Hojo Masashi, Yamamoto Masahiko, Okamura Kei
Department of Chemistry, Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan.
Phys Chem Chem Phys. 2015 Aug 14;17(30):19948-56. doi: 10.1039/c5cp02288f. Epub 2015 Jul 13.
The greatly enhanced oxidation ability of dilute aqueous nitric acid (0.10-2.0 mol L(-1)) containing bromide and iodide salts as well as chloride salts has been examined based on the dissolution kinetics of pure gold at 30-60 °C. It has been found that bromide salts are more effective than chloride salts in gaining the ability of dissolving gold in dilute aqueous nitric acid solution. At 60 °C, a piece of gold-wire (ca. 20 mg) is dissolved in 20 mL of as low as 0.10 mol L(-1) HNO3 solution containing 1.0-5.0 mol L(-1) NaBr and the dissolution rate constant, log(k/s(-1)), increases linearly (from -5.78 to -4.52) with the increasing NaBr concentration. The addition of organic solvents, such as acetonitrile and acetic acid, causes acceleration of gold dissolution in LiBr and NaBr solutions. With increasing MeCN contents, for instance, the log(k/s(-1)) value of 0.10 mol L(-1) HNO3 solution containing 2.0 mol L(-1) NaBr increases linearly from -5.30 to -4.61 at 30% (v/v) MeCN. The bromide salts affect the gold dissolution rate constant in the order of KBr < NaBr < LiBr < CaBr2. With increasing NaI concentration (0.20-3.0 mol L(-1)), some acceleration in log(k/s(-1)) of 0.50 or 1.0 mol L(-1) HNO3 solution has been observed; however, the slope of acceleration as the function of NaI concentration is much smaller than that of NaCl or NaBr. The gold dissolution ability has been examined also for nitrous acid containing chloride and bromide ions at 35 °C. The NaNO2 solution containing twice or more amounts of HX (X = Cl, Br) gives the maximum efficiency for gold dissolution, according to the log(k/s(-1)) values of the mixed solutions of NaNO2 (0.10-2.0 mol L(-1)) and HX of various concentrations. The influence of oxidation by dilute nitric and nitrous acids on the gold dissolution is discussed from the standpoint of the redox potentials in "modified" aqueous solutions and not of the changes in the activity coefficients of ions.
基于纯金在30 - 60°C下的溶解动力学,研究了含有溴化物、碘化物以及氯化物盐的稀硝酸水溶液(0.10 - 2.0 mol L⁻¹)显著增强的氧化能力。已发现,在稀硝酸水溶液中,溴化物盐在获得溶解金的能力方面比氯化物盐更有效。在60°C时,一根金线(约20 mg)可溶解于20 mL低至0.10 mol L⁻¹的含有1.0 - 5.0 mol L⁻¹ NaBr的HNO₃溶液中,溶解速率常数log(k/s⁻¹)随NaBr浓度的增加呈线性增加(从 - 5.78增加到 - 4.52)。添加有机溶剂,如乙腈和乙酸,会加速金在LiBr和NaBr溶液中的溶解。例如,随着MeCN含量的增加,在30%(v/v)MeCN时,含有2.0 mol L⁻¹ NaBr的0.10 mol L⁻¹ HNO₃溶液的log(k/s⁻¹)值从 - 5.30线性增加到 - 4.61。溴化物盐对金溶解速率常数的影响顺序为KBr < NaBr < LiBr < CaBr₂。随着NaI浓度(0.20 - 3.0 mol L⁻¹)的增加,观察到0.50或1.0 mol L⁻¹ HNO₃溶液的log(k/s⁻¹)有一定程度的加速;然而,作为NaI浓度函数的加速斜率远小于NaCl或NaBr的情况。还在35°C下研究了含有氯离子和溴离子的亚硝酸对金溶解能力的影响。根据NaNO₂(0.10 - 2.0 mol L⁻¹)与各种浓度的HX混合溶液的log(k/s⁻¹)值,含有两倍或更多量HX(X = Cl,Br)的NaNO₂溶液对金溶解具有最大效率。从“改性”水溶液中的氧化还原电位而非离子活度系数变化的角度讨论了稀硝酸和亚硝酸氧化对金溶解的影响。