Energetics and structure of the hydrated gaseous halide anions

Energetics and geometries for the hydrated gaseous halide anions have been computed from a simple model in which the molecular dipole of water was composed of two parts, one due to a lone pair on oxygen (60%) and the rest to formal charges on the nuclei. The calculations were made for both the symmetric and nonsymmetric structures. A variety of structures were used to compute potential energies and distances with up to six water molecules. The total energy consisted of a sum of electrostatic, polarization, dispersion, and repulsion terms. Various sets of repulsive potential parameters, ranging from those determined from molecular beam experiments to those determined using experimental ion–water distances or energies, have been employed to compute repulsive interaction energies. It was found that the range parameters play a significant role in deciding the magnitudes of the distances and energies, as the latter are most sensitive to them. It was also shown that with a simple correlation scheme the consistency of the experimental energies and distances can be tested separately without using repulsive potential parameters from other sources. It also suggests that a range of parameters can be used to compute repulsion energies. Despite the fact that the model is greatly simplified, the agreement of both the predicted ion-oxygen distances and energies with both experiment and other calculations is excellent. A detailed analysis of our calculation suggests that the negative ion clusters with one to three water molecules contain symmetric orientation of water molecules, while those with more than three may contain asymmetric orientations of water molecules or a mixture of both. From the log–log plots of hydration energies versus (R + radius of water molecule), we have proposed empirical expressions of the type ΔE_n?1,n = 10·0^x (R + 1.38)^?y with both Pauling's and Ladd's radii for univalent ions with which stepwise hydration energies of the latter can be predicted if we know thier radii. The values predicted for the alkali cations are in excellent agreement with the experimental and theoretical values, indicating the consistency of the simple model.     

Conformational Dependence of Triplet Energies in Rotationally Hindered N- and S-Heterocyclic Dimers: New Design and Measurement Rules for High Triplet Energy OLED Host Materials

A series of four heterocyclic dimers has been synthesized, with twisted geometries imposed across the central linking bond by ortho-alkoxy chains. These include two isomeric bicarbazoles, a bis(dibenzothiophene-S,S-dioxide) and a bis(thioxanthene-S,S-dioxide). Spectroscopic and electrochemical methods, supported by density functional theory, have given detailed insights into how para- vs. meta- vs. broken conjugation, and electron-rich vs. electron-poor heterocycles impact the HOMO–LUMO gap and singlet and triplet energies. Crucially for applications as OLED hosts, the triplet energy (E_T) of these molecules was found to vary significantly between dilute polymer films and neat films, related to conformational demands of the molecules in the solid state. One of the bicarbazole species shows a variation in E_T of 0.24 eV in the different media—sufficiently large to “make-or-break” an OLED device—with similar discrepancies found between neat films and frozen solution measurements of other previously reported OLED hosts. From consolidated optical and optoelectronic investigations of different host/dopant combinations, we identify that only the lower E_T values measured in neat films give a reliable indicator of host/guest compatibility. This work also provides new molecular design rules for obtaining very high E_T materials and controlling their HOMO and LUMO energies.     

Recoil properties of radionuclides formed in the photonuclear reactions onnatCu at intermediate energies

The recoil properties of 26 radionuclides produced in the photonuclear reactions on Cu at bremsstrahlung end-point energies (E ₀) of 250 to 1000 MeV have been investigated using the thick-target thick-catcher method. Kinematic properties of the product nuclei were calculated by the two-step vector velocity model. The calculated mean kinetic energies,T, of product nuclei increase with increase of the mass difference between products and target, reflecting the resonance natures and absorption mechanisms. TheT atE ₀≥600 MeV were well reproduced by a calculation performed by PICA code byGabriel andAlsmiller atE ₀=400 MeV, except for (γ,xn) products by giant-resonance.     

Cation–ligand interactions: Reproduction of extended basis set Ab initio SCF computations by the SIBFA 2 additive procedure

In the framework of the additive SIBFA 2 procedure, the intermolecular interaction energy is computed as a sum of five terms: ΔE = E_MTP + E_rep + E_pol + E_CT + E_disp. In order to assess the accuracy of the procedure to compute cation–ligand interactions, the interaction of alkali (Na⁺, K⁺) and alkaline-earth (Mg²⁺, Ca²⁺) cations with two representative ligands H₂O and HCOO^? has been studied and the results compared with those of ab initio SCF extended basis set computations. The additive procedure reproduces very satisfactorily the results of ab initio computations as concerns the numerical values of the interaction energies and the equilibrium cation–ligand distances, as well as the evolution of the energy components. A detailed study of these components at different distances helps, in particular, to delineate the relative weights of the charge-transfer and polarization contributions within the second-order energy.     

