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It is the science of the relations between heat, Work and the properties of the systems.
How to adopt these interactions to our benefit?
All currencies are not equal Like US$ or UK£ etc. have a better purchasing power than Indian Rupee or Thai Baht or Bangladesh Taka Similarly, all forms of energy are not the same. Human civilization has always attempted to obtain Shaft work Electrical energy Potential energy to make life easier
If we like to Rise the temperature of water in kettle Burn some fuel in the combustion chamber of an aero engine to propel an aircraft. aircraft Cool our room on a hot humid day. Heat up our room on a cold winter night. night Have our beer cool. What is the smallest amount of electricity/fuel we can get away with? with
On the other hand we burn, - Some coal/gas in a power plant to generate electricity. - Petrol in a car engine.
What is the largest energy we can get out of these efforts?
Thermodynamics finds solutions to some of these questions
In our study of thermodynamics, we will choose a small part of the universe to which we will apply the laws of thermodynamics. We call this subset a SYSTEM. SYSTEM
The thermodynamic system is analogous to the free body
diagram to which we apply the laws of mechanics, (i.e. Newton’s Laws of Motion).
The system is a macroscopically identifiable collection of
matter on which we focus our attention (eg: the water kettle or the aircraft engine).
The rest of the universe outside the system close enough to the system to have some perceptible effect on the system is called the surroundings. The surfaces which separates the system from the surroundings are called the boundaries as shown in fig below (eg: walls of the kettle, the housing of the engine).
Types of System
Closed system - in which no mass is permitted to cross the
system boundary i.e. we would always consider a system of constant mass.We do permit heat and work to enter or leave but not mass.
No mass entry or exit
Open system- in which we permit mass to cross the system
boundary in either direction (from the system to surroundings or vice versa). In analysing open systems, we typically look at a specified region of space, and observe what happens at the boundaries of that region. Most of the engineering devices are open system.
Isolated System - in which there is no interaction between
system and the surroundings. It is of fixed mass and energy, and hence there is no mass and energy transfer across the system boundary.
Macroscopic and Microscopic Approaches
In macroscopic approach, certain quantity of matter is approach considered,without a concern on the events occurring at the molecular level.These effects can be perceived by human In microscopic approach, the effect of molecular approach senses or measured by instruments. eg: pressure, temperature motion is Considered. eg: At microscopic level the pressure of a gas is not constant, the temperature of a gas is a function of the velocity of molecules. Most microscopic properties cannot be measured with common instruments nor can be perceived by human senses
It is some characteristic of the system to which some physically meaningful numbers can be assigned without knowing the history behind it.These are macroscopic in nature. Invariably the properties must enable us to identify the system.
Categories of Properties
Extensive property: whose value depends on the size or extent of the system (upper case letters as the symbols). eg: Volume,Mass (V,M).If mass is increased, the value of extensive property also increases. Intensive property: whose value is independent of the size or extent of the system. eg: pressure, temperature (p, T).
It is the value of an extensive property per unit mass of system. (lower case letters as symbols) eg: specific volume, density (v, ρ). It is a special case of an intensive property.
Most widely referred properties in thermodynamics:
Pressure; Volume; Temperature; Entropy; Enthalpy; Internal energy
It is the condition of a system as defined by the values of all its properties. It gives a complete description of the system. Any operation in which one or more properties of a system change is called a change of state.
It is a quantity of mass that is homogeneous throughout in chemical composition and physical structure. e.g. solid, liquid, vapour, gas. Phase consisting of more than one phase is known as heterogeneous system .
Path And Process
The succession of states passed through during a change of state is called the path of the system. A system is said to go through a process if it goes through a series of changes in state. Consequently: A system may undergo changes in some or all of its properties. A process can be construed to be the locus of changes of state Processes in thermodynamics are like streets in a city eg: we have north to south; east to west; roundabouts; crescents.
Types of Processes
•Isothermal (T) •Isobaric (p) •Isochoric (v) •Isentropic (s) •Isenthalpic (h) •Isosteric (concentration) •Adiabatic (no heat addition or removal)
As a matter of rule we allow one of the properties to remain a constant during a process. Construe as many processes as we can (with a different property kept constant during each of them) Complete the cycle by regaining the initial state
In thermodynamics a quasistatic process is a process that happens infinitely slowly. In practice, such processes can be done by performing them "very slowly". A quasistatic process often ensures that the system will go through a sequence of states that are infinitesimally close to equilibrium, in which case the process is typically reversible. An example of this is the slow heat exchange between two bodies at two finitely different temperatures, where the heat exchange rate is controlled by an approximately adiabatic partition between the two bodies no matter how slowly the process takes place, the states of the two bodies are never infinitesimally close to equilibrium.
A system is said to be in an equilibrium state if its properties will not change without some perceivable effect in the surroundings. Equilibrium generally requires all properties to be uniform throughout the system. There are mechanical, thermal, phase, and chemical equilibria Nature has a preferred way of directing changes.
- water flows from a higher to a lower level - Electricity flows from a higher potential to a lower one - Heat flows from a body at higher temperature to the one at a lower temperature
Types of Equilibrium
Between the system and surroundings, if there is no difference in
Pressure Potential Concentration of species Temperature Mechanical equilibrium Electrical equilibrium Species equilibrium Thermal equilibrium
No interactions between them occur. They are said to be in equilibrium. Thermodynamic equilibrium implies all those together. A system in thermodynamic equilibrium does not deliver anything.
