CN107525776B - Sample feeding method and device for atomic spectrometers - Google Patents
Sample feeding method and device for atomic spectrometers Download PDFInfo
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Abstract
The invention discloses a method and a device for sample injection of atomic spectrometers, which are characterized in that a solution of dithio formic acid (salt) containing amino is mixed with an element solution to be detected on line, the mixed solution is immediately subjected to gas-liquid separation and measurement, so that a volatile element complex enters an element analyzer for detection or is used for preparing a chemical vapor deposition film of the element.
Description
Technical Field
The invention belongs to the technical field of instrument analysis, and relates to a sample feeding method and device for atomic spectrometers.
Background
At present, most hydride generation sample injection systems used in atomic spectrometers use sodium (potassium) borohydride as a hydride generation reduction reagent, and after elements in a sample solution are reduced to gaseous hydrides by hydrogen in the sodium (potassium) borohydride, the elements are measured in the atomic spectrometers. Compared with the conventional pneumatic atomization sampling in atomic spectrum, the hydride sampling efficiency has higher sampling efficiency (the conventional pneumatic atomization sampling is only 3-5%, the determination sensitivity is lower, and the hydride sampling efficiency is close to 100%), so the hydride sampling efficiency has the characteristics of higher sensitivity and lower detection limit in determination. It has been used that hydrides of sodium (potassium) borohydride and nine elements (arsenic, antimony, bismuth, germanium, tin, lead, selenium, tellurium, mercury) which are traditionally easy to form hydrides are formed and measured by an atomic spectrometer.
In recent years, with the intensive research of scientific and technical personnel, workers engaged in analysis have successively found that other elements can also react with sodium (potassium) borohydride to generate hydrogenation reaction, and have published a plurality of research papers one after another.
Another defects caused by using sodium borohydride chemical vapor is that sodium borohydride is expensive and unstable, a solid reagent is decomposed into blocky sodium metaborate after long-term standing, and a solution is decomposed after long-term standing. needs to be prepared at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides brand-new methods and devices for sample injection of atomic spectrometers.
The technical scheme of the invention is as follows:
sample introduction method for atomic spectrometer, which is characterized in that the solution of dithioformic acid (salt) containing amido is mixed with the solution of element to be detected on line, the mixed solution is immediately subjected to gas-liquid separation and measurement, and the volatile element complex enters an element analyzer for detection or is used for preparing chemical vapor deposition film of the element.
The dithioformic acid (salt) containing amino group in the invention is soluble salt which is soluble in water.
The dithiocarbamate (salt) containing an amino group in the present invention is preferably a salt of diethyldithiocarbamate with an alkali metal, an alkaline earth metal and ammonia. Wherein the alkali metal is lithium, sodium and potassium; the alkaline earth metal is magnesium and calcium, preferably the salt of diethyldithiocarbamate with the alkali metals lithium, sodium and potassium, particularly preferably sodium dimethyldithiocarbamate (Na-DDTC)
The elements to be measured in the invention refer to part of main group elements, part of transition elements, noble metal elements and rare earth elements.
The present invention is characterized in that 0.005-35% (w/w) of a solution of dithiocarbamate containing an amine group is mixed in-line with a solution of an element to be measured having an acidity of 0.005-10.0M.
The invention is characterized in that the mass concentration of the dithio formic acid (salt) containing amino after being mixed with the element solution is 0.005-5%, preferably 0.01-1%; more preferably 0.015 to 0.5%.
The invention is characterised in that the acidity of the solution after the in-line mixing is between 0.01 and 3.0 mol/l, preferably between 0.02 and 1M,
more preferably, the acidity is 0.05 to 0.6M.
The element to be detected in the invention refers to a main group metal element excluding alkali metal and alkaline earth metal; a partial transition element; noble metal elements and rare earth elements. These elements include (but are not limited to): main group metal elements of indium, thallium, tin, lead and bismuth; transition elements of titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium and mercury; noble metal elements such as ruthenium, rhodium, palladium, silver, iridium, platinum and gold; the rare earth elements cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, uranium, thorium, and plutonium.
Preferred elements among the above elements refer to tin, lead, ruthenium, rhodium, palladium, silver, iridium, platinum, gold, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium and mercury.
typical embodiments of the present invention include the steps of (1) continuously pumping a sodium diethyldithiocarbamate solution having a mass concentration of 0.01 to 0.5% and an element-containing sample solution having an acidity of 0.02 to 0.3M at an equal flow rate of 1 to 5 ml, respectively, by using a peristaltic pump, (2) causing the two solutions to join together in a micro three-way tube and then immediately performing gas-liquid separation in a gas-liquid separator, and (3) introducing the separated gas into an atomic spectrometer for measurement.
