NORTHERN CARIBBEAN UNIVERSITY

DEPARTMENT OF BIOLOGY and CHEMISTRY

LECTURE NOTES
CHEM122: GENERAL CHEMISTRY II
Assistant Professor: Dr. Nicole White
Group 1A Chemistry
The elements found in group 1 of the periodic table, Li - Fr are known as the alkali metals. They
have one valence electron found in the s orbital, ns1. These elements have the lowest first
ionization energies and readily ionize to have a +1 charge by losing the electron and thus are
among the most powerful reducing agents in the periodic table. Alkali metals have a bright
silvery appearance for the most part (Li Rb; Cs has a silvery gold colour), are malleable, can be
cut with a dull knife, and are good conductors of electricity. These elements are too reactive to be
found free in nature. Sodium occurs mainly as NaCl (salt) in sea-water and dried-up sea beds.
Potassium is more widely distributed in minerals such as sylvite, KCl, but is also extracted from
sea-water. The alkali metals are so reactive they cannot be displaced by another element, so are
isolated by electrolysis of their molten salts. Alkali metals colour flames. When the element is
placed in a flame the heat provides sufficient energy to promote the outermost electron to a
higher energy level. On returning to ground level, energy is emitted and this energy has a
wavelength in the visible region:
Li

red

Na yellow

lilac

Rb red

Cs

blue

They react violently with water and air. These elements are good reducing agents, a property that
increases as you travel down the group.

The trends in some properties are:

1. You can see that the atomic radius increases as you go down the Group. The radius of an atom
is governed by the number of layers of electrons around the nucleus and the pull the outer
electrons feel from the nucleus.
Compare lithium and sodium:

Li
Na

1s22s1
1s22s22p63s1

2. First ionisation energy is the energy needed to remove the most loosely held electron from
each of one mole of gaseous atoms to make one mole of singly charged gaseous ions.

The first ionisation energy falls as you go down the group. Ionisation energy is governed by

the charge on the nucleus,

the amount of screening by the inner electrons,

the distance between the outer electrons and the nucleus.

3. Electronegativity is a measure of the tendency of an atom to attract a bonding pair of electrons.

All of these elements have a very low electronegativity. Notice that electronegativity falls as you
go down the Group. The atoms become less and less good at attracting bonding pairs of electrons.
4. The melting points and boiling points fall as you go down the Group. When you melt any of
these metals, the metallic bond is weakened enough to move around, and is broken completely
when you boil the metal. The fall in melting and boiling points reflects the fall in the strength of
the metallic bond.
The atoms in a metal are held together by the attraction of the nuclei to the delocalized electrons.
As the atoms get bigger, the nuclei get further from these delocalized electrons, and so the
attractions fall. That means that the atoms are more easily pulled apart to make a liquid and
finally a gas.

5. The density tends to increase as you go down the Group (apart from the fluctuation at
potassium). It is quite difficult to come up with a simple explanation for this, because the density
depends on two factors, both of which are changing as you go down the Group. All of these
metals have their atoms packed in the same way, so all you have to consider is how many atoms
you can pack in a given volume, and what the mass of the individual atoms is. How many you
can pack depends, of course, on their volume - and their volume, in turn, depends on their atomic
radius.
As you go down the Group, the atomic radius increases, and so the volume of the atoms increases
as well. That means that you can't pack as many sodium atoms into a given volume as you can
lithium atoms. However, as you go down the Group, the mass of the atoms increase. That means
that a particular number of sodium atoms will weigh more than the same number of lithium
atoms. So 1 cm3 of sodium will contain fewer atoms than the same volume of lithium, but each
atom will weigh more. What affect will that have on the density? It is completely impossible to
say unless you do some sums!
Chemical properties

Alkali metals are stored under oil. They cannot be stored under water because they react
with it to produce hydrogen and alkali hydroxides:
2M(s) + 2H2O(l) 2M+(aq) + 2OH-(aq) + H2(g)
eg 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

This reaction illustrates the increasing reactivity on descending the Group. Li reacts steadily with
water, with effervescence; sodium reacts more violently and can burn with an orange flame; K
ignites on contact with water and burns with a lilac flame; Cs sinks in water, and the rapid
generation of hydrogen gas under water produces a shock wave that can shatter a glass container.
Na dissolves in liquid ammonia to give a deep blue solution of sodium cations and solvated
electrons. This solution is used as a reducing agent. At higher concentrations the colour of the
solution changes to bronze and it conducts electricity like a metal.

