THE SULPHURIC ACID SOLVENT SYSTEM: PART IV. SULPHATOCOMPOUNDS OF ARSENIC (III)

1963 ◽  
Vol 41 (2) ◽  
pp. 450-459 ◽  
Author(s):  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Sulphuric Acid ◽  
Solvent System ◽  
Dilute Solutions ◽  
Polymeric Compound ◽  
Polymeric Species ◽  
System Part ◽  
Hydrogen Sulphate ◽  
Sulphur Trioxide

The cryoscopic and conductimetric behavior of arsenic (III) oxide in 100% sulphuric acid and in dilute oleum have been investigated. It is concluded that in very dilute solutions in 100% sulphuric acid, arsenic (III) oxide forms arsonyl (III) hydrogen sulphate, AsO.HSO4, which is partly ionized to give the AsO+ cation. Both these species probably exist mainly in solvated forms, e.g., As(OH)(SO4H)2, and As(OH)(SO4H)+ respectively. At higher concentrations polymeric species such as HO.As(HSO4)OAs(HSO4)2 are present in increasing amounts and eventually the insoluble polymeric compound [(AsO)2SO4]n separates from solution. In oleum the more sulphated species As(HSO4)3, [(HSO4)2As]2O, and [(HSO4)2As]2SO4 are formed. Related structures are proposed for some previously prepared compounds of arsenic (III) oxide and sulphur trioxide.

THE SULPHURIC ACID SOLVENT SYSTEM: PART VI. THE BASICITIES OF COMPOUNDS CONTAINING SULPHUR–OXYGEN BONDS

1964 ◽  
Vol 42 (5) ◽  
pp. 1113-1122 ◽  
Author(s):  
S. K. Hall ◽  
E. A. Robinson
Keyword(s):  
Nitrogen Atom ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Dimethyl Sulphoxide ◽  
Strong Base ◽  
Weak Bases ◽  
System Part ◽  
Sulphur Trioxide ◽  
Basic Behavior

Cryoscopic and conductimetric studies of a variety of compounds containing S—O bonds have shown that dimethyl sulphoxide behaves as a strong base in sulphuric acid whereas dialkyl sulphones behave as weak bases. In contrast diaryl sulphones and aryl sulphonic acids behave as non-electrolytes.A correlation is established between the basicities of the alkyl sulphones, H2SO4, and the HSO4− ion, and their sulphur–oxygen stretching frequencies. This relation is used to predict the basicities of other compounds containing S—O bonds. In particular it is shown that the basicity of monomeric sulphur trioxide is similar to that of sulphuric acid, and sulphamide is shown to behave as a strong base in sulphuric acid, which implies protonation on a nitrogen atom rather than on oxygen, since the S—O stretching frequencies indicate only weakly basic behavior for O-protonation.

THE SULPHURIC ACID SOLVENT SYSTEM: PART I. ACID-BASE REACTIONS

1960 ◽  
Vol 38 (8) ◽  
pp. 1363-1370 ◽  
Author(s):  
R. H. Flowers ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Electrical Conductivity ◽  
Sulphuric Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Conductivity Measurements ◽  
Acid Base ◽  
Acid And Base ◽  
System Part ◽  
Acids And Bases ◽  
Good Agreement

Acid–base reactions in the solvent sulphuric acid are discussed. Such reactions are conveniently studied by electrical conductivity measurements. A relation between the composition at which the conductivity has a minimum value and the strengths of the acid and base is derived. Values of the dissociation constants of acids and bases obtained in this way are shown to be in good agreement with values obtained by other methods.

