CN201803980U - Device for measuring free metal ion activity - Google Patents

Device for measuring free metal ion activity Download PDF

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Publication number
CN201803980U
CN201803980U CN2010205537922U CN201020553792U CN201803980U CN 201803980 U CN201803980 U CN 201803980U CN 2010205537922 U CN2010205537922 U CN 2010205537922U CN 201020553792 U CN201020553792 U CN 201020553792U CN 201803980 U CN201803980 U CN 201803980U
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pond
ion
solution
donor
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王代长
饶伟
杨喜田
刘世亮
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Henan Agricultural University
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Henan Agricultural University
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Abstract

The utility model discloses a device for measuring free metal ion activity, comprising a receptor pond unit and a donator pond unit, wherein the receptor pond unit comprises a receptor pond and a receptor solution; the receptor pond and the receptor solution form a circulating device through a peristaltic pump I; the donator pond unit comprises a donator pond and a donator solution; the donator pond and the donator solution form a circulating device through a peristaltic pump II; and the receptor pond and the donator pond are communicated through a cation-exchange membrane. The device for measuring free metal ion activity can be used for simultaneously measuring various metal ions and heavy metal ions, without mutual interference between the metal ions and the heavy metal ions. The device for measuring free metal ion activity has wide measurement range, not only is applicable to general constant analysis and microanalysis, but also is applicable to trace analysis.

Description

A kind of free metal ion activity determinator
Technical field
The utility model relates to a kind of free free metal ion activity determinator.
Background technology
In industry and agriculture field, mensuration for free ion is necessary, but, in most of the cases, be subjected to that free concentration of heavy metal ion is the main factor that its biology of decision is given property and toxicity in river, ocean and the soil liquid of heavy metal pollution.Set up at present the method for multiple measurement free metal ion concentration, as being subjected to the interference of other metallic ion in the measurement of ion-selective electrode method, its linear response range is all at high concentration region, and the concentration of metal ions that dissociates in most environmental sample is well below its responding range; The galvanochemistry voltammetry can directly be measured the concentration of heavy metal ion of low concentration, but in this method experimentation because the use of electric current has destroyed solution equilibria, the organic matter in the solution is adsorbed on easily on the electrode and influences the enrichment and the process in leaching of electrode; Cation exchange resin processes can be measured multiple free concentration of heavy metal ion in the environment solution simultaneously, yet this method need have very detailed understanding to the characterization of adsorption of selected resin, also must consider the composition of environment solution when carrying out morphological analysis.
The utility model content
The technical problems to be solved in the utility model provides a kind of free ion concentration determinator and method.
The technical solution of the utility model is: a kind of free metal ion activity determinator, it comprises acceptor pool unit and donor pool unit, the acceptor pool unit comprises acceptor pond and receptor solution, acceptor pond and receptor solution are formed a circulating device by the peristaltic pump I, the donor pool unit comprises donor pond and donor solution, donor pond and donor solution are formed a circulating device by the peristaltic pump II, the acceptor pond is connected by cation-exchange membrane with the donor pond, be fitted with conductance electrode I and ion-selective electrode I in the receptor solution, the conductance electrode I links to each other with conductivity meter, the ion-selective electrode I links to each other with potentiometer, be fitted with conductance electrode II and ion-selective electrode II in the donor solution, the conductance electrode II links to each other with conductivity meter, and the ion-selective electrode II links to each other with potentiometer.
Described ion-selective electrode is pH electrode or potassium ion-selective electrode.
The metallic ion of described mensuration is Cu, Zn, Ni, Cd, Pb.
