Intro Thermo Public in Felt A Partial
Intro Thermo Public in Felt A Partial
Intro Thermo Public in Felt A Partial
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THERMODYNAMICS
Pierre Infelta
BrownWalker Press
QD504.I54 2004
542’.369––dc22 2003027840
Foreword
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and is enriched with colored figures.
Pierre Infelta
School of Basic Sciences,
Swiss Federal Institute of Technology
Lausanne, Switzerland
Table of contents
3.1 Introduction
Energy exchanges between bodies do occur. One can observe :
15
16 Introductory Thermodynamics
Example
The work done on a gas during an adiabatic process is 1000 J. The change of its internal
energy for this process is :
UF – UI = wadiabatic = 1000 J
17
18 Introductory Thermodynamics
p
1
4 2
V
Figure 4.1 Example of a Carnot engine cycle.
An engine provides work to a user (w is negative). For a Carnot engine
cycle (or forward Carnot cycle), it can be shown that we have the
following relations :
w + qh + q = 0 qh 0
(4.3)
w0 q 0 and qh |q |
where w is the algebraic work done on the system during the cycle.
For any system undergoing a reversible Carnot cycle, one can show
that the ratio of the amount of heat received by a system from each
thermal reservoir is independent of the system and depends only on
the thermal reservoirs.
This fact is used to define a temperature scale that has a universal
character, the thermodynamic temperature. We write :
Th qh q q
h
=– + 0 (4.4)
T q Th T
This choice implies that the temperatures of the thermal reservoirs
have the same sign on this scale and are always positive. We also
have :
Th T (4.5)
4 Second Law of Thermodynamics 19
chapter 4.
4 Second Law of Thermodynamics 21
Example
Consider a system undergoing a Carnot cycle. For this cyclic process the entropy change
of the system is zero since the initial and final states of the system are the same. The
entropy changes of the thermal reservoirs are :
qh q
(SF – SI)therm h = – T (SF – SI)therm = – T
h
In virtue of Eq. 4.4, the global entropy change (system plus thermal reservoirs) is found to
be zero.
Example
Consider two containers with adiabatic walls separated by a stopcock. Initially, one
container contains one mole of an ideal gas at a pressure of 1 bar, while container 2 is
evacuated. Both containers have the same volume. The initial temperature of the gas
is 25°C.
We open the stopcock. An irreversible
expansion takes place and the gas Gas Vacuum
occupies the entire volume at its
disposal. Since the system is
adiabatic, q = 0, and the system
volume does not change, w = 0, the internal energy of the gas does not change.
UF – UI = 0 = w + q
The internal energy of an ideal gas depends only on its temperature (chapter 7). When the
system has reached equilibrium, its temperature has not changed. The change in the
entropy of the gas can be obtained starting from (Eq. 4.13) using also the ideal gas law :
p dV
dU = 0 = – p dV + T dS dS = T dV = n R V
VF dV VF
SF – SI = n R V = n R ln V = 8.3145 · ln 2 ≃ 5.76 J K–1
I
V
I
For this irreversible adiabatic process, the entropy of the system increases.
V
of the process.
qi sys is the amount of heat received by the system from the thermal
reservoir at temperature Ti. The equality is valid for a reversible
cycle while the inequality applies to any irreversible cycle.
Example
For a cyclic process of a system entering in contact with n thermal reservoirs, the entropy
change of the system is zero. From the amount of heat received by the thermal reservoir
at temperature Ti, we find the entropy change of that thermal reservoir to be :
n
qi sys qi sys
(SF – SI)therm i = – Ti (SF – SI)global = – Ti ≥0
i=1
We find using 4.12 that the global entropy change is positive for an irreversible cyclic
process and zero for a reversible one.
is constant. We obtain the expression for the change in entropy of an ideal gas
characterized by its temperature and volume :
TF VF
SF – SI = n CV,m ln T + R ln V
I I
Using the ideal gas law and Eq. 5.52, we find expressions for the entropy change when the
states are characterized by other variables :
pF VF VF pF VF
SF – SI = n CV,m ln p V + R ln V = n CV,m ln p + Cp,m ln V
I I I I I
T
F p T
I F T
F p
F
SF – SI = n CV,m ln T + R ln p T = n Cp,m ln T – R ln p
I F I I I
C p, mis the molar heat capacity of the gas at constant pressure (chapters 5 and 6.
