Unit 6

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Summary of periodic trends
Effective Nuclear Charge
Hydrogen
• The electronic configuration of H is (1s1) similar to alkali metals
and can loose one electron to form unipositive ions
• also look like elements of group 17 (Halogens) because hydrogen

just like halogens needs just one electron to acquire the configuration
of the nearest noble gas i.e. Helium
• H has three isotopes - Protium, deuterium and tritium
• In elemental form exists as a diatomic molecule H2 and is called

dihydrogen
production of hydrogen using sodium and water
• Sodium metal (Na) will react violently with water (H2O),

liberating hydrogen gas (H2), heat, and light. The reaction is
as follows:
Continued
• If the temperature is hot enough and the hydrogen is mixed with
oxygen, combustion can take place resulting in an explosion.
• If hydrogen is heated without oxygen, no reaction will take place.

This means that hydrogen does not support combustion; it is the
fuel.
reactions of metal with an acid to produce hydrogen
• Various metals react with acids to produce hydrogen gas (H2) and
metallic salts.
• The rate at which the acid reacts with the metals (speed at which
hydrogen gas is formed, bubbles) depends upon the reactivity of
the metal.
• The more active the metal is, in regard to hydrogen, the faster
hydrogen is produced. This is known as the order of reactivity.
Continued
• Some common reactions of metals with dilute hydrochloric acid
(HCl) are as follows:
Continued
• Various acids can also be rated with respect to how fast they react
with metals to produce hydrogen. The stronger the acid, the higher
the reactivity (more bubbles). The reactions are similar to above,
producing a metallic salt and hydrogen gas (H2).

Continued
• Commercially, hydrogen is produced by cracking hydrocarbons
while producing alkenes (catalyzed):
C2H6(g) C2H4(g) + H2(g)
• Another route to hydrogen gas is through the water-gas shift

reaction: (Industrialy)
H2O(g) + CH4(g) Ni catalyst, 1200K CO(g) + 3H2(g)
CO(g) + H2O(g) FeO catalyst, 700K CO2(g) + H2(g)
Classifications of Hydrides
• binary compounds of hydrogen with other elements are called
hydrides (ExHy)
• Hydrides can be classified as saline, metallic, or molecular
1. Ionic or Saline hydrides
– are formed with s-block elements (highly electropositive).
– Such hydrides are non-volatile, non-conducting, and crystalline.
– They are quite insoluble in organic solvents
– exhibit very active chemistry when placed in water:
NaH(s) + H2O(l) H2(g) + NaOH(aq)
CaH2(s) + H2O(l) H2(g) + Ca(OH)2(aq), LiH, CaH2

2. Metallic hydrides (Interstitial hydrides):
• are the compounds of hydrogen with transition metals of group 3-5

and 10-12, Cr metal of group 6, f-block element
• Some of these are classified as interstitial hydrides, where hydride

ions dissociate to form H2 molecules, trapped in the interstitial
spaces of a metallic lattice (these are often non-stoichiometric).
• These materials are considered to be a safe means of hydrogen

storage (example, some metal lattices have been shown to absorb
several hundred equivalent volumes of H2(g))
3. Molecular or Covalent hydrides
• involve non-metals, and are usually volatile, in contrast to metallic

hydrides. (H2O, CH4, NH3)
• are binary compounds of hydrogen with elements of comparatively

high electronegativity such as p-block elements
• There are three classes of molecular hydrides
1. Electron-deficient (BF3)
– not enough electrons for bonding, and thus multicenter bonds must
be formed. Examples of this are hydrides of group 13

2. Electron-precise (e.g. CH4):

– correct number of electrons for bond formation, with none left for
lone pairs
– have required number of electrons to write the conventional Lewis
structure. Elements of group 14 like carbon, silicon etc. form these
types of hydrides
3. Electron-rich (e.g. NH3):
– have excess electrons than required to form normal covalent bonds.
–Excess electrons are present as lone pairs
–Examples of this are hydrides of group 15, 16 and 17 such as
ammonia, water etc.
Uses of hydrogen
• Hydrogen is used extensively in chemical reactions for reductions
(hydrogenations) in inorganic and organic labs
H2(g) + RCHO  RCH2OH (catalyzed)
• Example: H2 can be used to reduce metal oxides to metals
MO2(s) + H2(g)  M(s) + H2O(l) (catalyzed rxn)
M2O3(s) + 3H2(g)  2M(s) + 3H2O(l)
• Production of Ammonia using the Haber process:
N2(g) + 3H2(g)  2NH3(g)
• Manufacture of hydrochloric acid
H2(g) + Cl2(g)  2HCl(g)  HCl(aq)
Group 1A - Alkali Metals (ns1)
• Lithium (Li), Sodium (Na); Potassium (K); Rubidium (Rb);
Cesium (Cs); Francium (Fr)
• All are soft, lustrous, reactive metals with low melting points.
• Almost all compounds are ionic, except for some Li and Na
organometallic compounds
• weak metallic bonding - attraction between delocalized electrons

and metal-ion cores in crystalline structure
• Powerful reducing agents – lose 1 electron becoming 1+ cations,

donating the electron to other elements
• Low Ionization Energy (IE) – Each alkali element has the largest
size and the lowest IE in its Period
• Size of atom decreases considerably when valence electron is lost
• Lattice Energy – The atomic radius increases as you move down a

group. Since the square of the distance is inversely proportional to
the force of attraction, lattice energy decreases as the atomic radius
increases
• For a given anion, the Lattice Energy become smaller as the cation
becomes larger
• Solubility – Despite strong ionic attractions, the Group 1A salts are
water soluble – attraction between the ions and the polar Water
molecule creates highly Exothermic Heat of Hydration (Hhydr)
• Entropy – Entropy increases as ions disperse going into solution

overcoming the high lattice energy
• Magnitude of Hydration Energy decreases as ionic size increases
(Li+ > Na+ > K+ > Rb+ > Cs+

Reactions & Compounds of Alkali Metals
– Alkali metals reduce Hydrogen in Water to form Hydrogen gas
2E(s) + 2H2O  2E+ + 2OH-(aq) + H2(g)
Where E = any alkali metal (Li, Na, K, Rb, Cs)
Reaction becomes more vigorous down group
– Alkali metals reduce oxygen, but product depends on the metal
4Li(s) + O2(g)  2Li2O(s) oxide
K(s) + O2(g)  KO2(s) superoxide
– Alkali metals reduce Hydrogen to form ionic hydrides
2E(s) + H2(g) 2EH(s)
Reactions & Compounds of Alkali Metals
• Alkali metals (E) reduce Halogens (X) to form Halides
2E(s) + X2  2EX(s) X = F, Cl, Br, I)
• Sodium Metal (Na) can be produced from Molten NaCl and

electricity
2NaCl(l)  2Na(l) + Cl2(g)
• Sodium Hydroxide (Lye) can be produced from Salt (NaCl), water

(H2O) and electrolysis
2NaCl(s) + H2O(l)  2NaOH(aq) + H2(g) + Cl2(g)

Production of Alkali Metals
• Li and Na are produced by electrolysis of molten chlorides (LiCl

and NaCl).
• All can be obtained by electrolysis of their molten salts.
Cathode: M+ + e– M
Anode: Cl– ½Cl2 + e–
• K is produced by displace method using molten KCl and Na vapor:
KCl(l) + Na(g)  K(g) + NaCl(l)

Reactivity
• All react with halogens, hydrogen, and water.
M + ½X2 MX X = F, Cl, Br, I
M + ½H2 MH
M + H2O MOH + ½H2
• Only Li reacts with N2(g) and is the only element that reacts with
nitrogen at room temperature.
6Li + N2 20 - 200 2Li3N

Cont…
• When burned in air, alkali metals form either the oxide, peroxide,
or superoxide as the principal product, depending on the size of the
cation.
4Li(s) + O2(g)  2Li2O(g) (simple oxide)
2Na(s) + O2(g)  Na2O2(s) (peroxide, O2 2–)
K(s) + O2(g)  KO2(s) (superoxide, O2 1–)
• Sodium also produces some Na2O along with Na2O2.
• The superoxide compounds are a rare example of a paramagnetic

binary non-transition element compound.
Alkali Metals in NH3(l)
• All alkali metals dissolve in liquid ammonia to give blue solutions

of solvated electrons.
Uses of Lithium and Lithium Compounds
• Lithium mainly used to make lithium batteries;
• LiCl is used in air-conditioning units as dehumidifier;
• Li2CO3 is used in porcelain enamels, manufacture of tough (pyrex)

glasses, and as medication for manic depression;
• Alloys of Li-Al-Mg for aircraft and space applications.

