Behaviour of cod liver oil during the autoxidation process

Prostaglandin‐like compounds, called isoprostanes, are generated by free enzyme‐independent radical peroxidation of the acids arachidonic (AA), eicosapentaenoic (EPA) and docosahexaenoic (DHA). Up to now, isoprostanes have been largely studied only in men and biological systems, but never in food. In this research, cod liver oil was used as a model system to study the oxidation mechanism in food containing high amounts of EPA and DHA. For comparison, under similar oxidation conditions, also the behaviour of a sunflower seed oil and an n‐3 long‐chain polyunsaturated fatty acid capsule supplement oil were studied. It was ascertained that EPA‐ and DHA‐derived compounds were formed during oxidation. These compounds were polar and easily isolatable by methanol from oxidised transmethylated oil. EPA and DHA oxidation derivatives showed maximal absorbance at 200 nm and were very potent pro‐oxidants at high temperatures. In oxidised sunflower oil, similar compounds did not form. Unfortunately, the chemical structures of the EPA and DHA oxidation derivatives were not discovered, but it is a realistic hypothesis that they could be isoprostane‐like compounds.     

Effect of heat processing on phenolic constituents and nutritional quality of sunflower flours

Heat processing of dehulled, defatted sunflower flour resulted in a reduction in phenolic constituents, the destruction of chlorogenic acid (CGA) being more than that of caffeic acid (CA) and quinic acid (QA). Considerable losses in the available lysine rather than total lysine content were observed when sunflower flour was autoclaved at 1 kg/cm² (120 C) for periods varying from 5 to 60 min. The N solubility of sunflower protein in 0.02N NaOH showed a progressive decrease as the duration of heat treatment increased. Moderate heat treatment (15 min at 120 C) of the flour had no significant beneficial effect on in vitro digestibility. Any advantage in decreasing the levels of CGA, CA and QA contents by moderate heat treatment apparently was lost by the decrease in available lysine content, thus lowering the protein efficiency ratio (PER) from 1.97 to 1.71 and Net Protein Utilization (NPU) from 62.7 to 54.8, respectively.     

Chemical Characterization of Virgin Almond and Hazelnut Oils and Their By‐Products

Various cultivars of almonds (“Ferragnes,” “Guara,” “Largueta,” and “Marcona”) and hazelnuts (“Negret,” “Pauetet,” and “Tonda”), particularly their virgin oils and by‐products, are evaluated in this study. The almond and hazelnut virgin oils present high contents of oleic acid (59–73% and 76–80%, respectively) and α‐tocopherol (420–542 and 310–378 mg kg^–1, respectively), as compared with other virgin vegetable oils. Aldehydes are the major contributors to their aromatic profile (54–74% almond oil and 30–40% hazelnut oil of total content), especially, benzaldehyde in almond oils (1.35–7.52 mg kg^–1), and hexanal in hazelnut oils (0.99–1.27 mg kg^–1). Statistical differences exist between the virgin almond and hazelnut oils and their varieties, for most of the chemical compounds studied. While all the nut varieties are high in polar phenolic compounds, “Ferragnes” almonds (1262 mg kg^–1) and “Negret” hazelnuts (1720 mg kg^–1) stand out. Accordingly, high antioxidant activity is also observed. Finally, the residual cakes may be considered a good source of polar phenolic compounds (823–2064 mg kg^–1 almond cakes, 2261–4179 mg kg^–1 hazelnut cakes), possessing high antioxidant capacity with potential applications of these by‐products as functional ingredients in food and non‐food formulations. Practical Applications: Virgin nut oils are gaining consumers’ preference due to their unique organoleptic attributes and potential health effects. It is therefore very relevant to establish their specific chemical composition, directly related to their properties, and that are greatly affected by the cultivar.     

