Clausius Clapeyron

Clausius-Clapeyron equation See Clapeyron-Clausius equation. 

Numerous mathematical formulas relating the temperature and pressure of the gas phase in equilibrium with the condensed phase have been proposed. The Antoine equation (Eq. 1) gives good correlation with experimental values. Equation 2 is simpler and is often suitable over restricted temperature ranges. In these equations, and the derived differential coefficients for use in the Hag-genmacher and Clausius-Clapeyron equations, the p term is the vapor pressure of the compound in pounds per square inch (psi), the t term is the temperature in degrees Celsius, and the T term is the absolute temperature in kelvins (r°C -I- 273.15). 

Vapor Pressures and Adsorption Isotherms. The key variables affecting the rate of destmction of soHd wastes are temperature, time, and gas—sohd contacting. The effect of temperature on hydrocarbon vaporization rates is readily understood in terms of its effect on Hquid and adsorbed hydrocarbon vapor pressures. For Hquids, the Clausius-Clapeyron equation yields... 

The vapor pressure for the soHd at 25°C has been calculated from the value for the Hquid at 70°C and the heats of vaporization and fusion using the Clausius-Clapeyron relationship. 

Fundamental Property Relation. The fundamental property relation, which embodies the first and second laws of thermodynamics, can be expressed as a semiempifical equation containing physical parameters and one or more constants of integration. AH of these may be adjusted to fit experimental data. The Clausius-Clapeyron equation is an example of this type of relation (1—3). 

If the latent heat of vaporization is then assumed to be constant over the temperature range of interest, equation 6 can be integrated to give the Clausius-Clapeyron expression ... 

Two empirical parameters are evident in equation 7, the heat of vaporization and the integration constant, I. Experimental data indicate that the linear relationship suggested by Clausius-Clapeyron may not be followed over a large temperature range (4) therefore additional adjustable parameters have been added to equation 7 to improve its correlating abiUty. The most prominent of these is the Antoine equation ... 

Reference Substances. Use of a reference substance has its origins in the work of Clausius-Clapeyron and equation 73, a form of equation 7 ... 

Curve fitting to data is most successhil when the form of the equation used is based on a known theoretical relationship between the variables associated with the data points, eg, use of the Clausius-Clapeyron equation for vapor pressure. In the absence of known theoretical relationships, polynomials are one of the most usehil forms to describe a curve. Polynomials are easy to evaluate the coefficients are linear and the degree, ie, the highest power appearing in the equation, is a convenient measure of smoothness. Lower orders yield smoother fits. 

Enthalpy of Vaporization The enthalpy (heat) of vaporization AHv is defined as the difference of the enthalpies of a unit mole or mass of a saturated vapor and saturated liqmd of a pure component i.e., at a temperature (below the critical temperature) anci corresponding vapor pressure. AHy is related to vapor pressure by the thermodynamically exact Clausius-Clapeyron equation ... 

As an example of how the approximate thermodynamic-property equations are handled in the inner loop, consider the calculation of K values. The approximate models for nearly ideal hquid solutions are the following empirical Clausius-Clapeyron form of the K value in terms of a base or reference component, b, and the definition of the relative volatility, Ot. 

Isosteric Heat of Adsorption The most useful heat of adsorption for fixed-bed calculations is the Isosteric heat of adsorption, which is given by the Clausius-Clapeyron type relation... 

Nomograph defined. This method assumes the application of the Clausius-Clapeyron equation, Henry s law, and... 

Better examples of shortcut design methods developed from property data are fractionator tray efficiency, from viscosity " and the Clausius-Clapeyron equation which is useful for approximating vapor pressure at a given temperature if the vapor pressure at a different temperature is known. The reference states that all vapor pressure equations can be traced back to this one. 

Unfortunately values of A// at sueh low temperatures are not readily available and they have to be eomputed by means of the Clausius-Clapeyron equation or from the equation given by Hildebrand and Scott" ... 

Clausius-Clapeyron Equation. This equation was originally derived to describe the vaporization process of a pure liquid, but it can be also applied to other two-phase transitions of a pure substance. The Clausius-Clapeyron equation relates the variation of vapor pressure (P ) with absolute temperature (T) to the molar latent heat of vaporization, i.e., the thermal energy required to vajxirize one mole of the pure liquid ... 

This suggests that a plot of P against 1/T should yield a line having a local slope of (-A, /R). A straight line is obtained only when is nearly constant, i.e., over a narrow range of temperatures. An integrated version of the Clausius-Clapeyron equation finds use in correlation of vapor pressure data ... 

Two estimates will be made using vapor pressure data from the CRC Handbook [63] and the integrated form of Clausius-Clapeyron equation ... 

This equation is known as the Clausius-Clapeyron equation. Rudolph Clausius (1822-1888) was a prestigious nineteenth-century German scientist B. P. E. Clapeyron (1799-1864), a French engineer, first proposed a modified version of the equation in 1834. 

In using the Clausius-Clapeyron equation, the units of AH and R must be consistent. If AH is expressed in joules, then R must be expressed in joules per mole per kehrin. Recall (Table 5.1, page 107) that... 

Strategy It is convenient to use the subscript 2 for the higher temperature and pressure. Substitute into the Clausius-Clapeyron equation, solving for Pi. Remember to express temperature in K and take R = 8.31 J/mol K. 

Use the Clausius-Clapeyron equation to relate vapor pressure to temperature. 

The Arrhenius equation can be expressed in a different form by following the procedure used with the Clausius-Clapeyron equation in Chapter 9. At two different temperatures, T2 and Tlt... 

As pointed out earlier, the equilibrium constant of a system changes with temperature. The form of the equation relating K to T is a familiar one, similar to the Clausius-Clapeyron equation (Chapter 9) and the Arrhenius equation (Chapter 11). This one is called the van t Hoff equation, honoring Jacobus van t Hoff (1852-1911), who was the first to use the equilibrium constant, K. Coincidentally, van t Hoff was a good friend of Arrhenius. The equation is... 

Clausius-Clapeyron equation An equation expressing the temperature dependence of vapor pressure ln(P2/Pi) = AHvapCl/Tj - 1/T2)/R, 230,303-305 Claussen, Walter, 66 Cobalt, 410-411 Cobalt (II) chloride, 66 Coefficient A number preceding a formula in a chemical equation, 61 Coefficient rule Rule which states that when the coefficients of a chemical equation are multiplied by a number n, the equilibrium constant is raised to the nth power, 327... 

Clausius-Clapeyron, 230,303-305 Gibbs-Helmholtz, 459,461 Henderson-Hasselbalch, 79-80 mass relation, 62-63 Nemst, 493-494 net ionic, 79-80 nonmetals, 575q nuclear, 513,530-531q Planck s, 135 redox, balancing, 90-92 Schrodinger, 140 thermochemical, 204... 

Corollary 3.—The Clausius-Clapeyron equation, in terms of reduced magnitudes, may be written... 

The Clausius-Clapeyron equation The Clapeyron equation can be used to derive an approximate equation that relates the vapor pressure of a liquid or solid to temperature. For the vaporization process... 

We have deduced the Clausius-Clapeyron equation for the vapor pressure of a liquid at two different temperatures ... 

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