Chemistry Review

A. Atomic Structure and Electronic Configuration

B. Chemical Bonding
C. Chemical Units and Calculations
D. Water Chemistry
E. Acids and Bases
F. Energy Relations of Thermodynamics

Atomic Structure and Electronic

Configuration

z Rutherford Model---Planetary

Coulomb attraction:
A
F = C.(e-.a+/r2)
+
e- = charge of electron
a+ = the charge of nucleus
r = distance
C = constant
 Atomic Structure and Electronic
Configuration

z Modern model--- Electrons behave like both

particle and wave, and the levels of energy
are quantized.
‹ Electron carries both kinetic and magnetic
radiation energy

Atomic Structure and Electronic Configuration

Atom has different energy levels depending where e- is

Spectroscopic observation: Energy level diagram of hydrogen

‹ Principal energy levels: n= 1, 2, 3….
‹ Sublevels or orbitals as s, p, d, f , …(spectrum term)
 z Based on wave functions:
‹ Orbital: defined as a region in space around nucleus where the
probability of finding the electron is the greatest

z Probability regions of s, p, d, and f orbitals

Energy level:
s<p<d<f

Probability regions of s, p, d, and f orbitals

S orbital: 1 space
orientation

d orbital: 5 space
orientations

p orbital: 3 space orientations F: 7 space orientations

z Pauli Exclusion Principle : No more than two
electrons may occupy any single probability
region (orbital) and only if they have opposite
spins

Maximum possible number of electrons can

occupy a principal energy level : 2 (n)2

Energy level (n) 2(n)2 Max e- population

1 2(1)2 2 (1s2 )
2 2(2)2 8 (2s22p6)
3 2(3)2 18 (3s23p63d10)
4 2(4)2 32 (4s24p64d104f14)
5 2(5)2 50 --
z Aufbau Principle

When building structure of an atom, electrons are

arranged by assigning the first ones to lowest energy
levels and then moving toward higher energy levels in
known order until all electrons are distributed among
orbitals

z NOTE:
Total energy required for an electron to occupy a d or f
orbital of a lower principal energy level may be higher
than the energy of an electron in the s or p orbital of the
principal energy level above it

Subdivision of energy levels

w

Sequence of filling atomic orbitals in atomic

“building”
 z Hund’s Rule (Principle of maximum
multiplicity)

In the filling of the p, d, and f orbitals, there must be at

least one electron in each orbital before pairing begins
for atoms in the ground state

z This means in the regions of equivalent probability

(e.g. px, py and pz), electrons require less energy to
occupy orbital singly than they do to pair off with
those of opposite spins

z Example 7N and 26Fe

z Quantum numbers to describe electron configuration in an

atom (Quanta/quantum --- discrete or non-continuous)

z Principal quantum number (n)

‹ n= 1, 2, 3, ….

z Orbital quantum number (l)

‹ l= 0, 1, 2, 3, … (n-1)

z Magnetic quantum number (ml)

‹ ml= +l, (l-1), …, 0, … (-l+1), -l

‹ It has 2l +1 values

z Spin quantum number (ms)

‹ ms= +1/2, -1/2
 z What does each quantum number mean?

‹ n (principal quantum #) --- relates to average

distance of the electron to nucleus

‹ l (orbital quantum #) --- defines shape of the

electron cloud

‹ ml (magnetic quantum #) --- represents the

direction of maximum extension in space in which
an electron would have the highest probability to
be found

‹ ms (spin quantum #) --- represents the magnetic

effect related to the electron spin

n indicates number of orbital type

Example : 8O

Spectroscopic notation:

1s2 2s2 2p4

↑↓ ↑↓ ↑↓ ↑ ↑

Quantum number:
n l ml Ms
1 0 0 +1/2, -1/2
2 0 0 +1/2, -1/2
2 1 +1 +1/2, -1/2
2 1 0 +1/2
2 1 -1 +1/2

Heavy metals: density > 3 g/cm3 Light metals: density < 3 g/cm3 (alkali and alkali earth and Al)
A closer look

Chemical Bonding
z What is chemical bond?

‹ Definition --- The force that holds atoms together

z All chemical bonds involve valence electrons of

atoms

z Valence electrons are those associated with the

highest principal quantum number (n) or principal
energy level
 The newly created structure associated with formation of
chemical bonds must have greater stability and lower energy
than do isolated atoms

Covalent bond --- those formed by

sharing electrons of two individual
atoms.
e.g. F2 between two 9F

Ionic bond --- Those formed by

attraction of oppositely charged
ions. e.g. Na+ . Cl-

Ions are formed by electron transfer from

one atom to another.

