Introduction in Thermodynamics

LESSON 1A What is Thermodynamics? The word thermodynamics was coined by William Thompson (Lord Kelvin) in 1749. It comes from the Greek words: therme (heat) and dynamis (power). The name heat-power is appropriate because thermodynamics developed from efforts to explain the conversion of heat into power by steam engines.

Timeline of the Early Developments of Thermodynamics 1712 Newcomen invented an improved steam engine 1798 Count Rumford began canon-boring experiments (dealing with the conversion of work into heat) 1840s Mayer (1842), Joule (1847) and Helmholtz (1847) independently arrived at the conservation of energy principle Carnot published "Reflections on the Motive Power of Fire" 1824 Clausius formulated the Second Law of Thermodynamics 1850
Reference : http://www.learnthermo.com/T1-tutorial/ch01/lesson-A/pg01.php
THERMODYNAMICS: the science of energy, specifically heat and work, and how the transfer of energy effects the properties of materials Thermodynamics is a physical science that studies the effects on material bodies, and on radiation in regions of space, of transfer of heat and of work done on or by the bodies or radiation. It interrelates macroscopic variables, such as temperature, volume and pressure, which describe physical properties of material bodies and radiation, which in this science are called thermodynamic systems. Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines, particularly through the work of French physicist Nicolas Lonard Sadi Carnot (1824) who believed that the efficiency of heat engines was the key that could help France win the Napoleonic Wars.[1] Scottish physicist Lord Kelvin was the first to formulate a concise definition of thermodynamics in 1854: Reference : http://en.wikipedia.org/wiki/Thermodynamics

LESSON 1B What are Dimensions ? For example, consider water in the beaker shown here: Can be calculated or derived by multiplying or dividing fundamental dimensions. Examples: area, velocity, density and volume 2. Derived Dimensions - Mass, Length, Time, Temperature, Moles and sometimes Force Fundamental dimensions can be directly measured or are independentlydefined. All other dimensions can be obtained from the fundamental dimensions. 1. Fundamental Dimensions - There are two types of dimensions. In science and engineering, numbers without units are not useful (unless they happen to be dimensionless).

Mass Density has derived dimensions made up of a combination of fundamental dimensions: is a fundamental dimension.

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LESSON 1C Three Key Terms For The Study of Thermodynamics

1. In Lesson 1A, we learned a little bit about the history and nature of thermodynamics. 2. In Lesson 1B, we learned the importance of dimensions and units and how to use them to help us solve problems. 3. Now, we need to learn the meaning of some key terms that we will use throughout this course. That is the goal of this lesson. 4. In this lesson, we will study the terms system, state and property. 5. You are probably already familiar with these terms, but they have very specific meanings when they are applied to thermodynamics. 6. Because these three terms form the basis for this entire course, it is very important to understand them very well before we move on.

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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 .
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LESSON1D Volume
Pressure, volume, and temperature are the three most important properties in classical thermodynamics because they are the easiest properties to measure. Volume The space occupied by the system. An important extensive property of a system. Units: SI = m3, AE = ft3

Molar Volume The volume of the system per mole of molecules within the system. (Intensive)

Density - The volume of the system per unit of mass within the system. (Intensive)

Specific Volume -The mass per unit volume of the system.

What is Pressure ? Pressure

Force per unit area exerted by a fluid (gas or liquid) on a solid surface. Pressure force acts in all directions and is due to the sum of all the random collisions of fluid molecules with the solid surface. The pressure force always acts on a surface in a direction perpendicular or normal to the surface.

SI Units: Pascal (Pa) 1 Pa = 1 N/m2 1 atm = 101.325 kPa AE Units: lbf /in2 (psia or psig) 1 psi = 6.895 kPa

1 kPa = 1000 Pa 1 bar = 100 kPa

1 MPa = 106 Pa

1 atm = 14.696 psia

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Types of Pressure: Definitions Pressure Force per unit area exerted by a fluid (gas or liquid) on a solid surface.

Absolute Pressure - Pressure measured relative to an absolute vacuum (absolute zero pressure). Gage Pressure - Pressure greater than atmospheric pressure that are measured relative to atmospheric pressure. Gage pressure is the difference between the absolute pressure and atmospheric pressure : Pgage = Pabs - Patm Vacuum Pressure
-

Pressure less than atmospheric pressure that are measured relative to atmospheric pressure. Vacuum pressure equals atmospheric pressure minus the absolute pressure: Pvac = Patm Pabs
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The

Barometer Equation Where is the pressure greater, at the surface of the water, 1, or at the bottom of the tank, 2 ? P2 > P 1 because atmospheric pressure plus the weight of all of the water in the tank is pushing down on the fluid at the bottom of the tank. If we assume the fluid in the tank is at equlibrium, then the forces acting on it must be balanced.

