THERMOCHEMISTRY Thermodynamics the study of energy and its transformations.

. Thermochemistry a branch of thermodynamics which concerns with the measurement, analysis & interpretation of heat that is involved in physical & chemical reactions. Energy - ability to do work or to transfer heat. - unit is Joule (J) 1 J = 1 kg-m2/s2 1 calorie = 4.184 J Work, W - the movement of an object against some force. - directed energy change resulting from a process. - 1 L-atm = 101.32 J Consider a cylinder with a movable piston, W = -P V * compression of gas

- the flow of energy from a body at higher temperature to one at a lower temperature when they are placed in thermal contact. System - the portion of the universe selected for a thermodynamic study. Surroundings - any part of the universe outside the system. surroundings boundary Types of Systems: type can exchange mass & energy with its open surroundings can exchange only energy with its surroundings but not mass cannot exchange mass & energy with its surroundings

system

example glass w/ water, tree

closed

thermometer

force

isolated gas Vi h

styrofor ice box

Vf Vi > Vf V = Vf Vi = (-) negative W = -PV = (+) positive *If work done on the system, W is positive * expansion of gas h force gas

Sign Convention for Heat & Work: W (+)

q (+)

system system

q (-) W (-)

Endothermic process - a process at which heat is absorbed or en ters the system Vf Vi < Vf V = Vf Vi = (+) positive W = -PV = (-) negative *If work done by the system, W is negative Heat, q
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Vi

Exothermic process - a process at which heat is released or ex its the system Internal Energy, E - the total energy possessed by a system - the change in internal energy, E can be also defined as: E = q + w. Enthalpy, H
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- a quantity defined as the sum of internal energy, E and PV. (H = E + PV) note: H = q enthalpy (as well as internal energy) cannot be measured directly, but it is actually the change in internal energy, H which can be measured. H = E + PV

E + PV = q P recall: E + PV = H P

Isothermal Process (temperature is constant) E = q + w E = 0 (for constant temp. process) 0=q+w q = -w Adiabatic Process (no heat enters or leaves the system) E = q + w q = 0 for adiabatic process E = w Exercises: A. Determine whether the following are open, closed or isolated system 1. coleman water jug 2. pressure cooker in use 3. burning wood 4. rice cooker in use 5. flat iron 6. student inside a classroom B. For the following processes, calculate the change in internal energy of the system & determine whether the process is endothermic or exothermic: 1. A balloon is heated by adding 670 J of heat. It expands, doing 332 J of work on the atmosphere. 2. A chemical reaction releases 8.65 kJ of heat & does no work on the surroundings C. The E of the system is 45 J. If 105 J of heat is being released, calculate w. Is the work done on or done by the system.

for processes involving solids and liquids: H = E - since the volumes of solids & liquids does not change significantly in the process for process involving gases: using ideal gas equation, PV = nRT PV = nRT H = E + nRT where n = # moles of gaseous products - # moles of gaseous reactants. State & Path Functions State Functions - are properties that are determined by the state of the system, regardless of how that condition was achieved. - the change in the magnitude of the state function depends only on the initial & final states of the system & not on how the change is accomplished. - examples are energy, pressure, volume, temperature & enthalpy Path Functions - properties that are determined via how the conditions are achieved - examples are work & heat First Law of Thermodynamics energy can be transformed from one form to another, but cannot be created or destroyed energy in the universe is constant qsys + qsurr = 0 qsys = -qsurr Isometric/Isochoric Process (volume is constant) E = q + w W = -PV -P V = 0 (since no change in volume) W = 0 E = q Isobaric Process (pressure is constant) E = q + w W = -PV -P E = q + (-PV) (-P

Calorimetry - the measurement of heat flow or heat changes as a result of a chemical reaction. - the apparatus used to measure heat flow is called calorimeter. Types of Calorimeter: 1. Bomb Calorimeter- a device used to measure the heat of combustion. A bomb calorimeter is considered a constant volume system. 2. Open-type Calorimeter- a device used to determine heat changes for non-combustion reactions (e.g. heat of solution, heat of neutralization, heat of dilution) - an open-type calorimeter is considered as a constant pressure system Specific Heat & Heat Capacity

