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BONDING

A. The Ionic Bond (Electrostatic Forces Between Ions)


1. Electrostatic energy q1q2/r : the greater the electrostatic energy, the stronger the
bond between them
2. Electrostatic energy lattice energy
3. Electrostatic force q1q2/r2
B. The Covalent Bond
Definition: a covalent bond is formed between atoms when each contributes one of its
unpaired valence electrons. By sharing a pair of electrons to form a bond, each atom may
acquire an octet configuration.
Single bond:
Double bond:
Triple bond:
1. Sigma and pi bonds
a. hybrid orbitals (sp3, sp2, sp, and respective geometries)
Number of Electron groups

Geometric Family

2
3
4
5
6

Linear
Trigonal planar
Tetrahedral
Trigonal bipyramidal
Octahedral

Hybridization of Central
Atom
sp
sp2
sp3
sp3d
sp3d2

b. valence shell electron-pair repulsion (VSEPR) theory, predictions of shapes of


molecules(e.g., NH3, H2O, CO2)
The shapes of simple molecules are predicted by VSEPR theory. Since electrons
repel one another, electron pairs, whether bonding or nonbonding, attempt to
move as far apart as possible.

2. Lewis electron dot formulas


Definition: place valence electrons as dots around the element
a. resonance structures: some molecules have equivalent Lewis structures called
resonance structures.
Resonance structures are two or more structure where only nonbonding electrons
and double and triple bonds may move around
Ex.
b. formal charge: the formal charges tells us if the atoms are sharing their valence
electrons in the best way. The best way is when the formal charges of each atom is
0 or the magnitude is minimized.
1
Formal charge (FC) = V BL
2
V- the number of valence electrons
B- the number of bonding electrons
L- the number of lone-paired (non-bonding) electrons
Note: when encounter this type of questions, count the number of valence
electrons first to make sure it matches the supposed numbers. Then, count the number of
electrons around each atom to make sure they dont exceed 8.
c. Lewis acids and bases
Coordinate covalent bond: when one atom donates both of the shared electrons in
a bond.
Lewis base: molecule donates a pair of electrons
Lewis acid: molecule accepts a pair of electrons
3. Partial ionic character
a. role of electronegativity in determining charge distribution
FONClBrISCH is with decreasing electronegativity. When there is a difference in
electronegativity, the element with smaller electronegativity will be partially
positive; the element with greater electronegativity will be partially negative. We
refer to this as polarity and say that the molecule has dipole moment.
b. dipole moment
The greater the difference between bonding elements, the greater the diploe
moment.

Ex. N2,OCS, CCl4


N2 is non-polar
OSC: O C S, OC bond is more polar than CS bond, therefore, the
molecule is polar
CCl4: each bond is polar, but since the bonds are symmetrically arranged around
C, the molecule is non-polar.
4. Types of solids
ionic solids: electrostatic attraction between cations and anions. Ionic bonds are
strong, and most ionic substance solid at room temperature
network solids: atoms are connected in a lattice of covalent bonds, meaning that
all interactions between atoms are covalent bonds. Network solids are very strong,
and tend to be very hard solids at room temperature.
metallic solids: can be thought of as a covalently bound lattice of nuclei and their
inner shell electrons. They have conduction electrons.
molecular solids: held together by one of 3 types of intermolecular interactions:
hydrogen bonds, dipole-dipole forces or London dispersion forces.

PHASES AND PHASE EQUILIBRIA


A. Gas Phase
1.
2.
3.
4.

5.

Absolute temperature, K: C + 273.15 K


Pressure, simple mercury barometer
1 atm = 760 mm Hg, mercury barometer still uses the principle of P = gh
Molar volume at 0C and 1 atm = 22.4 L/mol, this is called STP volume
Ideal gas
a. Definition: a gas which satisfies all these conditions
The molecules of a gas are so small compare to the average spacing
between them that the molecules themselves take up essentially no
volume. Treat them as point masses
The molecules of a gas are in constant motion. The pressure of the gas is
defined by the collision of the molecules with the wall of the container
All collisions are elastic
The gas molecules experiences no intermolecular forces
KEavg T
b. ideal gas law (PV = nRT)
i. Boyles law
If the temperature is constant, P 1/V
ii. Charless law
If the pressure is constant, V T
1 iii. Avogadros law
2 If two equal volume containers hold gas at the same P and T, then they contain
the same number of particles, regardless of the identity of the gas
Kinetic theory of gases
Agasiscomposedofaverylargenumberofextremelysmallparticles

6.

