Thermodynamics The first Law: the energy of the universe is constant or energy can neither be created or destroyed.

From the first law we can say that the internal energy of an isolated system is constant. An isolated system: closed and insulated to prevent the exchange of either matter or energy. The system and the surroundings make up the universe. There are 3 basic types of systems: 1. 2. 3. The system may be open able to exchange matter and energy with the surroundings. Closed able to exchange energy only. Isolated

Work (w) is defined as the energy expanded when moving against an opposing force. The units well typically use ar the Joule (J) and the J is defined by kg*m2/s2 In thermodynamics the capacity of a system to do work is its total internal energy (U). So the change in internal energy is U. Where: U = Ufinal - Uinitial The Greek letter is used to represent a change in. Summary of internal energy. If U is negative in an isolated system then the system has lost energy and done work on the surroundings. If U is positive in an isolated system then the system has gained energy and had work done in it by the surroundings. A system can do either expansion work, a change in volume, or nonexpansion work such as a chemical reaction that causes an electrical current. Expansion work Pressure is a force per area P = f/A Consider a movable piston in a cylinder of compressed gas.

Distance the piston moves multiplied by the area of the piston gives us the change in volume.

d*A = V Then we can calculate the work done by our system: W = - PexV In SI units we have Pascal (Pa) and m3. The basic units of a Pa are kg*m/(m2*s2 ) so Pa*V = J From our current definitions it stands to reason that if we do and expansion in the absence of an external pressure, say in a vacuum, we do zero work. We call this free expansion. Prob. 6.3 Given a piston diameter of 3.0 cm moving a distance of 20. cm with an external pressure of 2.00 atm. a. How much work is done in the compression? b. Is the work positive or negative with respect to the air in the pump (system)?

So far we have dealt with systems that expand or compress against a constant pressure. Now lets consider a gas that expands against a changing external pressure. In thermodynamics a reversible process is one that can be reversed by an infinitesimal change in a variable.

Working in an isolated system so that the temp is constant (isothermal). The area under the curve is the work done by the system. To calculate the area under the curve we need to use calculus. So, dw = -PdV from the ideal gas law P = nRT/V then,

So far we have done isothermal work by or on our system. Now we will consider systems that exchange heat, represented by q. From the 1st law we know that the energy of the system must be maintained. So, U = w + q But if we do our reaction in a system with fixed volume then w = 0 and U = q If heat/energy is supplied to the system then +q If heat/energy is given off by the system then q The easiest way to measure the heat change in a system is to measure the temperature. Since substances change temperature at different rates we use heat capacity (C) defined by the ratio q/T However, since heat capacity is also an extensive property, sample size dependent, we commonly use the specific heat capacity Cs = C/mass or molar heat capacity Cm = C/n The SI unit of heat is the J but commonly used is the calorie (cal). 1 cal = 4.184 J and Prob. 6.15 exactly

1 cal is the heat required to raise 1.0 g of liquid water 1.0oC

State function: a property with a value that depends only on the current state of the system. The importance of a state function in thermodynamics is that: if the system is changed from one state to another, the change in the state function is independent of the path that it took to get there.

The Origin of Internal Energy. Internal energy is stored as kinetic and potential energy. From the kinetic theory of gases we know that the average speed of molecules increases with increasing temperature. Therefore the kinetic energy of gases increases with temperature. Molecules in a gas can move in a variety of ways. The kinetic energy or translational kinetic energy is the energy from the molecule or atom as it moves through space. The rotational kinetic energy is only present in molecules as they rotate about a central point. The vibrational kinetic energy is the stored energy that molecules have as they are excited and vibrate at their bonds. Enthalpy In a constant volume system there is no expansion work, therefore U = q In chemistry, however, most reactions are run in open systems at atmospheric or constant pressure. We want to be able to account for the total change in internal energy if heat is supplied and volume changes at constant pressure. The state function that allows us to do this is enthalpy (H). H = U + PV Consider a process at constant pressure, P, with U and V. Then, H = U + PV Recall, So, Lets say the only work the system can do is expansion work. Now,

Then,

And since the system is open P = Pex

Therefore,

For a system that can do only expansion work at constant pressure,