Calorimetry Calorimetry is the measurement of the quantity of heat exchanged.

For example, if the energy from an exothermic chemical reaction is absorbed in a container of water, the change in temperature of the water provides a measure of the amount of heat added. Calorimeters are used to determine the energy content of foods by burning the foods in an oxygen atmosphere and measuring the energy yield in terms of the increase in temperature of the calorimeter. Calorimeters can also be used to measure the specific heat of a substance. Significant exchange of heat between the calorimeter and its content cannot be avoided. Thus, it is necessary to determine the heat capacity, C, of the calorimeter before it is used for heat of reaction measurements. The capacity of the calorimeter represents the quantity of heat required to raise the temperature of the device by 1C. *Equations and Problems* Therefore, C= (mass)(specific heat) Since the specific heat of water is 4.14 J/(gC), the heat capacity of 125g of water is: C= (mass)(specific heat) = (125 g) (is 4.14 J/(gC)) = 523 J/C This sample absorbs 523 J of heat for each degree that the temperature increases. Twice this amount of heat would be required to raise the temperature by 2C. In general, q= C (t2-t1) Where q is the heat absorbed by the sample, c, is the heat capacity of the sample, t2 is the final temperature, and t1 is the initial temperature. The heat absorbed by a 125gg sample water when it is heated from 20.0C to 25.00C can be calculated in the ff. way: q= C (t2-t1) = (523 J/C) (25C- 20C) = (523 J/C) (5C) = 2615 J or 2.62 kJ Problem: 1. What is the heat capacity of 325 g of water? 2. The specific heat of lead is 0.129 J/(gC). How many joules of heat is required to raise the temperature of 207g of lead from 22.25 C to 27.65 C? Heat of Reaction Reacting system may either absorb heat or evolve heat during chemical changes. The heat evolved or absorbed may be measured in a calorimeter. A calorimeter is like a thermos bottle. It is thermally insulated from its surroundings. Exothermic change- heat is absorbed by the water molecules thus the temperature rises Endothermic change- a decrease in temperature CaCl2 exothermic change CO (NH2)2- endothermic change Heat of Fusion and Heat of vaporization When a solid, such as ice is heated, the temperature changes as shown in the following graph: Notice that the temperature remains constant while solid is converted to liquid at the melting point. The heat added gives the molecule enough energy to move from solid to liquid state. The quantity of heat absorbed when a specific quantity of the solid is converted to liquid at its melting point is called heat of fusion. The heat of fusion is a properly of a substance. The value for water is 80cal/g at 0C and the value for ethyl alcohol is 26cal/g at its melting point -112C. The temperature also remains constant while the liquid is converted to a gas at the boiling point. The heat added gives the molecules enough energy to move from the liquid to the gas state. The quantity of heat absorbed when a specific quantity of the liquid is converted to gas at the boiling point is called heat of vaporization. The heat of vaporization is a property substance. The value for water is 540 cal/g at 100C and the value for ethyl alcohol is 204cal/g at 78C.

*Equations and Problems* Thermochemical equations Given the following thermochemical equations: 4 NH3 (g) + 3O2 (g) 2N2 (g) + 6 H2O (l) H= - 1531 kJ N2O (g) + H2 (g) N2 (g) + H2O H= - 367.4 kJ H2 (g) + O2 (g) H2O(l) H= -285.9 kJ Find the value of H for the reaction: 2 NH3 (g) + 3 N2O (g) 4N2 (g) + 3 H2O (l) Since the desired equation has 2 mol of NH3 on the left, we divide equation 5.13 by 2 and the H value by 2. We multiply equation 5.14 and the corresponding H value by 3 so that the coefficient of N2O in the final equation will be three. To eliminate the 3H2 added to the left in the last step, we reverse equation 5.15 and multiply it by 3; the corresponding H value is multiplied by 3 and its sign changed: 2 NH3 (g) + 3/2 O2 (g) N2 (g) + 3 H2O (l) H= - 765.5 kJ (5.13) 3 N2O (g) + 3 H2 (g) 3 N2 (g) + 3 H2O H= - 1102.2 kJ (5.14) 3 H2O(l) 3H2 (g) + 3/2 O2 (g) H= + 857.7 kJ (5.15) The equations and H values are added. Terms common to both sides of the final equation (3/2 O2, 2 H2 and 3 H2O) are cancelled: 2NH3 + 3N2O 4 N2 + 3 H2O H = - 1010.0 kJ Problems to solve: 1. Given: (a) H2S + 3/2 O2 H2O + SO2 H= -562.6 kJ (b) CS2 + 3O2 CO2 + 2SO2 H = - 1075.2 kJ Calculate the value of H for the reaction: CS2 + 2H2O CO2 + 2H2S 2. Given: (a) 2NH3 + 3N2O 4N2 + 3H2O H = -1010 kJ (b) 4NH3 + 3O2 2N2 + 6H2O H = -1531 kJ Calculate the value of H for the reaction: N2 + O2 N2O 3. Given: (a) 2NF3 + 2NO N2F4 + 2ONF H= - 82.9 kJ (b) NO + F2 ONF H = -156.9 kJ (c) Cu + F2 CuF2 H = -531.0 kJ Calculate the value of H for the reaction: 2NF3 + Cu N2F4 + CuF2 Oxidation-reduction reactions Oxidation-reduction reactions (or redox) reactions, are a type of reaction in aqueous solutions that involves a transfer of electrons between two species. An oxidation-reduction reaction is any chemical reaction in which the oxidation number of a

