Energy is a much-used term that represents a rather abstract concept.

For instance,
when we feel tired, we might say we havent 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. ( Chang, Raymond :
Energy is usually defi ned as the capacity to do work. In Chapter 5 we defined work as
force 3 distance, but we will soon see that there are other kinds of work. All forms of energy
are capable of doing work (that is, of exerting a force over a distance), but not all of them are
equally relevant to chemistry. 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
energythe energy produced by a moving objectis one form of energy that is of particular
interest to chemists. Others include radiant energy, thermal energy, chemical energy, and
potential energy. ( Chang, Raymond :
Radiant energy, or solar energy, comes from the sun and is Earths primary energy
source. Solar energy heats the atmosphere and Earths surface, stimulates the growth of
vegetation through the process known as photosynthesis, and infl uences global climate patterns.
( Chang, Raymond :
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. However, we need to distinguish carefully between
thermal energy and temperature. A cup of coffee at 70C has a higher temperature than a bathtub
fi lled with warm water at 40C, but much more thermal energy is stored in the bathtub water
because it has a much larger volume and greater mass than the coffee and therefore more water
molecules and more molecular motion. ( Chang, Raymond :
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.
(Chang, Raymond :
Potential energy is energy available by virtue of an objects 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. ( Chang, Raymond :
All forms of energy can be converted (at least in principle) from one form to another. We
feel warm when we stand in sunlight because radiant energy is converted to thermal energy on
our skin. When we exercise, chemical energy stored in our bodies is used to produce kinetic
energy. When a ball starts to roll downhill, its potential energy is converted to kinetic energy.
You can undoubtedly think of many other examples. Although energy can assume many different
forms that are interconvertible, scientists have concluded that energy can be neither destroyed
nor created. When one form of energy disappears, some other form of energy (of equal
magnitude) must appear, and vice versa. This principle is summarized by the law of
conservation of energy: the total quantity of energy in the universe is assumed constant. (Chang,
Raymond :

In every chemical reaction, heat is absorbed or released as reactants are converted to

products. The heat of reaction is the difference between the energy of the reactants and the
energy of the products. In an exothermic reaction, the energy of the reactants is greater than that
of the products. Thus, heat is released in exothermic reactions. (T i m b e r l a k e. 2012 : 199)
Chemical reactions that release heat to the surroundings are considered to be exothermic
reactions.
Lets look at the familiar combustion reaction of propane (C3H3).
C3H3 + 5O2
3CO2 + 4H2O
In truth this reaction is missing one very important product.
C3H3 + 5O2
3CO2 + 4H2O + Heat
When one mole of propane is burned it releases 2028,8 kJ of heat to the surroundings.
Due to convention the heat of reaction for the combustion of propane is expressed as -2028.8 kJ
mol-1. The negative sign is from the perspective of the reactants. The propane and the oxygen lost
heat as a consequence of the combustion reaction. (Pitzer, Edward.2014 :105)
In endothermic reactions, the energy of the reactants is lower than that of the products.
Thus, heat is absorbed in endothermic reactions. For example, when hydrogen and iodine react to
form hydrogen iodide, heat must be absorbed. For an endothermic reaction, the heat of reaction
is written on the same side as the reactants. (T i m b e r l a k e. 2012 : 200)
Chemical reactions that need to absorb heat from the surroundings in order to proceed
are known as endothermic reactions.
Lets look at the formation of nitrogen monoxide (NO) form nitrogen (N2) and oxygen (O2),
N2 (g) + O2 (g)
2NO (g)
Again this chemical equation does not tell not tell the entire story. The reaction will not proceed
unless energy, in the form of heat, is added to the reaction.
N2 (g) + O2 (g) + Heat
2NO (g) (Pitzer, Edward.2014 :105)
Thermochemistry is part of a broader subject called thermodynamics, which is the
scientifi c study of the interconversion of heat and other kinds of energy. The laws of
thermodynamics provide useful guidelines for understanding the energetics and directions of
processes. ( Chang, Raymond :
In thermodynamics, we study changes in the state of a system, which is defi ned 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 fi nal states of the system and not on how the
change is accomplished. The state of a given amount of a gas is specifi ed by its volume,
pressure, and temperature. Consider a gas at 2 atm, 300 K, and 1 L (the initial state). Suppose a
process is carried out at constant temperature such that the gas pressure decreases to 1 atm.
According to Boyles law, its volume must increase to 2 L. The final state then corresponds to 1
atm, 300 K, and 2 L. The change in volume ( V) is
V=V -V
f
i

=2L1L
=1L

where Vi and Vf denote the initial and fi nal volume, respectively. No matter how we arrive at the
fi nal state (for example, the pressure of the gas can be increased first and then decreased to 1
atm), the change in volume is always 1 L. Thus, the volume of a gas is a state function. In a
similar manner, we can show that pressure and temperature are also state functions.
Chemical thermodynamics is the study of the role of energy in chemical changes and in
determining the behavior of materials. It is based on a few laws that summarize centuries of
experimental observation. Each law is a statement about relationships between energy, heat,
work, and temperature. Because the laws manifest themselves in so many different ways and
underlie so many different phenomena, there are many alternative but equivalent ways to state
them. For ease of reference, the laws are identified by number and are called the first law, the
second law, and the third law of thermodynamics.
The first law of thermodynamics, which was discussed in Chapter 7, states that internal
energy may be transferred as heat or work but it cannot be created or destroyed. This law, you
recall, serves as the foundation for Hesss law, which we used in our computations involving
enthalpy changes in Chapter 7. Lets review the first law in more detail. Recall that the internal
energy of a system, which is given the symbol E, is the systems total energythe sum of all the
kinetic and potential energies of its particles. For a chemical reaction, a change in the internal
energy, E, is defined as
E = Eproducts - Ereactants

