Electron Arrangement and Emission Spectra

When excited (heated), electrons can temporarily jump to high levels, and release specific
wavelengths (including visible colours) or electromagnetic energy when they return to normal
In 1900 Max Planck proposed that electromagnetic radiation (EMR) is emitted in packets of
energy called photons. The energy of one photon is called one quantum of energy
Recall that electrons orbit the nucleus of an atom in specific energy levels or orbitals. When an
element is excited by absorbing photons of energy, electrons can temporarily jump to a higher
energy level. Falling back to its ground state releases specific wavelength of energy (in the
form of different colours)
Each photon pulses at a certain frequency and travels at the speed of light
o E = hf
This helped to explain
o Emission of light from hot objects
o Emission of electrons from metal surfaces when light shines on it (photoelectric effect)
o Emission of light from electronically excited gas atom
Bohr defined the ground state as n = 1, where n is any positive integer the energy (E) of the
transition between ground and excited states depends of the values of n1 and n2
Unlike white light which forms a continuous spectrum containing all frequencies smeared
together, atomic emission spectra form distinct line spectra where only distinct frequencies
can be emitted based on the energy levels of orbitals
Different elements produce different line spectra based on their number and position of
electrons orbitals are at fixed energy levels they are quantized
These unique line spectra are also known as Emission Spectra
They are produced when electrons in an atom are excited to higher energy levels and then emit
photons of energy as they fall back to their ground state (most stable energy level)

Emission Spectra vs. Absorption Spectra

An emission spectrum is generated from energy that are emitted by excited electrons in an
atom as they fall back from excited states to ground states.
An absorption spectrum is generated when white light is passed through an unexcited gas, and
then through a prism the wavelengths absorbed by the gas produce black lines on a
continuous spectrum

Quantum Mechanics

deBroglie proposed electrons have wave properties such as wavelength and frequency
deBroglie suggested that electrons are standing stationary waves
the Heisenberg Uncertainty Principle states that it is impossible to know both position and
momentum because, in order to calculate momentum, a disruption in the position of the
electron only though mathematically determined probability of orbitals
each electrons surrounding the nucleus id described by a set of quantum numbers

principal quantum number (n) orbital size and energy level

2n2 = maximum number of electrons at a given energy level
o Second quantum (l) orbital shape
s,p,d,f
o third quantum/ magnetic quantum number (m1) orbital orientation
-l to l
o Fourth quantum (ms) electron spin
Either plus or minus
The Pauli Excursion Principle = 2 electrons can occupy any one orbital; they must spin in
opposite directions
Aufbau Principle = electrons are placed into orbitals of the lowest energy level (remember that
4s is a lower energy level than 3d)
Hunds Rule = if there is more than one orbital available in a sub-level, electrons occupy
different orbitals with parallel spins
Orbital Diagrams fill horizontally
Energy Level Diagrams fill vertically
o

Periodic Trends in the Main Group Elements

Atomic Radius (size): decreases across a period, and increases going down a group the
effective nuclear charge increases across a period, thus attracting electrons closer to the nucleus
Nuclear Charge proton value
Effective Nuclear Charge based on the number of electrons between the nucleus and the
electron in question
Shielding Effect outer electrons experience less attraction to the nucleus because inner
electrons are blocking them
First Ionization Energy the energy required to remove 1 electron from an uncharged atom;
tends to increase across a period (the increase in effective nuclear charge causes an increase in
the attraction between the outer electrons and the nucleus and makes the electrons more
difficult to remove) , and decrease down a group (the electrons removed is from an electron
shell furthest from nucleus nuclear charges increase, the effective nuclear charge is about the
same, due to shielding of the inner electrons, and so the increased distance between the
electron and the nucleus reduces the attraction between them)
Electron Affinity energy lost/gained when an electron is added to an uncharged atom (the
lower the number, the greater electron affinity); decreases moving down a group, and increases
moving across a period the greater the attraction between an atom and an added electron
the more energy that will be released

