BOOK SUMMARY

Energy Relationships in Chemical Reactions

A. The Nature of Energy and Types of Energy
Energy is usually defi ned as the capacity to do work. “Energy” is a much-used term that
represents a rather abstract concept. For instance, when we feel tired, we might say we haven’t
any energy; and we read about the need to find alternatives to nonrenewable energy sources.
Unlike matter, energy is known and recognized by its effects. It cannot be seen, touched,
smelled, or weighed. The energy contained in tidal waves, for example, can be harnessed to
perform useful work, but the relationship between tidal waves and chemistry is minimal.
Chemists define work as directed energy change resulting from a process. Kinetic energy—the
energy produced by a moving object—is one form of energy that is of particular interest to
chemists. Others include radiant energy, thermal energy, chemical energy, and potential energy.
Radiant energy, or solar energy, comes from the sun and is Earth’s primary energy source.
Solar energy heats the atmosphere and Earth’s surface, stimulates the growth of vegetation
through the process known as photosynthesis, and influences global climate patterns.
Thermal energy is the energy associated with the random motion of atoms and molecules. In
general, thermal energy can be calculated from temperature measurements. The more vigorous
the motion of the atoms and molecules in a sample of matter, the hotter the sample is and the
greater its thermal energy.
Chemical energy is stored within the structural units of chemical substances; its quantity is
determined by the type and arrangement of constituent atoms. When substances participate in
chemical reactions, chemical energy is released, stored, or converted to other forms of energy.
Potential energy is energy available by virtue of an object’s position. For instance, because of
its altitude, a rock at the top of a cliff has more potential energy and will make a bigger splash if
it falls into the water below than a similar rock located partway down the cliff. Chemical energy
can be considered a form of potential energy because it is associated with the relative positions
and arrangements of atoms within a given substance.

B. Energy Changes in Chemical Reactions

Almost all chemical reactions absorb or produce (release) energy, generally in the form of heat.
It is important to understand the distinction between thermal energy and heat. Heat is the transfer
of thermal energy between two bodies that are at different temperatures. Thus, we often speak of
the “heat flow” from a hot object to a cold one. Although the term “heat” by itself implies the
transfer of energy, we customarily talk of “heat absorbed” or “heat released” when describing the
energy changes that occur during a process. Thermochemistry is the study of heat change in
chemical reactions.
To analyze energy changes associated with chemical reactions we must first define the system,
or the specific part of the universe that is of interest to us. The surroundings are the rest of the
universe outside the system. There are three types of systems. The first is an open system, this
system can exchange mass and energy, usually in the form of heat with the environment. The
second is a closed system, this system allows the transfer of energy (heat) but not mass. And the
last is an isolated system, this system does not allow the transfer of mass or energy.
If, the heat generated by the combustion process is transferred from the system to its
surroundings. This reaction is an example of an exothermic process, which is any process that
gives off heat that is, transfers thermal energy to the surroundings. For example the combustion
of hydrogen gas in oxygen is one of many chemical reactions that release considerable quantities
of energy.
2H2(g) + O2(g) → 2H2O(l) + energy
Now consider another reaction, the decomposition of mercury(II) oxide (HgO) at high
temperatures:
energy + 2HgO(s) → 2Hg(l) + O2(g)
This reaction is an endothermic process, in which heat has to be supplied to the system (that is,
to HgO) by the surroundings. In exothermic reactions, the total energy of the products is less
than the total energy of the reactants. The difference is the heat supplied by the system to the
surroundings. Just the opposite happens in endothermic reactions. Here, the difference between
the energy of the products and the energy of the reactants is equal to the heat supplied to the
system by the surroundings.

