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22 -- Part 4: Chemistry of the Main Group Elements II:
Sulfur Sulfur has more allotropes than most elements.
The S8 ring is the most common structural unit in the solid state, but there are other structures with up to 20 S atoms per ring.
S, S2, S4, S6, and S8 can all be found in sulfur vapor.
Liquid sulfur has long-chain mol ecules of sulfur atoms.
There is a stable solid at room temperature.
1Sb2 has a dif ferent crystal structure than Sa.
1Sl2 is a straw-colored liquid consisting of mostly S8 molecule but with other cyclic mole cules containing from 6 to 20 atoms.
The maximum chain length is 180 degrees.
The chains break up at higher temperatures.
S8 molecule break down into smaller mole cules at higher temperatures at the boiling point.
Plastic sulfur has rubberlike properties.
It becomes rhombic sulfur when standing.
After continued heating, the liquid becomes red.
Some of the transitions, especially those in the solid state, are sluggish, and additional phenomena are occasionally seen.
rhombic sulfur may fail to convert to monoclinic sulfur if it is heated quickly.
Monoclinic sulfur can freeze from this liquid and then melt again.
Oxygen is so important to the study of chemistry that we constantly refer to its physical and chemical properties in developing a framework of chemical principles.
Our discussion began with the reactions of substances with O21g2 to form products such as CO21g2, H2O1l2, and SO21g2.
In the presentation of thermochemistry, combustion reactions figured prominently.
Oxygen-rich species were described in many of the polyatomic anions.
The study of acid-base and other solution equilibria was one of the topics discussed.
The dual roles of hydrogen peroxide as an oxidizing agent and a reducing agent were described in Section 6.
Oxygen compounds can be studied in conjunction with the other elements.
The oxides of carbon were also considered in the discussion of boron chemistry in Chapter 21.
The important oxides of sulfur, nitrogen, and phosphorus are discussed in this chapter, as a result of the survey of the chemistry of the alkali and alkaline earth metals.
oxidation- reduction chemistry is a concern here as it is in the corresponding discussion for the halogens.
Sulfur dioxide, SO2, and SO3 are the most common oxides of sulfur.
The synthesis of SO3 is used to make H2SO4.
V2O5 is mixed with metal sulfates.
The catalyst has 21g2 and O21g2 on it.
O 31g2 was trapped inside the droplets.
A great loss of product and a huge pollution problem would result from this mist.
31g2 is bubbled through 98% H2SO4 in towers with a ceramic material.
The small amount of water increases the concentra S tion of the sulfuric acid.
Sufficient water is added to the tower to maintain the required concentration.
The strength is produced with water.
It reacts with metals to liberate sulfur and carbonates.
To conform to the observed strong affinity for water, strong enough that it will remove the H and O structures of SO2, S2O, and atoms from some compounds.
S2O has the same atoms as SO2 but with a different carbon content, as shown in the photo structure to SO2 but with a on the next page.
O angle is approx Concentrated sulfuric acid is a good oxidizer and can react with copper.
For a long time, sulfuric acid has ranked among the top manufactured ability to form ring chemicals, with annual production in the United States of about 45 million compounds.
The bulk of H2SO4 is used in the manufacture of fertilizers.
Other uses include the manufacture of titanium dioxide and oil refining.
It is added to cane sugar.
The reaction produces carbon.
In this reaction with H2S, sulfite ion can act as an oxidizing agent.
Both H2SO3 and H2SO4 are diprotic acids.
They ionize in two steps and make two types of salts.
NaHSO3 and NaHSO4 are sometimes used for salts because their anions are isolated as a solid.
H2SO4 is strong in the first step and weak in the second step, but H2SO3 is weak in the first step and weak in the second.
The hemihydrate (plaster of Paris) is made from calcium sulfate dihydrate.
Water treatment and sizing paper use aluminum sulfate.
Copper(II) sulfate is used in a number of ways.
The paper industry is the main application of sulfites.
The fibers are free for processing into paper.
Reducing agents and scavengers of O21aq2 are used in treating boiler water.
Sulfur(IV) has been used as a food stabilizer.
In winemaking, exposure to SO21g2 prevents the discoloration of dried fruits.