Free metal ion activity determinator of the present utility model is a Du Nan switch, and it is to be based upon on the theoretical foundation of Du Nan balance, and the Du Nan switch is the both-end circulating device.Confessing little chamber inner diameter is 2cm, dark 4.3cm, and volume is 13.5mL; Accepting the cell diameter is 2cm, dark 3.3cm, and volume is 10.3mL, and the diameter of amberplex is 3.0cm, and two Room spiral interfaces can be fixed amberplex, and amberplex is that two spiral interfaces are fixed by ring washer when screwing.Donor solution and receptor solution are separated by cation-exchange membrane, and reaction tank is divided into two parts: donor pond and acceptor pond.Cation-exchange membrane is Nafion 117 (Du Pont), and the surface is electronegative, and the kation of negative ion and complex state can't pass through, like this through entering the kation that has only free state in acceptor pond behind the exchange membrane.Matrix liquid is equipped with in the donor pond, and promptly with the solution or the complex solution of soil balance, be equipped with and the roughly the same concentration supporting electrolyte of donor liquid KNO in the acceptor pond 3Solution.During the experiment beginning,, will cause that the small ion that comprises in the solution of both sides spreads mutually because the chemical potential of both sides solution is unequal, cause chemical potential to equate at last, promptly reach the Du Nan balance, promptly donor liquid equates with the activity ratio (electric charge correction) that is subjected to metallic ion in the body fluid, that is:
Figure BSA00000294865500021
C The i donor, C The i acceptor, C The j donor, C The j acceptorBe respectively donor liquid and the activity that is subjected to free ion i and j in the body fluid.z iAnd z jIt is respectively the charge number of kation i and j.
Described device is measured the method for free metal ion activity, and its step is as follows:
(1) processing of cation-exchange membrane: exchange membrane is used 0.1mol/L nitric acid dousing 24 hours, soaks 5 hours with deionized water, uses 1mol/L KNO 3Soak after 24 hours, use 0.01mol/L KNO again 3Soaked 24 hours;
(2) the donor pond needs of packing into are measured the matrix liquid of free metal ion activity, and the acceptor pond concentration of packing into is the supporting electrolyte KNO of 0.5～2 times of donor pond solution concentration 3Solution;
(3) connect donor pond and donor solution, acceptor pond and receptor solution are by peristaltic pump composition closed circulation device separately;
(4) open conductivity meter and ion-selective electrode potentiometer, preheating 30～40 minutes;
(5) unlatching peristaltic pump, initial electric conductivity value of record conductivity meter and end electric conductivity value, the initial pH value of potentiometer and end pH value;
(6) value that do not change at 1～2 hour of the electric conductivity value of the donor solution measured of record conductivity meter and receptor solution judges that in view of the above both sides solution reaches the Du Nan balance;
(7) with the concentration of free metal ion in the graphite furnace atomic absorption spectrometry acceptor pond, detect and be limited to 10 -11Mol/L is with the activity of potassium ion in the potassium ion-selective electrode method mensuration acceptor pond;
(8) according to formula
Figure BSA00000294865500031
Calculate the free metal ion activity of donor liquid.
Test solution of the present utility model can separate with research system after experiment reaches balance, and by potassium ion-selective electrode measurement electrolyte potassium ion activity wherein, the concentration graphite furnace atomic absorption spectrometry of heavy metal ion detects and is limited to 10 again -11Mol/l just can calculate free heavy metal ion activity in the donor liquid by above formula.
The beneficial effects of the utility model are: acceptor pond and two Room, donor pond are spiral interface, amberplex can be fixed; Conductivity meter is measured electricity and is led, and can judge the time that the cationic ion diffusive equilibrium is carried out; The mensuration avaivable electrode method of the metallic ion in acceptor pond is directly measured the activity of metallic ion; This method can be measured multiple metal and heavy metal ion simultaneously, and can not disturb each other.Its measurement range is very wide, is not only applicable to general constant, microanalysis, but also is applicable to trace analysis; Can be used for the mensuration of the free heavy metal ion activity of the soil liquid, as load onto earth pillar, use lean solution KNO 3Drip washing earth pillar, solution enter the donor pond, and the solution in the donor pond is constantly by the earth pillar circulation, until reaching membrane equilibrium.Lean solution KNO is also used in the acceptor pond 3, the activity of mensuration acceptor pond heavy metal ion and potassium ion; The mensuration that can be used for complexation constant, complex ion can not pass through amberplex, and a certain amount of ligand ion and metallic ion are put in the donor pond, acceptor pond lean solution KNO 3, the activity of mensuration acceptor pond metallic ion is calculated the activity of metallic ion in the donor pond, thereby is calculated complexation constant.Method used herein can be measured multiple metallic element simultaneously on the basis that does not influence the reaction system balance, detect and be limited to 10 -11Mol/L, and can not disturb each other; And test system is what to be separated with reaction system, can also avoid the influence of other material to measuring in the reaction system.
