Chapter 2

The First Law of Thermodynamics

Energy and the First Law
The First Law of thermodynamics is the thermodynamic expression of one of the most basic laws of physics; the conservation of energy. This law is most simply stated by saying that energy cannot be created or destroyed o r that the energy of the universe is a constant More complicated statements can express the First Law in a way that is more closely related to how we will actually apply the conservation of energy principle, for example energy can be converted between one form and another with the total energy being constant . We can embellish these simple expressions to make a more precise statement such as: A given amount of energy in a particular form can be converted to energy of a dierent form and then transformed back into the same amount of the original form. The total energy during the conversion and reverse process being constant . The important thing to remember is that the First Law states that energy is conserved always. We ve already stated that we are not going to go into a series of heat engine arguments to prove the conservation of energy during a thermodynamic process since we ve all seen these arguments before and they are not useful for our purposes in this course. What we are going to do is state the state the First Law as an axiom. Before we do that let s look at why a conservation of energy principle is relevant 19

20

The First Law of Thermodynamics

to the study of the thermodynamics of materials. As we discussed in Chapter 1, thermodynamics is the eld which studies the transformations of energy. It is easy to understand that the rule which states that all energy transformations must leave the energy of the universe a constant is going to play a central role in thermodynamics. In this course the transformations of energy we are most interested in are those which involve materials and our main interest in the First Law is how it governs the interaction of energy with materials. Since we know that as a material changes structure, or as the individual atoms of the material increase their motion the energy of the material may change. However it changes, we know that the change in energy of the material must be balanced by an equal and opposite change in energy of the surroundings. So although we haven t developed much of the detail of how energy and materials interact, we do know that whatever the details of their interaction the total energy is a constant throughout the process. Let s call the quantity which refers to the energy of our system as U.

The Internal Energy

For this course we will ignore the energy of the system related to its location in space (potential energy) and macroscopic motion of our system through space (kinetic energy) so that U is then the internal energy of the system. Here then internal energy refers to that energy associated with the internal condition of the system, and not on its spatial location or motion. De nition 6 The internal energy U of a system is the energy associated with the internal condition of the system. For a material this includes the interatomic interactions and the energy associated with atomic motion. With this de nition of internal energy we would then say that the internal energy of a material on a fast moving airplane would be the same as for the material in a lab if the thermodynamic variables are the same. Likewise, the thermodynamics of a piece of iron is the same on my second oor lab as they are in the basement lab since the internal condition of a material isn t aected by potential energy. On the other hand, the internal energy of a piece of iron increases when it has been heated so that its atoms are moving in their potential wells with higher kinetic energy. The internal energy of a bar of iron under uniaxial stress would be higher than an unstressed bar because the atoms in the bar move relative to each other when under load to positions where their interactions are dierent. On the other hand, moving the material up a oor didn t change the relative positions of

The First Law of Thermodynamics

21

the atoms making up the material and consequently didn t aect the internal energy. The dierence here is that the overall position and motion of a material is irrelevant to thermodynamics, whereas the internal positions and motions of the atoms in a material determine the internal energy of that substance. Now that we ve informally brought up and discussed the notion of the First Law and Internal Energy, let s make a more formal and precise statement so we can use this Law with con dence later in this course.

The First Law

Axiom 1 The First Law of Thermodynamics: There exists a function U which; represents the energy of a system, is a function of the system variables of state, changes between two states an amount which is independent of the process by which system was taken. The change in U of our system is balanced by an equal and opposite change of U of the surroundings such that there is no change in U for the universe no matter what process we perform. So each system has an energy which depends on the condition of the system, but not on the process by which it arrived at that state. The change in this energy is balanced by a transfer of energy to or from the surroundings. If we have a closed system, then the change in U is the heat ow from the surroundings plus the work done on the system by the surroundings. In other words, the only way to change the internal energy of our system is to allow energy to ow between it and its surroundings through its boundaries. This consequence of the First Law is often written as: U =q+w In fact, this equation is often used as a statement of the First Law itself, while it is really just an accounting of how energy owed into and out of a system during some process. If our system is closed, then we can choose the variables of state to be any two of the set of temperature T , pressure P , and volume V . Let s choose our variables of state to be P and V . The energy function is then

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The First Law of Thermodynamics

U = U (P, V ) and a change in U that results from a process which changes P and or V is written as U = U2 U1 = U (P2 , V2 ) U (P1 , V1 )

Where the system has been taken from state 1 (P1 , V1 ) to state 2 (P2 , V2 ). Note that this is a consequence of U being a state function, not the First Law. Now in dierential form U becomes dU which is the total dierential of U. Let s pause here brie y to discuss the nature of dierentials of state functions and to remind ourselves of what total dierentials and exact dierentials are.

