What is a Process ?

In the previous lesson, we defined a state as the condition of a substance or system that is determined by its properties. We also learned that when the value of a property of the system changes, the system is in a different state. This is called a process .

What is a Process Path ?

In the previous lesson, we defined a state as the condition of a substance or system that is determined by its properties. We also learned that when the value of a property of the system changes, the system is in a different state. This is called a process A process

path is the series of states that a system passes through as it moves from an

initial state to a final state.

Ch1, Lesson D, Page 2 - What is a Process Path ?

During a process, the state of a system does not just abruptly jump from the initial state to the final state. No, the properties of the system change gradually from their initial values to their final values. So, during a process, the system moves through many different states before it reaches the final state.

The collection of all of the states that the system moves through during a process is called the process path. It is important to note that there are an infinite number of different process paths that lead from the initial state to the final state. Each of these different process paths represents a DIFFERENT process ! Now, lets talk about some special types of processes.

Special Types of Processes

In the previous lesson, we defined a state as the condition of a substance or system that is determined by its properties. We also learned that when the value of a property of the system changes, the system is in a different state. This is called a process .

We often study processes in which one property remains constant throughout the process. These types of processes have special names, such as: Isobaric - constant pressure

Isothermal - constant temperature

Isochoric - constant volume

Initial State
Ch1, Lesson D, Page 3 - Special Types of Processes

Final State

It is often helpful to consider processes in which one property remains constant. When one property remains constant, the process is generally easier to analyze. Youll learn more about that later. Anyway, these processes are so useful that they have their own names. The names usually begin with the prefix iso. Iso just means constant. So, an isothermal process is one in which the temperature of the system does not change.

In an isobaric process, the pressure does not change and in an isochoric process, the volume does not change. Well learn about some other iso type processes later in the course. It is customary to draw the process path for a process in which one property remains constant as either a vertical or horizontal line, as shown here. Well learn more about why drawing a process path is helpful in chapter 3.

What is a Thermodynamic Cycle ?

A cycle is a very special type of process in which the initial and final states are the same!

Initial State Final State

A system completes a thermodynamic cycle when it undergoes two or more processes and the system returns to its initial state. Thermodynamic cycles are a central topic in this course and we will discuss them in almost every chapter!
Ch1, Lesson A, Page 1 What is Thermodynamics?

A cycle is a process that begins and ends in the same state. You are probably wondering how such a process could be useful. Well, during the cycle, the system can put out or take energy in the form of heat and work. In fact, heat and work are the only forms of energy that CAN cross the boundary of a closed system ! Remember, in this course, heat and work are what its all about ! So, cycles are very important. Just one more topic and well wrap up this lesson.

What is Equilibrium ?
Equilibrium - A system is in equilibrium when no unbalanced potentials or driving
forces exist within the system boundary. The state of an isolated system at equilibrium cannot change. Equilibrium requires that all four of the different types of equilibria exist within the system simultaneously. 1. Thermal Equilibrium No temperature driving force exists within the system. 2. Chemical Equilibrium No chemical driving force exists within the system.

The temperature throughout the system is the same (uniform), so no heat transfer can occur. The forward rate of each chemical reaction is exactly equal to the reverse rate of the same reaction.

3. Phase Equilibrium The rate at which molecules are moving into No mass transfer driving force exists within the system. each phase is exactly equal to the rate at which molecules are moving out of that phase. 4. Mechanical Equilibrium For example, the pressure within a system in No unbalanced forces exist within the system. mechanical equilibrium is not necessarily uniform. The pressure at the bottom of a tank of water is higher than the pressure at the top, for instance. However, because the forces within the fluid tank are balanced, the pressure at each point within the system remains constant at mechanical equilibrium.
Ch1, Lesson D, Page 5 - What is Equilibrium ?

A system at equilibrium contains no un-balanced driving forces or potentials. It isnt that there or no forces or no motion within the system, it is that all forces and motion are balanced. Recall that an isolated system does not exchange mass or energy with its surroundings. Once an isolated system reaches equilibrium, its state can never change ! After all, what could possibly be the driving force for such a change ? OK. When we say that a system is in equilibrium, it means that the system is in ALL FOUR types of equilibrium listed here. Be sure to roll your mouse pointer over each gray box to see the roll-over text. A system is in THERMAL EQUILIBRIUM when the temperature is uniform.

A system is in CHEMICAL EQUILIBRIUM when all chemical reactions are going at the same rate in the forward direction as they are in the backward direction. So, reactions can occur, but they are BALANCED by the reverse reaction. So, no NET change occurs. A system is in PHASE EQUILIBRIUM when the mass and composition of all phases within the system remain constant. This is similar to chemical equilibrium. If 300 molecules per second are evaporating from the liquid phase into the gas phase, then 300 molecules per second must also be condensing from the gas phase into the liquid phase. This doesnt mean that no molecules are changing phases. It just means that there can be no NET change in the mass or composition of any phase at equilibrium. A system is in MECHANICAL EQUILIBRIUM when all of the mechanical forces within the system are balanced. You may be wondering how any vessel of liquid could ever be at equilibrium within a gravitational field. The gravitational field causes the pressure to be greater at the bottom of the tank than it is at the top of the tank. The catch is that the higher pressure near the bottom of the tank is BALANCED by the weight of the liquid on top of it. So, no NET force acts on the fluid and mechanical equilibrium is possible. Students often wonder how long they should wait for a system to reach equilibrium. The answer is that you must wait FOREVER for a system to reach perfect equilibrium. That isnt very practical, but you still need to wait a very long time for a system to even APPROACH equilibrium. Nonetheless, we will often consider the states of systems to be reasonable approximations of equilibrium.

What is Quasi-Equilibrium ?
No system can be in complete equilibrium as it undergoes a real process. However, some processes are almost in perfect equilibrium throughout the process.

Quasi-Equilibrium Process - A process during which the system only

deviates from equilibrium by an infinitessimal amount.
One example of a quasi-equilibrium process is a piston and cylinder device in which the contents are compressed very slowly.

As the piston compresses the gas inside the cylinder, the pressure inside the gas remains very nearly uniform at all times during the process. So, the system never deviates significantly from mechanical equilibrium.

Ch1, Lesson A, Page 1 What is Thermodynamics?

Whenever a system undergoes a process, it cannot be at equilibrium, because SOME driving force is causing the state of the system to change, right ? A quasi-equilibrium process is a process in which the driving forces that change the state of the system are infinitesimally small. With such tiny driving forces though, quasi-equilibrium processes proceed VERY slowly ! The compression process shown here could only be considered to be a quasi-equilibrium process as long as the piston moved slowly enough that the pressure in the cylinder remained uniform at all times. If the pressure were not uniform, then some regions of the gas would experience an unbalanced force and they would accelerate. That would indicate the system was not at mechanical equilibrium and the process could not be considered to be a quasi-equilibrium process. Believe it or not, Ive presented all the nomenclature youll need to get started in your study of thermodynamics. Read the Lesson Summary and try the quiz just to be sure you have retained everything I have presented Then, move on to Lesson E and learn about the three most important properties in this course: pressure, volume and temperature.