THE REACTION ISOTHERM (F=G Gibbs free energy)

Having defined the free energy of a substance as a function of the free energy
in the type state, we will now proceed to deduce the equation of the variation of
that energy in any type of transformation, whether physical or chemical. Let's
consider the reaction in general:
αA + bB + ... =cC + dD+ ... (61)
If the activities of A and B at the beginning are a A and B and those of C and D at
the end of the reaction are a c and D , then the free energies of each of these
substances per mole at temperature T are given by the expressions
F A = F oA + RT ln to A (62a)
F B = F or B + RT In a B (62b)
Fc = F oC +RT ln to c (62c)
o
F D = F D + RT ln to D (62d)
where each particular F O represents the free energies of the unit activity
of the respective species. By definition, ∆F is equal to
∆ F = (cF C + dF D + . . .) - (αF A + bF B + . . . ) (63)
and, from here
∆F=(c FoC + cRTIna c + d F oD + dRTIna D + ...) - (α F oA ,+ αRTlna A + b F oB , + bRTln to B
+.)
c d
o aC ∗a D∗…
∆F¿ ∆ F + RT ln α b (64)
a A∗aB∗…

The first term on the right side of equation (63) gives us the free energy of the
reaction in the type state, that is, the one that takes place when the materials in
their unit activity react forming products whose activity is also one. If we designate
this change by ∆F , equation (63) gives us Equation (64) gives us the variation in
free energy of the reaction as a function of the change in the type state and the
initial and final activities at a given temperature. any constant T.
For this reason, this equation, of great interest, is known as the reaction
isotherm. When the activities of the beginning and ending materials are all equal to
unity, the second term of equation (64) is zero, and ∆F = ∆F o .
If these activities are not worth unity, ∆F is given by the complete equation (61).
For any reaction ∆F o is a constant at a given temperature and is independent of
pressure. The variation of ∆F o with temperature, the same as for ∆ F , is given by
equations (33) or (37) but, in this case, in each particular value instead of ∆S and
∆H we will have the corresponding ∆S o and ∆ H O ; That is, the changes in heat
and entropy are referred to the reactions in the type states. Outside of these
differences, any calculation of ∆F o is handled the same as another of ∆F.

1
FREE ENERGIES TYPE OF TRAINING

Because of the direct relationship between ∆F o and the conditions that prevail
at equilibrium, which will be discussed in the next chapter, the evaluation of the
typical free energy change of a reaction is a major problem of physical chemistry.
The free energy variations are obtained from ∆H o and ∆S o from a reaction at a
particular temperature by means of equation (31) and by other procedures that will
be given later in this text. At this time, we will present a scheme used to calculate
free energies of formation of compounds from which the variations of these
energies can be calculated: in any class of reactions.
The free energy of formation of a compound is defined as the change that
accompanies its formation with a unit activity from its elements with equal activity :
The equation:

H 2(g) + 1/2O 2(g) = H 2 O (l)∆ F o298 K =¿ -56,690 cal (65)

gives us the change in free energy of formation of 1 mol of H 2 O (I) with a unit
activity from H 2 (g) and 1/2O 2 (g), both with an activity equal to unity. If we now
arbitrarily assume, as in the heats of formation, that the free energies of formation
o
of the elements in their type states at 25°C are zero, the value of∆ F 298 K above is
the free energy of formation of liquid water from the elements, and we can simply
write that Table 6-2 shows the free energies of formation for each mole of a
number of compounds at 25°C. These formation energies can be used to
calculate ∆ F of the reactions in a manner analogous to the heats of formation used
in the calculation of heats of reaction. Thus , for example, by taking the data from
the table, we find the typical free energy change at 25°C corresponding to the
reaction

1
N O( g) + O2(g) =N O 2(g)
2
∆ F o25 ° C =∆ F oNO 2−[ ∆ F oNO +1/2 ∆ F oO 2 ]
¿ 12390−20720−0
¿−8330 cal

2
BALANCE CRITERIA

Although the establishment of equilibrium in systems has been mentioned on

numerous occasions, no thermodynamic criteria for it have yet been specified. In
reality, it is possible to deduce a good number of criteria in terms of various
thermodynamic functions and the conditions under which equilibrium was
established. We will limit ourselves to disagreeing here on three criteria that are of
maximum interest and usefulness when working with chemical problems.

