Excess heat capacities and excess volumes of tetraalkyltin compounds: . Effect of correlations of molecular orientations and steric hindrance. Part 1

1984 ◽  
Vol 62 (6) ◽  
pp. 1008-1015 ◽  
Author(s):  
Bernard Riedl ◽  
Geneviève Delmas
Keyword(s):  
Steric Hindrance ◽  
Central Atom ◽  
Orientational Order ◽  
Excess Volumes ◽  
Pure Liquid ◽  
Flory Theory ◽  
Flow Calorimeter ◽  
Alkyl Chains ◽  
Chain Compounds ◽  
Long Chain

A Picker flow calorimeter has been used to obtain molar excess capacities [Formula: see text] through the concentration range at 25 °C for the systems [Formula: see text] where R is the alkyl group CnH2n+1, (n = 1, 2, 3, 4, 8, 12). Excess volumes have also been measured for the mixtures. Two contributions to [Formula: see text] and vE were investigated: those associated with disordering the long alkyl chains and with steric hindrance. The steric hindrance contribution has been found to occur for molecules having a highly substituted central atom. The sign of this contribution is negative in hE and positive in [Formula: see text], indicative of an ordering or loss of mobility for the molecules going from pure liquid to solution. The [Formula: see text] results confirm the more sterically hindered character of the ethyl and propyl derivatives already found with hE. The separation of the disorder and steric contribution is possible in systems involving long-chain compounds. It is found that the orientational order contribution diminishes more slowly with temperature than the steric hindrance effect. The trend of vE in the series is reasonably well predicted by the Prigogine–Patterson–Flory theory.

Heats of mixing of trialkylamines: disorder and steric hindrance contributions

1978 ◽  
Vol 56 (22) ◽  
pp. 2856-2865 ◽  
Author(s):  
Robert Philippe ◽  
Geneviève Delmas ◽  
Phuong Nguyen Hong
Keyword(s):  
Steric Hindrance ◽  
Significant Contribution ◽  
Orientational Order ◽  
Class A ◽  
Heats Of Mixing ◽  
Class B ◽  
Chain Compounds ◽  
Sterically Hindered ◽  
Long Chain ◽  
Long Chains

Nine trialkylamines, triethyl- to trihexylamine trioctyl-, tridodecyl, tri(methyl-2-butyl)-, and dimethyldodecylamine have been used for heats of mixing of the following systems at 298 K: A, fourteen systems made of all the possible binary mixtures (except one) of the six shorter amines; B, twelve systems made of a long chain amine, trioctyl-, tridodecyl- or dimethyldodecylamine with the four shorter members of the series; C, two systems consisting of the mixture of two long-chain compounds, trioctylamine with tridodecyl- and dimethyldodecylamine. Heats for the class A systems are less than or equal to 40 J/mol, indicating no net effect of the small polarity of the shorter members of the series. The experimental HE of these mixtures are compared with two theories. The Monte Carlo approach gives good predictions but the heats calculated with the Snider–Herrington theory are too negative. Heats of the class B systems are suitable for the investigation of two new contributions to the heats of mixing, the positive heat of disordering of long-chains HE(dis.) and the negative heat found in systems where one of the components is sterically hindered, HE(ster.hindr.). HE(dis.) found with the long-chain amines indicates an orientational order larger than in the case of the n-alkane of the same chain-length but equivalent to that found in the tetraalkyltin compounds of the same length. Recent work has shown that the tetrapropyl and tetraethyltin derivatives when mixed with long-chain alkanes or tin derivatives give rise to a HE(ster.hindr.) contribution. From this work and the present study, the steric hindrance contributions of five sterically hindered compounds tetraethyltin and tetrapropyltin, triethyl- and tripropylamine, and 3,3-diethylpentane mixed with different second components are calculated. The steric hindrance contribution is found proportional to the volume of the second component and increasing in the following order of the sterically hindered component: triethyl- < tripropylamine < tetraethyl- < tetrapropyltin < 3,3-diethylpentane. Heats of the class C systems are small without significant contribution of HE(dis.) due to the fitting of the long-chains in solution.

Excess heats of tri-n-alkylamines and tetraalkyl tin compounds in linear and branched alkanes: correlations of molecular orientations and steric hindrance effect

1979 ◽  
Vol 57 (5) ◽  
pp. 517-525 ◽  
Author(s):  
R. Philippe ◽  
G. Delmas ◽  
Phuong Nguyen Hong
Keyword(s):  
Steric Hindrance ◽  
Solution Structure ◽  
The Other ◽  
Short Chain ◽  
Flory Theory ◽  
Tin Compounds ◽  
Branched Alkanes ◽  
Linear Alkanes ◽  
Chain Compounds ◽  
Long Chain