(moleculesor,insomecases,atoms)inconstant,random,straightline
motion.
Moleculesofagasareseparatedbygreatdistances.Thegasismostly
emptyspace.(Themoleculesaretreatedassocalledpointmasses,as
thoughtheyhavemassbutnovolume.)
Moleculescollideonlyfleetinglywithoneanotherandwiththewallsof
theircontainer,andmostofthetimemoleculesarenotcolliding.
Thereareassumedtobenoforcesbetweenmoleculesexceptverybriefly
duringcollisions.Thatis,eachmoleculeactsindependentlyofalltheothers
andisunaffectedbytheirpresence,exceptduringcollisions.
Individualmoleculesmaygainorloseenergyasaresultofcollisions.Ina
collectionofmoleculesatconstanttemperature,however,thetotalenergy
remainsconstant

Deviation of real-gas behavior from ideal gas law

7.

8.

a. qualitative
The gas tends to be less ideal at high pressure and low temperature
The gas tends to be more ideal at low pressure and high temperature
Lower molecular weight or the smaller the size of its molecules, the
more ideal its behavior
Monatomic gases display ideal behavior more readily than do diatomic
gases
The weaker the intermolecular forces present, the more likely the gas
will behave ideally
b. quantitative (van der Waals equation)
(P+an2/V2)(Vnb)=nRT,whereaandbcanbelookedupfrom
tables.
Preal<Pideal:becauserealgasesdoexperienceintermolecularforces,
reducingcollisionwiththewallsofthecontainer
Vreal<Videal:realgasesdohavevolumethatreducestheeffective
volumeofthecontainer
Partial pressure, mole fraction
P=Pa+Pb+Pc
The partial pressure of a gas is equal to its mole fraction times the total
pressure
Daltons law relating partial pressure to composition
The total pressure is the sum of the partial pressures of all the constituent
gases.
9.Grahams law of Effusion
Definition of Effusion: The escape of a gas molecule through a very tiny
hole
Rate of effusionof Gas A
molar mass of Gas B

=
Rate of effusionof Gas b
molar mass of Gas A
rms vA
mB

=
rms vB
mA

B. Intermolecular Forces (Van der Waals forces)


ion-dipole: polar molecules are attracted to ions
dipole-dipole: attractions between the positive end of one polar molecule and the
negative end of another polar molecule. Hydrogen bonding is the strongest dipoledipole force. Hydrogen bond only occurs between H attached to an N, O or F
atom. They have higher boiling point compared to the atom in their group.
dipole-induced dipole: A permanent dipole in one molecule may induce a dipole
in a neighboring non-polar molecule
instantaneous dipole induced dipole (London dispersion fore): an instantaneous
dipole in a nonpolar molecule may induce a dipole in a neighboring nonpolar
molecule
C. Phase Equilibria

1.

Phase changes, phase diagrams


A key property of a physical change is that no intramolecular bonds are made or
broken, it only affects intermolecular forces between molecules
The average KE of the molecules affects its state or phase
Solid to liquid=fusion (melting), liquid to gas = vaporization (boiling), solid to
gas=sublimation
Gas to liquid = condensation, liquid to solid= crystallization (freezing), gas to solid
= deposition
Heats of phase change: q=n (mol) x H (J/mol)
Cal= the amount of heat required to raise the temperature of 1g of water by 1 oC.
1cal =4.2J
When a substance absorbs or releases heat, one of two thins can happen: either its
temperature changes or it will undergo a phase change but not both at the same
time.
q (heat)=m (mass)c (specific heat, an intrinsic property of the substance (also
depends on phase), it tells us how resistant it is to changing its temperature, the
higher it is, the smaller the change in temperature)T (change in temperature)
[q=mcT]
heat capacity, C=mc
phase transition diagram
o a substances heat of vaporization is always greater than its heat of fusion
o the slope of the non-flat line is 1/C
o At a fixed pressure, as long as two phases co-exist, the temperature does not
change

