“1ST Law of Thermodynamics”

On this topic, we are going to tackle about the 1st law of thermodynamics, also terms such

as system, surroundings, universe, open, closed, and isolated systems, as well as reversible and

irreversible processes will be encountered. But first we will talk about thermodynamics and its

first law. Thermodynamics is the study of heat energy and other types of energy, such as work,

and the various ways energy is transferred within chemical systems. “Thermo” refers to heat,

while “dynamics” refers to motion. It literally means “moving or evolving heat”. Sadi Carnot is

considered as one of the founders of thermodynamics. No work has been done if the object does

not move. Work is a measure of energy expended by moving an object, usually considered to be

force times distance. The object or collection of objects is called a system. For example, a system

could refer to a stream, an engine, or the human body.

Everything around the system is referred to as surroundings. The system and the

surroundings constitute the universe. A system is considered closed when no mass enters or

leaves the system. However, energy may be exchanged with surroundings. An example of a

closed system is a balloon as it is being heated so that the gas inside it expands. An open system

is one where mass and energy may be added or removed from the system. Plants and animals are

open systems because mass enters them in the form of food and oxygen. Mass also leaves these

systems in the form of waste products. A system is isolated if neither mass nor energy enters or

leaves the system. This law of thermodynamics compacts with the total amount of energy in the

universe. A version of the law of conservation of energy, specialized for thermo dynamical
systems, that states that the energy of an isolated system is constant and can neither be created

nor destroyed. Just like many power plants and engines operates by turning heat energy into

work. A heated gas can do work on mechanical turbines or pistons, causing them to move. This

law may also be considered as a restatement of the law of conservation of energy. This law of

thermodynamics applies the conservation of energy principle to systems where heat transfer and

doing work are the methods of transferring energy in and out of the systems. The first law may

be written as Q = ΔU + W, where Q is the heat added to the system. Heat, change in internal

energy, and work are expressed in Joules. Using this equation, the following sign conventions

must be applied. First, Q is positive (+) when heat is added to the system and negative (-) when

heat is removed from the system. Second, W is positive (+) when work is done by the system and

negative (-) when work is done on the system. This law also states that this total amount of

energy is constant. In other words, there has always been, and always will be, exactly the same

amount of energy in the universe. Energy exists in many different forms. Energy can be

transferred from place to place or changes between different forms, but it cannot be created and

destroyed. The transfers and transformations of energy take place around us all time. Now, we

are going to talk about the processes, A reversible process is one in which the system and its

surroundings can be returned to their initial state before undergoing a process. The opposite of

this process is called irreversible. Examples of irreversible processes are growing old, breaking a

glass, and burning pieces of paper. A cycle is a series of processes that states and ends at the

same conditions. Examples of a cycle are water cycle, refrigeration cycle, and carbon cycle.

Internal energy is the sum of the kinetic and potential energies possessed by the molecules of an

object due to their motions and positions relative to each other. The change in the internal energy

(ΔU) of a gas can be obtained using the formula ΔU = nCv ΔT, where n is the number of moles,
Cv is the molar specific heat at constant volume, and ΔT is the change in temperature. Any

thermodynamic system possesses a state variable called the internal energy (E). This picture

below shows between any two equilibrium states, the change in internal energy is equal to the

difference of heat transfer into the system and work done by the system. Work is the total

amount

amount of work done by a varying force may be solved graphically and analytically by calculus.

Given a graph of force versus displacement along the direction of force, the work done is the

area bounded by the graph and the x-axis. Getting the area under a curve is actually performing

integration. Work, therefore, is W = f x1x2 Fdx. However, the force F can be expressed as the

product of pressure and area. But Adx = change in volume = dV. Therefore, W = fv1v2PdV. A

graph called PV diagram, is a graph of pressure versus volume as being used instead of graph of

force versus displacement. When a system changes from it initial to final state, it may undergo a

series of intermediate states. This series of intermediate states between the initial and final states

is commonly termed as path in thermodynamics. Variables that depend only on the initial and
final states and not on the path taken are called state variables. Variables that depend on the path

are called process variables. The change in internal energy is a state variable. Heat and work are

process variables. Next, we will we talking about thermodynamics processes and PV diagrams, a

thermodynamic process is a change from an initial state to a final state of a system that usually

involves a change in its pressure, volume, or temperature. These processes are isochoric,

isobaric, isothermal and adiabatic. An isochoric process is also called a constant volume process.

