GENCHEM 2

✧.*second grading

Lesson 10: Energy Changed in Chemical Reactions and

The First Law of Thermodynamics

Thermodynamics
- Is the study of energy/ heat flow that accompanies a chemical reaction
and/or physical transformations.
*Thermochromism - Property to change color depending on the substance’s
temperature.
System - part of the universe being studied or which attention is focused.
Surroundings - includes everything else in the universe.
When heat (q) from the system to its surroundings, q is designated as
negative. Recall that the process with negative values q is described as
exothermic. However, when the system absorbs heat from the surroundings,
q is positive, meaning the corresponding process is endothermic.

Thermochemistry
- A branch of thermodynamics that deals with the interconversion of
energy between two forms; heat & work.
The energy of the system (ΔEsys) and the energy of its surroundings(ΔEsurr)
are related by the following equation:
ΔEsys = - ΔEsurr
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 any 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
The above equation implies that every chemical reaction is always
accompanied by an energy change and that energy change is driven by the
transfer of heat and the work done by either the system or surroundings.

If q is positive (q = +), energy of the system is increased.

q = + (endothermic); ΔE > 0
If q is negative (q = -), energy of the system is decreased.
q = - (exothermic); ΔE < 0

If work is done by the system, then w is negative. However, if the work is

done by the surroundings, then w is positive.

Calorimetry
The flow of energy (as heat) between the system and its surroundings is
measured through calorimetry. The amount of heat absorbed or released by
the system is a function of its change in temperature.

q = CΔT

ΔT = T final - T initial

From the equation, heat and temperature change are related by a

proportionality constant referred to as heat capacity (C), which is the
amount of energy needed to increase the temperature of a substance or
material by 1°C. this constant is expressed in the units J/°C. The heat
capacity of a substance can only be determined experimentally through
calorimetry.
For a pure substance, the heat of capacity is equal to the product of its mass
(m) and specific heat (c).

C = mc

Therefore,
q = mcΔT

The specific heat of the substance is the amount of

energy needed to increase the temperature of
one gram of the substance by 1°C. Its unit is J/g·°C.
The specific heat of a substance is constant.
Table 1 on the side lists the specific heat values
of some common substances. Different physical
states of the some have different values of
specific heat.

The calorimeter is an excellent insulator and absorbs only a negligible

amount of heat. Thus, the system is assumed to exchange heat only with
water in the calorimeter, and the expression is simplified to;

qsys = -| q calorimeter + qwater |

or
qsys = -qwater = -(mcΔT)water

Enthalpy of a Chemical Reaction

In addition to internal energy, pressure and volume, another state function is
enthalpy. For a system at constant pressure, PV work is employed.
ΔE = qp + W
The amount of heat and absorbed in a chemical reaction at constant
atmospheric pressure is called enthalpy (H).

H = E + PV

At constant pressure, the change in enthalpy ΔH is equal to qp, thus

ΔH = ΔE + PΔV

A chemical equation that shows the value and direction of heat involved in a
reaction is called thermochemical equation, which indicates the physical
state of the reactants and products involved in the reaction.

The difference between the enthalpy of products and the reactants is called
the enthalpy of a reaction ΔH.

ΔH = Hproduct + Hreactant
When ΔH is positive, the chemical reaction is described as endothermic.
When ΔH is negative, the chemical reaction is described as exothermic.

The standard molar enthalpy of formation (ΔH°f) of a compound is the

change in enthalpy when compound is formed from its elements under
standard conditions at (1 atm, 25°C).

The standard enthalpy of a reaction (ΔH°rxn) can thus be calculated by

subtracting the sum (Σ) of the enthalpies of formation of the products and the
sum of the enthalpies of formation of the reactants.

Consider the hypothetical equation:

aA + bB → cC + dD
...where a, b, c, and d are the respective coefficients of substances A, B, C,
and D in the balanced chemical equation.