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Specific Heat, S - amount of heat required to raise the temperature of one gram of a substance by one degree Celsius. - unit is J/gC J/g - the specific heat capacity of water is 4.184 J/gC J/g - if the amount of substance is one mole, it is called molar heat capacity Heat Capacity, C - the amount of heat required to raise the temperature of a given quantity of a substance by one degree Celsius. - unit is J/C J/ Measuring Heat Change C = mS q = mS t q = Ct where t = tfinal tinitial (change in temperature) Exercises: 1. A piece of silver of mass 362 g has a heat capacity of 85.7 J/C. What is the specific heat of silver. J/ 2. A 6.22 kg piece of Cu metal is heated from 20.5 C to 324.3 C. Calculate the heat absorbed by the metal. (SCu = 0.385 J/gC) J/g 3. Calculate the amount of heat liberated (in kJ) from 366 g of mercury when it cools from 77.0 C to 12.0 C. (SHg = J/gC) J/g Constant Volume Calorimetry - the device used is the bomb calorimeter qsys = qwater + qbomb + qrxn but qcal = qwater + qbomb qsys = qcal + qrxn qsys = 0 (since adiabatic) 0 = qcal + qrxn q rxn = -q cal q cal = C cal t where: Ccal heat capacity of calorimeter t change. in temperature Exercises: 1. A quantity of 1.922 g of methanol (CH3OH) was burned in a constant volume bomb calorimeter. Consequently, the temperature of the H2O rose by 4.20C. If the quantity of H2O surrounding the 4.20 calorimeter was exactly 2000.0 g and the heat capacity of the calorimeter was 2.02 kJ/C, calculate kJ/ the molar heat of combustion of methanol. 2. The combustion of 1.01 grams of sucrose, C12H22O11, in a bomb calorimeter causes the water temperature to rise from 24.92 to 28.33 oC. The heat capacity of
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the calorimeter assembly is 4.90 kJ/oC. What is the molar heat of combustion of sucrose? 3. A 1.567 gram sample of naphthalene, C10H8(s), is completely burned in a bomb calorimeter assembly and a temperature increase of 8.37 oC is noted. When a 1.227-gram sample of thymol, C10H14O(s), is burned in the same calorimeter assembly, the temperature increase is 6.12oC. If the heat of combustion of naphthalene is 5153.9 kJ/mole C10H8, what is the heat of combustion of thymol? Constant Pressure Calorimetry - the most common device used is the coffee-cup calorimeter qsys = qrxn + qmix + qcal qsys = 0 (since adiabatic) 0 = q rxn + q mix + q cal where: qmix is the heat of the mixture qrxn can be qneut, qdil, qsoln, etc.. qmix = mmixSmixt qcal = Ccalt qrxn = -qmix qcal = - m mix S mix t - C cal t

q rxn

Exercises: 1. A quantity of 100 mL of 0.500 M HCl is mixed with 100 mL of 0.500 M NaOH in a constant pressure calorimeter that has a heat capacity of 335 J/C. The J/ initial temperature of the HCl and NaOH solution is the same, 22.50 C, and the final temperature of the mixed solution is 24.90 C. Calculate the heat change for the neutralization reaction: NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) Assume that the densities and specific heats of the solutions are the same as for water (1.00 g/mL & 4.184 J/gC, respectively). J/g 2. When 50.0 mL of 0.100 M AgNO3 and 50.0 mL of 0.100 M HCl are mixed in a constant pressure calorimeter ( C = 335 J/oC), the temperature of the mixture increases from 22.30C to 23.11C. The 22.30 23.11 temperature increase is caused by this reaction: AgNO2(aq) + HCl(aq) AgCl(s) + HNO3(aq) Calculate H for this reaction, assuming that the combined solution has a mass of 100.0 g and a specific heat capacity of 4.184 J/gC. J/g

Thermochemical Equations - a balanced chemical equation that shows the associated enthalpy change. ex: 2H2(g) + O2(g) 2H2O(g) H = -483.6 kJ

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Enthalpy of Formation (or heat of formation), H f - energy released or absorbed when 1 mole of a compound is formed from its elements. ex: N2(g) + 3H2(g) NH3(g) Hf = -46.19 kJ Enthalpy of Reaction (or heat of reaction), H r - energy released or absorbed as a result of a certain reaction Hr = Hf products - Hf reactants Standard State of A Substance - pure form of a substance at atmospheric pressure (1 atm) and temperature of 25 C. Standard Enthalpy of Reaction, H r - is the enthalpy change when all reactants & products are in their standard states. The superscript indicates standard state conditions. Guidelines in Using Thermochemical Equations: 1. Enthalpy is an extensive property - H is dependent on the amount of reactant consumed in the process. ex: CH4(g) + 2O2(g) CO2(g) + 2H2O(l) H = -890 kJ 2CH4(g) + 4O2(g) 2CO2(g) + 4H2O(l) H = -1780 kJ 2. The change in enthalpy of a reaction is equal in magnitude but opposite in sign when the reaction is reversed. ex: SO3(g) + H2O(l) H2SO4(l) Hr = -130.2 kJ H2SO4(l) SO3(g) + H2O(l) Hr = 130.2 kJ 3. The enthalpy change for a reaction depends on the state of the reactants & products. ex: CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Hr = -890 kJ CH4(g) + 2O2(g) CO2(g) + 2H2O(g) Hr = -802 kJ Measuring H Direct Method Hr = nHf(prod) -nHf(react) - Exercises: 1. Calculate Hr for the following: a. C6H6(l) + 15/2O2(g) 6CO2(g) + 3H2O(l) b. NH3(g) + HCl(g) NH4Cl(s) c. 2H2S(g) + 3O2(g) 2H2O(l) + 2SO2(g) 2. Calculate the heat of formation of OSCl2(l) in the following reaction: OSCl2(l) + H2O(l) SO2(g) + 2HCl(g) Hr = 10.3 kJ
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Hesss Law (Indirect Method) - if a reaction is carried out in a series of steps, H for the reaction will be equal to the sum of the enthalpy changes for the individual steps. S(s) + O2(g) SO2(g) SO2(g) + O2(g) SO3(g) SO3(g) + H2O(l) H2SO4(l) Hr = -296.9 kJ Hr = -98.3 kJ Hr = -130.2 kJ

