ENTHALPY CHANGES IN CHEMICAL REACTIONS Hesss Law Purpose Test Hesss law (which says the heat of reaction

is the same whether the reaction is carried out directly or in several steps) by measuring the enthalpy changes for the same net chemical reaction carried out by two different paths. Make an approximate estimate, by an indirect measurement, of the enthalpy change for the dissociation of water into hydronium and hydroxide ions. Pre-Lab Preparation What accounts for the energy change in a chemical reaction? The simplest explanation is that in a chemical reaction, the positively charged nuclei and the negatively charged electrons of the reacting atoms rearrange themselves. It is the energy change associated with the rearrangement (or reconfiguration) of nuclei and electrons that produces the energy change of a chemical reaction. Thermochemistry deals with the thermal energy changes that accompany chemical reactions. These energy changes are usually called heats of reaction. When the reaction is carried out at constant pressure, the heat of reaction is called the enthalpy changes. Enthalpy changes may be classified into more specific categories: (1) the heat of formation is the amount of heat involved in the formation of one mole of the substance directly from its constituent elements, (2) the heat of combustion is the amount of heat produced when a mole of a combustible substance reacts with excess oxygen; (3) the heat of solution of a substance is the thermal energy change that accompanies the dissolving of a substance in a solvent; (4) the heats of vaporization, fusion and sublimation are related to the thermal energy changes that accompany changes in state; (5) the heat of neutralization is the enthalpy change associated with the reaction of an acid and base. In this experiment, you will measure the enthalpy changes for the following three reactions: (Reactions) In these reactions, the numbers in parentheses specify the molar concentrations of the reactants and products. Water is both the solvent and

a reaction product. In order to distinguish these two roles, we write H2O when we mean a reaction product and write solvent when water is used to dissolve the reactants and serve as the reaction medium. You will also see how the measurement of the enthalpy change of reaction (3) leads to an approximate estimate of the enthalpy of dissociation of water into hydronium ions and hydroxide ions. Reactions (1) and (3) can be regarded as neutralization reactions. Reactions (2) could be called a solution reaction, and we will call the enthalpy change for this process the heat of solution. Note also that if we add reactions (2) and (3), we get reaction (1). Thus, reaction (1) and the sum of reaction (2) and (3) represent two different pathways by which we can get from the same initial state to the same final state. Experimental Procedure Preparing the calorimeters. Prepare two calorimeters, ach like that shown in figure. Using a pen, label the calorimeters as calorimeters 1 and 2. In each experiment, you will be measuring initial temperatures of two solutions and the final temperature of the mixed solutions. You must be careful to use the same thermometer to measure the initial and final temperatures in an experiment because inexpensive lab thermometers often give readings that do not perfectly agree. If you are using a thermometer with 1 C intervals, estimate the temperature reading to the nearest 1/s of a degree. 1. The heat of solution and neutralization of 10 M H2SO4 and 1 M NaOH. Place 50 ml of 1 M NaOH and 45 ml of deionized or distilled water in calorimeter 1. Measure out exactly 5 ml of 10 M H2SO4 in a 5 or 10 ml graduated cylinder. Measure the temperature of the 10 M H2SO4 and record the reading. Remove the thermometer and readjust the volume to exactly 5 ml, if necessary, using a polyethylene transfer pipet (or a medicine dropper). Then rinse and dry the thermometer and insert it into calorimeter 1, which contains the NaOH solution. Stir the solution gently; read and record the temperature. Then add the 5 ml of 10 M H2SO4. Stir for 30 s (or until the reading is steady or only slowly decreasing) and record the temperature (to the nearest 0,2 C if you are using a thermometer with 1 C intervals). Neutralize the solution with 5 g of sodium bicarbonate and discard the solution down the drain. Rinse and dry the cups and carry out a duplicate set of measurements. Then rinse and dry the cups in preparation for part 2. 2. The Heat of solution of 10 M H2SO4. Measure 90 ml of deionized or distilled water in a graduated cylinder and put into calorimeter 1.

Measure out 10 ml of 10 M H2SO4 in a 10 ml graduated cylinder. Measure and record the temperature of the 10 M H2SO4. Remove the thermometer and readjust the volume to exactly 10 ml, if necessary. Then rinse and dry the thermometer, place it in calorimeter 1 (which contains the water), and gently stir. Read and record the initial temperature of the water as soon as the reading is steady. Then pour the 10 M H2SO4 into the calorimeter 1. Continue to stir for 30 s (or until the reading is steady), then read and record the final temperature of the solution. Neutralize the solution with 10 g of sodium bicarbonate and discard the solution down the drain. Rinse and dry the calorimeter cups and carry out a set of duplicate measurements. Rinse and dry the cups to prepare for part 3. 3. The heat of neutralization of 1 M H2SO4 and 1 M NaOH. Place 50 ml of 1 M NaOH in calorimeter 1 and 50 ml of 1 M H2SO4 in calorimeter 2. Put the thermometer in calorimeter 1 and stir gently until the temperature reading is steady, read and record the temperature of the sulfuric acid solution. Then pour the H2SO4 solution in calorimeter 2 quickly and completely into calorimeter 1. Stir for 30 s (or until the reading is steady) and record the final temperature after stirring. Neutralize the solution with 5 g of sodium bicarbonate and discard the solution down the drain. Rinse and dry the cups. Carry out a duplicate set of measurements. Calculations. For each reaction in parts 1, 2 and 3, determine the temperature change for the solution in calorimeter 1 and the added reactant solution by subtracting the initial temperature from the final temperature. The enthalpies of the several common reactions or physical processes can be measured quite accurately with the Styrofoam-cup calorimeter. Try measuring: a) Mg(s), Zn(s), Compare your results to those found from Hesss law and tabulated enthalpies of formation. Does stirring the water in your calorimeter change the temperature? Try to duplicate Joules original experiment to determine the mechanical equivalent of heat.