C. Introduction to Thermodynamics
Thermochemistry is part of a broader subject called thermodynamics, which is the scientific
study of the interconversion of heat and other kinds of energy. In thermodynamics, we study
changes in the state of a system, which is defined by the values of all relevant macroscopic
properties, for example, composition, energy, temperature, pressure, and volume. Energy,
pressure, volume, and temperature are said to be state functions—properties that are determined
by the state of the system, regardless of how that condition was achieved. In other words, when
the state of a system changes, the magnitude of change in any state function depends only on the
initial and final states of the system and not on how the change is accomplished. The state of a
given amount of a gas is specified by its volume, pressure, and temperature.
The First Law of Thermodynamics
The first law of thermodynamics, which is based on the law of conservation of energy, states that
energy can be converted from one form to another, but cannot be created or destroyed. We can
test the validity of the first law by measuring only the change in the internal energy of a system
between its initial state and its final state in a process. The change in internal energy ∆U is given
by :

∆U = Uf − Ui
where Ui and Uf are the internal energies of the system in the initial and final states,
respectively.

The internal energy of a system has two components: kinetic energy and potential energy. The
kinetic energy component consists of various types of molecular motion and the movement of
electrons within molecules. Potential energy is determined by the attractive interactions between
electrons and nuclei and by repulsive interactions between electrons and between nuclei in
individual molecules, as well as by interaction between molecules.

Work and Heat

 Work
We have seen that work can be defined as force F multiplied by distance d:
w = Fd
In thermodynamics, work has a broader meaning that includes mechanical work (for example, a
crane lifting a steel beam), electrical work (a battery supplying electrons to light the bulb of a
flashlight), and surface work (blowing up a soap bubble). One way to illustrate mechanical work
is to study the expansion or compression of a gas. Many chemical and biological processes
involve gas volume changes. Breathing and exhaling air involves the expansion and contraction
of the tiny sacs called alveoli in the lungs. Another example is the internal combustion engine of
the automobile. The successive expansion and compression of the cylinders due to the
combustion of the gasoline-air mixture provide power to the vehicle.
 Heat
The other component of internal energy is heat, q. Like work, heat is not a state function. For
example, it takes 4184 J of energy to raise the temperature of 100 g of water from 20°C to 30°C.
This energy can be gained (a) directly as heat energy from a Bunsen burner, without doing any
work on the water; (b) by doing work on the water without adding heat energy (for example, by
stirring the water with a magnetic stir bar); or (c) by some combination of the procedures
described in (a) and (b). This simple illustration shows that heat associated with a given process,
like work, depends on how the process is carried out.
In summary, heat and work are not state functions because they are not properties of a system.
They manifest themselves only during a process (during a change). Thus, their values depend on
the path of the process and vary accordingly.

D. Enthalpy of Chemical Reactions

If a chemical reaction is run at constant volume, then ∆V 5 0 and no P-V work will result from
this change. From the following equation:
∆U = q − P∆V
= qv
We add the subscript “v” to remind us that this is a constant-volume process. This equality may
seem strange at first, for we showed earlier that q is not a state function. The process is carried
out under constant-volume conditions, however, so that the heat change can have only a specific
value, which is equal to ∆U.

Enthalpy of Reactions
Because most reactions are constant-pressure processes, we can equate the heat change in these
cases to the change in enthalpy. For any reaction of the type:
reactants → products
we define the change in enthalpy, called the enthalpy of reaction, ∆H, as the difference between
the enthalpies of the products and the enthalpies of the reactants:
∆H = H(products) − H(reactants)
The enthalpy of reaction can be positive or negative, depending on the process. For an
endothermic process (heat absorbed by the system from the surroundings), ∆H is positive (that is,
∆H > 0). For an exothermic process (heat released by the system to the surroundings), ∆H is
negative (that is, ∆H < 0).

E. Calorimetry
In the laboratory, heat changes in physical and chemical processes are measured with a
calorimeter, a closed container designed specifically for this purpose.

Specific Heat and Heat Capacity

The specific heat (s) of a substance is the amount of heat required to raise the temperature of one
gram of the substance by one degree Celsius. The heat capacity (C) of a substance is the amount
of heat required to raise the temperature of a given quantity of the substance by one degree
Celsius. Specific heat is an intensive property, whereas heat capacity is an extensive property.
The relationship between the heat capacity and specific heat of a substance is :
C = ms

If we know the specific heat and the amount of a substance, then the change in the sample’s
temperature (∆t) will tell us the amount of heat (q) that has been absorbed or released in a
particular process. The equations for calculating the heat change are given by :

q = ms∆t

q = C∆t

Where ∆t is the temperature change:

∆t = tfinal − tinitial

The sign convention for q is the same as that for enthalpy change; q is positive for endothermic
processes and negative for exothermic processes.
Constant-Volume Calorimetry
Heat of combustion is usually measured by placing a known mass of a compound in a steel
container called a constant-volume bomb calorimeter, which is fi lled with oxygen at about 30
atm of pressure. The closed bomb is immersed in a known amount of water.

