Aqueous solutions enthalpy

Notably, pKa values pertaining to solution equilibria are not usually distorted by special solvation effects. The same acidity order for 4-substituted pyridinium ions is found in the gas phase. In fact, a linear free energy (aqueous solution)-enthalpy (gas phase) relationship exists substituent effects are 3.5 times larger in the gas phase. In other words, the aqueous solvent, relative to the gas phase, attenuates the effect of substituents by its higher dielectric constant and by hydrogen bonding.52... 

Thermodynamic properties of solutions are not only useful for estimating the feasibility of reactions in solution, but they also offer one of the better methods of investigating the theoretical aspects of solution structure. This is particularly true for the standard partial molal entropy, heat capacity, and volume of the solutes, values of which are sensitive to the arrangement of solvent molecules around a solute molecule. They have been examined extensively in aqueous solution for the purpose of structure interpretation and more recently in non-aqueous solutions. Enthalpies and free energies of solvation and transfer between... 

Table 5.1 also shows typical nonmonotonous dependences of CMC on temperatirre for [C Cj2Pyrr]Br and [C CgPyrr]Br, which can be interpreted as the interplay between the two driving forces that concur to miceUization in aqueous solutions enthalpy- versus... 

Table 7.3 lists data for several common ions in aqueous solution. Enthalpies of formation in solution depend on the solute concentration. These data are representative for dilute aqueous solutions (abouf 1 M), fhe fype of solution that we normally deal with. Some of fhese dafa are used in Example 7-13. 

Fluoroacetic acid [144-49-OJ, FCH2COOH, is noted for its high, toxicity to animals, including humans. It is sold in the form of its sodium salt as a rodenticide and general mammalian pest control agent. The acid has mp, 33°C bp, 165°C heat of combustion, —715.8 kJ/mol( —171.08 kcal/mol) (1) enthalpy of vaporization, 83.89 kJ /mol (20.05 kcal/mol) (2). Some thermodynamic and transport properties of its aqueous solutions have been pubHshed (3), as has the molecular stmcture of the acid as deterrnined by microwave spectroscopy (4). Although first prepared in 1896 (5), its unusual toxicity was not pubhshed until 50 years later (6). The acid is the toxic constituent of a South African plant Dichapetalum i mosum better known as gifirlaar (7). At least 24 other poisonous plant species are known to contain it (8). 

Studies on metal-pyrazole complexes in solution are few. The enthalpy and entropy of association of Co(II), Ni(II), Cu(II) and Zn(II) with pyrazole in aqueous solution have been determined by direct calorimetry (81MI40406). The nature of the nitrogen atom, pyridinic or pyrrolic, involved in the coordination with the metal cannot be determined from the available thermodynamic data. However, other experiments in solution (Section 4.04.1.3.3(i)) prove conclusively that only the N-2 atom has coordinating capabilities. 

The standard enthalpies of formation of ions in aqueous solution listed at the bottom of Table 8.3 are relative values, established by taking... 

The relationship of thermodynamic functions of selective bonding of Hb to a series of carboxylic CP in the variation of the degree of ionization of carboxylic groups is expressed by the effect of enthalpy-entropy compensation (Fig. 18). The compensation effect of enthalpy and entropy components is the most wide-spread characteristic of many reactions in aqueous solutions for systems with a cooperative change in structure [78],... 

In recent years, aqueous solutions of Xe03 have been used to oxidize a species in solution, from which A[H°m can be calculated when AH for the oxidation reaction is combined with AH for other reactions. The noble gas oxide Xe03 is used as an oxidant because of its stability and the fact that the final reaction product is Xe(g), which has a zero enthalpy of formation and is easily removed from the reaction mixture. As an example, O Hare4 has reported AfHcm for UCI4. We will not go through the details of his procedure, but the critical step involved measuring A TH for the reaction... 

Table 9.2 Standard heat capacities, entropies, enthalpies, and Gibbs free energies of formation of some common ions in aqueous solution at T= 298.15 K...

Because reactions in the body take place in aqueous solution, this value is not the same as the enthalpy change for the reaction in the body. However, the two values are fairly close. Therefore, the oxidation of glycine, which we have found to be exothermic, is a potential source of energy in the body. 

Fig. 1.2 Standard enthalpy changes of (a) the complexing of lanthanide ions in aqueous solution by EDTA" ( left-hand axis) (b) the standard enthalpy change of reaction 2, the dichloride being a di-f...

