3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The catalytic rearrangement of the cyclopentasiloxanes _mD_5-m, where represents a 3, 3, 3-trifluoropropyl(methyl)siloxane link and D a dimethylsiloxane link, and m=2–5 has been studied by the method described previously [1]. The rate of rearrangement and the rate of formation of a linear polysiloxane rise with an increase in m from 2 to 4. The equilibrium concentration of the linear polysiloxane formed from _mD_5-m and from _mD_4-m (m=0–4) [1] is inversely proportional to the molar fraction of links in the ring and rises with an increase in the total concentration of siloxane links in solution. Results have been obtained on the kinetics of the formation of the cyclosiloxanes _mD_n (where m=0–5, n=0–5, and m+n=3-6) during the rearrangement of the cyclopentasiloxanes _mD_5-m. It has been established that at equilibrium a mixture of cyclosiloxanes _mD_n containing practically constant ratios of tetramers, pentamers, and hexamers (m+n=4, 5, and 6) is obtained, regardless of the composition and structure of the initial cyclosiloxane and of the conditions of rearrangement (polymerization). The cyclopentasiloxanes _mD_5-m are less active in the process of rearrangement than the cyclotetrasiloxanes _mD_4-m. The activity of the cyclosiloxanes in rearrangement in the presence of a base rises in the sequence D₄D_{3 2}D₃<₃D₂<₄D < ₂D₂ < ₃D.For part II, see [1].     

VUV-Photolyse von Methanol bei 1236 Å

Zusammenfassung Es wird über die indirekte und die direkte VUV-Photolyse von luftfreiem Methanol in flüssiger Phase bei 1236 Å berichtet. Bei der Bestrahlung von wäßr. 0,01m-Methanol wurden folgende Produkte und Ausbeuten erhalten: (H₂)=1,00, (HCHO)=0,27, (CH₂OH)₂=0,12, (CH₂OH·CHO)=0,04 und (HCOOH)=0,02. Die Photolyse von flüssigem Methanol lieferte die gleichen Produkte, jedoch mit höheren Ausbeuten: (H₂)=1,50, (HCHO)=0,98, (CH₂OH)₂=0,28 und (CH₂OH·CHO)=0,06. Unter Anwendung von Methanol als Radikalfänger konnte auch die Quantenausbeute der Wasserphotolyse bei 1236 Å, (H,OH)=1,025 verifiziert werden. Wahrscheinliche Reaktionsmechanismen werden diskutiert.

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V.U.V.-Photolysis of methanol at 1236 Å

The indirect and the direct v.u.v.-photolysis of air free methanol in liquid phase at 1236 Å is reported. After irradiation of aqueous 0.01M-methanol the following products were obtained: (H₂)=1.00, (HCHO)=0.27, (CH₂OH)₂=0.12, (CH₂OH·CHO)=0.04 and (HCOOH)=0.02. The photolysis of liquid methanol yielded the same compounds, however with higher amount as follows: (H₂)=1.50, (HCHO)=0.98, (CH₂OH)₂=0.28 and (CH₂OH·CHO)=0.06. Using methanol as a scavenger for the H and OH radicals the quantum yield of the water photolysis at 1236 Å could be verified to be (H,OH)=1.025. Probable reaction mechanisms are discussed.

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Mit 3 Abbildungen

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Herrn Prof. Dr.E. Broda zum 60. Geburtstag gewidmet.     

Photochemische Carbonylierung und Oxydation von wässerigem Methanol bei 1470 Å

Zusammenfassung Das photochemische Verhalten von wässerigem Methanol, gesättigt mit Argon, CO bzw. O₂ wurde bei 1470 Å als Funktion der VUV-Dosis und der Methanolkonzentration untersucht. Als Reaktionsprodukte wurden Wasserstoff, Formaldehyd, Glykolaldehyd, Glykol, Ameisensäure und in Gegenwart von Sauerstoff auch Peroxyd nachgewiesen. In 10^–2 m-Methanol, gesättigt mit Argon, betrug (H₂)=0,69 und (HCHO)=0,22, in Gegenwart von 7·10^–4 m-CO war (H₂)=0,10 und (HCHO)=0,29, während bei Sättigung mit O₂ (10^–3 mO₂) (H₂)=0,01, (HCHO)=0,33, (HCOOH)=0,20 und (H₂O₂)=0,22 gefunden wurde. Die -Werte der übrigen Produkte, die unter den angegebenen Bedingungen erhalten wurden, waren <0,07. Durch Erhöhung der Methanolkonzentration bis zu reinem Methanol, gesättigt mit Argon, stieg die Ausbeute von H₂, HCHO und (CH₂OH)₂ entsprechend an, während die von HCOOH und CH₂OHCHO sich praktisch nicht änderte. Bei reinem, mit Argon gesättigtem Methanol war (H₂)=0,89 und (HCHO)=0,73. Das Glykol erreichte bei etwa 2m-Methanol eine Höchstausbeute von =0,38. Reaktionsmechanismen werden diskutiert.