Graphs of Periodic Table Trends

Melting Point based on 2 factors: attractive forces between particles & the way in which
articles are packed in a solid state

o
o
o

The process of melting involves moving particles (atoms, molecules and/or ions) further
apart = greater motion. Trends appear within groups because forces of attraction tend
to be similar
Alkali Metals (Group 1) b/c they posse strong metallic bonds, melting point
decreases going down a group
Halogens (Group 7) b/c they have weak intermolecular forces, melting point
increases down a group
Alltropes vary in melting point because of nonconventional structure such as
graphite, and diamond in the case of Carbon

Metals, Metalloids and Non-Metals

Metals
o Form ionic oxides such as Na2O, MgO, Al2O3; all white solids with high melting/boiling
points
o they are good conductors of electricity --> due to the mobility of their outer electrons
o they have low densities
o they are very reactive --> low ionization level
o they form ionic compounds with non metals
o are basic
o can be decomposed by electrolysis
Reaction With Water (Neutralizing Acid)

the alkali metals react with water to produce hydrogen and the metal hydroxide
Metal Oxide + Acid Salt + Water
the metals are called alkali metals because the resulting solution is alkaline
owing to the presence of the hydroxide ion
the reactions become most vigorous as we descend down a group as the
ionization energies decrease

Non Metals
o Form covalent bonds
o Relatively low melting and boiling point
o exist as diatomic
o they are coloured
o they show a gradual change from gases (F2 and Cl2) to liquid (Br2) to solids (I2 and At2)
o they are very reactive non-metals --> reactivity decreases down the group
o they form ionic compounds with metals or ionic compounds with other non-metals
o the trend in reactivity can be explained by their readiness to accept electrons the
nuclei have a high effective charge, and so exert a strong pull on any electrons from
other atoms; this electron can they occupy the outer energy level of the halogen atom
and complete a stable octet. The attraction is greatest for the smallest atom fluorine

reactivity decreases down the group as the atomic radius increases and the attraction
for the outer electrons decreases
Neutralize Bases

Non-metal Oxide + Base Salt + Water

Reaction with the Group 1 Metals

the halogens react with the group 1 metals to form ionic halides
the halogen atom gains one electron from the group 1 elements to form a
halide ion X-

Displacement Reactions
the relative reactivity of the elements can also be seen by placing them in direct
competition for an extra electron
the more reactive halogen displaces the ions of the less reactive halogen
The Halides
the halogens form insoluble salts with silver
adding a solution containing the halide to a solution containing silver ions
produces a precipitate which is useful in identifying the halide

Metalloids (semi-metals)
o Generally have characteristics that are intertwining

Oxides and Chlorides of the Third Period

Chlorides
o NaCl, MgCl3, AlCl3, SiCl4, PCl5 and PCl2, Cl2
o Note that as more valence electrons are added, more bonds with chlorine atoms
become possible. Also, phosphorous, which bonds covalently with chlorine, is able to
form more chloride compound
o Metal chlorides of the third period are ionic compounds with crystalline structures and
high melting and boiling points they readily dissociate in water Eg. NaCl = Na+ + Clo Like metal oxides their liquid (molten) states are conductors
o Non-metal chlorides of the third period are covalently bonded molecular structures
with weak intermolecular attractions and therefore low melting points and boiling
points when mixed with water HCL solutions are produced along with a gas
o Like non-metal oxides, their liquid (molten) states are not conductors
Oxides
o Na2O, MgO, Al2O3, SiO2, P4O6 and P4O10, SO2, SO3, Cl2O and Cl2O7

Period 3 oxides can be characterized based on their metallic/non-metallic properties as

described in the previous lesson (i.e decreasing conductivity across the period, or
whether they form acid or basic solutions)

