GENERAL CHEMISTRY 2

Physical Properties
of Solutions
Electrolytes and Physical Properties of Solutions

When studying the colligative properties of solutions, we consider

classification of the solute as an electrolyte or a nonelectrolyte.
Electrolytes are substances that dissociate or form ions when dissolved
in water. They allow water to conduct electricity. Electrolytes are
further classified into strong and weak electrolytes. Strong electrolytes
are compounds that dissociate or ionize completely in water. These
include most of the ionic compounds or salts forming only ions in
solution.
 On the other hand, weak electrolytes are compounds that
dissociate or ionized slightly in water. Therefore, both ions and
molecules exist in solutions of weak electrolytes. Nonelectrolytes are
substances that do not dissociate or ionize in water. These are
molecular compounds and do not allow water to conduct electricity.
Typically, electrolyte solutions contain more solute particles than
nonelectrolyte solutions of the same concentration. Therefore, the
same concentration of an electrolyte in a solvent has a greater effect in
the colligative properties than that of a nonelectrolyte.
 There are many modern laboratory techniques and procedures
used to determine the concentration of certain substances on different
samples. The most common and basic procedure for concentration
determination is through volumetric analysis, also known as titration.
Titration is the process of determining the concentration of a substance
in a solution by reacting it with a solution of a different substance with
known concentration.
Common titration involves small additions of a solution with
known concentration of some substance (titrant) to a solution
containing the substance whose concentration is to be measured
(analyte). The titrant and analyte undergo a chemical reaction of
known stoichiometry. The volume of titrant solution required for
complete reaction with the analyte solution is the equivalence point
and it allows calculation of the analyte concentration.
 GENERAL CHEMISTRY 2

THERMOCHEMISTRY
The First Law of Thermodynamics
The energy relationships and changes involved in chemical reactions are as
important as mass relationships when studying matter. Most chemical reactions
occur with the absorption or release of energy in the form of heat. Heat is the
transfer of thermal energy between substances or matter at different
temperatures. Temperature is distinct from heat; it is defined as the
manifestation of thermal energy while heat is the process of transferring that
energy. On the other hand, thermal energy is the energy involved in the
random motions of atoms and molecules. This energy or heat changes involved
in chemical reactions are studied by thermochemistry. Thermochemistry is
involved with quantities of heat and work, typically in Joules (J) which is the SI
unit of energy.
 Before studying the energy changes in chemical reactions, the
matter involved in the reactions must be identified first. The system is
the part of the universe that is studied and the rest of the universe that
is uninvolved with the reaction is considered as the surroundings.
There are types of systems to be considered: (1) open systems can
exchange matter and energy with surroundings, (2) closed systems only
allow exchange of energy but not matter, and (3) isolated systems does
not allow any transfer for both matter and energy. In addition to the
systems, we must also describe the reactions based on the type of
energy transfers involved. When chemical reactions release energy to
the surroundings, the process is known as an exothermic process.
While the chemical reactions that absorb energy from the surroundings
undergo endothermic process.
The first law of thermodynamics states that energy cannot be
created nor destroyed but can be converted from one form to
another. The exact energy (internal energy) of a system cannot be
determined but the changes in the energy states can be determined
and is represented in chemical reactions by,
 GENERAL CHEMISTRY 2

ENTHALPY
Most chemical reactions that occur in the environment, in living
organisms and in the laboratory are under conditions of constant
pressure (atmospheric pressure). The heat change in the system and
surroundings at constant pressure is known as the change in enthalpy.
Like the internal energy, exact values of enthalpy cannot be
determined and instead the enthalpy change between the products
and reactants is calculated and is expressed as,
 A positive ∆� indicates that the system absorbed energy from the
surroundings and undergone an endothermic process while a negative ∆�
indicates that the system released energy to the surroundings and
undergone an exothermic process.
In chemical reactions, the change in enthalpy (∆� � � � ) is
determined by the difference between the sum of all the product
enthalpies and the sum of all the reactant enthalpies, represented by the
equation,
 For chemical reactions, the balanced chemical equation can
represent the enthalpic and the mass relationships of the products and
reactants and is called the thermochemical equation. When writing
and interpreting thermochemical equations, we must remember the
following:
1. The physical states of the reactants and products must always be
specified because the enthalpy changes depend on it.
2. If the thermochemical equation is multiplied by a factor n, then
enthalpy is multiplied by the same factor since enthalpy is an extensive
property.
3. When we reverse an equation, we change the roles of the reactants
and the products. The magnitude of the enthalpy remains the same but
the sig
 GENERAL CHEMISTRY 2

