Title: The Representative Elements
1The Representative Elements
- Representative elements
- chemical properties are determined by the valence
s and p electrons - include elements in group IA through VIIIA
- Diagonal line divides the metals from the
nonmetals - 8 metalloids exhibit both metallic and
nonmetallic properties
2The Representative Elements
- Metals vs. Nonmetals
- Metals tend to lose valence electrons to form
cations - Nonmetals tend to gain valence electrons to form
anions - Metallic character increases going down a group
(I.E. Decreases going down a group)
3The Representative Elements
- Size and Group Anomalies
- Different properties between elements in the
first row of a group than the elements in the
second row due to the large differences in the
atomic radii - H is very different from Li due to Hs very small
size - H has a greater attraction for electrons than Li,
so H can form covalent bonds, Li and the other
Group I elements lose electrons
4The Representative Elements
- Oxides of Group IIA are basic except
- BeO is amphoteric
- because Be is so small, BeO has some covalent
character - Dramatic difference between C chemistry and
silicon chemistry - Organic chemistry - deals with stable compounds
with many C - C bonds - Silicon chemistry - mostly Si - O bonds.
- Compounds with Si-Si bonds are more reactive
5The Representative Elements
- Carbon
- can form p bonds, CC, CO, etc.
- Silicon
- difficult to form p bonds
- Sis 3p orbital cannot overlap with Os 2p
orbital ...due to differences in size
6The Representative Elements
- Nitrogen
- forms p bonds, e.g. N N, very very stable
- Phosphorus
- like Si, does not form p bonds, though it does
form aggregates of atoms, like P4 - Oxygen
- forms bonds, e.g. OO, very stable
- Sulfur
- Sulfur atoms form aggregates, such as the cyclic
S8
7The Representative Elements
- Still on the subject of size...
- F has a smaller electron affinity than Cl, which
is the reverse of the expected trend - Why? F is so small that the electron pairs tend
to repel each other. - The F2 bond is weaker than the Cl2 bond, again
because Fs small size allow the lone pairs to
get closer together, repelling each other, and so
weakening the bond
8The Representative Elements
- Abundance and Preparation
- In the earths crust, oceans and atmosphere
- Oxygen 49.2
- Silicon 25.7
- Aluminum 7.50
- Iron 4.71
- Calcium 3.39
9The Representative Elements
- Abundance and Preparation
- In the human body
- Oxygen 65.0
- Carbon 18.0
- Hydrogen 10.0
- Nitrogen 3.0
- Calcium 1.4
10The Representative Elements
- Abundance and Preparation
- Only 1/4 of the elements occur naturally in the
free state - Metallurgy - process of obtaining a metal from
its ore - usually involves the reduction of the metal
- Carbon is the usual choice for a reducing agent
- Electrolysis is used to reduce the most active
metals
11The Representative Elements
- Preparation of Nonmetals
- Liquefaction/distillation of air to obtain N2 and
O2 - based on their different boiling points
- N2 - second in amount manufactured in the U.S.
- O2 - fourth in amount manufactured in the U.S.
