Determination of Heats of Adsorption on Carbon Blacks and Bone Mineral by Chromatography Using the Eluted Pulse Technique
Determination of Heats of Adsorption on Carbon Blacks and Bone Mineral by Chromatography Using the Eluted Pulse Technique
复制标题
使用洗脱脉冲技术通过色谱法测定炭黑和骨矿物质的吸附热
DOI：
10.1021/j100785a020
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发表时间：
1964
期刊：
影响因子：
--
通讯作者：
R. Beebe
中科院分区：
文献类型：
--
作者：
R. Gale;R. Beebe
等量吸附热已来自于在气-固色谱法中测得的洗脱脉冲的保留时间的温度依赖性，使我们能够作出比较与热量测定的吸附热在低覆盖率。用氮、氧、氩、氯甲烷和氯乙烷、氨、水、二氧化碳、甲烷、六氟化硫、六氟乙烷和八氟丙烷作吸附质，用牛骨矿（“Ossar”）和一系列炭黑、Spheron、Graphon、以及Sterling FT（Sterling FT-G）和Sterling MT（Sterling MT-G）的石墨化形式。除了少数可以理解的例外情况，我们的色谱数据与量热法所得的色谱数据大体上是一致的。我们对色谱数据的处理假定了线性吸附等温线，我们已经表明，在本工作中研究的相对低的覆盖率下，通常接近这种条件，尽管并不总是严格达到。在理想的色谱（吸附-解吸平衡）中，不对称峰和保留体积随脉冲大小的变化表明偏离了等温线的线性。我们已经推导出方程，该方程将柱端和沿其长度沿着的任何点的表面覆盖度与已知的柱和洗脱曲线参数相关联。
Isosteric heats of adsorption have been derived from the temperature dependence of retention times for eluted pulses measured in gas-solid chromatography, enabling us to make a comparison with heats of adsorption determined by calorimetric measurements at low coverage. Chromatographic heat data were obtained for various systems using nitro-gen, oxygen, argon, methyl and ethyl chlorides, ammonia, water, carbon dioxide, methane, sulfur hexafluoride, hexafluoroethane, and octafluoropropane as adsorbates and, as adsorbents, bovine bone mineral (“Ossar”) and a series of carbon blacks, Spheron, Graphon, and the graphitized forms of Sterling FT (Sterling FT-G) and Sterling MT (Sterling MT-G). With a few understandable exceptions, the agreement of our chromatographic data with those obtainedby the calorimetric method is generally good. Our treatment of the chromatographic data assumes a linear adsorption isotherm, a condition which we have shown was usually approached, though not always strictly attained, at the relatively low coverages studiedin the present work. In ideal chromatography (adsorption-desorption equilibrium) an asymmetric peak and variation of the retention volume with pulse size are indicative of a departure fromlinearity ofthe isotherm. We have derived equations which relate the surface coverage at the end of the column and any point along its length to the known column and elution curve parameters.