Module No. 5 Energy Relationships in Chemical Reactions Energy the capacity to do work or to transfer heat Forms of Energy 1.

. Kinetic energy 2. Thermal energy 3. Potential energy 4. Radiant energy 5. Chemical energy

Heat the transfer of thermal energy between two bodies that are at different temperature Thermochemistry the study of heat change in chemical reactions System part of the universe set aside for study Surroundings part of the universe outside the system Types of systems 1. Open system can exchange mass and energy usually in the form of heat with its Surroundings ex. tree 2. Closed system allows transfer of energy but not mass ex. steel 3. Isolated system does not allow the transfer of either mass or energy ex. Coleman jug Types of energy or heat transfer 1. Exothermic process gives off heat to its surroundings 2H2(g) + O2(g) 2H2O(l) + energy 2. Endothermic process absorbs heat from its surroundings Energy + 2HgO(s) 2Hg(l) + O2(g)

Thermodynamics - study of the interconversion of heat and other kinds of energy Thermodynamic state of a system defined by a set of condition that completely specifies all the properties of the system, such as temperature, pressure, composition (identity and amount) and physical state (gas, liquid, solid) State Function depends only on the state of the system and not on the way in which it came to be in that state (P,V, T). A change in a state function describes a difference between two states. It is independent of the process or pathway by which the change occurs. X = Xfinal - Xinitial The First Law of Thermodynamics 1. Energy can be converted from one form to another but cannot be created or destroyed. 2. The total energy of the isolated system is constant. 3. The sum of all energy changes for all system participating in a process must be zero. __________________________________________________________________ Module 5: Thermochemistry Page 1 of 8

Mathematical Statement: Energy of the system +

Energy of the surroundings = 0

Internal Energy (E) the total energy of the system due to potential and kinetic energies E = Efinal - Einitial Eststem + Esurroundings = o Esystem = -Esurroundings The change in internal energy (E) is determined by the heat flow (q) and the work (w).

E = q + w
Sign Conventions for Work and Heat Process Work done by the system on the surroundings Work done on the system by the surroundings Heat absorbed by the system from the surroundings Heat absorbed by the surroundings from the system Sign + +

Practice Exercise 6.1: The work done when a gas is compressed in a cylinder is 462J. During the process, there is a heat transfer of 128J from the gas to the surroundings. Calculate the energy change for this process. In most chemical and physical changes, the only kind of work is pressure-volume work. For gas expansion against a constant external pressure, p p V gas

W = - PV

Practice Exercise 6.2: A sample of gas expands by 22.4L against an average pressure of 2.5atm. How much work (kJ) is done in the process? Is the work done by the system or by the surrounding?

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Special Cases of Processes 1. Constant Volume Process V = 0 Therefore: E = qv 2.

PV = 0

Constant Pressure Process E = q + w E = qp - PV qp = E + PV

Enthalphy (H) the sum of internal energy and work H = E + PV H = E + (PV) At constant pressure,

H = E + PV
Enthalphy of Reactions For any reaction of the type:

Reactants Products, H = H (products) H (reactants)

A thermochemical equation expresses the following: 1. Weight relationships 2. Physical states of reactant and products 3. Temperature 4. Pressure 5. Heat evolved or absorbed in the reaction Characteristics of Hrxn 1. For any reaction, Hrxn = H (products) H (reactants). 2. It depends on the state of the substance. H2(g) + O2(g) H2O(l) Hrxn = -285.8 kJ H2(g) + O2(g) H2O(g) Hrxn = -241.8 kJ It is proportional to the amount of reactants and products. H2(g) + O2(g) H2O(l) Hrxn = -285.8 kJ 2H2(g) + O2(g) 2H2O(l) Hrxn = -571.6 kJ It changes sign when a process is reverse. H2O(l) H2(g) + O2(g) H = +285.8 kJ

3.

4.

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Practice Exercise 6.3: Calculate the heat involved when 74.6g of SO2 (molar mass = 64.07g/mol) is converted to SO3. SO2(g) + O2(g) SO3(g) H = -99.1kJ/mol Comparison of H and E E = H - PV

For the process involving gases, from the ideal gas law equation: PV = nRT PV = nRT

E = H - nRT

where n = no. of moles of gases in the products no. of moles of gases in the reactants R = 8.314 J/mol-K Practice Exercise 6.4: Calculate the change in internal energy when 2 moles of CO are converted to 2 moles of CO2 at 1 atm and 25oC. 2CO(g) + O2(g) 2CO2(g) H = -566.0kJ/mol Calorimetry - experimental techniques of determining the amount of energy (heat) associated with any chemical or physical processes; based on observing the temperature change when a system absorbs or releases energy in the form of heat. Specific heat of a substance, s amount of heat required to raise the temperature of one gram of the substance one degree Celsius (or one Kelvin) with no change in phase. It has a unit J/g-oC. For water: S = 4.186 J/g-oC Heat capacity of a body, C the amount of heat required to raise its temperature 1oC. Its unit is J/oC.

