The hydrolysis of soap solutions. III. Values of pH and the absence of fatty acid as free liquid or solid

Summary The pH of the laurates, myristates, palmitates, and stearates of sodium and potassium at 25° and 50°C. was determined by use of a glass electrode. pH:concentration curves were constructed, and hydroxyl ion activity was calculated. In general, the concentration of hydroxyl ion ranges from 0.001 to 0.0001 N; for the less dilute solutions of the higher soaps, the upper limit is exceeded by several fold, and in the more dilute solutions the concentration may fall beneath the lower value. Solubilized hexane reduced the pH of potassium and sodium laurate but very slightly. Potassium or sodium chloride reduced the pH of soap solutions over a certain range but caused a slight increase in a narrow intermediate range. Using the pH values obtained, the actual concentration of fatty acid in the soap solutions was calculated, and was found to beless than the saturation concentrations obtained by conductivity measurements through the entire range investigated. Free fatty acid therefore never separates as such from pure soap solutions unless acted upon by excess of acid such as carbon dioxide. Percentage hydrolysis was calculated and curves were constructed. In general, the potassium soaps are hydrolyzed more than the corresponding sodium soaps; the difference is slight for the laurates but is considerably greater for the myristates, palmitates, and stearates in higher concentrations at 25°C. The difference is appreciably smaller at 50° than at 25°. Percentage hydrolysis for the laurates is very much less than for the higher soaps.     

An expedient synthesis of methyl vinyl sulfide from dimethyl disulfide and acetylene

Dimethyl disulfide reacts with acetylene under atmospheric pressure in basic reductive systems MOH (M=Na, K)–N₂H₄?·?H₂O–N-methylpyrrolidone and Na₂S?·?9H₂O–N₂H₄?·?H₂O–N-methylpyrrolidone to form methyl vinyl sulfide in up to 79% yield.     

Soluble conducting polypyrrole doped with DBSA–CSA mixed acid

Soluble conductive polypyrrole (PPy) with room temperature conductivity (2–18 S/cm) has been synthesized by doping polypyrrole with mixed acid containing camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA). The solubility and the room temperature conductivity of PPy doped with mixed acid were measured as a function of component of CSA–DBSA mixed acid, and the structure of PPy was characterized by Fourier transform infrared (FTIR), ultraviolet–visible (UV-vis) spectra, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). PPy doped with DBSA–CSA mixed acid is soluble in m-cresol although PPy doped only by CSA is completely insoluble in any solvent. The solubility of PPy doped with mixed acid increases with an increase in the fraction of DBSA in the mixed acid, while the room temperature conductivity of the PPy increases with increasing CSA molar fraction. The UV-vis spectra and electron spin resonance (ESR) measurements showed that both polaron and bipolaron are the charge carrier in the doped PPy with mixed acid. It was proposed that the contribution of CSA to the solubility of PPy doped with mixed acid is to decrease the interaction among PPy chains due to the large molecular size of CSA, while DBSA contributes to the solubility by its good solvating effect derived from its long alkyl chain. These may be a reason that both the solubility and conductivity of PPy are improved by the presence of CSA compared with those of PPy doped only with DBSA. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 1277–1284, 1998     

The effect of fatty acid composition on the acrylation kinetics of epoxidized triacylglycerols

Epoxidized oils, epoxidized triacylglycerols, and epoxidized fatty acid methyl esters were made by reaction with performic acid formed in situ. The extent of epoxidation was ca. 95% for all of the epoxidized samples, as determined by ¹H nuclear magnetic resonance. The epoxidized samples were reacted with an excess of acrylic acid for different reaction times. The acrylation reaction was found to have a first-order dependence on the epoxide concentration for all oils, pure triacylglycerols, and fatty acid methyl esters. However, the rate constant of acrylation was found to depend on the composition of the epoxidized material. The acrylation rate constant for 9,10-epoxystearic acid was 96 L²/(mol²·min). The rate constant of acrylation for the epoxides on 9,10,12,13-diepoxystearic acid was 60 L²/(mol²·min). The acrylation rate constant for the epoxides on 9,10,12,13,15,16-triepoxystearic acid was 50 L²/(mol²·min). Thus, the rate constant of acrylation increased as the number of epoxides per fotty acid decreased. Multiple epoxides per fatty acid decrease the reactivity of the epoxides because of steric hindrance effects, and the oxonium ion, formed as an intermediate during the epoxyacrylic acid reaction, is stabilized by local epoxide groups. These results were used to derive an acrylation kinetic model that predicts rate constants from fatty acid distributions in the oil. The predictions of the model closely match the experimentally determined rate constants.     