Excess heats of the following mixtures of trialkylamines and tetraalkyl tin compounds with branched and linear alkanes have been measured at 25 °C: five trialkylamines NR3 (R = C2H5, C3H7, C4H9, C10H21, C12H25) with six linear alkanes, n-C5, n-C6, n-C8, n-C10, n-C12, n-C16, and three highly branched alkanes, 2,2,4-trimethylpentane, 2,2,4,6,6-pentamethylheptane, and 2,2,4,4,6,8,8-heptamethylnonane (br-C16). Further measurements were carried out on tetrapropyl tin (SnPr4) with n-C8, n-C16, and br-C16.Measurements were made to obtain more information on the heats of disordering of long chain compounds and on an exothermic contribution to the heats coming possibly from the sterically hindered character of one of the components of the mixture. The three short-chain trialkylamines have large heats with the linear long alkanes and small heats with the branched alkanes. On the other hand, the two long-chain trialkylamines have very small heats with linear alkanes and large heats with the branched alkanes. These results are interpreted as indicating no change of liquid or solution 'structure' when two ordered compounds (long alkanes and long-chain amines) are mixed but a change of 'structure' when an ordered compound (long alkane or long-chain amine) is mixed with a non-ordered one (branched alkane or short-chain amine). The heat of disordering of n-hexadecane is obtained with many order breakers and found to depend to some extent on the expansion coefficient of the order breaker. HE values for the series of the shorter NR3 do not vary regularly with molecular weight but are smaller for the propyl (and possibly the ethyl) derivative. Similarly, HE of SnPr4 in n-C16, br-C16, and n-C8 are much lower than the corresponding heats with SnEt4 and SnBut4. This is attributed to the presence of the exothermic contribution to the heats, HE(steric hindrance). The X12 parameter of the Flory theory has been calculated and is interpreted in terms of the disorder and steric hindrance contributions to the heats.

Spin-crossover iron(II) long-chain complex with slow spin equilibrium at low temperature

2021 ◽  
Author(s):  
Qi Zhao ◽  
Jin-Peng Xue ◽  
Zhi-Kun Liu ◽  
Zi-Shuo Yao ◽  
Jun Tao
Keyword(s):  
Low Temperature ◽  
Single Crystal ◽  
Spin Crossover ◽  
Chain Complex ◽  
Mononuclear Complex ◽  
X Ray ◽  
Alkyl Chains ◽  
Long Chain

A mononuclear complex with long alkyl chains, [FeII(H2Bpz2)2(C9bpy)] (1; H2Bpz2 = dihydrobis(1-pyrazolyl)borate, C9bpy = 4,4'-dinonyl-2,2'-bipyridine), was synthesized. Single-crystal X-ray crystallographic studies revealed that - and - forms of the complex...

scholarly journals Stereospecific Hydroxylation of Long Chain Compounds by a Species of Torulopsis

1969 ◽  
Vol 244 (4) ◽  
pp. 882-888 ◽  
Author(s):  
E Heinz ◽  
A P Tulloch ◽  
J F T Spencer
Keyword(s):  
Chain Compounds ◽  
Long Chain

Polytypic structure and low-frequency Raman spectra of long-chain compounds: Stearic acid E form

1993 ◽  
Vol 24 (8) ◽  
pp. 527-532 ◽  
Author(s):  
Fumitoshi Kaneko ◽  
Masamichi Kobayashi ◽  
Hirotoshi Sakashita
Keyword(s):  
Stearic Acid ◽  
Raman Spectra ◽  
Low Frequency ◽  
Chain Compounds ◽  
Long Chain

scholarly journals Self-assembly of alkyl chains of fatty acids in papermaking systems: A review of related pitch issues, hydrophobic sizing, and pH effects

BioResources ◽  
2020 ◽  
Vol 15 (2) ◽  
pp. 4591-4635
Author(s):  
Martin A. Hubbe ◽  
Douglas S. McLean ◽  
Karen R. Stack ◽  
Xiaomin Lu ◽  
Anders Strand ◽  
...  
Keyword(s):  
Fatty Acids ◽  
Self Assembly ◽  
Review Article ◽  
Ph Effects ◽  
Monolayer Films ◽  
Alkyl Chains ◽  
Ph Values ◽  
Self Association ◽  
Long Chain

This review article considers the role of fatty acids and the mutual association of their long-chain (e.g. C18) alkyl and alkenyl groups in some important aspects of papermaking. In particular, published findings suggest that interactions involving fatty acids present as condensed monolayer films can play a controlling role in pitch deposition problems. Self-association among the tails of fatty acids and their soaps also helps to explain some puzzling aspects of hydrophobic sizing of paper. When fatty acids and their soaps are present as monolayers in papermaking systems, the pH values associated with their dissociation, i.e. their pKa values, tend to be strongly shifted. Mutual association also appears to favor non-equilibrium multilayer structures that are tacky and insoluble, possibly serving as a nucleus for deposition of wood extractives, such, as resins and triglyceride fats, in pulp and paper systems.

Discotic Liquid Crystals of Transition metal Complexes 23: Synthesis and Mesomorphism of Tetrakis(3,4-di-n-alkylphenyl)porphyrin Derivatives and Their Metal Complexes

1999 ◽  
Vol 03 (04) ◽  
pp. 249-258 ◽  
Author(s):  
KAZUCHIKA OHTA ◽  
MASAHIRO ANDO ◽  
IWAO YAMAMOTO
Keyword(s):  
Liquid Crystal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Room Temperature ◽  
Discotic Liquid Crystals ◽  
X Ray ◽  
Alkyl Chains ◽  
Porphyrin Derivatives ◽  
Crystal Phases ◽  
Long Chain

Five novel long-chain-substituted porphyrin derivatives, tetrakis(3,4-dialkylphenyl)porphyrins (abbreviated as (Cn)8 TPPH 2 (n = 8, 12, 18), ( C 18)8 TPPCu and ( C 18)8 TPPNi ), were synthesized and their mesomorphism was investigated. It was found that the (Cn)8 TPPH 2 (n = 8, 12), derivatives are isotropic liquids at room temperature and that each of the ( C 18)8 TPPM ( M ≡ H 2, Cu , Ni ) derivatives has two liquid crystal phases M1 and M2 and two unidentified phases X1 and X2. It was revealed by X-ray studies that the M2 phase is a discotic lamellar (DL) phase. Interestingly, these porphyrin derivatives exhibit not a columnar but a lamellar mesophase, even though they have a disk-like central core with eight alkyl chains in the surroundings.

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