Thiosulfates can be prepared by boiling sulfur in water.
Both of them to thiosulfate ion.
They are also used in conjunction with other analytical reagents.
CuI(s) and triiodide ion, I 3 are produced by the addition of O iodide ion.
SF2 and S2F2 are known as O compounds.
SF4 and SF6 activities are different.
A powerful fluorinating agent is found in 4.
BCl3 is converted to BF3.
The best halide is S 2Cl2 and SCl4.
Mustard gas is a volatile liquid and not a gas.
During World War I it was sprayed as mist that stayed close to the ground and was blown onto the enemy.
After four or five weeks, exposure to mustard gas causes death.
Industrial smog consists of particles (ash and smoke), SO21g2, and H2SO4 mist.
The main contributors to atmospheric releases of SO21g2 are power plants burning coal or high-sulfur fuel oils.
Water is converted to steam in a chamber where coal, limestone, and air are introduced.
The production of NO(g) from N21g2 and O21g2 is minimized by the use of a relatively low temperature.
The bed ash formed CaSO31s2 in a Lewis Feed water acid-base reaction.
H2SO4 mist is a component of acid rain because SO3 can react with water in the atmosphere.
Particles of 1NH422SO4 are produced by the reaction of H2SO4 with NH3.
The effect of low concentrations of SO2 and H2SO4 on the body is not well understood, but it is clear that these substances are respiratory irritants.
Potentially harmful levels are above 0.10 ppm.
The coal reacts with CaO1s2 to form deposits of CaSO31s2.
The chemistry of the group 15 elements is an extensive subject.
The special significance of these two elements to living matter will be discussed later in the text, but you should get a sense of their chemistry here.
The elements in group 15 have the same electron configuration.
This configuration doesn't give any clues as to metallic character that might exist.
Table 22.11 shows the usual decrease of ionization energy with increasing atomic number.
The order of metallic character within the group is suggested by the values and physical properties taken together.
Nitrogen, phosphorus, arsenic, and antimony are not metallic.
The first and third ionization energy of magnesium and aluminum are both less than the first and third ionization energy of bismuth.
The electronegativities show a high degree of nonmetallic character for nitrogen and less for the rest of the group.
White and red phosphorus are the common forms at room temperature.
The metallic forms of arsenic and antimony are more stable.
These forms have limited abilities to conduct electricity.
Even though it has a low electrical conductivity, it is still better than other metals and almost as good as mercury.
The nonmetals and metals are distinguishable by their oxides.
Group 18, 17, 16, 15, and Hydrogen react with water.
This is typical for nonmetal oxides.
Arsenic(III) oxide and antimony(III) oxide are amphoteric, which is a property of metal oxides.
Nitrogen Nitrogen occurs in the atmosphere.
Its abundance in Earth's solid crust is very low.
Fossilized remains of ancient plant life, as well as plant and animal protein, are other natural sources of nitrogen containing compounds.
The sources of pure nitrogen and its compounds were limited until about 100 years ago.
The Bosch process for converting nitrogen to ammonia was published in 1908.
Viruses can be made from ammonia.
Nitrogen has many important uses in it's own right, as well as being a precursor of manufactured nitrogen.
Table 22.12 has some uses listed.
Although it is the eleventh most abundant element, it was not discovered until 1669.
It was isolated from putrefied urine.
An electric furnace is used to heat coke, 1SiO22, andphosphate rock.
6 CaSiOl2 + 10 CO1g2 + P41g2 are under water.
The element itself is not widely used because it is important to living organ isms.
P4O10 is used in the manufacture of high-purity phosphoric acid.
The rest is used to make match heads.
Arsenic is obtained by heating metal sulfides.
The As1g2 can be used to make other compounds.
The reduction of arsenic(III) oxide with CO1g2 has some arsenic obtained.
The main source of antimony is its sulfide ores.
The by-product of refining other metals is bismuth.
In making other metals, As and Sb are used.
Adding As and Sb to Pb creates an alloy that has desirable properties for use in lead-acid batteries.
Semiconductor materials, such as GaAs, GaSb, and InSb, are produced using arsenic and antimony.
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