CN104764819A - Method for rapidly measuring halogenated semi-volatile organic pollutant sub-cooled vapor pressure in environment - Google Patents
Method for rapidly measuring halogenated semi-volatile organic pollutant sub-cooled vapor pressure in environment Download PDFInfo
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- CN104764819A CN104764819A CN201510159392.0A CN201510159392A CN104764819A CN 104764819 A CN104764819 A CN 104764819A CN 201510159392 A CN201510159392 A CN 201510159392A CN 104764819 A CN104764819 A CN 104764819A
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Abstract
The invention discloses a method for rapidly measuring halogenated semi-volatile organic pollutant sub-cooled vapor pressure in an environment, and belongs to the field of environment oriented analysis. The vapor pressure refers to an important physicochemical parameter for describing an environment behavior of compounds and can be used for characterizing the tendency of the compounds escaping from liquid or solids and the adsorption effect of particulate matters on the compounds, and the migration and fate behaviors of the compounds are further researched. The method disclosed by the invention comprises the following steps: by adopting a gas chromatographic method, selecting a sub-cooled vapor pressure value of a standard compound according to an inverse proportional relationship between the retention volume or retention time of a solute in a gas chromatographic column and the solute, performing regression on a vapor pressure and temperature relation equation by virtue of data statistics software by using a least square method, and measuring the sub-cooled vapor pressure under different ambient temperatures. The constructed detection method has high repeatability and reliability, and according to verifications of different compounds, accuracy and usability of the method are proved.
Description
Technical field
The present invention relates to the method for Fast Measurement halo half volatile organic contaminant supercooled vapor pressure, belong to Environment Oriented analysis technical field, be specifically related to the method for half volatile organic contaminant supercooled vapor pressure in a kind of Fast Measurement environment.
Background technology
Along with the development of industrial society, increasing half volatile material enters in various surrounding medium (as air, water, soil) in a large number.Because these semi-volatile compounds may constitute a serious threat to health and ecologic environment and more and more receive the concern of people.As typical emerging halo environmental contaminants, many bromobiphenyl ether (PBDEs) and polychlorinated biphenyl ether (PCDEs) cause the toxicology harm such as effect (carcinogenic, teratogenesis, mutagenesis), thyroid hormone disturbing effect, nerve and genotoxicity owing to having three, have been the study hotspot of current environment worker.In order to understand this kind of halo half volatile material migration situation in the environment better, obtaining some environment physical and chemical parameters exactly and being very important.
Supercooled vapor pressure (p) is the important the physical-chemical parameters describing compound environmental behaviour, it can the characterizing compounds trend of escaping from liquid or solid and particle to its adsorption effect, so as to studying migration and the fate behavior of this compound further.In general, for the compound of low-vapor pressure, can adopt saturated air-flow method, effusion method measures its p value, but for PBDEs and PCDE
sthis kind of halogenated compound, because molecular weight is comparatively large, has half volatile, thus when using saturated air-flow method or effusion method measures, absolute concentration in gas phase is very low, only has and could measure p value by highly sensitive detection means, causes the p Value Data of this compounds comparatively deficient; And due to the limitation of method itself, measured value can be made to produce very large deviation, and measured value neither be very accurate.
Vapor-phase chromatography is a kind of environmental analysis technology of easy also widespread use fast, according to the retention volume V of solute in gas chromatographic column
ror retention time t
rand the relation that the vapor pressure p of solute is inversely proportional to and carat wear dragon (Clapeyron) equation to represent the relation between vapor pressure p and temperature T, can obtain equation 1/ Δ
vaphd (lnp)=1/ (RT
2) dT, then can consider the supercooled vapor pressure value p selecting appropriate criteria compound
ref, calculate the supercooled vapor pressure value p of halo half volatile material
i.At present, the rare report of the vapor pressure values of halo half volatile organic contaminant.Thus, build a kind of practical and method of the supercooled vapor pressure value of halo half volatile organic contaminant in the simple Fast Measurement environment of algorithm, for inquiring into this kind of emerging halo half volatile organic contaminant in environment at the Transport And Transformation of environment with return the research of degradation behavior to have important scientific meaning, and to the environmental risk assessment of this kind of organic contaminant and supervision, there is practical significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide the easy of halo half volatile organic contaminant supercooled vapor pressure value in a kind of quick testing environment, fast, accurately, and the method for applied range.
