Hess’ Law: Hess’ Law takes advantage of the fact that enthalpy is a state

function. Hess’ Law applies to the change in enthalpy that takes place
when some set of reactants is converted to some set of products.
Simply stated, Hess’ Law says:

The change in enthalpy (ΔH) is the same whether the process takes place in
a single step or in a series of steps.

 An Example of Hess’ Law (pp. 242-3): Let us consider the oxidation

of N2 to produce nitrogen dioxide (NO2). We can write it as a single-step
reaction in which 2 oxygen molecules combine with 1 nitrogen
molecule to form 2 nitrogen dioxide molecules:

N2 (g) + 2O2 (g) ——> 2NO2 (g) ΔH1 = 68 kJ

The alternative is to regard the reaction as taking place in two steps. In
the first step, 1 molecule of oxygen combines with 1 molecule of
nitrogen to form 2 nitrogen monoxide molecules. Then in the second
step, a second oxygen molecule combines with the 2 nitrogen
monoxide molecules to form the final products, 2 nitrogen dioxide
molecules. We write separate equations (and enthalpy changes) for the
two steps, then we add them together to obtain the final, equation and
enthalpy change for the overall reaction:
N2 (g) + O2 (g) —— 2NO (g) ΔH2 = 180 kJ
>
2NO (g) + O2 (g) —— 2NO2 (g) ΔH3 = —112 kJ
>
N2 (g) + 2O2 (g) —— 2NO2 (g) ΔH2 + ΔH3 = (180 —112) kJ
+ 2NO (g) > + 2NO (g)
N2 (g) + 2O2 (g) —— 2NO2 (g) ΔH1 = 68 kJ
>
Note that the net reaction, and its enthalpy change are identical,
whether we run the reaction in a single step or in two steps. A
comparison of the one step process versus the two step process is
shown in Figure 6.7 from your text:
 While the foregoing example demonstrates Hess’ Law, it does not
prove it. Any proof lies in the consistency between Hess’ Law and the
First Law.

 Characteristics of Enthalpy Changes: Suppose we know the

stoichiometry and the change in enthalpy for some particular reaction.
Take, for example:

Xe (g) + 2F2 (g) ——> XeF4 (s) ΔH = —251 kJ

Suppose we needed to use this reaction in a Hess’ Law problem, but at
double the quantities of reactants and products. What happens to the
change in enthalpy? Because enthalpy change is an extensive
property, it is proportional to the amounts of material. In this case, we
know the enthalpy change for the production of 1 mole of XeF 4 (s). So,
if we make 2 moles instead of 1, we double the change in enthalpy.
The equation for that case is:

2Xe (g) + 4F2 (g) ——> 2XeF4 (s) ΔH = —502 kJ

Suppose instead, we needed to use the (first) reaction in another Hess’
Law problem, but in reverse? What then, would be the change in
enthalpy? In the (first) reaction the system transfers 251 kJ of heat to
the surroundings, so one would expect that the reverse reaction would
require that the same amount of heat would be transferred from the
 surroundings into the system. Thus ΔH would have the same
magnitude, but the opposite sign:

XeF4 (s) ——> Xe (g) + 2F2 (g) ΔH = +251 kJ

These characteristics apply in general, and can be expressed as rules:
o 1) The magnitude of ΔH is directly proportional to the
quantities of reagents (reactants and products) involved in
the reaction. If the coefficients in the reaction are
multiplied by some factor, the enthalpy change must be
multiplied by the same factor.
o 2) If the direction of the reaction is reversed, the sign of
ΔH is also reversed. (Note that you could derive this rule
from the first rule by using —1 as the factor by which the
coefficients and ΔH are multiplied.)

