CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 2.1.

THE THERMODYNAMIC NETWORK In the preceding chapter, we encountered several important partial differential thermodynamic properties of the type: (X/Y)Z; where X, Y and Z were all thermodynamic variables. We could start our survey by letting them be any permutation of three of the eight properties (U, H, A, G) and (p, T, S and V). There are 336 such permutations. We shall, however, limit ourselves to cases where X is one of the four energy functions (U, H, A, G) and Y and Z any permutation of two of the four remaining variables (p, T, S and V). That reduces the number of possibilities to 48. We should introduce a parenthetic note that all of the other 288 partial differentials can be evaluated from experimental estimates of this set of 48. We shall not be concerned, at this stage, with situations in which the composition is a variable. 2.2 systems: The Basic Equations. We begin with the four basic equations for static closed

dU dH dA
and

= = = =

T dS T dS - S dT - S dT

+ +

p dV V dp p dV V dp

(1a) (1b) (1c) (1d)

dG

It is convenient to group the 48 differential properties into four sets: one for each property (Y), with respect to which the energies are being differentiated. We shall differentiate both sides of equations 1a 1d with respect to the temperature, pressure, volume and entropy, in that order.

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 1. Temperature Derivatives.

(U/T)p (U/T)V (U/T)S (H/T)p (H/T)V (H/T)S (A/T)p (A/T)V (A/T)S (G/T)p (G/T)V (G/T)S

= = = = = = = = = = = =

T (S/T)p T (S/T)V

p (V/T)p

(1.1) (1.2)

T (S/T)p T (S/T)V

p (V/T)S

(1.3) (1.4)

+ V (p/T)V V (p/T)S

(1.5) (1.6) (1.7) (1.8)

- S - S - S - S - S - S

p (V/T)p

p (V/T)S

(1.9) (1.10)

+ +

V (p/T)V V (p/T)S

(1.11) (1.12)

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 2. Pressure Derivatives.

(U/p)T (U/p)V (U/p)S (H/p)T (H/p)V (H/p)S (A/p)T (A/p)V (A/p)S (G/p)T (G/p)V (G/p)S

= = = = = = = = = = = =

T (S/p)T T (S/p)V

p (V/p)T

(2.1) (2.2)

T (S/p)T T (S/p)V + +

p (V/p)S V V V

(2.3) (2.4) (2.5) (2.6) (2.7) (2.8)

- S (T/p)V - S (T/p)S -

p (V/p)T

p (V/p)S V

(2.9) (2.10) (2.11) (2.12)

- S (T/p)V - S (T/p)S

+ +

V V

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 3. Volume derivatives.

(U/V)T (U/V)p (U/V)S (H/V)T (H/V)p (H/V)S (A/V)T (A/V)p (A/V)S (G/V)T (G/V)p (G/V)S

= = = = = = = = = = = =

T (S/V)T T (S/V)p

p p p V (p/V)T

(3.1) (3.2) (3.3) (3.4) (3.5)

T (S/V)T T (S/V)p

V (p/V)S - S (T/V)p - S (T/V)S p p p V (p/V)T - S (T/V)p - S (T/V)S + V (p/V)S

(3.6) (3.7) (3.8) (3.9) (3.10) (3.11) (3.12)

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 4. Entropy Derivatives.

(U/S)T (U/S)p (U/S)V (H/S)T (H/S)p (H/S)V (A/S)T (A/S)p (A/S)V (G/S)T (G/S)p (G/S)V

= = = = = = = = = =

T T T T T T

p (V/S)T p (V/S)p

(4.1) (4.2) (4.3)

V (p/S)T

(4.4) (4.5)

+ -

V (p/S)V p (V/S)T

(4.6) (4.7)

- S (T/S)p - S (T/S)V

p (V/S)p (4.8) (4.9) V (p/S)T (4.10) (4.11) + V (p/S)V (4.12)

= - S (T/S)p = - S (T/S)V

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 48 differential properties appear on the left hand sides of the equations of the foregoing tables. They can all be calculated from experimental values for T, p, V and S together with those of the 24 differential quantities that appear on the right hand sides. They are of the type (X/Y)Z where X, Y and Z may be any permutation of three of those same four properties. 2.3 Reduction of the number of independent variables: Our goal is to determine those 48 differential properties for a specific state of the system. That means that T and p must be fixed and therefore can no longer be treated as variables.