As follows in order to solve above technical matters the technical solution used in the present invention:
A method for halo half volatile organic contaminant supercooled vapor pressure value in quick testing environment, adopts vapor-phase chromatography, according to the retention volume (V of solute in gas chromatographic column
r) or retention time (t
r) relation that is inversely proportional to the vapor pressure (p) of solute, select the supercooled vapor pressure value (p of appropriate criteria compound
ref), and appear cold vapor pressure (p) and temperature (T) relation equation by data statistics recurrence, the supercooled vapor pressure (p at varying environment temperature can be measured
i).Its concrete grammar is as follows:
(1) first step, according to the relation that the vapor pressure p of the retention volume V of halo half volatile organic contaminant in gas chromatographic column or retention time t and halo half volatile organic contaminant is inversely proportional to, draws:
V
R,i/V
R,ref＝p
ref/p
i＝t
R,i/t
R,ref(1)
Again according to vapor pressure p and its heat of evaporation Δ of halo half volatile organic contaminant
vaprelation between H, when halo half volatile organic contaminant reaches biphase equilibrium in gas chromatographic column, represents the relation between vapor pressure p and temperature T according to carat pendant dragon (Clapeyron) equation:
dp/dT＝Δ
vapH/T·ΔV (2)
In formula (2), Δ
vaph is heat of evaporation, and the molar volume that Δ V equals gas deducts the molar volume of liquid, and because the molar volume of gas is much bigger relative to the molar volume of liquid, therefore Δ V can be approximately equal to the molar volume V of gas
g.In addition the vapor pressure due to halo half volatile organic contaminant is very low, and therefore can suppose that its steam is ideal gas, so equation (2) can be rewritten as:
dp/dT＝Δ
vapH·p/(R·T
2) (3)
Wherein R is gas law constant.Further derivation formula (3) obtains (4):
1/Δ
vapH·dlnp＝1/(R·T
2)·dT (4)
According to equation (4), due to Δ
vaph is unknown, therefore can not calculate the supercooled vapor pressure of halo half volatile organic contaminant according to equation (4).
(2) second step, select the n-compound of known vapor pressure, this n-compound is similar to halo half volatile organic contaminant structure to be determined, has half volatile, compresses into row measure the supercooled vapor of halo half volatile organic contaminant to be measured.Concrete grammar is as follows:
Selection standard compound (representing with ref), and represent i-th halo half volatile organic contaminant to be measured with i, then at the same temperature, formula (4) can be write as:
1/Δ
vapH
ref·dlnp
ref＝1/(R·T
2)·dT
1/Δ
vapH
i·dlnp
i＝1/(R·T
2)·dT
dlnp
i＝(Δ
vapH
i/Δ
vapH
ref)·dlnp
ref(5)
Can obtain formula (5) integration:
lnp
i＝(Δ
vapH
i/Δ
vapH
ref)·lnp
ref+C (6)
Known according to formula (1):
lnp
i＝lnp
ref-ln(t
Ri/t
Rref) (7)
Wushu (6) and formula (7) combine and obtain formula (8):
Adopt least square method, according to formula (8) to the ln (t under different temperatures
ri/ t
rref) and lnp
refcarry out linear regression analysis, the coefficient delta in formula (6) can be obtained
vaph
i/ Δ
vaph
refwith constant term C.Through type (6), according to the vapor pressure values p of n-compound
ref, just can to the supercooled vapor pressure p of halo half volatile organic contaminant
imeasure.
(3) the 3rd steps, in order to ensure the accuracy of gas chromatography determination vapor pressure values, with the halo half volatile organic contaminant of known vapor pressure be correct compound, by the correlation analysis to the saturated vapor pressure values lnp of air-flow method mensuration and the vapor pressure values lnp of gas chromatography determination, and then gas chromatography determination value is corrected.
(4) the 4th steps, the recurrence of equation parameter between the vapor pressure p of halo half volatile organic contaminant and temperature T, calculates the supercooled vapor pressure value p under varying environment temperature conditions
i.
Consider that pressure is the function of temperature, along with the change of temperature, the vapor pressure of compound is also in continuous change.Under normal circumstances, in a less temperature range (if environment temperature is usually between 0-30 DEG C), the relation of vapor pressure and temperature can be expressed as:
Can measure under five ambient temperature conditions (as 0 DEG C according to the vapor-phase chromatography introduced above (GC), 5 DEG C, 15 DEG C, 25 DEG C, 30 DEG C) vapor pressure values, returned out A, B parameter of their vapor pressure p and temperature T relation equation by mathematical statistics software least square method, then can calculate the vapor pressure values under varying environment temperature conditions.
The invention has the beneficial effects as follows, adopt the inventive method can realize the method for halo half volatile organic contaminant supercooled vapor pressure in a kind of Fast Measurement environment, the method is easy and quick, accurately reliable, strong support can be provided for probing into halo half volatile material transport conversion behavior in environment.Use the halo half volatile organic contaminant supercooled vapor pressure pH-value determination pH result of this patent of invention, important basic data can be provided for study mechanism work, and to environmental ecology venture analysis and evaluation, there is important scientific meaning.
