Characteristic Trend (left to right)

Reason

Atomic radius decreases in size from left to

right

increased attractive force (acting on the same

energy shell) of the nucleus increases as the
number of protons increases

Ionic radius

decreases across the period until In general as above. The sudden increase on
formation of the negative ions
formation of negative ions is due to the new
then there is a sudden increase (larger) outer shell
followed by a steady decrease to
the end

Electronegati Increases
vity
Metallic
character

More electron attracting power of the larger

nuclear charge as we move to the right

Decreases - Na, Mg, Al metals; Si Metallic character is a measure of the ease of

metalloid; P, S, Cl, Ar non-metals loss of electrons from the outer shell. This
decreases with increasing nuclear charge.

Melting point Na

Al steady increase

Increasing availability of electrons in the

metallic bonding associated with greater
charge density of the metal ion

Si massive increase

Si giant macromolecular structure

P large decrease

P4 molecules

S small increase

S8 crown shaped molecules

Cl

Cl2 molecules and Ar atoms

Ar decrease

======================
E-Z NOTATION FOR GEOMETRIC ISOMERISM

This page explains the E-Z system for naming geometric

isomers.

Important! If you have come straight here

via a search engine, you should be aware
that this page follows on from
an introductory page about geometric
isomerism. Unless you are already confident
about how geometric isomers arise, and the
cis-trans system for naming them, you
should follow this link first. You will find
links back to this current page at suitable
points on that page.

The E-Z system

The problem with the cis-trans system for naming
geometric isomers
Consider a simple case of geometric isomerism which
we've already discussed on the previous page.

You can tell which is the cis and which the trans form
just by looking at them. All you really have to remember
is that trans means "across" (as in transatlantic or
transcontinental) and that cis is the opposite. It is a
simple and visual way of telling the two isomers apart.
So why do we need another system?
There are problems as compounds get more complicated.
For example, could you name these two isomers using
cis and trans?

Because everything attached to the carbon-carbon

double bond is different, there aren't any obvious things
which you can think of as being "cis" or "trans" to each
other. The E-Z system gets around this problem
completely - but unfortunately makes things slightly
more difficult for the simple examples you usually meet
in introductory courses.

How the E-Z system works

We'll use the last two compounds as an example to
explain how the system works.
You look at what is attached to each end of the double
bond in turn, and give the two groups a "priority"
according to a set of rules which we'll explore in a
minute.
In the example above, at the left-hand end of the bond,
it turns out that bromine has a higher priority than
fluorine. And on the right-hand end, it turns out that
chlorine has a higher priority than hydrogen.

If the two groups with the higher priorities are on the

same side of the double bond, that is described as the
(Z)- isomer. So you would write it as (Z)-name of
compound. The symbol Z comes from a German word
(zusammen) which means together.

Note: I'm not getting bogged down in the

names of these more complex compounds.
As soon as I put the proper full names in,
the whole thing suddenly looks much more
complicated than it really is, and you will
start to focus on where the whole name
comes from rather than on if it is a (Z)- or
(E)- isomer.

If the two groups with the higher priorities are on

opposite sides of the double bond, then this is the (E)isomer. E comes from the German entgegen which means
opposite.
So the two isomers are:

Summary

(E)- : the higher priority groups are on opposite

sides of the double bond.

(Z)- : the higher priority groups are on the same

side of the double bond.

Note: Three possible suggestions for

remembering this:

E is for "Enemies", which are on

opposite sides.

You don't, of course, need a way of

remembering the Z as well - it's just the
other way around from E.

In Z isomers, the higher priority

groups are on zee zame zide. That
works best if you imagine you are an
American speaking with a stage
German accent!

This is the way I remembered it when I

first came across E-Z notation. It is
more visual than the other methods.

It relies on the fact that the shapes of E and

Z isomers are the opposite of the shapes of
the letters E and Z.
In the letter E, the horizontal strokes are all
on thesame side; in the E isomer, the higher
priority groups are on opposite sides. In the
letter Z, the horizontal strokes are
on opposite sides; in the Z isomer, the
groups are on the same side.
Choose whichever of these methods make
most sense to you.