The sum of the enthalpies of formation of the products is calculated as:

ΣΔH°f (products) = c ΔH°f (C) + d ΔH°f (D)

And for the reactants:

ΣΔH°f (reactants) = a ΔH°f (A) + b ΔH°f (B)

Then, the standard molar enthalpy of the hypothetical reaction is calculated

as,
ΔH°rxn = ΣΔH°f (products) - ΣΔH°f (reactants)

The standard molar enthalpies of each of the reactants and products can be
obtained from the table.
If a reaction is an overall process that can be attained through a series of steps
of reactions, then the enthalpy of this overall reaction can be calculated from
the thermochemical equations defining the reactions leading to it. This
approach can be summarized by Hess's law, which states that the enthalpy of
a sum of a series of reactions is equal to the sum of the enthalpies of those
two reactions. In such cases, the following rules must be considered;
Rule 1: Enthalpy is an extensive property; it depends on the amount of
reactants and products.
Rule 2: The ΔH for a forward reaction is equal in magnitude but opposite in
sign to its reverse reaction.
Rule 3: The ΔH for a reaction is the same whether it occurs in one step or in
a series of steps.

Lesson 11: Chemical Kinetics: Slow and Fast Reactions

Chemical kinetics refers to the study of the rates and mechanisms of

chemical reactions. In the study of chemical kinetics, note that the system is
not in equilibrium. Chemical kinetics is important in several applications,
particularly in understanding the behavior of a chemical system.

Homogeneous reactions - occur in one phase.

ex. 2NO2(g) → 2NO2(g) + O2(g); the decomposition of nitrogen dioxide, a
gaseous pollutant.
Heterogeneous reactions - involve substances in two or more phases.
ex. (C6H5N2)Cl → C6H5Cl(g) + N2(g); decomposition of benzene
diazonium chloride, in which reactant is present in solution (aqueous), and
the products nitrogen (N2) and chlorobenzene (C6H5Cl) are a gas and a
liquid, respectively.
Rate of a Reaction
The rate of a reaction can be defined as the change in the concentration of a
reactant or product per change in time. The concentration of a reactant or
product is represented in square brackets “[ ]”.

The rate of a reaction can be expressed as;

By convention, a negative sign is attached to the change in the concentration

of the reactant, which underscores the fact that the concentration of the
reactants decreases as the reaction proceeds. This convention maintains the
positive sign for the rate.

Rate Law for a Reaction

The rate law is a mathematical expression that shows how the rate of
reaction depends on the concentration of the reactants. The rate law for this
reaction is expressed as;

...where k is the rate constant, and the power x is the order of the reaction
with respect to the reactant A. The rate of reaction is expressed in molar per
second (M/s).

Order of a Reaction
I. Zero-order Reaction (x = 0) has a constant rate that is equal to its rate
constant regardless of the changes in the concentration of the reactant.
 II. First-order Reaction (x = 1) is the rate that doubles when the
concentration of a reactant is doubled.

III. Second-order Reaction (x = 2), increasing the reactant concentration

to twice as much as quadruples the original reaction rate.

Determining the Order of a Reaction

The rate law for a reaction can be experimentally determined through the
method of initial rates. The technique determines how the rate is affected by
concentrations by comparing the initial rates of a reaction at different initial
concentrations of reactants. To illustrate this, consider the hypothetical
reaction;
A+B→C

Obtained from three separate experiments, the following data table shows the
initial concentrations of reactants A and B and their reaction rates.
Mathematically, the order can be determined using two rate laws;

Since reactant B should have the same concentration, the equation

summarizes into;

Applying the equation for reactant A in experiment I and II,

Therefore, this is a first-order reaction with respect to reactant A.

The same method is applied to determine the order with respect to reactant B.
In experiment I and III, the initial concentration of reactant A are the same
and thus will not contribute to the change in the initial reaction rate.
Setting up the ratio of the two rate equations and solving for x.