Cation --- atom loses electron and becomes

positively charged ion. e. g. 11Na+

Anion --- atom gains electron and becomes

negatively charged ion . e. g. 17 Cl-
Ionization energy --- The energy necessary
to remove an electron from atom in the
gaseous state
z Coordinated covalent bond (or polar covalent
bond)

‹ Definition --- electron sharing between different

atoms that have different electron attracting ability
(e.g. 1H and 53I)

‹ Coordinated or polar covalent bonds are commonly

weaker than non-polar covalent bonds of sharing
electrons between same element (e.g. I2)
 Non-polar
covalent
↑

Polar covalent
↑

Ionic

Conceptual illustration of structural difference from

ionic structure to covalent molecule

z Electronegativity

‹ Definition --- The relative value of the

electron-attracting ability

‹ It relates to the nuclear charge and

atomic size

‹ It is a periodic property of atoms. It

increases from left to right and
decreases from top to bottom
 w

Electronegativity values of elements

Electronegativity has same trend as ionization energy

z Rule of Thumb:

ΔEN Bond Type % Ionic

< 0.5 Non-polar covalent bond < 8%

0.5--1.7 Polar covalent bond 8--50%

>1.7 Ionic bond > 50%

 Result of forming covalent and ionic bond:
To make the out shell of an atom have more stable
configuration (e.g. P orbital satisfied)

z Example: 11Na and 9F form ionic bond

11Na 9F

1s22S22P63S1 1s22S22P5

11Na 9F
+ -

1s22S22P6 1s22S22P6

• Common cations with likely valence or charge

K+, Ca2+, Mg2+, Cu+, Cu2+, Cd2+, Pb2+, Al3+, Fe3+, Fe2+, Si4+

z Polarity of multi-atom molecules

‹ Geometry vs. electronegativity effect on
polarity (e.g. HI vs. CH4)

z Hydrogen Bonding

‹ Definition--- close dipole-dipole interaction

involving polar molecules containing
hydrogen bonded to a small, and highly
electronegative atom

z Network Bond

‹ Result of complex and extensive covalent

bonding so that huge crystals rather than
simple molecules are formed
(e.g. diamond of C network bonding)
 Chemical Units and Calculations
Commonly used units

‹ Mole: fundamental unit for chemical reaction

• 1 mole = 6.02X1023 particles (atoms, molecules, or ions), (Avogadro’s
number)

‹ Atomic weight (AW): Weight in grams of a mole of selected atoms (all

isotopes)
• Atomic mass of a exact isotope expressed as relative to C atom (C-12
isotope), which is assigned as exact 12.00 amu or daltons

‹ Formula weight (FW): Weight in grams of a mole of the selected compound

‹ Molarity (M): mole per liter (mol/L).

• 1 mol/L =1000mmol/L=1000,000 μmol/L =106 μmol/L

‹ Molality: mole per kilogram (mol/kg)

Chemical Units and Calculations

‹ Equivalent (Eq): mass in gram to react with 1 mole of electrons
• Equivalent weight = mole weight/charge

‹ Normality (N): Eq/L

‹ meq/100g = cmol/kg

‹ mg/L = μg/mL = ppm (part per million) for solution

‹ Mg/kg = μg/g =ppm for solid (10000ppm =1%)

z Common calculations

‹ M (mol/L) x Valence (z) = N (Eq/L)

‹ C1V1 = C2V2
 Water Chemistry
z Polar molecule (dipole)

z Excellent solvent

z Hydrogen bonding

Cluster of water
molecules
(cohesion)

Water Chemistry
z Adhesion: hydrogen bonding between H2O and
solid surface
‹ Hydrophilic vs. Hydrophobic

z Some characteristics of water

‹ Surface tension
• Difference in intermolecular attraction force of liquid at
interface between liquid and other medium ( e.g. air)
Surface Tension of Water Relative to Other
Liquids
Substance Surface tension (dyne/cm)
_____________________________________________
Water 73
Ethanol 22
Benzene 29
Mercury 430
_____________________________________________
Higher surface tension suggests that the liquid likely stays together to
reduce surface area
Water stay together able to reach the highest leaves in a tall tree
(e.g. redwoods)

Specific Heat Capacity of Water Relative to

Other Substances
Substance Specific Heat Capacity
(Cal/deg/gm)

_____________________________________________
Water 1.00
Ice 0.50
Iron 0.11
Dry soil 0.20
Air 0.17

_____________________________________________
Amount of heat in calorie required to raise temperature of 1oC per gram of
substance
Heat Transformation of Water Relative to Other
Liquids
Substance Liquid to Gaseous State (Cal/gm)
_____________________________________________
Water 540
Methanol 263
Ethanol 204
Acetone 125
_____________________________________________

80 Cal/gm is required for water transforming from solid to liquid phase.

In drought condition, liquid water can often be still found.