Thus,

E is positive if energy flows into a system and negative if energy flows out. The first

law of thermodynamics considers two ways by which energy can be exchanged between a
system and its surroundings. One is by the absorption or release of heat, which is given the
symbol q. The other involves work, w. If work is done on a system, as in the compression of a
gas, the system gains and stores energy. Conversely, if the system does work on the surroundings,
as when a gas expands and pushes a piston, the system loses some energy by changing part of its
potential energy to kinetic energy, which is transferred to the surroundings. The first law of
thermodynamics expresses the net change in energy mathematically by the equation
E=q+w
In Chapter 7 you learned that a positive sign on an energy change indicates energy gained
by the system, whereas a negative sign indicates energy lost by the system. Thus, when . . .
q is (+) Heat is absorbed by the system.
q is (-) Heat is released by the system.
w is (+) Work is done on the system.
w is (-) Work is done by the system.
In the lab you may observe the reaction beaker becoming cool if q has a positive sign and you
may feel it warm when heat is released. Similarly, you might observe the system expanding,
especially when a gas is evolved, when work has a negative sign. ( Jespersen.2012.
In Chapter 7 you also learned that DE is the difference between two state functions, Efinal Einitial, which means that its value does not depend on how a change from one state to another is
carried out. The values of q and w strongly depend on how the system changes, as we illustrated
in Figure 7.8 on page 270, and are not state functions. Engineers often try to maximize the work
obtained for a given change while minimizing the loss of energy in the form of heat. The ratio of
w/ E is called the thermodynamic efficiency of a given process. ( Jespersen.2012.

There are two kinds of work that chemical systems can do (or have done on them) that
are of concern to us. One is electrical work, which is examined in Chapter 20 and will be
discussed there. The other is work associated with the expansion or contraction of a system under
the influence of an external pressure. An example is the work you perform on a gas when you
compress it to fill a tire (Figure 19.2). Such pressure volume or PV work was discussed in
Chapter 7, where it was shown that this kind of work is given by the equation
w=P V
where P is the external pressure on the system. If PV work, similar to the work that powers the
diesel engine in Figure 19.3, is the only kind of work involved in a chemical change, the
equation for E takes the form
E = q + (-P V ) = q -P V

In Chapter 7, we also showed that when a reaction takes place in a container whose volume
cannot change, the entire energy change must appear as heat. Therefore, E is called the heat
at constant volume (qv)

E = qv

Over an extended period of time, any differences in process variables, such as

temperature, psessure and chemical potential, will equilibrate in an isolated system, this includes
entropic terms and a system will tend to increase its entropy where possible, giving rise to
irreversible processes. The second law of thermodynamics has several different versions:
The Clausius statement says that no process is possible whose sole result it the transfer of heat
from a body of lower temperature to a body of higher temperature meaning that heat cannot
flow from cold to hot regions without the use of external work.
The Kelvin statement says that no process is possible in which the sole result is the absoption
of heat from a reservoir and its complete conversion into work, which means that in the process
of extracting heat energy from a high temperature source of energy with the aim to convert all
the energy to work, some heat is lost.
The principle of Caratheodory states that in every neighbourhood of any state S of an
adiabatically isolated system there are states inaccessible from S, leading to the derivation of
entropy and an initial insight into adiabatic accessibility, essentially defining a process as
adiabatic if it exhibits a vanishingly infinitesimally small heat change over a given time.
(Fletcher.2012:71)
The final value of H for the overall process is the sum of all the enthalpy changes.

For example, to vaporize 1 mole of H2O 100C and 1 atm, the process absorbs 41 kJ of heat,
H = +41 kJ.

If a different path to the formation of 1 mole of gasous H2O is taken, the same amount of net heat
will still be absorbed. Reversing

Reversing the first reaction, then adding the two reactions together and cancelling common
terms, results in the original reaction, and the amount of heat absorbed by the system

( Hoenig.2002)
Molecules, which contain cylic phosphoric fragments, represent the big interest within
many decades a biochemical objects. Nucleosides and phosphates of sugars are representative of
the important classes of esters of a phosphorous acid. However their thermochemistry, having
essential value for the much deeper. Detailed understanding of their important biochemical
function, is poorly investigated. For this reason we have undertaken the theoretical calculation of
the heats of combustion (
H) and then on this basis the heats of formation ( H
comb

in the condensed state of organic phosphor-nucleotides of a cyclic structure, kinetics and

thermochemistry of hydrolysis of which has been investigated earlier experimentally.
(Ovchinnikov, Vitally.2011)
The main principle of thermochemical TES is based on a reaction that can be reversed:
C + heat A + B

In this reaction, a thermochemical material (C) absorbs energy and is converted chemically into
two components (A and B), which can be stored separately. The reverse reaction occurs when
materials A and B are combined together and C is formed. Energy is released during this reaction
and constitutes the recovered thermal energy from the TES. The storage capacity of this system
is the heat of reaction when material C is formed. ( Abedin, Ali.2011)