- H2 - obtained from the electrolysis of water and
the decomposition of methane - Sulfur - found underground in elemental form,
recovered using the Frasch process
12The Representative Elements
- Group IA Elements
- ns1 outer electron configuration
- very active metals (except for hydrogen)
- the alkali metals
- react vigorously with water to produce hydrogen
gas - 2M 2 H2O(l) --gt 2 M 2 OH- H2
- Li is the only alkali metal to form the oxide in
presence of excess oxygen - 2Li(s) O2(g) --gt 2Li2O(s)
13The Representative Elements
- 2 Na(s) O2(g) --gt Na2O(s) (in limited oxygen)
- In excess oxygen, sodium forms the peroxide
- 2Na O2 --gt Na2O2
- the sodium peroxide reacts with water to form
hydrogen peroxide - Na2O2 2H2O --gt H2O2 2 Na 2OH-
- Potassium, rubidium and cesium react with oxygen
to produce superoxides, MO2 - Ex K(s) O2(g) --gt KO2(s)
- The superoxides release oxygen gas in water or
carbon dioxide
14The Representative Elements
- 2KO2 2H2O --gt 2K 2OH- O2 H2O2
- 4KO2 2CO2 --gt 2K2CO3(s) 3O2
- these superoxides are used in the breathing
apparatus used by firefighters - Lithium is the only alkali metal to react with
nitrogen gas - 6Li N2 --gt 2Li3N(s)
15The Representative Elements
- Element Source Method of Preparation
- Lithium silicate minerals electrolysis of molten
LiCl - Sodium NaCl electrolysis of molten NaCl
- Potassium KCl electrolysis of molten KCl
-
16The Representative Elements
- Hydrogen
- colorless, odorless gas composed of H2 molecules
- low MM, nonpolar, very low B.P. (-253oC), very
low M.P. (-253oC) - highly flammable, explosive
- Industrial source reaction of methane and water
- CH4 H2O --gt CO 3H2
- Also a byproduct of cracking large hydrocarbons
in gasoline production
17The Representative Elements
- Hydrogen
- pure hydrogen can be produced by the electrolysis
of water, but not economically feasible - Industrial uses
- production of ammonia (Haber process)
- hydrogenation of unsaturated vegetable oils
- Chemical Behavior
- typical nonmetal
- forms covalent compounds with other nonmetals
- forms salts with active metals
18The Representative Elements
- Hydrides
- Ionic (saltlike) hydrides
- when hydrogen combines with very active metals
from Group I or Group II - the hydride ion (H-) is a strong reducing agent
- ionic hydrides react violently in water
- LiH H2O --gt H2 Li OH-
- Covalent hydrides
- when hydrogen combines with other nonmetals, e.g.
in HCl, NH3, CH4, and H2O
19The Representative Elements
- Metallic hydrides
- formed when transition metal crystals are treated
with hydrogen gas - the hydrogen atoms migrate into the crystal
structure to occupy holes or interstices - a solid solution is formed
- when these interstitial hydrides are heated, H2
gas is released - use these intersitial hydrides for hydrogen gas
storage
20The Representative Elements
- Group IIA Elements
- ns2 outer electron configuration
- very reactive
- alkaline earth metal elements
- the oxides of the Group II elements form bases in
water MO(s) H2O --gt M2 2 OH- - BeO can act as an acid as well
- BeO(s) 2 OH- H2O --gt Be(OH)4-2
- Group II metals react with water to form H2
- M(s) 2H2O(l) --gt M2 2 OH- H2(g)
21The Representative Elements
- Source of Group II elements
- electrolysis of molten chlorides of the Group II
elements - Heavier Group II elements react with nitrogen or
hydrogen to form the nitride or hydride salts - 3 Ca(s) N2 --gt Ca3N2(s)
- Ca(s) H2 --gt CaH2(s)
22The Representative Elements
- Practical importance of alkaline earth metals
- Calcium
- found in structural minerals in bones and teeth
- Magnesium
- as Mg2 plays a vital role in metabolism and
muscle function - used to produce the bright light for photographic
flash units 2 Mg O2 --gt 2MgO light - useful structural material, especially when
alloyed with aluminum (low density and moderate
strength) - both Ca2 and Mg2 make water hard
- hard water interferes with detergent action and
prevents soaps from lathering
23The Representative Elements
- Group IIIA Elements
- ns2np1
- metallic character increases going down the group
- Boron
- BH3 is actually unstable, while diborane, B2H6,
is stable - boranes are electron deficient, so are very
reactive - Aluminum
- most abundant metal on earth
- has metallic physical properties (high thermal
and electrical conductivities, lustrous
appearance) - bonds covalently to nonmetals
- Al2O3 is amphoteric
24The Representative Elements
- Gallium
- unusually low melting point (30oC)
- largest liquid range between the mp and bp (b.p.
