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1.
The standard (po = 101.325 kPa) molar enthalpies of combustion in oxygen at 298.15 K were measured by static-bomb calorimetry and the standard molar enthalpies of sublimation at 298.15 K were measured by microcalorimetry for 1,2-dihydroxybenzene (catechol) and six alkylsubstituted catechols:
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2.
The enthalpies of formation in the crystalline state at 298.15 K of o-, m-, and p-t-butyl-benzoic acids have been determined by static-bomb calorimetry. Vapour-pressure determinations were made by the Knudsen-effusion technique and the sublimation enthalpies at the mean temperatures of the measurement ranges have been derived for the three acids. The values obtained are:
cHmo(cr)/(kJ·mol?1)ΔsubHmo/(kJ·mol?1)
Catechol2864.5 ± 0.886.6 ± 1.6
3-Methylcatechol3505.4 ± 0.593.2 ± 1.0
4-Methylcatechol3504.6 ± 0.694.9 ± 1.0
3-isoPropylcatechol4808.8 ± 1.197.8 ± 1.7
4-terButylcatechol5461.9 ± 0.999.3 ± 1.4
3-Methyl-6-isopropylcatechol5460.2 ± 0.996.6 ± 0.9
3,5-diterButylcatechol8082.7 ± 1.8100.1 ± 0.6
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3.
The energies of combustion of 3,4- and 3,5-dimethylbenzoic acids have been revised by combustion calorimetry. Vapour pressures of very pure samples of the six dimethylbenzoic acids have been determined over a range of temperatures near 298 K by the Knudsen-effusion technique. From the experimental results and our previously published thermochemical quantities the following results for the six C6H3(CH3)2CO2H isomers at 298.15 K have been derived.
ΔHfo(c, 298.15 K)/kJ mol?1ΔHs/kJ mol?1
o-t-butylbenzoic acid476.2 ± 1.999.8 ± 0.4(at 314.6 K)
m-t-butylbenzoic acid504.3 ± 1.6103.0 ± 0.5(at 326.5 K)
p-t-butylbenzoic acid502.9 ± 1.7103.8 ± 0.4(at 334.1 K)
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4.
Spectrophotometric investigation of the deep blue colored, water-soluble complex of
1. Stability constant and free energy of formation of Cu-NMS complex at 30 ± 1 °C
IsomerΔfHmo(cr)ΔsubHmoΔfHmo(g)
kJ·mol?1kJ·mol?1kJ·mol?1
2,6-?440.7 ± 1.799.1 ± 0.2?341.6 ± 1.7
2,3-?450.4 ± 1.7104.6 ± 0.4?345.8 ± 1.7
2,5-?456.1 ± 1.6105.0 ± 0.6?351.1 ± 1.7
2,4-?458.5 ± 1.7103.5 ± 0.3?355.0 ± 1.7
3,4-?468.8 ± 1.9106.4 ± 0.3?362.4 ± 1.9
3,5-?466.8 ± 1.7102.3 ± 0.3?364.5 ± 1.7
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5.
Enthalpies of combustion and vaporization at 298.15 K have been measured for 3,5-dithiaheptane and 3,6-dithiaoctane. Enthalpies of formation at 298.15 K have been derived for the compounds in the liquid and gaseous states. The results are:
MethodlogKsΔF (Kcal/mole)
Mukherji and Dey (4)4.11?5.70
Subhrana and Raghavrao (6)4.80?6.66
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6.
Enthalpies of reaction, ΔHr, of the monouranates of lithium, potassium, and rubidium with 1 mol dm?3 HCl have been measured calorimetrically. From these measurements, and auxiliary determinations of the enthalpies of solution in acid of the chlorides of lithium, potassium, and rubidium and of uranyl chloride, the standard enthalpies of formation of the uranates, ΔHfo, have been derived. The results obtained are as follows:
ΔHfo(l)/kJ mol?1ΔHfo(g)/kJ mol?1
3,5-Dithiaheptane?116.0 ± 1.5?65.2 ± 1.5
3,6-Dithiaoctane?142.5 ± 1.5?83.0 ± 1.5
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7.