Rules for determining priorities

These are known as Cahn-Ingold-Prelog (CIP) rules after
the people who developed the system.
The first rule for very simple cases
You look first at the atoms attached directly to the
carbon atoms at each end of the double bond - thinking
about the two ends separately.

The atom which has the higher atomic number is

given the higher priority.

Let's look at the example we've been talking about.

Just consider the first isomer - and look separately at the

left-hand and then the right-hand carbon atom. Compare
the atomic numbers of the attached atoms to work out
the various priorities.

Notice that the atoms with the higher priorities are both
on the same side of the double bond. That counts as the
(Z)- isomer.
The second isomer obviously still has the same atoms at
each end, but this time the higher priority atoms are on
opposite sides of the double bond. That's the (E)- isomer.

What about the more familiar examples like 1,2dichloroethene or but-2-ene? Here's 1,2-dichloroethene.

Think about the priority of the two groups on the first

carbon of the left-hand isomer.
Chlorine has a higher atomic number than hydrogen, and
so has the higher priority. That, of course, is equally true
of all the other carbon atoms in these two isomers.
In the first isomer, the higher priority groups are on
opposite sides of the bond. That must be the (E)- isomer.
The other one, with the higher priority groups on the
same side, is the (Z)- isomer.

And now but-2-ene . . .

This adds the slight complication that you haven't got a
single atom attached to the double bond, but a group of
atoms.
That isn't a problem. Concentrate on the atom directly
attachedto the double bond - in this case the carbon in
the CH3 group. For this simple case, you can ignore the
hydrogen atoms in the CH3 group entirely. However, with
more complicated groups youmay have to worry about
atoms not directly attached to the double bond. We'll
look at that problem in a moment.
Here is one of the isomers of but-2-ene:

The CH3 group has the higher priority because its carbon
atom has an atomic number of 6 compared with an
atomic number of 1 for the hydrogen also attached to
the carbon-carbon double bond.
The isomer drawn above has the two higher priority
groups on opposite sides of the double bond. The
compound is (E)-but-2-ene.

A minor addition to the rule to allow for isotopes of, for

example, hydrogen
Deuterium is an isotope of hydrogen having a relative
atomic mass of 2. It still has only 1 proton, and so still
has an atomic number of 1. However, it isn't the same as
an atom of "ordinary" hydrogen, and so these two

compounds are geometric isomers:

The hydrogen and deuterium have the same atomic

number - so on that basis, they would have the same
priority. In a case like that, the one with the higher
relative atomic mass has the higher priority. So in these
isomers, the deuterium and chlorine are the higher
priority groups on each end of the double bond.
That means that the left-hand isomer in the last diagram
is the (E)- form, and the right-hand one the (Z)-.

Extending the rules to more complicated molecules

If you are reading this because you are doing a course
for 16 - 18 year olds such as UK A level, you may well not
need to know much about this section, but it really isn't
very difficult!
Let's illustrate this by taking a fairly scary-looking
molecule, and seeing how easy it is to find out whether it
is a (Z)- or (E)- isomer by applying an extra rule.

Focus on the left-hand end of the molecule. What is

attacheddirectly to the carbon-carbon double bond?
In both of the attached groups, a carbon atom is
attached directly to the bond. Those two atoms
obviously have the same atomic number and therefore
the same priority. So that doesn't help.
In this sort of case, you now look at what is
attached directly to those two carbons (but without
counting the carbon of the double bond) and compare
the priorities of these next lot of atoms.

You can do this in your head in simple cases, but it is

sometimes useful to write the attached atoms down,
listing them with the highest priority atom first. It makes
them easier to compare. Like this . . .
In the CH3 group:
The atoms attached to the carbon are H H H.
In the CH3CH2 group:
The atoms attached directly to the carbon of the
CH2 group are C H H.
In the second list, the C is written first because it has the
highest atomic number.
Now compare the two lists atom by atom. The first atom
in each list is an H in the CH3 group and a C in the
CH3CH2 group. The carbon has the higher priority
because it has the higher atomic number. So that gives
the CH3CH2 group a higher priority than the CH3 group.
Now look at the other end of the double bond. The extra
thing that this illustrates is that if you have a double
bond, you count the attached atom twice. Here is the
structure again.