Effects of milk fat replacement by PUFA enriched fats on n‐3 fatty acids,conjugated dienes and volatile compounds of fermented milks

A study was carried out to determine the profiles of fatty acids in fermented milks and dairy derivatives made with milk fat substituted by polyunsaturated fatty acid (PUFA)‐enriched fat. In order to improve the organoleptic properties of those products, whey protein concentrates (WPC) were added during the manufacturing process. Interest was focused during manufacturing and storage period on the contents of “healthy” fatty acids, mainly conjugated linoleic acid and n‐3 PUFA. Contents of these fatty acids were not affected by the manufacture practices and neither did addition of WPC during manufacturing nor cold storage cause their decrease. Percentages of total n‐3 fatty acids in fat from dairy derivatives enriched in PUFA after 21 d of storage (1.45%) were very close to those obtained before processing (1.39%). Contents did not differ either substantially when WPC were added during manufacturing (1.46%). The increase of volatile compounds was also examined. Although a slight decrease in the total volatile content was observed, percentages of different compounds were not modified when milk fat was substituted by PUFA enriched fat.     

Hydrochloric acid‐catalyzed levulinic acid formation from cellulose: data and kinetic model to maximize yields

In this study, the kinetics of the acid catalyzed hydrolysis of microcrystalline cellulose (Avicel PH101) to levulinic (LA) and formic (FA) acids was investigated in a batch reactor over the following range of conditions: 160–200°C, hydrochloric acid concentrations of 0.309–0.927 M (11.3–33.8 g/l), cellulose concentrations of 49.8–149 mM (8.06–24.1 g/l), and residence times of 0–50 min. The maximum LA yield of around 60% of theoretical was achieved for an initial cellulose concentration of 99.6 mM, acid concentration 0.927 M, and 180–200°C. A mathematical model and its analytical solution were developed to predict conversion of cellulose to LA and FA through glucose and hydroxymethyl‐2‐furfural based on an irreversible pseudo‐first order reaction. Rate analysis of each reaction indicated that the rate‐controlling step shifted from LA formation initially to HMF formation later. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Synthesis of alkyl‐branched fatty acids

Alkyl‐branched fatty compounds are of interest for industrial products in the cosmetics and lubricant areas. In this review, clay‐ and zeolite‐catalyzed isomerizations of unsaturated fatty compounds, especially of oleic acid, are discussed. While clay‐catalyzed reactions give most complex mixtures of dimeric fatty acids and of monomeric so‐called “isostearic acid”, the zeolite‐catalyzed process yields preferentially an isomeric mixture of isostearic acids having the methyl branch on the 8–14 positions of the alkyl chain. Synthetically useful additions of alkyl radicals can only be performed on ω‐unsaturated fatty compounds, whereas perfluoroalkyl iodides were added to fatty compounds with terminal as well as internal double bonds using electron transfer‐initiated radical addition reactions. Electrophilic additions of alkyl carbenium ions generated by decomposition of alkyl chloroformates by ethylaluminum sesquichloride give well‐defined alkyl‐branched oleochemicals with good yields.     

Evaluation of Simple and Inexpensive High-Throughput Methods for Phytic Acid Determination

High‐throughput/low‐cost/low‐tech methods for phytic acid determination that are sufficiently accurate and reproducible would be of value in plant genetics, crop breeding and in the food and feed industries. Variants of two candidate methods, those described by Vaintraub and Lapteva (Anal Biochem 175:227–24, 1988 ; “VL” methods) and Huang and Lantzsch (J Sci Food Agric 34:1423–1426, 1983 ; “HL” methods), were evaluated. The primary concern with these methods is that, due to interference of matrix constituents including inorganic P, they can overestimate phytic acid and are ineffective at low levels of phytic acid. Twelve seed flours, representing lines of soybean, maize, barley and dry bean, containing a wide range of phytic acid levels, were analyzed by a minimum of eight cooperating laboratories using three variants of the VL method and two variants of the HL method. No method had consistently acceptable (?2.0”) “Horwitz ratios”, a measure of reproducibility, although some treatments approached that. For example, one variant of the VL method when used to assay a soybean flour with a “standard” level of phytic acid had a Horwitz ratio of 2.15. Some variants of the VL method were adequate for analyses of cereal grains regardless of phytic acid level but none accurately measured phytic acid when at low levels in soybean flours. One variant of the HL method in which the 0.2 N HCl extraction media is modified to contain 10% Na₂SO₄, did accurately measure phytic acid levels in both cereal and legume flours regardless of endogenous phytic acid levels or matrix constituents.     

