The Enthalpy of Neutralization of Water

Experimental Problem Determine the enthalpy of neutralization of water. Educational Purpose Experimental Problem Determine the products formed by the decomposition reaction of hydrogen peroxide. To introduce thermodynamic calculations and chemical reactions. Educational Purpose To Logger Pro as a laboratory datareactions. collection method To introduce introduce Vernier stoichiometric calculations and chemical To study regression analysis What To Turn In 1. The prelab and postlab

Background Thermodynamics, or the relation between heat and energy is an extremely old science, dating back to the nineteenth century when in 1824, Carnot published his Reflections on the Motive Power of Fire, which detailed his research and presented a well-reasoned theoretical treatment for the perfect (but unattainable) heat engine, now known as the Carnot cycle This was a few years before Rudolf Clausius who also stated the second law in a paper published in 1854 as, Heat can never pass from a colder to a warmer body without some other change, connected therewith, occurring at the same time The fundamental thermodynamic variables that are measured in the laboratory are the familiar variables of pressure, temperature and volume and from these are calculated through various mathematical manipulations, the thermodynamic functions, energy, E; enthalpy, H; Gibbs free energy, G; and Helmholtz free energy, A. The First Law of Thermodynamics is the law of conservation of energy applied to macroscopic systems and introduces the concepts of work and heat and system and surroundings. Since energy is a state function (i.e. the value of the property is dependent on the initial and final states only), while both work and heat are path functions (i.e. the value of the property is dependent on the path taken to go from the initial to the final state), the function E can be mathematically defined by dU = q + w

where dU is the change in energy of the system when the system undergoes a heat transfer of q units to the system and w units of work are done on the system. Similarly, enthalpy, H can be defined by, dH = dU + PdV where P and V are the usual laboratory variables of pressure and temperature and U has already been defined as the energy. The other thermodynamic variables, the Helmholtz free energy, A, and the Gibbs free energy, G, can be likewise defined in terms of U and H and the laboratory variables of temperature, pressure and volume through the relationships, dA = dU TdS for isothermal processes, where S is the entropy of the system and dG = dH TdS once again restricted to isothermal processes. In the laboratory, temperature changes in chemical reactions are easily measured and have been used extensively to elucidate various thermochemical values. This has been achieved through the use of Hess Law which states that the heat evolved or absorbed in a chemical process is the same whether the process takes place in one or in several steps. This is also known as the law of constant heat summation. To illustrate Hess's law, This example problem demonstrates strategies
and how to use Hess's Law to find the enthalpy change of a reaction using enthapy data from similar reactions. Diagrammatically one can show a set of reactions as below,

0 kJ ------------ C(graphite) + O2 | | -110 kJ | | V | CO + 0.5 O2 ----| | | -393 kJ | | -283 kJ | | | | V V ------------ CO2

For reactions taking place in solution and under laboratory conditions, (Constant P, varying T and V), the basic definitions H involving an energy term dU is not suitable and must be altered so that fundamental properties can be measured. In the chemical environment where one deals with mixing reagents it is volume that is altered and temperature that changes as a consequence of reaction. The variation of H used in this case depends on knowing the heat capacity (Cp)(energy required to raise 1mol of reagent by 10K) of all reagents (reactants and products) involved in the reaction and the equation used is Hrxn = Hprod - Hreact Where H of each individual component is calculated by H = mCp T

Problem: To evaluate the enthalpy of formation of CO

C + O2 -> CO2, dH = -393 kJ/mol 1 CO + /2 O2 -> CO2, dH = -283 kJ/mol.

Subtracting the second equation from the first gives

C + 1/2 O2 -> CO,

dH = -393 -(-283) = -110 kJ/mol

Problem:

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
Solution

Hess's law says the total enthalpy change does not rely on the path taken from beginning to end. Enthalpy can be calculated in one grand step or multiple smaller steps. To solve this type of problem, we need to organize the given chemical reactions where the total effect yields the reaction needed. There are a few rules that must be followed when manipulating a reaction. 1. The reaction can be reversed. This will change the sign of Hf. 2. The reaction can be multiplied by a constant. The value of Hf must be multiplied by the same constant. 3. Any combination of the first two rules may be used. Finding a correct path is different for each Hess's law problem and may require some trial and error. A good place to start is to find one of the reactants or products where there is only one mole in the reaction. We need one CO2 and the first reaction has one CO2 on the product side.

