Heat of Fusion and Heat of Vaporization ‘The present experiment deals with changes of phase, that is, the changing of a substance from the solid to the lig- uid state and from the liquid to the gaseous state. These three states, or phases, are normally exhibited by all sub- stances, but the temperatures at which changes from one state to another take place and the heat involved vary widely. Its the purpose of this experiment to study the THEORY When a solid body is heated, its temperature rises at a rate determined by the rate at which heat is being sup- plied and the heat capacity of the body. However, when ‘certain temperature called the melting point is reached. the body starts to melt, and as melting proceeds the tem- perature remains constant even though heat is being continually supplied. Increasing the supply rate merely increases the rate at which the solid changes to aliquid. No change in temperature oecurs until the body has completely melted. after which further heating will raise the temperature of the resulting liquid at a rate deter- mined by the liquid’s heat capacity (its mass multiplied hheat) and the rate at which heat is being Eventually, a temperature called the boiling point ‘will be reached. Here the liquid changes rapidly to a va- por, and again there is no change in temperature while this is going on even though the addition of heat contin- ues, When all the liquid has been evaporated, continued addition of heat to the resulting gas (which must now be contained in a suitably sealed vessel) will once more raise the substance's temperature—this time at arate de- termined by the heat supply rate and the heat capacity (mass times specific heat) of the gas, Upon cooling, the gas begins to condense when the boiling point is reached. and again there is no change in temperature while condensation takes place. The same amount of heat is removed during this condensation process as was added during vaporization: this heat rep- resents the difference in the energy of the molecules in the gaseous state and their energy when bound (although loosely) in the liguid. Similarly, once the temperature has been reduced to the freezing point (which is the same as the melting point), further removal of heat ‘causes the liquid to solidify. No change of temperature ‘occurs during this process, and the heat removed (which is the same as the heat added during melting) represents the difference in the molecular energy when the mole- heats involved in the change of water from a solid to a liquid and from a liquid to a gas by the method of mix- ‘ures. This method has been described in detail in Exper: iment 19 on calorimetry, and a review of the Theory section of that experiment will be helpful preparation for the present work. cules ure loosely bound in the liquid and when they are tightly bound in the solid, You should note that vaporization takes place at all temperatures, because there are always a few molecules inthe liquid with enough eneray to break the bonds atthe surface and emerge into the space above. One can thus think of a vapor pressure due to these escaped molecules above any liquid surface. Naturally. the higher the tem- perature, the more molecules will have enough energy to break through the surface and the higher the vapor pressure will be. Ifthe liquid surface is exposed to the at- mosphere, atmospheric pressure will prevent molecules entering the gaseous state near this surface from forming bubbles until the vapor pressure and atmospheric pres sure become equal. At this point. the vapor can form bub bles in opposition to the pressure of the atmosphere and the action we call boiling occufS_Molecules can then break from the liquid in large numbers, energy in the form of heat must be added to the liquid to replace the energy of the departing molecules, and a high rate of heat supply merely permits more molecules to evaporate per second, Nore, however, thatthe boiling point is now seen to be that temperature at which the liquid’s vapor pres- sure becomes equal to atmospheric pressure and is there fore highly dependent on the atmospheric pressure’s value, This is why water boils at a lower temperature on {op of a mountain, where the atmospheric pressure is less than at sea level. Thus, when the boiling point ofa liquid is given without further information, normal sea-level at- _mospheric pressure is assumed, Because there is usually a small volume change when a solid changes to a liquid or vice versa, the melting point may also be affected by the external pressure, but this effect is usually so small ‘that it can be ignored, ‘The amount of heat required to change a unit mass of a substance from the solid to the liquid state without a change in temperature is called the latent heat of fusion of the substance, or simply its heat of fusion. Similarly. 149150. HEAT OF FUSION AND HEAT OF VAPORIZATION the amount of heat required to change a unit mass of a substance from the liquid to the vapor state without a ‘change in temperature is called its latent heat of vapor- ization, of simply the heat of vaporization, Since evapo- ration can go on at any temperature and the heat of vaporization is different at different temperatures, the temperature should be quoted when a heat of vaporiza- sion is given. However, heats of vaporization are usually ‘aiven without this information, it being assumed that the temperature ofthe boiling point is meant. Since this tem- perature is dependent on the atmospheric pressure, nor- ‘mal sea-level pressure is also assumed. In doing heat experiments where the quantity of heat added to of taken from a substance is to be determined, the range of temperature should extend equally above and below room temperature so that the amount of heat absorbed from the surroundings during the course of the experiment will be approximately equal to the amount of heat radiated to the surroundings. Best results will thus, bbe obtained by starting with a calorimeter of warm water When the heat of fusion of ice is to be measured and starting with a calorimeter of cold water for the measure- ‘ment of the heat of vaporization of steam. This is easily accomplished by measuring first one and then the other of the two latent heats of water. Its the purpose of this experiment to carry out these two measurements. ‘The experimental determination of the heat of fusion of ice and the heat of vaporization of water is made by the method of mixtures. This makes use of the principle that when a heat interchange takes place between two bodies initially at different temperatures, the quantity of | hheat lost by the warmer body is equal to that gained by the cooler body, and some intermediate equilibrium tem- perature is finally reached. This is true provided no heat is gained from or lost to the surroundings. ‘In determining the heat of fusion of ice, a few small pieces of ice are placed, one by one, into a calorimeter containing water. As the ice melts, heat is absorbed from the water and calorimeter until the mixture comes to af nal equilibrium temperature. The heat absorbed by the APPARATUS 1, Calorimeter 2, Boiler and tripod stand or electrically heated steam generator 3. Water trap 4. Rubber bing 5. Bunsen burner (if needed) PROCEDURE 1. Weigh the empty calorimeter. Note that you are finding the calorimeter's mass in grams. 