Description of drawings
Accompanying drawing is free metal ion activity determinator figure.
Embodiment
Embodiment 1
As shown in drawings, a kind of free metal ion activity determinator, it comprises acceptor pool unit and donor pool unit, the acceptor pool unit comprises acceptor pond 1 and receptor solution 2, acceptor pond 1 is formed a circulating device with receptor solution 2 by peristaltic pump I 3a, the donor pool unit comprises donor pond 4 and donor solution 5, donor pond 4 is formed a circulating device with donor solution 5 by peristaltic pump II 3b, acceptor pond 1 is connected by cation-exchange membrane 10 with donor pond 4, be fitted with conductance electrode I 6a and potassium ion-selective electrode I 7a in the receptor solution 2, conductance electrode I 6a links to each other with conductivity meter 8, potassium ion-selective electrode I 7a links to each other with potentiometer 9, be fitted with conductance electrode II 6b and potassium ion-selective electrode II 7b in the donor solution 5, conductance electrode II 6b links to each other with conductivity meter 8, and potassium ion-selective electrode II 7b links to each other with potentiometer 9.
Cation-exchange membrane is the Nafion of Du Pont 117 exchange membranes (perfluoro sulfonic acid membrane), buys in E.I.Du Pont Company thickness: 183 microns; Density: 360g/m 2Conductivity: 0.083S/cm; Exchange capacity: 0.89.
The assay method of free metal ion activity, its step is as follows:
(1) processing of cation-exchange membrane: exchange membrane is used 0.1mol/l nitric acid dousing 24 hours, soaks 5 hours with deionized water, uses 1mol/l KNO again 3Soak after 24 hours, use 0.01mol/l KNO again 3Soaked 24 hours;
(2) donor pond dress needs to measure the matrix liquid of free metal ion activity, and acceptor pond dress concentration is the supporting electrolyte KNO of 0.5～2 times of donor pond solution concentration 3Solution;
(3) connect donor pond and donor solution, acceptor pond and receptor solution are by peristaltic pump composition closed circulation device separately;
(4) open conductivity meter and ion-selective electrode potentiometer, preheating 30～40 minutes;
(5) open peristaltic pump, initial electric conductivity value of record conductivity meter and end electric conductivity value; The initial pH value of potentiometer and end pH value;
(6) till the electric conductivity value of the donor solution of record conductivity meter mensuration and receptor solution did not change in 1～2 hour, judge that in view of the above both sides solution reaches the Du Nan balance;
(7) with the concentration of free metal ion in the graphite furnace atomic absorption spectrometry acceptor pond, detect and be limited to 10 -11Mol/L is with the activity of potassium ion in the potassium ion-selective electrode method mensuration acceptor pond;
(8) according to formula
Figure BSA00000294865500051
Calculate the free metal ion activity of donor liquid.
Concrete numerical value is as follows:
50mL 10 is contained in the acceptor pond -3Mol/L KNO 3Solution, donor pond solution contains 10 -3Mol/L KNO 3, 10 -4Mol/L Cu and 10 -4Mol/L citric acid solution 150mL.
Acceptor pond: during beginning: it is 120.6 μ s/cm that electricity is led, and the pH value is respectively 6.64.