A system in equilibrium represents a balance of driving and opposing forces, that

is, a condition of reversibility. Additionally, no work is obtained from a system in this
state. Under these conditions, equation (17) from the last chapter gives us:

TdS - dU - PdV = 0 (67)

The volume and energy are constant here, so dU = dV = 0:

and also dS = 0. Therefore, we can write for a system in equilibrium
when U and V are constant, which in an infinitesimal change

3
 (∂s) U,V =. 0 (68a)
and in a finite change
(∆S) U,V = 0 (68b)
Equations (68a) and (68b) correspond to a maximum in the entropy of the system
for the following reason. The spontaneous process tends to proceed with an
increase in entropy, that is, with positive dS . At the same time, a non-spontaneous
process carried out with constant G and V must have negative dS. Hence at
equilibrium dS = 0, the entropy must be a maximum.
The equilibrium criterion when T and V are constant is expressed as a function of
the Helmholtz free energy. By differentiating equation (1)
we obtain
dA = dU - SdT - TdS
either
TdS - dU = -dA - SdT
By substituting the last expression in equation (67) we obtain
dA + SdT + PdV = 0 (69)
If T and V are constant
¿ (70a)
In an infinitesimal change, and for a finite change

¿ (70b)

PHYSICAL BALANCES THAT INCLUDE PURE SUBSTANCES

For a pure substance in a single phase, such as liquid or gaseous water, the
change in free energy is given by equation (27)
For phase equilibrium to exist, dF must be 0 when T and P are constant, so dT =
dP = 0; which tells us that the phase is in equilibrium when the pressure and
temperature are constant and uniform throughout it.
Let us consider a more interesting situation, the transition of a pure substance from
one phase to another. For example, the passage of a substance from one
crystalline form to another. the change from solid to liquid, the sublimation of a
solid and the vaporization of a liquid. All these changes are represented by the
equation
A1=A2

or, for
∆F = F 2 – F 1 (73)

4
where F 1 and F 2 are the molar free energies of the substance in the final and
initial states, respectively. All transformations will reach equilibrium when ∆ G = 0
at constant temperature and pressure. Imposing this condition on equation (73), it
gives us F 2 = F 1 ; or, in other words, all these transformations will be in
equilibrium at constant pressure and temperature when the molar free energy of
the substance is equal in both phases.
Suppose that there are two phases in equilibrium and that the pressure of the
system varies in dP. The temperature of the system will change by dT in order to
preserve equilibrium. In such a situation, dP and dT are related as follows: Since F
2 is equal to F 1 , we will also have dF 2 = dF 1 . But by equation (27) dF 2 = -S 2 dT

+ V 2 dP and dF 1 , = -S 1 dT + V,dP. By equating these expressions,

CLAPEYRON EQUATION

where ∆S = S 2 – S 1 is the change in entropy and ∆V = V 2 – V 1 is the change in

volume of the process. Furthermore, equation (20) with ∆F = 0, gives us ∆S =
∆HIT, where ∆H is the enthalpy change in the reversible transformation that occurs
at temperature T. Substituting this value of ∆S into equation (74) gives

dP ∆ H
= (75)
dT T ∆ V

Equation (75), known as the Clapeyron equation, relates the change in

temperature that must accompany the change in pressure in a two-phase system
of a pure substance in equilibrium. Again, the equation teaches that dP/dT is
related directly to the transition enthalpy and inversely to the temperature and
volume change that accompany the transformation.
To integrate equation (75), ∆H and ∆V must be known as functions of
temperature or pressure. Since such information is not ordinarily available,
equation (75) is used in differential form, that is:
P 2−P1 ∆ H
= (76)
T 2−T 1 T ∆ V

5
where T is the average between T 1 and T 2 , or the equation is integrated under
the assumption that ∆ H and ∆V are constants. Then we get:

Modified Clapeyron equation (77)

equation somewhat more exact than (76) and preferable in calculations that
include
noticeable temperature changes

USE OF THE CLAPEYRON EQUATION

In the previous form it is mainly used to calculate the equilibrium in

condensed phases, that is: equilibria that include solids and liquids. Its use is best
illustrated in the following discussion: It was shown in Chapter 2 that the fusion of a
pure solid occurs at a fixed temperature for a fixed pressure, and is accompanied
by a heat absorption equal to ∆H f = H l - H s , where the value of ∆H f is the molar
heat of fusion, and H l and H s , are respectively the molar enthalpies of the liquid
and solid. At the same time, the process is accompanied by a change in volume ∆
V f = V l – V s , where V l and V s are the molar volumes of the liquid and solid. If we
now change the total portion of the system from P 1 to P 2 , then the equilibrium
temperature varies from T 1 to T 2 .
To calculate the extent of change using the Clapeyron equation, let us
specifically consider the following example. In acetic acid the point of
fusion at 1 atm pressure is 16.61°C, ∆H f = 2,800 cal/mol, and ∆V f = 9.614 cd/mol.
What will be its melting point at 11 atm pressure? From equation (76) we deduce

T ( P2−P1 ) ∆ V
t 2−t 1=
( 41.29 ) ∆ H
where the factor 41.29 converts calories to cc. -atm. By placing the data for acetic
acid we obtain
289.76 ( 10 )( 9.614 )
t 2−t 1= =0.241 ° C
2,800 ( 41.29 )
and from here