Pressure forces at the bottom and top of the water act in opposite directions and the weight of the water acts in the downward direction:

The

Barometer Equation

Ch1, Lesson E, Page 4 - The Barometer Equation

Lets start by looking at the open tank of water, shown here. Where do you think the pressure is greater, at the surface of the water or at the bottom of the liquid in the tank ? Ill bet you know that P2 is greater than P1. Basically, at the bottom of the tank you have the weight of all of the atmosphere pushing down PLUS all the weight of all the water in the tank pushing down. As a result the pressure is greater at the bottom of the tank. Now, lets see if we can quantify the difference between P1 and P2. If the water in the tank is at equilibrium, then all the forces acting on it must be balanced. In particular, the force acting upwards on the water due to the pressure at the bottom of the tank must be equal to the force due to atmospheric pressure acting downward on the surface of the water PLUS the weight of the water itself. This is exactly what the first equation says. The forces due to pressure are just the pressure multiplied by the area over which the pressure acts. You may be worried about some horizontal component of the pressure force due to waves on the surface of the water, but we are only interested in the vertical component of the pressure force in this case. I used Newton 1st law to express the weight of the water.

In the 2nd equation, I show how we can express the mass of the water in terms of its density, the cross-sectional area of the tank and the depth of the water, h. When we plug this expression for the mass back into our force balance, an interesting thing happens. The cross-sectional area cancels out. This makes sense though. When you dive into a pool, the pressure depends on how deep the pools is, but it doesnt depend on the surface area of the pool, now does it ? After a slight rearrangement we obtain the Barometer Equation. This equation tells us how pressure varies with depth in a gravitational field. It may be interesting to note that this equation is slightly easier to apply in the AE System than in the SI System. Why you may ask ? Because in the AE System, g over gc = 1 lbf / lbm. Cool. Now, lets see what we can do with this equation.

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The Basic Manometer

A simple device to modest pressure differences is the manometer. If P4 = 1 atm, then what is the pressure of the gas inside the tank ? If the tank contains a gas and gas << m, then: What is the relationship between P1 and P3 ?

The pressures at two points within a fluid are equal if :

The two points are connected by a stagnant fluid All of the fluid in the path connecting the two points has the same density. How do these facts help us determine Ptank ?

The Manometer Equation

The Differential Manometer A differential manometer measures the pressure difference between two points, in this case P1 - P5. Given h, m and w, determine P1 - P5. What do we know ?

Apply the Barometer Equation to determine P2relative to P1 and P3 relative to P5.

The Differential Manometer Equation Cancel and then group terms to get:

Other Types of Pressure Measurement Devices Pressure Measurement Devices: Bourdon Tube Pressure Gauge (C-type) Pressure Transducers

P = 1 atm

P = 9.5 atm

As the pressure inside the Bourdon tube increases, the tube deflects and this action, through a linkage and a pinion gear, rotates the needle on the gauge. Ch1, Lesson E, Page 7 - Other Types of Pressure Measurement Devices
Common pressure measurement devices include the Bourdon Gauge and the pressure transducer. Pressure gauges are common in existing industrial plants, but pressure transducers are more common in laboratories and are becoming more common in new industrial plants. Two C-type Bourdon Gauges are shown here. At atmospheric pressure the curled tube inside the gauge is undeflected or relaxed and the gauge reads a GAUGE pressure of ZERO. At higher pressures, the Bourdon tube begins to uncoil. This action is translated into a rotation of the gauge needle by a series of gears. This gauge reads 8.5 atm GAUGE because the pressure within the tank is 8.5 atm above atmospheric pressure.

There are many different types of Bourdon Gauges. The C-type is just the easiest to sketch ! They all work in a very similar manner. Pressure transducers are entirely different. Usually, pressure transducers work by measuring the deflection of a diaphragm placed between two regions at different pressures. When the transducer is built to read absolute pressure, one side of the diaphragm is exposed only to a vacuum. Transducers designed to read gauge pressure have one side open to the atmosphere. In either case, the deflection of the diaphragm is generally measured using strain gauges. Pressure transducers are small, inexpensive and rugged. In addition, because they produce an electrical signal, it is very easy to digitize the signal and record the pressure. That explains why they have become so popular. Now, lets wrap us this lesson with a look at temperature and temperature measuring devices.