It should be self evident that: (X/Y)Z = (Y/X)Z-1 (2) That dramatically reduces the number of independent partial derivatives from 24 to 12.
2)

1)

There are two theorems that relate trios of partial derivatives. The first of them is fairly obvious:

(X/Y)Z
giving:

= = = = =

(X/Q)Z(Q/Y)Z (S/p)T(p/V)T (S/T)p(T/V)p (p/S)V(S/T)V (p/V)S(V/T)S

(3) (4) (5) (6) (7)

(S/V)T (S/V)p (p/T)V

and

(p/T)S

The second theorem states that:

(X/Y)Z

- (X/Z)Y(Z/Y)X

(8)
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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Proof: Consider Z = Z[X,Y] dZ = At constant Z, Then which gives: is a function of X and Y.

(Z/X)Y dX + (Z/Y)X dY

dZ = 0 (X/Y)Z = - (X/Z)Y(Z/Y)X

(S/V)T (S/V)p (p/T)V

= = = =

- (S/T)V(T/V)S - (S/p)V(p/V)S - (p/V)T(V/T)p - (p/S)T(S/T)p

(9) (10) (11) (12)

and

(p/T)S

Whichever of these two theorems we employ, we eliminate four more of the 12 remaining derivative properties. We note that we have arranged matters in such a way that all of the eight properties that remain are extensive. They are:

(V/T)p and (S/T)p and (V/p)T and (S/p)T and

(V/T)S (S/T)V (V/p)S (S/p)V

3) Further reductions are possible by making use of a theorem due to

Maxwell.

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010

James Clerk Maxwell If Q is some function of the two variables, x and y, and the integral of dQ between two different combinations of values of x and y is path independent then dQ is said to be an exact differential. Since U, H, A and G are state properties, dU, dH, dA and dG, as expressed in the equations 1a-1d, satisfy that requirement. That being the case, if we write

dQ
The theorem states that:

f dX = = =

g dy

(13) (14)

(f/Y)X
Thus, since

(g/X)y T dS - p dV

dU (T/V)S

- (p/S)V = - (S/p)V

(15)

and thus:

(V/T)S

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Proof: = ((U/V)S/S)v ((U/S)v/V)S and from

dH (T/p)S

= =
=

TdS

V dp

(V/S)p

Proof:

((H/S)p/p)S

((H/p)S/S)p

and from

dA

- S dT =
=

pdV

(S/V)T
Proof: ((A/T)V/V)T

(p/T)V

((A/V)T/T)V

and from

dG (S/p)T

= =
=

- S dT

V dp (16)

- (V/T)p
((G/p)T/T)p

Proof:

((G/T)p/p)T

Equations 15 and 16 eliminate two more of the partial differentials from the list of independent variables. (S/p)T and (S/p)V were chosen for elimination.
4) The last theorem links pairs of differentials that are identical apart

from the nature of the imposed constraint. The theorem states that:

(X/Y)Z
Proof: If At constant Q,

(X/Y)Q

(X/Q)Y (Q/Y)Z

(17)

X = X[Y,Z]

dX = (X/Y)Z dY + (X/Z)Y dz (X/Y)Q = (X/Y)Z + (X/Z)Y (Z/Y)Q

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Thus

(V/T)S =

(V/T)p -

(V/p)T (p/T)S

(V/T)p

(V/p)T(p/S)T(S/T)p

= (V/T)p +
and

(V/p)T(T/V)p(S/T)p (18) + (V/T)p (T/p)S

(V/p)S =

(V/p)T -

(V/p)T

(V/T)p (S/p)T(T/S)p

= (V/p)T + (V/T)p (V/T)p(T/S)p (19)

also

(S/T)V = =

(S/T)p -

(S/p)T (p/T)V

(S/T)p

(S/p)T(p/V)T(V/T)p

(S/T)p + (V/T)p(p/V)T(V/T)p (20)

We find it to be convenient, at this point, to make use of the standard symbolism.