The method of mensuration halo half volatile organic contaminant vapor pressure values provided by the invention has following several advantage: (1), by selecting appropriate criteria compound, can use the supercooled vapor pressure value of gas chromatography determination halo half volatile organic contaminant.(2) recurrence of vapor pressure and temperature relation equation parameter, can calculate the supercooled vapor pressure value under varying environment temperature conditions further, is more conducive to the fate behavior research of this compounds in physical environment, has more practical significance.
Accompanying drawing explanation
Fig. 1 is halo half volatile organic contaminant (MeO-PBDEs) to be measured and the logarithm value ln (t of the ratio of n-compound retention time
ri/ t
rref) and the logarithm value lnp of supercooled vapor pressure of n-compound
reflinear relationship, can formula be obtained from figure
in coefficient delta
vaph
i/ Δ
vaph
refwith constant term C.
Fig. 2 is the logarithm value lnp of halo half volatile organic contaminant (MeO-PBDEs) supercooled vapor pressure
refwith the graph of a relation of temperature T, formula can be obtained from figure
in parameter A, B value.
Embodiment
The specific embodiment of the present invention is further illustrated below in conjunction with accompanying drawing and technical scheme.
Embodiment 1
(1) select p, p`-DDT is as n-compound, and Preliminary Determination MeO-PBDEs is in the saturated vapour pressure value of several temperature spot.
The GC being furnished with ECD monitor at Hp-6890 analyzes, measure the retention time of MeO-PBDEs under condition of different temperatures, and to the retention time of each MeO-PBDEs and p, the ratio of the retention time of p`-DDT and p, the vapor pressure values of p`-DDT has carried out correlation analysis, thus obtains the coefficient delta in equation (6)
vaph
i/ Δ
vaph
refwith constant term C, by the vapor pressure values of p, p`-DDT under equation (6) and different temperatures, primary Calculation the saturated vapour pressure value of MeO-PBDEs at several temperature spot can be gone out.GC analysis condition: N2 is carrier gas, and the 1ml of DB1 becomes mildewed thin glass tube chromatographic column, and column diameter is 0.25 μm, and constant current conditions linear velocity is 3.5ml/min, temperature conditions: the retention time measured in 90-200 DEG C of temperature range under 6-8 isocratic condition is analyzed.The 30m of DB5 becomes mildewed thin glass tube chromatographic column, and column diameter is 0.25mm, thickness be 0.25 μm for analyzing MeO-PBDEs, Cheng Sheng condition: 90 DEG C (2.0min), 30 DEG C of min
-1, 200 DEG C, 1.5 DEG C of min
-1, 325 DEG C (7.0min), furnace temperature has been corrected by thermocouple thermometer.
(2) (0 is measured under five ambient temperature conditions according to the GC method of above-mentioned introduction, 5,15,25,30 DEG C) vapor pressure values, by A, B parameter using mathematical statistics software least square method to return out vapor pressure and temperature relation equation, then can calculate the vapor pressure values under varying environment temperature conditions.
Thus, the ln (t of MeO-PBDEs can be obtained
ri/ t
rref) and lnp
reflinear relationship chart and A, B parameter of vapor pressure and temperature relation equation.
Embodiment 2
(1) select p, p`-DDT is as n-compound, and Preliminary Determination PCDEs is in the supercooled vapor pressure value of several temperature spot.
The GC being furnished with ECD monitor at Hp-6890 analyzes, measure the retention time of PCDEs under condition of different temperatures, and to the retention time of each PCDEs and p, the ratio of the retention time of p`-DDT and p, the vapor pressure values of p`-DDT has carried out correlation analysis, thus obtains the coefficient delta in equation (6)
vaph
i/ Δ
vaph
refwith constant term C, by the vapor pressure values of p, p`-DDT under equation (6) and different temperatures, primary Calculation the supercooled vapor pressure value of PCDEs at several temperature spot can be gone out.GC analysis condition: N2 is carrier gas, and the 1ml of DB1 becomes mildewed thin glass tube chromatographic column, and column diameter is 0.25 μm, and constant current conditions linear velocity is 3.5ml/min, temperature conditions: the retention time measured in 90-200 DEG C of temperature range under 6-8 isocratic condition is analyzed.The 30m of DB5 becomes mildewed thin glass tube chromatographic column, and column diameter is 0.25mm, thickness be 0.25 μm for analyzing PCDEs, Cheng Sheng condition: 90 DEG C (2.0min), 30 DEG C of min
-1, 200 DEG C, 1.5 DEG C of min
-1, 325 DEG C (7.0min), furnace temperature has been corrected by thermocouple thermometer.
(2) (0 is measured under five ambient temperature conditions according to the GC method of above-mentioned introduction, 5,15,25,30 DEG C) vapor pressure values, by A, B parameter using mathematical statistics software least square method to return out vapor pressure and temperature relation equation, then can calculate the vapor pressure values under varying environment temperature conditions.
