data in Table 1, the average molar volume and relative viscosity of each of the three series of mixtures were calculated, and the excess viscous flow activation Gibbs free energy (Δ) was calculated. G ≠E ). Through Δ G ≠E Fitting the RK equation to the mole fraction of DES, plotting Δ at different temperatures. G ≠E The relationship curve between the mole fraction of DES and water. Determining the optimal ratio of the DES-water binary mixture system, expressed as Δ... G ≠E The minimum value corresponds to the optimal ratio.

[0055] Excess viscous flow activation Gibbs free energy (Δ) G ≠E The following calculation process is used to obtain the result:

[0056] First, the average molar volume of the binary mixture system V Calculated using formula (1):

[0057] (1);

[0058] In the formula: V The average molar volume (cm³) of the binary mixture system 3 ·mol -1 ); x 1. x 2 represents the mole fraction of the component and the solvent, respectively; M1 and M2 represent the molar masses (g·mol⁻¹) of DES and water, respectively. -1 ); r The density (g·cm³) of the binary mixture system -3 ).

[0059] Secondly, relative viscosity is introduced ( or r The correlation between viscosity and intermolecular forces is as follows: Relative viscosity is defined as the ratio of the actual viscosity of a mixture to the ideal viscosity of the mixture, as shown in the following formula:

[0060] (2);

[0061] In the formula: or r The relative viscosity (mPa·s) of the binary mixture system. or The actual viscosity (mPa·s) of the binary mixture system. or 1. or 2 represents the viscosity (mPa·s) of DES and water, respectively. x 1. x 2 represents the mole fractions of DES and water, respectively. When or r When the value is less than 1, it indicates that the intermolecular interaction between DES and water is weakened, and the viscosity of the mixed system decreases.

[0062] The viscous flow characteristics of quasi-binary mixtures of eutectic solvents and water follow Eyring's liquid viscosity theory, and the viscosity expression for the actual mixture is:

[0063] (3);

[0064] The viscosity expression for an ideal mixture (with no additional intermolecular interactions) is:

[0065] (4);

[0066] In the formula: h Planck constant (6.626 × 10⁻⁶) -34 J·s), N A For Avogadro's constant (6.022 × 10⁻⁶), 23 mol -1 ),V The average molar volume (cm³) of the binary mixture system 3 ·mol -1 ), V 0 = x 1 V 1 0 + x 2 V 2 0 ( V 1 0 and V 2 0 (representing the average molar volume of DES and water, respectively). T The absolute temperature is K. R The representative gas constant (8.314 J·K) -1 ·mol -1 ), Δ G ≠ This represents the activation Gibbs free energy (kJ·mol⁻¹) of viscous flow during actual mixing. -1 ), Δ G ≠0 Gibbs free energy (kJ·mol) represents the activation energy of viscous flow under ideal mixing. -1 ).

[0067] Furthermore, combining the definition of relative viscosity (Equation 2) with the Eyring theoretical expressions (Equations 3 and 4), we obtain:

[0068] (5);

[0069] According to the definition of the excess function, Δ G ≠ – Δ G ≠0 This is the excess viscous flow activation Gibbs free energy (Δ). G ≠E Substituting into Formula 5, and further, after rearranging terms, the final calculation formula is:

[0070] (6);

[0071] In the formula: Δ G ≠E The activation Gibbs free energy (kJ·mol) for excess viscous flow -1 ), R The gas constant is 8.314 J·K. -1 ·mol -1 T represents absolute temperature (K). or r The relative viscosity (mPa·s) of the binary mixture system.V The average molar volume (cm³) of the binary mixture system 3 ·mol -1 ), x 1. x 2 represents the mole fractions of DES and water, respectively. V 1 0 , V 2 0 The average molar volumes (cm³) of DES and water are respectively. 3 ·mol -1 ).

[0072] The above Δ G ≠E The calculation method is used to screen for the optimal ratio, where different mole fractions are calculated using Formula 6. x 1) Δ of the mixed system G ≠E , with Δ G ≠E The vertical axis is , x Plotting x1 on the x-axis, the minimum value of the curve corresponds to x1, which is the optimal ratio of DES to water (e.g., ...). Figure 1 At this ratio, the original hydrogen bond network inside DES is moderately weakened, forming a new hydrogen bond structure with water molecules that facilitates flow, resulting in the lowest system viscosity and the best flowability.

