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1.
Conditions were found under which manganese(III) acetate can be electrochemically generated at a platinum anode with 100% current efficiency. It was found that even traces of
5. Time Dependence of the Consumption of the Oxidizing Reagent in the Indirect Determination of Hydroquinone with Coulometric Generated Manganese(III) Acetate
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2.
Sulfite ion reacts with mercury(II) ion in acid solution to form the mercury(I) ion. The reaction is rapid and quantitative. The mercury(I) ion absorbs at 237 nm with a molar
5. Beer's law Data for Sulfite Complexes of Covalent Mercury(II) Compounds
Time (min)05103060
Consumption of Mn(III) (mol/mol)2.001.992.002.012.00
SO2 (ppm)?HgCl2a?HgBr2?Hg(Ac)2b?Hg(SCN)2
2.012,50010,00010,0009,200
4.012,50011,50010,0009,000
6.012,50011,50010,0009,200
8.012,00011,00010,5009,800
a
Molar absorptivity based on sulfite ion at 230 nm. Solution was 6.86 buffer.
b
Mercuric acetate solutions seemed to be somewhat unstable. absorptivity of about 25,000. The absorbance is linear over a range of approximately 0.5–5.0 ppm as SO2. Covalent mercury(II) compounds form a complex with sulfite, Hg(SO3)22?, which absorbs at 230 nm and shows a linear response over a range of 1–8 ppm as SO2.
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3.
A sensitive spectrofluorimetric procedure with rhodamine B in the presence of aluminum chloride is given for determining submicrogram and microgram quantities of thallium in silicate rocks. Samples are decomposed with a mixture of hydrofluoric and nitric acids and then treated with hydrochloric acid. Thallium is extracted as its dithizonate with chloroform from an alkaline medium containing ascorbate, citrate, and cyanide and then back-extracted with dilute nitric acid. After destruction of the organic matter and treatment with bromine, hydrochloric acid, aluminum chloride, and rhodamine B, the
T001. Determination of thallium in U.S. Geological Survey standard rocks by different laboratories
Thallium (p.p.m.)MethodRef.
G-1W-1
1.060.102Neutron activation analysis1
1.080.121, 0.116Neutron activation analysis2
1.30.17Neutron activation analysis3
1.30.11Spectrographic4
0.105–0.110Flameless atomic absorption spectroscopy5
1.3a0.13a19
1.24b0.110b20
1.09 ± 0.010.110 ± 0.005SpectrofluorimetricPresent method
a
Values given by Fleischer.
b
Average value given by Flanagan. fluorescence intensity of the benzene-extracted rhodamine B chlorothallate is measured. The limit of determination is approximately 0.01 p.p.m. for a 1.0-g sample. The thallium contents of U.S. Geological Survey standard rocks G-1 and W-1 were found to be 1.09 ± 0.01 and 0.110 ± 0.005 p.p.m., respectively.
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4.
A simple, rapid, and accurate method for determination of total sulfur and inorganic sulfate in biological materials by barium chloranilate colorimetry is presented. Criteria required
3. Precision of S Determination, Whole Blood, Blood Plasma, TCA Extracts, and Urine
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5.
A kinetic method is described for the determination of trace amounts of magnesium in the presence of calcium. The procedure is based on the inhibition of the manganese(II) catalyzed aerial oxidation of 1,4-dihydroxyphthalimide dithiosemicarbazone reaction by
2. Effect of Transition Metalsa
SampleDeterminationsMean (μg)SD (μg)
Whole blood10100421
Blood plasma105434
TCA extracts10242
Urine (totals)1059831
Urine (inorganic S)10374.419
Transition metalConcentration (M)Percentage inhibitionMg(II) found (×l05M)
Fe(II)3.6.10?554.14.62
Fe(III)3.6.10?547.84.48
Co(II)3.4.10?550.04.53
Ni(II)3.4.10?550.04.53
Cu(II)3.1.10?552.04.56
Zn(II)3.0.10?554.14.62
Cd(II)1.7.10?552.04.56
Hg(II)9.9.10?645.84.44
Sn(II)2.1.10?650.04.52
Pb(II)1.2.10?654.14.62
a
Conditions: 4.53.10?5M Mg(II), 35 ng Mn ml?1, 0.429 M ammonia, 1.6.10?4M OH-PDT.