Definition Of Temperature and Zeroth Law Of Thermodynamics
Temperature is a property of a system which determines the degree of hotness. eg: A hot cup of coffee is at a higher temperature than a block of ice. On the other hand, ice is hotter than liquid hydrogen. Thermodynamic temperature scale is under evolution. when two systems are at the same temperature they are in thermal equilibrium (They will no exchange heat).
“If two thermodynamic systems are in thermal equilibrium with a third, they are also in thermal equilibrium with each other.” other
All temperature measurements are based on this LAW.
Three temperature scales are in common use in science and industry. Two of those scales are SI metric: The degree Celsius (°C) scale was devised by dividing the range of temperature between the freezing and boiling temperatures of pure water at standard atmospheric conditions (sea level pressure) into 100 equal parts. The kelvin (K) temperature scale is an extension of the degree Celsius scale down to absolute zero, a hypothetical temperature characterized by a complete absence of heat energy.
The degree Fahrenheit (°F) non-metric temperature scale was devised and evolved over time so that the freezing and boiling temperatures of water are whole numbers, but not round numbers as in the Celsius temperature scale.
Some baseline temperatures in the three temperature scales:
First law of thermodynamics
“The first law of thermodynamics is often called the Law of Conservation of Energy. This law suggests that energy cannot be created nor destroyed .It can only be transferred from one system to another in different forms. “
When a closed system undergoes a cycle the cyclic integral of heat is equal to the cyclic integral of work. Mathematically δQ = δW
For a process we can have Q=0 or W=0 We can extract work without supplying heat(during a process) but sacrificing the energy of the system. We can add heat to the system without doingwork(in process) which will go to increasing the energy of the system. Energy of a system is an extensive property
When we need to derive some work, we must expend thermal/internal energy. The first law introduces a new property of the system called the energy of the system. HEAT and WORK are not properties because they depend on the path and end states.
To sum up:
I law for a cycle: I law for a process is For an isolated system Therefore ΔE=0 δQ = δW Q-W = ΔE Q=0 and W=0.
Perpetual Motion Machines-First Kind
A perpetual motion machine of the first kind is one which produces power without energy uptake. Such a machine would, once started, operate indefinitely. This is forbidden by the law of conservation of energy.
The above engine is not possible. Perpetual motion machine of the second kind is not possible.
II Law of Thermodynamics
There are many ways of formulating the 2nd Law of Thermodynamics.
Kelvin-Planck Statement “It is impossible to construct a heat engine which will operate continuously and convert all the heat it draws from a reservoir into work” Implications
II Law applies only for a cycle - not for a process!! !!There is nothing like a 100% efficient heat engine!!
All processes in nature occur unaided or spontaneously in one direction. But to make the same process go in the opposite direction one needs to spend energy. Heat flows from a body at higher temperature to a body at lower temperature
A hot cup of coffee left in a room becomes cold. We have to expend energy to rise it back to original temperature Fluid flows from a point of Water on a tank down from higher pressure or potential spontaneously. To get it back to the tank you have to spend energy
All processes occur unaided in one direction but to get them go in the other direction there is an expenditure - money, energy, time, peace of mind? ….
“It is impossible to construct a heat pump which will transfer heat from a low temperature reservoir to a high temperature reservoir without using external work.”
The existence of a magic fridge which is forbidden by the First Law of Thermodynamics. Heat goes into the fridge, heat goes out, no energy is destroyed. So we are in genuine need of a second law to say that this can't be done.
The Clausius statement implies the Kelvin-Planck statement
Suppose that we violated the Kelvin-Planck statement and constructed a magic heat engine. Then we could take its work output and use it to power fridge, which draws heat from a cooler thermal reservoir and discharges this heat into the thermal reservoir that the magic heat engine runs off, Then this combined system of the fridge and the magic heat engine is a magic fridge, since it moves heat from a lower temperature to a higher temperature while having no other effect on its environment - in particular, without having an external power source.
“A measure of the disorder or randomness in a closed system.”
Quantitatively symbolized by S, is defined by the differential quantity
dS = δQ / T,
where δQ is the amount of heat absorbed in a reversible process in which the system goes from one state to another T is the absolute temperature. Entropy is one of the factors that determines the free energy of the system.
- Spontaneous changes occur with an increase in entropy
It is an extensive state function - It accounts for the effects of irreversibility in thermodynamic systems.
Whenever energy (in whatever form) is out of equilibrium with its surroundings, a potential exists for producing change that, following the second law, is spontaneously minimized.
- The most efficient heat engine cycle allowed by physical laws - It consists of two isothermal processes and two adiabatic processes. - To approach the Carnot efficiency, the processes involved in the heat engine cycle must be reversible and involve no change in entropy. - The Carnot cycle is an idealization
Carnot cycle is a four stage reversible sequence consisting of 1. adiabatic compression 2. isothermal expansion at high temperature 3. adiabatic expansion 4. isothermal compression at low temperature 5. back to stage 1 and continue. The efficiency of a perfect engine is given by
Note that the efficiency of a perfect heat engine, following a Carnot cycle, is always less than 100%. Real heat engines involve losses to friction, among other things. When energy is lost to friction, it is irrecoverable. Thus the real heat engine is less efficient that the Carnot cycle engine.
Importance of the Carnot's Cycle
- The Carnot's cycle is important since it describes an optimal system, where heat energy is used at its best. - It can be used to describe theoretical limits of the transformation of heat into physical work. - One of the consequences of the second law of thermodynamics is that heat cannot be transformed completely in work. Heat is a type of energy that has high entropy.. Thus, this gives a limit on the amount of energy that can be tranfered from heat to work. Carnot's cycle is a physical expression of the consequence of the 2nd law of thermodynamics for engines and other related physical systems.