Geometry,basis set,and correlation energy dependence of computed protonation energies of imino bases

The nitrogen protonation energies of the imino bases HN?CHR, where R is H, CH₃, NH₂, OH, and F, have been evaluated to determine the dependence of absolute and relative protonation energies on geometry, basis set, and correlation effects. Reliable absolute protonation energies require a basis set larger than a split-valence plus polarization basis, the inclusion of correlation, and optimized geometries of at least Hartree–Fock 4-31G quality. Consistent relative protonation energies can be obtained at the Hartree–Fock level with smaller basis sets. Extending the split-valence basis set by the addition of polarization functions on all atoms decreases the computed absolute Hartree–Fock nitrogen protonation energies of the imino bases HN?CHR except when R is F, but increases the oxygen protonation energies of the carbonyl bases O?CHR.     

Kinetic Parameters of Alkyl,Alkoxy, and Peroxy Radical Isomerization

The parabolic model of radical abstraction reactions is used to analyze experimental data on monomolecular hydrogen-atom transfer in the reactionsRC^.H(CH₂) _n CH₂R¹ RCH₂(CH₂) _n C^.HR¹(n= 2, 3, 4)RCH(O^.)(CH₂)₂CH₂R¹ RCH(OH)(CH₂)₂C^.HR¹ RCH(OO^.)(CH₂) _n CH₂R¹ RCH(OOH)(CH₂) _n C^.HR¹(n= 1, 2).The activation energies and rate constants that specify each class of these reactions are calculated. Alkyl radical isomerization is characterized by the following activation energies of a thermally neutral reaction depending on the cycle size in the transition state (nis the number of atoms in a cycle): E _{e , 0}(kJ/mol) = 46.6 (n= 6), 59.4 (n= 5), and 57.1 (n= 7). Alkoxy radicals isomerize with E _{e , 0}(kJ/mol) = 53.4 (n= 6), whereas peroxy radicals isomerize with E _{e , 0}(kJ/mol) = 53.2 (n= 6) and E _{e , 0}(kJ/mol) = 54.8 (n= 7). The E _{e , 0}value varies with changes in the cycle size and the strain energy in cycloparaffin C _n H_2n in the same manner. The activation energies E _{e , 0}for the intra- and intermolecular H-atom abstractions are compared. It is found that E _{e , 0}(isomerization) < E _{e , 0}(R^.+ R¹H) for alkyl radicals and that E _{e , 0}(isomerization) E _{e , 0}(RO^.(RO^.) + R¹H) for alkoxy and peroxy radicals.     

Critical phenomena in isoelectronic diatomic sequences—the 14-electron sequence

A theory of isoelectronic molecules which describes stable and metastable members of a sequence has been developed. To achieve this synthesis, it has been necessary to require that the total electronic energy surface E(R,Z,Z') for the sequence contain critical points—that is, values of the nuclear charges Z and Z' at which energy minimum, maximum [at R_e(min) and R_e(max)], and horizontal inflection points occur. For ground state sequences a primary physical source of these extreme points is the screened, coulombic repulsion of like-charged atomic centers in the diatomics. With this realization, we can write analytical forms that have the correct scaling behavior and which properly model the screened, coulombic repulsion for E along certain straight-line trajectories in the (Z,Z') plane. This leads to the observation that R_e(max) values diverge logarithmically in λ-like transitions wherever the screened coulombic repulsion becomes small as the nuclear charges vary along those trajectories. At the horizontal inflection points the E surface contains A₂ folds, as required by Thom's theorem for analytical surfaces containing one control parameter. Within the isoelectronic sequence molecular subgroups have been noted and explained in terms of the underlying atomic shell structures of the molecules' constituent atoms. Using input data for seven stable molecules together with the analytical surface selected for study, we have estimated the equilibrium bond distances R_e(min), dissociation energies D_e(min), and harmonic force constants E⁽²⁾(min) for 18 other neutral and charged species.     