CHEMICAL KINETICS
 Chemical reactions occur in different rates. There some reactions that
occur in mere seconds, some takes minutes, hours, days and some reactions
take millions of years to complete. The measure of how fast reactions occur is
known as the rate of reaction or reaction rates. The branch of chemistry
concerned with the speeds or rates at which chemical reactions occur is
chemical kinetics. Chemical kinetics defines reaction rate as the change in the
concentration of the reactant or product with respect to time. The rates of
reactions are studied for theoretical and practical reasons. The rates of
reactions are studied in order to understand why certain reactions occur in a
fraction of seconds while other can take thousands to millions of years to
complete. The rates of reactions are also studied for practical applications such
as drug design, pollution control, food processing and materials synthesis.
Chemical reactions are generally characterized by the following equation,

� � � � � � � � � →� � � � � � � �
 During the chemical reaction, the reactants are being consumed to
form the products. As time passes, the amount of reactants is decreasing
while the amount of products is increasing. This observable change in
concentration over time is the basis of determining the rates of chemical
reaction. The rate is represented by,
 In order to understand these differences in reactions rates, we
must examine the different factors that affects rates of chemical
reactions:
• Nature of the Reactants
• Concentration of Reactants
• Temperature of Reaction System
• Presence of Catalyst
Nature of the Reactants
In order for chemical reactions to occur, the reactants must interact with one
another. One factor that affects this interaction is chemical reactivity. Some substances
readily react to other substances while others are naturally stable and unreactive like the
noble gases. These substances with low reactivity usually require certain conditions
forchemical reaction to occur. The rate of reaction is also influenced by the physical state of
the reactants. In terms of physical states, reactions can be classified as homogenous or
heterogenous. Homogenous reactions are reactions in which of all the reactant are in the
same phase, either all liquids or all gases. On the other hand, heterogenous reactions are
reactions that involve reactant in different phases. For this type of reactions, the chemical
reaction is limited to the area of contact between the reactants. This limitation is overcome
by increasing the surface area, in reactions involving solids.
Concentration of Reactants
Rates of chemical reactions tend to increase when the
concentrations of one or more reactants is increased. A greater
concentration of reactants translates into greater number of
interactions between reactants resulting to faster formation of
products.
Temperature of Reaction System
As discussed in thermochemistry, some reactions need to absorb
energy in order to proceed. Exposing certain reaction systems to higher
temperatures increase the reaction rate since it provides the energy
needed by the reaction itself. In addition, molecules move faster at
higher temperatures. This fast movement results into a greater chance
of interaction between reactant molecules forming the products.
Presence of Catalyst
A catalyst are substances that are introduced to a reaction to
increase reaction rates without them being consumed. They react with
the reactants and are regenerated once the products are produced.
Catalysts change the conditions of the reaction system to allow the
reaction to proceed in rates that are otherwise impossible.
 Rate Law
When the concept of reaction rate is introduced, the chemical
reaction only included a single reactant and product. However, reactions
may involve more than one set of reactants and products. In addition, most
reactions have different stoichiometric coefficients for the reactants and
products. To account for the stoichiometric relationships in chemical
reaction, we must adjust our description of reaction rate. For the general
reaction,