TF TF
HF – HI = Cp dT + Cp dT = Cp (TF – T1) + Cp (TF – T2) = 0
T1 T2
TF =
T1 + T2
2
(4.15)
The entropy change of the system during the process is :
4 Second Law of Thermodynamics 25
T1 T2
TF Cp TF Cp TF TF
SF – SI = dT + dT = Cp ln + Cp ln (4.16)
T T T1 T2
T1 T2
T2F (T1 + T2 )2
SF – SI = Cp ln = Cp ln
T1 T2 4 T1 T2
(4.17)
(T1 – T2 )2
SF – SI = Cp ln 1 +
4 T1 T2
The entropy change of this closed adiabatic system is always positive,
except if both blocks are at the same temperature. Then no process
takes place, since the blocks are already in thermal equilibrium.
Example
Let us examine how the ratio (SF – SI )/Cp varies with the ratio T2/T1 of the initial
temperatures of the blocks. We have :
2
1 – T
T2 0.5
SF – SI 1
)IS Ð FS(
Cp = ln 1 +
4T
pC
T2
1
Figure 4.3 Isothermal expansion of an ideal gas. The walls of the cylinder are in
thermal contact with a thermal reservoir. The mobile piston is
adiabatic.
A system contains n moles of an ideal gas in a cylinder closed by a
mobile adiabatic piston (Fig. 4.3). The other walls of the cylinder are
in thermal contact with a thermal reservoir at temperature T.
The external pressure stays identical to the pressure inside the
system, pext ≃ pint, for all states during the process. The internal
energy of the ideal gas remains constant (See chapter 7). We have :
UF – UI = 0 = wsys + qsys
qsys = n R T ln
V
I
The entropy change of the system is :
F
1 qsys VF
(SF – SI)sys = dqrev = = n R ln (4.19)
T T V
I I
Example
Let us find the work done on 0.1 mole of an ideal gas during a reversible isothermal
process at 400 K when its volume doubles.
4 Second Law of Thermodynamics 27
VF
wsys = – n R T ln V = – 0.1 · 8.3145 · 400 ln 2 ≃ – 230.5 J
I
The amount of heat received (from the thermal reservoir) by the system and its entropy
change are :
VF
qsys = – wsys ≃ 230.5 J (SF – SI)sys = n R ln V ≃ 0.58 J K–1
I
The internal energy of the gas stays constant during the process. The work obtained
comes integrally from the thermal reservoir. The entropy change of the thermal reservoir
is :
qtherm qsys
(SF – SI)therm = T = – T ≃ – 0.58 J K–1
The global entropy change for this reversible process is zero.
4.3.9 Monothermal Irreversible Expansion of an Ideal Gas
Consider now the irreversible expansion of the ideal gas where the
initial and final states of the gas are the same as in the case just
examined (Fig.4.3).
The external pressure is now assumed to remain constant during the
process and has the value pF pI. Entropy is a state function, the
entropy change of the system is :
VF pI
(SF – SI)sys = n R ln = n R ln (4.22)
V p
I F
The work done on the system is :
VF VF
wsys = – pext dV = – pF dV = – pF (VF – VI) (4.23)
VI VI
The final temperature of the gas is the same as its initial temperature
and equal to the thermal reservoir temperature. The first law
provides :
UF – UI = 0 = wsys + qsys qsys = – wsys = pF (VF – VI) (4.24)
The entropy change of the thermal reservoir is :
qtherm = – qsys = – pF (VF – VI)
(SF – SI)therm=
qtherm
=–
pF (VF – VI)
=–
pFVF
1 –
VI
T T T
VF
= – n R 1 –
VI
= – n R 1 –
pF
VF
pI
(4.25)
28 Introductory Thermodynamics
Combining 4.22 and 4.25, we obtain the entropy change of the global
system (gas plus thermal reservoir) :
pI pF
(SF – SI)global = n R ln – 1 – (4.26)
pF pI
We show in Fig. 4.4 how the global entropy changes as a function of
the ratio pF /pI. The entropy of the global system increases except if
pF = pI (when no process takes place).
pF
pI
Figure 4.4 Entropy changes for a monothermal irreversible process (expansion or
compression) of an ideal gas at constant external pressure pF.