Important Compounds of Sodium
• NaCl:
1. As an ingredient in food – Na+ is essential to the body for

electrolyte balance;
2. Production of sodium metal by electrolysis of molten NaCl;
2NaCl(l)  2Na(s) + Cl2(g)
3. Production of NaOH by electrolysis of aqueous NaCl;
2NaCl(l)  2NaOH(aq) + H2(g) + Cl2(g)

Important Compounds of Potassium
• K+ is essential for nervous system;
• K2O is important component in fertilizers;
• KO2 is used in confined places like submarines for removal of CO2

and production of O2:
4KO2(s) + 2CO2(g)  2K2CO3(s) + 3O2(g)

Group 2A - Alkaline Earth Metals (ns2)
• Be, Mg, Ca, Sr, Ba, Ra (E2+ ions)
• Oxides (except Be) give basic (alkaline) solutions: Ca(OH)2,

Mg(OH)2
• High melting points (higher lattice energy than 1A)
• Atomic & Ionic sizes
– Smaller radii and higher ionization energy
– Harder & more dense than Alkali metals, but soft and
lightweight compared to transition metals (Fe, Cr, etc)
• Even though, have higher ionization potential, they still form ionic
compounds (E2+), but Beryllium (Be) is an exception forming
covalent bonds
• Like Alkali metals, Alkaline Earth metals are strong reducing

agents
• are reactive because the higher lattice energy of their compounds

more than compensates for the large total Ionization Energy (IE) to
form the 2+
• The higher Lattice Energy (from the smaller cation size) and higher
Charge Density results in lower solubility
• The anomalous behavior of Beryllium
– Beryllium has smallest size; highest Ionization energy, and highest

Electronegativity of the Alkaline Earth elements
– Combined with the high charge density of the ion (Be2+) it polarizes
the nearby electron clouds very strongly and causes extensive orbital
overlap; this results in covalent bonding
– BeF2 is the most ionic of the Beryllium compounds, but its melting
point and electrical conductivity are relatively low
– Unlike the other Alkaline Earth Metals, whose oxides are basic, BeO
is amphoteric and does not react with water to form OH- ions
• Reactions & Compounds (E = Mg, Ca, Sr, Ba)
– Metals reduce Oxygen (O2) to form Oxides
2E(s) + O2(g)  2EO(s)
Ba + O2  BaO2 (Barium Peroxide)
– Larger metals reduce water to form hydrogen gas
E(s) + 2H2O(l)  E2+aq) + 2OH- (aq) + H2(g)
– Metals reduce Halogens to form ionic halides
E(s) + X2  EX2(s) (X = F, Cl, Br, I)
– Most metals (Be exception) reduce Hydrogen to form ionic
hydrides
E(s) + H (g)  EH (s) (except Be)
Reactions & Compounds (E = Mg, Ca, Sr, Ba) (Cont’d)

• Most elements reduce Nitrogen to form ionic Nitrides
3E(s) + N2(g)  E3N2(s) (except Be)
2 M3N2 + 6H2O 6M(OH)2 + 2NH3
• Element Oxides are Basic (except for amphoteric BeO)
EO(s) + H2O(l)  E2+(aq) + 2OH-(aq)
• All Carbonates undergo thermal decomposition to the oxide
ECO3(s)  EO(s) + CO2(g) (CaO – Lime)
Extraction of Mg from Seawater
1. Mg2+(aq) + CaO(s) + H2O(l)  Mg(OH)2(s) + Ca2+(aq)
2. Mg(OH)2(s) + 2HCl(aq)  MgCl2(aq) + 2H2O(l)
3. MgCl2(aq)  MgCl2(s)  MgCl2(l)
4. MgCl2(l) electrolysis  Mg(s) + Cl2(g);
Extraction of Calcium from CaCO3
1. CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(l) + CO2(g);
2. CaCl2(aq)  CaCl2(s)  CaCl2(l);
3. CaCl2(l) electrolysis  Ca(s) + Cl2(g)

Uses of Some Alkaline Earth Metals
Beryllium:
1. a component in alloys for making tough springs and non-

sparking tools
2. Used as X-ray tube window;
3. A neutron source in nuclear reactor;

Magnesium is used:
1. in the manufacture of light-weight alloys for aircraft body and

parts;
2. as reducing agent in the extraction of silicon, titanium and

beryllium;
3. in Grignard reagents for organic synthesis;
4. An ingredient in fireworks and warning flare;
Calcium is also used as reducing agent in the extraction of other

metals, such as Sc and W;
Important Compounds of Magnesium
• Mg2+ is essential to life;
• Many enzymes require Mg2+; Mg2+ is an essential component of

chlorophyll;
• MgO is a component in ceramic and used in refractory furnace

lining;
• Mg(OH)2 is active component of antacid “Milk of Magnesia”
• MgSO4 found in fertilizers and food supplements

Important Compounds of Calcium
• In cell physiology, movements of Ca2+ in and out of cytoplasm
function as signal for many cellular processes;
• Ca5(PO4)3(OH) - in teeth and bone structures;
• CaCO3 – forms protective coverings, as in egg and sea shells;
• CaCO3 (limestone) - most abundant mineral;
1. Pure CaCO3 are used as fillers in paint, toothpaste, paper,
plastics,
2. the source for calcium metal and quicklime:
Calcination: CaCO3(s)  CaO(s) + CO2(g)
Important Compounds of Calcium (Cont’d)
• CaO – also called quicklime, uses:
1. important ingredient of Portland cement;
2. industrial base;
3. extraction of Mg from seawater;
4. in metallurgy – as base in steel production;
5. As scrubber to remove toxic gas SO2 from industrial “flu-

gas”:
CaO(s) + SO2(g)  CaSO3(s)

