Enthelpy of vaporization from Clausius–Clapeyron

In summary, the Clausius-Clapeyron equation can be used to solve for the enthalpy of vaporization, however, the resulting value is not a simple average over the temperature range. This is because the enthalpy of vaporization is dependent on temperature and therefore needs to be integrated. Additionally, for substances like carbon dioxide that exhibit unusual behavior, the assumptions made in deriving the Clausius-Clapeyron equation may not be valid, such as the assumption that the liquid volume is much smaller than the vapor phase and that the vapor phase behaves like an ideal gas.
  • #1
nod32
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Homework Equations



d ln(Psat) / d (1/T) = -ΔHvap/R (Clausius-Clapeyron)

The Attempt at a Solution



When solving for the enthalpy of vaporization using the Clausius-Clapeyron equation, is the resulting value an average over the temperature range? I assume this is the case, because enthalpy of vaporization is dependent on temperature.

I found the enthalpy of vaporization for carbon dioxide from 220K to 300K to be 16.59 kJ/mol (using the Clausius-Clapeyron equation) and tabulated saturation pressures.

I'm comparing this to the value I get from Hv-Hl=ΔHvap. When I take an average (arithmetic mean) of these values over the same temperature range, I get a value of 11.4 kJ/mol.

Why is there such a difference between using these two methods?
 
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  • #2
nod32 said:
When solving for the enthalpy of vaporization using the Clausius-Clapeyron equation, is the resulting value an average over the temperature range? I assume this is the case, because enthalpy of vaporization is dependent on temperature.

It is not a simple average. On the left you have a derivative, ΔH is a function of the temperature - so you need to integrate, and integration can be thought of as a weighted average.
 
  • #3
But if the values are over evenly spaced intervals (say 5K)?

I remember my prof talking about how carbon dioxide can behave unusually (I don't recall under what circumstances). Could this unusual behavior void some of the assumptions that are made in deriving the Clausius-Clapeyron equation?

Which according to my course notes are
-liquid volume<<vapor phase
-vapor phase acts as an ideal gas
 

1. What is the Clausius-Clapeyron equation and how is it related to the enthalpy of vaporization?

The Clausius-Clapeyron equation is a thermodynamic equation that relates the vapor pressure of a liquid to its temperature. It is used to calculate the enthalpy of vaporization, which is the amount of energy required to convert a liquid into a gas at a constant temperature.

2. How is the enthalpy of vaporization affected by temperature?

The enthalpy of vaporization typically decreases with increasing temperature. This is because as temperature increases, the intermolecular forces holding the liquid together weaken, making it easier for molecules to escape into the gas phase.

3. What factors can affect the enthalpy of vaporization?

The enthalpy of vaporization can be affected by factors such as the type of substance, temperature, pressure, and intermolecular forces. Substances with stronger intermolecular forces will have a higher enthalpy of vaporization, while those with weaker forces will have a lower enthalpy of vaporization.

4. How is the enthalpy of vaporization measured?

The enthalpy of vaporization can be measured experimentally using techniques such as differential scanning calorimetry (DSC) or by using the Clausius-Clapeyron equation. DSC involves measuring the heat flow required to maintain a constant temperature as a liquid is vaporized, while the Clausius-Clapeyron equation uses vapor pressure data at different temperatures to calculate the enthalpy of vaporization.

5. Why is the enthalpy of vaporization important in various industries?

The enthalpy of vaporization is an important thermodynamic property that is used in various industries, such as in the design and operation of distillation processes, refrigeration systems, and power plants. It also plays a crucial role in understanding the behavior of substances in different phases and their physical properties.

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