Example
Let us find the work done on 0.1 mole of an ideal gas during the irreversible monothermal
process of § 4.3.9 when its volume doubles (same initial and final states as in the previous
example). The temperature of the gas is 400 K in its initial and final states. The work done
on the system is :
VI
wsys = – pF (VF – VI) = – pF VF 1 – V
F
VI
= – n R T 1 – V = – 0.1 · 8.3145 · 400 · 0.5 ≃ – 166.3 J
F
The amount of heat received by the system is :
qsys = – wsys ≃ 166.3 J
The entropy change of the system is the same as in the reversible process (previous
example) since entropy is a state function. The entropy change of the thermal reservoir is :
qtherm qsys 166.3
(SF – SI)therm = T = – T ≃ – 400 ≃ – 0.42 J K–1
4 Second Law of Thermodynamics 29
The change of the entropy of the global system (system + thermal reservoir) is :
(SF – SI)global = (SF – SI)sys + (SF – SI)therm ≃ 0.58 – 0.42 = 0.16 J K–1
As expected from the second law, it is a positive quantity.
dq = dU – dw = CV dT + p dV = 0 (4.27)
Since the process is reversible, we can express p with the ideal gas
law, we obtain :
dV dV
CV dT + n R T =0 CV dT + (Cp – CV) T = 0 (4.28)
V V
We replaced n R by its value in terms of the heat capacities of the
system (Eq. 5.52). We can divide Eq. 4.28 by the number of moles n
and, assuming constant molar heat capacities, we can integrate the
resulting differential equation.
T2 V2
CV, m ln + (Cp, m – CV, m) ln = 0 (4.29)
T1 V1
CV, m and Cp, m are the molar heat capacities. We can obtain various
forms of this relation :
Cp, m
– 1
C
T2 V1 V, m V1 ( – 1)
Cp , m
=
T1 V2
=
V
2
with =
CV, m
(4.30)
using p V = n R T p 1V1 = p 2V2
The entropy change of the system is zero. This process is an
isentropic process. During an isothermal change of an ideal gas, the
product p V remains constant, while during an isentropic change, it is
the product p V that remains constant. In a diagram giving p vs. V,
and at a specific point p0, V0, the slope of an isothermal curve is
- p0/V0 while that, on an adiabatic curve going through the same point,
is – p0/V0. The ratio of the heat capacities at constant pressure and
at constant volume, , is always larger than 1 (see Fig. 4.5). The
absolute value of the slope of the adiabatic curve is always larger than
that of the isothermal curve going through the same point.
30 Introductory Thermodynamics
p Isothermal curve
2 3 4 5
x10
-2
6 7 8
Adiabatic curve
p0
V0 V
Figure 4.5 Comparison of reversible adiabatic and isothermal curves for an
ideal gas.
Example
Use C V, m= 5 R/2 = 20.8 J mol–1K–1 for a monoatomic gas assumed to behave ideally. A
reversible adiabatic compression brings one mole of the gas at 300 K, 1 bar to 2 bar.
From Eq. 4.29 using the ideal gas law, we get :
T2 V2 T2 T2 p1
C V, m ln T + R ln V = 0 C V, m ln T + R ln p T = 0
1 1 1 2 1
R
T2 p1 p2 C
C p, m ln T + R ln p = 0 T2 = T1 p p, m = 300 · 20.4 = 396 K
1 2 1
Th
4 Second Law of Thermodynamics 31
1 T 1 2
p
4 2
3 4 3
V S
Figure 4.6 Representation of a Carnot cycle. In the direction used here, this is
an engine cycle. The area inside either curve represents the work
done on the system.
Example
A system undergoes a Carnot cycle. The thermal reservoirs temperatures are Th = 1300 K
and T = 300 K. Let us find what the entropy change from state 1 to state 2 needed to
obtain 1000 J of usable work (w = – 1000 J). We have :
w 1000
S2 – S1 = – T – T = 1300 – 300 = 1 J K–1
h
Thermal q q Thermal
reservoir h reservoir
Machine T
Th
Figure 4.7 Heat and work exchanges taking place in a thermodynamic machine, in
contact with two thermal reservoirs. The indicated heat and work are
those received by the machine which here constitutes the system.
For refrigerators and heat pumps, this ratio is often larger than 1 and
is usually called the coefficient of performance. In Fig. 4.7, we show
the energy exchanges that take place using the sign convention
mentioned earlier.
e = 1 +
qh
1–
Th
The efficiency of a real engine isalways smaller than that of a
reversible engine and always smaller than 1.
Example
Let us find the maximum efficiency for a thermal engine that exchanges heat with only two
thermal reservoirs at 2000 K and 300 K.
