Ion Chromatographic Method for the Determination of Chlorine Content in Titanium Sponge

doi:10.19894/j.issn.1000-0518.210444

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (9): 1412-1420.DOI: 10.19894/j.issn.1000-0518.210444

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Ion Chromatographic Method for the Determination of Chlorine Content in Titanium Sponge

Mi-Fang DU¹(), Guo-Liang CHANG¹, Pan LIU¹, Yi ZHANG¹, Xin-Yao ZHANG¹^,²^,³, Jing-Bin LI¹

^1.Luo Yang Ship Materials Institute，Luoyang 471023，China
^2.Henan Key Laboratory of Technology and Application of Structural Materials for Ships and Marine Equipments，Luoyang 471023，China
^3.National New Material Production and Application Demonstration Platform （Advanced Marine Engineering and High-tech Ship Materials），Luoyang 471023，China

Received:2021-09-01 Accepted:2022-01-05 Published:2022-09-01 Online:2022-09-08
Contact: Mi-Fang DU
About author:du_mifang@725.com.cn
Supported by:
the National New Material Production and Application Demonstration Platform （Advanced Marine Engineering and High?tech Ship Materials） Fund Project(TC180A6MR/2)

Abstract

Abstract:

Chlorine affects the properties of titanium-based materials. At present， the problems are that the analytical process of chlorine in titanium sponge is long， many reagents are required， and it is only qualitative. In this study， ion chromatography method was used for the determination of chlorine in titanium sponge. Through the study of the treatment method of titanium sponge， analysis of titanium removal effect， determination of gradient elution procedure， anti-jamming experiments， etc.， the effects of solvents， acidity and chromatographic conditions on the results were investigated， the chromatographic conditions were optimized， and the difficult technical problem of separating chlorine from titanium matrix was solved. An ion chromatography method for the chlorine content in titanium sponge was established. It is found that ①Hydrofluoric acid will affect the application effect of H-type cation exchange pretreatment column （H column for short）； ②The treated sponge titanium solution needs to be diluted first and then filtered， so the effect of removing heavy metals is better； ③After adding nitric acid， sponge titanium treated with sulfuric acid nitric acid must be heated to drive away nitrogen dioxide； ④As the use time of chromatographic column becomes longer， the column efficiency decreases， and the resolution of Cl^-with $S O 4 2 -$ and $N O 3 -$ decreases. The separation effect can be improved by changing the gradient elution procedure. H column was used to remove titanium cations； The gradient elution procedure was used to elute the solution with KOH solution （1.0 mL/min）， the inhibitory conductivity detection was used， and the chlorine was quantitatively determined by external standard method. The limit of detection and limit of quantification of the methods are 0.0039 μg/mL and 0.013 μg/mL， respectively. The relative standard deviation （RSD） is not more than 5.0%， and the recovery of standard addition is 94%~110%. It can analyze 0.005%~2.0% chlorine in titanium sponge. It is wider than that of the national standard GB/T 4698.25-2017 （0.010%~0.40%）， and the results are in good agreement with those of the national standard photometry， which can meet the requirements of the determination of chlorine content in titanium sponge.

Key words: Ion chromatography, Titanium sponge, Chlorine, Determination

CLC Number:

O657.7

Mi-Fang DU, Guo-Liang CHANG, Pan LIU, Yi ZHANG, Xin-Yao ZHANG, Jing-Bin LI. Ion Chromatographic Method for the Determination of Chlorine Content in Titanium Sponge[J]. Chinese Journal of Applied Chemistry, 2022, 39(9): 1412-1420.

Figures/Tables 11

References 17

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试样编号 Sample No.	海绵钛质量 m（titanium sponge）/g	定容体积 Constantvolume/mL	稀释倍数 Dilution factor	钛含量 Titanium ion content/（μg·mL^-1）		使用的过滤柱个数 Number of filter columns used
试样编号 Sample No.	海绵钛质量 m（titanium sponge）/g	定容体积 Constantvolume/mL	稀释倍数 Dilution factor	H柱过滤前（半定量分析） Before filtering by H?filter column （Semi?quantitative analysis）	H柱过滤后 After filtering by H?filter column	使用的过滤柱个数 Number of filter columns used
1#	0.103 23	100	10	97.79	0.0045	2
2#	0.101 36	100	10	99.74	0.048	1
3#	0.099 57	100	10	99.94	0.074	1
4#	0.101 55	100	10	99.89	0.042	1
5#	0.102 70	100	10	97.91	0.021	1
6#	0.102 72	100	10	97.57	0.016	1
7#	0.104 10	100	10	98.27	0.048	1
8#	0.104 21	100	10	98.73	0.033	1
9#	0.104 36	100	10	97.79	0.052	1
10#	0.101 52	100	10	98.90	0.048	1
11#	0.104 00	100	10	未测（约100） Unmeasured （about 100）	0.053	1
12#	0.102 34	100	10	未测（约100） Unmeasured （about 100）	0.064	1
13#	0.099 99	100	10	未测（约100） Unmeasured （about 100）	0.059	1
14#	0.100 35	100	10	未测（约100） Unmeasured （about 100）	0.015	1

