Thermodynamics be measured and quantified, it is similar in saying that

change in the (E) energy of the system must result in a

Laboratory Solution Preparation change in the energy of the surroundings. If the heat
Titration is a process by which we determine the flows into a system or the surroundings do work on it
volume of a standard solution which then reacts to a (on the system), internal energy increases and the
sample weight or volume of substance. Determining values of q and w are positive. On the other hand,
the concentration of an acid or base is known as acid- heat flow out of the system or work done by the
base titration. This is done by measuring the amount system (on the surroundings), the internal energy
of titrant, solution with known concentration reacting decreases because q and w are both negative.
completely with a solution of unknown concentration,
the analyte. At the end of the titration known as the
equivalence point happens where it is determined by
the use of an indicator which changes color at the
desired point. Sample Problem: Calculate ΔE if 100 kJ of heat energy
is absorbed by the system and 30 kJ of work is done
The First Law of Thermodynamics on the surroundings.

The first law of thermodynamics states that energy Solution: The addition of heat increases the energy of
can neither be created nor destroyed; it can only be the system by 100 kJ but doing work decreases the
transformed from one form to another. This is also energy of the system by 30 kJ.
known as the Law of Conservation of Energy. For
example, the flow of electron produces light in a bulb, Given: q= +100 kJ (absorbed by the system, + )
it appears (light) energy is produced in a bulb, w = -30 kJ (done by the system: sign is - )
however, it is through the conversion of electrical Required: ΔE (internal energy)
energy to light. Strategy:ΔE =q+w
= 100 kJ + (-30 kJ)
Internal energy is a state function, meaning it does = 70 kJ
not depend on the path of the process. The value is
the same regardless of the pathway and depends only Enthalpy of Chemical Reactions
on the initial and final states of the system.
ΔE = Efinal - Einitial The term enthalpy originates from the Greek word
Change in Internal Energy is used in expressing the enthalpein that means “to warm”. Enthalpy is the
first law of thermodynamics, wherein change in the energy transferred under constant pressure,
internal energy (∆E) is the sum of the heat (q) that represented by the symbol H. Also, it is known as the
flows across its boundaries and the work (w) done on heat content. Just like (E) internal energy, H is also a
the system by the surroundings. state function which is defined by the change from
the final to the initial state.
ΔH = Hfinal -Hinitial
Enthalpy change, is called heat of reaction which is
based on the net energy change from the breaking
and making of bonds. It represents heat absorbed or
released when the reactants are converted intro
products, at a constant pressure.
Mathematically it is expressed as: ΔH = Hproducts -Hreactants
ΔE = q + w ΔH = q (at a constant pressure)
The enthalpy of chemical reactions is composed of the
This law says that there are two kinds of processes, reactants and products and their corresponding bond
heat and work, that can lead to a change in the energies, the amount of energy to break the bonds or
internal energy of a system. Since both heat and work released in forming the bonds. The sign of ΔH
can be measured and quantified, this is the same as determines the direction of heat transfer. A positive
saying that any change in the energy of a system must ΔH means an absorption of heat from the
result in a corresponding change in the energy of the surroundings, also known as endothermic reaction. A
surroundings outside the system. In other words, negative value of ΔH indicates an exothermic reaction,
energy cannot be created or destroyed. a heat releasing process.
As the equation says, we have two kinds of processes,
heat and work, that defines the change in the internal The enthalpy relation between reactants and products
energy of the system. Since both heat and work can is usually shown in a thermochemical equation. This is
a balanced equation wherein the value of ΔH with the
appropriate sign, is usually written at the right side.
Since both the physical state and amount of
substances involved in the process affects the
magnitude of ΔH, a thermochemical equation also
shows whether the substance is a solid, liquid gas or
aqueous, while the coefficients represent the number
of moles of reactants and products. Furthermore,
reversing the reaction would lead to a ΔH value that
has the same magnitude but opposite in sign.

