菊花粉水分吸附等温线及热力学特性

为提高菊花粉的贮藏稳定性，分别在20、30 ℃和40 ℃下，采用静态称量法对黄山贡菊粉和金丝皇菊粉的水分吸附等温线进行研究，同时探讨水分吸附过程净等量吸附热、微分熵、熵-焓互补理论、固体单位吸附表面积及有效孔径等热力学特性。结果表明，黄山贡菊粉和金丝皇菊粉的水分吸附遵循II型等温线。Peleg模型最适合描述菊花粉水分吸附特性，其次为GAB模型。在20、30 ℃和40 ℃下，黄山贡菊粉的单分子层水含量分别为0.065 2、0.062 4、0.054 3 g/g（干基）；金丝皇菊粉分别为0.059 4、0.058 1、0.055 7 g/g（干基）。水分吸附过程中，2 种菊花粉的净等量吸附热和微分熵均随平衡水分含量升高呈指数递减。菊花粉水分吸附是一个焓驱动的、非自发的过程。在20、30 ℃和40 ℃下，黄山贡菊粉的固体单位吸附表面积分别为231.22、221.29 m2/g和192.56 m2/g；金丝皇菊粉分别为210.61、206.04 m2/g和197.35 m2/g。随着温度和水分含量升高，菊花内有效孔径也随之增加，其中黄山贡菊粉和金丝皇菊粉的变化范围分别为1.022～10.115 nm和1.029～10.185 nm。本研究可为菊花的干制工艺及贮藏条件的选择提供理论依据。     

南美白对虾壳与虾肉热力学性质比较研究

为了解南美白对虾壳(PV-S)与虾肉(PV)水分活度(aw)、含水率与温度关系,研究了PV-S与PV的吸附等温线及热力学性质。PV-S与PV水分吸附分别呈Ⅱ型和Ⅲ型等温线,描述PV-S与PV吸附特性的最适模型分别为Blahovec-Yanniotis和GAB模型。PV-S与PV净等量吸附热、微分熵随含水率增加而降低。扩张压力随aw增加而升高,随温度升高而降低。PV积分焓随含水率增加而降低,PV-S积分焓随含水率增加呈先增加后降低趋势。PV积分熵随含水率增加而增加,PV-S积分熵随含水率增加呈先降低后增加趋势。PV-S与PV水分吸附过程为焓驱动且符合熵-焓互补理论。含水率0.20 g/g时,PV-S净等量吸附热、微分熵高于PV。PV扩张压力与积分熵低于PV-S,而PV积分焓则高于PV-S。含水率为0.07 g/g时,PV-S积分焓与积分熵分别达到最大值(1.91 k J/mol)与最小值[-14.34 J/(mol K)]。研究结果可为南美白对虾干制工艺及干制品贮藏稳定性提供科学依据。     

干制“储良”龙眼吸附等温线与热力学特性研究

为考察干制"储良"龙眼含水率与水分活度、贮藏温度之间的关系,以及探讨净等量吸附热、焓变、熵变和自由能等热力学特性,采用静态称重法,测定干制"储良"龙眼在20、30、40℃和水分活度为0. 113～0. 946条件下的吸附平衡含水率,并绘制其吸附等温线。采用6种常用的农产品吸附模型,对实验结果进行拟合分析。结果表明,干制"储良"龙眼的水分吸附呈Ⅲ型等温线,Halsey模型是描述吸附等温线的最适模型。热力学特性结果表明,净等量吸附热随含水率的升高而降低,当平衡含水率Me大于30%d. b.(干基)时趋近于0;净等量吸附热与焓变相等,其范围为0. 2～467. 69 kJ/mol;熵变随含水率的增加而降低,但温度对其影响不显著;干制"储良"龙眼的水分吸附过程可用焓-熵互补理论解释,此过程是焓驱动过程。研究结果可为"储良"龙眼的加工、包装和安全贮藏提供参考。     

基于玻璃化转变理论的蓝莓粉吸湿机制

以‘珠宝’和‘海岸’这两个品种蓝莓为原料制作蓝莓粉,研究吸湿前后蓝莓粉的品质差异;采用静态称量法测定两种蓝莓粉在不同温度（5、15、25、35、45℃）下的吸湿等温线,并构建状态图;探讨了水分吸附过程净等量吸附热、微分熵、熵焓互补等热力学特性。结果表明,两种蓝莓粉吸湿后品质下降,粉体颗粒黏聚,流动性降低;水分吸湿等温线均呈典型的“J”型曲线,GAB模型为描述蓝莓粉水分吸附特性的最适模型。从状态图可知,‘珠宝’和‘海岸’分别在水分含量小于等于0.104 5、0.107 7 g/g（干基）,贮藏温度小于等于-30.30、-32.66℃时,有较好的稳定性。熵焓互补理论表明,两品种蓝莓粉水分吸附过程均为熵驱动的非自发过程。研究结果可为蓝莓粉加工和贮藏条件的选择提供理论依据。     