The chemistry of Li shows some anomalies, as the cation Li + is so small it polarises anions and so
introduces a covalent character to its compounds. Li has a diagonal relationship with magnesium.

Oxides: The alkali metals form ionic solid oxides of composition M2O when burnt in air.
However, Na also forms the peroxide Na2O2 as the main product, and K forms the
superoxide KO2, also as the main product.

Hydroxides: Alkali metal hydroxides are white ionic crystalline solids of formula MOH,
and are soluble in water. They are all deliquescent (the property of a substance that
inclines the substance to absorb moisture from the atmosphere until it dissolves) except
LiOH. The aqueous solutions are all strongly alkaline (hence the name of this Group) and
therefore dangerous to handle. They neutralise acids to form salts, eg:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
[In general OH-(aq) + H+(aq) H2O(l)]

Halides: Alkali metal halides are white ionic crystalline solids. They are all soluble in
water except LiF, which has a very high lattice enthalpy arising from the strong
electrostatic interaction of the small Li+ and F- ions.

Group 2A Chemistry
The elements found in group 2 of the periodic table, Be - Ra are known as the alkaline earth
metals. They have two valence electrons found in the s orbital, ns 2. The Group 2 elements are all
metals with a shiny, silvery-white colour. The alkaline earth metals are high in the reactivity
series of metals, but not as high as the alkali metals of Group 1. These elements are all found in
the Earths crust, but not in the elemental form as they are so reactive. Instead, they are widely
distributed in rock structures. The main minerals in which magnesium is found are carnellite,
magnesite and dolomite. Calcium is found in chalk, limestone, gypsum and anhydrite.
Magnesium is the eighth most abundant element in the Earths crust, and calcium is the fifth.
Of the elements in this Group only magnesium is produced on a large scale. It is extracted from
sea-water by the addition of calcium hydroxide, which precipitates out the less soluble

magnesium hydroxide. This hydroxide is then converted to the chloride, which is electrolysed in
a Downs cell to extract magnesium metal.
The metals of Group 2 are harder and denser than sodium and potassium, and have higher
melting points. These properties are due largely to the presence of two valence electrons on each
atom, which leads to stronger metallic bonding than occurs in Group 1.
Three of these elements give characteristic colours when heated in a flame:
Mg Brilliant white

Ca

Brick-red

Sr

crimson

Ba

apple green

Trends:

Atomic and ionic radii increase smoothly down the Group. The ionic radii are all much
smaller than the corresponding atomic radii. This is because the atom contains two
electrons in an s level relatively far from the nucleus, and it is these electrons which are
removed to form the ion. The radius of an atom is governed by the number of layers of
electrons around the nucleus and the pull the outer electrons feel from the nucleus.

Compare beryllium and magnesium:

Be
Mg

1s22s2
1s22s22p63s2

Remaining electrons are thus in levels closer to the nucleus, and in addition the increased
effective nuclear charge attracts the electrons towards the nucleus and decreases the size of the
ion.

Notice that first ionisation energy falls as you go down the group. Ionisation energy is
governed by

the charge on the nucleus,

the amount of screening by the inner electrons,

the distance between the outer electrons and the nucleus.

As you go down the Group, the increase in nuclear charge is exactly offset by the increase in the
number of inner electrons. Similar to the atomic radius, in each of the elements in this Group, the
outer electrons feel a net attraction of 2+ from the centre.
However, as you go down the Group, the distance between the nucleus and the outer electrons
increases and so they become easier to remove - the ionisation energy falls.

Notice that electronegativity falls as you go down the Group. The atoms become less and
less good at attracting bonding pairs of electrons. As the metal atoms get bigger, any
bonding pair gets further and further away from the metal nucleus, and so is less strongly
attracted towards it. In other words, as you go down the Group, the elements become less
electronegative. As you go down the Group, the bonds formed between these elements
and other things such as chlorine become more and more ionic. The bonding pair is
increasingly attracted away from the Group 2 element towards the chlorine (or whatever).

You will see that (with the exception of magnesium) the melting point falls as you go
down the Group.