Standard Enthalpy of Reaction: Hess’ Law

There are reactions wherein the direct measurement

of enthalpy change is not possible. There are also
compounds that cannot be formed from their
elements because the reaction is either very slow or
there are side reactions that result in products other
than what is desired. Hess’ Law provides an indirect
method of determining heat of reaction using a basis
related chemical reactions with predetermined values
of ΔHf°. Hess's Law of Constant Heat Summation (or
just Hess's Law) states that regardless of the multiple
stages or steps of a reaction, the total enthalpy
change for the reaction is the sum of all changes. This
law is a manifestation that enthalpy is a state Reaction Rates, Factors Affecting Reaction Rates, and
function. Collision Theory

Hess’ Law states that... The Rate of a Chemical Reaction

1. Reverse reaction – reverse sign (If we reverse the The study of the rate of a chemical reaction is called
reaction, we have to reverse the sign in that change in chemical kinetics.
enthalpy)
2. Enthalpy of the reaction is equal to the sum of the What is the “rate" of a reaction?
parts. The rate of a reaction is the speed of the reaction. It is
not “how much” of a product is made, but instead
“how quickly” a reaction takes place.
Reaction Rate = Reactants → Products
Time
Reaction Rate is defined as the rate at which reactants
change into products over time.
How can we measure the rate?
➢ The rate of a chemical reaction can be studied by
measuring either:
• How quickly a reactant is used up, or
• How quickly a product is formed.
Consider the reaction:
REACTANTS PRODUCTS
zinc + hydrochloric acid —> zinc chloride + hydrogen
 The rate of a reaction is the speed of the reaction. It e. Reactions involving the breaking of fewer bonds per
is not “how much” of a product is made, but instead reactant proceed faster than those involving the
“how quickly” a reaction takes place. breaking of a larger number of bonds per reactant.
➢ Kerosene burns more slowly than methane
There are two possible ways of measuring the rate: because there are more bonds to be broken per
1) measure how quickly one of the products (e.g. the molecule of kerosene than there are per molecule of
hydrogen) is made methane. Kerosene is a larger molecule.
2) measure how quickly one of the reactants (e.g. the Fast CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
zinc) disappears methane
Slow C13H28(g) + 20 O2(g) → 13 CO2(g) + 14 H2O(g)
Factors That Affect Rate of a Chemical Reaction kerosene
Almost any reaction rate can be changed by varying
the conditions under which the reaction takes place 2. Concentration of reactants
1. Nature of the reactants • Concentration refers to how much solute is
• Substances vary in their chemical reactivity. It is a dissolved in a solution.
major factor that determines the rate of a reaction. • When the concentration of all the reactants
• Chemists believe that the type, strength and increases, more molecules orions interact to form
number of chemical bonds or attractions between new compounds, and the rate of reaction increases.
atoms determines with what speed the particles have • When the concentration of a reactant decreases,
to collide with each, to create an effective reaction. there are fewer of that molecule or ion present, and
a. Reactions involving simple ions are most often the rate of reaction decreases.
instantaneous. This is due to the fact that the positive
and negative charges attract each other and no bonds
have to be broken in creating the new substances.
IONS=FAST
Cr^2+(aq)+Fe^3+(aq)-->Cr^3+(aq)+Fe^2+(aq)

b. Reactions between molecules are usually slower 3. Temperature of reaction system