Ca2+ & Mg2+ in Water
• Ca2+ and Mg2+ causes water hardness;
Soaps do not form leather due to formation of precipitates

with Ca2+ & Mg2+;
• These ions can be removed by ion-exchange process.
• Cation-exchange resins – large molecules that have many -SO3-

sites, with Na+ as counter ions;
• Ca2+ and Mg2+ bound more strongly to anionic sites and displace
Na+.
A Schematic Representation of a Typical Cation Exchange Resin
Group 3A – Boron Family (ns2np1)
• B, Al, Ga, In, and Tl;
• Group 3A elements show increasing metallic character going down

the group.
• group contains one metalloid and five metals
• Reactive
• solids at room temperature
• Boron: a metalloid, forms covalent network solid, and highest

melting point in the group
Oxidation-Reduction (REDOX) behavior in Group 3A
– Presence of Multiple Oxidation States
• In Groups 3A – 6A many of the larger elements (down the

group) exhibit an oxidation state “two lower” than the A-
Group number
• This lower state occurs when the atoms lose their np

electrons, not the ns electrons.
• The lower oxidation state is the result of lower bond energies
• Bond energies decrease as the size of the atom and the bond
length increase for elements lower in the group
– Increasing prominence of the low oxidation state
• When a group exhibits more than one oxidation state, the

lower state becomes more prominent going down the Group
• All members of the 3A group exhibit the +3 state, but the +1

state appears first with some compounds of Gallium (Period
4)
• The +1 state becomes the most important state of Thallium

(Period 6)
• Relative Basicity of Group 3 oxides
– In general, oxides with the element in a lower oxidation state

(less positive) are more basic than oxides with the element in a
higher oxidation state
– For Indium oxides in Group 3A, In+12O acts more like a metal
and is more basic than In+32O3
– The lower charge density of In+1 does not polarize the O-2 ion as
much as the In+3 ion
– Thus, in E2O compounds, the E-O bonding is more ionic than in

E2O3 compounds, thus; the O-2 ion is more available to act as a
Reactions & Compounds
• Elements react sluggishly, if at all, with water (H2O)
2 Ga(s) + 6H2O(hot)  2Ga3+(aq) + 6OH-(aq) + 3H2(g)
2Tl(s) + 2H2O(steam)  2Tl+(aq) + 2OH-(ag) + H2(g)
• All members form oxides when heated in pure O2
4E(s) + 3O2(g)  2E2O3(s) (E = B, Al, Ga, In)
4Tl(s) + O2  2Tl2O3(s)
• Oxide acidity decreases down the group:
B2O3 > Al2O3 > Ga2O3 > In2O3 > (Tl2O3 > TlO2)
(weakly acidic) (strongly basic)
• Reactions & Compounds
– All members reduce Halogens
2E(s) + 3X2  2EX3 (E = B, Al, Ga, In)
2Tl(s) + X2  2TlX(s)
 Trihalides of Al, Ga, In are mostly ionic but

exist as dimers in the gas phase
 Acid (H2SO4) treatment of Al2O3 produces Al2SO4, a colloid

(coagulant) used in water purification
• Al2O3 + 3H2SO4  Al2SO4(s) + 3H2O(l)

• Boron Chemistry
– Boron compounds are covalent (unique within group)
– Forms network covalent compounds or large molecules with

metals, H, O, N
– Electron deficient; uses two approaches to complete octet
1. Accepting a Bonding Pair from Electron-Rich atom
BF3(g) + NH3(g)  F3B-NH3(g)
(BF3 acts as acts as Lewis acid in accepting the electron pair from
the Nitrogen in NH3)
Boron Chemistry (cont’d)
2. Forming Bridge Bonds with Electron-Poor Atoms
– Boron Hydrides - Boranes
– 2 types of B – H bonds
» Normal electron-pair bond
o sp3 orbital of B overlaps 1s orbital of H in each of the

four terminal B-H bonds
Boron Chemistry (con’t)
• Hydride Bridge Bond (3-center, 2 electron bond)
o Each B – H – B grouping is held together by only two electrons
o Two sp3 orbitals, one from each B, overlap an H 1s orbital

between them
o Two electrons move through this extended bonding orbital –

one from one of the B atoms and the other form the H atom –
and join the 2 B atoms via the H atom bridge
• Boron Halides:
 are highly reactive, volatile, covalent compounds with trigonal
planar geometry.
 are Lewis acids by using the vacant 2p orbital to accept

electrons.
• Boron Hydrides (Boranes; B2H6):
 are volatile, covalent compounds with formulas BnHm.
NaBH4 + I2 B2H6, H2, and NaI.

Applications of Boron
• B(OH)3 is a Lewis acid, boric acid that people love to call the
“natural” or “organic” way to kill pests. Sure.
• Boron also forms some very interesting compounds with nitrogen

called boron nitrides which have the same electronic configuration
as graphite and C60 and consequently have prompted a lot of
interest in them for new materials.
• 2B + 2NH3 2BN + 3H2

Aluminum chemistry
• Obtained mainly from bauxite (Al2O3·2 H2O).
• Main oxide is Al2O3. Impurities give ruby (Cr) and sapphire (Fe and
Ti).
• Main halide is AlX3 but can be more complex.
• Forms nitrides AlN.
• Aluminum forms bridged compounds with some organic molecules
• Aluminum chloride forms a dimer.
• Aluminum hydride forms a polymer.

Aluminum Production
• Extracted from bauxite, Al2O3nH2O;
• Produced by the Hall-Heroult process - electrolysis of molten

Al2O3-Na3AlF6 (cryolite) mixture at ~ 960oC
1. Ore dressing
2. Chemical treatment of bauxite
2NaOH + Al2O3→ Na2Al2O3 + H2O
Na2Al2O3 + 4H2O 2Al(OH)3 + 2NaOH
2Al(OH)3Al2O3 + 3H2O
3. Reduction of aluminium from aluminium oxide

Reactions of Aluminum
1. With strong acids:
• 2Al(s) + 6 HCl(aq)  2AlCl3(aq) + 3H2(g);
• 2Al(s) + 3H2SO4(aq)  Al2(SO4)3(aq) + 3H2(g);
• 2Al(s) + 2HNO3(aq)  Al2O3(s) + 2NO(g) + H2O(l)
(The third reaction does not occur completely because the oxide
forms protective coating to prevent further reaction.)
1. With a strong base:
• 2Al(s) + 6H2O(l) + 2NaOH(aq)  2NaAl(OH)4(aq) + 3H2(aq);

Important Compounds of Aluminum
• Al2O3 – source of aluminum metal and forms protective coating

to the metal to prevent corrosion;
• Al2(SO4)3 – most important industrial compound;
1. use in municipal water treatment plants;
2. papermaker’s alum
3. Prepared by reaction of H2SO4 with Al2O3 or Al(OH)3:
Al2O3(s) + 3H2SO4(aq)  Al2(SO4)3(s) + 3H2O(l)
2Al(OH)3(s) + 3H2SO4(aq)  Al2(SO4)3(s) + 6H2O(l)

Important Compounds Aluminum
• Forms strong, lightweight alloys with copper and magnesium for

aircraft bodies and parts;
• High resistance to corrosion - extensively used to make beverage

containers (soda drinks cans);
• Also used as reducing agent in the fuel during space shuttle

launching.
• most famously, the production of paper.
• Aluminum oxides are also the basis of many valuable gems when
combined with trace metals
Group 4A – Carbon Family (ns2np2)
• The whole range of elemental behavior occurs within the 4A group
– Non metallic Carbon (C)
– Metalloids (Silicon (Si) & Germanium (Ge)
– Metallic (Tin (Sn) & Lead (Pb)
– Newly synthesized element at bottom of group

• Bonding effects on Physical Properties
– Silicon has a much lower melting point than Carbon because of

the longer, weaker bonds.
– The melting point difference between Germanium (Ge) and Tin