Phase diagram shows how its phases are determined by temperature and pressure
Normal melting point: draw a horizontal line at 1 atm pressure level, the
temperature at the point where this line crosses the solid-liquid boundary
Normal boiling point: draw a horizontal line at 1 atm pressure level, the
temperature at the point where this line crosses the liquid-gas boundary
Triple point: the temperature and pressure at which all three phases exist
simultaneously in equilibrium
Critical point: end of the liquid-gas boundary. Beyond this point, the substance
display properties of both a liquid and a gas. This substance is called supercritical
fluid, and no amount of increased pressure can force the substance back into its
liquid phase
The phase diagram for water is special: the solid-liquid boundary line is slightly
negatively sloped. At fix temp, when increasing pressure, water will favor the

liquid phase. Others, for example, CO2 will never turn to liquid with increased
pressure.

2.

3.

4.

5.
6.

Freezing point, melting point, boiling point, condensation point


Boiling point of a liquid is defined as the temperature at which the vapor
pressure of the solution is equal to the atmosphere pressure over the
solution.
Molality
moles of solute
molality=
This does not change with temperature or
kg of solvent
pressure
Colligative properties
Definition: properties of this sort, whose values depend only on the concentration
of solute particles in solution and not on what the solute is are called colligative
properties.
c. vapor pressure lowering (Raoults law)
definition: vapor pressure is the pressure exerted by the gaseous phase of a
liquid that evaporated from the exposed surface of the liquid
easily vaporized liquidshigh vapor pressurevolatile
Raoults law: Pa=Xa(mole fraction)*Pa(pure)
Ptot=Pa+Pb
d. boiling point elevation (Tb = iKbm)
ivant Hoff factor: tells us how many ions one unit of a substance
will produce in a solution
m is molality
for a given solution, the more solute particles, the greater the boiling
point elevation
e. freezing point depression (Tf = -iKfm)
f. osmotic pressure
Definition of osmosis: describes the net movement of water from
region of low solute concentration to region of high solute
concentration
Definition of osmotic pressure: the pressure it would take to stop
osmosis from occurring
=MiRT, where M is molarity of the solution, T is in K
Colloids
Henrys law

SOLUTION CHEMISTRY
A. Ions in Solution
1. Anion, cation (common names, formulas, and charges for familiar ions; e.g., NH +,
ammonium; PO 3+, phosphate; SO42-, sulfate)
Ionic substance are strong electrolytes
Not completed dissolved (remain ion-paired to some extent) are weak electrolytes
Covalent compounds are nonelectrolytes
Salt Solubility rules:
o All group 1 and NH + salts are soluble
o All NO3-, ClO4-, and C2H3O2- salts are soluble
o All Ag+, Pb2+/Pb3+, and Hg22+/Hg2+ slats are insoluble, except for their salts
mentioned above.
o Cl2, Br2, and I2 are soluble
o Carbonates (CO3 2-), phosphates (PO4 3-), sulfides oxides (SO4 2-) and
hydroxides (OH-) are insoluble (sulfides of group 2 cations and hydroxides of
Ca2+,Sr2+, and Ba2+ are slightly soluble)
o Sulfates are soluble except for those of calcium, strontium and barium
Phase solubility rules
o Solubility of solid in liquid increase with temperature
o Solubility of gas in liquid decrease with temperature
o Solubility of gas in liquid increase with pressure
2. Hydration, the hydronium ion
4

B. Solubility: like dissolves like


Solutes will dissolve best in solvents where the intermolecular forces being broken in the
solute are being replaced by equal or stronger intermolecular forces between the solvent
and the solute
1. Units of concentration (e.g.,molarity)
moles of solute
molarity=

Liters of solution
moles of solute
molality=

This does not change with temperature or


kg of solvent
pressure
total

moles of substance S
mole fractionof S=
moles of solution

2. Solubility product constant, the equilibrium expression


3. Common-ion effect, its use in laboratory separations
4. Complex ion formation
5. Complex ions and solubility
6. Solubility and pH
Definition: solubility refers to the amount of solute that will saturate a particular
solvent
Solubility of solid in liquid mostly increases with T, solubility of gas in liquid mostly
decrease with T
Solution can involve any of the 3 phases of matter