2400oC) - makes gallium useful for thermometers, especially
for high temperatures - expands like water when it freezes
- is amphoteric like aluminum
25The Representative Elements
- Indium
- chemistry is similar to aluminum and gallium
- can form 1 ion as well as 3 ions
- Thallium
- completely metallic
- Tl2O3 is a basic oxide
- has a 1 and 3 oxidation state
26The Representative Elements
- Group IVA Elements
- ns2np2
- contains two of the most important elements on
earth Carbon and Silicon - all Group IVA elements can form four covalent
bonds to nonmetals CH4, SiH4, GeBr4, SnCl4, and
PbCl4 - form tetrahedral molecules with sp3 hybridization
27The Representative Elements
- Carbon
- can form p bonds
- C-C bond is stronger than the Si-Si bond, so
carbon chemistry is dominated by the C-C bond,
while silicon chemistry is dominated by the Si-O
bond - 2 allotropic forms found in the earths crust
- diamond and graphite
- buckminsterfullerene, C60, and other related
substances have been characterized
28The Representative Elements
- Three oxides of carbon
- CO, carbon monoxide, by-product of incomplete
combustion of carbon compounds - CO2, carbon dioxide, product of human and animal
respiration and combustion of fossil fuels,
produced in fermentation - dissolves in water to form an acidic solution
- CO2 H2O --gt H HCO3-
- OCCCO, carbon suboxide!!
29The Representative Elements
- Silicon
- second most abundant element on earth
- metalloid
- distributed in silica and silicates
- 85 of the earths crust is composed of these
silica and silicates - major use is in semiconductors
30The Representative Elements
- Germanium
- relatively rare element, metalloid, used in
semiconductors - Tin
- soft, silvery white metal
- used in alloys such as bronze (Sn Cu), solder
(Sn Pb), and pewter (Sn, Cu, Bi, and Sb) - three allotropes
- white tin, gray tin, and brittle tin (all stable
at different temperatures)
31The Representative Elements
- Tin
- current use - protective coating (applied
electrolytically) for steel, especially in food
containers - 2 and 4 oxidation states
- Tin(IV) halides contain covalent Sn-X bonds, not
ionic bonds, behave more like molecular compounds
than ionic compounds - Tin(IV) halides are very volatile
- Tin (II) halides are probably ionic, and are less
volatile - SnF2 was used in toothpaste
32The Representative Elements
- Lead
- obtained from the ore, galena, PbS
- melts at a low temperature
- may have been the first metal every obtained from
its ore (lead was used as early as 3000 B.C.) - lead is toxicRoman civilization may have
crumbled partly due to lead poisoning as analysis
of bones from that era show high lead
concentrations - largest commercial use of lead is for electrodes
in the lead storage battery
33The Representative Elements
- Lead
- forms 2 and 4 oxidation states
- lead (II) halides exhibit ionic properties
- only PbCl4 and PbBr4 exist (only possible lead
(IV) halides) - PbO (lead (II) oxide) - used to glaze ceramics
- PbO2 (lead (IV) oxide) does not exist in nature
34The Representative Elements
- Group VA elements
- ns2np3
- varied chemical properties among the members of
the group - metallic character increases going down the group
- N and P are nonmetals
- Bi and Sb are metallic
- too much energy is required to remove 5
electrons, so no ionic compound containing Bi5
or Sb5 exist - SbCl5 and BiF5 are actually molecular
35The Representative Elements
- Bi and Sb are strong oxidizing agents in the 5
oxidation state - BiF5 is a good fluorinating agent
- BiF5 --gt BiF3 F2
- Bi3 and Sb3 salts are quite common
- All of the Group VA elements, except for N, can
form molecules with 5 covalent bonds - N cannot form molecules with covalent bonds
because of its small size and lack of d orbitals
36The Representative Elements
- Elements in Group VA, except for N, do not
readily form pi bonds - N2 consists of a triple bond between the nitrogen
atoms - P4, As4, and Sb4 are all singly bonded
37The Representative Elements
- The Chemistry of Nitrogen
- all elemental nitrogen on earth exists as N2 with
a very strong triple bond (941 kJ/mole) - N2 is very unreactive it can coexist with most
