Why do the temperature drop if we take down the pressure?

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Discussion Overview

The discussion revolves around the phenomenon of temperature drop when pressure is decreased in a gas-liquid system, particularly in the context of hydrocarbons in a column. Participants explore theoretical and practical implications, including the behavior of gases and liquids under varying pressures.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • Some participants inquire why temperature drops when pressure is lowered in a gas-liquid column, specifically mentioning hydrocarbons at high pressures.
  • One participant describes a piston-cylinder system to illustrate that compressing gas increases internal energy and temperature, while expansion decreases heat per unit volume, but does not change total energy.
  • Another participant emphasizes that lowering pressure leads to more vapor formation, which requires energy, thus drawing energy from the liquid and lowering its temperature.
  • Concerns are raised about the relationship between molecular spacing and temperature, questioning if increased space between molecules affects collisions and energy transfer.
  • One participant explains that for a liquid to vaporize, energy is needed, which results in a temperature drop when pressure is released.
  • Another participant references the ideal gas law, suggesting that reducing pressure in a rigid container leads to a decrease in temperature, although they note practical challenges in achieving this.
  • Some participants argue against the notion that compressing gas does not add energy to the system, asserting that mechanical work increases energy and temperature.
  • There is mention of alternative equations of state, like the Redlich-Kwong, as potentially better approximations than the ideal gas law, with a caution that not all gases cool upon expansion.

Areas of Agreement / Disagreement

Participants express differing views on the mechanisms behind temperature changes due to pressure variations, with no consensus reached on the explanations provided. Some participants agree on certain principles, while others challenge or refine these ideas, indicating an ongoing debate.

Contextual Notes

Participants discuss various assumptions regarding energy transfer, the behavior of gases and liquids under pressure changes, and the limitations of the ideal gas law. The discussion reflects a range of interpretations and applications of thermodynamic principles.

charlie95
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why do the temperature drop if we take down the pressure?

If you have a column with mehane, ethane and butane in a gas liquid phase(at 100 bars),why do the temperature drop if we lower the pressure?
 
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lets understand this with the help of practical example...
suppose you have a piston and cylinder system contains gas in it and assume that system is isolated from surrounding. Mean no heat and mass transfer in surroundings.
System isolation means the total enthalpy of system remains constant.
so if you compress the gas then all internal energy say heat (enthalpy + other energy) collected in a less volume. So amount of heat per meter cube increased. But in case of expansion the amount of heat per meter cube is decreases...
Their is no change in total energy occurs.
hope it is helpful.
thanks
 


Forget the piston and cylinder. I am talking about a coulumn( a fraction coulmn in the gas industry).

If we have a column with liquid and gas(hydrocarbons) at 100bar.. If we now open all valves to depresurise(depresurize to atmosphere) the column down to 20 bar, we will see that the temperature drops. Why??
I have looked at a phase envelope for methane, ethane etc and have seen that when you take down the pressure, you will get more vapour. And i have been told that vapour needs energy and the energy it takes from the surroundings, which in this case is the liquid in the column. And that is why the temperature goes down(i have been told). But do this have anything to do with the molecules(more space between molecules less collision )??
 


Forget the piston and cylinder. I am talking about a coulumn( a fraction coulmn in the gas industry).

If we have a column with liquid and gas(hydrocarbons) at 100bar.. If we now open all valves to depresurise(depresurize to atmosphere) the column down to 20 bar, we will see that the temperature drops. Why??
I have looked at a phase envelope for methane, ethane etc and have seen that when you take down the pressure, you will get more vapour. And i have been told that vapour needs energy and the energy it takes from the surroundings, which in this case is the liquid in the column. And that is why the temperature goes down(i have been told). But do this have anything to do with the molecules(more space between molecules less collision )??
 


Its because of the evaporation of the liquid. If you look at the vapor pressure of the gas vs temperature you will see that, for any given temperature a liquid will fill the empty volume of its container with vapor at a certain pressure. The higher the temp, the higher the pressure. It takes some energy for the molecules to change from a liquid state to a gaseous state, which lowers the temperature. If you open a valve and release some of the pressure, the liquid will try to return the pressure to what it was before (and then the temperature decreases and the vapor pressure goes down a little). The column you speak of can exist in equilibrium between the gas and liquid at 20 bar only at a lower temperature than 100 bar. This affect is what makes Liquid N2 useful for cooling things.

Helium evaporation is used to get way down to about 3.4 degrees kelvin, below the superconducting temperature of most elemental superconductors.

In response to the piston example, be careful. When you compress a gas with a piston you increase the momentum of the gas particles with each collision between the particles and the moving piston. This increases the temperature according to the kinetic theory of gasses. On the other hand, consider a volume with a divider in the middle, with a volume of gas with temperature T on one side and a vacuum on the other. At time t the divider vanishes. What is the resulting temperature of the gas? The answer is the final temperature equals T. This was a question on my statistical mechanics final which I got wrong...

ParamTv said:
if you compress the gas then all internal energy say heat (enthalpy + other energy) collected in a less volume. So amount of heat per meter cube increased. But in case of expansion the amount of heat per meter cube is decreases...
Their is no change in total energy occurs.
thanks

This is not true. In order to compress the gas you must do mechanical work, this adds energy to the system. Heat is not a quantity that you can have per cubic meter, its an amount of energy transferred from one body to another through an interface, and carries a connotation of entropy increase.
More particles with the same energy in a constant volume -> higher pressure, same temp.
Same particles with the same energy in a smaller volume -> higher pressure, same temp.
You did work on the system -> higher pressure, higher temp
You rounded up all of the particles of the system and somehow convinced them to occupy less space without removing entropy from the system -> you violated 2nd law of thermodynamics
 
Last edited:


"Ideal gas law": PV= nRT where P is the pressure on a gas, V its volume, n the number of molecules, R Avogadro's constant and T is temperature in degrees Kelvin. If your gas is in a rigid container, so that V is constant, and no gas can escape so n is constant, reducing P reduces PV so nRT must reduce which means that T must reduce.

Of course, if your gas is in a rigid container, how do you reduce P without reducing either n? Usually, it is done the other way. You can reduce the temperature from outside so reducing the pressure.
 


Greg-ulate said:
This is not true. In order to compress the gas you must do mechanical work, this adds energy to the system. Heat is not a quantity that you can have per cubic meter, its an amount of energy transferred from one body to another through an interface, and carries a connotation of entropy increase.
More particles with the same energy in a constant volume -> higher pressure, same temp.
Same particles with the same energy in a smaller volume -> higher pressure, same temp.
You did work on the system -> higher pressure, higher temp
You rounded up all of the particles of the system and somehow convinced them to occupy less space without removing entropy from the system -> you violated 2nd law of thermodynamics

thanks its very helpful for me.
 


thanks...
u made it easy to understand :D
 


Be careful. The ideal gas law is always a rough approximation. The Redlich-Kwong seemed to be a better approximation of the PV relationships in my experience.

BUT, not all gases cool upon expansion.
 

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