Hydroxyalkylation of parabanic acid. I. Reactions with formaldehyde

The results of investigations into the reaction of parabanic acid with formaldehyde at different molar ratios of the reagents are presented. A fast and effective method of synthesis of N,N′‐bis(hydroxymethyl)parabanate was developed. The reaction of parabanic acid with an excess of formaldehyde was analyzed and the structure of the products proposed. Conditions at which the hydroxymethyl derivatives of parabanic acid undergo self‐condensation as well as prospects of using them in subsequent oxyalkylation with oxiranes are specified. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2858–2872, 2002; DOI 10.1002/app.10274     

Hydroxyalkylation of barbituric acid. III. Product analysis and reaction pathway

Polyetherols containing a thermally stable pyrimidine ring were obtained upon the reaction of hydroxymethyl derivatives of barbituric acid with an excess of ethylene or propylene oxide. The reaction was monitored by ¹H‐NMR and IR spectroscopy for the systems with variable starting molar ratios of reagents. We found that formaldehyde rearranged from N‐hydroxymethyl and oxymethylene bridges into the end of the polyetherol chain during the reaction. Simultaneously, the O‐hydroxymethyl groups underwent blocking by oxirane. The structures of the polyetherols was deduced on the basis of the course of the reaction and the analytical data. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

liquid–liquid extraction of lactic acid with Alamine 336

The extraction of lactic acid (HL) from aqueous solutions by Alamine 336 (B) dissolved in toluene was studied. Experiments were performed in the temperature range of 25–60°C and for two amine concentrations of 20 and 40% (v/v) in toluene. The extent to which the organic phase (amine + toluene) may be loaded with lactic acid is expressed as a loading ratio, Z = C_HL /C_B. Z values are independent of the amine concentration and, hence, the extracted complex contains only one molecule of amine. Z decreases with increasing temperature. Experimental results indicate that the system presents overloading, i.e. Z > 1. The extraction equilibrium may be interpreted as a result of consecutive formation of three acid–amine species with stoichiometries of 1:1, 2:1 and 3:1.     

Synthesis,Characterization and Fluorescence Properties of Poly(styrene-co-n-caprylamide maleic acid) and Its Europium(III) and Terbium(III) Complexes

Copolymer of poly(styrene-co-n-caprylamide maleic acid) (PSCMA, defined as HL) and its lanthanide complexes Ln(L)₃·6H₂O (Ln = Eu and Tb) had been synthesized and characterized by elemental analysis, X-ray diffraction, Fourier transform infrared spectra, UV-spectrophotometer and thermal analysis (TG–DTA). The fluorescence properties of the HL ligand and the Ln(L)₃·6H₂O complexes in the solid state were investigated. At room temperature, the HL ligand had a strong broad emission band at 410–575 nm (λmax = 458 nm) under excitation at 380 nm, while the respective characteristic emission of Eu(III) and Tb(III) ions was observed in Ln(L)₃·6H₂O complexes. This demonstrated that the HL ligand in the extra-framework channels succeeded in sensitizing Eu(III) and Tb(III) ions emission. Compared with the Eu(L)₃·6H₂O complex, the fluorescence intensity of the Tb(L)₃·6H₂O complex was much stronger. This indicated that the lowest excited triplet state energy level of HL matched well with the excited state energy level of Tb(III). With the increase of the Ln(III) ions content below 15 wt%, the fluorescence intensity increased monotonically. All the Ln(L)₃·6H₂O complexes exhibited high quantum yield, long fluorescence lifetime and good thermal stability.     