T 300
e(rev) = 1 – T = 1 – 2000 = 0.85
h
4 Second Law of Thermodynamics 33
q q
h
+
q
0 –
h
Th
Th T
q T
q q 1 1 (4.40)
r = = =
w – qh – q qh
Th
–
q
–1
T
–1
Example
We calculate the maximum value of the coefficient of performance for a refrigerator that
operates reversibly in a room at 298 K while the inside is kept at 278 K :
1 1
r = T = 298 = 13.9
h
T – 1 278 – 1
If 100 W of work is provided, the maximum amount of heat that can be extracted from the
refrigerator in 1 hour is :
w = 100 · 3600 = 3.6 105 J q= r · w = 13.9 · 100 · 3600 ≃ 5 MJ
In practice this type of efficiency can never be achieved of course.
The heat of fusion of ice is 6000 J mol–1. The maximum amount of water already at
freezing temperature that can be transformed in ice is :
18 10–3 kg mol–1· 5 106 J
m= ≃ 15 kg
6000 J mol–1
34 Introductory Thermodynamics
q
h
Th
+
q
T
0
q
qh
–
T
Th
– qh – qh 1 1
(4.41)
HP =
w
=
– qh– q
=
q
T
1+
qh
1–
Th
The efficiency or coefficient of performance is found to be lower
than that of an ideal machine operating reversibly between the same
heat sources.
Example
We calculate the coefficient of performance of a heat pump that operates reversibly to
warm up a house at 298 K while the outside temperature is 273 K.
1 1
HP = T = 273 ≃ 11.9
1–T 1 – 298
h
If work is provided at the rate of 100 W, the maximum amount of heat, qh, that can be
released inside the house in 1 hour is :
w = 100 · 3600 = 3.6 105 J qh= HP · w = 11.9 · 100 · 3600 ≃ 4.29 MJ
p 3
4
2
1
V
Figure 4.8 Representation of the Otto cycle (or Beau de Rochas cycle).
q T1 – T4
e= 1+ =1+ (4.44)
qh T3 – T2
Example
For a mixture of gases with = 1.4 and a compression ratio of a = 8, the efficiency is :
1
e = 1 – (1.4 – 1) = 0.56
8
After compression the gas mixture, initially at 300 K has reached :
VF ( – 1) 0.4
T2 = T1 V = 300 · 8 = 689 K
I
To obtain 1000 J of useful work we must supply :
w – 1000
qh = – = – 0.56 ≃ 1786 J
e
Assuming we have 0.04 mol of gas mixture (1 liter of gas at 300 K) with a molar heat
capacity, CV, m= 20.8 J mol–1 K–1, the temperature reached by the gas at the end of the
combustion is :
qh 1786
T3 = T2 + n C = 689 + 0.04 · 20.8 ≃ 2836 K
V, m
p 3 Isothermal Tl
Isothermal Th
4.0 3.5 3.0 2.5
x10
5
2.0 1.5 1.0 Isochoric
4
2
1
V
Figure 4.9 Schematic representation of the Stirling cycle.
4 Second Law of Thermodynamics 37
V1
– w = (q + qh ) = n R (Th – T) ln (4.48)
V
2
w T
e= – =1– (4.49)
qh Th
Example
Let us examine a Stirling cycle of 0.05 mol of N2 behaving ideally. The thermal reservoir
temperatures are 300 K and 600 K. The heat capacity of the gas is assumed to be
constant and we use CV, m = 5 R/2 = 20.8 J mol–1K–1. In state 1, the pressure of the gas
is 105 Pa. The volume V2 is 1/10 of V1. Volumes and pressures are :
0.05 · 8.3145 · 300 V1
V1 = ≃ 1.247 10 –3 m3 p = p = 106 Pa
105 2 1V
2
Th V2
p3 = p2 T = 2 106 Pa p4 = p3 V = 2 105 Pa
1
We have the following results :
q = – w = 0.05 · 8.3145 · 300 ln 0.1 ≃ – 287 J
w ≃ – 287 J
qh = – wh = 0.05 · 8.3145 · 600 ln 10 ≃ 574 J
The cyclic process produces work. The heat received by the system during step 2–3 is :
Th
qi = n CV, m dT = 0.05 · 20.8 · (600 – 300) ≃ 312 J
T
38 Introductory Thermodynamics
This amount of heat is usually obtained mostly from a heat exchanger that is heated during
step 4–1 when the system receives – qi, warming up the heat exchanger in the process.