Chemical properties
The chemical properties of Group 2 elements are dominated by the strong reducing power of the
metals. The elements become increasingly electropositive on descending the Group.
Once started, the reactions with oxygen and chlorine are vigorous:
2Mg(s) + O2(g) 2MgO(s)
Ca(s) + Cl2(g) CaCl2(s)

All the metals except beryllium form oxides in air at room temperature which dulls the surface of
the metal. Barium is so reactive it is stored under oil.
All the metals except beryllium reduce water and dilute acids to hydrogen:
Mg(s) + 2H+(aq) Mg(aq) + H2(g)
Magnesium reacts only slowly with water unless the water is boiling, but calcium reacts rapidly
even at room temperature, and forms a cloudy white suspension of sparingly soluble calcium
hydroxide.
Calcium, strontium and barium can reduce hydrogen gas when heated, forming the hydride:
Ca(s) + H2(g) CaH2(s)
The hot metals are also sufficiently strong reducing agents to reduce nitrogen gas and form
nitrides:
3Mg(s) + N2(g) Mg3N2(s)
Magnesium can reduce, and burn in, carbon dioxide:
2Mg(s) + CO2(g) 2MgO(s) + C(s)
This means that magnesium fires cannot be extinguished using carbon dioxide fire extinguishers.
-

Oxides: The oxides of alkaline earth metals have the general formula MO and are basic.
They are normally prepared by heating the hydroxide or carbonate to release carbon
dioxide gas. They have high lattice enthalpies and melting points. Peroxides, M2O2, are
known for all these elements except beryllium, as the Be 2+ cation is too small to
accommodate the peroxide anion.

Hydroxides: Calcium, strontium and barium oxides react with water to form hydroxides:
CaO(s) + H2O(l) Ca(OH)2(s)

Calcium hydroxide is known as slaked lime. It is sparingly soluble in water and the resulting
mildly alkaline solution is known as lime water which is used to test for the acidic gas carbon
dioxide.
-

Halides: The Group 2 halides are normally found in the hydrated form. They are all ionic
except beryllium chloride. Anhydrous calcium chloride has such a strong affinity for water
it is used as a drying agent.

Group 7A Elements (Halogens)

With the exception of He, Ne, and Ar, all of the elements in the periodic table form halides. Ionic
or covalent halides are among the most important and common compounds. They are often the
easiest to prepare and are widely used as source materials for the synthesis of other compounds.
The members of this group are all reactive non-metals, F At. All tend to react by forming ions
with one negative charge as they are each one electron short of a full outer shell. All the elements
exist as diatomic molecules with an E-E single bond. The compounds are too reactive to be found
uncombined. The reactivity decreases down the group. At room temperature fluorine is a pale
yellow gas, chlorine a greenish gas, bromine a volatile red-brown liquid and iodine a shiny black
solid which gives off a purple vapour on gentle heating.
Trends

The atomic radius increases as you go down the Group. The radius of an atom is governed
by the number of layers of electrons around the nucleus and the pull the outer electrons
feel from the nucleus.

Compare fluorine and chlorine:

F

2,7

Cl

2,8,7

Electronegativity falls as you go down the Group. The atoms become less good at
attracting bonding pairs of electrons. As the halogen atoms get bigger, any bonding pair
gets further and further away from the halogen nucleus, and so is less strongly attracted
towards it. In other words, as you go down the Group, the elements become less
electronegative.

The tendency is for the electron affinities to decrease (in the sense that less heat is given
out), but the fluorine value is out of line.

The electron affinity is a measure of the attraction between the incoming electron and the
nucleus. The higher the attraction the higher the electron affinity. In the bigger atom, the
attraction from the more positive nucleus is offset by the additional screening electrons, so each
incoming electron feels the effect of a net 7+ charges from the centre - exactly as when you are
thinking about atomic radius or electronegativity.
As the atom gets bigger, the incoming electron is further from the nucleus and so feels less
attraction. The electron affinity therefore falls as you go down the Group.
But what about fluorine? That is a very small atom, with the incoming electron quite close to the
nucleus. Why isn't its electron affinity bigger than chlorine's? There is another effect operating.
When the new electron comes into the atom, it is entering a region of space already very
negatively charged because of the existing electrons. There is bound to be some repulsion,
offsetting some of the attraction from the nucleus. In the case of fluorine, because the atom is

very small, the existing electron density is very high. That means that the extra repulsion is
particularly great and lessens the attraction from the nucleus enough to lower the electron affinity
below that of chlorine.