On the reaction of (S)-trifluoroacetoxysuccinic anhydride with amines to produce hydroxysuccinamic (malamic) acid derivatives

L-Malic acid ( 2 ) reacts with trifluoroacetic anhydride under anhydrous conditions to give (S)-trifluoroacetoxy-succinic acid anhydride ( 3 ). The anhydride 3 undergoes regioselective ring opening with an excess of anilines or primary aliphatic amines leading to N-substituted-(S)-3-hydroxy-succinamic acids ( 4a – g ). Structural elucidation of the reaction products 4a – g was based on analytical and spectroscopic data and on an X-ray structure analysis of 4b . Secondary aliphatic amines react with 3 by condensation and subsequent elimination to furnish N,N′-disubstituted fumaric acid amides 5a , b . Some N-substituted-2-hydroxysuccinamic acids ( 7a , b ) were also prepared for spectral comparison with the 3-hydroxy compounds.     

Characterisation of a coordinated imidazole as a structural model for superoxide dismutase

The copper complex [Cu(HL)](ClO₄)₂·2H₂O, where HL is N-[2-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)ethyl]–N-(benzimidazol-2-yl)methanimine, has been prepared and characterised by X-ray crystallography and solution absorption spectroscopy. Deprotonation of the benzimidazole moiety in this complex has been investigated by electronic spectroscopy. The results show a definite shift in λ_max for [Cu(HL)]²⁺, at 632–818 nm for the deprotonated [CuL]⁺, in acetonitrile. This complex has been synthesised as a structural homologue to half of the enzyme Cu–Zn superoxide dismutase (SOD) which contains a bridged imidazolate moiety between the two Cu and Zn metal ions.     

Synthesis and characterization of ferromagnetic polyaniline with conductivity in an applied magnetic field

Ferromagnetic polyaniline (PANI) with conductivity was synthesized with peroxydisulfate as an oxidant and horseradish peroxidase as a catalyst in an N′‐a‐hydroxythylpiperazine‐N′‐ethanesulfanic acid buffer solution containing aniline, HCl, and NiCl₂·6H₂O in an applied magnetic field. The result of an electron paramagnetic resonance spectrum indicated that there were unpaired electrons in the resulting product, the spin density of which was 7.60 × 10¹⁹ spins/g. The curve of the magnetization versus the magnetic field showed that PANI had soft ferromagnetic behavior at about 300 K. The saturation magnetization and coercive force of PANI were 0.033 emu/g and 5 Oe, respectively. Ultraviolet–visible and Fourier transform infrared spectra indicated that there was interaction between Ni²⁺ and PANI chains but the structure of the backbone chains of PANI synthesized in the presence of a magnetic field hardly changed compared with that of PANI synthesized without NiCl₂·6H₂O. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Intercalation of conducting poly(N‐propane sulfonic acid aniline) in V2O5 xerogel

Poly(N‐propane sulfonic acid aniline) (PSPAN) can be formed between the lamellas of V₂O₅ xerogel by in situ oxidative polymerization/intercalation of N‐propane sulfonic acid aniline in the presence of air (V₂O₅ being the oxidation agent). The PSPAN/V₂O₅ nanocomposites were characterized by XRD, TEM, TGA, FTIR, UV–vis‐NIR, and conductivity measurement. The results show that the V₂O₅ maintains lamellar structure, but its interlayer spacing has increased from 1.18 to 1.31 nm. The FTIR spectra indicate that there is interaction between negatively charged oxygen of the sulfonic group of PASPN and the vanadium ion in V₂O₅ matrix. The electrical conductivity of PSPAN/V₂O₅ nanocomposite reached the value of 1.2 × 10^?2 S/cm, which is 10⁴ times higher than that of the V₂O₅ xerogel, and is 10² times more than that of the PSPAN. It was found that the aging in air facilitated the chain growth of PSPAN between the V₂O₅ lamellas, resulting in the increase of the electrical conductivity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2569–2574, 2007     

Preparation and characterization of acrylic acid/itaconic acid hydrogel coatings containing silver nanoparticles