Thus, the ln (t of PCDEs can be obtained
ri/ t
rref) and lnp
reflinear relationship chart and A, B parameter of vapor pressure and temperature relation equation.
Claims (1)
1. the method for halo half volatile organic contaminant supercooled vapor pressure in Fast Measurement environment, it is characterized in that, step is as follows:
The first step, according to the relation that the vapor pressure p of the retention volume V of halo half volatile organic contaminant in gas chromatographic column or retention time t and halo half volatile organic contaminant is inversely proportional to, draws:
V
R,i/V
R,ref＝p
ref/p
i＝t
R,i/t
R,ref(1)
According to vapor pressure p and its heat of evaporation Δ of halo half volatile organic contaminant
vaprelation between H, when halo half volatile organic contaminant reaches biphase equilibrium in gas chromatographic column, represents the relation between vapor pressure p and temperature T according to C1apeyron equation:
dp/dT＝Δ
vapH/T·ΔV (2)
In formula (2), Δ
vaph is heat of evaporation, and the molar volume that Δ V equals gas deducts the molar volume of liquid, and the molar volume of gas is much bigger relative to the molar volume of liquid, Δ V is approximately equal to the molar volume V of gas
g; The vapor pressure of halo half volatile organic contaminant is very low, assuming that its steam is ideal gas, formula (2) is rewritten as:
dp/dT＝Δ
vapH·p/(R·T
2) (3)
Wherein R is gas law constant; Further formula (4):
1/Δ
vapH·d ln p＝1/(R·T
2)·dT (4)；
Second step, selects the reference compound of known vapor pressure, and this reference compound is similar to halo half volatile organic contaminant structure to be determined, has half volatile, compresses into row measure the supercooled vapor of unknown halo half volatile organic contaminant; Concrete grammar is as follows:
Select reference compound, represent with ref, and represent i-th unknown halo half volatile organic contaminant with i, at the same temperature, formula (4) is write as:
1/Δ
vapH
ref·d ln p
ref＝1/(R·T
2)·dT
1/Δ
vapH
i·d ln p
i＝1/(R·T
2)·dT
d ln p
i＝(Δ
vapH
i/Δ
vapH
ref)·d ln p
ref(5)
Formula (5) integration is obtained:
ln p
i＝(Δ
vapH
i/Δ
vapH
ref)·ln p
ref+C (6)
Know according to formula (1):
ln pi＝ln p
ref-ln(t
Ri/t
Rref) (7)
Wushu (6) and formula (7) combine and obtain formula (8):
Adopt least square method, according to formula (8) to the ln (t under different temperatures
ri/ t
rref) and ln p
refcarry out linear regression analysis, namely obtain the coefficient delta in formula (6)
vaph
i/ Δ
vaph
refwith constant term C; Through type (6), according to the vapor pressure values p of reference compound
ref, to the supercooled vapor pressure p of halo half volatile organic contaminant
imeasure;
(3) the 3rd steps, ensure the accuracy of gas chromatography determination vapor pressure values, with the halo half volatile organic contaminant of known vapor pressure be correct compound, by the correlation analysis to the saturated vapor pressure values lnp of air-flow method mensuration and the vapor pressure values lnp of gas chromatography determination, gas chromatography determination value is corrected;
(4) the 4th steps, the recurrence of equation parameter between the vapor pressure p of halo half volatile organic contaminant and temperature T, calculates the supercooled vapor pressure value p under varying environment temperature conditions
i;
Pressure is the function of temperature, and along with the change of temperature, the vapor pressure of compound is also in continuous change, and the relation of vapor pressure and temperature is expressed as:
According to the vapor pressure values under gas chromatography determination varying environment temperature conditions, returned out A, B parameter of vapor pressure p and temperature T relation equation by mathematical statistics method least square method, then calculate the vapor pressure values under varying environment temperature conditions.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111189869A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for measuring key parameters of semi-volatile organic compound release in building decoration material |
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2015
- 2015-04-03 CN CN201510159392.0A patent/CN104764819A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900711A (en) * | 2006-06-02 | 2007-01-24 | 中国石油兰州石油化工公司 | Method and device for detecting micro oxygen containing compound in low boiling point hydrocarbon |
Non-Patent Citations (3)
| Title |
|---|
| 成海容等: "青海瓦里关大气中多环芳烃的研究", 《中国环境科学》 * |
| 赵洪霞等: "气相色谱法测定多溴联苯的蒸气压", 《色谱》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111189869A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for measuring key parameters of semi-volatile organic compound release in building decoration material |
| CN111189869B (en) * | 2018-11-15 | 2022-04-08 | 中国科学院大连化学物理研究所 | Method for determining SVOC release key parameters in building decoration material |
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Application publication date: 20150708 |