molecule, atom, or ion changes by gaining or losing an e-. They occur every day and are vital to some of the basic functions of life. Some examples include photosynthesis (within plants), respiration (within animals), combustion, and corrosion or rusting. To understand these types of reactions, you must first understand oxidation numbers or states. Rules for Assigning Oxidation States The oxidation number corresponds to the number of electrons, e-, that an atom loses, gains, or appears to use when joining with other atoms in compounds. When determining the Oxidation State of an atom there are seven guidelines to follow: 1. The Oxidation State of an individual atom is 0. 2. The total Oxidation State of all atoms in: a neutral species is 0 and in an ion is equal to the ion charge. 3. Group 1 metals have an Oxidation State of +1 and group 2 an Oxidation State of +2 4. The Oxidation State of fluorine is -1, when in compounds 5. Hydrogen generally has an Oxidation State of +1 in compounds 6. Oxygen generally has an Oxidation State of -2 in compounds 7. In binary metal compounds, group 17 elements have an Oxidation State of -1, group 16 of -2, and group 15 of -3. (Note: The sum of the oxidation states is equal to zero for neutral compounds and equal to the charge for polyatomic ion species.) Sample Problems: Determine the oxidation states: 1. Fe(s) + O2(g) Fe2O3(g) 2. Fe2+ 3. Ag(s) + H2S Ag2S(g) + H2(g) Solutions 1. Fe and O2 are free elements, therefore they have an O.S. of "0" according to Rule #1. The product has a total O.S. equal to "0" and following Rule #6, O3 has an O.S. of -2, which means Fe2 has an O.S. of +2. 2. The O.S. of Fe corresponds to its charge, therefore the O.S. is +2. 3. Ag has an O.S. of 0, H2 has an O.S. of +1 according to Rule #5 and S has an O.S. of -2 according to Rule #7. Example 1: Determine the oxidation state of the bold element in each of the following: 1. Na3PO3 2. H2PO4Example 2: Determine which element is oxidized and which element is reduced in the following reactions (be sure to include the oxidation state of each): 1. Zn + 2H+ Zn2+ + H2 2. 2Al + 3Cu2+2Al3+ +3Cu 3. CO32- + 2H+ CO2 + H2O Oxidizing and Reducing Agents An atom is oxidized when it oxidation number increases, the reducing agent, and an atom is reduced when its oxidation number decreases, the oxidizing agent. In other words, what is oxidized is the reducing agent and what is reduced is the oxidizing agent. (Note: the oxidizing and reducing agents can be the same element or compound). Oxidation-Reduction Reactions Redox reactions are comprised of two parts, a reduced half and an oxidized half, that always occur together. The reduced half gains electrons and the oxidation number decreases, while the oxidized half losses electrons and the oxidation number increases. Simple ways to remember this are the mnemonic devices OIL RIG meaning "oxidation is loss" and "reduction is gain" or LEO says GER meaning "loss of e- = oxidation" and "gain of e- = reduced." There is no net change in the number of electrons in a redox reaction. Those given off in the oxidation half reaction are taken on by another species in the reduction half reaction. The two species that exchange electrons in a redox reaction are given special names. The ion or molecule that accepts electrons is called the oxidizing agent; by accepting electrons it brings about the oxidation of another species. Conversely, the species that donates electrons is called the reducing agent; when reaction occurs it reduces the other species. In other words, what is oxidized is the reducing agent and what is reduced is the oxidizing agent. A good example of a redox reaction is the thermite reaction in which iron atoms of ferric oxide lose (or give up) O atoms to Al atoms, producing Al2O3. Fe2O3(s) + 2Al(s) Al2O3(s) + 2Fe (l) Another example of the redox reaction is the reaction between Zinc and Copper sulfate. Example 3. Using the equations from the previous examples determine what is oxidized? 1. Zn + 2H+ Zn2+ + H2 Example 4. What is reduced?

1. Zn + 2H+ Zn2+ + H2 Half Reactions Before one can balance an overall redox equation, one has to be able to balance two half-equations, one for oxidation (electron loss) and one for reduction (electron gain). Collectively, oxidation and reduction are known as redox, or an electron transfer reaction. After balancing the two half-equation one can determine the total net reaction. Each equation is balanced by adjusting coefficients and adding H2O, H+, and e- in this order: 1) Balance the number of atoms of each element. 2) Balance the number of electrons transferred. 3) Balance the total charge on reactants and products (Note: If #1 and #2 are done correctly, #3 will follow. Thus, it serves as a means of checking your work). Electrochemistry The bridge acts as a barrier between the two different electrolytes while allowing the flow of charges. Problems to solve: Predict the ox/rd reaction and ox/rd agent: (a) Zn + Cl2 ZnCl2 Ox rxn: Rd rxn: Ox agent: Rd agent: (b) 2ReCl5 + SbCl3 2ReCl4 + SbCl5 Ox rxn: Rd rxn: Ox agent: Rd agent: (c) Mg + CuCl2 MgCl2 + Cu Ox rxn: Rd rxn: Ox agent: Rd agent: (d) 2NO + O2 2NO2 Ox rxn: Rd rxn: Ox agent: Rd agent: (e) WO3 + 3H2 W + 3H2O Ox rxn: Rd rxn: Ox agent: Rd agent: (f) Cl2 + 2NaBr 2NaCl + Br2 Ox rxn: Rd rxn: Ox agent: Rd agent: (g) Zn + 2HCl ZnCl2 + H2 Ox rxn: Rd rxn: Ox agent:

Rd agent: (h) Fe2O3 + 2Al Al2O3 + 2Fe Ox rxn: Rd rxn: Ox agent: Rd agent: (i) OF2 + H2O O2 + 2 HF Ox rxn: Rd rxn: Ox agent: Rd agent: (j) 2HgO 2 Hg + O2 Ox rxn: Rd rxn: Ox agent: Rd agent: