Chemistry

2. Atomic structure (SL)

2.1 The Nuclear atom

Mass + change distribution

- mass concentrated in nucleus  contain the heaviest subatomic particles
- mass of electron can be ignored
- nucleus is + charge due to proton
- electron orbit around nucleus create cloud of negative charge
- electrostatic attraction between positive nucleus + electrons

Atomic structure
Name symbol charge Relative mass
electron e- -1 1 / 1840
Proton P+ +1 1
Neutron n 0 1

Isotopes
- same no. of proton + electron but different no. of neutron
- following the carbon 12 scale
Proton
- atom + ions have same no. of proton
- atomic number = proton number
- mass number = proton no. + neutron no.

Electrons
- atoms are neutral  same no. of proton + electron
- ions = different no. of electron
- positive ions = less electrons
- negative ions = more electrons

Formula of relative atomic mass = (% abundance x mass A) + (%abundance x mass B) / 100%

2.2 The electromagnetic spectrum

Electromagnetic spectrum / continuous spectrum

- range of frequencies cover all radiation + respective wavelengths + energy
- divide into regions
- spectrum shows the relationship of frequency
- frequency = how many waves pass per second
- wavelength = distance between two peaks of waves

2.3 Emission spectra

Emission spectrum
- electrons move rapidly around the nucleus
- energy increase = jump to higher energy level (further away from nucleus)
- reversible process = electrons can return to original energy level
- emit of mixture frequencies = many possibilities of electron to jump at
energy level

Line of emission spectra

- each line = specific energy value = electrons can only pass through these
value
- convergence = frequency of emission closer together at high F
- reach to maximum amount of energy = ionization energy

Hydrogen emission spectrum: line spectrum has only lines of sharp / discrete / specific wavelength

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Bohr’s model
1. several energy levels are available + electron transition exists between orbits
2. energy difference between energy shell is not identical
3. energy difference decrease as the no. of shell increase

Limitations Bohr’s model

1. cannot explain with more than one electron
2. position of electron are not in circular trajectory
3. impossible to determine the position of electrons

U2.4 Electron energy level

Shells
- arrangement of electrons = electronic configuration
- arrange around nucleus in principal energy level
- lower principal = close nucleus
- each principal has fixed no. of electron:
o N =1: 2 electrons
o N=2: 8 electrons
o N=3: 18 electrons
o N=4 32 electrons

Subshells
- Sub levels of electron shells SPDF

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Orbitals
- subshells contain one or more atomic orbitals
- exist at specific energy levels + electrons can only find at these specific levels
- each orbital occupies

Ground state
- most stable electronic configuration  lowest amount of energy
- achieve by filling subshells from lowest energy first  Aufbau principle

Sub levels + energy

- increase energy: S<P<D<F
- 4s orbital slightly lower than 3d orbital
- all subshell has same energy

1. S-orbital
- include in every energy level
- spherical shape
- each orbital hold 2 electrons
- increase in size when increase energy level

2. P-orbital
- dumbbell shape
- start at second energy level
- oriented perpendicular to one another
- lobes of P orbital become larger + longer with increase shell
number

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Electron configuration laws:
1. Aufloau principal  electron place in lowest energy level first
2. Paul’s exclusive principle  at least 2 electrons per orbital in opposite spin (repulsion)
3. Hund’s rule  orbital of equal energy is single filled first (stability)

Determining electronic configuration

1. full electronic configuration  arrangement of all electrons
2. shorthand electronic configuration  nearest noble gas + rest of electrons
- lose and gain of electrons
o Negative ions  gain electrons
o Positive ions  lose electrons
o Transition metal fill 4S subshell before 3d subshell  lose
electrons from 4S first
- blocks of periodic table:

- Cr: [Ar] 3d5 4s1 not 3d4 4s2

- Cu: [Ar] 3d10 4s1 not 3d9 4s2
- they are energetically favorable
- gain extra stability

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12. Electrons in atoms (HL)
Ionization energy: minimum energy requires to remove 1 mole of electron from 1 gaseous state atom

+ -
X →X +e
(g) (g)

Ionization energy = endothermic reaction  absorb energy to break bonds

Emission spectra
- Electrons move rapidly around nucleus in energy shells
- Heat / electricity can excite electrons to higher energy level  range from N=1 to N=
infinity
- Electrons fall back to ground state  release electromagnetic energy
- Emitted energy in visible range = line of emission spectrum

Limit of Convergence (LOC)