Introduction to D-Block Elements

D-Block Elements are those elements that occur in the central block of the periodic table, in
which the d-subshell is filled across the period; partially filled d-subshell in one or more
oxidation states = transition metals
Oxidation State the charge an atom in a molecule/compound would have if all of the
electrons in its bonds belonged entirely to the more electronegative atoms
o Rules:
O is always -2, unless with F or in peroxides
H is always +1, unless with metal hydride (e.g NaH)
Groups 1 & 2 are always +1, and +2 respectively
Characteristics of transition metals include
o Variable oxidation states
o Ability to form complex ions
o Catalytic behavior
o Formation of coloured complexes

D-Block Elements (Part 2):

Variable Oxidation States

o S-block elements easily lose their valence electrons, but a substantial amount of energy
is required to remove anything past that
o Transition metals have a high first ionization energy due to their higher effective nuclear
charges, the energy required to remove subsequent electrons does not increase by as
much as it does in the s-block metals because 3d and 4s are very similar in energy;
therefore the most common oxidation state among the transition metals is +2
Formation of Complex Ions
o D-block elements are relatively small in size but have a high nuclear charges (small but a
very positive nuclei)
o Therefore, their ions tend to attract electron rich particles, particularly ions and
molecules that have non-bonding electron pairs
o These electron-rrich chemical species which react with transition metals are referred to
as ligands. They form dative or co-ordinate covalent bonds with transition metals
in order to form complex ions
o A common ligand is H2O, which is polar, electron rich and abundant
o Many transition metal ions exist most commonly as heavily hydrated complex ions
o However, other ligands can displace water molecules
o The number of lone pairs bonding to the metal ion is known as the co-ordination
number

Complexes with a co-ordination number of 6 are octahedral in shape, those with 4 are
tetrahedral (square planer), those with 2 are usually linear

D-Block Elements Part 3

In a transition metal, 5 orbitals, are degenerate = they are at the same energy level (d)
when binds with ligand and forms complex through the sharing of electrons the presence of the
ligands affects the d-orbitals, because the like-charge repulsion with the bonding electrons
this results in a splitting of the d-orbital split means that within the d-subshell, there are now
different energy levels, whereas without the ligands, the five d-orbitals that make up of the d
subshell all have the same energy
Transition metal complexes are colored because their central transition metal atoms have a
partially filled d subshell that is split by the surrounding ligands
All of the 3d orbital experience an increase in energy level, but the dz2-y2 and dz2 orbitals
experience a greater increase due to their orientations
The energy differs based on the ligands involved, but corresponds to frequencies within the
visual spectrum when white light passes through a transition metal compound, light of a
particular wavelength is absorbed and an electron of a lower energy orbital will be given a
longer frequency wavelength
Empty d-orbitals cannot produce colour because they lack electrons electrons are needed to
move from a lower energy d orbital to a higher energy d orbital by absorbing a photon of visible
light Sc3+ are colourless because Sc3+ has an empty d orbital
o If a complex has an empty d shell, there are no electrons to move.
o If a complex has a full d shell, there are no vacancies in any d orbitals for an electron to
move into
Complexes of Zn2+ and Cu+ are colourless because their d orbitals are full
The colours of wavelength we see are actually the complimentary colour to the frequency that is
absorbed

Factors Affecting the Colours of Transition Metal Complexes

1. The nature of the transition element: Even though Mn2+ and Fe3+ have the same electron
configuration (theyre isoelectronic) they have different numbers of protons in their nuclei, and
therefore the E between split d-orbitals are different. Consequently, in aqueous solutions
Mn2+ is pink and Fe3+ is yellow
2. Oxidation state of the same metal: eg. Fe2+ is green while Fe3+ is yellow
3. Identity of the ligand: [CrF6]3- is green, [Cr(H2O)6]3+ is violet, [Cr(CN)6]3- is yellow. The
spectrochemical series ranks ligands based on their ability to increase the E gap. The higher
the energy absorbed, the higher the frequency. This determines the complimentary colour that
is seen.
o Stereochemistry: the three dimensional structure of the molecule or ion.

