Acidity indicated

The dotted lines represent hydrogen bonds. The high boiling point and viscosity of the pure acid indicate strong intermolecular forces of this kind. 

We are not concerned here with the mechanism of nitrosation, but with the anticatalytic effect of nitrous acid upon nitration, and with the way in which this is superseded with very reactive compounds by an indirect mechanism for nitration. The term nitrous acid indicates all the species in a solution which, after dilution with water, can be estimated as nitrous acid. 

Metanil yellow, diphenylaminoazo-m-benzene sulfonic acid (indicator) dissolve 0.25 g in 100 mL alcohol pH range red 1.2-2.3 yellow. 

Trinitrobenzoic acid, 2,4,6-trinitrobenzoic acid (indicator) dissolve 0.1 g in 100 mL water pH range colorless 12.0-13.4 orange-red. 

This interesting conversion of a five- into a six-membered heterocyclic ring was proven by the isolation of the enzyme GTP-cyclohydrolase from E. coli (71MI21600) and a similar one from Lactobacillus platarum (B-71MI21601) which catalyzes the reaction (300)(303). Dephosphorylation leads to 7,8-dihydro-D-neopterin (304), which is then cleaved in the side-chain to 6-hydroxymethyl-7,8-dihydropterin (305), the direct precursor of 7,8-dihy-dropteroic acid and 7,8-dihydrofolic acid (224). The alcohol (305) requires ATP and Mg " for the condensation with p-aminobenzoic and p-aminobenzoylglutamic acid, indicating pyrophosphate formation to (306) prior to the substitution step. 

At times the reaction is slow in starting. Not more than 50-60 g. of benzyl chloride is added at first, and the mixture is heated until the evolution of hydrochloric acid indicates that the reaction is under way. If too much benzyl chloride is present when the reaction starts, the contents of the flask may boil over. 

Tsai then applied thick films of the polyamic acid of PMDA and 4-BDAF to polished silver substrates and thermally imidized the films. The substrates were immersed into liquid nitrogen, causing the films to delaminate and XPS was used to examine the polyimide and silver fracture surfaces (see Fig. 33). The C(ls) spectra of the silver fracture surface were very similar to those of neat polyamic acid, indicating that imidization was inhibited by interaction of the polyamic acid with the silver substrate. This was evident from the observation of two peaks near... 

When trigonelline is heated in closed tubes with baryta water at 120°, it gives rise to methylamine, whilst similar treatment with hydrochloric acid at 260° furnishes methyl chloride and nicotinic acid (pyridine-3-carboxylic acid), indicating that it is the methylbetaine of nicotinic acid. 

The mechanism of the reaction of ethyl glyoxylate 4 with 2,3-dimethyl-l,3-hutadiene 5 leading to the ene product 7 is shown in Scheme 4.5. This brief introduction to the reaction mechanism for cycloaddition reactions of carhonyl compounds activated hy Lewis acids indicates that many factors influence the course of the reaction. 

Schimmel Co. have proposed to detect esters of fixed acids by an estimation of the amount of volatile acids obtained by distilling the acidified saponification residues, and comparing this figure with the amount of acid indicated by the saponification value. 

The mechanism shown in Figure 21.7 is supported by isotope-labeling studies. When ethyl propanoate labeled with lsO in the ether-like oxygen is hydrolyzed in aqueous NaOH, the l80 label shows up exclusively in the ethanol product. None of the label remains with the propanoic acid, indicating that saponification occurs by cleavage of the C-OR bond rather than the CO—R bond. 

The following experiment was performed to determine the equilibrium constant in (43). A 1.22 gram sample of benzoic acid was dissolved in 1.00 liter of water at 25°C. With dyes whose color is sensitive to acidity (indicators) the concentration of H+(aq) was estimated to be 8 X 10 4 M. 

Procedure. Weigh out accurately an amount of the salt which will contain about 0.25 g of chromium, and dissolve it in 50 mL distilled water. Add 20 mL of ca 0.1 M silver nitrate solution, followed by 50 mL of a 10 per cent solution of ammonium or potassium persulphate. Boil the liquid gently for 20 minutes. Cool, and dilute to 250 mL in a graduated flask. Remove 50 mL of the solution with a pipette, add 50 mL of a 0.1 M ammonium iron(II) sulphate solution (Section 10.97, Procedure A), 200 mL of 1M sulphuric acid, and 0.5 mL of /V-phenylanthranilic acid indicator. Titrate the excess of the iron(II) salt with standard 0.02M potassium dichromate until the colour changes from green to violet-red. 