The energies of combustion of 2,3-, 2,4-, 2,6-, 3,4-, and 3,5-dimethoxybenzoic acids have been determined by static-bomb calorimetry. The enthalpies of formation in the crystalline state at 298.15 K have been derived for these five acids. The values obtained are:
ΔHr/kcalth mol?1ΔHfo(c, 298.15 K)/kcalth mol?1
α-Li2UO4?(41.77±0.02)?(463.31±0.84)
K2UO4?(42.07±0.05)?(451.39±0.83)
Rb2UO4?(41.30±0.05)?(452.00±0.85)
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8.
We present the heat capacities measured by adiabatic calorimetry from 6 to 350 K, and by differential scanning calorimetry from 300 to 500 K, of CsCrCl3 and RbCrCl3. A first-order transition at Tc = (171.1±0.1) K was detected for CsCrCl3. The RbCrCl3 showed at Tc = (193.3±0.1) K a transition with thermal hysteresis at temperatures just below the maximum. At T1 = (440±10) K a continuous transition was also detected. Furthermore, at TN ≈ 16 K, and for both compounds, a small bump due to magnetic long-range ordering was observed. The thermodynamic functions at 298.15 K are
?ΔHfo(c)/kJ mol?1
2,3-dimethoxybenzoic acid687.0 ± 1.4
2,4-dimethoxybenzoic acid712.2 ± 1.4
2,6-dimethoxybenzoic acid693.8 ± 1.4
3,4-dimethoxybenzoic acid714.0 ± 1.4
3,5-dimethoxybenzoic acid724.0 ± 1.5
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9.
10.
Calorimetric measurements of the enthalpy of solution of cesium chromate gave ΔHsoln = (7622 ± 24) calth mol?1 for a dilution of Cs2CrO4·21128H2O. This result, along with the enthalpy of dilution gave the standard enthalpy of solution, ΔHsolno = (7512 ± 31) calth mol?1, whence the standard enthalpy of formation, ΔHf0(Cs2CrO4, c, 298.15 K), was calculated to be ?(341.78 ± 0.46) kcalth mol?1. Recomputed thermodynamic data for the formation of the other alkali metal chromates have been tabulated. From their solubilities and enthalpies of solution, the standard entropies, S0(298 K), of BaCrO4 and PbCrO4 were estimated to be (38.9 ± 0.9) and (43.7 ± 1.2) calth K?1 mol?1, respectively. There is evidence that ΔHf0(SrCrO4, c, 298.15 K) may be in error. Thermochemical, solubility, and equilibrium data, have been combined to update the thermodynamic properties of the aqueous chromate (CrO42?), bichromate (HCrO4?), and dichromate (Cr2O72?) ions. The new values at 298.15 K are as follows:
Cp,mRSmoR{Hmo(T)?Hmo(0)}RK?{Gmo(T)?Hmo(0}RT
CsCrCl315.3826.493503.214.735
RbCrCl315.7625.993556.814.384
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11.
12.
The acidic dissociation constants of three vic-dioximes have been determined from spectrophotometric data. The results may be summarized as follows:
S0/calth K?1 mol?1ΔHf0/kcalth mol?1ΔGf0/kcalth mol?1
CrO42?(aq)(13.8 ± 0.5)?(210.93 ± 0.45)?(174.8 ± 0.5)
HCrO4?(aq)(46.6 ± 1.8)?(210.0 ± 0.7)?(183.7 ± 0.5)
Cr2O72?(aq)(67.4 ± 3.9)?(356.5 ± 1.5)?(312.8 ± 1.0)
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13.
14.
Cobalt ions in aqueous thiocyanate solution react with Aliquat-336-xylene solution to form anion-association complex which is easily extracted into the organic phase. A typical extraction procedure involves extracting a solution which is 10 ppm in cobalt and 0.06 M,
5. Stripping of Cobalt from 2% Aliquat-336-Xylene Solutions
pK1pK2
2,3-butanedionedioxime10.6 ± 0.111.9 ± 0.3
1,2-cyclohexanedionedioxime10.6 ± 0.212.4 ± 0.5
1,2-cycloheptanedionedioxime10.7 ± 0.212.3 ± 0.5
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15.