Stereoselektive Totalsynthese von natürlichem Phytol und Phytolderivaten und deren Verwendung zur Herstellung von natürlichem Vitamin K1

Steroselective Total Synthesis of Natural Phytol and Derivatives thereof; Use of these Compounds in the Synthesis of Natural Vitamin K₁ The Li₂CuCl₄-catalyzed couplings of the easily accessible bifunctional C₅ allylic acetates (E)- 18a and (E)- 18b with racemic hexahydrofarnesylmagnesium bromide ((3 RS/RS, 7 RS/SR)- 19a ) proceed with high chemo- and stereoselectivity (≥98% (E)-retention) to give the (2E, 7 RS/RS, 11 RS/SR)-phytol derivatives 1a and 1b , respectively, in yields of 72–80% (Scheme 5). The same couplings performed with optically active hexahydrofarnesylmagnesium bromide (3 R, 7 R)- 19a yielded the (E)-phytol derivatives of the natural series (7 R, 11R)- 1a and (7 R, 11 R)- 1b. Acid-catalyzed hydrolysis of(2 E, 7 R, 11 R)- 1b gave natural phytol((2 E, 7 R, 11 R)- 1c ) Friedel-Crafts alkylation of ‘menadiol monobenzoate’ 11b with (2 E, 7 R, 11 R)- 1a or (2 E, 7 R, 11 R)- 1b gave the dihydrovitamine K₁ derivative (2 E/Z, 7′ R, 11′R)- 12b ((E/Z)≈? 9:l). Conversion of configurationally pure (2 E, 7′ R, 11′ R)- 12b (yield 73%; obtained after chromatographic removal of the (Z)-isomer) into natural vitamine K₁ ((2 E,7′ R, 11′ R)- 2 ) was achieved in the usual way by saponification and oxidation with air. Some further investigations of the coupling reactions of bifunctional C₅ allylic synthons with hexahydrofarnesylmagnesium bromide (3 RS/RS, 7 RS/SR)- 19a showed the outcome of these reactions to be critically dependent on the nature of the leaving group, the double-bond geometry and the nature and concentration of the catalyst. Thus, the Li₂CuCl₄-catalyzed couplings of (3 RS/RS,7 RS/SR)- 19a with the allylic halides 29a and 29c as well as with p-toluenesulfonate 29b yielded besides the phytol derivatives 1a and 1b - also the S_N2′-type products 30a and 30b (Scheme 8, Table 2); the same result was found for the coupling with the cis-configurated allylic acetates (Z)- 18a and (Z)- 18b (Table 3). A similar loss of chemo selectivity as well as the loss of stereoselectivity in the coupling reactions of 19 with the bifunctional (E)-olefins of type 18 was observed when the Li₂CuCl₄-catalyst concentration was increased from 0.2 to 25 mol-% or upon substitution of Li₂CuCl₄ by copper (I) chloride or iodide (Table 4).     

The repulsive wall of the Tang-Toennies potential for He2 reexamined

In the case of He₂, Aziz et al. [Z. Phys. D 21,251 (1991)] proposed a modification to the original Tang-Toennies potential form (TT) [J. Chem. Phys. 80, 3726 (1984)] which allows for a more accurate repulsive wall. The total interaction energyE _int can, in principle, be considered as the sum of uncorrelated and correlated energies, i.e.E _int (r)=E _unc(r)+E _c (r).E _unc is represented by the (SCF) Hartree-Fock interaction energyE _SCF for the rare gas dimer.E _c , which is expressed in terms of ab initio dispersion coefficients and a suitable damping function to account for charge overlap effects, is dominated by the van der Waals attraction in the long range. While the other literature potentials reproduce some of the data, only the TT model as modified by Aziz et al. properly characterizesE _int over the entire range andE _SCF over its range of significance.     

The first ionization potentials and conjugation in benzene derivatives containing organosilicon, organogermanium, organotin, and organolead substituents

The inductive and resonance effects of silicon-, germanium-, tin-, and lead-containing and some organic substituents on the HOMO energies (E _HOMO) for 43 monosubstituted andp-disubstituted benzene derivatives were analyzed in the Koopmans approximation. A linear dependence between the perturbation energy δE and the resonanceσ _R ⁺ parameters of the substituents was established. The Koopmans approximation is a rough approximation for the compounds studied, since to provide for its rigorous fulfilment, the δE values must depend on the σ _R ⁰ parameters of the substituents. The principal regularities of increasing the σ,π-conjugation between the organoelement substituents and the π-system caused by a positive charge on the benzene ring were established. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 70–75, January 1997.     