(sn) is due to the change from network covalent to metallic
– Going from Group 3 to group 4 there are large increases in

melting point and the Hfus because of the change from metallic
to network covalent bonding
Allotropism: Different Forms of an Element
• Different crystalline & molecular forms with different physical

properties
Carbon Allotropes:
1. Graphite:
 Black, “greasy”, soft, more stable than diamond
 has sp2 hybridization; conduct electric current;
 It is what makes up soot, activated charcoal, and of course,

pencil lead.
2. Diamond:
 Colorless, electrical insulator, extremely hard
 contains sp3 hybridization and forms covalent network solids;

does not conduct electricity; lacking in bonds, doesn’t have a
 is pretty and shiny, engineers like because it is the hardest

compound known and the best heat conductor known.
 This means that being able to make it synthetically by

subjecting graphite to high pressures and temperatures,
produces a really great abrasive (the best sandpaper known.)
3. Bucky-Balls (Buckminsterfullerene):
 soccer ball-shaped with the formula C60
 it is conducting,
 it is a molecule and so can be dissolved in solvents (like

benzene),
 is a cage that you can put things in, like metal that become
superconducting at high temperatures,
 it is of a more general class that includes nano tubes.
• Tin Allotropes
– -tin (stable at room To. And above ) and -tin (stable < 13oC)
• Bonding Changes in Group 4A
– Carbon – Covalent (intermediate EN)
– Si & Ge – strong polar bonds (silicate minerals)
– Tin (Sn) & Lead(Pb) – Metallic (Ionic)
• Multiple Oxidation States
– Carbon (+4)
– Silicon (+4 more stable than +2)
– Lead (+2 more stable than +4)
– Elements with lower oxidation states act more like metals (more
basic)
Highlights of Carbon Chemistry
• Carbon, like other elements in “Period 2, is the anomalous element

in the group
• Carbon forms bonds with:
– Smaller Group 1A & 2A metals
– Many transition metals, Halogens, Neighbors B, Si, N, O, P, S
– Exhibits all possible oxidation states from +4 in CO2, and

Halides to -4 in CH4
Highlights of Carbon Chemistry (Cont’d)
• Carbon forms sp, sp2, and sp3 hybridizations;
• In sp hybridization, each carbon forms 2s- and 2p- bonds; example
in H―C≡C―H
• In sp2, each carbon forms 3s- and a p- bonds;
• In sp3 hybridization each carbon forms 4s-bonds;
• Two main features of Carbon Chemistry
1. Catenation: Carbon can form chains, branches, and rings
(aromatic & aliphatic)
2. Formation of Multiple bonds – sigma (), Pi (), Triple ()
Carbon compounds
1. Carbon monoxide is a colorless, odorless, toxic gas formed by

incomplete combustion of carbon.
2 C(s) + O2(g) 2 CO(g) H° = – 221 kJ
2 CO(g) + O2(g) 2 CO2(g) H° = – 566 kJ
• Carbon monoxide toxicity results from its ability to bind to the

Fe(II) atom of hemoglobin. O2-bonded hemoglobin is called
oxyhemoglobin. CO-bonded hemoglobin is called
carboxyhemoglobin.
Carbon compounds (Cont’d)
2. Carbon dioxide is a colorless, odorless, nontoxic gas formed by

complete combustion of carbon, by food metabolism, or by
treatment of metal carbonates with heat or acid.
C(s) + O2(g) CO2(g) H° = – 394 kJ
C6H12O6(aq) + Yeast 2CH3CH2OH(aq) + 2CO2(g)
Na2CO3(s) + 2H +(aq) 2Na+(aq) + CO2(g) + H2O(l)
CaCO3(s) + heat CaO(s) + CO2(g)

3. Carbonic acid (H2CO3) does not exist out of solution, but can be
converted to carbonates and hydrogen carbonates (bicarbonates).
4. Anhydrous sodium carbonate (Na2CO3) is used to make glass.

Its hydrated form (Na2CO3·10 H2O) is used as washing soda.
• Carbonate ions (CO3–) can be used to remove Ca2+ and Mg2+

from hard water, and in fabric degreasing.
Hydrogen cyanide is a highly toxic, volatile substance produced by

acidifying the cyanide ion.
CN–(aq) + H +(aq) HCN(aq, Ka = 4.9 ´ 10–10)
• Cyanide toxicity results from its ability to bind to the Fe(III) in

cytochrome oxidase.
• Cyanides are used to extract gold and silver:
4 Au(s) + 8CN –(aq) + O2( g) + 2H2O(l) 4 Au(CN)2 – (aq) +

4OH–(aq)
Zn(s) + 2Au(CN) 2– (aq) Zn(CN)4 2– (aq) + 2Au(s)

• Carbides: Carbon combines with metals to form ionic carbides

such as CaC2 and Be2C where carbon is in the form C2 2– and C 4–
• Carbides are strong Brønsted bases :
C2 2– (aq) + 2H2O(l) 2OH–(aq) + C2H2(g)
C 4– (aq) + 4H2O(l) 4OH–(aq) + CH4(g)
• Silicon carbide, SiC, is called carborundum:
SiO2(s) + 3C(s) SiC(s) + 2CO(g)

Use of Carbon Compounds
• CO – toxic gas (binds to hemoglobin); forms during combustion of

carbon in limited oxygen supply; used in methanol production.
• CO2 is essential to life – used by plants in photosynthesis;
• NaHCO3 – used as baking soda for cooking and as in fire-

extinguishers;
• Na2CO3 – used in glass manufacture;
• CaCO3 – used in steel production;

Use of Carbon Compounds
• CH4 – major component of natural gas; used as fuel and for the
production of hydrogen gas;
• C3H8 and C4H10 – used as fuel;
• C6H14, C7H16, C8H18, and C9H20 are components in gasoline
• C6H12, (cyclohexane), C6H14 (hexane), and C6H6 as organic

solvents;
• C2H4, C2H3Cl, C2F4, and H2NCH2CH2CH2CH2CH2CH2NH2 are

important monomers for polymers, such as polyethylene, PVC,
Teflon, nylon, and polyester.
Silicon Chemistry
• Silicon is a hard, gray, semiconducting solid that melts at 1410°C.
• The most common natural form is SiO2;
• Silicon Halides are more reactive than Carbon Halides because Si

(3s, 3p, 3d orbital's) has empty 3d orbital's for bond formation
• The Si – X bond is long but stronger than corresponding C – X

bond
• Si – X bond has some double bond character because of the

presence of a  bond and a different type of  bond
Group 4A – Silicon
Silicon Chemistry (Cont’d)
• Silicon is purified in a three-step process:
Step 1: Si(s) + 2Cl2(g) SiCl4(l)
Step 2: SiCl4(g) + 2H2(g) Si(s) + 4HCl(g)
Step 3 (Zone Refining):
• Is a process in which a heater melts a narrow zone of silicon rod.
• Impurities are more soluble in the liquid phase than the solid one.
• Sweeping the heater down the rod concentrates the impurities at the
end.
Group 4A – Silicon
• Silicates: are ionic compounds that contain the silicon oxoanion
along with cations such as Na +, K +, Mg 2+, or Ca 2+.
• The basic structure is an SiO4 tetrahedron that occurs as a simple
orthosilicate (SiO4 4–) in the mineral zircon (ZrSiO4).
 The Orthosilicate (–SiO4 –) grouping is the building unit for Silicate
minerals
 Zircon ZrSiO4 1 Unit
 Hemimorphite 2 Units [Zn4(OH2Si2O7H2O]
 Beryl 6 Units [Be3Al2Si6O18]

 Silicon Polymers
 Manufactured Substances
 Alternating Si & O atoms with two Organic groups bonded to
each Silicon atom
Chemistry of Tin and Lead
• Both are soft metals; Tm(oC): Sn (232) & Pb (327)
• Both metals form +2 and +4 oxidation states;
• Reacts with O2  SnO(I) and PbO(I)
SnO2(m) and PbO2(m);
• Reacts with Cl2  SnCl2(I) and PbCl2(I)
SnCl4(m) and PbCl4(m);
Where: I = ionic; m = molecular