So, again, the atoms attached directly to the carboncarbon double bond are both carbons. We therefore need
to look at what is attached to those carbons.
In the CH2OH group:
The atoms attached directly to the carbon are O H H.
In the CHO group:
The atoms attached directly to the carbon are O O H.
Remember that the oxygen is counted twice because of
the carbon-oxygen double bond.
In both lists, the oxygens are written first because they

have a higher atomic number than hydrogen.

So, what is the priority of the two groups? The first atom
in both lists is an oxygen - that doesn't help. Look at the
next atom in both lists. In the CH2OH group, that's a
hydrogen; in the CHO list, it's an oxygen.
The oxygen has the higher priority - and that gives the
CHO group a higher priority than the CH2OH group.
The isomer is therefore a (Z)- form, because the two
higher priority groups (the CH3CH2 group and the CHO
group) are both on the same side of the bond.
That's been a fairly long-winded explanation just to make
clear how it works. With a bit of practice, it takes a few
seconds to work out in any but the most complex cases.

One more example to make a couple of additional minor

points . . .
Here's an even more complicated molecule!

Before you read on, have a go at working out the relative

priorities of the two groups on the left-hand end of the
double bond, and the two on the right-hand end. There's
another bit of rule that I haven't specifically told you yet,
but it isn't hard to guess what it might be when you start
to look at the problem. If you can work this out, then you
won't have any difficulty with any problem you are likely
to come across at this level.
Look first at the left-hand groups.
In both the top and bottom groups, you have a CH2 group
attached directly to the carbon-carbon double bond, and
the carbon in that CH2 group is also attached to another

carbon atom. In each case, the list will read C H H.

There is no difference between the priorities of those
groups, so what are you going to do about it? The
answer is to move out along the chain to the next group.
And if necessary, continue to do this until you have
found a difference.
Next along the chain at the top left of the molecule is
another CH2 group attached to a further carbon atom.
The list for this group is again C H H.
But the next group along the chain at the bottom left is a
CH group attached to two more carbon atoms. Its list is
therefore C C H.
Comparing these lists atom by atom, leads you to the
fact that the bottom group has the higher priority.
Now look at the right-hand groups. Here is the molecule
again:

The top right group has C H H attached to the first

carbon in the chain.
The bottom right one has Cl H H.
The chlorine has a higher atomic number than carbon,
and so the bottom right group has the higher priority of
these two groups.
The extra point I am trying to make with this bit of the
example is that you must just focus on one bit of a chain
at a time. We never get around to considering the
bromine at the extreme top right of the molecule. We
don't need to go out that far along the chain - you work
out one link at a time until you find a difference.
Anything beyond that is irrelevant.
For the record, this molecule is a (Z)- isomer because the

higher priority groups at each end are on the same side

of the double bond.

Can you easily translate cis- and trans- into (Z)- and (E)-?
You might think that for simple cases, cis- will just
convert into (Z)- and trans- into (E)-.
Look for example at the 1,2-dichloroethene and but-2ene cases.

But it doesn't always work! Think about this relatively

uncomplicated molecule . . .

This is clearly a cis- isomer. It has two CH3 groups on the

same side of the double bond. But work out the priorities
on the right-hand end of the double bond.
The two directly attached atoms are carbon and
bromine. Bromine has the higher atomic number and so
has the higher priority on that end. At the other end, the
CH3 group has the higher priority.
That means that the two higher priority groups are on

opposite sides of the double bond, and so this is an (E)isomer - NOT a (Z)-.
Never assume that you can convert directly from one of
these systems into the other. The only safe thing to do is
to start from scratch in each case.
Does it matter that the two systems will sometimes give
different results? No! The purpose of both systems is to
enable you to decode a name and write a correct
formula. Properly used, both systems will do this for you
- although the cis-trans system will only work for very
straightforward molecules.

================================================
isomer

melting point (C)

boiling point (C)

cis

-80

60

trans

-50

48

In each case, the higher melting or boiling point is shown in red.

