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1985 Volume 1 Issue 3
1985, 1(03): 205-206
doi: 10.3866/PKU.WHXB19850301
Abstract:
The conformations of title compound in the crystal and in the isolated state have been calculated by means of QCFF/PI+MCA (Quantum Mechanical Extension of the Consistent Force Field to PI Electron System+Molecular Crystal Analysis) computer program. The results of investigation indicated that the twist angle between the two phenyl rings of biphenyl in the molecule is about 18.9° in the gas phase and 1.3° in the crystalline phase. The conformation of the molecule in the crystal is in agreement with that obtained by X-ray crystal structure determination. We have calculated equilibrium geometries and vibrational frequencies of 4,4'-diben-zoylbiphenyl. The observed and some calculated vibrational frequencies are listed in Table 1.
The conformations of title compound in the crystal and in the isolated state have been calculated by means of QCFF/PI+MCA (Quantum Mechanical Extension of the Consistent Force Field to PI Electron System+Molecular Crystal Analysis) computer program. The results of investigation indicated that the twist angle between the two phenyl rings of biphenyl in the molecule is about 18.9° in the gas phase and 1.3° in the crystalline phase. The conformation of the molecule in the crystal is in agreement with that obtained by X-ray crystal structure determination. We have calculated equilibrium geometries and vibrational frequencies of 4,4'-diben-zoylbiphenyl. The observed and some calculated vibrational frequencies are listed in Table 1.
1985, 1(03): 207-210
doi: 10.3866/PKU.WHXB19850302
Abstract:
The three dimensional X-ray data were collected by Nicolet R3 four circle diffractometer. Compound(Ⅰ)crystallized in monoclinic crystal system and space group P 21/n with a=1.1464(4) nm, b=0.6285(2) nm, c=2.1175(8) nm, β=111.06°(5), V=1.4236 nm, z=4. Compound (Ⅱ) crystallized in triclinic crystal system and space group P 1 with a=0.8129(3) nm, b=1.0371(2) nm, c=1.0762(3) nm, a=64.86°(2), β=83.97°(2), γ=80.43°(2), V=0.8094 nm, Z=2.
The crystal structures were solved by direct method and refined by block matrix least square program. The final R factors are 0.039 for compound (Ⅰ) and 0.052 for compound (Ⅱ). The CNDO/2 calculations were applied for both compounds.
The compound (Ⅱ) was given evidence of the tranquil activity and low toxicity in mice.
The three dimensional X-ray data were collected by Nicolet R3 four circle diffractometer. Compound(Ⅰ)crystallized in monoclinic crystal system and space group P 21/n with a=1.1464(4) nm, b=0.6285(2) nm, c=2.1175(8) nm, β=111.06°(5), V=1.4236 nm, z=4. Compound (Ⅱ) crystallized in triclinic crystal system and space group P 1 with a=0.8129(3) nm, b=1.0371(2) nm, c=1.0762(3) nm, a=64.86°(2), β=83.97°(2), γ=80.43°(2), V=0.8094 nm, Z=2.
The crystal structures were solved by direct method and refined by block matrix least square program. The final R factors are 0.039 for compound (Ⅰ) and 0.052 for compound (Ⅱ). The CNDO/2 calculations were applied for both compounds.
The compound (Ⅱ) was given evidence of the tranquil activity and low toxicity in mice.
1985, 1(03): 211-212
doi: 10.3866/PKU.WHXB19850303
Abstract:
The photofragmentation of CH_3I at 249 nm has been investigated by means of our crossed laser-molecular beam apparatus with rotatable supersonic beam source. The measured I~*/I yield ratio is about 4/1. The C—I bond dissociation energy obtained is 56±1 kcal mol~(-1). The vibrational energy distribution of CH_3 fragments has been roughly estimated.
The photofragmentation of CH_3I at 249 nm has been investigated by means of our crossed laser-molecular beam apparatus with rotatable supersonic beam source. The measured I~*/I yield ratio is about 4/1. The C—I bond dissociation energy obtained is 56±1 kcal mol~(-1). The vibrational energy distribution of CH_3 fragments has been roughly estimated.
1985, 1(03): 213-214
doi: 10.3866/PKU.WHXB19850304
Abstract:
The molar execess enthalpies of C_1 to C_5 normal alcohols with 1,4-dioxane have been measured with a Picker flow microcalorimeter. From our measurements we can come to the following results. Mixing n-alcohols with 1,4-dioxane are all endothermic processes. The maximum values of H~E are situated near 0.49 mole fraction of n-alcohols. H~E of these systems increase with increasing chain length of the alcohols, whereas the increments for two neighbour-alcohols decrease with increasing the number of carbon.