Chemistry of Tin and Lead (Cont’d)
• Tin is obtained from the mineral cassiterite (SnO2), by reduction

with carbon:
SnO2(s) + 2C(s) + Heat Sn(l) + 2CO(g)
• Lead is obtained from the mineral galena (PbS), by roasting to

PbO and reduction with CO.
2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)
PbO(s) + CO(g) Pb(l) + CO2(g)

Important Compounds of Tin and Lead
• Tin - used mainly in tin-plating for making food cans, for making
solders, bronze, and pewter's;
• Lead - mainly used to make automobile batteries; some are used as
lead shots and radiation shields;
• SnCl2 – used as reducing agent, tin plating, catalyst;
• SnF2 – additive in toothpaste to prevent cavity;
• PbO – used in ceramic glaze, and cement;
• PbO2 – oxidizing agent and battery electrodes;
• PbCrO4 – for making yellow pigment for paint;
Important Reactions
– Group 4A elements are Oxidized by Halogens
E(s) + 2X2  EX4 (E = C, Si, Ge)
The +2 Halides are more stable for Tin (Sb) & Lead (Pb)
SnX2 PbX2
The Elements are oxidized by Oxygen (O2)
E(s) + O2(g)  EO2 (E = C, Si, Ge, Sn)
The oxides are more basic (metallic) going down the group
Lead (Pb) forms the + 2oxide (PbO) - basic
In natural streams, Carbon Dioxide (CO2) forms a weakly “acidic”
solution
CO2 + H2O ⇄ H2CO3(aq) ⇄ H+(aq) + HCO3-(aq)
Important Reactions (Cont’d)
• Air & Steam passed over hot coke (carbon) produce gaseous fuel
mixtures – producer gas & water gas
C(s) + H2O(g) + air(g)  CO(g) + CO2(g) + N2(g) + H2(g)
• Hydrocarbons react with O2 to form CO2 & H2O, a source of heat to

yield steam (H2O) for electrical generation
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) + Heat
• Certain metal Carbides react with water to produce Acetylene (H-

CC-H), used in oxyacetylene torches
CaC2(s) + 2H2O(g)  Ca(OH)2(aq) + C2H2(g)

Important Reactions
• Freon (chlorofluorocarbon) is formed from fluorinating Carbon

Tetrachloride
CCl4(l) + HF(g)  CFCl3(g) + HCL(g)
Production of Trichlorofluoromethane (Freon-11) is being discontinued

because it is an atmospheric pollutant
• Silica (SiO2)is reduced to form elemental Silicon used in the manufacture

of computer chips
SiO2(s) + 2C(s)  Si(s) + CO2(g)

Group 5A – Nitrogen Family (ns2np3)
Exhibits varied chemical properties.
1. N and P are nonmetals;
2. As and Sb are metalloids;
3. Bi is a metal (the heaviest non-radioactive element)

• Some Physical Properties, Sources, and Methods of Preparation

• Arsenic (As) and Antimony (Sb) are network covalent metalloids
with highest melting points in group
• Bismuth (Bi) exhibits metallic bonding
• Nitrogen (N) exists as diatomic molecules, which interact through

very weak dispersion force producing a boiling point 200 oC below
room temperature
• Phosphorus (P) is heavier and more polarizable than Nitrogen with

stronger dispersion forces – higher melting point 44oC
Chemical Behavior in Group 5A Patterns
• Nitrogen forms a maximum of 4 covalent bonds

• The other elements in the group can expand the valence shell by
using empty ‘d’ orbitals
• As in groups 3A & 4A, fewer oxidation states occur moving down
the group with the lower oxidation state becoming prominent
– Oxidation states
• Nitrogen – from +5 to -3
• P, As, Sb – +5 & +3
• Bi – +3
Oxides of Group 5A Elements
• Nitrogen: N2O, NO, N2O3, NO2, N2O4, N2O5;
• Phosphorus: P4O6 & P4O10;
• Arsenic: As2O3 (As4O6) & As2O5;
• Antimony: Sb2O3 & Sb2O5
• Bismuth: Bi2O3 & Bi2O5

Chlorides of Group 5A Elements
• Nitrogen: only NCl3;
• Phosphorus: PCl3 and PCl5;
• Arsenic: AsCl3 and AsCl5;
• Antimony: SbCl3 and SbCl5;
• Bismuth: BiCl3
• All are molecular compounds.

Reactions of Oxides and Chlorides
• 3NO2(g) + H2O(l)  2HNO3(aq) + NO(g);
• N2O5(g) + H2O(l)  2HNO3(aq)
• P4O10(s) + 6H2O(l)  4H3PO4(aq);
• As2O5(s) + 3H2O(l)  2H3AsO4(aq);
• PCl5(s) + 4H2O(l)  H3PO4(aq) + 5HCl(aq);
• AsCl5(s) + 4H2O(l)  H3AsO4(aq) + 5HCl(aq);
• 2SbCl5(s) + 5H2O(l)  Sb2O5(s) + 10HCl(aq);

The Chemistry of Nitrogen
• Main mineral source is KNO3 and NaNO3 and also from NH4NO2.
• Most compounds are covalent, although certain metals form the N3– ion.
• The triple bonds (NN) in N2 provide high stability to the molecule;
• Many reactions involving nitrogen gas are endothermic and compounds

containing nitrogen decompose exothermically to the elements.
• N2(g) + O2(g)  2NO(g) H = 180 kJ
• 2NO2(g)  N2(g) + O2(g); H = -68 kJ
N2H4(g)  N2(g) + 2H2(g); H = -95 kJ

Nitrogen Fixation
• The process of transforming N2 to other nitrogen–containing

compounds.
• Atmospheric fixation (occurs naturally during thunderstorm):
• N2(g) + O2(g)  2NO(g); DHo = 180 kJ
• 2NO(g) + O2(g)  2NO2(g); DHo = -112 kJ
• 3NO2(g) + H2O(l)  2HNO3(aq) + NO(g);

DHo = -140 kJ
Biological Nitrogen Fixation
• Fixation of atmospheric N2 by bacteria living in soils and water;

some live in root nodules;
• Plants such as legumes and alfalfa have root nodules that contain
nitrogen-fixing bacteria – they benefit directly from these bacteria;
• Other plants benefit when the bacteria die and release absorbable
forms of nitrogen (NH3, NH4+, and NO3-) to the soils;
Biological Nitrogen Fixation (Cont’d)
• In nitrogen-fixing bacteria
1. Atmospheric N2 is first reduced to NH3;
2. In bacterial cells, NH3 becomes NH4+, oxidized to NO2- and

then to NO3-;
3. NH3, NH4+, and NO3- can be released into the surroundings

(water or soils) and become available to plants;
• Denitrifying bacteria (in soils) change NO3- back to NO2-, NH3,

and finally to N2 to complete the biological nitrogen cycle.
Biological Fixation and The Nitrogen Cycle
Industrial Nitrogen Fixation
• Industrial Fixation (the Haber Process):
N2(g) + 3H2(g)  2NH3(g) H = -92 kJ
• Most NH3 are converted to:
1. Fertilizers (~70%)
2. Nitric acid, HNO3 (~20%)
3. Hydrazine, N2H4, and monomers for various plastics and

nylons.
Important Hydrides of Nitrogen
Ammonia, NH3
• A colorless, pungent gas with a polar trigonal pyramidal geometry.
3 H2 (g) + N2(aq) 2NH3(g) (H° = –92.2 kJ)
Liquid ammonia autoionizes:
2NH3(l) æ NH4 +(aq) + NH2 –(aq) (NH2 – = amide ion)
 Production of fertilizers (NH4NO3, (NH4)2SO4, (NH4)3PO4, and
CO(NH2)2), HNO3, and N2H4

