自发拉曼光谱法测量O2(1Δ)产率中氯气荧光干扰的消除

利用自发拉曼光谱法测量O₂(1Δ)产率的过程中发现O₂(1Δ)和O2(³∑)拉曼光谱上叠加有氯气荧光光谱, 严重影响了O₂(1Δ)产率的测量. 为此,利用气体分子的拉曼光谱具有偏振特性,而荧光光谱没有偏振特性的特点对测量O₂(1Δ)产率的自发拉曼光谱法进行了改进. 实验结果表明,这一改进可有效消除氯气荧光干扰,使单重态氧发生器在氯气利用率为88%时的O₂(1Δ)产率可很容易地被确定为(42.4±7.4)%.     

射流式单重态氧发生器研究

单重态氧O2 (a1Δg)是迄今唯一能用纯化学反应高效产生的具有长寿命的亚稳激发态分子 .为了考察提出的用两个O2 (1Δ)能量汇集反应生成氧第二单重激发态O2 (b1Σ+ g)以实现近可见短波长化学激光方案的现实性 ,设计和实验了一个氯流量为 3～ 10mmol/s的射流式单重态氧发生器 (JSOG) .考察了三种具有不同孔径和孔数目的喷头、氯气流量和脱水冷阱温度等对JSOG出口的O2 (1Δ)浓度、O2 (1Δ)分压、氯利用率及水蒸气含量的影响 .发现用聚氯乙烯管作冷阱时 ,最佳冷阱介质温度为 - 140～ - 15 0℃ ,对此提出了O2 (1Δ)表面脱活与脱水互相竞争的解释 .在最佳条件下 ,可将O2 (1Δ)气中水分压降低至 4Pa ,这一结果是首次报导     

单重态氧发生器出口气流中O_2(~1Δ)及水汽绝对浓度的测量

单重态氧发生器是氧碘化学激光器的核心部件 ,O2 (1Δ)和水汽的粒子数密度 (绝对浓度 )是单重态氧发生器的两个重要参量 ,其中O2 (1Δ)是氧碘化学激光器的能源 ,而水汽对氧碘化学激光器的发光介质—I 有强烈的淬灭作用。如何简单准确地测量这两个参量 ,一直是氧碘化学激光器研究中的一个难题。利用体光源模拟标定法 ,得到了O2 (1Δ)和水汽的绝对浓度 ,并且成功地用一套实验装置对射流式单重态氧发生器的上述两个参量进行了实时测量 ,得到了两个参量的变化曲线 ,同时还提供了O2 (1Δ)的产率以及水汽体积浓度等参量的变化曲线 ,通过大量实验结果 ,给出了各参量的变化规律 ,为射流式单重态氧发生器研究提供了有力的参考依据。     

横向射流式单重态氧发生器的性能实验研究

 对氧碘化学激光器的单重态氧发生器（SOG）进行了改进，采用横向射流方式，并对该横向射流式单重态氧发生器的性能进行了检测。实验中过氧化氢碱溶液温度控制在－16℃左右,氯气流量为530mmol/s，He与氯气的流量比为3;采用PS法测量单重态氧分子的产率,吸收法测量氯气的利用率和相对水含量。得出如下结论:在不使用冷阱和分离器的情况下，最高单重态氧分子产率达到58%, 氯气利用率在80%以上,相对水含量小于等于0.5;气体达到最大流量时,发生器仍然能稳定地工作。     

喷射型单重态氧发生器性能研究

单重态氧发生器作为氧碘化学激光的核心部件,为化学激光器提供化学能。通过对工业喷射器及旋风分离器的研究,结合产生单重态氧的化学反应环境,进行了大量模拟及设计改进工作,研制了一种新型喷射型单重态氧发生器,并进行了相关实验研究。喷射型单重态氧发生器利用喷嘴能够产生比传统发生器类型更多的气液表面,获得足够的反应效率,可以大幅度降低发生器液体使用量,从而减小发生器辅助系统,提高体积效率。为满足O2（1）停留时间短及分离效率高的要求,利用气液两相喷射的高初速度以旋风分离器完成气液分离。新型发生器氯气利用率可达97%~99%,其O2（1）产率为40%~50%。     

利用喇曼光谱测量氧碘化学激光器氯气利用率的实验研究

 介绍了利用自发喇曼散射光谱测量氧碘化学激光器单态氧发生器氯气利用率的原理及实验装置，并给出了在以氮气作为稀释气的0.1mol/s射流式氧发生器上测试的结果，测试相对误差小于12%。由于该方法只需要通过测量喇曼谱线相对强度之比，即可算出氯的利用率，因此不需要另外的标定实验，从而避免了因标定带来的影响。该方法减小了测试误差，简化了实验过程，提高了测试效率。     