 Sample Exercise 6.7 (p. 244): Graphite and diamond are two
allotropic forms of carbon shown in the following illustration:

Their properties are strikingly different as are their “molecular”

structures. Graphite is a soft, black, slippery substance used for
 lubrication and as pencil “lead;” Diamond is a brilliant, crystal-clear
substance used for gemstones and as an industrial abrasive. The
enthalpies of combustion for graphite and for diamond are,
respectively, —394 kJ/mol and —396 kJ/mol. Calculate ΔH for the
conversion of graphite to diamond. (This problem illustrates the use of
Hess’ Law to compute an enthalpy change that is most impractical to
measure directly.)
o We start by writing equations for the conversion reaction and
for the two combustion reactions:
C (graphite) —— C (diamond) ΔH = ?
>
C (graphite) + O2 (g) —— CO2 (g) ΔH = —394 kJ
>
C (diamond) + O2 (g) —— CO2 (g) ΔH = —396 kJ
>
o Now we solve the problem by reversing the reaction for the
combustion of diamond and adding it to the reaction for the
combustion of graphite:
C (graphite) + O2 (g) —— CO2 (g) ΔH = —394 kJ
>
CO2 (g) —— C (diamond) + O2 (g) ΔH = +396 kJ
>
C (graphite) —— C (diamond) ΔH = (396 — 394) kJ
+ O2 (g) + CO2 (g) > + O2 (g) + CO2 (g)
C (graphite) —— C (diamond) ΔH = 2 kJ
>

 Sample Exercise 6.8 (p. 245): (This exercise illustrates the kind of
systematic procedure often necessary for the solution of a complex
Hess’ Law problem.) Calculate ΔH for the synthesis of diborane (B2H6
(g)) from its elements, boron (B (s)) and hydrogen (H2 (g)):

2B (s) + 3H2 (g) ——> B2H6 (g)

Use the following data for the calculation:
(a) 2B (s) + 3/2O2 (g) —— B2O3 (s) ΔH = —1273 kJ
>
(b) B2H6 (g) + 3O2 (g) —— B2O3 (s) + 3H2O(g) ΔH = —2035 kJ
>
(c) H2 (g) + ½O2 (g) —— H2O (l) ΔH = —286 kJ
>
(d) H2O (l) —— H2O(g) ΔH = +44 kJ
 >
o Our objective is to combine the four reactions so that we
assemble our reactants, B (s) and H2 (g), on the left hand side
and our product, B2H6 (g), on the right, while we make all the
intermediate reagents cancel out. The solution in the text
begins by combining (a) with the reverse of (b), and that is
perfectly valid. But it is also perfectly valid to begin by
combining (a) with 3 x (c), and that is what we will do.
(a) 2B (s) + 3/2O2 (g) —— B2O3 (s) ΔH = —1273 kJ
>
3 x (c) 3H2 (g) + 3/2O2 (g) —— 3H2O (l) ΔH = 3(—286 kJ)
>
(1) 2B (s) + 3H2 (g) —— B2O3 (s) ΔH = —1273 —858 kJ
+ 3O2 (g) > + 3H2O (l) = —2131 kJ
This accomplishes the objective of assembling the right
amounts of both reactants on the left hand side.
o Now we can continue by combining our first intermediate
result (1) with the reverse of (b).
(1) 2B (s) + 3H2 (g) —— B2O3 (s) ΔH = —2131 kJ
+ 3O2 (g) > + 3H2O (l)
— (b) B2O3 (s) + 3H2O(g) —— B2H6 (g) + 3O2 (g) ΔH = + 2035 kJ
>
2B (s) + 3H2 (g) —— B2H6 (g) ΔH = —96 kJ
+ 3O2 (g) + B2O3 (s) > + 3O2 (g) + B2O3 (s)
+ 3H2O(g) + 3H2O (l)
(2) 2B (s) + 3H2 (g) —— B2H6 (g) ΔH = —96 kJ
+ 3H2O(g) > + 3H2O (l)
This accomplishes the objective of assembling the right
amount of product on the right hand side. It also gets rid of
most of the intermediate reagents. But we still need to
eliminate 3H2O(g) from the left hand side and 3H2O (l) from the
right.
o Now we can finish by combining our second intermediate
result (2) with 3 x reaction (d).
(2) 2B (s) + 3H2 (g) —— B2H6 (g) ΔH = —96 kJ
+ 3H2O(g) > + 3H2O (l)
3 x(d) 3H2O (l) —— 3H2O(g) ΔH = +3x44 kJ
>
2B (s) + 3H2 (g) —— B2H6 (g) ΔH = —96 + 132 kJ
+ 3H2O (l) > + 3H2O (l)
+ 3H2O(g)
 + 3H2O(g)
2B (s) + 3H2 (g) —— B2H6 (g) ΔH = +36 kJ
>
o We are done! The synthesis of one mole of diborane from its
elements is slightly endothermic. Assuming that all the
measured enthalpy changes for reactions (a) – (d) were made
under standard conditions (1 atm pressure and 25 °C), we
have thus determined that the standard enthalpy of formation
of diborane is +36 kJ/mol. We will discuss standard enthalpies
of formation in detail in the next section.