Hydrazine (H2NNH2):
• A colorless, poisonous liquid.
• Rocket propellant, manufacture of plastics, agricultural pesticides;
Formation: 2NH3(aq) + OCl – N2H4(aq) + H2O(l) + Cl –(aq)
Oxygen Reaction: N2H4(l) + O2(g) N2(g) + 2H2O(l)
• Monomethylhydrazine, CH3N2H3
 Rocket fuels
Oxides of Nitrogen
• In its oxides nitrogen has oxidation states ranging from +1 to +5.
1. N2O (+1)
2. NO (+2)
3. N2O3 & HNO2 (+3)
4. NO2 (+4)
5. N2O5 & HNO3 (+5)
 In other compounds, nitrogen could have oxidation states of -
1 to -3.
 NH2OH (-1), N2H4 (-2), and NH3 (-3)
Nitrous Oxide (N2O):
• A colorless gas commonly known as “laughing gas.”
Formation: NH4NO3 N2O(g) + 2H2O(g)
Decomposition: 2 N2O(g) 2N2(g) + O2(g)

• Nitric Oxide (NO): A colorless, paramagnetic gas.
Nitrogen fixation: N 2(g) + O2(g) æ 2 NO(g) G°= 173.4 kJ
• Nitrogen Dioxide (NO2): A toxic, yellow –brown,

paramagnetic gas that dimerizes to form N2O4.
• Prepared from copper and nitric acid:
Cu(s) + 4 HNO3(aq) Cu(NO3)2(aq) + 2 H2O(l) + 2

NO2(g)
Production of HNO3
-The Ostwald Process
1. NH3(g) + O2(g)  NO(g) + H2O(g);
2. 2NO(g) + O2(g)  NO2(g);
3. 3NO2(g) + H2O(l)  2HNO3(aq) + NO(g);

Reactions of Nitric Acid
• HNO3 - a strong acid and an oxidizing agent;
• Reactions with metals does not produce H2
1. Cu(s) + 4HNO3(16 M)  Cu(NO3)2(aq) + 2NO2(g) +

2H2O(l);
2. 3Cu(s) + 8HNO3(aq, 6 M)  3Cu(NO3)2(aq) + 2NO(g) +

4H2O(l);
3. 4Zn(s) + 10HNO3(aq, 3 M)  4Zn(NO3)2(aq) + N2O(g) +

2H2O(l);
• Nitric Acid (HNO3): A powerful oxidizing agent for many

metals. HNO3 decomposes spontaneously:
4HNO3(l) 4NO2(g) + 2H2O(l) + O2(g)
• Nitrous Acid (HNO2): is formed from the reaction of nitrogen

dioxide with water.
2NO2(g) + H2O(l) HNO2(aq) + H+(aq) + NO3 –(aq)

Allotropes of Phosphorus
• White Phosphorus: P4 (tetrahedral) - toxic and very reactive
• Black Phosphorus: crystalline structure - much less reactive
• Red Phosphorus: amorphous with P4 chains
P(white)  P(red)

heat, 1 atm, no air
P(white) or P(red) 

 P(black) high pressure
Oxides of Phosphorus
• Reaction of white phosphorus with oxygen:
1. P4(s) + 3O2(g)  P4O6(l); (o.s. of P = +3)
2. P4(s) + 5O2(g)  P4O10(s); (o.s. of P = +5)
• Reactions of phosphorus oxides with water:
1. P4O6(l) + 6H2O(l)  4H3PO3(aq);
2. P4O10(s) + 6H2O(l)  4H3PO4(aq);

Oxyacids of Phosphorus
• Most commonly found as phosphate rock such as Ca3(PO4)2, and

Ca5(PO4)3 F.
• Elemental phosphorus is obtained from the decomposition of Ca

3(PO4)2.
• Phosphoric acid, H3PO4 - triprotic
• Phosphorous acid, H3PO3 - diprotic
• Hypophosphorous acid, H3PO2 - monoprotic

Phosphorus Halides (PX3, PX5)
• Reactions of white phosphorus with halogens:
1. P4(s) + 6X2  4PX3(l);
2. P4(s) + 10X2  4PX5(s);
• Examples of reactions:
1. P4(s) + 6Cl2(g)  4PCl3(l);
2. P4(s) + 10Cl2(g)  4PCl5(s);
3. PCl3(l) + Cl2(g) ⇄ PCl5(s);
• Solid PCl5 exists as [PCl4+] and [PCl6 –]

Reactions of Phosphorus Halides
Reactions with water:
• PCl3(l) + 3H2O(l)  H3PO3(aq) + 3HCl(aq);
• PCl5(s) + 4H2O(l)  H3PO4(aq) + 5HCl(aq);

Hydrides of phosphorus
• Most important is phosphine.
• PH3 a very poisonous gas:
P4(s) + 3NaOH(aq) + 3H2O(l) 3NaH2PO4(aq) + PH3(g)
• PH3 is a strong reducing agent and burns in air:
PH3(g) + 2O2(g) H3PO4(l)

Important Compounds of Phosphorus
• Ca3(PO4)2 & Ca5(PO4)3F : source of phosphorus
• Ca5(PO4)3(OH) : forms bones and teeth
• P4O10 : formation of H3PO4
• H3PO4 : production of fertilizers & phosphates
• H2PO4- & HPO42- : phosphate buffers
• Na3PO4 : scouring powder and paint remover
• Na5P3O10 : fabric softeners
• ADP & ATP : storage of metabolic energy
• PCl5 : precursor for lithium hexafluorophosphate (LiPF6), an electrolyte
in lithium ion batteries;
Group 6 – Oxygen Family (ns2np4)
– First two members of group – gaseous nonmetallic

oxygen (O) & solid nonmetallic sulfur (S) are among
most important elements in industry, the environment
and living organisms
– Selenium (Se) & Tellurium (Te) are metalloids
– Polonium (Po) is radioactive and only metal in the

group
Oxygen Family vs. Nitrogen Family
• Groups 5A & 6A have similar Physical & Chemical Properties
• Nitrogen & Oxygen are low-boiling Diatomic gases
• Phosphorus & Sulfur occur as polyatomic molecules – P4 & S8
• Arsenic (Ar) & Selenium (Se) occur as gray metalloids
• Antimony (Sb) & Tellurium more metallic than preceding group

members, but display network covalent bonding
• Bismuth & Polonium are metallic crystals
• Electrical conductivity increases down group as bonding changes

from molecules to metalloid networks to metallic solids
Oxygen Family vs. Nitrogen Family (Cont’d)
Allotropism
• Oxygen has 2 allotropes
1. Dioxide (O2):
• is colorless, odorless,
• paramagnetic, and thermally stable
2. Ozone (O3):
• is bluish, has pungent odor,
• is diamagnetic,
• decomposes in heat and Ultraviolet light.

