Tsankova Gergana, Richter Markus, Stanwix Paul L, May Eric F, Span Roland
Thermodynamics, Ruhr-Universität Bochum, Universitätsstr. 150, 44801, Bochum, Germany.
Fluid Science and Resources Division, School of Mechanical and Chemical Engineering, The University of Western Australia, 35 Stirling Highway, Crawley, Western Australia, 6009, Australia.
Chemphyschem. 2018 Mar 19;19(6):784-792. doi: 10.1002/cphc.201701085. Epub 2018 Feb 15.
Accurate measurements of carbon monoxide's electrical properties were carried out at high pressure for the first time enabling stringent comparisons with theoretical values calculated ab initio. Dielectric permittivity measurements were conducted utilising a microwave re-entrant cavity resonator over the temperature range from (255 to 313) K and at pressures up to 8 MPa with a relative combined expanded uncertainty (k=2) less than or equal to 52 ppm. The new data enable carbon monoxide's molar polarizability to be correlated within 0.5 %, significantly improving upon existing literature data, which have a relative scatter of about 10 %. The measured molecular polarizability and electric dipole moment of carbon monoxide were determined to be 2.176×10 C m J and 0.107 D. Literature values from ab initio calculations for these properties are within 0.28 % and 3.9 %, respectively, of the measured quantities. Moreover, our measurement of the electric dipole moment at finite temperature agrees within 2.2 % with the value derived from accurate spectroscopic measurements for the ground rovibrational state. The second dielectric virial coefficient of carbon monoxide was determined experimentally for the first time to be b =(1.015±0.044) cm mol , which compares reasonably with ab initio estimates.
首次在高压下对一氧化碳的电学性质进行了精确测量,从而能够与从头算计算得出的理论值进行严格比较。在(255至313)K的温度范围内,使用微波凹腔谐振器在高达8 MPa的压力下进行了介电常数测量,相对合成扩展不确定度(k = 2)小于或等于52 ppm。新数据使一氧化碳的摩尔极化率的相关性达到0.5%以内,大大优于现有文献数据,现有文献数据的相对离散度约为10%。测得的一氧化碳分子极化率和电偶极矩分别为2.176×10 C m J和0.107 D。这些性质的从头算计算文献值分别在测量值的0.28%和3.9%以内。此外,我们在有限温度下对电偶极矩的测量值与基态振转态精确光谱测量得出的值在2.2%以内相符。首次通过实验确定一氧化碳的第二介电维里系数为b =(1.015±0.044)cm mol,与从头算估计值相当合理。