The molar execess enthalpies of C_1 to C_5 normal alcohols with 1,4-dioxane have been measured with a Picker flow microcalorimeter. From our measurements we can come to the following results. Mixing n-alcohols with 1,4-dioxane are all endothermic processes. The maximum values of H~E are situated near 0.49 mole fraction of n-alcohols. H~E of these systems increase with increasing chain length of the alcohols, whereas the increments for two neighbour-alcohols decrease with increasing the number of carbon.
1985, 1(03): 215-221
doi: 10.3866/PKU.WHXB19850305
Abstract:
Nickel, electrodeposited from twelve typical plating baths, were investigated by positron annihilation lifetime spectroscopy. In view of the impurity presented in Ni deposits, the theoretical analysis was based on four state trapping model.
The estimation of concentration of vacancy-like and void-type defect of as-deposited sample, as a function of the annihilation parameters, was obtained from twocomponent fitting.
The annealing behavior of sample No.1O had been studied. Based on the resulting curves of an...
Nickel, electrodeposited from twelve typical plating baths, were investigated by positron annihilation lifetime spectroscopy. In view of the impurity presented in Ni deposits, the theoretical analysis was based on four state trapping model.
The estimation of concentration of vacancy-like and void-type defect of as-deposited sample, as a function of the annihilation parameters, was obtained from twocomponent fitting.
The annealing behavior of sample No.1O had been studied. Based on the resulting curves of an...
1985, 1(03): 222-231
doi: 10.3866/PKU.WHXB19850306
Abstract:
MoO_3/γ-Al_2O_3, MoO_3/TiO_2 and MoO_3/SiO_2 samples prepared by impregnation method have been studied by various techniques, including XPS, XRD, and extraction of molybdenum with ammonium solution or water. The result of extraction of molybdenum with ammonium solution shows that if the MoO_3 content is lower than certain amount, a constant fraction (71% for MoO_3/γ-Al_2O_3 system and 66% for MoO_3/TiO_2 system) of MoO_3 can be dissolved in 3wt.% solution of NH_4OH and if the MoO_3 content is higher than that amount, surplus MoO_3 can be dissolved completly. The turning point of both systems is in line with the dispersed threshold value obtained by XPS and XRD methods. It means that MoO_3 dispreses as monolayer on these carriers before the turning point and forms crystalite grain after that. The constant dissolved fraction of MoO_3 in ammonium solution shows that there are two different surface species in monolayer state, one is soluble and another is not. Two kinds of species coexist in monolayer with constant ratio, which have also been confirmed by XPS experiment for samples before and after extraction. The samples which soluble species was thoroughly removed were recalcined at certain temperture and again soaked into ammonium solution a lot of soluble species were reproduced then. The dissolved fraction of them approched that of the samples before extraction with a rise in temperature and a prolonging of time. We suggest that the monolayer dispersed MoO_3 on γ-Al_2O_3 or TiO_2 surface can be divided into two kinds of surface species, one is located in octahedral vacancy of O~(2-) and another in tetrahedra vacancy. They join each other by sharing oxygen ions and form monolayer aggregate patch′ in a special way (similar to γ-molybdena Mo_4O_(11)). It is a thermodynamic favorable state in both systems. For MoO_3/SiO_2 samples, however, the situation is quite different. All of MoO_3 species in the monolayer is soluble thoroughly in ammonium solution. It shows that the mutual interaction between MoO_3 in monolayer state and the surface of SiO_2 carrier is much weaker than that of two other systems.