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Photochemical carbonylation and oxidation of aqueous methanol at 1470 Å

The photochemical behaviour of aqueous methanol saturated with argon, CO and O₂, resp., has been investigated at 1470 Å as a function of the v.u.v. dose and the methanol concentration. Hydrogen, formaldehyde, glycolaldehyde, glycol, formic acid and, in the presence of oxygen, also peroxide were detected. In 10^–2 M-CH₃OH saturated with argon (H₂)=0,69 and (HCHO)=0,22 were found; in the presence of 7·10^–4 M-CO the yields are (H₂)=0,10 and (HCHO)=0,29, whereas under saturation with oxygen (10^–3 M O₂) (H₂)=0,01, (HCHO)=0,33, (HCOOH)=0,20 and (H₂O₂)=0,22. The quantum yields of all other products obtained under the conditions mentioned above are <0.07. With increasing methanol concentration up to pure argon saturated methanol, the quantum yields of H₂, HCHO and (CH₂OH)₂ increase correspondingly, whereas the yields of HCOOH and CH₂OHCHO remain practically unchanged. When irradiating pure, argon saturated methanol, (H₂)=0,89 and (HCHO)=0,73 were found. A maximum yield of (CH₂OH)₂=0,38 was achieved using 2M-CH₃OH. Reaction mechanisms are discussed.

     

Seawater—A test of multicomponent electrolyte solution theories. I. The apparent equivalent volume,expansibility, and compressibility of artificial seawater

The apparent equivalent volume _V, expansibility _E, and compressibility _K of an artificial seawater solution containing10 ionic components (Na⁺, Mg²⁺, Ca²⁺, K⁺, Sr²⁺, Cl^–, SO ₄ ^2– , HCO ₃ ^– , Br^–, and F^–) and one nonionic component (H₃BO₃) has been determined from0 to40°C (in5° intervals) and from0.1 to0.8 m ionic strength at1 atm. The concentration dependence (I_v=volume ionic strength) of the _V's, _E's, and _K's have been examined by using a Masson-type equation, = ^° +S'I _V ^1/2, and a Redlich-type equation, = ^° +SI _V ^1/2 +BI _V, where ^° is the infinite-dilution value, S is the empirical Masson slope, S is the theoretical Debye-Hückel slope, and B is an empirical deviation constant. By using Young's rule, = E_i(i), the apparent equivalent volumes, expansibilities, and compressibilities for sea salt have been estimated from the ionic and nonionic components making up the mixture. The estimated apparent molal quantities agree very well with the directly measured values providing the concentration terms, S _i and B_i, are weighted according to the methods of Wood and Reilly.Contribution Number 1599 from the University of Miami.     

The Influence of Dimerization of Water-Soluble Metalloporphyrins as Photosensitizers on the Efficiency of Generation of Singlet Oxygen

Quantum yields () for the generation of singlet oxygen sensitized by Pd(II) complexes of water-soluble porphyrins: meso-tetrakis(4-N-methylpyridyl)porphine [PdTMPyP]⁴⁺ ( = 0.9), meso-tetrakis(4-N,N,N-trimethylaminophenyl)porphine [PdTTMAPP]⁴⁺ ( = 0.8), meso-tetrakis(4-carboxyphenyl)porphine [PdTCPP]^4– ( = 0.7), and meso-tetrakis(4-sulfonatophenyl)porphine [PdTSPP]^4– ( = 0.5) were determined using a chemical method. It was found that the dimerization and aggregation of metalloporphyrins greatly influence the value. The quantum yields evaluated for the formation of singlet oxygen sensitized by metalloporphyrin monomeric and dimeric forms are _{, M} 0.9 and _{, D} 0.2, respectively, and do not depend on the porphyrin nature.     