花生壳/仁的吸附等温线与热力学特性

为了解花生壳与花生仁的含水率、水分活度(a_w)与温度的关系,提高花生的贮藏稳定性。研究花生壳与花生仁在10、20、30℃时的吸附等温线;探讨花生壳与花生仁的净等量吸附热(q_(st))、微分熵(S_d)、扩张压力、积分熵、积分焓、熵-焓互补、玻璃化转变温度(T_g)等热力学特性。结果表明,花生壳与花生仁的水分吸附呈Ⅲ型等温线。温度一定时,花生壳与花生仁的干基含水率随a_w增加而增加。描述花生壳与花生仁吸附特性的最适模型为GAB模型。花生壳与花生仁的q_(st)与S_d均随含水率增加而降低。扩张压力随a_w增加而升高,但随温度升高而降低。积分焓随含水率增加而降低,而积分熵随含水率增加而升高。花生壳的q_(st)和S_d均高于花生仁,而同一温度条件下花生仁的扩张压力高于花生壳。含水率相同时,花生仁积分焓低于花生壳,而花生仁的积分熵则高于花生壳。花生壳与花生仁水分吸附过程均为焓驱动、自发过程。花生壳与花生仁的T_g随含水率增加而降低,相同含水率时,花生壳的T_g值高于花生仁。根据状态图得到温度为10℃时,花生壳与花生仁的临界水分活度与临界含水率分别为0.80、0.175 4 g/g与0.68、0.095 5 g/g。研究结果可为花生干制工艺及其干制品贮藏稳定性提供理论依据。     

干燥方式对桑葚粉热力学特性与贮藏稳定性影响

研究了喷雾干燥、冷冻干燥对桑葚粉吸附等温线与热力学性质的影响,探讨了2种干燥方式对桑葚粉玻璃化转变温度(glass transition temperature,T_g)与状态图的影响,比较了2种干燥方式所得桑葚粉的贮藏稳定性。结果表明,桑葚粉水分吸附等温线为Ⅲ型。Blahovec-Yanniotis为描述桑葚粉水分吸附特性的最适模型。桑葚粉的净等量吸附热与微分熵随含水率增加而降低并逐渐趋于恒定值;扩张压力随温度升高而降低,但随水分活度(water activity,aw)增加而升高;积分焓随含水率增加而降低并逐渐趋于恒定;但是积分熵随含水率增加先降低至最低值,而后升高并逐渐趋于恒定。桑葚粉水分吸附遵循熵焓互补理论,该过程为焓驱动、非自发过程。相同含水率/aw时,喷雾干燥桑葚粉的净等量吸附热、微分熵、积分熵高于冷冻干燥桑葚粉,但积分焓低于冷冻干燥桑葚粉。桑葚粉的T_g随含水率增加而降低,相同含水率时,冷冻干燥桑葚粉的T_g略高于喷雾干燥桑葚粉。25℃下,喷雾干燥与冷冻干燥桑葚粉的临界水分活度分别为0.095、0.115,临界含水率分别为0.076 1、0.079 2 g/g。     

热风干燥冬瓜片的贮藏稳定性

为深入了解热风干燥冬瓜片吸附过程中的水分变化特性,提高冬瓜干制产品的贮藏稳定性,测定了冬瓜干制产品在25℃下的吸附等温线,并采用6种常见的数学模型对其进行非线性拟合,得到最优模型;采用差示扫描量热法测定了不同水分含量冬瓜干制产品的玻璃化转变温度T_g,探讨了冬瓜干制产品的适宜贮藏条件。研究结果表明,冬瓜的吸附等温线属于Ⅲ型等温线,描述干制冬瓜吸附特性的最优模型为GAB模型,热风干燥冬瓜片的T_g值随着含水率的降低而升高。当温度为25℃时,冬瓜的临界含水率为9.67%,临界水分活度为0.237 4。该研究结果为热风干燥冬瓜片的实际产业化生产控制提供理论依据,为适宜贮藏条件的确立提供参考。     

