Molecular chlorine atoms

Chang J P, Arnold J C, Zau G C H, Shin H-S and Sawin H H 1997 Kinetic study of low energy ion-enhanced plasma etching of polysilicon with atomic/molecular chlorine J. Vac. Sc/. Technol. A 15 1853-63... 

In a process similar to that described in the previous item, the stored data can be used to identify not just a series of compounds but specific ones. For example, any compound containing a chlorine atom is obvious from its mass spectrum, since natural chlorine occurs as two isotopes, Cl and Cl, in a ratio of. 3 1. Thus its mass spectrum will have two molecular ions separated by two mass units (35 -i- 2 = 37) in an abundance ratio of 3 1. It becomes a trivial exercise for the computer to print out only those scans in which two ions are found separated by two mass units in the abundance ratio of 3 1 (Figure 36.10). This selection of only certain ion masses is called selected ion recording (SIR) or, sometimes, selected ion monitoring (SIM, an unfortunate... 

Naturally occurring isotopes of any element are present in unequal amounts. For example, chlorine exists in two isotopic forms, one with 17 protons and 18 neutrons ( Cl) and the other with 17 protons and 20 neutrons ( Cl). The isotopes are not radioactive, and they occur, respectively, in a ratio of nearly 3 1. In a mass spectrum, any compound containing one chlorine atom will have two different molecular masses (m/z values). For example, methyl chloride (CH3CI) has masses of 15 (for the CH3) plus 35 (total = 50) for one isotope of chlorine and 15 plus 37 (total = 52) for the other isotope. Since the isotopes occur in the ratio of 3 1, molecular ions of methyl chloride will show two molecular-mass peaks at m/z values of 50 and 52, with the heights of the peaks in the ratio of 3 1 (Figure 46.4). 

Partial mass spectra showing the isotope patterns in the molecular ion regions for ions containing carbon and (a) only one chlorine atom, (b) only one bromine atom, and (c) one chlorine and one bromine atom. The isotope patterns are quite different from each other. Note how the halogen isotope ratios appear very clearly as 3 1 for chlorine in (a), 1 1 for bromine in (b), and 3 4 1 for chlorine and bromine in (c). If the numbers of halogens were not known, the pattern could be used in a reverse sense to decide their number. 

Molecular Structure and Monomer Addition Orientation. The addition of vinyl monomer to a growing PVC chain can be considered to add in a head-to-tail fashion, resulting in a chlorine atom on every other carbon atom, ie,... 

Selective chlorination of the 3-position of thietane 1,1-dioxide may be a consequence of hydrogen atom abstraction by a chlorine atom. Such reactions of chlorine atoms are believed to be influenced by polar effects, preferential hydrogen abstraction occurring remotely from an electron withdrawing group. The free radical chain reaction may be propagated by attack of the 3-thietanyl 1,1-dioxide radical on molecular chlorine. 

Structural drawings (molecular models, too) can be deceiving. For example, the chlorine atoms in 1,2-dichlorocyclohexane seem much closer to each other in a drawing of the trans stereoisomer than in the cis. Make a molecular model of each, and measure the distance between the chlorines. What do you find ... 

Chloroform, CHCla, is an example of a polar molecule. It has the same bond angles as methane, CH4, and carbon tetrachloride, CCLi- Carbon, with sp3 bonding, forms four tetrahedrally oriented bonds (as in Figure 16-11). However, the cancellation of the electric dipoles of the four C—Cl bonds in CCL does not occur when one of the chlorine atoms is replaced by a hydrogen atom. There is, then, a molecular dipole remaining. The effects of such electric dipoles are important to chemists because they affect chemical properties. We shall examine one of these, solvent action. 

Dichloronitrotoluenes are indicated by the presence of an odd molecular ion with chlorine isotopes showing two chlorine atoms and losses of 30 and 46 Daltons. Again, when the chlorine atoms are on the benzene ring, the loss of chlorine from the molecular ion does not occur. An M - Cl ion indicates that at least one of the chlorines is on the alkyl group. 

The molecular ion must contain the highest number of atoms of each element present. For example, if a lower-mass ion contains four chlorine atoms, but the highest-mass ion observed contains only three, then at least 35 Daltons should be added to the highest-mass ion observed to deduce the molecular ion. 

The mass spectrum of the unknown compound showed a molecular ion at m/z 246 with an isotope pattern indicating that one chlorine atom and possibly a sulfur atom are present. The fragment ion at m/z 218 also showed the presence of chlorine and sulfur. The accurate mass measurement showed the molecular formula to be C]3FI7OSCl R + DB = 10. 

The presence of three chlorine atoms is easily determined by the isotope ratios. The odd molecular weight shows the presence of nitrogen. The loss of m/z 30 and 46 from the molecular ions shows the presence of the nitro group. 

The molecular ion for chlordane can be observed in Figure 25.1. Note the pattern for eight chlorine atoms. The most abundant fragment ion is the loss of a chlorine atom at m/z 373. 

The molecular ion is apparent in the mass spectrum of DDT (Figure 25.2) at m/z 352 with the classic isotope pattern for five chlorine atoms (see Appendix 11). The major fragment ion is the loss of CCI3 at m/z 235. 

Self-Test 3.8A Describe (a) the electron arrangement, (b) the molecular shape, and (c) the hybridization of the central chlorine atom in chlorine trifluoride. 

FIGURE 16.44 The structure of a molecular magnet. The nano-size molecular torus contains 84 manganese atoms and is approximately 4 nm in diameter. The manganese atoms are bonded to groups of carbon atoms in the form of acetate ions, water molecules, and chlorine atoms. In this molecule the manganese atoms act as terromagnets. 

There are three cases The original p orbital may have contained two, one, or no electrons. Since the original double bond contributes two electrons, the total number of electrons accommodated by the new orbitals is four, three, or two. A typical example of the first situation is vinyl chloride, CH2—CH—CI. Although the p orbital of the chlorine atom is filled, it still overlaps with the double bond. The four electrons occupy the two molecular orbitals of lowest energies. This is our first example of resonance involving overlap between unfilled orbitals and a filled orbital. Canonical forms for vinyl chloride are... 

Chlorine molecules must be broken apart into chlorine atoms. Table gives the bond energy BE) of molecular chlorine, 240 kJ/mol. We need — mole of CI2 to form 1 mole of NaCl, so the energy... 

Use the Lewis structure of CIF3 to determine the steric number of the chlorine atom. Obtain the molecular shape from the orbital geometry after placing lone pairs in appropriate positions. 

Events that take place on a grand scale often can be traced to the molecular level. An excellent example is the depletion of the ozone layer in the Earth s stratosphere. The so-called ozone hole was first observed above the Antarctic in the 1980s and is now being observed above both the Arctic and Antarctic poles. The destruction of ozone in the stratosphere is caused primarily by reactions between chlorine atoms and ozone molecules, as depicted in our molecular inset view. 

Chlorine atoms react with O3 molecules to produce O2 and CIO, as shown by the molecular pictures in Figure 15-19. This is a catalytic process because chlorine monoxide reacts with an oxygen atom to produce a second O2... 

---