Hydrogel silver nanocomposites have been used in applications with excellent antibacterial performance. Acrylic acid (AA)/itaconic acid (IA) hydrogels silver nanocomposites were prepared and applied as a coating on a textile substrate. Hydrogel matrices were synthesized first by the polymerization of an AA/IA aqueous (80/20 v/v) solution and mixed with 2‐2‐azobis(2‐methylpropionamide) diclorohydrate and N,N′‐methylene bisacrylamide until the hydrogel was formed. Silver nanoparticles were generated throughout the hydrogel networks with an in situ method via the incorporation of the silver ions and subsequent reduction with sodium borohydride. Cotton (C) and cotton/polyester (CP) textile fibers were then coated with these hydrogel silver nanocomposites. The influence of these nanocomposite hydrogels on the properties of the textile fiber were investigated by infrared spectroscopy (attenuated total reflectance), scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and antibacterial tests against Pseudomona aeruginosa and Staphylococcus aureus. The better conditions, in which no serious aggregation of the silver nanoparticles occurred, were determined. It was proven that the textiles coated with hydrogels containing nanosilver had an excellent antibacterial abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2713–2721, 2013     

Graft copolymerization of acrylic acid onto cellulose: Effects of pretreatments and crosslinking agent

The graft copolymerization of acrylic acid (AA) and 2‐acrylamido 2‐methylpropane sulfonic acid (AASO₃H) onto cellulose, in the presence or absence of crosslinking agent N,N′‐methylene bisacrylamide (NMBA), by using different concentrations of ceric ammonium nitrate (CAN) initiator in aqueous nitric acid solution at either 5 or 30°C was investigated. To investigate the effect of pretreatment of cellulose on the copolymerization, before some grafting reactions cellulose was pretreated with either 2 or 20 wt % NaOH solutions or heated in distilled water/aqueous nitric acid (2.5 × 10^?3 M) at 55°C. To determine how the excess of initiator affects the grafting and homopolymerization, separate reactions were carried out by removing the excess of ceric ions by filtration of the mixture of initiator solution and cellulose before the monomer addition. Extraction‐purified products were characterized by grafting percentage and equilibrium swelling capacity. Pretreatment of cellulose with NaOH solutions decreased the grafting percentage of copolymers. In the case of AA–AASO₃H mixtures, nonpretreated cellulose gave a higher grafting percentage than NaOH‐pretreated cellulose. Filtration also lowered the grafting of AA on the cellulose in the cases of pretreatment with either water or nitric acid. Copolymers with the highest grafting percentage (64.8%) and equilibrium swelling value (105 g H₂O/g copolymer) were obtained in grafting reactions carried out in the presence of NMBA at 5°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2267–2272, 2001     

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln³⁺) from the minor actinides (MAs) Am³⁺ and Cm³⁺. Traditional TALSPEAK organic phase is comprised of the monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0–2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. This process balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. In this study, the aqueous phase has been modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2), and separations were performed without any effect on phase-transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H⁺] 1.6–3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.     

The Effect of Ethanol on Nanostructures of Mixed Cationic and Anionic Surfactants

Micellization of tetradecyl trimethyl ammonium bromide (TTAB) and sodium dodecyl sulfate (SDS) in water–ethanol (ET) micellar solutions, with the weight percent of ET changing within the range 0–30, was studied by means of surface tension and conductivity measurements. Surface tension measurements also provided information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. Information about the degree of counterion dissociation and phase transition was obtained through conductivity measurements. Cyclic voltammetry (CV) and dynamic light scattering (DLS) was also employed to investigate the mixed micellar behavior of the binary mixtures. It was shown that an excess of cationic surfactant and ET resulted in a phase transition of vesicles and large micelles to mixed micelles. The regular solution theory approximation was used to determine various micellar parameters of ideal systems. The regular solution interaction parameter (β) suggests that the formation of mixed micelles is due to the synergistic interactions in the case of TTAB/SDS systems and becomes affected by the water/ET ratio.     