试样编号 Sample No.	海绵钛质量 m（titanium sponge）/g	定容体积 Constantvolume/mL	稀释倍数 Dilution factor	钛含量 Titanium ion content/（μg·mL^-1）		使用的过滤柱个数 Number of filter columns used
试样编号 Sample No.	海绵钛质量 m（titanium sponge）/g	定容体积 Constantvolume/mL	稀释倍数 Dilution factor	H柱过滤前（半定量分析） Before filtering by H?filter column （Semi?quantitative analysis）	H柱过滤后 After filtering by H?filter column	使用的过滤柱个数 Number of filter columns used
1#	0.103 23	100	10	97.79	0.0045	2
2#	0.101 36	100	10	99.74	0.048	1
3#	0.099 57	100	10	99.94	0.074	1
4#	0.101 55	100	10	99.89	0.042	1
5#	0.102 70	100	10	97.91	0.021	1
6#	0.102 72	100	10	97.57	0.016	1
7#	0.104 10	100	10	98.27	0.048	1
8#	0.104 21	100	10	98.73	0.033	1
9#	0.104 36	100	10	97.79	0.052	1
10#	0.101 52	100	10	98.90	0.048	1
11#	0.104 00	100	10	未测（约100） Unmeasured （about 100）	0.053	1
12#	0.102 34	100	10	未测（约100） Unmeasured （about 100）	0.064	1
13#	0.099 99	100	10	未测（约100） Unmeasured （about 100）	0.059	1
14#	0.100 35	100	10	未测（约100） Unmeasured （about 100）	0.015	1

淋洗液浓度 Eluent concentration/（mmol·L^-1）	保留时间 Retention time/min		半峰宽 Half width/min	氯与邻近峰的保留时间差 The retention time difference between the peak of Cl^- and the adjacent peak/min	分离度 Resolution
淋洗液浓度 Eluent concentration/（mmol·L^-1）	氯峰 Chloride peak	邻近峰 Adjacent peak	氯 Chloride		分离度 Resolution
10	7.410	9.20	0.223	1.79	4.78
15	5.863	7.10	0.166	1.237	3.93
20	5.117	6.04	0.133	0.923	3.68
30	4.337	5.01	0.114	0.673	3.57

淋洗液浓度 Eluent concentration/（mmol·L^-1）	保留时间 Retention time/min		半峰宽 Half width/min	氯与邻近峰的保留时间差 The retention time difference between the peak of Cl^- and the adjacent peak/min	分离度 Resolution
淋洗液浓度 Eluent concentration/（mmol·L^-1）	氯峰 Chloride peak	邻近峰 Adjacent peak	氯 Chloride		分离度 Resolution
10	7.410	9.20	0.223	1.79	4.78
15	5.863	7.10	0.166	1.237	3.93
20	5.117	6.04	0.133	0.923	3.68
30	4.337	5.01	0.114	0.673	3.57

试样编号 Sample No.	试样中氯质量分数 Found/%	加入量 Added/ （μg·mL^-1）	测得值 Found/（μg·mL^-1）		平均值 Average	回收率 Recovery/%
试样编号 Sample No.	试样中氯质量分数 Found/%	加入量 Added/ （μg·mL^-1）	1	2	平均值 Average	回收率 Recovery/%
7997	0.056	0.50	0.555	0.550	0.553	99
7887?1	0.050	0.50	0.579	0.577	0.578	106
7887?2	0.062	0.05	0.111	0.107	0.109	94
6613	0.039	0.03	0.069	0.066	0.068	97
7371	0.018	0.01	0.027	0.031	0.029	110

Ion Chromatographic Method for the Determination of Chlorine Content in Titanium Sponge

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样品编号 Sample No.	氯质量分数 Found/%			允许差 Allowable deviation/%	结果情况 Comparison result
样品编号 Sample No.	离子色谱法 Ion chromatography	光度法 Photometry	氯化银比浊法 Silver chloride turbidimetry	允许差 Allowable deviation/%	结果情况 Comparison result
4010	0.037	0.036	<0.060	0.010	Good agreement
4518	0.057	0.055	<0.060	0.022	Good agreement
5002?1	0.043	0.046	<0.060	0.012	Good agreement
5082	0.029	0.028	<0.060	0.009	Good agreement
5329?1	0.039	0.041	<0.060	0.010	Good agreement

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