3.

5 Enthalpy, the heat of reaction 49

3.5.2 Enthalpy of formation from the elements

A major problem arises from the definition of enthalpy, Equation (3.15). The
problem is that we cannot measure it. This arises from the nature of energy
itself, because we can only measure energy changes, not absolute energies.
Therefore we can only measure enthalpy changes, and changes in any other
property which includes the energy U (or U ).
The problem this creates is that we do not want to have to tabulate an
enthalpy change for every process or chemical reaction which might become
of interest to us – there are too many. We would like to be able to associate
an enthalpy with every substance – solids, liquids, gases, and solutes – for
some standard conditions, so that having tabulated these, we could then easily
calculate an enthalpy change between any such substances under those standard
conditions. After that, we could deal with the changes introduced by impurities
and other nonstandard conditions. The method developed to allow this is to
determine, for every pure compound, the difference between the enthalpy of the
compound and the sum of the enthalpies of the elements, each in its most stable
state, which make up the compound. This quantity is called f H  , the standard
molar enthalpy of formation from the elements. For aqueous ions, the quantity
determined is a little more complicated (Chapter 15), but the principle is the
same. It is this enthalpy quantity which is invariably tabulated in compilations
of data.
For example, the standard enthalpy of formation of anhydrite is

f H CaSO 
= HCaSO4 s

− HCas 
− HSs − 2 HO 2 g (3.19)
4 s

where the superscript  refers to the standard conditions (see below). None of
the individual H  quantities is determinable, but the difference is determinable
by calorimetry. Now if we want to know the heat liberated or absorbed in a
chemical reaction, we need only look up these f H  values for each reactant and
product. For example, for the formation of gypsum from anhydrite, we write

CaSO4 s + 2 H2 Ol = CaSO4 · 2 H2 Os (3.20)

for which the “standard molar heat of reaction,” r H  , is

r H  = f H CaSO − f H CaSO − 2f H H (3.21)

4 ·2H2 O 4 2 Ol

 
= HCaSO4 ·2H2 O
− HCaSO4
− 2 HH 2 Ol (3.22)

Note that in balanced reactions the H  terms for all the elements cancel out,
and we are left with the “real” enthalpy difference (Equation 3.22) between
products and reactants, with no contribution from arbitrary conventions or
assumptions. It is, however, a heat of reaction for standard conditions only.
50 The first law of thermodynamics

Standard states
It is often assumed that the “standard conditions” are 25  C, 1 bar. Actually it
is a bit more complicated in two respects.
1. Knowing the T and P of the state is not sufficient – we must also specify the physical
state of the substance. For solids and liquids, it is simply the pure substance (as in
our anhydrite-gypsum-water example) but for gases it is the gas acting ideally at one
bar (or 105 Pa), and for solutes it is the solute acting ideally at a concentration of
one molal. The reasons for these choices will be discussed later (Chapter 8).
2. While the temperature and pressure of the standard conditions are indeed 25  C and
one bar for purposes of tabulating data, we can and often do have standard conditions
at any T and P.

These more complete definitions of our “standard conditions” define our stan-
dard states, which will be seen to become particularly useful when we later
define the concept of activity (§8.2).

3.5.3 The heat capacity

An older name for the enthalpy is the “heat content.” This name is somewhat
discredited for good reasons, but nevertheless it helps a little in conveying
the essential idea behind the next concept, the heat capacity. The molar heat
capacity can be defined as the amount of heat required to raise the temperature
of one mole of a substance by one degree. Of course, some substances require
much more heat to do this than do others.
The formal definition is
 
dH
= CP (3.23)
dT P

or
 
dH
= CP (3.24)
dT P

or
 
dH 
= CP (3.25)
dT P

Thus heat capacity is the rate of change in H or H with T . A large CP means

that H or H changes a lot for a given change in T , i.e., it takes a lot of heat
to raise the temperature.
It takes a different amount of heat to raise the temperature of a system
depending on whether the volume or the pressure is kept constant, giving two
different quantities, CP and CV . CV is rarely used in geochemistry, but the heat
capacity at constant pressure, CP , is a surprisingly important quantity. It can