Both melting points and boiling points rise as you go down the Group. All of the halogens
exist as diatomic molecules - F2, Cl2, and so on. The intermolecular attractions between
one molecule and its neighbours are van der Waals dispersion forces. As the molecules get
bigger there are obviously more electrons which can move around and set up the
temporary dipoles which create these attractions. The stronger intermolecular attractions
in the larger molecules means that you have to supply more heat energy to turn them into
either a liquid or a gas - and so their melting and boiling points rise.

Chemical properties

The reaction of halide salts with concentrated sulphuric acid: In the reaction with
chlorides, H2SO4 acts as an acid displacing the more volatile HCl. The concentrated
sulphuric acid gives a hydrogen ion to the halide ion to produce a hydrogen halide.
Because this is a gas, it immediately escapes from the system. If the hydrogen halide is
exposed to moist air, you see it as steamy fumes.

With bromides and iodides, the halide ions are more easily reducible and the halogen is
produced as well as other products. The reactions of the sodium salts are typical.
NaCl(s) + H2SO4(l) NaHSO4(s) + HCl(g)
NaBr(s) + H2SO4(l) NaHSO4(s) + HBr(g)
2HBr(g) + H2SO4(l) Br2(g) + SO2(g) + 2H2O(l)
NaI(s) + H2SO4(l) NaHSO4(s) + HI(g)
2HI(g) + H2SO4(l) I2(s) + SO2(g) + 2H2O(l)

The displacement reactions of halide ions by halogens: Chlorine will displace both
bromide and iodide ions; bromine will displace iodide ions. We are going to look at the
reactions between one halogen (chlorine, say) and the ions of another one (iodide ions,
perhaps). The iodide ions will be in a solution of a salt like sodium or potassium iodide.
The sodium or potassium ions will be spectator ions, and are completely irrelevant to the
reaction.
Cl2(aq) + 2I (aq) 2Cl (aq) + I2(aq)
Br2(aq) + 2I (aq) 2Br (aq) + I2(aq)
Cl2(aq) + 2Br (aq) 2Cl (aq) + Br2(aq)

In each case, a halogen higher in the Group can oxidise the ions of one lower down.

First Row Transition Elements

The first row transition series are remarkably similar in their physical and chemical properties.
This general similarity in properties has been explained in terms of their relatively small
difference in effective nuclear charge over the series. This occurs because each additional
electron enters the penultimate 3d shell providing an effective shield between the nucleus and the
outer

4s

shell.

Thus, the transition elements can be defined as those in which the d electron shells are being
filled and so we generally ignore Sc and Zn where Sc(III) is d0 and Zn(II) is d10.
Physical properties
Transition elements:

have large charge/radius ratio;

are hard and have high densities;

have high melting and boiling points;

form compounds which are often paramagnetic;

show variable oxidation states;

form coloured ions and compounds;

form compounds with profound catalytic activity;

form stable complexes.

A major difference between the transition metals and other metals lies with the ability of the
transition metals to form coordination compounds. In these types of compounds, molecules
with an unshared electron pair, such as water or ammonia, donate the unshared pair to a transition
metal or ion. The transition metals are able to accommodate the extra electrons by placing them
into vacant d orbitals.
The melting points and the molar enthalpies of fusion of the transition metals are both high in
comparison to main group elements. This arises from strong metallic bonding in transition metals
which occurs due to delocalization of electrons facilitated by the availability of both d and s
electrons.
The electronic configuration of the atoms of the first row transition elements are basically the
same. It can be seen in the table above that there is a gradual filling of the 3d orbitals across the
series starting from scandium. This filling is, however, not regular, since at chromium and copper
the population of 3d orbitals increase by the acquisition of an electron from the 4s shell. This
illustrates an important generalization about orbital energies of the first row transition series. At
chromium, both the 3d and 4s orbitals are occupied, but neither is completely filled in preference
to the other. This suggests that the energies of the 3d and 4s orbitals are relatively close for atoms
in this row. In the case of copper, the 3d level is full, but only one electron occupies the 4s orbital.
This suggests that in copper the 3d orbital energy is lower than the 4s orbital. Thus the 3d orbital
energy has passed from higher to lower as we move across the period from potassium to zinc.
Just in case you forgot
Electronic configuration is a representation of the electrons in the various shells of an atom. An
atomic shell consists of subshells and orbitals - an orbital can hold a maximum of 2 electrons.
There are different subshells each holding a different number of electrons; s (1 orbital), p (3