During end: it is 152 μ s/cm that electricity is led, and the pH value is respectively 3.84.
The activity of K ion is: 1.14 * 10 -3Mol/L
The activity of Cu ion is: 4.12 * 10 -5Mol/L
The donor pond: to lead be 415 μ s/cm to electricity during beginning, pH value 2.89.
To lead be 353 μ s/cm to electricity during end, and the pH value is respectively 3.40.
The activity of K ion is: 8.25 * 10 -4Mol/L
According to formula:
Figure BSA00000294865500052
Calculate:
The activity calculated value of Cu ion is 2.17 * 10 in the donor pond -5Mol/L.
The mensuration of condition complexation constant: supposition Cu and citric acid generate complex compound at 1: 1:
Figure BSA00000294865500061
Concentration when initial (mol/L): 10 -410 -4
Concentration during balance (mol/L): 10 -4-(10 -4-2.17 * 10 -5) 2.17 * 10 -5(10 -4-2.17 * 10 -5)
Design conditions complex compound constant: K=(HL -Cu)/(HL 2-) (Cu 2+)
lgK＝lg((10 -4-2.17×10 -5)/((10 -4-(10 -4-2.17×10 -5))×2.17×10 -5))
＝5.22
Embodiment 2
Free metal ion activity determinator and assay method are with embodiment 1.Measure the activity of Zn ion in the solution.
50mL 10 is contained in the acceptor pond -3Mol/L KNO 3Solution, donor pond solution contains 10 -3Mol/L KNO 3, 10 -3Mol/L Zn and 10 -3Mmol/L citric acid solution 150mL, ion-selective electrode are the pH electrode.
Acceptor pond: during beginning: it is 117.2 μ s/cm that electricity is led, and the pH value is respectively 6.64.
During end: it is 288 μ s/cm that electricity is led, and the pH value is respectively 3.38.
The activity of K ion is: 1.32 * 10 -3Mol/L
The activity of Zn ion is: 3.633 * 10 -4Mol/L
The donor pond: to lead be 1319 μ s/cm to electricity during beginning, pH value 2.97.
To lead be 1085 μ s/cm to electricity during end, and the pH value is respectively 3.09.
The activity of K ion is: 9.56 * 10 -4Mol/L
According to formula:
Figure BSA00000294865500062
The activity calculated value that calculates Zn ion in the donor pond is 1.92 * 10 -4Mol/L.
The mensuration of condition complexation constant: supposition Zn and citric acid generate complex compound at 1: 1:
Figure BSA00000294865500071
Concentration when initial (mol/L): 10 -310 -3
Concentration during balance (mol/L): 10 -3-(10 -3-1.92 * 10 -4) 1.92 * 10 -4(10 -3-1.92 * 10 -4)
Design conditions complex compound constant: K=(HL-Zn)/(HL 2-) (Zn 2+)
lgK＝lg((10 -3-1.92×10 -4)/((10 -3-(10 -3-1.92×10 -4)×1.92×10 -4))
＝4.34
Be under 0.001mol/l and the 0.0001mol/l condition relatively at citric acid concentration, the condition complexation constant of Zn has certain difference, and main cause is that the pH value of system is respectively 3.40 and 3.09, reduces with pH, the condition complexation constant drops to 4.34 by 5.22, and this phenomenon is very normal.
Embodiment 3
Free metal ion activity determinator and assay method are with embodiment 1.Measure the activity of Pb ion in the solution.
50mL 10 is contained in the acceptor pond -3Mol/L KNO 3Solution, donor pond solution contains 10 -3Mol/L KNO 3, 10 -4Mol/L Pb and 10 -4Mol/L EDTA solution 150mL.
Acceptor pond: during beginning: it is 123.0 μ s/cm that electricity is led, and the pH value is respectively 5.74.
During end: it is 229 μ s/cm that electricity is led, and the pH value is respectively 4.04.