[0073] Furthermore, to further elucidate the microscopic mechanism of the system under optimal proportions, we can base our analysis on the obtained Δ... G ≠E Further derivation of the value of viscous flow activation excess entropy (Δ) S ≠E ) and viscous flow activation excess enthalpy (Δ H ≠E The calculation formula is as follows:

[0074] (7);

[0075] (8);

[0076] (9);

[0077] Where, Δ G ≠E The activation Gibbs free energy (kJ·mol) for excess viscous flow -1 ), reflecting the degree to which the system deviates from the ideal mixing and flow state; Δ H ≠E The activation excess enthalpy (kJ·mol) for viscous flow -1 ), characterizing the change in intermolecular interaction energy during the mixing process; ΔS ≠E Activating excess entropy (kJ·K) for viscous flow -1 ·mol -1 This reflects the structural orderliness of the system and the changes in the degrees of freedom of molecular motion; T The absolute temperature is (K). This is determined by simultaneously considering Δ... G ≠E Δ H ≠E With Δ S ≠E This study can fully reveal the flow behavior mechanism of the mixed system from the two dimensions of energy and entropy effect, clarify the thermodynamic essence of microstructure recombination and molecular environment adaptation corresponding to the optimal ratio, and further enhance the theoretical depth and guiding value of ratio screening.

[0078] Figure 1 The results show:

[0079] DES1 (choline chloride-ethylene glycol) - water at all temperatures Δ G ≠E Minimum value corresponds to x 1 = 0.15~0.16;

[0080] DES2 (choline chloride-propylene glycol) - water at all temperatures Δ G ≠E Minimum value corresponds to x 1 = 0.14~0.15;

[0081] DES3 (choline chloride-glycerol) - water at all temperatures Δ G ≠E Minimum value corresponds to x 1 = 0.14~0.15.

[0082] The optimal ratio of eutectic solvent-water solution obtained through the above screening forms a stable intermolecular interaction network and an optimized solution microenvironment within the range of 288.15K to 318.15K. Its microstructure is conducive to molecular mass transfer and energy transfer.

[0083] As shown in Table 2, with the increase of mole fraction, the viscous flow activation excess entropy (Δ) of the mixture increases. S ≠E ) and viscous flow activation excess enthalpy (Δ H ≠E All showed an upward trend; at the same time, it can be found that the activation excess enthalpy (Δ) of viscous flow increased. H ≠E The value of ) is less than the product of temperature and viscous flow activation excess entropy ( T Δ S ≠EThis result indicates that the decrease in the viscosity of the mixture is mainly dominated by the activation enthalpy change of viscous flow.

[0084] Table 2. Thermodynamic parameter values ​​(excess viscous flow activation Gibbs free energy Δ) of the DES1(1ChCl:2EG)-water binary mixture system as an example. G ≠E (kJ·mol) -1 ), viscous flow activation excess enthalpy Δ H ≠E (kJ·mol) -1 The product of temperature and viscous flow activation excess entropy, TΔ S ≠E (kJ·mol) -1 ) and viscous flow activation excess entropy Δ S ≠E (kJ·K) -1 ·mol -1 ))

[0085]

[0086] Example 2: Verification of the solubilization application of the optimally proportioned binary mixture system

[0087] Taking DES1 (choline chloride-ethylene glycol) as an example, its optimal ratio system was selected ( x 1=0.15), pure aqueous solution ( x A non-optimal system with 1=0.00 (non-optimal ratio) and DES molar fraction of 0.40 was used as a solvent to disperse the same surfactant (1-hexyl-2-methyl-3-hexanoic acid imidazole bromide [C6MHAmim][Br]). The CMC value of the surfactant in each system was determined by the surface tension-density method under the same conditions.

[0088] like Figure 2 Experimental results show that the optimal ratio system for DES1 ( x The CMC of the surfactant in (1=0.15) is 0.0001 mol·kg⁻¹. -1 Compared to the DES1 system with a mole fraction of 0.00, the CMC is 0.0009 mol·kg⁻¹. -1 It was reduced by 88%; and compared to the system with a DES1 mole fraction of 0.40, the CMC was 0.00027 mol·kg⁻¹. -1 The ratio was reduced by 63%. The results show that the optimal ratio system screened by activating Gibbs free energy through excess viscous flow exhibits excellent performance in practical applications, proving that the optimal ratio screening method of this invention has significant advantages.

[0089] Furthermore, using the poorly soluble pesticide cypermethrin as a model solute, the solubilizing ability of the optimal formulation system was verified. Figure 3 As shown, cypermethrin has extremely low solubility in pure water (0.000005 g·L⁻¹). -1 At low concentrations of surfactant (0.002 mol·kg⁻¹) -1 In the presence of DES, the solubility of cypermethrin significantly increased with the introduction of DES: 38,540 times that of pure water in a pure water system; 44,260 times in a solution with a DES molar fraction of 0.4%; and reaching a maximum of 49,080 times when the DES molar fraction was 0.15%. These data indicate that the optimal DES-water system ratio selected by the method of this invention can effectively enhance the solubilizing effect of surfactants, further confirming the practical value and superiority of this ratio optimization method.

