This work reports the development of a certified reference material (CRM) of holmium(III) oxide Ho2O3 in acidic solution for the wavelength scale calibration of UV-Vis spectrophotometers. A 4.0% Ho2O3 solution was gravimetrically prepared in 10% perchloric acid and bottled in 5.0 mL glass ampoules. Homogeneity, stability and characterization were assessed according to ISO 17034 and ISO Guide 35. The material certification was undertaken by two laboratories by using UV-Vis spectrophotometry for characterization of the 14 peaks of minimum transmittance of Ho2O3, using a spectral bandwidth of 1.00 nm and a scanning speed of 30.0 nm min‒1. The material property values in wavelength (nm) were obtained for these 14 peaks, together with the expanded uncertainty (U) of 0.12 nm, for a coverage factor (k = 2.00) corresponding to a probability of approximately 95%, which took into account the standard uncertainties obtained in each study performed for the certification of the produced reference material.

Inicialmente, para adquirir experiência na determinação coulométrica da pureza do dicromato, realizou-se uma comparação bilateral entre os institutos nacionais de metrologia (INM) do Brasil e da Rússia. Em seguida, objetivando comparar os resultados das medições do dicromato de potássio (K2Cr2O7) entre os INM que utilizam a coulometria com elevada precisão para certificar materiais de referência (MR) de compostos puros, o Inmetro participou de uma comparação-chave denominada CCQM-K96. A partir dessas comparações, certificou-se um lote do MR de K2Cr2O7. Este trabalho objetiva apresentar os resultados das comparações internacionais, bem como os estudos necessários ao desenvolvimento do material de referência certificado (MRC) de K2Cr2O7 tornando-o um padrão primário para titulações de oxirredução. Para o lote certificado, considerou-se tanto os estudos de homogeneidade quanto de caracterização, obtendo-se o valor da pureza, em fração mássica do K2Cr2O7 de 99,974% ± 0,011%, para k = 2 e probabilidade de abrangência de aproximadamente 95%.

Initially, for acquiring experience in determining the purity of the dichromate by coulometry, a bilateral comparison between the national metrology institutes (NMIs) from Brazil and Russia was carried out. Next, to evaluate the comparability of the measurement results among the NMIs that use high-precison constant-current coulometry for certifying reference materials (RMs) of pure compounds, National Institute of Metrology, Quality and Technology (Inmetro) participated in a key-comparison named CCQM-K96. Because of both comparisons, a batch of the RM of K2Cr2O7 was certified. This work aims to present the international comparison results, as well as the studies needed to develop a certified reference material (CRM) of K2Cr2O7 for redox titrations. In the certification of the batch, studies of homogeneity and characterization were considered. The K2Cr2O7 batch was certified in mass fraction of 99.974% ± 0.011%, for k = 2 and coverage probability of approximately 95%.

A coulometria é considerada o método de maior qualidade metrológica para medição de quantidade de substância de padrões primários. Entretanto, a contaminação de sais de elevada pureza está presente em níveis traços sendo necessária a sua identificação e quantificação. Este trabalho apresenta os estudos desenvolvidos pelo Inmetro (Instituto Nacional de Metrologia, Normalização e Qualidade Industrial, Brasil) para determinar a pureza do cloreto de potássio (KCl) por titulação coulométrica a corrente constante, além da determinação do brometo como seu principal contaminante por cromatografia iônica (IC). Esses estudos foram necessários para desenvolver material de referência certificado (MRC) de KCl para garantir a qualidade dos resultados das medições químicas principalmente as de titulometria. A caracterização do candidato a MRC de KCl apresentou pureza de 99,9662%, a qual foi obtida após a correção do brometo, em fração mássica, obtido por IC, de 182,47 ± 3,03 mg kg-1 (incerteza expandida, k = 2, para um nível de confiança de aproximadamente de 95%).

Coulometry is considered the highest metrological method for measuring the amount of substance of high-purity compounds. However, the contamination of the high purity salts is present in trace levels and its identification and quantification are necessary. This work aims to present the studies performed by Inmetro (National Institute of Metrology, Standardization and Industrial Quality, Brazil) to determine the purity of potassium chloride (KCl) by constant-current coulometric titration, as well as the determination of bromide as the main impurity in the KCl through ion chromatography (IC). These studies were needed to develop certified reference material (CRM) of KCl to guarantee the quality of the chemical measurements, mainly those performed by titrimetric analysis. The characterization of the candidate CRM of KCl by coulometric titration presented the purity of 99.9662%. This value was obtained after bromide correction of 182.47 ± 3.03 mg kg-1 (expanded uncertainty for k = 2, for a confidence level of approximately 95%) for the mass fraction bromide assayed by IC.