THERMODYNAMICS

Thermodynamics is the scientific 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.
This is now the first law of thermodynamics. It states that energy cannot be created not destroyed, that means that
energy is constant. This allows us to define a thermodynamic system, which in the case of chemistry is a reaction, with the
surroundings being everything else. So what do we mean by the reaction is a thermodynamic system?
All substances have their own stored chemical potential energy that is released when reaction takes place. Let's use
hypothetical substances in an exothermic reaction; A, B (reactants) and C (product) then, values of heat content.
THIS IS ITS POSSIBLE REPRESENTATION:
A+B C
20kcal 30kcal 15kcal
50kcal = 15kcal + 35 kcal
The product C has less heat content than the reactants and the extra 35kcal is released to the surroundings.

 During a chemical reaction, the energy of the

system changes as bonds in reactant are broken
and the atoms rearrange to form the new bonds
of the products. These new bonds are typically
higher or lower in energy. If the products store
more energy in their bonds, that energy must
come from somewhere, and so it is transferred
into the system from the surroundings.
 In this case of combustion, the products are
lower in energy and so that energy is transferred
to the surroundings. The key point here is as a
reaction proceeds, energy flows into or out of
the system, depending on whether energy is
absorbed or released as the products are formed.
 The First Law of Thermodynamics or simply
the Law of Conservation of Energy applies to
all chemical reactions, in which the total amount of energy is constant and it's just changed from one form to another.
Just like in an Endothermic process, like in photosynthesis where in the plants take Energy from the surroundings to
store more energy.
You might have heard someone say that plants "make energy from the sun." Plants actually convert solar energy
(sunlight) into molecular potential energy, in the form of sugar. Remember, plants do not "make" energy. Photosynthesis
converts light energy (a form of kinetic energy) into chemical energy. This first law could be considered "bookkeeping." It
states that the energy used and released in any reaction must be balanced.
The energy stored in glucose can also be released through cellular respiration. This process allows plant and animal
organisms to access the energy stored in carbohydrates, lipids, and other macromolecules through the production of ATP. This
replication, mitosis, meiosis, cell movement, endocytosis, exocytosis and apoptosis.
The challenge for all living organisms is to obtain energy from their surroundings in forms that they can transfer or
transform into usable energy to do work. Living cells have evolved to meet this challenge very well. Chemical energy stored
within organic molecules such as sugars and fats transform through a series of cellular chemical reactions into energy within
ATP molecules. Energy in ATP molecules is easily accessible to do work. Examples of the types of work that cells need to do
include building complex molecules, transporting materials, powering the beating motion of cilia or flagella, contracting muscle
fibers to create movement, and reproduction.

ENTHALPY OF REACTION
The internal energy of a system is the sum of the KE and PE of all its components. It is the change in internal energy
that produces heat plus work. To measure the energy changes that occur in chemical reactions, chemists usually use a related
thermodynamic quantity called enthalpy.
The enthalpy of a system is defined as the sum of its internal energy (U) plus the product of its pressure P and volume V:
H = U + PV
Since internal energy, pressure and volume are all state functions, enthalpy is also a state function. So we can define a
change in enthalpy:
ΔH = Hfinal – Hinitial
The figure on explore part pertains to enthalpy. Energy changes in chemical reactions are usually measured in changes
in enthalpy. When heat flows from a system to its surroundings, the enthalpy of the system decreases, so the enthalpy of a
reaction is negative, and the reaction is exothermic.
Conversely, if heat flows from the surroundings to a system, the enthalpy of the system increases, so the enthalpy of a reaction
is positive, and the reaction is endothermic.
Enthalpy is simply the change in the energy that happens in a chemical reaction. The enthalpy of a reaction is simply the
difference in enthalpy between products and reactants.
 One way to report the heat absorbed or released would be to compile a massive set of references tables that list the
enthalpy changes for all possible chemical reactions, which would require an incredible amount of effort. Fortunately, since
enthalpy is a state function, all we have to know is the initial and final states of the reaction. This allows us to calculate enthalpy
change for virtually conceivable chemical reaction using a relatively small set of tabulated data such as the following enthalpies
of reaction:
1. Enthalpy of combustion – the change in enthalpy that occurs during combustion reaction. Enthalpy changes have been
measured for the combustion of virtually any substance that will burn in oxygen; these
values are reported as the enthalpy of combustion per mole of substance.
2. Enthalpy of fusion – the enthalpy change that accompanies the melting (fusion) of 1 mol of a substance. The enthalpy
change that accompanies the melting, or fusion of 1 mol of a substance; these values have been measured for almost all the
elements for most simple compounds.
3. Enthalpy of vaporization – the enthalpy change that accompanies the vaporization of 1 mol of a substance; these values
have also been measured for nearly all the elements and for most volatile compounds.
4. Enthalpy of solution – the change in enthalpy that occurs when a specified amount of solute dissolves in a given quantity of
solvent. The enthalpy change when a specified amount of solute dissolved in a given quantity of solvent.

A simpler device than the constant-volume calorimeter is the constant-pressure calorimeter, which is used to determine
the heat changes for noncombustion reactions. A crude constant-pressure calorimeter can be constructed from two Styrofoam
coffee cups, as shown in the figure on the right. 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). As in the case of a constant-volume calorimeter, we treat the calorimeter as
an isolated system.

HESS’S LAW
Hess’s Law, or in some reference, Hess’s Law of Constant Heat Summation 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 of a state
function.
Enthalpy change cannot be accurately measured during an actual chemical reaction in a laboratory. That is why we use
steps in order for us to solve for the enthalpy change in a chemical reaction using the Hess’s Law.
There are no definite steps in solving for the enthalpy change, but these are the steps that are commonly used to solve
for enthalpy change.
1. Balance the individual equation
2. If necessary, look up standard enthalpies
3. Flip equations around if necessary to cancel out terms on opposite sides
4. Changing the equation around requires a sign change of the H of that individual step
5. Sum up the individual steps
To recall, 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 ΔHo rxn can be
measured, we can calculate ΔHo rxn for the overall reaction. Hess’s law is based on the fact that because H is a state function,
ΔH 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.
Let’s say we are interested in the standard enthalpy of formation of carbon monoxide (CO). We might represent the
reaction as:
C(graphite) + ½ O2(g) CO(g)
However, burning graphite also produces some carbon dioxide (CO2), so we cannot measure the enthalpy change for
CO directly as shown. Instead, we must employ an indirect route, based on Hess’s law. It is possible to carry out the following
two separate reactions, which do go to completion:

Because chemical equations can be added and subtracted just like algebraic equations, we carry out the operation (a) +
(c) and obtain:
 Thus, ΔHof (CO) = -110.5 kJ/mol. Looking back, we see that the overall reaction is the formation of CO2 [Equation
(a)], which can be broken down into two parts [Equations (d) and (b)]. Take note also that if the is positive, the reaction is
endothermic and when it is negative, it means that the reaction is exothermic.
The general rule in applying Hess’s law is to arrange a series of chemical equations (corresponding to a series of steps)
in such a way that, when added together, all species will cancel except for the reactants and products that appear in the overall
reaction. This means that we want the elements on the left and the compound of interest on the right of the arrow. Further, we
often need to multiply some or all of the equations representing the individual steps by the appropriate coefficients.