Electrical conduction (dc) studies are made with pure and cobalt(II)-doped single crystals of NH4H2PO4 and KH2PO4. The effect of the dopant concentration on the enthalpy for the migration of protons and the enthalpy for the rotation of the H2PO4 group have been studied. It is suggested that proton migration occurs through a synchronous phosphate rotation mechanism. Tritium diffusion studies in KDP and 32PO4 diffusion in ADP crystals have been made. The mechanisms for the conduction and diffusion processes are found to be different in nature. The distribution coefficients of Co(II) dopant in ADP (2.92 × 10?3) and KDP (1.14 × 10?3) are calculated. The following enthalpy values are obtained.
StrippantCobalt stripped (%)
Na2S (M) 1.018.3
2.010.7
Na2SO3 (M) 0.110.7
0.549.6
1.052.9
EDA (%) 2.576.6
NaOH (M) 0.14.1
0.574.1
1.090.8
2.076.8
NH4OH (M) 0.124.1
0.591.8
1.097.5
2.099.9
EDTA (M) 0.02>99.9
0.05>99.9
0.1>99.9
EDTA (%) 0.1>99.9
0.5>99.9
1.0>99.9
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16.
With the help of the Chcvcnard thcrmobalancc the authors have determined the minimum temperatures necessary for quantitatively converting the derivatives of gallium into oxide Ga203.
KDP (eV)ADP (eV)
Enthalpy for the migration of protons0.01 ± 0.010.15 ± 0.02
Enthalpy for the rotation of phosphate group0.71 ± 0.010.66 ± 0.01
Enthalpy for T-diffusion0.14 ± 0.01
Enthalpy for 32PO4 diffusion0.24 ± 0.01
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17.
A polarographic method for the determination of antimony in lead-antimony alloys has been developed. It was found that the interference due to the presence of varying concentrations of lead and hydrochloric acid would be eliminated by the addition of potassium chloride.
t001. The method gave satisfactory results within the range:
Hydroxide by ammonium hydroxide408°
Hydroxide by ammonia400°
Hydroxide by urea475°
Hydroxide by aniline546°
Hydroxide by sulpliitc813°
Hydroxide by tannin520°
Cupfcrron745°
Camphoratc478°
Dibromo-oxinate817°
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18.
19.
Two stereoselective routes for the synthesis of trienes having a central cis double bond have been devised. These were employed for the synthesis of (Z)-1-(cyclohexen-1-yl)-1,3-butadiene (1), (Z,E)-1-(cyclohexen-1-yl)-1,3-pentadiene (2), (Z,Z)-1-(cyclohexen-1-yl)-1,3-pentadiene (3), 1,2-divinyleyclohexene (4), (E,Z)-1-phenyl-1,3,5-hexatriene (5), (Z,Z)-1-phenyl-1,3,5-hexatriene (6) and (E,Z)-1-(p-chlorophenyl)-1,3,5-hexatriene (7). Rates of the thermal electrocyclization and activation parameters were measured for these in inert solvents. The results are tabulated below.
Hydrochloric acid4 — 8M
Lead0 — 0.03M
Antimony0 — 0.002M
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20.
The authors discuss several aspects of the chemistry of indium, giving evidence for a hydrate 2ln2O3.H2O and studying in detail the behaviour of indium sulphide heated in air. Compared with that of gallium, the oxinate is particularly stable.Compounds used for the gravimetric determination of indium should be heated to the following temperatures in order to give correct results:
Compoundk1 x 105(sec?1)Temp (°C)ΔH3ΔS3
112·813229?6
212·513229?1
32·617334?5
43·8612525?15
516·014528?8
63·0195
715·014525?18(?)
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Hydroxide by ammonia345°
Hydroxide by hexamethylene tetramine546°
Hydroxide by cyanate475°
Sulphide94–221°, 320–544°, 690°
Phosphate477°
Luteocobaltic indichloride100–105°
Oxinate100–285°
Diethyldithiocarbamate100–210°
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