THE SULPHURIC ACID SOLVENT SYSTEM: PART III. THE PREPARATION AND STRUCTURES OF SOME COMPLEX SULPHATOBORATES

1962 ◽  
Vol 40 (5) ◽  
pp. 1009-1017 ◽  
Author(s):  
R. J. Gillespie
Keyword(s):  
Boric Acid ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Membered Ring ◽  
Acid Solutions ◽  
Sodium Potassium ◽  
System Part

By neutralizing sulphuric acid solutions of tetra(hydrogensulphato)boric acid with various metal hydrogensulphates, sodium, potassium, ammonium, and strontium salts have been prepared. From the compositions of these salts, and from the results of cryoscopic and conductimetric measurements on their solutions in sulphuric acid, it is concluded that they are best formulated as polysulphatoborates containing the six-membered ring [Formula: see text]It is shown that previously described sulphato compounds of boron can also be satisfactorily formulated on this basis.

THE SULPHURIC ACID SOLVENT SYSTEM: PART II. CONDUCTIVITY MEASUREMENTS ON SOLUTIONS OF SOME ACIDS

1961 ◽  
Vol 39 (6) ◽  
pp. 1266-1273 ◽  
Author(s):  
J. Barr ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Dissociation Constant ◽  
Sulphuric Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Acid Dissociation ◽  
Acid System ◽  
Conductivity Measurements ◽  
Acid Dissociation Constants ◽  
Strong Base ◽  
System Part

Conductivity measurements have been made on solutions of the following substances in sulphuric acid: HClO4, HSO3F, HSO3Cl, HPO2F2, HAs(HSO4)4, CH3SO3H, and CF3CO2H. Of these substances HSO3F, HSO3Cl, HAs(HSO4)4, and probably HClO4, behave as acids, CF3CO2H is a non-electrolyte, and HPO2F2, and probably CH3SO3H, are bases of the sulphuric acid system. Acid dissociation constants for HSO3F, HSO3Cl, and HAs(HSO4)4 have been determined by comparing the conductivities of their solutions with those of H2S2O7, whose dissociation constant is known from other measurements, and also by conductimetric titration with a strong base, e.g. KHSO4. These acids of the sulphuric acid system decrease in strength in the order HSO3F > HAs(HSO4)4 > HSO3Cl > HClO4.

THE SULPHURIC ACID SOLVENT SYSTEM: PART V. SOLUTIONS OF SOME ORGANOSILICON COMPOUNDS

1963 ◽  
Vol 41 (10) ◽  
pp. 2464-2471 ◽  
Author(s):  
R. H. Flowers ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Coordination Number ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Organosilicon Compounds ◽  
Initial Product ◽  
System Part ◽  
Bridging Groups

The cryoscopic and conductimetric behavior of solutions of hexamethyldisiloxane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, and tetraphenylsilane in 100% sulphuric acid has been investigated. The measurements show that stable non-electrolytes such as (CH3)3Si·HSO4 and (CH3)2Si(HSO4)2 are formed from the tri- and di-alkyl compounds. Species such as CH3Si(HSO4)3, which are presumably formed in the reaction of monoalkyl compounds, and Si(HSO4)4, which it is reasonable to suppose is the initial product from the cleavage of tetraphenylsilane, are unstable and polymerize to give polymers containing Si—O—Si bridging groups. No evidence was obtained for the formation of siliconium ions or for the formation of compounds containing silicon with a coordination number greater than four.

THE SULFURIC ACID SOLVENT SYSTEM: PART VII. SOLUTIONS OF SOME TIN(IV) AND LEAD(IV) COMPOUNDS

1966 ◽  
Vol 44 (10) ◽  
pp. 1197-1202 ◽  
Author(s):  
R. J. Gillespie ◽  
R. Kapoor ◽  
E. A. Robinson
Keyword(s):  
Sulfuric Acid ◽  
Sulfonic Acid ◽  
Solvent System ◽  
Lead Tetraacetate ◽  
Benzene Sulfonic Acid ◽  
Tin Compounds ◽  
Cationic Species ◽  
Stannic Acid ◽  
System Part

Solutions of tetramethyl tin trimethyl tin sulfate, di-n-butyl tin diacetate, tetraphenyl tin, and triphenyl tin hydroxide in. 100% sulfuric acid have been investigated by cryoscopic and conductimetric methods. Tetramethyl tin reacts with sulfuric acid with the evolution of methane and the formation of trimethyl tin hydrogensulfate. Trialkyl tin hydrogensulfates and dialkyl tin dihydrogensulfates behave as strong bases. It is probable that the cationic species formed are protonated hydrogensulfates rather than "stannonium" ions. Phenyl-substituted tin compounds are cleaved in sulfuric acid with the formation of benzene sulfonic acid and the complex hexa(hydrogensulfato) stannic acid, H2Sn(HSO4)6, and its anions. Lead tetraacetate gives yellow solutions containing hexa(hydrogensulfato) plumbic acid, H2PB(HSO4O6, and its anions.

