The Laboratory of the Government Chemist (LGC) is a focal point for the production, analysis and certification of reference
materials. Within the field of thermal analysis the LGC is concerned with the development of purity standards and materials
certified for enthalpy of fusion and melting point. For some time the LGC has been concerned with the significant differences
in purity data which can be produced by the different manufactures' differential scanning calorimeters. This paper will highlight
the initiatives the LGC is undertaking in overcoming this uncertainty in purity measurements through the use of certified
Gamma-ray spectrometry of liquid or finely divided solid samples may be facilitated by incorporating standard activity additions. The count rate rises linearly with added activity, and the intercept and slope of the 1.s.f. line permits the intrinsic activity of the sample to be found. Applications of this method in the determination of210Pb and Th activity are described.
Three standard reference materials were analyzed by a method of absolute INAA. Two different light water pool-type reactors
were used to produce equivalent analytical results even though the epithermal to thermal flux ratio in one reactor was higher
than that in the other by a factor of two.
Authors:K. Singh Mudher, K. Krishnan, R. Khandekar, M. Yadav, N. Jayadevan, and D. Sood
Rubidium uranium trisulphate [Rb2U(SO4)3] was prepared as a high purity compound of uranium in different lots of 250 g each. The compound was characterised and evaluated
by chemical, atomic spectrosopic, infrared, X-ray diffraction and thermogravimetric methods for its use as a chemical assay
standard for uranium. The compound is stoichiometric, pure, homogeneous and stable in atmospheric conditions. The solubility
studies showed that Rb2U(SO4)3 is easily soluble in mineral acids. An experiment based on Randomised Block Design was carried out to assign a value to the
uranium content in Rb2U(SO4)3 from the statistically analysed chemical data. The assigned value of [34.167±0.042]% to the uranium content is in close agreement
with the theoretical value of 34.152%. Based on these studies, Rb2U(SO4)3 is recommended as a chemical assay standard for uranium.
Authors:Z. Řanda, M. Vobecký, J. Kuncír, and J. Benada
The application of multielement standards (MES) in routine neutron activation analysis brings a whole range of advantages.
This paper deals with the experience obtained during many years of application of these MES. Nine of these MES contain a total
of 50 elements in suitable combinations and concentrations; thus, the determination of most of the common elements by NAA
can be carried out simultaneously. This refers to the following elements: Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Ag, Cd, In, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf,
W, Re, Au, Hg, Th and U. For the determination of the remaining elements such as Zr, Ta, Ir etc., single element standards
(SES) are used.
Standard enthalpies of formation of amorphous platinum hydrous oxide PtH2.76O3.89 (Adams' catalyst) and dehydrated oxide PtO2.52 at T=298.15 K were determined to be -519.61.0 and -101.3 5.2 kJ mol-1, respectively, by micro-combustion calorimetry. Standard enthalpy of formation of anhydrous PtO2 was estimated to be -80 kJ mol-1 based on the calorimetry. A meaningful linear relationship was found between the pseudo-atomization enthalpies of platinum
oxides and the coordination number of oxygen surrounding platinum. This relationship indicates that the Pt-O bond dissociation
energy is 246 kJ mol-1 at T=298.15 K which is surprisingly independent of both the coordination number and the valence of platinum atom. This may provide
an energetic reason why platinum hydrous oxide is non-stoichiometric.
Authors:V. Lukyanova, T. Papina, K. Didenko, and A. Alikhanyan
The standard enthalpy of combustion of crystalline silver pivalate, (CH3)3CC(O)OAg (AgPiv), was determined in an isoperibolic calorimeter with a self-sealing steel bomb, ΔcH0 (AgPiv, cr)= −2786.9±5.6 kJ mol−1. The value of standard enthalpy of formation was derived for crystalline state: ΔfH0(AgPiv,cr)= −466.9±5.6 kJ mol−1. Using the enthalpy of sublimation, measured earlier, the enthalpy of formation of gaseous dimer was obtained: ΔfH0(Ag2Piv2,g)= −787±14 kJ mol−1. The enthalpy of reaction (CH3)3CC(O)OAg(cr)=Ag(cr)+(CH3)3CC(O)O.(g) was estimated, ΔrH0=202 kJ mol−1.
Authors:H. Sakurai, M. Fukuda, Y. Hayashibe, Y. Sayama, K. Masumoto, and T. Ohtsuki
A highly sensitive determination of fluorine in standard rocks by photon activation using the19F(,n)18F reaction combined with pyrohydrolysis for the separation of18F has been reported. The irradiation energy was operated at 20 MeV to avoid the interference from Na, because Na is one of the major element in rocks and18F is also produced from Na via23Na(,n)18F reaction above its threshold energy, 20.9 MeV. After irradiation, fluorine was extracted by pyrohydrolysis and separated as LaF3 precipitate. It was ascertained that the average recovery of fluorine in standard rocks was about 90% and the precipitate was of high radiochemical purity. This method was applied to the analysis of ten GSJ rock reference samples and two USGS standard rocks issued by the Geological Survey of Japan and the United States Geological Survey, respectively. The detection limit of this method was 0.02 g/g, and the results obtained by this method were in good agreement with the recommended values. This method was easily applied to the determination of a few ppm level of fluorine in rock samples, such as ultrabasic rock and feldspar.
Ionic temperature detectors are described and discussed as possible internal temperature standards for thermal analysis and calorimetry. The available scale from 200 °C to 900 °C is shown, together with the miniature dimensions.
The goal of this research is to prepare a series of alloys having sharp, reproducible magnetic transitions for calibrating
temperature in thermogravimetry from the magnetic transition temperature of pure cobalt (1121°C) to below room temperature.
Alloys in the Ni-Co and Ni-Cu systems were prepared by the thermal decomposition of coprecipitated oxalates in argon. The
alloys were subsequently annealed under 5% hydrogen.
Magnetic transition temperatures were measured using simultaneous thermomagnetometry/differential thermal analysis. Transition
temperatures were corrected using well known meltingpoint standards. Magnetic transition temperatures along with precision
are reported as a function of composition.