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Why does adding solutes to pure water lower the the specific heat?
Why do higher concentration salt solutions heat up more quickly?
Why do higher concentration salt solutions heat up more quickly? |
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This question has been asked before and already has an answer. If those answers do not fully address your question, please ask a new question.
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One spurious reason is that the salt suppresses evaporation, but this is not essential, and you would only see it in open containers. The essntial reason is explained here: Why does adding solutes to pure water lower the the specific heat? . The salt becomes ions, and the ions hold a rigid cage of water molecules around them which are not allowed to vibrate individually. The reduction in the vibration degrees of freedom due to these cages reduces the specific heat by an amount roughly commensurate with the specific heat of the introduced salt, at most maybe 10 times bigger, since it's order-1 moelcules in the cage per salt atom. The reason that you get freezing out near ions is that the water is a polar molecule, and charged ions have interactions with the water molecules on the atomic scales that is two orders of magnitude bigger than kT. This allows the cage to form and to stay rigid enough that its oscillations are quantum mechanically frozen out. Without quantum mechanics, any spring, no matter how rigid, contributes almost the same amount to the specific heat, since classical systems have equipartition which doesn't allow the specific heat to go below .5 kT per degree of freedom (the kinetic energy), which is usually one kT per degree of freedom (harmonic spring), and which is not sensitive to the stiffness of the spring, only to the shape of the potential. The strength of the polar-molecule ion interaction is estimated in this answer: Please explain the physics of a Cloud Chamber |
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Having claimed that solutes don't affect the specific heat not only do I have to admit I'm wrong, but I've found a paper explaining the effect by no less a person than Fritz Zwicky, better known to many of us as a cosmologist. Anyhow, the paper is at http://authors.library.caltech.edu/8821/1/ZWIpnas26a.pdf Zwicky finds that the biggest effect is, to use his words: the water molecules act as rigid electric dipoles, and a dipole in the inhomogenous field of an ion will be attracted to it. The result of this attraction is a high pressure around the ion, and because the specific heat of water is strongly changed by pressure this effect has a big effect on the specific heat. There are several other possible contributions, but Zwicky shows these are small compared to the pressure effect. The paper is beautifully written and I strongly recommend having a look at it. |
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Adding salt in water will definitely lower the specific heat capacity of the solution but it will also increase the boiling point of the solution. i.e. Salt water would DEFINITELY get to 100° more quickly, but would it would reach 102° C or 103° C or whatever temperature before it boils. Put in vapor pressure terms, a liquid boils at the temperature when its vapor pressure equals the surrounding pressure. For the solvent, the presence of the solute decreases its vapor pressure by dilution. A non-volatile solute has a vapor pressure of zero, so the vapor pressure of the solution is less than the vapor pressure of the solvent. Thus, a higher temperature is needed for the vapor pressure to reach the surrounding pressure, and the boiling point is elevated. Put in chemical potential terms, at the boiling point, the liquid phase and the gas (or vapor) phase have the same chemical potential (or vapor pressure) meaning that they are energetically equivalent. The chemical potential is dependent on the temperature, and at other temperatures either the liquid or the gas phase has a lower chemical potential and is more energetically favorable than the other phase. This means that when a non-volatile solute is added, the chemical potential of the solvent in the liquid phase is decreased by dilution, but the chemical potential of the solvent in the gas phase is not affected. This means in turn that the equilibrium between the liquid and gas phase is established at another temperature for a solution than a pure liquid, i.e., the boiling point is elevated. |
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