亚磷酸三苯酯臭氧化合物分解产生单重态氧的研究

现在世界上功率最大的短波长化学激光、氧碘化学激光是以亚稳态的O2 (a1△)作为储能分子,通过近共振碰撞传能给碘原子,使碘原子激发而发射激光,因此,O2 (a1△)的发生是其主要关键技术.目前使用的方法是H2 O2 的碱溶(BHP)与Cl2 气反应[1] .它具有化学效率高的优点,但此方法产生的O2 (a1△)中含有水份,而水对碘原子具有强的猝灭作用;另外,BHP不能长期保存;氯气还有毒性.196 1年Thompson发现,在- 78℃时亚磷酸三苯酯(TPP)与O3加成为亚磷酸三苯酯臭氧化合物(TPPO3) [2 ] ,并在高于- 35℃分解产生O2 (a1△) .　(C6 H5O) 3P +O3-78℃(…     

单重态氧发生器出口气流中O2(1△)及水汽绝对浓度的测量

单重态氧发生器是氧碘化学激光器的核心部件．O2(^1△)和水汽的粒子数密度(绝对浓度)是单重态氧发生器的两个重要参量，其中O2(^1△)是氧碘化学激光器的能源，而水汽对氧碘化学激光器的发光介质-I^ 有强烈的淬灭作用。如何简单准确地测量这两个参量，一直是氧碘化学激光器研究中的一个难题。利用体光源模拟标定法，得到了O2(^1△)和水汽的绝对浓度，并且成功地用一套实验装置对射流式单重态氧发生器的上述两个参量进行了实时测量，得到了两个参量的变化曲线，同时还提供了O2(^1△)的产率以及水汽体积浓度等参量的变化曲线，通过大量实验结果，给出了各参量的变化规律，为射流式单重态氧发生器研究提供了有力的参考依据。     

单重态氧的气固化学反应发生体系的热力学分析

 采用Gaussian程序软件包，在RHF/Lanl2dz计算水平上，计算了由4类无机固体反应物(包括碱金属的过氧化物或超氧化物、碱土金属的过氧化物或超氧化物)与3类气体反应物(包括卤素气体、卤化氢气体和卤化氘气体)所组合的12种可产生单重态氧(O2(1Δg))的气固化学反应体系的热力学参数(如反应焓变、Gibbs反应自由能变化值以及化学反应平衡常数)。计算结果结合O2(1Δg)在氧碘化学激光器(COIL)中的实际应用，分析比较了不同固体反应物和不同气体反应物对气固化学反应体系产生O2(1Δg)的影响。分析结果表明：大部分的上述气固化学反应体系的Gibbs反应自由能变化值为负值，反应可自发进行；但在所有的气固化学反应体系组合中，由碱金属超氧化物与F2或Cl2组成的气固化学反应体系的反应生成热是比较少的，这有利于气固化学反应体系产生的O2(1Δg)用于COIL中。分析同时表明由碱金属超氧化物(如LiO2，NaO2或KO2)与卤素气体(如F2或Cl2)所组成的气固化学反应体系能更高效地产生O2(1Δg)，较适合用于COIL中。     

用吸收光谱法测量COIL的水汽含量

 分析了利用吸收光谱法测量氧碘化学激光器的水汽含量的原理，在氯气流量为0.1 mol/s的N₂-COIL上进行了测试实验。实验结果显示，在常规工作条件下，由于BHP温度变化所引起的水汽百分含量变化仅为0.1%，可以忽略；水汽含量随稀释气体流量增大而增加，气体流速是引起水汽含量变化的主要原因，实验中应把氯气和氧气的比例控制在4∶1之内。     

射流式单重态氧发生器理论模型

 射流式单重态氧发生器(JSOG)是化学氧碘激光器十分重要的能源部分，它主要是通过解气相、液相扩散方程来求解发生器出口的氯的利用率和单重态氧的产率。在实际工作中的射流发生器非常复杂，其扩散方程和边界条件为非线性，非齐次边界条件，非齐次泛定方程组，求解难度较大。通过边界条件，采用试探解的方法，解得氯、总氧、单重态氧的气相、液相扩散方程，得到了氯的利用率，及单重态氧产率的解析解，与实验结果基本相符。     

利用喇曼光谱测量氧碘激光器氧发生器的O2（a^1△）产率

利用自发喇曼成像技术实时监测氧碘激光器O2（a^1△）发生器流场组分，得到了发生器气流中O2（a^1△）和O2（X^3∑）以及N2的自发喇曼散射光谱，由此得到了不同条件下的O2（a^1△）产率。测量误差不超过8%。     