3. Determination of Magnesium in Natural Waters
Mg(II) found (M)b
Natural waterCa(II) presentaAtomic absorption
sampleMKinetic absorptionmethod
Commercial3.45 · 10?41.65 · 10?31.74 · 10?3
Commercial5.46 · 10?41.57 · 10?41.81 · 10?4
Untreated6.13 · 10?42.16 · 10?42.40 · 10?4
Treated4.95 · 10?41.93 · 10?42.17 · 10?4
a
EDTA titration less the magnesium.
b
Average of three separate determinations. traces of magnesium(II). The reaction is followed spectrophotometrically by measuring the rate of change in absorbance at 594 nm. The calibration graph (percentage inhibition vs magnesium concentration) is linear in the range 329–535 · 10?5M with an accuracy and precision of 1.2%. The method has been applied to the determination of magnesium in natural waters at low concentrations.
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6.
Cadmium ions react with the collector, ethylhexadecyldimethylammonium bromide (EHDABr), to form a surface-active sublate which can be removed from aqueous bromide
a. Effect of Foreign Metal Ions on the Flotation of Cadmiuma
Foreign ionForeign ion concentration (M) (×10?5)Foreign ion removed (%)Cadmium removed (%)
None99.21
Zn2+6.110.0698.41
Cu2+6.293.6497.80
Pb2+3.864.8091.78
Cr6+7.6930.7599.07 solutions by ion flotation. A typical ion flotation procedure involves passing air through a 250-ml solution containing 5 ppm Cd2+, 0.05 M Br?1, and 1.7 × l0?3M EHDABr at a flow rate of 40 ml/min for 1 hr. The procedure was simple and efficient. Chromium, copper, and zinc ions do not interfere under the experimental conditions.
a
Cd2+, 4.46 × 10?5M; EHDABr, 4.25 × 10?4; Br?, 5 × 10?2M; flow rate, 40 ml/min; time, 60 min.
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7.
Spectrophotometric investigation of the deep blue colored, water-soluble complex of
1. Stability constant and free energy of formation of Cu-NMS complex at 30 ± 1 °C
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8.
Nitron and tetraphenylarsonium chloride react with a cobaltous salt in the presence of thiocyanate to form blue ion-association complexes, which can be extracted with organic solvents. This fact has been made the basis for the analysis of mixtures of nitrate and perchlorate by difference spectrophotometry. An aliquot of the sample solution is treated with a known excess of tetraphenylarsonium chloride to precipitate perchlorate only. After separating off the precipitate, the excess of reagent is determined in the supernatant liquid as tetraphenylarsonium cobaltothiocyanate and the perchlorate content can be found from a calibration curve. Another aliquot is treated with an excess of nitron to precipitate both anions; the excess of nitron is then determined as nitron
2. Analysis of Nitrate-Perchlorate Mixtures
MethodlogKsΔF (Kcal/mole)
Mukherji and Dey (4)4.11?5.70
Subhrana and Raghavrao (6)4.80?6.66
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9.
A polarographic method for the determination of antimony in lead-antimony alloys has been developed. It was found that the interference due to the presence of varying concentrations of lead and hydrochloric acid would be eliminated by the addition of potassium chloride.
t001. The method gave satisfactory results within the range:
PerchlorateNitrate
Taken (μg)Found (μg)Error (%)Taken (μg)Found (μg)Error (%)
400404+ 1.00248250+0.81
4004000.00496492?0.81
4004000.009929920.00
800796?0.502482480.00
600602+0.33248245?1.21
800792?1.25496498+0.40
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10.
In summary, this report describes the conditions under which luminol has been utilized to measure phagocytosis-associated metabolic events in activated human PMNs and rabbit and dog alveolar macrophages. We feel that this system may have wide applicability to both clinical and experimental situations. Some possible applications are shown in the following table.
Potential Applications of Luminol-Amplified Chemiluminescence
Hydrochloric acid4 — 8M
Lead0 — 0.03M
Antimony0 — 0.002M
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11.
The acidic dissociation constants of three vic-dioximes have been determined from spectrophotometric data. The results may be summarized as follows:
Cell typeApplications
Human polymorphonuclear leukocytes(1) Detection of bactericidal defects, particularly chronic granulomatous disease
(2) Detection of host opsonic defects (both immunoglobulin and complement ?C3b opsonic defects).
(3) Analysis of drug effects on host cellular and opsonic defenses (9,11).
(4) Characterization of bacteria or other particulate matter in terms of ability to generate opsonic activity and/or be ingested by phagocytic cells (3,7).
Alveolar macrophages(1) Detection of environmental pollutant effects on respiratory defense mechanisms (against both particulate and soluble matter).
(2) Analysis of drug effects on respiratory defense mechanisms, particularly drugs administered in the treatment of respiratory diseases.
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12.