黄秋葵水分吸附热力学性质与状态图研究

研究了黄秋葵在不同温度和水分活度(a_w)范围内的吸附等温线。探讨了黄秋葵的热力学性质,测定了黄秋葵的玻璃化转变温度(Tg),建立了黄秋葵的状态图。结果表明:黄秋葵的水分吸附等温线为Ⅲ型,平衡干基含水率随温度升高而降低,随a_w增加而增加。GAB模型为描述黄秋葵水分吸附特性的最适模型。黄秋葵的净等量吸附热、微分熵与积分焓随含水率增加而降低。积分熵为负值,且随着含水率增加而升高。扩张压力随a_w增加而升高。黄秋葵的水分吸附过程遵循熵焓互补理论,其过程为熵驱动、自发过程。黄秋葵的Tg随含水率增加而降低。根据状态图,得到黄秋葵最大冷冻浓缩溶液时的玻璃化转变温度为-61.14℃,对应的溶质含量为0.7263 g/g(即非冻结水含量为0.2737 g/g)。     

大豆水分解吸-吸附等温线拟合模型

为给在干燥、贮藏及运输过程中保证大豆的品质提供理论依据,实验测定了大豆在室温（25 ℃）条件下的水分解吸-吸附等温线。采用非线性回归分析,应用常见的5 种模型Oswin、Halsey、Hendenson、GAB、Chung-Pfost对大豆在室温条件下测得的水分进行解吸-吸附等温线拟合分析,以确定最佳拟合模型及其参数。结果表明：大豆的解吸等温线属于第Ⅱ种类型;吸附等温线属于第Ⅲ种类型;在整个水分活度范围内,大豆的解吸-吸附等温线均存在着滞后现象;最佳的解吸-吸附等温线拟合方程都是Oswin模型,它们的决定系数均高于0.993;Oswin模型拟合大豆解吸等温线的参数A和B分别为0.075和0.500,吸附等温线的参数A和B分别为0.075和0.498。     

甘蓝型油菜籽水分解吸等温线及热力学性质

为了提高油菜籽储藏期间的稳定性,延长其保质期。采用静态称量法对油菜籽在20、30、40℃温度条件下的解吸特性进行研究,将实验数据用5种常见数学模型进行拟合并对最佳模型进行解析。采用净等量吸附热(q_(st))、扩张压力(Φ)、微分熵(ΔS)、净积分焓(q_(in))、净积分熵(ΔS_(in))以及焓熵互补等特征参数对其热力学性质进行描述。结果表明,油菜籽等温线属于Type Ⅱ类曲线,油菜籽的平衡含水率与水分活度呈正相关,一定水分活度下,平衡含水率与温度呈负相关;描述水分活度与平衡含水率关系最佳模型为GAB模型,不同温度条件下模型决定系数R~2的平均值为0.993 7,卡方x~2的范围为1.396 5×10~(-5)～0.778,残差平方和RSS最低值为4.189 6×10~(-6);较高Φ值能提高干燥速率,储藏过程中,较低Φ值能延长物料保质期;对ΔS_(in)与平衡含水率的关系分析得到最低ΔS_(in)值,在20、30、40℃条件下,籽粒内结合水和单分子层吸附水分子最稳定的平衡含水率分别为5.03%、4.92%以及4.88%。     

The fitting of various models to water sorption isotherms of tea stored in a chamber under controlled temperature and humidity

The moisture sorption characteristics of tea stored in a chamber regulated by an atomizing humidification system were investigated at 25, 35 and 45 °C for water activity ranging from 0.1 to 0.9. The sorption isotherms of tea were typical type II sigmoidal curves according to BET classification. In both adsorption and desorption, an increase in temperature resulted in lower equilibrium moisture contents at corresponding values of water activity. The sorption isotherms exhibited hysteresis over the whole water activity range. GAB, BET, Henderson, Iglesias and Chirife, Oswin, Peleg, Smith and Caurie models were applied for analysing the experimental data. Nonlinear regression analysis was used for the determination of the parameters in the equations. Estimated parameters and fitting ability for sorption models were evaluated. The Peleg model was found to be the most suitable for describing the relationship between equilibrium moisture content and water activity for the whole range of temperatures and relative humidities studied. The surface area of monolayer was calculated. The BET equation was solved for the monolayer moisture content and the corresponding a_w values at which monolayer forms were presented. Sorption isotherm data were used to determine the thermodynamic functions such as isosteric heat of sorption, sorption entropy, spreading pressure, net integral enthalpy and entropy. The Clausius-Clapeyron equation was used to evaluate the isosteric heats of sorption. The isosteric heats of sorption and sorption entropy decreased with increasing moisture content. The heat of desorption was little higher than that of adsorption at low moisture content. The enthalpy-entropy compensation theory could be successfully applied to water sorption by tea. This theory showed that the moisture sorption of tea was governed by enthalpy-controlled mechanisms. The spreading pressure increased with increase in water activity and decreased with increasing temperature. The net integral enthalpy decreased with moisture content while the net integral entropy increased.     