Oxygen Chemistry vs. Nitrogen Chemistry
• Oxygen & Sulfur occur as anions more often than Nitrogen &
Phosphorus
• Oxygen & Sulfur bond covalently with almost all nonmetals
• Selenium & Tellurium do some covalent bonding, whereas

Polonium behaves like a metal
• Oxygen has few oxidation states (O2- most common)
• The other elements in the family exhibit +6. +4,
• 2 oxidation states, with the +4 state most common in Tellurium and

Polonium
Highlights of Oxygen Chemistry
– Most free Oxygen (O2) has biological origin from photosynthesis in algae
and multicellular plants
– Although much more complicated, the basic reaction between oxygen, CO2
and light to form carbohydrates can be represented as:
nH2O(l) + nCO2(g)  nO2(g) + (CH2O)n
– The reverse process of combustion and respiration produce CO2
– Every element, except He, Ne, Ar (noble gases) form at least one oxide
– Some oxides have Endothermic heats of reaction, while others have

Exothermic ones
Various Forms of Oxides
• Metal oxides (ionic)
1. Nonconductor – example: MgO
2. Semiconductor – example: NiO
3. Conductor – example: ReO3
4. Superconductor – example: YBa2Cu3O7
• Nonmetal oxides (covalent):
Molecular oxides – examples: CO2, NO, NO2, N2O, SO2,
P4O10, etc.
Covalent network oxide – SiO2
Characteristics of Oxides
• Metallic oxides – basic or amphoteric
Examples: Na2O (basic); Al2O3 (amphoteric)
• Semi-metallic oxides – mild to weakly acidic
Example: B2O3
• Nonmetallic oxides – weak to strong acids
Examples:
1. SO2(g) + H2O(l)  H2SO3(aq) (weak acid);
2. SO3(g) + H2O(l)  H2SO4(aq) (strong acid);

Highlights of Sulfur Chemistry
• Two important oxides – SO2 & SO3
– Sulfur Dioxide (+4 oxidation state) is a colorless choking gas

that forms when S, H2S, or a metal sulfide burns in air (oxygen)
2H2S (g) + 3O2(g)  2H2O(g) + 2SO2(g)
FeS2(s) + 11O2(g)  2Fe2O3(s) + 8SO2(g)
– Sulfur Dioxide dissolves in water to form Sulfurous acid

(H2SO3) – weak acid - which dissociates into an equilibrium
solution of hydrated SO2, H+ ions, & Bisulfite (HSO3-) ions
SO2(g) + H2O(l) ⇄ [H2SO3(aq)] ⇄ H+(aq) + HSO3-(aq)

• S in the Sulfite ion (SO32-) is in the 4+ state and can be easily
oxidized to 6+ state.
• Thus, Sulfites are good Reducing Agents
• SO3 (Sulfur Trioxide) is produced by oxidizing SO2
SO2(g) + 1/2O2 ⇄ SO3(g)
• Sulfuric Acid (H2SO4) is a strong acid and the most common

industrial chemical
It is prepared from SO3, H2O, & conc H2SO4
SO3(g) + conc H2SO4 + H2O  H2SO4(l)
• Conc Sulfuric acid is an excellent dehydrating agent

• Sulfur is found in nature both in large deposits of the free element
and in ores such as:
• Galena = PbS,
• Cinnabar = HgS,
• Pyrite = FeS2,
• Gypsum = CaSO42H2O),
• Epsomite = MgSO4.7H2O, and
• Glauberite = Na2Ca(SO4)2
Sulfur Oxides and Oxyacids
S(s) + O2(g)  SO2(g)
2SO2(g) + O2(g)  2SO3(g)
SO2(g) + H2O(l)  H2SO3(aq)
SO3(g) + H2O(l)  H2SO4(aq)
• H2SO3 – diprotic; weak acid
• H2SO4 – diprotic; strong acid

Sulfuric Acid
• Productions:
1. S8(s) + 8 O2(g)  8SO2(g);
2. 2H2S(g) + 3 O2(g)  2SO2(g) + 2H2O(l);
3. FeS2(s) + 11 O2(g)  Fe2O3(s) + 8SO2(g);
1. 2SO2(g) + O2(g)  2SO3(g); (V2O5/K2O catalyst)
2. 2SO3(g) + H2SO4(l)  H2S2O7(l);
3. H2S2O7(l) + H2O(l)  2H2SO4(l);

Important Compounds of Sulfur
• H2SO4 – most important compound, for manufacture of fertilizer,

soap, detergents, metal and textile processing, sugar refinery, and
organic syntheses;
• SF4 – for fluoridation
• SF6 – as insulating and inert blanket
• Na2S2O3 – as reducing agent and complexing agent for Ag+ in

photography (called “hypo”);
• P4S3 – in “strike-anywhere” match heads

Group 6A – Sulfur
• Hydrogen Sulfide:
• A toxic, colorless gas with the odor of rotten eggs.
• H2S is more dangerous than HCN.
• Reacts with Fe 3+ to give S, Fe 2+, and H +.

Group 7 – Halogen Family (ns2np5)
Trends in Selected Physical Properties

Some Physical Properties, Sources, and Methods of Preparation

Highlights of Halogen Chemistry
• The Hydrogen Halides (HX) are formed from the reaction of metal
halides and a concentrated acid
CaF2(s) + H2SO4(l)  CaSO4(s) + 2HF(g)
2NaBr(s) + H3PO4(l)  Na3PO4(s) + 3HBr(g)
2NaCl(s) + H2SO4(aq)  2HCl(g) + Na2SO4(aq)
• HBr is usually formed from PBr3 and H2O:
PBr3(l) + 3 H2O(l) 3HBr(g) + H3PO3(aq)

• Hydrogen Fluoride, with its short, strong bond forms a weak acid
(Hydrofluoric acid) with water
HF(g) + H2O(l)  H3O+ + F-
• The other Hydrogen Halides (Cl ,Br, I) dissociate completely to

form stoichiolmetric amounts of H3O+ ions – strong acids
HBr(g) + H2O(l)  H3O+(aq) + Br-(aq)

• Halogens react Exothermically with one another to form many

“Interhalogen” compounds
Cl2(g) + 3F2(g)  2ClF3(g);
Br2(l) + 3F2(g)  2BrF3(l);
Br2(l) + 5F2(g)  2BrF5(l);
I2(s) + 3Cl2(g)  I2Cl6(s); (dimeric form
• The more electronegative atom has the 1- charge; the other less
electronegative atom has 1+ charge
Halogen Oxyacids and Oxyanions
• All halogens except fluorine combine with various numbers of

oxygen atoms to form oxyacids.
• Strengths of oxyacids vary directly to the number of oxygen

atoms bonded to the halogen - acid strength increases as more
oxygens are added.
Hypohalous acid: HXO
Halous acid: HXO2
Halic acid: HXO3
Perhalic acid: HXO4

The Known Oxyacids of the Halogens
Reactions of Interhalogen Compounds
• ClF3 & BrF3 – fluoridating agents
1. 2B2O3(s) + 2BrF3(l)  4BF3(g) + Br2(l) + 3 O2(g)
2. P4(s) + 5ClF3(g)  4PF3(g) + Cl2(g) + 3ClF(g)
• Reaction with water is explosive:
1. ClF3(g) + 2H2O(l)  HClO2(aq) + 3HF(aq);
2. BrF5(l) + 3H2O(l)  HBrO3(aq) + 5HF(aq);