other elements without any significant reaction - N2 makes a good inert atmosphere to run reactions
with substances that normally react with oxygen
or water - Because of N2s triple bond, most binary
compounds containing nitrogen decompose
exothermically to form N2 - e.g. N2O --gt N2 1/2 O2 DHo -82 kJ
38The Representative Elements
- Thermodynamic stability of N2
- nitrogen based explosives
- 4C3H5N3O9(l) --gt 6 N2(g) 12 CO2(g) 10H2O(g)
O2(g) energy - nitroglycerin
- 4 moles of liquid nitroglycerin yields 29 moles
of gaseous products, producing a large increase
in volume as well as very stable molecules with
strong bonds, hence an explosion occurs with hot,
rapidly expanding gases - Dynamite - invented by Alfred Nobel in 1867
- absorb this highly unstable nitroglycerin onto
porous silica to make its handling safer
39The Representative Elements
- More Nitrogen based explosives
- most high explosives are organic compounds that
contain nitro (-NO2) groups to produce nitrogen
and other gases as products - TNT - trinitotoluene
- 2C7H5N3O6(s) --gt 12CO(g) 5H2(g) 2C(s) energy
40The Representative Elements
- Nitrogen fixation
- transforming N2 to other nitrogen containing
compounds - Haber process, the synthesis of ammonia, is an
example of nitrogen fixation - the ammonia can be applied to the soil as a
fertilizer - high temperature combustion process in automobile
engines - nitrogen reacts with oxygen to form NO
- NO reacts with oxygen to form NO2 (contributor to
photochemical smog) - NO2 reacts with moisture to form nitrate salts,
which are plant nutrients
41The Representative Elements
- Natural nitrogen fixation
- N2 O2 react together to form nitrogen oxides
with the help of lightning to disrupt the strong
bonds - studies indicate that lightning may account for
half of the fixed nitrogen available on earth - Nitrogen fixing bacteria in the root nodules of
legumes such as beans,peas, and alfalfa, allow
for the conversion of N2 to ammonia and other
nitrogen containing compounds useful to plants - much more efficient than the Haber process
(bacteria work at soil temperature and 1 atm
pressure, the Haber process runs at 400oC and 250
atm!
42The Representative Elements
- The Nitrogen Cycle
- 10 million more tons more nitrogen is currently
being fixed by natural and human processes than
is being returned to the atmosphere - the fixed nitrogen accumulates in the soil,
lakes, rivers, and oceans where it promotes algae
growth as well as growth of other undesirable
organisms - Denitrification - bacteria can return the
nitrogen in nitrogen containing compounds to the
atmosphere as nitrogen gas
43The Representative Elements
- Nitrogen Hydrides
- Ammonia - most important of the nitrogen hydrides
- toxic, colorless gas, manufactured in large
quantities (30 billion pounds per year, used
mainly in fertilizers - unusually high B.P. (-33.4oC), for a substance
with such a low MM, due to Hydrogen bonding - Hydrazine, N2H4
- colorless liquid with an ammonia-like odor
- powerful reducing agent
- used as a rocket propellant
- used as a blowing agent (because it produces
N2(g) upon decomposition) in the manufacture of
plastics - used in agricultural pesticides
44The Representative Elements
- Nitrogen Oxides
- Nitrogen forms a series of oxides in which
nitrogen has oxidation states from 1 to 5 - N2O - dinitrogen monoxide, aka, nitrous oxide,
aka, laughing gas - also a mild anesthetic, a propellant in aerosol
cans of whipped cream - exists in the atmosphere as a result of soil
microorganisms, helps to control the earths
temperature because it can absorb infrared
radiation
45The Representative Elements
- Nitrogen Monoxide
- NO, commonly called nitric oxide
- colorless gas produced when nitric acid reacts
with copper metal - in oxygen, the NO is oxidized to form the brown
gas, NO2 - may behave as a neurotransmitter in the body
- has an odd number of electrons, is paramagnetic
(use MO diagrams), and is thermodynamically
unstable - 3NO(g) --gt N2O(g) NO2(g)
46The Representative Elements
- Nitrogen Dioxide
- NO2, also contains an odd number of electrons, is
paramagnetic, and dimerizes to form N2O4 - 2NO2 --gt N2O4
- Dinitrogen Trioxide
- N2O3 - least common, a blue liquid that