A direct amperometric titration of copper is described; o-(p-tolylsulfonamido) aniline serves as titrant. The optimum conditions are discussed and the method is applied to the analysis of copper in brass alloys.
t001. IV. Analysis of various samples in which copper was determined (Values given as percentages)
pK1pK2
2,3-butanedionedioxime10.6 ± 0.111.9 ± 0.3
1,2-cyclohexanedionedioxime10.6 ± 0.212.4 ± 0.5
1,2-cycloheptanedionedioxime10.7 ± 0.212.3 ± 0.5
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13.
Rotational spectra have been assigned for four isotopic species of the linear HCN dimer in the vibrational ground state. The spectroscopic constants are
ConstituentsThorn Smith # 30Thorn Smith # 54NBS # 37ENBS # 63C
Cu present59.3084.0469.6180.48
Zn37.811.45227.850.093
Pb0.18.5901.009.35
SnTrace5.7371.009.03
Sb0.52
NiTrace0.530.32
P0.145
S0.060
As0.023
Fe1.220.0040.0013
Al1.15
Mn0.35
Cu found59.0983.6469.68a80.54aaAverage of 3 determinations.
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14.
A potentiometric method is described for the determination of thiosemicarbazones involving the formation of a complex with Ag(I). This method is proposed for thiosemicarbazones of the following carbonyl compounds: salicylaldehyde, p-hydroxybenzaldehyde, benzaldehyde, picolinaldehyde, 6-methylpicolinaldehyde and p-dimethylaminebenzaldehyde. Stability constants of the complexes are determined by Ringbom and Harju's method.
FIG. 2. Variation of pAg + logαPAT (H) + log ([Ag?PAT)]/[PAT])
2. Formation Constants of the Silver-Thiosemicarbazonates
isotope-B0 (MHz)DJ (kHz)xN1 (MHz)xN2 (MHz)
HC14N-HC14N1745.80973(50)2.133(30)?4.0973(200)?4.4400(190)
HC14N-HC15N1700.30190(30)1.939(40)?4.1059(10)-
HC15N-HC14N1729.92082(20)2.023(30)-?4.4339(6)
HC15N-HC15N1684.28825(25)1.900(30)--
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15.
With the help of the Chcvcnard thcrmobalancc the authors have determined the minimum temperatures necessary for quantitatively converting the derivatives of gallium into oxide Ga203.
ThiosemicarbazoneLog Kf
-Benzaldehyde15.5 ± 0.1
-Picolinaldehyde14.0 ± 0.
-6-Methylpicolinaldehyde14.5 ± 0.
-Salicylaldehyde15.7 ± 0.1
-p-Hydroxybenzaldehyde15.6 ± 0.
-p-Dimethylaminebenzaldehyde17.2 ± 0.1
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16.
Cobalt ions in aqueous thiocyanate solution react with Aliquat-336-xylene solution to form anion-association complex which is easily extracted into the organic phase. A typical extraction procedure involves extracting a solution which is 10 ppm in cobalt and 0.06 M,
5. Stripping of Cobalt from 2% Aliquat-336-Xylene Solutions
Hydroxide by ammonium hydroxide408°
Hydroxide by ammonia400°
Hydroxide by urea475°
Hydroxide by aniline546°
Hydroxide by sulpliitc813°
Hydroxide by tannin520°
Cupfcrron745°
Camphoratc478°
Dibromo-oxinate817°
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17.
The hydrogen-bonded heterodimer formed between oxetane and hydrogen fluoride is identified and characterised by means of its IR and microwave spectra. The following rotational constants (MHz) and centrifugal distortion constants (kHz) have been derived:
StrippantCobalt stripped (%)
Na2S (M) 1.018.3
2.010.7
Na2SO3 (M) 0.110.7
0.549.6
1.052.9
EDA (%) 2.576.6
NaOH (M) 0.14.1
0.574.1
1.090.8
2.076.8
NH4OH (M) 0.124.1
0.591.8
1.097.5
2.099.9
EDTA (M) 0.02>99.9
0.05>99.9
0.1>99.9
EDTA (%) 0.1>99.9
0.5>99.9
1.0>99.9
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18.
The authors discuss several aspects of the chemistry of indium, giving evidence for a hydrate 2ln2O3.H2O and studying in detail the behaviour of indium sulphide heated in air. Compared with that of gallium, the oxinate is particularly stable.Compounds used for the gravimetric determination of indium should be heated to the following temperatures in order to give correct results:
ABCΔJΔJK
(CH2)O3?HF92172575.12350.611.3?57.0
(CH2)3O?DF9157(ass)2544.72329.39.9?56
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19.
