1、INTERNATIONAL STANDARD IS0 12169 First edition 1996-04-01 Nickel oxide - Determination of nickel content - Electrolytic deposition method Oxyde de nickel - Dosage du nickel - MBthode par d mwl is the mass, in grams, of the weighing bottle and test portion before drying; m,2 is the mass, in grams, of
2、 the weighing bottle and test portion after drying. 8.1.2 Calculate the content of nickel in the test por- tion, WNi, as a percentage by mass, corrected for the moisture content, by using the formula: 1 O4 (ml - mCu - mCo + mNJ ONi = m0x(lOO-o,) where m0 is the mass, in grams, of the test portion; m
3、l is the mass, in grams, of nickel (plus Cu and Co) plated on the cathode (7.2.6); mCu is the mass, in grams, of copper found in the electroplated nickel (7.4); mCo is the mass, in grams, of cobalt found in the electroplated nickel (7.4); mNi is the mass, in grams, of residual nickel found in the el
4、ectrolyte solution (7.3). 8.2 Precision 8.2.1 Laboratory tests Nine laboratories in four countries participated in the testing of this procedure using five samples of nickel oxide: NIST-671, NIST-672, NIST-673, S-1003 (acid- soluble black oxide), and S-l 900 (refractory sinter). Each laboratory repo
5、rted three results for each sample. Two of the three determinations were carried out as duplicates on day I. The third determination was carried out separately on a different day, day 2. 8.2.2 Statistical analysis 8.2.2.1 Results from the interlaboratory test pro- gramme were evaluated according to
6、IS0 5725 2). The data were tested for statistical outliers by the Cochran and Grubb tests (see IS0 5725-2). 8.2.2.2 The principle of the Cochran test is that a set of results is an outlier if the within-laboratory variance is too large in relation to others. The Grubb test is to determine if the mea
7、n from a laboratory is too far from the other laboratory means. Both tests were applied at the 95 % confidence level. 2) IS0 5725:1986, Precision of test methods - Determination of repeatability and reproducibility for a standard test method by inter-laboratory test (now withdrawn), was used to obta
8、in the precision data. 4 Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-0 IS0 IS0 12169:1996(E) 8.2.2.3 From the two values obtained on day 1 the repeatability (r) and r
9、eproducibility (RI were calculated at the 95 % confidence level using the procedure specified in IS0 5725 2). From the mean value of the duplicates on day 1 and the value obtained on day 2, the within-laboratory reproducibility b) the results of the analysis; c) the number of independent replicates;
10、 d) any unusual features noted during the analysis; e) any operation not specified in this International Standard or regarded as optional. Sample Table 1 - Results of statistical analysis Nickel content, % (m/m) Precision data Mean Grand mean Repeatability Reproducibility (day I) (day1 + day2) r R I
11、 Rw 1 (NIST-671) 77,00 76.99 0,316 0,334 0,168 2 (NIST-672) 77,30 77,32 0,068 0,159 0,141 3 (NET-673) 77,80 77.78 0,099 0,089 0,108 4 (S-1003) 76,85 76,82 0,099 0,203 0,224 5 (S-1900) 76,49 76,49 0,090 0,160 0,126 Copyright International Organization for Standardization Provided by IHS under license
12、 with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-IS0 12169:1996(E) I 0 IS0 Determination A.1 General Annex A (normative) of nickel in spent electrolyte by atomic absorption spectrometry A.3.3 Pipette, of capacity 25 ml, in accordance with IS0 648, class A.