On a variational method for determining excited state wave functions

A variational method is proposed which results in an approximate wave function for an excited state which has the maximum overlap with the true excited state eigenfunction. The method involves the calculation of the quantities E=¦H¦ and =¦(H-E)²¦, but is free of the constraint that the trial function must remain orthogonal to all states of the same symmetry which lie beneath it. One must know, however, an approximation to the true eigenvalue. A discussion is given on how one might gain the latter information, lacking knowledge of the spectrum, from the repeated application of the method.

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Zusammenfassung Es wird eine Variationsmethode vorgeschlagen, die auf eins genäherte Wellenfunktion für einen angeregten Zustand führt, welche sich maximal mit der wahren Eigenfunktion des angeregten Zustandes überlappt. Die Methode ermöglicht die Berechnung der Größen: E=¦H¦ und =¦(H-E)²¦, ist aber frei von der Nebenbedingung, daß die Versuchsfunktion orthogonal zu allen benachbarten Zuständen mit derselben Symmetrie bleiben muß. — Man will jedoch eine Näherung des wahren Eigenwertes wissen. — Eine Diskussion darüber, wie man durch wiederholte Anwendung der Methode letztere Information gewinnen kann, ohne Kenntnisse über das Spektrum zu besitzen, wird durchgeführt.

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Résumé Méthode variationnelle pour la détermination d'une fonction d'onde d'un état excité présentant le recouvrement maximum avec la fonction d'onde exacte. La méthode implique le calcul de E=¦H¦ et =¦(H-E)²¦ mais ne comporte pas la contrainte d'orthogonalité de la fonction d'essai à tous les états inférieurs de même symétrie. On doit cependant connaître une valeur approchée de la valeur propre exacte. Discussion sur la manière dont on peut obtenir cette valeur approchée sans connaître le spectre, par application répétée de la méthode.

     

De la possibilité d'utiliser une base de Slater uniquement s dans les calculs relatifs aux atomes et aux molécules

A 2p STO may be replaced by a linear combination of 1s and 2s orbitals, = (1s_A-1s_f) + (2s_A-2s_B). Such a should improve LCAO-MO-SCF calculations in minimal STO basis set with simpler programs.     

r 12-Dependent terms in the wave function as closed sums of partial wave amplitudes for large l

The ansatz = (1+1/2r₁₂)+ with the bare nuclear (or screened nuclear) wave function and expanded in products of one-electron functions is explored for second-order perturbation theory and for variational calculations of the ground state of Helium-like ions.The energy increments E _l ⁽²⁾ corresponding to the partial wave expansion of go asymptotically as l^–8, while conventional partial wave increments go as l^–4. is coupled to by a residual interaction U₁₂ that has no singularity for r₁₂=0. With the present ansatz it is sufficient to include l-values up to 5 in order to get the second-order energy accurate to one microhartree. For the same accuracy l4 is sufficient in a CI with correlated reference function while in conventional CI one must go to l50. The surprisingly faster convergence of the variational approach as compared to second-order perturbation theory is explained. The slow convergence of the traditional partial wave expansion is entirely due to the attempt to represent the quantity 1=¦r₁₂r₁₂ ^–1¦ by its partial wave expansion. The best reference function shows very little shielding and resembles closely the eigenstate of the bare nuclear Hamiltonian. The generalization to arbitrary systems is discussed and it is pointed out that the calculation of difficult integrals can be avoided without a significant loss in accuracy.     

EXAFS Study of Ph3GeMn(CO)5 Structure Evolution on Exposure to X-Radiation

Ge K-edge and Mn K-edge EXAFS spectroscopy was used to study changes in the local environment of germanium and manganese atoms during radiolysis of the Ph₃GeMn(CO)₅ complex. On exposure to X-radiation, the metal complex undergoes a number of transformations depending on the radiant exposure (). It was shown that at = (6–8) × 10⁶ J/m², the initial metal complex decomposes into the [Ph₃Ge] and [Mn(CO) _n ] fragments with partial detachment of the CO groups from Mn atoms. When = 1.3 × 10⁷ J/m², Mn atoms lose completely the CO groups to form finely dispersed metal nanoparticles, which interact with the surrounding atoms (carbon or nitrogen). With further increase in , the local environment of the Mn atoms no longer changes. The Ge atoms remain coordinated to the Ph groups as increases up to 2 × 10⁷ J/m², but starting with = 1.6 × 10⁷ J/m², metal–metal bonds are formed; subsequently, the amount of this phase increases and when = 2.6 × 10⁸ J/m², it becomes predominant. Since manganese and germanium atoms lose their ligands at different values, one can conclude that germanium and manganese nanoparticles are the final products in the radiolysis of Ph₃GeMn(CO)₅.     