Total and Exact Dierentials

The expression C1(X1 , X2 , . . . Xn )dX1 + C2 (X1 , X2 , . . . Xn )dX2 + . . . is an exact dierential when it is equal to the total dierential of a function written here as dY =
Y X1 Xj

dX1 +
n

Y X2

Xj

dX2 + . . . +
Xj

Y Xn

Xj

dXn =

i=1

Y Xi

dXi

where the Xi are independent variables. The necessary conditions for exactness are then that the functions Ci be equal to their correspondY ing partial derivatives of Y ; Ci = X where the Ci and Xi are i
Xj

said to be conjugate to each other. The dierential is then exact and dY = Ci dXi . In the case of the total dierential of U we mentioned above with the independent variables P and V dU =
U V P

dV +

U P V

dP

For a dierent choice of independent variables we d get a dierent total dierential, for example: dU =
U V T

dV +

U T V

dT

Now that we re clear on exact and total dierentials let s get back to that consequence of the rst law which is often used as an alternative expression of the rst law; that the change in internal energy of a system during a process is equal to the sum of q, the heat that ows into the system from the surroundings and w the work done on the system by the surroundings during the process

The First Law of Thermodynamics

23

U = q + w + w + w + ... where we have divided the work into its dierent forms; w refers to the mechanical work done on the system and where the primed ws refer to other forms of work. In dierential form this expression becomes (ignoring other forms of work for now) dU = q + w where the dierential denotes the fact that q and w are inexact dierentials. Why are they not exact? Because they are not state functions. Notice that although q and w are inexact dierentials their sum is an exact dierential dU . In other words, although q and w are not state functions, their sum U is. This alternative way of stating the conservation of energy, that U = q + w will be our working statement of the rst law. Let s discuss work and heat in a little more detail here.

Work and Heat

Work
We ve already alluded to the fact that work plays an important role in thermodynamics. This is because energy, our central concept is itself de ned as the potential to do work and work in thermodynamics represents a transfer of energy between the system and its surroundings. If this transfer of energy occurs due to some driving force other than a temperature gradient, then the energy transfer is due to work. Energy transfers due to gradients in temperature are heat ows. Now for ows of energy to a system other than heat the transfer can happen by the surroundings doing various dierent kinds of work on the system. Mechanical work can be done on the system, say by compressing the system (if the system boundary is movable). Work is the transfer of energy that changes the motion of atoms in the system in a uniform way. An example of electrical work being done on the system is moving charges in the system by the application of an external electric eld. Generally, the work done is determined by the product of the generalized force projected onto a generalized displacement. Since work can be done by many dierent kinds of forces, to nd the total work we add together the mechanical work, electrical work, chemical work, magnetic work, etc. That is w = F d xi . For now we ll assume that only mechanical work is done on our sys tem and write W = F d l where an external force F displaces

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The First Law of Thermodynamics

our system boundary an amount d l . We will often focus on simple systems where only mechanical work is done on or by the system. The negative sign insures that when our system is compressed, W the work done on the system is positive since d l will be negative. Mechanical work done on the system due to compression increases the internal energy of the system, whereas an expansion is associated with a decrease in the internal energy. The work to compress a gas or uid at pressure P an in nitesimal amount d l is w= F dl = P Adl = P dV

where A is the area over which the force is acting. Note that mechanical work is done on a system when there is a pressure gradient; that is pressure is the potential to do mechanical work. Now if this compression is done on a system which has adiabatic walls, that is where heat cannot be exchanged with the surroundings then q = 0 and so dU = P dV.

Heat
Like work, heat is a form of energy exchange between a system and its surroundings. The energy exchange between two objects by heat transfer occurs only when there is a temperature dierence, or gradient between those two systems. Heat ows from regions of high temperatures to regions of low temperature. So like pressure, temperature is a potential for transferring energy, speci cally the potential to transfer energy as heat. If the transfer occurs by conduction, then the rate of heat transfer is proportional to both the dierence in temperature T, and the thermal conductivity k. From an atomic point of view, heat is the transfer of energy that occurs through the chaotic motion of matter at the molecular scale. The atoms in a hot region of a material vibrate chaotically more than atoms in a cooler region of a material. As atoms vibrate, they impart a forces to their neighbors and cause them to move. The hotter the atoms, the more vigorous their motion and the larger the forces they impose on their neighboring atoms. This random motion that is passed from one point to another in the material results in energy transfer and eventually leads to a uniform amount of chaotic motion once the random motion of energetic atoms has owed so that no temperature gradients persist. This transfer of kinetic energy to neighboring atoms accomplished through ow of random atomic motion is called heat transfer. So random, chaotic motion is disordered and classi ed as thermal motion, whereas work causes ordered, organized motion of the atoms in a system in a uniform manner.

