First Law of Thermodynamics; Enthalpy

We introduced the thermodynamic property of enthalpy, H, in Chapter 6. There we

noted that the change in enthalpy equals the heat of reaction at constant pressure. Now
we want to look at this property again, but define it more precisely, in terms of the
energy of the system. We begin by discussing the first law of thermodynamics.

First Law of Thermodynamics

Thermodynamics is normally described in terms of three laws. The first law of ther-
modynamics is essentially the law of conservation of energy applied to thermody-
According to the law of conservation namic systems. < To state the law, you need to understand what the internal energy
of energy, the total energy remains of a system is and how you can change the internal energy.
constant; energy is neither created The internal energy, U, is the sum of the kinetic and potential energies of the par-
nor destroyed.
ticles making up the system. The kinetic energy includes the energy of motion of elec-
trons, nuclei, and molecules. The potential energy results from the chemical bonding
of atoms and from the attractions between molecules.
Internal energy is a state function. That is, it is a property of a system that depends
only on its present state, which is completely determined by variables such as tem-
perature and pressure. Thus, 1 mol of water at 0C and 1 atm pressure has a definite
quantity of energy. When a system changes from one state to another, its internal
energy changes from one definite value to another. You can calculate the change in
internal energy,
U, from the initial value of the internal energy, Ui, and the final
value of the internal energy, Uf.

U  Uf  Ui
Normally you are interested in changes in internal energy rather than in absolute
values. You measure these changes for a thermodynamic system by noting the
exchanges of energy between the system and its surroundings. These exchanges of
 18.1 First Law of Thermodynamics; Enthalpy 733

Work energy are of two kinds: heat and work. Heat, you will recall, is energy that moves
into or out of the system because of a temperature difference between the system and
its surroundings. Work, on the other hand, is the energy exchange that results when a
Weight force F moves an object through a distance d; work (w) equals F  d.
The distinction between heat and work is illustrated in the system shown in Fig-
Piston
ure 18.2. This system consists of a gas in a vessel equipped with a movable piston.
On top of the piston is a weight, which you can consider as part of the surroundings.
Heat Gas You momentarily fix the position of the piston so it does not move. Suppose the tem-
perature of the surroundings is raised, and as a result, heat passes from the sur-
roundings to the vessel. If you find that the energy of the surroundings decreases by
▼ 165 J in this way, you know from the law of conservation of energy that the internal
FIGURE 18.2
energy of the system must have increased by just this quantity. You write q  165 J,
Exchanges of heat and work with using the sign convention that heat (denoted by the symbol q) absorbed by the sys-
the surroundings
tem is positive (energy is added to the system) and that heat evolved by the system
A gas is enclosed in a vessel with a
is negative (energy is subtracted from the system).
piston. Heat flows into the vessel from the
surroundings, which are at a higher As the temperature of the gas in the vessel increases, the gas pressure increases
temperature. As the temperature of the at fixed volume. You now allow the piston to move, so the gas expands and lifts the
gas increases, the gas expands, lifting the piston and the weight on top of it. In lifting the weight, the system does work. The
weight (doing work). energy gained by the weight equals the force of gravity on the weight times the height
to which the weight was raised (the distance it was moved). Suppose this energy is
92 J. Because the surroundings, which include the weight, have gained 92 J of energy,
the system must have lost 92 J of energy (energy cannot be created or destroyed). You
write w  92 J, adhering to the sign convention that work done on the system is
positive (energy is added to the system) and work done by the system is negative
The convention given here is that (energy is subtracted from the system). <
adopted by IUPAC (International The system in Figure 18.2 gains internal energy from the heat absorbed and loses
Union of Pure and Applied internal energy via the work done. In general, the net change of internal energy equals
Chemistry).
heat plus work.

U  q  w

The first law of thermodynamics states that the change in internal energy of a sys-
tem,
U, equals q  w. For the system shown in Figure 18.2,

U  (165 J)  (92 J)  73 J

Exercise 18.1 A gas is enclosed in a system similar to that shown in Figure 18.2.
More weights are added to the piston, giving a total mass of 2.20 kg. As a result, the gas is
compressed and the weights are lowered 0.250 m. At the same time, 1.50 J of heat evolves
from (leaves) the system. What is the change in internal energy of the system,
U? The force
of gravity on a mass m is mg, where g is the constant acceleration of gravity (g  9.80 m/s2).

■ See Problems 18.31 and 18.32.

Heat of Reaction and Internal Energy

Now consider a chemical system—for example, the reaction of zinc metal with
hydrochloric acid. The reaction is
Zn(s)  2H3O(aq) ±£ Zn2(aq)  2H2O(l)  H2(g)
When this reaction is carried out in a beaker open to the atmosphere, the reaction is
exothermic, evolving 152.4 kJ of heat per mole of zinc consumed. You write qp 
152.4 kJ, where the subscript p indicates that the process occurs at constant pres-
sure (the pressure of the atmosphere).
734 18 Thermodynamics and Equilibrium

