The Latent Heat Calorimeter Patricia Neville January 2011

Abstract An analysis of the breakdown of classical theory of Specific Heat Capacity at low temperatures was undertaken. The specific heat capacities of 5 different samples were calculated firstly when the samples were at room temperature, and secondly when the samples were at the temperature of dry ice. The latent heat of nitrogen was also found to be 203.48.8 KJ/KG.

1. Introduction It was thought, until recently, that the specific heat capacity of a material was constant, however this has been shown not to be the case and it is, in fact, temperature dependant. In 1918 Dulong and Petit, two French physicists, predicted a description of specific heat capacity at high temperatures and that had a specific value per mole of material.[REF] Einstein improved upon this model in 1907 to develop a better understanding of specific heat capacity of a solid. He suggested that a solid could be seen as a large number of identical harmonic oscillators, and hence at low temperatures, the specific heat capacity becomes exponentially shaped.[REF] Also, fundamentally, Einsteins equation reduces to the Dulong and Petit equation at high temperatures. Although Einstein explained why specific heat capacity became temperature dependant at low temperatures, his model was not quite correct and it was the Debye model in 1912 that fully described the relationship. Debye, a Dutch physicist, made a more precise description by eliminating some of the assumptions that Einstein made. Agreement on the specific heat capacity at different temperatures is rare and hence specific heat capacity is still a main research focus. 1.1. Aims The primary focus of this analysis is to find the specific heat capacities of samples of lead, aluminium, zinc, copper and carbon. This is to be done by measuring the mass difference in the boil off of the liquid nitrogen between two temperature differences. It also allows for a look at the temperature dependence of the specific heat capacity and associated theories, hence allowing comparisons to be drawn between the theories. Although the main objective is to investigate specific heat capacity and its dependence on temperature, from the first investigation, an accurate determination of the latent heat of nitrogen is necessary. A discussion of the different methods is then enabled. 2. Theory

2.1 Latent Heat Latent heat is ...If a resistance heater of configuration of FIG INSERT is connected and placed into a sample of liquid, the latent heat of the liquid can be calculated by the following theory. The electrical power supplied to the resistance heater is simply [1] Where V is the voltage across the coil in volts, I is the current in the heater coil (A). If the rate of mass boil off is measure with and without the heater connected, and the power through the heater is known the latent heat of the liquid can be found: | | [2]

Where MH is the mass when the resistance heater is connected and MB is the mass when the resistance heater is not connected and L is the latent heat in Kj/kg. 2.2 Specific Heat Capacity Specific heat capacity is the amount of heat required to change one gram of a substance by one degree in temperature. It is to be measured in this experiment by recording the change in mass due to the introduction of samples of different materials into liquid nitrogen and dry ice. By comparing of loss of mass by the introduction of the sample, the specific heat capacity can be determined. [3] Where Q is the thermal energy in joules, m is the change in mass in kg. However, thermal energy can also be written as; [4] Where m is the mass of the sample in kg, c is the specific heat capacity in J/K/g and T is the difference in mass between the materials. Hence: [5] Also, it can therefore be seen that the error on C, the specific heat capacity is equal to: [ And the error on the latent heat capacity is: [ ] Dulong and Petit They discovered that the energy per mole: [9] Where K is the Boltzmann constant in m2kgs-2K-1, T is the temperature in Kelvin, and NA is Avogadros number in mol-1. The specific heat capacity of this material is simply the differential of this with respect to temperature. [10] They discovered that this was equal to 24.94J per mole of material [UNIV] University Physics Ref Einstein [ ] [ ] [7] ] [ ] [6]

Einstein suggested that instead of specific heat capacity being completely described by classical mechanics, in order to explain the effects at low temperatures, a solid could be viewed as a vibrating lattice, all with the same frequency. He described each harmonic oscillator with a series of quantised states that were equally spaced with a separation of hf. (where h is Plancks constant and f was the frequency of the vibrations). Einstein noted that if the energy for a quantum oscillator was less than KT, different statistics (called Einstein Bose Statistics) had to be applied and hence a different equation for specific heat capacity was determined: [REFERENCES] [11]