The activity of K ion is: 1.76 * 10 -3Mol/L
The activity of Pb ion is: 9.98 * 10 -7Mol/L
The donor pond: to lead be 413 μ s/cm to electricity during beginning, pH value 3.69.
To lead be 334 μ s/cm to electricity during end, and the pH value is respectively 3.89.
The activity of K ion is: 9.01 * 10 -4Mol/L
According to formula:
Figure BSA00000294865500072
Calculate
The activity calculated value of Pb ion is 2.62 * 10 in the donor pond -7Mol/L.
The mensuration of condition complexation constant: supposition is Pb and 1: 1 complex compound of EDTA generation when pH4.0:
Figure BSA00000294865500081
Concentration when initial (mol/L): 10 -410 -4
Concentration during balance (mol/L): 10 -4-(10 -4-2.62 * 10 -7) 2.62 * 10 -7(10 -4-2.62 * 10 -7)
Design conditions complex compound constant: K=(EDTA-Pb)/(EDTA 2-) (Pb)
lgK＝lg((10 -4-2.62×10 -7)/((10 -4-(10 -4-2.62×10 -7))×2.62×10 -7))
＝9.16
Embodiment 4
50mL 10 is contained in the acceptor pond -3Mol/L KNO 3Solution, donor pond solution contains 10 -3Mol/L KNO 3, 10 -3Mol/L Cu and 10 -3Mmol/L EDTA solution 150mL.
Acceptor pond: during beginning: it is 119.1 μ s/cm that electricity is led, and the pH value is respectively 6.43.
During end: it is 208.1 μ s/cm that electricity is led, and the pH value is respectively 6.39.
The activity of K ion is: 1.33 * 10 -3Mol/L
The activity of Cu ion is: 3.76 * 10 -6Mol/L
The donor pond: to lead be 1433 μ s/cm to electricity during beginning, pH value 6.19.
To lead be 1216 μ s/cm to electricity during end, and the pH value is respectively 6.23.
The activity of K ion is: 9.1 * 10 -4Mol/L
According to formula:
Figure BSA00000294865500082
Calculate
The activity calculated value of Cu ion is 1.94 * 10 in the donor pond -6Mol/L.
The mensuration of condition complexation constant: supposition Cu and EDTA when pH6.2 also generate 1: 1 complex compound:
Figure BSA00000294865500083
Concentration when initial (mol/L): 10 -310 -3
Concentration during balance (mol/L): 10 -3-(10 -3-1.94 * 10 -6) 1.94 * 10 -6(10 -3-1.94 * 10 -6)
Design conditions complex compound constant: K=(EDTA -Cu)/(EDTA 2-) (Cu)
lgK＝lg((10 -3-1.94×10 -6)/((10 -3-(10 -3-1.94×10 -6))×1.94×10 -6))
＝8.42
Embodiment 5
Free metal ion activity determinator and assay method are with embodiment 1.Measure the activity of Ni ion in the solution.
50mL 1.2 * 10 is contained in the acceptor pond -3Mol/L KNO 3Solution, donor pond solution contains 1.2 * 10 -3Mol/L KNO 3, 5.0 * 10 -5Mol/L Ni and 10 -4Mmol/L malic acid solution 50mL.
Acceptor pond: during beginning: it is 110.2 μ s/cm that electricity is led, and the pH value is respectively 6.56.
During end: it is 100.6 μ s/cm that electricity is led, and the pH value is respectively 6.25.
The activity of K ion is: 7.2 * 10 -4Mol/L
The activity of Ni ion is: 2.5 * 10 -7Mol/L
The donor pond: to lead be 410 μ s/cm to electricity during beginning, pH value 5.83.
To lead be 426 μ s/cm to electricity during end, and the pH value is respectively 5.56.
The activity of K ion is: 1.7 * 10 -3Mol/L
According to formula:
Figure BSA00000294865500091
Calculate
The activity calculated value of Ni ion is 1.4 * 10 in the donor pond -6Mol/L.