the rate of the reaction is represented by,

where a, b, c, and d are the stoichiometric coefficients, ∆[� ], ∆[� ], ∆[� ], and ∆[� ] are
changes in concentration of the reactants and products, ∆� is the change in time. To study
the relationship between the concentration and rate, experimental data are gathered using
the initial concentrations and initial rates of certain reactions. Using these experimental
data, we can summarize the relationship between concentration and rate in terms of the
reactant. The equation used to show how rate is dependent on the reactant concentration
is the rate law. For the general reaction,
� � +� � →� � +� �
the rate law is generally expressed as,
� � � � = � [� ]� [� ]�
where [A] and [B] are the concentrations of the reactants, m and n are numbers that are
not equal to the stoichiometric coefficients of the reactants. The importance of these
numbers will be introduced later on. The constant k is the rate constant, which a quantity
that is temperature dependent.
 GENERAL CHEMISTRY 2

Reaction Orders
As mentioned for the general reaction above, the general form of the
rate law is,
� � � � = � [� ]� [� ]�
In this equation, m and n are reaction orders. Reaction orders
indicate the effect of the concentration of the specific reactant on the
rate of the reaction. The values for reactions orders are typically 0, 1, or
2 but may also have fractional or negative values. These orders of
reactions are determined experimentally.

For example, consider the following chemical reaction and rate law,
H2(g) + I2(g) → 2HI(g); rate = k[H2][I2]
Both H2 and I2 have a rate order of 1. This means that increasing the
concentration of H2 by a certain factor also increases the rate of the
reaction by the same factor. The rate is described as first-order in H2.
The same applies when the concentration of I2 is increased.
Consequently, the rate is also first-order in I2. However, these two
reactants affect the rate of reaction simultaneously. To account for this,
the overall order of the reaction is determined by getting the sum of
all reaction orders with respect to the reactant represented in the rate
law. Therefore, for this particular reaction the overall order of reaction
is 2 and the reaction is second-order overall.
First Order Reactions
First-order reactions are reactions whose rates are dependent on a
single reactant concentration. The rate for reactant A is,

� � � � = − ∆[� ] ∆� = k[A]

This form of rate law which expresses the relationship of concentration

and rate is the differential rate law. Using integration, the rate law is
transformed to an equation that relates the initial concentration to
concentration at any other time, t. The first-order integrated rate law is
expressed as,
ln[� ]� = −� � + ln[� ]�
Second Order Reactions
Second-order reactions are reactions whose rates are dependent on either a single
reactant concentration raised to the second power or two reactant concentrations both
raised to the first power. To simplify the rate law, for second-order reactions we will only
consider the rates dependent on a single reactant concentration raised to the second
power. The rate for reactant A is,
� � � � = − ∆[� ] ∆� = � [� ]2
The integrated rate law for second-order reactions is expressed as,
1[� ]� = � � + 1[� ]�
where 1/[A]o is the reciprocal of the initial concentration, 1/[A]t is the reciprocal of the
concentration at time t, and k is the rate constant. Similar to the integrated rate law for first
order, the equation follows the form of a linear equation. A second order reaction
produces a linear graph when 1/[A]t is plotted against t.
Zero Order Reaction
Zero order reactions are reactions whose rates are independent of the
reactant concentration. The rate for reactant A is,
� � � � = − ∆[� ] ∆� = �
The integrated rate law for zero-order reactions is expressed as,
[A]t = - kt + [A]o
where [A]o is the initial concentration, 1/[A]t is the concentration at time t,
and k is the rate constant. Similar to the integrated rate law for first and
second order, the equation follows the form of a linear equation. A zero-
order reaction produces a linear graph when [A]t is plotted against t.
Half-Life
Half-life, denoted as t1/2, is time needed for the concentration of reactant
to reach half of its initial concentration. Like the rate constant, the half-life
is also used to describe how fast a reaction is. Reactions with a short half-
life are considered as fast reactions. The half-life for a first-order reaction
is derived using the integrated rate law and is expressed as,
� 1⁄2 = 0.693�
Based on the formula, first-order half-life is independent of the initial
concentration.
Thus, the first-order half-life remains constant throughout the reaction.
 GENERAL CHEMISTRY 2