The enthalpy of decomposition of this peracid is relatively high (AHcj = -1.83 kJ/g - average risk according to CHETAH criterion C,). Its aqueous solutions are unstable. Solutions that contain 80% of peracid detonate when they are stirred (even at -10°C). The usual way of preparing this peracid involves the effect of hydrogen peroxide when metaboric acid is present however, although this operating method was followed, serious accidents have occurred. 

The EA/CA ratio was proposed as a measure of hardness of the Lewis acid, and EB/CB as hardness of the Lewis base in aqueous solution (17). It now seems that the E/C ratio is not a measure of hardness in the sense in which Pearson (5,5a) defined hardness. Rather, the E/C ratio for a Lewis acid or base is a measure of the tendency to ionicity in the M-L bonds formed. The EAICA ratio should rather be called IA, and the EbICb ratio IB, the tendency to ionic bonding in forming the M-L bond. Acids and bases in Tables I and II are placed in order of increasing tendency towards ionicity in the M-L bond, according to the E/C ratios IA and 7b. A justification for this interpretation is that the order of IA values for metal ions in aqueous solution strongly resembles the order of hardness derived by Pearson (19) from enthalpies of complex forma-... 

Fig. 8. Correlation between Pearson s hardness parameter (7P) derived from gas-phase enthalpies of formation of halide compounds of Lewis acids (19), and the hardness parameter in aqueous solution (/A), derived from formation constants of fluoride and hydroxide complexes in aqueous solution (17). The Lewis acids are segregated by charge into separate correlations for monopositive ( ), dipositive (O), and tripositive ( ) cations, with a single tetrapositive ion (Zr4+, ). The /P value for Tl3+ was not reported, but the point is included in parentheses to show the relative ionicity of Tl(III) to ligand bonds. 

If a substance is to be dissolved, its ions or molecules must first move apart and then force their way between the solvent molecules which interact with the solute particles. If an ionic crystal is dissolved, electrostatic interaction forces must be overcome between the ions. The higher the dielectric constant of the solvent, the more effective this process is. The solvent-solute interaction is termed ion solvation (ion hydration in aqueous solutions). The importance of this phenomenon follows from comparison of the energy changes accompanying solvation of ions and uncharged molecules for monovalent ions, the enthalpy of hydration is about 400 kJ mol-1, and equals about 12 kJ mol-1 for simple non-polar species such as argon or methane. 

Figure 3 shows the excess enthalpy v . composition measured for aqueous solutions of n-butanol and water at 30.0 °C Figure 4 shows corresponding results for the amphiphilic side of the miscibility gap at... 

So far we have not touched on the fact that the important topic of solvation energy is not yet taken into account. The extent to which solvation influences gas-phase energy values can be considerable. As an example, gas-phase data for fundamental enolisation reactions are included in Table 1. Related aqueous solution phase data can be derived from equilibrium constants 31). The gas-phase heats of enolisation for acetone and propionaldehyde are 19.5 and 13 keal/mol, respectively. The corresponding free energies of enolisation in solution are 9.9 and 5.4 kcal/mol. (Whether the difference between gas and solution derives from enthalpy or entropy effects is irrelevant at this stage.) Despite this, our experience with gas-phase enthalpies calculated by the methods described in this chapter leads us to believe that even the current approach is most valuable for evaluation of reactivity. 

Papisov et al. (1974) performed calorimetric and potentiometric experiments to determine the thermodynamic parameters of the complex formation of PMAA and PAA with PEG. They investigated how temperature and the nature of the solvent affected the complex stability. They found that in aqueous media the enthalpy and entropy associated with the formation of the PMAA/PEG complex are positive while in an aqueous mixture of methanol both of the thermodynamic quantities become negative. The exact values are shown in Table II. The viscosities of aqueous solutions containing complexes of PMAA and PEG increase with decreasing temperature as a result of a breakdown of the complexes. 

Cations in aqueous solutions have an effective radius that is approximately 75 pm larger than the crystallographic radii. The value of 75 pm is approximately the radius of a water molecule. It can be shown that the heat of hydration of cations should be a linear function of Z /r where is the effective ionic radius and Z is the charge on the ion. Using the ionic radii shown in Table 7.4 and hydration enthalpies shown in Table 7.7, test the validity of this relationship. 

Enthalpies, Entropies, and Gibb s Energies of Transition Metal Ion Oxidation-Reduction Reactions with Hydrogen Peroxide in Aqueous Solution (T = 298 K) [23]... 

At 13.5 kN/m2 water boils at 325 K and in the absence of data as to the boiling-point rise, this will be taken as the temperature of evaporation, assuming an aqueous solution. The total enthalpy of steam at 325 K is 2594 kJ/kg. 

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