6
 t 2 =16.61 + 0.24 = 16.85 °C
It will be observed that the effect of pressure on the melting point is not great, and
with small variations in pressure it can be ruled out. Water is an interesting
example of a substance that has V s greater than V l and therefore its melting point
decreases when pressure is applied.
The temperature at which a modification of the solid phase of a substance
carries out a transformation to another form, is, as in fusion, a function of pressure,
and in this case, too, is again given, by the equation Clapeyron, but ∆H and ∆V are
now the change in enthalpy and volume that accompany the transformation, that is,
we will represent them by ∆H t and ∆V t . For these transitions ∆H t is always
positive if the transformation is from a form stable at low temperatures to one that
is stable at higher temperatures, and negative for reverse transformations.

THE VAPOR PRESSURE OF LIQUIDS

Attention has been drawn to the fact that a liquid placed in a vessel will partially
evaporate to establish a vapor pressure above the liquid that depends on the
nature of the liquid, and is: at equilibrium, constant at any set temperature. This
pressure is known as the sutured vapor pressure of the corresponding liquid. As
long as this is maintained, the liquid no longer exhibits a tendency to evaporate,
but at a lower pressure there is a new transformation towards the gas phase, and
at a higher pressure, condensation occurs, until the equilibrium pressure is
restored.
For any liquid, vaporization is accompanied by the absorption of heat and the
amount of heat required for a given temperature and pressure: required to heat a
certain weight of liquid, which is known as the heat of vaporization and is the
difference in vapor enthalpies. and liquid, that is, ∆H v = H g – H l : where ∆H is the
heat of vaporization and H g and H l are the enthalpies of vapor and liquid.
In evaporation ∆H v is always positive. while in a condensation it is negative
and numerically equal to the heat absorbed in vaporization. As might be expected
from the definition of ∆ H ; ∆H v . is the difference between the internal energy of
the vapor and the liquid ∆ Uv = U g – U l and the work of expansion in the phase
change: that is,
∆ H v =∆ U v + P ∆V v

where P is the vapor pressure and ∆V v = V g – V l There are several procedures for
measuring the vapor pressure of a liquid that are classified as static and dynamic.
In the former, the liquid is allowed to establish its vapor pressure without that there
is any
disturbance, while in dynamic ones the liquid boils or an inert stream of gas is
passed through it.
The line between these methods is not always clear, and a particular
procedure is sometimes a combination of the two. The isoteniscopic method of
Menzies and Smith is accurate, flexible and convenient for measuring the vapor

7
pressures of a substance over a wide temperature range. A simple laboratory
device is shown in Figure 6-2. Bulb B is filled approximately half or three-quarters
with the test liquid, and in the U -shaped portion of tube C, 2 or 3 cm high of said
liquid is placed: then the isoteniscope is connected to the rest of the apparatus and
immerse it in a water bath A, whose temperature is measured with a thermometer
D. The device is equipped with a barometric tube to measure pressure, while G is
a large bottle that attenuates pressure fluctuations in the system. This bottle
connects well to a suction or air pump. In the operation, the system is evacuated
until the liquid boils vigorously in B, in order to expel all the air from BC.

Bath A is adjusted to the desired temperature and air is slowly admitted to the
system until the liquid levels in G-shaped tube C are
exactly the same. In these conditions. The pressures on both sides of the U-tube
must be equal. It is evident that then the vapor pressure at B must be equal to the
rest of the apparatus and can be obtained from the reading of the barometer and
the column of mercury at E. The difference between the barometric pressure and
that of E is the vapor pressure of the liquid in B at the temperature of the bath. The
reading at different temperatures is obtained when we change them in bath A and
repeat the operation.
A simple dynamic method is presented in Figure 6-3. The test liquid B is boiled
after removing the air it contains under a measured external pressure and the
condensation temperature of the vapor is read with a thermometer T. The
barometric pressure minus the pressure P is the pressure at which the liquid boils,
and is the vapor pressure of the liquid at temperature T.
If we change the pressure P, the liquid boils at different temperatures and the
corresponding vapor pressure is obtained. The function of the flask collected
vapor, then the partial pressure of the vapor P which is equal to that of vapor of the

8
liquid in the saturation condition is to condense any escape of vapor and prevent
distillation of the liquid in the mercury manometer
.
Walker proposed a more elaborate dynamic method that consists of saturation
with some inert gas such as nitrogen. with vapor by bubbling a measured amount
of gas through the liquid at a constant temperature and then condensing or
absorbing it to weigh the vapor of the Liquid. If P t is the pressure in the apparatus
under saturation conditions, n g the moles of gas passing through it, and n v = W
v /M v the number of moles of vapor collected, then the partial pressure of the vapor

P which is equal to that of vapor of the liquid in the saturation condition is:

P=
( nv
ng + nv ) (79)

PRESSURE VARIATION. STEAM WITH TEMPERATURE

The vapor pressure of a liquid is constant at a given temperature, but increases

as the temperature increases up to the critical point of the liquid. Above the critical
temperature. There is no longer any liquid, and therefore the concept of saturated
vapor pressure is not valid.
It is easy to understand the increase in vapor pressure considering the kinetic
theory. As the temperature increases, the portion of molecules that acquire enough
energy to escape from the liquid phase increases, and consequently, greater
pressure is required to establish an equilibrium between the vapor and the liquid.