What is Temperature?
Temperature is a physical property of matter that quantitatively expresses the common notions of hot and cold. Objects of low temperature are cold, while various degrees of higher temperatures are referred to as warm or hot. Quantitatively, temperature is measured with thermometers, which may be calibrated to a variety of temperature scales.
Thermal vibration of a segment of protein alpha helix. The amplitude of the vibrations increases with temperature.

Temperature plays an important role in all fields of natural science, including physics, geology, chemistry, atmospheric sciencesand biology. In a microscopic explanation, the temperature of a body varies with the speed of the fundamental particles that it contains, raised to the second power. Therefore, temperature is tied directly to the mean kinetic energy of particles moving relative to the center of mass coordinates for that object.

We think of temperature as the numerical measurement of "hotness" or "coldness".

From our senses, we assign the "hotter" cup with a higher temperature.

Ch1, Lesson E, Page 8 - What is Temperature?

The concept of temperature seems to be pretty straightforward as well. We all know hot and cold when we tough it, right ? But our senses can deceive us. When we perceive an object to be hot, what our senses are really telling us is that the rate of heat transfer into our skin from the object is high. That doesnt always indicate that an object is hot. Well clear up this little mystery in chapter 4. For now, we need to think about how we can QUANTIFY hotness or temperature. Flip the page to see how.

The Zeroth Law of Thermodynamics Zeroth Law of Thermodynamics states that if two objects are in thermal equilibrium with a third object then they are equilibrium with each other. This law may seem obvious but it very important because it allows the temperature of an object to be determined by calibrating it with an object of known temperature. Liquid Thermometer

Thermometers are common temperature measuring devices that are based on the zeroth law of thermodynamics. Thermocouples are are electrical devices in which two different metals are bonded. A small electrical potential, called a junction potential, is created by the junction between the two metals. The juntion potential increases with increasing temperature.

Both thermometers and thermocouples must be calibrated using substances at known temperatures, like the normal boiling point and melting point of water.

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Temperature Scales in the SI & AE Systems Temperature Scales Used in the SI System: 1. The Celsius temperature scale uses degrees Celsius (oC). Defined such that: 0oC corresponds to the freezing point of water 100oC corresponds to the boiling point of water. 2. The Kelvin temperature scale is an absolute or thermodynamic scale in which temperature is measure in Kelvins (K). 1 K = 1oC. Conversion Factors T(K) = T(oC) + 273.15 T(R) = T(oF) + 459.67 T(R) = 1.8 T(K) T(oF) = 1.8 T(oC) + 32 Temperature Scales Used in the AE System: 1. The Fahrenheit temperature scale uses degrees Fahrenheit (oF). Defined such that: 32oF corresponds to the freezing point of water 212oF corresponds to the boiling point of water. 2. The Rankine temperature scale is an absolute or thermodynamic scale in which temperature is measure in degrees Rankine (oR). 1oR = 1oF.

The Ideal Gas Thermometer

A bulb containg a very small amount of an ideal gas is allowed to come to thermal equilibrium with the system, in this case, a bath of water. The right leg of the manometer is raised or lowered to keep the level of the manometer fluid in the left leg constant. We do this to keep the volume that the ideal gas occupies constant. Use the manometer reading, h, to calculate the pressure of the gas. Ideal Gas "Law": P V = n R T One equation, but three unknowns: V, n, & T

Two problems:
1. The gas thermometer must be calibrated 2. No real gas is actually an ideal gas except

at zero pressure !

Flip the page to see how these problems can be resolved to make our gas thermometer more accurate. Gas Thermometer:

Ch1, Lesson E, Page 11 - The Ideal Gas Thermometer

A gas thermometer consists of a small bulb that contains the gas and is connected by a small tube to a manometer. The density of the manometer fluid must be much greater than the density of the gas if the device is going to work well. As the gas comes to thermal equilibrium with some warm water, it expands and pushes the manometer fluid up into the right leg of the manometer, as shown here. The trick is that you can MOVE the right manometer leg up and down.

