STKK

1032 General Chemistry Practical

Experiment 4
Heats of Reaction Hesss Law
Introduction Heat is associated with nearly all chemical reactions. In such instances, the reaction either liberates heat (exothermic) or absorbs heat (endothermic). When a reaction is carried out under constant pressure (as in an open beaker), the heat associated with the reaction is known as enthalpy. The symbol of enthalpy is H. It is most often too difficult to directly measure the enthalpy change for a reaction. What can be done is to measure the heat change that occurs in the surroundings by monitoring temperature changes. Conducting a reaction between two substances in aqueous solution, allows the enthalpy of the reaction to be indirectly calculated with the following equation : q = Cp m T The term q represents the heat energy that is gained or lost. Cp is the specific heat of water, m is the mass of the water, and T is the temperature change of the reaction mixture. The specific heat and mass of water are used because water will either gain or loss heat energy in a reaction that occurs in aqueous solution. Hesss Law Germain Hess (1802 1850) discovered the principle of how the enthalpy value for a given reaction can be calculated from the enthalpy values of other reactions. This principle (Hesss law) states that the enthalpy change for a reaction depends on the products and reactants and is independent of the pathway or the number of steps between reactants and products. In other words, if a reaction is carried out in a series of steps, the enthalpy (H) for the reaction will be equal to the sum of the enthalpy changes for the individual steps. Therefore, the enthalpy change for a given reaction is calculated by adding the individual chemical equations and taking the sum of the enthalpy changes associated with each of these individual chemical equations. Sample Hesss Law Problem Use the thermochemical equations given below to calculate the enthalpy change for the following reaction. N2O4(g) 2NO2(g) H =? N2(g) + 2O2(g) 2NO2(g) H = +66.36 kJ (1) N2(g) + 2O2(g) N2O4(g) H = +9.16 kJ (2) N2O4(g) N2(g) + 2O2(g) H= 9.16 kJ N2(g) + 2O2(g) 2NO2(g) H = +66.36 kJ N2O4(g) 2NO2(g) H = +57.2 kJ

 STKK 1032 General Chemistry Practical Objectives In this experiment, the temperature change of two reactions will be measured, and Hesss law will be used to determine the enthalpy change, H of a third reaction. You will use a simple Styrofoam calorimeter to measure the heats of reaction for the following three reactions: You will Reaction Reaction Equation determine 1 NaOH(s) Na+(aq) + OH-(aq) Solid NaOH is dissolved in water Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) Na+(aq) + Cl-(aq) + H2O(l) Solutions of NaOH and HCl are equally mixed NaOH(s) + H+(aq) + Cl-(aq) Na+(aq) + Cl-(aq) + H2O(l) Solid NaOH is dissolved in a HCl solution H1 H2 H3

The third reaction is actually a combination of the first two reactions. Notice that the equation for reaction 3 can be obtained by adding together reactions 1 and 2. By calculating the heats of reaction for all three reactions you will be attempting to verify Hesss Law:

Safety precaution must be strictly followed. If you are unable to actually perform the experiment, use the following set of experiment data to plot the graphs and answer the questions at the end of the lab session. Materials and Methods Your demonstrator will provide you with a list of the materials and equipment required for this lab, and the procedures to follow. Procedure: i. Reaction 1 NaOH(s) Na+(aq) + OH-(aq) 2.0 g of solid NaOH is dissolved in 100 mL of water. The initial and final temperatures are measured and recorded. The heat of solution is calculated (H1). ii. Reaction 2 Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) Na+(aq) + Cl-(aq) + H2O(l)

H3 = H1 + H2

 STKK 1032 General Chemistry Practical 50 mL of 1.0 M hydrochloric acid solution is mixed with 50 mL of 1.0 M sodium hydroxide solution. The initial and final temperatures are recorded, and the heat of the reaction is calculated (H2). iii. Reaction 3 NaOH(s) + H+(aq) + Cl-(aq) Na+(aq) + Cl-(aq) + H2O(l) 2.0 g of solid NaOH is dissolved in 200 mL of 0.50 M HCl. The heat of reaction is calculated (H3). Data Analysis and Calculations Record your calculations in Table 2. Step 1. Calculate the mass of reaction mixture for each reaction. We will assume that the density of the solutions (the HCl and NaOH solutions) have the same density as pure water, 1.0 g/mL. Thus, 100.0 mL will have a mass of 100.0 g. Reaction 1: Add the mass of water used + mass NaOH. Reaction 2: The volume of HCl used will be numerically equivalent to its mass, expressed in grams. Add mass NaOH + mass HCl. Reaction 3: Add the masses of the two solutions: mass NaOH + mass HCl. Step 2. Calculate the change in temperature for each of reactions. Steps 3 6. Calculate the amount of heat released, in kJ, during each of the reactions, using the same equation as mentioned above: q = Cp m T Steps 7 9. These steps convert mass or volume of materials used into moles. To convert mass of a solid into moles: 3