The invention further discloses a sample introduction device applicable to an atomic spectrometer, which is characterized by comprising an element-containing sample solution introduction pipe 1, an amino-containing dithioformic acid (salt) solution introduction pipe 2, a peristaltic pump 3, a three-way pipe 4, a gas-liquid separator 5, a gas-liquid separator, a gas-liquid permeable and water-tight semipermeable membrane made of a porous glass sintered plate, a carrier gas inlet 6, a carrier gas outlet 7 and a waste liquid discharge pipe 8, wherein the peristaltic pump 3 extracts two solutions, then the two solutions are mixed through a tee joint and then are connected with the gas-liquid separator 5, the gas-liquid separator is provided with the carrier gas inlet 6 and the carrier gas inlet 7, and waste liquid for separating gas volatile matters is discharged through the waste liquid discharge pipe 8 by the peristaltic pump.
The invention further discloses an application of the sample injection method of atomic spectrometer in chemical vapor deposition and preparation of inorganic coating gaseous precursor.
The typical sample introduction device for atomic spectrometer (see attached figure 1 in description) comprises an element-containing sample solution introduction pipe, an amino-containing dithioformic acid (salt) solution introduction pipe, a peristaltic pump, a three-way pipe, a gas-liquid separator (containing porous glass sintered plate and other gas-permeable and water-impermeable semipermeable membranes), a carrier gas inlet, a carrier gas outlet and a waste liquid discharge pipe 8, wherein the peristaltic pump extracts two solutions, the two solutions are converged in the three-way pipe to react and then connected with the gas-liquid separator, the gas-liquid separator is provided with the carrier gas inlet and the carrier gas inlet, and waste liquid for separating gas volatile matters is discharged by the peristaltic pump through a waste liquid discharge pipe.
A second exemplary sample introduction device for an atomic spectrometer (see the attached drawing 2 in the specification) suitable for the present invention comprises an element-containing sample solution introduction tube 1, an amine group-containing dithioformic acid (salt) solution introduction tube 2, a peristaltic pump 3, a three-way tube 4, an atomizer 9 for atomization sample introduction of atomic absorption or inductively coupled plasma emission spectroscopy (or mass spectrometry), a mist chamber (a cyclone mist chamber or a Scott mist chamber) 5 for atomic absorption or inductively coupled plasma emission spectroscopy (or mass spectrometry), a carrier gas inlet 6, a carrier gas outlet 7 and a waste liquid discharge tube 8; the peristaltic pump extracts the two solutions, the two solutions are mixed through the tee joint and then enter the atomizer, the atomizer sprays the two solutions and then enters the fog chamber, the gas-liquid separator is provided with a carrier gas inlet and a carrier gas outlet, and waste liquid of separated gas volatile matters is discharged by the peristaltic pump through a waste liquid discharge pipe.
Description of the drawings:
FIG. 1 is a diagram of an apparatus suitable for sample injection in an atomic spectrometer;
FIG. 2 is a diagram of a sample injection device of a suitable atomic spectrometer with an atomizer;
1. sample solution introducing tube for element, 2 dithioformic acid (salt) solution introducing tube containing amino group
3. A peristaltic pump 4, a three-way pipe 5, a gas-liquid separator 6, a carrier gas inlet,
7 carrier gas outlet 8 and waste liquid discharge pipe 9 atomizer.
Detailed Description
In order to more fully explain the practice of the invention, the following preparative examples of the invention are provided. These examples are merely illustrative and do not limit the scope of the invention.
Example 1
(1) Respectively preparing sample solutions containing gold and silver elements (the element content is 500ppb, the nitric acid acidity is 0.3M) and 0.4% sodium diethyldithiocarbamate (copper reagent, DDTC) solutions, and then respectively pumping the two solutions at the flow rate of 2 ml/min by adopting a peristaltic pump so that the two solutions are converged in three-way pipes and then react.
(2) Separating the generated element volatile matters and the solution after reaction in an gas-liquid separator;
(3) the reaction solution from the three-way outlet pipe immediately flows into gas-liquid separator, where the volatile element (DDTC and element complex) is separated by bubbling through a porous glass sintered plate, and the volatile element is introduced into an atomic spectrometer atomization or ionization device for spectral or mass spectrometric measurement, the measured element sensitivity is 25-40 times that of the solution without DDTC under conditions, the measurement sensitivity is greatly improved, and the detailed illustration is shown in figure 1 of the specification.
Example 2
(1) Sample solutions containing element mercury (element content is 500ppb, nitric acid acidity is 0.10M) and 0.4% sodium diethyldithiocarbamate (copper reagent, DDTC) solutions are prepared respectively, and then the two solutions are extracted by a peristaltic pump at the flow rate of 1.8 ml/min respectively, so that the two solutions are converged in tee pipes and then react.
(2) Separating the generated element volatile matters and the solution after reaction in an gas-liquid separator;
(3) the reaction solution from the three-way outlet pipe immediately flows into gas-liquid separator, where the volatile element (DDTC and element complex) is separated by bubbling through a porous glass sintered plate, and the volatile element is introduced into an atomic spectrometer atomization or ionization device for spectral or mass spectrometric measurement, the measured element sensitivity is 25-40 times that of the solution without DDTC under conditions, the measurement sensitivity is greatly improved, and the detailed illustration is shown in figure 1 of the specification.