MoO_3/γ-Al_2O_3, MoO_3/TiO_2 and MoO_3/SiO_2 samples prepared by impregnation method have been studied by various techniques, including XPS, XRD, and extraction of molybdenum with ammonium solution or water. The result of extraction of molybdenum with ammonium solution shows that if the MoO_3 content is lower than certain amount, a constant fraction (71% for MoO_3/γ-Al_2O_3 system and 66% for MoO_3/TiO_2 system) of MoO_3 can be dissolved in 3wt.% solution of NH_4OH and if the MoO_3 content is higher than that amount, surplus MoO_3 can be dissolved completly. The turning point of both systems is in line with the dispersed threshold value obtained by XPS and XRD methods. It means that MoO_3 dispreses as monolayer on these carriers before the turning point and forms crystalite grain after that. The constant dissolved fraction of MoO_3 in ammonium solution shows that there are two different surface species in monolayer state, one is soluble and another is not. Two kinds of species coexist in monolayer with constant ratio, which have also been confirmed by XPS experiment for samples before and after extraction. The samples which soluble species was thoroughly removed were recalcined at certain temperture and again soaked into ammonium solution a lot of soluble species were reproduced then. The dissolved fraction of them approched that of the samples before extraction with a rise in temperature and a prolonging of time. We suggest that the monolayer dispersed MoO_3 on γ-Al_2O_3 or TiO_2 surface can be divided into two kinds of surface species, one is located in octahedral vacancy of O~(2-) and another in tetrahedra vacancy. They join each other by sharing oxygen ions and form monolayer aggregate patch′ in a special way (similar to γ-molybdena Mo_4O_(11)). It is a thermodynamic favorable state in both systems. For MoO_3/SiO_2 samples, however, the situation is quite different. All of MoO_3 species in the monolayer is soluble thoroughly in ammonium solution. It shows that the mutual interaction between MoO_3 in monolayer state and the surface of SiO_2 carrier is much weaker than that of two other systems.
1985, 1(03): 232-238
doi: 10.3866/PKU.WHXB19850307
Abstract:
Electrochemical reduction of nickel sandwich complex-cations Ni(h~5-C_5eR_5) (h~4-C_4R'_4)~+, where R=H, CH_3; R'=CH_3, C_6H_5 was investigated at a Pt-electrode by means of cyclic voltametry, chronopotentiometry and chronoamperometry in dichloromethane, acetonitrile, tetrahydrofuran and propylenecarbonate (PC). The reduction are reversible and single electron processes for the compounds with R=H, R'=C_6H_5; R=CH_3, R'=C_6H_5 and the products are characteristic of “19-electron” nickel complexes. The complex cations exhibit an irreversible processes with coupled chemical reaction when R=H, R′=CH_3; R=CH_3, R′=CH_3. The stability of the reduction products was investigated further by bulk electrolysis. The reversibility of the electrochemical reduction tend to be reduced in THF.
Electrochemical reduction of nickel sandwich complex-cations Ni(h~5-C_5eR_5) (h~4-C_4R'_4)~+, where R=H, CH_3; R'=CH_3, C_6H_5 was investigated at a Pt-electrode by means of cyclic voltametry, chronopotentiometry and chronoamperometry in dichloromethane, acetonitrile, tetrahydrofuran and propylenecarbonate (PC). The reduction are reversible and single electron processes for the compounds with R=H, R'=C_6H_5; R=CH_3, R'=C_6H_5 and the products are characteristic of “19-electron” nickel complexes. The complex cations exhibit an irreversible processes with coupled chemical reaction when R=H, R′=CH_3; R=CH_3, R′=CH_3. The stability of the reduction products was investigated further by bulk electrolysis. The reversibility of the electrochemical reduction tend to be reduced in THF.
1985, 1(03): 239-248
doi: 10.3866/PKU.WHXB19850308
Abstract:
A new oscillatory system has been investigated by the quadripole mass-spectrometer. It is recognized that nature of this gas-liquid two phase system is of a physical one.
For a propylene-butyl aldehyde or benzene mixture the oscillation of the concentration of propylene in the gas phase can be maintained in a certain region of pressure. The experimental work has shown that the oscillatory behavior of the releasing process of the dissolved gas requests a threshold on its flow rate and is sensitive to the change of temperature. The pressure and the stiring condition are not the origin of this oscillatory phenomenon, though they really change the period and the amplitude of the oscillation. The synthetic gas, added into this system, will play a “concert” role in their concentration oscillation, but the oscillatory directions of the concentrations of hydrogen and carbonmonoxide are opposite to that of propylene.
...
A new oscillatory system has been investigated by the quadripole mass-spectrometer. It is recognized that nature of this gas-liquid two phase system is of a physical one.
For a propylene-butyl aldehyde or benzene mixture the oscillation of the concentration of propylene in the gas phase can be maintained in a certain region of pressure. The experimental work has shown that the oscillatory behavior of the releasing process of the dissolved gas requests a threshold on its flow rate and is sensitive to the change of temperature. The pressure and the stiring condition are not the origin of this oscillatory phenomenon, though they really change the period and the amplitude of the oscillation. The synthetic gas, added into this system, will play a “concert” role in their concentration oscillation, but the oscillatory directions of the concentrations of hydrogen and carbonmonoxide are opposite to that of propylene.
