Partial molal volumes of organic compounds in carbon tetrachloride. 1. Alkanes: conformational effects

1978 ◽  
Vol 82 (21) ◽  
pp. 2310-2313 ◽  
Author(s):  
John T. Edward ◽  
Patrick G. Farrell ◽  
Fereidoon Shahidi
1979 ◽  
Vol 57 (22) ◽  
pp. 2892-2894 ◽  
Author(s):  
John T. Edward ◽  
Patrick G. Farrell ◽  
Fereidoon Shahidi

The partial molal volumes [Formula: see text] or 47 mono- or polycyclic alkanes, ethers, alcohols, ketones, and bromides have been determined in carbon tetrachloride at 25 °C. [Formula: see text] of most of these compounds can be calculated with moderate (±1–2%) accuracy using an equation containing parameters previously developed for acyclic compounds, and an additional cyclization parameter C, which is roughly linear with the number n of atoms in the ring, from n = 3 (C = +5.3 mL mol−1) to n = 10 (C = −21.0 mL mol−1). Substituted cyclohexanols and some polyfunctional compounds had [Formula: see text] considerably lower than calculated.


1979 ◽  
Vol 44 (6) ◽  
pp. 950-953 ◽  
Author(s):  
Fereidoon Shahidi ◽  
Patrick G. Farrell ◽  
John T. Edward ◽  
Persephone Canonne

1979 ◽  
Vol 57 (19) ◽  
pp. 2585-2592 ◽  
Author(s):  
John T. Edward ◽  
Patrick G. Farrell ◽  
Fereidoon Shahidi

The partial molal volumes [Formula: see text] in carbon tetrachloride at 25 °C of 13 ketones, 18 alcohols, and 17 mono- or poly-functional ethers, all acyclic, have been determined. Results are in reasonable agreement with [Formula: see text] calculated from an equation developed previously, using previous parameters plus the following: increments (in mL mol−1) of 8.72 for carbonyl, 6.1 for hydroxyl, 4.4 for oxygen in a monofunctional ether, and 5.8 for oxygen in a polyfunctional ether; decrements δ (in mL mol−1) of −1.68 for [Formula: see text] for [Formula: see text] for [Formula: see text] for [Formula: see text], and −1.93 for [Formula: see text]. The increments for carbonyl and hydroxyl are smaller than the van der Waals volumes of these groups, and indicate some degree of complexation to carbon tetrachloride. Only a roughly linear relation is found between [Formula: see text] of alcohols in water and [Formula: see text] in carbon tetrachloride, possibly because of the intrusion of additional effects such as structure-promotion in water.


1979 ◽  
Vol 57 (22) ◽  
pp. 2887-2891 ◽  
Author(s):  
John T. Edward ◽  
Patrick G. Farrell ◽  
Fereidoon Shahidi

The partial molal volumes of n-alkanes and n-alkanols dissolved in benzene, ethanol, or cyclohexane are given with satisfactory accuracy by the equation previously developed for solutions in carbon tetrachloride, if certain parameters (the covolume, the volume increment for the hydroxyl group, and the volume decrement for some gauche interactions) are changed. Additionally, it is necessary to postulate a greater coiling of the alkyl chains when dissolved in cyclohexane.


1979 ◽  
Vol 83 (3) ◽  
pp. 419-422 ◽  
Author(s):  
Fereidoon. Shahidi ◽  
Patrick G. Farrell ◽  
John T. Edward

1983 ◽  
Vol 61 (7) ◽  
pp. 1414-1416 ◽  
Author(s):  
Fereidoon Shahidi

The partial molal volumes at infinite dilution [Formula: see text] for a number of halobenzenes are measured and related to their van der Waals volumes. Results indicate larger volume increments for halogen atoms in halobenzenes than those in alkyl halides. Possible explanations are forwarded. The effect of steric overcrowding in ortho-substituted benzenes on the [Formula: see text] values are evaluated.


1986 ◽  
Vol 64 (2) ◽  
pp. 387-393 ◽  
Author(s):  
Ester F. G. Barbosa ◽  
Isabel M. S. Lampreia

Apparent molal volumes, [Formula: see text], of secondary and tertiary amines and linear hydrocarbons were determined in benzene at 25 °C, using a vibrating tube densimeter. These quantities have been extrapolated to infinite dilution to obtain partial molal volumes. The contribution to partial molal volume of the amine groups, calculated using a simple additive scheme, [Formula: see text], were interpreted in terms of conformational effects present in these molecules. A first attempt to find a measure of the contribution to the partial molal volume of the specific interaction amine–benzene in tertiary and secondary amines was made. The results agree well in the two different approaches used.


1983 ◽  
Vol 61 (12) ◽  
pp. 2684-2687 ◽  
Author(s):  
G. Ronald Brown ◽  
Julian K. Edward ◽  
John T. Edward

At 25 °C both molar volumes V and partial molal volumes [Formula: see text] in carbon tetrachloride of cyclohexane-d12 and of acetone-d6 are smaller than V and [Formula: see text] of the corresponding protio compounds. However, both V and [Formula: see text] of acetonitrile-d3 are larger than V and [Formula: see text] of acetonitrile-h3, and in solvent cyclohexane [Formula: see text] of acetone-d6 and of acetone-h6 are approximately equal. Apparently deuteration has not only a steric effect, but (in polar compounds) a counter-balancing effect, which may be polar.


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