Note that steps 2–3 and 4–1 can be reversible only if the system can get in contact with an
infinite number of thermal reservoirs always at the system temperature as its pressure and
temperature change. If, at step 2, the system is brought in contact with the thermal
reservoir at high temperature, then the heat exchange is irreversible. In this case, we can
use the result of example of § 4.3.5 to find the entropy change for the global system during
step 2–3 is :
(S3 – S2)global = (S3 – S2)sys + (S3 – S2)therm
Th qi
= n CV, m ln T – T
h
312
= 0.05 · 20.8 · ln 2 – 600 ≃ 0.20 J K–1
The positive result obtained agrees with the second law. If the isochoric process takes
place when the system is in contact with the cold thermal reservoir then we find :
(S1 – S4)global = (S1 – S4)sys + (S1 – S4)therm
T qi
= n CV, m ln T + T
h
1 312
= 0.05 · 20.8 · ln 2 + 300 ≃ 0.319 J K–1
7. Thermodynamics of Gases
p
dp p
d = R T p =0(T) + R T ln 0
p
(7.3)
0 p0
The chemical potential of a pure ideal gas has the value 0(T) at
pressure p0. 0(T) is a function of temperature only.
69
70 Introductory Thermodynamics
Example
Let us calculate the change in the chemical potential of an ideal gas when its pressure
varies from 1 bar to 2 bar at 300 K. We have :
2
(T, 2) – (T, 1) = 8.3145 · 300 · ln 1 ≃ 1729 J mol –1
At a temperature T, the difference of the standard chemical potentials using 1 bar or 1 atm
as the standard pressure is :
_o _o p_ob
b – a = R T ln _ = – T where = R ln 1.01325 = 0.10944 J mol–1 K–1
o
pa
At 298.15 K the difference of the two standard potentials is 32 J mol–1.
_ (7.5)
o
where S (T) is the standard molar entropy of the _ideal gas
o
considered, at temperature T. Since only depends on T, S depends
only on T as well. Various expressions of the molar enthalpy are :
Hm = +T Sm
_
o
d
_
o
= + R T ln p + T – – R ln p
dT
G = H – TS
_o
d
_
o
d
T
_
o _
o
= –T = –T 2 =H
dT dT
_ (7.6)
o
Hm is identical to the standard molar enthalpy, H , independent of
pressure.
7.2 Mixtures of Ideal Gases
7.2.1 Basic Properties. Ideal Gas Mixture. Dalton’s Law
A mixture of ideal gases is an ideal gas mixture if both of the
following properties are valid :
•
The internal energy of the mixture at temperature T is the
sum of the internal energy of the species (ideal gases) of the
mixture taken separately at the same temperature T.
7 Thermodynamics of Gases 71
U = U i (7.7)
i
• The enthalpy of the mixture at temperature T is the sum of
the enthalpy of the species (ideal gases) of the mixture taken
separately at the same temperature T.
H = H i (7.8)
i
The equation of state of a pure ideal gas and the definition of H allow
us to write :
H =U+pV= (U + p V ) = U + n R T = U + n R T
i i i i (7.9)
i i
The number of moles n identifies with the sum of the number of moles
of the species as it should.
Example
Consider an ideal gas mixture containing two species. Assume that the heat capacities at
constant volume are constant. The change of the internal energy of the mixture, when the
temperature changes, is :
U2 – U1 = (n1 CV, m 1 + n2 CV, m 2) (T2 – T1 )
unaffected by volume.
The change of the enthalpy is, using 5.52 :
H2 – H1 = (n1 CV, m 1 + n2 CV, m 2)(T2 – T1 ) + (n1 + n2) R (T2 – T1)
= (n1 Cp, m 1 + n2 Cp, m 2)(T2 – T1 )
unaffected by pressure.
If the ni moles of species i occupied by themselves the entire volume,
the pressure as given by the equation of state would be :
pi V = ni R T (7.10)
The pressure pi is known as the partial pressure of species i in the
mixture. We can write using the fact that there are n moles of gas :
p i
R T p1 pi i p
= = … = =…= = using p V =n R T (7.11)
V n1 ni n
ni
i
ni
p= pi pi = p xi xi =
n (7.12)
i
72 Introductory Thermodynamics
V = … = ni pR T = …
= V dp – S dT + i dni with
i
dG
i dp = i dpi (7.14)
ni R T
= pi dn
dpi – S dT + i i
i i
We can find the variation of i with the partial pressures. Using
Schwartz theorem, we find :
7 Thermodynamics of Gases 73
∂ ni R T
∂ i
RT
∂pi p ,T, n , n = ∂ni pi p , p ,T, n = pi
j i j i j
j
(7.15)
∂ i ∂ nj R T
∂pj p ,T, n , n = ∂ni pj p , p ,T, n = 0
i i j i j j
From Eq. 7.15 and 6.12, one can find the expression for the chemical
potential of an ideal gas in a mixture.
pi
_
o _
o
i = i (T) + R T ln pi = i (T) + R T ln _
_
p
o
(7.16)
o
= i (T)
+ R T ln p + R T ln xi
From this expression, we can get expressions for other
thermodynamic properties. Using 6.29, we get :
_o
∂ i
H i = – T 2
∂ i
= – T 2
∂T T p, n , n
i j
∂T T p, n , n
i j
_o
i
(7.17)
d
T _
o
=–T2 = H i = Hi, m
dT
The partial molar entropy of an ideal gas in an ideal gas mixture
depends on the composition of the mixture.