(S/T)p = T-1Cp

and

(S/T)V

T-1CV

Cp and CV are respectively the isobaric (constant pressure) and isochoric (constant volume) heat capacities. Most authors have chosen to use the symbolism:

(V/p)T

- KT

and

(V/p)S

- KS

where the extensive property KT, that I shall refer to as the molar isothermal compressibility, is related to the coefficient of isothermal compressibility T by:

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010

KT = V T T = - V-1(V/p)T
We note a tendency for some authors to use the symbol instead of . Less frequent is the use of:

(V/T)p =
where

Ep

and

(V/T)S =

ES

Ep, the molar expansivity is related to the coefficient of

isobaric expansion p by :

Ep = V p p = V-1 (V/T)p

Some authors use Ap in preference to Ep. From the foregoing, it is apparent that we can express the 48 differential properties of Tables 1-4 in terms of just five experimental variables. V and S are essential as are one from each of the three pairs Ep and ES, KT and KS and Cp and CV. Equations 18 20 can be rephrased in the following manner.

ES KS CV

= = =

Ep KT Cp

KT Cp / TEp T Ep2 / Cp T Ep2 / KT

(21) (22) (23)

Tables 1-4 can now be rewritten in the form:

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 5 Temperature Derivatives.

(U/T)p (U/T)V (U/T)S (H/T)p (H/T)V (H/T)S (A/T)p (A/T)V (A/T)S (G/T)p (G/T)V (G/T)S

= = = = = = = = = = = = -S

Cp CV

p Ep

(5.1) (5.2)

Cp CV +

p ES

(5.3) (5.4)

V Ep / KT V Cp / T Ep

(5.5) (5.6) (5.7) (5.8)

p Ep

- S - S - S - S - S + + V Ep / KT V Cp / T Ep p ES

(5.9) (5.10) (5.11) (5.12)

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 6. Pressure Derivatives

(U/p)T (U/p)V (U/p)S (H/p)T (H/p)V (H/p)S (A/p)T (A/p)V (A/p)S (G/p)T (G/p)V (G/p)S

= = = = = = = = = = = =

- T Ep - T ES

p KT

(6.1) (6.2)

+ - T Ep - T ES + +

p KS V V V p KT

(6.3) (6.4) (6.5) (6.6) (6.7) (6.8)

- S KT / Ep - T S Ep/ Cp + p KS V - S KT / Ep + V V

(6.9) (6.10) (6.11) (6.12)

- T S Ep / Cp +

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 7. Volume derivatives.

(U/V)T (U/V)p (U/V)S (H/V)T (H/V)p (H/V)S (A/V)T (A/V)p (A/V)S (G/V)T (G/V)p (G/V)S

= = = = = = = = = = = =

T Ep / KT Cp/ E p

p p p V /KT

(7.1) (7.2) (7.3) (7.4) (7.5)

T Ep / KT Cp/ E p

- S / Ep - S / ES - S / Ep - S / ES -

V /KS p p p V / KT

(7.6) (7.7) (7.8) (7.9) (7.10) (7.11)

V / KS

(7.12)

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 Table 8. Entropy Derivatives.

(U/S)T (U/S)p (U/S)V (H/S)T (H/S)p (H/S)V (A/S)T (A/S)p (A/S)V (G/S)T (G/S)p (G/S)V

= = = = = = = = = = = =

T T T T T T

p KT/ Ep p T Ep / Cp

(8.1) (8.2) (8.3)

V / Ep

(8.4) (8.5)

V / ES p KT / Ep

(8.6) (8.7)

- S T / Cp - S T / CV

p T Ep / Cp (8.8) (8.9)

- S T / Cp - S T / CV -

V / Ep

(8.10) (8.11)

V / ES

(8.12)

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 2.4 Sources of Data. From the set of tables 5 8, it is apparent that one need to have access to experimental values for five molar properties, to be in a position to evaluate the various partial derivatives of the four energy functions. These properties are represented as those of one mole of the pure substance or mixture. The volume and entropy are two of the five properties. In addition, one requires one of each of the two heat capacities, the two expansivities and the two compressibilities. 2.4.1 Volumes: The molar volumes of gases at a desired temperature and pressure can be determined in a relatively straightforward manner. For an ideal gas, the equation of state is:

Vm = RT / p
Numerous equations of state exist for imperfect gases. The molar volumes of liquids are typically derived from density measurements. The conventional technique was that of pyknometry, which is still quite widely used. . For the past thirty years, vibrating tube densimetry has been the dominant method for precision measuring of liquid densities. This technique is capable of a precision of 10-5 g cm-3. For 16

CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 liquid mixtures, the technique of dilatometry has been used to determine the volumes changes due to mixing. The following figure shows the design of a vibrating tube densimeter. This drawing includes the capability of making measurements at very high pressures.