The Coulometrics Inc. CO2 coulometer has been shown to be an accurate and reliable CO2 measuring device. The coulometric efficiency is essentially 100%. This means that the method can be considered as a standard reference method for CO2. As with a CO2 absorption tube, certain potential interferences must be considered, however, the removal of these interferences is well documented in the literature.The CO2 coulometer has found a variety of applications in the author's
3. effect of flow rate on absorption of CO2 by coulometer
Hydroxide by ammonia345°
Hydroxide by hexamethylene tetramine546°
Hydroxide by cyanate475°
Sulphide94–221°, 320–544°, 690°
Phosphate477°
Luteocobaltic indichloride100–105°
Oxinate100–285°
Diethyldithiocarbamate100–210°
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20.
Multielement determinations by high-flux absolute n.a.a. require careful methodology to avoid systematic error. The ORNL high-flux facility with a thermal flux of 5 ·1014 cm-2 s-1 and a thermal-to-resonance flux ratio of
T004. Analysis of Knoxville tree-core samplesa
CaCO3 (mg)C (mg)Flow rate (cm3/min)C found (mg)C (%)
27.9893.3591003.366912.03
28.6043.4322003.434312.00
29.2593.5113003.514912.01
33.8084.0574004.038111.94
5.6290.6755000.676012.01
10.3111.2375001.233711.96
15.6471.8785001.870611.95
35.2144.2265004.198211.92
40.7334.8885004.821211.84
59.6787.1615007.026311.77
30.3863.6467803.594111.83
29.7813.5747803.536111.87
28.1133.37411503.253411.57
ElementIncrement no.20 (1832–1838)Increment no.8 (1932–1838)Increment no.3 (1858–1863)Increment no.1 (1868–1872)
Core NumberCore NumberCore NumberCore Number
13131313
Na12.9(1.1)2.67(3.3)33.8(1.0)11.2(1.6)15.6(1.5)31.4(1.2)22.4(0.93)9.9(1.8)
Mgcc160(12)b80(27)b100(21)b100(30)bcc
Al15.2(5.4)5.6(6.1)12.5(3.8)11.0(4.4)7.8(6.6)8.4(7.4)6.5(14)6.6(6.2)
Cl15.4(9.1)ND66(5.4)NDND55(6.1)26(5.5)22(5.1)
K205(2.6)223(3.3)493(1.8)b457(1.9)b478(1.9)b439(2.1)b449(1.8)570(1.7)
Ca1600(11)NDNDNDNDNDNDND
CrNDNDNDbNDb0.3(>30)b0.6(>30)b0.6(>30)bND
Mn109(0.30)107(0.23)64.1(042)108(0.32)46.7(051)66.8(0.44)38.9(0.39)45.0(0.34)
FeNDNDNDNDND19(19)25(18)ND
CoND0.02(>30)NDNDNDND0.30(>30)ND
Zn7.2(7)7.4(4.2)13.0(2.4)9.2(3.3)5.6(4.0)4.5(4.7)ND2.4(8.8)
Br0.10(20)ND0.07(12)ND0.024(13)ND0.04(>30)ND
RbNDND0.9(13)0.8(18)0.8(15)0.7(17)ND1.1(18)
AgNDND1.06(3.0)15.3(0.71)0.15(15)0.69(4.8)0.11(28)ND
Ba11(7.3)10(13)3.2(16)ND3.0(15)2.9(18)ND3(32)
WNDNDNDNDNDND0.06(29)ND
a
Results in p.p.m followed by (per cent counting statistical error).
b
Computer forced result.Also V,Se,Sr,Sb,Cs and au (forced) were not detected.
c
Element possibly present but missed by peak-finding routine.7 35–45, was used in developing an instrumental absolute multielement method. The detector was calibrated for absolute counting with two independent sets of radioactivity standards for four detector- -source distances; the absolute activities of the standards were reproducible within accuracies of 9%. Five sources of systematic error were investigated: (a) correction for counting of cylindrical sources for 26 γ-ray energies reached 14–17% for photon energies below 500 keV; (b) flux variation during bombardment and within the irradiation capsule volume was not significant; (c) samples were sufficiently stable during high-flux bombardment; (d) multi-element impurities in accessory materials (polyethylene and “Nucleopore” filters) were not significant; (e) correction for sample activation during rabbit transfer was necessary for short bombardments, e.g., 8.6 % for 6 s and 19.6 % for 4 s. This methodology resulted in accuracies of 10–15 % for most elements, as determined by analysis of N.B.S. orchard leaves and coal and of Bowen's kale standards. The method was applied to a preliminary chronological study of environmental baselines and contamination levels, based on tree ring samples, covering a period of 100 years.
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