American Chemical Society Join Schrenk Society! Who: Anyone with a love of chemistry! Where: Schrenk 139 When: Mondays at noon Thermochemistry (Heat of Reaction) Purpose of the Experiment Determine the heat of neutralization for the reaction of a strong acid and base; and for a weak acid with a strong base. Determine the heat of fusion of ice. What is the Heat of Reaction? Definition of Enthalpy Thermodynamic Definition of Enthalpy (H): H = E + PV E = energy of the system P = pressure of the system V = volume of the system At Constant Pressure Recall, by definition a change in energy equals heat transferred (q) plus work (w): E = q + w Consider a process carried out at constant pressure. At constant pressure, work involves only a change in volume. We can then substitute -PV for w. E = qp - PV Then if we want to solve for the heat transferred, qp, at constant pressure, we simply rearrange the equation. qp = E + PV Enthalpy = Heat Transferred Recall our original definition of enthalpy: H = E + PV Then for a change in enthalpy: H = E + (PV) If we set P constant, then: H = E + P V Since qp = E + PV Then H = qp The change in enthalpy, H, is then equal to the heat transferred at constant pressure, qp. In a chemical reaction H = H products – H reactants If H <0, then qp <0 The reaction is Exothermic. Heat goes from the system into the surroundings. If H >0, then qp >0 The reaction is Endothermic. Heat goes from the surroundings into the system. An example of an exothermic reaction: http://www.youtube.com/watch?v=rdCsbZf1_Ng An example from the S&T mining dept: http://www.youtube.com/watch?v=CIGJPWAynDQ Heat Capacity, C “C” is an extensive property; so a large object has a larger heat capacity than a small object made of the same material. Using the Equation: C heat absorbed q increase in tempera ture T Looking at the figures on the left, it can be seen that the temperature change is constant, but the heat absorbed by the larger object is greater. This results in a larger heat capacity for the larger object because more heat is absorbed. Specific heat capacity: The energy (joules) required to raise the temperature of 1 gram of substance by 1C Unit: J g-1K-1 or J g-1C-1 C Cs m Molar heat capacity: The energy (joules) required to raise the temperature of 1 mol of substance by 1C Unit: J mol-1 K-1 or J mol-1C-1 C Cm n Specific Heat, Cs Substance (cal/gram°C) (J/kg °C) Pure water 1.00 4,186* Wet mud 0.60 2,512 Ice (0 °C) 0.50 2,093 Sandy clay 0.33 1,381 Dry air (sea level) 0.24 1,005 Quartz sand 0.19 295 Granite 0.19 294 1 calorie = 4.186 joules *The high heat capacity of water makes it ideal for storing heat in solar heating systems. Neutralization The reaction between an acid and a base which results in a salt plus water. For example, hydrochloric acid and sodium hydroxide: HClaq + NaOHaq NaClaq + H2O acid + base salt + water Another example, cyanic acid and a hydroxide ion. Heat of Neutralization Net ionic equation for neutralization: H+(aq) + OH-(aq) H2O(l) Energy released by reaction = Energy absorbed by solution Specific heat capacity, Cs, is defined as the quantity of heat transferred, q, divided by the mass of the substance times the change in temperature. A value of Cs is specific to the given substance. Cs = q / [(mass) (Tfinal-Tinitial)] This can then be rearranged to solve for the heat transferred. q = Cs (mass) (Tfinal-Tinitial) Enthalpy of Fusion (Melting) Enthalpy of Fusion is defined as the heat that is absorbed when the melting occurs at constant pressure. If the substance freezes, the reaction is reversed, and an equal amount of heat is given off to the surroundings; i.e., ΔHfreez = - ΔHfus solid liquid Melting (fusion) is an endothermic process H fus H m (liquid ) H m ( solid ) Calorimetry A calorimeter can be created by doing something as simple as inserting one Styrofoam cup inside another. Science of measuring heat based on observing the temperature change when a body absorbs or loses energy as heat. Calorimetry A Calorimeter may be used to determine the Heat Capacity, Cs, of a material by measuring the temperature change when a known mass of the material at a higher temperature is placed in a known mass of water, usually at room temperature, and the system is allowed to reach a final intermediate temperature. Heat lost by hot object = Heat gained by cold water Csmaterial(mass)material(Tfinal-Tinitial)material = Cswater(mass)water(Tfinal-Tinitial)water Note: The heat capacity is related to the atomic mass and the intermolecular forces in the material. Calorimetry A Calorimeter may be used in a similar manner to determine the enthalpy change associated with other processes, such as: Chemical reactions* (bond energies) Phase changes* (intermolecular forces) Mixing (intermolecular forces) Solvation (intermolecular forces) *These are the processes you will be learning today. A Bomb Calorimeter is used to determine the caloric value of food and of fuels, by burning them in excess oxygen and measuring the amount of heat evolved. A basic combustion reaction: CxHy + O2(excess) --> x CO2 + y/2 H2O + heat The Computer Display Setup for the Experiments 50 Temperature (oC) 40 30 20 10 0 100 200 300 400 500 600 700 800 900 1000 Time (seconds) Parameters: Temperature: 10-50 oC Time: 0-1000 seconds (Check: Probe should display 15-25 oC resting on lab bench and should read higher when warmed by hand.) The Heat of Neutralization Experiments 50 HCl (or acetic acid) and NaOH mixed, reaction begins Temperature (oC) 40 30 Reaction is completed, heat released, begin slow cooling to ambient 20 10 0 100 200 300 400 500 600 700 800 900 1000 Time (seconds) Temperature change is important. Exact time is not important. Temperature will drift toward ambient before and after reaction Transition will be faster if NaOH is added rapidly and well stirred. (That is you will have a more nearly vertical temp. rise) The Heat of Fusion Experiment 50 Temperature (oC) 40 30 Melting complete, begin slow warming Ice cube added 20 10 0 100 200 300 400 500 600 700 800 900 1000 Time (seconds) IMPORTANT: Use only 1 ice cube, the entire cube must melt. Checkout 1-Calorimeter – Return to stockroom. 1-styrofoam cup – Return to stockroom. Reagents in Lab _____M HCl (record) _____M CH3CO2H (record) _____M NaOH (record) Important: Use distilled water from carboys*, NOT from the tap. (*Distilled water from the tap is normally not at room temp.) Hazards HCl, strong acid, corrosive CH3CO2H, weak acid, corrosive (neutralize acid spills with solid NaHCO3) NaOH, strong base, pH>14, corrosive Waste Liquid waste labeled “Calorimetry” or “Heat of Neutralization”’ For October 18-21 *Thermochemistry pp 9, 11, 13, & 17 and a calculations page are due. *Read over “Radiochemistry” pp 19-30 & remember to bring your student id.