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We can break the universe into two parts, the system and the surroundings.

The part we are looking at is the system, and everything else is the surroundings. There are a number of ways in which these two interact.

An open system is one where both matter andenergy can freely cross from the system to the surroundings and back. eg an open test tube.

A closed system is one where energy can cross the boundary, but matter cannot. eg a sealed test tube

An isolated system is one where neither matter nor energy can cross between the system and the surroundings. The universe itself is an isolated system (as there are no surroundings to exchange matter or energy with).

Another important thermodynamic concept is work. Work is done when something is moved against an opposing force. The units of work are joules, the same units as energy. This implies a link between the two quantities. Consider lifting an object - work is done during the process as the object is moved upwards against the opposing force of its own weight. Energy is required to carry out the process (we must expend energy to raise the object, as its potential energy is increased). We can see that the more energy a system has, the more work it can do. The energy of a system is a measure of the amount of work it can do. From this it follows that when an isolated system does some work, its energy is reduced (it can now do less work than it could to start with). Conversely, when work is done to a system, it can do more work than it could originally, so its energy has increased. Work is an ordered transfer of energy. It may also be transferred by a disordered or chaotic motion, when it is known as heat. Heat is transferred to or from a system when there is a temperature difference between the system and the surroundings. (Temperature determines the direction of that heat flow, from hot to cold.) Again resulting in an energy change of the system, heat is measured in joules. Barriers that allow heat transfer are called diathermic, and those that don't are called adiabatic:

If, for example, an exothermic reaction takes place in an isolated system (which must necessarily have adiabatic walls), the temperature of the system will rise. Anendothermic reaction taking place in a diathermic container will result in the temperature of the system remaining the same as that of the surroundings (both should lower).

As we said in the introduction, there are two ways in which we can change the Internal energy. They are work and heat. So, U=q+w where q is the heat supplied to the system and where w is the work done on the system. This is the first law of thermodynamics. The change in internal energy of the system is the sum of the heat supplied to the system and the work done on the system. Thus if the system is in an adiabatic container (ie no heat can be supplied to system from the surroundings), the change in internal energy of the system is the same as the work done on the system. Conversely, if the system is in a fixed volume, with no other way of doing work (like a battery), then the change in internal energy is the same as the heat supplied to the system. This is quite useful since it is the basis of finding how the internal energy of a substance changes with temperature:

Since U = q + w, and w = 0, then U = q.


As we heat the water bath, heat is supplied to the system. Unsurprisingly therefore, the internal energy changes and we can conclude that internal energy will change with the temperature. This introduces the heat capacity at constant volume or Cv.

It is normally more useful to look at the molar heat capacity, (ie: the heat capacity per mole) as this quantity may be compared between different substances. It is given the symbol Cvm.

Lets start by considering work done by the system. We know that work = force x distance, so if we consider a gas expanding against a constant pressure thenwork = pressure x volume pushed out, or w = - p. V The '-' sign arrives from the idea that if the final volume is larger than the first, ( V greater than zero) the gas has done work. Our definition of w is the work done onthe system. Hence the '-' sign ensures consistency. What if the external pressure was zero? This is called free expansion. Since w = - p. V, and p=0, therefore w=0 also. The work done is always 0 for expansion into a vacuum. However, suppose the external pressure is not constant, then we must integrate the pressure

with respect to the volume change, ie: w = - ViVf p dVViVf p dV Finally, what if the expansion took place in a diathermic container? The temperature would have remained the same, and if we also assume a perfect gas, we can use the equation of state to write pV = nRT. So p = nRT/V and our integral becomes w = - ViVf nRT/V dV since nRT is a constant, we have w = - nRT ViVf V-1 dV

Boyles Law gives us this pressure - volume graph. The work done is the area under the line. (a) w = - p. V (b) w = - ViVf p dV

We said, on the previous page, that if the system is in a fixed volume, with no other way of doing work (like a battery), then the change in internal energy is the same as the heat supplied to the system. However, if we make that walls of this fixed volume container of an adiabatic substance, then there is no way of influencing the internal energy of the system with the surroundings. The system is closed. This is a very useful situation, since we can now run chemical reactions inside the container and see how the internal energy of the system changes as a direct result of the reaction at a particular temperature.

The closest we can come to this situation is an adiabatic bomb calorimeter. The volume is fixed, but the container will change in temperature if the reaction does, however, we can measure the change in temperature of the container. The temperature change will be proportional to the 'heat of reaction' and so we can calculate U

Enthalpy is a state function. This means that its value is only dependent upon the current state and properties of the system and is completely independent of how the system arrived at this state. Since enthalpy is a state function, this reinforces Hess's Law:

The standard enthalpy change for any process is the same, no matter which route the process took. The system has a specific enthalpy value at A and another different value at B and again a different value at C.

Enthalpy is defined in terms of the internal energy, pressure and volume of the system: H = U + pV If the system is maintained at constant pressure throughout a process, then the heat supplied to the system is equal to the enthalpy change of the system. (This is the case when the system is free to expand and does no other work.) We can prove this from H = U + pV: H = U + pV @H + dH = U + dU + (p +dp)(V - dV) since at constant pressure dp = 0 @H + dH = U + dU + pV - pdV since H = U + pV @dH = dU - pdV since dU = q + w

@dH = q + w - pdV since w = pdV @dH = q Since dH = dU + pdV, changes involving solids and liquids, where dV is negligible, dH dU. However, changes involving perfect gases, we can use the equation of state, pV = nRT, giving H = U + nRT, so if a change involves a change in the number of moles of gas, we can relate this to the difference between the enthalpy change and the internal energy change. The fact that dH = q implies that if we supply heat to the system, the enthalpy of the system will increase. This is indeed true, and we have that