A kind of measuring method of mercury vapor pressure
Technical field
The present invention relates to a kind of measuring method of mercury vapor pressure, be specifically related to the mercurous thing of lighting field---be commonly referred to as the saturated mercury vapor pressure of solid mercury and the measuring method that saturated mercury vapor pressure varies with temperature characteristic.
Background technology
The pressure that reaches liquid (or solid and gas) balance under constant temperature in the closed system claims saturated vapor pressure, and its value only becomes with substance classes (liquid person's character) and temperature, and is all irrelevant with container size, liquid number or other mixed gass.Saturated vapor pressure is relevant with temperature: temperature raises, and molecular motion is quickened, thereby the gas molecule in space number increases in the unit interval, and vapour pressure raises.
Vapour pressure is along with the available clapeyron-Clausius equation of the variation of absolute temperature is represented:
P is the saturated vapor pressure (Pa) of liquid when temperature T in the formula, and T is thermodynamic temperature (K), and Δ Hm is liquid mole heat of gasification (Jmol
-1), R is a gas law constant.If the scope of temperature variation is little, Δ Hm can be considered constant.
What the method for measurement saturated vapor pressure was at present known mainly contains three kinds: dynamic method, saturated air-flow method and static method.Static method is applicable to the measurement of solid heating and decomposition equilibrium pressure force measurement and volatile liquid saturated vapor pressure, and accuracy is higher.Therefore the measurement of mercury vapor pressure suits to adopt static method.
Static method is meant test substance is placed in the closed system, directly measures vapour pressure under different temperature, and it requires inclusion-free gas in the system.Normally use balance pipe (claiming the equipotential meter again) to measure.Balance pipe is formed by connecting by a bulb and a U-shaped pipe, as shown in Figure 1, test substance places in the bulb A, places fluid to be measured B in the U-shaped pipe, balance pipe 1 is connected with extract system R, pressure gauge 2, at a certain temperature, when the liquid level in the U-shaped pipe during, show that the pressure of U-shaped pipe two arm liquid levels top equates in same level, write down the temperature and pressure of this moment, then manometric indicating value is exactly the saturated vapor pressure of liquid under this temperature, and in other words, measured temperature is exactly the boiling point under this pressure.Utilize balance pipe to obtain and the maintenance system in be the saturated vapour of pure sample, the liquid in the U-shaped pipe plays fluid-tight and balance indicative function.
Use static method can measure the saturated vapor pressure of liquid mercury under different temperatures.According to data with existing, can get the mercury vapor pressure curve P of fluid mercury correspondence under different temperatures
Hg, but static method desired in closed system the test condition of inclusion-free gas, use difficult realization the in the operating process in reality.
In the check of the solid mercury of lighting field, measurement, design, need to measure the solid temperature variant characteristic of mercury mercury vapor pressure, adopt static method that solid mercury is measured in the vapour pressure under the different temperatures, have operation inconvenience and occur the danger that mercuryvapour is revealed easily.
In the known technology, the saturated mercury vapor pressure of solid mercury (abbreviation mercury vapor pressure) of lighting field adopts the method for atomic absorption to measure usually, accepts to place the airtight cavity that is filled with mercury atom between the sensor at ultraviolet source and ultraviolet, and mercury atom is to 253; The 7nm ultraviolet light produces intrinsic and absorbs, and mercury atom concentration is high more, and is many more to UV Absorption, and there are corresponding relation in photosensitive value and mercury atom concentration that ultraviolet is accepted sensor, uses liquid mercury with reference to contrast, can measure the mercury vapor pressure of solid mercury; The solid mercury temperature of change can record the mercury vapor pressure under the different temperatures, obtains solid mercury mercury vapor pressure temperature characterisitic.Mention a kind of mercury vapor pressure measurement mechanism at Jap.P. JP2002055009, employing be the measuring method of atomic absorption.
Low-pressure mercury discharge lamp is because the fluorescent tube footpath is different, reach the required mercury vapor pressure value of optimal luminescent efficient difference, except needs are known solid mercury mercury vapor pressure temperature characterisitic, Gu mercury designs, the user more wishes to measure solid mercury light in the lamp of specific caliber and exports temperature variant characteristic.The method of atomic absorption can't be measured the light relatively of specific standard lamp and export temperature variant characteristic.
