Thermochemistry and Hess’s Law Purpose: The purpose of this lab is to prove Hess’s Law.

10/5/11

Background: Thermochemistry is the study of energy in chemical reactions. Stored energy in a substance is known as enthalpy, or heat constant. It is impossible to measure the total enthalpy of a reaction, but it is possible to measure the change in enthalpy. If heat is given off by the system in a reaction, it is classified as exothermic and the enthalpy change is negative. If heat is absorbed by the system in a reaction, it is classified as endothermic and the enthalpy change is positive. Change in enthalpy is found from equation 1 below where H stands for enthalpy, or heat content. Eq 1: ∆Hrxn = Hfinal – Hinitial Enthalpy, which is the same as heat, can be found through equation 2 below, where q stands for heat, m stands for mass, C stands for specific heat of a substance, and T is a temperature. Eq 2: q = mC∆T Hess’s Law states that the heat energy in a reaction is the same if it is done in one step or several steps. This means enthalpy is a state function because it only depends on the start and end states of the equation. Hess’s Law manipulates equations to find the ∆H of a reaction that is very difficult to do in a lab. Materials:      Hydrochloric acid 2.0M Sodium hydroxide 2.0M 2, 50-mL graduated cylinders Magnetic stirrer and stirring bar CBL 2, temperature probe     Ammonia 2.0 M Ammonium chloride 2.0M Coffee cup calorimeter Hot plate

Procedure: A. Find the heat capacity of the calorimeter 1. Start heating water to 70°C and get a CBL. 2. Plug temperature probe into CBL. Start the “DATAMATE” program on the calculator. 3. Choose time graph #2 from modes. Set it to take 18 samples at 10 second intervals. 4. Measure 25.0mL of distilled water at room temperature and put it in a calorimeter. 5. Measure 25.0mL of the hot water near 70°C. 6. Put the stirrer into the room temperature water in the calorimeter. Add the hot water, put the CBL thermometer into the calorimeter, and start the CBL. 7. When it is done, Hit “STO” and then check your calculator’s stats to see if the data was transferred there. Delete the first entry for x and y. 8. Find the line of best fit through these stats. The y-intercept is the Tmix. Print this graph. B. Find the heat of the reactions (assume density of solutions is 1.03 g/mol and C = 4.184 J/0C 1. Clear the statistics tables. 2. Set the “DATAMATE” program up the same way as above. 3. Put 25.0mL of 2.0M HCl in the calorimeter. Measure the initial temperature. Put a stirrer in the calorimeter. 4. Measure 25.0mL of 2.0M NaOH. 5. Put the NaOH into the calorimeter with HCl. Put the top and thermometer in, start the “DATAMATE” and turn the stirrer on. 6. When done, hit “STO” and delete the first entry for x and y. 7. Find the line of best fit through the statistics. The y-intercept is the Tmix. 8. Graph this line and find the y-intercept. Print the graph. 9. Repeat steps 1-7 for NH4Cl and NaOH. 10. Repeat steps 1-7 for NH3 and HCl. 11. Calculate the ∆H of each reaction using the equation below. qrxn = -[(msol x Csol x ∆Trxn) + (Ccal x ∆Trxn)] 12. Since each solution used was 2.0M, you must divide the ∆H by the total amount of moles used. So for 25.0mL of each reactant, or 50mL of 2.0M solution total, there is 0.10 moles. Dividing the ∆H by 0.10 gives kJ/mol.

C. Verify Hess’s Law 1. Write the net ionic equations for all three equations. Arrange the equations so that the first two, when added together, give you the same reactants and products as the third equation. 2. Calculate ∆H for the third reaction using the first two equations and Hess’s Law. Compare to the results you got in lab. 3. Calculate percent error. Observations: All of the reactions were exothermic. The HCl and NaOH reaction was the most exothermic reaction. All of the reactants used were clear, but most had distinct odors which were pungent. All reactants were liquid. Analysis: The results found in lab were moderately close to the results found through Hess’s Law. The percent error would be 7.32%. This is probably due to the fact that we used NH4OH for the third reaction instead of NH3 because NH3 is a gas. The third reaction was easy to formulate using Hess’s Law from the reactions because all we had to do was reverse the second reaction and add the first to get the third reaction. Some heat might have been lost through the hole cut for the calorimeter, thus resulting in slightly less accurate data. The temperature probe could not get a temperature of the instant the reaction happened, so we had to use a line of best fit through the measurements taken throughout the reaction. This also would cause less accurate results.

Answers to Questions: Q1. What is meant by Calorimetry? Calorimetry is a way of measuring heat in reactions by keeping the pressure the same. When the pressure of a reaction is kept the same, the only change in energy is through heat, so all energy transferred in a reaction is in the form of heat. Q2. How does the graphical temperature analysis improve the accuracy of your data? The graphical analysis allows us to predict what the temperature would be at the instance the reaction occurs because the thermometer cannot register this quickly; however, being an estimate, it is not the exact temperature of when the reaction first starts. Q3. How could you modify the method to achieve greater accuracy? We could use more accurate instruments, find the specific heat and density of the solution ourselves instead of assuming, and delete the first reading from the CBL (which we did). Q4. The equation used to find the heat evolved in each reaction is qrxn = -*(msol x Csol x ∆Trxn) + (Ccal x ∆Trxn)+. What does the negative sign mean? Since qrxn = -qsol and you can only measure the heat of the solution, the negative sign is to switch the heat of the solution to the heat of the reaction. Conclusion: The heat of the final reaction based on Hess’s Law was -28.7 kJ/mol. The heat of the final reaction in lab was -30.8 kJ/mol. The third reaction was equal to the first and the inverse of the second, so -30.3 kJ/mol + 1.61 kJ/mol yields approximately -28.7 kJ/mol for the final reaction. The first reaction would provide the HCl in the reactants of the goal equation. The inverse of the second reaction would provide the rest of the reactants and products of the goal equation while eliminating the extra compounds from the first equation. Since these two equations added together result in the final equation, Hess’s Law can be used to determine what the enthalpy change should be. Since Hess’s Law states that enthalpy is a state function and it does not matter how you arrive at your final equation, the enthalpy change calculated from Hess’s Law comes very close to the enthalpy change observed of the goal reaction in lab.