dissociates into NO and NO2, and N2O5
47The Representative Elements
- Oxyacids of Nitrogen
- Nitric acid - HNO3
- 10 million tons produced per year
- used in the manufacture of many products such as
nitrogen based explosives and ammonium nitrate - produced commercially by the oxidation of ammonia
in the Ostwald process - 4NH3 5O2 --gt 4NO 6 H2O
- 2NO O2 --gt 2NO2
- 3NO2 H2O --gt 2HNO3 NO
48The Representative Elements
- Nitric acid
- colorless, fuming liquid with a pungent odor
- decomposes in sunlight
- 4HNO3 --gt 4NO2 2 H2O O2
- turns yellow as it ages because of the NO2
- strong oxidizing agent
- reacts with metal oxides, hydroxides, and
carbonates to form nitrate salts which are
generally very soluble in water
49The Representative Elements
- Nitrous Acid
- HNO2, a weak acid, forms pale yellow nitrite
salts - nitrites are very stable, even at high
temperatures - nitrites are prepared by bubbling nitric oxide,
nitrogen dioxide, and a metal hydroxide - NO NO2 2NaOH --gt 2NaNO2 H2O
50The Representative Elements
- The Chemistry of Phosphorus
- very different properties from those of nitrogen
- due to
- Ns ability to form pi bonds
- greater electronegativity of N
- larger size of P
- availability of d orbitals on phosphorus
- several solid forms of phosphorus
- white phosphorus, P4, with a tetrahedral geometry
- very reactive, bursts into flames on contact with
air (it is pyrophoric)
51The Representative Elements
- Black phosphorus and red phosphorus - covalent
network solids - Black phosphorus is crystalline, and is obtained
from white or red phosphorus - Red phsophorus is amorphous and is obtained from
heating white phosphorus in the absence of air - Phosphide salts react with water to produce
phosphine, PH3, a toxic, colorless gas
52The Representative Elements
- Phosphorus oxides and oxyacids
- Phosphorus reacts with oxygen to form oxides in
which P has oxidation states 5 and 3. - P4O6, P4O7, P4O8, P4O9, and P4O10 can be obtained
by burning phosphorus in oxygen - P4O10 is powerful dehydrating agent
- it can convert HNO3 and H2SO4 to their parent
oxides, N2O5 and SO3 - P4O10 reacts with water to form phosphoric acid
- P4O10 6H2O --gt 4H3PO4
53The Representative Elements
- Phosphoric acid undergoes condensation reactions
- water is eliminated as two molecules of
phosphoric acid are joined together - H3PO3 is actually a diprotic acid as one H is
bonded to the P - H3PO2 is actually a monoprotic acid as two Hs
are bonded to the P
54The Representative Elements
- Phosphorus is essential for plant growth
- usually present as insoluble phosphate minerals,
inaccessible to plants - make accessible with soluble phosphate fertilizers
55The Representative Elements
- Phosphorus Halides
- PX3 and PX5 exist for all halides except PI5 does
not exist - PX3 reacts with water to form phosphorus acid
- PCl3 3H2O --gt H3PO3 3HCl
- PCl5 and PBr5 form ionic solidsPCl5 contain a
mixture of the PCl6- ion and PCl4 ion - PBr5 contains a mixture of PBr4 and Br- ion
- PX5 reacts with water to form phosphoric acid
- PX5 4H2O --gt H3PO4 5HX
56The Representative Elements
- Group VIA elements
- ns2np4
- metallic behavior increases going down the group,
but none of the Group 6A elements behaves as a
typical metal - can form covalent bonds with other nonmetals
- Te and Po can exist as 4 cations, but their
chemistry is limited
57The Representative Elements
- Selenium
- studies show an inverse relationship between
incidence of cancer of selenium levels in
soili.e., the more selenium in the soil, the
lower the incidence of cancer - involved in the activity of Vitamin E and other
enzymes - selenium deficiency is connected to occurrence of
congestive heart failure - used as semiconductors
58The Representative Elements
- Polonium
- discovered by Marie Curie in 1898
- has 27 isotopes
- highly toxic and very radioactive
- 210Po is found in tobacco, is an alpha particle
emitter, and so may be responsible for the
incidence of cancer in smokers
59The Representative Elements
- The Chemistry of Oxygen
- Most abundant element in and near the earths
crust - Present as O2, in oxide, silicate, and carbonate