Sorption isotherms and thermodynamic properties of grated Parmesan cheese

This study focuses on isotherms, isosteric heat of sorption and enthalpy–entropy mechanism of water sorption of grated Parmesan cheese at simulating conditions of storage and drying processes. Isotherms were determined by gravimetric method using different saturated salt solutions. Samples were submitted to different temperatures, and several models were used to fit experimental data, GAB and modified GAB being those which best represented experimental data in all temperature ranges. The isosteric heat of sorption was calculated by Clausius–Clapeyron equation, and higher values of integral isosteric sorption heat were verified for storage temperatures. Besides it, both conditions showed higher values of sorption heat corresponding to low water content. This phenomenon was supported by the enthalpy–entropy compensation study, which demonstrated a higher spontaneity of water sorption for storage temperatures, confirming that the lower the water content of food products is, the stronger the intermolecular bonds of water are.     

Sorption isotherms and thermodynamic properties of freeze‐dried colostral whey powders with different additives

Moisture adsorption isotherms of colostral whey (CW) powders with different additives (maltodextrin and sucrose) were determined using gravimetric static method at 15–35 °C in the water activity range of 0.067–0.76. The moisture adsorption isotherms obtained were typical sigmoid curves, and the modified‐Halsey and Guggenheim–Anderson–de Boer (GAB) equations gave the best fit to experimental data among five well‐known equations. Addition with maltodextrin into CW powders could effectively decrease equilibrium moisture content (EMC), whereas addition with sucrose increased EMC in the water activity of 0.43–0.76 at 15 and 25 °C and in the water activity of 0.21–0.76 at 35 °C, respectively. Thermodynamic properties including net isosteric heat of sorption and differential entropy were determined from adsorption data using Clausius–Clapeyron equation. The results showed that net isosteric heat of sorption of all the samples decreased exponentially with increasing EMC. Enthalpy–entropy compensation theory was applicable for adsorption process of all the samples, and the adsorption processes were enthalpy‐driven.     

Moisture sorption isotherms and thermodynamic properties of walnut kernels

The moisture sorption isotherm data of walnut kernels stored in a chamber, the relative humidity (r.h.) of which is regulated by atomizing humidifier, were determined at three different temperatures (25, 35 and 45 °C) and r.h. ranging from 10% to 90%. Eight models, namely the GAB, BET, Henderson, Iglesias and Chirife, Oswin, Peleg, Smith and Caurie equations, were fitted to the sorption data. Several statistical tests were adopted as the criteria to evaluate the fitting performance of the models. Of the models tested, the Peleg model gave the best fit to experimental data. The surface area of a monolayer was calculated. The BET equation was applied to the monolayer moisture content and the corresponding a_w values at which a monolayer forms are presented. The experimental data were also used to determine the thermodynamic functions such as isosteric heat of sorption, sorption entropy, spreading pressure, net integral enthalpy and entropy. The sorption isosteric heats for walnut kernels were determined by the application of the Clausius-Clapeyron equation to sorption isotherms obtained from the best-fitting equation. Isosteric heats decreased with increase in moisture content and approached the latent heat of pure water. Adsorption entropy increased with increasing moisture content, and then it decreased sharply with increase in moisture content. The spreading pressures (adsorption and desorption) increased with increasing water activity. Net integral enthalpy of adsorption increased slightly with moisture content to a maximum value. Thereafter, it remained constant. Net integral entropy of adsorption was negative in value and it decreased with increase in moisture content to a minimum value, and then increased slightly with increase in moisture content.     

Water Sorption Isotherms and Crispness of Fried Yam Chips in the Temperature Range from 293K to 313K

Water sorption isotherms of fried yam chips were determined using a static gravimetric method with saturated salt solutions in the range of water activity between 0.22 and 0.85 at 293, 303 and 313K. Four sorption models namely GAB, Peleg, modified Mizrahi, and BET were fitted with the sorption data generated. The GAB model followed by Peleg and modified Mizrahi models were found to best represent the experimental data in the a_w range of 0.22–0.85. However, the BET model was more applicable between a_w range of 0.22–0.55. The adsorption isotherm of fried yam chips clearly showed the influence of temperature, decreasing the moisture content at a fixed water activity value with higher temperature. The net isosteric heats of sorption of water were estimated by applying the Clausius–clapeyron equation to the adsorption isotherms at different temperatures. The net isosteric heat of sorption was observed to be decreasing as moisture content increases. Samples stored in desiccators of 0.44 and 0.55 a_w at 303 and 313K, respectively, were rated higher in terms of textural properties investigated.     

