《ADVANCED PHYSICO-CHEMICAL EXPERINENTS》

Ⅰ.ANALYSIS1

1.The Beer-Lambert Law（including Vierordt’smethod）3

2.Chronopotentiometric analysis6

3.“Dead-stop”end-point titrations（amperometric）13

4.Differential conductimetric titration of very weak bases in aqueous solution17

5.Differential potentiometric titrations of mixtures of acids21

6.Estimation of isomers by infra-red absorption25

7.Lewis acids and bases29

8.Morton’s spectrophotometric method32

9.Potentiometric differentiation of alkali metals in mixed solvents36

10.Qualitative analysis of metals by emissionspectroscopy39

11.Quantitative spectrochemical trace analysis by the copper-spark method41

Ⅱ.COMPLEX FORMATION45

12.Chelating ligands in analysis47

13.Chelation and pH51

14.Composition of co-ordination compounds by the method of continuous variation54

15.Hagenmuller’s modification of the method of continuous variation59

16.Composition and stability constant of the uranyl-5-sulphosalicylate complex by the limiting logarithmic method67

17.Polarographic determination of stability con-stants of complex compounds71

18.Stability constants of co-ordination compounds by Bjerrum’s（potentiometric） method76

19.Stability constants of co-ordination compounds（Turner-Anderson method）81

20.Thermodynamics of chelation（effect of metalions）84

Ⅲ.ELECTROCHEMISTRY89

21.Activity coefficient of HC1 in aqueous solution91

22.Activity coefficients and solubilities of sparinglysoluble electrolytes95

23.Analytical boundary method for transportnumbers98

24.The Bronsted theory of acids （strengths of inorganic acids in glacial acetic acid）103

25.Conductimetric titration of mixtures109

26.The Debye-Hǖckel theory and weak electrolytes112

27.Ion-association:Bjerrum’s theory（ion-pair and triple-ion formation）115

28.Ionic product for water(Kw)by the e.m.f.method121

29.The Onsager equation and its modifications124

30.Potentiometry at constant intensity128

31.Thermodynamic ionization constants of weakelectrolytes133

32.Thermodynamic transfer quantities by e.m.f.measurements136

33.“Zwitterions”140

Ⅳ.KINETICS147

34.Catalytic decomposition of hydrogen peroxide149

35.Conductimetric study of the kinetics of hydrolysis of tertiary butyl iodide153

36.Decomposition of ammonia on a tungstensurface158

37.Dilatometric study of reaction kinetics162

38.Energies and entropies of activation of isomericrearrangements166

39.Isomerization equilibrium and kinetics in aqueous solution172

40.Method of ratio variation176

41.Primary salt effect179

42.Secondary salt effect185

43.Spectroscopic study of the alcoholysis of cinnamal chloride190

44.Stirred-flow reactor193

Ⅴ.PHOTOCHRMISTRY197

45.Photobromination of cinnamic acid（chainreaction）199

46.Photocatalysis:the photolysis of uranyl oxalate（uranyl-oxalate aotinometer）203

47.Photochemical dimerization of anthraoene（photo-stationary state）207

48.Photohydrolysis of monochloroacetic acid（quan-tum efficiency）213

49.Photosensitization of chemical reactions（the Eder reaction）218

50.The oxidation of ferrous iron by iodine under the action of ultra-violet radiation221

Ⅵ.SPECTROSCOPY225

51.Deviations from the Beer-Lambert Law227

52.Indicator constants by spectrophotometry233

53.Infra-red spectra and chemical properties of molecules236

54.Ion-association by spectrophotometry240

55.Isobiestic point245

56.Moment of inertia, internuclear distance, and bond strength of HI by infra-red spectra250

57.Quenching of fluorescence257

58.Spectrophotometric determination of molecularweights264

59.Spectroscopic determination of equilibrium con-stants of molecular compounds（charge-transfer spectra）267

60.Spectroscopic study of the dimerization of ethanol in non-polar solvents270

Ⅶ. THERMODYNAMICS275

61.Activities of electrolytic solutes by the freezing-point method277

62.Activities from vapour-pressure data281

63.Activity of thallium in amalgams at 25℃286

64.Partial molal volumes291

65.Partial molal volumes in regular solutions296

66.Solubility of naphthalene in various solvents（ideal and non-ideal solutions）299

67.Thermal dissociation of ferric bromide304

68.Thermodynamic functions of the reaction be-tween malonic acid and some lanthanons308

69.Thermodynamics of vaporization of liquids314

Ⅷ.VARIOUS319

70.Azeotropie distillation（determination of water content）321

71.Dipole moment of 1:8-dichloronaphthalene by Guggenheim’s method326

72.Donnan equilibria329

73.Enthalpy titrations334

74.The Hammett indicator acidity function H340

75.Liquid-liquid adsorption of soluble fatty acids（Gibbs’ and Szyszkowski’s equations）347

76.Magnetic susceptibility （by the Gouy method）353

77.Molecular weight determination by “isothermic distillation” （Barger’s opposed twin capillary method）357

78.The reciprocal salt effect and the Janecke projec-tion （phase rule study）361

79.The ternary diagram by the wet-residue method（phase rule study）368

80.The ternary diagram by the synthetic-complex method （phase rule study）372

81.Thermal decomposition of solids （Prout-Tomp-kins’equation）375

82.The determination of surface areas of adsorbents by means of the B.E.T.isotherm （physicaladsorption）380

Appendix:Erros,mistakes,and deviations.Method of least squares389

Index399