Frigorific mixture
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A frigorific mixture is a mixture of two or more components that reaches an equilibrium temperature that is independent of the temperature of any of its components before they are mixed. The temperature is also independent of the quantity of components used as long as sufficient amounts of each are present.
Ice
Liquid water and ice, for example, form a frigorific mixture at 0 °C or 32 °F. This mixture is used to define 0 °C. A mixture of ammonium chloride, water, and ice form a frigorific mixture at about −17.8 °C or 0 °F. This mixture is used to define 0 °F.
Explanation
The chemistry of a frigorific mixture is a direct result of the enthalpy of fusion. Because the water cannot get any colder without freezing, and the ice cannot get any warmer without melting, as long as both are present, the temperature will remain near 0°C.
Other examples
Other examples of frigorific mixtures include:[1]
| Materials | Parts (w/w) [2] | Equilibrium temperature |
|---|---|---|
| Ammonium chloride (NH4Cl) | 5 | −12 °C / 10 °F / 261 K |
| Potassium nitrate (KNO3) | 5 | |
| Water | 16 | |
| Ammonium chloride (NH4Cl) | 5 | −15.5 °C / 4 °F / 257.5 K |
| Water | 16 | |
| Ammonium nitrate (NH4NO3) | 1 | −15.5 °C / 4 °F / 257.5 K |
| Water | 1 | |
| Sodium sulfate (Na2SO4) | 3 | −16 °C / 3 °F / 257 K |
| Dilute Nitric acid (HNO3) | 2 | |
| Sodium sulfate (Na2SO4) | 8 | −18 °C / 0 °F / 255 K |
| Hydrochloric acid (HCl) | 5 | |
| Snow/ice | 1 | −18 °C / 0 °F / 255 K |
| Common salt (NaCl) | 1 | |
| Snow/ice | 1 | −26 °C / −15 °F / 247 K |
| Potassium hydroxide, Crystallized (KOH) | 1 | |
| Snow/ice | 1 | −51 °C / −60 °F / 222 K |
| Sulphuric acid, dilute (H2SO4) | 1 | |
| Snow/ice | 2 | −55 °C / −67 °F / 218 K |
| Calcium chloride (CaCl2) | 3 | |
| Sulphuric acid, dilute (H2SO4) | 10 | −68 °C / −90 °F / 205 K |
| Snow/ice | 8 |
Uses
The most common use of a frigorific mixture is to melt ice. When ammonium chloride salt is placed on ice when the ambient temperature is greater than −17.8 °C (0 °F), the salt melts some of the ice and the temperature drops to −17.8 °C. Since the mixture is colder than the ambient temperature, heat is absorbed and the temperature rises. This causes the salt to melt more of the ice to drive the temperature down again. The process continues until all of the salt is dissolved in the melted ice. If there is enough salt present, then all of the ice will be melted.
Frigorific mixtures are commonly used in laboratories as a convenient way to generate reference temperatures for calibrating thermometers.
They are also useful for creating low temperatures when mechanical refrigeration is not available, for example to tightly fit two parts of machined metal: one part is soaked in a frigorific mixture, causing it to cool and contract, and then placed into the uncooled second part. As the first part warms, it expands to fit tightly within the second part.
Limitations of acid base slushes
Mixtures relying on the use of acid base slushes are of limited practical value beyond producing melting point references as the enthalpy of dissolution for the melting point depressant is often significantly greater (e.g. ΔH -57.61 kJ/mol for KOH) than the enthalpy of fusion for water itself (ΔH 6.02 kJ/mol); for reference, ΔH for the dissolution of NaCl is 3.88 kJ/mol. [3] This results in little to no net cooling capacity at the desired temperatures and an end mixture temperature that is higher than it was to begin with. The values claimed in the table are produced by first precooling and then combining each subsequent mixture with it surrounded by a mixture of the previous temperature increment; the mixtures must be 'stacked' within one another. [4][5][6] The enthalpy of vapourisation for carbon dioxide (dry ice) is 15.326 kJ/mol at –57.5 °C.
Such acid base slushes are corrosive and therefore present handling problems. Additionally, they can not be replenished in the same manner as the dry ice acetone slushes frequently used for laboratory cooling, as the volume of the mixture increases with each addition of refrigerant; the container (be it a bath or cold finger) will eventually need emptying and refilling to prevent it from overflowing. This makes these mixtures largely unsuitable for use in synthetic applications, as there will be no cooling surface present during the emptying of the container.
See also
References
- ^ The Ordnance Manual for the Use of the Officers of the United States Army, Third Edition, 1862, page 462
- ^ Walker, R. (1788). Experiments on the Production of Artificial Cold. By Mr. Richard Walker, Apothecary to the Radcliffe Infirmary at Oxford. In a Letter to Henry Cavendish, Esq. F.R.S. and A.S. Philosophical Transactions of the Royal Society of London, 78(0), pp.395-402.
- ^ Enthalpy of solution of analytes, CRC
- ^ Gray, S. (1828). The operative chemist. London: Hurst, Chance. Page 166.
- ^ Walker, R. (1788). Experiments on the Production of Artificial Cold. By Mr. Richard Walker, Apothecary to the Radcliffe Infirmary at Oxford. In a Letter to Henry Cavendish, Esq. F.R.S. and A.S. Philosophical Transactions of the Royal Society of London, 78(0), pp.395-402.
- ^ Walker, R. and Wall, M. (1795). Observations on the Best Methods of Producing Artificial Cold. By Mr. Richard Walker. Communicated by Martin Wall, M. D. F. R. S. Philosophical Transactions of the Royal Society of London, 85(0), pp.270-289.