Procedure. Weigh out accurately about 0.2 g of arsenic(III) oxide, previously dried at 105-110 °C for 1-2 hours, and transfer to a 500 mL beaker or to a 500 mL conical flask. Add 20 mL of approx. 2M sodium hydroxide solution, and warm the mixture gently until the arsenic(III) oxide has completely dissolved. Cool to room temperature, and add 100 mL water, followed by 25 mL 2.5M sulphuric acid. Then add 3 drops 0.01 M osmium tetroxide solution (0.25 g osmium tetroxide (CARE FUME CUPBOARD) dissolved in 100 mL 0.05M sulphuric acid) and 0.5 mL AT-phenylanthranilic acid indicator (or 1-2 drops of ferroin). Titrate with the 0.1 M cerium(IV) sulphate solution until the first sharp colour change occurs (see Discussion above). Repeat with two other samples of approximately equal weight of arsenic(III) oxide. 

The kinetics and mechanism of formation of 2,3-naphthotriazole (6.49) were studied by Oh and Williams (1989). In aqueous solutions of 0.2-1.0 m HC104 the dependence of the reaction on acidity indicated simultaneous involvement of the protonated and unprotonated substrates (6.47 and 6.48 respectively). The unproton-ated form of 2,3-diaminonaphthalen (6.48) reacts with the nitrosyl ion (NO+) on encounter (rate constant k ). The 2-NH3 substituent reduces the reactivity of 6.47 by a factor of about 800 (ki/k2). The rate-limiting formation of the diazonium ion (Scheme 6-33) is followed by a rapid cyclization (Scheme 6-34). 

Katritzky et al.508 have measured rates of deuteration of aminopyridine by deuterated sulphuric acid (Table 146), and for the 4-amino and 2-amino-5-methyl compounds, the general increase in rate with increasing acidity, dlogkjd (—H0) 0.6, shows reaction to be occurring on the conjugate acids. For the latter compound this is only true at acidities > —H0 = 4.0, below which rates are relatively independent of acidity indicating reaction on the free base. For the 2,6-dichloro... 

Rate coefficients have been determined for protodeboronation of benzene- and thiophene-boronic acids in a range of aqueous perchloric acid mixtures at temperatures between 25 and 90 °C630. First-order rate coefficients are given in Table 204, but not all of the rates were measured at the acidities indicated (see Table footnote), but were corrected to these making use of the linear relationship which was found, in preliminary experiments, to exist between log rate and H0. Similarly, the relative reactivities to thiophene-2-, thiophene-3-, and benzene-boronic acid (8.5 x 10s, 7.1 x 103, and 1.0, respectively) were obtained at an H0... 

Stability constants as a function of temperature and the calculated complexation enthalpies and entropies of the associated reactions are given in Table II. The results of duplicate experiments at 2.0 M acidity and ionic strength are shown as the last entry in the table. Comparison of the results at 25°C, and 1.0 and 2.0 M acidity indicate an approximate inverse first order stoichiometry in [IT "] for the Kj and acid independence for K2. 

Pult+, and HSOIJ, this result combined with our results at 1 M acidity indicates an inverse first power stoichiometry in [H+] for the 1 1 complex, and acid independence in the formation of the second complex. If we assume n = m 1 in equation 2, the equilibria and associated stability constants in this system are... 

McMillan has reviewed the chemistry of Ag(II) and Ag(IlI). Paramagnetism and electron spin resonance studies confirm the presence of Ag(ll) (as opposed to equimolar Ag(I)+Ag(III)). The colours of Ag(II) solutions in various mineral acids indicate the existence of complexes, the oxidising power of which is apparent from their decomposition even at 0 °C, although high acidity promotes stability. Rapid isotope exchange between Ag(I) and Ag(n) is considered to result from the equilibrium... 

Although Ce(IV) oxidation of carboxylic acids is slow and incomplete under similar reaction conditions , the rate is greatly enhanced on addition of perchloric acid. No kinetics were obtained but product analysis of the oxidations of -butyric, isobutyric, pivalic and acetic acids indicates an identical oxidative decarboxylation to take place. Photochemical decomposition of Ce(IV) carbo-xylates is highly efficient unity) and Cu(ll) diverts the course of reaction in the same way as in the thermal oxidation by Co(IIl). Direct spectroscopic evidence for the intermediate formation of alkyl radicals was obtained by Greatorex and Kemp ° who photoirradiated several Ce(IV) carboxylates in a degassed perchloric acid glass at 77 °K in the cavity of an electron spin resonance spectro-... 

