ChemInform Abstract: Chemometrics: An Important Tool for the Modern Chemist, an Example from Wood-Processing Chemistry.

This study briefly outlines the idea of principal component analysis and cross-correlation calculations (applied chemometrics) and presents an illustrative example from wood-processing chemistry. The applicability of chemometric data analysis was demonstrated by investigating the various structural changes that take place in dissolved and degraded lignin ("kraft lignin") during laboratory-scale kraft pulping of Scots pine (Pinus sylvestris) and silver birch (Betula pendula). The structural data (31P NMR and size exclusion chromatographic data) on kraft lignin were further processed by chemometric multivariate techniques (PCA and 2DCC), confirming, for example, that the cleavage of beta-aryl…

Chemometric Study on Alkaline Pre-treatments of Wood Chips Prior to Pulping

Alkaline pre-treatments were performed for the production of organics-containing effluents from silver/white birch (Betula pendula/pubescens) and Scots pine (Pinus sylvestris) chips prior to chemical pulping. Pre-treatment conditions were varied with respect to time (from 30 min to 120 min), temperature (130 °C and 150 °C), and alkali charge (1, 2, 3, 4, 6, and 8% of NaOH on oven-dried wood). The analytical data (total content, weight average molar mass, and molar mass distribution) on dissolved lignin were subjected to principal component analysis to examine the relationship between molar mass and molar mass distributions in lignin removed from different wood species under varying alkaline…

Chemometrics:  An Important Tool for the Modern Chemist, an Example from Wood-Processing Chemistry

This study briefly outlines the idea of principal component analysis and cross-correlation calculations (applied chemometrics) and presents an illustrative example from wood-processing chemistry. The applicability of chemometric data analysis was demonstrated by investigating the various structural changes that take place in dissolved and degraded lignin ("kraft lignin") during laboratory-scale kraft pulping of Scots pine (Pinus sylvestris) and silver birch (Betula pendula). The structural data (31P NMR and size exclusion chromatographic data) on kraft lignin were further processed by chemometric multivariate techniques (PCA and 2DCC), confirming, for example, that the cleavage of beta-aryl…

Multivariate Correlation between Analysis Data on Dissolved Organic Material from Scots Pine (Pinus sylvestris) Chips and their Autohydrolysis Pre-Treatment Conditions

Various chemometric techniques were used to establish the relationship between the autohydrolysis conditions prior to pulping and the chemical compositions of the soluble organic materials removed from Scots pine (Pinus sylvestris) wood chips. The aqueous chip pre-treatments (autohydrolysis) were administered at 130 °C and 150 °C for 30, 60, 90, and 120 min, and the hydrolysates obtained were characterized in terms of total carbohydrates (various mono-, oligo-, and polysaccharides together with uronic acid side groups), volatile acids (acetic and formic acids), lignin, and furans (furfural and 5-(hydroxymethyl)furfural). Based on the analytical data gathered, a relatively accurate model for…

1H,13C and17O NMR spectroscopic study of four bicyclo [3.1.1]heptenes (derivatives of α-pinene) and four bicyclo[3.1.1]heptanes (derivatives of β-pinene)

Four derivatives of 2, 6, 6-trimethylbicyclo[3.1.1]hept-2-ene (α-pinene) and four derivatives of 2-methylene-6, 6-dimethylbicyclo[3.1.1]heptane (β-pinene) were synthesized and their 1H, 13C and 17O NMR spectra were measured, analysed and assigned. The 1H NMR spectral parameters were obtained by computer-aided analyses of the very complex multi-spin, second-order spectra. Some of the 13C NMR chemical shift assignments of these compounds reported in the literature should be changed, based on these accurate 1H NMR spectral analyses and carbon-proton chemical shift correlated spectra (COSY). The new assignments are supported by the 1J(C, H) values, which show a strong dependence on the bond ang…

A spectroscopic method for determining lignin content of softwood and hardwood kraft pulps

Abstract A rapid method for determining the kappa number of unbleached and oxygen-delignified kraft pulps in the range 3–35 is presented. This novel method was based on the multivariate analysis of VIS spectral data on pulp samples. The calculated models and the test results indicated that partial least squares (PLS) and principal component regression (PCR) models yielded similar results, PLS being slightly more accurate. It was also found that for practical purposes a separate model for each wood feedstock and delignification process is needed.

Multivariate Correlation between Analytical Data for Various Organics Dissolved during Autohydrolysis of Silver Birch (Betula pendula) Chips and Treatment Conditions

Autohydrolysis pre-treatments were performed for the production of hemicellulose-rich autohydrolysates from silver birch (Betula pendula) chips prior to chemical pulping. Pre-treatment conditions were varied with respect to time (from 30 to 120 min) and temperature (130 and 150 °C), covering a P-factor range from 10 to 238. Hydrolysates were analyzed in terms of carbohydrates, lignin, volatile organic acids, and furanoic compounds. The analytical data were subjected to various chemometric techniques to establish the relationships between dissolved organic components, hardwood and softwood used in the experiments, and applied pre-treatment conditions. Using this method, differences between t…

Multivariate correlation between13C and31P NMR spectral data on dissolved lignin and the combustion properties of kraft black liquor

Chemometric investigation on structural changes in pine kraft lignin during pulping

Abstract Various structural changes which take place in dissolved lignin during the laboratory-scale kraft pulping of Scots pine (Pinus sylvestris) were studied. Lignin samples were subjected to the alkaline cupric oxide oxidation and the analytical data further processed by various multivariate chemometric techniques (principal component analysis, PCA; principal component regression, PCR; and projection to latent structures, PLS). Several models applicable to the indirect measurement of common pine kraft pulp properties (i.e., total cooking yield, kappa number and ISO brightness) were produced.

Dithionite bleaching of thermomechanical pulp: factors having effects on bleaching efficiency

The efficiency of dithionite bleaching of Norway spruce (Picea abies) thermomechanical pulp was studied by applying various multivariate data analysis techniques to analytical data (temperature, pH, ion chromatographic and energy-dispersive X-ray fluorescence data). In addition, modeling the residual sulfur content of bleached pulp by means of diffuse reflectance UV-vis spectral data from laboratory-scale bleaching experiments was attempted. The results indicated that this lignin-preserving bleaching process could be evaluated by means of the analytical data using either PCR or PLS models. These models also indicated that wavelengths below 400 nm should not be used in measuring the pulp bri…