Therefore, the reaction with respect to reactant B, is a second-order reaction.

The rate law of the hypothetical reaction, A + B → C is therefore written as;

Note that the reaction is third order overall. The rate constant (k) can be
calculated from the rate law of any of the experiment runs. Using experiment
1, k is calculated as;

Integrated Rate Law

In chemical industries, it is important to determine the time it takes for an
amount of chemical to be consumed, or the remaining amount of reactant
(expressed as concentration) that would be left after a certain period of
reaction time. An integrated rate law, which relates these two variables, is
from the rate law expression for the reaction.
Suffice to say that the result is a linear equation;

y = mx + b

I. Zero-order Reaction
The rate is independent of the concentration on the reactant. It remains
constant throughout the course of the reaction and is equal to the rate
constant.

The concentration of the reactant at any given time of the reaction can be
obtained using the equation. The half-life (t1/2) of a reaction is the time it
takes for an initial amount of reactant to be reduced to half. For zero order
reaction, it is given by;

As shown, the half-life depends on the initial concentration of the rate

constant of a zero-order reaction.

II. First-order Reactions

The integrated rate law for a first-order reaction gives a linear equation.

The natural logarithm (ln) of the concentration plotted against the time gives
a linear graph with slope equal to the negative of the rate constant. The
equation for the half-life of the first order reaction can be derived from its
integrated rate law equation and takes the form
The equation shows that the half-life depends only on the rate constant. The
initial concentration of the reactant does not affect its half-life.

III. Second-order Reactions

Based on the rate law expression for a second-order reaction, the integrated
rate law shows a linear relationship between the reciprocal of the reactant
concentration and time.

The half-life for a second-order reaction can also be derived from the
integrated rate law and is expressed as an equation showing dependence on
both rate constant and initial concentration.

Reaction Mechanism and Molecularity

A reaction mechanism is a sequence of reaction steps that show how the
reactants are converted into products. It consists of two or more elementary
steps that sum up to an overall reaction.

As seen from the mechanism, the first step involves a reaction between two
nitrogen dioxide molecules, producing one of the products of the overall
reaction – nitric oxide (NO). The other product – nitrogen trioxide (NO3) – is
called a reaction intermediate, which is a species that is eventually
consumed in the second step of the mechanism. A reaction intermediate does
not appear in the overall reaction.
The second step produces the other product of the overall reaction – carbon
dioxide (CO2). This step also regenerates one of the nitrogen dioxide
molecules used up in the previous step.

This slow reaction limits the rate of the overall reaction no matter how fast
the other steps are; thus, it is called the rate-determining step, which dictates
the rate law for the reaction.

In the given example, the slow step is the reaction between two NO2
molecules , thus the rate law can be written as;

This means that the reaction is zero-order with respect to the CO. It can be
inferred from the rate law that the reaction is bimolecular in terms of NO2.

The principle is called the molecularity of the reaction, which indicates the
number of molecules that are involved in the rate-determining step. It is also
related to the order of the reaction.
Models for the Reaction Rate
Aside from reactant concentration, other factors influence the favorability of
a chemical reaction to occur and the rate at which it occurs. These include;
● Reactant particle collision
● Activation energy
● The presence of catalysts
● The reaction temperature
The Collision Theory
For a chemical reaction to occur, there must be contact between reactants
through collision. This theory can be practically explained using the effect of
stirring. The stirring motion causes the reactant particles to move faster,
thereby increasing the probability of collision. However, not all particle
collisions lead to a successful reaction. It is imperative that the reactants are
in proper orientation during that moment of collision.

The Activation Energy

Aside from colliding with one another, the reactant particles must also have
sufficient energy during collision. They must be able to surpass an energy
barrier, called activation energy of the transition stage (Ea) to successfully
form the products. At the transition state, the reactants form an activated (or
transition) complex that eventually forms the product.

