Measuring total porosity in shale gas reservoir samples remains a challenge because of the fine-grained texture, low porosity, ultra-low permeability, and high content of organic matter (OM) and clay mineral. The composition content porosimetry method, which is a new method for the evaluation of the porosity of shale samples, was used in this study to measure the total porosity of shale gas reservoir samples from the Lower Silurian Longmaxi Formation in Southeast Chongqing, China, based on the bulk and grain density values. The results from the composition content porosimetry method were compared with those of the Gas Research Institute method. The results showed that the composition content porosimetry porosity values of shale gas reservoir samples range between 2.05% and 5.87% with an average value of 4.04%. The composition content porosimetry porosity generally increases with increasing OM and clay content, and decreases with increasing quartz and feldspar content. The composition content porosimetry results are similar to the gas research institute results, and the differences between the two methods range from 0.05% to 1.52% with an average value of 0.85%.

Five model compounds with representative chemical structures were selected for use in simulation experiments of pyrolytic gas production. The gas production and isotopic fractionation characteristics were observed and analyzed. Then, the factors affecting carbon isotope fractionation during natural gas generation were discussed, and a fractionation model was established and calibrated. We concluded that the final hydrocarbon gas (C_1–5) yield of octadecane, octadecylamine, octadecanoic acid, decahydronaphthalene, and 9‐phenylanthracene decreased in turn with the effective hydrogen content. Compared with linear alkanes or alkyl compounds, cycloalkanes have higher thermal stability and generate gas later. The variation in the carbon isotopic composition of natural gas is primarily controlled by the following three factors: (a) the thermal evolution of organic matter results in a gradually heavier isotopic composition for the main gas production stage. (b) Gas inherits the isotopic composition of its parent material, and this effect is evident when the chemical structure and gas generation mechanism between parent materials are similar. (c) The structure of organic matter determines the reaction mechanism of gas generation, which has a significant influence on the range and trend of carbon isotope fractionation in the process of methane generation. An improved chemical kinetic model can accurately characterize carbon isotope fractionation during gas generation.