than ions. In molecules bonds have to be broken and • Generally speaking, an increase in temperature will
new bonds reformed. This slows down reaction rates. increase the reaction rate.
MOLECULES = SLOW 2CO(g)+O2(g)-->2CO2(g) • Similarly, decreasing temperature will decrease the
reaction rate.
c. Gases tend to react faster than solids or liquids:
➢ It takes energy to separate particles from each 4. Presence of a catalyst
other. In order to burncandle wax, the solid wax has • A catalysts is a substance that affects the reaction
to be melted and then vaporized before it reacts with rate without being used up in the reaction.
oxygen. Methane gas is already in the gas state so it • The presence of a catalyst usually increases reaction
burns faster than wax. rate.
Fast CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
Slow C25H52(s) + 38O2(g) → 25CO2(g) + 26H2O(g) 5. Surface Area
• Surface area is the exposed matter of a solid
d. Aqueous ions tend to react faster than species in substance.
other states of matter. • An increase in surface area will result in an increase
➢ Solid Pb(NO3)2 will react with solid KI, but the of the exposure of reactants to one another.
reaction is really, really slow. That's because the ionic • The greater the exposure, the greater the reaction
bonding in each reactant is strong and the ions in rate.
each compound are hard to separate from each other.
➢ When aqueous solutions of these compounds are
mixed, the formation of PbI2 iodide is rapid. In
aqueous solutions, the ions of each compound are
dissociated. When the two the solutions are mixed
together, all that is required for a reaction to occur is
contact between the lead(II) ions and the iodide ions.
Fast Pb(NO3)2(aq) + 2KI(aq) → PbI2(s) + 2KNO3(aq)
Slow Pb(NO3)2(s) + 2KI(s) → PbI2(s) + 2KNO3(s)
The Collision Theory
Collision theory states that for a chemical reaction to
occur, the reacting particles must collide with one
another.
• In a chemical reaction, products are formed due to
the collision between the reactant molecules.
• The conditions for the collisions to form products
are:
1. Effective Collisions
2. Sufficient Energy
3. Right Orientation

A. Collisions should be effective.

✓ The reactant particles must collide with each other.
Collisions between reactant molecules convert the
reactants into the products of the reaction.
Any non-zero number to the zero power equals one.
But remember...
NOT EVERY COLLISION LEADS TO REACTION!!!!!
• In order for collisions to be effective, there must be
considerable FORCE
in the collisions.
• The slower moving molecules do not have enough
kinetic energy to react when they collide...they
bounce off one another and retain their identity.
Only those molecules moving at high speed have
enough energy for collisions to result in a reaction.

B. The right orientation of reactant molecules towards

each other.

c. All molecules should possess a minimum amount of

energy to form product molecules.
➢ The minimum amount of energy required to
initiate a chemical reaction is called activation energy,
Ea (expressed in kJ).
(Activation energy will be further discuss in the next
module.)
 reaction to happen which has a lower activation
energy.
In other words, to move the activation energy on the
graph like this:

As before, particles which don't have enough

energy at a particular time will at some time in
the future gain energy from random collisions,
just as other particles will lose energy. You
mustn't get the idea that those particles in the
blue area of the graph can never react - given
time they will.

Adding a catalyst has exactly this effect of shifting

the activation energy. A catalyst provides an
alternative route for the reaction. That
alternative route has a lower activation energy.
Showing this on an energy profile:

The process of
speeding up a reaction by reducing its activation
energy is known as catalysis, and the factor that's
added to lower the activation energy is called a
catalyst. Biological catalysts are known as
Catalyst Affecting Reaction Rate
enzymes, and we’ll examine them in detail in the
THE EFFECT OF CATALYSTS ON REACTION RATES next section.
Catalysts and activation energy
To increase the rate of a reaction you need to increase
the number of successful collisions. One possible way
of doing this is to provide an alternative way for the Three Types of Catalyst:
A. Homogeneous Catalysis imbalance, which is offset by a proton (i.e., a
A reaction is considered homogeneously hydrogen ion).
catalyzed when the catalyst and the reactant(s) C. Enzymes
are in the same physical state or phase. This most Enzymes are proteins that function as catalysts in
living systems. These enzymes have components
often happens with gaseous catalyst-reactant
called substrate binding sites, or active sites, where
pairs. Types of homogeneous catalysts include
the molecules involved in the reaction under catalysis
organic acids in which the donated hydrogen become attached. The component parts of all proteins
atom is replaced by a metal, a number of are amino acids, and each of these individual acids has
compounds blending carbon and metal elements an uneven charge distribution from one end to the
in some form, and carbonyl compounds joined to other. This property is the main reason enzymes
cobalt or iron. possess catalytic capabilities.

