Ionic compound hydrated

The enthalpy of solution is quite small for many simple ionic compounds and can be either positive or negative. It is the difference between two large quantities, the sum of the hydration enthalpies and the lattice energy. 

Prediction of solubility for simple ionic compounds is difficult since we need to know not only values of hydration and lattice enthalpies but also entropy changes on solution before any informed prediction can be given. Even then kinetic factors must be considered. 

The small lithium Li" and beryllium Be ions have high charge-radius ratios and consequently exert particularly strong attractions on other ions and on polar molecules. These attractions result in both high lattice and hydration energies and it is these high energies which account for many of the abnormal properties of the ionic compounds of lithium and beryllium. 

It is soluble in organic solvents (a characteristic of a covalent compound). but dissolves in water and can form hydrates (a characteristic of an ionic compound), hence the hydrated must be... 

The oxide (p. 1209), chalcogenides (p. 1210) and halides (p. 1211) have already been described. Of them, the only ionic compound is HgF2 but other compounds in which there is appreciable charge separation are the hydrated salts of strong oxoacids, e.g. the nitrate, perchlorate, and sulfate. In aqueous solution such salts are extensively hydrolysed (HgO is only very weakly basic) and they require acidification to prevent the formation of polynuclear hydroxo-bridged species or the precipitation of basic salts such as Hg(OH)(N03) which contains infinite zigzag chains ... 

Ionic compounds often separate from water solution with molecules of water incorporated into the solid. Such compounds are referred to as hydrates. An example is hydrated copper sulfate, which contains five moles of H20 for every mole of CuS04. Its formula is CuS04- 5H20 a dot is used to separate the formulas of the two compounds CuS04 and H20. A Greek prefix is used to show the number of moles of water the systematic name of CuS04- 5H20 is copper(ll) sulfate pentahydrate. 

Ionic compounds are named by starting with the name of the cation (with its oxidation number if more than one charge is possible), followed by the name of the anion hydrates are named by adding the word hydrate, preceded by a Greek prefix indicating the number of water molecules in the formula unit. 

The hydrated ion [Cu(H20)6]2+ is an example of a complex, a species consisting of a central metal atom or ion to which a number of molecules or ions are attached by coordinate covalent bonds. A coordination compound is an electrically neutral compound in which at least one of the ions present is a complex. However, the terms coordination compound (the overall neutral compound) and complex (one or more of the ions or neutral species present in the compound) are often used interchangeably. Coordination compounds include complexes in which the central metal atom is electrically neutral, such as Ni(CO)4, and ionic compounds, such as K4[Fe(CN)6]. 

Many ionic compounds can have water molecules incorporated into their solid structures. Such compounds are called hydrates. To emphasize the presence of discrete water molecules in the chemical structure, the formula of any hydrate shows the waters of hydration separated from the rest of the chemical formula by a dot. A coefficient before H2 O indicates the number of water molecules in the formula. Copper(II) sulfate pentahydrate is a good example. The formula of this beautiful deep blue solid is C11SO4 5 H2 O, indicating that five water molecules are associated with each CuSOq unit. Upon prolonged heating, CuSOq 5 H2 O loses its waters of hydration along with its color. Other examples of hydrates include aluminum nitrate nonahydrate, A1 (N03)3 9 H2 O,... 

Whereas we can deduce the ratios of anions to cations in an ionic compound from the eiectricai charges on the individuai ions, we cannot determine the number of water moiecuies in a hydrate from the nature of the anions and cations in the ionic compound. The number of water moiecuies, which can range from 0 to as high as 18, must be determined by doing experiments. In fact, some ionic substances exist in several different forms with different numbers of water moiecuies. 

In cases where the solvation energies are large, as for example when ionic compounds dissolve in water, these hydrophobic effects, based on adverse changes in entropy, are swamped. Dissolving such compounds can be readily accomplished due to the very large energies released when the ions become hydrated. 

Many ionic compounds contain what used to be referred to as water of crystallization . For example, magnesium chloride can exist as a fully hydrated salt which was formerly written MgCla.bHjO, but is more appropriately written Mg(OH2)eCl2, since the water molecules occupy coordination sites around the magnesium ions. This is typical. In most compounds that contain water of crystallization, the water molecules are bound to the cation in an aquo complex in the manner originally proposed by Alfred Werner (1866-1919) in 1893 (Kauffman, 1981). Such an arrangement has been confirmed in numerous cases by X-ray diffraction techniques. 

When an ionic compound dissolves in water, energy is needed to break the ionic bonds of the crystal. As the ions attach to the water molecules and become hydrated, energy is released. The process is endothermic if the energy needed to break the bonds is greater than the energy released when the ions attach to water. 

Water is the most common solvent used to dissolve ionic compounds. Principally, the reasons for dissolution of ionic crystals in water are two. Not stated in any order of sequence of importance, the first one maybe mentioned as the weakening of the electrostatic forces of attraction in an ionic crystal known, and the effect may be alternatively be expressed as the consequence of the presence of highly polar water molecules. The high dielectric constant of water implies that the attractive forces between the cations and anions in an ionic salt come down by a factor of 80 when water happens to be the leaching medium. The second responsible factor is the tendency of the ionic crystals to hydrate. 

When an ionic compound is dissolved in a solvent, the crystal lattice is broken apart. As the ions separate, they become strongly attached to solvent molecules by ion-dipole forces. The number of water molecules surrounding an ion is known as its hydration number. However, the water molecules clustered around an ion constitute a shell that is referred to as the primary solvation sphere. The water molecules are in motion and are also attracted to the bulk solvent that surrounds the cluster. Because of this, solvent molecules move into and out of the solvation sphere, giving a hydration number that does not always have a fixed value. Therefore, it is customary to speak of the average hydration number for an ion. 

The water that is trapped within the crystal structure of some ionic compounds (the water of hydration) can be removed easily by heating. The amount of the water present in a given sample can be determined by weighing the sample before and after this heating. The weight loss that occurs is the weight of the water in the sample. The percent of water in the hydrate is calculated as it is in a loss-on-drying experiment. 

Reactive ionic compounds are therefore useless to derive hydration enthalpies (or more generally, solvation enthalpies). Fortunately, there are many alternatives. Take lithium chloride, for example, and data from the NBS Tables [ 17]. The enthalpy of solution of this solid in water, at infinite dilution, is given by... 

In Investigation 9-A, you will collect solubility data and use these data to determine a Ksp for calcium hydroxide, Ca(OH)2. When you calculate Ksp, you assume that the dissolved ionic compound exists as independent hydrated ions that do not affect one another. This assumption simplifies the investigation, but it is not entirely accurate. Ions do interfere with one another. As a result, the value of Ksp that you calculate will be just an approximation. iCp values that are calculated from data obtained from experiments such as Investgation 9-A are generally higher than the actual values. 

Type I spectra are associated with hydrated ionic compounds such as the MnCl2 4H2O and with many other compounds having a single octahedral coordination sphere. These spectra are sensitive to ionic charge and to radius of coordination sphere. 

The roles of hydration enthalpies and entropies in determining the solubilities of ionic compounds... 

Hydrates Some ionic compounds incorporate a fixed number of water molecules into their formula unit. The compound that contains the water is called a hydrate, and removal of the water affords the anhydrous salt. Compounds that have a strong tendency to absorb water are called hygroscopic. To name a hydrate, you simply name the ions and then add the appendage hydrate, along with a multiplier to indicate the number of water molecules in the formula. 

---