orbitals), d (5 orbitals) and f (7 orbitals) are the most common. These subshells are of differing
energy levels, the lowest being s and the highest being f; they are arranged in increasing energy in
the previous sentence. The electronic configurations shows the number of electrons located in the
various subshells, also there arrangement within the atom the electron occupy the subshells
with the lowest energy first. In the 1st shell only the s subshell subshell is found. The 2nd shell has
the s and p subshells and so on.
Example
1. Li this atom has 3 electrons but only 1 valence electron. A valence electron is an
electron present in the final shell of the atom.
1s2 2s1
2. Ca this has 20 electrons, 2 valence electrons.
1s2 2s2 2p6 3s2 3p6 4s2
When an electron is added an anion is formed and the electronic configuration should reflect this
change in electron number.
Cl 1s2 2s2 2p6 3s2 3p5
Cl- - 1s2 2s2 2p6 3s2 2p6
Writing the electronic configuration for elements starting from period 4 becomes interesting
because one must take into consideration the d subshells. One might expect that since electron
begin to electrons from the 3rd shell that the electronic configurations of the 3 rd shell should show
this. On the periodic table in the 4th shell we notice the appearance of the transition metals which
have electrons in the d subshells though the d subshell is observed at the 4 th period it actually
belongs to the 3rd shell. The s subshells have lower energy levels than the preceding d subshells
and so they tend to be filled first.
Sc
Ti
V
Cr

1s22s22p63s23p63d14s2
1s22s22p63s23p63d24s2
1s22s22p63s23p63d34s2
1s22s22p63s23p63d54s1

Chromium breaks the sequence. In chromium, the electrons in the 3d and 4s orbitals rearrange so
that there is one electron in each orbital.
Mn
Fe
Co
Ni
Cu
Zn

1s22s22p63s23p63d54s2
1s22s22p63s23p63d64s2
1s22s22p63s23p63d74s2
1s22s22p63s23p63d84s2
1s22s22p63s23p63d104s1
1s22s22p63s23p63d104s2

(back to being tidy again)

(another awkward one!)

Also, as observed the s orbital again transfers one of its electrons to the d subshells for the same
reason as for chromium; a filled or half filled subshell.
A shortcut way of writing the electronic configuration for elements with many shells is to write
the nearest inert gas/ group 8 element in square brackets and write the remaining configuration as
before, for example, Ba is [Xe] 6s2.
With these basic rules and examples you should be able to write the configuration for any
element asked.

Born Haber cycle

The BornHaber cycle is an approach to analyzing reaction energies. It involves the formation of
an ionic compound from the reaction of a metal with a non-metal. BornHaber cycles are used
primarily as a means of calculating lattice energies (or more precisely enthalpies) which cannot
otherwise be measured directly. The lattice enthalpy is the enthalpy change involved in formation
of the ionic compound from gaseous ions. Some chemists define it as the energy to break the
ionic compound into gaseous ions. The former definition is invariably exothermic and the latter is
endothermic.
A Born-Haber cycle may be considered a pictorial way of viewing the steps in the formation of
an ionic solid from its elements. The reaction between a metal and a non-metal involves the
transfer of electrons as well as energy. The energy released when an anion is formed is

insufficient to offset the amount required to produce a cation; this would make the reaction
unfavourable. For the reaction to be favourable, the electrostatic attractions between product
cations and anions along with the formation of an ionic solid must be factored in.
The reactants must be atomized, ionized and then combined. Atomized the reactants must be
in the gaseous form. This involves the enthalpyof sublimation in the case of a solid to a gas or
enthalpy of dissociation in the case of a diatomic molecule. If one atom is needed then the value
wold is half of the enthalpy of dissociation. Ionized this involved the ionization energy as well
as the electron affinity depending on whether the cation or anion is formed. Combined this is
the lattice energy involved in forming the ionic solid. Hess law is applied and the enthalpy of
formation of the ionic solid is calculated.
The steps are a theoretical practice only in understanding the formation of ionic solids, as
these reactions in reality are happening all at once.
NaCl

Rearrange to determine the lattice energy

The reaction is favourable if the Hlattice < 0