The hydrogen gas that is produced increases the volume of the

system. As hydrogen is evolved, work must be done by the system to
push back the atmosphere. How can you calculate this work? Imag-
H2 ine for the moment that the atmosphere is replaced by a piston and
weights, whose downward force from gravity F creates a pressure on
Heat
the gas equivalent to that of the atmosphere. The pressure P equals F
HCl divided by the cross-sectional area of the piston, A. (See Figure 18.3.)
Zn Suppose the increase in volume of the system due to the produc-
tion of hydrogen is
V. Because the volume of a cylinder equals its
height h times its cross-sectional area A, the change in volume is
V 
A B
▼ A  h, and h 
V/A. The work done by the system in expanding
FIGURE 18.3 equals the force of gravity times the distance the piston moves.
Reaction of zinc metal with hydrochloric acid at

V F
constant pressure w  F  h  F    
V
(A) The beginning of the reaction. The constant pressure of the A A
atmosphere has been replaced by a piston and weight to give
The negative sign is given because w is work done by the system and
an equivalent pressure. (B) The reaction produces hydrogen gas.
This increases the volume of the system, so that the piston and represents energy lost by it. Note that F/A is the pressure, P, which
weight are lifted upward. Work is done by the system on the equals that of the atmosphere. Therefore,
piston and weight.
w  P
V

This formula tells you that you can calculate the work done by a chemical reac-
tion carried out in an open vessel by multiplying the atmospheric pressure P by the
change in volume of the chemical system,
V. For example, when 1.00 mol Zn reacts
with excess hydrochloric acid, 1.00 mol H2 is produced. At 25C and 1.00 atm (
1.01  105 Pa), this amount of H2 occupies 24.5 L ( 24.5  103 m3). The work
done by the chemical system in pushing back the atmosphere is
w  P
V  (1.01  105 Pa)  (24.5  103 m3)
 2.47  103 J, or 2.47 kJ
If you apply the first law to this chemical system, you can relate the change in
internal energy of the system to the heat of reaction. You have

U  qp  w  qp P
V
For the reaction of Zn with HCl, qp  152.4 kJ and w  P
V  2.47 kJ, so

U  152.4 kJ  2.47 kJ  154.9 kJ
We can now summarize what happens when 1.00 mol Zn reacts with excess
hydrochloric acid. When the reaction occurs, the internal energy changes as the kinetic
and potential energies change in going from reactants to products. This energy change,

U, equals 154.9 kJ. Energy leaves the system mostly as heat (qp 152.4 kJ) but
partly as expansion work (w  2.47 kJ).

Exercise 18.2 Consider the combustion (burning) of methane, CH4, in oxygen.

CH4(g)  2O2(g) ±£ CO2(g)  2H2O(l)
The heat of reaction at 25C and 1.00 atm is 890.2 kJ. What is the change in volume
when 1.00 mol CH4 reacts with 2.00 mol O2? (You can ignore the volume of liquid water,
which is insignificant compared with volumes of gases.) What is w for this change? Cal-
culate
U for the change indicated by the chemical equation.

■ See Problems 18.33 and 18.34.

 18.1 First Law of Thermodynamics; Enthalpy 735

Enthalpy and Enthalpy Change

In Chapter 6, we defined enthalpy tentatively in terms of the relationship of
H to
the heat of reaction at constant pressure, qp. We now define enthalpy, H, precisely as
the quantity U  PV. Because U, P, and V are state functions, H is also a state func-
tion. This means that for a given temperature and pressure, a given amount of a sub-
stance has a definite enthalpy. Therefore, if you know the enthalpies of substances,
you can calculate the change of enthalpy,
H, for a reaction.
Let us now show the relationship of
H to the heat of reaction qp. Note that
H
is the final enthalpy Hf minus the initial enthalpy Hi.

H  Hf  Hi
Now, substitute defining expressions for Hf and Hi, using the subscripts f and i to indi-
cate final and initial, respectively. Note, however, that the pressure is constant.

H  (Uf  PVf)  (Ui  PVi)  (Uf  Ui)  P(Vf  Vi) 
U  P
V
Earlier we found that
U  qp  P
V. Hence,
Spontaneous process
H  (qp  P
V)  P
V  qp
This shows that
H  qp, as noted in Chapter 6.
In practice, what you do is measure certain heats of reaction and use them to tab-
ulate enthalpies of formation,
Hf. The standard enthalpy change for a reaction is

H   n
Hf (products)   m
Hf (reactants)
Standard enthalpies of formation for selected substances and ions are listed in Table
6.2 and in Appendix C.
Suppose you would like to know how much heat is absorbed or evolved in the
Nonspontaneous process reaction between NH3 and CO2 to produce urea and water, which is the reaction
▼ given in the chapter opening. The following are standard enthalpies of formation
FIGURE 18.4
at 25C for the substances indicated (in kJ/mol): NH3(g), 45.9; CO2(g), 393.5;
Examples of a spontaneous and a
NH2CONH2(aq), 319.2; H2O(l), 285.8. Substituting into the previous equation
nonspontaneous process
yields
Top: The rolling of a rock downhill is a
spontaneous process. The rock eventually
H  [(319.2  285.8)  (2  45.9  393.5)] kJ  119.7 kJ
comes to equilibrium at the bottom of the
hill. Bottom: The rolling of a rock uphill is a From the minus sign in the value of
H, you conclude that heat is evolved. The reac-
nonspontaneous process. tion is exothermic.