Extraction of Carboxylic Acids from Aqueous Solutions with the Extractant System Alcohol/Trin‐Alkylamines

A frequent problem in the production of organic compounds via partial oxidation are unwanted byproducts, like acetic acid. Here, the convenient method for working‐up the aqueous acidic effluents (containing up to 10 wt.‐% acid) after removing the main product is the extraction. The influence of various extractant systems containing organic solvents and trialkylamines on distribution coefficients and selectivities of acids has been studied. Acetic acid and lactic acid served as model compounds for acidic byproducts and acidic fermentation products, respectively. Experimental results indicate that combinations of tri‐n‐hexylamine and an alcohol show greatest synergistic effects and as a consequence comparably high distribution coefficients.     

Evaluation of thermo‐viscosity parameters of dextran in polar and nonpolar solvent

Some thermo‐viscosity parameters like Viscosity‐molecular weight constant (K), the short‐range parameter, (A) and long‐range parameter (B) have been evaluated for the polymer “Dextran” of three different molecular weights (M?_w = 19,500, 75,000, and 250,000) in three different solvents like 6 (M) aqueous urea, 2 (M) aqueous glycine, and 50% aqueous glucose at temperatures ranging from 25 to 50°C. The study reveals that the viscosity‐molecular weight constant (K) decreases with increase in temperature for polar solvents like aqueous urea and aqueous glycine. The value of “K” increases with the rise in temperature within the range of 25 to 35°C in case of a nonpolar solvent aqueous glucose and then “K” decreases with the increase in temperature within the range of 40 to 50°C for the nonpolar solvent aqueous glucose. The short‐range parameter (A) shows the same trend as shown by “K” and the long‐range parameter “B” exhibits no definite trend with the variation of temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 440–452, 2001     

Calcium Sulfate as a Possible Oxidant in “Green” Silicon‐based Pyrotechnic Time Delay Compositions

Chemical time delay detonators are used to control blasting operations in mines and quarries. Slow burning Si BaSO₄ pyrotechnic delay compositions are employed for long time delays. However, soluble barium compounds may pose environmental and health risks. Hence inexpensive anhydrous calcium sulfate was investigated as an alternative “green” oxidant. EKVI simulations indicated that stoichiometry corresponds to a composition that contains less than 30 wt‐% Si. However combustion was only supported in the range of 30–70 wt‐% Si. In this range the bomb calorimeter data and burn tests indicate that the reaction rate and energy output decrease with increasing silicon content. The measured burning rates in rigid aluminum elements ranged from 6.9 to 12.5 mm s⁻¹. The reaction product was a complex mixture that contained crystalline phases in addition to an amorphous calcium containing silicate phase. A reaction mechanism consistent with these observations is proposed.     

Thermodynamic modeling of HNO3‐H2SO4‐H2O ternary system with symmetric electrolyte NRTL model

The nitric acid concentration/sulfuric acid concentration (NAC/SAC) process has been widely used for concentrating dilute aqueous nitric acid and recovering spent sulfuric acid. Dilute nitric acid (65 to 80 wt %) is concentrated using sulfuric acid to bind water and break the nitric acid‐water azeotrope at approximately 68 wt % nitric acid. To support heat and mass balance calculations and process simulation for NAC/SAC processes, we develop a comprehensive thermodynamic model for nitric acid‐sulfuric acid‐water ternary system based on previously published thermodynamic models of nitric acid‐water and sulfuric acid‐water binary systems with eNRTL equation. The ternary system model correlates well the isobaric vapor‐liquid equilibrium data at one atmosphere and the water and nitric acid activities data at 273.15 K for the ternary. Contour plots of boiling points, vapor phase composition, and specific heat capacity of the ternary system, as well as a Merkel enthalpy‐concentration chart are generated for engineering use. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3110–3117, 2017     