9
Above the critical temperature the escape tendency of the molecules is so high that
no applied pressure is sufficient to keep them together in the liquid state, and the
entire mass persists as a gas.

Figure 6-4 shows how vapor pressure varies with temperature. There is a slow
ascent at low temperatures, and then a very rapid one as could be observed by the
increase in the slope of the curves. This variation

of vapor pressure with temperature is expressed mathematically with the Clausius-

Clapeyron equation. For the transition from liquids to vapor P is the pressure at
temperature T, ∆H = ∆ H v the heat of vaporization of a given weight of liquid, and
V 1 = V L the volume of the liquid, while V 2 = V g is the volume of the same weight
of steam.
Consequently, for vaporization the Clausius-Clapeyron equation can be written
as follows:
dP ∆ H v
= (86)
dT T ¿ ¿
At a temperature not very close to the critical V l is very small compared to V g
and can be neglected. Thus at 100°C, V g of water is 1.671 cc. per gram, while V I

10
is only 1.04 cc. per gram. Furthermore, if we assume that the vapor behaves
essentially as an ideal gas, then V g per mole is given by V g = RTIP and equation
(80) becomes:
dP ∆ Hv ∆ Hv P . ∆ H v
= = = rearranging
dT T (∆ V ) T V g RT
2

dP ∆ H v dT
= ec (81)
P R T2
Where the eq. (81) is known as the Clausius-Clapeyron equation

In order to integrate it, it is necessary that ∆H v , molar heat of vaporization, be

known as a function of temperature. If we assume as an approximation, however,
that throughout the problem interval ∆H v remains constant, the integration leads to:

( )
∆ H v −1
por integración lnP= +C (82a)
R T
EITHER
−∆ H v 1
logP= ( )
2.303 R T
+C
'
(82b) where C' and C are

integration constants. Equation (82) predicts that the logarithm of the vapor
pressure should be a function of the reciprocal of the absolute temperature .
Furthermore, comparison of the equation with that of a straight line, that is, y = mx
+ b, suggests that if log 10 P for a liquid is graphed against 1/T, the graph must be a
straight line with a slope m = (- ∆H V /2.303R), ey - intercept b = C which is in
accordance with the facts observed in Figure 6-5, where the data shown in Figure
6-4 are now graphed as log 10 P versus 1/T. From the slopes of the lines, the heats
of vaporization of various liquids are deduced, thus

34. ch6 (Maron and Prutton)

The heat of fusion of ice is 79.7 cal/g at 0°C. The densities of ice and water at
that temperature are 0.9168 and 0.9999 g/cc , respectively. Calculate the melting
point of ice at 325 atm pressure, and compare the answer with the observed
value , which is -2.5°C.
L
3.2933 atm−
∆ P=P2−P1=
∆ Hv
∆V ( )
T
ln 2 ; 324=
T1
( 1
− )
1
g
( )
x 10−3 L /g
T
ln 2
T1
0.9999 0.9168

( )
T2 −3
−3 −8.9183 x 10
ln =−8.9183 x 10 ; entonces T 2=T 1 e =270.72 K=−2.425 ° C
T1

11
39. At the normal boiling point, 61.5°C, the heat of vaporization of CHCl 3
is 59.0 cal/g. Assuming that steam behaves like an ideal gas, and that the
volume of the liquid is negligible compared to that of the vapor, what is the value
of ∆ U per mole in the vaporization process?
∆ H v =∆ U + P ∆V =¿ ∆ U + P V g
From the general gas equation
59.0 cal cal 1mol cal
∆ U =∆ H v −Ru T ; ∆ U = −1.987 x 334.65 x =53.426 =6376.700 cal/mol
g mol−K 119.35 g g
41. The heat of vaporization of ethyl ether is 83.9 cal/g while its pressure
of vapor at 30°C is 647.3 mm. What will be the vapor pressure at 0°C?

( )
cal
83.9
ln 647.3=−
1.987
g
cal
x 74
g
x
1
(
mol 303.15 k
+C )
mol−K

12
 [( ) ]
cal
−83.9
6.4728=−10.307+C ; C=16.7799 ; P=exp
1.987
g
cal
x 74
g
x( 1
mol 273.15 k)+16.7799 =208.66 mm Hg
mol−K

13