THERMODYNAMIC PROPERTIES AND CALCULATION

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THERMODYNAMIC PROPERTIES
A quantity which is either an attribute of an entire system or is a function of position which is continuous and does not vary rapidly over microscopic distances, except possibly for abrupt changes at boundaries between phases of the system; examples are temperature, pressure, volume, concentration, surface tension, and viscosity. Also known as macroscopic property.

BASIC CONCEPTS-1
First Law of Thermodynamic: Although energy assumes many forms, the total quantity of energy is constant, and when energy disappears in one form it appears simultaneously in other forms. (Energy of the system) + (Energy of surroundings) = 0 Ut = Q + W (nU) = Q + W dUt = dQ + dW d(nU) = dQ + dW There exists a form of energy, known as internal energy U.

BASIC CONCEPTS-2

PV diagram

Virial Equations of State PV = a + bP + cP2 + ...... Ideal gas: Z=1 or PV = RT Van Der Waals Equation of State

For Ideal Gas: Equation for Calculation

dQ + dW = CvdT dW = PdV dQ = CvdT + PdV Let V=RT/P :

BASIC CONCEPTS-3
Statements of the Second Law: Statement 1: No apparatus can operate in such a way that its only effect (in system and surroundings) is to convert heat absorbed by a system completely into work done by the system.
Statement 2: No process is possible which consists solely in the transfer of heat from one temperature level to a higher one

PRIMARY THERMODYNAMIC PROPERTIES P, V, T, S & U

dU = TdS PdV dH = TdS + VdP dA = PdV SdT dG = VdP SdT

Maxwells equation

EXAMPLE 1

Air at 1 bar and 298.15K (25) is compressed to 5 bar and 298.15K by two different mechanically reversible processes: (a) Cooling at constant pressure followed by heating at constant volume. (b) Heating at constant volume followed by cooling at constant pressure. Calculate the heat and work requirements and U and H of the air for each path. The following heat capacities for air may be assumed independent of temperature: CV= 20.78 and CP=29.10 J mol-1 K-1 Assume also for air that PV/T is a constant, regardless of the changes it undergoes. At 298.15K and 1 bar the molar volume of air is 0.02479 m3 mol-1.

KEYS

SOLUTIONS:

In suche case take the system as 1 mol of air contained in an imaginary piston/cyclinder arrangement. Since the processes considered are mechanically reversible, the piston is imagined to move in the cylinder withour friction. The final volume is (a) During the first step the air is cooled at the constant pressure of 1 bar until the final volume of 0.004958 m3 is reached. The temperature of the air at the end of this cooling step is:

SOLUTIONS

Also,
During the second step the volume is held constant at while the air is heated to its final state.

= = = 6,941 1 105 0.004958 0.02479 = 4,958J

The complete process represents the sum of its steps. Hence, Q = -6,941 + 4,958 = -1,938J U = -4,958 + 4,958 = 0J Since the first law applies to the entire process, , and therefore, 0 = -1,983 + W W = 1,983J

SOLUTIONS
, also applies to the entire process. But

and therefore, Hence , and

SOLUTIONS

Two different steps are used in this case to reach the same final state of the air. In the first step the air is heated at a constant volume equal to its initial valve until the final pressure of 5 bar is reached. The air temperature at the end of this step is: For this step the volume is constant, and

During the second step the air is cooled at the constant pressure of 5 bar to its final state:

SOLUTIONS

Also,
For the two steps combined, Q =24,788-34,703 = -9,915J U =24,788-24,788=0J

= = = 34,703 5 105 0.004958 0.02479 = 24,788J

and as before During the second step the volume is held constant at V2 while the air is heated to its final state. The property changes and calculated for the given change in state are the same for both paths. On the other hand the answers to parts (a) and (b) show that Q and W depend on the path.

EXAMPLE 2

Air is compressed from an initial condition of 1 bar and 25 to a final state of 5 bar and 25 by three different mechanically reversible processes in a closed system: (a) Heating at constant volume followed by cooling at constant pressure. (b) Isothermal compression. (c)Adiabatic compression followed by cooling at constant volume. Assume air to be an ideal gas with the constant heat capacities, CV= (5/2)R and CP = (7/2)R. Calculate the work required, heat transferred, and the changes in internal energy and enthalpy of the air for each process.

KEYS

SOLUTIONS
Choose the system as 1 mol of air, contained in an imaginary frictionless piston/cylinder arrangement. For R=8.314 J mol-1K-1, CV=20.785 CP=29.099J mol-1 K-1 The initial and final conditions of the air are identical with those of Ex.1, where the molar volumes are given as: V1=0.02479 V2=0.004958m3 Moreover, since the initial and final temperatures are the same, then for all parts of the problem:

SOLUTIONS

(a) The heat transferred, from Ex.1(b) is Q=9.915J. Thus by the first law applied to the entire process: (b) Equation for the isothermal compression of an ideal gas applies here:

(c) The intial adiabatic compression of the air takes it to its final volume of 0.004958m3. The temperature and pressure at this point are:

SOLUTIONS

V1 T2 = T1 V2

0.02479 0.4 = 298.15 ( ) = 567.57K 0.004958

V1 0.02479 1.4 P2 = P1 = 1( ) = 9.52bar V2 0.004958 For this step Q=0, and W = CV T = 20.785 567.57 298.15 = 5,600J For the second step at constant V, W=0. For the overall process, W = 5,600 + 0 = 5,600J

SOLUTIONS

Moreover,

, and by the first law,

Q = = 0 5,600 = 5,600J

Although the property changes and are zero for each process, Q and W are path-dependent. Since the work for each of these mechanically reversible processes is given by , the work for each process is proportional to the total area below the paths on the PV diagram representing the process. The relative sizes of these areas correspond to the numerical values of W.

EXAMPLE 3

Determine the enthalpy and entropy changes of liquid water for a change of state from 1 bar and 25 to 1,000 bar and 50. The following data for water are availbale:
t/
25 25

P/bar
1 1,000

CP/J mol-1 K- V/cm3 mol- /K-1

75.305 ......

18.071 18.012

25610-6 36610-6

50
50

1
1,000

75.314
......

18.234
18.174

45810-6
56810-6

KEYS

SOLUTIONS

For application to the change of state described, equations require integration. Since enthalpy and entropy are state functions, the path of integration is arbitrary. Since the data indicate that CP is a weak function of T and that both V and are weak functions of P, integration with arithmetic means is satisfactory. The integrated forms of Eqs that result are:

SOLUTIONS

For P=1 bar,

and for t=50

SOLUTIONS

Substitution of these numerical values into the equation for gives:

1 513 106 323.15 18.204 (1,000 1) H = 75.310 323.15 298.15 + 10cm3 bar J1
Similarly for , 323.15 513 106 18.204 (1,000 1) S = 75.310ln 298.15 10cm3 bar J1 Note that the effect of a pressure change of almost 1,000 bar on the enthalpy and entropy of liquid water is less than that of a temperature change of only 25

THERMODYNAMIC PROPERTIES AND THEIR