RAMAN SPECTRA OF THE H2SO4–SO3 AND D2SO4–SO3 SYSTEMS: EVIDENCE FOR THE OCCURRENCE OF POLYSULPHURIC ACIDS

1962 ◽  
Vol 40 (4) ◽  
pp. 658-674 ◽  
Author(s):  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Sulphuric Acid ◽  
Raman Spectra ◽  
Ionic Species ◽  
The Self ◽  
Experimental Results ◽  
Similar Work ◽  
Stretching Vibrations ◽  
Sulphur Trioxide ◽  
High Concentrations

The Raman spectra of oleums, i.e. mixtures of sulphur trioxide and sulphuric acid, have been re-examined. Similar measurements on the sulphur trioxide – deuterosulphuric acid (D2SO4) system are also reported. The experimental results and conclusions of previous similar work on oleums are discussed. By comparison of the spectra of oleums with those of the polysulphuryl halides it is shown that the polysulphuric acids H2S2O7 and H2S3O10 are present in this system. The increase in the frequency of the SO2 stretching vibrations with increasing concentration of sulphur trioxide gives evidence for the existence of higher polysulphuric acids such as H2S4O13 at high concentrations of sulphur trioxide. In relatively concentrated oleum, sulphur trioxide monomer and trimer are also present. It is shown that the self-dissociation of liquid H2S2O7 gives mainly molecular H2S2O10 and H2SO4 and not ionic species. The conclusions reached from the interpretation of the Raman spectra of the D2SO4–SO3 system are similar to those arrived at for sulphuric acid oleums. The spectra of solutions of NaHSO4 in oleums were also examined, and are discussed.

scholarly journals Rhodamine-Sulphuric Acid -A New Visualization Reagent for the Determination of Sucralose by HPTLC

2010 ◽  
Vol 7 (s1) ◽  
pp. S559-S565 ◽  
Author(s):  
Mohd Idris ◽  
Seema Srivastava ◽  
T. R. Baggi ◽  
S. K. Shulka ◽  
A. K. Ganjoo
Keyword(s):  
Sulphuric Acid ◽  
Limit Of Detection ◽  
Solvent System ◽  
Artificial Sweetener ◽  
Yellow Fluorescence ◽  
Relative Standard ◽  
Golden Yellow ◽  
Solvent Systems ◽  
Olive Green

Sucralose a UV-visible inactive compound was separated on silica gel plate without any plate treatment prior to analysis, derivatized with rhodamine - sulphuric acid reagent and detected densitometrically at 456 nm as olive green band. With this reagent sucralose also shows golden yellow fluorescence at 366 nm. Two new solvent systemsi.e. chloroform: methanol: toluene (v/v 5:3.5:1.5) (solvent system-I) and chloroform: ethanol: benzene (v/v 5:3:2) (solvent system-II) were developed and giving Rfvalues of 0.62 and 0.45 respectively. The method was found to be sensitive with good limit of detection (LOD) for two solvent systems. The method imparts specificity to the method as at 456 nm sucralose only gives olive green color spots where as other artificial sweeteners did not show any response to this reagent, where as carbohydrates gives black color spots. Similarly sucralose gives golden yellow fluorescence at 366 nm which is not given by any other artificial sweetener. The method was highly reproducible with relative standard deviation (RSD)≤3% (n=3) and was applied for the determination of sucralose in different matrices like cola drinks, lemon juices, sugar free sweets, tabletop sweeteners etc.etc.

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