Electronegativity of the Halogen
• Relative strengths of the Halogen Oxoacids depend on two factors
1. Electronegativity of the Halogen
• The more electronegative the halogen, the more electron density it
removes from the O-H bond, and the more easily the proton is lost
• Among Oxoacids with the oxidation state of the Halogen in each
Halogen the same, the Acidity (acid strength) decreases as the
Halogen’s Electronegativity (EN) decreases
Electronegativity – Cl > Br > I
Acidity – HOClO2 > HOBrO2 > HOIO2
2. Oxidation state of the Halogen
– The oxidation number is a number identical with the valency

but with a sign, expressing the nature of the charge of the
species in question when formed from the neutral atom
– The oxidation number of Chlorine in Chlorine Oxoacids
• Hydrochloric Acid (HCl) -1
• Hypochlorous acid (HOCl) +1
• Chlorous Acid (HOCLO or HClO2) +3
• Chloric acid (HClO3 or HOCLO2) +5
• Perchloric acid (HClO4 or HOCLO3) +7

Oxidation State of the Halogen(Con’d)
• Among Oxoacids of a given Halogen, such as Chlorine, acid

strength decreases as the oxidation state of Halogen decreases
• The higher the oxidation state (also stated as the number of

attached O atoms) of the Halogen, the more electron density it
pulls from the O-H bond
HOCL+7O3 > HOCL+5O2 > HOCl+3O > HOCl+1
Perchloric Chloric Chlorous Hypochlorous

Acid Acid Acid Acid
Chemistry of Chlorine
• Most important halogen
• Laboratory preparation from MnO2, NaCl and H2SO4:
2NaCl(s) + MnO2(s) + 2H2SO4(l)  Cl2(g) + MnSO4(s) +

Na2SO4(s) + 2H2O(l)
• Industrial production:
Chlorine is a by-product in the electrolysis of NaCl, MgCl2,

CaCl2, ScCl3, etc.
Oxides and Oxyacids of Chlorine
• Oxides of chlorine and its oxidation number (in parenthesis):
• Cl2O (+1), Cl2O3 (+3), ClO2 (+4; unstable), Cl2O5 (+5), Cl2O7 (+7;
highest possible)
• Chlorine oxyacids in increasing acid strength
• HOCl < HClO2 < HClO3 < HClO4;
• HClO4 is a strong oxidization agent

Major Uses of Chlorine

NaClO is an oxidising
• Production of chlorinated organic compounds; agent and the active
ingredient in bleach
• Production of hydrochloric acid;
• Production of bleach solution and bleach powder;
– Cl2(g) + 2NaOH(l) → NaClO(aq) + NaCl(aq) + H20(l)
– 2Cl2(g) + 2Ca(OH)(aq)  Ca(OCl)2(s) + CaCl2(aq) +

2H2O(l)
• Treatment of municipal water.
– Cl2(g) + H2O(l) ↔ HClO(aq) + HCl(aq Oxidising agent that

kills bacteria.
Important Compounds of Chlorine
• NaCl – for electrolyte balance
• NaOCl – household bleach solution
• Ca(OCl)2 – bleach for water & sewage treatment
• ClO2 – bleach for paper production
• NaClO3 – production of industrial bleach (ClO2)
• KClO3 – oxidizer in fireworks and matches
• NaClO4 – production of HClO4 and NH4ClO4
• NH4ClO4 – oxidizer in booster rocket fuel

Group 8 – Noble Gas Family (ns2np6)
• The Noble gases have completed outer s & p shells
• Noble gases are generally not reactive – nearly inert
• Behave more like “Ideal Gases” than any other gases
• The smallest radii in their period
• Condense and solidify only at very low temperatures
• colorless, odorless gases at room temperature
• A few Noble gas compounds have been prepared
PtF6 + Xe  XePtF6
• Other Xenon compounds
Xe+2F2 Xe+4F4 Xe+6F6 Xe+8O4
• He and Ne form no compounds.
• Kr and Xe have been observed to form compounds with oxygen

and fluorine:
Xe(g) + 2F2(g)  XeF4(s)
Xe(g) + 3F2(g)  XeF6(s)
XeF6(s) + 3H2O(l)  XeO3(aq) + 6HF(aq)
XeF6(s) + 2H2O(l)  XeO2F2(aq) + 4HF(aq)
XeF6(s) + H2O(l)  XeOF4(aq) + 2HF(aq)


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• also look like elements of group 17 (Halogens) because hydrogen

• H has three isotopes - Protium, deuterium and tritium

• In elemental form exists as a diatomic molecule H2 and is called

• Sodium metal (Na) will react violently with water (H2O),

• If hydrogen is heated without oxygen, no reaction will take place.

producing a metallic salt and hydrogen gas (H2).

C2H6(g) C2H4(g) + H2(g)

• Another route to hydrogen gas is through the water-gas shift

• Hydrides can be classified as saline, metallic, or molecular

1. Ionic or Saline hydrides

– are formed with s-block elements (highly electropositive).

– Such hydrides are non-volatile, non-conducting, and crystalline.

– They are quite insoluble in organic solvents

– exhibit very active chemistry when placed in water:

NaH(s) + H2O(l) H2(g) + NaOH(aq)

CaH2(s) + H2O(l) H2(g) + Ca(OH)2(aq), LiH, CaH2

• are the compounds of hydrogen with transition metals of group 3-5

• Some of these are classified as interstitial hydrides, where hydride

• These materials are considered to be a safe means of hydrogen

• involve non-metals, and are usually volatile, in contrast to metallic

• are binary compounds of hydrogen with elements of comparatively

• There are three classes of molecular hydrides

be formed. Examples of this are hydrides of group 13

2. Electron-precise (e.g. CH4):

• Almost all compounds are ionic, except for some Li and Na

• weak metallic bonding - attraction between delocalized electrons

• Powerful reducing agents – lose 1 electron becoming 1+ cations,

• Size of atom decreases considerably when valence electron is lost

• Lattice Energy – The atomic radius increases as you move down a

• Entropy – Entropy increases as ions disperse going into solution

• Magnitude of Hydration Energy decreases as ionic size increases

(Li+ > Na+ > K+ > Rb+ > Cs+

• Alkali metals (E) reduce Halogens (X) to form Halides

2E(s) + X2  2EX(s) X = F, Cl, Br, I)

• Sodium Metal (Na) can be produced from Molten NaCl and

2NaCl(l)  2Na(l) + Cl2(g)

• Sodium Hydroxide (Lye) can be produced from Salt (NaCl), water

2NaCl(s) + H2O(l)  2NaOH(aq) + H2(g) + Cl2(g)

Production of Alkali Metals

• Li and Na are produced by electrolysis of molten chlorides (LiCl

• All can be obtained by electrolysis of their molten salts.

Anode: Cl– ½Cl2 + e–

• K is produced by displace method using molten KCl and Na vapor:

KCl(l) + Na(g)  K(g) + NaCl(l)

M + ½X2 MX X = F, Cl, Br, I

M + H2O MOH + ½H2

6Li + N2 20 - 200 2Li3N

4Li(s) + O2(g)  2Li2O(g) (simple oxide)

2Na(s) + O2(g)  Na2O2(s) (peroxide, O2 2–)

K(s) + O2(g)  KO2(s) (superoxide, O2 1–)

• Sodium also produces some Na2O along with Na2O2.

• The superoxide compounds are a rare example of a paramagnetic

• All alkali metals dissolve in liquid ammonia to give blue solutions

Uses of Lithium and Lithium Compounds

• Lithium mainly used to make lithium batteries;

• LiCl is used in air-conditioning units as dehumidifier;

• Li2CO3 is used in porcelain enamels, manufacture of tough (pyrex)

• Alloys of Li-Al-Mg for aircraft and space applications.

1. As an ingredient in food – Na+ is essential to the body for

2. Production of sodium metal by electrolysis of molten NaCl;

2NaCl(l)  2Na(s) + Cl2(g)

3. Production of NaOH by electrolysis of aqueous NaCl;