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Answer the following questions based on the P-T phase diagram of carbon dioxide:
(a) At what temperature and pressure can the solid, liquid and vapour phases of CO2 co-exist in equilibrium?
(b) What is the effect of decrease of pressure on the fusion and boiling point of CO2?
(c) What are the critical temperature and pressure for CO2? What is their significance?
(d) Is CO2 solid, liquid or gas at (a) –70 °C under 1 atm, (b) –60 °C under 10 atm, (c) 15 °C under 56 atm?
(a) The P-T phase diagram for CO2 is shown in the following figure.
C is the triple point of the CO2 phase diagram. This means that at the temperature and pressure corresponding to this point (i.e., at –56.6°C and 5.11 atm), the solid, liquid, and vaporous phases of CO2 co-exist in equilibrium.
(b) The fusion and boiling points of CO2 decrease with a decrease in pressure.
(c) The critical temperature and critical pressure of CO2 are 31.1°C and 73 atm respectively. Even if it is compressed to a pressure greater than 73 atm, CO2 will not liquefy above the critical temperature.
(d) It can be concluded from the P-T phase diagram of CO2 that:
(a) CO2 is gaseous at –70°C, under 1 atm pressure
(b) CO2 is solid at –60°C, under 10 atm pressure
(c) CO2 is liquid at 15°C, under 56 atm pressure
Answer the following questions based on the P–T phase diagram of CO2:
(a) CO2 at 1 atm pressure and temperature – 60 °C is compressed isothermally. Does it go through a liquid phase?
(b) What happens when CO2 at 4 atm pressure is cooled from room temperature at constant pressure?
(c) Describe qualitatively the changes in a given mass of solid CO2 at 10 atm pressure and temperature –65 °C as it is heated up to room temperature at constant pressure.
(d) CO2 is heated to a temperature 70 °C and compressed isothermally. What changes in its properties do you expect to observe?
(a) No
(b) It condenses to solid directly.
(c) The fusion and boiling points are given by the intersection point where this parallel line cuts the fusion and vaporisation curves.
(d) It departs from ideal gas behaviour as pressure increases.
Explanation:
(a) The P-T phase diagram for CO2 is shown in the following figure.
At 1 atm pressure and at –60°C, CO2 lies to the left of –56.6°C (triple point C). Hence, it lies in the region of vaporous and solid phases.
Thus, CO2 condenses into the solid state directly, without going through the liquid state.
(b) At 4 atm pressure, CO2 lies below 5.11 atm (triple point C). Hence, it lies in the region of vaporous and solid phases. Thus, it condenses into the solid state directly, without passing through the liquid state.
(c) When the temperature of a mass of solid CO2 (at 10 atm pressure and at –65°C) is increased, it changes to the liquid phase and then to the vaporous phase. It forms a line parallel to the temperature axis at 10 atm. The fusion and boiling points are given by the intersection point where this parallel line cuts the fusion and vaporisation curves.
(d) If CO2 is heated to 70°C and compressed isothermally, then it will not exhibit any transition to the liquid state. This is because 70°C is higher than the critical temperature of CO2. It will remain in the vapour state, but will depart from its ideal behaviour as pressure increases.
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