...
1985, 1(03): 249-257
doi: 10.3866/PKU.WHXB19850309
Abstract:
The kinetics and mechanism of the thermolysis of tetralin, commonly used as a hydrogen donor in coal liquefaction, was studied under about 100 atm and within 385—485 ℃. Analysis of the products was carried out by G.C.with glass capillary column and F.I.D., G.C.-M.S., N.M.R.. The reaction was performed in a microreactor which was contructed by a small stainless steel tube. Dehydrogenation of tetralin to naphthylene and isomerization to l-methylindan were found to be dominate paths, while cracking of the C_B—C bound of tetralin to butyl benzene is subordinated. The small quantities of indan, toluene and ethylbenzene are believed to be derived from the further thermolysis of methyl indan and butylbenzene.
A detailed kinetic analysis was given and the kinetic parameters were obtained. Combined with the thermokinetics calculations, a mechanism of the tetralin thermolysis was suggested.
The kinetics and mechanism of the thermolysis of tetralin, commonly used as a hydrogen donor in coal liquefaction, was studied under about 100 atm and within 385—485 ℃. Analysis of the products was carried out by G.C.with glass capillary column and F.I.D., G.C.-M.S., N.M.R.. The reaction was performed in a microreactor which was contructed by a small stainless steel tube. Dehydrogenation of tetralin to naphthylene and isomerization to l-methylindan were found to be dominate paths, while cracking of the C_B—C bound of tetralin to butyl benzene is subordinated. The small quantities of indan, toluene and ethylbenzene are believed to be derived from the further thermolysis of methyl indan and butylbenzene.
A detailed kinetic analysis was given and the kinetic parameters were obtained. Combined with the thermokinetics calculations, a mechanism of the tetralin thermolysis was suggested.
1985, 1(03): 258-264
doi: 10.3866/PKU.WHXB19850310
Abstract:
On the theoritical basis of thermokinetics proposed in previous articles, the thermokinetics for saponification of the ethyl esters of acetic, propionic, and normal butyric acids have been studied at 20 and 30 ℃ in 85% ethyl alcohol aqueous solution with the method of dimensionless parameter for the first order reactions. The rate canstants and the activation energies of these reactions are in reasonable agreement with the values in literature. The activation free-energies of the reaction have been calculated.
The studied region for initial concentration of reactant and rate constant of reaction limited by cooling constant of calorimeter has also been discussed in this paper.
On the theoritical basis of thermokinetics proposed in previous articles, the thermokinetics for saponification of the ethyl esters of acetic, propionic, and normal butyric acids have been studied at 20 and 30 ℃ in 85% ethyl alcohol aqueous solution with the method of dimensionless parameter for the first order reactions. The rate canstants and the activation energies of these reactions are in reasonable agreement with the values in literature. The activation free-energies of the reaction have been calculated.
The studied region for initial concentration of reactant and rate constant of reaction limited by cooling constant of calorimeter has also been discussed in this paper.
1985, 1(03): 265-269
doi: 10.3866/PKU.WHXB19850311
Abstract:
A series of zinc phthalocyanines was synthesized. Their redox potentials, E_(ox) and E_R were measured by means of cyclic voltammetry. Their kinetic datum, κ_qτ of fluorescence quenching by typical electron acceptor was determined. The theoretical relation of the fluorescence quenching rate constant, κ_q vs. the electron transfer free enthalpy change, △G was calculated from redox potential and spectral datum, and κ_q was calculated from the theoretical relation between κ_q and △G. By substituting κ_q into κ_qτ, the lifetime of dye's fluorescence can be evaluated by non-transient experiments and simple calculations. In comparing with data in literature, the average fluorescence lifetime of the dye obtained is receivable.
A series of zinc phthalocyanines was synthesized. Their redox potentials, E_(ox) and E_R were measured by means of cyclic voltammetry. Their kinetic datum, κ_qτ of fluorescence quenching by typical electron acceptor was determined. The theoretical relation of the fluorescence quenching rate constant, κ_q vs. the electron transfer free enthalpy change, △G was calculated from redox potential and spectral datum, and κ_q was calculated from the theoretical relation between κ_q and △G. By substituting κ_q into κ_qτ, the lifetime of dye's fluorescence can be evaluated by non-transient experiments and simple calculations. In comparing with data in literature, the average fluorescence lifetime of the dye obtained is receivable.