利用喇曼光谱测量氧碘激光器氧发生器的O2（a1Δ）产率

 利用自发喇曼成像技术实时监测氧碘激光器O₂(¹Δ)发生器流场组分，得到了发生器气流中O₂(¹Δ)和 O₂(X³Σ)以及N₂的自发喇曼散射光谱，由此得到了不同条件下的O₂(¹Δ)产率，测量误差不超过8%。     

p-τ值对COIL的影响的实验研究

 实验研究了单重态氧发生器（SOG）的p-τ值，即初始氯气分压与停留时间的乘积，对化学氧碘激光器（COIL）的影响，并分析了诸多实验因素对SOG的p-τ值的影响。对于提高COIL的化学效率具有很重要的实际意义。     

Spray generator of singlet oxygen for a chemical oxygen-iodine laser

A spray type of singlet oxygen generator for driving the Chemical Oxygen-Iodine Laser was developed. Singlet oxygen, O₂(¹Δ_g), is generated by a fast reaction of chlorine with basic hydrogen peroxide solution in the form of a dense spray. A mathematical model of this reaction system showed that O₂(¹Δ_g) can be generated in this system with a high yield (0.70–0.80), high utilization of chlorine (0.75–0.95), and effective utilization of liquid (0.36–0.54) at very high generator pressures (35–75 kPa). Experimental studies of this reaction system without an efficient separation of liquid proved an efficient O₂(¹Δ_g) production characterized by a rather high product of chlorine utilization and O₂(¹Δ_g) yield (0.4–0.9) at very high generator pressures (30–80 kPa). This pressure is much higher than the operation pressure used in other generators, which should be beneficial for a pressure recovery system of the COIL. These results provided the basis for designing a centrifugal spray generator with an efficient separation of liquid from the gas flow, which is the subject of the following paper.     

Systematic discrepancy of theoretical predictions of NMR chemical shifts for chlorinated aromatic carbons using the GIAO DFT method

Theoretical calculations of carbon-13 NMR chemical shifts using the gauge including atomic orbitals (GIAO) DFT approach with a moderately large set of basis functions usually yield quite satisfactory results. In the case of chlorinated aromatic carbons, however, abnormally large differences between experimental and calculated values have been noticed. This discrepancy has been proven not to be caused by improper referencing, or the basis set effect, and probably not by neglect of vibrational corrections. One of the possible sources of the chlorine effect could be the impact of relativistic phenomena on electrons moving about the chlorine nucleus. The second, probably more important factor is the influence of electron correlations, ignored in Hartree–Fock SCF and only partially included in DFT calculations. Surprisingly, however, the observed divergence has been significantly larger for DFT than for Hartree–Fock results. In the latter case the observed divergence between theoretical and experimental ¹³C NMR chemical shifts of chlorine-bonded carbons is systematic but rather small (3.4–4.4ppm).     

Migration of chlorine in the X-ray fluorescence analysis of rocks

The intensity of the analytical ClKα-line continuously increases during the measurement of a rock sample. The main cause of this effect is the migration of chlorine into the irradiated (emitting) part of the sample. The hypothesis was credibly proved through the experiment in which a rock sample was measured first on one side, and then on the other. An increase in the intensity of the analytical line was observed in both measurements. The intensity in the second measurement registers an increase from the same or even the lower level than in the first part. The following chlorine migration model is proposed. Negative chlorine ions arise in the rock sample under the influence of primary X-ray radiation. X-ray photons knock out part of the ions from the sample; therefore, a positive electric field is formed in it at the sample–vacuum interface. It attracts chlorine ions from the depths of the sample, as well as chlorine ions flying outside. Thus, the number of chlorine atoms in the surface layer of the sample increases and consequently, the intensity of the analytical line of chlorine increases. Formation of chlorine ions, their migration, and concentration in the surface layer of the sample occur only under the influence of primary X-ray radiation.     

Investigation of singlet-oxygen formation in chemical reactions

Conclusion We have reported here the results of investigations of new possibilities of obtaining O₂ ^* by a chemical method. In searches for new sources of O₂ ^* we synthesized solid peroxide-containing substances that interact with chlorine to release the oxygen intensively.The purpose of the investigations was a quantitative measurement of the O₂ ^* yield from the reaction of chloride with solid peroxyhydrates of inorganic salts, and to prove the advantages of the new method of obtaining O₂ ^* for OIL development.We developed for this purpose a universal measurement system that makes it possible to determine, by a combined optical and calorimetric method, the content of singlet oxygen at the exit from a chemical SOG. Measurements of the singlet-oxygen yield from the reaction of chlorine with solid peroxyhydrates have shown that in this case the yield is close to 100%. Experiments performed with an alkaline solution of hydrogen peroxide and comparison of our results with data of others have demonstrated the fitness of the developed procedure and prove the reliability of the results.Translated from Preprint No. 18, Lebedev Physics Institute, Academy of Sciences of the USSR, Moscow, 1991.