[REF the equation] Debye By using Plancks notion that the energy of an oscillator was proportional the frequency of the oscillations, Debye improved upon Einsteins idea. Instead of assuming that all the modes of vibrations had one frequency, he reasoned that they would have a distribution of frequencies, with a maximum value due to the maximum modes of vibrations. He treated the solid as long wave frequencies, due to the low temperature and was hence able to predict the relationship between temperature and specific heat capacity. Using these ideas he was able to derive the following equation[REF McQaurrie];

[12] Where D is the Debye temperature, [Ref other McQuarrie]

Specific Heat Capacity (C)

Temperature Figure 2.1 Showing how Debyes model (solid line) varies from Einsteins model (dotted line)

As can be seen from figure 2.1, the Debye model predicts specific heat capacities higher than that expected from Einsteins model at lower temperatures.

The Leidenfrost effect The exact definition of the leidenfrost effect is the temperature when the total evaporation time of a drop reaches a maximum and the heat flux assumes a local minimum. [REFERENCE THE ENCYCLOPEDIA] What this describes, more simply, is the effect that occurs when a mass that is significantly higher in temperature comes into contact with a liquid. A layer of vapour occurs between the mass and the liquid which insulates it and thus preventing the liquid from rapidly boiling off. The liquid would otherwise boil off at a rapid rate, however due to the layer of vapour; the impact of the coolant on the thermal energy of the mass of higher temperature is affected. Due to this, in this experiment, there will be a time when the leidenfrost effect comes to an end hence causing a period of rapid boil off of liquid nitrogen due to the introduction of the sample.

3. Experimental Methods
Cork bung with opening

Power Supply

Heater Dewer Flask Liquid

Electronic Mass Balance Connected to a computer programme

Fig 3.1 Showing the set up of the Dewer Flask and the electronic mass balance with the heater.

3.1 Measuring the Latent Heat of Nitrogen In order to measure the latent heat of Nitrogen, firstly the background boil off of Nitrogen has to be measured. The equipment was set up as shown in 3.1 and a computer programme was used to measure the mass every second for a certain number of minutes. The Dewer flask was filled to about full of liquid nitrogen and left to settle for 20 minutes. This was to ensure that the boil off of the nitrogen was not being affected by the movement of particles. The mass change (Mt) due to the natural warming of the liquid nitrogen was first measured to gain a value for the background boil off. This was achieved simply by recording the mass change over time. Secondly the increased mass change was recorded when a heater was placed into the liquid nitrogen. This was done by placing the unconnected heater into the flask, recording the boil off for 2 minutes before connecting the heater, recording the boil off during 2 minutes of the connected heater and again for another 2 minutes without the heater being connected. By using the different rates of boil off and the power sent through the heater, a value of the latent heat of nitrogen was determined. The latent heat of nitrogen was found at power outputs of 3.66 Watts and 11.88 Watts and an average taken. 3.2 Measuring the Specific Heat Capacities of Different Materials Method 1 The apparatus was set up as shown in Fig 3.1 except with the heater removed. In order to measure the specific heat capacities of different samples of materials, the mass change due to the sample being introduced to the liquid was to be measured. Firstly, the mass of each sample of material was measured. Then one sample was connected to a clamp stand by thin string, at a length such that if the sample was placed into the dewer flask then it would sit on the bottom. The scales were then set to zero and the mass change recorded for 2 minutes with the sample placed on top of the flask, 2 minutes where the sample was placed into the liquid and finally another 2 minutes where the sample was returned to the top of the flask. This was done so that when the mass change was determined, it was simply the difference between the height of the gradient of background boil off before the introduction of the sample and the height of the gradient of background boil off after the introduction. This can be seen in Figure 3.2 where the mass change is indicated in the diagram. This value is then substituted into equation 5 to gain a value for the specific heat of the material of the sample. The specific heat was calculated for samples of lead, aluminium, zinc, copper and carbon. This was repeated for each sample so that an average could be taken for each material. Specific care was taken to ensure that neither the flask nor the scales were disrupted during the readings, especially when introducing the sample into the liquid. It was ensured that the sample was placed into the flask in the quickest time without causing disturbance to the mass balance. Method 2 Method 1 was then repeated, with a few changes, in order to calculate the specific heat capacities the samples using dry ice. Firstly here, the samples were placed into the dry ice container for about 4 hours to ensure that the difference in temperature between the samples was negligible. Then the same method was applied, instead with the difference in temperature being measured by an electrical thermometer placed inside the dry ice container. Again, the difference in mass change due to the introduction of the sample was measured and again

values of the specific heat capacities of each material was calculated and an average taken of each.