Moisture adsorption isotherms of guar (Cyamposis tetragonoloba) grain and guar gum splits

Moisture adsorption isotherms of guar grain and guar gum splits were determined at 10, 20, 30 and 40 °C and 23-96% relative humidities using gravimetric method. The sorption data were fitted to six well-known sorption isotherm models (modified Chung-Pfost, modified Halsey, modified Henderson, modified Oswin, Chen-Clayton, and GAB models) using non-linear least square method. The GAB model was found the most satisfactory for representation of the equilibrium moisture content data for guar grain and guar gum splits. The equilibrium moisture content of guar gum splits was found to be significantly higher (p < 0.05) than that of guar grain. The isosteric heat of sorption was determined from the equilibrium moisture adsorption data using Clausius-Clapeyron type equation. Exponential relationship described well the dependence of isosteric heat of sorption on the equilibrium moisture content. The enthalpy-entropy compensation theory applied to sorption isotherms indicated enthalpy controlled sorption process.     

Water Sorption Enthalpy-Entropy Compensation Based on Isotherms of Plum Skin and Pulp

ABSTRACT: The net isosteric heat and entropy of water sorption were calculated for plum, based on sorption isotherms obtained by the static gravimetric method at different temperatures (20 to 70 °C). The Guggenheim-Andersonde Boer model was applied to the experimental data giving a good agreement between experimental and calculated values. The net isosteric heat of water sorption, estimated by applying Claussius-Clapeyron equation to sorption isotherms, was found to be different for plum skin and pulp, mainly at low moisture contents, and could be well adjusted by an empirical exponential relationship. Plots of enthalpy in contrast to entropy provided the isokinetic temperatures for skin and pulp, indicating an enthalpy-controlled sorption process. Thermodynamic data on water sorption for plums are not found in literature, as opposed to prunes for which the data are abundant.     

Moisture sorption characteristics of dried acid casein from buffalo skim milk

Adsorption and desorption isotherms of dried acid casein prepared from buffalo skim milk were determined at 25°, 35° and 45 °C over a water activity range of 0.11-0.97 using static moisture gain/loss from test samples. Both the adsorption and desorption isotherms exhibited sigmoid shape corresponding to type II, typical to many foods. There was generally a negative temperature effect on equilibrium moisture content. The effect of temperature was, however, statistically not significant over the temperature range of 25-45 °C. Of the seven sorption models tested for fitting the sorption data, the GAB model gave the best fit at all the three temperatures. The temperature dependence of GAB parameters has been determined in the form of Clausius-Clapeyron equation. The calculated values of monolayer moisture content from BET isotherm equation have been found to be lower than the corresponding values found by using GAB equation. However, in both cases the monolayer moisture was higher in desorption than the adsorption and deceased with increase in temperature. The net isosteric heat of sorption decreased exponentially with increasing moisture content and approached a constant value of 0.331 kJ/mol at moisture content 28 g/100 g (d.b.). The moisture sorption hysteresis observed at 25°, 35° and 45 C was statistically significant. The extent of hysteresis was negligible in monolayer moisture content region, occurred predominantly in the water activity range 0.35-0.60 and decreased at higher water activities. Total hysteresis energy was evaluated from the sorption data using Everett and Whitton plot. The effect of increase in temperature was to decrease the amount of hysteresis.     

豆粕平衡水分及吸着等热研究

采用静态称重法测定了国产6个豆粕样品的平衡水分吸附/解吸等温线,并采用修正MCPE、MHAE、MHE、MGAB、MOE及STYE 6个方程进行拟合,得出MGAB、MHAE、MOE均适合描述豆粕平衡水分-平衡相对湿度之间的关系,并可用于分析豆粕水分吸附/解吸等热。当水分小于15%时,豆粕吸附/解吸等热均随水分增大而快速减小,同温度下的解吸吸着等热显著高于吸附吸着等热。当水分大于15%时,豆粕吸附/解吸等热均随水分增大而变化平缓,同温度下的解吸吸着等热趋同于吸附吸着等热。当水分小于15%时,较低温度下的豆粕吸附吸着等热与解吸吸着等热均高于较高温度下的。在水分17.5%的游离水临界点,豆粕的吸着等热(汽化热)接近纯水的潜热,约为2 500 kJ/kg。由等温线分析的25℃豆粕绝对安全水分为12.48%,相对安全水分为13.90%。