Rapid formation of flexible silk fibroin gel‐like films

Flexible silk fibroin gel‐like films with microporous morphology were prepared from B. mori silk fibroin fibers directly solubilized in formic acid/CaCl₂ solvent. These films were characterized by several analysis techniques to determine the structure and properties of films. The pore size of gel‐like films can be adjusted through SF concentration and Ca ions concentration. The controllable pore size in gel‐like films was grew from 3–5 μm to 100 μm under the increase of fibroin concentration from 1.0 wt % to 8.0 wt %. At the same time, the water content of silk fibroin gel‐like film decreased from 83.5 ± 3.4% to 68.2 ± 2.6%. With increasing Ca ions contents from 2.0 wt % to 10.0 wt % in dissolution process, the pore size and water content of silk fibroin gel‐like films grew larger, especially its water content values reached 86.2 ± 4.0% at 10.0 wt % Ca ions concentration. At wet condition, the gel‐like film with β‐sheet structure showed higher breaking stress (4.26 ± 0.31 MPa) and elongation (45.45 ± 15.79%) at 8.0 wt % concentration. With the preparation method, the membrane is hydrophilic and the pore size is adjustable, which contributes to high toughness and favorable cell growth environment, suggesting that these silk fibroin gel‐like films can be a potential candidate scaffold for biomedical applications, such as wound dressing, facial mask, contact lenses, etc. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41842.     

Pervaporation of water/alcohol mixtures through chitosan/cellulose acetate composite hollow‐fiber membranes

For the purpose of separating aqueous alcohol by the use of pervaporation technique, a composite membrane of chitosan (CT) dip‐coated cellulose acetate (CA) hollow‐fiber membranes, CT‐d‐CA, was investigated. The effects of air‐gap distance in the spinning of CA hollow‐fiber membranes, chitosan concentration, and sorts of aqueous alcohol solutions on the pervaporation performances were studied. Compared with unmodified CA hollow‐fiber membrane, the CT‐d‐CA composite hollow‐fiber membrane effectively increases the permselectivity of water. The thickness of coating layer increases with an increase in chitosan concentration. As the concentration of chitosan solution increased, the permeation rate decreased and the concentration of water in the permeate increased. In addition, the effects of feed composition and feed solution temperature on the pervaporation performances were also investigated. The permeation rate and water content in permeate at 25°C for a 90 wt % aqueous isopropanol solution through the CT‐d‐CA composite hollow‐fiber membrane with a 5‐cm air‐gap distance spun, 2 wt % chitosan dip‐coated system were 169.5 g/m² h and 98.9 wt %, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1562–1568, 2004     

Chemo‐enzymatic synthesis and evaluation of novel structured phenolic lipids as potential lipophilic antioxidants

Chemo‐enzymatic synthesis of structured triacylglycerol bearing ferulic acid as a phenolic acid at sn‐1/3 position is described in the present work. Four compounds of varying chain lengths, namely 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐hexanoyloxy‐propyl ester, 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐octanoyloxy‐propyl ester, 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐dodecanoyloxy‐propyl ester, and 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐9‐octadecenoyloxy‐propyl ester were synthesized, and their structures were confirmed by IR, NMR, and MS. Antioxidant activity of the structured phenolic lipids were evaluated using three different in vitro antioxidant assays such as 2, 2‐diphenyl‐1‐picrylhydrazyl free radical (DPPH^•) scavenging, antioxidant potency in lipid matrix using rancimat, and by the rate of inhibition of autoxidation of linoleic acid in micelles. Ferulic acid and dodecylgallate were used as reference antioxidant compounds. DPPH^• assay did not show any improvement in the antioxidant activity of ferulic acid with lipophilic modification. However, the antioxidant potency of the structured phenolic lipids measured by rancimat method as well as by the rate of inhibition of autoxidation of linoleic acid in micelle showed improvement in antioxidant activity compared to ferulic acid. This is probably due to better solubility of the synthesized phenolic lipids in a hydrophobic medium and appropriate anchorage in Tween 20 micelle. The observed activities of the structured phenolic lipids are comparable to dodecyl gallate in rancimat assay, but superior to dodecyl gallate in Tween 20 micellar system.     

Effect on adhesion of new polymerization initiator systems comprising 5‐monosubstituted barbituric acids,aromatic sulfinate amides,and tert‐butyl peroxymaleic acid in dental adhesive resin

