Water adsorption properties are necessary for determining and analyzing water sorption in dried and roasted cocoa beans during storage. Thus, this study aimed to determine the water adsorption isotherms and thermodynamic properties at temperatures of 25, 30, and 40°C and water activities between 0.10 and 0.85 using dynamic dew point method. Thirteen different models were fitted to experimental data to represent the dependence of the equilibrium moisture content. Additionally, the thermodynamic properties were determined using the best-fit isotherm model. The isotherms of dried and roasted cocoa beans showed typical behavior of products rich in soluble components, according to Brunauer-Emmett-Teller (BET) classification, which was satisfactorily modeled using the Iglesias and Chirife and Kuhn equations, respectively. The thermodynamic properties showed that the net isosteric heat of adsorption and the Gibbs free energy decreased with the equilibrium moisture content, indicating the energy changes and spontaneity during the adsorption process. The integral entropy of adsorption indicated the best conditions for product stability during storage.

Sorption isotherms represent an efficient and valuable tool for predicting the equilibrium moisture content of foods under different humidities and temperatures; thus, they are useful for determining shelf-life and safe storage conditions. The aims of this work were to determine the sorption isotherms of parchment specialty coffee at water activity values of 0.1−0.8 and temperatures of 25, 30, and 40 °C using the dynamic dew point method. The experimental sorption data were modeled using 12 different equations to represent the dependence of equilibrium moisture content on water activity and temperature. Thermodynamic properties were also obtained from the experimental data. The results showed a type II sigmoid shape according to Brunauer-Emmett-Teller (BET) classification, and the double log polynomial (DLP) equation successfully modeled the effects of temperature on the sorption isotherms, obtaining a good fit (R2adj = 0.99 and RMSE = 0.1 % dry basis). The dynamic dewpoint isotherm (DDI) method was advantageous for modelling due to its high availability of experimental data. Thermodynamic analyses showed that the net isosteric heat of sorption, Gibbs free energy, and sorption entropy decreased as equilibrium moisture content increased, and the compensation theory provided evidence that the sorption process was controlled by enthalpy (Tβ > Thm). Key words: Water activity; equilibrium moisture content; hygroscopicity; non-spontaneous; molecular ordering; compensation theory.

Generally, the taxonomic classification of cocoa beans is based on the theobromine/caffeine ratio determined using high-performance liquid chromatography (HPLC). However, this technique involves laborious and time-consuming calculations. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy is a valuable, effective, and rapid tool for analyzing the chemical composition of food products. The objective of this study was to examine the potential of ATR-FTIR combined with chemometric tools such as principal component analysis (PCA), linear discriminant analysis (LDA), and partial least squares regression-discriminant analysis (PLS-DA) to discriminate between the Trinitario and Forastero dry bean cocoa varieties defined by theobromine and caffeine measurements via HPLC. The cocoa varieties were evaluated using HPLC analysis of 36 dry cocoa bean samples to determine the theobromine/caffeine ratio. Moreover, ATR-FTIR spectra were analyzed in the mid-infrared (MIR) region, and signals associated with theobromine and caffeine were identified and analyzed using the LDA and PLS-DA models. The LDA and PLS-DA models allowed the satisfactory differentiation between cocoa varieties, providing overall prediction capacity values of 98.2 ± 1.8% and 96.1 ± 2.4%, respectively. The results show the potential of ATR-FTIR spectroscopy for the reliable, fast, and easy differentiation of dried cocoa beans.

Specialty coffee is highly differentiated product because of its sensorial attributes: aroma, body and brand reputation. In specialized markets, these products are highly valued, and sometimes up to six times their commercial value is paid. Thus, it is essential to preserve their freshness. Sorption isotherms are necessary for determining and studying water sorption changes in specialty coffee during storage. This study aimed to determine the adsorption isotherms of specialty ground roasted-coffee at temperatures of 25 °C, 30 °C and 40 °C and water activities between 0.1 and 0.8 using the dynamic dewpoint method (DDI). The experiment sorption data were modeled using 12 different equations with non-linear regression to represent the dependence of the equilibrium moisture content with both water activity and temperature. In addition, the thermodynamic properties were determined with the experiment adsorption data. The results showed that type III isotherms were obtained according to the Brunauer classification, and the Weibull equation satisfactorily modeled the effect of the temperature on the hygroscopic equilibrium in the specialty ground roasted-coffee. The results of thermodynamic analysis showed that the net isosteric heat of adsorption and Gibbs free energy decreased as the equilibrium moisture content increased, indicating the amount of energy released, a strong bond energy between water molecules in the product components and spontaneity in the adsorption process. The entropy of the adsorption increased with the moisture content, leading to product stability conditions during storage. The results were similar to those reported for the roasted and ground coffee of others cultivars.