6.4 Standard Enthalpies of Formation: We saw in Section 6.2 that

constant pressure calorimetry is a method we can apply to make
measurements of enthalpy changes (i. e., heats of reaction) for
reactions that take place in solution under ambient pressure.
Additionally, constant volume calorimetry (into which we did not delve
to any great extent) can be used to determine heats of combustion for
a wide variety of substances. But what do we do about reactions that
do not lend themselves to calorimetry? How do we obtain enthalpy
changes for such reactions? (A good example is the reaction for the
conversion of graphite into diamond, where we obtained the enthalpy
change from the heats of combustion of graphite and of diamond.)
Would it help if someone has already tabulated the enthalpy changes
for a list of reactions that encompass all the compounds we might ever
be interested in? Actually, there is such a list in the back of your text.

 Standard Enthalpy of Formation, a Definition: The standard

enthalpy of formation (ΔHf°) of a compound is defined as the change in
enthalpy that accompanies the formation of one mole of the
compound from its elements with all substances in their standard
states. The degree sign in the symbol, ΔHf°, indicates that this is the
case.
 Standard States: The definition for standard enthalpy of formation
stipulates that all substances be in their standard states. So we need
to define the conditions that make a state standard:
o All Substances: A temperature of exactly 25 °C is required.
o Any Gaseous Compound: The pressure must be exactly 1
atmosphere. (This may soon change. The IUPAC has adopted
a new standard pressure of exactly 1 bar, or 100,000 Pa. By
comparison, 1 atmosphere = 101,325 Pa.)
o Any Pure Substance in a Condensed State (liquid or
solid): The standard state is the pure liquid or solid.
 o Any Substance in Solution: The standard state is a
concentration of exactly one mole per liter (1 M).
o An Element: The standard state of an element is the form in
which the element exists under the conditions of 1
atmosphere pressure and 25 °C. (The standard state for
oxygen is O2 (g) at 1 atm.; the standard state for carbon is
graphite; the standard state for mercury is Hg (l); the
standard state for sodium is Na (s), etc.)

 Examples of Standard Enthalpies of Formation: We follow the

discussion on p. 247 of your text:
o Nitrogen Dioxide (NO2 (g)): We write the reaction for the
formation of one mole of product:

½ N2 (g) + O2 (g) ——> NO2 (g) ΔHf° = 34 kJ/mol

The standard states are all gases at 25 °C. The picture shows a
sample of NO2 (g) in a Florence flask.

o Methanol (CH3OH (l)): We write the reaction for the

formation of one mole of product:

C (s) + 2H2 (g) + ½ O2 (g) ——> CH3OH (l) ΔHf° = —239 kJ/mol
The standard state of carbon is graphite; the standard states
of hydrogen and oxygen are both gases; and the standard
state of methanol is the liquid, with all reagents at a
temperature of 25 °C.
o Oxygen (O2 (g)): We write this “reaction” as:

O2 (g) ——> O2 (g) ΔHf° = 0 kJ/mol

Notice that the enthalpy of formation of oxygen, or any other
element, in its standard state is necessarily zero, by virtue of
no real reaction having taken place.
o Lists of Values of Standard Enthalpies of Formation: A
short list is given in Table 6.2 in the text:

A more complete list can be found in Appendix 4, on pp. A19-

A22. The list includes two other properties, ΔGf°, and S°. We
will discuss these properties later in the year.
 Using Standard Enthalpies to Calculate Standard Enthalpy
Changes (Heats of Reaction): We will follow the example from the
text, the combustion of methane. We wish to calculate the standard
enthalpy of combustion:
o We start by writing the reaction. (It should be an “old friend”
by now.)