The method of measuring the light output of lamp at present is to survey the visible light luminous flux of lamp with integrating sphere (being called the logical ball of light again), integrating sphere is the complete spherical shell of a hollow, inwall coating white diffuse reflector, and the diffusion of ball inwall each point is even, light source is to be formed by stacking by the illuminance that reflected light repeatedly produces in the illuminance that produces on arbitrarily a bit on the ball wall, and the illuminance of optional position on the ball wall (retaining removes direct sunshine according to the back) is directly proportional with the luminous flux phi of lamp.Utilize integrating sphere, luminous flux that can the matching measurement light source is put into the same position of integrating sphere respectively with standard sources and light source to be measured, measures the illumination of their a certain identical points on spherical shell, and comparison can be obtained the luminous flux of light source then.Present integrating sphere can not carry out large-scale temperature adjustment, can not survey ultraviolet light, can't be used to measure the characteristic of solid mercury.
Summary of the invention
The objective of the invention is for overcoming above-mentioned deficiency, a kind of method of measuring mercurous thing mercury vapor pressure is provided, both can directly measure use mercurous thing lamp relatively light export temperature variant characteristic, can measure mercurous thing mercury vapor pressure and the temperature variant characteristic of mercury vapor pressure again.In the check of the solid mercury of lighting field, measurement, design, this method is simple, safety, directly, kills two birds with one stone.
The light output of lamp can be 253.7nm ultraviolet light illumination or luminous flux, also can be visible light illumination or luminous flux; Light output refers to the ratio of light output valve with the maximum light output valve of lamp of specified temp lamp relatively, represents that with η η can be the ratio of brightness value, and η also can be the ratio of light flux values, adopts brightness value more easily to realize.
A kind of measuring method of mercury vapor pressure is characterized in that:
Be by measure lamp that mercurous thing does the mercury source relatively light output compare calculating with the characteristic of mercurous thing temperature variation with liquid mercury, record the method that mercurous thing mercury vapor pressure and mercury vapor pressure vary with temperature characteristic.
Realize that technical scheme of the present invention is: it comprises that making one is provided with the also low-pressure mercury discharge lamp of built-in mercurous thing of cold junction; A same specification low-pressure mercury discharge lamp that is provided with cold junction and built-in liquid mercury, when the output temperature of the light relatively characteristic of this specification lamp liquid mercury through checking repeatedly, can be used as known reference object, need not make; But the high-low temperature chamber of a temperature adjustment; The small-sized oil bath device of control cold junction temperature; One is measured wavelength is the ultraviolet light illumination meter or the visible light illuminometer of 253.7nm ultraviolet radiation intensity; A recording storage computing machine.
Make the low-pressure mercury discharge lamp that not dusting is manufactured in the mercury source with mercurous thing, lamp is provided with the effect cold junction and mercurous thing is placed in one, and the temperature of mercurous thing is equal to cold junction temperature, and effectively cold junction is meant that cold junction temperature is lower than light temperature all the time.Effectively cold junction usually greater than 2 centimetres, and places the oil bath vessel from the region of discharge distance, to guarantee homogeneity, the accuracy of cold junction temperature.Effectively cold junction temperature is adjustable continuously.But lamp places in the high-low temperature chamber of temperature adjustment, and effectively the temperature adjustable extent of cold junction and high-low temperature chamber includes but not limited to-40 ℃-200 ℃, and lamp zone of living in should avoid wind that the lamp parameter generating is influenced.
Perforate placement measurement wavelength is a 253.7nm ultraviolet light illumination meter on the high-low temperature chamber, in the process of lighting a lamp, change effective cold junction temperature, after treating that cold junction temperature and brightness value are all stable, write down cold junction temperature, ultraviolet light illumination value respectively, record the characteristic of the light output of lamp with mercurous thing temperature variation, simple conversion promptly obtains light output relatively with the characteristic of mercurous thing temperature variation.The light output valve of lamp, light output is the stationary value of mercury vapor pressure when saturated relatively.Replace the low-pressure mercury discharge lamp of not dusting with the low-pressure mercury discharge lamp of dusting, with visible light illumination displacement 253.7nm ultraviolet light illumination meter, can measure visible light relatively light output with the characteristic of mercurous thing temperature variation.But through the integrating sphere of special repacking temperature adjustment, can measure the visible light luminous flux with the characteristic of mercurous thing temperature variation in the lamp, if the integrating sphere inwall is coated with the coating of reflection 253.7nm ultraviolet light, then can measure the characteristic of ultraviolet light luminous flux with mercurous thing temperature variation.The temperature characterisitic of fluorescent powder can be brought influence to measurement result when measuring visible light illumination, usually measure ultraviolet light illumination, but can compare with the measurement result of visible light and the measurement result of ultraviolet light, determine visible light and ultraviolet light difference with the cold junction temperature variation characteristic.
