Physical Chemistry Thermodinamics

CHANGES IN STATE AT CONSTANT
VOLUME AND TEMPERATURE

&
THE RELATION BETWEEN CP AND CV
CHANGES IN STATE AT CONSTANT
VOLUME AND TEMPERATURE
INTRODUCTION OF THERMODYNAMIC
Thermochemistry is part of a broader subject called thermodynamics, which

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. In this section we will concentrate on the
first law of thermodynamics, which is particularly relevant to the study of
thermochemistry.
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 change in volume (∆ V) is
where Vi and Vf denote the initial and final 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.
Energy is another state function. Using potential energy as an example, we find
that the net increase in gravitational potential energy when we go from the same
starting point to the top of a mountain is always the same, regardless of how we
get there.
Isotermic Process
Boyle's law states that at constant temperatures, gas pressure

inversely with the volume. Circumstances in accordance with the Boyle's
law is called isotermic. (Isothermal). So, the isotermic process is the
system state changes at a fixed temperature. According to Boyle's Law, in
this process apply the following equations.
P V = constant
The temperature in the isotermic process is maintained fixed, ∆T = 0.
Based on the equation of energy changes in (∆U = Q - W ), obtained that
the effort made is equal to the number of calorific given. So, in the isotermic
process the following equations apply.
∆U = 0 and Q = W
On explained earlier, we have obtained an equal effort that system if the
pressure (P) and volume (V) change at all times. Business in this state is
expressed with the following equations.
By substantiateing equations P= nRT/V the following equations:

Graph of the relationship of pressure and volume in the isothermal process
From the chart, the efforts made by the system are widely stated area
below the curve (shaded area).
Isokhoric Process
The law that explains gas behavior on fixed volumes is the Lussac Gay Law.
According to Gay Lussac law, if the volume is kept constant, then the gas pressure
will be directly proportional to the temperature of the gas. The state of the gas if
the volume is made remains called an isokhoric state. While the system change
process on a fixed volume is called an isokhoric process isovolume process.
In the isoclectric process, the system does not undergo volume changes, although
a number of calorifics enter or exit the system. This gives the sense that the
system does not conduct or accept efforts. In other words, the effort made by the
system or the environment on the system is equal to zero (W = 0). So, in the
isokhoric process there are similarities:
W = 0 dan ∆U = Q
In the isokhoric process, the volume of the system is kept constant.
Because the system volume is always constant, then the system does not
perform work on the environment.
Graph of pressure and volume relationship in isokhoric process
Thus instead, the environment does not do work on the system.

THE RELATION BETWEEN CP AND CV
The Relation Between Cp and Cv
Constant volume and constant pressure heat capacities are very important in the
calculation of many changes. The ratio Cp/CV=γ appears in many expressions as
well (such as the relationship between pressure and volume along an adiabatic
expansion.) It would be useful to derive an expression for the difference Cp–CV as
well. As it turns out, this difference is expressible in terms of measureable
physical properties of a substance, such as α, κT, p, V, and T.
The difference is thus

Calorific Capacity at Fixed Volume (Cv)
Calorific capacity at a fixed volume means that the calorific is required

to raise the temperature of a single kelvin substance at a fixed volume so
that the given calorific is kept constant. Because the volume on the system
is always constant, a system cannot do the work in the environment as
well as vice versa. Thus, the calorific added to the system is used to raise
energy in a system.
The calorific capacity of a substance in a constant volume state can be
suppose the system is forced to have a fixed volume and cannot do any
work. The calorific required to change the dT temperature is with Cv as
the calorific capacity at a fixed volume.
Nevertheless, because dU = dqv so that it can be written as follows
based on these equations Cv can be expressed with a fixed volume. If one or more
variables are kept as long as the other variable changes, the derivative is referred to as a
partial derivative of the changed variable. Then for notation d is replaced with and the
variable created remains are added as subscript where this time the created fixed is the
temperature (T), so it is obtained:
Calorific Capacity at Fixed Pressure (Cp)
Gas calorific capacity is the calorific required to raise the temperature of a

single Kelvin substance at a fixed pressure of a system. So the energy
changes in, calorific, and work on this process are nothing worth zero. Let's
say the system gets a fixed pressure and can adjust or shrink when heated.
The calorific is required to produce the same temperature changes and is
stated as in this case the system can change its volume, so that the
amount of energy provided as a calorific can be returned to its environment
as a work and is not devoted to raising the system temperature.
 Therefore, in general Cv is different from Cp. Because
At cp fixed pressurized calorific capacity is different from cv fixed
volume calorific capacity, in a work required to change the system volume if
the pressure is made fixed. This work is formed in two ways: the first way is
the work of pushing back the atmosphere, and the second is the work of
stretching the bonds in the material, including weak intermoleculal
interactions.
Substitution of the equations of the first law of thermodynamics into
the energy equation in the system , so:
And Pl = P, so:
Rearrange:
Divided by dT, so:
Because , so:
Joule's experiment got:
Substitution, so:
THANK YOU

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CHANGES IN STATE AT CONSTANT

VOLUME AND TEMPERATURE

Thermochemistry is part of a broader subject called thermodynamics, which

In thermodynamics, we study changes in the state of a system, which is

Boyle's law states that at constant temperatures, gas pressure

By substantiateing equations P= nRT/V the following equations:

Graph of pressure and volume relationship in isokhoric process

Thus instead, the environment does not do work on the system.

The difference is thus

Calorific capacity at a fixed volume means that the calorific is required

Gas calorific capacity is the calorific required to raise the temperature of a

Divided by dT, so:

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