Ionic graft copolymerization. VI. Graft copolymerization of β-propiolactone and N-vinylcarbazole onto trunk polymer containing carboxylic acid,sulfonic acid,and their salts

It was pointed out in previous papers that both cationic and anionic polymerization might be involved simultaneously in grafting onto trunk polymers containing ? COOH or ? SO₃Na. The graft copolymerization of β-Propiolactone (βPL)–N-vinylcarbazole (NVCZ) onto styrene-divinylbenzene copolymers containing carboxylic acid, sulfonic acid, and their salts was carried out in order to distinguish between the polymers produced by anionic and cationic mechanisms. The polymer obtained by the polymerization of βPL–NVCZ with BF₃·OEt₂, a typical cationic catalyst, consisted mainly of NVCZ units, but the polymer obtained with BuLi, a typical anionic catalyst, consisted mainly of βPL units. In the graft copolymerization of NVCZ–βPL onto trunk polymer containing ? COOH, the NVCZ contents of the branch polymer and the tolueneinsoluble fraction were estimated to be ca. 50 mole-%; therefore these polymers were produced by both cationic and anionic mechanisms. In the case of graft copolymerization onto the trunk polymer containing SO₃Na, it was found that both cationic and anionic polymerization also occurred simultaneously.     

Studies on the synthesis and properties of thermotropic liquid crystalline copoly(amide–ester–imide) derived from N-(hydroxyphenyl)phthalimide-4-carboxylic acid with amino acid

Three series of copoly(amide–ester–imide)s were prepared from amino acid (4-aminobenzoic acid, 3-aminobenzoic acid, or 6-aminohexanoic acid) and N-(4-hydroxyphenyl)phthalimide-4-carboxylic acid (M1), N-(3-hydroxyphenyl)phthalimide-4-carboxylic acid (M2), or N-(2-methyl-4-hydroxyphenyl)phthalimide-4-carboxylic acid (M3) in the presence of diphenylchlorophosphate (DPCP) and pyridine as direct condensation agents. The inherent viscosities of copoly(amide–ester–imide)s were in the range of 0.13–0.95 dL/g. Thermotropic liquid crystalline (LC) behavior of these polymers was examined by differential scanning calorimetry (DSC) and optical polarizing microscopy. These copoly(amide–ester–imide)s ( IIa, IIe, IIIa , and IIIc ) polymerized from 3-aminobenzoic acid or 6-aminohexanoic acid with M1 or M3, respectively, showed thermotropic liquid crystalline behavior in the range of 190–426°C. © 1995 John Wiley & Sons, Inc.     

Effect of lecithins partly replacing rumen‐protected fat on fatty acid digestion and composition of cow milk

The effects on fatty acid digestibility and milk fat composition of calcium soaps of palm oil fatty acids and of a 25% replacement of the Ca soaps by four different lecithins (raw, deoiled and deoiled/partially hydrolysed soy lecithin, raw canola lecithin) and soybean oil were investigated in six lactating cows each. The complete diets contained the lipid supplements at proportions of 30 g fatty acids/kg dry matter. Partial replacement of Ca soaps by soy or canola lecithins and soybean oil had small but significant effects on fatty acid digestion and utilisation, as well as the fatty acid profile in milk. Relative to Ca soaps alone, C 16:0 digestibility was slightly higher with lecithins, and percentage of conjugated linoleic acid and trans C 18:1 in milk fat increased while proportion of C 16:0 decreased. Deoiling of lecithins slightly reduced the effects on C 16:0 digestibility and excretion with milk. The influence of lecithin processing was higher than the differences between raw soy and raw canola lecithin. Nevertheless, most of the few effects observed may be related to the fatty acids supplied with the lecithins but, regarding C 18:1 trans‐11 and odd chain fatty acids, there is some evidence that lecithins impair rumen microbial activity less than soybean oil.     

Studies on synthetic-polymer plates with high surface energy. II. Diethylene glycol bis(allyl carbonate)–unsaturated carboxylic acid system

Polymer plates with high surface energy were prepared by the procedure described in the previous paper, using diethylene glycol bis(allyl carbonate) as a substrate polymer and acrylic acid or methacrylic acid as a hydrophilic monomer. By the alkali treatment (immersing in an aqueous 0.1N NaOH solution for 2 h), the resulting polymer plates had good water wettability (contact angle for water = 10°) and sufficient mar resistance (the scratching hardness = 45–50 g) in a dry state, and their clarities were higher than those for DAP systems previously reported. The surface densities of carboxyl groups on the polymer plate estimated by use of the McBain's equation were 0.18–0.46 molecule/Ų.