2. Fill the calorimeter half full of water about 10° above room temperature and weigh it. Replace it in the ice in melting plus the heat absorbed by the ice water thus produced is equal to the heat lost by the warm water ‘and calorimeter. The working equation is ML, + Mexity—0) where M is the mass of ice in grams, Ly is the latent heat of fusion of ice, fis the equilibrium temperature, fis the initial temperature of the water and calorimeter, m isthe -mass of warm water, cy is the specific heat of water. m, i the mass of the calorimeter, and cy isthe specific heat Of the material of which the calorimeter is made. Note that if all masses are in grams and specific heats in calo~ ries per gram per degree Celsius, cy has the numerical value 1 and mc; is the water equivalent of the calorime ter. Note also that the zero in Equation 20. is the tem- perature of the ice water produced by the melting ice and that we have further assumed the original pieces of ice to be at 0°C when they were put in the water, Thus one shouldn't take these pieces directly out of some deep freeze for this experiment unless we include in Equation 20.1 a term giving the heat lost by the ice in coming trom its initial temperature (whatever that may be) up to 0°C. ‘The heat of vaporization of water is determined in similar manner by the method of mixtures. A quantity of steam is passed into a known mass of cold water in x calorimeter, where it condenses and raises the tempera- ture of the water. The heat lost by the steam in condens- ing plus the heat lost by the condensed steam is equal to the heat absorbed by the cold water and calorimeter. ‘The working equation is, (mc + meth =f) (20.1) ML + McqA100 — 12) = (mc. + met — 1) (20.2) where M is the mass of steam in grams, L, is the latent heat of vaporization of water, fis the equilibrium tem perature, fis the initial temperature of the water and calorimeter, m is the mass of cold water, cx isthe specitic heat of water, my is the mass ofthe calorimeter, and ¢y 1s the specific heat of the calorimeter material as betore, Note here also that the steam is assumed to be at 100°C when it enters the water. ‘Triple-beam balance 0-100°C thermometer 0-50°C thermometer Ice Paper towels ‘outer calorimeter jacket and record the temperature of the water, 3. Dry some small pieces of ice on a paper towel 2 ‘and add them to the water without touching the ice with =your fingers, so as not to melt it. Add the ice until the {temperature is about 10° below room temperature, keep- ing the mixture well stirred with the 0-50°C thermome- ter, Record the equilibrium temperature when the ice is entirely melted. Weigh the calorimeter with its contents ‘again, but without the thermometer. 4. Fill the calorimeter three-quarters full of water about 15° below room temperature and again weigh it. Replace it in the outer calorimeter jacket. '5. Set up the steam generator as shown in Fig. 20.1 ‘and adjust itso that the steam passes through the water trap and flows freely from the steam tube. Record the temperature of the cold water and quickly immerse the steam tube. Allow the steam to pass in and condense un- til the temperature of the water is about 15° above room temperature, stirring continuously with the 0-100°C thermometer. Remove the steam tube and record the ‘equilibrium temperature, Weigh the calorimeter with its ‘contents again, but without the thermometer. DATA Mass of calorimeter Heat of Fusion ‘Mass of calorimeter and water Mass of water Initial temperature of water Equilibrium temperature Mass of calorimeter, water, and melted ice Heat of Vaporization ‘Mass of calorimeter and water Mass of water Initial temperature of water Equilibrium temperature Mass of calorimeter, water, and condensed steam Section Dae —____ EXPERIMENT 20181 Figure 20.1 Heat of vapor tom apparatus Specific heat of calorimeter Mass of ice Calculated heat of fusion of ice Accepted value of heat of fusion of ice Percent error Mass of steam Calculated heat of vaporization of water Accepted value of heat of vaporization of water Percent error SA Cee eee ee eee 1. From the data of Procedures 1-3, compute the heat of fusion of ice.182. HEAT OF FUSION AND HEAT OF VAPORIZATION 2. From the data of Procedures 4 and 5, compute the heat of vaporization of water. 3. Compare your results for the heat of fusion and the heat of vaporization with the known values by finding the percent error. QUESTIONS e 1, Di ss the principal sources of error in this experiment. 2. Why is it necessary to stir the mixtures?” 3. What error would have been introduced if the ice had not been dry?EXPERIMENT 20 153 Name econ Dae 4. Suppose the steam generator produced steam so fast that some of it bubbled up through the water and, escaped from the calorimeter without condensing. Would this cause an error in your results? Explain $. In the Theory section of this experiment it was pointed out that Equation 20.1 assumed the ice was at O°C before it was put in the water and that, similarly, Equation 20.2 assumed the entering steam to be at 100°C. (a) How good do you think these assumptions are? (b) What should you have done to make sure they're very good? (c) How should Equations 20.1 and 20.2 be modified if the above assumptions are nor ‘200d—that is, ifthe ice is much colder than 0°C and the steam much hotter than 10°C when they are put in the water? (d) Could you run the experiment on this basis? 6. (a) What is the purpose of the water trap in determining the heat of vaporization? (b) How would its absence have affected the results?154 HEATOF FUSION AND HEAT OF VAPORIZATION 7. The Theory section of this experiment suggests that when a liquid starts to boil, the formation of bub- bles should begin near the surface. Why do the bubbles actually form first at the bottom of the containing vessel? 8 A glass tumbler of 200 g mass and 5 em inside diameter is filled to a depth of 10 cm with tap water whose temperature is 10°C, and 50 g of ice at 0°C are then added. At the end of an hour, it is noted that the ice has just finished melting. What was the average rate, in calories per second, at which heat flowed into the glass from its surroundings?