GENERAL CHEMISTRY

I. IDEAL GAS LAW:

Ideal gas: is a theoretical gas composed of randomly moving, non-interacting
point particles.

nRT =PV
R = 0.082 atm.l/K (the same constant as R 8.314J/K)
Change of unit goes like this: P= F/S (N/m 2 = 1kgm/(sm)2 = 1Pa= 101 325
atm)
=> R= 0.082atm.l/K * 101 325 pa/atm * 0.001m3/l = 8.314 J/K.
Real gas Van der Waals model:

nRT = P+

a
( V b )
V2

In which, a and b are parameters that are determined empirically for each gas.
II. DETERMINE THE ATOMIC AND MOLAR MASS:
Boiling point elevation or freezing point depression:

M=

1000 mct
k t mdd

Dulong and Petit method:

M c=6.3

cal
J
=26
mol C
mol C

c: specific heat in J/g.C

Mass spectrometry: used to discover the mass/ charge of atoms. This can also
be used to find different isotopes of an element and their percentages.
How it works:
Stage 1: Ionization
The atom is ionized by knocking one or more electrons off to give a
positive ion (even for atoms which you normally expect to be negative:
chlorine, oxygen). Mass spectrometers always work with positive ions.
Stage 2: Acceleration
The ions are accelerated so that they all have the same kinetic energy

Stage 3: Deflection
The ions are then deflected by a magnetic field according to their masses.
The lighter they are the more they are deflected. The amount of deflection
also depends on the number of positive charges on the ion in other
words, on how many electrons were knocked off in the first stage. The
more ion is charged, the more it gets deflected.
Stage 4: Detection
The beam of ions passing through the machine is detected electrically.

M atom
H2
2
=Ker h
n
V
n: Number of electron separate from the atom
K: a constant
r: radius of the curve
H: Magnetic field intensity
V: voltage
III. STRUCTURE OF ATOMS:
Heinsenberg uncertainty principle:

xp

h
4

Slaters rules [semi-empirical]: In a many-electron atom, each electron is

said to experience less than the actual nuclear charge owing to shielding or

screening by the other electrons. For each electron, Slaters rules provide a value
for screening constant, which relates the effective/actual nuclear charges:

Z eff =Z s
The shielding constant is determined as followed.
Step 1: electrons are arranged into a sequence of group:
[1s] [2s,2p] [3s,3p] [3d] [4s,4p] [4d] [4f] [5s, 5p] [5d] etc.
Fe: [1s]2 [2s2p]8 [3s3p]8 [3d]6 [4s]2
Step 2:

Group

Other
electrons in
the same
group

[1s]

0.30

Electrons in
group(s)
with
principal
quantum
number n
and
azimuthal
quantum
number < l
-

[ns np]

0.35

0.85

[nd] or [nf]

0.35

Electrons in
group(s)
with
principal
quantum
number n-1

Electron in
all group(s)
with
principal
quantum
number < n1

Ex: Fe
4s :

0.35 1+0.85 14 +1.00 10=22.25= Z eff ( 4 s )=2622.25=3.75

3d :

0.35 5+1.00 18=19.75= Z eff ( 3 d )=2619.75=6.25

3s, 3p :

0.35 7+ 0.85 8+1.00 2=11.25= Z eff ( 3 s , 3 p )=2611.25=14.75

2s, 2p :

0.35 7+ 0.85 2=4.15= Z eff ( 2 s , 2 p )=264.15=21.85

1s :

0.3 1=0.3= Z eff ( 1 s )=260.3=25.7

Application of STOs (Slater Type Orbitals):

Calculation of the energy of any electron in any atom or ion by the formula:

E=2.18 10

18

Z
Z
J =13.6 eV

n
n

( )

( )

While the value of n* in accord to n:

n
n*

1
1

2
2

3
3

4
3.7

5
4.0

6
4.2

Example: Predict the energy of a 4s electron in Fe:

E=13.6

3.75 2
eV =13.97 eV
3.7

( )

Example: Calculation of the first ionization energy (IE) of Fe

0

+EFe
IE=E Fe
+
EFe 4s :