- Frequency of emission line become closer and closer
- Towards a higher frequency
- energy given to electron reach to LOC = IE
- frequency of radiation in LOC can determine the IE

Calculating first IE
ν=c÷λ
- V = frequency
- Λ = wave length
- C = speed of light (3.00 x 10^8)

ΔE = h ν
- E = first IE
- H = plank’s constant (6.63 x 10^ -34)
- V = frequency

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12.2 Trends in ionisation energy
- Shows the periodicity across periodic table

1. Group 1 element have lowest IE value

- electrons are put in higher energy level
- further from the nucleus = attractive force is weaker

2. Size of the nuclear charge

- increase nuclear charge  increased number of protons
- all electrons in same energy level  screening / shielding effect
- valence electrons experience stronger attractive force from the nucleus + gets pull in

3. Shielding effect
- lower shielding effect  higher IE
- reduction in the effective nuclear charge on electron cloud
- due to different attraction force in the nucleus

4. Fall in IE
- fall from Be to B  P orbital is in a higher energy level + electron further away from nucleus + experience
more shielding
- fall from N to O  electron of N not paired in P orbital  O have paired electrons in P orbital  easier to
remove because of repulsion  O have lower IE

5. general trend from Na to Ar

- nuclear charge increase  increase proton number  pull shells towards nucleus
- experience similar screening (shielding) effect  valence electrons have stronger to nucleus
Successive ionization energy

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6. trend down the group
- down the group  IE decrease  down the group nuclear charge increase  shielding effect increase due to
extra electrons added  extra protons compensate extra electrons -> additional distance between outer
electrons to nucleus  IE decrease

X + 2+ -
+ energy  X + e
(g) (g)
Second ionization energy: energy require to remove one mole of electron from one mole gaseous
state cation ion

Third ionization energy: energy require to remove one mole of electron from gaseous double charged
ion

IE always increases
- Remove 2nd electron  remove electron from positively charge ion  less electron 
electron repulsion  attract closer to nucleus  higher IE

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13. Transition metal
13.1 Transition metal
- element with incomplete subshell
- form at least one stable cation with incomplete d-subshell
o Anomalies:
1. Scandium: form ions Sc3+  configuration [Ar] 3d0
2. Zinc: form ions Zn2+  configuration [Ar] 3d10

Electron configuration
- follow the Aufbau principle
- electrons occupy the lowest energy subshells
first
- fill 4s first then 3d

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General properties
1. variable oxidation state
2. form complex ions
3. form-colored compounds
4. behave as catalyst
5. have magnetic properties

13.2 Variable oxidation state

Loss of electrons
- lose from 4s first
- repulsion pushes 4s to higher energy state  higher than 3d
- 4s is outer shell  lose electrons first
- lose of 4s electrons  +2 common oxidation state in transition metal

IE of removing successive electrons from titanium + vanadium

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- first few IE are close together  energy difference with removing small number of electrons enable
transition metal to have varying oxidation state
- +2 / +3 are all shown in transition metal
- +3 state is more stable till chromium + +2 state more stable in later elements
- transition metal with +3 oxidation state or above:
1. polarizing
2. have covalent character in bonds
3. high charge density+ pull electrons to themselves

13.3 Complex ions

Complex ions
- form complexes consist central metal ion + ligand
- ligand  molecule / ion that form co-ordinate bond with transition metal
- Lewis’s base  donate pair of electrons to bond
- ligands are negative charge / have lone pair electrons to donate
- ligand = electron pair donor
- ligand can form one co-ordinate bond / multi co-ordinate bond

Co-ordinate number = number of co-ordinate bonds

Common ligands
- water molecules are common ligands
- water make single bond with metal ion using one pair from O atom
- lone pair partially filled d-subshell of transition metal ion

Representing complex ions

- square brackets are used to group together the ligands + metal ion

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 - group in geometrical arrangement
- overall charge of complex = sum of oxidation state of all species
- ligands are neutral  overall charge = same as oxidation state of
metal ion

Co-ordination number
- coordination number = number of coordinate bonds to metal ions
- same as the no. of ligands
- can be bi- or multidentate ligands

Naming complexes:
- prefix for number of ligands  ligand name  element -> oxidation no.
- prefixes: di, tetra, hexa for 2,4,6
- overall anion  name modified end with ‘ate’

Bidentate ligands
- each from two co-ordinates bonds to central metal ion
- each ligand contains two atoms with lone pair of electrons

Multidentate ligands
- some ligands contain more than wo atoms with lone pair of electrons
- from two dative bonds  multidentate / polydentate ligands