13、This annex describes the procedure for the determi- nation of residual nickel in the electrolyte after the electrolytic deposition of nickel (see 7.3). A.2 Reagents In the analysis use only reagents of recognised ana- lytical grade and only grade 2 water as specified in IS0 3696. A.2.1 Nickel, stand
14、ard reference solution (I 000 mg/l). Weigh, to the nearest 0,001 g, 1 g of nickel metal of 99,9 % (m/m) minimum purity, transfer to a 600 ml beaker and dissolve in 40 ml of nitric acid (4.3). Evap- orate to a viscous syrup, cool and add 20 ml of hydro- chloric acid (pzc = 1 ,I 8 g/ml). Digest in a c
15、overed beaker until the frothing ceases and evaporate just to dryness. Dissolve the salts in 50 ml of hydrochloric acid (4.1) and transfer the solution to a 1 000 ml one- mark volumetric flask. Make up to the mark with water and mix. A.2.1.1 Nickel, standard solution (100 mg/l). Pipette 25,0 ml of t
16、he nickel standard reference sol- ution (A.2.1) into a 250 ml one-mark volumetric flask and add 10 ml of hydrochloric acid (4.1). Make up to the mark with water and mix. A.3 Apparatus Ordinary laboratory glassware, and A.3.1 Burette, of capacity 25 ml, graduated in div- isions of 0,l ml, in accordan
17、ce with IS0 385-1, class A. A.3.2 Volumetric flasks, of capacities 250 ml and 1 000 ml, in accordance with IS0 1042, class A. A.3.4 Atomic absorption spectrometer, equipped with a burner head for an air-acetylene flame and a nickel hollow cathode lamp. The spectrometer used in this method shall meet
18、 the instrument performance parameters given in annex C. A.4 Procedure A.4.1 Adjustment of atomic absorption spectrometer Set the required instrument parameters according to the manufacturers instructions. Adjust the wave- length to 232,0 nm and the nickel lamp current as rec- ommended. Light the bu
19、rner and adjust the flows of air and acetylene to obtain an oxidizing, clean, non- luminescent flame while aspirating water. Adjust the instrument to zero. A.4.2 Preparation of the set of calibration solutions Transfer, using a burette, 0 ml, 5,0 ml, IO,0 ml, 15,0 ml and 20,O ml of the nickel standa
20、rd solution (A.2.1 .I) to each of five 250 ml one-mark volumetric flasks. Add 20 ml of hydrochloric acid (4.11, make up to the mark with water and mix. These calibration solutions cor- respond to 0 mg, 0,5 mg, I,0 mg, I,5 mg and 2,0 mg of Ni in the 250 ml volume. A.4.3 Atomic absorption measurements
21、 A.4.3.1 Aspirate each of the calibration solutions (A.4.21, starting with the zero member and note the absorbance reading. Flush the system by aspirating water between each reading. A.4.3.2 Aspirate the analysed solution (7.3) and note the absorbance reading. Repeat the measurement of calibration s
22、olutions and the test solution such that 6 Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-0 IS0 the measurement of the test solution lies between the measurement of two
23、calibration solutions. A.4.4 Preparation of the calibration graph Plot the instrument reading against the nickel content of the calibration solutions (see A.4.3.1). A.5 Expression of results A.5.1 Using the calibration curve (A.4.4) read the amount of nickel corresponding to the measured ab- sorbanc
24、e of the test solution (A.4.3.2). IS0 12169:1996(E) A.5.2 The nickel content of the spent electrolyte, mNi, expressed as a mass, in grams, to be applied as a correction in 8.1.2, is given by the formula mNi = CNi X 1 O-3 where CNi is the mass, in milligrams, of nickel found in the test solution (7.3
25、). NOTES 4 For some atomic absorption instruments it may be necessary to use scale expansion. 5 If the nickel content of the analysed solution (7.3) is high, the solution may be diluted and an appropriate correc- tion made. Copyright International Organization for Standardization Provided by IHS und
26、er license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-IS0 12169:1996(E) Annex B (normative) Determination of cobalt and copper in electrodeposited nickel by atomic absorption spectrometry B.l General This annex describes the procedure for the determi-
27、nation of cobalt and copper in the electrolytically de- posited nickel (see 7.4). B.2 Reagents In the analysis use only reagents of recognised ana- lytical grade and only grade 2 water as specified in IS0 3696. 5.2.1 Cobalt, standard reference solution (I 000 mg/l). Weigh, to the nearest 0,001 g, 1
28、g of cobalt metal of 99,9 % (m/m) minimum purity and transfer to a 600 ml beaker. Add 30 ml of hydrochloric acid (4.1) and heat to complete dissolution. Cool, transfer to a 1 000 ml one-mark volumetric flask and add 25 ml of hydro- chloric acid (4.1). Make up to the mark with water, mix and store in
29、 a polyethylene bottle. B.2.1.1 Cobalt, standard solution (I 00 mg/l). Pipette 50,O ml of the cobalt standard reference sol- ution (B.2.1) into a 500 ml one-mark volumetric flask and add 25 ml of hydrochloric acid (4.1). Make up to the mark with water and mix. B.2.2 Copper, standard reference soluti
30、on (I 000 mg/l). Weigh, to the nearest 0,001 g, 1 g of copper metal of 99,9 % (m/m) minimum purity and transfer to a 600 ml beaker. Add 40 ml of nitric acid (4.3) and allow to stand until the reaction ceases. Heat to complete the dissolution and evaporate just to dryness. Cool, add 25 ml of hydrochl
31、oric acid (pzO = 1 ,I 8 g/ml), digest in a covered beaker until the frothing ceases and evap- orate just to dryness. Dissolve the salts in 50 ml of hydrochloric acid (4.11, heating if necessary. Cool and transfer to a 1 000 ml one-mark volumetric flask. Make up to the mark with water, mix and store