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25

The First Law for Ideal Processes

Let s consider the First Law for several simple processes. First, let s only consider mechanical work so that dU = q + w = q P dV

which states that the dierential change in the internal energy of a system is equal to the heat ow into the system minus the product of the system pressure and the dierential change in the system volume. If we carry out this process in an adiabatic container we see that there is no heat ow between the system and the surroundings q=0 so that the change in internal energy is just dU = P dV.

Now if instead of carrying out the process in an adiabatic container we kept the temperature of the system constant so that the process is isothermal then dUT = qT PT dVT

Likewise, if we carry out this process in conditions where the pressure doesn t change then we see that for an isobaric process dUP = qP PP dVP

and nally for an isometric process the change in internal energy is just equal to the heat ow into the system dUV = qV since no work is done. Note that in order to determine the change in internal energy for any of these idealized processes on a real system we need to know P (T, V ) and the heat ow for the process. The functional relationship between pressure, volume and temperature would be the equation of state for this system, which can be simple, as in the case of ideal gases, or complicated, as in the case of multicomponent solids. Let s consider ideal gases here so that we can get an idea of how the First Law works in a simple system. In the case of ideal gases we have the Ideal Gas Law which states that:

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The First Law of Thermodynamics

P V = nRT or that P V = RT if we only consider one mole of gas. R is the universal gas constant. We saw above that for the constant pressure process dUP = qP so that
P2 ,V2

PP dVP

UP = qP
P1 ,V1

PP dVP V1 ) = qP R (T 2 T1 )

UP = qP

P (V2

Of course, we could have just substituted the Ideal Gas Law into the First Law for the isobaric process to obtain dUP = qP RdTP

which we could have integrated trivially to obtain the above result as well. Remember that for an ideal gas we assume that the gas particles do not interact and that they do not have any volume. If this is the case then the internal energy of the system will not depend on the volume or pressure of the system, but only on the temperature. Notice that this is evident in the dierential change in internal energy of a constant pressure process we just considered. Thus if we consider an isothermal process we should nd that we have no change in the internal energy of the system. Thus for an isothermal process: dU = 0 qT = wT = P dVT

Substituting P = RT /V in here results in wT = so that

V2

RT dV V

wT =

RT
V1

dV V

2 RT ln V V1

and since P1 V1 = P2 V2 for an isothermal process

2 wT = RT ln P = P1

qT

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27

Heat Capacities
Before we consider an adiabatic process lets make a de nition, De nition 7 The constant volume Heat Capacity is the dierential increase in internal energy of a system caused by a dierential increase in temperature of the system with the volume held constant. The constant volume heat capacity is written as CV =
U T V

q T V

In the case of ideal gases it is not necessary for the volume to be held constant since the internal energy is only a function of the temperature. In the case of constant pressure we de ne a dierent heat capacity De nition 8 The constant pressure heat capacity is the dierential heat ow into a system caused by a dierential increase in temperature of the system held at constant pressure. The constant pressure heat capacity is written as CP = Notice that CP =
U +P dV T P q T P

U T P

+P

V T

and that for an ideal gas

U T P

U T V

U T

= CV

where we have placed no restriction on the partial derivative since the internal energy of an ideal gas doesn t depend on pressure or volume because there are no particle interactions in an ideal gas. CP = U + P V T T P RT = CV + P T P P CP = CV + R
P

Thus the isobaric heat capacity is always larger than the isometric heat capacity. This is because the isobaric heat capacity not only includes the heat ow into the gas when we raise its temperature an in nitesimal amount, but also the work of expansion done against the constant pressure that is not performed in the isometric case. Returning to the adiabatic expansion of an ideal gas we use the de nition for isometric heat capacity

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The First Law of Thermodynamics

dU = CV dT = q + w = w = P dV CV dT = P dV = RT dV V Separating variables gives CV

dT T

R dV V

and integration results in the expression

2 CV ln T = T1 2 R ln V V1

which we rearrange to give

2 ln T = ln T1

V1 V2

R/CV

and
T2 T1

V1 V2

R/CV

P2 P1

R/CP

which implies that P V CP /CV is a constant.

Calorimetry
As we discussed previously we cannot measure the energy of any system directly. We can however device methods for measuring other quantities which can be used to calculate the changes in energy of a system. The calorimeter is a device which allows us to do just this. If we design this calorimeter to con ne our process to a constant volume vessel then we have an isometric process and so no mechanical work is done on the system. If we don t allow any other form of work to be done on the system then dU = qV If our vessel has insulated walls so that no heat ows into the calorimeter and if we keep the water bath surrounding the vessel at a temperature equal to the vessel so that no heat ows into or out of the system except directly through the heater used to maintain the bath water temperature we know that the change in internal energy of the system during the process is just equal to the heat input through the heater to maintain the bath water temperature. Again, for this device to work properly the vessel must be of constant volume.