The liquid sample is allowed to flow into the flexible vibrating tube, shown in the lower thermostatted compartment. The apparatus can be operated in a static mode, or a gravity induced flow mode. The tube is caused to vibrate by an electromagnetic circuit which sends an oscillating current to a measuring device.

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 The vibration (oscilation) time constant . is related to the density,, of the fluid contained in the tube by:
2

=A+B
The apparatus should be calibrated frequently to provide the values for the constants A and B. Enhanced accuracy can be obtained by alternately measuring the frequency for the sample of interest and a suitable calibrant (DDI water). The molar volumes of solids may also be determined by pyknometry. For pure crystalline substances, the unit cell volumes may serve as another basis for density evaluation.

Vm = NAv . v (cell) / n
Where NAv. Is Avogadros number, v(cell) is the unit cell volume and n is the number of formula units per unit cell.

2.4.2

Isobaric Expansivities:

The determination of molar volumes at several different temperatures, but the same pressure, leads to the determination of the isobaric expansivity. Since the expansivity is itself temperature dependent, it is desirable to have molar volumes for at least five different temperatures. There exist some techniques for measuring expansivities directly. For an ideal gas:

Ep.m = Vm / T
For liquids and liquid mixtures, a simple quadratic function can usually be fitted to the excess molar volume data with acceptable results..

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 2.4.3 Isobaric Heat Capacities. Numerous techniques have been devised to determine isobaric heat capacities. Differential scanning calorimetry of solids provides a means of monitoring heat input and temperature simultaneously. A calorimeter of this kind records the integrated heat required to maintain a constant rate of temperature increase.

Cp.m

= (dqp / dT) . Mm / w

where Mm is the molar mass and w is the sample weight. The technique of Picker flow microcalorimetry has proved invaluable for determining the heat capacities of liquids, liquid mixtures and solutions. This kind of calorimeter compares the ratio of the electrical heating powers, W,for a sample fluid and a standard that produce identical rates of temperature rise. The two fluids travel along matched parallel tubes at identical rates. Cp.m = (standard) . (W(sample) / W(standard )) . Vm (sample) where (standard) is the volumetric specific heat of the standard and W(standard) is the heating power (wattage) applied to it.

2.4.4 Entropies: The determination of entropies is based upon a combination of two important equations.

(S/T)p = T-1Cp

(24)

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010 and

S(>) =

T-1 H(>)

(25)

where (>) represents a phase change with an enthalpy change of

H(>) .
Equation 24 leads to:

S (T1 -> T2) = T-1Cp dT

(26)

With a few glaring exceptions, one may adopt the premise of the so called third law of thermodynamics and set S(0 K) = 0. It is then possible to determine S(T/K) at any other absolute temperature T from a knowledge of the isobaric heat capacities and, if required, the standard enthalpies of fusion and vaporization. Statistical (molecular) thermodynamics provides an alternative means of estimating molar entropies from spectroscopic data. It is a useful exercise to compare the so-called calorimetric entropies with the spectroscopic.

2.4.5 It is a

Isothermal Compressibilities. relatively simple matter to determine the isothermal

compressibilities of gases. For an ideal gas:

KT.m

= RT / p2

It is possible to determine the isothermal compressibilities of liquids from density measurements performed at a variety of pressures. However, the measurement process is very demanding. Liquid and solid compressibilities are very small and good precision is difficult to attain.

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CHEMICAL THERMODYNAMICS CHAPTER TWO 2/19/2010

2.4.5 Isentropic Compressibilities. A somewhat unexpected source of compressibility information comes from the measurement of ultrasonic speeds. The passage of an acoustic wave through a fluid sample leads to a sequence of alternating compressions and rarefactions. The process occurs rapidly enough to be described as adiabatic. When the process is reversible, in the sense that the sample returns to its initial equilibrium state, it is also isentropic. The isentropic compressibility, Ks is related to the ultrasonic speed, u, by: KS.m = Vm2 / (Mmu2) (27) High precision speeds of sound are measured by recording the time taken for an acoustic pulse to travel the length of a calibrated cell and trigger a new pulse.

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