Early Evolution of Gas Chromatography in East Germany. Part I: Beginnings, Instrument and Column Development and Organizations

The early evolution of gas chromatography in the former German Democratic Republic (GDR) is surveyed and instrument development is outlined, describing the most important models manufactured in the GDR. The organization of the Arbeitsgemeinschaft für Gas-Chromatographie (Working Group for GC) is chronicled and its activities are discussed. Subsequent parts of this article will deal with the six symposia organized by the Arbeitsgemeinschaft between 1958 and 1968.     

Heat of adsorption and density distribution in slit pores with defective walls: GCMC simulation studies and comparison with experimental data

The adsorption behavior (capacity, density distribution and packing density) and the isosteric heat versus loading in a slit pore whose walls contain defective graphene layers are investigated in this paper. The defective wall is characterized by the extent and size of the defect. Simulation results obtained with the Grand Canonical Monte Carlo method reveal complex patterns of isosteric heat, and this complex behavior is a result of the interplay between three factors: (i) the surface heterogeneity (solid-fluid interaction, sites with varying degree of affinity), (ii) fluid-fluid interaction and (iii) the overlapping of potentials exerted by the two defective walls. We illustrate this with argon adsorption in pores of various sizes, and results obtained from the simulation agree qualitatively with the experimental data at 77 K on Saran microporous S600H and micro-mesoporous S84 charcoals of Beebe et al. [R.A. Beebe, B. Millard, J. Cynarski, J. Am. Chem. Soc. 75 (1953) 839]. The S600H was found to contain pores predominantly in the neighborhood of 7 Å with 30% of defect and a defective size of 2.84 Å. This is consistent with the argument made by Beebe et al. that this sample is a microporous solid and most pores can accommodate only one layer. The other sample, S84, has larger pores than S600H, and it is found that it has a wider pore size distribution and the pore width is centered at about 12 Å.     

Enzymes immobilized on montmorillonite: comparison of performance in batch and packed-bed reactors

Summary The enzymes a-amylase, invertase and glucoamylase were immobilized on acid activated montmorillonite using two techniques, viz. adsorption and covalent binding, and their activities were tested in a batch and packed-bed reactor and were compared. The packed-bed reactor showed an improved performance for all immobilized enzymes, which was attributed to lowering of diffusional restrictions to mass transfer. Lower activity in case of batch reactor for immobilized invertase was due to a combined effect of loss of native conformation of enzyme on account of immobilization and mass transfer resistances due to improper diffusion of substrate to the active site of enzyme. For immobilized glucoamylase, the packed-bed reactor demonstrated exceptionally high activity that was very close to the free enzyme. Covalently bound glucoamylase showed higher activity than the free enzyme.     

New methodologies in trace analysis of volatile organic compounds

Two methods for sampling and concentration of volatile organic compounds are reported. In the first method, traps coated with a very thick film (ca. 100 μm) of cross-linked silicone stationary phase are employed. Such thick films can be prepared with a modified dynamic coating procedure, which is briefly described. The low phase ratio traps can be utilized for enrichment of volatiles from gaseous as well as aqueous matrices. The second technique is based on chromatographic evaporation of a solvent in a capillary tube, where the process is sustained by a repeated sample injection and a cyclic flow reversal. In this way, large solvent volumes can be handled by a small volume system. Under optimal conditions, when using a solvent barrier, quantitative recovery is possible even for compounds of comparatively high volatility. Another important application of the technique is extraction of trace components from gases such as headspace samples, polluted air, etc.     

气体放电击穿过程的物理和数值研究

本文对低气压（１０＾－２Ｐａ）热阴极气体放电的击穿过程给出了物理描述和相应的双流体数学型，并发展了一种选择和调整未知初始条件的有效算法，可以通过伴随试射法得到对初始条件十分敏感的非线性两点边值常微分方程组的数值解，从而给出这类气体放电中击穿过程的定量描述。     

Solubility of carbon dioxide in aqueous solutions of sodium chloride: Experimental results and correlation

The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's⁽¹⁾ equations as well as the Chen and Evans⁽²⁾ model were used to correlate the new data. Results are reported and compared to literature data and correlations.     

Determination of the boiling point distribution of sulfur compounds in light cycle oil using GC with a flame photometric detector and pyrolyzer

A method has been developed to determine the boiling point distribution of sulfur compounds in light cycle oils (LCO'S). The method chosen for this analysis was GC with a flame photometric detector (FPD) and pyrolyzer. Tests were carried out to evaluate the recovery efficiency, repeatability, and accuracy of the method. Repeatabilities within 2% were obtained. The recovery of benzothiophenes and dibenzothiophenes was close to 100%; this was important because these are the major sulfur components in LCO's. No hydrocarbon or solvent interferences were observed with the use of the pyrolyzer, even for a 95% solvent level. Comparison with results from other techniques showed that the method accurately determined the levels of sulfur compounds in the LCO boiling point range.     

Use of a long-spacer-side-chain liquid crystalline polysiloxane containing a crown ether as a stationary phase for capillary gas chromatography

A new kind of side chain liquid crystalline polysiloxane containing a crown ether with a longer spacer (PSC-11) has been prepared and coated on a fused silica capillary column. The main chroma-tographic characteristics including efficiency, polarity, and selectivity have been examined. The phase exhibits the retention properties of both liquid crystal and crown ether stationary phases and possesses higher efficiency and better selectivity than PSC-3, which has a shorter spacer between the main polysiloxane chain and liquid crystalline side chain.     

Native ethylene glycol in wine: Application of a dead volume free,very fast “deans heart-cut” system on-line with multi-chromatography

Data about the existence of native HO? CH₂? CH₂? OH (MEG) in natural wines and champagne has led to delicate questions because of legal decisions already made to declare wine or champagne illegal for sale if the MEG concentrations found are above 10 mg/liter. Action has been taken because of the DEG (diethylene glycol) disaster in European wines of 1985…86. An incorrect legal decision was made due to the belief that MEG cannot be produced biochemically by grape vines. A further reason may be lack of correct data on native MEG trace concentrations, as a result of the special behavior of this diol. As first member of a homologous series whose higher members (C₄) are normally found in all wines at quite high concentration levels, MEG shows extremely adsorptive behavior. The solution of the chromatographic problems is summarized in this paper. MEG concentrations in Riesling as example are in the range of 2 to 6 mg/liter and can easily be increased by biotechnological steps to a level of around 10 to 60 mg/liter. This is again due to the specific adsorptive behavior of MEG, which can be enriched on filter surfaces and displaced when the wine acidity changes with changing types. In order to control and guarantee the qualitative and quantitative results of MEG analyses we used a combination of Deans heart cutting on-line with Multi-Chromatography. It was easy to produce false data by many otherwise useful single column or two-dimensional separation processes, etc.