For cinnamic acid at 9.6 °C, a = 0.107, b = 1.25 and k = 0.69 l.mole .sec E = 26.7 0.5 kcal.mole" and AS = 34.5 eu. Identification of products of oxidation of a number of acids indicates two concurrent mechanisms. Predominating is direct attack on the double bond to give, ultimately, cleavage products, e.g. benzaldehyde from cinnamic acid (some phenylacetaldehyde is also found, indicating oxidative decarboxylation to occur) and also acetophenone from 3-phenylcrotonic acid. 

The mechanism suggested by these kinetics depends on the simultaneous oxidation of two ions in substrate-metal ion complexes so that free radicals are not produced. A few data on Cr(II) reduction of these unsaturated acids indicate simple second-order kinetics ... 

A differential vapour-pressure technique has been used to determine the molecular weights of phosphonic and phosphinic acids in 95% ethanol. Cryoscopic and n.m.r. studies have been made on solutions of phosphinic acids in sulphuric acid and oleum. Mass spectrometry has indicated the ready formation of phosphinylium ions after electron bombardment of phosphonic and phosphinic acids and their derivatives. However, the cryoscopic results in sulphuric acid indicated that reaction did not proceed beyond protonation, and the n.m.r. study on oleum solutions suggested that sulphonation occurred. 

Fig. 1. Amino acid sequence homology between the neonatal fast-twitch and slow-twitch skeletal muscle forms of the Ca -ATPase. The sequence of the slow Ca -ATPase is shown above the neonatal fast-twitch form, with nonhomologous amino acids indicated by asterisks. The sequence of the slow ATPase is shifted to the right by one residue at residue 505 to allow realignment after the difference in sequence length. Ml-MlO, membrane spanning regions S1-S5, stalk sectors Tl, T2, major tryptic cleavage sites P,...

The pH indicator shows the acid or basic properties of sample molecnles. Commonly used for acid indicating are solutions of bromocresol green (20 mg dissolved in 10 ml of ethanol combined with 1 ml of 0.1-molar aqueous NaOH) or bromophenol blue (20 mg dissolved in 10 ml of ethanol, pH-adjusted with 0.1-molar NaOH or 0.2% aqneous citric acid). In the presence of acids, 2,6-dichloroindophenol (40 mg dissolved in 100 ml of ethanol) changes the color from blue to red. The fluorescent dye acridine orange (20 mg dissolved in 100 ml of ethanol) changes pH-dependently the color of its flnorescence from yellow-green to yellow. 

Hydrolysis of polyamide-based formulations with 6 N HC1 followed by TLC allows differentiation between a-aminocaproic acid (ACA) and hexamethylenedi-amine (HMD) (hydrolysis products of PA6 and PA6.6, respectively), even at low levels. The monomer composition (PA6/PA6.6 ratio) can be derived after chromatographic determination of the adipic acid (AA) content. Extraction of the hydrolysate with ether and derivatisa-tion allow the quantitative determination of fatty acids (from lubricants) by means of GC (Figure 3.27). Further HC1/HF treatment of the hydrolysis residue, which is composed of mineral fillers, CB and nonhydrolysable polymers (e.g. impact modifiers) permits determination of total IM and CB contents CB is measured quantitatively by means of TGA [157]. Acid hydrolysis of flame retarded polyamides allows to determine the adipic acid content (indicative of PA6.6) by means of HPLC, HCN content (indicative of melamine cyanurate) and fatty acid (indicative of a stearate) by means of GC [640]. Determination of ethylene oxide-based antistatic agents... 

What makes indicators change color in the presence of acids and bases A color change is often the sign that a chemical reaction has occurred, and this is no exception Acid-base indicators are actually acids or bases themselves. They change colors because the acid and its conjugate base (or the base and its conjugate acid) are different colors. For example, suppose an acidic indicator, abbreviated HIn (this is not really a chemical formula, it is just a way to show an indicator that has hydrogen ions to donate), is dissolved in water. It... 

Notice that this is a reversible reaction. If the acidic indicator (HIn) is phenolphthalein and an acid is introduced into the solution, more hydrogen ions are available to react with the In- molecule. This shifts the reaction more to the left-hand side, and... 

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