POINTERS TO REVIEW:

Kinetic Molecular Theory

 all solids have fixed shapes and volumes

 all liquids have fixed volumes but has no definite shape
 gases assume both the shapes and volumes of their containers

Intermolecular Forces of Attraction (sample of molecules with the following IMFA)

 London Dispersion
 Dipole-Dipole
 Hydrogen bonding
 Ion-Dipole
Properties of Liquid (Viscosity, Density, Molar Heat of vaporization, surface tension, capillary
action, etc.)
Phase Diagram (Critical Point, Triple point, Interpreting diagram)
Heating and Cooling Curve
Concentration of Solution

 Percent by mass and volume

 Molarity

 Molality

 Ppm
  Mole Fraction

Colligative Properties

 Vapor Pressure Lowering

P1 = X1P1 °
 Boiling point elevation
The boiling point elevation is the difference between the boiling point of a solution and the
boiling point of a pure solvent.
Note: The boiling point of a solution is always higher than that of the pure solvent.
ΔTb = Tb -Tb0
Where:
Tb = boiling point of a solution
Tb0 = boiling point of a pure solvent

ΔTb = i Kb m

Where:
Tb = boiling point elevation
Kb = molal boiling point elevation constant of pure solvent
m = molality
i = van’t Hoff factor
 Sample Problem 1: What is the new boiling point of a solution prepared by adding 96.0 g of
sodium acetate to 0.383 kg of water? The boiling point constant for water is 0.52 °C/m.

Given:
i (NaCl) = 2
mass of solute = 96 g
kg of solvent = 0.383 kg
Kb = 0.52 °C/m
Tb = ?
m=?

Solution:
a.) m = ?
m = moles of solute/kg of solvent
moles of solute = 96 g x 1 mol/58.443 g = 1.64 moles
m = 1.64 moles / 0.383 kg
m = 4.28 molal
b.) ΔTb = i Kb m
ΔTb = (2) (0.52 °C kg/mol) (4.28884 mol/kg)
ΔTb = 4.46 °C

Thus, the new boiling point is 104.46 °C. (100 °C + 4.46 °C)
  Freezing point depression

Solutions freeze at lower temperature than the pure solvent.

ΔTf = Kf m
Sample Problem 1. What are the boiling and freezing points of a solution containing 478 g
of ethylene glycol (EG) in 3202 g of water? (MMEG = 62.07g/mol; Kb = 2.26°C/m; Kf =
1.86°C/m)
Answer: 105.4°C ; -4.48°C

 Osmotic Pressure
The osmotic pressure (π) is directly proportional to the number of solute particles in each
volume of the solution. That is, the molarity (M) of the solution and the proportionality
constant R, times the absolute temperature (T). Thus,

R = 0.0821 L-atm/mol-K
T = Kelvin unit (Celsius + 273)

760 mm Hg = 1 atm
Molarity = moles of solute/ Volume of sol’n in Liters

MW=mRT/πV

Sample Problem 1. A solution is prepared by dissolving 35.0 g of hemoglobin (Hb) in

enough water to make up 1L in volume. The osmotic pressure of the solution is found to be
10.0 mmHg at 25°C.
A. What is the molarity concentration of the solution?

M = π / RT
M = 0.01316 atm / 0.0821 L-atm/mol-K (298 K)
M = 0.000538 M

B. What is the molar mass of hemoglobin?

MW=mRT/πV
MW = 35 g (0.0821 L-atm/mol-K) (298 K) / 0.01316 atm (1L)
MW = 65, 068.61 g/mol

Thermodynamics
First Law of Thermodynamics:

 In a closed system, the difference between the heat added to the system and the work done by the
system is equal to the change in the internal energy.
 "energy cannot be created nor destroyed
 It can be transformed into another form, but the total amount of energy remains the same.
ΔEsys = –ΔEsurr
The energy of the system (ΔEsys)
The energy of its surroundings (ΔEsurr)
Note that: The negative sign indicates the flow of energy. As the system releases energy, the
surroundings absorb it. Whatever amount of energy that is lost by the surroundings must be
gained by the system.

The First Law of Thermodynamics states that in the process, the change in energy of a system is equal to
the heat absorbed (q) by the system and the work (w) done on it.
ΔEsys = q + w
or
ΔU = q + w

Where:
ΔEsys or ΔU is the total change in internal energy of a system
q is the heat exchanged between a system and its surroundings
w is the work done by or on the system.

Sample Problem
A gas in a system has constant pressure. The surroundings around the system lose 62 J of heat and
do 474 J of work onto the system. What is the internal energy of the system?
ΔEsys = q + w
ΔEsys = (62J) + (474J)
ΔEsys = 536J (Endothermic)

Enthalpy of a Chemical Reaction

The enthalpy of a system is defined as the sum of its internal energy ΔE plus the product of its pressure P
and volume V:
H= ΔE + PV
Because internal energy, pressure, and volume are all state functions, enthalpy is also a state function. So,
we can define a change in enthalpy (ΔH) accordingly by the equation:
ΔH = Hfinal −Hinitial
The enthalpy change of a reaction is the difference between the energy released by bond formation
and the energy consumed by bond cleavage during a chemical reaction.
If a chemical change occurs at constant pressure (i.e., for a given P, ΔP = 0), the change in enthalpy (ΔH)
is :
ΔH = qp
Where:
ΔH = change in enthalpy
qp = heat at constant pressure
If heat flows from a system to its surroundings, the enthalpy of the system decreases, so ΔHrxn is
negative.
Conversely, if heat flows from the surroundings to a system, the enthalpy of the system increases, so
ΔHrxn is positive. Thus:
ΔHrxn <0 for an exothermic reaction, and
ΔHrxn >0 for an endothermic reaction.