An example of this type of catalysis involving The active site on the enzyme fits together with the
liquids is the conversion of persulphate and correct part of the substrate (reactant) rather like a
iodide ions to sulfate ion and iodine: key going into a lock. Note that the catalysts described
earlier often catalyze an array of dissimilar reactions
S2O8^2- +2I- →2SO4^2- +I2
and therefore do not possess the degree of chemical
specificity that enzymes do.
This reaction would have a difficult time
proceeding on its own despite the favorable In general, when more substrate and more of an
energetics, because both reactants are negatively enzyme are present, the reaction will proceed more
charged and therefore their electrostatic qualities quickly. But if more and more substrate is added
are in opposition to their chemical qualities. But if without adding more enzyme as well, all of the
iron ions, which carry a positive charge, are enzymatic binding sites become saturated, and the
added to the mix, the iron "distracts" the reaction has reached its maximum rate for that
negative charges and the reaction moves forward enzyme concentration. Each reaction catalyzed by an
quickly. enzyme can be represented in terms of the
intermediate products formed owing to the presence
of the enzyme. That is, instead of writing:
A naturally occurring gaseous homogeneous
S→P
catalysis is the conversion of oxygen gas, or O2, in to show a substrate being transformed into a product,
the atmosphere to ozone, or O3, where oxygen you can depict this as:
radicals (O-) are intermediates. Here, ultraviolet E + S → ES → E + P
light from the sun is the true catalyst, but every wherein the middle term is the enzyme-substrate (ES)
physical compound present is in the same (gas) complex.
state.
Enzymes, although classified as category of catalyst
B. Heterogeneous Catalysis distinct from those listed above, can be either
A reaction is considered heterogeneously catalyzed homogeneous or heterogeneous.
when the catalyst and the reactant(s) are in different
phases, with the reaction occurring at the interface Enzymes function optimally within a narrow
between them (most commonly, the gas-solid temperature range, which makes sense given that
"border"). Some of the more common heterogeneous your body temperature does not fluctuate by more
catalysts include inorganic – that is, non-carbon- than a few degrees in ordinary conditions. Extreme
containing – solids such as elemental metals, sulfides heat destroys many enzymes and causes them to lose
and metallic salts, as well as a smattering of organic their specific three-dimensional shape, a process
substances, among them hydroperoxides and ion called denaturing that applies to all proteins.
exchangers.
Thermodynamics
Zeolites are an important class of heterogeneous
catalysts. These are crystalline solids made up of Spontaneity and Entropy
repeating units of SiO4. Units of four of these Consider the following examples: a waterfall flows
joined molecules are linked together to form different downhill, but neverup, heat flows from a warmer
ring and cage structures. The presence of an object to a cooler one, but the reverse never happens
aluminum atom in the crystal creates a charge spontaneously. Iron exposed to water and oxygen
forms rust, but rust does not spontaneously change
back into iron. Chemical processes can be This is simply implies that entropy change is the factor
spontaneous as well. An example is spontaneous that can account for the spontaneity of endothermic
combustion, wherein a flammable substance burns by processes. There are several factors that influence the
itself even without direct application of spark or amount of entropy present in a system at a particular
flame. The spontaneous reaction between magnesium state. These factors are the following:
ribbon and hydrochloric acid wherein the magnesium 1.Change in Phase. Solid particles are confined to fixed
metal instantly disappears with the evolution of heat positions or compactly arranged so that they can
and gas is irreversible. This type of process does not hardly move, thus, entropy is relatively low. In liquids,
need the application of energy to take place is said to the particles are slightly far from each other, allowing
be spontaneous process. limited movement, which results in higher entropy as
compared to solids. Whereas in gases, the particles
Conversely, a nonspontaneous process cannot are
proceed unless there is a driving force or outside help very far apart, hence, there is a great freedom of