Study of interaction between trimethyl-substituted silanes and silica surface

Interaction mechanism of (CH₃)₃SiX silanes (X=Br, I, N₃, NCS, NCO, CN, NCNSi(CH₃)₃ and SO₄Si(CH₃)₃ with dehydrated silica surface has been studied by IR spectroscopy. It has been established that (CH₃)₃SiCN, (CH₃)₃SiBr, (CH₃)₃SiI and [(CH₃)₃Si]₂SO₄ can be used as soft silylating agents for endcapping.

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(CH₃)₃SiX (X=Br, I, N₃, NCS, NCO, CN, NCNSi(CH₃)₃, SO₄Si(CH₃)₃) -. , (CH₃)₃SiCN, (CH₃)₃SiBr, (CH₃)₃SiI [(CH₃)₃Si]₂SO₄ .

     

Vibrational isotope effect by the low rank perturbation method

Mathematical formalism of the low rank perturbation method (LRP) is applied to the vibrational isotope effect in the harmonic approximation. A pair of two n-atom isotopic molecules A and B which are identical except for isotopic substitutions at atomic sites is considered. Relations which express vibrational frequencies _k and normal modes _k of the perturbed isotopic molecule B in terms of the vibrational frequencies _i and normal modes _i of the unperturbed molecule A are derived. In these relations complete specification of the unperturbed normal modes _i is not required. Only amplitudes | _i of normal modes _i at sites affected by the isotopic substitution are needed.     

An Alternative Method of Introducing Fugacity

In current textbooks fugacity is introduced according to its differential or integral mathematical formulation. In this article an alternative method of explanation is offered. It is suggested that the real state of a pure gas can be described by comparing it to a hypothetical idealized state. The differences between these two states can then be expressed in terms of a function, , defined as (T,P) = _real(T,P) - _ideal(T,P) where _real and _ideal are the chemical potentials of the gas in its real and ideal states, respectively. The function is a molar excess quantity and is expressed as (T,P) = RT1n where is the fugacity coefficient. This approach introduces fugacity deductively through the function, which leads to , the fugacity coefficient. This method is also appropriate for introducing the activity of solution components and the fugacity of a real gas in gaseous mixtures.     

Partial molal expansibilities of organic compounds in aqueous solution. I. Alcohols and ethers

The temperature dependence of limiting apparent molal volumes ° in water for some alcohols (methanol, ethanol, 1-propanol, 2-butanol, 3-pentanol, 3-hexanol, 2,5-hexanediol, cyclopentanol, cyclohexanol, cycloheptanol, and 1,4-cyclohexanediol) and ethers (trimethylene oxide, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, 1,3-dioxepane, 1,3,5-trioxane, dimethoxymethane, 1,2-dimethoxyethane, diethoxymethane, and diethyl ether) has been studied in the temperature range 10–50°C by means of an automatic digital-readout dilatometer. Values of the thermal expansion coefficient * = (1/°)(°/T)_p have been obtained at several temperatures and discussed together with literature data on expansibilities of related compounds. The data show a wide spectrum of values of ^* at low temperatures which is narrowed at the higher ones. The expansibilities of monofunctional alcohols increase with increasing temperature; the opposite effect is observed for polyhydric alcohols. The ^*'s of ethers are very slightly temperature dependent and are much higher, at low temperature, than those of alcohols having the same ratio ofn _o/n_c. These results are discussed in terms of solutewater interactions, and a possible interpretation is put forward.     

Total chromatographic optimization (TOCO) I. Simultaneous optimization of many variables in liquid chromatography

Summary The following chromatographic variables are totally optimized based on the recently developed information theory of optimization: mobile phase composition, column length, flow rate, wavelength, and the amount of internal standard. The optimal internal standard is selected from among six candidates. Two types of optimal conditions (- and -optimals) are proposed: the -optimal is defined as the most precise analysis (the maximal ) while the -optimal is the most efficient (rapid) analysis (the maximal ). The observation times for the determination of an antipyretics mixture (three components) in liquid chromatography are ca. 50 s for the -optimal and ca. 8 min for the -optimal. The reliability of the - and -optimals is verified by experiments.     