Dielectric Constant of Water Relative to Others

Substance Dielectric Constant
_____________________________________________
Water 80
Methanol 33
Ethanol 24
Acetone 21

Vacuum 1 (by definition)

_____________________________________________
Dielectric constant = ratio of material capacitance to vacuum capacitance,
measuring the amount of electrical energy a substance can withstand at a
given electric field.
z Hydration: Water molecules adsorbed
on to ions or compounds

Hydration
sphere of
sodium

z Hydrolysis: Adsorbed H2O dissociates to satisfy ion

electronegativity
Ca2+ + H2O → Ca(OH)+ + H+

z Amphoteric (can act as acid or base) depending on the

substance water is reacting with

H2O → H+ + OH-

‹ [H+][OH-] =Kw = 1.0x10-14 at 25 oC

‹ pH + pOH = pKw =14
• Kw is ion activity product of water
• pKw ranges from 14.93 at 0 oC to 13.26 at 50 oC
 Acids and Bases

z Bronsted-Lowry Concept

‹ acid --- proton donor

‹ base --- proton acceptor

‹ Strong --- 100 % dissociates in water

• Examples

‹ Weak --- <100% dissociation in water (often <1%)

• Examples

z Lewis concept

‹ acid --- capable of accepting an electron pair

‹ base --- capable of donating an electron pair

‹ Relatively strong acids and bases

• Examples: acids: Al3+ , cations with valence > 2
• bases: PO43- , anions with valence > 2

‹ Weak acids and bases

• Examples: acids: K+, cations with valence < 2
• bases: Cl- , anions with valence <2
 z Weak monoprotic acids

‹ Single dissociable H+
‹ Dissociation constant, Ka

Examples: Iodic acid, HIO3 Acetic acid, CH3COOH

z Weak polyprotic acids

‹ more than one dissociable H+
Examples
H3PO4 pKa1 = 2.3 H2CO3 pKa1 = 6.3
H2PO4- pKa2 = 7.2 HCO3- pKa2 = 10.3
HPO42- pKa3 = 12.3

HOOCCOOH (oxalic) pKa1 = 1.3

HOOCCOO- pKa2 = 4.3

z Henderson-Hasselbalch equation

pH=pKa + log[(base form)/(acid form)]

[HA]<[A-]

[HA]>[A-]

[HA]=[A-]
Polyprotic acid titration

Titration curve of a monoprotic weak acid

(lag of reaching equivalent point)
z Environmental buffer

‹ Acid-base buffer at pKa

‹ Natural buffer

z Open system
↔ H+ + HCO3-

z Closed system

z Isolated system

Energy Relations of Chemical Thermodynamics

¾ Definition: Energy change in macroscopic system

¾ Objective:
¾ Determine & interpret occurrence and direction of processes
¾ Establish equilibrium conditions

¾ Usage: Calculation of properties of states

¾ State properties of a matter or system : P, V, T, mass,

surface area, composition (e.g. mole fraction), etc.
 ‰ Energy relations of thermodynamics
‹ First Law (Conservation of Energy Principle )
• Total energy of an isolated system remains constant regardless any
change to occur in the system

• Etotal = U + Epotential + Ekinetic

• ΔU = ΔQ – ΔW

• When only PV work is concerned, ΔU = ΔQ – Δ(PV) = ΔQ – (PΔV + VΔP)

(PV, the work required to displace the surrounding atmosphere in order
to vacate the space to be occupied by the system)

• First law: ΔU = ΔQ – PΔV or dU = dQ – PdV

• Also: ΔU + PΔV = ΔQ = ΔH (U + PV =H, defined as enthalpy or heat

content)
ΔH measured as heat absorbed or released by system at constant pressure, Qp

• Therefore, ΔH = ΔU + PΔV or dH = dU + PdV

‰ Energy relations of thermodynamics

‹ Second Law (Direction of spontaneous process)

• No process is possible in which the sole result is the absorption of heat from a
reservoir and its conversion into work (without expense of energy on somewhere)

• Entropy (S), a measure of the chaotic dispersal (randomness) of energy and the
natural tendency of spontaneous change, always increases towards states of higher
entropy

• Defined: ΔS = ΔQ/T
ΔS measured by heat transported into the system then divided by temperature
ΔQ = TΔS

• In irreversible process for an isolated system: ΔS > 0

• Reversible process: ΔS = 0
(in reversible process, any change is finely balanced so that the system is in
equilibrium with its environment at every stage)

• Free Energy: Maximum work that can be carried out for an isothermal reversible
process
– Helmholtz free energy, F (at constant T and V) ΔF = ΔU – TΔS
– Gibbs free energy, G (at constant T and P) ΔG = ΔH – TΔS (most commonly used)
TΔS is referred to “bound energy”
‰ Energy relations of thermodynamics

‹ Second Law (Direction of spontaneous process)

• Driving force for a spontaneous process is to reduce its free energy
• For any spontaneous process, ΔS > 0 and ΔG < 0
• At equilibrium, ΔS = 0 ΔG = 0

H
U PV
TS F PV

TS G

‰ Energy relations of thermodynamics

‹ For a chemical reaction: A + B = C + D
(T =25oC and P = 1 atm, standard state)

ΔGro = ∑ΔGfoproducts – ∑ΔGforeactants

(Gfo = standard free energy of formation)

ΔGro = -RTlnKeq

ΔGro = ΔHro – TΔSro

ΔHro = ∑ΔHfoproducts – ∑ΔHforeactants (>o, Endothermic vs. <0, Exothermic)

ΔSro = ∑ΔSfoproducts – ∑ΔSforeactants