You must raise or lower the right leg to adjust the level of the manometer fluid in the left leg back to its original level. You do this in order to keep the volume that the gas occupies CONSTANT. You use the manometer reading, h, to calculate the pressure of the gas. You are probably familiar with the Ideal Gas Law, but if not, dont worry. Well lear a lot more about it in the next chapter. We have a problem though. We know P and R, but the volume, temperature and number of moles of gas are unknown and we only have ONE equation. We have some other issues as well. We know that thermometers generally need to be calibrated and the gas thermometer is no exception. The other problem is that there is NO SUCH THING as an ideal gas except at ZERO pressure ! Why do we bother dealing with all these problems ? Because the gas thermometer is a very precise instrument when it is built and used properly.

Calibrating an Ideal Gas Thermometer Measure the pressure in the gas thermometer when it has equilibrated with a system at a well known reference temperature, such as the triple point of water, Tref = 0.01oC. Measure the pressure in the gas thermometer when it has equilibrated with your system at the unknown temperature, Tunk.

If you repeat this experiment with different masses of gas in the bulb

and extrapolate back to zero pressure, you will find that the intercept is absolute zero or -273.15 oC. Therefore, the ideal gas temperature scale is identical to the Kelvin scale as long as the gas in the bulb does not condense or dissociate. If you use a different gas in the bulb, you will get a different slope, but the intercept will still be -273.15 oC. Ch1, Lesson E, Page 12 - Calibrating an Ideal Gas Thermometer
Calibrating a gas thermometer is similar to calibrating any other type of thermometer. You must let the gas bulb equilibrate thermally with a system at a very well known reference temperature, such as the triple point of water. Next, you use the manometer to measure the pressure. Ill call this pressure Pref. Then, you let the gas bulb equilibrate with the unknown system and then measure the pressure. Ill call this pressure Punk. If you write the Ideal Gas Law for each of these two systems and take the ratio of the two equations, as shown here, some good things happen. V, n and R all cancel. Two of our unknown variable have cancelled. Cool ! Now, all we need to do is solve for Tunk. The result appears in the yellow box. This equation looks simple enough, right ? Sure, but dont forget that these temperatures must be ABSOLUTE ! So, use Kelvin or Rankine. Now, lets think about this thermometer for a moment. What would happen if we had put LESS gas in the bulb but we adjusted the gas volume to the same point ? Well, ALL of the pressures that we measure would be lower. Consider the three curves for different masses of gas in the bulb shown in the diagram: A, B and C. The interesting part is that all of the lines converge at zero pressure to a temperature of 273.15oC or 0 K ! What does this mean ? It means that, as long as the gas in the bulb doesnt condense or dissociate (at very high temperatures), the ideal gas thermometer is a thermodynamic temperature scale that exactly coincides with the Kelvin or Rankine scales ! This is very cool, but has this little thought experiment given you any ideas about how to handle the problem that real gases are not ideal gases ? What happens as we put less and less gas in the thermometer bulb ? Flip the page and lets see.

High Precision Gas Thermometry Extrapolating Gas Thermometry to Zero Pressure Use the gas thermometer to estimate Punk / Pref using the method described on the previous page.

Repeat the procedure with a smaller and smaller mass of gas in the bulb. Note that the volume occupied by the gas must be same in all trials.

Plot Punk / Pref as a function of Pref, as shown here.

Extrapolate back to determine Punk / Pref when Pref is zero. Since all gases are ideal at zero pressure, this extrapolated value of Punk / Pref is our most precise value.

Use the extrapolated value of Punk / Pref in the boxed equation, above, to determine our most precise value ofTunk.

Ch1, Lesson E, Page 13 - High Precision Gas Thermometry

At zero pressure all gases are ideal gases. So we need to extrapolate the results from our gas thermometer back to the point where the pressure is zero. On the last page, we discussed how to measure Punk and Pref. Here we take the ratio or Punk to Pref. Then, we repeat the experiment and measure Punk / Pref with LESS gas in the thermometer bulb. We repeat this several times and construct a plot of Punk / Pref as a function of Pref, like the one shown here. If we extrapolate back to Pref = zero, we obtain the value of Punk / Pref that we would measure if the pressure in the bulb were zero. In other words, we get the value of Punk / Pref that we would get if the gas in the bulb were really an ideal gas ! This is very cool because we can take this very precise value of Punk / Pref and plug it back into the boxed equation from the previous page and get a very precise value for the unknown temperature, Tunk.

This extrapolation back to the ideal gas state of zero pressure is why this technique is often called ideal gas thermometry. That concludes our discussion of pressure, volume and temperature. Now, take a look at a couple of example problems. Then, read the lesson summary and try the quiz for this lesson.

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