Vibrational isotope effect of linear and planar molecules: Deuterated bromoethenes

Linear (planar) molecules A and B which are identical except for isotopic substitutions at the atomic sites are considered. Stretching (bending, out-of-plane) frequencies _k and normal modes _k of the isotopically perturbed molecule B are expressed in terms of stretching (bending, out-of-plane) frequencies _i and the corresponding normal modes _i of the unperturbed molecule A. Complete specification of the unperturbed normal modes is not required. All that is needed are stretching (bending, out-of-plane) amplitudes | _i of the normal modes _i at those sites that are affected by isotopic substitution. The rule which interlaces frequencies _k of molecule A with frequencies _i of molecule B is derived. Given two isotopic molecules A and B that differ by a single isotopic substitution at site , the inversion relation is derived. This relation expresses unperturbed stretching (bending, out-of-plane) amplitudes at the site in terms of stretching (bending, out-of-plane) frequencies of molecules A and B . As an example, out-of-plane vibrations of deuterated bromoethene were considered. In the simplest method 12 out-of-plane frequencies of four polydeuterated bromoethenes were calculated from 12 out-of-plane frequencies of bromoethene and three monodeuterated bromoethenes. Standard deviation of thus calculated frequencies from experimental frequencies is =2.74 cm^–1. In another method, 15 out-of-plane frequencies of four polydeuterated bromoethenes and selected monodeuterated bromoethene are calculated from 9 out-of-plane frequencies of bromoethene and the remaining two monodeuterated bromoethenes. Depending on which monodeuterated bromoethene is selected (1-, cis- or trans-), standard deviation of thus obtained frequencies from experimental frequencies is 1=2.84 cm^–1, c=2.96 cm^–1 and t=2.72 cm^–1.     

n-Hexane cracking over heteropoly acids, 3. Silica supported heteropoly acids

Silica supported heteropoly acids are active in n-hexane cracking, while the pure compounds (except H₃PW₁₂O₄₀) are inactive. This result is explained by a partial transformation of H₆P₂W₁₈O₆₂ and H₆P₂W₂₁O₇₁ (H₂O)₃ into H₃PW₁₂O₄₀. In the case of H₄SiW₁₂O₄₀, the polyanion in interaction with silica leads to superacidic species upon thermal treatment.

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, , -, ( H₃PW₁₂O₄₀) . H₆P₂W₁₈O₆₂ H₆P₂W₂₁O₇₁ (H₂O)₃ H₃PW₁₂O₄₀. H₄SiW₁₂O₄₀ , , .

     

Relative enthalpies and related thermodynamic functions of some organic compounds by drop calorimetry

The values of thermodynamic functions of the following eight organic compounds under non-reacting conditions within the temperature range 298.15 – 550 K are given: N,N dimethylformamide, CHO · N(CH₃)₂; 4-nitro-1-chlorobenzene, Cl · C₆H₄ · NO₂; sodiump-nitrophenoxide, NO₂ · C₆H₄ · ONa; 1-methyl-2-pyrrolidone, 4,4-dinitrodiphenyl ether, (NO₂ · C₆H₄)₂O; 4,4-diaminodiphenyl ether, (NH₂ · C₆H₄)₂O; bis-(4-aminophenyl)methane, (NH₂ · C₆H₄)₂CH₂; bis(4-maleic acidimidphenyl)methane, The relative enthalpy was obtained from calorimetric data by drop calorimetry. The heat capacity and relative entropy are functions derived from the foregoing. The equations of the temperature variation of the relative enthalphy were obtained by computer processing of the calorimetric data by the least squares method. The parameters of solid-liquid transitions were determined from the discontinuity of the temperature variation of the relative enthalpy.