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13.4 Catalytic + magnetic properties

Properties
- used as catalyst
- ability of transition metal to form more than one stable oxidation state
- enable redox reaction
- two types:
1. heterogenous  different physical state from reactant
2. homogenous  same physical state

Catalytic converter
- used to reduce air pollution
- transition metals convert pollutants (CO / NO2) to less harmful products
2NO (g) + 2CO (g) → N2 (g) + 2CO2 (g)

CH3CH2CH3 (g) + 5 O2 (g) → 3CO2 (g)  + 4H2O (g)  

- minimise cost + maximise efficiency:

1. increase surface area for catalyst

Diamagnetism
- diamagnetic material have paired electrons
- spinning electrons create tiny magnetic dipole
- paired electrons spin to create opposite external field
- very weak repulsion force

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Para magnetism
- attract to external magnetic field
- unpaired electron can be temporally aligned to magnetic field

- most transition metal are paramagnetic (unpaired electrons)

- increase magnetism when unpaired electrons increase

Color in transition metal

Perception of color
- transition metal absorb visible light from electromagnetic spectrum
- color absorb is complementary to color observed

Crystal Field theory

- five orbitals in D orbital have similar energy  degenerate
- ligands attach to transition metal cause D orbital to repel
- dative bonding from ligands cause D orbital to split
- two sets of orbitals are not equal in energy  nondegenerate orbitals

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Splitting in octahedral complexes
- six ligands bind with transition metal
- lone pair of electrons in ligands repel in x2y2 + Z2 orbitals more than other 3 orbitals
- x2y2 + z2 orbitals line with dative bonds of octahedral shape
- incoming ligands bond with central metal ions
- electrons in x2y2 + z2 closer to bonding electrons  more repulsion
- higher energy in x2y2 + z2

Absorption of light
- visible light pass-through transition metal
- D orbital splits
- electron in lower energy excite to higher energy D orbital
- light absorbed will transmit complementary color

Factors affect color

1. Size + type of ligand
- ligands vary in their charge density
- greater charge density = stronger attraction between orbitals
+ ligand
- absorb higher energy

2. Nuclear charge
- attraction between metal ions + one pair of electrons in ligand
- depend on charge of metal ions
- stronger interaction with ligand
- absorb higher energy

3. Oxidation state
- same metal in higher oxidation state create higher interaction with ligands

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3. periodicity

4. ionic bond
Ionic structure
- ions are packed together in a regular lattice structure
- arrangement of ions depends on ion’s charge and size

Physical property
1. volatility  tendency to become gas
-low
- strong electrostatic force of attraction between ions

2. electrical conductivity
- solid: none
- liquid: yes
- mobile ions to conduct electricity

3. solubility
- dissolves in polar solvent: water
- water with partial charge is attracted to the ions
- pull individual ions out t from lattice
- ions form ion-dipole interaction with water

- not soluble in non-polar solvent: hexane

- no attraction between solvent molecules and ions

Covalent bonds
- nonmetal atoms seek to gain electrons to have full outer shell
- shared pair of electrons between two nuclei

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- electrostatic force of attraction between the shared electron pair and the positively charge nuclei holds the
compound together

Bond length
- distance between the two bonded nuclei

Bond strength
- energy needed to break the bond

1. increased number of shared electrons

- stronger electrostatic force of attraction between shared electrons and bonded nuclei
- greater pulling power to bring nuclei closer together ‘
- shorter and stronger covalent bond

Polar covalent bond

- unequal sharing of electrons
- difference in electronegativity
- high electronegativity attract electrons closer
- have more ionic bond character
- become bond dipole

Coordinate covalent bond

- seen in formation of metal complex
- shared electron pair comes from only one of the bonding atom
- arrow to show origin of bonding electrons

- resonance involves using two or more Lewis structures to represent a particular molecule or ion
- resonance structure is one or two more alternative Lewis structures for a molecule or ion that cannot be
described fully with one Lewis structure alone

Delocalized electrons
- delocalization involves electrons that are shared between all atoms in a molecule or ion as opposed to being
localized between pair of electrons
- delocalization makes the chemical species more stable
- identical bond lengths and bond angle

Degree of repulsion
LP-LP > LP-BP > BP-BP
Linear
Trigonal planar
Tetrahedral
Trigonal bipyramidal
Octahedral

Draw Lewis structure

Find electron domain
Predict electron domain geometry and molecular geometry
Find the angle

One lone pair will make the angle decrease 2.5 degree
- nonbonding electron pair cause more repulsion and smaller angle

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