The mensuration of condition complexation constant: supposition Ni and malic acid negative ion when pH5.56 also generate 1: 1 complex compound:
Figure BSA00000294865500092
Concentration when initial (mol/L): 10 -45 * 10 -5
Concentration during balance (mol/L): 10 -4-(5 * 10 -5-1.8 * 10 -6) 1.4 * 10 -6(5 * 10 -5-1.4 * 10 -6)
Design conditions complex compound constant: K=(LNi)/(L 2-) (Ni 2+)
lgK＝lg((5×10 -5-1.4×10 -6)/((10 -4-(5×10 -5-1.4×10 -6))×1.4×10 -6))
＝5.82
Embodiment 6
Free metal ion activity determinator and assay method are with embodiment 1.Measure the activity of Cd ion in the solution.
50mL 1.5 * 10 is contained in the acceptor pond -3Mol/L KNO 3Solution, donor pond solution contains 1.5 * 10 -3Mol/LKNO 3, 5.0 * 10 -4Mol/L Cd and 10 -4Mol/L tartaric acid solution 50mL.
Acceptor pond: during beginning: it is 119.0 μ s/cm that electricity is led, and the pH value is respectively 6.43.
During end: it is 108.1 μ s/cm that electricity is led, and the pH value is respectively 6.69.
The activity of K ion is: 7.7 * 10 -4Mol/L
The activity of Cd ion is: 3.3 * 10 -7Mol/L
The donor pond: to lead be 433 μ s/cm to electricity during beginning, pH value 6.19.
To lead be 465 μ s/cm to electricity during end, and the pH value is respectively 6.23.
The activity of K ion is: 2.2 * 10 -3Mol/L
According to formula:
Figure BSA00000294865500101
Calculate
The activity calculated value of Cd ion is 2.7 * 10 in the donor pond -6Mol/L.
The mensuration of condition complexation constant: supposition Cd and tartrate negative ion when pH6.23 also generate 1: 1 complex compound:
Figure BSA00000294865500102
Concentration when initial (mol/L): 10 -45 * 10 -5
Concentration during balance (mol/L): 10 -4-(5 * 10 -5-2.7 * 10 -6) 2.7 * 10 -6(5 * 10 -5-2.7 * 10 -6)
Design conditions complex compound constant: K=(L-Cd)/(L 2-) (Cd 2+)
lgK＝lg((5×10 -5-2.7×10 -6))/((10 -4-(5×10 -5-2.7×10 -6))×2.7×10 -6))
＝5.52?。

Claims (2)

1. free metal ion activity determinator, it is characterized in that: it comprises acceptor pool unit and donor pool unit, the acceptor pool unit comprises acceptor pond and receptor solution, acceptor pond and receptor solution are formed a circulating device by the peristaltic pump I, the donor pool unit comprises donor pond and donor solution, donor pond and donor solution are formed a circulating device by the peristaltic pump II, the acceptor pond is connected by cation-exchange membrane with the donor pond, be fitted with conductance electrode I and ion-selective electrode I in the receptor solution, the conductance electrode I links to each other with conductivity meter, the ion-selective electrode I links to each other with potentiometer, be fitted with conductance electrode II and ion-selective electrode II in the donor solution, the conductance electrode II links to each other with conductivity meter, and the ion-selective electrode II links to each other with potentiometer.
2. free metal ion activity determinator according to claim 1 is characterized in that: described ion-selective electrode is pH electrode or potassium ion-selective electrode.
CN2010205537922U 2010-10-09 2010-10-09 Device for measuring free metal ion activity Expired - Fee Related CN201803980U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102445475A (en) * 2010-10-09 2012-05-09 河南农业大学 Free metal ion activity measuring device and measuring method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102445475A (en) * 2010-10-09 2012-05-09 河南农业大学 Free metal ion activity measuring device and measuring method thereof

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