1985, 1(03): 270-280
doi: 10.3866/PKU.WHXB19850312
Abstract:
The catalytic behavior of H_(3+n)PMo(12-n)V_nO_(40) (abbreviated to HPA-n hereafter) +H_2O_2 system in the direct hydroxylation of benzene is completely different from that of well-known Fenton reagent(Fe_(2+)+H_2O_2). The comparison experiments showed that the kinetics of the decomposition of H_2O_2 in HPA-n system generally gave Sshaped curves, which is different from that in Fenton system(Fig.2). The sensitivity of active species generated in the HPA_(-n)+H_2O_2 system toward benzene is far less than that generated in Fenton system, which parallels with the response to the concentration of H~+. Phenol is the only product in the HPA-n system. Data obtained from the hydroxylation experiments under different conditions and kinetic studies of the decomposition of H_2O_2 showed that, although the substituted number (n) of vanadium ion in heteropoly anion and the concentration of the catalyst had a great effect on the rate of the decomposition, they had little effect on the product yield (based on H_2O_2). On the other hand, the initial concentration of oxidant had little to do with the initial stage rate of decomposition, but affected the induced period and product yield to certain extent. Electronic spectra showed that during the decomposition of H_2O_2, two intermdiates might formed (Fig.9). Based on these facts, the mechanism of the activation of H_2O_2 and hydroxylation of benzene by molybdovanadophosphoric acid was suggested. It seems that the vanadium ion in hte heteroply anion might associated with H_2O_2 to form the transient “peracid like” species, followed by the transformation into side-on peroxo compound by auto catalytic process. The latter complex, which acted as an active species, played a major role in the activation of H_2O_2 and hydroxylation of benzene. The kinetic equation deduced from the suggested mechanism is as follows:
-(d[H_2O_2])/(dt)=k_1[I]+2k_4[H_2O_2]{[III][HPA]exp[HPA]k_3(t-τ)}{[HPA]+[III]exp[HPA]k_3(t-τ)}
[I] is the concentration of complex HPA·H_2O_2
...
The catalytic behavior of H_(3+n)PMo(12-n)V_nO_(40) (abbreviated to HPA-n hereafter) +H_2O_2 system in the direct hydroxylation of benzene is completely different from that of well-known Fenton reagent(Fe_(2+)+H_2O_2). The comparison experiments showed that the kinetics of the decomposition of H_2O_2 in HPA-n system generally gave Sshaped curves, which is different from that in Fenton system(Fig.2). The sensitivity of active species generated in the HPA_(-n)+H_2O_2 system toward benzene is far less than that generated in Fenton system, which parallels with the response to the concentration of H~+. Phenol is the only product in the HPA-n system. Data obtained from the hydroxylation experiments under different conditions and kinetic studies of the decomposition of H_2O_2 showed that, although the substituted number (n) of vanadium ion in heteropoly anion and the concentration of the catalyst had a great effect on the rate of the decomposition, they had little effect on the product yield (based on H_2O_2). On the other hand, the initial concentration of oxidant had little to do with the initial stage rate of decomposition, but affected the induced period and product yield to certain extent. Electronic spectra showed that during the decomposition of H_2O_2, two intermdiates might formed (Fig.9). Based on these facts, the mechanism of the activation of H_2O_2 and hydroxylation of benzene by molybdovanadophosphoric acid was suggested. It seems that the vanadium ion in hte heteroply anion might associated with H_2O_2 to form the transient “peracid like” species, followed by the transformation into side-on peroxo compound by auto catalytic process. The latter complex, which acted as an active species, played a major role in the activation of H_2O_2 and hydroxylation of benzene. The kinetic equation deduced from the suggested mechanism is as follows:
-(d[H_2O_2])/(dt)=k_1[I]+2k_4[H_2O_2]{[III][HPA]exp[HPA]k_3(t-τ)}{[HPA]+[III]exp[HPA]k_3(t-τ)}
[I] is the concentration of complex HPA·H_2O_2
...
1985, 1(03): 281-288
doi: 10.3866/PKU.WHXB19850313
Abstract:
MoO_3-SnO_2 catalysts prepared by precipitation, impregnation and high temperature calcination of the relevant mixtures have been investigated by using XRD, IR and ESR, It is shown that there is a strong interaction between MoO_3 and SnO_2. An electron transfer process occurs between two components and leads to the formation of Mo~(5+) from Mo~(6+), surface acid site with pKα≤+3.3 as well as active center for methanol selective oxidation.