E0Fe=13.6

+=13.6

0.35 0+ 0.85 14+1.00 10=21.9= Z eff ( 4 s ) =2621.9=4.1

[( ) ( ) ( ) ( ) ( ) ]
3.75 2
6.25 2
14.75 2
21.85 2
25.7 2
2+
6+
7+
7+
1
3.7
3
3
2
1

[( ) ( ) ( ) ( ) ( ) ]
4.1 2
6.25 2
14.75 2
21.85 2
25.7 2
1+
6+
7+
7+
1
3.7
3
3
2
1
E Fe

[( ) ( ) ]
2

4.1
3.75
IE=13.6
1
2 =11.24 eV
3.7
3.7
In the same sense, the electron affinity can be measured.
Relation between principal quantum number and energy level:
Solution for the Schrodinger shows that electron can only have some specific
energy state. For atom with only one single electron, its energy equation is as
follow:

E n=

2
me 4
Z2
2
18 Z

Z
=2.18
10
J
=13.6
eV
8 20 n 2 h2
n2
n2

IV. STRUCTURE OF MOLECULE:

VB and VSEPR theories:
Lewis theory and Lewis acid/base.
VSEPR theory:

Geometry notes on the theory:

1. Although lone pairs (unbounded electron pairs) are clearly smaller than
atoms, they need to be closer to the nucleus of an atom than a bonding
pair. Being closer to the central atom causes lone-pairs take up more of
the available 'bonding space'.
2. The lone electron takes less space than a bond (Ex: NO2 has the O-N-O
angle of 134o
3. Repulsion between Lone pair - Lone pair > Lone Pair - Bond pair > Bond
pair - Bond pair => the change of shape when number of bonding
electrons decrease (Ex: for d2sp3 octahedral square pyramidal Square
planar )
4. Triple bonds > double bonds > single bonds in taking up space (still not
taking up as much space as lone pairs)
5. Electronegativity

The repulsion between electron pairs increases with increase in

electronegativity of central atom and hence the bond angle increases. The
bond pairs are closer and thus by shortening the distance between them,
which in turn increases the repulsion. Hence the bonds tend to move away
from each other.
However the bond angle decreases when the electronegativities of ligand
atoms are more than that of central atom. There is increase in the
distance between bond pairs since they are now closer to ligand atoms.
Due to this, they tend to move closer resulting in the decrease in bond
angle.
6. Size of atoms:
The bond angle decreases with increase in the size of central atom.
The bond angle increases with increase in the size of ligand atoms, which
surround the central atom.
7. Equatorial bonds are shorter than axial bonds.
What Ive come across about MOLECULAR ORBITAL THEORY

Fig. 1: MO model for homogenous molecule in the end of the 2 nd period (O2, F2)

Fig. 2: MO model for monatomic molecules in the beginning of the 2 nd period (B2,
C2, and N2) and diatomic molecules (NO, CO). The energy level of orbital shift
because there is hybridization between 2s orbital on one atom to interact with
the 2pz orbital on the other, which can affect the energy levels more on those in
the beginning of the period because the difference in energy between 2s and 2pz
is not too great.
After filling out electrons into the model, we can get the
Bond order:

Bond order=

Bonding electronsanitbonding electrons

2

Oxygen paramagnetic property : a molecule is paramagnetic when it has

unpaired electron(s) and is diamagnetic if it has no unpaired electron. Lewis
structure cant explain the paramagnetic property of oxygen (at least in its liquid
form; for gas, the kinetic energy was too large for the magnetic field to have an
effect on it) while MO model can.
Geometry of the MO orbitals:

Conjugated system MOs:

First lets take a look at the formation of 2p and 2p*

Then the bond MO of ethene from two 2p orbitals: There are two electron on
the 2p

In the same sense, conjugated system can be constructed. The energy levels
increase as the number of nodes increases.
Examples:

Butadiene MOs

A bond and a lone pair conjugated system

Benzene MOs

Hexatriene
Hckel method/ How to draw these conjugated MOs correctly: