Formaldehyde kinetics

Hippel, P.H. von, Wang, K.-Y. Dynamic aspects of native DNA structure kinetics of the formaldehyde reaction with calf thymus DNA. J. Mol. Biol. 61 (1971) 587-613... 

Anhydrous, monomeric formaldehyde is not available commercially. The pure, dry gas is relatively stable at 80—100°C but slowly polymerizes at lower temperatures. Traces of polar impurities such as acids, alkahes, and water greatly accelerate the polymerization. When Hquid formaldehyde is warmed to room temperature in a sealed ampul, it polymerizes rapidly with evolution of heat (63 kj /mol or 15.05 kcal/mol). Uncatalyzed decomposition is very slow below 300°C extrapolation of kinetic data (32) to 400°C indicates that the rate of decomposition is ca 0.44%/min at 101 kPa (1 atm). The main products ate CO and H2. Metals such as platinum (33), copper (34), and chromia and alumina (35) also catalyze the formation of methanol, methyl formate, formic acid, carbon dioxide, and methane. Trace levels of formaldehyde found in urban atmospheres are readily photo-oxidized to carbon dioxide the half-life ranges from 35—50 minutes (36). 

Nifurtoinol. Treatment of nitrofurantoin with formaldehyde gives nihirtoinol, 3-hydroxymethyl-l-[5-nitro-2-furanyl)methyleneamino]-2,4-imidazohdinedione, a urinary tract antibacterial (46). The kinetics of decomposition of this dmg and its potential as a prodmg of nitrofurantoin have been reported (47). 

In general, the reaction between a phenol and an aldehyde is classified as an electrophilic aromatic substitution, though some researchers have classed it as a nucleophilic substitution (Sn2) on aldehyde [84]. These mechanisms are probably indistinguishable on the basis of kinetics, though the charge-dispersed sp carbon structure of phenate does not fit our normal concept of a good nucleophile. In phenol-formaldehyde resins, the observed hydroxymethylation kinetics are second-order, first-order in phenol and first-order in formaldehyde. 

The study of PF polymerization is far more difficult than that of methylolation due to the increased complexity of the reactions, the intractability of the material, and a resulting lack of adequate analytical methods. When dealing with methylolation, we saw that every reactive ring position had its own reaction rate with formaldehyde that varied with the extent of prior reaction of the ring. Despite this rate sensitivity and complexity, all reactions kinetics were second-order overall, first-order in phenol reactive sites and first-order in formaldehyde. This is not the case with the condensation reactions. 

Alkaline co-condensation to yield commercial resins and the products of reaction obtained thereof [93,94] as well as the kinetics of the co-condensation of mono methylol phenols and urea [104,105] have also been reported [17]. Model reactions in order to prove an urea-phenol-formaldehyde co-condensation (reaction of urea with methylolphenols) are described by Tomita and Hse [98,102, 106] and by Pizzi et al. [93,104] (Fig. 1). 

Interestingly, true hydrides, such as NaH and KH, do not reduce carbonyl groups. Using energies of hydride and methoxide (at left), calculate AH xn for the reduction of formaldehyde by H. Is this reaction more or less favorable than those based on ZH4 Can the low reactivity of NaH and KH be attributed to thermodynamic factors, or must kinetic factors be responsible ... 

The addition of water across carbon-carbon double bonds, a reaction thoroughly investigated by Lucas and Taft, requires strong activation and is catalyzed by hydrogen ions and hydroxyl ions. Addition of water across the 0= =0 bond of aldehydes has also been studied kinetically. Whereas chloral and formaldehyde are largely hydrated (at equilibrium in dilute aqueous solution), acetaldehyde and other... 

DFT molecular dynamics simulations were used to investigate the kinetics of the chemical reactions that occur during the induction phase of acid-catalyzed polymerization of 205 [97JA7218]. These calculations support the experimental finding that the induction phase is characterized by the protolysis of 205 followed by a rapid decomposition into two formaldehyde molecules plus a methylenic carbocation (Scheme 135). For the second phase of the polymerization process, a reaction of the protonated 1,3,5-trioxane 208 with formaldehyde yielding 1,3,5,7-tetroxane 209 is discussed (Scheme 136). 

Some results which are consistent with this mechanism have been obtained by Ishii and Yamashita385, who found that the kinetics of the reaction of m-xylene with formaldehyde and hydrogen chloride (to give the 4-substituted product) were third-order overall. However, this was followed by a slow di-chloromethylation which was of zeroth-order, but no interpretation or further mechanistic details are available. 

Base-catalyzed phenol-formaldehyde reactions exhibit second-order kinetics [Eq. (5)]. Several alkylphenols such as cresols also follow this rate equation ... 

The reaction conditions, formaldehyde-to-phenol ratios, and concentration and type of catalyst govern the mechanisms and kinetics of resole syntheses. Higher formaldehyde-to-phenol ratios accelerate the reaction rates. This is to be expected since phenol-formaldehyde reactions follow second-order kinetics. Increased hydroxymethyl substitution on phenols due to higher formaldehyde compositions also leads to more condensation products.55... 