CH4 (g) + 2O2 (g) ——> CO2 (g) + 2H2O (l)

Note that the water is in its liquid state. This follows from our
requirement that the reaction begin and end at 25 °C. This
does not restrict it from taking place (as we know it does) at a
much higher temperature. We simply invoke the fact that
enthalpy is a state function, and we can pick any path, as long
as it starts with reactants at standard conditions and ends
with products at standard conditions.
o We can set the path so as to allow us to break the reaction up
into a series of reactions whose enthalpy changes can be
found in our tables. A particularly useful series of reactions is
the one where we assume that our reactants “un-form”
themselves back to their elements (in standard states) then
re-form as the products. We see this diagrammed in Figure
6.8 from your text

o This analysis gives us the following set of reactions:

(a) CH4 (g) —— C (s) + 2H2 (g) ΔHa° = 75 kJ
>
(b) 2O2 (g) —— 2O2 (g) ΔHb° = 0 kJ
>
(c) C (s) + O2 (g) —— CO2 (g) ΔHc° = —394 kJ
>
(d) 2H2 (g) + O2 (g) —— 2H2O (l) ΔHd° = —572 kJ
>
Reaction (a) is the reverse of the reaction to form 1 mole of
methane from its elements. According to Appendix A4, p. A20,
methane has a heat of formation of —75 kJ/mol, so we change
the sign to get ΔHa° = 75 kJ.
Reaction (c) is the reaction to form 1 mole of CO2 (g) from its
elements and we can find ΔHc° = —394 kJ in Table 6.2.
Reaction (d) is the reaction to form 2 moles of liquid water
from its elements, so we double the value of —286 kJ/mol we
 find in Table 6.2 for the standard enthalpy of formation of
water and obtain ΔHd° = —572 kJ.
(We have already discussed why ΔHb° = 0 kJ.)
o Now we can recombine the four reactions and add the 4
enthalpy changes to get the final result:
(a) CH4 (g) —— C (s) + 2H2 (g) ΔHa° = 75 kJ
>
(b) 2O2 (g) —— 2O2 (g) ΔHb° = 0 kJ
>
(c) C (s) + O2 (g) —— CO2 (g) ΔHc° = —394 kJ
>
(d) 2H2 (g) + O2 (g) —— 2H2O (l) ΔHd° = —572 kJ
>
CH4 (g) + 2O2 (g) —— CO2 (g) + 2H2O (l) ΔH° = —891 kJ
>
o Let’s look at this problem another way:
CH4 (g) + 2O2 (g) —— CO2 (g) + 2H2O (l)
>
ΔHf° —75 kJ 0 kJ —394 kJ —286 kJ
x —1 —2 +1 +2
ΔH° +75 kJ +0 kJ —394 kJ —572 kJ
=
ΔH° —891 kJ
=
The (balanced) equation for the reaction is written in the first
row.
The standard (molar) enthalpies of formation then are written
in the second row for each component of the reaction.
The third row contains a set of multipliers where the
magnitude of each multiplier is the stoichiometric coefficient
from the reaction equation and the signs are “—” for each
reactant and “+” for each product.
The fourth row contains terms that are obtained by
multiplying together the entries in the second and third rows.
When the terms in the fourth row are added together, the
result (fifth row) is the standard enthalpy change for the
reaction, our desired result.

