SummaryDirect conversion of isothermal to temperature programmed indices is not possible. In this work it is shown that linear temperature programmed retention indices can only be calculated from isothermal retention data if the temperature dependence of both the distribution coefficients and the column dead time are taken into account.Procedures are described which allow calculation of retention temperatures and from these, accurate programmed retention indices. Within certain limits the initial oven temperature and programming rate can be chosen freely.The prerequisite forthis calculation is the availability of reliable isothermal retention data (retention times, retention factors, relative retention times, or retention indices) at two different temperatures for one column.The use of compiled isothermal retention indices at twodifferent temperatures for the calculation of retention temperatures and thus temperature programmed indices is demonstrated. For the column for which programmed retention indices have to be determined, the isothermal retention times of the n-alkanes and the column dead time as a function of temperature have to be known in addition to the compiled data for a given stationary phase.Once the programmed retention indices have been calculated for a given column the concept allows the calculation of temperature programmed indices for columns with different specifications. The characteristics which can be varied are: column length, column inner diameter, phase-ratio, initial oven temperature, and programming rate.

It is demonstrated that linear injection characteristics are obtained for a wide boiling point range sample using a temperature‐programmed injector in combination with wide‐bore fused silica columns. The applicability of the described combination for high temperature simulated distillation is described. The method, using external standardization, gives accurate and repeatable results for different types of samples in the boiling range between 50 and 750°C. The lifetime of the fused silica wide‐bore columns was found to be acceptable, viz. over 80 temperature‐programmed cycles between ambient and 430°C. Some comments are made on the accuracy of boiling points for normal alkanes.

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