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Thermodynamic Data

It is not possible to know the absolute value of U ˆ or H ˆ for a pure substance, but you can determine the change in U ˆ (  U ˆ ) or Hˆ ( Hˆ ) corresponding to a specified change of state (, , and phase). The change is actually often what we want to know.

A common practice is to arbitrarily designate a reference state for a substance at which U ˆ and H ˆ are arbitrarily set to be equal to zero, and then tabulate U ˆ and/or H ˆ for the substance relative to the reference state. For example,

ˆ CO (g, 0C, 1 atm) CO (g,100C, 1 atm): HCO  2919 J/mol ˆ ˆ reference state  HCO HCO 0  2919 J/mol

We say: “The specific enthalpy of CO at 100C and 1 atm relative to CO at 0C and 1 atm is 2919 J/mol”. CHEE 221 1 Reference States and State Properties

 Most (all?) enthalpy tables report the reference states (T, P and State) on which the values of H ˆ are based; however, it is not necessary to know the reference state to calculate  H (change in enthalpy) for the transition from one state to another. ˆ ˆ –H from state 1 to state 2 equals H 2  H 1 regardless of the reference state upon which ˆ and ˆ were based H1 H 2 – Caution: If you use different tables, you must make sure they have the same reference state

 This result is a consequence of the fact that H ˆ (and U ˆ ) are state properties, that is, their values depend only on the state of the species (temperature, pressure, state) and not on how the species reached its state. When a species passes from one state to another, both  U ˆ and  H ˆ for the process are independent of the path taken from the first state to the second one. CHEE 221 2 Example 7.5-1

The following entries are taken from a data table for saturated methyl chloride: ˆ 3/ ˆ State T(F) P (psia) V (ft lbm ) H (Btu/lbm )

Liquid -40 6.878 0.01553 0.000

Vapour 0 18.90 4.969 196.23

Vapour 50 51.99 1.920 202.28

1. What reference state was used to generate the given enthalpies? 2. Calculate  H ˆ and  U ˆ for the transition of saturated methyl chloride vapour from 50F to 0F.

CHEE 221 3 Tables

Tables located in the back of F&R can be used to estimate  U ˆ , Hˆ and Vˆ for and steam (water vapour) at any specified temperature and pressure.

Recall the phase diagram for water:

Vapour-liquid equilibrium (VLE) curve or saturation line – water may Subcooled liquid exist as saturated water, saturated steam (vapour) or mixture of both. superheated steam

CHEE 221 4 Steam Tables

Saturated Steam Tables: Data taken along the VLE curve or saturation line.

 Table B.5 Saturated Steam: Properties of saturated water and saturated steam as a function of temperature from 0.01C (triple point) to 102C. Note boiling points at various P values and vapour at T values.

 Table B.6 Saturated Steam: Properties of saturated water and saturated steam as a function of pressure (same data as Table B.5 but over a much larger range of and pressures).

Superheated Steam Table: Data taken from points below the VLE curve or saturation line – vapour heated above its saturation temperature.

 Table B.7 Superheated Steam: Properties of superheated steam at any temperature and pressure – includes data for liquid water (data in the enclosed region), and saturated water and saturated steam.

CHEE 221 5 Notes on the Steam Tables

 Reference state for the tabulated thermodynamic data in the steam tables is liquid water at the triple point (0.01C and 0.00611 bar) [triple point is where all three phases of water can coexist] kJ kJ  Units are on a mass basis: Uˆ  and Hˆ  kg kg  Heat of vapourization (evaporation) is the difference between vapour and liquid enthalpies

 Properties of liquid water are not a strong function of pressure at constant temperature, therefore H ˆ  U ˆ since volume change is small

 Volumetric properties of steam are extensively tabulated: when steam tables are available, don’t use the ideal law.

 Remember: Hˆ (P,T )  Uˆ  PVˆ

CHEE 221 6 Steam Tables – Interpolation

 Sometimes you need to an estimate of specific enthalpy, specific or specific volume at a temperature and pressure that is between tabulated values (Usually B7)  Use linear interpolation:

use this equation to estimate y for an x between

x0 and x1

–E.g.; superheated steam at 20 bar, with enthalpy of 3065 kJ/kg. What T is the steam at? –Steam at 400 °C and 25 bar. What is the specific enthalpy?

CHEE 221 7 Example 7.5-2

1. Determine the vapour pressure, specific internal energy, and specific enthalpy of saturated steam at 133.5C.

2. Show that water at 400C and 10 bar is superheated steam and determine its specific volume, specific internal energy, and specific enthalpy relative to liquid water at the triple point.

3. Show U ˆ and H ˆ for superheated steam depend strongly on temperature and relatively slightly on pressure.

CHEE 221 8 Example

Steam at 80 bar absolute with 155C of superheat is fed to a turbine at a rate of 2000 kg/h. The turbine operation is adiabatic, and the effluent is saturated steam at 1 bar. Calculate the output of the turbine in kilowatts, neglecting kinetic and potential energy changes.

CHEE 221 9 Example 7.6-3

Saturated steam at 1 atm is discharged from a turbine at a rate of 1150 kg/h. Superheated steam at 300C and 1 atm is needed as a feed to a heat exchanger; to produce it, the turbine discharge stream is mixed with superheated steam available from a second source at 400C and 1 atm. The mixing unit operates adiabatically. Calculate the amount of superheated steam at 300C produced and the required volumetric flow rate of the 400C steam.

CHEE 221 10 Problem 7.26 F&R

Liquid water is fed to a at 24C at 10 bar and is converted at constant pressure to saturated steam. Use the steam tables to calculate  H ˆ ( kJ / kg ) for this process, and then calculate the heat input required to produce 15,000 m3/h of steam at the exiting conditions. Assume that the kinetic energy of the entering liquid is negligible and that the steam is discharged through a 15 cm ID (inner diameter) pipe.

CHEE 221 11