Gaseous atoms

The heats of formation of the gaseous atoms, 4, are not very different clearly, it is the change in the bond dissociation energy of HX, which falls steadily from HF to HI, which is mainly res ponsible for the changes in the heats of formation. 6. We shall see later that it is the very high H—F bond energy and thus the less easy dissoeiation of H—F into ions in water which makes HF in water a weak aeid in comparison to other hydrogen halides. 

C. The energy of formation of CH4 in the gaseous state from the gaseous atoms is found from the difference... 

Assuming a 2sf 2pf electron distribution for the carbon atoms, calculate the energy of fomiation of ethylene from the gaseous atoms. 

Kij tire 10-5 Eormation of Gaseous Atoms from Elements in the Standard State. 

The minimum amount of energy required to remove the least strongly bound electron from a gaseous atom (or ion) is called the ionization energy and is expressed in MJ moE. Remember that 96.485 kJ = 1.000 eV = 23.0605 kcal. In Table 4.2 the successive stages of ionization are indicated by the heading of each column I denotes first spectra arising from a neutral atom viz.,... 

Atomization The most important difference between a spectrophotometer for atomic absorption and one for molecular absorption is the need to convert the analyte into a free atom. The process of converting an analyte in solid, liquid, or solution form to a free gaseous atom is called atomization. In most cases the sample containing the analyte undergoes some form of sample preparation that leaves the analyte in an organic or aqueous solution. For this reason, only the introduction of solution samples is considered in this text. Two general methods of atomization are used flame atomization and electrothermal atomization. A few elements are atomized using other methods. 

Atomization and Excitation Atomic emission requires a means for converting an analyte in solid, liquid, or solution form to a free gaseous atom. The same source of thermal energy usually serves as the excitation source. The most common methods are flames and plasmas, both of which are useful for liquid or solution samples. Solid samples may be analyzed by dissolving in solution and using a flame or plasma atomizer. 

Associative ionization. Occurs when two excited gaseous atoms or molecular moieties interact and the sum of their internal energies is sufficient to produce a single, additive ionic product. 

Spark (source) ionization. Occurs when a solid sample is vaporized and partially ionized by an intermittent electric discharge. Further ionization occurs in the discharge when gaseous atoms and small molecular moieties interact with energetic electrons in the intermittent discharge. It is recommended that the word source be dropped from this term. 

Table 3. Electronic Configurations for Gaseous Atoms of Lanthanide and Actinide Elements...

Figure 3.7 The Lennard-Jones potential of the interaction of gaseous atoms as a function of the internuclear distance...

The differential optica) absorption spectrometer (DOAS) is based on the differential absorption of gaseous atoms or molecules.The Lamherr-Beer law gives the concentration... 

Because these photons are produced when an electron moves from one energy level to another, the electronic energy levels in an atom must be quantized, that is, limited to particular values. Moreover, it would seem that by measuring the spectrum of an element it should be possible to unravel its electronic energy levels. This is indeed possible, but it isn t easy. Gaseous atoms typically give off hundreds, even thousands, of spectral lines. 

In this section, you will learn how to predict the electron configurations of atoms of elements. There are a couple of different ways of doing this, which we consider in turn. It should be emphasized that, throughout this discussion, we refer to isolated gaseous atoms in the ground state. (In excited states, one or more electrons are promoted to a higher energy level)... 

Hund s rule, like the Pauli exclusion principle, is based on experiment It is possible to determine the number of unpaired electrons in an atom. With solids, this is done by studying their behavior in a magnetic field. If there are unpaired electrons present the solid will be attracted into the field. Such a substance is said to be paramagnetic. If the atoms in the solid contain only paired electrons, it is slightly repelled by the field. Substances of this type are called diamagnetic. With gaseous atoms, the atomic spectrum can also be used to establish the presence and number of unpaired electrons. 

Ionization energy is a measure of how difficult it is to remove an electron from a gaseous atom. Energy must always be absorbed to bring about ionization, so ionization energies are always positive quantities. 

The (first) ionization energy is the energy change for the removal of the outermost electron from a gaseous atom to form a +1 ion ... 

Bond enthalpies for a variety of single and multiple bonds are listed in Table 8.4. Note that bond enthalpy is always a positive quantity heat is always absorbed when chemical bonds are broken. Conversely, heat is given off when bonds are formed from gaseous atoms. Thus... 

The vapor pressure of a molten metal can be measured with a device called a Knudsen cell. This is a container closed across the top by a thin foil pierced by a small, measured hole. The cell is heated in a vacuum, until the vapor above the melt streams from the small hole (it effuses). The weight of the material escaping per second tells the rate at which gaseous atoms leave. 

The amount of energy required to remove the most loosely bound electron from a gaseous atom is called the ionisation energy. We can represent this process by the equation... 

The ease of removal of an electron from a gaseous atom, the ionization energy, is one of the factors that is important in fixing E°. Refer back to Table 21-111 and predict the trend in E° that this factor would tend to cause. 

The purpose of the nebuliser-burner system is to convert the test solution to gaseous atoms as indicated in Fig. 21.2, and the success of flame photometric methods is dependent upon the correct functioning of the nebuliser-burner system. It should, however, be noted that some flame photometers have a very simple burner system (see Section 21.13). 

A) Cold vapour technique. This procedure is strictly confined to the determination of mercury,45 which in the elemental state has an appreciable vapour pressure at room temperature so that gaseous atoms exist without the need for any special treatment. As a method for determining mercury compounds the procedure consists in the reduction of a mercury(II) compound with either... 

This apparatus may also be adapted for what are termed hydride generation methods (which are strictly speaking flame-assisted methods). Elements such as arsenic, antimony, and selenium are difficult to analyse by flame A AS because it is difficult to reduce compounds of these elements (especially those in the higher oxidation states) to the gaseous atomic state. 

The production of ground-state gaseous atoms which is the basis of flame spectroscopy may be inhibited by two main forms of chemical interference (a) by stable compound formation, or (b) by ionisation. 

Increase in flame temperature often leads to the formation of free gaseous atoms, and for example aluminium oxide is more readily dissociated in an acetylene-nitrous oxide flame than it is in an acetylene-air flame. A calcium-aluminium interference arising from the formation of calcium aluminate can also be overcome by working at the higher temperature of an acetylene-nitrous oxide flame. 

Ionisation. Ionisation of the ground-state gaseous atoms within a flame... 

Solutions in organic solvents may, with certain reservations, be used directly, provided that the viscosity of the solution is not very different from that of an aqueous solution. The important consideration is that the solvent should not lead to any disturbance of the flame an extreme example of this is carbon tetrachloride, which may extinguish an air-acetylene flame. In many cases, suitable organic solvents [e.g. 4-methylpentan-2-one (methyl isobutyl ketone) and the hydrocarbon mixture sold as white spirit ] give enhanced production of ground-state gaseous atoms and lead to about three times the sensitivity... 

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