Since, volume is constant there is no work done during an isochoric process. All the heat added

to the system goes into increasing its internal energy. A vertical line in a PV diagram represents

an isochoric process. This vertical line is called an isochor. Heating in a closed rigid container is

an example of an isochoric process. An isobaric process is also referred to as a constant pressure

process. The work done by the system, change in its internal energy, and the heat added to the

system are not zero in this process. The work done during isobaric process is equal to the product

of the constant pressure and the change in volume. A horizontal line called an isobar represents

an isobaric process in a PV diagram. A change of phase such as boiling is an example of a

constant pressure process. An isothermal process is also called a constant temperature process.

Here, the change in internal energy is equal to zero. An adiabatic process is a process where

there is no transfer occurring between the system and it surroundings. This could be achieve if

the system is well-insulated or that the process takes place very fast, leaving no time for heat to

flow between the system and the environment. Since heat is equal to zero, then the change in

internal energy is equal to the negative of work. Here are the different diagrams of

thermodynamics processes.
 Now, we will try to solve for PV diagrams and thermodynamics processes. The problem

is two moles of an ideal gas are taken around the cycle as shown in the PV diagram. Calculate

the (a) temperature at states A, B, and C, (b) change in internal energy of the gas, (c) total heat,

and (d) total work done by the gas for the entire cycle.

Solution:

We are given the following: n = 2 and y = 1.4.

a. To solve for the temperature at each state, the ideal gas law,

PV = nRT, is used.

For state A: (2.00x105 Pa)(2.0x10-3m3) = 2(8.314 J/mol K) Ta

Ta = 24.06 K =24 K

For state B: Tb = Ta = 24K since process AB is isothermal.

For state C: (0.38x105 Pa) (4.0x10-3m3) = 2(8.314 J/mol K) Tc

Tc = 9.14K K = 9.1K

b. We need to solve for Cv:

y = Cp/Cy = 1.4; Cp = 1.4Cv

Using the equation,

Cv + 8.314 J/mol K = 1.4 Cv

Cv = 20.785 J/mol K = 20.8 J/mol K

Recall that internal energy is a state variable. Hence, the change in internal energy depends only

on the initial state and final state. Since for a cycle, the initial and final states are identical.

c. For process AB, W = nRT In V2/V1, substituting values,

W = 2(8.314 J/mol K) In 4.0x10-3m3 / 2.0x10-3m3 = 276.62 J = 280 J

 For process BC, W = 0 since the process is isochoric.

For process CA, from the equation, -W = ΔU = -620 J

For the whole cycle, Q = 276.62 J + (-619.84 J) = -343.22 J = -343 J

d. Using the first law of thermodynamics,

Work for the cycle = ΔU of the cycle + Q for the cycle = 0 + Q = -343 J.

This first law of thermodynamics states that the change in the internal energy ΔU of a

closed system is equal to the amount of heat Q supplied to the system, minus the amount of work

W done by the system on its surroundings. An equivalent statement is that perpetual motion

machines of the first kind are impossible.

References:

http://nuclearpowertraining.tpub.com/h1012v1/css/First-Law-Of-Thermodynamics-Summary-94.htm

https://courses.lumenlearning.com/introchem/chapter/the-first-law-of-
thermodynamics/#targetText=The%20first%20law%20of%20thermodynamics%20deals%20with%20the
%20total%20amount,amount%20of%20energy%20is%20constant.&targetText=According%20to%20the
%20first%20law%20of%20thermodynamics%2C%20energy%20can%20be,cannot%20be%20created
%20or%20destroyed.

https://www.khanacademy.org/science/physics/thermodynamics/laws-of-thermodynamics/a/what-is-
the-first-law-of-thermodynamics?
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