Net rxn : S(s) + 3/2O2(g) + H2O(l) H2SO4(l) Hr = (-296.9)+(-98.3)+(-130.2) H r = -525.4 kJ Exercises: 1. Given the following thermochemical equations: H2S(g) + 3/2O2 H2O(l) + SO2(g) Hr = -562.6 kJ CS2(l) + 3O2(g) CO2(g) + 2SO2(g)Hr = -1075.2 kJ Calculate the value of Hr for the reaction: CS2(l) + 2H2O(l) CO2(g) + 2H2S(g) 2. Given the following thermochemical equations: 4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l) Hr=-1531 kJ N2O(g) + H2(g) N2(g) + H2O(l) Hr=-367.4 kJ H2(g) + O2(g) H2O(l) Hr=-285.9 kJ Calculate the value of Hr for the reaction: H 2NH3(g) + 3N2O(g) 4N2(g) + 3H2O(l)

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Heat of Formations of different substances at 25 o C:

Substance Ag(s) AgBr(s) AgCl(s) AgI(s) Ag2O(s) Al(s) Al2O3(s) BaCl2(s) BaCO3(s) BaO(s) BaSO4(s) C(graphite) CCl4(l) CF4(g) CH4(g) C2H2(g) C2H4(g) C2H6(g) C6H6(l) CH3COOH(l) CH3Cl(g) CHCl3(l) CH3NH2(g) CH3OH(g) CH3OH(l) C2H5OH(l) CO(g) CO2(g) COCl2(g) KCl(s) KClO3(s) KF(s) KNO3(s) Li2CO3(s) LiOH(s) MgCl2(s) MgCO3(s) MgO(s) Mg(OH)2(s) MnO(s) MnO2(s) NH3(g) NH4Cl(s) NO(g) NO2(g) N2O(g) N2O4(g) NOCl(g) NaCl(s) Na2CO3(s) NaF(s) NaHCO3(s) NaNO(s) NaOH(s)
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H f (kJ/mole) 0 -99.50 -127.0 -62.38 -30.6 0 -1669.8 -860.06 -1218.8 -588.1 -1465.2 0 -139.3 -679.9 -74.85 +226.7 +52.3 -84.68 +49.04 -487.0 -82.0 -132.0 -28.0 -201.2 -238.6 -277.63 -110.5 -393.5 -223.0 -435.89 -391.2 -562.6 -492.7 -1215.6 -487.2 -641.8 -1113.0 -601.8 -924.7 -384.9 +520.9 -46.19 -315.4 +90.36 +33.8 +81.55 +9.67 +52.59 -411.0 -1130.9 -569.0 -947.7 -424.8 -426.7

Substance PH3(g) POCl3(l) CS2(l) Ca(s) CaCl2(s) CaCO3(s) CaO(s) Ca(OH)2(s) CaSO4(s) Cl2(g) Cr2O3(s) CuO(s) Cu2O(s) CuS(s) CuSO4(s) FeO(s) Fe2O3(s) Fe3O4(s) HBr(g) HCl(g) HCN(g) HF(g) HI(g) HNO3(l) H2O(g) H2O(l) H2S(g) H2SO4(l) HgO(s) HgS(s) KBr(s) PbBr2(s) PbCl2(s) PbCO3(s) PbO(s) PbO2(s) Pb3O4(s) SO2(g) SO3(s) SiCl4(g) SiF4(g) SiO2(s) SnCl4(l) SnO(s) SnO2(s) ZnO(s) ZnS(s) ZnSO4(s) CF4(g) N2H4(l)

H f (kJ/mole) +9.25 -592.0 +87.86 0 -795.0 -1206.9 -635.5 986.59 -1432.7 0 -1128.4 -155.2 -166.7 -48.5 -769.9 -271.9 -822.2 -1117.1 -36.2 +92.3 +130.5 -269 +25.9 -173.2 -241.8 -285.9 -20.2 -811.32 -90.7 -58.16 -392.2 -277.0 -359.2 -700.0 -217.9 -276.6 -918.4 -296.9 -395.2 -640.2 -1548.0 -859.4 -545.2 -286.2 -580.7 -348.0 -202.9 -978.6 +1.88 +50.63

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NiO(s) PCl3(g) PCl5(g)

-244.3 -306.4 -398.9

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