 Equation 6.1 (p. 249): The procedure we have just used to obtain the
standard enthalpy of combustion of methane can be generalized so
 that it applies to any reaction where the initial and final states
correspond to standard conditions. The standard enthalpy change for a
given reaction can be calculated by subtracting the enthalpies of
formation of the reactants from the enthalpies of formation of the
products. (These enthalpies of formation are calculated for the actual
numbers of moles of each component in the reaction.) Mathematically,
this statement can be written as Equation 6.1:

ΔH°reaction = Σnp ΔHf°(products) — Σnr ΔHf°(reactants) (6.1)

In Equation 6.1, the symbol, Σ (sigma), means to compute the sum of

the terms, the np’s represent the stoichiometric coefficients of the
products, and the nr’s represent the stoichiometric coefficients of the
reactants.
The “five row” procedure that we just used is a systematic and
compact way to apply Equation 6.1 to a standard enthalpy change
problem. We listed the molar enthalpies of formation (ΔHf°) in the
second row for each component in the reaction, and we listed the
stoichiometric coefficients (the np’s and the nr’s) in the third row (with
“—“ signs for the nr’s). Then we computed the individual terms of the
summation in row four (np ΔHf° and — nr ΔHf°) and did the final
summation in row five to get the desired answer.

 Sample Exercise 6.9 (pp. 249-51): Compute the standard enthalpy

change for the reaction of ammonia burning in air to produce nitrogen
dioxide and water. Refer to Table 6.2 for standard enthalpies of
formation.

The text spreads this calculation over two full pages; we’ll do it in five
lines:
4NH3 (g) + 7O2 (g) —— 4NO2 (g) + 6H2O (l)
>
ΔHf° —46 kJ 0 kJ 34 kJ —286 kJ
x —4 —7 +4 +6
ΔH° = +184 kJ +0 kJ +136 kJ —1716 kJ
ΔH° = —1396 kJ

 Sample Exercise 6.10 (p. 251): Compute the standard enthalpy

change for the reaction of aluminum metal with iron (III) oxide to form
aluminum oxide and iron metal. (This is commonly called the
“thermite” reaction.)
 We will again do it in five lines:
2Al (s) + Fe2O3 (s) —— Al2O3 (s) + 2Fe (s)
>
ΔHf° 0 kJ —826 kJ —1676 kJ 0 kJ
x —2 —1 +1 +2
ΔH° = +0 kJ +826 kJ —1676 kJ +0 kJ
ΔH° = —850. kJ

 Sample Exercise 6.11 (p. 252): Compare the standard enthalpy of

combustion of one gram of (liquid) methanol (CH 3OH (l)) with that of
one gram of gasoline. Assume that gasoline is pure liquid octane
(C8H18).
We will first compute the standard molar enthalpies of the two fuels,
then convert to enthalpies per gram for the comparison. The
calculation for (one mole of) methanol is:
CH3OH (l) + 3/2O2 (g) —— CO2 (g) + 2H2O (l)
>
ΔHf° —239 kJ 0 kJ —394 kJ —286 kJ
x —1 —3/2 +1 +2
ΔH° = +239 kJ +0 kJ —394 kJ —572 kJ
ΔH° = —727. kJ
This result is the heat of combustion of methanol in units of kJ/mol. To
convert this to kJ/g, we divide by the molar mass of methanol (32.0
g/mol). Thus the desired result is:

ΔH° = —(727. kJ/mol)/(32.0 g/mol) = —22.7 kJ/g

The calculation for (one mole of) octane (C 8H18) is:
C8H18 (l) + 25/2O2 (g) —— 8CO2 (g) + 9H2O (l)
>
ΔHf° —269 kJ 0 kJ —394 kJ —286 kJ
x —1 —25/2 +8 +9
ΔH° +269 kJ +0 kJ —3152 kJ —2574 kJ
=
ΔH° —5457. kJ
=
This result is the heat of combustion of octane in units of kJ/mol. To
convert this to kJ/g, we divide by the molar mass of octane (114.2
g/mol). Thus the desired result is:

ΔH° = —(5457 kJ/mol)/(114.2 g/mol) = —47.8 kJ/g

(Since our data are precise to 3 significant figures, we express this
result to 3 significant figures.) We have just demonstrated that the
enthalpy of combustion of gasoline (octane) is slightly more than twice
that of methanol.