_
∂i
Si =– =–
o
d i
– R ln p – R ln xi
∂T p, n , n
i j
dT
(7.18)
=
_
o
– R ln p – R ln xi = S*i, m – R ln xi
S i (T)
_
o
the standard molar entropy of species i. S *i, m is the molar
S i (T)is
entropy of species i pure at pressure p. The superscript * is
conventionally used to indicate a pure species property.
Example
Consider an ideal gas mixture assuming that the Cp,m i are constant. From the enthalpy of
the pure species, we obtain the partial molar enthalpy :
Hi = ni Hm i(T0) + Cp, m i (T – T0)
∂Hi _o
H i = ∂n = Hm i(T0) + Cp, m i (T – T0) = H i (T)
i T,p
74 Introductory Thermodynamics
mixS =
ni S i – ni S*i, m = – ni R ln xi (7.19)
i i i
Since the mole fractions xi are smaller than 1, the system entropy
increases during the mixing process. We also have :
mixH = HF – HI = 0
mixG = GF – GI = mixH – T mixS
(7.20)
= T n R ln x
i i
i
The enthalpy and internal energy of mixing are zero and the
Helmholtz energy of mixing is given by :
mixU = UF – UI = 0
mixA = AF – AI = mixU – T mixS
(7.21)
= T n R ln x
i i
i
Note that the change in A is equal to the work done on the system
during this reversible process. Since the internal energy of the gases
does not change (T is constant), the system also receives heat during
this reversible process.
7 Thermodynamics of Gases 75
i
We find, as expected, that the entropy change of the global system is positive.
C2 C1
Einteraction = – 6 (7.22)
r12 r
76 Introductory Thermodynamics
E r
r
n
_
o
i = i (T) + R T ln p + R T ln xi G= i i
i
xi =
ni
=
n 0i + i
(10.3)
n (n j
0
j + j )
j j
and finally :
0
n i + i
G() = (n i + i ) i (T) + R T ln p
_
o 0
(10.4)
i (n j + j ) 0
j
10.1.2 Schematic Representation
The function G() depends on pressure, temperature, stoichiometric
coefficients of the reaction, chemical potential of the species in their
standard state and on the extent of reaction. We have given in
Fig. 10.1 a schematic representation of G() as a function of , for
isobaric and isothermal conditions. The state of equilibrium for this
system corresponds to the value of for which the Gibbs energy is
minimum (See 5.7). The system tends to spontaneously evolve towards
this state. We can now look in more detail at the equilibrium criterion
and the spontaneity of chemical reactions under various conditions.
G(x)
x min 0 x eq x max x
Figure 10.1 Schematic representation of G() as a function of the reaction extent
for isobaric and isothermal conditions.
10 Chemical Equilibria 119
=0
Chemical equilibrium is reached
rG = i i
G has reached its minimum value (10.5)
i
Example
Consider an isothermal isobaric (pressure ptot) system where the following reaction takes
place between ideal gases :
2 A(g) A (g) 2
Pressures are proportional to number of moles and depend on the reaction extent. Using
the properties of equal ratios, we have :
nA = nA0 + pA pA ptot
2 2 2
= =
nA = nA0 – 2 nA0 + 0
nA – 2 0
nA + nA0 –
2 2
The value of the reaction extent eq that corresponds to the equilibrium is the value of
solution of :
_o nA0 + _ nA0 – 2
rG = 0 A + R T ln
2
p – 2 o + R T ln ptot = 0
0 0 0 0
2 nA + n A – tot A nA + nA –
2 2
The equilibrium state depends on the temperature, the standard chemical potential of the
species and the pressure imposed to the system. The volume at equilibrium is different
from the initial volume.
(nA0 + nA0 – eq) R T
2
V= ptot
120 Introductory Thermodynamics
dA = – p dV – S dT + dn = d
i i i i
i i
(10.6)
∂A
=
∂ V, T
d = rG d
According to the sign of rG, we obtain the same conclusions as in the
isothermal isobaric case (in general, the system pressure changes).
