Thermodynamic properties of pure phases

B. Mishra

PART 1
Thermodynamic properties of pure phases

Introduction

This introductory section deals with some of the integral properties of chemical
thermodynamics along with the most pertinent expressions and finally derivation of
equation of state (EOS) for pure phases involving G, H, S, V and Cp at equilibrium P-T.
System:

The study of any special branch of physics starts with separation of a restricted

region of space or finite portion of matter separated from the rest of the universe by a
distinct boundary. The portion that is set aside (in the imagination) and on which the
attention is focused is called the system, and everything outside the system, which has a
direct bearing on its behaviour, is known as the surroundings. Hence, system is a
restricted region of space or a finite portion of matter separated from the rest of the
universe by a distinct boundary. Furthermore, there are open-, closed- and isolated
systems, depending on transfer of energy (heat) and matter (mass). While open systems
transfer both, the closed ones only transfer energy not mass. Isolated systems, on the
other hand, do not transfer either energy or mass.

Phase: A phase is defined as a system or a part of the system composed of any number
of chemical constituents satisfying the requirements that, (a) it is chemically
homogenous, and (b) it has a definite boundary.

Components: The minimum number of chemical species necessary to explain the

chemical variability of a system (system component) or phase (phase component).
Thermodynamic coordinates of a system

In thermodynamics, the attention is directed to the interior of a system, and the need to
evolve a set of parameters that have bearing on the internal state of a system. These
parameters (macroscopic or microscopic) are then related through equation of state that,

Thermodynamic properties of pure phases

B. Mishra

describes the equilibrium condition of a system. These parameters are called

thermodynamic coordinates.
Say for e.g., a system consisting of one mole of gas and at a low pressure has the
equation of state
PV = RT

(1a)

where P, V and T are thermodynamic coordinates.

Again, at high pressures, the equation of state is represented as

P 2 V b = RT
V

(1b)

Eqns. (1a) and (1b) represent equations of state of one mole of gas respectively at low
and high pressure but with the same thermodynamic coordinates (P, V, T). Geochemical
thermodynamics commonly involve macroscopic coordinates, which in contrast to
microscopic coordinates have the following common characteristics.
(a) they involve no special assumption concerning crystal structure.
(b) only a few coordinates are needed.
(c) Macro-coordinates are suggested more or less directly by our sense of perception.
(d) Macro-coordinates can in general be directly measured.

Equation of state: At equilibrium, there exists an equation of equilibrium that connects

the thermodynamic coordinates and makes one of its independent. Such an equation is
called as an equation of state (EOS).
a

For e.g., PV = RT or P 2 V b = RT (for one mole) are EOS in P, V, T. Once

V

any two coordinates (say T, V) are chosen, the value of the other (P) is determined by
nature.
State variables are those that describe the microscopic state of the system. State variables
may be extensive or intensive. While the extensive ones are those that depend on the
amount of material e.g., V, H, S and G the intensive variables include those, which do
not depend on the amount of the material. E.g. P, T, , X and R.I.

Thermodynamic properties of pure phases

B. Mishra

For a state function z and its differential dz, the following statements are valid:
(i) the differential dz is mathematically exact.
Any expression that may be written as M(x,y)dx + N(x,y)dy is an exact differential if

there exists a function z(x,y) that is written as

z
z
dz dx dy Mdx Ndy
x y
y x

if dz is an exact differential, then

M N

, which is equivalent to
y
x

x x y

The rule of reciprocity relation or cross differentiation is a necessary and sufficient test of
exactness. i.e., if dz is exact then z is a continuous function of x and y and z is uniquely
defined for every value of x and y, then

z

x y

y x

For example, if a function V = V (T, P) is V = RT/P, where R is a constant term.