Dynamic DSC scans of resole resins show two distinguishable reaction peaks, which correspond to formaldehyde addition and die formation of edier and metiiy-lene bridges characterized by different activation energies. Kinetic parameters calculated using a regression analysis show good agreement widi experimental values.75... 

Methanol oxidation on Pt has been investigated at temperatures 350° to 650°C, CH3OH partial pressures, pM, between 5-10"2 and 1 kPa and oxygen partial pressures, po2, between 1 and 20 kPa.50 Formaldehyde and C02 were the only products detected in measurable concentrations. The open-circuit selectivity to H2CO is of the order of 0.5 and is practically unaffected by gas residence time over the above conditions for methanol conversions below 30%. Consequently the reactions of H2CO and C02 formation can be considered kinetically as two parallel reactions. 

Figure 8.46. Effect of Pt catalyst dimensionless potential ]1=FUwr/RT on the kinetic constants of formation of formaldehyde (a) and CO2 (b) during CH3OH oxidation on Pt/YSZ Conditions as in Fig. 8.45.50 Reprinted with permission from Academic Press.

Typical non-enolising aldehydes are formaldehyde and benzaldehyde, which are oxidised by Co(III) Ce(IV) perchlorate and sulphate , and Mn(III) . The main kinetic features and the primary kinetic isotope effects are the same as for the analogous cyclohexanol oxidations (section 4.3.5) and it is highly probable that the same general mechanism operates. kif olko20 for Co(III) oxidation of formaldehyde is 1.81 (ref. 141), a value in agreement with the observed acid-retardation, i.e. not in accordance with abstraction of a hydroxylic hydrogen atom from H2C(OH)2-The V(V) perchlorate oxidations of formaldehyde and chloral hydrate display an unusual rate expression, viz. 

The Co(ni) perchlorate oxidation of substituted and unsubstituted benzal-dehydes has kinetics and a low isotope effect (2.3 at 10 °C) in complete analogy with cyclohexanol and formaldehyde . Ring-substitution by electronegative groups accelerates reaction. 

The oxidations of formic acid by Co(III) and V(V) are straightforward, being first-order with respect to both oxidant and substrate and acid-inverse and slightly acid-catalysed respectively. The primary kinetic isotope effects are l.Sj (25°C)forCo(IU)and4.1 (61.5 C°)for V(V). The low value for Co(lII) is analogous to those for Co(IIl) oxidations of secondary alcohols, formaldehyde and m-nitrobenzaldehyde vide supra). A djo/ h20 for the Co(III) oxidation is about 1.0, which is curiously high for an acid-inverse reaction . The mechanisms clearly parallel those for oxidation of alcohols (p. 376) where Rj and R2 become doubly bonded oxygen. 

The oxidation of the non-enolising formaldehyde to formic acid by Cu(n) sulphate in the presence of glycerol follows kinetics ... 

The Holy Grail of catalysis has been to identify what Taylor described as the active site that is, that ensemble of atoms which is responsible for the surface reactions involved in catalytic turnover. With the advent of atomically resolving techniques such as scanning tunnelling microscopy it is now possible to identify reaction centres on planar surfaces. This gives a greater insight also into reaction kinetics and mechanisms in catalysis. In this paper two examples of such work are described, namely CO oxidation on a Rh(llO) crystal and methanol selective oxidation to formaldehyde on Cu(llO). 

Finally, we have discussed the effect of incomplete Cj oxidation product formation for fuel cell applications and the implications of these processes for reaction modeling. While for standard DMFC applications, formaldehyde and formic acid formation will be negligible, they may become important for low temperature applications and for microstructured cells with high space velocities. For reaction modeling, we have particularly stressed the need for an improved kinetic data base, including kinetic data under defined reaction and transport conditions and kinetic measurements on the oxidation of Ci mixtures with defined amounts of formaldehyde and formic acid, for a better understanding of cross effects between the different reactants at an operating fuel cell anode. 

Nakabayashi S, Tamura M, Uosaki K. 1998. Kinetic coupling of formaldehyde oxidation and oxide formation on a platinum electrode. Bull Chem Soc Jpn 71 67-71. 

The complex batch reaction between formaldehyde. A, and sodium p-phenol sulphonate, B, proceeds in accordance with the following complex reaction scheme. All the reactions follow second-order kinetics. Components C, D and F are intermediates, and E is the final product. 

According to R. Brdicka and K. Vesely the carbonyl form of formaldehyde is reduced and the limiting kinetic current is given by the rate of the chemical volume reaction of dehydration. An analogous situation occurs for the equilibria among complexes, metal ions and complexing agents if the rates of complex formation and decomposition are insufficient to preserve the equilibrium. A simple example is the deposition of cadmium at a mercury electrode from its complex with nitrilotriacetic COO"... 

---