The preparation method has significant effect on the interaction between MoO_3 and SnO_2 and the catalytic behavior of the catalysts. MoO_3 can dissolve in SnO_2 forming solid solution in the catalyst prepared by precipitation method, while Mo ions diffuse into the bulk of SnO_2 in hte catalyst prepared by impregnation. Below a certain level, MoO_3 can disperse as a monolayer on the SnO_2 surface in the ctalyst prepared by high temperature calcination.
...
MoO_3-SnO_2 catalysts prepared by precipitation, impregnation and high temperature calcination of the relevant mixtures have been investigated by using XRD, IR and ESR, It is shown that there is a strong interaction between MoO_3 and SnO_2. An electron transfer process occurs between two components and leads to the formation of Mo~(5+) from Mo~(6+), surface acid site with pKα≤+3.3 as well as active center for methanol selective oxidation.
The preparation method has significant effect on the interaction between MoO_3 and SnO_2 and the catalytic behavior of the catalysts. MoO_3 can dissolve in SnO_2 forming solid solution in the catalyst prepared by precipitation method, while Mo ions diffuse into the bulk of SnO_2 in hte catalyst prepared by impregnation. Below a certain level, MoO_3 can disperse as a monolayer on the SnO_2 surface in the ctalyst prepared by high temperature calcination.
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1985, 1(03): 289-292
doi: 10.3866/PKU.WHXB19850314
Abstract:
The crystal of tetrahydrothiazole-2-thione belongs to triongal system, space group R3c. There are six molecules in a unit cell with parameter a=b=1.5402(5), c=1.2528(19) nm, γ=120°. The three dimensional intensity data were obtained with PW-1100 four-circle diffractometer. 522 independent reflexions with I>1.3σ(I) were considered observed and used in structure analysis. The structure was solved by direct method(RANTAN) and refined by full matrix least-squares method, the final R=0.049, R_w=0.044.
The crystal structure of tetrahydrothiazole-2-thione copper complex shows that Cu is four coordinated and has nearly tetrahedron configuration.
The crystal of tetrahydrothiazole-2-thione belongs to triongal system, space group R3c. There are six molecules in a unit cell with parameter a=b=1.5402(5), c=1.2528(19) nm, γ=120°. The three dimensional intensity data were obtained with PW-1100 four-circle diffractometer. 522 independent reflexions with I>1.3σ(I) were considered observed and used in structure analysis. The structure was solved by direct method(RANTAN) and refined by full matrix least-squares method, the final R=0.049, R_w=0.044.
The crystal structure of tetrahydrothiazole-2-thione copper complex shows that Cu is four coordinated and has nearly tetrahedron configuration.
1985, 1(03): 293-298
doi: 10.3866/PKU.WHXB19850315
Abstract:
The excess volumes of ten binary systems namely benzene +2-butanone, +acetonitrile, +acrylonitrile, +ethyl acetate, +methyl acrylate; toluene +2-butanone, +acetonitrile, +acrylonitrile, +ethyl acetate, +methyl acrylate have been measured over entire composition range at 293.15 K.
The results indicate that the excess volumes for systems containing nitriles or ketone are negative, a double bond in the nitrile causes a significant decrease in V~E. Inversely, the excess volumes for systems containing esters are positive or slight negative, a double bond in it causes a significant increase in V~E. It may be conclude that the dipole interaction is not the only cause of the deviation, and there are a specific interaction between aromatic and nitrile or ketone molecules, while the unlike interaction between aromatic and ester belongs to van der Waals type.
The excess volumes of ten binary systems namely benzene +2-butanone, +acetonitrile, +acrylonitrile, +ethyl acetate, +methyl acrylate; toluene +2-butanone, +acetonitrile, +acrylonitrile, +ethyl acetate, +methyl acrylate have been measured over entire composition range at 293.15 K.
The results indicate that the excess volumes for systems containing nitriles or ketone are negative, a double bond in the nitrile causes a significant decrease in V~E. Inversely, the excess volumes for systems containing esters are positive or slight negative, a double bond in it causes a significant increase in V~E. It may be conclude that the dipole interaction is not the only cause of the deviation, and there are a specific interaction between aromatic and nitrile or ketone molecules, while the unlike interaction between aromatic and ester belongs to van der Waals type.