[0090] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for optimizing the sizing of a binary mixture system based on the activation Gibbs free energy of excess viscous flow, characterized in that, Includes the following steps: S1) Prepare a binary mixture system covering the entire mole fraction range, wherein the binary mixture system is a component-solvent binary mixture system; S2) Under a pressure of 0.1 MPa, the density and viscosity of the binary mixture at different temperatures were measured in the temperature range of 298.15 K to 318.15 K. S3) Calculate the excess viscous flow activation Gibbs free energy Δ based on the density and viscosity measured in step S2). G ≠E , through Δ G ≠E Fitting the RK equation to the mole fraction of the components, plotting Δ at different temperatures. G ≠E The relationship curve between the component mole fraction and the stoichiometric ratio is used to determine the optimal ratio of the binary mixture system, expressed as Δ. G ≠E The minimum value corresponds to the optimal ratio; Among them, the excess viscous flow activation Gibbs free energy Δ G ≠E Calculated using formula (6): （6）； In the formula: Δ G ≠E The activation Gibbs free energy for excess viscous flow is kJ·mol⁻¹. -1 ; R =8.314 J·K -1 ·mol -1 , where is the gas constant; T K represents absolute temperature. η r ρ represents the relative viscosity of the binary mixture, in mPa·s; V The average molar volume of the binary mixture is given in cm³. 3 ·mol -1 ; x 1. x 2 represents the mole fraction of the component and the solvent, respectively; V 1 0 , V 2 0 The average molar volumes of the components and solvent are shown in cm. 3 ·mol -1 ; The average molar volume of the binary mixture system V Calculated using formula (1): （1）； In the formula: M1 and M2 are the molar masses of the component and solvent, respectively, in g·mol⁻¹. -1 ; ρ The density of the binary mixture is given in g·cm³. -3 ; The relative viscosity of the binary mixture system η r Calculate using formula (2): （2）； In the formula: η The viscosity of the binary mixture is given in mPa·s. η 1, η 2 represents the viscosity of the component and the solvent, respectively, in mPa·s.

2. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow as described in claim 1, characterized in that, In step S1), the total mole fraction range is the component x 1 = 0.0000~1.0000.

3. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow as described in claim 1, characterized in that, The binary mixture system is selected from one of the following: solvent 1-solvent 2, ionic liquid-water, and eutectic solvent DES-water binary mixture system.

4. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow as described in claim 3, characterized in that, The binary mixture system is a eutectic solvent DES-water binary mixture system.

5. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow according to claim 4, characterized in that, The synthesis method of DES is as follows: choline chloride, a hydrogen bond acceptor, is mixed with a hydrogen bond donor in a 1:1 molar ratio and refluxed in an oil bath at 69–71°C for 11.5–12.5 hours.

6. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow according to claim 5, characterized in that, The hydrogen bond donor is selected from one of ethylene glycol, propylene glycol, and glycerol, all with a purity of 99.9% or higher; the choline chloride has a purity of 99.5% or higher.

7. The method for optimizing the sizing of a binary mixture system based on the activation Gibbs free energy of excess viscous flow according to claim 1, characterized in that, In step S2), the density was measured using a DMA4500M densitometer, calibrated with anhydrous ethanol of 99.7% or higher purity before measurement; the viscosity was measured using a Lovis 2000ME viscometer, with a capillary tube of 1.59 mm or 1.80 mm diameter selected according to the viscosity range of the system; all measurement data are the average of three parallel experiments, with a relative standard deviation ≤0.3%.

8. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow according to claim 1, characterized in that, The method further includes step S4): based on the calculated Δ G ≠E The values ​​are further derived to identify the activation excess entropy and activation excess enthalpy of viscous flow. The calculation formulas are as follows: （8）； （9）； In the formula: Δ S ≠E For viscous flow, the activation excess entropy is kJ·K -1 ·mol -1 ;Δ H ≠E The excess enthalpy for activation of viscous flow is kJ·mol⁻¹. -1 ; T The absolute temperature is (K). By examining Δ simultaneously G ≠E Δ S ≠E With Δ H ≠E This study reveals the behavioral mechanism of the system's mixing process from two dimensions: energy and entropy effects.

9. The method for optimizing the proportions of a binary mixture system based on the activation Gibbs free energy of excess viscous flow according to claim 1, characterized in that, The binary mixture system exhibits a stable molecular interaction network and a suitable solution microenvironment within the temperature range of 298.15K to 318.15K.

10. The application of the optimal binary mixture system selected by the binary mixture system ratio optimization method based on the activation Gibbs free energy of excess viscous flow as described in any one of claims 1-9 in surfactant solubilization, drug carrier, biomass treatment, extraction separation or catalytic reaction.

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