You will notice that:

the trans isomer has the higher melting point;

the cis isomer has the higher boiling point.

=======================================

================================
The standard enthalpy of formation
"The enthalpy of formation is the energy change when 1 mole of a
substance is formed from its constituent elements in their standard
states"
Particular points to note:

The elements are in their usual states under standard conditions. i.e
at 25C and 1 atmosphere pressure (100 kPa).

The enthalpy of formation of an element in its standard state is zero

by this definition.

The energy is given per mole of substance.

The standard enthalpy of formation is represented by the symbol

Hf .

Example: Give the equation for the enthalpy of formation of sulfuric

acid
The enthalpy of formation of sulfuric acid is represented by the
following equation:
H2(g) + S(s) + 2O2(g)

H2SO4(l)

Hf = -811 kJ mol-1

Example: The enthalpy of formation of calcium carbonate is

represented by the following equation:
Ca(s) + C(s) + 1O2(g)
mol-1

CaCO3(s)

Hf = -1207 kJ

The sign of the enthalpy of formation of a compound gives us the relative

stability of the compound being formed with respect to its constituent
elements.
A negative value tells us that it is an exothermic compound (compared to
its elements). It DOES NOT tell us that the elements can be made to react
directly together to form the compound
Similarly, a positive enthalpy of formation value tells us that the
compound is relatively unstable with respect to its elements, it is an
endothermic compound.
It DOES NOT mean that it is unstable, only that in comparison with its
constituent elements its formation would require energy. Once again there
is no implication regarding the possibility of direct formation from the
elements.

top
Ionisation enthalpy
This is defined as the energy required to remove 1 mole of electrons from
1 mole of gaseous particles producing 1 mole of ions. It can be stated as
1st ionisation energy, 2nd ionisation energy etc.
The 1st ionisation energy is the energy required to remove 1 mole of
electrons from 1 mole of gaseous atoms to produce 1 mole of singly
charged positive ions. It is always endothermic.
Key points to remember are:

The value is quoted per mole of species

The particles must be gaseous

Example: The first ionisation energy of sodium
Na(g)

Na+(g)

H = +496 kJ mol-1

top
Enthalpy of atomisation
This is the energy needed to transform an element in its standard state
into 1 mole of gaseous atoms. It is always endothermic.
Example: The enthalpy of atomisation of sodium
Na(s)

Na(g)

H = +107 kJ mol-1

top
Bond dissocation enthalpy
This is energy required to break 1 mole of a specific bond in a specific
compound. It is not the same as the bond energy term, which is an
average measured over many compounds.
Example: The first dissociation of methane
CH4(g)

CH3+ H

H = +412 kJ mol-1

top
The electron affinity
This is the energy change when 1 mole of electrons are captured by 1
mole of gaseous atoms forming 1 mole of negative ions. Once again the
electron affinity may be quoted in terms of 1st electron affinity, 2nd
electron affinity etc.

This value is usually negative, but in the case of second electron affinities
may be positive, as some processes are exothermic, while others are
endothermic.
Example: The first electron affinity of chlorine
Cl(g)

Cl-(g)

H = -349 kJ mol-1

top
Lattice enthalpy
The is possible to define from two points of view:

Forming of 1 mole of a crystal lattice from gaseous ions (exothermic)

Separating 1 mole of a crystal lattice into gaseous ions at infinite

separation (endothermic).

The way you define it is not important providing that you understand the
consequences for the enthalpy change in terms of the exo- and
endothermic processes.
Example: The lattice enthalpy of sodium chloride
Na+(g) + Cl-(g)

NaCl(s)

H = -786 kJ mol-1

Note that in this definition the enthalpy change is exothermic

(negative)

top
Enthalpy of hydration
This is the energy change when 1 mole of a gaseous species dissolves in
an infinite volume of water. It is caused by the solvent water molecules
bonding to the dissolving species. It is always an exothermic process as
bonds are being formed.
Example: The hydration enthalpy of the sodium ion
Na+(g) + (aq)

Na+(aq)

H = -405 kJ mol-1

top
Enthalpy of solution
Definition
The energy change when 1 mole of a substance is dissolved in a solution
to infinite dilution.
MgSO4(s)

Mg2+(aq) + SO42-(aq)

Clearly, the idea of infinite dilution is not to be taken literally. It just

means that a solution is prepared by dissolving the solute to such a
dilution as would produce no further energy change.
Enthalpy of solution data
Processes involved
At face value, dissolution is a simple process, however it comprises at
least two stages.

