1st Law of Thermodynamics The 1st Law of Thermodyamics simply states that energy can be neither created nor

destroyed (conservation of energy). Thus power generation processes and energy sources actually involve conversion of energy from one form to another, rather than creation of energy from nothing. For example: terms of their energy conversion processes. Automobile Engine Heater/Furnace Hydroelectric Solar Nuclear Battery Food Photosynthesis Chemical Chemical Kinetic Heat Electrical

Gravitational Optical Nuclear Chemical Chemical Optical

Electrical Heat, Kinetic, Optical Electrical Heat, Kinetic Chemical

As you can see conversion between chemical energy and other forms of energy are extremely important, whether you are veterinarian or a mechanical engineer. That is what we will focus on for the remainder of this chapter.

System and Surroundings

The 1st Law of Thermodynamics tells us that energy is neither created nor destroyed, thus the energy of the universe is a constant. However, energy can certainly be transferred from one part of the universe to another. To work out thermodynamic problems we will need to isolate a certain portion of the universe

(the system) from the remainder of the universe (the surroundings). For example consider the pendulum example given in the last section. In real life there is friction and the pendulum will gradually slow down until it comes to rest. We can define the pendulum as the system and everything else as the surroundings. Due to friction there is a small but steady transfer of heat energy from the system (pendulum) to the surroundings (the air and the bearing upon which the pendulum swings). Due to the 1st law of thermodynamics the energy of the system must decrease to compensate for the energy lost as heat until the pendulum comes to rest. [Remember though the total energy of the universe remains constant as required by the 1st Law.] When it comes time to work homework, quiz and exam problems (not to mention to design a power plant or computer chip) the 1 st Law of Thermodynamics will be much more useful if we can express it as an equation. E = q + w (1st Law of Thermodynamics) The change internal energy of the system, q The heat transferred into/out of the system, w The work done by/on the system. This reformulation of the 1st Law tells us that once we define a system (remember we can define the system in any way that is convenient) the energy of the system will remain constant unless there heat added or taken away from the system, or some work takes place. E

Internal Energy
We have already discussed work and heat extensively, but a few comments are in order regarding internal energy. The internal energy encompasses many different things, including:

The kinetic energy associated with the motions of the atoms, The potential energy stored in the chemical bonds of the molecules, The gravitational energy of the system. It is nearly impossible to sum all of these contributions up to determine the absolute energy of the system. That is why we only worry about E, the change in the energy of the system. This saves all of us a lot of work, for example: if the temperature doesnt change we can ignore the kinetic energy of the atoms, if no bonds are broken or destroyed we can ignore the chemical energy of the system, if the height of the system doesnt change then we can ignore gravitational potential energy of the system. Our convention for E is to subtract the initial energy of the system from the final energy of the system. E = E(final) E(initial) = q + w In a chemical reaction the energy of the reactants is E(initial) and the heat of the products is E(final).

Sign Convention
When working numerical problems we will quickly become confused if we dont adopt a universal convention for when we use a positive sign or a negative sign. Sign Convention for heat, q Heat is transferred into the system q > 0 Heat is transferred out of the system q < 0 Sign Convention for work, w

Work is done upon the system by the surroundings w > 0 Work is done by the system on the surroundings w < 0 Lets look at some processes to get a better feel for defining a thermodynamic system and using the proper sign convention. Example Hold a piece of ice in your hand until it melts Solution A System You Surroundings Ice + the rest of the universe q < 0 Heat flows out of the system (you) into the ice. Solution B System Ice Surroundings You + the rest of the universe q > 0 Heat flows into the system (ice) from you. You can see that the answer changes depending upon how you define the system, but the physical reality is exactly the same, but both solutions A and B are correct. It doesnt matter how you define the system as long as you are consistent.

Exothermic and Endothermic Reactions

Since heat transfer is an important component of many processes special words have been created to describe the direction of heat flow in a process. Primarily we will use these terms when referring to chemical reactions. Exothermic Reactions q<0 reaction releases heat (heat leaves the system)

heat is a product of the reaction (i.e. explosions, combustions, etc.) Endothermic Reactions q>0 reaction absorbs heat (heat enters the system) heat is a reactant in the reaction

P-V Work
Most chemical reactions either give off or absorb heat, but not all chemical reactions do a significant amount of work. By far the most common types of work associated with chemical reactions are: Electrical work (i.e. batteries, fuel cells, etc.) Mechanical work done by an expanding or contracting gas At this point in the course we will not concern ourselves with electrical work (until chapter 20). Therefore, we only have to worry about work when a gaseous product or reactant is involved (for example the previous example of the reaction that takes place in the automobile cylinder). Let us return to 1st Law equation with the restriction that the only type of work we will consider is done by the expansion/ contraction of a gas (think of the cylinder example). E = q + w = q - (F d) = q - F h

where F is the force opposing the upward push of the cylinder, and h is the distance we move the cylinder upwards against this force. The negative sign in front of the second term comes from the sign convention for work. If the gas expands then h will be positive and the system will do work on the surroundings (the piston), and when that happens work must be negative. Now we use the relationship:

P = F/A

F = PA

where F = force, P = pressure, and A = Area, so that: E = q - PA h but the cross sectional area of the cyliner (piston) multiplied times h is simply the change in the volume of the cylinder: E=q-P V Of course this expression is only useful if the pressure is constant throughout the reaction. Under such conditions we will call the heat transfer by a special name, enthalpy (H). The first law then becomes: E= H-P V Where H is the change in enthalpy that occurs at constant pressure H = H(final) H(initial) = qp At first you might think that constant pressure reactions are a special case, so that enthalpy isnt a terribly useful concept. As it turns out any reaction which is carried out in an open container (such as a beaker or a test tube) is a constant pressure reaction. Therefore, as you will soon see enthalpy is a concept that we will use over and over again.