Example 3
sample introduction device for atomic spectrometer, comprising an element-containing sample solution introduction tube 1, an amino group-containing dithioformic acid (salt) solution introduction tube 2, a peristaltic pump 3, a three-way tube 4, and a gas-liquid separator, wherein the gas-liquid separator comprises a gas-permeable and water-impermeable semipermeable membrane made of a porous glass sintered plate, a carrier gas inlet, a carrier gas outlet and a waste liquid discharge tube, the peristaltic pump draws the two solutions, then the two solutions are converged in the three-way tube for reaction, and then the gas-liquid separator is connected with the gas-liquid separator, the gas-liquid separator is provided with the carrier gas inlet and the carrier gas inlet, and the waste liquid for separating gas volatile matters is discharged by the.
It will be apparent to those skilled in the art that various changes and modifications can be made in the above embodiments without departing from the scope and spirit of the invention, and it is intended that all simple changes, equivalents and modifications made to the above embodiments in accordance with the technical spirit of the invention shall fall within the scope of the invention.
Claims (1)
- The sample introduction method of atomic spectrometers is characterized in that sodium diethyldithiocarbamate solution and element solution to be detected are mixed on line, the mixed solution is immediately subjected to gas-liquid separation and determination, and volatile element complex enters the atomic spectrometer for detection;the method comprises the following steps:(1) continuously pumping a sodium diethyldithiocarbamate solution with the mass concentration of 0.01-0.5% and a to-be-detected element solution with the acidity of 0.02-1.0M at the same speed of 1-5 ml/min by using a peristaltic pump;(2) the two solutions are converged and reacted in a three-way pipe, and then gas-liquid separation is immediately carried out in a gas-liquid separator;(3) the separated gas is introduced into an atomic spectrometer for measurement;the device adopted by the method comprises an element solution inlet pipe (1) to be detected, a sodium diethyldithiocarbamate solution inlet pipe (2), a peristaltic pump (3), a three-way pipe (4), a gas-liquid separator (5), a carrier gas inlet (6), a carrier gas outlet (7) and a waste liquid discharge pipe (8); the peristaltic pump (3) extracts the element solution to be detected and the sodium diethyldithiocarbamate solution, the two solutions are mixed after passing through the three-way pipe (4) and then are connected with the gas-liquid separator (5), the gas-liquid separator contains a permeable and impermeable semipermeable membrane made of a porous glass sintered plate, the gas-liquid separator is provided with a carrier gas inlet (6) and a carrier gas outlet (7), and the waste liquid for separating gas volatile matters is driven by the peristaltic pump (3) to be discharged through a waste liquid discharge pipe (8).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610557720.7A CN106248593A (en) | 2016-07-15 | 2016-07-15 | A kind of method and apparatus of atom spectrometer sample feeding |
| CN2016105577207 | 2016-07-15 |
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| CN107525776A CN107525776A (en) | 2017-12-29 |
| CN107525776B true CN107525776B (en) | 2020-01-31 |
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| CN201710545032.3A Active CN107525776B (en) | 2016-07-15 | 2017-07-06 | Sample feeding method and device for atomic spectrometers |
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| CN108535185A (en) * | 2018-04-25 | 2018-09-14 | 天津师范大学 | A kind of sample injection method occurred for atomic spectrograph gaseous state chelate |
| CN108732162A (en) * | 2018-05-29 | 2018-11-02 | 四川理工学院 | The device for fast detecting and detection method of arsenic concentration in a kind of water |
| CN109709054A (en) * | 2019-01-21 | 2019-05-03 | 广西科技大学鹿山学院 | Flame atomic absorption spectrophotometer aeration sample introduction regulating device |
| CN109900683A (en) * | 2019-03-26 | 2019-06-18 | 攀钢集团攀枝花钢铁研究院有限公司 | The online internal standard hybrid system of Element detection |
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- 2016-07-15 CN CN201610557720.7A patent/CN106248593A/en active Pending
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- 2017-07-06 CN CN201710545032.3A patent/CN107525776B/en active Active
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| CN1437013A (en) * | 2002-02-04 | 2003-08-20 | 李学璧 | Sample entering method for atomic spectrometer |
| CN101082546A (en) * | 2007-06-29 | 2007-12-05 | 天津师范大学 | Compounds used for element forming volatile matter |
| CN101339126A (en) * | 2008-07-09 | 2009-01-07 | 天津师范大学 | Atom spectrometer sample feeding method |
| CN101738377A (en) * | 2008-11-12 | 2010-06-16 | 同济大学 | Flow injection unequal flow complexation detection method |
| CN102230897A (en) * | 2011-06-27 | 2011-11-02 | 天津师范大学 | Method for improving gaseous sample introduction efficiency of atomic spectrum |
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| CN107525776A (en) | 2017-12-29 |
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