1 The solute is bonded together in some way. These bonds must be

broken.

2 The separated solute particles must bond to the water (or solvent)
molecules.

MgSO4(s)

Mg2+(g) + SO42-(g)

Mg2+(g) + SO42-(g) + (aq)

Mg2+(aq) + SO42-(aq)

If an ionic substance is being dissolved then the individual ions must be

dealt with separately in the second stage.
===============
Exothermic Reactions
Exothermic and endothermic reactions cause energy level differences and therefore
differences inenthalpy (H), the sum of all potential and kinetic energies. H is
determined by the system, not the surrounding environment in a reaction. A system
that releases heat to the surroundings, an exothermic reaction, has a negative H
by convention, because the enthalpy of the products is lower than the enthalpy of
the reactants of the system (Figure 1).
C(s)+O2(g)CO2(g)(H = 393.5 kJ)
H2(g)+1/2O2(g)H2O(l)(H = 285.8 kJ)

The enthalpies of these reactions are less than zero, and are therefore exothermic
reactions.
======================
A system of reactants that absorbs heat from the surroundings in an endothermic
reaction has a positive H, because the enthalpy of the products is higher than the
enthalpy of the reactants of the system.
N2(g)+O2(g)2NO(g)(H = +180.5 kJ > 0)
C(s)+2S(s)CS2(l)(H = +92.0 kJ > 0)
Because the enthalpies of these reactions are greater than zero, they
are endothermic reactions.
=====================
Lewis acids and bases

Lewis acid accept electron pairs. They don't have lone pairs on the central
atom. eg. BF3

Lewis bases donate electron pairs. They have lone pairs on their central
atom. eg. NH3

Periodic trends of the oxides have been thoroughly studied. In any given period, the bonding in
oxides progresses from ionic to covalent, and their acid-base character goes from strongly basic
through weakly basic, amphoteric, weakly acidic, and finally strongly acidic. In general, basicity
increases down a group (e.g., in the alkaline earth oxides, BeO < MgO < CaO < SrO <
BaO). Acidity increases with increasing oxidation number of the element. For example, of the
five oxides of manganese, MnO (in which manganese has an oxidation state of +2) is the least
acidic and Mn2O7 (which contains Mn7+) the most acidic. Oxides of the transition metals with
oxidation numbers of +1, +2, and +3 are ionic compounds consisting of metal ions and oxide
ions. Those transition metal oxides with oxidation numbers +4, +5, +6, and +7 behave as
covalent compounds containing covalent metal-oxygen bonds. As a general rule, the ionic
transition metal oxides are basic. That is, they will react with aqueous acids to form solutions of
salts and water; for example,CoO + 2H3O+ Co2+ + 3H2O.The oxides with oxidation numbers of
+5, +6, and +7 are acidic and react with solutions of hydroxide to form salts and water; for
example,CrO3 + 2OH- CrO42 + H2O.Those oxides with +4 oxidation numbers are
generally amphoteric (from Greekamphoteros, in both ways), meaning that these compounds
can behave either as acids or as bases. Amphoteric oxides dissolve not only in acidic solutions
but also in basic solutions. For example, vanadium oxide (VO2) is an amphoteric oxide,
dissolving in acid to give the blue vanadyl ion, [VO]2+, and in base to yield the yellow-brown

