426 CHAPTER 12.

Solution Thermodynamics: Applications

12.4 HEAT EFFECTS OF MIXING PROCESSES

The heat of mixing, defined in accord with Eq. (12.29), is:

It gives the enthalpy change when pure species are mixed at constant T and P to form one
mole (or a unit mass) of solution. Data are most commonly available for binary systems, for
which Eq. (12.39) solved for H becomes:

This equation provides for the calculation of the enthalpies of binary mixtures from enthalpy
data for pure species 1 and 2 and from the heats of mixing. Treatment is here restricted to
binary systems.
Data for heats of mixing are usually available for a very limited number of temperatures.
If the heat capacities of the pure species and of the mixture are known, heats of mixing are
calculated for other temperatures by a method analogous to the calculation of standard heats
of reaction at elevated temperatures from the value at 298.15 K (25°C).
Heats of mixing are similar in many respects to heats of reaction. When a chemical
reaction occurs, the energy of the products is different from the energy of the reactants at the
same T and P because of the chemical rearrangement of the constituent atoms. When a mixture
is formed, a similar energy change occurs because interactions between the force fields of like
and unlike molecules are different. These energy changes are generally much smaller than
those associated with chemical bonds; thus heats of mixing are generally much smaller than
heats of reaction.

Heats of Solution
When solids or gases are dissolved in liquids, the heat effect is called a heat of solution, and
is based on the dissolution of 1 mol ofsolute. If species 1 is the solute, then xl is the moles of
solute per mole of solution. Since A H is the heat effect per mole of solution, A H / x l is the
12.4. Heat Effects of Mixing Processes 427

heat effect per mole of solute. Thus,

-
A H = --
AH
x1

where A-H is the heat of solution on the basis of a mole of solute.

Solution processes are conveniently represented by physical-change equations analogous
to chemical-reactionequations. When 1 rnol of LiCl(s) is mixed with 12 mol of H20,the process
is represented by:

The designation LiC1(12H20) represents a solution of 1 rnol of LiCl dissolved in 12 rnol of

H20. The heat of solution for this process at 298.15 K (25°C) and 1 bar is KH
= -33 614 J.
This means that a solution of 1 rnol of LiCl in 12 rnol of H 2 0 has an enthalpy 33 614 J less
than the combined enthalpies of 1 rnol of pure LiCl(s) and 12 rnol of pure H20(1). Equations
for physical changes such as this are readily combined with equations for chemical reactions.
This is illustrated in the following example, which incorporates the dissolution process just
described.

Often heats of solution are not reported directly but must be determined from heats of
formation by the reverse of the calculation just illustrated. Typical are data for the heats of
formation of 1 rnol of ~ i ~ 1 : ' ~

16''~heNBS Tables of Chemical Thermodynamic Properties," J. Phys. Chem. Rej Data, vol. 11, suppl. 2, pp. 2-291
and 2-292, 1982.
428 CHAPTER 12. Solution Thermodynamics: Applications

LiCl in 3 mol HzO -429 366 J

LiCl in 5 mol H 2 0 -436 805 J
LiCl in 8 mol H 2 0 -440 529 J
LiCl in 10 mol H 2 0 -441 579 J
LiCl in 12 mol H 2 0 -442 224 J
LiCl in 15 mol H 2 0 -442 835 J

Heats of solution are readily calculated from these data. Consider the dissolution of 1 rnol
of LiCl(s) in 5 rnol of H20(1). The reaction representing this process is obtained as follows:

Li + + 5H20(1) + LiC1(5H20) AH,",, = -436 805 J

This calculation can be carried out for each quantity of Hz0 fo~whichdata are given.

-
The results are then conveniently represented graphically by a plot of A H , the heat of solution
per mole of solute, vs. Z, the moles of solvent per mole of solute. The composition variable,
Z nz/nl, is related to xl:

1
Whence, x1 = -
l+Z

The following equations therefore relate AH, the heat of mixing based on 1 rnol of solution,
and A%, the heat of solution based on 1 rnol of solute:

Figure 12.14 shows plots of A% vs. Z for LiCl(s) and HCl(g) dissolved in water at 298.15 K
(25°C). Data in this form are readily applied to the solution of practical problems.
Since water of hydration in solids is an integral part of a chemical compound, the heat
of formation of a hydrated salt includes the heat of formation of the water of hydration. The
dissolution of 1 rnol of LiC1.2H20(s)in 8 rnol of H 2 0 produces a solution containing 1 rnol
LiCL in 10 rnol of H20, represented by LiC1(10H20).The equations which sum to give this
12.4. Heat Effects of Mixing Processes 429
430 CHAPTER 12. Solution Thermodynamics: Applications

process are:
Li + ;c12 + 10H20(1)+ LiC1(10H20) AH;", = -441 579 J
LiC1.2H20(s) -+ Li + ;c12 + 2H2 + 0 2 AH& = 1012 650 J
2H2 + 0 2 + 2H20(1) AH&, = (2)(-285 830) J
12.4. Heat Effectsof Mixing Processes 431
432 CHAPTER 12. Solution Thermodynamics: Applications