To develop a multipurpose dental adhesive resin, the effects of polymerization initiator systems comprising 5‐monosubstituted barbituric acid (5‐MSBA), aromatic sulfinate amide (ASA), and tert‐butyl peroxymaleic acid (t‐BPMA) with 4‐acryloxyethyltrimellitic acid (4‐AET) or its anhydride (4‐AETA) on adhesion and curing time were investigated. Tensile bond strength values of a Ni Cr alloy are affected by the inclusion of t‐BPMA, and the optimum concentration of t‐BPMA in a 5‐MSBA–ASA–t‐BPMA‐type initiator system was found to be 0.5–2.0 wt %, and it was noteworthy that the correlation between the tensile bond strength and curing time on the t‐BPMA‐concentration showed a highly negative correlation of a benzenesulfinate morphoride (BSMo) series adhesive: r = −0.957, and a p‐toluenesulfinate morphoride (p‐TSMo) series adhesive: r = −0.949. The combination of 1‐cyclohexyl‐5‐ethylbarbiturioc acid (CEBA) with ASA provides a high level of tensile bond strength to the Ni Cr alloy, and the optimum concentration of CEBA in a CEBA–ASA–t‐BPMA‐type initiator and the bond strength values were found to be 0.75 wt % CEBA: 52.3 MPa (with BSMo), and 1.0 wt % CEBA: 50.9 MPa (with p‐TSMo), respectively. It was suggested that 5‐MSBA, ASA, and t‐BPMA and their combinations provided the environment where 4‐AETA exhibited good bonding performance with increasing wettability to metal without interference of a charge‐transfer complex derived from a polymerization initiator system such as benzoyl peroxide (BPO)–amine. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1655–1668, 1999     

Study on transparent poly(propylene) nucleated by the “in situ” reaction products of dehydroabietic acid and sodium stearate

Dehydroabietic acid (DHA), sodium stearate (NaSt), DHA/NaSt (1/1 wt/wt) mixture, the reaction products of DHA/NaSt (1/1 wt/wt) mixture after heating at 220°C for 10 min and sodium dehydroabietate (DHAA‐Na) were qualitatively analyzed by Fourier transform infrared spectrometry (FTIR) and wide angle X‐ray diffractometry (WAXD). The crystallization behavior, spherulitic morphology, optical and mechanical properties of iPP samples nucleated by DHA, NaSt, DHA/NaSt (1/1 wt/wt) mixture, and DHAA‐Na under the same concentration (0.3 wt %) were investigated by differential scanning calorimetry (DSC), polarized light microscope (PLM), optical and mechanical measurements. The results showed that an “in situ” reaction occurred between DHA and NaSt, and an effective transparent nucleating agent (DHAA‐Na) was produced during the melting blending of iPP and DHA/NaSt (1/1 wt/wt) mixture in the twin screw extruder. The crystallization onset and peak temperatures, the gloss and the mechanical properties were improved markedly; the crystallization half‐time, the spherulitic size, and the haze were reduced substantially when iPP samples are nucleated by DHA/NaSt (1/1 wt/wt) mixture. The optimum composition ratio of DHA/NaSt should be kept at ≈ 1/1 wt/wt and above 0.4 wt %/0.4 wt %. The DHA/NaSt bi‐component nucleator was effective for iPP with different MFR values. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of a small amount of sulfur on the physical and mechanical properties of peroxide‐cured fully saturated HNBR compounds

Sulfur can be used as crosslink coagent in unsaturated elastomer. In this work, a fully saturated HNBR with 39 wt % nitrile content was selected to investigate the effect of a small amount of sulfur acting as crosslink coagent on the physical and mechanical properties of peroxide‐cured vulcanizates. First, selective cleavage of polysulfide (? Sx? ) and monosulfide(? S? ) bond by combined thiol‐piperidine treatment were performed and the existence of poly/monosulfide bond in sulfur‐contained HNBR compounds was verified. Then, no‐filler HNBR compounds with various content of sulfur were investigated to detect the influence of sulfur on the crosslink density and cure kinetics. The MDR results showed that the crosslink density of HNBR compounds reduced only when the amount of sulfur is 0.25 phr and above. Besides, the curing rate of no‐filler HNBR compounds increased with the increasing of the amount of sulfur and reached a maximum at a dosage of 0.25 phr sulfur. Finally, physical and mechanical properties of fully formulated compounds were evaluated and it was found that the addition of small amounts of sulfur in fully saturated HNBR compounds could improve the dynamic properties of peroxide‐cured HNBR compounds remarkably but at a cost of slightly higher compression set values and a small loss in heat aging resistance. In a conclusion, small amount of sulfur can impart the peroxide vulcanizates some “sulfide properties” like dynamic property, tensile strength, but at the same time, due to the introduction of sulfur, some “peroxide vulcanizates property” like heat‐resistance property, hot air resistance were weakened slightly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41612.     