The equilibrium is achieved when the Gibbs energy of reaction is
zero :
=0
Chemical equilibrium is reached
rG = i i
A has reached its minimum value (10.7)
i
Example
Consider an isothermal isochoric system (volume V) where the following reaction takes
place between ideal gases :
2 A(g)
A2 (g)
Here again, pressures are proportional to number of moles and depend on the reaction
extent. The system pressure depends also on the reaction extent.
nA = nA0 + pA pA ptot RT
2 2 2
= = = V
nA = nA0 – 2 nA0 + 0
nA – 2 0
nA + nA0 –
2 2
The value of the reaction extent eq that corresponds to the equilibrium is the solution of :
_o R T _o R T
rG = A + R T ln (nA0 + ) 0
V – 2 A + R T ln (nA – 2 ) V = 0
2 2
writing
_
o
A* (T, p) = A (T) + R T ln _
o
p
A(l)
= A * (T, p) + R T ln x
A
139
140 Introductory Thermodynamics
KA= exp
RT
We get back more than assumed, since we obtain the dependence of
KA on p. We have (6.25) :
* VA (l) V *
∂ ln KA 1 ∂ A (T, p) A, m
= = RT = RT (11.7)
∂p T R T ∂p T
*
where V A, m is the molar volume of pure A liquid. The variation of KA
with pressure is rather small since, in general, the molar volume of a
liquid is small compared to R T.
Example
For H2O at 25°C, we have :
∂ ln KA
Vm = 18 10–6 m3 = 7.3 10 –9 Pa–1
∂p T
For a pressure change of 1 bar (105 Pa), the relative change of KA is 7.3 10–4.
When xA is close to 1, the solution is ideal and we see that KA
corresponds to the vapor pressure of liquid A pure at pressure p. We
can write the following relations neglecting the effect of the pressure
on the chemical potential of pure A :
11 Perfect and Ideal Solutions 141
_
o
A* (T, p) ≃ A (T) + R T ln p A* (T)
_
o *
KA p ≃ p A (T) = kR A Raoult’s constant
(11.8)
*
pA ≃ xA p A Raoult’s Law
A species in a solution is said to obey Raoult’s law when the last
equation of 11.8 is experimentally verified. This type of behavior is
experimentally observed in the case of liquid mixtures of species of a
similar nature as well as for the solvent in dilute solutions. The
constant kR A is Raoult's constant for species A. It is equal to the
vapor pressure of pure A. The standard chemical potential of A in the
liquid is related to the standard chemical potential of A in the gas
phase and to the vapor pressure of A by the first equation of 11.8.
Example
At 320 K, the vapor pressure of pure liquid hexane in equilibrium with its vapor is
48248 Pa. In an ideal solution with a mole fraction of hexane xhex = 0.4, the partial
pressure of hexane when liquid vapor equilibrium is achieved is :
phex = 0.4 · 48248 = 19299 Pa
%$&
'
V
Liquid
L
O ("
Vapor '
p p,#
&
x y
Figure 11.1 Partial vapor pressures and total pressure in a binary system at
350 K. The system contains hexane and triethylamine.
*
pA xA p A pB xB p B*
yA = = yB = = (11.10)
p xA p A* + xB p B* p xA p A* + xB p B*
The curve giving the pressure of the system at equilibrium as a
function of the vapor composition is the condensation curve or the
dew point curve.
Example
In the data presented in Fig. 11.1, the vapor pressures of the pure species (hexane and
triethylamine) at 350 K are p *A = 129761 Pa and p B* = 68429 Pa. For a composition of the
liquid phase where xhex = 0.6, the equilibrium pressure is :
p = 0.6 · 129761 + 0.4 · 68429 ≃ 105229 bar
The vapor composition is :
0.6 · 129761
yhex = 105229 ≃ 0.740
We have :
yA xA
yB xB if
p A* p B*
yA pA xA p A*
= = (11.11)
yB pB x p * y x
B B
yAB xAB if p A p B
* *
11 Perfect and Ideal Solutions 143
We find the ratio of the number of moles in the vapor phase to the number of moles in the
liquid phase to be :
n(g) (zhex – xhex) 0.4 – 0.335
n(l) = (y – z ) = 0.489– 0.4 ≃ 0.73
hex hex
All these results can be graphically estimated on Fig. 11.1.