EnthalpyIConcentrationDiagrams
The enthalpy/concentration ( H x ) diagram is a convenient method for representing enthalpy
data for binary solutions. These diagrams are graphs of the enthalpy plotted as a function of
composition (mole fraction or mass fraction of one species) with temperature as parameter.
The pressure is a constant and is usually 1 atmosphere. Figure 12.17 shows a partial diagram
for the H2S04/H20 system.
Enthalpy values are given for a mole or a unit mass of solution, and Eq. (12.40) is directly
applicable:
+
H = x l H 1 x2H2 A H + (12.40)
Values of H for the solution depend not only on heats of mixing, but also on enthalpies HIand
Hz of the pure species. Once these are known for a given T and P, H is fixed for all solutions at
the same T and P , because A H has a unique and measurable value for each composition. Since
absolute enthalpies are unknown, arbitrary zero points are chosen for the enthalpies of the pure
species. Thus, the basis of an enthalpylconcentration diagram is HI = 0 for some specified
state of species 1 and Hz = 0 for some specified state of species 2. The same temperature need
not be selected for these states for both species. In the case of the H2S04/H20diagram shown
in Fig. 12.17, HI = 0 for pure liquid H 2 0 at the triple point [=273.16 K (O.Ol°C)],and Hz = 0
12.4. Heat Effects of Mixing Processes 433

Figure 12.17 Hx diagram for H2S04/H20(Redrawn from data of Technical Note

270-3, National Bureau of Standards, USA, 1968; T.R. Bump and W. L. Sibbitt, Ind.
Eng. Chem., vol. 47, pp.1665-1670, 1955; and C. M. Gable, H. F. Betz and S. H. Maron,
J. of Am. Chem. Soc., vol. 72, pp. 1445-1448, 1950. By permissions.)
434 CHAPTER 12. Solution Thermodynamics: Applications

0 1

1
Pure 2
x,, mole or mass fraction of
species 1 in solution
t
Pure 1
1 I
Figure 12.18 Graphical constructions on an Hx diagram

for pure liquid H2S04 at 298.15 K (25°C). In this case the 273.15 K ( P C ) isotherm terminates
at H = 0 at the end of the diagram representing pure liquid H20, and the 298.15 K (25°C)
isotherm terminates at H = 0 at the other end of the diagram representing pure liquid H2S04.
The advantage of taking H = 0 for pure liquid water at its triple point is that this is the
base of the steam tables. Enthalpy values from the steam tables can then be used in conjunction
with values taken from fhe enthalpylconcentration diagram. Were some other base used for the
diagram, one would have to apply a correction to the steam-table values to put them on the
same basis as the diagram.
For an ideal solution, isotherms on an enthalpylconcentration diagram are straight lines
connecting the enthalpy of pure species 2 at xl = 0 with the enthalpy of pure species 1 at
= 1, as illustrated for a single isotherm in Fig. 12.18 by the dashed line. The solid curve
represents an isotherm for a real solution. Also shown is a tangent line from which partial
enthalpies may be determined in accord with Eqs. (11.15) and (11.16). Equations (11.79) and
(12.40) combine to give A H = H - H"; A H is therefore the vertical distance between the
curve and the dashed line of Fig. 12.18. Here, the actual isotherm lies below the ideal-solution
isotherm, and AH is everywhere negative. This means that heat is evolved whenever the pure
species at the given temperature are mixed to form a solution at the same temperature. Such a
system is exothermic. The H2S04/H20system is an example. An endothermic system is one
for which the heats of solution are positive; in this case heat is absorbed to keep the temperature
constant. An example is the methanolhenzene system.
One feature of an enthalpylconcentration diagram which makes it particularly useful is
the ease with which problems involving adiabatic mixing may be solved. The reason is that
all solutions formed by adiabatic mixing of two solutions are represented by points lying on a
straight line connecting the points that represent the initial solutions. This is shown as follows.
12.4. Heat Eflects of Mixing Processes 435

Let the superscripts a and b denote two initial binary solutions, consisting of nu and n b
moles respectively. Let superscript c denote the final solution obtained by simple mixing of
solutions a and b in an adiabatic process. This process may be batch mixing at constant pressure
or a steady-flow process involving no shaft work or change in potential or kinetic energy. In
either case,

and for the overall change in state:

In addition, the material balance for species 1 is:

These two equations may be rearranged as:

Division of the first equation by the second gives:

Our purpose now is to show that the three points c, a , and b represented by ( H C , x ; ) ,
a
( H , x f ) , and ( H ~x f, ) lie along a straight line on an H x diagram. The equation for a straight
line in these coordinates is:

If this line passes through points a and b,

Ha = m x : + k and H~ = m x f + k

Each of these equations may be subtracted from the general equation, Eq. (B):

Dividing the first of these by the second yields:

Any point with the coordinates ( H , x l ) which satisfies the last equation lies on the straight line
that contains points a and b. Equation ( A ) shows that ( H C , x i ) is such a point.
The use of enthalpylconcentration diagrams is illustrated in the following examples for
the NaOH/H20 system; an H x diagram is shown in Fig. 12.19.
436 CHAPTER 12. Solution Thermodynamics: Applications
12.4. Heat Effects of Mixing Processes 437
438 CHAPTER 12. Solution Thermodynamics: Applications
12.4. Heat Effectso f Mixinn Processes 439

. Chase, Jr., et al., "JANAF Thermochemical Tables," 3d ed., J. Phys. Chem. Ref: Data, vol. 14, suppl. 1,
1 7 ~ W.
p. 1243, 1985.