Thermodynamic aspects of phosphorus compounds with particular reference to those containing the phosphorus-phosphorus bond

Hameed, Abdul

(1971)

Hameed, Abdul (1971) Thermodynamic aspects of phosphorus compounds with particular reference to those containing the phosphorus-phosphorus bond.

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Abstract

The enthalpies of sublimation for triiodophosphine and diphosphorus tetraiodide have been determined via an effusion manometric technique as 15.2 +-0.9 (63.6 +- 3.8 KJ. mole-1) and 16.7 +- 0.5 kcal mole-1 (69.9 +- 2.1 KJ. mole-1) respectively. Incorporating these values in thermodynamic cycles along with anciliaiy literature data has resulted in a phosphorus-phosphorus bond energy in diphosphorus tetraiodide of 62 kcal mole-1 (259 KJ. mole 1). Mass spectrometrie measurement of the appearance potentials for tri-iodophoshine and diphosphorus tetraiodide gave 11.9 +- 0.15 and 12.8 +- 0.15 eV respectively. These data in combination with known ionization potentials give 73 +- 6 kcal mole -1(305 +- 25 KJ. mole -1) for the bond dissociation energy of the phosphorus-phosphorus bond in diphosphorus tetraiodide. Cracking patterns for some mononuclear adducts of the type X3PBX3 (X = Br or I) are reported. Reproducible synthetic routes for pentapherylcyclopentaphosphine and polymeric pherjylphosphine have been established. Thermocbeinical investigations have been made for the pentameric and polymeric phosphobenzenes by reaction-solution calorimetry and thermal analysis techniques. The standard heat of formation of tricyanophosphine (crystal) is derived via thermochemical measurements as 133.6 +- 0.4 kcal mole -1 (559.0 +- 1.7 KJ. mole -1) at 25?C. The enthalpy of complexing of diphosphorus tetraiodide-boron tribromide (1:2) adduct from diphosphorus tetraiodide and boron tribromide in carbon disulphide has been measured as -2.13 +- and the standard heat of formation of this molecular adduct is derived as -144.0 +- 1.6 kcal mole-1 (602.5 +- 6.7 KJ. mole-1). The enthalpy of hydrolysis of pentabroraophosphorane-boron tribromide is also recorded from which the standard heat of formation is found to be -142.0 +- 1.3 kcal mole 1 (-594.1)

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This is a Accepted version
This version's date is: 1971
This item is not peer reviewed

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https://repository.royalholloway.ac.uk/items/e7607af9-3a01-4801-ac33-e73613d825d4/1/

Item TypeThesis (Doctoral)
TitleThermodynamic aspects of phosphorus compounds with particular reference to those containing the phosphorus-phosphorus bond
AuthorsHameed, Abdul
Uncontrolled KeywordsPhysical Chemistry; Pure Sciences; Aspects; Bond; Compounds; Containing; Particular; Phosphorus; Phosphorus Compounds; Phosphorus Compounds; Reference; Thermodynamic; Those
DepartmentsDepartment of Chemistry

Identifiers

ISBN978-1-339-60870-9

Deposited by () on 01-Feb-2017 in Royal Holloway Research Online.Last modified on 01-Feb-2017

Notes

Digitised in partnership with ProQuest, 2015-2016. Institution: University of London, Royal Holloway College (United Kingdom).


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