In same lamp or same specification lamp, liquid mercury is done the mercury source and make lamp equally, record the characteristic of the output of light relatively of liquid mercury lamp with liquid mercury temperature variation.In same lamp or same specification lamp, there are corresponding relation in the output valve η of light relatively and the mercury vapor pressure value of lamp, the maximal value 100% corresponding best mercury vapor pressure value of η, and η is the para-curve Changing Pattern with the characteristic that mercury vapor pressure changes, and sees the curve η among Fig. 4
HgAt the same end of the output of light relatively peak value, the η value of lamp is identical, and the mercury vapor pressure value is identical.The relatively light output valve of mercurous thing under temperature T 1 is η 1, light is exported the same end of peak value relatively, it is T2 that liquid mercury reaches η 1 pairing liquid mercury temperature, looks into liquid mercury mercury vapor pressure-temperature table of comparisons or analog computation formula and calculates the mercury vapor pressure value P of liquid mercury under temperature T 2
T2, the mercury vapor pressure value P of mercurous thing under temperature T 1
T1=P
T2According to this method, the lamp of mercurous thing each relatively light output valve η value relatively calculate with liquid mercury respectively, can record the mercury vapor pressure value of its corresponding temperature.
This method be ignore same lamp difference constantly difference or ignore same specification lamp to each other difference under equal manufacturing conditions, through repetition test, Gu mercury and liquid mercury are made the lamp of same specification at equal conditions, the same end of light output peak value relatively separately, light output valve η is identical relatively, and the pairing mercury vapor pressure value of η is identical, and repeatability better, with other method verification, the provable difference of ignoring for the influence of required measurement result be Be Controlled within the acceptable range.This method is measured the light output valve of lamp, light output η is the stationary value of mercury vapor pressure when saturated relatively.
Description of drawings
Fig. 1 is a device synoptic diagram of measuring mercury vapor pressure with static method.
Fig. 2 is a proving installation synoptic diagram of the present invention.
Fig. 3 is for to measure Zn-Hg (50%) mercury vapor pressure-temperature characteristics according to the present invention, wherein:
Description of reference numerals:
P
Hg: be known liquid mercury mercury vapor pressure-temperature characteristics;
P
Zn-Hg (50%): be Zn-Hg (50%) mercury vapor pressure-temperature characteristics;
η
Hg: be liquid mercury light output-temperature characteristics relatively in φ 12mm fluorescent tube;
η
Zn-Hg (50%): be Zn-Hg (50%) light output-temperature characteristics relatively in φ 12mm fluorescent tube.
Bi-Pb-Sn-Hg (3.5%) mercury vapor pressure-temperature characteristics of Fig. 4 for measuring according to the present invention, wherein:
P
Bi-Pb-Sn-Hg (3.5%): be Bi-Pb-Sn-Hg (3.5%) mercury vapor pressure-temperature characteristics;
η
Bi-Pb-Sn-Hg (3.5%): be Bi-Pb-Sn-Hg (3.5%) light output-temperature characteristics relatively in φ 12mm fluorescent tube.
Fig. 5 is for to measure Bi-In-Hg (5%) mercury vapor pressure-temperature characteristics according to the present invention, wherein:
P
Bi-In-Hg (5%): be Bi-In-Hg (5%) mercury vapor pressure-temperature characteristics;
η
Bi-In-Hg (5%): be Bi-In-Hg (5%) light output-temperature characteristics relatively in φ 12mm fluorescent tube.
Embodiment
Provide specific embodiment below, further describe the present invention.
Embodiment 1:
Measure Zn-Hg (50%) the temperature variant characteristic of mercury vapor pressure of mercury admittedly by the inventive method, the solid mercury of Zn-Hg (50%) is meant that mercury content is 50% right cylinder zinc amalgam.