Then
V
V
R
RT
dV
dT
dP dT 2 dP
T p
P t
P
P

We can check the exactness by cross differentiation in the following manner

R
RT

2
P P R
P

T
P2

T
P

Thermodynamic properties of pure phases

B. Mishra

(ii) For any process Z 1 Z 2 , the change Z is independent of the path chosen to effect
that change. Thus, Z can be calculated from the initial and final states of the system
2

only, i.e., dZ Z 2 Z 1 Z
1

(iii) In a close cycle, the net change in Z is always zero.

Hence, dZ 0

The state of a system

Based on the changes in state variables, we can classify systems as follows. The
equilibrium state is the one in which state variables do not change with space and time,
whereas in the steady state, state variables change in space, but not in time. Additionally,
we come across the transient states, where the state variables change both in space and
time.
The Equilibrium state can be of the following types.

Stable equilibrium: is one characterized by the lowest free energy

Metastable equilibrium: is an equilibrium state that is time-space invariant, but

not in the lowest free energy configuration, and which may convert to stable
equilibrium if kinetic barriers are removed.

Partial equilibrium: is the state of the system in which some variables are timespace invariant, but other variables are not.

From the first law of thermodynamics, the internal energy (U) of a system is related to
work done (W) and heat involved (Q) through the relation

dU = dW + dQ (dQ = dU dW)

(1)

Mathematically, the first law is related two important properties of the system: heat and
work. From classical mechanics, the work done by applying a force to a body is simply
defined as,

W=

F.dx , where F is the force vector and dx is the differential displacement

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Thermodynamic properties of pure phases

B. Mishra

Work done on the system = Force dis tan ce

Force dx
P. A dx
P( Adx) Pdv
dW PdV

(the negative sign stems from the opposing directions of work done and pressure
exerted by the gas to oppose compression)

We can explain the first law in a different way with the help of a special kind of work
relating compression or PV work, which is especially important in thermodynamics.
Let us consider a gas held under pressure by a piston in a vertical cylinder. If the piston is
released, the gas will expand a distance dx against the external pressure, which is
equivalent to the atmospheric force on the piston divided by the cross sectional area A
of the cylinder. For a differential amount of work done, we can write
dW = Fdx = Pex dAdx Pex dV

If the change is reversible, then the external pressure ( Pex ) = pressure (P) of the system so

that dWrev PdV . If any gas leaves the system, as in the performance of work by an
expanding gas, then the sign of the energy term is negative.

From the second law of thermodynamics, entropy (S) is related to heat through the
relation dS

dQ
(For reversible and irreversible processes)
T

For reversible processes, dS = dQ/T or dQ = TdS

(2)

Thermodynamic properties of pure phases

B. Mishra

Now, dU = dW + dQ

dU dQ PdV

(1)

Combining equations (1) & (2), we get

(3)

dU = TdS PdV

Eqn. (3) does not involve any transfer of matter between the system and the surroundings,
i.e. equation for a closed system.
For open system, eqn. (3) is modified to

dU TdS PdV i dni

(4)

where i is the chemical potential, expressed as i

ni S ,V ,n j i

Since S, V and n are extensive properties, eqn. (4) can be written in the integral form
U = TS PV +

n
i

and its differential form can be expressed as

dU = TdS + SdT PdV VdP +

dn n d
i

Now inserting eqn. (4), dU = TdS PdV + i dni , in the above eqn., we get

SdT VdP + ni d i 0

(5)

Eqn. (5) is termed as the Gibbs-Duhem equation that relates the intensive and extensive
properties of a phase. It is evident that amongst n variables, (n 1) can change
independently. However, for a pure phase eqn. (5) is simplified to

SdT VdP =0

(6a)

Thermodynamic properties of pure phases

B. Mishra

For condensed pure phases, the enthalpy (H), Gibbs free energy (G), entropy (S) and
internal energy (U) are related by the following relations.