D-Block Elements Part 4

The fact that transition metals often form coloured complexes can be used to quantify the
concentrations of their solutions.
The Beer-Lambert law is a mathematical relationship that allows chemists to determine the
concentration of a solution based on its absorbance of light
A = log10(I0 / I) = lc
o Where:
A = Absorbance (no units)
I0 = Initial intensity of light before passing though solution
I = Intensity of light after passing through solution
(epsilon) = Molar extinction coefficient. A measure of how strongly a
particular substance absorbs light. (L mol-1 cm-1)
l = Path length of the light (cm)
c = Concentration of the solution (mol L-1)

The Beer-Lambert law can also be expressed in terms of percentage transmission (T), the
percentage of light that is not absorbed by the solution.
T = (I / I0) x 100

Absorbance Spectrometer

Absorbance or transmission is measured by a device called an absorbance spectrometer.

Catalytic Behavior of D-Block Elements

Catalysts are substances which increase the rate of a chemical reaction without being
permanently altered themselves.
Transition metals act as catalysts because they form complex ions which can donate electron
pairs, which results in close contact between the metal and ligands & have a wide variety of
oxidation states which allows them to readily gain or lose electrons.

D-block elements can be either homogeneous catalysts (same state as reactants) or

heterogeneous catalysts (different state).

3.3 Chemical Properties

chemical properties of an element are largely determined by the number of electrons in the
outer shell
Group 0: Noble Gases

colourless gases
monatomic
very unreactive inability of their atoms to lose of gain electrons
highest ionization energies
Group 1: Alkali Metals

good conductors of electricity --> mobility of their outer electrons

low densities
very reactive --> low ionization level
ionic compounds with non metals
Reaction With Water
o
o
o

produce hydrogen and the metal hydroxide

the metals are called alkali metals because the resulting solution is alkaline owing to teh
presence of the hydroxide ion
vigorous as descend down a group because the ionization energies decrease

Group 7: The Halogens

diatomic
coloured
gradual change from gases (F2 and Cl2) to liquid (Br2) to solids (I2 and At2)
very reactive non-metals --> reactivity decreases down the group
ionic compounds with metals or ionic compounds with other non-metals
Reactivity because of readiness to accept electrons nuclei have a high effective charge, and
so strong pull on any electrons from other atoms; electron can they occupy the outer energy
level of the halogen atom and complete a stable octet. The attraction is greatest for the smallest
atom fluorine
reactivity decreases down the group as the atomic radius increases and the attraction for the
outer electrons decreases

Reaction with the Group 1 Metals

the halogens react with the group 1 metals to form ionic halides
the halogen atom gains one electron from the group 1 elements to form a
halide ion XDisplacement Reactions

the relative reactivity of the elements can also be seen by placing them in direct
competition for an extra electron
the more reactive halogen displaces the ions of the less reactive halogen
13.1 Trends Across Period 3
Bonding of the Period 3 Chlorides

Group
Formula of
Chloride
Conductivity
of Molten
Chloride
Structure
and
Bonding

1
NaCl
1074 (s)
+
Giant
ionic

2
MgCl2
987 (s)
+
Giant
ionic

3
AlCl3
463 (s)
Ionic/covalent

4
SiCl4
203 (l)
Simple
molecular

5
PCl5
435 (s)
Simple
molecular

6
S2Cl2
193 (l)
Simple
molecular

7
Cl2
172 (g)
Simple
molecular

Typical Bonding with Water

NaCl
MgCl2
AlCl3
SiCl4
PCl5

Dissolves readily, negligible heat change, colourless solution formed which contains Na + and
Cl aqueous ions. No hydrolysis; pH7
Dissolves slight heat change, colourless solution formed which contains Mg2+ and Cl
aqueous ions. Slight hydrolysis: pH 5 6
Reacts vigoursly, heat and sound produced, colourless solution formed which contains
[Al(H2O)6]3+ (aq) ions. Some hydrolysis: pH 2 3
Reacts violently, heat and steamy fumes of hydrogen chloride produced, gelatinous white
precipitate of hydrated SiO2 produced. Complete hydrolysis: pH 0 1
Reacts violently, heat and steamy fumes of hydrogen chloride produced, colourless solution
of phosphoric acid produced. Complete hydrolysis: pH 1 - 2

Explanations
The Cl- ion has a low surface density of charge and does not attract H20 sufficiently strongly for it to
hydrolyse significantly. Therefore, any reaction depends upon the element attached to chlorine.