THE RELATIONSHIP BETWEEN CARCINOGENIC ACTIVITIES OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR SINGLET, TRIPLET, AND SINGLET-TRIPLET SPLITTING ENERGIES AND PHOSPHORESCENCE LIFETIMES

Abstract— The energies of the lowest excited singlet, E_s, and triplet, E_t, states, and singlet-triplet splitting energies, ΔE_s,t, were determined on 18 carcinogenic and 31 noncarcinogenic polycyclic aromatics. A highly significant correlation was found between carcinogenic activity and the energy of the excited singlet state. Compounds with an E_s < 312 kJ/mol were 4.8 times more likely to be carcinogens than those compounds with E_s 312 kJ/mol (P= 0.015). Compounds whose singlet energies fell within the narrow range of 297 ≤E_s≤ 310 kJ/mol were 22.8 times more likely to be carcinogens than those compounds which fell outside this range (P= 0.00006). A significant correlation between carcinogenic activity and E_t energies was not found, while the correlation involving ΔE_s,t energies was intermediate between the E_s and E_t correlations. The phosphorescence lifetimes, τ_p, of the 18 carcinogenic aromatics and 27 of the noncarcinogenic aromatip were determined, and were shown not to be correlated with carcinogenic activity. When either the E_t or ΔE_s,t energies were plotted as a function of E_s it was found that the carcinogens tended to form in an elliptical cluster. Compounds whose E_s and E_t energies placed them within the ellipse were 9.7 times more likely to be carcinogens than those compounds which fell outside the ellipse (P= 0.002), while with the E_s, ΔE_s,t ellipse, compounds which fell inside were 20.6 times more likely to be carcinogens than those which fell outside (P= 0.0004). E_s, E_t, ΔE_s,t and τ_p values were also determined on 12 carcinogenic and 4 noncarcinogenic alkyl substituted benz[a]anthracenes. There was no significant difference between the carcinogens and noncarcinogens and the “elliptical” correlation predicted both the carcinogens and noncarcinogens to be carcinogenic. The results suggest that either some property(ies) of the lowest excited singlet state, but not its energy, or some molecular property(ies) which runs parallel to singlet state energies may be important in determining carcinogenic activity in polycyclic aromatics.     

Homolytic substitution in trialkyltin iodides by photochemically generated iodine atoms. I. Kinetics

The kinetics of the homolytic substitution of several trialkyltin iodides by iodine atoms are presented. Rate constants have been determined at three different temperatures and the following activation parameters calculated: A, E_a, and ΔS°^≠. The observation that the activation energy, ΔG^≠, is related to the driving force of the ion-pair formation, leads to the conclusion that the charge-transfer model is a valid approach for substitution in the reaction between R₃SnI compounds and iodine atoms.     

Magnitude and origin of the attraction and directionality of the halogen bonds of the complexes of C6F5X and C6H5X (X = I, Br, Cl and F) with pyridine

The geometries and interaction energies of complexes of pyridine with C₆F₅X, C₆H₅X (X=I, Br, Cl, F and H) and R_FI (R_F=CF₃, C₂F₅ and C₃F₇) have been studied by ab initio molecular orbital calculations. The CCSD(T) interaction energies (E_int) for the C₆F₅X–pyridine (X=I, Br, Cl, F and H) complexes at the basis set limit were estimated to be ?5.59, ?4.06, ?2.78, ?0.19 and ?4.37 kcal mol^?1, respectively, whereas the E_int values for the C₆H₅X–pyridine (X=I, Br, Cl and H) complexes were estimated to be ?3.27, ?2.17, ?1.23 and ?1.78 kcal mol^?1, respectively. Electrostatic interactions are the cause of the halogen dependence of the interaction energies and the enhancement of the attraction by the fluorine atoms in C₆F₅X. The values of E_int estimated for the R_FI–pyridine (R_F=CF₃, C₂F₅ and C₃F₇) complexes (?5.14, ?5.38 and ?5.44 kcal mol^?1, respectively) are close to that for the C₆F₅I–pyridine complex. Electrostatic interactions are the major source of the attraction in the strong halogen bond although induction and dispersion interactions also contribute to the attraction. Short‐range (charge‐transfer) interactions do not contribute significantly to the attraction. The magnitude of the directionality of the halogen bond correlates with the magnitude of the attraction. Electrostatic interactions are mainly responsible for the directionality of the halogen bond. The directionality of halogen bonds involving iodine and bromine is high, whereas that of chlorine is low and that of fluorine is negligible. The directionality of the halogen bonds in the C₆F₅I– and C₂F₅I–pyridine complexes is higher than that in the hydrogen bonds in the water dimer and water–formaldehyde complex. The calculations suggest that the C? I and C? Br halogen bonds play an important role in controlling the structures of molecular assemblies, that the C? Cl bonds play a less important role and that C? F bonds have a negligible impact.     