Catalyst
They speed up the rate of a chemical reaction by providing an alternate route
for the reaction to occur with lower activation energy. Catalysts are not
consumed in a reaction; they are used but generated during the reaction.

Heterogeneous Catalysis - uses a catalyst that is of a different phase from

that of the reactants and products.
Homogeneous Catalysis - uses a catalyst that is of the same phase as that of
the reactants and products.

Arrhenius Equation: Effect of Temperature on Reaction Rate

Increasing the temperature of the reaction system causes the reactant particles
to move faster, thereby increasing the chances of sufficiently energetic and
successful collision. Furthermore, the increase in energy allows the reactants
to reach the activation energy faster.

...where k is the rate constant, A is the reaction frequency factor, Ea, is the
activation energy, R is the universal constant equal to 8.314 J/mol · K, and T
is the temperature in Kelvin.

Lesson 12: Spontaneous Processes & The Law of

Thermodynamics
Spontaneity only tells whether a reaction will occur or not. It does not
predict the rate of a process (i.e., how fast or slow it occurs). The
combustion of alcohol is fast, while the rusting of iron is slow; but both
processes occur spontaneously.

According to the Thomsen-Berthelot principle, almost all exothermic

chemical processes are spontaneous. This principle was proposed
independently by Danish chemist Julius Thomsen (1826- 1909) and French
chemist Pierre-Eugène-Marcellin Berthelot (1827-1907).

Entropy
Entropy is a measure of molecular randomness. A solid with a rigid
structure has low entropy. Gases whose molecules are in constant random
motion in various directions are described to have very high entropy.
Similar to enthalpy, entropy is a state function; it only depends on the
initial and final states of the system. It does not take into consideration how
the final state was attained.

A positive ΔS indicates an increase in randomness of a system; a negative

ΔS indicates a decrease in randomness.

Factors That Influence Entropy

A change in temperature can result in change in entropy. Raising the
temperature of a system increases the average kinetic energy and the
freedom of motion of the particles in the system; thus, increasing the entropy
of the system. Conversely, lowering the temperature of the system will
lead to a decrease in entropy. This implies that if the temperature is
reduced indefinitely, a system will reach a condition with zero entropy.
This is what the third law of thermodynamics states that a perfectly
ordered pure crystalline solid at zero Kelvin will have zero entropy.
Consider the spontaneous decomposition of calcium carbonate (CaCO3). For
every mole of CaCO3 used, two moles of products are produced.

Chemical reactions with fewer product particles that the reactants are
described to have negative entropy and are thus non-spontaneous. Such is the
case for ammonia (NH3) production.

The change in entropy, however,

is affected not only by temperature
and number of particles. This generals
trend is observed for all substances:
a steady increase in entropy as the
temperature is raised for a
particular phase, the abrupt increased
once the temperature for a phase
change is reached.

Entropy of the System

Spontaneous reactions are associated with an increase in entropy, or the
disorderliness of a system and its surroundings. Here, the increase should
refer to the total or net entropy, wherein the sum should be positive. The
entropy of the universe tends to always increase. This increase in entropy
is the essence of the second law of thermodynamics.

The entropy of a substance depends on the temperature and on its physical

phase. Entropy changes are based on a change in volume and on a change in
heat, given by;

For an ideal gas that is undergoing a reversible compression from V1 to V2,

For isothermal expansion-compression of ideal gas, change in entropy can be
calculated using

Dependence of Entropy on Temperature

The change in entropy for a given change in temperature can be calculated
using the following formulas.
At constant pressure,

At constant volume,

Calculating Entropy Change Associated with Phase Change

Melting is a reversible process. The change in entropy associated with a
phase change can be calculated using;

As shown, qrev = ΔHfusion. Similarly, for the boiling process, the change in
entropy can be determined by using
Standard Molar Entropy
The standard molar entropy (S°) of a substance is the entropy of one mole of
a substance at the standard conditions (1 atm and 25°C). Note that unlike
enthalpy, the standard molar entropy of substances in their elemental form is
not zero; those of pure substances are always positive values (S° > 0).
As a state function, the standard entropy of reaction (ΔS°) can be calculated
from the difference between the standard molar entropies of the products and
the reactants involved in the reaction.