Example:
 In this reaction,
-The change in enthalpy results from heat release.
-The enthalpies of the reactants are greater than the products.
-There is a decrease in enthalpy.

To calculate for the standard molar enthalpy, consider the hypothetical equation,

aA + bB → cC + dD
Enthalpy of formation of product:
ΣΔHf (products) = cΔHf(C) + ΔHf(D)
Enthalpy of formation of reactant:
Σ ΔHf (reactants) = aΔHf(A) + bΔHf(B)
Then the standard molar enthalpy of the hypothetical reaction is calculated as,
Σ ΔHf (rxn) = ΔHf (products) – ΔHf (reactants)
Example:
What would be the change in the enthalpy for the following reaction?
C3H8(g) + 5O2(g)    3CO2(g)+ 4H2O(l)
ΔHf C3H8 = -103.8 kJ/mol
ΔHf O2 = 0
ΔHf CO2 = – 393.5 kJ/mol
ΔHfH2O = – 285.83 kJ/mol
Σ ΔHf (rxn) = ΔHf (products) – ΔHf (reactants)
ΔHf (products) = 3(– 393.5 kJ/mol) + 4(– 285.83 kJ/mol)
ΔHf (products) = - 1180.5 + (-1143.32)
ΔHf (products) = -2323.82 kJ/mol
ΔHf (reactants) = 1(-103.8 kJ/mol) + 5(0 kJ/mol)
ΔHf (reactants) = -103.8 kJ/mol
Σ ΔHf (rxn) = ΔHf (products) – ΔHf (reactants)
Σ ΔHf (rxn) = -2147.7 kJ/mol – (-103.8 kJ/mol)
Σ ΔHf (rxn) = -2220.02 kJ/mol

Second Law of Thermodynamics

 Heat never flows spontaneously from a colder body to a hotter body.
 Any process that involves heat transfer from a hotter object to a colder object is not
reversible.
 Entropy is a measure of a system’s disorder.
 Heat flows from objects of high temperature to objects at low temperature because this
process increases the disorder of the system.
 The entropy of the universe never decreases.

ΔSuniv = ΔSsys + ΔSsurr

 A positive ∆Suniv indicates that the process is spontaneous and nonspontaneous if the said
quantity is negative. With this condition, we could predict the spontaneity of unfamiliar
processes occurring around us.

Standard Entropy Of The Reaction ΔSsys

ΔSOrxn = [ Σ xSO (product) - Σ zSO (reactant) ]
Entropy of the surrounding (ΔSsurr)
(ΔSsurr) = -ΔHOrxn / T
Standard Enthalpy Of The Reaction
ΔHOrxn = [ Σ xHO (product) - Σ zHO (reactant) ]
TOTAL ENTROPY CHANGE
ΔSuniv = ΔSsys + ΔSsurr

Third Law of Thermodynamics

 At absolute zero Kelvin, the entropy of a perfect crystal is considered to be zero.

Chemical Reaction
A. Activation Energy - The energy required to break the bonds of reactant molecules. (Note
that A decreased in the activation energy in a chemical reaction will increase the rate of the
reaction)
B. Catalyst is usually a substance that, when added to reacting mixture, increases the rate of the
reaction without being consumed in the process. (Note that catalysts lower the activation
energy and provide a new path for the reaction)
heterogenous catalyst - in different phase from the reactants
Five (5) factors Affecting the Rate of Chemical Reaction:
1. Surface Area of Reactants / Particle Size
Example: If you burn it as one big block or log of wood, it will take a few hours before the whole
block gets totally burned. But if you use wood shavings, chips, or sawdust, it would take only a
few minutes to burn it all up.
A block of wood has 6 sides. Each of the surfaces comes in contact with oxygen in the air. If you
make the particle size of the wood smaller, it increases the number of surface areas exposed. This
consequently results in an increase in the contact area between the wood and oxygen. Thus the
rate of burning increases.
Example: Smaller pieces of calcium carbonate will react faster with dilute hydrochloric acid to
form the carbon dioxide gas needed by plants than large pieces of calcium carbonate.

2. Concentration of Reactants
The Collision Theory suggests that reacting particles must bump properly with each other with a
sufficient amount of energy so that a chemical reaction can occur. An increase in the
concentration of the reactants means that there will be more particles colliding with each other in
a given amount of time, thus increasing the possibilities that a reaction takes place.
3. Nature or Reactivity of Reactants
The reaction rate varies with the nature and reactivity of the substances involved. Generally, fast
reactions include acid reactions, the formation of salts, and ion exchange. Reactions tend to be
slow when covalent bond formation takes place between the molecules and when large molecules
are formed.

4. Temperature
 Temperature is directly proportional to kinetic energy. This means that at higher temperatures,
molecules are more in motion. The frequent the motion will be, the greater is the chance for
colliding molecules to result in a faster reaction.
Example: Gas particles interact much faster in random motion due to collision of particles when
temperature is increased.
5. Presence of a Catalyst
A catalyst is usually a substance that, when added to reacting mixture, increases the rate of the
reaction without being consumed in the process and can be recovered after the reaction is
completed. Catalysts are the opposite of inhibitors, which slow down reactions.