Pressure Clapeyron 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). 

This expression describes the variation of the pressure-temperature coordinates of a first-order transition in terms of the changes in S and V which occur there. The Clapeyron equation cannot be applied to a second-order transition (subscript 2), because ASj and AVj are zero and their ratio is undefined for the second-order case. However, we may apply L Hopital s rule to both the numerator and denominator of the right-hand side of Eq. (4.47) to establish the limiting value of dp/dTj. In this procedure we may differentiate either with respect to p. 

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... 

This equation follows from equation 66, because vaporization occurs at the constant pressure Moreover, the heat of vaporization is related to the slope of the vapor—Hquid saturation curve through the Clapeyron equation ... 

Cluusius-Clupeyron Eijliation. Derived from equation 1, the Clapeyron equation is a fundamental relationship between the latent heat accompanying a phase change and pressure—volume—temperature (PVT data for the system (1) ... 

The Clapeyron equation is most often used to represent the relationship between the temperature dependence of a pure hquid s vapor pressure curve and its latent heat of vaporization. In this case, dT is the slope of the vapor pressure—temperature curve, ADis the difference between the... 

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. 

Correlation Methods Vapor pressure is correlated as a function of temperature by numerous methods mainly derived from the Clapeyron equation discussed in the section on enthalpy of vaporization. The classic simple equation used for correlation of low to moderate vapor pressures is the Antoine S equation (2-27). 

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 ... 

Known as the Clapeyron equation, this is an exacl thermodynamic relation, providing a vital connection between the properties of the liquid and vapor phases. Its use presupposes knowledge of a suitable vapor pressure vs. temperature relation. Empirical in nature, such relations are approximated by the equation... 

Figure 26-65 illustrates that Eq. (26-90) provides a linear approximation to the nonlinear relationship between two-phase specific volume and reciprocal pressure (v vs. P or vs. T ). For single components, me initial slope of the curve is found using me Clapeyron equation to give ... 

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. 

This differs from the water pressure equation of Clapeyron, which lacks the last term. If pj = 0 or dp, = 0, then Eq. (4.102) is identical to the Clapeyron equation, as it should be. 

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 ... 

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. 

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... 

While the Gibbs phase rule provides for a qualitative explanation, we can apply the Clapeyron equation, derived earlier [equation (5.71)], in conjunction with studying the temperature and pressure dependences of the chemical potential, to explain quantitatively some of the features of the one-component phase diagram. 

Line db in Figure 8.1 represents the equilibrium melting line for C02. Note that the equilibrium pressure is very nearly a linear function of T in the (p, T) range shown in this portion of the graph, and that the slope of the line, (d/ /d7 )s ], is positive and very steep, with a magnitude of approximately 5 MPa-K-1. These observations can be explained using the Clapeyron equation. For the process... 

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... 

Chapters 7 to 9 apply the thermodynamic relationships to mixtures, to phase equilibria, and to chemical equilibrium. In Chapter 7, both nonelectrolyte and electrolyte solutions are described, including the properties of ideal mixtures. The Debye-Hiickel theory is developed and applied to the electrolyte solutions. Thermal properties and osmotic pressure are also described. In Chapter 8, the principles of phase equilibria of pure substances and of mixtures are presented. The phase rule, Clapeyron equation, and phase diagrams are used extensively in the description of representative systems. Chapter 9 uses thermodynamics to describe chemical equilibrium. The equilibrium constant and its relationship to pressure, temperature, and activity is developed, as are the basic equations that apply to electrochemical cells. Examples are given that demonstrate the use of thermodynamics in predicting equilibrium conditions and cell voltages. 

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

STRATEGY We expect the vapor pressure of CC14 to be lower at 25.0°C than at 57.8°C. Substitute the temperatures and the enthalpy of vaporization into the Clausius-Clapeyron equation to find the ratio of vapor pressures. Then substitute the known vapor pressure to find the desired one. To use the equation, convert the enthalpy of vaporization into joules per mole and express all temperatures in kelvins. 

The vapor pressure of a liquid increases as the temperature increases. The Clausius—Clapeyron equation gives the quantitative dependence of the vapor pressure of a liquid on temperature. 

STRATEGY Use the Clausius-Clapeyron equation to find the temperature at which the vapor pressure has risen to 1 atm (101.325 kPa). 

Use the Clausius-Clapeyron equation to estimate the vapor pressure or boiling point of a liquid (Examples 8.1 and 8.2). 

Using the Clausius-Clapeyron Equation Living Graph on the Web site for this book, plot on the same set of axes the lines for AH = 15, 20., 25, and 30. kj-mol 1. Is the vapor pressure of a liquid more sensitive to changes in temperature if AH is small or large ... 

This latent heat of evaporation, Le, also appears in the fundamental description of the dependence of the vapor pressure of water, p, on temperature, T - the Clausius-Clapeyron equation ... 

The saturation vapor pressure is strictly a function of temperature as indicated by the Clausius-Clapeyron equation... 

If one measures the boiling points at several pressures, including that of atmospheric pressure, one can then extrapolate to obtain the vapor pressure of a material at ambient temperature. This is done using the Clausius-Clapeyron equation, i.e.-... 

It is of interest to consider the variation of vapor pressure with temperature. The vapor pressure of a liquid is constant at a given temperature. It increases with increasing temperature upto the critical temperature of the liquid. The liquid is completely in the vapor state above the critical temperature. The variation of the vapor pressure with temperature can be expressed mathematically by the Clapeyron-Clausius equation. Clausius modified the Clapeyron equation in the following manner by assuming that the vapor behaves like an ideal gas. 

Use the vapor composition and the Clausius/Clapeyron equation in reverse to roughly estimate AHvap. This requires two points on the vapor pressure chart. 

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