In‐Situ Formation of Viscoelastic Wormlike Micelles in Mixtures of Non‐Surface‐Active Compounds

Viscoelastic fluids based on surfactant self‐assembled wormlike micelles have been in focus over the past decade. In this work, we report wormlike micellar solutions formed in situ by simply mixing two non‐surface‐active compounds, N‐(3‐(dimethylamino)propyl)palmitamide (C16AMPM) and salicylic acid (HSal), without specialized organic synthesis of a surfactant. In the absence of HSal, C16AMPM is poorly soluble in pure water; after introducing HSal, C16AMPM is protonated into quaternary ammonium, behaving like a cationic surfactant with a low critical micellar concentration (0.25 mM) and a small area per molecule, which favors the formation of long cylindrical wormlike micelles. Above the overlapping concentration (~28 mM), the wormlike micelles formed entangle each other into viscoelastic networks, enhancing the viscosity by several orders of magnitude. In contrast to the worms formed by a single ultra‐long‐chain surfactant, the current system shows the advantages of a smaller flow activation energy and end‐cap energy, simpler formulation and lower cost, which make it more suitable for practical use.     

Synthesis and characterization of nylon 6/clay nanocomposites prepared by ultrasonication and in situ polymerization

Nylon 6 nanocomposites were prepared by the in situ polymerization of ε‐caprolactam with ultrasonically dispersed organically modified montmorillonite clay (Cloisite 30B®). Dispersions of the clay platelets with concentrations in the range 1–5 wt % in the monomer were characterized using rheological measurements. All mixtures exhibited shear‐thinning, signifying that the clay particles were dispersed as platelets and forming a “house of cards” structure. Samples with Cloisite concentrations above 2 wt % showed a drop in viscosity between the initial shearing and repeated shearing, indicative of shearing breaking down the initial “house of cards” structures formed on sonication. DMTA measurements of the samples showed an increase in the β‐relaxation temperature with increasing clay concentration. The bending modulus, at temperatures below T_g, showed an increase with increasing clay concentration up to 4 wt %. X‐ray diffraction measurements showed that all nylon 6/Cloisite 30B samples were exfoliated apart from the 5 wt %, which showed that some intercalated material was present. The nylon crystallized into the α‐crystalline phase, which is the most thermodynamically stable form. Preference for this form may be a consequence of the long time associated with the postcondensation step in the synthesis or the influence of the platelets on the nucleation step of the crystal growth. DSC measurements showed a retardation of the crystallization rate of nanocomposite samples when compared with that of pure nylon 6, due to the exfoliated clay platelets hindering chain movement. This behavior is different from that observed for the melt‐mixed nylon 6/clay nanocomposites, which show an enhancement in the crystallization rate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Photocatalytic degradation of malic acid using a thin coated TiO2‐film: Insights on the mechanism of photocatalysis

Decontamination of opaque fluids using photocatalysts and near Ultraviolet (UV) irradiation involves major technical challenges. This study considers a thin TiO₂ layer placed in a new Chemical Reactor Engineering Centre (CREC)‐photoreactor cell. This new photoreactor cell is used for the photocatalytic degradation of malic and malonic acids, typical apple juice components. Conversion of organic species can only proceed through the “dark side” of the TiO₂ layer, which is in direct contact with the fluid. Under the selected operating conditions both external mass‐transfer limitations and photolysis are found to be negligible. Macroscopic radiation balance shows that 92% of near UV radiation is absorbed by the ‘back side” of the TiO₂‐film. Photocatalytic degradation experiments with 10, 20, 30, and 40 ppm malic acid initial concentrations, show that malonic acid is a main intermediate. Complete malic acid conversion occurs after 5–8 h of irradiation. Kinetic modeling of malic and malonic acid photodegradation with kinetic parameter estimation is performed using both an “in series” and an “in series‐parallel” reaction networks. The “in series‐parallel” reaction network displays better ability for predicting CO₂ formation, showing maximum quantum yields of 14.2%. Given that in the CREC‐photoreactor cell with a thin TiO₂‐film, photocatalysis can only proceed via the transfer of mobile “h⁺” sites from the irradiated side to the “dark side', this study demonstrates the significance of this step on the overall photocatalysis mechanism. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3286–3299, 2014