Mass Change due to the introduction of the sample

Mass (Grams)

Time (Seconds) Fig 3.2 Showing how to calculate the mass boil off due to the introduction of the sample

4. Observations and Results Sample Lead Copper Zinc Carbon Aluminium Mass/g (0.0005g) 32.09 26.12 19.36 10.78 7.33

Fig 4.0.1 Showing the masses of the different samples that were used.

4.1 The Latent Heat of Nitrogen Using the method outlined in section INSERT, the latent heat of Nitrogen was found to be 210.39.6KJ/KG for a power output of 3.66W and 196.48.0 KJ/KG for a power output of 11.88W. This averages to give a value of 203.48.8 KJ/KG which is within 1.7% of the expected value (200 KJ/KG [REF])

4.2. The Specific Heat Capacities of Different Samples

4.2.1
30 25 20 15 10 M(t)/g 5 0 0 -5 -10 -15 -20 Time/s 50 100 150 200 250 300 350 400

Graph to show the mass change for Copper when placed in liquid nitrogen

Fig 4.2.1 Showing the mass change against time for copper when introduced to liquid nitrogen

Figure 4.2.1 shows how the mass changes with time for copper when it is placed into liquid nitrogen around 120 seconds(s) and removed at 240s. Graphs like this were produced for each sample and all samples followed a similar pattern. Before 120s and after 250s the background boil off of nitrogen due to the temperature difference between the liquid and the air temperature. It was seen from this graph a period of quick increase in mass when the sample was introduced followed by an almost constant rate of boil off at a faster rate than the background boil off. This continued to a point around 205s whereby a sharp decrease in the mass could be seen. This sharp drop was seen on all of the samples except carbon which had an almost constant decrease in mass for the first 20s after the mass was placed into the liquid nitrogen. The point at which this sharp decrease occurs changed depending on the material of the sample, the quickest being lead followed by zinc then aluminium, the slowest being copper.

30 25 20 15 M(t)/g 10 5 0 0 -5 -10 -15

Graph to show mass change for Copper when placed in Dry Ice

50

100

150

200

250

300

350

400

Time/s Fig 4.2.2 Showing the mass change for copper when placed in dry ice.

Figure 4.2.2 shows the mass change for copper when it was placed into dry ice at 120s and removed at 240s. Again, graphs like this were produced for the different samples, and all graphs were of similar shape. No sharp decrease was seen with method 2 and the time it took for the sample to reach the same temperature as the liquid nitrogen was, as expected, a lot shorter. As with before, an increase in mass was seen as the sample was introduced followed by a period of almost constant decrease until the sample made no difference to the boil off. It was seen that method 1 had a greater change in mass of liquid nitrogen.

Sample

Expected Value of C 0.129 0.385 0.387 0.897 0.710

Method 1 from Room Temp C Error 0.01 0.03 0.03 0.04 0.01

Method 2 from Dry Ice C 0.111 0.448 0.437 1.176 0.150 Error 0.03 0.03 0.02 0.04 0.01

Lead Copper Zinc Aluminium Carbon

0.144 0.413 0.455 0.997 0.303

Fig 4.2.3 Showing the specific heat capacities for the different methods used where C is measured in kj/kg

Figure 4.2.3 shows the results achieved for the specific heat capacity, C using the two different methods. It can be seen that, apart from carbon, method one provided more accurate results in achieving a value for C compared to the expected results. It was also seen that, apart from carbon, method 1 provided results that were higher than the expected value whereas method 2 provided results that were lower. All the results achieved for method 1, except for carbon are all within 20% of the expected value.