C = ms

where m = mass of substance in grams Calculating heat change

q = mst
where t = tfinal - tinitial

q = Ct

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Practice Exercise 6.6: A 466g sample of water is heated from 8.50oC to 74.60oC. Calculate the amount of heat absorbed (in kilojoules) by the water. Calorimeter - apparatus used to determine the heat of reaction TYPES OF CALORIMETER 1. Constant-Volume Calorimeter used to determine the heat of combustion

where Ccal = heat capacity of calorimeter t = change in temperature Practice Exercise 6.7: A quantity of 1.435g of naphthalene C10H8, a pungent-smelling used in moth repellants, was burned in a constant-volume bomb calorimeter. Consequently, the temperature of the water rose from 20.28oC to 25.95oC. If the heat capacity of the bomb plus water was 10.17kJ/oC, calculate the heat combustion of naphthalene on a molar basis; that is, find the molar heat of combustion. (molar mass of C10H8 = 128.2g)

qcal + qrxn = 0 qrxn = - qcal qcal = Ccalt

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2. Constant-Pressure Calorimeter used to measure qP for reactions in solution at constant pressure

Practice Exercise 6.8: A quantity of 100 mL of 0.5M HCl was mixed with 100 mL of 0.5M NaOH in a constant-pressure calorimeter of negligible heat capacity. The initial temperature of the HCl and NaOH solutions was the same, 22.5oC, and the final temperature of the mixed solution was 25.86oC. Calculate the heat change for the neutralization reaction on a molar basis. NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) Assume that the densities and specific heats of the solutions are the same as for water (1.00g/mL and 4.186J/g oC respectively). The thermodynamic standard state of a substance is its most stable pure form under standard pressure (1 atm) and some specific temperature (25oC or 298 K unless specified). Standard molar enthalphies of formation, Hfo - energy released or absorbed when one mole of a compound is formed from its elements For elements and diatomic elements such as H2, N2, O2, Cl2, F2, and Br2: Hfo = 0. Standard enthalpy of reaction, Hrxno - energy released or absorbed as a result of the complete chemical reaction of the reactants

Hrxno = Hfo (products) - Hfo (reactants)

The Direct Method Use of table of Standard Enthalphies of Formation to calculate enthalphies of reactions. Hrxno = Hfo (products) - Hfo (reactants)

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Practice Exercise 6.9: Calculate the standard heat of reactions, Hrxno, for the following using standard heat of formation data. a. CaCO3(s) CaO(s) + CO2(g) b. 2NO(g) + O3(g) NO2(g) + O2(g) The Indirect Method Based on Hesss Law of heat summation which states that: When a reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps. Practice Exercise 6.10: Given the following thermochemical equations: 4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l) Hrxno=-1531kJ N2O(g) + H2(g) N2(g) + H2O (l) Hrxno=-367.4kJ H2(g) + O2(g) H2O(l) Hrxno=-285.9kJ Calculate the value of Hrxno for the reaction 2NH3(g) + 3N2O(g) 4N2(g) + 3H2O(l)

Standard Enthalphies of Formation Compound AgBr(s) AgCl(s) AgI(s) Ag2O(s) Ag2S(s) Al2O3(s) BaCl2(s) BaCO3(s) BaO(s) BaSO4(s) CaCl2(s) CaCO3 CaO(s) Ca(OH)2(s) CaSO4(s) CCl4(l) CH4(g) CHCl3(l) CH3OH(l) -99.5 -127.0 -62.4 -30.6 -31.8 -1669.8 -860.1 -1218.8 -558.1 -1465.2 -795.0 -1207.0 -635.5 -986.6 -1432.7 -139.5 -74.8 -131.8 -238.6 Hf (kJ/mol) Compound C2H2(g) C2H4(g) C2H6(g) C3H8(g) n-C4H10(g) n-C5H12(l) C2H5OH(l) CoO(s) Cr2O3(s) CuO(s) Cu2O(s) CuS(s) CuSO4(s) Fe2O3(s) Fe3O4(s) HBr(g) HCl(g) HF(g) HI(g) Hf (kJ/mol) +226.7 +52.3 -84.7 -103.8 -124.7 -173.1 -277.6 -239.3 -1128.4 -155.2 -166.7 -48.5 -769.9 -822.2 -1120.9 -36.2 -92.3 -268.6 +25.9

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CO(g) CO2(g) H2O(l) H2O2(l) H2S(g) H2SO4(l) HgO(s) HgS(s) KBr(s) KCl(s) KClO3(s) KF(s) MgCl2(s) MgCO3(s) MgO(s) Mg(OH)2(s) MgSO4(s) MnO(s) MnO2(s) NaCl(s) NaF(s) NaOH(s) NH3(g)

-110.5 -393.5 -285.8 -187.6 -20.1 -811.3 -90.7 -58.2 -392.2 -435.9 -391.4 -562.6 -641.8 -1113 -601.8 -924.7 -1278.2 -384.9 -519.7 -411.0 -569.0 -426.7 -46.2

HNO3(l) H2O(g) NH4Cl(s) NH4NO3(s) NO(g) NO2(g) NiO(s) PbBr2(s) PbCl2(s) PbO(s) PbO2(s) Pb3O4(s) PCl3(g) PCl5(g) SiO2(s) SnCl2(s) SnCl4(l) SnO(s) SnO2(s) SO2(g) So3(g) ZnO(s) ZnS(s)

-173.2 -241.8 -315.4 -365.1 +90.4 +33.9 -244.3 -277.0 -359.2 -217.9 -276.6 -734.7 -306.4 -398.9 -859.4 -349.8 -545.2 -286.2 -580.7 -296.1 -395.2 -348.0 -202.9

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