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Zusamenfassung Die Werte der thermodynamischen Funktionen folgender 8 organischer Verbindungen werden unter nicht-reagierenden Bedingungen im Temperaturbereich von 298.15 bis 550 K angegeben: Dimethylformamid, CHO · N(CH₃)₂;p-Nitrochlorbenzol, Cl · C₆H₄NO₂; Natrium-p-Nitrophenoxid, NO₂ · C₆H₄ONa; N-Methylpyrrolidon, 4-4-Dinitrodiphenyläther, (NO₂ · C₆H₄)₂O; 4-4-Diaminodiphenyläther, (NH₂C₆H₄)₂O; 4-- 4-Diaminodiphenylmethan, (NH₂ · C₆H₄)₂CH₂; 4-4-bis-Maleinimid-Diphenylmethan, Die relative Enthalpie wird aus kalorimetrischen Daten der Temperaturgefällekalorimetrie erhalten. Die Wärmekapazität und die relative Entropie sind Funktionen der erwähnten Werte. Die Gleichungen der Temperaturänderung der relativen Enthalpie wurden mittels Computerverarbeitung der kalorimetrischen Daten, mit der Methode der kleinsten Quadrate erhalten. Die Parameter der fest-flüssig Übergänge wurden an Hand der Diskontinuität der Temperaturänderung der relativen Enthalpie bestimmt.

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Résumé On donne les valeurs des fonctions thermodynamiques des 8 composés organiques suivants, en conditions non réactionnelles, dans l'intervalle de températures 298.15–550 K: diméthylformamide CHO · N(CH₃)₂,p-nitrochlorobenzène Cl · C₆H₄ · NO₂,p-nitrophé noxysodium NO₂ · C₆H₄ · ONa, N-méthylpyrrolidone dinitrodiphényl-4,4 éther (NO₂ · C₆H₄)₂O, diaminodiphényl-4,4 méthane (NH₂ ·H ₄CH₂, 4-4 bis maléinimide diphénylméthane L'enthalpie relative a été obtenue à partir de données calorimétriques fournies par un calorimètre à chute. La chaleur spécifique et l'entropie relative sont des fonction dérivées de la précédente. Les équations donnant la variation de l'enthalpie relative en fonction de la température sont obtenues par traitement des données calorimétriques sur ordinateur par la méthode des moindres carrés. Les paramètres des transitions solide-liquide ont été déterminés à partir de la discontinuité de la variation de l'enthalpie relative avec la température.

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, 298,15–550 , : — · N(CH₃)₂;- — l · ₆₄ · NO₂.- -NO₂·₆₄·ONa; N-—₃·N··₂·₂₂; 4,4- — (NO₂·₆₄)₂; 4,4- — (NH₂·₆₄)₂; 4,4- — (NH₂·₆₄)₂₂; 4,4-- —(₆₄.N. . :. )₂₂. . , . . - .

     

The activity of Ni/AlPO4, Ni/AlPO4?Al2O3 and Ni/AlPO4?SiO2 catalysts in the hydrogenation of e-cinnamaldehyde

Liquid-phase catalytic hydrogenatio of E-cinnamaldehyde was carried out by using new supported nickel catalysts (Ni/AlPO₄, Ni/AlPO₄–Al₂O₃ and Ni/AlPO₄–SiO₂) in methanol as solvent under low hydrogen pressure (4.1 bar) and 298 K. The kinetic orders are zero in H₂ and aldehyde. The selectivity to the hydrogenaton of the C=C double bond is very high (>99%)

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- (Ni/AlPO₄, Ni/AlPO₄–Al₂O₃ Ni/AlPO₄–SiO₂) (4,1 ) 298 . H₂ . C–C (>90%).

     

Rate constant of unimolecular decomposition of the radical (CH3)2juvyCCH(CH3)2

The energy of activation of CH ₃ ^. radical rupture from the radical (CH₃)₂juvyCCH(CH₃)₂ is 142.2 kJ mol^–1; the selfcombination rate constant is k_c {(CH₃)₂juvyCCH(CH₃)₂}=10^7.3 dm³ mol^–1 s^–1.

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CH ₃ ^. (CH₃)₂juvyCCH(CH₃)₂ 142,2 /, k_c {(CH₃)₂juvyCCH(CH₃)₂}=10^{7,3 3–1 –1}.

     

Photolysis of water-carbon tetrachloride and water-chlorobenzene saturated solutions and their two-phase systems. Quantum yields of chloride ions

The quantum yields of formation of chloride ions were determined in photolysis (=254 nm) of watercarbon tetrachloride organic phase of CCl₄(Cl^–)=0.89±0.04 water-chlorobenzene (_PhCl(Cl^–)=0.137± ±0.005) two-phase systems and saturated aqueous solutions of carbon tetrachloride (_CCl4(Cl^–)=18.9±5.6 and chlorobenzene _PhCl(Cl^–)=0.56±0.03. The quantum yields of chloride ions obtained from these systems are compared with partial radiation yields in the same systems. A mechanism for formation of Cl^– ions is proposed.