H = U + PV
and

G = U + PV TS

(6b)

The differential of eqn. (6b) is

dG = dU + PdV + VdP TdS SdT
Substituting eqn. (3) (dU = TdS PdV), the above eqn. reduces to

dG = SdT + VdP

(7)

Again, since G = G (P, T) for a pure phase

G
G
dG =
dP
dT
P T
T p

(8)

Comparing eqns. (7) and (8) we get

G

S
T P
G

V
P T

(9)

Similarly since S = S (P, T) and H = H (P, T)

S
S
dS
dT dP
P T
T P
H
H
dH
dT
dP
T P
P T

(10)

It is now important to express the differentials in eqn. (10) in terms of determinable

parameters, namely Cp and V.
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Thermodynamic properties of pure phases

B. Mishra

Q
S
Since C P
T

T P
T P
C
S

P
T
T P

(11a)

G
Further, by substituting for
from eqn. (9), in the LHS of the eqn. below, we
T P

obtain
G
H S

S

T S
T P
T P T P
Cp
H
S
Hence,
Cp
=
T = T
T
T P T P

(11b)

Again, as G is a state variable and thus an exact differential, its crossed partial derivatives
are equal

2G
2G

PT T , P TP P ,T
G

PT T ,P
2

T
P

P ,T

G
P

T P

(12a)

G
T
S
( S )

P
P T
P T

(12b)

From eqns. (12a) and (12b)

V
S

P T T P

(13)

Thermodynamic properties of pure phases

B. Mishra

H
Finally,
can be derived as follows.
P

Since, G = H TS
or, H = G + TS
H
G
S

T
P T P T
P T
V
H

V T
T P
P T

(14)

S
S
Thus from eqn. (10a) replacing the differential
eqn.(11a )and (eqn.13) we
T P
P T

get

Cp
V
dS
dT
dP
T
T P

(15a)

H
Similarly from eqn. (10b), replacing the differential
(eqn.11b)and (eqn.14), we
T P

obtain,

V
dH CpdT V T
dP
T P

(15b)

Integration of eqns. (15a) and (15b) between the standard state ( P0 , T0 ) to any desired
state (P, T) leads to

V
H P ,T H P0T 0 C P dT V T
dP

P
T0
P0
T

Thermodynamic properties of pure phases

B. Mishra

and

V
C
P dT
dP
T
T

T0
P0
T

S P ,T S P0T0

G P ,T H P ,T TS P ,T
T
P

V
CP
V
C P dT V T
dP T S P0T0
dT
dP
T
T P
T P
T0
P0
T0
P0

GP ,T H P T

0 0

G P ,T H P0 ,T0 TS P0 ,T0

T
P
T
Cp
Cp.dT T
dT V .dP
T
P0
T0
T0

(16)

Fig.1 A typical Cp T plot

But as seen from the above figures Cp is commonly a function of T and can be derived as
a polynomial in T. Typically Cp is expressed in the form

Cp a bT cT 2 dT 0.5
where a, b, c, d, e and f are constants of Cp (Cp coefficients).

a bT cT

T0

T0

Cp.dT

dT 0.5 .dT

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Thermodynamic properties of pure phases

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b
1 1
2
0.5
Cp (T ).dT a(T T0 ) (T 2 T0 ) c( ) 2d (T 0.5 T0 )
2
T T0
T

(17)

Again,

a bT cT 2 dT 0.5
Cp
.dT
T dT T
T
T0
0
T

(18)

T
c 1
1
1
1
Cp
dT a ln b(T T0 ) ( 2 2 ) 2d ( 0.5 0.5 )
T
T0
T
2 T
T0
T0
T0
T

Combining eqns. (17) and (18)

T
T
Cp
.
Cp
dT

dT

T0
T0

T b
1 1 cT
a (T T0 ) aT ln (T 2 T0 2 ) bT (T T0 ) c
T0 2
T T0 2

1
1
2 2
T0
T

1
1
0.5
0.5
2d T T0 2d .T 0.5 0.5
T0
T

(19a)
Eqn. (19a) can be written as
T
T
Cp
Cp.dT T
dT
T
T0
T0

2
2
0.5
0.5

b
T T0
T
c T T0
2
a T 1 ln T0 (T T0 )
2d

T0
T 0.5
2 2T T02

2

where T0 = 298.15K

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(19b)

Thermodynamic properties of pure phases

B. Mishra

Now, let us solve the last term

V .dP in eqn. (16) in terms of differentiable parameters.