hypovanadate ion, [V4O9]2. Amphoterism among the main group oxides is primarily found with
the metalloidal elements or their close neighbours.
==========================
If you place a piece of aluminum metal into a solution of barium nitrate nothing will happen. Just because
someone writes an equation on paper, doesn't meant that it will actually occur in practice. Aluminum is
below barium in the activity series, which tells us that aluminum metal cannot reduce barium ions.
Therefore, there is no AlCl3(aq) and Ba as you might have expected. If Ba metal was produced we could
not have left it simply as Ba(s). It would have reacted with water to make Ba(OH)2(aq) and H2 gas.
============== Follow up ===============
Here is perfect example of why you must specify the states of the compounds and the conditions. In
solution, the nitrate ion does nothing, but when aluminum powder is combined with solid barium nitrate
powder then a reaction can occur between the aluminum metal and the decomposing barium nitrate.
Individual reactions:
2Ba(NO3)2(s) ---> 2BaO(s) + 4NO2(g) + O2(g)
4Al(s) + 3O2(g) --> 2Al2O3(s)
Overall reaction:
2Al(s) + 3Ba(NO3)2(s) --> 3BaO(s) + 6NO2(g) + Al2O3(s)
========================

The Octet Rule and Its Exceptions

The octet rule states that atoms below atomic number 20 tend to combine so that
they each have eight electrons in their valence shells, which gives them the same
electronic configuration as a noble gas. The rule is applicable to the maingroup elements, especially carbon, nitrogen, oxygen, and the halogens, but also
to metals such as sodium and magnesium.
Valence electrons can be counted using a Lewis electron dot diagram. In carbon
dioxide, for example, each oxygen shares four electrons with the central carbon.
These four electrons are counted in both the carbon octet and the oxygen octet
because they are shared.

Carbon dioxide
A Lewis dot diagram for carbon dioxide.
Hydrogen and Lithium
However, many atoms below atomic number 20 often form compounds that do not
follow the octet rule. For example, with the duet rule of the first
principal energy level, the noble gas helium, He, has two electrons in its outer level.
Since there is no 1p subshell, 1s is followed immediately by 2s, and thus level 1 can
only have at most two valence electrons. Hydrogen only needs one additional
electron to attain this stable configuration, through either covalent sharing of
electrons or by becoming the hydride ion (:H-), while lithium needs to lose one by
combining ionically with other elements. This leads to hydrogen and lithium both
having two electrons in their valence shellthe same electronic configuration as
heliumwhen they form molecules by bonding to other elements.
Boron and Aluminum
There are also a variety of molecules in which there are too few electrons to provide
an octet for every atom. Boron and aluminum, from Group III (or 13), display

different bonding behavior than previously discussed. These atoms each have three
valence electrons, so we would predict that these atoms want to bond covalently in
order to gain 5 electrons (through sharing) to fulfill the octet rule. However,
compounds in which boron or aluminum atoms form five bonds are never observed,
so we must conclude that simple predictions based on the octet rule are not reliable
for Group III.
Consider boron trifluoride (BF3). The bonding is relatively simple to model with
a Lewis structure if we allow each valence level electron in the boron atom to be
shared in a covalent bond with each fluorine atom. In this compound, the boron
atom only has six valence shell electrons, but the octet rule is satisfied by the
fluorine atoms.

Lewis structure of boron trifluoride

Each pair of dots represents a pair of electrons. When placed between two atoms,
the electrons are in a bond. A bond can be drawn as a line between two atoms,
which also indicates two electrons. Notice that the central boron atom has only 6
electrons in the final Lewis diagram/structure of this molecule.
We might conclude from this one example that boron atoms obey a sextet rule.
However, boron will form a stable ion with hydrogen, BH 4-, in which the boron atom
does have a complete octet. In addition, BF 3 will react with ammonia (NH3), to form
a stable compound, NH3BF3, for which a Lewis structure can be drawn that shows
boron with a complete octet.

Boron trifluoride-ammonia complex

This covalent compound (NH3BF3) shows that boron can have an octet of electrons
in its valence level.
Compounds of aluminum follow similar trends. Aluminum trichloride (AlCl 3),
aluminum hydride (AlH3), and aluminum hydroxide (Al(OH)3) indicate a valence of
three for aluminum, with six valence electrons in the bonded molecule. However,

the stability of aluminum hydride ions (AlH 4-) indicates that Al can also support an
octet of valence shell electrons.
Although the octet rule can still be of some utility in understanding the chemistry of
boron and aluminum, the compounds of these elements are harder to predict than
for other elements.
==================================================
=================