Ab initio study of reactions of hydroxyl radicals with chloro‐ and fluoro‐substituted methanes

Ab initio calculations at the unrestricted Hartree–Fock (UHF) level have been performed to investigate the hydrogen abstraction reactions of ^? OH radicals with methane and nine halogen‐substituted methanes (F, Cl). Geometry optimization and vibrational frequency calculations have been performed on all reactants, adducts, products, and transition states at the UHF/6‐31G* level. Single‐point energy calculations at the MP2/6‐31++G* level using the UHF/6‐31G* optimized geometries have also been carried out on all species. Pre‐ and postreaction adducts have been detected on the UHF/6‐31G* potential energy surfaces of the studied reactions. Energy barriers, ΔE^?, reaction energies, ΔE_r, reaction enthalpies, ΔH_r, and activation energies, E_a, have been determined for all reactions and corrected for zero‐point energy effects. Both E_a and ΔH_r come into reasonable agreement with the experiment when correlation energy is taken into account and when more polarized and diffuse basis sets are used. The E_a values, estimated at the PMP2/6‐31++G* level, are found to be in good agreement with the experimental ones and correctly reproduce the experimentally observed trends in fluorine and chlorine substitution effects. A linear correlation between E_a and ΔH_r is obtained, suggesting the presence of an Evans–Polanyi type of relationship. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 426–440, 2001     

Catalytic enantioselective conjugate addition of dialkyl zinc reagents to α,β-unsaturated ketones mediated by new phosphite ligands containing binaphthalene/1,2-diphenylethane moieties: a practical synthesis of (R)-(−)-muscone

New diastereoisomeric phosphites based on either (R)- or (S)-2,2′-dihydroxy-1,1′-binaphthyl (BINOL) and having the chiral alcoholic moiety derived from the monobenzyl ether of (R,R)-1,2-diphenylethane-1,2-diol have been prepared and used as chiral ligands in the enantioselective copper-catalyzed 1,4-addition of diethylzinc to chalcone and 2-cyclohexen-1-one (enantiomeric excesses up to 48%). With the (aR,R,R) ligand dimethylzinc adds enantioselectively to (E)-cyclopentadecen-2-en-1-one to give (R)-(−)-muscone (68% yield, 78% ee). This provides an efficient access to a valuable ingredient of the perfume industry. However, with the (aS,R,R) ligand, (S)-(+)-muscone is obtained with longer reaction times (37% yield and 10% ee) with a very high double diastereoselection effect being observed.     

Energy distribution among reaction products. H + NOCl,H + ICl

The infrared chemiluminescence technique has been used to obtain k(V′, R′, T′) (V′, R′, Tt? are product vibrational, rotational and translational energies) for the reactions (i) H + ClNO → HCl + NO (energy-release E_tot′ = 68.5 kcal mole^?1) and (ii) H + CII → HCl + I (E_tot′ = 55.8 kcal mole^?1). Reaction (i) exhibits inefficient conversion of energy-release into vibration in the new bond, characteristic of a light attacking atom reacting on a repulsive energy-surface. Reaction (ii) has a bimodal HCl product-energy-distribution suggesting that 18% of the reaction proceeds by direct attack at the Cl end of CII to yield low V′ and R′, and 82% by indirect reaction from the 1 end to give high V′ and R′.     