COLLISION THEORY
The collision theory was proposed to explain why reactions occur.
According to collision theory, two conditions must be satisfied for a
chemical reaction to occur:
1. the particles of the reactants must collide with one another at the
proper orientation; and
2. colliding particles must have sufficient energy
 T h e c o l l i s i o n t h e o r u sta t e s t h a t re a c t i n g
substances must come into contact (collide) with
enough activation enrgy, and in the correct orientation
(dacing the corret way). so that their electron shells can
rearrange to form the products of the reaction.
Therefore, any factor which changes the frequency or
energy of the collisions will change the rate of the
reaction.
Try to analyze the illustrations given below:

As shown in the picture, the diatomic Nitrogen gas

reacts with diatomic Oxygen gas to yield two molecules
of Nitrogen ocide. the shared atoms form a bond by
completing the valence shells of both atoms.
 A chemical reaction does not take place if the collision
between molecules does nit have sufficient energy to break the
bonds in the reactants and if the molecules are not properly
oriented.
In order to form products, the reactants must have an effective collision.
An effective collision occurs when the reactant particles collide at the
proper orientation and both have sufficient energy to support the
collision. Therefore, some collisions occur without the formation of
products. We can assume from the collision theory that the greater the
number of collisions, the greater the chances of an effective collision,
and the greater the amount of products formed per unit of time. Thus,
greater number of collisions result to faster reaction rates.
Catalysts and Speed of Reactions
• Catalysts are substances that influence a chemical reaction without
being consumed in the reaction.
• They can be used several times and can be recovered since it does not
change or participate in the formation of the product of a chemical
reaction.
Catalysts and Speed of Reactions
• In a chemical reaction, bond breaking in the reactants first takes place
before new bonds can form as the reactants are converted into
products.
• This process of bond breaking requires sufficient energy for the
reaction to occur.
• It is called as the activation energy.
• However, if this energy barrier is very high, only a few reacting
molecules will be converted into products, making the reaction a slow
process.
Catalysts and Speed of Reactions
• A method that can be used to increase reaction rate without
increasing the temperature is to add a catalyst.
• Catalysts provide an alternative reaction pathway for the process of
bond breaking, resulting in lower activation energy.
• Lower activation energy leads to higher rates of chemical reaction.
• This means that the energy barrier has a lower energy requirement,
allowing more reacting molecules to be converted into products.
Thereby, speeding up the reaction.
Homogeneous and Heterogeneous Catalysis
• Homogeneous catalysts work by forming an intermediate
compound with the reactants. They are usually in the form of
a gas or in a contained single liquid phase.
• Heterogeneous catalysts are usually in the form of a solid
with reactants that are liquids or gases. In a heterogeneous
reaction, the catalyst has a different phase with the reactants.
 Homogeneous and Heterogeneous Catalysis
• Catalytic converters are used
to change poisonous
molecules such as nitrogen
oxides and carbon
monoxides into harmless
molecules, such as nitrogen
and carbon dioxide.
• Metals such as platinum and
palladium are usually used
for these reactions.
 Autocatalysis
• Autocatalysis is a process where
the chemical reaction is
catalyzed by one of its products.
• Shown below is a graph for a
general autocatalytic reaction.
• It starts slowly then speeds up
and eventually slows down until
the reaction stops.
 A catalyst is a substance that is introduced to a reaction system
that alters the pathway in which a reaction occurs without itself being
consumed. Catalysts have varying effects depending on their
classification.
A positive catalyst lowers the activation energy by proceeding on
an alternative path. This results to a faster reaction rates. On the other
hand, a negative catalyst increases the activation energy of a reaction,
thus, slowing the reaction rate down. Inhibitory drugs are examples of
negative catalysts. Some products of a reaction acts as a catalyst to the
same reaction allowing it to proceed faster. These products are
autocatalysts. Induced catalysts influence the rate of other reactions,
which do not occur under
normal conditions.