NaCl and MgCl2 are ionic and water soluble. Although Mg2+ has a higher surface density of charge than
Na+, it does not hydrolyse well
AlCl3 shows covalent properties it sublimes, it is soluble in organic solvents, and forms a dimer (al2Cl6)
when it sublimes. In water, the meal ions formed have sufficient surface density of charge for hydrolysis
to occur. This is relatively small, but enough to give an acidic solution
[Al(H20)6]3+ (aq) + H2O(l) [Al(H2O)5(OH)]2+ (aq) + H30+ (aq) Note that the hydrogen ion cannot
exist in solution therefore forms an oxonium ion H3O+
The remaining chlordies are covalently bonded bc of chlorines electronegativity it induces a positive
charge on the atom attached. When they are added to water these chlorides are hydrolysed. The VIGOR
of the reaction increases across period 3 as the number of chlorine atoms bonded to the element
increase
Period 3 Oxides
Group
Formula &
State at
298K
Conductivity
of Molten
Oxide
Structure
and
Bonding

1
Na2O
(s)

2
MgO
(s)

3
Al2O3
(s)

4
SiO2
(s)

5
P4O10
(s)

6
SO2
(g)

7
Cl2O
(g)

+
Giant
ionic

+
Giant
ionic

+
Giant
ionic

Giant
Simple
Simple
Simple
molecular molecular molecular molecular

Typical Reaction With Water

Na2O
MgO
Al2O3
SiO2
P4O10
SO2

Dissolves readily, no heat formed, colurless

alkaline solution formation
SLIGHTY soluble in water, leaves fine white
suspension in alkaline solution
Insoluble in H2O but reacts with both acids and
bases to form salts amphoteric oxide
Insoluble in water but reacts with base to form salt
acidic oxide
Very exothermic reaction on adding water to
produce acidic solution
A gas which dissolves readily in water to produce a
colourless acidic solution

Explanations
1) Reactions of Sodium Oxide and Magnesium Oxide with Water

Hydrated ions are formed when ionic compounds dissolve in H2O. If the ionic radius is small and the
charge on ion is high, hydrolysis occurs. When sodium oxide and magnesium oxide are dissolved in
water, the small highly charged oxide ions strongly attract water molecules so after hydrating there is
hydrolysis to produce hydroxide ions:
O2- (aq) + H20(l) 2OH- (aq)
2) Reaction of Aluminum Oxide
Aluminum oxide has properties, which are intermediate between those of metallic oxide and those of
non metallic oxide:
Al2O3 (s) + 6H+ (aq) + 3H2O(l) 2[Al(H2O)6] (aq) AS A BASE
Al2O3 (s) + 2OH- (aq) + 3H2O (l) 2 [Al(OH)4] (aq) AS AN ACID
3) Reactions of Silicon Dioxide
The structure of silicon dioxide (SiO2) is an extended network of SiO4 units. Each central silicon atom is
bonded covalently to four oxygen atoms, but only has half share in four atoms. This structure is similar
to diamond. Because of giant covalent structure, it is insoluble in water, and has high melting point.
Acid Base Character of the Period 3 Oxides

Oxides of metals are ionic and basic

Oxides of the non-metals are covalent and acidic
Oxides of the metalloids are amphoteric both acid and base properties
Basic Oxides

A basic oxide reacts with an acid to form a salt and water

The oxide combines with two H+ ions to form water
Alkalis are bases which are soluble in water they form hydroxide ions in
aqueous solutions
Acidic Oxides

Non-metallic oxides react with water to produce acidic solutions

High melting points are associated with ionic or covalent giant structures; low
melting points with molecular covalent structures