Tuning the Electronic Coupling in Cyclometalated Diruthenium Complexes through Substituent Effects: A Correlation between the Experimental and Calculated Results

A common bridging ligand, 3,3′,5,5′‐tetrakis(N‐methylbenzimidazol‐2‐yl)biphenyl, and four terpyridine terminal ligands with various substituents (amine, tolyl, nitro, and ester groups) have been used to synthesize ten cyclometalated diruthenium complexes 1 ²⁺– 10 ²⁺. Among them, compounds 1 ²⁺– 6 ²⁺ are redox nonsymmetric, and others are symmetric. These complexes show two Ru^III/II processes and an intervalence charge transfer (IVCT) transition in the one‐electron oxidized state. The potential separation (ΔE) of 1 ²⁺– 10 ²⁺ has been correlated to the energy difference ΔG⁰, the energy of the IVCT band E_op, and the ground‐state delocalization coefficient α². Time‐dependent (TD)DFT calculations suggest that the absorptions in the visible region of 1 ²⁺– 6 ²⁺ are mainly associated with the metal‐to‐ligand charge‐transfer transitions from both ruthenium ions and to both terminal ligands and the bridging ligand. However, the energies of these transitions vary significantly. DFT calculations have been performed on 1 ²⁺– 6 ²⁺ and 1 ³⁺– 6 ³⁺ to give information on the electronic structures and spin populations of the mixed‐valent compounds. The TDDFT‐predicted IVCT excitations reproduce well the experimental trends in transition energies. In addition, three monoruthenium complexes have been synthesized for a comparison study.     

Investigation on molecular interaction studies of binary mixture of DEHPA and petrofin at 298.15 K

The present article reports the values of density (ρ₁₂), molar volume (V₁₂), apparent molar volume (V_?), dielectric constant (?₁₂), molar polarisation (P₁₂) and molar refraction (R₁₂) of binary mixture of di-2-ethylhexyl phosphoric acid (DEHPA) and petrofin at various compositions. The excess properties such as V^E, ?^E, ΔnD, P^E and R^E have been calculated to throw light on the existence of interaction between the DEHPA and petrofin molecules in the binary mixture. The values of V^E and R^E were found to be positive while the values of ?^E, ΔnD and P^E were negative over the entire composition showing weak interaction between the two unlike molecules in the mixture. The Kirkwood-correlation factors (g) have been evaluated to know the nature of interaction prevailing in DEHPA and petrofin. These data provide useful information regarding interaction between self-associated protic DEHPA and non-associated petrofin which in turn helps the metallurgist to use DEHPA diluted with petrofin as effective solvent in extraction of metals.     

Topological and Thermodynamic Studies for Binary Mixtures of 1,4-Dioxane with Anilines at 308.15 K

Excess molar volumes, V ^E, excess molar enthalpies, H ^E, speeds of sound, u, and vapor-liquid equilibrium data of 1,4-dioxane (1) + aniline or N-methyl aniline or o-toluidine (2) binary mixtures have been measured as a function of composition at 308.15 K. Isentropic compressibility changes that occur for mixing, k_S^E\kappa_{S}^{\mathrm{E}}, and excess Gibb’s energies, G ^E, have been determined by employing speeds of sound and vapor-liquid equilibrium data. The V^E, H^E,k_S^EV^{\mathrm{E}}, H^{\mathrm{E}},\kappa_{S}^{\mathrm{E}} and G ^E values have been estimated by (i) graph theory and (ii) the Prigonone-Flory-Patterson theory (PFP). It was observed that values of V^E, H^E,k_S^EV^{\mathrm{E}}, H^{\mathrm{E}},\kappa_{S}^{\mathrm{E}} and G ^E predicted by graph theory compare well, relative to the PFP theory, with their corresponding experimental values.     

Study of Intermolecular Interaction in Dimethylsulphoxide + 1-Alkanols (1-Butanol, 1-Hexanol, 1-Octanol) At 303.15 K

Abstract

The ultrasonic velocity, u, viscosity, η, and density, ρ of dimethylsulphoxide (DMSO), 1-butanol, 1-hexanol, 1-octanol, and of their binary mixtures, where DMSO is common component, have been measured at 303.15 K. From the experimental data, excess isentropic compressibility, K ^E _s, excess intermolecular free length, L^E _f, excess velocity, u ^E, excess acoustic impedance, Z ^E, excess viscosity, η^E, excess free energy of activation of viscous flow, G?^E, and excess rheochore, [R ^E] have been calculated. The behaviours of excess functions with composition of the mixtures suggest that the structure-breaking effect dominates over the interaction effect between the component molecules. Furthermore, the experimental values of u and η were fitted by empirical equations stating their dependence on composition of the mixtures. The experimental values of u have been compared with those calculated by using Nomoto and Van Dael relations.