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# Experiment 4 Calibration of Calorimeter

Objectives 1. To determine the heat capacity of the entire calorimeter system (calorimeter and water). 2. To determine change in temperature of hot water and cold tap water. 3. To calibrate a calorimeter by measuring the increase in temperature.

Introduction Experimentally, measuring heat flows is somewhat difficult. We do not have a heat meter that we can use to directly measure the amount of heat released/absorbed by matter when a thermodynamic process occurs. Thermometers, however, can be used to measure changes in temperature that can be utilized as indirect measures of heat flow. In order to precisely correlate measured temperature changes to the flow of particular amounts of thermal energy, a proportionality constant that relates these two quantities called the heat capacity of a material is used. It indicates the amount of heat required to raise the temperature of a sample of that material by 1C. Heat capacity is an extensive property of matter, meaning that it varies with sample size. To account for this fact, experimentally measured heat capacities are routinely corrected to account for a measurement on a 1 g sample, giving rise to a slight variation called the specific heat capacity (c) that indicates the amount of heat required to raise the temperature of 1 g of the substance by 1C. Since specific heat capacities are positive constants for a given material, heat flow is directly proportional to changes in temperature. Thus if the change in temperature T is positive, then q is also positive indicating the absorption of heat by the sample (an endothermic process). Alternatively, if T is negative then q is also negative indicating the loss of heat by the sample (an exothermic process). When a measurement is made in a calorimeter, we must account for the fact that the calorimeter itself can release heat into or absorb heat out of the process we are investigating while our measurement is being recorded. The calorimeter is in thermal contact with the matter we are interested in studying (the system of interest), so heat can be transferred between the system and the calorimeter (a portion of the surroundings). While we may not be particularly interested in studying the heat flow into or out of the calorimeter, it is essential that we account for it to prevent errors in the measurement of the heat flow pertaining to the system of interest. Since our calorimeter is a fixed mass, we can rearrange the expression for the specific heat capacity of the calorimeter and take the product of the specific heat capacity of the calorimeter (ccal) and the mass of the calorimeter as a new constant called the calorimeter constant (Ccalorimeter) as shown below:

qcal = mcal ccal Tcal qcal = Ccal Tcal (Eqn 3.1) (where Ccal = Calorimeter Constant = mcal

ccal

To measure the magnitude of the calorimeter constant we will carry out a measurement in which hot water is mixed with cold water in the calorimeter. Common experience tells us that the temperature of the water after mixing should lie between the initial hot and cold values. The First Law of Thermodynamics tells us that the sum of all of the thermal energy present in the calorimeter and in the two samples of water must stay constant throughout our measurement. (Remember, energy cannot be created or destroyed.) However, it will redistribute itself among all three components (the hot water, the cold water, and the calorimeter). Mathematically, the First Law for this mixing process can be written as: 0 = qhot + qcold + qcal (Eqn 3.2)

We know from our everyday experience that heat will exit the hot water and enter the cold water and the calorimeter, so we can rearrange Eqn. 3.2 to give: -qhot = qcold + qcal (Eqn 3.3)

Notice that this expression can be interpreted as an exothermic process from the perspective of the hot water (-q, heat lost) and an endothermic process from the perspective of the cold water and the calorimeter (+qs, heat gained). Since we know the heat capacity of liquid water (4.184 J/g C), and we can easily measure the masses of the hot water and the cold water that we pour into the calorimeter as well as the initial and final temperatures for each component, we can make the following substitutions into Eqn 3.3: qhot = mhot chot Thot qcold = mcold ccold Tcold qcal = Ccal Tcal (from Eqn 3.1) (We assume that Tcal = Tcold because the cold water is in contact with the calorimeter at all times during the experiment, allowing these two components to maintain thermal equilibrium throughout the experiment.) The resulting mathematical equation (that you should derive) contains only one unknown, the calorimeter constant, Ccal. The value we determine for this constant is true for your calorimeter, and it will be incorporated into the next two portions of the experiment.

## Apparatus and Materials Calorimeter Thermometer Measuring cylinder Beaker

Experimental Data 100 cm3 of tap water is measured into your calorimeter and the water is allowed to reach room temperature. The temperature is measured every minute until the temperature stays the same for 5 minutes. This temperature is recorded as the initial temperature. About 70 cm3 of tap water is heated in the beaker to 70 80 C. About 50 cm3 of hot tap water is poured into a graduated cylinder. The volume is measured and recorded. The temperature is recorded as the initial hot-water temperature. Immediately after measurement all of the hot tap water is poured into the calorimeter with the cool water. The lid is put on and the calorimeter is gently swirled rests for 30 seconds. The highest temperature attained by the mixture is recorded as the final temperature for the hot tap water, the cold water, and the calorimeter

Observations and Calculations Temperature of cold water Time (min) Temp (C) 1 28 2 27 3 27 4 27 5 27 6 27 T initial = 27 C (For cold water) Volume of cold water = Mass of cold water = 100 g Temperature of hot water = 66 C Volume of hot water = Mass of hot water = 50 g Final temperature of cold water, hot water and calorimeter = 38 C Thot = 38 C - 27 C = 11 C Tcold = 38 C - 66 C = -28 C Heat released by the hot water: qhot = mhot chot Thot qhot = 100 g x 4.184 J/g C x 11 C = 4602.4 J Heat absorbed by the hot water: qcold = mcold ccold Tcold qcold = 50 g x 4.184 J/g C x -28 C = -5857.6 J Heat capacity of calorimeter: -qhot = qcold + qcal -qhot = qcold + (Ccal

Tcal)

Ccal = -qhot - qcold Tcal Ccal = -(-5857.6 J) 4602.4 J 38 C 27 C Ccal = 114.11 J/ C Heat capacity of calorimeter, Ccal = 114.11 J/ C

## Discussion Mathematically, the proportionality can be expressed as shown below. Q released/absorbed = m c T

where c is the specific heat capacity (in J/(g C)), q is the quantity of thermal energy released/absorbed (in J), m is the mass of the sample (in g), and T is the change in  temperature (in C), which is taken as T final T initial for the sample.

Conclusion

References 1. Leggett and Hardesty. (n.d.). Collin College. Retrieved from http://www.collin.edu/chemistry/Handouts/1411/Calorimetry Lab FY09.pdf