32、in a polyethylene bottle. B.2.2.1 Copper, standard solution (50 mg/l). Pipette 25,0 ml of the copper standard reference sol- ution (B.2.2) into a 500 ml one-mark volumetric flask and add 25 ml of hydrochloric acid (4.1). Make up to the mark with water and mix. B.3 Apparatus Ordinary laboratory glass
33、ware, and 5.3.1 Burette, of capacity 25 ml, graduated in div- isions of 0,l ml, in accordance with IS0 385-1, class A. B.3.2 Volumetric flasks, of capacities 100 ml, 500 ml and 1 000 ml, in accordance with IS0 1042, class A. B.3.3 Pipettes, of capacities 10 ml, 20 ml, 25 ml and 50 ml, in accordance
34、with IS0 648, class A. B.3.4 Atomic absorption spectrometer, equipped with a burner head for an air-acetylene flame and co- balt and copper hollow cathode lamps. The spectrom- eter used in this method shall meet the instrument performance parameters given in annex C. B.4 Procedure B.4.1 Adjustment o
35、f atomic absorption spectrometer Set the required instrument parameters according to the manufacturers instructions. Adjust the wave- lengths to either 240,7 nm for cobalt or 324,8 nm for copper. Set the lamp currents as recommended by the manufacturer. Light the burner and adjust the flows of air a
36、nd acetylene to obtain an oxidizing, clean, non-luminescent flame while aspirating water. Adjust the instrument to zero. 8 , Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,
37、-,-0 IS0 IS0 12169:1996(E) B.4.2 Preparation of test solutions B.4.2.1 Determination of cobalt Transfer an aliquot of IO,0 ml of the solution (7.4) into a 100 ml one-mark volumetric flask. Add 5 ml of hydrochloric acid (4.1). make up to the mark with water and mix. B.4.2.2 Determination of copper Tr
38、ansfer an aliquot of 20,O ml of the solution (7.4) into a 100 ml one-mark volumetric flask. Add 5 ml of hydrochloric acid (4.1), make up to the mark with water and mix. NOTE 6 If the content of cobalt or copper in the dilute test solution (B.4.2) is high, a smaller aliquot of the original sol- ution
39、 (7.4) may be taken. B.4.3 Preparation of calibration solutions Transfer, using a burette, 0 ml, 4,0 ml, 8,0 ml, 12,0 ml and 16,0 ml of each of the cobalt and copper standard solutions (B.2.1.1 and B.2.2.1) to each of five 100 ml one-mark volumetric flasks. Add 5 ml of hydrochloric acid (4.11, make
40、up to the mark with water and mix. These calibration solutions correspond to 0 mg, 0,4 mg, 0,8 mg, I,2 mg and I,6 mg of cobalt, and 0 mg, 0,2 mg, 0,4 mg, 0,6 mg and 0,8 mg of copper in the 100 ml volume. / 8.4.4 Atomic absorption measurement B.4.4.1 Aspirate each of the calibration solutions lB.4.3)
41、 starting with the zero member and note the absorbance reading. Flush the system by aspirating water between each reading. B.4.4.2 Aspirate the test solutions (B.4.2) and note the respective cobalt and copper absorbance read- ings. For each element, repeat the measurement of calibration solutions an
42、d the test solution such that the measurement of the test solution lies between the measurement of two calibration solutions, re- spectively. B.4.5 Preparation of calibration graph Plot the instrument readings against the cobalt and copper contents of the calibration solutions (B.4.4.1). B.5 Express
43、ion of results B.5.1 Using the calibration curve (B.4.5) read the amounts of cobalt and copper corresponding to the measured absorbances of the test solutions (B.4.4.2). B.5.2 Calculate the cobalt and copper contents in the electrodeposited nickel, mCo and mCu, expressed as a mass, in grams, of coba
44、lt and copper, to be applied as corrections in 8.1, by using the formula rnCo=CCoF10-3 mCu = C,-X FX 10e3 where Cc0 is the mass, in milligrams, of cobalt found in the analysed test solution (B.4.2.1); Cc” is the mass, in milligrams, of copper found in the analysed test solution (B.4.2.2); F is the v
45、olume ratio of the test solution (7.4) and the respective aliquot taken in B.4.2. Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-IS0 12169:1996(E) Annex C (normative) Ch
46、ecking of atomic absorption spectrometer performance parameters C. 1 Introduction The performance of atomic absorption spectrometers of the same or different manufacture may vary from instrument to instrument. It is therefore essential to establish that a particular instrument meets certain performa
47、nce requirements before it is used in this In- ternational Standard. C.2 Initial instrument adjustments C.2.1 Set up the atomic absorption spectrometer to operate with an air/acetylene flame using a single slot (normally about 10 cm) laminar flow burner head ac- cording to the manufacturers instruct
48、ions. C.2.2 Use a single element hollow cathode lamp as the light source for the element under test. Operate the source as recommended by the manufacturer. NOTE 7 The use of multi-element lamps is not generally recommended although some binary alloy lamps give a more stable emission than single elem
49、ent lamps. C.2.3 Light the burner and aspirate water until thermal equilibrium is reached. C.2.4 Aspirate a mid-range calibration solution of the element under test and adjust the instrument to give optimum absorption. Use the wavelengths specified in the relevant part of annex A or annex B of this In- ternational Standard and the slit setting or bandpass recommended by the instrument manufacturer for the element under test. C.2.5 Flush the burner system by aspiratin