For a general reaction;

aA + bB → cC + dD

...a, b, c, and d are the coefficient of the substances in the balanced equation,
the balanced entropy of the reaction is calculated as;

Second Law of Thermodynamics

The second law of thermodynamics explains the relationship between entropy
change and spontaneity of a process. It states that for any spontaneous
process, there is a net increase in the total entropy of the system and its
surroundings.

Thus, even if ΔSsys is negative, the process can be spontaneous as long as

ΔSsurr is positive and has greater magnitude than ΔSsys. If the system is a
chemical reaction, ΔSsys is simply the ΔS° of the reaction calculated from the
S° values of the reactants and products.

Calculating ΔSsurr however, requires recalling the first law of

thermodynamics, which states that energy is exchanged between the system
and its surroundings in the form of heat and work. The entropy change in the
surroundings is directly proportional to the enthalpy change of the reaction
and inversely proportional to the absolute temperature (in Kelvin) of the
surroundings.

Gibbs Free Energy and Spontaneity

From earlier discussions, the spontaneity of a process depends on two
thermodynamic quantities: enthalpy and entropy. Combining these two into a
single equation introduces a third thermodynamic quantity that ultimately
determines spontaneity. This quantity is referred to as the Gibbs free energy
(G), named after the American mathematician and physicist Josiah Willard
Gibbs.
Free energy is a portion of the total energy of a system that is available to do
useful work. The three thermodynamic quantities are related by the equation;

G = H − TS
As such, considering the final and initial states involved in a process, the
equation above can be modified to give the Gibbs-Helmholtz equation
expressed as;
ΔG = ΔH − TΔS

The value of ΔG determines the spontaneity of a chemical reaction at

constant pressure and temperature. A reaction is spontaneous if ΔG is
negative; it is non-spontaneous if ΔG is positive. This follows that for a
reaction to be spontaneous, either of these two conditions must be met:
• ΔH must be negative, while ΔS is positive.
• If ΔH is positive, ΔS must be large or T must be high enough so that ΔG
will be negative.

Under standard conditions of 1 atm and 25°C, the standard free energy
change (ΔG°) of a chemical reaction can be obtained from the standard
enthalpy change (ΔH°) and standard entropy change (ΔS°) The
Gibbs-Helmholtz equation then becomes;

The standard free energy change of a reaction can also be calculated from the
standard free energy of formation ΔGf° of the reactants and products.

Similar to enthalpy, the ΔGf° of elements is zero.

Lesson 13: The State of Equilibrium for Reversible

Reaction

Reversible Chemical Reaction

Chemical reactions that can proceed in either direction (to the right or to the
left) are considered as reversible reactions. For example;

The double-headed arrow signifies that the previous reaction is a reversible

one. Both forward (toward product formation) and backward reactions
(toward the reactants) take place at the same time, wherein reactants
combine to form the products, and products react to yield the reactants.
Chemical equilibrium refers to the state in a chemical reaction wherein the
concentrations of the reactants and the products remain constant. It is also
called the dynamic equilibrium, in which the rates of the forward and
reverse reactions are the same.

Recall from the rate law in chemical kinetics that the rate of a reaction
increases at higher concentrations of the reactants. In the context of a
reversible reaction, this concept suggests that as the forward reaction
proceeds, more products are formed, which in turn serve as the reactants
for the reverse reaction. Thus, as the reaction proceeds, the rate of the
forward reaction decreases as the reactants are consumed. At the same time,
the rate of the reverse reaction increases as more products are formed. The
system will eventually reach a point where the rate of the forward reaction
becomes equal to the rate of the reverse reaction. At this point, the system is
said to have reached a state of dynamic equilibrium. Hence, the reaction does
not go to completion.