5. Discussion Section 4.1 shows the value for the latent heat of nitrogen to be calculated as within 1.7% of the expected value and hence improves the reliability of our results. The errors on this value were calculated using equation 7. This is a reasonably reliable value for L although it is thought that with more repeats, the value of the latent heat of nitrogen would tend towards the expected value. Figure 4.2.3 shows the final values that were calculated for the specific heat capacities of the different samples. It can be seen that Carbon has the biggest difference compared to the expected value. There may be a few reasons for this however the most likely is that the sample of carbon was a different shape than the rest of the samples. This posed two separate problems, the first being that placing the sample into the liquid was tricky as the sample did not fit through the gap in the bung, meaning that disturbance was caused to the balance as the bung was removed and replaced, hence causing large fluctuations in our results. The other issue being that a difference in shape would cause a different heating rate than the rest of the samples, due to a larger surface area being in contact with the liquid. This would again cause disturbance to our results. This table also shows that none of the results achieved were within the error boundary to the excepted value, therefore affecting the reliability of the results. The main reason for this is because; due to large fluctuations in the individual results achieved, the average value was affected and it is expected that with repeated results, the values would tend towards the excepted values. Figure 4.2.3 also shows that the results for method 1 provided more accurate results, and all of these results for the metals are within 20% of the expected value and are all higher than the expected value. This can be explained by figure 2.1 which shows that according to the Debye model, the specific heat capacity will be higher than expected when measured at low temperatures. The graphs such as Figure 4.2.1 show a steep fall in mass which is due to the leidenfrost effect, as outlined in section 2.3, however some graphs do not show this. Carbon does not show the end of the leidenfrost effect because it is graphite and hence it does not have any free electrons. This means that transfer of heat through the sample is much more gradual as heat transfer is by conduction through the particles only. This means that different parts of the sample will reach the temperature needed for the liedenfrost effect to finish at different times and hence there is no steep drop in mass. The leidenfrost effect is also not seen in method 2 due to the fact that the change in temperature between the sample and the liquid nitrogen is only 63.9 Kelvin and is therefore not large enough to cause the vapour layer to occur. It may also be noted here that a correlation between surface area of the samples and the mass loss due to the introduction is expected as more liquid nitrogen would be in contact with the thermal energy of the sample. Although the values achieved during method 1 are quite near what was expected, they can be up to 17% away. This is because there are some systematic errors with this experiment.

Firstly, it can be seen that the method used of calculating the change in mass was dependant on the reader of the graph and the point at which it was seen to go back to background boil off. An effort was made to ensure that the same point was taken on all graphs but small changes in the change in mass would have large effects on the overall C obtained. It was thought that this could have an error of up to 5% of the change in mass, hence causing a fluctuation of 2% of the final value calculated for the specific heat capacity. Finally, it was noted that the boil off rate of the nitrogen was directly related to the height of the liquid within the dewer flask, and as the sample was introduced, this caused the liquid height to change and hence the boil off rate to change. An investigation into this could be applied and potentially could provide more accurate results of the specific heat capacity. It also should be noted that small vibrations to the equipment such as knocking the table caused changes in the mass recorded and hence would have affected our results. It can also be seen that in Figure 4.2.3 that method 2 did not provide as accurate results as method 1. Perhaps the main reason for this was because the value of T was reduced and hence if this value was not quite the value of the sample then a wrong value for C would be calculated. This problem was enhanced by the fact that the sample was removed from the dry ice about 3 minutes before it was placed into the liquid nitrogen, meaning that the temperature at which it entered the liquid nitrogen was very likely to be higher than was accounted for. 6. Conclusions An accurate value of the latent heat of nitrogen was achieved of 203.48.8 KJ/KG and values of the specific heat capacity(C) were calculated for samples of lead, aluminium, zinc, copper and carbon from two different temperatures. It was seen that measuring C from room temperature provided more accurate results than from the temperature of dry ice. The main reason for this was due to a lack of accuracy of the exact temperature difference between the sample and the liquid nitrogen. It was also seen that the leidenfrost effect was not seen on carbon as it is graphite, nor was it seen when the samples were reduced to the temperature of dry ice as the difference in temperature was too small. It was also noted that the biggest sources of error in the experiment were due to reading the mass change off the graphs and should be minimised by careful experimental practice. The value for carbons specific heat capacity were significantly different to those expected, however the difference in shape of the sample caused problems in gathering an accurate reading. Overall, although the values calculated for some of the materials of the specific heat capacity were near what was expected, the many sources of error causes the data obtained here to be less valid. 7. References Encyclopdia of Physics Engel book from powerpoint presentation Introduction to Phonons and Electrons book