C(s) + O2(g) CO2(g), Hf = -393.5 kJ/mol This gives us the CO2 we need on the product side and one of the O2 moles we need on the reactant side. To get two more O2 moles, use the second equation and multiply it by two. Remember to multiply the Hf by two as well. 2 S(s) + 2 O2(g) 2 SO2(g), Hf = 2(-326.8 kJ/mol) Now we have two extra S and one extra C molecule on the reactant side we don't need. The third reaction also has two S and one C on the reactant side. Reverse this reaction to bring the molecules to the product side. Remember to change the sign on Hf. CS2(l) C(s) + 2 S(s), Hf = -87.9 kJ/mol When all three reactions are added, the extra two sulfur and one extra carbon atoms are cancelled out, leaving the target reaction. All that remains is adding up the values of Hf. H = -393.5 kJ/mol + 2(-296.8 kJ/mol) + (-87.9 kJ/mol) H = -393.5 kJ/mol - 593.6 kJ/mol - 87.9 kJ/mol H = -1075.0 kJ/mol Answer: The change in enthalpy for the reaction is -1075.0 kJ/mol. Problem How much energy must be absorbed by 20.0 g of water to increase its temperature from 283.0 C to 303.0 C? (Cp of H2O = 4.184 J/g C) Solution H = mCp T = 20.0 x 4.184 x (303.0 283.0) = 1673.6 J Problem When 10mL of 1.00M AgNO3 solution is added to 10mL of 1.00M NaCl solution at 250C in a calorimeter, a white precipitate of AgCl forms and the temperature of the aqueous mixture rises to 32.60C. Assuming that the specific heat of the aqueous mixture is 4.18J/g/0C, that the density

of the mixture is 1.00g/mL and that the calorimeter absorbs a negligible amount of heat, calculate H (in kJ) for the reaction. Solution Because the temperature rises in the reaction, heat must be liberated and H must be negative. The amount of heat evolved during the reaction is equal to the amount of heat absorbed by the mixture: Heat evolved = (mass) x (specific heat) x (Temp change) Mass = 20mL x (1.00g/mL) = 20g Specific Heat = 4. 18J/g/0C Temp Change = 32.60C -25.00C = 7.60C Heat Evolved = 20(g) x 4. 18J/g/0C x 7.60C = 6.4 x 102 J According to the balanced equation, the number of moles of AgCl produced equals the number of moles of Ag+ reacted: Moles of Ag+ = (10mL)(1.00mol/1000mL) = 1.00x10-2 mol Ag+ Moles AgCl = 1. 00x10-2 mol AgCl Heat evolved per mole of AgCl = 6.4 x 102 J/ 1. 00x10-2 mol AgCl = 64 kJ/mol AgCl Therefore H = -64kJ

Problem From the equations below derive the enthalpy for the reaction C + 2H2 -> CH4 dHf /(kJ/mol) (1) H2(g) + 0.5 O2(g) -> H2O(l) -285.8 (2) C(graphite) + O2(g) -> CO2(g) -293.5 (3) CH4(g) + 2O2(g) -> CO2(g) + 2H2O(l) -890.4 1. Calculate the enthalpy of the reaction CH4 + 2 O2(g) -> CO2(g) + 2 H2O(g) Use the data from the following reactions

CH4 + 2O2 -> CO2 + 2H2O H2O(l) -> H2O(g)

dHo = -890 kJ/mol dHo = 44 kJ/mol at 298 K

Objective In our experiment we shall use the dHf of the various components present in the reaction mixture in order to compute the heat of neutralization of water. 1. Measure the change in temperature of the reaction between NaOH and HCl 2. Calculate the enthalpy of neutralization of water 3. Compare the calculated value with the accepted value 4. We shall use dHf(NaOH) = -426.7kJ/mol, dHf(HCl) = -92.3kJ/mol, dHfNaCl) = -411.0kJ/mol Procedure: Work in pairs 1. 2. 3. 4. 5. Connect a Temperature probe to Channel 1 of the Vernier computer interface Start the Logger Pro program on your computer. Place a stir plate on the ring stand and plug into the stir function at a low speed. Measure out 50 mL of 0.2M NaOH into the insulated beaker and place on stir plate. Place a clean, dry stir bar into the beaker and make sure that the solution does not splash 6. Suspend the temperature probe from the ring stand, lower into the NaOH solution. CAUTION: do not let the probe touch the stir bar 7. Rinse and then fill a buret with 0.2M HCl and position above the beaker. Conduct the experiment. a. Your monitor should show temperature on the y axis and volume on the xaxis. b. Setup data collection parameters: Goto Experiment Data Collection Mode Time based Duration 350sec Sampling rate 5 seconds per sample. Done c. Click *Collect* to begin the data collection and to obtain the initial temperature of NaOH. d. When the initial temperature is stable, (15 sec, 4 or 5 readings at the same temperature) start adding HCl e. The temperature of the solution will start to rise. f. Add HCl solution 2mL at a time until 50mL have been added. g. After the run is over analyze the data with Analyze i)Find the initial temp of the NaOH solution using the R= function

ii) Take the sloping down portion of the curve and interpolate to the y-axis to find the best final temp. iii) Use these and information given to you to find H for the neutralization of H2O. h. Submit it with your postlab. Make sure that all information is clearly marked, all axes are labeled, the graph is titled and the difference in temperature shown. Postlab 1. What are Ti and Tf for your reaction solutions and what are the R2 values for each? 2. For each run, what is the calculated value of Hneutralization(H2O)? 3. Take the average of the values you have obtained - what is the % error in your value? 4. Calculate H0 for the fermentation of glucose to make ethyl alcohol, the reaction that occurs during the production of alcoholic beverages: C6H12O6(s) 2C5H5OH(l) + 2CO2(g) Using the heats of formation information: H0f(C6H12O6) = -1260 kJ, H0f(C2H5OH) = -277.7kJ , H0f(CO2) = -393.5 kJ