Figure. A constant-volume bomb calorimeter. The

calorimeter is filled with oxygen gas before it is
placed in the bucket. The sample is ignited
electrically, and the heat produced by the reaction
can be accurately determined by measuring the
temperature increase in the known amount of
surrounding water.

The sample is ignited electrically, and the heat produced by the combustion reaction can be
calculated accurately by recording the rise in temperature of the water. The heat given off by the
sample is absorbed by the water and the bomb. The special design of the calorimeter enables us
to assume that no heat (or mass) is lost to the surroundings during the time it takes to make
measurements. Therefore, we can call the bomb and the water in which it is submerged an
isolated system.
Constant-Pressure Calorimetry
A simpler device than the constant-volume calorimeter is the constant-pressure calorimeter,
which is used to determine the heat changes for noncombustion reactions. This device measures
the heat effects of a variety of reactions, such as acid-base neutralization, as well as the heat of
solution and heat of dilution. Because the pressure is constant, the heat change for the process
(qrxn) is equal to the enthalpy change (∆H).

Figure, A constant-pressure calorimeter made of two

Styrofoam coffee cups. The outer cup helps to insulate the
reacting mixture from the surroundings. Two solutions of
known volume containing the reactants at the same
temperature are carefully mixed in the calorimeter. The
heat produced or absorbed by the reaction can be
determined by measuring the temperature change.

F. Standard Enthalpy of Formation and Reaction

Chemists have agreed on an arbitrary reference point for enthalpy. The “sea level” reference
point for all enthalpy expressions is called the standard enthalpy of formation (∆H° f).
Substances are said to be in the standard state at 1 atm, hence the term “standard enthalpy.” The
superscript “°” represents standard-state conditions (1 atm), and the subscript “f” stands for
formation. By convention, the standard enthalpy of formation of any element in its most stable
form is zero. Take the element oxygen as an example.
The Direct Method
This method of measuring ∆H° f works for compounds that can be readily synthesized from their
elements. Suppose we want to know the enthalpy of formation of carbon dioxide. We must
measure the enthalpy of the reaction when carbon (graphite) and molecular oxygen in their
standard states are converted to carbon dioxide in its standard state
The Indirect Method
Many compounds cannot be directly synthesized from their elements. In some cases, the reaction
proceeds too slowly, or side reactions produce substances other than the desired compound. In
these cases, ∆H° f can be determined by an indirect approach, which is based on Hess’s law of
heat summation, or simply Hess’s law, named after the Swiss chemist Germain Hess. Hess’s law
can be stated as follows: When reactants are converted to products, the change in enthalpy is the
same whether the reaction takes place in one step or in a series of steps. In other words, if we can
break down the reaction of interest into a series of reactions for which ∆H°rxn can be measured,
we can calculate ∆H°rxn for the overall reaction. Hess’s law is based on the fact that because H is
a state function, ∆H depends only on the initial and final state (that is, only on the nature of
reactants and products). The enthalpy change would be the same whether the overall reaction
takes place in one step or many steps.
 CRITICAL BOOK REVIEW
COURSES : ENGLISH FOR CHEMISTRY

NAME : FILDZAH NUR KHALISHAH

CLASS: CHEMISTRY NK - 19A
MAJOR: CHEMISTRY
PROGRAM: S1 CHEMISTRY Non-Educational
NIM: 4193210004

Supporting Lecturer : Elfrida Ginting , Ph.D.

FACULTY MATHEMATICHS AND NATURAL SCIENCES

AT STATE UNIVERSTY OF MEDAN
2019