 STKK 1032 General Chemistry Practical

moles =

mass MolecularWeight

To convert the volume of a solution into moles: a. The unit for concentration of solutions is M, which represents mol/L. b. moles = Volume of solution (in L) concentration (in mol/L) For example: If 55.0 mL of a 1.0 M NaOH solution is used, then mol = (0.055 L) (1.0 mol/L) = 0.055 mol Step 10. Calculate the heat of reaction per mole of NaOH by dividing the heat released (your answer to Step 6) by moles NaOH used (answer to step 9). Questions and Conclusions 1. Show that adding together the equations for Reaction 1 and Reaction 2 produce the equation for Reaction 3. 2. Calculate the sum of H1 and H2. How does this compare with the experimentally determined value for H3? 3. Calculate the percent difference between H3 and (H1 + H2). 4. Percent Difference =
H 3 ( H1 + H 2 ) 100 H 3

For the decomposition of hydrogen peroxide, it is known that H2O2(l) H2O(l) + 1/2 O2(g); H = -98.2 kJ Using this information, determine H for the reaction: 2 H2O(l) + O2(g) 2 H2O2(l)

5. What is the value for H for the following reaction? CS2(l) + 2 O2(g) CO2(g) + 2 SO2(g) Given: C(s) + O2(g) CO2(g); Hf = -393.5 kJ/mol S(s) + O2(g) SO2(g); Hf = -296.8 kJ/mol C(s) + 2 S(s) CS2(l); Hf = 87.9 kJ/mol

 STKK 1032 General Chemistry Practical Table 1A. Data recording sheet for Reactions 1 and 3 Reaction 1 NaOH (s) Na+ + OH- Reaction 3 NaOH (s) + H+ + Cl- Na+ + Cl- + H2O

Volume H2O or HCl used (mL) Mass of solid + container (g) Mass of empty container (g) Mass of solid used (g) Initial water/HCl temperature (C) water/HCl temperature Final (C) in temperature, T (C) Change Table 1B. Data recording sheet for Reaction 2. Reaction 2 Na+ + OH- + H+ + Cl- Na+ + Cl- + H2O Volume NaOH solution (mL) Volume HCl solution (mL) Total solution volume (mL) Initial temperature HCl solution (C) Initial temperature NaOH solution (C) Average temperature (C) Final temperature of mixture (C) Change in temperature, T (C)

 STKK 1032 General Chemistry Practical Sample Data Use the following sample data if you are not able to perform the experiment. Table 1A. Data recording sheet for Reactions 1 and 3 Reaction 1 Reaction 3 + + OH- NaOH (s) Na NaOH (s) + H+ + Cl- Na+ + Cl- + H2O Volume H2O or HCl used (mL) Mass of solid + container (g) Mass of empty container (g) Mass of solid used (g) Initial water/HCl temperature (C) Final water/HCl temperature (C) Change in temperature, T (C) Table 1B. 98.2 3.58 1.60 18.6 21.2 96.6 3.65 1.60 19.0 25.2

Data recording sheet for Reaction 2. Reaction 2 Na+ + OH- + H+ + Cl- Na+ + Cl- + H2O 48.6 47.8 18.8 18.4 22.0

Volume NaOH solution (mL) Volume HCl solution (mL) Total solution volume (mL) Initial temperature HCl solution (C) Initial temperature NaOH solution (C) Average temperature (C) Final temperature of mixture (C) Change in temperature, (C)

 STKK 1032 General Chemistry Practical Table 2. Calculating Heats of Reaction Steps Reaction 1 NaOH (s) Na+ + OH-

1. Total mass of water or solution used 2. Change in temperature 3. Specific heat of water 4.18 J/g C 4. Energy absorbed/lost by the water (J) (Multiply steps 1 2 3) 5. Energy absorbed/lost by the reaction (J) (same as result for step 4, but opposite sign) 6. Energy absorbed/lost (kJ) (convert answer in step 5 to kilojoules) 7. Rxn 1: Mass of NaOH used (g) Rxn 2: Volume of NaOH used (L) Rxn 3: Mass of NaOH used (g) 8. Rxn 1: Molar mass of NaOH (g/mol) Rxn 2: Concentration of NaOH (aq) (mol/L) Rxn 3: Molar mass of NaOH (g/mol) 9. Moles of NaOH actually used (mol) Rxn 1: moles = (g) / (g/mol) Rxn 2: moles = (L) (mol/L) Rxn 3: moles = (g) / (g/mol) 10. Heat of Reaction H (kJ/mol)

Reaction 2 Na+ + OH- + H+ + Cl- Na+ + Cl- + H2O 4.18 J/g C

Reaction 3 NaOH (s) + H+ + Cl- Na+ + Cl- + H2O 4.18 J/g C

1.0 mol L