Figure 11.3 Osmotic pressure. Only pure solvent can go through the membrane
separating the two compartments. At equilibrium, a pressure
difference must exist between the two compartments.
nsolute
x solv = 1 – xsolute and ln (1 – xsolute) ≃ – xsolute ≃ –
nsolv
= p’ – p ≃
RT
xsolute ≃
nsolute R T
V *m, solv Vsolv
(11.32)
Example
Let us evaluate the osmotic pressure at 300 K for a system where we have a solution of
10 g of methanol in 100 g of water separated from pure water by a membrane permeable
only to water. We use MH2O = 18.05, MMeOH = 32.04 and Vm(H2O) = 18.11 10–6 m3 mol–1.
We have :
100
nH O = 18.05 ≃ 5.54 mol nH O
2 2
10 x solv = nH O + nMeOH ≃ 0.947
nMeOH = 32.04 ≃ 0.312 mol 2
Activity —, 17, 30
coefficient and molality, 164 reverse —, 18
coefficient in the concentration Change
scale, 166 isothermal reversible — of a gas, 11
coefficient of a species in a real of a state variable, 5
solution, 151 of the Gibbs energy in a mixture of
coefficient using convention I, 155 chemical species, 114
coefficient using convention II, 160 of the Gibbs energy with the
effect of pressure and extent of reaction, 114, 115
temperature on the — Characteristic variables, 40–45
coefficient, 153 Châtelier
of a species in a real solution, 151 Le —’s principle, 132
Activity Chemical
of a pure condensed phase, 122 conversion of — energy into work,
Adiabatic 110, 111
chemical equilibrium of an — independent — reactions, 125
isobaric system, 117 reaction, 100
chemical equilibrium of an — Chemical equilibrium
isochoric system, 119 effect of an inert gas on a —, 134
closed — system, 20, 51, 53 effect of pressure on a —, 133
enclosure, 2, 16 effect of temperature on a —, 132
process, 16 effect of volume on a —, 133
reversible process, 17 of an adiabatic isobaric system, 117
reversible process of an ideal gas, of an adiabatic isochoric system,
28 119
Auxiliary of an isobaric isothermal system,
functions, 38 115
state variable, 3 of an isothermal isochoric system,
Azeotropy, 156–60 116
Beau de Rochas cycle, 34 Chemical potential
Binary definition, 42
mixture, 135, 140 of a multiphase system at
system, 156 equilibrium, 87
Boiling point of a pure condensed phase, 122
—, 137, 140 of a pure ideal gas, 67
elevation of the — of a solvent in of a pure liquid, 136
the presence of a solute, 146 of a pure real gas, 74
Bubble point, 137 of a real gas in a mixture, 80
Carnot cycle of a species in a real solution, 151
I
2 Introductory Thermodynamics
explicit expression for the —, 60 —s and the law of mass action, 123
of a mixture of reactants, 114 Homogeneous
of formation of hydrogen ions, 171 functions, 57
of mixing, 72, 142, 152 system, 1
of mixing in solutions, 142 Hydrogen ion convention for aqueous
of mixing of real gases, 82 solutions, 171
of reaction, 101, 102 Ideal
Gibbs function, 3, 38 gas mixture, 68
Gibbs-Duhem equation, 60 mixture of gases, 83
Gibbs-Helmholtz equations, 45 perfect and — solutions, 135–49
Global entropy species, 136
—, 26, 52 Ideal gas
and spontaneity, 27 Chemical potential of a pure —, 67
Half-cell standard potential, 173 definition, 49
Heat law of mass action for —es, 121
—, 15 mixture of —es, 68
engine, 31 partial pressure of an —, 69
engine, 17 Identity
pump, 31 Euler's —, 57
pump, 33 Implications
source, 1, 17, 51 of the first law, 16
system in contact with one — of the second law, 20
source, 17, 51, 53, 115, 116 of the third law, 98
system in contact with several — Independent reactions
sources, 22 —, 125
system in contact with two — and the law of mass action, 129
sources, 17 number of —, 125
transfer, 24 Inert
Heat capacity effect of an — gas on chemical
at constant pressure, 40 equilibria, 134
at constant volume, 39 Infinitesimal process, 16
of reaction, 102 Intensive
Helmholtz energy properties of — variables, 58
—, 3, 38, 42, 51 variable, 59
at 0 K, 98 variable, 2, 3, 38, 44
explicit expression for the —, 60 Internal energy
of reaction, 102 of an ideal gas mixture, 68
Helmholtz function, 3, 38, 42 Internal energy
Henry’s —, 15, 41
constant, 161 differential expression for the —,
law, 161 23
Hess’ law, 105 explicit expression for the —, 59
Heterogeneous system expression for the —, 23
—, 1 Internal energy
Index 7