Step 1: the solid mercury 3 of Zn-Hg (50%) is placed in effective cold junction 4,9 for diameter be the ultraviolet lamp tube of φ 12mm, earlier lamp after seasoned at normal temperatures 15 hours, but put thermoregulation range into in-40 ℃-200 ℃ the constant temperature oven 8, effectively cold junction 4 places oil bath ware 5, insert the probe 6 of tie point temperature meter in the oil bath ware 5, ultraviolet light illumination meter 7 is placed in the constant temperature oven perforate.In the process of lighting a lamp, change cold junction 4 temperature, after treating that cold junction temperature and brightness value are all stable, write down each cold junction temperature and ultraviolet brightness value respectively, calculate the relative ultraviolet light output under each cold junction temperature, can obtain the solid mercury of Zn-Hg (50%) and export the family curve η that changes with cold junction temperature at the light relatively of φ 12mm ultraviolet lamp tube
Zn-Hg (50%), specifically with reference to Fig. 2.
Step 2: get the fluorescent tube of same specification, replace solid mercury with liquid mercury and carry out same test according to the method described above, can obtain liquid mercury and export the family curve η that changes with cold junction temperature at the light relatively of φ 12mm ultraviolet pipe
Hg
Step 3: the mercury vapor pressure curve P of liquid mercury under different temperatures
HgBe recited as according to the prior art data known, the same end of light output peak value relatively, curve η
HgOn value and curve P
HgOn value have one-to-one relationship.
Curve η among Fig. 3
HgOn: liquid mercury is in temperature T
1The time, light output valve η 1 reaches maximal value 100% relatively, and corresponding mercury vapor pressure value is P1, curve η
Zn-Hg (50%)On: consolidate the mercury temperature T 2 times at Zn-Hg (50%), light output valve η 2 reaches maximal value 100% relatively, and corresponding solid mercury mercury vapor pressure value is P2, then consolidates the mercury vapor pressure value P2=P1 of mercury under its temperature T 2.The left side of η 1, η 2, η 3=η 4=95%, the liquid mercury temperature T 3 of η 3 correspondences, liquid mercury mercury vapor pressure value is P3, then consolidates the mercury vapor pressure value P4=P3 of mercury under its temperature T 4.The right of η 1, η 2, η 5=η 6=95%, the liquid mercury temperature T 5 of η 5 correspondences, liquid mercury mercury vapor pressure value is P5, then consolidates the mercury vapor pressure value P6=P5 of mercury under its temperature T 6.Can relatively calculate mercury vapor pressure value under each η value corresponding temperature by solid mercury η value and liquid mercury equally, draw P
Zn-Hg (50%)Curve.
Measure the mercury vapor pressure value temperature variant family curve of multiple solid mercury when need, all need use η at same specification φ 12mm ultraviolet pipe
HgAs the reference curve, through the curve η that verifies or calibrate repeatedly
HgCan reuse, need not repeating step two.
Embodiment 2:
Measure the Bi-Pb-Sn-Hg-3.5 temperature variant characteristic of mercury vapor pressure of mercury admittedly by the inventive method, the solid mercury of Bi-Pb-Sn-Hg-3.5 is meant that mercury content is 3.5% spheroid bismuth slicker solder mercury alloy.
Step according to embodiment 1, replace the solid mercury of Zn-Hg (50%) with the solid mercury of Bi-Pb-Sn-Hg (3.5%), obtain the solid mercury of Bi-Pb-Sn-Hg (3.5%) and export the family curve that changes with cold junction temperature at the light relatively of φ 12mm ultraviolet pipe, according to the step 3 of embodiment 1, obtain the solid mercury vapor pressure-temperature curve P of mercury under φ 12 ultraviolet pipe different temperatures of Bi-Pb-Sn-Hg-3.5
Bi-Pb-Sn-Hg (3.5%)Specifically with reference to Fig. 4.
Embodiment 3:
Measure Bi-In-Hg (5%) the temperature variant characteristic of mercury vapor pressure of mercury admittedly by the inventive method, the solid mercury of Bi-In-Hg (5%) is meant that mercury content is 5% spheroid bismuth indium mercury alloy.
Step according to embodiment 1, replace the solid mercury of Zn-Hg (50%) with the solid mercury of Bi-In-Hg (5%), obtain the solid mercury of Bi-In-Hg (5%) and export the family curve that changes with cold junction temperature at the light relatively of φ 12mm ultraviolet pipe, according to the step 3 of embodiment 1, obtain the solid mercury vapor pressure-temperature curve P of mercury under φ 12 ultraviolet pipe different temperatures of Bi-In-Hg (5%)
Bi-In-Hg (5%)Specifically with reference to Fig. 5.