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29

Enthalpy
Although the relationship between the change in internal energy and the heat ow into the system for a constant volume system is simple and convenient, many processes occur at constant pressure, rather than at constant volume. This is because in many laboratory experiments our system is exposed to atmospheric pressure, rather than kept in a constant volume vessel. If the process is isobaric then the heat associated with this process is q P = ( U + P V )P the quantity U + P V shows up often in thermodynamics and for convenience we ll de ne it as the enthalpy. De nition 9 The enthalpy is the heat associated with a constant pressure process and is expressed as H = U + P V and H= U +P V

Previously we saw that the heat associated with an isometric process was just equal to the change in internal energy. If volume is not held constant, the equality between the heat and the internal energy no longer holds because some of the energy supplied as heat to the system is returned to the surroundings as work, and thus dU < q since w < 0. Although the heat supplied to the system is no longer equal to the internal energy of the system, it is equal to another thermodynamic property of the system, the enthalpy H. Note from the above de nition that a) enthalpy has the units of energy, and b) that enthalpy is a state function since U, P and V all are. How does H change for a constant pressure process? H + dH = U + dU + (P + dP )(V + dV ) since dP = 0 we have H + dH = U + dU + P (V + dV ) and using the de nition H = U + P V we get that dH = dU + P dV From the First Law and considering only mechanical work we can substitute in dU = qP P dV to get

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The First Law of Thermodynamics

dH = qP and nally that

P dV + P dV

dH = qP Now if we go back to our constant volume calorimeter and take o its top so that our process occurs at the laboratory pressure we can equate the heat we supply to the system to the enthalpy change of our system for that process. If the system that we are studying happens to have a very small volume change during the constant pressure process, and if the pressure isn t too large (these are the conditions for P dV being small) we see that dH = dU + P dV dU

This is exactly the case we nd for processes involving condensed phases for low to moderate pressures. In the case of condensed phases at moderate pressures the change in volume during a process does very little work against the atmospheric pressure and so the change in internal energy of the system is approximately equal to the change in enthalpy of the system. Example 1 Consider the conversion of one mole of calcite to argonite. This process results in a 210J increase in the internal energy of the system. The density of CaCO3 as calcite is 2.71 g/cm3 and the density of argonite is 2.93g/cm3 . One mol of calcite has a mass of 100grams and thus the volume of calcite is 37cm3 and the volume of argonite is 34cm3 . If this conversion takes place at one bar (or equivalently 105 Pa) then the dierence between the change in internal energy and change in enthalpy for this phase change results from the expansion against the one bar of pressure. That is: H= U +P V

and the work done during the process is H is then just P V = (105 Pa )(34cm3 37cm3 )(10
6 m3 ) cm3

U =P V

0.3J U = 210J

U = 0.3J which is small compared to So, H So in this case, H is about 99.9 percent of U.

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31

Here let s consider dierential change in enthalpy with respect to temperature holding the pressure constant:
(U +P V ) T P P V U P V + + T P T P T P q dU +P dV CP = = T P dT P H T P

= =

Previously we de ned the constant pressure heat capacity to be CP =

q T P

but we could have made the alternative de nition that CP =

H T P

Chapter 2 Main Points

1. The energy of the universe is a constant. Any change in energy of some subset of the universe is balanced by an opposite change in the surroundings. This change in energy of the surroundings must be transferred to the system through either heat or work. 2. The internal energy U of a system is the energy is a function of internal condition of the system. For a material this includes the interatomic interactions and the energy associated with random atomic motion. It does not include the macroscopic kinetic energy or potential energy of the system as a whole. 3. The First Law of Thermodynamics: There exists a function U called the internal energy of a system which; is a function of the system variables of state, changes between two states an amount which is independent of the process path by which system was taken to its nal state, the change in U of our system is balanced by an equal and opposite change of U of the surroundings such that there is no change in U for the universe no matter what process we perform.

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The First Law of Thermodynamics

4. Work is the transfer of energy that occurs by causing a uniform change in the motion of atoms in a system. 5. Heat is the transfer of energy that occurs by causing a change in the random motion of atoms in the system. 6. An accounting of the energy ow into and out of a system results in the expression: dU = q + w 7. The heat evolved or absorbed during a constant pressure process is called the enthalpy of the system. For condensed systems the enthalpy and internal energy are nearly equal. 8. The dierential heat ow into a system at constant pressure or volume caused by a dierential dierential change in temperature is the constant pressure and constant volume heat capacity, respectively.