At equilibrium, no apparent change in the state of the system is observed.

This is because when the rates of the forward and reverse reactions become
equal, the concentrations of the reactants and products remain constant over
time. This principle is known as the law of mass action.

The Equilibrium Constant

The concentrations of the reactants and products remain constant at
equilibrium. Thus, the ratio of the equilibrium concentrations of these
substances should also be constant.

At equilibrium,

Using the rate law,

The equilibrium constant (Kc) is expressed as,

A high Kc value (>> 1) means that there are relatively more products
than reactants at equilibrium, indicating that formation of products is highly
favorable (forward reaction).

A low Kc value (<< 1), on the other hand, places the equilibrium far to the
left, indicating that only a smaller portion of the reactants are being converted
to products.

The equilibrium constant K is usually expressed as a unitless value. In the

thermodynamic definition of an equilibrium constant, the concentrations are
divided by the standard state value of 1 M (or 1 atm in case of pressures).
Thus, the units cancel out, leaving K dimensionless.

Significance of Kc
The magnitude of Kc describes the extent to which the reaction favors either
the forward reaction or the reverse reaction at equilibrium. Typically, when
the reaction strongly favors a forward reaction, Kc is very large, equal to
or greater than 1000. (The equilibrium position shifts to the right.)

On the other hand, small values of Kc that are equal to or less than 1000
indicate that a backward reaction is strongly favored. Here, the equilibrium
position shifts to the left. Kc = 1 then the concentrations of the reactants and
the products are the same at equilibrium.

Homogeneous & Heterogeneous Equilibria

A homogeneous equilibrium involves reactants and products that are
present in only one phase. It only involves gas, such as the system in the
formation of ammonia (NH3).

A heterogeneous equilibrium consists of reactants and products that exist in

different phases. Solids and liquids do not appear in the equilibrium
constant expression.

Predicting the Direction of the Reaction

At non-equilibrium conditions (e.g., at the start of a reaction), the
instantaneous ratio of the concentrations of the products and reactants gives
the reaction quotient (Q) expressed as;

If only the reactants are present at the start of a reaction, the reaction will just
proceed forward. The same will be true for the reverse reaction if only the
products (which are the reactants of the reverse reaction) are present at the
start of the reaction.

But if all species of the reactants and products are present at the start of the
reaction, three possibilities may occur depending on the relative values of Q
and K.
Le Chatelier’s Principle
Le Chatelier's principle states that when stress is introduced into a system
in equilibrium, the system will adjust to relieve the stress and regain
equilibrium. The stress is relieved as the reaction shifts either to the left
(reverse) or the right (forward) of the reversible reaction.

One factor that can affect systems in equilibrium is the change in the
amount of either the reactants or the products. Adding more reactants to a
reaction that is already in equilibrium will cause it to shift to the right (since
Q will become smaller than K).

Adding more of the products will favor the reverse reaction (since Q will
become greater than K). The opposite effect results when either a reactant
or a product is removed from the reaction. In any case, the system adjusts
by favoring the reaction direction that consumes the excess (reactant
or product) to attain a new equilibrium.
Another factor that facilitates shifts in equilibrium is the change in the
temperature of the reaction system. Recall in thermochemistry that if a
forward reaction is endothermic, its reverse reaction is exothermic, and
vice versa.

Increasing the temperature is equivalent to adding energy to the action,

which favors the direction of the endothermic reaction. Decreasing the
temperature favors the direction of the exothermic reaction.

Another factor that can affect systems in equilibrium is catalysts. Catalysts

can increase the rate of a chemical reaction, but they have no net effect on
a system in equilibrium. If a catalyst can speed up the forward reaction, it
can also speed up the reverse reaction. The only effect it will have been that
the system will reach equilibrium faster.

Good luck!