minerals, in water, and in many more molecules - O2 makes up 21 by volume of the atmosphere
- freezes at -219oC and boils at -183oC
- can be obtained from liquid air after N2 has been
removed - a pale blue liquid
- paramagnetic (see M.O. model)
60The Representative Elements
- The Chemistry of Oxygen
- Ozone - an allotrope of oxygen, O3
- can be prepared by passing an electric discharge
through O2 - pale blue, highly toxic gas
- powerful oxidizing agent, can be used instead of
chlorine in water purification - exists naturally in the upper atmosphere of the
earth - protects from uv, the O3 absorbs the energy and
splits - O3 --gt O2 O
61The Representative Elements
- The Chemistry of Sulfur
- found as the free element
- found in ores such as galena (PbS), cinnabar
(HgS), pyrite (FeS), gypsum (CaSO4.2H2O), etc. - 60 of the sulfur produced in the U.S. comes from
deposits of underground sulfur from Texas and
Louisiana - Sulfur is recovered using the Frasch process
developed by Herman Frasch in the 1890s
62The Representative Elements
- The Chemistry of Sulfur
- Frasch Process
- superheated water is pumped into the deposit to
melt the sulfur - the molten sulfur is forced to the surface using
air pressure - the remaining 40 of the sulfur comes from the
purification of fossil fuels, from the sulfur
dioxide obtained from the burning of sulfur
containing fuels
63The Representative Elements
- Sulfur atoms from strong s bonds than p bonds
- large aggregates of S6and S8 and Sn exist
- Most stable form rhombic sulfur which consists
of stacked rings of S8 - An allotropic form of the rhombic sulfur is the
monoclinic sulfur which is also S8, but which are
stacked differently than in rhombic sulfur - A plastic sulfur also exists which contains Sn
chains and has rubber like qualities.
64The Representative Elements
- Sulfur Oxides
- S burns in air to give SO2
- SO2 is an effective antibacterial agent and is
used to preserve dry fruit - 2SO2 O2 --gt 2SO3
- produced when sulfur containing fuels are burned
- a slow reaction that requires a catalyst
- SO3 is a corrosive gas
- forms H2SO4 when it reacts with moisture in the
air, a culprit in acid rain
65The Representative Elements
- Oxyacids of Sulfur
- SO2 H2O --gt H2SO3
- SO3 H2O --gt H2SO4 (very violent reaction)
- Sulfuric acid
- manufactured in greater amounts than any other
chemical - 60 of the H2SO4 is used to produce fertilizers
- 40 is used in lead storage batteries, in
petroleum refining, steel manufacturing and in
other chemical industries
66The Representative Elements
- Sulfuric Acid
- high affinity for water - acts as a dehydrating
agent - dry gases by bubbling gases through concentrated
sulfuric acid - it can even remove H and O in a 21 ratio from
sugar - C12H22O11 11H2SO4 --gt 12C(s) 11 H2SO4. H2O
- strong oxidizing agent, especially at high
temperatures - SO4-2--gt SO2
67The Representative Elements
- Other Compounds of Sulfur
- Oxidation states of sulfur 6, 4, 2, 0, and -2
- H2S - sulfur has a -2 oxidation state
- toxic, foul smelling gas
- good reducing agent
- produces a milking looking suspension of sulfur
as one of the products H2S(g) --gt S(s)
68The Representative Elements
- Other Compounds of Sulfur
- thiosulfate ion S2O3-2
- similar to a sulfate ion, but one of the oxygens
has been replaced with a sulfur atom - used in photography
- S(s) SO3-2 --gt S2O3-2
- good reducing agent S2O3-2 --gt S4O6-2 (used to
analyze for Iodine) - sulfur reacts with halogens to form a variety of
compounds S2Cl2, SF4, SF6, S2F10, etc.
69The Representative Elements
- Group VIIA elements
- halogens
- ns2np5
- all nonmetals whose properties vary smoothly
going down the group - exceptions include the low electron affinity of F
and the bond energy of the F2 molecule which is
lower than expected - Astatines isotopes are all radioactive
70The Representative Elements
- Halogens
- all high electronegativity values, especially F
- tend to form polar covalent bonds with other
nonmetals - form ionic bonds with metals in their lower
oxidation states - the bonds become polar covalent when a halogen is
bonded with a metal in a higher oxidation state,
e.g. TiCl4 or SnCl4 (both covalent compounds and
liquids under normal conditions)