P0

Since volume is a state variable, for a pure phase we can write

V = V (P, T)
V
V
Hence, dV =
dT
dP
T p
P T

(20)

The two partial derivatives in eqn. (20) are expressed in terms of thermal expansivity
( ) and isothermal compressibility ( ), as follows.

1 V
V

or ,
VP0 ,T0
VP0 ,T0 T P T P

1 V
V

or ,
VP0 ,T0
VP0 ,T0 P T P T

where VP0 ,T0 refers to molar volume at the chosen standard state (P0, T0). By substituting
values of the partial derivatives in eqn. (20), we get

dV V P0 ,T0 ( .dT .dP )

(21)

Now, both and can be expressed as linear function of T and P respectively, as

follows.

(T ) 0 1T
( P) 0 1 P

Substituting the above two equations in eqn. (21), we obtain

dV V P0 ,T0 (T ).dT ( P).dP


Now on integrating the above differential for dV assuming
0 and
0
P T
T P

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Thermodynamic properties of pure phases

PT

PT

dV

P0T0

B. Mishra

VP0T0 0 1T dT 0 1 P dP

P0T0

VP ,T VP0T0 1 0 (T T0 ) 0.51 (T 2 T0 2 ) 0 ( P P0 ) 0.51 ( P 2 P0 2 )

1 2
P

2
V .dP P VP0T0 1 0 (T T0 ) 2 (T T0 ) dP P VP0T0
P0
0
0
P

V .dP V

P0T0

1 2

2
0 ( P P0 ) 2 ( P P0 ) dP

(22)

1 2
0 1

2
1 0 (T T0 ) 2 (T T0 2 6 P 2 ( P 1) ( P 1)

(23a)

Observing that the integral of a difference is identical to the difference is identical to the
P

difference in the integrals, we may derive

VdP

for any reaction as follows

V .dP V

P0T0

1
1

2
2
( 0VP0T0 )(T T0 ) (1VP0T0 )(T T0 ( 0VP0T0 ) ( 1VP0T0 ) P 2 ( P 1) ( P 1)
2
6

(23b)
Now, eventually substituting eqns. (19b) and (23a) into eqn. (16) leads to eqns. (24)
which is applicable for pure phases at P0 = 1 bar and T0 = 298.15K.
GP ,T

2
T
c T 298

b
2
H1,298 TS1,298 a T 1 ln

T0 (T 298 )
298
2 2T 2982

2

0.5

(24)
2
0.5
T 298
1 2

0 1

2
2d
V1,298 1 0 T 298 2 (T 298 2 6 ( P 2) ( P 1) ( P 1)
2980.5

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Thermodynamic properties of pure phases

B. Mishra

Eqn. (24) is the most fundamental eqn. for expressing Gibbs free energy of a pure phase
at any desired equilibrium P, T. The determinable/known thermodynamic coordinates
are
(i) H 0,1, 298 , S 0,1, 298 , and V0,1, 298 which are standard state enthalpy, entropy and volume of the
pure phase.
(ii) The Cp coefficients (a, b, c, d, e, f) that are obtained from the variation of Cp with T.
(iii) 0 , 1 and 0 , 1 are independently known from experiments.
If the above coordinates are known, then

G0, P ,T is a function of T & P, i.e. if P, T are

known for a pure phase G is automatically defined.

For any reaction such as A = B + C, eqn. (24) can be written as

2
T
c T 298

b
2

T
GPT H1,298 T S1,298 a T 1 ln

298
298

298
2 T 2982

2

T 0.5 2980.5 2
V1,298 1 0 (T 298) 1 (T 2 2982 0 1 ( P 2) ( P 1) ( P 1)
2d
0.5

298
2
6

(25)
where in stead of absolute values (G, H, S, V etc), we rather calculate the changes in
them (G, H, S, V etc).

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