that acts on the system. For example, a ball cannot be movement and increase kinetic energy, giving rise to
brought uphill unless someone pushes it. Spontaneity greater entropy as compared to liquids. On the other
of a process can be determined from the change in hand, conversion of gas to liquid, and from liquid to
entropy and change in free energy of a system. the solid, result in a decrease in entropy.
universe. Entropy, S, can be viewed as a measure of 2. Change in Temperature. Rising the temperature
randomness, or disorder. Nature spontaneously increases the average kinetic energy of molecules.
proceeds toward the states that have the most With an increase in temperature, solid particles
“spread out energy”, or the highest probabilities of vibrate more energetically, while liquid and gas
existing. In other words, towards an arrangement particles move about more rapidly. Hence, increasing
where energy can be contained in the greatest the temperature increases the entropy of a system
number of ways. while a decrease in temperature results in lowering of
entropy.
The driving force for a spontaneous process is an 3. Number of particles. The phrase “ the more the
increase in the entropy of the universe. Everyone will merrier” can certainly be applied to entropy. It is
agree that a person usually spends more time and definitely “merrier” when there are more people in
effort in arranging or organizing things as compared to gathering. When a lot of people are present, there will
creating a mess. An orderly room becomes messy with be more movement, more
time. Neatly arranged items on a shelf do not stay noise, more wastes, and definitely greater disorder.
orderly for long. They tend to become disordered as Consider a chemical system presented by the
time passes by. This is inevitable, because creating a following equation,
mess is a more natural and spontaneous process. A2B ------ 2A + B
Hence, if we will compare the entropies of 1 mole of a At the left arrow, only one particle is present as
substance in the three physical states based on the reactant, but at the right side, a total of two particles
kinetic molecular theory theory, molar entropy of the are produced from the reaction. Since there are more
gaseous state will be highest, molar entropy of the particles in products as compared to the reactants,
liquid state will be intermediate, and molar entropy of there is a corresponding increase in disorder.
the solid state will be the lowest. The change in Generally, an increase in the number of particles,
entropy, ∆S, depends only on the entropies of the increase the entropy.
final and initial states of the system.
∆S = Sfinal-Sinitial Example. Predict whether the entropy increases or
decreases, and consider the degree of disorder, from
A positive value of ∆S (∆S>0), indicates that the final initial to final state or form.
state is more random or disordered than the initial CO2 (s) --------- CO2 (g)
state. A negative ∆S value (∆S<0), indicates that the Solution: Entropy increases and ∆S is > 0, because
final state is more ordered than the initial state. once the solid is converted to gas, the particles are
Spontaneity of a process is not solely determined by more scattered and are no longer confined to a
the tendency of a system to proceed to a state of limited volume of space, thus leading to greater
lower energy. It is also dependent on the state of disorder.
disorder. The direction in which a chemical reaction A numerical value for entropy can be possibly
proceeds is governed by the tendency to attain a state determined for any substance under a given set of
that is statistically more probable. In other words, an conditions. The change in entropy is related to heat
increase in disorder or entropy is thermodynamically transferred during the process. The relationship of ∆S
favorable for a reaction to proceed spontaneously. and the heat transferred under constant pressure. For
processes occurring at constant temperature and
pressure, the change entropy can be calculated using
the equation, ∆S = qrev/T where: is change in entropy
in J/K ( it is negative if heat is released by the system
and positive if heat is absorbed by the system), q=
heat transferred at a particular temperature, in J and
T= temperature in Kelvin, (K). However, this equation
applies only to processes that are almost reversible.
Any process that can go back to its original state due
to a very slight change in condition is reversible. A
typical example is the melting and freezing.